莱州湾表层沉积物中多氯联苯的测定方法及分布特征探究

以加速溶剂萃取法 (ASE)、索氏提取法/气相色谱法测定了莱州湾表层沉积物中的12种PCBs的浓度水平,探讨了它的分布特征并将两种方法进行了对比;同时测定了渤海湾北部海域表层沉积物中PCBs的含量,与莱州湾进行了比较。结果表明,莱州湾海域表层沉积物检测出8种多氯联苯(PCBs),浓度范围是N.D.~48.40 ng ·g ^-1dw。该海域多氯联苯的分布特征是近岸高,离岸低,由近岸向湾外延伸方向依次递减;渤海湾PCBs的浓度范围是0.15~68.30 ng ·g ^-1dw,和莱州湾差别不大。索氏提取法测定12种多氯联苯类化合物的基质加标回收率为78.00%~104.85%,相对标准偏差为0.95%~3.64%;加速溶剂萃取法的基质加标回收率为90.00%~102.00%,相对标准偏差为0.65%~2.75%;相对于渤海湾北部海域而言,莱州湾区域只是受到轻度污染,属于低风险生态区,不会对生物产生毒副作用;而前者则处于中度污染水平,可能会对生物产生毒副作用。     

南四湖表层沉积物中多氯联苯的空间分布特征

采用气相色谱-电子俘获检测(GC-ECD)方法对从南四湖湖区采集表层沉积物中的12种多氯联苯(PCBs)同系物进行了分析测定。PCBs的含量范围为7.84~42.8ng/g,主要以低氯代物为主。湖内各监测点位的PCBs浓度要高于入湖河口各监测点位;湖内各监测点位中,上级湖各点位的浓度要高于下级湖的点位。污染物来源分析表明,PCBs主要来自造纸漂白过程和焚烧炉排放。与类似水体相比,南四湖表层沉积物中PCBs含量属中低含量水平。整体而言,南四湖表层沉积物中PCBs的含量属于低生态风险水平。     

对卧龙自然保护区作为清洁背景地区研究POPs迁移规律的合理性分析

以卧龙自然保护区土壤中POPs的含量为研究对象,利用MS-MS方法测定POPs在该地区土壤中的含量,其中PCBs含量范围为0.046~1.14ng/g,DDT含量范围为0.42~8.88ng/g,HCH含量范围为0~56.61ng/g,HCB含量范围为7.77~28.41ng/g,并与它们在世界其他地区的含量进行比较,论证了其作为清洁对照区研究POPs迁移规律的合理性。     

沉积物中多氯联苯分析的纯化条件优化研究

比较了各种填料层析柱和洗脱液的差别,并根据有机溶剂使用量较少的样品纯化方案,建立了适用低有机质含量水体表层沉积物中不同极性多氯联苯(PCBs)的分析方法.结果表明,该方法检测限在0.11 ng/g～0.35 ng/g(干重)之间,对主要多氯联苯同族体的回收率是77.9%～112.1%.用该法分析了长江中下游水体表层沉积物中的PCBs,质控结果表明,该纯化方法的效果理想.     

全自动固相萃取-GC-MS/MS法测定水中多氯联苯

采用全自动固相萃取-气相色谱/三重四极杆串联质谱法(SPE-GC-MS/MS)分析水中7种指示性多氯联苯,通过优化测定条件,使PCBs在0.100μg/L～100μg/L范围内线性良好,方法检出限为0.07 ng/L～0.1 ng/L,回收率为72.1%～102%,RSD为5.8%～12.9%。将该方法用于实际水样测定,结果城市污水处理厂的出水中PCBs检出率较高,而废旧电容器封存点周边地表水易受到PCBs的污染。     

燃煤电厂煤中汞含量对烟气中汞排放水平的影响

对江苏省9家燃煤电厂入炉煤中ω（汞）及烟气中ρ（汞）进行了测试，结果表明，9家燃煤电厂入炉煤中ω（汞）为54．5～297 ng／g，平均值为139 ng／g，低于我国煤中ω（汞）的平均值（220 ng／g）。燃煤电厂排放烟气中ρ（汞）为0．08～16．97μg／m^3，远低于《火电厂大气污染物排放标准》（GB 13223－2011）汞及其化合物标准限值（30μg／m^3）。通过对燃煤电厂入炉煤中ω（汞）与最终排放的烟气中ρ（汞）进行分析，两者之间有一定的相关性。     

搬迁化工厂区土壤中多环芳烃污染及来源分析

分析南通某搬迁化工厂区土壤中16种优控多环芳烃（PAHs）污染物的含量特征及污染水平。结果表明，车间和仓库土壤中多环芳烃总量为200—300ng／g，在南通市耕地土壤污染水平范围内。停车场土壤中PAHs含量为3435ng／g，污染水平高于普通耕地，与交通干线两侧土壤相当，土壤中PAHs以4环及4环以上PAHs为主，为汽车尾气污染，若继续用于道路或停车场等功能无需进行PAHs修复。     

固相膜萃取-高效液相色谱法测定地下水中的多环芳烃

采用C18固相膜萃取对地下水中15种多环芳烃进行富集净化，以二氯甲烷作洗脱溶剂，高效液相色谱法，荧光检测器测定。对萃取、浓缩和色谱条件进行优化，在1．ooixg／L～40．0μg／L范围内测定标准系列溶液并绘制标准曲线，相关系数R2〉0．999；15种多环芳烃的仪器检出限为0．4ng／L～3．0ng／L；对地下水样品加标，平均回收率在75．7％～96．7％之间；标准溶液平行测定7次的RSD为3．1％～11．9％。     

毛细管低温吸附气相色谱法同时测定空气中痕量甲硫醇和硫化氢

建立了毛细管低温吸附气相色谱同时测定空气中痕量甲硫醇和硫化氢的方法，介绍了冷冻吸附装置的制备方法和样品冷凝吸附流程。甲硫醇和硫化氢分别在0.467ng～5.16ng和0.327ng～3.60ng范围内线性良好，当进样体积为1L时，检出限为0．205μg/m^3和0．213μg／m^3，空白加标平均回收率为88．6％和90．2％，RSD为6.0％和6．5％。     

氢化物原子荧光法同时测定地表水中砷和汞

用氢化物原子荧光法同时测定饮用水中As和Hg．通过选择最佳的条件，进行样品处理方法及酸度、干扰离子等的研究,结果方法的检出限：As为0．29ng／mL、Hg为0．05ng／mL，方法的精密度、相对标准偏差在6．8％以下，As、Hg加标回收率分别为85．7%～112．6％和82．6%～108．4％，标准物质的测定值和标准值相符。     

One-year monitoring survey of organic compounds (PAHs, PCBs, TBT), heavy metals and biomarkers in blue mussels from the Arcachon Bay, France

Marine mussels Mytilus sp. were transplanted on a monthly basis in cages over one year to oyster farms and harbours in the Arcachon Bay (France) in order to assess the water quality of the bay. Contaminant levels (organotin compounds, trace metals, PCBs and PAHs) were measured in tissues of transplanted mussels and mussels from a reference station, along with physiological parameters of the mussels (condition indexes, lipid content and dry weight). Four biomarkers (AChE: acetylcholinesterase activity, GST: gluthathione S-transferase activity, CAT: catalase activity and TBARS: thiobarbituric acid-reactive substance content) were also monitored. The remote stations monitored (oyster parks) exhibited no accumulation pattern of pollutants. Their respective concentrations therefore constitute a background level of the contamination in the bay ([TBT]= 30 ng Sn g(-1) dw, [SigmaHAPs]= 100 ng g(-1) dw, [SigmaPCBs]= 35 ng g(-1) dw). The elevated chemical contamination of the largest harbour of the bay, the Arcachon harbour, can be interpreted in terms of persistence of organotin compounds ([SigmaOTs]= 1500-2000 ng Sn g(-1) dw) and PAHs ([SigmaHAPs]= 4500-5000 ng g(-1) dw) in sediments and, to a lesser extent, of direct inputs of copper ([Cu]= 20 microg g(-1) dw in harbours versus 7 in oyster parks) and petrogenic PAHs ([methylphenanthrenes]= 1600 ng g(-1) dw in the dockyard versus 170 at the gas stations), related to the use of copper-based antifouling paints and to dockyard activity, respectively. However, the Arcachon Bay presents a low contamination level by PCBs and metals, including harbour stations. Furthermore, higher levels of other PAHs (particularly alkyl PAHs such as methylphenanthrenes/1600 ng g(-1) dw) not included in the 16 PAHs from the EPA priority list (usually studied in biomonitoring programmes/1500 ng g(-1) dw) in the Arcachon harbour underline the need to integrate these compounds in biomonitoring of highly PAH-polluted areas such as harbours in order to avoid misinterpretation of the biological responses observed. Biomarker responses were not able to discriminate the different chemical contamination levels recorded in the Arcachon Bay and rather reflected changes in environmental factors. Furthermore, the strong intraspecies variability of biological responses could be due to genetic differences of mussels from the Arcachon Bay. It is the first time that such an integrated monitoring is performed in the Arcachon Bay, also taking into account seasonal variations of chemical contents and biomarkers levels in mussel tissues.     

Distribution of Chlorinated Organic Pollutants in Harbor Sediments of Livorno (Italy): A Multivariate Approach to Evaluate Dredging Sediments

Dredging is a very important procedure for harbor management. InItaly the guidelines for the offshore dumping of dredged materials are issued by the Ministry of Environment. Theydescribed a few steps of dredging activities, such as thesampling strategy, but do not deal with limits or guide-valuesfor the chemical, physical and biological composition of theresulting sediments. The quality of dredged materials is mainlydependent on the presence of inorganic and organic pollutants.In particular, polychlorinated biphenyls (PCBs) and organo-chlorinated pesticides are seen as a high priority inmarine environment by international organizations because oftheir persistence, toxicity and bioaccumulation capacity.In this article the presence of some PCBs and organo-chlorinatedpesticides in sediment samples collected from the harbor ofLivorno (Northern Tyrrhenian Sea) was investigated. Theconcentration of HCHs, Aldrin, Chlordanes, DDEs, DDTs, and PCBsin 12 representative sites ranged between <1 g kg^–1and 95, 19, 32, 35, 107, and 111 g kg^–1, respectively.The application of univariate and multivariate statisticaltechniques, such as linear regression analysis and principalcomponent analysis, to the experimental data showed a differentdistribution of PCBs in the two sediment layers. On thecontrary, the vertical distribution of the other investigatedpollutants was more homogeneous and affected by randomvariability. The multivariate approach was an important tool to establish more rational criteria for the management of dredged materials.     

Assessing organic contaminant fluxes from contaminated sediments following dam removal in an urbanized river

In this study, methods and approaches were developed and tested to assess changes in contaminant fluxes resulting from dam removal in a riverine system. Sediment traps and passive samplers were deployed to measure particulate and dissolved polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the water column prior to and following removal of a small, low-head dam in the Pawtuxet River, an urbanized river located in Cranston, RI, USA. During the study, concentrations of particulate and dissolved PAHs ranged from 21.5 to 103 μg/g and from 68 to 164 ng/L, respectively. Overall, temporal trends of PAHs showed no increases in either dissolved or particulate phases following removal of the dam. Dissolved concentrations of PCBs were very low, remaining below 1.72 ng/L at all sites. Particulate PCB concentrations across sites and time showed slightly greater variability, ranging from 80 to 469 ng/g, but with no indication that dam removal influenced any increases. Particulate PAHs and PCBs were sampled continuously at the site located below the dam and did not show sustained increases in concentration resulting from dam removal. The employment of passive sampling technology and sediment traps was highly effective in monitoring the concentrations and flux of contaminants moving through the river system. Variations in river flow had no effect on the concentration of contaminants in the dissolved or particulate phases, but did influence the flux rate of contaminants exiting the river. Overall, dam removal did not cause measurable sediment disturbance or increase the concentration or fluxes of dissolved or particulate PAHs and PCBs. This is due in large part to low volumes of impounded sediment residing above the dam and highly armored sediments in the river channel, which limited erosion. Results from this study will be used to improve methods and approaches that assess the short- and long-term impacts ecological restoration activities such as dam removal have on the release and transport of sediment-bound contaminants.     

Survey and evaluation of contaminants in earthworms and in soils derived from dredged material at confined disposal facilities in the Great Lakes Region

Soils derived from dredged material were collected, together with earthworms from nine confined disposal facilities located in the Great Lakes Region. These samples were analyzed for 18 elements, 11 organochlorine pesticides, PCBs, and 24 polycyclic aromatic hydrocarbons. The concentrations detected in earthworms were evaluated in terms of their potential hazard to wildlife, which for the sake of the evaluation were assumed to prey entirely either on earthworms or on other soil invertebrates having similar concentrations. The soil concentrations (dry wt.) of the contaminants of greatest concern were <1.9 to 32 ppm Cd, <0.053 to 0.94 ppm Hg, 4.6 to 550 ppm Pb, and <0.1 to 1.0 ppm PCBs. The concentrations in earthworms (dry wt., ingested soil included) were as high as 91 ppm Cd, 1.6 ppm Hg, 200 ppm Pb, and 1.8 ppm PCBs. Based on laboratory toxicity studies of relatively sensitive species, and on concentration factors calculated from the earthworm and soil data, we estimated that lethal or serious sublethal effects on wildlife might be expected at concentrations of 10 ppm Cd, 3 ppm Hg, 670 ppm Pb, and 1.7 ppm PCBs in alkaline surface soils derived from dredged material. Concentrations of polycyclic aromatic hydrocarbons in earthworms were well below those in soil.     

三重串联四极杆气相质谱联用仪测定饮用水源地水体中的多氯联苯

建立了以液-液萃取、三重串联四极杆气相质谱多反应监测法同时测定饮用水源地水体中18种多氯联苯的方法,给出了测量线性范围,线性关系良好,相关系数大于0.998。水中加标浓度为1.00、5.00、10.0ng/L时,平均加标回收率分别为75.6%～96.0%、90.6%～105%和92.4%～102%,相对标准偏差分别为19.8%～11.8%、4.2%～12.9%和4.3%～9.9%,检出限为0.29～0.57ng/L。结果表明,在测定水体中痕量多氯联苯方面,三重串联四极杆气相质谱相对于气相色谱-电子捕获检测和气相色谱质谱-选择离子检测具有更高的灵敏度和准确度,具有更广泛的应用。     

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.     

Source and risk assessment of PCBs in sediments of Fenhe reservoir and watershed, China

The concentrations of polychlorinated biphenyls (PCBs) in sediments from the Fenhe reservoir and watershed were detected at 28 sites in wet and dry seasons. The ∑(123)PCBs ranged from n.d. to 126.49 ng g(-1) dw. The dominated congeners were tri-PCBs (34.29%) and tetra-PCBs (24.05%). In the Fenhe reservoir, ∑(123)PCBs presented a decreasing trend, while percentages of low chlorinated congeners showed an increasing trend. For the temporal variations, PCBs homologues profiles of sediment samples and spatial distribution of ∑(123)PCBs for the two periods were similar (with CD = 0.021 and r(2) = 0.999 respectively), although PCBs concentrations in the wet season were significantly higher than in the dry season. PCA was applied to analyze the possible sources for PCBs, suggesting that PCBs might be mainly influenced by Aroclor 1016 and 1242. Compared with 3 established sediment quality guidelines, levels of PCBs in sediments of the investigated watershed might have a potential biological impact, especially in the wet season.     

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.     

Assessment of prenatal exposure to persistent organohalogen compounds from cord blood serum analysis in two Mediterranean populations (Valencia and Menorca)

Prenatal levels of organohalogen compounds (OHCs), including polybromodiphenyl ethers (PBDEs), polychlorobiphenyls (PCBs), hexachlorobenzene (HCB), hexachlorocyclohexanes and DDTs, have been investigated in two different cohorts from the Spanish Mediterranean area, Valencia and Menorca, by analysis of cord blood serum. Comparison of the observed median concentrations to other cohorts shows low PBDE levels (2.8-6.5 ng g(-1) lipid) but high values of HCB (0.68 ng ml(-1), 260 ng g(-1) lipid) and PCBs (0.65 ng ml(-1), 240 ng g(-1) lipid) in the cohort of Menorca indicating that Mediterranean areas, and not only high latitude regions, may contain population groups highly exposed to some of these pollutants. Significant differences in the concentrations of these compounds have been found between the two cohorts. Differences in maternal population such as age or body mass index cannot explain this variation. One possible cause of variability is the seven year time period elapsed between the two cohort recruitments but the strong differences observed do not allow exclusion of local diet differences. Thus, the different average PCB congener distributions between the two cohorts suggest an influence from materials containing diverse PCB mixtures. The congener mixtures found in Menorca could reflect a diet contribution from some western Mediterranean fish species. These results provide baseline information on prenatal OHC background levels in the Mediterranean area.