渤海北部典型芳香烃类化合物污染状况及生态风险评价

为探究渤海北部海上油气区及周边近岸海域典型芳香烃类化合物污染状况,2015年5月现场采集了32个站位的海水样品,针对7种苯系物(BTEX)和17种多环芳烃(PAHs)进行测定,并采用商值法和毒性当量法对污染物开展单一和联合生态风险评估。结果显示,研究海域海水中7种苯系物总含量范围为65.1～222.6 ng·L~(-1),以甲苯含量最高,表层含量略低于底层,油气区平均含量低于周边近岸,受到陆源污染输入的影响特征明显。表层海水中ΣPAHs含量范围为98.9～356.0 ng·L~(-1),平均值为184.5 ng·L~(-1),以低环芳烃占优势,总体处于中等水平,比值法判定该海域PAHs可能主要来源于石油及其加工产品。该海域海水中苯并(a)芘的风险商RQ值大于0.1,表现出低度风险,其余3种处于可接受水平。4种芳香烃类化合物联合生态风险等级为低度风险,对生态系统具有潜在的不利影响,但不同区域仍存在一定差异性,海上石油开采与陆源输入是影响该海域个别区域生态风险较高的重要因素。     

环渤海北部沿海地区表层土壤中PAHs的污染特征及风险评价

系统采集了环渤海北部沿海地区31个表层土壤样品,利用GC/MS分析了16种USEPA优控多环芳烃(PAHs)的含量和组分特征,运用主成分因子载荷法揭示了其污染来源,并初步评价了其风险水平.结果表明,沿海地区65%的土壤已被污染,最高污染样点PAHs含量达920.4ng·g-1,平均含量309.5ng·g-1,与国内外相关研究比较,处于中低等污染水平.各类燃料的不完全燃烧是该地区土壤中PAHs的主要来源,石油类挥发或泄漏对采油区土壤中PAHs的累积影响显著.     

Organochlorine pesticides (HCHs and DDTs) in soils along the north coastal areas of the Bohai Sea,China

A systematic survey of organochlorine pesticides (OCPs) including hexachlorocyclohexane isomers (α-HCH, β-HCH, γ-HCH, δ-HCH and ΣHCH) and dichlorodiphenyltrichloroethane metabolites (p,p′-DDT, p,p′-DDE, o,p′-DDT, p,p′-DDD and ∑DDT) in soils along the north coastal areas of the Bohai Sea, China, has been lacking. In this study, 31 representative surface soil samples were collected along the north coastal and riverine areas of the Bohai Sea to characterise the potential for adverse effects of ∑HCH, ∑DDT and their individual isomers and transformation products. Concentrations of ΣHCH and ΣDDT in soils ranged from less than the limit of detection (1 ng · g^?1 dw (mean: 3.5 ng · g^?1 dw) and2 ng · g^?1 dw (mean: 1.7 × 10¹ ng · g^?1 dw), respectively. Compared with studies of OCPs in soils from other locations, concentrations of HCHs and DDTs observed in this study were moderate. Concentrations of OCPs observed in soils were generally less than proposed reference values. HCH residues were a mixture of historical technical HCH and current lindane sources. The pattern of DDTs was consistent with historical releases of technical DDTs. Selected soil physicochemical properties did not explain the sorption and/or partitioning of HCHs or DDTs.     

上海市河流表层沉积物中的氯酚、溴酚及多环芳烃

应用气相色谱/质谱（GC/MS）分析了上海市黄浦江、苏州河及蕰藻浜表层底泥样品中19种氯酚（CPs）、2种溴酚（BPs）和美国环保局（EPA）优先控制的16种多环芳烃（PAHs）的含量.结果表明,黄浦江底泥中19种CPs的总平均浓度最高（18.3 ng.g-1干重（dw））,苏州河次之（14.8 ng.g-1dw）,蕰藻浜最低（4.44 ng.g-1dw）,而两种BPs的含量相当.4-氯酚（4-CP）和五氯酚（PCP）是占主导的污染物,表明底泥中CPs可能受人类生活生产活动的影响较大;而BPs的来源有待进一步深入的研究.CPs的毒性当量贡献值随着氯原子取代数的增加而增加.底泥中16种PAHs的总浓度范围是132—6800 ng.g-1dw（平均值为3050 ng.g-1dw）.PAHs组成特征及源解析表明,底泥中PAHs主要来自燃烧源.生态风险分析显示,上海市水体底泥中的PAHs均未超过生态风险评价中值（ERM）,表明不存在严重和频发的PAHs生态毒理风险.     

黄海近岸表层沉积物中多环芳烃来源解析

采集了黄海近岸(日照岚山海域)12个站位的表层沉积物样品,利用气相色谱-质谱仪(GC-MS)分析了样品中16种多环芳烃(PAHs)的含量,结果显示16种PAHs含量范围在76.384～7512.023 ng·g-1,平均值为2622.576 ng·g-1.低环PAHs组分所占比重较大,中高环PAHs相对较小.利用比值法定性解析PAHs的来源,初步判断PAHs可能来自燃煤、燃油、焦化、柴油泄漏等污染源.进一步引用相关源成分谱,应用化学质量平衡模型(CMB8.2)对PAHs的来源进行定最解析,拟合计算结果表明研究海域表层沉积物中PAHs的主要来源为燃煤源、燃油源(主要为柴油燃烧)和焦炉源,其相对贡献率分别为53.99%、25.57%和13.97%.     

离子强度对土壤与沉积物吸附多环芳烃的影响研究

以黄河三角洲表层沉积物与湿地土壤为对象,研究了离子强度对菲、苯并[a]芘在土壤和沉积物上吸附行为的影响。结果表明:不同Ca2 离子强度下,土壤与沉积物对菲、苯并[a]芘的吸附速率均较快,48h吸附能够达到平衡,Ca2 离子强度对土壤和沉积物影响程度不同;土壤和沉积物的吸附等温线均呈线形,能较好地符合线性方程,可决系数R2在0.98以上,菲的KD值在24~130mL·g-1之间,苯并[a]芘的KD值在3517~5081mL·g-1;随着体系离子强度的增大,土壤与沉积物对PAHs的吸附能力均降低,而且两者之间的吸附量差距明显降低,表明离子强度对土壤影响程度明显大于沉积物。     

Multiphase redistribution differences of polycyclic aromatic hydrocarbons (PAHs) between two successive sediment suspensions

Successive sediment suspensions often happen in estuary, yet little research has probed into the difference in the release behaviors of organic compounds among different suspensions. This study took polycyclic aromatic hydrocarbons (PAHs) as typical organic contaminants and investigated the release behaviors between two successive suspensions with a particle entrainment simulator (PES). Results showed that successive sediment suspensions lowered the concentration of dissolved PAHs in the overlying water via facilitating the re-adsorption of dissolved PAHs onto the suspended particles. Fast-release and slow-release periods of PAHs were successively observed in the both suspensions. The concentration changes of dissolved PAHs in the second suspension were generally similar with but hysteretic to those in the first suspension. More vigorous desorption and re-absorption of PAHs were induced in the second suspension. Successive sediment suspensions obviously decreased the concentrations of mineral composition and organic matters in the overlying water, which significantly affects multiphase distribution of PAHs.     

环渤海渔港沉积物多环芳烃的污染特征和生态风险评价

2019年5-6月采集了环渤海20个渔港的沉积物样品,采用高效液相色谱紫外成光检测器串联方法对16种多环芳烃(PAHs)进行检测,分析了其分布和组成特征,采用比值法和正定矩阵因子模型法(PMF)对PAHs进行定量源解析,采用效应区间中低值法和中值商法评估其生态风险.10种PAHs的检出率达到100％,表明PAHs在沉积...     

Sources and spatial distribution of polycyclic aromatic hydrocarbons in coastal sediments of the Basque Country (Bay of Biscay)

This contribution characterises the sources and distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Basque coast (Bay of Biscay). Different source characterisation approaches (i.e. GIS assisted-chemometrics, PAH diagnostic ratios and analyses of composition profiles) were used in combination to successfully identify the factors determining the origin and distribution of PAHs. Urban/industrial combustion processes were identified as the main PAH source. However, the analysis of PAH composition patterns and diagnostic ratios identified secondary natural and petrogenic PAH sources on small spatial scales. The median ∑18PAH concentration ranged from 66 μg kg^?1 (d.w.) to 7021 μg kg^?1 (d.w.). The Ibaizabal estuary, which supports most of the anthropogenic pressure in the region (i.e. urban development, industrialisation, commercial and recreational harbours), also showed the highest PAH concentrations. On the shelf, human activities, hydrodynamic conditions and geomorphological features led to spatial differences in the PAH concentrations among sectors: the offshore and west sectors were characterised by higher concentrations, while the lowest values were found in the mid and east sectors. The results enhance the knowledge on PAH-related contamination processes and could be used to support the environmental assessment process required under current European marine legislation.     

土壤与沉积物对多环芳烃类有机物的吸附作用

吸附作用是疏水性有机物在土壤和沉积物环境中的重要迁移转化行为之一。多环芳烃是环境中一种重要的疏水性有机污染物。文章着重阐述了多环芳烃类有机物在土壤和沉积物中有机质和粘土矿物吸附机理，指出土壤、沉积物有机质的结构异质性是导致非线形吸附的重要原因；分析了影响多环芳烃吸附过程的诸多因素，并提出该研究领域存在的问题以及今后发展的方向。     

Comparison of extraction methods for polycyclic aromatic hydrocarbon determination in sediments

Different sample preparation methods for the determination of polycyclic aromatic hydrocarbons (PAHs) in lake and river sediments were compared and evaluated. Freeze‐dried sediment materials were extracted using Soxhlet extraction, ultrasonic agitation and digestion with various solvents and solvent mixtures. Similarly, clean‐up methods using various types of sorbents for separation of PAHs tested.

The following method gives the best results for the determination of PAHs: freeze‐dried sediment samples were extracted using Soxhlet extractor with dichloromethane (6 hr, dark), extracts were cleanup using Silica gel and a mixture of n‐hexa‐ne‐dichloromethane was used for the elution of PAHs.

This method was used for the determination of 7 selected PAHs in sediment samples from Finnish lakes and Czech streams.     

杭州市郊区表层土壤中多环芳烃的风险分析

采集杭州市郊区表层土壤中多环芳烃的样品,用色谱-质谱技术对多环芳烃化合物进行定量分析。美国环保总署推荐优先控制的16种多环芳烃单体质量分数在1.49～87.43 ng.g-1之间,萘、芴、苊等低分子量芳烃质量分数相对较低;、茚并[1,2,3-cd]芘、苯并[ghi]苝等高分子量芳烃质量分数相对较高,其中苯并[ghi]苝质量分数最高。对照荷兰的土壤标准,杭州市郊区表层土壤中的荧蒽、、茚并[1,2,3-cd]芘、苯并[ghi]苝超标比较严重,超标率100%;多环芳烃的Bap等效毒性当量是荷兰规定目标值的2倍;因此,杭州市郊区表层土壤中存在一定的潜在风险。多环芳烃Ant/（Phe＋Ant）、BaA/（Chr＋BaA）、Flua/（Pyr＋Flua）等参数表明,多环芳烃主要来源于燃烧源,且以机动车尾气为主;BeP/（BeP＋BaP）比值偏高,可能与土壤中的多环芳烃主要来源于大气沉降有关。     

钢铁工业区周边农业土壤中多环芳烃(PAHs)残留及评价

对某大型矿业企业周边农业土壤中多环芳烃(PAHs)残留量进行了调查。结果表明,PAHs总残留量范围为312. 2~27 580. 9ng·g-1,且以4环以上多环芳烃组分为主。所有土样中均检出PAHs,单一污染物以芘、艹屈、荧蒽、苯并[a]芘、蒽、菲、苯并[a]蒽、苯并[k]荧蒽、茚并[1,2,3 cd]芘、苯并[g,h,i]苝为主。PAHs残留量与有机质含量相关性较好。不同样区土壤PAHs残留量受常年风向影响明显。以加拿大农业区域土壤PAHs的治理标准值为指标,用内梅罗综合指数法进行评价表明,研究区农业土壤达重污染水平的占37%,中度污染的占19%,轻污染的占25%,另有13%的采样点污染程度处于警戒限,仅有6%的采样点尚处于安全级。     

环渤海近岸海域表层沉积物及底栖生物中PBDEs的赋存特征及富集行为

多溴联苯醚(PBDEs)作为一种新型的持久性有机污染物,在海洋环境中广泛存在,研究PBDEs在不同介质中的赋存状态对于理解其环境行为及归趋具有重要的意义。通过采集不同区域沉积物及生物样品,考察了PBDEs在环渤海近岸海域表层沉积物及底栖生物中的含量及空间分布特征、污染模式及生物-沉积物富集因子。结果表明,环渤海沿岸表层沉积物中PBDEs总量(Σ10PBDEs)的浓度范围在0.446~26.8 ng·g-1(干重,dw)之间,中值为1.02 ng·g-1(dw),底栖生物中PBDEs(Σ9PBDEs)的浓度范围为0.053~9.90 ng·g-1(dw),中值为1.25 ng·g-1dw;沉积物中BDE-209为最主要的单体,平均丰度达到90.5%,生物体中主要以低溴代BDEs为主,其中单体BDE-47的含量最高,平均丰度范围为43.2%~49.7%;沉积物和生物中PBDEs的含量在空间上存在显著的差异,其中莱州湾和锦州附近区域的结果明显高于其他区域;5种不同的底栖生物对PBDEs均表现出一定的生物富集性,其中∑9PBDEs的BSAF值按从大到小的顺序为菲律宾蛤仔(0.43~4.06,mean=1.19)紫贻贝(0.34~2.86,1.03)四角蛤蜊(0.17~1.95,0.82)麻蛤(0.13~2.33,0.61)牡蛎(0.09~1.20,0.52)。辛醇水分配系数(log KOW)与不同物种BSAF值的相关性分析结果表明,除BDE-17单体外,其他单体的BSAF值表现出随log KOW的升高而下降的趋势。     

渤海典型海域表层沉积物正构烷烃特征比较

对渤海典型海域表层沉积物正构烷烃特征进行比较研究.分别采集葫芦岛市近岸海域(1#)、东营市近岸海域(2#)、营口市近岸海域(3#)9个站点的表层沉积物样品,经索氏提取、柱净化后进行GC-MS分析.结果表明,各站位都表现为双峰型,显示了陆源与海源双重贡献特征,但主导峰各不相同;正构烷烃含量(∑n-alk)均值分别为5.43μg.g-1、2.27μg.g-1、4.30μg.g-1;三海域碳优势指数CPI、奇偶优势指数OEP、姥鲛烷和植烷比值Pr/Ph等特征比值基本相同,指示混合来源及中性偏氧化的沉积环境;C31/C19均值分别为11.19、4.51、6.73,短/长链比值L/H均值分别为0.50、1.48、1.31,类脂物比值TAR均值分别为3.61、1.03、1.19,综合显示葫芦岛市近岸海域正构烷烃来源主要为陆源高等植物,而营口及东营近岸海域沉积物正构烷烃更多来源于内生浮游生物源及石油源,三海域沉积物受人类污染影响程度从高到低分别为2#海域(东营)>3#海域(营口)>1#海域(葫芦岛市),且东营近岸海域沉积物受石油污染特征明显.这些特征都与3个海域周边城市发展与污染输入特征有直接的关系.     

Polycyclic aromatic hydrocarbons in red mullet (Mullus bavbatus) and sediments from the Eastern Aegean Sea

The distribution of polycyclic aromatic hydrocarbons (PAHs) was investigated in red mullet (Mullus barbatus) and sediment samples in the eastern Aegean Sea. The data were collected during cruises in July and November 1994, in the framework of National Marine Measurement and Monitoring Programme in the Aegean Sea. PAHs were detected in the tissue of Mullus barbatus of different sex and size from nine sampling sites throughout the study area ranging from 0.03 to 0.46 ug/g (fresh weight). The observations show the high levels of PAHs were found in tissues of females. The average concentration of PAHs in Aegean Sea sediments ranged from 0.20 to 1.8 ug/g (dry weight). No significant correlation was observed between PAH and sedimentary organic carbon.     

Distribution of polycyclic aromatic hydrocarbons in Datuo karst Tiankeng of South China

Levels of polycyclic aromatic hydrocarbons (PAHs) were measured in surface soils of Datuo karst Tiankeng (large sinkholes) in South China with the use of a gas chromatography-mass spectroscopy (GC-MS) system. This paper provides data on the levels and distribution of PAHs from the top to the bottom of the Datuo karst Tiankeng. The results showed that the sum of the 16 EPA priority PAHs from the sampled locations from top to bottom had a relative increment in PAHs concentration. summation operatorPAHs ranged from 16.93 ng/g to 68.07 ng/g with a mean concentration of 42.15 ng/g. The correlated results showed the bottom of the large sinkhole, which accounts for the higher concentrations, probably acts like a trap for the PAHs. Thus, the low evaporation rate at the bottom may play a key role in controlling the high concentration of PAHs at the bottom.     

The application of solid-phase micro-extraction (SPME) to the analysis of polycyclic aromatic hydrocarbons (PAHs)

There are many established extraction techniques regularly used in the isolation and analysis of PAHs and similar organic compounds from various phases. These include Soxhlet or ultrasonic extractions from solids, and liquid-liquid or solid-phase extraction from aqueous samples. However, these methods have some inherent disadvantages; most require large volumes of organic solvents, they can be time consuming and many involve multi-step processes that always present the risk of the loss of some analytes (Zhang et al., 1994). Solid-phase micro-extraction (SPME) is a relatively new technique that has been used with much success in the analysis of a variety of compounds including PAHs. Experiments are being carried out to determine the optimum range of conditions for the extraction of a range of PAHs. Parameters under investigation include temperature, equilibration time, salinity and compound concentration. Presented here are some preliminary experiments into the applicability of SPME for PAH analysis. Further work will investigate the reproducibility of the technique, limits of detection and matrix effects. When an optimised method has been developed the technique will be used in investigations into PAH profiles in sediment cores.     

渤海湾海岸带表层沉积物中黑碳的分布特征

在渤海湾西海岸潮间带、近海和主要河流采集了85个表层沉积物样品,对黑碳（BC）的质量分数及其分布规律进行了研究,并探讨了BC与沉积物粒度的关系。结果表明：（1）渤海湾海岸带表层沉积物中BC的平均质量分数为（0.65±0.42）mg·g^-1,占总有机碳的比例为16.8%±7.5%,均高于我国其它海岸带;（2）潮间带沉积物中BC的质量分数存在明显的南北分区差异（以天津港码头为界）,北区（0.92mg·g^-1）比南区（0.22mg·g^-1）平均高4倍以上;近海和河流样品BC的质量分数也有一定程度的＂北高南低＂趋势,表明BC在海岸带运移扩散的继承性,河流输入可能是主要途径;（3）潮间带沉积物粒度表现为＂北区细＂（以粘土质粉砂主）而＂南区粗＂（以砂为主）,反映两个区域的水动力条件和沉积环境不同,是造成BC质量分数区域差异的主要原因。     

黄渤海表层沉积物中正构烷烃和甾醇的分布及来源研究

在黄海、渤海湾和莱州湾采集64个表层沉积物样品,分析正构烷烃（C15～C33）和甾醇（菜子甾醇、菜油甾醇、谷甾醇和豆甾醇）的质量分数和分子组合特征,探讨其来源,比较物质来源的空间差异。结果表明：（1）黄海表层沉积物中类脂生物标志物主要呈现陆源和海源共同影响的特征,其中北黄海以陆源输入为主,高碳数正构烷烃（〉C24）具有明显的奇碳优势,陆源高等植物的贡献较大;南黄海陆源输入与海洋自身贡献相当;渤海湾与莱州湾接受来自河流的大量陆源物质;（2）来源于陆源高等植物的甾醇（包括菜油甾醇、谷甾醇和豆甾醇）在黄海表层沉积物中的质量分数远小于渤海湾和莱州湾,但指示硅藻来源的菜子甾醇在整个研究区域均具有较高的质量分数。