Occurrence and behaviour of organophosphorus insecticides in the River Wuchuan,southeast China

Organophosphorus (OP) insecticides are used worldwide, yet their persistence in the environment is not well understood. This paper summarises recent research on 17 OP insecticides in the River Wuchuan, an important catchment in China, by determining their concentrations in water, soil, sediment and plants by gas chromatography with flame photometric detection (GC-FPD). The concentrations of the total OP insecticides ranged from 92.77 to 229 ng l-1 in river water, 1.61 to 9.93 ng g-1 dry weight in soil, 1.24 to 7.56 ng g-1 dry weight in sediment and 75.28 to 326 ng g-1 dry weight in plants. There was a relatively high abundance of methamidophos, dichlorvos, malathion, omethoate and dimethoate in all water, soil, sediment and plant samples. On average, these five compounds collectively accounted for 64%, 71%, 71% and 54% of the total OP insecticide concentration in water, soil, sediment and plants, respectively, which was similar to the composition of OP insecticides in application formulations used in our study area and in China as a whole. The results therefore reflect the application pattern to some extent, and suggest that the sources of the OP insecticides are mainly from current usage. When compared with other areas, the levels of OP insecticides in the River Wuchuan were moderate. The animal and human risks from exposure to OP insecticides in water and plants were evaluated against relevant threshold values. The results therefore provide important information on the current contamination status of a key agricultural watershed in China, and point to the need for urgent action to control the use of some excessively applied and potentially persistent agrochemicals, such as methamidophos, omethoate and dimethoate.     

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.     

Seasonal variation of nonylphenol concentrations and fluxes with influence of flooding in the Daliao River Estuary, China

Nonylphenol is an endocrine disruptor with harmful effects including feminization and carcinogenesis on various organisms. This study aims to investigate the distribution and ecological risks of nonylphenol in the Daliao River Estuary, China. Nonylphenol, together with other phenolic endocrine disruptors (bisphenol A, 4-t-butylphenol, 4-t-octylphenol, and 2,4-dichlorophenol), was detected in surface water and sediment on three cruises in May 2009, June 2010, and August 2010, respectively. A large flooding occurred during our sampling campaign in August and its effect on nonylphenol concentrations and fluxes in the estuary was therefore evaluated. The results showed that nonylphenol with a concentration range between 83.6–777 ng l^?1 and 1.5–456 ng?g^?1 dw in surface water and sediment was the most abundant among the phenolic compounds, accounting for 59.1–81.0 and 79.9–92.1 % of the total phenolic concentration in surface water and sediment, respectively. The concentrations recorded in May and June were comparable, whereas those in August were considerably higher, mainly due to the flush of flooding. The flooding also caused a 50 times increase in nonylphenol flux from the estuary into the adjacent Bohai Sea. Nonylphenol concentrations in the estuary have exceeded the threshold level of undesirable effects with a potential risk of harm to local species, especially benthic organisms.     

Total estrogenic activity and nonylphenol concentration in the Donggang River, Taiwan

We report a survey on the occurrence and distribution of nonylphenol (NP) and 17β-estradiol equivalent quotient (EEQ) concentrations in Donggang River, Taiwan. Concentrations of NP were measured with a high-performance liquid chromatography/fluorescent system and EEQs were carried with an MVLN cell line. Concentrations of NP ranged from less than 93 to 511 ng/L; EEQs ranged from less than 0.16 to 8.64 ng-E2/L. Concentrations of NP were higher in the dry season than in the wet season, which was affected by a high flow rate. In the main watercourse, higher EEQ occurred in the wet season than in the dry season; rainfall may have flushed substances containing estrogenic activity. NP and EEQ concentrations occurred in seawater only in the dry season, especially high EEQ values, and were not detected in the wet season. The reasons are not clear at this moment. Furthermore, NP concentrations provided low contribution to the total estrogenic activity.     

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.     

Occurrence of organotins in the Yangtze River and the Jialing River in the urban section of Chongqing, China

The occurrence of organotins in the Yangtze River and the Jialing River in the urban section of Chongqing, China and their impact on drinking water waterworks are reported in this study. Water samples were extracted by solid-phase microextraction and measured using a gas chromatograph with mass spectrometer. The results showed that the rivers studied were polluted by both butyltins and phenyltins and that the butyltin species was the dominant pollutant. Butyltins, especially monobutyltin, were detected in all 18 sampling stations, and phenyltins were detected only in 11 sampling stations. Majority of the organotins were MBTs with concentrations varying from 27.3 to 1,145.8 ng Sn L^?1. Diphenyltin and dibutyltin were the second most common with the highest levels of 113.7 and 202.5 ng Sn L^?1, respectively. Monophenyltin, tributyltin, and triphenyltin had the lowest detection rates with concentration levels of 9.7, 161.8, and 37.2 ng Sn L^?1, respectively. Some of the organotins were also detected in drinking water waterworks, which posed a threat to the water quality of Chongqing.     

Occurrence of dissolved PAHs in the Jinsha River (Panzhihua)--upper reaches of the Yangtze River,Southwest China

16 priority polycyclic aromatic hydrocarbons (PAHs) were determined in water samples from the Jinsha River (Panzhihua part), Southwest China. Total dissolved PAH concentrations varied from 21.89 microg l(-1) to 382.8 microg l(-1). It was found that the concentration of PAHs decreased along the flow direction due to the higher density distribution of coal chemical industry in the upstream of our study rivers. The pollution levels in our study area are significantly higher than previously reported values in other waters both in China and other countries. The predominance of benzo[k]fluoranthene and indeno[1,2,3-cd]pyrene was clearly observed in all water samples. On average these two compounds accounted for 98.3% of the total dissolved PAH concentration in water. The results showed the positive correlations among total dissolved PAHs, benzo[k]fluoranthene and indeno[1,2,3-cd]pyrene, which suggested that these two predominant PAHs have similar source and environmental behaviors in our study area. When compared with the survey results of organic micropollutants two decades ago, it was found that hydrocarbon pollution both predominated and even increased with the development of coal chemical industry in this area during the past 20 years. The results therefore provide important information on the current contamination status of a key industrial city in China, and points to the need for urgent action to investigate the relationship between the PAH composition and concentration in water from the Jinsha River and the wastewater discharge from coal chemical industry, and to identify the source, transport pathway and fate of PAHs in the area. It should then be necessary to adopt appropriate and instant measures to control the pollution around this area.     

Occurrence of phthalic acid esters in Gomti River Sediment, India

Cadmium and lead are important environmental pollutants with high toxicity to animals and human. Soils, though have considerable metal immobilizing capability, can contaminate food chain via plants grown upon them when their built-up occurs to a large extent. Present experiment was carried out with the objective of quantifying the limits of Pb and Cd loading in soil for the purpose of preventing food chain contamination beyond background concentration levels. Two separate sets of pot experiment were carried out for these two heavy metals with graded levels of application doses of Pb at 0.4–150 mg/kg and Cd at 0.02–20 mg/kg to an acidic light textured alluvial soil. Spinach crop was grown for 50 days on these treated soils after a stabilization period of 2 months. Upper limit of background concentration levels (C _ul) of these metals were calculated through statistical approach from the heavy metals concentration values in leaves of spinach crop grown in farmers’ fields. Lead and Cd concentration limits in soil were calculated by dividing C _ul with uptake response slope obtained from the pot experiment. Cumulative loading limits (concentration limits in soil minus contents in uncontaminated soil) for the experimental soil were estimated to be 170 kg Pb/ha and 0.8 kg Cd/ha. Based on certain assumptions on application rate and computed cumulative loading limit values, maximum permissible Pb and Cd concentration values in municipal solid waste (MSW) compost were proposed as 170 mg Pb/kg and 0.8 mg Cd/kg, respectively. In view of these limiting values, about 56% and 47% of the MSW compost samples from different cities are found to contain Pb and Cd in the safe range.     

Occurrence,sources, and ecological risks of PBDEs,PCBs, OCPs,and PAHs in surface sediments of the Yangtze River Delta city cluster,China

Polybrominated diphenyl ethers (PBDEs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) in 25 surface sediments in three cities (Nantong, Wuxi, and Suzhou) in the Yangtze River Delta, eastern China were measured. The mean concentrations were 378, 45.8, 1.98, 4,002 ng/g for PBDEs, OCPs, PCBs, and PAHs, respectively. Their levels in the sediments in the three cities were generally consistent with the city industrialization. PBDEs and OCPs were markedly dominated by deca-BDE (>90 %) and DDTs (>70 %). A principle component analysis of the analytes identified three major factors suggesting different sources of the contaminants in the sediments. PBDEs and the organic carbon in the sediments have common sources from industrial activities; whereas OCPs and PCBs, correlated with the second factor, were mainly from historical sources. The third factor with loadings of PAHs is indicative of various combustion sources. Ecological risk assessment indicated that the potential highest risk is from DDTs, for which 22 sites exceed the effects range low (ERL) values and three sites exceed the effects range median (ERM) value.     

Occurrence and behaviour of 4-nonylphenol in river water of Germany

An analytical method composed of solid-phase-extraction (SPE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed to investigate the occurrence and the behaviour of the endocrine disruptor 4-nonylphenol (4-NP) in river water of Germany. 16 Para-isomers of the complex mixture of 4-NP isomers have been resolved in the SPE-extracts of river water samples. The mass spectra indicate the presence of four distinct groups of isomers. The different groups are characterised by different base peaks of the mass spectra dependent on the substitution of the alpha-carbon on the alkyl chain. The different isomers show (i) alpha-methyl, alpha-ethyl (base peak 149), (ii) alpha-dimethyl (base peak 135), (iii) alpha-methyl, alpha-propyl, alpha-butyl (base peak 121) and (iv) alpha-methyl, alpha-propyl, alpha-butyl (base peak 107) configuration of the alkyl chain. The recovery of the unbranched compound 4-n-NP was > or = 90%. Detection limit and determination limit of the whole analytical procedure were 6 ng L(-1) and 25 ng L(-1), respectively with a relative standard deviation of 11.7%. The concentration of the sum of the 4-NP isomers in all samples of river water ranged from 28 ng L(-1) (Elbe River) to 1220 ng L(-1)(Oder River). In a period of a higher river water level, a higher amount of 4-NP was detected in the Oder River than in a period of a lower water level. Therefore dilution was not the determinant factor of the 4-NP concentration in river water. The diurnal dynamics of the sewage treatment works (STWs) have to be considered as an influencing factor for the presence of 4-NP in river water.     

Occurrence of PAHs and PCBs in the Alna River, Oslo (Norway)

Thirty two polychlorinated biphenyl congeners (PCBs), hexachlorobenzene (HCB) and pentachlorobenzene (PeCB) were analysed in passive sampler extracts from surface water-exposed semipermeable membrane devices (SPMDs) and in bed sediment samples from a small urban watercourse, the River Alna (Oslo, Norway). Performance reference compound-corrected data from the passive samplers deployed at three sites along the river were used to track PCB contamination in the overlying water. SPMDs were able to detect an increase in dissolved PCB concentrations at the site furthest downstream that was corroborated by bed sediment concentrations. In comparison, no major increase in concentration of HCB, PeCB or PAHs could be observed. Comparison of passive sampling-based overlying water concentrations with total concentrations measured in bed sediments supports the possibility of further PCB sources upstream of the study area. Diagnostic PAH ratios (from SPMDs) and PCB congener pattern (from sediments) were used in an attempt to identify possible contaminant sources to the Alna River. Selected PAH diagnostic ratios support a multiple emission source scenario and demonstrate the complexity of identifying specific sources of these compounds to surface waters. PCB congener patterns in sediments from all three sites tend to indicate a source of highly chlorinated PCBs (of the Archlor 1260 type) and either a source of lower chlorinated PCBs or the less-likely occurrence of dechlorination in sediment. Information collected during the present screening study also confirms the Alna River as a continuous source of PCBs to the Oslofjord.     

Occurrence and behavior of non-steroidal anti-inflammatory drugs and lipid regulators in wastewater and urban river water of the Pearl River Delta, South China

Occurrence of five non-steroidal anti-inflammatory drugs (salicylic acid, ibuprofen, naproxen, indomethacin and diclofenac) and three lipid regulators (bezafibrate, clofibric acid and gemfibrozil) was investigated in wastewater, sewage sludge, and river water of the urban section of the Pearl River at Guangzhou in South China. Behavior and fate of the pharmaceuticals during treatment in two sewage treatment plants (STPs) were also studied in depth by determining concentrations in the influents and effluents at major treatment units and the sewage sludge. Concentrations of the pharmaceuticals in the raw wastewater were mostly at ng L(-1) levels except salicylic acid whose concentrations ranged from 9.6 to 23.3 μg L(-1). No significant amount of the pharmaceuticals was detected in the suspended particulate matter of wastewater and sewage sludge. Salicylic acid, indomethacin, and naproxen were almost completely removed (≥ 99%); gemfibrozil, ibuprofen and bezafibrate were significantly removed (>75%), whereas diclofenac and clofibric acid were removed by 60-70% during treatment in the STPs. Generally, biodegradation was the governing process for elimination of the investigated pharmaceuticals. Anaerobic biodegradation was responsible for most of the removal of diclofenac whereas aerobic biodegradation also played an important role in elimination of the other pharmaceuticals except SA, which was nearly completely removed after the anoxic process. In the Pearl River, the pharmaceuticals were widely detected. Both the concentrations and detection frequency were higher in March 2008 than those in the other seasons, which may be ascribed mainly to less dilution caused by lower precipitation. Besides the STPs, urban canals directly connected with the Pearl River may also be important contributors to the pharmaceutical contamination in the river.     

贵阳市夏季大气颗粒物及多环芳烃污染特征研究

采集贵阳市老城区夏季5个典型监测点(太慈桥、贵州师范大学、大西门、省政府及省植物园)的样品进行PM2.5、PM10质量浓度分析。同时对PM2.5中PAHs的质量浓度进行分析。结果表明:贵阳市夏季PM2.5和PM10浓度排序均为太慈桥省政府大西门贵州师范大学省植物园,且PM2.5和PM10之间有良好的相关性,PM10=0.931 3 PM2.5+0.019 4,R2=0.996 7,PM2.5污染较重。此外,5个监测点总PAHs和苯并(a)芘的分析结果均为太慈桥省政府大西门贵州师范大学省植物园,苯并(a)芘浓度均未超标。     

Occurrence and behavior of pharmaceuticals, steroid hormones, and endocrine-disrupting personal care products in wastewater and the recipient river water of the Pearl River Delta, South China

The occurrence and behavior of β-blockers, antiepileptic drug carbamazepine and its metabolites, X-ray contrast agent iopromide, natural and synthetic hormones, and several groups of hormone-like personal care products (PCPs), including antiseptics (triclocarban, triclosan, and 2-phenylphenol), parabens and bisphenol A, were investigated in municipal wastewater, sewage sludge, and urban river water of the Pearl River Delta, South China. The pharmaceuticals, natural hormones and PCPs were ubiquitously detected in the raw wastewater from a sewage treatment plant (STP). Only triclocarban and triclosan were detected at significant amounts in the dewatered sludge. Iopromide and the PCPs were greatly removed/transformed from the aqueous phase of the wastewater. The β-blockers were only moderately removed/transformed. Carbamazepine passed through the STP almost unchanged. Biodegradation was the dominant process for elimination/transformation of the pharmaceuticals, hormones, and most PCPs in the STP. However, sorption also played an important role in the fate of triclocarban with nearly 50% of the mass load entering the STP ended up and persisted in the dewatered sludge. The pharmaceuticals, estrone, and PCPs were also widely detected in the Pearl River at Guangzhou. Bisphenol A had the highest concentration. The pharmaceutical concentrations in the Pearl River were higher in March than in May, most likely due to less dilution by lower precipitation. The omnipresence and high levels of the pharmaceuticals and PCPs in the Pearl River may be associated with direct discharge of untreated wastewater and pose potential risks to the ecological system.     

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。     

贵阳市小车河“白水”现象的初步分析

通过对小车河从阿哈水库大坝取水口至南明河入口段采集的水样进行p H值、温度及主要离子浓度测定分析,研究该段水体的水化学特征,并从溶解度方面初步分析,发现小车河"白水"现象是由于水中Ca2+浓度过高,使水体形成过饱和的Ca SO4和Ca CO3水溶液,析出大量白色Ca SO4和Ca CO3颗粒,与河水形成溶胶导致。     

Occurrence and distribution of organochlorine pesticides (DDT and HCH) in sediments from the middle and lower reaches of the Yellow River, China

Sediments used in this study were selected from 23 stations in the middle and lower reaches of the Yellow River and its tributaries in November 2005. The levels and distribution patterns of selected organochlorine pesticides (OCPs = p,p ^′-DDT, o,p ^′-DDT, p,p ^′-DDE, p,p ^′-DDD, α-, β-, γ-, and δ-HCH) in samples were investigated by analysis of gas chromatography coupled with micro-electronic capture detector. Concentration of OCPs in the sediments from the Yellow River ranged from 0.05 to 5.03 ng g^???1 (mean, 1.02 ng g^???1) for ∑DDT, 0.09–12.89 ng g^???1 (mean, 1.08 ng g^???1) for ∑HCH. The concentration distribution of ∑DDT and ∑HCH varied significantly with different sampling station, indicating their different contamination sources. Composition analyses demonstrated that residues of DDTs in sediments came from the previous inputs of organochlorine pesticides, while β-HCH and γ-HCH significantly dominated in the sediments for HCHs.     

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.