铁丝原位自转化-固相微萃取新涂层应用于萃取环境水样中多环芳烃的性能研究

多环芳烃(PAHs)是一类具有致癌作用且难以降解的持久性有机污染物,广泛存在于环境中。环境中痕量PAHs的直接分析往往因检测手段的检出限达不到要求而存在困难,需要结合分离富集手段。常规的样品前处理技术如索氏提取、液液萃取等存在耗时长、使用大量有机溶剂等问题。因此为了提高效率、避免对自然环境的二次污染,有必要开发一种简便、环境友好的新型样品前处理技术。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)等技术联用可实现复杂基质中痕量有机物的快速富集和检测。目前SPME技术的研究热点主要集中在改善涂层的萃取性能以及提高其机械强度方面。本文采用铁丝(IW)作为载体,同时又提供了铁离子来源,以原位自转化的方式在具有良好机械稳定性的铁丝上生长出一层多孔结构的金属有机骨架化合物多孔膜[MIL-53(Fe)];将其作为固相微萃取涂层[IW@MIL-53(Fe)],以7种难挥发的稠环PAHs作为目标分析物,以浸入式模式进行萃取,并结合GC-MS作为检测手段验证其萃取性能。结果表明:新涂层的萃取性能是商用100μm PDMS涂层的1～2倍,且涂层可稳定使用120次以上。该方法的检出限为0.03～2.25ng/L,线性范围为250～10000ng/L,相关系数为0.9903～0.9991。将建立的方法应用于自然水体中PAHs的检测,加标回收率为80.1%～108.5%。本研究不仅为高性能SPME涂层简单、快速制备提供了新思路,而且所建立的方法有望应用于水体中痕量有机污染物的准确和高灵敏检测。     

PAH-biodegradation potential of indigenous microorganisms: evidence from the respiratory activity of surface sediments in the Quanzhou Bay in China

Seven stations were established in the Quanzhou Bay (24.73°-24.96°N, 118.50°-118.70°E) in China on three cruises to determine the concentrations of polycyclic aromatic hydrocarbons (PAHs) and the numbers of PAH-degrading bacteria in surface sediments. Assessing the biodegradation poten- tial of indigenous microorganisms by measuring the respiratory intensity with the addition of PAHs in sediment samples was also one of the aims of this study. The results show that the total PAH concentrations of the sedimen...     

Seismic characteristics of a reef carbonate reservoir and implications for hydrocarbon exploration in deepwater of the Qiongdongnan Basin,northern South China Sea

Our analysis of approximately 40,000 km of multichannel 2-D seismic data, reef oil-field seismic data, and data from several boreholes led to the identification of two areas of reef carbonate reservoirs in deepwater areas (water depth ≥ 500 m) of the Qiongdongnan Basin (QDNB), northern South China Sea. High-resolution sequence stratigraphic analysis revealed that the transgressive and highstand system tracts of the mid-Miocene Meishan Formation in the Beijiao and Ledong–Lingshui Depressions developed reef carbonates. The seismic features of the reef carbonates in these two areas include chaotic bedding, intermittent internal reflections, chaotic or blank reflections, mounded reflections, and apparent amplitude anomalies, similar to the seismic characteristics of the LH11-1 reef reservoir in the Dongsha Uplift and Island Reef of the Salawati Basin, Indonesia, which house large oil fields. The impedance values of reefs in the Beijiao and Ledong–Lingshui Depressions are 8000–9000 g/cc × m/s. Impedance sections reveal that the impedance of the LH11-1 reef reservoir in the northern South China Sea is 8000–10000 g/cc × m/s, whereas that of pure limestone in BD23-1-1 is >10000 g/cc × m/s. The mid-Miocene paleogeography of the Beijiao Depression was dominated by offshore and neritic environments, with only part of the southern Beijiao uplift emergent at that time. The input of terrigenous sediments was relatively minor in this area, meaning that terrigenous source areas were insignificant in terms of the Beijiao Depression; reef carbonates were probably widely distributed throughout the depression, as with the Ledong–Lingshui Depression. The combined geological and geophysical data indicate that shelf margin atolls were well developed in the Beijiao Depression, as in the Ledong–Lingshui Depression where small-scale patch or pinnacle reefs developed. These reef carbonates are promising reservoirs, representing important targets for deepwater hydrocarbon exploration.     

Polycyclic aromatic hydrocarbons in water,mussels (Brachidontes sp., Tagelus sp.) and fish (Odontesthes sp.) from Bahía Blanca Estuary,Argentina

Polycyclic aromatic hydrocarbons (PAHs), one of the major groups of anthropogenic environmental pollutants, were firstly identified and measured in coastal waters, native mussels and fish of an industrialized South American estuary.     

Distributions and sources of bulk organic matter and aliphatic hydrocarbons in surface sediments of the Bohai Sea, China

Surface sediment samples from a matrix of fifty-five sites covering virtually the entire Bohai Sea (Bohai), China were analyzed for total organic carbon (TOC), total nitrogen (TN), n-alkanes, unresolved complex mixture (UCM), biomarkers and stable carbon isotopic composition (δ¹³C), and principal component analysis was performed for source identification of organic matter (OM). The distribution of organic carbon correlated well with sediment grain size with the finest sediments having the highest concentration, suggesting the influence of hydrodynamics on the accumulation of sedimentary organic matter (SOM). The corrected TOC/ON (organic nitrogen) ratios and δ¹³C indicated mixed marine and terrestrial sources of SOM. Results suggested that δ¹³C could be used as a potential indicator to observe the dispersion of Huanghe-derived sediments in Bohai. Total n-alkane concentrations varied over 10-fold from 0.39 to 4.94 μg g^− 1 (dry weight) with the maximum terrigenous/aquatic alkane ratio observed at the Huanghe River Estuary (HRE) due to more higher plant OM from riverine inputs. C₁₂–C₂₂ n-alkanes with even-to-odd predominance were observed in several central-eastern Bohai sites. The HRE and its adjacent area is the main sink for the Huanghe river-derived OC. The ubiquitous presence of UCM, biomarkers (hopanes and steranes) and PCA results indicated the presence of petroleum contamination in Bohai, mainly from offshore oil exploration, discharge of pollutants from rivers, shipping activities and atmospheric deposition.     

多环芳烃的海洋环境行为及其代谢产物的研究进展

多环芳烃是一类广泛存在于环境中的持久性有机污染物,具有"三致"作用.环境中多环芳烃的某些不完全代谢产物同样可能具有持久性,有些甚至比母体多环芳烃的毒性更强,有可能对环境造成更大的危害.本文介绍了近年来国内外有关多环芳烃的海洋环境行为及其代谢产物毒性方面的研究进展,并重点对代谢产物的分析方法,包括高效液相色谱、气相色谱、气相色谱-质谱联用和液相色谱-质谱联用等,进行了总结,最后对该领域的研究方向进行了展望.     

固相萃取-高效液相色谱-荧光检测法测定海水中的多环芳烃

建立了用固相萃取-高效液相色谱-荧光检测法测定海水中多环芳烃的方法,优化了色谱条件和萃取条件。除苊不能用荧光检测器检出外,其余15种多环芳烃的空白加标回收率在64.5%(苯并[g,h,i],茚并[1,2,3-cd]芘)～88.7%(苯并[a]蒽)之间,相对标准偏差(n=5)为4.9%(荧蒽,苯并[b]荧蒽)～11.1%(苯并[g,h,i],茚并[1,2,3-cd]芘),方法的检出限在0.72(蒽)～14.10 ng/L(荧蒽)之间,基本上达到了痕量分析的要求。利用该方法测得青岛湾表层海水中多环芳烃的浓度在0.125(苯并[k]荧蒽)～25.996 ng/L(萘)之间,但苯并[a]芘未检出。     

珠江虎门潮汐水道多环芳烃的分布、组成及来源分析

采用GF／F玻璃滤膜对珠江虎门潮汐水道水样进行过滤，分离出颗粒相和溶解相多环芳烃：定量分析结果显示，2001年洪、枯季水体中多环芳烃总最分别是786～2098ng／L和11360～34338ng／L，16种优控多环芳烃含量分别为223～614ng／L和6559～20031ng／L。广州前航道多环芳烃的含量高于狮子洋水样的含量：珠江虎门潮汐水道水体中多环芳烃的含量、分布具有明显的季节变化特征，枯季多环芳烃总量高于洪季1个数量级。多环芳烃的组成及其特祉参数分析表明，珠江虎门潮汐水道水体中多环芳烃主要来源于矿物燃料燃烧和汽车排放。     

Petroleum potential of Baikal deposits

We analyzed oils, gases, and bitumens of bottom sediments from natural shows on the southeastern shore of Lake Baikal, in the mouth of the Stvolovaya River near Capes Tolstyi and Gorevoi Utes. Based on a set of geological data, we have established that: (1) the lake oils underwent biodegradation to a variable degree: “Fresh” nondegraded paraffin oil floats up near Cape Gorevoi Utes; in the mouth of the Stvolovaya River and near Cape Tolstyi, aromatic-naphthene oil lacks n-alkanes, monomethyl alkanes, and acyclic isoprenoids; (2) Cenozoic oil originated from the organic matter of fresh-water basins with significant amounts of higher land plant remains, including angiosperm plants (oleanane), which suggests the lake or delta genesis of oil source formations of Cretaceous and younger ages. Judging from the carbon isotope composition (average δ¹³C = −43.84‰), methane from the bottom sediments near Cape Gorevoi Utes is catagenetic. The initial in-place resources in the Baikal sedimentary basins are estimated by the volumetric-statistical method at 500 mln tons of equivalent hydrocarbons.     

Polycyclic aromatic hydrocarbons (PAHs) in transplanted Manila clams (Tapes philippinarum) from the Lagoon of Venice as assessed by PAHs/shell weight index: A preliminary study

Variation of polycyclic aromatic hydrocarbons (PAHs) levels was assessed in Tapes philippinarum from the Lagoon of Venice. Clams were transplanted from a polluted area next to Porto Marghera to two rearing areas of the Southern Lagoon. Analyses of PAHs were made in sediments and clams by GC/MS at first sampling and after 30, 60 and 180 days. Principal component analysis was performed to elucidate bioaccumulation and depuration pattern and input sources. Biota-Sediment-Accumulation-Factor (BSAF) was applied to evaluate the PAHs input sources from sediment. Condition index was calculated to compare the seasonal variation of clam tissue to PAHs levels. To propose results not affected by seasonal changes in flesh weight of clams, the approach based on the calculation of PAHs/SW index was applied. From the results, it was concluded that PAHs/SW index is more recommendable to asses temporal variation of PAHs levels in Manila clams.