稻瘟酰胺在水/沉积物中的降解及生物富集性研究

稻瘟酰胺是一种新型内吸型杀菌剂,其在水体环境中的归趋备受关注。采用室内模拟试验方法,研究了稻瘟酰胺在水-沉积物中的降解特性和在斑马鱼中的生物富集性。结果表明,在水-沉积物降解中,好氧条件下河流与湖泊水-沉积物系统中农药总量的降解半衰期分别为169.1、60.3 d,厌氧条件下的降解半衰期分别为173.3、126.0 d,湖泊体系的降解速率快于河流体系。稻瘟酰胺在水-沉积物体系中主要存在于沉积物中,系统降解速率主要受沉积物中的降解速率影响。稻瘟酰胺在斑马鱼中的生物富集系数BCF_(8d)达64.8~189.1,具有中等富集性。稻瘟酰胺在水体环境中具有较强稳定性,且具有一定的生物富集性,可能会对水体和水体生物造成一定的污染影响。     

戊唑醇在环境中的降解迁移和生物富集性研究

戊唑醇属于内吸性三唑类杀菌农药,在国内广泛用于田间病虫防治,故其在环境中的归趋备受关注。采用室内模拟试验方法,研究了戊唑醇在水-沉积物中的降解特性、土壤中的吸附性和在斑马鱼中的生物富集性。结果表明:好氧条件下,戊唑醇在河流与湖泊水-沉积物系统中农药总量的降解半衰期分别为533.2、433.2 d;厌氧条件下,河流与湖泊水-沉积物系统中降解半衰期分别为364.8、1 732.9 d;沉积物系统降解半衰期较长,降解速率主要受水中戊唑醇的降解速率影响。戊唑醇在江西红壤、太湖水稻土、常熟乌杉土、东北黑土中的吸附性符合Freundlich方程,Kd值分别为7.4、11.8、11.2和15;吸附性大小次序为东北黑土太湖水稻土常熟乌杉土江西红壤;以有机碳含量表示的土壤吸附常数KOC在698.9~1 635.5之间;影响戊唑醇土壤吸附性的主要因素为土壤有机质含量和p H。戊唑醇在斑马鱼中的生物富集系数BCF8 d为21.52~25.30,具有中等富集性。戊唑醇在水体环境中具有较强稳定性,不易被土壤吸附,且具有一定的生物富集性,可能会对水体和水体生物造成一定的污染。     

戊唑醇对斑马鱼的急性毒性及生物富集效应

为评价杀菌剂戊唑醇对水生生态系统的影响,以斑马鱼(Brachydanio rerio)为试验生物,采用半静态法分别研究了戊唑醇原药和其6种不同剂型对斑马鱼的急性毒性以及戊唑醇原药对斑马鱼的生物富集效应。结果表明:97.4%戊唑醇原药、25%戊唑醇水乳剂、430 g·L-1戊唑醇悬浮剂、25%戊唑醇可湿性粉剂、80 g·L-1戊唑醇悬浮种衣剂、250 g·L-1戊唑醇乳油、80%戊唑醇水分散粒剂对斑马鱼96 h-LC50分别为8.73、3.35、6.44、9.68、4.60、0.892和6.81 mg·L-1;选择97.4%戊唑醇原药进行斑马鱼生物富集试验,在9.00×10-2和0.900 mg·L-12个处理浓度下连续暴露8 d,相应的富集系数(BCF8 d)分别为27.7和25.4。根据《化学农药环境安全评价试验准则》毒性划分标准,除250 g·L-1戊唑醇乳油对斑马鱼急性毒性属于高毒,其他剂型均为中毒,且戊唑醇属于中等富集性农药。该研究为戊唑醇田间安全使用提供理论依据。     

磺胺类抗生素在斑马鱼体内的生物富集性及模型预测评估

针对磺胺类抗生素在鱼体内的生物富集特性,采用半静态生物富集测试法,研究磺胺二甲嘧啶(SMT)和磺胺甲恶唑(SMX)在斑马鱼(Brachydanio rerio)体内的生物富集规律及生物富集系数(bio-concentration factor,BCF),并选用3种常用预测模型对2种磺胺类抗生素的BCF值进行估算,比较了估算值与实际测定值,为磺胺类抗生素生物富集性的预测提供依据。研究结果表明,当暴露浓度为0.01 mg·L~(-1)~1.00 mg·L~(-1)时,鱼体对SMT的最大生物富集系数BCF值为1.11,最大富集量出现在暴露24~48 h期间;SMX的最大BCF值为1.15,最大富集量处于暴露96~168 h之间。根据磺胺类抗生素的理化性质,通过比较3种生物富集预测模型获得SMT和SMX的BCF值,发现其中Kow预测模型所得估算值最为接近实测值。因此可利用该模型作为磺胺类抗生素富集性的预测工具,为我国兽药抗生素的环境风险预测和评价提供依据。     

叶菌唑对斑马鱼的急性毒性及生物富集效应

为评价杀菌剂叶菌唑对水生生态系统的影响,以斑马鱼(Brachydanio rerio)为试验生物,采用半静态法研究了叶菌唑原药对斑马鱼的急性毒性以及生物富集效应。结果表明,95%叶菌唑原药对斑马鱼96 h的半数致死浓度(96 h-LC_(50))为3.89 mg·L~(-1),选用在3.90×10~(-1)和3. 90×10~(-2)mg·L~(-1)这2个处理浓度下连续暴露8 d,在3. 90×10~(-1)mg·L~(-1)浓度下生物富集系数(BCF)为53.3;在3.90×10~(-2)mg·L~(-1)浓度暴露下生物富集系数(BCF8d)为26.2。根据《化学农药环境安全评价试验准则》毒性划分标准,叶菌唑原药属于中等富集性农药。研究结果为叶菌唑田间安全使用提供理论依据。     

新型杀菌剂氟吡菌胺对9种环境生物的急性毒性及其在斑马鱼体内的生物富集

为评价新型杀菌剂氟吡菌胺对环境生物的毒性风险,避免其在使用过程中对我国特有的环境生物产生危害,测定了氟吡菌胺对意大利蜜蜂、日本鹌鹑、斑马鱼、家蚕、斜生栅藻、大型溞、玉米螟赤眼蜂、赤子爱胜蚓和黑斑蛙蝌蚪等9种代表性环境生物的急性毒性,并以斑马鱼为试材,研究了氟吡菌胺的生物富集性,即根据鱼类急性毒性结果 LC50(96 h)=1.489 mg·L~(-1),设计生物富集试验水样浓度为LC50的1/2、1/10和1/100,即0.745 mg·L~(-1)、0.149 mg·L~(-1)和0.0149 mg·L~(-1),连续暴露8 d,采用液相色谱法测定3个浓度下氟吡菌胺在斑马鱼体内的富集量。结果表明,氟吡菌胺对斑马鱼、斜生栅藻和大型溞3种水生生物的急性毒性为中毒级,对黑斑蛙蝌蚪急性毒性为高毒级,其对蜜蜂、鸟类、家蚕、蚯蚓和天敌赤眼蜂等环境生物均为低毒或低风险;斑马鱼在0.745、0.149和0.0149 mg·L~(-1)的氟吡菌胺水溶液中暴露192 h时,生物富集系数BCF分别为33.65、26.39和193.25;根据化学农药环境安全评价试验准则评价标准,10BCF≤1000,氟吡菌胺属于中等富集性农药。     

啶酰菌胺在斑马鱼体内的富集特性及其对SDH和复合物Ⅱ活性的抑制

为进一步探索啶酰菌胺对水生生物的毒性,选择斑马鱼为供试生物,采用半静态法,研究了啶酰菌胺在斑马鱼体内的富集与消除规律及对其肝脏和鳃的毒性作用。结果表明,斑马鱼暴露于0.08、0.32 mg·L~(-1)中,14 d后均达到富集平衡,28 d生物富集系数(BCF_(28 d))分别为35.50和36.72。在0.16、0.32 mg·L~(-1)浓度下,斑马鱼的比肝重(HSI)和比鳃重(BSI)均明显高于对照组,而肝脏和鳃中琥珀酸脱氢酶(SDH)和线粒体呼吸链复合物II活性均明显低于对照组,浓度低于0.08 mg·L~(-1)时,对斑马鱼无明显影响。由此可知,啶酰菌胺对斑马鱼为中等富集性,并对其肝脏和鳃有一定毒性作用。     

虫螨腈对斑马鱼的急性毒性及生物富集性研究

以斑马鱼(Brachydanio rerio)为试验生物,采用半静态法测定虫螨腈对斑马鱼的急性毒性和生物富集系数。试验结果表明,虫螨腈对斑马鱼96 h-LC50为0.015 mg·L-1,其95%的置信限为0.011 mg·L-1~0.12 mg·L-1,属于高毒。在两个处理浓度2.0×10-4mg·L-1和2.0×10-3mg·L-1下,连续暴露8 d,斑马鱼对虫螨腈的生物富集系数(BCF8d)分别为1 211.6和1 549.7,属于高富集性农药。     

虫螨腈对斑马鱼的急性毒性及生物富集性

以斑马鱼(Brachydanio rerio)为试验生物,采用半静态法测定虫螨腈对斑马鱼的急性毒性和生物富集系数。试验结果表明,虫螨腈对斑马鱼96 h-LC50为0.015 mg·L-1,其95%的置信限为0.011 mg·L-1~0.12 mg·L-1,属于高毒。在两个处理浓度2.0×10-4mg·L-1和2.0×10-3mg·L-1下,连续暴露8 d,斑马鱼对虫螨腈的生物富集系数(BCF8d)分别为1 211.6和1 549.7,属于高富集性农药。     

配套养殖体系中部分抗生素的污染特征

采用超声提取-固相萃取-高效液相色谱串联质谱技术分析配套养殖体系粪便、水体和沉积物中4种磺胺类(SAs)、2种四环素类(TCs)、2种大环内酯(MLs)和2种喹诺酮类(QLs)抗生素的含量和分布特征.研究结果显示,在水体中共检出8种抗生素,浓度在ND—382 ng·L-1,2种四环素类抗生素未被检出,且水体中抗生素的浓度呈现旱季高于雨季;沉积物中共检出7种抗生素,其浓度分别在ND—3400μg·kg-1范围内,磺胺嘧啶(SDZ)、磺胺甲噁唑(SMX)和罗红霉素(RTM)未被检出;在猪粪和鸭粪中均检出甲氧苄啶(TMP)、诺氟沙星(NFX)、脱水红霉素(ETM-H2O)和罗红霉素(RTM),同时猪粪中还检出2种四环素类,鸭粪中检出磺胺二甲嘧啶(SMZ)和环丙沙星(CFX),其中鸭粪中甲氧苄啶的最高浓度达到6.11 mg·kg-1.研究结果表明,不同介质中抗生素的含量存在一定差异,其中磺胺类抗生素在水体中浓度最高,喹诺酮类和四环素类在沉积物中的浓度最高;粪便中抗生素的种类与施药的种类密切相关,并且可能会加剧抗生素对水体环境的污染.     

北江流域抗生素污染水平和来源初探

北江是发源于湖南(武水)和江西(浈水),汇于广东韶关,流经广东全境并入海的三大河流之一。为了解整个北江抗生素污染情况,共设置44个采样点,并采集了河水及部分沉积物样品,较全面地分析了各样品中12种典型抗生素含量并初步探究了其污染来源。研究发现,包括北江源头在内的全河段均有抗生素的检出,5类抗生素在表层水和沉积物中的平均浓度分别为77.8 ng·L~(-1)和3.6 ng·g~(-1)。其中,大环内酯类污染最为严重,其含量范围为11.7~114.6 ng·L~(-1)和0~435.3 ng·g~(-1),远高于其他类抗生素。表层水中磺胺类的磺胺甲恶唑和氯霉素类的检出率达100%,其中以磺胺甲恶唑(14.7 ng·L~(-1))和阿奇霉素(25.0 ng·L~(-1))为主,而沉积物中以阿奇霉素(35.9 ng·g~(-1))、氧氟沙星(5.4 ng·g~(-1))和四环素(3.3 ng·g~(-1))为主。由于流域污染源种类和数量不同,各抗生素在北江中的分布也存在差异。表层水中抗生素含量水平表现为下游高于上中游,在沉积物中则主要集中于中、下游之间河段。这反映了人类活动强度对北江抗生素污染的直接影响。     

Geochemical distribution of trace element concentrations in the vicinity of Boroo gold mine, Selenge Province, Mongolia

The environmental impacts of Boroo gold mine project in Mongolia was evaluated by chemical characterization of trace element concentrations in water, soils and tailing dam sediment samples. The results showed that concentrations of B, Cd, Ni and Se in the water samples were within the accepted levels of the Mongolia water quality standard (MNS4586: 1998). However, the concentrations of Al, As, Cu, Mn, Fe, Pb, U and Zn were higher than the maximum allowable concentration especially in the monitoring and heap leach wells. The average concentrations of As, Cd, Cu, Ni, Pb and Zn in the tailing dam sediment were 4419, 58.5, 56.0, 4.8, 20.6 and 25.7 mg/kg, respectively. Generally, arsenic and heavy metals in the soil samples were within the acceptable concentrations of the soil standard of Mongolia (MNS 5850: 2008). The chemical characterization of As solid phase in tailing dam sediment showed that the majority of As were found in the residual fraction comprising about 74% of total As. Assessing the potential risk to humans, simple bioavailability extraction test was used to estimate bioavailability of arsenic and heavy metals, and the concentrations extracted from tailing dam sediment were; 288.2 mg/kg As, 7.2 mg/kg Cd, 41.1 mg/kg Cu, 13.5 mg/kg Pb, 4.7 mg/kg Ni and 23.5 mg/kg Zn, respectively. From these results, the Boroo gold mine project has presently not significantly impacted the environment, but there is a high probability that it may act as a source of future contamination.     

莱州湾近岸海域中典型抗生素与抗性细菌分布特征及其内在相关性

为了揭示海陆衔接区环境中抗生素与抗性细菌分布特征及其内在相关性,以莱州湾及其主要入海河流为研究区域,利用HPLC-MS/MS分析样品中15种磺胺类抗生素(SAs)和6种喹诺酮类抗生素(QNs)的浓度,并通过改良的Method 1604(US EPA)评估海水与沉积物中2种典型水传病原微生物大肠杆菌(E.coli)与金黄色葡萄球菌(S.aureus)的抗生素抗性水平,进而探讨该区域水体中抗性菌株的分布特点以及微生物抗性率与相应抗生素浓度的相关性。结果显示,莱州湾水体与沉积物中普遍存在磺胺与喹诺酮类抗生素残留及抗性污染问题。两大类抗生素在水体中平均残留浓度分别为3.89 ng·L~(-1)(SAs)和234.68ng·L~(-1)(QNs),在沉积物中分别为0.91 ng·g~(-1)(SAs)和49.37 ng·g~(-1)(QNs),且分布特征基本呈现自河流向海洋逐渐递减的趋势,说明河流输入是莱州湾抗生素污染的主要来源。在水体中,具有磺胺类抗性的E.coli和S.aureus平均检出量分别达到2 018和4 683 CFU·L~(-1),抗性率范围分别在0%~37.3%和10.6%~45.8%之间;而2种喹诺酮类抗性病原微生物的平均检出量则相对较低,分别为1 315 CFU·L~(-1)(E.coli)和1 461 CFU·L~(-1)(S.aureus),抗性率分别为0%~50.0%和0%~20.8%;此外,相比于E.coli,S.aureus为沉积物中的主要抗性病原微生物,磺胺与喹诺酮类抗性S.aureus检出率均高于80%,平均检出量分别为24CFU·g~(-1)和18 CFU·g~(-1)。相关性分析表明,莱州湾近岸海域水体中磺胺类抗生素浓度与磺胺类抗性微生物总量之间具有良好的线性关系,然而其与微生物抗性率之间并未表现出相似的规律,说明近岸海洋环境中抗生素的残留量不是影响抗性菌株丰度的唯一因素。     

镉"加标"沉积物对泥鳅(Misgurnus anguillicaudatus)生物毒性研究

选择泥鳅(Misgurnus anguillicaudaus)作为受试生物,以泥鳅死亡率、血液红细胞数量、红细胞体积、红细胞微核率和核异常率作为测试指标,考察了沉积物中"加标"金属镉(Cd)的毒性状况,探讨了水体沉积物中重金属的生物毒性影响.结果表明:高有机质的粘土粉砂性沉积物能够有效吸附重金属镉;镉加标暴露组泥鳅的死...     

Interaction of alongshore sediment transport and habitat conditions at Laguna La Mancha, Veracruz, Mexico

The habitats of La Mancha Lagoon, located midway along the coast of Veracruz, Mexico, are responding to the change of sediment supply reaching its primary inlet at the Gulf of Mexico. Until several decades ago, an abundant alongshore supply of sediment created a periodic opening and closing of the La Mancha inlet. The hydrologic regime of the lagoon consisted of raised water level and lower salinity during the closures, whereas the open inlet favored lower water level, higher salinity, and sediment accumulation in the flood tidal delta. Currently, diminished alongshore sediment supply has affected the inlet morphology and the discharge regime. Associated with the reduced sediment supply, the inlet is open longer in its periodic cycle, the water level variation is reduced, the salinity contrasts are reduced, and the rate of sedimentation in the flood-tide delta is increased. This combination of alterations to the inlet area is changing the flooding regime and affecting the conditions in a very well-developed mangrove habitat at the lagoon margins as well as conditions within the aqueous portions of the lagoon. Management options produce a conflict between supporting the direction of change or preserving the existing habitats.     

Distributions, cycling and recovery of amino acids in estuarine waters and sediments

Acid hydrolysis of estuarine water samples for the determination of amino acids (AAs) was tested and found to be effective at high (250 μM) nitrate concentrations when the anti-oxidant, ascorbic acid, was added to the samples. Hydrolysable AA concentrations were then determined in surface sediments collected from low and high salinity regions of the Tamar Estuary (UK) during winter 2003 and 2004, and in overlying water when simulated resuspension of sediment particles was performed. Concentrations of AAs in sediment samples comprised <50% of particulate nitrogen, fitting the paradigm that most sedimentary nitrogen is preserved within an organic matrix. When sediment samples were resuspended in overlying water (salinity 17.5), the rapid, measured increase in dissolved AA concentrations almost equalled the reported nitrate concentration in the lower estuary, with the subsequent decrease in the total dissolved AA levels suggested that bacterial uptake was occurring. Our data concur with previous studies on nitrogen desorption from sediments and suggest that an understanding of organic nitrogen cycling will be an important aspect of future effective estuarine management.     

近海沉积物DlPCBs对斑马鱼胚胎EROD和cyp1a mRNA的影响

为探究湛江近海域海洋沉积物中类二噁英多氯联苯(dioxin-like polychlorinated biphenyls,Dl PCBs)的生物学毒性效应,选取湛江近海域2个地点(近工业区TS和近生活区JSW)采集沉积物样品,制备近海域沉积物Dl PCBs提取物,将斑马鱼胚胎暴露于不同浓度的Dl PCBs提取物,测定斑马鱼胚胎7-乙氧基异吩恶唑脱乙基酶(ethoxyresorufin-O-deethylase,EROD)活性和cyp1a m RNA相对表达量。结果发现,JSW采样点Dl PCBs提取物染毒组EROD酶活性变化与TS采样点Dl PCBs提取物一致,在各染毒浓度下,斑马鱼仔鱼EROD酶活性为对照组的1.1~1.8倍。TS和JSW采样点不同浓度Dl PCBs提取物暴露斑马鱼胚胎96 h后,使斑马鱼仔鱼cyp1a m RNA相对表达量是对照组的3.36~19.45倍。说明一定浓度的近海沉积物Dl PCBs能诱导斑马鱼仔鱼EROD酶活性和cyp1a m RNA表达量升高,且呈现浓度-效应关系。     

Simultaneous quantification of several classes of antibiotics in water,sediments, and fish muscles by liquid chromatography–tandem mass spectrometry

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

Hydrocarbon bioaccumulation from contaminated sediment by the deposit-feeding polychaeteAbarenicola pacifica

This study examines the role of the organic carbon content of sediment in aromatic hydrocarbon bioaccumulation and assesses the importance of two routes of hydrocarbon uptake: (1) the uptake of the particulate contaminant fraction from ingested sediment; (2) the uptake of the dissolved contaminant fraction from interstitial or overlying water. The lugwormAbarenicola pacifica was collected from San Juan Island, Washington, USA, in January 1989, and exposed to three sediments contaminated with [³H]benzo (a) pyrene (BaP). By manipulating the organic content of these sediments, it was possible to establish three treatments with similar BaP concentrations in the interstitial water, but differing in the amount of BaP in the bulk sediment. BaP bioaccumulation over the first few days of exposure was correlated with feeding rate, suggesting that ingested sediments were a source of BaP. The greatest body burden, however, was attained in those individuals held in sediments with the lowest organic carbon content and the lowest BaP concentration. Body burden at steady state was not correlated with either BaP concentrations in bulk sediment (dry weight or organic carbon-normalized bases) or the interstitial water. Increased organic matter decreased BaP bioavailability in a non-linear fashion. Bioaccumulation factors relative to water and organic content were relatively constant between 1 and 2% organic carbon in the sediment, but these same accumulation factors substantially underestimated body burden if applied to sandy sediments with little (0.3%) organic carbon.     

古廖涌黑臭水体生物修复及维护试验

利用生物氧化塘、底泥生物氧化、水体生物修复和河道生态恢复等技术，对广州市古廖涌黑臭水体进行治理．结果表明，在进水流量5000～8000m^3／d的高负荷工业废水和生活污水冲量下，通过生物治理，消除了水体黑臭现象，从上游到下游，水色由暗黄逐步转为黄、黄绿；在上游不断流入污水情况下，CODcr除去率达50％以上，NH3-N除去率为70％，H2S除去率达80％以上．从2003年8月到2004年3月，河道生物多样性逐步增加，先后出现枝角类、桡足类动物和鱼类．表明对于暂时无法截污的城郊河道，可以利用废弃的鱼塘、空地等对污水进行预处理，再通过上述措施和技术进行生物治理，可取得良好治理效果．本研究为城市黑臭河道，特别是暂时无法截污的城郊河道的治理和养护提供了一套切实可行的方法．图3参18