河流沉积物中有机污染物的分析研究进展

总结了近年来河流沉积物中有机污染物的研究进展 ,集中评述了国内有关沉积物中多环芳烃、有机氯农药和多氯联苯的分析研究现状 ,包括样品采集、样品前处理和样品分析 ,并对今后河流、湖泊及水库沉积物中污染物的分析工作作了展望     

Levels, distribution, and risk assessment of organochlorines in surficial sediments of the Red Sea coast, Egypt

The analyses of environmentally persistent pollutants like polychlorinated biphenyls (PCBs), hexachlorocyclohexane (HCH) isomers, and dichlorodiphenyltrichloroethane (DDT) and its metabolites in surficial sediment samples collected from 17 locations along with the coast of the Red Sea in Egypt were carried out using gas chromatography–mass spectrometry. Several potential organic contaminants from agricultural (e.g., DDT and its breakdown products, lindane, endrin, dieldrin, and endosulfan) and industrial (PCBs) sources were measured. The levels of 20 organochlorine pesticides (OCPs) and ten PCB congeners in sediment collected from 17 stations along ~1,200 km were investigated. Concentrations of PCBs, HCHs, DDTs, and cyclodienes ranged from 0.40 to 6.17, 0.01 to 0.09, n.d. to 0.46, and 0.08 to 0.90 ppb dry weight. Two statistical programs were applied on the data (principal component analysis, PCA, and cluster analysis, CA), and it was concluded that it is impossible to predict the distribution patterns of the OCPs in a contaminated area. Risk assessment of the organochlorines contaminated in the sediments of the studied area was investigated.     

水体沉积物中有毒有机污染物的监测研究进展

介绍了水体沉积物中有毒有机污染物监测的预处理技术,重点评述了我国水体沉积物中主要有毒有机污染物多环芳烃、多氯联苯和有机氯农药的监测研究现状,认为水体沉积物中有毒有机污染物研究领域今后发展的重点和方向是广泛开展国内主要河流、湖泊、海洋的监测研究和其在水体环境中的迁移及转化机理、生殖毒性以及污染消减与修复技术研究;加强新型预处理技术及其与大型仪器联用技术的研究;尽早建立水体沉积物中有毒有机污染物的监测方法标准及污染评价标准。     

Distribution of polychlorinated biphenyls and organochlorine pesticides in wild mussels from two different sites in central Croatian Adriatic coast

Levels of 24 organochlorine compounds were investigated in wild mussels collected at two locations (Krka estuary and Ka?tela Bay) on the Croatian Adriatic coast in 2003, 2005, 2006, 2007, and 2008. PCB and OCP ranges found at the two locations overlapped and followed similar profiles despite the differences between the two locations indicating that they share a common pollutants source. Among organochlorine pesticides, the dominant compound was DDT. Among indicator PCBs, the dominant compound was PCB-153, while PCB-118 was dominant among the remaining 11 congeners. Generally, the sum of six indicator PCBs was constantly greater than the sum of 11 congeners at both locations. α-HCH/γ-HCH and DDE/DDT ratios were below 1, indicating recent input of γ-HCH and DDT into the marine environment. In the investigated period, almost all organochlorine compounds reached the highest values in 2006. The levels of PCBs and OCPs in this study were considerably below the Croatian maximum permissible levels, confirming that they do not pose any threat for human health.     

Distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides in soils from the East Antarctic coast

Concentrations of hexachlorobenzene (HCB), alpha-, beta- and gamma-hexachlorocyclohexane (HCH) isomers, 6 o,p'-and p,p'-isomers of DDT and 28 PCB congeners have been measured in eleven soil samples and one lichen collected on the Eastern coast of Antarctica from 5 Russian stations. For samples with low concentrations of PCBs (range 0.20-0.41 ng g(-1) dry weight) and pesticides (0.86-4.69 ng g(-1) and 0.11-1.22 ng g(-1) dry weight for HCHs and DDTs, respectively), atmospheric long-range transport from Africa, South America or Australia was suggested as the sole source of contamination. The profile of PCB congeners was dominated by the more volatile tri-, tetra- and penta-PCBs congeners, thus supporting long-range transport hypothesis. Four samples contained moderate levels of PCBs (range 1.98-6.94 ng g(-1) dry weight) and variable concentrations of pesticides (gamma-HCH, p,p'-DDT and o,p'-DDT being the main contaminants). For samples with high concentrations of PCBs (range 90.26-157.45 ng g(-1)) and high concentrations of pesticides, the presence of high molecular weight PCB congeners such as: 153, 180, 187, 170 etc, strongly suggest a local source (biotic) of PCBs rather than atmospheric transport. It is likely that on a local scale, biotic focussing of pollutants, due to bird activities (nesting and excrement) can cause high contamination levels and become more significant than contaminant input via abiotic pathways.     

Determination of organochlorinated compounds and petroleum hydrocarbons in sediment sample IAEA-408. Results from a world-wide intercalibration exercise

A sediment sample from the intertidal mudflats of the Tagus estuary was prepared, homogenised and distributed globally to laboratories as the IAEA-408 intercomparison material for the analyses of organochlorinated pesticides, PCBs and petroleum hydrocarbons (PHs). A total of 48 laboratories from 36 countries reported their results. The data from participants show that there still remain some difficulties with the accurate determination of organic contaminants such as pesticides and polycyclic aromatic hydrocarbons (PAHs). More consistent interlaboratory results were obtained for PCBs congeners. The final results of this intercomparison exercise enable individual participants to assess their performance and, where necessary, to introduce appropriate modifications in their analytical procedures. Furthermore, as a series of statistical criteria was fulfilled for a number of compounds, the sample IAEA-408 can now be used as a reference material for quality control in the determination of some persistant organic pollutants (POPs) in marine sediment samples.     

利用Triolein半渗透膜采样技术测定洋河水中的优先污染物

应用Ｔｒｉｏｌｅｉｎ半渗透膜采样器采集了河北洋河宣化至官厅水库河段水样，根据测定采样器中多氯联苯污染物（ＰＣＢｓ）及其它优先污染物浓度，可以估算这些污染物在河段水体中的平均浓度。将结果与同时同地采集的水样，经萃取浓缩后分析得到的结果比较，发现对于不同类型污染物，二者符合程度不同。本研究证明半渗透膜被动采样技术可用于水中多氯联苯等难降解污染物的定量监测，有可能在我国的优先污染物监测工作中发挥作用     

Concentrations, distributions, and sources of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in bed sediments of the water reservoirs in Slovakia

Dredging water reservoirs is necessary to maintain accumulation capacity and to prevent floodings. As a first step, the quality of the bed sediments in water reservoirs must be determined before dredging operations. In this study, sediment samples from 34 stations of three selected water reservoirs (Zemplinska Sirava, Velke Kozmalovce, and Ruzin) were collected to investigate concentrations, distributions, and hazards of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) and to predict their possible sources. Total PCB concentrations were in the range of 20.4 to 2,325?ng/g. The maximum concentrations of PCBs were found in sediments from Zemplinska Sirava, which is in the vicinity of a former manufacturer of PCBs. The composition of PCBs was characterized by tri- and hexa-CB congeners, indicating the influence of contamination from the use of specific Delor mixtures, formerly produced and massively used on the territory of Slovakia. The data showed that the highest total PAH concentrations were associated with the sediments from the Velke Kozmalovce, ranging from 7,910 to 29,538?ng/g. On the other hand, the lowest total PAH concentrations (84?C631?ng/g of dry weight) were found in the sediments of Zemplinska Sirava, an important recreational area in eastern Slovakia. The distribution of individual PAHs was similar among the three water reservoirs, and this, together with principal component analysis and diagnostic PAH ratios, suggests mainly pyrolytic contamination of the sediments. However, petrogenic inputs appear to be important in the Zemplinska Sirava sediments.     

Impact of urbanization on the concentrations and distribution of organic contaminants in boreal lake sediments

The main goal of this study was to evaluate the impacts of a middle-sized Finnish urban area on the quality of sediments in an adjacent boreal lake. We investigated the sources and distribution of organic pollutants (polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs)) in the sediments from urban stormwater traps and from Lake Vesijärvi. Grab surface sediment samples were taken from Lake Vesijärvi at various distances (25–2,000 m) from four major stormwater drainage outlets and at 15 urban stormwater traps in areas with different degrees of urbanization. These samples were analysed for 16 PAHs and 28 PCBs with gas chromatography–mass spectrometry. The concentrations of pollutants in the lake sediments were elevated in the vicinity of the urban shore (∑PAH 3–16, ∑PCB up to 0.02–0.3 mg/kg dw) and decreased as a function of distance (∑PAH 0.1–2.5, ∑PCB 0.01–0.3 mg/kg dw at a distance of more than 500 m from the shore), whereas contamination levels in suburban areas were notably lower (∑PAH 0.1–3, ∑PCB?<?LOQ–0.03 mg/kg dw; did not decline with distance). Possible sources and pathways of contamination were also investigated. The majority of stormwater trap sediments contained predominantly asphalt-derived PAHs due to pulverized pavement. PAHs in lake sediments were of pyrogenic origin, including the combustion of gasoline, diesel and coal. Suggested pathways of lake contamination are urban runoff discharge, boat traffic and atmospheric deposition.     

An assessment of persistent organic pollutants in Scottish coastal and offshore marine environments

Concentrations of persistent organic pollutants (POPs), including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined in sediment and biota (fish liver) from around Scotland. The concentrations were investigated using assessment criteria developed by OSPAR and ICES. Organic contaminant concentrations, PAHs, PCBs and PBDEs in sediment, and PCBs and PBDEs in fish liver, were significantly higher in the Clyde compared to all other sea areas. This is mainly due to historic industrial inputs. Highest PCB and PAH concentrations were found in the strata furthest up the Clyde estuary, with concentrations of POPs in these strata being at levels such that there is an unacceptable risk of chronic effects occurring in marine species. Furthermore, for PAHs in Clyde sediment there was a significant negative gradient going from north to south towards the open sea. PAH and PCB concentrations in sediment and biota in all other Scottish sea areas (except for PCBs in sediment from East Scotland) were unlikely to give rise to pollution effects, being below relevant assessment criteria. Although no assessment criteria are available for PBDEs, the concentrations observed in Scottish sediments were low with all congeners below the limit of detection (LoD; 0.03 μg kg(-1) dry weight) in 140 out of a total of 307 samples analysed. Where PBDEs were detected, the dominant congeners were BDE47 and BDE99. PBDEs were detected in fish livers, although concentrations were less than 150 μg kg(-1) lipid weight in all sea areas except the Clyde where concentrations ranged between 8.9 and 2202 μg kg(-1) lipid weight. Few trends were detected in contaminant concentrations in biota or sediment at any Scottish site with more than five years data. Downward trends were detected in PAHs in sediment from the Clyde, Irish Sea and Minches and Malin Sea and PCBs in fish liver from the Moray Firth. Rules were developed for the aggregation of the contaminant data across a sea area. An overall assessment for each sea area was then assigned, looking at the frequency of sites or strata within each sea area that were above or below the relevant assessment criteria. Overall the status of the various sea areas, with respect to the assessed POPs, can be considered to be acceptable in that they were below concentrations likely to result in chronic effects for all sea areas except the Clyde.     

Retrospective monitoring of persistent organic pollutants,including PCBs,PBDEs, and polycyclic musks in blue mussels (Mytilus edulis) and sediments from New Bedford Harbor,Massachusetts, USA: 1991–2005

Blue mussels (Mytilus edulis) and sediments collected from 1991 to 2005 from New Bedford Harbor (NBH), MA, were analyzed for two polycyclic musks (HHCB or Galaxolide® and AHTN or Tonalide®), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs). HHCB and AHTN were found in mussel tissues at mean concentrations of 836 and 376 ng/g lipid weight (lw), respectively, which were two- to seven-fold higher than those found at a reference site. Mean concentrations of HHCB and AHTN in NBH sediments were 12 and 6.3 ng/g dry weight (dw), respectively. Four- and five-ringed PAHs, such as phenanthrene, anthracene, fluoranthene, and pyrene, collectively accounted for 61 % of the ∑PAHs concentrations in mussels from NBH. Mean ΣPCB concentrations in mussels from upper and lower NBH were 942 and 182 μg/g lw, respectively, and were dominated by tetra- and penta-chlorobiphenyl congeners, collectively accounting for 61 % of the ΣPCB concentrations. The mean concentration of ∑PBDEs in mussels from NBH was 277 ng/g lw, and no significant difference existed in the concentrations between upper and lower NBH. DDTs were the major OCP found in mussels, found at a mean concentration of 778 ng/g lw. The concentrations of HHCB, AHTN, ΣPBDEs, ΣPAHs, and DDTs in mussels decreased significantly (r ²?≥?0.56, p?≤?0.052) from 1991 to 2005. The concentrations of PCBs and chlordanes did not exhibit a decreasing trend in mussel tissues (r ²?<?0.50; p?>?0.076) from 1991 to 2005. Based on the temporal trends in the concentrations of HHCB, AHTN, ∑PAHs, and ∑PBDEs found in mussels from NBH, it was estimated that between 5.5 and 12 years were required for the concentrations of these compounds to decrease by half (i.e., environmental halving time) of the levels found in 1991.     

Sediment Contamination, by Habitat, in the Tampa Bay Estuarine System (1993–1999): PAHs, Pesticides and PCBs

More than 760 Tampa Bay (Florida, U.S.A.) sediment samples have been analyzed for organic contaminants (PAHs, organochlorine pesticides, and PCBs) since 1993. Data were analyzed to assess status by habitat (defined by overlapping salinity zones and sediment type). The habitats most degraded by PAHs and pesticides were generally located in lower salinity, fine-grained sediment habitats, which are typically confined to the Hillsborough River. PCB contamination was more common in mesohaline waters of the Palm and Hillsborough rivers. Higher salinity portions of the bay, where medium to coarse sand-sized sediments predominate, showed little evidence of contamination by PAHs, PCBs and pesticides other than lindane.     

Contaminant concentrations in whole-body fish and shellfish from US estuaries

Persistent bioaccumulative and toxic (PBT) pollutants are chemical contaminants that pose risks to ecosystems and human health. For these reasons, available tissue contaminant data from the US EPA Environmental Monitoring and Assessment Program’s National Coastal Assessment were examined to estimate to what areal extent PBTs are found in US estuarine resources. The data document composite, whole-body tissue chemical concentrations for 736 sampling sites across Northeast, Southeast, Gulf of Mexico, and West Coast estuaries. Tissue chemical concentrations were compared to US EPA non-cancer risk guidelines for recreational fishers, because of a lack of ecological guidelines for these chemical concentrations. Samples were analyzed for 23 PAH compounds, 21 PCB congeners, 6 DDT derivatives and metabolites, 14 chlorinated pesticides (other than DDT) and 13 metals, including mercury. Total PCBs were found to exceed recreational fisher guidelines most frequently (31% of samples evaluated), followed by mercury (29%), total PAHs (21%), and DDT and its metabolites, DDD and DDE (11%). Toxaphene, cadmium and dieldrin were found but in fewer than 1% of the samples.     

Assessment of polycyclic aromatic hydrocarbon influx and sediment contamination in an urbanized estuary

Sediments from the Patos Lagoon Estuary in Southern Brazil and sludge from incoming effluents were assessed for the distribution of polycyclic aromatic hydrocarbons (PAHs). Shallow sediments adjoining the City of Rio Grande were found to be contaminated by PAHs mainly near urban effluent discharge, as well as in the port area. Effluents clustered into four groups according to their sources (sewage, industrial, runoff, and mixed), with each demonstrating different contributions of PAHs to the estuary. There was a predominance of runoff and mixed sources. Navigation activity was the second most important source of PAHs to sediments. The PAHs ratio identified the origin of these contaminants as essentially pyrolytic. The impact of PAHs as a result of uncontrolled disposal or accidental discharge of PAH-rich residues was suggested for several points. These points were primarily near gas stations and motor workshops. In about 30% of sampled sediments, the concentration of benzo[a]pyrene surpassed the Threshold Effects Level adopted for marine environments.     

Occurrence,sources, and ecological risks of PBDEs,PCBs, OCPs,and PAHs in surface sediments of the Yangtze River Delta city cluster,China

Polybrominated diphenyl ethers (PBDEs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) in 25 surface sediments in three cities (Nantong, Wuxi, and Suzhou) in the Yangtze River Delta, eastern China were measured. The mean concentrations were 378, 45.8, 1.98, 4,002 ng/g for PBDEs, OCPs, PCBs, and PAHs, respectively. Their levels in the sediments in the three cities were generally consistent with the city industrialization. PBDEs and OCPs were markedly dominated by deca-BDE (>90 %) and DDTs (>70 %). A principle component analysis of the analytes identified three major factors suggesting different sources of the contaminants in the sediments. PBDEs and the organic carbon in the sediments have common sources from industrial activities; whereas OCPs and PCBs, correlated with the second factor, were mainly from historical sources. The third factor with loadings of PAHs is indicative of various combustion sources. Ecological risk assessment indicated that the potential highest risk is from DDTs, for which 22 sites exceed the effects range low (ERL) values and three sites exceed the effects range median (ERM) value.     

Persistent organic pollutants in sediment from the southern Baltic: risk assessment

The concentrations of organochlorine pesticides, PCBs, and PCDD/Fs were measured in sediment samples collected from the Gulf of Gdańsk, the Gdańsk Deep, the Vistula Lagoon and the off-shore waters in the southern Baltic Sea. The determinations were conducted in the fraction <63 μm. The highest levels of pollutants were found in sediments from the Gulf of Gdańsk and the Gdańsk Deep. In these sediments, concentrations of pp'-DDT and its metabolites (pp'-DDE and pp'-DDD) ranged from 2 to 11 μg kg(-1) dw. Concentrations of HCB were between 0.1 and 1.0 μg kg(-1) dw. Concentrations of the sum of α-, β-, γ-HCH were between 0.3 and 2.58 μg kg(-1) dw. Concentrations of marker PCBs ranged from about 2 to 11 μg kg(-1) dry weight. Total TEQ PCDD/F/dl-PCB values in the studied samples varied between 1 and 18 ng kg(-1) dw. The data were evaluated in terms of ecotoxicological criteria based on the environmental impact of the pollutant effects. Our research indicated that in the sediment from the southern Baltic Sea, the PCDD/F and PCBs occurred at concentrations which could be dangerous to marine organisms.     

Aliphatic and polycyclic aromatic hydrocarbons in the surface sediments of the Mediterranean: assessment and source recognition of petroleum hydrocarbons

Coastal marine sediment samples were collected from ten sampling stations along the Egyptian Mediterranean coast in April 2010. All sediment samples were analyzed for aliphatic (C7 to C34) and polycyclic aromatic hydrocarbons (PAHs) as well as total organic carbon (TOC) contents and grain size analysis. Total aliphatic hydrocarbons ranged from 1621.82 to 9069.99 ng/g (dry weight), while aromatic hydrocarbons (16 PAHs) varied between 208.69 and 1020.02 ng/g with an average of 530.68?±?225.86 ng/g?dwt. Good correlations observed between certain PAH concentrations allowed to identify its origin. The average TOC percent was varied from 0.13 to 1.46 %. Principal component analysis was used to determine the sources of hydrocarbon pollutants in sediments of Mediterranean. Additionally, special PAHs compound ratios suggest the petrogenic origins.     

A complex investigation of the extent of pollution in sediments of the Sava River: part 2: persistent organic pollutants

Sediment pollution of the biggest Danube tributary, the Sava River, was investigated within the sixth framework European Union project “Sava River Basin: Sustainable Use, Management and Protection of Resources” (SARIB). The extent of pollution was estimated by determining the amount of inorganic and persistent organic pollutants in sediment samples at 20 selected sampling sites along the Sava River. For the purpose of clarity, the findings are presented and published separately (part I: selected elements and part II: persistent organic pollutants). This study presents an investigation into the presence of organic pollutants in the Sava River sediment. According to the Water Framework Directive, the following persistent organic pollutants were investigated: polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), selected chlorinated pesticides and organotin compounds. The results reveal that PAHs were present in moderate concentrations (sum of 16 PAHs: up to 4,000 ng g^???1) and their concentrations increased downstream. Concen trations of PCB were low (sum of seven indicator PCBs: below 4 ng g^???1) and among the pesticides analyzed only p,p-dichlorodiphenyltrichloroethane was found in moderate concentrations at two sampling sites in Croatia (up to 3 ng g^???1) and hexachlorobenzene was found in a high concentration in the city of Belgrade (91 ng g^???1), although the use of these persistent pesticides has been banned for decades. Repeated sampling at the same location revealed point pollution near Belgrade. Among the organic pollutants surveyed, organotin compounds were not detected. Overall results reveal the presence of persistent organic pollutants in 20 of the Sava River sediments tested that is, in general, comparable or lower than the levels in the Danube River and other moderately polluted European rivers.     

Detecting and characterising sources of persistent organic pollutants (PAHs and PCBs) in surface sediments of an industrialized area (harbour of Trieste, northern Adriatic Sea)

A sediment sampling based on a two-dimensional mapping was performed in the harbour of Trieste (northern Adriatic Sea), considering 28 sites exposed to pollutant inputs from harbour and industrial activities. Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined in surface sediments, because these very persistent pollutants seem to be responsible for the depletion of benthic populations observed in this area. The correlation matrix indicates that PAHs and PCBs are non-correlated, and probably have different sources. Both cluster analysis performed on the sampling sites and graphical drawing of the PAH sediment contents make it possible to locate along the shoreline a band of more polluted sediments, clustered around a site facing a steelmaking factory, to be considered as the main source point for PAHs. The evaluation of phenanthrene to anthracene (P/AN) and fluoranthene to pyrene (FL/PY) ratios permits the assessment of the pyrolytic, industrial origin of these PAHs, rejecting a second possible source of hydrocarbons (i.e., an oil-pipeline terminal, situated near the steelmaking factory). Graphical drawing of the total PCB iso-concentrations reveals a different source-point for this other category of very persistent pollutants.     

Comparison of SFE with Soxhlet in the analyses of PCDD/PCDFs and PCBs in sediment

The efficiency of supercritical fluid extraction (SFE) for the isolation of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) from sediments was investigated by comparing SFE with Soxhlet. Five sediments obtained from an international interlaboratory study were used as a test material. SFE was performed with an automatic system where extracted analytes were collected by solid-phase trapping using carbon mixed with Celite as an adsorbent. For the first time, SFE of the most toxic PCBs, coplanar PCBs, was studied with real sediment samples. The majority of PCBs investigated, a total of 38 congeners from tri- to decachlorinated, were quantitatively extracted from sediment by SFE with pure CO2 at pressure 400 atm and temperature 100 degrees C. Under these conditions a successful extraction was obtained also for PCDD/PCDFs except for hepta- and octachlorinated congeners. Copper powder added to the sediment efficiently prevented the transfer of sulfur from the sample during SFE. The TEQs of both PCDD/PCDFs and PCBs obtained by SFE corresponded well with those obtained by the Soxhlet-based method. The reproducibility of SFE was high for both groups.