Ab initio infra-red spectra of iron-polycyclic aromatic hydrocarbon compounds: a model case

C₁₀H₆-Fe⁺ complexes were observed by Fourier transform mass spectrometry by Marty et al. (Chem. Phys. Lett. 256 (1996) 669). In this article, we present the infra-red (IR) spectra of the two isomers calculated by ab initio methods of quantum chemistry. In the past, the same approach has predicted successfully unexpected features of the IR spectra of polycyclic aromatic hydrocarbon (PAH) cations which were confirmed by measurements in matrices (J. Phys. Chem. 98 (1994) 9187). The C₁₀H₆-Fe⁺ systems are models for larger PAHs-Fe⁺ complexes, which are believed to play a key rôle in space chemistry.     

徐州土壤多环芳烃的环境地球化学迁移特征

选择江苏徐州黄棕壤进行不同深度层位多环芳烃含量的定量分析,研究并探讨了多环芳烃在土壤深度剖面中的地球化学迁移特征。研究结果显示,多环芳烃在徐州土壤剖面中主要集中在地表0~20 cm内。其中低环多环芳烃化合物的迁移能力较强,4~6环等高环化合物相对较难迁移,主要残留于地表生态系统环境中。     

Development of two novel CYP-antibodies and their use in a PCB exposure experiment with Mytilus edulis

In an attempt to learn more about the cytochrome P450 (CYP) system of mussels, we used protein databases and alignment software to extract highly conserved CYP sequences. From these alignments synthetic peptides were produced and used for rabbit immunisation, which yielded polyclonal antibodies against the CYP families 2 and 4. The antibodies were evaluated with Western Blot and ELISA assays, using digestive gland microsomal samples from the mussel Mytilus edulis. Western Blots revealed immunoreactions for both antibodies. The anti-CYP2 sequence rendered one major immunopositive protein of ≈49 kDa size, and weak signals for proteins of ≈41 and 56 kDa size. The anti-CYP4 sequence rendered two major bands of ≈56 and 59 kDa size, and also a weak immunoreaction with a protein of ≈43 kDa size. ELISA rendered only weak signals even with a 1:50 dilution of IgG-purified serum. A 10-day exposure to Aroclor 1254 did not appear to affect any of the immunopositive proteins, while total PCBs in soft bodies increased from 14–40 ng/g DW in controls to 373–638 ng/g DW in exposed mussels.     

Photoinduced toxicity single and binary mixtures of four polycyclic aromatic hydrocarbons to the marine diatom Skeletonema costatum

Diatom Skeletonema costatum Cleve is one of the main predominant phytoplankton species in the Changjiang Estuary in China. In order to provide some basic information for future assessment of the potential risk on phytoplankton communities in this estuary caused by polycyclic aromatic hydrocarbons(PAHs), this alga was selected as a representative to investigate the photoinduced toxicity of PAHs, in single and mixture. Four PAHs including three-ring phenanthrene and anthracene, four-ring fluoranthene and pyrene were tested in the laboratory. The single toxicity of each PAH on this microalga was compared with and without the simulated solar UV radiation. The results showed that this microalga was sensitive to PAH's photoinduced toxicity. Ratios of the 72 h median effect concentration obtained for fluorescent and UV light tests were about 8.4 for phenanthrene, 13.0 for anthracene, 6.5 for fluoranthene, and 5.7 for pyrene, indicating that UV light enhanced the PAH toxicity to this alga significantly. Under the fluorescent radiation (lacking UV), the dose-response curves based on chemical concentrations revealed that the order of toxic strength was fluoranthene greater than pyrene greater than anthracene greater than phenanthrene; while under the UV radiation (476 μW/cm2 for UVA, 6.5 μW/cm2 for UVB) it became fluoranthene approximately equaling anthracene greater than pyrene greater than phenanthrene, indicating that the UV light also changed its relative toxicity to this alga. The photoinduced toxicity of PAHs to the marine diatom S. costatum might be a synergistic effect of photosensitization reactions (e.g., generation of single-state oxygen) and photomodification (photooxidation and/or photolysis).The combined effects of six binary mixtures on the marine diatom S. costatum were investigated using the additive-index method. Four binary-mixtures (phenanthrene plus anthracene; phenanthrene plus pyrene; anthracene plus fluoranthene; anthracene plus pyrene) were found to be synergistic joint action mode, while two binary-mixtures (phenanthrene plus fluoranthene; fluoranthene plus pyrene) displayed antagonist, revealing a complex pattern of possible interactions. The combined action mode of PAHs might be related to various factors such as the mixture compounds, mixture ratios and test conditions, etc.     

Methyl halide production and loss rates in sea water from field incubation experiments

Experiments were conducted in the field to determine the non-chemical loss rate of methyl iodide in seawater and to examine production rates of methyl halides. The loss rate of added C13 labelled methyl iodide, present at concentrations similar to those found in seawater, corrected for chemical loss due to reaction with Cl⁻ varied from < 1 to 18% day^− 1, with a mean value of 7%. This rate of loss is much lower than that which was proposed by Bell et al. [Bell, N., Hsu, L., Jacob, D. J., Schultz, M. G., Blake, D. R., Butler, J. H., King, D. B., Lobert, J. M., Maier-Reimer, E., 2002. Methyl iodide: Atmospheric budget and use as a tracer of marine convection in global models, Journal of Geophysical Research-Atmospheres 107(D17), 4340-4351.] to account for the large discrepancies between observed and predicted mid-latitude concentrations of CH₃I based on their global photochemical source model. The suitability of several types of container for seawater incubations was studied and only quartz tubes appeared to be free of experimental artifact. Collapsible polyvinyl fluoride containers showed major production of methyl halides on irradiation with simulated sunlight. Polyethylene containers caused spurious production of methyl iodide at lower rates.     

Assessing degradation capability of aerobic indigenous microflora in PAH-contaminated brackish sediments

A study was conducted to determine polycyclic aromatic hydrocarbons (PAHs) distribution and microbial population changes in brackish sediments from an Italian lagoon included in the Ramsar List of Wetlands of International Importance. The presence and level of PAH-degrading bacteria were estimated by the most probable number (MPN) enumeration technique, whereas degradation capability towards target compounds was checked against loss of spiked PAHs (Phenanthrene, Anthracene and Fluoranthene) in MPN tubes after incubation in optimal conditions. Chemical analyses and microbiological counts suggested a potential for PAHs biodegradation by natural occurring populations of sediment microorganisms, thus indicating an "optimal range" in sediment PAHs concentrations, outside of which the natural selection of the indigenous microflora did not occur. The MPN procedure here described, provided an effective and reliable way to simultaneously determine microbial population densities and subsequent confirmation of the biodegradation capability of sediment indigenous microflora when exposed to laboratory and environmental concentrations of PAHs.     

Petroleum geochemistry of the Kimmeridge Clay of onshore Southern and Eastern England

The Kimmeridge Clay is considered a major oil source rock for the North Sea hydrocarbon province. The formation is also developed onshore in an organic-rich mudstone facies. This paper examines the possibility of onshore oil generation from the Kimmeridge Clay. Geochemically, onshore basin margin sediments contain rich, potential source horizons with mainly Type l/Type ll oil-prone kerogen, but are immature. Some deeper Cleveland Basin sediments have reached marginal maturity. Burial history reconstruction suggests significant formation palaeoburial depths in central areas of the Cleveland and Wessex Basins. Computed vitrinite isoreflectance contours show the Wealden and Isle of Wight Kimmeridge Clay to be thermally mature. Basin modelling suggests an early Palaeogene onset of oil generation in parts of the Cleveland Basin, while maximum oil generation could have been reached by the formation base in the Isle of Wight area during the late Cretaceous. Although basin subsidence ceased in the Neogene, in the Weald and Isle of Wight, where the formation is still deeply buried, oil generation probably continued for some time during uplift. Thus significant quantities of oil could have been generated. Whether or not this oil is present today however, would depend on the correct timing of suitable migration and trap structures.     

南海北部含油气构造上方化探异常研究

在南海北部利用地球化学方法作为油气勘探的一种辅助手段。在6个航次中采集了沉积物、底层海水及海面大气样品，测定了近50种化探指标，并采用稳健统计方法进行了数据处理和异常圈定。化探结果在油气藏上方发现了清晰的、具不同指标组合的综合化探异常，与邻近空构造形成鲜明的对照。圈闭顶部的块状异常和圈闭周绿的环状、半环状异常是下伏油气藏的良好指示，而剖面上呈锯齿状、平面上呈线状的异常则与断裂带有关。实践表明，建立已知油气藏上方的化探异常模式及解剖已知空构造上方的地球化学特征对于指导本区或邻区的化探异常评价是十分必要的。     

Hydrocarbons in bivalve mollusks of Port Valdez, Alaska: Consequences of five years' permitted discharge

Petroleum hydrocarbons were investigated in Mytilus edulis and Macoma balthica at six intertidal sites in Port Valdez, Alaska after three to five years of oil terminal operation. Information about the concentrations of total hydrocarbons, unresolved complex mixture, normal alkanes, isoprenoids, olefins, hopanes and polycyclic aromatic hyrocarbons shows that petroleum accumulation in these bivalve mollusks is greatest at the Valdez municipal boat harbor and a crude oil terminal which has been permitted to discharge 170 kg oil day⁻¹. Accumulation two- to ten-fold less were observed at 3 km from the terminal and boat harbor. The temporal trends in petroleum hydrocarbon concentrations in M. edulis and M. balthica reflect the effects of selective retention and depuration of different hydrocarbon classes as well as variation in hydrocarbon sources. It is not clear whether the petroleum concentrations in Port Valdez bivalves had reached steady state by 1982, the final sampling time reported here.     

The impact of salt water inflows on the distribution of polycyclic aromatic hydrocarbons in the deep water of the Baltic Sea

Salt-water inflows into the Baltic Sea are important events for renewing the deep and bottom waters of the deep basins of the Baltic Sea. These events occur only at irregular intervals. The last strong event was in January 1993 followed by minor inflows in winter 1993/1994. As a result of these inflows, the deep water of the central Baltic basins was completely renewed.Based on extensive observations of polycyclic aromatic hydrocarbons (PAHs) in water, fluffy layer material and surface sediments between 1992 and 1998, the transformation of PAHs and the modification of their distribution in the Baltic deep water is discussed in connection with the spreading of the inflowing highly saline and oxygen-rich water along its pathway from the sills into the central basins. In the course of the inflows in 1993/1994, the PAH concentration in the deep water of the different basins increased significantly. The concentrations were elevated, at least by a factor of 2 and as much as seven to eight times (for the four-ring PAHs) compared to the previous and the following years. Two hypotheses for the causes were discussed: the inflowing salt water may have entrained more highly polluted surface water in the western Baltic Sea, or it may have entrained contaminated fluffy layer material or sediment particles along the route of transport.