夏季珠江口水体中多环芳烃的分布、组成及来源

利用1999年7月对珠江口海域的调查资料,对该区表层海水中优控多环芳烃的分布、组成及来源进行了分析和讨论,结果表明:(1)夏季珠江口海域表层海水中14种溶解态多环芳烃[苊、芴、菲、蒽、荧蒽、芘、苯并(a)蒽、艹屈、苯并(b)荧蒽、苯并(k)荧蒽、苯并(a)芘、二苯并(a,h)蒽、苯并(g,h,i)艹北、茚并(1,2,3-cd)艹比]的质量浓度为63.8~171.7 ng/L,且沿着冲淡水流向呈降低趋势;(2)颗粒态中15种多环芳烃[萘、苊、芴、菲、蒽、荧蒽、芘、苯并(a)蒽、艹屈、苯并(b)荧蒽、苯并(k)荧蒽、苯并(a)芘、二苯并(a,h)蒽、苯并(g,h,i)艹北、茚并(1,2,3-cd)艹比]的质量浓度为60.7~186.7 ng/L,其分布与水体载沙量及悬浮颗粒物的性质、粒径有关,具有从河口内向外海降低的分布特征;(3)多环芳烃组成和特征参数比值的分析表明,珠江口海域高温裂解来源的多环芳烃在伶仃洋海区输入最多,且主要为人类活动中煤燃烧排放的,而在香港岛周围海区的输入则相对较少,且主要为油燃烧排放的;(4)与法国塞纳河及长江口等河口相比,珠江三角洲海域水体中存在高菲含量排放源。     

Biotransformation of polycyclic aromatic hydrocarbons in marine polychaetes

Deposit-feeding polychaetes constitute the dominant macrofauna in marine environments that tend to be depositional centers for organic matter and contaminants. Polychaetes are known to accumulate polycyclic aromatic hydrocarbons (PAHs) from both particulate and dissolved phases but less is known about the mechanisms underlying elimination of accumulated PAHs. An important pathway of elimination is through biotransformation which results in increased aqueous solubility of the otherwise hydrophobic PAHs. Biotransformation in marine polychaetes proceeds in a two phased process similar to those well studied in vertebrates, phase I enzymes belonging to the Cytochrome P450 (CYP) enzyme family, along with a few phase II enzymes have been identified in marine polychaetes. In this review we aim at highlighting advances in the mechanistic understanding of PAH biotransformation in marine polychaetes by including data obtained using analytical chemistry and molecular techniques. In marine polychaetes induction of CYP enzyme activity after exposure to PAHs and the mechanism behind this is currently not well established. Conflicting results regarding the inducibility of CYP enzymes from polychaetes have led to the suggestion that induction in polychaetes is mediated through a different mechanistic pathway, which is corroborated by the apparent lack of an AhR homologous in marine polychaetes. Also, none of the currently identified CYP genes from marine polychaetes are isoforms of those regulated by the AhR in vertebrates. Relatively few studies of phase II enzymes in marine polychaetes are currently available and most of these studies have not measured the activity of specific phase II enzymes and identified phase II metabolites but used an extraction technique only allowing determination of the overall amount of phase II metabolites. Studies in insects and various marine invertebrates suggest that in invertebrates, enzymes in the important phase II enzyme family, UDP-glucuronosyl transferases primarily use glucoside as co-substrate as opposed to the vertebrate cosubstrate glucuronic acid. Recent studies in marine polychaetes have however identified glucuronidation of PAHs indicating no mechanistic difference in co-substrate preference among UDP-glucuronosyl transferases between vertebrates and marine polychaetes but it might suggest a mechanistic difference between marine polychaetes and insects.     

Immune inhibition in marine mussels by polycyclic aromatic hydrocarbons

Polycyclic aromatic pollutants produced by a range of industrial processes and the combustion of fossil fuels. They eventually enter the marine environment, and are bioaccumulated in the tissues of sessile, filter-feeding bivalves, causing a variety of sublethal effects. Few studies, however, have examined immune inhibition in molluscs by these xenobiotics. Here, the immunotoxic effects of PAHs were investigated in marine mussels (Mytilus edulis) by means of in vivo exposure experiments. Animals were exposed to a PAH cocktail of anthracene, fluoranthene and phenanthrene for 2 or 4 weeks. The haemolymph was then extracted, and phagocytosis and lysosomal neutral red retention assays performed to examine the effects of PAHs on particle uptake by haemocytes and lysosome integrity, respectively. PAHs were found to inhibit phagocytosis and damage lysosomes. It is hypothesized that PAHs exert their toxicity directly on the lysosomes. A possible consequence of such lysosomal damage will be immune impairment in mussels leading to reduced resistance to infectious diseases.     

Observation of abnormal solubility behavior of aromatic hydrocarbons in seawater

The Setschenow and McDevit—Long equations are applied to aromatic hydrocarbons in seawater by using solute surface area and recently available solubility data to evaluate the Setschenow constant. It is demonstrated that this approach avoids a previously encountered problem with the McDevit-Long equation while also pointing out fundamental theoretical discrepancies. Compounds that do not fit the presented semi-empirical relationship are of interest as they may exhibit abnormal partitioning behavior in seawater. Using this approach it is suggested that 1,2-benzanthracene and benzo(a)pyrene exhibit abnormal solution behavior in seawater.     

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.     

Effect of environmental factors on photodegradation of polycyclic aromatic hydrocarbons (PAHs) in the water-soluble fraction of Kuwait crude oil in seawater

Photodegradation of PAHs in the water-soluble fraction of Kuwait crude oil in seawater was investigated under various environmental factors (temperature, light intensity, oxygen levels and presence of a sensitizer) in laboratory conditions. All factors investigated had significant effect on the degradation rates of PAHs. At 15 °C almost all PAHs optimally degraded at an oxygen level of 4 ppm. For lower molecular weight PAHs a light intensity of 500 W/m² in the presence of the sensitizer worked well. Higher molecular weight PAHs degraded at faster rates at a light intensity 750 W/m². At 30 °C, most of the PAHs degraded optimally at an oxygen level of 0 ppm and light intensity of 500 or 750 W/m² in presence of the sensitizer. At 40 °C, most of PAHs degraded optimally at low oxygen concentrations (0 and 4 ppm) and a light intensity of 500 W/m² in the presence of the sensitizer. Linear regression indicated that for most of the compounds, light intensity had the greatest effect on degradation rates.     

Metabolic activation of polycyclic aromatic hydrocarbons by fish liver cytochrome P-450

The incidence of hepatoma, epidermal and other forms of cancerous growths in fish is well documented (Halver, 1967; Matsushima & Sugimura, 1976; Dawe et al., 1964). In fish, as in mammals, cancer may be a result of metabolically activated carcinogens. In mammals the primary enzyme system involved in the activation of environmental carcinogens is the cytochrome P-450 linked mixed-function oxidase (MFO). The hepatic microsomes of the species offish studied contain variable levels of cytochrome P-450. Liver microsomes of the trout Salmo trutta lacustris are surprisingly active in metabolising benzo-[a]pyrene (BP) and other compounds preferentially metabolised by polycyclic aromatic hydrocarbon (PAH)-specific cytochrome P-450. This finding may be significant, because it is apparent that the detrimental effects of PAHs require metabolic activation.We have studied the production of reactive intermediates of BP by following their binding to DNA and by measuring the specific nucleotide-BP metabolite complexes by chromatography. Untreated S. trutta liver microsomes catalyse the production of reactive intermediates of BP which bind to nucleotides of DNA at a rate that is 3–4 times higher than that catalysed by control rat liver microsomes. The most prominent DNA-BP metabolite adducts produced by trout liver microsomes are the nucleoside adduct of BP-7, 8-diol-9,10-epoxide and 9-OH-BP-4,5-oxide and other phenol oxides. In contrast to the trout, another fish species, roach (Rutilus rutilus), has extremely low activity. Although the in vitro binding of BP to DNA is not strictly correlated to in vivo binding or biological effects, our results show that reactive intermediates are formed by trout liver and thus the prerequisite for chemical carcinogenesis or mutagenesis is ful filled. This is further supported by the fact that in Ames's test, trout liver preparations produce mutagenic products from promutagens.     

Implications from a field study regarding the relationship between polycyclic aromatic hydrocarbons and glutathione S-transferase activity in mussels

An aluminium smelter on the west coast of Scotland discharges an aqueous effluent containing polycyclic aromatic hydrocarbons (PAHs) at the head of Loch Leven. The loch also supports two mussel (Mytilus edulis) farms. Data are presented on burdens of PAHs in the soft tissues of mussels and the effect of these contaminants on glutathione S-transferase (GST) activity in mussel hepatopancreas. GST activity is shown to be correlated with total PAH burden and also with the concentrations of certain individual PAHs. These field data show that high molecular weight PAHs are closely correlated to GST activity, whereas low molecular weight PAHs are not. This suggests that 5- and 6-ring PAHs have a more pronounced role than 2- to 4-ring compounds in inducing GST activity in mussels from Loch Leven. It is proposed that it may be more appropriate to link GST activity with 5- and 6-ring compounds only, rather than with the total PAH burden.     

Cellular responses to polycyclic aromatic hydrocarbons and phenobarbital in Mytilus edulis

Certain polycyclic aromatic hydrocarbons and phenobarbital induced an increase in the activity of microsomal NADPH neotetrazolium reductase (linked to mixed function oxygenase systems) in the blood cells of Mytilus edulis. Phenanthrene and methylated naphthalenes caused lysosomal destabilisation which is believed to be directly related to the mechanism of cytotoxicity in the digestive cells. The use of these cytochemical techniques as indices of aromatic hydrocarbon contamination is discussed.     

Transport and behavior of marine oil spill containing polycyclic aromatic hydrocarbons in mesocosm experiments

Polycyclic aromatic hydrocarbons(PAHs) are one of the most important groups in oil,and re sponsible for major toxic and/or carcinogenic impact on humans and wildlife.It is important to understand the behavior of PAHs in marine environment after an oil-spill incident.However,interaction between petroleum PAHs and microbial communities in a marine environment remains unclear.Therefore,a series of mesocosm experiments were conducted.in which water-accommodated fraction(WAF) of oil was generated to ...     

长江口外沉积物中多环芳烃结构类型的分布

本文采用色谱—质谱—质谱—计算机系统技术,分析了长江口外两个表层沉积物中多环芳烃组分,并探讨了其有机质的来源和地球化学特征。     

Accumulation of polycyclic aromatic hydrocarbons from contaminated soil by Kandelia candel

The purpose of this study was to investigate the accumulation behavior of two typical PAHs,phenanthrene(PHE) and fluoranthene(FLA),uptaken by the mangrove Kandelia candel in various treated sandy soils.The experiment lasted for three months.Soil and plant samples were collected after 3,6,9 and 13 weeks of the incubation and the levels of PAHs were analyzed using a GC/MS(HP6890-5975B).The results showed that the root accumulations of PHE and FLA were elevated with the increase of the PAH concentrations in the soil.With prolonged exposure time,PHE and FLA concentrations of the roots increased significantly in comparison with the control.PHE and FLA concentrations of root after 13 weeks of treatment ranged from 0.28 to 4.36 μg·g^-1 and 0.79 to 35.76 μg·g^-1,respectively.The calculated mean values of the root concentration factors were 0.58 for PHE and 0.71 for FLA.This indicated that root accumulation of FLA was greater than PHE,which would result from the higher octanol-water partition coefficient(K_ow) of FLA.These results underline the ability of mangroves to remove PAHs from contaminated marine substrates and hence their potential use in bioremediation and the removal of PAHs from the marine food chain.     

南中国海海水中多环芳烃的分布特征及源分析

利用气相色谱-质谱联用(GC-MS)技术,对2012年10月采自南中国34个站位的表层、500 m层、底层海水中的16种多环芳烃(16PAHs)进行了检测分析。结果显示:南中国海海水中16PAHs的含量相对于其他类似广阔水域较低,分布特征大致呈现500 m层表层底层。经特征PAHs组分分析判定南中国海海水中PAHs主要来源于石油及其产品。     

Geochemistry of polycyclic aromatic hydrocarbons in the bottom sediments of the eastern Arctic shelf

Sources and pathways of supply of polycyclic aromatic hydrocarbons (PAH) in the surface sediments of the Laptev and East Siberian seas were identified based on an analysis of the lithological-geochemical characteristics and distribution of organic matter (OM). The distribution of organic carbon, humic acids, bitumoids, and hydrocarbons demonstrates the determining role of the riverine runoff in the formation of the recent sediments. The total average content of PAH in the sediments of this region approximates 37 ng/g, not exceeding 80 ng/g of dry sediment. The biogenic components of the PAH (alkylphenanthrenes, alkylchrysenes, perylene) dominate in the estuarine-shelf and coastal-shelf sediments enriched with plant detritus and significantly decrease in the pelagic zone. The anthropogenic influence is observed in sediments of the port of Tiksi, where the total content of PAH with dominant pyrogenic components is two orders of magnitude higher as compared with the background values in the study region.     

Implications from a field study regarding the relationship between polycyclic aromatic hydrocarbons and glutathione S-transferase activity in mussels

An aluminium smelter on the west coast of Scotland discharges an aqueous effluent containing polycyclic aromatic hydrocarbons (PAHs) at the head of Loch Leven. The loch also supports two mussel (Mytilus edulis) farms. Data are presented on burdens of PAHs in the soft tissues of mussels and the effect of these contaminants on glutathione S-transferase (GST) activity in mussel hepatopancreas. GST activity is shown to be correlated with total PAH burden and also with the concentrations of certain individual PAHs. These field data show that high molecular weight PAHs are closely correlated to GST activity, whereas low molecular weight PAHs are not. This suggests that 5- and 6-ring PAHs have a more pronounced role than 2- to 4-ring compounds in inducing GST activity in mussels from Loch Leven. It is proposed that it may be more appropriate to link GST activity with 5- and 6-ring compounds only, rather than with the total PAH burden.     

九龙江河口表层水体中溶解态多环芳烃及六溴环十二烷的分布特征及来源解析

持久性有机污染物因其与环境和人类健康息息相关而受到国内外研究学者的持续关注。本研究以类持久性有机污染物—多环芳烃(polycyclic aromatic hydrocarbons, PAHs)和新型持久性有机污染物—六溴环十二烷(hexabromocyclododecanes, HBCDs)为研究对象,于2019年1月和2月对九龙江河口表层水体进行了采样分析,采用固相萃取-气质联用(GC-MS)方法,分析其表层水体中18种溶解态多环芳烃及3种六溴环十二烷的含量分布特征和组分特征,探究其来源并进行污染评价。结果表明,表层水体中溶解态多环芳烃ΣPAHs含量范围为38.49～256.00 ng/L,各组分以2环和3环为主,4环次之,5环及以上仅有个别站位检出,其来源以石油源为主,主要来源于石油类化石燃料燃烧。ΣHBCDs的含量范围为ND～49.951 ng/L,以α-HBCD为主,γ-HBCD次之,β-HBCD最少。与国内外其他港湾及流域相比,九龙江河口PAHs含量依然处于较高水平,HBCDs含量则处于相对较低水平。     

Trace elements and polycyclic aromatic hydrocarbons (PAHs) concentrations in deep Gulf of Mexico sediments

The concentrations of polycyclic aromatic hydrocarbons (PAHs) and trace elements were determined for surface (top 2 cm) sediment samples collected during the deep Gulf of Mexico benthos (DGoMB) study .These elements and compounds are known to be toxic to organisms at high concentrations and may affect biological communities. There is no indication of major anthropogenic input of the elements Be, Co, Cr, Fe, Si, Tl, V, K, Mg, Ca, Sr and Zn, based on normalization to Al. The concentrations of these metals in the sediment are a function of the relative amounts of trace-metal-rich Mississippi River-derived silicate material and trace-metal-poor plankton-derived carbonate. This is not true for the elements Ba, Ni, Pb, Cd, As, Cu and Mn, whose concentrations show considerable scatter when normalized to Al and a general enrichment. On a normalized basis, Mn is enriched 5–10 fold, Cu and Ni 2–3 fold and Pb 2 fold over Mississippi River-derived material. These enrichments are likely the result of remobilization of metals from depths in the sediment column where reducing conditions exist. The Ba concentrations at selected sites are higher than those of average clay-rich sediments, but are typical of sediments from near oil well platforms in the northern Gulf of Mexico. In the case of Ba, it seems likely that the enrichments, as high as a factor of 10, are due to disposal of oil well drilling mud. The Ba-enriched samples are from the three shallowest water sites in the Mississippi Trough (sites MT1, 2 and 3) and from site C1 and WC5. All are in an area of intense petroleum exploration and development. PAH concentrations are also elevated at MT1, MT3 and C1. The total PAH concentration ranged from not detected (ND) to 1033 ng/g with a mean of 140 ng/g. Even at the sites most enriched in PAHs and trace elements, the concentrations are not at the levels expected to adversely affect the biota. However, these predicted non-effects are based on research using mostly near-shore estuarine species, not on the indigenous species at the sampling sites.     

Acute toxicity of heavy metals, tributyltin, ammonia and polycyclic aromatic hydrocarbons to benthic amphipodgrandidierella japonica

Benthic amphipod,Grandidierella japonica widely inhabits the Korean coastal waters and is developed as a standard test species for sediment toxicity tests. We exposedG . japonica to various pollutants including 4 kinds of inorganic metals (Ag, Cd, Cu and Hg), tributyltin [TBT], ammonia and 7 polycyclic aromatic hydrocarbon (PAH) compounds (acenaphthene, chrysene, fluoranthene, fluorene, naphthalene, phenanthrene and pyrene) to estimate the no observed effect concentration (NOEC) and the median lethal concentration (LC50) of each pollutant during the 96-hour acute exposure. Among all tested pollutants, TBT was most toxic toG. japonica, and Hg was most toxic among inorganic metals. The toxicity of pyrene toG. japonica was greatest among PAH compounds, followed by fluoranthene, phenanathrene, acenaphthene, fluorene and naphthalene. The toxicity of PAH compounds was closely related to their physico-chemical characteristics such as K_ow and water solubility.G. japonica responded adequately to pollutant concentrations and exposure durations, and the sensitivity ofG. japonica to various inorganic and organic pollutants was generally comparable to other amphipods used as standard test species in ecotoxicological studies, indicating this species can be applied in the assessment of environments polluted by various harmful substances.     

Measurement of a time-weighted average concentration of polycyclic aromatic hydrocarbons in seawater: An improved procedure of blue rayon hanging technique for monitoring benzo(a)pyrene

We have proposed a time-weighted measurement using blue rayon that selectively adsorbs and concentrates polycyclic aromatic hydrocarbons (PAH), e.g. benzo(a)pyrene (BaP). Though the method was demonstrated to be a convenient way to monitor PAH, the amount adsorbed to the blue rayon depends on the intensity of water stream and the level of PAH. The intensity of water stream was measured by ‘plaster ball’ method, while TWA of PAH in water was measured by a portable sampler using solid phase extraction cartridge. A level of BaP measured by the original blue rayon technique was corrected in this way by the water stream intensity, which correlated well with the TWA of BaP measured by the portable sampler. The improved blue rayon hanging method was applied to several field sites in the Seto Inland Sea of Japan. TWA of BaP ranged from 0.08 to 3.78 ngl⁻¹. These results showed the possibility that the method could be used to evaluate pollution in aquatic environment.