ALBERT

Description: The input of nitrogen (N) to ecosystems has increased dramatically over the past decades. While total (wet + dry) N deposition has been extensively determined in temperate regions, only very few data sets of N wet deposition exist for tropical ecosystems, and moreover, reliable experimental information about N dry deposition in tropical environments is lacking. In this study we estimate dry and wet deposition of inorganic N for a remote pasture site in the Amazon Basin based on in-situ measurements. The measurements covered the late dry (biomass burning) season, a transition period and the onset of the wet season (clean conditions) (12 September to 14 November 2002) and were a part of the LBA-SMOCC (Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall, and Climate) 2002 campaign. Ammonia (NH3), nitric acid (HNO3), nitrous acid (HONO), nitrogen dioxide (NO2), nitric oxide (NO), ozone (O3), aerosol ammonium (NH4+) and aerosol nitrate (NO3-) were measured in real-time, accompanied by simultaneous meteorological measurements. Dry deposition fluxes of NO2 and HNO3 are inferred using the ''big leaf multiple resistance approach'' and particle deposition fluxes are derived using an established empirical parameterization. Bi-directional surface-atmosphere exchange fluxes of NH3 and HONO are estimated by applying a ''canopy compensation point model''. N dry and wet deposition is dominated by NH3 and NH4+, which is largely the consequence of biomass burning during the dry season. The grass surface appeared to have a strong potential for daytime NH3 emission, owing to high canopy compensation points, which are related to high surface temperatures and to direct NH3 emissions from cattle excreta. NO2 also significantly accounted for N dry deposition, whereas HNO3, HONO and N-containing aerosol species were only minor contributors. Ignoring NH3 emission from the vegetation surface, the annual net N deposition rate is estimated to be about −11 kgN ha-1 yr-1. If on the other hand, surface-atmosphere exchange of NH3 is considered to be bi-directional, the annual net N budget at the pasture site is estimated to range from −2.15 to −4.25 kgN ha-1 yr-1.

Description: Understanding sources, concentrations, and transformations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere is important because of their potent mutagenicity and carcinogenicity. The measurement of particle-bound PAHs by three different methods during the Mexico City Metropolitan Area field campaign in April 2003 presents a unique opportunity for characterization of these compounds and intercomparison of the methods. The three methods are (1) collection and analysis of bulk samples for time-integrated gas- and particle-phase speciation by gas chromatography/mass spectrometry; (2) aerosol photoionization for fast detection of PAHs on particles' surfaces; and (3) aerosol mass spectrometry for fast analysis of size and chemical composition. This research represents the first time aerosol mass spectrometry has been used to measure ambient PAH concentrations and the first time that fast, real-time methods have been used to quantify PAHs alongside traditional filter-based measurements in an extended field campaign. Speciated PAH measurements suggest that motor vehicles and garbage and wood burning are important sources in Mexico City. The diurnal concentration patterns captured by aerosol photoionization and aerosol mass spectrometry are generally consistent. Ambient concentrations of particle-phase PAHs typically peak at ~110 ng m-3 during the morning rush hour and rapidly decay due to changes in source activity patterns and dilution as the boundary layer rises, although surface-bound PAH concentrations decay faster. The more rapid decrease in surface versus bulk PAH concentrations during the late morning suggests that freshly emitted combustion-related particles are quickly coated by secondary aerosol material in Mexico City's atmosphere and may also be transformed by heterogeneous reactions.

Description: The largest uncertainty in the radiative forcing of climate change over the industrial era is that due to aerosols, a substantial fraction of which is the uncertainty associated with scattering and absorption of shortwave (solar) radiation by anthropogenic aerosols in cloud-free conditions (IPCC, 2001). Quantifying and reducing the uncertainty in aerosol influences on climate is critical to understanding climate change over the industrial period and to improving predictions of future climate change for assumed emission scenarios. Measurements of aerosol properties during major field campaigns in several regions of the globe during the past decade are contributing to an enhanced understanding of atmospheric aerosols and their effects on light scattering and climate. The present study, which focuses on three regions downwind of major urban/population centers (North Indian Ocean (NIO) during INDOEX, the Northwest Pacific Ocean (NWP) during ACE-Asia, and the Northwest Atlantic Ocean (NWA) during ICARTT), incorporates understanding gained from field observations of aerosol distributions and properties into calculations of perturbations in radiative fluxes due to these aerosols. This study evaluates the current state of observations and of two chemical transport models (STEM and MOZART). Measurements of burdens, extinction optical depth (AOD), and direct radiative effect of aerosols (DRE – change in radiative flux due to total aerosols) are used as measurement-model check points to assess uncertainties. In-situ measured and remotely sensed aerosol properties for each region (mixing state, mass scattering efficiency, single scattering albedo, and angular scattering properties and their dependences on relative humidity) are used as input parameters to two radiative transfer models (GFDL and University of Michigan) to constrain estimates of aerosol radiative effects, with uncertainties in each step propagated through the analysis. Constraining the radiative transfer calculations by observational inputs increases the clear-sky, 24-h averaged AOD (34±8%), top of atmosphere (TOA) DRE (32±12%), and TOA direct climate forcing of aerosols (DCF – change in radiative flux due to anthropogenic aerosols) (37±7%) relative to values obtained with "a priori" parameterizations of aerosol loadings and properties (GFDL RTM). The resulting constrained clear-sky TOA DCF is −3.3±0.47, −14±2.6, −6.4±2.1 Wm−2 for the NIO, NWP, and NWA, respectively. With the use of constrained quantities (extensive and intensive parameters) the calculated uncertainty in DCF was 25% less than the "structural uncertainties" used in the IPCC-2001 global estimates of direct aerosol climate forcing. Such comparisons with observations and resultant reductions in uncertainties are essential for improving and developing confidence in climate model calculations incorporating aerosol forcing.

Description: An Aerodyne Aerosol Mass Spectrometer (AMS) was deployed at the CENICA Supersite, during the Mexico City Metropolitan Area field study (MCMA-2003) from 31 March-4 May 2003 to investigate particle concentrations, sources, and processes. The AMS provides real time information on mass concentration and composition of the non-refractory species in particulate matter less than 1 µm (NR-PM1) with high time and size-resolution. In order to account for the refractory material in the aerosol, we also present estimates of Black Carbon (BC) using an aethalometer and an estimate of the aerosol soil component obtained from Proton-Induced X-ray Emission Spectrometry (PIXE) analysis of impactor substrates. Comparisons of AMS + BC + soil mass concentration with other collocated particle instruments (a LASAIR Optical Particle Counter, a PM2.5 Tapered Element Oscillating Microbalance (TEOM), and a PM2.5 DustTrak Aerosol Monitor) show that the AMS + BC + soil mass concentration is consistent with the total PM2.5 mass concentration during MCMA-2003 within the combined uncertainties. In Mexico City, the organic fraction of the estimated PM2.5 at CENICA represents, on average, 54.6% (standard deviation σ=10%) of the mass, with the rest consisting of inorganic compounds (mainly ammonium nitrate and sulfate/ammonium salts), BC, and soil. Inorganic compounds represent 27.5% of PM2.5 (σ=10%); BC mass concentration is about 11% (σ=4%); while soil represents about 6.9% (σ=4%). Size distributions are presented for the AMS species; they show an accumulation mode that contains mainly oxygenated organic and secondary inorganic compounds. The organic size distributions also contain a small organic particle mode that is likely indicative of fresh traffic emissions; small particle modes exist for the inorganic species as well. Evidence suggests that the organic and inorganic species are not always internally mixed, especially in the small modes. The aerosol seems to be neutralized most of the time; however, there were some periods when there was not enough ammonium to completely neutralize the nitrate, chloride and sulfate present. The diurnal cycle and size distributions of nitrate suggest local photochemical production. On the other hand, sulfate appears to be produced on a regional scale. There are indications of new particle formation and growth events when concentrations of SO2 were high. Although the sources of chloride are not clear, this species seems to condense as ammonium chloride early in the morning and to evaporate as the temperature increases and RH decreases. The total and speciated mass concentrations and diurnal cycles measured during MCMA-2003 are similar to measurements during a previous field campaign at a nearby location.

Description: As part of the Large Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC) campaign, detailed surface and airborne aerosol measurements were performed over the Amazon Basin during the dry to wet season from 16 September to 14 November 2002. Optical and physical properties of aerosols at the surface, and in the boundary layer (BL) and free troposphere (FT) during the dry season are discussed in this article. Carbon monoxide (CO) is used as a tracer for biomass burning emissions. At the surface, good correlation among the light scattering coefficient (σs at 545 nm), PM2.5, and CO indicates that biomass burning is the main source of aerosols. Accumulation of haze during some of the large-scale biomass burning events led to high PM2.5 (225 μg m−3), σs (1435 Mm−1), aerosol optical depth at 500 nm (3.0), and CO (3000 ppb). A few rainy episodes reduced the PM2.5, number concentration (CN) and CO concentration by two orders of magnitude. The correlation analysis between σs and aerosol optical thickness shows that most of the optically active aerosols are confined to a layer with a scale height of 1617 m during the burning season. This is confirmed by aircraft profiles. The average mass scattering and absorption efficiencies (545 nm) for small particles (diameter Dp

Description: The largest uncertainty in the radiative forcing of climate change over the industrial era is that due to aerosols, a substantial fraction of which is the uncertainty associated with scattering and absorption of shortwave (solar) radiation by anthropogenic aerosols in cloud-free conditions (IPCC, 2001). Quantifying and reducing the uncertainty in aerosol influences on climate is critical to understanding climate change over the industrial period and to improving predictions of future climate change for assumed emission scenarios. Measurements of aerosol properties during major field campaigns in several regions of the globe during the past decade are contributing to an enhanced understanding of atmospheric aerosols and their effects on light scattering and climate. The present study, which focuses on three regions downwind of major urban/population centers (North Indian Ocean (NIO) during INDOEX, the Northwest Pacific Ocean (NWP) during ACE-Asia, and the Northwest Atlantic Ocean (NWA) during ICARTT), incorporates understanding gained from field observations of aerosol distributions and properties into calculations of perturbations in radiative fluxes due to these aerosols. This study evaluates the current state of observations and of two chemical transport models (STEM and MOZART). Measurements of burdens, extinction optical depth (AOD), and direct radiative effect of aerosols (DRE – change in radiative flux due to total aerosols) are used as measurement-model check points to assess uncertainties. In-situ measured and remotely sensed aerosol properties for each region (mixing state, mass scattering efficiency, single scattering albedo, and angular scattering properties and their dependences on relative humidity) are used as input parameters to two radiative transfer models (GFDL and University of Michigan) to constrain estimates of aerosol radiative effects, with uncertainties in each step propagated through the analysis. Constraining the radiative transfer calculations by observational inputs increases the clear-sky, 24-h averaged AOD (34±8%), top of atmosphere (TOA) DRE (32±12%), and TOA direct climate forcing of aerosols (DCF – change in radiative flux due to anthropogenic aerosols) (37±7%) relative to values obtained with "a priori" parameterizations of aerosol loadings and properties (GFDL RTM). The resulting constrained TOA DCF is −3.3±0.47, −14±2.6, −6.4±2.1 Wm−2 for the NIO, NWP, and NWA, respectively. Constraining the radiative transfer calculations by observational inputs reduces the uncertainty range in the DCF in these regions relative to global IPCC (2001) estimates by a factor of approximately 2. Such comparisons with observations and resultant reductions in uncertainties are essential for improving and developing confidence in climate model calculations incorporating aerosol forcing.

Description: Sources of PM2.5 at the Fresno Supersite during high PM2.5 episodes occurring from 15 December 2000–3 February 2001 were estimated with the Chemical Mass Balance (CMB) receptor model. The ability of source profiles with organic markers to distinguish motor vehicle, residential wood combustion (RWC), and cooking emissions was evaluated with simulated data. Organics improved the distinction between gasoline and diesel vehicle emissions and allowed a more precise estimate of the cooking source contribution. Sensitivity tests using average ambient concentrations showed that the gasoline vehicle contribution was not resolved without organics. Organics were not required to estimate hardwood combustion contributions. The most important RWC marker was the water-soluble potassium ion. The estimated cooking contribution did not depend on cholesterol because its concentrations were below the detection limit in most samples. Winter time source contributions were estimated by applying the CMB model to individual and average sample concentrations. RWC was the most significant source, contributing 29–31% of the measured PM2.5. Hardwood and softwood combustion accounted for 16–17% and 12–15%, respectively. Secondary ammonium nitrate and motor vehicle emissions accounted for 31–33% and 9–15%, respectively. The gasoline vehicle contribution (3–10%) was comparable to the diesel vehicle contribution (5–6%). The cooking contribution was 5–19% of PM2.5. Fresno source apportionment results were consistent with those estimated in previous studies.

Description: High-resolution paleo-environmental and paleo-ecological archives in laminated sequences are present in selected areas from the upper continental Peruvian margin within the oxygen minimum zone. We present initial results of a multidisciplinary study (the PALEOPECES project) that aims to reconstruct environmental and ecosystem variability during the past 200 years from high-resolution records. We report chronology development, sediment structure, elemental, organic, and mineralogical compositions of a box core collected at 300 m depth off Pisco, central Peru. An average sedimentation rate of 2.2 mm y-1 was estimated from downcore excess 210Pb activities for the last 100-150 years. Extending this rate further downcore indicates that a slump located at 52 cm depth from the top of the core can be correlated with a large tsunami that struck the coast of central Peru in 1746. X-ray analyses reveal laminated structures composed of couplets of light and dark laminae. Observations under polarized microscope show that light laminae are dominated by more dense, detrital and terrigenous material, while dark laminae are less dense with greater concentrations of amorphous biogenic silica. Downcore variations in dry bulk density and X-ray radioscopy of gray level show similar patterns, including a major shift at 34 cm depth (ca. mid-nineteenth century). A finely laminated sequence, which may include annual varves, is present between 34 cm depth and the slump layer. Sediment characteristics of the sequence suggest increased seasonality of terrigenous versus biogenous sedimentation during the corresponding period. In addition to a mid-nineteenth century change and considerable multidecadal variability in TOC, there is a positive trend in the past 50 years. Mineralogical analyses from a Fourier Transformed Infrared Spectroscopy (FTIR) of the upper core covering the last 25 years, indicate higher concentrations of the mineral fraction (quartz, feldspar, kaolinite and illite) in layers including large El Niño events (1982-1983, 1986-1987 and 1997-1998), with the largest peak during the 1997-1998 episode. These results confirm that anoxic sediments off Pisco are suitable archives to investigate interannual and decadal changes in oceanographic conditions and climate of the northern Humboldt upwelling system.

Description: We report here on post-midnight uplifts near the magnetic equator. We present observational evidence from digital ionosondes in Brazil, a digisonde in Peru, and other measurements at the Jicamarca Radio Observatory that show that these uplifts occur fairly regularly in the post-midnight period, raising the ionosphere by tens of kilometers in the most mild events and by over a hundred kilometers in the most severe events. We show that in general the uplifts are not the result of a zonal electric field reversal, and demonstrate instead that the uplifts occur as the ionospheric response to a decreasing westward electric field in conjunction with sufficient recombination and plasma flux. The decreasing westward electric field may be caused by a change in the wind system related to the midnight pressure bulge, which is associated with the midnight temperature maximum. In order to agree with observations from Jicamarca and Palmas, Brazil, it is shown that there must exist sufficient horizontal plasma flux associated with the pressure bulge. In addition, we show that the uplifts may be correlated with a secondary maximum in the spread-F occurrence rate in the post-midnight period. The uplifts are strongly seasonally dependent, presumably according to the seasonal dependence of the midnight pressure bulge, which leads to the necessary small westward field in the post-midnight period during certain seasons. We also discuss the enhancement of the uplifts associated with increased geomagnetic activity, which may be related to disturbance dynamo winds. Finally, we show that it is possible using simple numerical techniques to estimate the horizontal plasma flux and the vertical drift velocity from electron density measurements in the post-midnight period.

Description: Experimental results from the Tromsø and Sura heating experiments at high and mid-latitudes are examined. It is shown that the combination of HF-induced target and bi-static HF Doppler radio scatter observations is a profitable method for probing medium-scale traveling ionospheric disturbances (TIDs) at high and mid-latitudes. HF ionospheric modification experiments provide a way of producing the HF-induced scatter target in a controlled manner at altitudes where the sensitivity to TIDs is highest. Bi-static HF Doppler radio scatter observations were carried out on the London-Tromsø-St. Petersburg path in the course of a Tromsø heating experiment on 16 November 2004 when the pump wave was reflected from an auroral Es-layer. During Sura heating experiments on 19 and 20 August 2004, when the HF pump wave was reflected from the F2 ionospheric layer, multi-position bi-static HF Doppler radio scatter observations were simultaneously performed at three reception points including St. Petersburg, Kharkov, and Rostov-on-Don. Ray tracing and Doppler shift simulations were made for all experiments. A computational technique has been developed allowing the reconstruction of the TID phase velocities from multi-position bi-static HF Doppler scatters. Parameters of medium-scale TIDs were found. In all experiments they were observed in the evening and pre-midnight hours. TIDs in the auroral E-region with periods of about 23 min were traveling southward at speeds of 210 m/s. TIDs in the mid-latitudinal F-region with periods from 20 to 45 min travelled at speeds between 40 and 150 m/s. During quiet magnetic conditions the waves were traveling in the north-east direction. In disturbed conditions the waves were moving in the south-west direction with higher speeds as compared with quiet conditions. Possible sources for the atmospheric gravity waves at middle and high latitudes are discussed.