Bioaccessibility of trace elements as affected by soil parameters in smelter-contaminated agricultural soils: a statistical modeling approach

An investigation was undertaken to identify the most significant soil parameters that can be used to predict Cd, Pb, and Zn bioaccessibility in smelter-contaminated agricultural soils. A robust model was established from an extended database of soils by using: (i) a training set of 280 samples to select the main soil parameters, to define the best population to be taken into account for the model elaboration, and to construct multivariate regression models, and (ii) a test set of 110 samples to validate the ability of the regression models. Total carbonate, organic matter, sand, P(2)O(5), free Fe-Mn oxide, and pseudototal Al and trace element (TE) contents appeared as the main variables governing TE bioaccessibility. The statistical modeling approach was reasonably successful, indicating that the main soil factors influencing the bioaccessibility of TEs were taken into account and the predictions could be applicable for further risk evaluation in the studied area.     

Assessment of potential health risk for inhabitants living near a former lead smelter. Part 1: metal concentrations in soils, agricultural crops, and homegrown vegetables

Soil contamination by metals engenders important environmental and health problems in northern France where a smelter (Metaleurop Nord) was in activity for more than a century. This study aims to look at the long-term effects of the smelter after its closedown by combining data on the degree of soil contamination and the quality of the crops grown (agricultural crops and homegrown vegetables) in these soils for a better assessment of the local population’s exposure to Cd, Pb, and Zn. Seven years after the Metaleurop Nord closedown, (1) the agricultural and urban topsoils were strongly contaminated by Cd, Pb, and Zn; (2) the kitchen garden topsoils were even more polluted than the agricultural soils, with great variability in metal concentrations within the gardens studied; (3) a high proportion of the agricultural crops for foodstuffs did not conform with the European legislation; (4) for feedstuffs, most samples did not exceed the Cd and Pb legislation limits, indicating that feedstuffs may be an opportunity for most agricultural produce; and (5) a high proportion of the vegetables produced in the kitchen gardens did not conform with the European foodstuff legislation. The high contamination level of the soils studied continues to be a risk for the environment and the population’s health. A further investigation (part 2) assesses the associated potential health risk for local inhabitants through consumption of homegrown vegetables and ingestion of soil particles by estimating the site-specific human health assessment criteria for Cd and Pb.     

Assessing Cd,Pb, Zn human bioaccessibility in smelter-contaminated agricultural topsoils (northern France)

The extractability of Cd, Pb, and Zn was investigated in contaminated agricultural topsoils located in an area highly affected by the past atmospheric emissions of two smelters in northern France in order to assess their mobility and human bioaccessibility. The determination of Cd, Pb, and Zn bioaccessibility (Unified Barge Method, in vitro test) was made to evaluate the absolute trace element (TE) bioavailability. The results highlighted differences in bioaccessibility between Cd, Pb, and Zn (Cd > Pb > Zn). The mean values of the bioaccessible fractions of Cd, Pb, and Zn during the gastric phase were 82, 55, and 33%, respectively, of the pseudototal concentrations, whereas during the gastrointestinal phase, the bioaccessible fractions of metals decreased to 45, 20, and 10%, respectively. Stepwise multiple regression analysis showed that human bioaccessibility was affected by various physicochemical parameters (i.e., sand, carbonates, organic matter, assimilated P, free Al oxides, and pseudototal Fe contents). Sequential extractions were performed as an indication of the TE availability in these soils. Cadmium occurred in the more available fractions, Pb was mostly present as bound by oxides, and a significant contribution to the pseudototal Zn concentration was defined as the unavailable residual form related to the crystalline structures of minerals. The concepts of bioavailability and bioaccessibility are important for quantifying the risks associated with exposure to environmental pollutants and providing more realistic information for human health.     

Vertical distribution of Cd, Pb and Zn in soils near smelters in the North of France

The analysis of the horizons of 12 soil profiles confirm occasionally significant levels of Cd, Pb and Zn contamination in the areas surrounding two lead and zinc smelters in the North of France. A pedological approach enabled the original Cd, Pb and Zn content of the horizons to be estimated, based on physico-chemical characteristics of soil unaffected by contamination. The main contamination was found in the upper 20-30 cm. Traces of Cd and Zn contamination were found at a depth of around 2 m. The mobility of the metals may be classified in the following order: Cd>Pb> or =Zn. The concentration profile of a metal seems insufficient to evaluate its movement as the metal could have been leached beyond the contaminated horizons. The depth reached by the metals increases with their concentration in the surface horizon; a decrease in pH and an increase in sand content seem to facilitate their movement. The depth reached by Zn increases with the organic carbon content in the surface horizon. Earthworm galleries act as paths via which metals migrate downwards     

Assessment of potential health risk for inhabitants living near a former lead smelter. Part 2: site-specific human health risk assessment of Cd and Pb contamination in kitchen gardens

Metal contamination of urban soils and homegrown products has caused major concern. In Part 1, we investigated the long-term effects of a former smelter on the degree of kitchen garden-soil contamination and the quality of the homegrown vegetables from these gardens. The results showed that the soils retained a high level of contamination and that a large proportion of the vegetables produced did not comply with the legislation on the levels of metals allowed for human consumption. The present study aims to assess the associated potential health risk to local inhabitants through consumption of homegrown vegetables and ingestion of soil particles using a land use-based approach. For lead (Pb), the standard hazard quotient (HQ)-based risk assessment method was used to determine the HQ. For cadmium (Cd), the approach consisted of calculating the HQs and then deriving site-specific assessment criteria (SSAC) using the SNIFFER method. The results suggested that the exposure pathways considered should not engender any form of deleterious health effects for adults. For children, Pb was the main concern and induced a relatively high health risk through soil particle ingestion, and most total soil Cd concentrations exceeded the derived SSAC, in particular, through consumption of vegetables. The metal bioaccessibility in soils was incorporated into the methods to establish more realistic risk assessment measures. This study proposes an approach to integrate different human health risk assessment methods. Further investigations should complete the assessment to improve risk determination, e.g., the determination of metal bioaccessibility in vegetables.     

Impact of a smelter closedown on metal contents of wheat cultivated in the neighbourhood

BACKGROUND: The contamination of soils by heavy metals engenders important environmental and sanitary problems in Northern France where a smelter has been located for more than one hundred of years. It has been one of the most important Pb production sites in Europe until its closedown in March 2003. Ore smelting process generated considerable atmospheric emissions of dust. Despite an active environmental strategy, these emissions were still significant in 2002 with up to 17 tonnes of Pb, 32 tonnes of Zn and 1 tonne of Cd. Over the years, the generated deposits have led to an important contamination of the surrounding soils. Previous studies have shown pollutant transfers to plants, which can induce a risk for human and animal health. The objective of this study was to evaluate the consequences of the smelter closedown on the Cd and Pb contents of wheat (grain and straw) cultivated in the area. METHODS: Paired topsoil and vegetable samples were taken at harvest time at various distances to the smelter. The sample sites were chosen in order to represent a large range of soil metal contamination. Sampling was realised on several wheat harvests between 1997 and 2003. 25 samples were collected before the smelter closedown and 15 after. All ears of about 1 m long of two rows were manually picked and threshed in the lab. Similarly, straw was harvested at the same time. Total metal contents in soil and wheat samples were quantified. RESULTS: A negative correlation between metal concentrations in soil and the distance to the smelter was shown. The wheat grain and straw showed significant Cd and Pb contents. The straw had higher metal contents than the grain. During the smelter activity, the grain contents were up to 0.8 mg kg(-1) DM of Cd and 8 mg kg(-1) DM of Pb. For the straw, maximum contents were 5 mg kg(-1) DM of Cd and 114 mg kg(-1) DM of Pb. After the smelter closedown, we observed a very large decrease of Pb in the grain (82%) and in the straw (91%). A smaller decrease was observed for Cd in grain. Despite this improvement, 80% of the studied samples remained non-acceptable for human consumption, according to the European legislation values, due to a high Cd content. DISCUSSION: Results highlighted a difference in metal accumulation in the plant organs as well as a difference in metal uptake. The approach pointed out the importance of atmospheric fallout in the wheat contamination pathways for Pb. The smelter closedown has lead to a decrease of the Pb content in wheat. It is interesting to relate this finding with the lead blood levels in children living close to the smelter. CONCLUSIONS: Those results have confirmed the importance of dust fallout in the plant contamination pathways. Before the closedown, Pb measured in the plant was principally originating from the smelter dust emissions. It raised the question of the sanitary risks for humans and animals living in the surrounding a of the smelter. RECOMMENDATIONS AND PERSPECTIVES: In the literature, very few articles take the dust deposit as contamination pathways for crops into consideration. However, in highly contaminated sites, this pathway can be very important. Thus, it would be worthy studying the uptake of metal contaminants by plants through the foliar system.     

Dissolved and colloidal transport of Cd, Pb, and Zn in a silt loam soil affected by atmospheric industrial deposition.

As a result of processing of metal ores, trace metals have contaminated large areas of northern France. Metal migration from the soil to groundwater presents an environmental risk that depends on the physico-chemical properties of each contaminated soil. Soil water samples were obtained over the course of 1 year with zero-tension lysimeters from an acidic, loamy, metal contaminated soil. The average trace metal concentrations in the soil water were high (e.g. for Zn 11 mg l-1 under the surface horizon), but they varied during the sampling period. Zn concentrations were not correlated with pH or total organic carbon in the solutions but were correlated with Cd concentrations. On average, 95% of the Zn and Cd but only 50% of Pb was present in a dissolved form. Analytical transmission electron microscopy was used to identify the Zn or Pb carriers. Colloids containing Pb and Zn were biocolloids, whereas colloids containing only Zn were smectites.     

Recombinant luminescent bacterial sensors for the measurement of bioavailability of cadmium and lead in soils polluted by metal smelters

Environmental hazard of heavy metals in soils depends to a large extent on their bioavailability. The approach used in this study enables the determination of bioavailable metals in solid-phase samples. Two recombinant bacterial sensors, one responding specifically to cadmium and the other to lead and cadmium by increase of luminescence (firefly luciferase was used as a reporter) were used to determine the bioavailability of these metals in soil-water suspensions (a contact assay) and respective particle-free extracts. Fifty agricultural soils sampled near zinc and lead smelters in the Northern France containing up to (mg/kg) 20.1 of Cd, 1050 of Pb and 1390 of Zn were analysed. As the soil matrix interferes with the assay, recombinant luminescent control bacteria lacking the metal recognizing protein and corresponding promoter (thus, being not metal-inducible) but otherwise comparable to the sensor bacteria (the same host bacterium and plasmid encoding luciferase) were used in parallel to take into account the possible quenching and/or stimulating effects of the sample on the luminescence of the sensor bacteria. Both, chemical and sensor analysis showed that only microg/l levels of metals were extracted from the soil into the water phase (0.1% of the total Cd, 0.07% of Pb and 0.5% of Zn). However, 115-fold more Cd and 40-fold more Pb proved bioavailable if the sensor bacteria were incubated in soil suspensions (i.e., in the contact assay). The bioavailability of metals in different soils varied (depending probably on soil type) ranging from 0.5% to 56% for cadmium and from 0.2% to 8.6% for lead.     

From environmental data acquisition to assessment of gardeners’ exposure: feedback in an urban context highly contaminated with metals

Environmental Science and Pollution Research - Although growing vegetables in urban gardens has several benefits, some questions in relation with the safety of foods remain when the self-production...     

Influence of fly ash aided phytostabilisation of Pb, Cd and Zn highly contaminated soils on Lolium perenne and Trifolium repens metal transfer and physiological stress

Due to anthropogenic activities, large extends of soils are highly contaminated by Metal Trace Element (MTE). Aided phytostabilisation aims to establish a vegetation cover in order to promote in situ immobilisation of trace elements by combining the use of metal-tolerant plants and inexpensive mineral or organic soil amendments. Eight years after Coal Fly Ash (CFA) soil amendment, MTE bioavailability and uptake by two plants, Lolium perenne and Trifolium repens, were evaluated, as some biological markers reflecting physiological stress. Results showed that the two plant species under study were suitable to reduce the mobility and the availability of these elements. Moreover, the plant growth was better on CFA amended MTE-contaminated soils, and the plant sensitivity to MTE-induced physiological stress, as studied through photosynthetic pigment contents and oxidative damage was lower or similar. In conclusion, these results supported the usefulness of aided phytostabilisation of MTE-highly contaminated soils.