Trace metals and organic compounds in sediment samples from the River Danube in Russe and Lake Srebarna (Bulgaria)

 In 1995 the contamination status of accumulated fine surface sediments and effluent material from the River Danube in Russe (Bulgaria) was analysed for trace metals (Hg, Cd, Pb, Cu, Zn, Cr, Ni, As), polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), hexachlorobenzene (HCB), 1,1,1-trichloro-2,2-bis [chlorophenyl] ethane (DDT), 1,1-dichloro-2,2-bis [chlorophenyl] ethylene (DDE), 1,1-dichloro-2,2-bis [chlorophenyl] ethane (DDD), and hexachlorocyclohexanes (α-, β-, γ- and δ-HCH) to achieve basic information about the River Danube in Bulgaria. The range of trace-metal levels came close to or below the intended quality criteria for the River Elbe in Germany. The only exceptions were Pb in a shipyard, exceeding the final criteria by a factor of 17, and Cr downflow from a metal factory. In one sample from a shipyard (D8) the highest trace metal concentrations were analysed in the fraction 125–2000 μm. The maximum measured PAH contents exhibited a contamination on the lower μg g^–1 d.w.-level (dry weight base), traces of PCBs, HCB and DDD/DDE were analysed in the ng g^–1 d.w.-range. DDT and HCHs were not detected in any sample. The trace-metal and organic-compounds level in sediments from Lake Srebarna (UNESCO-Biosphere Reserve) displayed completely background character. Received: 18 March 1997 · Accepted: 21 July 1998     

Laboratory experiments of Titan tholin formed in cold plasma at various pressures: implications for nitrogen-containing polycyclic aromatic compounds in Titan haze

Titan, the largest satellite of Saturn, has a thick nitrogen/methane atmosphere with a thick global organic haze. A laboratory analogue of Titan's haze, called tholin, was formed in an inductively coupled plasma from nitrogen/methane=90/10 gas mixture at various pressures ranging from 13 to 2300 Pa. Chemical and optical properties of the resulting tholin depend on the deposition pressure in cold plasma. Structural analyses by IR and UV/VIS spectroscopy, microprobe laser desorption/ionization mass spectrometry, and Raman spectroscopy suggest that larger amounts of aromatic ring structures with larger cluster size are formed at lower pressures (13 and 26 Pa) than at higher pressures (160 and 2300 Pa). Nitrogen is more likely to incorporate into carbon networks in tholins formed at lower pressures, while nitrogen is bonded as terminal groups at higher pressures. Elemental analysis reveals that the carbon/nitrogen ratio in tholins increases from 1.5-2 at lower pressures to 3 at 2300 Pa. The increase in the aromatic compounds and the decrease in C/N ratio in tholin formed at low pressures indicate the presence of the nitrogen-containing polycyclic aromatic compounds in tholin formed at low pressures. Tholin formed at high pressure (2300 Pa) consists of a polymer-like branched chain structure terminated with CH₃, NH₂, and CN with few aromatic compounds. Reddish-brown tholin films formed at low pressures (13-26 Pa) shows stronger absorptions (almost 10 times larger k-value) in the UV/VIS range than the yellowish tholin films formed at high pressures (160 and 2300 Pa). The tholins formed at low pressures may be better representations of Titan's haze than those formed at high pressures, because the optical properties of tholin formed at low pressures agree well with that of Khare et al. (1984a, Icarus 60, 127-137), which have been shown to account for Titan's observed geometric albedo. Thus, the nitrogen-containing polycyclic aromatic compounds we find in tholin formed at low pressure may be present in Titan's haze. These aromatic compounds may have a significant influence on the thermal structure and complex organic chemistry in Titan's atmosphere, because they are efficient absorbers of UV radiation and efficient charge exchange intermediaries. Our results also indicate that the haze layers at various altitudes might have different chemical and optical properties.     

贮藏时间和加热温度对凡纳滨对虾虾仁ATP关联化合物及品质的影响

【目的】研究贮藏时间和加热温度对凡纳滨对虾(Litopenaeus vannamei)虾仁三磷酸腺苷(ATP)关联化合物及虾仁品质的影响。【方法】利用高效液相色谱法分析凡纳滨对虾中6种ATP关联化合物,通过比较不同贮藏时间的凡纳滨对虾虾仁在加热过程中的ATP关联化合物,分析加热前后虾仁的感官品质,以及鱼虾类鲜度指标K值、G值、P值的变化。【结果与结论】随贮藏时间的增加,ATP、二磷酸腺苷(ADP)、腺苷酸(AMP)含量呈下降趋势,肌苷酸(IMP)先上升后下降,次黄嘌呤(HX)和肌苷(HXR)上升;随着加热温度的增加,ATP和ADP下降,AMP增长,IMP、HX、HXR先增加后降低。贮藏2 d后的生虾和贮藏3 d后再加热的虾仁均将达到最大感官可接受上限。随着贮藏时间的增加,加热前后K值、G值和P值线性增加,但生虾的G值与鲜度的相关性较差,不适宜作为鲜度指标,K值和P值可作为生虾的鲜度指标。加热后的K值、G值、P值与贮藏时间、感官质量评定值(QI值)的线性回归方程的决定系数较好,表明K值、G值、P值可以用来表征熟虾的品质。     

吹扫捕集-气相色谱/质谱联用同时测定饮用水源地水中痕量挥发性有机物

为满足饮用水源地监测要求,采用吹扫捕集-气相色谱/质谱法同时测定饮用水源地水中乙醛、环氧氯丙烷、丙烯醛、苯系物等27种挥发性有机物。实验中运用程序升温,在26 min内完成检测,采用全扫描(SCAN)方式扫描,提高了化合物的定性能力。方法检出限均低于我国饮用水源地标准限值,回收率为75.6%~111.0%。     

Applicability of Carbazole Migration Indices in Continental Rift Basins: A Case Study of Western Lujiapu Depression in Kailu Basin, NE China

<正>Kailu Basin in which the Western Lujiapu Depression is located is a typical continental rift basin.Biomarker parameters of the oils indicate that depositional facies and environments vary between the Bao 1 and Bao 14 fault blocks with a higher saline environment in the Bao 1 fault block, but such difference has no significant impact on carbazole abundance and distribution.Maturity and migration distance are the main controls on carbazole abundance and distribution in the Western Lujiapu Depression.The commonly used migration indices,such as ratios of nitrogen shield isomers to nitrogen exposed isomers(1-/4-methylcarbazole ratio,1,8-/2,4-dimethylcarbazole(DMC) ratio and half-shield/exposed-DMC ratio),absolute concentrations of alkylated carbazoles and BC ratio(=benzo [a]carbazole/(benzo[a]carbazole+benzo[c]carbazole)) increase at the low mature range and decrease at a higher mature range with increasing maturity.At relatively low maturity stage(Rc0.77%), maturation has reversal effects with migration on the ratios of nitrogen shield isomers to nitrogen exposed isomers,which may cover migration influence and makes these parameters fail to indicate migration effects.Valid migration indicators at this maturity stage are concentrations of alkylated carbazoles and BC ratios,which can provide ideal tools for migration direction assessment even within short migration distance.Maturity effects should be taken into account when carbazole compounds are applied to indicate migration direction,and at different maturity stages,these commonly used parameters have different validity in tracing migration direction.Coupled with our previous study in the Eastern Lujiapu Depression,a conceptual model of the variation of nitrogen migration indices can be established for terrestrial rifted basins,that is,strong fractionation lateral migration model through sandy beds,weak fractionation vertical migration model along faults,and maturity impacts on migration assessment.     

以多硫、多碘化合物为缓冲剂发射光谱法测定化探样品中As、Sb、Bi、Cd、Tl、In 元素

本方法建立了以多硫化合物、多碘化合物为缓冲剂(液体缓冲剂),上电极为光谱纯石墨电极、下电极为光谱纯石墨加罩电极的方式,采用控制试样法绘制工作曲线,电弧发射光谱法同时测定区域地球化学样品中As、Sb、Bi、Cd、Tl、In等6元素的测定方法。方法检出限为As1.0μg/g,Sb0.2μg/g,Bi0.1μg/g,Cd0.05μg/g,Tl0.1μg/g,In0.01μg/g;精密度(RSD,n=12)为As8.36%,Sb7.17%,Bi7.60%,Cd7.39%,Tl7.13%,In6.76%。方法用于测定国家一级标准物质GSD-1～GSD-12中As、Sb、Bi、Cd、Tl、In,测定值与标准值或参考值吻合。通过对1:50000区域地球化学调查样品中As、Sb、Bi、Cd、Tl、In实际分析,结果成图效果良好,具有简便快捷、成本低、检出限低、精度高等特点。     

The effects of dissolved organic matter on the aqueous partitioning of polynuclear aromatic hydrocarbons

The partitioning of six polynuclear aromatic hydrocarbons into aqueous solutions containing dissolved organic matter from various coastal environments was investigated by liquid chromatography. Specific hydrocarbon-organic matter interactions were observed. The greatest interactions occurred with the very low solubility hydrocarbons and with organic matter of terrestrial origin. Ultrafiltration experiments suggested that it was the relatively high (greater than approximately 500) molecular weight organic matter that was interacting with the hydrocarbons.     

Variations in structures and distributions of C25 highly branched isoprenoid (HBI) alkenes in cultures of the diatom, Haslea ostrearia (Simonsen)

The highly branched isoprenoid (HBI) alkenes of three batch cultures of the diatom Haslea ostrearia have been examined and the occurrence of C₂₅ tri-, tetra- and pentaenes confirmed. Growth of cultures outside at ambient temperature, under natural sunlight, in May (6 days) and June (10 days) 1995 and monitoring of HBI concentrations in samples collected daily and stored frozen, revealed that in May greater concentrations of HBIs (ca 6500 fg cell⁻¹) were produced than in June and at a much earlier stage of growth. Furthermore, in May the HBIs were more unsaturated (predominantly a tetraene rather than a triene). The reasons for these differences are at present unknown and future investigations of the effect of irradiance, temperature, salinity and other environmental variables are required. Such experiments may allow the various HBI distributions in the alga and in sediments to be better understood and, like some other polyunsaturated lipids, HBI alkenes may become useful environmental and palaeoenvironmental indicators. Two previously unreported alkenes, 2,6,10,14-tetramethyl-7-(3-methylpent-4-enyl)pentadec-2,5,9,13-ene (GC retention index, 2201_DB-1) and 2,6,10,14-tetramethyl-7-(3-methylene pent-4-enyl)pentadec-2,5,9,13-ene (GC RI, 2248_DB-1) from a batch culture of Haslea ostrearia grown in October/November 1993 and stored frozen for over a year, have also been isolated and characterised by ¹³C and ¹H NMR, epoxide derivatisation and mass spectrometry. Such structural characterisation studies of HBI alkenes should also aid our understanding of the geochemical fate of these widely distributed hydrocarbons.     

The Gas Phase Reaction of Unsaturated Oxygenates with Ozone: Carbonyl Products and Comparison with the Alkene-Ozone Reaction

Carbonyl products have been identified and their formation yields measured in the gas phase reaction of ozone with unsaturated oxygenates in experiments carried out at ambient T, p = 1 atm. of purified humid air (RH = 50%) and with sufficient cyclohexane added to scavenge the hydroxyl radical. The compounds studied are the esters methyl acrylate, vinyl acetate and cis-3-hexenyl acetate, the carbonyl crotonaldehyde, the hydroxy-substituted diene linalool, the ether ethylvinyl ether and the keto-ether trans-4-methoxy-3-buten-2-one. The alkene 1-pentene was included for comparison. The nature and formation yields of the carbonyl products from this study and those measured in earlier work under the same conditions are compared to those of alkenes and are supportive of a reaction mechanism that is similar to that for the reaction of ozone with alkenes, i.e. O₃ + R₁R₂C=CR₃X (R₁COR₂ + R₃XCOO) + (1 – )(R₃COX + R₁R₂COO), where R_i are the alkyl substituents, X is the oxygen-containing substituent (–CHO for aldehydes; –C(O)R for ketones; –C(O)OR and –OC(O)R for esters; –OH and hydroxyalkyl for alcohols; and –OR for ethers), R₁COR₂ is the primary carbonyl, R₃COX is the other primary product and R₁R₂COO and R₃XCOO are the carbonyl oxide biradicals. The biradicals lead to carbonyls in reactions that are also analogous to those involved in carbonyl formation from biradicals in the ozone-alkene reaction. These features make it possible to predict the nature and formation yields of the major carbonyl products of the reaction of ozone with unsaturated oxygenates that may be components of biogenic emissions.     

油藏色谱指纹非均质性形成机理及其稳定性实验模拟

从油田开发动态地球化学监测的基本地质概念模型出发，应用油藏流体非均质性理论，分析了不同地质时期原油色谱指纹变化的地质因素。通过指纹GC／MS鉴定和实验模拟地下不同温度和不同时间的开采条件，分析了油藏开采过程中色谱指纹的变化规律。结果表明：原油色谱指纹稳定性主要和化合物的性质、含量以及色谱柱分离度有关。油藏开采过程中，适当碳数范围内的原油色谱指纹在井底和井口的不同温度条件下以及同一单层在一定的观测时间范围内具有稳定性。研究结果对进一步开拓原油色谱指纹在油田开发管理中的应用具有重要的理论价值。