ALBERT

Beschreibung: A new 21.3m firn core was drilled in 2015 at a coastal Antarctic high-accumulation site in Adélie Land (66.78◦ S; 139.56◦ E, 602 m a.s.l.), named Terre Adélie 192A (TA192A). The mean isotopic values (−19.3 ‰ ± 3.1 ‰ for δ18O and 5.4 ‰±2.2 ‰ for deuterium excess) are consistent with other coastal Antarctic values. No significant isotope–temperature relationship can be evidenced at any timescale. This rules out a simple interpretation in terms of local temperature. An observed asymmetry in the δ18O seasonal cycle may be explained by the precipitation of air masses coming from the eastern and western sectors in autumn and winter, recorded in the d-excess signal showing outstanding values in austral spring versus autumn. Significant positive trends are observed in the annual d-excess record and local sea ice extent (135–145◦ E) over the period 1998–2014. However, process studies focusing on resulting isotopic compositions and particularly the deuterium excess–δ18O relationship, evidenced as a potential fingerprint of moisture origins, as well as the collection of more isotopic measurements in Adélie Land are needed for an accurate interpretation of our signals.

Beschreibung: The timing and intensity of snowmelt processes on sea ice are key drivers determining the seasonal sea-ice energy and mass budgets. In the Arctic, satellite passive microwave and radar observations have revealed a trend towards an earlier snowmelt onset during the last decades, which is an important aspect of Arctic amplification and sea ice decline. Around Antarctica, snowmelt on perennial ice is weak and very different than in the Arctic, with most snow surviving the summer. Here we compile time series of snowmelt-onset dates on seasonal and perennial Antarctic sea ice from 1992 to 2014/15 using active microwave observations from European Remote Sensing Satellite (ERS-1/2), Quick Scatterometer (QSCAT) and Advanced Scatterometer (ASCAT) radar scatterometers. We define two snowmelt transition stages: A weak backscatter rise indicating the initial warming and destructive metamorphism of the snowpack (pre-melt), followed by a rapid backscatter rise indicating the onset of thaw-freeze cycles (snowmelt). Results show large interannual variability with an average pre-melt onset date of 29 November and melt onset of 10 December, respectively, on perennial ice, without any significant trends over the study period, consistent with the small trends of Antarctic sea ice extent. There was a latitudinal gradient from early snowmelt onsets in mid-November in the northern Weddell Sea to late (end-December) or even absent snowmelt conditions in the southern Weddell Sea. We show that QSCAT Ku-band (13.4 GHz signal frequency) derived pre-melt and snowmelt onset dates are earlier by 20 and 18 days, respectively, than ERS and ASCAT C-band (5.6 GHz) derived dates. This offset has been considered when constructing the time series. Snowmelt onset dates from passive microwave observations (37 GHz) are later by 14 and 6 days than those from the scatterometers, respectively. Based on these characteristic differences between melt onset dates observed by different microwave wavelengths, we developed a conceptual model which illustrates how the seasonal evolution of snow temperature profiles may affect different microwave bands with different penetration depths. These suggest that future multi-frequency active/passive microwave satellite missions could be used to resolve melt processes throughout the vertical snow column of thick snow on perennial Antarctic sea ice.

Beschreibung: Although quantitative isotope data from speleothems has been used to evaluate isotope-enabled model simulations, currently no consensus exists regarding the most appropriate methodology through which to achieve this. A number of modelling groups will be running isotope-enabled palaeoclimate simulations in the framework of the Coupled Model Intercomparison Project Phase 6, so it is timely to evaluate different approaches to using the speleothem data for data–model comparisons. Here, we illustrate this using 456 globally distributed speleothem δ18O records from an updated version of the Speleothem Isotopes Synthesis and Analysis (SISAL) database and palaeoclimate simulations generated using the ECHAM5-wiso isotope-enabled atmospheric circulation model. We show that the SISAL records reproduce the first-order spatial patterns of isotopic variability in the modern day, strongly supporting the application of this dataset for evaluating model-derived isotope variability into the past. However, the discontinuous nature of many speleothem records complicates the process of procuring large numbers of records if data–model comparisons are made using the traditional approach of comparing anomalies between a control period and a given palaeoclimate experiment. To circumvent this issue, we illustrate techniques through which the absolute isotope values during any time period could be used for model evaluation. Specifically, we show that speleothem isotope records allow an assessment of a model’s ability to simulate spatial isotopic trends. Our analyses provide a protocol for using speleothem isotope data for model evaluation, including screening the observations to take into account the impact of speleothem mineralogy on δ18O values, the optimum period for the modern observational baseline and the selection of an appropriate time window for creating means of the isotope data for palaeo-time-slices.

Beschreibung: We present here the first results, for the preindustrial and mid-Holocene climatological periods, of the newly developed isotope-enhanced version of the fully coupled Earth system model MPI-ESM, called hereafter MPI-ESM-wiso. The water stable isotopes H16O, H18O and HDO have been implemented into all components of the coupled model setup. The mid-Holocene provides the opportunity to evaluate the model response to changes in the seasonal and latitudinal distribution of insolation induced by different orbital forcing conditions. The results of our equilibrium simulations allow us to evaluate the performance of the isotopic model in simulating the spatial and temporal variations of water isotopes in the different compartments of the hydrological system for warm climates. For the preindustrial climate, MPI-ESM-wiso reproduces very well the observed spatial distribution of the isotopic content in precipitation linked to the spatial variations in temperature and precipitation rate. We also find a good model–data agreement with the observed distribution of isotopic composition in surface seawater but a bias with the presence of surface seawater that is too 18O-depleted in the Arctic Ocean. All these results are improved compared to the previous model version ECHAM5/MPIOM. The spatial relationships of water isotopic composition with temperature, precipitation rate and salinity are consistent with observational data. For the preindustrial climate, the interannual relationships of water isotopes with temperature and salinity are globally lower than the spatial ones, consistent with previous studies. Simulated results under mid-Holocene conditions are in fair agreement with the isotopic measurements from ice cores and continental speleothems. MPI-ESM-wiso simulates a decrease in the isotopic composition of precipitation from North Africa to the Tibetan Plateau via India due to the enhanced monsoons during the mid-Holocene. Over Greenland, our simulation indicates a higher isotopic composition of precipitation linked to higher summer temperature and a reduction in sea ice, shown by positive isotope–temperature gradient. For the Antarctic continent, the model simulates lower isotopic values over the East Antarctic plateau, linked to the lower temperatures during the mid-Holocene period, while similar or higher isotopic values are modeled over the rest of the continent. While variations of isotopic contents in precipitation over West Antarctica between mid-Holocene and preindustrial periods are partly controlled by changes in temperature, the transport of relatively 18O-rich water vapor near the coast to the western ice core sites could play a role in the final isotopic composition. So, more caution has to be taken about the reconstruction of past temperature variations during warm periods over this area. The coupling of such a model with an ice sheet model or the use of a zoomed grid centered on this region could help to better describe the role of the water vapor transport and sea ice around West Antarctica. The reconstruction of past salinity through isotopic content in sea surface waters can be complicated for regions with strong ocean dynamics, variations in sea ice regimes or significant changes in freshwater budget, giving an extremely variable relationship between the isotopic content and salinity of ocean surface waters over small spatial scales. These complicating factors demonstrate the complexity of interpreting water isotopes as past climate signals of warm periods like the mid-Holocene. A systematic isotope model intercomparison study for further insights on the model dependency of these results would be beneficial.

Beschreibung: Recent studies pointed to a high ice nucleating activity (INA) in the Arctic sea surface microlayer (SML). However, related chemical information is still sparse. In the present study, INA and free glucose concentrations were quantified in Arctic SML and bulk water samples from the marginal ice zone, the ice-free ocean, melt ponds, and open waters within the ice pack. T50 (defining INA) ranged from −17.4 to −26.8 °C. Glucose concentrations varied from 0.6 to 51 μg/L with highest values in the SML from the marginal ice zone and melt ponds (median 16.3 and 13.5 μg/L) and lower values in the SML from the ice pack and the ice-free ocean (median 3.9 and 4.0 μg/L). Enrichment factors between the SML and the bulk ranged from 0.4 to 17. A positive correlation was observed between free glucose concentration and INA in Arctic water samples (T50(°C) = (−25.6 ± 0.6) + (0.15 ± 0.04)·Glucose(μg/L), RP = 0.66, n = 74). Clustering water samples based on phytoplankton pigment composition resulted in robust but different correlations within the four clusters (RP between 0.67 and 0.96), indicating a strong link to phytoplankton-related processes. Since glucose did not show significant INA itself, free glucose may serve as a potential tracer for INA in Arctic water samples.

Beschreibung: In this study, we present results obtained from modelling the mid-Pliocene warm period using the Community Earth System Models (COSMOS, version: COSMOS-landveg r2413, 2009) with the two different sets of boundary conditions prescribed for the two phases of the Pliocene Model Intercomparison Project (PlioMIP). Boundary conditions, model forcing, and modelling methodology of the two phases of PlioMIP, tagged PlioMIP1 and PlioMIP2,differ considerably in palaeogeography, in particular with regards to the state of ocean gateways, ice-masks, vegetation and topography. Further differences between model setups as suggested for PlioMIP1 and PlioMIP2 consider updates to the concentration of atmospheric carbon dioxide (CO2), that is specified as 405 and 400 parts per million by volume (ppmv) for PlioMIP1 and PlioMIP2, respectively, as well as minor differences in the concentrations of methane (CH4) and nitrous oxide (N2O) due to changes in the protocol of the Paleoclimate Model Intercomparison Project (PMIP) from phase 3 to phase 4. With this manuscript, we bridge the gap between our contributions to PlioMIP1 (Stepanek and Lohmann, 2012) and PlioMIP2 (Stepanek et al., 2019). We highlight some of the effects that differences in the chosen Mid-Pliocene model setup (PlioMIP2 vs. PlioMIP1) have on the climate state as derived with the COSMOS, as this information will be valuable in the framework of the model-model and model-data-comparison within PlioMIP2. We evaluate the model sensitivity to improved mid-Pliocene boundary conditions using PlioMIP’s core mid-Pliocene experiments for PlioMIP1 and PlioMIP2, and present further simulations where we test model sensitivity to variations in palaeogeography, orbit and concentration of CO2. Firstly,we highlight major changes in boundary conditions from PlioMIP1 to PlioMIP2 and also the limitations recorded from the initial effort. The results derived from of our simulations show that COSMOS simulates a mid-Pliocene climate state that is 0.08 K colder in PlioMIP2, if compared to PlioMIP1. On one hand, high-latitude warming,which is supported by proxy evidence of the mid-Pliocene, is underestimated in simulations of both PlioMIP1 andPlioMIP2. On the other hand, spatial variations in surface air temperature (SAT), sea surface temperature (SST) as well as the distribution of sea ice suggest improvement of simulated SAT and SST in PlioMIP2 if employing the updated palaeogeography. The PlioMIP2 Mid-Pliocene simulation produces warmer SSTs in the Arctic and North Atlantic Ocean than derived from the respective PlioMIP1 climate state. The difference in prescribed CO2accountsfor 1.1 K of warming in the Arctic, leading to an ice-free summer in the PlioMIP1 simulation, and a quasi-ice-free summer in PlioMIP2. Furthermore, employing different orbital forcings in simulating the Mid-Pliocene lead to pronounced annual and seasonal variations, which is not accounted for by marine and terrestrial reconstruction of the time-slice.

Beschreibung: The Antarctic temperature changes over the past millennia remain more uncertain than in many other continental regions. This has several origins: (1) the number of high-resolution ice cores is small, in particular on the East Antarctic plateau and in some coastal areas in East Antarctica; (2) the short and spatially sparse instrumental records limit the calibration period for reconstructions and the assessment of the methodologies; (3) the link between isotope records from ice cores and local climate is usually complex and dependent on the spatial scales and timescales investigated. Here, we use climate model results, pseudo-proxy experiments and data assimilation experiments to assess the potential for reconstructing the Antarctic temperature over the last 2 millennia based on a new database of stable oxygen isotopes in ice cores compiled in the frame- work of Antarctica2k (Stenni et al., 2017). The well-known covariance between δ18O and temperature is reproduced in the two isotope-enabled models used (ECHAM5/MPI-OM and ECHAM5-wiso), but is generally weak over the different Antarctic regions, limiting the skill of the reconstructions. Furthermore, the strength of the link displays large variations over the past millennium, further affecting the potential skill of temperature reconstructions based on statistical methods which rely on the assumption that the last decades are a good estimate for longer temperature reconstructions. Using a data assimilation technique allows, in theory, for changes in the δ18O–temperature link through time and space to be taken into account. Pseudoproxy experiments confirm the benefits of using data assimilation methods instead of statistical methods that provide reconstructions with unrealistic variances in some Antarctic subregions. They also confirm that the relatively weak link between both variables leads to a limited potential for reconstructing temperature based on δ18O. However, the reconstruction skill is higher and more uniform among reconstruction methods when the reconstruction target is the Antarctic as a whole rather than smaller Antarctic subregions. This consistency between the methods at the large scale is also observed when reconstructing temperature based on the real δ18O regional composites of Stenni et al. (2017). In this case, temperature reconstructions based on data assimilation confirm the long-term cooling over Antarctica during the last millennium, and the later onset of anthropogenic warming compared with the simulations without data assimilation, which is especially visible in West Antarctica. Data assimilation also allows for models and direct observations to be reconciled by reproducing the east–west contrast in the recent temperature trends. This recent warming pattern is likely mostly driven by internal variability given the large spread of individual Paleoclimate Modelling Intercomparison Project (PMIP)/Coupled Model Intercomparison Project (CMIP) model realizations in simulating it. As in the pseudoproxy framework, the reconstruction methods perform differently at the subregional scale, especially in terms of the variance of the time series produced. While the potential benefits of using a data assimilation method instead of a statistical method have been highlighted in a pseudoproxy framework, the instrumental series are too short to confirm this in a realistic setup.

Beschreibung: Ice-wedge polygons are common features of lowland tundra in the continuous permafrost zone and prone to rapid degradation through melting of ground ice. There are many interrelated processes involved in ice-wedge thermokarst and it is a major challenge to quantify their influence on the stability of the permafrost underlying the landscape. In this study we used a numerical modelling approach to investigate the degradation of ice wedges with a focus on the influence of hydrological conditions. Our study area was Samoylov Island in the Lena River delta of northern Siberia, for which we had in situ measurements to evaluate the model. The tailored version of the CryoGrid 3 land surface model was capable of simulating the changing microtopography of polygonal tundra and also regarded lateral fluxes of heat, water, and snow. We demonstrated that the approach is capable of simulating ice-wedge degradation and the associated transition from a low-centred to a high-centred polygonal microtopography. The model simulations showed ice-wedge degradation under recent climatic conditions of the study area, irrespective of hydrological conditions. However, we found that wetter conditions lead to an earlier onset of degradation and cause more rapid ground subsidence. We set our findings in correspondence to observed types of ice-wedge polygons in the study area and hypothesized on remaining discrepancies between modelled and observed ice-wedge thermokarst activity. Our quantitative approach provides a valuable complement to previous, more qualitative and conceptual, descriptions of the possible pathways of ice-wedge polygon evolution. We concluded that our study is a blueprint for investigating thermokarst landforms and marks a step forward in understanding the complex interrelationships between various processes shaping ice-rich permafrost landscapes.

Beschreibung: Warming of the Arctic led to an increase in permafrost temperatures by about 0.3 �C during the last decade. Permafrost warming is associated with increasing sediment water content, permeability, and diffusivity and could in the long term alter microbial community composition and abundance even before permafrost thaws. We studied the long-term effect (up to 2500 years) of submarine permafrost warming on microbial communities along an onshore–offshore transect on the Siberian Arctic Shelf displaying a natural temperature gradient of more than 10 �C. We analysed the in situ development of bacterial abundance and community composition through total cell counts (TCCs), quantitative PCR of bacterial gene abundance, and amplicon sequencing and correlated the microbial community data with temperature, pore water chemistry, and sediment physicochemical parameters. On timescales of centuries, permafrost warming coincided with an overall decreasing microbial abundance, whereas millennia after warming microbial abundance was similar to cold onshore permafrost. In addition, the dissolved organic carbon content of all cores was lowest in submarine permafrost after millennial-scale warming. Based on correlation analysis, TCC, unlike bacterial gene abundance, showed a significant rank-based negative correlation with increasing temperature, while bacterial gene copy numbers showed a strong negative correlation with salinity. Bacterial community composition correlated only weakly with temperature but strongly with the pore water stable isotopes �18O and �D, as well as with depth. The bacterial community showed substantial spatial variation and an overall dominance of Actinobacteria, Chloroflexi, Firmicutes, Gemmatimonadetes, and Proteobacteria, which are amongst the microbial taxa that were also found to be active in other frozen permafrost environments. We suggest that, millennia after permafrost warming by over 10 �C, microbial community composition and abundance show some indications for proliferation but mainly reflect the sedimentation history and paleoenvironment and not a direct effect through warming.

Beschreibung: The Global Ocean Data Analysis Project (GLODAP) is a synthesis effort providing regular compilations of surface to bottom ocean biogeochemical data, with an emphasis on seawater inorganic carbon chemistry and related variables determined through chemical analysis of water samples. This update of GLODAPv2, v2.2019, adds data from 116 cruises to the previous version, extending its coverage in time from 2013 to 2017, while also adding some data from prior years. GLODAPv2.2019 includes measurements from more than 1.1 million water samples from the global oceans collected on 840 cruises. The data for the 12 GLODAP core variables (salinity, oxygen, nitrate, silicate, phosphate, dissolved inorganic carbon, total alkalinity, pH, CFC-11, CFC-12, CFC-113, and CCl4) have undergone extensive quality control, especially systematic evaluation of bias. The data are available in two formats: (i) as submitted by the data originator but updated to WOCE exchange format and (ii) as a merged data product with adjustments applied to minimize bias. These adjustments were derived by comparing the data from the 116 new cruises with the data from the 724 quality-controlled cruises of the GLODAPv2 data product. They correct for errors related to measurement, calibration, and data handling practices, taking into account any known or likely time trends or variations. The compiled and adjusted data product is believed to be consistent to better than 0.005 in salinity, 1 % in oxygen, 2 % in nitrate, 2 % in silicate, 2 % in phosphate, 4 µmol kg−1 in dissolved inorganic carbon, 4 µmol kg−1 in total alkalinity, 0.01–0.02 in pH, and 5 % in the halogenated transient tracers. The compilation also includes data for several other variables, such as isotopic tracers. These were not subjected to bias comparison or adjustments. The original data, their documentation and DOI codes are available in the Ocean Carbon Data System of NOAA NCEI (https://www.nodc.noaa.gov/ocads/oceans/GLODAPv2_2019/, last access: 17 September 2019). This site also provides access to the merged data product, which is provided as a single global file and as four regional ones – the Arctic, Atlantic, Indian, and Pacific oceans – under https://doi.org/10.25921/xnme-wr20 (Olsen et al., 2019). The product files also include significant ancillary and approximated data. These were obtained by interpolation of, or calculation from, measured data. This paper documents the GLODAPv2.2019 methods and provides a broad overview of the secondary quality control procedures and results.

Beschreibung: We present a Lagrangian convective transport scheme developed for global chemistry and transport models, which considers the variable residence time that an air parcel spends in convection. This is particularly important for accurately simulating the tropospheric chemistry of short-lived species, e.g., for determining the time available for heterogeneous chemical processes on the surface of cloud droplets. In current Lagrangian convective transport schemes air parcels are stochastically redistributed within a fixed time step according to estimated probabilities for convective entrainment as well as the altitude of detrainment. We introduce a new scheme that extends this approach by modeling the variable time that an air parcel spends in convection by estimating vertical updraft velocities. Vertical updraft velocities are obtained by combining convective mass fluxes from meteorological analysis data with a parameterization of convective area fraction profiles. We implement two different parameterizations: a parameterization using an observed constant convective area fraction profile and a parameterization that uses randomly drawn profiles to allow for variability. Our scheme is driven by convective mass fluxes and detrainment rates that originate from an external convective parameterization, which can be obtained from meteorological analysis data or from general circulation models. We study the effect of allowing for a variable time that an air parcel spends in convection by performing simulations in which our scheme is implemented into the trajectory module of the ATLAS chemistry and transport model and is driven by the ECMWF ERA-Interim reanalysis data. In particular, we show that the redistribution of air parcels in our scheme conserves the vertical mass distribution and that the scheme is able to reproduce the convective mass fluxes and detrainment rates of ERA-Interim. We further show that the estimated vertical updraft velocities of our scheme are able to reproduce wind profiler measurements performed in Darwin, Australia, for velocities larger than 0.6 m s−1. SO2 is used as an example to show that there is a significant effect on species mixing ratios when modeling the time spent in convective updrafts compared to a redistribution of air parcels in a fixed time step. Furthermore, we perform long-time global trajectory simulations of radon-222 and compare with aircraft measurements of radon activity.

Beschreibung: Holocene permafrost from ice wedge polygons in the vicinity of large seabird breeding colonies in the Thule District, NW Greenland, was drilled to explore the relation between permafrost aggradation and seabird presence. The latter is reliant on the presence of the North Water Polynya (NOW) in the northern Baffin Bay. The onset of peat accumulation associated with the arrival of little auks (Alle alle) in a breeding colony at Annikitisoq, north of Cape York, is radiocarbon-dated to 4400 cal BP. A thick-billed murre (Uria lomvia) colony on Appat (Saunders Island) in the mouth of the Wolstenholme Fjord started 5650 cal BP. Both species provide marine-derived nutrients (MDNs) that fertilize vegetation and promote peat growth. The geochemical signature of organic matter left by the birds is traceable in the frozen Holocene peat. The peat accumulation rates at both sites are highest after the onset, decrease over time, and were about 2-times faster at the little auk site than at the thick-billed murre site. High accumulation rates induce shorter periods of organic matter (OM) decomposition before it enters the perennially frozen state. This is seen in comparably high C=N ratios and less depleted 13C, pointing to a lower degree of OM decomposition at the little auk site, while the opposite pattern can be discerned at the thick-billed murre site. Peat accumulation rates correspond to 15N trends, where decreasing accumulation led to increasing depletion in 15N as seen in the little-auk-related data. In contrast, the more decomposed OM of the thick-billed murre site shows almost stable 15N. Late Holocene wedge ice fed by cold season precipitation was studied at the little auk site and provides the first stable-water isotopic record from Greenland with mean 18O of 8:00:8, mean D of 36:25:7, mean d excess of 7:70:7, and a 18O-D slope of 7.27, which is close to those of the modern Thule meteoric water line. The syngenetic ice wedge polygon development is mirrored in testacean records of the little auk site and delineates polygon low-center, dry-out, and polygon-high-center stages. The syngenetic permafrost formation directly depending on peat growth (controlled by bird activity) falls within the period of neoglacial cooling and the establishment of the NOW, thus indirectly following the Holocene climate trends.

Beschreibung: Author Posting. © American Chemical Society, 2019. This article is posted here by permission of American Chemical Society for personal use, not for redistribution. The definitive version was published in Kivenson, V., Lemkau, K. L., Pizarro, O., Yoerger, D. R., Kaiser, C., Nelson, R. K., Carmichael, C., Paul, B. G., Reddy, C. M., & Valentine, D. L. (2019). Ocean Dumping of Containerized DDT Waste Was a Sloppy Process. Environmental Science and Technology (2019), doi:10.1021/acs.est.8b05859.

Beschreibung: Industrial-scale dumping of organic waste to the deep ocean was once common practice, leaving a legacy of chemical pollution for which a paucity of information exists. Using a nested approach with autonomous and remotely operated underwater vehicles, a dumpsite offshore California was surveyed and sampled. Discarded waste containers littered the site and structured the suboxic benthic environment. Dichlorodiphenyltrichloroethane (DDT) was reportedly dumped in the area, and sediment analysis revealed substantial variability in concentrations of p,p-DDT and its analogs, with a peak concentration of 257 μg g–1, ∼40 times greater than the highest level of surface sediment contamination at the nearby DDT Superfund site. The occurrence of a conspicuous hydrocarbon mixture suggests that multiple petroleum distillates, potentially used in DDT manufacture, contributed to the waste stream. Application of a two end-member mixing model with DDTs and polychlorinated biphenyls enabled source differentiation between shelf discharge versus containerized waste. Ocean dumping was found to be the major source of DDT to more than 3000 km2 of the region’s deep seafloor. These results reveal that ocean dumping of containerized DDT waste was inherently sloppy, with the contents readily breaching containment and leading to regional scale contamination of the deep benthos.

Beschreibung: This material is based upon work supported by the National Science Foundation Graduate Research Fellowship for V.K. under Grant No. 1650114. Expeditions AT-18-11 and AT-26-06 were funded by the NSF (OCE-0961725 and OCE-1046144). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. We thank the captain and crew of the RV Atlantis, the pilots and crew of the ROV Jason, the crew of the AUV Sentry, the scientific party of the AT-18-11 and AT-26-06 expeditions, Justin Tran for assistance with the preparation of multibeam data, M. Indira Venkatesan for a helpful discussion of the NOAA datasets, and Nathan Dodder for advice on the procedure for compound identification.

Beschreibung: Author Posting. © American Chemical Society, 2019. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Environmental Science and Technology 53(16), (2019): 9398-9406, doi:10.1021/acs.est.9b02395.

Beschreibung: Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range = 0.010–0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p 〈 0.001, ρ = 0.90, range = 145–15,900 mg/L), Mn + Fe concentrations (p 〈 0.001, ρ = 0.82, range = 〈0.005–18.5 mg/L), and pH (p 〈 0.001, ρ = −0.67, range = 6.2–9.2), indicating Ra in groundwater was influenced by salinity, redox, and pH. Ra-rich groundwater was mixed with up to 45% oil-field water at some locations, primarily infiltrating through unlined disposal ponds, based on Cl, Li, noble-gas, and other data. Yet 228Ra/226Ra ratios in pond-impacted groundwater (median = 3.1) differed from those in oil-field water (median = 0.51). PHREEQC mixing calculations and spatial geochemical variations suggest that the Ra in the oil-field water was removed by coprecipitation with secondary barite and adsorption on Mn–Fe precipitates in the near-pond environment. The saline, organic-rich oil-field water subsequently mobilized Ra from downgradient aquifer sediments via Ra-desorption and Mn/Fe-reduction processes. This study demonstrates that infiltration of oil-field water may leach Ra into groundwater by changing salinity and redox conditions in the subsurface rather than by mixing with a high-Ra source.

Beschreibung: This article was improved by the reviews of John Izbicki and anonymous reviewers for the journal. This work was funded by the California State Water Resources Control Board’s Regional Groundwater Monitoring in Areas of Oil and Gas Production Program and the USGS Cooperative Water Program. A.V., A.J.K., and Z.W were supported by USDA-NIFA grant (#2017-68007-26308). Any use of trade, firm, or product names is for description purposes only and does not imply endorsement by the U.S. Government.

Beschreibung: Author Posting. © American Chemical Society, 2019. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Environmental Science and Technology 53(14), (2019):8244-8251, doi:10.1021/acs.est.9b02344.

Beschreibung: Perylene is a frequently abundant, and sometimes the only polycyclic aromatic hydrocarbon (PAH) in aquatic sediments, but its origin has been subject of a longstanding debate in geochemical research and pollutant forensics because its historical record differs markedly from typical anthropogenic PAHs. Here we investigate whether perylene serves as a source-specific molecular marker of fungal activity in forest soils. We use a well-characterized sedimentary record (1735 to 1999) from the anoxic-bottom waters of the Pettaquamscutt River basin, RI, USA to examine mass accumulation rates and isotope records of perylene, and compare them with total organic carbon and the anthropogenic PAH fluoranthene. We support our arguments with radiocarbon (14C) data of higher plant leaf-wax n-alkanoic acids. Isotope-mass balance calculations of perylene and n-alkanoic acids indicate that ~40 % of sedimentary organic matter is of terrestrial origin. Further, both terrestrial markers are pre-aged on millennial time-scales prior to burial in sediments and insensitive to elevated 14C concentrations following nuclear weapons testing in the mid-20th Century. Instead, changes coincide with enhanced erosional flux during urban sprawl. These findings suggest that perylene is definitely a product of soil derived fungi, and a powerful chemical tracer to study spatial and temporal connectivity between terrestrial and aquatic environments.

Beschreibung: We thank John King, Sean Sylva, Brad Hubeny, Peter Sauer, and Jim Broda for their help in sampling; Carl Johnson and Daniel Montluçon for their incessant help with analyses; as well as Mark Yunker for critical discussion on the perils of perylene. Professor Phil Meyers and two anonymous reviewers provided comments that improved the quality of the manuscript. U.M.H. acknowledges the Swiss National Science Foundation for his postdoctoral fellowship and T.I.E. and K.A.H. acknowledges the NSF for research grants CHE-0089172 and OCE-9708478.

Beschreibung: 2020-06-19

Beschreibung: Recent studies pointed to a high ice nucleating activity (INA) in the Arctic sea surface microlayer (SML). However, related chemical information is still sparse. In the present study, INA and free glucose concentrations were quantified in Arctic SML and bulk water samples from the marginal ice zone, the ice-free ocean, melt ponds, and open waters within the ice pack. T50 (defining INA) ranged from −17.4 to −26.8 °C. Glucose concentrations varied from 0.6 to 51 μg/L with highest values in the SML from the marginal ice zone and melt ponds (median 16.3 and 13.5 μg/L) and lower values in the SML from the ice pack and the ice-free ocean (median 3.9 and 4.0 μg/L). Enrichment factors between the SML and the bulk ranged from 0.4 to 17. A positive correlation was observed between free glucose concentration and INA in Arctic water samples (T50(°C) = (−25.6 ± 0.6) + (0.15 ± 0.04)·Glucose(μg/L), RP = 0.66, n = 74). Clustering water samples based on phytoplankton pigment composition resulted in robust but different correlations within the four clusters (RP between 0.67 and 0.96), indicating a strong link to phytoplankton-related processes. Since glucose did not show significant INA itself, free glucose may serve as a potential tracer for INA in Arctic water samples.