渤海湾不同站点四角蛤蜊软体部重金属含量及AhR 通道研究

渤海湾沿岸人口密集，工农、航运发达，渤海自身净化能力非常有限。因此，渤海湾 环境污染的压力越来越大，主要污染物包括重金属和持久性有机污染物的。四角蛤蜊广泛 分布于渤海湾海域，是一种重要的经济贝类，对污染物具有较强的富集能力。为了研究不 同站点渤海湾四角蛤蜊软体部重金属含量，选择大港油田、高沙岭码头、涧河村三个断面 进行研究，对不同站点四角蛤蜊软体部重金属含量进行了分析和讨论，最后对水生动物的 POPs 毒理调控通道进行了探索性研究，得到以下结果： 1. 通过比较渤海不同站点四角蛤蜊软体部重金属含量分布特征和方差分析，发现四 角蛤蜊软体部必需重金属元素含量较高，而非必需重金属元素含量较低，这是由于必需重 金属元素具有重要的生理功能作用。侧重比较A、B 两个断面各站位间四角蛤蜊软体部重 金属含量，发现虽然各站位间分布规律不明显，但各站位间差异显著。 2. 利用简单相关回归分析金属元素间及其与生物学性状间的关系，发现Mn 与Zn 之 间，Cu 与Zn 间均存在显著正相关，Se 与As、Cd 间存在显著正相关。另外，A 断面，BL 与Cd 含量显著负相关其回归方程为：Y（Cd）=－1395.97＋88.34（BL）；R=0.633；在B 断面，利用BW 和BH 分别与Cd 和As 显著负相关和显著正相关，其回归方程分别为：BW 和Cd 的回归方程为：Y（Cd）=－1968.80＋220.72（BW）；R=0.656。BH 和As 的回归方 程为：Y（As）=1496.86＋227.82（BH）；R=0.656。 3. 利用PLS（偏最小二乘分析）方法分析，发现五个生物学性状都与Co、As 呈正相 关，而与Cr、Pb、Se 呈负相关，而与必须重金属元素相关不明显。进一步分析表明表明 渤海湾海域中Co、As 含量低于四角蛤蜊正常生长发育的需要，而Cr、Pb、Se 的含量超过 四角蛤蜊正常生长发育所需的量。最后，通过PLS-DA 分析方法，发现C 站点样品能与A、 B 两个断面的站点区分开，而A、B 间未能区分开，反映了渤海湾三个断面的实际污染状 况。 4. 四角蛤蜊软体部重金属含量进行风险评价，首先，利用单因子污染指数法比较分析， 发现从1997 年-2008 年，渤海湾四角蛤蜊软体部Cd 的污染水平在不断降低，现在其含量 已低于《海洋生物质量标准》（第二类）标准。而Cr、As 有污染的趋势，需要引起重视。 然后，利用金属污染指数法进行比较研究，发现B 断面＞A 断面＞C 断面。最后，利用《人 体消费卫生标准》进行比较分析，发现Cd、Ni 存在轻度污染，因此需要加强其污染源的 控制。 5. 渤海湾污染物除了重金属外，还存在一些典型持久性有机污染物。为进一步揭示 二者间协同毒理机制，利用分子系统学方法，对芳香烃受体通道进行了探索性研究，发现 水生动物AhR通道基因在进化过程中发生了适应性进化，对进一步研究重金属和POPs对双 壳贝类的毒理机制具有参考价值。

Effect of copper, cadmium and Cu.Cd mixture on amino acid content in the poslarvae of penaeid shrimp, Penaeus monodon and P. penicillatus

This study document effects of short-term (96h) sublethal levels of copper, cadmium and their mixture on the amino acid composition of postlarvae of the penaeid shrimp, P.monodon and P.penicillatus . All experimental conditions were kept constant, temperature between 25-27•C and salinity 21-22 ppt. The estimated LD50 for Cu was 200 ug/L, for Cd 177.5 ug/L and for Cu.Cd mixture 250ug/L. In P. penicillatus at the same concentration of each metal, there was significant reduction in amino acid content, which was 8.01% higher than the control. Almost similar reduction in some amino acids was observed in P.monodon. At the maximum concentration of 400 ug/L, cadmium caused higher reduction in amino acid composition than did copper. Thus, amino acid composition may be regarded as a sensitive biochemical indicator of Cu and Cd toxicity because of the effect of these metals on protein synthesis, a signal of physiological stress in marine organisms subjected to heavy metal pollution.

Cadmium leachability and microbial population dynamics in a stabilized and bioaugmented model contaminated soil

This article presents a laboratory study on the consequences of the application of combined soil stabilization and bioaugmentation in the remediation of a model contaminated soil. Stabilization and bioaugmentation are two techniques commonly applied independently for the remediation of heavy metal and organic contamination respectively. However, for a cocktail of contaminants combined treatments are currently being considered. The model soil was contaminated with a cocktail of organics and heavy metals based on the soil and contaminant conditions in a real contaminated site. The soil stabilization treatment was applied using either zeolite or green waste compost as additives and a commercially available hydrocarbon degrading microbial consortium was used for the bioaugmentation treatment. The effects of stabilization with or without bioaugmentation on the leachability of cadmium and copper was observed using an EU batch leaching test procedure and a flow-through column leaching test, both using deionized water at a pH of 5.6. In addition, the population of hydrocarbon degrading microorganisms was monitored using a modified plate count procedure in cases where bioaugmentation was applied. It was found that while the stabilization treatment reduced the metal leachability by up to 60%, the bioaugmentation treatment increased it by up to 100% Microbial survival was also higher in the stabilized soil samples.

Purification and properties of Aspartate aminotransferase (E.C. 2.6.1.1) from skeletal muscle of Cirrhina mrigala

Aspartate aminotransferase (E.C. 2.6.1.1.) from the skeletal muscle of fresh water fish Cirrhina mrigala has been purified 40 fold by ammonium sulphate fractionation, adsorption on alumina Csub(8) gel and chromatography using DEAE-cellulose column and the properties of the purified enzyme studied. The pH optimum of the enzyme is 7.8. The Km value of aspartic acid and 2-oxoglutaric acid are found to be 2.8 x 10sub(-3) M and 1.0 x 10sub(-4) M respectively. The activity of enzyme is inhibited by p-chloromercurybenzoate, hydroxylamine hydrochloride and sodium cyanide. The inhibition by pchloromercurybenzoate is reversed by reduced glutathione, B-mercaptoethanol and cysteine. Dicarboxylic acids such as maleic acid, malic acid and succinic acid inhibit the enzyme activity. The enzyme is not activated by any of the metal ions tested and heavy metal ions such as mercury and silver strongly inhibit the enzyme activity.

Ecological risk assessment of pollution in sediment on benthic fauna in coast of Bandar Abbas

Ecological risk assessment is determination of the probability of an adverse effect occurring to an ecological system. This investigation was carried out to assess the ecological risk of sediment in coast of Bandar Abbass in 9 stations including Shilat Jetty, Hotel Amin, Poshte-Shahr, Souro, Bahonar Jetty, Powerhouse, Refinery and Rajaee Jetty from autumn 2013 to summer 2014. Results showed that Polychaete with 1177 , 1109 , 414 , 573 , ind.m2 in autumn 91 , winter 91 , spring 92 and summer 92 were the most abundant in frequency respectively. Among ecological indices, the Margalof that ranged from 4 to 7 was in a good situation while Shanoon and Berger – Parker with 1.2 (at most) and 0.32 (at least) respectively indicated an environment with probable stress. Heavy metal distribution obtained as Cd>Pb>Cu>Zn in sediment. In tissue, the distribution of heavy metals were as Crab>polychaete>Bivalve>gastropod for Pb, Gastropod>Bivalve>Polychaete>Crab for Cd, Gastropod>Crab>Polychaete>Bivalve for Cu and Gastropod>Bivalve>Crab>Polychaete for Zn. Maximum and Minimum of TOM obtained 10.16 and 1.96 percent in Posht-e-Shahr and shilat Jetty respectively and clay was the dominant grain in most area. Bioaccumulation coefficient of Zn and Cu was high in all stations. Igeo as a single index was high for Cd indicating a high risk in all stations. Potential Ecological Risk was high for Cu and Zn and goes increasingly from shilat Jetty to Rajee Jetty but goes down for Pb. Pollution index for Cu and Pb was nearly the same as Potential Ecological Risk but for Zn goes constantly. Among PAH, 5-ring and 6-ring PAhs were more concentrate comparison to other compounds in sediment. 2-ring and 3-ring, 3-ring, 4-ring and 5-ring and 5-ring PAHs were more concentrate in Gastropod, Bivalve, Crab and Polychaete respectively. HI as an index of PAH obtained 1. Ecological Risk Indices showed that the heavy metals are a serious risk for invertebrate in sediment but PAHs are not a risk for benthic community.

Effect of microbial activities on the mobility of copper in stabilised contaminated soil

Stabilisation, using a wide range of binders including wastes, is most effective for heavy metal soil contamination. Bioremediation techniques, including bioaugmentation to enhance soil microbial population, are most effective for organic contaminants in the soil. For mixed contaminant scenarios a combination of these two techniques is currently being investigated. An essential issue in this combined remediation system is the effect of microbial processes on the leachability of the heavy metals. This paper considers the use of zeolite and compost as binder additives combined with bioaugmentation treatments and their effect on copper leachability in a model contaminated soil. Different leaching test conditions are considered including both NRA and TCLP batch leaching tests as well as flow-through column tests. Two flow rates are applied in the flow-through tests and the two leaching tests are compared. Recommendations are given as to the effectiveness of this combined remediation technique in the immobilisation of copper. © 2005 Taylor & Francis Group.

Light water breeding with nitride fuel

This scoping study proposes using mixed nitride fuel in Pu-based high conversion LWR designs in order to increase the breeding ratio. The higher density fuel reduces the hydrogen-to-heavy metal ratio in the reactor which results in a harder spectrum in which breeding is more effective. A Resource-renewable Boiling Water Reactor (RBWR) assembly was modeled in MCNP to demonstrate this effect in a typical high conversion LWR design. It was determined that changing the fuel from (U,TRU)O2 to (U,TRU)N in the assembly can increase its fissile inventory ratio (fissile Pu mass divided by initial fissile Pu mass) from 1.04 to up to 1.17. © 2011 Elsevier Ltd. All rights reserved.

Effects of cadmium on chlorophyll content, photochemical efficiency, and photosynthetic intensity of Canna indica Linn.

The effects of cadmium (Cd2+) on growth status, chlorophyll (Chl) content, photochemical efficiency, and photosynthetic intensity were studied on Canna indica Linn. Plant specimens that were produced from a constructed wetland and precultivated hydroponically in 20 L of 1/10 Hoagland solution under greenhouse conditions for I week were exposed to cadmium in concentrations of 0, 0.4, 0.8, 1.6 and 3.2 mg L- Cd2+, respectively. The results show that leaves were injured in the Cd2+ solution by the third day of exposure and the injury became more serious with an increase in the applied heavy metal. Under 3.2 mg L-1 Cd2+ treatment, growth retardation, the decrease of chlorophyll content from 0.70 to 0.43 mg g(-1) FW, and a decrease in Chl a/b ratio from 2.0 to 1.2 were observed. Chl a was more sensitive than Chl b to Cd2+ stress. The decrease was the same with photochemical efficiency. Photosynthetic intensity decreased by 13.3% from 1.5X10(4) mumol m(-2)s(-1) CO2 in control to 1.3x10(4) mumol m(2)s(-1) CO2 in the treatment of 3.2 mg L-1. Because Canna species are used in heavy metal phytoremediation, these results show that C. indica can tolerate 0.4 to 0.8 mg L-1 Cd2+. Therefore, it is a potential species for phytoremediation of cadmium with some limitations only at higher concentrations.

Species transformation of trace elements and their distribution prediction in dyestuff residue incineration

The release of heavy metals from the combustion of hazardous wastes is an environmental issue of increasing concern. The species transformation characteristics of toxic heavy metals and their distribution are considered to be a complex problem of mechanism. The behavior of hazardous dyestuff residue is investigated in a tubular furnace under the general condition of hazardous waste pyrolysis and gasfication. Data interpretation has been aided by parallel theoretical study based on a thermodynamic equilibrium model based on the principle of Gibbs free energy minimization. The results show that Ni, Zn, Mn, and Cr are more enriched in dyestuff residue incineration than other heavy metals (Hg, As, and Se) subjected to volatilization. The thermodynamic model calculation is used for explaining the experiment data at 800 degrees C and analyzing species transformation of heavy metals. These results of species transformation are used to predict the distribution and emission characteristics of trace elements. Although most trace element predictions are validated by the measurements, cautions are in order due to the complexity of incineration systems.

Hg胁迫对两种基因型小麦生长及其过氧化物酶活性的影响

用不同浓度Hg处理两种基因型小麦种子,较低浓度的Hg对小麦种子萌发影响比较小,对抗旱品种的小麦种子(陕合)的萌发有略微的刺激作用。小剂量、短时间的重金属处理可以提高POD的活性,发芽后受到Hg胁迫的陕合对Hg的耐受性低于发芽前就受到Hg胁迫的陕合,也低于同样胁迫处理的小麦品种(郑引)。发芽后进行Hg胁迫处理情况下,陕合对于Hg胁迫比较敏感,POD活性随着Hg浓度的升高而下降;而郑引,低浓度Hg对其POD活性有促进作用。在小麦发芽前就受到Hg胁迫的情况下,陕合和郑引的POD活性都随着Hg浓度增加表现为先上升而后下降趋势。

板栗壳对水中Cu~(2+)吸附性能的研究

研究食品加工剩余物板栗壳对水中Cu2+的吸附性能,为其用于含铜废水的处理提供理论依据。【方法】研究吸附质溶液pH、Cu2+质量浓度、吸附剂用量、粒径、吸附温度和时间对板栗壳吸附Cu2+效果的影响,探讨吸剂和吸附剂循环利用次数对解吸和再生的影响;并采用穿透曲线和洗脱曲线对动态吸附进行了分析。【结果】吸附质溶液pH值为6、Cu2+起始质量浓度为20 mg/L、吸附剂粒径为0.25 mm时的吸附效果较好,该吸附为放热过程,升高温度虽然可以加快吸附进程,但却降低了吸附量和去除率。Na+和Ca2+对Cu2+的解吸置换能力较弱,0.1mol/L HCl可使96.1%的Cu2+得以解吸回收。通过Thomas模型预测,在固定床柱吸附条件下饱和吸附量为10.94mg/g。【结论】板栗壳对水中Cu2+的吸附性能较好,因而具有很好的应用前景。

Investigation on Fe, Mn, Zn, Cu, Pb and Cd fractions in the natural surface coatings sampled and surficial sediments collected in the Songhua River, China

Natural surface coatings sampled (NSCSs) from the surface of shingles and surficial sediments (SSs) in the Songhua River, China were employed to investigate the similarities and difference in fractions of heavy metals (Fe, Mn, Zn, Cu, Pb, and Cd) between NSCSs and SSs using the modified sequential extraction procedure (MSEP). The results show that the differences between NSCSs and SSs in Fe fractions were insignificant and Fe was dominantly present as residual phase (76.22% for NSCSs and 80.88% for SSs) and Fe-oxides phase (20.33% for NSCSs and 16.15% for SSs). Significant variation of Mn distribution patterns between NSCSs and SSs was observed with Mn in NSCSs mainly present in Mn-oxides phase (48.27%) and that in SSs present as residual phase (45.44%). Zn, Cu, Pb and Cd were found dominantly in residual fractions (>48%), and next in solid oxides/hydroxides for Zn, Pb and Cd and in easily oxidizable solids/compounds form for Cu, respectively. The heavy metal distribution pattern implied that Fe/Mn oxides both in NSCSs and SSs were more important sinks for binding and adsorption of Zn, Pb and Cd than organic matter (OM), and inversely, higher affinity of Cu to OM than Fe/Mn oxides in NSCSs and SSs was obtained. Meanwhile, it was found that the distributions of heavy metals in NSCSs and SSs were similar to each other and the pseudo-total concentrations of Zn, Cu, Pb and Cd in NSCSs were greater than those in SSs, highlighting the more importance for NSCSs than SSs in controlling behaviours of heavy metals in aquatic environments.

长期重金属污染胁迫下农田土壤微生物特征研究

本论文以沈阳张士污灌区土壤为例，首次采用传统微生物生态学与现代微生物分子生态学相结合的研究方法系统地研究了污灌区长期重金属污染胁迫下原位农田土壤微生物特征。结果表明，虽然已经停止污灌十多年，张士灌区土壤耕作层（0～30 cm）仍然存在普遍的Cd污染，灌区土壤Cd含量高达1.75～3.89 mg kg-1。部分区域土壤Cd呈现向下迁移的趋势,且同时伴随有Cu、Zn复合污染。灌区土壤Cd含量较高时清水灌溉能降低土壤表层Cd含量，灌区土壤Cd含量下降到一定程度（约2 mg kg-1）后，清水灌溉对消除土壤表层Cd污染的作用消失。重金属元素中Cd对土壤微生物的影响最突出，在三个不同季节中土壤Cd与土壤微生物生物量（MBC）和微生物商（qM）呈显著负相关，与土壤微生物代谢商（qCO2）呈显著正相关。所检测的微生物指标中qM和qCO2与多种重金属元素呈显著相关性，可作为评价一定程度重金属污染的微生物指标。土壤营养元素（除P外）与微生物特征呈显著正相关性，土壤营养元素对微生物的刺激作用有可能在某种程度上掩盖了重金属对土壤微生物的负面影响。 用16S rDNA-PCR-DGGE方法，研究了不同浓度Cd胁迫下土壤Cd抗性细菌群落结构的动态变化，结果表明在Cd的胁迫下Cd抗性细菌多样性显著增加，不同土壤样品中Cd抗性细菌群落结构向相似的方向偏移，群落结构最终将可能趋向一致。Cd胁迫使敏感菌Pontibacter消失，而伯克氏菌（Burkholderia）、罗尔斯通氏菌（Ralstonia）、芽孢杆菌（Bacillus）和节杆菌（Arthrobacter）则富集成为优势菌。 从张士灌区Cd污染土壤中分离出32株Cd抗性细菌，研究了Cd抗性细菌和Cd抗性基因cadA的分布特征。这32株Cd抗性细菌分别归属于拟杆菌门(Bacteroidetes)（37.5%）、变形菌门(Proteobacteria) （37.5%）、放线菌门(Actinobacteria)（9.4%） 和厚壁菌门(Firmicutes)（15.6%）。在液体LB培养基中对Cd的抗性浓度都大于2 mmol L-1，对Zn抗性浓度介于5～13 mmol L-1。首次从Cetobacillus属的Cd抗性菌株S1基因组DNA中扩增出cadA基因的部分片断。在芽孢杆菌属(Bacillus)的4株菌N7，N9，N10和N11的基因组DNA中扩增出cadA基因的部分片断。序列分析结果表明这5株菌的cadA基因序列相似性为99％～93％，它们与坚强芽孢杆菌（Bacillus firmus） cadA 基因序列(M90750）相似性为94％～92％。系统发育分析结果表明这5株菌的cadA都与Bacillus firmus cadA 基因有着较近的亲缘关系。不同属的Cd抗性细菌间cadA基因的高度相似性揭示了cadA基因能在不同种属间转移的特性。

典型沉积物组分结合的重金属对芦苇的植物有效性研究

沉积物中的重金属，与无机、有机胶体通过吸附、配位体交换、络合、共沉淀等作用与沉积物中不同组分结合，由于污染来源、环境条件、赋存时间的不同，重金属可以有不同的化学形态。不同赋存形态的重金属具有不同的生物环境地球化学过程及生物有效性规律。 5种氧化物矿物吸附态Cd的富集实验表明，芦苇对吸附在含铝矿物表面的Cd吸收最多，其次为铁锰矿物。比表面积较大、等电点较低的矿物与Cd的吸附强度和稳定性较强，进而造成Cd的植物有效性较低。可能对Cd的吸附解吸产生影响的是植物根系分泌的有机酸，有机酸对不同矿物吸附Cd的解吸规律与芦苇对Cd的吸收规律一致。有机酸本身性质，如羧基数量、电离常数等影响Cd解吸量。 环境中与水合氧化物结合（吸附和共沉淀）的Cd生物有效性研究表明，两种结合形式的Cd均被芦苇富集，不同处理体系中富集强度不同，根中富集量9.1 ~ 37.8 mg/kg；地上部分富集量为0 ~ 10.0 mg/kg。由于共沉淀处理增加了矿物的比表面积和吸附位点密度，并且在预先混合的过程中Cd进入氧化物内部使结合了Cd的水合氧化物更加稳定，因此吸附态Cd的植物有效性大于共沉淀。老化处理可使Cd向水合氧化物晶格内部扩散，因而显著地降低吸附态Cd的富集。由于Fe(OH)3的等电点较低、阳离子交换容量较大，因此与Fe(OH)3 结合的Cd有效性较低。采用2种低分子量有机酸对Cd进行解吸，Cd的解吸规律与芦苇对镉的富集规律一致。 与无定形铁氧化物结合（吸附和共沉淀）的多金属富集实验表明，芦苇对不同金属的富集强度不同。金属离子与铁氧化物的亲合力由金属阳离子水合半径和水化数决定，本研究中金属与铁矿物结合亲合力遵循：Pb > Cd > Cu > Ni，因此芦苇对金属的富集规律大致为Ni > Cu > Cd > Pb。在多金属处理体系中，金属之间往往竞争相同的吸附位点，形成相似络合物，从而改变吸附强度和稳定性。Ni和Cd在根中富集量较少，可能是体系中Pb的投加产生了竞争作用。此外，植物对金属的选择性吸收也影响金属的植物有效性。解吸实验表明，吸附处理的金属解吸量大于共沉淀，单一金属投加体系中，重金属的解吸量：Ni > Cu > Cd > Pb；多种金属投加体系中，Pb的解吸量增加，Cd的解吸量下降。根系分泌的低分子量有机酸对沉积物中的重金属有重要的活化作用，这可能是植物吸收污染沉积物或土壤中重金属的重要因素之一。 针铁矿和不溶性腐殖酸吸附态Cd的富集实验表明，水溶态金属的有效性最大，其次为针铁矿吸附态，最难被植物吸收的是腐殖酸吸附态金属。由于腐殖酸结构复杂、表面多官能团和吸附位点，因此与金属的亲合力较大，结合牢固，不易被芦苇吸收富集。解吸实验验证了相同条件下，柠檬酸对腐殖酸吸附态金属的解吸量小于针铁矿结合态。pH值是影响金属与沉积物中活性组分结合强度和稳定性的重要因素。较低的pH值，水相中H+浓度较高，与金属离子竞争吸附位点，降低针铁矿或腐殖酸对金属离子的吸附容量和稳定性。另外，环境pH值较低（低于矿物等电点）时，矿物表面趋于带正电，增加了金属离子吸附的难度。 水体－沉积物体系中，可溶性腐殖酸影响重金属的迁移和生物有效性。不同的腐殖酸浓度和投加顺序对金属的生物有效性影响研究表明，单一金属投加体系中，金属在芦苇体内的富集规律为：Cu > Cd > Ni > Pb，金属在植物不同部位的分布遵循：根 > 叶 > 茎 > DCB，腐殖酸浓度的增加降低了金属的富集（除Ni外）。混合金属投加体系中，金属的富集遵循：Ni > Cu > Cd > Pb（HA 5 ppm）；Cd > Ni > Cu > Pb（HA 20 ppm）。与单一金属投加相比，金属的富集量降低，DCB提取态金属含量增加。腐殖酸浓度的增加降低了金属的生物有效性。腐殖酸加入顺序显著影响的金属与针铁矿的吸附，进而影响金属的生物有效性。