山东省主要河流中抗生素污染组成及空间分布特征

采用固相萃取-液相色谱/串联质谱法研究了山东省境内四大流域主要河流中抗生素污染组成及空间分布特征,涉及我国用量最大的6类共20种抗生素。结果表明:20种抗生素均有检出,且大环内酯类、喹诺酮类和四环素类抗生素整体检出浓度较高。就流域而言,半岛诸河流域抗生素污染较小,平均总质量浓度61.4 ng/L;海河流域、小清河流域和淮河流域相对较为严重,平均总质量浓度分别为232、175、118 ng/L。抗生素空间分布呈现一定的规律,检出浓度较高的点位主要集中在人口密集区下游,抗生素污染与周边生活污水、养殖企业废水和城市污水处理厂排水密切相关,而且抗生素组成可从一定程度上反映出污染来源。     

Distribution pattern, behavior, and fate of antibacterials in urban aquatic environments in South China

Occurrence, behavior and fate of several groups of antibacterials were investigated in municipal wastewater, sewage sludge, and urban river water in China. Fluoroquinolones (e.g., ciprofloxacin, norfloxacin, and ofloxacin), macrolides (dehydroerythromycin, roxithromycin, and clarithromycin), sulfonamides (sulfamethoxazole and sulfamethazine) and trimethoprim were ubiquitously detected in the wastewater in China. Fluoroquinolones were generally the most abundant in the raw sewage, with a maximum concentration of up to 6415 ng L(-1) observed for norfloxacin. Sulfonamides and macrolides transported predominantly in the aqueous phase. A median percentage of 67% of sulfonamides and 86% of macrolides remained in the final effluent after treatment in sewage treatment plants. On the contrary, sorption played a significant role in transport of fluoroquinolones and approximately half of the fluoroquinolones finally ended up and persisted in the dewatered sludge. In the urban section of the Pearl River at Guangzhou, sulfonamides, trimethoprim, and macrolides were widely present at median concentrations of 22-735 ng L(-1), whereas fluoroquinolones were only occasionally detected at 2-152 ng L(-1), probably due to their strong tendency of partition to sediment and/or photodegradability. The result of principal components analysis suggests input of non-sewage derived sulfamethazine in the Pearl River. Seasonal variations of the antibacterials distribution in the wastewater are mainly ascribed to different consumption. Dilution effect by precipitation, however, also plays an important role in seasonal distribution of the antibacterials in the Pearl River.     

Occurrence, distribution and bioaccumulation of antibiotics in the Haihe River in China

The occurrence, distribution and bioaccumulation of 22 antibiotics, including eight fluoroquinolones (FQs), nine sulfonamides (SAs) and five macrolides (MLs), in the Haihe River were investigated. Surface water, sediment and fish samples were analyzed by HPLC-MS/MS. Ofloxacin, sulfamethoxazole, sulfadiazine, erythromycin and roxithromycin were found in all surface water samples. SAs were the predominant antibiotics in surface water samples in the mainstream of Haihe River, with the maximum concentration of 201 ng L(-1) for sulfamethoxazole. Compared with Haihe River, higher concentrations of antibiotics were found in the surface water samples in the Dagu and Chentaizi Drainage Rivers. The antibiotics pollution in the mainstream of Haihe River may derive from its tributaries, whereas the wastewater from fish ponds was not the main source of FQs, SAs and MLs in the river water. In sediment samples, FQs were the most frequently detected antibiotics and their concentrations were much higher than SAs and MLs. The high concentrations and detection frequencies of FQs in sediments indicate that sediments are an important reservoir for FQs as they are strongly adsorbed onto sediments. Ciprofloxacin and erythromycin exhibited potential bioaccumulation in crucian carp, with mean bioaccumulation factors of 3262 L kg(-1) and 4492 L kg(-1), respectively.     

Different hydrodynamic processes regulated on water quality (nutrients,dissolved oxygen,and phytoplankton biomass) in three contrasting waters of Hong Kong

The subtropical Hong Kong (HK) waters are located at the eastern side of the Pearl River Estuary. Monthly changes of water quality, including nutrients, dissolved oxygen (DO), and phytoplankton biomass (Chl-a) were routinely investigated in 2003 by the Hong Kong Environmental Protection Department in three contrasting waters of HK with different prevailing hydrodynamic processes. The western, eastern, and southern waters were mainly dominated by nutrient-replete Pearl River discharge, the nutrient-poor coastal/shelf oceanic waters, and mixtures of estuarine and coastal seawater and sewage effluent of Hong Kong, respectively. Acting in response, the water quality in these three contrasting areas showed apparently spatial–temporal variation pattern. Nutrients usually decreased along western waters to eastern waters. In the dry season, the water column was strongly mixed by monsoon winds and tidal currents, which resulted in relatively low Chl-a (<5 μg l^?1) and high bottom DO (>4 mg l^?1), suggesting that mixing enhanced the buffering capacity of eutrophication in HK waters. However, in the wet season, surface Chl-a was generally >10 μg l^?1 in southern waters in summer due to halocline and thermohaline stratification, adequate nutrients, and light availability. Although summer hypoxia (DO <2 mg l^?1) was episodically observed near sewage effluent site and in southern waters induced by vertical stratification, the eutrophication impacts in HK waters were not as severe as expected owing to P limitation and short water residence time in the wet season.     

Receptor modeling for analyzing PCDD/F and dioxin-like PCB sources in Hong Kong

A total of 96 ambient air samples were collected from January 2004 to December 2004 for the investigation of dioxins (polychlorinated dibenzo-para-dioxins and polychlorinated dibenzofurans [PCDD/Fs]) and dioxin-like profile for polychlorinated biphenyls (PCBs) in the atmosphere of Hong Kong. Two-day back-trajectories were obtained using the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model from National Oceanic and Atmospheric Administration (NOAA) Air Resources Laboratory. Receptor models – potential source contribution function (PSCF) and concentration-weighted trajectory (CWT) – were built based on the measured PCDD/Fs and dioxin-like PCBs total toxic equivalent (TEQ) concentrations. Both models were modified in this study so as to integrate the information obtained from three sampling sites in Hong Kong. The PSCF modeling resolved two main PCDD/F and dioxin-like PCB polluting paths from Mainland China. In line with previous studies, the northerly path around the Pearl River Delta might be one of the pollution sources of Hong Kong air. On the other hand, the receptor models also indicated another potential northeasterly source from Yangtze River Delta, which was seldom mentioned as the source region of Hong Kong air. Results from the CWT modeling suggested that the most toxic air mass affecting Hong Kong is probably attributable to the northeast path rather than the north path.     

Sources and seasonal variation of PAHs in the sediments of drinking water reservoirs in Hong Kong and the Dongjiang River (China)

The main objective of this study was to investigate occurrence of polycyclic aromatic hydrocarbons (PAHs) in the sources of the drinking water supply of Hong Kong. The main emphasis was on the Dongjiang River in mainland China which is the major source, supplying 80% of the total consumption in Hong Kong (the remaining 20% is obtained from rain water). Sediments were collected from four sites along the Dongjiang River and four reservoirs in Hong Kong during both the dry and wet weather seasons. The concentrations of total PAHs in the sediments ranged between 36 and 539 microg/kg dry wt. The lower levels were detected at the upstream site on the Dongjiang River and at the reservoirs in Hong Kong (44-85 microg/kg dry wt), while the mid- and downstream sites on the Dongjiang River were more polluted (588-658 microg/kg dry wt). Examination of the PAH profiles revealed that the mid- and downstream sections of the Dongjiang River contained high percentages of 4,5,6-ring PAHs, similar to the amounts of atmospheric particulate matter and road dust collected during the dry weather season from the Pearl River Delta region as reported in the literature. Seasonal changes were revealed in the reservoirs of Hong Kong, with higher PAH levels in the wet weather season than in the dry weather season. For those reservoirs in Hong Kong that store water from the Dongjiang River, a distinct seasonal pattern was also observed, namely, that under dry weather season conditions the PAHs found in the sediments were primarily from petrogenic source, while under wet weather season conditions they were from pyrolytic sources. No such pattern was detected in the reservoirs which stored only rain water.     

PAHs in soils and estimated air�Csoil exchange in the Pearl River Delta, South China

In this study, 74 soil samples collected from the Pearl River Delta were analyzed for polycyclic aromatic hydrocarbons (PAHs). The PAH mixture in the soils is mainly of low molecular weight compounds, with naphthalene (21.4%) and phenanthrene (21.8%) being dominant. Soil PAH levels from the Pearl River Delta are relatively low (28?C711 ng/g, averaged 192 ng/g) compared to those from urban soils in temperate regions. The mean concentration of ??PAHs generally decrease with increasing distance from the city center, with ??PAHs of paddy soils > crop soil > natural soil. PAHs in the air were measured during a year-round sampling campaign using semipermeable membrane devices, and the transfer of chemicals between the soil and air compartments were estimated. Soil?Cair fugacity quotient calculations showed a highly uncertain equilibrium position of PAHs, with net volatilization of naphthalene and fluorene, whereas net deposition of phenanthrene, fluoranthene, and pyrene, indicating a capacity for the air to supply the soil with more substances.     

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).     

珠三角典型河道49种抗生素污染现状及风险评估

为评估抗生素在珠三角地表水中的生态及健康风险,在石岐河布设20个监测点位,分别采集丰水期和枯水期样品,用固相萃取/超高效液相色谱-质谱法对4大类共49种抗生素进行检测。结果显示,在丰水期和枯水期样品中共检出抗生素30种,检出种类和抗生素总浓度都呈现出枯水期明显大于丰水期的现象。从总量上看,喹诺酮类是影响石岐河生态环境安全的主要抗生素类别。石岐河抗生素浓度在枯水期主要受污水处理设施出水的影响,在丰水期主要受沿岸养殖业排水的影响。采用风险熵法对生态风险进行评估,发现枯水期生态风险高于丰水期,头孢匹啉、克林霉素、诺氟沙星3种抗生素处于高生态风险级别,罗红霉素、磺胺二甲异恶唑和奥索利酸3种抗生素处于中等生态风险级别,另有4种抗生素处于低生态风险级别,应引起重视。采用健康风险评价模型对人群健康风险进行评价,发现石岐河抗生素致癌风险和非致癌风险皆处于可接受的健康风险范围内。     

Pollution by oestrogenic endocrine disruptors and β-sitosterol in a south-western European river (Mira,Portugal)

The Mira River is a Portuguese water body widely known for its wilderness and is advertised as one of the less polluted European rivers. On this presumption, the levels of endocrine-disrupting compounds (EDCs) in Mira waters were never measured. However, because environmentalists have claimed that the Mira could be moderately polluted, a range of 17 EDCs were measured not only at the estuary but also along the river. The targeted EDCs included natural and pharmaceutical oestrogens (17β-oestradiol, oestrone and 17α-ethynylestradiol), industrial/household pollutants (octylphenols, nonylphenols and their monoethoxylates and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, genistein) and the phytosterol sitosterol (SITO). For this propose, waters from six sampling sites were taken every 2 months, over a 1-year period (2011), and analysed by gas chromatography–mass spectrometry. Unexpectedly high levels of oestrogens and of industrial/household pollutants were measured at all sampling sites, including those located inside natural protected areas. Indeed, the annual average sum of EDCs was ≈57 ng/L for oestrogens and ≈1.3 μg/L for industrial/household chemicals. In contrast, the global average levels of phytoestrogens (≈140 ng/L) and of SITO (≈295 ng/L) were lower than those reported worldwide. The EDC concentrations were normalised for ethynylestradiol equivalents (EE_2eq). In view of these, the oestrogenic load of the Mira River attained ≈47 ng/L EE_2eq. In addition, phosphates were above legal limits at both spring and summer (>1 mg/L). Overall, data show EDCs at toxicant relevant levels in the Mira and stress the need to monitor rivers that are allegedly less polluted.     

River water quality and pollution sources in the Pearl River Delta, China

Some physicochemical parameters were determined for thirty field water samples collected from different water channels in the Pearl River Delta Economic Zone river system. The analytical results were compared with the environmental quality standards for surface water. Using the SPSS software, statistical analyses were performed to determine the main pollutants of the river water. The main purpose of the present research is to investigate the river water quality and to determine the main pollutants and pollution sources. Furthermore, the research provides some approaches for protecting and improving river water quality. The results indicate that the predominant pollutants are ammonium, phosphorus, and organic compounds. The wastewater discharged from households in urban and rural areas, industrial facilities, and non-point sources from agricultural areas are the main sources of pollution in river water in the Pearl River Delta Economic Zone.     

Passive air sampling of DDT, chlordane and HCB in the Pearl River Delta, South China: implications to regional sources

The Pearl River Delta (PRD) is one of the largest fast-developing economic zones in China. Hong Kong and the mainland part of the PRD differed in socio-economic development history and chemical management policies. Polyurethane foam (PUF)-passive air sampling (PAS) was deployed at 21 regional air quality monitoring stations across the PRD in summer and winter, respectively. Dichloro-diphenyl-trichloroethane (DDT), chlordane and hexachlorobenzene (HCB) were analyzed with GC-MS. High total DDT (240-3700 pg m(-3)) and chlordane (100-2600 pg m(-3)) concentrations were observed. Concentrations of DDTs and chlordane were higher in summer than winter; HCB vice versa. Spatially, the mainland part of the PRD generally displayed higher DDT concentrations than Hong Kong. Antifouling paint for fishing ships in coastal China was suggested to be an important current DDT source in the coast. The reason is unknown for the very low trans-/cis-chlordane (TC/CC) ratios (0.27) found in the mainland in winter. HCB concentrations were relatively uniform across the PRD, and long range transport of HCB from inland/North China to the PRD in winter was suggested.     

Perfluorooctane sulfonate (PFOS) distribution and effect factors in the water and sediment of the Yellow River Estuary, China

The distribution of perfluorooctane sulfonate (PFOS) was investigated in a total of 15 water and sediment samples from the Yellow River Estuary, China in April 2011. The results indicated that the concentrations of PFOS in the water and sediment samples averaged 157.5 ng/L and 198.8 ng/g and ranged from 82.30 to 261.8 ng/L and 75.48 to 457.0 ng/g, respectively. The concentrations of PFOS in the sediment column increased from 45.32 to 379.98 ng/g with the decrease of the sampling depth, which showed that the increased PFOS pollution in the sediment appeared in this region in over recent years. The distribution coefficient (K _d) of PFOS between water and sediment linearly increased from 0.37 to 4.80 L/g as the salinity (S‰) increased from 0.18 to 4.47. Correlation analysis revealed that K _d was significantly and positively correlated to the contents of total organic carbon and clay of the sediment, and salinity. Therefore, salinity was an important parameter in controlling the sediment–water interactions and the fate or transport of PFOS in the aquatic environment. The results of this study showed that the estuary was an important sink for PFOS and suggested that PFOS might be carried with the river water and transported for long distances before it reached to the sea and largely scavenged to the sediment in the estuaries due to the change in salinity.     

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。     

Occurrence of selected antibiotics in Jiulongjiang River in various seasons, South China

The concentrations of six sulfonamides (SAs) and three tetracyclines (TCs) were investigated in Jiulongjiang River during the low water season and the high water season. They were monitored in both surface water and sediment. Total concentrations of all these antibiotics varied from 31 to 25,771 ng g(-1) in sediment samples. In water they ranged from 60 to 2607 ng L(-1) during the low water season and from ND (not detected) to 134 ng L(-1) during the high water season. At the sites nearby breeding farms, chlorotetracycline was found to have the highest concentration of 1036 ng L(-1) in water and 14,666 ng g(-1) in sediments. According to the published data, the concentrations of sulfamethazine, sulfameter and TCs at these sites were higher than that in most rivers. The concentrations during the low water season were tens to hundreds of times higher than that in the high water season. The lower concentrations of TCs in the high water season might result from both dilution and photo-degradation, while dilution and bio-degradation might lead to the lower concentrations of SAs. However, further study is needed to clarify the specific reasons. Concerning the relationship between sediment and water samples, the pseudo-partitioning values of TCs were much higher than SAs. It indicates that the TCs are prone to accumulate in the sediment.     

Development of a novel solid-phase extraction element for the detection of nonylphenol in the surface water of Hangzhou

Nonylphenol (NP) is a representative environmental endocrine-disrupting chemical and persistent toxic pollutant. Previous studies have shown that the average concentration of NP in environmental waters was approximately tens to hundreds of ng L(-1) and it could even reach up to tens of μg L(-1). A simple, fast and accurate method employing a novel solid-phase extraction element named "Magic Chemisorber" (MC) followed by high-performance liquid chromatography (HPLC) using a fluorescence detector (FLD) was used for detecting NP. The most important parameters that affect the extraction process, including extraction time, desorption time, desorption solvent and repeatability, were optimized. The MC-HPLC method showed good linearity with concentrations of NP from 10 to 200 μg L(-1), a correlation coefficient of 0.9995 and the limit of detection (LOD) and limit of quantification (LOQ) of this method was 0.44 and 1.47 μg L(-1), respectively. Compared to commercial polydimethylsiloxane (PDMS) glass fiber, MC had both higher capacity and recovery and it could be used repeatedly. Using the MC-HPLC method we found that the concentration of NP in river water from Hangzhou city ranged from 8.54 ± 1.23 μg L(-1) (Qiantang River) to 65.77 ± 3.69 μg L(-1) (Tiesha River), which was similar to that of international regions heavily polluted with NP and higher than that of Bohai Bay, the Yellow River and the Pearl River Delta in China. This level of NP pollution is possibly related to the rapid development of the textile, printing and paper industries of Zhejiang province.     

Quantitative analyses of selected polychlorinated biphenyl (PCB) congeners in water,soil, and sediment during winter and spring seasons from Msunduzi River,South Africa

The lack of information and the need for knowledge on the organic pollutants within the area of KwaZulu-Natal together with the global problem of water supply have prompted our investigation into the analyses of eight polychlorinated biphenyl (PCB) congeners in the Msunduzi River of KwaZulu-Natal, South Africa. Soil, sediment, and water samples were collected at ten different sites along the river during winter and spring seasons. Soil and sediment samples were extracted using ultra sonication with dichloromethane while water samples were liquid-liquid extracted using dichloromethane. All sample extracts were cleaned-up using a multi-layer silica gel column and analyzed with gas chromatography-mass spectrometry. Quality assurance measures were also determined. The percentage recoveries for water were 53–128 for all the PCBs analyzed, while sediment recoveries ranged between 69 and 105%. The highest total concentrations of the PCBs in sediment were 214.21–610.45 ng/g dw at the Du Toit sampling site and 30.86–444.43 ng/g dw basis at the wastewater treatment inlet for winter and spring, respectively. Soil PCB concentrations were 76.53–397.75 ng/g dw at the Msunduzi Town sampling site and 20.84–443.49 ng/g (dry weight) at the Du Toit sampling site for winter and spring, respectively. In addition, high PCB concentrations were found in effluent of the wastewater treatment inlet compared to other sampling sites, which ranged between 0.68–22.37 and 2.53–35.69 ng/mL for winter and spring seasons, respectively. In all the sampling sites selected for this study, Du Toit afforded the highest PCB concentration levels and the lowest was after chlorination at the Darvill wastewater treatment plant. The results presented are new and it is the first study of organic pollutants such as PCBs that has been carried out on this river.     

Organochlorinated Compounds in Waters of the Pearl River Delta Region

Samples of river water and sewage water were analysed for ten PCB congeners, chlorobenzenes and chlorinated pesticides (BHCs and DDT) in three cities (Guangzhou, Shenzhen and Zhaoqing) in the Pearl River Delta, The results showed that the sewage water in Shengzhen had the highest concentration of total PCBs at about 10ng/L, and Dasha River (Shengzhen), the lowest at about 1.0ng/L. In general, the sewage waters in the three cities had higher concentrations of PCBs than river waters. Chlorobenzenes were investigated in the water samples. The total concentrations of chlorobenzenes ranged from 0.02~0.13g/L, the Dasha River had the highest level of chlorobenzenes, and the sewage water in the city of Zhaoqing had the next highest. The result may be related to the discharges from paper production factories nearby the sampling sections of the Dasha River (Shenzhen) and sewage water in Zhaoqing. The concentrations of organochlorinated pesticides (-BHC, -BHC, -BHC, DDT and DDE) changed little in all water samples except for the sewage water in Guangzhou. It seemed that these pesticides are more a residual signal than a direct discharge from point sources.     

Occurrences and fate of selected human antibiotics in influents and effluents of sewage treatment plant and effluent-receiving river Yamuna in Delhi (India)

Antibiotics consumption has increased worldwide, and their residues are frequently reported in aquatic environments. It is believed that antibiotics reach aquatic water bodies through sewage. Medicine consumed for healthcare practices are often released into sewage, and after sewage treatment plant, it reaches the receiving water bodies of lakes or rivers. In the present study, we determined the fate of some commonly used antibiotics in a sewage treatment plant (STP) located in Delhi and the environmental concentration of these antibiotics in the Yamuna River, which receives the sewage and industrial effluent of Delhi. There are many reports on antibiotics occurrences in STP and river water worldwide, but monitoring data from the Indian subcontinent is sparse. Samples were taken from a STP and from six sampling sites on the Yamuna River. Several antibiotics were tested for using offline solid-phase extraction followed by high-performance liquid chromatography equipped with photodiode array analysis. Recoveries varied from 25.5–108.8 %. Ampicillin had the maximum concentration in wastewater influents (104.2?±?98.11 μg l^?1) and effluents (12.68?±?8.38 μg l^?1). The fluoroquinolones and cephalosporins had the lower concentrations. Treatment efficiencies varied between 55 and 99 %. Significant amounts of antibiotics were discharged in effluents and were detected in the receiving water body. The concentration of antibiotics in the Yamuna River varied from not detected to 13.75 μg l^?1 (ampicillin) for the compounds investigated.