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1.
Microbiol Spectr ; 10(3): e0114021, 2022 06 29.
Article in English | MEDLINE | ID: mdl-35438512

ABSTRACT

The distribution of pathogenic Legionella in the environmental soil and water of China has not been documented yet. In this study, Legionella was detected in 129 of 575 water (22.43%) and 41 of 442 soil samples (9.28%) by culture. Twelve Legionella species were identified, of which 11 were disease-associated. Of the Legionella-positive samples, 109 of 129 (84.50%) water and 29 of 41 (70.73%) soil were positive for L. pneumophila, which accounted for about 75% of Legionella isolates in both water and soil, suggesting L. pneumophila was the most frequent species. Soil showed a higher diversity of Legionella spp. as compared with water (0.6279 versus 0.4493). In contrast, serogroup (sg) 1 was more prevalent among L. pneumophila isolates from water than from soil (26.66% versus 12.21%). Moreover, many disease-associated sequence types (STs) of L. pneumophila were found in China. Intragenic recombination was acting on L. pneumophila from both water and soil. Phylogeny, population structure, and molecular evolution analyses revealed a probable existence of L. pneumophila isolates with a special genetic background that is more adaptable to soil or water sources and a small proportion of genetic difference between water and soil isolates. The detection of viable, clinically relevant Legionella demonstrates soil as another source for harboring and dissemination of pathogenic Legionella bacteria in China. Future research should assess the implication in public health with the presence of Legionella in the soil and illustrate the genetic and pathogenicity difference of Legionella between water and soil, particularly the most prevalent L. pneumophila. IMPORTANCE Pathogenic Legionella spp. is the causative agent of Legionnaires' disease (LD), and L. pneumophila is the most common one. Most studies have focused on L. pneumophila from water and clinical samples. However, the soil is another important reservoir for this bacterium, and the distribution of Legionella spp. in water and soil sources has not been compared and documented in China yet. Discovering the distribution of Legionella spp. and L. pneumophila in the two environments may help a deep understanding of the pathogenesis and molecular evolution of the bacterium. Our research systematically uncovered the distributions of Legionella spp. in different regions and sources (e.g., water and soil) of China. Moreover, phylogeny, population structure, and molecular evolution study revealed the possible existence of L. pneumophila with a special genetic background that is more adaptable to soil or water sources, and genetic difference may exist.


Subject(s)
Legionella pneumophila , Legionella , Legionnaires' Disease , Humans , Legionella/genetics , Legionnaires' Disease/epidemiology , Soil , Water , Water Microbiology
2.
Clin Immunol ; 237: 108989, 2022 04.
Article in English | MEDLINE | ID: mdl-35358679

ABSTRACT

Primary Sjögren's Disease (pSjD) is considered a B cell-mediated disease. Toll-like receptor 10 (TLR10) is highly expressed in human B cells, indicating that TLR10 probably plays a vital role in pSjD. We examined TLR10 expression in peripheral B subsets of pSjD patients and analyzed their association with disease activity. We observed that TLR10 expression in total, naïve, memory, and switched memory B cells was significantly increased in low-activity pSjD patients as compared with healthy controls and high-activity patients. TLR10 expression in the above mentioned B subsets (except naïve B) was negatively correlated with serum levels of anti-SSA antibody and BAFF, respectively. Moreover, a higher proportion of high-activity pSjD patients was observed in TLR10 low- than high-expressed patients. Our study concluded that TLR10 expression in CD19+ B and memory B was negatively correlated with pSjD disease activity, suggesting that TLR10 might take part in the progression of pSjD.


Subject(s)
B-Lymphocytes , Sjogren's Syndrome , Toll-Like Receptor 10 , Antigens, CD19/metabolism , Humans , Lymphocyte Count , Sjogren's Syndrome/pathology , Toll-Like Receptor 10/metabolism
3.
PeerJ ; 9: e12000, 2021.
Article in English | MEDLINE | ID: mdl-34458026

ABSTRACT

Effector proteins translocated by the Dot/Icm type IV secretion system determine the virulence of Legionella pneumophila (L. pneumophila). Among these effectors, members of the SidE family (SidEs) regulate several cellular processes through a unique phosphoribosyl ubiquitination mechanism mediated by another effector, SidJ. Host-cell calmodulin (CaM) activates SidJ to glutamylate the SidEs of ubiquitin (Ub) ligases and to make a balanced Ub ligase activity. Given the central role of SidJ in this regulatory process, studying the nature of evolution of sidJ is important to understand the virulence of L. pneumophila and the interaction between the bacteria and its hosts. By studying sidJ from a large number of L. pneumophila strains and using various molecular evolution algorithms, we demonstrated that intragenic recombination drove the evolution of sidJ and contributed to sidJ diversification. Additionally, we showed that four codons of sidJ which are located in the N-terminal (NTD) (codons 58 and 200) and C-terminal (CTD) (codons 868 and 869) domains, but not in the kinase domain (KD) had been subjected to strong positive selection pressure, and variable mutation profiles of these codons were identified. Protein structural modeling of SidJ provided possible explanations for these mutations. Codons 868 and 869 mutations might engage in regulating the interactions of SidJ with CaM through hydrogen bonds and affect the CaM docking to SidJ. Mutation in codon 58 of SidJ might affect the distribution of main-chain atoms that are associated with the interaction with CaM. In contrast, mutations in codon 200 might influence the α-helix stability in the NTD. These mutations might be important to balance Ub ligase activity for different L. pneumophila hosts. This study first reported that intragenic recombination and positive Darwinian selection both shaped the genetic plasticity of sidJ, contributing to a deeper understanding of the adaptive mechanisms of this intracellular bacterium to different hosts.

4.
Environ Sci Technol ; 52(5): 2898-2908, 2018 03 06.
Article in English | MEDLINE | ID: mdl-29420883

ABSTRACT

Halobenzoquinones (HBQs) are a class of emerging disinfection byproducts. Chronic exposure to chlorinated drinking water is potentially associated with an increased risk of human bladder cancer. HBQ-induced cytotoxicity involves depletion of cellular glutathione (GSH), but the underlying mechanism remains unclear. Here we used ultrahigh performance liquid chromatography-high resolution mass spectrometry and electron paramagnetic resonance spectroscopy to study interactions between HBQs and GSH and found that HBQs can directly react with GSH, forming various glutathionyl conjugates (HBQ-SG) in both aqueous solution and HepG2 cells. We found that the formation of HBQ-SG varies with the initial molar ratio of GSH to HBQ in reaction mixtures. Higher molar ratios of GSH to HBQ facilitate the conjugation of more GSH molecules to an HBQ molecule. We deduced the reaction mechanism between GSH and HBQs, which involves redox cycling-induced formation of halosemiquinone (HSQ) free radicals and glutathione disulfide, Michael addition, as well as nucleophilic substitution. The proposed reaction rates are in the following order: formation of HSQ radicals > substitution of bromine by GSH > Michael addition of GSH on the benzoquinone ring > substitution of chlorine by GSH > substitution of the methyl group by GSH. The conjugates identified in HBQ-treated HepG2 cells were the same as those found in aqueous solution containing a 5:1 ratio of GSH:HBQs.


Subject(s)
Drinking Water , Glutathione , Disinfection , Hep G2 Cells , Humans , Tandem Mass Spectrometry
5.
Environ Sci Technol ; 49(16): 9898-904, 2015 Aug 18.
Article in English | MEDLINE | ID: mdl-26196663

ABSTRACT

Halobenzoquinones (HBQs) widely occur in drinking water treatment plant (DWTP) effluents; however, HBQ precursors and their removal by treatments remain unclear. Thus, we have investigated HBQ precursors in plant influents and their removal by each treatment before chlorination in nine DWTPs. The levels of HBQ precursors were determined using formation potential (FP) tests for 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-dibromo-1,4-benzoquinone (DBBQ). HBQ precursors were present in all plant influents. DCBQ precursors were the most abundant (DCBQ FP up to 205 ng/L). Coagulation removed dissolved organic carbon (DOC) (up to 56%) and HBQ precursors (up to 39% for DCBQ). The level of removal of DOC was significantly greater than the level of removal of HBQ FP, suggesting that organic matter removed by coagulation had a high proportion of non-HBQ-precursor material. Granular activated carbon (GAC) decreased the level of HBQ FPs by 10-20%, where DOC removal was only 0.2-4.7%, suggesting that the GAC was not in the adsorption mode and biodegradation of HBQ precursors may have been occurring. Ozonation destroyed/transformed HBQ FPs by 10-30%, whereas anthracite/sand filtration and UV irradiation appeared to have no impact. The results demonstrated that the combined treatments did not substantially reduce HBQ precursor levels in water.


Subject(s)
Benzoquinones/isolation & purification , Drinking Water/chemistry , Water Pollutants, Chemical/isolation & purification , Water Purification/methods , Benzoquinones/chemistry , Carbon/analysis , Charcoal/chemistry , Filtration , Ozone/chemistry , Ultraviolet Rays , Waste Disposal, Fluid , Water Quality
6.
Environ Sci Technol ; 49(1): 459-66, 2015 Jan 06.
Article in English | MEDLINE | ID: mdl-25471701

ABSTRACT

We report here that tobacco-specific nitrosamines (TSNAs) are produced from specific tobacco alkaloids during water chloramination. To identify the specific precursors for the formation of specific TSNAs in drinking water, we have developed a solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method for simultaneous determination of five TSNAs and three tobacco alkaloids. Using this method, we detected nicotine (NIC) at 15.1 ng/L in a source water. Chloramination of this source water resulted in the formation of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) (0.05 ng/L) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) (0.2 ng/L) along with the reduction of NIC to 1.1 ng/L, suggesting that NNK and NNAL were formed from NIC. To confirm that tobacco alkaloids are the precursors of TSNAs, we chloraminated water-leaching samples of tobacco from three brands of cigarettes and found that the formation of TSNAs coincides with the reduction of the alkaloids. Chloramination of individual alkaloids confirms that NNK and NNAL are produced from NIC, N-nitrosonornicotine (NNN) from nornicotine (NOR), and N-nitrosoanabasine (NAB) from anabasine (ANA). Furthermore, we have identified specific intermediates of these reactions and proposed potential pathways of formation of TSNAs from specific alkaloids. These results confirm that NNK and NNAL are the disinfection byproducts (DBPs) resulting from NIC in raw water.


Subject(s)
Chloramines/chemistry , Drinking Water/chemistry , Nicotiana/chemistry , Nitrosamines/analysis , Pyridines/analysis , Alkaloids/chemistry , Chromatography, Liquid/methods , Halogenation , Mass Spectrometry , Nicotine/analogs & derivatives , Nicotine/chemistry , Nitrosamines/chemical synthesis , Pyridines/chemical synthesis , Solid Phase Extraction/methods , Tandem Mass Spectrometry/methods , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemical synthesis
7.
Anal Chem ; 87(2): 1330-6, 2015 Jan 20.
Article in English | MEDLINE | ID: mdl-25526384

ABSTRACT

N-Nitrosamines, probable human carcinogens, are a group of disinfection byproducts under consideration for drinking water regulation. Currently, no method can determine trace levels of alkyl and tobacco-specific nitrosamines (TSNAs) of varying physical and chemical properties in water by a single analysis. To tackle this difficulty, we developed a single solid-phase extraction (SPE) method with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for the determination of 14 nitrosamines of health concern with widely differing properties. We made a cartridge composed of a vinyl/divinylbenzene polymer that efficiently concentrated the 14 nitrosamines in 100 mL of water (in contrast to 500 mL in other methods). This single SPE-HPLC-MS/MS technique provided calculated method detection limits of 0.01-2.7 ng/L and recoveries of 53-93% for the 14 nitrosamines. We have successfully demonstrated that this method can determine the presence or absence of the 14 nitrosamines in drinking water systems (eight were evaluated in Canada and the U.S.), with occurrence similar to that in other surveys. N-Nitrosodimethylamine (NDMA), N-nitrosodiphenylamine, and the TSNA 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol were identified and quantified in authentic drinking water. Formation potential (FP) tests demonstrated that NDMA and TSNA precursors were present in (1) water samples in which tobacco was leached and (2) wastewater-impacted drinking water. Our results showed that prechlorination or ozonation destroyed most of the nitrosamine precursors in water. Our new single method determination of alkylnitrosamines and TSNAs significantly reduced the time and resource demands of analysis and will enable other studies to more efficiently study precursor sources, formation mechanisms, and removal techniques. It will be useful for human exposure and health risk assessments of nitrosamines in drinking water.


Subject(s)
Carcinogens/analysis , Drinking Water/analysis , Nitrosamines/analysis , Solid Phase Extraction/methods , Tandem Mass Spectrometry/methods , Water Pollutants, Chemical/analysis , Chromatography, High Pressure Liquid/methods , Humans , Limit of Detection , Smoking , Nicotiana/chemistry
8.
PLoS One ; 9(9): e106596, 2014.
Article in English | MEDLINE | ID: mdl-25210744

ABSTRACT

BACKGROUND: We investigated the relationships between the ALOX5AP gene rs10507391 and rs4769874 polymorphisms, serum levels of leukotriene (LT) B4, and risk of acute coronary syndrome (ACS). METHODS: A total of 709 participants, comprising 508 ACS patients (ACS group) and 201 noncoronary artery disease patients with chest pain (control group) were recruited from the Han population of the Changwu region in China. Two polymorphic loci were genotyped using polymerase chain reaction and restriction fragment length polymorphism analysis. Serum LTB4 level was determined by enzyme-linked immunosorbent assay. RESULTS: Serum LTB4 levels were significantly higher (P<0.001) in the ACS group (median/interquartile range, 470.27/316.32 pg/ml) than in the control group (233.05/226.82 pg/ml). No statistical differences were observed between genotype, allele and haplotype frequencies for the tested loci in either the ACS group or the control group, even after adjustments were made for conventional risk factors by multivariate logistic regression. This suggests there is no association between the ALOX5AP rs10507391 and rs4769874 polymorphisms and ACS risk. Elevated serum LTB4 level was closely linked to ACS risk, and may be independent of traditional risk factors as a risk factor for ACS (P<0.001). There was no significant association between serum LTB4 levels and the two variants in either the ACS group or the control group. CONCLUSIONS: Rs10507391, rs4769874 and its haplotypes in ALOX5AP are unrelated to ACS risk in the Chinese Han population of Changwu, but elevated serum LTB4 level is strongly associated with ACS risk. Serum LTB4 level is not subject to the influence of either the rs10507391, rs4769874 or the haplotype.


Subject(s)
5-Lipoxygenase-Activating Proteins/genetics , Acute Coronary Syndrome/genetics , Genetic Predisposition to Disease , Leukotriene B4/genetics , Acute Coronary Syndrome/pathology , Aged , Alleles , Asian People , China , Female , Genetic Association Studies , Haplotypes , Humans , Male , Middle Aged , Polymorphism, Single Nucleotide
9.
J Chromatogr A ; 1359: 156-61, 2014 Sep 12.
Article in English | MEDLINE | ID: mdl-25085815

ABSTRACT

Acesulfame (ACE) and sucralose (SUC) have become recognized as ideal domestic wastewater contamination indicators. Liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) analysis is commonly used; however, the sensitivity of SUC is more than two orders of magnitude lower than that of ACE, limiting the routine monitoring of SUC. To address this issue, we examined the ESI behavior of both ACE and SUC under various conditions. ACE is ionic in aqueous solution and efficiently produces simple [M-H](-) ions, but SUC produces multiple adduct ions, limiting its sensitivity. The formic acid (FA) adducts of SUC [M+HCOO](-) are sensitively and reproducibly generated under the LC-MS conditions. When [M+HCOO](-) is used as the precursor ion for SUC detection, the sensitivity increases approximately 20-fold compared to when [M-H](-) is the precursor ion. To further improve the limit of detection (LOD), we integrated the large volume injection approach (500µL injection) with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), which reduced the method detection limit (MDL) to 0.2ng/L for ACE and 5ng/L for SUC. To demonstrate the applicability of this method, we analyzed 100 well water samples collected in Alberta. ACE was detected in 24 wells at concentrations of 1-1534ng/L and SUC in 8 wells at concentrations of 65-541ng/L. These results suggest that wastewater is the most likely source of ACE and SUC impacts in these wells, suggesting the need for monitoring the quality of domestic well water.


Subject(s)
Chromatography, High Pressure Liquid/methods , Sucrose/analogs & derivatives , Sweetening Agents/analysis , Tandem Mass Spectrometry/methods , Thiazines/analysis , Water Pollutants, Chemical/analysis , Fresh Water/chemistry , Limit of Detection , Mass Spectrometry , Spectrometry, Mass, Electrospray Ionization/methods , Sucrose/analysis
10.
Anal Chem ; 86(10): 4982-8, 2014 May 20.
Article in English | MEDLINE | ID: mdl-24734972

ABSTRACT

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 µM. While HBQs are 2-fold more toxic than OH-HBQs, both HBQs and OH-HBQs are substantially more toxic than the regulated DBPs.


Subject(s)
Benzoquinones/analysis , Benzoquinones/toxicity , Disinfectants/analysis , Disinfection/methods , Drinking Water/analysis , Animals , CHO Cells , Chromatography, High Pressure Liquid , Cricetinae , Cricetulus , Halogenation , Tandem Mass Spectrometry
11.
Environ Technol ; 35(9-12): 1427-35, 2014.
Article in English | MEDLINE | ID: mdl-24701941

ABSTRACT

A full-scale system, composed of one anoxic fixed biofilm reactor, four oxic fixed biofilm reactors and an activated sludge membrane bioreactor, was used to treat heavily organic loaded, high toxic and saline fluorescent whitening agent wastewater. This system was running steady during the experimental period of three months. Treatment performance and membrane fouling characteristics were investigated. The concentrations of chemical oxygen demand (COD), NH4+, NO3- and total nitrogen (TN) in effluent were 447, 27, 14 and 114 mg L(-1), corresponding to the removal rates of 89%, 76%, 68% and 64%, respectively. A series of analyses, including Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, confocal laser scanning microscopy, scanning electron microscopy and protein and polysaccharide concentration measurements, represented that the sludge layer formed on the membrane surface contained both organic and inorganic foulants. Polysaccharides in bound extracellullar polymeric substances in mixed liquor were the main contributor to membrane fouling. Off-line tap water rinsing was proved to be a cost-effective method of fouling control.


Subject(s)
Bioreactors , Wastewater/chemistry , Water Purification , Benzene Derivatives , Biofilms , Biological Oxygen Demand Analysis , Membranes, Artificial , Spectroscopy, Fourier Transform Infrared
12.
Environ Sci Technol ; 48(3): 1828-34, 2014.
Article in English | MEDLINE | ID: mdl-24422428

ABSTRACT

Tobacco-specific nitrosamines (TSNAs) exist in environmental waters; however, it is unknown whether TSNAs can be produced during water disinfection. Here we report on the investigation and evidence of TSNAs as a new class of disinfection byproducts (DBPs). Using five common TSNAs, including (methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) as the targets, we first developed a solid phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) method capable of rapidly determining these TSNAs at levels as low as 0.02 ng/L in treated water. Using this highly sensitive method, we investigated the occurrence and formation potential (FP) (precursor test conducted in the presence of chloramines) of TSNAs in treated water from two wastewater treatment plants (WWTPs) and seven drinking water treatment plants (DWTPs). NNAL was detected in the FP samples, but not in the samples before the FP test, confirming NNAL as a DBP. NNK was detected in the treated wastewater before the FP test, but its concentration increased significantly after chloramination in two of three tests. Thus, NNK could be a DBP and/or a contaminant in wastewater. Moreover, these TSNAs were detected in FP tests of wastewater-impacted DWTP plant influents in 9 of 11 samples. However, TSNAs were not detected at full-scale DWTPs, except for at one DWTP with high ammonia where breakpoint chlorination was not achieved. The concentration of the sum of five TSNAs (0.3 ng/L) was 100-fold lower than NDMA, suggesting that TSNAs have a minor contribution to total nitrosamines in water. We examined several factors in the treatment process and found that chlorine or ozone may destroy TSNA precursors and granular activated carbon (GAC) treatment may remove the precursors. Further research is warranted into the efficiency of these processes at different DWTPs using sources of varying water quality.


Subject(s)
Chromatography, Liquid/methods , Nitrosamines/analysis , Pyridines/analysis , Solid Phase Extraction/methods , Tandem Mass Spectrometry/methods , Water Purification , Chloramines , Chlorine , Disinfection , Mass Spectrometry , Ozone , Nicotiana , Water/analysis , Water Quality
13.
Environ Sci Technol ; 47(9): 4426-33, 2013 May 07.
Article in English | MEDLINE | ID: mdl-23560392

ABSTRACT

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-DCMBQ) 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.


Subject(s)
Benzoquinones/chemistry , Drinking Water/chemistry , Halogens/chemistry , Ultraviolet Rays , Chromatography, High Pressure Liquid , Spectrophotometry, Ultraviolet , Tandem Mass Spectrometry
14.
Anal Chem ; 85(9): 4520-9, 2013 May 07.
Article in English | MEDLINE | ID: mdl-23573789

ABSTRACT

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(-•). 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 µL/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(-•) → Br(-). The UPLC efficiently separates all HBQs including some HBQ isomers, while the MS/MS offers exquisite limits of detection (LODs) at subng/mL 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.


Subject(s)
Benzoquinones/analysis , Drinking Water/chemistry , Chromatography, High Pressure Liquid , Molecular Structure , Pressure , Spectrometry, Mass, Electrospray Ionization
15.
Environ Sci Technol ; 47(7): 3275-82, 2013 Apr 02.
Article in English | MEDLINE | ID: mdl-23410080

ABSTRACT

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.


Subject(s)
Benzoquinones/analysis , Household Products/analysis , Hydrocarbons, Halogenated/analysis , Swimming Pools , Water Pollutants, Chemical/analysis , Adolescent , Adult , Benzoquinones/chemistry , Child , Chromatography, Liquid , Disinfection , Female , Halogenation , Humans , Hydrocarbons, Halogenated/chemistry , Ions , Male , Mass Spectrometry , Solid Phase Extraction , Thermodynamics , Water Pollutants, Chemical/chemistry , Water Supply , Young Adult
16.
Molecules ; 15(11): 8518-33, 2010 Nov 22.
Article in English | MEDLINE | ID: mdl-21102378

ABSTRACT

The transformation of phosphorus (P) is a major factor of lake eutrophication, and phosphate releasing bacteria play an important role in the release process. Experiments were conducted to investigate P content and characterize phosphate solubilizing bacterial composition at the molecular level in a shallow eutrophic lake and a wetland. Results showed that P concentrations were relatively high and derived from agricultural runoff and domestic or industrial pollution. Enumeration and molecular identification of these strains indicated that these bacterial groups were abundant in the ecosystem and various kinds of bacteria participated in the phosphorus release process. Twelve phosphate solubilizing bacteria, including eight organic P-solubilizing bacteria (OPBs) and four inorganic P-solubilizing bacteria (IPBs), which belonged to three different families, were isolated and identified. Cupriavidus basilensis was found for the first time to have the ability to mineralize organic P (OP). Laboratory tests on P release ability revealed that IPBs were more effective at releasing P than OPBs. The most efficient IPB strain could accumulate over 170 mg·L-1 orthophosphate, while the equivalent OPB strain only liberated less than 4 mg·L-1 orthophosphate in liquid culture. The results obtained from this investigation should help clarify the roles of microorganisms in aquatic systems and the mechanisms of eutrophication.


Subject(s)
Fresh Water/microbiology , Geologic Sediments/microbiology , Phosphates/metabolism , Phosphorus/metabolism , Wetlands , Bacteria/classification , Bacteria/genetics , Bacteria/isolation & purification , Bacteria/metabolism , Calcium Phosphates/metabolism , Cupriavidus/classification , Cupriavidus/genetics , Cupriavidus/isolation & purification , Cupriavidus/metabolism , Eutrophication , Phylogeny , RNA, Ribosomal, 16S/genetics
17.
Ying Yong Sheng Tai Xue Bao ; 21(7): 1892-8, 2010 Jul.
Article in Chinese | MEDLINE | ID: mdl-20879552

ABSTRACT

Phosphorus (P) release from sediments is one of the most important causes of lake eutrophication, while the activity of P is determined by P chemical form. Due to its advantages in improving our knowledge about the P fractions in environmental samples, the 31P nuclear magnetic resonance (31P NMR) technology has received extensive attention. This paper summarized the current studies on the characterization, translocation, and transformation of P fractions in sediments by using this technology, and described the technical principles, classification, analytical procedures, and specific application fields of this technology. At present, the researches of sediment P by using 31P NMR technology were focused on the characterization of different P forms, the effects of microbes on the P translocation and transformation, and the quantitative analysis of different P fractions. The studies on the P-extracting agents and extraction methods were the hot topics as well. The potential issues and research trends about the application of 31P NMR technology in environmental samples were also discussed.


Subject(s)
Geologic Sediments/chemistry , Magnetic Resonance Spectroscopy/methods , Phosphorus/chemistry , Water Pollutants, Chemical/analysis , Fresh Water/analysis , Phosphorus/analysis , Phosphorus Isotopes/chemistry , Water Pollutants, Chemical/chemistry
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