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The removal of Co, Ni, Cu and Zn from synthetic industrial wastewater was studied in subsurface flow constructed wetland microcosms filled with gravel or a gravel/straw mixture. Half of the microcosms were planted with Phragmites australis and half were left unplanted. All microcosms received low-strength wastewater (1 mg L−1 of Co, Ni, and Zn, 0.5 mg L−1 Cu, 2,000 mg L−1 SO4) during seven 14-day incubation batches. The pore water was regularly monitored at two depths for heavy metals, sulphate, organic carbon and redox potential. Sorption properties of gravel and straw were assessed in a separate experiment. A second series of seven incubation batches with high-strength wastewater (10 mg L−1 of each metal, 2,000 mg L−1 SO4) was then applied to saturate the substrate. Glucose was added to the gravel microcosms together with the high-strength wastewater. Sorption processes were responsible for metal removal during start-up, with the highest removal efficiencies in the gravel microcosms. The lower initial efficiencies in the gravel/straw microcosms were presumably caused by the decomposition of straw. However, after establishment of anaerobic conditions (Eh∼−200 mV), precipitation as metal sulphides provided an additional removal pathway in the gravel/straw microcosms. The addition of glucose to gravel microcosms enhanced sulphate reduction and metal removal, although Phragmites australis negatively affected these processes in the top-layer of all microcosms.

Enhanced phytoextraction proposes the use of soil amendments to increase the heavy-metal content of above-ground harvestable plant tissues. This study compares the effect of synthetic aminopolycarboxylic acids [ethylenediamine tetraacetatic acid (EDTA), nitriloacetic acid (NTA), and diethylenetriamine pentaacetic acid (DTPA)] with a number of biodegradable, low-molecular weight, organic acids (citric acid, ascorbic acid, oxalic acid, salicylic acid, and NH 4 acetate) as potential soil amendments for enhancing phytoextraction of heavy metals (Cu, Zn, Cd, Pb, and Ni) by Zea mays. The treatments in this study were applied at a dose of 2 mmol/kg −1 1 d before sowing. To compare possible effects between presow and postgermination treatments, a second smaller experiment was conducted in which EDTA, citric acid, and NH 4 acetate were added 10 d after germination as opposed to 1 d before sowing. The soil used in this screening was a moderately contaminated topsoil derived from a dredged sediment disposal site. This site has been in an oxidized state for more than 8 years before being used in this research. The high carbonate, high organic matter, and high clay content characteristic to this type of sediment are thought to suppress heavy-metal phytoavailability. Both EDTA and DTPA resulted in increased levels of heavy metals in the above-ground biomass. However, the observed increases in uptake were not as large as reported in the literature. Neither the NTA nor organic acid treatments had any significant effect on uptake when applied prior to sowing. This was attributed to the rapid mineralization of these substances and the relatively low doses applied. The generally low extraction observed in this experiment restricts the use of phytoextraction as an effective remediation alternative under the current conditions, with regard to amendments used, applied dose (2 mmol/kg −1 soil), application time (presow), plant species (Zea mays), and sediment (calcareous clayey soil) under study.

The objective of this study was to characterise pollution with heavy metals in surface soils sampled at various dredged sediment disposal sites in the Flemish region (Belgium). The sites selected varied in the period since sediment disposal ceased and in current vegetation and land use. Total metal contents (Cd, Co, Cu, Fe, Mn, Ni, Pb, and Zn) in the surface soils varied widely. For some disposal sites Cd and Zn concentrations greatly exceeded reference values for clean soil. The distribution of the metals as determined by sequential extraction differed between elements, but was simular for all the soils. This suggested that metals in these sediment derived surface soils were accumulated and transformed in a similar way. Residual fractions were low compared to total contents (2 - 4% for Cd, 25% - 35% for Co, 7 - 18% for Mn, 4 - 22% for Zn, 12 - 41% for Ni, 11 - 42% for Pb, 20 - 45% for Cu, < 10% for Zn). High metal concentrations in the acid-extractable and reducible fractions may indicate pollution from anthropogenic sources. DTPA-extractable metals, which may be considered indicative of plant-available contents, were relatively high compared to the total contents. The relative extractability, expressed as the ratio of DTPA-extractable to total contents, decreased in the order Cd (38%) > Cu (28%) = Zn (26%) > Pb (13%) > Ni (10%) > Co (3%). Most of the sites studied would be of concern if they were used for agricultural activities. No trends in metal availability in the period following disposal were apparent from the data.

Water soluble and/or dissolved metals represent the most ecotoxicologically relevant fraction of metals in the environment. However, water extractions may be prone to errors. This study aims to evaluate the performance of 5 filters as well as Rhizon soil moisture samplers, with respect to metal adsorption and/or release by the filter. In addition, the effect of equilibration time on water extractions of different types of soils was evaluated (silty loam, silty clay loam, loamy sand). Filtrations of synthetic solutions containing 40 μg 1^sup -1^ Zn, 20 μg 1^sup -1^ Cu, Ni and Pb, 10 μg 1^sup -1^ Cr and 2 μg 1^sup -1^ Cd were conducted using the different filters. The synthetic solutions either contained (i) no other competitive cations (Ca, Mg, Na, K, Fe, Mn, Al) (A ^sub 1^), (ii) competitive cations at concentrations similar to those observed in soil solutions (A ^sub 2^), (iii) competitive cations at 10 times lower concentrations than those in the synthetic soil solution (A ^sub 3^). Whiteband filters were observed to retain considerable amounts of trace metals (except Cr), both in the presence and absence of other competitive cations. Millipore filters did not exhibit metal retention. Rhizon soil moisture samplers did not retain trace metals from the synthetic soil solution (A ^sub 2^), whereas at lower concentrations of competitive cations (A ^sub 1^, A ^sub 3^) retention of Cu and Pb was observed. Whiteband filters without a predefined pore diameter allowed colloidal material of unknown particle size to pass into the filtrate, making interpretation of results very difficult and comparison between studies using different filters impossible. Millipore filters with a predefined pore diameter are to be recommended for this purpose. However, particular attention must be paid to potential constitutive Zn release by the sintered glass filter holders, the effect of which can be reduced by rigorous acid washing prior to and following every use. Rhizon samplers were also considered to be useful tools with well-defined and sufficiently small pore diameters to withhold colloidal material. However, in the absence or at reduced concentrations of competitive cations (A ^sub 1^, A ^sub 3^) retention of trace metals by the Rhizons, particularly Cu and Pb, was observed. Finally, short equilibration times may be insufficient for full assessment of the water extractable pool of trace metals in the soil.[PUBLICATION ABSTRACT]

Since 2003, the pig industry in Flanders (Belgium) is obliged to process a portion of the nutrient overproduction. In general, pig manure processing occurs as follows: i) separation into liquid and solid fractions, ii) conversion of the solid fraction to an exportable product (e.g. composting) and iii) reduction of nutrient contents in the liquid fraction before discharge into surface water or spreading on arable land. The aim of this study was to evaluate the potential of constructed wetlands (CWs) planted with Phragmites australis to reduce nitrogen (N), phosphorus (P) and chemical oxygen demand (COD) in the liquid fraction to levels below discharge criteria. In addition, the removal efficiency of heavy metals (Cu, Zn) present at elevated levels in the liquid fraction was evaluated. A greenhouse experiment was conducted with subsurface flow (SSF) reed beds (2 × 0.125 × 0.11 m) filled with sand, loam, clayey sand or expanded clay (argex). The liquid manure load was set at 1 mm per day. Removal efficiencies varied between 64-75% for COD, 73-83% for N and 71-92% for P, depending on the matrix material used. However, effluent levels still remained significantly above the Flemish legal discharge criteria of 2 mgl^sup -1^, 15 mgl^sup -1^ and 125 mgl^sup -1^ for P, N and COD respectively.[PUBLICATION ABSTRACT]

Heavy metals in dredged sediment disposal sites may be transported through runoff and percolation. In the present study metal fluxes by runoff and percolation were determined under simulated rainfall at a slope of 19% and a rainfall intensity of approximately 40 mm h super(-1). These circumstances correspond to half the mean annual erosivity of rain under Belgian weather conditions. Surface runoff and percolating water samples were analysed for suspended solids, total dissolved carbon and Cd, Cr, Cu, Ni, Pb and Zn.Runoff rate and sediment yields were highest for asilt loam sediment, characterised by a low clay andorganic matter content. Metal concentrations in runoff and percolating water varied widely between these diments studied and were related to the total metal content in the sediment. In runoff and percolating water from the contaminated sediments, metal concentrations strongly exceeded the Netherlands Areference values for ground water quality. Very high metal fluxes were observed for the recently oxidised dredged sediment. Metal transport per unit surface area through percolating water was from two to more than twenty times greater than that in surface runoff.

A model was developed that allowed for the evaluation of a soil metal cleaning technique in a rapid and cost effective manner. Metal flow (Pb, Cu, Zn, and Cd) during a counter-current soil-acid extraction procedure, consisting of a decarbonation, solubilisation, and washing step, was determined. Required input data are total soil metal content and metal equilibrium distribution coefficients, derived from batch equilibration experiments. The model was calibrated and validated against experimentally obtained results. Model predictions adequately described metal behaviour and removal in each of the extraction steps. Based on the results, optimum operating conditions for the steps involved in the extraction procedure were determined and the feasibility of the counter-current extraction procedure for heavy metal removal from a contaminated soil evaluated.

Previous research by the National Contaminant Biomonitoring Program found fish from Manoa Stream, Hawaii, to have the highest concentrations of Pb in the nation. To explore possible source linkages we sampled background (uncontaminated) soil, roadside soil, and road deposited sediment in Manoa watershed and analyzed them for total and extractable concentrations of Al, Co, Cu, Fe, Mn, Ni, Pb, and Zn. Our concentration and enrichment ratio data indicate that Al, Co, Fe, Mn, and Ni were controlled by natural source variations, and Cu, Zn, and particularly Pb were anthropogenically enhanced. Labile Pb concentrations, extracted with either dilute HCl or EDTA, reached a maximum of 3,560 mg/kg compared to background values of <10 mg/kg. Additionally, 25% of the 169 contaminated samples analyzed had EDTA-extractable Pb enrichment ratios > or =11.5, where a value of 1 separates uncontaminated from contaminated media. Given the proximity of most samples to roadways it is reasonable to conclude that automotive emissions plus vehicle wear were the primary contributors of trace metals to the roadside system. These data are discussed in context with previous work on the fluvial bed sediments in this watershed in an attempt to examine the potential linkage with the biological accumulation of Pb in fish from Manoa watershed.

An experiment was set up to assess the factors affecting metal mobility in five wetland soils of the Scheldt estuary at different sampling depths when subjecting the soils to various water table levels. Pore water metal concentrations were monitored for 10 months at four sampling depths (10, 30, 60 and 90 cm) upon adjusting the water table level to 0, 40 and 80 cm below the surface of the soils. Nickel (Ni) release is facilitated by reductive conditions. These reductive conditions mainly occur below the water table. The fate of chromium (Cr) under reductive conditions seems to be promoted by the presence of dissolved organic matter. However, Cr fate seems to be inconsistent between the soils, as it is affected by a series of counteracting mechanisms. Copper (Cu), zinc (Zn) and especially cadmium (Cd) are all primarily released above the water table under high salinity conditions. These elements are also released below or just above the water table when organic matter is being decomposed, resulting in calcium (Ca), manganese (Mn), Ni and/or iron (Fe) release upon CO₂ accumulation and Fe/Mn oxide reduction, without being accompanied by sulphide production. Their mobility is low under reducing conditions, i.e. in the presence of sulphides, whereas the complexation by soluble organic matter especially seems to promote Cu mobility.

High biomass producing plant species, such as Helianthus annuus, have potential for removing large amounts of trace metals by harvesting the aboveground biomass if sufficient metal concentrations in their biomass can be achieved. However, the low bioavailability of heavy metals in soils and the limited translocation of heavy metals to the shoots by most high biomass producing plant species limit the efficiency of the phytoextraction process. Amendment of a contaminated soil with ethylene diamine tetraacetic acid (EDTA) or citric acid increases soluble heavy metal concentrations, potentially rendering them more available for plant uptake. This article discusses the effects of EDTA and citric acid on the uptake of heavy metals and translocation to aboveground harvestable plant parts in Helianthus annuus. EDTA was included in the research for comparison purposes in our quest for less persistent alternatives, suitable for enhanced phytoextraction. Plants were grown in a calcareous soil moderately contaminated with Cu, Pb, Zn, and Cd and treated with increasing concentrations of EDTA (0.1, 1, 3, 5, 7, and 10 mmol kg −1 soil) or citric acid (0.01, 0.05, 0.25, 0.442, and 0.5 mol kg −1 soil). Heavy metal concentrations in harvested shoots increased with EDTA concentration but the actual amount of phytoextracted heavy metals decreased at high EDTA concentrations, due to severe growth depression. Helianthus annuus suffered heavy metal stress due to the significantly increased bioavailable metal fraction in the soil. The rapid mineralization of citric acid and the high buffering capacity of the soil made citric acid inefficient in increasing the phytoextracted amounts of heavy metals. Treatments that did not exceed the buffering capacity of the soil (<0.442 mol kg −1 soil) did not result in any significant increase in shoot heavy metal concentrations. Treatments with high concentrations resulted in a dissolution of the carbonates and compaction of the soil. These physicochemical changes caused growth depression of Helianthus annuus. EDTA and citric acid added before sowing of Helianthus annuus did not appear to be efficient amendments when phytoextraction of heavy metals from calcareous soils is considered.