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1.
Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments, and fish muscles were developed. In water samples, drugs were extracted with solid-phase extraction (SPE) by passing 1000 mL of water through hydrophilic lipophilic balanced (HLB) SPE cartridges. Sediment samples were solvent-extracted, followed by tandem SPE (strong anion exchange (SAX) + HLB) clean-ups. Fish muscles were extracted by a mixture of acetonitrile and citric buffer (80:20, v/v) solution, and cleaned by SPE. Liquid chromatography-tandem mass spectrometry (LC-MS/ MS) with multiple reaction monitoring (MRM) detection was employed to quantify all compounds. The recoveries for the antibiotics in the spiked water, sediment, and fish samples were 60.2%-95.8%, 48.1%-105.3%, and 59.8%- 103.4%, respectively. The methods were applied to samples taken from Dianchi Lake, China. It showed that concentrations of the detected antibiotics ranged from limits of quantification (LOQ) to 713.6 ng- L1 (ofloxacin) in surface water and from less than LOQ to 344.8 μg·kg-1 (sulphamethoxazole) in sediments. The number of detected antibiotics and the overall antibiotic concentrations were higher in the urban area than the rural area, indicating the probable role of livestock and human activities as important sources of antibiotic contamination. In fish muscles, the concentration of norfioxacin was the highest (up to 38.5 μg·kg-1), but tetracyclines and macrolides were relatively low. Results showed that the methods were rapid and sensitive, and capable of determining several classes of antibiotics from each of the water, sediment, and fish matrices in a single run.  相似文献   

2.
Degradation of diuron by the electro-Fenton process   总被引:2,自引:0,他引:2  
The degradation of the herbicide diuron has been undertaken by electrochemical advanced oxidation in aqueous solution. This process generates catalytically hydroxyl radicals that are strong oxidizing reagents for the oxidation of organic substances. Hydroxyl radicals degrade diuron in less than 10 min. Kinetic results evidence a pseudo-first-order degradation, with a rate constant of reaction between diuron and hydroxyl radicals of 4.8x109 M–1 s–1. Several degradation products were identified by chromatography-mass spectrometry (LC-MS). The mineralization degree of a 1.7x10–4 M diuron solution reached 93% at 1,000 coulombs.  相似文献   

3.
Cooking fumes contain compounds that may give rise to oxidative stress and mutations when inhaled. The aim of this study was to evaluate if cooking fumes from frying of bacon induce oxidative stress by measurement of urinary 8-oxo-7,8-dihydro-2 deoxyguanosine, a marker of oxidatively damaged DNA. Three non-smoking women fried bacon for 3 h. Urine samples were taken as early morning void at the same time on four days; the morning before frying, the morning after first frying, the morning after three days of frying and one week after first urine sample. 8-Oxo-7,8-dihydro-2 deoxyguanosine, 1-hydroxypyrene and 2-hydroxyphenanthrene, metabolites of polycyclic aromatic hydrocarbons, were measured by liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS). 8-Oxo-7,8-dihydro-2 deoxyguanosine correlated weakly with concentrations of 1-hydroxypyrene (r = 0.31, p = 0.042), but it did not correlate with 2-hydroxyphenanthrene (r = ?0.074; p = 0.64). Average urinary 8-oxo-7,8-dihydro-2 deoxyguanosine concentrations increased from the day before frying (16.3 ± 4.2 nmol/L) to the third day of frying (26.2 ± 10.2 nmol/L), although not statistically significantly. Our pilot study shows that frying of bacon may result in increased oxidative stress which further emphasises the possible carcinogenic potential of cooking fumes.  相似文献   

4.
Perfluoroalkyl and polyfluoroalkyl substances are occurring in consumer and industrial products. They have been found globally in the aquatic environment including drinking water sources and treated wastewater effluents, which has raised concern of potential human health effects because these substances may be bioaccumulative and extremely persistent. The saturated carbon–fluorine bonds of the substances make them resistant to degradation by physical, chemical, and biological processes. There is therefore a need for advanced remediation methods. Iron-based methods involving high-valent compounds are appealing to degrade these substances due to their high oxidation potentials and capability to generate environmentally friendly by-products. This article presents for the first time the oxidation ability of tetraoxy anions of iron(V) (FeVO4 3?, Fe(V)), and iron(IV) (FeIVO4 4?, Fe(IV)), commonly called ferrates, in neutral and alkaline solutions. Solid compounds of Fe(V) (K3FeO4) and Fe(IV) (Na4FeO4) were added directly into buffered solution containing perfluorooctansulfonate and perfluorooctanoic acid at pH 7.0 and 9.0, and mixed solutions were subjected to analysis for remaining fluoro compounds after 5 days. The analysis was performed by liquid chromatography–mass spectrometry/mass spectrometry technique. Fe(IV) showed the highest ability to oxidize the studied contaminants; the maximum removals were 34 % for perfluorooctansulfonate and 23 % for perfluorooctanoic acid. Both Fe(V) and Fe(IV) had slightly higher tendency to oxidize contaminants at alkaline pH than at neutral pH. Results were described by invoking reactions involved in oxidation of perfluorooctansulfonate and perfluorooctanoic acid by ferrates in aqueous solution. The results demonstrated potentials of Fe(V) and Fe(IV) to degrade perfluoroalkyl substances in contaminated water.  相似文献   

5.
为了研究畜禽粪便中雌激素的污染特征及其环境影响,建立了一种同时提取、分离和检测畜禽粪便中雌酮(E1)、17α-雌二醇(17α-E2)、17β-雌二醇(17β-E2)、雌三醇(E3)、17α-炔雌醇(17α-EE2)和己烯雌酚(DES)共6种雌激素的高选择性和高灵敏性方法——同位素内标-固相萃取-高效液相色谱-串联质谱法。对提取剂、淋洗剂、洗脱剂、色谱分离条件和质谱测定条件等进行了优化。最终的优化方法为:粪便样品加入100 ng同位素内标后,先后用乙腈重复超声提取3次(每次10 mL,每次15 min),离心后合并上清液,旋转蒸发近干再复溶于1 mL甲醇,加7 mL纯水稀释并超声混匀后离心,上清液过0.45μm滤膜后用HLB固相萃取柱净化,经10 mL 15%乙腈水溶液淋洗后,用10 mL的甲醇进行洗脱,氮吹浓缩定容至1 mL,过0.22μm滤膜后测定。用2 mM氟化铵-甲醇为流动相,经TAB色谱柱分离后采用电喷雾离子源和选择反应监测负离子扫描模式进行检测,同位素内标定量。在5、50、200、1000 ng·g?1加标水平下,6种雌激素的平均回收率为90.2%—103.2%,相对标准偏差为0.09%—9.08%,方法检出限(LOD)和方法定量限(LOQ)分别为0.25—0.95 ng·g?1和1.00—3.82 ng·g?1。应用此方法检测了6个猪粪、3个牛粪和3个鸡粪样品中6种雌激素的含量,结果为?1(干质量)。该方法灵敏度高,定量准确且定量范围广,适用于畜禽粪便中6种雌激素的定性定量分析。  相似文献   

6.
以亚热带坡地毛竹林地为试验背景,结合室内控制条件下的降解试验,研究咪唑烟酸在土壤中的分布与归趋,以指导咪唑烟酸在类似地区的安全使用。结果表明,实验室条件下,咪唑烟酸在土壤中的微生物降解较缓慢,降解半衰期为77 d,可能是因为纯毛竹林地土壤中可降解咪唑烟酸的微生物较少或活性较低所致。田间条件下,咪唑烟酸残留主要分布在0~20 cm深度土层。当施用前期咪唑烟酸浓度较高时,随降水作用咪唑烟酸淋溶现象明显,径流损失也较严重;施用后期土壤中咪唑烟酸浓度较低时,其消解受降水影响较小,主要表现为微生物降解作用。咪唑烟酸在土壤中具有一定的移动性和稳定性,在降水量较大的山区使用时,应注意其对下游水源和环境生物的影响。  相似文献   

7.
A solution of atrazine in a TiO2 suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s−1, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H2O2 displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.  相似文献   

8.
A simple and rapid method has been optimised to determine glyoxal and methylglyoxal in atmospheric particulate matter by extraction and derivatisation with 2,4-dinitrophenylhydrazine solutions. Minimal sample preparation was required by mixing a portion of filter charged with atmospheric particulate matter with 5?mL of a saturated solution of 2,4-dinitrophenylhydrazine (1.6?g?L?1) in acetonitrile and acidified by H2SO4 (50?µL?L?1). Chromatographic analyses were carried out 1?h after derivatisation solution was mixed. Finally, the proposed method was applied to quantify these dicarbonyls in atmospheric particulate matter samples, which were obtained as part of a large field study to characterise atmospheric aerosol from a rural area of Madrid. Glyoxal concentrations averaged 0.24?ng?m?3, whereas mean values of methyl glyoxal were around 0.95?ng?m?3. Methyl glyoxal levels showed a clear relationship with the particulate matter levels, whereas glyoxal data did not show such a correlation. This could indicate that both dicarbonyls come from different sources.  相似文献   

9.
Degradation of the herbicide imazapyr by Fenton reactions   总被引:4,自引:0,他引:4  
The degradation of the herbicide imazapyr has been carried out by three advanced oxidation processes involving iron ions as catalysts: Fentons reagent, photo-Fenton and electro-Fenton. We show that all processes are rapid and efficient. The kinetic rate constant was found to be k=5.4×109 M–1 s–1. The mineralization of imazapyr is almost complete using the photo-Fenton and electro-Fenton processes.  相似文献   

10.
采用激光脱附/电离飞行时间质谱技术测定了蒽、二苯并(a,h)蒽,晕苯四种多环芳烃化合物在266nm激光作用下的“软”电离飞行时间质谱,对蒽、二苯并(a,h)蒽、晕苯四种化合物进行的分析结果表明激光脱附/电离飞行时间质谱是一种简单、快速、高灵敏度分析多环芳烃化合物的方法,对晕苯,检出限可达10^16mol。  相似文献   

11.
A solution of atrazine in a TiO2 suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s?1, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H2O2 displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.  相似文献   

12.
Profiles of diarrhetic shellfish poisoning (DSP) toxins produced throughout the growth cycle and the cell cycle of the toxigenic marine dinoflagellate Prorocentrum lima were studied in triplicate unialgal batch cultures. Cells were pre-conditioned at 18 ± 1 °C, under a photon flux density (PFD) of 90 ± 5 μmol m−2 s−1 on a 14 h light:10 h dark photoperiod. In exponential growth phase, cultures were synchronized in darkness for 17 d. After dark synchronization, cultures were transferred back to the original photoperiod regime. Cells were harvested for DSP toxin analysis by LC-MS (liquid chromatography with mass spectrometry), and double-stranded (nuclear) DNA was quantified by flow cytometry. The cell populations became asynchronous within approximately 3 d after transition from darkness to the 14 h light:10 h dark photoperiod. This may be due to the prolonged division cycle (5 to 7 d) that is not tightly phased by the photoperiod. Unlike other planktonic Prorocentrum spp., cytokinesis in P. lima occurred early in the dark and ceased by “midnight”. Cellular levels of the four principal DSP toxins, okadaic acid (OA), OA C8-diol-ester (OA-D8), dinophysistoxin-1 (DTX1) and dinophysistoxin-4 (DTX4), ranged from 0.37 to 6.6, 0.02 to 1.5, 0.04 to 2.6, and 1.8 to 7.8 fmol cell−1, respectively. No toxin production was evident during the extended period of dark synchronization nor during the initial period when NH4 was consumed as the major nitrogen source. Soon after the cells were returned to the 14 h light:10 h dark cycle and they began to take up NO3, cellular levels of all four toxins gradually increased. This increase in DSP toxins usually occurred in the light, marked by a rise in DTX4 levels that preceded an increase in the cellular concentration of OA and DTX1 (delayed by 3 to 6 h). Thus, DTX4 synthesis is initiated in the G1 phase of the cell cycle and persists into S phase (“morning” of the photoperiod), whereas OA and DTX1 production occurs later during S and G2 phases (“afternoon”). No toxin production was measured during cytokinesis, which happened early in the dark. The evidence indicates that toxin synthesis is restricted to the light period and is coupled to cell cycle events. Received: 3 September 1998 / Accepted: 30 March 1999  相似文献   

13.
Several household consumer products were analyzed for their content of perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), and fluorotelomer alcohols (FTOH) by nanoflow ultra performance liquid chromatography – mass spectrometry and gas chromatography – mass spectrometry. Among the investigated products, which are applied as sprays, were impregnating agents, cleaning agents, lubricants, and conditioners. In 14 of the 26 products analyzed, at least one polyfluorinated compound (PFC) was detected in 14 samples. 8?:?2 FTOH was the dominating PFC with concentrations up to 149?µg?mL?1. The maximum concentration of PFOA was 14.5?µg?mL?1, whereas PFOS was not detected in any sample. Investigated PFCs were mostly found in impregnating agents and lubricants, but were not detected in cleaning agents and conditioners. In FTOH-containing impregnating agents, similar ratios between 6?:?2 FTOH, 8?:?2 FTOH, and 10?:?2 FTOH were found. FTOH proportions in PFC-containing lubricants were similar as well. Total human exposure to PFC from consumer product aerosols for three different scenarios was estimated to be between 42.8 and 464?ng?kg?1?per day.  相似文献   

14.
汕头经济特区土壤中优控多环芳烃的分布   总被引:16,自引:0,他引:16  
运用气相色谱-质谱方法对汕头经济特区131个土样中的美国EPA优控多环芳烃(PAHs)进行定性、定量测定,讨论了PAHs的分布特征。结果表明,该区表层土壤中优控PAHs的总质量分数范围从22.1 ng/g到1256.9 ng/g之间,平均质量分数为(317.3210.2) ng/g。其分布随采样点的位置不同而有显著变化:工业区附近多环芳烃的质量分数最高,城市中心次之,郊区最低。大多数样点中?PAHs质量分数和单种PAH质量分数都呈现w(5~20 cm)> w(0~5 cm)>w(20~40 cm)>w(40~100 cm)的垂直分布规律。该区土壤PAHs以3环和4环化合物为主,单种PAH以萘、菲和苯并[b]萤蒽为主。  相似文献   

15.
Rates of benthic denitrification were measured using two techniques, membrane inlet mass spectrometry (MIMS) and isotope ratio mass spectrometry (IRMS), applied to sediment cores from two NO3(-)-rich streams draining agricultural land in the upper Mississippi River Basin. Denitrification was estimated simultaneously from measurements of N2:Ar (MIMS) and 15N[N2] (IRMS) after the addition of low-level 15NO3- tracer (15N:N = 0.03-0.08) in stream water overlying intact sediment cores. Denitrification rates ranged from about 0 to 4400 micromol N x m(-2) x h(-1) in Sugar Creek and from 0 to 1300 micromol N x m(-2) x h(-1) in Iroquois River, the latter of which possesses greater streamflow discharge and a more homogeneous streambed and water column. Within the uncertainties of the two techniques, there is good agreement between the MIMS and IRMS results, which indicates that the production of N2 by the coupled process of nitrification/denitrification was relatively unimportant and surface-water NO3- was the dominant source of NO3- for benthic denitrification in these streams. Variation in stream NO3- concentration (from about 20 micromol/L during low discharge to 1000 micromol/L during high discharge) was a significant control of benthic denitrification rates, judging from the more abundant MIMS data. The interpretation that NO3- concentration directly affects denitrification rate was corroborated by increased rates of denitrification in cores amended with NO3-. Denitrification in Sugar Creek removed < or = 11% per day of the instream NO3- in late spring and removed roughly 15-20% in late summer. The fraction of NO3- removed in Iroquois River was less than that of Sugar Creek. Although benthic denitrification rates were relatively high during periods of high stream flow, when NO3 concentrations were also high, the increase in benthic denitrification could not compensate for the much larger increase in stream NO3- fluxes during high flow. Consequently, fractional NO3- losses were relatively low during high flow.  相似文献   

16.
Arthrobacter sp. strain CN2, capable of degrading 4-nitrophenol, was isolated from activated sludge. Degradation of 4-nitrophenol was optimized at pH 7.7, 30?°C, and 0.53% of glucose. Salt tolerance of 4-nitrophenol degradation was as high as 6% (w/v). Several biodegradation intermediates were identified and quantified by high-performance liquid chromatography and mass spectrometry. 4-Nitrocatechol is involved in the degradation of 4-nitrophenol by CN2. Scale-up of 4-nitrophenol degradation was conducted in a bioreactor with different salinity. When the salinity was below 7%, the degradation rate of 4-nitrophenol was above 90% (100 mg L?1, 3 L).  相似文献   

17.
Background, aim and scope The application of nanosilver is increasing. Knowledge on the fate and behavior of nanosilver in wastewater and wastewater treatment plants is scarce. Studies under real world conditions are completely lacking. We studied (1) the impact of nanosilver on the nitrification of sewage sludge, (2) quantified the mass flow of nanosilver in a pilot-plant, and (3) verified the mass balance in a full-scale municipal wastewater treatment plant where nanosilver is introduced to the municipal plant by an indirect discharger. Materials and Methods The addition of four different nanosilver additives on ammonia oxidation in activated sludge has been studied in batch-reactors at two concentrations (1, 100?mg/L Ag) with two exposure times (2?h, 6?days). The pilot-plant treating 70 population equivalents of domestic wastewater is operated with a 12?day sludge age. Nanosilver was applied to the activated sludge tank within two sludge ages. The silver concentrations were measured in sludge and effluent samples during dosing and the following two sludge ages. The adsorption and speciation of silver particles has been analyzed using scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX). Influent, effluent and sludge were sampled on a full-scale plant (60?000 equivalent inhabitants) and analyzed for silver. Results Silver nitrate, metallic nanosilver, nano-scaled silver chloride and microcomposite silver did not show any effect on ammonia oxidation after the addition of 1?mg/L Ag to the activated sludge (corresponding to 250?mg Ag per kg solids). In contrast, 100?mg/L Ag inhibited the nitrification process by 100?% after the addition of silver nitrate and 20–30?% after addition of colloidal polymer-coated nanosilver. A complete mass balance of the pilot-plant, a steady-state system with known fluxes, demonstrates significant enrichment of silver in the sewage sludge (96?%) after the addition of silver chloride to the plant and small losses of silver into the secondary effluent (4?%). The mass fluxes are similar to metallic colloidal nanosilver investigated under the same conditions. The mass balance has been consistently confirmed by the full-scale study in a municipal wastewater treatment plant. The silver fluxes correspond to the fluxes of the suspended solids in sludge and effluent. Overall, it is estimated that from public wastewater treatment plants about 4–40?mg/a Ag per inhabitant equivalent are discharged annually to the receiving water. The analysis by SEM-EDX demonstrates adsorption and incorporation of nanosilver on biological flocs. This method yields first insight into complex building and transformation of silver associated with sulfide after adding metallic nanosilver and silver chloride to wastewater. Discussion Silver ions released from nanosilver react immediately with large amounts of chloride present in wastewater to form silver chloride. Silver ions may react with organic ligands or sulfide groups additionally. Consequently, even silver nitrate added with 1?mg/L Ag (250?mg Ag/kg TS) to activated sludge did not inhibit nitrification activity. Very high amounts of nanosilver, i.?e. 100?mg/L Ag, overburdened the system and equilibrium condition between silver ion release and ligands was not reached. The mass balance reflects the excellent attachment of nanosilver to activated sludge and biological flocs. Therefore, the main elimination process of nanosilver is attachment to the activated sludge. The elimination of nanosilver is high compared to organic and inorganic micro pollutants omnipresent in wastewater. Any further reduction of suspended solids in the effluent water will reduce the silver load. Conclusions Generally, in wastewater nanosilver occurs bonded to activated sludge flocs and therefore the elimination of nanosilver is efficient under operation conditions typical for wastewater treatment plants. The major fraction of nanosilver is removed from the system by the excess sludge withdrawal. Nonetheless, the efficiency may be further improved by a tertiary filtration step. All analyses of influent, effluent and sludge confirmed that silver exists as silver sulfide. Due to a negligible water solubility of this silver species, silver ions are not subsequently released. Recommendations and perspectives Nanosilver research should be driven to the identification of transformation processes in real environmental matrices and the influence of coatings on the adsorption behavior. There is no need for action to take special measures for nanosilver removal in the area of municipal wastewater treatment plants compared to ubiquitous hazardous organic pollutants may present in wastewater. Nevertheless, source control measures following the precautionary principle should be performed.  相似文献   

18.
王泽远  杨方星 《环境化学》2022,41(1):205-214
本文建立了一种同时测定鱼血清中19种精神活性物质的分析方法.该方法基于QuEChERS方法对样品进行提取和净化,待测物采用超高效液相色谱-串联质谱法(UPLC-MS/MS)进行分析,检测的19种精神活性物质均采用同位素内标法定量.该方法的方法检测限(MDL)范围为0.02-0.06 ng.mE-1,基质效应处于76.7...  相似文献   

19.
Baltic salmons were caught from two Latvian rivers during the spawning seasons of 2010 and 2011 for the determination of seventeen 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and 12 dioxin-like polychlorinated biphenyls (PCBs). A partially automated clean-up procedure was used for sample preparation, followed by capillary gas chromatography hyphenated to high-resolution mass spectrometry. The concentrations of PCDD/F&;PCB-TEQ ranged from 6.6 to 18.2?ng?kg?1 fresh weight and this confirms the previous reports of relatively high concentrations of PCDD/Fs, and especially of dioxin-like PCBs in Baltic wild salmon, in most samples exceeding maximum recommended levels (MRLs) in toxicity equivalency quotients (PCDD/F-PCB-TEQ) of the World Health Organization (WHO 1998) according to EC COMMISSION REGULATION No 1881/2006. The results suggest that high consumption of Baltic wild salmon could entail the risk of exceeding the TDI for adults and teenagers. Extra care must be taken when Baltic wild salmon is included in childrens's diet to avoid exceedance of the recommended TDI of 4?pg?kg?1 body weight for this group.  相似文献   

20.
Summary. Benzoic acid is a known stimulant of olfactory receptor cells in trichoid sensilla on the antennae of adult females of Bombyx mori. Exposure of freshly excised antennae, from B. mori females and males, to vapours of [14C]-benzoic acid revealed that the adsorbed acid is rapidly metabolized (15% conversion in 10 s), suggesting the presence of a highly active enzymatic system. The major product could be identified as N-benzoylserine by use of [2H5]-benzoic acid, and mass spectrometry linked to a gas chromatograph (GC-MS) or a liquid chromatograph (LC-MS), for analysis of the metabolites. The conjugation of benzoic acid with an amino acid apparently represents a novel mode for the rapid deactivation of odorant molecules. Received 26 March 2001.  相似文献   

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