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1.
A method to measure the emissive concentration of 5-ethylidene-2-norbornene (ENB), a reactive compound used in industrial synthesis of terpolymers, has been developed. The starting points for the development of the presented method are European and Italian reference methods for the quantification of nonreactive volatile organic compounds in industrial emission. In this study, sampling conditions and desorption solvent have been optimized in laboratory and the method was applied in an industrial plant. The laboratory tests showed a good recovery (88–95 %). The concentrations of ENB in industrial emission obtained with the developed method were compared with an online gas chromatography–flame ionization results (R 2?>?0.97). In addition, several manual measurements were performed in parallel, and the resulting %RSD repeatability was <9 %. The developed method provides a discontinuous technique to measure reactive volatile organic compounds using easy-to-use instruments and assures a very good accuracy and precision even with high-humidity gas flows. The method could be extended to other reactive compounds of the same class.  相似文献   

2.
Ozone uptake into plant leaves was measured in gas exchange chambers using a mass balance and a variable conductance approach. The variable conductance approach was found to more reliably measure ozone flux through stomata. Measurements using this approach were contrasted with estimates obtained by measuring stomatal conductance g(sw) and modeling ozone uptake using a diffusion equation, assuming a negligible ozone concentration in the substomatal cavity. Actual measurements of uptake were close, but slightly higher than modeled values, providing some support to the idea that substomatal ozone concentrations are close to zero. However, the difference between measured and modeled uptake values suggests either that (i) variable conductance approach measures more ozone uptake than caused by stomatal uptake alone or (ii) ozone conductance is underestimated.  相似文献   

3.
In this study, biotransformation rate constants are estimated for a large set of organic compounds. Biotransformation (km) is considered part of the total elimination, further consisting of physico-chemical elimination to water (kw), depuration by feces (kf) and growth dilution (gamma). Existing models are used to estimate kw and kf, and gamma. The difference between measured elimination rate constants and the sum of predicted elimination rate constants for water, feces and growth indicates the ration of biotransformation in the total elimination. In all examined animal classes, polycyclic aromatic hydrocarbons seem to be metabolized at an intermediate rate. Because of the relative low hydrophobicity of some of the studied compounds, their physico-chemical elimination rate constant is relatively high, and the relative contribution of metabolism to total elimination of these compounds is therefore relatively low. Fish seem to be capable of metabolizing chlorodibenzo-p-dioxins and -furans, DDT, chloroanilines and phenol.  相似文献   

4.
Two scenarios for future pig meat production were constructed. The first was a "business as usual" scenario, where the pig feed was based on domestic grain and imported soy-meal, and no efforts were made to reduce pesticide use. The second scenario had a strong environmental focus, and both peas and rapeseed were grown at pig-farm level to produce grain and protein feed. Preventive measures, such as a more diverse crop rotation and mechanical weed control, were combined to reduce pesticide use. The two scenarios were environmentally assessed by Life Cycle Assessment (LCA) and a pesticide risk indicator model (PRI-Farm). The results showed environmentally sound possibilities to reduce pesticide dependency and risks by using altered plant protection strategies in pig-feed production. Organizing on-farm feed production so that protein feed crops are integrated with grain crops contributes to a more diverse crop rotation.  相似文献   

5.
Aldicarb and aldoxycarb pesticides were applied to potato fields in central Wisconsin to study the degradation and movement of their carbamate residues within the soil profile. Aldicarb and aldoxycarb residues degraded at similar rates with half-lives ranging from 0.9 to 1.4 months. Although unsaturated-zone residue measurements indicated relatively minor differences among the three plots, residues were detected in shallow groundwater beneath plots treated with aldicarb or aldoxycarb at planting. Residues beneath the plot treated with aldicarb at emergence were much lower and the timing of these residues suggests they might have resulted from migration of residues from the plot treated with aldicarb at planting. This study confirms the results of previous and concurrent research programs which suggest that emergence applications of aldicarb reduce the potential for residues to enter shallow groundwater without reducing insect control or potato yields.  相似文献   

6.
Understanding the environmental burdens associated with aquafeeds is a critical component for assessing and improving the environmental performance of aquaculture. The aim of the study was to assess the environmental impacts associated with feeds for rainbow trout production in France, using Life Cycle Assessment (LCA). The stages assessed are: the extraction of the raw materials, the production and transformation of the primary ingredients used, the manufacturing of the feeds, the use of the feeds at the farm, transport at all stages, and the production and use of energy resources. The assessment revealed that the use of fishery resources (such as biotic resource use) and nutrient emissions at the farm (such as eutrophication potential) contribute most to the potential environmental impacts of salmonid aquafeeds. Improvements in feed composition and management practices seem to be the best ways for improving the environmental profile of aquafeeds.  相似文献   

7.
Argentinian agricultural production is fundamentally based on a technological package that combines no-till and glyphosate in the cultivation of transgenic crops. Transgenic crops (soybean, maize and cotton) occupy 23 million hectares. This means that glyphosate is the most employed herbicide in the country, where 180–200 million liters are applied every year.  相似文献   

8.
Sabaté J  Viñas M  Solanas AM 《Chemosphere》2006,63(10):1648-1659
When hydrocarbon-contaminated soil is subjected to bioremediation technology, hydrocarbon depletion is typically marked by an initially rapid reduction rate. This rate decreases over time and frequently a residual concentration remains in the soil. This kinetic has been attributed primarily to the enrichment of more recalcitrant fractions, as well as to the lack of resting hydrocarbon bioavailability. Thus, at the end of the bioremediation process, a part of the residual hydrocarbon soil concentration represents the non-bioavailable fraction, which is difficult to degrade by microbial populations and which poses a minor hazard. Therefore, determination of the bioavailable fraction in a bioremediation project represents both an estimation of the maximum level of achievable biodegradation, as well as an additional indication of the environmental health hazard. In the present study, aged creosote-contaminated soil was subjected to biostimulation processes, and the bioavailable fraction for several target polycyclic aromatic hydrocarbons (PAHs) was calculated using a mild extraction with cyclodextrines. The amount of PAH extracted corresponded to the desorbing fraction and can be regarded as the bioavailable fraction. The non-desorbing fraction data obtained from this procedure were compared to the remaining PAH concentrations following bioremediation treatment of soil microcosms. These results permitted the establishment of a theoretical biodegradation limit based on the desorbing fraction. In addition, neither accumulation of intermediate metabolites, nor the formation of bound-residues or reduced acute toxicity was observed.  相似文献   

9.
BACKGROUND: In 1996, the Committee on the Assessment of Wartime Exposure to Herbicides in Vietnam of the National Academy of Sciences' Institute of Medicine (IOM) issued a report on an exposure model for use in epidemiological studies of Vietnam veterans. This exposure model would consider troop locations based on military records; aerial spray mission data; estimated ground spraying activity; estimated exposure opportunity factors; military indications for herbicide use; and considerations of the composition and environmental fate of herbicides, including changes in the TCDD content of the herbicides over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of the herbicides into the ground. When the final report of the IOM Committee was released in October 2003, several components of the exposure model envisioned by the Committee were not addressed. These components included the environmental fate of the herbicides, including changes in the TCDD content over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of herbicides into the ground. This paper is intended to help investigators understand better the fate and transport of herbicides and TCDD from spray missions, particularly in performing epidemiological studies. METHODS: This paper reviews the published scientific literature related to the environmental fate of Agent Orange and the contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), and discusses how this affected the potential exposure to TCDD of ground troops in Vietnam. Specifically, the mechanisms of dissipation and degradation as they relate to environmental distribution and bioavailability are addressed. RESULTS: The evaluation of the spray systems used to disseminate herbicides in Vietnam showed that they were capable of highly precise applications both in terms of concentrations sprayed and area treated. Research on tropical forest canopies with leaf area indices (a measure of foliage density) from 2 to 5 indicated that the amount of herbicide and associated TCDD reaching the forest floor would have been between 1 and 6% of the total aerial spray. Studies of the properties of plant surface waxes of the cuticle layer suggested that Agent Orange, including the TCDD, would have dried (i.e., be absorbed into the wax layer of the plant cuticle) upon spraying within minutes and could not be physically dislodged. Studies of Agent Orange and the associated TCDD on both leaf and soil surface have demonstrated that photolysis by sunlight would have rapidly decreased the concentration of TCDD, and this process continued in shade. Studies of 'dislodgeable foliar residues' (DFR, the fraction of a substance that is available for cutaneous uptake from the plant leaves) showed that only 8% of the DFR was present 1 hr after application. This dropped to 1% of the total 24 hrs after application. Studies with human volunteers confirmed that after 2 hrs of saturated contact with bare skin, only 0.15-0.46% of 2,4,5-T, one of the phenoxy acetic acid compounds that was an active ingredient of Agent Orange, entered the body and was eliminated in the urine. CONCLUSIONS: The prospect of exposure to TCDD from Agent Orange in ground troops in Vietnam seems unlikely in light of the environmental dissipation of TCDD, little bioavailability, and the properties of the herbicides and circumstances of application that occurred. Photochemical degradation of TCDD and limited bioavailability of any residual TCDD present in soil or on vegetation suggest that dioxin concentrations in ground troops who served in Vietnam would have been small and indistinguishable from background levels even if they had been in recently treated areas. Laboratory and field data reported in the literature provide compelling evidence on the fate and dislodgeability of herbicide and TCDD in the environment. This evidence of the environmental fate and poor bioavailability of TCDD from Agent Orange is consistent with the observation of little or no exposure in the veterans who served in Vietnam. Appreciable accumulation of TCDD in veterans would have required repeated long-term direct skin contact of the type experienced by United States (US) Air Force RANCH HAND and US Army Chemical Corps personnel who handled or otherwise had direct contact with liquid herbicide, not from incidental exposure under field conditions where Agent Orange had been sprayed.  相似文献   

10.
Vale Canada Limited owns and operates a large nickel smelting facility located in Sudbury, Ontario. This is a complex facility with many sources of SO2 emissions, including a mix of source types ranging from passive building roof vents to North America's tallest stack. In addition, as this facility performs batch operations, there is significant variability in the emission rates depending on the operations that are occurring. Although SO2 emission rates for many of the sources have been measured by source testing, the reliability of these emission rates has not been tested from a dispersion modeling perspective. This facility is a significant source of SO2 in the local region, making it critical that when modeling the emissions from this facility for regulatory or other purposes, that the resulting concentrations are representative of what would actually be measured or otherwise observed. To assess the accuracy of the modeling, a detailed analysis of modeled and monitored data for SO2 at the facility was performed. A mobile SO2 monitor sampled at five locations downwind of different source groups for different wind directions resulting in a total of 168 hr of valid data that could be used for the modeled to monitored results comparison. The facility was modeled in AERMOD (American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model) using site-specific meteorological data such that the modeled periods coincided with the same times as the monitored events. In addition, great effort was invested into estimating the actual SO2 emission rates that would likely be occurring during each of the monitoring events. SO2 concentrations were modeled for receptors around each monitoring location so that the modeled data could be directly compared with the monitored data. The modeled and monitored concentrations were compared and showed that there were no systematic biases in the modeled concentrations.

Implications:

This paper is a case study of a Combined Analysis of Modelled and Monitored Data (CAMM), which is an approach promulgated within air quality regulations in the Province of Ontario, Canada. Although combining dispersion models and monitoring data to estimate or refine estimates of source emission rates is not a new technique, this study shows how, with a high degree of rigor in the design of the monitoring and filtering of the data, it can be applied to a large industrial facility, with a variety of emission sources. The comparison of modeled and monitored SO2 concentrations in this case study also provides an illustration of the AERMOD model performance for a large industrial complex with many sources, at short time scales in comparison with monitored data. Overall, this analysis demonstrated that the AERMOD model performed well.  相似文献   


11.
土壤重金属铬(Cr)污染形势严峻,对人群健康和生态环境构成了严重威胁。通过固化/稳定化技术降低土壤中金属的毒性或迁移性,是Cr污染场地常用的修复技术之一。由于Cr的环境行为变化多端、机制复杂,故导致固化/稳定化修复后场地存在Cr污染反弹的环境风险。综述了Cr在土壤中的氧化还原、吸附与解吸、沉淀与溶解,以及植物、微生物吸收与转化等多种环境行为;并梳理了已修复的Cr污染场地案例及场地长期跟踪监测数据,探讨了固化/稳定化修复后Cr的环境归趋及其影响因素,以期为修复后场地的风险管理提供参考。  相似文献   

12.
MacLeod M  Mackay D 《Chemosphere》1999,38(8):1777-1796
Systematic modelling of the fate of benzene and the chlorobenzenes is presented which follows a four-stage process of chemical classification, quantifying discharge rates and environmental concentrations, evaluative assessment of fate and regional mass balance modelling has been carried out for the southern Ontario region. The EQC model was applied to determine the principal transport and transformation processes experienced by this group of chemicals, which vary considerably in volatility and hydrophobicity. Observed environmental concentrations are in satisfactory agreement with the predictions of the steady state Level III ChemCAN model of chemical fate. A multiple pathway human exposure model which estimates intake of contaminants by residents of southern Ontario has been developed and applied to these chemicals. A novel method of deducing maximum tolerable environmental concentrations is presented. Results suggest that benzene and 1,4-dichlorobenzene are present in the environment at levels sufficient to cause exposures near allowable daily intake (ADI) levels for the general population, but the other substances are present at levels which result in exposure ranging from 1/10 to 1/1000 of the ADI.  相似文献   

13.
Tsui MT  Chu LM 《Chemosphere》2008,71(3):439-446
Mai Po Nature Reserve (Hong Kong) is an internationally important wetland for waterbirds. Roundup, a formulation based on glyphosate, has been used to control the widespread weeds within the reserve for many years but the fate and non-target impact of the herbicide is unknown. To fill this knowledge gap, we applied Roundup by hand-held sprayer to an estuarine and a freshwater pond in the dry season of year 2002. The surface water and sediment were sampled routinely for glyphosate concentrations following one month of application. In situ bioassays using local edible fish species were performed along with the herbicide application. Up to 52% of glyphosate in the surface water was transported to the unapplied regions by wind-driven current in the estuarine pond at 1 DPT (day post treatment). For both ponds, glyphosate concentrations in the water decreased rapidly after 1-3 DPT, but then decreased gradually over time. Both physical adsorption to the bottom sediments and microbial degradation are thought to contribute to these decreases. Interestingly, the persistence of glyphosate in the freshwater pond was longer than in the estuarine system, which is likely due to the considerably higher concentrations of chelating metals (i.e. Cu and Fe) present in the sediment (4.5 and 11-fold higher, respectively) which potentially reduced the bioavailability of glyphosate to the microbial decomposers. Lastly, fishes used in the in situ bioassays (both in applied and unapplied areas) showed similar survival rates, indicating that the use of Roundup at the provided application rate posed no serious hazard.  相似文献   

14.
Staples CA  Gulledge W 《Chemosphere》2006,65(4):691-698
Ethylene oxide (EO) is mainly used as a chemical intermediate and as a fumigant and sterilizing agent. Through its manufacturing and intended uses, EO may be released into the environment. Therefore, an assessment of the environmental significance of those potential emissions was conducted. Data were collected describing pertinent physical properties, degradation and other loss mechanisms that control the fate of EO in the environment. Available aquatic and terrestrial ecotoxicity data were assembled and used as the basis of calculating critical toxicity values to characterize hazard. Environmental compartment concentrations of EO were calculated using Level III fugacity-based modeling. Six scenarios were developed to account for different climatic conditions in various portions of the US. Finally, potential regional-scale risks to aquatic and terrestrial wildlife were determined. In the conceptual model that was developed in this assessment, EO diffuses into air, partitions between environmental compartments, is transported out of the different compartments via advection, and undergoes abiotic and biological degradation within each compartment. All known emissions within the continental USA were assumed to enter a modeled region roughly the size of the State of Ohio. Organisms (receptors) were assumed to dwell in both terrestrial and aquatic compartments. Receptors were assumed to include small mammals, soil invertebrates, water column (pelagic) organisms, and sediment benthos. The goal of this assessment was to characterize any potential adverse risks to terrestrial and aquatic wildlife populations. Hazard Quotients (HQ) were calculated by dividing predicted concentrations of EO in air, water, sediment, and soil by their critical toxicity values. Maximum calculated HQ values in air were 1.52x10(-7), in water were 1.17x10(-5), in sediment were 2.25x10(-4), and in soil were 1.37x10(-5). The results of this assessment suggest that EO as currently manufactured and used does not pose adverse risks to aquatic or terrestrial wildlife. In all cases, the HQ values were much less than the maximum desired HQ value of 1.0 (4,400-6,600,000 times), indicating that the potential for diffuse emissions of EO to pose adverse environmental risks is quite low.  相似文献   

15.
The effects of the solar eclipse on 11 August 1999 on surface ozone at two sites, Thessaloniki, Greece (urban site) and Hohenpeissenberg, Germany (elevated rural site) are investigated in this study and compared with model results. The eclipse offered a unique opportunity to test our understanding of tropospheric ozone chemistry and to investigate with a simple photochemical box model the response of surface ozone to changes of solar radiation during a photolytical perturbation such as the solar eclipse. The surface ozone measurements following the eclipse display a decrease of around 10–15 ppbv at the urban station of Eptapyrgio at Thessaloniki while at Hohenpeissenberg, the actual ozone data do not show any clear effect of eclipse on surface ozone. For Thessaloniki, the model results suggest that solely photochemistry can account for a significant amount of the observed surface ozone decrease during the eclipse but transport effects mask part of the photochemical effect of eclipse on surface ozone. For Hohenpeissenberg, the box model predicted an ozone decrease, due to the eclipse, of about 2 ppbv in relative agreement with the magnitude of the observed ozone decrease from the 2 h moving average while at the same time it inhibits the foreseen diurnal ozone increase. However, this modeled ozone decrease during the eclipse is small compared to the diurnal ozone variability due to transport effects, and hence, transport really masks such relative small changes. The different magnitude of the surface ozone decrease between the two sites indicates mainly the role of the NOx levels. Measured and modeled NO and NO2 concentrations at Hohenpeissenberg during the eclipse are also compared and indicate that the partitioning of NO and NO2 in NOx is influenced clearly from the eclipse. This is not observed at Thessaloniki due to local NOx sources.  相似文献   

16.
Semifluorinated n-alkanes (SFAs) with carbon chain lengths of 22 to approximately 36 atoms are present in fluorinated ski waxes to reduce the friction between ski base and snow, resulting in a better glide. Semifluorinated n-alkenes (SFAenes) are byproducts in the production process of SFAs and are also found in ski waxes. Snow and soil samples from a ski area in Sweden were taken after a large skiing competition and after snowmelt, respectively, and analyzed for SFAs and SFAenes. Single analyte concentrations in snow (analyzed as melt water) ranged from a few ng L−1 up to 300 μg L−1. ∑SFA concentrations decreased significantly from the start to the finish of the ski trail. Single analyte concentrations in soil ranged up to 9 ng g−1 dw. ∑SFA concentrations in soil did not show a trend along the ski trail. This may be due to the fact that concentrations in soil, although strongly influenced by the competition, reflect inputs during the whole skiing season. The chemical inventory in snow was greater than the inventory in soil for shorter chain SFAs (C22C28) and for all SFAenes. Additionally, a significant change in SFA patterns between snow and soil samples was found. These observations suggested volatilization of shorter chain SFAs and of SFAenes during snowmelt. Evidence for long-term accumulation of SFAs in surface soil over several skiing seasons was not found.  相似文献   

17.
Toxicity potentials are standard values used in life cycle assessment (LCA) to enable a comparison of toxic impacts between substances. In most cases, toxicity potentials are calculated with multi-media fate models. Until now, unrealistic system settings were used for these calculations. The present paper outlines an improved model to calculate toxicity potentials: the global nested multi-media fate, exposure and effects model USES-LCA. It is based on the Uniform System for the Evaluation of Substances 2.0 (USES 2.0). USES-LCA was used to calculate for 181 substances toxicity potentials for the six impact categories freshwater aquatic ecotoxicity, marine aquatic ecotoxicity, freshwater sediment ecotoxicity, marine sediment ecotoxicity, terrestrial ecotoxicity and human toxicity, after initial emission to the compartments air, freshwater, seawater, industrial soil and agricultural soil, respectively. Differences of several orders of magnitude were found between the new toxicity potentials and those calculated previously.  相似文献   

18.
Whelan MJ  Estrada E  van Egmond R 《Chemosphere》2004,57(10):1427-1437
Volatile methyl siloxanes break down in the atmosphere by reacting with OH radicals to form OH-substituted silanols. As the silanols become increasingly OH substituted they are increasingly likely to be removed from the atmosphere by wet and dry deposition. A simple equilibrium partitioning model was constructed to explore the relative rates of removal by different mechanisms (reaction vs. deposition) for siloxanes and their resultant silanols. A mass balance is calculated for the parent siloxane molecule and for each silanol, characterised by the number of OH substitutions. The model includes the effect of incomplete equilibrium between the vapour, adsorbed and dissolved phases of silanols in the atmosphere using a non-equilibrium factor (epsilon) expressing relative departure from equilibrium. Model results show: (1) maximum vapour-phase concentrations for non-substituted siloxanes and single-OH-substituted silanols; (2) maximum dissolved-phase and adsorbed-phase concentrations for two-OH-substituted silanols; (3) >99% of the original material will be removed in wet deposition and <1% in dry deposition as silanols. For increasing OH-substitutions, the decreasing concentration of precursor molecules (as a consequence of combined removal processes) means that concentrations are negligible, in all phases, beyond three or four substitutions. Predictions were relatively insensitive to assumed departures from phase equilibrium. Predictions of silanol hydrolysis in liquid water droplets suggest that the mix of diol chain lengths in precipitation may not be in thermodynamic equilibrium and will depend on atmospheric residence time and pH.  相似文献   

19.
K M Erstfeld 《Chemosphere》1999,39(10):1737-1769
The aquatic fate and persistence of synthetic pyrethroids under spray drift and field runoff treatment regimens were determined in outdoor pond microcosms. In this paper, the experimental design and construction of outdoor microcosms is presented, as well as the aquatic fate of tralomethrin and deltamethrin. Tralomethrin is rapidly degraded to deltamethrin, with a half-life of 12.7 hours under spray drift conditions. Degradation profiles of tralomethrin in water indicated rapid conversion of deltamethrin and to less active isomers and then to decamethrinic acid (BR2CA). After 24 hours, the percent radioactivity of tralomethrin was 25% of the test material in the water column. In sediment, tralomethrin was immediately converted to deltamethrin. Deltamethrin is rapidly degraded with a half-life of 8 to 48 hours, depending on mechanisms of introduction into water. Degradation profiles of deltamethrin in water indicated rapid conversion of deltamethrin to decamethrinic acid (BR2CA), comprising approximately 90% of the radioactivity in the aqueous phase at 168 hours. Extraction and analysis of fathead minnows (Pimephales promelas) after 96 hours revealed that tissue residues contained parent compounds and metabolites alpha-R-deltamethrin, trans-deltamethrin and Br2CA. Fish residues are directly related to aqueous concentrations, thus bioavailability under field runoff regimes were an order of magnitude lower than tissue residues under spray drift conditions. Plant tissue was found to significantly accumulate pyrethroids.  相似文献   

20.
Impacts of an old contaminated sawmill site located in Eastern Finland were studied, with emphasis on transportation and bioaccumulation of wood preservatives in the surrounding water system. To assess the transportation of chlorophenols and chromated copper arsenate (CCA) from the sawmill to the nearby lake, the concentrations of these compounds in selected sediment samples were analyzed. To assess the contribution of a pulp mill further upstream, the concentration of extractable organic halogens (EOX) was analyzed. Bioaccumulation of wood preservatives from sediments was examined using Lumbriculus variegatus as test organism. In sediments collected from the sawmill area, concentrations of chlorophenols, arsenic, chromium and copper were high. In the surrounding area the concentrations of these compounds were slightly elevated at some sampling points but were mostly within the natural range of variation. Thus, it can be concluded that transportation of wood preservatives from the sawmill area to its surroundings is fairly low. However, 60 microg/l of arsenic and 50 microg/l of copper were found in water taken from a brook that runs through a landfill area of the sawmill to the nearby river, and the concentration of arsenic in the surface sediment at one sampling point in the lake was slightly elevated. The total amount of organohalogens in sediment was higher in the river and the lake than in the sawmill area. Of all the wood preservatives studied, only arsenic was found to bioaccumulate in present conditions, reaching a tissue concentration of 362 microg/g dw in organisms exposed for 28 days to sediment from the brook. High concentration of arsenic in oligochaeta tissue was related to high concentration of arsenic in the pore water.  相似文献   

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