Article

The influence of a NAPL on the loss and biodegradation of 14C-phenanthrene residues in two dissimilar soils

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Abstract

This study was carried out to assess the influence of diesel, applied over a log concentration range, on the loss and extractability of phenanthrene (measured as putative 14C-phenanthrene residues) in two different soils. The influence of diesel on the ability of a cyclodextrin based extraction method to predict the microbial bioavailability of 14C-residues was also assessed. An increase in loss of 14C-residues with increasing diesel concentration from 0 to 2000 mg kg-1 was generally observed with time in both soils. It is suggested that this trend is attributable to competitive sorption for soil sorption sites and to a lesser extent to displacement of 14C-residues from soil sorption sites by diesel resulting in greater compound availability and therefore greater loss by degradation via the actions of indigenous microorganisms. However, in the 20000 mg kg-1 diesel treatments of both soils, results indicated a delayed loss. It is suggested that this retarded loss was due to the formation of a discrete NAPL-phase into which 14C-phenanthrene residues partitioned, thereby decreasing their availability and as a consequence their degradation. Furthermore, it is suggested that nutrient limitation may have slowed down degradation rates as diesel concentrations increased. Comparison between cyclodextrin-extractability and microbial mineralisation supported the use of cyclodextrin to assess microbial bioavailability of 14C-residues after 50 d or more ageing up to diesel concentrations of 2000 mg kg-1. However, results suggested that at high diesel concentrations (specifically 20000 mg kg-1) co-extraction of 14C-phenanthrene residues may have occurred as a result of the combined solvation powers of both the cyclodextrin and the diesel. Furthermore, mineralisation of 14C-phenanthrene residues may have been affected by extreme nutrient limitation in this treatment.

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Phenanthrene was rapidly and extensively mineralized by a bacterium in the presence of glass or polystyrene beads with no pores, silica beads with 2.5−15 nm pores, 3-aminopropyl-bonded silica beads with 6-nm pores, and diatomite beads with 5.4 μm pores. These beads sorbed 10−99% of the compound in 15 h, but 48−100% of the sorbed hydrocarbon was desorbed in 240 h. Although little phenanthrene was desorbed from octadecyl-bonded silica beads with 6-nm pores, the hydrocarbon was rapidly and extensively degraded. In contrast, the bacterium mineralized <7% of the phenanthrene sorbed to polystyrene beads with 5- or 300−400-nm pores, and little of the compound was desorbed. These findings are consistent with the hypothesis that sequestration and reduced bioavailability occur when hydrophobic compounds enter into nanopores having hydrophobic surfaces.
Article
The widely accepted dissolution (partition) model of sorption to soil organic matter (SOM) has been challenged by evidence that SOM has a non-uniform sorption potential. This study presents data supporting a previously sug gested alternative dual-mode model of sorption in which dissolution and hole-filling mechanisms take place concurrently, as in glassy organic polymers. The holes are postulated to be nanometer-size voids within the organic matrix that provide complexation sites. The main focus was on sorption of chlorobenzene, 1,2-dichlorobenzene, and 1,3-dichlorobenzene, but some experiments were carried out also on 2,4-dichlorophenol and the herbicide metolachlor. Sorption from water to high-organic soils, humic acid particles, and poly(vinyl chloride) is nonlinear, competitive, and predictably responsive to conditions that affect hole populations such as temperature and co-solvent addition. Sorption to a peat soil and its components became progressively nonlinear and competitive in the order humic acid, native peat, humin; this order reflects the increasing “glassy”i.e., rigid, condensednature of organic matter according to modern concepts of humic structure. Gas adsorption isotherms (N2 at 77 K and CO2 at 273 K) reveal the presence of internal microvoids accessible only by diffusion through the solid phase. The degree of nonlinearity and competition correlate with the CO2-measured microvoid volumes of the sorbents. The hole-filling mech anism is more important for the kinetically slow fraction.
Article
Bioavailability of oil components in contaminated soils is an important regulating factor for biodegradation rates. Changes in the composition of mineral oil can provide information regarding the bioavailability restrictions in contaminated soils. The fate of oil components was studied in a lysimeter experiment and laboratory incubations. A shift in the n-alkane ratios in the range n-C16:n-C20 was observed around 4.0 g kg-1, indicating that two different mechanisms control the bioavailability of the oil. At higher concentrations, the bioavailability was controlled by solubilization from a non-aqueous-phase liquid into the aqueous soil water phase. The ratios remained constant with decreasing oil concentration in this stage. Below 4.0 g kg-1, desorption and diffusion became rate-limiting factors:  a shift was observed in the n-alkane ratios, showing that biodegradation rates of n-alkanes increased with decreasing carbon number. The monitoring of n-alkane ratios can be used to improve the efficiency of bioremediation treatments.
Article
A study was conducted to determine the feasibility of devising a chemical assay to predict the bioavailability of organic compounds that become sequestered in soil. The recovery of atrazine and phenanthrene freshly added to soil varied appreciably among individual solvents, but the quantity extracted by each solvent declined as the test compounds persisted in soil. The percentage recovered by some extractants approximated either the percentage uptake by earthworms or bacterial degradation. Recovery by one extractant predicted bioavailability to both organisms. The data suggest that it is feasible to predict bioavailability of persistent organic compounds in soil by chemical procedures.
Article
Biodegradation of phenanthrene, biphenyl, or di(2 ethylhexyl) phthalate initially present in a variety of nonaqueous phase liquids (NAPLs) was slow in samples of soil and aquifer solids The NAPLs were hexadecane, dibutyl phthalate, 2,2,4,4,6,8,8-heptamethylnonane, cyclohexane, commercial oils, crude oil, creosote, and kerosene Slurrying the soil or aquifer solids markedly enhanced the rate and extent of mineralization of the test compounds initially in many of the NAPLs Both the low rate and the extent of mineralization of the three compounds initially in dibutyl phthalate in soil slurries and of di(2 ethylhexyl) phthalate in heptamethylnonane present in slurries of aquifer solids were increased by inoculation of acclimated microbial cultures Increasing the NAPL volume decreased phenanthrene biodegradation in soil, but the effect of larger NAPL volume could be alleviated by slurrying and inoculation The rate or extent of mineralization in aquifer slurries of di(2-ethylhexyl) phthalate initially in some NAPLs was increased by addition of N and P, and inoculation further enhanced the degradation
Article
A study was conducted to determine the effects of biodegradability of nonaqueous-phase liquids (NAPLs) and microbial competition on the biodegradation in soil of a constituent of the NAPLs. The rates of mineralization of phenanthrene dissolved in 8 mg of 2,2,4,4,6,8,8-heptamethylnonane (HMN), di(2-ethylhexyl) phthalate (DEHP), or pristane per g of soil were faster than the rates when the compound was dissolved in hexadecane or dodecane. Addition of inorganic N and P to the soil increased the mineralization rate in the first two but not the last two NAPLs. N and P addition did not enhance mineralization of phenanthrene when added in 500 μg of hexadecane, pristane, or HMN per g of soil. Hexadecane was rapidly degraded, pristane was slowly metabolized, DEHP was still slower, and HMN was not mineralized in the test period. Mixing the soil stimulated mineralization of phenanthrene dissolved in HMN but not in hexadecane. Mineralization of phenanthrene dissolved in HMN was the same if the gas phase contained 21%, 2.1%, or traces of O2. In contrast, the biodegradation of phenanthrene dissolved in hexadecane, although the same at 21 and 2.1% O2, was not observed if traces of O2 were present. The mineralization was slower in unshaken soil–water mixtures if phenanthrene was added in hexadecane than in HMN or pristane, but the rates with the 3 NAPLs were increased by shaking the suspensions. We suggest that the biodegradability of major components of NAPLs and microbial competition for N, P, or O2 will have a major impact on the rate of transformation of minor constituents of NAPLs.
Article
A study was conducted to determine the relationship between bioavailability of unaged and aged polycyclic aromatic hydrocarbons (PAHs) in soil and the amounts detected by mild solvent extraction. More aged than unaged anthracene remained in Lima loam following introduction of earthworms (Eisenia foetida), a mixed culture containing anthracene-degrading microorganisms, or earthworms or wheat after bacterial biodegradation of the compound. Aging decreased the percentage of anthracene recovered by mild extraction with n-butanol from soil following introduction of earthworms, growth of wheat, biodegradation by bacteria, or when maintained sterile. Biodegradation resulted in a marked decrease in the percentage of aged and unaged anthracene recovered from soil by mild extraction with n-butanol or ethyl acetate. Aging of fluoranthene and pyrene decreased the amount removed by mild extraction with n-butanol, ethyl acetate, and propanol. The uptake of aged and unaged anthracene, fluoranthene, and pyrene by earthworms was correlated with the amounts recovered from soil by mild extraction with n-butanol, propanol, and ethyl acetate (r values in the range 0.911–0.992). The retention of aged and unaged anthracene by wheat and barley was correlated with the amounts recovered from soil by the same procedure (r values in the range 0.892–0.945). We suggest that mild extraction with organic solvents can be used to predict the bioavailability of PAHs in soil.
Article
Less of the desorption-resistant fractions of phenanthrene and naphthalene than freshly added phenanthrene and naphthalene was mineralized in columns of aquifer solids, loam, or muck. Slurrying columns of hydrocarbon-amended aquifer solids, loam, or muck enhanced the rate and extent of mineralization of desorption-resistant phenanthrene and naphthalene, but degradation was still less than in slurries amended with fresh compound. A substantial portion of the desorption-resistant compound remained undegraded in the slurry. A surfactant and methanol increased the mineralization of resistant phenanthrene in slurries of loam. A mixed culture of microorganisms enriched on desorption-resistant phenanthrene degraded twice as much of this fraction of compound as a pseudomonad. We suggest that predictions of the environmental fate of toxic chemicals require information on the biodegradability of the fraction of a compound that is resistant to desorption.
Article
This paper describes the validation and application of a simple flask-based 14C-respirometer system designed to assess mineralisation of 14C-labelled substrates under defined conditions. Validation of this respirometer system indicated stoichiometric CO2 trapping up to a maximum of 400 μmol of CO2 (in a single trap). Polycyclic aromatic hydrocarbon (PAH)-degrading bacteria were used to measure growth-linked biodegradation of [14C]naphthalene to 14CO2. A 14C activity balance of 101.7±8.9% (n=6), after 74 h incubation time and 10 respirometer-opening events, indicated the suitability of the system for monitoring substrate mineralisation. This respirometric apparatus was then successfully applied to assess: (i) the PAH catabolism of microbes in a field contaminated soil, where naphthalene and phenanthrene were rapidly mineralised and (ii) soil-associated organic contaminant bioavailability, where increased soil–phenanthrene contact time resulted in a reduction in phenanthrene mineralisation in the soil. The described respirometer system differs from existing respirometer systems in that the CO2 trap can be removed and replaced quickly and easily. The system is efficient, reproducible, adaptable to many situations, easy to construct and simple to use, it therefore affords advantages over existing systems.
Article
A study was conducted to find ways to increase the biodegradability of compounds that have aged in soil or aquifer material and become less bioavailable. Slurrying enhanced the rate and extent of biodegradation by individual bacterial strains of aged and unaged phenanthrene and di(2-ethylhexyl) phthalate in soils and aquifer solids. After bacterial degradation of aged phenanthrene in unslurried soil had largely ceased, the residual compound was metabolized if the soil was slurried and reinoculated with a phenanthrene-degrading bacterium. The rate and extent of biodegradation of aged phenanthrene by Pseudomonas sp. were enhanced when anthracene or pyrene was added to the soil at the same time as the bacterium, although the organism could not metabolize anthracene or pyrene. Moreover, anthracene or pyrene increased the amount of aged phenanthrene removed from soil by a mild extractant. The data show that the bioavailability of organic compounds that become sequestered by aging can be altered by appropriate soil treatments.
Article
A study was conducted to determine the mineralization in soil and subsoil of hydrophobic organic compounds present in several nonaqueous-phase liquids (NAPLs). When present in soil in some NAPLs, di(2-ethylhexyl) phthalate (DEHP) was not appreciably mineralized, phenanthrene was slowly transformed after an acclimation phase, and hexadecane and naphthalene were biodegraded rapidly. The extent of suppression of biodegradation of test compounds varied with different solvents as NAPLs. The rate of mineralization in subsoil of phenanthrene dissolved in some NAPLs was very slow, but additions of N and P enhanced the degradation. The addition of N and P to soil did not increase the mineralization of DEHP dissolved in NAPLs. The existence of a NAPL in polluted environments may thus markedly affect the susceptibility of organic compounds to biodegradation.
Article
Competitive sorption to natural solids among mixtures of organic compounds has been documented in the literature. This study was conducted to determine co-solute competitive effects on the biological and physical availability of polycyclic aromatic hydrocarbons in soils after long contact periods (aging). Sterile suspensions of Mount Pleasant silt loam (Mt. Pleasant, NY, USA) and Pahokee peat soils were spiked with phenanthrene and allowed to age for 3 or 123 d before inoculation with a phenanthrene-degrading bacterium in the presence or absence of the nonbiodegradable co-solute pyrene. As expected, mineralization decreased with aging in the samples not amended with pyrene. However, addition of pyrene just prior to inoculation at 123 d significantly mitigated this decrease; that is, the extent of mineralization was greater in the 123-d pyrene-amended samples than in the 123-d nonamended samples. Parallel experiments on sterile soils showed that pyrene increased the physical availability of phenanthrene by competitive displacement of phenanthrene from sorption sites. First, the addition of pyrene increased recovery of 123-d-aged phenanthrene by mild solvent extraction. Second, addition of pyrene (at three concentrations) dramatically reduced the apparent distribution coefficient (Kappd) of several concentrations of 60-, 95-, and 111-d-aged phenanthrene. At the lowest phenanthrene and highest pyrene concentrations, reductions in the Kappd of phenanthrene in the peat soil reached 83%. The competitive displacement effect observed in this study adds further support to the dual mode model of sorption to soil organic matter. The displacement of an aged contaminant by a nonaged co-solute might also prove useful in the development of novel remediation strategies.
Article
A study was conducted to determine whether the time that a compound remains in a soil affects its biodegradability and the ease of its extraction. Phenanthrene and 4-nitrophenol were aged in sterilized loam and muck, and bacteria able to degrade the compounds were then added to the soils. increasingly smaller amounts of phenanthrene in the muck and 4-nitrophenol in both soils were mineralized with increasing duration of aging. Aging also increased the resistance of phenanthrene to biodegradation in nutrient-amended aquifer sand. The rate of miner- alization of the two compounds in both soils declined with increasing periods of aging. The amount of phenanthrene and 4-nitrophenol added to sterile soils that was recovered by butanol extraction declined with duration of aging, but subsequent Soxhlet extraction recovered phenanthrene from the loam but not the muck. The extents of mineralization of phenanthrene previously incubated for up to 27 days with soluble or insoluble organic matter from the muck were similar. Less aged than freshly added phenanthrene was biodegraded if aggregates in the muck were sonically disrupted. The data show that phenanthrene and 4-nitrophenol added to soil become increasingly more resistant with time to biodegradation and extraction.
Article
Sorption kinetics of hydrophobic organic chemicals to and from suspended sediment and soil particles is described by a radial diffusive penetration model modified by a retardation factor reflecting microscale partitioning of the sorbate between intraaggregate pore fluids and the solids making up the aggregate grains. In light of this and other sorption kinetics models, a closed-loop-stripping apparatus with a photoionization detector operating in-line was used to examine the effects of sorbate hydrophobicity, sorbent particle size, and system temperature on solid-solution exchange over times of seconds to days. The authors results indicate that a single effective diffusivity parameter, which is predictable from compound solution diffusivity, octanol-water partition coefficient, and sorbent organic content, density, and porosity, can be used to quantify the sorption kinetics.
Article
Fitzpatrick first published a text book on soils in 1971, and it has been completely rewritten for this new edition. The problem of the many classifications of soils used in the world has led the author to use three sets of terminlogy simultaneously, although the first 4 chapters are presented without the need to resort to such jargon. As far as classification is concerned the large number of systems are described while chapter 6 dicusses the soil classes of the world in alphabetical order using the FAO nomenclature - this consists of about one third of the book. -Keith Clayton
Article
This paper describes the validation and application of a simple flask-based (14)C-respirometer system designed to assess mineralisation of (14)C-labelled substrates under defined conditions. Validation of this respirometer system indicated stoichiometric CO(2) trapping up to a maximum of 400 micromol of CO(2) (in a single trap). Polycyclic aromatic hydrocarbon (PAH)-degrading bacteria were used to measure growth-linked biodegradation of [(14)C]naphthalene to (14)CO(2). A (14)C activity balance of 101.7+/-8.9% (n=6), after 74 h incubation time and 10 respirometer-opening events, indicated the suitability of the system for monitoring substrate mineralisation. This respirometric apparatus was then successfully applied to assess: (i) the PAH catabolism of microbes in a field contaminated soil, where naphthalene and phenanthrene were rapidly mineralised and (ii) soil-associated organic contaminant bioavailability, where increased soil-phenanthrene contact time resulted in a reduction in phenanthrene mineralisation in the soil. The described respirometer system differs from existing respirometer systems in that the CO(2) trap can be removed and replaced quickly and easily. The system is efficient, reproducible, adaptable to many situations, easy to construct and simple to use, it therefore affords advantages over existing systems.
Article
A study was conducted to investigate whether cyclodextrins and surfactants can be used to predict polycyclic aromatic hydrocarbon (PAH) bioavailability in contaminated sediments. Two sediment samples were extracted with aqueous solutions of hydroxypropyl-beta-cyclodextrin (HPCD) and Triton X-100. PAH removal during extraction was compared with PAH removal during biodegradation and solid-phase extraction. The latter two methods were used as reference methods to establish which part of the PAHs could be biodegraded and to what extent biodegradation was governed by bioavailability limitations. It was demonstrated that HPCD extraction followed solid-phase extraction and removed primarily readily bioavailable PAHs, while Triton X-100 extracted both readily and poorly bioavailable PAHs. Moreover, HPCD did not affect the degradation of PAHs in biodegradation experiments, while Triton X-100 enhanced the degradation of low molecular weight PAHs. It was concluded that HPCD extraction may provide a good method for the prediction of PAH bioavailability. Triton X-100 extraction is unfit for the prediction of PAH bioavailability.
Article
Oil is ubiquitous in aquatic sediments and may affect partitioning and bioavailability of hydrophobic organic chemicals (HOCs). In contrast to other sedimentary hydrophobic carbon phases (natural organic matter, soot-like materials), oil residues have hardly received any attention as far as it concerns effects on HOC sorption. This paper describes experimental work dealing with such effects of oil on polycyclic aromatic hydrocarbon (PAH) sorption to sediments. Three different oils were spiked to a marine sediment in concentrations between 0 and 100 g/kg. Sediment-water distribution coefficients (Kd) for six deuterated PAHs were then determined either directly after spiking the oil or after a semi-natural weathering process in the lab (lasting for more than 2 yr). Resulting Kd values demonstrated sorption-reducing (competitive) effects at relatively low oil concentrations and sorption-enhancing effects at high oil concentrations. The latter effects only occurred above a certain threshold [i.e., ca. 15% (w/w) of oil on a sedimentary organic carbon basis] marking the oil concentration at which the hydrocarbon mixture presumably starts forming separate phases. Assuming a two-domain (organic carbon + oil) distribution model, oil-water distribution coefficients (K(oil)) for PAHs were estimated. For fresh oils, log K(oil) values appeared to be very similar for different types of oils, proportional to log K(OW) values and indistinguishable from log K(OC) values. For weathered oils, K(oil) values were also rather independent of the type of oil, but the affinity of low molecular weight PAHs for weathered oil residues appeared to be extremely high, even higher than values reported for most types of soot. Because affinities of high molecular weight PAHs for oils had not changed upon weathering, sorption of all PAHs studied (comprising a log K(OW) range of 4.6-6.9) to the weathered oil residues appeared to be more or less constant (averaged log K(oil) = 7.0 +/- 0.24). These results demonstrate that it is crucial to take the presence of oil and its weathering state into account when assessing the actual fate of PAHs in aquatic environments.
Article
The aim of this study was to investigate the influence of diesel on the loss and bioavailability of soil-associated [14C]phenanthrene with time. In addition, the temporal development of phenanthrene catabolic activity and the impact of co-contaminant mixtures on the soil microflora were also assessed. With respect to compound fate, the results suggested that competitive effects between dissimilar co-contaminants did influence [14C]phenanthrene loss. Where diesel was present at a concentration of 0, 20, 200 and 2000 mg kg(-1), increased phenanthrene loss was observed with increasing diesel concentrations. In the 20,000 mg kg(-1) diesel treatment, however, a significantly higher amount of the initial [14C]activity remained after 225 days. Furthermore, initial degradation of phenanthrene in this treatment was retarded as a result of repressed phenanthrene catabolic activity. These results were complemented by a 4-fold increase in total culturable bacterial cell numbers in the 20,000 mg kg(-1) treatment when compared with the 2000 mg kg(-1) after 225 days of incubation time.
Soils and their Use in Eastern England Organic chemicals in contaminated land: analysis, significance and research priorities. Land Contam
  • C A H Hodge
  • R G O Burton
  • W M Corbett
  • R Evans
  • R S Seale
  • Harpenden
  • K C Jones
  • R E Alcock
  • D L Johnson
  • G L Northcott
  • K T Semple
  • P J Woolgar
Hodge, C.A.H., Burton, R.G.O., Corbett, W.M., Evans, R., Seale, R.S., 1984. Soils and their Use in Eastern England. Harpenden. Jones, K.C., Alcock, R.E., Johnson, D.L., Northcott, G.L., Semple, K.T., Woolgar, P.J., 1996. Organic chemicals in contaminated land: analysis, significance and research priorities. Land Contam. Reclam. 4, 189–197.
Soils in Norfolk V, Soil Survey Record No. 64, Sheet TG11 (Attledbridge)
  • D J Eldridge
Eldridge, D.J., 1980. Soils in Norfolk V, Soil Survey Record No. 64, Sheet TG11 (Attledbridge). Bartholomew Press.
Soils and their Use in Eastern England
  • C A H Hodge
  • R G O Burton
  • W M Corbett
  • R Evans
  • R S Seale
Hodge, C.A.H., Burton, R.G.O., Corbett, W.M., Evans, R., Seale, R.S., 1984. Soils and their Use in Eastern England. Harpenden.