The current socio-economic, environmental and public health challenges that countries are facing clearly need common-defined strategies to inform and support our transition to a sustainable economy. ...Here, the technology-critical elements (which includes Ga, Ge, In, Te, Nb, Ta, Tl, the Platinum Group Elements and most of the rare-earth elements) are of great relevance in the development of emerging key technologies—including renewable energy, energy efficiency, electronics or the aerospace industry. In this context, the increasing use of technology-critical elements (TCEs) and associated environmental impacts (from mining to end-of-life waste products) is not restricted to a national level but covers most likely a global scale. Accordingly, the European COST Action TD1407: Network on Technology-Critical Elements (NOTICE)—from environmental processes to human health threats, has an overall objective for creating a network of scientists and practitioners interested in TCEs, from the evaluation of their environmental processes to understanding potential human health threats, with the aim of defining the current state of knowledge and gaps, proposing priority research lines/activities and acting as a platform for new collaborations and joint research projects. The Action is focused on three major scientific areas: (i) analytical chemistry, (ii) environmental biogeochemistry and (iii) human exposure and (eco)-toxicology.
An automated biogeochemical microcosm system allowing controlled variation of redox potential (EH) in soil suspensions was used to assess the effect of various factors on the mobility of mercury (Hg) ...as well as on the methylation of Hg in two contaminated floodplain soils with different Hg concentrations (approximately 5 mg Hg kg−1 and >30 mg Hg kg–1). The experiment was conducted under stepwise variation from reducing (approximately −350 mV at pH 5) to oxidizing conditions (approximately 600 mV at pH 5). Results of phospholipid fatty acids (PLFA) analysis indicate the occurrence of sulfate reducing bacteria (SRB) such as Desulfobacter species (10Me16:0, cy17:0, 10Me18:0, cy19:0) or Desulfovibrio species (18:2ω6,9), which are considered to promote Hg methylation. The products of the methylation process are lipophilic, highly toxic methyl mercury species such as the monomethyl mercury ion MeHg+, which is named as MeHg here. The ln(MeHg/Hgt) ratio is assumed to reflect the net production of monomethyl mercury normalized to total dissolved Hg (Hgt) concentration. This ratio increases with rising dissolved organic carbon (DOC) to Hgt ratio (ln(DOC/Hgt) ratio) (R2 = 0.39, p<0.0001, n= 63) whereas the relation between ln(MeHg/Hgt ratio and lnDOC is weaker (R2 = 0.09; p<0.05; n = 63). In conclusion, the DOC/Hgt ratio might be a more important factor for the Hg net methylation than DOC alone in the current study. Redox variations seem to affect the biogeochemical behavior of dissolved inorganic Hg species and MeHg indirectly through related changes in DOC, sulfur cycle, and microbial community structure whereas EH and pH values, as well as concentration of dissolved Fe3+/Fe2+ and Cl– seem to play subordinate roles in Hg mobilization and methylation under our experimental conditions.
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.
Palladium is used in several industrial applications and, given its high intrinsic value, intense efforts are made to recover the element. In this hydrometallurgic perspective, ion-exchange (IEX) ...technologies are principal means. Yet, without incorporating the chemical and physical properties of the Pd present in real, plant-specific conditions, the recovery cannot reach its technical nor economic optimum. This study characterized a relevant Pd-containing waste stream of a mirror manufacturer to provide input for a speciation model, predicting the Pd speciation as a function of pH and chloride concentration. Besides the administered neutral PdCl2 form, both positively and negatively charged PdCln(2-n) species occur depending on the chloride concentration in solution. Purolite C100 and Relite 2AS IEX resins were selected and applied in combination with other treatment steps to optimize the Pd recovery. A combination of the cation and anion exchange resins was found successful to quantitatively recover Pd. Given the fact that Pd was also primarily associated with particles, laboratory-scale experiments focused on physical removal of the Pd-containing flow were conducted, which showed that particle-bound Pd can already be removed by physical pre-treatment prior to IEX, while the ionic fraction remains fully susceptible to the IEX mechanism.
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
×
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
mg
kg
−1 in the top soil layer.
The effect of the flood water salinity on the mobility of heavy metals was studied for intertidal sediments of the Scheldt estuary (Belgium). Soils and sediments of 4 sampling sites were flooded with ...water of different salinities (0.5, 2.5, and 5
g
NaCl
L
−1). Metal concentrations were monitored in pore water and surface water. To study the potential effects of flood water salinity on metal bioavailability, duckweed (
Lemna minor) was grown in the surface water. The salinity was found to primarily enhance the mobility of Cd and its uptake by duckweed. Cadmium concentrations in pore water of soils and sediments and surrounding surface waters significantly exceeded sanitation thresholds and quality standards during flooding of initially oxidized sediments. Moreover, the effect was observed already at lower salinities of 0.5
g
NaCl
L
−1. This implies that risks related to Cd uptake by organisms and Cd leaching to ground water are relevant when constructing flooding areas in the brackish zones of estuaries. These risks can be reduced by inducing sulphide precipitation because Cd is then immobilised as sulphide and its mobility becomes independent of flood water salinity. This could be achieved by permanently flooding the polluted sediments, because sulphates are sufficiently available in the river water of the brackish part of the estuary.
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.
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.
Naturally occurring pyroclastic materials, quartz-rich tuffs (Qz) and stellerite tuffs, were evaluated for their capacities to remove As(V) from aqueous solutions. The mechanism of As(V) uptake was ...evaluated using sequential extraction of As(V)-loaded adsorbent which entailed that the plausible removal mechanism is sorption to short-range ordered hydrous oxides of iron and aluminum. In addition, buffering effects of adsorbents could form favorable charges upon them through hydrolysis of amphoteric oxides, enhancing the performance of sorption. The influence of anions co-existing with As(V) in water such as carbonate, bicarbonate, nitrate, chloride, phosphate, and sulfate was studied in a batch sorption process. The impact of most anions on As(V) removal was found to be negligible except phosphate. The sorption behavior well fitted to Langmuir and Freundlich models. Estimated maximum sorption capacities of 0.42 and 0.23 mg/L were observed using quartz-rich tuffs and stellerite tuffs, respectively. As(V) concentration of 0.8 mg/L was easily decreased to below the drinking water standard of 0.01 mg/L using Qz adsorbent, whereas 0.1 mg/L As(V) decreased to below this limit upon the use of stellerite tuffs under similar conditions. The buffering capacity of quartz-rich tuffs and stellerite tuffs induced a pH increase to 5.76 and 5.40, respectively, from initial pH of 3.50, which will incur an important asset in real applications.
This study assessed the accumulation of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in the sediment and biomass of P. australis (Cav.) Trin. ex Steud. in a combined constructed wetland (CW) designed for ...the treatment of domestic wastewater of 750 population equivalents. The CW consists of two vertical subsurface flow (VSSF) reed beds followed by two horizontal subsurface flow (HSSF) reed beds. The sediment in the VSSF reed bed was contaminated with Cu (201 ± 27 mg kg-¹ DM) and Zn (662 ± 94 mg kg-¹ DM) after 4 years of operation. Concentrations of Cd, Cu, Pb and Zn in the sediment generally decreased along the treatment path of the CW. On the contrary, higher Al, Cr, Fe, Mn and Ni concentrations were observed in the sediment of the inlet area of the HSSF reed bed. Redox conditions were presumably responsible for this observed trend. Metal concentrations in the reed biomass did not show excessive values. Accumulation in the aboveground reed biomass accounted for only 0.5 and 1.4% of, respectively, the Cu and Zn mass load in the influent. The sediment was the main pool for metal accumulation in the CW.
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