Specific accumulation and temporal trends of organochlorine contaminants in Dall's porpoises (Phocoenoides dalli) from Japanese coastal waters

Organochlorine compounds (OCs) such as polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane related compounds, hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), tris(4-chlorophenyl) methane (TCPMe) and tris(4-chlorophenyl) methanol were determined in the blubber of Dall's porpoises (Phocoenoides dalli) collected from Japanese coastal waters in 1998/1999. Among OCs analyzed, PCBs were the predominant contaminants with concentrations ranging from 1.5 to 39 microg/g on a wet weight basis. OCs concentrations were relatively low and less variable in mature females possibly due to the lactational excretion from their bodies, while in males the concentrations were increased with body length. Concentrations and compositions of DDTs and HCHs showed significant differences between the truei-type population off the Pacific coast of northern Japan and dalli-type from the Sea of Japan/Okhotsk, suggesting its usefulness to discriminate different populations. OCs levels detected in truei-type porpoises collected in 1998/1999 were lower than those collected in 1984, except TCPMe. On the other hand, except DDTs, the residue levels of other organochlorines in dalli-type porpoises showed no significant decrease since 1984.     

Toxicological and chemical assessment of ordinance compounds in marine sediments and porewaters

Toxicological and chemical studies were performed with a silty and a sandy marine sediment spiked with 2,6-dinitrotoluene (2,6-DNT), 2,4,6-trinitrophenylmethylnitramine (tetryl), or 2,4,6-trinitrophenol (picric acid). Whole sediment toxicity was analyzed by the 10-day survival test with the amphipod Ampelisca abdita, and porewater toxicity tests assessed macro-algae (Ulva fasciata) zoospore germination and germling growth, sea urchin (Arbacia punctulata) embryological development, and polychaete (Dinophilus gyrociliatus) survival and reproduction. Whole sediments spiked with 2,6-DNT were not toxic to amphipods. The fine-grained sediment spiked with tetryl was also not acutely toxic. The tetryl and picric acid LC50 values in the sandy sediment were 3.24 and 144 mg/kg dry weight, respectively. The fine-grained sediment spiked with picric acid generated a U-shaped concentration-response curve in the amphipod test, with increased survival both in the lowest and highest concentration. Grain-size distribution and organic carbon content strongly influenced the behavior of ordnance compounds in spiked sediments. Very low concentrations were measured in some of the treatments and irreversible binding and biodegradation are suggested as the processes responsible for the low measurements. Porewater toxicity varied with its sedimentary origin and with ordnance compound. The sea urchin embryological development test tended to be the least sensitive. Tetryl was the most toxic chemical in all porewater tests, and picric acid the least toxic. Samples spiked with 2,6-DNT contained a degradation product identified as 2-methyl-3-nitroaniline (also known as 2-amino-6-nitrotoluene), and unidentified peaks, possibly degradation products, were also seen in some of the picric acid- and tetryl-spiked samples. Degradation products may have played a role in observed toxicity.     

An analytical model for vapor‐phase volatile organic compound diffusion through landfill composite covers

One‐dimensional mathematical models for vapor‐phase volatile organic compound (VOC) diffusion through composite cover barriers are presented. An analytical solution to the model was obtained by the method of separation of variables. The results obtained by the proposed solution agree well with those obtained by a numerical analysis. Based on the proposed analytical model, the VOC breakthrough curves of five different composite covers are compared. The effects of degree of saturation of geosynthetic clay liner (GCL) or compacted clay liner (CCL) on VOC migration in the composite covers are then presented. Results show that the composite cover barriers provide much better diffusion barriers for VOC than the single CCL. The top surface steady‐state flux for a composite barrier, consisting of a 1.5 mm geomembrane (GM) and a 20 cm CCL, can be 8.3 times lower than that for a 30 cm CCL. The surface steady‐state flux for the case with (1.5 mm GM + 6 mm GCL) was found to be 2.3 times lower than that for the case with (1.5 mm GM + 20 cm CCL). The degree of saturation S_r of the CCL has a great influence on VOC migration in composite covers when S_r is larger than 0.5. The steady‐state flux at the surface of GM for the case with S_r = 0.7 can be 1.8 times lower than that for the case with S_r = 0.2. The proposed analytical model is relatively simple and can be used for verification of complicated numerical models, analysis of experimental data and performance assessment of composite cover barriers. Copyright © 2016 John Wiley & Sons, Ltd.     

Trends of persistent organic pollutants in the suspended matter of the River Rhine

Recently amended European (EU) water policies call for an adequate monitoring of the chemical status of sediments and suspended matter (SM) in rivers. In this study, we focus on long‐term time series of particle‐bound hexachlorobenzene (HCB) and selected polychlorinated biphenyls (PCB‐138 and PCB‐153) that were monitored biweekly to monthly at eight stations in the River Rhine catchment. Our aims are (1) to detect trends in the concentration series HCB, PCB‐138 and PCB‐153, (2) to estimate the uncertainty of loads caused by SM collection techniques and load calculation procedures and (3) to detect trends in the subsequently calculated annual load series. HCB concentration in the SM for the period 1995–2008 significantly (p < 0·01) decreased at six of the eight monitoring stations. Decreasing PCB‐138 and PCB‐153 concentrations are significant at six of the eight and seven of the eight monitoring stations, respectively. A two‐way analysis of variance (ANOVA) that tested the effect of two collection techniques and four load calculation procedures on annual loads indicates homogeneity of the methods at four of the five monitoring stations. At Weil, only the loads of HCB, PCB‐138 and PCB‐153 are significantly affected by the collection technique. The trend analysis of an extended series (1985–2007) of annual HCB loads at Koblenz showed a significant decrease from about 110 kg year^?1 to about 15–23 kg year^?1; however, in the shorter period (1995–2007) only at two of the eight monitoring stations decreasing trends of annual contaminant load could be detected. We conclude that any of the tested load calculation procedures can be applied, as loads do no differ systematically. Although a high uncertainty in load estimation exists (e.g. maximum percentage error of E = [18·1, 122·5]% for HCB), the monitoring programme at the Rhine is adequate for analysing the long‐term chemical status of SM. Copyright © 2011 John Wiley & Sons, Ltd.     

Use of magnetic measures to assess soil redistribution following deforestation in hilly region

Limited information is available about the use of magnetic susceptibility property to determine soil redistribution in hilly areas of the semi-arid regions. This study was conducted to evaluate the use of magnetic properties to determine soil redistribution along a hill slope following deforestation. The study area is located in the Quaternary hilly region of Lordegan district in west Iran. Ten transects were established in two land uses that included natural Querqus forested and cultivated lands. Soil samples were collected at different positions along the slope and magnetic properties (χlf, χhf, SIRM, ARM, and χfd) and selected physico-chemical properties were determined. The results (based on the χfd, SIRM/ARM) showed that the magnetic susceptibly in the calcareous materials is pre-dominantly derived during the pedogenic processes and the superparamagnetic particles which were transported to lower positions of hill slope following deforestation. The results confirmed that this methodology could be applied for monitoring soil redistribution along the slope in calcareous hilly areas in the semi-arid regions.     

山东地区三类典型制药企业的VOCs源成分谱及排放特征研究

制药行业因在提取等过程中使用有机溶剂排放大量挥发性有机物（VOCs）而备受关注.本研究在山东省选择化学合成、生物发酵、中药共三家制药企业开展了107种VOCs组分的监测和分析,并建立制药企业的VOCs源成分谱.研究结果表明：化学合成类和生物发酵类制药企业排放总质量浓度均超过20 mg/m³,中药制药企业的样品的平均质量浓度相对较小,为902.66 μg/m³.本研究所分析的107种组分中,以含氧挥发性有机物（OVOCs）为主,三家企业均超过75%,其中,化学合成制药类卤代烃物种的占比较高.企业类型、生产环节、收集排放措施等是影响VOCs成分的重要因素.     

德州市冬季大气挥发性有机物污染特征及其对臭氧和二次有机气溶胶生成的贡献

利用气相色谱-质谱仪/火焰离子检测器（Online-GC-MS/FID）对2017年冬季山东德州大气中99种挥发性有机物（VOCs）进行连续测量,研究了VOCs浓度和组分特征、日变化趋势、来源及其对臭氧（O₃）、二次有机气溶胶（SOA）生成的贡献.结果表明,德州大气VOCs平均体积分数为（47.74±33.11）×10^-9,烷烃占比最大,为40.66%.总VOCs及其组分表现出早晚体积分数高、中午体积分数低的日变化规律.德州大气中丙烷、丙烯、苯及甲苯和二氯甲烷分别受到液化石油气挥发、生物质燃烧、机动车排放和溶剂使用等人为源的影响.反向轨迹模型分析发现,北方内陆气团对德州VOCs体积分数具有一定贡献.烷烃、烯烃、芳香烃的臭氧生成潜势分别为（34.87±33.60）、（120.48±118.76）和（59.77±94.14）μg/m³,乙烯、丙烯、甲苯和间/对二甲苯的贡献较大.芳香烃氧化主导了SOA生成,其贡献率为93.7%,甲苯、间/对二甲苯、苯对SOA生成的贡献最大.为解决大气复合污染问题、实现臭氧和PM_2.5协同控制,德州应重点控制甲苯、间/对二甲苯等芳香烃的排放.     

Coal mine workers' pneumoconiosis

 The fibrogenic and cytotoxic potential of coal mine dust is independent of the amount of quartz and other inorganic parameters. Results of coal petrographical and organic geochemical investigations of coals and coal mine dust from the Ruhr and Ibbenbüren Region of Germany demonstrate variations of organic dust amount possibly influencing these noxious properties. Coal mine dust of high rank coals is characterized by a pronounced fibrogenic risk. This risk, independent of the quantity of quartz, is probably based on shape variations of different coal macerals. With increasing coalification of the corresponding seam, the vitrinite is enriched in its dust; however, lower concentrations have been determined for inertinite. Vitrinite shows constant shapes and sizes independent of the rank of coal. Inertinite particles with elongated to fibrous shapes tend to larger sizes with increasing coalification. Strikingly, coal mine dust from miners' lungs with high degrees of coal mine workers' pneumoconiosis (CWP) is enriched in inertinite. In contrast, high cytotoxicities in cell tests are known for coal mine dust from low coalified coals. High concentrations of phenolic compounds can be extracted by dichloromethane from low coalified coal mine dust. These compounds, which are characterized by a high water solubility and therefore high bioavailability, explain the high cytotoxicities of coal mine dust. Contamination of dust by diesel emissions in the coal mine can act as additionally supporting parameters for extended cytotoxicities. Received: 18 August 1995 · Accepted: 15 October 1995     

Sulfur isotopic composition of individual organic compounds from Cariaco Basin sediments

Reactions between reduced inorganic sulfur and organic compounds are thought to be important for the preservation of organic matter (OM) in sediments, but the sulfurization process is poorly understood. Sulfur isotopes are potentially useful tracers of sulfurization reactions, which often occur in the presence of a strong porewater isotopic gradient driven by microbial sulfate reduction. Prior studies of bulk sedimentary OM indicate that sulfurized products are ³⁴S-enriched relative to coexisting sulfide, and experiments have produced ³⁴S-enriched organosulfur compounds. However, analytical limitations have prevented the relationship from being tested at the molecular level in natural environments. Here we apply a new method, coupled gas chromatography – inductively coupled plasma mass spectrometry, to measure the compound-specific sulfur isotopic compositions of volatile organosulfur compounds over a 6 m core of anoxic Cariaco Basin sediments. In contrast to current conceptual models, nearly all extractable organosulfur compounds were substantially depleted in ³⁴S relative to coexisting kerogen and porewater sulfide. We hypothesize that this ³⁴S depletion is due to a normal kinetic isotope effect during the initial formation of a carbon–sulfur bond and that the source of sulfur in this relatively irreversible reaction is most likely the bisulfide anion in sedimentary porewater. The ³⁴S-depleted products of irreversible bisulfide addition alone cannot explain the isotopic composition of total extractable or residual OM. Therefore, at least two different sulfurization pathways must operate in the Cariaco Basin, generating isotopically distinct products. Compound-specific sulfur isotope analysis thus provides new insights into the timescales and mechanisms of OM sulfurization.     

气相色谱法分析固体废物中苯酚类物质

通过一系列筛选实验,确定了一种使用国产毛细管色谱柱分离固体废弃物中苯酚类物质的气相色谱分析方法,固体废弃物中苯酚类物质的回收率均可达70%以上,5次测定的相对标准偏差RSD＜6%,检出限(mg/kg)苯酚为0.033,邻甲酚为0.039,对甲酚为0.046,间甲酚为0.054,可以满足固体废弃物中苯酚类物质测定的要求.