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This study was undertaken to investigate denitrification and nitrous oxide production in sediments and the key environmental factors influencing these within selected river systems of the LOIS (Land-Ocean Interaction Study) area in North-East England and southern Scotland. Seasonal and spatial trends were evident in both environmental and denitrification data measured monthly for 1.5 years along the Swale-Ouse system from source to tidal limits. Denitrification, measured in sediment cores using acetylene inhibition and expressed by unit area of sediment, increased with distance from source down to freshwater tidal limits. Results from a supplementary survey of the freshwater tidal reaches of the Yorkshire Ouse showed a decrease from the tidal limits. Denitrification activity showed a spring (March to May) peak, particularly in the lowland sites. The highest rate (883±134 µmol N m(^-2) h(^-1)) was measured on the River Wiske, a highly eutrophic lowland tributary to the Swale. A high degree of colinearity was evident between environmental variables, although a significant relationship between denitrification, nitrate and temperature was found through multiple regression. For comparison, measurements were made in the less populated Tweed river system. The seasonal and spatial trends evident in both the environmental and denitrification data from the River Tweed, under a more limited sampling programme, were generally consistent with those observed in the Swale-Ouse system. An intensive field investigation of 50 river sites showed that both potential denitrification rate and N(_2)O production in sediment slurries were positively correlated with nitrate water concentration, sediment water content and percentage of fine (<100 µm) sediment particles. An experimental study investigating the kinetic parameters for denitrification, found that sediment cores taken along the Swale-Ouse exhibited a saturation type curve with added nitrate. Apparent affinity and estimates of apparent maximum velocity for mixed populations of denitrifying bacteria showed an increase on moving downstream and were highest on the Wiske.

This study looks at spatial variation of groundwater nitrate in Texas and its fluctuations at 10 year increments using data from the Texas Water Development Board. While groundwater nitrate increased in the Ogallala and Seymour aquifers across the time period, the overall rate in Texas appears to be declining as time progresses. However, the available data is limited. Findings show that a much more targeted, knowledge based strategy for sampling would not only reduce the cost of water quality analysis but also reduce the risk of error in these analyses by providing a more realistic picture of the spatial variation of problem contaminants, thereby giving decision-makers a clearer picture on how best to handle the reduction and elimination of problem contaminants.

A range of ion selective electrodes (ISEs) for the determination of nitrate has been produced using polymeric membranes containing immobilised quaternary ammonium salts as the ion exchanger. The use of the conventional solvent casting technique gave rise to a relatively low cross-link density, two sided response and poor thickness control. The development of a hot pressing technique resolved all the se problems and would readily suit large scale manufacturing. In this work poly(acrylonitrilebutadiene)(NBr) was selected as the membrane matrix and was robust, gave enhanced selectivity coefficients and extended membrane lifetime. The best electrode fabricated contained 6-5% m/m triallyloctylammonium bromide, 7-2% m/m dicumyl peroxide and 39-7% m/m2 -nitrophenyloctyl ether in a 50% ACN content N Br polymer matrix. The electrode had a lifetime in excess of 665 days and the response to nitrate was Nernstian in the range I x 10&quot; to I x 10' mol dm-1 of nitrate. The limit of detection was 4-5 x IW mol dm-1 and the selectivity coefficient k Pot NO,,- - C1 was 5.3 xIW. The immobilised ion exchanger membrane electrode offered superior lifetime and mechanical strength. The cross-link density of the membranes was determined by solvent swelling and the use of the Flory-Rehner equation. The role of cross-link density upon the electroanalytical properties of membranes was investigated in the range 0-6 x 10' to 11-0 x 10' mol cross-link cm-'. The membranes were studied using electron microscopy and the conditioning process monitored using ion exchange chromatography. Two different response mechanisms were proposed dependent on the membrane composition and the inclusion of solvent mediator.

Thesis (Ph.D.)--Boston University / Due to the necessity of recovering uranium from reactor fuels, a number of separation methods have been investigated in recent years. Of these, the method of solvent extraction has proved to be a practical one. Long chain symmetrical phosphine oxides have been shown to extract uranium and a number of other metals under different conditions. It was the object of the present investigation to establish the nature of the species resulting from uranyl nitrate-R3Po (R =alkyl group) interaction. The two phosphine oxides selected for the study were: (i) Tri-n-octylphosphine oxide (TOPO) and (ii) Tris(2-ethylhexyl)phosphine oxide (TEHPO). An attempt was made to obtain pure TEHPO. Though the attempt has not met with complete success, yet significant conclusions concerning the stoichiometry and relative stability of the uranyl nitrate-TEHPO complex could be drawn. [TRUNCATED]

Green rusts (GRs), a group of layered Fe(II)-Fe(III) hydroxide salts, have been observed to be effective reductants for degrading organic and inorganic contaminants under suboxic conditions. Furthermore, the addition of a transition metal to GRs can produce high-activity modified green rusts (HMGRs) that demonstrate higher degradation rates. Methods of modifying GRs to obtain high reactivity for degradation of PCE and nitrate were developed and reduction kinetics of PCE and nitrate by HMGRs were characterized in this study. First, the most promising HMGRs were developed through screening tests. GRs modified with Pt, Cu, Ag, or Pb were found to be effective in improving degradation rates of PCE. GR-F(Pt) and GR-F(Cu) were chosen because they showed high reactivity and produced non-chlorinated by-products. Pt and Cu showed the capability of improving reduction kinetics of nitrate by GRs. GR-F(Pt) and GR-F(Cu) were selected for further study. Second, degradation of PCE by GR-F(Cu) and GR-F(Pt) was characterized using a batch reactor system. The reaction kinetics of PCE degradation by GR-F(Cu) and GR-F(Pt) was strongly dependent on pH over the range of pH 7.5-11, with the fastest rate at pH 11. Increasing concentrations of Cu(II) over the range of 0 to 5 mM resulted in improving the reduction kinetics by a factor of more than 400, although the rate at 7.5 mM of Cu(II) was unexpectedly lower than that at 5 mM. Surface saturation behavior was observed in the rates of dechlorination of PCE by GR-F(Cu). Finally, nitrate reduction by GR-F(Cu) and GR-F(Pt) was further studied to determine the effects on degradation rates of pH, Cu(II) addition, and initial nitrate concentration. A reaction model with four sequential steps was proposed to describe the process of nitrate being reduced to ammonium and GR being oxidized to magnetite. The reaction rates of nitrate reduction by GR-F(Cu) and GR-F(Pt) was highest at pH 9. The reaction rates of GR-NO3 were improved by three orders of magnitude when Cu(II) was added in the range of 0 to 2.5 mM, while reaction rate decreased at concentrations above 2.5 mM. Saturation behavior was also observed in nitrate reduction by GR-F(Cu).

Green rusts (GRs), a group of layered Fe(II)-Fe(III) hydroxide salts, have been observed to be effective reductants for degrading organic and inorganic contaminants under suboxic conditions. Furthermore, the addition of a transition metal to GRs can produce high-activity modified green rusts (HMGRs) that demonstrate higher degradation rates. Methods of modifying GRs to obtain high reactivity for degradation of PCE and nitrate were developed and reduction kinetics of PCE and nitrate by HMGRs were characterized in this study. First, the most promising HMGRs were developed through screening tests. GRs modified with Pt, Cu, Ag, or Pb were found to be effective in improving degradation rates of PCE. GR-F(Pt) and GR-F(Cu) were chosen because they showed high reactivity and produced non-chlorinated by-products. Pt and Cu showed the capability of improving reduction kinetics of nitrate by GRs. GR-F(Pt) and GR-F(Cu) were selected for further study. Second, degradation of PCE by GR-F(Cu) and GR-F(Pt) was characterized using a batch reactor system. The reaction kinetics of PCE degradation by GR-F(Cu) and GR-F(Pt) was strongly dependent on pH over the range of pH 7.5-11, with the fastest rate at pH 11. Increasing concentrations of Cu(II) over the range of 0 to 5 mM resulted in improving the reduction kinetics by a factor of more than 400, although the rate at 7.5 mM of Cu(II) was unexpectedly lower than that at 5 mM. Surface saturation behavior was observed in the rates of dechlorination of PCE by GR-F(Cu). Finally, nitrate reduction by GR-F(Cu) and GR-F(Pt) was further studied to determine the effects on degradation rates of pH, Cu(II) addition, and initial nitrate concentration. A reaction model with four sequential steps was proposed to describe the process of nitrate being reduced to ammonium and GR being oxidized to magnetite. The reaction rates of nitrate reduction by GR-F(Cu) and GR-F(Pt) was highest at pH 9. The reaction rates of GR-NO3 were improved by three orders of magnitude when Cu(II) was added in the range of 0 to 2.5 mM, while reaction rate decreased at concentrations above 2.5 mM. Saturation behavior was also observed in nitrate reduction by GR-F(Cu).