中国沿海三省主要饮用水源有机物监测

采用固相萃取、吹扫捕集和气相色谱-质谱联用仪(GC-MS)对江苏、浙江、山东省的21个主要地表饮用水源、126份水样中的25种VOCs、38种SVOCs进行定量检测。结果有19种VOCs、10种SVOCs至少在一个水源地多次被检出,其中挥发性氯代烃、苯系物、氯代苯类、酚类、硝基苯类、酞酸酯类、农药为中国或美国环境保护局提出的"水中优先控制污染物",最高检出量为27.79μg/L。三省主要地表水受到有机物轻度污染,水体中VOCs、SVOCs含量尚未超过《地表水环境质量标准》(GB 3838-2002)和《生活饮用水卫生标准》(GB 5749-2006)限值,工业废水排放及农田雨水径流是地表水有机物的重要来源。     

Determination of CH4, CO2 and N2O in air samples and soil atmosphere by gas chromatography mass spectrometry, GC-MS

A method for determination of the climate gases CH4, CO2 and N2O in air samples and soil atmosphere was developed using GC-MS. The method uses straightforward gas chromatography (separation of the gases) with a mass spectrometric detector in single ion mode (specific determination). The gases were determined with high sensitivity and high sample throughput (18 samples h(-1)). The LOD (3sigma) for the gases were 0.10 micro L L(-1) for CH4, 20 microL L(-1) for CO2 and 0.02 microL L(-1) for N2O. The linear range (R2 = 0.999) was up to 500 microL L(-1) for CH4, 4000 microL L(-1) for CO2 and 80 microL L(-1) for N2O. The samples were collected in 10 mL vials and a 5 microL aliquot was injected on column. The method was tested against certified gas references, the analytical data gave an accuracy within +/-5% and a precision of +/-3%. The presence of < or = 10% by volume of C2H2 (often used experimentally to prevent N2 formation from N2O) did not interfere with detection for the targeted trace gases.     

固相萃取- GC/MS法测定水中有机氯农药

建立了固相萃取-气相色谱／质谱联用测定水中痕量六六六、滴滴涕和环氧七氯的方法。采用C18固相萃取柱富集水样，二氯甲烷／丙酮混合溶剂洗脱，加入菲-d10作为内标，利用气相色谱／质谱联用仪选择离子监测模式检测，内标法定量，定性、定量准确，线性响应良好，干扰小，按采样1 L计算，方法检出限为4．26ng／L～19、2ng／L，RSD在0、4％-6、3％之间，平均加标回收率在77．7％～118％之间，实际样品测定结果表明方法能满足环境水体中痕量有机氯农药的监测要求。     

气相色谱—串联质谱法检测水中苯霜灵、甲霜灵、噁霜灵残留量

建立水中甲霜灵、苯霜灵、噁霜灵农药残留量的气相色谱—串联质谱(GC-MS/MS)的检测分析方法。样品采用乙腈提取、固相萃取(SPE)柱净化。采用GC-MS/MS分析时,三种农药在15 mim内完全分离并流出。添加浓度加标回收率为80.6%~88.4%,相对标准偏差(RSD)小于5.0%。在0.01~0.20 mg/L质量浓度范围之间线性关系良好(r~20.999 0)。该方法的灵敏度、精密度和准确度均满足农药残留分析要求,适用于水中的农药残留的快速筛查与定性、定量分析。     

Occurrence and behaviour of 4-nonylphenol in river water of Germany

An analytical method composed of solid-phase-extraction (SPE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed to investigate the occurrence and the behaviour of the endocrine disruptor 4-nonylphenol (4-NP) in river water of Germany. 16 Para-isomers of the complex mixture of 4-NP isomers have been resolved in the SPE-extracts of river water samples. The mass spectra indicate the presence of four distinct groups of isomers. The different groups are characterised by different base peaks of the mass spectra dependent on the substitution of the alpha-carbon on the alkyl chain. The different isomers show (i) alpha-methyl, alpha-ethyl (base peak 149), (ii) alpha-dimethyl (base peak 135), (iii) alpha-methyl, alpha-propyl, alpha-butyl (base peak 121) and (iv) alpha-methyl, alpha-propyl, alpha-butyl (base peak 107) configuration of the alkyl chain. The recovery of the unbranched compound 4-n-NP was > or = 90%. Detection limit and determination limit of the whole analytical procedure were 6 ng L(-1) and 25 ng L(-1), respectively with a relative standard deviation of 11.7%. The concentration of the sum of the 4-NP isomers in all samples of river water ranged from 28 ng L(-1) (Elbe River) to 1220 ng L(-1)(Oder River). In a period of a higher river water level, a higher amount of 4-NP was detected in the Oder River than in a period of a lower water level. Therefore dilution was not the determinant factor of the 4-NP concentration in river water. The diurnal dynamics of the sewage treatment works (STWs) have to be considered as an influencing factor for the presence of 4-NP in river water.     

固相微萃取-气相色谱-质谱法测定饮用水中土嗅素和2-甲基异茨醇

采用固相微萃取法富集,气相色谱-质谱联用法定性和定量测定饮用水中致嗅物质土嗅素和2-甲基异茨醇。研究并讨论优化了纤维头的类型、盐的种类和浓度、温度、萃取时间等因素对异味化合物萃取量的影响。土嗅素和2-甲基异茨醇的检出限分别为1.02、2.13 ng/L,相对标准偏差分别为4.96%、7.74%。2种异味化合物在5~1 000 ng/L的范围内线性关系良好,相关系数均大于0.985。因此,用该方法能够很好地分析水中痕量的异味化合物。     

饮用水源中痕量联苯胺的检测方法

建立了固相萃取高效液相色谱水中联苯胺的检测方法。选择Waters HLB固相萃取小柱富集水样,二氯甲烷/丙酮洗脱,以甲醇-水(pH=8,0.02 mol/L磷酸盐缓冲体系)作为流动相,保留时间为3.850 min,检测波长285 nm,0.1～10.0 mg/L范围内线性关系好,相关系数为0.999,检出限达到8×10-6mg/L,相对标准偏差为4.0%～9.5%,不同浓度样品加标回收率为80.5%～102.5%。     

LLE-GC-MS法测定水中27种有机农药

建立了同时测定水中27种有机农药的LLE-GC-MS法。该法前处理前需调节水样pH值2,不加甲醇作为改性剂,以1:1(V/V)正己烷-石油醚为萃取溶剂进行液液萃取,GC-MS法进行检测。方法在各目标化合物质量浓度0.010~0.500 mg/L范围内线性良好,相关系数R2均0.995,检出限为0.021~0.250μg/L,加标回收率为73.6%~113.6%,相对标准偏差RSD为4.0%~14.1%,适用于水中27种有机农药的检测。     

液相色谱-串联质谱法同时测定污水中10种精神活性物质

建立了采用液相色谱-串联质谱法(LC-MS/MS)同时测定污水中10种精神活性物质的分析方法。污水样品经甲酸与甲酸铵调节pH后,加入氘代内标混匀,离心并过滤膜后可直接上样分析。研究表明,在1~250 ng/L的线性范围内,10种精神活性物质的线性相关系数均大于0.992,定量限均低于0.5 ng/L。在3个加标水平下,10种精神活性物质的加标回收率为87.2%~114%,相对标准偏差为0.53%~3.60%(n=3)。将该方法应用于某区域10份生活污水样品的检测,在3份水样中检出吗啡、甲基苯丙胺、氯胺酮等精神活性物质,对应的质量浓度范围分别为3.41~9.55、0.90~1.63、1.06~1.78 ng/L。与经固相萃取前处理后的分析方法相比,该方法可在10 min内完成分离和检测的全过程,具有简单、快速、节约的优点,可用于污水样品中10种痕量水平精神活性物质的定量分析。     

Simplification and validation of a large volume polyurethane foam sampler for the analysis of persistent hydrophobic compounds in drinking water

The use of a large volume polyurethane foam (PUF) sampler was validated for rapid extraction of persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), in raw water and treated water from drinking water plants. To validate the recovery of target compounds in the sampling process, a (37)Cl-labeled standard was spiked into the 1st PUF plug prior to filtration. An accelerated solvent extraction method, as a pressurized liquid extractor (PLE), was optimized to extract the PUF plug. For sample preparation, tandem column chromatography (TCC) clean-up was used for rapid analysis. The recoveries of labeled compounds in the analytical method were 80-110% (n = 9). The optimized PUF-PLE-TCC method was applied in the analysis of raw water and treated potable water from seven drinking water plants in South Korea. The sample volume used was between 18 and 102 L for raw water at a flow rate of 0.4-2 L min(-1), 95 and 107 L for treated water at a flow rate of 1.5-2.2 L min(-1). Limit of quantitation (LOQ) was a function of sample volume and it decreased with increasing sample volume. The LOQ of PCDD/Fs in raw waters analyzed by this method was 3-11 times lower than that described using large-size disk-type solid phase extraction (SPE) method. The LOQ of PCDD/F congeners in raw water and treated water were 0.022-3.9 ng L(-1) and 0.018-0.74 ng L(-1), respectively. Octachlorinated dibenzo-p-dioxin (OCDD) was found in some raw water samples, while their concentrations were well below the tentative criterion set by the Japanese Environmental Ministry for drinking water. OCDD was below the LOQ in the treated drinking water.     

气相色谱/质谱法测定水中15种酞酸酯类化合物

采用固相萃取-气相色谱/质谱法测定水中15种酞酸酯类化合物,确定方法的最优条件为:依次用10 m L正己烷和丙酮混合溶剂(V/V=5∶1)、甲醇和空白试剂水活化C18固相萃取柱后,水样以5 m L/min过柱萃取,再以8 m L正己烷:丙酮(V/V=5∶1)混合溶剂洗脱后,浓缩至1 m L,进气相色谱/质谱测定。该法的检出限为0.18~0.38μg/L,在0.50~20.0 mg/L范围内线性良好,相关系数均0.996。空白水样的加标回收率为71.8%~120%,相对标准偏差为1.73%~12.7%;实际废水水样的加标回收率为64.8%~135%,相对标准偏差为2.75%~18.0%。     

SPE-GCMS法分析饮用水源水中痕量半挥发性有机物

采用C 18固相萃取柱富集,乙酸乙酯、二氯甲烷和丙酮混合溶剂以1∶1∶1比例洗脱、自动固相萃取的前处理方法,气相色谱质谱连用,分析水源水中33种半挥发性有机物,并与液液萃取前处理方法进行比较。结果表明:在500~5 000μg/L范围内,33种SVOC线性良好,相关系数0.990,回收率为70.1%~114.2%,相对标准偏差为2.4%~13.4%,方法检出限为0.06~0.25μg/L;而且该方法较液液萃取,检出样品种类多。适用于饮用水源水中半挥发性有机物的监测。     

毛细管柱气相色谱法同时测定水中甲醇、乙醇和N,N-二甲基甲酰胺

采用HP-PLOT Q毛细管柱,气相色谱氢火焰离子化检测器同时测定地表水和废水中甲醇,乙醇,N,N-二甲基甲酰胺,方法不受水中苯系物的干扰,在甲醇,乙醇,N,N-二甲基甲酰胺分别为7.92~792 mg/L,7.98~798 mg/L和9.45~945 mg/L范围内线性良好,相关系数均0.999,准确度高,加标回收率均94.2%,精密度好,相对标准偏差均≤5.79%,检出限分别为1.17,1.31和2.05 mg/L。     

Occurrence and removal efficiencies of eight EDCs and estrogenicity in a STP

The occurrence and removal of eight endocrine disrupting compounds (EDCs), including estrone (E(1)), 17β-estradiol (E(2)), estriol (E(3)), 17α-ethinylestradiol (EE(2)), diethylstilbestrol (DES), bisphenol A (BPA), nonylphenol (NP) and octylphenol (OP), and their estrogenicities were investigated in a sewage treatment plant in Harbin city, China. The EDCs were extracted from wastewater samples by solid phase extraction (SPE) method and analyzed with gas chromatography coupled with mass spectrometry (GC-MS). The average concentrations in the influents and effluents ranged from 6.3 (EE(2)) to 1725.8 ng L(-1) (NP) and from 相似文献   

吹扫捕集-气相色谱联用同时测定水中致嗅挥发性有机硫化物

建立了一种利用吹扫捕集(PT)-气相色谱(GC)/火焰光度检测器(FPD)同时测定水中16种致嗅类有机硫化物的分析方法。研究并优化了捕集阱类型、吹扫温度、吹扫时间,解吸温度以及解吸时间对PT的影响。实验表明:大部分硫醚类和硫醇类化合物分别在1~100 ng/L和3~300 ng/L范围内线性良好,线性相关系数大于0.99;相对标准偏差小于9.47%(n=6);加标回收率为81.68%~115.18%。定量下限(10倍信噪比)范围从0.19 ng/L(二乙基二硫醚)到2.67 ng/L(2-甲基-1-丙硫醇)。采用此方法对北京市3条河流水样进行了检测,除1-丙基二硫醚和2-甲基-2-丙硫醇外,其他14种有机硫化物都有检出,质量浓度为1.95~1 282.35 ng/L。     

气相色谱-质谱法快速筛查气态制冷剂产品中的热点管控类卤代烃

建立了利用气相色谱-质谱法快速筛查气态制冷剂产品中的10种热点管控类卤代烃的分析方法。采用气密性微量注射器对气态制冷剂样品进行取样,刺透瓶盖隔垫加入到顶空瓶中,自动进样;以GS-GasPro(多孔层开管,60 m×0.32 mm)为色谱柱,采用电子轰击离子源,全扫描模式采集。测试结果显示:目标物的体积分数在0.50%~100.00%范围内,相对响应因子的相对标准偏差(RSD)均小于20%;线性相关系数r均在0.999以上;检出限(3.143倍标准偏差)为0.01%~0.05%。对实际样品进行加标回收,回收率为79.5%~102%,测定值RSD为0.5%~3.1%。该方法可为快速、准确、批量筛查气态制冷剂产品中的多种热点管控类卤代烃提供技术支撑。     

加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱测定土壤和沉积物中8种多溴联苯醚

建立了土壤和沉积物中8种多溴联苯醚(PBDEs,BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209)加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱(ASE-GC-MS-MS)的分析方法。通过优化加速溶剂萃取与弗罗里硅土在线净化和串联质谱多反应监测模式的条件,较好地去除基质干扰,并提高了三重四极杆串联质谱定性的准确性及定量的灵敏性。该方法采用改进的色谱柱能同时分析包括高溴代联苯醚BDE-209在内的8种PBDEs,其浓度范围为1～100 ng/mL(BDE-209为10～1 000 ng/mL),线性良好,线性回归系数均大于0.997。方法检出限为0.004～0.1 ng/g,方法回收率为75%～110%,方法精密度为2.4%～15.6%。适于批量处理土壤和沉积物中含有多组分痕量PBDEs的样品。     

Determination of organophosphorus fire retardants and plasticizers in wastewater samples using MAE-SPME with GC-ICPMS and GC-TOFMS detection

Determination of organophosphorus fire retardants and plasticizers at trace levels in wastewater is described. In this work, microwave assisted extraction (MAE) and solid-phase microextraction (SPME) are used for sample preparation to extract and preconcentrate the analytes, followed by analysis by gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) for phosphorus-specific detection. Gas chromatography coupled to time of flight mass spectrometry (GC-TOF-MS) was used to confirm the organphosphorus fire retardants in wastewater. The detection limits of organophosphorus fire retardants (OPFRs) were 29 ng L(-1) for tri-n-butyl phosphate (TnBP), 45 ng for L(-1) for tris(2-butoxyethyl)phosphate (TBEP), and 50 ng L(-1) for tris(2-ethylhexyl)phosphate (TEHP). Optimized extraction conditions were performed at 65 degrees C for 30 min and with 10% NaCl. Application of MAE during the sample preparation prior to the SPME allowed the detection of tris(2-ethylhexyl) phosphate, which has been difficult to determine in previous work. Application of the method to wastewater samples resulted in detecting 3.1 microg L(-1) P from TnBP, 5.0 microg L(-1) P from TBEP, and 4.0 microg L(-1) P from TEHP. The presence of these compounds were also confirmed by SPME-GC-TOF-MS.     

Occurrence of estrogenic chemicals in South Korean surface waters and municipal wastewaters

Broad scale monitoring of estrogenic compounds was performed at 19 sampling points throughout the Yeongsan and Seomjin river basins and 5 wastewater treatment plants (WWTPs) adjacent to the Gwangju area, Korea, from December 2005 to August 2007. The concentrations of estrogenic compounds, including estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), bisphenol-A, nonylphenol (NP) and 4-octylphenol (OP), in the samples was measured with gas chromatography/mass spectrometry (GC-MS). In addition, the estrogenic activities throughout the river were investigated using the E-screen assay. Of the six estrogenic chemicals, NP (114.6-336.1 ng L(-1)) and EE2 (0.23-1.90 ng L(-1)) were detected at the highest and lowest levels, respectively in both the river waters and the WWTP effluents. Bisphenol-A showed the largest concentration range, from 7.5 to 335 ng L(-1). The concentrations of E1, E2 and octylphenol ranges were 3.6-69.1, 1.2-10.7, and 2.2-16.9 ng L(-1), respectively. According to the calculated estradiol equivalent concentration (EEQ); however, no estrogenic contribution was observed due to the phenolic compounds in the river waters and effluents. E1 and E2 dominated in both the river water and effluent samples, with contributions to the calculated EEQ of over 79 and 77%, respectively. Conversely, EE2 was rarely detected in the river waters (21%) and effluents (0%). The largest contribution of EE2 to the calculated EEQ was 21% in the river water at S-7. The levels of E1, E2, and EE2 were remarkably decreased in the effluents, indicating that the 5 WWTPs did not contribute to the estrogenic effect of the receiving streams. Overall, the WWTPs did not contributed to the estrogenic activity of the receiving waters, but the livestock industry or wildlife may play an important role in the estrogenic contribution to river water.     

固相萃取-高效液相色谱法测地表水中11种酚类化合物

建立了固相萃取-高效液相色谱法同时测定地表水中11种酚类化合物的方法。水样经过全自动固相萃取仪富集,以HLB柱为萃取柱,乙腈(含1%乙酸)为洗脱剂,用高效液相色谱仪分析定量。该方法在0.5~5.0 mg/L范围内线性良好,相关系数为0.999 6~0.999 9,11种酚类化合物的纯水加标回收率为82.0%~111%,地表水加标回收率为98.5%~116%,精密度为3.58%~4.67%,检出限为1×10-4~5×10-4mg/L,该方法简单实用、准确可靠,可用于地表水中酚类化合物的同时测定。