Performance comparison of hematite (α-Fe2O3)-polymer composite and core-shell nanofibers as point-of-use filtration platforms for metal sequestration.

Point-of-use water treatment technologies can help mitigate risks from drinking water contamination, particularly for metals (and metalloids) that originate in distribution systems (e.g., chromium, lead, copper) or are naturally occurring in private groundwater wells (e.g., arsenic). Here, composite nanofibers of polyacrylonitrile (PAN) with embedded hematite (α-Fe2O3) nanoparticles were synthesized via a single-pot electrospinning synthesis. A core-shell nanofiber composite was also prepared through the subsequent hydrothermal growth of α-Fe2O3 nanostructures on embedded hematite composites. Properties of embedded hematite composites were controlled using electrospinning synthesis variables (e.g., size and loading of embedded α-Fe2O3 nanoparticles), whereas core-shell composites were also tailored via hydrothermal treatment conditions (e.g., soluble iron concentration and duration). Although uptake of Cu(II), Pb(II), Cr(VI), and As(V) was largely independent of the core-shell variables explored, metal uptake on embedded nanofibers increased with α-Fe2O3 loading. Both materials exhibited maximum surface-area-normalized sorption capacities that were comparable to α-Fe2O3 nanoparticle dispersions and exceeded that of a commercial iron oxide based sorbent. Further, both types of composite exhibited strong performance across a range of environmentally relevant pH values (6.0-8.0). Notably, core-shell structures, with a majority of surface accessible α-Fe2O3, performed far better than embedded composites in kinetically limited flow through systems than was anticipated from their relative performance in equilibrium batch systems. Core-shell nanofiber filters also retained much of the durability and flexibility exhibited by embedded nanofibers. Additional tests with authentic groundwater samples demonstrated the ability of the core-shell nanofiber filters to remove simultaneously both As and suspended solids, illustrating their promise as a nano-enabled technology for point-of-use water treatment.

Tailored synthesis of photoactive TiO 2 nanofibers and Au/TiO 2 nanofiber composites: structure and reactivity optimization for water treatment applications.

Titanium dioxide (TiO2) nanofibers with tailored structure and composition were synthesized by electrospinning to optimize photocatalytic treatment efficiency. Nanofibers of controlled diameter (30-210 nm), crystal structure (anatase, rutile, mixed phases), and grain size (20-50 nm) were developed along with composite nanofibers with either surface-deposited or bulk-integrated Au nanoparticle cocatalysts. Their reactivity was then examined in batch suspensions toward model (phenol) and emerging (pharmaceuticals, personal care products) pollutants across various water qualities. Optimized TiO2 nanofibers meet or exceed the performance of traditional nanoparticulate photocatalysts (e.g., Aeroxide P25) with the greatest reactivity enhancements arising from (i) decreasing diameter (i.e., increasing surface area), (ii) mixed phase composition [74/26 (±0.5) % anatase/rutile], and (iii) small amounts (1.5 wt %) of surface-deposited, more so than bulk-integrated, Au nanoparticles. Surface Au deposition consistently enhanced photoactivity by 5- to 10-fold across our micropollutant suite independent of their solution concentration, behavior that we attribute to higher photocatalytic efficiency from improved charge separation. However, the practical value of Au/TiO2 nanofibers was limited by their greater degree of inhibition by solution-phase radical scavengers and higher rate of reactivity loss from surface fouling in nonidealized matrixes (e.g., partially treated surface water). Ultimately, unmodified TiO2 nanofibers appear most promising for use as reactive filtration materials because their performance was less influenced by water quality, although future efforts must increase the strength of TiO2 nanofiber mats to realize such applications.

Partial nitritation ANAMMOX in submerged attached growth bioreactors with smart aeration at 20 °C.

Submerged attached growth bioreactors (SAGBs) were operated at 20 °C for 30 weeks in smart-aerated, partial nitritation ANAMMOX mode and in a timer-controlled, cyclic aeration mode. The smart-aerated SAGBs removed 48-53% of total nitrogen (TN) compared to 45% for SAGBs with timed aeration. Low dissolved oxygen concentrations and cyclic pH patterns in the smart-aerated SAGBs suggested conditions favorable to partial nitritation ANAMMOX and stoichiometrically-derived and numerically modeled estimations attributed 63-68% and 14-44% of TN removal to partial nitritation ANAMMOX in these bioreactors, respectively. Ammonia removals of 36-67% in the smart-aerated SAGBs, with measured oxygen and organic carbon limitations, further suggest partial nitritation ANAMMOX. The smart-aerated SAGBs required substantially less aeration to achieve TN removals similar to SAGBs with timer-controlled aeration. Genomic DNA testing confirmed that the dominant ANAMMOX seed bacteria, received from a treatment plant utilizing the DEMON® sidestream deammonification process, was a Candidatus Brocadia sp. (of the Planctomycetales order). The DNA from these bacteria was also present in the SAGBs at the conclusion of the study providing evidence for attached growth and limited biomass washout.

Nitrogen removal from wastewater by an aerated subsurface-flow constructed wetland in cold climates.

The objective of this study was to assess the role of cyclic aeration, vegetation, and temperature on nitrogen removal by subsurface-flow engineered wetlands. Aeration was shown to enhance total nitrogen and ammonia removal and to enhance removal of carbonaceous biochemical oxygen demand, chemical oxygen demand, and phosphorus. Effluent ammonia and total nitrogen concentrations were significantly lower in aerated wetland cells when compared with unaerated cells. There was no significant difference in nitrogen removal between planted and unplanted cells. Effluent total nitrogen concentrations ranged from 9 to 12 mg N/L in the aerated cells and from 23 to 24 mg N/L in unaerated cells. Effluent ammonia concentrations ranged from 3 to 7 mg N/L in aerated wetland cells and from 22 to 23 mg N/L in unaerated cells. For the conditions tested, temperature had only a minimal effect on effluent ammonia or total nitrogen concentrations. The tanks-in-series and the PkC models predicted the general trends in effluent ammonia and total nitrogen concentrations, but did not do well predicting short-term variability. Rate coefficients for aerated systems were 2 to 10 times greater than those for unaerated systems.

Diversity of the chlorite dismutase gene in low and high organic carbon rhizosphere soil colonized by perchlorate-reducing bacteria.

Chlorite dismutase (cld) is an essential enzyme in the biodegradation of perchlorate. The objective of this study was to determine the change in sequence diversity of the cld gene, and universal bacterial 16S rRNA genes, in soil samples under varying conditions of organic carbon, bioaugmentation, and plant influence. The cld gene diversity was not different between high organic carbon (HOC) and low organic carbon (LOC) soil. Combining results from HOC and LOC soil, diversity of the cld gene was decreased in soil that had been bioaugmented or planted. However, with both bioaugmentation and planting the cld diversity was not decreased. These observations were repeated when focusing on LOC soil. However, in HOC soil the cld diversity was not affected by reactor treatment. General bacterial diversity as measured with 16S rRNA was significantly greater in HOC soil than in LOC soil, but no significant difference was observed between reference soil and planted or bioaugmented soil. Different sequences of the cld gene occur in different species of microorganisms. In LOC soil, combining bioaugmentation and planting results in a highly diverse population of perchlorate degraders. This diverse population will be more resilient and is desirable where perchlorate reduction is a critical remediation process. Supplemental materials are available for this article. Go to the publisher's online edition of International Journal of Phytoremediation to view the supplemental file.

Effect of sulfide inhibition and organic shock loading on anaerobic biofilm reactors treating a low-temperature, high-sulfate wastewater.

To assess the long-term treatment of sulfate- and carbon-rich wastewater at low temperatures, anaerobic biofilm reactors were operated for over 900 days at 20 degrees C and fed wastewater containing lactate and sulfate. Results showed the reactors could be operated at 20 degrees C with a load rate of 1.3 g-chemical oxygen demand (COD)/L x d or less and a sulfur loading rate (SLR) of 0.2 g-S/L x d, with no significant deterioration in performance. With acclimation periods, load rates of 3.4 g-COD/L x d and SLR of 0.3 g/L x d could be tolerated. Effluent dissolved sulfide and hydrogen sulfide levels were approximately 600 and 150 mg-S/L, respectively, during this period. The effect of organic shock loading was also assessed. Reactors appeared to recover from one, but not two, lactate spikes of approximately 5000 mg-COD/L. Long-term stability was achieved in reactors containing large, stable populations of lactate- and propionate-degrading sulfate-reducing bacteria and aceticlastic methanogens.

Influence of electron donor, oxygen, and redox potential on bacterial perchlorate degradation.

Experiments were conducted to assess the influence of electron donor, redox potential, and dissolved oxygen on bacterial perchlorate degradation. Microcosms containing a diverse, perchlorate-acclimated, bacterial culture fed lactate at a 1:1 electron donor-to-perchlorate ratio (electron-equivalent basis) degraded perchlorate more slowly (k = 0.038 mg ClO4-/mg VSS h) and to a lesser extent than microcosms fed lactate at 2:1 and 4:1 ratios (k = 0.045 mg ClO4-/mg VSS h). The optimal COD/ClO4- ratio to consume all perchlorate and all electron donor was approximately 1.2 mg COD/mg ClO4-. In experiments where the redox potential was held constant, the extent of perchlorate degradation increased with decreasing redox potential, and 100% removal was only achieved at the lowest redox potential examined (-220 mV); however, perchlorate degradation (32% of added perchlorate) was observed as high as +180 mV. Additions of oxygen to actively degrading treatments did not adversely effect perchlorate degradation. It appears, therefore, that addition of excess electron donor is sufficient to negate potential inhibitory effects of molecular oxygen. If the redox conditions are more oxidized, however, the rate and extent of perchlorate degradation will be significantly decreased. This is the first report of perchlorate degradation under oxidized conditions using an environmentally relevant, diverse, bacterial enrichment culture, and this is also the first report of perchlorate reduction occurring at appreciable dissolved oxygen concentrations in a batch system.

Stimulation and molecular characterization of bacterial perchlorate degradation by plant-produced electron donors.

Root homogenate from poplar trees (Populus deltoides x nigra DN34, Imperial Carolina) stimulated perchlorate degradation in microcosms of soil and water samples collected at a perchlorate contaminated site, the Longhorn Army Ammunition Plant (LHAAP), located outside Karnack, Texas. Direct use of root products by perchlorate-degrading bacteria was shown for the first time as six pureculture bacteria isolated from LHAAP perchlorate-degrading microcosms degraded perchlorate when given root products as the sole exogenous source of carbon and electron donor. Nonenriched environmental consortia were able to utilize root products for perchlorate degradation, regardless of prior exposure to perchlorate. Microcosms that contained perchlorate-contaminated groundwater (MW-3) or uncontaminated surface water (Harrison Bayou) as inoculum degraded approximately 240 and 160 mg L(-1) perchlorate, respectively, using root products (approximately 440 mg L(-1) as COD) over 38 days. The predominant bacterial species in these aqueous microcosms, identified by DGGE, depended only upon the source inoculum as similar sequences were obtained whether root products or lactate was the electron donor. Sequences from DGGE bands that matched species within Dechloromonas, a genus consisting of many perchlorate degraders, were identified in all perchlorate-degrading microcosms. This study demonstrates the ability of root products to drive perchlorate respiration by bacteria and the potential for successful achievement of perchlorate rhizodegradation using in situ phytoremediation.

Hexahydro-1,3,5-trinitro-1,3,5-triazine transformation by biologically reduced ferrihydrite: evolution of Fe mineralogy, surface area, and reaction rates.

Microbial respiration of Fe(III) oxides has been shown to produce reduced Fe phases that are capable of transforming a variety of oxidized contaminants. Little data, however, are available on how these Fe phases evolve over time and how this evolution may affect their ability to reduce contaminants. Here,the evolution and reactivity of biologically reduced ferrihydrite were monitored over a period of 14 months. Solids were collected from a culture of Geobacter metallireducens (GS-15) thatwas incubated with ferrihydrite (as the electron acceptor) for 0, 7, 10, 20, 75, and 400 days. Mineralogical composition and surface area of the biologically reduced solids were characterized using Mössbauer spectroscopy, X-ray diffraction, and BET with N2 adsorption. By day 10, ferrihydrite began to transform, and a nanoparticle magnetite/maghemite phase, as well as two ferrous phases, was observed. One of the ferrous phases was identified as siderite, whereas the other could not be positively identified. Likely candidates, however, include Fe(OH)2(s) or an adsorbed Fe(II) species. Over the next few months, ferrihydrite was completely reduced and evolved into a mixture containing about 70% magnetite/maghemite, 19% siderite, and 11% of the second Fe(II) phase. The effect of incubation time on the reactivity of the biologically reduced solids was evaluated by measuring the kinetics of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) transformation. The only products observed were the three reduced nitroso products. Rate coefficients (k) for RDX transformation were dramatically influenced by incubation time with half-lives of about 1 month observed in the presence of solids incubated for 10 and 20 days, 3 months with solids incubated for 75 days, and negligible removal with solids incubated for 400 days. The loss of reactivity was not directly correlated to any one mineralogical variable but may be due to particle size or surface chemistry changes in the reactive Fe phase or to cell die-off and the accumulation of cell lysis products after consumption of the electron acceptor. The dramatic effect of incubation time on the rate of RDX removal highlights a potential limitation of studying complex systems, as we have here, in batch reactors and suggests that incubation time is an important variable to consider when measuring and comparing rates of contaminant reduction.

Isolation and characterization of autotrophic, hydrogen-utilizing, perchlorate-reducing bacteria.

Recent studies have shown that perchlorate (ClO(4) (-)) can be degraded by some pure-culture and mixed-culture bacteria with the addition of hydrogen. This paper describes the isolation of two hydrogen-utilizing perchlorate-degrading bacteria capable of using inorganic carbon for growth. These autotrophic bacteria are within the genus Dechloromonas and are the first Dechloromonas species that are microaerophilic and incapable of growth at atmospheric oxygen concentrations. Dechloromonas sp. JDS5 and Dechloromonas sp. JDS6 are the first perchlorate-degrading autotrophs isolated from a perchlorate-contaminated site. Measured hydrogen thresholds were higher than for other environmentally significant, hydrogen-utilizing, anaerobic bacteria (e.g., halorespirers). The chlorite dismutase activity of these bacteria was greater for autotrophically grown cells than for cells grown heterotrophically on lactate. These bacteria used fumarate as an alternate electron acceptor, which is the first report of growth on an organic electron acceptor by perchlorate-reducing bacteria.

Inhibition of bacterial perchlorate reduction by zero-valent iron.

Perchlorate was reduced by a mixed bacterial culture over a pH range of 7.0-8.9. Similar rates of perchlorate reduction were observed between pH 7.0 and 8.5, whereas significantly slower reduction occurred at pH 8.9. Addition of iron metal, Fe(0), to the mixed bacterial culture resulted in slower rates of perchlorate reduction. Negligible perchlorate reduction was observed under abiotic conditions with Fe(0) alone in a reduced anaerobic medium. The inhibition of perchlorate reduction observed in the presence of Fe(0) is in contrast to previous studies that have shown faster rates of contaminant reduction when bacteria and Fe(0) were combined compared to bacteria alone. The addition of Fe(0) resulted in a rise in pH, as well as precipitation of Fe minerals that appeared to encapsulate the bacterial cells. In experiments where pH was kept constant, the addition of Fe(0) still resulted in slower rates of perchlorate reduction suggesting that encapsulation of bacteria by Fe precipitates contributed to the inhibition of the bacterial activity independent of the effect of pH on bacteria. These results provide the first evidence linking accumulation of iron precipitates at the cell surface to inhibition of environmental contaminant degradation. Fe(0) was not a suitable amendment to stimulate perchlorate-degrading bacteria and the bacterial inhibition caused by precipitation of reduced Fe species may be important in other combined anaerobic bacterial-Fe(0) systems. Furthermore, the inhibition of bacterial activity by iron precipitation may have significant implications for the design of in situ bioremediation technologies for treatment of perchlorate plumes.

Abiotic transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine by Fe(II) bound to magnetite.

RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), a nitramine explosive, is often found as a subsurface contaminant at military installations. Though biological transformations of RDX are often reported, abiotic studies in a defined medium are uncommon. The work reported here was initiated to investigate the transformation of RDX by ferrous iron (Fe(II)) associated with a mineral surface. RDX is transformed by Fe(II) in aqueous suspensions of magnetite (Fe3O4). Negligible transformation of RDX occurred when it was exposed to Fe(II) or magnetite alone. The sequential nitroso reduction products (MNX, DNX, and TNX) were observed as intermediates. NH4+, N2O, and HCHO were stable products of the transformation. Experiments with radiolabeled RDX indicate that 90% of the carbon end products remained in solution and that negligible mineralization occurred. Rates of RDX transformation measured for a range of initial Fe(II) concentrations and solution pH values indicate that greater amounts of adsorbed Fe(II) result in faster transformation rates. As pH increases, more Fe(II) adsorbs and k(obs) increases. The degradation of RDX by Fe(II)-magnetite suspensions indicates a possible remedial option that could be employed in natural and engineered environments where iron oxides are abundant and ferrous iron is present.

Kinetics of 1,1,1-trichloroethane transformation by iron sulfide and a methanogenic consortium.

To evaluate the effect of potential interactions between methanogenic bacteria and iron sulfide minerals during transformation of 1,1,1-trichloroethane (1,1,1-TCA), we measured the kinetics of 1,1,1-TCA transformation by mackinawite (FeS(1 - x), but abbreviated as FeS) and a methanogenic consortium enriched on lactate (termed LEC). Results from batch kinetic experiments show that 1,1,1-TCA transformation by FeS and resting LEC can be described by second-order rate expressions, with rates depending on 1,1,1-TCA concentration (M), FeS surface area concentration (m2 L(-1)), and LEC concentration (as measured by mg L(-1) volatile suspended solids (VSS)). In reactors containing FeS alone, 1,1-dichloroethane (1,1-DCA) and 2-butyne were identified as products, but only accounted for 6% of the 1,1,1-TCA transformed. In reactors containing LEC alone, the only identified product was 1,1-DCA, which accounted for 46 +/- 8% of the 1,1,1-TCA transformed. Supernatant from LEC-alone reactors also transformed 1,1,1-TCA, suggesting that 1,1,1-TCA may be transformed by some non-cell component (such as a extracellular compound excreted by the organisms) that either reacts directly with 1,1,1-TCA or with the abiotic media to form a reactive species. Comparison of 1,1,1-TCA transformation rates from experiments with combinations of FeS (varying surface area concentrations) and LEC (varying VSS concentrations) to those with just FeS alone or LEC alone suggests some synergism occurs between the two reactive species. Observed enhancements took the form of faster 1,1,1-TCA transformation and faster 1,1-DCA appearance but less production of 1,1-DCA per unit of 1,1,1-TCA transformed. These observations suggest that the faster 1,1,1-TCA transformation in the combined systems (compared to the FeS-alone and LEC-alone experiments) is due to increased reactivity of both FeS and LEC, possibly due to production of soluble microbial products that make the FeS more reactive or less inhibition of LEC by 1,1,1-TCA due to FeS transformation of 1,1,1-TCA.