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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

Postal Subscription Code 80-973

2018 Impact Factor: 3.883

Front Envir Sci Eng    2012, Vol. 6 Issue (6) : 770-777    https://doi.org/10.1007/s11783-012-0412-0
RESEARCH ARTICLE
Detecting N-nitrosamines in water treatment plants and distribution systems in China using ultra-performance liquid chromatography-tandem mass spectrometry
Chengkun WANG, Xiaojian ZHANG, Jun WANG, Chao CHEN()
School of Environment, Tsinghua University, Beijing 100084, China
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Abstract

N-nitrosodimethylamine (NDMA) and several other N-nitrosamines have been detected as disinfection by-products in drinking waters in many countries around the world. An ultra-performance liquid chromatography-tandem mass spectrometry method with solid phase extraction sample preparation was developed to study the occurrence of N-nitrosamines in several water treatment plants and distribution systems in China. Isotope labeled N-nitrosodi-n-propylamine-d14 (NDPA-d14) was selected as the internal standard for quantification. The solid phase extraction procedures including pH, enrichment process and MS/MS parameters including capillary voltage, cone gas flow, cone voltage, collision energy were optimized to give average recoveries of 26% to 112% for nine N-nitrosamine species. The instrument detection limits were estimated to range from 0.5 to 5 μg·L-1 for the nine N-nitrosamine species. NDMA and several other N-nitrosamines were found at fairly high concentrations in several water treatment plants and distribution systems. NDMA was found in all locations, and the highest concentrations in cities B, G, T, and W were 3.0, 35.7, 21.3, and 19.7 ng·L-1, respectively. A wide range of N-nitrosamines concentrations and species were observed in different locations. Higher concentrations of N-nitrosamines were detected in distribution systems that were further away from the treatment plants, suggesting that the contact time between the residual disinfectant and natural organic matter may play an important role in the formation of these compounds.

Keywords N-nitrosamines      water treatment plant      distribution system      ultra-performance liquid chromatography-tandem mass spectrometry     
Corresponding Author(s): CHEN Chao,Email:chen_water@tsinghua.edu.cn   
Issue Date: 01 December 2012
 Cite this article:   
Chengkun WANG,Xiaojian ZHANG,Jun WANG, et al. Detecting N-nitrosamines in water treatment plants and distribution systems in China using ultra-performance liquid chromatography-tandem mass spectrometry[J]. Front Envir Sci Eng, 2012, 6(6): 770-777.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-012-0412-0
https://academic.hep.com.cn/fese/EN/Y2012/V6/I6/770
N-nitrosamineprecursor ion [M+ H]+product ions [M+ H]+(qualify, confirm)cone voltage /Vcollision energy/eVIDLs/(μg·L-1), (RSD/%, n = 3)
NDMA75(43, 58)25185 (9.4)
NMEA89(61, 43)22131 (2.0)
NPYR101(55, 83)22201 (11)
NDEA103(75, 47)28155 (3.0)
NPIP115(69, 41)22202 (6.4)
NMOR117(87, 45)22142 (9.0)
NDPA131(89, 43)22185 (2.2)
NDPA-d14145(96, 50)2215NA
NDBA159(103, 57)22151 (6.2)
NDPhA199(169, 66)22180.5 (3.6)
Tab.1  Multiple reactions monitoring transitions, MS/MS parameters, and instrument detection limits for nine nitrosamines
Fig.1  Typical LC-MS/MS chromatograms for nine nitrosamines (50 μg·L) showing the retention time for each nitrosamine
N-nitrosaminesrecovery±RSD /%, (100 ng·L-1, n = 3)
pH= 3pH= 5pH= 7pH= 9
NDMA84±1078±1585±1496±8
NMEA84±993±370±3793±7
NPYR71±465±857±1563±1
NMOR86±1575±669±1070±1
NDEA68±585±21NA64±0
Npip64±862±852±854±14
NDPA64±569±13NA67±21
NDBA48±241±149±532±16
NDPhANA31±8NA26±10
Tab.2  Recovery of each nitrosamine at different pH values (25°C)
N-nitrosaminesrecovery±RSD /%, (100 ng·L-1, n = 3, pH= 9)
spiked blanksspiked matrix samples
NDMA96±886±12
NMEA93±7112±15
NPYR63±178±6
NMOR70±1109±4
NDEA64±060±9
NPIP54±1486±14
NDPA67±2154±12
NDBA32±1666±7
NDPhA26±1034±11
Tab.3  Recovery of spiked matrix and blank samples
locationconcentrations /(ng·L-1)±SD
NDMANMORNPYRNPIPNMEANDPANDPhA
City TSWn.d.3.5±1.4n.d.n.d.n.d.n.d.n.d.
SE6.3±1.02.2±0.6n.d.n.d.n.d.n.d.n.d.
FE3.9±1.04.8±1.2n.d.n.d.n.d.n.d.n.d.
CE12.1±4.42.5±1.12.4±0.7n.d.n.d.n.d.n.d.
DS110.1±2.710.1±2.05.4±0.7n.d.n.d.n.d.n.d.
DS221.3±3.05.9±1.46.3±1.6n.d.n.d.n.d.n.d.
DS317.7±3.012.1±4.03.4±1.0n.d.n.d.n.d.n.d.
City BSWn.d.n.d.n.d.n.d.n.d.n.d.n.d.
DS11.0n.d.7.05.0n.d.n.d.6.0
DS2n.d.n.d.6.010.0n.d.n.d.1.0
DS33.0n.d.13.023.0n.d.n.d.n.d.
City GSWndn.d.n.d.n.d.n.d.n.d.n.d.
CE21.1±2.5n.d.n.d.4.7±0.24.5±0.335.6±0.4n.d.
DS123.4±4.7n.d.n.d.7.1±0.53.1±0.559.2±6.1n.d.
DS222.4±7.2n.d.n.d.7.5±0.63.0±0.854.3±5.4n.d.
DS335.7±2.5n.d.n.d.4.7±0.42.9±0.379.4±3.7n.d.
CityWSWn.d.n.d.n.d.4.1±0.2n.d.n.d.n.d.
SEn.d.n.d.n.d.10.9±0.1n.d.n.d.n.d.
CE12.3±3.5n.d.n.d.12.2±1.4n.d.n.d.n.d.
DS119.7±5.4n.d.n.d.20.9±1.9n.d.n.d.n.d.
Tab.4  Concentrations of nitrosamines in drinking water distribution system ( = 3, n.d., not detected, chloramine used as disinfectant in all plants). SW is source water; SE is sedimentation effluent; FE is filtration effluent; CE is clear effluent; and DS is distribution system
Fig.2  Typical LC-MS/MS chromatograms for nine nitrosamines (50 μg·L) showing the retention time for each -nitrosamines
Fig.3  Average concentrations of NDMA detected in distribution systems and selected water quality parameters in raw water from City T, City G, and City W
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