Photo-oxidation and Photo-toxicity of Crude and Refined Oils

The fate and effects of an oil spill are effected by solar radiation through the action of photo-oxidation and photo-toxicity. Photo-oxidation, an important process in the weathering of oil, produces a variety of oxidized compounds, including aliphatic and aromatic ketones, aldehydes, carboxylic acids, fatty acids, esters, epoxides, sulfoxides, sulfones, phenols, anhydrides, quinones and aliphatic and aromatic alcohols. Some of these compounds contribute to the marine biota toxicity observed after an oil spill. Photo-toxicity occurs when uptake of certain petroleum compounds, e.g. certain polycyclic aromatic hydrocarbons and benzothiophenes, is followed by solar exposure which results in much greater toxicity than after dark uptake. The mechanism of PAH photo-toxicity includes absorbance of solar radiation by the PAH which produces a free radical and this free radical in turn reacts with oxygen to produce reactive oxygen species that can damage DNA and other cellular macromolecules. While most studies on photo-toxicity have been carried out in the laboratory, there are studies showing that water from an oil spill is photo-toxic to bivalve embryos for at least a few days after the spill. Other studies have found that oil contaminated sediments are photo-toxic to several marine invertebrates. More studies are required to determine if marine fauna at an oil spill site are effected by the action of photo-toxicity and photo-oxidation.     

多环芳烃的健康风险评价以及暴露参数的敏感性分析

在暴露情景假设和评估模型的确定下,有必要对污染场地的风险计算结果有影响的模型参数开展敏感性分析,以便在开展土壤健康风险评估工作时,提高评估的准确性和科学性,节约修复成本。以上海市某污染场地为例,对模型参数敏感性开展敏感性分析。贡献率结果显示,经口摄入土壤和皮肤接触土壤为场地表层污染土壤的主要致癌风险暴露途径。敏感性分析结果显示,致癌风险与体重呈反向变化,当体重参数减小时,暴露风险将向不利的方向移动。当体重参数在大范围减小时,敏感程度较高。致癌风险与暴露周期、暴露频率、每日摄入土壤量、暴露皮肤表面积、皮肤表面土壤粘附系数呈同向变化,当这些参数增大时,暴露风险将向不利的方向移动;其中暴露周期和暴露频率的敏感程度中等。上海市敏感用地下苯并(a)蒽、苯并(b)荧蒽、茚并(1,2,3-c,d)芘、苯并(a)芘、二苯并(a,h)蒽风险控制值分别为0.726、0.726、0.726、0.072 6、0.072 6 mg/kg。     

基质固相分散-快速溶剂萃取-GC/MS法同时测定土壤中有机氯农药和多环芳烃

建立了基质固相分散-ASE提取-GC/MS法同时测定土壤中8种有机氯农药和16种多环芳烃的方法。对方法的线性、检出限、精密度、回收率及土壤质控样品进行了分析,结果表明,8种有机氯农药和16种多环芳烃线性良好,相关系数为0.997 5～0.999 8,方法检出限为0.39～1.57μg/kg,空白加标样品的相对标准偏差小于20%,实际土壤样品加标回收率为60.6%～125%,土壤质控样品结果均在范围内。该方法能够满足土壤中8种有机氯农药和16种多环芳烃的检测要求。     

Polycyclic aromatic hydrocarbons in indoor and outdoor air in Turkey: Estimations of sources and exposure

The aim of the current study was to measure polycyclic aromatic hydrocarbons (PAHs) in eight indoor (In both kitchen and living room) air sampling locations using a passive sampling method for collection. Passive outdoor air samples were also collected from 3 of the same sampling locations as the indoor air sampling sites. Sampling was conducted in three seasons. The summer season, when windows are generally open, was between 18th July and 01st September, 2014; the autumn and winter seasons, when windows are mostly closed, was between 18^th October and 01^st December, 2014, and 01^st December, 2014, and 18^th January, 2015, respectively.

Average PAH concentrations in summer were 22 ± 21 ng/m³ and 17 ± 12 ng/m³ in the living room and kitchen, respectively, whereas living room and kitchen average PAH concentrations were 23 ± 16 ng/m³ and 20 ± 9 ng/m³, respectively, in autumn and 23 ± 13 ng/m³ and 23 ± 24 ng/m³, respectively, in winter. Outdoor air PAH concentrations in summer, autumn and winter were 7 ± 0.4 ng/m³, 22 ± 13 ng/m³ and 209 ± 33 ng/m³, respectively. An increase in outdoor PAH concentrations was measured in winter compared to the concentrations in summer and autumn, which paralleled the lower outdoor air temperature. However, PAH concentrations in the indoor environment vary according to the household characteristics and personal habits.     

玻璃表面PAHs垂向分布特征与室内外对比研究

利用GC-MS对上海市玻璃表面有机膜中PAHs浓度进行了定量分析。结果表明随着楼层的增加,10层居民楼玻璃表面PAHs浓度出现先增加后减少的趋势,最高浓度出现在3层(736 ng/m~2),最低在9层(346 ng/m2);17层公寓楼PAHs浓度则是先减少后增加再减少的趋势,最高浓度出现在9层(2 338 ng/m~2),最低在16层(564 ng/m~2)。TOC与PAHs相关性分析暗示除TOC外,玻璃表面PAHs富集可能还受控于其他因素。10层居民楼主要以3环和4环PAHs为主;而17层公寓楼则以4环为主。玻璃外表面PAHs浓度(555 ng/m~2)远高于内表面(308 ng/m~2);外表面主要以Phe、Pyr、Chry、Fluo和Fl为主;内外表面低环PAHs比值接近于1,高环比值基本上低于0.6。TEQ值虽然较低,但生态风险仍不能忽视。     

植物-微生物修复石油烃污染土壤与根际微生态环境变化

石油烃作为一类持久性难降解有机污染物对土壤环境质量产生严重的危害。以天津大港油田原油污染土壤中筛选出的耐低温高效石油烃降解菌为靶细胞,以小麦、紫花苜蓿作为供试植物,利用盆栽试验,对植物-外源菌协同修复体系中的脱氢酶活性和土壤微生物多样性进行研究,分析其变化及其与石油烃降解率的关系。结果表明植物-微生物协同修复对石油烃具有较好的降解能力,其中小麦-固定化外源菌组具有最高的降解率,石油烃含量从最初的30 600 mg獉kg-1下降为24 300 mg獉kg-1,降解率为20.6%,并且其试验后期石油烃的降解率最大,远远高于其他时期,表现出良好的修复潜力。外源菌投加的初始阶段会迅速提高脱氢酶活性,然而这种影响随着降解时间延长而逐渐减弱。初期脱氢酶活性与总石油烃的降解存在较好的相关性,脱氢酶活性可以在一定程度上表征土壤石油烃的降解情况。微生物多样性与总石油烃降解也存在一定的相关性。     

难降解有机物生物抑制特性的研究

对杂环化合物及多环芳烃的好氧生物降解抑制特性研究结果表明：咔唑、联苯等５种物质具有类似的抑制特性,表现在急性持久抑制及抑制强度大２方面,其抑制机理为不逆抑制;喹啉、吲哚等５种物质在高浓度时对苯酚的降解产生明显的初期抑制,历经诱导期,恢复期,最后进入正常降解期,其抑制机理为可逆抑制,萘的抑制属于竞争性抑制范畴。     

焦化厂土壤中多环芳烃分布特征及淋洗粒级分割点确定

土壤粒径分布和污染物在不同粒级土壤中的分布特征是污染土壤淋洗可处理性的重要依据,淋洗粒级分割点则是淋洗工艺的重要参数.根据土壤异位淋洗的技术要求,在焦化厂污染场地进行了采样,测定了土样的粒径分布曲线及不同粒级土壤中美国EPA优控的16种多环芳烃(PAHs)的初始浓度,并采用Tween 80和Triton X-100溶液对不同粒级污染土样进行了振荡清洗实验.结果表明,16种PAHs在6个粒级中的总浓度在6.27～40.18 mg/kg范围,呈双峰分布模式,单个PAH污染物的最高浓度大多出现在250～500 μm的颗粒中, 50～75 μm的颗粒中污染物浓度最低;PAHs去除率与其初始浓度及土壤特性有关,初始浓度越低,去除率越高,粗颗粒中由于有机碳含量较高,PAHs去除效率反而低于细颗粒.根据清洗效果并从废物减量化角度出发,确定以50 μm作为土壤淋洗的粒级分割点,这样减容率可以达到82.95％.     

Contaminant Exposure of Barn Swallows Nesting on Bayou D'Inde, Calcasieu Estuary, Louisiana, USA

Current and historical point source discharges, storm water runoff, and accidental spills have contaminated the water, sediment, and biota within the Calcasieu Estuary in southwestern Louisiana. In 2003, barn swallow (Hirundo rustica) eggs and nestlings were collected beneath two bridges that cross Bayou d′Inde, the most contaminated waterway within the Calcasieu Estuary. Samples were also collected from a bridge over Bayou Teche, a reference site in south central Louisiana. Polychlorinated biphenyl (PCB) concentrations in barn swallow eggs and nestlings were significantly higher at the downstream site on Bayou d′Inde (2.8 μ g/g PCBs in eggs and 1.5 μ g/g PCBs in nestlings) than at the other two sites (< 0.2 μ g/g PCBs in eggs and nestlings at both sites). Ethoxyresorufin-O-dealkylase activity in nestling livers was significantly higher at the downstream site on Bayou d′Inde (50 pmol/min/mg) compared to the other two locations (24 pmol/min/mg, each), probably because of exposure to PCBs. Polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran concentrations in eggs and polycyclic aromatic hydrocarbons in nestlings were at background concentrations at all sites. Trace element concentrations in barn swallow eggs and nestling livers were at background levels and did not differ among the three sites. A biomarker of DNA damage did not differ among sites.     

Lethal and sublethal effects of naphthalene and 1,2-dimethylnaphthalene on naupliar and adult stages of the marine cyclopoid copepod Oithona davisae

Short-term (24 h) exposure experiments have been conducted to determine the effects of two environmental relevant polycyclic aromatic hydrocarbons (PAHs), naphthalene (NAPH) and dimethylnaphthalene (C2-NAPH), on the naupliar and adult stages of the marine cyclopoid copepod Oithona davisae. To resemble more realistic conditions, those exposure experiments were conducted under the presence of food. The naupliar stages evidenced lower tolerance to PAH exposure regarding narcotic and lethal effects than adults. Copepod feeding activity showed to be very sensitive to the presence of the studied PAHs, detrimental effects occurring at toxic concentrations ca. 2-3 fold lower than for narcotic effects. In addition we report PAH-mediated changes in cell size and growth rate of the prey item, the heterotrophic dinoflagellate Oxyrrhis marina, that could indirectly affect copepod feeding and help explain hormesis-like responses in our feeding experiments.