MODELING THE FATE AND TRANSPORT OF HYDROPHOBIC ORGANIC COMPOUNDS IN AN UNSTEADY RIVER-ESTUARINE SYSTEM

1 INTRODUCTION Extensive literature (Brown et al., 1985; Sawhney et al., 1981; Bierman and Swain, 1982; Connolly, 1980; Lopez-Avila and Hites, 1980; O扖onnor, 1988) described lots of sorbed pollutants or toxic substances in bed sediments of rivers, even after the effluent was halted for a long time. This is particularly true for hydrophobic organic compounds that can be sorbed on the particles and accumulated in the river bed sediments (Karickhoff et al., 1979). Pollution events of…     

Preservation of diagenetic products of β-carotene in sedimentary rocks from the Lopare Basin (Bosnia and Herzegovina)

Sedimentary rocks from the saline formation of the Lopare Basin were investigated. Sediments contain a moderate amount of immature to marginally mature algal organic matter deposited under slightly reducing to anoxic and slightly saline to hypersaline conditions. Almost all of the samples contain β-carotane in a relatively high quantity, and in some, it represents the most abundant compound in the total distribution of hydrocarbons. The objective of the study was to determine the conditions that are favourable to precursors of β-carotene and/or the preservation of the carotenoid hydrocarbon skeleton. Moreover, the dominant transformation pathways of β-carotene under different redox and salinity conditions, which lead to the formation of aromatic carotenoids were defined.     

Characterization of Estuarine and Fluvial Dissolved Organic Matter by Thermochemolysis using Tetramethylammonium Hydroxide

Selected samples of dissolved organic matter (DOM) isolated by ultrafiltration (UDOM) have been analyzed by thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH). This technique cleaves ester and ether bonds of bio‐ and geological macromolecules and releases monomer subunits and methylates them in situ as their methyl ethers and methyl esters. Compared with conventional pyrolysis, TMAH thermochemolysis avoids decarboxylation of preexisting carboxylic moieties and produces aromatic acids as their methyl esters. Various phenolic derivatives, which might originate from incorporated lignin‐derived structures, from the highly aliphatic and resistant biopolymer cutan and also from proteinaceous materials, were identified among the products produced from UDOM upon thermochemolysis. The presence of lignin derivatives in UDOM indicates input of organic matter derived from terrestrial sources. Various aromatic acids, perhaps representing the final steps in the oxidation of the side‐chain during microbial oxidation of lignin, were released upon TMAH thermochemolysis, suggesting they are structural constituents of the UDOM. Different ratios of lignin‐derived materials, commonly determined using the CuO oxidation method, such as the Δ value, indicative of the amount of lignin present, the acid/aldehyde ratio (Ad/Al)_G, indicative of the extent of oxidative degradation of the lignin component, and the syringyl/guaiacyl (S/G) and p‐hydroxyphenyl/guaiacyl (P/G) ratios, indicative of the contribution for the different types of lignin, were determined.     

The feasibility of isolation and detection of fullerenes and carbon nanotubes using the benzene polycarboxylic acid method

The incorporation of fullerenes and carbon nanotubes into electronic, optical and consumer products will inevitably lead to the presence of these anthropogenic compounds in the environment. To date, there have been few studies isolating these materials from environmental matrices. Here we report a method commonly used to quantify black carbon (BC) in soils, the benzene polycarboxylic acid (BPCA) method, for measurement of two types of single walled carbon nanotubes (SWCNTs), two types of fullerenes and two forms of soot. The distribution of BC products (BPCAs) from the high pressure and high temperature oxidation illustrates the condensed nature of these compounds because they form predominantly fully substituted mellitic acid (B6CA). The conversion of carbon nanoparticles to BPCAs was highest for fullerenes (average of 23.2 ± 4.0% C recovered for both C₆₀ and C₇₀) and lowest for non-functionalized SWCNTs (0.5 ± 0.1% C). The recovery of SWCNTs was 10 times higher when processed through a cation-exchange column, indicating the presence of metals in SWCNTs compromises the oxidation chemistry. While mixtures of SWCNTs, soot and sediment revealed small losses of black carbon during sample processing, the method is suitable for quantifying total BC. The BPCA distribution of mixtures did not agree with theoretical mixtures using model polyaromatic hydrocarbons, suggesting the presence of a matrix effect. Future work is required to quantify different types of black carbon within the same sample.     

柴达木盆地西部第三系咸水湖相原油地球化学特征

在系统分析柴达木盆地西部各油田40余个原油样品碳同位素和饱和烃、芳烃组成的基础上,全面剖析了该地区第三系湖相原油的地球化学特征.研究结果表明,这些原油具有特殊的碳同位素组成和异常的生物标志物分布.其全油碳同位素偏重(-26‰～-24‰);正构烷烃系列单体烃碳同位素分布曲线呈水平状,表现出类同于海相有机质的碳同位素组成特征.它们的生物标志物中正烷烃系列兼具奇碳和偶碳优势双重碳数分布模式;呈强植烷优势,Pr/Ph值大多<0.6;伽玛蜡烷普遍异常丰富,C35藿烷含量高,表征高盐、厌氧的咸水湖相沉积环境性质.芳烃组份以萘、菲系列为主,而二苯并噻吩等含硫有机化合物相对含量较低,反映该地区咸水湖相原油源岩沉积相的特殊性.柴西各油田原油地球化学参数在区域上呈规律性变化趋势,与其源岩沉积相的时空变迁相一致.     

Analytical perspective on trace element species of interest in exploration

Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH₂OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH₂OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.     

藏东南大气中多环芳烃的污染特征及来源分析

为探究青藏高原东南部大气中多环芳烃(Polycyclic Aromatic Hydrocarbons,简称PAHs)的污染、源及输送特征,利用鲁朗地区(29.77°N,94.73°E)总悬浮颗粒物(Total Suspended Particles,简称TSP)和大气中的14种PAHs含量,结合同期气象环境数据进行了综合分析。结果表明,该地区TSP中PAHs和气相的PAHs质量浓度变化范围分别为0.22～5.05 ng m^-3和0.83～63.75 ng m^-3,平均值分别为2.13 ng m^-3和11.33 ng m^-3。薪柴和柴油的燃烧是污染的主要方式,汽油燃烧等其他排放为次要方式。PAHs来自本地污染和远距离传输(Long Range Transmission,简称LRT)共同的影响。本地污染在四季各个源地均不相同。冬春季本地污染大,源在东南及正南方,夏秋季受本地和外来输送共同作用,本地源在东南方且占比小,LRT占比大。LRT受西北气流、西风气流和西南气流三支气流影响,污染严重时西南气流占主导...     

应重视选用芳烃演化参数评价高演化碳酸盐岩

现被广泛应用的测定高演化碳酸盐岩成熟度指标的多项有机岩石学评价方法，各有其不同的局限性，应用效果并不理想。研究发现，可利用芳烃演化新参数来代替其它失效的分子参数来评价碳酸盐岩有机质。芳烃因其结构、组成的特殊性和稳定性，在高演化阶段与油气生成及煤源岩成熟度有着良好的相关性，具有成为高演化碳酸盐岩成熟度指标的基础。从生产实践的角度看，芳烃演化参数有特殊适用性及选取的可行性。     

Thermogenic organic matter dissolved in the abyssal ocean

Formation and decay of thermogenic organic matter are important processes in the geological carbon cycle, but little is known about the fate of combustion-derived and petrogenic compounds in the ocean. We explored the molecular structure of marine dissolved organic matter (DOM) for thermogenic signatures in different water masses of the Southern Ocean. Ultrahigh-resolution mass spectrometry via the Fourier transform-ion cyclotron resonance technique (FT-ICR-MS) revealed the presence of polyaromatic hydrocarbons (PAHs) dissolved in the abyssal ocean. More than 200 different PAHs were discerned, most of them consisting of seven condensed rings with varying numbers of carboxyl, hydroxyl, and aliphatic functional groups. These unambiguously thermogenic compounds were homogenously distributed in the deep sea, but depleted at the sea surface. Based on the structural information alone, petrogenic and pyrogenic compounds cannot be distinguished. Surface depletion of the PAHs and first estimates for their turnover rate (> 1.2 · 10¹² mol C per year) point toward a primarily petrogenic source, possibly deep-sea hydrothermal vents, which is thus far speculative because the fluxes of combustion-derived and petrogenic matter to the ocean are not well constrained. We estimate that > 2.4% of DOM are thermogenic compounds, and their global inventory in the oceans is > 1.4 · 10¹⁵ mol C, significantly impacting global biogeochemical cycles.