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Infrared multiple photon dissociation action spectra of the protonated forms of the cytidyl nucleosides, 2'-deoxycytidine, [dCyd+H](+), and cytidine, [Cyd+H](+), are acquired over the IR fingerprint and hydrogen-stretching regions. Electronic structure calculations are performed at the B3LYP/6-311+G(d,p) level to determine the stable low-energy tautomeric conformations of these species generated upon electrospray ionization (ESI) and to generate the linear IR absorption spectra of these protonated nucleosides. Comparison between the experimental and theoretical spectra allows the tautomeric conformations of [dCyd+H](+) and [Cyd+H](+) populated by ESI to be determined. B3LYP predicts N3 as the preferred protonation site for both [dCyd+H](+) and [Cyd+H](+), whereas MP2 suggests that protonation at O2 is more favorable. The 2'-hydroxyl substituent does not significantly alter the structures of the B3LYP N3 and MP2 O2 protonated ground tautomeric conformations of [dCyd+H](+) vs [Cyd+H](+). [dCyd+H](+) and [Cyd+H](+) exhibit very similar spectral signatures in both regions. Nonetheless, the 2'-hydroxyl does affect the relative intensities of the IRMPD bands of [dCyd+H](+) vs [Cyd+H](+). The spectral features observed in the hydrogen-stretching region complement those of the fingerprint region and allow the N3 and O2 protonated tautomeric conformations to be readily distinguished. Comparison between the measured and computed spectra indicates that both N3 and O2 protonated tautomeric conformations coexist in the experiments, and the populations are dominated by the most stable N3 and O2 protonated tautomeric conformations. Least-squares fitting of the IRMPD spectra to the IR spectra for these most stable conformers suggests relative populations of ∼55% N3 vs 45% O2 protonated conformers of [dCyd+H](+), whereas ∼47% N3 vs 53% O2 protonated conformers of [Cyd+H](+). This change in the preferred site of protonation indicates that the 2'-hydroxyl substituent plays an important role in controlling the reactivity of the cytidyl nucleosides.

A horizontal flow biofilm reactor (HFBR) designed for the treatment of synthetic wastewater (SWW) was studied to examine the spatial distribution and dynamics of nitrogen transformation processes. Detailed analyses of bulk water and biomass samples, giving substrate and proportions of ammonia oxidising bacteria (AOB) and nitrite oxidising bacteria (NOB) gradients in the HFBR, were carried out using chemical analyses, sensor rate measurements and molecular techniques. Based on these results, proposals for the design of HFBR systems are presented. The HFBR comprised a stack of 60 polystyrene sheets with 10-mm deep frustums. SWW was intermittently dosed at two points, Sheets 1 and 38, in a 2 to 1 volume ratio respectively. Removals of 85.7% COD, 97.4% 5-day biochemical oxygen demand (BOD(5)) and 61.7% TN were recorded during the study. In the nitrification zones of the HFBR, which were separated by a step-feed zone, little variation in nitrification activity was found, despite decreasing in situ ammonia concentrations. The results further indicate significant simultaneous nitrification and denitrification (SND) activity in the nitrifying zones of the HFBR. Sensor measurements showed a linear increase in potential nitrification rates at temperatures between 7 and 16 degrees C, and similar rates of nitrification were measured at concentrations between 1 and 20mg NH(4)-N/l. These results can be used to optimise HFBR reactor design. The HFBR technology could provide an alternative, low maintenance, economically efficient system for carbon and nitrogen removal for low flow wastewater discharges., (Copyright 2010 Elsevier Ltd. All rights reserved.)

This study investigated the performance of a horizontal-flow biofilm reactor in treating domestic-strength synthetic wastewater (SWW) under three hydraulic and chemical oxygen demand (COD) loading rates (phases 1 to 3) ranging from 152 L/m2 x d and 58.9 g COD/m2 x d to 497 L/m2 x d and 192.7 g COD/m2 x d, respectively; the rates were based on the top surface plan area (TSPA) of the reactor. The reactor comprised a stack of 30 horizontal polystyrene sheets. The SWW, intermittently dosed onto the unit, flowed over and back along sequential sheets in the stack before exiting at the bottom of the unit. Maximum average removals of > 98% biochemical oxygen demand and 96.2% total ammonium-nitrogen (NH4-N) were observed. The TSPA COD and NH4-N removal rates were high for all phases. The unit provides a high-performance, economic, low-maintenance, and flexible alternative for removing carbon and ammonium from low-flow point sources.

The performance of a 10 L sequencing batch reactor (SBR) treating slaughterhouse wastewater was examined at ambient temperature. The influent wastewater comprised 4672+/-952 mg chemical oxygen demand (COD)/L, 356+/-46 mg total nitrogen (TN)/L and 29+/-10 mg total phosphorus (TP)/L. The duration of a complete cycle was 8 h and comprised four phases: fill (7 min), react (393 min), settle (30 min) and draw/idle (50 min). During the react phase, the reactor was intermittently aerated with an air supply of 0.8L/min four times at 50-min intervals, 50 min each time. At an influent organic loading rate of 1.2g COD/(Ld), average effluent concentrations of COD, TN and TP were 150 mg/L, 15 mg/L and 0.8 mg/L, respectively. This represented COD, TN and TP removals of 96%, 96% and 99%, respectively. Phase studies show that biological phosphorus uptake occurred in the first aeration period and nitrogen removal took place in the following reaction time by means of partial nitrification and denitrification. The nitrogen balance analysis indicates that denitrification and biomass synthesis contributed to 66% and 34% of TN removed, respectively.

Nutrient removal from domestic strength synthetic wastewater by an alternating pumped flow sequencing batch biofilm reactor (APFSBBR) was investigated in this laboratory study. The APFSBBR comprised two reactor tanks (Reactors 1 and 2) with two identical biofilm modules of vertical tubular plastic media with a high specific surface area, one in each tank. The APFSBBR was operated in cycles of four phases: fill, anaerobic, aerobic, and draw. During the fill phase, Reactor 1 was half-filled with domestic strength synthetic wastewater. During the subsequent anaerobic phase, most of the phosphorus release took place from the submerged biofilm in this reactor. In the aerobic phase, the wastewater was circulated by pumps between Reactors 1 and 2, resulting in denitrification at the start of the aerobic phase due to low oxygen concentrations, followed by nitrification and luxury uptake of phosphorus when oxygen concentrations increased. During the draw phase, Reactor 2 was half-emptied of the treated water. At the chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP) loading rates on the total biofilm area of 3.20 g COD, 0.33 g TN, and 0.06 g TP m(-2) d(-1), the removal efficiencies were 97, 85, and 92% for COD, TN, and TP, respectively.

A stratified sand filter column, operated in recirculation mode and treating synthetic effluent resembling high-strength dairy wastewaters was studied over a 342-d duration. The aim of this paper was to examine the organic, total suspended solids (TSS) and nutrient removal rates of the sand filter, operated in recirculation mode, under incrementally increasing hydraulic and organic loading rates and to propose a field filter-sizing criterion. Best performance was obtained at a system hydraulic loading rate of 10 L m(-2) d(-1); a higher system hydraulic loading rate (of 13.4 L m(-2) d(-1)) caused surface ponding. The system hydraulic loading rate of 10 L m(-2) d(-1) gave a filter chemical oxygen demand (COD), TSS, and total kjeldahl nitrogen (TKN) loading rate of 14, 3.7, and 2.1 g m(-2) d(-1), respectively, and produced consistent COD and TSS removals of greater than 99%, and an effluent NO(3)-N concentration of 42 mg L(-1) (accounting for an 86% reduction in total nitrogen (Tot-N)). As the proportional surface area requirement for the sand filter described in this study is less than the recommended surface area requirement of a free-water surface (FWS) wetland treating an effluent of similar quality, it could provide an economic and sustainable alternative to conventional wetland treatment.

Collision-induced dissociation of complexes of Cu+ bound to a variety of N-donor ligands (N-L) with Xe is studied using guided ion beam tandem mass spectrometry. The N-L ligands examined include pyridine, 4,4-dipyridyl, 2,2-dipyridyl, and 1,10-phenanthroline. In all cases, the primary and lowest-energy dissociation channel observed corresponds to the endothermic loss of a single intact N-L ligand. Sequential dissociation of additional N-L ligands is observed at elevated energies for the pyridine and 4,4-dipyridyl complexes containing more than one ligand. Ligand exchange processes to produce Cu+Xe are also observed as minor reaction pathways in several systems. The primary cross section thresholds are interpreted to yield 0 and 298 K bond dissociation energies (BDEs) after accounting for the effects of multiple ion-neutral collisions, the kinetic and internal energy distributions of the reactants, and dissociation lifetimes. Density functional theory calculations at the B3LYP/6-31G* level are performed to obtain model structures, vibrational frequencies, and rotational constants for the neutral N-L ligands and the Cu+(N-L)x complexes. The relative stabilities of the various conformations of these N-L ligands and Cu+(N-L)x complexes as well as theoretical BDEs are determined from single point energy calculations at the B3LYP/6-311+G(2d,2p) level of theory using B3LYP/6-31G* optimized geometries. Excellent agreement between theory and experiment is observed for all complexes containing one or two N-L ligands, while theory systematically underestimates the strength of binding for complexes containing more than two N-L ligands. The ground-state structures of these complexes and the trends in the sequential BDEs are explained in terms of stabilization gained from sd-hybridization and repulsive ligand-ligand interactions. The nature of the binding interactions in the Cu+(N-L)x complexes are examined via natural bond orbital analyses.

Recirculation of fully nitrified effluent from a laboratory horizontal-flow biofilm reactor (HFBR) to a mixed pre-denitrification reactor (DR) was used to remove organic carbon and nitrogen from synthetic dairy wastewater. Three recirculation ratios of 2, 4, and 6 were examined in this study and the average filtered chemical oxygen demand (CODf) and total nitrogen (TN) removals were up to 97.4% and 85.5%, respectively, at 11 degrees C. In the DR, the nitrate nitrogen removal efficiencies and rates were 86-96% and 22-34 g N/m3 d. In the HFBR, the ammonium nitrogen removal rates were 293-337 mg N/m2 d.

An alternating pumped sequencing batch biofilm reactor (APSBBR) system was developed to treat small-scale domestic wastewater. This laboratory system had two reactor tanks, Reactor 1 and Reactor 2, with two identical plastic biofilm modules in each reactor. Reactor 1 of the APSBBR had five operational phases--fill, anoxic, aerobic, settle and draw. In the aerobic phase, the wastewater was circulated between the two reactor tanks with centrifugal pumps and aeration was mainly achieved through oxygen absorption by microorganisms in the biofilms when they were exposed to the air. This paper details the performance of the APSBBR system in treating synthetic domestic wastewater over 18 months. The effluent from the APSBBR system satisfied the European Wastewater Treatment Directive requirements, with respect to COD, ammonium-nitrogen and suspended solids. The biofilm growth in the two reactor tanks was different due to the difference in substrate loadings and growth conditions.

In this study, a biological nitrogen removal process using a vertically moving biofilm system was used to treat synthetic wastewater. The process consisted of two pre-denitrification units, one combined carbonaceous removal/nitrification unit and three nitrification units. Each unit employed biofilm growth on a plastic module. In the anoxic units, the modules were vertically moved, while always submerged, in the bulk fluid; in the aerobic units, they were moved vertically up into the air and down into the wastewater. Three small-scale experiments, having different recirculation ratios and influent loadings, were conducted at a controlled temperature of 11 degrees C. In this system, the carbonaceous removal efficiency was in the range of 94-96% and the total nitrogen removal efficiency was 77-82%. In the anoxic units, the denitrification efficiency was 94-98% and the areal denitrification rates, based on the surface area of the biofilm modules, were 2.9-3.8 g NO3-N/(m2 x d). The nitrification efficiency occurring in the aerobic tanks was up to 95% and the maximum areal ammonium removal rates were 1.3-1.8 g NH4-N/(m2 x d)., (Copyright 2003 Elsevier Ltd.)

In this paper, the performance of a sequencing batch biofilm reactor (SBBR) using an anoxic/anaerobic phase followed by an aerobic phase for nutrient removal from wastewater was investigated. In the laboratory SBBR unit, biofilm was grown on a plastic biofilm media module, which was vertically moved up into the air and down into the bulk fluid during the aerobic phase. The vertical movement of the biofilm module supplied oxygen to the microorganisms. The module was submerged in the wastewater during the anoxic/anaerobic phase. The percentage removals of total chemical oxygen demand (COD), total nitrogen (TN) and soluble orthophosphate (PO4-P) were 95.4%, 68.3% and 89.5% respectively at influent concentrations of COD 773 mg l(-1), TN 49.9 mg l(-1) and PO4-P 16.5 mg l(-1). The effluent COD was 35 mg l(-1), NH4-N 10.2 mg l(-1), NO3-N 5.5 mg l(-1), soluble PO4-P 1.7 mg l(-1) and suspended solids (SS) 19 mg l(-1).

The on-site treatment of wastewaters from single dwellings requires simple, low maintenance systems that reduce the chemical and biochemical oxygen demand (COD and BOD respectively), ammonium-nitrogen (NH4-N), orthophosphate (PO4-P), phosphorus (P), and microorganisms to acceptable concentrations. Sand filters have the potential to achieve these reductions. In this study, a sand tank model of a percolation trench and filter was constructed in the laboratory, loaded with wastewater, and monitored for a period of 293 days. The silty sand filter was seeded for 153 days with effluent from an aerobic biofilm treatment unit. The filter was then loaded with synthetic wastewater of domestic strength for 193 days, when the average organic and hydraulic loading rates on the percolation trench were 13.33 g BOD/m2 d and 75 L/m2 d respectively. Removal rates of 90% for total COD, 99.3% for BOD5, >99% for total NH4-N, 89% for total PO4-P, and 96% for total suspended solids (TSS) were recorded during the study. No excessive clogging of the sand filter was observed. During the study very good dispersion of the wastewater over the sand filter by the percolation trench was recorded. The sand filter was simple to construct and operate and achieved excellent results.

The aim of this laboratory study was to establish the efficacy of a new experimental biofilm system for the removal of nitrogen from synthetic wastewater. The system consisted of six reactors in series: one anaerobic, one anoxic and four aerobic reactors. In both the anaerobic and anoxic reactors, a plastic cuboid module was repeatedly moved up and down in the wastewater, while being totally submerged at all times. In each of the aerobic reactors, an identical module to that used in the anaerobic and anoxic reactors was intermittently and repeatedly immersed in and lifted out of the wastewater. All the individual reactors had a bulk fluid volume of 28.2 litres and the average temperature of the wastewater was about 10 degrees C. Each module consisted of crossflow corrugated plastic sheets with a surface area of 1.824 m2. The nitrate recycle flow from the fourth aerobic tank to the anoxic tank was twice the inflow to that tank. In the anoxic reactor, filtered COD was removed at an average rate of 2.22 kg COD/m3 x d and nitrate-nitrogen was denitrified at a rate of 0.42 kg NO3-N/m3 x d. The average nitrification rate in the second aerobic reactor was 0.12 kg NH4-N/m3 x d. The new biofilm system was simple to construct and operate.

A novel horizontal flow biofilm reactor (HFBR) has been adapted and tested for its efficiency in treating hydrogen sulphide (H2S) and methane (CH4) gas. Six pilot-scale HFBR reactors were commissioned, three each treating CH4 and H2S respectively. The reactors were operated at 10 °C, often typical of ambient temperatures in Ireland, and were simultaneously dosed with an air mixture containing the gas in question and with synthetic wastewater (SWW). Three reactors (HFBR 1, 2 and 3), treating an air mixture containing CH4, were operated over three phases (Phases 1-3) lasting 180 days in total. During each phase the air mixture flow rate (AFR) and the plastic media top plan surface area (TPSA) loading rate to HFBR 1, 2 and 3 were 1.2 m³/m³/h and 0.6 m³/m² TPSA/h respectively. In Phase 1 the reactors were operated in triplicate and were loaded with 8.6 g CH4/m³ reactor/h (4.3 g CH4/m² TPSA/h) and a synthetic wastewater (SWW) similar to domestic sewage at 10 °C. During Phase 2 (reactors also operated in triplicate) the effect of temperature on the reactor performance was examined. During Phase 3 the reactors were operated independently in order to examine the effects of omitting organic carbon and adding additional nitrogen in the formof nitrate-nitrogen (NO3-N), rather than ammonium-nitrogen (NH4-N). During Phase 3, CH4 removal efficiencies (RE) of up to 92.8% were achieved at an empty bed retention time (EBRT) of 50 min, equating to a maximum removal of 8.0 g CH4/m³ reactor/h. Three additional reactors (HFBR 4, 5 and 6) were used to treat an air mixture containing H2S and were loaded at an AFR of 15 m³/m³ reactor/h (7.5 m³/m² TPSA/h) with an average H2S loading rate of 3.34 g H2S/m³ reactor/h (1.67 g H2S/m² TPSA/h). After 50 days of operation, the RE reached 100% for all three reactors at an EBRT of 4 min. In each reactor, profile samples of biofilm, air and liquid were taken periodically from various regions of the HFBR. These allowed detailed description of removal processes and optimisation of the reactors by detailing changes in air, liquid and biofilm composition as air moved through the reactor. [ABSTRACT FROM AUTHOR]

Analyzes the removal of organic matter, nitrogen and phosphorus from synthetic dairy parlor washings when three-quarters of the nitrified effluent is recirculated through the anoxic zone of the sand filter system in Ireland. Chemical oxygen demand; Hydraulic loading rates; Volumetric moisture content.