Adsorptive-Photocatalytic Performance for Antibiotic and Personal Care Product Using Cu0.5Mn0.5Fe2O4.

The amount of antibiotics and personal care products entering local sewage systems and ultimately natural waters is increasing and raising concerns about long-term human health effects. We developed an adsorptive photocatalyst, Cu0.5Mn0.5Fe2O4 nanoparticles, utilizing co-precipitation and calcination with melamine, and quantified its efficacy in removing paraben and oxytetracycline (OTC). During melamine calcination, Cu0.5Mn0.5Fe2O4 recrystallized, improving material crystallinity and purity for the adsorptive-photocatalytic reaction. Kinetic experiments showed that all four parabens and OTC were removed within 120 and 45 min. We found that contaminant adsorption and reaction with active radicals occurred almost simultaneously with the photocatalyst. OTC adsorption could be adequately described by the Brouers-Sotolongo kinetic and Freundlich isotherm models. OTC photocatalytic degradation started with a series of reactions at different carbon locations (i.e., decarboxamidation, deamination, dehydroxylation, demethylation, and tautomerization). Further toxicity testing showed that Zea mays L. and Vigna radiata L. shoot indexes were less affected by treated water than root indexes. The Zea mays L. endodermis thickness and area decreased considerably after exposure to the 25% (v/v)-treated water. Overall, Cu0.5Mn0.5Fe2O4 nanoparticles exhibit a remarkable adsorptive-photocatalytic performance for the degradation of tested antibiotics and personal care products.

Enhanced degradation of herbicides in groundwater using sulfur-containing reductants and spinel zinc ferrite activated persulfate.

A challenge to successfully implementing an injection-based remedial treatment in aquifers is to ensure that the oxidative reaction is efficient and lasts long enough to contact the contaminated plume. Our objective was to determine the efficacy of zinc ferrite nanocomposites (ZnFe2O4) and sulfur-containing reductants (SCR) (i.e., dithionite; DTN and bisulfite; BS) to co-activate persulfate (S2O82-; PS) and treat herbicide-contaminated water. We also evaluated the ecotoxicity of the treated water. While both SCRs delivered excellent PS activation in a 1:0.4 ratio (PS:SCR), the reaction was relatively short-lived. By including ZnFe2O4 in the PS/BS or PS/DTN activations, herbicide degradation rates dramatically increased by factors of 2.5 to 11.3. This was due to the SO4- and OH reactive radical species that formed. Radical scavenging experiments and ZnFe2O4 XPS spectra results revealed that SO4- was the dominant reactive species that originated from S(IV)/PS activation in solution and from the Fe(II)/PS activation that occurred on the ZnFe2O4 surface. Based on liquid chromatography mass spectrometry (LC-MS), atrazine and alachlor degradation pathways are proposed that involve both dehydration and hydroxylation. In 1-D column experiments, five different treatment scenarios were run using 14C-labeled and unlabeled atrazine, and 3H2O to quantify changes in breakthrough curves. Our results confirmed that ZnFe2O4 successfully prolonged the PS oxidative treatment despite the SCR being completely dissociated. Toxicity testing showed treated 14C-atrazine was more biodegradable than the parent compound in soil microcosms. Post-treatment water (25 %, v/v) also had less impact on both Zea Mays L. and Vigna radiata L. seedling growth, but more impact on root anatomies, while ≤4 % of the treated water started to exert cytotoxicity (<80 % viability) on ELT3 cell lines. Overall, the findings confirm that ZnFe2O4/SCR/PS reaction is efficient and relatively longer lasting in treating herbicide-contaminated groundwater.

Developing a Slow-Release Permanganate Composite for Degrading Aquaculture Antibiotics.

Copious use of antibiotics in aquaculture farming systems has resulted in surface water contamination in some countries. Our objective was to develop a slow-release oxidant that could be used in situ to reduce antibiotic concentrations in discharges from aquaculture lagoons. We accomplished this by generating a slow-release permanganate (SR-MnO4-) that was composed of a biodegradable wax and a phosphate-based dispersing agent. Sulfadimethoxine (SDM) and its synergistic antibiotics were used as representative surrogates. Kinetic experiments verified that the antibiotic-MnO4- reactions were first-order with respect to MnO4- and initial antibiotic concentration (second-order rates: 0.056-0.128 s-1 M-1). A series of batch experiments showed that solution pH, water matrices, and humic acids impacted SDM degradation efficiency. Degradation plateaus were observed in the presence of humic acids (>20 mgL-1), which caused greater MnO2 production. A mixture of KMnO4/beeswax/paraffin (SRB) at a ratio of 11.5:4:1 (w/w) was better for biodegradability and the continual release of MnO4-, but MnO2 formation altered release patterns. Adding tetrapotassium pyrophosphate (TKPP) into the composite resulted in delaying MnO2 aggregation and increased SDM removal efficiency to 90% due to the increased oxidative sites on the MnO2 particle surface. The MnO4- release data fit the Siepmann-Peppas model over the long term (t < 48 d) while a Higuchi model provided a better fit for shorter timeframes (t < 8 d). Our flow-through discharge tank system using SRB with TKPP continually reduced the SDM concentration in both DI water and lagoon wastewater. These results support SRB with TKPP as an effective composite for treating antibiotic residues in aquaculture discharge water.

Fabrication of Ternary Nanoparticles for Catalytic Ozonation to Treat Parabens: Mechanisms, Efficiency, and Effects on Ceratophyllum demersum L. and Eker Leiomyoma Tumor-3 Cells.

The use of parabens in personal care products can result in their leakage into water bodies, especially in public swimming pools with insufficient water treatment. We found that ferrite-based nanomaterials could catalytically enhance ozone efficiency through the production of reactive oxygen species. Our objective was to develop a catalytic ozonation system using ternary nanocomposites that could minimize the ozone supply while ensuring the treated water was acceptable for disposal into the environment. A ternary CuFe2O4/CuO/Fe2O3 nanocomposite (CF) delivered excellent degradation performance in catalytic ozonation systems for butylparaben (BP). By calcining with melamine, we obtained the CF/g-C3N4 (CFM) nanocomposite, which had excellent magnetic separation properties with slightly lower degradation efficiency than CF, due to possible self-agglomeration that reduced its electron capture ability. The presence of other constituent ions in synthetic wastewater and actual discharge water resulted in varying degradation rates due to the formation of secondary active radicals. 1O2 and •O2− were the main dominant reactive species for BP degradation, which originated from the O3 adsorption that occurs on the CF≡Cu(I)−OH and CF≡Fe(III)−OH surface, and from the reaction with •OH from indirect ozonation. Up to 50% of O3-treated water resulted in >80% ELT3 cell viability, the presence of well-adhered cells, and no effect on the young tip of Ceratophyllum demersum L. Overall, our results demonstrated that both materials could be potential catalysts for ozonation because of their excellent degrading performance and, consequently, their non-toxic by-products.

A biological and chemical approach to restoring water quality: A case study in an urban eutrophic pond.

Efforts to improve water quality of eutrophic ponds often involve implementing changes to watershed management practices to reduce external nutrient loads. While this is required for long-term recovery and prevention, eutrophic conditions are often sustained through the recycling of internal nutrients already present within the waterbody. In particular, internal phosphorus bound to organic material and adsorbed to sediment has the potential to delay lake recovery for decades. Thus, pond and watershed management techniques are needed that not only reduce external nutrient loading but also mitigate the effects of internal nutrients already present. Therefore, our objective was to demonstrate a biological and chemical approach to remove and sequester nutrients present and entering an urban retention pond. A novel biological and chemical management technique was designed by constructing a 37 m2 (6.1 m × 6.1 m) floating treatment wetland coupled with a slow-release lanthanum composite inserted inside an airlift pump. The floating treatment wetland promoted microbial denitrification and plant uptake of nitrogen and phosphorus, while the airlift pump slowly released lanthanum to the water column over the growing season to reduce soluble reactive phosphorus. The design was tested at the microcosm and field scales, where nitrate-N and phosphate-P removal from the water column was significant (α = 0.05) at the microcosm scale and observed at the field scale. Two seasons of field sampling showed both nitrate-N and phosphate-P concentrations were reduced from 50 µg L-1 in 2020 to <10 µg L-1 in 2021. Load calculations of incoming nitrate-N and phosphate-P entering the retention pond from the surrounding watershed indicate the presented biological-chemical treatment is sustainable and will minimize the effects of nutrient loading from nonpoint source pollution.

Modeling the release and spreading of permanganate from aerated slow-release oxidants in a laboratory flow tank.

Aerated, slow-release oxidants are a relatively new technology for treating contaminated aquifers. A critical need for advancing this technology is developing a reliable method for predicting the radius of influence (ROI) around each drive point. In this work, we report a series of laboratory flow tank experiments and numerical modeling efforts designed to predict the release and spreading of permanganate from aerated oxidant candles (oxidant-wax composites). To mimic the design of the oxidant delivery system used in the field, a double screen was used in a series of flow tank experiments where the oxidant was placed inside the inner screen and air was bubbled upward in the gap between the screens. This airflow pattern creates an airlift pump that causes water and oxidant to be dispersed from the top of the outer screen and drawn in at the bottom. Using this design, we observed that permanganate spreading and ROI increased with aeration and decreased with advection. A coupled bubble flow and transport model was able to successfully reproduce observed results by mimicking the upward shape and spreading of permanganate under various aeration and advection rates.

Remediating 1,4-dioxane-contaminated water with slow-release persulfate and zerovalent iron.

1,4-dioxane is an emerging contaminant that was used as a corrosion inhibitor with chlorinated solvents. Metal-activated persulfate can degrade dioxane but reaction kinetics have typically been characterized by a rapid decrease during the first 30 min followed by either a slower decrease or no further change (i.e., plateau). Our objective was to identify the factors responsible for this plateau and then determine if slow-release formulations of sodium persulfate and Fe0 could provide a more sustainable degradation treatment. We accomplished this by conducting batch experiments where Fe0-activated persulfate was used to treat dioxane. Treatment variables included the timing at which the dioxane was added to the Fe0-persulfate reaction (T = 0 and 30 min) and including various products of the Fe0-persulfate reaction at T = 0 min (Fe2+, Fe3+, and SO42-). Results showed that when dioxane was spiked into the reaction at 30 min, no degradation occurred; this is in stark contrast to the 60% decrease observed when added at T = 0 min. Adding Fe2+ at the onset (T = 0 min) also severely halted the reaction and caused a plateau. This indicates that excess ferrous iron produced from the Fe0-persulfate reaction scavenges sulfate radicals and prevents further dioxane degradation. By limiting the release of Fe0 in a slow-release wax formulation, degradation plateaus were avoided and 100% removal of dioxane observed. By using 14C-labeled dioxane, we show that ∼40% of the dioxane carbon is mineralized within 6 d. These data support the use of slow-release persulfate and zerovalent iron to treat dioxane-contaminated water.

A five-year performance review of field-scale, slow-release permanganate candles with recommendations for second-generation improvements.

In 2009, we identified a TCE plume at an abandoned landfill that was located in a low permeable silty-clay aquifer. To treat the TCE, we manufactured slow-release potassium permanganate cylinders (oxidant candles) that had diameters of either 5.1 or 7.6 cm and were 91.4 cm long. In 2010, we compared two methods of candle installation by inserting equal masses of the oxidant candles (7.6-cm vs 5.1-cm dia). The 5.1-cm dia candles were inserted with direct-push rods while the 7.6-cm candles were housed in screens and lowered into 10 permanent wells. Since installation, the 7.6-cm oxidant candles have been refurbished approximately once per year by gently scraping off surface oxides. In 2012, we reported initial results; in this paper, we provide a 5-yr performance review since installation. Temporal sampling shows oxidant candles placed in wells have steadily reduced migrating TCE concentrations. Moreover, these candles still maintain an inner core of oxidant that has yet to contribute to the dissolution front and should provide several more years of service. Oxidant candles inserted by direct-push have stopped reducing TCE concentrations because a MnO2 scale developed on the outside of the candles. To counteract oxide scaling, we fabricated a second generation of oxidant candles that contain sodium hexametaphosphate. Laboratory experiments (batch and flow-through) show that these second-generation permanganate candles have better release characteristics and are less prone to oxide scaling. This improvement should reduce the need to perform maintenance on candles placed in wells and provide greater longevity for candles inserted by direct-push.

Removing PAHs from urban runoff water by combining ozonation and carbon nano-onions.

Ozone (O3) is a chemical oxidant capable of transforming polycyclic aromatic hydrocarbons (PAHs) in urban runoff within minutes but complete oxidation to CO2 can take days to weeks. We developed and tested a flow-through system that used ozone to quickly transform PAHs in a runoff stream and then removed the ozone-transformed PAHs via adsorption to carbon nano-onions (CNOs). To quantify the efficacy of this approach, (14)C-labeled phenanthrene and benzo(a)pyrene, as well as a mixture of 16 unlabeled PAHs were used as test compounds. These PAHs were pumped from a reservoir into a flow-through reactor that continuously ozonated the solution. Outflow from the reactor then went to a chamber that contained CNOs to adsorb the ozone-transformed PAHs and allowed clean water to pass. By adding a microbial consortium to the CNOs following adsorption, we observed that bacteria were able to degrade the adsorbed products and release more soluble, biodegradable products back into solution. Control treatments confirmed that parent PAH structures (i.e., non-ozonated) were not biologically degraded following CNO adsorption and that O3-transformed PAHs were not released from the CNOs in the absence of bacteria. These results support the combined use of ozone, carbon nano-onions with subsequent biological degradation as a means of removing PAHs from urban runoff or a commercial waste stream.

A combined chemical and biological approach to transforming and mineralizing PAHs in runoff water.

The water quality of lakes, rivers and streams associated with metropolitan areas is declining from increased inputs of urban runoff that contain polycyclic aromatic hydrocarbons (PAHs). Our objective was to transform and mineralize PAHs in runoff using a combined chemical and biological approach. Using (14)C-labeled phenanthrene, (14)C-benzo(a)pyrene and a mixture of 16 PAHs, we found that ozone transformed all PAHs in a H2O matrix within minutes but complete mineralization to CO2 took several weeks. When urban runoff water (7.6 mg CL(-1)) replaced H2O as the background matrix, some delays in degradation rates were observed but transforming a mixture of PAHs was still complete within 10 min. Comparing the biodegradability of the ozonated products to the parent structures in unsaturated soil microcosms showed that the 3-ring phenanthrene was more biodegradable (as evidence by (14)CO2 released) than its ozonated products but for the 5-ring benzo(a)pyrene, the products produced by ozone were much more biodegradable (22% vs. 3% mineralized). For phenanthrene, we identified diphenaldehyde as the initial degradation product produced from ozonation. By continuing to pump the ozonated products ((14)C-labeled diphenaldehyde or ozone-treated benzo(a)pyrene) onto glass beads coated with microorganisms, we verified that biological mineralization could be achieved in a flow-through system and mineralization rates improved with acclimation of the microbial population (i.e., time and exposure to the substrate). These results support a combined ozone and biological approach to treating PAHs in urban runoff water.

Improving the treatment of non-aqueous phase TCE in low permeability zones with permanganate.

Treating dense non-aqueous phase liquids (DNAPLs) embedded in low permeability zones (LPZs) is a particularly challenging issue for injection-based remedial treatments. Our objective was to improve the sweeping efficiency of permanganate (MnO4(-)) into LPZs to treat high concentrations of TCE. This was accomplished by conducting transport experiments that quantified the penetration of various permanganate flooding solutions into a LPZ that was spiked with non-aqueous phase (14)C-TCE. The treatments we evaluated included permanganate paired with: (i) a shear-thinning polymer (xanthan); (ii) stabilization aids that minimized MnO2 rind formation and (iii) a phase-transfer catalyst. In addition, we quantified the ability of these flooding solutions to improve TCE destruction under batch conditions by developing miniature LPZ cylinders that were spiked with (14)C-TCE. Transport experiments showed that MnO4(-) alone was inefficient in penetrating the LPZ and reacting with non-aqueous phase TCE, due to a distinct and large MnO2 rind that inhibited the TCE from further oxidant contact. By including xanthan with MnO4(-), the sweeping efficiency increased (90%) but rind formation was still evident. By including the stabilization aid, sodium hexametaphosphate (SHMP) with xanthan, permanganate penetrated 100% of the LPZ, no rind was observed, and the percentage of TCE oxidized increased. Batch experiments using LPZ cylinders allowed longer contact times between the flooding solutions and the DNAPL and results showed that SHMP+MnO4(-) improved TCE destruction by ∼16% over MnO4(-) alone (56.5% vs. 40.1%). These results support combining permanganate with SHMP or SHMP and xanthan as a means of treating high concentrations of TCE in low permeable zones.

Improving the sweeping efficiency of permanganate into low permeable zones to treat TCE: experimental results and model development.

The residual buildup and treatment of dissolved contaminants in low permeable zones (LPZs) is a particularly challenging issue for injection-based remedial treatments. Our objective was to improve the sweeping efficiency of permanganate into LPZs to treat dissolved-phase TCE. This was accomplished by conducting transport experiments that quantified the ability of xanthan-MnO4(-) solutions to penetrate and cover (i.e., sweep) an LPZ that was surrounded by transmissive sands. By incorporating the non-Newtonian fluid xanthan with MnO4(-), penetration of MnO4(-) into the LPZ improved dramatically and sweeping efficiency reached 100% in fewer pore volumes. To quantify how xanthan improved TCE removal, we spiked the LPZ and surrounding sands with (14)C-lableled TCE and used a multistep flooding procedure that quantified the mass of (14)C-TCE oxidized and bypassed during treatment. Results showed that TCE mass removal was 1.4 times greater in experiments where xanthan was employed. Combining xanthan with MnO4(-) also reduced the mass of TCE in the LPZ that was potentially available for rebound. By coupling a multiple species reactive transport model with the Brinkman equation for non-Newtonian flow, the simulated amount of (14)C-TCE oxidized during transport matched experimental results. These observations support the use of xanthan as a means of enhancing MnO4(-) delivery into LPZs for the treatment of dissolved-phase TCE.

Using slow-release permanganate candles to remediate PAH-contaminated water.

Surface waters impacted by urban runoff in metropolitan areas are becoming increasingly contaminated with polycyclic aromatic hydrocarbons (PAHs). Slow-release oxidant candles (paraffin-KMnO(4)) are a relatively new technology being used to treat contaminated groundwater and could potentially be used to treat urban runoff. Given that these candles only release permanganate when submerged, the ephemeral nature of runoff events would influence when the permanganate is released for treating PAHs. Our objective was to determine if slow-release permanganate candles could be used to degrade and mineralize PAHs. Batch experiments quantified PAH degradation rates in the presence of the oxidant candles. Results showed most of the 16 PAHs tested were degraded within 2-4 h. Using (14)C-labled phenanthrene and benzo(a)pyrene, we demonstrated that the wax matrix of the candle initially adsorbs the PAH, but then releases the PAH back into solution as transformed, more water soluble products. While permanganate was unable to mineralize the PAHs (i.e., convert to CO(2)), we found that the permanganate-treated PAHs were much more biodegradable in soil microcosms. To test the concept of using candles to treat PAHs in multiple runoff events, we used a flow-through system where urban runoff water was pumped over a miniature candle in repetitive wet-dry, 24-h cycles. Results showed that the candle was robust in removing PAHs by repeatedly releasing permanganate and degrading the PAHs. These results provide proof-of-concept that permanganate candles could potentially provide a low-cost, low-maintenance approach to remediating PAH-contaminated water.

Using slow-release permanganate candles to remove TCE from a low permeable aquifer at a former landfill.

Past disposal of industrial solvents into unregulated landfills is a significant source of groundwater contamination. In 2009, we began investigating a former unregulated landfill with known trichloroethene (TCE) contamination. Our objective was to pinpoint the location of the plume and treat the TCE using in situ chemical oxidation (ISCO). We accomplished this by using electrical resistivity imaging (ERI) to survey the landfill and map the subsurface lithology. We then used the ERI survey maps to guide direct push groundwater sampling. A TCE plume (100-600 µg L(-1)) was identified in a low permeable silty-clay aquifer (K(h)=0.5 md(-1)) that was within 6m of ground surface. To treat the TCE, we manufactured slow-release potassium permanganate candles (SRPCs) that were 91.4 cm long and either 5. cm or 7.6 cm in dia. For comparison, we inserted equal masses of SRPCs (7.6-cm versus 5.1-cm dia) into the low permeable aquifer in staggered rows that intersected the TCE plume. The 5.1-cm dia candles were inserted using direct push rods while the 7.6-cm SRPCs were placed in 10 permanent wells. Pneumatic circulators that emitted small air bubbles were placed below the 7.6-cm SRPCs in the second year. Results 15 months after installation showed significant TCE reductions in the 7.6-cm candle treatment zone (67-85%) and between 10% and 66% decrease in wells impacted by the direct push candles. These results support using slow-release permanganate candles as a means of treating chlorinated solvents in low permeable aquifers.

Developing slow-release persulfate candles to treat BTEX contaminated groundwater.

The development of slow-release chemical oxidants for sub-surface remediation is a relatively new technology. Our objective was to develop slow-release persulfate-paraffin candles to treat BTEX-contaminated groundwater. Laboratory-scale candles were prepared by heating and mixing Na(2)S(2)O(8) with paraffin in a 2.25 to 1 ratio (w/w), and then pouring the heated mixture into circular molds that were 2.38 cm long and either 0.71 or 1.27 cm in diameter. Activator candles were prepared with FeSO(4) or zerovalent iron (ZVI) and wax. By treating benzoic acid and BTEX compounds with slow-release persulfate and ZVI candles, we observed rapid transformation of all contaminants. By using (14)C-labeled benzoic acid and benzene, we also confirmed mineralization (conversion to CO2) upon exposure to the candles. As the candles aged and were repeatedly exposed to fresh solutions, contaminant transformation rates slowed and removal rates became more linear (zero-order); this change in transformation kinetics mimicked the observed dissolution rates of the candles. By stacking persulfate and ZVI candles on top of each other in a saturated sand tank (14×14×2.5 cm) and spatially sampling around the candles with time, the dissolution patterns of the candles and zone of influence were determined. Results showed that as the candles dissolved and persulfate and iron diffused out into the sand matrix, benzoic acid or benzene concentrations (C(o)=1 mM) decreased by >90% within 7 d. These results support the use of slow-release persulfate and ZVI candles as a means of treating BTEX compounds in contaminated groundwater.

Transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by permanganate.

The chemical oxidant permanganate (MnO(4)(-)) has been shown to effectively transform hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) at both the laboratory and field scales. We treated RDX with MnO(4)(-) with the objective of quantifying the effects of pH and temperature on destruction kinetics and determining reaction rates. A nitrogen mass balance and the distribution of reaction products were used to provide insight into reaction mechanisms. Kinetic experiments (at pH ∼ 7, 25 °C) verified that RDX-MnO(4)(-) reaction was first-order with respect to MnO(4)(-) and initial RDX concentration (second-order rate: 4.2 × 10(-5) M(-1) s(-1)). Batch experiments showed that choice of quenching agents (MnSO(4), MnCO(3), and H(2)O(2)) influenced sample pH and product distribution. When MnCO(3) was used as a quenching agent, the pH of the RDX-MnO(4)(-) solution was relatively unchanged and N(2)O and NO(3)(-) constituted 94% of the N-containing products after 80% of the RDX was transformed. On the basis of the preponderance of N(2)O produced under neutral pH (molar ratio N(2)O/NO(3) ∼ 5:1), no strong pH effect on RDX-MnO(4)(-) reaction rates, a lower activation energy than the hydrolysis pathway, and previous literature on MnO(4)(-) oxidation of amines, we propose that RDX-MnO(4)(-) reaction involves direct oxidation of the methylene group (hydride abstraction), followed by hydrolysis of the resulting imides, and decarboxylation of the resulting carboxylic acids to form N(2)O, CO(2), and H(2)O.

Abiotic transformation of high explosives by freshly precipitated iron minerals in aqueous FeII solutions.

Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated Fe(II) phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE). Our objective was to determine the transformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene) by freshly precipitated iron Fe(II)/Fe(III) minerals. This was accomplished by quantifying the effects of initial Fe(II) concentration, pH, and the presence of aquifer solids (Fe(III) phases) on HE transformation rates. Results showed that at pH 8.2, freshly precipitated iron minerals transformed RDX, HMX, and TNT with reaction rates increasing with increasing Fe(II) concentrations. RDX and HMX transformations in these solutions also increased with increasing pH (5.8-8.55). By contrast, TNT transformation was not influenced by pH (6.85-8.55) except at pH values <6.35. Transformations observed via LC/MS included a variety of nitroso products (RDX, HMX) and amino degradation products (TNT). XRD analysis identified green rust and magnetite as the dominant iron solid phases that precipitated from the aqueous Fe(II) during HE treatment under anaerobic conditions. Geochemical modeling also predicted Fe(II) activity would likely be controlled by green rust and magnetite. These results illustrate the important role freshly precipitated Fe(II)/Fe(III) minerals in aqueous Fe(II) solutions play in the transformation of high explosives.

Using gas-phase molecular descriptors to predict dechlorination rates of chloroalkanes by zerovalent iron.

Reductive dehalogenation of chlorinated compounds is the most important process occurring within the zerovalent iron (Fe0) barrier. The relative reaction rates of individual halocarbons with Fe0 can vary considerably. This variability has been the stimulus for using various chemical descriptors for a priori predictions of transformation rates via linear free-energy relationships (LFERs). Our objective was to determine the efficacy of four molecular descriptors to describe the transformation rates of three chloromethanes, three chloroethanes, and six chloropropanes by Fe0. This was accomplished by generating an internally consistent set of rate constants under controlled environmental conditions (16 degrees C, anaerobic) and regressing the surface-area normalized rate constants (k(SA)) against (i) energy of the lowest unoccupied molecular orbital (E(LUMO)); (ii) vertical attachment energies (VAE); (iii) thermal electron attachment rate constants; and (iv) the molar response from a commercial electron capture detector (ECD). Results showed good correlations between k(SA)'s and all four descriptors (r2: 0.72-1.0), but a separate trend line was required for the chloromethanes and the chloro- ethanes/ propanes. Given the availability and ease with which ECD response can be obtained, this physical measurement may provide a practical means of determining relative rates of reactivity of various halocarbons in permeable reactive iron barriers.

Dechlorinating chloroacetanilide herbicides by dithionite-treated aquifer sediment and surface soil.

The prevalent use of chloroacetanilide herbicides has resulted in nonpoint contamination of some groundwater and surface water. We determined the efficacy of dithionite-treated sediment and soils to transform chloroacetanilides. When used alone, dithionite rapidly dechlorinates chloroacetanilides in water, with the following order of reactivity: propachlor > alachlor > acetochlor > metolachlor. Stoichiometric release of chloride occurs during reaction with dithionite, and thiosulfate herbicide derivatives are produced. Treating aquifer sediment with dithionite reduces native Fe(lII), creating a redox barrier of Fe(ll)-bearing minerals and surface-bound Fe(ll). Washing the reduced sediment (buffered with citrate-bicarbonate) with oxygen-free water removed Fe(ll) and excess dithionite and no alachlor transformation was observed. In contrast, a dithionite-treated surface soil, rich in clay and iron, effectively dechlorinated alachlor after washing. Exposing alachlor to aquifer sediment treated with dithionite in potassium carbonate buffer (pH 8.5-9.0) produced dechlorinated alachlor as the major degradation product. Our results provide proof-of-concept that dechlorination of chloroacetanilide herbicides by dithionite and dithionite-treated aquifer sediment and soil is a remediation option in natural environments where iron-bearing minerals are abundant.

Electron capture detector response and dissociative electron attachment cross sections in chloroalkanes and chloroalkenes.

Electron capture detectors (ECDs) are widely used in gas chromatography to detect electronegative compounds. In this work, we examine the connections between the ECD response and the cross sections for dissociative electron attachment (DEA) determined from low energy electron beam studies in the chloroalkane family, stressing in particular the role of temporary anion state energies. We show that attachment rate coefficients computed from these cross sections are well correlated with ECD response, and that the latter decreases exponentially with increasing energies of the lowest anion states. ECD measurements are also carried out in monochloroalkanes substituted with unsaturated ethenyl and phenyl moieties, and the response is shown to depend strongly on the mixing between the unsaturated pi* and the C-Cl sigma* temporary anions as exhibited by the vertical attachment energies (VAEs) of these states. The results show good correlations between the chloroalkene and phenyl chloride ECD responses and the VAEs for the mixed states.