超声提取-分散液液微萃取-气相色谱串联质谱法测定大气PM10中的7种有机磷酸酯阻燃剂

建立了超声提取-分散液液微萃取联合气相色谱串联三重四极杆质谱测定大气中7种有机磷酸酯阻燃剂(磷酸三丙酯(TPrP)、磷酸三异丁酯(TiBP)、磷酸三正丁酯(TnBP)、磷酸三(1-氯-2-丙基)酯(TCIPP)、磷酸三(1,3-二氯-2-丙基)酯(TDCPP)、磷酸三苯酯(TPP)、磷酸三甲苯酯(TCP))的方法.本实...     

环境中有机磷酸酯阻燃剂分析方法的研究进展

有机磷酸酯广泛应用于塑料、纺织品、电子设备、建筑材料中作为阻燃剂或塑化剂,其使用量逐渐增长,已经导致可以在多种环境介质中检测到.本文综述了近几年国内外对有机磷酸酯的分析方法的研究进展,介绍了从空气、沉积物、生物、水等环境介质中提取、净化和检测有机磷酸酯的多种方法和技术手段,讨论了实验过程中替代标、内标的选择及空白污染控制措施.最后,对未来相关分析方法的发展趋势进行了展望.     

污水处理厂中有机磷酸酯的研究进展

有机磷酸酯(OPEs)作为阻燃剂和增塑剂被广泛用于建筑、电子、化学和纺织等行业中。由于有机磷酸酯大多以物理方法掺加于产品中,更易被释放进入环境中。有机磷酸酯具有神经毒性、致癌性和基因毒性,关于有机磷酸酯产生、迁徙和削减的研究受到了学界的广泛注意。污水处理厂作为地表水环境中污染物的重要来源,在有机磷酸酯进入环境的过程中发挥了重要作用。本文总结了各国污水处理厂中有机磷酸酯研究现状,随着技术的发展被监测的有机磷酸酯种类越来越多;欧洲国家污水中有机磷酸酯检出的最高浓度普遍高于其他国家和地区;极性有机磷酸酯更倾向于转移至污水中,非极性的更倾向于吸附到污泥中;氯代有机磷酸酯普遍去除率很低,有的经过污水处理工艺反而增加,烷基和芳基有机磷酸酯有较高的去除率。     

超高效液相色谱-串联质谱法测定污水中14种有机磷酸酯阻燃剂

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)联用法同时测定污水中14种有机磷酸酯阻燃剂(OPEs)的分析方法.样品采集后,经GF/C膜过滤,HLB固相萃取小柱净化后进样分析.以BEH C18色谱柱为分离柱,乙腈和水混合液为流动相(0.2 mL min-1)梯度洗脱,15 min内可完成14种OPEs的分离.在电喷雾正离子模式下,采用多反应监测模式(MRM)进行质谱测定.在加标浓度为1.0μg·L-1时,14种OPEs在污水处理厂进水和出水中的回收率分别为52.1%—119%、43.6%—114%,相对标准偏差(RSD)分别为1.2%—16.2%、0.4%—9.2%,方法的检出限(LOD)在0.3—6.0 ng·L-1间.方法精密度好,准确度高,可满足同时对污水样品中的14种OPEs进行定性及定量分析的要求.     

有机磷酸酯类阻燃剂毒性效应研究进展

有机磷酸酯类阻燃剂(organophosphate flame retardants,OPFRs)作为多溴联苯醚等溴代阻燃剂(brominated flame retardants,BFRs)的替代品被广泛应用,由此带来的环境影响广受关注。目前针对OPFRs的生物毒性研究仍相对有限,需要更全面调查其在多环境介质中的暴露状况、环境归趋、生物毒性效应等研究成果,在此基础上才能综合评价其可能引起的生态风险。因此,综述了OPFRs对水生生物、哺乳动物和人类等多种生物体的急性毒性、生殖与发育毒性、神经毒性、脏器毒性、基因毒性与致突变性和内分泌干扰性。OPFRs的多种生物毒性已得到证实,但相关致毒机制研究尚不完整深入。最后对OPFRs的进一步研究存在的问题进行分析,提出了研究展望,以期促进开展OPFRs的环境风险和人体健康风险研究。     

有机磷酸酯阻燃剂降解方法的研究进展

有机磷阻燃剂(OPFRs)已取代溴代阻燃剂广泛应用于各行业,并很容易通过挥发、磨损等方式进入各环境介质中.目前,已在水体、土壤等环境介质中检测到了 OPFRs的存在.本文总结了目前已有的OPFRs在环境中的降解方式,据其原理主要可分为化学法和生物法,化学法主要包含Fenton/类Fenton氧化法、紫外-双氧水法(UV...     

有机磷酸酯在岷江干流鱼体中的分布

有机磷酸酯(organophosphate esters,OPEs)进入水环境中后,可通过生物富集放大最终对人体健康带来威胁.然而目前对OPEs在各流域生物体内的赋存及生物富集效应报道甚少.本文定量测定了岷江干流新津、宜宾和乐山3个站点不同种鱼体的鳃、肝脏、肾脏和肌肉等组织中6种OPEs的含量,包括磷酸丁酯(TnBP)...     

有机磷酸酯对斑马鱼的早期神经毒性作用研究

国内外研究已证实,有机磷酸酯广泛分布于多种环境介质中,但目前仍缺乏足够的数据阐明有机磷酸酯具有早期神经毒性效应及其可能的毒性作用机制。本研究采用模式动物斑马鱼(Danio rerio)作为研究对象,选择了环境中3种典型的有机磷酸酯类化合物包括磷酸三苯酯(TPP)、2-乙基己基二苯基磷酸酯(EHDPP)和磷酸三(2-氯)乙酯(TCEP),从斑马鱼运动行为、氧化应激和神经发育关键基因的转录等方面阐述有机磷酸酯的早期神经毒性作用及可能的作用机制。研究发现,TPP(0.1和1 mg·L~(-1))、EHDPP(0.2和2 mg·L~(-1))和TCEP(0.5和5 mg·L~(-1))可能通过诱导氧化应激并下调神经发育关键基因(mbp和syn2a)的转录从而显著抑制斑马鱼的运动行为。本研究可以为有机磷酸酯类阻燃剂及其替代产品的生产、使用和危险度评估提供直接依据。     

典型有机磷酸酯阻燃剂分析方法研究进展

有机磷酸酯(OPEs)是一类重要的有机磷阻燃剂,近些年逐渐取代了溴代阻燃剂,广泛应用于各行各业,也因此导致在多种环境介质中有较高的暴露量和潜在风险。已有研究表明,OPEs具有一定的毒理效应,对人体及其他生物均有潜在危害。本文综述了近年来国内外OPEs的检测技术,详述了不同环境介质OPEs的前处理方法。结果表明,目前固相萃取(SPE)和固相微萃取(SPME)仍是水样前处理的主要方法;对于固体样品,加速溶剂萃取/加压液相萃取(ASE/PLE)和微波辅助萃取(MAE)应用较多;虽然大气样品仍以固体吸附剂方式为主,但已向在线一体化方向发展;而生物样品的前处理方法多与水样和固体样品方法相似;但是对于复杂环境介质中OPEs样品的前处理较为困难,方法有待改善;气相色谱-质谱联用(GC-MS)和气相色谱-氮磷检测器(GC-NPD)对弱极性和易挥发的OPEs分析效果好,而强极性和难挥发的OPEs多用液相色谱-质谱联用(LCMS);气相色谱-质谱串联(GC-MS/MS)、液相色谱-质谱串联(LC-MS/MS)和高效液相色谱-质谱串联(UPLC-MS/MS)等对多种复杂的环境介质中的OPEs均有较好的检测分析效果,但并未普及。最后,对OPEs分析测试方法的发展趋势提出了展望。     

在线固相萃取-超高效液相色谱法检测水中14种有机磷酸酯

与传统固相萃取耗时长、工作量大、有机溶剂使用量多相比,本文建立了一种在线固相萃取-超高效液相色谱串联质谱方法同时测定地表水中14种有机磷酸酯的新方法.地表水样过膜后,直接注入在线固相萃取净化装置,经净化后进入分离柱分离,用乙腈和0.1%的甲酸水溶液梯度洗脱,采用电喷雾离子源正离子多反应监测模式,对14种有机磷酸酯类化合物进行检测,内标法定量.该方法分析时长13.0 min,方法的线性相关系数R~20.98,地表水和自来水样品的加标回收率在64.8%—113%,相对标准偏差RSD在1.2%—9.3%,检出限为0.1—2.7 ng·L~(-1).与常规方法相比,该方法提高了分析通量和灵敏度,准确度好,操作简便,适用于地表水和自来水中有机磷酸酯的检测.     

Particulate organic carbon and nitrogen in the eastern pacific ocean

Particulate organic carbon and nitrogen in sea water were measured in samples collected along a line 155°W; 50° N-15°S, during the cruise of R.V. “Hakuho-Maru” (KH-69-4). High concentrations of particulate matter were generally found at or near the sea surface; the concentrations decreased rapidly with depth. A consistent minimum was located in the depth range 150 to 250 m through the entire section sampled. The subsurface maximum layers roughly coincided with the chlorophyll maximum, but several irrregularities were noted. One of the most remarkable features of the vast stratum below 200 m depth was the presence of distinctively regional variation in concentration of particulate material through the entire section. In the section, we could define at least 6 large water parcels, vertically oriented, all with significantly different concentrations of both carbon and nitrogen. Variation in the deep water ranged from less than 5 μgC/l to more than 50 μgC/l. Correlation analysis between carbon concentration and apparent oxygen utilization (AOU) of ambient water for all samples showed that the carbon from particle-poor water parcels consistently decreased with increasing AOU, levelling to a practically constant low of around 5 to 10 μgC/l, whereas the carbon from particle-rich parcels was anomalously high (10 to 50 μgC/l) in the range of high AOU, and showed no consistent trend of convergence. The intergrated amount of particulate carbon in the total water column at each station was in the range 20 to 150 gC/m². More than 90% of this total amount was in the water column below 200 m depth, and the correlation of total amount of particulate material between the surface layer (0 to 200 m) and the water column below 200 m depth was highly significant. These observations are considered to indicate that the downward transport of these materials may be much quicker than so far estimated, at least in some localized areas.     

1,2,4-三氯苯对3种海洋微藻的毒性效应

1,2,4-三氯苯(1,2种,4-TCB)是环境中普遍存在的持久性有机污染物之一,而1,2,4-TCB对藻类的毒性作用报道很少。以1,2,4-TCB处理后,3种海洋微藻(金藻Isochrysis Zhanjiangensis、角毛藻Platymonas Subcordiformis和扁藻Chaetoceros miielleri)的生长状况、蛋白质质量分数和叶绿素质量分数的改变来检测1,2,4-TCB对海洋微藻的毒性效应。结果表明:1,2,4-TCB对3种海洋微藻的生长均有一定的抑制作用,该效应表现出一定的浓度和时间依赖性;1,2,4-TCB处理4d后,3种海洋微藻细胞蛋白质质量分数和叶绿素质量分数下降,呈现一定的浓度—效应关系,这表明1,2,4-TCB对3种海洋微藻产生毒害效应,其作用机制可能与藻类光合作用功能降低和蛋白质功能受损有关。1,2,4-TCB在一定程度上降低了藻类饵料的利用价值,而且对食物链下游生物具有潜在的危害性。     

The addition of FeOOH binds phosphate in organic matter-rich sediments

Due to climate change and anthropogenic nutrients’ runoff into freshwater or shallow lakes, eutrophication caused by phosphorus (P) can be seen in the frequent occurrence of cyanobacterial blooms and excessive growth of macrophytes. Subsequently, decomposition of cyanobacterial bloom biomass (CBB) and macrophytes leads to massive autochthonous organic matter (OM) and creates hypoxia in bodies of water. In this study, we investigated the effects of OM and iron on phosphorus release from lake sediments under anaerobic conditions. As with CBB, the addition of cellulose also enhanced P release from sediments during microcosm experiments, while total phosphorus (TP) concentration in the overlying water displayed an inverse relationship to cellulose amendment, with high TP concentration (0.41?±?0.07?mg?L^?1) observed in the treatment of less cellulose amendment (1?g of cellulose). In addition, P release from OM-rich sediments was effectively inhibited when amorphous FeOOH was added to the microcosms. P release was inhibited by 66–92% when the weight ratio between total Fe and total P in sediments varied from 18 to 60. Thus, iron treatment was useful to inhibit P release from OM-rich sediments, and could alleviate eutrophication problems.     

Primary productivity and sizes of pools of organic carbon in the mixed layer of the ocean

We estimated primary productivity and distributions of carbon in the phytoplankton, micro-zooplankton, and suspended and dissolved matter in various areas of the World Ocean to increase our information about the organic carbon cycle in the surface layer of the sea. Primary productivity ranged from about 0.1 gC m^–2 day^–1 in the Gulf of Mexico to 9 gC m^–2 day^–1 in nutrient-rich water off Peru. Phytoplankton carbon ranged from less than 10 g/l in the former to 750 g/l in the latter and in nutrient-rich water off southwest Africa. Micro-zooplankton carbon usually was less than 50 g/l in all waters, and was dominated by ciliates, copepodids, and copepod nauplii in all areas. Concentrations of particulate carbon ranged from 12 g/l off the east coast of South America to 850 g/l off southwest Africa. Concentrations of dissolved organic carbon varied between 0.5 and 1.5 mg/l in all areas except off Peru, where maximum values of 4.5 mg/l were observed. Turnover rates of carbon by small standing crops of micro-flagellates (1 to 5 longest dimension) and dinoflagellates in nutrient-poor waters were lower than those by large standing crops of diatoms and micro-flagellates in nutrient-rich waters. Concentrations of phytoplankton usually accounted for 20 to 55% and micro-zooplankton for 2 to 30% of the particulate carbon in the surface layer of the sea. Concentrations of dissolved organic carbon were not related to concentrations of particulate carbon in most waters except off Peru, where they appear to be directly related.     

Determination of volatile organic sulfur compounds in contaminated groundwater

A practical method for the quantification of total purgeable organic sulfur (POS) in highly contaminated groundwater is described. Volatile organic sulfur compounds (VOSC) are purged from the water samples by a stream of oxygen and combusted. The emerging sulfur dioxide is absorbed in H₂O₂ and converted to sulfate which is quantified by ion chromatography and reported as mass sulfur equivalent. The overall limit of quantification is 0.03 mg l⁻¹. The content of POS is balanced with the total VOSC determined by GC-AED after liquid–liquid extraction. Separate determination of the non-volatile organic sulfur compounds by direct combustion of the water sample and adsorption to charcoal yielded a mass balance of the total sulfur content. Semi-quantitative GC-MS after purge & trap accumulation revealed that the VOSC mixture is composed of C₁–C₄ alkyl sulfides. The implementation of the developed methodology for the quantification of VOSC as potential catalyst poison in a cleaning plant for groundwater contaminated with volatile haloorganics (VOX) is presented.     

水体中挥发性有机物分析方法研究进展

本文主要对水中挥发性有机物分析的研究进展做了较全面的介绍,简述了近年来样品的采集与保存技术、前处理方法及分析测试技术.对采集后的样品进行前处理的方法主要有吹扫捕集法、顶空固相微萃取法、液相微萃取法、动态针捕集阱等;分析测试技术主要有气相色谱法、气相色谱质谱法、质子转移反应质谱法等,对比了每种方法的优缺点,并展望未来分析检测技术的发展方向,为准确快速测定水中挥发性有机物提供参考.     

Turnover mechanisms of organic conformation on turbidity in drinking water

The turbidity variation in artificial water and samples from a water plant was investigated in the presence of organics with different relative molecular mass. The results show that recessive turbidity existed when water chemical conditions were changing. The formation of turbidity depended on organic relative molecular mass and their conformations on particles. At higher pH and lower ionic strength, the organic chains with a more extended conformation resulted in rising turbidity of the suspension. At lower pH, the reconformation of organics took place due to charge neutralization by the proton, resulting in a decline in turbidity. The addition of NaCl and MgCl₂ at pH 7.00 also resulted in a decrease of turbidity in the suspension. It is believed that the occurrence of recessive turbidity has a significant influence on the stability of water supply quality.     

基于改进微库仑法的海水可吸附有机卤素测定

对可吸附有机卤素(adsorable organic halogens,AOX)测定方法的研究主要集中在河流湖泊等饮用水相关的领域,而海水中的测定方法关注较少.受海水中高浓度的无机卤素离子的影响,传统的微库仑法在测定海水中AOX时精密度会下降并产生较大的正偏差.通过对传统的微库仑法进行改进,采用活性炭振荡吸附法-玻璃棒...     

Determination of selected semi-volatile organic compounds in water using automated online solid-phase extraction with large-volume injection/gas chromatography/mass spectrometry

A rapid, sensitive, and cost-effective analytical method was developed for the analysis of selected semi-volatile organic compounds in water. The method used an automated online solid-phase extraction technique coupled with programmed-temperature vaporization large-volume injection gas chromatography/mass spectrometry. The water samples were extracted by using a fully automated mobile rack system based on x-y-z robotic techniques using syringes and disposable 96-well extraction plates. The method was validated for the analysis of 30 semivolatile analytes in drinking water, groundwater, and surface water. For a sample volume of 10 mL, the linear calibrations ranged from 0.01 or 0.05 to 2.5 ??g·L^?1, and the method detection limits were less than 0.1 ??g·L^?1. For the reagent water samples fortified at 1.0 ??g·L^?1 and 2.0 ??g·L^?1, the obtained mean absolute recoveries were 70%?C130% with relative standard deviations of less than 20% for most analytes. For the drinking water, groundwater, and surface water samples fortified at 1.0 ??g·L^?1, the obtained mean absolute recoveries were 50%?C130% with relative standard deviations of less than 20% for most analytes. The new method demonstrated three advantages: 1) no manipulation except the fortification of surrogate standards prior to extraction; 2) significant cost reduction associated with sample collection, shipping, storage, and preparation; and 3) reduced exposure to hazardous solvents and other chemicals. As a result, this new automated method can be used as an effective approach for screening and/or compliance monitoring of selected semi-volatile organic compounds in water.