REVERSIBLE ADSORPTION OF AQUEOUS DIVALENT COPPER ION BY ESTUARINE SEDIMENTS1

Sediments were equilibrated with solutions containing divalent copper ion. A colorimetric method using the triethylenete-tramine complex of the metal ion was employed to measure changes in uptake of copper by the sediments. Studies were made with sediments from rivers in the British Isles which were in the proximity of areas which had been mined for metals for several hundred years. For comparison, similar studies were performed with a sample of sand and a soil with a high organic content. It was possible to follow the uptake of copper ion by the materials and estimate their abilities to adsorb copper ion. In particular, a strong correlation was observed between the organic content of the sediment and the total amount of copper adsorbed by the sample. Under the employed circumstances it was possible to demonstrate that the adsorption of the metal ion was reversible.     

含铜废水处理技术现状

含铜废水主要来源于工业生产过程，如不经过适当处理排入环境，将给环境带来极大危害。含铜废水的主要处理方法有化学沉淀法、离子交换法、电解法等。由于各生产过程不同，废水中铜的存在状态与价态都各有差异，对于不同类型含铜废水的处理应依据废水性质，选用不同工艺或工艺组合对废水进行处理，以满足排放标准的要求。同时在处理含铜废水时，应考虑处理后出水的回用和废水中铜的资源化问题。     

The potential of cost-effective coconut husk for the removal of toxic metal ions for environmental protection

Coconut (Cocos nucifera) husk, an agricultural waste, has been thoroughly investigated for the removal of toxic Cd(II), Cr(III) and Hg(II) ions from aqueous media. The parameters like nature and composition of electrolyte, concentration of toxic ions, dosage of coconut husk, and equilibration time between the two phases were optimized for their maximum accumulation onto the solid surface. The effect of common ions on the uptake of metal ions has been monitored under optimal conditions. The variation of retention of each metal ion with temperature was used to compute the thermodynamic quantities DeltaH, DeltaS and DeltaG. The values 18.1+/-0.6 kJmol(-1), 74+/-2 Jmol(-1)K(-1), and -3.8+/-0.04 kJmol(-1) at 298 K; 10.8+/-0.8 kJmol(-1), 48.8+/-2.7 Jmol(-1)K(-1), and -4.6+/-0.3 kJmol(-1) at 298 K; and -37.4+/-2k Jmol(-1), 105+/-7 Jmol(-1)K(-1) and -2.58+/-0.5 kJmol(-1) at 298 K were obtained for Cd(II), Cr(III) and Hg(II) ions, respectively. The sorption data were analysed by applying different sorption isotherms. The sorption capacity and energy were evaluated for each metal ion. The values of the Freundlich constants 1/n and C(m) were 0.92+/-0.04 and 52.6+/-22.2 mmolg(-1); 0.85+/-0.05 and 56.0+/-0.03 mmolg(-1); and 0.88+/-0.03 and 6.84+/-0.45 mmolg(-1) for Cd(II) Cr(III) and Hg(II) ions, respectively. Similarly, the Dubinin-Radushkevich (D-R) constants beta, X(m,) and E were evaluated for the three metal ions. To check the selectivity of the sorbent, sorption of a number of elements was measured under similar conditions. Separation of Zn(II) from Cd(II); Cr(III) from I(I), Zr(IV), Se(IV), and Hg(II) from Se(IV) and Zn(II) can be achieved using this sorbent. This cheap material has potential applications in analytical chemistry, water decontamination, industrial effluent treatment and in pollution abatement.     

Biosorption of copper(II) and lead(II) onto potassium hydroxide treated pine cone powder

Pine cone powder surface was treated with potassium hydroxide and applied for copper(II) and lead(II) removal from solution. Isotherm experiments and desorption tests were conducted and kinetic analysis was performed with increasing temperatures.As solution pH increased, the biosorption capacity and the change in hydrogen ion concentration in solution increased. The change in hydrogen ion concentration for lead(II) biosorption was slightly higher than for copper(II) biosorption. The results revealed that ion-exchange is the main mechanism for biosorption for both metal ions. The pseudo-first order kinetic model was unable to describe the biosorption process throughout the effective biosorption period while the modified pseudo-first order kinetics gave a better fit but could not predict the experimentally observed equilibrium capacities. The pseudo-second order kinetics gave a better fit to the experimental data over the temperature range from 291 to 347 K and the equilibrium capacity increased from 15.73 to 19.22 mg g^?1 for copper(II) and from 23.74 to 26.27 for lead(II).Activation energy was higher for lead(II) (22.40 kJ mol^?1) than for copper(II) (20.36 kJ mol^?1). The free energy of activation was higher for lead(II) than for copper(II) and the values of ΔH* and ΔS* indicate that the contribution of reorientation to the activation stage is higher for lead(II) than copper(II). This implies that lead(II) biosorption is more spontaneous than copper(II) biosorption.Equilibrium studies showed that the Langmuir isotherm gave a better fit for the equilibrium data indicating monolayer coverage of the biosorbent surface. There was only a small interaction between metal ions when simultaneously biosorbed and cation competition was higher for the Cu-Pb system than for the Pb-Cu system. Desorption studies and the Dubinin–Radushkevich isotherm and energy parameter, E, also support the ion-exchange mechanism.     

Interparticle diffusion and thermodynamic modeling studies for the removal of heavy metals using mixed adsorbents in industrial effluents

Pollution of water, air, and soil by industrial effluents is a major problem nowadays. A variety of contaminants are too responsible for changing the physicochemical properties of the receiving body. There are practical treatment solutions available to clean up contaminants from various resources. The term “adsorption” refers to one of them. The purpose of the research work is to remove heavy metals from industrial effluent. Mixed adsorbents prepared from activated charcoal and bone charcoals were used to remove the copper and cadmium ions. The experiment carried out in a batch operation and modeling of these data for intraparticle diffusion and thermodynamic calculations were reported in this research work. At optimum operating condition pH 6; metal ion concentration 50 mg/L; dose 5 g/L; agitation 180 rpm and temperature 40°C maximum 99.41% copper ions and 88.12% cadmium ion removal was achieved. Cadmium ions were well fitted in the thermodynamic model compared to copper ions, as demonstrated by the higher correlation coefficient R² (0.9824) value. Intra particle diffusion demonstrated that film diffusion was a rate-limiting step at the start of the reaction, while microporous intraparticle diffusion was the rate-determining phase later on. A Fourier transformation infrared spectroscopy, X-ray diffraction, and scanning electron micrography analysis confirmed the suitability of mixed adsorbents for the removal of cadmium and copper metal ions.     

Time and moisture effects on total and bioavailable copper in soil water extracts

Environmental risk assessment of heavy metals in soil frequently involves testing of freshly spiked soils kept under stable humidity conditions, but it has been questioned whether these assessments are representative of the field situation. Furthermore, the poor correspondence that is often found between total metal content and metal toxicity calls for integrated chemical and biological analysis. The aim of this work was to determine time- and moisture-dependent changes in total water-extractable Cu as well as bioavailable Cu in soil water extracts. Measurements of total water-extractable copper ([Cu]tot) were performed using furnace atomic absorption spectrometry. An in vitro assay employing a Cu-specific Pseudomonas fluorescens reporter strain was used to estimate Cu that was biologically available to the reporter strain. We refer to this copper fraction as "bioavailable," [Cu]bio. We found a time-dependent decrease in [Cu]tot and [Cu]bio during incubation for up to 220 d at field capacity. Hence the [Cu]bio was reduced to between 32 and 40% of the initial values. Furthermore, the [Cu]bio to [Cu]tot ratio correlated positively with the amount of added Cu and tended to increase with time. The moisture content of the soil was important for Cu retention. Dry soil had higher [Cu]tot concentrations than humid soil, but the [Cu]bio to [Cu]tot, ratio was lower in the dry soil. Alternating drying and wetting did not lead to a more rapid Cu retention than observed under constant humid conditions. Our observations underline the need for considering both time and moisture effects when interpreting short-term toxicity studies and when making predictions concerning possible long-term effects of Cu in the soil environment.     

Influences of Water and Sediment Quality and Hydrologic Processes on Mussels in the Clinch River

Segments of the Clinch River in Virginia have experienced declining freshwater mussel populations during the past 40 years, while other segments of the river continue to support some of the richest mussel communities in the country. The close proximity of these contrasting reaches provides a study area where differences in climate, hydrology, and historic mussel distribution are minimal. The USGS conducted a study between 2009 and 2011 to evaluate possible causes of the mussel declines. Evaluation of mussel habitat showed no differences in physical habitat quality, leaving water and sediment quality as possible causes for declines. Three years of continuous water‐quality data showed higher turbidity and specific conductance in the reaches with low‐quality mussel assemblages compared to reaches with high‐quality mussel assemblages. Discrete water‐quality samples showed higher major ions and metals concentrations in the low‐quality reach. Base‐flow samples contained high major ion and metal concentrations coincident to low‐quality mussel populations. These results support a conceptual model of dilution and augmentation where increased concentrations of major ions and other dissolved constituents from mined tributaries result in reaches with declining mussel populations. Tributaries from unmined basins provide water with low concentrations of dissolved constituents, diluting reaches of the Clinch River where high‐quality mussel populations occur.     

Chromated copper arsenate-treated fence posts in the agronomic landscape: soil properties controlling arsenic speciation and spatial distribution

Soils adjacent to chromated copper arsenate (CCA)-treated fence posts along a fence line transecting different soil series, parent material, drainage classes, and slope were used to determine which soil properties had the most influence on As spatial distribution and speciation. Metal distribution was evaluated at macroscopic (total metal concentration contour maps) and microscopic scales (micro-synchrotron X-ray fluorescence maps), As speciation was determined using extended X-ray absorption fine structure spectroscopy, and redox status and a myriad of other basic soil properties were elucidated. All geochemical parameters measured point to a condition in which the mobilization of As becomes more favorable moving down the topographic gradient, likely resulting through competition (Meh-P, SOM), neutral or slightly basic pH, and redox conditions that are favorable for As mobilization (higher Fe(II) and total-Fe concentrations in water extracts). On the landscape scale, with hundreds of kilometers of fence, the arsenic loading into the soil can be substantial (～8-12 kg km). Although a significant amount of the As is stable, extended use of CCA-treated wood has resulted in elevated As concentrations in the local environment, increasing the risk of exposure and ecosystem perturbation. Therefore, a move toward arsenic-free alternatives in agricultural applications for which it is currently permitted should be considered.     

Reduction of copper(II) by iron(II)

Laboratory and field investigations have clearly demonstrated the important role of reduced iron (Fe(II)) in reductive transformations of first-row transition metal species. However, interactions of Fe(II) and copper (Cu) are not clearly understood. This study examined the reduction of Cu(II) by Fe(II) in stirred-batch experiments at pH 5.2 and 5.5 as influenced by chloride (Cl-) concentration (0.002-0.1 M), initial metal concentration (0.1-9.1 mM), and reaction time (1-60 min) under anoxic conditions. Reduction of Cu(II) to Cu(I) by dissolved Fe(II) was rapid under all experimental conditions and the stability of the products explains the driving force for the redox reaction. Under conditions of low [Cl-] and high initial metal concentration, >40% of total Cu and Fe were removed from solution after 1 min, which accompanied formation of a brownish-red precipitate. X-ray diffraction (XRD) patterns of the precipitates revealed the presence of cuprite (Cu2O), a Cu(I) mineral, based on d-spacings located at 0.248, 0.215, 0.151, and 0.129 nm. Fourier transform infrared (FTIR) spectroscopy corroborated XRD data for the presence of Cu2O, with features located at 518, 625, and 698 cm(-1). Increasing [Cl-] stabilized the dissolved Cu(I) product against Cu2O precipitation and resulted in more Fe precipitated from solution (relative to Cu) that appears to be present as poorly crystalline lepidocrocite (gamma-FeOOH). This process may be important in anoxic soil environments, where dissolved Fe(II) levels can accumulate.     

STRATEGIES FOR SEPARATING METALS FROM ACID MINE WATERS1

ABSTRACT: Strategies for the precipitation and separation of the primary metal ions, Fe(II), Cu(II), Zn(II), Mn(II), and Cd(II) in acid waste waters such as those in tributaries of the upper Sacramento River in northern California, are discussed. The strategies exploit the: (1) differential oxygen and hydrogen peroxide oxidation and precipitation properties of the metal ions as a function of pH, (2) the addition of ions, such as Mg^{2 +} and Cl^-, to reduce unfavorable coprecipitation, and (3) the facilitation of oxidation-reduction reactions between metal ions and the stabilization of particular oxidation states. This may be accomplished with specific complexing agents such as thiocyanate, SCN^-, and thiourea (TU), S = C(NH₂)₂ in order to separate copper at low pH as Cu(I) using Fe(II) as a reducing agent.     

SENSITIVITY ANALYSIS: A NECESSITY IN WATER PLANNING1

ABSTRACT In water planning activities, major emphasis has been placed on the development of procedures for devising “optimum plans.” These plans are defined as those which meet prespecified demands for water at “minimum cost.” However, all plans are developed subject to postulated conditions regarding the state of the physical system and of nature. Because planning takes place in a dynamic and uncertain environment in which postulated conditions are known to change, it is imperative that the planner be apprised in the planning phase of the effect of changes which can occur. Using “this information, a planner can temper his judgment with a knowledge of the effect of the uncertainty resulting from changes in the system state variables. This paper presents results of the use of a computer simulation and optimization model to quantify possible variations in system response which could occur as a result of uncertainty in the postulated physical and economic conditions under which the proposed water development system was to perform. The possible effects of these variable responses on planning decision-making is discussed.     

Effects of Metal Mining and Milling on Boundary Waters of Yellowstone National Park, USA

/ Aquatic resources in Soda Butte Creek within Yellowstone National Park, USA, continue to be threatened by heavy metals from historical mining and milling activities that occurred upstream of the park's boundary. This includes the residue of gold, silver, and copper ore mining and processing in the early 1900s near Cooke City, Montana, just downstream of the creek's headwaters. Toxicity tests, using surrogate test species, and analyses of metals in water, sediments, and macroinvertebrate tissue were conducted from 1993 to 1995. Chronic toxicity to test species was greater in the spring than the fall and metal concentrations were elevated in the spring with copper exceeding water quality criteria in 1995. Tests with amphipods using pore water and whole sediment from the creek and copper concentrations in the tissue of macroinvertebrates and fish also suggest that copper is the metal of concern in the watershed. In order to understand current conditions in Soda Butte Creek, heavy metals, especially copper, must be considered important factors in the aquatic and riparian ecosystems within and along the creek extending into Yellowstone National Park.KEY WORDS: Mining; Metals; Toxicity; Biomonitoring; Copper; Yellowstone National Park     

P(4-vinyl pyridine) hydrogel use for the removal of UO(2)(2+) and Th(4+) from aqueous environments

4-vinyl pyridine (4-VP) based hydrogels with 2-hydroxyethylmetacrylate (HEMA) and magnetic composites were prepared and tested for use in the removal of UO(2)(2+) and Th(4+) ions from aqueous environments. It was found that the absorption of these metal ions from aqueous environments decreased with an increase in the amount of HEMA contained within p(4-VP-co-HEMA) hydrogels between 0.498?mmol for pure p(4-VP) and 0.027?mmol for pure p(HEMA). The characterization of the hydrogels was determined by swelling experiments, FT-IR and thermal analysis. The effects of initial metal ion concentration, hydrogel amount and the temperature of the medium on absorption of the ions were investigated. Langmuir and Freundlich isotherms were constructed for the absorption of UO(2)(2+) and Th(4+). Both isotherms demonstrated that these metal ions complied with monolayer absorption kinetics.     

Development of a highly sensitive extractive spectrophotometric method for the determination of nickel(II) from environmental matrices using N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone

Nickel(II) reacts with N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone (ECCT) and forms a yellow colored complex, which was extracted into n-butanol from sodium acetate and acetic acid buffer at pH 6.0. The absorbance value of the Ni(II)-ECCT complex was measured at different intervals of time at 400nm, to ascertain the time stability of the complex. The extraction of the complex into the solvent was instantaneous and stable for more than 72h. The system obeyed Beer's law in the concentration range of 1.2-5.6mugml(-1) of nickel(II), with an excellent linearity and a correlation coefficient of 0.999. The molar absorptivity and Sandell's sensitivity of the extracted species were found to be 1.114x10(4)Lmol(-1)cm(-1) and 5.29x10(-3)mugcm(-2) at 400nm, respectively. Hence, a detailed study of the extraction of nickel(II) with ECCT has been undertaken with a view to developing a rapid and sensitive extractive spectrophotometric method for the determination of nickel(II) when present alone or in the presence of diverse ions which are usually associated with nickel(II) in environmental matrices like soil and industrial effluents. Various standard alloy samples (CM 247 LC, IN 718, BCS 233, 266, 253 and 251) have been tested for the determination of nickel for the purpose of validation of the present method. The results of the proposed method are comparable with those from atomic absorption spectrometry and were found to be in good agreement.     

MOBILITY AND AQUATIC TOXICITY OF COPPER IN AN URBAN WATERSHED1

ABSTRACT: Abundant use of copper based products has resulted in increased violation of copper water quality criteria in runoff from urban storm water systems. The objectives of this work were to understand the mobility and toxicity of copper in an urban watershed and to apportion the amount of copper entering the freshwater receiving stream from different urban land covers using a mass balance approach. Sixteen rainfall events collected from the University of Connecticut study watershed between August 1998 and September 2000 were analyzed to assess copper flux in an urban storm water system. Mean flow weighted dissolved copper concentrations observed in the study for copper based architectural material runoff, pervious area runoff, impervious area runoff, and in the receiving stream were 1210 ± 840, 9 ± 3, 8 ± 2, and 14 ± 7 μg/L, respectively. Mean dissolved copper concentrations in the receiving stream exceeded Connecticut's water quality criteria. Despite exceeding the dissolved concentration based criteria, cupric ion concentrations at the system outlet remained below 0.05 μg/L for all storms analyzed, and no acute toxicity (using Daphnia pulex as the test organism) was measured in samples collected from the stream.     

GEOCHEMICAL CHARACTERIZATION OF SHALLOW GROUND WATER IN THE EUTAW AQUIFER,MONTGOMERY, ALABAMA1

ABSTRACT: Ground water samples were collected from 30 wells located in, or directly down gradient from, recharge areas of the Eutaw aquifer in Montgomery, Alabama. The major ion content of the water evolves from calcium‐sodium‐chloride‐dominated type in the recharge area to calcium‐bicarbonate‐dominated type in the confined portion of the aquifer. Ground water in the recharge area was under saturated with respect to aluminosilicate and carbonate minerals. Ground water in the confined portion of the aquifer was at equilibrium levels for calcite and potassium feldspar. Dissolved oxygen and nitrite‐plus‐nitrate concentrations decreased as ground water age increased; pH, iron, and sulfate concentrations increased as ground water age increased. Aluminum, copper, and zinc concentrations decreased as ground water age and pH increased. These relations indicate that nitrate, aluminum, copper, and zinc are removed from solution as water moves from recharge areas to the confined areas of the Eutaw aquifer. The natural evolution of ground water quality, which typically increases the pH and decreases the dissolved oxygen content, may be an important limiting factor to the migration of nitrogen based compounds and metals.     

Adsorption characterization of Pb(II) and Cu(II) ions onto chitosan-tripolyphosphate beads: Kinetic,equilibrium and thermodynamic studies

Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (ΔH°), Gibbs free energy (ΔG°) and entropy (ΔS°) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.     

Copper and zinc speciation in the solution of a soil-sludge mixture

Only a small fraction of the transition metals content in sludge-amended soils is soluble, and yet this fraction is a major contributor to the mobility and bioavailability of the metals. The chemical species of zinc (Zn) and copper (Cu) in the soluble fractions of soil-sludge mixtures were characterized with respect to their charge, molecular weight, and stoichiometry using ion exchange resin and gel chromatography procedures. The change in the metals' species with time after sludge application was followed for 100 d. Copper in the water extracts of the sludge-sand mixtures was found almost exclusively in low molecular weight (below 1000 Da) complexes. Higher molecular weight (around 2500 Da) dissolved organic carbon (DOC) was present in the extracts as well, but this DOC fraction exhibited little complexation. Copper was present in the extracts mainly as negatively charged species throughout the incubation period, and zinc tended to form zwitter ions. As incubation progressed, the relative content of positively charged Zn in solution increased. Complexation capacity of DOC in sludge water extract, extrapolated to infinite dilution, was 8.75 mM Ca g(-1) DOC. When the complexation capacity of the extract is near saturation, a mean Cu-DOC complex can be defined. It consists of 1.9 Cu atoms attached to DOC species containing 5.6 C atoms. Thus, the organic Cu complexes consist primarily of about two Cu ions attached to DOC species containing only five or six C atoms. Amino acids and small peptides or polycarboxylic acids, such as citric acid, thus may be important complexing agents of the metal.     

QUALITY STUDY OF GRAYWATER TREATMENT SYSTEMS1

ABSTRACT: A residential single family dwelling was retrofitted to recycle graywater for landscape irrigation and toilet flushing. The objective of this study was to determine improvements in graywater quality by evaluating five simple graywater treatment systems that were easily adapted to the household plumbing. The treatment systems consisted of (1) water hyacinths and sand filtration, (2) water hyacinths, copper ion disinfection, and sand filtration, (3) copper ion disinfection and sand filtration, (4) copper/silver ion disinfection and sand filtration, and (5) 20–μm cartridge filtration. Water quality parameters measured were fecal and total coliform indicator bacteria, nitrates, suspended solids, and turbidity. Reductions in bacterial concentration, suspended solids and turbidity were achieved by all systems tested. Treatment reduced nitrate concentrations to an average of 2.6 mg/liter. Reductions in suspended solids, and turbidity were influenced more by the quality of the graywater entering the treatment system than the efficiency of the systems themselves. The water hyacinths and sand filtration system provided the best graywater quality in terms of the concentrations of fecal indicator bacteria. The system providing the best water quality in regard to average suspended solids after treatment was the water hyacinths, copper ion, and sand filtration system, and the best average turbidity was achieved by the copper/silver ion generating unit with sand filtration. All systems were capable of significant reductions in fecal indicator bacteria, suspended solids, and turbidity; however, additional treatment or disinfection would be necessary to further reduce the level of coliform and fecal coliform bacteria to achieve regulatory standards in the State of Arizona.