Response of soil catalase activity to chromium contamination

The impact of chromium(III) and (VI) forms on soil catalase activity was presented. The Orthic Podzol, Haplic Phaeozem and Mollic Gleysol from di erent depths were used in the experiment. The soil samples were amended with solution of Cr(III) using CrCl3, and with Cr(VI) using K2Cr2O7 in the concentration range from 0 to 20 mg/kg, whereas the samples without the addition of chromium served as control. Catalase activity was assayed by one of the commonly used spectrophotometric methods. As it was demonstrated in the experiment, both Cr(III) and Cr(VI) have an ability to reduce soil catalase activity. A chromium dosage of 20 mg/kg caused the inhibition of catalase activity and the corresponding contamination levels ranged from 75% to 92% for Cr(III) and 68% to 76% for Cr(VI), with relation to the control. Catalase activity reached maximum in the soil material from surface layers (0–25 cm), typically characterized by the highest content of organic matter creating favorable conditions for microorganisms.     

Electro-oxidation of Ni (II)-citrate complexes at BDD electrode and simultaneous recovery of metallic nickel by electrodeposition

The simultaneous electro-oxidation of Ni (II)-citrate and electrodeposition recovery of nickel metal were attempted in a combined electro-oxidation-electrodeposition reactor with a boron-doped diamond (BDD) anode and a polished titanium cathode. Effects of initial nickel citrate concentration, current density, initial pH, electrode spacing, electrolyte type, and initial electrolyte dosage on electrochemical performance were examined. The efficiencies of Ni (II)-citrate removal and nickel metal recovery were determined to be 100% and over 72%, respectively, under the optimized conditions (10 mA/cm², pH 4.09, 80 mmol/L Na₂SO₄, initial Ni (II)-citrate concentration of 75 mg/L, electrode spacing of 1 cm, and 180 min of electrolysis). Energy consumption increased with increased current density, and the energy consumption was 0.032 kWh/L at a current density of 10 mA/cm² (pH 6.58). The deposits at the cathode were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). These characterization results indicated that the purity of metallic nickel in cathodic deposition was over 95%. The electrochemical system exhibited a prospective approach to oxidize metal complexes and recover metallic nickel.     

Biosorption of Cr(III) from aqueous solution by freeze-dried activated sludge: Equilibrium, kinetic and thermodynamic studies

Batch biosorption experiments were conducted to remove Cr(III) from aqueous solutions using activated sludge from a sewage treatment plant. An investigation was conducted on the effects of the initial pH, contact time, temperature, and initial Cr(III) concentration in the biosorption process. The results revealed that the activated sludge exhibited the highest Cr(III) uptake capacity (120 mg·g⁻¹) at 45°C, initial pH of 4, and initial Cr(III) concentration of 100 mg·L⁻¹. The biosorption results obtained at various temperatures showed that the biosorption pattern accurately followed the Langmuir model. The calculated thermodynamic parameters, ΔGo° ( − 0.8–4.58 kJ·mol⁻¹), ΔH° (15.6–44.4 kJ·mol⁻¹), and ΔS° (0.06–0.15 kJ·mol⁻¹·K⁻¹) clearly indicated that the biosorption process was feasible, spontaneous, endothermic, and physical. The pseudo first-order and second-order kinetic models were adopted to describe the experimental data, which revealed that the Cr(III) biosorption process conformed to the second-order rate expression and the biosorption rate constants decreased with increasing Cr (III) concentration. The analysis of the values of biosorption activation energy (E _a = −7 kJ·mol⁻¹) and the intraparticle diffusion model demonstrated that Cr(III) biosorption was film-diffusion-controlled.     

Kinetics of hexavalent chromium reduction by iron metal

The kinetics of Cr(VI) reduction to Cr(III) by metallic iron (Fe⁰) was studied in batch reactors for a range of reactant concentrations, pH and temperatures. Nearly 86.8% removal efficiency for Cr(VI) was achieved when Fe⁰ concentration was 6 g/L (using commercial iron powder (< 200 mesh) in 120 min). The reduction of hexavalent chromium took place on the surface of the iron particles following pseudo-first order kinetics. The rate of Cr(VI) reduction increased with increasing Fe⁰ addition and temperature but inversely with initial pH. The pseudo-first-order rate coefficients (k _obs) were determined as 0.0024, 0.010, 0.0268 and 0.062 8 min⁻¹ when iron powder dosages were 2, 6, 10 and 14 g/L at 25°C and pH 5.5, respectively. According to the Arrehenius equation, the apparent activation energy of 26.5 kJ/mol and pre-exponential factor of 3 330 min⁻¹ were obtained at the temperature range of 288–308 K. Different Fe⁰ types were compared in this study. The reactivity was in the order starch-stabilized Fe⁰ nanoparticles > Fe⁰ nanoparticles > Fe⁰ powder > Fe⁰ filings. Electrochemical analysis of the reaction process showed that Cr(III) and Fe(III) hydroxides should be the dominant final products.     

Endogenous nitric oxide mediates alleviation of cadmium toxicity induced by calcium in rice seedlings

The effect of calcium chloride (CaCl₂) on rice seedling growth under cadmium chloride (CdCl₂) stress, as well as the possible role of endogenous nitric oxide (NO) in this process, was studied. The growth of rice seedlings was seriously inhibited by CdCl₂, and the inhibition was significantly mitigated by CaCl₂. However, hemoglobin (Hb) and 2-(4-carboxyphenyl)-4, 4,5,5-tetramethylimidazolinel- oxyl-3-oxide (cPTIO) weakened the promotion effect of CaCl₂. The results of NO fluorescence localization suggest that growth accelerated by CaCl₂ might be associated with elevated NO levels. The content of Cd, protein thiols (PBT), and nonprotein thiols (NPT) in cell walls, cell organelles, and soluble fractions, respectively, of rice seedlings decreased considerably in the presence of CaCl₂, whereas the content of pectin, hemicellulose 1 (HC1), and hemicellulose 2 (HC2) increased significantly. Elimination of endogenous NO in Cd+Ca treatment could promote the transportation of Cd²⁺ to cell organelles and soluble fractions and increase the content of NPT and PBT in leaves. In addition, transportation of Cd²⁺ to cell organelles and soluble fractions was retarded in roots, the content of NPT increased, and the content of PBT decreased. With elimination of endogenous NO in Cd+Ca treatment, the content of pectin, HC1, and HC2 decreased significantly. Thus, Ca may alleviate Cd toxicity via endogenous NO with variation in the levels of NPT, PBT, and matrix polysaccharides.     

藻类水体Cd2+毒性快速监测新方法研究

采用藻类生长抑制试验和光合活性抑制试验两种方法对蛋白核小球藻受不同浓度Cd2+胁迫作用下叶绿素浓度及藻活性荧光参数进行测量,依据Sigmoidal曲线拟合及单因素方差分析(one-way ANOVA)的方法对Cd2+不同胁迫时间下藻活性抑制率和96 h比生长率抑制率的相关性进行研究.结果表明,48、53、72、77和96 h的藻活性抑制率和96 h比生长率抑制率间具有较好的S函数关系(R2>0.95),因此可采用藻活性抑制率48 h-EC10和53 h-EC10来代替96 h的藻类半数比生长率抑制率EC50进行Cd2+藻类毒性实验评价.进一步分析了蛋白核小球藻受Cd2+胁迫48 h和53 h藻活性抑制率和Cd2+毒性当量的剂量-效应关系.该方法为实验室内单一Cd2+毒性的监测提供了一种快速有效的新方法,为水环境综合毒性预警提供了一种切实可行的方法依据.     

Adsorption of Cr(Ⅲ) from acidic solutions by crop straw derived biochars

Cr（Ⅲ） adsorption by biochars generated from peanut, soybean, canola and rice straws is investigated with batch methods. Adsorption of Cr（Ⅲ） increased as pH rose from 2.5 to 5.0. Adsorption of Cr（Ⅲ） led to peak position shifts in the FFIR-PAS spectra of the biochars and made zeta potential values less negative, suggesting the formation of surface complexes between Cr^3＋ and functional groups on the biochars. The adsorption capacity of Cr（Ⅲ） followed the order： peanut straw char 〉 soybean straw char 〉 canola straw char 〉 rice straw char, which was consistent with the content of acidic functional groups on the biochars. The increase in Cr^3＋ hydrolysis as the pH rose was one of the main reasons for the increased adsorption of Cr（Ⅲ） by the biochars at higher pH values. Cr（llI） can be adsorbed by the biochars through electrostatic attraction between negative surfaces and Cr^3＋, but the relative contribution of electrostatic adsorption was less than 5%. Therefore, Cr（Ⅲ） was mainly adsorbed by the biochars through specific adsorption. The Langumir and Freundlich equations fitted the adsorption isotherms well and can therefore be used to describe the adsorption behavior of Cr（Ⅲ） by the crop straw biochars. The crop straw biochars have great adsorption capacities for Cr（Ⅲ） under acidic conditions and can be used as adsorbents to remove Cr（Ⅲ） from acidic wastewaters.     

十溴二苯醚及其降解产物对浮游生物的毒性

十溴二苯醚(BDE-209)是我国环境中主要的多溴二苯醚(PBDEs)同系物.为研究BDE-209及其降解产物对水环境的影响,以初级消费者浮游动物大型蚤(Daphnia magna)和初级生产者浮游植物水华微囊藻(Microcystis flos-aquae)为染毒对象,研究BDE-209及其降解不同阶段产物对浮游生物的毒性.结果表明,大型蚤方面,繁殖毒性大于生长毒性,48 h半数致死浓度(48h-LC50)大小为:还原降解中间产物(0.80 mg·L~(-1),高毒)BDE-209(8.74 mg·L~(-1),中毒)还原降解终产物(15.27 mg·L~(-1),低毒),还原-氧化降解终产物的死亡率与溶剂空白一致,表明其基本无毒.水华微囊藻方面,染毒物质的毒性大小顺序与大型蚤一致,1 mg·L~(-1)的BDE-209、还原中间产物、还原终产物及还原-氧化终产物对水华微囊藻的抑制率分别为15.7%、93.7%、6.6%和1.3%.BDE-209降解过程中易生成毒性较大的中间产物,彻底还原脱溴可降低其毒性,后续辅以氧化降解,可消除其环境毒性.     

Cr(Ⅵ)在Fe(Ⅲ)-柠檬酸盐体系中紫外光还原研究

研究了在紫外光照射下,Fe(Ⅲ)-柠檬酸盐溶液对Cr(Ⅵ)的光还原反应.同时,考察了溶液pH值、Fe(Ⅲ)浓度、柠檬酸盐浓度、Cr(Ⅵ)初始浓度对光还原效率的影响,并分析了光还原反应的动力学.研究结果表明,Fe(Ⅲ)-柠檬酸盐体系能光还原Cr(Ⅵ),在pH为2.0～6.0的范围内,Cr(Ⅵ)的还原率随着溶液初始pH值的降低而增大.当pH值为2.0、Fe(Ⅲ)浓度为10μmol·L-1、柠檬酸盐浓度为250μmol·L-1及Cr(Ⅵ)初始浓度为19.2μmol·L-1时,光照反应8min后Cr(Ⅵ)的最大还原率达到100%,但当pH值增加到6.0时,Cr(Ⅵ)的最大还原率下降到19%;当Cr(Ⅵ)的初始浓度在9.6～96.0μmol·L-1的范围内时,Cr(Ⅵ)光还原反应的初始速率随着Fe(Ⅲ)、柠檬酸盐(cit3)、Cr(Ⅵ)初始-浓度的增加而增加.表观动力学方程为:-dCCr(Ⅵ)/dt=0.1019[Cr(Ⅵ)]0.[Fe(Ⅲ)]0.[cit3]0..536-25     

UV/TiO2光催化过程对二级处理出水多重生物效应的削减特性研究

为了考察复杂体系的二级处理出水在UV光解及UV/TiO_2光催化反应过程中生物效应的变化,本文探究了反应前后发光细菌的荧光抑制毒性、SOS/umu遗传毒性、小球藻光合抑制效应3种生物效应的变化,并分析了物化指标的变化与生物效应之间的关系.结果表明,UV光降解过程并不能高效削减二级处理出水的荧光抑制毒性,但可以高效削减遗传毒性和光合抑制效应,其削减率分别达到61%和81%;在低辐照强度下,UV/TiO_2光催化过程对3种生物效应的削减率分别为38%、84%和80%.增大辐照强度后,3种生物效应的削减率进一步提高,尤其是荧光抑制毒性,其削减率可提高至62%.在UV光降解条件下,二级处理出水的遗传毒性、光合抑制效应与荧光强度、UV_(254)之间存在很好的线性关系;在UV/TiO_2光催化条件下,二级处理出水的3种生物效应都与荧光强度、UV_(254)之间具有很好的线性关系.这为二级处理出水生物效应的控制及生态安全的保障提供了一定的依据.     

软水中EPS对铜管/硅酸盐体系溶解性铜释放影响

以海藻酸钠模拟水体中的EPS,研究了软水体系中海藻酸钠对铜管,硅酸盐体系缓蚀效果的影响.结果表明,当有低浓度海藻酸钠存在时,体系中的溶解性铜浓度显著增加,且老化1 a的铜管溶解性铜释放浓度明显高于老化3 a和10 a的铜管,释放溶解性铜浓度大小顺序为c1a>c3a>c10a;但随着海藻酸钠浓度的增加,老化1 a的铜管的溶解性铜释放浓度增加,而3 a和10 a铜管的溶解性铜释放浓度减小,表明水体中EPS的存在降低硅酸盐对铜管的缓蚀效果.在pH值7.5和海藻酸钠为16mg/L条件下,不同停留时间溶解性铜释放呈现逐渐增加-降低-逐渐增加的趋势,表明海藻酸钠、硅酸盐、铜离子和管壁进行了复杂的相互作用.在低pH值条件下,海藻酸钠对铜管溶解性铜释放影响更加显著,随着pH值增加和铜管老化时间延长,其溶解性铜释放浓度降低,表明海藻酸钠对溶解性铜释放影响降低.     

基于物种敏感度分布法建立中国土壤中锑的环境基准

基于Sb（锑）的植物及动物毒理学数据缺乏以及保护生态受体的土壤Sb的环境基准尚未建立的现状,通过收集和筛选文献中Sb的毒理学数据并补充开展不同土壤类型的跳虫和植物的毒理学试验,建立了Sb的生物毒性预测模型,并以此为依据对收集及试验毒理学数据进行归一化处理,以消除土壤性质的影响.此外,进一步利用SSD（species sensitivity distribution,物种敏感度分布法）推导我国4种典型情景土壤中Sb的HC₅（hazardous concentration,能够保护95%物种的生态安全阈值）,最终建立基于土壤性质参数的环境基准计算模型.结果表明:①不同土壤中Sb对跳虫的毒性差异较大,跳虫毒性阈值EC₁₀（effect concentration,10%抑制效应浓度）与土壤pH呈负相关,与w（SOC）（SOC为土壤有机碳）呈正相关,即随着土壤pH增加或w（SOC）降低,Sb对跳虫的生物有效性随之增加,进而导致EC₁₀降低.②通过毒性阈值与土壤性质之间的多元回归分析可知,土壤pH和SOC可较好地预测Sb的生物毒性,植物和无脊椎动物的R2（决定系数）分别为0.778和0.867.③利用SSD得到11个物种在4种典型情景土壤中的HC₅分别为55.12、28.28、28.08及14.55 mg/kg,推导出PNEC_total（predicted no effect concentration,预测无效应浓度）分别为28.96、15.54、15.44及8.68 mg/kg,计算模型为PNEC_total=-5.811pH+0.587[SOC]+55.480+C_b（[SOC]为土壤有机碳含量,C_b土壤Sb背景浓度）.鉴于此,建议以中性土壤中Sb的环境基准值作为我国农用地土壤Sb污染风险筛选值制订的参考依据,即农用地土壤w（Sb）限值定为15 mg/kg.      

基于批式呼吸计量法的溶解性COD组分划分

利用批式好氧呼吸计量法结合溶解性慢速水解COD(S_H)水解动力学拟合提出了溶解性COD(SCOD)的组分划分方案.上海2个污水处理厂进水的SCOD组分划分结果表明,A厂沉砂池出水(典型生活污水)的SCOD中含有43.5%～58.6% S_H、 21.8%～35.2%易生物降解COD(S_S)和15.4%～30.9%溶解性惰性COD(S_I); B厂沉砂池出水(长距离输送的合流制污水)SCOD中含有34.5%～45.2% S_H、 29.3%～37.7% S_S和25.6%～31.2% S_I. 9组不同水样的试验拟合结果表明,一级动力学能够很好地描述S_H的水解过程,A厂和B厂进水S_H的水解速率常数分别为28.00～39.77 d^-1和26.48～29.52 d^-1.该组分划分方案能够实现S_S积分区域的理论划分,并消除溶解性微生物产物对S_I测定的影响.     

Cd对小白菜生长及氮素代谢的影响研究

采用水培的方法,研究了不同Cd2 水平(0、1、2.5、5、10 mg·L-1)对小白菜叶片中铵态氮、硝态氮、可溶性蛋白质、游离脯氨酸、叶绿素、部分营养元素含量以及蛋白水解酶、硝酸还原酶、谷氨酰胺转化酶与合成酶活性的影响.结果表明,低浓度的Cd处理(1 mg·L-1)刺激了小白菜的生长,提高了小白菜的生物量、叶绿素含量以及硝酸还原酶、谷氨酰胺合成酶与转化酶活性.Cd处理降低了小白菜对Cu、Ca、Fe、Mg的吸收,但促进了P的吸收.10 mg·L-1的Cd处理显著降低了可溶性蛋白质含量、硝酸还原酶、谷氨酰胺合成酶和转化酶活性(p＜0.05),提高了蛋白水解酶活性,不利于叶片中铵态氮与硝态氮的同化,造成叶片中铵态氮和硝态氮的累积.小白菜叶片中游离脯氨酸含量与铵态氮含量成极显著正相关(p＜0.01),说明小白菜叶片中游离脯氨酸的累积在一定程度上缓解了铵的毒害.     

Toxic effects of enrofloxacin on Scenedesmus obliquus

In this article, the toxic effects of Enrofloxacin (ENFX) on Scenedesmus obliquus were studied, through investigating the growth, photosynthetic pigments, and protein contents. The possible toxic mechanisms of ENFX were analyzed by determining the superoxide dismutase (SOD) activity, malondialdehyde (MDA) content, proline content, and superoxide anion (O₂⁻) generation rate. Results showed that the growth of algae was inhibited by ENFX and the 50% effective concentration (EC₅₀) values for 24, 48, 72, and 96 h of ENFX were 88.39, 63.86, 45.10, and 59.16 mg·L⁻¹, respectively. After treated with ENFX for 96 h, the contents of photosynthetic pigments decreased with the increase of ENFX concentration, the content of soluble protein and the activity of SOD increased and then decreased, and the generation rate of superoxide anion (O₂⁻) increased continually. The contents of MDA and proline changed little in lower ENFX concentration groups, but increased rapidly when treated with higher concentration groups. These results suggested that ENFX affected the growth of S. obliquus, and the main toxicity mechanism was that algal cells generated the reactive oxygen species under ENFX stress, and then the reactive oxygen species (ROS) induced the oxidation damages of biologic macromolecules and changed the biomembrane permeability further.     

应用ICE和PCA方法评价硝基芳烃的综合毒性

应用种间相关估算(ICE)方法预测50种硝基芳烃缺失的生物毒性数据,对通过ICE计算获得的各种生物毒性数据进行主成分分析(PCA),计算综合毒性因子(ITI),进行综合毒性评价.结果表明,除了黄瓜种子发芽抑制毒性以外,其他各种生物毒性都在1%的显著水平上呈显著的线性正相关.硝基芳烃的这些生物毒性机制基本相似,因此应用ICE方法预测其毒性数据是可行的.QSAR分析表明,ITI与分子最低未占轨道能E_lumo有显著的相关性,r=0.869,表明亲电反应性是硝基芳烃的各种生物毒性所综合反映的主要致毒机理.基于ICE和PCA方法计算得到的ITI与基于QSAR和PCA方法计算得到的ITI的大小趋势具有一致性,ICE与PCA方法的联合应用可以成功地评价和预测硝基芳烃的综合毒性.     

Identification and characterization of the chromium（Ⅵ） responding protein from a newly isolated Ochrobactrum anthropi CTS-325

A Gram-negative, chromium(VI) tolerant and reductive strain CTS-325, isolated from a Chinese chromate plant, was identified as Ochrobactrum anthropi based on its biochemical properties and 16S rDNA sequence analysis. It was able to tolerate up to 10 mmol/L Cr(VI) and completely reduce 1 mmol/L Cr(VI) to Cr(III) within 48 h. When the strain CTS-325 was induced with Cr(VI), a protein increased significantly in the whole cell proteins. Liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis revealed that this protein was a superoxide dismutase (SOD) homology. The measured superoxide dismutase activity was 2694 U/mg after three steps of purification. The SOD catalyzes the dismutation of the superoxide anion (O₂^·−) into hydrogen peroxide and molecular oxygen. This protein is considered to be one of the most important anti-oxidative enzymes for O. anthropi as it allows the bacterium to survive high oxygen stress environments, such as the environment produced during the reduction process of Cr(VI).     

植物化感物质壬酸和焦酚对大型溞生长繁殖的毒性效应

为评估植物化感抑藻物质的生态安全性,通过48 h急性毒性实验和21 d慢性毒性实验,研究了穗花狐尾藻（Myriophyllum spicatum）典型化感物质壬酸和焦酚对大型溞（Daphnia magna）生长和繁殖的毒性效应.结果显示,壬酸对大型溞24 h和48 h的LC₅₀分别为75.08 mg·L^-1和38.55 mg·L^-1,焦酚对大型溞24 h和48 h的LC₅₀分别为18.89 mg·L^-1和13.71 mg·L^-1.21 d慢性毒性实验中,2.0 mg·L^-1的壬酸和焦酚对大型溞生长仍没有显著影响（p>0.05）,但在高于0.5 mg·L^-1浓度水平即显著延长大型溞首次产溞时间,降低其产溞个数（p<0.05）.大型溞净增殖率和内禀增长率随壬酸和焦酚浓度增加而减小,2.0 mg·L^-1壬酸和焦酚对大型溞净增殖率的抑制率分别为42.40%和38.86%,对大型溞内禀增长率的抑制率分别为25.00%和20.83%.研究表明,壬酸和焦酚对大型溞的繁殖过程产生一定程度的影响,但仍需结合原位试验在更大尺度上评估植物化感抑藻物质的生态安全性.     

Diatomaceous silica filter aid filtration for the effectiveseparation of colloidal Cr(OH)3 precipitatefrom tanning wastewater

ＤｉａｔｏｍａｃｅｏｕｓｓｉｌｉｃａｆｉｌｔｅｒａｉｄｆｉｌｔｒａｔｉｏｎｆｏｒｔｈｅｅｆｆｅｃｔｉｖｅｓｅｐａｒａｔｉｏｎｏｆｃｏｌｌｏｉｄａｌＣｒ（ＯＨ）＿３ｐｒｅｃｉｐｉｔａｔｅｆｒｏｍｔａｎｎｉｎｇｗａｓｔｅｗａｔｅｒＺｈａｏＹｏｕｃａｉ；Ｘ...     

Characterization of cytotoxicity of airborne particulates from urban areas of Lahore

A number of species (organic and inorganic) in airborne particulates cause the toxicity to living being. The potential of in vitro test methods were explored for toxicity assessment of trace toxic elements (inorganic species) present in ambient air on human being (lungs). A year long sampling of airborne particles (PM_2.5) was carried (April 2008 to March 2009) in Lahore, Pakistan. A total of thirty nine samples were collected on 47 mm Zefluor Teflon filter membranes and each was analysed to characterize for the elements: Sb, As, Be, Cd, Cr, Co, Pb, Mn, Hg using ICP-MS in water extract and total acid digestate. The samples cytotoxicity was also established using lung derived cells and MTS colorimetric assays. This generated dose response curves and IC₅₀ values for the elemental mixtures identified on the Teflon filter membrane. The results indicated that even at low concentrations airborne elemental mixtures displayed an additive toxic effect.