在线富集-液相色谱法检测水中多环芳烃

建立了一种在线富集-液相色谱法检测水体中多环芳烃的方法,通过优化色谱条件,可不经萃取浓缩直接上机检测水样,取样体积仅为2.5 ml。除苊烯不能用荧光检测器检测外,其余15种多环芳烃的加标回收率为70.24%(苊)~117.25%(二苯并(a,h)蒽),相对标准偏差(n=5)在1.70%()~11.21%(茚并(1,2,3-c,d)芘)之间,检出限在1.51 ng/L(苯并(k)荧蒽)~44.4 ng/L(茚并(1,2,3-c,d)芘)之间,基本满足痕量分析要求。利用该方法测定实际样品中多环芳烃的浓度为0.053 ng/L(苊)~2.751 ng/L(芴)。     

量子点与多环芳烃复合体系荧光共振能量转移的研究

本研究合成了水溶性CdZnSeS/ZnS绿光量子点和CdSe/CdS/ZnS红光量子点作为荧光探针,与典型多环芳烃（萘、芘、苯并芘、荧蒽）复合构建荧光共振能量转移体系,探讨了量子点-多环芳烃复合体系的部分参数。数据结果表明,量子点与四种多环芳烃之间存在共振能量转移作用,而且在CdZnSeS/ZnS量子点-芘/苯并芘复合体系中,量子点荧光变化幅度与芘/苯并芘浓度在一定范围内存在线性关系,这证明通过构建量子点-多环芳烃复合物荧光共振能量转移体系,可以实现对地下水中多环芳烃的定量分析。     

多环芳烃污染农田土壤生态修复标准研究——辽宁省地方标准(DB 21/T 2274-2014)的建立及其依据

为指导正确评价多环芳烃污染农田土壤生态修复效果及环境风险,根据辽宁省农田土壤多环芳烃污染状况、多环芳烃污染农田土壤生态修复技术特点,参考国内外相关标准,应用生态风险模型,建立辽宁省地方标准(DB 21/T 2274-2014)——多环芳烃污染农田土壤生态修复标准,提出了生态修复完成后农田土壤中总多环芳烃浓度和苯并[a]芘环境当量总浓度限值。主要内容为:生态修复完成后农田土壤中总多环芳烃浓度低于2 mg/kg,生态修复完成后农田土壤中苯并[a]芘环境当量总浓度低于0.53 mg/kg。     

多环芳烃类污染场地的分布特征及来源分析

以某发电厂污染地块为研究对象,分析该场地污染物含量,并研究了多环芳烃类物质在不同功能区域的分布特征。结果表明:场区内土层分布自上而下依次为粉质粘土、淤泥质黏土和粘土,垂直渗透系数范围为1.0×10~(-8)~1.0×10~(-6)cm/s;该场区浓度较高的污染物主要为苯并(a)蒽、苯并(b)荧蒽和苯并(a)芘,主要集中在杂填土层。初步勘察筛选出的浓度偏高的多环芳烃类物质虽未超过标准,但必要时仍需实施场地环境管理措施。     

大庆地区总悬浮微粒中苯溶物及多环芳烃的测定与评价

通过对大庆地区总悬浮微粒（TSP）中主要化学组成──苯溶物、多环芳烃的测定分析得知：苯溶物占TSP的百分含量，年均值为10．31％，在空气中的平均浓度为12．5μg／m3。与北京燕山地区1983～1984年3个生活区（迎风、东风、东炼）苯溶物年平均值比较，大庆地区苯溶物含量较低。而对总悬浮微粒中多环芳烃的测定结果可明显看出各点采暖期苯并（a）芘、多环芳烃总量的浓度虽都明显高于非采暖期，但其致癌强度和浓度都比北京市、太原市及兰州市弱、低。     

岷江成都段水中多环芳烃污染现状分析

运用高效液相色谱对岷江成都段水中多环芳烃的污染现状进行调查,并对其中8种化合物的危害进行讨论。结果显示。岷江成都段受多环芳烃污染比较严重,特别是苯并[a]芘并出现超标情况。     

小麦秸秆生物炭对石油烃污染土壤的修复作用

以小麦秸秆为原材料,在300℃下缺氧裂解3、6、8 h制备生物炭,比较了3种生物炭的产率、pH值、灰分以及C、H、N元素含量,表征了300℃、6 h生物炭的表面形态,并用其作为修复材料,对大港油田的石油污染土壤进行修复。结果表明,随裂解时间的延长,生物炭产率下降,pH值升高,灰分含量增加,H/C值下降,但产率、pH值、灰分和H/C值都是从3h到6h差异显著,6h到8h差异不显著。C元素含量先升高后下降。石油污染土壤经生物炭修复14 d和28 d后,总石油烃降解率分别为45.48％和46.88％,均显著高于对照组。修复14 d后土壤中的萘、苊、苯并[a]蒽、屈、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、茚并[1,2,3-cd]芘也都有不同程度的下降,其中苯并[a]芘含量下降幅度达98.18％,其他几种PAH的降解率也都高于对照组,28 d后这些PAH的含量又有上升趋势。这说明小麦秸秆裂解时间对生物炭的性质有影响;300℃、6 h生物炭可以用来修复石油污染的土壤。     

四川省南充市大气中多环芳烃的分布

用超声波萃取，抽滤，减压蒸发浓缩，硅胶柱净化，再逍缩至干，定客溶解的方法处理了南充市5个监测点冬，夏季乘集的大气颗粒物样品，然后用高效液相色谱法分析其中9种多环芳烃含量，大气中苯并[a]芘的年平均含量为31．5ng/m3，略低于成都市1988年测定的年平均值，南充市大气中多环芳烃的主要来源是居民生活用煤，其次是汽车尾气，改变燃料结构，集中供热，加强城市交通管理，是减少多环芳烃污染的途径。     

镇江东部地区土壤中多环芳烃的污染特征及来源解析

分析了镇江东部扬中地区土壤中16种优先控制的多环芳烃（PAHs）污染物的含量特征及污染水平。结果表明,该地区土壤的多环芳烃总量为2．4～49．9μg／Kg,其中荧蒽的含量最高,同我国其他地区相比,其污染水平比较低。5个采样点PAHs含量表明有两个点受工业企业影响,其他3个点具有类似的面源污染即地质成因来源。     

东营市大气颗粒物中有机污染物的色谱－质谱分析

报道了应用气相色谱和气相色谱。质谱联用法对东营市大气颗粒物中正构烷烃和多环芳烃的分析结果，实际分析中共鉴定出正构烷烃２１种，多环芳烃６３种。定量测定结果表明，东营市冬季大气颗粒物中的总正构烷烃浓度和苯并（ａ）芘浓度均低于国内其他大城市。     

Polycyclic aromatic hydrocarbons in mountain soils of the subtropical Atlantic

Surface soil samples from various altitudes on Tenerife Island, ranging from sea level up to 3400 m above mean sea level, were analyzed to study the distribution of 26 polycyclic aromatic hydrocarbons (PAHs) in a remote subtropical area. The stable atmospheric conditions in this island define three vertically stratified layers: marine boundary, trade-wind inversion, and free troposphere. Total PAH concentrations, 1.9 to 6000 microg/kg dry wt., were high when compared with those in tropical areas and in a similar range to those in temperate areas. In the marine boundary layer, fluoranthene (Fla), pyrene (Pyr), benz [a]anthracene (BaA), and chrysene (C + T) were largely dominant. The predominance of Fla over Pyr may reflect photo-oxidative processes during atmospheric transport, although coal combustion inputs cannot be excluded. The PAHs found in higher concentration in the soils from the inversion layer were benzo[b + j]fluoranthene (BbjF) + benzo[k]fluoranthene (BkF) > benzo[e]pyrene (BeP) approximately indeno[1,2, 3-cd]pyrene (Ind) > benzo[a]pyrene (BaP) approximately benzo[ghi]perylene (Bghi) > coronene (Cor) approximately dibenz[a,h]anthracene (Dib), reflecting that high temperatures and insolation prevent the accumulation of PAHs more volatile than BbjF in significant amounts. These climatic conditions involve a process of standardization that prevents the identification of specific PAH sources such as traffic, forest fires, or industrial inputs. Only soils with high total organic carbon (TOC) (e.g., 10-30%) preserve the more volatile compounds such as phenanthrene (Phe), methylphenanthrenes (MPhe), dimethylphenanthrenes (DMPhe), and retene (Ret). However, no relation between PAHs and soil TOC and black carbon (BC) was found. The specific PAH distributions of the free tropospheric region suggest a direct input from pyrolytic processes related to the volcanic emission of gases in Teide.     

Integrating biodegradation and electroosmosis for the enhanced removal of polycyclic aromatic hydrocarbons from creosote-polluted soils

This paper presents a hybrid technology of soil remediation based on the integration of biodegradation and electroosmosis. We employed soils with different texture (clay soil and loamy sand) containing a mixture of polycyclic aromatic hydrocarbons (PAH) present in creosote, and inoculation with a representative soil bacterium able to degrade fluorene, phenanthrene, fluoranthene, pyrene, anthracene, and benzo[a]pyrene. Two different modes of treatment were prospected: (i) inducing in soil the simultaneous occurrence of biodegradation and electroosmosis in the presence of a biodegradable surfactant, and (ii) treating the soils sequentially with electrokinetics and bioremediation. Losses of PAH due to simultaneous biodegradation and electroosmosis (induced by a continuous electric field) were significantly higher than in control cells that contained the surfactant but no biological activity or no current. The method was especially successful with loamy sand. For example, benzo[a]pyrene decreased its concentration by 50% after 7 d, whereas 22 and 17% of the compound had disappeared as a result of electrokinetic flushing and bioremediation alone, respectively. The use of periodical changes in polarity and current pulses increased by 16% in the removal of total PAH and in up to 30% of specific compounds, including benzo[a]pyrene. With the aim of reaching lower residual levels through bioremediation, an electrokinetic pretreatment was also evaluated as a way to mobilize the less bioaccessible fraction of PAH. Residual concentrations of total biodegradable PAH, remaining after bioremediation in soil slurries, were twofold lower in electrokinetically pretreated soils than in untreated soils. The results indicate that biodegradation and electroosmosis can be successfully integrated to promote the removal of PAH from soil.     

Polycyclic aromatic hydrocarbon removal from soil by surfactant solubilization and Phanerochaete chrysosporium oxidation

Surfactant soil washing can remove polycyclic aromatic hydrocarbons (PAHs) from contaminated soil, and the white rot fungus, Phanerochaete chrysosporium Burdsall in Burdsall & Eslyn, can oxidize PAHs. The objective of this study was to develop a novel bioremediation technology using a combination of abiological surfactant soil washing followed by PAH biological oxidation in soil washwater using P. chrysosporium in a rotating biological contactor (RBC) reactor. Soil used for experimentation was an 11-month aged contaminated soil spiked with a total of nine PAHs: acenaphthene, fluorene, phenanthrene, fluoranthene, pyrene, chrysene, benzo(a)pyrene, dibenz(a-h)anthracene, and benzo(ghi)perylene. After 11 months of aging, recovery percentages of high molecular weight PAHs [i.e., from chrysene to benzo(ghi)perylene] were greater than 86%, while those of low molecular weight PAHs (i.e., from acenaphthene to pyrene) were less than 19%. Total removal efficiency for any of the nine PAHs was greater than 90% using a combination of surfactant soil washing and P. chrysosporium oxidation of soil washwater in the RBC reactor when used in batch operation, and greater than 76% when used in continuous operation. The treatment of PAH-contaminated soil using a combination of surfactant soil washing and subsequent PAH removal from the resultant washwater in an RBC reactor, in the presence of immobilized P. chrysosporium, permits (i) a rapid abiological cleanup of soil for compliance with relevant soil quality standards and (ii) PAH biological removal in soil washwater for compliance with aqueous discharge standards.     

Modeling the fate of benzo[a]pyrene in the wastewater-irrigated areas of Tianjin with a fugacity model

A Level III fugacity model was applied to characterize the transfer processes and environmental fate of benzo[a]pyrene in wastewater-irrigated areas of Tianjin, China. The physical-chemical properties and transfer parameters of benzo[a]pyrene were used in the model and the concentration distribution of benzo[a]pyrene in sediment, soil, water, air, fish, and crop compartments, as well as transfer fluxes across the compartments, were then derived under steady-state assumptions. The calculated results were compared with monitoring data for air, soil, water, and sediment collected from the literature. The results indicate that there was generally good agreement and the differences were within an order of magnitude for air, soil, and sediment. The concentration of benzo[a]pyrene in the ambient air in the area was very low with a majority present sorbed to aerosol. In the water compartment, approximately 70% of benzo[a]pyrene dissolved in water phase. Relatively high concentrations of the compound were found in the soil and sediment, with the soil serving as the dominant sink in the area. Benzo[a]pyrene, with a slow metabolic rate, was found to accumulate in fish in the area.     

大连城市大气中多环芳烃的污染特征和毒性评价

通过对大连市工业区、居民区和城市背景区3种类型区域连续7个月大气样品的采集,分析PAHs在大气中的污染特征,并对其毒性进行评价。结果显示,城市工业区大气中PAHs含量最高,其次是居民区,城市背景区最低。3种类型采样点大气中PAHs的组成相似,菲是含量最多的物质,其次是荧蒽、芴和芘。16种PAHs基于苯并[a]芘的总毒性当量浓度为:工业区5.1 ng/m^3;居民区3.6 ng/m^3;城市背景区4.6 ng/m^3。3种类型功能区大气中PAHs的TEQ值都高于我国的《空气质量标准》(GB 3095-2012)中规定的大气中苯并[a]芘的年平均浓度(1 ng/m^3)或24 h平均浓度(2.5 ng/m^3)。     

Prediction of microbial accessibility of carbon-14-phenanthrene in soil in the presence of pyrene or benzo[a]pyrene using an aqueous cyclodextrin extraction technique

Traditionally, solvent extractions are routinely used in the assessment of contaminated land. However, vigorous solvent extractions only give total concentrations rather than that relating to the bioaccessible fraction. Recently, less harsh, aqueous-based extraction methods have been shown to be a better estimate of the microbial degradation of polycyclic aromatic hydrocarbons (PAHs). The aqueous-based hydroxypropyl-beta-cyclodextrin (HPCD) extraction technique was tested using 14C-PAHs in soils and compared against indigenous microbial mineralization (a measure of bioaccessibility) of 14C-phenanthrene in the presence of pyrene or benzo[a]pyrene (B[a]P) over a range of concentrations (0, 5, 10, or 50 mg kg(-1)) and aged for 0, 25, 50, and 100 d in four soils. At each time point, the total loss, extractability, and mineralization of 14C-phenanthrene was measured in each of the soils. The presence of the other PAHs had little effect on the behavior of 14C-phenanthrene in any of the soils. Comparisons between the amounts of 14C-phenanthrene extracted using HPCD and mineralized were made and showed that there was a correlation (1:1). This study demonstrates that HPCD extraction is able to predict the microbial accessibility fraction of 14C-phenanthrene in the presence of other PAHs in a range of soils, further supporting the applicability of this technique.     

A minimum data set of water quality parameters to assess and compare treatment efficiency of stormwater facilities

Urban stormwater runoff is often of poor quality, impacting aquatic ecosystems and limiting the use of stormwater runoff for recreational purposes. Several stormwater treatment facilities (STFs) are in operation or at the pilot testing stage, but their efficiencies are neither well documented nor easily compared due to the complex contaminant profile of stormwater and the highly variable runoff hydrograph. On the basis of a review of available data sets on urban stormwater quality and environmental contaminant behavior, we suggest a few carefully selected contaminant parameters (the minimum data set) to be obligatory when assessing and comparing the efficiency of STFs. Consistent use of the minimum data set in all future monitoring schemes for STFs will ensure broad-spectrum testing at low costs and strengthen comparability among facilities. The proposed minimum data set includes: (i) fine fraction of suspended solids (<63 μm), (ii) total concentrations of zinc and copper, (iii) total concentrations of phenanthrene, fluoranthene, and benzo(b,k)fluoranthene, and (iv) total concentrations of phosphorus and nitrogen. Indicator pathogens and other specific contaminants (i.e., chromium, pesticides, phenols) may be added if recreational or certain catchment-scale objectives are to be met. Issues that need further investigation have been identified during the iterative process of developing the minimum data set.     

Direct link between fluoranthene biodegradation and the mobility and sequestration of its residues during aging

The aim of this study was to assess the influence of the polycyclic aromatic hydrocarbons (PAH)-degrading activity in the fate of fluoranthene in soils. Three soil samples with different degrading activities (an industrial soil, the same industrial soil after biostimulation, and an agricultural soil) were spiked with 14C-fluoranthene and incubated for 6 mo with monitoring of biodegradation and mineralization. To follow the distribution of the 14C-fluoranthene residues (i.e., 14C-fluoranthene and its degradation products) among the soil compartments, we performed successively leaching, centrifugation (to collect intra-aggregate pore water), solvent extraction, and combustion of the soil columns. In the industrial soil, no mineralization of 14C-fluoranthene was observed, and only 3% of the initial 14C-activity was non-extractable (with acetone:dichloromethane) after 165 d of incubation. The biostimulation (addition of unlabeled polycyclic aromatic hydrocarbons) increased the degrading activity in this soil (59% of 14C-fluoranthene was mineralized) and increased the residues sequestration (13% of 14C-activity was non-extractable). The microflora of the agricultural soil mineralized 14C-fluoranthene more slowly and to a lesser extent (25%) than the biostimulated soil, but a higher amount of 14C-activity was sequestered (41%). Thus, the rate and extent of 14C-fluoranthene mineralization seemed to be related to the 14C-activity sequestration by controlling the accumulation of degradation products in the soil. 14C-Fluoranthene biodegradation enhanced the concentration of 14C-polar compounds in the intra-aggregate pore water. Our results point out the close link between fluoranthene biodegradation and two key aging processes, diffusion and sequestration, in soils. Biodegradation controls the mobility and sequestration of residues by transforming fluoranthene into more polar molecules that can diffuse into the intra-aggregate pore water and then might become bound to the matrix or entrapped in the microporosity.     

Sequential supercritical fluid extraction (SSFE) for estimating the availability of high molecular weight polycyclic aromatic hydrocarbons in historically polluted soils

Sequential supercritical fluid (CO2) extraction (SSFE) was applied to eight historically contaminated soils from diverse sources with the aim to elucidate the sorption-desorption behavior of high molecular weight polycyclic aromatic hydrocarbons (PAHs). The method involved five extraction phases applying successively harsher conditions by increasing fluid temperature and density mobilizing target compounds from different soil particle sites. Two groups of soils were identified based on readily desorbing (available) PAH fractions obtained under mildest extraction conditions (e.g., readily desorbing fractions of fluoranthene and pyrene significantly varied between the soils ranging from <10 to >90%). Moreover, extraction behavior strongly correlated with molecular weight revealing decreasing available PAH fractions with increasing weight. Physicochemical soil parameters such as particle size distribution and organic dry mass were found to have no distinct effect on the sorption-desorption behavior of PAHs in the different soils. However, PAH profiles significantly correlated with readily available pollutant fractions; soils with relatively less mobile PAHs had higher proportions of five- and six-ring PAHs and vice versa. Eventually, biodegradability corresponded well with PAH recoveries under the two mildest extraction phases. However, a quantitative relationship was only established for soils with biodegradable PAHs. Out of eight soils, five showed no biodegradation including the four soils with the lowest fraction of readily desorbing PAHs. Only one soil (which was found to be highly toxic to Vibrio fischeri) did not match the overall pattern showing no PAH biodegradability but large fractions of highly mobile PAHs, concluding that mass transfer limitations may only be one of many factors governing biodegradability of PAHs.