N-nitrosodimethylamine Reduction Research Articles

Effects of transition-metal ions on the reduction of N-nitrosodimethylamine in water by zinc

The influencing factors, products and mechanism of N-nitrosodimethylamine (NDMA) reduction by zinc (Zn) in the presence of transition-metal ions (Mn2+, Co2+ and Ni2+), were investigated. The NDMA removal by Zn was significantly improved by them, and the promoting effect of Co2+ and Ni2+ were better than Mn2+. With the decrease of pH values and dissolved oxygen concentrations, the removals of NDMA were enhanced in all reaction systems. NDMA was mainly reduced to unsymmetrical dimethylhydrazine (UDMH) in Zn and Zn/Mn2+ systems. It was mainly reduced to dimethylamine (DMA) and ammonium (NH4+) in Zn/Co2+ and Zn/Ni2+ systems. There were undetected products in all reaction systems. Catalytic hydrogenation was the main mechanism, and active hydrogen atom was the main active species. The presence of Mn2+, Co2+ and Ni2+ promoted the corrosion of Zn and changed the surface morphology of Zn. The formation of type I film on Zn surface was promoted in the presence of Co2+ and Ni2+, which was conducive to the continuous corrosion of Zn and hydrogen generation. While type II film which would inhibit the corrosion of Zn formed on Zn surface in the presence of Mn2+. MnO2, Co3O4 and Ni(OH)2 were formed in Zn/Mn2+, Zn/Co2+ and Zn/Ni2+ systems, respectively. They would facilitate more generation of active hydrogen atoms.

Highly effective electrocatalytic reduction of N-nitrosodimethylamine on Ru/CNT catalyst

N-Nitrosodimethylamine (NDMA) is a commonly identified carcinogenic and genotoxic pollutant in water. In this study, we prepared Ru catalysts supported on carbon nanotube (Ru/CNT) and studied the electrocatalytic reduction of N-nitrosamines on Ru/CNT electrode in a three-electrode system. The results show that Ru-based catalyst exhibits a high activity of 793.3 μmol L−1 gCat−1 h−1 for electrochemical reduction of NDMA. Reaction mechanism study discloses that the electrocatalytic reduction of NDMA is accomplished by both direct electron reduction and atomic H* mediated indirect reduction pathways. Further product analysis indicates that NDMA is finally reduced to dimethylamine (DMA) and ammonia. The reduction efficiency of NDMA strongly relies on cathode potential, initial NDMA concentration and solution pH. To verify the universality of Ru/CNT electrode, electrocatalytic reduction of three dialkyl N-nitrosamines with different alkyl groups was performed and Ru catalyst has high catalytic activities for the three N-nitrosamines, while the catalytic efficiency differs with their structures. Simultaneous electrochemical reduction of the three N-nitrosamines indicates that the reduction rates of N-nitrosamines follow the same order in the multiple-component system as that in the single-component system. Catalyst recycling results demonstrate that after 5 consecutive recycling runs Ru/CNT electrode remains almost identical catalytic activity to the fresh catalyst, manifesting the high catalytic stability of Ru/CNT electrode.

Performance and mechanism of nickel hydroxide catalyzed reduction of N-nitrosodimethylamine by iron

Since iron (Fe) was first proven to have a strong reduction ability, it has been successfully applied to remove pollutants from water. In this study, nickel hydroxide (Ni(OH)2), a catalyst commonly used in hydrogen evolution reactions, was added to improve the activity of Fe to remove N-nitrosodimethylamine (NDMA). The results showed that with the increasing Ni(OH)2 dosages, the reactions accelerated. The NDMA removal rates increased when the pH value was 6 or 7. Further, when the dissolved oxygen concentration was in the range of 0–12.0 mg∙L−1, it had little effect on the Fe/Ni(OH)2 system, and all the reactions obeyed pseudo-first-order kinetics. 1,1-dimethylhydrazine and dimethylamine were formed during NDMA degradation. The capture of active substances and electron spin resonance method confirmed that the main active species were active hydrogen atoms, which participated in the removal of NDMA. Ni(OH)2 acting as a catalyst was confirmed using wide-angle X-ray diffraction, X-ray photoelectron spectroscopy and Ni2+ dissolution. Further, catalytic hydrogenation was proposed as the main removal mechanism as Ni(OH)2 promotes the corrosion of Fe and dissociation of water, thereby generating more active hydrogen atoms. In addition, Ni(OH)2 may activate both Fe and NDMA. This technique could be employed as an alternative for NDMA reduction and expand the application field of Ni(OH)2.

N-nitrosodimethylamine reduction by Lactobacillus pentosus R3 in fermented cooked sausages

This study investigated the effects of Lactobacillus pentosus R3 on N-nitrosodimethylamine (NDMA) in the production and cooking of fermented sausages. L. pentosus significantly decreased the content of NDMA in fermented sausages, especially after the ripening and cooking steps (P < 0.05). Dimethylamine and carbonyl content, thiobarbituric acid reactive substances value, and content of non-haem iron of the sausages inoculated with L. pentosus were significantly lower than those of the control (P < 0.05). It means that L. pentosus may decrease NDMA content in the sausages through direct degradation, indirect reduction of its precursors, weakened oxidation, and a decrease in the non-haem iron content. In addition, the lower pH and water activity of the inoculated sample may also inhibit the formation of NDMA by improving the microbial quality of the sausages. Therefore, inoculating L. pentosus R3 into fermented cooked sausages is an effective way to reduce NDMA content.

Assessment of 265-nm UV-LED for direct photolysis and advanced oxidation of N-nitrosamines and 1,4-dioxane

Abstract The advanced oxidation process (AOP), using conventional low-pressure mercury (LP Hg)-vapor UV lamps, forms a critical barrier for pathogens and contaminants of emerging concern (CECs) in potable water reuse. In recent years, UV-light-emitting diode (UV-LED) has attracted considerable attention as an alternative UV source because it has a long lifetime and is mercury-free. This study assesses the effectiveness of 265-nm UV-LED in removal of characteristic CECs, 1,4-dioxane (100 μ g/L) and N-nitrosamines (500 ng/L), including N-nitrosodimethylamine (NDMA), in recycled potable water. Direct photolysis using a UV-LED lamp, at the maximum UV dose of 900 mJ/cm2, achieved a maximum of 31% NDMA reduction, as opposed to a 93% reduction by a conventional LP Hg UV lamp. We attributed this to the longer emission wavelength of the UV-LED (265 nm) than that for the LP Hg UV lamp (254 nm). Both UV lamps failed to photolyze 1,4-dioxane. Using hydrogen peroxide or monochloramine remarkably enhanced the effectiveness of the LP Hg UV-based AOP in removing 1,4-dioxane, and the percentage of NDMA removed also increased slightly; however, it did not improve the effectiveness of the UV-LED-based AOP. We conclude from this study that despite the advantages of the UV-LED over the conventional LP Hg UV lamp, the former performs ineffectively at attenuating major CECs in recycled water.

Effects of Sulfidation and Nitrate on the Reduction of N-Nitrosodimethylamine by Zerovalent Iron

Competition among oxidizing species in groundwater and wastewater for the reductive capacity of zerovalent iron (ZVI) makes the selectivity of ZVI for target contaminant degradation over other reduction pathways a major determinant of the feasibility of ZVI-based water treatment processes. The selectivity for reduction of contaminants over water is improved by sulfidation, but the effect of sulfidation on other competing reactions is not known. The interaction between these competing reactions was investigated using N-nitrosodimethylamine (NDMA) as the target contaminant, nitrate as a co-contaminant, and micrometer-sized ZVI with and without sulfidation. Unsulfidated ZVI reduced NDMA to dimethylamine via N,N-dimethylhydrazine, but the addition of nitrate decreased the rate of NDMA reduction and increased the quantity of intermediate observed. With sulfidated ZVI, the kinetics and products of NDMA reduction were similar to those with unsulfidated ZVI, but no inhibitory effect of nitrate was observed. Conversely, the reduction of nitrate-which dominated NDMA reduction in unsulfidated ZVI systems-was strongly inhibited by sulfidation. H2 and Fe2+ generation by sulfidated ZVI was almost independent of nitrate concentration. Therefore, sulfidation improved the efficiency of NDMA reduction by ZVI in the presence of nitrate mainly by inhibiting nitrate reduction. The shift in selectivity of ZVI for NDMA over nitrate upon sulfidation was due to replacement of Fe0/FexOy surface sites with FeS.

Water-Mediated Reduction of Aqueous N-Nitrosodimethylamine with Pd.

Pd-catalyzed reduction has emerged as a promising treatment strategy to remove the recalcitrant disinfection byproduct N-nitrosodimethylamine (NDMA). However, the reaction pathways remain unexplored, and questions remain about how water solvent influences NDMA reduction mechanisms and selectivity. Here, we compute the energies and barriers of all relevant elementary steps in NDMA reduction by H2 on Pd(111) using density functional theory. We further calculate water-assisted H-shuttling for all hydrogenation reactions explicitly and include water solvation for all elementary reactions implicitly. We parametrize microkinetic models to predict product formation rates and selectivities over a wide range of NDMA concentrations. We show that H2O-mediated H-shuttling lowers the reaction barriers for all hydrogenation reactions involved in NDMA reduction while implicit solvation has negligible impact on the reaction and activation energies. We further conduct batch experiments with SiO2-supported Pd nanoparticles and compare them with the microkinetic models. The predicted rates, selectivity, and apparent activation energy from the model parametrized with both explicit H2O-mediated H-shuttling and implicit solvation correspond well with experimental observations. Models that ignore water as an H-shuttle or solvent fail to recover the experimental rates and apparent activation energy. We identified the rate-determining steps of the reaction and show the reaction flow pathways of the complicated reaction network. Finally, we demonstrate that water-mediated H-shuttling changes the rate-determining steps and reaction flows of elementary reactions.

Simultaneous Adsorption and Electrochemical Reduction of N-Nitrosodimethylamine Using Carbon-Ti4O7 Composite Reactive Electrochemical Membranes.

This study focused on synthesis and characterization of Ti4O7 reactive electrochemical membranes (REMs) amended with powder-activated carbon (PAC) or multiwalled carbon nanotubes (MWCNTs). These composite REMs were evaluated for simultaneous adsorption and electrochemical reduction of N-nitrosodimethylamine (NDMA). The carbon-Ti4O7 composite REMs had high electrical conductivities (1832 to 2991 S m-1), where carbon and Ti4O7 were in direct electrical contact. Addition of carbonaceous materials increased the residence times of NDMA in the REMs by a factor of 3.8 to 5.4 and therefore allowed for significant electrochemical NDMA reduction. The treatment of synthetic solutions containing 10 μM NDMA achieved >4-log NDMA removal in a single pass (liquid residence time of 11 to 22 s) through the PAC-REM and MWCNT-REM with the application of a -1.1 V/SHE cathodic potential, with permeate concentrations between 18 and 80 ng L-1. The treatment of a 6.7 nM NDMA-spiked surface water sample, under similar operating conditions (liquid residence time of 22 s), achieved 92 to 97% removal with permeate concentrations between 16 and 40 ng L-1. Density functional theory calculations determined a probable reaction mechanism for NDMA reduction, where the rate-limiting step was a direct electron transfer reaction.

Copper Corrosion Products Catalyzed Reduction of N-Nitrosodimethylamine with Iron.

Copper corrosion products (Cu(OH)2, Cu2O, CuO and Cu2CO3(OH)2) were applied to catalyze the reduction of N-Nitrosodimethylamine (NDMA) with iron. All the copper corrosion products showed catalytic abilities. Lower pH values and DO concentrations facilitated NDMA reduction in most cases. 1,1-dimethylhydrazine (unsymmetrical dimethylhydrazine, UDMH) and dimethylamine (DMA) formed during the degradation of NDMA. There were also some undetected products. Catalytic hydrogenation was proposed as the mechanism. The catalytic systems did not promote the formation of hydrogen atoms. The dissolved copper ions in these systems were too sparse to enhance the reaction. The smooth iron surface and formation of Cu2O in each catalytic system explained the enhancement of NDMA removal. Different surface morphologies and states of Cu2O accounted for the differences in NDMA removal and kinetics between the reaction systems. This technique could be an alternative for NDMA reduction and could broaden the application of copper corrosion products.

Liquid-phase hydrogenation of N-nitrosodimethylamine over Pd-Ni supported on CeO2-TiO2: The role of oxygen vacancies

Catalytic liquid-phase hydrogenation of N-nitrosodimethylamine (NDMA) over CeO2, TiO2 and CeO2-TiO2 (CexTi, x referred to the molar ratio of Ce to Ti) supported Pd-Ni bimetallic catalysts (Pd-Ni/CexTi) was investigated. Characterization results indicated that Ce-O-Ti solid solutions formed through the incorporation of Ti4+ into the CeO2 lattice, resulting in increased specific surface areas and reduced average crystal sizes of CexTi. Ti doping also promoted the generation of oxygen vacancies (Ov) on the surface of CexTi. For Pd-Ni/CexTi, the amount of oxygen vacancies first increased and then decreased with the increasing of Ti content, and the maximum content of Ov was observed on Pd-Ni/Ce4Ti. Consequently, Pd-Ni/Ce4Ti had the smallest metal particle sizes, due to the strong metal-support interaction formed between Pd-Ni and Ov. Pd-Ni/CexTi exhibited much higher catalytic activities than that of Pd/CeO2 and Pd/TiO2 for NDMA reduction, and the Pd-Ni/Ce4Ti had the highest activity. The catalytic activity of Pd-Ni/CexTi was relevant to the oxygen vacancies on the support, which influenced the metal dispersion and the adsorption of intermediate product of NDMA reduction.

Reduction of N-nitrosodimethylamine formation from ranitidine by ozonation preceding chloramination: influencing factors and mechanisms.

Formation of toxic N-nitrosodimethylamine (NDMA) by chloramination of ranitidine, a drug to block histamine, was still an ongoing issue and posed a risk to human health. In this study, the effect of ozonation prior to chloramination on NDMA formation and the transformation pathway were determined. Influencing factors, including ozone dosages, pH, hydroxyl radical scavenger, bromide, and NOM, were studied. The results demonstrated that small ozone dosage (0.5mg/L) could effectively control NDMA formation from subsequent chloramination (from 40 to 0.8%). The NDMA molar conversion was not only influenced by pH but also by ozone dosages at various pre-ozonation pH (reached the highest value of 5% at pH8 with 0.5mg/L O3 but decreased with the increasing pH with 1mg/L O3). The NDMA molar yield by chloramination of ranitidine without pre-ozonation was reduced by the presence of bromide ion due to the decomposition of disinfectant. However, due to the formation of brominated intermediate substances (i.e., dimethylamine (DMA), dimethyl-aminomethyl furfuryl alcohol (DFUR)) with higher NDMA molar yield than their parent substances, more NDMA was formed than that without bromide ion upon ozonation. Natural organic matter (NOM) and hydroxyl radical scavenger (tert-butyl alcohol, tBA) enhanced NDMA generation because of the competition of ozone and more ranitidine left. The NDMA reduction mechanism by pre-ozonation during chloramination of ranitidine may be due to the production of oxidation products with less NDMA yield (such as DMA) than parent compound. Based on the result of Q-TOF and GC-MS/MS analysis, three possible transformation pathways were proposed. Different influences of oxidation conditions and water quality parameters suggest that strategies to reduce NDMA formation should vary with drinking water sources and choose optimal ozone dosage.

The role of Cu(II) in the reduction of N-nitrosodimethylamine with iron and zinc

The role of Cu(II) in the reduction of N-nitrosodimethylamine (NDMA) with zero-valent metals was investigated by determining the effects of Cu(II) on the removal, kinetics, products, and mechanism. NDMA removal was enhanced, and all reactions followed a pseudo-first-order kinetic model except for the Fe and Fe/0.1 mM Cu(II) systems. The iron mass-normalized pseudo-first-order rate constants (kMFe) increased with the Cu(II) concentration. The zinc mass-normalized pseudo-first-order rate constants (kMZn) were identical to those with the Cu(II) concentrations from 0.1 mM to 1.0 mM and were higher with 2.0 mM Cu(II). The types of products detected were unchanged. Some unknown products were also found. NDMA was reduced to 1,1-dimethylhydrazine (unsymmetrical dimethylhydrazine, UDMH). Then, UDMH was reduced into dimethylamine (DMA) by the Fe/Cu(II) and Zn/Cu(II) systems. Catalytic hydrogenation was proposed as the reduction mechanism. Several copper species, such as Cu(OH)2 in the Fe/Cu(II) system and Cu2O and Cu(OH)2 in the Zn/Cu(II) system enhanced NDMA reduction. Differences between the Fe/Cu(II) and Zn/Cu(II) systems were caused by the reduction potentials and surface conditions of the different metals and the copper species in the various systems.

Catalytic Reduction of N-Nitrosodimethylamine by Palladium/ Iron Bimetallic Composite Catalytic Fiber

The polypropylene (PP) fibers were chosen as substrate materials. Functional fibers containing iron were prepared by UV irradiation-coordination method, and then Pd/Fe bimetallic composite catalytic fibers were prepared by replacement reaction and used for the removement of N-nitrosodimethylamine (NDMA). The effect of monomer concentration, the pH of the reaction system and reaction temperature on NDMA catalytic degradation was investigated. The results indicate that the degradation rate of NDMA can reach 69.97% when the AA monomer concentration is 20%, which is the best catalytic reduction effect of composite catalytic fiber on NDMA. The pH of solution and reaction temperature can not greatly influence the catalytic reduction of NDMA.

Reduction of N-Nitrosodimethylamine (NDMA) in Aqueous Solution by Nanoscale Fe/Al2(SO4)3

N-Nitrosodimethylamine (NDMA) is recently defined as one of nitrogenous disinfection by-products with high carcinogenicity and can be frequently detected in finished water. The decomposition of NDMA in water using nanoscale zero-valent iron (NZVI) in the presence of aluminum and iron salts was investigated in this paper. The results showed that some salts can enhance the removal of NDMA by commercial NZVI in the order of Al2(SO4)3 >> AlCl3 > FeSO4 > Na2SO4 ≈ NZVI alone, and the highest NDMA removal was 87.3 % in the presence of Al2(SO4)3. NDMA removal varied with the addition of Al2(SO4)3, NZVI dosage, initial NDMA concentration, solution pH, and temperature. The reduction of NDMA increased with the dosage of Al2(SO4)3 and NZVI, which follows a pseudo-first-order kinetics model. The removal of NDMA by NZVI was higher in acidic pHs than in alkaline ones, and the highest removal was found at pH 5. Higher reaction temperature can improve the removal of NDMA and reduce the reaction time. Based on the total nitrogen balance, most nitrogen of NDMA was converted to ammonium and dimethylamine.

Reduction of N-Nitrosodimethylamine with zero-valent zinc

N-Nitrosodimethylamine (NDMA) is known as the disinfection by-product and the pollutant in the source water. Reduction with zero-valent zinc (Zn(0)) was investigated as a potential technology to treat NDMA. The results showed that Zn(0) was effective for NDMA reduction at initial pH 7.0. There were lag period and rapid period during the process, the corresponding zero-order rate constant (kzero) was 2.968 ± 0.245 μg L−1 h−1 ([Zn(0)]0 = 10g L−1),the mass normalized pseudo-first-order rate (kM) was 0.1215 ± 0.0171 L g−1 h−1. The reactivity of zinc on NDMA removal was consistent with the zinc corrosion rate. NDMA had little effect on the corrosion of zinc. Lower solution pH benefited the reduction of NDMA with Zn(0). The consumption of the oxygen and the localized acidification should be the cause of the shift from lag to rapid reaction period in the aerobic experiments. 1,1-dimethylhydrazine (unsymmetrical dimethylhydrazine, UDMH), dimethylamine (DMA) were detected as the products of NDMA degradation. The nitrogen mass balance at 24 h was 56%, the loss can be due to the formation of ammonium, the degradation of UDMH and other unmeasured products. DMA formed during the degradation of UDMH with Zn(0), the nitrogen loss could be caused by the formation of unmeasured products. Catalytic hydrogenation is proposed to be the mechanism based on the results and the redox properties of zinc and NDMA. One reduction process is: the active hydrogen atoms initially cleave and reduce the N=O bond in NDMA, generating UDMH. Then the N–N bond in UDMH is cleaved to form DMA and ammonium.

Effects of wavelength and water quality on photodegradation of N-Nitrosodimethylamine (NDMA)

N-Nitrosodimethylamine (NDMA) is a potent carcinogen that yields a cancer risk of 10−6 at concentrations as low as 0.7ngL−1. Tentative guideline values are set at 3ngL−1 in California, USA; 9ngL−1 in Ontario, Canada; 40ngL−1 nationwide in Canada; and 100ngL−1 by the World Health Organization. NDMA is a great concern in treating reclaimed water as well as drinking water. UV degradation can be considered effective degradation method. A 1-log reduction of NDMA is achieved by 1000mJcm−2 of a 254-nm low pressure (LP) mercury UV lamp. However, a higher degradation efficiency than that provided by LP lamps is desired in practical treatment. In this study, the effects of wavelength and water quality were investigated to achieve higher degradation efficiency. The effects of wavelength were examined by comparing three UV lamps: a 222-nm Kr Cl Excimer UV lamp, a 254-nm LP mercury UV lamp, and a 230- to 270-nm filtered medium pressure (FMP) mercury UV lamp. The 222-nm lamp and FMP lamp achieved 4 times and 2.8 times higher degradation efficiency, respectively, than the conventional 254-nm LP lamp. Effects on water quality were also simulated by using absorption spectrum data of nitrate solutions and process water from a drinking-water treatment plant. In the simulation, the 222-nm lamp was affected by UV-absorbing compounds in the water, whereas the FMP lamp showed more stable degradation efficiency. Appropriate use of these three types of lamps could enhance the efficiency of degradation of NDMA.

DFT Comparison of N‐Nitrosodimethylamine Decomposition Pathways Over Ni and Pd

AbstractRecent experimental studies report rapid and efficient reduction of N‐nitrosodimethylamine (NDMA) and related aquatic micropollutants mediated by palladium (Pd) and nickel (Ni) surfaces, but differing mechanisms have been reported for the surface reactions. Here, NDMA adsorption and fragmentation on Ni and Pd surfaces has been studied using supercell slab density functional theory (DFT) calculations. NDMA adsorbs in two stable configurations on each surface. Upright binding through the NO fragment is slightly preferred energetically and provides entrance to an exothermic NO dissociation pathway with moderately high activation barriers. Flat binding through the NNO plane is somewhat less favorable but leads to a facile and exothermic dissociation across the NN bond. These results suggest that both mechanisms are in competition and may contribute to the observed catalytic reduction of NDMA over these metals in aqueous solution.

Enhancement of Oxyanion and Diatrizoate Reduction Kinetics Using Selected Azo Dyes on Pd-Based Catalysts

Azo dyes are widespread pollutants and potential cocontaminants for nitrate; we evaluated their effect on catalytic reduction of a suite of oxyanions, diatrizoate, and N-nitrosodimethylamine (NDMA). The azo dye methyl orange significantly enhanced (less than or equal to a factor of 5.24) the catalytic reduction kinetics of nitrate, nitrite, bromate, perchlorate, chlorate, and diatrizoate with several different Pd-based catalysts; NDMA reduction was not enhanced. Nitrate was selected as a probe contaminant, and a variety of azo dyes (methyl orange, methyl red, fast yellow AB, metanil yellow, acid orange 7, congo red, eriochrome black T, acid red 27, acid yellow 11, and acid yellow 17) were evaluated for their ability to enhance reduction. Hydrogenation energies of azo dyes were calculated using density functional theory and a volcano relationship between hydrogenation energies and reduction rate enhancement was observed. A kinetic model based on Brønsted-Evans-Polanyi (BEP) theory matched the volcano relationship and suggests sorbed azo dyes enhance reduction kinetics through hydrogen atom shuttling between reduced azo dyes (i.e., hydrazo dyes) and oxyanions or diatrizoate. This is the first research that has identified this synergetic effect, and it has implications for designing more efficient catalysts and reducing Pd costs in water treatment systems.

Palladium−Indium Catalyzed Reduction of N-Nitrosodimethylamine: Indium as a Promoter Metal

An emerging technology for the removal of N-nitrosodimethylamine (NDMA) from drinking and groundwater is reductive destruction using noble metal catalysts and hydrogen gas as a reducing agent. Bimetallic palladium-indium (Pd-In) supported on alumina combines the ability of Into activate NDMA with the hydrogen activating properties of Pd. This study examined the effect of In addition to a commercial 5% Pd by weight on gamma-Al2O3 catalyst on the efficacy of NDMA reduction. The pseudo-first-order rate constant increased proportionately to In loading from 0.057 h(-1) for 0% In to a maximum of 0.25 h(-1) for 1% In and then decreased with additional in loading. Data suggest that hydrogen activation occurred only on Pd surfaces and In activated NDMA 20 times more effectively than Pd on a mass basis. The rate-limiting factor was NDMA activation for In loadings below 1%. The decrease at higher loadings is interpreted as In blocking pore spaces and limiting access to Pd sites, suggesting monatomic hydrogen limitation. The only products detected were dimethylamine and ammonium with carbon and nitrogen balances in excess of 92%, consistent with a mechanism involving reductive N-N bond cleavage. Results from this study serve as a basis for optimizing bimetallic catalysts for treating NDMA contaminated waters.

Rapid Reduction of N-Nitrosamine Disinfection Byproducts in Water with Hydrogen and Porous Nickel Catalysts

There is a need for new technologies to rapidly and economically treatwater contaminated with N-nitrosodimethylamine (NDMA) and related compounds because of their high toxicity and recent detection in drinking water sources as a consequence of industrial releases and chlorine disinfection of wastewater effluent Treatment of N-nitrosamines with H2 in conjunction with a high surface area porous nickel material, a model nonprecious metal catalyst, has been evaluated. Experiments show that NDMA is reduced rapidly and catalytically to dimethylamine and N2 (e.g., t1/2 = 1.5 min for 500 mg/L catalyst and PH2 = 1 atm), and kinetic trends are consistent with a surface-mediated mechanism involving scission of the N-nitrosamine N-N bond and subsequent reactions with adsorbed atomic hydrogen. The metal-loading-normalized pseudo-first-order rate constant (77.9 +/- 13.1 L g(Ni)(-1) h(-1)) exceeds values reported for Pd-based catalysts. Several related N-nitrosamines react at rates similar to those of NDMA, indicating a weak dependence on structure. The reaction rates for NDMA reduction are not significantly affected by changing pH, and the presence of high concentrations of many common water constituents (Na+, Ca2+, Mg2+, Cl-, SO4(2-), HCO(3-), and NOM) exerts only a small effect on reaction rates. Nitrate is also reduced by the Ni catalyst, and high nitrate concentrations competitively inhibit the reduction of NDMA. (Bi)sulfide poisons the catalyst by strong chemisorption to the Ni surface. Cost-normalized rate constants for the Ni catalyst are highly favorable compared to Pd-based catalysts, indicating that, with further development, Ni-based catalysts may become attractive alternatives to precious metal catalysts.