固相微萃取-气相色谱串联质谱法测定饮用水及水源水中的环氧氯丙烷

通过对环氧氯丙烷的气相色谱串联质谱、固相微萃取试验条件的摸索,建立了采集10mL的水样,对水中环氧氯丙烷含量进行检测的固相微萃取-气相色谱串联质谱方法。曲线范围0.1~5μg/L,线性相关系数可达0.999 8,方法检出限为0.002μg/L。对国标限量浓度点0.4μg/L的8次重复检测,相对偏差为3.04%;对苏州市某自来水公司的出厂水、水源水进行低、中、高3种浓度(0.4μg/L、2μg/L、4μg/L)加标回收试验,回收率在74.27%~105.2%,可以满足分析检测和对国标限量浓度的检测要求。     

顶空固相微萃取-气相色谱-质谱联用技术测定水中8种致臭物质方法优化

研究建立了顶空固相微萃取-气相色谱-质谱联用测定水中8种致臭物质的方法。通过试验研究确立了顶空固相微萃取的最优化条件:氯化钠加入量0.4g/mL,萃取时间40min,萃取温度70℃,搅拌速率500r/min,解析时间3 min,无需调节pH。在试验条件下,8种致臭物质在1~100ng/L内线性关系良好,R2为0.997~0.999 9,最低检出限为0.5~1ng/L,相对标准偏差为1.6%~3.8%,加标回收率为89.2%~105.4%。     

固相微萃取(SPME)-气质(GC/MS)联用法分析饮用水中痕量碘代三卤甲烷

碘代消毒副产物(I-DBPS)是饮用水消毒过程中发现的一类暂未受控的新兴高致毒性消毒副产物。为了便于对饮用水中I-DBPS进行研究,可采用固相微萃取(SPME)-气质(GC/MS)联用技术来检测分析,介绍了固相微萃取的装置、操作及萃取方法,着重论述了其工作条件的选择,得出最佳优化条件:以DVB/CAR/PDMS作为萃取膜,萃取温度为65℃,萃取时间为45min,离子强度用25%(W/V)Na2SO4调节,搅拌速率为250r/min,并且在气相色谱中的解析温度为220℃,解析时间为30s。同时进行重复性和再现性试验对方法的检测限、精确度与准确度进行了评价。结果表明,采用SPME-GC/MS方法,分析物的检测限在10~50ng/L,可以用来检测ng/L级水平的痕量碘代三卤甲烷(I-THMS),且在分析物标准浓度为0.1μg/L时,重复性试验的相关标准偏差(RSD)在0.4%~1.5%,再现性试验的RSD在4%~12.5%,这表明该方法应用于痕量I-DBPS的分析检测是精确可靠的。     

固相微萃取-气质联用法在水体嗅味物质测定中的应用

采用固相微萃取-气质联用法对水体中常见嗅味物质土臭素(GEO)和2-甲基异莰醇(2-MIB)进行分析测定。选取65μm PDMS/DVB纤维萃取头,经实验确定最佳萃取条件:Na Cl投加量为6 g;水浴温度为70℃;萃取时间为30 min。用内标法测定结果显示:GEO和2-MIB在5~900 ng/L范围内标准曲线线性良好,且该法检出限低,对GEO和2-MIB的检出限分别为0.5 ng/L和0.7 ng/L;精密度(RSD)分别为0.31%和0.94%;加标回收率分别为107%和103%,能够满足分析测试要求。     

再生水厂处理工艺对邻苯二甲酸酯去除效果分析

以北京城区4座不同处理工艺的再生水厂进出水为研究对象,采用固相萃取(SPE)预处理和气相色谱-质谱法(GC-MS)方法对再生水标准中涉及到的邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)两类污染物进行了检测,对比分析不同再生水处理工艺的去除效果。结果表明,各水厂进水中DBP和DEHP的浓度范围分别为1.99～5.36μg/L和0.97～6.44μg/L,与上游污水处理厂所采用的处理工艺无明显关联性;出水中DBP浓度为1.74～5.59μg/L,DEHP浓度范围0.42～4.93μg/L,均低于景观环境用水的国家标准限值;常规混凝-过滤-消毒处理工艺的去除效果并不明显,而膜工艺由于膜污染等实际运行问题也没有达到理想去除效果,去除率不足60%。     

固相萃取-气相色谱/质谱法测定水中氯苯类化合物

采用固相萃取-气相色谱/质谱法同时测定水中12种氯苯类化合物。方法线性关系良好,水中氯苯类的最低检出限分别为:氯苯0.04mg/L,二氯苯0.1μg/L,三氯苯0.01μg/L,四氯苯0.01μg/L,五氯苯0.01μg/L、六氯苯0.01μg/L,加标回收率在83.8%~97.2%之间,RSD在1.2%~4.5%之间。     

固相萃取-高效液相色谱三重四级杆质谱联用法在北方河流水体氯霉素类抗生素测定中的应用

建立了固相萃取-高效液相色谱三重四级杆质谱联用法,同时测定水中的4种氯霉素类抗生素(氯霉素、甲砜霉素、氟苯尼考和氟苯尼考胺)残留,采用MRM扫描方式在正/负模式下,在10 min内完成对氯霉素类抗生素的分析,该方法线性范围为1~100μg/L,相关系数R20.99,实际水样加标回收率为92.8%~117.48%。利用该方法对北方河流水样进行采样调查,其中氟苯尼考检出率较高为26%,达526.36 ng/L。该方法操作简便,灵敏度高,重现性好,具有一定的推广价值。     

超高效液相色谱-串联质谱法测定水中8种微囊藻毒素

微囊藻毒素主要是由水中蓝绿藻凋亡后产生的一类常见的环肽肝脏毒素,对水生生物及人体健康具有非常大的危害性。建立准确、快速检测微囊藻毒素的方法对中国民众饮水安全非常重要。对固相萃取、色谱和质谱等条件进行优化,建立了超高效液相色谱-串联质谱同时检测水中8种微囊藻毒素(LR、RR、YR、WR、LW、LA、LF、LY)的方法。该方法检出限为0.002～0.006μg/L,定量限为0.006～0.018μg/L,加标回收率为85.3%～107.5%,相对标准偏差小于11%。该方法可为地表水中微囊藻毒素的日常检测提供技术支持。     

地下水中21种半挥发性有机物测定方法的优化研究

为研究建立同时测定地下水中21种半挥发性有机物的固相萃取-气相色谱-串联质谱(SPE-GC/MS)法,采用C_(18)和HLB固相萃取柱对地下水样品进行富集萃取,DB-5MS毛细管柱(30 m×0.25 mm×0.25μm)进行气相分离,单离子监测(SIM)扫描模式进行分析,并对进样速率、洗脱剂和pH等样品前处理条件进行优化,建立了固相萃取-气相色谱-质谱测定地下水中21种半挥发性有机物的检测方法。研究结果显示:21种半挥发性有机物的标准曲线在0.1～1μg/mL范围内,线性关系良好。平均回收率基本在80%～120%之间,精密度在1.70%～8.79%之间,检出限在0.022～0.045μg/L之间,均低于《地下水质量标准》(GB/T 14848—2017)一类水限值。研究结果表明,本方法操作简便、有机试剂消耗量少、灵敏、准确,可用于地下水中多种半挥发性有机物的同时检测。     

吹扫捕集-气相色谱-质谱联用法测定饮用水中痕量1,2-二溴乙烯与五氯丙烷

建立了同时检测饮用水中顺式-1,2-二溴乙烯、反式-1,2-二溴乙烯和五氯丙烷的吹扫捕集-气相色谱-质谱联用方法。结果表明：该方法在0.02～1.0μg/L范围内线性良好,方法检出限分别为0.0021μg/L、0.0012μg/L和0.0012μg/L。实际水样低（0.02μg/L）、中（0.2μg/L）、高（1.0μg/L）质量浓度加标7次平行测定相对标准偏差在1.51％～4.52％之间,加标回收率在92.3％～104.5％之间。     

Determination of brominated flame retardants in Jukskei River catchment area in Gauteng, South Africa

Brominated flame retardants (BFRs) are considered to be environmental pollutants due to their toxicity, persistence and ubiquity in the environment. Little information is known about the presence of brominated flame retardants in South Africa's water systems. Therefore, this study examined and compared different extraction methods (liquid-liquid (LL) vs. solid phase (SP) for water, Soxhlet extraction (SE) vs. ultrasonic for sediment) for extraction efficiencies in the determination of polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyls (PBBs) in water and sediment from Jukskei River. Clean-up of sample extracts was performed using disposable Pasteur pipettes containing neutral, acidified and basic silica gel. Final extracts, after concentration and dilution to 200 μL were analyzed by injecting 1 μL in the GC-ECD and GC-MS. Results obtained showed good recoveries for most of the tested analytes in water; for LLE, values ranged between 80.5 ± 10.22% and 126.6 ± 1.94%; SPE, 70.41 ± 2.01%-124.78 ± 3.78% (n = 3) and for sediment (73-114%, with an RSD <17%) using SE. The ultrasonic extraction method gave less than 50% recovery for most of the congeners. The concentrations of the BFRs in water samples were less than the detection limit while the concentrations in sediment ranged from 1.95 to 36.61 ng g(-1) dry weight for Σ(11) BFRs. Dichloromethane and n-hexane : acetone (2 : 1, v/v) gave optimum value of recovery for water and sediment respectively.     

Picogram determination of N-nitrosodimethylamine in water

N-nitrosodimethylamine (NDMA) persistence within surface waters is a major concern for downstream communities exploiting these waters as drinking water supplies. The objective of this study is to develop a novel and efficient analytical method for NDMA via different technologies: pulsed splitless gas chromatography-nitrogen phosphorus detector (GC-NPD), large volume injection (LVI) gas chromatography-mass spectrometry (GC/MS) via programmable temperature vaporizer (PTV) inlet or PTV-gas chromatography-triple quadruple mass spectrometry (GC-MS/MS) and continuous liquid-liquid extraction. It was found that the sensitivity required for NDMA analysis by GC-NPD can only be achieved when the NPD bead is extremely clean. LVI via PTV can greatly improve GC-MS system sensitivity for analyzing NDMA. With the help of DB-624 (25 m x 200 microm x 1.12 microm) connected with DB-5MS (30 m x 250 microm x 0.25 microm) in series, PTV-GC/MS could overcome the matrix interference for the trace analysis of NDMA. Variable instrument conditions were studied in detail, with the optimized process being validated via precision and accuracy studies. PTV- triple quadruple GC-MS/MS system could efficiently remove the interference on a single DB-5MS (30 m x 250 microm x 0.25 microm) column with good sensitivity and selectivity. The developed methods have been successfully applied to test NDMA in different types of water samples with satisfactory results.     

Sensory evaluation of the odors produced during bromophenol formation using a multi-level statistical model.

In response to reports of medicinal taste and odor problems in suburban Paris, a lab scale study was conducted to investigate the contribution of different water quality parameters--pH, phenol, bromide, chlorine, temperature and dissolved oxygen levels--on bromophenol medicinal odor formation using the Flavor Profile Analysis (FPA) method. A study of six parameters at 2 levels (64 experiments) analyzed by the FPA method suggests that chlorine at high concentration is more important as a controlling agent than phenol under similar conditions and the ratio of HOBr:Phenol and the time for reaction will control subsequent brominated products of reaction. Results from a three-level statistical model indicate that high pH was associated with lower odor intensities, whereas high levels of chlorine, phenol and temperature were associated with high odor intensities. Potential worst case scenarios of water quality conditions were determined for evaluation by chemical identification and kinetics.     

Optimization of stir bar sorptive extraction applied to the determination of odorous compounds in drinking water.

The off-flavour compounds 2-methylisoborneol (MIB), geosmin, 2,4,6-trichloroanisole, 2,3,6-trichloroanisole, 2,3,4-trichloroanisole and 2,4,6-tribromoanisole were analyzed in water samples by Stir Bar Sorptive Extraction (SBSE) followed by on-line thermal desorption (TD)-capillary GC/MS. Quantification was performed using MS in the single ion monitoring mode (SIM) with 2,4,6-trichloroanisol-D5 as internal standard. Quantification limits are 0.1 ng/l to 0.2 ng/l for the haloanisoles, 0.5 ng/l for geosmin and 1 ng/l for MIB. The relative standard deviations at the quantification limit are ranging from 7 to 14.6%. SBSE-recovery was evaluated by spiking real water samples and varied from 87 to 117%. More than twenty samples per day can be analyzed by SBSE-TD-capillary GC-MS. The same technique in combination with olfactometry was used to elucidate unknown odorous compounds in water samples.     

苯酚废水的高级氧化处理技术

以催生·OH自由基为主要氧化剂来氧化处理废水中难降解有机物的高级氧化技术正成为国内外研究的热点课题.分析了多种高级氧化技术对苯酚废水处理的共同作用机理,阐述了催化湿式氧化法、光催化氧化法、电催化技术、超声声化学氧化、超临界水氧化等在含酚废水高级氧化处理中的研究进展及发展趋势.     

Phenol adsorption by activated carbon produced from spent coffee grounds

The present work highlights the preparation of activated carbons (ACs) using spent coffee grounds, an agricultural residue, as carbon precursor and two different activating agents: water vapor (ACW) and K(2)CO(3) (ACK). These ACs presented the microporous nature and high surface area (620-950 m(2) g(-1)). The carbons, as well as a commercial activated carbon (CAC) used as reference, were evaluated as phenol adsorbent showing high adsorption capacity (≈150 mg g(-1)). The investigation of the pH solution in the phenol adsorption was also performed. The different activating agents led to AC with distinct morphological properties, surface area and chemical composition, although similar phenol adsorption capacity was verified for both prepared carbons. The production of activated carbons from spent coffee grounds resulted in promising adsorbents for phenol removal while giving a noble destination to the residue.     

Removal of hormones and pharmaceuticals in the Advanced Water Recycling Demonstration Plant in Queensland, Australia.

An advanced water recycling demonstration plant was employed to investigate the effectiveness of a number of treatment technologies in the removal of some residuals of commonly prescribed pharmaceuticals as well as natural and synthetic hormones found in sewage. Analysis of targeted compounds was carried out by solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS). Initial tests were undertaken to determine the background concentrations of the analytes during various stages of treatment. Subsequent tests, undertaken by spiking with standard solutions of the target compounds provided further information on the removal efficiencies of some selected treatment modules. The results of the study indicate that while ozonation, microfiltration and nanofiltration were partially effective, treatment by reverse osmosis was the most universally successful in the removal of the target residuals. While significantly more data is required for a full evaluation, this initial investigation suggests that reverse osmosis may be an effective means of removing a wider range of pharmaceutically active residuals and hormones from treated sewage.     

杭嘉湖地区饮用水源半挥发性有机物污染现状

采用固相萃取-GC-MS法对杭嘉湖地区16个集中式饮用水源水体中的氯代苯、多环芳烃、硝基苯、多氯联苯、邻苯二甲酸酯等43种半挥发性有机物（SVOCs）进行了分析检测。结果表明,16个集中式饮用水源水共检出10余种有机污染物,浓度范围为0.01~4.26μg/L,检出率为5%~100%;邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸双（2-二乙基己酯）、2,6-二硝基甲苯等化合物的检出率为超过50%;在平水期、丰水期、枯水期,被检出的有机污染物种类分别为12,9,14种,被检出污染物的浓度范围分别为0.05~4.26,0.01~0.20,0.01~1.00μg/L。     

Analytical approaches to characterising fish tainting potential of oil sands process waters.

A three-stage study has been carried out with rainbow trout (Oncorhyncus mykiss) to develop analytical approaches which can provide a fingerprint for tainting by oil sands chemicals from process-affected waters and natural sources. The objective was to find a simpler alternative to sensory evaluation. In the first stage, a set of seven test compounds was added to fish tissue which was analysed by headspace and solvent (dichloromethane, DCM) extraction followed by gas chromatography-mass spectrometry (GC-MS). In the second stage, fingerlings (5-20 g) were exposed for 96 hours to the test compound mixture at 1.0 and 0.5 times the estimated tainting threshold concentrations. In the final stage, fingerlings were exposed for 96 hours to an oil sands process water at 5, 10, 20 and 50% concentrations in clean water. None of the test compounds was identified in DCM extracts of tissue from exposed fish. Two long-chain aldehydes, hexadecanal and 9-octadecenal, were tentatively identified in these extracts by matching of mass spectra with library spectra.