Arsenic speciation in food in Belgium. Part 2: Cereals and cereal products.

This study reports results of total arsenic (Astot) and various As species in 75 samples of cereals and cereal products bought on the Belgian market. In addition to rice, the samples were wheat, pasta, bread and some breakfast cereals. The inorganic species arsenite (AsIII) and arsenate (AsV), and the organic As compounds dimethyl arsinate (DMA) and monomethyl arsonate (MA) were the only As species detected. Mean Astot was 0.150 ±â€¯0.089 mg kg-1 in rice and 0.012 ±â€¯0.008 mg kg- in the non-rice cereals. The inorganic arsenic fraction (Asi = AsIII + AsV) dominated in all samples and was in the range 55%-100%. Significantly higher Astot and Asi concentrations were observed in white rice and brown rice compared to Basmati rice. Within the group of non-rice cereals bread and pasta showed significantly lower concentrations compared to wheat. All 30 rice samples were conform to the European maximum limits for Asi, laid down in Commission Regulation (EU) 2015/1006. Although regulatory limits certainly can help to protect consumer health, our results suggest that the currently fixed European maximum levels are, in Belgium, not expected to have any impact on the human exposure to Asi, which is a known carcinogenic substance.

Accumulation of atmospheric deposition of As, Cd and Pb by bush bean plants.

Bush bean (Phaseolus vulgaris) was exposed to atmospheric deposition of As, Cd and Pb in a polluted and a reference area. The atmospheric deposition of these elements was significantly related to the concentrations in leaves, stems and pods at green harvest. Surprisingly there was also a clear relation for As and Pb in the seeds at dry harvest, even though these seeds were covered by the husks. Root uptake of accumulated atmospheric deposits was not likely in such a short term experiment, as confirmed by the fact that soil pore water analysis did not reveal significant differences in trace element concentrations in the different exposure areas. For biomonitoring purposes, the leaves of bush bean are the most suitable, but also washed or unwashed pods can be used. This means that the obtained relationships are suitable to estimate the transfer of airborne trace elements in the food chain via bush bean.

Comparing responses to different selenium sources and dosages in laying hens.

Developing new sources of organic Se has potential benefit for animal production and human nutrition via animal-based foods enriched in Se. The objectives of this trial were to compare L-selenomethionine with another organic Se source, Se-enriched yeast (SelPlex 2300), and sodium selenite, an inorganic Se source, against a commercial control diet. The effect of source and the dosage of Se supplementation on Se in eggs and blood variables was investigated. Ten treatments were used with 18 laying hens per group. In addition to the control diet, the control diet was supplemented with L-selenomethionine, Se-enriched yeast, or sodium selenite at 0.1, 0.3, or 0.5 mg/kg of Se. The feeding trial lasted 8 wk. Birds in the different treatment groups all showed good performance. At d 0 and 56, Se and glutathione peroxidase (GPx) were analyzed in 10 blood samples per group. After supplementing the diets for 56 d, significantly higher Se levels in serum and egg contents were reached for the Se-supplemented groups compared with the control. Supplementing 0.3 and 0.5 mg/kg of L-selenomethionine or Se-enriched yeast instead of 0.1 mg/kg significantly increased the serum Se levels, whereas no significant increase was found for sodium selenite. No effect of Se source or dosage was observed on serum GPx levels. Selenium in eggs was significantly affected by dosage and source of Se. The Se supplementation level in the feed was reflected in the eggs, with the highest and lowest values for 0.5 and 0.1 mg/kg, respectively, and values in between for the 0.3 mg/kg supplementation level. A dose response was most pronounced for L-selenomethionine, followed by Se-enriched yeast, and was least when Se was added as sodium selenite. It can be concluded that Se from organic sources was more bioavailable than the inorganic Se source as evidenced by blood and egg Se levels. Within the organic Se sources, L-selenomethionine showed higher Se transfer to eggs than Se-enriched yeast.

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.

Economic viability of phytoremediation of a cadmium contaminated agricultural area using energy maize. Part I: effect on the farmer's income.

This paper deals with the economic viability of using energy maize as a phytoremediation crop in a vast agricultural area moderately contaminated with metals. The acceptance of phytoremediation as a remediation technology is, besides the extraction rate, determined by its profitability, being the effects it has on the income of the farmer whose land is contaminated. This income can be supported by producing renewable energy through anaerobic digestion of energy maize, a crop that takes up only relatively low amounts of metals, but that can be valorised as a feedstock for energy production. The effect on the income per hectare of growing energy maize instead of fodder maize seems positive, given the most likely values of variables and while keeping the basic income stable, originating from dairy cattle farming activities. We propose growing energy maize aiming at risk-reduction, and generating an alternative income for farmers, yet in the long run also generating a gradual reduction of the pollution levels. In this way, remediation is demoted to a secondary objective with sustainable risk-based land use as primary objective.

Long-term sustainability of metal immobilization by soil amendments: cyclonic ashes versus lime addition.

A soil column leaching experiment was used to gain insight into the long-term metal immobilization capacity of cyclonic ashes (CAH) compared to lime (LIME). Twenty six years of rainfall were simulated. Initially, all amended soils were brought to an equal soil pH. This was done to obtain optimal conditions for the detection of metal immobilization mechanisms different from just a pH effect. During the simulation period, soil pH in all treatments decreased in parallel. However, the evolution of metal mobility and phytoavailability showed a clearly distinct pattern. The strong reduction in metal immobilizing efficiency observed in the lime treatment at the end of the simulation period was much less pronounced, or even absent, in the CAH treatments. Moreover, metal accumulation in plants grown on the CAH amended soil was significantly lower compared to the untreated and the lime treated soil. CAH + SS treatment delivered the strongest reductions in metal mobility and bioavailability.

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.

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.

Potential use of the plant antioxidant network for environmental exposure assessment of heavy metals in soils.

In recent years, awareness has risen that the total soil content of pollutants by itself does not suffice to fully assess the potential ecotoxicological risks involved. Chemical analysis will require to be complemented with biological assays in a multidisciplinary approach towards site specific ecological risk assessment (SS-ERA). This paper evaluates the potential use of the plants' antioxidant response to metal-induced oxidative stress to provide a sensitive biological assay in SS-ERA. To this end, plants of Phaseolus vulgaris were grown for two weeks on 15 soils varying in contamination level. Morphological parameters and enzymatic plant responses were measured upon harvest. Foliar concentrations of the (heavy) metals Al, Cu, Cd, Cr, Fe, Mn, Ni, Pb, Zn were also determined. Metal mobility in the soil was further assessed by determining soil solution and NH4OAc extractable levels. In general more significant correlations were observed between plant responses and foliar metal concentrations or exchangeable/soluble levels than between plant responses and the total soil content. The study demonstrates the potential use of the plants' antioxidant defence mechanisms to assess substrate phytotoxicity for application in SS-ERA protocols. However, the system, based on calculation of a soil Phytotoxicity Index (PI), will require adaptation and fine-tuning to meet the specific needs for this type of environmental monitoring. Large variation was observed in phytotoxicity classification based on the various test parameters. The thresholds for classification of the various morphological and enzymatic response parameters may require adaptation according to parameter stress sensitivity in order to decrease the observed variation. The use of partial PI's (leaves and roots separately) may in addition increase the sensitivity of the system since some metals show specific effects in one of both organs only. Loss of biological functionality of enzymes, as was observed for ICDH in one of the more strongly contaminated soils, may also be recognized as an additional stress symptom when assigning phytotoxicity classification, whereas the current system only considers increasing enzymatic capacities. Other easily distinguishable parameters, which could be added to the current indexation are: failure to germinate and the incapacity to develop roots in the toxic substrate. Additional research will be required to determine the possible application range of soil properties for this biological assay and to further improve its performance in SS-ERA.

Phytostabilization of a metal contaminated sandy soil. I: Influence of compost and/or inorganic metal immobilizing soil amendments on phytotoxicity and plant availability of metals.

In a lysimeter set-up, compost addition to an industrial contaminated soil slightly reduced phytotoxicity to bean seedlings. The "Phytotoxicity Index" (on a scale from 1 to 4) decreased from 3.5 to 2.8. The same treatment also reduced metal accumulation in grasses: mean Zn, Cd and Pb concentrations decreased respectively from 623 to 135, from 6.2 to 1.3 and from 10.7 to <6 mg kg-1 dry weight. When combined with inorganic metal immobilizing amendments, compost had a beneficial effect on plant responses additional to the inorganic amendments alone. Best results were obtained when using compost (C)+cyclonic ashes (CA)+steel shots (SS). The "Phytotoxicity Index" decreased to 1.7, highest diversity of spontaneously colonizing plants occurred, and metal accumulation in grasses reduced to values for uncontaminated soils. Based on the first year evaluation, C+CA+SS showed to be an efficient treatment for amendment assisted phytostabilization of the contaminated Overpelt soil.

Phytostabilization of a metal contaminated sandy soil. II: Influence of compost and/or inorganic metal immobilizing soil amendments on metal leaching.

A lysimeter approach (under natural climatologic conditions) was used to evaluate the effect of four metal immobilizing soil treatments [compost (C), compost+cyclonic ashes (C+CA), compost+cyclonic ashes+steel shots (C+CA+SS)) and cyclonic ashes+steel shots (CA+SS)] on metal leaching through an industrially contaminated soil. All treatments decreased Zn and Cd leaching. Strongest reductions occurred after CA+SS and C+CA+SS treatments (Zn: -99.0% and -99.2% respectively; Cd: -97.2% and -98.3% respectively). Copper and Pb leaching increased after C (17 and >30 times for Cu and Pb respectively) and C+CA treatment (4.4 and >3.7 times for Cu and Pb respectively). C+CA+SS or CA+SS addition did not increase Cu leaching; the effect on Pb leaching was not completely clear. Our results demonstrate that attention should be paid to Cu and Pb leaching when organic matter additions are considered for phytostabilization of metal contaminated soils.

Potential of Brassic rapa, Cannabis sativa, Helianthus annuus and Zea mays for phytoextraction of heavy metals from calcareous dredged sediment derived soils.

Remediation of soil pollution is one of the many current environmental challenges. Anthropogenic activity has resulted in the contamination of extended areas of land, the remediation of which is both invasive and expensive by conventional means. Phytoextraction of heavy metals from contaminated soils has the prospect of being a more economic in situ alternative. In addition, phytoextraction targets ecotoxicologically the most relevant soil fraction of these metals, i.e. the bioavailable fraction. Greenhouse experiments were carried out to evaluate the potential of four high biomass crop species in their potential for phytoextraction of heavy metals, with or without with the use of soil amendments (EDTA or EDDS). A calcareous dredged sediment derived surface soil, with high organic matter and clay content and moderate levels of heavy metal pollution, was used in the experiments. No growth depression was observed in EDTA or EDDS treated pots in comparison to untreated controls. Metal accumulation was considered to be low for phytoextraction purposes, despite the use of chelating agents. The low observed shoot concentrations of heavy metals were attributed to the low phytoavailability of heavy metals in this particular soil substrate. The mobilising effects induced by EDTA in the soil were found to be too long-lived for application as a soil amendment in phytoextraction. Although EDDS was found to be more biodegradable, higher effect half lives were observed than reported in literature or observed in previous experiments. These findings caution against the use of any amendment, biodegradable or otherwise, without proper investigation of its effects and the longevity thereof.

Comparison of EDTA and EDDS as potential soil amendments for enhanced phytoextraction of heavy metals.

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.