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Electricity driven remediation of arsenic and PAH contaminated soil in situ
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.ORCID iD: 0009-0001-8512-4453
2025 (English)Doctoral thesis, comprehensive summary (Other academic)Alternative title
Eldriven in situ-sanering av jord förorenad med arsenik och PAH (Swedish)
Abstract [en]

Contaminated soil is a global problem due to its association with environmental and health risks. The wood impregnation industry is one example that has left many sites co-contaminated with polycyclic aromatic hydrocarbons (PAH) and metal(loid)s, such as arsenic. 

Despite the negative environmental and economic aspects of landfilling, this is the most common soil remediation technology in Sweden and Europe.

This study sought to investigate the effects of electricity driven remediation on soil contaminated with arsenic and PAH, to contribute to the knowledge about using it as an alternative to landfilling.

The technology can be practiced in situ, since it uses electricity applied over electrodes inserted into the soil. The intentionally corroding iron rod electrodes sought to amend the soil with iron. This was done to allow for formation of iron oxides in the soil, that could immobilise arsenic by chemical adsorption, thereby reducing the risk of spreading of arsenic and lowering of its toxicity.  Simultaneously, the intention was to degrade PAH with hydroxyl radicals, forming from hydrolysis of water molecules in the soil. To test the effects of the technology on arsenic immobilisation and PAH degradation in sand and peat, experiments were set up on laboratory and intermediate scales. An additional experiment was performed in microcosms to test how varying redox conditions affect arsenic immobilisation in treated soil. 

Results showed that the concentrations of arsenic and PAH decreased in both soil and soil solution. However, low redox conditions and high organic matter content were two factors reducing the remediation efficiency. During anoxic conditions, an increase was shown in the exchangeable arsenic fraction. Moreover, the treatment was more efficient in sand than in peat, most likely due to its lower organic matter content. 

This study showed that electricity driven remediation can be suitable for arsenic immobilisation and simultaneous PAH degradation. It could be a potential alternative to landfilling, especially when taking site-specific conditions into account, and when combining it with other remediation techniques. However, more studies are needed to confirm that, and the exchangeable arsenic fraction needs to be reduced prior industrial implementation.

Abstract [sv]

Förorenad mark är ett globalt problem på grund av dess påverkan på hälsa och miljö. Träimpregneringsindustrin är ett exempel som har lämnat många platser samförorenade med polycykliska aromatiska kolväten (PAH) och metall(loider), såsom arsenik.

Trots de negativa miljömässiga och ekonomiska aspekterna av deponering är detta den vanligaste marksaneringstekniken i Sverige och Europa.

Denna studie syftade till att undersöka effekterna av eldriven sanering av mark förorenad med arsenik och PAH, för att bidra till kunskapen om att använda den som ett alternativ till deponering.

Tekniken kan praktiseras in situ, eftersom den använder elektricitet applicerad över elektroder som förs ner i jorden. Avsiktligt korroderande järnelektroderna syftade till att tillsätta järn till jorden, för att möjliggöra bildandet av järnoxider. Dessa järnoxider skulle kunna immobilisera arsenik genom kemisk adsorption och därigenom minska arsenikföroreningens toxicitet samt minska risken för dess spridning. Avsikten var att samtidigt bryta ner PAH med hydroxylradikaler, bildade genom hydrolys av vattenmolekyler i jorden. För att testa teknikens effekter på immobilisering av arsenik och nedbrytning av PAH i sand och torv, genomfördes experiment på laboratorie- och mellanstor skala. Ett ytterligare experiment utfördes i mikrokosmer för att testa hur varierande redoxförhållanden påverkar immobilisering av arsenik i behandlad jord.

Resultaten visade att koncentrationerna av arsenik och PAH minskade i både jord och grundvatten. Låga redoxförhållanden och hög halt organiskt material var dock två faktorer som minskade saneringseffekten. Under anoxiska förhållanden ökade den utbytbara arsenikfraktionen. Dessutom var behandlingen mer effektiv i sand än i torv, mest troligen på grund av sandens lägre innehåll av organiskt material.

Studien visade att eldriven sanering kan vara lämplig för immobilisering av arsenik och samtidig nedbrytning av PAH. Den skulle kunna vara ett potentiellt alternativ till deponering, särskilt när man tar hänsyn till platsspecifika förhållanden och när man kombinerar den med andra saneringstekniker. Fler studier behövs dock för att bekräfta detta och den utbytbara arsenikfraktionen behöver reduceras före industriell implementering.

Place, publisher, year, edition, pages
Luleå: Luleå University of Technology, 2025.
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
Keywords [en]
electrokinetic remediation, electrooxidation, iron(oxyhydr)oxides, soil solution
Keywords [sv]
förorenad mark, elektrokinetik, järnodixer, grundvatten
National Category
Other Environmental Engineering
Research subject
Waste Science and Technology
Identifiers
URN: urn:nbn:se:ltu:diva-113455ISBN: 978-91-8048-863-1 (print)ISBN: 978-91-8048-864-8 (print)OAI: oai:DiVA.org:ltu-113455DiVA, id: diva2:1970803
Public defence
2025-10-13, E632, Luleå University of Technology, Luleå, 09:00 (English)
Opponent
Supervisors
Available from: 2025-06-17 Created: 2025-06-17 Last updated: 2025-06-23Bibliographically approved
List of papers
1. Immobilisation of arsenic and simultaneous degradation of polycyclic aromatic hydrocarbons in soil in situ by modified electrooxidation
Open this publication in new window or tab >>Immobilisation of arsenic and simultaneous degradation of polycyclic aromatic hydrocarbons in soil in situ by modified electrooxidation
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2025 (English)In: Environmental Science and Pollution Research, ISSN 0944-1344, E-ISSN 1614-7499, Vol. 32, no 5, p. 2656-2667Article in journal (Refereed) Published
Abstract [en]

Improper management of wood impregnation chemicals and treated wood has led to soil contamination at many wood treatment sites, particularly with toxic substances like creosote oil and chromated copper arsenate (CCA). The simultaneous presence of these pollutants complicates the choice of soil remediation technologies, especially if they are to be applied in situ. In this laboratory study, we attempted to immobilise arsenic (As) and simultaneously degrade polycyclic aromatic hydrocarbons (PAHs) (constituents of creosote oil) by applying a modified electrochemical oxidation method. The supply of iron (Fe) amendments in contaminated soil was done using corroding Fe electrodes as an Fe source and applying an alternating polarity electrical current. Soil with a large fraction of organic matter (25%) and containing 505 mg kg−1 As and 5160 mg kg−1 16-PAHs was placed in Plexiglas cells equipped with porewater samplers and an iron electrode pair connected to a power supply unit. The porewater and percolating solution were periodically sampled and analysed over an 8-week period. The modified electrochemical soil treatment led to a decrease in the total concentration of 16-PAHs in soil by 56–68%. The amount of poorly crystalline Fe oxides in the soil substantially increased, especially close to the electrodes, enabling 76–89% of As to be bound to this most reactive Fe fraction. Nevertheless, over 10% of soil As remained in the most soluble and available fraction (exchangeable), most likely due to the decline in soil redox potential over time. This study suggests that electrochemical oxidation of organic soil with mixed contaminants could be used for in situ soil remediation but needs further improvement to achieve more efficient As immobilisation.

Place, publisher, year, edition, pages
Springer, 2025
Keywords
In situ remediation, Electrokinetics, Creosote, Wood impregnation, PAH
National Category
Other Environmental Engineering Soil Science
Research subject
Waste Science and Technology
Identifiers
urn:nbn:se:ltu:diva-111669 (URN)10.1007/s11356-024-35878-z (DOI)39808259 (PubMedID)2-s2.0-85217179371 (Scopus ID)
Funder
EU, Horizon 2020, 965945
Note

Full text license: CC BY

Available from: 2025-02-19 Created: 2025-02-19 Last updated: 2025-06-17
2. Immobilisation of arsenic in contaminated soil by electrokinetics in an outdoor experiment
Open this publication in new window or tab >>Immobilisation of arsenic in contaminated soil by electrokinetics in an outdoor experiment
2024 (English)In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 918, article id 170656Article in journal (Refereed) Published
Abstract [en]

Although landfilling is environmentally and economically unsustainable, it is the dominant soil remediation method in EU member states. This paper describes part of a study on mixed contaminants that investigated the stabilisation of arsenic (As) in contaminated soil in an outdoor box experiment with electrokinetic treatment (EK). The experiment was conducted in two 1 m3 boxes, each containing a 20 cm bottom layer of sand, overlaid with 20 cm of peat. In EK, a pulsating, low-voltage current was applied with the intention of corroding the zerovalent iron (Fe) electrodes, migrating ionic Fe species, and forming secondary iron minerals, thereby immobilizing As. Porewater samples were collected over two seasons to determine whether the treatment decreased the concentration of dissolved As. Sequential extraction was performed on the soil samples to determine whether the fraction of Fe-bound As increased. Reed canary grass was planted in one of the boxes during the second season and analysed for As uptake. The results showed that the treatment decreased the porewater As concentration in sand by 50–54 %, while the concentration of Fe increased. The sequential extraction of sand showed that the fraction of As bound to poorly crystalline Fe oxides increased during this time. This treatment effect was less visible in the peat. Moreover, the exchangeable As fraction increased in both peat and sand, most likely because of the decrease in redox potential at the end of the experiment. The plants grown in treated soil accumulated less As than those grown in untreated soil, indicating that the phytoavailable As fraction decreased. This study showed that EK remediation can be a suitable in situ remediation technique, mostly in sand. Future research should focus on redox control to further optimise EK remediation and ensure long-term As stability in treated soils.

Place, publisher, year, edition, pages
Elsevier B.V., 2024
Keywords
Electrokinetic remediation, Iron(oxyhydr)oxides, Phalaris arundinacea, Reed canary grass, Stabilisation
National Category
Other Environmental Engineering
Research subject
Waste Science and Technology
Identifiers
urn:nbn:se:ltu:diva-104319 (URN)10.1016/j.scitotenv.2024.170656 (DOI)001184123200001 ()38320707 (PubMedID)2-s2.0-85184522192 (Scopus ID)
Funder
EU, Horizon 2020, 965945
Note

Validerad;2024;Nivå 2;2024-02-20 (joosat);

Full text license: CC BY

Available from: 2024-02-20 Created: 2024-02-20 Last updated: 2025-06-17Bibliographically approved
3. Electrochemical oxidation of polycyclic aromatic hydrocarbons in soil co-contaminated with arsenic
Open this publication in new window or tab >>Electrochemical oxidation of polycyclic aromatic hydrocarbons in soil co-contaminated with arsenic
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2025 (English)In: Journal of Environmental Management, ISSN 0301-4797, E-ISSN 1095-8630, Vol. 388, article id 125978Article in journal (Refereed) Published
Abstract [en]

The wood preservation industry has contaminated numerous sites with polycyclic aromatic hydrocarbons (PAH). The aim of this study was to investigate the use of electrochemical oxidation (EO), without chemical additives, for in situ degradation of PAHs in soil co-contaminated with arsenic. Two 1 m3 boxes, each containing a 20 cm layer of contaminated sand overlaid with 20 cm of peat, were equipped with iron electrodes and placed outdoors. EO was applied using a pulsating direct current with alternating polarity, and its impact on PAH concentrations in soil and soil solution, as well as on the associated microbial community was assessed. Soil solution was sampled from the boxes over two seasons and analysed for PAH16 concentrations, showing an average decrease of 82 % by the end of the second season. This reduction was mainly observed in the medium and high molecular weight PAH fractions, suggesting that EO can effectively degrade more recalcitrant PAH compounds. The least reduction was seen in the low molecular weight PAH16, likely due to the replenishment from PAHs sorbed to the soil. Soil samples were taken from 12 different locations within the boxes, showing that PAH16 concentrations significantly decreased in 10 out of 12 sampling points, with a greater average reduction in sand (84 % decrease) compared to peat (69 % decrease). Microbial analyses of the soil samples revealed no significant changes in DNA concentrations across all taxa over time, with Gammaproteobacteria remaining the most abundant microorganisms in all samples, suggesting its ability to persist complex contamination.

Place, publisher, year, edition, pages
Elsevier, 2025
Keywords
PAH, soil solution, In situ soil remediation, Microbiological analyses
National Category
Environmental Sciences
Research subject
Waste Science and Technology
Identifiers
urn:nbn:se:ltu:diva-113051 (URN)10.1016/j.jenvman.2025.125978 (DOI)001502304800002 ()40446785 (PubMedID)2-s2.0-105006677037 (Scopus ID)
Funder
EU, Horizon 2020, 965945Swedish Research Council Formas, 2022-00864
Note

Validerad;2025;Nivå 2;2025-06-09 (u8);

Full text license: CC BY

Available from: 2025-06-09 Created: 2025-06-09 Last updated: 2025-06-24Bibliographically approved

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