Low levels of iron enhance UV/H2O2 efficiency at neutral pH.

While the presence of iron is generally not seen as favorable for UV-based treatment systems due to lamp fouling and decreased UV transmittance, we show that low levels of iron can lead to improvements in the abatement of chemicals in the UV-hydrogen peroxide advanced oxidation process. The oxidation potential of an iron-assisted UV/H2O2 (UV254 + H2O2 + iron) process was evaluated at neutral pH using iron levels below USEPA secondary drinking water standards (<0.3 mg/L). Para-chlorobenzoic acid (pCBA) was used as a hydroxyl radical (HO) probe to quantify HO steady state concentrations. Compounds degraded by different mechanisms including, carbamazepine (CBZ, HO oxidation) and N-nitrosodimethylamine (NDMA, direct photolysis), were used to investigate the effect of iron on compound degradation for UV/H2O2 systems. The effects of iron species (Fe2+ and Fe3+), iron concentration (0-0.3 mg/L), H2O2 concentration (0-10 mg/L) and background water matrix (low-carbon tap (LCT) and well water) on HO production and compound removal were examined. Iron-assisted UV/H2O2 efficiency was most influenced by the target chemical and the water matrix. Added iron to UV/H2O2 was shown to increase the steady-state HO concentration by approximately 25% in all well water scenarios. While CBZ removal was unchanged by iron addition, 0.3 mg/L iron improved NDMA removal rates in both LCT and well water matrices by 15.1% and 4.6% respectively. Furthermore, the combination of UV/Fe without H2O2 was also shown to enhance NDMA removal when compared to UV photolysis alone indicating the presence of degradation pathways other than HO oxidation.

Degradation of N-nitrosodimethylamine (NDMA) and its precursor dimethylamine (DMA) in mineral micropores induced by microwave irradiation.

Removal of N-nitrosodimethylamine (NDMA) in drinking water treatment poses a significant technical challenge due to its small molecular size, high polarity and water solubility, and poor biodegradability. Degradation of NDMA and its precursor, dimethylamine (DMA), was investigated by adsorbing them from aqueous solution using porous mineral sorbents, followed by destruction under microwave irradiation. Among the mineral sorbents evaluated, dealuminated ZSM-5 exhibited the highest sorption capacities for NDMA and DMA, which decreased with the density of surface cations present in the micropores. In contrast, the degradation rate of the sorbed NDMA increased with the density of surface cations under microwave irradiation. Evolutions of the degradation products and C/N ratio indicate that the sorbed NDMA and DMA could be eventually mineralized under continuous microwave irradiation. The degradation rate was strongly correlated with the bulk temperature of ZSM-5 and microwave power, which is consistent with the mechanism of pyrolysis caused by formation of micro-scale "hot spots" within the mineral micropores under microwave irradiation. Compared to existing treatment options for NDMA removal, microporous mineral sorption coupled with microwave-induced degradation has the unique advantages of being able to simultaneously remove NDMA and DMA and cause their full mineralization, and thus could serve as a promising alternative method.

Phototransformation of wastewater-derived trace organic contaminants in open-water unit process treatment wetlands.

Open-water cells in unit process treatment wetlands can be used to exploit sunlight photolysis to remove trace organic contaminants from municipal wastewater effluent. To assess the performance of these novel systems, a photochemical model was calibrated using measured photolysis rates for atenolol, carbamazepine, propranolol, and sulfamethoxazole in wetland water under representative conditions. Contaminant transformation by hydroxyl radical ((•)OH) and carbonate radical ((•)CO3(-)) were predicted from steady-state radical concentrations measured at pH values between 8 and 10. Direct photolysis rates and the effects of light screening by dissolved organic matter on photolysis rates were estimated using solar irradiance data, contaminant quantum yields, and light screening factors. The model was applied to predict the land area required for 90% removal of a suite of wastewater-derived organic contaminants by sunlight-induced reactions under a variety of conditions. Results suggest that during summer, open-water cells that receive a million gallons of water per day (i.e., about 4.4 × 10(-2) m(3) s(-1)) of nitrified wastewater effluent can achieve 90% removal of most compounds in an area of about 15 ha. Transformation rates were strongly affected by pH, with some compounds exhibiting faster transformation rates under the high pH conditions associated with photosynthetic algae at the sediment-water interface and other contaminants exhibiting faster transformation rates at the circumneutral pH values characteristic of algae-free cells. Lower dissolved organic carbon concentrations typically resulted in increased transformation rates.

The formation of reactive species having hydroxyl radical-like reactivity from UV photolysis of N-nitrosodimethylamine (NDMA): kinetics and mechanism.

This study focuses on the detailed mechanism by which N-nitrosodimethylamine (NDMA) is photolyzed to form oxidized products, i.e., NO(2)(-) and NO(3)(-), and reveals a key reactive species produced during the photolysis of NDMA. Under acidic conditions, NO(2)(-) formed from the photodecomposition of NDMA was more prevalent than NO(3)(-). In this result, key species for the formation of NO(2)(-) are presumably N(2)O(3) and N(2)O(4) as termination products as well as NO and O(2) as reactants. Conversely, under alkaline conditions, NO(3)(-) was more prevalent than NO(2)(-). For this result, a key species for NO(3)(-) formation is presumably peroxynitrite (ONOO(-)). A detailed mechanistic study was performed with a competition reaction (or kinetics) between NDMA and p-nitrosodimethylaniline (PNDA) probe for hydroxyl radical (OH). It is fortuitous that the second-order rate constant for NDMA with an unknown reactive species (URS) was 5.13×10(8) M(-1) s(-1), which was similar to its published value for the reaction of NDMA+OH. Our study results showed that a key reactive species generated during NDMA photo-decomposition had hydroxyl radical-like reactivity and in particular, under alkaline conditions, it is most likely ONOO(-) as a source of nitrate ion. Therefore, for the first time, we experimentally report that an URS having OH-like reactivity can be formed during photochemical NDMA decomposition. This URS could contribute to the formations of NO(2)(-) and NO(3)(-).

Authors' response to comments on "Inhibiting the regeneration of N-nitrosodimethylamine in drinking water by UV photolysis combined with ozonation" by F. Xiao.

Previous published paper "Inhibiting the regeneration of N-nitrosodimethylamine (NDMA) in drinking water by UV photolysis combined with ozonation" by our research group, was commented by Dr. Xiao. This comment was criticized and doubted from several aspects including the research topic, experimental design and interpretation of data. We thanked Dr. Xiao for the useful suggestion for our future research. However, we do not fully agree with other comments. In this letter, we now take the opportunity of responding, some issues are discussed here in more detail.

Inhibiting the regeneration of N-nitrosodimethylamine in drinking water by UV photolysis combined with ozonation.

N-Nitrosodimethylamine (NDMA) is a highly carcinogenic compound that is suspected of carcinogenic activity in the human body. A variety of methods are used to remove NDMA from water, but the main degradation products, dimethylamine (DMA) and NO(2)(-), are also precursors for NDMA formation. UV irradiation combined with ozonation (UV/O(3)) was examined in this investigation for its ability to inhibit the regeneration of NDMA after degradation. Both the degradation products and the regeneration potential of NDMA were compared between UV irradiation alone and UV/O(3). The yields of DMA and NO(2)(-) in the UV/O(3) process were less than for UV irradiation alone. Yields of DMA and NO(2)(-) were 2.25 mg L(-1) and 3.22 mg L(-1) from UV irradiation, while they were 0.92 mg L(-1) and 0.45 mg L(-1) from the UV/O(3) process. Furthermore, the regeneration of NDMA was also less after the UV/O(3) process than after UV irradiation. The concentration of regenerated NDMA was more than 51.8 microg L(-1) after UV irradiation regardless of the dosage of Cl(2). However, the concentration of regenerated NDMA in the UV/O(3) process was less than 7.37 microg L(-1) under the same conditions. Consequently, the UV/O(3) process was more effective than UV irradiation alone in inhibiting NDMA regeneration. The inhibition of NDMA regeneration was due to a decrease in DMA and NO(2)(-) produced by the UV/O(3) process. As the major products generated from NDMA, NO(2)(-) and DMA were likely to be oxidized by ozone and hydroxyl radicals (OH). In addition, the reaction between NDMA and OH would possibly generate methylamine as the only product, leading to a decrease in the production of DMA by the UV/O(3) process.

Degradation of dimethylnitrosoamine catalysed by physical and chemical agents.

Decomposition of dimethylnitrosoamine (DMNA) by chemical and physical agents was further investigated. Both photoirradiation with sunlight or ultraviolet ray and reductive reactions under acid conditions (likely occurring in the stomach) led to the formation of formaldehyde, formic acid, and N-methydrazine, in addition to denitrosated compounds such as methylamine, dimethylamine, and N-methylhydroxylamine. N-Methylhydrazine was the only compound which was not detected by photoirradiation under neutral conditions. The agreement between physiochemical and metabolic degradation products and the possible biological meaning are discussed together with the problem of environmental contamination by the nitroso compound.