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We studied the interaction between toxic stress and accumulation in the earthworm Aporrectodea caliginosa, as induced by different soil copper pools and soil constituents (especially pH). Earthworms were exposed in quartz sand, spiked soils, and field soils with different Cu concentrations and varying soil composition. The copper content in the earthworms was determined in the following: the cytosolic fraction, a granular fraction and a fraction consisting of tissue fragments, cell membranes and intact cells. The highest amount of Cu was found in the cytosolic fraction. The other fractions varied only slightly in response to changes in any of the copper pools in soil. Cytosolic copper was the best predictor of Cu availability to earthworms collected from soils at constant pH, as statistically significant correlations were obtained with pore water pCu at constant pH in earthworms exposed in quartz sand. This correlation was lost for cytosolic Cu concentrations in earthworms exposed to spiked soils and field soils at differing pHs. Instead, cytosolic copper correlated well to Cu in either pore water or solid phase. Soil pH not only plays an important role in the availability of metals and therefore on their uptake fluxes, but internal competition of Cu2+ and H+ at physiologically active binding sites also explained these apparent contradictions and increased the predictability of body burdens significantly. [ABSTRACT FROM AUTHOR]

The volatilization of pesticides from crop canopies in the field should be modeled within the context of evaluating environmental exposure. A model concept based on diffusion through a laminar air-boundary layer was incorporated into the PEARL model (pesticide emission assessment at regional and local scales) and used to simulate volatilization of the pesticides parathion and chlorothalonil from a potato crop in a field experiment. Rate coefficients for the competing processes of plant penetration, wash off, and phototransformation in the canopy had to be derived from a diversity of literature data. Cumulative volatilization of the moderately volatile parathion (31% of the dosage in 7.6 days) could be simulated after calibrating two input data derived for the related compound parathion-methyl. The less volatile and more slowly transformed chlorothalonil showed 5% volatilization in 7.6 days, which could be explained by the simulation. Simulated behavior of the pesticides in the crop canopy roughly corresponded to published data. [ABSTRACT FROM AUTHOR]

The extent of bioaccumulation of the syn- and anti-isomers of Dechlorane Plus (DP) is assessed in archived food web samples from Lake Winnipeg and Lake Ontario. Concentrations of the isomers were determined using purified analytical solutions of individual isomers as opposed to the technical mixture. The syn-isomer was consistently detected in all samples from both lakes; the anti-isomer was detected in all Lake Ontario samples, but only 45% of the samples from Lake Winnipeg. The pattern of bioaccumulation was different for the isomers in Lake Winnipeg. The anti-isomer was dominant in higher trophic level (TL) organisms like walleye [arithmetic mean ±1 × standard error: 730 ± 120 pg/g, lipid weight (lw)] and gold eye (760 ± 170 pg/g, lw) while the syn-isomer dominated the lower TL organisms like zooplankton (550 ± 40 pg/g, lw) and mussels (430 ± 140 pg/g, lw). In Lake Ontario, the extent of bioaccumulation of the isomers and concentrations was greatest in the lower TL benthic organism, Diporeia (syn, 1307 ± 554; and anti, 3108 ± 898 pg/g lw) and also high in zooplankton (syn, 719; and anti, 1332 pg/g lw). This suggests that the isomers are bioavailable in sediment and that, despite their molecular size, diffusion from the water column into zooplankton can occur. Differences in the mean fractional abundance of the anti-isomer (mean fanti = mean concentration of the anti-isomer divided by sum of mean syn- and anti-concentrations) were pronounced in sediments between lakes (Lake Winnipeg mean fanti = 0.610, Lake Ontario mean fanti = 0.860) and the extent of enrichment (anti-) and depletion (syn-) of the isomers were more marked in Lake Winnipeg biota. There were also differences in the biomagnification potentials, as measured by the trophic magnification factor (TMF), between the isomers in the Lake Winnipeg food web; no statistically significant TMFs for either isomer were found for the Lake Ontario food web. A TMF of 2.5 (r² = 0.12, p = 0.04) for the anti isomer and <1 (r² = 0.17, p = 0.01) for the syn isomer suggests that differences in bioaccumulation in the Lake Winnipeg food web are not driven solely by configuration of the pendent chlorocyclopentene moieties. [ABSTRACT FROM AUTHOR]

We measured the concentrations of 11 polyfluoroalkyl compounds (PFCs), including perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) in 1562 serum samples collected from a representative U.S. population 12 years of age and older in the 1999–2000 National Health and Nutrition Examination Survey. Participants represented both sexes, three race/ethnicities (non-Hispanic blacks, non-Hispanic whites, and Mexican-Americans), and four age categories (12–19 years, 20–39 years, 40–59 years, and 60 years and older). PFCs were extracted from 100 μL of serum using on-line solid-phase extraction coupled to isotope dilution-high performance liquid chromatography-tandem mass spectrometry; limits of detection ranged from 0.05 to 0.2 ng/mL. PFOS, PFOA, PFHxS, and perfluorooctane sulfonamide were detected in all samples analyzed; 2-(N-ethyl-perfluorooctane sulfonamido) acetic acid, 2-(N-methyl-perfluorooctane sulfonamido) acetic acid, and perfluorononanoic acid were detected in more than 90% of samples, which suggests prevalent exposures to several PFCs in the U.S. population. The concentrations of most PFCs were similar regardless of the participants' ages but were higher in males than in females. Mexican Americans had lower concentrations than non-Hispanic blacks and non-Hispanic whites, whose concentrations were similar. Higher education was associated with higher concentrations of PFOS and PFOA. These data will serve as a nationally representative baseline of the U.S. population's exposure to PFCs to which other populations can be compared, and will play an important role in public health by helping set research priorities, ranging from health effects studies to defining sources and pathways of exposure. [ABSTRACT FROM AUTHOR]

The release of particulate-phase trace metals due to sediment resuspension has been investigated by combining erosion chamber experiments that apply a range of shear stresses typically encountered in coastal environments with a shear stress record simulated by a hydrodynamic model. Two sites with contrasting sediment chemistry were investigated. Sediment particles enriched in silver, copper, and lead, 4–50 times greater than the bulk surface-sediment content, were the first particles to be eroded. As the shear-stress level was increased in the chamber, the total mass eroded increased, but the enrichment of these trace metals fell, approaching the bulk-sediment content. From the temporal distribution of shear stress generated by the hydrodynamic model for a site in Boston Harbor, resuspension fluxes were estimated. The erosion threshold of this site is exceeded during spring tides, releasing the particles enriched in trace metals into the water column. Due to the higher trace metal content and the regularity of resuspension, low-energy resuspension events (up to a shear stress of 0.2 N/m²) contribute up to 60% of the resuspension metal flux in an average year. The estimated annual quantity of copper and lead resuspended into the water column is higher than estimates of the total riverine flux for these metals. These results indicate that sediment resuspension is a very important mechanism for releasing metals into the water column and provide new insight into the chemical and physical processes controlling the long-term fate of trace metals in contaminated sediments. [ABSTRACT FROM AUTHOR]

Copper is mobilized in soil by dissolved organic matter (DOM) but the role of DOM quality in this process is unclear. A one-step resin-exchange method was developed to measure the Cu-Mobilizing-Potential (CuMP) of DOM at pCu 11.3 and pH 7.0, representing background values. The CuMP of DOM was measured in soil solutions of 13 uncontaminated soils with different DOM extraction methods. The CuMP, expressed per unit dissolved organic carbon (DOC), varied 10-fold and followed the order water extracts > 0.01 M CaCl2 extracts > pore water. Soil solutions, obtained from soils that were stored air-dry for a long time or were subjected to drying-wetting cycles, had elevated DOC concentration, but the DOM had a low CuMP. Prolonged soil incubations decreased the DOC concentration and increased the CuMP, suggesting that most of the initially elevated DOM is less humified and has lower Cu affinity than DOM remaining after incubation. A significant positive correlation between the specific UV-absorption of DOM (indicating aromaticity) and CuMP was found for all DOM samples (R² = 0.58). It is concluded that the DOC concentration in soil is an insufficient predictor for the Cu mobilization and that DOM samples isolated from air-dried soils are distinct from those of soils kept moist. [ABSTRACT FROM AUTHOR]

Low-cost, practicable techniques are required to limit the release of volatile organic compound-containing fumigants such as 1,3-D to the atmosphere. In this study, we aimed to quantify 1,3-D diffusion and emission from laboratory soil columns maintained under realistic conditions and thereby assess the efficacy of soil irrigation as a technique for reducing emissions. In two soils (one relatively high, and one relatively low, in organic matter), irrigation led to a limiting of upward diffusion of the fumigant and to the maintenance of higher soil gas concentrations. Therefore, rather than being emitted from the column, the 1,3-D was maintained in the soil where it was ultimately degraded. As a consequence, emission of 1,3-D from the irrigated columns was around half of that from the nonirrigated columns. It is concluded that surface irrigation represents an effective, low-cost, and readily practicable approach to lessening the environmental impact of 1,3-D fumigant use. In addition, the higher organic matter soil exhibited emissions of around one-fifth of the lower organic matter soil in both irrigated and nonirrigated treatments, due to markedly enhanced degradation of the fumigant. Organic matter amendment of soils may, therefore, also represent an extremely effective, relatively low-cost approach to reducing 1,3-D emissions. [ABSTRACT FROM AUTHOR]

This study presents the number, surface and volume concentrations, and size distribution of particles next to the 1-710 freeway during February through April 2006. 1-710 has the highest ratio (up to 25%) of heavy-duty diesel vehicles in the Los Angeles highway network. Particle concentration measurements were accompanied by measurements of black carbon, elemental and organic carbon, and gaseous species (CO, CO2). Using the incremental increase of CO2 over the background to calculate the dilution ratio, this study makes it possible to compare particle concentrations measured next to the freeway to concentrations measured in roadway tunnels and in vehicle exhaust. In addition to the effect of the dilution ratio on the measured particle concentrations, multivariate linear regressions showed that light and heavy organic carbon concentrations are positively correlated with the particle volume in the nucleation and accumulation modes, respectively. Solar radiation was also positively correlated with the particle surface concentration and the particle volume in the accumulation (40–638 nm) mode, presumably as a result of secondary particle formation. The methods developed in this study may be used to decouple the effect of sampling position, meteorology, and fleet operation on particle concentrations in the proximity of freeways, roadway tunnels, and in street canyons. [ABSTRACT FROM AUTHOR]

Bioaccumulation of synthetic musks in a marine food chain was investigated by analyzing marine organisms at various trophic levels, including lugworm, clam, crustacean, fish, marine mammal, and bird samples collected from tidal flat and shallow water areas of the Ariake Sea, Japan. Two of the polycyclic musks, HHCB and AHTN, were the dominant compounds found in most of the samples analyzed, whereas nitro musks were not detected in any of the organisms, suggesting greater usage of polycyclic musks relative to the nitro musks in Japan. The highest concentrations of HHCB were detected in clams (258–2730 ng/g lipid wt.), whereas HHCB concentrations in mallard and black-headed gull were low, and comparable with concentrations in fish and crab. These results are in contrast to the bioaccumulation pattern of polychlorinated biphenyls; for which a positive correlation between the concentration and the trophic status of organisms was found. Such a difference in the bioaccumulation is probably due to the metabolism and elimination of HHCB in higher trophic organisms. Temporal trends in concentrations of synthetic musks were examined by analyzing tissues of marine mammals from Japanese coastal waters collected during 1977–2005. HHCB concentrations in marine mammals have shown significant increase since the early 1990s, suggesting a continuous input of this compound into the marine environment. Comparison of the time trend for HHCB with those for PCBs and PBDEs suggested that the rates of increase in HHCB concentrations were higher than the other classes of pollutants. To examine the geographical distribution of HHCB, we have analyzed tissues offish, marine mammals, and birds collected from several locations. Synthetic musks were not detected in a sperm whale (pelagic species) from Japanese coastal water and in eggs of south polar skua from Antarctica. While the number of samples analyzed is limited, these results imply a lack of long-range transportation potential of synthetic musks in the environment. [ABSTRACT FROM AUTHOR]

The reaction of polycyclic aromatic hydrocarbons (PAHs) previously adsorbed on silica gel or diatomaceous earth with sodium hypochlorite was carried out to elucidate their reactivity to aqueous chlorine. It was demonstrated that the PAHs adsorbed on silica reacted more rapidly than the PAHs themselves in water, leading to the formation of many chlorinated and oxidized derivatives. A similar reaction in the presence of potassium bromide was found to preferentially produce corresponding brominated derivatives. These reactions seem to proceed through PAHs adsorbed on the silica surface and halogenating agents, the electrophilicity of which may be raised by the catalytic effect of the silanol group of the silica surface. These findings from the environmental viewpoint suggest that the reaction of hydrophobic compounds adsorbed on sediment cannot be neglected. [ABSTRACT FROM AUTHOR]

The Duluth Boat Club (DBC) Beach, located in the Duluth-Superior harbor of Lake Superior, is frequently closed in summer due to high counts of Escherichia coli, an indicator of fecal contamination. However, the sources of bacteria contributing to beach closure are currently unknown. In this study, we investigated the potential sources of E. coli contaminating the DBC beach by using modified rep-PCR (HFERP) DNA fingerprinting. Over 3600 E. coli strains were obtained from 55 lake water, 25 sediment, and 135 sand samples taken from five transects at the DBC beach at 11 different times during the summer through fall months of 2004 and 2005. Potential sources of E. coli at this beach were determined by using a known-source DNA fingerprint library containing unique E. coli isolates from wildlife, waterfowl, and treated wastewater obtained near Duluth, MN. Amounts E. coli in the samples were enumerated by membrane filtration counting, and the presence of potentially pathogenic E. coli was determined by using multiplex PCR. E. coli counts in all samples increased during the summer and early fall (July to September). While E. coli in spring samples originated mainly from treated wastewater effluent, the percentage of E. coli from waterfowl increased from summer to fall. DNA fingerprint analyses indicated that some E. coli strains may be naturalized, and autochthonous members of the microbial community in the beach sand and sediments were examined. However, multiplex PCR results indicated that <1% of the E. coli strains at the DBC was potentially pathogenic. Our results also suggest that wave action may influence the early colonization and homogeneous distribution of E. coli in beach sand and the subsequent release of sand or sediment-borne E. coli into lake water. Taken together, these results indicate that sand and sediment serve as temporal sources and sinks of human and waterfowl-derived E. coli that contribute to beach closures. [ABSTRACT FROM AUTHOR]

A first case of temperature-dependent distribution of polybromodiphenyl ethers (PBDEs) in remote areas is shown. Analysis of these compounds in fish from Pyrenean lakes distributed along an altitudinal transect shows higher concentrations at lower temperatures, as predicted in the global distillation model. Conversely, no temperature-dependent distribution is observed in a similar transect in the Tatra mountains (Central Europe) nor in fish from high mountain lakes distributed throughout Europe. The fish concentrations of polychlorobiphenyls (PCBs) examined for comparison showed significant temperature correlations in all these studied lakes. Cold trapping of both PCBs and PBDEs concerned the less volatile congeners. In the Pyrenean lake transect the concentrations of PCBs and PBDEs in fish were correlated despite the distinct use of these compounds and their 40 year time lag of emissions to the environment. Thus, temperature effects have overcome these anthropogenic differences constituting at present the main process determining their distributions. These cases of distinct PBDEs and PCBs behavior in high mountains likely reflect early stages in the environmental distribution of the former since they have been under secondary redistribution processes over much shorter time than the latter. [ABSTRACT FROM AUTHOR]

Passive air samplers (polyurethane foam disks) were deployed at 23 background locations along a broadly west-east transect in 8 northern European countries and analyzed for PCBs, PBDEs, PAHs, and a range of organochlorine pesticides (HCB, DDTs, and DDEs). PCBs and PAHs were highest at the center of the transect (Denmark) and lowest in northern Norway. HCB was relatively uniformly distributed, reflecting its persistence and high degree of mixing in air. Higher DDE and DDT levels occurred in Eastern Europe and at several sites in Central Europe. PBDE levels were generally similar at all sites, but lower for some locations in Eastern Europe and Ireland. Emissions information for PCBs, HCB, and PBDEs was used as input for a multi-media chemical fate model, to generate predicted air concentrations and compare with these measured values. Different scenarios were highlighted by this exercise: (i) country and compound combinations where the national inventory gave predicted air concentrations in close agreement with those measured (e.g., PCBs in the UK); (E) country and compound combinations where predicted concentrations were well below those measured, but where advection of emissions from elsewhere is likely to be important (e.g., PCBs in Norway); (iii) consistent underestimation of compound concentrations by the emissions modeling (i.e., HCB); and (iv) general overestimation of ambient concentrations (i.e., PBDEs). Air mass trajectory analysis showed the likely role of long-range atmospheric transport (LRAT) on national levels. In general, advection from the south and west of Europe appeared to contribute to ambient POPs levels for countries in the center and northeast of the transect. Guidelines are presented as to how countries that want to assess their POPs source inventories can do so with this relatively cheap initial screening approach. [ABSTRACT FROM AUTHOR]

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in preserved paddy soils periodically collected from 7 sites around Japan since 1960 to trace the changes in concentrations, to elucidate their sources, and to estimate their mass balance in Japanese paddy fields. Concentrations of ΣPCDD/Fs in paddy soils from all sites increased during the 1960s and the 1970s, then decreased. The results of principal component analysis and chemical mass balance based on functional relationship analysis indicate that the increase in ΣPCDD/F concentrations in paddy soils was due to the increased use of pentachlorophenol (PCP) and chlornitrofen (CNP); more than 95% of PCDD/Fs in all paddy soils were derived from impurities in these herbicides. The half-lives of PCDD/F for disappearance from the paddy soils were estimated to be 10 to 20 years (mean: 17.3 years). The estimated PCDD/F mass balance using the above half-life during the past 40 years in paddy fields indicates that about 80% of PCDD/Fs have disappeared. The soil puddling (mechanically mixing of paddy soil with pooled irrigation water) is implied as one reason for the PCDD/F disappearance from paddy fields. However, as the amounts of PCDD/Fs added through the use of PCP and CNP were extremely large, PCDD/F concentrations in Japanese paddy soils will decrease gradually, and PCDD/F runoff from paddy fields to surrounding catchments will continue. [ABSTRACT FROM AUTHOR]

We report the largest market basket survey of arsenic (As) in U.S. rice to date. Our findings show differences in transitional-metal levels between polished and unpolished rice and geographical variation in As and selenium (Se) between rice processed in California and the South Central U.S. The mean and median As grain levels for the South Central U.S. were 0.30 and 0.27 μg As g-1, respectively, for 107 samples. Levels for California were 41% lower than the South Central U.S., with a mean of 0.17 μg As g-1 and a median of 0.16 μg As g-1 for 27 samples. The mean and median Se grain levels for the South Central U.S. were 0.19 μg Se g-1. Californian rice levels were lower, averaging only 0.08 and 0.06 μg Se g-1 for mean and median values, respectively. The difference between the two regions was found to be significant for As and Se (General Linear Model (GLM): As p < 0.001; Se p < 0.001). No statistically significant differences were observed in As or Se levels between polished and unpolished rice (GLM: As p = 0.213; Se p = 0.113). No significant differences in grain levels of manganese (Mn), cobalt (Co), copper (Cu), or zinc (Zn) were observed between California and the South Central U.S. Modeling arsenic intake for the U.S. population based on this survey shows that for certain groups (namely Hispanics, Asians, sufferers of Celiac disease, and infants) dietary exposure to inorganic As from elevated levels in rice potentially exceeds the maximum intake of As from drinking water (based on consumption of 1 L of 0.01 mg L-1 ln. As) and Californian state exposure limits. Further studies on the transformation of As in soil, grain As bioavailability in the human gastrointestinal tract, and grain elemental speciation trends are critical. [ABSTRACT FROM AUTHOR]

From May to September 2005, five passive air samples were deployed over five, 1-month periods at five elevations on the CN Tower in Toronto, Canada, to investigate the vertical distribution, seasonality, and sources of organochlorine pesticides. A strong seasonality was observed between spring and the end of summer. Vertical profiles differed for different pesticide classes. For instance, α- and γ-hexachlorocyclohexane exhibited higher concentrations (60°80 pg m-3, respectively) near the ground during the spring and early summer, suggesting that surface-air exchange within the city or nearby Lake Ontario may be important sources. The vertical profile for chlordane isomers was variable, suggesting that both advective and local inputs are important. For dieldrin, no obvious trend with elevation was observed, suggesting that concentrations could reflect a regional air mass contamination. Strongest seasonality was observed for the endosulfans, a widely used pesticide in North America, that reached peak concentrations of 750–850 pg m-3 during June/July. Advective inputs of endosulfan from regional or more distant agricultural regions can explain the relatively uniform concentrations with elevation throughout the study period. The approach used in this study demonstrates that monthly average vertical concentration profiles differ between pesticide groups and reflect their use as well as the relative magnitude of input from local versus regional sources. [ABSTRACT FROM AUTHOR]

We simulate and analyze long-term dynamics of coastal nitrogen (N) loading and the inland source changes and processes that may have determined its development over the past 60-year period and may govern its possible future responses to various N source management scenarios. With regard to processes, the results show that average basin-scale N delivery fractions to the coast may not be representative of the coastal impacts of either diffuse or point inland sources. The effects of inland source changes may be greatly redistributed in space-time and delayed by slow N transport and mass transfer processes in the subsurface water system of coastal catchments. Extrapolation of current N transport-attenuation conditions for quantification of future abatement effects may therefore be misleading if the extrapolation models do not realistically represent delayed long-term influences of slow subsurface processes. With regard to policy, the results show that and why national Swedish and international Baltic Sea region policies for coastal N load abatement may be difficult or impossible to achieve by inland source abatement only. Large mitigation of both point and diffuse sources may be necessary to achieve targeted coastal N load reductions fast and maintain them also in the long term. [ABSTRACT FROM AUTHOR]

The atmospheric histories of two potent greenhouse gases, tetrafluoromethane (CF4) and hexafluoroethane (C2F6), have been reconstructed for the 20th century based on firn air measurements from both hemispheres. The reconstructed atmospheric trends show that the mixing ratios of both CF4 and C2F6 have increased during the 20th century by factors of ∼2 and ∼10, respectively. Initially, the increasing mixing ratios coincided with the rise in primary aluminum production. However, a slower atmospheric growth rate for CF4 appears to be evident during the 1990s, which supports recent aluminum industry reports of reduced CF4 emissions. This work illustrates the changing relationship between CF4 and C2F6 that is likely to be largely the result of both reduced emissions from the aluminum industry and faster growing emissions of C2F6 from the semiconductor industry. Measurements of C2F6 in the older firn air indicate a natural background mixing ratio of <0.3 parts per trillion (ppt), demonstrating that natural sources of this gas are negligible. However, CF4 was deduced to have a preindustrial mixing ratio of 34 ± 1 ppt (∼50% of contemporary levels). This is in good agreement with the previous work of Harnisch et al. (18) and provides independent confirmation of their results. As a result of the large global warming potentials of CF4 and C2F6, these results have important implications for radiative forcing calculations. The radiative forcings of CF4 and C2F6 are shown to have increased over the past 50 years to values in 2001 of 4.1 × 10-3 Wm-2 and 7.5 × 10-4 Wm-2, respectively, relative to preindustrial concentrations. These forcings are small compared to present day forcings due to the major greenhouse gases but, if the current trends continue, they will continue to increase since both gases have essentially infinite lifetimes. There is, therefore, a large incentive to reduce perfluorocarbon emissions such that, through the implementation of the Kyoto Protocol, the atmospheric growth rates may decline in the future. [ABSTRACT FROM AUTHOR]

This article discusses on the environmental performance of the Czech Republic. According to a 2006 report from the Yale Center for Environmental Law and Policy, the Czech Republic ranks 4th among 133 countries in terms of its environmental performance. The report was presented at the World Economic Forum in Davos, Switzerland on February 2006. Moreover, the report establishes a new Environmental Performance Index and has triggered a serious discussion of environmental quality in the Czech Republic.

The author argues that the expansion of the European Union (EU) will have major impact on it environment policy. The new member have no tradition of environment management and could exert a downward pull on existing member states. All the new member states have submitted step-by-step implementation plans and have to report on their progress to the European Commission. In the meantime, the EU has agreed to let all the new states transition to the tougher laws, mainly for regulation of water, waste, and industrial pollution.