A COLORIMETRIC METHOD FOR THE DETERMINATION OF TRACE COPPER CONCENTRATIONS IN WATER1

Trace quantities of copper (II) ion can be found in natural water as waste products from industrial, mining, and agricultural operations. Because low concentrations of copper can be toxic to plant life, many workers have devised methods of analysis for this metal in water. These methods require expensive equipment and skilled technicians. The described study illustrates a simple method in which copper (II) ion is concentrated by a batch ion exchange technique and estimated colorimetrically after formation of the blue triethylenetetramine complex. Using the visible absorption peak of the complex at 600 nm it was possible to obtain accurate estimations of original copper concentrations in the range 0.5-3 ppm. Using the complex absorption peak at 260 nm in the ultra-violet region of the spectrum increased the sensitivity by a factor of twenty. Because of the dependence of the complex formation reaction on solution acidity it is possible to optimize conditions for the detection of copper (II) in the presence of other metal ions. This type of method, which could be extended to the analysis of other metal ions, could be performed by a relatively unskilled technician under field conditions.     

Fractionation of selected metals in the sediments of Cochin estuary and Periyar River, southwest coast of India

Cochin estuary is one of the highly polluted aquatic systems of the southwest coast of India. The present study focuses on the assessment of heavy metals (Zn, Cd, Pb, and Cu) present in the sediments of Cochin estuary and the adjoining Periyar River. The sediments were analyzed for total metal content and various chemically bound fractions such as exchangeable, carbonate bound, easily reducible, organic, and residual. Total metal content of sediment was found higher than the average values reported from other Indian rivers. The mean concentration of Zn, Cd, Pb, and Cu in the sediments was 1,249.44, 9.5, 221.37, and 166.14???g/g, respectively. The results of sequential extraction showed that the concentration of Cd was high in the first two weakly bound fractions (exchangeable and carbonate bound) than the other metals, which are high in residual and organic bound fractions. Risk-assessment code analysis and environmental indices (enrichment factor and pollution load index) suggest that the sediments are highly polluted with metals, especially Cd.     

Impact of Dredging on Phosphorus Transport in Agricultural Drainage Ditches of the Atlantic Coastal Plain1

Abstract: Drainage ditches can be a key conduit of phosphorus (P) between agricultural soils of the Atlantic Coastal Plain and local surface waters, including the Chesapeake Bay. This study sought to quantify the effect of a common ditch management practice, sediment dredging, on fate of P in drainage ditches. Sediments from two drainage ditches that had been monitored for seven years and had similar characteristics (flow, P loadings, sediment properties) were sampled (0‐5 cm) after one of the ditches had been dredged, which removed fine textured sediments (clay = 41%) with high organic matter content (85 g/kg) and exposed coarse textured sediments (clay = 15%) with low organic matter content (2.2 g/kg). Sediments were subjected to a three‐phase experiment (equilibrium, uptake, and release) in recirculating 10‐m‐long, 0.2‐m‐wide, and 5‐cm‐deep flumes to evaluate their role as sources and sinks of P. Under conditions of low initial P concentrations in flume water, sediments from the dredged ditch released 13 times less P to the water than did sediments from the ditch that had not been dredged, equivalent to 24 mg dissolved P. However, the sediments from the dredged ditch removed 19% less P (76 mg) from the flume water when it was spiked with dissolved P to approximate long‐term runoff concentrations. Irradiation of sediments to destroy microorganisms revealed that biological processes accounted for up to 30% of P uptake in the coarse textured sediments of the dredged ditch and 18% in the fine textured sediments of the undredged ditch. Results indicate that dredging of coastal plain drainage ditches can potentially impact the P buffering capacity of ditches draining agricultural soils with a high potential for P runoff.     

The feasibility of decontamination of reduced saline sediments from copper using the electrokinetic process

The remediation of metal contamination in estuarine and reduced sediments is another challenge for the electrokinetic process. Problems result from the complex chemical composition of saline reduced sediments. In the experiments described here copper was added into saline reduced sediments to simulate the natural situation. Two constant voltages were applied across the electrokinetic cell to investigate the effect of an increase in potential difference on the electrokinetic process. Acetic acid at pH 6 and 4 was also added to the cathode in separate experiments to enhance copper removal. The results from this study showed that in the unenhanced experiments most of copper remained in the soil and was unaffected by the electrokinetic process. At the end of unenhanced electrokinetic experiments, the copper concentration was found only to be slightly changed in the anode region. Up to 21% of the copper was found precipitated near the anode when the applied voltage was 10V and this increased to 25% when the applied voltage was 7V. In the enhanced electrokinetic experiments up to 98% of copper was removed from section 1 and precipitated again in sections 2 and 3. This indicates that a significant amount copper removal from the saline sediments may be achieved by the enhanced electrokinetic process.     

Dredged Illinois River sediments: plant growth and metal uptake

Sedimentation of the Illinois River in central Illinois has greatly diminished the utility and ecological value of the Peoria Lakes reach of the river. Consequently, a large dredging project has been proposed to improve its wildlife habitat and recreation potential, but disposal of the dredged sediment presents a challenge. Land placement is an attractive option. Previous work in Illinois has demonstrated that sediments are potentially capable of supporting agronomic crops due to their high natural fertility and water holding capacity. However, Illinois River sediments have elevated levels of heavy metals, which may be important if they are used as garden or agricultural soil. A greenhouse experiment was conducted to determine if these sediments could serve as a plant growth medium. A secondary objective was to determine if plants grown on sediments accumulated significant heavy metal concentrations. Our results indicated that lettuce (Lactuca sativa L.), barley (Hordeum vulgare L.), radish (Raphanus sativus L.), tomato (Lycopersicon lycopersicum L.), and snap bean (Phaseolus vulagaris L. var. humillis) grown in sediment and a reference topsoil did not show significant or consistent differences in germination or yields. In addition, there was not a consistent statistically significant difference in metal content among tomatoes grown in sediments, topsoil, or grown locally in gardens. In the other plants grown on sediments, while Cd and Cu in all cases and As in lettuce and snap bean were elevated, levels were below those considered excessive. Results indicate that properly managed, these relatively uncontaminated calcareous sediments can make productive soils and that metal uptake of plants grown in these sediments is generally not a concern.     

pH-dependent release of cadmium,copper, and lead from natural and sludge-amended soils

The pH-dependent release of cadmium, copper, and lead from soil materials was studied by use of a stirred flow cell to quantify their release and release rates, and to evaluate the method as a test for the bonding strength and potential mobility of heavy metals in soils. Soil materials from sludge-amended and nonamended A horizons from a Thai coarse-textured Kandiustult and a Danish loamy Hapludalf were characterized and tested. For each soil sample, release experiments with steady state pH values in the range 2.9 to 7.1 and duration of 7 d were performed. The effluent was continuously collected and analyzed. Release rates and total releases were higher for the Hapludalf than the Kandiustult and higher for the sludge-amended soils than the nonamended soils. With two exceptions the relative release rates (release rate/total content of metal in soil) plotted vs. steady state pH followed the same curves for each metal, indicating similar bonding strengths. These curves could be described by a rate expression of the form: relative release rate = k[H+]a, with specific a (empirical constant) and k (rate constant) parameters for each metal demonstrating that metal release in these systems can be explained by proton-induced desorption and dissolution reactions. With decreasing pH, pronounced increases in release rates were observed in the sequence cadmium > lead > copper, which express the order of metal lability in the soils. The flow cell system is useful for comparison of metal releases as a function of soil properties, and can be used as a test to rank soils with respect to heavy metal leaching.     

Nonlinear and competitive sorption of apolar compounds in black carbon-free natural organic materials

Numerous studies have reported a spectrum of sorption phenomena in soils, sediments, and organic matter isolates of those materials that are inconsistent with a partition model proposed in the late 1970s and early 1980s, a model predicated on a hypothesis that sorption is linear and noncompetitive. To explain these nonideal phenomena, prior studies have proposed a hard-soft (glassy-rubbery) model for SOM (soil and sediment organic matter), while others have attributed them singularly to BC (black carbon: soot and charcoal) particles present in topsoils and sediments. In this study, we demonstrated nonideal sorption behavior (isotherm nonlinearity, competitive effects) for a group of apolar compounds in a large set of natural and model organic materials, including a commercial lignin and humic acids from different sources. Complete oxidation of samples by an acidic dichromate method was taken to signify the absence of BC. (However, polymethylene units are stable even if functionalized on both ends, making the technique unreliable for quantifying BC.) Other samples were inferred free of BC by their source and method of preparation. Characterization by thermalanalytical methods indicated the glassy character of the organic materials. The origin of the nonideal behaviors appears to be the glassy character of these materials. Sorption nonlinearity increased or decreased by changing temperature, cosolvent content, or degree of cross-linking by metal ions as predicted for organic solids in a glassy state. We conclude that macromolecular humic substances in the environment may exhibit nonideal sorption behavior in soils and sediments, quite apart from any such behaviors attributable to BC.     

INPUTS OF COPPER‐BASED CROP PROTECTANTS TO COASTAL CREEKS FROM PASTICULTURE RUNOFF1

ABSTRACT: Inputs of copper‐based crop protectants from tomato fields grown under plastic mulch agriculture (plasticulture) to an estuarine creek were investigated. Copper was measured in runoff from diverse land‐uses including conventional agriculture, plasticulture, residences, and natural areas. Water column and sediment copper concentrations were measured in plasticulture and control (nonagriculture) watersheds. Copper concentrations in plasticulture‐impacted creeks exceeded background levels episodically. High concentrations occurred during or immediately after runoff‐producing rains. Concentrations of 263 μg/L total copper and 126 μg/L dissolved copper were measured in a tidal creek affected by plasticulture; concentrations exceeded the shellfish LC₅₀ values and the water quality criteria of 2.9 μg/L dissolved copper. Control watersheds indicated background water column levels of ≤ 4 μg/L dissolved copper with similar copper levels during periods with and without rain. The copper concentrations in tomato plasticulture field runoff itself contained up to 238 μg/L dissolved copper. Copper concentrations in runoff from other land‐uses were less than 5 μg/L dissolved copper. Creek sediment samples adjacent to a plasticulture field contained significantly higher copper concentrations than sediments taken from nonplasticulture watersheds.     

THE IMPACT OF URBANIZATION ON THE DISTRIBUTION OF HEAVY METALS IN BOTTOM SEDIMENTS OF THE SADDLE RIVER1

ABSTRACT: A three-year study has been conducted on a 4.6 mile stretch of the Saddle River near Lodi, New Jersey. The primary objectives of this investigation were (1) to provide baseline information on the concentration and distribution of heavy metals in bottom sediments of the Saddle River; (2) to qualitatively evaluate which parameters affect this distribution; and (3) to determine the effect of urbanization on the concentration and distribution of these materials. Significant enrichments of several heavy metals were observed in bottom sediments of the lower Saddle River near Lodi, New Jersey, as compared to the upper Saddle River. Attempts to correlate metal concentrations in bottom sediments with chemical-oxygen demand were not successful in demonstrating a relationship between these two factors. Metal concentrations were found to be strongly dependent upon particle size. In general, metal concentrations in bottom sediments increased with decreasing partical diameter. However, metals enrichment was observed to be considerably greater in the larger sediment fractions studied (>420μ) than the smaller sediment fractions as one proceeded downstream through the urban area. Since the larger sediment fractions are least effected by scour and transport they may best reflect the effect of urbanization on the distribution of heavy metals over an extended period of time at a given location.     

Copper availability in seven Israeli soils incubated with and without biosolids

Land application is becoming a preferred option for disposal of sewage sludge (biosolids) from wastewater treatment plants. However, it creates potential risks due to the heavy metal contents of these materials, with copper (Cu) being of chief concern. The long-term fate of biosolid metals applied to agricultural soils is not well understood, particularly in the soils of the Middle East. This investigation was conducted to determine whether the availability of Cu changes with time in biosolid-amended and nonamended soils from Israel. Seven soils, typifying the span of properties and formation environments encountered in Israel, were incubated with and without biosolids for 7 yr, and changes in organic carbon (OC) content and labile Cu concentration were determined. Isotopic exchange techniques, using 64Cu, and ion activity measurements, using a Cu2+ ion selective electrode, revealed that the available Cu concentration remained relatively low and stable over the 7-yr incubation. This was despite substantial reductions in OC. This study shows that, with regard to Cu, application of such biosolids to these soils at rates of up to 250 Mg ha(-1) does not pose a threat to the environment in the short to medium term.     

Electrochemical remediation of copper (II) from an industrial effluent Part II: three-dimensional foam electrodes

A batch recycle removal of copper ions from an industrial effluent by means of copper foam cathodes was tested. A constant current of 750 A was applied to the cell in order to perform the reduction. Copper depletion was investigated at different solution flow rates and a removal greater than 98% was obtained with a flow rate of 1000 l/h. The influence of initial metal concentration on copper deposition and current efficiency is also discussed.     

Dissolution kinetics of heavy metals in Dutch carbonate- and sulfide-rich freshwater sediments

In two sulfide-rich freshwater sediments from the Biesbosch and Kromme Rijn River in the Netherlands differing in carbonate content and acid volatile sulfide (AVS) content, metal and sulfide dissolution kinetics were studied at different acid concentrations by varying both the procedure of acid addition and the extraction time. The establishment of equilibrium was monitored by measuring the pH in time, which reached a near constant value. The equilibrium pH was reached quickly when large amounts of acid were added and slowly when small amounts of acid were added. This observation was confirmed by the yield of extracted metals after either a 45-min or 24-h extraction over a pH range from 0 to 5. The pH factor seemed to be of more influence than time for the dissolution of metals. The amount of extracted metals was highly dependent on the metal itself due to its physico-chemical behavior. Although the sediments studied varied in carbonate content, acid volatile sulfide (AVS), and total metal content, the extracted fraction of metals compared with their total content in the sediment was similar for most metals. Finally, the AVS content as well as the ratio of simultaneously extracted metals (SEM; sum of Cd, Cu, Ni, Pb, and Zn) to AVS decreased with increasing pH. Because the SEM to AVS ratio may be used to set environmental quality criteria for the sediment compartment, this observation is of significance.     

Relationships between bacterial tolerance levels and forms of copper and zinc in soils

The effects of various fractions of copper (Cu) and zinc (Zn) on soil bacteria were evaluated by the heavy metal tolerance level of the bacterial community (IC50) in soil samples collected near a mine. The IC50 values had no relationship with the total concentrations of Zn and Cu in the soils, but were weakly correlated with the 0.05 M CaCl2-extractable form of each metal in the soils (Cu: R2 = 0.670, p < 0.01; Zn: R2 = 0.453, p < 0.05). It was found that the IC50 correlated strongly with the total concentration of each metal in the extracts from water-saturated soil samples, described below as "soil solution" (Cu: R2 = 0.789, p < 0.01; Zn: R2 = 0.617, p < 0.01). The speciation of these metals in the soil solutions was estimated using an equilibrium thermodynamic computer model, SOILCHEM. Simulated free Cu ion ranged from 18 to 98% of total Cu, and organic complexes of Cu ranged from < 1 to 56%. In all samples, Zn existing as the free ion was estimated to be more than 80% of total Zn in the soil solutions. The IC50 values were also correlated with the estimated free metal ion activities, but with slightly lower correlation coefficients than found for total concentration in the soil solutions (Cu: R2 = 0.735, p < 0.01; Zn: R2 = 0.610, p < 0.01). The results suggest that not only high metal ion activities, but also total dissolved metal concentrations in soil solutions may affect the bacterial community.     

Accumulation, distribution, and toxicity of copper in sediments of catfish ponds receiving periodic copper sulfate applications

Copper sulfate (CuSO4) is applied periodically to commercial channel catfish (Ictalurus panctatus) ponds as an algicide or parasiticide. Current understanding of the chemistry of copper in soil-water systems suggests that copper may accumulate in pond sediments, although the forms and potential bioavailability of copper in catfish pond sediments are not known. This study investigated the accumulation and distribution of copper in the sediment of catfish ponds receiving periodic additions of CuSO4.5H2O. All ponds were constructed in Sharkey (very-fine, smectitic, thermic Chromic Epiaquert) soil. Nine 0.40-ha ponds received 59 applications of 2.27 kg CuSO4.5H2O per application per pond over 3 yr; no CuSO4.5H2O applications were made to nine additional ponds. Total Cu concentration in the sediments of CuSO4.5H2O-amended catfish ponds (172.5 mg kg(-1)) was four to five times higher than that in the sediments of nonamended ponds (36.1 mg kg(-1)). Copper accumulated in catfish pond sediments at a rate of 41 microg kg(-1) dry sediment for each 1 kg ha(-1) of CuSO4. 5H2O applied to ponds. Copper in the sediments of amended ponds was mainly in the organic matter-bound (30.7%), carbonate-bound (31.8%), and amorphous iron oxide-bound (22.1%) fractions with a considerable fraction (3.4%; 3 to 8 mg kg(-1)) in soluble and exchangeable fractions. This indicates that Cu accumulates differentially in various fractions, with proportionally greater initial accumulation in potentially bioavailable forms. However, toxicity bioassays with amphipods (Hyallela azteca) and common cattail (Typha latifolia L.) indicated that the effect of exposure to amended or nonamended pond sediments was not different.     

Seven thousand years in the service of humanity—the history of copper, the red metal

Measured by weight, copper is the third most important metal used by man. The annual value of its 2007 output was on a par with the GDP of e.g. Ukraine. Copper is also one of the oldest metals, its employment going back 7000 years. For millennia, it was predominantly employed for decorative purposes, coinage and in warfare. Technical breakthroughs in antiquity, like smelting and alloying, expanded its production and enhanced its utility. Copper's true heyday occurred after 1850, with the usage of electricity. In the period since then, volumes increased 300-fold, while costs and prices declined. With impressive progress in the technology of its production and consumption, the red metal has been able to hold its own, despite the emergence over history of formidable substitutes like iron, aluminum, plastics and optic fiber.     

Oxytetracycline sorption to organic matter by metal-bridging

The sorption of oxytetracycline to metal-loaded ion exchange resin and to natural organic matter by the formation of ternary complexes between polyvalent metal cations and sorbent- and sorbate ligand groups was investigated. Oxytetracycline (OTC) sorption to Ca- and Cu-loaded Chelex-100 resin increased with increasing metal/sorbate ratio at pH 7.6 (OTC speciation: 55% zwitterion, 45% anion). Greater sorption to Cu- than Ca-loaded resin was observed, consistent with the greater stability constants of Cu with both the resin sites and with OTC. Oxytetracycline sorption to organic matter was measured at pH 5.5 (OTC speciation: 1% cation, 98% zwitterion, 1% anion). No detectable sorption was measured for cellulose or lignin sorbents that contain few metal-complexing ligand groups. Sorption to Aldrich humic acid increased from "clean" < "dirty" (no cation exchange pretreatment) < Al-amended < Fe(III)-amended clean humic acid with K(d) values of 5500, 32000, 48000, and 250000 L kg(-1) C, respectively. Calcium amendments of clean humic acid suggested that a portion of the sorbed OTC was interacting by cation exchange. Oxytetracycline sorption coefficients for all humic acid sorbents were well-correlated with the total sorbed Al-plus-Fe(III) concentrations (r(2) = 0.87, log-log plot), suggesting that sorption by ternary complex formation with humic acid is important. Results of this research indicate that organic matter may be an important sorbent phase in soils and sediments for pharmaceutical compounds that can complex metals by the formation of ternary complexes between organic matter ligand groups and pharmaceutical ligand groups.     

Cadmium and zinc in vegetation and litter of a voluntary woodland that has developed on contaminated sediment-derived soil

Vegetation that develops spontaneously on metal-contaminated soils presents an opportunity to evaluate both metal bioavailability and the risks posed to biota. The behavior of Cd and Zn in the species of a spontaneously developed woodland, colonizing a canal embankment, has been investigated. Nitric-acid-extractable metal concentrations in the sediment-derived substrate ranged between 5.0 to 376 mg kg(-1)dry wt. Cd and 83.0 to 784 mg kg(-1)dry wt. Zn. The woodland is dominated by Willow (Salix) species. Salix caprea selectively accumulated Cd in all stem tissues, in contrast to S. viminalis, which regulated tissue Cd content. Both species showed an effective regulation of tissue Zn. Cadmium uptake by S. caprea was correlated with differences in soil pH, while Zn uptake was not. There was no relationship between tissue metal concentrations and soil metal nitric acid-extractable concentrations. Other aspects of ecosystem function appeared unaffected by the elevated Cd flux in S. caprea; leaf litter organisms present represented all major groups and there was no accumulation of organic matter. The woodland represents a potentially sustainable option for remediating a low value site with difficult access that does not involve removal of the contaminated material to a landfill or making a permanent inert cover.     

Assessing potential bioavailability of metals in sediments: A proposed approach

Due to anthropogenic inputs, elevated concentrations of metals frequently occur in aquatic sediments. In order to make defensible estimates of the potential risk of metals in sediments and/or develop sediment quality criteria for metals, it is essential to identify that fraction of the total metal in the sediments that is bioavailable. Studies with a variety of benthic invertebrates indicate that interstitial (pore) water concentrations of metals correspond very well with the bioavailability of metals in test sediments. Many factors may influence pore water concentrations of metals; however, in anaerobic sediments a key phase controlling partitioning of several cationic metals (cadmium, nickel, lead, zinc, copper) into pore water is acid volatile sulfide (AVS). In this paper, we present an overview of the technical basis for predicting bioavailability of cationic metals to benthic organisms based on pore water metal concentrations and metal-AVS relationships. Included are discussions of the advantages and limitations of metal bioavailability predictions based on these parameters, relative both to site-specific assessments and the development of sediment quality criteria.     

Effect of the Prestige oil spill on salt marsh soils on the coast of Galicia (northwestern Spain)

At four estuarine sites on the coast of Galicia (northwestern Spain), all of which were affected by the Prestige oil spill, soil samples were taken from polluted and unpolluted areas and their petroleum hydrocarbon contents, heavy metal contents, and other chemical and physical characteristics were measured. Oil pollution altered both chemical and physical soil properties, aggregating soil particles in plaques, lowering porosity, and increasing resistance to penetration and hydrophobicity. The chromium, nickel, copper, iron, lead, and vanadium contents of polluted soils were between 2 and 2500 times higher than those of their unpolluted counterparts and the background concentrations in Galician coastal sediments. In the cases of Cr, Cu, Ni, Pb, and V, their origin in the polluting oil was corroborated by the high correlation (r >/= 0.74) between the concentrations of these metals and the total petroleum hydrocarbon (TPH) content of the polluted soils. Soil redox potentials ranged from -19 to -114 mV in polluted soils and 112 to 164 mV in unpolluted soils, and were negatively correlated with TPH content (p < 0.01). The low values in the polluted soils explain why the soluble fractions of their total heavy metal contents were very small (generally less than 3%, and in many cases undetectable).     

CARBON CONTENT OF SEDIMENTS OF SMALL RESERVOIRS1

ABSTRACT: Carbon content was measured in sediments deposited in 58 small reservoirs across the United States. Reservoirs varied from 0.2 to 4000 km2 in surface area. The carbon content of sediment ranged from 0.3 to 5.6 percent, with a mean of 1.9 ± 1.1 percent. No significant differences between the soil and sediment carbon content were found using a paired t-test or ANOVA. The carbon content of sediments in reservoirs was similar to the carbon content of surface soils (0–10 cm) in the watershed, except in watersheds with shrub or steppe (desert) vegetation. Based on the sediment accumulation rates measured in each reservoir, the calculated organic carbon accumulation rates among reservoirs ranged from 26 to 3700 gC m^-2yr^-1, with a mean of 675 ± 739 gC m^-2yr^-1. The carbon content and accumulation rates were highest in sediments from grassland watersheds. High variability was found in carbon content, carbon accumulation, and sediment accumulation rates due to individual watershed and reservoir characteristics rather than to any broad physiographic patterns. The carbon accumulation rates in these reservoir sediments indicate that reservoir sediments could be a significant sink for organic carbon.