水体内藻类的生物地球化学

藻类对水体内生命元素的转化及其分布、迁移的影响．是目前水体内藻类生物地球化学研究的重点内容。藻通过光合作用和生物矿化，控制着C、N、Si、P、S、Ca等元素在水体内的循环；驱动着C和S在水体和大气之间的交换，进而影响大气中的C和S。藻生物积累及其对环境变化的及时反馈，使藻类成为地球化学环境变化的生物指示物。本文对水体内藻类的生物地球化学进行了综述。     

介微孔复合沸石分子筛对重金属离子吸附性能的实验研究

以介微孔复合沸石分子筛MCM-41／ZSM-3为吸附剂，采用静态吸附方法初步研究了其对重金属离子Cu^2 、Zn^2 、Pb^2 、Cd^2 的吸附性能。结果表明：对于配置的60mg／dm^3重金属离子溶液，使用分子筛用量为10g／dm^3时，在较宽的pH范围内MCM-41／ZSM-3对Cu^2 、Zn^2 、Pb^2 、Cd^2 的吸附率可达90％以上；对等温吸附曲线的回归分析得出Cu^2 、Zn^2 、Pb^2 、Cd^2 在实验浓度范围内符合Langmuir单吸附位吸附曲线且具有较大的吸附容量。     

广东大宝山矿区速溶性矿物的理化特征及其生物毒性效应

通过理化分析及生物检测方法，对大宝山矿区土层中速溶性矿物的理化特征及其生物毒性进行了初步分析。结果表明，大宝山矿区土层中的矿物组成成分较为复杂，含有大量的氧化性硫酸盐及其他致酸物质和重金属。矿物易溶于水，所得溶液pH较低（pH〈2．15），并富含大量的重金属Cu、Pb、压、Cd以及Fe、Mn等元素，因而具有极强的生物毒性。矿物水溶液的稳定性较差，溶液的理化指标变化较大。急性和慢性生物毒性试验表明，即使溶液pH被中和至7．22以上，但溶液仍显示出较强的生物毒性，3．117mg／L的矿物溶液即会使试验生物在24h内的死亡率达到100％，说明该水溶性矿物的生物毒性除了受强酸性物质的影响外，还与矿物中多种组分共存时的联合生物毒性有关。在一般的水体中，该水溶性矿物的安全排放浓度仅为0．006mg／L。研究结果可为对矿山废物外排对下游生态环境的影响及生态风险评价提供理论依据。     

密云水库水体的地球化学特征

研究了密云水库在2001年一个完整水文年的水体地球化学特征。结果表明：该水库水质清澈，透明度平均为2．54m，pH平均值为8．81；水中溶解氧丰富，平均为6．98mg／L；有机物耗氧量平均为2．07mg／L；平均矿化度为246．97mg／L，水型属重碳酸盐类、钙组Ⅱ型水(CⅡ^Ca)。水体中的主要生物营养元素氮含量较高，总氮平均为0．96mg／L，磷含量较低，总磷平均为0．025mg／L。水库氮、磷浓度比为38．4：1，显示磷为该水体生物生产力的主要限制性营养元素。水体中重金属铬、镍的含量变化特征反映了原始老变质基岩成分的有关特点；而重金属铁、杨、铅、汞、砷的含量变化规律则显示密云水库水体已受到上游流域工业活动的影响。     

坡缕石对Zn^2＋的吸附性能及吸附工艺条件优化研究

从坡缕石粘土提纯人手，进行了坡缕石吸附Zn^2 的实验研究，结果表明坡缕石对水中Zn^2 的吸附性能主要受振荡速度、吸附时间、溶液pH值、吸附剂用量等因素影响，30℃时坡缕石对Zn^2 的等温吸附曲线同时符合Langmuir方程和BET方程。在本实验条件下，坡缕石对水中的Zn^2 (20mL，Zn^2 浓度均为50mg／L)的最佳吸附工艺条件为：振荡速度150r／min，吸附时间120min，吸附剂用量0．120g，溶液pH为6．2，此条件下去除率达到T95．5％。     

水介质中多金属海水矿瘤砷吸附的研究

本文详细报告了水介质中多金属海水矿瘤吸附砷（Ⅲ）和砷（Ⅴ）的研究结果。海水矿瘤的元素成分主要由铁、锰、硅（含有微量铝）、铜、钴和镍。海水矿瘤对砷（Ⅴ）的吸附取决于水介质的pH值，而砷（Ⅲ）的吸附不受水介质pH值的影响。砷吸附数据大体上符合兰米尔（Langmuir）等温线。砷（Ⅲ）和砷（Ⅴ）的动力学数据满足一种假定的二级动力学模型。海水矿瘤去除砷的效果取决于砷的初始浓度。当水介质中砷（Ⅲ）的初始浓度为0．34mg／L或砷（Ⅴ）的初始浓度为0．78mg／L时，海水矿瘤的最佳剂量为0．74mg／g。砷（Ⅲ）的吸附一般取决于离子环境。除PO4^3-以外，砷（Ⅲ）的吸附不受阴离子的影响，但受阳离子的影响显著。另一方面，砷（Ⅴ）的吸附受阴离子的影响显著，但不受阳离子的影响。试验结果表明，海水矿瘤吸附的砷（Ⅲ）主要为内部结核复合物，而吸附的砷（Ⅴ）为部分内部结核和部分外部结核复合物。当水介质的pH值为2-10时，吸附的砷（Ⅲ）和砷（Ⅴ）的解吸附较小。当水介质的pH值为6或更高时，海水矿瘤能被用于吸附地下水中的砷（Ⅲ）和砷（Ⅴ）物种。海水矿瘤被成功地用于去除采于印度西孟加拉邦的6种受砷污染地下水样中的砷（6种地下水样中砷的浓度范围为0．04-0．18mg／L）。     

流动注射分光光度法同时测定水中挥发酚及氰化物

在单针进样器的基础上，增加一个三通流路同时进样，在线消解-流动注射分光光度法测定水中挥发酚及氰化物。实验结果表明，挥发酚浓度在0mg/L～0．2mg／L、氰化物浓度在0mg/L～0．5mg／L范围内具有良好的线性关系。通过在线气体扩散分离技术，提高了分析速度，每小时可完成12个～15个样品的分析。方法的相对标准偏差〈5％，回收率在90．4％～108．5％之间。     

多目标生态地球化学调查土壤样品中砷硒锑有效态分析方法的商榷

以0．10mol／L NaH2PO4和0．50mol／L NaHCO3为浸提剂，试验了其对土壤样品中As、Se、Sb的浸提效果；以氢化物发生-原子荧光法(HG-AFS)测定了浸提液中As、Se、Sb的含量。方法在武汉、宁镇测区应用试验表明：采用0．50mol／L的NaHCO3为As、Se、Sb的有效态浸提剂，以HG—AFS法测定其含量的方案可行，检出限分别为：0．006mg／kg、0．001mg／kg、0．002mg／kg。精密度试验，6个标准样品的RSD(n=12)As、Se、Sb均≤10．15％。     

活性炭对无机汞和苯基汞的吸附行为探讨

试验了活性炭对无机汞和苯基汞的吸附和解吸行为。结果表明，在活性炭用量为0．2g，ψ=0．5％的王水介质中搅拌1．5h，无机汞和苯基汞的吸附率均达96％以上，无机汞和苯基汞的吸附容量分别为82．5μg/g和66．0μg/g。吸附后的无机汞和苯基汞分别用含有60mg EDTA的2．8mol/L HNO3溶液和5．6mol/L HNO3-1．0mol/L H2SO4溶液定量洗脱，用冷原子吸收光谱法测定，实现了无机汞和苯基汞的定量分离。对2μg/L的无机汞和苯基汞进行测定，相对标准偏差(n=11)分别为5．4％和6．2％。在实际水样中加标回收和测定，无机汞和苯基汞的回收率分别为97．8％～108％、94．0％～106％。     

含石英二元矿物复配物对聚丙烯酰胺吸附的协同效应

选择了粒径为50—154μm的6种储层标准矿物，以石英作为参比矿物，固相总质量为2．0000g，分别配成了2：0，1：1，0：2(g／g)3种质量组合，以1：10的固／液比与浓度为1000mg／L的聚丙烯酰胺(蒸馏水配制)溶液在常温25℃下作了静态吸附实验，分别反应8h、36h、72h和120h，高速分离后用酸/漂白液沉淀浊度法检测聚丙烯酰胺浓度，并计算吸附量。结果表明了如下的吸附量顺序：石膏＞蒙脱石＞高岭石＞黑云母＞白云母＞石英。多种矿物共存时存在吸附量与矿物配比不成比例的协同效应。当石膏或蒙脱石存在时，对聚丙烯酰胺的吸附趋势和吸附量由石膏或蒙脱石控制。该研究为聚合物驱油施工方案的优化设计提供了必要的理论依据。     

Isolation and molecular characterization of some copper biosorped strains

The biosorption of copper (II) from aqueous solution using different bacterial strains was studied. Copper-biosorbing bacteria were isolated from tannery effluent collected from Borg Al-Arab, Alexandria, Egypt. These isolates displayed different degrees of copper biosorption under aerobic conditions. Based on 16S rDNA gene sequence analysis, three of them (S2, S5 and S7) were identified as Chryseobacterium sp., Enterobacter sp. and Stenotrophomonas sp., respectively. Initial copper (II) ion concentrations from 25–250 mg/L at constant temperature 30 °C were studied. The residual copper (II) concentration and its toxicity effect in solution were determined using atomic absorption spectrophotometer and bioluminescent bioreporter. The bioluminescence inhibition of strain (S5) reached to 91.4 % as compared with the strain (S7) reached to 83.3 % at 225 mg/L of copper ion where the maximum biosorption efficiency for S5 and S7 were 71 % and 70.1 % correspondingly using atomic absorption. The bioluminescent bioreporter was proved to be fast and accurate technique for measurement the toxicity effect of residual copper (II) in solution.     

Study of mango biomass (Mangifera indica L) as a cationic biosorbent

Unfertilizable fruiting buds of mango plant Mangifera Indica L, an agrowaste, is used as a biomass in this study. The efficacy of the biosorbent was tested for the removal of lead, copper, zinc and nickel metal ions using batch experiments in single and binary metal solution under controlled experimental conditions. It is found that metal sorption increases when the equilibrium metal concentration rises. At highest experimental solution concentration used (150 mg/L), the removal of metal ions were 82.76 % for lead, 76.60 % for copper, 63.35 % for zinc and 59.35 % for nickel while at lowest experimental solution concentration (25 mg/L), the removal of metal ions were 92.00% for lead, 86.84 % for copper, 83.96 % for zinc and 82.29 % for nickel. Biosorption equilibrium isotherms were plotted for metal uptake capacity (q) against residual metal concentrations (C_f) in solution. The q versus C_f sorption isotherm relationship was mathematically expressed by Langmuir and Freundlich models. The values of separation factor were between zero and one indicating favourable sorption for four tested metals on the biosorbent. The surface coverage values were approaching unity with increasing solution concentration indicating effectiveness of biosorbent under investigation. The non-living biomass of Mangifera indica L present comparable biosorption capacity for lead, copper, zinc and nickel metal ions with other types of biosorbent materials found in literature and is effective to remove metal ions from single metal solutions as well as in the presence of other co-ions with the main metal of solution.     

Removal of uranium(VI) from aqueous solutions using Eucalyptus citriodora distillation sludge

Adsorption and desorption of uranium(VI) from dilute aqueous solutions by Eucalyptus citriodora distillation sludge was studied in a batch mode. The potential of Eucalyptus citriodora distillation sludge to remove uranium(VI) from aqueous solutions has been investigated at different conditions of solution pH, metal ion concentrations, biosorbent dosage, biosorbent particle size, contact time and temperature. The results indicated that biosorption capacity of Eucalyptus citriodora distillation sludge was strongly affected by the medium pH, the biosorbent dose, metal ion concentrations and medium temperature. Reduction in particle size increased the biosorption capacity. Langmuir and Freundlich isotherm models were applied to biosorption data to determine the biosorption characteristics. An optimum biosorption capacity (57.75 mg/g) was achieved with pH 4.0, particle size 0.255 mm, biosorbent dose 0.5 g/100 mL and initial uranium(VI) concentration of 100 mg/L. Uranium(VI) removal by Eucalyptus citriodora distillation sludge was rapid, the equilibrium was established within 60 min and pseudo-second-order model was found to fit with the experimental data. The biosorption process decreased with an increase in the temperature indicating its exothermic nature. Pretreatments of biomass with different reagents affected its biosorption capacity. A significant increase (34 %) in biosorption capacity (83.25 mg/g) was observed with benzene treatment. Fourier-transform infra-red studies showed the involvement of carbonyl, carboxyl and amide groups in the biosorption process. The results indicated that sulfuric acid had the best effects as an eluent showing 93.24 % desorption capacity.     

Biosorption of ammoniacal nitrogen from aqueous solutions with low-cost biomaterials: kinetics and optimization of contact time

The biosorption of ammoniacal nitrogen (N-NH₄ ⁺) from aqueous solutions by dead biomass of brown seaweed Cystoseira indica and Jatropha oil cake (JOC), which is generated in the process of biodiesel recovery from its seeds, was studied under diverse experimental conditions. The N-NH₄ ⁺ biosorption was strictly pH dependent, and maximum uptake capacity of C. indica (15.21 mg/g) and JOC (13.59 mg/g) was observed at initial pH 7 and 3, respectively. For each biosorbent–N-NH₄ ⁺ system, kinetic models were applied to the experimental data to examine the mechanisms of sorption and potential rate-controlling steps. The generalized rate model and pseudo-second-order kinetic models described the biosorption kinetics accurately, and the sorption process was found to be controlled by pore and surface diffusion for these biosorbents. Results of four-stage batch biosorber design analysis revealed that the required time for the 99 % efficiency removal of 40 mg/L N-NH₄ ⁺ from 500 L of aqueous solution were 76 and 96 min for C. indica and JOC, respectively. The Fourier transform infrared spectroscopy analysis before and after biosorption of ammonium onto C. indica and JOC revealed involvement of carboxylic and hydroxyl functional groups.     

Behavior of metals (Cu,Zn and Cd) in the initial stage of water system contamination: Effect of pH and suspended particles

The fate of potentially harmful metals (PHM) after their entry into an unpolluted fresh water body depends on the physicochemical and biological parameters of the aquatic ecosystem. This paper considers the effect of pH and suspended particles (SP) on the behavior of Cu, Zn and Cd when they enter a fresh water reservoir. In a field experiment, four mesocosms were constructed in the Novosibirskoye Reservoir to allow systematic variation of SP concentration (15 or 250 mg/L) and pH (8.5 or 6.5). The initial concentrations of Cu, Zn and Cd in the mesocosms were 1000, 1000 and 200 μg/L, respectively. Natural bottom sediments were used to provide additional mineral SP, and water hyacinth was used as a floating plant species. Over 11 days, measurements were made of several indicators: residual metal concentration in solution ([PHM]_w); metal concentration in SP ([PHM]_s); primary productivity of the phytoplankton community; mass of settled SP; PHM concentration in settled SP; and PHM bioaccumulation by water hyacinth. The ratio [PHM]_w/[PHM]_s in the water varied in the order Cu < Zn < Cd and was higher at pH 6.5 than at pH 8.5. This observation reflects different PHM sorption (Cu > Zn > Cd) onto mineral SP and PHM biosorption by planktonic organisms. Phytoplankton acts as a renewable source of organic SP and plays an important role in metal removal from the water in the mesocosms. After 11 days the residual concentrations of Cu, Zn and Cd in the mesocosm without SP addition (initial SP concentration was 15 mg/L) were 272, 355 and 84 μg/L, respectively. The residual concentrations of Cu, Zn and Cd in mesocosms with SP addition were 57, 100 and 14 μg/L at pH 8.5 and 80, 172 and 20 μg/L at pH 6.5, respectively. Therefore, addition of SP resulted in faster and more complete removal of metals into the bottom sediments. Floating plants (water hyacinth) accumulated PHM (Cu > Zn > Cd) more effectively at pH 8.5 than at pH 6.5, and PHM concentrations in the roots were higher than in settling SP. The general trends of PHM removal from contaminated water via sedimentation and bioaccumulation are compared with changes of metal speciation in solution.     

ZH型重金属螯合纤维对水溶液中Sr2+的吸附行为

研究了ZH型重金属螯合纤维对水溶液中Sr~(2+)的吸附行为,考察了pH值、纤维加入量、Sr~(2+)初始浓度、作用时间等对吸附行为的影响,并采用SEM、EDS和FTIR等现代分析测试手段探讨了ZH型重金属螯合纤维对Sr~(2+)的吸附机制。结果表明,在pH值为7.0、纤维加入量为2.0 g/L、Sr~(2+)初始质量浓度为50 mg/L的条件下,纤维对Sr~(2+)的吸附在4 h左右基本达到平衡。实验条件下ZH型重金属螯合纤维对Sr~(2+)的最大吸附量可达26.22 mg/g。等温吸附拟合结果表明,ZH型重金属螯合纤维对Sr~(2+)的吸附可能是以单分子层为主的单分子层和多分子层吸附共同作用的结果。纤维对Sr~(2+)的动力学吸附过程符合准二级动力学模型。红外光谱分析表明Sr~(2+)与纤维上—NH_2和—COOH等基团进行配位络合从而吸附在纤维表面,—CH_2—和C=CH_2等基团参与此吸附过程。能谱分析表明Sr~(2+)与纤维上Na~+和Ca~(2+)还存在着离子交换作用。     

Biosorption of lead from acid solution using chitosan as a supporting material for spore forming-fungal biomass encapsulation

Asexual spores of the filamentous fungus Rhizopus arrhizus were used as the resting biomass as they tolerate chitosan gelling for mycelia growing in chitosan beads. Biosorption of lead using the dead detergent pre-treated chitosan-immobilised and grown fungal beads was performed with initial lead (II) nitrate concentrations ranging from 9.02 to 281.65 mg/L. The adsorption data were best correlated with equilibrium adsorption isotherms in the order Redlich–Peterson, Langmuir, Freundlich and Fritz–Schlünder by non-linear regression. The biosorption kinetic model of pseudo second-order (R ² > 0.99) fitted better than pseudo first-order and modified pseudo first-order models. Among the four pseudo second-order kinetic models, the Blanchard model was the best fit for the experimental biosorption data. The rate-limiting step of biosorption of lead was shown to be intraparticle diffusion controlled according to Weber and Morris model fitting. The beads could be regenerated using 1 M nitric acid solution. This illustrated the good performance of the beads for regenerated sorption/desorption at least five cycles.     

The concentration control of soluble copper in a mine tailings stream

Comparison of decreasing total copper content and increasing pH of an abandoned copper mine drainage stream to the stability fields of malachite, tenorite, and cupric hydroxide indicates that soluble copper is not lost by precipitation but by sorption on the stream sediments.     

锰矿石脱硫产物处理含铜废水动态实验研究

氧化型锰矿石脱硫产物含大量硫化锰,利用这种材料装填固定床进行净化水中铜离子的动态试验.在材料粒径0.45～0.9mm、进水pH=5.8、进水滤速4.58 m/h条件下,1 t锰矿石脱硫产物可以处理923 tρ(Cu~(2+))=50 mg/L的含铜废水,出水ρ(Cu~(2+))<0.5 mg/L,低于国家一级排放标准.控制进水pH在4～9之间、降低进水滤速、采用较小粒径的材料有利于提高锰矿石脱硫产物处理含铜废水的容量.利用X射线粉末衍射(XRD)和扫描电镜-能谱分析(SEM-EDS)对材料和产物进行表征,证明锰矿石脱硫产物去除水中铜离子是基于离子交换反应的原理.     

微藻CO2同化过程的稳定碳同位素分馏值

研究微藻CO2同化过程中的碳同位素分馏值,对研究微藻在碳效应过程中的作用具有重要意义。目前还没有获取微藻CO2同化过程的稳定碳同位素分馏值的在体实验方法。文章以莱茵衣藻、蛋白核小球藻、及野外红枫湖混合藻三种岩溶湖泊微藻为例,利用双向标记建立了能在体获得此分馏值的方法,并通过此分馏值定量了微藻的各种无机碳利用途径份额。获得各自CO2同化过程中的碳同位素分馏值分别为15.3‰、14.8‰、21.7‰。三种藻分馏值差异主要与藻的种类及其细胞体积大小有关。利用此分馏值计算出衣藻、小球藻、混合藻自然培养下的碳酸氢根离子途径利用份额分别为100%、81.1%、97.8%,表明了生长在岩溶湖泊的微藻利用无机碳的途径主要为碳酸氢根离子。