响应面法优化聚丙烯酸/腐殖酸/累托石吸附剂的制备条件

以累托石、丙烯酸及腐殖酸为原料制备出能同时吸附重金属和多环芳烃的吸附剂聚丙烯酸/腐殖酸/累托石,采用响应面试验设计法优化吸附剂的制备条件。利用Design Expert软件,建立了预测吸附剂对Cd2+、菲吸附量的二次回归模型,对回归模型进行了方差分析,并确定了吸附剂的最佳制备条件。结果表明,二次回归模型能较好地模拟Cd2+、菲的吸附量与影响因子丙烯酸中和度、引发剂量和交联剂量之间的关系。各因子对Cd2+吸附量的影响次序为:交联剂量>引发剂量>丙烯酸中和度;对菲吸附量的影响次序为引发剂量>交联剂量>丙烯酸中和度。吸附剂的最佳制备条件为:累托石、丙烯酸和腐殖酸三者的质量比为65∶30∶5,丙烯酸中和度、引发剂量和交联剂量分别为75.16%、2.57%和0.44%。在此优化条件下制备的吸附剂对Cd2+和菲的吸附量分别为170.19 mg/g和7.36 mg/g。     

Air quality assessment by tree bark biomonitoring in urban, industrial and rural environments of the Rhine Valley: PCDD/Fs, PCBs and trace metal evidence

Tree barks were used as biomonitors to evaluate past atmospheric pollution within and around the industrial zones of Strasbourg (France) and Kehl (Germany) in the Rhine Valley. The here estimated residence time for trace metals, PCBs and PCDD/Fs in tree bark is >10 years. Thus, all pollution observed by tree bark biomonitoring can be older than 10 years. The PCB baseline concentration (sum of seven PCB indicators (Σ₇PCB_ind)) determined on tree barks from a remote area in the Vosges mountains is 4 ng g⁻¹ and corresponds to 0.36 × 10⁻³ ng toxic equivalent (TEQ) g⁻¹ for the dioxin-like PCBs (DL-PCBs). The northern Rhine harbor suffered especially from steel plant, waste incinerator and thermal power plant emissions. The polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) concentrations analyzed in tree barks from this industrial area range between 392 and 1420 ng kg⁻¹ dry-weight (dw) corresponding to 3.9 ng TEQ_PCDD/Fs kg⁻¹ to 17.8 ng TEQ_PCDD/Fs kg⁻¹, respectively. Highest PCDD/F values of 7.2 ng TEQ kg⁻¹ to 17.8 ng TEQ kg⁻¹ have been observed close to and at a distance of <2 km southwest of the chemical waste incinerator. However, very close to this incinerator lowest TEQ dioxin-like PCB (TEQ_DL-PCB) values of 0.006 ng TEQ g⁻¹ have been found. On the other hand close to and southwest and northeast of the steel plant the values are comparatively higher and range between 0.011 ng TEQ g⁻¹ and 0.026 ng TEQ g⁻¹. However, even stronger Σ₇PCB_ind enrichments have been observed at a few places in the city center of Kehl, where ΣDL-PCB values of up to 0.11 ng TEQ g⁻¹ have been detected. These enrichments, however, are the result of ancient pollutions since recent long-term measurements at the same sites indicate that the atmospheric PCB concentrations are close to baseline. Emissions from an old landfill of waste and/or great fires might have been the reasons of these PCB enrichments. Other urban environments of the cities of Kehl and Strasbourg show significantly lower Σ₇PCB_ind concentrations. They suffer especially from road and river traffic and have typically Σ₇PCB_ind concentrations ranging from 11 ng g⁻¹ to 29 ng g⁻¹. The PCB concentration of 29 ng g⁻¹ has been found in tree bark close to the railway station of Strasbourg. Nevertheless, the corresponding TEQ_DL-PCB are low and range between 0.2 × 10⁻³ ng TEQ g⁻¹ and 7 × 10⁻³ ng TEQ g⁻¹. Samples collected near road traffic are enriched in Fe, Sb, Sn and Pb. Cd enrichments were found close to almost all types of industries. Rural environments not far from industrial sites suffered from organic and inorganic pollution. In this case, TEQ_DL-PCB values may reach up to 58 × 10⁻³ ng TEQ g⁻¹ and the corresponding V, Cr, Co, Ni, and Cd concentrations are comparatively high.     

The effects of dietary nickel on the detoxification enzymes, innate immunity and resistance to the fungus Beauveria bassiana in the larvae of the greater wax moth Galleria mellonella

In this study, we tested the effects of dietary nickel on the activity of glutathione S-transferase (GST), esterases, phenoloxidase, and encapsulation in the haemolymph of larvae of the greater wax moth Galleria mellonella. We also explored the effects of dietary nickel on larval resistance to infection by the fungus Beauveria bassiana. Larvae fed a low dose of nickel (10 μg g⁻¹) had significantly higher GST, phenoloxidase activity and encapsulation responses than controls fed on a nickel-free diet. We also found that larvae fed a sublethal dose of nickel (50 μg g⁻¹) had increased GST, esterase activity and encapsulation rates but decreased phenoloxidase activity. Although, a sublethal dose of dietary nickel enhanced innate immunity, we found that this reduced resistance against the real pathogen. Our results suggest that enhanced immunity and detoxification enzyme activity of insects may not be beneficial to resistance to fungal infection. It appears that there is a trade off between different resistance mechanisms in insects under different metal treatments.     

Atmospheric particle characterization, distribution, and deposition in Xi'an, Shaanxi Province, Central China

Physical characterization and chemical analysis of settled dusts collected in Xi’an from November 2007 to December 2008 show that (1) dust deposition rates ranged from 14.6 to 350.4 g m⁻² yr⁻¹. The average deposition rate (76.7 g m⁻² yr⁻¹) ranks the 11th out of 56 dust deposition rates observed throughout the world. The coal-burning power was the major particle source; (2) on average (except site 4), ∼10% of the settled dusts having size <2.6, ∼30% having size <10.5, and >70% having size <30 μm; (3) the concentrations for 20 out of 27 elements analyzed were upto 18 times higher than their soil background values in China. With such high deposition rates of dusts that contain elevated levels of toxic elements, actions should be taken to reduce emission and studies are needed to assess the potential impacts of settled particles on surface ecosystem, water resource, and human health in the area.     

Body metal concentrations and glycogen reserves in earthworms (Dendrobaena octaedra) from contaminated and uncontaminated forest soil

Stress originating from toxicants such as heavy metals can induce compensatory changes in the energy metabolism of organisms due to increased energy expenses associated with detoxification and excretion processes. These energy expenses may be reflected in the available energy reserves such as glycogen. In a field study the earthworm, Dendrobaena octaedra, was collected from polluted areas, and from unpolluted reference areas. If present in the environment, cadmium, lead and copper accumulated to high concentrations in D. octaedra. In contrast, other toxic metals such as aluminium, nickel and zinc appeared to be regulated and kept at low internal concentrations compared to soil concentrations. Lead, cadmium and copper accumulation did not correlate with glycogen reserves of individual worms. In contrast, aluminium, nickel and zinc were negatively correlated with glycogen reserves. These results suggest that coping with different metals in earthworms is associated with differential energy demands depending on the associated detoxification strategy.     

Plant communities in relation to flooding and soil contamination in a lowland Rhine River floodplain

Using canonical correspondence analysis (CCA), relationships were investigated between plant species composition and flooding characteristics, heavy metal contamination and soil properties in a lowland floodplain of the Rhine River. Floodplain elevation and yearly average flooding duration turned out to be more important for explaining variation in plant species composition than soil heavy metal contamination. Nevertheless, plant species richness and diversity showed a significant decrease with the level of contamination. As single heavy metal concentrations seemed mostly too low for causing phytotoxic effects in plants, this trend is possibly explained by additive effects of multiple contaminants or by the concomitant influences of contamination and non-chemical stressors like flooding. These results suggest that impacts of soil contamination on plants in floodplains could be larger than expected from mere soil concentrations. In general, these findings emphasize the relevance of analyzing effects of toxic substances in concert with the effects of other relevant stressors.     

大宝山矿区水体和沉积物中重金属的污染评价

分别于丰水期和枯水期对广东省大宝山矿区铁龙拦泥坝至凉桥河段水体中溶解态的重金属进行了调查,应用EPA推荐的健康风险评价模型发现,水体中非致癌物通过饮水途径所导致平均个人年风险排列顺序是Cu〉Pb〉Zn,最大值的平均个人年风险在丰水期和枯水期的平均值分别是2.14×10-7 a-1和4.13×10-7 a-1,小于国际防辐射委员会（ICRP）推荐的最大可接受平均个人年风险5.0×10-5a-1。致癌物Cd的平均个人年风险在丰水期和枯水期的平均值分别是3.52×10-4 a-1和4.53×10-4 a-1,大于ICRP推荐的最大可接受值,同时也大于非致癌物3～4个数量级。另外,通过对枯水期沉积物的重金属总量分析,发现凉桥槽对坑支流受水体pH的影响,导致其沉积物重金属的浓度最高。根据Long和Macdonald利用生物效应数据库法建立的沉积物质量基准,发现除冷水泾外,其他采样点的平均效应中值指数（mERMQ）值都大于1.5,可见沉积物中的重金属会对当地底栖生物产生毒害作用。     

Concentration of trace elements in feathers of three Antarctic penguins: Geographical and interspecific differences

Antarctica is often considered as one of the last pristine regions, but it could be affected by pollution at global and local scale. Concentrations of Al, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Cd and Pb were determinated by ICP-MS in feathers (n = 207 individuals) of gentoo, chinstrap and Adélie penguin collected in 8 locations throughout the Antarctic Peninsula (2006-2007). The highest levels of several elements were found in samples from King George Island (8.08, 20.29 and 1.76 μg g⁻¹ dw for Cr, Cu and Pb, respectively) and Deception Island (203.13, 3.26 and 164.26 μg g⁻¹ dw for Al, Mn and Fe, respectively), where probably human activities and large-scale transport of pollutants contribute to increase metal levels. Concentrations of Cr, Mn, Cu, Se or Pb, which are similar to others found in different regions of the world, show that some areas in Antarctica are not utterly pristine.     

Marine and farmed fish on the Polish market: comparison of the nutritive value and human exposure to PCDD/Fs and other contaminants

Chemical analyses were performed in nine fish species that are popular on the Polish market. These included Baltic fish (cod, herring, salmon), fish farmed in Poland (carp, trout), marine fish imported from China (Alaska pollock, sole), and farmed fish imported from Vietnam and China (sutchi catfish, tilapia). The nutritional composition (amino acid, micro- and macronutrients, fat-soluble vitamins - A₁, D₃, E) and certain contaminants (organochlorine pesticides, OCPs; indicator polychlorinated biphenyl, PCB₆; polychlorinated dibenzo-paradioxins and polychlorinated dibenzofurans, PCDD/Fs; dioxin-like polychlorinated biphenyls, dl-PCBs; organotin compounds, OCTs; dyes, malachite green and crystal violet; veterinary drug residues, nitrofurans and chloramphenicol; toxic metals, Cd, Pb, Hg) in the muscle tissues of fish were determined. It was confirmed that the fish species analyzed were excellent sources of amino acids, and were rich in phosphorous and selenium. Baltic Sea fish (salmon, herring), fish farmed in Poland (carp and trout), and tilapia were also rich in vitamin D₃.Traces of OCP, PCB₆, OCT, dyes, veterinary drug residues, and heavy metals were detected in concentrations which do not pose a threat to consumers at the current rate of fish consumption in Poland. However, the problem might arise from the content of PCDD/Fs and dl-PCBs in fatty Baltic fish. The fish species analyzed, differed in their nutritional values and degrees of contamination. We suggest that for optimum health and safety, it is advisable that consumers include a variety of different fish species in their diets.