Environmental Pollution

In the winter of 1982-83 an experiment was initiated at the University of Hohenheim to investigate the long-term effects of near ambient concentrations of O(3), SO(2), and simulated acidic rain and fog, alone and in combination, on mineral cycling, physiology, biochemistry and anatomy of Norway spruce (Picea abies L. Karst.), Silver fir (Abies alba Mill.) and European beech (Fagus silvatica L.) seedlings in model ecosystems. Open-top chambers above soil lysimeters were protected with shelters 1 m above the open-top against intrusion of ambient dust and rain. The soil, a replaced acid brown earth with a base saturation of 20-30% was from the Black Forest region of the Federal Republic of Germany. This paper describes the technical design aspects of the study, including chamber construction and ventilation, SO(2) and O(3) application and monitoring, simulated precipitation forms and dispensing features, and the environmental parameters monitored. A short description of the plants used and the soil status is also presented. Chamber climatic and edaphic conditions allowed tree seedling normal growth over the five years of study. The pollutant levels within the appropriate chambers were comparable to ambient concentrations found at southwest German forest sites and varied with weather conditions.

The authors used a global High Resolution Biosphere Model (HRBM), consisting of a biome model and a carbon cycle model, to estimate the changes of carbon storage in the major pools of the terrestrial biosphere from 18 000 BP to present. The climate change data to drive the biosphere for 18 000 BP were derived from an Atmospheric General Circulation Model. Using the AGCM anomalies interpolated to a 0.5 degrees grid, the HRBM data base of the present climate was recalculated for 18 000 BP. The most important processes which influenced the carbon storage include (1) climate-induced changes in biospheric processes and vegetation distribution, (2) the CO(2) fertilization effect, (3) the inundation of lowland areas resulting from the sea level rise of 100 m. Two scenarios were investigated. The first scenario, which ignored the CO(2) fertilization effect, led to total carbon losses from the terrestrial biosphere of -460 x 10(9) t. Scenario 2, which assumed that the model formulation of the CO(2) fertilization effect as used for preindustrial to present could be extrapolated to the glacial 200 microl litre(-1) (ppmv, parts per million per volume), gave a carbon fixation in the terrestrial biosphere of +213 x 10(9) t. The two scenarios were compared with CO(2) concentration data and isotopic ratios from air in ice cores. The results of Scenario 1 are not in agreement with the data. Scenario 2 gives realistic delta(13)C shifts in the atmosphere but the biospheric carbon storage at the end of the glacial period seems too large. The authors suggest that the low atmospheric CO(2) concentration may have favoured the C-4 plants in ice age vegetation types. As a consequence the influence of the low CO(2) concentration was eventually reduced and the glacial carbon storage in vegetation, litter, and soil was increased.

The impact of interactions between the earthworms Eisenia foetida and Lumbricus terrestris and the plants Cucurbita pepo and Cucurbita maxima on the uptake of weathered p,p'-DDE from soil was determined. Although some combinations of earthworm and plant species caused significant changes in the p,p'-DDE burden in both organisms, the effects were species specific. Contaminant bioconcentration in C. pepo was increased slightly by E. foetida and by 3-fold when the plant was grown with L. terrestris. E. foetida had no effect on the contaminant BCF by C. maxima, but L. terrestris caused a 2-fold reduction in p,p'-DDE uptake by the plant. Contaminant levels in E. foetida and L. terrestris were unaffected by C. pepo. When grown with C. maxima, the concentration of p,p'-DDE decreased by approximately 4-fold and 7-fold in E. foetida and L. terrestris, respectively. The data suggest that the prediction of contaminant bioavailability should consider interactions among species.

Polyhalogenated 1,1'-dimethyl-2,2'-bipyrroles (PDBPs) are halogenated natural products (HNPs) previously shown to bioaccumulate in marine mammals and birds. Since their discovery in 1999, six hexahalogenated and a few lesser halogenated congeners have been identified in diverse marine mammal samples. Here we report the identification of 17 additional hexahalogenated PDBPs in the blubber extract of a humpback dolphin (Sousa chinensis) from Queensland, Australia. Thirteen of these new PDBPs were also detected in an Australian sea cucumber (Holothuria sp.). Additional samples were also tested positive on several new PDBPs, including an Australian venus tuskfish (Choerodon venustus) as well as a white whale (Delphinapterus leucas) and a sperm whale (Physeter macrocephalus) from the Northern Hemisphere. GC/ECNI-MS-SIM quantification of the molecular ions was carried out with the help of synthesized standards. The sum concentration of PDBPs was 1.1 mg/kg lipid in the humpback dolphin and 0.48 mg/kg lipid in the sea cucumber.

Short-term (24h) exposure experiments have been conducted to determine the effects of two environmental relevant polycyclic aromatic hydrocarbons (PAHs), naphthalene (NAPH) and dimethylnaphthalene (C2-NAPH), on the naupliar and adult stages of the marine cyclopoid copepod Oithona davisae. To resemble more realistic conditions, those exposure experiments were conducted under the presence of food. The naupliar stages evidenced lower tolerance to PAH exposure regarding narcotic and lethal effects than adults. Copepod feeding activity showed to be very sensitive to the presence of the studied PAHs, detrimental effects occurring at toxic concentrations ca. 2-3 fold lower than for narcotic effects. In addition we report PAH-mediated changes in cell size and growth rate of the prey item, the heterotrophic dinoflagellate Oxyrrhis marina, that could indirectly affect copepod feeding and help explain hormesis-like responses in our feeding experiments.

In this study, the effectiveness of bioremediating 1,2-dichloroethane (DCA)-contaminated groundwater under different oxidation-reduction processes was evaluated. Microcosms were constructed using indigenous bacteria and activated sludge as the inocula and cane molasses and a slow polycolloid-releasing substrate (SPRS) as the primary substrates. Complete DCA removal was obtained within 30 days under aerobic and reductive dechlorinating conditions. In anaerobic microcosms with sludge and substrate addition, chloroethane, vinyl chloride, and ethene were produced. The microbial communities and DCA-degrading bacteria in microcosms were characterized by 16S rRNA-based denatured-gradient-gel electrophoresis profiling and nucleotide sequence analyses. Real-time polymerase chain reaction was applied to evaluate the variations in Dehalococcoides spp. and Desulfitobacterium spp. Increase in Desulfitobacterium spp. indicates that the growth of Desulfitobacterium might be induced by DCA. Results indicate that DCA could be used as the primary substrate under aerobic conditions. The increased ethene concentrations imply that dihaloelimination was the dominate mechanism for DCA biodegradation. Copyright © 2015 Elsevier Ltd. All rights reserved.

In laboratory experiments the mineralisation of 14C-labelled 1,2,4-trichlorobenzene (1,2,4-TCB) in soils was studied by direct measurement of the evolved 14CO2. The degradation capacity of the indigenous microbial population was investigated in an agricultural soil and in a soil from a contaminated site. Very low mineralisation of 1% within 23 days was measured in the agricultural soil. Whereas in the soil from the contaminated site the mineralisation occurred very fast and in high rates; up to 62% of the initially applied amount of 1,2,4-TCB were mineralised within 23 days. The transfer of the adapted microbial population into the agricultural soil significantly enhanced the mineralisation of 1,2,4-TCB in this soil, reflecting, that the transferred microbial population survived and maintained its degradation ability in the new microbial ecosystem. Additional nutrition sources ((NH4)2HPO4) increased the mineralisation rates in the first days significantly in the contaminated soil. In the soil from the contaminated site high amounts of non extractable 14C-residues were formed.

Phosphor imager autoradiography is a technique for rapid, sensitive analysis of the localization of xenobiotics in plant tissues. Use of this technique is relatively new to research in the field of plant science, and the potential for enhancing visualization and understanding of plant uptake and transport of xenobiotics remains largely untapped. Phosphor imager autoradiography is used to investigate the uptake and translocation of the explosives 1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene within Populus deltoides x nigra DN34 (poplar) and Panicum vigratum Alamo (switchgrass). In both plant types, TNT and/or TNT-metabolites remain predominantly in root tissues while RDX and/or RDX-metabolites are readily translocated to leaf tissues. Phosphor imager autoradiography is further investigated for use in semi-quantitative analysis of uptake of TNT by switchgrass.

Soil and topical tests were employed to investigate the effect of two N-nitroso metabolites of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) on earthworm reproduction. The lowest observed effect concentration (LOEC) for cocoon production and hatching was 50mg/kg for both hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX) in soil. MNX and TNX also significantly affected cocoon hatching in soil (p<0.001) and in topical tests (p=0.001). The LOECs for cocoon hatching were 1 and 10mg/kg for MNX and TNX in soil, respectively, and 10mg/L in the topical test. Greater than 100mg/kg MNX and TNX completely inhibited cocoon hatching. In soil, the EC20 values for MNX were 8.7 and 8.8mg/kg for cocoon and juvenile production, respectively, compared to 9.2 and 9.1mg/kg for TNX, respectively. The EC20 values for the total number of cocoon hatchlings were 3.1 and 4.7mg/kg for MNX and TNX, respectively, in soil and 4.5 and 3.1mg/L in the topical test. Both MNX and TNX inhibited cocoon production and hatching, suggesting that they may have a negative affect on soil ecosystems at contaminated sites.

To help elucidate the mechanism of dechlorination of chlorinated triazines via metallic iron, terbutylazine (TBA: 2-chloro-4-ethylamino-6-terbutylamino-1,3,5-triazine), deisopropyl atrazine (DIA: 2-amino-4-chloro-6-ethylamino-1,3,5-triazine), and chlorinated dimethoxy triazine (CDMT: 2-chloro-4,6-dimethoxy-1,3,5-triazine) were degraded via zero valent iron under controlled pH conditions. The lower the solution pH the faster the degradation, with surface area normalized pseudo first order rate constants ranging from 2 (+/- 1)x10(-3) min(-1) m(-2) l for TBA at pH 2.0 to 4 (+/- 2)x10(-5) min(-1) m(-2) l for CDMT at pH 4.0. Hydrogenolysis (dechlorinated) products were observed for TBA and CDMT. Electrochemical reduction on mercury showed similar behavior for all of the triazines studied; the initial product of CDMT bulk electrolysis was the dechlorinated compound. The iron results are consistent with a mechanism involving the addition of surface hydrogen to the surface associated triazine.

The effect of two major hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) metabolites, hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX), on cricket (Acheta domesticus) survival and reproduction was studied. RDX metabolites did not have adverse effects on cricket survival, growth, and egg production. However, MNX and TNX did affect egg hatching. MNX and TNX were more toxic in spiked-sand than in topical tests. TNX was more toxic to egg than MNX. Developmental stage and exposure time affected hatching. After 30 days exposure to MNX or TNX, the EC20, EC50, and EC95 were 47, 128, and 247 microg/g for TNX, and 65, 140, and 253 microg/g for MNX in topical tests. The ECs for 20, 50, and 95 were 21, 52, and 99 microg/g for MNX, and 12, 48, and 97 microg/g for TNX in sand. No gross abnormalities in cricket nypmhs were observed in all experiments indicating that neither TNX or MNX is teratogenic in this assay.

The sublethal and chronic effects of the environmental contaminant and explosive octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in artificial soil were assessed using the earthworm (Eisenia andrei). Based on various reproduction parameters (total and hatched number of cocoons, number of juveniles and their biomass), fecundity was reduced at the different concentrations of HMX tested (from 280.0 +/- 12.3 to 2502.9 +/- 230.0 mg kg-1 dry soil) in spiked artificial soil (LOEC: 280.0 +/- 12.3 mg kg-1 dry soil). The growth of adult E. andrei was also reduced at the different concentrations tested, though no mortality occurred, even at the highest tested concentrations. The number of juveniles produced was correlated with the number of total and hatched cocoons, and the biomass of juveniles was correlated with the number of cocoons. Pooled results of these and earlier studies on explosives (TNT, RDX) using the E. andrei reproduction test confirm that effects of HMX on cocoon production are indicative of some reproductive consequences (number of juvenile and their biomass), whereas adult growth, in general, does not correlate strongly with change in reproduction capacity.

The effect of high hydrostatic pressures on the ecotoxicological profile of pollutants is an unexplored research area. Using Pomatoceros lamarcki as a surrogate organism for this eco-barotoxicological study, it was found that in a 48 h larval bioassay with water accommodated fractions (WAF) of crude oil of up to 15.1 mg L(-1) (total hydrocarbon content) and hydrostatic pressures up to 300 bar (3000 m), an additive response was found (p < 0.001) rather than any synergism (p = 0.881). Comprehensive cytogenetic analysis of 6-h (15 degrees C) embryos exposed to WAF (0.19 mg L(-1)) at 100 bar showed no effects on mitotic fidelity or cell division rate over the 1 bar treatment. However, embryo's treated with the clastogen mitomycin-c at 100 bar exhibited a significant increase in mitotic aberrations over 1 bar treated as was the case with hypo/hypersaline treatments (p < 0.05). Conversely, an increase in hydrostatic pressure actually reduced the effects of spindle inhibition by the aneugen colchicine (p < 0.05).

This paper summarizes some results from a monograph which focused on ecological and biogeographical aspects of the biota in Norwegian lakes and rivers with particular reference to the snail fauna. Field studies were made in the course of 20 summers within the period of 1953-1987. Acidic water is the main reason why snails are absent from some 4000 lakes in a low-calcium area in southern Norway ('Acid south'). This area is heavily influenced by acidic precipitation. Snails were not detected in lakes with pH below 5.2. In one lake, three snail species disappeared in parallel with acidification from pH 5.2 to 4.2. The calcium level modified the effect of low pH.

We have developed a model which successfully reconstructs the lifetime polychlorinated biphenyl (PCB)-101 burden of the UK population for individuals born between 1920 and 1980. It not only follows burdens and clearance of persistent organic contaminants throughout a human lifetime--taking changes in age and body composition into account--but also, importantly, incorporates changing environmental concentrations of the compound of interest. Predicted results agree well with available measured lipid concentrations in human tissues. Its unique construction takes into account both changing environmental concentrations of PCBs in principal food groups and changing dietary habits during the time period. Because environmental burdens of persistent organic contaminants have changed over the last 60 years, residues in food will also have mirrored this change. Critically in this respect, the year in which an individual was born determines the shape and magnitude of their exposure profile for a given compound. Observed trends with age represent an historical legacy of exposure and are not simply a function of equal yearly cumulative inputs. We can demonstrate that the release profile of PCB-101 controls levels in the food supply and ultimately the burden of individuals throughout their life. This effect is expected to be similar for other PCB congeners and persistent organic compounds such as polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs). Models of this type have important applications as predictive tools to estimate the likely impact of source-reduction strategies on human tissue concentrations.

A previously unknown s-triazine species present in commercially available Irgarol-1051, a booster biocide additive in copper-based antifouling paints for the replacement of organotin-based antifoulants, has been identified in the coastal aquatic environment. After careful isolation, purification and characterization by high resolution MS-MS and (1)H NMR, the molecular structure of that unknown species is found to be N,N'-di-tert-butyl-6-methylthiol-s-triazine-2,4-diamine (designated as M3). Levels of Irgarol-1051, its major degradation product (M1) and the newly identified M3 in the coastal waters of Hong Kong, one of the world's busiest ports located in the southern coast of China, were monitored by SPME-GC-MS and SPME-GC-FID. Water samples from five locations within Hong Kong waters were analysed and the levels of Irgarol-1051, M1 and M3 were found to be 0.1-1.6 microg l(-1), 36.8-259.0 microg l(-1) and 0.03-0.39 microg l(-1), respectively. Our results indicate that M3 is relatively stable against photo- and bio-degradation and may pose considerable risk to primary producer communities in the coastal marine environment.

Laboratory-based relationships that model the phytotoxicity of metals using soil properties have been developed. This paper presents the first field-based phytotoxicity relationships. Wheat (Triticum aestivum L.) was grown at 11 Australian field sites at which soil was spiked with copper (Cu) and zinc (Zn) salts. Toxicity was measured as inhibition of plant growth at 8 weeks and grain yield at harvest. The added Cu and Zn EC10 values for both endpoints ranged from approximately 3 to 4760 mg/kg. There were no relationships between field-based 8-week biomass and grain yield toxicity values for either metal. Cu toxicity was best modelled using pH and organic carbon content while Zn toxicity was best modelled using pH and the cation exchange capacity. The best relationships estimated toxicity within a factor of two of measured values. Laboratory-based phytotoxicity relationships could not accurately predict field-based phytotoxicity responses.

A field survey was conducted at a deserted arsenic (As) mine in Guangxi Province, China to explore new potential As hyperaccumulators. In addition, young plants of 11 Pteris taxa were grown in glasshouse conditions for 12 weeks on As-amended soils with 0, 50 and 200 mg As kg(-1). Results of the field survey showed that the fern Pteris fauriei accumulated over 1000 mg As kg(-1) in its fronds. Of the 11 Pteris taxa, Pteris aspericaulis, Pteris cretica var. nervosa, P. fauriei, Pteris multifida, P. multifida f. serrulata, and Pteris oshimensis were all found to hyperaccumulate As in addition to P. cretica 'Albo-Lineata' and Pteris vittata (already reported as As hyperaccumulators). However, Pteris ensiformis, Pteris semipinnata and Pteris setuloso-costulata showed no evidence of As hyperaccumulation. Results also revealed a constitutive property of As hyperaccumulation in different populations of P. cretica var. nervosa, P. multifida, P. oshimensis and P. vittata.

Loblolly pine (Pinus taeda L.) seedlings were exposed to 0.120 micromol mol(-1) (ppm) ozone for 7 h per day, 5 days per week for 12 weeks. No visible damage resulted from this regime. A short-lived radioisotope of carbon ((11)C) was used to characterize changes in plant physiology caused by ozone, the first time this technique has been used for ozone exposure studies. In comparison to plants kept in charcoal-filtered air, pines exposed to ozone exhibited reductions in photosynthesis (16%), speed of phloem transport (11%), phloem photosynthate concentration (40%) and total carbon transport toward roots (45%). Photosynthate not transported to the roots appeared to accumulate in the stems. Primary branches of pines exposed to ozone were some 50-60% heavier than those of control pines. Ozone was thus shown to have a significant short-term impact on phloem transport processes that results in a shift in allocation of photosynthate favoring stems.

In the new European Pesticide Regulation (EC) No. 1107/2009, the harmonisation of approaches for estimation of the environmental exposure of pesticides is considered a major goal. Several member states currently require their own models for the calculation of predicted environmental concentrations (PEC) in surface water. The variety of methods makes risk evaluations rather time-consuming for both notifiers and evaluating authorities. In the present study we compare surface water concentrations of 19 compounds using EU and country-specific models and risk assessment approaches to evaluate to which extent the resulting estimated exposure concentrations differ. Our results show that EU and country specific approaches and the resulting surface water concentrations differ considerably regarding basic model assumptions and assessment methods. The results indicate that the aimed harmonisation of risk assessment approaches within the EU will be difficult based on current models. New scenarios may help to achieve a harmonisation taking country-specific features into account.

Groups of zebra mussels (Dreissena polymorpha) and asiatic clams (Corbicula fluminea) were exposed to cadmium and zinc with the aim of studying the effect of these metals on the 57Co, 110Ag and 134Cs uptake and depuration by these freshwater bivalves. In the presence of zinc, the 57Co concentration factor for the whole organism of the two species was halved, notably because of a decrease of the uptake parameter. Conversely, Zinc and the Cd + Zn mixture increased the 110mAg uptake process by clams and mussels. The two metals also increased the depuration of this radionuclide in mussels, whereas this phenomenon was only observed in clams exposed to cadmium. In comparison with 57Co and 110mAg, the 134Cs bioconcentration was 5-10 times lower in D. polymorpha and not detected in C. fluminea. This weak contamination by this radionuclide resulted from a lower uptake and a higher depuration parameters.

Golden Bear Oil (GB-1111; legal trade name for GB-1313) is a petroleum distillate that is used in the United States and other countries as a larvicide for mosquito suppression. As part of a multi-species evaluation of the potential effects of GB-1111 on birds, red-winged blackbird eggs were collected, artificially incubated, and treated with one of five amounts of GB-1111 varying from 0 to 10 times the expected exposure from a spray application of the maximum recommended amount (X=47 l/ha, 5 gal/ac). The application of 10 X caused a significant reduction in hatching success. A dose-related reduction of hepatic microsomal monooxygenase activity (EROD) was detected. Among body weights, skeletal measurements, and age at death, only crownrump length was different among experimental groups. Overall, the potential hazard to embryos of a representative wetland passerine appears minimal until the application rate exceeds 3 X.

Golden Bear Oil (GB-1111; legal trade name for GB-1313) is a petroleum distillate used in the United States and other countries as a mosquito larvicide. As part of an evaluation of the potential effects of GB-1111 on birds, fertile eggs of mallards (Anas platyrhynchos) and bobwhite (Colinus virginianus) were incubated in the laboratory, and treated on day 4 of incubation with external applications equivalent to either 0, 1/3, 1, 3 or 10 times the maximum rate (X) of 47 l/ha (5 gal/A) of field application of GB-1111. Hatching success was significantly reduced in mallards treated at 3 and 10 times the maximum field application, with a calculated approximate LD50 of 1.9 times the maximum field application. Most mortality occurred within a week of treatment. Hepatic P450-associated monooxygenase activity (ethoxyresorufin-O-dealkylase; EROD) was negatively related to dose. In the 3X group there was a significant increase in the concentration of hepatic reduced glutathione (GSH) but a decrease in protein-bound thiols (PBSH). Hatching success of bobwhite was marginally reduced at the highest level of treatment (10X). Other effects at this level in bobwhite included a significant increase in incidence of abnormal embryos or hatchlings, lower body and liver weights, and a two-fold increase in hepatic microsomal EROD activity in hatchlings. The recommended maximum rate of field application of GB-1111 is unlikely to impair the survival or development of bobwhite embryos but is potentially toxic to mallard embryos under conditions of larvicide drift or spray overlap.

A field study was undertaken to determine whether 207Pb and 111Cd, applied to the exterior bark of sugar maple (Acer saccharum Marsh.), white ash (Fraxinus americana L.) and white pine (Pinus strobus L.), could enter xylem tissue. Stable isotope tracers (3 microg Pb ml(-1); 2 microg Cd ml(-1)) were applied separately to bark in simulated rainfall, acidified to pH 4.5, in multiple doses over a 4 month (July-October) period. Tree cores were extracted from the region of application in the following March, and Pb and Cd isotopes were measured in bark and the outer tree rings using inductively coupled plasma mass spectrometry. The majority of the applied stable isotope tracer recovered (over 94%) was present in bark tissue, although a small amount of each metal tracer entered the outer (1-3) tree rings in all trees. Despite high concentrations of excess 207Pb in bark (up to 50 microg g(-1)), the maximum concentration of excess 207Pb measured in tree rings was only around 50 ng g(-1), which represents less than 30% of the background Pb concentration in wood at the study site. High excess 111Cd concentrations in bark (up to 35 microg g(-1)) also resulted in small increases in 111Cd in wood (up to 50 ng g(-1)), but due to lower background Cd concentrations in wood, such increases more than doubled the amount of Cd in wood compared with background levels. However, at sites where such high bark Cd concentrations are found, uptake from Cd-contaminated soil would probably be much greater than found at our study site. It appears that Cd and Pb applied to bark can enter woody tissue, but that this route of uptake is likely to be a minor contributor to the metal burden in wood.

The level of production of nanoparticles will inevitably lead to their appearance in air, water, soils, and organisms. A theoretical framework that relates properties of nanoparticles to their biological effects is needed to identify possible risks to human health and the environment. This paper considers the properties of dispersed metallic nanoparticles and highlights the relationship between the chemical stability of these nanoparticles and their in vitro toxicity. Analysis of published data suggests that chemically stable metallic nanoparticles have no significant cellular toxicity, whereas nanoparticles able to be oxidized, reduced or dissolved are cytotoxic and even genotoxic for cellular organisms.

Following the introduction of automobile catalysts in the middle of the 1980s in Germany there is an increasing emission of the platinum-group-metals platinum, palladium (Pd) and rhodium. Still, it remains unclear if these metals are bioavailable for aquatic animals and to which extent they become accumulated by the aquatic biosphere. Because of analytical problems in detecting Pd in small biological samples the present investigation concentrates on the bioavailability of this metal. To answer the question of a Pd uptake by aquatic organisms experimental studies were conducted with European eels maintained in water containing road dust at a concentration of 10 kg/100 l. Following an exposure period of four weeks, samples of liver and kidney were analysed by total-reflection X-ray fluorescence analysis after co-precipitation of Pd with mercury. These experiments revealed an uptake of traffic related Pd by European eels which showed a mean liver Pd concentration of 0.18 +/- 0.05 ng/g (wet wt.), whereas the Pd concentration in the kidney ranged below the detection limit. Thus, in this study we can demonstrate for the first time that automobile catalyst emitted Pd is bioavailable for aquatic animals.

The transformation of landscapes from non-urban to urban land use has the potential to greatly modify soil carbon (C) pools and fluxes. For urban ecosystems, very little data exists to assess whether urbanization leads to an increase or decrease in soil C pools. We analyzed three data sets to assess the potential for urbanization to affect soil organic C. These included surface (0-10 cm) soil C data from unmanaged forests along an urban-rural gradient, data from "made" soils (1 m depth) from five different cities, and surface (0-15 cm) soil data of several land-use types in the city of Baltimore. Along the urban-rural land-use gradient, we found that soil organic matter concentration in the surface 10 cm varied significantly (P=0.001). In an analysis of variance, the urban forest stands had significantly (P=0.02) higher organic C densities (kg m(-2) to 1 m depth) than the suburban and rural stands. Our analysis of pedon data from five cities showed that the highest soil organic C densities occurred in loamy fill (28.5 kg m(-2)) with the lowest occurring in clean fill and old dredge materials (1.4 and 6.9 kg m(-2), respectively). Soil organic C densities for residential areas (15.5 +/- 1.2 kg m(-2)) were consistent across cities. A comparison of land-use types showed that low density residential and institutional land-uses had 44 and 38% higher organic C densities than the commercial land-use type, respectively. Our analysis shows that as adjacent land-use becomes more urbanized, forest soil C pools can be affected even in stands not directly disturbed by urban land development. Data from several "made" soils suggests that physical disturbances and inputs of various materials by humans can greatly alter the amount C stored in these soils.

The top 2 cm of forest soils were collected along a 120 km long south-north transect running through Norway's largest city Oslo. Forty samples were analysed for their polycyclic aromatic hydrocarbon (PAH(16) as defined by the U.S. Environmental Protection Agency) concentrations and compositions. Local variations in the PAH values are high and the reported concentrations are in general low (maximum sumPAH16: 2.6 mg/kg). The transect shows distinct differences of sumPAH16 values from south to north. PAH concentrations are substantially lower in the less populated areas at the north end of the transect than at the urbanised and much more populated south end. Several high values occur in a forested area to the north of Oslo, used for recreation purposes. The PAH distribution patterns point towards a predominantly pyrogenic origin. Local Cambrian carbon-rich black shales can be excluded as sources for PAHs in the forest soils.

Nanoscale zerovalent iron (nZVI) has potential for the remediation of organochlorine-contaminated environments. Environmental safety concerns associated with in situ deployment of nZVI include potential negative impacts on indigenous microbes whose biodegradative functions could contribute to contaminant remediation. With respect to a two-step polychlorinated biphenyl remediation scenario comprising nZVI dechlorination followed by aerobic biodegradation, we examined the effect of polyacrylic acid (PAA)-coated nZVI (mean diameter = 12.5 nm) applied at 10 g nZVI kg(-1) to Aroclor-1242 contaminated and uncontaminated soil over 28 days. nZVI had a limited effect on Aroclor congener profiles, but, either directly or indirectly via changes to soil physico-chemical conditions (pH, Eh), nZVI addition caused perturbation to soil bacterial community composition, and reduced the activity of chloroaromatic mineralizing microorganisms. We conclude that nZVI addition has the potential to inhibit microbial functions that could be important for PCB remediation strategies combining nZVI treatment and biodegradation.

In this study, the green-lipped mussel, Perna viridis (L.), was exposed to two concentrations of benzo[a]pyrene (B[a]P) (0.3 microg l(-1); 3 microg l(-1)) and two concentrations of Aroclor 1254 (0.5 microg l(-1); 5 microg l(-1)). In addition, a mixture of the contaminants was used (0.3 microg l(-1) B[a]P+0.5 microg l(-1) Aroclor 1254; 3 microg l(-1) B[a]P+5 microg l(-1) Aroclor 1254). All concentrations were nominal. A suite of enzymes [glutathione S transferase (GST), superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), glutathione reductase (GR)], glutathione (GSH) level and lipid peroxidation (LPO) in the mussel gill and hepatopancreas were monitored over 18 days. CAT and GSH in gill tissue were positively correlated with concentration of Aroclor 1254. Activity of hepatic GST and SOD was significantly related to body burden of Aroclor 1254. LPO, GR and GPx in gill and hepatopancreas and hepatic GST were positively correlated with B[a]P concentration. The results indicate the importance of using biomarkers specific to the type of contaminant(s) that are likely to be present. Controlled laboratory experiments, such as this study, are useful in ascertaining biomarkers suitable for use with complex contaminant mixtures in the marine environment.

The nature of soil organic matter (SOM) functional groups associated with sorption processes was determined by correlating partitioning coefficients with solid-state (13)C nuclear magnetic resonance (NMR) and diffuse reflectance mid-infrared (DRIFT) spectral features using partial least squares (PLS) regression analysis. Partitioning sorption coefficients for n-pentadecane (n-C(15)) were determined for three alternative models: the Langmuir model, the dual distributed reactive domain model (DRDM) and the Freundlich model, where the latter was found to be the most appropriate. NMR-derived constitutional descriptors did not correlate with Freundlich model parameters. By contrast, PLS analysis revealed the most likely nature of the functional groups in SOM associated with n-C(15) sorption coefficients (K(F)) to be aromatic, possibly porous soil char, rather than aliphatic organic components for the presently investigated soils. High PLS cross-validation correlation suggested that the model was robust for the purpose of characterising the functional group chemistry important for n-C(15) sorption.

The biodegradation of nonextractable residues (NER) of pesticides in soil is still poorly understood. The aim of this study was to evaluate the influence of NER ageing and fresh soil addition on the microbial communities responsible for their mineralisation. Soil containing either 15 or 90-day-old NER of (13)C-2,4-D (NER15 and NER90, respectively) was incubated for 90 days with or without fresh soil. The addition of fresh soil had no effect on the mineralisation of NER90 or of SOM, but increased the extent and rate of NER15 mineralisation. The analyses of (13)C-enriched FAME (fatty acids methyl esters) profiles showed that the fresh soil amendment only influenced the amount and structure of microbial populations responsible for the biodegradation of NER15. By coupling biological and chemical analyses, we gained some insight into the nature and the biodegradability of pesticide NER.

Haloacetic acids (HAAs) are contaminants of aquatic ecosystems with numerous sources, both anthropogenic and natural. The toxicity of HAAs to aquatic plants is generally uncharacterized. Laboratory tests were conducted with three macrophytes (Lemna gibba, Myriophyllum sibiricum and Myriophyllum spicatum) to assess the toxicity of five HAAs. Myriophyllum spp. has been proposed as required test species for pesticide registration in North America, but few studies have been conducted under standard test conditions. The HAAs in the present experiments were monochloroacetic acid (MCA), dichloroacetic acid (DCA), trichloroacetic acid (TCA), trifluoroacetic acid (TFA) and chlorodifluoroacetic acid (CDFA). MCA was the most toxic to Myriophyllum spp. with EC50 values ranging from 8 to 12.4 mg/l depending on the endpoint, followed by DCA (EC50 range 62-722.5 mg/l), TCA (EC50 range 49.5-1702.6 mg/l), CDFA (EC50 range 105.3 to >10,000 mg/l) and with TFA (EC50 range 222.1 to 10,000 mg/l) the least toxic. Generally, L. gibba was less sensitive to HAA toxicity than Myriophyllum spp., with the difference in toxicity between them approximately threefold. The range of toxicity within Myriophyllum spp. was normally less than twofold. Statistically, plant length and node number were the most sensitive endpoints as they had the lowest observed coefficients of variation, but they were not the most sensitive to HAA toxicity. Toxicological sensitivity of endpoints varied depending on the measure of effect chosen and the HAA, with morphological endpoints usually an order of magnitude more sensitive than pigments for all plant species. Overall, mass and root measures tended to be the most sensitive indicators of HAA toxicity. The data from this paper were subsequently used in an ecological risk assessment for HAAs and aquatic plants. The assessment found HAAs to be of low risk to aquatic macrophytes and the results are described in the second manuscript of this series.

Perennial ryegrass plants (Lolium perenne L.) were exposed in "Closed-Top Chambers" to different ozone concentrations and to charcoal filtered ambient air to study the effect of ozone on the development of pollen. Ozone at ambient (65 nl l(-1), 8h) and elevated (110 nl l(-1), 4h) concentrations affected the maturing of pollen by inhibiting starch accumulation in pollen throughout the anther. Affected pollen persisted in the vacuolated state while normal pollen in the same anther were filled with amyloplasts. The percentage of underdeveloped pollen-determined in transversal sections-was significantly higher in exposed plants than in plants grown in filtered air. Results indicate that ozone stress was responsible for the disrupted development of pollen in L. perenne.

Sources of mercury contamination in aquatic systems were studied in a comprehensive literature review. The results show that the most important anthropogenic sources of mercury pollution in aquatic systems are: (1) atmospheric deposition, (2) erosion, (3) urban discharges, (4) agricultural materials, (5) mining, and (6) combustion and industrial discharges. Capping and dredging are two possible remedial approaches to mercury contamination in aquatic systems, and natural attenuation is a passive decontamination alternative. Capping seems to be an economical and effective remedial approach to mercury-contaminated aquatic systems. Dredging is an expensive remedial approach. However, for heavily polluted systems, dredging may be more effective. Natural attenuation, involving little or no cost, is a possible and very economical choice for less contaminated sites. Proper risk assessment is necessary to evaluate the effectiveness of remedial and passive decontamination methods as well as their potential adverse environmental effects. Modeling tools have a bright future in the remediation and passive decontamination of mercury contamination in aquatic systems. Existing mercury transport and transformation models were reviewed and compared.

Biosurfactants are surfactants that are produced extracellularly or as part of the cell membrane by bacteria, yeasts and fungi. Examples include Pseudomonas aeruginosa which produces rhamnolipids, Candida (formerly Torulopsis) bombicola, one of the few yeasts to produce biosurfactants, which produces high yields of sophorolipids from vegetable oils and sugars and Bacillus subtilis which produces a lipopeptide called surfactin. This review includes environmental applications of these biosurfactants for soil and water treatment. Biosurfactant applications in the environmental industries are promising due to their biodegradability, low toxicity and effectiveness in enhancing biodegradation and solubilization of low solubility compounds. However, more information is needed to be able to predict and model their behaviour. Full scale tests will be required. The role of biosurfactants in natural attenuation processes has not been determined. Very little information is available concerning the influence of soil components on the remediation process with biosurfactants. As most of the research until now has been performed with rhamnolipids, other biosurfactants need to be investigated as they may have more promising properties.

The distributions of radionuclides in plant components as to radionuclide transfer to animals are important for understanding the dynamics of radionuclides in an agricultural field. Most of the non-edible parts in these components are returned to the soil as organic fertilizer where they may again be utilized in the soil-plant pathway and/or are mixed with feed for livestock. Rice plants were grown in an experimental field and separated at harvest into different components, including polished rice, rice bran, hull, leaves, stem and root, and then the distributions of radioactive 137Cs, stable 133Cs and K in these components were determined. The distribution of 137Cs in polished rice and rice bran was similar to that of 133Cs, while that of K was different. The concentration ratios of 133Cs/K in leaf blade positions increased with aging, which means that the translocation rate of 133Cs in rice plants was slower than that of K. At harvest the distribution of dry weight in polished rice to entire rice plants was 34%, and the distributions of 133Cs in the polished rice and the non-edible parts were 7 and 93%, respectively, whereas those of K in the polished rice and the non-edible parts were 2 and 98%, respectively. Findings suggest that the transfer and distribution of 133Cs, not of K, provide better information on the long-term fate of 137Cs in an agricultural environment.

This paper presents an attempt to reach natural background levels of heavy metals in surficial sediments of the Gulf of Lions (NW Mediterranean). To correct for the grain-size effect, normalization procedures based on a clay mineral indicator element are commonly used, after a first grain size separation by sieving. In our study, we tested the applicability of this method with respect to commonly used normalizer elements, and found that stable Cs shows the best ability to reflect the fine sediment fraction. Background levels were successfully reached for Co, Cr, Cu, Ni and Pb, compared to various literature references. Nevertheless, in the case of lead, the normalized data depicted a general enrichment in all samples, and the natural levels could only be reached when concentrations were corrected for the atmospheric contribution by analysing lead isotope ratios. Also for Zn, a general enrichment was found in our samples, although less important.

The Peach Bottom Atomic Power Station (PBAPS) has contributed measurable quantities of radioactivity to Conowingo Reservoir, an impoundment of the lower Susquehanna River. As part of an ongoing radiological assessment program, concentrations of plant-related radionuclides in sediments have been monitored in spring and fall since 1980. Mass balance estimates derived from grab samples of surface sediments (< 10 cm) indicate that less than 20% of reactor released (60)Co, (65)Zn, (134)Cs and (137)Cs is present in these sediments. Significant seasonal variations in radionuclide trapping efficiency by the reservoir are not apparent. Deep core samples (c. 200 cm) confirm that some, but not all, of this surface sediment radionuclide inventory remains within the reservoir-trapped in discrete locations by subsequent sediment accumulation. The remaining radionuclide mass, in dissolved or particle-associated form, appears to be transported downstream, through Conowingo Dam, to upper Chesapeake Bay. The detection of PBAPS-derived radionuclides in the sediments of upper Chesapeake Bay, primarily the Susquehanna Flats, confirms the transport of these radionuclides from the lower Susquehanna River.

Amaranthus tricolor L. and Amaranthus cruentus L. were grown in pots containing 7.5 kg soils artificially contaminated with three levels of 134Cs activity: 5.55 x 10(5) Bq pot-1, 1.11 x 10(6) Bq pot(-)1, and 1.665 x 10(6) Bq pot(-1), respectively. Forty-nine days after sowing and growth, plants were harvested. The plants growing in soils with increasing 134Cs concentrations showed increasing concentration of this radionuclide in shoots. There were significant differences in uptake of 134Cs applied to soils between and within the plant species, depending on the initial 134Cs concentrations. The plant species showed different responses to the addition of (NH4)2SO4 to soils. Biomass production of both species was reduced in pots treated with (NH4)2SO4. (NH4)2SO4 application decreased the uptake of 134Cs by A. tricolor but increased the accumulation of 134Cs by A. cruentus, showing that chemicals with the highest efficiency to enhance the desorption of 134Cs might play an unexpected role in transferring the radionuclide to shoots.

In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces.

Dispersal of (137)Cs from Komsomolets and K-159 is simulated using realistic rates and hypothetical scenarios. Furthermore, spatiotemporal (137)Cs concentrations in Northeast Arctic cod and capelin are estimated based on survey data. The results indicate that only pulse discharges from K-159 will cause concentrations of (137)Cs in cod muscle exceeding the intervention level of 600 Bq/kg fresh weight. A discharge of ≥10% of the (137)Cs-inventory will result in concentrations in muscle of cod exceeding the intervention level for approximately two years. In fact, a discharge of 10% of the (137)Cs-inventory results in an overlap of 8-30% between the different size groups of cod and levels that exceed the intervention level during the first year after the discharge. For capelin, individuals less than one year old during the first year after a discharge are more likely to be severely affected by discharges comprising ≥50% of the inventory.

The distribution coefficient of (137)Cs has been determined in 58 soils from 12 sampling points from Biscay by treating 10 g with 25 ml of an aqueous solution with an activity of 1765 Bq in the radionuclide, by shaking during 64 h and measuring the residual activity with a suitable detector. Soils were characterised by sampling depth, particle size analysis and the usual chemical parameters. Soils were thereafter treated to fix the chemical forms of (137)Cs speciation by successive extractions in order to determine fractions due to exchangeable, associated with carbonates, iron oxide and organic matter fractions, obtaining by difference the amount taken by the rest of the soil constituents. For this research, 16 soils from four points were selected from the previous samples. The greatest mean percentages of (137)Cs sorption were with the rest (69.93), exchangeable (13.17) and organic matter (12.54%) fractions. This paper includes also the calculation of partial distribution coefficients for chemical species as well as relations of distribution coefficients both among them and with soil parameters.

The Chernobyl accident, and the general acidification of Swedish water systems, form the base for this project. The aims of the work have been to present results on the linkage between the concentration of Cs-137 in fish, lake load of Cs and lake characteristics, to give a preliminary prognosis on the recovery, and to put the results within a wider framework of environmental hazard analysis. A broad set of data on limnology, morphometry and drainage area conditions from 41 lakes were collected during 1986 and 1987. Cs-137 was determined in 1 + perch (Cs-pe, 1-year-old perch), water, material collected by sediment traps and from surficial sediments. The main results are as follows. The average value of Cs-pe for all lakes has dropped from 9800 Bq kg(-1) (wet) to 5040 between the 2 years. Generally, the decrease is between 5 and 90%. We have tested if any factor(s) could be specifically linked to this decrease-no such factors have been found. The concentrations of Cs in sediment traps have, on average, decreased by 80%. Very high correlations exist between Cs-pe and the caesium load as determined from the sediment traps. Between 1 and 10% (mean 3.9%) of the initial fall-out deposition to the drainage area was transported from land to water during June to August 1986. The variation in initial fall-out deposition explains 65-69% of the variability in Cs-pe; the degree of explanation (= coefficient of determination, r2) increases to about 85% if one also takes into account the lake water hardness and totP. A map showing with lakes likely to have 1 + perch with higher mean Cs-concentrations than 1500 Bq kg(-1) wet is presented. Between 4000 and 7000 lakes in Sweden appear to have Cs-pe higher than 1500 Bq kg(-1) wet, figures which emphasize the serious impact of the Chernobyl accident on the environmental conditions in Sweden.

We estimated the flux of caesium-137 adsorbed to suspended sediment in the Kusaki Dam reservoir in the Fukushima region of eastern Japan, which was contaminated by the Fukushima Nuclear Power Plant accident. The amount and rate of reservoir sedimentation and the caesium-137 concentration were validated based on the mixed-particle distribution and a sediment transport equation. The caesium-137 and sediment flux data suggested that wash load, suspended load sediment, and caesium-137 were deposited and the discharge and transport processes generated acute pollution, especially during extreme rainfall-runoff events. Additionally, we qualitatively assessed future changes in caesium-137 and sediment fluxes in the reservoir. The higher deposition and discharge at the start of the projection compared to the 2090s are most likely explained by the radioactive decay of caesium-137 and the effects of reservoir sedimentation. Predictions of the impacts of future climate on sediment and caesium-137 fluxes are crucial for environmental planning and management.

Soils from a local reservoir had been analyzed for their physical and chemical properties, distribution coefficients Kd and sorption rates for 137Cs. It was found that soils in Hong Kong were relatively low in organic matter and more acidic than those in some other countries. In sorption experiments, the rates of decrease in water activity concentration were initially very high, higher for larger mass of soils added, and then slowed down. The larger the mass, the shorter was the time for equilibrium. Three isotherms had been obtained by varying one of the three parameters (initial water activity concentration, slurry ratio and particle size) at a time. For constant initial water activity concentration and random sizes, percent sorption increased with slurry ratio. For soils of constant mass and random sizes. percent sorption decreased with increasing initial water activity concentration. For constant initial water activity concentration and slurry ratio, percent sorption increased with decreasing size of soil particles. A simple logistic model was developed to explain some of the findings.

CRS and SIT are two (210)Pb-based models widely used in the radiometric dating of recent sediments. (210)Pb chronologies should be validated using at least one independent tracer, such as (137)Cs. This paper demonstrates that simple methods based on the identification of (137)Cs fallout peaks cannot provide a definitive support for CRS and SIT chronologies. Two main arguments will support this assertion: Firstly, the (137)Cs time-marks cannot support a CRS or SIT chronology if the derived sedimentation rates cannot explain the whole (137)Cs activity profile without postulating mixing. Secondly, the support by the (137)Cs time-marks for a given CRS or SIT chronology cannot be considered as definitive if other dating models can equally explain the whole set of data, thereby producing a different chronology. Several case studies selected from the literature are used to support the present discussion.

Following the Chernobyl accident in late April 1986, central Finland was subjected to considerable radioactive fallout. The radioactive isotope of caesium, (137)Cs, was potentially the most harmful isotope in the fallout because of its long half-life (30 years). (137)Cs activities remained unexpectedly low within the biota (algae, zooplankton, aquatic moss, fish) of some humic forest lakes in southern Finland compared to the clear water lakes within the same district. This observation suggested that humic substances, by binding (137)Cs chemically, may reduce its bioavailability in lake water. Our laboratory experiments (throughflow systems; gel chromatography) demonstrated that binding of (137)Cs by humic substances was negligible in untreated lake waters; only when most of the alkali metals had been removed with an ion exchange resin was any binding of (137)Cs by low molecular humic fractions apparent. Instead, the concentrations of cations (especially potassium) were of overwhelming importance for the bioavailability of (137)Cs within the lacustrine ecosystems. The concentrations of (137)Cs within food chains are expected to stay at a high level for many years especially in lakes with long water renewal times.