Effect Of pH on the complexation of U(II) with organic matter dissolved in resh waters

In the present work we study the effect of pH on the complexation of copper with organic matter dissolved in fresh surface waters. Samples collected in rivers of Galicia (NW of Spain) were titrated with copper solution at pH values in the range 5.5–7.5. Copper concentration was measured by DPASV technique. The complexation parameters were obtained from the simple model of 1 : 1 complex formation. The obtained values show a linear increase of the logarithm of the conditional stability constant as the pH increases.     

鲤鱼鱼鳃微环境酸碱条件与铜形态分布模拟

用鱼鳃微环境测定装置和化学平衡计算方法,研究了在人工河水中暴露于铜的鲤鱼鳃部微环境的pH、碱度、粘液含量和铜形态分布.结果发现,鱼鳃pH平衡点为6.92,人工河水pH高于或低于此值时,鱼鳃微环境pH偏低或偏高.变化幅度约达-0.6至0.4 个pH单位.根据实测结果分别建立了计算人工河水和鱼鳃微环境碱度以及鱼鳃粘液分泌量随暴露铜含量和pH变化的定量模型.化学平衡计算结果说明,在pH6至9范围内,人工河水中优势态铜从游离态铜过渡到羟基络合态铜.由于粘液和pH差异的影响,鱼鳃微环境中生物有效态铜含量显著低于人工河水.这样的差别在酸性条件下尤为显著.     

聚丙烯中空纤维膜萃取水溶液中铜离子的研究

研究了聚丙烯中空纤维膜萃取二(2-乙基己基)膦酸(D2EHPA)水溶液中铜离子的工艺条件.结果表明,两相流速、膜面积对萃取率基本无影响;而水溶液的pH值和有机相初始铜离子浓度的改变使萃取率在40%-99%之间变化.整个萃取过程的传质阻力主要来源于D2EHPA和 Cu2 的界面配位络合反应阻力,铜浓度比较高时,传质阻力与铜浓度无关;而当铜浓度降低时,传质阻力随着铜浓度的降低而增大.     

Electrochemical determination of the effect of lead(II) on the photochemical degradation of the pesticide metamitron

The complexation of the pesticide Metamitron by lead(II) was investigated by polarography and stripping voltammetry. The influence of the pH on the complexation was determined and a maximum value for the conditional stability constant of the lead‐metamitron complex (logβ’ = 3.1) was obtained at pH 5.6.

An investigation into the photochemical degradation of the pesticide demonstrated that lead decreases the degradation rate of metamitron by 13% within the first 30 days, due to stabilisation by complexation.     

Heavy metal distribution and speciation in the Northern Adriatic Sea

In the present study the concentrations of cobalt, copper, iron, manganese, zinc were analysed and the speciation of copper and zinc performed, with a summer and winter sampling, for two areas in the Northern Adriatic Sea and crossing at the farthest zones of the Po river-sea water interface. Results show that when salinity increases the concentrations of all investigated metals (with the exception of cobalt) present some degree of biogeochemical cycling. Copper is the element whose dissolved phase has the highest importance in metal transport across the salinity gradient. Results of speciation analysis demonstrate that the presence of excess amounts (5-8 fold) of unbound ligands confers a buffering capacity for potential inputs of dissolved metals into the Northern Adriatic Sea. The speciation of both copper and zinc in the dissolved phase was dominated by organic complexation.     

HEAVY METAL DISTRIBUTION AND SPECIATION IN THE NORTHERN ADRIATIC SEA

In the present study the concentrations of cobalt, copper, iron, manganese, zinc were analysed and the speciation of copper and zinc performed, with a summer and winter sampling, for two areas in the Northern Adriatic Sea and crossing at the farthest zones of the Po river-sea water interface. Results show that when salinity increases the concentrations of all investigated metals (with the exception of cobalt) present some degree of biogeochemical cycling. Copper is the element whose dissolved phase has the highest importance in metal transport across the salinity gradient. Results of speciation analysis demonstrate that the presence of excess amounts (5-8 fold) of unbound ligands confers a buffering capacity for potential inputs of dissolved metals into the Northern Adriatic Sea. The speciation of both copper and zinc in the dissolved phase was dominated by organic complexation.     

Bioavailability of dissolved copper to the American oyster Crassostrea virginica. I. Importance of chemical speciation

The effect of complexation on the accumulation of dissolved copper by the American oyster Crassostrea virginica was determined in chemically defined exposure media. The speciation of copper was varied by varying the concentrations of total copper and model chelator, nitrilotriacetic acid (NTA). Accumulation of copper in 14-d experiments was related to the cupric ion activity and not the concentration of chelated copper. Rapid accumulation of copper occurred at cupric ion activities above 10^-10 M and there was no measurable accumulation at 10^-11 M.Southeast Fisheries Center Contribution No. 81-45B. Reprint request should be addressed to this author     

Experimental study of chromium adsorption on minerals in the presence of phthalic and humic acids

The effect of phthalic acid (benzene 1,2 dicarboxylic acid), a surrogate compound for natural organic matter, and of humic acid, on the adsorption of chromium to the surface of minerals was observed. In ternary systems involving phthalic acid, chromium(III) adsorption decreases on clays, probably because of aqueous Cr(III)-phthalate complexation, preventing ionic-exchange. Phthalic acid was also found to reduce chromium(VI) adsorption onto alumina, because of a competitive effect. In ternary systems involving humic acid, Cr(III) adsorption is increased in the low pH range because of the formation of surface ternary complex S-L-Cr(III) and is decreased in the high pH range because of aqueous Cr(III)-humate complexation.     

内蒙古若干江湖水体中铜的表观络合容量

本文对内蒙古若干江湖水样中天然配体与铜的表观络合容量进行了阳极溶出伏安法测定，并计算总条件稳定常数和络合容量指数。实验表明，富集电位，ｐＨ值，碳酸根对络合容量的测定影响不同；天然ｐＨ值下，铜的表观络合容量为呼伦湖最大，乌梁素海最小，其余水样相近。     

Cadmium removal mechanistic comparison of three Fe-based nanomaterials: Water-chemistry and roles of Fe dissolution

● nZVI, S-nZVI, and nFeS were systematically compared for Cd(II) removal. ● Cd(II) removal by nZVI involved coprecipitation, complexation, and reduction. ● The predominant reaction for Cd(II) removal by S-nZVI and nFeS was replacement. ● A simple pseudo-second-order kinetic can adequately fit Fe(II) dissolution. Cadmium (Cd) is a common toxic heavy metal in the environment. Taking Cd(II) as a target contaminant, we systematically compared the performances of three Fe-based nanomaterials (nano zero valent iron, nZVI; sulfidated nZVI, S-nZVI; and nano FeS, nFeS) for Cd immobilization under anaerobic conditions. Effects of nanomaterials doses, initial pH, co-existing ions, and humic acid (HA) were examined. Under identical conditions, at varied doses or initial pH, Cd(II) removal by three materials followed the order of S-nZVI > nFeS > nZVI. At pH 6, the Cd(II) removal within 24 hours for S-nZVI, nFeS, and nZVI (dose of 20 mg/L) were 93.50%, 89.12% and 4.10%, respectively. The fast initial reaction rate of nZVI did not lead to a high removal capacity. The Cd removal was slightly impacted or even improved with co-existing ions (at 50 mg/L or 200 mg/L) or HA (at 2 mg/L or 20 mg/L). Characterization results revealed that nZVI immobilized Cd through coprecipitation, surface complexation, and reduction, whereas the mechanisms for sulfidated materials involved replacement, coprecipitation, and surface complexation, with replacement as the predominant reaction. A strong linear correlation between Cd(II) removal and Fe(II) dissolution was observed, and we proposed a novel pseudo-second-order kinetic model to simulate Fe(II) dissolution.     

Biosorption of zinc (II) using Spirogyra species from electroplating effluent

Zinc was removed from the metal plating effluent with the biosorbent consisting of filamentous algae Spirogyra sp. The sorption was pH dependent with best adsorption at pH 2.5. The metal uptake increased from 3.9% (for no dilution) to 36.8% (for 10 times dilution), indicating that sorption increased with dilution of sample. The adsorption was faster at initial contact time, gradually decreased and remains constant after certain optimum time. Percentage removal of zinc increased from 20.3% to 63.6% with increase in the temperature from 25 degrees C to 35 degrees C but further increase resulted in the decrease in adsorption. Freundlich isotherm was applied and it holds good for the adsorption data.     

农用污泥中铜的生态安全阈值研究

本论文采用污泥和土壤外源铜的活性差异系数法研究了农用污泥中铜的生态安全阈值。首先通过比较确定不同土壤条件下污泥中铜和水溶性铜的活性差异的系数,然后利用系数法得到相应土壤条件下污泥铜HC5值(即能够保护95%物种的浓度),并建立了土壤理化性质参数与污泥铜HC5值的量化关系和预测模型。最后与我国现行污泥农用标准值进行了比较,提出了修改建议。结果表明,土壤中来源污泥的铜活性均值约为来源水溶性盐的40%左右。土壤阳离子交换量(CEC)是影响土壤中污泥源铜的毒性的主控因子,可影响污泥铜HC5值变异的84.6%,而土壤pH值和有机碳含量(OC)分别可影响污泥铜HC5值变异的8.4%和1.8%。基于土壤pH、OC和CEC的三因子模型进行预测优于基于土壤pH和CEC的两因子模型,其相关性达到94.8%。与模型预测值相比,我国现行污泥农用标准GB4284-84与CJ/T309-2009中对铜限值的规定均存在着不同程度的保护不足或保护过度问题。     

Surface characteristics of shales and implication on metal sorption

Differences in surface characteristics between alkaline and acidic shales are demonstrated in the present study. The alkaline shales are characterized by convex surface titration profiles, while the acidic shale exhibits a concave titration profile. Analysis of surface functional groups reveal that carboxylic acids predominate in alkaline shales and the acidic shale is characterized by C=S, C=N (pyridine derivative) and urea (C=O) functional groups, while it lacks –COOH group. The close proximity between pH and point of zero charge for the most acidic and alkaline shales indicate that surface complexation may not play a dominant role in sorption when the system pH is controlled by these sediments.     

Physiological responses ofCalanus finmarchicus andMetridia longa (Copepoda: Calanoida) during the winter-spring transition

The effect of pH on the biological availability of copper to the brine shrimp Artemia franciscana was studied with acclimated and non-acclimated individuals for the pH range 5.5 to 8.5. A chemical speciation model was used to calculate the speciation of copper in a chemically-defined saline solution as a function of pH. The lipid solubility of inorganic copper species was determined in hexadecane/saline and octanol/saline extraction systems. Copper is absorbed across the gut epithelium and accumulation is proportional to time over a 120 min experimental period. The biological availability of copper decreases with a decrease in the pH of the salt solution and a concomitant increase of the cupric ion concentration. Acclimation to the experimental pH has a marked effect on the uptake process, which depends on the buffer used. There is no extraction of copper in hexadecane, but a small amount goes in octanol. There is, however, no direct relation between the accumulation of copper in the shrimps and the extraction of copper in octanol. Multiple regression of the accumulation rates for non-acclimated animals on the calculated copper species concentrations shows that much of the variation in accumulation rate with pH is explained when copper hydroxide and/or copper carbonate species are considered to be the biologically available forms. Alternatively, the observations can be interpreted as the result of competitive binding of protons and copper species for carrier systems.     

Copper(II) ions’ removal from aqueous solution using green horse-chestnut shell as a low-cost adsorbent

The adsorption of copper(II) ions from aqueous solutions by the green horse-chestnut shell was studied in a batch adsorption system. It was determined how the parameters of the adsorption process, such as time, pH, copper(II) ions concentration and sorbent dose, influence the effectiveness of copper(II) ions’ removal. The adsorption process was fast and equilibrium was established about 10?min, and near 95–97% of Cu(II) ions were removed from aqueous solution. Maximum copper(II) ions’ adsorption occurred at around pH 5. The adsorption kinetics are also described, using pseudo-first-order model and pseudo-second-order model of type 1 and 2. A comparison of the kinetics models on the overall adsorption rate showed that the adsorption system was best described by the pseudo-second-order model of type 1 (r²?=?0.999) for all initial concentrations. Another key part of this study was the use of the Freundlich model to determine the adsorption isotherm and the experimental data were in strong correspondence with this model.     

Extra- and intracellular acid-base balance and ionic regulation in cod (Gadus morhua ) during combined and isolated exposures to hypercapnia and copper

Cod (Gadus morhua) were exposed to hypercapnia (water Pco₂ = 7.5 mmHg), elevated copper level (0.4 ppm) or a combination of both in order to study extra- and intracellular acid-base regulation and the influence hereupon of copper. During pure hypercapnia, the extracellular respiratory acidosis was completely compensated within 12 to 24 h via a chloride-mediated increase in extracellular [HCO₃ ⁻]. Exposure to copper in normocapnic seawater caused a large and progressive increase in plasma [Na⁺] and [Cl⁻] and a metabolic acidosis. Exposure to copper in hypercapnic seawater was associated with smaller elevations of plasma [Na⁺] and [Cl⁻] than in normocapnic seawater, showing that hypercapnia had a protective effect on the copper-induced osmoregulatory disturbances. The compensation of the hypercapnic acidosis was, however, slow and incomplete in fish exposed to both copper and hypercapnia. Extracellular pH remained depressed by 0.3 pH units after 72 h. The data reveal that acid-base regulation was immediately and persistently inhibited by copper. The limited acid-base regulation during combined copper and hypercapnia exposure was chloride-mediated as during hypercapnia alone. Intracellular pH recovery was complete and very rapid in ventricular and skeletal muscle tissues during environmental hypercapnia, whereas acid-base compensation in liver tissue was slower, the kinetics being similar to that in the extracellular compartment. Intracellular pH compensation was significantly slowed down by copper. Copper concentration increased drastically in gill tissue already at 3 h, while copper concentrations in liver, muscle and plasma were significantly elevated only after 48 h, with liver showing the largest elevation. Received: 15 November 1996 / Accepted: 2 December 1996     

有机磺酸类化合物的络合萃取研究

本文以三烷基胺为络合剂,正辛醇,煤油,氯仿,四氯化碳等为稀释剂,测定了络合萃取剂对于对甲基苯磺酸,磺基水杨酸稀溶液的相平衡分配系数,讨论了稀释剂,体系ＰＨ值和７３０１络合剂含量对萃取相平衡分配系数Ｄ值的影响,确定了形成的萃合物的组成。     

香港河流沉积物中有机碳对铜的吸附特性

采用厌氧序列分批滴定装置（ＡＳＢＴ）研究了香港青山湾避风塘和屯门河、城门河、林村河感潮河段沉积物中有机碳对铜的吸附特性。结果表明,在ｐＨ１６和ｐＨ７的条件下,沉积物中有机碳对铜的吸附特性可用Ｌａｎｇｍｕｉｒ等温式描述,铜在不同河流沉积物有机碳中的分配系数差别较大,吸附容量差别较小,Ｈ＾＋可以结合沉积物有机碳的重金属结合位点,导致吸附容量和分配系数随ｐＨ增大而增大。     

腐殖酸对As(V)在覆铁砂介质中吸附行为的影响

对腐殖酸(HA)进行了成分分析及红外表征,并从HA浓度、pH值、As(Ⅴ)初始浓度等方面,研究了HA对As(Ⅴ)在覆铁砂介质中吸附行为的影响.结果表明,随着HA浓度的升高,总砷去除率逐渐降低.当HA浓度增加到25mg.l-1时,与不存在HA条件下相比,总砷去除率降低了12%左右.溶液pH值影响As(Ⅴ)的去除,pH值从6升高到8时,总砷去除率从52.1%降到了39%.其中的作用机理主要是HA与As(Ⅴ)在覆铁砂表面形成竞争吸附,HA争夺了As(Ⅴ)的吸附点位.此外,HA与Fe(Ⅲ)的络合作用也是导致覆铁砂对砷的去除率降低的一个重要原因.     

铜的形态分布与Daphnia magna急性毒性关系

本文利用化学平衡模式ＭＩＮＴＥＡＱ２研究不同酸度,碱度和有机配体存在下铜的形态分布特点,通过Ｄａｐｈｎｉａ ｍａｇｎａ毒性试验获得形态变化时的毒性变化规律。结果显示：无论是总量,还是游离态浓度,都不能反映出铜的毒性大小。