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Trihalomethanes analysis in drinking water

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 Journal of Mass Spectrometry - Peer review proof only

Methods validation for THMs determination in drinking water

Journal: Journal of Mass Spectrometry

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Manuscript ID: JMS-06-0087.R2

Wiley - Manuscript type: Research Article

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Date Submitted by the
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Author:
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Complete List of Authors: Culea, Monica; Babes-Bolyai Univ, Biomedical Physics

Cozar, Onuc; Babes-Bolyai Univ, Biomedical Physics
Ristoiu, Dumitru; Babes-Bolyai Univ, Environmental Dept.

THMs, drinking water, SIM-GC-MS, validation of the method,,

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Keywords: liquid?liquid extraction, headspace extraction, purge and trap

extraction
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4 Methods validation for THMs determination in drinking water
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6 Monica Culea, Onuc Cozar and Dumitru Ristoiu
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Babes Bolyai University of Cluj-Napoca, M. Kogalniceanu str. 1., 400084 Cluj-Napoca, Romania, e-
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mail:mculea@phys.ubbcluj.ro
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12 Drinking water supplies has been made safer by chlorination. Proper chlorination kills the
13 majority of bacteria, viruses and parasites responsible for diseases such as typhoid fever,
14 cholera and dysentery. Unfortunately, there are several disinfection by-products (DBPs)
15 of drinking water of possible risk, such as trihalomethanes (THMs), haloacetic acids
16 (HAAs), bromate and chlorite. Volatile DBPs in drinking water could be determined by
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different analytical methods: liquid-liquid extraction gas chromatography-electron
capture detection (LLE-GC-ECD)1,9, LLE - gas chromatography-mass spectrometry
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20 (LLE-GC-MS)1,9, purge and trap (PT-GC-MS)3,6, headspace –GC-MS1, headspace- GC-
21 ECD2 or solid phase microextraction-gas chromatography-mass spectrometry (SPME-
22 GC-MS)4,5,8,10. These methods are applied for THMs (CHX3, X=halogen): chloroform
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(CHCl3), bromodichloromethane (CHBrCl2), dibromochloromethane (CHBr2Cl) and
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bromoform (CHBr3). In UE and in our country the maximum concentration level for
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26 TTHMs is still of 100 @g l-1. Applications are related although on the high concentrations
27 of THMs found in swimming pools9,12. Epidemiological studies have linked the
28 consumption of chlorinated surface waters to an increased risk of two major causes of
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29 human mortality, colorectal and bladder cancer13,14. Maternal exposure to THMs may be
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associated with fetal growth retardation, stillbirth, congenital malformations, cancer, and
more recently, with adverse reproductive outcomes.
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33 This study presents the development and comparison of some analytical methods for
34 THMs quantitation in drinking water. The techniques used for the determination of DBPs
35 in drinking water include water extraction procedure as liquid-liquid extraction (LLE),
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purge and trap (PT) or headspace followed by gas chromatographic (GC) separation and
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38 mass spectrometric (MS) detection. The development of most sensitive methods for
39 THMs quantitation are useful in the kinetics studies for the optimization of drinking
40 water treatment, for monitoring and maintaining the lowest values of THMs into the
41 drinking water.
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42 LLE-GC-MS method. Standard THMs, active charcoal and solvents were obtained
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from Merck (Darmstadt, Germany). Halothane (2-bromo-2chloro-1,1,1-trifluoroethane)
45 was obtaine from Laboratoire Belamont (Paris, France). Standard solutions containing
46 different known amounts of THMs and the same quantity of the internal standard in
47 distilled water were prepared. Halothane was used as internal standard. 0.5 g sodium
48 sulphate anhydrous and 0.5 ml methyl tert-butyl ether (MTBE) was added to 7 ml water
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(drinking water or standard solutions) in a 10 ml glass capped vial (a modified EPA
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51 Method 551.1). After mixing 1 min, the vial was centrifuged 2 min, and 1 @l of the ether
52 phase was injected into the GC.
53 Purge and trap-GC-MS method. The purge and trap concentrator was active charcoal.
54 100 ml standard solutions or drinking water warmed at 30oC was extracted with a 12
55 ml/min He, 20 min and followed by desorption at 120oC for 3 min or by mixing 1 min the
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charcoal in a capped vial with 1ml methyl-tert-butyl ether (MTBE). 100 @g of halothane,
58 the internal standard, was added to each sample and 3 @l were injected into the GC.
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Headspace-GC-MS method. Standard solutions or drinking water (10ml) was placed
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5 in 20 ml headspace vials and 10@g halothane, the internal standard, was added. The vials
6 were placed in a send bath at 60oC for 45 min. Then 500 @l of the gas phase was injected
7 into the GC with a gas syringe.
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9 Apparatus. A Trace DSQ ThermoFinnigan quadruple mass spectrometer coupled with
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a Trace GC was used. A Rtx-5MS capillary column, 30 m length x 0.25 mm, 0.25 @m
12 film thickness, by using two different temperature programs: (1) from 31oC (1 min), then
13 increased to 40oC at 1oC/min and then with 80oC/min to 200oC and (2) from 31oC, 1 min,
14 1oC/min to 33oC, 100oC/min to 200oC, followed by MS detection in the selected ion
15 monitoring (SIM) mode. In the SIM mode the following important ions have been used:
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m/z 83, 85, 118, 120 for chloroform, m/z 83, 85, 127, 129 for dichlorobromomethane,
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18 m/z 127, 129 for dibromochloromethane, m/z 173, 175, 252 for bromoform and m/z 117
and 198 for the internal standard (halothane). The method was validated in different
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20 ranges: 0 – 20 @gl-1 , 0 – 80 @gl-1 0 – 400 @gl-1 and linearity, precision, accuracy and limit
21 of detection parameters have been studied.
22 The methods validation. LLE-GC-MS: Aliquot samples containing 20, 40, 60, 80,
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100, 200, 300 and 400 @gl-1 of the four THMs were extracted by LLE as described before
and 100 @g of halothane, the internal standard, was added at each sample. The regression
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26 curves obtained by LLE-GC-MS method, in the range 0-80 @gl-1 and respectively, 0-400
27 @gl-1 (in brackets) were: y=0.0026x+0.0301, (y=0.0032x+0.0222), r=0.991 (0.960) for
28 chloroform, y=0.0027x+0.0061, (y=0.0029x+0.0173), r=0.970 (0.970) for
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dibromodichloromethane, y=0.0023x+0.0066, (y=0.0023x+0.0206), r=0.960 (0.960) for
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31 dibromochloromethane and y=0.0014x+0.0058, (y=0.0016x+0.0122), r=0.960 (0.960) for
bromoform. In brackets are presented the regression curves for the range 0-400@gl-1. The
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33 regression curves were used to calculate the THMs, after adding the same quantity of
34 internal standard to the sample and by using the methods described before. Precision
35 studied for the aliquot samples of 40 and 80 @gl-1 showed R.S.D. values between 13.1 –
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26.4 % and respectively between 10.7-21.2%. The accuracy R.S.D. calculated were
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38 between 0.9-11.3% for the sample of 40 @gl-1 (n=3) and between 5.8-10.6% for the
39 sample of 80 @gl-1 (n=4). Table 1 presents the results obtained for precision and accuracy.
40 A limit of detection lower than 0.1 @gl-1 was obtained for the THMs studied (0,02 @gl-1
41 (CHCl3), 0,05@gl-1 (CHCl2Br), 0,2 @gl-1 (CHClBr2) and 0,1 @gl-1 (CHBr3), signal/noise
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10/1. The limit of quantitation was 1 @gl-1, the RSD obtained being between 0.1-28%.
44 PT-GC-MS: Aliquot samples containing 20, 40, 60, 80 @gl-1 of the four THMs were
45 extracted by purge and trap extraction and 100 @g of halothane, the internal standard, was
46 added at each sample. The regression curves obtained by PT-GC-MS method, in the
47 range 0-80 @gl-1 were y=0.0029x+0.038, r=0.930 for chloroform, y=0.00008x+0.0003,
48 r=0.880 for dibromodichloromethane, y=0.00004x-0.0005, r=0.890 for
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50 dibromochloromethane and y=0.00001x-0.00001, r=0.840 for bromoform. The regression
51 curves were used for the calculation of the THMs, after the addition of the same quantity
52 of internal standard to the sample. Further work is needed in PT-GC-MS method for
53 better linearity values, using longer time of extraction and higher gas flow. Precision
54 studied for the aliquot samples of 20 @gl-1 showed R.S.D. values between 2.63 – 30.35 %.
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The limit of detection of 1 @gl-1 was obtained for the THMs studied, depending of the
57 helium flow, time and desorption procedure. The following VOCs, separated and
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identified in a drinking water sample (tap water) analysed by purge and trap GC-MS, in
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5 scan mode, are the highest among 40 identified compounds: butyl formiate, 1,1-
6 diethoxyetane, toluene, trimethylcyclobutane, ethyl benzene, p-xylene, cyclohexanone,
7 1,2dichlorbenzene, dibutylformamide, dodecanoic acid, undecylbenzoate,
8 dibutylphtalate. The identified compounds imposed the selection of halothane as internal
9 standard instead of benzene or chlorbenzene, VOCs identified into the drinking water.
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Headspace-GC-MS: Aliquot samples containing 20, 40, 60, 80,100, 200, 300 @gl-1 of
12 each of the four THMs and 100@g of halothane, the internal standard, added at each
13 sample, were extracted and analyzed by headspace-GC-MS method described before, The
14 regression curves obtained by LLE-GC-MS method, in the range 0-80 @gl-1 (0-300 @gl-1)
15 were y=0.0037x+0.0031, (y=0.0046x+0.036), r=0.980 (0.997) for chloroform,
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y=0.0024x-0.0015, (y=0.0029x-0.019), r=0.990 (r=0.980) for dibromodichloromethane,
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18 y=0.0008x+0.0021, (y=0.001x-0.007), r=0.970 (r=0.980) for dibromochloromethane and
y=0.0003x+0.001, (y=0.0003x-0.0008), r=0.980 (r=0.970) for bromoform. In brackets
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20 are presented the regression curves for the range 0-300 @gl-1. Precision studied for the
21 aliquot samples of 40 and 60 @gl-1 showed R.S.D. values between 14.97 – 31.95 % and
22 respectively between 17.93-25.49%. The accuracy R.S.D. values were between 5.07-
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10.36% for the sample of 40 @gl-1 and between 6.00-32.78% for the sample of 60 @gl-1.
Table 1 presents the results obtained for precision and accuracy. A limit of detection
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26 lower than 0.1 @gl-1 was measured, signal/noise ratio 10, RSD between 1- 18%.
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28 Table 1 Precision and accuracy of the headspace-GC-MS method for THMs
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Compound Concentration(@gl ) Comp/IS Precision Accuracy
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34 n Added Measured SD RSD(%) RSD(%)
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36 CHCl3 3 40 39.06 0.14 0.02 14.97 2.28
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38 CH3Br 3 40 35.86 0.08 0.02 22.29 10.36
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CH2Br2 3 40 37.97 0.03 0.01 27.87 5.07
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CHBr3 3 40 36.17 0.01 0.003 31.95 9.56

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CHCl3 4 60 63.60 0.26 0.05 17.93 6.00
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CH3Br 4 60 68.48 0.18 0.03 18.59 14.13
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CH2Br2 4 60 79.67 0.07 0.02 21.55 32.78
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CHBr3 4 60 76.02 0.02 0.01 25.49 26.69
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The total trihalomethanes (TTHM) mean value (@gl-1) in our laboratory tap water in
55 different months was 40.99 ± 17.4, the highest value being measured in summer time.
56 The THMs separation chromatogram in the rapid temperature programs used is presented
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in Fig. 1, headspace extraction method. The low temperature of start (31oC) was needed
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5 especially for halothane and chloroform separation.
6 The comparison of the three analytical methods showed preference for headspace
7 extraction method because of sensitivity, simplicity and also for the possibilities to be
8 used in automatic extraction (autosamplers, robot injectors). PT-GC-MS is also good for
9 automatic extraction8, but should be improved by optimizing the analytical parameters as
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higher helium flow, higher time of sampling and thermal desorption. Further work is
12 needed in PT-GC-MS method for better linearity values. Purge and trap is preferred for
13 trace level pollutants identification, when longer extraction time is used. The LLE-GC-
14 MS is simple and rapid, but the use of methyl tert-butyl ether solvent is an disadvantage
15 when this solvent is of interest in some waters4,5. A disadvantage of the liquid-liquid
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extraction technique is also the inability to concentrate the extract because of the
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18 potential for the loss of the volatile compounds. Recovery was found between 70-90% in
the methods studied. The selection of a proper internal standard, not found in the drinking
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20 water, is also important because recovery become not very important and the extraction
21 duration could be rapid.
22 The development of THMs analytical methods will have an impact in optimization of
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the current treatment practice, the improvement of drinking water treatment and quality
to reduce DBPs contamination of water. The optimization of chlorine or ozone doses for
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26 disinfection processes correlated with frequent bacterial analysis of drinking water will
27 permit the assessment of the risks caused by THM contamination of drinking water in our
28 country. The major impact will be the improvement of the quality of drinking water and
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of the health of the consumers, by the reduction of THM concentrations in drinking
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31 water. Some alternative disinfectants as coagulation, sedimentation, use of
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33 to the removal of THM precursors prior to disinfection.
34 Acknowledgements
35 This study was funded by the Swiss Agency for Development and Cooperation (SDC) in
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the framework of the Swiss–Romanian Cooperation Project ESTROM (Environmental
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38 Science and Technology in Romania).
39 References
40 1. D. Nikolaou , T. D. Lekkas, S. K. Golfinopoulos,M. N. Kostopoulou, Application of
41 different analytical methods for determination of volatile chlorination by-products in
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drinking water Talanta 2002; 56: 717.
44 2. Gellard H, Von Gunten U, Chlorination of natural organic matter: kinetics of
45 chlorination and of THM formation Watter Res 2002; 36: 65.
46 3. Zoccolillo L, Amendola L, Cafaro C, Insogna S., Improved analysis of volatile
47 halogenated hydrocarbons in water by purge-and-trap with gas chromatography and
48 mass spectrometric detection, J Chromatogr A. 2005, 10:181.
49
50 4. Bonin MA, Silva LK, Smith MM, Ashley DL, Blount BC, Measurement of
51 trihalomethanes and methyl tert-butyl ether in whole blood using gas chromatography
52 with high-resolution mass spectrometry, J Anal Toxicol. 2005;2981.
53 5. Cardinali FL, Ashley DL, Morrow JC, Moll DM, Blount BC, Measurement of
54 trihalomethanes and methyl tertiary-butyl ether in tap water using solid-phase
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microextraction GC-MS, J Chromatogr Sci. 2004;42:200.
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6. Ohmichi K, Ohmichi M, Machida K., Volatile organic compounds of the tap water in
4
5 the Watarase, Tone and Edo River system, Nippon Eiseigaku Zasshi. 2004;59:45
6 7. Richardson SD, Thruston AD Jr, Rav-Acha C, Groisman L, Popilevsky I, Juraev O,
7 Glezer V, McKague AB, Plewa MJ, Wagner ED, Tribromopyrrole, brominated acids,
8 and other disinfection byproducts produced by disinfection of drinking water rich in
9 bromide, Environ Sci Technol. 2003; 1:3782.
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8. Chen TC, Her GR, On-line monitoring of trihalomethanes in drinking water using
12 continuous-flow purge and cryofocusing gas chromatography-mass spectrometry, J
13 Chromatogr A. 2001; 24:229
14 9. Golfinopoulos SK, Nikolaou AD, Disinfection by-products and volatile organic
15 compounds in the water supply system in Athens, Greece, J Environ Sci Health A Tox
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Hazard Subst Environ Eng. 2001;36:483
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18 10. Stack MA, Fitzgerald G, O'Connell S, James KJ, Measurement of trihalomethanes in
potable and recreational waters using solid phase micro extraction with gas
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20 chromatography-mass spectrometry, Chemosphere. 2000;41:1821.
21 11. Chang CC, Her GR, On-line monitoring trihalomethanes in chlorinated water by
22 membrane introduction-fast gas chromatography mass-spectrometry J Chromatogr A.
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2000; 29:169.
12. Chu H, Nieuwenhuijsen M J, Distribution and determinants of trihalomethane
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26 concentrations in indoor swimming pools, Occup. Environ. Med. 2002;59:243.
27 13. Geter DR, Chang LW, Hanley NM, Ross MK, Analysis of in vivo and in vitro DNA
28 strand breaks from trihalomethane exposure, Journal of Carcinogenesis 2004; 3: 2.
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14. Keller HL, Borger DC, Willet LB, Uptake and excretion of organochlorine
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31 compounds in neonatal calves, J. Anim. Sci. 2001; 79:155.
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34 Corresponding author:
35 Dr. Monica Culea
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Babes-Bolyai University Cluj-Napoca
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38 Dept. Biomedical Physics,
39 Kogalniceanu str. 1, 400084 Cluj-Napoca,
40 ROMANIA
41 Tel. +40-264-504300/5152
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Fax.+40-264-595355
44 e-mail:mculea@phys.ubbcluj.ro; culea_monica@yahoo.com
45 Running title:
46 THMs determination in drinking water
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48 Number of text pages:Text 5 pag, figures 1, tables 1
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9 RT: 0.00 - 5.70
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Figure 1 SIM-GC-MS chromatograms of a standard samples of 1 µgl-1 analyzed by headspace-
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26 GC-MS (fast temperature program: 31oC, 1min, 1oC/min to 33oC, 100oC/min to 200oC):
27 halothane, 2.38 min (IS), chloroform, 2.90 min, dichlorobromomethane, 3.79 in,
28 chlorodibromomethane, 4.44 min, and bromoform, 4.90 min
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