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Challenges in geochemical modelling of metal(loid) solubility and binding mechanisms along a soil profile at a multi-contaminated site
Linnaeus University, Faculty of Health and Life Sciences, Department of Biology and Environmental Science. Linnaeus University, Linnaeus Knowledge Environments, Sustainable Health.ORCID iD: 0009-0007-5381-2773
Linnaeus University, Faculty of Health and Life Sciences, Department of Biology and Environmental Science. Linnaeus University, Linnaeus Knowledge Environments, Water.
Swedish Geotechnical Institute, Sweden;Swedish University of Agricultural Sciences, Sweden.
Stockholm University, Sweden.
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2024 (English)In: Applied Geochemistry, ISSN 0883-2927, E-ISSN 1872-9134, Vol. 170, article id 106063Article in journal (Refereed) Published
Sustainable development
SDG 15: Protect, restore and promote sustainable use of terrestrial ecosystems, sustainably manage forests, combat desertification, and halt and reverse land degradation and halt biodiversity loss
Abstract [en]

Recognising the need for robust models in predicting groundwater contamination risks from metal(loid)s in contaminated topsoil, this study focuses on the geochemical behaviour of As, Cd, Cu, Pb, Sb and Zn in one of Sweden’s most heavily contaminated areas. Samples were collected from the waste zone and underlying subsoil down to 5 meters and batch experiments were carried out to assess pH-dependent solubility. The results indicate that Cd, Cu, Pb and Zn are efficiently immobilized in the waste zone, while As(V) and Sb(V) are more easily leached. With the exception of Pb and Cu at high pH, the mobilized metals appear to be predominantly in a truly dissolved state, as confirmed by ultrafiltration at 10 kDa.

Speciation modelling using Visual MINTEQ did not suggest a significant role of precipitates such as Zn or Pb arsenates and phosphates, although their involvement could not be ruled out. To better understand sorption/desorption patterns, a multi-surface geochemical model was established, drawing on the Stockholm Humic and CD-MUSIC models for organic matter and Fe/Al (hydr)oxide sorption. However, when default parameters were used, the model consistently overestimated the solubility of Cd, Cu, Pb and Zn in both the waste zone and the uncontaminated subsoil. In contrast, As(V) solubility was generally underestimated, also when the reactive surface area of the Fe- and Al (hydr)oxides was decreased in the model. The model's performance was better for Sb(V), though not without imperfections. When the parameters for organic matter were adjusted such that 100% of the solid-phase organic matter was active with respect to ion binding, but only 25% of the dissolved organic matter, the model description improved considerably for Pb and Cu in the upper soil layers. The model revealed distinct differences in the adsorption behaviour of the metal cations, with Pb being sorbed mostly to Fe/Al (hydroxides), whereas a considerable part of Cu was sorbed to organic matter, particularly in the waste zone.

Possibly, the dissolution of easily weatherable metal-containing mineral phases may have contributed to the poor model performance for Cd, Zn and for Cu in the deeper soil layers, although other factors, such as a contribution of hydrous SiO2 or Mn oxides to metal binding, could not be ruled out. Metal sorption to carbonate phases may also have been a contributing factor in the waste zone. Lastly, the reactivity of Fe- and Al (hydr)oxides may have been overestimated by oxalate extraction when default parameters for high-surface-area ferrihydrite were applied. 

These findings provide valuable insights for environmental management and underscore the need for a more detailed characterization of metal(loid) sorption in contaminated soils, as well as the development of improved modelling strategies to enhance solubility predictions.

Place, publisher, year, edition, pages
Elsevier, 2024. Vol. 170, article id 106063
Keywords [en]
Lead, Cadmium, Arsenic, Antimony, pH-dependent solubility, Geochemical modelling
National Category
Earth and Related Environmental Sciences
Research subject
Natural Science, Environmental Science
Identifiers
URN: urn:nbn:se:lnu:diva-129658DOI: 10.1016/j.apgeochem.2024.106063ISI: 001253000500001Scopus ID: 2-s2.0-85195585309OAI: oai:DiVA.org:lnu-129658DiVA, id: diva2:1862071
Funder
The Geological Survey of Sweden (SGU), 36-1778/2014Available from: 2024-05-29 Created: 2024-05-29 Last updated: 2025-02-11Bibliographically approved
In thesis
1. Leachability and transport of metal(loid)s from contaminated land: Geochemical processes and health risks
Open this publication in new window or tab >>Leachability and transport of metal(loid)s from contaminated land: Geochemical processes and health risks
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Alternative title[sv]
Lakbarhet och transport av metal(loid)er från förorenad mark : Geokemiska processer och hälsorisker
Abstract [en]

Heavy metal contamination of land poses severe risks to human health and the environment on a global scale. This thesis aims, firstly, to fill knowledge gaps regarding the general risk of metals spreading from contaminated soil into local groundwater across Sweden. Secondly, it addresses the conditions affecting metal solubility and migration into groundwater specifically around Swedish glassworks sites. To understand the spread of metal from contaminated soil, detailed geochemical studies of the main study object (Pukeberg glasswork) were conducted. These studies complemented analyses of metal solubility in the waste zone with analyses of the underlying soil.

We found that high metal concentrations in soil alone are generally not reliable indicators of the risk of groundwater contamination. For instance, the investigated glassworks sites are examples where generic risk assessment models would predict a significant deterioration in groundwater quality, but this is not actually the case. Despite high concentrations and a high leachability of the waste zone material at Pukeberg, metal cations are efficiently immobilized in the natural soil underneath the source. Anions have a higher leachability, but are also retained close to the source area. The geochemical model used, however, had clear difficulties in predicting the observed solubility of most metal(loid)s, and was thus unable to fully uncover the processes behind the observed retention/solubility of metals. Our results underscore the necessity of developing methods and understanding which adsorbent phases are most influential under different scenarios.

The thesis also assesses the risks associated with consumption of vegetables grown near glassworks sites, or drinking water from private wells. The results showed that concentrations of As, Cd and Pb in vegetables were moderately elevated in glassworks villages, but still high enough to result in a daily intake of As and Cd above toxicological values for high-exposure individuals. Regarding drinking water exposure, As was the only metal out of five (As, Cd, Sb, Ba, Pb) that resulted in an intake above tolerable levels for high-exposure individuals, but this was not because of As concentrations in drinking water being elevated relative regional background concentrations, but rather because of the low doses that are tolerated for this element.

Abstract [sv]

Metallförorenad mark utgör globalt sett stora risker för människors hälsa och miljön. I denna avhandling kartläggs hur stor den generella risken är för att metaller sprider sig från förorenad mark i Sverige till lokala grundvattenmagasin i sådan grad så att grundvattnets tjänlighet äventyras. Avhandlingen undersöker vidare de förhållanden som påverkar metallers löslighet och spridning till grundvatten specifikt runt glasbruk i Glasriket i Småland. Eftersom spridning av metaller från förorenad mark inte bara påverkas av förutsättningarna i den förorenade källzonen, så utfördes de geokemiska analyserna för ett av studieobjekten (Pukebergs glasbruk) både på provmaterial från källzonen och från den underliggande jorden.

Resultaten visar att enbart metallkoncentrationer i jord generellt ger en dålig uppfattning om risken för kontaminering av grundvatten. De undersökta glasbruken är ett exempel på områden där generella riskbedömningsmodeller förutsäger en betydande förorening av lokalt grundvatten, men så är inte fallet i realiteten. Trots höga metallkoncentrationer och en hög lakbarhet av materialet på deponin i Pukeberg, så immobiliseras metallkatjoner effektivt i den naturliga jorden. Anjoner har en högre lakbarhet, men även deras spridning bort från källområdet är begränsad. Den geokemiska modell som tillämpades på datan från Pukeberg hade dock tydliga svårigheter att prediktera den observerade lösligheten hos de flesta metall(oid)er, och kunde således inte helt avslöja processerna bakom den observerade retentionen/lösligheten av metaller. Våra resultat understryker nödvändigheten av att fortsatt utveckla metoder och förstå vilka mekanismer som är mest inflytelserika för föroreningars fastläggning/frisättning från förorenad jord och dess omgivning.

Avhandlingen bedömer också riskerna med att konsumera grönsaker som odlats nära glasbruksområden, samt att dricka vatten från privata brunnar. Resultaten visade att koncentrationerna av As, Cd och Pb i grönsaker var måttligt förhöjda, men tillräckligt höga för att kunna resultera i ett dagligt intag av As och Cd över toxikologiska gränsvärden för individer med hög exponering. När det gäller exponeringen via dricksvatten var As den enda metall av fem (As, Cd, Sb, Ba, Pb) med potential att resultera i ett intag över tolerabla nivåer för individer med hög vattenkonsumtion. Detta berodde dock inte på att As-koncentrationerna i dricksvatten från privata brunnar var förhöjda relativt regionala bakgrundsnivåer, utan snarare på de låga doser som tolereras för detta element.

Place, publisher, year, edition, pages
Växjö: Linnaeus University Press, 2024. p. 48
Series
Linnaeus University Dissertations ; 530
Keywords
Heavy metals, Metalloids, Solubility, Mobility, Geochemical modelling, Contaminated soil and groundwater, Metal uptake by homegrown vegetables, Exposure assessment, Health risk assessment, Tungmetaller, Metalloider, Löslighet, Mobilitet, Geokemisk modellering, Förorenad mark och grundvatten, Metallupptag av hemodlade grönsaker, Exponeringsbedömning, Hälsoriskbedömning
National Category
Environmental Sciences
Research subject
Natural Science, Environmental Science
Identifiers
urn:nbn:se:lnu:diva-129660 (URN)10.15626/LUD.530.2024 (DOI)9789180821681 (ISBN)9789180821698 (ISBN)
Public defence
2024-08-20, Lapis (Vi1158), Hus Vita, Norra Kajplan 6, Kalmar, 09:00 (English)
Opponent
Supervisors
Funder
The Geological Survey of Sweden (SGU), 36- 1778/2014Linnaeus UniversitySwedish Research Council Formas, 2012-790Medical Research Council of Southeast Sweden (FORSS)The Kamprad Family FoundationSwedish Geotechnical Institute
Available from: 2024-06-03 Created: 2024-05-29 Last updated: 2025-03-26Bibliographically approved

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Uddh Söderberg, TereseAugustsson, AnnaÅström, Mats E.

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