城市污水中PCBs的分析及其QA/QC研究

报道了一种城市污水中痕量PCBs的分析方法,并进行了QA/QC研究,采用二氯甲烷萃取剂对城市污水进行液-液萃取,联合运用浓硫酸和硅胶层析柱将PCBs与杂质分离,以毛细管GC-ECD和内标法对PCBs定量.空白加标回收试验得出,PCBs的回收率为58%～125%,标准偏差为0.00173～0.00778μg/L,相对标准偏差为1.58%～12.43%.以实际城市污水作为加标基质,得出加入污水中的19种PCBs的分析方法回收率为57.6%～129.2%,方法的检测限为0.010～0.056μg/L,满足了US EPA对PCBs回收率要求.经过3次平行测定,测得实际城市污水中PCBs含有9种PCBs,PCBs总量的平均值为0.0235μg/L,相对标准偏差为9.63%,该分析方法所需的仪器简便、容易操作.     

弗罗里硅土净化和凝胶色谱净化在土壤苯并(a)芘测定中的应用

采用ASE萃取-弗罗里硅土净化-HPLC法和ASE萃取-GPC净化-HPLC法测定土壤中苯并(a)芘,并将2种方法的测定结果作比对。试验表明,方法在0.02 mg/L~0.500 mg/L之间线性良好,当取样量为10 g时,弗罗里硅土净化土壤样品方法检出限为8.93×10~(-5)mg/kg,平均加标回收率为72.7%~73.8%,3次测定结果的RSD为4.0%~4.5%;凝胶色谱净化土壤样品方法检出限为1.98×10~(-5)mg/kg,平均加标回收率为88.8%~90.2%,3次测定结果的RSD为2.1%~2.8%。     

SPE-GC-MS法测定地下水中26种有机氯农药

采用固相萃取(SPE)技术,结合气相色谱/质谱(GC-MS)选择离子检测法(SIM)对水样中26种有机氯农药(OCPs)进行提取、净化、浓缩前处理,优选了固相萃取小柱填料及萃取、净化条件,优化了GC-MS的工作参数,建立了地下水中26种有机氯农药的SPE-GC-MS分析方法。针对不同的组分,本法加标回收率为76.422%~112.512%,相对标准偏差为4.905%~15.524%,检出限为0.014~0.089μg/L。该方法操作简单,消耗费用低,分析速度快,具有较高的灵敏度和回收率。     

超高效液相色谱-串联质谱法同时检测溴代阻燃剂

采用Acquity BEH C18色谱柱,以甲醇-乙腈混合液和水为流动相,辅以电喷雾正离子模式多反应监测(MRM)进行定性定量分析,建立了一种同位素稀释超高效液相色谱-串联质谱(UPLC-MS/MS)同时检测四溴双酚A(TBBPA)、三-(2,3-二溴丙基)异氰脲酸酯(TBC)和3种六溴环十二烷(HBCD)异构体的方法。水样通过固相萃取进行净化,回收率达到85.3%~96.1%。土壤和底泥样品经加速溶剂萃取后,采用酸性硅胶和中性硅胶柱进行净化,回收率达到81.5%~102.7%。该方法对TBBPA、TBC、α-HBCD、β-HBCD、γ-HBCD在水和土壤中的检测限分别为1.0、1.2、2.0、0.8、1.2 ng/L和0.10、0.12、0.20、0.08、0.12 ng/g。     

自动净化-高分辨气相色谱/高分辨质谱测定废气中二(口恶)英

采用自动净化-高分辨气相色谱/高分辨质谱(HRGC/HRMS)测定废气中的17种2,3,7,8位取代的多氯代二噁英和呋喃(PCDD/Fs)。废气样品经索氏提取,DEXTech系统全自动净化,浓缩和定容后,以HRGC/HRMS对废气样品中的PCDD/Fs进行了定性和定量分析。结果表明,17种二噁英和呋喃采样内标平均回收率为93%~99%,提取内标平均回收率为80%~97%;17种二噁英和呋喃自动净化实测结果与手工净化测试结果基本一致。该方法不但满足相关国家标准要求,还极大提高了样品的净化速度,减少人体对有机试剂的暴露。     

凝胶渗透色谱-硅胶柱-气相色谱-负化学离子源质谱测定生物介质中49种BFRs类化合物

建立了生物介质内22种多溴联苯(PBBs)和27种多溴联苯醚(PBDEs)的净化和分析方法。通过分析不同时间段凝胶渗透色谱(GPC)洗脱液中49种化合物含量,得出不同化合物凝胶色谱洗脱曲线。样品经过凝胶渗透色谱-混合硅胶柱净化后,再使用GC-(NCI)/MS对样品进行检测。实验结果表明,PBBs和PBDEs检出限分别为0.02~0.88 pg/g和0.01~74.00 pg/g。对实验过程进行验证发现,样品不同浓度加标回收率为80%~120%,相对标准偏差小于20%。该方法具有良好的净化效果、准确度和精密度,拥有良好的线性范围及检出限,满足生物介质中溴代阻燃剂的检测分析实际要求。     

固相萃取-GC/MS法测定地表水中3-甲基吲哚

采用微球硅胶键合C_(18)固相萃取柱萃取水样中的3-甲基吲哚,并用气质联用法测定,方法在0 mg/L~10.0 mg/L范围内线性良好,方法检出限为0.2μg/L。空白水样3个质量浓度水平的加标回收率为89%~94%,7次测定结果的RSD为2.3%~6.9%。用该方法测定7个实际地表水样品,其中4个地表水样品检出3-甲基吲哚,地表水样的加标回收率为81.5%~97.0%。     

生物组织样品中微量多环芳烃的测定

采用快速溶剂萃取法(ASE)提取生物组织中的有机组分,经硅胶、氧化铝、凝胶色谱法(GPC)等净化除干扰后,进行GC MS分析。本法采用选择离子监测(SIM)采集数据,内标法定量,对24种多环芳烃进行了测定,检出限达到0.002～0.005mg kg,经过复杂前处理过程的方法回收率为58%～77%,样品的标准偏差小于15%。     

加速溶剂萃取-气相色谱质谱法同时测定土壤及沉积物中34种有机氯农药及18种多氯联苯类化合物

建立了加速溶剂萃取-气相色谱质谱法同时测定34种有机氯农药(OCPs)和18种多氯联苯类化合物(PCBs)的方法。当取样量为10. 0 g时,52种有机化合物的检出限为0. 03～0. 29μg/kg,以空白样品为基体进行加标回收试验,平均回收率为44. 7%～123. 0%,相对标准偏差(RSD,n=7)为1. 8%～21. 5%。该方法灵敏度高,实现了低浓度有机化合物的定量分析,分析结果准确可靠,满足土壤和沉积物中34种有机氯农药和18种多氯联苯类化合物分析的要求。     

快速溶剂萃取-气相色谱-串联质谱法测定底泥中的有机氯农药

采用快速溶剂萃取、中性硅胶-中性氧化铝复合柱对底泥样品进行提取和净化,采用气相色谱-串联质谱法测定底泥中的30种有机氯农药。该方法的检测限为0.01~0.05 μg/kg,加标回收率为80.6%~110.5%,样品重复测定6次,均能得到较好的精密度,其相对标准偏差小于20%。结果证明,该方法灵敏度高、重复性好、准确度高、且快速简便,完全满足底泥中有机氯农药的测定要求。     

Determination of Trace Organochlorinated Pesticides and Polychlorinated Biphenyls in Water

A modified steam distillation liquid-liquid extraction (SDE) device is developed for the enrichment of trace organochlorinated pesticides (OCPs) and polychlorinated biphenyls (PCBs) in up to one litre of water samples. One ml of n-hexane is sufficient to extract the analytes. The extract can be analysed directly by a capillary gas chromatography-electron capture detector. The recoveries range from 84.6 to 102.3% for OCPs and 80.5 to 106.2% for PCBs, respectively. Matrice materials such as lipids and humic substances were removed by the SDE method from the extract and no further cleanup and concentration steps were needed.     

Endocrine disrupting chemicals in New Orleans surface waters and Mississippi Sound sediments

Endocrine disrupting compounds (EDCs), represented by steroid hormones, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and bisphenol A have been determined in four sediment cores from the Gulf of Mexico, from New Orleans surface water (Lake Pontchartrain and Mississippi River), and from the influent and effluent of a New Orleans municipal sewage treatment plant. During the five-month monitoring of selected EDCs in the Mississippi River (MR) and Lake Pontchartrain (LP) in 2008, 21 of 29 OCPs in MR and 17 of 29 OCPs in LP were detected; bisphenol A was detected in all of the samples. Steroid hormones (estrone, 17β-estradiol and 17α-ethinylestradiol) were detected occasionally. Total EDC (OCPs + PCBs + steroid hormones + bisphenol A) concentrations in the two surface water samples were found to vary from 148 to 1112 ng L(-1). Strong correlation of the distribution of total OCPs, total PCBs and total EDCs between solid and water phases was found in LP, while moderate or no correlation existed in MR. OCPs, PCBs, steroid hormones, and bisphenol A were all detected in the ocean sediments, and total EDCs were measured in the range of 77 to 1796 ng g(-1) dry sediment weight. The EDCs were also found in untreated and treated municipal sewage samples with a removal efficiency of 83% for OCPs but no removal efficiency for 17α-ethinylestradiol.     

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.     

快速溶剂萃取-气相色谱/串联质谱法测定农作物中的有机氯农药

建立快速溶剂萃取,固相萃取柱净化,气相色谱/串联四极杆质谱检测分析农作物中23种有机氯农药残留的方法。以油菜为样品,加标浓度为5、10、25、50μg/kg时,平均回收率在72%~101%之间,相对标准偏差3%~14%(n=5)。8种农作物(莴笋、黄瓜、蒜苗、辣椒、油菜、茄子、玉米和水稻)加标浓度为25μg/kg时的平均回收率在71%~113%之间,相对标准偏差3%~16%(n=5)。方法检出限0.75~1.76μg/kg之间。     

Distribution and risk assessment of organochlorine contaminants in surface water from River Chenab, Pakistan

Concentrations in surface waters (including particulate phase) of the River Chenab ranged from 27-1100 ng L(-1) and 25-1200 ng L(-1) for OCPs and 7.7-110 ng L(-1) and 13-99 ng L(-1) for PCBs during summer and winter, respectively from 2007-2009. DDTs exhibited the highest concentration, followed by HCHs > chlordane > ∑(24)PCBs > ∑other OCPs. Different indicative ratios for organochlorines suggest that current use, long range transport and also past application of these chemicals contribute to the total burden. Statistical analysis highlighted agricultural and industrial activities and municipal waste disposal as main sources of OCPs and PCBs in the riverine ecosystem of the River Chenab. Risk Quotients (RQ(CCCs)) > 10 for DDTs and PCBs levels in collected water samples from the River Chenab suggest that risk from DDTs and PCBs is moderate to severe and fluxes calculated for OCPs and PCBs from the River Chenab to the Indus River were 7.5 tons per year and 1.0 tons per year, respectively.     

Heavy metals and organochlorinated compounds in the European eel (Anguilla anguilla) from the Adour estuary and associated wetlands (France)

Heavy metals and organic pollutants were investigated in the Adour estuary (South West France) and associated wetlands using the European eel (Anguilla anguilla) as a bioindicator. Heavy metals (Cu, Cd, Zn, Pb, and Ag) were measured in soft tissue of yellow eels. Mercury (total Hg and MeHg) and organochlorinated compounds (7 PCBs, 11 OCPs) were analysed in muscle. Concentrations in muscle were in agreement with moderately contaminated environments in Europe and were below the norms fixed for eel consumption for heavy metals and OCPs. Analyses of liver showed a higher pressure of Ag and Zn in the downstream estuary than in the freshwater sites whereas Cd was lower in the estuary probably because of the salinity influence. According to quality classes 100% of eels from freshwater sites indicated clean or slightly polluted environments. However, total mercury concentrations were close to the thresholds fixed by the European Community in the downstream estuary, whereas the sum of PCBs was found to be greatly above the fixed value. 100% of the individuals from the estuary were classified in quality classes corresponding to polluted or highly polluted sites. These first results highlight the need of further investigations focused on mercury and PCBs in this area taking the seasonal temperature influence into account for a better understanding of the pollution distribution and the possible threat on the eel population from the Adour basin.     

Monitoring and Assessment of Persistent Organochlorine Residues in Sediments from the Daliaohe River Watershed, Northeast of China

Surface sediment samples from 12 sites of the three selected rivers in Daliaohe River watershed (Hunhe River, Taizihe River and Daliaohe River) were analyzed with the objective of establishing sources and hazard of the organochlorinae pesticides (OCPs) and polychlorinated biphenyl (PCBs) in surface sediments. The total concentrations of OCPs varied from 3.06 to 23.24 ng g⁻¹. ∑HCH (α-HCH, β-HCH, δ-HCH, γ-HCH), ∑DDT (p, p′-DDE, p, p′-DDD, o, p′-DDT, p, p′-DDT) and ∑Cyclodiene (Heptachlor, Aldrin, Heptachlor epoxide, Dieldrin, Endrin) ranged from 1.86 to 21.48, 0.5 to 2.81 and 0.56 to 1.53 ng g⁻¹, respectively. Results of OCPs also illustrate that the most dominant pollutants among the OCPs was ∑HCH, and γ-HCH was the most dominant isomer in HCH, which was evidence of recent input of lindane. It possibly came from the runoff of polluted soils and long-scale transportation. Total PCB concentrations ranged between 1.88 and 16.88 ng g⁻¹. The peak concentrations of PCBs were found in sediments from station T5 and D3, which are in the vicinity of industrial areas and ferry, respectively. These data show a moderate level of OCPs and PCBs contaminations compared to that in other countries.     

Long-range atmospheric transport of persistent organochlorinated compounds from south and mainland south-eastern Asia to a remote mountain site in south-western China

A range of organochlorinated compounds have been consumed in China, India and the countries of mainland southeast Asia (MSA). Considering their persistence in the environment and ability in long-range atmospheric transport (LRAT), the potential outflow of these compounds from this region is therefore of great concern in the context of the global distribution of toxic chemicals. As part of a monitoring campaign aimed at investigating the LRAT of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) from southern China, MSA and northern India, atmospheric levels of OCPs and PCBs were measured once a week from October 2005 through December 2006 at Tengchong Mountain (TM), a remote site located in south-western China. The average concentrations of OCPs were found to be higher than those in other remote stations in the Arctic and the Tibetan plateau, except for α-hexachlorocyclohexane (α-HCH). A high level of β-HCH and low α-HCH/β-HCH ratio was attributed to an accidental release of β-HCH from unknown sources, besides obvious evidence of lindane (γ-HCH) and technical HCH usage. Temporal variations of chlordanes and endosulfan were related to the usage pattern of these compounds, as well as LRAT. In contrast, dichlorodiphenyltrichloroethane (DDT) exhibited a relatively minor seasonal variation. The OCP levels at the monitoring site were found to be related to the air parcel back trajectories on the basis of four distinct clusters. Elevated levels of HCHs and DDTs were observed when air parcels originated from northern India where considerable OCP usage was reported recently, while high levels of γ-HCH and TC (trans-chlordane) were mainly associated with air masses from southern China and northern MSA. The study highlighted the high background level of OCPs as well as their temporal patterns of trans-boundary LRAT in the MSA region.     

土壤和沉积物中多氯联苯单体测定的净化方法研究

对浓硫酸净化、铜粉脱硫、氟罗里硅土柱、硅胶柱、石墨碳柱等净化方法在土壤和沉积物多氮联苯单体测定中的应用进行了研究.浓硫酸对多氯联苯单体的净化回收率达92.4％～109％;氟罗里硅土柱用正己烷/丙酮混合溶液淋洗,净化洗脱液体积为8 mL～10 mL时,回收率达85.7％ ～ 108％;硅胶柱用正己烷淋洗,净化洗脱液体积为...     

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.