大气PM_(10)中多环芳烃的污染特征

利用GC-MS对2008年5月至11月淮南市5个采样点大气可吸入颗粒物(PM10)样品进行分析,总结了研究区内PM10及其中16种PAHs的浓度特征、季节变化规律和来源解析.结果表明,不同采样点PM10浓度均偏高,超标率为14%—238%;PM10浓度水平为谢家集田十五小大通三小淮化集团理工校园.研究区内16种PAHs浓度总量的范围在15.20ng.m-3—111.58ng.m-3之间,平均浓度为64.36ng.m-3,4环以上的稠环芳烃占总浓度的86%.PAHs总量的季节变化与采样时环境温度显示出较好的负相关性,即秋季春季夏季.运用多环芳烃比值综合判断,淮南市大气PM10中PAHs主要以燃煤和机动车尾气混合来源为主,石油源和木材燃烧来源的贡献较小.     

南昌市秋季PM_(2.5)中多环芳烃的污染特征、风险评价及来源分析

用气相色谱-质谱法(GC-MS)定量分析了2013年9月南昌市PM_(2.5)中16种优控多环芳烃(PAHs)含量.结果表明,PAHs总浓度平均值为17.95 ng·m~(-3),变化范围为3.55—39.97 ng·m~(-3).不同环数多环芳烃占总浓度比例由大到小依次为:5环(50.45%)4环(19.32%)6环(17.99%)2环(6.34%)3环(5.90%),表现出明显的机动车尾气排放特征.通过计算PAHs的苯并[a]芘(BaP)毒性当量浓度(9.458—14.454 ng·m~(-3)),表明南昌市PAHs对人体健康存在潜在危害.特征化合物比值法和主成分分析法结果表明,燃煤、机动车尾气、农业燃烧及少量的石油挥发是南昌市PM_(2.5)中PAHs的主要污染源.     

天津市土壤多环芳烃污染特征、源解析和生态风险评价

采用气相色谱-质谱联机方法(GC-MS)分析了天津市不同功能区10个采样点表层土壤样品中16种多环芳烃(PAHs)的浓度,并对其污染特征、来源和生态风险进行了分析.结果表明:天津市土壤中16种多环芳烃的总浓度(∑PAHs)范围为142—1.49×103ng·g-1,平均浓度765 ng·g-1,Bap浓度范围7.06—118 ng·g-1,平均值37.6 ng·g-1.∑PAHs浓度均值呈工业区近郊区城区远郊区趋势.采用PAHs成分谱、污染物的特征比值和主成分分析的污染来源解析结果表明:工业区PAHs主要来源于焦化、煤和天然气的燃烧,以及机动车的污染排放;城区和郊区土壤中PAHs除来自于煤和焦炭的燃烧外,机动车污染是一个非常重要的污染源.根据荷兰土壤质量标准,所有采样点均有PAHs单体超标,其中西青、津南、北辰、汉沽、塘沽和大港采样点超过荷兰土壤标准规定的10种多环芳烃的苯并(a)芘(Bap)毒性当量浓度(TEQ Bap10)限值33 ng·g-1,说明天津近郊区和工业区土壤已受到PAHs的污染,存在潜在的生态风险.     

北京大气颗粒物中多环芳烃浓度季节变化及来源分析

使用大流量滤膜采样器,从2006年9月至2007年8月,每周同时采集北京城市大气可吸入颗粒物(PM10)和细粒子样品(PM2.5)各一次,二氯甲烷超声抽提一气相色谱/质谱分析了17种多环芳烃(PAHs)浓度,结果表明,春、夏、秋、冬四季北京大气PM10和PM2.5中PAHs总量分别为63.8±44.6ng·m-3、43.2±4.5ng·m-3、84.7±108.3ng·m-3、348.0±250.0ng·m-3和54.7±17.3ng·m-3、40.3±8.6ng·m-3、66.1±81.5ng·m-3、337.7±267.2ng·m-3;约有70%的PAHs存在于细粒子PM2.5中,其质量浓度有明显季节变化,冬季>秋季>春季>夏季;颗粒物中PAHs主要以4、5、6环存在,其中4环以上占79.4%.源解析表明,北京大气颗粒物中的PAHs主要来自燃煤,同时汽油、柴油燃烧排放也不能忽略.结合气象要素分析,温度升高和太阳辐射增强易造成多环芳烃挥发和反应,湿沉降有利于多环芳烃随颗粒物清除.     

大型钢铁厂及其周边土壤多环芳烃污染现状调查、评价与源解析

采用气相色谱-质谱联机方法(GC-MS)分析了东北某钢铁厂及周边居住区、风景区共11个采样点表层土壤样品16种多环芳烃(PAHs),结果表明,钢铁工业区16种PAHs(∑PAHs)浓度范围为3.39×103—1.54×105ng·g-1,平均浓度3.21×104ng·g-1;居住区∑PAHs浓度范围为587—6.70×103ng·g-1,平均浓度3.82×103ng·g-1;风景区千山∑PAHs浓度385 ng·g-1.∑PAHs和Bap浓度均呈工业区>居住区>风景区趋势.与国内外其他研究结果相比,该钢铁工业区及其周边居住区土壤PAHs污染相对较为严重,11个采样点中有9个采样点土壤∑PAHs为严重污染,4个采样点苯并(a)芘(Bap)浓度超过加拿大土壤质量基准.利用特征比值法(Diagnostic Rate)和主成分分析法(Principal component analysis,PCA)对钢铁工业区及其周边地区土壤进行了源解析,结果表明,钢铁工业区土壤中PAHs主要来源于焦炉、燃煤、柴油燃烧等污染源,周边地区土壤除受工业污染源排放影响外,机动车汽油、柴油污染排放也有重要影响.     

南京市可吸入颗粒物中多环芳烃的源解析

采集南京市燃煤、焦化、机动车和烹调四种污染源样品,采用高效液相色谱仪测定其中的PAHs含量,建立四种源的成分谱.根据所得数据,运用化学质量平衡(CMB)受体模型对PM10中的PAHs进行源解析研究,以确定燃煤源、焦化源、交通源和烹调源对PM10中PAHs的贡献率.     

太原市不同功能区环境空气中挥发性有机物特征与来源解析

采集太原市3个不同功能区夏季和冬季环境空气样品,使用色谱-质谱仪测定挥发性有机物(VOCs)的组成,分析VOCs浓度变化和日变化特征,计算臭氧生成潜势(OFP),利用特征比值法和正定矩阵因子分析法(PMF)研究环境空气中VOCs的来源.结果表明,观测期间太原市环境空气中VOC总浓度变化范围为(36.27—210.67)μg·m~(-3),夏季和冬季VOCs化合物平均质量浓度为49.73μg·m~(-3)和205.19μg·m~(-3),冬季环境空气中VOCs浓度是夏季VOCs的4.13倍;VOCs日变化受到机动车排放和光化学反应显著影响,且夏季影响大于冬季;夏季OFP最大的物种为烯烃类化合物,冬季OFP最大的物种为芳香烃类化合物.太原市环境空气中VOCs主要包括五类污染源,分别为燃煤源28.10%、机动车源27.41%、挥发源22.90%、液化石油/天然气源14.90%和植物源6.69%;不同功能区主要污染源存在差异,太原市夏季工业交通区最主要排放源为燃煤源,居民商业混合区和居民交通区受燃煤源和机动车排放源共同影响,冬季太原市燃煤源是环境空气中VOCs的最主要污染源.     

北京市冬季大气气溶胶中PAHs的污染特征

利用大流量颗粒物采样器采集了2005-2006年冬季北京市大气气溶胶中PM10和PM2.5样品,采用气相色谱/质谱技术对样品中的多环芳烃进行检测.结果表明:北京市冬季大气颗粒物PM10和PM2.5中PAHs总量分别为520.5±476.9ng·m-3和326.8±294.3ng·m-3,且大部分存在于细粒子中,4环以上的稠环芳烃占总浓度的87%.根据荧蒽/芘等比值指标判别,北京市冬季PAHs主要以燃煤排放为主,其次是石油燃烧交通排放.风速增大和太阳辐射曝辐量增强,都会降低颗粒物中多环芳烃浓度.     

徐州市城市大气中的PAHs来源解析

采用化学质量平衡模型（CMB）对徐州市大气颗粒物中的多环芳烃（PAHs）进行来源分析,从而来确定各个源对大气的PAHs贡献值。主要通过利用大流量采样器配置PM10切割头在冬季和夏季对不同功能区,即生活区、工业区和旅游区采样大气中的可吸入颗粒物（PM10）样品,并用高效液相色谱法（HPLC）重点分析和研究了美国环保局（EPA）列出的16种PHAS优先污染物。研究结果表明：徐州市PM10污染比较严重,PM10污染质量浓度水平冬季是（288.81μg·m-3）大于夏季（276.34μg·m-3）,特别是工业区,污染数值达到393.13μg·m-3。夏季的总PAHs质量浓度为22.89 ng·m-3,分别是生活区28.35 ng·m-3、工业区21.75 ng·m-3和旅游区18.58 ng·m-3。冬季的总PAHs质量浓度为306.29 ng·m-3,分别是工业区388.03 ng·m-3、生活区276.29 ng·m-3和旅游区254.28 ng·m-3。夏季和冬季情况下,旅游区的污染相对来说都是最低的PM10中多环芳烃的源解析结果为,煤烟尘污染源的全年贡献率为64.00%,冬季煤烟尘污染源的贡献率为66.51%,夏季煤烟尘污染源的贡献率为57.21%,说明煤烟尘是PM10中多环芳烃的主要贡献源,土壤尘次之,全年贡献率为24.90%,冬季为25.48%,夏季为28.97%,因此,扬尘和烟煤尘的污染是徐州市的PM10中PAHs的最主要来源。     

吉林省典型城市大气中PAHs来源解析

通过对吉林省4个典型城市,即吉林、白城、四平和通化市大气颗粒物中多环芳烃（PAHs）的采样和分析,得到16种PAHs的成分谱,应用主因子分析和特征比值法对其进行定性研究,得到吉林省大气中PAHs的2种主要来源--车辆尾气和燃煤。并应用绝对主因子分析法进一步定量计算这2种源对PAHs的浓度贡献值及贡献率,结果表明：吉林省典型城市PAHs解析值为772.39μg·g-1,绝大多数解析值与监测值之间的比值接近于1,车辆尾气对各PAH的贡献率为2.6%~67.6%,燃煤源的贡献率为24.1%~121.2%。另外,该研究还计算了已识别的2种源对于不同环数的PAHs的贡献,2~3环的PAHs大部分来自于燃煤,约占总体的89%,车辆尾气仅占11%;4环的PAHs约58%来源于燃煤,42%来源于车辆尾气;5环的PAHs约45%来源于燃煤,55%来源于车辆尾气;6环PAHs来源于燃煤的占61%,来源于车辆尾气的占39%。     

Effects of nano-silicon and common silicon on lead uptake and translocation in two rice cultivars

The current study investigated the effects of nano-silicon (Si) and common Si on lead (Pb) toxicity, uptake, translocation, and accumulation in the rice cultivars Yangdao 6 and Yu 44 grown in soil containing two different Pb levels (500 mg·kg⁻¹ and 1000 mg·kg⁻¹). The results showed that Si application alleviated the toxic effects of Pb on rice growth. Under soil Pb treatments of 500 and 1000 mg·kg⁻¹, the biomasses of plants supplied with common Si and nano-Si were 1.8%–5.2% and 3.3%–11.8% higher, respectively, than those of plants with no Si supply (control). Compared to the control, Pb concentrations in rice shoots supplied with common Si and nano-Si were reduced by 14.3%–31.4% and 27.6%–54.0%, respectively. Pb concentrations in rice grains treated with common Si and nano-Si decreased by 21.3%–40.9% and 38.6%–64.8%, respectively. Pb translocation factors (TFs) from roots to shoots decreased by 15.0%–29.3% and 25.6%–50.8%, respectively. The TFs from shoots to grains reduced by 8.3%–13.7% and 15.3%–21.1%, respectively, after Si application. The magnitudes of the effects observed on plants decreased in the following order: nano-Si treatment>common Si treatment and high-grain-Pb-accumulating cultivar (Yangdao 6)>low-grain-Pb-accumulating cultivar (Yu 44) and heavy Pb stress (1000 mg·kg⁻¹)>moderate Pb stress (500 mg·kg⁻¹)>no Pb treatment. The results of the study indicate that nano-Si is more efficient than common Si in ameliorating the toxic effects of Pb on rice growth, preventing Pb transfer from rice roots to aboveground parts, and blocking Pb accumulation in rice grains, especially in high-Pb-accumulating rice cultivars and in heavily Pb-polluted soils.     

铬对生活污水中氮磷的植物净化效果及体内氮磷含量的影响

采用水培法,设置4个Cr6＋质量浓度（0,1,10,20mg·L-1）处理风车草（Cyperus alternifolius）和薏米（Coix aquatica Roxb）,以此研究铬对生活污水中氮磷净化效果及植物体内氮磷质量分数的影响。结果表明：（1）试验期内,铬质量浓度为1mg·L-1时促进风车草和薏米对总氮的去除,铬质量浓度为20mg·L-1时则抑制;总氮去除率因处理时间不同而不同,表现在处理17d时0mg·L-1、1mg·L-1铬处理显著高于处理7d,但20mg·L-1处理则相反;除Cr20处理外,薏米对总氮的去除率显著高于风车草。（2）风车草和薏米对生活污水中总磷的去除率随铬处理时间延长而降低,表现在处理17d时10mg·L-1、20mg·L-1铬处理显著低于处理7d;在20mg·L-1铬处理下皆显著低于对照;风车草对总磷的去除率在10mg·L-1、20mg·L-1铬处理下显著高于薏米。（3）不同质量浓度Cr6＋处理下风车草和薏米体内氮、磷质量分数的变化不同,其中20mg·L-1铬处理下风车草茎和薏米根、茎及叶片皆显著低于对照。     

珠江广州河段及其邻近河流表层沉积物中烷基酚的污染状况

为确定珠江广州河段及其邻近河流水体沉积物中烷基酚的时空分布状况,对该河段表层沉积物采样并应用气相色谱-质谱单离子扫描模式进行了烷基酚(APs)含量分析。结果表明壬基酚(NP)和辛基酚(OP)在样品中均有检出,其含量(以干质量计)范围分别在36.04～24694.10ng·g-1之间(中值为3717.52ng·g-1)和0.36～498.54ng·g-1之间(中值为21.10ng·g-1);珠江广州河段整体含量明显高于其邻近支流各采样点。所研究的表层沉积物样品中烷基酚含量普遍高于世界上其它都市和工业中心附近地区的污染水平,其中壬基酚含量均低于对摇蚊属昆虫(Chironomus riparius)的10d半致死浓度(LC50),但两个含量最高值均已与壬基酚对小虾(shrimp)的亚急性毒性最低效应浓度(LOEC)相接近,且大部分样品中的辛基酚含量都超过了对淡水螺(Potamopyrgus antipodarum)的8周最低效应浓度值(LOEC)标准。因此,烷基酚对该区生物造成的生态风险是一个必须加以认真对待的问题。     

Elemental concentrations in air, water, and aquatic biota in two rural provinces in northern Vietnam

The present study on environmental pollution in northern Vietnam investigates elemental concentrations in fine particulate matter (PM_2.5), freshwater, and aquatic biota at two sites with differing levels of industrial activities. An Thin is situated 47 km east of Hanoi in the neighbourhood of a coal combustion power plant, whereas the reference site, Duy Minh, is situated in the agricultural province of Ha Nam, 40 km south of Hanoi. Elemental concentrations were analysed using energy-dispersive X-ray fluorescence, total reflection X-ray fluorescence, and graphite furnace atomic absorption spectro-metry. All investigated elements in fine particles (PM_2.5) had significantly higher concentrations in An Thin, thus identifying the air at this site as polluted. In contrast to the aerosol samples, elemental concentrations as well as quantitative differences between the sampling sites were low in freshwater and biota, indicating that the impact of atmospheric deposition was limited.     

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.     

土壤样品中四溴双酚A和六溴环十二烷的测定

建立了LC-MS/MS法同时测定土壤样品中四溴双酚A(Tetrabromobisphenol A,TBBPA)和六溴环十二烷(Hexabromocyclododecanes,HBCDs)的分析方法.样品经索氏抽提后,采用去活化硅胶柱进行净化.TBBPA、α-HBCD、β-HBCD和γ-HBCD的方法检出限分别为0.0315 ng.g-1、0.767 ng.g-1、0.197 ng.g-1和0.163 ng.g-1,方法加标回收率为59.0%—69.4%,可用于土壤样品中痕量TBBPA和HBCDs的测定.经过严格的质量控制,采用本方法对某郊区土壤样品进行了测定,其TBBPA和HBCDs的含量均在pg.g-1量级.     

Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

• Regulation of redox conditions promotes the generation of free radicals on HM. • HM-PFRs can be fractionated into active and inactive types depending on stability. • The newly produced PFRs readily release electrons to oxygen and generate ROS. • PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM. The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H₂O₂ and L-ascorbic acid (VC) (assigned as H₂O₂-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H₂O₂ at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H₂O₂-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O₂, inducing the formation of reactive oxygen species (ROS, i.e., ^•OH and ^•O₂⁻). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.     

GC-MS/MS法结合顶空进样测定原料药厄贝沙坦中N-亚硝基二甲胺(NDMA)与N-亚硝基二乙胺(NDEA)含量

本文使用三重四极杆气质联用仪GCMS-TQ8050结合顶空进样建立了一种快速检测原料药厄贝沙坦中N-亚硝基二甲胺(NDMA)与N-亚硝基二乙胺(NDEA)的方法.在浓度范围0.025—100μg两种物质均表现出良好线性,相关系数达到0.999以上,0.025μg标液信噪比(S;N)NDMA为11.7,NDEA为19.7.标准品连续进样6针,0.1μg与5μg峰面积RSD%分别小于3%与2%.0.1、0.2、5μg的加标平均回收率在96.2%—106.4%之间.该方法简单方便,可以较好的应用于厄贝沙坦原料药中NDMA和NDEA的含量的测定.     

铅胁迫下黄瓜幼苗内源多胺变化动态的初步研究

以黄瓜幼苗为材料,采用高效液相色谱法测定黄瓜幼苗叶和茎中内源多胺的含量,研究了铅胁迫下黄瓜幼苗生长及内源多胺的变化。结果表明:铅质量浓度为100mg·L-1时促进黄瓜幼苗的生长,铅质量浓度高于100mg·L-1时,黄瓜幼苗茎高和根长逐渐下降;铅胁迫下黄瓜幼苗地上部的腐胺含量明显高于对照值,且随着铅质量浓度增加和处理时间的延长呈下降趋势。黄瓜幼苗叶片精胺和亚精胺在处理第5d时高于对照值,茎中精胺和亚精胺含量在处理第7d高于对照值,而其它时间内的都低于对照值,而且其含量均随铅质量浓度的增加而呈下降趋势;过氧化物酶活性变化与内源多胺含量(腐胺、精胺和亚精胺之和)的变化相似,表明铅胁迫能改变黄瓜幼苗内源多胺的含量和调节过氧化物酶活性,从而影响着黄瓜植株的生长。     

Quantitative and structural analyses of hazardous elements in Chinese medicines and herbs

Thirty samples of Chinese medicines and herbs were analyzed using instrumental neutron activation analysis (INAA) and X-ray diffraction (XRD) methods, mainly noting on the hazardous elements arsenic (As), mercury (Hg), chromium, antimony and cobalt. The three Niuhuang Jiedu Pian samples contained 8.6%, 8.3% and 2.2% As. Two out of four Liushen Wan samples contained approximately7% of both As and Hg. Despite being identically named, the other two Liushen Wan samples did not contain such high concentrations. Japanese Liushen Wan for children contained 1.2 ± 0.03% As and 31 ± 12 mg/kg Hg, whereas Liushen Wan for adults manufactured by another Japanese company contained 550 ± 22 mg/kg As and 1.2 ± 0.05 mg/kg Hg. All the chemical structural formulas of As and Hg in the high-concentration Niuhuang Jiedu Pian and Liushen Wan were realgar (As₄S₄), uzonite (As₄S₅) and cinnabar (HgS). Although the human body is generally not believed to absorb sulphides, continuous intake of these Chinese medicines is potentially no good because it is possible that some arsenic-sulfides will dissolve in gastric acid and then alter their chemical structures. Additionally, many herbs contained low concentrations of Hg, and their chemical structures were unknown.