This research examined the impacts of water quality, phosphate-based corrosion inhibitors and pipe wall exposure on free chlorine (HOCl)/chloramine (NH2Cl) degradation and haloacetic acid (HAA)/N-nitrosodimethylamine (NDMA) formation in simulated distribution system water mains and household plumbing at bench-scale and pilot scale. In bench-scale bottle tests, the reactivity of fresh/pre-corroded pipe materials with HOCl/NH2Cl in decreasing order was: ductile iron, copper, lead. The addition of phosphate-based corrosion inhibitors generally increased HOCl/NH2Cl degradation for fresh iron coupons, but decreased HOCl/NH2Cl decay only for fresh copper coupons. Generally, these corrosion inhibitors did not impact HAA formation. Copper corrosion products, including Cu(II), Cu2O, CuO and Cu2(OH)2CO3, catalyzed HAA and NDMA formation. For HAAs, copper catalysis increased with increasing pH from 6.6 to 8.6 and/or increasing concentrations of these copper corrosion products. Interactions of copper with natural organic matter (NOM), likely by complexation, and the subsequent increase in the reactivity of NOM were proposed to be the primary reason for the increased HAA formation.NDMA formation increased with increasing Cu(II) concentrations, DMA concentrations, alkalinity and hardness but was inhibited by the presence of NOM. The transformation of NH2Cl to dichloramine (NHCl2) and complexation of copper with DMA were proposed to be involved in elevating the formation of NDMA at pH 7.0. Finally, in pilot-scale modified pipe loop tests, copper catalysis of NDMA formation was confirmed, especially under laminar flow conditions, and iron was shown to possibly catalyze NDMA formation under turbulent conditions. Orthophosphate increased the catalytic effects of iron but decreased copper catalysis on NDMA formation by either modifying the properties of the iron-associated suspended particles or reducing the dissolved metal concentrations. Orthophosphate increased chloramine decay when in contact with iron, likely by promoting nitrite formation, but orthophosphate decreased chloramine decay for copper and lead by reducing the availability of metal corrosion products.

N-Nitrosodimethylamine (commonly known as NDMA) is a probable human carcinogen that has been recognized as an emerging drinking water contaminant in recent years. Previous studies have shown that certain N-containing organic compounds may form NDMA in reaction with chlorine or monochloramine and the NDMA yield is affected by the structure of the organic-N compounds, water conditions and treatment parameters. Many amine-based water treatment polymers contain organic-N functional groups and thus have been suspected as potential NDMA precursors in water treatment systems. The purpose of this research was to systematically assess the potential NDMA formation from different structural types of water treatment polymers in reactions with various oxidants and probe the possible factors that influence the NDMA formation. Robust analytical methods for detection of NDMA and the well-known NDMA precursor dimethylamine (DMA) in the reaction samples were established. The cationic polyacrylamide (cationic PAMS), aminomethylated polyacrylamide (Mannich), poly-diallyldimethylammonium chloride (polyDADMAC) and polyamine polymers were evaluated in reactions with nitrite, free chlorine, monochloramine or chlorine dioxide in aqueous solutions at circumneutral pH and room temperature conditions. This study employed high dosages of polymer and oxidant and long reaction time in order to assess the maximum potential to form NDMA. A range of operational parameters that may affect the above reactions were also evaluated.

This research examined the impacts of water quality, phosphate-based corrosion inhibitors and pipe wall exposure on free chlorine (HOCl)/chloramine (NH2Cl) degradation and haloacetic acid (HAA)/N-nitrosodimethylamine (NDMA) formation in simulated distribution system water mains and household plumbing at bench-scale and pilot scale. In bench-scale bottle tests, the reactivity of fresh/pre-corroded pipe materials with HOCl/NH2Cl in decreasing order was: ductile iron, copper, lead. The addition of phosphate-based corrosion inhibitors generally increased HOCl/NH2Cl degradation for fresh iron coupons, but decreased HOCl/NH2Cl decay only for fresh copper coupons. Generally, these corrosion inhibitors did not impact HAA formation. Copper corrosion products, including Cu(II), Cu2O, CuO and Cu2(OH)2CO3, catalyzed HAA and NDMA formation. For HAAs, copper catalysis increased with increasing pH from 6.6 to 8.6 and/or increasing concentrations of these copper corrosion products. Interactions of copper with natural organic matter (NOM), likely by complexation, and the subsequent increase in the reactivity of NOM were proposed to be the primary reason for the increased HAA formation.NDMA formation increased with increasing Cu(II) concentrations, DMA concentrations, alkalinity and hardness but was inhibited by the presence of NOM. The transformation of NH2Cl to dichloramine (NHCl2) and complexation of copper with DMA were proposed to be involved in elevating the formation of NDMA at pH 7.0. Finally, in pilot-scale modified pipe loop tests, copper catalysis of NDMA formation was confirmed, especially under laminar flow conditions, and iron was shown to possibly catalyze NDMA formation under turbulent conditions. Orthophosphate increased the catalytic effects of iron but decreased copper catalysis on NDMA formation by either modifying the properties of the iron-associated suspended particles or reducing the dissolved metal concentrations. Orthophosphate increased chloramine decay when in contact with iron, likely by promoting nitrite formation, but orthophosphate decreased chloramine decay for copper and lead by reducing the availability of metal corrosion products.

Dietary nitrite intake has been implicated in numerous gastrointestinal cancers in humans due to the formation of a group of carcinogens called N-nitroso compounds. The need to estimate their intake is vital in establishing at risk population and to monitor and perhaps one day manage their dietary intake. This is the first study to estimate nitrate and nitrite in selected vegetables, cured and fresh meat in Australian food supply using ion-paired reversed-phased HPLC. Nitrite content in meat products analysed ranged from 0 to 83.9 mg/kg in medallion beef and Frankfurt, respectively; nitrate content ranged from 18.7 mg/kg in minced beef to 142.5 mg/kg in salami. The nitrite content was below the maximum limit set by the Food Standards Australia and New Zealand. Nitrate content in selected vegetables ranged from 123 to 4850 mg/kg in Iceberg lettuce and English spinach, respectively; only minimal nitrite at 20 mg/kg was present in Gai choy, which was most likely due to bacterial contamination during storage. Based on the food consumption pattern of Australians, the dietary nitrite and nitrate intake from bacon were 1.51 and 3.42 mg per capita per day, which was below the Adequate Daily Intake set by the European Union Scientific Committee for food in 1995. Taking into considerations of oral nitrate reduction to nitrite and the endogenous nitrate formation, the upper extreme of dietary nitrite and nitrate intake in Australians were 44 and 2.4 times over the ADI, respectively. However, this does not take into effect of other dietary promoters and inhibitors. Eighteen healthy human volunteers were put on a low nitrate, nitrite and antioxidant diet for three days during which they were fed one serving of cured meat with and without 500 mg of vitamin C. Using GC-MS, N-nitrosodimethylamine was not detected in the urine before or after vitamin C supplementation, suggested that a diet low on nitrate and nitrite cannot produce NDMA and thus may reduce the risk of developing gastrointestinal cancers. Different extraction methods and combination of herbs and spices were demonstrated in vitro to show inhibition against B. cereus, Escherichia coli, Listeria monocytogenes, Salmonella Enteritidis and Staphylococcus aureus. In addition, autoclaved turmeric powder at 0.3 % (w/v), hot water extracted turmeric with ginger at 0.5 % and rosemary at 1.0 % showed growth inhibition against Clostridium sporogenes, which was used as a surrogate for Clostridium botulinum. The use of these combinations of herbs and spices may replace or at least reduce the use of nitrite as a preservative in cured meat products to prevent botulism and reduce dietary nitrite intake.

Dietary nitrite intake has been implicated in numerous gastrointestinal cancers in humans due to the formation of a group of carcinogens called N-nitroso compounds. The need to estimate their intake is vital in establishing at risk population and to monitor and perhaps one day manage their dietary intake. This is the first study to estimate nitrate and nitrite in selected vegetables, cured and fresh meat in Australian food supply using ion-paired reversed-phased HPLC. Nitrite content in meat products analysed ranged from 0 to 83.9 mg/kg in medallion beef and Frankfurt, respectively; nitrate content ranged from 18.7 mg/kg in minced beef to 142.5 mg/kg in salami. The nitrite content was below the maximum limit set by the Food Standards Australia and New Zealand. Nitrate content in selected vegetables ranged from 123 to 4850 mg/kg in Iceberg lettuce and English spinach, respectively; only minimal nitrite at 20 mg/kg was present in Gai choy, which was most likely due to bacterial contamination during storage. Based on the food consumption pattern of Australians, the dietary nitrite and nitrate intake from bacon were 1.51 and 3.42 mg per capita per day, which was below the Adequate Daily Intake set by the European Union Scientific Committee for food in 1995. Taking into considerations of oral nitrate reduction to nitrite and the endogenous nitrate formation, the upper extreme of dietary nitrite and nitrate intake in Australians were 44 and 2.4 times over the ADI, respectively. However, this does not take into effect of other dietary promoters and inhibitors. Eighteen healthy human volunteers were put on a low nitrate, nitrite and antioxidant diet for three days during which they were fed one serving of cured meat with and without 500 mg of vitamin C. Using GC-MS, N-nitrosodimethylamine was not detected in the urine before or after vitamin C supplementation, suggested that a diet low on nitrate and nitrite cannot produce NDMA and thus may reduce the risk of developing gastrointestinal cancers. Different extraction methods and combination of herbs and spices were demonstrated in vitro to show inhibition against B. cereus, Escherichia coli, Listeria monocytogenes, Salmonella Enteritidis and Staphylococcus aureus. In addition, autoclaved turmeric powder at 0.3 % (w/v), hot water extracted turmeric with ginger at 0.5 % and rosemary at 1.0 % showed growth inhibition against Clostridium sporogenes, which was used as a surrogate for Clostridium botulinum. The use of these combinations of herbs and spices may replace or at least reduce the use of nitrite as a preservative in cured meat products to prevent botulism and reduce dietary nitrite intake.