P.F.A.M. Römkens

Critical Soil Concentrations of Cadmium, Lead, and Mercury in View of Health Effects on Humans and Animals

Assessment of the risk of elevated soil metal concentrations requires appropriate critical limits for metal concentrations in soil in view of ecological and human toxicological risks. This chapter presents an overview of methodologies to derive critical total metal concentrations in soils for Cd, Pb, and Hg as relevant to health effects on animals and humans, taking into account the effect of soil properties. The approach is based on the use of nonlinear relationships for metals in soil, soil solution, plants, and soil invertebrates, including soil properties that affect metal availability in soil. Results indicate that the impact of soil properties on critical soil metal concentrations is mainly relevant for Cd because of significant soil-plant, soil-solution, and soil-worm relationships. Critical Cd levels in soil thus derived are sometimes lower than those related to ecotoxicological impacts on soil organisms/processes and plants, which is especially true for critical soil Cd concentrations in view of food quality criteria for wheat, drinking water quality, and acceptable daily intakes of worm-eating birds and mammals. There are, however, large uncertainties involved in the derivation from assumptions made in the calculation and uncertainties in acceptable daily intakes and in relationships for Cd in soil, soil solution, plants, and soil invertebrates. Despite these uncertainties, the analyses indicate that present Cd concentrations in parts of the rural areas are in excess of the critical levels at which effects in both agricultural and nonagricultural systems can occur.

Prediction of cadmium uptake by brown rice and derivation of soil-plant transfer models to improve soil protection guidelines.

Cadmium (Cd) levels in paddy fields across Taiwan have increased due to emission from industry. To ensure the production of rice that meets food quality standards, predictive models or suitable soil tests are needed to evaluate the quality of soils to be used for rice cropping. Levels of Cd in soil and rice grains were measured in 19 paddy fields across the western plains in Taiwan. Cadmium levels in soil range from less than 0.1 mg kg(-1) to 30 mg kg(-1). Measured Cd levels in brown rice were predicted very well (R(2) > 0.8) based on Cd and Zinc in a 0.01 M CaCl(2) extract or a soil-plant transfer model using the reactive soil Cd content, pH, and cation exchange capacity. In contrast to current soil quality standards used in Taiwan, such models are effective in identifying soils where Cd in rice will exceed food quality standards.

Feasibility of phytoextraction to remediate cadmium and zinc contaminated soils

A Cd and Zn contaminated soil was mixed and equilibrated with an uncontaminated, but otherwise similar soil to establish a gradient in soil contamination levels. Growth of Thlaspi caerulescens (Ganges ecotype) significantly decreased the metal concentrations in soil solution. Plant uptake of Cd and Zn exceeded the decrease of the soluble metal concentrations by several orders of magnitude. Hence, desorption of metals must have occurred to maintain the soil solution concentrations. A coupled regression model was developed to describe the transfer of metals from soil to solution and plant shoots. This model was applied to estimate the phytoextraction duration required to decrease the soil Cd concentration from 10 to 0.5 mg kg(-1). A biomass production of 1 and 5 t dm ha(-1) yr(-1) yields a duration of 42 and 11 yr, respectively. Successful phytoextraction operations based on T. caerulescens require an increased biomass production.

Evaluation of an approach for the characterization of reactive and available pools of twenty potentially toxic elements in soils: Part I – The role of key soil properties in the variation of contaminants’ reactivity

Harmful effects of potentially toxic elements (PTEs) in soils relate to their geochemically reactive fraction. To assess the degree of the reactivity, specific extractions or models are needed. Here we applied a 0.43 M HNO(3) chemical extraction to assess reactive pools of a broad range of PTEs in 136 contaminated and non-contaminated soils. Furthermore we derived Freundlich-type models based on commonly available soil properties (pH, organic carbon and clay) as well as extended models that used other properties such as amorphous Al and Fe oxides and evaluated their possible use in risk assessment. The approach allowed to predict the reactivity of As, Hg, Co, U, Ba, Se, Sb, Mo, Li, Be (r(2): 0.55-0.90) elements not previously included in such studies, as well as that of Cd, Zn, Cu, Pb, Ni and Cr (r(2): 0.73-0.90). The inclusion of pH, organic carbon and clay improved the performance of all models except for Be and Mo, although the role of clay is not completely clear and requires further investigation. The ability of amorphous metal oxides to affect the reactivity of As, Hg, Cu, Ni, Cr, Sb, Mo and Li was expressed by the models in agreement with known geochemical processes leading to the retention of PTEs by the solid matrix. Hence, such approach can be a useful tool to account for regional differences in soil properties during the identification of risk areas and constitute a significantly more powerful tool than the analysis of total pools of PTEs in soils.

Effect of plant growth on copper solubility and speciation in soil solution samples.

The effect of plant growth on copper solubility and speciation was studied in a 10-week pot experiment. A copper-tolerant grass variety (Agrostis capillaris L. var. Parys Mountain) was grown in pots that contained either clean (copper-total approx. 30 mg kg(-1)) or copper contaminated soil (copper-total approx. 170 mg kg(-1)) at two pH levels (4.7 and 5.5). Also, similar pots without vegetation were included in the study. Due to the addition of NH(4)NO(3) fertilizer and subsequent nitrification of ammonia to nitrate, soil pH decreased from 4.7 to 3.5 and from 5.5 to 4, respectively. In the planted pots, soil pH recovered faster after depletion of NH(4)(+). This resulted in a decrease in the calcium solution concentrations and an increase in the dissolved organic carbon (DOC) concentrations in the planted pots. However, this was only observed in the clean soil; in the contaminated soil no difference in DOC levels between bare and planted pots was observed. Copper solubility in the contaminated soil was lower in the presence of plants; in the clean soil no differences were observed between the bare and planted pots. In the planted pots, copper activities in solution in both clean and contaminated soils were two orders of magnitude lower than in the bare pots. Copper activities in the non-planted contaminated soil reached potentially toxic levels ([Cu]+/-10(-5) to 10(-6) M) in contrast to the lower levels in the planted pots ([Cu]+/-10(-7) to 10(-10) M). Data and model results show that plant growth improves pH, DOC and calcium in solution to such an extent that both the total dissolved copper concentration and the free metal activity in soils can be reduced. This stresses the potential beneficial role of plants for the immobilization and detoxification of metals in contaminated soils.

Soil–plant–animal transfer models to improve soil protection guidelines: A case study from Portugal

Food chain models are essential tools to assess risks of soil contamination in view of product quality including fodder crops and animal products. Here we link soil to plant transfer (SPT) models for potentially toxic elements (PTEs) including As, Ba, Cd, Co, Cu, Hg, Ni, Pb, Sb, U and Zn with models describing accumulation in animal organs. Current EU standards for food products and acceptable daily intake levels (ADI) for humans were used as critical limits. The combined model is used to assess the impact of soil contamination on animal health, product quality and human health using data from 100 arable fields. Results indicate that 42 existing arable fields near industrial and mining sites are unsuitable for animal grazing in view of food safety due to elevated intake of Cd, Cu, Hg and Pb by cows and sheep. At 10 sites daily intake levels of As by cows exceeded threshold concentrations regarding the quality of animal products. The food chain model also was used inversely to derive soil threshold concentrations in view of EU fodder standards. Calculated threshold levels in soil for As, Cd, Cu, Pb, Hg and Zn appear to be in line with those proposed or used in other EU countries. As such the approach applied here can form a conceptual basis for a more harmonized risk assessment strategy regarding the protection of animal and human health.

Evaluation of an approach for the characterization of reactive and available pools of 20 potentially toxic elements in soils: Part II – Solid-solution partition relationships and ion activity in soil solutions

To assess environmental risks related to contaminants in soil it is essential to predict the available pool of inorganic contaminants at regional scales, accounting for differences between soils from variable geologic and climatic origins. An approach composed of a well-accepted soil extraction procedure (0.01 M CaCl(2)) and empirical Freundlich-type models in combination with mechanistically based models which to date have been used only in temperate regions was applied to 136 soils from a South European area and evaluated for its possible general use in risk assessment. Empirical models based on reactive element pools and soil properties (pH, organic carbon, clay, total Al, Fe and Mn) provided good estimations of available concentrations for a broad range of contaminants including As, Ba, Cd, Co, Cu, Hg, Mo, Ni, Pb, Sb, Se and Zn (r(2): 0.46-0.89). The variation of the pools of total Al in soils expressed the sorptive capacity of aluminosilicates and Al oxides at the surfaces and edges of clay minerals better than the actual variability of clay contents. The approach has led to recommendations for further research with particular emphasis on the impact of clay on the solubility of As and Sb, on the mechanisms controlling Cr and U availability and on differences in binding properties of soil organic matter from different climatic regions. This study showed that such approach may be included with a good degree of certainty for first step risk assessment procedures to identify potential risk areas for leaching and uptake of inorganic contaminants in different environmental settings.

Impact of model uncertainty on soil quality standards for cadmium in rice paddy fields

At present, soil quality standards used for agriculture do not consider the influence of pH and CEC on the uptake of pollutants by crops. A database with 750 selected paired samples of cadmium (Cd) in soil and paddy rice was used to calibrate soil to plant transfer models using the soil metal content, pH, and CEC or soil Cd and Zn extracted by 0.01 M CaCl₂ as explanatory variables. The models were validated against a set of 2300 data points not used in the calibration. These models were then used inversely to derive soil quality standards for Japonica and Indica rice cultivars based on the food quality standards for rice. To account for model uncertainty, strict soil quality standards were derived considering a maximum probability that rice exceeds the food quality standard equal to 10 or 5%. Model derived soil standards based on Aqua Regia ranged from less than 0.3 mg kg⁻¹ for Indica at pH 4.5 to more than 6 mg kg⁻¹ for Japonica-type cultivars in clay soils at pH 7. Based on the CaCl₂ extract, standards ranged from 0.03 mg kg⁻¹ Cd for Indica cultivars to 0.1 mg kg⁻¹ Cd for Japonica cultivars. For both Japonica and Indica-type cultivars, the soil quality standards must be reduced by a factor of 2 to 3 to obtain the strict standards. The strong impact of pH and CEC on soil quality standards implies that it is essential to correct for soil type when deriving national or local standards. Validation on the remaining 2300 samples indicated that both types of models were able to accurately predict (> 92%) whether rice grown on a specific soil will meet the food quality standard used in Taiwan.

Risks associated with the transfer of toxic organo-metallic mercury from soils into the terrestrial feed chain.

Although the transfer of organo-metallic mercury (OrgHg) in aquatic food webs has long been studied, it has only been recently recognized that there is also accumulation in terrestrial systems. There is still however little information about the exposure of grazing animals to OrgHg from soils and feed as well as on risks of exposure to animal and humans. In this study we collected 78 soil samples and 40 plant samples (Lolium perenne and Brassica juncea) from agricultural fields near a contaminated industrial area and evaluated the soil-to-plant transfer of Hg as well as subsequent trophic transfer. Inorganic Hg (IHg) concentrations ranged from 0.080 to 210mgkg(-1) d.w. in soils, from 0.010 to 84mgkg(-1) d.w. in roots and from 0.020 to 6.9mgkg(-1) d.w. in shoots. OrgHg concentrations in soils varied between 0.20 and 130μgkg(-1) d.w. representing on average 0.13% of the total Hg (THg). In root and shoot samples OrgHg comprised on average 0.58% (roots) and 0.66% (shoots) of THg. Average bioaccumulation factors (BAFs) for OrgHg in relation to soil concentrations were 3.3 (for roots) and 1.5 (for shoots). The daily intake (DI) of THg in 33 sampling sites exceeded the acceptable daily intake (ADI) of THg of both cows (ADI=1.4mgd(-1)) and sheep (ADI=0.28mgd(-1)), in view of food safety associated with THg in animal kidneys. Estimated DI of OrgHg for grazing animals were up to 220μgd(-1) (for cows) and up to 33μgd(-1) (for sheep). This study suggested that solely monitoring the levels of THg in soils and feed may not allow to adequately taking into account accumulation of OrgHg in feed crops and properly address risks associated with OrgHg exposure for animals and humans. Hence, the inclusion of limits for OrgHg in feed quality and food safety legislation is advised.

Evaluation of the Single Dilute (0.43 M) Nitric Acid Extraction to Determine Geochemically Reactive Elements in Soil

Recently a dilute nitric acid extraction (0.43 M) was adopted by ISO (ISO-17586:2016) as standard for extraction of geochemically reactive elements in soil and soil like materials. Here we evaluate the performance of this extraction for a wide range of elements by mechanistic geochemical modeling. Model predictions indicate that the extraction recovers the reactive concentration quantitatively (>90%). However, at low ratios of element to reactive surfaces the extraction underestimates reactive Cu, Cr, As, and Mo, that is, elements with a particularly high affinity for organic matter or oxides. The 0.43 M HNO3 together with more dilute and concentrated acid extractions were evaluated by comparing model-predicted and measured dissolved concentrations in CaCl2 soil extracts, using the different extractions as alternative model-input. Mean errors of the predictions based on 0.43 M HNO3 are generally within a factor three, while Mo is underestimated and Co, Ni and Zn in soils with pH > 6 are overestimated, for which possible causes are discussed. Model predictions using 0.43 M HNO3 are superior to those using 0.1 M HNO3 or Aqua Regia that under- and overestimate the reactive element contents, respectively. Low concentrations of oxyanions in our data set and structural underestimation of their reactive concentrations warrant further investigation.