Investigations into a small fraction of volatile hydrocarbons: I. Contamination of Atlantic and Baltic Sea surface waters with C3-alkylated benzenes

A uniform pattern of alkylated benzenes was encountered in water samples from a transect through the Baltic Sea and the central Atlantic. The data resembled findings of others at a coastal sampling site. The distribution of alkylated benzenes appears to be dominated by large-scale transport in the atmosphere and in water masses.     

海洋浮游植物的生物富集热力学模型——对疏水性污染有机物生物富集双箱热力学模型

依据疏水性有机物（ＨＯＣ）在有机相／水相之间简单物理化学分配的基本原理,提出了浮游植物对ＨＯＣ生物富集双箱热力学模型。得出浮游植物对ＨＯＣ的生物富集因子ＢＣＦ与浮游植物比表面积Ｓ,有机物正辛醇／水分配系数ｋｏｗ,有机物在水中浓度Ｃｗ之间皆存在ｌｏｇ－ｌｏｇ相关性的结论,并且由海洋浮游植物对氯代苯的生物富集实验结果验证了该模型。     

Chemical and GC-MS characterization of marine particulate lipids

The lipid fraction of particulate organic matter in seawater was analyzed by gravimetry, liquid chromatography, gas chromatography (GS), and gas chromatography—mass spectrometry (GS—MS). Gravimetric concentrations in the Gulf of Mexico were in the range of 12–70 μg 1^?1 for near-surface samples and 9–52 μg 1^?1 for near-bottom samples. The lipids accounted for ～20% of the particulate organic carbon. Particulate lipids were found to be a much more complex mixture of organic compounds than the dissolved lipids and their composition was much more variable. The majority of the extracted weight was recovered in the polar liquid chromatography fraction (49–85%). The major components of the analyzable particulate lipids were similar to those of the dissolved lipids, namely, n-alkanes, pristane, phytane, and methyl, ethyl and propyl fatty acid esters. Often olefins, alkylated benzenes, quinones, and the unresolved GC area contribute a substantial part to the total particulate lipids. Minor components included ketones, phenols, indanes, acids, benzoates, aromatics and possibly derivatives of inositol, dioxane, and pyran. The low concentrations observed confirm that the area is relatively pristine though some evidence for chronic low-level oil pollution was present. Seasonal, diurnal, vertical and areal variations were observed in the particulate lipids. Lipid concentrations not only decreased with depth but they were also a decreased percentage of the organic carbon present. This may indicate the loss of labile carbon with depth due to reworking in the euphotic zone. Anoxic conditions appeared to promote the preservation of lipid materials in the particulate phase, n-Alkanes and fatty acid esters were common to both the particulate and dissolved phases and had similar distributions.     

On the sensitized photo-oxidation of alkylbenzenes in seawater

Several homologous monoalkylated benzenes were photo-oxidized as surface films on and dissolved in pure water and purified natural seawater by solar and equivalent artificial UV irradiation in the presence of anthraquinone as photo-sensitizer. The main reaction products were the 1-phenylalkanones, the corresponding secondary alcohols, benzaldehyde and, when the side chain contained four or more carbon atoms, the products of what appears to be a Norrish type II photo-degradation. The detection among the reaction products of an aldehyde with one carbon atom less than the olefin produced by the Norrish type II photo-degradation suggests a photolytic decomposition of 1-alkenes, resulting in the formation of highly reactive compounds capable of abiotic reactions in the electronic ground state with a variety of organic compounds occurring in seawater.     

Estimates of PAHs burdens in a population of ampeliscid amphipods at the head of the Mississippi Canyon (N. Gulf of Mexico)

The bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) by a dense population of ampeliscid amphipods (12,094±2499 ind m⁻²) in the head of the Mississippi Canyon at a depth of 480 m is examined and compared with estimation for amphipods from a shallow-water location, the Houston Ship Channel. The distribution of individual PAHs in sediments varies from the distribution in the organisms both in deep and shallow water, suggesting preferential uptake/depuration or uptake from pore or bottom waters. The average bioaccumulation factor (4.36±2.55) and the biota sediment accumulation factor (0.24±0.13) of total PAHs by the ampeliscid amphipods at the canyon's head are within the range reported for other benthic invertebrates. The average bioaccumulation factors are highest for dibenzothiophenes (up to 132 for C1-dibenzothiophenes) and alkylated PAHs and lowest for parent high molecular weight PAHs (HPAHs). Shallow-water amphipods are similar to deep-water amphipods in showing high preference to bioaccumulate alkylated PAHs and low preference to bioaccumulate parent HPAHs.     

Degradation of alkyl-substituted benzenes and their photo-oxidation products by a marine mixed bacterial population

Oxidation of alkyl-substituted benzenes by a marine mixed bacterial population showed no accumulation of phenyl acetic and phenyl acrylic acids, although more than 90 % of the substrates were converted to microbial cells and carbon dioxide. Photo-oxidation products were also used by bacteria to form assimilable intermediates. These reactions with mixed population constitute an interesting example of favourable interaction between bacterial degradation and photo-oxidation and can explain the disappearance of compounds listed as recalcitrant substrates. Key intermediates have been identified by gas chromatography and mass spectrometry. A mechanism based on their chemical structure is proposed for the degradation of alkyl-substituted benzenes containing side chains with odd and even numbers of carbon atoms.     

The impact of musk ketone on reproduction in zebrafish (Danio rerio).

Nitro musks are a group of nitrated benzenes mainly used by the fragrance industry as a substitute for natural musk. Two of the most common nitro musks, musk xylene and musk ketone, have been detected in water, fish, human adipose tissue, as well as in human breast milk. In this study, female zebrafish were dietary-exposed to musk ketone, prior to spawning with unexposed males. The fish were exposed for 8 weeks at two different dose levels. Accumulation of the compound in the fish as well as reproductive success were studied. Exposed females had reduced body weight and length, as well as reduced liver- and gonad somatic index. The results from the reproduction study showed a dose-dependent reduction in fecundity. Early life-stage mortality was increased and the median survival time was reduced. In addition, an embryo/larvae toxicity test was performed, using newly fertilized zebrafish eggs from unexposed parental fish. Eggs were exposed to a series of different concentrations of musk ketone via the surrounding water. A NOEC value of 10 micrograms/l and a LOEC value of 33 micrograms/l was determined. Conclusively, the present study clearly shows that musk ketone negatively affects reproduction and early life-stage survival in zebrafish.     

The impact of musk ketone on reproduction in zebrafish (Danio rerio)

Nitro musks are a group of nitrated benzenes mainly used by the fragrance industry as a substitute for natural musk. Two of the most common nitro musks, musk xylene and musk ketone, have been detected in water, fish, human adipose tissue, as well as in human breast milk. In this study, female zebrafish were dietary-exposed to musk ketone, prior to spawning with unexposed males. The fish were exposed for 8 weeks at two different dose levels. Accumulation of the compound in the fish as well as reproductive success were studied. Exposed females had reduced body weight and length, as well as reduced liver- and gonad somatic index. The results from the reproduction study showed a dose-dependent reduction in fecundity. Early life-stage mortality was increased and the median survival time was reduced. In addition, an embryo/larvae toxicity test was performed, using newly fertilized zebrafish eggs from unexposed parental fish. Eggs were exposed to a series of different concentrations of musk ketone via the surrounding water. A NOEC value of 10 μg/l and a LOEC value of 33 μg/l was determined. Conclusively, the present study clearly shows that musk ketone negatively affects reproduction and early life-stage survival in zebrafish.     

A chemical investigation of the transport and fate of petroleum hydrocarbons in littoral and benthic environments: The TSESIS oil spill

The fate of saturated and aromatic hydrocarbons discharged into the coastal Baltic Sea environment from the TSESIS oil spill has been studied in the acute and postacute (one year) phases of the spill. Periodic samples of Mytilus edulis (mussels) from eight littoral zone stations and Macoma balthica from nine soft bottom stations were obtained as well as sediment trap samples and surface sediment samples. Glass capillary gas chromatography and gas chromatographic mass spectrometry were used as the analytical tools to determine saturated and aromatic hydrocarbon composition and concentrations in these samples.Sediment trap samples indicated that sizable quantities of chemically and microbially weathered oil were sedimented, and available for benthic uptake shortly after the spill. After initial uptake of sedimented oil (500 to 1000 μ/g dry weight), Macoma populations appear to have begun slow depuration through the first winter after the spill, but TSESIS oil was again introduced to the benthic stations studied during the following summer. Mytilus populations in the region were severely impacted by the oil. Initial depuration of spilled oil during the first month was rapid and nearly complete at all but the most heavily impacted stations one year after the spill. The post-spill depuration of assimilated hydrocarbons was characterised by a relative retention of alkylated dibenzothiophenes and alkylated phenanthrenes compared to their unsubstituted parent compounds and compared with the entire homologous naphthalene series.These data suggest that petroleum hydrocarbons from the TSESIS spill have become a chronic source of degraded saturated and aromatic hydrocarbons to the soft bottom benthic communities. Petroleum hydrocarbons in the benthic environment from this spill appear to reside in the difficulty sampled and mobile flucculent layer at the sediment/water interface and may affect epifaunal communities for an extended period of time.     

Partitioning of polycyclic aromatic hydrocarbons between water and particles compared to bioaccumulation in mussels: a harbour case

Water and particles from three sites located in Halifax Harbour, near and further away from combined municipal sewage effluents (CMSE) were analysed for parental and alkylated polycyclic aromatic hydrocarbons (par and alkPAH). Bioavailability of PAH was compared for inter-tidal mussels collected at the same sites in April and November. The PAH fingerprint determined over 9 sampling times covering a period of 19 months differed more between phases (water and particles) and seasons, than between sites. In the spring, more alkPAH associated with diesel and gasoline were detected in the soluble phase, along with more bioaccumulation of alkPAH in inter-tidal mussels. A broader number of parPAH were detected in mussels collected in the fall. The mean sum of dissolved alkPAH concentrations was higher in water at the site closer to raw CMSE than at the other two sites and particles of that site. However, lowest bioconcentration factors (BCF) were determined in mussels of this more contaminated site. Similar biota-particle accumulation factors (BPAF) were determined for parPAH in mussels from the three sites, all lower than the BCF of alkPAH. The study indicates that sewage treatment plants will reduce the amount of parPAH especially larger than fluoranthene and pyrene from being deposited in the harbour; that alk naphthalenes and fluorenes present in water will continue to be discharged; that the disturbance of sediments can make particle-bound PAH available to mussels.     

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。     

Distinguishing human from animal faecal contamination in water: A review

Management of faecal contamination of water would be improved if sources could be accurately identified through water analysis. Human faeces are generally perceived as constituting a greater human health risk than animal faeces, but reliable epidemiological evidence is lacking. United States waterborne disease data suggest that human‐specific enteric viruses account for over half the documented outbreaks. However, in New Zealand, where there is a high grazing animal:human ratio (increasing the relative importance of water‐transmissible zoonoses), it seems prudent to assume that human and animal faecal pollution both constitute a risk to human health. Irrespective of the relative risks, the ability to identify sources would assist in overall management of microbial water quality. Faecal streptococci do not appear to provide reliable faecal source identification. Human and animal sources, respectively, maybe distinguishable by two tests on Bifidobacterium spp.—growth at 45°C in trypticase phytone yeast broth and sorbitol fermentation. Different species of Bacteroides tend to be present in humans and animals, but poor survival in water is a problem. Phages of the Bacteroides fragilis strain HSP40 appear to be human specific, but low counts in effluent in some countries, including New Zealand, may limit their usefulness. Different F‐RNA phage subgroups appear to be associated with human and animal faecal sources. The actinomycete Rhodococcus coprophilus has potential as a grazing animal indicator but it is persistent, and existing culturing techniques are time consuming. The development of DNA‐based techniques, such as polymerase chain reaction (PCR), may assist in the assay of some microbial faecal source indicators. Various faecal sterol isomers offer the possibility of distinguishing between human and animal sources, and even between different animals. Washing powder constituents such as fluorescent whitening agents, sodium tripolyphosphate and linear alkyl benzenes, offer useful human source identifiers. It is unlikely that any single determinand will be useful in all situations, but statistical analysis of appropriate “baskets” of microbial and chemical determinands offers the possibility of identifying and apportioning human and animal faecal inputs to natural waters.     

Linear alkyl benzenes (LABs) in sediments of Port Phillip Bay (Australia)

Linear alkyl benzenes (LABs), which have been proposed as markers of the hydrocarbon component of domestic wastes, were measured in sediments from three areas of Port Phillip Bay (Australia). The concentrations found (0–19 μg g⁻¹) were generally lower than those reported for other coastal sediments from the USA and Japan. This is thought to reflect the small quantity of domestic wastes entering Port Phillip Bay.Compositional profiles showed that both physical and biological processes had acted to remove LABs during deposition.At one site, unusual alkyl benzene compounds, but no conventional LABs, were detected. These compounds were probably synthesised terrestrially by the bacteria of a nearby sewage farm.     

珠江虎门潮汐水道水体中多环芳烃的分布及季节变化

采用GF/F玻璃滤膜对珠江虎门潮汐水道6个表层水样进行过滤分离出多环芳烃的颗粒相和溶解相,并根据美国EPA标准对多环芳烃进行了定量分析.结果显示,洪、枯季水体中16种优先控制多环芳烃总量分别是223～614,6 559～20 031 ng/dm3;洪、枯季多环芳烃总量分别为786～2 098,11 360～34 338 ng/dm3;广州前航道的污染较狮子洋严重.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,枯季多环芳烃的浓度高于洪季1个数量级以上,且二环多环芳烃的含量占95%以上,主要呈溶解相形式出现;洪季高环多环芳烃的含量明显升高,主要呈颗粒相形式输运.     

Acute and sublethal toxicity of naphthalene and three methylated derivatives to the estuarine copepod, Eurytemora affinis

The bi-cyclic aromatic hydrocarbon naphthalene (N) and its alkylated derivatives 2-methylnaphthalene (MN), 2,6-dimethylnaphthalene (DMN) and 2,3,5-trimethylnaphthalene (TMN) were used to investigate possible relationships between increased methylation and toxicity during acute high level and chronic low level exposure experiments using the calanoid copepod Eurytemora affinis Poppe. The 24-h LC₅₀ levels determined indicated an approximate twofold increase in toxicity per methyl group addition: N-3798 μg/litre; MN-1499 μg/litre; DMN-852 μg/litre and TMN-316 μg/litre. Low level chronic exposure of E. affinis to the various naphthalenes in sea water concentrations of about 10 μg/litre for the duration of their adult life (maximum twenty-nine days) resulted in significant reductions in length of life, total numbers of nauplii produced and mean brood size. Exposure to all the naphthalenes at this level (10 μg/litre) resulted in reduced rates of egg production which were, on average, about 50% of those of control animals. Results are discussed in relation to previous work on the fate and effect of petroleum hydrocarbons in marine copepods.     

计算毒理学在海洋溢油事故特征污染物甄选中的应用研究

鉴于溢油及其风化产物的组分复杂性,本文应用计算毒理学方法对溢油中的主要毒性特征污染物进行甄选。首先结合美国溢油事件中的主要污染物分类方法,针对溢油事故的潜在特征污染物进行持久性、生物富集性和毒性判别,然后建立基于密度泛函理论(DFT)分子结构参数的定量结构-活性相关模型,尝试筛选出海洋溢油事故的12种特征污染物,包括3种多环芳烃(PAHs)、8种烷基化PAHs及1种PAH的氧化衍生物。本文首次应用DFT方法进行溢油中特征污染物的甄选研究,研究结果可为海洋环境管理部门在溢油污染物监管和灾后处置等方面提供参考。     

我国几种常见润滑油的指纹分析

采用气相色谱/质谱方法(GC/MS)对7 种常见润滑油中的生物标志化合物(正构烷烃、姥鲛烷、植烷、甾烷、萜烷、多环芳烃)进行定性分析, 并基于其生物标志化合物指纹信息进行了多元统计分析。结果表明, 润滑油的气相色谱图中不可分辨的混合物(UCM)具有明显优势; 润滑油中含有丰富的甾、萜烷类稠环生物标志化合物, 仅含有非常少量的饱和链烷烃(正构烷烃、姥鲛烷、植烷)和多环芳烃类(目标多环芳烃、烷基化多环芳烃、二苯并噻吩同系物)生物标志化合物; 基于甾、萜烷类生物标志化合物指纹信息的主成分分析与聚类分析所得的结果高度一致, 均可用于有一定差异的润滑油的鉴别分析。     

我国几种常见润滑油的指纹分析

采用气相色谱／质谱方法（GC／MS）对7种常见润滑油中的生物标志化合物（正构烷烃、姥鲛烷、植烷、甾烷、萜烷、多环芳烃）进行定性分析,并基于其生物标志化舍物指纹信息进行了多元统计分析。结果表明,润滑油的气相色谱图中不可分辨的混合物（UCM）具有明显优势;润滑油中含有丰富的甾、萜烷类稠环生物标志化合物,仅含有非常少量的饱和...     

A seasonal survey of the sterol composition of the cockle cerastoderma edule: A comparison of polluted and non-polluted environments

The sterol composition of a cockle population from an unpolluted environment in South Wales was monitored by monthly sampling over a 12-month period. In spite of the likely variation in dietary sterols during this period, the component sterols of the cockles showed no significant seasonal variation, indicating that the cockle was able to exhibit a high degree of control over the composition of its functional sterols.Dramatic differences were observed in the sterol compositions of a nearby cockle population from a highly polluted environment, near a sewage outfall; only three out of the ten sterols present were common to the unpolluted cockles. Forty-five per cent of the sterols from the ‘polluted’ samples contained fully reduced systems and included three new alkylated C-29, C-30 and C-31 stanols. It is considered possible that these structural changes may affect the stereochemistry of the functional sterols and hence alter the permeability of the animal's membranes. This may reflect a biochemical response to the polluted environment.     

Hydrocarbon geochemistry of the Puget Sound region—III. Polycyclic aromatic hydrocarbons in sediments

Polycyclic aromatic hydrocarbon (PAH) distributions and sources are characterized in 96 sediment samples from 24 ²¹⁰Pb-dated cores collected at locations in the greater Puget Sound. The highest PAH concentrations are found within a few kilometers of several sources including industrial facilities in northern Puget Sound, urban areas in central Puget Sound, and river systems draining coal-bearing strata. Regional patterns of combustion-derived PAH in surficial sediments indicate little atmospheric or waterborne exchange of PAH between different regions of the Sound. Significant subsurface maxima in combustion-derived PAH concentrations (²¹⁰Pb dated at the 1950s) occur only in sediment cores collected near urban centers. Perylene apparently derives from erosion of a terrestrial source with little or no evidence of in situ production at depth in sediment cores. Coal fragments are carriers of a characteristic suite of alkylated phenanthrene, chrysene, and picene derivatives concentrated near river mouths in central and southern Puget Sound.