Self-regenerating tubing bioreactor for removal of toxic substrates: Operational strategies in response to severe dynamic loading conditions.

A tubing TPPB (Two-Phase Partitioning Bioreactor) was operated with the objective of verifying the effective treatment of a phenolic synthetic wastewater with simultaneous polymeric tubing bioregeneration by introducing tubing effluent recycle and modifications to the Hydraulic Retention Time (HRT). 2,4-dichlorophenol (DCP) was employed as the target substrate and the bioreactor was operated for a 3 month period under severe loading conditions (from 77 to 384 mg/L d) with HRT in the tubing in the range of 2-4 h. Tubing effluent recycle (recycle flow rate/influent flow rate ratio = 0.3) was applied when a loss of performance was detected arising from the increased load. For HRT values of 3 and 4 h, almost complete DCP removal was achieved after a few days (1-5) of operation while for the 2 h HRT (i.e. in the most severe loading condition) the DCP removal was ≥97%. A beneficial effect on the process performance arising from recycle application was evident for all the operating conditions investigated, and was confirmed by statistical analysis. Essentially complete polymer bioregeneration was achieved when the bioreactor was operated at the lowest HRT (i.e. 2 h), combined with the application of tubing effluent recycle. The results of this study highlighted several advantages of the tubing TPPB configuration in a comparative analysis of different regeneration options, including the possibility of operating continuously with simultaneous bioregeneration and without the need for additional units or operational steps and extra-energy consumption.

Using poly(vinyldodecylimidazolium bromide) for the in-situ product recovery of n-butanol.

The mitigation of end-product inhibition during the biosynthesis of n-butanol is demonstrated for an in-situ product recovery (ISPR) system employing a poly(ionic liquid) (PIL) absorbent. The thermodynamic affinity of poly(vinyldodecylimidazolium bromide) [P(VC12 ImBr)] for n-butanol, acetone and ethanol versus water was measured at conditions experienced in a typical acetone-ethanol-butanol (ABE) fermentation. In addition to providing a high n-butanol partition coefficient (PC = 6.5) and selectivity (αBuOH/water = 46), P(VC12 ImBr) is shown to be biocompatible with Saccharomyces cerevisiae and Clostridium acetobutylicum. Furthermore, the diffusivity of n-butanol in a hydrated PIL provides absorption rates that support ISPR applications. Using a 5 wt% PIL phase fraction relative to the aqueous phase mass, P(VC12 ImBr) improved the volumetric productivity of a batch ABE ISPR process by 31% relative to a control fermentation. The concentration of n-butanol in the P(VC12 ImBr) phase was sufficient to increase the alcohol concentration from 1.5 wt% in the fermentation medium to 25 wt% in the saturated PIL, thereby facilitating downstream n-butanol recovery.

The biological treatment of synthetic fracking fluid in an extractive membrane bioreactor: Selective transport and biodegradation of hydrophobic and hydrophilic contaminants.

The biodegradation of selected organic constituents present in hydraulic fracturing wastewater were examined in an extractive membrane bioreactor (EMB) operating with Hytrel™ 3548 tubing. Synthetic hydraulic fracturing wastewater was generated via an extensive literature review and contained high concentrations (1000 mg L-1) of contaminant compounds of varied hydrophobicity, viz. methyl ethyl ketone, benzene, phenol and acetic acid, as well as 30-120 g L-1 of Cl- at low pH. This hostile wastewater was circulated through the polymeric tubing, selectively transporting the organic compounds through the membrane for biological degradation by an enriched bacterial consortium. 16S rDNA analysis revealed the presence of five dominant microbial strains within the consortium, including: Pseudomonas sp., Comamonas sp., Achromobacter sp., Lysinibacillus sp., and Oxalobacter sp. EMBs in batch operation achieved 99% removal of methyl ethyl ketone, benzene, and phenol after 72 h and effectively removed acetic acid up to its ionization point. Continuous EMB operation provided 99% removal of benzene and phenol, 96% removal of methyl ethyl ketone, and 53% of acetic acid. The treatment of synthetic hydraulic fracturing fluid demonstrated the effectiveness of carefully selected amphiphilic polymers in EMBs for treating the hydrophilic and hydrophobic organic profile found in hydraulic fracturing wastewaters.

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.

On the applicability of a hybrid bioreactor operated with polymeric tubing for the biological treatment of saline wastewater.

Effective biological treatment of high salt content wastewater requires consideration of both salt and organic toxicity. This study treated a synthetic saline wastewater containing NaCl (100gL-1) and 2,4-dimethylphenol (1.2gL-1) with a hybrid system consisting of a biological reactor containing spiral-coiled polymeric tubing through which the mixed feed was pumped. The tubing wall was permeable to the organic contaminant, but not to the salt, which allowed transfer of the organic into the cell-containing bioreactor contents for degradation, while not exposing the cells to high salt concentrations. Different grades of DuPont Hytrel polymer were examined on the basis of organic affinity predictions and experimental partition and mass transfer tests. Hytrel G3548 tubing showed the highest permeability for 2,4-dimethylphenol while exerting an effective salt barrier, and was used to verify the feasibility of the proposed system. Very high organic removal (99% after just 5h of treatment) and effective biodegradation of the organic fraction of the wastewater (>90% at the end of the test) were observed. Complete salt separation from the microbial culture was also achieved.

A novel continuous two-phase partitioning bioreactor operated with polymeric tubing: Performance validation for enhanced biological removal of toxic substrates.

A continuous two-phase partitioning bioreactor (C-TPPB), operated with coiled tubing made of the DuPont polymer Hytrel 8206, was tested for the bioremediation of 4-chlorophenol, as a model toxic compound. The tubing was immersed in the aqueous phase, with the contaminated water flowing tube-side, and an adapted microbial culture suspended in the bioreactor itself, with the metabolic demand of the cells creating a concentration gradient to cause the substrate to diffuse into the bioreactor for biodegradation. The system was operated over a range of loadings (tubing influent concentration 750-1500 mg L-1), with near-complete substrate removal in all cases. Distribution of the contaminant at the end of the tests (96 h) highlighted biological removal in the range of 87-95%, while the amount retained in the polymer ranged from ∼1 to 8%. Mass transfer of the substrate across the tubing wall was not limiting, and the polymer demonstrated the capacity to buffer the substrate loadings and to adapt to microbial metabolism. The impact of C-TPPB operation on biomass activity was also investigated by a kinetic characterization of the microbial culture, which showed better resistance to substrate inhibition after C-TPPB operation, thereby confirming the beneficial effect of sub-inhibitory controlled conditions, characteristic of TPPB systems.

Sequential anaerobic-aerobic decolourization of a real textile wastewater in a two-phase partitioning bioreactor.

This work describes the application of a solid-liquid two-phase partitioning bioreactor (TPPB) for the removal of colour from a real textile wastewater containing reactive azo-dyes. Four polymers were tested over the pH range of 4-9 to select the most effective absorbant to be used as the partitioning phase in the TPPB. The best results were obtained with Hytrel 8206 at pH4 achieving ~70% colour removal, based on the dominant wavelength, in the first 5h of contact time, and 84% after 24h. Wastewater treatment was undertaken in a solid-liquid TPPB operated with Hytrel 8206 in sequential anaerobic-aerobic configuration. The reaction time of 23h was equally distributed between the anaerobic and aerobic phases and, to favour colour uptake, the pH was controlled at 4.5 in the first 4h of the anaerobic phase, and then increased to 7.5. Colour removal (for the dominant wavelength, 536nm) increased from 70 to 85% by modifying the bioreactor operation from single-phase to TPPB mode. Based on COD measurements nearly complete biodegradation of the intermediates produced in the anaerobic phase was obtained, both in the single-phase and two-phase mode, with better performance of the TPPB system reaching 75% CODDye removal.

Towards a continuous two-phase partitioning bioreactor for xenobiotic removal.

The removal of a xenobiotic (4-chlorophenol) from contaminated water was investigated in a simulated continuous two-phase partitioning bioreactor (C-TPPB), fitted with coiled tubing comprised of a specifically-selected extruded polymer, Hytrel 8206. Wastewater flowed inside the tubing, the pollutant diffused through the tubing wall, and was removed in the aqueous bioreactor phase at typical biological removal rates in the C-TTPB simulated by varying aqueous phase throughput to the reactor. Operating over a range of influent substrate concentrations (500-1500mgL(-1)) and hydraulic retention times in the tubing (4-8h), overall mass transfer coefficients were 1.7-3.5×10(-7)ms(-1), with the highest value corresponding to the highest tubing flow rate. Corresponding mass transfer rates are of the same order as biological removal rates, and thus do not limit the removal process. The C-TPPB showed good performance over all organic and hydraulic loading ranges, with removal efficiencies of 4CP in the tubing wastewater stream always ≥96%. Additionally, the presence of the Hytrel tubing was able to buffer increases in organic loading to the hybrid system, enhancing overall process stability. Biological testing of the C-TPPB confirmed the abiotic test results demonstrating even higher 4-chlorophenol removal efficiency (∼99%) in the tubing stream.

Heavy metals species affect fungal-bacterial synergism during the bioremediation of fluoranthene.

The co-occurrence of polycyclic aromatic hydrocarbons (PAHs) with heavy metals (HMs) is very common in contaminated soils, but the influence of HMs on fungal-bacterial synergism during PAH bioremediation has not been investigated. The bioremediation of fluoranthene-contaminated sand using co-cultures of Acremonium sp. P0997 and Bacillus subtilis showed increases of 109.4 and 9.8 % in degradation compared to pure bacterial and fungal cultures, respectively, removing 64.1 ± 1.4 % fluoanthene in total. The presence of Cu(2+) reduced fluoranthene removal to 53.7 ± 1.7 %, while inhibiting bacterial growth, and reducing translocation of bacteria on fungal hyphae by 49.5 %, in terms of the bacterial translocation ratio. Cu(2+) reduced bacterial diffusion by 46.8 and 31.9 %, as reflected by D (a bulk random motility diffusional coefficient) and D eff (the effective one-dimensional diffusion coefficient) compared to the control without HM supplementation, respectively. However, Mn(2+) resulted in a 78.2 ± 1.9 % fluoranthene degradation, representing an increase of 21.9 %, while enhancing bacterial growth and bacterial translocation on fungal hyphae, showing a 12.0 % increase in translocation ratio, with no observable impact on D and D eff. Hence, the presence of HMs has been shown to affect fungal-bacterial synergism in PAH degradation, and this effect differs with HM species.

Selecting polymers for two-phase partitioning bioreactors (TPPBs): Consideration of thermodynamic affinity, crystallinity, and glass transition temperature.

Two-phase partitioning bioreactor technology involves the use of a secondary immiscible phase to lower the concentration of cytotoxic solutes in the fermentation broth to subinhibitory levels. Although polymeric absorbents have attracted recent interest due to their low cost and biocompatibility, material selection requires the consideration of properties beyond those of small molecule absorbents (i.e., immiscible organic solvents). These include a polymer's (1) thermodynamic affinity for the target compound, (2) degree of crystallinity (wc ), and (3) glass transition temperature (Tg ). We have examined the capability of three thermodynamic models to predict the partition coefficient (PC) for n-butyric acid, a fermentation product, in 15 polymers. Whereas PC predictions for amorphous materials had an average absolute deviation (AAD) of ≥16%, predictions for semicrystalline polymers were less accurate (AAD ≥ 30%). Prediction errors were associated with uncertainties in determining the degree of crystallinity within a polymer and the effect of absorbed water on n-butyric acid partitioning. Further complications were found to arise for semicrystalline polymers, wherein strongly interacting solutes increased the polymer's absorptive capacity by actually dissolving the crystalline fraction. Finally, we determined that diffusion limitations may occur for polymers operating near their Tg , and that the Tg can be reduced by plasticization by water and/or solute. This study has demonstrated the impact of basic material properties that affects the performance of polymers as sequestering phases in TPPBs, and reflects the additional complexity of polymers that must be taken into account in material selection.

Biocompatibility of low molecular weight polymers for two-phase partitioning bioreactors.

Two phase partitioning bioreactors (TPPBs) improve the efficiency of fermentative processes by limiting the exposure of microorganisms to toxic solutes by sequestering them into a non-aqueous phase (NAP). A potential limitation of this technology, when using immiscible organic solvents as the NAP, is the cytoxicity that these materials may exert on the microbes. An improved TPPB configuration is one in which polymeric NAPs are used to replace organic solvents in order to take advantage of their low cost, improved handling qualities, and biocompatibility. A recent study has shown that low molecular weight polymers may confer improved solute uptake relative to high molecular weight polymers (i.e., have higher partition coefficients), but it is unknown whether sufficiently low molecular weight polymers may inhibit cell growth. This study has investigated the biocompatibility of a range of low molecular weight polymers, and compared trends in biocompatibility to the well-established "critical log P" concept. This was achieved by determining the biocompatibility of polypropylene glycol polymers over a molecular weight (MW) range of 425-4,000 to Saccharomyces cerevisiae and Pseudomonas putida, two organisms which have been previously used in TPPB systems. The lower MW polymers were shown to have lower average log P values, and showed more cytotoxicity than polymers of the same structure but with higher molecular weight. Since polymers are generally polydisperse (i.e., polymer samples contain a distribution of MWs), removal of the lower MW fractions via water washing was found to result in improved polymer biocompatibility. These results suggest that the critical log P concept remains useful for describing the toxicity of polymeric substances of different MWs, although it is complicated by the presence of the low MW fractions in the polymers arising from polydispersity.

Rapid and effective decontamination of chlorophenol-contaminated soil by sorption into commercial polymers: concept demonstration and process modeling.

Solid phase extraction performed with commercial polymer beads to treat soil contaminated by chlorophenols (4-chlorophenol, 2,4-dichlorophenol and pentachlorophenol) as single compounds and in a mixture has been investigated in this study. Soil-water-polymer partition tests were conducted to determine the relative affinities of single compounds in soil-water and polymer-water pairs. Subsequent soil extraction tests were performed with Hytrel 8206, the polymer showing the highest affinity for the tested chlorophenols. Factors that were examined were polymer type, moisture content, and contamination level. Increased moisture content (up to 100%) improved the extraction efficiency for all three compounds. Extraction tests at this upper level of moisture content showed removal efficiencies ≥70% for all the compounds and their ternary mixture, for 24 h of contact time, which is in contrast to the weeks and months, normally required for conventional ex situ remediation processes. A dynamic model characterizing the rate and extent of decontamination was also formulated, calibrated and validated with the experimental data. The proposed model, based on the simplified approach of "lumped parameters" for the mass transfer coefficients, provided very good predictions of the experimental data for the absorptive removal of contaminants from soil at different individual solute levels. Parameters evaluated from calibration by fitting of single compound data, have been successfully applied to predict mixture data, with differences between experimental and predicted data in all cases being ≤3%.

The use of high pressure CO2 -facilitated pH swings to enhance in situ product recovery of butyric acid in a two-phase partitioning bioreactor.

Through the use of high partial pressures of CO2 (pCO2 ) to facilitate temporary pH reductions in two-phase partitioning bioreactors (TPPBs), improved pH dependent partitioning of butyric acid was observed which achieved in situ product recovery (ISPR), alleviating end-product inhibition (EPI) during the production of butyric acid by Clostridium tyrobutyricum (ATCC 25755). Through high pressure pCO2 studies, media buffering effects were shown to be substantially overcome at 60 bar pCO2 , resulting in effective extraction of the organic acid by the absorptive polymer Pebax® 2533, yielding a distribution coefficient (D) of 2.4 ± 0.1 after 1 h of contact at this pressure. Importantly, it was also found that C. tyrobutyricum cultures were able to withstand 60 bar pCO2 for 1 h with no decrease in growth ability when returned to atmospheric pressure in batch reactors after several extraction cycles. A fed-batch reactor with cyclic high pCO2 polymer extraction recovered 92 g of butyric acid to produce a total of 213 g compared to 121 g generated in a control reactor. This recovery reduced EPI in the TPPB, resulting in both higher productivity (0.65 vs. 0.33 g L(-1) h(-1) ) and yield (0.54 vs. 0.40). Fortuitously, it was also found that repeated high pCO2 -facilitated polymer extractions of butyric acid during batch growth of C. tyrobutyricum lessened the need for pH control, and reduced base requirements by approximately 50%. Thus, high pCO2 -mediated absorptive polymer extraction presents a novel method for improving process performance in butyric acid fermentation, and this technique could be applied to the bioproduction of other organic acids as well.

The use of used automobile tyres in a partitioning bioreactor for the biodegradation of xenobiotic mixtures.

Waste tyres were utilized as the sorption phase in a two-phase partitioning bioreactor (TPPB) for the biodegradation of a binary mixture of 2,4-dichlorophenol (DCP) and 4-nitrophenol (4NP). These compounds are extensively used in the chemical industry and are found in many industrial effluents. Although both compounds are toxic and are on the EPA list of priority pollutants, a higher inhibitory effect on microorganisms is exerted by DCP, and our experimental tests were focused on strategies to reduce its negative impact on microbial activity. Sorption/desorption tests for the DCP-4NP mixture were first performed to verify the related uptake/release rates by the tyres, which showed that the tyres had a higher capacity for DCP uptake and practically no affinity for 4NP. An acclimatized mixed culture was then utilized in a sequencing batch reactor (SBR) operated in conventional and two-phase mode. For the binary DCP-4NP mixture a significant reduction in DCP toxicity, and a concomitant enhancement in substrate removal efficiency (up to 83%for DCP and approximate 100% for 4NP) were clearly seen for the TPPB operated with 10% and 15% v/v tyres, for influent concentrations up to 180 mg/L, with practically negligible biodegradation in the conventional single phase reactor. The long-term utilization of tyres was confirmed at an influent loading of 180 mg/L with a test performed over 20 work cycles showing an improvement of the removal performance for both compounds.

Effect of bioconversion conditions on vanillin production by Amycolatopsis sp. ATCC 39116 through an analysis of competing by-product formation.

This study investigated the effects of transformation conditions such as initial pH, the initial concentration of glucose and yeast extract in the medium, and the separate addition of ferulic acid and vanillic acid, on the production of vanillin through an analysis of competing by-product formation by Amycolatopsis sp. ATCC 39116. The extent and nature of by-product formation and vanillin yield were affected by initial pH and different initial concentrations of glucose and yeast extract in the medium, with a high yield of vanillin and high cell density obtained at pH 8.0, 10 g/l glucose, and 8 g/l yeast extract. High concentrations of ferulic acid were found to negatively affect cell density. Additional supplementation of 100 mg/l vanillic acid, a metabolically linked by-product, was found to result in a high concentration of vanillin and guaiacol, an intermediate of vanillin. Via an analysis of the effect of these transformation conditions on competing by-product formation, high concentrations of ferulic acid were transformed with a molar yield to vanillin of 96.1 and 95.2 %, by Amycolatopsis sp. ATCC 39116 and Streptomyces V1, respectively, together with a minor accumulation of by-products. These are among the highest performance values reported in the literature to date for Streptomyces in batch cultures.

Transformation of ferulic acid to vanillin using a fed-batch solid-liquid two-phase partitioning bioreactor.

Amycolatopsis sp. ATCC 39116 (formerly Streptomyces setonii) has shown promising results in converting ferulic acid (trans-4-hydroxy-3-methoxycinnamic acid; substrate), which can be derived from natural plant wastes, to vanillin (4-hydroxy-3-methoxybenzaldehyde). After exploring the influence of adding vanillin at different times during the growth cycle on cell growth and transformation performance of this strain and demonstrating the inhibitory effect of vanillin, a solid-liquid two-phase partitioning bioreactor (TPPB) system was used as an in situ product removal technique to enhance transformation productivity by this strain. The thermoplastic polymer Hytrel(®) G4078W was found to have superior partitioning capacity for vanillin with a partition coefficient of 12 and a low affinity for the substrate. A 3-L working volume solid-liquid fed-batch TPPB mode, using 300 g Hytrel G4078W as the sequestering phase, produced a final vanillin concentration of 19.5 g/L. The overall productivity of this reactor system was 450 mg/L. h, among the highest reported in literature. Vanillin was easily and quantitatively recovered from the polymers mostly by single stage extraction into methanol or other organic solvents used in food industry, simultaneously regenerating polymer beads for reuse. A polymer-liquid two phase bioreactor was again confirmed to easily outperform single phase systems that feature inhibitory or easily further degraded substrates/products. This enhancement strategy might reasonably be expected in the production of other flavor and fragrance compounds obtained by biotransformations.

Demonstration of in situ product recovery of butyric acid via CO2 -facilitated pH swings and medium development in two-phase partitioning bioreactors.

Production of organic acids in solid-liquid two-phase partitioning bioreactors (TPPBs) is challenging, and highly pH-dependent, as cell growth occurs near neutral pH, while acid sorption occurs only at low pH conditions. CO2 sparging was used to achieve acidic pH swings, facilitating undissociated organic acid uptake without generating osmotic stress inherent in traditional acid/base pH control. A modified cultivation medium was formulated to permit greater pH reduction by CO2 sparging (pH 4.8) compared to typical media (pH 5.3), while still possessing adequate nutrients for extensive cell growth. In situ product recovery (ISPR) of butyric acid (pKa = 4.8) produced by Clostridium tyrobutyricum was achieved through intermittent CO2 sparging while recycling reactor contents through a column packed with absorptive polymer Hytrel® 3078. This polymer was selected on the basis of its composition as a polyether copolymer, and the use of solubility parameters for predicting solute polymer affinity, and was found to have a partition coefficient for butyric acid of 3. Total polymeric extraction of 3.2 g butyric acid with no CO2 mediated pH swings was increased to 4.5 g via CO2 -facilitated pH shifting, despite the buffering capacity of butyric acid, which resists pH shifting. This work shows that CO2 -mediated pH swings have an observable positive effect on organic acid extraction, with improvements well over 150% under optimal conditions in early stage fermentation compared to CO2 -free controls, and this technique can be applied other organic acid fermentations to achieve or improve ISPR.

Production of 4-valerolactone by an equilibrium-limited transformation in a partitioning bioreactor: impact of absorptive polymer properties.

The biotransformation of levulinic acid to 4-valerolactone (4VL) is pH-dependent and equilibrium limited, distinct from the more common irreversible biotransformations that are constrained by product toxicity or biocatalyst inhibition. Our processing strategy for this system was to selectively remove the product, 4VL, which is in equilibrium with its precursor, 4-hydroxyvalerate (4HV), to pull the reaction to a greater extent of conversion. 4VL is challenging to separate from the aqueous phase due to its water miscibility, necessitating the use of water-absorbing polymers to provide affinity toward the hydrophilic product. Manipulating the composition of copolymers, thereby varying the architecture of polymer chains, conferred drastically different extents of water absorption and caused different biotransformation outcomes. A custom-synthesized random copolymer designed to maximize the proportion of material with affinity for the solute had high water uptake, which resulted in the poor selectivity for the target molecule relative to its precursor. Conversely, a moderately water-absorbing commercial segmented block copolymer, Hytrel(®) 8206, demonstrated selectivity toward 4VL relative to its precursor, 4HV, and increased 4VL production by approximately 30 % by shifting the equilibrium toward the product. This work has shown that water absorption is an important, previously neglected criterion in evaluating polymer affinity and selectivity toward hydrophilic target molecules.

In situ product removal in fermentation systems: improved process performance and rational extractant selection.

The separation of inhibitory compounds as they are produced in biotransformation and fermentation systems is termed in situ product removal (ISPR). This review examines recent ISPR strategies employing several classes of extractants including liquids, solids, gases, and combined extraction systems. Improvement through the simple application of an auxiliary phase are tabulated and summarized to indicate the breadth of recent ISPR activities. Studies within the past 5 years that have highlighted and have discussed "second phase" properties, and that have an effect on fermentation performance, are particular focus of this review. ISPR, as a demonstrably effective processing strategy, continues to be widely adopted as more applications are explored; however, focus on the properties of extractants and their rational selection based on first principle considerations will likely be key to successfully applying ISPR to more challenging target molecules.

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.