G. Du Laing

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.

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.

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.

COST action TD1407: network on technology-critical elements (NOTICE)—from environmental processes to human health threats

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.

Factors affecting metal mobility and bioavailability in the superficial intertidal sediment layer of the Scheldt estuary

Many factors and variables govern trace metal behaviour in soils and sediments in complex ways. Understanding metal behaviour in intertidal wetland systems is further complicated because it concerns highly dynamic systems that are continuously subjected to quickly changing environmental conditions governed by alternating low and high tides. We studied the effects of various influencing factors, such as hydraulic regime, organic matter and salinity on metal mobility and bioavailability in the superficial calcareous intertidal sediment layer of the Scheldt estuary. These sediments contain elevated levels of particularly Cd, Cr and Zn. Flooding regime and the supply of organic matter significantly affect pore water metal concentrations and hence potential mobility and bioavailability. Fe, Mn and Ni pore water contents in the upper intertidal sediment layer increased as a result of frequent flooding, whereas Cd, Cu and Zn contents decreased. Organic matter can act as a sink for metals, but it can also induce dissolution of metals which were previously bound to solid sediment compartments, especially Fe, Mn and Ni. Salinity particularly favoured Cd mobility and bioavailability in oxidised sediments, which was confirmed by field monitoring data, but it also affected Zn, Fe and Mn mobility. More detailed speciation analysis of metals in the pore water is needed to improve our understanding about the contribution and importance of various processes in determining the observed metal behaviour.

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.

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.

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 ecosystems 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.

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.