Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Substance-related environmental monitoring

Background  Due to the requirements of the EU Water Framework Directive and other legal regulations (e.g., national laws like the German Federal Soil Protection Act), but also due to the implementation of the new EU chemicals management system REACH, environmental monitoring will gain increasing importance for the surveillance of environmental quality as well as for the assessment of chemicals. Against this background, the Work Group on ‘Environmental Monitoring’ of the Division of ‘Environmental Chemistry and Ecotoxicology’ within the German Chemical Society has compiled a position paper on substance-related environmental monitoring. Scope  Core elements of this position paper are the definitions of important terms like monitoring, exposure monitoring, effect monitoring, and integrated monitoring. Moreover, temporal and spatial aspects (monitoring of spatial distributions, trend monitoring, and retrospective monitoring) and their applications are discussed. The main focus of this position paper is the coverage of aspects which have to be observed for the preparation and implementation of a monitoring program. Essential is the clear specification of the targets of the monitoring which determine the development of the monitoring concept and its realization, e.g., if environmental media (compartments) or organisms are most appropriate as samples for the aim of the study. Of course, also the properties of the target substances are important (e.g., lipophilicity/bioaccumulation as pre-requisite for an exposure monitoring with organisms). Finally, the monitoring phases of sample planning, sampling, storage and transport of samples, selection of analytical methods, quality assurance measures as well as reporting are discussed. Perspectives  An important issue for the future is to link the quantification of chemicals in environmental compartments (exposure and pollution monitoring) more closely to the study of biological effects (effect monitoring) than has been the case up to now. Furthermore, by inclusion of a spatial differentiation, a comprehensive evaluation of the state of an ecosystem can be obtained and the relevance of the results improved. Practical examples of monitoring studies which illustrate various aspects covered in this position paper will be presented in a series of publications by members of the Work Group in the following issues of this journal.

Models at the interface between science and society: impacts and options

Within the CLEAR project a new approach to integrated assessment modelling has been developed for the participatory integrated assessment of regional climate change involving citizens' focus groups. The climate change decision problem was structured by focusing separately on climate impacts and mitigation options. The attempt was made to link the different scales of the problem from the individual to the global level. The abstract topic of climate change was related to options on the level of a citizen's individual lifestyle. The option of a low energy society was emphasised in order to embed the climate change decision problem in a wider range of societal concerns. Special emphasis was given to the characterisation and communication of uncertainties. The chosen approach allows different kinds of uncertainties in one framework to be addressed. The paper concludes with a summary of the experience made, and recommendations for the use of models in participatory integrated assessments. This revised version was published online in July 2006 with corrections to the Cover Date.     

Net methylmercury production as a basis for improved risk assessment of mercury-contaminated sediments

Sediments contaminated by various sources of mercury (Hg) were studied at 8 sites in Sweden covering wide ranges of climate, salinity, and sediment types. At all sites, biota (plankton, sediment living organisms, and fish) showed enhanced concentrations of Hg relative to corresponding organisms at nearby reference sites. The key process determining the risk at these sites is the net transformation of inorganic Hg to the highly toxic and bioavailable methylmercury (MeHg). Accordingly, Hg concentrations in Perca fluviatilis were more strongly correlated to MeHg (p < 0.05) than to inorganic Hg concentrations in the sediments. At all sites, except one, concentrations of inorganic Hg (2-55 microg g(-1)) in sediments were significantly, positively correlated to the concentration of MeHg (4-90 ng g(-1)). The MeHg/Hg ratio (which is assumed to reflect the net production of MeHg normalized to the Hg concentration) varied widely among sites. The highest MeHg/Hg ratios were encountered in loose-fiber sediments situated in southern freshwaters, and the lowest ratios were found in brackish-water sediments and firm, minerogenic sediments at the northernmost freshwater site. This pattern may be explained by an increased MeHg production by methylating bacteria with increasing temperature, availability of energy-rich organic matter (which is correlated with primary production), and availability of neutral Hg sulfides in the sediment pore waters. These factors therefore need to be considered when the risk associated with Hg-contaminated sediments is assessed.     

Bioconcentration, biomagnification and metabolism of 14C-terbutryn and 14C-benzo[a]pyrene in Gammarus fossarum and Asellus aquaticus

The contribution of bioconcentration and biomagnification of 14C-terbutryn and 14C-benzo[a]pyrene via food and water to the bioaccumulation in Gammarus fossarum and Asellus aquaticus was investigated in single species-tests. In this investigation the uptake of 14C-terbutryn and 14C-benzo[a]pyrene via food and water by G. fossarum (L.) and A. aquaticus (L.) was examined. Bioconcentration factors (BCFs) and biomagnification factors (BMFs) were determined. Calculated BCFs were clearly higher than BMFs, indicating that water is the primary route of uptake. The uptake of terbutryn and benzo[a]pyren via water in G. fossarum and A. aquaticus is faster than uptake via food. The elimination and metabolism of the two chemicals by G. fossarum and A. aquaticus were studied. Terbutryn was eliminated almost completely in both species. In general, the elimination of terbutryn from G. fossarum and A. aquaticus was fast with half-life of 5 h. The elimination of terbutryn by G. fossarum after biomagnification is slower than after bioconcentration. No difference was found in elimination of terbutryn by A. aquaticus after biomagnification and after bioconcentration. Metabolites of terbutryn in G. fossarum and A. aquaticus were analyzed by HPLC. After the bioconcentration experiment a higher percentage of metabolites was found in G. fossarum than in A. aquaticus. This was confirmed for the experiment with uptake via food. The spectrum of metabolites was similar in both species, with hydroxyterbutryn being the major metabolism product in water. 14C-B[a]P could nearly completely be eliminated by G. fossarum (rest of activity 2%) after uptake via water. 14C-B[a]P could not be eliminated by G. fossarum and A. aquaticus after uptake via food. The metabolite could not be identified.     

XAFS studies of cobalt(II) binding by solid peat and soil-derived humic acids and plant-derived humic acid-like substances

This work has examined cobalt(II) binding by a variety of solid humic acids (HAs) isolated from peat, plant and soil sources at temperatures down to 60K. The results confirm that X-ray absorption near-edge spectroscopy (XANES) measurements cannot distinguish between aquo and carboxylato ligands in the inner coordination sphere of Co(II). However, between 1 and 2 inner-sphere carboxylato ligands can be detected in all the peat, plant and soil-derived HA samples by extended X-ray absorption fine structure (EXAFS) measurements, indicating inner-sphere coordination of HA-bound Co(II). The precision of C(carboxylate) detection is limited by the extent and quality of the data and the contribution from inner-sphere O to the Fourier transformed peaks used to detect carbon. Putative chelate ring formation is consistent with a relatively negative entropy change in step A, the stronger Co(II) binding step by HA functional groups, and could relate to 'non-exchangeable' metal binding by HSs.     

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.     

The influence of EDDS and EDTA on the uptake of heavy metals of Cd and Cu from soil with tobacco Nicotiana tabacum

Phytoextraction, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. In order to enhance phytoextraction the use of chelating agents has been proposed. This study aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposed, as an alternative to ethylene diamine tetraacetate (EDTA). EDDS revealed a higher toxicity to tobacco (Nicotiana tabacum) in comparison to EDTA, but no toxicity to microorganisms. The uptake of Cu was increased by the addition of EDTA and EDDS, while no increase was observed in the uptake of Cd. Both chelating agents showed a very low root to shoot translocation capability and the translocation factor was lower than the one of the control. Heavy metals where significantly more phytoavailable than in the control, even after harvesting, resulting in a high heavy metal leaching possibility, probably owing to a low biodegradation rate of EDDS. New seedlings which were transplanted into the EDDS treated pots 7d after the phytoextraction experiment, showed signs of necrosis and chlorosis, which resulted in a significantly lower biomass in comparison to the control. The seedlings on the EDTA treated pots showed no toxicity signs. Contrary to previous opinions the results of this study revealed the chelating agents EDTA and EDDS as unsuitable for enhanced phytoextraction using tobacco.