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Pressurised hot water extraction ofn-alkanes and polyaromatic hydrocarbons in soil and sediment from the oil shale industry district in estonia

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Abstract

Background

Organic pollutants formed during thermal treatment of oil shale and then released from the solid waste (semicoke) to aquatic life are a major concern in Estonia. Efficient environmentally friendly techniques are being sought for the analysis of soil and sediments for pollutants and for the clean up of contaminated areas. The altered physico-chemical properties of pressurised hot water can be exploited in the extraction of organics from solid samples. For example, the relative permittivity, hydrogen bonding ability and viscosity of water are decreased and diffusivity is increased with temperature. In addition, water is environmentally friendly, cheap, non-flammable and readily available. In small-scale or pilot-scale operations, pressurised hot water extraction (PHWE) can also be used in the purification of contaminated soil and sediments.

Objective

PHWE and conventional Soxhlet extraction were applied to extract organic compounds from soil and sediment samples collected from various locations around a semi-coke mound in a mining district in northeastern Estonia. One important aim was to compare the extraction efficiencies of the two techniques. Another aim was to determine the pollutants in soil in the vicinity of the semi-coke mound and the sediments of two rivers (the Purtse River flowing to the Gulf of Finland and the Kohtla River feeding into the Purtse) and in canals between the Kohtla River and the semi-coke mound.

Methods

The PHWE equipment was self-constructed and applied with temperatures of 300 and 350°C (P = ca. 200 bar). Soxhlet extraction was carried out for 20 h with dichloromethane as a solvent. All extracts were cleaned up with a silica gel column, concentrated and analysed by gas chromatography-mass spectrometry (GC-MS). Organic matter contents of the samples were determined.

Results and Discussion

Alkanes and polyaromatic hydrocarbons (PAHs) were the main compounds found in the GC-MS analysis after.PHWE and Soxhlet extractions. In general, recoveries for short-chainn-alkanes (C10-C16) and PAHs with two benzene rings (i.e. naphthalene, acenaphthylene, acenaphthene and fluorene) were better with PHWE at 350°C than with Soxhlet extraction. These compounds are relatively volatile and may be lost during Soxhlet extraction. For longer chainn-alkanes, recoveries were better with Soxhlet extraction than with PHWE. The longer chain compounds are less polar than the shorter chain compounds and not so easily recovered by PHWE. For PAHs with more than two benzene rings, PHWE at 350°C produced roughly similar recoveries as Soxhlet extraction. PHWE extraction efficiency forn-alkanes was better at 350°C than at 300°C due to the lower polarity and increased diffusivity of water and better thermal desorption of the compounds at higher temperatures. For the same reasons, PHWE was generally more efficient at 350°C than at 300°C for PAHs, especially for the compounds with highest molar masses. Organic matter content was the greatest in the samples with high PAH and alkane concentrations, showing that organic matter is a good sink for hydrophobic micropollutants. The highest concentrations ofn-alkanes (maximum individual alkane concentrations ca. 8 µg/g) and PAHs (maximum individual PAH concentrations ca. 20 µg/g) were found in the soil under the semi-coke mound, showing that the compounds were flushed down with water. Almost concentrations ofn-alkanes and PAHs as high as under the mound were found within the mound and in sediment from the canal ca. 10 m from the mound. Sediment from the Kohtla River where it meets the Purtse River, ca. 14 km from the semi-coke mound, was also contaminated with the compounds. Only somen-alkanes were found at the mouth of the Purtse River indicating that the major part of the pollutants were accumulated in the sediments of the Kohtla River.

Conclusions

The PHWE equipment was reliable and safe to use. PHWE produced better recoveries for short-chain alkanes (C10-C16) and PAHs with two benzene rings than did Soxhlet extraction, but it was less efficient than Soxhlet for larger compounds. The two extraction methods together thus provide a good tool for extractingn-alkanes and PAHs. PAH and alkane concentrations were the most abundant in the samples with high organic matter content. The samples collected near the semi-coke mound and in the Kohtla River were contaminated withn-alkanes and PAHs, but only somen-alkanes were found in the Purtse River, showing that the heaviest contamination of soil and sediments was localised relatively close to the semi-coke mound.

Recommendations and Outlook

With PHWE, the hazardous organic solvents used in extraction processes can be replaced with water. Increasing the volume of the extraction vessel and applying a more efficient heating system and higher flow rate would enable the use of PHWE on a pilot-scale in the remediation of contaminated soil and sediments. With the present equipment, the PHWE-treated samples can also be oxidised directly on-line under supercritical conditions by feeding oxidant to the reactor situated after the extraction vessel. Organics can be completely destroyed with water and carbon monoxide, the main reaction products.

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Authors and Affiliations

  1. Department of Chemistry, Laboratory of Analytical Chemistry, University of Helsinki, PO Box 55, FIN-00014, Finland

    Juhani Kronholm, Johannes Kettunen, Kari Hartonen & Marja-Liisa Riekkola

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  1. Juhani Kronholm
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  2. Johannes Kettunen
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  3. Kari Hartonen
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  4. Marja-Liisa Riekkola
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Correspondence to Juhani Kronholm or Kari Hartonen.

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Kronholm, J., Kettunen, J., Hartonen, K. et al. Pressurised hot water extraction ofn-alkanes and polyaromatic hydrocarbons in soil and sediment from the oil shale industry district in estonia. J Soils & Sediments 4, 107–114 (2004). https://doi.org/10.1007/BF02991054

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