Cu, Cr and As distribution in soils adjacent to CCA-treated utility poles in Eastern Blacksea Region of Turkey

In this study, the main objective was to asses the distribution of Cu, Cr, and As in soils adjacent to CCA-treated utility poles in Eastern Blacksea Region of Turkey (Trabzon, Rize and Artvin ) and determine the influence of soil composition.

Surface (0–5 cm) and subsurface soil samples (30–40 cm) were collected near CCA-treated utility poles and control soil samples away from CCA-treated utility poles were also collected. Water holding capacity, pH and mechanical properties of soil samples were determined for both depth levels.

Results showed that Cu, Cr and As concentration in soil samples taken from all three cities in 0–5 cm depth was higher than soil samples taken from 30–40 cm depth. Cu, Cr and As concentrations were much higher in soil samples taken from city of Rize     

Dislodgeable copper,chromium and arsenic from CCA-treated wood surfaces

Chromated copper arsenate (CCA) is commonly used to preserve wood, but its use poses risk of arsenic exposure. In order to evaluate the extent of exposure to As from physical contact with CCA-treated wood, dislodgeable As from treated wood surfaces (as well as Cu and Cr) was determined as a function of weathering time using dampened polyester wipe materials. Six sets of 2.5-m-long CCA-treated boards, three-four boards per set, were purchased from lumber yards and cut into 30- or 60-cm coupons. A total of 44 such coupons were placed outdoors and the dislodgeable CCA components from the surfaces of the wooden coupons were periodically determined over a 1- or 2-year period by a systematic wipe method followed by nitric acid extraction of the CCA components from the cloth. In all 316 samples, appreciable amounts of the three elements, Cu, Cr and As, were detected. The amounts of surface-dislodgeable As, the most potentially hazardous element and the one of major concern in this study, varied from 5 to 122 microg/100 cm(2) with an average value of 37+/-22 microg/100 cm(2). There was considerable variation in As dislodged among coupons, boards, sets and time. Test coupons that tended to release relatively higher (or lower amounts) over time initially, continued to do so over time. However, the amounts of arsenic dislodged over time did not follow a simple pattern. While the As dislodged tended to decrease with time during the first year, it approached the initial value or increased somewhat during the second year, presumably due to surface rejuvenation effects caused by erosion and weathering. When all the data were normalized to the initial values, no trend emerged, as indicated by the average normalized value of 1.0+/-0.4 for As dislodged over time. Apparently, on installations constructed with CCA-treated wood, arsenic may remain available for a number of years.     

Evaluation of effect of leaching medium on the release of copper,chromium, and arsenic from treated wood

There is increasing public concern about environmental contamination from preservative treated wood due to release of toxic preservative components to the environment. Leaching of wood preservatives from treated wood in service can be affected by a number of factors such as wood and preservative treatment characteristics and properties of water and soil substrate in which treated wood is placed i.e. salinity, pH, and temperature. Laboratory leaching tests usually require distilled or deionized water for leaching procedure however treated wood is generally exposed to different types of water and soil conditions. This study evaluates the release of copper, chromium and arsenic elements from chromated copper arsenate (CCA)-treated wood exposed to either distilled water, tap water, sea water or humic acid. Leaching tests were conducted in laboratory conditions using wood blocks treated with CCA wood preservative at either low or high retention levels. Results showed that tap water resulted in less preservative release when compared to the other leaching media used in the study. Humic acid was the most effective medium causing more element leaching. The percentage of components leached was always higher in wood blocks treated at the high retention in comparison with the low retention level. Our results from the leaching tests can be important in developing more realistic standard leaching methods to evaluate preservative components to be released from treated wood.     

Distribution and mobility of chromium, copper, and arsenic in soils collected near CCA-treated wood structures in Korea

Chromated copper arsenate (CCA) is currently the most commonly used wood preservative in Korea. Questions, however, have been raised regarding the potential environmental impacts of metal leaching from CCA-treated wood to soil. Although a number of researchers from other countries have reported that chromium, copper, and arsenic do leach from CCA-treated wood over time, to date few field studies have been performed on those metals in soils adjacent to CCA-treated wood structures in Korea. The present study was conducted to determine the lateral and vertical distributions and accumulation of chromium, copper, and arsenic in soils collected from CCA-treated wood structures. A total of fifty-five composite soil samples were collected from four CCA-treated wood structures of approximately one year in age. The samples were analyzed for physicochemical properties as well as for the total chromium, copper, and arsenic concentrations. The chromium, copper, and arsenic concentrations in soil samples adjacent to the structures were as high as 79.0, 98.9, and 128 mg/kg, respectively, compared to background soil samples (48.2, 26.9, and 6.27 mg/kg, respectively). Arsenic was more mobile in soil than chromium and copper. The concentration gradient of arsenic in soil was observed only to the depth of approximately 5 cm in one year of outdoor exposure, whereas chromium and copper apparently remained near the surface (approximately less than 1 cm) after their release. Future efforts should be made to observe seasonal impacts on the release of metals and incorporate metal speciation into determining more detailed mobility and distribution.     

Partitioning and speciation of chromium, copper, and arsenic in CCA-contaminated soils: influence of soil composition

This study focused on the influence of soil composition and physicochemical characteristics on the retention and partitioning of Cu, Cr and As in nine chromated copper arsenate (CCA) artificially contaminated soils. A statistical mixture design was used to set up the number of soils and their respective composition. Sequential extraction and modified solvent extraction were used to assess Cu and Cr partitioning and As speciation [As(III) or As(V)]. It was found that peat had a strong influence on CEC (232 meq/100 g), on buffer capacity and on Cu and Cr retention, whereas kaolinite's contribution to the CEC was minor (38 meq/100 g). Average metal retention in mineral soils was low (58% for Cu and 23% for Cr) but increased dramatically in highly organic soils (96% for Cu and 78% for Cr). However, both organic and mineral soils demonstrated a very high sorption of added As (71-81%). Levels of Cu and Cr in a soluble or exchangeable form (F1) in highly organic soils were very low, whereas the levels strongly bound to organic matter were much higher. Conversely, in mineral soils, 47% of Cu and 18% of Cr were found in F1. As a result, Cr and Cu in moderately and highly organic contaminated soils were present in less mobile and less bioavailable forms, whereas in mineral soils, the labile fraction was higher. The modified method used for selective determination of mineral As species in CCA-contaminated soils was found to be quantitative and reliable. Results revealed that arsenic was principally in the pentavalent state. Nevertheless, in organic soils, arsenite was found in significant proportions (average value of 29% in highly organic soils). This indicates that some reduction of arsenate to arsenite occurred since the original species in CCA is As(V).     

Mobility of copper, chromium and arsenic from treated timber into grapevines

The use of chromated copper arsenate (CCA) treated timber posts as support structures in New Zealand vineyards has raised concerns regarding the release of heavy metal(loid)s from the treated timber into the environment. A laboratory experiment was set up to evaluate if post sealing by painting reduces the release rate of CCA metal(loid)s from timber posts. Three posts were painted (Gripset 38, Multi Purpose Bitumen Rubber) on the bottom part, submerged in freshwater, and the concentrations of copper (Cu), chromium (Cr) and arsenic (As) in the water were monitored over a period of 8 months. Three additional, unpainted posts were also used. The CCA contents in the water showed a clear difference between the painted and the unpainted posts, and painting the bottom of the posts reduced the release rate by 50-75%. To monitor the possible mobility of CCA from treated posts into grapevines further, an experiment with four-year-old grapevines planted into sixteen lysimeters was set up in a greenhouse. To half the lysimeters Cu, Cr and As were added to the soil surface at rates of 16, 20, and 12.5 mg/month from 15 November 2005 to 5 May 2006. The other lysimeters acted as a control. Soil solutions were collected at 50, 150 and 300 mm depths using suction cups after seven application of the CCA solution. The results showed that all the elements moved to a depth of 50 mm. Grape fruit, leaves and rachis were analysed for CCA metal(loid)s, but did not show any differences between the CCA-treated and control lysimeters. This indicated either that these metals were not taken up by grapevines or that their translocation from roots to the upper part of the vine was negligible. Further monitoring of CCA metal(loid)s in various parts of the grapevines, including roots, needs to be undertaken.     

Leaching of copper, chromium and arsenic from treated vineyard posts in Marlborough, New Zealand

There have been conflicting reports as to the extent that copper-chromium-arsenic (CCA) treatments leach from timber. In New Zealand, vineyards utilise CCA-treated posts at a rate of 579 posts per hectare. This represents a potential CCA burden on the soil of 12, 21, and 17 kg/ha, respectively, for the three elements. Given a replacement rate of 4% per year, the use of CCA-treated posts may result in an accumulation of these elements in the soil, possibly leading to groundwater contamination. We undertook a general survey to determine the extent of CCA leaching from treated vineyard posts. Treated Pinus radiata posts were sampled at six sites around the Marlborough region of New Zealand to represent a range of post ages and soil types. For each post, above- and belowground wood samples were taken. As well, the soil adjacent to the post was sampled at a 50 mm horizontal and 100 mm vertical distances from the post. The belowground wood samples of the posts had significantly lower CCA concentrations than the aboveground portions, which were not significantly different from new posts. This indicates leaching. Soils surrounding the posts had significantly higher CCA concentrations than control soils. Higher CCA concentrations were measured under the posts than laterally. Some 25% of the samples exceeded 100 mg/kg As, the Australian National Environment Protection Council (ANEPC) guideline level for As in agricultural soil, and 10% exceeded 100 mg/kg Cr, the ANEPC limit for chromium. At one site, we found a significant positive correlation between post age and CCA-leaching. The CCA issue could be eliminated by using alternative posts, such as steel, concrete, or untreated woods such as Eucalyptus or beech. Alternatively, CCA-treated posts could, for example, be lacquered or otherwise protected, to reduce the rate of CCA leaching.     

Removal of copper,nickel, cobalt and manganese from aqueous solution by kaolinite

The removal of some heavy metals such as Mn(II), Co(II), Ni(II), and Cu(II) from aqueous solution is studied using a raw kaolinite. The sorption of these metals on kaolinite conformed to linear form of Langmuir adsorption equation. Langmuir C(m) constants for each metal were found as 0.446 mg/g (Mn), 0.919 mg/g (Co), 1.669 mg/g (Ni), 10787 mg/g (Cu) at 25 degrees C, respectively. Also, kinetic and thermodynamic parameters such as enthalpy (deltaH), free energy (deltaG) and entropy (deltaS) were calculated and these values show that adsorption of heavy metal on kaolinite was an endothermic process and the process of adsorption was favoured at high temperatures.     

Geochemical factors complicating the use of aufwuchs to monitor bioaccumulation of arsenic, cadmium, chromium, copper and zinc

Material accumulating on submerged glass slides was sampled from five sites associated with coal ash settling basins and a control site. Correlation analyses demonstrated a strong, positive correlation between the five elements, arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu) and zinc (Zn) and concentrations of associated iron or manganese. Negative, weak or nonsignificant correlations were noted between the concentrations of these five elements and microfloral cell densities or per cent ash free weight of the material. Scanning electron microscopy and X-ray analyses indicated that the majority of the material was abiotic and the elemental levels associated with the abiotic components were generally higher than those of the biotic components. Hydrous iron and manganese oxides likely play dominant roles in determining the trace element concentrations in these procedurally-defined aufwuchs. These findings indicate the potential for misinterpretation of biomonitoring data employing procedurally-defined aufwuchs.     

Removal of chromium from aqueous solutions and plating bath rinse by an electrochemical method

In this work, a bipolar packed bed electrolytic cell having steel Raschig rings behaving as electrodes has been used to remove chromium in the form of Cr(VI) from aqueous solutions and a sample of plating bath rinse.

Fe²⁺ ions generated at the anode side of the electrodes have reacted with OH^‐ ions generated at the cathode side forming Fe(OH)₂ in this electrolytic cell.Cr(VI) have coprecipitated as Cr(OH)₃ with Fe(OH)₃ forming after the redox reaction between Fe(OH)₂ and Cr(VI). Meanwhile other impurities have also removed besides Cr(VI) using this process. Removal rate of 100% for Cr(VI) has been achieved in the experiments done with different initial Cr(VI) concentration, duration of electrolysis and applied potential. Fully removal of Cr(VI) has also been achieved from the sample of plating bath rinse.     

Removal of anionic dye Congo red from aqueous solution by raw pine and acid-treated pine cone powder as adsorbent: equilibrium, thermodynamic, kinetics, mechanism and process design

Pine cone a natural, low-cost agricultural by-product in Australia has been studied for its potential application as an adsorbent in its raw and hydrochloric acid modified form. Surface study of pine cone and treated pine cone was investigated using Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The modification process leads to increases in the specific surface area and decreases mean particle sizes of acid-treated pine cone when compared to raw pine cone biomass. Batch adsorption experiments were performed to remove anionic dye Congo red from aqueous solution. It was found that the extent of Congo red adsorption by both raw pine cone biomass and acid-treated biomass increased with initial dye concentration, contact time, temperature but decreased with increasing solution pH and amount of adsorbent of the system. Overall, kinetic studies showed that the dye adsorption process followed pseudo-second-order kinetics based on pseudo-first-order and intra-particle diffusion models. The different kinetic parameters including rate constant, half-adsorption time, and diffusion coefficient were determined at different physico-chemical conditions. Equilibrium data were best represented by Freundlich isotherm model among Langmuir and Freundlich adsorption isotherm models. It was observed that the adsorption was pH dependent and the maximum adsorption of 32.65 mg/g occurred at pH of 3.55 for an initial dye concentration of 20 ppm by raw pine cone, whereas for acid-treated pine cone the maximum adsorption of 40.19 mg/g for the same experimental conditions. Freundlich constant 'n' also indicated favourable adsorption. Thermodynamic parameters such as ?G(0), ?H(0), and ?S(0) were calculated. A single-stage batch absorber design for the Congo red adsorption onto pine cone biomass also presented based on the Freundlich isotherm model equation.     

Removal of copper and nickel ions from aqueous solutions by grape stalks wastes

In the present work, the usefulness of grape stalks wastes generated in the wine production process has been investigated for the removal of copper and nickel ions from aqueous solutions. The sorption process was relatively fast and equilibrium was reached after about 60 min of contact. The influence of pH, sodium chloride and metal concentration on metal removal has been studied. Uptake showed a pH-dependent profile. Maximum sorption for both metals was found to occur at around pH 5.5-6.0. An increase of sodium chloride concentration caused a decrease in metal removal. Langmuir isotherms, at pH 6.0, for each metal were used to describe sorption equilibrium data. Maximum uptake obtained was 1.59x10(-4) mol of copper and 1.81x10(-4) mol of nickel per gram of dry sorbent. Sorption of copper and nickel on grape stalks released an equivalent amount of alkaline and alkaline earth metals (K+, Mg2+, Ca2+) and protons, indicating that ionic exchange is predominantly responsible for metal ion uptake. Fourier transform infrared (FTIR) spectrometry analysis indicated that lignin C-O bond might be involved in metal uptake. Equilibrium batch sorption studies were also performed using a two metal system containing (Cu(II)+Ni(II)). In the evaluation of the two metal sorption system performance, single isotherm curves had to be replaced by three-dimensional sorption isotherm surface. In order to describe the isotherm surface mathematically, the extended-Langmuir model was used. Nickel was found to be much more sensitive to the presence of copper than copper is to the presence of nickel.     

Removal of zinc, copper and lead by natural zeolite-a comparison of adsorption isotherms

An uptake of zinc (Zn), copper (Cu), and lead (Pb) from aqueous solutions by ion exchange on natural zeolitic tuff has been studied. The Croatian zeolite clinoptilolite from the Donje Jesenje deposit has been used as a natural ion exchanger. The efficiency of removal is higher for Pb and Cu than for Zn ions. Measured concentrations of Si in the liquid phase identify the detachment of the aluminosilicate structure during ion exchange in the presence of H(+) and OH(-) ions. The adsorption isotherm equations; Langmuir-Freundlich, Redlich-Petersen, Toth, Dubinin-Radushkevich, modified Dubinin-Radushkevich, and Lineweawer-Burk were derived from the basic empirical equations, and used for calculation of ion exchange parameters. The best fitting of experimental results to the proposed isotherms was observed in models that assume that ionic species bind first at energetically most favorable sites, with multi-layer adsorption taking place subsequently.     

Bioaccumulation and toxicity of copper as affected by interactions between humic acid and water hardness

This study evaluated the effects of water hardness and humic acid (HA) on the acute and chronic toxicity of copper to Daphnia pulex and on its accumulation by D. magna. Hardness had little effect on either the acute (3-day) or the chronic (42-day) toxicity of copper. Humic acid significantly reduced both the acute and chronic toxicity of copper when added to waters having hardnesses of 58, 115 and 230 mg l^?1 as CaCO₃. The effect, per unit of HA, on chronic toxicity was very similar for soft and medium water but less in hard water. At each of two HA concentrations, copper was chronically more toxic in hard water than in either medium or soft water. Bioaccumulation of copper varied with relative hardness and HA concentration and this was further affected by age at exposure. For 1-day-old animals, an increase in either hardness or HA- or any combination of the two, tended to decrease bioaccumulation. Results for 7-day-old animals were in general agreement except for animals exposed to copper in hard water at an intermediate HA concentration. These animals accumulated significantly more copper in the presence of HA. This agrees with the fact that this concentration of HA also increased the chronic toxicity of copper in hard water. Both of those phenomena are probably due to the displacement of Cu²⁺ from HA by competition from the increased concentrations of Ca²⁺ and Mg²⁺. The fact that HA had the opposite effect on copper accumulation by young animals in hard water could not be explained.     

Removal of co-present chromate and arsenate by zero-valent iron in groundwater with humic acid and bicarbonate

The interactions of co-present Cr(VI) and As(V), and the influences of humic acid and bicarbonate in the process of Cr(VI) and As(V) removal by Fe⁰ were investigated in a batch setting using simulated groundwater with 5 mM NaCl, 1 mM Na₂SO₄, and 0.8 mM CaCl₂ as background electrolytes at an initial pH value of 7. Cr(VI) and As(V) were observed to be subject to different impacts induced by co-existing As(V) or Cr(VI), humic acid and bicarbonate, originating from their distinct removal mechanisms by Fe⁰. Cr(VI) removal is a reduction-dominated process, whereas As(V) removal principally involves adsorption onto iron corrosion products. Experimental results showed that Cr(VI) removal was not affected by the presence of As(V) and humic acid. However, As(V) removal appeared to be inhibited by co-present Cr(VI). When the Cr(VI) concentration was 2, 5, and 10 mg/L, in the absence of humic acid and bicarbonate, As(V) removal rate constants were decreased by 27.9%, 49.0%, and 61.2%, respectively, which probably resulted from competition between Cr(VI) and As(V) for adsorption sites of the iron corrosion products. Furthermore, the presence of humic acid significantly varied As(V) removal kinetics by delaying the formation and aggregation of iron hydroxides due to the formation of soluble Fe-humate complexes and stably dispersed fine iron hydroxides colloids. In the presence of bicarbonate, both Cr(VI) and As(V) removal was increased and the inhibitory effect of Cr(VI) on As(V) removal was suppressed, resulting from the buffering effects and the promoted iron corrosion induced by bicarbonate, and the formation of CaCO₃ in solution, which enhanced As(V) adsorption.     

Removal of atrazine, lindane and diazinone from water by organo-zeolites

Systematic adsorption tests were carried out to determine the efficiency of organo-zeolite (OZ) for removal of atrazine, lindane and diazinone from water. The hydrophobic character of OZ-pesticide interactions was confirmed by measuring the amount of pesticides sorbed on zeolite samples modified with 25, 50, 75 and 150 mmol of stearyldimethylbenzylammoniumchloride (SDBAC)/kg of zeolite. The effects of adsorbent particle size, solid content in the suspension and the initial pesticide concentration in the solutions were also investigated. For effective adsorption of diazinone onto an OZ, it is necessary for the SDBAC/diazinon ratio to be higher than 25. The adsorption capacities, calculated by fitting the experimental data to the Langmuir-Freundlich equation, were 2.0 micromol/g (atrazine), 4.4 micromol/g (diazinone) and 3.4 micromol/g (lindan). At lower initial concentrations of pesticide solution, a linear dependence existed between the amount adsorbed and the equilibrium concentration of pesticide. Column experiments showed that at volumetric flow of 6 cm3/ min, the breakthrough points (at C/C0 = 0.1) were 560 bed volume (BV) for lindane and 620 for diazinone.     

Dietary ascorbic acid and alpha-tocopherol mitigates oxidative stress induced by copper in the thornfish Terapon jarbua

The protective effects of vitamins C and E against oxidative stress were evaluated in various tissues of thornfish Terapon jarbua exposed to copper. Preliminary bioassay tests performed with copper and T. jarbua revealed that 4.0, 2.5 and 1.0 mg L(-1) of copper were lethal (LC(100)), medial lethal (LC(50)) and sublethal (LC(0)) respectively. Oxidative stress parameters viz. lipid peroxidation, superoxide dismutase, catalase, glutathione peroxidase, and glutathione were evaluated in control and experimental fishes. Lipid peroxidation activity increased in tissues of copper exposed fishes, while the antioxidant system exhibited a reduction in their activity. On the contrary copper stressed fishes fed with vitamins C and E enriched pellet feed showed significant reduction in lipid peroxidation activity and the antioxidant levels increased reaching near normal levels comparable to control values. Bioaccumulation of copper was studied in addition to oxidative stress. Substantial copper residue was detected in the tissues of T. jarbua exposed to copper and the level of copper in tissues reduced when the fishes were treated with vitamins ensuring copper depuration and thereby protecting them against stress. We concluded that vitamin supplementation offered significant reduction of the oxidative stress mediated by copper and we discuss the possible application of vitamins in costal aquaculture process.     

Removal of Cr,Ni and Co in the water of chromium mining areas by using Lemna gibba L. and Lemna minor L

This study investigated the use of Lemna gibba and Lemna minor plant species to absorb Cr, Ni and Co from Alacakaya mining area water. Lemna gibba and L. minor were separately placed to feed into two reactors. Water and plant samples were collected for eight consecutive days, and the pH, electric conductivity and temperature of the water were measured. The plants were washed, dried and burned at 300°C for 24 h in a drying oven. The samples were then analysed by ICP‐MS (inductively coupled plasma mass spectroscopy) for concentrations of Cr, Ni and Co, which were 1.2, 0.9 and 0.5 μg L^?1 respectively. On Day 8, the determined uptake of L. gibba and L. minor were: 196 and 398% for Cr; 307 and 1473% for Ni; and 166 and 223% for Co respectively. Lemna gibba and L. minor were thus effective in absorbing Cr, Ni and Co from mining water.