珠江水体表层沉积物中PAHs的含量与来源研究

沿珠江白鹅潭水域及大学城官州河流域设立6个采样点,利用沉积物捕获器收集沉积物。参照美国EPA8000系列方法及质量保证和质量控制,对各采样点表层沉积物中16种多环芳烃（polycyclic aromatic hydrocarbons,PAHs）进行分析,以阐明珠江广州河段表层沉积物中PAHs的含量和分布特征,并结合特征化合物指数对其来源作初步探讨。珠江广州河段表层沉积物中PAHs总量介于4 787.5～8 665 ng·g^-1,平均值为7 078 ng·g^-1,黄沙码头河涌出口沉积物中总量为最高（8 665 ng·g^-1）,芳村码头为最低（4 787.5 ng·g^-1）。16种多环芳烃中菲、荧蒽、芘含量较高,分别占PAHs总量的16.11%、14.47%和17.77%。特征化合物荧蒽/202比值均小于0.5,茚并[1,2,3-cd]芘/276比值均大于0.2,表明珠江广州段表层沉积物中PAHs主要来源于化石燃料的不完全燃烧。     

测定5种高环多环芳烃毒性当量因子并应用于太湖梅梁湾表层沉积物分析

作用位点和作用机理相同的污染物通常具有毒性加合作用,但是各个污染物对总体毒性的贡献并不相同,因此需要采用等毒性当量方法进行归一化．本研究选取了5种具有较强芳烃受体效应的多环芳烃(PAHs),通过大鼠肝癌细胞株H4ⅡE体外EROD酶诱导试验,得到相应的剂量／效应关系曲线,并计算了单个PAH的毒性当量因子 (EROD-TEF)．研究结果表明,不同PAH对EROD响应的EC50有较大区别,毒性相对强弱按照苯并[k]荧蒽>茚并 [1,2,3-cd]芘>苯并[a]芘>苯并[b]荧蒽>苊的顺序递减,对应的EROD-TEF值分别为1．1×10-4、3．0×10-5、3．9×10-6、 2．8×10-6和1．5×10-6．利用所得到的EROD-TEF值和气相色谱-质谱(GC-MS)联用方法测定的太湖梅梁湾地区表层沉积物中16种PAHs的浓度,计算得到5种PAHs的2,3,7,8-TCDD毒性当量TEQPAH,并与体外EROD酶诱导生物测试方法测得的表层沉积物毒性当量EROD-TEQ进行了比较．结果显示,两者间存在较好的线性关系(r2=0．65, p<0．05),证明实验测得的EROD-TEF值能够用于实际样品的分析;所研究的沉积物样品中5种PAHs对总芳烃受体效应的贡献均大于50％,表明PAHs是太湖梅梁湾地区表层沉积物中主要的芳烃受体效应活性物质,其可能引起的环境风险应得到进一步重视．     

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.     

基于统计方法的辽东湾沉积物中多环芳烃来源特征分析

为研究辽东湾表层沉积物中多环芳烃(PAHs)的来源特征,2014年5月采集了20个辽东湾海域表层沉积物样品,并利用气相色谱质谱联用仪对优先控制的16种PAHs进行测定,采用聚类分析、主成分分析-多元线性回归分析、异构体比值3种统计方法对辽东湾表层沉积物中PAHs来源特征进行了研究。结果表明,辽东湾表层沉积物中PAHs含量范围88.5~199.3 ng·g-1,平均值为(126.3±35.3)ng·g-1,其中,萘、菲和荧蒽是PAHs优势组分。通过统计分析结果表明,辽东湾北部表层沉积物中PAHs含量低于西南部,沉积物中PAHs的来源包括石油燃烧来源、煤炭、木材等生物质燃烧来源和石油来源,其中燃烧来源是主要来源,煤炭、木材等生物质燃烧来源占49.9%,石油燃烧来源和石油来源占50.1%。     

绿色食品产地土壤中PAHs测定方法研究

对绿色食品产地土壤中多环芳烃的气相色谱质谱联用分析法进行了研究。样品经索氏提取后硅胶氧化铝复合柱净化,最后用GC/MS内标法进行定性定量分析。方法相关系数除苯并(a,h)蒽的相关系数R2=0.9970外,其余目标化合物的相关系数R2均大于0.9991,各化合物线性关系良好。方法加标回收率大多在70%至90%间,各目标化合物的方法检测限为2.2～40ng/kg。     

Sediment nutrient flux in a coastal lake impacted by diverted Mississippi River water

The internal nutrient load from bottom sediment to the water column of a Louisiana Barataria Basin lake (Lake Cataouatche) receiving diverted Mississippi River water was determined. Dissolved reactive phosphorus (DRP), ammonium (NH₄-N) and nitrate (NO₃-N) flux from sediment to water column were measured. The DRP flux averaged-0.22 mg m^-2 d^-1 under aerobic water column conditions, as compared with that 3.29 mg m^-2 d^-1 under anaerobic conditions. The average NH₄-N released under anaerobic conditions (1.42 mg m^-2 d^-1) was significantly greater than rates under aerobic conditions (-0.02 mg m^-2 d^-1), indicating a strong relationship between nutrient flux and oxygen availability in the water column. The average NO₃-N flux was 2.13 mg m^-2 d^-1 under aerobic conditions as compared with-0.24 mg m^-2 d^-1 under anaerobic conditions in the sediment-water column. When the water column maintained under anaerobic conditions was switched to aerobic conditions, the DRP, NH₄-N, and NO₃-N concentrations in overlying water decreased rapidly over a short period of time. The mean annual internal DRP and NH₄-N load from the sediment to the overlying water was estimated to be 69.26 and 29.9 tonnes (Mg) yr^-1 respectively, which represents a significant portion of the total nutrient load to the Lake. Results demonstrate that the internal flux of nutrients from sediments can contribute a significant portion of the total nutrient load to the water column and should be considered in decisions on impact of nutrient in diverted Mississippi River on water quality of Barataria Basin.     

Historical record of anthropogenic polycyclic aromatic hydrocarbons in a lake sediment from the southern Tibetan Plateau

High-altitude lake sediments can be used as natural archives to reconstruct the history of pollutants. In this work, the temporal distribution of polycyclic aromatic hydrocarbons (PAHs) was determined in a sediment core collected from the southern Tibetan Plateau (TP), which was dated by using the ²¹⁰Pb dating method and validated with the ¹³⁷Cs fallout peak. The concentrations of the anthropogenic PAHs (Σ₈PAH) in the sediment core ranged from 0.83 to 12 ng/g dw, and the fluxes of the Σ₈PAH were in the range of 2.1–27 g/cm²/year. The temporal variations in the concentration and input flux of anthropogenic PAHs were low with little variability before the 1950s, and then gradually increased from the 1950s to the 1980s, and an accelerated increase was observed after the early 1980s. The content of total organic carbon played an insignificant role in affecting the time trends of PAHs in the sediment core. Diagnostic concentration fractions of PAH components indicate PAHs in the lake sediment of the southern TP which are mainly from biomass burning and/or from long-range atmospheric transport.     

土壤和沉积物中的聚合有机质对多环芳烃分布和提取的影响

为了研究土壤和沉积物中凝聚型有机碳(碳黑、干酪根)的含量及其对多环芳烃(PAHs)分布和提取的影响,分别用三氟醋酸(TFA)和在375℃下通氧燃烧的方法从珠江三角洲2个污染土壤和5个河口沉积物样品中提取酸非水解有机碳(NHC)和碳黑(BC);用索氏抽提法和不同溶剂的加速溶剂萃取法(包括连续加速萃取法ASESum和标准溶剂萃取法ASESTD)抽提土壤和沉积物中的多环芳烃,并在不同温度梯度(25℃到150℃)下用水为溶剂加速溶剂萃取其水溶态.结果表明,1)NHC是珠江三角洲土壤和沉积物中总有机碳的重要组成部分,NHC碳明显高于BC碳,NHC和BC分别占土壤和沉积物中有机碳的25.6%￣73.8%和4.64%￣17.3%.2)3种有机溶剂(丙酮、甲苯1、甲苯2)连续抽提的PAHs含量是索氏抽提的2.11倍;5种ASE方法(丙酮、甲苯1、甲苯2、ASESum、ASESTD)提取的PAHs含量与NHC含量存在明显的相关性,而且比PAHs含量与BC或无定型有机碳(AOC)含量的相关性更明显.3)在不同温度梯度下水溶态PAHs浓度符合Van’tHoff方程.研究说明除了BC外,非水解有机碳对土壤和沉积物中PAHs的分布和提取具有重要影响.     

Analyses of PAHs (polycyclic aromatic hydrocarbons) and mutagenicity in raw and chlorinated water

Both raw water and chlorinated drinking water samples were collected from and the Liu‐Du water treatment plant in northern Taiwan from October 1990 to April 1992. The polycyclic aromatic hydrocarbons (PAHs) and mutagenicity in these water samples were analyzed by GC/MS and Ames test. The Mutagenicity/DMSO (Dimethyl Sulfoxide) ratio in S. typhimurium TA98 and TA100 with or without S9 mixture increased, even higher than 2, following the sequence of unit process. It was observed that the mutagenicity with TA98 (S9+) was highly related to most of PAHs in the raw water; while the mutagenicity with TA98 (S9+) was only correlated with DbA and BghiPr in the treated water. It could be expected that the mutagenicity level was controlled by other predominant components after the raw water was treated, for example, the chlorination process.     

厌氧-膜生物反应器处理垃圾渗滤液中多环芳烃的研究

采用固相萃取前处理和气相色谱／质谱联用的方法,分析厌氧．膜生物反应器处理垃圾渗滤液中多环芳烃的去除效果．结果表明,对多环芳烃的总去除效率超过80％;大部分三环、四环和五环的芳烃可在处理过程中被厌氧降解．多环芳烃的主要降解反应发生在厌氧滤池工艺段,然而SCOD(溶解性化学耗氧量),BOD和TOC的主要去除工艺段则是膜生物反应器．     

室内空气中多环芳烃污染的测量和特征性研究

本文就室内空气中多环芳烃典型污染源－室内燃煤和室内吸烟排放的多环芳烃组成和含量进行了测定，并同室外大气（对照）中多环芳烃组成含量进行了对比，研究了室内环境不同污染源排放多环烃组成和含量的特征性，结果表明，室内燃煤污染同燃煤型室外大气源排放多环芳烃具有相似组成含量特征，而室朵烟草烟雾污染源的多环芳烃组成含量特征，则与室外煤型和交通型均有显著区别。     

Enrichment and transfer of polycyclic aromatic hydrocarbons (PAHs) through dust aerosol generation from soil to the air

● Compositional patterns of PAHs in dust aerosol vary from soil during dust generation. ● The EF of PAH in dust aerosol is affected by soil texture and soil PAH concentration. ● The sizes of dust aerosol play an important role in the enrichment of HMW-PAHs. Polycyclic aromatic hydrocarbons (PAHs) are major organic pollutants in soil. It is known that they are released to the atmosphere by wind via dust aerosol generation. However, it remains unclear how these pollutants are transferred through the air/soil interface. In this study, dust aerosols were generated in the laboratory using soils (sandy loam and loam) with various physicochemical properties. The PAH concentrations of these soils and their generated dust aerosol were measured, showing that the enrichment factors (EFs) of PAHs were affected by soil texture, PAH contamination level, molecular weight of PAH species and aerosol sizes. The PAHs with higher EFs (6.24–123.35 in dust PM_2.5; 7.02–47.65 in dust PM₁₀) usually had high molecular weights with more than four aromatic rings. In addition, the positive correlation between EFs of PAHs and the total OC_aerosol content of dust aerosol in different particle sizes was also statistically significant (r = 0.440, P < 0.05). This work provides insights into the relationship between atmospheric PAHs and the contaminated soils and the transfer process of PAHs through the soil-air interface.     

Spatial variability in characteristics and trace metal levels in sediments from watercourses

Assessing sediment quality requires sampling designs which address variability. Often however, only one sample or composited sample is collected at a sample site. Existing studies on sediment variability or sampling strategies primarily concern lake or marine sediments. Two rivers and one canal were sampled to assess sediment variability. Further, it was determined if sediment contamination in running water could be predicted by using visual criteria and/or knowledge of the presence of depositional and erosion areas. Metal concentrations and sediment characteristics were measured in different visually distinct areas of the river. At all sample sites the coefficient of variance was relatively high for most sediment characteristics (1.4‐ > 100%) and metal levels (15.3–63.6%). In one river the majority of sediment characteristics variation was between two sediment types and detected by visually distinct differences. Significant differences in cadmium and zinc concentrations were also detected. Contrary to what was expected, cadmium, and zinc levels were highest in the coarse fraction. No differences were found in the second river. In the canal a greater concentration of fine grained sediments and metals were found in the deep areas. It was not possible to predict sediment areas with the highest levels of metal contamination using visual criteria or knowledge of the erosion and sedimentation pattern of the river.     

云南宣威肺癌高发区C1煤燃烧排放颗粒物中PAHs的组成特征及健康风险

宣威煤燃烧排放产物与其所导致的肺癌高发率一直是国际学术界关注的热点,但煤燃烧排放颗粒物中的关键致毒组分还不清楚。以肺癌高发区产出的晚二叠世C1煤燃烧排放不同粒径颗粒物为研究对象,分析其中主要有害有机污染物多环芳烃(PAHs)的分布特征及其健康风险。结果表明宣威煤燃烧排放的颗粒物中16种PAHs的总质量浓度为77 359.21 ng·m-3,其中含量最高的是苯并(g,h,i)苝,其他主要的PAHs依此为:屈、苯并(b)荧蒽、苯并(a)蒽、荧蒽、二苯并(a,h)蒽、菲、苯并(k)荧蒽、茚并(1,2,3-cd)芘;强致癌化合物苯并a芘(Ba P)总浓度亦可达到10 060.13 ng·m-3;这些有害有机物主要分布在细颗粒物中;不同粒径颗粒物的毒性当量存在明显差异,细颗粒的毒性当量占可吸入颗粒物中PAHs总毒性当量的87.4%,远高于粗颗粒(12%)和超细颗粒物(0.4%)的毒性当量。     

汕头经济特区土壤中优控多环芳烃的分布

运用气相色谱-质谱方法对汕头经济特区131个土样中的美国EPA优控多环芳烃(PAHs)进行定性、定量测定,讨论了PAHs的分布特征。结果表明,该区表层土壤中优控PAHs的总质量分数范围从22.1 ng/g到1256.9 ng/g之间,平均质量分数为(317.3210.2) ng/g。其分布随采样点的位置不同而有显著变化:工业区附近多环芳烃的质量分数最高,城市中心次之,郊区最低。大多数样点中?PAHs质量分数和单种PAH质量分数都呈现w(5~20 cm)> w(0~5 cm)>w(20~40 cm)>w(40~100 cm)的垂直分布规律。该区土壤PAHs以3环和4环化合物为主,单种PAH以萘、菲和苯并[b]萤蒽为主。     

广东清远电子垃圾处理地沉积物对伸展摇蚊的慢性毒性效应

电子垃圾拆解引起的环境污染和生态风险已成为全球关注的热点问题,不适当的电子垃圾拆解过程造成处理区水体沉积物受到多类有机化合物和重金属污染,直接威胁生活在沉积物中的底栖动物。在典型电子垃圾处理地广东清远采集沉积物,测定样品中以烃类为主的色谱难分离混合物(unresolved complex mixture,UCM)的含量,开展伸展摇蚊全生命周期慢性毒性测试。结果表明,清远沉积物中的UCM浓度(0.08±0.01)%接近于这类污染物对伸展摇蚊的慢性半致死性效应浓度(0.073±0.022)%。同时发现清远沉积物对以摇蚊为代表的底栖无脊椎动物具有显著慢性毒性效应,且可通过测定UCM含量初步估算。这为开展以电子垃圾处理地沉积物为代表的,受到以麻醉作用为主要致毒机制的混合物污染的沉积物的毒性评价提供了一种有效方法。     

京津潮白河多环芳烃及其衍生物分布

采用固相萃取-气相色谱质谱联用仪测定京津潮白河中的多环芳烃(PAHs)及其衍生物(SPAHs)的污染水平,并采用絮凝法分析水样中自由态PAHs/SPAHs和结合态PAHs/SPAHs的分布。结果表明,京津潮白河中PAHs和SPAHs总质量浓度分别为55.06～215.02 ng·L~(-1)和92.37～227.33 ng·L~(-1),上游河段PAHs和SPAHs质量浓度均低于下游河段。7种致癌PAHs占比为22%～41%,需引起重视。本研究中的SPAHs包括三类物质:氧化PAHs(OPAHs)、甲基PAHs(MPAHs)和氯代PAHs(Cl PAHs)。其中,OPAHs对SPAHs贡献最大(59%～71%),其次是Cl PAHs(22%～32%)和MPAHs(7%～14%)。京津潮白河中PAHs和SPAHs主要以自由态形式存在,总浓度可以准确估计污染物的环境风险。     

Polyzyklische aromatische Kohlenwasserstoffe aus diffusen Quellen

Goal and Scope

Polycyclic aromatic hydrocarbons (PAHs) are one group of persistent organic pollutants which are ubiquitous distributed in soils, even in rural areas. After their release into the atmosphere, transportation and deposition, they tend to accumulate in topsoils and sediments. Similar distribution pattern of PAHs in atmospheric deposition, soil samples as well as sediment samples indicate a close relationship between atmospheric input and accumulation of PAHs in the terrestrial environment. The intention of this paper was to estimate the time when precautionary values of the German law of soil protection will be exceeded in rural areas. Furthermore, current soil concentrations will be linked to the historical record of PAHs by means of enrichment factors.

Methods

The historical record of the atmospheric deposition rates of PAHs can be obtained from investigation of sediment cores. Based thereon, enrichment factors of PAHs in the environment were calculated. With these enrichment factors it was possible to estimate the recent PAH concentration in soils in rural areas from currently measured annual deposition rates. Furthermore, concentrations of PAHs in soils and deposition rates can be used to calculate the time when precautionary values will be reached.

Results and Conclusion

PAH deposition rates have been decreasing since about 1960 by a factor of 2–3, but stabilized during the last decade on a level high above pre-industrial time. Thus, further enrichment of PAH in topsoils has to be expected. Actual deposition rates in connection with historical enrichment factors allow to determine the median concentrations of PAHs in rural soils. The time when precautionary values will be reached was calculated to about 300 Years.

Outlook

The database to predict the further development of atmospheric deposition rates is very weak. There was a lack of validated methods concerning direct measurements of atmospheric POP deposition. Meanwhile, a national draft of a standard base on time-integrated passive sampling exists. This method can be implemented to establish a combined soil and deposition-monitoring program in order to assess the risk of further accumulation of POPs in soils.     

An approach to uncertainty estimation in determining polycyclic aromatic hydrocarbons in fuel-contaminated soils

An estimation of uncertainty contribution in the entire set of the analytical data of polycyclic aromatic hydrocarbons (PAHs) in soil during a full year is presented. The analyses were performed as part of a project devoted to the assessment of the natural attenuation of selected PAHs in agricultural soil contaminated by a fuel spill. In particular, we investigated the effect of natural attenuation on the PAH dissipation rate in plots of two types of scenarios in agricultural soils. One of them was previously affected by an accidental fuel spill 10 years ago, and the other one was non-affected. The major components for estimating uncertainty contributions have been evaluated based on intermediate precision from different levels of PAH mass fraction, sample locations, and long term data set. An analysis of variance (ANOVA) test was applied to the mass fractions of clean or blank soil sub-samples versus contaminated soil sub-samples for grouping comparable data. Variables of influence in this study were site, month, and lysimeter of sampling (referring to a stainless steel box, with side lengths of 50 cm). Study sites or the spatial arrangement of lysimeter showed a clear effect in sub-sample results with the lowest mass fraction levels for heavier PAH, while monthly sampling was the variable of most significant influence for the more strongly contaminated sub-sample results.

Finally, the results of the PAH mass fractions in contaminated soil sub-samples indicated a monthly variation for which lighter, volatile PAHs rapidly decreased while the less volatile did not change.     

Sources of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Biobio River in south central Chile

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment; there are concerns about them due to their toxic properties. Human activities could significantly contribute to the total PAH burden in river sediments. In this work, we document the analysis of PAHs in sediments taken in the middle stretch of the Biobio River in south central Chile. This river is a principal system, draining more than 24,000 km² and subjected to a diverse variety of human-made stressors (pulp mill and urban effluents, agricultural drainage systems, etc). During 2003, several sediment samples were taken in more than 45 sampling sites located in the river’s middle stretch. Due to the granulometric characteristics (mainly sandy sediments), only 17 samples were analyzed, taking into consideration the presence of a fine section within the sediment sample. Using HPLC with fluorescence detection, 15 EPA priority PAHs and perylene were analyzed. The composition of PAHs in the sediment samples is rather similar between sites and levels averaged 104 ± 78 ng g⁻¹ d.w. The highest levels were detected downstream from an industrial discharge. A good correlation was observed between PAH levels and organic carbon content in the tested sediments; however, concentrations above 134 ng g⁻¹ d.w. did not indicate correlation. The samples PAH ratios (Flu/Pyr and Chr/B(a)A) reveal a strong pyrolytic PAH pattern in the sediments tested, supporting evidence indicating that PAHs come mainly from pyrolytic sources. This result contrasts with previous records that have shown a natural influence in the upper basin and a petrogenic pattern near the mouth.