长江三角洲地区土壤环境质量与修复研究Ⅴ.废旧电子产品拆解场周边农田土壤含氯有机污染物残留特征

对长江三角洲地区某废旧电容器拆解场地周边农田基本保护区表层水稻土中含氯有机化合物的组成及含量进行初步研究。结果表明,供试土壤中20种PCBs总含量在84.19~377.4μg kg-1之间,平均含量为204.8μg kg-1,其中二氯、三氯、四氯代同系物总和占总PCBs的73.7%~96.2%,存在着PCBs的外源输入。HCH的总含量为10.61~33.11μg kg-1,DDT总含量为11.36~33.28μg kg-1,残留水平较低,但β-HCH、γ-HCH、∑HCH和∑DDT的平均含量均高于荷兰土壤标准的目标值。此外,DDT与土壤有机碳呈显著负相关,而其他含氯有机化合物的含量并未呈现出与土壤有机碳的相关性。     

Organochlorine insecticide residues in the rain water in Delhi,India

Rain water samples were regularly collected from three sites, namely, Netaji Nagar, Moti Nagar and Town Hall within the Delhi city area from July, 1980 to June, 1982. The pesticide residues were adsorbed on polyurethane foam coated with 0.5 % DC-200 and subsequently extracted and analyzed for DDT, HCH and their metabolites/isomers. The concentration of total DDT ranged from 0.22 to 108 μg L^?1 with a mean value of 12.5 μg L^?1. The samples of rain water contained varying levels of 4,4-DDT, 2,4-DDT, 4,4-DDE, and 4,4-DDD. The 4,4-DDT, 4,4-DDE and 2,4-DDT were the main components of total DDT. The range of HCH residues in rain water was from 0.08 to 43 μg L^?1 with a mean of 5.3 μg L^?1. The residues of HCH consisted mainly of α- and γ-isomers with traces of β and δ-isomers. The α- and γ-isomers accounted for 76 and 24% of total HCH, respectively. The concentrations of DDT and HCH in rain water were generally less than 10 μg L^?1 and exceeded 10 in only 4 and 3 cases, respectively. The residues of these insecticides were generally higher during October to December. Residues of DDT were higher at Moti Nagar which is near a DDT factory. Residues of HCH were maximum at Town Hall, a commercial area of the city.     

Organochloride insecticide residues in air in Delhi,India

Regular monitoring of air at three different sites, namely, Netaji Nagar, Moti Nagar and Town Hall in the metropolitan city of Delhi, India from June, 1980 to May, 1982 revealed varying levels of residues of DDT and HCH. The concentration of total DDT residues varied from 4 to 232 ng m^?3 with an average of 60 ng m^?3. Total HCH ranged from 0 to 21797 ng m^?3 with an average of 438 ng m^?3. Comparatively higher levels of total DDT (73 ng M^?3) were detected at Moti Nagar, the site near a DDT factory. The total HCH was highest at Town Hall (931 ng m^?3). Normally, higher quantities of the residues of DDT and HCH were detected during October to December. The insecticide residues consisted mainly of p, p′-DDT, p, p′-DDE, o, p′-DDT and p, p′-DDD, α- and γ-HCH. Only p, p′-DDT and p, p′-DDE were detected in all the samples and accounted for the bulk of total DDT. The HCH residues were mainly due to the α-isomer. Generally the concentration of HCH was higher than DDT in the air samples collected during the survey.     

Congener-specific evaluation of biota-sediment accumulation factor model for HCHs and DDTs under small-scale in situ riverine condition

Purpose

The congener-specific biota-sediment accumulation factors (BSAFs) model for hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) was evaluated for four different freshwater fish species (Orienus plagiostomus, Tor putitora, Glyptothorax punjabensis, and Cyprinus carpio) in in situ riverine conditions of Kabul River, Pakistan.

Materials and methods

The congeners of HCH and DDT were quantified using gas chromatograph (GC-ECD). The BSAF for each congener (HCHs and DDTs) was calculated from paired observation of congener’s measured concentrations in fish and sediment taken at the same site. Pearson’s correlation and linear regression analyses were performed to determine the influence of sediment organic carbon fraction (f _soc ) and organism lipid fraction (f _lipid ) on BSAF, and the relationship between BSAFs and logarithm of octanol-water partition coefficients (log K _ows) of HCH and DDT congeners, respectively.

Results and discussion

The BSAFs for total HCH (t-HCH) and total DDT (t-DDT) ranged from 0.6 to 1.5 and from 0.2 to 1.6, respectively. The model was significantly influenced by both fish (p = 0.004) and chemical types (p = 0.002) at 95 % confidence level. The sediment organic carbon fraction (f _soc ) and fish lipid fraction (f _lipid ) had not-too-weak effects on BSAF values for all fish species. The BSAF values were linearly fitted with logarithmic octanol-water partition coefficients (log K _ows) of HCH and DDT congeners, despite the different chemical structures, and different compound class significant negative correlations between log K _ows and BSAF values were found, indicating that hydrophobicity is one of the key factors influencing the bioaccumulation potential of the investigated compounds.

Conclusions

The present study confirmed the applicability of the BSAF model as a screening tool for predicting bioaccumulation of sediment-associated HCH and DDT congeners in investigated fish species under small-scale in situ riverine conditions of Kabul River and suite the model for benthic fish (G. punjabensis) on the basis of the 25th and 75th percentiles of congener-specific BSAF values.

     

Levels of some high molecular chlorinated hydrocarbons in sediment samples from the eastern Adriatic coastal waters

It is well documented that synthetic chlorinated hydrocarbon residues are widespread through the oceanic ecosystem. The Adriatic Sea, as semi-enclosed body of water, is of special interest for an evaluation of the entry, extent and fate of the pollution by chlorinated hydrocarbons. Sediments samples were collected from 1976 to 1990 at seven areas and over forty stations located on the eastern Yugoslav coastal waters. Concentrations of chlorinated insecticides and polychlorinated biphenyls in surface sediment samples ranged from <0.1 to 93.9 for DDTs and from <0.5 to 294 μg kg^?1 for PCBs on dry weight basis. It is very important to stress that all these samples were analyzed from a single analytical group (mostly by the same analyst), using a uniform methodology. Total DDT and PCB concentration do not exhibit Gausian distribution in the investigated area and collecting period, so it is necessary to be very careful in interpreting the concentration data using parametric statistics. Very often, the pollutant levels in sediment samples differ significantly in samples collected at the same time at nearby stations.     

In Situ partitioning and biomagnification of mercury in industrially polluted Husainsagar Lake,Hyderabad, India

The distribution of Hg in water, sediment, plankton and fish along with the in situ biomagnification of the metal in Husainsagar Lake, India were measured. The concentration of Hg in the water was 10 μg L^?1 and exceeded the water quality criteria standards. Sediments of the lake at different sites had Hg concentrations several thousand fold more than that of the overlying water column and showed relationship with the water content of the wet sediment. Sediments in the lake acted as a `sink' for the metal. The concentrations of Hg increased from nanoplankton → phytoplankton -> zooplankton. Fish, an end organism in the food chain, had Hg concentrations higher than that of nanoplankton and lower than those of phytoplankton and zooplankton. This trend did not illustrate the expected pattern of food chain enrichment in the classical sense as noted for chlorinated hydrocarbons (DDT).     

Dyke-protected floodplains: A possible chemical time bomb?

For more than a century contaminated sediment has been deposited on the Rhine floodplains. Freshly deposited sediment samples from the regularly flooded dyke-protected floodplain were obtained in 1958, 1970, 1972, 1981 and 1988. Heavy metals and arsenic as well as chemically persistent organic micropollutants [polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB) and DDT derivatives] were determined in the air-dried samples stored in a specimen bank. Pollutant levels showed a tendency to decrease; for PCBs and HCB the highest levels were present in the 1970s. Concentrations exceed natural background levels and in some instances are well above alarm levels established for the Netherlands. Although a decrease has been seen in the average annual input of pollutants onto the floodplain, accumulation in the upper layer of the floodplain sediments continues. as a consequence of the general chemical characteristics of the sediment (high organic matter, calcium carbonate and clay contents) the pollutants remain tightly bound to the sediment particles. as the pollutant levels are high, changes which reduce the organic matter and calcium carbonate contents May, cause severe environmental problems: enhanced bioavailability and leaching of pollutants May, result from the increased solubilization of pollutants.     

Chlorinated pesticide occurrence in the Uruguay River (Argentina-Uruguay)

Water samples, collected trimonthly along the Uruguay River between February 1988 and December 1989, were analyzed for alpha- and gamma-HCH, heptachlor and its epoxide, aldrin, dieldrin, and the o-p′ and p-p′ isomers of DDE, DDD and DDT to assess the present status of the contamination in this South American region. In general, chlorinated pesticides were encountered at very low concentrations. HCH isomers were the most commonly detected compounds with concentrations ranging from the detection limits to 10 ng L^?1. Heptachlor, heptachlor epoxide, aldrin, dieldrin, p-p′ DDE and p-p′ DDT were occasionally encountered while o-p′ DDE, p-p′ DDD, o-p′ DDD and o-p′ DDT were never detected. Compared to previous studies in the area, the present data seems to indicate that there was a decrease in the concentrations of these compounds.     

肯尼亚水稻土和甘蔗地土壤中~(14)C-六氯苯和~(14)C-滴滴涕的自然消解

氯代持久性有机污染物的农田土壤污染呈现污染浓度低、面积大、新源污染不断输入的特点。农田土壤本身微生物种类丰富,对氯代有机污染物具有较大的降解潜力和未知性。本试验以典型高氯代和低氯代持久性有机污染物——六氯苯(HCB)和滴滴涕(DDT)为研究对象,结合~(14)C同位素示踪技术,研究HCB和DDT在热带水稻土和甘蔗地土壤的矿化现象,同时监测HCB和DDT在两种土壤中的挥发、降解产物以及结合残留。结果表明,经84 d好氧培养,HCB和DDT在两种土壤中的矿化量分别仅为0.14%和3%,低氯代有机污染物DDT的矿化速率显著高于高氯代有机污染物HCB。然而,两种土壤对HCB或DDT的矿化没有显著性差异。HCB或DDT在水稻土中的挥发量略微高于甘蔗地土壤,两种土壤中HCB和DDT的挥发量在0.1%~0.6%之间,表明挥发不是其主要的环境过程。在DDT污染水稻土和甘蔗地土壤中添加1.25%的堆肥增加了DDT在土壤中的矿化与结合残留,减少了DDT的挥发。本研究结果表明土壤在好氧条件下对氯代持久性有机污染物的自然消解能力非常弱,而有机肥的使用有助于土壤中持久性氯代有机污染物的矿化消除。     

Ambient concentration and precipitation scavenging of atmospheric organic pollutants

Trace organic compounds were measured in air and rainfall at a rural site in Texas. Chlorinated hydrocarbons and phthalic acid esters (PAEs) were present at concentrations of ng m^?3 in air and ng L^?1 in precipitation. The most abundant compounds measured in air were PAEs > toxaphene > chlordane > hexachlorocyclohexanes (HCHs) > others. In rainfall the concentration order was PAEs > toxaphene > HCHs > DDTs > chlordane >- PCBs > others. An inverse correlation between concentration and rainfall amount was observed for most compounds. A model of precipitation scavenging of these compounds considered both scavenging of gas-phase and particle-bound compounds from the atmosphere. Good agreement was obtained between theoretical and measured concentrations. Results indicate that scavenging of a small amount of particle-bound compound can account for >98% of wet deposition for insoluble organic pollutants. Gas-phase scavenging is important for the more soluble compounds such as HCH.     

堆肥对有机氯农药挥发和降解的效果

选用鸡粪和玉米秸秆为堆肥原料,进行高温好氧堆肥试验,研究了堆肥处理对六六六（HCH）和滴滴涕（DDT）挥发和降解的影响。研究表明,30 d内,堆肥过程的高温和通气条件导致HCH和DDT的挥发比例分别为20.6%、13.8%;扣除堆肥过程中高温和通气等因素对有机氯挥发的影响后,未添加菌剂处理HCH和DDT的降解率分别为37.2%和14.9%,添加菌剂处理HCH和DDT的降解率分别为42.1%和24.2%,与未添加菌剂处理差异显著;α-HCH、δ-HCH的降解率高于β-HCH、γ-HCH,pp'-DDT、op'-DDT的降解率高于pp'-DDD、pp'-DDE。试验结果说明,堆肥过程中高温和通气促使了HCH和DDT向气相中挥发,而该过程的生化反应有助于HCH和DDT等有机氯农药的降解。     

The use of comprehensive two-dimensional gas chromatography and structure–activity modeling for screening and preliminary risk assessment of organic contaminants in soil, sediment, and surface water

Purpose

This article aims to investigate the use and benefits of using comprehensive two-dimensional gas chromatography (GC?×?GC) and structure?Cactivity relationship modeling for screening and prioritization of organic contaminants in complex matrices. The benefit of applying comprehensive screening techniques to samples with high organic contaminant content is primarily that compounds with diverse physicochemical properties can be analyzed simultaneously. Here, a heavily contaminated industrial area was surveyed for organic pollutants by analyzing soil, sediment, and surface water samples. The hazard of the pollutants were ranked using SARs.

Material and methods

The water samples were liquid?Cliquid extracted using dichloromethane and directly analyzed by GC?× GC?Ctime-of-flight mass spectrometry (GC?×?GC?CTofMS). Soil and sediment samples were extracted with dichloromethane in an ultrasonic bath and subjected to gel permeation chromatography to eliminate lipids and humic matter. The low molecular weight fraction was then analyzed with GC?×?GC?CTofMS.

Results and discussion

More than 10,000 components were found in each sample, of which ca. 300 individual compounds were unambiguously identified using the National Institute of Standards and Technology mass spectra library and authentic reference standards. Alkanes, polycyclic aromatic hydrocarbons, and phthalates were generally the most abundant and were found in all matrices. In contrast, chlorinated compounds such as chlorophenols, biphenyls, and chlorinated pesticides were only detected in samples from a few hotspot regions. The toxicities of the most frequently detected compounds and of the compounds detected at the highest concentrations in samples from hotspot regions were estimated by ecological structure?Cactivity relationships. The ratio of the measured concentration to the predicted toxicity level was then calculated for each compound and used for an initial risk assessment in order to prioritize compounds for further transport and fate modeling, complementary measurements, and more advanced risk assessments.

Conclusions

The advantage of using of GC?×?GC?CTofMS for preliminary screenings of contaminated areas was evaluated at a polluted area in northern Sweden. The area was found to carry organic pollutants such as polyaromatic hydrocarbons, aliphatic hydrocarbons, polychlorinated biphenyls, phthalic compounds, and many chlorinated pesticides. Preliminary risk assessments indicate which compounds to use for subsequent remediation experiments based on their availability on the site or toxicity.     

Organic priority pollutants in groundwater and surface water at three landfills in north central Florida

The occurence of organic priority pollutants in groundwater and surface water impacted by municipal landfill leachate was studied at the Orange County Landfill in Orange County, Florida. The results of the investigation were compared to existing data from two municipal landfills in Alachua County, Florida. The investigation in Orange County evaluated existing wells and surface water stations through sampling of groundwater, surface water, sediment, and aquatic biota. Very few organic priority pollutants were detected. The constituents most frequently found were volatile organic compounds, particularly aromatic organic constituents. Volatile organic compounds were detected in groundwater at total concentrations of less than 100 Μg L^?1. Few base/neutral and acid extractable organic priority pollutants were detected. Data from the Alachua County landfills indicated the presence of volatile organic compounds in groundwater at both landfill sites but few organic priority pollutants in the base/neutral and acid extractable group were fouund. Any organic priority pollutants that were present in the solid waste as deposited were likely metabolized by microorganisms or otherwise degraded, sorbed on particulate matter, or diluted to such an extent as to be non-detected.     

Determination of Volatile Organic Compounds in Indoor Air of Buildings in Nuclear Power Plants, Taiwan

This study investigates the composition and concentrations of volatile organic compounds (VOCs) in air-conditioned office space and low-level waste (LLW) repository sites of nuclear power plants located in Taiwan. Air samples were collected in the office space and technical rooms of administration buildings of the three nuclear power plants and in LLW repository site using canisters. Thirty-six toxic organic compounds including aromatics, CFCs and chlorinated hydrocarbons were identified and quantified using gas chromatograph/mass spectrometer (GC/MS). The results indicated that the concentrations of most determined species were similar to that in urban areas; however, the air at the LLW building contained abundant trichlorotrifluoroethane (CFC-113), trichloroethylene, toluene, 1,2,4-trimethylbenzene and CFC-12 in concentrations markedly higher than the background levels. Only toluene and 1,2,4-trimethylbenzene were detected with low concentrations in the air of LLW repository site. In addition, comparison of the ambient air concentration at several major industries and urban atmosphere revealed that the nuclear power plants emitted and/or leaked higher concentration of chlorinated hydrocarbons among them.     

DDT and HCH Residues in Basmati Rice (Oryza sativa) Cultivated in Dehradun (India)

Organochlorine pesticides were used earlier for agricultureproduction. Their residues may still be present in soil and mayaccumulate in food crops, posing potential health problems to consumers. DDT, HCH, their isomers and metabolites were analyzedin samples of soil and rice plants collected from ten differentvillages of a well-known Basmati rice growing area in Dehradun.Residues of both pesticides were found in all samples ofsoil and different parts of rice plants except for a few grainsamples. Maximum residue was observed in husk and minimum ingrains. The average concentration of DDT in soil ranged from0.013 to 0.238 ppm. p,p′-DDE was the major metabolite (>63%). Theaverage concentration of DDT in rice grain varied from 0.002 to 0.040 ppm. o,p′-DDT was the main isomer (>93%). Theaverage concentration of HCH in soil ranged from 0.122 to 0.638 ppm. β-HCH was the predominant (43%) isomerfollowed by α-HCH (21%). The average HCH concentrationin rice grain ranged between 0.013 and 0.113 ppm. All four isomers were present in grains. The levels of DDT and CHCin grains were similar in magnitude as those from differentIndian states, but well below the maximum residue limit of 0.1 ppm for DDT and 0.05 ppm for HCH prescribed by the Government ofIndia and WHO/FAO. As such, the pesticide residue levels in thisexport commodity are not of hazardous nature.     

作物根系对土壤中老化HCH-DDT的富集作用

在室温条件下,采用盆栽试验方法研究了小麦和玉米作物根系对自然污染土壤中不同水平老化HCH、DDT的富集作用及其影响机制。通过连续提取,将根系富集的有机氯农药分为弱吸着、强吸着和吸收3种不同形态。结果表明,作物对老化HCH、DDT的富集存在选择性。在60d的试验周期内,玉米根系富集的HCH、DDT中55．4％～62．2％为根表强吸着,23．3％～36．9％为根内吸收;而小麦根系中HCH,DDT的73．8％-76．9％被根表强吸着,仅15．4％-20．5％可以进入根系组织内部。不同形态组分中异构体及代谢物的组成比例差异化明显,其中吸收态以β-HCH为主,强吸着态以P,p＇-DDT、p,p＇-DDE和P,p＇-DDD为主。随着土壤污染水平的增加,小麦和玉米根系对HCH、DDT的富集总浓度增加,而生物蓄积系数逆浓度梯度增加,小麦根系的富集能力强于玉米。在控制污染水平的条件下,作物根系对土壤老化HCH、DDT的富集量与其根系比表面积大小和总脂含量极显著正相关,而向根系深层组织运移的过程主要受总脂含量控制。     

Statistical models for the accumulation of PAH,chlorinated hydrocarbons and trace metals in epiphytic Hypnum cupressiforme

Concentrations of PAH (1.12-benzoperylene, 3.4-benzopyrene, fluoranthene), chlorinated hydrocarbons (α-BHC, lindane, PCB) and trace metals (Zn, Pb, Cu) in bulk precipitation, as well as PAH and trace metal concentrations in atmospheric dust samples from 14 sites in Bavaria, F.R.G. are presented for two vegetation periods (1979 and 1980). The same substances were also analyzed in epiphytic moss (Hypnum cupressiforme var. filiforme) sampled from tree trunks in October 1979 and 1980. Using mean immission values and the amount of precipitation as predictors and concentrations of pollutants in moss samples as criteria, a number of multiple regression models were computed in order to quantify the relationships between absolute air pollution data and accumulated trace substance values. Beta values of all variables help to determine whether bulk precipitation or atmospheric particulate matter has dominant influence on the uptake of trace substances by mosses. The study shows that epiphytic mosses can be used to monitor both heavy-metal, PAH and chlorinated hydrocarbons.     

Polychlorinated biphenyl uptake and translation by Spartina alterniflora loisel

This paper presents the findings of initial investigation of the role of Spartina alterniora Loisel. in the movement of chlorinated hydrocarbons. ¹⁴C-polychlorinated biphenyls and technical Aroclor® 1254 were used for the determinations. The findings demonstrate that Spartina accumulates ¹⁴C-radioactivity from sand and organic mud soil systems treated with ¹⁴C-PCB's. These findings also demonstrate that this plant has the capacity to accumulate ¹⁴C-radioactivity to levels elevated above that in the treated soil. Other experiments with Aroclor® 1254 demonstrate that cogeners of Aroclor® 1254 are present in Spartina stem and root extracts. These experiments also suggest that the chlorinated hydrocarbon uptake process is modulated by the plant and that this results in selective cogener uptake. The selectivity appears to be for the lesser chlorinated components of the commercial mixture. Overall, this study suggests that Spartina may act as an initial vector for mobilization of sediment bound chlorinated hydrocarbons to the estuarine food chain.     

Composition, Distribution, and Characterization of Organochlorine Pesticides in Sandstorm Depositions in Beijing, China

Sandstorms which distribute a great number of particles are a special atmospheric occurrence and are uncommon in northern China. This study was conducted to determine, for the first time, the concentration of organochlorine pesticides (OCPs) in sandstorm depositions. Samples were collected from urban areas of Beijing and a total of eight OCPs were measured. All samples contained OCP residues. The total hexachlorocyclohexane (HCHs) concentration ranged from 20.6 to 59.8ng g^?1 and the total dichlorodiphenyltrichloroethane (DDTs) concentration ranged from 12.0 to 14.3ng g^?1. Furthermore, increasing HCH contamination was observed from the northwest to the southeast and a uniform distribution of DDT contamination was discovered in Beijing. Analysis of the sources of contamination showed that HCHs in the sandstorm depositions were derived from a relatively old source of lindane, and DDTs mainly originated from an old source of dicofol in Beijing. The preliminary pollution assessment of the samples indicated that HCH levels might be categorized as low pollution and DDT levels might be categorized as no pollution. The present study suggests that sandstorm depositions may not produce the special risk of adverse health effect from OCPs for the residents of Beijing, China.     

Suspended matter and associated contaminants in Danish streams: a national analysis

Purpose

Suspended matter (SM) in streams is usually considered of minor importance in Danish environmental management. However, SM has some ecological effects as it may (1) clog fish spawning grounds and (2) act as an important agent for transport and exposure of biota to chemical substances, such as phosphorus and toxic inorganic (e.g. heavy metals) and organic (e.g. pesticides) substances.

Materials and methods

A large national data set of >?100,000 water samples analysed for SM and loss on ignition was investigated for spatial concentration patterns, sediment yields and temporal trends. Moreover, the importance of SM as a transport agent for phosphorus and heavy metals in streams was investigated through a correlation analysis.

Results and discussion

The mean suspended matter concentration (SMC) (including organic matter) amounted to 12 mg l^?1, with an organic content of 4.9 mg l^?1 (41%). A clear difference in SMC temporal trends over the sampling period was found between geographical regions. Sediment yields were calculated for all major catchments revealing low sediment yields (1–15 t km^?2 year^?1) compared to neighbouring countries and showed clear geographical patterns. Statistically significant relationships were established between SMCs, suspended sediment concentrations (SSCs) (excluding organic matter) and organic matter concentrations (OMCs) and particulate phosphorus (PP) concentrations, and again spatial patterns appeared. However, it was clearly shown that SMC/SSC/OMC could not be used as a robust, nationwide, indicator for PP concentrations. Analyses of the relationship between SMC and particle-bound heavy metal concentrations generally revealed weak correlations except for Pb and Ni (median R²?>?0.3).

Conclusions

Relatively low SM concentrations and sediment yields were found. SM is, in some geographical regions, an important transport agent for PP. Clear geographical patterns occurred in the relationships between SMC/SSC/OMC and both river water discharge and PP, as well as for sediment yields and for temporal trends in SMC.