海水中大分子有机质对铂族元素的吸附动力学研究

Adsorption kinetics of the interaction between Pt, Pd and Rh(defined here as platinum group elements, PGEs)ions and macromolecular organic compounds(MOCs, 10 kDa), including humic acid, carrageenan and bovine serum albumin, and different cutoff fractions of natural organic matter(1 kDa and 3 kDa) obtained from seawater using centrifugal ultrafiltration devices were investigated. For a given element, all the adsorption kinetics did not reach equilibrium except the interaction between Pt and 1 kDa cutoff, and between Pd and humic acid.For all the tested MOCs, the adsorption kinetics could be divided into two stages, a rapid adsorption process in the first 8 h and the desorption stage after the first 8 h until the equilibrium. The change trend of partition coefficient(log_(10)K_d) values with experiment time was consistent with that of the kinetic curves. However, in the interaction between PGE ions and natural dissolved organic matter(NDOM), an obvious difference in the change trends of log_(10)K_d and kinetic curves was observed. It indicated that the partition behavior of PGE ions interacting with NDOM in seawater was a combined effect of different organic constituents. The adsorption and log_(10)K_d of PGEs in the 1 kDa NDOM fraction were higher and more stable than those in the 3 kDa NDOM fraction. The results also indicated that the 1–3 kDa NDOM may dominate the interaction between PGEs ions and NDOM. Moreover, no kinetic model could perfectly simulate the adsorption process. It indicated that the colloidal struction and morphology of MOCs or NDOM in seawater might be inhomogeneous. Hence, the interaction between PGE ions and organic matter in seawater was a complicated process and needs further research.     

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.     

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.     

衍生化气相色谱-质谱法测定复垦土地样品中19种酚类污染物

酚类化合物是一类常见的环境污染物,由于浓度低、极性较强且样品基质复杂,对其分析检测前需采用样品前处理技术以进行有效地分离和富集。固相微萃取（SPME）是一种集采样、富集、进样于一体的无溶剂前处理技术,与气相色谱-质谱（GC-MS）等联用可实现复杂基质中痕量有机物的快速富集和检测。本文采用无溶剂合成策略,一步合成了氨基改性的共价有机骨架（COFs）材料（TpPa-NH₂）,合成方法简单绿色,无需溶剂。将其制备成SPME涂层,以5种酚类化合物作为目标分析物,基于顶空模式进行萃取,结合GC-MS作为检测手段,建立了SPME-GC-MS检测酚类化合物的新方法。与未氨基改性的TpPa-1涂层相比,TpPa-NH₂萃取酚类化合物的性能是其3~5倍,表明氨基官能团可有效地提高萃取酚类化合物的性能。在最佳条件下,该方法线性范围为10~5.0×10⁴ng/L,线性相关系数为0.996~0.999,检出限为1.30~5.35ng/L。涂层批内的相对标准偏差（RSD）在4.2%~8.9%之间,批间的RSD在2.6%~8.2%之间,且该涂层可以重复使用90次以上。基于TpPa-NH₂涂层材料建立的SPME-GC-MS检测酚类化合物的分析方法,已成功应用于环境水样标准物质中酚类化合物的检测。

     

珠江口盆地陆丰15披覆构造带油藏地球化学特征及油源对比

珠江口盆地陆丰15披覆构造带南、北部分别与陆丰22洼、陆丰15洼毗邻,常规的油源对比指标无法确定构造带上S2-1和S5-1油藏的油源,2个洼陷都有可能向其供烃。为揭示原油的成因来源,对该地区原油及烃源岩开展了生物标志物、碳同位素及含氮化合物等特征的精细对比。在研究区原油及源岩中新检测出4个C24四环萜烷：脱-A-奥利烷、脱-A-羽扇烷、新C24四环萜烷及C24 17,21-开环藿烷。研究对比发现,S2-1和S5-1油藏原油中C24四环萜烷分布特征与陆丰22洼文昌组烃源岩更加吻合,具有更强的亲缘关系。此外,全油碳同位素和正构烷烃单体烃碳同位素指示S2-1和S5-1油藏明显区别于陆丰15洼生成的原油,预示着其原油具有陆丰22洼烃源岩的贡献。含氮化合物示踪参数指示S2-1油藏具有近源充注特征,进一步验证了陆丰22洼烃源岩对S2-1和S5-1油藏的重要贡献。     

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.