硝基芳香化合物的植物作用研究进展

硝基芳香化合物是环境中难以降解的污染物之一。因其用途广泛，大量残留于土壤，水体和大气中，造成的环境污染日趋严重。多种植物对该类污染物具有吸收、富集和代谢降解作用，利用植物对其环境污染进行治理是一种有效的方法。文章在总结国内外有关硝基芳香化合物的植物作用研究基础上，重点阐述了植物对硝基芳香化合物的吸收、转运和代谢过程，分析了吸收、代谢机理以及影响吸收的因素；硝基芳香化合物的理化特性、浓度和植物自身特性及其它外界条件都会影响植物对该类化合物的吸收，植物可以通过体内降解、体外联合代谢、根部释放酶催化的机制实现该类化合物的降解。目前，硝基芳香化合物进入植物细胞膜的机理认知不足，模拟模型缺乏有力数据验证；代谢机制中参与反应的酶、化合物等体系和反应产物环境特性仍不明确，植物修复可行性缺乏有力证据。未来将在模型预测构建、降解机理和修复工程的实际应用方面作进一步探究，以形成系统的认知，为硝基芳香化合物污染土壤和农产品的生态风险评价以及植物修复提供理论依据。     

部分硝基芳烃对鲤鱼的急性毒性及定量构效关系

本文报告了２６个硝基芳烃大对鲤鱼的急性毒性，应用ＬＳＥＲ法得出了相关关系显著的ＱＳＡＲ方程。化合物分子的本征体积是毒性的主要影响因素。硝基芳烃的毒性随着分子本征体积，αｍ和Ｉ值的增大而增大，随着βｍ值的增大而减小。     

稀土元素在鱼体中的生物富集作用

研究了鲤鱼若干部分对轻、中和重稀土元素的生物富集作用。结果表明:鲤鱼对水体中可溶性稀土元素的富集能力较低。其最大生物浓缩因子BCF的顺序为内脏>鳃>骨骼>肌肉,且发现鲤鱼对于混合稀土溶液没有协同作用和拮抗作用。重稀土元素在鲤鱼若干部分的生物富集能力最低,而轻稀土和中稀土元素的生物富集能刀则显示出很小的差异。     

菲和镉单一及复合污染条件下在毛蚶体内的富集动力学研究

采用室内半静态双箱动力学模型实验,研究了菲和镉单一及复合污染条件下在毛蚶(Anadara subcrenata)体内的生物富集,通过对富集与释放过程中毛蚶体内菲和Cd的富集量进行非线性曲线拟合,获得了菲和Cd单一及复合污染条件下在毛蚶体内的吸收速率常数k1、释放速率常数k2、生物富集因子BCF、生物半衰期B1/2和平衡状态下最大富集量CA max等动力学参数。实验结果表明,菲和Cd在实验前期富集速率较高,8 d以后富集速率减缓,释放阶段与富集阶段相似。毛蚶对菲的BCF值为37.80,远大于Cd的BCF值13.12,且生物半衰期时间更长,菲更容易在生物体内富集。菲和Cd联合暴露条件下,在毛蚶体内的CA max和BCF值均大于单一作用,说明二者同时暴露时,毛蚶对菲和镉的吸收富集均有所增强。实验模型拟合度较好,输出值和实测值之间无显著性差异,拟合方程和拟合参数可信。     

多效唑在大型溞体内富集与释放行为

本文探讨了大型在含藻（系统Ａ）和不含藻（系统Ｂ）水体内，对￣３Ｈ多效唑的生物富集以及释放行为。用药物动力学模型分析了多效唑在大型－水体之间的转移。结果表明：在实验初期，由于大型对小球藻的摄食作用，大型在系统Ａ的生物富集系数显著大于系统Ｂ，存在生物放大作用。而在实验后期，两个系统中大型对多效唑的生物富集系数趋于相近。多效唑在大型体内的释放行为符合一级动力学过程，半衰期为６ｈ．实验结束后，多效唑在大型体内的残留量占总量的２０％。     

环境样品中炸药的痕量富集及HPLC分析

炸药对环境的影响主要来自于军工企业及军事单位的武器生产、贮存及试验过程中的污染.痕量炸药的分析一般采用高效液相色谱法,如美国环保局(EPA)批准的方法(SW846中的方法8330),Waters最近推出的环境样品中炸药的痕量富集及HPLC分析方法,对于现有的方法提出了以下改进.1.固相萃取技术富集样品为了改进现有方法及减少有机溶剂的使用量,EPA正在就使用新的样品处理技术替代传统的液-液萃取进行探讨.固相萃取由于快速、经济、操作简便而倍受青睐.Waters生产的Porapak RDX预处理柱由一种低萃取度树脂制成,专门用于水中芳香硝基化合物及硝氨的富集,这种柱子具有很高的选择性,回收率达到90%以上.Ippb和10ppb样品富集,分析的变异系数分别好于7%和5%.图1为纯水中含lppb各化合物经Porapak RDX柱富集40倍后在waters反相色谱系统上的分离谱图.     

应用生物模拟采样法快速评估水中邻苯二甲酸酯的生物富集性

利用三油酸甘油酯-醋酸纤维素半透复合膜(TECAM)对12种邻苯二甲酸酯类化合物(PAEs)进行微耗式快速富集试验(24 h),估算生物模拟采样方法对PAEs化合物的富集动力学参数以及富集系数,比较了膜富集系数(MCF)与生物富集系数(实验测定、模型预测)之间的相关性,及其随化合物的辛醇-水分配系数(KOW)的变化趋势。结果表明:(1)随着疏水性的增强,化合物在TECAM膜中具有不同的富集趋势:弱疏水性化合物能快速平衡,中疏水性化合物先经历线性富集阶段随后到达曲线富集阶段,中强疏水性化合物一直处于线性阶段;(2)膜对PAEs的富集系数随KOW的增加先上升后下降,与BCF随KOW的变化趋势一致,同时两种富集系数对KOW均符合二次曲线模型,并且MCF的相关性更好;(3)对MCF整体高于BCF的结果做出了解释——生物代谢使得BCF偏低,而TECAM对PAEs的富集不涉及代谢过程。尽管MCF不能表征生物体对邻苯二甲酸酯等可生物降解目标化合物的代谢过程,但该方法不受物种个体差异影响,具有估算水生生物富集目标化合物的潜在能力,更利于化合物之间的评估比较,并可作为对比研究生物代谢对BCF的影响。     

土壤中结合残留态农药的生态环境效应

土壤中农药结合残留态的形成，导致其活性暂时降低，但并未从土壤中消失，在特定的环境条件下又重新释放到环境中并表现出较高的生物有效性，从而威胁农产品质量安全与环境质量。文章论述了土壤中结合残留态农药的定义、形成过程及影响因素、老化和释放过程及机制。土壤中结合残留态农药主要通过吸附过程、化学反应及物理镶嵌等作用而形成，其形成过程受农药的结构和化学特性、土壤理化性质、环境条件和农艺措施的影响。老化是化合物和土壤组分紧密结合，减少被普通提取方法提取出来的数量，降低了化合物的生物有效性。同时老化的物质在土壤环境条件改变的情况下又重新释放到土壤溶液中或进行矿化，此过程可以通过物理一化学机制或生物化学作用而发生。重新释放到环境中的结合残留态农药又表现出较高的生物有效性，可能被植物、动物或微生物所吸收，并沿食物链富集和放大或进入水体污染水产品和造成水质恶化，从而威胁人体健康。文章还分析了土壤结合残留态农药可能带来的环境问题，提出了此问题今后研究的方向。     

有机化合物生物富集因子快速测定方法

本文运用二室模型，研究了挥发和非挥发性有机物在鲤鱼体内生物富集因子快速测定方法。     

0#柴油和原油水溶性成分在黑鲷(Sparusmacrocephlus)体内的富集动力学

石油是海洋环境中的一类重要污染物,为探索石油烃在海洋生物体内的生物富集动力学特征,应用半静态双箱动力学模型在室内模拟了黑鲷(Sparus macrocephlus)对0#柴油和东海平湖原油水溶性成分(Water accommodated fraction,WAF)的生物富集实验,通过对富集与释放过程中黑鲷体内石油烃的动态检测以及对检测结果的非线性曲线拟合,获得黑鲷对0#柴油、原油WAF的吸收速率常数k1、释放速率常数k2、生物富集因子BCF、平衡状态下黑鲷体内石油烃含量CAmax和生物学半衰期B1/2等动力学参数.拟合结果得到的各动力学参数分别为:黑鲷对0#柴油WAF的吸收速率常数k1范围为3.46-4.87、k2为0.047 6-0.070 8、BCF为48.79-102.30、CAmax为1.53-2.93 mg/kg、B1/2为9.79-14.57 d;黑鲷对原油WAF的吸收速率常数k1范围为2.12-5.75、k2为0.036 3-0.050 5、BCF为58.35-147.21、CAmax为4.01-7.00 mg/kg、B1/2为13.71-19.08 d.黑鲷对0#柴油、原油WAF的吸收速率常数k1、BCF均随外部水体中石油烃浓度的增大而减少,对0#柴油和原油WAF的释放速率常数k2与外部水体中石油烃浓度无明显相关性,CAmax整体随外部水体中石油烃浓度的增大而增大.对模型的拟合优度检验结果显示,模型的拟合优度良好.研究表明,0#柴油在黑鲷体内的富集量低于原油WAF、释放量略高于原油WAF,不同种类石油的烃类组分可能是主要控制因子之一.     

Uptake and depuration of organic contaminants by blue mussels (Mytilus edulis) exposed to environmentally contaminated sediment

Experiments were designed to expose blue mussels (Mytilus edulis) to contaminated sediment collected from Narragansett Bay, Rhode Island, USA in 1982. Measurements were taken to allow comparisons of the uptake and depuration of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). In addition, concentration factors in the mussels were calculated separately against the dissolved and particulate phase concentrations and the results from the exposure and control systems were compared. Both PAHs and PCBs were rapidly accumulated by the mussels exposed to the contaminated sediment. After the mussels were transferred to control seawater, individual PAHs were depurated with half-lives ranging from 12 to 30 d. Individual PCBs showed depuration half-lives which ranged from 16 to 46 d. Concentration factors in the mussels calculated against the particulate phase concentrations were very different in the exposure and control systems. Concentration factors calculated using only the dissolved phase concentrations (bioconcentration factors) showed excellent agreement in the two systems, possibly an indication that the dissolved phase was the direct source of the contaminants accumulated by the mussels. The bioconcentration factors for PCBs were higher than those of PAHs when compounds with similar n-octanol/water partition coefficients were compared.     

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。     

Biologische Sanierung von Rüstungsaltlasten

Many sites of former ammunition plants are contaminated with the explosive 2,4,6-trinitrotoluene, its derivatives and reduction products. Such nitroaromatic compounds have a high human and ecotoxic potential. Plant uptake of these organic pollutants is known and could be confirmed under field conditions. In this paper rhizospheric soil was analyzed to characterize the effect of vegetation on TNT-contaminated soil. Common beans (Phaseolus vulgaris) were used as test plants. The experiments were performed on two areas with different TNT concentrations. The data reveal a significant decrease of extractable TNT in rhizospheric soil by a factor of 5 to 6 during the vegetation period. On the area with high TNT concentration, an enrichment of nitroaromatic compounds in root tissue was found compared to the rhizospheric soil. Aminodinitrotoluene could be confirmed as the primary pollutant in the root. These results refer to a potential application of plants to biological remediation of soil contaminated with ammunition-specific pollutants.     

有机污染物对发光菌和鱼的毒性相关性研究

研究有机污染物对不同水生生物毒性的种间关系有助于探讨有机污染物对水生生物的毒性作用模式。本文应用1 470种有机化合物对发光菌的毒性数据和949种有机化合物对鱼的毒性数据,研究有机化合物对发光菌和鱼的种间毒性作用模式。结果表明,有机化合物对发光菌和鱼的毒性呈正相关,但种间相关性较差。通过计算毒性比率TR值表明多数类别有机化合物具有相似的种间毒性作用模式。基线和弱惰性化合物对发光菌和鱼的毒性均与辛醇水分配系数log Kow具有良好的线性关系,这说明基线和弱惰性化合物在发光菌和鱼体内的残余量CBR值均为一个常数。这些化合物对发光菌和鱼具有相似的毒性作用模式和生物吸收过程。另外,一些亲水性化合物的log TR值具有较大的种间差异,即对发光菌和鱼的毒性效应具有较大的种间差异,表明亲水性化合物对发光菌为反应型化合物,而对鱼为麻醉型化合物。有机化合物对发光菌和鱼的毒性种间相关性通过引入疏水性参数得到了一定的改善,这表明这些亲水性化合物毒性效应的种间差异有一部分归因于有机化合物在发光菌和鱼体内的生物富集不同,而不是由于与生物分子的反应性不同。这些亲水性化合物相对于鱼的腮和皮肤更容易通过发光菌的细胞膜,与生物分子发生化学反应,从而具有较高的毒性效应。Log Kow大于7的化合物对发光菌和鱼均具有较低的毒性,说明有机化合物在生物体内的富集能力对有机化合物剩余毒性的判别起着重要作用。     

Bioconcentration of Cd and Ni in various tissues of two marine bivalves living in different habitats and exposed to heavily polluted seawater

Two marine bivalves, Mytilus galloprovincialis and Callista chione, were exposed to various concentrations of cadmium and nickel (0.5, 1.0, 2.5 and 20 ppm), for 20 days, plus 10 days’ depuration period, in a laboratory experiment. Animals from each experimental condition were dissected and the bioaccumulation and distribution of Cd and Ni were determined in their gills, mantles and remaining bodies. The concentrations of Fe and Zn were also measured. Heavy metal tolerance, bioconcentration and distribution of heavy metals in tissues were considerably different in M. galloprovincialis and C. chione: (i) both animals were tolerant to Ni pollution, even at the highest concentration used; (ii) C. chione was more tolerant to Cd; (iii) M. galloprovincialis was a better Cd and Ni accumulator, with the exception of the highest Cd concentration tested, where C. chione accumulated more Cd; (iv) Fe and Zn levels were much more affected in M. galloprovincialis; (v) in general, accumulation and distribution of Ni and Cd in the tissues were metal-, species- and time of exposure- dependent; (vi) significant amounts of heavy metals remained in the tissues after 10 days’ depuration. Our results support a hypothesis for a two competing processes mechanism for metal accumulation and detoxification.     

生物体内环形挥发性甲基硅氧烷的分布、行为及效应研究进展

近年来,环形挥发性甲基硅氧烷(cVMSs)因其优异的物化特性而被广泛应用在工业生产和日常生活的各个方面,特别是经常被添加到个人护理品(PCPs)等各类消费品中。目前,人们对cVMSs在环境介质中的污染水平及其迁移转化行为有了一定的了解。另外,cVMSs兼有疏水性和挥发性,且难以进行生物降解,因此该类物质进入环境后潜在的生态风险,特别是其生物富集、生物累积、生物放大和毒性效应等已成为关注的热点。本文综述了cVMSs在全球生物体内的残留水平,并在此基础上总结了cVMSs生物效应等相关研究成果。总体上,众多研究表明cVMSs在某些水生生物体内呈现中等的生物富集性和累积性。然而,与其相对明确的生物富集/累积性相比,目前文献针对cVMSs生物放大效应的研究结果存在明显差异。建议后续的研究能够深入探索其生物效应,尤其是结合其在生物体内的降解过程以及中间产物的毒性数据,进一步评估其生态环境效应和人类健康风险。     

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。     

Untersuchungen zur Umweltchemie,Kontaminationserkundung und -bewertung

Leachate and groundwater have been investigated at a site contaminated with ammunition residues. The presence of nitroaromatic compounds and their degradation products was investigated by GC-MS-screening methods. Nitro-, amino-nitro-, and amino-aromatic substances of the ?TNT type“ were analyzed along with polar substances such as 3,5-dinitro-o-cresol and 4,6-dinitro-o-cresol. Investigation of these primary metabolites is important for risk assessment and for determining clean-up measures     

Uptake and depuration of cesium in the green mussel Perna viridis

 The accumulation and depuration of Cs in the green mussels (Perna viridis) commonly found in the subtropical and tropical waters were studied under the laboratory conditions using radiotracer techniques. Following an initial rapid sorption onto the mussel's tissues, uptake of Cs exhibited linear patterns over a short exposure time (8 h) at different ambient Cs concentrations. The concentration factor was independent of ambient Cs concentration. The calculated uptake rate and initial sorption constant of Cs were directly proportional to the ambient Cs concentration. The calculated uptake rate constant from the dissolved phase in the mussels was as low as 0.026 l g⁻¹ d⁻¹. Uptake rates of Cs in the mussels were inversely related to the ambient salinity. Uptake increased about twofold when the salinity was reduced from 33 to 15 ppt. The effect of salinity on Cs uptake was primarily due to the change in ambient K⁺ concentration. The uptake rate decreased in a power function with increasing tissue dry weight of the mussels, although the initial sorption was not related to the mussel's body size. The efflux rate constant of Cs in the mussels was 0.15 to 0.18 d⁻¹, and was the highest recorded to date among different metals in marine bivalves. The efflux rate constant also decreased in a power function with increasing tissue dry weight of mussels. A simple kinetic model predicted that the bioconcentration factor of Cs in the green mussels was 145, which was higher than measurements taken in their temperate counterparts. The bioconcentration factor also decreased in a power function with increasing tissue dry weight of mussels. Received: 27 October 1999 / Accepted: 16 June 2000