Page 1. VIEWPOINT▼ Defining BIOAVAILABILITY and Bioaccessibilityof Contaminated Soiland Sedimenti... more Page 1. VIEWPOINT▼ Defining BIOAVAILABILITY and Bioaccessibilityof Contaminated Soiland SedimentisComplicated KIRK. T. SEMPLE KIERON J. DOICK KEVIN C. JONES LANCASTER UNIVERSITY (UK) PETER BURAUEL FORSCHUNGSZENTRUM JÜLICH (GERMANY) ...
Laboratory based studies on the fate of organic contaminants in soil typically requires the test ... more Laboratory based studies on the fate of organic contaminants in soil typically requires the test compound(s) to be spiked into the test medium. Consequently, such studies are inherently dependent on the homogeneity of the contaminant within the spiked soil. Three blending methods were compared for the addition of a phenanthrene-transformer oil mixture into field-wet soil. Spiking homogeneity, reproducibility and artefacts were assessed based on dichloromethane and hydroxypropyl-beta-cyclodextrin chemical extractability, and bacterial mineralization. Spiking using a stainless-steel spoon, consistently produced good spike homogeneity as determined by sample oxidation, chemical extraction and mineralization, and was consistently more reliable than either the Waring blender or modified bench drill. Overall, neither transformer oil-concentration nor blending method influenced chemical extractability or mineralization of the PAH following 1 day equilibration. In general, spiking procedures require validation prior to use, as homogeneity cannot be assured.
Page 1. VIEWPOINT▼ Defining BIOAVAILABILITY and Bioaccessibilityof Contaminated Soiland Sedimenti... more Page 1. VIEWPOINT▼ Defining BIOAVAILABILITY and Bioaccessibilityof Contaminated Soiland SedimentisComplicated KIRK. T. SEMPLE KIERON J. DOICK KEVIN C. JONES LANCASTER UNIVERSITY (UK) PETER BURAUEL FORSCHUNGSZENTRUM JÜLICH (GERMANY) ...
Organic matter is considered to be the single most importantfactor limiting availability and mobi... more Organic matter is considered to be the single most importantfactor limiting availability and mobility of persistent organic pollutants (POPs) in soil. This study aimed to characterize the distribution of 14C-PCB (congeners 28 and 52) and 14C-PAH (fluoranthene and benzo[a]pyrene) residues in an Orthic Luvisol soil obtained from two lysimeter studies initiated in 1990 at the Agrosphere Institute (Forschungszentrum Jülich GmbH, Germany). The lysimeter soils contained a low-density OM fraction, isolated during soil washing, which contained a significant fraction (3-12%) of the total 14C-activity. Soils were also fractionated according to three particle sizes: >20, 20-2, and <2 microm. Relative affinity values of 14C-activity for the different particle sizes varied in the order 20-2 microm > (<2 microm) approximately (>20 microm) for the PCBs. Relative affinity values of 14C-activity for the different particle sizes varied in the order 20-2 microm > (<2 microm) > (>20 microm) for the PAHs. The distribution of 14C-PCB or 14C-PAH residues in the organic and inorganic matrixes of the particle-size fractions was determined using methyl isobutyl ketone (MIBK). 14C-PCB and 14C-PAH-associated activities were primarily located in the humin fraction of the 20-2 and <2 microm particle-size fractions of the soil. A small fraction was associated with the fulvic and humic acid fractions; these were quantitatively more important for the PAHs than the PCBs. There appeared to be a high degree of association of 14C-activity with the mineral fraction following MIBK separation of the humic fractions, ranging between 8 and 52% for 14C-PCBs and 57-80% for 14C-PAHs. The mineral (inorganic) component of the soils apparently played a significant (previously unreported) role in the sequestration of both PCBs 28 and 52 and the PAHs fluoranthene and benzo[a]pyrene.
Sequestration of hydrophobic organic contaminants (HOCs) in soils limits chemical and biological ... more Sequestration of hydrophobic organic contaminants (HOCs) in soils limits chemical and biological availability. Concerns exist regarding the long-term stability of sequestered contaminants in the environment, and stability needs to be demonstrated if bioavailability considerations are to be adopted into the risk assessment and remediation of contaminated land. The aim of the present study was to test the short-term influence of two organic amendments on the chemical extractability of HOC residues that had been present in soils for more than 12 years. The amendments investigated were cyclodextrin and transformer oil (a light, nonaqueous phase liquid [LNAPL]). The contaminants investigated were fluoranthene and benzo[a]pyrene in one soil and the polychlorinated biphenyls (PCBs) 28 and 52 in a second soil. The addition of cyclodextrin to the soils did not result in a significant increase in chemical extractability of the residues after a 36-d contact time. The addition of transformer oil resulted in an increase in chemical extractability of the PCBs after a 14-d soil-LNAPL contact time and a further increase after a 36-d contact time. The present study demonstrates that the chemical availability of aged HOCs in soil may be influenced by the presence of other chemicals and has implications for the long-term management of contaminated land.
Environmental Science and Pollution Research, 2013
Bioavailability has been used as a key indicator in chemical risk assessment yet poorly quantifie... more Bioavailability has been used as a key indicator in chemical risk assessment yet poorly quantified risk factor. Worldwide, the framework used to assess potentially contaminated sites is similar, and the decisions are based on threshold contaminant concentration. The uncertainty in the definition and measurement of bioavailability had limited its application to environment risk assessment and remediation. Last ten years have seen major developments in bioavailability research and acceptance. The use of bioavailability in the decision making process as one of the key variables has led to a gradual shift towards a more sophisticated risk-based approach. Now a days, many decision makers and regulatory organisations 'more readily accept' this concept. Bioavailability should be the underlying basis for risk assessment and setting remediation goals of those contaminated sites that pose risk to environmental and human health. This paper summarises the potential application of contaminant bioavailability and bioaccessibility to the assessment of sites affected by different contaminants, and the potential for this to be the underlying basis for sustainable risk assessment and remediation in Europe, North America and Australia over the coming decade.
The bioavailability of organic chemicals in soil and sediment is an important area of scientific ... more The bioavailability of organic chemicals in soil and sediment is an important area of scientific investigation by environmental scientists, but it is still poorly understood by regulators and industry working in the environmental sector. Regulators are starting to consider bioavailability within retrospective risk assessment frameworks for organic chemicals: by doing this, realistic decision-making on polluted environments is achievable, rather than relying on the traditional approach of using total extractable concentrations. However, implementation is not straightforward because the developments of bioavailability science have not always been translated into ready-to-use approaches for regulators. Similarly, bioavailability still remains largely unexplored within prospective regulatory frameworks dealing with approval and regulation of organic chemicals. This article discusses bioavailability concepts and methods, as well as possible pathways for the implementation of bioavailabil...
The aim of this study was to characterize the behaviour of a PAH-degrading bacterium to determine... more The aim of this study was to characterize the behaviour of a PAH-degrading bacterium to determine whether mineralization plateaus as a result of substrate removal, a decrease in microbial activity or nutrient availability in sterile soils over time. To investigate this, the mineralization of 14C-phenanthrene was measured until it plateaued; subsequently, additional 14C-phenanthrene, catabolic inocula or nutrients were introduced and mineralization was measured for a further 10 d. Cell numbers were also measured together with 14C-uptake into microbial biomass. Freshly added 14C-phenanthrene was rapidly metabolised by the microorganisms. Neither the addition of a catabolic inoculum nor nutrients affected the extent of 14C-phenanthrene mineralization. Cell numbers remained constant over time, with only a small amount of the 14C-activity incorporated into the microbial biomass. This study indicated that the termination of mineralization was due to the removal of available phenanthrene a...
There has been and continues to be considerable scientific interest in predicting bioremediation ... more There has been and continues to be considerable scientific interest in predicting bioremediation rates and endpoints. This requires the development of chemical techniques capable of reliably predicting the bioavailability of organic compounds to catabolically active soil microbes. A major issue in understanding the link between chemical extraction and bioavailability is the problem of definition; there are numerous definitions, of varying degrees of complexity and relevance, to the interaction between organic contaminants and microorganisms in soil. The aim of this review is to consider the bioavailability as a descriptor for the rate and extent of biodegradation and, in an applied sense, bioremediation of organic contaminants in soil. To address this, the review will (i) consider and clarify the numerous definitions of bioavailability and discuss the usefulness of the term 'bioaccessibility'; (ii) relate definition to the microbiological and chemical measurement of organic ...
Artificial soil is an important standard medium and reference material for soil ecotoxicity bioas... more Artificial soil is an important standard medium and reference material for soil ecotoxicity bioassays. Recent studies have documented the significant variability of their basic properties among different laboratories. Our study investigated (i) the variability of ten artificial soils from different laboratories by means of the fate, extractability and bioavailability of phenanthrene and lindane, and (ii) the relationships of these results to soil properties and ageing. Soils were spiked with (14)C-phenanthrene and (14)C-lindane, and the total residues, fractions extractable by hydroxypropyl-β-cyclodextrin, and the fractions of phenanthrene mineralizable by bacteria were determined after 1, 14, 28 and 56 days. Significant temporal changes in total residues and extractable and mineralizable fractions were observed for phenanthrene, resulting in large differences between soils after 56 days. Phenanthrene mineralization by indigenous peat microorganisms was suggested as the main driver ...
Oral bioavailability of benzo[a]pyrene (B[a]P) was studied in a swine model using eight spiked so... more Oral bioavailability of benzo[a]pyrene (B[a]P) was studied in a swine model using eight spiked soil samples after incubation for 50 and/or 90 days. Silica sand was used as a reference material and the relative bioavailability (RB) of B[a]P in soils was calculated as the quotient of the area under the plasma B[a]P curve (AUC) for soil and AUC for the silica sand. Significantly reduced RB was observed in all study soils after 90 days ageing, ranging from 22.1±0.4% to 62.7±10.1%, except for one very sandy soil (sand content 87.6%) where RB was unchanged (108.1±8.0%). Apart from this, bioavailability decreased during ageing with the decrease (from day 50 to day 90) being only significant for a clayey soil containing expandable clay minerals. Statistical analyses of B[a]P RB at day 90 (eight soils) and soil properties showed no direct correlation between RB and specific soil properties such as total organic carbon (TOC) and clay content which were commonly linked to organic contaminant s...
The application of plant protection products has the potential to significantly affect soil micro... more The application of plant protection products has the potential to significantly affect soil microbial community structure and function. However, the extent to which soil microbial communities from different trophic levels exhibit resistance and resilience to such compounds remains poorly understood. The resistance and resilience responses of a range of microbial communities (bacteria, fungi, archaea, pseudomonads, and nematodes) to different concentrations of the strobilurin fungicide, azoxystrobin were studied. A significant concentration-dependent decrease, and subsequent recovery in soil dehydrogenase activity was recorded, but no significant impact on total microbial biomass was observed. Impacts on specific microbial communities were studied using small subunit (SSU) rRNA terminal restriction fragment length polymorphism (T-RFLP) profiling using soil DNA and RNA. The application of azoxystrobin significantly affected fungal and nematode community structure and diversity but had...
Page 1. VIEWPOINT▼ Defining BIOAVAILABILITY and Bioaccessibilityof Contaminated Soiland Sedimenti... more Page 1. VIEWPOINT▼ Defining BIOAVAILABILITY and Bioaccessibilityof Contaminated Soiland SedimentisComplicated KIRK. T. SEMPLE KIERON J. DOICK KEVIN C. JONES LANCASTER UNIVERSITY (UK) PETER BURAUEL FORSCHUNGSZENTRUM JÜLICH (GERMANY) ...
Laboratory based studies on the fate of organic contaminants in soil typically requires the test ... more Laboratory based studies on the fate of organic contaminants in soil typically requires the test compound(s) to be spiked into the test medium. Consequently, such studies are inherently dependent on the homogeneity of the contaminant within the spiked soil. Three blending methods were compared for the addition of a phenanthrene-transformer oil mixture into field-wet soil. Spiking homogeneity, reproducibility and artefacts were assessed based on dichloromethane and hydroxypropyl-beta-cyclodextrin chemical extractability, and bacterial mineralization. Spiking using a stainless-steel spoon, consistently produced good spike homogeneity as determined by sample oxidation, chemical extraction and mineralization, and was consistently more reliable than either the Waring blender or modified bench drill. Overall, neither transformer oil-concentration nor blending method influenced chemical extractability or mineralization of the PAH following 1 day equilibration. In general, spiking procedures require validation prior to use, as homogeneity cannot be assured.
Page 1. VIEWPOINT▼ Defining BIOAVAILABILITY and Bioaccessibilityof Contaminated Soiland Sedimenti... more Page 1. VIEWPOINT▼ Defining BIOAVAILABILITY and Bioaccessibilityof Contaminated Soiland SedimentisComplicated KIRK. T. SEMPLE KIERON J. DOICK KEVIN C. JONES LANCASTER UNIVERSITY (UK) PETER BURAUEL FORSCHUNGSZENTRUM JÜLICH (GERMANY) ...
Organic matter is considered to be the single most importantfactor limiting availability and mobi... more Organic matter is considered to be the single most importantfactor limiting availability and mobility of persistent organic pollutants (POPs) in soil. This study aimed to characterize the distribution of 14C-PCB (congeners 28 and 52) and 14C-PAH (fluoranthene and benzo[a]pyrene) residues in an Orthic Luvisol soil obtained from two lysimeter studies initiated in 1990 at the Agrosphere Institute (Forschungszentrum Jülich GmbH, Germany). The lysimeter soils contained a low-density OM fraction, isolated during soil washing, which contained a significant fraction (3-12%) of the total 14C-activity. Soils were also fractionated according to three particle sizes: >20, 20-2, and <2 microm. Relative affinity values of 14C-activity for the different particle sizes varied in the order 20-2 microm > (<2 microm) approximately (>20 microm) for the PCBs. Relative affinity values of 14C-activity for the different particle sizes varied in the order 20-2 microm > (<2 microm) > (>20 microm) for the PAHs. The distribution of 14C-PCB or 14C-PAH residues in the organic and inorganic matrixes of the particle-size fractions was determined using methyl isobutyl ketone (MIBK). 14C-PCB and 14C-PAH-associated activities were primarily located in the humin fraction of the 20-2 and <2 microm particle-size fractions of the soil. A small fraction was associated with the fulvic and humic acid fractions; these were quantitatively more important for the PAHs than the PCBs. There appeared to be a high degree of association of 14C-activity with the mineral fraction following MIBK separation of the humic fractions, ranging between 8 and 52% for 14C-PCBs and 57-80% for 14C-PAHs. The mineral (inorganic) component of the soils apparently played a significant (previously unreported) role in the sequestration of both PCBs 28 and 52 and the PAHs fluoranthene and benzo[a]pyrene.
Sequestration of hydrophobic organic contaminants (HOCs) in soils limits chemical and biological ... more Sequestration of hydrophobic organic contaminants (HOCs) in soils limits chemical and biological availability. Concerns exist regarding the long-term stability of sequestered contaminants in the environment, and stability needs to be demonstrated if bioavailability considerations are to be adopted into the risk assessment and remediation of contaminated land. The aim of the present study was to test the short-term influence of two organic amendments on the chemical extractability of HOC residues that had been present in soils for more than 12 years. The amendments investigated were cyclodextrin and transformer oil (a light, nonaqueous phase liquid [LNAPL]). The contaminants investigated were fluoranthene and benzo[a]pyrene in one soil and the polychlorinated biphenyls (PCBs) 28 and 52 in a second soil. The addition of cyclodextrin to the soils did not result in a significant increase in chemical extractability of the residues after a 36-d contact time. The addition of transformer oil resulted in an increase in chemical extractability of the PCBs after a 14-d soil-LNAPL contact time and a further increase after a 36-d contact time. The present study demonstrates that the chemical availability of aged HOCs in soil may be influenced by the presence of other chemicals and has implications for the long-term management of contaminated land.
Environmental Science and Pollution Research, 2013
Bioavailability has been used as a key indicator in chemical risk assessment yet poorly quantifie... more Bioavailability has been used as a key indicator in chemical risk assessment yet poorly quantified risk factor. Worldwide, the framework used to assess potentially contaminated sites is similar, and the decisions are based on threshold contaminant concentration. The uncertainty in the definition and measurement of bioavailability had limited its application to environment risk assessment and remediation. Last ten years have seen major developments in bioavailability research and acceptance. The use of bioavailability in the decision making process as one of the key variables has led to a gradual shift towards a more sophisticated risk-based approach. Now a days, many decision makers and regulatory organisations 'more readily accept' this concept. Bioavailability should be the underlying basis for risk assessment and setting remediation goals of those contaminated sites that pose risk to environmental and human health. This paper summarises the potential application of contaminant bioavailability and bioaccessibility to the assessment of sites affected by different contaminants, and the potential for this to be the underlying basis for sustainable risk assessment and remediation in Europe, North America and Australia over the coming decade.
The bioavailability of organic chemicals in soil and sediment is an important area of scientific ... more The bioavailability of organic chemicals in soil and sediment is an important area of scientific investigation by environmental scientists, but it is still poorly understood by regulators and industry working in the environmental sector. Regulators are starting to consider bioavailability within retrospective risk assessment frameworks for organic chemicals: by doing this, realistic decision-making on polluted environments is achievable, rather than relying on the traditional approach of using total extractable concentrations. However, implementation is not straightforward because the developments of bioavailability science have not always been translated into ready-to-use approaches for regulators. Similarly, bioavailability still remains largely unexplored within prospective regulatory frameworks dealing with approval and regulation of organic chemicals. This article discusses bioavailability concepts and methods, as well as possible pathways for the implementation of bioavailabil...
The aim of this study was to characterize the behaviour of a PAH-degrading bacterium to determine... more The aim of this study was to characterize the behaviour of a PAH-degrading bacterium to determine whether mineralization plateaus as a result of substrate removal, a decrease in microbial activity or nutrient availability in sterile soils over time. To investigate this, the mineralization of 14C-phenanthrene was measured until it plateaued; subsequently, additional 14C-phenanthrene, catabolic inocula or nutrients were introduced and mineralization was measured for a further 10 d. Cell numbers were also measured together with 14C-uptake into microbial biomass. Freshly added 14C-phenanthrene was rapidly metabolised by the microorganisms. Neither the addition of a catabolic inoculum nor nutrients affected the extent of 14C-phenanthrene mineralization. Cell numbers remained constant over time, with only a small amount of the 14C-activity incorporated into the microbial biomass. This study indicated that the termination of mineralization was due to the removal of available phenanthrene a...
There has been and continues to be considerable scientific interest in predicting bioremediation ... more There has been and continues to be considerable scientific interest in predicting bioremediation rates and endpoints. This requires the development of chemical techniques capable of reliably predicting the bioavailability of organic compounds to catabolically active soil microbes. A major issue in understanding the link between chemical extraction and bioavailability is the problem of definition; there are numerous definitions, of varying degrees of complexity and relevance, to the interaction between organic contaminants and microorganisms in soil. The aim of this review is to consider the bioavailability as a descriptor for the rate and extent of biodegradation and, in an applied sense, bioremediation of organic contaminants in soil. To address this, the review will (i) consider and clarify the numerous definitions of bioavailability and discuss the usefulness of the term 'bioaccessibility'; (ii) relate definition to the microbiological and chemical measurement of organic ...
Artificial soil is an important standard medium and reference material for soil ecotoxicity bioas... more Artificial soil is an important standard medium and reference material for soil ecotoxicity bioassays. Recent studies have documented the significant variability of their basic properties among different laboratories. Our study investigated (i) the variability of ten artificial soils from different laboratories by means of the fate, extractability and bioavailability of phenanthrene and lindane, and (ii) the relationships of these results to soil properties and ageing. Soils were spiked with (14)C-phenanthrene and (14)C-lindane, and the total residues, fractions extractable by hydroxypropyl-β-cyclodextrin, and the fractions of phenanthrene mineralizable by bacteria were determined after 1, 14, 28 and 56 days. Significant temporal changes in total residues and extractable and mineralizable fractions were observed for phenanthrene, resulting in large differences between soils after 56 days. Phenanthrene mineralization by indigenous peat microorganisms was suggested as the main driver ...
Oral bioavailability of benzo[a]pyrene (B[a]P) was studied in a swine model using eight spiked so... more Oral bioavailability of benzo[a]pyrene (B[a]P) was studied in a swine model using eight spiked soil samples after incubation for 50 and/or 90 days. Silica sand was used as a reference material and the relative bioavailability (RB) of B[a]P in soils was calculated as the quotient of the area under the plasma B[a]P curve (AUC) for soil and AUC for the silica sand. Significantly reduced RB was observed in all study soils after 90 days ageing, ranging from 22.1±0.4% to 62.7±10.1%, except for one very sandy soil (sand content 87.6%) where RB was unchanged (108.1±8.0%). Apart from this, bioavailability decreased during ageing with the decrease (from day 50 to day 90) being only significant for a clayey soil containing expandable clay minerals. Statistical analyses of B[a]P RB at day 90 (eight soils) and soil properties showed no direct correlation between RB and specific soil properties such as total organic carbon (TOC) and clay content which were commonly linked to organic contaminant s...
The application of plant protection products has the potential to significantly affect soil micro... more The application of plant protection products has the potential to significantly affect soil microbial community structure and function. However, the extent to which soil microbial communities from different trophic levels exhibit resistance and resilience to such compounds remains poorly understood. The resistance and resilience responses of a range of microbial communities (bacteria, fungi, archaea, pseudomonads, and nematodes) to different concentrations of the strobilurin fungicide, azoxystrobin were studied. A significant concentration-dependent decrease, and subsequent recovery in soil dehydrogenase activity was recorded, but no significant impact on total microbial biomass was observed. Impacts on specific microbial communities were studied using small subunit (SSU) rRNA terminal restriction fragment length polymorphism (T-RFLP) profiling using soil DNA and RNA. The application of azoxystrobin significantly affected fungal and nematode community structure and diversity but had...
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