Potential of thermal treatment for decontamination of mercury containing wastes from chlor-alkali industry.

Old dumps of mercury waste sludges from chlor-alkaline industry are an environmental threat if not properly secured. Thermal retortion can be used to remove mercury from such wastes. This treatment reduces the total mercury content, and also may reduce the leachability of the residual mercury. The effects of treatment temperature and treatment time on both residual mercury levels and mercury leachability according to the US EPA TCLP leaching procedure, were investigated. Treatment for 1h at 800°C allowed to quantitatively remove the mercury. Treatment at 400°C and above allowed to decrease the leachable Hg contents to below the US EPA regulations. The ultimate choice of treatment conditions will depend on requirements of further handling options and cost considerations.

Presence and mobility of arsenic in estuarine wetland soils of the Scheldt estuary (Belgium).

We aimed to assess the presence and availability of arsenic (As) in intertidal marshes of the Scheldt estuary. Arsenic content was determined in soils sampled at 4 sampling depths in 11 marshes, together with other physicochemical characteristics. Subsequently, a greenhouse experiment was set up in which pore water arsenic (As) concentrations were measured 4 times in a 298-day period in 4 marsh soils at different sampling depths (10, 30, 60 and 90 cm) upon adjusting the water table level to 0, 40 and 80 cm below the surface of these soils. The As content in the soil varied significantly with sampling depth and location. Clay and organic matter seem to promote As accumulation in the upper soil layer (0-20 cm below the surface), whereas sulfide precipitation plays a significant role at higher sampling depths (20-100 cm below the surface). The As concentrations in the pore water of the greenhouse experiment often significantly exceeded the Flemish soil sanitation thresholds for groundwater. There were indications that As release is not only affected by the reductive dissolution of Fe/Mn oxides, but also by e.g. a direct reduction of As(V) to As(III). Below the water table, sulfide precipitation seems to lower As mobility when reducing conditions have been sufficiently established. Above the water table, sulfates and bicarbonates induce As release from the solid soil phase to the pore water.

Spatial distribution of arsenic in the intertidal sediments of River Scheldt, Belgium.

A study was carried out to assess the spatial distribution of arsenic in the intertidal sediments of the River Scheldt in Belgium. Sediment samples were collected from different locations along the River Scheldt up to 100 cm depth and analysed for the major physicochemical properties. The study reveals that the arsenic contents in the sediment samples vary in a wide range, from 2.3 to 140.2 mg kg(-1) dry weight. Moreover, the arsenic concentrations are generally below the background concentrations and remediation thresholds of arsenic in Flanders, Belgium. The occurrence of arsenic is found closely related to some physicochemical properties of the sediments. Arsenic has a strong positive correlation with organic matter and clay contents. On the contrary, a negative correlation exists between arsenic, sand and pH. It is recommended to develop and use organic matter control practices for lowering further accumulation of arsenic within the sediments.

Chemically assisted phytoextraction: a review of potential soil amendments for increasing plant uptake of heavy metals.

The contamination of soils by trace metals has been an unfortunate sideeffect of industrialization. Some of these contaminants can interfere with vulnerable enduses of soil, such as agriculture or nature, already at relatively low levels of contamination. Reversely, conventional civil-technical soil-remediation techniques are too expensive to remediate extended areas of moderately contaminated soil. Phytoextraction has been proposed as a more economic complementary approach to deal with this specific niche of soil contamination. However, phytoextraction has been shown to be a slow-working process due to the low amounts of metals that can be annually removed from the soil under normal agronomic conditions. Therefore, extensive research has been conducted on process optimization by means of chemically improving plant availability and the uptake of heavy metals. A wide range of potential amendments has been proposed in the literature, with considerable attention being spent on aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA). However, these compounds have received increasing criticism due to their environmental persistence and associated risks for leaching. This review presents an overview of potential soil amendments that can be employed for enhancing metal uptake by phytoextraction crops, with a distinct focus on more degradable alternatives to persistent compounds such as EDTA.

Degradability of ethylenediaminedisuccinic acid (EDDS) in metal contaminated soils: implications for its use soil remediation.

Previous research has identified ethylenediaminedisuccinate (EDDS) as a promising biodegradable alternative for persistent compounds such as EDTA for application in soil washing or enhanced phytoextraction of heavy metals. This study examines heavy metal mobilization in three polluted soils varying in soil composition, with specific attention for competitive behaviour for complexation between the various metals and major elements, such as Al, Fe, Mn, Ca and Mg. In addition, amendment biodegradability was compared between the different soil types. The selected soils included a moderately contaminated calcareous clayey soil, a dredged sediment derived surface soil with similar soil characteristics yet more heavily polluted with Cd, Cr and Zn, and a sandy soil moderately contaminated by historical smelter activity (atmospheric deposition). Biodegradability of EDDS in the three soils varied distinctly. This was mainly expressed in the duration of the lag phase prior to metal complex degradation, and not so much in the half life when degradation effectively did set in. Differences in the lag phase were attributed to differences in soil pollution. However, EDDS was fully degraded within a period of 54 d in all soils regardless of initial delay. Assessment of the cation mobilisation patterns in the three soils under study revealed that mainly Ca, Fe and Al can reduce effectiveness of heavy metal mobilisation by competition for complexation.

Effects of sorption, sulphate reduction, and Phragmites australis on the removal of heavy metals in subsurface flow constructed wetland microcosms.

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, 2,000mg 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 approximately -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.

Influence of hydrological regime on pore water metal concentrations in a contaminated sediment-derived soil.

Options for wetland creation or restoration might be limited because of the presence of contaminants in the soil. The influence of hydrological management on the pore water concentrations of Cd, Cr, Cu, Fe, Mn, Ni and Zn in the upper soil layer of a contaminated overbank sedimentation zone was investigated in a greenhouse experiment. Flooding conditions led to increased Fe, Mn, Ni and Cr concentrations and decreased Cd, Cu and Zn concentrations in the pore water of the upper soil layer. Keeping the soil at field capacity resulted in a low pore water concentration of Fe, Mn and Ni while the Cd, Cu, Cr and Zn concentrations increased. Alternating hydrological conditions caused metal concentrations in the pore water to fluctuate. Formation and re-oxidation of small amounts of sulphides appeared dominant in determining the mobility of Cd, Cu, and to a lesser extent Zn, while Ni behaviour was consistent with Fe/Mn oxidation and reduction. These effects were strongly dependent on the duration of the flooded periods. The shorter the flooded periods, the better the metal concentrations could be linked to the mobility of Ca in the pore water, which is attributed to a fluctuating CO(2) pressure.

Enhanced phytoextraction: I. Effect of EDTA and citric acid on heavy metal mobility in a calcareous soil.

Phytoextraction, the use of plants to extract heavy metals from contaminated soils, could be an interesting alternative to conventional remediation technologies. However, calcareous soils with relatively high total metal contents are difficult to phytoremediate due to low soluble metal concentrations. Soil amendments such as ethylene diaminetetraacetate (EDTA) have been suggested to increase heavy metal bioavailability and uptake in aboveground plant parts. Strong persistence of EDTA and risks of leaching of potentially toxic metals and essential nutrients have led to research on easily biodegradable soil amendments such as citric acid. In our research, EDTA is regarded as a scientific benchmark with which degradable alternatives are compared for enhanced phytoextraction purposes. The effects of increasing doses of EDTA (0.1,1,10 mmol kg(-1) dry soil) and citric acid (0.01, 0.05, 0.25, 0.442, 0.5 mol kg(-1) dry soil) on bioavailable fractions of Cu, Zn, Cd, and Pb were assessed in one part of our study and results are presented in this article. The evolution of labile soil fractions of heavy metals over time was evaluated using water paste saturation extraction (approximately soluble fraction), extraction with 1 M NH4OAc at pH 7 (approximately exchangeable fraction), and extraction with 0.5 M NH4OAc + 05 M HOAc + 0.02 M EDTA at pH 4.65 (approximately potentially bioavailable fraction). Both citric acid and EDTA produced a rapid initial increase in labile heavy metal fractions. Metal mobilization remained constant in time for soils treated with EDTA, but a strong exponential decrease of labile metal fractions was noted for soils treated with citric acid. The half life of heavy metal mobilization by citric acid varied between 1.5 and 5.7 d. In the following article, the effect of heavy metal mobilization on uptake by Helianthus annuus will be presented.

Enhanced phytoextraction: II. Effect of EDTA and citric acid on heavy metal uptake by Helianthus annuus from a calcareous soil.

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.

Enhanced phytoextraction: in search of EDTA alternatives.

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 NH4 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 NH4 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.

Short- and longer-term effects of the willow root system on metal extractability in contaminated dredged sediment.

Willow (Salix spp.) stands are often proposed as vegetation covers for the restoration and stabilization of contaminated and derelict land. Planting willows on dredged sediment disposal sites for biomass production can be an alternative to traditional capping techniques. However, with the introduction of willow stands on dredged sediment disposal sites, the possibility of increased contaminant availability in the root zone must be acknowledged as it can increase the risk of leaching. Two trials investigated the availability of Cd, Zn, Cu, and Pb in the root zones of willows grown on contaminated sediment. To assess the effects of willow root growth on metal extractability and mobility, bulk and rhizosphere sediment samples were extracted with deionized water, ammonium acetate at pH 7, and ammonium acetate-EDTA at pH 4.65. A rhizobox experiment was used to investigate the short-term effect of willow roots on metal availability in oxic and anoxic sediment. Longer-term effects were assessed in a field trial. The rhizobox trial showed that Cd, Zn, and Cu extractability in the rhizosphere increased while the opposite was observed for Pb. This was attributed to the increased willow-induced oxidation rate in the root zone as a result of aeration and evapotranspiration, which masked the direct chemical and biological influences of the willow roots. The field trial showed that Cu and Pb, but not Cd, were more available in the root zone after water and ammonium acetate (pH 7) extraction compared with the bulk sediment. Sediment in the root zone was better structured and aggregated and thus more permeable for downward water flows, causing leaching of a fraction of the metals and significantly lower total contents of Cd, Cu, and Pb. These findings indicate that a vegetation cover strategy to stabilize sediments can increase metal availability in the root zone and that potential metal losses to the environment should be considered.

Characterisation of Malian and Belgian solid waste composts with respect to fertility and suitability for land application.

Two composts, a Malian (C1) and a Belgian (C2), and a peat substrate (C3) were analyzed for their suitability for land application. The results revealed that the materials can be used in agriculture but only the application of the peat substrate may create N immobilization. Composts had higher P, Ca, and Mg contents and lower C and K contents and C/N ratio than the peat substrate. The available P extracted from the three materials ranged from 15% (for C2) to 48% (for C3) and available K from 36% (in the composts) to 48% (for C3) of the total elements respectively. The fractionation of Mn, Fe, Zn and Cu in operationally defined fractions (water soluble, exchangeable, complexed, organically bound and residual) allows an estimation of the availability of metals for uptake. For example, 16% of the total Mn in the composts (C1 and C2) and 22% in the peat substrate would be plant available. Available Fe in the three materials was less than 2%. Available Zn varied between 10 and 25%. The fractionation allowed an estimation of the potential for contamination of groundwater following the applications of composts to agricultural lands.

Effects of a municipal solid waste compost and mineral fertilization on plant growth in two tropical agricultural soils of Mali.

A pot experiment was conducted to compare the effects of compost and mineral fertilization on the growth and chemical composition of ryegrass (Lolium perenne L.) in two Malian agricultural soils (Baguinéda, abbreviated as Bgda, 12 degrees 23' S, 7 degrees 45' W and Gao. 16 degrees 18' N, 0 degrees GM). Treatments included: control, NPK alone, NPK + C25, NPK + C50, NPK + C100, PK + C50, NK + C50, NP + C50, K + C50, P + C50, N + C50 and C50 alone, where NPK represents the non-modified Hoagland's solution (corresponding to 271, 95 and 172 kg/ha of N, P and K respectively) and C25, C50 and C100 the different rates (25, 50 and 100 T/ha) of compost. Compost and mineral fertilization significantly increased dry matter production. The application of 50 T/ha of compost alone increased the dry matter yield by 10% and 17.5% while mineral NPK alone, by 69.7% and 65% for Gao and Bgda soils, respectively. The combination of compost and mineral NPK (NPK + C25 for Gao and NPK + C50 for Bgda) showed the highest crop yields.

Effect of wood ash application on soil solution chemistry of tropical acid soils: incubation study.

The objective of this study was to determine the effect of wood ash application on soil solution composition of three tropical acid soils. Calcium carbonate was used as a reference amendment. Amended soils and control were incubated for 60 days. To assess soluble nutrients, saturation extracts were analysed at 15 days intervals. Wood ash application affects the soil solution chemistry in two ways, as a liming agent and as a supplier of nutrients. As a liming agent, wood ash application induced increases in soil solution pH, Ca, Mg, inorganic C, SO4 and DOC. As a supplier of elements, the increase in the soil solution pH was partly due to ligand exchange between wood ash SO4 and OH- ions. Large increases in concentrations of inorganic C, SO4, Ca and Mg with wood ash relative to lime and especially increases in K reflected the supply of these elements by wood ash. Wood ash application could represent increased availability of nutrients for the plant. However, large concentrations of basic cations, SO4 and NO3 obtained with higher application rates could be a concern because of potential solute transport to surface waters and groundwater. Wood ash must be applied at reasonable rates to avoid any risk for the environment.

Chemical characteristics of Malian and Belgian solid waste composts.

Two composts, a Malian (C1) and a Belgian (C2), and a peat substrate (C3) were analyzed for their suitability for land application. The results revealed that the materials can be used in agriculture but only the composts can supply all macro-nutrients necessary for plant growth. The fractionation of Mn, Fe, Zn and Cu in operationally defined fractions (water soluble, exchangeable, complexed, organically bound and residual) allows estimation of the availability of metals for uptake. For example, 16% of the total Mn in the composts (C1 and C2) and 22% in the peat substrate would be plant available. Available Fe in the three materials was less than 2%. Available Zn varied from 10% to 25%. The fractionation also allowed estimation of the potential for contamination of groundwater following the applications of composts to agricultural lands.

Metal extraction from road sediment using different strength reagents: impact on anthropogenic contaminant signals.

Washoff of road deposited sediment into storm drain systems is one of the major contributors to nonpoint source pollution in urban fluvial networks. These sediments contain a variety of potentially toxic organic and inorganic contaminants. Road sediment from 13 locations in an urban (non-industrialized) drainage basin, and soil from 10 background (control) locations were collected to assess total and labile fractions of Al, Co, Cu, Fe, Mn, Ni, Pb and Zn. Four digestions, of varying strength, were used to assess contaminant levels, these included: a total four-acid digestion, a microwave-assisted digestion with concentrated nitric acid (USEPA Method 3051), a 0.5 M 'cold' HCl, and a 0.05 M EDTA (pH 7). Road sediment data indicate that Al, Co, Fe, Mn and Ni were primarily lithogenic in origin, while Cu, Pb and Zn showed very significant anthropogenic signals, most probably from vehicle-related sources. Median Pb concentration enrichment ratios for the EDTA extraction were about 42, indicating an extreme anthropogenic signal. The weak extractants (HCI and EDTA) are considered in this study to be superior in their ability to characterize the degree of anthropogenic contamination and should be utilized more widely in environmental contaminant studies.

Mercury contamination in freshwater, estuarine, and marine fishes in relation to small-scale gold mining in Suriname, South America.

The extent of mercury contamination in Surinamese food fishes due to small-scale gold mining was investigated by determination of the total mercury concentration in 318 freshwater fishes, 109 estuarine fishes, and 110 fishes from the Atlantic Ocean. High background levels were found in the piranha Serrasalmus rhombeus (0.35 microg Hg x g(-1) muscle tissue, wet mass basis) and the peacock cichlid Cichla ocellaris (0.39 microg x g(-1)) from the Central Suriname Nature Reserve. Average mercury levels in freshwater fishes were higher in piscivorous species than in nonpiscivorous species, both in potentially contaminated water bodies (0.71 and 0.19 microg x g(-1), respectively) and in the control site (0.25 and 0.04 microg x g(-1), respectively). Mercury concentrations in piscivorous freshwater fishes were significantly higher in rivers potentially affected by gold mining than in the control site. In 57% of 269 piscivorous freshwater fishes from potentially contaminated sites, mercury levels exceeded the maximum permissible concentration of 0.5 microg Hg x g(-1). The highest mercury concentrations (3.13 and 4.26 microg x g(-1)) were found in two piranhas S. rhombeus from the hydroelectric reservoir Lake Brokopondo. The high mercury levels in fishes from Lake Brokopondo were to some extent related to gold mining because fishes collected at eastern sites (i.e., close to the gold fields) showed significantly higher mercury concentrations than fishes from western localities. In the estuaries, mercury levels in ariid catfish (0.22 microg x g(-1)) and croakers (0.04-0.33 microg x g(-1)) were distinctly lower than those in piscivorous fishes from contaminated freshwater sites. In the isolated Bigi Pan Lagoon, the piscivores snook Centropomus undecimalis (0.04 microg x g(-1)) and tarpon Megalops atlanticus (0.03 microg x g(-1)) showed low mercury levels. Mercury levels were significantly higher in marine fishes than in estuarine fishes, even with the Bigi Pan fishes excluded. High mercury concentrations were found in the shark Mustelus higmani (0.71 microg x g(-1)), the crevalle jack Caranx hippos (1.17 microg x g(-1)), and the barracuda Sphyraena guachancho (0.39 microg x g(-1)), but also in nonpiscivorous species such as Calamus bajonado (0.54 microg x g(-1)), Haemulon plumieri (0.47 microg x g(-1)), and Isopisthus parvipinnis (0.48 microg x g(-1)). Mercury levels were positively correlated with the length of the fish in populations of the freshwater piscivores S. rhombeus, Hoplias malabaricus, and Plagioscion squamosissimus, in estuarine species (Arius couma, Cynoscion virescens, and Macrodon ancylodon), and in S. guachancho from the Atlantic Ocean.

Characteristics of wood ash and influence on soil properties and nutrient uptake: an overview.

Wood industries and power plants generate enormous quantities of wood ash. Disposal in landfills has been for long a common method for removal. New regulations for conserving the environment have raised the costs of landfill disposal and added to the difficulties for acquiring new sites for disposal. Over a few decades a number of studies have been carried out on the utilization of wood ashes in agriculture and forestry as an alternative method for disposal. Because of their properties and their influence on soil chemistry the utilization of wood ashes is particularly suited for the fertility management of tropical acid soils and forest soils. This review principally focuses on ash from the wood industry and power plants and considers its physical, chemical and mineralogical characteristics, its effect on soil properties, on the availability of nutrient elements and on the growth and chemical composition of crops and trees, as well as its impact on the environment.

Guidelines for sampling in Flanders (Belgium).

In Flanders, sampling guidelines for investigations on contamination of soils are in development. One detailed sampling guideline is currently available with respect to the prospective investigation in the frame of the decree related to soil sanitation. Four strategies for sampling may be followed as a function of available information about pollution sources. Guidelines indicate what has to be sampled (top soil, deeper soil, soil water), how sampling points must be determined, how the number of samples and analyses is determined and what parameters need to be analysed. The example given shows that sampling guidelines will strongly depend on the ultimate goal of a particular sampling. A sampling procedure should be developed with close consideration of practical aspects and limitations, in order to be practical, realistic and cost-effective.