Polybrominated diphenyl ethers in soils of the modern Yellow River Delta, China: occurrence, distribution and inventory

The Yellow River is the second largest river in China. In this study, the levels of polybrominated diphenyl ethers (PBDEs) in the modern Yellow River Delta (mYRD) were firstly reported. Twenty PBDE congeners in soil/sediment samples from mYRD were measured. The total PBDE concentrations ranged from non-detectable to 18 257 ng kg⁻¹ with a mean value of 836 ng kg⁻¹. BDE-209 was the dominant congener, accounting for ∼86.1-99.5% of the total PBDEs. The congener profiles of PBDEs with higher abundances of BDE-153 and BDE-183 were similar to those in sediment of the Bohai Sea, indicating that they shared similar sources. The concentrations and congener patterns varied among different regions. Higher levels of PBDEs were found in the middle area (MA), and more complicated congener compositions were also observed in the MA, whereas lower levels of PBDEs were found in the modern course (MC) and the old course (OC). Much more PBDEs were detected in the top layer (TL) soil where more congeners were also held compared to lower soil layers, implying that more PBDEs were emitted into this area in recent years/decades. Organic matter controlled the PBDE distribution in the soil. Soil in this area might be a source of BDE209 for the Bohai Sea.     

Occurrence, distribution and seasonal variation of antibiotics in the Huangpu River, Shanghai, China

Water samples were collected from 19 sampling sites along the Huangpu River in June and December 2009. The occurrence, distribution and seasonal variation of 22 antibiotics, including four tetracyclines, three chloramphenicols, two macrolides, six fluoroquinolones, six sulfonamides and trimethoprim were investigated. It was found that all 19 sampling sites were contaminated by antibiotics. Four antibiotics (sulfamerazine, norfloxacin, fleroxacin and sarafloxacin) were not detected. The detection frequencies of the other 18 antibiotics were in the range of 5.3-100%. The median concentrations of the detected antibiotics ranged from quantification limits to 36.71 ng L⁻¹ (tetracycline) in June and to 313.44 ng L⁻¹ (sulfamethazine) in December. The number of detected antibiotics and the overall antibiotic concentrations were higher in December than in June due to the different river flow conditions. Different dominant antibiotics were observed for each group of antibiotics between June and December. Higher total concentrations of veterinary antibiotics such as tetracyclines were observed in suburban sampling sites than in unban sites, indicating the role of livestock and agricultural activities as an important source of antibiotic contamination.     

Effects of Fe2O3, organic matter and carbonate on photocatalytic degradation of lindane in the sediment from the Liao River,China

Fourteen sediment samples with different content of Fe₂O₃ were collected from the lower reaches of the Liao River in China. The photodegradation of lindane on the surfaces of these sediments was investigated to observe the effects of Fe₂O₃ and other photoinducable substances, such as TiO₂ and organic substances, on photodegradation of lindane. A partial least-squares (PLS) analysis model was developed to find out the statistical relationship between the photodegradation and the contents of these photoinducable substances. It was concluded from the PLS analysis that inorganic carbon and organic carbon have negative effects, whereas Fe₂O₃ and TiO₂ accelerate the photodegradation of lindane in the sediment samples when 365 nm UV light was used as light source. In all cases of the experiments, the photodegradation of lindane in the sediment samples were fitted for pseudo-first-order kinetics.     

Heavy metal pollution status in surface sediments of Swan Lake lagoon and Rongcheng Bay in the northern Yellow Sea

The national ‘Shandong Peninsula Blue Economic Zone Development Plan’ compels the further understanding of the distribution and potential risk of metals pollution in the east coast of China, where the rapid economic and urban development have been taken off and metal pollution has become a noticeable problem. Surface sediments collected from the largest swan habitat in Asia, the Swan Lake lagoon and the surrounding coastal area in Rongcheng Bay in northern Yellow Sea, were analyzed for the total metal concentrations and chemical phase partitioning of five heavy metals (Cu, Zn, Pb, Cd, and Cr). Metal contents in the studied region have increased significantly in the past decade. The speciation analyzed by the sequential extraction showed that Zn and Cr were present dominantly in the residual fraction and thus of low bioavailability, while Cd, Pb and Cu were found mostly in the non-residual fraction thus of high potential availability, indicating significant anthropogenic sources. Among the five metals, Cd is the most outstanding pollutant and presents high risk, and half of the surface sediments in the studied region had a 21% probability of toxicity based on the mean Effect Range-Median Quotient. At some stations with comparable total metal contents, remarkably different non-residual fraction portions were determined, pointing out that site-specific risk assessment integrating speciation is crucial for better management practices of coastal sediments.     

黄河干流表层沉积物中重金属形态分析与风险评价

对黄河全流域表层沉积物样品中重金属元素 (As、Cd、Cr、Cu、Ni、Pb、Zn、V、Co) 的赋存形态进行分析,发现Cd的可利用态占比较高,其余重金属以残渣态为主。基于可利用态重金属含量计算重金属风险评价标准、次生相和原生相分布比值,从而对表层沉积物中重金属的生态风险进行评估。结果表明,整个流域中Cd的生态风险最高。此外,Cd和Pb等重金属在M6点位迁移性较高,存在一定的生态风险。对可利用态重金属进行人体健康风险评价,发现M6点位儿童的致癌 (8.76×10⁻⁶) 和非致癌风险总值 (0.32) 最高。成人与儿童非致癌健康风险总值中As的贡献率最大 (61.28%和62.71%) ,致癌健康风险总值中As的贡献率也最大 (75.91%和75.98%) ,但总体均未超过美国环境总署推荐的人体最大可接受范围。本研究可为识别黄河干流表层沉积物中重金属风险及制定相应污染防控策略提供参考。     

Occurrence and source analysis of typical veterinary antibiotics in manure, soil, vegetables and groundwater from organic vegetable bases, northern China

The residue of antibiotics is becoming an intractable environmental problem in many organic vegetable bases. However, their residual levels and distribution are still obscure. This work systematically analyzed the occurrence and migration of typical veterinary antibiotics in organic vegetable bases, northern China. The results showed that there was no obvious geographical difference in antibiotic distribution between soil and manure. A simple migration model can be easy and quick to predict the accumulation of antibiotics in soil. Antibiotics were mainly taken up through water transport and passive absorption in vegetables. The distribution of antibiotics in a plant was in the sequence leaf > stem > root, and performed biological accumulation. The residues of antibiotics in all samples in winter were significantly higher than those in summer. Overall, this work can lay the foundation for understanding ecological risk of antibiotics and their potential adverse effects on human health by food chain.     

黄河三角洲实验区表层沉积物重金属污染特征及防控策略

分析了黄河三角洲实验区内表层沉积物中重金属的空间分布特征,评价了其污染状况和生态风险,并根据评价结果提出了相应的重金属污染防控措施。结果表明：表层沉积物(0~20 cm)中Cu、Zn、Cr、Cd、Pb、Ni、As和Hg的平均质量分数分别为24.87,73.75,78.16,0.21,25.66,34.66,13.68,0.02 mg·kg⁻¹;各重金属均呈现南岸高于北岸的空间分布特征,且所有元素质量分数的最高值均出现在景区“鸟岛”处;内梅罗综合污染指数分析表明,鸟岛属于中污染到重污染,其余采样点均为轻污染;地累积指数评价表明沉积物中Cd和Hg污染相对严重;潜在生态风险指数表明研究区总体属于轻微-中等生态危害。黄河三角洲邻近核心区的实验区表层沉积物中重金属综合污染程度较低,但存在局部污染较重的区域,Cd和Hg是主要的潜在生态风险因子。基于以上研究结果,建议针对黄河三角洲实验区采取预防为主的防控策略,同时应加强区内Cd和Hg的监测并适时开展修复工作。     

Occurrence and partition of perfluorinated compounds in water and sediment from Liao River and Taihu Lake, China

The concentrations of four perfluorinated sulfonate acids (PFSAs) and 10 perfluorinated carboxylate acids (PFCAs) were measured in water and sediment samples from Liao River and Taihu Lake, China. In the water samples from Taihu Lake, PFOA and PFOS were the most detected perfluorinated compounds (PFCs); in Liao River, PFHxS was the predominant PFC followed by PFOA, while PFOS was only detected in two of the samples. This suggests that different PFC products are used in the two regions. PFOS and PFOA in both watersheds are at similar level as in the rivers of Japan, but significantly lower than in Great Lakes. The contributions of PFOS and long chain PFCAs in sediments were much higher than in water samples of both watersheds, indicating preferential partition of these PFCs in sediment. The concentrations of PFOS and PFOA were three orders of magnitude of lower than that of polycyclic aromatic hydrocarbons in the same sediments. The average sediment-water partition coefficients (log K_oc) of PFHxS, PFOS and PFOA were determined to be 2.16, 2.88 and 2.28 respectively.     

Assessing estrogenic activity in surface water and sediment of the Liao River system in northeast China using combined chemical and biological tools

This paper investigated some selected estrogenic compounds (4-t-octylphenol: 4-t-OP; 4-nonylphenols: 4-NP; bisphenol-A: BPA; diethylstilbestrol: DES; estrone: E1; 17β-estradiol: E2; 17α-Ethinylestradiol: EE2; triclosan: TCS) and estrogenicity in the Liao River system using the combined chemical and in vitro yeast screen bioassay and assessed their ecological risks to aquatic organisms. The estrogenic compounds 4-t-OP, 4-NP, BPA, E1, E2 and TCS were detected in most of the samples, with their concentrations up to 52.1 2065.7, 755.6, 55.8, 7.4 and 81.3 ng/L in water, and up to 8.6, 558.4, 33.8, 7.9, <LOQ and 33.9 ng/g in sediment, respectively. However, DES and EE2 were not detected in the Liao River. The estrogen equivalents (EEQ) of the water and sediment samples were also measured by the bioassay. High estrogenic risks to aquatic organisms were found in the river sections of metropolitan areas and the lower reach of the river system.     

Occurrence of veterinary antibiotics in animal wastewater and surface water around farms in Jiangsu Province, China

The objective of this investigation was to obtain a broad profile of veterinary antibiotics residues in animal wastewater and surface water around large-scale livestock and poultry farms in Jiangsu Province of China. Therefore, 53 samples collected from 27 large-scale animal farms in 11 cities and counties of Jiangsu Province in 2009, were monitored for 10 selected veterinary antibiotics using solid phase extraction and high performance liquid chromatography/electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS) techniques. Ten veterinary antibiotics were found in animal wastewaters, eight antibiotics were detected in pond waters, and animal farm-effluents and river water samples were contaminated by nine antibiotics. The most frequently detected antibiotics were sulfamethazine (75%), oxytetracycline (64%), tetracycline (60%), sulfadiazine (55%) and sulfamethoxazole (51%) which were detected with a maximum concentration of 211, 72.9, 10.3, 17.0 and 63.6 μg L⁻¹, respectively. The maximum concentration of 0.55 μg L⁻¹ for cyromazine, 3.67 μg L⁻¹ for chlortetracycline, 0.63 μg L⁻¹ for sulfadoxine, 39.5 μg L⁻¹ for doxycycline and 0.64 μg L⁻¹ for sulfaquinoxaline were determined in the collected samples. In general, the maximum concentration of the selected veterinary antibiotics was detected in animal wastewaters except for chlortetracycline in animal farm-effluents. In addition, residue levels of selected veterinary antibiotics in animal wastewater and surface water around the farms were related to animal species and have a high spatial variation.     

Occurrence of antibiotics in water, sediments, aquatic plants, and animals from Baiyangdian Lake in North China

This study investigated the presence and distribution of 22 antibiotics, including eight quinolones, nine sulfonamides and five macrolides, in the water, sediments, and biota samples from Baiyangdian Lake, China. A total of 132 samples were collected in 2008 and 2010, and laboratory analyses revealed that antibiotics were widely distributed in the lake. Sulfonamides were the dominant antibiotics in the water (0.86-1563 ng L⁻¹), while quinolones were prominent in sediments (65.5-1166 μg kg⁻¹) and aquatic plants (8.37-6532 μg kg⁻¹). Quinolones (17.8-167 μg kg⁻¹) and macrolides [from below detection limit (BDL) to 182 μg kg⁻¹] were often found in aquatic animals and birds. Salvinia natans exhibited the highest bioaccumulation capability for quinolones among three species of aquatic plants. Geographical differences of antibiotic concentrations were greatly due to anthropogenic activities. Sewage discharged from Baoding City was likely the main source of antibiotics in the lake. Risk assessment of antibiotics on aquatic organisms suggested that algae and aquatic plants might be at risk in surface water, while animals were likely not at risk.     

Analyzing trophic transfer of heavy metals for food webs in the newly-formed wetlands of the Yellow River Delta, China

Nine heavy metals sampled from water, sediments, and aquatic organisms in the newly-formed wetlands of the Yellow River Delta (YRD) of China were analyzed to evaluate their concentrations and trophic transfer in food webs. The stable carbon (δ¹³C) and nitrogen (δ¹⁵N) isotopes were used to investigate trophic interactions. Results show that most of heavy metals detected in water and sediments are lower than that in Yangtze River Delta and Pearl River Delta. The longest food web is approximately 4 with the highest trophic level of birds. The difference of heavy metal concentrations between endangered Saunders’s Gull and other three kinds of protected birds is not obvious. Cd, Zn, and Hg were identified to have an increase with the trophic level (TL), while As, Cr, Cu, Mn, Ni and Pb show an opposite trend, however, the biomagnification of the selected nine heavy metals in the food webs is not significant.     

Residual veterinary antibiotics in swine manure from concentrated animal feeding operations in Shandong Province, China

The scientific interest in the occurrence and fate of antibiotics in animal husbandry has increased during the past decades because of the emergence and development of antimicrobial resistance in pathogenic bacteria. This study developed a method for simultaneous detection of five sulfonamides, three tetracyclines and one macrolide in swine manure with stable recoveries (73.0-110.6%) and high sensitivity (limit of quantification <90 μg kg⁻¹). Thereafter, a total of 126 swine manure samples, collected from 21 concentrated animal feeding operations (CAFOs) in Shandong Province of China during summer and winter, were analyzed. The potential influences of different sampling seasons, swine types and food sources on residual antibiotic concentrations were examined in detail. The maximum concentration of residual antibiotic could reach up to 764.4 mg kg⁻¹ (chlortetracycline), and the detection frequencies were 84.9-96.8% for tetracyclines, 0.8-51.6% for sulfonamides and 4.8% for macrolide. These data reveal that antibiotics were extensively used in CAFOs in this district and the manure may act as a non-specific source of antibiotic residue in farmlands and aquatic environments.     

Characteristics of organic phosphorus fractions in different trophic sediments of lakes from the middle and lower reaches of Yangtze River region and Southwestern Plateau, China

In this study, the characteristics of organic phosphorus (Po) fractions in sediments of six lakes from the middle and lower reaches of Yangtze River region and Southwestern China Plateau, China were investigated using a soil Po fractionation scheme, and the relationships between Po, inorganic phosphorus (Pi) and pollution status were also discussed. The results show that the rank order of Po fractions was: residual Po>HCl-Po>fulvic acid-P>humic acid-P>NaHCO3-Po, with their average relative proportion 8.7:4.6:3.2:2.1:1.0. Po fractions, especially nonlabile Po, were significantly correlated with organic matter, Po and NaOH-Pi. Different distribution patterns of P fractions were observed in those two different regions. Po fractions in the heavily polluted sediments were higher than those in moderately and no polluted sediments, it is suggested that Po should be paid more attention in the lake eutrophication investigation.     

Polycyclic aromatic hydrocarbons in the surface sediments from Yellow River, China

Fourteen surface sediment samples were collected from Lanzhou Reach of Yellow River, China in July 2005. The concentrations of 16 priority polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatography equipped with a mass spectrometry detector (GC-MS). Total concentrations of the PAHs ranged from 464 to 2621 ng/g dry weight. Sediment samples with the highest PAH concentrations appeared at the downstream of Lanzhou City, where there was the biggest wastewater discharge pipeline from Lanzhou Oil Refinery Factory and Lanzhou Chemical Industry Company. Municipal sewage also contributed to the PAH contamination in the sediments. A correlation existed between the sediment organic carbon content (f(oc)) and the total PAH concentrations (r(2)=0.57), suggesting that sediment organic carbon content played an important role in controlling the PAHs levels in the sediments. According to the observed molecular indices, PAHs contamination in Lanzhou Reach of Yellow River originated both from the high-temperature pyrolytic processes and from the petrogenic source, showing a mixed PAH input pattern, which was also confirmed by the results of a principal component analysis (PCA). According to the numerical effect-based sediment quality guidelines (SQGs) of the United States, the levels of PAHs at most studied sites in Lanzhou Reach of Yellow River should not exert adverse biological effects. Although at some sites (such as S10, S12, etc.) one PAH may exceed the effects range low (ERL), individual PAH did not exceed the effects range median (ERM). The results indicated that sediments in all sites should have potential biological impact, but should have no impairment.     

Occurrence and distribution of sediment-associated insecticides in urban waterways in the Pearl River Delta, China

Sediment-associated pesticides, including organochlorine (OCP), organophosphate (OP), and pyrethroid insecticides, were analyzed in urban waterways in three cities (Guangzhou, Dongguan, and Shenzhen) in the Pearl River Delta (PRD), China. The OCPs represented 27.2% of the detectable insecticides in sediment, and chlordanes, DDTs, and endosulfans were the most frequently detected OCPs. The currently used insecticide chlorpyrifos was the only OP detected above the reporting limit (RL), with concentrations ranging from <RL to 100 ng g⁻¹ dry weight (dw). Additionally, pyrethroids were detected in all sediments with the sum pyrethroid concentrations ranging from 4.26 to 384 ng g⁻¹ dw and this represented 64.9% of the sum insecticide concentration. Despite their widespread use, no studies have been conducted investigating the occurrence and distribution of pyrethroids in China. As the first report of pyrethroids in urban waterways in China, the current study found cypermethrin was the most abundant insecticide detected in the PRD at concentrations ranging from 1.44 to 219 ng g⁻¹ dw. Spatially, sediment from more populous and urbanized areas (Shenzhen and Tianhe district in Guangzhou) had higher insecticide residues than less populous agricultural areas. In the more modernized city of Shenzhen, the OCPs were seldom detected, whereas more diverse patterns of pyrethroids were observed. Potential sources of these insecticides, especially the frequently detected pyrethroids, were most likely from pest control during urban landscaping maintenance and from abatement programs targeting mosquitoes and ants. Results suggested that a shift in application pattern and elevated urbanization increased accumulation of currently used insecticides like pyrethroids in sediment, and made them the predominate insecticides in the PRD urban waterways.     

Occurrence and distribution of antibiotics in coastal water of the Bohai Bay, China: impacts of river discharge and aquaculture activities

The presence of 21 antibiotics in six different groups was investigated in coastal water of the Bohai Bay. Meantime, to illuminate the potential effects caused by the river discharge and aquaculture activities, wastewater from three breeding plants and surface water from six rivers flowing into the Bohai Bay were also analyzed for the selected antibiotics. The result revealed that measured antibiotics in the North Bobai Bay were generally higher than those in the South, highlighting the remarkable effects of high density of human activities on the exposure of antibiotics in environment. The antibiotics found in the six rivers were generally higher than those in the Bohai Bay reflecting the important antibiotics source of river discharge. This study reveals that the high consumption of some antibiotics in aquaculture activities may pose high ecological risk to the bay.     

黄河入海口水质评价与预测

对黄河入海口2004-2011年的水质进行评价与预测,采用灰色聚类法分析水体DO、CODMn、NH3-N 3项指标,总结水质年均变化情况.建立水质GM(1,1)灰色预测模型,用实际水质指标值检验其精度,并用此模型预测未来4年水质变化趋势.结果表明,2004-2015年期间,黄河入海口水质在2004-2007年波动较大,但将越来越好,CODMn、NH3-N呈下降趋势,DO、达标率呈上升趋势,并通过灰色关联分析方法分析水质变化原因以期对黄河入海口水质分析预测与水体保护工作提供参考.     

Occurrence and possible sources of polychlorinated biphenyls in surface sediments from the Wuhan reach of the Yangtze River, China

Twenty-seven surface sediment samples were collected from the mainstream and eight tributaries of the Wuhan reach of the Yangtze River, China, in 2005, in order to assess the distribution, possible sources, and potential risk of polychlorinated biphenyls (PCBs) in the environment. The total concentrations of PCBs (the sum of 39 congeners) ranged from 1.2 to 45.1 ng g⁻¹ dry weight, with a mean value of 9.2 ng g⁻¹. Sediment samples with the highest PCB concentrations came from the tributary sites, which are closer to PCB sources. Conversely, PCB concentrations in the sediment from the mainstream sites of Yangtze River were relatively low. The observed PCB levels were higher than those found in the sediments of other rivers in China, but lower than those in river sediments from other urban areas and harbors around the world. Low-chlorinated PCBs, dominated by tetra-PCBs and penta-PCBs, were identified as being prevalent in the surface sediments. Correlation analyses between the PCBs and the geochemistry and heavy metal content of the sediments suggest that the washing of these compounds from the land into the river by floods and heavy rains, or industrial wastewater and domestic sewage, may be the major sources of the PCBs. According to established sediment quality guidelines, the risk of adverse biological effects from the levels of PCBs recorded at most of the studied sites should be insignificant, although the higher concentrations at other sites could cause acute biological damage.     

Sources and distribution of polychlorinated-dibenzo-p-dioxins and -dibenzofurans in soil and sediment from the Yellow Sea region of China and Korea

Polychlorinated-dibenzo-p-dioxins and -dibenzofurans (PCDD/Fs) were measured in soils and sediments from the Yellow Sea region. Korean soils and sediments mostly contained detectable PCDD/Fs and showed a widespread distribution among locations. Soil and sedimentary PCDD/Fs from China were comparable to or less than those in Korea. The patterns of relative concentrations of individual congeners in soils were different between the two countries, but similar in sediments. Sources of PCDD/Fs in China and Korea were found to be independent of each other and their distributions reflected matrix-dependent accumulation. Spatial distribution indicated some point sources in Korea while Chinese sources were more widespread and diffuse. PCDD/Fs measured in the coastal areas of the Yellow Sea were comparable to or less than those previously reported in for eastern Asia. However, ∑TEQs in soils and sediments were near to or, in some cases exceeded environmental quality guidelines.