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.
Vanadium (V), although serving as an important component of industrial activities, has bioinorganic implications to pose highly toxic hazards to humans and animals. Soils and sediments throughout the ...world exhibit wide ranges of vanadium concentrations. Although vanadium toxicity varies between different species, it is mainly controlled by soil redox potential (EH). Nonetheless, knowledge of the redox geochemistry of vanadium lags in comparison to what is known about other potentially toxic elements (PTEs). In particular, the redox-induced speciation and mobilization of vanadium in soils and sediments and the associated risks to the environment have not been reviewed to date. Therefore, this review aims to address 1) the content and geochemical fate of vanadium in soils and sediments, 2) its redox-induced release dynamics, 3) redox-mediated chemical reactions between vanadium and soil organic and inorganic colloidal materials in soil solution, 4) its speciation in soil solution and soil-sediments, and 5) the use of advanced geochemical and spectroscopic techniques to investigate these complex systems. Vanadium (+5) is the most mobile and toxic form of its species while being the thermodynamically stable valence state in oxic environments, while vanadium (+3) might be expected to be predominant under euxinic (anoxic and sulfidic) conditions. Vanadium can react variably in response to changing soil EH: under anoxic conditions, the mobilization of vanadium can decrease because vanadium (+5) can be reduced to relatively less soluble vanadium (+4) via inorganic reactions such as with H2S and organic matter and by metal-reducing microorganisms. On the other hand, dissolved concentrations of vanadium can increase at low EH in many soils to reveal a similar pattern to that of Fe, which may be due to the reductive dissolution of Fe(hydr)oxides and the release of the associated vanadium. Those differences in vanadium release dynamics might occur as a result of the direct impact of EH on vanadium speciation in soil solution and soil sediments, and/or because of the EH-dependent changes in soil pH, chemistry of (Fe)(hydr)oxides, and complexation with soil organic carbon. Release dynamics of vanadium in soils may also be affected positively by soil pH and the release of aromatic organic compounds. X-ray absorption spectroscopy (XAS) is a powerful tool to investigate the speciation of vanadium present in soil. X-ray absorption near edge structure (XANES) is often used to constrain the average valence state of vanadium in soils and sediments, and in limited cases extended X-ray absorption fine structure (EXAFS) analysis has been used to determine the average molecular coordination environment of vanadium in soil components. In conclusion, this review presents the state of the art about the redox geochemistry of vanadium and thus contributes to a better understanding of the speciation, potential mobilization, and environmental hazards of vanadium in the near-surface environment of uplands, wetlands, and agricultural ecosystems as affected by various colloidal particles. Further research is needed to elucidate the geochemistry and speciation of vanadium in the dissolved, colloidal, and soil sediments phases, including the determination of factors that control the redox geochemistry of vanadium.
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•The review presents the state of the art of the redox geochemistry of Vanadium (V).•The EH-dependent changes of pH, Fe oxides, and organic carbon affect V mobilization.•XAS is a powerful tool to investigate the speciation of V present in soil.•XANES is used to constrain the average valence state of V in soils and sediments.•The review contributes to a better understanding of the environmental hazards of V.
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.
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•Brassica species can be considered a potential candidate for Cd phytoremediation.•Brassica species can accumulate most of the soil Cd in its parts.•Different amendments can be applied to enhance Cd tolerance in Brassica species.•Integrated agricultural practices can be used to enhance Cd uptake in Brassica species.
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.
The hydrological regime is a key factor in determining the metal concentration in the pore water of a contaminated sediment-derived soil.
•Biochar significantly immobilized soil Cd and Zn over a 3-year period.•Compost and peat increased available Cd and Zn in soil.•Metal immobilization was attributed to the consistently higher pH and ...lower DOC concentrations in the biochar treatments.•DGT measurements were used to assess the short-term metal resupply kinetics.•The resupply of Cd and Zn from the solid phase to the soil solution was low (R ≤ 0.4) in all treatments.
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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.
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.
Phytoextraction has been proposed as an alternative remediation technology for soils polluted with heavy metals or radionuclides, but is generally conceived as too slow working. Enhancing the ...accumulation of trace pollutants in harvestable plant tissues is a prerequisite for the technology to be practically applicable. The chelating aminopolycarboxylic acid, ethylene diamine tetraacetate (EDTA), has been found to enhance shoot accumulation of heavy metals. However, the use of EDTA in phytoextraction may not be suitable due to its high environmental persistence, which may lead to groundwater contamination. This paper aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposes. A laboratory experiment was conducted to examine mobilisation of Cd, Cu, Cr, Ni, Pb and Zn into the soil solution upon application of EDTA or EDDS. The longevity of the induced mobilisation was monitored for a period of 40 days after application. Estimated effect half lives ranged between 3.8 and 7.5 days for EDDS, depending on the applied dose. The minimum observed effect half life of EDTA was 36 days, while for the highest applied dose no decrease was observed throughout the 40 day period of the mobilisation experiment. Performance of EDTA and EDDS for phytoextraction was evaluated by application to
Helianthus annuus. Two other potential chelators, known for their biodegradability in comparison to EDTA, were tested in the plant experiment: nitrilo acetic acid (NTA) and citric acid. Uptake of heavy metals was higher in EDDS-treated pots than in EDTA-treated pots. The effects were still considered insufficiently high to consider efficient remediation. This may be partly due to the choice of timing for application of the soil amendment. Fixing the time of application at an earlier point before harvest may yield better results. NTA and citric acid induced no significant effects on heavy metal uptake.
In the transition from a fossil to a bio-based economy, it has become an important challenge to maximally recycle valuable nutrients that currently end up in waste streams. Nutrient resources are ...rapidly depleting. Significant amounts of fossil energy are required for the production of synthetic fertilizers, whereas costs for energy and fertilizers are increasing. Meanwhile, biogas production through anaerobic digestion produces nutrient-rich digestates, which could potentially be reused as green fertilizers in agriculture, thereby providing a sustainable substitute for synthetic fertilizers. The aim of this study was to evaluate the impact of using bio-digestion waste derivatives instead of synthetic fertilizers and/or animal manure on soil and crop production. In a field trial, nutrient balances were assessed and the physicochemical soil fertility and quality were evaluated. The biogas yield of the harvested energy crops was determined. An economic and ecological evaluation was conducted. Application of bio-digestion waste derivatives induced small, albeit statistically insignificant improvement in crop yield, soil fertility and quality compared to current common practices using animal manure and synthetic fertilizers. Moreover, the use of these products might stimulate nutrient mobilization from the soil, thereby increasing the use efficiency of soil minerals. For all reuse scenarios the calculated economic and ecological benefits were significantly higher than the reference. It is clear that the reuse of bio-based products as nutrient supply in agriculture should be stimulated in European legislation. Further field research is on-going in order to validate the results and evaluate the impact on soil quality in the longer term.
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► We study the reuse of bio-digestion waste as synthetic fertilizer substitutes. ► Through a field-trial we evaluate their impact on soil and crop production. ► Application of these products slightly increased the soil quality and crop yield. ► The use of bio-digestion waste stimulated the soil nutrient use efficiency. ► Synthetic fertilizer substitution results in important economic & ecological benefits.
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.
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•Liquid fraction was used as a partial or complete substitute of synthetic N.•The impact on soil fertility, crop yield and economic use was examined.•No significant differences in crop yield and soil quality were observed at harvest.•Liquid fraction has a potential to be used as N fertilizer.•In manure surplus market, the use of liquid fraction can result in economic gain.
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.
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