基于Tenax脱附技术评价沉积物中不同碳质对菊酯类农药生物有效性的影响研究

本文选取泥炭、生物质炭、木炭和活性炭4种含碳材料,结合以经济底栖生物菲律宾蛤仔(Venerupis philippinarum)为受试生物的生物累积实验和Tenax连续萃取法,阐述不同碳质对沉积物中4种菊酯类农药生物有效性的影响,并将Tenax萃取结果与底栖生物的累积结果进行了相关分析。结果表明,碳质的添加导致沉积物中菊酯类农药的快速脱附组分(Frap)降低,极慢速脱附组分(Fv s)增大,生物有效性降低,且4种碳质对Frap的影响有所不同,然而因为菊酯类农药的理化性质,Frap的差异并不显著。Tenax 6 h和24 h的单点萃取组分与快速脱附组分相关性显著(P0.0001),基本可以代替完整的脱附动力学评价生物有效性,但是对于组成复杂,有机碳(OC)和黑炭(BC)含量高的沉积物进行研究评价时仍应注意由此产生的偏离。Tenax快速脱附组分与2种底栖生物累积结果之间具有显著的相关性(R2=0.38,P0.0001),表明在OC和BC含量不同的沉积物中,Tenax萃取技术也可以预测菊酯类农药在经济底栖生物菲律宾蛤仔体内的累积量,进而为沉积物中HOCs的环境质量和相关水产品的质量评估提供更为快捷、有效的参考依据。     

基于Tenax脱附动力学的沉积物中菊酯类农药生物有效性研究

菊酯类农药已被广泛应用于农业、林业和渔业生产中,因其高疏水和亲脂性使其更易残留在沉积物中,因此研究其生物有效性对沉积物的环境质量和风险评价具有重要意义。采用强吸附性树脂(Tenax)连续萃取法研究洋山港潮间带表层沉积物中4种代表性菊酯类农药(高效氯氟氰菊酯、联苯菊酯、氯菊酯和甲氰菊酯)的脱附动力学,评价菊酯类农药在沉积物中的生物有效性,并将Tenax萃取结果与海洋经济底栖生物菲律宾蛤仔(Ruditapes philippinarum)的累积试验进行比较。结果表明,在有机碳(OC)含量较低的洋山港潮间带表层沉积物中,菊酯类农药的快速解吸组分比例(Frap)高达50%以上,快速、慢速和极慢速解吸速率常数数量级分别为10-1、10-2和10-5~10-3。与Frap相比,Tenax单点萃取结果可用于评价沉积物中菊酯类农药的生物有效性,并且在应用上更加快速、经济有效。与菲律宾蛤仔体内菊酯类浓度(Cb)之间相关性研究表明,Tenax 24 h萃取结果(Cs,24 h)更适用于生物体内污染物累积的预测(lg Cb=4.03 lg Cs,24 h-17.02,R2=0.88,P<0.05)。该研究结果不仅可以简单、快速地评价沉积物中菊酯类污染物的生物有效性,为海洋沉积物的环境质量和风险评价提供可靠依据;还可以有效地预测经济双壳类底栖动物体内菊酯类污染物的生物累积,为养殖领域沉积物环境风险评价及相关水产品的食品风险评价提供更为简单快捷的方法。     

基于Tenax脱附技术评价洋山港海域悬浮物中多环芳烃的生物有效性

在测定海洋生物对洋山港海域悬浮物中多环芳烃(Polycyclic Aromatic Hydrocarbons,PAHs)富集系数的基础上,结合Tenax连续萃取法研究悬浮物中PAHs的脱附动力学,为评价洋山港悬浮物中PAHs的生物有效性提供简单、快速的评价方法。结果表明,洋山港海域生物对悬浮物中PAHs的生物-底泥富集因子(BSAF)处于0.02~0.21之间,说明该海域生物体对悬浮物中PAHs的富集程度较低;悬浮物中PAHs的快速脱附比例(Frap)处在20~40%之间,且快速、慢速和极慢速脱附速率常数数量级分别为10~(-1)、10~(-2)和10~(-4);此外Tenax 6 h单点萃取的PAHs浓度与大多数海洋生物体内的累积浓度相关性良好(0.64r20.80,P0.01),表明Tenax 6 h单点萃取比例可以简便、快速地预测悬浮物中PAHs在海洋生物体内的累积量。该方法可用于评价海域悬浮物PAHs的污染并为相关海产品的质量安全和食用风险提供生物有效性评价依据。     

固相微萃取在评价沉积物中菊酯类农药生物有效性及生物累积中的仿生研究

菊酯类农药已广泛用于农用、卫生、渔业等领域,因高疏水性累积于沉积物中的此类污染物的生物有效性评价对环境风险研究具有重要意义。采用PDMS(聚二甲基硅氧烷)高聚物作为固相微萃取材料,基于热力学平衡微损耗性方法测定了沉积物孔隙水中高效氯氟氰菊酯、联苯菊酯、氯菊酯和甲氰菊酯的自由溶解态浓度(Cfree);同时将PDMS上菊酯类农药的浓度与菲律宾蛤仔体内生物累积浓度的相关性进行了比较研究。结果表明,该方法可以准确测定菊酯类农药在沉积物孔隙水中的Cfree(23.3~255 ng·L-1)并用于评价此类物质(菊酯类农药)的生物有效性;菲律宾蛤仔对四种菊酯类农药的富集系数(BCF)为27.8~301,相对较小;菊酯类农药在PDMS上的浓度和菲律宾蛤仔体内的浓度满足lg Cb,lip=11.64lg CPDMS-51.29(R2=0.980)的定量关系,相关性极显著(P=0.009)。但生物—沉积物富集系数(BSAF)和PDMS-沉积物富集系数(PSAF)的分析比较发现,基于PDMS和生物体内菊酯浓度极显著相关的仿生应用还有待污染物在菲律宾蛤仔体内生物转化数据的进一步补充和校正。     

海洋沉积物中的镉及不同形态镉的生物有效性

镉是一种生物非必需的毒副作用很强的重金属元素.进入海洋环境中的镉,最终有相当部分进入沉积物中,并对底栖生物造成危害.通过测定不同镉质量浓度暴露条件下海水、沉积物和生物体内的镉的形态和含量,研究了海洋沉积物中不同形态镉的生物有效性.结果表明,菲律宾蛤仔对Cd的蓄积随着时间增加,呈现先快速增加的趋势,在24 h内其蓄积速率最大,96 h后生物体内镉的质量分数出现缓慢下降趋势.在蓄积时间一定的条件下,在任何Cd含量沉积物下,菲律宾蛤仔都可以蓄积Cd,而且随着沉积物中镉质量分数升高,生物体内蓄积的镉的质量分数也呈现上升趋势.活性镉(可交换态)是沉积物中镉存在的主要形式(45.48x.96%),硅酸盐结合态和黄铁矿结合态的金属只占较小的比例,活性镉是影响沉积物中重金属镉生物可利用性的最有效形态.     

河蚬在我国沉积物毒性评价与鉴定中的应用研究

河蚬作为原产并广泛分布于我国及东南亚的双壳类淡水软体动物,是我国众多水域的底栖优势种。河蚬对水体污染物具有较强累积能力,已成功用于水体沉积物生物富集及生物毒性效应研究。但应用于沉积物毒性鉴别评估(TIE)研究整体上仍处于起步阶段,尚未形成一套标准指标测定方法和技术体系。为此,本研究在调查底栖生物在我国沉积物毒性研究的基础上,以河蚬为主要研究对象,探讨其在我国生态分布等生物学背景,系统分析其对重金属和有机污染物的生物富集特征以及相关生物毒性效应方面的研究进展,以期为河蚬作为我国特色的沉积物毒性鉴别评估(TIE)受试生物提供参考依据。     

137 Cs在我国滨海核电周边海洋生物的富集及生态风险研究

铯-137(~(137)Cs)是滨海核电站液态流出物中主要人工放射性核素和重要监控指标之一,易被水生生物累积,有关核电周边海域内海洋生物的核素富集状况备受关注。通过分析海洋生物富集放射性~(137)Cs的方式、生物富集系数的种群特征、人工放射性核素在生物体内的辐射剂量率状况,结果显示:1)滨海核电周边海域内~(137)Cs的放射性水平较低; 2)海洋生物对于~(137)Cs的富集未呈现显著的种群规律; 3)目前对放射性铯的富集能力较高的生物主要是底栖生物; 4)核电厂周边海域内海洋生物通常未达到可导致电离辐射损伤的辐射剂量率水平。随着滨海核电在我国的大力发展,对能够快速反映环境放射性状况的指示生物的筛选、生物放射性质量安全及其生态健康风险需进一步关注。     

氨氮胁迫下菲律宾蛤仔肝胰腺内参基因的筛选

利用荧光定量PCR技术对目标基因进行转录水平分析,选择合适的内参基因作为对照是其前提条件.随着氨氮胁迫菲律宾蛤仔毒性效应的深入研究,需要准确评价氨氮对蛤仔肝胰腺组织基因表达的影响.然而,不同浓度氨氮条件下的菲律宾蛤仔肝胰腺组织的内参基因的筛选尚未报道.本研究以2种不同氨氮浓度暴露菲律宾蛤仔14 d的肝胰腺组织cDNA为qRT-PCR的模板,利用geNorm、NormFinder、BestKeeper和RefFinder软件评估β-肌动蛋白(Actin)、延伸因子1-α(EF-1α)、β-微管蛋白(Tubu)、18S核糖体RNA(18S)、泛素(Ubi)和亲环蛋白A(CyPA)6个内参基因的表达稳定性.结果表明,肝胰腺组织中备选内参基因的表达稳定性依次为:Actin>18S>CyPA>Ubi>Tubu>EF-1α,即Actin为表达最稳定的内参基因.本研究为进一步分析氨氮胁迫下菲律宾蛤仔肝胰腺组织的基因表达情况,提供了可靠的内参基因.     

全氟辛酸(PFOA)对菲律宾蛤仔体内酶活性的影响

采用半静态毒性实验方法,将菲律宾蛤仔(Ruditapes philippinarum)分别暴露于0.2、2、20μg·L-1的全氟辛酸(perfluorooctanoic acid,PFOA)中,在处理后第1、3、6、10、15、21天分别取样,测定整体组织中超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、过氧化物酶(POD)、谷胱甘肽-S-转移酶(GST)、7-乙氧基异吩噁唑酮脱乙基酶(EROD)活性和过氧化脂质(LPO)含量。酶活性分析结果显示:PFOA对菲律宾蛤仔组织SOD、CAT和POD活性均呈现先促进后抑制的作用;低浓度组SOD活性在暴露第1天达到最高,显著高于对照组(P<0.01);中高浓度组SOD活性在暴露第6天达到最低;暴露1~15 d,低浓度组CAT活性均显著高于对照组(P<0.05);高浓度组CAT活性在暴露第6天得到显著诱导,其余时间基本处于抑制状态;中浓度组POD活性在暴露第3天即达到最高,高浓度组POD活性基本一直处于抑制状态;随着PFOA暴露时间的延长,菲律宾蛤仔组织LPO含量呈现了先降低后升高的趋势;各浓度组中EROD的活力都显著被诱导(P<0.01),与处理浓度呈正相关;中高浓度组的GST活性在胁迫期间变化比较显著,呈现诱导-抑制的变化规律。研究表明,PFOA暴露能够引起菲律宾蛤仔组织抗氧化酶和生物转化酶的变化,可以与其他敏感性指标一起作为指示早期海洋PFOA污染的生物标志物。     

环渤海近岸海域表层沉积物及底栖生物中PBDEs的赋存特征及富集行为

多溴联苯醚(PBDEs)作为一种新型的持久性有机污染物,在海洋环境中广泛存在,研究PBDEs在不同介质中的赋存状态对于理解其环境行为及归趋具有重要的意义。通过采集不同区域沉积物及生物样品,考察了PBDEs在环渤海近岸海域表层沉积物及底栖生物中的含量及空间分布特征、污染模式及生物-沉积物富集因子。结果表明,环渤海沿岸表层沉积物中PBDEs总量(Σ10PBDEs)的浓度范围在0.446~26.8 ng·g-1(干重,dw)之间,中值为1.02 ng·g-1(dw),底栖生物中PBDEs(Σ9PBDEs)的浓度范围为0.053~9.90 ng·g-1(dw),中值为1.25 ng·g-1dw;沉积物中BDE-209为最主要的单体,平均丰度达到90.5%,生物体中主要以低溴代BDEs为主,其中单体BDE-47的含量最高,平均丰度范围为43.2%~49.7%;沉积物和生物中PBDEs的含量在空间上存在显著的差异,其中莱州湾和锦州附近区域的结果明显高于其他区域;5种不同的底栖生物对PBDEs均表现出一定的生物富集性,其中∑9PBDEs的BSAF值按从大到小的顺序为菲律宾蛤仔(0.43~4.06,mean=1.19)紫贻贝(0.34~2.86,1.03)四角蛤蜊(0.17~1.95,0.82)麻蛤(0.13~2.33,0.61)牡蛎(0.09~1.20,0.52)。辛醇水分配系数(log KOW)与不同物种BSAF值的相关性分析结果表明,除BDE-17单体外,其他单体的BSAF值表现出随log KOW的升高而下降的趋势。     

污染水体中河蚬的生物毒性响应研究进展

河蚬作为广泛分布于世界各国的典型底栖生物,由于其活动性低、滤食性等特征被广泛用作指示生物研究多种水体污染物的生物有效性。但迄今为止,尚没有系统论述污染水体中河蚬生物毒性响应的研究进展。为此,本文从污染物种类、测试指标、试验参数等角度探讨了过去30多年间河蚬在氨、重金属、有机污染物生物富集及生物毒性效应等方面的研究过程及主要成果。以往研究主要以河蚬生物体内累积、形态学及行为学观察、生化指标、代谢组学、基因完整性等指标表征污染水体的生物毒性效应,并随着分子生物学的发展已逐步由多指标全面表征代替单一指标测试。此外,现有研究多偏重于重金属和持久性有机污染物,对氨、新型污染物及纳米材料的河蚬生物毒性效应探讨尚处于起步阶段。河蚬在自然水体污染状况评估、污染水体的生物修复、水体毒性预测等方面具有较高适用性,但河蚬在沉积物毒性鉴定评估(TIE,Toxicity Identification and Evaluation)中的应用研究依然较为缺乏,有待进一步开展。     

Linear alkylbenzene sulphonates (LAS) and bioaccumulation of heavy metals (Cu and Pb) in Ruditapes philippinarum

The effect of linear alkylbenzene sulphonate (LAS) on copper and lead bioaccumulation in Ruditapes philippinarum was studied. The in vitro and in vivo effect of LAS on acid and alkaline phosphatase activities was also examined. For lead, significant differences (P<0.01) were observed between organisms exposed to lead and to the mixture of LAS and lead. In the case of copper, these differences were only significant in the digestive gland (P<0.05). In vitro acid phosphatase was inhibited by LAS and the mixture of LAS with copper showed the effect of decreasing the enzymatic activity. Nevertheless, in vivo no significant differences in the digestive gland and gills (P < 0.05) were observed.     

Aufnahmepfade von POPs in Biota

POPs (persistent organic pollutants) associated with aquatic sediments can pose a risk to aquatic food chains, since they can be re-introduced to the food web. One major pathway is the bioaccumulation of POPs by endobenthic, sedimentingesting invertebrates (especially tubificid oligochaetes). These worms serve as food for benthivorous fish, which thereby ingest the sediment-borne chemicals and may accumulate contaminant concentrations far higher than from water exposure alone, and consequently transfer them to organisms of higher trophic levels. In order to evaluate such a potential biomagnification, a laboratory test was developed. It consisted of a two-step food chain including the sediment dwelling freshwater oligochaete Tubifex tubifex (Müller) and the three-spined stickleback (Gasterosteus aculeatus, Linné), a small teleost fish which often feeds primarily on benthic invertebrates. Artificial sediment and reconstituted water were used. To examine the influence of benthic prey on the bioaccumulation of a POP in the predator, fish were exposed to ¹⁴C-labelled hexachlorobenzene via spiked water, spiked sediment, pre-contaminated prey organisms, and to combinations of these exposure routes. Summarising the results of these experiments, it could be shown that the exposure to HCB via different routes resulted in a significantly higher accumulation in fish than an exposure to single pathways. It was concluded that the major uptake routes for fish were the overlying water and the food, whereas the contribution of spiked sediment itself was relatively small. HCB was biomagnified in the rested laboratory food chain. Therefore, concerning secondary poisoning, the environmental risk assessment of POPs like HCB should not be based on existing bioaccumulation tests alone, since they focus only on exposure via the water pathway. Instead, the influence of food and sediment as exposure routes should be considered as well, using comprehensive food chain modelling and/or laboratory studies.     

沉积物中重金属Pb和Cd对河蚬的毒性效应研究

以河蚬为受试生物,以存活率、呼吸抑制率为测试终点,研究了沉积物和上覆水中重金属Pb、Cd对底栖生物的毒性效应,并探讨了沉积物中酸挥发性硫化物(acid volatile sulfide,AVS)和同时提取金属(simultaneously extracted metals,SEM)对重金属生物有效性的影响。结果表明,沉积物中Pb、Cd对河蚬致死效应较低,当Pb、Cd浓度分别为400、100 mg獉kg-1,连续暴露21 d时,致死率低于20%;沉积物中Pb、Cd对河蚬14 d的呼吸抑制率EC50分别为519和151 mg獉kg-1;上覆水中Pb和Cd离子浓度较低,对生物毒性效应贡献可以忽略;SEM/AVS值和生物呼吸抑制率有着明显的线性相关性,当SEMPb/AVS1,SEMCd/AVS0.6时,重金属对河蚬有明显的毒性效应。     

Concentrations and classification of HCHs and DDTs in soil from the lower reaches of the Jiulong River, China

Soil is an important source to other environmental media and organisms for organochlorine pesticides (OCPs) bioaccumulation. Twenty-four representative surface soil samples were collected from the lower reaches of the Jiulong River, China, in 2009. The concentrations of hexachlorocyclohexane isomers (HCHs) ranged from 0.38 to 39.52 ng·g^?1, with a mean value of 9.51 ng·g^?1. The concentrations of dichlorodiphenyltrichloroethanes (DDTs) and their metabolites were within the ranges of 0.94–700.99 ng·g^?1, with a mean value of 71.17 ng·g^?1. The concentrations of HCHs and DDTs in the soil were lower than the first grade level (50 ng·g^?1) of the Chinese Environmental Quality Standard (GB15618-1995). Hierarchical Cluster Analysis (HCA) and Pearson’s bivariate Correlations Analysis (PCA) were used to analyse the distribution and contamination levels of OCPs in this region. The results showed that DDTs were the major contaminants and there were no significant correlations between various OCPs concentrations and the total organic carbon (TOC) contents. A significant positive correlation was observed between HCHs and DDTs (p<0.01), which indicates that HCHs and DDTs may have similar sources and fate in the study area.     

Organochlorine pesticide in water and bottom sediment from Aiba Reservoir (Southwestern Nigeria)

Levels of organochlorine pesticides (OCPs) in water and sediment from Aiba reservoir (Southwestern Nigeria) have been assessed. The aim of the study was to investigate the pollution status of the reservoir water and the bottom sediment. Analytical measurements were carried out for 20 OCPs using standard literature methods. The results showed higher levels of OCPs in the bottom sediment than the water. Significant positive correlations at p<0.05 level were observed for OCPs compounds in water except γ-BHC and endosulfan III, whereas in sediments α-chlordane, dieldrin, endosulfan II, pp-DDT, endrin ketone and methoxychlor did not show any correlation, and aldrin was negatively correlated with pp-DDD. The mean levels of OCPs in both water and sediments were higher, in most cases, than recommended levels for drinking water. Owing to possible toxicity and bioaccumulation tendency of OCPs by the aquatic habitats, the levels of OCPs detected in water and sediment samples could be a source of future health problems. Environmental monitoring of the reservoir is highly recommended.     

Interlinked temporal changes in environmental conditions, chemical characteristics of sediments and macrofaunal assemblages in an estuarine intertidal sandflat (Seto Inland Sea, Japan)

Five field surveys were conducted in an estuarine intertidal sandflat of the Seto Inland Sea (Japan) between April 1994 and April 1995. Chlorophyll a, pheopigments, total organic carbon and acid-volatile sulphides (AVS) of surface and subsurface sediments, and macrofaunal assemblages were investigated in parallel at 15 stations. Monthly hydrological data of low-tide creek water adjacent to the flat were used as a complementary environmental characterisation of the study area. Strong temporal changes were found among sampling dates, most remarkably in autumn with a major increase of algal detritus and AVS, a sharp reduction in macrofaunal abundances and species richness, and a massive mortality of the clam Ruditapes philippinarum. This dystrophic event was preceded by a photoautotrophic and hypertrophic spring–summer characterized by abundant fresh (i.e., living) algal material, including microphytobenthos and macroalgae (Ulva sp.). In summer, abundant macrofaunal assemblages reached the highest biomass values (455 g wet weight m⁻² or 60.6 g ash free dry weight m⁻²), with a major contribution of filter-feeding bivalves Musculista senhousia and R. philippinarum. These are among the highest values reported in the literature for sedimentary shores. From autumn, there was a progressive recolonisation of macrofauna, initiated by few opportunistic polychaetes (e.g., Cirriformia tentaculata and Polydora sp.), apparently promoting a fast sediment recovery in winter, and followed by new bivalve recruits in the next spring. This study provides the first evidence of significant and interlinked within-year changes in chemical characteristics of sediments and macrofaunal assemblages in an estuarine intertidal flat at a small spatial scale (i.e., tens of meters). This demonstrates the high temporal variability of species–environment relations in these systems and a close relationship in seasonally driven trophodynamic processes among primary producers and benthic consumers. We conclude that a thorough parallel evaluation of the temporal changes in chemical characteristics of sediments should be taken into account in assessing the year-round distribution and changes of intertidal macrofauna, particularly in eutrophic, estuarine intertidal flats.An erratum to this article can be found at     

镉和铅对菲律宾蛤仔脂质过氧化及抗氧化酶活性的影响

为了研究亚致死浓度的重金属对海洋贝类的毒性效应,探讨其可能的作用机理,在实验生态条件下以菲律宾蛤仔(Ru-ditapes philip pinarum)为目标生物,采用半静态毒性实验方法,研究了不同浓度Cd2+(0.0948、0.237和0.474mg·L-1)和Pb2+(0.276、0.690和1.380mg·L-1)对菲律宾蛤仔鳃和消化腺组织中超氧化物歧化酶(SOD)、过氧化氢酶(CAT)活性以及丙二醛(MDA)含量的影响。结果显示:(1)鳃和消化腺中的抗氧化酶及MDA的变化呈现出类似的趋势,在胁迫初期,各浓度处理组菲律宾蛤仔鳃和消化腺组织SOD和CAT与对照组相比活性都显著升高(P<0.01),呈现出明显的诱导效应,而MDA含量与对照组相比差异不显著(P>0.05);随着胁迫时间的延长,高浓度Cd2+(0.474mg·L-1)和Pb2+(1.380mg·L-1)处理组中SOD、CAT活性快速下降,与对照组相比差异显著;低浓度处理组中的抗氧化活性虽然也较对照组有所下降,但总体下降幅度不如高浓度组明显,并且所历暴露时间较长。各浓度处理组中MDA含量变化一致,均呈现出先升高后降低的趋势,且含量均高于对照组。(2)通过相关性分析,菲律宾蛤仔消化腺组织中的SOD活性与Cd2+浓度的相关性大于鳃组织,与Pb2+浓度的相关性则小于鳃组织;消化腺组织中的CAT活性与Cd2+、Pb2+浓度呈抛物线型相关,与鳃组织CAT活性相关性不十分显著。这说明消化腺组织中SOD活性对Cd2+的敏感性大于鳃组织,消化腺组织中CAT活性对Cd2+、Pb2+的敏感性大于鳃组织。因此,菲律宾蛤仔消化腺中SOD、CAT对水环境中的重金属反应敏感,且存在一定的剂量-效应关系,消化腺组织中SOD和CAT活性与其他敏感性指标一起可以作为指示早期海洋重金属污染的生物标志物。