Detailed analysis of polybrominated biphenyl congeners in bird eggs from Norway

Individual eggs of six species of birds from Norway representing different food chains were analysed for residues of polybrominated biphenyls (PBBs). In all species, the residue pattern was dominated by hexaBBs. The dominating congeners were PBB 153, PBB 154, and PBB 155. Whereas PBB 153 is present in technical hexabromobiphenyl, PBB 154 and PBB 155 are formed by the reductive debromination of decabromobiphenyl. This was evidenced by the detection of several heptaBBs and octaBBs all of which are typical degradation intermediates of PBB 209. Hepta- and octaBBs were more than one order of magnitude less abundant than the hexaBBs. The second most prevailing homologue group was pentaBBs. The most relevant pentabrominated isomers were PBB 99 and PBB 101. Concentrations of the three hexaBBs - PBB 153, PBB 154, and PBB 155 - amounted to 1.3-13 ng/g wet weight or 3-23% of the contamination with polybrominated diphenyl ethers.     

Anaerobic transformation of polybrominated biphenyls with the goal of identifying unknown hexabromobiphenyls in Baltic cod liver

Polybrominated biphenyls (PBBs) have been introduced as flame retardants in 1970. Despite decreasing application rates since the mid-1970s, PBB residues are still reported in the environment. Furthermore, environmental PBB residues often do not match the PBB pattern in technical products. To get insights into the structures of environmentally-relevant PBBs, the congener patterns of technical hexabromobiphenyl (THBB), octabromobiphenyl (TOBB), synthesized PBB 209 were compared to PBB residues in a cod liver sample from the Baltic Sea. The most relevant PBB congeners in Baltic cod liver were not present in the technical products and therefore most likely metabolites. For this reason, TOBB and HPLC-fractions obtained from this technical product were incubated with super-reduced cyanocobalamine. Reductive debromination was found to be the predominant transformation process. Bromine substituents in ortho-positions proved to be more recalcitrant, and several of the unknown PBBs were tri- and tetra-ortho substituted congeners. Furthermore, the key-PBBs determined in Baltic cod liver were formed during this process. The most important hexabromobiphenyl in Baltic cod liver was identified as PBB 155 by parallel synthesis. PBB 155 which was not detected in the technical PBB product analyzed was suggested as an indicator PBB congener suited to decide whether PBB residues originate from the previous use of THBB (low relative abundance of PBB 155) or TOBB/TDBB (high relative abundance of PBB 155). The latter scenario was found to be valid for the Baltic cod liver sample. Thus, PBBs in the Baltic Sea appeared to originate from partially-weathered residues of PBB 209.     

Determination of PCBs, PCDDs and PCDFs in insulating oil samples from stored Chinese electrical capacitors by HRGC/HRMS

Homologue and congener profiles of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in commercial PCBs formulations are key information for the source identification of PCBs contamination as well as for the risk assessment caused by potential exposure. The isotope dilution technology in combination with high resolution gas chromatography-high resolution mass spectrometry (HRGC/HRMS) has made the accurate determination of such profiles possible. So far, various commercial PCB formulations except Chinese products have been successfully determined. Two PCBs containing insulating oil samples from stored Chinese electrical capacitors have been determined with the same methodology for comparability. The total concentration PCBs in two oil samples were 790 000 μg g⁻¹ and 720 000 μg g⁻¹, respectively. TriCBs, TetraCBs, and DiCBs were found to be most abundant. Concentration of dioxins contamination in two samples is 650-670 ngTEQ g⁻¹, of which 69-71 ngTEQ g⁻¹ from PCDD/Fs with the predominant congeners of 1,2,7,8-TeCDF; 2,3,7,8-TeCDF; 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDF. The contributions of DL-PCBs in total TEQ in both samples were more than 85%. The dioxin-like toxicity in insulating oils contained in electrical capacitors could be considered receive attention as an important dioxins source if such wastes are not managed in an environmentally sound manner.     

Pilot-study on GIS-based risk modelling of a climate warming induced tertian malaria outbreak in Lower Saxony (Germany)

This project was designed to establish baseline aquatic biological community structure and physical habitat conditions in select wadeable streams within the California Central Valley. A secondary objective was to evaluate possible water quality differences between site types and seasons. Two agricultural and two urban streams were monitored in spring and fall for two consecutive years beginning in the fall of 2002. Bioassessment sampling was conducted according to modified US EPA methods. The study included physical habitat assessment, water and sediment chemical analysis and characterization of the benthic macroinvertebrate community at each site. Water samples were analyzed for selected organophosphate insecticides, pyrethroid insecticides and herbicides, while sediment samples were analyzed for pyrethroids only. All sites had substantial physical habitat and water quality impairments, and the absence of pollution intolerant macroinvertebrates and dominance of pollution tolerant macroinvertebrates were indications of biological impairment. Due to the limited amount of water quality and pesticide data collected, it was not possible to definitively demonstrate any cause and effect relationships between BMI community structure and water quality or pesticide concentrations. Though most physical habitat parameters were similar and EPA physical habitat scores revealed on no significant differences between urban and agricultural sites (P? = ?0.290), a significant difference was seen in substrate embeddedness (P? = ?0.020). Dominant taxon found at all sites were chironomids, amphipods, and oligochaetes. Benthic macroinvertebrate metrics were significantly different between both types of sites (P? = ?0.001) and seasons (P? = ?0.014). Chironomidae taxon and those of the functional feeding group scrapers were greater at urban sites, while those of the functional feeding group filterers were greater at agricultural sites. In addition, the metric groups Chironomidae, filterers, and predators were found in greater numbers in the spring than the fall.     

一种基于MMS的改进降水径流模型在中国西北地区黑河上游流域的应用

以黑河流域上游为研究对象,通过对山区自然产水区的产汇流机理的研究,基于分布式水文模型集成环境的开发思想,利用MMS(modular modeling system)模型库中与降水径流相关的模块,通过综合各种产流(包括超渗、蓄满产流)机理、并且根据寒区产汇流的特点对USGS开发的流域PRMS(precipitation-runoff models)模型进行了改进,增加了土壤水运动中降雨入渗补给的多层土壤滞后效应模块以及积雪融雪和冻土面积识别模型,建立了适合于寒区流域的分布式PRMS模型。利用该模型对黑河上游出山径流过程进行了模拟与预报,模型研究结果表明:利用MMS建立的黑河上游改进的PRMS模型不仅完全可以模拟和预测黑河上游的产汇流过程,在考虑了冻土的情况下,预测年出山径流量误差小于2.7%;而且模型可以对黑河上游径流组成成分进行分析计算,对黑河上游产汇流机理做进一步阐明。利用改进的PRMS模型,预测分析了黑河上游未来气候和土地覆盖变化情景下流域出山径流变化的趋势,为黑河流域水资源合理利用和管理提供科学依据。     

农户庭院型生态工艺原位处理源分离后的洗涤废水

选择长江三角洲地区有一定代表性的乡村家庭,开展了厌氧池-多级布水模块化人工湿地原位处理源分离后的废水的实例研究,旨在掌握乡村家庭源分离后废水的水质特征,并通过厌氧池-多级布水模块化人工湿地,重点解决乡村家庭源分离后的废水原位净化达标排放问题。结果表明,耗氧有机物(以COD计)、BOD₅、LAS (linear alkylbenzene sulfonates)是洗涤废水、灰水中的主要污染物质;季节变化、进水浓度对厌氧池-多级布水模块化人工湿地处理源分离后的废水中的耗氧有机物、LAS影响不显著,但季节变化对粪大肠菌群影响显著。总体上,2户农户的设施出水均符合《农田灌溉水质标准》(GB 5084-2005)水作作物的相关规定。     

Spatial variability of nitrous oxide and methane emissions from an MBT landfill in operation: Strong N2O hotspots at the working face

Mechanical biological treatment (MBT) is an effective technique, which removes organic carbon from municipal solid waste (MSW) prior to deposition. Thereby, methane (CH₄) production in the landfill is strongly mitigated. However, direct measurements of greenhouse gas emissions from full-scale MBT landfills have not been conducted so far. Thus, CH₄ and nitrous oxide (N₂O) emissions from a German MBT landfill in operation as well as their concentrations in the landfill gas (LFG) were measured. High N₂O emissions of 20–200 g CO₂ eq. m^?2 h^?1 magnitude (up to 428 mg N m^?2 h^?1) were observed within 20 m of the working face. CH₄ emissions were highest at the landfill zone located at a distance of 30–40 m from the working face, where they reached about 10 g CO₂ eq. m^?2 h^?1. The MBT material in this area has been deposited several weeks earlier. Maximum LFG concentration for N₂O was 24.000 ppmv in material below the emission hotspot. At a depth of 50 cm from the landfill surface a strong negative correlation between N₂O and CH₄ concentrations was observed. From this and from the distribution pattern of extractable ammonium, nitrite, and nitrate it has been concluded that strong N₂O production is associated with nitrification activity and the occurrence of nitrite and nitrate, which is initiated by oxygen input during waste deposition. Therefore, CH₄ mitigation measures, which often employ aeration, could result in a net increase of GHG emissions due to increased N₂O emissions, especially at MBT landfills.     

Schadstoff-Ferntransport in die Arktis

The Arctic is still considered as one of the few unpolluted regions in the world. This is true if one compares the Arctic region with middle latitude regions which are influenced more by human activities. However, the Arctic region is not isolated from all human impacts. In recent years, high concentrations of persistent pollutants (organic chemicals, metals) were detected in top predators of the Arctic food chain and indigenous peoples from the Canadian and Greenland Arctic, although no local contamination sources are known. The comprehensive, scientific investigation of the past 20 years confirmed that the combination of atmospheric and waterborne long-range transport is the major source of the high concentrations of persistent organic pollutants (POPs) in the pristine Arctic environment. However, also pelagic marine organisms (e.g. Atlantic cod, marine mammals) can transport large amounts of persistent pollutants in their lipids and introduce contaminants into the Arctic food web. Thus, the pollutants are transported into the Arctic and subsequently accumulated through the short and unbranched Arctic food web of the top predators. The most accepted theory nowadays describes the long-range transport of persistent pollutants as a combination of atmospheric and sea current transport, or as a ‘global distillation’ process. Depending on such physical properties of the substances as vapour pressure and the ambient tempeature, persistent (semivolatile) contaminants are transported over different distances prior to deposition (sea surface, sediment, soil). After the deposition, however, and depending on the weather conditions and surrounding temperature, persistent pollutants will be re-evaporated into the atmosphere and undergo further atmospheric transport to the Arctic region. This process is also called the ‘grasshopper effect’. The global transport of persistent pollutants into Arctic regions can be described as a repeatedly occurring combination of atmospheric and waterborne transport in which the main transport vehicle depends on the physical properties of the transported compound. The role of characteristic meteorological conditions in the respective climate zones through which the contaminant is transported must not be underestimated. Strong seasonal differences in temperature and precipitation rule the global weather situation. Therefore, seasonal pattern differences occur for the distribution of some persistent pollutants in the Arctic environment depending on average temperature, main wind and sea current directions, humidity and day time light conditions (causing photochemical degradation). The consumption of traditionally hunted marine mammals (seals, whales) was identified as one of the main reasons for high contamination burdens in the Canadian and Greenland Inuit populations. Consequences and counter measures against high contamination loads in the Arctic human populations and ecosystems are currently under discussion. However, no comprehensive measures concerning restrictions of hunting traditions are taken by the respective governments to date due to the primary social consequences which are to be expected. The advising experts argue that such a restriction would destroy the original social structures of the Inuit populations. Therefore, the drawbacks of such a hunting restriction would weigh heavier than the expected positive effects of the reduction of contaminant burdens ‘Arctic dilemma’.     

Biomonitoring of polychlorinated biphenyls in Bavaria/Germany—long-term observations and standardization

In the 1980s, it was demonstrated that semi-volatile organic compounds (SVOCs) like polychlorinated biphenyls (PCBs) accumulate in plant leaves. Plants are at the base of the food chain, and therefore a starting point for transfer of PCBs to animals and related human exposure. For two decades, the Environment Agency of the German federal state of Bavaria (LfU) has been operating long-term monitoring stations to measure the impact of organic air pollutants. Standardized ryegrass, curly kale, and spruce needles are used as bioindicators for the atmospheric entries of PCBs into vegetation. From the end of 1990s to 2009, there was a marked decline in the concentrations of indicator PCBs (i-PCBs) and a minor decline in PCB-TEQ levels. After 2009, the concentrations leveled off. In rural areas, the median concentrations of Σ6 i-PCB in ryegrass and curly kale were about 3 and 4 μg/kg dm in 2000, and have been about 0.5 and 1 μg/kg dm since 2009, respectively. Concentrations in spruce needles fell from 0.9 to 0.4 μg/kg dm. Median PCB-TEQ concentrations in the bioindicator plants ranged from 0.05 to 0.23 ng/kg dm between 2002 and 2009 and from 0.15 to 0.05 ng/kg dm after 2009. Indicator PCB and PCB-TEQ concentrations were several times higher at the urban station in Munich than at the rural areas, reflecting the emissions from in-use PCB stocks in the building sector. The likely reason of the slower decrease of PCB-TEQ compared to i-PCBs is the formation of PCB-126 by dechlorination of industrial PCBs in open applications.