Scattered literature is harnessed to critically review the possible sources, chemistry, potential biohazards and best available remedial strategies for a number of heavy metals (lead, chromium, arsenic, zinc, cadmium, copper, mercury and nickel) commonly found in contaminated soils. The principles, advantages and disadvantages of immobilization, soil washing and phytoremediation techniques which are frequently listed among the best demonstrated available technologies for cleaning up heavy metal contaminated sites are presented. Remediation of heavy metal contaminated soils is necessary to reduce the associated risks, make the land resource available for agricultural production, enhance food security and scale down land tenure problems arising from changes in the land use pattern.

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Heavy Metals in Contaminated Soils: A Review of Sources, Chemistry, Risks and Best Available Strategies for Remediation

Engineered nanomaterials (ENM) are already used in many products and consequently released into environmental compartments. In this study, we calculated predicted environmental concentrations (PEC) based on a probabilistic material flow analysis from a life-cycle perspective of ENM-containing products. We modeled nano-TiO2, nano-ZnO, nano-Ag, carbon nanotubes (CNT), and fullerenes for the U.S., Europe and Switzerland. The environmental concentrations were calculated as probabilistic density functions and were compared to data from ecotoxicological studies. The simulated modes (most frequent values) range from 0.003 ng L−1 (fullerenes) to 21 ng L−1 (nano-TiO2) for surface waters and from 4 ng L−1 (fullerenes) to 4 μg L−1 (nano-TiO2) for sewage treatment effluents. For Europe and the U.S., the annual increase of ENMs on sludge-treated soil ranges from 1 ng kg−1 for fullerenes to 89 μg kg−1 for nano-TiO2. The results of this study indicate that risks to aquatic organisms may currently emanate from nano-Ag, n...

Modeled Environmental Concentrations of Engineered Nanomaterials (TiO2, ZnO, Ag, CNT, Fullerenes) for Different Regions

Occurrence, behavior and effects of nanoparticles in the environment.

Natural zeolites as effective adsorbents in water and wastewater treatment

Microbial communities play a pivotal role in the functioning of plants by influencing their physiology and development. While many members of the rhizosphere microbiome are beneficial to plant growth, also plant pathogenic microorganisms colonize the rhizosphere striving to break through the protective microbial shield and to overcome the innate plant defense mechanisms in order to cause disease. A third group of microorganisms that can be found in the rhizosphere are the true and opportunistic human pathogenic bacteria, which can be carried on or in plant tissue and may cause disease when introduced into debilitated humans. Although the importance of the rhizosphere microbiome for plant growth has been widely recognized, for the vast majority of rhizosphere microorganisms no knowledge exists. To enhance plant growth and health, it is essential to know which microorganism is present in the rhizosphere microbiome and what they are doing. Here, we review the main functions of rhizosphere microorganisms and how they impact on health and disease. We discuss the mechanisms involved in the multitrophic interactions and chemical dialogues that occur in the rhizosphere. Finally, we highlight several strategies to redirect or reshape the rhizosphere microbiome in favor of microorganisms that are beneficial to plant growth and health.

The rhizosphere microbiome: significance of plant beneficial, plant pathogenic, and human pathogenic microorganisms

Chelant-enhanced phytoextraction has received a lot of attention in the past decade. In theory, this technique could cleanse metal polluted soils by solubilizing contaminating metals, allowing them to be taken up by plants that would subsequently be removed from the site. We review the processes of metal solubilization, uptake by plants, and leaching during chelant-enhanced phytoextraction. A large excess of chelant is required to solubilize the target metal due to the co-solubilization of Ca and Fe. Chelated metals are taken up via the apoplastic pathway. Disruption of the Casparian Band is required to achieve the high shoot concentrations needed for phytoextraction. Therefore, adding chelants to a soil increases not only the total dissolved metal concentration but also changes the primary route of plant metal-uptake from the symplastic to the apoplastic pathway. Depending on metal, plant species, and chelant concentration, significant increases in metal uptake are likely. Soil solution chelate concentrations of at least several mM are required to induce appreciable shoot concentrations. A simple calculation reveals that at such soil solution concentrations plants will remove only a small fraction of the solubilized metals. Leaching, exacerbated by preferential flow processes, is unavoidable. Chelant-enhanced phytoextraction is therefore limited to areas where the connection with groundwater has been broken, orwhere leaching is unimportant. Chelant-enhanced phytoextraction may nonetheless have a role in enhancing the uptake of essential trace metals. Such a role warrants further investigations into the use of biodegradable chelants such as ethylenediaminedisuccinic acid (EDDS).

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Critical assessment of chelant-enhanced metal phytoextraction.

In this study, we investigated the removal of Fe, Pb, Cd, and Zn from synthetic mine waters by a natural zeolite. The emphasis was given to the zeolite's behavior toward a few cations in competition with each other. Pb was removed efficiently from neutral as well as from acidic solutions, whereas the uptake of Zn and Cd decreased with low pH and high iron concentrations. With increasing Ca concentrations in solution, elimination of Zn and Cd became poorer while removal of Pb remained virtually unchanged. The zeolite was stable in acidic solutions. Disintegration was only observed below pH 2.0. Forward- and back-titration of synthetic acidic mine water were carried out in the presence and absence of zeolite to simulate the effects of a pH increase by addition of neutralizing agents and a re-acidification which can be caused by subsequent mixing with acidic water. The pH increase during neutralization causes precipitation of hydrous ferric oxides and decreased dissolved metal concentrations. Zeolite addition further diminished Pb concentrations but did not have an effect on Zn and Cd concentrations in solution. During re-acidification of the solution, remobilization of Pb was weaker in the presence than in the absence of zeolite. No substantial differences were observed for Fe, Cd, and Zn immobilization. The immobilization of the metals during pH increase and the subsequent remobilization caused by re-acidification can be well described by a geochemical equilibrium speciation model that accounts for metal complexation at hydrous ferric oxides, for ion exchange on the zeolite surfaces, as well as for dissolution and precipitation processes.

Removal of Heavy Metals from Mine Waters by Natural Zeolites

The influence of EDDS on the uptake of heavy metals in hydroponically grown sunflowers.

A pot experiment was conducted to investigate the relationship between soluble concentrations of arsenic (As) in soil and its accumulation by maize (Zea mays), English ryegrass (Lolium perenne), rape (Brassica napus) and sunflower (Helianthus annuus) on two different soils: a calcareous Regosol (silty loam) and a non-calcareous Regosol (sandy loam). Arsenic (Na2HAsO4·7H2O) was applied to obtain comparable soluble As concentrations in the two soils. In both soils, soluble As concentrations, extracted with 0.1 M NaNO3, were found to correlate better with As concentrations in plants after 4 month of growth than total soil concentrations, extracted with 2 M HNO3. With all four plant species, the relationship between the soluble As concentration in the soil and As that in the plants was non- linear, following “Michaelis-Menten” kinetics. Similar soluble As concentrations in the two soils did not result in a similar As concentration in the plants. Except for maize, arsenic transport from roots to shoots was significant, resulting in As concentrations in the leaves and grains above the Swiss tolerance limits for fodder and food crops (4 and 0.2 mg As kg−1, respectively). Based on these results we suggest that beside As solubility, P availability and P demand, which are plant specific, have to be taken into account to predict the uptake of As by crop plants from As contaminated soils and to predict the risk of arsenic entering into the food chain.

Arsenic accumulation of common plants from contaminated soils

A possible remediation strategy for metal polluted soils is washing with chelants. Here, we compare the efficiency of batch and column extraction of Cu, Zn, and Pb from three soils using the biodegradable chelant EDDS. A total of 53-80% of Cu was extracted in batch and 18-26% in column extraction. For Zn, the extractability was 16-50% in batch and 20-64% in columns and for Pb 25-52 and 18-91%, respectively. Column leaching was therefore equally or better suited for Zn and Pb removal. The longer extraction time in the column resulted in more formations of Fe(III)EDDS by slow dissolution of iron oxides. Zn was uniformly washed from the column, while Cu and Pb were extracted in the top layers and deposited in the bottom layers, presumably by biodegradation of the metal-EDDS complexes and slow dissolution of iron oxides. Between 18 and 42% of the applied EDDS was lost through biodegradation after 7 weeks. In short time experiments, only 6% of EDDS was degraded. Using EDDS concentrations in excess of available heavy metals caused pronounced leaching of organic matter and clogging of the column. Our results prove that heap leaching using EDDS is a promising approach to reduce the heavy metal content of polluted soils.

Rainer Schulin

Papers

Critical assessment of chelant-enhanced metal phytoextraction.

Removal of Heavy Metals from Mine Waters by Natural Zeolites

The influence of EDDS on the uptake of heavy metals in hydroponically grown sunflowers.

Arsenic accumulation of common plants from contaminated soils

Column extraction of heavy metals from soils using the biodegradable chelating agent EDDS.