Reviews - Multi-Compound - HAAs - HANs - HAMs - HNMs - Halobenzoquinones - Bromate

Other - LC/MS Methods - Large Studies

(See also: DBP Degradation)


Major Reports & Review Papers on Analysis of DBPs
Citation Notes Abstract
Richardson, S.D. (2012) Environmental Mass Spectrometry: Emerging Contaminants and Current Issues. Analytical Chemistry 84(2), 747-778.
The Biennial MS Review in An. Chem.  
Richardson, S.D. and Ternes, T.A. (2011) Water Analysis: Emerging Contaminants and Current Issues. Analytical Chemistry 83(12), 4614-4648. Biennial Review of water analysis  
Richardson, S.D. (2010) Environmental Mass Spectrometry: Emerging Contaminants and Current Issues. Analytical Chemistry 82(12), 4742-4774. The Biennial MS Review in An. Chem.  


Multi-Compound Methods
Citation Notes Abstract



Citation Notes Abstract
Luo, Q., Wang, D.H., Wei, Z. and Wang, Z.J. (2013) Optimized chromatographic conditions for separation of halogenated acetic acids by ultra-performance liquid chromatography-electrospray ionization-mass spectrometry. Journal of Chromatography A 1277, 26-34.
UPLC, ion pair method Emerging halogenated acetic acids (HAAs), especially mixed halogenated acids such as chlorobromo, chloroiodo- and bromoiodo-acetic acids, are unregulated disinfection by-products in drinking water. Because these compounds are hydrophilic and strongly acidic, they are difficult to detect at trace levels using approved analytical methods. In the present study, 13 HAM were effectively separated on three ultra-performance liquid chromatography columns. The effects of changing in the aqueous mobile phase, acidic solutions and cationic volatile ion pair reagents were investigated. The samples were pretreated by filtration, and extraction, while derivatization and concentration procedures were not required. The limits of quantitation for regulated HAAs were between 0.5 mu g/L and 1.7 mu g/L, and for unregulated HAAs were 1.2 and 5.8 mu g/L, especially for the iodinated acetic acids were 1.5 and 2.1 mu g/L. The method was applied to two finished water samples collected in China (Shanghai and Xuzhou) from water treatment plants that use chlorine for disinfection. Multiple unregulated HAAs were found in the two samples, but iodoacids were only detected in the water sample from Shanghai, which could be attributed to the characteristics of the source water. The presence of unregulated HAAs, especially mixed bromo- and iodoacetic acids, in the finished water samples could affect human health, and this warrants further investigation.
Prieto-Blanco, M.C., Alpendurada, M.F., Lopez-Mahia, P., Muniategui-Lorenzo, S., Prada-Rodriguez, D., Machado, S. and Goncalves, C. (2012) Improving methodological aspects of the analysis of five regulated haloacetic acids in water samples by solid-phase extraction, ion-pair liquid chromatography and electrospray tandem mass spectrometry. Talanta 94, 90-98.
ion pair method Haloacetic acids (HAAs) are organic pollutants originated from the drinking water disinfection process, which ought to be controlled and minimized. In this work a method for monitoring haloacetic acids (HAAs) in water samples is proposed, which can be used in quality control laboratories using the techniques most frequently available. Among its main advantages we may highlight its automated character, including minimal steps of sample preparation, and above all, its improved selectivity and sensitivity in the analysis of real samples. Five haloacetic acids (HAA5) were analyzed using solid-phase extraction (SPE) combined with ion-pair liquid chromatography and tandem mass spectrometry. For the optimization of the chromatographic separation, two amines (triethylamine, TEA and dibutylamine. DBA) as ion pair reagents were compared, and a better selectivity and sensitivity was obtained using DBA, especially for monohaloacetic acids. SPE conditions were optimized using different polymeric adsorbents. The electrospray source parameters were studied for maximum precursor ion accumulation, while the collision cell energy of the triple quadrupole mass spectrometer was adjusted for optimum fragmentation. Precursor ions detected were deprotonated, dimeric and decarboxylated ions. The major product ions formed were: ionized halogen atom (chloride and bromide) and decarboxylated ions. After enrichment of the HAAs in Lichrolut EN adsorbent, the limits of detection obtained by LC-MS/MS analysis (between 0.04 and 0.3 ng mL(-1)) were comparable to those obtained by GC-MS after derivatization. Linearity with good correlation coefficients was obtained over two orders of magnitude irrespective of the compound. Adequate recoveries were achieved (60-102%). and the repeatability and intermediate precision were in the range of 2.4-6.6% and 3.8-14.8%, respectively. In order to demonstrate the usefulness of the method for routine HAAs monitoring, different types of water samples were analyzed. In swimming pool water samples the Sigma HAAs were determined between 76 and 154 ng mL(-1).
Li, Y.T., Whitaker, J.S. and McCarty, C.L. (2012) Analysis of iodinated haloacetic acids in drinking water by reversed-phase liquid chromatography/electrospray ionization/tandem mass spectrometry with large volume direct aqueous injection. Journal of Chromatography A 1245, 75-82.

HPLC/Quattro Micro, C18, 1000 uL inject

MDL=0.5-2.3 ng/L

A large volume direct aqueous injection method was developed for the analysis of iodinated haloacetic acids in drinking water by using reversed-phase liquid chromatography/electrospray ionization/tandem mass spectrometry in the negative ion mode. Both the external and internal standard calibration methods were studied for the analysis of monoiodoacetic acid, chloroiodoacetic acid, bromoiodoacetic acid, and diiodoacetic acid in drinking water. The use of a divert valve technique for the mobile phase solvent delay, along with isotopically labeled analogs used as internal standards, effectively reduced and compensated for the ionization suppression typically caused by coexisting common inorganic anions. Under the optimized method conditions, the mean absolute and relative recoveries resulting from the replicate fortified deionized water and chlorinated drinking water analyses were 83-107% with a relative standard deviation of 0.7-11.7% and 84-111% with a relative standard deviation of 0.8-12.1%, respectively. The method detection limits resulting from the external and internal standard calibrations, based on seven fortified deionized water replicates, were 0.7-2.3 ng/L and 0.5-1.9 ng/L, respectively.
Duan, J.M., Li, W., Si, J. and Mulcahy, D. (2011) Rapid determination of nine haloacetic acids in water using ultra-performance liquid chromatography-tandem mass spectrometry in multiple reactions monitoring mode. Analytical Methods 3(7), 1667-1673.

UPLC with T3 column, LODs=0.06-0.16 ug/L

UMass approach

A simple and rapid detection method for nine haloacetic acids (HAAs) in water has been developed using ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) in multiple reactions monitoring (MRM) mode. Addition of a small amount of formic acid (FA) as a modifier for the methanol-water eluent was found to be critical for separation of the analytes with smaller molecular size (i.e. the mono and di-haloacetic acids). Without the need of sample preconcentration, very low limits of detection (LODs) for the nine HAAs were achieved (0.06-0.16 mu g L(-1)). The linear calibration range extended from 0.5 up to 100 mu g L(-1) (R(2) = 0.9993-0.9997, n = 6). The water matrix effect has been examined, and seems to be related to the ions in real water samples. Interestingly, an adjustment of the pH of the tap water samples to an acidic value of 3 or below basically eliminated the matrix effect. The method has been tested using tap water samples sourced from both surface water (total dissolved solid (TDS): 145 +/- 3mgL(-1)) and groundwater (TDS: 362 +/- 1mgL(-1)) with high precision and recovery. A separation mechanism of the ionic analytes using a reversed phase liquid chromatographic column (HSS T3) possessing a hydrophilic affinity has been proposed and discussed.
Meng, L.P., Wu, S.M., Ma, F.J., Jia, A. and Hu, J.Y. (2010) Trace determination of nine haloacetic acids in drinking water by liquid chromatography-electrospray tandem mass spectrometry. Journal of Chromatography A 1217(29), 4873-4876.

UPLC/Quattro Premier using C8

MDLs=0.16-9 ug/L

A simple, fast and sensitive liquid chromatography-electrospray tandem mass spectrometry method was established for trace levels of nine haloacetic acids (HAAs) in drinking water. Water samples were removed of residual chlorine by adding L-ascorbic acid, and directly injected after filtered by 0.22 mu m membrane. Nine HAAs were separated by liquid chromatography in 7.5 min, and the limits of detection were generally between 0.16 and 0.99 mu g/L except for chlorodibromoacetic acid (1.44 mu g/L) and tribromoacetic acid (8.87 mu g/L). The mean recoveries of nine target compounds in spiked drinking water samples were 80.1-108%, and no apparent signal suppression was observed. Finally, this method was applied to determine HAAs in the tap water samples collected from five waterworks in Shandong, China. Nine HAAs except for monochloroacetic acid, monobromoacetic acid, dibromochloroacetic acid and tribromoacetic acid were detected, and the total concentrations were 7.79-36.5 mu g/L. The determination results well met the first stage of the Disinfectants/Disinfection By-Products (D/DBP) Rules established by U.S.EPA and Guidelines for Drinking-water Quality of WHO.
Dixon, A.M., Delinsky, D.C., Bruckner, J.V., Fisher, J.W. and Bartlett, M.G. (2004) Analysis of dichloroacetic acid in drinking water by ion exchange HILIC-LC/MS/MS. Journal of Liquid Chromatography & Related Technologies 27(15), 2343-2355.
HILIC method Dichloroacetic acid (DCA) is a small, polar compound that individuals are exposed to as a result of drinking water consumption. The occurrence of DCA in drinking water is of concern because DCA has been shown to cause cancer in laboratory animals. To date, no validated LC/MS/MS methods are available for quantitative analysis of DCA. In addition, most methods use a derivatizing reagent that can artificially inflate the levels of DCA. Presented in this paper, is a validated LC/MS/MS method for the analysis of DCA in drinking water. An amino column was used with ion-exchange hydrophilic interaction chromatography (HILIC).


Citation Notes Abstract



(related info may be found in: DBP Degradation and Nonregulated DBP pages)
Citation Notes Abstract
Liew, D., K.L. Linge, C.A. Joll, A. Heitz, and J.W.A. Charrois. 2011. Determination of halonitromethanes and haloacetamides: An evaluation of sample preservation and analyte stability in drinking water. Journal of Chromatography A 1241:117-122.   Simultaneous quantitation of 6 halonitromethanes (HNMs) and 5 haloacetamides (HAAms) was achieved with a simplified liquid-liquid extraction (LLE) method, followed by gas chromatography-mass spectrometry. Stability tests showed that brominated tri-HNMs immediately degraded in the presence of ascorbic acid, sodium sulphite and sodium borohydride, and also reduced in samples treated with ammonium chloride, or with no preservation. Both ammonium chloride and ascorbic acid were suitable for the preservation of HAAms. Ammonium chloride was most suitable for preserving both HNMs and HAAms, although it is recommended that samples be analysed as soon as possible after collection. While ground-water samples exhibited a greater analytical bias compared to other waters, the good recoveries (>90%) of most analytes in tap water suggest that the method is very appropriate for determining these analytes in treated drinking waters. Application of the method to water from three drinking water treatment plants in Western Australia indicating N-DBP formation did occur, with increased detections after chlorination. The method is recommended for low-cost, rapid screening of both HNMs and HAAms in drinking water.
Chu, W.H. and Gao, N.Y. (2009) Determination of Nitrogenous Disinfection Byproducts Chloroacetamides in Drinking Water by Gas Chromatography-Mass Spectrometry. Chinese Journal of Analytical Chemistry 37(1), 103-106.   A new method for the determination of nitrogenous disinfection byproducts chloroacetamides (CAcAms) in drinking water by gas chromatography mass spectrometry (GC-MS) is described. In the method, the effects of different detecting instrument (GC/ECD and GC/MS) and sample pretreatment were investigated. Direct liquid-liquid extraction-GC/MS method was superior to acid-catalyzed hydrolysis + GC/ECD according to recovery comparison, and extraction effect of ethyl acetate (ETAC) excels methyl tert-butyl ether (MTBE). Good relativeity (r > 0.9995) was obtained when the linear range was 10 - 1000 mu g/L. The recoveries of CAcAms were 82.0% - 111.9%. The relative standard deviations were less than 10.0%. The determination limit is less than 1 mu g/L. The advantage of this method is simple, rapid and sensitive.
Choi, Y.W. and Reckhow, D.A. (2004) Fluorimetric determination of dichloroacetamide by RPLC with postcolumn detection. Bulletin of the Korean Chemical Society 25(6), 900-906.   An RPLC-postcolumn detection method has been developed for the fluorimetric determination of dichloroacetamide (DCAD) in water. After ammonia and DCAD were separated on a C-18 nonpolar stationary phase with 2.5% methanol-0.02 M phosphate buffer at pH 3, the column eluant was reacted with post column reagents, o-phthaldialdehyde (OPA) and sulfite ion at pH 11.5, to produce a highly fluorescent isoindole fluorophore, which was measured with a fluorescence detector (lambda(ex) = 363 nm, lambda(em) = 425 nm). With the optimized conditions for RPLC and the postcolumn derivatization, the calibration curve was found to be linear in the concentration ranges of 0.5 and 20 muM for DCAD, and the detection limit for DCAD was 0.18 muM (23 mug/L). This corresponded to 18 pmol per 100 muL injection volume for a signal-to-noise ratio of 3, and the repeatability and reproducibility of this method were 1.0% and 2.5% for five replicate analyzes of 2 muM DCAD, respectively. The degradation yields DCAD to ammonia were 94 and 99%, and the percent recoveries of DCAD from 4 and 6 muM DCAD-spiked tap water were shown mean more than 97%


Citation Notes Abstract


(most HBQ references are in: Non-Regulated DBPs, see also: Degradation, DBP Occurrence and DBP Health)
Citation Notes Abstract
Wang, W., Qian, Y.C., Li, J.H., Moe, B., Huang, R.F., Zhang, H.Q., Hrudey, S.E. and Li, X.F. (2014) Analytical and Toxicity Characterization of Halo-hydroxyl-benzoquinones as Stable Halobenzoquinone Disinfection Byproducts in Treated Water. Analytical Chemistry 86(10), 4982-4988. Supplemental Info.
  Exposure to chlorination disinfection byproducts (DBPs) is potentially associated with an increased risk of bladder cancer. Four halobenzoquinones (HBQs) have been detected in treated drinking water and have shown potency in producing reactive oxygen species and inducing damage to cellular DNA and proteins. These HBQs are unstable in drinking water. The fate and behavior of these HBQs in drinking water distribution systems is unclear. Here we report the high-resolution mass spectrometry identification of the transformation products of HBQs as halo-hydroxyl-benzoquinones (OH-HBQs) in water under realistic conditions. To further examine the kinetics of transformation, we developed a solid-phase extraction with ultrahigh-performance liquid chromatography tandem mass spectrometry (SPE-UHPLC-MS/MS) method to determine both the HBQs and OH-HBQs. The method provides reproducible retention times (SD < 0.05 min), limits of detection (LODs) at subnanogram per liter levels, and recoveries of 68%-96%. Using this method, we confirmed that decrease of HBQs correlated with increase of OH-HBQs in both the laboratory experiments and several distribution systems, supporting that OH-HBQs were more stable forms of HBQ DBPs. To understand the toxicological relevance of the OH-HBQs, we studied the in vitro toxicity with CHO-K1 cells and determined the IC50 of HBQs and OH-HBQs ranging from 15.9 to 72.9 mu M. While HBQs are 2-fold more toxic than OH-HBQs, both HBQs and OH-HBQs are substantially more toxic than the regulated DBPs.
Huang, R.F., Wang, W., Qian, Y.C., Boyd, J.M., Zhao, Y.L. and Li, X.F. (2013) Ultra Pressure Liquid Chromatography-Negative Electrospray Ionization Mass Spectrometry Determination of Twelve Halobenzoquinones at ng/L Levels in Drinking Water. Analytical Chemistry 85(9), 4520-4529.
  We report here the characterization of twelve halobenzoquinones (HBQs) using electrospray ionization (ESI) high resolution quadrupole time-of-flight mass spectrometry. The high resolution negative ESI spectra of the twelve HBQs formed two parent ions, [M + H+ + 2e(-)], and the radical M-center dot. The intensities of these two parent ions are dependent on their chemical structures and on instrumental parameters such as the source temperature and flow rate. The characteristic ions of the HBQs were used to develop an ultra pressure liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method. At the UPLC flow rate (400 mu L/min) and under the optimized ESI conditions, eleven HBQs showed the stable and abundant transitions [M + H+ + 2e(-)] -> X- (X- representing Cl-, Br-, or I-), while dibromo-dimethyl-benzoquinone (DBDMBQ) showed only the transition of M-center dot -> Br-. The UPLC efficiently separates all HBQs including some HBQisomers, while the MS/MS offers exquisite limits of detection (LODs) at subng/rnL levels for all HBQs except DBDMBQ, Combined with solid phase extraction (SPE), the method LOD is down to ng/L. The results from analysis of authentic samples demonstrated that the SPE-UPLC-MS/MS method is reliable, fast, and sensitive for the identification and quantification of the twelve HBQs in drinking water.
Qian, Y.C., Wang, W., Boyd, J.M., Wu, M.H., Hrudey, S.E. and Li, X.F. (2013) UV-Induced Transformation of Four Halobenzoquinones in Drinking Water. Environmental Science & Technology 47(9), 4426-4433. Supplemental Info.
  Halobenzoquinones (HBQs) are a group of emerging disinfection byproducts (DBPs) found in treated drinking water. Because the use of UV treatment for disinfection is becoming more widespread, it is important to understand how the HBQs may be removed or changed due to UV irradiation. Water samples containing four HBQs, 2,6-dichloro-1,4-benzoquinone (DCBQ), 2,3,6-trichloro-1,4-benzoquinone (TCBQ), 2,6-dichloro-3-methyl-1,4-benzoquinone (DCMBQ), and 2,6-dichloro-1,4-benzoquinone (DBBQ), were treated using a modified bench scale collimated beam device, mimicking UV treatment. Water samples before and after UV irradiation were analyzed for the parent compounds and products using a high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) method. As much as 90% of HBQs (0.25 nmol L-1) in both pure water and tap water were transformed to other products after UV254 irradiation at 1000 mJ cm(-2). The major products of the four HBQs were identified as 3-hydroxyl-2,6-dichloro-1,4-benzoquinone (OH-DCBQ). from DCBQ 5-hydroxyl-2,6-dichloro-3-methyl-1,4-benzoquinone (OH-DC/VIBQ) from DCMBQ, 5-hydroxyl-2,3,6-trichloro-1,4-benzoquinone (OH-TCBQ) from TCBQ and 3-hydroxyl-2,6-dibromo-1,4-benzoquinone (OH-DBBQ) from DBBQ These four OH-HBQs were further modified to monohalogenated benzoquinones when the UV dose was higher than 200 mJ cm(-2). These results suggested possible pathways of UV induced transformation of HBQs to other compounds. Under the UV dose commonly used in water treatment plants, it is likely that HBQs are partially converted to other halo-DBPs. The occurrence and toxicity of these mixed DBPs warrant further investigation to understand whether they pose a health risk
Wang, W., Qian, Y.C., Boyd, J.M., Wu, M.H., Hrudey, S.E. and Li, X.F. (2013) Halobenzoquinones in Swimming Pool Waters and Their Formation from Personal Care Products. Environmental Science & Technology 47(7), 3275-3282. Supplemental Info.
  Halobenzoquinones (HBQs) are a class of disinfection byproducts (DBPs) of health relevance. In this study, we aimed to uncover which HBQs are present in swimming pools. To achieve this goal, we developed a new method capable of determining eight HBQs while overcoming matrix effects to achieve reliable quantification. The method provided reproducible and quantitative recovery (67-102%) and detection limits of 0.03-1.2 ng/L for all eight HBQs. Using this new method, we investigated water samples from 10 swimming pools and found 2,6-dichloro-1,4-benzoquinone (2,6-DCBQ) in all the pools at concentrations of 19-299 ng/L, which was as much as 100 times higher than its concentration in the input tap water (1-6 ng/L). We also identified 2,3,6-trichloro-(1,4)benzoquinone (TriCBQ), 2,3-dibromo-5,6-dimethyl-(1,4)-benzoquinone (DMDBBQ), and 2,6-dibromo-(1,4)benzoquinone (2,6-DBBQ) in some swimming pools at concentrations of <0.1-11.3, <0.05-0.7, and <0.05-3.9 ng/L, respectively, but not in the input tap water. We examined several factors to determine why HBQ concentrations in pools were much higher than in the input tap water. Higher dissolved organic carbon (DOC), higher doses of chlorine and higher temperatures enhanced the formation of HBQs in the pools. In addition, we conducted laboratory disinfection experiments and discovered that personal care products (PCPs) such as lotions and sunscreens can serve as precursors to form additional HBQs, such as TriCBQ 2,6-dichloro-3-methyl-(1,4)benzoquinone (DCMBQ), and 2,3,5,6-tetrabromo-(1,4)benzoquinone (TetraB-1,4-BQ). These results explained why some HBQs existed in swimming pools but not in the input water. This study presents the first set of occurrence data, identification of new HBQ DBPs, and the factors for their enhanced formation in the swimming pools.
Anichina, J., Zhao, Y.L., Hrudey, S.E., Le, X.C. and Li, X.F. (2010) Electrospray Ionization Mass Spectrometry Characterization of Interactions of Newly Identified Water Disinfection Byproducts Halobenzoquinones with Oligodeoxynucleotides. Environmental Science & Technology 44(24), 9557-9563.   Four halobenzoquinones, 2,6-dibromo-1,4-benzoquinone, 2,6-dichloro-1,4-benzoquinone, 2,6-dichloro-3-methyl-1,4-benzoquinone, and 2,3,6-trichloro-1,4-benzoquinone, were recently identified as drinking water disinfection byproducts. Understanding their interactions with biomolecules could provide useful insights into their potential toxic effects. We report here electrospray ionization mass spectrometry characterization of the interactions between these new halobenzoquinone disinfection byproducts and oligodeoxynucleotides. The study demonstrates that 2,6-dibromo-1,4-benzoquinone exhibits much stronger binding to single- and double-stranded oligodeoxynucleotides than chlorobenzoquinones. The binding affinity of 2,6-dibromo-1,4-benzoquinone to oligodeoxynucleotides is similar to that of ethidium bromide, a well-known intercalator and carcinogen. Tandem mass spectrometry characterization confirms the formation of 1:1 and 2:1 complexes of 2,6-dibromo-1,4-benzoquinone binding to oligodeoxynucleotides. Collision-induced dissociation analysis of these adducts demonstrates neutral loss and charge separation, suggesting that 2,6-dibromo-1,4-benzoquinone binds to oligodeoxynucleotides through partial intercalation and H-bonding modes. The three chlorobezoquinones also form 1:1 adducts with the oligodemmucleotides, but their binding to the oligodeoxynucleotides was much weaker compared to that of 2,6-dibromo-1,4-benzoquinone. The relative binding affinity of the studied disinfection byproducts to oligodeoxynucleotides is in the order of 2,6-dibromo-1,4-benzoquinone>>2,6-dichloro-1,4-benzoquinone > 2,6-dichloro-3methyl-1,4-benzoquinone similar to 2,3,6-trichloro-1,4-benzoquinone, indicating potential structural effects on the interactions of halobenzoquinones with oligodeoxynucleotides.
Zhao, Y.L., Qin, F., Boyd, J.M., Anichina, J. and Li, X.F. (2010) Characterization and Determination of Chloro- and Bromo-Benzoquinones as New Chlorination Disinfection Byproducts in Drinking Water. Analytical Chemistry 82(11), 4599-4605.   We report the characterization and determination of 2,6-dichloro-1,4-benzoquinone and three new disinfection byproducts (DBPs): 2,6-dichloro-3-methyl-1,4-benzoquinone, 2,3,6-trichloro-1,4-benzoquinone, and 2,6-dibromo-1,4-benzoquinone. These haloquinones are suspected bladder carcinogens and are likely produced during drinking water disinfection treatment. However, detection of these haloquinones is challenging, and consequently, they have not been characterized as DBPs until recently. We have developed an electrospray ionization tandem mass spectrometry technique based on our observation of unique ionization processes. These chloro- and bromo-quinones were ionized through a reduction step to form [M + H](-) under negative electrospray ionization. Tandem mass spectra and accurate mass measurements of these compounds showed major product ions, [M + H - HX](-), [M + H - HX - CO](-), [M + H - CO](-), and/or X- (where X represents Cl or Br). The addition of 0.25% formic acid to water samples was found to effectively stabilize the haloquinones in water and to improve the ionization for analysis. These improvements were rationalized from the estimates of pK(a) values (5.8-6.3) of these haloquinones. The method of tandem mass spectrometry detection, combined with sample preservation, solid phase extraction, and liquid chromatography separation, enabled the detection of haloquinones in chlorinated water samples collected from a drinking water treatment plant. The four haloquinones were detected only in drinking water after chlorination treatment, with concentrations ranging from 0.5 to 165 ng/L, but were not detectable in the untreated water. This method will be useful for future studies of occurrence, formation pathways, toxicity, and control of these new halogenated DBPs.


Other Compounds
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Broad LC/MS and ESI-MS Methods
Citation Notes Abstract
Zhang, X.R., J.W. Talley, B. Boggess, G.Y. Ding, and D. Birdsell. 2008. Fast selective detection of polar brominated disinfection byproducts in drinking water using precursor ion scans. Environmental Science & Technology 42:6598-6603.
MS/MS with precursor scans Brominated disinfection byproducts (DBPs), formed from the reaction of disinfectant(s) with natural organic matter and bromide in raw water, are generally more cytotoxic and genotoxic than their chlorinated analogues. Brominated DBPs have been intensively studied over the past 35 years, yet only a fraction of the total organic bromine formed during disinfection has been identified. A significant portion of the unaccounted total organic bromine may be attributed to polar/highly polar brominated HIPS. In this work, a method for fast selective detection of polar/highly polar brominated DBPs in drinking water was developed using negative ion electrospray ionization-triple quadrupole mass spectrometry (ESI-tqMS) by setting precursor ion scans of m/z 79 and 81. This method was conducted without liquid chromatography separation. The results demonstrate that the ESI-tqMS precursor ion scan is an effective tool for the selective detection of electrospray ionizable bromine-containing compounds in a complex mixture. Many polar/highly polar bromine-containing HIPS were tentatively found in two drinking water samples, and some of them may be new brominated DBPs that have not been previously reported. This method was also extended for the selective detection of polar bromine-containing compounds/contaminants in groundwater, surface water and wastewater.
Zhang, X.R., R.A. Minear, Y.B. Guo, C.J. Hwang, S.E. Barrett, K. Ikeda, Y. Shimizu, and S. Matsui. 2004. An Electrospray Ionization-Tandem Mass Spectrometry Method for Identifying Chlorinated Drinking Water Disinfection Byproducts. Water Research 38:3920-3930. optimizing MS/MS for Cl ion Identification of chlorinated drinking water disinfection byproducts (DBPs) was investigated by using electrospray ionization-mass spectrometry/mass spectrometry (ESI-MS/MS). Chlorine-containing compounds were found to form chloride ion fragments by MS/MS, which can be used as a 'fingerprint' for chlorinated DBPs. Instrumental parameters that affect the formation of chloride ions by ESI-MS/MS were examined, and appropriate conditions for use in finding specific structural information were evaluated. The results show that maximizing the formation of chloride ions by MS/MS required a relatively high collision energy and collision gas pressure; also, limiting the scan range to m/z 30-40 allowed improved sensitivity for detection; but obtaining structural information required the use of lower collision energies. The conditions obtained were demonstrated to be effective in identifying chlorinated DBPs in a standard sample with relatively low concentrations of each component and in a chlorinated humic substance sample. Sample pretreatment techniques including ultrafiltration and size exclusion chromatography appeared to be helpful for identifying highly polar or high molecular weight chlorine-containing DBPs by ESI-MS/MS.


Large DBP Studies with some Method Development
Citation Notes Abstract