Modeling of the Solid−Solution Partitioning of Heavy Metals and Arsenic in Embanked Flood Plain Soils of the Rivers Rhine and Meuse

Schröder, Thomas J.; Hiemstra, Tjisse; Vink, Jos P.M.; Zee, S.E.A.T.M. van der

doi:10.1021/es048154s

Cited by 65 publications

(54 citation statements)

References 45 publications

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“…Sample digestion was performed by accurately weighing 0.25g of soil into a Savillex™ vial and adding HF, HNO 3 and HClO 4 concentrated and analytical grade acids, with a subsequent stepped heating program up to 170°C overnight, the purpose being the digestion of silicate and oxide phases. The dry 45 residue was re-constituted after warming with MQ water, HNO 3 and H 2 O 2 , to 25 mL of 5% v/v HNO 3 and stored in HDPE bottles. Reference materials (NIST SRM2710, SRM2711, GSS-6, BGS102 and BCR-2), duplicated samples and blanks were all prepared in a similar manner to check accuracy of the analytical 50 and digestion method.…”

Section: Total Metal Concentrations Of Soil Samplesmentioning

confidence: 99%

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Lability, solubility and speciation of Cd, Pb and Zn in alluvial soils of the River Trent catchment UK

Izquierdo

Tye

Chenery

2013

Environ. Sci.: Processes Impacts

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5Alluvial soils can store a wide range of metal contaminants originating from point and diffuse sources. The biological health of these soils is important as they act as an interface between terrestrial and aquatic environments, therefore playing an important role in maintaining the quality of surface waters. The aim of this work was to examine the lability, solubility and bioavailability of Pb, Zn and Cd in the top (0-15 cm) and sub soil (35-50 cm) of metal contaminated alluvial soils from the Trent catchment, U.K. Samples 10 (n=46) were collected from within 10m of the river bank. Sources of contamination include historical mining, industry, sewage treatment works and energy production. Enrichment factors based on total metal concentrations showed that contamination in soils declined with distance from the mining areas before rising again as a result of general urbanisation and identified point sources (e.g. river dredging activities). Pore waters were extracted and isotopic dilution and single extraction assays were undertaken on the soils 15 to assess the lability and solubility of the metals. Multi-element isotopic dilution assays were used to determine the labile pool or E-value of these metals in the soil. E-value concentrations were found to range between 0.5-14 mg/kg, 11-350 mg/kg and 25-594 mg/kg for Cd, Pb and Zn, respectively. Comparison of the E-value assay with the EU standard extraction assay for trace element availability (0.05M EDTA) showed that EDTA extractions generally over-estimated the E-value for Zn and Pb,with 20 the difference being greater as contamination levels increased. Bioavailability of the metals was assessed by speciating the pore waters [M Sol ] using WHAM 7 to obtain estimates of free ion activities (M 2+ ). Values of (M 2+ ) were compared to published 'median critical limits' for soils that estimate levels of protection for 95% of biological species. For each of the three metals, (M 2+ ) was found to exceed these critical limits at some sites. Solubility of the metals are reported using K d values expressed using both the 25 total and E-value as the solid phase. Finally we examine the use of different metal pools (total, E-value, EDTA-extractable) and different measures of Fe oxide pools (total, free total, free amorphous), in predicting [M Sol ] concentrations and (M 2+ ) using WHAM 7 in assemblage modelling mode. Overall best simultaneous model predictions for the three metals were obtained using the E-values. Larger overestimates of [M Sol ] and (M 2+ ) were produced using the EDTA and total metal pools whereas a better 30 fitting in the prediction was obtained when models used either the total or the free total FeOx pools. IntroductionAlluvial soils act as archives for fluvially dispersed metal contaminants from numerous sources [1][2][3][4][5] . These soils are often used in intensive agricultural systems. Several studies in the UK 35 have previously noted the potential for metal transfer into cattle, when grazing grass grown on contaminated alluvial soils [6][7] . In a...

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Section: Total Metal Concentrations Of Soil Samplesmentioning

confidence: 99%

“…Alluvial soils act as archives for fluvially dispersed metal contaminants from numerous sources [1][2][3][4][5] . These soils are often used in intensive agricultural systems.…”

Section: Introductionmentioning

confidence: 99%

Lability, solubility and speciation of Cd, Pb and Zn in alluvial soils of the River Trent catchment UK

Izquierdo

Tye

Chenery

2013

Environ. Sci.: Processes Impacts

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“…Hence, our third aim is to derive solid-solution partitioning models for metals based on the 0.01 M CaCl 2 extracts. Dilute salt extracts and soil-solution partitioning models are used as practical tools in risk assessment studies in well-aerated soils (Peijnenburg et al 1999;Pueyo et al 2004;Schröder et al 2005;Meers et al 2007), but it is unclear if they are applicable for predicting the directly available metal pools in paddy fields as well which are characterized by a frequent shift from aerobic to anaerobic conditions during the growing season. Shifting redox conditions can lead to a change in the directly available pool and our fourth aim, therefore, is to compare the size of the directly available pool at the two harvest times.…”

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Characterization of soil heavy metal pools in paddy fields in Taiwan: chemical extraction and solid-solution partitioning

et al. 2009

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Background, aim, and scope Ongoing industrialization has resulted in an accumulation of metals like Cd, Cu, Cr, Ni, Zn, and Pb in paddy fields across Southeast Asia. Risks of metals in soils depend on soil properties and the availability of metals in soil. At present, however, limited information is available on how to measure or predict the directly available fraction of metals in paddy soils. Here, the distribution of Cd, Cu, Cr, Ni, Zn, and Pb in 19 paddy fields among the total, reactive, and directly available pools was measured using recently developed concepts for aerated soils. Solid-solution partitioning models have been derived to predict the directly available metal pool. Such models are proven to be useful for risk assessment and to derive soil quality standards for aerated soils. , and directly available metal pools (0.01 M CaCl 2 ) were determined. Solid-solution partitioning models were derived by multiple linear regressions using an extended Freundlich equation using the reactive metal pool, pH, and the cation exchange capacity (CEC). The influence of Zn on metal partitioning and differences between both sampling events (May/November) were evaluated. Results Total metals contents range from background levels to levels in excess of current soil quality standards for arable land. Between 3% (Cr) and 30% (Cd) of all samples exceed present soil quality standards based on extraction with AR. Total metal levels decreased with an increasing distance from the irrigation water inlet. The reactive metal pool relative to the total metal content is increased in the order Cr << Ni = Zn < Pb < Cu < Cd and ranged from less than 10% for Cr to more than 70% for Cd. Despite frequent redox cycles, Cd, Pb, and Cu appear to remain rather reactive. The methods to determine the reactive metal pool in soils yield comparable results, although the 0.43 M HNO 3 extraction is slightly stronger than HCl and EDTA. The close correlation between these methods suggests that they release similar fractions from soils, probably those reversibly sorbed to soil organic matter (SOM) and clay. The average directly available pool ranged from less than 1% for Cu, Pb, and Cr to 10% for Ni, Zn, and Cd when compared to the reactive metal pool. For Cd, Ni, Zn, and to a lesser extent for Cu and Pb, solid-solution partitioning models were able to explain up to 93% (Cd) of the observed variation in the directly available metal pool. CaCl 2 extractable Zn increased the directly available pool for Ni, Cd, and Cu but not that of Pb and Cr. In the polluted soils, the directly available pool was higher in November compared to that in May. Differences in temperature, rainfall, and changes in soil properties such as pH are likely to contribute to the differences observed within the year. The solid-solution partitioning model failed to explain the variation in the directly available Cr pool, probably because Cr is present in precipitates rather than being adsorbed onto SOM and clay. Despite obvious differences in parent material, source of pollu...

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“…These calculations were performed with the chemical speciation model BIOCHEM-ORCHESTRA (Vink and Meeussen 2007). This model is based on the chemical module BIOCHEM (Schröder et al 2005;Vink and Schröder 2006) which was modified with the NICA-DONNAN concept for complexation of metals to DOM (Benedetti et al 1995), and coupled to the ORCHESTRA framework (Meeussen 2003). Unlike most chemical speciation models, BIOCHEM-ORCHESTRA is capable of simulating redox changes over time by relating water saturation and duration to reduction potential for each layer.…”

Section: Speciation Modellingmentioning

confidence: 99%

Delayed immobilization of heavy metals in soils and sediments under reducing and anaerobic conditions; consequences for flooding and storage

Vink

Harmsen²,

Rijnaarts

2010

J Soils Sediments

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Purpose The consequences of permanent inundation and storage of flood plain soils and aquatic sediments on metal mobility were studied. The main goal was to quantify kinetic mobilisation processes in order to pinpoint the conditions that pose emission risks to groundwater and surface waters. Materials and methods Anaerobic pore water compositions of six existing depots, containing sediments from either aquatic or terrestrial origin, were measured to obtain reliable field references. Reduction experiments were performed with SOFIE cells, in which time-dynamic measurements of reducing pore waters were carried out at the reigning redox conditions. A parallel experiment tested the possibility if sulfide-deficiencies could be compensated by the reduction of added gypsum, thus increasing the available pool of reactive S. Model calculations were performed to distinguish between the thermodynamic and kinetic processes. Results and discussion Reduction of flood plain soils showed that dissolved organic matter (DOM) concentrations increased up to 7-fold over time, as a result of nutrient-mediated metabolic boost of organic matter degrading microorganisms. The association of metals to DOM increased significantly due to the loss of reactive Mn-oxide and Fe-oxyhydroxide sorption phases during reduction. DOM released metals only slowly, therefore kinetically hindering the phase shifting to stable metalsulfide precipitates. The observed effects lasted at least 10 months. In aquatic sediments, reduction rates of sulphates were six times faster, and the release of DOM occurred in lower amounts than in soils from terrestrial origin. It is shown that the addition of gypsum stimulates the formation of sulfides, thereby decreasing dissolved concentrations of most metals. On the short term however, the addition of gypsum leads to elevated concentrations of Zn and Cd due to increased electrolyte strength and subsequent Ca-metal-competition for sorption sites. This effect may be eliminated by not only adding an electron acceptor to the sediment, but also an effective donor, e.g., degradable organic matter. Conclusions For depots containing flood plain soils, the same kinetic mechanisms were observed as in the reduction experiments (elevated production of DOM and associated metals). It was concluded that reduction of flood plain soils may not necessarily result in efficient metal trapping. When storage is considered, a distinction should be made between sediments of terrestrial and aquatic origin.

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Modeling of the Solid−Solution Partitioning of Heavy Metals and Arsenic in Embanked Flood Plain Soils of the Rivers Rhine and Meuse

Cited by 65 publications

References 45 publications

Lability, solubility and speciation of Cd, Pb and Zn in alluvial soils of the River Trent catchment UK

Lability, solubility and speciation of Cd, Pb and Zn in alluvial soils of the River Trent catchment UK

Characterization of soil heavy metal pools in paddy fields in Taiwan: chemical extraction and solid-solution partitioning

Delayed immobilization of heavy metals in soils and sediments under reducing and anaerobic conditions; consequences for flooding and storage

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