Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

Estimated Variability of National Atmospheric Deposition Program/Mercury Deposition Network Measurements Using Collocated Samplers

The National Atmospheric Deposition Program/Mercury Deposition Network (MDN) provides long-term, quality-assured records of mercury in wet deposition in the USA and Canada. Interpretation of spatial and temporal trends in the MDN data requires quantification of the variability of the MDN measurements. Variability is quantified for MDN data from collocated samplers at MDN sites in two states, one in Illinois and one in Washington. Median absolute differences in the collocated sampler data for total mercury concentration are approximately 11% of the median mercury concentration for all valid 1999–2004 MDN data. Median absolute differences are between 3.0% and 14% of the median MDN value for collector catch (sample volume) and between 6.0% and 15% of the median MDN value for mercury wet deposition. The overall measurement errors are sufficiently low to resolve between NADP/MDN measurements by ±2 ng·l⁻¹ and ±2 μg·m⁻²·year⁻¹, which are the contour intervals used to display the data on NADP isopleths maps for concentration and deposition, respectively.     

Results of An Indoor Size Fractionated PM School Sampling Program in Libby, Montana

Libby, Montana is the only PM_2.5 nonattainment area in the western United States with the exceptions of parts of southern California. During January through March 2005, a particulate matter (PM) sampling program was conducted within Libby’s elementary and middle schools to establish baseline indoor PM concentrations before a wood stove change-out program is implemented over the next several years. As part of this program, indoor concentrations of PM mass, organic carbon (OC), and elemental carbon (EC) in five different size fractions (>2.5, 1.0–2.5, 0.5–1.0, 0.25–0.5, and <0.25 μm) were measured. Total measured PM mass concentrations were much higher inside the elementary school, with particle size fraction (>2.5, 0.5–1.0, 0.25–0.5, and <0.25 μm) concentrations between 2 and 5 times higher when compared to the middle school. The 1.0–2.5 μm fraction had the largest difference between the two sites, with elementary school concentrations nearly 10 times higher than the middle school values. The carbon component for the schools’ indoor PM was found to be predominantly composed of OC. Measured total OC and EC concentrations, as well as concentrations within individual size fractions, were an average of two to five times higher at the elementary school when compared to the middle school. For the ultrafine fraction (<0.25), EC concentrations were similar between each of the schools. Despite the differences in concentrations between the schools at the various fraction levels, the OC/EC ratio was determined to be similar.     

Removal of added nitrate in the single, binary, and ternary systems of cotton burr compost, zerovalent iron, and sediment: Implications for groundwater nitrate remediation using permeable reactive barriers

Recent research has shown that carbonaceous solid materials and zerovalent iron (Fe(0)) may potentially be used as media in permeable reactive barriers (PRBs) to degrade groundwater nitrate via heterotrophic denitrification in the solid carbon system, and via abiotic reduction and autotrophic denitrification in the Fe(0) system. Questions arise as whether the more expensive Fe(0) is more effective than the less expensive carbonaceous solid materials for groundwater nitrate remediation, and whether there is any synergistic effect of mixing the two different types of materials. We carried out batch tests to study the nature and rates of removal of added nitrate in the suspensions of single, binary, and ternary systems of cotton burr compost, Peerless Fe(0), and a sediment low in organic carbon. Cotton burr compost acted as both organic carbon source and supporting material for the growth of indigenous denitrifiers. Batch tests showed that cotton burr compost alone removed added nitrate at a greater rate than did Peerless Fe(0) alone on an equal mass basis with a pseudo-first-order rate constant k=0.0830+/-0.0031 h(-1) for cotton burr compost and a k=0.00223+/-0.00022 h(-1) for Peerless Fe(0); cotton burr compost also removed added nitrate at a faster rate than did cotton burr compost mixed with Peerless Fe(0) and/or the sediment. Furthermore, there was no substantial accumulation of ammonium ions in the cotton burr compost system, in contrast to the systems containing Peerless Fe(0) in which ammonium ions persisted as major products of nitrate reduction. It is concluded that cotton burr compost alone may be used as an excellent denitrification medium in a PRB for groundwater nitrate removal. Further study is needed to evaluate performance of its field applications.     

QSARs for the toxicity of polychlorinated dibenzofurans through DFT-calculated descriptors of polarizabilities, hyperpolarizabilities and hyper-order electric moments

DFT-B3LYP method with 6-31G(**) basis set was employed to fully optimize the electronic structures of 135 polychlorinated dibenzofurans and parent compound, namely dibenzofuran. It was demonstrated that polarizability anisotropy and mean polarizability could change sensitively and systematically with chlorine number and substitution pattern. And new quantitative structure-activity relationships (QSARs) focused on the binding affinities of aryl hydrocarbon receptor (AhR), aryl hydrocarbon hydroxylase (AHH) and 7-ethoxyresorufin O-deethylase (EROD) induction potencies of PCDFs were developed. It was concluded that polarizability anisotropy in conjunction with hyperpolarizabilties and hyper-order electric moments, e.g. octupole moments could well interpret the variation of toxicity of different congeners and dispersion interaction should be the leading form among various interactions. Although the terms of hyperpolarizabilities and hyper-order electric moments were not the same significant ones as polarizability anisotropy, the long-range interactions characterized by them should not be ignored in explaining the toxicity.     

Characterization of gas/particle concentrations and partitioning of polychlorinated biphenyls (PCBs) measured in an urban site of Turkey

Air concentrations of polychlorinated biphenyls (PCBs) in both gas and particle phases were measured in an urban site (BUTAL-Merinos) of the city of Bursa, Turkey between August 2004 and May 2005. The mean of total (particle+gas) PCB concentrations was about 491.8+/-189.4pg/m(3). The main contributors for PCBs in the sampling site were the local sources and long-range atmospheric transport supported by back trajectory analysis. Lower molecular weight PCB congeners generally dominated in the samples. The particle phase of the measured PCBs accounted for 15% of the total PCB concentrations. Gas/particle distribution was investigated using different approaches such as log K(P)-log P(L)(o), log K(P)-log K(OA) and the Junge-Pankow model. Regression analysis among log K(P), log P(L)(o) and log K(OA) exhibited significant correlation at p<0.05. Correlation between PCB homologs and meteorological parameters was formed to investigate the possible relationships.     

Differential responses of the freshwater wetland species Juncus effusus L. and Caltha palustris L. to iron supply in sulfidic environments

Sulfur pollution can lead to serious problems in freshwater wetlands, including phosphorus eutrophication and sulfide toxicity. We tested the effects of anaerobic iron-rich groundwater discharge in fens, simulated by iron injection, on two characteristic species (Juncus effusus and Caltha palustris) in a sulfidic environment. Biomass production of C. palustris roots showed an optimum response to the combined addition of iron and sulfide, with highest values at intermediate concentrations of both substances. Iron deficiency apparently occurred at low iron concentrations, while at high iron concentrations, growth was decreased. For J. effusus, in contrast, no toxic effects were found of both iron and sulfide. This could be explained by larger radial oxygen loss (ROL) of J. effusus and could not be explained by differences in phosphorous concentrations. The results of our experiments confirm that iron-rich groundwater discharge has the potential to affect vegetation composition through toxicity modification in sulfidic environments.     

Age and seasonal variability of polybrominated diphenyl ethers in free-ranging East Greenland polar bears (Ursus maritimus)

Polybrominated diphenyl ethers (PBDEs) were analysed in adipose tissue from 92 East Greenland polar bears (Ursus maritimus) sampled during 1999-2001. Mean SigmaPBDE concentrations were 70 ng/g lipid weight (lw) (range: 22-192 ng/g lw) and showed no relationship with age or sex. Of the 32 analysed PBDE congeners; BDE47, BDE153, BDE99 and BDE100 dominated, and comprised 99.6% of the SigmaPBDE concentration. The SigmaPBDE concentration had a highly significant correlation with SigmaPCB, SigmaCHL, dieldrin, HCB and SigmaHCH concentrations. We found a seasonal pattern of median SigmaPBDE concentration with 1.2 to 1.8 times higher concentrations in March to July than the rest of the year. The seasonal variation also provides a clue to the seasonal exposure, bio-availability, toxic exposure and degradation. We suggest that future geographical PBDE data comparisons may not need corrections for sex or age, but such data sets should be corrected for seasonal variability, using the presented correctional trigonometric regression.     

Comparative toxicity of chlorpyrifos, diazinon, malathion and their oxon derivatives to larval Rana boylii

Organophosphorus pesticides (OPs) are ubiquitous in the environment and are highly toxic to amphibians. They deactivate cholinesterase, resulting in neurological dysfunction. Most chemicals in this group require oxidative desulfuration to achieve their greatest cholinesterase-inhibiting potencies. Oxon derivatives are formed within liver cells but also by bacterial decay of parental pesticides. This study examines the toxicity of chlorpyrifos, malathion and diazinon and their oxons on the foothill yellow-legged frog (Rana boylii). R. boylii is exposed to agricultural pesticides in the California Central Valley. Median lethal concentrations of the parental forms during a 96 h exposure were 3.00 mg/L (24h) for chlorpyrifos, 2.14 mg/L for malathion and 7.49 mg/L for diazinon. Corresponding oxons were 10 to 100 times more toxic than their parental forms. We conclude that environmental concentrations of these pesticides can be harmful to R. boylii populations.     

Real time remote monitoring of air pollutants and their online transmission to the web using internet protocol

Recent advances in both information and sensor technologies have enabled the development of Real Time Remote Monitoring (RTRM) capabilities for environmental management. An online and real time remote monitoring system for air pollution has been designed and installed at a traffic police station at Punjagutta in Hyderabad, India. The system is optimized using electrochemical sensors and a real time particulate matter analyzer. The system also monitors meteorological parameters such as temperature, humidity, rainfall, barometric pressure, wind speed and wind direction. The system periodically monitors both pollution and meteorological parameters at pre- programmed intervals of hr during peak periods and 1 hr during non peak periods of the day and continuously uploads to a predestinated web site (www.appcb.org/home.htm) using File Transfer Protocol. The web site renders a quick, simple and graphical display of air pollution levels and meteorological parameters and their significance to humans. The present paper highlights design considerations of a pollution monitoring system, system hardware and software requirements and practical limitations and future directions for real time remote monitoring of air pollution.