搬迁化工厂区土壤中多环芳烃污染及来源分析

分析南通某搬迁化工厂区土壤中16种优控多环芳烃（PAHs）污染物的含量特征及污染水平。结果表明，车间和仓库土壤中多环芳烃总量为200—300ng／g，在南通市耕地土壤污染水平范围内。停车场土壤中PAHs含量为3435ng／g，污染水平高于普通耕地，与交通干线两侧土壤相当，土壤中PAHs以4环及4环以上PAHs为主，为汽车尾气污染，若继续用于道路或停车场等功能无需进行PAHs修复。     

天津城郊土壤中PAHs含量特征及来源解析

以天津市郊环城四区为研究对象,系统采集了环城四区95个表层土壤样品,利用高效液相色谱仪对16种PAHs进行分析测定,结果表明,西青、东丽、津南和北辰土壤中16种PAHs的总量范围分别为62.6～1 994.9、36.1～4 074.7、20.1～2 502.5、22.1～707.7μg/kg;平均含量分别为445.8、841.8、509.5、242.5μg/kg。四区中都以高环多环芳烃为主,西青、东丽、北辰和津南高环多环芳烃分别占多环芳烃总比例的45.4%、42.2%、38.8%和38.7%。空间分析的结果表明,靠近天津市市区样点土壤中多环芳烃的含量要明显高于远离市区土壤中多环芳烃的含量。利用环数PAHs的相对丰度和比值法对天津市郊环城四区土壤中多环芳烃的污染来源进行了解析,研究区土壤监测样点的PAHs主要来自燃烧源,少部分来自石油类来源或几种污染源的共同复合累加的作用。     

福建省茶园土壤中多环芳烃的分布、来源分析及生态风险评价

利用高效液相色谱分析技术对福建省茶园土壤中16种多环芳烃进行了定量分析,结果表明,PAHs的总量在0.622~812.0μg/kg之间,平均值为48.4μg/kg。其组成以3环的为主,4环次之,主成分分析和PAHs特征参数分析发现,福建省茶园土壤中多环芳烃主要以燃油、木柴和煤燃烧来源为主,部分样点存在油类排放污染。生态风险评价结果显示,福建省茶园土壤中多环芳烃已具有不利生物影响效应。     

灌河口表层土壤多环芳烃污染调查

为了解灌河口工业区表层土壤中多环芳烃的污染水平及健康风险。于2017年4月份在灌河口化工园区、火力发电厂和钢铁工业园区采集30个表层土壤样品,利用气相色谱-质谱联用仪(GC-MS)对16种优控ω(PAH)进行了检测。结果表明,30个采样点16种PAH的ω(T-PAHs)总为1 212.8~12 264.5 ng/g,平均值为3 504.8 ng/g。其中单体PAH以Fl为主,平均比例高达19.4%,其次为Pyr(16.7%)和B[a]P(9.6%)。单体PAH相关性分析表明了污染物来源的一致性,主要来源于本地工业区原油、生物质和煤的燃烧过程。根据加拿大土壤环境质量标准,灌河口工业区87%的土壤PAHs污染超过了安全值,存在潜在的生态风险。     

灌河口表层土壤多环芳烃污染调查与评价

为了解灌河口工业区表层土壤中多环芳烃的污染水平及健康风险。于2017年4月份在灌河口化工园区、火力发电厂和钢铁工业园区采集30个表层土壤样品,利用气相色谱-质谱联用仪(GC-MS)对16种优控ω(PAH)进行了检测。结果表明,30个采样点16种PAH的ω(T-PAHs)总为1 212.8~12 264.5 ng/g,平均值为3 504.8 ng/g。其中单体PAH以Fl为主,平均比例高达19.4%,其次为Pyr(16.7%)和B[a]P(9.6%)。单体PAH相关性分析表明了污染物来源的一致性,主要来源于本地工业区原油、生物质和煤的燃烧过程。根据加拿大土壤环境质量标准,灌河口工业区87%的土壤PAHs污染超过了安全值,存在潜在的生态风险。     

武汉市东西湖农场表层土壤中多环芳烃的含量分布特征

对武汉市东西湖农场土壤中多环芳烃的含量调查表明,除紧靠马路边、居民区的土壤中多环芳烃的浓度高于荷兰制定的土壤修复标准之外,其余地方均在此标准值之内,其中主要是高环多环芳烃含量超标严重。证明了汽车尾气所排放的多环芳烃要高于居民日常生活的排放量。多环芳烃在水平方向上的迁移存在色谱效应。     

云南省宣威市和富源县空气和土壤中多环芳烃污染水平研究

宣威市和富源县位于我国云南省东北部,是全世界肺癌发病率最高的地区之一。当地居民在不通风的房间内燃烧烟煤做饭或取暖造成了严重的室内空气污染。研究表明,长期暴露在燃煤造成的污染物中是导致两地居民肺癌持续高发的主要原因,多环芳烃是最可疑的致病因子之一。2008年1月,分别用聚胺脂泡沫和玻璃纤维滤膜采集了当地9个点位室内、室外空气中气相和颗粒物相中的多环芳烃,同时采集了对应点位的土壤样品。通过对样品的分析,考察了当地空气和土壤中多环芳烃的污染水平、特征以及来源。结果证明,当地空气和土壤中存在严重的多环芳烃污染,室内污染显著高于室外,然而随着当地工业的发展室外污染同样不可忽视,主成分分析结合比值法证明,当地室内外多环芳烃的主要污染源来自于煤炭的燃烧。对空气颗粒物和土壤中多环芳烃浓度进行了比较,对土壤中多环芳烃的来源进行了验证。     

南昌市周边农田土壤中多环芳烃的污染特征及来源分析

采集南昌市周边三个县的18个农田表层土壤样品,采用液固萃取-层析净化-高效液相色谱分析技术,研究了土壤中16种优控多环芳烃类物质的含量和组分特征,运用主成分因子荷载方法分析了其污染来源,并初步评价了其风险水平。结果表明,该区域内农田土壤33.3%轻度污染,最高污染样点PAHs含量为422.8ng/g,最低污染样点PAHs含量为75.2ng/g,平均含量为197.9ng/g,且远离城市的农田土壤残留水平明显低于靠近城市的农田土壤;PAHs的组分特征为以毒性水平较低的低环化合物为主;其污染来源主要是煤、天然气和汽油燃烧组成的混合源。     

气溶胶与降尘中多环芳烃的含量分布研究

通过广东省茂名市区四个不同功能点大气气溶胶和降尘中多环芳烃的含量分布研究发现 :1、气溶胶中优控多环芳烃大大高于降尘中的含量 ,为降尘的 5.97～ 1 9.3倍 ;以石化厂区为例 ,非优控多环芳烃在气溶胶中的相对含量更高 ,为降尘的 2 4 .7倍。2、气溶胶中优控多环芳烃和非优控多环芳烃的分布为随分子量增加而含量增高的趋势 ,但降尘中优控多环芳烃的高含量相对集中于萤蒽至苯并 (b)萤蒽之间。3、不同功能区由于排放源的差别所表现出的气溶胶和降尘中优控多环芳烃总量及总量比值、部分强致癌和致癌物含量及含量比值均存在差异。4、对气溶胶和降尘中多环芳烃研究可以对降尘中非优控多环芳烃降解和溶解量进行估算。以石化厂区为例 ,降尘中非优控多环芳烃比原始含量已减少76%。     

香烟燃烧排放的主流烟气中PAHs的含量检测研究

研究10种不同价格香烟燃烧烟气的多环芳烃(PAHs)含量特征,结果表明,每种香烟烟气都含有多环芳烃,但是含量差别较大,平均值为405.405ng/g。在检测出来的多环芳烃中,主要是以2,3环多环芳烃为主,占据的比例达到80%左右。因此香烟烟气中的多环芳烃应该引起人们的广泛关注。     

石家庄市大气颗粒物中水溶性无机离子污染特征研究

用超声萃取－离子色谱法分析了石家庄市大气颗粒物中8种水溶性无机离子。结果表明，NO3－、SO2－4、NH4＋及 Ca2＋为主要组分；各个离子的质量浓度均有季节及空间变化差异；不同粒径颗粒物中 SO2－4和 NO3－相关性均很好，NH4＋与 SO2－4、NO3－在细颗粒物中具有良好的相关性，Ca2＋在粗粒子中与 NO3－和 SO2－4的相关性也较好。SO2－4／NO3－质量比季节变化表明，春、夏季固定源与流动源对大气颗粒物贡献相当，秋季流动源贡献较大，冬季固定源贡献较大。PM2．5中SO2与SO2－4、NO2与 NO3－转化率表明，SO2－4、NO3－主要是由二次转化而来。     

高压密闭消解土壤砷、汞、铅、镉酸体系比较

采用高压密闭消解系统消解土壤,氢化物发生-原子荧光光谱法(HG-AFS)测定As和Hg,石墨炉原子吸收光度法(GF-AAS)测定Pb和Cd,对比了不同消解酸体系对国家土壤标准参考样中As、Hg、Pb、Cd的消解效果。结果表明,盐酸-硝酸体系对As、Hg、Pb和Cd的消解平均回收率分别为26.1%、100.6%、69.7%、87.3%;硝酸-高氯酸-氢氟酸体系中As、Hg、Pb和Cd消解平均回收率分别为109.9%、84.7%、87.5%、90.1%;硝酸-双氧水体系对Hg、Pb、Cd消解平均回收率分别为104.8%、95.1%、93.3%,对As的回收率虽只有69.2%,但数据精密度最好。此外,从简化试验步骤,减少误差,提高检测效率及减少试验危险性等方面综合评价,认为硝酸-双氧水消解体系是采用高压密闭系统消解土壤重金属的最理想酸体系。     

南通市冬季PM2.5中水溶性离子污染特征

根据南通市2016和2017年冬季大气多参数站自动监测PM2.5数据和在线离子色谱分析仪Marga监测的PM2.5中水溶性离子数据,分析了南通市冬季PM2.5中水溶性离子污染特征。结果表明,南通市2016和2017年冬季,ρ(PM2.5)分别为58和54μg/m 3,均高出其年均值(14μg/m^3);ρ(水溶性离子)总占ρ(PM2.5)百分比分别为74.5%和74.3%;二次离子ρ(NO3^-、SO4^2-和NH4^+)占ρ(PM2.5)百分比分别为66.8%和66.6%;各水溶性离子占比大小依次为:NO3^-、SO4^2-、NH4^+、Cl^-、K^+、Na^+、Ca^2+、Mg^2+。对ρ(NO3^-)/ρ(SO 4^2-)分析表明,移动源已经成为南通市冬季的主要污染源,且呈逐年增强趋势。对氯氧化率和硫氧化率的分析表明,南通市冬季存在较明显的二次污染,SO2的转化程度大于NO2。除Na^+和Mg^2+外,其他离子与PM2.5均呈显著相关性,NO3^-、SO4^2-与NH4^+之间的相关系数最高,Cl^-与除Na^+外的所有阳离子均呈显著相关性。     

乌鲁木齐市可吸入颗粒物水溶性离子特征及来源解析

采暖期时在乌鲁木齐市采集了环境空气中的可吸入颗粒物,对可吸入颗粒物质量浓度及8种水溶性离子的特征和来源进行了分析。结果表明,细粒子和粗粒子的月平均质量浓度分别是53.5～233.3μg/m3和38.9～60.9μg/m3;细粒子和粗粒子中水溶性离子主要由SO24-、NH4+和NO3-组成;粗粒子中NH4+与NO3-和SO24-的相关性分别是0.70和0.66,细粒子中NH4+与NO3-和SO24-的相关性分别是0.89和0.93,铵盐是乌鲁木齐可吸入颗粒物主要存在形式;煤烟尘是乌鲁木齐市采暖期可吸入颗粒物的主要来源。     

大气痕量有机硫化物的光电离色谱法测定及硫酸铵在湿浸土壤中释放有机硫化物的研究

采用国产光电离色谱仪(GC-PID)对有机硫化物:乙基硫醇,二甲基硫,二甲基二硫进行了分离分析,其最小检知量在亚微克/升级,并对北京郊区的某些天然源环境样品进行了有机硫化物浓度的测定,实验数据证实,在鸡场,猪场,水稻田与塑料蔬菜大棚等环境大气中含有机硫化物。研究了硫酸铵作为氮肥加入到水浸土壤中后,由于缺氧而生成有机硫化物的现象,观察了其对有机硫化物的释放规律及硫酸铵与葡萄糖分别作为硫源与碳源对有机硫化物生成的影响,实验结果认为:硫酸铵在五种不同类型的水浸土壤中(环境温度25℃),均可解离释放出有机硫化物,随其在土壤中加入量的增多,释放气中的有机硫浓度增加,二甲基硫的释放量最大。     

Growth impact of O3, NO2 and/or SO2 on pinus taeda

Seedlings of two full-sib families of loblolly pine expressing different degrees of sensitivity to O₃ were exposed to 0.05 ppm O₃, 0.10 ppm NO₂, and/or 0.14 ppm SO₂ for 6 hr/day for 28 consecutive days. The treatments were O₃, NO₂, SO₂ (each used alone), O₃+SO₂, O₃+NO₂, and O₃+NO₂+SO₂. Significant growth suppressions were noted with the relatively sensitive family in all but the the NO₂ alone treatments. The O₃+SO₂ treatment had a more significant effect than O₃ alone, but adding NO₂ had an inconsistent effect. Significant growth suppressions were noted for the relatively non-sensitive family only in the O₃+SO₂ and O₃+SO₂+NO₂ combination treatments. Adding NO₂ to O₃+SO₂ had a slightly stimulatory effect. The relatively sensitive pine family suffered a 30% height growth suppression versus a 14% height growth suppression for the relatively insensitive family when exposed to the 3 pollutant combination. Symptoms were noted on less than 4% of the foliage in the most severe treatments. The pollutant concentrations used in this study were below the National Ambient Air Quality Standards (NAAQS) for each pollutant.     

不同模式版本对长三角区域大气污染物模拟结果对比评估

选取2015年1、4、7、10月(分别代表冬、春、夏、秋4季),应用CMAQv4.7.1和CMAQv5.1模式模拟长三角区域的空气质量,对比了NO2、SO2、O3、PM2.54个常规污染物的模拟结果,表明CMAQv5.1对NO2、SO2和PM2.5的模拟效果优于CMAQv4.7.1,而CMAQv4.7.1的O3模拟效果优于CMAQv5.1;CMAQv5.1的NO2模拟值更接近地面观测值,比起不同版本的化学机制对NO2模拟效果的影响,NO2的模拟偏差受排放高估的影响更大;2个版本SO2的模拟值差距较小,且都与地面观测值之间差异较小;CMAQv5.1 PM2.5的模拟值比CMAQv4.7.1更接近观测值,气溶胶模块机制的更新(例如新增细分的PM2.5模式物种和部分二次有机气溶胶生成机制的改进等)对PM2.5模拟效果的改善显著;CMAQv5.1的O3模拟值比CMAQv4.7.1高,CMAQv5.1的O3模拟值在O3观测值的高值时段更接近观测值,而CMAQv4.7.1的O3模拟值在低值时段更接近观测值,CMAQv5.1在日最大8小时平均(MDA8)O3观测浓度超标日的O3模拟效果相比CMAQv4.7.1有一定程度的改善,但在非超标日模拟效果变差,CMAQv5.1的O3模拟效果总体相比CMAQv4.7.1并未得到有效提升。提出,未来针对低值时段和低值区域的O3模拟机制的改进将进一步提升O3模拟效果。     

Determination of selected microbial volatile organic compounds by diffusive sampling and dual-column capillary GC-FID--a new feasible approach for the detection of an exposure to indoor mould fungi?

A new, analytically valid procedure is described to assess the exposure of human beings to the so-called microbial volatile organic compounds (MVOCs) in air. The method can be used routinely for large sample numbers and is especially valuable as a basis for further research on the correlation between single MVOCs and indoor mould growth. The procedure is based on the fact that fungi produce a variety of volatile organic compounds, such as 3-methylbutan-1-ol, 3-methylbutan-2-ol, fenchone, heptan-2-one, hexan-2-one, octan-3-one, octan-3-ol, pentan-2-ol, alpha-terpineol, and thujopsene, which they emit into the indoor environment. Using diffusive samplers, these MVOCs are adsorbed onto charcoal during a sampling interval of four weeks. The described method is thus superior to existing methods which use short-term active sampling. After desorption with carbon disulfide, the MVOCs were determined by dual-column gas chromatography with flame ionization detection using the large-volume injection technique for sample introduction. The detection limits ranged between 0.15 and 0.53 microgram m-3, within-series precision was found to range between 6.5 and 19.0%, and recovery was between 77 and 118%. The procedure has been successfully applied in the context of a large field study to measure the indoor MVOC exposure in children's rooms of 132 dwellings. The objective of the study was to examine the relation between indoor mould growth, the indoor MVOC exposure and the prevalence of adverse health effects. Information about mould formation has been obtained by a questionnaire and by the determination of colony forming units of mould fungi in mattress dust. With the exception of 3-methylbutan-2-ol, fenchone, nonan-2-one, octan-2-one, and thujopsene, indoor air concentrations of all MVOCs under investigation were significantly higher inside damp and mouldy dwellings. From the primary MVOCs under investigation, 3-methylbutan-1-ol, hexan-2-one, heptan-2-one, and octan-3-ol were found to be most reliable indicators for mould formation. A correlation was also found between selected MVOCs and the occurrence of mould species in mattress dust. Aspergillus sp. correlated with heptan-2-one, hexan-2-one, octan-3-ol, octan-3-one, and alpha-terpineol, while the occurrence of Eurotium sp. was correlated with higher indoor air concentrations of 3-methylbutan-1-ol, 3-methylbutan-2-ol, heptan-2-one, hexan-2-one, octan-3-ol, and thujopsene. Children living in dwellings with elevated MVOC levels had a higher prevalence of asthma, hay fever, wheezing, and irritations of the eyes. These positive associations persisted after controlling for confounding factors such as age, sex, body-mass index, number of siblings, social status, passive smoking, type of heating, and ventilation habits. However, they were not statistically significant. This lack of significance may be a result of the small number of investigated samples.     

Triethoxysilyl-substituted aminoethanethiol ligands for zinc and cadmium complexes and aminoethanethiol-modified silica gel. Evaluation of the corresponding supported molecular trap for metallic pollutant uptake (Cd2+, Hg2+ and Pb2+)

The reaction of 2-[3-(triethoxysilyl)propylamino]ethanethiol (LH, a) and 1-methyl-2-[3-(triethoxysilyl)propylamino]ethanethiol (LH, b) with ZnX2 and CdX2 (X = Cl, Br, I, NO3) in tetrahydrofuran (THF) or CH2Cl2 gives several complexes depending on the experimental conditions. Elemental analyses, IR, Raman, 13C[1H], 1H NMR and mass spectroscopies indicated the formation of mononuclear and dinuclear complexes. In the absence of NEt3 as proton quencher, the protonated ligands react in their zwitterionic form giving dinuclear [M(LH)X2]2 [M = Zn (1), Cd (2); LH = a, b; X = Cl, Br, I] or mononuclear M(NO3)2(LH)2 [M = Zn (5), Cd (6); LH = a] complexes. In both cases, coordination occurs through the S atoms, the ligands acting as terminal and bridging species. With NEt3, the deprotonated ligands are chelated through their N and S atoms and bridging occurs through the S atoms in [MLX]2 [M = Zn (3), Cd (4); LH = a; X = Cl, Br] complexes. The LH ligand is chemically grafted onto silica, the procedure optimized and the resulting material characterized by 13C and 29Si cross-polarization, magic-angle spinning (CP-MAS) NMR and DRIFT. This material is evaluated as a supported molecular trap for binding heavy metals (Cd2+, Hg2+, Pb2+) in aqueous solution. In both batch and column processes, it appears that Hg2+ and Pb2+ are trapped more than Cd2+, but in all cases values lower than those allowed were obtained.     

Atmospheric wet deposition of soluble macro-nutrients in the Cilician Basin, north-eastern Mediterranean sea

In order to estimate wet deposition atmospheric fluxes of macro-nutrients into the eastern Mediterranean coastal waters, soluble inorganic phosphate (PO4(3-)), nitrate (NO3-) and nitrite (NO2-) concentrations in precipitation (from February 1996 to June 1997) have been measured at a coastal sampling site, Erdemli, Turkey. Water-soluble inorganic PO4(3)-P, a reactive, bioavailable, limiting macro-nutrient in the oligotrophic waters of the eastern Mediterranean was studied with respect to its contribution to biological productivity. Reactive PO4(3-)-P and NO2(-) + NO3(-)-N concentrations were found to be highly variable in rainwater samples. One of the aims of the study was to determine the contribution of dust transport to the soluble macro-nutrient budget of the eastern Mediterranean. No differences were found between the mean reactive P and NO(2-) + NO3(-)-N concentrations of "red rain" and normal rain events. Most likely as a result of low solubility of crustal phosphorus, dust episodes were not found to be important sources of reactive P, in terms of wet deposition. The annual wet deposition fluxes of reactive PO4(3-)-P and NO2(-) + NO3(-)-N into the Cilician Basin were respectively estimated to be 0.010 g P m(-2) per year and 0.23 g N m(-2) per year, which are comparable to the fluxes from land-based sources in the north-eastern Mediterranean. The incorporation of water soluble bioavailable PO4(3-)-P and NO2(-) + NO3(-)-N delivered via atmospheric wet deposition could be responsible for approximately 3.3% (0.40 g C m(-2) per year) and 11.0% (1.31 g C m(-2) per year) respectively, of the mean annual new production in the north-eastern Mediterranean.