Polymer extraction and ex situ biodegradation of xenobiotic contaminated soil: Modelling of the process concept.

An integrated model of a two-step process for the ex situ bioremediation of xenobiotic contaminated soil has been formulated. The process is characterized by an initial extraction step of the organic contaminants from the polluted soil by contact with inexpensive and commercially-available polymer beads, followed by release and biodegradation of the xenobiotics, with parallel polymer bioregeneration, in a Two-Phase Partitioning Bioreactor (TPPB). The regenerated polymer is cyclically reused in the extraction step, so reflecting the robust and otherwise-inert properties of such polymers. The model was calibrated and validated for a soil contaminated with 4-nitrophenol (4NP) and treated with the DuPont polymer Hytrel 8206. In the model calibration, the partition coefficient polymer-soil, Pps, and the mass transfer coefficient, K, were evaluated, as 105.3 and 0.24 h-1 respectively. A diffusion coefficient within the polymer of 6.3 10-8 cm2 s-1 was determined from the fitting of sorption/desorption data. The model was then tested for two alternative process configurations consisting of either one or two soil extraction units, followed by the biodegradation/bioregeneration step. The latter configuration resulted in more effective polymer utilization and is suitable if each extraction step requires a shorter time than the regeneration step. The model predicted that an extraction time of 12 h was sufficient to reach removal efficiencies ≥90% while the biodegradation/bioregeneration step required 24 h to reach efficiencies ≥93%, with a good agreement with experimental data (R2 > 0.98 for both cases). The simulation of the process operated with two extraction units showed a better performance with a final concentration ∼0.2 g4NP kgds-1 vs. 1.69 g4NP kgds-1 obtained with single extraction unit, for a soil contaminated with 10 g4NP kgds-1. Corresponding extraction efficiencies were 96 and 83%, respectively.

Ex situ remediation of polluted soils by absorptive polymers, and a comparison of slurry and two-phase partitioning bioreactors for ultimate contaminant degradation.

The present study has provided a comparison between a conventional ex situ method for the treatment of contaminated soil, a soil slurry bioreactor, with a novel technology in which a contaminant is rapidly and effectively removed from the soil by means of absorptive polymer beads, which are then added to a two-phase partitioning bioreactor (TPPB) for biodegradation of the target molecule. 4-nitrophenol (4NP) was selected as a model contaminant, being representative of a large class of xenobiotics, and the DuPont thermoplastic Hytrel™ 8206 was utilized for its extraction from soil over ranges of soil contamination level, soil moisture content, and polymer:soil ratios. Since the polymers were able to rapidly (up to 77% and 85% in 4 and 24h respectively) and selectively remove the contaminant, the soil retained its nutrient and microflora content, which is in contrast to soil washing which can remove these valuable soil resources. After 4h of reaction time, the TPPB system demonstrated removal efficiency four times higher (77% vs 20%) than the slurry system, with expected concomitant savings in time and energy. A volumetric removal rate of 75 mg4NPh(-1) L(-1) was obtained in the TPPB, significantly greater than the value of 1.7 obtained in the slurry bioreactor. The polymers were readily regenerated for subsequent reuse, demonstrating the versatility of the polymer-based soil treatment technology.

2,4-Dichlorophenol removal in a solid-liquid two phase partitioning bioreactor (TPPB): kinetics of absorption, desorption and biodegradation.

The applicability of a sequencing batch two phase partitioning bioreactor (TPPB) to the biodegradation of a highly toxic compound, 2,4-dichlorophenol (DCP) (EC(50)=2.3-40 mgL(-1)) was investigated. A kinetic study of the individual process steps (DCP absorption into the polymer, desorption and biodegradation) was performed and, based on favourable absorption/desorption characteristics (DCP diffusivity of 6.6×10(-8)cm(2)s(-1)), the commercial polymer Tone P787 (Dow Chemical), was utilized as the sequestering phase for TPPB operation. Batch kinetic biodegradation tests were performed in both single- and two-phase modes, and the Haldane equation kinetic parameters were estimated (k=1.3×10(-2) mgDCP mgVSS(-1)h(-1), K(I)=35 mgDCPL(-1) and K(s)=18 mgDCPL(-1)), confirming the highly toxic nature of DCP. Consistent with these findings, operation of the single-phase system showed that for an initial DCP concentration of 130 mg L(-1) the biomass was completely inhibited and DCP was not degraded, while the two-phase system achieved near-complete DCP removal. In sequencing batch mode the TPPB had a removal efficiency of 91% within 500 min for a feed of 320 mg L(-1), which exceeds the highest concentration previously degraded. These results have confirmed the effectiveness of the use of small amounts (5%, v/v) of inexpensive commercial polymers as the partitioning phase in TPPB reactors for the treatment of a highly toxic substrate at influent loads that are prohibitive for conventional single-phase operation, and suggest that similar detoxification of wastewater influents is achievable for other target cytotoxic substrates.

Solid-liquid two-phase partitioning bioreactors (TPPBs) operated with waste polymers. Case study: 2,4-dichlorophenol biodegradation with used automobile tires as the partitioning phase.

Used automobile tire pieces were tested for their suitability as the sequestering phase in a two-phase partitioning bioreactor to treat 2,4-dichlorophenol (DCP). Abiotic sorption tests and equilibrium partitioning tests confirmed that tire "crumble" possesses very favourable properties for this application with DCP diffusivity (4.8 × 10(-8) cm(2)/s) and partition coefficient (31) values comparable to those of commercially available polymers. Biodegradation tests further validated the effectiveness of using waste tires to detoxify a DCP solution, and allow for enhanced biodegradation compared to conventional single-phase operation. These results establish the potential of using a low-cost waste material to assist in the bioremediation of a toxic aqueous contaminant.

Treatment of substituted phenol mixtures in single phase and two-phase solid-liquid partitioning bioreactors.

The biological treatment of phenolics is constrained by the inherent cytotoxicity of these compounds. One method to alleviate such toxicity is to add a sequestering phase to absorb, and subsequently release, the substrate(s) to the micro-organisms; such a system is termed a Two Phase Partitioning Bioreactor. Here we have compared the performance of a TPPB, relative to single phase operation, in which a small volume (5%, v/v) of beads of the polymer Hytrel 8206 was used to treat aqueous mixtures of 2,4-dimethylphenol and 4-nitrophenol. Hytrel 8206 was selected from a range of polymers that were tested for their partition coefficients (PCs) for the target molecules, with the more hydrophobic compound (2,4-dimethylphenol) having a higher PC value (201) than 4-nitrophenol (143). Significantly increased removal rates for both substrates were demonstrated in TPPB mode relative to single phase operation. Additionally, the differential release of the compounds to the aqueous phase and their distinct PC values changed the kinetic pattern of the biotreatment system, smoothing out the cellular oxygen demand. Release of the substrates by the polymer over 60 operating cycles was virtually complete (>97%) demonstrating the reusability and robustness of the use of polymers in overcoming cytotoxicity of phenolic substrates.

Two-phase partitioning bioreactors operating with polymers applied to the removal of substituted phenols.

Significant improvement in biodegradation performance has been demonstrated arising from the reduction of cytotoxicity provided by the sequestering of 4-nitrophenol (4NP) within Hytrel polymer beads added to a two-phase partitioning bioreactor (TPPB) operating in sequencing batch reactor (SBR) mode. This reduced toxicity is particularly apparent as the feed substrate concentration is increased; in fact it was shown that at a feed of 1000 mg/L 4NP, the inhibitory effect of the substrate completely prevents degradation from occurring in a single-phase system, whereas at only a 5% polymer loading, rapid and compete biodegradation is achieved. Different polymer/aqueous phase ratios were used to detoxify varying feed concentrations, and degradation rates were enhanced through the use of increased polymer loadings. As demonstrated in oxygen uptake experiments, the addition of polymers also reduces the maximum demand for oxygen, relative to single-phase operation, and smoothes the demand for oxygen throughout the degradation process. Polymer regeneration has also been further characterized by quantifying the number of methanol washes required to achieve satisfactory 4NP residuals, and the addition of a small amount of cosolvent has been shown to dramatically increase the rate of bioregeneration to produce beads ready for reuse.

Biodegradation of 4-nitrophenol in a two-phase system operating with polymers as the partitioning phase.

The present study has demonstrated the enhanced performance of a two-phase bioreactor, operating with polymers as a partitioning phase, as an alternative to both single phase biotreatment and to the use of an immiscible organic solvent partitioning phase, to deliver a toxic substrate (4-nitrophenol, or 4NP) to a microbial consortium in batch and repeated batch mode. Three commercial polymers were tested, Hytrel, Tone, and Elvax, and were shown to have superior properties related to the use of a consortium, including complete biocompatibility with the biomass and nonbiodegradability. Repeated kinetic tests performed with short reaction times demonstrated the accumulation of 4NP within the polymers in the range of 6-8 mg/g polymer, which reduced polymer performance in subsequent batch operations. Hytrel gave the best performance with residuals of up to 4 mg/g polymer showing no reduction in subsequent use, while for the other polymers a 4NP value lower than 2 mg/g polymer was required to have acceptable performance during repeated polymer use. Polymer reuse without affecting the process efficiency was confirmed with regeneration tests. A conventional methanol extraction method, as well as biological regeneration of the polymers by prolonged contact with the biomass, were assessed for their ability to remove the residual 4NP. Parallel kinetic tests performed with newand regenerated polymers showed a complete overlap of the 4NP concentration profiles indicating that a simple biological regeneration method provides a means of completely restoring polymer performance for repeated batch operation.

Biodegradation of 4-nitrophenol in a two-phase sequencing batch reactor: concept demonstration, kinetics and modelling.

The objectives of this work were to demonstrate the potential of a two-phase sequencing batch reactor in degrading xenobiotics and to evaluate the kinetic parameters leading to a mathematical model of the system. 4-Nitrophenol (4NP), a typical representative of substituted phenols, was selected as the target xenobiotic; this compound has never been remediated in a two-phase bioreactor before. Partition tests were conducted to determine the most appropriate partitioning solvent, and among the three investigated solvents (1-undecanol, 2-undecanone and oleyl alcohol), 2-undecanone was chosen because of its favourable partition coefficient and its negligible emulsion-forming tendencies. Moreover, the selected solvent showed satisfactory biocompatibility characteristics with respect to the biomass, with only minor effects on the intrinsic microbial kinetics. Kinetic tests were then performed in a sequencing batch reactor (2-l volume) operated in both conventional one- and two-phase configurations, with the two-phase system showing a significant improvement in the process kinetics in terms of reduced inhibition and increased maximum removal rate. The obtained kinetic parameters suggest that the two-phase sequencing batch system may find full-scale application, as the maximum removal rate k(max) (approximately 3 mg 4NP mgVSS(-1) day(-1)) is of the same order of magnitude of heterotrophic bacteria operating in wastewater treatment plants.

4-nitrophenol biodegradation in a sequencing batch reactor operating with aerobic-anoxic cycles.

The study regards 4-nitrophenol removal performed in a lab-scale sequential batch reactor with an integrated aerobic-anoxic cycle. The purpose of the study was to examine the kinetics of 4-nitrophenol biological oxidation and denitrification in order to test the feasibility of the proposed technological solution for xenobiotic removal. The results obtained show that high removal efficiency of 4-nitrophenol is easily achieved when the compound is fed into the reactor as the sole carbon source. Residual concentrations of 4-nitrophenol and nitrous/nitric nitrogen in the effluent lower than 1 mg L(-1) were observed in the range of applied feed concentration (200-320 mg L(-1)). Low concentrations of dissolved oxygen (< or =2 mg L(-1)) in the feed and aerobic phases lead to appreciable simultaneous denitrification. As regards the denitrification process, while no carbon-limiting effects were observed at COD/N ratios > or = 3, a significant decrease in the rate of denitrification is detected for COD/N ratios < or = 2. The denitrification rate obtained in tests with no external carbon addition proved very low and unsuitable for practical application. A model of the denitrification process taking into account both the limiting effect of nitrogen and carbonaceous substrate has been proposed and applied for experimental data correlation.

4-nitrophenol biodegradation in a sequencing batch reactor: kinetic study and effect of filling time.

Biodegradation kinetics of 4-nitrophenol (4NP) was investigated in a lab-scale sequencing batch reactor fed with the compound as the sole carbon source. The experimental results showed that complete 4NP removal can be easily achieved with acclimatized biomass, even if an inhibition kinetics is observed; furthermore, an improvement in the removal kinetics is obtained if the substrate concentration peak, reached in the reactor at the end of the filling time, is maintained to quite a low value. Both long feed phase and high biomass concentration are effective in reducing the substrate concentration peak and then improving the process efficiency. Kinetic test data are well correlated by the Haldane equation, with a saturation constant Ks and an inhibition constant KI, of 17.6 and 30.7 (mg l(-1) 4NP), respectively, whereas the maximum removal rate was in the range of 3.3-8.4 (mg 4NP mg VSS(-1) d(-1)) depending on the substrate concentration peak reached in the reaction phase.

Kinetics of 4-nitrophenol biodegradation in a sequencing batch reactor.

In this paper, the biodegradation process of 4-nitrophenol (4NP) in a sequencing batch reactor has been investigated. Kinetic tests have been carried out on biomass grown on mixed substrate (4NP plus biogenic substrate) both in the presence of a biogenic substrate fraction in the feed and with 4NP as the sole carbon source. Removal kinetics for all tests is well described by the typical substrate inhibition pattern as predicted by the Haldane equation. In both sets, estimated kinetic parameters are very similar: no beneficial effect of the biogenic fraction is observed on the 4NP removal while increasing trend of 4NP maximum removal rate with the 4NP/COD(TOT) ratio in the feed has been observed. This finding has been modelled by estimating the fraction of the total biomass involved in 4NP biodegradation as a function of 4NP concentration in the feed. High removal rates, short acclimation times and good settling characteristics of produced sludge (observed during the whole working period) confirm the suitability of periodic systems in enhancing the bacterial potentialities for biodegradation of xenobiotic compounds.