In-situ methylation of strongly polar organic acids in natural waters supported by ion-pairing agents for headspace GC-MSD analysis

Strongly polar organic substances like halogenated acetic acids have been analyzed in surface water and groundwater in the catchment area of the upper Elbe river in Saxony since 1992. Coming directly from anthropogenic sources like industry, agriculture and indirectly by rainfall, their concentrations can increase up to 100 μg/L in the aquatic environment of this catchment area. A new static headspace GC-MSD method without a manual pre-concentration step is presented to analyze the chlorinated acetic acids relevant to the Elbe river as their volatile methyl esters. Using an ion-pairing agent as modifier for the in-situ methylation of the analytes by dimethylsulfate, a minimal detection limit of 1 μg/L can be achieved. Problems like the thermal degradation of chlorinated acetic acids to halogenated hydrocarbons and changing reaction yields during the headspace methylation, could be effectively reduced. The method has been successfully applied to monitoring bank infiltrate, surface water, groundwater and water works pumped raw water according to health provision principles. Received: 17 July 1997 / Revised: 29 September 1997 / Accepted: 2 October 1997     

Determination of volatile chlorinated hydrocarbons in water samples by static headspace gas chromatography with electron capture detection

A simple, efficient, solvent‐free, and commercial readily available approach for determination of five volatile chlorinated hydrocarbons in water samples using the static headspace sampling and gas chromatography with electron capture detection has been described. The proposed static headspace sampling method was initially optimized and the optimum experimental conditions found were 10 mL water sample containing 20% w/v sodium chloride placed in a 20 mL vial and stirred at 50ºC for 20 min. The linearity of the method was in the range of 1.2–240 μg/L for dichloromethane, 0.2–40 μg/L for trichloromethane, 0.005–1 μg/L for perchloromethane, 0.025–5 μg/L for trichloroethylene, and 0.01–2 μg/L for perchloroethylene, with coefficients of determination ranging between 0.9979 and 0.9990. The limits of detection were in the low μg/L level, ranging between 0.001 and 0.3 μg/L. The relative recoveries of spiked five volatile chlorinated hydrocarbons with external calibration method at different concentration levels in pure, tap, sea water of Jiaojiang Estuary, and sea water of waters of Xiaomendao were in the range of 91–116, 96–105, 86–112, and 80–111%, respectively, and with relative standard deviations of 1.9–3.6, 2.3–3.5, 1.5–2.7, and 2.3–3.7% (n = 5), respectively. The performance of the proposed method was compared with traditional liquid–liquid extraction on the real water samples (i.e., pure, tap, and sea water, etc.) and comparable efficiencies were obtained. It is concluded that this method can be successfully applied for the determination of volatile chlorinated hydrocarbons in different water samples.     

Chlorinated di- and triphenylmethanes in sediments of the Mulde and Elbe rivers

Congeneric groups of chlorinated diphenylmethanes (ClDPM) and triphenylmethanes (ClTPM) identified by coupled GC/MS investigations of Elbe and Mulde river sediments were not as yet noticed as environmental contaminants of aquatic sediments. ClDPM and ClTPM are structurally related to other polychlorinated aromatic compounds and form complex mixtures of congeners. Individual ClDPM/ClTPM as well as mixtures of congerers were synthesized, and served as reference compounds for isomer identification and quantitative analysis. In addition to mass spectra, GC/FTIR-investigations and retention indices proved to be valuable for structural assignments. Sediments from the Mulde river contained up to 220 μg/kg ClTPM and 170 μg/kg ClDPM. The spatial distribution of ClDPM/TPM concentrations indicated a strong localized source of emisson at the lower Mulde river, from where the compounds enter sediments and suspended matter of the Elbe river. The occurrence of ClTPM in the Hamburg harbour at comparable levels in samples of recent and older sediments indicates emissions over a prolonged period.     

Determination of volatile organic compounds by headspace trap

A new analytical method for the determination of halogenated and aromatic volatile organic compounds in groundwater, mineral water, and drinking water at concentrations ranging between 1-10000 ng/L is developed. A new type of headspace sampler that combines static headspace sampling with a trap is used, yielding very low detection limits and good repeatability without carryover effects. An unexpected transformation of 1,1,2,2-tetrachloroethane into trichloroethene is observed and explained.     

Coupling of SPME with MCC/UV–IMS as a tool for rapid on-site detection of groundwater and surface water contamination

The combination of headspace solid phase microextraction (HS-SPME) [1] with fast chromatographic pre-separation by means of multi-capillary columns (MCC) coupled to an ion mobility spectrometer equipped with a 10.6 eV photoionisation source was applied to rapid on-site monitoring of ground and surface water contaminations. Under field conditions, water contaminants were directly detectable down to the upper g/L range. The potential of the developed method is illustrated by measurements of BTEX, naphthalene, chlorinated alkenes and chlorinated benzenes in water. Practical results from investigations of contaminated groundwater at a former gasworks site and groundwater from the site of a metal processing plant, focusing on the key substances benzene, naphthalene and tetrachloroethene, demonstrate the feasibility of the system for field studies.Dedicated to the memory of Wilhelm Fresenius. One of the authors (D. Klockow) feels very much indebeted to Prof. Fresenius because of the steady support and advice he received through him, as a professional and as a private person.     

Simultaneous Determination of Haloacetic Acids in Environmental Waters using Electrospray Ionization Liquid Chromatography Mass Spectrometry

Negative ionization electrospray liquid chromatography mass spectrometry was developed for the simultaneous determination of all nine haloacetic acids containing bromine and chlorine. Haloacetic acids were separated on a crosslinked polystyrene resin column using 3% acetic acid dissolved in acetonitrile:water (20:80) as mobile phase. The precision of this method varied from ±2.2 to ±7.1% for nine haloacetic acids. In addition, quantitative results obtained with spiked water samples at three different concentrations are described. The limit of detection of the proposed method using 200 mL of water samples was between 0.003 and 0.070 μg/L. This method was successfully applied to the trace determination of haloacetic acids in waste water, river water, and seawater.     

Solid‐phase microextraction with a graphene‐composite‐coated fiber coupled with GC for the determination of some halogenated aromatic hydrocarbons in water samples

In this work, a graphene composite was coated onto etched stainless‐steel wire through a sol–gel technique and it was used as a solid‐phase microextraction (SPME) fiber. The prepared fiber was characterized by SEM, which revealed that the fiber had a highly porous structure. The application of the fiber was evaluated through the headspace SPME of five halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, 1,3‐dichlorobenzene, 1,2‐dichlorobenzene, and 1,2,4‐trichlorobenzene) in water samples followed by GC with flame ionization detection. The main factors influencing the extraction efficiency, including headspace volume, extraction time, extraction temperature, stirring rate, ionic strength of sample solution, and desorption conditions, were studied and optimized. Under the optimum conditions, the linearity of the method ranged from 2.5 to 800.0 μg/L for 1,2,4‐trichlorobenzene and from 2.5 to 500.0 μg/L for chlorobenzene, bromobenzene, 1,3‐dichlorobenzene, and 1,2‐dichlorobenzene, with the correlation coefficients (r) ranging from 0.9962 to 0.9980, respectively. The LODs (S/N = 3) of the method for the analytes were in the range between 0.5 and 1.0 μg/L. The recoveries of the method for the analytes obtained for the spiked water samples at 50.0 and 250.0 μg/L were from 76.0 to 104.0%.     

SPE-GC-MS for the Determination of Halogenated Acetic Acids in Drinking Water

The development and optimization of analytical methods for the better monitoring of disinfection by-products especially haloacetic acids in water are key step in order to estimate human exposure to such products after chlorination. A reliable and accurate analytical method is needed in order to reach the levels of concentration required by United States Environmental Protection Agency regulations. In this study a method was developed for determining halogenated acetic acids in drinking water, involving solid phase extraction, methylation derivatization, and GC-MS. The new SPE-GC-MS-SIM method is capable of analyzing all nine acids at extremely low μg L^–1 level. Run time is significantly reduced without compromising analytical results. The major advantages of the method are the simplicity of the chromatography, short run time and low detection limits. The method performance, limits of detection and spiking recovery were evaluated and the results proved that the accuracy and precision were good. This method outperforms previous GC-MS methods especially for the determination of dibromoacetic, dibromochloroacetic, dichlorobromoacetic and tribromoacetic acids. The method has been used to analyse domestic tap water and water samples collected at a local water treatment plant.     

Simple and automatic determination of aldehydes and acetone in water by headspace solid-phase microextraction and gas chromatography-mass spectrometry

We describe a simple and automatic method to determine nine aldehydes and acetone simultaneously in water. This method is based on derivatization with 2,2,2-trifluoroethylhydrazine (TFEH) and consecutive headspace-solid-phase microextraction and gas chromatography-mass spectrometry. Acetone-d(6) was used as the internal standard. Aldehydes and acetone in water reacted for 30 min at 40°C with TFEH in a headspace vial and the formed TFEH derivatives were simultaneously vaporized and adsorbed on polydimethylsiloxane-divinylbenzene. Under the established condition, the method detection limit was 0.1-0.5 μg/L in 4 mL water and the relative standard deviation was less than 13% at concentrations of 0.25 and 0.05 mg/L. This method was applied to determine aldehydes and acetone in 5 mineral water and 114 surface water samples. All mineral water samples had detectable levels of methanal (24.0-61.8 μg/L), ethanal (57.7-110.9 μg/L), propanal (11.5-11.7 μg/L), butanal, pentanal (3.3-3.4 μg/L) and nonanal (0.3-0.4 μg/L). Methanal and ethanal were also detected in concentration range of 2.7-117.2 and 1.2-11.9 μg/L, respectively, in surface water of 114 monitoring sites in Korea.     

Simultaneous liquid-liquid microextraction/methylation for the determination of haloacetic acids in drinking waters by headspace gas chromatography

A novel analytical method that combines simultaneous liquid-liquid microextraction/methylation and headspace gas chromatography-mass spectrometry for the determination of nine haloacetic acids (HAAs) in water was reported. A mechanistic model on the basis of mass transfer with chemical reaction in which methylation of HAAs was accomplished in n-pentane-water (150 microl-10 ml) two-phase system with a tetrabutylammonium salt as phase transfer catalyst was proposed. Derivatisation with dimethylsulphate was completed in 3 min by shaking at room temperature. The methyl ester derivatives and the organic phase were completely volatilised by static headspace technique, being the gaseous phase analysed. Parameters related to the extraction/methylation and headspace generation of HAAs were studied and the results were compared with methyl haloacetate standards to establish the yield of each step. The thermal instability of HAAs, by degradation to their respective halogenated hydrocarbon by decarboxylation, and the possible hydrolysation of the methyl esters were rigorously controlled in the whole process to obtain a reliable and robust method. The proposed method yielded detection limits very low which ranges from 0.02 to 0.4 microg l(-1) and a relative standard deviation of ca. 7.5%. Finally, the method was validated with the US Environmental Protection Agency (EPA) method 552.2 for the analysis of HAAs in drinking and swimming pool water samples containing concentrations of HAAs that must be higher than 10 microg l(-1) due to the fact that this method is less sensitive than the proposed one.     

SPE-GC-MS for the Determination of Halogenated Acetic Acids in Drinking Water

The development and optimization of analytical methods for the better monitoring of disinfection by-products especially haloacetic acids in water are key step in order to estimate human exposure to such products after chlorination. A reliable and accurate analytical method is needed in order to reach the levels of concentration required by United States Environmental Protection Agency regulations. In this study a method was developed for determining halogenated acetic acids in drinking water, involving solid phase extraction, methylation derivatization, and GC-MS. The new SPE-GC-MS-SIM method is capable of analyzing all nine acids at extremely low μg L^–1 level. Run time is significantly reduced without compromising analytical results. The major advantages of the method are the simplicity of the chromatography, short run time and low detection limits. The method performance, limits of detection and spiking recovery were evaluated and the results proved that the accuracy and precision were good. This method outperforms previous GC-MS methods especially for the determination of dibromoacetic, dibromochloroacetic, dichlorobromoacetic and tribromoacetic acids. The method has been used to analyse domestic tap water and water samples collected at a local water treatment plant.

     

N-/P-pesticides in the Czech and German part of the river Elbe — Analytical methods and trends of pollution

A GC/MS screening procedure and an analytical routine method with GC/NP-detection is described for N-/P-pesticides in the river Elbe. The GC/MS screening procedure allows the separate analysis of pesticides in suspended particulate matter (SPM) and water (centrifugate). For the pesticides identified only a negligible (<1%) amount was bound to SPM compared to the “dissolved” amount in the centrifugate. N-/P-pesticide concentrations as time series and Elbe length-profiles are presented showing a drastical decrease of the pesticide pollution of the Elbe from 1989 to 1994. Major compounds were dimethoate, parathion-methyl, atrazine and simazine found in the μg/l range in the Elbe downstream of its tributary Mulde obviously stemming from a former East German pesticide production site.     

Problems of the control of volatile halogenated hydrocarbons in tap and waste waters

The concentration of volatile halogenated hydrocarbons in chlorinated tap water does not stay constant but increases during its passage through water supply systems, which indicates a certain incompleteness and the continuation of the transformation of humic substances upon the chlorination of water. The known official (certified) procedures, including the State Standard ones, seven in number, which are based on headspace gas chromatography, do not take into account such a peculiarity of tap water and deal with the quantification of free halogenated derivatives of hydrocarbons only. The comparative evaluation of official procedures is performed, and the sources of errors exceeding the acceptable level are inventoried; methods of optimization of all analytical steps are proposed to elaborate procedures ensuring the minimal error and reliable information on the concentration of volatile halogenated hydrocarbons in tap and waste waters.     

Determination of chlorinated toluenes in raw and treated water samples from the Llobregat river by closed loop stripping analysis and gas chromatography-mass spectrometry detection

A study of the occurrence of chlorinated toluenes in Llobregat river (NE Spain) has been carried out. These compounds are currently being used in local textile industries as dye carriers and have replaced the common trichlorobenzene mixtures. Closed loop stripping analysis (CLSA), routinely used to monitor the quality of river water for a broad range of volatile compounds, has been employed as an analytical tool to determine them at ng/L levels in wastewater and textile industry effluents and also in raw and treated water from two drinking water treatment plants situated in the river course. The CLSA extracts were analyzed by HRGC/MS. Ring halogenated dichloro- and, to a lesser extent, mono- and trichlorotoluenes have been identified. These compounds have not been reported to our knowledge as common water pollutants.     

Vortex‐assisted liquid–liquid microextraction for the rapid screening of short‐chain chlorinated paraffins in water

The rapid screening of trace levels of short‐chain chlorinated paraffins in various aqueous samples was performed by a simple and reliable procedure based on vortex‐assisted liquid–liquid microextraction combined with gas chromatography and electron capture negative ionization mass spectrometry. The optimal vortex‐assisted liquid–liquid microextraction conditions for 20 mL water sample were as follows: extractant 400 μL of dichloromethane; vortex extraction time of 1 min at 2500 × g; centrifugation of 3 min at 5000 × g; and no ionic strength adjustment. Under the optimum conditions, the limit of quantitation was 0.05 μg/L. Precision, as indicated by relative standard deviations, was less than 9% for both intra‐ and inter‐day analysis. Accuracy, expressed as the mean extraction recovery, was above 91%. The vortex‐assisted liquid–liquid microextraction with gas chromatography and electron capture negative ionization mass spectrometry method was successfully applied to quantitatively extract short‐chain chlorinated paraffins from samples of river water and the effluent of a wastewater treatment plant, and the concentrations ranged from 0.8 to 1.6 μg/L.     

Fluorometric determination of formaldehyde

A simple, selective and sensitive fluorometric method is presented for the determination of formaldehyde in water based on its reaction with 3,4-diaminoanisole in alkaline ethanol-water solution to give a strongly fluorescing Schiff base. The dependence of the fluorescence intensity on the solvent composition, quenching by acetic and sulphuric acid, heating time and interference by other compounds is discussed. The detection limit of the method is 0.6 μg/L. The recovery of formaldehyde spiked into river water is 93% with an R.S.D of 6.05% at a concentration level of 10 μg/L.     

气相色谱法同时测定水中12种挥发性消毒副产物

建立液-液萃取气相色谱法电子捕获检测器(GC/ECD)同时测定饮用水中12种挥发性消毒副产物(Disinfection byproducts, DBPs)的方法.采用过程标准校正降低预处理过程中引入的误差,方法检出限为0.08~0.21 μg/L, 全部组分在21.50 min内测定完成.不同浓度的DBPs在自来水和地表水中的回收率为80.9%~115.7%,相对标准偏差在0.9%~9.9%之间.各组分在0.5~200 μg/L浓度范围内线性关系良好,相关系数R>0.99.应用本方法测定了饮用水和地表水及其氯化后样品中DBPs的含量.本方法简便、快速、稳定,满足饮用水中挥发性DBPs的检测要求.     

Stir bar sorptive extraction for the analysis of short‐chain chlorinated paraffins in water

An optimised method using stir bar sorptive extraction (SBSE) and a thermal desorption‐GC‐electron capture detector (GC‐ECD) for the determination of short‐chain chlorinated paraffins from water samples was developed. Recoveries near to 100% were obtained by using 20 mm×0.5 mm (length×film thickness) PDMS commercial stir bars from 200 mL spiked water samples and 20% methanol addition with an extraction period of 24 h. Method sensitivity, linearity and precision were evaluated for surface water and wastewater spiked samples. A LOD of 0.03 and 0.04 μg/L was calculated for surface and wastewater, respectively. The precision of the method given as an RSD was below 20% for both matrices. The developed method was applied for the analysis of two real samples from a contaminated river and a wastewater treatment plant. Results were in accordance with those obtained using a previously developed method based on solid phase microextraction (SPME).     

Low nanogram per liter determination of halogenated nonylphenols,nonylphenol carboxylates,and their non-halogenated precursors in water and sludge by liquid chromatography electrospray tandem mass spectrometry

A new LC-MS-MS method for quantitative analysis of nonylphenol (NP), nonylphenol carboxylates (NPECs), and their halogenated derivatives: brominated and chlorinated nonylphenols (BrNP, ClNP), brominated and chlorinated nonylphenol carboxylates (BrNPE(1)C and ClNPE(1)C) and ethoxycarboxylates (BrNPE(2)C and ClNPE(2)C) in water and sludge has been developed. Electrospray negative ionization MS-MS was applied for the identification of above mentioned compounds. Upon collision-induced dissociation, their deprotonated molecules gave different fragments formed by the cleavage of the alkyl moiety and/or (ethoxy)carboxylic moiety. For halogenated compounds a highly diagnostic characteristic pattern of isotopic doublet signals was obtained and fragmentation yielded, in addition to above mentioned ions, [Br](-) and [Cl](-), respectively. Quantitative analysis was done in the multiple reaction monitoring (MRM) mode, using two specific combinations of a precursor-product ion transitions for each compound. Additionally, for halogenated compounds two specific channels for each transition reaction, corresponding to two isotopes, were monitored and the ratio of their abundances used as an identification criterion. The method has been validated in terms of sensitivity, selectivity, accuracy, and precision and was applied to the analysis of water and sludge samples from drinking water treatment plant (DWTP) of Barcelona (Catalonia, NE Spain). Halogenated NP and NPECs were detected in prechlorinated water in concentrations up to 315 ng/L, BrNPE(2)C being the most abundant compound. In the DWTP effluent non-halogenated compounds were detected at trace levels (85, 12 and 10 ng/L for NP, NPE(1)C, and NPE(2)C, respectively), whereas concentration of halogenated derivatives never exceeded 10 ng/L. Nonylphenol, brominated and chlorinated NPs were found in flocculation sludge in concentrations of 150, 105, and 145 microg/kg, respectively. Acidic polar metabolites were found in lower concentrations up to 20 microg/kg.     

Determination of halonitromethanes in treated water

As halonitromethanes (HNMs) have begun to play an increasingly important role as disinfection by-products, the development of a highly sensitive method for their analysis has become a priority. The mass spectrometric behavior of the 9 HNMs revealed that trihalonitromethanes are more unstable than di- or monohalonitromethanes under common chromatographic conditions. The absence of a comprehensive method for HNMs has given rise to the development of the first method for the whole array of these species, involving the selection of a solventless technique. Single drop microextraction in the headspace mode (HS-SDME) was selected as it is inexpensive and easy to operate. Comparative measurements through EPA liquid-liquid extraction (LLE) method for halogenated volatile compounds, show this approach to be superior to the manual LLE procedure (the average limits of detection (LODs) for the 9 HNMs were 0.5 and 1 μg/L for the HS-SDME and EPA methods, respectively), adequate precision (8.2 and 7.0% for HS-SDME and EPA methods, respectively) and does not consume excessive solvent since the total extract (～2 μL) was injected completely into the GC-MS instrument. The method was used to measure HNMs in treated water and the results were compared to the EPA method in parallel.