Pei C. Chiu

Degradation of 2,4-dinitrotoluene by persulfate activated with zero-valent iron

The oxidation of 2,4-dinitrotoluene (DNT) by persulfate (S(2)O(8)(2-)) activated with zero-valent iron (Fe(o)) was studied through a series of batch experiments. The mechanism for Fe(o) activation was investigated by comparing with Fe(2+), and the effects of persulfate-to-iron ratio and pre-reduction on DNT oxidation were examined. DNT was stable in the presence of persulfate and transformed only when Fe(o) was added. Most DNT was degraded oxidatively by Fe(o)-activated persulfate, whereas direct reduction of DNT by Fe(o) was unimportant. The rate of DNT degradation increased with higher Fe(o) dose, presumably due to increasing activation of persulfate by Fe(o) and Fe(2+). In contrast to the Fe(o)-persulfate system, where complete oxidation DNT was achieved, only </=20% of DNT was degraded and the reaction was terminated rapidly when Fe(o) was replaced with equimolar Fe(2+). This indicates that Fe(o) is more effective than Fe(2+) as activating agent and potentially more suitable for environmental applications. The reduction products of DNT were more rapidly oxidized by persulfate than DNT, suggesting that converting the nitro groups of NACs to amino groups prior to oxidation can greatly enhance their oxidation. This suggests that a sequential Fe(o) reduction-persulfate oxidation process may be an effective strategy to promote NAC degradation.

Enhancing Fenton oxidation of TNT and RDX through pretreatment with zero-valent iron

The effect of reductive treatment with elemental iron on the rate and extent of TOC removal by Fenton oxidation was studied for the explosives 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) using a completely stirred tank reactor (CSTR). The results support the hypothesis that TNT and RDX are reduced with elemental iron to products that are oxidized more rapidly and completely by Fentons reagent. Iron pretreatment enhanced the extent of total organic carbon (TOC) removal by approximately 20% and 60% for TNT and RDX, respectively. Complete TOC removal was achieved for TNT and RDX solutions with iron pretreatment under optimal conditions. On the other hand, without iron pretreatment, complete TOC removal of TNT and RDX solutions was not achieved even with much higher H(2)O(2) and Fe(2+) concentrations. Nitrogen was recovered as NH(4)(+) and NO(3)(-) when Fe(0)-treated TNT and RDX solutions were subjected to Fenton oxidation. The bench-scale iron treatment-Fenton oxidation integrated system showed more than 95% TOC removal for TNT and RDX solutions under optimal conditions. These results suggest that the reduction products of TNT and RDX are more rapidly and completely degraded by Fenton oxidation and that a sequential iron treatment-Fenton oxidation process may be a viable technology for pink water treatment.

Biochar-mediated reductive transformation of nitro herbicides and explosives.

Biochar, a subset of black carbon produced via pyrolysis of biomass, has received much attention in recent years due to its potential to address many important issues, from energy and climate to agriculture and environmental quality. Biochar is known to influence the fate and transport of organic contaminants, although its role has been generally assumed to be as an adsorbent. In this study, the authors investigated the ability of biochar to catalyze the reductive reactions of nitro herbicides and explosives. Two biochars, derived from poultry litter and wastewater biosolids, were found to promote the reductive removal of the dinitro herbicides pendimethalin and trifluralin and the explosives 2,4-dinitrotoluene and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by dithiothreitol. Parallel experiments using another black carbon material, graphite powder or granular activated carbon, in place of a biochar resulted in comparable rate enhancement to show reduction products, such as 2,4-diaminotoluene and formaldehyde. A cyclization product of trifluralin and reduction products of dinitrotoluene and RDX were detected only when biochar and dithiothreitol were both present, supporting the ability of biochar to promote redox reactions. Three possible catalysts, including graphene moieties, surface functional groups, and redox-active metals, in biochar may be responsible for the biochar-mediated reactions. The environmental significance, implications, and applications of this previously unrecognized role of biochar are discussed.

Reductive dehalogenation of chlorinated ethenes with elemental iron: the role of microorganisms.

Trichloroethene (TCE) transformation and the product distribution in an aqueous medium containing zero-valent iron (Fe(0)) was investigated in the presence of an anaerobic mixed culture to assess the potential role of microorganisms in permeable iron barriers. The presence of the culture increased the rate of TCE disappearance and changed the product distribution. Rapid formation and degradation of cis-dichloroethene (cis-DCE) was observed in reactors containing cells plus Fe(0) or H2 as a bulk reducing agent. High levels of vinyl chloride (VC) were formed and very similar profiles were obtained in the Fe(0) plus cell and H2 plus cell reactors, but not in Fe(0)-only reactors. The similar trends observed in Fe(0)-cell and H2-cell reactors suggest that most cis-DCE and VC in the Fe(0)-cell reactors were produced and transformed biologically rather than abiotically. Accumulation of methane in the Fe(0)-cell system indicates that hydrogen gas generated during anaerobic iron corrosion could support a methanogenic culture. Digital confocal images showed that the microorganisms were able to colonize the iron surface. The results suggest that potential development of dechlorinating populations in Fe(0) barriers may alter the TCE reduction pathway and produce VC, which would have significant impact on the performance of Fe(0) barriers.

SONOCHEMICAL DECOMPOSITION OF DIBENZOTHIOPHENE IN AQUEOUS SOLUTION

Dibenzothiophene is decomposed rapidly by sonication in aqueous solution. Decomposition of dibenzothiophene follows a first-order reaction kinetics. The rate constant was found to increase with increasing ultrasonic energy intensity, temperature, and pH and decrease with increasing initial dibenzothiophene concentration. The activation energy was 12.6 kJ mol in the temperature range of 15-50 degrees C, suggesting a diffusion-controlled reaction. Hydroxydibenzothiophenes and dihydroxydibenzothiophenes were identified as reaction intermediates. It is proposed that dibenzothiophene is oxidized by OH radical to hydroxy-dibenzothiophenes and then to dihydroxy-dibenzothiophenes. Kinetic analysis suggests that approximately 72% of the dibcnzothiophene decomposition occurred via OH radical addition. A pathway and a kinetic model for the sonochemical decomposition of dibenzothiophene in aqueous solution are proposed.

Phosphorus release behaviors of poultry litter biochar as a soil amendment.

Phosphorus (P) may be immobilized and consequently the runoff loss risks be reduced if poultry litter (PL) is converted into biochar prior to land application. Laboratory studies were conducted to examine the water extractability of P in PL biochar and its release kinetics in amended soils. Raw PL and its biochar produced through 400°C pyrolysis were extracted with deionized water under various programs and measured for water extractable P species and contents. The materials were further incubated with a sandy loam at 20 g kg(-1) soil and intermittently leached with water for 30 days. The P release kinetics were determined from the P recovery patterns in the water phase. Pyrolysis elevated the total P content from 13.7 g kg(-1) in raw PL to 27.1 g kg(-1) in PL biochar while reduced the water-soluble P level from 2.95 g kg(-1) in the former to 0.17 g kg(-1) in the latter. The thermal treatment transformed labile P in raw PL to putatively Mg/Ca phosphate minerals in biochar that were water-unextractable yet proton-releasable. Orthophosphate was the predominant form of water-soluble P in PL biochar, with condensed phosphate (e.g., pyrophosphate) as a minor form and organic phosphate in null. Release of P from PL biochar in both water and neutral soils was at a slower and steadier rate over a longer time period than from raw PL. Nevertheless, release of P from biochar was acid-driven and could be greatly promoted by the media acidity. Land application of PL biochar at soil pH-incorporated rates and frequency will potentially reduce P losses to runoffs and minimize the adverse impact of waste application on aquatic environments.

Reductive transformation of 2,4,6-trinitrotoluene, hexahydro-1,3,5-trinitro-1,3,5-triazine, and nitroglycerin by pyrite and magnetite

Reductive transformation of 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and nitroglycerin (NG) by pyrite (FeS(2)) and magnetite (Fe(3)O(4)) was investigated to determine the role of Fe(II)-bearing minerals on the fate of toxic explosives in Fe/S-rich natural environment. Results from batch experiments showed that 65% of TNT and 45% of RDX were transformed from solution in the presence of pyrite under pH 7.4 buffered conditions within 32 days. Without a buffered solution, transformation of TNT and RDX decreased. NG was continuously and rapidly transformed by pyrite under both conditions. Complete removal of NG was achieved in 32 days under buffered conditions. NH(4)(+) was identified as a reduction product for RDX and NG in the pyrite-water system. Reductive transformation of RDX and NG by magnetite was slower than that by pyrite. The results suggest that abiotic transformation of the explosives by pyrite and magnetite may be considered when determining the fate of explosives in Fe/S-rich subsurface environments.

Reductive transformation of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine, octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine, and methylenedinitramine with elemental iron

Reductive (pre)treatment with elemental iron is a potentially useful method for degrading nitramine explosives in water and soil. In the present study, we examined the kinetics, products, and mechanisms of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) degradation with elemental iron. Both RDX and HMX were transformed with iron to formaldehyde, NH4+, N2O, and soluble products. The yields of formaldehyde were relatively constant (71% +/- 5%), whereas the yields of NH4+ and N2O varied, depending on the nitramine and the mechanism. The reactions most likely were controlled by a surface process rather than by external mass transfer. Methylenedinitramine (MDNA) was an intermediate of both RDX and HMX and was transformed quantitatively to formaldehyde with iron. However, product distributions and kinetic modeling results suggest that MDNA represented a minor reaction path and accounted for only 30% of the RDX reacted and 14% of the formaldehyde produced. Additional experiments showed that RDX reduction with elemental iron could be mediated by graphite and Fe2+ sorbed to magnetite, as demonstrated previously for nitroaromatics and nitrate esters. Methylenedinitramine was degraded primarily through reduction in the presence of elemental iron, because its hydrolysis was slow compared to its reactions with elemental iron and surface-bound Fe2+. Our results show that in a cast iron-water system, RDX may be transformed via multiple mechanisms involving different reaction paths and reaction sites.

The role of black carbon as a catalyst for environmental redox transformation

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983–6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC—graphite, activated carbon, and diesel soot—to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H2S. All three types of BC enhanced DNT and DBP reduction. H2S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.

Black carbon-mediated reductive transformation of nitro compounds by hydrogen sulfide

The objective of this study is to investigate the fate of redox-sensitive nitro compounds in the presence of black carbon (BC) materials in electron-rich subsurface environments. The ability of various types of BC was examined, including graphite, carbon nanotubes, chemically converted graphene, activated carbon, diesel soot, and biochar, to promote the reduction of 2,4-dinitrotoluene, pendimethalin, and trifluralin by hydrogen sulfide, a naturally occurring reductant, through batch experiments. Compared to removal in sorption control experiments with BC materials and direct transformation with hydrogen sulfide, the presence of BC markedly enhanced the reduction of nitro compounds by hydrogen sulfide, indicating that BC can be an electron-transfer mediator in the presence of hydrogen sulfide. Possible mechanisms and environmental implications of BC-mediated reduction reactions in soils and sediments are discussed.