三苯基锡对青萍生长及酶活性的影响

以青萍(Lemna mino)为实验生物,通过研究不同浓度(0、0.04、0.08、0.12、0.16、0.20mg·L-1)的三苯基锡(TPT)对青萍生长发育及过氧化氢酶(CAT)和过氧化物酶(POD)活性的影响,初步探讨了TPT对水生浮萍植物的毒性作用,以期为及时发现并排除TPT污染提供理论和直观依据.实验结果表明:培养4d后,TPT对青萍叶片生长量的半数抑制浓度(IC50)为0.10mg·L-1;CAT、POD活性随TPT处理浓度的升高显著升高(各暴露组与对照组均差异显著,p<0.05).结果显示,TPT对青萍具有明显的毒性作用,CAT和POD活性的变化可作为反映TPT污染胁迫的敏感指标.     

三苯基锡对假微型海链藻(Thalassiosira pseudonana)的生长抑制及温度的影响

在我国近岸海域环境中,三苯基锡分布十分广泛。本研究以假微型海链藻(Thalassiosira pseudonana)为目标物种,研究了4个不同温度条件下(10℃、15℃、25℃与30℃)三苯基锡暴露对其细胞生长以及光合作用参数(Fv/Fm与ФII)的影响。结果表明,假微型海链藻的细胞生长速率在高温与低温条件下均显著下降,而光合作用参数仅在30℃条件下受到显著影响。在暴露温度为10℃、15℃、25℃与30℃时,三苯基锡(triphenyltin,TPT)对假微型海链藻的生长抑制IC50值分别为1.81、1.69、1.09与0.73μg·L-1。TPT对假微型海链藻光合作用抑制的IC50随着温度的升高呈降低趋势。Two-way ANOVA分析结果显示,温度与三苯基锡的相互作用显著影响假微型海链藻的光合作用。上述研究结果可以为了解不同温度下三苯基锡对海洋微藻的毒性效应提供科学依据。     

三苯基锡和五氯酚胁迫斑马鱼生理生化的影响

以斑马鱼(Brachy danio rerio)作为受试生物,分析不同暴露浓度、不同暴露时间三苯基锡(TPT)、五氯酚(PCP)对斑马鱼生理生化指标的影响,在0,1.05,2.09,4.18,6.27,8.36μg·L-1的TPT和0,5.01,10.02,20.04,40.08,80.16μg·L-1的PCP暴露下,...     

长江口崇明渔港表层沉积物中丁基锡赋存特征及生态风险

在长江口及崇明岛沿岸渔港采集表层沉积物样品,通过超声萃取-乙基化衍生技术提取沉积物中的丁基锡化合物,用气相色谱-质谱联用仪分析沉积物中的丁基锡赋存特征。结果显示,在长江口的参考点沉积物中均未发现有机锡化合物,而在各调查的渔港沉积物中均检出丁基锡,总浓度在1.6~58.8 ng Sn·g-1(干重,以下同)之间变化。表层沉积物的三丁基锡(TBT)、二丁基锡(DBT)和一丁基锡(MBT)浓度范围分别为ND~28.7 ng Sn·g-1,ND~22.1 ng Sn·g-1,1.6~8 ng Sn·g-1。其中,堡镇港TBT污染水平最高;老滧港和奚家港口门处沉积物中TBT浓度与新河港差不多(平均为17.2 ng Sn·g-1),而在港口内部沉积物中均未检出TBT,仅有MBT残存。检出TBT的样点,均在大型渔船码头、客运游艇码头或船厂附近,其浓度均超过澳大利亚和新西兰推荐的TBT沉积物质量基准(ISQG)触发值,即5 ng Sn·g-1。同时各样点暴露浓度(PECsed)与预测无效应浓度(PNECsed)的商值均大于1,SQG和PECsed/PNECsed两个方面均反映了崇明岛渔业港口沉积物中的TBT存在生态风险。综上,长江口地区沉积物中有机锡化合物形态和浓度差异很大,码头或船厂附近沉积物中有机锡污染问题值得优先关注。     

三丁基锡对中国近海常见海洋微藻的毒性效应

研究三丁基氯化锡(TBT)对中国近海常见5种硅藻和甲藻(硅藻中丹麦细柱藻(Leptocylindrus danicus)、派格棍形藻(Bacilaria paxillifera)、聚生角毛藻(Chaetoceros socialis),甲藻中微型原甲藻(Prorocentrum minimum)、简裸甲藻(Gymnodinium simplex))的毒性效应,考察了有机锡对浮游藻光合活性(Fv/Fm)、粒径、生长的影响。结果表明:派格棍形藻、聚生角毛藻、简裸甲藻的光合活性(Fv/Fm)受TBT影响较显著;微型原甲藻、丹麦细柱藻的光合活性受TBT影响较小。高质量浓度TBT胁迫下海洋微藻峰值粒径显著减小,低质量浓度TBT对峰值粒径影响不显著。低质量浓度TBT对派格棍形藻、聚生角毛藻、简裸甲藻、微型原甲藻均有较强的毒性作用,非检测毒性浓度(NDEC)分别为1.17、1.07、0.23、3.73μg.L-1,丹麦细柱藻对TBT具有很强耐受性,NDEC为112.62μg.L-1。     

茶多酚对三丁基锡诱导的小鼠氧化损伤的保护作用

为研究茶多酚对三丁基锡诱导的小鼠氧化损伤是否具有保护作用,采用灌胃方法,对雄性小鼠进行TBT染毒, 然后分别用不同剂量的茶多酚进行保护．结果表明,茶多酚保护组小鼠肝组织活性氧(ROS)活性和丙二醛(MDA)含量均明显低于TBT对照组;彗星实验发现茶多酚保护组小鼠淋巴细胞尾长较正常,而尾相与TBT对照组相比没有显著改变．电镜观察结果表明茶多酚保护组胸腺细胞核和线粒体损伤明显减轻．因此茶多酚对TBT诱导的氧化损伤具有一定的预防作用,并且对细胞核损伤也有一定的保护作用．茶多酚对TBT所引起的细胞核损伤的保护作用机制可能是抑制脂质过氧化反应,防止细胞氧化损伤,从而保护DNA．     

我国海水水质基准的构建:以三丁基锡为例

我国近岸海域污染形势严峻、污染物种类繁多、生态健康风险复杂,现有的海水水质标准难以满足当前海洋环境污染评价、管理和监控的需求,亟需适宜我国海洋区系特征的海水水质基准作为水质标准修订与制定的理论依据.借鉴美国、欧盟和荷兰等国家水质基准的制定方法,提出了构建我国海水水质基准的思路,并给出了数值型双值基准的数据要求、定值方法和相应的计算模式等.以三丁基锡化合物(TBT)为例,按照论文建立的方法,计算了保护我国海洋水生生物的TBT基准.结果表明:我国TBT化合物海水水质基准高值(HSWC)和海水水质基准低值(LSWC)分别为0.43μg·L-1和0.002μg·L-1,与美国,加拿大和英国等国家的推荐基准值略有不同.研究结果将为我国海水水质基准的制定与研究提供帮助.     

基于被动采样技术的水体中有机锡污染筛查取证研究

将三油酸甘油酯-醋酸纤维素复合膜(TECAM)用作被动采样器,开展水体中一甲基锡(MMT)、二甲基锡(DMT)、一丁基锡(MBT)、二丁基锡(DBT)、三丁基锡(TBT)、二苯基锡(DPhT)和三苯基锡(TPhT)等7种有机锡氯化物的富集实验,膜样品经甲醇/醋酸溶液提取、乙基化衍生和正己烷萃取等前处理后,用气相色谱-质谱法(GC-MS)进行定性和定量检测,得到水体中痕量有机锡污染的相关指纹信息。结果表明,7种目标化合物均可在TECAM膜上富集,48 h后均可达到平衡状态;有机锡富集能力差异较大,其TECAM膜/水分配系数(log KTECAM)与其辛醇-水分配系数(log Kow)呈现显著正相关性(r=0.97, n=7)。甲基锡富集能力较低,但可定性筛查;而苯基锡和丁基锡等5种目标化合物在TECAM膜上的被动采样速率在0.06～0.16 L·g~(-1)·d~(-1)范围变化,经反演所得其在水体中的时间加权平均浓度与传统的主动采样法所得浓度没有显著差异(P0.05)。因此,基于TECAM被动采样技术可以实现水体中极性范围较广的痕量有机锡污染筛查取证。     

三丁基锡对中国近海常见海洋微藻的毒性效应

研究三丁基氯化锡（TBT）对中国近海常见5种硅藻和甲藻（硅藻中丹麦细柱藻（Leptocylindrus danicus）、派格棍形藻（Bacilaria paxillifera）、聚生角毛藻（Chaetoceros socialis）,甲藻中微型原甲藻（Prorocentrum minimum）、简裸甲藻（Gymnodinium simplex））的毒性效应,考察了有机锡对浮游藻光合活性（Fv/Fm）、粒径、生长的影响。结果表明：派格棍形藻、聚生角毛藻、简裸甲藻的光合活性（Fv/Fm）受TBT影响较显著;微型原甲藻、丹麦细柱藻的光合活性受TBT影响较小。高质量浓度TBT胁迫下海洋微藻峰值粒径显著减小,低质量浓度TBT对峰值粒径影响不显著。低质量浓度TBT对派格棍形藻、聚生角毛藻、简裸甲藻、微型原甲藻均有较强的毒性作用,非检测毒性浓度（NDEC）分别为1.17、1.07、0.23、3.73μg.L-1,丹麦细柱藻对TBT具有很强耐受性,NDEC为112.62μg.L-1。     

使用底栖和浮游桡足类生物测试评估沉积物修复方案的效果

三丁基锡（TBT）是一种常见于船舶防污涂料中的有机锡化合物。尽管该化学物已于2008年被禁用,但在ports和港口等海上交通区域仍可检出致毒水平（浓度）的TBT。一项补救方案在新西兰的一个港口实施,以将TBT和铜的浓度降低到可接受的（浓度）值。这项研究使用分析化学和桡足类生物测试相结合的方法评估了该方案的有效性。在港口内的三个空间梯度上采集沉积物和水样,并在修复前后测定了有机锡和金属含量。利用底栖和浮游桡足类生物测试估算了沉积物和淘析样品的毒性。虽然底泥样品的急性毒性在修复后减少,但对底栖桡足类的繁殖率仍有影响。本研究所采用的方法有望评估沿海地区修复过程的效果。     

十溴联苯醚(BDE-209)对土壤跳虫的急、慢性毒性效应

为揭示溴代阻燃剂对土壤生态系统的潜在危害,采用回避实验和繁殖实验评价了十溴联苯醚(BDE-209)对2种土壤跳虫Folsomia candida和Folsomia fimetaria的急/慢性毒性。48h的急性回避实验中,BDE-209对F.candida和F.fimetaria产生毒性效应的EC_(50)值分别为1.27和0.79mg·kg~(-1),LOEC值均小于0.5mg·kg~(-1)。慢性繁殖实验中,BDE-209对F.candida和F.fimetaria繁殖毒性的EC_(50)值分别为0.81和0.56mg·kg~(-1),LOEC值分别为<0.25和<0.5mg·kg~(-1)。研究表明,土壤BDE-209污染对跳虫的繁殖和环境行为有显著影响,且在较低暴露浓度下(0.25mg·kg~(-1))即对跳虫繁殖产生抑制效应;有性生殖的F.fimetaria比孤雌生殖的F.candida对BDE-209污染的毒性响应更为敏感。     

通过式固相萃取/超高效液相色谱-串联质谱法测定蔬菜中18种农药残留

建立了超高效液相色谱-串联质谱(UPLC-MS;MS)快速测定蔬菜中18种农药残留的方法.样品经乙腈提取后,经Oasis PRiME HLB固相萃取柱净化,采用ACQUITY UPLC HSS T3 C18(50 mm×2.1 mm,1.8μm)色谱柱进行分离,以0.1%甲酸水溶液和乙腈作为流动相进行梯度洗脱.采用电喷雾电离源、正离子模式下以多反应监测(MRM)进行定性和定量分析.结果表明,18种农药在0.5—50μg·L^-1范围内线性关系良好(r2>0.995),方法最低检出限为0.4—1.5μg·kg^-1,最低定量限为1.4—5.0μg·kg^-1.在韭菜、芹菜、番茄、白菜基质中,5、10、50μg·kg^-1添加水平下的加标回收率为60.2%—126.9%,相对标准偏差(RSD)为0.4%—21.6%(n=3).     

多环麝香对蚯蚓的急性和亚急性毒性效应

为探讨多环麝香对土壤动物的毒性效应,以赤子爱胜蚓(Eisenia fetida)为供试生物,采用滤纸接触法与自然土壤法,考察了吐纳麝香(AHTN)和佳乐麝香(HHCB)对蚯蚓的急性和亚急性毒性效应。结果显示,滤纸法测得的AHTN和HHCB对蚯蚓的急性经皮毒性为中等毒性,对蚯蚓的48h-LC_(50)分别为20.76和11.87μg·cm~(-2),而自然土壤法测得的AHTN和HHCB对蚯蚓的14d-LC_(50)分别为436.3和392.4μg·g~(-1),2种多环麝香皆属低毒物质。HHCB对蚯蚓的急性毒性大于AHTN,但2种毒性测定方法中不同的染毒介质和毒性作用途径使AHTN和HHCB的急性毒性等级的界定有所差异。AHTN和HHCB对蚯蚓繁殖率的抑制作用较对生长速率更为明显,2种多环麝香对蚯蚓繁殖率的无可见效应浓度(NOEC)均为30μg·g~(-1),最低可见效应浓度(LOEC)均为50μg·g~(-1)。研究表明,蚯蚓繁殖率可作为一种潜在的生物标志物,用于监测或表征土壤中多环麝香的污染水平及其亚急性毒性效应。     

六溴环十二烷及其复合污染脑发育期暴露对大鼠甲状腺激素代谢过程的影响

研究六溴环十二烷（HBCD）及其复合污染对发育期幼鼠甲状腺激素代谢过程的影响。设计HBCD单一暴露剂量（10、50、100、300ttg·kg-1）,及HBCD与等浓度商用多溴联苯醚DE-71按2：1复合暴露剂量（10、50、100、300gg·kg-1）,对新生3d的SD大鼠进行为期42d的暴露,放射免疫法测定血清中甲状腺激素（TT3,TT4,FT3,FT4,TSH）水平,并分别测定肝脏和脑组织中甲状腺激素脱碘酶（D1,D2）活性及其对应基因的相对表达水平。与对照组相比较,经HBCD暴露后,大鼠血清中TT4、TT3、FT4、FT3浓度随着暴露剂量增大呈现先升高后下降的趋势,其中10μg·kg-1剂量组的FT3质量分数显著升高（P〈0．05）,300μg·kg-1剂量组的FT4质量分数显著下降（P〈0．05）;TSH则呈现下降趋势。lO、50及300μg·kg-1剂量组的TSH质量分数均显著下降（P〈0．05）。HBCD／DE-7l复合暴露后,大鼠血清中TT4、TT3、FT4、FT3浓度随着暴露剂量的增大呈升高趋势,其中50μg·kg-1剂量组TT4质量分数显著升高（P〈0．05）,50μg·kg-1及300μg·kg-1剂量组FT4质量分数显著升高（P〈0．05）,300μg·kg-1剂量组FT3质量分数显著升高（P〈0．05）。单一暴露后,D1活性及基因表达水平均呈下降趋势,300gμg·kg-1剂量组基因表达水平下降显著（P〈0．05）;D2活性及基因表达水平则均呈现下降趋势,50μg·kg-1剂量组均显著下降（P〈0．05）;HBCD／DE-71复合暴露后,D1、D2活性及其基因表达水平则均呈升高趋势,其中100μg·kg-1剂量组D1活性及基因表达水平均显著性升高（P〈0．05）,300μg·kg-1剂量组D2活性显著性升高（P〈0．05）。HBCD及HBCD／DE-71复合污染物均能通过改变甲状腺激素代谢酶的活性及mRNA表达水平进一步影响机体甲状腺激素的内稳态平衡,且HBCD单一暴露与HBCD／DE-71复合暴露对机体毒性作用途径及所产生的毒性效果存在着很大的差异。     

上海市公园绿地常见落叶树木叶片汞浓度时空特征及环境意义

植物叶片汞浓度与大气气态单质汞(GEM/Hg0)浓度的线性关系表明叶片汞浓度大小可用于指示植物生长区内GEM浓度的高低水平.通过分析上海市绿地公园(25座)中常见落叶树木樱花、水杉、法桐叶片汞浓度的时空变化特征,探究区域内GEM含量水平及分布特征.2017年5-10月对7座公园中这3种树木叶汞浓度进行连续监测,结果显示...     

A new procedure combining GC-MS with accelerated solvent extraction for the analysis of phthalic acid esters in contaminated soils

An optimized procedure based on gas chromatography-mass spectrometry (GC-MS) combined with accelerated solvent extraction (ASE) is developed for the analysis of six phthalic acid esters (PAEs), which are priority soil pollutants nominated by United States Environmental Protection Agency (USEPA). Quantification of PAEs in soil employs ultrasonic extraction (UE) (USEPA 3550) and ASE (USEPA 3545), followed by clean up procedures involving three different chromatography columns and two combined elution methods. GC-MS conditions under selected ion monitoring (SIM) mode are described and quality assurance and quality control (QA/QC) criteria with high accuracy and sensitivity for target analytes were achieved. Method reliability is assured with the use of an isotopically labeled PAE, di-n-butyl phthalate-d4 (DnBP-D4), as a surrogate, and benzyl benzoate (BB) as an internal standard, and with the analysis of certified reference materials (CRM). QA/QC for the developed procedure was tested in four PAE-spiked soils and one PAE-contaminated soil. The four spiked soils were originated from typical Chinese agricultural fields and the contaminated soil was obtained from an electronic waste dismantling area. Instrument detection limits (IDLs) for the six PAEs ranged 0.10–0.31 μg·L^-1 and method detection limits (MDLs) of the four spiked soils varied from a range of 20–70 μg·kg^-1 to a range of 90– 290 μg·kg^-1. Linearity of response between 20 μg·L^-1 and 2 mg·L^-1 was also established and the correlation coefficients (R) were all>0.998. Spiked soil matrix showed relative recovery rates between 75 and 120% for the six target compounds and about 93% for the surrogate substance. The developed procedure is anticipated to be highly applicable for field surveys of soil PAE pollution in China.     

Whole pictures of halogenated disinfection byproducts in tap water from China’s cities

When bromide/iodide is present in source water, hypobromous acid/hypoiodous acid will be formed with addition of chlorine, chloramine, or other disinfectants. Hypobromous acid/hypoiodous acid undergoes reactions with natural organic matter in source water to form numerous brominated/iodinated disinfection byproducts (DBPs). In this study, tap water samples were collected from eight cities in China. With the aid of electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 35, m/z 81, and m/z 126.9, whole pictures of polar chlorinated, brominated, and iodinated DBPs in the tap water samples were revealed for the first time. Numerous polar halogenated DBPs were detected, including haloacetic acids, newly identified halogenated phenols, and many new/unknown halogenated compounds. Total organic chlorine, total organic bromine, and total organic iodine were also measured to indicate the total levels of all chlorinated, brominated, and iodinated DBPs in the tap water samples. The total organic chlorine concentrations ranged from 26.8 to 194.0 μg·L^–1 as Cl, with an average of 109.2 μg·L^–1 as Cl; the total organic bromine concentrations ranged from below detection limit to 113.3 μg·L^–1 as Br, with an average of 34.7 μg·L^–1 as Br; the total organic iodine concentrations ranged from below detection limit to 16.4 μg·L^–1 as I, with an average of 9.1 μg·L^–1 as I; the total organic halogen concentrations ranged from 31.3 to 220.4 μg·L^–1 as Cl, with an average of 127.2 μg·L^–1 as Cl.     

Dilution sampling and analysis of particulate matter in biomass-derived syngas

Thermochemical biomass gasification, followed by conversion of the produced syngas to fuels and electrical power, is a promising energy alternative. Real-world characterization of particulate matter (PM) and other contaminants in the syngas is important to minimize damage and ensure efficient operation of the engines it powers and the fuels created from it. A dilution sampling system is demonstrated to quantify PM in syngas generated from two gasification plants utilizing different biomass feedstocks: a BioMax^?15 Biopower System that uses raw and torrefied woodchips as feedstocks, and an integrated biorefinery (IBR) that uses rice hulls and woodchips as feedstocks. PM_2.5 mass concentrations in syngas from the IBR downstream of the purification system were 12.8–13.7 μg·m^-3, which were significantly lower than the maximum level for catalyst protection (500 μg·m^-3) and were 2–3 orders of magnitude lower than those in BioMax^?15 syngas (2247–4835 μg·m^-3). Ultrafine particle number concentration and PM_2.5 chemical constituents were also much lower in the IBR syngas than in the BioMax^?15. The dilution sampling system enabled reliable measurements over a wide range of concentrations: the use of high sensitivity instruments allowed measurement at very low concentrations (~1 μg·m^-3), while the flexibility of dilution minimized sampling problems that are commonly encountered due to high levels of tars in raw syngas (~1 g·m^-3).     

Haloacetic acids in swimming pool and spa water in the United States and China

The objective of this study is to investigate the occurrence of haloacetic acids （HAAs）, a group of disinfection byproducts, in swimming pool and spa water. The samples were collected from six indoor pools, six outdoor pools and three spas in Pennsylvania, the United States, and from five outdoor pools and nine indoor pools in Beijing, China. Five HAAs （HAA5）, including monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid were analyzed. Total chlorine, pH and total organic carbon concentration were analyzed as well. Results indicated that the levels of HAA5 in swimming pools and spas in the United States ranged from 70 to 3980μg·L^-1, with an arithmetic average at 1440μg·L^-1 and a median level at 1150μg·L^-1. These levels are much higher than the levels reported in chlorinated drinking water and are likely due to organic matters released from swimmers＇ bodies. The levels of HAA5 in swimming pools in China ranged from 13 to 332μg·L^-1, with an arithmetic average at 117μg·L^-1 and a median level at 114μg·L^-1. The lower HAA levels in swimming pools in China were due to the lower chlorine residuals. Results from this study can help water professionals to better understand the formation and stability of HAAs in chlorinated water and assess risks associated with exposures to HAAs in swimming pools and spas.