Simultaneous determination of 2-phenylbenzotriazole-type mutagens, PBTA-1 through -8, in river water by liquid chromatography-tandem mass spectrometry

We describe a method for the simultaneous determination of eight kinds of phenylbenzotriazole-type mutagens (PBTA-1, -2, -3, -4, -5, -6, -7 and -8) in river water based on liquid chromatography-tandem mass spectrometry (LC/MS/MS). The application of dopant-assisted atmospheric pressure photoionization (APPI) for the detection of the PBTAs was studied. The APPI technique provided higher PBTA signal intensities than those obtained with an electrospray ionization (ESI) source, and the APPI method was used for the determination of the PBTAs. A solid-phase extraction procedure was used for the extractions of PBTA-1 through -8 from river water. The procedure was rapid and the relative standard deviations were below 15%. The detection limits of PBTA-1 through -8 in river water using the proposed method were found to range from 0.04 to 0.5 ng L(-1) and PBTAs were successfully detected in river water at sub-ng L(-1) levels.     

固相萃取-液质联用分析药物和个人护理品

建立了固相萃取-液质联用分析药物和个人护理品(PPCPs)的方法,采用Oasis HLB固相萃取柱分别在酸性条件下和碱性条件下对PPCPs进行富集提取,该法对于宜兴地区能够检出的30种PPCPs均具有良好的线性,相关系数为0.990~0.999,检出限为1.37~10.12 ng/L。应用该法对宜兴地区地表水中存在的PPCPs进行分析,结果显示30种PPCPs均有不同程度检出,分布最广泛的7种分别为避蚊胺、阿替洛尔、对乙酰氨基酚、普鲁卡因、β-雌二醇、卡马西平和苯佐卡因,阿替洛尔浓度较高,普遍为5~600 ng/L。避蚊胺虽然出现频率最高,但其在各个采样点浓度偏低,普遍为1~50 ng/L。     

A preliminary study on the occurrence and behavior of carbamazepine (CBZ) in aquatic environment of Yangtze River Delta, China

The occurrence and behavior of carbamazepine (CBZ) was investigated in aquatic environment of Yangtze River Delta, East China. The water samples were enriched by solid-phase extraction and analyzed by high-performance liquid chromatography with diode array detector. The validation of the analytical method included linearity (0.1?C1 mg/L), recovery studies, and determination of limits of quantification. Limits of quantification of CBZ in various aquatic samples were in the range of 0.1?C0.2 ??g/L. CBZ was detected in the Tongji University Intramural River, the Huangpu River, and the Suzhou River with the highest concentration of 1,090 ng/L, but not detected in the Nanhengyin River and the Caojia River. In sewage water samples, CBZ was not detected in one of the sewage treatment plants (STPs) but was detected in the raw influents and effluents at the other three selected STPs in Shanghai, with the concentrations ranging from 230 to 1,110 ng/L. CBZ was not completely eliminated after secondary treatment (with the active sludge process).     

Presence of steroid hormones and antibiotics in surface water of agricultural, suburban and mixed-use areas

The occurrence of pharmaceutically active chemicals (PACs) in the natural aquatic environment is recognized as an emerging issue due to the potential adverse effects these compounds pose to aquatic life and humans. This study presents the monitoring of two major categories of PACs in surface water: steroid hormones and antibiotics. Surface water samples were collected in the fall season from 21 locations in suburban (4), agricultural (5) and mixed (12) use suburban and agricultural areas. The water samples collected were analyzed using GC/MS for aqueous concentration of eleven steroid hormones: six natural (17alpha-estradiol, 17beta-estradiol, estrone, estriol, 17alpha-dihydroequilin, progesterone) and five synthetic (gestodene, norgestrel, levonorgestrel, medrogestone, trimegestone). In addition, 12 antibiotics (oxytetracycline, chlorotetracycline, tetracycline, sulfamethoxazole, sulfamethazine, trimethoprim, lincomycin, norfloxacin, ofloxacin, roxithromycin, erythromycin, tylosin tartrate) were analyzed using LC/MS. Steroid hormones detected in surface water were: 17alpha-estradiol, 17beta-estradiol, 17alpha-dihydroequilin, estriol, estrone, progesterone and trimegestone. Estrone had the highest detection frequency of >90% with concentrations ranging from 0.6 to 2.6 ng/l. The second most frequently detected estrogen was estriol (>80%) with concentrations ranging from 0.8 to 19 ng/l. The detection frequency varied at different sampling locations. No antibiotics were detected in the 21 streams sampled. This study aims to give a better understanding on the presence, fate and transport of PACs derived from humans and animals.     

微波消解-ICP/MS法同时测定水产品中13种元素

用硝酸-双氧水体系微波消解，以In、Sc为内标，采用电感耦合等离子体质谱法（ICP／MS）同时测定水产品中V、Cr、C0、Ni、Cu、Zn、As、Se、Cd、Sb、Ba、T1、Pb等13种元素。各元素的检出限在0．05ng／g～0．064μg／g之间，样品平行测定4次的RSD〈5％，鲢鱼样品的加标回收率在81％～117％之间。     

U PLC- ESI- MS/MS法同时测定水中7种抗生素

采用超高效液相色谱-电喷雾二级质谱联用技术同时测定水中7种抗生素,优化了试验条件.磺胺甲恶唑、诺氟沙星、环丙沙星、氧氟沙星、四环素在1.00 ng/L～1000 ng/L范围内线性良好,定量下限为1 ng/L,土霉素、金霉素在10.0 ng/L-2 000 ng/L范围内线性良好,定量下限为10 ng/L,去离子水和地表水样加标回收率为72.1%-112%,RSD为0.6%～9.2%.     

Compartment modeling of MTBE in the generic environment and estimations of the aquatic MTBE input in Germany using the EQC model

The use of the gasoline additive methyl tert-butyl ether (MTBE) has caused serious concern about groundwater and surface water contamination. The behavior of MTBE in the two most relevant compartments, surface water and air in a generic environment and in a simulated German environment is investigated using the equilibrium criterion (EQC) model. Due to lack of literature data, the half-life time of MTBE in river water is estimated to about 80-120 d (105 d) at 18 degrees C and roughly 1.5 a (year)(533 d) at 4 degrees C from a batch experiment. The EQC model considers four compartments, air, surface water, soil and sediment in an environment of typically 100,000 km2 with about 10% of the area covered with water. The user can progress through the tiered sequence of Level I to III with increasing complexity which reveals more information about the the fate of the considered chemical. The equilibrium mass distribution of MTBE calculated with the Level I model shows that 87% partitions into air and 13% into surface water at 10 degrees C. The results of the Level II calculations indicate that 50% of MTBE in the air is transported from the system and 38% in the air is degraded at 10 degrees C. The resulting total persistence time of 3 d for MTBE in the generic environment of the Level II model can be compared to the calculated value for chlorobenzene. The MTBE input into water is significantly more sensitive to the 'mode of entry' than input into air. The MTBE concentration in surface water is almost exclusively the result of direct emission into water, whereas the atmosphere can additionally be loaded by volatilization from water. The total aquatic MTBE emission in Germany and the average MTBE concentration in German surface waters were roughly estimated to 20-80 t a(-1) (tons per year)(50 t a(-1)) and 50 ng L(-1), respectively. Surface water concentrations calculated with the underlying assumptions of the model can neither be explained by exposure through waste water and industrial effluents nor with an estimated loss of industrially used MTBE in Germany. For the year-round scenario at 10 degrees C, MTBE concentrations of 19 ng L(-1) (surface water) and 167 ng m(-3) (air) result. However, it remains unclear whether the assumptions of the model, the lack of analyses from industrial effluents or both are responsible for the difference. Additional aquatic emission sources could result from gasoline transport on and storage near rivers. The comparison of winter and summer scenarios shows that in summer, atmospheric (25%) and aqueous (50%) concentrations are lower than in winter due to higher degradation rates.     

Preliminary occurrence studies of antibiotic residues in Hong Kong and Pearl River Delta

An improved liquid chromatography–tandem mass spectrometry (LC-MS/MS) method was developed and validated to investigate the occurrence of selected antibiotic residues in Hong Kong and Pearl River Delta. LC and MS parameters were optimized to produce the maximum analytical responses for each compound. The established method targeted five groups of antibiotics, namely, macrolides, sulfonamides, tetracyclines, quinolones, and amphenicols. The method was validated for three types of environmental water matrices, namely, reservoir, river, and estuarine waters. Low detection limits of 0.17–0.18 ng/L for macrolides, 0.22–0.34 ng/L for quinolones, 0.67–1.65 ng/L for tetracyclines, and 0.27–0.56 ng/L for sulfonamides were obtained. No apparent interferences were observed in the chromatograms of all antibiotics groups. The developed method was preliminarily used to analyze water samples collected from Yuen Long River in New Territories, Hong Kong and four sites along the Pearl River Delta. Results showed that high level of tetracycline was found among the groups tested in the local river samples. In Pearl River Delta, we identified significant levels of erythromycin, roxithromycin, and sulfadiazine in Shenzhen Reservoir.     

高效液相色谱-串联质谱法测定废水中5种喹诺酮类抗生素

建立高浓度有机废水中5种喹诺酮类抗生素的高效液相色谱-串联质谱测定方法。水样经HLB固相萃取小柱富集净化,12 ml甲醇洗脱、浓缩并加入内标溶液后,定容至1 mL待测。以C18柱为分离柱,含0.01%甲酸的甲醇-含0.01%甲酸的水溶液为流动相,目标物质在10 min内分离。在0.25~1 250 ng/mL范围内,目标物质线性关系良好(R20.99)。基质加标试验结果表明,纯水中的回收率为61.40%~91.92%,废水中的回收率为54.92%~101.87%,检出限为0.25~2.5 ng/L,方法定量限为0.36~3.99 ng/L。应用该方法对21家猪场的64份废水样品进行分析,5种喹诺酮类抗生素的检出频率为47%~95%,平均检出浓度为980~5 734 ng/L。该方法快速、准确,适用于高浓度有机废水中喹诺酮类抗生素的同时测定。     

Aquatic humus from an unpolluted Brazilian dark-brown stream: general characterization and size fractionation of bound heavy metals

The main pool of dissolved organic carbon in tropical aquatic environments, notably in dark-coloured streams, is concentrated in humic substances (HS). Aquatic HS are large organic molecules formed by micro-biotic degradation of biopolymers and polymerization of smaller organic molecules. From an environmental point of view, the study of metal humic interactions is often aimed at predicting the effect of aquatic HS on the bioavailability of heavy metal ions in the environment. In the present work the aquatic humic substances (HS) isolated from a dark-brown stream (located in an environmental protection area near Cubat?o city in S?o Paulo-State, Brazil) by means of the collector XAD-8 were investigated. FTIR studies showed that the carboxylic carbons are probably the most important binding sites for Hg(II) ions within humic molecules. 13C-NMR and 1H-NMR studies of aquatic HS showed the presence of constituents with a high degree of aromaticity (40% of carbons) and small substitution. A special five-stage tangential-flow ultrafiltration device (UF) was used for size fractionation of the aquatic HS under study and for their metal species in the molecular size range 1-100 kDa (six fractions). The fractionation patterns showed that metal traces remaining in aquatic HS after their XAD-8 isolation have different distributions. Generally, the major percentage of traces of Mn, Cd and Ni (determined by ICP-AES) was preferably complexed by molecules with relatively high molecular size. Cu was bound by fractions with low molecular size and Co showed no preferential binding site in the various humic fractions. Moreover, the species formed between aquatic HS and Hg(II), prepared by spiking (determined by CVAAS), appeared to be concentrated in the relatively high molecular size fraction F1 (> 100 kDa).     

Distribution of perfluorinated compounds in water, sediment, biota and floating plants in Baiyangdian Lake, China

The distribution of perfluorinated compounds (PFCs) in Baiyangdian Lake, China, was determined in this study. Perfluorooctanoic acid (PFOA) was the dominant PFC in lake water (1.70-73.5 ng L(-1), median 9.72 ng L(-1)), while perfluorooctane sulfonate (PFOS) was the dominant PFC in sediments (0.06-0.64 ng g(-1) dry wt, median 0.19 ng g(-1) dry wt) and in aquatic animals (0.57-13.7 ng g(-1) wet wt, median 2.56 ng g(-1) wet wt). Significant differences in PFC levels were observed among various aquatic animals. We also determined, for the first time, the PFC levels in floating plants, including Ceratophyllum demersum L., Hydrocharis dubia (Bl.) Backer and Salvinia natans (L.), and we found that PFOA and PFNA were the dominant PFCs in these plants. Furthermore, floating plants were observed to have different composition profiles compared to aquatic animals. Geographical differences in PFC levels were also observed, with higher PFC levels in samples from the north part of Baiyangdian Lake than those in the south. The differences in human and industrial activities in different parts of the lake and the discharged wastewater from the Fuhe River may be the major contributors for these geographical differences.     

长江南京段新兴污染物污染特征及风险评估

在长江南京段上游至下游依次布设6个采样点采集水样,使用固相萃取和LC-MS/MS相结合的方法对5种选定药物的质量浓度进行测定,并采用风险熵模型评估其生态风险。结果表明,6个采样点均检测到药物存在。其中,四环素、红霉素、罗红霉素和氯霉素的检出率为100%,最高检出值为10.29 ng/L(氯霉素)。与国内外其他地表水相比,长江南京段水中的药物质量浓度较低。生态风险评估结果表明,长江南京段水中5种药物的风险熵值均低于1,对水生生物不存在高风险。     

Mass Spectrometric Detection and Identification of Polar Pesticides and their Degradation Products - A Comparison of Different Ionization Methods

Due to increasing use of polar pesticides, they are found together with their degradation products in ground- and surface waters serving for drinking water treatment. The triazine derivatives acetamido-atrazine, ametryne, atrazine, cyanazine, deethylatrazine, deethyldeisopropyl-hydroxyatrazine, deethyl-hydroxyatrazine, deisopropyl-atrazin, deisopropyl-hydroxyatrazine, desmetryn, hydroxyatrazine, prometryne, propazine, simazine, terbumeton, terbutryne and terbutylazine, and the pesticides 2,4-D, dichlorprop, isoproturon, diuron, metolachlor, glyphosate, metsulfuronmethyl and dalapon, all of them belonging to this type of pesticides, have been studied. For determination of triazine derivatives UV detection by means of diode array detector (DAD) as well as mass spectrometric (MS) detection coupled by thermospray interface (TSP) have been used successfully after liquid chromatoraphic (LC) separation. Interfaces like thermospray (TSP), electrospray (ESP) and atmospheric pressure chemical ionisation (APCI) were examined with regard to their suitability for substance-specific detection of polar pesticides by flow injection analysis (FIA) with MS- and tandem mass spectroscopic detection (MS/MS) without preceding LC separation. Optimised detection conditions for these pesticides using FIA are presented, and solutions for occurring problems are offered.     

液相色谱-串联质谱法同时测定污水中10种精神活性物质

建立了采用液相色谱-串联质谱法(LC-MS/MS)同时测定污水中10种精神活性物质的分析方法。污水样品经甲酸与甲酸铵调节pH后,加入氘代内标混匀,离心并过滤膜后可直接上样分析。研究表明,在1~250 ng/L的线性范围内,10种精神活性物质的线性相关系数均大于0.992,定量限均低于0.5 ng/L。在3个加标水平下,10种精神活性物质的加标回收率为87.2%~114%,相对标准偏差为0.53%~3.60%(n=3)。将该方法应用于某区域10份生活污水样品的检测,在3份水样中检出吗啡、甲基苯丙胺、氯胺酮等精神活性物质,对应的质量浓度范围分别为3.41~9.55、0.90~1.63、1.06~1.78 ng/L。与经固相萃取前处理后的分析方法相比,该方法可在10 min内完成分离和检测的全过程,具有简单、快速、节约的优点,可用于污水样品中10种痕量水平精神活性物质的定量分析。     

Occurrence of perfluorinated compounds in the aquatic environment as found in science park effluent,river water,rainwater, sediments,and biotissues

The current article maps perfluoroalkyl acids (PFAAs) contamination in the largest Science Park of Taiwan. The occurrence of ten target PFAAs in the effluent of an industrial wastewater treatment plant (IWWTP), its receiving rivers, rainwater, sediment, and the muscles and livers of fish was investigated. All target PFAAs were found in effluent of IWWTP, in which perfluorooctane sulfonate (PFOS) (6,930 ng/L), perfluorohexyl sulfonate (PFHxS) (2,662 ng/L) and perfluorooctanoic acid (PFOA) (3,298 ng/L) were the major constituents. Concentrations of PFBS and PFOS in the IWWTP downstream areas have exceeded safe concentration levels of avian and aquatic life, indicating a potential risk to wildlife in those areas. In sediment samples, predominant contaminants were PFOS (1.5–78 ng/g), PFOA (0.5–5.6 ng/g), and perfluorododecanoic acid (PFDoA) (nd–5.4 ng/g). In biological tissue samples, concentrations as high as 28,933 ng/g of PFOS were detected in tilapia and catfish liver samples. A positive correlation for log (C _sediment/C _water) and log (C _tissue/C _water) was found. The concentration and proportion (percentage of all PFAAs) of PFOS found in biotissue samples from the Keya River (which receives industrial wastewater) were found to be much greater (200 times) than those of samples from the Keelung River (which receives mainly domestic wastewater). These findings suggest that the receiving aquatic environments and, in turn, the human food chain can be significantly influenced by industrial discharges.     

Butyltin contamination in sediments and seawater from Kaohsiung Harbor, Taiwan

The distribution of butyltin (BT) compounds in the sediments and seawater, at the river outfalls, fishing ports, shipyards, and industrial zone docks of Kaohsiung Harbor, Taiwan were investigated. Twenty sediment and seawater samples were collected from various locations in the Harbor in 2006 and analyzed for monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT). Results showed that the concentration of total BTs varied from 1.5 to 151 ng/g in sediment samples, with TBT being the major component of the sediment samples. This suggests that sediments could be the most possible sink of TBT brought by the sorption mechanism. The concentrations of BTs ranged from 9.7 to 270 ng/L in seawater samples, whereas DBT and MBT, the degradation byproducts of TBT, were mainly the most abundant BT compounds of the seawater samples. This indicates that the abiotic or biotic degradation potential of TBT was significant. Spatially, the highest concentrations of BTs were observed in both water and sediment samples collected from the shipyard and fishing port areas. This indicates that the shipping-related activities (e.g., navigation, ship repair, and ship building) would contribute most of BTs in the environment. Results show that the concentrations of degradation products (DBT and MBT) were related closely to temperature, salinity, dissolved oxygen (DO), and chlorophyll-a of the seawater. This implies that seasonal changes of the water parameters controlled the degradation of TBT in seawater. The observed levels of BT compounds in both seawater and sediments were much higher than those required to induce toxic effects on marine organisms, suggesting that appropriate TBT control strategies should be taken in Kaohsiung Harbor.     

Occurrence and behaviour of nonylphenol and octylphenol in Nanming River, Guiyang City, China

Occurrence, variation and behaviour of nonylphenol (NP) and octylphenol (OP) were studied in surface water and groundwater in Guiyang, Guizhou Province, southwestern China. Discharge of wastewater from Guiyang City was the main source of alkylphenols (APs) entering the aquatic environment. The concentrations of NP and OP in river water ranged from 40 to 1582 ng L(-1) and from below the lowest limit of detection (LOD) to 67 ng L(-1), respectively. NP and OP were also detected in groundwater. Both NP and OP exhibited spatial and temporal variations in river water and groundwater. It was found that concentrations of NP and OP in river water was low upstream and dramatically increased downstream, and higher concentration of NP was found in winter compared to that in summer. Proportions of NP and OP were trapped by suspended particulate matter (SPM), which accounted for 7.6-50.0% and 3.4-25.6% of their total concentration in the river water system, respectively. Seasonal changes in water flow were responsible for the temporal variations of APs. To determine the behaviour of APs along the river, a mass balance equation based on chloride was used. The results showed that a mixing process was the predominant factor to determine upstream APs concentrations; while the discharge of wastewater controlled the concentrations of APs downstream. Considering the adverse effect of APs on organisms, combined effect modeling was used to assess the toxicity to fish. It was found that the predicted mixture effect for APs in river water on fish vitellogenin induction was low upstream and medium downstream, respectively.     

Development of an integrative passive sampler for the monitoring of organic water pollutants

The development of convenient and competitive devices and methods for monitoring of organic pollutants in the aquatic environment is of increasing interest. An integrative passive sampling system has been developed which consists of a solid poly(dimethylsiloxane) (PDMS) material (tube or rod), acting as hydrophobic organic receiving phase, enclosed in a water-filled or an air-filled low-density polyethylene (LDPE) membrane tubing. These samplers enable the direct analysis of the pollutants accumulated during exposure in the receiving phase by thermodesorption-GC/MS, avoiding expensive sample preparation and cleanups. The capabilities of these sampling devices were studied for the sampling of 20 persistent organic pollutants (chlorobenzenes, hexachlorocyclohexanes, p,p'-DDE, PAHs, and PCBs) in laboratory exposure experiments. For the three sampler designs investigated the uptake of all target analytes was integrative over exposure periods up to 9 days (except PCB 101). The determined sampling rates range from 4 to 1340 microl h(-1) for the water-filled samplers and from 20 to 6360 microl h(-1) for the air-filled ones, respectively. The sampling rate of the analytes is dependent on their molecular weight, partition between water and sampler media (PDMS, polyethylene, water, air) and also of the sampler design. The passive samplers enable the estimation of time-weighted average (TWA) concentration of water pollutants in the lower ng l(-1) to pg l(-1) range.     

Occurrence of selected pharmaceuticals in river water in Japan and assessment of their environmental risk

The existence of pharmaceuticals in the water environment is thought to be a potential problem for aquatic organisms. In this study, we conducted a nationwide survey to clarify the occurrence of 24 selected pharmaceuticals in major Japanese rivers and evaluated their environmental risk to aquatic organisms. We found a total of 22 substances in river waters at concentrations from several nanograms per liter to several micrograms per liter. We found the highest, which was 2.4 μg/L of caffeine, followed by 1.5 μg/L of crotamiton and 1.4 μg/L of sulpiride. We conducted an environmental risk assessment of the 22 pharmaceuticals detected in river water, for which predicted no-effect concentration (PNEC) values for crustacea and algae had been obtained. The measured environmental concentration/PNEC values of four substances, caffeine, carbamazepine, clarithromycin, and ketoprofen, exceeded 0.1 with the maximum value of 9.0 for clarithromycin. As clarithromycin exhibits a high environmental risk to aquatic organisms, particular attention is required.     

Silver near municipal wastewater discharges into western Lake Ontario,Canada

Because of the widespread use of silver nanoparticles in commercial products, discharges of municipal wastewater may be a point source of silver in the aquatic environment. We monitored two sites in western Lake Ontario impacted by discharges from wastewater treatment plants serving the City of Toronto. Concentrations of silver were elevated in bottom sediments and suspended sediments collected at the two sites. We also deployed two types of passive samplers in the water column at the two sites, the newly developed Carbon Nanotube Integrative Samplers for monitoring “CNIS-labile” silver and Diffusive Gradient in Thin Film samplers for monitoring “DGT-labile” silver. Results from these passive samplers indicated that the concentrations of silver at the two sites were either below detection limits or were in the ng/L range. In laboratory experiments where the sediments were re-suspended in Milli-Q water, a small proportion of the silver (i.e., <?25%) was labile and partitioned as colloidal or dissolved silver into the liquid phase after agitation. Nanoparticles tentatively identified as silver nanoparticles were detected by single-particle ICP-MS in suspension after agitation of both suspended and bottom sediments. Therefore, there is a need to assess whether silver species, including silver nanoparticles are transported from wastewater treatment plants into sediments in the aquatic environment. This study is unique in focusing on the in situ distribution of silver in natural waters and in sediments that are potentially impacted by urban sources of nanoparticles.