Using bald eagles to indicate the health of the Great Lakes' environment

The bald eagle (Haliaeetus leucocephalus) is one of the most studied birds of North America, and a great amount of natural life‐history information, including the response of various stressors on the eagles' ability to reproduce, are well known. In Michigan, the eagle has been chosen to track the trends of bioaccumulative compounds of concern across watersheds in the state. The state has been divided into major watersheds, and 20% of these are surveyed each year. A control area in northern Minnesota, Voyageurs National Park, is also sampled annually. We report here on the methods used, the preliminary results of the 1999 field season, and how differences in mercury concentrations varied over a 10‐year period. Mercury in feathers of nestling eagles declined over time only in Lakes Michigan and Huron, but have not decreased among other subpopulations in Michigan. Concentrations of polychlorinated biphenyls (PCBs) and 4,4′‐DDE in blood plasma from nestling eagles have declined over time for most subpopulations; however, they remain greater for breeding areas associated with the Great Lakes' food web. Sea eagles of the genus Haliaeetus are a good sentinel species to track trends in bioaccumulative compounds in aquatic systems.     

Organochlorine Contaminants of Wintering Ducks Foraging on Detroit River Sediments

Organochlorine analysis was performed on carcasses of 13 diving ducks from a 1981 wintering population that foraged on contaminated sediments in the lower Detroit River. Mean total PCB concentrations were 10 mg/kg for seven lesser scaups (Aythya affinis), 11 mg/kg for three greater scaups (A. marila), and 7.6 mg/kg for three goldeneyes (Bucephala clangula). Highest mean levels of other residues were measured for hexachlorobenzene (1.7 mg/kg) in goldeneyes, and transnonachlor (0.33 mg/kg) and 4,4’-DDE (1.3 mg/kg) in greater scaup. Quantitative analysis of 72 PCB congeners also was applied to water, seston, sediment, benthie oligochaetes, and carp from the same site. Principal congeners in most of the samples included some of the more toxic and persistent PCBs. Results of a multivariate analysis indicated that ratios of more conservative to less conservative PCBs did not vary significantly among ducks (α = .05), but differed from those in carp, oligochaetes, and sediment. For the February through March period of fat mobilization, concentrations of total PCB in lipid were inversely correlated with percent lipid (r = 0.76) in ducks. The percentage of conservative PCBs increased slightly. The distribution and partitioning of organochlorines, including toxic PCB congeners, varied considerably within this water column-sediment-fauna ecosystem. Estimates of toxic exposure based on total PCB values may be unreliable.     

Preliminary Assessment of Contaminants in Soft Sediments of the Detroit River

Soft sediments from the Detroit River were analyzed for the USEPA priority pollutants to generally characterize contaminant distribution. Forty-three were detected. Highest heavy metal concentrations were found in the Trenton Channel and immediately downstream of Grosse Ile. They ranged from an area mean (N = 2) of 0.19 mg/kg mercury to 338.7 mg/kg zinc (dry weight). Polynuclear aromatic hydrocarbons ranged from 0.1 mg/kg to 38.8 mg/kg (mean, N = 2) with the highest levels near Grosse Ile. PCBs ranged from 0.015 mg/kg to 1.7 mg/kg (mean, N = 2). Organochlorine pesticides were not detected except for a trace of heptachlor in one sample. Sediment contamination in the Detroit River is widespread with higher concentrations on the U.S. side downstream of the Rouge River and in the Trenton Channel. The significance of these in-place pollutants to biota and as a source to Lake Erie is still unknown.     

固相萃取净化-气相色谱-质谱法测定染料中7种指示性多氯联苯

本文建立了以固相萃取(SPE)前处理净化、结合气相色谱-质谱(GC-MS)测定染料中7种指示性多氯联苯的分析方法。该法将染料样品经溶剂萃取后,通过固相萃取(SPE)净化、浓缩,气相色谱-质谱采用选择离子监测模式(SIM)测定,以保留时间和特征离子定性,外标法定量。     

加速溶剂萃取/GC-ECD分析土壤中多氯联苯的研究

为研究加速溶剂萃取土壤中的多氯联苯的方法,以土壤中8种多氯联苯为标样,进行了加速溶剂提取实验,并用佛罗里硅土柱净化,再用GC ECD气相色谱仪测定。实验优化了萃取条件,在20 g土壤样中添加50 ng多氯联苯混标,在实验温度100℃,萃取压力为10.3 MPa,萃取时间为20 min条件下用35 mL丙酮/正己烷混合液提取,并用GCECD测得多氯联苯回收率为95.63%~100.2%;相对标准偏差为0.95%~9.58%;方法检出限为0.089~0.882 ng/g。为进行比较,同时进行了超声波辅助提取和索式提取实验。结果表明:加速溶剂提取时间短,有机溶剂用量少,并且提取回收率高。     

无机盐离子对鼠李糖脂增溶多氯联苯的影响研究

探讨了几种具代表性的无机盐离子对鼠李糖脂(RL)增溶2,2’,4,4’-四氯联苯的影响。结果表明,适当增加Na+、Mg2+、Ca2+的浓度对RL增溶2,2’,4,4’CB有显著的促进作用,且Mg2+的促进作用比Na+的大,但当Mg2+浓度大于0.8 mmol/L时,促进作用减弱。当Ca2+浓度超过0.2mmol/L时,RL开始产生沉淀,导致RL对2,2’,4,4’CB的增溶作用逐渐降低。无机阴离子对RL增溶2,2’,4,4’CB的影响很小。     

Partitioning of PCBs from air to clothing materials in a Danish apartment

Polychlorinated biphenyl (PCB) contamination of buildings continues to pose an exposure threat, even decades after their application in the form of calks and other building materials. In this research, we investigate the ability of clothing to sorb PCBs from contaminated air and thereby influence exposure. The equilibrium concentration of PCB‐28 and PCB‐52 was quantified for nine used clothing fabrics exposed for 56 days to air in a Danish apartment contaminated with PCBs. Fabric materials included pure materials such as cotton and polyester, or blends of polyester, cotton, viscose/rayon, and/or elastane. Air concentrations were fairly stable over the experimental period, with PCB‐28 ranging from 350 to 430 ng/m³ and PCB‐52 ranging from 460 to 550 ng/m³. Mass accumulated in fabric ranged from below detection limits to 4.5 mg/g of fabric. Cotton or materials containing elastane sorbed more than polyester materials on a mass basis. Mass‐normalized partition coefficients above detection limits ranged from 10^5.7 to 10^7.0 L/kg. Clothing acts as a reservoir for PCBs that extends dermal exposure, even when outside or in uncontaminated buildings.     

二噁英、多氯联苯和氯丙醇的痕量与超痕量检测技术研究

为建立食品中二噁英、多氯联苯和氯丙醇的检测技术并达到国际水平，将稳定性同位素稀释质谱技术应用到中国食品安全和环境分析领域，针对不同目标化合物分别建立了高分辩磁质谱、四极杆低分辩质谱和离子阱串联质谱的标准化检测技术，特别是采用双同位素稀释同时测定4种氯丙醇的技术。通过对EPA1613A／1668A、FDA4084和EPSI／RM／31、AOAC2000．01等国际先进方法用食品（鱼、鱼油、鹿肉、奶粉和猪油）和环境样品（飞灰、土壤和底泥）开展对比筛选和一系列实验室闻协同性验证，确立了二噁英和多氯联苯的稳定性同位素稀释质谱检测方法，建立了用双稳定性同位素进行酱油中单氯取代和双氯取代氯丙醇同时测定的方法，提出了符合国际规范的技术方案，作为国家标准方法待颁布。利用该检测技术在中国首次开展鱼贝类和土壤中污染的二噁英和多氯联苯同系物类型特征指纹库研究和酱油中氯丙醇的大规模调查，获得了中国人群膳食二噁英毒性当量和氯丙醇摄入状况的暴露数据，不仅证明所建立的方法实用、可行，也为我国履行承诺摸清了家底，提供了依据。     

Methods for determining pesticides and polychlorinated biphenyls in food samples--problems and challenges

Determination of residual amounts of pesticides and polychlorinated biphenyls (PCBs) in food samples requires the use of specific techniques regarding sample preparation as well as instrumental analysis which should be characterized by a very low detection limit. A problem associated with the use of pesticides and PCBs is the need for controlling their residues in the environment, particularly in food, as these chemicals show a propensity to accumulate. The analysis of food samples for the presence of pesticides and PCBs brings on many difficulties because of the specificity of sample preparation consisting of multistep purification procedures of samples that contain trace amounts of an analyte. Concentration determinations of pollutants that easily dissolve in complex matrices, particularly in the presence of a large apportionment of interfering substances, pose a big challenge. Therefore, the basic step in food analysis for the presence of pesticides and PCBs is sample preparation which mainly consists of analyte enrichment and the removal of interfering substances. But all steps of the analytical procedure that include sample collection and preparation, extraction of analytes from matrix, extract purification, and final determination, are very significant; their precision and correct application have a decisive effect on the final result.     

PCBs and OCPs in human milk and selected foods from Luqiao and Pingqiao in Zhejiang, China

This study was conducted to measure the levels of 23 PCB congeners and 6 organochlorine pesticides (OCPs) in human milk and three food types collected from Luqiao and Pingqiao in Zhejiang Province, China. An effort was also made to explore the potential health risk for the mothers and breast-fed infants living in these two localities. Luqiao was selected as the sampling site because it is the largest place for the disassembly of obsolete transformers and electrical waste in China. Pingqiao, located 100 km NW of Luqiao, is not known to be a place for any electronic or electrical waste and hence was chosen as the control site. Both localities are important agricultural places in the province. The organochlorines were measured in the samples using the GC-muECD technique. Micro-EROD bioassay method was also used as a complement of the chemical analysis to estimate the TEQ levels of dioxin-like PCBs in human milk. The data showed that the human milk, rice, hen egg, and fish samples from Luqiao were more heavily contaminated with PCBs than those from Pingqiao, suggesting that the mothers and their breast-fed infants in Luqiao tended to receive greater exposure to PCBs than those living in Pingqiao. The OCP levels in the two localities were found comparable, suggesting that the major source of contamination with these pesticides was from their agricultural uses. Significant correlation (R2 = 0.87, P<0.001) of PCB TEQs was found between the bioassay and chemical analysis method, suggesting that micro-EROD is an effective method for comprehensive determination of TEQ levels in human milk. Comparison with literature data showed that the PCB levels in milk samples from Luqiao were significantly higher than those from localities in other Chinese provinces and comparable to those in developed or industrialized countries.