胶束电动毛细管色谱法测定海底表层沉积物中的苯系化合物

用胶束电动毛细管色谱法对海底表层沉积物中的苯系化合物进行了分析测定。采用57cm×50μm毛细管柱，以50mmol/L十二烷基硫酸钠-2.0mmol/L四硼酸钠溶液（pH9.16）作为操作缓冲溶液，并加入φ=20%的甲醇作为有机改性剂，电压25kV，检测波长200nm，15min内苯、甲苯、乙苯和二甲苯可获得良好的分离。用峰面积定量，线性范围为2～100mg/L，最小检测浓度分别为0.75mg/L苯，0.45mg/L甲苯，0.39mg/L乙苯，0.1mg/L邻-二甲苯，0.31mg/L对-二甲苯。将该法用来分析石油勘探远景区域海底表层沉积物中的苯系化合物，检测浓度范围为(0.0x～0.x)μg/g。     

Water and organic carbon fluxes from an irregularly flooded brackish marsh on the upper Texas coast,U.S.A.

Water flows, concentrations of total (TOC), dissolved (DOC), and particulate (POC) organic carbon and seston were monitored for 52 diel periods in the single creek draining a 270-ha Spartina patens-Distichlis spicata marsh on the upper Texas coast. Rainfall, creek water flows, and water levels in the creek and on the marsh were measured by recording instruments.Rainfall accounted for most marsh flooding, and water outflow was significantly correlated with both rainfall and marsh water level. Creek flows were predominantly outward because microtopographic features and dense vegetation restricted overmarsh water flows and thereby reduced tidal flooding while extending the time of precipitation runoff. Concentrations of organic carbon in water leaving the marsh were highest in spring and summer and averaged 25·62, 21·41 and 3·35 mg l^?1 of TOC, DOC and POC, respectively. These were 9·34, 9·93 and 0·04 mg l^?1, respectively, higher than bay water. Most POC was 0·3–28 μm in diameter. Seston > 28μ leaving the marsh was 95% amorphous material; the rest was plankton, grass particles and fecal pellets. Loss of organic carbon was directly correlated with net water flux, and thus rainfall accounted for most carbon loss. Net carbon loss averaged 196 kg TOC, 150 kg DOC and 32 kg POC per day. Net annual loss was 2·4–5·5% of net aerial primary productivity (NAPP), or 21·55-30·09 g TOC m^?2 year^?1.Export from this marsh falls within the range found for other marshes and the data collectively indicate that coastal marshes are not losing as much organic carbon as has been suggested by indirect measurements. The discrepancy between potential and realized export is explained by the fact that export is not a simple removal of excess detritus by tidal action but is a more complicated process mediated by the interaction of additional factors such as rainfall, vegetation structure, microtopographic variation and decomposition, which can serve to reduce the amount and quality of NAPP exported.     

利用芳烃化合物预测生物降解原油的粘度

利用薄层色谱-氢火焰离子检测和溶剂选择抽提-定量GC/MS分析技术,对辽河油田冷43/37断块区21个原油样品进行了粘度与饱和烃、芳烃化合物相关性研究.结果发现原油粘度随饱和烃族组成含量降低而升高,与芳烃族组成无关,但与萘、菲、二苯并噻吩系列芳烃化合物的绝对浓度及其在总芳烃中的百分含量关系密切.就不同粘度范围的原油,其芳烃化合物参数与粘度的相关性亦不尽相同.文中还初步建立了适应不同粘度范围的一系列粘度预测模型。     

低熟油、烃源岩中含氮化合物分布规律及其地球化学意义

对八面河地区原油、油砂以及不同成熟度和岩性有异的烃源岩中吡咯类化俣物的分布特征及其潜在的地球化学意义进行了探讨。结果表明，随着成熟度的增加，八面河地区烃源岩中吡咯类化合物中屏蔽化程度高的异构体比屏蔽化程度低的异构体富集，咔唑及苯并咔唑系列中低相对分子质量的同系物比高相对分子质量的同系物富集，苯并[a]咔唑比苯并[c]咔唑富集。八面河地区原油中吡咯类化合物有较为明显的运移分馏效应，观察到高、低相对分子质量的同系物间的运移分馏效应比不同类型异构体间的分馏效应更为显著，而前者受成熟度的影响可能相对小于后者；发现吡咯类化合物的油气运移分馏效应不仅体现于不同氮官能团屏蔽、半屏蔽和暴露三类异构体间，同样体现于同一类型的同分导师构体之间，指示此类化合物有较强的活性。吡咯类化俣物与烃类化合物一样具有多方面潜在的地球化学意义。     

库捷尔太铀矿床的生物标志化合物研究

在研究砂岩型铀矿床时，发现铀与有机质的关系密切。通过对新疆伊犁盆地库捷尔太铀矿床的正烷烃、甾烷和萜烷等有机地球化学及生物标志化合物的研究表明，主峰碳数以C29，C3l为主，具有明显的奇偶优势。因此，认为库捷尔太铀矿床中有机质的先质母体主要为高等植物，个别样品为混合物源输入。同时。笔者结合地质实际情况和某些生物标志化合物参数，判断该地区为淡水沉积环境，这种沉积环境有利于高等植物的生长和保存。而铀的富集与高等植物的繁盛有关。所以，这种沉积环境对铀的沉淀富集具有非常重要的作用，主要表现为还原沉淀和物理吸附。     

Biogenic emissions from Pinus halepensis: a typical species of the Mediterranean area

Volatile organic compounds (VOCs) emissions by vegetation present in the Mediterranean area are not well known. They may contribute with anthropogenic VOC emissions to the tropospheric ozone formation that reaches important level in the European Mediterranean region. The present work, carried out as part of the European ESCOMPTE project «fiEld experimentS to COnstrain Models of atmospheric Pollution and Transport of Emissions», adds a new contribution to the inventory of the main natural hydrocarbons sources likely to participate in the ozone production. The corresponding measurement campaign was conducted in La Barben, a site close to Marseilles (France), with the aim to quantify the terpenic emission pattern and the behaviour of Pinus halepensis, an important Mediterranean species slightly studied.The determination of biogenic emissions from P. halepensis was done by the enclosure of an intact branch in a Teflon cuvette. Main emitted monoterpenes were β trans-ocimene and linalool. The total monoterpenic emission rates thus recorded were found to reach maximum values around 30 μg g_{dry weight}⁻¹ h⁻¹. The normalized emission rates calculated at 30 °C and 1000 μmol m⁻² s⁻¹ with Guenther's algorithm was 14.76, 8.65 and 4.05 μg g_{dry weight}⁻¹ h⁻¹, respectively, for the total monoterpenes, β trans-ocimene and linalool.     

Quality issues in harvested rainwater in arid and semi-arid Loess Plateau of northern China

Loess soils cover vast areas in the arid and semi-arid regions of northern China. Due to the lack of reliable surface water and ground-water, rainwater harvesting has played a prominent role in farmers’ domestic usage and agricultural irrigation. An economical and valid type of water storage cistern with optimum design of components has been introduced to rural areas in the Loess Plateau. Different collection alternatives showed apparent variations in rainwater quality. By using different catchments, such as mortar roofs and cement-paved courtyards, compacted land or road surfaces, rainwater can be effectively collected for storage in cisterns. This study focused mainly on the quality of rainwater harvested from the different catchment systems and stored for different periods of time. By analysis of the water samples stored in these cisterns, it was evident that rainwater quality could be improved significantly by self-purification during the storage. With emphasis on rainwater quality affected by the different catchment systems, it was found that the measured inorganic compounds in the rainwater harvested from roof-yard catchment systems generally matched the WHO standards for drinking water, while the concentrations of some inorganic compounds in the rainwater collected from land and road surfaces appeared to be higher than the guideline values for drinking water, but generally not beyond the maximum permissible concentrations. However, Fecal Coliform, which is an important bacteriological parameter for the three catchment systems, exceeded the limits of drinking water to a greater extend. Trace amounts of 55 organic pollutants were identified, including aliphatic hydrocarbons, aromatic compounds and phthalate esters, etc. The analytical results indicated that roof-yard catchments that included the “first flush” usually provided safe drinking water with low organic contents, even for rainwater collected immediately after rainfall. In contrast, rainwater harvested from road surfaces had poor quality with respect to the organic constituents, regardless of stored time.     

Organochlorines and dioxin-like compounds in green-lipped mussels Perna viridis from Hong Kong mariculture zones

Concentrations of persistent organic pollutants including polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides and dioxin-like compounds were measured in green-lipped mussels, Perna viridis, collected from seven mariculture zones in Hong Kong between September and October in 2002 in order to evaluate the status, spatial distribution and potential sources of pollution in these areas. Concentrations ranged from 300 to 4400 ng/g lipid weight for total OCs and 170–1000 ng/g lipid weight for total PCBs (based on 28 congeners). Relatively smaller DDT concentrations in mussels compared with previous studies suggest reduced discharges of DDTs from nearby regions into Hong Kong waters. Detection of a mixture of HCH isomers in the mussels indicated that Hong Kong waters were predominantly contaminated by technical HCHs rather than lindane. Mussel samples from all sampling locations elicited significant dioxin-like activity in the H4IIE-luc bioassay. The greatest magnitude of dioxin-like response (39 pg TEQ/g wet wt.) was detected in mussels from Ma Wan in the western waters of Hong Kong, which is strongly influenced by the Pearl River discharge. Human health risk assessment was undertaken to evaluate potential risks associated with the consumption of the green-lipped mussels. Risk quotient (RQ) for dioxin-like compounds was greater than unity suggesting that adverse health effects may be associated with high mussel consumption.     

Solid-solute phase equilibria: From thermodynamic basis information to multicomponent systems

Solubility equilibria in aqueous media are a powerful source of information on Gibbs energy functions of pure ionic compounds and solid-solutions. Because solid-solid phase transformations and/or recrystallizations are often much slower than equilibration between solids and solutes, it is sometimes possible to obtain reliable data from measurements on metastable systems.Thermodynamic quantities of geochemically and industrially important sparingly soluble metal oxides, hydroxides, carbonates and sulfides have been determined by solubility techniques. Activity coefficient variations of the reacting species are either minimized by the method of constant ionic media, or else corrected for by using the Pitzer equations. Measurements carried out at various fixed ionic strengthsI may be used to calculate the value of the solubility constantK _s ⁰ at infinite dilution. Given the availability of Pitzer parameters of sufficient quality, values ofK _s ⁰ extrapolated by this method lead to accurate Gibbs energies of formation. Moreover, when Pitzer parameters are known up to saturation, solubilities of highly soluble salts can easily be exploited for the calculation of Gibbs functions.A consistent set of equilibrium constants for the homogeneous and heterogeneous reactions occurring in the systems under investigation is used in the general Gibbs energy minimizing program ChemSage. Master variables for the depiction of the pertinent solid-solute phase diagrams are deduced from generalized Gibbs-Duhem equations. Application of the resulting data to geochemical and industrial problems is discussed.     

A comparison of organosulphur compounds produced by pyrolysis of asphaltenes and those present in related crude oils and tar sands

Asphaltenes and NSO fractions from a variety of oils and tar sands have been characterized by pyrolysis-gas chromatography (Py---GC) using both flame ionization and flame photometric detectors. Organosulphur compounds were not always produced by pyrolysis of the asphaltenes isolated from the biodegraded tar sand extracts although pyrolysis of the NSO fractions produced a series of thiophenes from all of the samples examined. These observations suggest that under certain conditions, asphaltene fractions may be affected by biodegradation, leading to preferential removal of the sulphur containing compounds. In addition, it was observed that Py---GC of asphaltenes permitted oils to be differentiated on the basis of their source rock lithology. Oils derived from carbonate source rocks produced thiophene/benzothiopene ratios <1 whilst the same ratio was >1 for oils derived from shales. Thiophene/dibenzothiophene ratios could be used in a similar manner.