缢蛏中邻苯二甲酸酯的气相色谱-质谱测定方法研究

建立了超声波振荡提取、固相萃取(SPE)小柱净化、气相色谱-质谱(GC-MS)同时测定缢蛏(Sinonovacula Constricta)中13种邻苯二甲酸酯(PAEs)的方法.样品用二氯甲烷超声波振荡提取和硅胶-中性氧化铝(2∶1,m∶m)固相萃取小柱对待测PAEs净化后,使用GC-MS对PAEs进行定性、定量分析.在优化实验条件下,方法的相对标准偏差(RSD)≤9.5 ％(20 ng/g,n=5);缢蛏样品中添加标准的回收率,除邻苯二甲酸二甲酯(DMP,58.6％)、邻苯二甲酸二乙酯(DEP,62.6％)和邻苯二甲酸二丙酯(DPRP,75.5％)偏低外,其他组分在87.9％(邻苯二甲酸丁苄酯,BBP)～111.1％[邻苯二甲酸二(2-乙基己基)酯,DEHP]之间.方法的定量检出限范围为6.3 ng/g (DMP)～ 32.8 ng/g(邻苯二甲酸二异丁酯,DiBP),可满足海洋生物缢蛏中痕量PAEs日常监测的需要.市售缢蛏样品中共检出3种PAEs,分别为DiBP(31.2 ～55.3 ng/g)、邻苯二甲酸二丁酯DnBP(39.7～51.6 ng/g)和DEHP(22.3 ～ 149.2 ng/g),与缢蛏生长环境受PAEs污染种类及PAEs理化性质有关.DEHP污染的地区差异,是样品中DEHP含量差异的原因之一.     

利用半透膜渗透装置富集-超声萃取分析表层沉积物间隙水PCBs的方法

本文建立了半透膜渗透装置(semi-permeable membrane device,SPMD)富集-超声萃取-凝胶渗透色谱净化-气相色谱法测定沉积物间隙水中多氯联苯(PCBs)的方法。比较了有机溶剂透析法与超声萃取法从膜袋内提取PCBs的回收率,发现超声萃取法在节省时间和溶剂方面有明显优势。应用凝胶渗透色谱分离与净化SPMD提取物,收集11—17min的流出液能达到最佳分离效果。基于此方法测定了大连湾沉积物间隙水中自由溶解态PCBs的含量(C_(W-SPMD)),同时又分析了沉积物中PCBs的总量(C_(SED))、间隙水中PCBs的含量(有机碳含量校正法,C_(W-SED))和间隙水中PCBs的总含量(离心法,C_(PW))。结果表明,C_(PW)值显著高于C_(W-SED)和C_(W-SPMD)值。因此,考虑到生物可利用性,无论采用沉积物中或者间隙水中的PCBs总量进行污染物生态风险评价均会造成风险被高估,建议采用间隙水中可溶解态含量。     

刻蚀不锈钢丝固相微萃取-气相色谱法检测海水中多氯联苯

用氢氟酸刻蚀不锈钢丝制作了固相微萃取(solid-phase microextraction, SPME)纤维,与气相色谱(gas chromatography, GC)联用直接测定了海水水样中的痕量多氯联苯(polychlorinated biphenyls, PCBs),优化了萃取时间、萃取温度、搅拌速率、解吸温度和解吸时间对SPME的萃取效率的影响。本方法的线性范围可达两个数量级,PCB28和PCB52的线性范围是1.0～100.0 ng/L,其他8种PCBs的线性范围是0.5～50.0 ng/L(除PCB198外,r²均在0.99以上),检出限为0.01～0.10 ng/L。单个纤维间及纤维与纤维间的相对标准偏差分别为2.4%～7.2%和4.9%～8.7%。实际海水样品的加标回收率为80.9%～106.0%。微萃取纤维机械强度高、耐海水腐蚀、寿命长、制作成本低,该方法适用于测定海水水样中的痕量PCBs。     

高效液相色谱-串联质谱法同时测定海洋沉积物中27种有机磷酸酯

应用广泛且具有毒性的有机磷酸酯(organophosphate esters,OPEs)类阻燃剂,通过水、气输送等多种途径进入海洋环境,可能会导致人类和海洋生物面临潜在的健康风险。因此,建立高效可靠的分析方法对于揭示OPEs在海洋环境中的赋存状况,评估其生态风险具有重要的科学意义。文章建立了同时测定沉积物中27种OPEs的超声提取、固相萃取(SPE)净化以及高效液相色谱-串联质谱(HPLC-MS/MS)检测的分析方法。结果表明:30mL乙酸乙酯(EA)和乙腈(ACN)混合溶剂(体积比为3︰7)的提取效果明显优于单独使用甲醇(MeOH)、二氯甲烷(DCM)、EA和ACN;用5mL EA经LC-C18固相萃取小柱洗脱两次回收率最好;以MeOH和含0.0025%甲酸的水溶液作为流动相时,质谱离子丰度最高。27种OPEs的线性范围为5~500 ng/g (R²>0.99),方法检出限(MDL)范围为0.004~1.250 ng/g,定量限(LOQ)为0.01~4.17 ng/g。三个加标水平(低、中、高)基质加标样品的平均回收率在45%~130%之间,相对标准偏差(RSD)最高11.0%,表明此方法可靠,精密度和灵敏度较高。采用优化的方法分析我国长江口、杭州湾入海口以及东海和黄海交界处海域表层沉积物中OPEs的含量,共检出了21种OPEs,浓度范围为9.83~48.70 ng/g,平均浓度为28.40 ng/g。该方法检测结果高效准确,可用于海洋沉积物中27种OPEs的同时测定。     

大连湾和杭州湾表层沉积物中多氯联苯和有机氯农药及风险评价

对大连湾与杭州湾沉积物样品中多氯联苯(Polychlorinated Biphenyls,PCBs)和有机氯农药(Organochlorine Pesticides,OCPs)进行了分析测定。结果表明,大连湾和杭州湾沉积物中PCBs的含量为0.72~14.87 ng/g和0.76~3.86 ng/g,其中3、4、5氯联苯比例较高,其和超过总含量的70%;OCPs的含量为2.98~32.23 ng/g和1.61~4.71 ng/g,其中主要成分为六六六(Hexachlorocyclohexanes,HCHs)和滴滴涕(Dichlorodiphenyldichloroethylenes,DDTs)。大连湾和杭州湾表层沉积物中HCHs主要来自农业使用,而且大连湾有新的DDTs输入,杭州湾表层沉积物中的DDTs则主要来自历史残留。生态风险评价的结果表明,PCBs几乎不会对研究区域产生生态风险,OCPs对杭州湾也不会造成潜在的生态风险,但大连湾的OCPs处于中等风险水平,应当引起关注。     

三沙湾表层沉积物中有机污染物的含量及风险评价

利用气相色谱/质谱方法对三沙湾表层沉积物中多氯联苯(PCBs)、多环芳烃(PAHs)和有机氯农药(OCPs)进行测定,结果表明,PCBs、PAHs和OCPs的含量均值分别为1.28、61.76和1.18ng/g。与早期研究结果相比,PCBs含量浓度明显降低,表明其污染已得到有效控制;PAHs中高分子量组分普遍存在,通过分析菲/蒽和荧蒽/芘比值,判断其主要来源为燃料的高温燃烧;HCHs和DDTs是主要的有机氯农药污染物,二者的残留特征表明其主要来源为早期历史残留,且表层沉积物受到厌氧微生物降解。总体而言,三沙湾表层沉积物中PCBs、PAHs和OCPs的污染程度及生态风险均处于较低水平。     

利用化学传感器检测海水中的多氯联苯

为建立一种简单快捷的多氯联苯检测方法, 本研究应用化学传感器对宁波沿海重点陆源排污口及周边海水中的多氯联苯进行了检测, 采用HS-SPME-GC-MS(顶空固相微萃取-气质联用)对结果进行了验证。利用化学传感器测定海水中的多氯联苯, 在LDA(线性判别分析)中, 总判别率为99.81%。海水体积增大到5mL时, LDA 最低检测限达到了0.01ng/L。建立的模型中, 欧氏距离、相关性、判别函数法和马氏距离对样品浓度鉴别的正确率分别达到了100%、100%、92%、84%。采用Loading分析法简化了传感器阵列, 使BP神经网络总的MSE达到了5.6548e?006, 总的相关系数0.99998, 而最大误差只有1.0300e?002的水平。HS-SPME-GC-MS对海水中多氯联苯浓度的检测限最 低为0.001?g/L, 远高于化学传感器的0.01ng/L, 回收率在100%—120%之间。     

厦门岛东部和闽江口沿岸经济贝类中持久性有机氯农药和多氯联苯的残留水平

1995－1996年间，在厦门岛东部和闽江口沿岸养殖区的7个站点采集了贝类样品，样品先去壳匀浆，再经冷冻干燥，萃取浓缩和净化分离后，用GC法分析测定其六六六（HCHs)，滴滴涕（DDTs)和多氯联苯（PCBs）的含量，厦门岛东部HCHs，DDTs和PCBs的含量范围分别为0．18－345，75．2－2143，ND－234ng/g干重；闽江口分别为ND－5．07，21．5－2396，ND－6．78ng/g干重，结果表明，贝类样品的有机氯污染物含量因不同采样地点，不同生物种类及不同采样时间而异，但总体上高于沉积物，牡蛎对DDT的富集尤为显著，本文除了对调研区经济贝类的HCHs,DDTs和PCBs含量与组成分布进行分析评价，还就海区有机氯污染生物监测的可行性，经济贝类的食用卫生水平等问题作了探讨。     

基于电子鼻的青蛤(Cyclina sinensis)软组织多氯联苯的快速检测方法研究

为建立一种简单快捷的水产品中多氯联苯(PCBs)检测方法,本研究应用电子鼻对青蛤(Cyclina sinensis)软组织中富集的多氯联苯进行检测,并采用HS-SPME-GC-MS(顶空固相微萃取-气质联用)对结果进行了验证。首先利用电子鼻制作PCB15浓度梯度模版,检测PCB15处理72h以及144h的青蛤软组织中残留量,采用LDA和PCA两种方法统计并同模板的浓度进行比较。结论:青蛤软组织中PCB15浓度能明显分开,并随着处理时间的延长,区分效果愈加明显,区分度愈大。PCA的分辨效果明显优于LDA。运用欧氏距离、马氏距离、判别函数法和相关性对含有PCB15的样品浓度分别进行鉴别和验证,四种方法总的鉴别率均达到90%以上,能够较准确地对样品进行验证。电子鼻检测青蛤软组织中的多氯联苯的最低检测限为0.05μg/L,GC-MS为0.5μg/L。     

舟山渔场软体生物中PCBs的残留及潜在生态风险

本文测定了舟山渔场附近6个沿海城市5种软体动物体内多氯联苯的污染水平,并进一步探讨了其潜在来源以及生态风险。结果显示,样品中PCBs的总含量水平为18.0~95.9 ng/g干重,平均含量为51.9 ng/g干重,与世界其他海域相比处于中等污染水平。组分分析表明,五氯联苯和二氯联苯为主要组成。PCBs的健康风险HR值均远低于1,表明日常食用不会对人体健康产生明显危害。     

超声波萃取-高效液相色谱法在海洋沉积物样品多环芳烃分析中的运用

建立用超声波萃取-高效液相色谱法同时检测海洋沉积物中16种优先监控的多环芳烃(PAH s)的方法。本方法采用丙酮作为萃取溶剂,在超声波作用下萃取出泥样中的PAH s,萃取液经浓缩后直接进行高效液相色谱分析。经对色谱条件和萃取条件进行优化后,各PAH组分的线性范围为1~500 ng之间,相关系数0.9921~0.999,检出限0.1~4.6 ng,达到海洋沉积物PAH s的检测要求。运用本法对粤东大规模增养殖区柘林湾表层沉积物PAH s进行检测,各PAH组分加标回收率为69.2%~108%,总平均达89.2%,相对标准偏差为0.5%~10.3%。本方法只需要萃取、浓缩和定容三个步骤,具有简便、迅速、高效、分析成本低的特点。     

海水中丙烯酸的高效液相色谱法建立及应用

建立了一种测定海水介质中丙烯酸的高效液相色谱法。采用耐纯水相和较低pH的Agilent SB-Aq-C18柱(100 mm×4.6 mm i.d.,5 μm), 0.35%磷酸溶液(pH=2)为流动相,使用紫外检测器,检测波长为210 nm,外标法定量测定。丙烯酸的保留时间在14.2~ 14.9 min,方法的检出限为4 nmol/dm3(S/N=3),在0.01~10 μmol/dm3的范围内均有良好的线性关系,相关系数可达0.999 6,加标回收率为95.4%~98.1%,相对标准偏差为1.3%~1.6%(1.04~2.32 μmol/dm3)。采用0.2 μm滤膜重力过滤冷藏的办法来保存海水丙烯酸样品。检测出2011年5月份青岛近海海水中丙烯酸的平均浓度为(0.101±0.069) μmol/dm3;海洋微藻球形棕囊藻在整个生长周期内培养体系中丙烯酸的浓度为0.339~2.219 μmol/dm3。     

Chlorinated hydrocarbons in the open mediterranean ecosystem and implications for mass balance calculations

Studies on the biogeochemical cycling of organic contaminants in the Mediterranean have demonstrated the importance of polychlorinated biphenyls (PCBs) as relatively stable markers of recent anthropogenic influence in ocean systems. This paper presents results of hydrocarbon analyses of deep water profiles, sediments and their associated surface flocculent layers, and zooplankton samples collected in the western basin. Seawater concentrations were higher than those previously reported for the eastern basin and were consistent with the presence of industrial sources in the northwestern segment. In the water column, the percent of PCBs associated with filterable particles was related to the ambient concentrations of total suspended matter, distance from coastal input sources and on depth. The occurrence of deep water residues primarily in the dissolved phase and observations of subsurface maxima in seawater concentrations during a season of high surface productivity were consistent with the predictions of vertical transport models based on residues associated with sinking particles and equilibrium partitioning. Flocculent layers at the sea/sediment interface contained two and three orders of magnitude, respectively, more PCBs and petroleum hydrocarbons (PHCs) than their associated surface sediments. The flocculent particles also contained several biogenic hydrocarbons presumably originating from plankton and relatively soluble and labile contaminants such as hexachlorohexane isomers (HCH) and hexachlorobenzene (HCB), thus confirming that the majority of the flux of hydrocarbons to sediments is carried on rapidly settling large particles. By combining the sediment and flocculents data with published sedimentation rates for the deep basins of the Mediterranean, a yearly flux rate of PCBs to the open sea sediments was estimated as 13 μg m⁻² yr⁻¹ or less than half of the rate measured in a coastal sediment trap experiment. Analytical results are placed in the context of other distribution data for PCBs and long-term flux studies to construct a partial mass balance budget for this semi-enclosed sea. The computed coastal inventory showed that about 35% remains suspended in the water column while the majority of residues are deposited in coastal sediments. However in the open sea, the deep water column may contain up to 70% of the total inventory and may be a continually increasing reservoir of stable organic contaminants reaching the ocean. The budget shows that priority for improved research and monitoring efforts in ocean systems should be given to continued advancement in techniques for the precise measurement of deep water concentrations and for measuring current atmospheric inputs and sedimentation rates in order to develop more accurate ocean flux models.     

Colorimetric determination of nanomolar concentrations of silicate in natural waters after liquid-liquid extraction using methyl isobutyl ketone

A sensitive solvent extraction method for the determination of nonamolar concentrations of silicate in natural waters is developed. According to the traditional aqueous silicate method, silicomolybdenum blue formed by the reaction between silicate and ammoni- um molydate and reduced by metol-sulfite reagent is extracted by methyl isobutyl ketone. The absorbance can be enhanced substantially up to 10-folds. The detection limit of silicate is 8 nmol/dm^3 , which is one tenth smaller than the traditional method, with the precision of 4.0% at a silicate level of 50 nmol/dm^3 and 3.2% at a silicate level of 6 μmol/dm^3. Comparing the calibration curves in the distilled water and seawater, it can be seen that the salt effect also exists in the extraction method. However, the salt effect is a linear function of the salinity and can be corrected by simple calibration. The proposed method is successfully applied to the determination of silicate in natural waters. Natural concentrations of arsenate, arsenite and phosphate cause negligible interference.     

Distribution,behavior and fate of PCBs in the marine environment

I am extremely grateful and honored for being awarded the Okada Prize (1985) for my study. The present article reviews my research on the distribution, behavior and fate of PCBs in the marine environment. The outline of this study is summarized as follows:

1. Polychlorinated biphenyls (PCBs) were detectable in the wide range of environmental media and biota of the Seto-Inland Sea, Japan, in which much high concentrations were found in sediment and biological samples due to their hydrophobic, lipophilic and less biodegradable properties as well as their extensive production and use in estuarine and coastal regions.
2. PCBs extend the boundaries of their distribution all over the global environment, being evidenced by their occurrence in open ocean atmosphere, hydrosphere and biosphere, even in Antarctica. The global contamination of PCBs is much more prominent in northern hemisphere than in southern hemisphere.
3. The sinking rate of PCBs from surface to deeper layers in open ocean water column is relatively slower in tropical waters than in high latitude ones. This implies the possible prolonged contamination of persistent synthetic organic chemicals in the tropical marine environment.
4. The bioaccumulation processes in marine ecosystems can be explained by the physicochemical and biochemical properties of PCBs and the metabolic capacity of organisms. In higher animals, additional factors such as parturition and lactation are also related to this process.
5. Total PCB load in global environment was estimated to be about 370 thousand tons. Of this, most amounts were in coastal sediment and open ocean water. Presently, about 780 thousand tons of PCBs are still in use mainly in electrical equipments. In order to reduce the PCB levels in marine environment, pertinent measures to prevent the further discharge and safe disposal of PCBs are required.

     

桑沟湾水体中有机氯农药和多氯联苯的浓度水平及分布特征

以气相色谱-电子捕获检测器(GC/ECD)分析并结合外标法,定量测定了桑沟湾海域水体中15种有机氯农药和多氯联苯类化合物的含量.结果表明:桑沟湾海域表层水体中有机氯农药浓度范围为20.34～52.86 ng/L,底层水中的浓度范围为31.7～58.68 ng/L.该海域水体中共检出有机氯农药6种,DDTs类化合物是水体...     

基于声暴露级向量的海洋工程噪声信号自动提取方法

为从海量的海洋原始噪声数据中快速和准确地提取海洋工程噪声信号,完善大型海洋工程的海洋噪声评估方法,文章提出基于声暴露级向量的海洋工程噪声信号自动提取方法,并进行实验验证。研究结果表明:基于声暴露级向量的信号自动提取方法实现的核心是计算疑似信号与样本信号声暴露级向量(包括声暴露级和有效时间长度)的标准化欧氏距离,结合变步长截取分析、半波包络双阈值触发和中心位置触发等方法,提高信号提取的效率和准确率;与传统的人工提取方法相比,该自动提取方法具有稳健、准确和高效的性能,可替代人工提取方法并广泛应用。     

Determination of experimentally enriched15N in nitrate nitrogen based on an improved method of azo dye formation

A method has been developed for determination of¹⁵N isotope ratio in nitrate nitrogen, which is a major analytical step in tracer experiments for studies of nitrate metabolism in the marine environment. The method is based on diazotization of nitrite with sulfanilic acid following reduction of nitrate to nitrite by a cadmium-copper column. The diazonium compound is then subject to the azo coupling reaction with 2-naphthol, and the azo dye formed is extracted by a solid phase extraction column. The dye eluted from the column is collected, and total nitrogen and¹⁵N content of the dye are determined by mass spectrometry. Sulfanilic acid can also remove preexisting nitrite by heating the sample under acidic conditions before passing through the cadmium-copper reduction column. The average recovery of nitrate nitrogen was 86%. A procedure for reducing the background nitrogen that derives from the analytical operations has been developed; background nitrogen was limited to about 0.25 μg-atomN. The variation in the background nitrogen levels reflects the range of error in¹⁵N determination of nitrate nitrogen by this method. Application of the present method to a¹⁵NO₃ ⁻ isotope dilution experiment for determination of nitrification rate in sea water is demonstrated.     

浙江三门湾表层沉积物重金属含量分布、赋存形态及生态风险评价

以三门湾表层沉积物为研究对象,对5种重金属(Zn、Cr、Cd、Cu、Pb)的含量分布、赋存形态进行分析,并运用潜在生态危害指数法、Risk Assessment Code(RAC)法、次生相与原生相比值法对重金属生态风险进行了评价。结果表明:三门湾表层沉积物重金属的含量分布整体表现为湾内高于湾外海域,人类活动是主要影响因素。运用BCR法对沉积物中重金属进行分级提取,结果显示 Zn、Cd、Cr、Cu均以残渣态为主要赋存形态(Zn:79.20%~84.25%、Cr:93.24%~96.16%、Cd:34.71%~57.58%、Cu:66.06%~79.51%),而Pb以可还原态为主(56.58%~76.44%)。评价结果中,潜在生态危害指数法和次生相与原生相比值法均显示湾内的重金属污染比湾外严重,而RAC法指出Pb污染为湾外高于湾内海域;潜在生态危害指数法和RAC均指出Cd是主要污染元素;在次生相与原生相比值法中Pb则是主要危害元素,Cd次之。