Mineralisation Of 14C-phenanthrene Research Articles

Using supercritical fluid extraction to measure the desorption and bioaccessibility of phenanthrene in soils

The aim of this paper was to measure the changing desorbable fraction and bioaccessibility of phenanthrene in two different soils with increasing soil-phenanthrene contact time using supercritical fluid extractions (SFE). Both soils were spiked with 100 mg kg(-1) phenanthrene and aged for 28d. Desorption profiles were measured every 7d using selective SFE conditions and the results were compared to 14C-phenanthrene mineralisation assays. Selective SFE showed significant differences in the rates and extents of desorption in the two soils, likely to be due to different organic matter composition. Post-extraction fitting of data yielded consistent SFE extraction times within ageing soils for bioaccessibility prediction.

Impact of Black Carbon in the Extraction and Mineralization of Phenanthrene in Soil

During the past century, increased biomass burning and fossil fuel consumption have drastically increased the input of black carbon (BC) into the environment, and that has been shown to influence the behavior of organic contaminants in soil. A study was conducted to investigate the effects of BC on the relationship between aqueous hydroxypropyl-beta-cyclodextrin (HPCD) extraction and microbial mineralization (bioaccessibility) of 14C-phenanthrene (10 mg kg(-1)) in four soils amended with 0, 0.1, 0.5, 1, 2.5, and 5% (% dry wt soil) activated charcoal, a type of BC. Mineralisation was monitored over 20 d incubation, within respirometric assays, using an inoculum containing a phenanthrene-degrading pseudomonad and compared to HPCD extraction (24 h) using 50 mM aqueous solution; analyses were conducted after 1, 25, 50, and 100 d soil-phenanthrene contact time. Statistical analyses revealed that for each soil the addition of BC led to significant (P < 0.001) reductions in both HPCD extractability and microbial mineralization. Linear correlations for BC concentrations of 0% (r2 = 0.95; slope = 0.89) and 0.1% (r2 = 0.67; slope = 0.95) revealed a highly significant (P < 0.01) relationship between HPCD extractability and total mineralization (20 d), indicating a direct prediction of phenanthrene bioaccessibility by HPCD. However, in soils amended with 0.5, 1, 2.5, and 5% BC exhibited r2 values ranging 0.51-0.13 and slopes of 2.19-12.73. This study has shown that BC strongly sorbs phenanthrene causing reductions in extractability and, to a lesser extent, bioaccessibility to degrading microorganisms.

Prediction of Microbial Accessibility of Carbon‐14‐Phenanthrene in Soil in the Presence of Pyrene or Benzo[a]pyrene using an Aqueous Cyclodextrin Extraction Technique

Traditionally, solvent extractions are routinely used in the assessment of contaminated land. However, vigorous solvent extractions only give total concentrations rather than that relating to the bioaccessible fraction. Recently, less harsh, aqueous-based extraction methods have been shown to be a better estimate of the microbial degradation of polycyclic aromatic hydrocarbons (PAHs). The aqueous-based hydroxypropyl-beta-cyclodextrin (HPCD) extraction technique was tested using 14C-PAHs in soils and compared against indigenous microbial mineralization (a measure of bioaccessibility) of 14C-phenanthrene in the presence of pyrene or benzo[a]pyrene (B[a]P) over a range of concentrations (0, 5, 10, or 50 mg kg(-1)) and aged for 0, 25, 50, and 100 d in four soils. At each time point, the total loss, extractability, and mineralization of 14C-phenanthrene was measured in each of the soils. The presence of the other PAHs had little effect on the behavior of 14C-phenanthrene in any of the soils. Comparisons between the amounts of 14C-phenanthrene extracted using HPCD and mineralized were made and showed that there was a correlation (1:1). This study demonstrates that HPCD extraction is able to predict the microbial accessibility fraction of 14C-phenanthrene in the presence of other PAHs in a range of soils, further supporting the applicability of this technique.

Mathematical analysis of the whole core injection method accuracy for measuring phenanthrene biodegradation rates in undisturbed marine sediments

Rates of 14C-phenanthrene mineralization in contaminated, undisturbed marine sediments were measured using the whole core injection method to assess microbial natural attenuation activity as a function of sediment depth. Submerged sediments were sampled from Eagle Harbor, a marine superfund site in Puget Sound. Experiments show significant biodegradation activities (0.0012-0.0036 day(-1)) in the sediment horizons from 0 to 10 cm. The purpose and scope of this paper is to evaluate the range of experimental conditions giving valid results; a mathematical simulation described competing contaminant 14C-phenanthrene diffusion and simultaneous biodegradation (Monod kinetics), both retarded by sorption. The effect of aging was examined with two sorption models in presumed pseudo-homogenous sediments having effective properties. The simulation predictions provide quantitative guidelines for the successful use of the whole core injection method. (1) The effective Monod constant KS' in sediment is increased by a large partition coefficient KP between sediment and water and makes the apparent 14C-phenanthrene biodegradation approach first-order kinetics. (2) When KS'>1 mg(-1) l(-1), the measured 14C-phenanthrene biodegradation extent is biased by inadequately distributed injected tracer only when less than 7% of the sediment horizon is initially probed and mixed with injected tracer. (3) A short incubation time (<20 days) is necessary when a mobile indicator, e.g., gaseous 14CO2, is used. For longer incubation times, predictions show that a 14CO2 indicator diffuses to adjacent horizons, thus smearing the depth profile of biodegradation. (4) This method employing a radiolabeled tracer provides accurate biodegradation rates for freshly contaminated sediments, and represents an upper limit to the natural phenanthrene biodegradation extents if the contaminant is aged over 50 days.

Depth-related influences on biodegradation rates of phenanthrene in polluted marine sediments of Puget Sound, WA

A whole-core injection method was used to determine depth-related rates of microbial mineralization of 14C-phenanthrene added to both contaminated and clean marine sediments of Puget Sound, WA. For 26-day incubations under micro-aerobic conditions, conversions of 14C-phenanthrene to 14CO 2 in heavily PAH-contaminated sediments from two sites in Eagle Harbor were much higher (up to 30%) than those in clean sediments from nearby Blakely Harbor (<3%). The averaged 14C-phenanthrene degradation rates in the surface sediment horizons (0–3 cm) were more rapid (2–3 times) than in the deeper sediment horizons examined (>6 cm), especially in the most PAH polluted EH9 site. Differences in mineralization were associated with properties of the sediments as a function of sediment depth, including grain-size distribution, PAH concentration, total organic matter and total bacterial abundance. When strictly anaerobic incubations (in N 2/H 2/CO 2 atmosphere) were used, the phenanthrene biodegradation rates at all sediment depths were two times slower than under micro-aerobic conditions, with methanogenesis observed after 24 days. The main rate-limiting factor for phenanthrene degradation under anaerobic conditions appeared to be the availability of suitable electron acceptors. Addition of calcium sulfate enhanced the first order rate coefficient ( k 1 increased from 0.003 to 0.006 day −1), whereas addition of soluble nitrate, even at very low concentration (<0.5 mM), inhibited mineralization. Long-term storage of heavily polluted Eagle Harbor sediment as intact cores under micro-aerobic conditions also appeared to enhance anaerobic biodegradation rates ( k 1 up to 0.11 day −1).

Comparison of mineralization of solid-sorbed phenanthrene by polycyclic aromatic hydrocarbon (PAH)-degrading Mycobacterium spp. and Sphingomonas spp.

The mineralization of 14C-phenanthrene, sorbed to porous synthetic amberlite sorbents, i.e., IRC50, XAD7-HP, and XAD2, by three phenanthrene-degrading Mycobacterium soil isolates, i.e., strains VM552, VM531, and VM451 and three phenanthrene-degrading Sphingomonas soil isolates, i.e., strains LH162, EPA505 and LH227, was compared. In P-buffer and in the presence of IRC50, for all strains the maximum rate of mineralization of 14C-phenanthrene was significantly higher (1.1-1.9 ng ml(-1) h(-1)) than the initial abiotic desorption rate (0.2 ng ml(-1) h(-1)), indicating that both Mycobacterium and Sphingomonas utilize sorbed phenanthrene with a higher rate than can be explained by abiotic desorption. Because all Mycobacterium and Sphingomonas strains belonged to different species, it can be suggested that this feature is intrinsic to those genera rather than a specific feature of a particular strain. The final mineralization extent in P-buffer in the presence of IRC50 was about a factor of two higher for the Mycobacterium strains compared to the Sphingomonas strains. Moreover, a significantly higher normalized phenanthrene mineralization ratio in the presence of IRC50 to the control (without IRC50) was found for the Mycobacterium strains compared to the normalized ratio found for the Sphingomonas strains. Addition of minimal nutrients had a more beneficial effect on phenanthrene mineralization by Sphingomonas compared to Mycobacterium, resulting into similar mineralization extents and rates for both types of strains in the presence of IRC50. Our results show that Mycobacterium is better adapted to utilization of sorbed phenanthrene compared to Sphingomonas, especially in nutrient-poor conditions.

Impact of compost amendments and operating temperature on diesel fuel bioremediation

A laboratory study was conducted to investigate the performance of composting bioremediation of a sand material contaminated with diesel fuel and radio-labeled phenanthrene. The material was amended with either fresh feedstock material or finished compost and then incubated at either thermophilic or mesophilic temperatures for 126 d. In controls that were not amended with compost, no mineralization of 14C phenanthrene was detected, whereas treatments that received compost amendments had significant phenanthrene mineralization, ranging from 25% to 42% of initial concentrations. The lowest extractable diesel range organic residual (1092 mg kg–1 total solids) was observed in the treatment receiving fresh compost amendment and incubated at thermophilic temperatures, whereas the highest residual (8507 mg kg–1 total solids) was observed in the control without any amendment. Whereas all the treatments that received amendment dramatically outperformed the control reactors, significant differences were observed among the treatment performances. This suggests that amendment type and operating temperature were important factors impacting bioremediation performance. Key words: compost amendments, bioremediation, diesel fuel, phenanthrene, temperature.

A Model for the Effect of Rhizodeposition on the Fate of Phenanthrene in Aged Contaminated Soil

Microcosm data were used to develop a deterministic model to describe how rhizodeposition affects the fate of phenanthrene in aged contaminated soil. Microbial mineralization and soil sequestration of 14C-phenanthrene were compared in microcosms amended weekly with phenolic-rich mulberry root extracts versus unamended controls. Mineralization was higher in the amended soils simulating the rhizosphere (57.7 +/- 0.9%) than in controls simulating bulk (unplanted) soils (53.2 +/- 0.7%) after 201 days (p < 0.05). Humin was the main soil sink for the residual 14C-label. Whereas the total 14C-label associated with humin remained constant in biologically active soils (at about 30%), it increased up to 80% after 201 days in sterile controls. The initial phenanthrene extraction with n-butanol (commonly used to assess bioavailability) slightly underestimated the fraction thatwas mineralized (assessed by 14CO2 recovery). Changes in the unextractable fraction (determined by combustion in a biological oxidizer) suggested the presence of two soil sequestration domains: (1) irreversibly bound residue, and (2) an intermediate transition phase that is unextractable by solvents at a given point in time but could become bioavailable due to physicochemical or biological transformations of the binding matrix. The fate of phenanthrene was accurately modeled by considering the transfer of the 14C label between different soil compartments as first-order kinetic processes. Model simulations suggested that the system was approaching a stable end-point after 201 days of simulated rhizoremediation, and corroborated that microorganisms have a significant impact on the fate of phenanthrene in soil.

Can microbial mineralization be used to estimate microbial availability of organic contaminants in soil?

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 and not decreasing cellular activity or cell death. The mineralization values also correlated with 14C-phenanthrene extractability using β-cyclodextrin.

Effect of linear alkylbenzene sulphonate (LAS) on the mineralization, metabolism and uptake of 14C-phenanthrene in a model ecosystem (water–lava–plant–air)

The aim of this work was to evaluate the effect of linear alkylbenzene sulfonate (LAS, 200 mg l −1) on the fate of phenanthrene in a model ecosystem “water–lava–hydrophytes–air”. The experiments were conducted using two closed cultivation chamber systems. Rushes ( Juncus effesus) were selected as a representative hydrophyte. Five hundred micrograms per liter of phenanthrene in a culture solution containing a 14C-activity of 75 μCi per chamber was applied (i) to investigate the degradation of the labeled test substance and the transfer processes within the system; (ii) to determine the mass-balance possible and (iii) to detect the occurrence of volatile test substances, their volatile metabolites and the degradation end-product CO 2 in the gas phase. Most of the applied 14C-activity was found in the plant (41–45%), in which ≈95% was associated with plant roots and ≈5% with shoots. The 14C-activity recovered in the form of VOCs and CO 2 was measured in lava (18–29%, 8–11%), and in the culture solution (10–14% and 1%), respectively. Majority of the applied 14C-activity existed in two forms, i.e. (1) polar metabolites (26%), of which 91% were found in plant roots, and (2) un-extractable residues (23%), most of which were in plant roots (40%) and bounded to lava (58%). The presence of LAS significantly increased the volatilization of phenanthrene and its metabolites, inhibited its mineralization and decreased the level of 14C-activity in lava. Moreover, LAS reduced the phenanthrene level in plant roots.

Microbial Degradation of Phenanthrene in a Constructed Wetland

Abstract The removal of phenanthrene was investigated in a horizontal-vertical flow, constructed wetland (Aquaplant®), designed by Umweltschutz Nord GmbH & Co. Contamination of the system with a two component “artificial wastewater” (phenanthrene / Tween80®) lead to the establishment of a specialized microbial population capable of degrading phenanthrene. Besides phenanthrene, a typical bacterial phenanthrene metabolite, 1-hydroxy-2-naphthoic acid, was detected and quantified. Laboratory scale 14C-phenanthrene mineralization experiments confirmed the degradation potential of the system.

Evaluation of Biological Treatability of Soil Contaminated with Manufactured Gas Plant Waste

ABSTRACT The biological treatability of subsurface soil contaminated with manufactured gas plant (MGP) waste was evaluated. Mineralization assays incorporating 14C-phenanthrene were used to evaluate the biotransformation potential of indigenous microorganisms at the site. Multi-phase laboratory microcosms were used to evaluate the interphase transfer potential and chemical mass distribution of phenanthrene. The Microtox™ bioassay was used to evaluate detoxification trends at the site. Mineralization results indicated that indigenous microorganisms at the site were capable of transforming phenanthrene, a component of coal-tar creosote. Results also indicated that spiked 14C-phenanthrene mineralization was influenced by nutrient addition and by the amount of contamination. The chemical mass distribution of 14C-phenanthrene indicated that volatilization may be an important transport mechanism for chemicals residing in, or migrating to the vadose zone of soil. Following removal of the coal-tar waste source at...

Estuarine ecology of phenanthrene-degrading bacteria

Phenanthrene degrading bacteria were ubiquitously distributed in waters and sediments of the Great Bay Estuary, NH, as determined using a 14C-phenanthrene mineralization assay. Similar activities were observed in water samples collected in March and June when these were incubated at 18 °C even though ambient water temperatures were 1–4 °C and 10–22 °C, respectively. This observation indicated the constant presence of a mesophilic phenanthrene-degrading bacterial population in the estuary. Among water samples, the highest biodegradation activities were associated with samples collected downstream from a dredging operation which introduced high concentrations of coal tar PAH (polycyclic aromatic hydrocarbons) into the Cocheco River, and in areas receiving PAH from pleasure and commercial boating activities. Mid-estuarine maxima in biodegradation activity during both sampling trips suggested adaptation of the microbial flora to the salinities prevailing in the low turnover, high residence time portion of the Estuary at the time of sampling. Despite the hydrophobicity of phenanthrene, no correlation between biodegradation rates and particulate matter concentrations were observed. Similarly, concentrations of nutrients and dissolved and particulate organic matter correlated poorly with biodegradation rates. Better agreements between 14C-phenanthrene mineralization potentials and plate counts on a phenanthrene/toluene agar (PTA) medium were observed. Phenanthrene biodegradative activities and numbers of culturable bacteria growing on PTA were governed by the degree of previous exposure to PAH.