Physicochemical soil parameters affecting sequestration and mycobacterial biodegradation of polycyclic aromatic hydrocarbons in soil

Six soils, obtained from grasslands and wooded areas in Northeastern Illinois, were physicochemically characterized. Measured parameters included total organic carbon (TOC) content, contents of humic acid, fulvic acid and humin, pore volume and pore size distribution, and chemical makeup of soil organic matter (determined using solid-state ¹³C-NMR). Moistened, gamma-sterilized soils were spiked with 200 ppm of either phenanthrene or pyrene (including ¹⁴C label); following 0, 40, or 120 days of aging, the contaminant-spiked soils were then inoculated with Mycobacterium austroafricanum strain GTI-23, and evolution of ¹⁴CO₂ was assessed over a 28-day period. Results for both phenanthrene and pyrene indicated that increased contact time led to increased sequestration and reduced biodegradation, and that TOC content was the most important parameter governing these processes. One soil, although only tested with phenanthrene, showed significantly lower-than-expected sequestration (higher-than-expected mineralization) after 40 days of aging, despite a very high TOC value (>24%). Because the level of sequestration in this soil was proportional to the others after 120 days of aging, this implies some difference in the temporal progression of sequestration in this soil, although not in its final result. The primary distinguishing feature of this soil was its considerably elevated fulvic acid content. Further experiments showed that addition of exogenous fulvic acid to a soil with very low endogenous humic acids/fulvic acids content greatly enhanced pyrene mineralization by M. austroafricanum. Extractabilities of 13 three- to six-ring coal tar PAHs in n-butanol from the six soils after 120 days of sequestration were strongly TOC-dependent; however, there was no discernible correlation between n-butanol extractability and mycobacterial PAH mineralization.     

Sorption of atrazine and metolachlor by earthworm surface castings and soil

Atrazine and metolachlor were more strongly retained on earthworm (Lumbricus terrestris L.) castings than on soil, suggesting that earthworm castings at the surface or at depth can reduce herbicide movement in soil. Herbicide sorption by castings was related to the food source available to the earthworms. Both atrazine and metolachlor sorption increased with increasing organic carbon (C) content in castings, and Freundlich constants (Kf values) generally decreased in the order: soybean-fed > corn-fed > not-fed-earthworm-castings. The amount of atrazine or metolachlor sorbed per unit organic carbon (Koc values) was significantly greater for corn-castings compared with other castings, or soil, suggesting that the composition of organic matter in castings is also an important factor in determining the retention of herbicides in soils. Herbicide desorption was dependent on both the initial herbicide concentration, and the type of absorbent. At small equilibrium herbicide concentrations, atrazine desorption was significantly greater from soil than from any of the three casting treatments. At large equilibrium herbicide concentrations, however, the greater organic C content in castings had no significant effect on atrazine desorption, relative to soil. For metolachlor, regardless of the equilibrium herbicide concentration, desorption from soybean- and corn-castings treatments was always less than desorption from soil and not-fed earthworm castings treatments. The results of this study indicate that, under field conditions, the extent of herbicide retention on earthworm castings will tend to be related to crop and crop residue management practices.     

Sorption of atrazine and metolachlor by earthworm surface castings and soil

Abstract

Atrazine and metolachlor were more strongly retained on earthworm (Lumbricus terrestris L.) castings than on soil, suggesting that earthworm castings at the surface or at depth can reduce herbicide movement in soil. Herbicide sorption by castings was related to the food source available to the earthworms. Both atrazine and metolachlor sorption increased with increasing organic carbon (C) content in castings, and Freundlich constants (K_f values) generally decreased in the order: soybean‐fed > corn‐fed > not‐fed‐earthworm‐castings. The amount of atrazine or metolachlor sorbed per unit organic carbon (K_oc values) was significantly greater for corn‐castings compared with other castings, or soil, suggesting that the composition of organic matter in castings is also an important factor in determining the retention of herbicides in soils. Herbicide desorption was dependent on both the initial herbicide concentration, and the type of absorbent. At small equilibrium herbicide concentrations, atrazine desorption was significantly greater from soil than from any of the three casting treatments. At large equilibrium herbicide concentrations, however, the greater organic C content in castings had no significant effect on atrazine desorption, relative to soil. For metolachlor, regardless of the equilibrium herbicide concentration, desorption from soybean‐ and corn‐castings treatments was always less than desorption from soil and not‐fed earthworm castings treatments. The results of this study indicate that, under field conditions, the extent of herbicide retention on earthworm castings will tend to be related to crop and crop residue management practices.     

Evaluation of impacts of soil fractions on phenanthrene sorption

Phenanthrene sorption to soils and soil fractions was investigated using two contrasting soils with different clay mineral and organic carbon (OC) contents in an attempt to evaluate the contribution of each soil fraction to phenanthrene sorption and the applicability of the carbon-normalized distribution constant (K(OC)) in soils. Sorbents were characterized using surface analysis, solid-state (13)C NMR analysis, and glass transition temperature (T(g)) analysis to gain a insight into the chemical nature of OC in soils. Dissolved organic carbon (DOC) in the soil solution impeded the phenanthrene sorption, while humins accounted for the predominant phenanthrene sorption in soils. The contribution of OC to phenanthrene sorption in soil would be overestimated if only a K(OC)-approach was adopted, since clay minerals could account for much of the sorption, especially when OC was low in soils. Nitrogen gas was shown to be inappropriate for probing non-polar sorption capacity. The results obtained highlight the importance of clay minerals in governing the sorption of phenanthrene in soil, and emphasize the inapplicability of the carbon-normalized distribution coefficient K(OC) in soils.     

Pesticide adsorption on a calcareous soil modified with sewage sludge and quaternary alkyl-ammonium cationic surfactants

BACKGROUND, AIM AND SCOPE: Pesticides are often found in soil as a result of their application to control pests. They can be transported on soil particles to surface waters or they can lixiviate and reach other environmental compartments. Soil modification with amendments, such as sewage sludge, and with surfactants, h been proposed to reduce pesticide environmental fate. METHODS: The sorption of atrazine, methidathion and diazinon using the batch technique has been studied on non-modified soil and soil modified with sewage sludge and cationic surfactants, as well as the effect of their addition on soil properties such as organic carbon (OC) content and exchange cations. RESULTS AND DISCUSSION: The OC content of the surfactant modified soils was the highest with the surfactant with the longest hydrocarbon chain (hexadecyltrimethyl ammonium bromide, HDTMA). The results of the OC content run in parallel with the increase in pesticide retention. When the sorption was n malized to soil OC content, the retention induced by addition of HDTMA was still the highest, which is an indication that the organic matter derived from the organic cations is a more effective medium to retain dissolved contaminants, than organic matter from native soil. The addition of sewage sludge to the soil did only result in a slight increase of the soil CEC and, hence, moderately affected the ability of the cationic surfactant to retain the pesticides. CONCLUSIONS: The addition of cationic surfactants to soil would possibly reduce the movement to groundwater of atrazine, methidathion and diazinon. In the case of HDTMA, the decrease in sorption at high surfactant loadings was very slow, being that the surfactant was able to retain the pesticides at concentration values which clearly exceeded the monolayer coverage. RECOMMENDATIONS AND PERSPECTIVES: Contamination by pesticides, which are present in the soil due to their direct input in this medium or to spills or illegal tipping, may be hindered from migration to groundwater by application of a cationic surfactant.     

Effect of soil aggregation on the biodegradation of phenanthrene aged in soil

A study was conducted to determine the possible role of soil aggregates in the sequestration of phenanthrene and thus in the declined biodegradation of the hydrocarbon. Phenanthrene aged in Lima loam (2-mm aggregates) showed declined biodegradation with time of aging to the test bacterium P5-2 capable of using sorbed phenanthrene. In contrast, the compound aged in a soil reconstructed with 68% clay-silt and 32% sand that had been separated from the Lima loam was readily mineralized. The percentages of each fraction used were the same as those of the original soil. Biodegradation of aged phenanthrene was not affected significantly by varying the ratios of each fraction in reconstructed mixtures. In experiments with Lima loam, its clay-silt fraction, and its sand fraction, mineralization extent was much lower in soil aggregates compared with the other samples while all had similar organic carbon content of ca. 1.51%. This suggests that aggregation may be another important determinant in the reduced biodegradation of aged phenanthrene.     

Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

Separating the effects of organic matter-mineral interactions and organic matter chemistry on the sorption of diuron and phenanthrene

Even though it is well established that soil C content is the primary determinant of the sorption affinity of soils for non-ionic compounds, it is also clear that organic carbon-normalized sorption coefficients (K(OC)) vary considerably between soils. Two factors that may contribute to K(OC) variability are variations in organic matter chemistry between soils and interactions between organic matter and soil minerals. Here, we quantify these effects for two non-ionic sorbates-diuron and phenanthrene. The effect of organic matter-mineral interactions were evaluated by comparing K(OC) for demineralized (HF-treated) soils, with K(OC) for the corresponding whole soils. For diuron and phenanthrene, average ratios of K(OC) of the HF-treated soils to K(OC) of the whole soils were 2.5 and 2.3, respectively, indicating a substantial depression of K(OC) due to the presence of minerals in the whole soils. The effect of organic matter chemistry was determined by correlating K(OC) against distributions of C types determined using solid-state (13)C NMR spectroscopy. For diuron, K(OC) was positively correlated with aryl C and negatively correlated with O-alkyl C, for both whole and HF-treated soils, whereas for phenanthrene, these correlations were only present for the HF-treated soils. We suggest that the lack of a clear effect of organic matter chemistry on whole soil K(OC) for phenanthrene is due to an over-riding influence of organic matter-mineral interactions in this case. This hypothesis is supported by a correlation between the increase in K(OC) on HF-treatment and the soil clay content for phenanthrene, but not for diuron.     

Effect of Pinus radiata derived biochars on soil sorption and desorption of phenanthrene

Biochars are anthropogenic carbonaceous sorbent and their influences on the sorption of environmental contaminants need to be characterized. Here we evaluated the effect of Pinus radiata derived biochars on soil sorption and desorption of phenanthrene. Two biochars separately produced at 350 °C and 700 °C and three soils were tested. Biochar amendment generally enhanced the soil sorption of phenanthrene. The biochar produced at 700 °C generally showed a greater ability at enhancing a soil’s sorption ability than that prepared at 350 °C. The single-step desorption measurement showed an apparent hysteresis in biochar-amended soils. After 28 d equilibration, the sorptive capacity of biochar-amended soil (with an organic carbon content of 0.16%) significantly decreased. This study clearly suggested that biochar application enhanced soil sorption of hydrophobic organic compounds, but the magnitude of enhancement depended on the preparation of biochars, the indigenous soil organic carbon levels, and the contact time between soil and biochar.     

The effect of soil organic matter on fate of polycyclic aromatic hydrocarbons in soil: A microcosm study

A microcosm study was conducted to address the influences of air-soil partition and sequestration on the fate of polycyclic aromatic hydrocarbons (PAHs) in soil. Sterilized and unsterilized soils with soil organic carbon (SOC) content ranging from 0.23 to 7.06% were incubated in a chamber with six PAHs supplied through air. After 100 d of incubation when the system approached pseudo-steady state, the PAHs concentrations in the unsterilized soils still correlated with SOC significantly, while the association did not exist for those sterilized. The lower degradation rate in the soil with higher SOC was likely the major reason for the association between SOC and PAHs concentrations, while the decreased surface porosity likely suppressed such correlation for the sterilized samples. The results indicated that the sequestration was likely the major mechanism for the accumulation of PAHs in soils, while both of the soil porosity and PAHs properties had observed influences.     

Enhancement of phenanthrene adsorption on a clayey soil and clay minerals by coexisting lead or cadmium

Phenanthrene is commonly present together with heavy metals at many contaminated sites. This study investigated the influence of coexisting lead (Pb²⁺) or cadmium (Cd²⁺) on phenanthrene adsorption on soils. Batch experiments were conducted under different geochemical conditions including pH, mineral structure, organic matter content, and varying amounts of heavy metals. The results showed that the presence of heavy metals in solution at a fixed pH of 5.8 ± 0.1 enhanced phenanthrene adsorption, the extent of which was closely related to the concentrations and the electro-negativity of the metals. The enhancement on phenanthrene adsorption was positively correlated to the amount of adsorbed metals. Although Cd²⁺ is a softer Lewis acid, Pb²⁺ displayed a more significant effect as it was adsorbed to a greater extent on the soil surfaces. Thus, density of cation accumulation appears to be more influential than metal softness in enhancing phenanthrene adsorption. Moreover, with a portion of organic matter removed by heating at 550 °C, there was a stronger enhancement of phenanthrene adsorption by coexisting Pb²⁺, indicating an increasingly dominant mechanisms associated with Pb²⁺ at a lower organic matter content. Similar enhancement phenomenon was observed on bentonite and kaolinite, probably resulting from the cation-π bonding between the adsorbed soft metal cations and the aromatic ring of phenanthrene in solution. The desorption experiments further suggested that the bonding of phenanthrene adsorption was strengthened in the presence of Pb²⁺ and that a larger proportion of adsorbed phenanthrene remained on the soils (residual fraction) even after sequential methanol extractions. Further spectroscopic analyses and surface characterization are required to provide direct evidence of the formation and relative significance of cation-π bond for phenanthrene adsorption.     

Fugacity modelling to predict the distribution of organic contaminants in the soil:oil matrix of constructed biopiles

Level I and II fugacity approaches were used to model the environmental distribution of benzene, anthracene, phenanthrene, 1-methylphenanthrene and benzo[a]pyrene in a four phase biopile system, accounting for air, water, mineral soil and non-aqueous phase liquid (oil) phase. The non-aqueous phase liquid (NAPL) and soil phases were the dominant partition media for the contaminants in each biopile and the contaminants differed markedly in their individual fugacities. Comparison of three soils with different percentage of organic carbon (% org C) showed that the % org C influenced contaminant partitioning behaviour. While benzene showed an aqueous concentration worthy of note for leachate control during biopiling, other organic chemicals showed that insignificant amount of chemicals leached into the water, greatly reducing the potential extent of groundwater contamination. Level II fugacity model showed that degradation was the dominant removal process except for benzene. In all three biopile systems, the rate of degradation of benzo(a)pyrene was low, requiring more than 12 years for soil concentrations from a spill of about 25 kg (100 mol) to be reduced to a concentration of 0.001 microgg(-1). The removal time of 1-methylphenanthrene and either anthracene or phenanthrene was about 1 and 3 years, respectively. In contrast, benzene showed the highest degradation rate and was removed after 136 days in all biopile systems. Overall, this study confirms the association of risk critical contaminants with the residual saturation in treated soils and reinforces the importance of accounting for the partitioning behaviour of both NAPL and soil phases during the risk assessment of oil-contaminated sites.     

Influence of soil moisture on the sequestration of organic compounds in soil

A study was conducted as a part of continuing investigation of the effect of soil moisture on the sequestration of organic compounds aged in the soil. Here, experiments focused on the effects of moisture changes within the soil before, during, and after contaminant addition. The extractability of aged (68 d) phenanthrene was greater from soil that had been subjected to wetting and drying cycles prior to solute addition as compared to soil initially maintained at constant moisture. The recovery of phenanthrene added to moist soil was increased relative to extractability from soil that was air-dried at the time of the contaminant addition. Repeated wetting and drying of soil after the addition of atrazine or phenanthrene resulted in decreased extractability of the compounds as compared to samples maintained at constant moisture. A method for rapidly sequestering contaminants is proposed and may be useful in limiting the time required for laboratory studies involving “aged” contaminants. These data build upon the findings of earlier work from our laboratory and indicate that changes in the moisture conditions of soil can affect the availability of sequestered contaminants possibly through alterations in the structure of the natural solid.     

Bacterial communities and enzyme activities of PAHs polluted soils

Three soils (i.e. a Belgian soil, B-BT, a German soil, G, and an Italian agricultural soil, I-BT) with different properties and hydrocarbon-pollution history with regard to their potential to degrade phenanthrene were investigated. A chemical and microbiological evaluation of soils was done using measurements of routine chemical properties, bacterial counts and several enzyme activities. The three soils showed different levels of polycyclic aromatic hydrocarbons (PAHs), being their contamination strictly associated to their pollution history. High values of enzyme activities and culturable heterotrophic bacteria were detected in the soil with no or negligible presence of organic pollutants. Genetic diversity of soil samples and enrichment cultures was measured as bands on denaturing gradient gel electrophoresis (DGGE) of amplified 16S rDNA sequences from the soil and enrichment community DNAs. When analysed by Shannon index (H'), the highest genetic biodiversity (H'=2.87) was found in the Belgian soil B-BT with a medium-term exposition to PAHs and the poorest biodiversity (H'=0.85) in the German soil with a long-term exposition to alkanes and PAHs and where absence, or lower levels of enzyme activities were measured. For the Italian agricultural soil I-BT, containing negligible amounts of organic pollutants but the highest Cu content, a Shannon index=2.13 was found. The enrichment of four mixed cultures capable of degrading solid phenanthrene in batch liquid systems was also studied. Phenanthrene degradation rates in batch systems were culture-dependent, and simple (one-slope) and complex (two-slope) kinetic behaviours were observed. The presence of common bands of microbial species in the cultures and in the native soil DNA indicated that those strains could be potential in situ phenanthrene degraders. Consistent with this assumption are the decrease of PAH and phenanthrene contents of Belgian soil B-BT and the isolation of phenanthrene-degrading bacteria. From the fastest phenanthrene-degrading culture C(B-BT), representative strains were identified as Achromobacter xylosoxidans (100%), Methylobacterium sp. (99%), Rhizobium galegae (99%), Rhodococcus aetherovorans (100%), Stenotrophomonas acidaminiphila (100%), Alcaligenes sp. (99%) and Aquamicrobium defluvium (100%). DGGE-profiles of culture C(B-BT) showed bands attributable to Rhodococcus, Achromobacter, Methylobacterium rhizobium, Alcaligenes and Aquamicrobium. The isolation of Rhodococcus aetherovorans and Methylobacterium sp. can be consistent with the hypothesis that different phenanthrene-degrading strategies, cell surface properties, or the presence of xenobiotic-specific membrane carriers could play a role in the uptake/degradation of solid phenanthrene.     

The influence of pH and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants

The experiments were done to investigate the effect of soil pH and organic matter content on EDTA-extractable heavy metal contents in soils and heavy metal concentrations in rice straw and grains. EDTA-extractable Cr contents in soils and concentrations in rice tissues were negatively correlated with soil pH, but positively correlated with organic matter content. The combination of soil pH and organic matter content would produce the more precise regression models for estimation of EDTA-Cu, Pb and Zn contents in soils, demonstrating the distinct effect of the two factors on the availability of these heavy metals in soils. Soil pH greatly affected heavy metal concentrations in rice plants. Furthermore, inclusion of other soil properties in the stepwise regression analysis improved the regression models for predicting straw Fe and grain Zn concentrations, indicating that other soil properties should be taken into consideration for precise predicting of heavy metal concentrations in rice plants.     

Impact of long-term wastewater irrigation on sorption and transport of atrazine in Mexican agricultural soils

In the Mezquital Valley, Mexico, crops have been irrigated with untreated municipal wastewater for more than a century. Atrazine has been applied to maize and alfalfa grown in the area for weed control for 15 years. Our objectives were to analyse (i) how wastewater irrigation affects the filtering of atrazine, and (ii) if the length of irrigation has a significant impact. We compared atrazine sorption to Phaeozems that have been irrigated with raw wastewater for 35 (P35) and 85 (P85) years with sorption to a non-irrigated (P0) Phaeozem soil under rainfed agriculture. The use of bromide as an inert water tracer in column experiments and the subsequent analysis of the tracers’ breakthrough curves allowed the calibration of the hydrodynamic parameters of a two-site non equilibrium convection-dispersion model. The quality of the irrigation water significantly altered the soils’ hydrodynamic properties (hydraulic conductivity, dispersivity and the size of pores that are hydraulically active). The impacts on soil chemical properties (total organic carbon content and pH) were not significant, while the sodium adsorption ratio was significantly increased. Sorption and desorption isotherms, determined in batch and column experiments, showed enhanced atrazine sorption and reduced and slower desorption in wastewater-irrigated soils. These effects increased with the length of irrigation. The intensified sorption-desorption hysteresis in wastewater-irrigated soils indicated that the soil organic matter developed in these soils had fewer high-energy, easily accessible sorption sites available, leading to lower and slower atrazine desorption rates. This study leads to the conclusion that wastewater irrigation decreases atrazine mobility in the Mezquital valley Phaeozems by decreasing the hydraulic conductivity and increasing the soil's sorption capacity.     

Effect of arbuscular mycorrhizal fungus (Glomus caledonium) on the accumulation and metabolism of atrazine in maize (Zea mays L.) and atrazine dissipation in soil

Effects of an arbuscular mycorrhizal (AM) fungus (Glomus caledonium) on accumulation and metabolism of atrazine in maize grown in soil contaminated with different concentrations of atrazine were investigated in a series of pot experiments. Roots of mycorrhizal plants accumulated more atrazine than non-mycorrhizal roots. In contrast, atrazine accumulation in shoot decreased in mycorrhizal compared with non-mycorrhizal plants. No atrazine derivatives were detected in the soil, either with or without mycorrhizal colonization. However, atrazine metabolites, deethylatrazine (DEA) and deisopropylatrazine (DIA), were detected in plant roots and the AM colonization enhanced the metabolism. After plant harvest atrazine concentrations decreased markedly in the soils compared to the initial concentrations. The decreases were the most in rhizosphere soil and then near-rhizosphere soil and the least in bulk soil. Mycorrhizal treatment enhanced atrazine dissipation in the near-rhizosphere and bulk soils irrespective of atrazine application rates.     

The ratio of clay content to total organic carbon content is a useful parameter to predict adsorption of the herbicide butachlor in soils

Thirteen soils collected from 11 provinces in eastern China were used to investigate the butachlor adsorption. The results indicated that the total organic carbon (TOC) content, clay content, amorphous Fe2O3 content, silt content, CEC, and pH had a combined effect on the butachlor sorption on soil. Combination of the data obtained from the 13 soils in the present study with other 23 soil samples reported by other researchers in the literature showed that Koc would be a poor predictive parameter for butachlor adsorption on soils with TOC content higher than 4.0% and lower than 0.2%. The soils with the ratio of clay content to TOC content (RCO) values less than 60 adsorbed butachlor mainly by the partition into soil organic matter matrix. The soils with RCO values higher than 60 apparently adsorbed butachlor by the combination of the partition into soil organic matter matrix and adsorption on clay surface.     

Impact of chemical oxidation on soil quality

Oxidation treatment helps to reduce the polycyclic aromatic hydrocarbon (PAH) load in contaminated soils but it may also have an effect on the soil quality. The impact of permanganate and Fenton oxidation on soil quality is investigated. Soil quality is restricted here to the potential for plant growth. Soil samples were collected from an agricultural field (S1) and a former coking plant (S4). Agricultural soil was spiked with phenanthrene (PHE) and pyrene (PYR) at two concentrations (S2: 700 mg PHE kg⁻¹, S3: 700 mg PHE kg⁻¹ and 2100 mg PYR kg⁻¹). Soils were treated with both oxidation processes, and analyzed for PAHs and a set of agronomic parameters. A plant germination and growth test was run with rye-grass on treated soils. Results showed that both treatments produced the expected reduction of PAH concentration (from 64% to 97%). Besides, a significant loss of organic C and N, and strong changes in available nutrients were observed. Permanganate treatment increased the specific surface area and the cation exchange capacity in relation to manganese dioxide precipitation, and produced a rise in pH. Fenton oxidation decreased soil pH and increased the water retention capacity. Plant growth was negatively affected by permanganate, related to lower soil permeability and aeration. Both treatments had an effect on soil properties but Fenton oxidation appeared to be more compatible with revegetation.     

Hydroxypropyl-β-cyclodextrin extractability and bioavailability of phenanthrene in humin and humic acid fractions from different soils and sediments

Organic matter (OM) plays a vital role in controlling polycyclic aromatic hydrocarbon (PAH) bioavailability in soils and sediments. In this study, both a hydroxypropyl-β-cyclodextrin (HPCD) extraction test and a biodegradation test were performed to evaluate the bioavailability of phenanthrene in seven different bulk soil/sediment samples and two OM components (humin fractions and humic acid (HA) fractions) separated from these soils/sediments. Results showed that both the extent of HPCD-extractable phenanthrene and the extent of biodegradable phenanthrene in humin fraction were lower than those in the respective HA fraction and source soil/sediment, demonstrating the limited bioavailability of phenanthrene in the humin fraction. For the source soils/sediments and the humin fractions, significant inverse relationships were observed between the sorption capacities for phenanthrene and the amounts of HPCD-extractable or biodegradable phenanthrene (p?<?0.05), suggesting the importance of the sorption capacity in affecting desorption and biodegradation of phenanthrene. Strong linear relationships were observed between the amount of HPCD-extractable phenanthrene and the amount degraded in both the bulk soils/sediments and the humin fractions, with both slopes close to 1. On the other hand, in the case of phenanthrene contained in HA, a poor relationship was observed between the amount of phenanthrene extracted by HPCD and the amount degraded, with the former being much less than the latter. The results revealed the importance of humin fraction in affecting the bioavailability of phenanthrene in the bulk soils/sediments, which would deepen our understanding of the organic matter fractions in affecting desorption and biodegradation of organic pollutants and provide theoretical support for remediation and risk assessment of contaminated soils and sediments.