ALBERT

Description: Not all calcite ballast is created equal: differing effects of foraminiferan and coccolith calcite on the formation and sinking of aggregates Biogeosciences Discussions, 10, 14861-14885, 2013 Author(s): K. Schmidt, C. L. De La Rocha, M. Gallinari, and G. Cortese Correlation between particulate organic carbon (POC) and calcium carbonate sinking through the deep ocean has led to the idea that ballast provided by calcium carbonate is important for the export of POC from the surface ocean. While this idea is certainly to some extent true, it is worth considering in more nuance, for example, examining the different effects on the aggregation and sinking of POC of small, non-sinking calcite particles like coccoliths and large, rapidly sinking calcite like planktonic foraminiferan tests. We have done that here in a simple experiment carried out in roller tanks that allow particles to sink continuously without being impeded by container walls. Coccoliths were efficiently incorporated into aggregates that formed during the experiment, increasing their sinking speed compared to similarly sized aggregates lacking added calcite ballast. The foraminiferan tests, which sank as fast as 700 m d −1 , became associated with only very minor amounts of POC. In addition, when they collided with other, larger, foraminferan-less aggregates, they fragmented them into two smaller, more slowly sinking aggregates. While these effects were certainly exaggerated within the confines of the roller tanks, they clearly demonstrate that calcium carbonate ballast is not just calcium carbonate ballast- different forms of calcium carbonate ballast have notably different effects on POC aggregation, sinking, and export.

Description: Phenology as a strategy for carbon optimality: a global model Biogeosciences Discussions, 10, 15107-15152, 2013 Author(s): S. Caldararu, D. W. Purves, and P. I. Palmer Phenology is essential to our understanding of biogeochemical cycles and the climate system. We develop a global mechanistic model of leaf phenology based on the hypothesis that phenology is a strategy for optimal carbon gain at the canopy level so that trees adjust leaf gains and losses in response to environmental factors such as light, temperature and soil moisture, to achieve maximum carbon assimilation. We fit this model to five years of satellite observations of leaf area index (LAI) using a Bayesian fitting algorithm. We show that our model is able to reproduce phenological patterns for all vegetation types and use it to explore variations in growing season length and the climate factors that limit leaf growth for different biomes. Phenology in wet tropical areas is limited by leaf age physiological constraints while at higher latitude leaf seasonality is limited by low temperature and light availability. Leaf growth in grassland regions is limited by water availability but often in combination with other factors. This model will advance the current understanding of phenology for ecosystem carbon models and our ability to predict future phenological behaviour.

Description: Timing of sea ice retreat can alter phytoplankton community structure in the western Arctic Ocean Biogeosciences Discussions, 10, 15153-15180, 2013 Author(s): given_name prefix surname suffix, A. Fujiwara, T. Hirawake, K. Suzuki, I. Imai, and S.-I. Saitoh This study assesses the response of phytoplankton assemblages to recent climate change, especially with regard to the shrinking of sea ice in the northern Chukchi Sea of the western Arctic Ocean. Distribution patterns of phytoplankton groups in the late summers of 2008–2010 were analyzed based on HPLC pigment signatures and, the following four major algal groups were inferred via multiple regression and cluster analyses: prasinophytes, diatoms, haptophytes and dinoflagellates. A remarkable interannual difference in the distribution pattern of the groups was found in the northern basin area. Haptophytes dominated and dispersed widely in warm surface waters in 2008, whereas prasinophytes dominated in cold water in 2009 and 2010. A difference in the onset date of sea ice retreat was evident among years – the sea ice retreat in 2008 was 1–2 months earlier than in 2009 and 2010. The spatial distribution of early sea ice retreat matched the areas in which a shift in algal community composition was observed. Steel-Dwass's multiple comparison tests were used to assess the physical, chemical and biological parameters of the four clusters. We found a statistically significant difference in temperature between the haptophyte-dominated cluster and the other clusters, suggesting that the change in the phytoplankton communities was related to the earlier sea ice retreat in 2008 and the corollary increase in sea surface temperatures. Longer periods of open water during the summer, which are expected in the future, may affect food webs and biogeochemical cycles in the western Arctic due to shifts in phytoplankton community structure.

Description: Uptake of phytodetritus by benthic foraminifera under oxygen depletion at the Indian Margin (Arabian Sea) Biogeosciences Discussions, 10, 15305-15335, 2013 Author(s): A. J. Enge, U. Witte, M. Kucera, and P. Heinz Benthic foraminifera in sediments on the Indian margin of the Arabian Sea where the oxygen minimum zone (OMZ) impinges on the continental slope are exposed to particularly severe levels of oxygen depletion. Food supply for the benthic community is high but delivered in distinct pulses during upwelling and water mixing events associated with summer and winter monsoon periods. In order to investigate the response by benthic foraminifera to such pulsed food delivery under oxygen concentrations of less than 0.1 mL L −1 (4.5 μmol L −1 ), an in situ isotope labeling experiment ( 13 C, 15 N) was performed at the western continental slope of India at 540 m water depth (OMZ core region). The assemblage of living foraminifera (〉125 μm) in the uppermost centimeter at this depth is characterized by an unexpectedly high population density of 3982 ind. 10 cm −2 and a strong dominance by few calcareous species. For the experiment, we concentrated on the nine most abundant taxa, which constitute 93% of the entire foraminifera population at 0–1 cm sediment depth. Increased concentrations of 13 C and 15 N in the cytoplasm indicate that all investigated taxa took up the labeled phytodetritus during the 4 day experimental phase. In total, these nine species had assimilated 113.8 mg C m −2 (17.5% of the total added carbon). The uptake of nitrogen by the three most abundant taxa ( Bolivina aff. B. dilatata , Cassidulina sp., Bulimina gibba ) was 2.7 mg N m −2 (2% of the total added nitrogen) and showed the successful application of 15 N as tracer in foraminiferal studies. The short-term response to the offered phytodetritus varied largely among foraminiferal species with Uvigerina schwageri being by far the most important species in short-term processing whereas the most abundant taxa Bolivina aff. B. dilatata and Cassidulina sp. showed comparably low uptake of the offered food. We suggest that the observed species-specific differences are related to individual biomass of species and to specific feeding preferences. The high numbers of living foraminifera and their rapid response to deposited fresh phytodetritus demonstrate the importance of foraminifera in short-term carbon cycling under oxygen-depleted conditions. We propose that foraminifera at the studied site benefit from unique adaptations in their metabolisms to nearly anoxic conditions as well as from the exclusion of macrofauna and the resulting relaxation of competition for food and low predation pressure.

Description: Quantification of model uncertainty in aerosol optical thickness retrieval from Ozone Monitoring Instrument (OMI) measurements Atmospheric Measurement Techniques Discussions, 6, 8509-8541, 2013 Author(s): A. Määttä, M. Laine, J. Tamminen, and J. P. Veefkind We study uncertainty quantification in remote sensing of aerosols in the atmosphere with top of the atmosphere reflectance measurements from the nadir-viewing Ozone Monitoring Instrument (OMI). Focus is on the uncertainty in aerosol model selection of pre-calculated aerosol models and on the statistical modelling of the model inadequacies. The aim is to apply statistical methodologies that improve the uncertainty estimates of the aerosol optical thickness (AOT) retrieval by propagating model selection and model error related uncertainties more realistically. We utilise Bayesian model selection and model averaging methods for the model selection problem and use Gaussian processes to model the smooth systematic discrepancies from the modelled to observed reflectance. The systematic model error is learned from an ensemble of operational retrievals. The operational OMI multi-wavelength aerosol retrieval algorithm OMAERO is used for cloud free, over land pixels of the OMI instrument with the additional Bayesian model selection and model discrepancy techniques. The method is demonstrated with four examples with different aerosol properties: weakly absorbing aerosols, forest fires over Greece and Russia, and Sahara dessert dust. The presented statistical methodology is general; it is not restricted to this particular satellite retrieval application.

Description: Summertime canopy albedo is sensitive to forest thinning Biogeosciences Discussions, 10, 15373-15414, 2013 Author(s): J. Otto, D. Berveiller, F.-M. Bréon, N. Delpierre, G. Geppert, A. Granier, W. Jans, A. Knohl, A. Kuusk, B. Longdoz, E. Moors, M. Mund, B. Pinty, M.-J. Schelhaas, and S. Luyssaert Despite an emerging body of literature linking canopy albedo to forest management, understanding of the process is still fragmented. We combined a stand-level forest gap model with a canopy radiation transfer model and satellite-derived model parameters to quantify the effects of forest thinning, that is removing trees at a certain time during the forest rotation, on summertime canopy albedo. The effects of different forest species (pine, beech, oak) and four thinning strategies (light to intense thinning regimes) were examined. During stand establishment, summertime canopy albedo is driven by tree species. In the later stages of stand development, the effect of tree species on summertime canopy albedo decreases in favour of an increasing influence of forest thinning on summertime canopy albedo. These trends continue until the end of the rotation where thinning explains up to 50% of the variance in near-infrared canopy albedo and up to 70% of the variance in visible canopy albedo. More intense thinning lowers the summertime shortwave albedo in the canopy by as much as 0.02 compared to unthinned forest. The structural changes associated with forest thinning can be described by the change in LAI in combination with crown volume. However, forests with identical canopy structure can have different summertime albedo values due to their location: the further north a forest is situated, the more the solar zenith angle increases and thus the higher is the summertime canopy albedo, independent of the wavelength. Despite the increase of absolute summertime canopy albedo values with latitude, the difference in canopy albedo between managed and unmanaged forest decreases with increasing latitude. Forest management thus strongly altered summertime forest albedo.

Description: Oxygen minimum zone of the open Arabian Sea: variability of oxygen and nitrite from daily to decadal time scales Biogeosciences Discussions, 10, 15455-15517, 2013 Author(s): K. Banse, S. W. A. Naqvi, P. V. Narvekar, J. R. Postel, and D. A. Jayakumar The oxygen minimum zone (OMZ) of the Arabian Sea is the thickest of the three oceanic OMZs, which is of global biogeochemical significance because of denitrification in the upper part leading to N 2 and N 2 O production. The residence time of the OMZ water is believed to be less than a decade. The upper few hundred meters of this zone are nearly anoxic but non-sulfidic and still support animal (metazoan) pelagic life, possibly as a result of episodic injections of O 2 by physical processes. The very low O 2 values obtained with the new STOX sensor in the eastern tropical South Pacific probably also characterize the Arabian Sea OMZ, but there is no apparent reason as to why the temporal trends of the historic data should not hold. We report on discrete measurements of dissolved O 2 and NO 2 - , besides temperature and salinity, made between 1959 and 2004 well below the tops of the sharp pycno- and oxyclines near 150, 200, 300, 400, and 500 m depth. We assemble nearly all O 2 determinations (originally, 849 values, 695 in the OMZ) by the visual endpoint detection of the iodometric Winkler procedure, which in our data base yields about 0.04 mL L −1 (∼2 μM) O 2 above the endpoint from modern automated titration methods. We find 632 values acceptable (480 from 150 stations in the OMZ). The data are grouped in zonally-paired boxes of 1° lat. and 2° long. centered at 8°, 10°, 12°, 15°, 18°, 20°, and 21° N along 65° E and 67° E. The latitudes of 8–12° N, outside the OMZ, are only treated in passing. The principal results are as follows: (1) an O 2 climatology for the upper OMZ reveals a marked seasonality at 200 to 500 m depth with O 2 levels during the northeast monsoon and spring intermonsoon season elevated over those during the southwest monsoon season (median difference, 0.08 mL L −1 [3.5 μM]). The medians of the slopes of the seasonal regressions of O 2 on year for the NE and SW monsoon seasons are −0.0043 and −0.0019 mL L −1 a −1 , respectively (−0.19 and −0.08 μM a −1 ; n = 10 and 12, differing at p = 0.01); (2) four decades of statistically significant decreases of O 2 between 15° and 20° N but a trend to a similar increase near 21° N are observed. The balance of the mechanisms that more or less annually maintain the O 2 levels are still uncertain. At least between 300 and 500 m the annual reconstitution of the decrease is inferred to be due to lateral, isopycnal re-supply of O 2 , while at 200 (250?) m it is diapycnal, most likely by eddies. Similarly, recent models show large vertical advection of O 2 well below the pycno- cum -oxycline. The spatial (within drift stations) and temporal (daily) variability in hydrography and chemistry is large also below the principal pycnocline. The seasonal change of hydrography is considerable even at 500 m. There is no trend in the redox environment for a quarter of a century at a GEOSECS station near 20° N. In the entire OMZ the slopes on year within seasons for the quite variable NO 2 - (taken as an indicator of active denitrification) do not show a clear pattern. Also, future O 2 or nutrient budgets for the OMZ should not be based on single cruises or sections obtained during one season only. Steady state cannot be assumed any longer for the intermediate layers of the central Arabian Sea.

Description: The Greenhouse Gas Climate Change Initiative (GHG-CCI): comparative validation of GHG-CCI SCIAMACHY/ENVISAT and TANSO-FTS/GOSAT CO 2 and CH 4 retrieval algorithm products with measurements from the TCCON network Atmospheric Measurement Techniques Discussions, 6, 8679-8741, 2013 Author(s): B. Dils, M. Buchwitz, M. Reuter, O. Schneising, H. Boesch, R. Parker, S. Guerlet, I. Aben, T. Blumenstock, J. P. Burrows, A. Butz, N. M. Deutscher, C. Frankenberg, F. Hase, O. P. Hasekamp, J. Heymann, M. De Mazière, J. Notholt, R. Sussmann, T. Warneke, D. Griffith, V. Sherlock, and D. Wunch Column-averaged dry-air mole fractions of carbon dioxide and methane have been retrieved from spectra acquired by the TANSO-FTS and SCIAMACHY instruments on board GOSAT and ENVISAT using a range of European retrieval algorithms. These retrievals have been compared with data from ground-based high-resolution Fourier Transform Spectrometers (FTS) from the Total Carbon Column Observing Network (TCCON). The participating algorithms are the Weighting Function Modified Differential Optical Absorption Spectroscopy (DOAS) algorithm (WFMD, University of Bremen), the Bremen Optimal Estimation DOAS algorithm (BESD, University of Bremen), the Iterative Maximum A Posteriori DOAS (IMAP, Jet Propulsion Laboratory (JPL) and Netherlands Institute for Space Research algorithm (SRON)), the proxy and full-physics versions of SRON's RemoTeC algorithm (SRPR and SRFP respectively) and the proxy and full-physics versions of the University of Leicester's adaptation of the OCO (Orbiting Carbon Observatory) algorithm (OCPR and OCFP respectively). The goal of this algorithm inter-comparison was to identify strengths and weaknesses of the various so-called Round Robin data sets generated with the various algorithms so as to determine which of the competing algorithms would proceed to the next round of the European Space Agency's (ESA) Greenhouse Gas Climate Change Initiative (GHG-CCI) project, which is the generation of the so-called Climate Research Data Package (CRDP), which is the first version of the Essential Climate Variable (ECV) "Greenhouse Gases" (GHG). For CO 2 , all algorithms reach the precision requirements for inverse modelling ( 〈 8 ppb), with only WFMD having a lower precision (4.7 ppm) than the other algorithm products (2.4–2.5 ppm). When looking at the seasonal relative accuracy (SRA, variability of the bias in space and time), none of the algorithms have reached the demanding 〈 0.5 ppm threshold. For CH 4 , the precision for both SCIAMACHY products (50.2 ppb for IMAP and 76.4 ppb for WFMD) fail to meet the 〈 34 ppb threshold, but note that this work focusses on the period after the 2005 SCIAMACHY detector degradation. The GOSAT X CH 4 precision ranges between 18.1 and 14.0 ppb. Looking at the SRA, all GOSAT algorithm products reach the 〈 10 ppm threshold (values ranging between 5.4 and 6.2 ppb). For SCIAMACHY, IMAP and WFMD have a SRA of 17.2 ppb and 10.5 ppb respectively.

Description: Stable isotopes dissect food webs from top to the bottom Biogeosciences Discussions, 10, 14923-14952, 2013 Author(s): J. J. Middelburg Stable isotopes have been used extensively to study food web functioning, i.e. the flow of energy and matter among organisms. Traditional food-web studies are based on the natural variability of carbon and nitrogen isotopes and are limited to larger organisms that can be physically separated from their environment. Recent developments allow isotope ratio measurements of microbes and this in turn allows then measurement of entire food webs, i.e. from small producers at the bottom to large consumers at the top. Here, I provide a concise review on the use and potential of stable isotope to reconstruct end-to-end food webs. I will first discuss food web reconstruction based on natural abundances isotope data and will then show that the use of stable isotopes as deliberately added tracers provides complementary information. Finally, challenges and opportunities for end-to-end food web reconstructions in a changing world are discussed.

Description: The effect of phase partitioning of semivolatile compounds on the measured CCN activity of aerosol particles Atmospheric Measurement Techniques Discussions, 6, 8413-8433, 2013 Author(s): S. Romakkaniemi, A. Jaatinen, A. Laaksonen, A. Nenes, and T. Raatikainen The effect of inorganic semivolatile aerosol compounds on the CCN activity of aerosol particles was studied by using a computational model for a DMT-CCN counter, a cloud parcel model for condensation kinetics and experiments to quantify the modelled results. Concentrations of water vapour and semivolatiles as well as aerosol trajectories in the CCN column were calculated by a computational fluid dynamics model. These trajectories and vapour concentrations were then used as an input for the cloud parcel model to simulate mass transfer kinetics of water and semivolatiles between aerosol particles and the gas phase. Two different questions were studied: (1) how big fraction of semivolatiles is evaporated from particles before activation in the CCN counter? (2) How much the CCN activity can be increased due to condensation of semivolatiles prior to the maximum water supersaturation in the case of high semivolatile concentration in the gas phase? The results show that, to increase the CCN activity of aerosol particles, a very high gas phase concentration (as compared to typical ambient conditions) is needed. We used nitric acid as a test compound. A concentration of several ppb or higher is needed for measurable effect. In the case of particle evaporation, we used ammonium nitrate as a test compound and found that it partially evaporates before maximum supersaturation is reached in the CCN counter, thus causing an underestimation of CCN activity. The effect of evaporation is clearly visible in all supersaturations, leading to an underestimation of the critical dry diameter by 10 to 15 nanometres in the case of ammonium nitrate particles in different supersaturations. This result was also confirmed by measurements in supersaturations between 0.1 and 0.7%.

Description: Responses of carbon dioxide flux and plant biomass to drought in a treed peatland in northern Alberta: a climate change perspective Biogeosciences Discussions, 10, 14999-15031, 2013 Author(s): T. M. Munir, B. Xu, M. Perkins, and M. Strack Northern peatland ecosystems represent large carbon stocks that are susceptible to changes such as accelerated mineralization due to water table lowering expected under a climate change scenario. During the growing seasons of 2011 and 2012 we monitored CO 2 fluxes and plant biomass along a microtopographic gradient (hummocks-hollows) in an undisturbed dry continental boreal treed bog (control) and a nearby site that was drained (drained) in 2001. Ten years of drainage in the bog significantly increased coverage of shrubs at hummocks and lichens at hollows. Considering measured hummock coverage and including tree incremental growth, we estimate that the control site was a larger sink in 2011 of −40 than that of −13 g C m −2 in 2012 while the drained site was a source of 144 and 140 g C m −2 over the same years. We infer that, drainage induced changes in vegetation growth led to increased biomass to counteract a portion of soil carbon losses. These results suggest that spatial variability (microtopography) and changes in vegetation community in boreal peatlands will affect how these ecosystems respond to lowered water table potentially induced by climate change.

Description: The coccolithophores Emiliania huxleyi and Coccolithus pelagicus : extant populations from the Norwegian-Iceland Sea and Fram Strait Biogeosciences Discussions, 10, 15077-15106, 2013 Author(s): C. V. Dylmer, J. Giraudeau, V. Hanquiez, and K. Husum Extant coccolithophores and their relation to the governing oceanographic features in the northern North Atlantic were investigated along two zonal transects of surface water sampling, both conducted during summer 2011 and fall 2007. The northern transects crossed Fram Strait and its two opposing boundary currents (West Spitsbergen Current and East Greenland Current), while the southern transects sampled the Norwegian and Iceland Seas (passing the island Jan Mayen) from the Lofoten Islands to the continental margin off Eastern Greenland. The distribution of the dominant coccolithophore species Emiliania huxleyi and Coccolithus pelagicus is discussed in view of both the surface hydrology at the time of sampling and the structure of the surface mixed layer. Remote-sensing images as well as CTD and ARGO profiles are used to constrain the physico-chemical state of the surface water at the time of sampling. Both transects were characterized by strong seasonal differences in bulk coccolithophore standing stocks with maximum values of 53 × 10 3 cells L −1 for the northern transect and 72 × 10 3 cells L −1 for the southern transect in fall and summer, respectively. The highest recorded bulk cell densities are essentially explained by E. huxleyi . This species shows a zonal shift in peak abundance in the Norwegian-Iceland Seas from a summer maximum in the Lofoten gyre to peak cell densities around the island Jan Mayen in fall. Vertical mixing of Atlantic waters west of Lofoten Island, a phenomenom related to pervasive summer large scale atmospheric changes in the eastern Nordic Seas, on one hand, and strengthened influence of melt-water and related surface water stratification around the island Jan Mayen during fall, on the other hand, explains the observed seasonal migration of the E. huxleyi peak production area, as well as the seasonal change in dominating species within the Iceland Sea. In addition our datasets are indicative of a well-defined maximum boundary temperature of 6 °C for the production of C. pelagicus in the northern North Atlantic. The Fram Strait transects provides, to our knowledge, a first view of the zonal distribution of extant coccolithophores in this remote setting during summer and fall. Our datasets are indicative of a seasonal change in the species community from an E. huxleyi -dominated assemblage during summer to a C. pelagicus -rich population during fall. Here, higher irradiance and increased Atlantic water influence during summer favored the production of the opportunistic species E. huxleyi close to the Arctic Front, whereas the peak production area during fall, with high concentrations of C. pelagicus , lays in true Arctic/Polar waters.

Description: Anthropogenic and natural methane fluxes in Switzerland synthesized within a spatially-explicit inventory Biogeosciences Discussions, 10, 15181-15224, 2013 Author(s): R. V. Hiller, D. Bretscher, T. DelSontro, T. Diem, W. Eugster, R. Henneberger, S. Hobi, E. Hodson, D. Imer, M. Kreuzer, T. Künzle, L. Merbold, P. A. Niklaus, B. Rihm, A. Schellenberger, M. H. Schroth, C. J. Schubert, H. Siegrist, J. Stieger, N. Buchmann, and D. Brunner We present the first high-resolution (500 m × 500 m) gridded methane (CH 4 ) emission inventory for Switzerland, which integrates the national emission totals reported to the United Nations Framework Convention on Climate Change (UNFCCC) and recent CH 4 flux studies conducted by research groups across Switzerland. In addition to anthropogenic emissions, we also include natural and semi-natural CH 4 fluxes, i.e., emissions from lakes and reservoirs, wetlands, wild animals as well as uptake by forest soils. National CH 4 emissions were disaggregated using detailed geostatistical information on source locations and their spatial extent and process- or area-specific emission factors. In Switzerland, the highest CH 4 emissions in 2011 originated from the agricultural sector (150 Gg CH 4 yr −1 ), mainly produced by ruminants and manure management, followed by emissions from waste management (15 Gg CH 4 yr −1 ) mainly from landfills and the energy sector (12 Gg CH 4 yr −1 ), which was dominated by emissions from natural gas distribution. Compared to the anthropogenic sources, emissions from natural and semi-natural sources were relatively small (6 Gg CH 4 yr −1 ), making up only 3 % of the total emissions in Switzerland. CH 4 fluxes from agricultural soils were estimated to be not significantly different from zero (between −1.5 and 0 Gg CH 4 yr −1 ), while forest soils are a CH 4 sink (approx. −2.8 Gg CH 4 yr −1 ), partially offsetting other natural emissions. Estimates of uncertainties are provided for the different sources, including an estimate of spatial disaggregation errors deduced from a comparison with a global (EDGAR v4.2) and a European CH 4 inventory (TNO/MACC). This new spatially-explicit emission inventory for Switzerland will provide valuable input for regional scale atmospheric modeling and inverse source estimation.

Description: Seasonal trends of dry and bulk concentration of nitrogen compounds over a rain forest in Ghana Biogeosciences Discussions, 10, 15225-15255, 2013 Author(s): F. Fattore, T. Bertolini, S. Materia, S. Gualdi, A. Thongo M'Bou, G. Nicolini, R. Valentini, A. De Grandcourt, D. Tedesco, and S. Castaldi African tropical forests of the equatorial belt might receive significant input of extra nitrogen derived from biomass burning occurring in the north savanna belt and transported equator wards by NE winds. In order to test this hypothesis an experiment was set up in a tropical rain forest in the National park of Ankasa (Ghana) aiming at: quantifying magnitude and seasonal variability of concentrations of N compounds, present as gas and aerosol (dry nitrogen) or in the rainfall (bulk nitrogen), over the studied forest; relating their seasonal variability to trends of local and regional winds and rainfall and to variations of fire events in the region. Three Delta systems, implemented for monthly measurements of NO 2 , were mounted over a tower at 45 m height, 20 m above forest canopy to sample gas (NH 3 , NO 2 , HNO 3 , HCl, SO 2 ) and aerosol (NH 4 + , NO 3 − , and several ions), together with three tanks for bulk rainfall collection (to analyze NH 4 + , NO 3 − and ion concentration). The tower was provided with a sonic anemometer to estimate local wind data. The experiment started in October 2011 and data up to October 2012 are presented. To interpret the observed seasonal trends of measured compounds, local and regional meteo data and regional satellite fire data were analyzed. The concentration of N compounds significantly increased from December to April, during the drier period, peaking in December-February when North Eastern winds (Harmattan) were moving dry air masses over the West central African region and the inter tropical convergence zone (ITCZ) was at its minimum latitude over the equator. This period also coincided with peaks of fire in the whole region. On the contrary, N concentration in gas, aerosol and rain decreased from May to October when prevalent winds arrived from the sea (South-East), during the Monsoon period. Both ionic compositions of rain and analysis of local wind direction showed a significant and continuous presence of see-breeze at site. The ionic composition of rain water resulted much closer to see water and poorer in N compounds from May to October.

Description: Inferences from CO 2 and CH 4 concentration profiles at the Zotino Tall Tower Observatory (ZOTTO) on local summer-time ecosystem fluxes Biogeosciences Discussions, 10, 15337-15372, 2013 Author(s): J. Winderlich, C. Gerbig, O. Kolle, and M. Heimann The Siberian region is still sparsely covered by ecosystem observatories, which motivates to exploit existing datasets to gain spatially and temporally better-resolved carbon fluxes. The Zotino Tall Tower Observatory (ZOTTO, 60°48' N, 89°21' E) observations of CO 2 and CH 4 mole fractions as well as meteorological parameters from six different heights up to 301 m allow for an additional estimate of surface-atmosphere fluxes of CO 2 and CH 4 for the Middle-Siberian region since 2009. The total carbon flux is calculated from the storage and the turbulent flux component. The gradients between the different tower levels determine the storage flux component, which dominates the local fluxes, especially during night. As a correction term, the turbulent flux component was estimated by the modified Bowen ratio method based on the sensible heat flux measurements at the top of the tower. The gained average night time fluxes (23:00 to 04:00 local time) are 2.7 ± 1.1 μmol (m 2 s) −1 for CO 2 and 5.6 ± 4.5 nmol (m 2 s) −1 for CH 4 during the summer months June-September in 2009 and 2011. During day, the method is limited due to numeric instabilities from vanishing vertical gradients; however, the derived CO 2 fluxes exhibit reasonable diurnal shape and magnitude compared to the eddy covariance technique, which become available at the site in 2012. Therefore, the tall tower data facilitates the extension of the new eddy covariance flux dataset back in time. The diurnal signal of the CH 4 flux is predominantly characterized by a strong morning transition, which is explained by local topographic effects.

Description: Live foraminiferal faunas (Rose Bengal stained) from the northern Arabian Sea: links with bottom-water oxygenation Biogeosciences Discussions, 10, 15257-15304, 2013 Author(s): C. Caulle, K. A. Koho, M. Mojtahid, G. J. Reichart, and F. J. Jorissen Live (Rose Bengal stained) benthic foraminifera from the Murray Ridge, within and below the northern Arabian Sea Oxygen Minimum Zone (OMZ), were studied in order to determine the relationship between faunal composition, bottom-water oxygenation (BWO), pore-water chemistry and organic matter (organic carbon and phytopigment) distribution. A series of multicores were recovered from a ten-station oxygen (BWO: 2–78 μM) and bathymetric (885–3010 m depth) transect during the winter monsoon in January 2009. Foraminifera were investigated from three different size fractions (63–125 μm, 125–150 μm and 〉 150 μm). The larger foraminifera (〉 125 μm) were strongly dominated by agglutinated species (e.g. Reophax spp.). In contrast, in the 63–125 μm fraction, calcareous taxa were more abundant, especially in the core of the OMZ, suggesting an opportunistic behaviour. On the basis of a Principal Component Analysis, three foraminiferal groups were identified, reflecting the environmental parameters along the study transect. The faunas from the shallowest stations, in the core of the OMZ (BWO: 2 μM), were composed of "low oxygen" species, typical of the Arabian Sea OMZ (e.g., Rotaliatinopsis semiinvoluta , Praeglobobulimina spp. , Bulimina exilis, Uvigerina peregrina type parva ). These taxa are adapted to the very low BWO conditions and to high phytodetritus supplies. The transitional group, typical for the lower part of the OMZ (BWO: 5–16 μM), is composed of more cosmopolitan taxa tolerant to low-oxygen concentrations ( Globocassidulina subglobosa , Ehrenbergina trigona ). Below the OMZ (BWO: 26–78 μM), where food availability is more limited and becomes increasingly restricted to surficial sediments, more cosmopolitan calcareous taxa were present, such as Bulimina aculeata, Melonis barleeanus, Uvigerina peregrina and Epistominella exigua . Miliolids were uniquely observed in this last group, reflecting the higher BWO. At these deeper sites, the faunas exhibit a clear depth succession of superficial, intermediate and deep-infaunal microhabitats, because of the deeper oxygen and nitrate penetration into the sediment.

Description: Landscape-scale changes in forest structure and functional traits along an Andes-to-Amazon elevation gradient Biogeosciences Discussions, 10, 15415-15454, 2013 Author(s): G. P. Asner, C. Anderson, R. E. Martin, D. E. Knapp, R. Tupayachi, T. Kennedy-Bowdoin, F. Sinca, and Y. Malhi Elevation gradients provide opportunities to explore environmental controls on forest structure and functioning, but plot-based studies have proven highly variable due to limited geographic scope. We used airborne imaging spectroscopy and LiDAR (light detection and ranging) to quantify changes in three-dimensional forest structure and canopy functional traits in a series of 25 ha landscapes distributed along a 3300 m elevation gradient from lowland Amazonia to treeline in the Peruvian Andes. Canopy greenness, photosynthetic fractional cover and exposed non-photosynthetic vegetation varied as much across lowland forests (100–200 m) as they did from the lowlands to the Andean treeline (3400 m). Elevation was positively correlated with canopy gap density and understory vegetation cover, and negatively related to canopy height and vertical profile. Increases in gap density were tightly linked to increases in understory plant cover, and larger gaps (20–200 m 2 produced 25–30 times the response in understory cover than did smaller gaps ( 〈 5 m 2 . Scaling of gap size to gap frequency was, however, relatively constant along the elevation gradient, which when combined with other canopy structural information, indicates equilibrium turnover patterns from the lowlands to treeline. Our results provide a first landscape-scale quantification of forest structure and canopy functional traits with changing elevation, thereby improving our understanding of disturbance, demography and ecosystem processes in the Andes-to-Amazon corridor.

Description: Spectral Aerosol Extinction Monitoring System (SÆMS): setup, observational products, and comparisons Atmospheric Measurement Techniques Discussions, 6, 8647-8677, 2013 Author(s): A. Skupin, A. Ansmann, R. Engelmann, and H. Baars A Spectral Aerosol Extinction Monitoring System (SÆMS) is presented that allows us to continuously measure the spectral extinction coefficient of atmospheric aerosol particles along an about 2.7 km long optical path at 30–50 m height above ground at Leipzig (51.3° N, 12.4° E), Germany. The fully automated instrument measures the ambient aerosol extinction coefficients from 300–1000 nm. The main goal of SÆMS observations are long-term studies of the relationship between particle extinction and relative humidity from below 40 % to almost 100 %. The setup is presented and observations (a case study and statistical results for 2009) are discussed in terms of time series of 550 nm particle optical depth, Ångström exponent, and particle size distribution retrieved from the spectrally resolved extinction. The SÆMS measurements are compared with simultaneously performed EARLINET lidar, AERONET photometer, and in situ aerosol observations of particle size distribution and related extinction coefficients at the roof of our institute. Consistency between the different measurements is found which corroborates the quality of the SÆMS observations.

Description: Springtime phytoplankton dynamics in the Arctic Krossfjorden and Kongsfjorden (Spitsbergen) as a function of glacier proximity Biogeosciences Discussions, 10, 15519-15557, 2013 Author(s): A. M.-T. Piquet, W. H. van de Poll, R. J. W. Visser, C. Wiencke, H. Bolhuis, and A. G. J. Buma The hydrographic properties of the Kongsfjorden – Krossfjorden system (79° N, Spitsbergen) are affected by Atlantic water incursions as well as glacier meltwater runoff. This results in strong physical gradients (temperature, salinity and irradiance) within the fjords. Here, we tested the hypothesis that glaciers affect phytoplankton dynamics as early as the productive spring bloom period. During two campaigns in 2007 (late spring) and 2008 (early spring) we studied hydrographic characteristics and phytoplankton variability along 2 transects in both fjords, using HPLC-CHEMTAX pigment fingerprinting, molecular fingerprinting (DGGE) and sequencing of 18S rRNA genes. The sheltered inner fjord locations remained colder during spring as opposed to the outer locations. Vertical light attenuation coefficients increased from early spring onwards, at all locations, but in particular at the inner locations. During the end of spring, meltwater input had stratified surface waters throughout the fjords. The inner fjord locations were characterized by overall lower phytoplankton biomass. Furthermore HPLC-CHEMTAX data revealed that diatoms and Phaeocystis sp. were replaced by small nano- and picophytoplankton during late spring, coinciding with low nutrient availability. The innermost stations showed higher relative abundances of nano- and picophytoplankton throughout, notably of cyanophytes and cryptophytes. Molecular fingerprinting revealed a high similarity between inner fjord samples from early spring and late spring samples from all locations, while outer samples from early spring clustered separately. We conclude that glacier influence, mediated by early meltwater input, modifies phytoplankton biomass and composition already during the spring bloom period, in favor of low biomass and small cell size communities. This may affect higher trophic levels especially when regional warming further increases the period and volume of meltwater.

Description: Validation of SCIAMACHY O 2 A band cloud heights using Cloudnet radar/lidar measurements Atmospheric Measurement Techniques Discussions, 6, 8603-8645, 2013 Author(s): P. Wang and P. Stammes For the first time two SCIAMACHY O 2 A band cloud height products are validated using ground-based radar/lidar measurements between January 2003 and December 2011. The products are the ESA Level 2 (L2) version 5.02 cloud top height and the FRESCO (Fast Retrieval Scheme for Clouds from the Oxygen A band) version 6 cloud height. The radar/lidar profiles are obtained at the Cloudnet sites of Cabauw and Lindenberg, and are averaged for one hour centered at the SCIAMACHY overpass time to achieve an optimal temporal and spatial match. In total we have about 220 cases of single layer clouds and 200 cases of multi-layer clouds. The FRESCO cloud height and ESA L2 cloud top height are compared with the Cloudnet cloud top height and Cloudnet cloud middle height. We find that the ESA L2 cloud top height has a better agreement with the Cloudnet cloud top height than the Cloudnet cloud middle height. The ESA L2 cloud top height is on average 0.44 km higher than the Cloudnet cloud top height, with a standard deviation of 3.07 km. The FRESCO cloud height is closer to the Cloudnet cloud middle height than the Cloudnet cloud top height. The mean difference between the FRESCO cloud height and the Cloudnet cloud middle height is −0.14 km with a standard deviation of 1.88 km. The SCIAMACHY cloud height products are further compared to the Cloudnet cloud top height and the Cloudnet cloud middle height in 1 km bins. For single layer clouds, the difference between the ESA L2 cloud top height and the Cloudnet cloud top height is less than 1 km for each cloud bin at 3–7 km, which is 24 % percent of the data. The difference between the FRESCO cloud height and the Cloudnet cloud middle height is less than 1 km for each cloud bin at 0–6 km, which is 85 % percent of the data. The results are similar for multi-layer clouds, but the percentage of cases having a bias within 1 km is smaller than for single layer clouds. Since globally about 60 % of all clouds are low clouds and 42 % are single-layer low clouds, we expect that globally for a large percentage of cases the FRESCO cloud height would be close to the cloud middle height.

Description: Simulating microbial degradation of organic matter in a simple porous system using the 3-D diffusion based model MOSAIC Biogeosciences Discussions, 10, 15613-15640, 2013 Author(s): O. Monga, P. Garnier, V. Pot, E. Coucheney, N. Nunan, W. Otten, and C. Chenu This paper deals with the simulation of microbial degradation in soil within pore space at microscopic scale. Pore space was described using sphere network coming from a geometrical modeling algorithm. The biological model was improved regarding previous work in order to include transformation of dissolved organic compounds and diffusion processes. Our model was tested using experimental results of a simple substrate decomposition (Fructose) within a simple media (the sand). Diverse microbial communities were inoculated. Separated incubations in microcosms were carried out using 5 different bacterial communities at 2 different water potentials of −10 cm and −100 cm of water. We calibrated the biological parameters by means of experimental data obtained at high water content and we tested the model without any parameters change at low water content. Same as for experimental data, our simulation results showed the decrease in water content involved the decrease of mineralisation. The model was able to simulate the decrease of connectivity between substrate and microorganism due the decrease of water content.

Description: Influence of temperature and CO 2 on the strontium and magnesium composition of coccolithophore calcite Biogeosciences Discussions, 10, 15559-15586, 2013 Author(s): M. N. Müller, M. Lebrato, U. Riebesell, J. Barcelos e Ramos, K. G. Schulz, S. Blanco-Ameijeiras, S. Sett, A. Eisenhauer, and H. M. Stoll Marine calcareous sediments provide a fundamental basis for paleoceanographic studies aiming to reconstruct past oceanic conditions and understand key biogeochemical element cycles. Calcifying unicellular phytoplankton (coccolithophores) are a major contributor to both carbon and calcium cycling by photosynthesis and the production of calcite (coccoliths) in the euphotic zone and the subsequent long-term deposition and burial into marine sediments. Here we present data from controlled laboratory experiments on four coccolithophore species and elucidate the relation between the divalent cation (Sr, Mg and Ca) partitioning in coccoliths and cellular physiology (growth, calcification and photosynthesis). Coccolithophores were cultured under different seawater temperature and carbonate chemistry conditions. The partition coefficient of strontium ( D Sr ) was positively correlated with both carbon dioxide ( p CO 2 ) and temperature but displayed no coherent relation to particulate organic and inorganic carbon production rates. Furthermore, D Sr correlated positively with cellular growth rates when driven by temperature but no correlation was present when changes in growth rates were p CO 2 -induced. The results demonstrate the complex interaction between environmental forcing and physiological control on the strontium partitioning in coccolithophore calcite. The partition coefficient of magnesium ( D Mg ) displayed species-specific differences and elevated values under nutrient limitation. No conclusive correlation between coccolith D Mg and temperature was observed but p CO 2 induced a rising trend in coccolith D Mg . Interestingly, the best correlation was found between coccolith D Mg and chlorophyll a production suggesting that chlorophyll a and calcite associated Mg originate from the same intracellular pool. These results give an extended insight into the driving factors that lead to variations in the coccolith Mg / Ca ratio and can be used for Sr / Ca and Mg / Ca paleoproxy calibration.

Description: Forest NEP is significantly driven by previous year's weather Biogeosciences Discussions, 10, 15587-15611, 2013 Author(s): S. Zielis, S. Etzold, R. Zweifel, W. Eugster, M. Haeni, and N. Buchmann Understanding the response of forest net ecosystem productivity (NEP) to environmental drivers under climate change is highly relevant for predictions of annual forest carbon (C) flux budgets. Modeling annual forest NEP with soil–vegetation–atmosphere transfer models (SVATs), however, remains challenging due to unknown responses of forests to weather of the previous year. In this study, we addressed the influence of previous year's weather on the inter-annual variability of NEP for a subalpine spruce forest in Switzerland. Analysis of long-term (1997–2011) eddy covariance measurements showed that the Norway spruce forest Davos Seehornwald was a consistent sink for atmospheric CO 2 , sequestering 210 ± 88 g C m −2 per year on average. Previous year's weather strongly affected inter-annual variability of NEP, increasing the explained variance in linear models to 53% compared to 20% without previous year's weather. Thus, our results highlight the need to consider previous year's weather in modeling annual C budgets of forests. Furthermore, soil temperature in the current year's spring played a major role controlling annual NEP, mainly by influencing gross primary productivity early in the year, with spring NEP accounting for 56% of annual NEP. Consequently, we expect an increase in net CO 2 uptake with future climate warming, as long as no other resources become limiting.

Description: Characteristics of cloud liquid water path from SEVIRI on the Meteosat Second Generation 2 satellite for several cloud types Atmospheric Measurement Techniques Discussions, 6, 8743-8782, 2013 Author(s): A. Kniffka, M. Stengel, M. Lockhoff, R. Bennartz, and R. Hollmann In this study the temporal and spatial characteristics of liquid water path (LWP) of low, middle level and high clouds are analysed using space-based observations of the Spinning Enhanced Visible and Infrared Imager (SEVIRI) onboard the Meteosat Second Generation 2 (MSG2) satellite. Both geophysical quantities are part of the dataset CLAAS (CLoud property dAtAset using SEVIRI) and are generated by EUMETSAT's Satellite Application Facility on Climate Monitoring (CM SAF). In this article we focus on the statistical properties of LWP retrieved at daylight associated with the individual cloud type. Our results reveal that each cloud type possesses a characteristic LWP distribution. These frequency distributions are constant with time in the entire SEVIRI field of view, but vary for smaller regions like Central Europe. The average LWP is higher over land than over sea, in case of low clouds 15–27% for 2009 and the variance of the frequency distributions is enhanced. Also, the average diurnal cycle of LWP is related to cloud type where most pronounced diurnal variations were detected for middle level clouds. With SEVIRI it is possible to distinguish between intrinsic LWP variability and variations driven by cloud amount. The relative amplitude of the intrinsic diurnal cycle can exceed the cloud amount driven amplitude.

Description: Synoptic evaluation of carbon cycling in Beaufort Sea during summer: contrasting river inputs, ecosystem metabolism and air–sea CO 2 fluxes Biogeosciences Discussions, 10, 15641-15710, 2013 Author(s): A. Forest, P. Coupel, B. Else, S. Nahavandian, B. Lansard, P. Raimbault, T. Papakyriakou, Y. Gratton, L. Fortier, J.-É. Tremblay, and M. Babin The accelerated decline in Arctic sea ice combined with an ongoing trend toward a more dynamic atmosphere is modifying carbon cycling in the Arctic Ocean. A critical issue is to understand how net community production (NCP; the balance between gross primary production and community respiration) responds to changes and modulates air–sea CO 2 fluxes. Using data collected as part of the ArcticNet-Malina 2009 expedition in southeastern Beaufort Sea (Arctic Ocean), we synthesize information on sea ice, wind, river, water column properties, metabolism of the planktonic food web, organic carbon fluxes and pools, as well as air–sea CO 2 exchange, with the aim of identifying indices of ecosystem response to environmental changes. Data were analyzed to develop a non-steady-state carbon budget and an assessment of NCP against air–sea CO 2 fluxes. The mean atmospheric forcing was a mild upwelling-favorable wind (~5 km h −1 ) blowing from the N-E and a decaying ice cover ( 600 mg C m −2 d −1 ) over the shelf prior to our survey, (2) freshwater dilution by river runoff and ice melt, and (3) the presence of cold surface waters offshore. Only the Mackenzie River delta and localized shelf areas directly affected by upwelling were identified as substantial sources of CO 2 to the atmosphere (〉10mmol C m −2 d −1 ). Although generally

Description: Remote sensing of atmospheric trace gas columns: an efficient approach for regularization and calculation of total column averaging kernels Atmospheric Measurement Techniques Discussions, 6, 4999-5031, 2013 Author(s): T. Borsdorff, O. P. Hasekamp, A. Wassmann, and J. Landgraf A concept is proposed to retrieve the vertical column densities of atmospheric trace gases from remote sensing measurements. It combines the numerical simplicity of a least-squares profile scaling retrieval with the numerically robust calculation of the total column averaging kernel using an analytic expression. The approach enables calculation of the total column averaging kernel on arbitrary vertical grids. Formally, the proposed method is equivalent to Tikhonov regularization of the first kind with an infinite regularization strength. Due to its efficiency it is particularly suited for implementation in operational data processing with high demands on processing time. To demonstrate the method, we apply it to CO column retrieval from simulated measurements in the 2.3 μm spectral region and to O 3 column retrieval from the UV, which represents ideal measurements of a series of space-borne spectrometers like SCIAMACHY, TROPOMI, GOME, and GOME-2. For both spectral ranges, we consider clear-sky and cloudy scenes where clouds are modelled as an elevated Lambertian surface. Here, the smoothing error for the clear-sky and cloudy atmosphere is significant and reaches several percent, depending on the reference profile which is used for scaling. This underlines the importance of the column averaging kernel for a proper interpretation of retrieved column densities. Furthermore, we show that the total column smoothing error is affected by a discretization error when total column averaging kernels are not represented on a fine enough vertical grid. For both retrievals this effect becomes negligible by using a vertical grid with 20–40 equally thick layers between 0 and 50 km.

Description: Mixing layer height retrievals by multichannel microwave radiometer observations Atmospheric Measurement Techniques Discussions, 6, 4971-4998, 2013 Author(s): D. Cimini, F. De Angelis, J.-C. Dupont, S. Pal, and M. Haeffelin The mixing layer height (MLH) is a key parameter for boundary layer studies, including meteorology, air quality, and climate. MLH estimates are inferred from in situ radiosonde measurements or remote sensing observations from instruments like lidar, wind profiling radar, or sodar. Methods used to estimate MLH from radiosonde profiles are also used with atmospheric temperature and humidity profiles retrieved by microwave radiometers (MWR). This paper proposes an alternative approach to estimate MLH from MWR data, based on direct observations (brightness temperatures, Tb) instead of retrieved profiles. To our knowledge, MLH estimates directly from Tb observations has never been attempted before. The method consists of a multivariate linear regression trained with an a priori set of collocated MWR Tb observations (multi-frequency and multi-angle) and MLH estimates from a state-of-the-art lidar system. Results show that the method is able to follow both the diurnal cycle and the day-to-day variability as suggested by the lidar measurements, and also it can detect low MLH values that are below the full overlap limit (~ 200 m) of the lidar system used. Statistics of the comparison between MWR- and reference lidar-based MLH retrievals show mean difference within 10 m, RMS within 340 m, and correlation coefficient higher than 0.77. Monthly mean analysis for day-time MLH from MWR, lidar, and radiosonde shows consistent seasonal variability, peaking at ~ 1200–1400 m in June and decreasing down to ~ 600 m in October. Conversely, night-time monthly mean MLH from all methods are within 300–500 m without any significant seasonal variability. The proposed method provides results that are more consistent with radiosonde estimates than MLH estimates from MWR retrieved profiles. MLH monthly mean values agree well within 1 std with bulk Richardson number method applied at radiosonde profiles at 11:00 and 23:00 UTC. The method described herewith operates continuously and it is expected to work with analogous performances for the entire diurnal cycle, except during considerable precipitation, demonstrating new potential for atmospheric observation by ground-based microwave radiometry.

Description: Stratospheric aerosol particle size information in Odin-OSIRIS limb scatter spectra Atmospheric Measurement Techniques Discussions, 6, 5065-5099, 2013 Author(s): L. A. Rieger, A. E. Bourassa, and D. A. Degenstein The Optical Spectrograph and InfraRed Imaging System (OSIRIS) on-board the Odin satellite has now taken over a decade of limb scatter measurements that have been used to retrieve the Version 5 stratospheric aerosol extinction product. This product is retrieved using a representative particle size distribution to calculate scattering cross sections and scattering phase functions for the forward model calculations. In this work the information content of OSIRIS measurements with respect to stratospheric aerosol is systematically examined for the purpose of retrieving particle size information along with the extinction coefficient. The benefit of using measurements at different wavelengths and scattering angles in the retrieval is studied and it is found that incorporation of the 1530 nm radiance measurement is key for a robust retrieval of particle size information. It is also found that using OSIRIS measurements at different solar geometries simultaneously provides little additional benefit. Based on these results, an improved aerosol retrieval algorithm is developed that couples the retrieval of aerosol extinction and mode radius of a log-normal particle size distribution. Comparison of these results with coincident measurements from SAGE III show agreement in retrieved extinction to within approximately 10% over the bulk of the aerosol layer, which is comparable to Version 5. The retrieved particle size, when converted to Ångström coefficient, shows good qualitative agreement with SAGE II measurements made at somewhat shorter wavelengths.

Description: SAGE version 7.0 algorithm: application to SAGE II Atmospheric Measurement Techniques Discussions, 6, 5101-5171, 2013 Author(s): R. P. Damadeo, J. M. Zawodny, L. W. Thomason, and N. Iyer This paper details the SAGE version 7.0 algorithm and how it is applied to SAGE II. Changes made between the previous (v6.2) and current (v7.0) versions are described and their impacts on the data products explained for both coincident event comparisons and time-series analysis. Users of the data will notice a general improvement in all of the SAGE II data products, which are now in better agreement with more modern data sets (e.g. SAGE III) and more robust for use with trend studies.

Description: Foraminiferal survival after long term experimentally induced anoxia Biogeosciences Discussions, 10, 9243-9284, 2013 Author(s): D. Langlet, E. Geslin, C. Baal, E. Metzger, F. Lejzerowicz, B. Riedel, M. Zuschin, J. Pawlowski, M. Stachowitsch, and F. J. Jorissen Anoxia has been successfully induced in four benthic chambers installed on the Northern Adriatic seafloor from 1 week to 10 months. To accurately determine whether benthic foraminifera can survive experimentally induced prolonged anoxia, the CellTrackerGreen method has been applied. Numerous individuals have been found living at all sampling times and at all sampling depths, showing that benthic foraminifera can survive up to 10 months of anoxia with co-occurring hydrogen sulphides. However, foraminiferal standing stocks decrease with sampling time in an irregular way. A large difference in standing stock between two cores samples in initial conditions indicates the presence of a large spatial heterogeneity of the foraminiferal faunas. An unexpected increase in standing stocks after 1 month is tentatively interpreted as a reaction to increased food availability due to the massive mortality of infaunal macrofaunal organisms. After this, standing stocks decrease again in a core sampled after 2 months of anoxia, to attain a minimum in the cores sampled after 10 months. We speculate that the trend of overall decrease of standing stocks is not due to the adverse effects of anoxia and hydrogen sulphides, but rather due to a continuous diminution of labile organic matter.

Description: Environmental controls on the Emiliania huxleyi calcite mass Biogeosciences Discussions, 10, 9285-9313, 2013 Author(s): M. T. Horigome, P. Ziveri, M. Grelaud, K.-H. Baumann, G. Marino, and P. G. Mortyn Although ocean acidification is expected to impact (bio)calcification by decreasing the seawater carbonate ion concentration, [CO 3 2− ], there exists evidence of non-uniform response of marine calcifying plankton to low seawater [CO 3 2− ]. This raises questions on the role of environmental factors other than acidification and on the complex physiological responses behind calcification. Here we investigate the synergistic effect of multiple environmental parameters, including temperature, nutrient (nitrate and phosphate) availability, and seawater carbonate chemistry on the coccolith calcite mass of the cosmopolitan coccolithophore Emiliania huxleyi , the most abundant species in the world ocean. We use a suite of surface (late Holocene) sediment samples from the South Atlantic and southwestern Indian Ocean taken from depths lying well above the modern lysocline. The coccolith calcite mass in our results presents a latitudinal distribution pattern that mimics the main oceanographic features, thereby pointing to the potential importance of phosphorus and temperature in determining coccolith mass by affecting primary calcification and possibly driving the E. huxleyi morphotype distribution. This evidence does not necessarily argue against the potentially important role of the rapidly changing seawater carbonate chemistry in the future, when unabated fossil fuel burning will likely perturb ocean chemistry beyond a critical point. Rather our study highlights the importance of evaluating the combined effect of several environmental stressors on calcifying organisms to project their physiological response(s) in a high CO 2 world and improve interpretation of paleorecords.

Description: UV-induced carbon monoxide emission from living vegetation Biogeosciences Discussions, 10, 9373-9388, 2013 Author(s): D. Bruhn, K. R. Albert, T. N. Mikkelsen, and P. Ambus The global burden of carbon monoxide (CO) is rather uncertain. In this paper we address the potential for UV-induced CO emission by living terrestrial vegetation surfaces. Real-time measurements of CO concentrations were made with a cavity enhanced laser spectrometer connected in closed loop to either an ecosystem chamber or a plant-leaf scale chamber. Leaves of all examined plant species exhibited emission of CO in response to artificial UV-radiation as well as the UV-component of natural solar radiation. The UV-induced rate of CO emission exhibited a rather low dependence on temperature, indicating an abiotic process. The emission of CO in response to the UV-component of natural solar radiation was also evident at the ecosystem scale.

Description: Nutrient dynamics in tropical rivers, estuarine-lagoons, and coastal ecosystems along the eastern Hainan Island Biogeosciences Discussions, 10, 9091-9147, 2013 Author(s): R. H. Li, S. M. Liu, Y. W. Li, G. L. Zhang, J. L. Ren, and J. Zhang Nutrient dynamics were studied along the eastern Hainan Island based on field observations during 2006–2009, to understand nutrient biogeochemical processes and to have an overview of human perturbations on coastal ecosystems in this tropical region. The concentrations of nutrients in the rivers had seasonal variations enriched with dissolved inorganic nitrogen (DIN). High riverine concentrations of nitrate were mainly originated from agricultural fertilizer input. The ratios of DIN : PO 4 3− ranged from 37 to 1063, suggesting preferential PO 4 3− relative to nitrogen in the rivers. The areal yields of dissolved silicate (DSi) varied from 76 to 448 × 10 3 mol km −2 yr −1 due to erosion over the drainage area, inducing high levels of DSi among worldwide tropical systems. Aquaculture ponds contained high concentrations of NH 4 + (up to 157 μM) and DON (up to 130 μM). Particulate phosphorus concentrations (0.5 ∼1.4 μM) were in lower level comparied with estuaries around the world. Particulate silicate levels in rivers and lagoons were lower than global average level. Nutrient biogeochemistry in coastal areas were affected by human activities (e.g. aquaculture, agriculture), as well as natural events such as typhoon. Nutrient concentrations were low because open sea water dispersed land-derived nutrients. Nutrient budgets were built based on a steady-state box model, which showed that riverine fluxes would be magnified by estuarine processes (e.g. regeneration, desorption) in the Wenchanghe/Wenjiaohe Estuary, Wanquan River estuary, and the Laoyehai Lagoon except in the Xiaohai Lagoon. Riverine and groundwater input were the major sources of nutrients to the Xiaohai Lagoon and the Laiyehai Lagoon, respectively. Riverine input and aquaculture effluent were the major sources of nutrients to the eastern coastal of Hainan Island. Nutrient inputs to the coastal ecosystem can be increased by typhoon-induced runoff of rainwater, and phytoplankton bloom in the sea would be caused.

Description: Southern Hemisphere imprint for Indo–Asian summer monsoons during the last glacial period as revealed by Arabian Sea productivity records Biogeosciences Discussions, 10, 9315-9343, 2013 Author(s): T. Caley, S. Zaragosi, J. Bourget, P. Martinez, B. Malaizé, F. Eynaud, L. Rossignol, T. Garlan, and N. Ellouz-Zimmermann The monsoon is one of the most important climatic phenomena: it promotes inter-hemispheric exchange of energy and affects the economical prosperity of several countries exposed to its seasonal seesaw. Previous studies in both the Indian and Asian monsoon systems have suggested a dominant north hemispheric (NH) control on summer monsoon dynamics at the scale of suborbital-millennial climatic changes, while the forcing/response of Indian and Asian monsoons at the orbital scale remains a matter of debate. Here nine marine sediment cores distributed across the whole Arabian Sea are used to build a regional surface marine productivity signal. The productivity signal is driven by the intensity of Indian summer monsoon winds. Results demonstrate the existence of an imprint of suborbital Southern Hemisphere (SH) temperature changes (i.e., Antarctica) on the Indian summer monsoon during the last glacial period, challenging the traditional and exclusive NH forcing hypothesis. Meanwhile, during the last deglaciation, the NH plays a more significant role. The δ 18 O signal recorded in the Asian monsoon speleothem records could be exported by winds from the Indian summer monsoon region, as recently proposed in modelling exercise, explaining the SH signature observed in Asian cave speleothems. Contrary to the view of a passive response of Indian and Asian monsoons to NH anomalies, the present results strongly suggest that the Indo–Asian summer monsoon plays an active role in amplifying millennial inter-hemispheric asymmetric patterns. Additionally, this study helps to decipher the observed differences between Indian and Asian-speleothem monsoonal records at the orbital-precession scale.

Description: Technical Note: Aeolian dust proxies produce visible luminescence upon intense laser-illumination that results from incandescence of internally mixed carbon Atmospheric Measurement Techniques Discussions, 6, 5173-5194, 2013 Author(s): L. Ma, T. Cao, and J. E. Thompson Mineral dust mimics dispersed in air produced visible luminescence between 550–800 nm when illuminated with a high peak power (MW range) Nd:YAG laser beam at 532 or 1064 nm. The luminescence persists for a few microseconds after the laser pulse and the measured emission spectrum is roughly consistent with a blackbody emitter at ≈4300 K. Both observations are consistent with assigning laser-induced incandescence (LII) as the source of the luminescence. However, light emission intensity from the mineral dust proxies is 240–4600 less intense than incandescence from fresh kerosene soot on a per-mass basis at laser pulse energies 90% on average. Heating to 350 °C reduced emission by 45–72%. Since black carbon soot and char (BC) oxidizes at elevated temperatures and BC is known to be present in soils, we conclude emission of light from the mineral dust aerosol proxies is likely a result of black carbon or char internally mixed within the soil dust sample. The reduction in LII response for samples heated to temperatures of 250–350 °C may result from partial oxidation of BC, but alternatively, could implicate a role for carbon present within organic molecules. The study suggests laser-induced incandescence measurements may allow quantitation of black carbon in soils and that soil dust is not truly an interferent in BC analysis by LII, but rather, a BC containing material.

Description: Heterogeneity of impacts of high CO 2 on the North Western European Shelf Biogeosciences Discussions, 10, 9389-9413, 2013 Author(s): Y. Artioli, J. C. Blackford, G. Nondal, R. G. J. Bellerby, S. L. Wakelin, J.T. Holt, M. Butenschön, and J. I. Allen The increase in atmospheric CO 2 is a dual threat to the marine environment: from one side it drives climate change leading to changes in water temperature, circulation patterns and stratification intensity; on the other side it causes a decrease in pH (Ocean Acidification or OA) due to the increase in dissolved CO 2 . Assessing the combined impact of climate change and OA on marine ecosystems is a challenging task: the response of the ecosystem to a single driver is highly variable and still uncertain, as well as the interaction between these that could be either synergistic or antagonistic. In this work we use the coupled oceanographic-ecosystem model POLCOMS-ERSEM driven by climate forcing to study the interaction between climate change and OA. We focus in particular on primary production and nitrogen speciation. The model has been run in three different configurations in order to separate the impacts of ocean acidification from those due to climate change. The model shows significant interaction among the drivers and high variability in the spatial response of the ecosystem. Impacts of climate change and of OA on primary production have similar magnitude, compensating in some area and exacerbating in others. On the contrary, the direct impact of OA on nitrification is much lower than the one imposed by climate change.

Description: On the role of mesoscale eddies for the biological productivity and biogeochemistry in the eastern tropical Pacific Ocean off Peru Biogeosciences Discussions, 10, 9179-9211, 2013 Author(s): L. Stramma, H. W. Bange, R. Czeschel, A. Lorenzo, and M. Frank Mesoscale eddies seem to play an important role for both the hydrography and biogeochemistry of the eastern tropical Pacific Ocean (ETSP) off Peru. However, detailed surveys of these eddies are not available, which has so far hampered an in depth understanding of their implications for nutrient distribution and biological productivity. In this study three eddies along a section at 16°45' S have been surveyed intensively during R/V Meteor cruise M90 in November 2012. A coastal mode water eddy, an open ocean mode water eddy and an open ocean cyclonic eddy have been identified and sampled in order to determine both their hydrographic properties and their influence on the biogeochemical setting of the ETSP. In the thermocline the temperature of the coastal anticyclonic eddy was up to 2 °C warmer, 0.2 more saline and the swirl velocity was up to 35 cm s –1 . The observed temperature and salinity anomalies, as well as swirl velocities of both types of eddies were about twice as large as had been described for the mean eddies in the ETSP and the observed heat and salt anomalies (AHA, ASA) show a much larger variability than the mean AHA and ASA. We found that the eddies contributed significantly to productivity by maintaining pronounced subsurface maxima of chlorophyll. Based on a comparison of the coastal (young) mode water eddy and the open ocean (old) mode water eddy we conclude that the aging of eddies when they detach from the coast and move westward to the open ocean considerably influences the eddies' properties: chlorophyll maxima are weaker and nutrients are subducted. The coastal mode water eddy was found to be a hotspot of nitrogen loss in the OMZ, whereas, the open ocean cyclonic eddy was of negligible importance for nitrogen loss. Our results show that the important role the eddies play in the ETSP can only be fully deciphered and understood through dedicated high spatial and temporal resolution oceanographic/biogeochemical surveys.

Description: Soil moisture modifies the response of soil respiration to temperature in a desert shrub ecosystem Biogeosciences Discussions, 10, 9213-9242, 2013 Author(s): B. Wang, T. S. Zha, X. Jia, B. Wu, Y. Q. Zhang, and S. G. Qin The response of soil respiration (Rs) to soil temperature and moisture have been well documented in forests, but data and information from desert shrub ecosystems are limited. Soil CO 2 efflux from a desert shrub ecosystem was measured continuously with automated chambers in Ningxia, northwest China, from June to October 2012. The responses of Rs to Ts was strongly affected diurnally by soil moisture, with the diel variation in Rs being strongly related to 10 cm soil temperature (Ts) at moderate and high soil volumetric water content (VWC), but less related to Ts at low VWC. Ts typically lagged Rs by 3–4 h, however, the lag time varied in relation to VWC, with increased lag times at low VWC. Over the seasonal cycle, daily mean Rs was positively correlated with Ts when VWC exceeded 0.08 m 3 m −3 , but became decoupled from Ts when VWC dropped below this threshold. The annual temperature sensitivity of Rs ( Q 10 ) was 1.5. The short-term sensitivity of Rs to Ts, computed using three-day windows, varied significantly over the seasonal cycle; the short-term Q 10 was negatively correlated with Ts and positively correlated with VWC. These results suggest the potential for a negative feedback to climate warming in desert ecosystems, related to the impact of low soil moisture on Rs. The results highlight the biological causes of diel hysteresis between Rs and Ts and the need for carbon cycle models to account for the interacting effects of Ts and VWC as joint determinants of Rs in desert ecosystem.

Description: Do successive climate extremes weaken the resistance of plant communities? An experimental study using plant assemblages Biogeosciences Discussions, 10, 9149-9177, 2013 Author(s): F. E. Dreesen, H. J. De Boeck, I. A. Janssens, and I. Nijs The probability that plant communities undergo successive climate extremes increases under climate change. Exposure to an extreme event might elicit acclimatory responses and thereby greater resistance to a subsequent event, but might also reduce resistance if the recovery period is too short or resilience too low. Using experimental plant assemblages, we compared the effects of two successive extremes (either two drought extremes, two heat extremes or two drought + heat extremes) to those of assemblages being exposed only to the second extreme. Additionally, the recovery period between the successive extremes was varied (2, 3.5 or 6 weeks). Among the different types of climate extremes, combined drought + heat extremes induced substantial leaf and plant mortality, while the effects of drought and heat extremes were smaller. Preceding drought + heat extremes lowered the resistance in terms of leaf survival to a subsequent drought + heat extreme if the recovery period was 2 weeks, even though the leaves had completely recovered during that interval. No reduced resistance to subsequent extremes was recorded with longer recovery times or with drought or heat extremes. Despite mortality on the short term, the drought + heat and the heat extremes increased the end-of-season aboveground biomass, independent of the number of events or the recovery period. These results show that the effect of a preceding extreme event disappears quite quickly, but that recurrent climate extremes with short time intervals can weaken the resistance of herbaceous plant assemblages. This can however be compensated afterwards through rapid recovery and secondary, positive effects in the longer term.

Description: Climate and land use change impacts on global terrestrial ecosystems, fire, and river flows in the HadGEM2-ES Earth System Model using the Representative Concentration Pathways Biogeosciences Discussions, 10, 6171-6223, 2013 Author(s): R. A. Betts, N. Golding, P. Gonzalez, J. Gornall, R. Kahana, G. Kay, L. Mitchell, and A. Wiltshire A new generation of an Earth System Model now includes a number of land surface processes directly relevant to analyzing potential impacts of climate change. This model, HadGEM2-ES, allows us to assess the impacts of climate change, multiple interactions, and feedbacks as the model is run. This paper discusses the results of century-scale HadGEM2-ES simulations from an impacts perspective–specifically, terrestrial ecosystems and water resources–for four different scenarios following the Representative Concentration Pathways (RCPs), being used for next assessment report of the Intergovernmental Panel on Climate Change (IPCC). Over the 21st Century, simulated changes in global and continential-scale terrestrial ecosystems due to climate change appear to be very similar in all 4 RCPs, even though the level of global warming by the end of the 21st Century ranges from 2 °C in the lowest scenario to 5.5° in the highest. A warming climate generally favours broadleaf trees over needleleaf, needleleaf trees over shrubs, and shrubs over herbaceous vegetation, resulting in a poleward shift of temperate and boreal forests and woody tundra in all scenarios. Although climate related changes are slightly larger in scenarios of greater warming, the largest differences between scenarios arise at regional scales as a consequence of different patterns of anthropogenic land cover change. In the model, the scenario with the lowest global warming results in the most extensive decline in tropical forest cover due to a large expansion of agriculture. Under all four RCPs, fire potential could increase across extensive land areas, particularly tropical and sub-tropical latitudes. River outflows are simulated to increase with higher levels of CO 2 and global warming in all projections, with outflow increasing with mean temperature at the end of the 21st Century at the global scale and in North America, Asia, and Africa. In South America, Europe, and Australia, the relationship with climate warming and CO 2 rise is less clear, probably as a result of land cover change exerting a dominant effect in those regions.

Description: Horizontal distribution of Fukushima-derived radiocesium in zooplankton in the northwestern Pacific Ocean Biogeosciences Discussions, 10, 6143-6170, 2013 Author(s): M. Kitamura, Y. Kumamoto, H. Kawakami, E. C. Cruz, and K. Fujikura The magnitude of the 9.0 Tohoku earthquake and the ensuing tsunami on 11 March 2011, inflicted heavy damage on the Fukushima Dai-ichi nuclear power plant (FNPP1). Fission products were emitted, falling over a broad range in the northern hemisphere, and water contaminated with radionuclides leaked into the ocean. In this study, we described the horizontal distribution of the Fukushima-derived radiocesium in zooplankton and in seawater in the western North Pacific Ocean (500–2100 km from the FNPP1) 10 months after the accident. 134 Cs and 137 Cs were detected in zooplankton and seawater from all the stations. Because of its short half-lives, 134 Cs detected in our samples could only be derived from the FNPP1 accident. The highest 137 Cs activity in zooplankton was same order of magnitude as that one month after the accident, and average activity was one or two orders of magnitude higher than 137 Cs activities observed before the accident around Japan. Horizontally, the radiocesium activity concentrations in zooplankton were high at around 25° N while those in surface seawater were high at around the transition area between the Kuroshio and the Oyashio Currents (36–40° N). We observed subsurface radiocesium maxima in density range of the North Pacific Subtropical Mode Water and occurrence of many diel vertical migratory zooplanktons. These suggested that the high activity concentrations in the subtropical zooplankton at around 25° N were connected to the subsurface radiocesium and active vertical migration of zooplankton. However, the high activity concentrations of radiocesium in subsurface seawater did not necessarily follow the higher radiocesium activity in zooplankton. Biological characteristics of zooplankton community possibly influenced how large was contamination of radiocesium in the community but it is still unknown what kind of biological factors were important.

Description: Estimating carbonate parameters from hydrographic data for the intermediate and deep waters of the Southern Hemisphere Oceans Biogeosciences Discussions, 10, 6225-6257, 2013 Author(s): H. C. Bostock, S. E. Mikaloff Fletcher, and M. J. M. Williams Using GLODAP and CLIVAR ocean carbon data, we have developed several multiple linear regression (MLR) algorithms to estimate alkalinity and dissolved inorganic carbon (DIC) in the intermediate and deep waters of the Southern Hemisphere (south of 25° S) from only hydrographic data (temperature, salinity and dissolved oxygen). A Monte Carlo experiment was used to identify a potential density (σ θ ) of 27.5 as an optimal break point between the two regimes with different MLR algorithms. The algorithms provide a good estimate of DIC ( R 2 =0.98) and alkalinity ( R 2 =0.91), and excellent agreement for aragonite and calcite saturation states ( R 2 =0.99). Combining the algorithms with the CSIRO Atlas of Regional Seas (CARS), we have been able to map the calcite saturation horizon (CSH) and aragonite saturation horizon (ASH) for the Southern Ocean at a spatial resolution of 0.5°. These maps are more detailed and more consistent with oceanography than the gridded GLODAP data. The high resolution ASH map reveals a dramatic circumpolar shoaling at the Polar Front. North of 40° S the CSH is deepest in the Atlantic (~ 4000 m) and shallower in the Pacific Ocean (~ 2750 m), while the CSH sits between 3200 and 3400 m in the Indian Ocean.

Description: Productivity of aboveground coarse wood biomass and stand age related to soil hydrology of Amazonian forests in the Purus-Madeira interfluvial area Biogeosciences Discussions, 10, 6417-6459, 2013 Author(s): B. B. L. Cintra, J. Schietti, T. Emillio, D. Martins, G. Moulatlet, P. Souza, C. Levis, C. A. Quesada, and J. Schöngart The ongoing demand for information on forest productivity has increased the number of permanent monitoring plots across the Amazon. Those plots, however, do not comprise the whole diversity of forest types in the Amazon. The complex effects of soil, climate and hydrology on the productivity of seasonally waterlogged interfluvial wetland forests are still poorly understood. The presented study is the first field-based estimate for tree ages and wood biomass productivity in the vast interfluvial region between the Purus and Madeira rivers. We estimate stand age and wood biomass productivity by a combination of tree-ring data and allometric equations for biomass stocks of eight plots distributed along 600 km in the Purus-Madeira interfluvial area that is crossed by the BR-319 highway. We relate stand age and wood biomass productivity to hydrological and edaphic conditions. Mean productivity and stand age were 5.6 ± 1.1 Mg ha −1 yr −1 and 102 ± 18 yr, respectively. There is a strong relationship between tree age and diameter, as well as between mean diameter increment and mean wood density within a plot. Regarding the soil hydromorphic properties we find a positive correlation with wood biomass productivity and a negative relationship with stand age. Productivity also shows a positive correlation with the superficial phosphorus concentration. In addition, superficial phosphorus concentration increases with enhanced soil hydromorphic condition. We raise three hypotheses to explain these results: (1) the reduction of iron molecules on the saturated soils with plinthite layers close to the surface releases available phosphorous for the plants; (2) the poor structure of the saturated soils creates an environmental filter selecting tree species of faster growth rates and shorter life spans and (3) plant growth on saturated soil is favored during the dry season, since there should be low restrictions for soil water availability.

Description: Retrieval of aerosol parameters from the oxygen A band in the presence of chlorophyll fluorescence Atmospheric Measurement Techniques Discussions, 6, 3181-3213, 2013 Author(s): A. F. J. Sanders and J. F. de Haan We have investigated precision of retrieved parameters for a generic aerosol retrieval algorithm over vegetated land using the O 2 A band. Chlorophyll fluorescence is taken into account in the forward model. Fluorescence emissions are modeled as isotropic contributions to the upwelling radiance field at the surface and they are retrieved along with aerosol parameters. Precision is calculated by propagating measurement noise using the forward model's derivatives. We assume that measurement noise is dominated by shot noise; thus, results apply to grating spectrometers in particular. In a number of retrieval simulations, we describe precision for various atmospheric states, observation geometries and spectral resolutions of the instrument. Our results show that aerosol optical thickness, aerosol pressure, fluorescence emission and surface albedo can be simultaneously retrieved from the O 2 A band. We also show that most of the fluorescence signal is provided by filling-in of the O 2 A band and to a lesser extent by filling-in of Fraunhofer lines.

Description: Sources and fate of terrestrial dissolved organic carbon in lakes of a Boreal Plains region recently affected by wildfire Biogeosciences Discussions, 10, 6093-6141, 2013 Author(s): D. Olefeldt, K. J. Devito, and M. R. Turetsky Downstream mineralization and sedimentation of terrestrial dissolved organic carbon (DOC) render lakes important for landscape carbon cycling in the boreal region, with regulating processes potentially sensitive to perturbations associated with climate change including increased occurrence of wildfire. In this study we assessed chemical composition and reactivity (during both dark and UV incubations) of DOC from lakes and terrestrial sources within a peatland-rich western boreal plains region partially affected by a recent wildfire. While wildfire was found to increase aromaticity of DOC in peat pore-water above the water table, it had no effect on concentrations or composition of DOC from peatland wells and neither affected mineral well or lake DOC characteristics. Lake DOC composition reflected a mixing of peatland and mineral groundwater, with a greater influence of mineral sources to lakes in coarse- than fine-textured settings. Peatland DOC was less biodegradable than mineral DOC, but both mineralization and sedimentation of peatland DOC increased substantially during UV incubations through selective removal of aromatic humic and fulvic acids. DOC composition in lakes with longer residence times had characteristics consistent with increased UV-mediated processing. We estimate that about half of terrestrial DOC inputs had been lost within lakes, mostly due to UV-mediated processes. The importance of within-lake losses of aromatic DOC from peatland sources through UV-mediated processes indicate that terrestrial-aquatic C linkages in the study region are largely disconnected from recent terrestrial primary productivity. Together, our results suggest that characteristics of the study region (climate, surface geology and lake morphometry) render linkages between terrestrial and aquatic C cycling insensitive to the effects of wildfire by determining dominant terrestrial sources and within-lake processes of DOC removal.

Description: McClear: a new model estimating downwelling solar radiation at ground level in clear-sky conditions Atmospheric Measurement Techniques Discussions, 6, 3367-3405, 2013 Author(s): M. Lefèvre, A. Oumbe, P. Blanc, B. Espinar, B. Gschwind, Z. Qu, L. Wald, M. Schroedter-Homscheidt, C. Hoyer-Klick, A. Arola, A. Benedetti, J. W. Kaiser, and J.-J. Morcrette A new fast clear-sky model called McClear was developed to estimate the downwelling shortwave direct and global irradiances received at ground level under clear skies. McClear implements a fully physical modelling replacing empirical relations or simpler models used before. It exploits the recent results on aerosol properties, and total column content in water vapor and ozone produced by the MACC project (Monitoring Atmosphere Composition and Climate). It accurately reproduces the irradiance computed by the libRadtran reference radiative transfer model with a computational speed approximately 10 5 times greater by adopting the abaci, or look-up tables, approach combined with interpolation functions. It is therefore suited for geostationary satellite retrievals or numerical weather prediction schemes with many pixels or grid points, respectively. McClear irradiances were compared to 1 min measurements made in clear-sky conditions in several stations within the Baseline Surface Radiation Network in various climates. For global, respectively direct, irradiance, the correlation coefficient ranges between 0.95 and 0.99, resp. 0.86 and 0.99. The bias is comprised between −14 and 25 W m −2 , resp. −49 and +33 W m −2 . The RMSE ranges between 20 W m −2 (3% of the mean observed irradiance) and 36 W m −2 (5%), resp. 33 W m −2 (5%) and 64 W m −2 (10%). These results are much better than those from state-of-the-art models. This work demonstrates the quality of the McClear model combined with MACC products, and indirectly the quality of the aerosol properties modeled by the MACC reanalysis.

Description: Experimental quantification of contact freezing in an electrodynamic balance Atmospheric Measurement Techniques Discussions, 6, 3407-3437, 2013 Author(s): N. Hoffmann, A. Kiselev, D. Rzesanke, D. Duft, and T. Leisner Heterogeneous nucleation of ice in a supercooled water droplet induced by an external contact with a dry aerosol particle has long been known to be more effective than freezing induced by the same nucleus immersed in the droplet. However, the experimental quantification of contact freezing is challenging. Here we report an experimental method allowing to determine the temperature dependent ice nucleation probability of size selected aerosol particles. The method uses supercooled charged water droplets suspended in a laminar flow of air containing aerosol particles as contact freezing nuclei. The rate of droplet–particle collisions is calculated numerically with account for Coulomb attraction, drag force and induced dipole interaction between charged droplet and aerosol particles. The calculation is verified by direct counting of aerosol particles collected by a levitated droplet. By repeating the experiment on individual droplets for a sufficient number of times, we are able to reproduce the statistical freezing behavior of a large ensemble of supercooled droplets and measure the average rate of freezing events. The freezing rate is equal to the product of the droplet–particle collision rate and the probability of freezing on a single contact, the latter being a function of temperature, size and composition of the contact ice nuclei. Based on these observations, we show that for the types of particles investigated so far, contact freezing is the dominating freezing mechanism on the time scale of our experiment.

Description: Solute specific scaling of inorganic nitrogen and phosphorus uptake in streams Biogeosciences Discussions, 10, 6671-6693, 2013 Author(s): R. O. Hall Jr., M. A. Baker, E. J. Rosi-Marshall, and J. L. Tank Stream ecosystem processes such as nutrient cycling may vary with stream position in the watershed. Using a scaling approach, we examined the relationship between stream size and nutrient uptake length, which represents the mean distance that a dissolved solute travels prior to removal from the water column. Ammonium uptake length increased proportionally with stream size measured as specific discharge (discharge/stream width) with a scaling exponent = 1.01. In contrast, the scaling exponent for nitrate (NO 3 − ) was 1.19 and for soluble reactive phosphorus (SRP) was 1.35, suggesting that uptake lengths for these nutrients increased more rapidly than increases in specific discharge. Additionally, the ratio of nitrogen (N) uptake length to SRP uptake length declined with stream size; there was lower demand for SRP relative to N as stream size increased. Ammonium and NO 3 − uptake velocity positively related with stream metabolism, while SRP did not. Finally, we related the scaling of uptake length and specific discharge to that of stream length using Hack's law and downstream hydraulic geometry. Ammonium uptake length increased less than proportionally with distance from the headwaters, suggesting a strong role for larger streams and rivers in regulating nutrient transport.

Description: Responses of lower trophic-level organisms to typhoon passage on the outer shelf of the East China Sea: an incubation experiment Biogeosciences Discussions, 10, 6605-6635, 2013 Author(s): N. Yasuki, K. Suzuki, and A. Tsuda Typhoons can induce vertical mixing, upwelling, or both in the water column due to strong wind stress. These events can induce phytoplankton blooms in the oligotrophic ocean after typhoon passage. However, little is known about the responses of lower trophic-level organisms or changes in the community structure following the passage of typhoons, particularly in offshore regions. Therefore, we evaluated community succession on the outer shelf of the East China Sea through on-deck bottle incubation experiments simulating hydrographic conditions after the passage of a typhoon. Under all of the experimental conditions we tested, chlorophyll a concentrations increased more than 9-fold within 6 days, and these algal cells were mainly composed of large diatoms (〉10 μm). Ciliates also increased along with the diatom bloom. These results suggest that increases in diatom and ciliate populations may enhance biogenic carbon export in the water column. Typhoons can affect not only phytoplankton productivity, but also the composition of lower trophic-level organisms and biogeochemical processes in oligotrophic offshore regions.

Description: Separating mixtures of aerosol types in airborne High Spectral Resolution Lidar data Atmospheric Measurement Techniques Discussions, 6, 8269-8309, 2013 Author(s): S. P. Burton, M. A. Vaughan, R. A. Ferrare, and C. A. Hostetler Knowledge of aerosol type is important for source attribution and for determining the magnitude and assessing the consequences of aerosol radiative forcing. However, atmospheric aerosol is frequently not a single pure type, but instead occurs as a mixture of types, and this mixing affects the optical and radiative properties of the aerosol. This paper extends the work of earlier researchers by using the aerosol intensive parameters measured by the NASA Langley Research Center airborne High Spectral Resolution Lidar (HSRL-1) to develop a comprehensive and unified set of rules for characterizing the external mixing of several key aerosol intensive parameters: extinction-to-backscatter ratio (i.e. lidar ratio), backscatter color ratio, and depolarization ratio. We present the mixing rules in a particularly simple form that leads easily to mixing rules for the covariance matrices that describe aerosol distributions, rather than just scalar values of measured parameters. These rules can be applied to infer mixing ratios from the lidar-observed aerosol parameters, even for cases without significant depolarization. We demonstrate our technique with measurement curtains from three HSRL-1 flights which exhibit mixing between two aerosol types, urban pollution plus dust, marine plus dust, and smoke plus marine. For these cases, we infer a time-height cross-section of mixing ratio along the flight track, and partition aerosol extinction into portions attributed to the two pure types.

Description: Icehouse-greenhouse variations in marine denitrification Biogeosciences Discussions, 10, 14769-14813, 2013 Author(s): T. J. Algeo, P. A. Meyers, R. S. Robinson, H. Rowe, and G. Q. Jiang Long-term secular variation in the isotopic composition of seawater fixed nitrogen (N) is poorly known. Here, we document variation in the N-isotopic composition of marine sediments (δ 15 N sed ) since 660 Ma (million years ago) in order to understand major changes in the marine N cycle through time and their relationship to first-order climate variation. During the Phanerozoic, greenhouse climate modes were characterized by low δ 15 N sed (∼ −2 to +2‰) and icehouse climate modes by high δ 15 N sed (∼ +4 to +8‰). Shifts toward higher δ 15 N sed occurred rapidly during the early stages of icehouse modes, prior to the development of major continental glaciation, suggesting a potentially important role for the marine N cycle in long-term climate change. Reservoir box modeling of the marine N cycle demonstrates that secular variation in δ 15 N sed was likely due to changes in the dominant locus of denitrification, with a shift in favor of sedimentary denitrification during greenhouse modes owing to higher eustatic (global sea-level) elevations and greater on-shelf burial of organic matter, and a shift in favor of water-column denitrification during icehouse modes owing to lower eustatic elevations, enhanced organic carbon sinking fluxes, and expanded oceanic oxygen-minimum zones. The results of this study provide new insights into operation of the marine N cycle, its relationship to the global carbon cycle, and its potential role in modulating climate change at multimillion-year timescales.

Description: Technical Note: Disturbance of soil structure can lead to release of methane entrapped in glacier forefield soils Biogeosciences Discussions, 10, 14815-14834, 2013 Author(s): P. A. Nauer, E. Chiri, J. Zeyer, and M. H. Schroth Investigations of sources and sinks of atmospheric CH 4 are needed to understand the global CH 4 cycle and climate-change mitigation options. Glaciated environments might play a critical role due to potential feedbacks with global glacial meltdown. In an emerging glacier forefield, an ecological shift occurs from an anoxic, potentially methanogenic subglacial sediment to an oxic proglacial soil, in which soil-microbial consumption of atmospheric CH 4 is initiated. The development of this change in CH 4 turnover can be quantified by soil-gas profile analysis. We found evidence for CH 4 entrapped in glacier forefield soils when comparing two methods for the collection of soil-gas samples: a modified steel rod (SR) designed for one-time sampling and rapid screening (samples collected ~ 1 min after hammering the SR into the soil), and a novel multi-level sampler (MLS) for repetitive sampling through a previously installed access tube (samples collected weeks after access-tube installation). In glacier forefields on siliceous bedrock, sub-atmospheric CH 4 concentrations were observed with both methods. Conversely, elevated soil-CH 4 concentrations were observed in calcareous glacier forefields, but only in samples collected with the SR, while MLS samples all showed sub-atmospheric CH 4 concentrations. Time-series SR soil-gas sampling (additional samples collected 2, 3, 5, and 7 min after hammering) confirmed the transient nature of the elevated soil-CH 4 concentrations, which were decreasing from ~ 100 μL L −1 towards background levels within minutes. This hints towards the existence of entrapped CH 4 in calcareous glacier forefield soil that can be released when sampling soil-gas with the SR. Laboratory experiments with miniature soil cores collected from two glacier forefields confirmed CH 4 entrapment in these soils. Treatment by sonication and acidification resulted in a massive release of CH 4 from calcareous cores (on average 0.3–1.8 μg CH 4 (g d.w.) −1 ); release from siliceous cores was 1–2 orders of magnitude lower (0.02–0.03 μg CH 4 (g d.w.) −1 ). Clearly, some form of CH 4 entrapment exists in calcareous glacier forefield soils, and to a much lesser extent in siliceous glacier forefield soils. Its nature and origin remain unclear and will be subject of future investigations.

Description: Dynamics of particulate organic carbon flux in a global ocean model Biogeosciences Discussions, 10, 14715-14767, 2013 Author(s): I. D. Lima, P. J. Lam, and S. C. Doney The sinking of particulate organic carbon (POC) is a key component of the ocean carbon cycle and plays an important role in the global climate system. However, the processes controlling the fraction of primary production that is exported from the euphotic zone (export ratio) and how much of it survives respiration in the mesopelagic to be sequestered in the deep ocean (transfer efficiency) are not well understood. In this study, we use a three-dimensional, coupled physical-biogeochemical model (CCSM-BEC) to investigate the processes controlling the export of particulate organic matter from the euphotic zone and its flux to depth. We also compare model results with sediment trap data and other parameterizations of POC flux to depth to evaluate model skill and gain further insight into the causes of error and uncertainty in POC flux estimates. In the model, export ratios are mainly a function of diatom relative abundance and temperature while absolute fluxes and transfer efficiency are driven by mineral ballast composition of sinking material. The temperature dependence of the POC remineralization length scale is modulated by denitrification under low O 2 concentrations and lithogenic (dust) fluxes. Lithogenic material is an important control of transfer efficiency in the model, but its effect is restricted to regions of strong atmospheric dust deposition. In the remaining regions, CaCO 3 content of exported material is the main factor affecting transfer efficiency. The fact that mineral ballast composition is inextricably linked to plankton community structure results in correlations between export ratios and ballast minerals fluxes (opal and CaCO 3 ), and transfer efficiency and diatom relative abundance that do not necessarily reflect ballast or direct ecosystem effects, respectively. This suggests that it might be difficult to differentiate between ecosystem and ballast effects in observations. The model's skill at reproducing sediment trap observations is equal to or better than that of other parameterizations. However, the sparseness and relatively large uncertainties of sediment trap data makes it difficult to accurately evaluate the skill of the model and other parameterizations. More POC flux observations, over a wider range of ecological regimes, are necessary to thoroughly evaluate and test model results and better understand the processes controlling POC flux to depth in the ocean.

Description: Thin terrestrial sediment deposits on intertidal sandflats: effects on pore water solutes and juvenile bivalve burial behaviour Biogeosciences Discussions, 10, 14835-14860, 2013 Author(s): A. Hohaia, K. Vopel, and C. A. Pilditch Changes in land use and climate increase the supply of terrestrial sediment (hereafter, TS) to coastal waters worldwide but the effects of these sediments on benthic ecosystem functioning are not well known. Past experiments with defaunated, intertidal sediment suggested a link between the de-oxygenation of sediments underlying a thin (mm) layer of TS and reduced burial rates of juvenile macrofaunal recruits. We examined this link predicting that surficial TS deposits will still negatively affect burial when applied to sediments that are initially well oxygenated due to bioturbation (C) or depleted of organic matter (D). We observed the behaviour of post-settlement juveniles of the tellinid bivalve \textit{Macomona liliana} on the surface of four treatments; C, D, and the same sediments to which we added a thin layer of TS (CTS, DTS). Pore water analyses confirmed that the diffusive impedance of the 1.7–1.9 mm TS deposit decreased the oxygenation of the underlying intertidal sediment (CTS) but not that of the depleted sediment (DTS). Unexpectedly, (1) the application of a TS deposit significantly increased but not decreased the probability of burial, irrespectively of treatment, and (2) juveniles more likely buried into C than into D. We attribute the failure to document a negative effect of TS on the recruits' burial to the activity of the resident macroinfauna (CTS) or the absence of organic matter (DTS). Our results underline the important role of the resident macrofauna in mediating the stress response of benthic ecosystems.

Description: Lidar-based remote sensing of atmospheric boundary layer height over land and ocean Atmospheric Measurement Techniques Discussions, 6, 8311-8338, 2013 Author(s): T. Luo, R. Yuan, and Z. Wang Atmospheric boundary layer (ABL) processes are important in climate, weather and air quality. A better understanding of the structure and the behavior of the ABL is required for understanding and modeling of the chemistry and dynamics of the atmosphere on all scales. Based on the systematic variations of ABL structures over different surfaces, different lidar-based methods were developed and evaluated to determine the boundary layer height and mixing layer height over land and ocean. With Atmospheric Radiation Measurement Program (ARM) Climate Research Facility (ACRF) micropulse lidar (MPL) and radiosonde measurements, diurnal and season cycles of atmospheric boundary layer depth and ABL vertical structure over ocean (TWP_C2 cite) and land (SGP_C1) are analyzed. The new methods are also applied to satellite lidar measurements. The derived global marine boundary layer structure database shows good agreement with marine ABL stratiform cloud top height.

Description: Calcium carbonate corrosivity in an Alaskan inland sea Biogeosciences Discussions, 10, 14887-14922, 2013 Author(s): W. Evans, J. T. Mathis, and J. N. Cross Ocean acidification is the hydrogen ion increase caused by the oceanic uptake of anthropogenic CO 2 , and is a focal point in marine biogeochemistry, in part, because this chemical reaction reduces calcium carbonate (CaCO 3 ) saturation states (Ω) to levels that are corrosive (i.e. Ω ≤ 1) to shell-forming marine organisms. However, other processes can drive CaCO 3 corrosivity; specifically, the addition of tidewater glacial melt. Carbonate system data collected in May and September from 2009 through 2012 in Prince William Sound (PWS), a semi-enclosed inland sea located on the south-central coast of Alaska that is ringed with fjords containing tidewater glaciers, reveal the unique impact of glacial melt on CaCO 3 corrosivity. Initial limited sampling was expanded in September 2011 to span large portions of the western and central sound, and included two fjords proximal to tidewater glaciers: Icy Bay and Columbia Bay. The observed conditions in these fjords affected CaCO 3 corrosivity in the upper water column (

Description: Fast reconstruction of hyperspectral radiative transfer simulations by using small spectral subsets: application to the oxygen A band Atmospheric Measurement Techniques Discussions, 6, 8339-8370, 2013 Author(s): A. Hollstein and R. Lindstrot Hyperspectral radiative transfer simulations are a versatile tool in remote sensing but can pose a major computational burden. We describe a simple method to construct hyperspectral simulation results by using only a small spectral subsample of the simulated wavelength range, thus leading to major speedups in such simulations. This is achieved by computing principal components for a small number of representative hyperspectral spectra and then deriving a reconstruction matrix for a specific spectral subset of channels to compute the hyperspectral data. The method is applied and discussed in detail using the example of top of atmosphere radiances in the oxygen A band, leading to speedups in the range of one to two orders of magnitude when compared to radiative transfer simulations at full spectral resolution.

Description: Surface circulation and upwelling patterns around Sri Lanka Biogeosciences Discussions, 10, 14953-14998, 2013 Author(s): A. de Vos, C. B. Pattiaratchi, and E. M. S. Wijeratne Sri Lanka occupies a unique location within the equatorial belt in the northern Indian Ocean with the Arabian Sea on its western side and the Bay of Bengal on its eastern side. The region is characterised by bi-annually reversing monsoon winds resulting from seasonal differential heating and cooling of the continental land mass and the ocean. This study explored elements of the dynamics of the surface circulation and coastal upwelling in the waters around Sri Lanka using satellite imagery and the Regional Ocean Modelling System (ROMS) configured to the study region and forced with ECMWF interim data. The model was run for 2 yr to examine the seasonal and shorter term (∼10 days) variability. The results confirmed the presence of the reversing current system in response to the changing wind field: the eastward flowing Southwest Monsoon Current (SMC) during the Southwest (SW) monsoon transporting 11.5 Sv and the westward flowing Northeast Monsoon Current (NMC) transporting 9.5 Sv during the Northeast (NE) monsoon, respectively. A recirculation feature located to the east of Sri Lanka during the SW monsoon, the Sri Lanka Dome, is shown to result from the interaction between the SMC and the Island of Sri Lanka. Along the eastern and western coasts, during both monsoon periods, flow is southward converging along the south coast. During the SW monsoon the Island deflects the eastward flowing SMC southward whilst along the east coast the southward flow results from the Sri Lanka Dome recirculation. The major upwelling region, during both monsoon periods, is located along the south coast and is shown to be due to flow convergence and divergence associated with offshore transport of water. Higher surface chlorophyll concentrations were observed during the SW monsoon. The location of the flow convergence and hence the upwelling centre was dependent on the relative strengths of wind driven flow along the east and west coasts: during the SW (NE) monsoon the flow along the western (eastern) coast was stronger and hence the upwelling centre was shifted to the east (west). The presence of upwelling along the south coast during both monsoon periods may explain the blue whale ( Balaenoptera musculus ) aggregations in this region.

Description: An assessment of cloud top thermodynamic phase products obtained from A-Train passive and active sensors Atmospheric Measurement Techniques Discussions, 6, 8371-8411, 2013 Author(s): S. Zeng, J. Riedi, F. Parol, C. Cornet, and F. Thieuleux The A-Train observations provide an unprecedented opportunity for the production of high quality dataset describing cloud properties. We illustrate in this study the use of one year of coincident POLDER (Polarization and Directionality of the Earth Reflectance), MODIS (MODerate Resolution Imaging Spectroradiometer) and CALIOP (Cloud-Aerosol Lidar with Orthogonal Polarization) observations to establish a reference dataset for the description of cloud top thermodynamic phase at global scale. We present the results of an extensive comparison between POLDER and MODIS cloud top phase products and discuss those in view of cloud vertical structure and optical properties derived simultaneously from collocated CALIOP active measurements. These results allow to identify and quantify potential biases present in the 3 considered dataset. Among those, we discuss the impacts of observation geometry, thin cirrus in multilayered and single layered cloud systems, supercooled liquid droplets, aerosols, fractional cloud cover and snow/ice or bright surfaces on global statistics of cloud phase derived from POLDER and MODIS passive measurements. Based on these analysis we define criteria for the selection of high confidence cloud phase retrievals which in turn can serve for the establishment of a reference cloud phase product. This high confidence joint product derived from POLDER/PARASOL and MODIS/Aqua can be used in the future as a benchmark for the evaluation of other cloud climatologies, for the assessment of cloud phase representation in models and the development of better cloud phase parametrization in the general circulation models (GCMs).

Description: Strong sensitivity of Southern Ocean carbon uptake and nutrient cycling to wind stirring Biogeosciences Discussions, 10, 15033-15076, 2013 Author(s): K. B. Rodgers, O. Aumont, S. E. Mikaloff Fletcher, Y. Plancherel, L. Bopp, C. de Boyer Montégut, D. Iudicone, R. F. Keeling, G. Madec, and R. Wanninkhof Here we test the hypothesis that winds have an important role in determining the rate of exchange of CO 2 between the atmosphere and ocean through wind stirring over the Southern Ocean. This is tested with a sensitivity study using an ad hoc parameterization of wind stirring in an ocean carbon cycle model. The objective is to identify the way in which perturbations to the vertical density structure of the planetary boundary in the ocean impacts the carbon cycle and ocean biogeochemistry. Wind stirring leads to reduced uptake of CO 2 by the Southern Ocean over the period 2000–2006, with differences of order 0.9 Pg C yr −1 over the region south of 45° S. Wind stirring impacts not only the mean carbon uptake, but also the phasing of the seasonal cycle of carbon and other species associated with ocean biogeochemistry. Enhanced wind stirring delays the seasonal onset of stratification, and this has large impacts on both entrainment and the biological pump. It is also found that there is a strong sensitivity of nutrient concentrations exported in Subantarctic Mode Water (SAMW) to wind stirring. This finds expression not only locally over the Southern Ocean, but also over larger scales through the impact on advected nutrients. In summary, the large sensitivity identified with the ad hoc wind stirring parameterization offers support for the importance of wind stirring for global ocean biogeochemistry, through its impact over the Southern Ocean.

Description: Odin-OSIRIS detection of the Chelyabinsk meteor Atmospheric Measurement Techniques Discussions, 6, 8435-8443, 2013 Author(s): L. A. Rieger, A. E. Bourassa, and D. A. Degenstein On 15 February 2013 an 11 000 ton meteor entered Earth's atmosphere south east of Chelyabinsk creating a large fireball at 23 km altitude. The resulting stratospheric aerosol loading was detected by the Ozone Mapping and Profiler Suite (OMPS) in a high altitude polar belt. This work confirms the presence and lifetime of the stratospheric debris using the Optical Spectrograph and InfraRed Imaging System (OSIRIS) onboard the Odin satellite. Although OSIRIS coverage begins in mid-March, the measurements show a belt of enhanced scattering near 35 km altitude between 50° N and 70° N. Initially, enhancements show increased scattering of up to 15% over the background conditions, decaying in intensity and dropping in altitude until they are indistinguishable from background conditions by mid-May.

Description: Probabilistic approach to cloud and snow detection on AVHRR imagery Atmospheric Measurement Techniques Discussions, 6, 8445-8507, 2013 Author(s): J. P. Musial, F. Hüsler, M. Sütterlin, C. Neuhaus, and S. Wunderle The derivation of probability estimates complementary to geophysical data sets has gained special attention over the last years. The information about a confidence level of provided physical quantities is required to construct an error budget of higher level products and to correctly interpret final results of a particular analysis. Regarding the generation of products based on satellite data the common input consists of a cloud mask which allows discrimination between surface and cloud signals. Further the surface information is divided between snow and snow-free components. At any step of this discrimination process a misclassification in a cloud/snow mask propagates to higher level products and may alter their usability. Within this scope a novel Probabilistic Cloud Mask (PCM) algorithm suited for the 1×1 km Advanced Very High Resolution Radiometer (AVHRR) data is proposed which provides three types of probability estimates between: cloudy/clear-sky, cloudy/snow and clear-sky/snow conditions. As opposed to the majority of available techniques which are usually based on a decision-tree approach in the PCM algorithm all spectral, angular and ancillary information is used in a single step to retrieve the probability estimates from the pre-computed Look Up Tables (LUTs). Moreover, the issue of derivation of a single threshold value for a spectral test was overcome by the concept of multidimensional information space which is divided into small bins by an extensive set of thresholds. The discrimination between snow and ice clouds and detection of broken, thin clouds was enhanced by means of the Invariant Coordinate System (ICS) transformation. The study area covers a wide range of environmental conditions spanning from Iceland through central Europe to northern parts of Africa which exhibit diverse difficulties for cloud/snow masking algorithms. The retrieved PCM cloud classification was compared to the PPSv2012 and MOD35 collection 6 cloud masks, SYNOP weather reports, CALIPSO vertical feature mask version 3 and to MOD10A1 collection 5 snow mask. The outcomes of conducted analyses proved fine detection skills of the PCM method with comparable or better results than the reference PPS algorithm.

Description: Retrieval techniques for airborne imaging of methane concentrations using high spatial and moderate spectral resolution: application to AVIRIS Atmospheric Measurement Techniques Discussions, 6, 8543-8588, 2013 Author(s): A. K. Thorpe, C. Frankenberg, and D. A. Roberts Two quantitative retrieval techniques were evaluated to estimate methane (CH 4 ) enhancement in concentrated plumes using high spatial and moderate spectral resolution data from the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS). An Iterative Maximum a Posteriori Differential Optical Absorption Spectroscopy (IMAP-DOAS) algorithm performed well for an ocean scene containing natural CH 4 emissions from the Coal Oil Point (COP) seep field near Santa Barbara, California. IMAP-DOAS retrieval precision errors are expected to equal between 0.31 to 0.61 ppm CH 4 over the lowest atmospheric layer (height up to 1.04 km), corresponding to about a 30 to 60 ppm error for a 10 m thick plume. However, IMAP-DOAS results for a terrestrial scene were adveresly influenced by the underlying landcover. A hybrid approach using Singular Value Decomposition (SVD) was particularly effective for terrestrial surfaces because it could better account for spectral variability in surface reflectance. Using this approach, a CH 4 plume was observed immediately downwind of two hydrocarbon storage tanks at the Inglewood Oil Field in Los Angeles, California, with a maximum near surface enhancement of 8.45 ppm above background. At COP, the distinct plume had a maximum enhancement of 2.85 ppm CH 4 above background and was consistent with known seep locations and local wind direction. A sensitivity analysis also indicates CH 4 sensitivity should be more than doubled for the next generation AVIRIS sensor (AVIRISng) due to improved spectral resolution and sampling. AVIRIS-like sensors offer the potential to better constrain emissions on local and regional scales, including sources of increasing concern like industrial point source emissions and fugitive CH 4 from the oil and gas industry.

Description: Effects of solar activity and geomagnetic field on noise in CALIOP profiles above the South Atlantic Anomaly Atmospheric Measurement Techniques Discussions, 6, 8589-8602, 2013 Author(s): V. Noel, H. Chepfer, C. Hoareau, M. Reverdy, and G. Cesana By documenting noise levels in 6.5 yr of nighttime measurements by the spaceborne lidar CALIOP above the South Atlantic Anomaly (SAA), we show they contain information about the evolution of upwelling high-energy radiation levels in the area. We find the amount of noisy profiles is influenced by the 11 yr cycle of solar activity, fluctuates by ±5% between 2006 and 2013, and is anticorrelated with solar activity with a 1 yr lag. The size of the SAA grows as solar activity decreases, and an overall westward shift of the SAA region is detectable. We predict SAA noise levels will increase anew after 2014, and will affect future spaceborne lidar missions most near 2020. In other areas, supposedly unaffected by incoming sunlight, nighttime noise levels are much weaker but follow the same 11 yr cycle, superimposed with a one-year cycle that affects both hemispheres similarly and could be attributed to geomagnetic activity.

Description: Impact of seawater Ca 2+ on the calcification and calcite Mg/Ca of Amphistegina lessonii Biogeosciences Discussions, 11, 17463-17489, 2014 Author(s): A. Mewes, G. Langer, S. Thoms, G. Nehrke, G.-J. Reichart, L. J. de Nooijer, and J. Bijma Mg/Ca ratios in foraminiferal tests are routinely used as paleo temperature proxy, but on long timescales, also hold the potential to reconstruct past seawater Mg/Ca. Impact of both temperature and seawater Mg/Ca on Mg incorporation in foraminifera have been quantified by a number of studies. The underlying mechanism responsible for Mg incorporation in foraminiferal calcite and its sensitivity to environmental conditions, however, is not fully identified. A recently published biomineralization model (Nehrke et al., 2013) proposes a combination of transmembrane transport and seawater leakage or vacuolization to link calcite Mg/Ca to seawater Mg/Ca and explains inter-species variability in Mg/Ca ratios. To test the assumptions of this model, we conducted a culture study in which seawater Mg/Ca was manipulated by varying [Ca 2+ ] and keeping [Mg 2+ ] constant. Foraminiferal growth rates, test thickness and calcite Mg/Ca of newly formed chambers were analyzed. Results showed optimum growth rates and test thickness at Mg/Ca closest to that of ambient seawater. Calcite Mg/Ca is positively correlated to seawater Mg/Ca, indicating that not absolute seawater [Ca 2+ ] and [Mg 2+ ], but the telative ratio controls Mg/Ca in tests. These results demonstrate that the calcification process cannot be based only on seawater vacuolization, supporting the mixing model proposed by Nehrke et al. (2013). Here we, however, suggest a transmembrane transport fractionation that is not as strong as suggested by Nehrke et al. (2013).

Description: Fluxes of carbon and nutrients to the Iceland Sea surface layer and inferred primary productivity and stoichiometry Biogeosciences Discussions, 11, 15399-15433, 2014 Author(s): E. Jeansson, R. G. J. Bellerby, I. Skjelvan, H. Frigstad, S. R. Ólafsdóttir, and J. Ólafsson Fluxes of carbon and nutrients to the upper 100 m of the Iceland Sea are evaluated. The study utilises hydro-chemical data from the Iceland Sea time-series station (68.00° N, 12.67° W), for the years between 1993 and 2006. By comparing data of dissolved inorganic carbon (DIC) and nutrients in the surface layer (upper 100 m), and a sub-surface layer (100–200 m), we calculate monthly deficits in the surface, and use these to deduce the surface layer fluxes that affect the deficits: vertical mixing, horizontal advection, air–sea exchange, and biological activity. The deficits show a clear seasonality with a minimum in winter, when the mixed layer is at the deepest, and a maximum in early autumn, when biological uptake has removed much of the nutrients. The annual vertical fluxes of DIC and nitrate amounts to 1.7 ± 0.3 and 0.23 ± 0.07 mol m −2 yr −1 , respectively, and the annual air–sea uptake of atmospheric CO 2 is 4.4 ± 1.1 mol m −2 yr −1 . The biologically driven changes in DIC during the year relates to net community production (NCP), and the net annual NCP corresponds to export production, and is here calculated to 6.1 ± 0.9 mol C m −2 yr −1 . The typical, median C : N ratio during the period of net community uptake is 11, and thus clearly higher than Redfield, but is varying during the season.

Description: Technical Note: Artificial coral reef mesocosms for ocean acidification investigations Biogeosciences Discussions, 11, 15463-15505, 2014 Author(s): J. Leblud, L. Moulin, A. Batigny, P. Dubois, and P. Grosjean The design and evaluation of replicated artificial mesocosms are presented in the context of a thirteen month experiment on the effects of ocean acidification on tropical coral reefs. They are defined here as (semi)-closed (i.e. with or without water change from the reef) mesocosms in the laboratory with a more realistic physico-chemical environment than microcosms. Important physico-chemical parameters (i.e. pH, p O 2 , p CO 2 , total alkalinity, temperature, salinity, total alkaline earth metals and nutrients availability) were successfully monitored and controlled. Daily variations of irradiance and pH were applied to approach field conditions. Results highlighted that it was possible to maintain realistic physico-chemical parameters, including daily changes, into artificial mesocosms. On the other hand, the two identical artificial mesocosms evolved differently in terms of global community oxygen budgets although the initial biological communities and physico-chemical parameters were comparable. Artificial reef mesocosms seem to leave enough degrees of freedom to the enclosed community of living organisms to organize and change along possibly diverging pathways.

Description: Phytoplankton community structure in the North Sea: coupling between remote sensing and automated in situ analysis at the single cell level Biogeosciences Discussions, 11, 15621-15662, 2014 Author(s): M. Thyssen, S. Alvain, A. Lefèbvre, D. Dessailly, M. Rijkeboer, N. Guiselin, V. Creach, and L.-F. Artigas Phytoplankton observation in the ocean can be a challenge in oceanography. Accurate estimations of their biomass and dynamics will help to understand ocean ecosystems and refine global climate models. This requires relevant datasets of phytoplankton at a functional level and on a daily and sub meso scale. In order to achieve this, an automated, high frequency, dedicated scanning flow cytometer (SFC, Cytobuoy, NL), has been developed to cover the entire size range of phytoplankton cells whilst simultaneously taking pictures of the largest of them. This cytometer was directly connected to the water inlet of a~pocket Ferry Box during a cruise in the North Sea, 8–12 May 2011 (DYMAPHY project, INTERREG IV A "2 Seas"), in order to identify the phytoplankton community structure of near surface waters (6 m) with a high resolution spacial basis (2.2 ± 1.8 km). Ten groups of cells, distinguished on the basis of their optical pulse shapes, were described (abundance, size estimate, red fluorescence per unit volume). Abundances varied depending on the hydrological status of the traversed waters, reflecting different stages of the North Sea blooming period. Comparisons between several techniques analyzing chlorophyll a and the scanning flow cytometer, using the integrated red fluorescence emitted by each counted cell, showed significant correlations. The community structure observed from the automated flow cytometry was compared with the PHYSAT reflectance anomalies over a daily scale. The number of matchups observed between the SFC automated high frequency in situ sampling and the remote sensing was found to be two to three times better than when using traditional water sampling strategies. Significant differences in the phytoplankton community structure within the two days for which matchups were available, suggest that it is possible to label PHYSAT anomalies not only with dominant groups, but at the level of the community structure.

Description: Long term effects on regional European boreal climate due to structural vegetation changes Biogeosciences Discussions, 11, 15507-15547, 2014 Author(s): J. H. Rydsaa, F. Stordal, and L. M. Tallaksen Amplified warming at high latitudes over the past decades has led to changes in the boreal and arctic climate system, such as structural changes in high latitude ecosystems and soil moisture properties. These changes trigger land-atmosphere feedbacks, through altered energy partitioning in response to changes in albedo and surface water fluxes. Local scale changes in the arctic and boreal zone may propagate to affect large scale climatic features. In this study, MODIS land surface data are used with the Weather Research and Forecasting model (WRF V3.5.1) and Noah LSM, in a series of experiments to simulate the influence of structural vegetation changes over a Northern European boreal ecosystem. Emphasis is placed on surface energy partitioning and near surface atmospheric variables, in order to investigate changes in atmospheric response due to observed and anticipated structural vegetation changes. We find that a northward migration of evergreen needle leaf forest into tundra regions causes an increase in latent rather than sensible heat fluxes, increased near surface temperatures and boundary layer height. Shrub expansion in tundra areas has only small effects on surface fluxes. However, it influences near surface wind speeds and boundary layer height. Northward migration of mixed forest across the present southern border of the boreal forest has largely opposite effects on surface fluxes and the near surface atmosphere, and acts to moderate the overall mean regional effects of boreal forest migration on the near surface atmosphere.

Description: Spatial variability and hotspots of soil N 2 O fluxes from intensively grazed grassland Biogeosciences Discussions, 11, 15327-15360, 2014 Author(s): N. J. Cowan, P. Norman, D. Famulari, P. E. Levy, D. S. Reay, and U. M. Skiba One hundred N 2 O flux measurements were made from an area of intensively managed grazed grassland in central Scotland using a high resolution dynamic chamber method. The field contained a variety of features from which N 2 O fluxes were measured including a manure heap, patches of decaying grass silage, and areas of increased sheep activity. Individual fluxes varied significantly across the field varying from 2 to 79 000 μg N 2 O-N m −2 h −1 . Soil samples were collected at 55 locations to investigate relationships between soil properties and N 2 O flux. Fluxes of N 2 O correlated strongly with soil NO 3 − concentrations. Distribution of NO 3 − and the high spatial variability of N 2 O flux across the field are shown to be linked to the distribution of waste from grazing animals and the resultant reactive nitrogen compounds in the soil which are made available for microbiological processes. Features within the field such as shaded areas and manure heaps contained significantly higher available nitrogen than the rest of the field. Although these features only represented 1.1% of the area of the field, they contributed to over 55% of the total estimated daily N 2 O flux.

Description: Size-fractionated dissolved primary production and carbohydrate composition of the coccolithophore Emiliania huxleyi Biogeosciences Discussions, 11, 15289-15325, 2014 Author(s): C. Borchard and A. Engel Extracellular release (ER) by phytoplankton is the major source of fresh dissolved organic carbon (DOC) in marine ecosystems and accompanies primary production during all growth phases. Little is known, so far, on size and composition of released molecules, and to which extent ER occurs passively, by leakage, or actively, by exudation. Here, we report on ER by the widespread and bloom-forming coccolithophore Emiliania huxleyi grown under steady state conditions in phosphorus controlled chemostats (N : P = 29, growth rate of μ = 0.2 d −1 ). 14 C incubations were accomplished to determine primary production (PP), comprised by particulate (PO 14 C) and dissolved organic carbon (DO 14 C), and the concentration and composition of particulate combined carbohydrates (pCCHO), and of high molecular weight (〉1 kDa, HMW) dissolved combined carbohydrates (dCCHO) as major components of ER. Information on size distribution of ER products was obtained by investigating distinct size classes (

Description: Potential of the TROPOspheric Monitoring Instrument (TROPOMI) onboard the Sentinel-5 Precursor for the monitoring of terrestrial chlorophyll fluorescence Atmospheric Measurement Techniques Discussions, 7, 12545-12588, 2014 Author(s): L. Guanter, I. Aben, P. Tol, J. M. Krijger, A. Hollstein, P. Köhler, A. Damm, J. Joiner, C. Frankenberg, and J. Landgraf Global monitoring of sun-induced chlorophyll fluorescence (SIF) can improve our knowledge about the photosynthetic functioning of terrestrial ecosystems. The feasibility of SIF retrievals from spaceborne atmospheric spectrometers has been demonstrated by a number of studies in the last years. In this work, we investigate the potential of the upcoming TROPOspheric Monitoring Instrument (TROPOMI) onboard the Sentinel-5 Precursor satellite mission for SIF retrieval. TROPOMI will sample the 675–775 nm spectral window with a spectral resolution of 0.5 nm and a pixel size of 7 km × 7 km. We use an extensive set of simulated TROPOMI data in order to assess the uncertainty of single SIF retrievals and subsequent spatio-temporal composites. Our results illustrate the enormous improvement in SIF monitoring achievable with TROPOMI with respect to comparable spectrometers currently in-flight, such as the Global Ozone Monitoring Experiment-2 (GOME-2) instrument. We find that TROPOMI can reduce global uncertainties in SIF mapping by more than a factor 2 with respect to GOME-2, which comes together with an about 5-fold improvement in spatial sampling. Finally, we discuss the potential of TROPOMI to accurately map other important vegetation parameters, such as leaf photosynthetic pigments and proxies for canopy structure, which will complement SIF retrievals for a self-contained description of vegetation condition and functioning.

Description: Autonomous profiling float observations of the high biomass plume downstream of the Kerguelen plateau in the Southern Ocean Biogeosciences Discussions, 11, 17413-17462, 2014 Author(s): M. Grenier, A. Della Penna, and T. W. Trull Natural iron fertilisation from Southern Ocean islands results in high primary production and phytoplankton biomass accumulations readily visible in satellite ocean colour observations. These images reveal great spatial complexity with highly varying concentrations of chlorophyll, presumably reflecting both variations in iron supply and conditions favouring phytoplankton accumulation. To examine the second aspect, in particular the influences of variations in temperature and stratification, we deployed four autonomous profiling floats in the Antarctic Circumpolar Current near the Kerguelen plateau in the Indian sector of the Southern Ocean. Each "bio-profiler" measured more than 250 profiles of temperature ( T ), salinity ( S ), dissolved oxygen, chlorophyll fluorescence (Chl a ), and particle backscatter in the top 300 m of the water column, sampling up to 5 profiles per day along meandering trajectories extending up to 1000 km. Comparison of surface Chl a estimates (top 50 m depth; analogous to values from satellite images) with total water column inventories revealed largely linear relationships, suggesting that dilution of chlorophyll by mixed layer depth variations plays only a minor role in the spatial distributions observed by satellite, and correspondingly that these images provide credible information on total and not just surface biomass accumulations. Regions of very high Chl a accumulation (1.5–10 μg L -1 ) were associated predominantly with a narrow T – S class of surface waters, which appears to derive from the northern Kerguelen plateau. In contrast, waters with only moderate Chl a enrichments (0.5–1.5 μg L -1 ) displayed no clear correlation with water properties, including no dependence on mixed layer depth, suggesting a diversity of sources of iron and/or its efficient dispersion across filaments of the plume. The lack of dependence on mixed layer depth also indicates a limited influence on production by light limitation. One float became trapped in a cyclonic eddy, allowing temporal evaluation of the water column in early autumn. During this period, decreasing surface Chl a inventories corresponded with decreases in oxygen inventories on sub-mixed layer density surfaces, consistent with significant export of organic matter and its respiration and storage as dissolved inorganic carbon in the ocean interior. These results are encouraging for the expanded use of autonomous observing platforms to study biogeochemical, carbon cycle, and ecological problems, although the complex blend of Lagrangian and Eulerian sampling achieved by the floats suggests that arrays rather than single floats will often be required.

Description: On the use of the post-closure method uncertainty band to evaluate the performance of land surface models against eddy covariance flux data Biogeosciences Discussions, 11, 16911-16951, 2014 Author(s): J. Ingwersen, K. Imukova, P. Högy, and T. Streck The energy balance of eddy covariance (EC) flux data is normally not closed. Therefore, at least if used for modeling, EC flux data are usually post-closed, i.e. the measured turbulent fluxes are adjusted so as to close the energy balance. At the current state of knowledge, however, it is not clear how to partition the missing energy in the right way. Eddy flux data therefore contain some uncertainty due to the unknown nature of the energy balance gap, which should be considered in model evaluation and the interpretation of simulation results. We propose to construct the post-closure method uncertainty band (PUB), which essentially designates the differences between non-adjusted flux data and flux data adjusted with the three post-closure methods (Bowen ratio, latent heat flux (LE) and sensible heat flux ( H ) method). To demonstrate this approach, simulations with the NOAH-MP land surface model were evaluated based on EC measurements conducted at a winter wheat stand in Southwest Germany in 2011, and the performance of the Jarvis and Ball–Berry stomatal resistance scheme was compared. The width of the PUB of the LE was up to 110 W m –2 (21% of net radiation). Our study shows that it is crucial to account for the uncertainty of EC flux data originating from lacking energy balance closure. Working with only a single post-closing method might result in severe misinterpretations in model-data comparisons.

Description: Carbon, oxygen and biological productivity in the Southern Ocean in and out the Kerguelen plume: CARIOCA drifter results Biogeosciences Discussions, 11, 16877-16909, 2014 Author(s): L. Merlivat, J. Boutin, and F. d'Ovidio The Kerguelen Plateau region in the Indian sector of the Southern Ocean supports annually a large-scale phytoplankton bloom which is naturally fertilized with iron. As part of the second Kerguelen Ocean and Plateau compared Study expedition (KEOPS2) in austral spring (October–November 2011), one Carioca buoy was deployed east of the Kerguelen plateau. It drifted eastward downstream in the Kerguelen plume. Hourly surface measurements of p CO 2 , O 2 and ancillary observations were collected between 1 November 2011 to 12 February 2012 with the aim of characterizing the spatial and temporal variability of the biological Net Community Production (NCP) downstream the Kerguelen plateau, assess the impact of iron-induced productivity on the biological carbon consumption and consequently on the CO 2 flux exchanged at the air–sea interface. The trajectory of the buoy until mid-December was within the longitude range, 72–83° E, close to the polar front and then in the polar frontal zone, PFZ, until 97° E. From 17 November to 16 December, the buoy drifted within the Kerguelen plume following a filament carrying dissolved iron, DFe, for a total distance of 700 km. In the first part of the trajectory, the ocean surface waters are a sink for CO 2 and a source for CO 2 , with fluxes of respective mean values equal to −8 and +38 mmol CO 2 m −2 d −1 . Eastward, as the buoy escapes the iron enriched filament, the fluxes are in opposite direction, with respective mean values of +5 and −48 mmol O 2 m −2 d −1 . These numbers clearly indicate the strong impact of biological processes on the biogeochemistry in the surface waters within the Kerguelen plume in November-mid-December, while it is undetectable eastward in the PFZ from mid-December to mid-February. While the buoy follows the Fe enriched filament, simultaneous observations of dissolved inorganic carbon, DIC, and dissolved oxygen, O 2 , highlight biological events lasting from 2 to 4 days. Stoichiometric ratios, O 2 /C, between 1.1 and 1.4 are observed indicating new and regenerated production regimes. NCP estimates range from 60 to 140 mmol C m −2 d −1 . Based on the relationship between the time a water parcel has left the plateau and its iron content, we have highlighted that the main control on the value of NCP is the availability of iron in the upper water column, with the largest NCP occurring in waters that have recently left the plateau and presented the highest iron concentrations.

Description: Comparison of UV/Vis and FDOM sensors for in situ monitoring of stream DOC concentrations Biogeosciences Discussions, 11, 16855-16876, 2014 Author(s): G.-Y. Yoo, Y. Jeong, E.-J. Lee, J.-H. Park, and N.-H. Oh Optical measurements using ultra-violet/visible (UV/Vis) spectrophotometric sensors and fluorescent dissolved organic matter (FDOM) sensors have recently been used as proxies of dissolved organic carbon (DOC) concentrations of streams and rivers at high temporal resolution. Despite of the merits of the sensors, temperature changes and particulate matter in water can interfere the sensor readings, over- or under-estimating DOC concentrations. However, little efforts have been made to compare responses of the two types of the sensors in natural conditions. We conducted both laboratory experiments and in situ monitoring with a UV/Vis sensor and a FDOM sensor during the three storm events in the fall of 2012 and the spring of 2013 in a forest stream in Korea in order to compare their performance. Laboratory experiments using the Suwannee River natural organic matter, humic acid, and fulvic acid demonstrated strong linear relationships between both the sensor signals and measured DOC concentrations with R 2 ≥ 0.98. Although temperature compensation might not be needed for the UV/Vis sensor, it was sensitive to relativley small changes in turbidity. In contrast, the FDOM sensor was insenstive to relatively low turbidity while the FDOM sensor outputs decreased significantly as temperature increased, requiring temperature compensated FDOM (e.g. FDOM 20 for 20 °C) for in situ monitoring of DOC. The results suggest that both sensors can be employed as a~proxy for stream DOC concentrations after temperature and turbidity compensation in a forest stream where terrestrially derived humic-like materials are dominant components.

Description: Modeling the impact of riverine DON removal by marine bacterioplankton on primary production in the Arctic Ocean Biogeosciences Discussions, 11, 16953-16992, 2014 Author(s): V. Le Fouest, M. Manizza, B. Tremblay, and M. Babin The planktonic and biogeochemical dynamics of the Arctic shelves exhibit a strong variability in response to Arctic warming. In this study, in order to elucidate on the processes regulating the production of phytoplankton (PP) and bacterioplankton (BP) and their interactions, we employ a biogeochemical model coupled to a pan-Arctic ocean-sea ice model (MITgcm) to explicitly simulate and quantify the contribution of usable dissolved organic nitrogen (DON) drained by the major circum-Arctic rivers on PP and BP in a scenario of melting sea ice (1998–2011). Model simulations suggest that on average between 1998 and 2011, the removal of usable RDON by bacterioplankton is responsible of a ~26% increase of the annual BP for the whole Arctic Ocean. With respect to total PP, the model simulates an increase of ~8% on an annual basis and of ~18% in summer. Recycled ammonium is responsible for the PP increase. The recycling of RDON by bacterioplankton promotes higher BP and PP but there is no significant temporal trend in the BP : PP ratio within the ice-free shelves over the 1998–2011 period. This suggests no significant evolution in the balance between autotrophy and heterotrophy in the last decade with a constant annual flux of RDON into the coastal ocean although changes in RDON supply and further reduction in sea ice cover could potentially alter this delicate balance.

Description: The Level 2 research product algorithms for the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) Atmospheric Measurement Techniques Discussions, 4, 3593-3645, 2011 Author(s): P. Baron, J. Urban, H. Sagawa, J. Möller, D. P. Murtagh, J. Mendrok, E. Dupuy, T. O. Sato, S. Ochiai, K. Suzuki, T. Manabe, T. Nishibori, K. Kikuchi, R. Sato, M. Takayanagi, Y. Murayama, M. Shiotani, and Y. Kasai This paper describes the algorithms of the level-2 research (L2r) processing chain developed for the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES). The chain has been developed in parallel to the operational chain for conducting researches on calibration and retrieval algorithms. L2r chain products are available to the scientific community. The objective of version 2 is the retrieval of the vertical distribution of trace gases in the altitude range of 18–90 km. An theoretical error analysis is conducted to estimate the retrieval feasibility of key parameters of the processing: line-of-sight elevation tangent altitudes (or angles), temperature and O 3 profiles. The line-of-sight tangent altitudes are retrieved between 20 and 50 km from the strong ozone (O 3 ) line at 625.371 GHz, with low correlation with the O 3 volume-mixing ratio and temperature retrieved profiles. Neglecting the non-linearity of the radiometric gain in the calibration procedure is the main systematic error. It is large for the retrieved temperature (between 5–10 K). Therefore, atmospheric pressure can not be derived from the retrieved temperature, and, then, in the altitude range where the line-of-sight tangent altitudes are retrieved, the retrieved trace gases profiles are found to be better represented on pressure levels than on altitude levels. The error analysis for the retrieved HOCl profile demonstrates that best results for inverting weak lines can be obtained by using narrow spectral windows. Future versions of the L2r algorithms will improve the temperature/pressure retrievals and also provide information in the upper tropospheric/lower stratospheric region (e.g., water vapor, ice content, O 3 ) and on stratospheric and mesospheric line-of-sight winds.

Description: Near infrared nadir sounding of vertical column densities: methodology and application to SCIAMACHY Atmospheric Measurement Techniques Discussions, 4, 3685-3737, 2011 Author(s): S. Gimeno García, F. Schreier, G. Lichtenberg, and S. Slijkhuis Nadir observations with the shortwave infrared channels of SCIAMACHY onboard the ENVISAT satellite can be used to derive information on atmospheric gases such as CO, CH 4 , N 2 O, CO 2 , and H 2 O. For the operational level 1b–2 processing of SCIAMACHY data a new retrieval code BIRRA (Beer InfraRed Retrieval Algorithm) has been developed: BIRRA performs a nonlinear least squares fit of the measured radiance, where molecular concentration vertical profiles are scaled to fit the observed data. Here we present the forward modeling (radiative transfer) and inversion (least squares optimization) fundamentals of the code along with the further processing steps required to generate higher level products such as global distributions and time series. Moreover, various aspects of level 1 (observed spectra) and auxiliary input data relevant for successful retrievals are discussed. BIRRA is currently used for operational analysis of carbon monoxide vertical column densities from SCIAMACHY channel 8 observations, and is being prepared for methane retrievals using channel 6 spectra. A set of representative CO retrievals and first CH 4 results are presented to demonstrate BIRRA's capabilities.

Description: Volatilizable biogenic organic compounds (VBOCs) with two dimensional gas chromatography-time of flight mass spectrometry (GC × GC-TOFMS): sampling methods, VBOC complexity, and chromatographic retention data Atmospheric Measurement Techniques Discussions, 4, 3647-3684, 2011 Author(s): J. F. Pankow, W. Luo, A. N. Melnychenko, K. C. Barsanti, L. M. Isabelle, C. Chen, A. B. Guenther, and T. N. Rosenstiel Two dimensional gas chromatography (GC × GC) with detection by time-of-flight mass spectrometry (TOFMS) was applied in the rapid analysis of air samples containing highly complex mixtures of volatilizable biogenic organic compounds (VBOCs). VBOC analytical methodologies are briefly reviewed, and optimal conditions are discussed for sampling with both adsorption/thermal desorption (ATD) cartridges and solid-phase microextraction (SPME) fibers. Air samples containing VBOC emissions from leaves of two tree species ( Cedrus atlantica and Calycolpus moritzianus ) were obtained by both ATD and SPME. The optimized gas chromatographic conditions utilized a 45 m, 0.25 mm I.D. low-polarity primary column (DB-VRX, 1.4 μm film) and a 1.5 m, 0.25 mm I.D. polar secondary column (Stabilwax® 0.25 μm film). Excellent separation was achieved in a 36 min temperature programmed GC × GC chromatogram. Thousands of VBOC peaks were present in the sample chromatograms; hundreds of tentative identifications by NIST mass spectral matching are provided. Very few of the tentatively identified compounds are currently available as authentic standards. Method detection limit values for a 5 l ATD sample were 3.5 pptv (10 ng m −3 ) for isoprene, methyl vinyl ketone, and methacrolein, and ~1.5 pptv (~10 ng m −3 ) for monoterpenes and sesquiterpenes. Kovats-type chromatographic retention index values on the primary column and relative retention time values on the secondary column are provided for 21 standard compounds and for 417 tentatively identified VBOCs. 19 of the 21 authentic standard compounds were found in one of the Cedrus atlantica SPME samples. In addition, easily quantifiable levels of at least 13 sesquiterpenes were found in an ATD sample obtained from a branch enclosure of Calycolpus moritzianus . Overall, the results obtained via GC × GC-TOFMS highlight an extreme, and largely uncharacterized diversity of VBOCs, consistent with the hypothesis that sesquiterpenes and other compounds beyond the current list of typically determined VBOC analytes may well be important contributors to global atmospheric levels of organic particulate matter.

Description: An algorithm for detecting Trichodesmium surface blooms in the South Western Tropical Pacific Biogeosciences Discussions, 8, 5653-5689, 2011 Author(s): C. Dupouy, D. Benielli-Gary, J. Neveux, Y. Dandonneau, and T. K. Westberry Trichodesmium , a major colonial cyanobacterial nitrogen fixer, forms large blooms in NO 3 -depleted tropical oceans and enhances CO 2 sequestration by the ocean due to its ability to fix dissolved dinitrogen. Thus, its importance in C and N cycles requires better estimates of its distribution at basin to global scales. However, existing algorithms to detect them from satellite have not yet been successful in the South Western Tropical Pacific (SWTP). Here, a novel approach based on radiance anomaly spectra (RAS) observed in SeaWiFS imagery is used to detect Trichodesmium during the austral summertime in the SWTP. Selected pixels are characterized by a restricted range of parameters quantifying RAS spectra quantitative parameters (e.g. slope, intercept, curvature). The fraction of valid pixels identified as Trichodesmium surface blooms in the region 5° S–25° S 160° E–190° E is low (between 0.01 and 0.2 %), but is about 100 times higher than suggested by previous algorithms. This represents a total surface area which varies from 1500 to 20 000 km 2 . A monthly distribution of Trichodesmium surface accumulations in the SWTP is presented which demonstrates that the number of selected pixels peaks in November–February each year, consistent with field observations. This approach was validated with in situ observations of Trichodesmium surface accumulations for the period 1998–2010.

Description: Correcting orbital drift signal in the time series of AVHRR derived convective cloud fraction using rotated empirical orthogonal function Atmospheric Measurement Techniques Discussions, 4, 3877-3890, 2011 Author(s): A. Devasthale, K. Karlsson, J. Quaas, and H. Grassl The AVHRRs instruments onboard the series of NOAA satellites offer the longest available meteorological data records from space. These satellites have drifted in orbit resulting in shifts in the local time sampling during the life span of sensors onboard. Depending on the amplitude of a diurnal cycle of the geophysical parameters derived, orbital drift may cause spurious trends in their time series. We investigate tropical deep convective clouds, which show pronounced diurnal cycle amplitude, to bracket an upper bound of the impact of orbital drift on their time series. We carry out a rotated empirical orthogonal function analysis and show that the REOFs are useful in delineating orbital drift signal and, more importantly, in correcting this signal in the time series of convective cloud amount. These results will help facilitate the derivation of homogenized data series of cloud amount from NOAA satellite sensors and ultimately analyzing trends from them. However, we suggest detailed comparison of various methods and their rigorous testing before applying final orbital drift corrections.

Description: Rainfall patterns after fire differentially affect the recruitment of three Mediterranean shrubs Biogeosciences Discussions, 8, 5761-5786, 2011 Author(s): J. M. Moreno, E. Zuazua, B. Pérez, B. Luna, A. Velasco, and V. Resco de Dios In fire-prone environments, the "event-dependent hypothesis" states that plant population changes are driven by the unique set of conditions of a fire (e.g., fire season, climate). Climate variability, in particular changes in rainfall patterns, can be most important for seeder species, since they must regenerate after fire from seeds, and for Mediterranean shrublands, given the high yearly variability of rainfall in these ecosystems. Yet, the role of rainfall variability and its interaction with fire characteristics (e.g., fire season) on plant populations has received little attention. Here we investigated the changes in seedling emergence and recruitment of three seeder species ( Cistus ladanifer , Erica umbellata and Rosmarinus officinalis ) after fires lit during three different years and at two times during the fire season (early and late in the fire season) to account for potential changes in the soil seed-bank during the year. Three plots were burned at each season, for a total of 18 plots burned during the three years. After fire, emerged seedlings were tallied, tagged and monitored during three years (two the last burning year). Rainfall during the study period was rather variable, and in some years was well below average. Seedling emergence after fire varied by a factor of 3 to 10, depending on the species and on the burning year. The bulk of seedling emergence occurred in the first year after fire, and seedling recruitment at the end of the study period was tightly correlated with this early emergence. Seedling emergence in E umbellata and R officinalis , but not in C ladanifer , were correlated with precipitation in the fall and winter immediately after the fire, being E umbellata most sensitive to low rainfall. Fire season was generally not an important factor in controlling emergence and recruitment. We discuss how projected changes in rainfall patterns with global warming can alter the balance of species in this shrubland, and can drive some species to near local extinction.

Description: Phosphorus transformations as a function of pedogenesis: a synthesis of soil phosphorus data using Hedley fractionation method Biogeosciences Discussions, 8, 5907-5934, 2011 Author(s): X. Yang and W. M. Post In spite of the importance of phosphorus (P) as a limiting nutrient in terrestrial ecosystems, our understanding of terrestrial P dynamics and our ability to model P cycling are hampered by the lack of consistent measurements of soil P. The Hedley fractionation method provides a comprehensive assessment of soil P and has been widely used in recent decades. Here we expand an earlier study that summarized Hedley P data from the literature to create a larger Hedley P database and further investigate the relationships between distributions of different forms of P and the stages of soil development. Our expanded Hedley P database generally supports what the Walker and Syers (1976) conceptual model predicts: the gradual decrease and eventual depletion of primary mineral P (mainly apatite P); the continual increase and eventual dominance of occluded P; and the overall decrease of total P during soil development. However the analysis disagrees with Walker and Syers (1976) in that we found labile inorganic P(Pi) and secondary Pi (non-occluded P in Walker and Syers' model) to be a significant fraction of total P throughout all soil orders with different weathering stages. By analyzing the Hedley-labile P and vegetation P demand, we found that the amount of labile P is much greater than vegetation demand, even in highly weathered soils commonly considered P limited. We conclude that measured Hedley-labile P should not be defined as plant available P since most of this labile P likely ends up as immobilized by microbes. Our analysis of the database also shows that carbon (C) and nitrogen (N) in soil organic matter are closely linked in all soil orders, but P is decoupled from C and N in highly weathered soils with larger variations of nitrogen:organic P (N:Po) ratio and higher mean values of N:Po ratio, compared to slightly and intermediately weathered soils.

Description: Sensitivity studies for a space-based methane lidar mission Atmospheric Measurement Techniques Discussions, 4, 3545-3592, 2011 Author(s): C. Kiemle, M. Quatrevalet, G. Ehret, A. Amediek, A. Fix, and M. Wirth Methane is the third most important greenhouse gas in the atmosphere after water vapour and carbon dioxide. A major handicap to quantify the emissions at the Earth's surface in order to better understand biosphere-atmosphere exchange processes and potential climate feedbacks is the lack of accurate and global observations of methane. Space-based integrated path differential absorption (IPDA) lidar has potential to fill this gap, and a Methane Remote Lidar Mission (MERLIN) on a small satellite in Polar orbit was proposed by DLR and CNES in the frame of a German-French climate monitoring initiative. System simulations are used to identify key performance parameters and to find an advantageous instrument configuration, given the environmental, technological, and budget constraints. The sensitivity studies use representative averages of the atmospheric and surface state to estimate the measurement precision, i.e. the random uncertainty due to instrument noise. Key performance parameters for MERLIN are average laser power, telescope size, orbit height, surface reflectance, and detector noise. A modest-size lidar instrument with 0.45 W average laser power and 0.55 m telescope diameter on a 506 km orbit could provide 50-km averaged methane column measurement along the sub-satellite track with a precision of about 1 % over vegetation. The use of a methane absorption trough at 1.65 μm improves the near-surface measurement sensitivity and vastly relaxes the wavelength stability requirement that was identified as one of the major technological risks in the pre-phase A studies for A-SCOPE, a space-based IPDA lidar for carbon dioxide at the European Space Agency. Minimal humidity and temperature sensitivity at this wavelength position will enable accurate measurements in tropical wetlands, key regions with largely uncertain methane emissions. In contrast to actual passive remote sensors, measurements in Polar Regions will be possible and biases due to aerosol layers and thin ice clouds will be minimised.

Description: Information operator approach applied to the retrieval of the vertical distribution of atmospheric constituents from ground-based high-resolution FTIR measurements Atmospheric Measurement Techniques Discussions, 4, 3739-3785, 2011 Author(s): C. Senten, M. De Mazière, G. Vanhaelewyn, and C. Vigouroux The analysis of high spectral resolution Fourier Transform infrared (FTIR) solar absorption spectra is an important issue in remote sensing. If this is done carefully, one can obtain information, not only about the total column abundances, but also about the vertical distribution of various constituents in the atmosphere. This work introduces the application of the information operator approach for extracting vertical profile information from ground-based FTIR measurements. The algorithm is implemented and tested within the well-known retrieval code SFIT2, adapting the optimal estimation method such as to take into account only the significant contributions to the solution. In particular, we demonstrate the feasibility of the method in an application to ground-based FTIR spectra taken in the frame of the Network for the Detection of Atmospheric Composition Change (NDACC) at Ile de La Réunion (21° S, 55° E). A thorough comparison is made between the original optimal estimation method and this alternative retrieval algorithm, regarding information content, retrieval robustness and corresponding full error budget evaluation for the target species ozone (O 3 ), nitrous oxide (N 2 O), methane (CH 4 ), and carbon monoxide (CO). For O 3 and CH 4 , a comparison with the Tikhonov regularization method has also been made. It is shown that the information operator approach performs well and in most cases yields both a better accuracy and stability than the optimal estimation method. Additionally, the information operator approach has the advantage of being less sensitive to the choice of a priori information. The Tikhonov regularization results seem to be situated between both methods' results, as to profile retrievals, error budgets and column stability.

Description: Opportunistic validation of sulfur dioxide in the Sarychev Peak volcanic eruption cloud Atmospheric Measurement Techniques Discussions, 4, 3861-3875, 2011 Author(s): S. A. Carn and T. M. Lopez We report attempted validation of Ozone Monitoring Instrument (OMI) sulfur dioxide (SO 2 ) retrievals in the stratospheric volcanic cloud from Sarychev Peak (Kurile Islands) in June 2009, through opportunistic deployment of a ground-based ultraviolet (UV) spectrometer (FLYSPEC) as the volcanic cloud drifted over Central Alaska. The volcanic cloud altitude (~12–14 km) was constrained using coincident CALIPSO lidar observations. By invoking some assumptions about the spatial distribution of SO 2 , we derive averages of FLYSPEC vertical SO 2 columns for comparison with OMI SO 2 measurements. Despite limited data, we find minimum OMI-FLYSPEC differences of ~5–6 % which support the validity of the operational OMI SO 2 algorithm. These measurements represent the first attempt to validate SO 2 in a stratospheric volcanic cloud using a mobile ground-based instrument, and demonstrate the need for a network of rapidly deployable instruments for validation of space-based volcanic SO 2 measurements.

Description: Greenhouse gas flux measurements in a forestry-drained peatland indicate a large carbon sink Biogeosciences Discussions, 8, 5787-5825, 2011 Author(s): A. Lohila, K. Minkkinen, M. Aurela, J.-P. Tuovinen, T. Penttilä, and T. Laurila Drainage for forestry purposes changes the conditions in the peat and leads to increased growth of shrubs and trees. Concurrently, the production and uptake of the greenhouse gases carbon dioxide (CO 2 ), methane (CH 4 ) and nitrous oxide (N 2 O) are likely to change: due to the accelerated decomposition of oxic peat, drained peatlands are generally considered to loose peat carbon (C). We measured CO 2 exchange with the eddy covariance (EC) method above a drained nutrient-poor peatland forest in Southern Finland for 16 months in 2004–2005. The site, classified as a dwarf-shrub pine bog, had been ditched about 35 years earlier. CH 4 and N 2 O fluxes were measured at 2–5 week intervals with the chamber technique. Drainage had resulted in a relatively little change in the water table level, being on average 40 cm below the ground in 2005. The annual net ecosystem exchange was −870 g CO 2 m −2 yr −1 in the calendar year 2005, varying from −810 to −900 g CO 2 m −2 yr −1 during the 16 month period under investigation. The site was a small sink of CH 4 (−0.12 g CH 4 m −2 yr −1 ) and a small source of N 2 O (0.10 g N 2 O m −2 yr −1 ). Photosynthesis was detected throughout the year when the air temperature exceeded −3 °C. As the annual accumulation of C in the above and below ground tree biomass (550 g CO 2 m −2 ) was significantly less than the net exchange of CO 2 , about 300 g CO 2 m −2 yr −1 (~80 g C m −2 ) was likely to have accumulated as organic matter into the peat soil. This is a higher average accumulation rate than previously reported for natural northern peatlands, and the first time C accumulation has been shown, by EC measurements, to occur in a drained peatland. Our results suggest that forestry-drainage may significantly increase the CO 2 uptake rate of nutrient-poor peatland ecosystems.

Description: Inversion of tropospheric profiles of aerosol extinction and HCHO and NO 2 mixing ratios from MAX-DOAS observations in Milano during the summer of 2003 and comparison with independent data sets Atmospheric Measurement Techniques Discussions, 4, 3891-3964, 2011 Author(s): T. Wagner, S. Beirle, T. Brauers, T. Deutschmann, U. Frieß, C. Hak, J. D. Halla, K. P. Heue, W. Junkermann, X. Li, U. Platt, and I. Pundt-Gruber We present aerosol and trace gas profiles derived from MAX-DOAS observations. Our inversion scheme is based on simple profile parameterisations used as input for an atmospheric radiative transfer model (forward model). From a least squares fit of the forward model to the MAX-DOAS measurements, two profile parameters are retrieved including integrated quantities (aerosol optical depth or trace gas vertical column density), and parameters describing the height and shape of the respective profiles. From these results, the aerosol extinction and trace gas mixing ratios can also be calculated. We apply the profile inversion to MAX-DOAS observations during a measurement campaign in Milano, Italy, September 2003, which allowed simultaneous observations from three telescopes (directed to north, west, south). Profile inversions for aerosols and trace gases were possible on 23 days. Especially in the middle of the campaign (17–20 September 2003), enhanced values of aerosol optical depth and NO 2 and HCHO mixing ratios were found. The retrieved layer heights were typically similar for HCHO and aerosols. For NO 2 , lower layer heights were found, which increased during the day. The MAX-DOAS inversion results are compared to independent measurements: (1) aerosol optical depth measured at an AERONET station at Ispra; (2) near-surface NO 2 and HCHO (formaldehyde) mixing ratios measured by long path DOAS and Hantzsch instruments at Bresso; (3) vertical profiles of HCHO and aerosols measured by an ultra light aircraft. Depending on the viewing direction, the aerosol optical depths from MAX-DOAS are either smaller or larger than those from AERONET observations. Similar comparison results are found for the MAX-DOAS NO 2 mixing ratios versus long path DOAS measurements. In contrast, the MAX-DOAS HCHO mixing ratios are generally higher than those from long path DOAS or Hantzsch instruments. The comparison of the HCHO and aerosol profiles from the aircraft showed reasonable agreement with the respective MAX-DOAS layer heights. From the comparison of the results for the different telescopes, it was possible to investigate the internal consistency of the MAX-DOAS observations. As part of our study, a cloud classification algorithm was developed (based on the MAX-DOAS zenith viewing directions), and the effects of clouds on the profile inversion were investigated. Different effects of clouds on aerosols and trace gas retrievals were found: while the aerosol optical depth is systematically underestimated and the HCHO mixing ratio is systematically overestimated under cloudy conditions, the NO 2 mixing ratios are only slightly affected. These findings are in basic agreement with radiative transfer simulations.

Description: Effect of mosaic representation of vegetation in land surface schemes on simulated energy and carbon balances Biogeosciences Discussions, 8, 5849-5879, 2011 Author(s): R. Li and V. K. Arora Energy and carbon balance implications of representing vegetation using a composite or mosaic approach in a land surface scheme are investigated. In the composite approach the attributes of different plant functional types (PFTs) present in a grid cell are aggregated in some fashion for energy and water balance calculations. The resulting physical environmental conditions (including net radiation, soil moisture and soil temperature) are common to all PFTs and affect their ecosystem processes. In the mosaic approach energy and water balance calculations are performed separately for each PFT tile using its own vegetation attributes, so each PFT "sees" different physical environmental conditions and its carbon balance evolves somewhat differently from that in the composite approach. Simulations are performed at selected boreal, temperate and tropical locations to illustrate the differences caused by using the composite versus the mosaic approaches of representing vegetation. Differences in grid averaged primary energy fluxes are generally less than 5 % between the two approaches. Grid-averaged carbon fluxes and pool sizes can, however, differ by as much as 46 %. Simulation results suggest that differences in carbon balance between the two approaches arise primarily through differences in net radiation which directly affects net primary productivity, and thus leaf area index and vegetation biomass.

Description: Modeling the ascent of sounding balloons: derivation of the vertical air motion Atmospheric Measurement Techniques Discussions, 4, 3965-4012, 2011 Author(s): A. Gallice, F. G. Wienhold, C. R. Hoyle, F. Immler, and T. Peter A new model to describe the ascent of sounding balloons in the troposphere and lower stratosphere (up to ~30–35 km altitude) is presented. Contrary to previous models, detailed account is taken of both the variation of the drag coefficient with altitude and the heat imbalance between the balloon and the atmosphere. To compensate for the lack of data on the drag coefficient of sounding balloons, a reference curve for the relationship between drag coefficient and Reynolds number is derived from a dataset of flights launched during the Lindenberg Upper Air Methods Intercomparisons (LUAMI) campaign. The transfer of heat from the surrounding air into the balloon is accounted for by solving the radial heat diffusion equation inside the balloon. The potential applications of the model include the forecast of the trajectory of sounding balloons, which can be used to increase the accuracy of the match technique, and the derivation of the air vertical velocity. The latter is obtained by subtracting the ascent rate of the balloon in still air calculated by the model from the actual ascent rate. This technique is shown to provide an approximation for the vertical air motion with an uncertainty error of 0.5 m s −1 in the troposphere and 0.2 m s −1 in the stratosphere. An example of extraction of the air vertical velocity is provided in this paper. We show that the air vertical velocities derived from the balloon soundings in this paper are in general agreement with small-scale atmospheric velocity fluctuations related to gravity waves, mechanical turbulence, or other small-scale air motions measured during the SUCCESS campaign (Subsonic Aircraft: Contrail and Cloud Effects Special Study) in the orographically unperturbed mid-latitude middle troposphere.

Description: Contributions of agricultural plants and soils to N 2 O emission in a farmland Biogeosciences Discussions, 8, 5505-5535, 2011 Author(s): J. Li, X. Lee, Q. Yu, X. Tong, Z. Qin, and B. Macdonald The goal of this study was to quantify the roles of plants and soil in the N 2 O budget of a cropland in North China. Plant and soil N 2 O fluxes were measured with transparent and dark plant chambers and soil chambers, respectively, in three adjacent fields of fertilized cotton, fertilized maize and unfertilized soybean. During the observation period, the soil flux was 448 ± 89, 230 ± 74 and 90 ± 14 μg N 2 O m −2 h −1 in cotton, maize and soybean fields, respectively. The plant flux was 54 ± 43 and 16 ± 41 μg N 2 O m −2 h −1 , about 10 % and 26 % to the total ecosystem flux, for the cotton and the soybean field, respectively. Ignoring the contribution of plants would cause an obvious underestimation on the ecosystem N 2 O flux. The influence of sunlight on plant N 2 O flux was insignificant. However, in the cotton field, the responses of the plant N 2 O flux to air temperature and soil ammonium content were significant under sunlight but insignificant under darkness, suggesting that stomatal activity might influence the release process. In the cotton field, temperature sensitivity of plant N 2 O emission was 1.13, much lower than the value of soil flux (5.74). No relationship was found between plant N 2 O flux and soil nitrate content. It was implied that nitrate reduction in plants might not be the main source of plant N 2 O emission under field conditions. The seasonal patterns of the soil and plant N 2 O emissions were similarly affected by fertilization, indicating that plants might serve as a passive conduit transporting N 2 O produced in the soil.

Description: What controls biological productivity in coastal upwelling systems? Insights from a comparative modeling study Biogeosciences Discussions, 8, 5617-5652, 2011 Author(s): Z. Lachkar and N. Gruber The magnitude of the biological productivity in Eastern Boundary Upwelling Systems (EBUS) is traditionally viewed as directly reflecting the upwelling intensity. Yet, different EBUS show different sensitivities of productivity to upwelling-favorable winds (Carr and Kearns, 2003). Here, using a comparative modeling study of the California Current System (California CS) and Canary Current System (Canary CS), we show how physical and environmental factors, such as light, temperature and cross-shore circulation modulate the response of biological productivity to upwelling strength. To this end, we made a series of eddy-resolving simulations of the California CS and Canary CS using the Regional Ocean Modeling System (ROMS), coupled to a nitrogen based Nutrient-Phytoplankton-Zooplankton-Detritus (NPZD) ecosystem model. We find the nutrient content of the euphotic zone to be 20 % smaller in the Canary CS relative to the California CS. Yet, the biological productivity is 50 % smaller in the latter. This is due to: (1) a faster nutrient-replete growth in the Canary CS relative to the California CS, related to a more favorable light and temperature conditions in the Canary CS, and (2) the longer nearshore water residence times in the Canary CS which lead to larger buildup of biomass in the upwelling zone, thereby enhancing the productivity. The longer residence times in the Canary CS appear to be associated with the wider continental shelves and the lower eddy activity characterizing this upwelling system. This results in a weaker offshore export of nutrients and organic matter, thereby increasing local nutrient recycling and enhancing the coupling between new and export production in the Northwest African system. Our results suggest that climate change induced perturbations such as upwelling favorable wind intensification might lead to contrasting biological responses in the California CS and the Canary CS, with major implications for the biogeochemical cycles and fisheries in these two ecosystems.

Description: Impacts of UV radiation on plankton community metabolism along the Humboldt Current System Biogeosciences Discussions, 8, 5827-5848, 2011 Author(s): N. Godoy, A. Canepa, S. Lasternas, E. Mayol, S. Ruíz-Halpern, S. Agustí, J. C. Castilla, and C. M. Duarte The Humbolt Current System along the Chilean coast is one of the most productive regions in the world, where UV levels are particularly high due to stratospheric ozone depletion. Research has shown that phytoplankton photosynthesis can be severely inhibited by surface radiation and there are concerns that this will reduce not only algal carbon fixation, but also the carbon supply for higher trophic level. Experimental estimates of community metabolism (NCP, GPP and R) and the impacts of UV on community metabolism were assessed at 8 stations along the meridional track by the Humbold-2009 cruise (54.80° S–23.85° S) on board RV Hespérides from 5 to 15 March 2009. The results showed an increase UVB penetration towards the Equator, along the Humboldt Current System, suggesting a more important impact of UVB radiation towards the north. The metabolic rates observed were within average values reported for the Ocean Pacific and did not show the water mass investigated to be exceptionally productive at the time of the study. Experimental evaluation of the effect of UVB radiation on surface waters, those most strongly affected by UVB, showed that UVB radiation suppressed net community production, resulting in a dominance of heterotrophic communities in surface waters, compared to the prevalence of autotrophic communities inferred when materials, excluding UVB radiation, are used for incubation. These results show that UVB radiation, which has increased greatly in the study area, may have suppressed net community production of the plankton communities, possibly driving plankton communities in the Southwest Pacific towards CO 2 sources.

Description: Potential and limitations of the MAX-DOAS method to retrieve the vertical distribution of tropospheric nitrogen dioxide Atmospheric Measurement Techniques Discussions, 4, 4013-4072, 2011 Author(s): T. Vlemmix, A. J. M. Piters, A. J. C. Berkhout, L. F. L. Gast, P. Wang, and P. F. Levelt Muliple Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) instruments can measure from the ground the absorption by nitrogen dioxide (NO 2 ) of scattered sunlight seen in multiple viewing directions. This paper studies the potential of this technique to derive the vertical distribution of NO 2 in the troposphere. Such profile information is essential in validation studies in which MAX-DOAS retrievals play a role. The retrieval algorithm used is based on a pre-calculated look-up table and assumes homogeneous mixing of aerosols and NO 2 in layers extending from the surface to a variable height. Two retrieval models are compared: one including and one excluding an elevated NO 2 layer at a fixed altitude in the free troposphere. An ensemble technique is applied to derive retrieved model uncertainties. Sensitivity studies demonstrate that MAX-DOAS based retrievals can make a distinction between an NO 2 layer that extends from the surface to a certain height (having a constant mixing ratio, or a mixing ratio that decreases with altitude) and an elevated NO 2 layer. The height of the elevated NO 2 layer can only be retrieved accurately when the aerosol extinction profile is known and the measurement noise is low. The uncertainty in this elevated NO 2 layer height provides the main source of uncertainty in the retrieval of the free tropospheric contribution to the tropospheric NO 2 column. A comparison was performed with independent data, based on observations done at the CINDI campaign, held in the Netherlands in 2009. Comparison with lidar partial tropospheric NO 2 columns showed a correlation of 0.78, and an average difference of 0.1× 10 15 molec cm −2 . The diurnal evolution of the NO 2 volume mixing ratio measured by in-situ monitors at the surface and averaged over five days with cloud-free mornings, compares quite well to the MAX-DOAS retrieval: a correlation was found of 0.8, and an average difference of 0.2 ppb.

Description: Water isotopic ratios from a continuously melted ice core sample Atmospheric Measurement Techniques Discussions, 4, 4073-4104, 2011 Author(s): V. Gkinis, T. J. Popp, T. Blunier, M. Bigler, S. Schüpbach, and S. J. Johnsen A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We build an interface between an Infra Red Cavity Ring Down Spectrometer (IR-CRDS) and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ 18 O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100 % efficiency in a home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on humidity levels. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1 ‰ and 0.5 ‰ for δ 18 O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ 18 O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the framework of the NEEM deep ice core drilling project in Greenland, during the 2010 field season.

Description: Biomineralization of dolomite and magnesite discovered in tropical coralline algae: a biological solution to the geological dolomite problem Biogeosciences Discussions, 8, 5881-5906, 2011 Author(s): M. C. Nash, U. Troitzsch, B. N. Opdyke, J. M. Trafford, B. D. Russell, and D. I. Kline Dolomite is a magnesium-rich carbonate mineral abundant in fossil carbonate reef platforms but surprisingly rare in modern sedimentary environments, a conundrum known as the ''Dolomite Problem". Marine sedimentary dolomite has been interpreted to form by an unconfirmed, post-depositional diagenetic process, despite minimal experimental success at replicating this. Here we show that dolomite, accompanied by magnesite, forms within living crustose coralline alga, Hydrolithon onkodes , a prolific global tropical reef species. Chemical micro-analysis of the coralline skeleton reveals that not only are the cell walls calcitised, but that cell spaces are typically filled with magnesite, rimmed by dolomite, or both. Mineralogy was confirmed by X-ray diffraction. Thus there are at least three mineral phases present (magnesium calcite, dolomite and magnesite) rather than one or two (magnesium calcite and brucite) as previously thought. Our results are consistent with dolomite occurrences in coralline algae rich environments in fossil reefs. Instead of a theory of post-depositional dolomitisation, we present evidence revealing biomineralization that can account for the massive formations seen in the geologic record. Additionally, our findings imply that previously unrecognized dolomite and magnesite have formed throughout the Holocene. This discovery together with the scale of coralline algae dominance in past shallow carbonate environments raises the possibility that environmental factors driving this biological dolomitisation process have influenced the global marine magnesium/calcium cycle. Perhaps, most importantly, we reveal that what has been considered a geological process can be a biological process, having many implications for both disciplines.

Description: Transport and fate of hexachlorocyclohexanes in the oceanic air and surface seawater Biogeosciences Discussions, 8, 5537-5562, 2011 Author(s): Z. Xie, B. P. Koch, A. Möller, R. Sturm, and R. Ebinghaus Hexachlorocyclohexanes (HCHs) are ubiquitous organic pollutants derived from pesticide application. They are subject to long-range transport, persistent in the environment, and capable of accumulation in biota. Shipboard measurements of HCH isomers (α-, γ- and β-HCH) in surface seawater and boundary layer atmospheric samples were conducted in the Atlantic and the Southern Ocean in October to December of 2008. ΣHCHs concentrations (the sum of α-, γ- and β-HCH) in the lower atmosphere ranged from 11.8 to 36.9 pg m −3 (mean: 26.6 ± 11.0 pg m −3 ) in the Northern Hemisphere (NH), and from 1.5 to 4.0 pg m −3 (mean: 2.8 ± 1.1 pg m −3 ) in the Southern Hemisphere (SH), respectively. Water concentrations were: α-HCH 0.33–46.8 pg l −1 , γ-HCH 0.02–33.2 pg l −1 and β-HCH 0.11–2 pg l −1 . HCH concentrations decreased from the North Atlantic to the Southern Ocean, indicating historical use of HCHs in the NH. Spatial distribution showed increasing concentrations from the equator towards North and South latitudes illustrating the concept of cold condensation and less interhemispheric mixing process. In comparison to concentrations measured in 1987–1999/2000, gaseous HCHs were slightly lower, while dissolved HCHs decreased by factor of 2–3 orders of magnitude. Air-water exchange gradients suggested net deposition for α-HCH (mean: 3759 pg m −2 day −1 ) and γ-HCH (mean: 1987 pg m −2 day −1 ), whereas β-HCH varied between equilibrium (volatilization:

Description: Confocal Raman microscopy as a tool to describe different mineral and organic phases at high spatial resolution within marine biogenic carbonates: case study on Nerita undata (Gastropoda, Neritopsina) Biogeosciences Discussions, 8, 5563-5585, 2011 Author(s): G. Nehrke and J. Nouet Marine biogenic carbonates formed by invertebrates (e.g. corals and mollusk shells) represent complex composites of one or more mineral phases and organic molecules. This complexity ranges from the macroscopic structures observed with the naked eye down to sub micrometric structures only revealed by micro analytical techniques. Understanding to what extent and how organisms can control the formation of these structures requires that the mineral and organic phases can be identified and their spatial distribution related. Here we demonstrate the capability of confocal Raman microscopy applied to cross sections of a shell of Nerita undata to describe the distribution of calcite and aragonite including their crystallographic orientation with high lateral resolution (∼300 nm). Moreover, spatial distribution of functional groups of organic compounds can be simultaneously acquired, allowing to specifically relate them to the observed microstructures. The data presented in this case study highlights the possible new contributions of this method to the description of modalities of Nerita undata shell formation, and what could be expected of its application to other marine biogenic carbonates. Localization of areas of interest would also allow further investigations using more localized methods, such as TEM that would provide complementary information on the relation between organic molecules and crystallographic lattice.

Description: Exploring B/Ca as a pH proxy in bivalves: relationships between Mytilus californianus B/Ca and environmental data from the northeast Pacific Biogeosciences Discussions, 8, 5587-5616, 2011 Author(s): S. J. McCoy, L. F. Robinson, C. A. Pfister, J. T. Wootton, and N. Shimizu A distinct gap in our ability to understand changes in coastal biology that may be associated with recent ocean acidification is the paucity of directly measured ocean environmental parameters at coastal sites in recent decades. Thus, many researchers have turned to sclerochronological reconstructions of water chemistry to document the historical seawater environment. In this study, we explore the relationships between B/Ca and pH to test the feasibility of B/Ca measured on the ion probe as a pH proxy in the California mussel, Mytilus californianus . We compare the M. californianus B/Ca record to directly measured environmental data during mussel growth 1999–2009 to determine the correlation between B/Ca and seawater chemistry and discuss methods for assigning sample chronology when sampling an organism with variable growth rates.