Researches on Formation of Haloacetic Acids in Chlorination of Drinking Water by a Novel Technique

Haloacetic acids (HAAs) are formed during the chlorination of drinking water, which are harmful to peo-ple′s health due to their carcinogenic and mutagenic effects. In the present study, a detection method combin-ing methyl tert-butyl ether (MtBE) extraction with acid catalysis and gas chromatography coupled with anelectron capture detector (GC/ECD) was developed for determining HAAs. The detection limit of this method(MDL) and relative standard deviation (RSD) were below 0. 37μg/L and 6.2%, respectively. The laboratorychlorination experiments were conducted with the purpose of investigating the influences of reaction time,temperature, UV254, bromide and ammonia-nitrogen on the formation of HAAs. The results show that theformation amount of HAAs increases with increasing reaction time and temperature, respectively;and thereexists a linear relationship between the formation of HAAs and UV254. The formation amount of HAAs de-creases first and then increases as the bromide ion concentration increases, and adding NH4^ is a possible wayto control the formation of HAAs.     

饮用水中挥发性有机物(VOCs)的GC-MS分析

用顶空－毛细管气相色谱－质谱联用仪测定了北京主要区域的自来水,北京目前市场销售的瓶装饮用水（包括天然矿泉水,纯净水等）中２３种挥发性有机物（ＶＯＣｓ）（包括有机氯化物,有机溴代物及苯系物等）的浓度,并与其它城市（如天津,上海,兰州等地）的自来水中ＶＯＣｓ的浓度进行了比较,结果表明北京市区内自来水及大多数市售瓶瓶饮用水中ＶＯＣｓ含量很低。     

Sampling and Analysis of Odorous Compounds in Water Treatment Plants

Abstract

The following analytical method has been used to identify some odorous compounds in the air of the water treatment plant Werdholzli, Zurich: sampling of contaminated air with the help of activated carbon, desorption by the solvents carbon disulphide and methylene chloride, separation of the carbon disulfide extract into a polar and a nonpolar fraction by adsorption column chromatography on silica. Hereafter gaschromatographic analysis of the polar fraction on glass capillary column (Ucon HB 5100); detection and identification were achieved by flame ionisation, thermoionic nitrogen selective detector and computerized mass spectrometry (Finnigan 3200 F, data system 6110).

The results show the presence of sulfur compounds: thiophenes, thiazoles; nitrogen compounds: pyrazines; oxygen compounds: phenols, alcohols and some unsatured hydrocarbons. The malodorous compounds were sulfur and nitrogen compounds in the range of 0.01-0.1 ppm.     

气相色谱-质谱法测定饮用水中的卤乙酸

参照美国EPA Method 552.3方法中的液-液微萃取、酸化甲醇衍生化技术,以高纯水代替甲基叔丁基醚（MTBE）做溶剂配制标准贮备液,采用气相色谱/质谱联用技术对饮用水中的卤乙酸(HAAs)进行测定。结果表明:在所确立的检测条件下,样品分析时间短,内标、HAAs组分峰在谱图上能够得到很好的分离。低、中、高3个浓度水平的加标水样的HAAs回收率为82%~103%。该方法的检测限:二氯乙酸为0.72 μg/L、三氯乙酸为0.44 μg/L。用水做溶剂配制的标准贮备液在4 ℃条件下贮存时,贮存时间为2个月。     

Analysis of Semi-Volatile Aromatic Chlorinated Acids in Drinking Water by Liquid-Solid Extraction GC/MS

Abstract

An analytical procedure utilizing solid phase extraction with octadecylsilane bonded to silica (C₁₈) cartridges combined with gas chromatography/mass spectrometry (GC/MS) was developed to analyze semi-volatile chlorinated acids found in drinking water. A system has been designed which will enable the analysis of this class of compounds with minimum sample manipulation and detection limits in the low ng/L range. The overall accuracy and precision were comparable to other methods used for compliance purposes. Among the advantages of the developed methodology are its applicability for field sampling and at the same time, provides a simple and inexpensive mean for sample preservation.     

Surrogate Analysis of Trace Levels of Volatile Halogenated Organic Compounds in Drinking Water

Abstract

A supported liquid membrane coupled to an electron capture detector was found to be sensitive to chloroform concentrations in water in the 10 part per trillion range. No preconcentration of the water sample was required. The membrane consisted of silicone rubber tubing swollen with 10% by weight di-nonyl phthalate in decalin. The average response time was 34 minutes.     

顶空固相微萃取/气相色谱-三重四极杆串联质谱法测定地表水与饮用水中的挥发性有机物

采用部分因子试验设计筛选出顶空固相微萃取的主要影响参数,利用中心复合设计对主要影响参数的取值进行了优化,建立了顶空固相微萃取(HS-SPME)结合气相色谱-三重四极杆串联质谱(GC-MS/MS)测定地表水和饮用水中55种挥发性有机物(VOCs)的分析方法。取5.0 mL样品于顶空瓶中,加入0.75 g NaCl,使用CAR/PDMS 75μm纤维头,萃取温度40℃,萃取时间40 min,解析温度300℃,在GC-MS/MS选择反应监测(SRM)模式下检测,内标法定量。结果表明,55种VOCs在0.04～0.40、0.4～4.0、4.0～100μg/L质量浓度范围内线性良好,相关系数(r~2)均大于0.99,方法的检出限为0.03～80 ng/L,定量下限为0.1～300 ng/L。55种VOCs在0.2、2.0、40μg/L 3个加标水平下的平均回收率为77.3%～124%,相对标准偏差(RSD,n=6)为1.3%～17%。对3种地表水和3种饮用水进行测定,地表水中有37种VOCs被检出,饮用水中有25种VOCs被检出。实验证明,建立的HS-SPME和GC-MS/MS相结合的检测方法具有准确可靠、简单快速、灵敏度高等优点,适用于地表水和饮用水中VOCs的同时测定。     

饮用水含氮消毒副产物NDMA的形成与去除研究进展

N-亚硝基二甲胺(NDMA)是一种强致痛物质,普遍存在于食品、工业制品和污染大气之中.作为一种新发现的饮用水消毒副产物,NDMA已逐渐成为水环境化学研究领域的一个热点.介绍了饮用水消毒副产物NDMA的相关背景,重点评述了NDMA在水中的形成机制,主要包括亚硝化和非对称二甲肼氧化两种途径,强调NDMA的前体物还有待进一步确认.对水中NDMA的去除方法进行了总结,包括物理方法、光解作用、生物降解和高级氧化技术.最后提出了饮用水含氮消毒副产物NDMA的若干研究方向.     

Monitoring of Pollutants Content in Bottled and Tap Drinking Water in Italy

The concentration levels of thirteen organic pollutants and selected heavy metals were investigated in 40 plastics bottled and tap water samples. Some of the selected contaminants have an ascertained or suspected endocrine disrupting activity, such as Bisphenol A (BPA) and its analogs, and Bis 2-ethylhexyl phthalate (DEHP), which are used by industries as plasticizers. The most frequently detected pollutants were Bisphenol AF (BPAF) (detection frequency (DF) = 67.5%, mean 387.21 ng L⁻¹), DEHP (DF = 62.5%, mean 46.19 µg L⁻¹) and BPA (DF = 60.0%, mean 458.57 ng L⁻¹), with higher concentration levels found in tap waters. Furthermore, a possible level of exposure to thirteen pollutants via drinking water intake was calculated. Our findings show that, even though the occurrence of contaminants and heavy metals in drinking waters does not pose an immediate, acute health risk for the population, their levels should be constantly monitored and “hard-wired” into everyday practice. Indeed, the health impact to the continuous and simultaneous intake of a huge variety of xenobiotics from various sources by humans is complex and still not fully understood.     

重油催化裂化汽油中含氮化合物的分析

利用酸萃取技术浓缩分离重油催化裂化（RFCC）汽油中的氮化物，比较了两种萃取剂和两种油剂比对分离效果的影响，结果发现选用10％（体积分数）HCl作萃取剂，油剂比为10：1（体积比）时，碱性氮化物的提取率较高；浓缩分离出的氮化物用色谱－质谱联用方法对其进行了检测，结果表明RFCC汽油中的氮化物主要是C0－C2苯胺及少量吡啶类、喹啉类碱性氮化物。     

Study of Clethodim Degradation and By-Product Formation in Chlorinated Water by HPLC

Two of the most commonly used chlorinating agents for water disinfection, hypochlorite and chloramines, were employed to investigate the degradation of clethodim in conditions simulating tap water treatment. The main clethodim degradation products were identified by using liquid chromatography (LC) coupled with mass spectrometry (MS). The main degradation process was oxidation to sulfoxide and then to sulfone. Degradation half-life was calculated for both parent clethodim and the first degradation product, clethodim sulfoxide. Whereas some other different minor by-products were identified when the degradation occurs with either sodium hypochlorite or chloramines, no other chlorinated by-products were found under the conditions tested.     

Quantitative Analysis and Differential Evaluation of Radix Bupleuri Cultivated in Different Regions Based on HPLC-MS and GC-MS Combined with Multivariate Statistical Analysis

The quality of Radix Bupleuri is greatly affected by its growing environment. In this study, Radix Bupleuri samples that were harvested from seven different regions across northwest China were examined by high-performance liquid chromatography (HPLC) and gas chromatography (GC) coupled with mass spectrometry (MS) to reveal significant differences in quality contributed by the cultivation region. An HPLC-MS method was firstly established and used in the multiple reaction monitoring mode for the quantitative analysis of five saikosaponins in Radix Bupleuri so as to evaluate the difference in the absolute content of saikosaponins attributable to the cultivation region. The effect on the components of Radix Bupleuri was further investigated based on the profiles of the representative saponins and volatile compounds, which were extracted from the Radix Bupleuri samples and analyzed by HPLC-MS and GC-MS. Multivariate statistical analysis was employed to differentiate the Radix Bupleuri samples cultivated in different regions and to discover the differential compositions. The developed quantitative method was validated to be accurate, stable, sensitive, and repeatable for the determination of five saikosaponins. Further statistical tests revealed that the collected Radix Bupleuri samples were distinctly different from each other in terms of both saponins and volatile compounds, based on the provinces where they were grown. In addition, twenty-eight saponins and fifty-eight volatile compounds were identified as the differentially accumulated compositions that contributed to the discrimination of the Radix Bupleuri samples. The Radix Bupleuri samples grown in Shouyang county showed the highest content of saikosaponins. All of the results indicated that the cultivation region significantly affected the accumulation and diversity of the main chemical components of Radix Bupleuri. The findings of this research provide insights into the effect of the cultivation region on the quality of Radix Bupleuri and the differentiation of Radix Bupleuri cultivated in different regions based on the use of HPLC-MS and GC-MS combined with multivariate statistical analysis.     

重油催化裂化汽油中酚类化合物的分离分析

利用100g/L NaOH作萃取剂，二氯甲烷为反萃取剂，油剂比为5：1（体积比）时浓缩分离石家庄炼油厂和燕山石油化工公司的重油催化裂化（RFCC）稳定汽油和预碱洗后汽油中的酚类化合物；多面手利用色谱-质谱联用法对浓缩分离出的酚类化合物进行了检测，结果发现RFCC汽油中的酚类化合物主要是C0-C3苯酚，还有少量C4苯酚；所用稳定汽油和预碱洗后汽油的酚类组成相似，但碱洗后苯酚含量减少。     

Reduction and Coupling Reaction of Carbonyl Compounds by Aluminum Powder and a Small Amount of Oxalic Acid in Water

A convenient pinacol coupling of aromatic aldehydes and aryl methyl ketones has been achieved with high yields by aluminum powder in the presence of oxalic acid in water. However, the diastereoselectivities of pinacols were not satisfying, and most aliphatic aldehydes and diaryl ketones have been found to be unreactive under the same conditions.     

Membrane Extraction Combined with Thermodesorption/Gas Chromatography and Mass Selective Detection for the Analysis of Volatile Organic Compounds in Water

The range of application of a commercial thermodesorption-cryofocussing unit connected to a gas chromatograph/mass selective detector was extended to water analysis by using it in conjunction with membrane extraction. A flow of nitrogen passes through a silicone hollow fiber immersed in the water sample and extracted volatile organic compounds are enriched in a sorption tube mounted on top of the extraction cell. The sorption tube is then placed in the thermodesorption unit and analyzed by GC/MS. The optimal extraction parameters of this combined method were found to be 30 min extraction at 20°C with a stirring speed of 1,250 rpm and a flow rate of 100 mL/min nitrogen using a silicone hollow fiber of 0.3 m length. Under these conditions the reproducibility of the method was 5.2–10.5% RSD. The linear dynamic range of the optimized method spans three orders of magnitude and detection limits were found to be 0.02–0.1 μg/L for cis/trans-1,2-dichloroethene, benzene, trichloroethene, chlorobenzene, bromobenzene, ethylbenzene, 1,1,2,2-tetrachloroethane, and 1,2/1,4-dichlorobenzene. The method was found to be suitable for compounds with boiling points up to 220°C as memory effects increased considerably from dichloro- to hexachlorobenzene. Highly contaminated groundwater samples were analyzed. Quantitative results corresponded well with those achieved with conventional headspace-GC/FID.     

Solid-phase Extraction for Analysis of Short-Chain Chlorinated Paraffins in Water Samples

A method for analysis of short-chain chlorinated paraffins (SCCPs) in water based on solid-phase extraction (SPE) was established using electron capture negative chemical ionization mass spectrometry (GC-ENCI-MS). The SPE parameters, including the sorbent, eluent and elution volume were optimized. The Agilent Bond Elut-C₁₈ was precleaned with 3 mL of hexane and 3 mL of methanol, and subsequently conditioned with 3 mL H₂O prior to use. After the water samples were enriched by the cartridge, the sample was washed with 3 mL of 10% (V/V) methanol and eluted with 3 mL of hexane-dichloromethane (1:1, V/V) solution. The results indicated that the limits of detection (LOD) for SCCPs were 18 ng L^?1, while the corresponding limits of quantitation (LOQ) were 60 ng L^?1. The spiked recovery range was 90%–135%, with a relative standard deviation of less than 10%. Finally, 20 surficial water samples around Beijing were collected and SCCPs contents were analyzed using the proposed method. The SCCPs concentrations ranged from less than LOD to 682 ng L^?1 with a mean concentration of 216 ng L^?1.     

Analysis of Pesticides in Water Samples Using GC-ECD and GC-MS/MS Techniques

Abstract

A pesticide multiresidue method for determining dichlorvos, naled. lindane, diazinon. chlorpyri-fos-methyl, dichlofluanid, chlorpyrifos, folpet, α– and β-endosulfan, endosulfan-sulphate, fen-propathrin and acrinathrin in water samples at the levels required by the EEC Drinking Waters Directive has been developed. The pesticides were selected among the most used during die last 20 years in Almeria (Spain), where there is a high agricultural activity. Solid Phase Extraction (SPE) was selected as extraction method after being compared with Liquid-Liquid Extraction (LLE). Moreover, different gas chromatographic detectors (Electron Capture Detector, ECD; Mass Spectrometer, MS; Tandem Mass Spectrometer, MS/MS) were compared. The best results of repeatability and sensitivity were obtained for ECD and MS/MS.     

Optimization of HS-SPME for GC-MS Analysis and Its Application in Characterization of Volatile Compounds in Sweet Potato

Volatile compounds are the main chemical species determining the characteristic aroma of food. A procedure based on headspace solid-phase microextraction (HP-SPME) coupled to gas chromatography-mass spectrometry (GC-MS) was developed to investigate the volatile compounds of sweet potato. The experimental conditions (fiber coating, incubation temperature and time, extraction time) were optimized for the extraction of volatile compounds from sweet potato. The samples incubated at 80 °C for 30 min and extracted at 80 °C by the fiber with a divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) coating for 30 min gave the most effective extraction of the analytes. The optimized method was applied to study the volatile profile of four sweet potato cultivars (Anna, Jieshu95-16, Ayamursaki, and Shuangzai) with different aroma. In total, 68 compounds were identified and the dominants were aldehydes, followed by alcohols, ketones, and terpenes. Significant differences were observed among the volatile profile of four cultivars. Furthermore, each cultivar was characterized by different compounds with typical flavor. The results substantiated that the optimized HS-SPME GC-MS method could provide an efficient and convenient approach to study the flavor characteristics of sweet potato. This is the basis for studying the key aroma-active compounds and selecting odor-rich accessions, which will help in the targeted improvement of sweet potato flavor in breeding.     

Influence of Freezing and Different Drying Methods on Volatile Profiles of Strawberry and Analysis of Volatile Compounds of Strawberry Commercial Jams

Strawberry is the most consumed berry fruit worldwide due to its unique aroma and flavor. Drying fruits to produce a powder represents one of the possible conservation methods to extend their shelf-life. The aim of the present study was to compare the influence of freezing and different drying methods on the volatile profile of strawberry using the HS-SPME/GC–MS method, in addition to analysis of strawberry jam volatiles. A total of 165 compounds were identified, accounting for 85.03–96.88% of the total volatile compositions. Results and PCA showed that freezing and each drying process affected the volatile profile in a different way, and the most remarkable representative differential volatiles were ethyl hexanoate, hexyl acetate, (E)-2-hexenyl acetate, mesifurane, (E)-nerolidol, γ-decalactone, 1-hexanol, and acetoin. Shade air-dried, frozen, freeze-dried, and oven-dried 45 °C samples retained more of the fruity and sweet aromas of strawberry, representing more than 68% of the total aroma intensity according to the literature. In contrast, the microwave-drying method showed drastic loss of fruity esters. Strawberry jams demonstrated complete destruction of esters and alcohols in most jams, while terpenes were significantly increased. These findings help better understand the aroma of strawberry and provide a guide for the effects of drying, freezing, and jam processing.