Metal sorption by biochars: A trade-off between phosphate and carbonate concentration as governed by pyrolysis conditions.

Three feedstocks, pine wood, grass and cow manure, were pyrolyzed under various conditions and tested on their ability to sorb metals in aquatic systems. The feedstocks were pyrolyzed at 2 different temperatures (350 °C and 550 °C) and 2 different residence times (10 and 60 min) and resulting biochars were assessed on their capability to immobilize Pb, Cu, Cd and Zn. Manure-based chars, and to a lesser extent grass-based chars, featured high concentrations of phosphates and carbonates. These anions play an important role in metal sorption because they form insoluble complexes with the metals. Washing reduced the concentration of these anions, leading to a reduced sorption of metals by the biochar. The carbonate concentration on the biochars' surface increased at higher reactor temperature and longer residence times. The opposite trend was observed for the phosphate concentration and the cation exchange capacity. Accordingly, the optimal temperature-residence time combination for sorption was a trade-off between these properties. Biochar produced from cow manure and pyrolyzed at 550 °C for 10 min showed the best sorption for all metals considered.

Cadmium phytoremediation potential of Brassica crop species: A review.

Cadmium (Cd) is a highly toxic metal released into the environment through anthropogenic activities. Phytoremediation is a green technology used for the stabilization or remediation of Cd-contaminated soils. Brassica crop species can produce high biomass under a range of climatic and growing conditions, allowing for considerable uptake and accumulation of Cd, depending on species. These crop species can tolerate Cd stress via different mechanisms, including the stimulation of the antioxidant defense system, chelation, compartmentation of Cd into metabolically inactive parts, and accumulation of total amino-acids and osmoprotectants. A higher Cd-stress level, however, overcomes the defense system and may cause oxidative stress in Brassica species due to overproduction of reactive oxygen species and lipid peroxidation. Therefore, numerous approaches have been followed to decrease Cd toxicity in Brassica species, including selection of Cd-tolerant cultivars, the use of inorganic and organic amendments, exogenous application of soil organisms, and employment of plant-growth regulators. Furthermore, the coupling of genetic engineering with cropping may also help to alleviate Cd toxicity in Brassica species. However, several field studies demonstrated contrasting results. This review suggests that the combination of Cd-tolerant Brassica cultivars and the application of soil amendments, along with proper agricultural practices, may be the most efficient means of the soil Cd phytoattenuation. Breeding and selection of Cd-tolerant species, as well as species with higher biomass production, might be needed in the future when aiming to use Brassica species for phytoremediation.

Impact of organic amendments (biochar, compost and peat) on Cd and Zn mobility and solubility in contaminated soil of the Campine region after three years.

To determine the long-term impact of organic amendments on metal (Cd and Zn) immobilization, soil from the Campine region was amended with holm oak-derived biochar, compost, and peat, and monitored over a 3-year period. Pot experiments were conducted by mixing the amendments independently at 2% and 4% (g/g) with the soil. The mobility and solubility of metals in the treatments were assessed by means of rhizon soil moisture samplers, sequential BCR extractions, and diffusive gradient in thin films (DGT). Over the three-year period, the 2% biochar addition resulted in an average decrease in pore water concentration of 40% for Cd and 48% for Zn whereas the 4% addition led to an average decrease of 66% for Cd and 77% for Zn. The immobilization effect in the biochar treatments was attributed to the consistently higher pH and lower concentrations of dissolved organic carbon (DOC) in the soil. The latter may have been caused by sorption of DOC onto the surface of biochar thereby increasing its negatively charged functional groups that are able to sorb cations. On the other hand, compost and peat had the unwanted effect of significantly increasing the concentrations of Cd and Zn in the soil pore water. This was partly due to the formation of soluble organo-metallic complexes as significantly higher DOC concentrations were found in the compost and peat treatments. Results from the DGT measurements, after a 24 h deployment time, revealed a low resupply (R ≤ 0.4) of Cd and Zn from the solid phase to the soil solution in both amended and unamended soil. This suggests a case of slow metal desorption kinetics in the soil that was relatively unchanged by the presence of organic amendments.

Limitations for phytoextraction management on metal-polluted soils with poplar short rotation coppice-evidence from a 6-year field trial.

Poplar clones were studied for their phytoextraction capacity in the second growth cycle (6-year growth) on a site in the Belgian Campine region, which is contaminated with Cd and Zn via historic atmospheric deposition of nearby zinc smelter activities. The field trial revealed regrowth problems for some clones that could not be predicted in the first growth cycle. Four allometric relations were assessed for their capacity to predict biomass yield in the second growth cycle. A power function based on the shoot diameter best estimates the biomass production of poplar with R2 values between 0.94 and 0.98. The woody biomass yield ranged from 2.1 to 4.8 ton woody Dry Mass (DM) ha-1 y-1. The primary goal was to reduce soil concentrations of metals caused by phytoextraction. Nevertheless, increased metal concentrations were determined in the topsoil. This increase can partially be explained by the input of metals from deeper soil layers in the top soil through litterfall. The phytoextraction option with poplar short rotation coppice in this setup did not lead to the intended soil remediation in a reasonable time span. Therefore, harvest of the leaf biomass is put forward as a crucial part of the strategy for soil remediation through Cd/Zn phytoextraction.

Rapid and irreversible sorption behavior of 7Be assessed to evaluate its use as a catchment sediment tracer.

Beryllium-7 (7Be) has been used as a sediment tracer to evaluate soil redistribution rates at hillslopes and as a tool to estimate sediment residence time in river systems. A key assumption for the use of 7Be as a sediment tracer is the rapid and irreversible sorption of 7Be upon contact with the soil particles. However, recent studies have raised questions about the validity of these assumptions. Seven soil types were selected to assess the adsorption rate of 7Be on the soil particles, subsequently an extraction experiment was performed to assess the rate of desorption. Next, different treatments were applied to assess the impact of soil pH, fertilizer, humic acid and organic matter on the adsorption of Be. Finally, the influence of regularly occurring cations present on the soil complex on the adsorption of Be on pure clay minerals was evaluated. The adsorption rate experiment showed a rapid and nearly complete sorption of Be for Luvisols and Cambisols under agriculture. For a temperate climate Stagnosol under forest and two highly weathered tropical Ferralsols sorption of Be was less rapid and less complete. This may result in an incomplete adsorption of 7Be on these three soils when runoff initiates, which could lead to an overestimation of erosion rates and sediment residence time. Additional observations were made during the extraction experiment, showing a significant loss of Be from the forest Stagnosol and a stable binding of Be to the arable soils. Of the different treatments applied, only pH showed to be of influence. Finally, Ca2+ and NH4+ on the soil complex had only a limited effect on the adsorption of Be, while Al3+ in combination with a low pH inhibits the adsorption of Be on the exchange complex of the pure clay minerals. All these findings more rigorously support the use of 7Be as a soil redistribution tracer in arable soils in a temperate climate at a hillslope scale. The use of 7Be in highly weathered Ferralsols or forest rich environments should be limited to avoid overestimations of erosion rates. The spatially extended use of 7Be to evaluate residence times of sediments should be avoided in catchments with rapid changing environmental parameters as they might influence the sorption behavior of 7Be.

Fertilizer performance of liquid fraction of digestate as synthetic nitrogen substitute in silage maize cultivation for three consecutive years.

Following changes over recent years in fertilizer legislative framework throughout Europe, phosphorus (P) is taking over the role of being the limiting factor in fertilizer application rate of animal manure. This results in less placement area for spreading animal manure. As a consequence, more expensive and energy demanding synthetic fertilizers are required to meet crop nutrient requirements despite existing manure surpluses. Anaerobic digestion followed by mechanical separation of raw digestate, results in liquid fraction (LF) of digestate, a product poor in P but rich in nitrogen (N) and potassium (K). A 3-year field experiment was conducted to evaluate the impact of using the LF of digestate as a (partial) substitute for synthetic N fertilizer. Two different fertilization strategies, the LF of digestate in combination with respectively animal manure and digestate, were compared to the conventional fertilization regime of raw animal manure with synthetic fertilizers. Results from the 3-year trial indicate that the LF of digestate may substitute synthetic N fertilizers without crop yield losses. Through fertilizer use efficiency assessment it was observed that under-fertilization of soils with a high P status could reduce P availability and consequently the potential for P leaching. Under conditions of lower K application, more sodium was taken up by the crop. In arid regions, this effect might reduce the potential risk of salt accumulation that is associated with organic fertilizer application. Finally, economic and ecological benefits were found to be higher when LF of digestate was used as a synthetic N substitute. Future perspectives indicate that nutrient variability in bio-based fertilizers will be one of the greatest challenges to address in the future utilization of these products.

Mild hydrothermal conditioning prior to torrefaction and slow pyrolysis of low-value biomass.

The aim of this research was to establish whether hydrothermal conditioning and subsequent thermochemical processing via batch torrefaction or slow pyrolysis may improve the fuel quality of grass residues. A comparison in terms of fuel quality was made of the direct thermochemical processing of the feedstock versus hydrothermal conditioning as a pretreatment prior to thermochemical processing. Hydrothermal conditioning reduced ash content, and particularly nitrogen, potassium and chlorine contents in the biomass. The removal of volatile organic matter associated with thermochemical processes can increase the HHV to levels of volatile bituminous coal. However, slow pyrolysis only increased the HHV of biomass provided a low ash content (<6%) feedstock was used. In conclusion, hydrothermal conditioning can have a highly positive influence on the efficiency of thermochemical processes for upgrading low-value (high-ash) biomass to a higher quality fuel.

Phosphorus retention capacity in red ferralitic soil.

In this study the main physical-chemical characteristics of red ferralitic soil to use as substrate in subsurface wetlands was determined. The P-removal was evaluated in a short-term isotherm batch experiment and in a column percolation experiment. The acid characteristic and high content of iron minerals in the red ferralitic soil facilitated the phosphorus removal. Also the sorption isotherms at two different temperatures were obtained. The results showed that the sorption capacity increases with an increase in solution temperature from 25 to 35 °C. The experimental data were fitted to Langmuir and Freundlich models, having a better fit to the Freundlich isotherms. The maximum P-sorption capacities estimated using the Langmuir isotherm were 0.96 and 1.13 g/kg at 25 and 35 °C respectively. Moreover a column experiment was carried out at two different flows. Sequential extractions of the phosphorus-saturated soil indicated that phosphorus is mainly bound with iron or aluminum minerals. The results have demonstrated a good potential for red ferralitic soil for phosphorus removal from urban wastewater.

Effect of composting on the Cd, Zn and Mn content and fractionation in feedstock mixtures with wood chips from a short-rotation coppice and bark.

Micronutrient content and availability in composts may be affected by the addition of wood chips or tree bark as a bulking agent in the compost feedstock. In the first part of this study, micronutrient levels were assessed in bark and wood of poplar and willow clones in a short-rotation coppice. Large differences between species were observed in bark concentrations for Cd, Zn and Mn. In the second part of the study, we aimed to determine the effect of feedstock composition and composting on Cd, Zn and Mn concentrations and availability. By means of three composting experiments we examined the effect of (a) bark of different tree species, (b) the amount of bark, and (c) the use of bark versus wood chips. In general, compost characteristics such as pH, organic matter and nutrient content varied due to differences in feedstock mixture and composting process. During the composting process, the availability of Cd, Zn and Mn decreased, although the use of willow and poplar bark or wood chips resulted in elevated total Cd, Zn or Mn concentrations in the compost. Cd concentrations in some composts even exceeded legal criteria. Cd and Zn were mainly bound in the reducible fraction extracted with 0.5M NH2OH⋅HCl. A higher acid-extractable fraction for Mn than for Cd and Zn was found. Higher Cd concentrations in the compost due to the use of bark or wood chips did not result in higher risk of Cd leaching. The results of the pH-stat experiment with gradual acidification of composts illustrated that only a strong pH decline in the compost results in higher availability of Cd, Zn and Mn.

Safe use of metal-contaminated agricultural land by cultivation of energy maize (Zea mays).

Production of food crops on trace element-contaminated agricultural lands in the Campine region (Belgium) can be problematic as legal threshold values for safe use of these crops can be exceeded. Conventional sanitation of vast areas is too expensive and alternatives need to be investigated. Zea mays on a trace element-contaminated soil in the region showed an average yield of 53 ± 10 Mg fresh or 20 ± 3 Mg dry biomass ha(-1). Whole plant Cd concentrations complied with legal threshold values for animal feed. Moreover, threshold values for use in anaerobic digestion were met. Biogas production potential did not differ between maize grown on contaminated and non-contaminated soils. Results suggested favorable perspectives for farmers to generate non-food crops profitably, although effective soil cleaning would be very slow. This demonstrates that a valuable and sustainable alternative use can be generated for moderately contaminated soils on which conventional agriculture is impaired.

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.

Economic viability of phytoremediation of a cadmium contaminated agricultural area using energy maize. Part I: effect on the farmer's income.

This paper deals with the economic viability of using energy maize as a phytoremediation crop in a vast agricultural area moderately contaminated with metals. The acceptance of phytoremediation as a remediation technology is, besides the extraction rate, determined by its profitability, being the effects it has on the income of the farmer whose land is contaminated. This income can be supported by producing renewable energy through anaerobic digestion of energy maize, a crop that takes up only relatively low amounts of metals, but that can be valorised as a feedstock for energy production. The effect on the income per hectare of growing energy maize instead of fodder maize seems positive, given the most likely values of variables and while keeping the basic income stable, originating from dairy cattle farming activities. We propose growing energy maize aiming at risk-reduction, and generating an alternative income for farmers, yet in the long run also generating a gradual reduction of the pollution levels. In this way, remediation is demoted to a secondary objective with sustainable risk-based land use as primary objective.

Arsenic in drinking water wells on the Bolivian high plain: Field monitoring and effect of salinity on removal efficiency of iron-oxides-containing filters.

In the rural areas around Oruro (Bolivia), untreated groundwater is used directly as drinking water. This research aimed to evaluate the general drinking water quality, with focus on arsenic (As) concentrations, based on analysis of 67 samples from about 16 communities of the Oruro district. Subsequently a filter using Iron Oxide Coated Sand (IOCS) and a filter using a Composite Iron Matrix (CIM) were tested for their arsenic removal capacity using synthetic water mimicking real groundwater. Heavy metal concentrations in the sampled drinking water barely exceeded WHO guidelines. Arsenic concentrations reached values up to 964 µ g L⁻¹ and exceeded the current WHO provisional guideline value of 10 µ g L⁻¹ in more than 50% of the sampled wells. The WHO guideline of 250 mg L⁻¹ for chloride and sulphate was also exceeded in more than a third of the samples, indicating high salinity in the drinking waters. Synthetic drinking water could be treated effectively by the IOCS- and CIM-based filters reducing As to concentrations lower than 10 µ g L⁻¹. High levels of chloride and sulphate did not influence As removal efficiency. However, phosphate concentrations in the range from 4 to 24 mg L⁻¹ drastically decreased removal efficiency of the IOCS-based filter but had no effects on removal efficiency of the CIM-based filter. Results of this study can be used as a base for further testing and practical implementation of drinking water purification in the Oruro region.

Chemically enhanced phytoextraction of Pb by wheat in texturally different soils.

A pot study was used to examine the effects of amendments such as EDTA and elemental sulfur on the growth potential, gas exchange features, uptake and mobilization of Pb by wheat (Triticum aestivum L.) in two texturally different contaminated soils at three levels of EDTA (2, 4, 8 mmol kg(-1) dry soil) and two levels of elemental sulfur (100, 200 mmol kg(-1) dry soil). EDTA resulted in more solubilization of Pb than elemental sulfur in both soils. Application of EDTA and elemental sulfur increased shoot dry matter in the loamy sand soil, whereas in the sandy clay loam soil EDTA treated plants produced lower shoot dry matter compared to that observed with elemental sulfur. Application of EDTA 10d prior to harvest increased the amount of Pb accumulated into wheat shoots with more Pb accumulated by plants from the loamy sand than from the sandy clay loam soil. However, evaluation of the relative extraction efficiency expressed as the percentage of solubilized Pb that is subsequently also effectively accumulated by the plant shoots reveals that the relatively low efficiency does not warrant the massive mobilization induced by the environmentally persistent EDTA chelator. More modest mobilization of Pb induced by elemental sulfur and the higher relative extraction of mobilized Pb therefore deserves further attention in future research. In particular, attention needs to be paid to determining soil types in which elemental sulfur can induce significant impact on soil pH and metal mobility after application of a practically realistic dosage.

Hydrological regime and salinity alter the bioavailability of Cu and Zn in wetlands.

In the context of the European Water Framework Directive, controlled flooding of lowlands is considered as a potential water management strategy to minimise the risk of flooding of inhabited areas. However, due to historical pollution and overbank sedimentation, metal levels are elevated in most wetlands, which can cause adverse effects on the ecosystem's dynamics. Additionally, salinity affects the bioavailability of metals present or imported into these systems. The effect of different flooding regimes and salinity exposure scenarios (fresh- and brackish water conditions) on Cu and Zn accumulation in the oligochaete Tubifex tubifex (Müller, 1774) was examined. Metal mobility was closely linked to redox potential, which is directly related to the prevalent hydrological regime. Flooded, and thus more reduced, conditions minimized the availability of metals, while oxidation of the substrates during a drier period was associated with a rapid increase of metal availability and accumulation in the oligochaetes.

The use of bio-energy crops (Zea mays) for 'phytoattenuation' of heavy metals on moderately contaminated soils: a field experiment.

Worldwide there are numerous regions where conventional agriculture is affected by the presence of elevated amounts of plant-available trace elements, causing economic losses and food and feed quality and safety. The Belgian and Dutch Campine regions are a first-class example, with approximately 700 km(2) diffusely contaminated by historic atmospheric deposition of Cd, Zn and Pb. Primary land use in this region is agriculture, which is frequently confronted with crops exceeding the European standards for heavy metal contents in food and feed-stuffs. Phytoremediation as a soil remediation technology only appears feasible if the produced biomass might be valorised in some manner. In the current case, we propose the use of energy maize aiming at risk-reduction and generation of an alternative income for agriculture, yet in the long run also a gradual reduction of the pollution levels. Since the remediation aspect is demoted to a secondary objective with sustainable risk-based land use as first objective, we introduce the term 'phytoattenuation': this is in analogy with 'natural attenuation' of organic pollutants in soils where also no direct intended remediation measures but a risk-based management approach is implemented. In the current field experiment, cultivation of energy maize could result in 33,000-46,000 kW h of renewable energy (electrical and thermal) per hectare per year which by substitution of fossil energy would imply a reduction of up to 21 x 10(3)kg ha(-1) y(-1) CO(2) if used to substitute a coal fed power plant. Metal removal is very low for Cd and Pb but more significant for Zn with an annual reduction of 0.4-0.7 mgkg(-1) in the top soil layer.

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.

EDTA-assisted Pb phytoextraction.

Pb is one of the most widespread and metal pollutants in soil. It is generally concentrated in surface layers with only a minor portion of the total metal found in soil solution. Phytoextraction has been proposed as an inexpensive, sustainable, in situ plant-based technology that makes use of natural hyperaccumulators as well as high biomass producing crops to help rehabilitate soils contaminated with heavy metals without destructive effects on soil properties. The success of phytoextraction is determined by the amount of biomass, concentration of heavy metals in plant, and bioavailable fraction of heavy metals in the rooting medium. In general, metal hyperaccumulators are low biomass, slow growing plant species that are highly metal specific. For some metals such as Pb, there are no hyperaccumulator plant species known to date. Although high biomass-yielding non-hyperaccumulator plants lack an inherent ability to accumulate unusual concentrations of Pb, soil application of chelating agents such as EDTA has been proposed to enhance the metal concentration in above-ground harvestable plant parts through enhancing the metal solubility and translocation from roots to shoots. Leaching of metals due to enhanced mobility during EDTA-assisted phytoextraction has been demonstrated as one of the potential hazards associated with this technology. Due to environmental persistence of EDTA in combination with its strong chelating abilities, the scientific community is moving away from the use of EDTA in phytoextraction and is turning to less aggressive alternative strategies such as the use of organic acids or more degradable APCAs (aminopolycarboxylic acids). We have therefore arrived at a point in phytoremediation research history in which we need to distance ourselves from EDTA as a proposed soil amendment within the context of phytoextraction. However, valuable lessons are to be learned from over a decade of EDTA-assisted phytoremediation research when considering the implementation of more degradable alternatives in assisted phytoextraction practices.

Trace metal behaviour in estuarine and riverine floodplain soils and sediments: a review.

This paper reviews the factors affecting trace metal behaviour in estuarine and riverine floodplain soils and sediments. Spatial occurrence of processes affecting metal mobility and availability in floodplains are largely determined by the topography. At the oxic-anoxic interface and in the anoxic layers of floodplain soils, especially redox-sensitive processes occur, which mainly result in the inclusion of metals in precipitates or the dissolution of metal-containing precipitates. Kinetics of these processes are of great importance for these soils as the location of the oxic-anoxic interface is subject to change due to fluctuating water table levels. Other important processes and factors affecting metal mobility in floodplain soils are adsorption/desorption processes, salinity, the presence of organic matter, sulphur and carbonates, pH and plant growth. Many authors report highly significant correlations between cation exchange capacity, clay or organic matter contents and metal contents in floodplain soils. Iron and manganese (hydr)oxides were found to be the main carriers for Cd, Zn and Ni under oxic conditions, whereas the organic fraction was most important for Cu. The mobility and availability of metals in a floodplain soil can be significantly reduced by the formation of metal sulphide precipitates under anoxic conditions. Ascending salinity in the flood water promotes metal desorption from the floodplain soil in the absence of sulphides, hence increases total metal concentrations in the water column. The net effect of the presence of organic matter can either be a decrease or an increase in metal mobility, whereas the presence of carbonates in calcareous floodplain soils or sediments constitutes an effective buffer against a pH decrease. Moreover, carbonates may also directly precipitate metals. Plants can affect the metal mobility in floodplain soils by oxidising their rhizosphere, taking up metals, excreting exudates and stimulating the activity of microbial symbionts in the rhizosphere.