Physical-chemical treatment of rainwater runoff in recovery and recycling companies: lab-scale investigation.

Scrap material recovery and recycling companies are producing wastewater in which common pollutants (such as COD, nutrients and suspended solids), toxic metals, polyaromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB) frequently can exceed the discharge limits. Lab-scale optimisation of different possible physical-chemical treatment techniques was performed on the wastewater originating from three different companies in view of further testing at pilot-scale testing and implementation at full-scale. The lab-scale tests demonstrate that sedimentation or hydrocyclone treatment as stand-alone technique cannot be used for proper treatment of this type of wastewater. Dual bed filtration or coagulation/flocculation proved to be more promising with removal efficiencies of about 71-95% (dual bed filtration) and 61-97% (coagulation/flocculation) for the above-mentioned pollutants (metals, PAH and PCB).

Chemical fractionation and speciation modelling for optimization of ion-exchange processes to recover palladium from industrial wastewater.

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.

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.

Impact of a trace element supplementation programme on health and performance of cross-breed (Bos indicus x Bos taurus) dairy cattle under tropical farming conditions: a double-blinded randomized field trial.

Small-scale urban dairy farms (n = 16) in and around Jimma, Ethiopia with cross-bred (Bos indicus × Bos taurus) cows were enrolled in a double-blinded intervention study to investigate the effect of a trace element supplementation programme on trace element status and milk concentrations as well as performance [body condition score (BCS), milk yield, leptin], milk composition, antioxidant status (ferric-reducing ability of plasma (FRAP), thiobarbituric acid-reactive substances (TBARS)], blood biochemistry, serum proteins and immune response (antibody titre upon rabies vaccination). The farms were allocated to a (1) placebo or (2) Cu, Zn, Se, Co and I supplementation treatment for 150 d. On days 0 and 120, four lactating cows per farm were sampled for milk and plasma, and on day 150 for serum, following primo-vaccination. Cu deficiency was present in 17% and marginal Se deficiency in 30% of initially sampled cows, while no Zn shortage was detected. Over 120 days, trace element supplementation caused a bigger increase in plasma Se and Cu concentrations, but also a larger decrease of plasma Fe concentrations. A larger increase in milk Se concentrations was observed in the supplemented group, whereas none of the other elements were affected. BCS decreased more over time in the supplemented group. None of the other parameters of performance and antioxidant status nor milk composition or blood biochemistry was affected by treatment. Antibody response to rabies vaccination did not differ between groups, whereas α1-globulins tended to be lower and ß-globulins tended to be higher in the supplemented group. In conclusion, despite improved Cu and Se status and Se concentrations in milk, cows on tropical urban dairy farms did not seem to benefit from trace element supplementation, with respect to the parameters investigated.

Leaching behaviour of different scrap materials at recovery and recycling companies: full-, pilot- and lab-scale investigation.

Scrap material recovery and recycling companies are confronted with waste water that has a highly fluctuating flow rate and composition. Common pollutants, such as COD, nutrients and suspended solids, potentially toxic metals, polyaromatic hydrocarbons and poly chlorinated biphenyls can exceed the discharge limits. An analysis of the leaching behaviour of different scrap materials and scrap yard sweepings was performed at full-scale, pilot-scale and lab-scale in order to find possible preventive solutions for this waste water problem. The results of these leaching tests (with concentrations that frequently exceeded the Flemish discharge limits) showed the importance of regular sweeping campaigns at the company, leak proof or covered storage of specific scrap materials and oil/water separation on particular leachates. The particulate versus dissolved fraction was also studied for the pollutants. For example, up to 98% of the polyaromatic hydrocarbons, poly chlorinated biphenyls and some metals were in the particulate form. This confirms the (potential) applicability of sedimentation and filtration techniques for the treatment of the majority of the leachates, and as such the rainwater run-off as a whole.

A disparate trace element metabolism in zebu (Bos indicus) and crossbred (Bos indicus × Bos taurus) cattle in response to a copper-deficient diet.

Copper deficiency is a commonly diagnosed problem in cattle around the globe. In Jimma, Ethiopia, 8 zebu (Bos indicus) and 8 zebu ×: Holstein Friesian cross (Bos taurus ×: Bos indicus) heifers were used in an 11-wk study to investigate breed type differences and effects of Cu deficiency on concentrations of trace elements in plasma and edible tissues as well as mRNA expression of Cu-related genes. Heifers were fed a grass diet (6.4 ± 0.2 [SEM] mg Cu/kg DM) supplemented with 1 mg Mo/kg DM in wk 1 to 4 and 2 mg Mo/kg DM in wk 5 to 11, with blood samples collected every 2 wk and tissue collection postmortem. Plasma, liver, kidney, and semitendinosus and cardiac muscle were analyzed for Zn, Cu, Fe, Se, Mo, Co, and Mn. Expression of mRNA Cu-related genes was measured in aorta (lysyl oxidase [LOX]), liver (Cu transporting ß-polypeptide [Atp7b], Cu chaperone for superoxide dismutase [CCS], cytochrome c oxidase assembly homolog 17 [Cox17], Cu transporter 1 homolog [Ctr1], and superoxide dismutase 1 [Sod1]), and duodenum (diamine oxidase [DAO] and metallo-thionein-1A [Mt1a]) as well as the Se-related glutathione peroxidase 1 (Gpx1). Zebu cattle maintained initial plasma Cu concentrations just below the threshold value for deficiency, whereas crossbred cattle gradually became severely Cu deficient over time (P < 0.001). In contrast, plasma Zn and Co were greater in zebu cattle at the onset of the trial but became similar to crossbred cattle towards the end of the trial (P < 0.001). Liver Cu (P = 0.002) and Fe (P ≤ 0.001), kidney Se (P < 0.001), and kidney and cardiac muscle Co (P ≤ 0.001) concentrations were greater in zebu than in crossbred cattle. Increased hepatic mRNA expression of the Cu regulatory genes Atp7b, Ctr1 (P = 0.02), CCS (P = 0.03), and Cox17 (P = 0.009) and Cu-related Sod1 (P = 0.001) as well as the Se-related Gpx1 (P ≤ 0.001) were greater in zebu than in crossbred cattle. However, duodenal mRNA expression of DAO (P = 0.8) and Mt1a (P = 0.2) and aortic expression of LOX (P = 0.8) were not different. Both the differences in Cu status indices (plasma and liver concentrations) and hepatic mRNA expression of Cu regulatory genes point to the possibility of a more efficient use of dietary Cu in B. indicus as compared to B. taurus ×: B. indicus cattle resulting in greater sensitivity to Cu deficiency in B. taurus crossbred cattle.

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.

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 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.

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.

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.

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.

Influence of flooding, salinity and inundation time on the bioavailability of metals in wetlands.

Controlled flooding of lowlands is considered as a potential water management strategy to minimize the risk of flooding of inhabited areas during high water periods. However, due to industrial activities, river water, sediments and soils are often contaminated with metals which may have adverse effects on the ecosystem's structure and functioning. Additionally, salinity may greatly affect the bioavailability and toxicity of metals present or imported into these systems. The effect of contaminated soils under different flooding and salinity exposure scenarios on the growth, reproduction and metal accumulation in the oligochaete Tubifex tubifex (Müller, 1774) were examined. In these bioassays metal contaminated soils were flooded with water of different salinities (0 and 3 psu), and tested after 0, 6 and 12 months of permanent inundation. We indeed found that inundation time had significant decreasing effects on Cu and Zn accumulation; although initial accumulation of Cu and Zn was higher in the previously unflooded soil at the start of the flooding treatment, these differences seem to disappear after 6 months of permanent inundation. Moreover, the complex interaction between substrate type and salinity suggests that redox potential is probably of major importance.

Influence of hydrological regime on pore water metal concentrations in a contaminated sediment-derived soil.

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.