Formation of dioxins during exposure of pesticide formulations to sunlight

Chlorinated pesticides can contain impurities of dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and their precursors, as a result of various manufacturing processes and conditions. As precursor formation of PCDD/Fs can also be mediated by ultraviolet light (UV), this study investigated whether PCDD/Fs are formed when currently used pesticides are exposed to natural sunlight. Formulations containing pentachloronitrobenzene (PCNB; n = 2) and 2,4-dichlorophenoxyacetic acid (2,4-D; n = 1) were exposed to sunlight in quartz tubes, and the concentration of 93 PCDD/F congeners were monitored over time. Considerable formation of PCDD/Fs was observed in both PCNB formulations (by up to 5600%, to a maximum concentration of 57 000 μg ∑PCDD/F kg⁻¹) as well as the 2,4-D formulation (by 3000%, to 140 μg ∑PCDD/F kg⁻¹). TEQ also increased by up to 980%, to a maximum concentration of 28 μg kg⁻¹ in PCNB, but did not change in the 2,4-D formulation. Assuming similar yields as observed in the present study as a worst case scenario the use of PCNB in Australia may result in the formation of 155 g TEQ annum⁻¹, contributed primarily by OCDD formation. This warrants detailed evaluations on the contemporary release of PCDD/Fs to the environment after the use of pesticides. Changes in congener profiles (including the ratio of PCDDs to PCDFs (DF ratio)) suggest that pesticide sources of PCDD/Fs after sunlight exposure may not be recognized based on matching source fingerprints established from manufacturing impurities. These changes also provide preliminary insights into the possible formation routes and types of precursors involved.     

The Forum of the International HCH and Pesticides Association—a platform for international cooperation

The unsustainable life cycle management of pesticides in the last 60 years has created large pesticide stockpiles. The two major working areas of the International HCH and Pesticide Association (IHPA; www.ihpa.info) address a part of these legacies and are shortly introduced here: (1) The assessment and support of the management of the worlds single largest POPs stockpile: the globally dumped 4 to 7 million tonnes hexachlorocyclohexane (HCH) wastes from lindane production, and (2) the support for the management of the obsolete pesticides legacy in Eastern Europe, the Caucasus and Central Asia (EECCA) countries of ~240,000 t, leaving these pesticides in unregulated storages without adequate safety control being a huge risk to the environment and human health. The integrative approach IHPA takes—promoting international cooperation and the exchange of knowledge and experiences—is shortly explained. IHPA has developed various supporting tools for its work: the IHPA web page and newsletter informing on the threats and challenges, but also on the progresses of managing pesticide stockpiles; the joint GIZ-PAN-IHPA exhibition on awareness of the pesticide stockpile challenge; and the ‘International HCH and Pesticides Forum’ as most important tool to progress the integrative work and mission of IHPA. Finally, a summary of the 11th International HCH and Pesticides Forum held in Gabala, Azerbaijan is given which brought together more than 120 scientists, policy-makers, non-governmental and international organisations, industry and students from more than 40 countries to progress the obsolete pesticides and hazardous chemical waste challenge in EECCA countries. The event finished with adoption of ‘Gabala Declaration’, which aims to mobilise efforts of all stakeholders for prevention and elimination of POPs, obsolete pesticides, and hazardous chemical waste in the region.     

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.     

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。     

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.     

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.     

Combustion features under different center of heat release of a diesel engine using dimethyl carbonate/diesel blend

Experiments were performed in a single cylinder common-rail diesel engine that adopts a low temperature premixed charge compression ignition (PCCI) mode. Combustion features of dimethyl carbonate (DMC)-diesel blends under various centers of heat release (COHRs) were revealed in details. With retarding of COHR, all the peaks of pressure and pressure rise rate and bulk gas temperature are postponed and declined in sequence. Normally, the crank angle of peak pressure is quite close to the COHR, while the peak of bulk gas temperature appears about 7°CA after COHR as a rule. The prolongation can be demonstrated at every stage of combustion such as q₁₀ and q₉₀ with the COHR being put backward. In addition, the heat release of diesel is completely slower than that of D10 fuel at various stages. Unfortunately, retarding of COHR implies a declining thermal efficiency of engines as well as a higher cyclic variation in general. Nevertheless, D10 blend has higher thermal efficiency than diesel thanks to high oxygen content of DMC and low boiling point that prompts better fuel atomization and complete combustion. Meanwhile, the cyclical variation of D10 is greater than diesel fuel owing to the low heat value, high latent heat of vaporization, and poor flammability of DMC. As a total, a comprehensive understanding of PCCI combustion features under different COHRs can be conducive to conducting effective management of combustion process and manipulating the subsequent emission performance to a favorable level.     

Increased metal concentrations in exhaled breath condensate of industrial welders

It was the aim of this study to evaluate the effect of different devices on the metal concentration in exhaled breath condensate (EBC) and to prove whether working conditions in different welding companies result in diverse composition of metallic elements. The influence of two collection devices (ECoScreen, ECoScreen2) on detection of metallic elements in EBC was evaluated in 24 control subjects. Properties of ECoScreen and a frequent use can alter EBC metal content due to contamination from metallic components. ECoScreen2 turned out to be favourable for metal assessment. Concentrations of iron, nickel and chromium in EBC sampled with ECoScreen2 were compared between non-exposed controls and industrial welders. Metal concentrations in EBC were higher in 36 welders recruited from three companies. Exposure to welding fumes could be demonstrated predominantly for increased iron concentrations. Concentrations of iron and nickel differed by working conditions, but chromium could not be detected in EBC.