1. It is shown that in contradistinction to the marked stability of ascorbic acid in acid solution towards nitrate is its sensitiveness towards nitrite. 2. The primary major product of the action of the nitrite is dehydroascorbic acid, which appears to be relatively stable towards the nitrite. 3. The nutritional and other physiological implications of these findings are discussed.
The permeable (sandy) sediments that dominate the world's coastlines and continental shelves are highly exposed to nitrogen pollution, predominantly due to increased urbanisation and inefficient agricultural practices. This leads to eutrophication, accumulation of drift algae and changes in the reactions of nitrogen, including the potential to produce the greenhouse gas nitrous oxide (N2O). Nitrogen pollution in coastal systems has been identified as a global environmental issue, but it remains unclear how this nitrogen is stored and processed by permeable sediments. We investigated the interaction of drift algae biomass and nitrate (NO3-) exposure on nitrogen cycling in permeable sediments that were impacted by high nitrogen loading. We treated permeable sediments with increasing quantities of added macroalgal material and NO3- and measured denitrification, dissimilatory NO3- reduction to ammonium (DNRA), anammox, and nitrous oxide (N2O) production, alongside abundance of marker genes for nitrogen cycling and microbial community composition by metagenomics. We found that the presence of macroalgae dramatically increased DNRA and N2O production in sediments without NO3- treatment, concomitant with increased abundance of nitrate-ammonifying bacteria (e.g. Shewanella and Arcobacter). Following NO3- treatment, DNRA and N2O production dropped substantially while denitrification increased. This is explained by a shift in the relative abundance of nitrogen-cycling microorganisms under different NO3- exposure scenarios. Decreases in both DNRA and N2O production coincided with increases in the marker genes for each step of the denitrification pathway (narG, nirS, norB, nosZ) and a decrease in the DNRA marker gene nrfA. These shifts were accompanied by an increased abundance of facultative denitrifying lineages (e.g. Pseudomonas and Marinobacter) with NO3- treatment. These findings identify new feedbacks between eutrophication and greenhouse gas emissions, and in turn have potential to inform biogeochemical models and mitigation strategies for marine eutrophication.
We report the growth of gallium-based compounds, i.e., gallium oxynitride (GaON) and gallium oxide (Ga2O3) on multilayer graphene (MLG) on insulator using a mixture of ammonium nitrate (NH4NO3) and gallium nitrate (Ga(NO3)3) by electrochemical deposition (ECD) method at room temperature (RT) for the first time. The controlling parameters of current density and electrolyte molarity were found to greatly influence the properties of the grown structures. The thicknesses of the deposited structures increase with the current density since it increases the chemical reaction rates. The layers grown at low molarities of both solutions basically show grain-like layer with cracking structures and dominated by both Ga2O3 and GaON. Such cracking structures seem to diminish with the increases of molarities of one of the solutions. It is speculated that the increase of current density and ions in the solutions helps to promote the growth at the area with uneven thicknesses of graphene. When the molarity of Ga(NO3)3 is increased while keeping the molarity of NH4NO3 at the lowest value of 2.5 M, the grown structures are basically dominated by the Ga2O3 structure. On the other hand, when the molarity of NH4NO3 is increased while keeping the molarity of Ga(NO3)3 at the lowest value of 0.8 M, the GaON structure seems to dominate where their cubic and hexagonal arrangements are coexisting. It was found that when the molarities of Ga(NO3)3 are at the high level of 7.5 M, the grown structures tend to be dominated by Ga2O3 even though the molarity of NH4NO3 is made equal or higher than the molarity of Ga(NO3)3. When the grown structure is dominated by the Ga2O3 structure, the deposition process became slow or unstable, resulting to the formation of thin layer. When the molarity of Ga(NO3)3 is increased to 15 M, the nanocluster-like structures were formed instead of continuous thin film structure. This study seems to successfully provide the conditions in growing either GaON-dominated or Ga2O3-dominated structure by a simple and low-cost ECD. The next possible routes to convert the grown GaON-dominated structure to either single-crystalline GaN or Ga2O3 as well as Ga2O3-dominated structure to single-crystalline Ga2O3 structure have been discussed.
Nutrient solution plays an essential role in providing macronutrients to hydroponic plants. Determining nitrogen in the form of nitrate is crucial, as either a deficient or excessive supply of nitrate ions may reduce the plant yield or lead to environmental pollution. This work aims to evaluate the performance of feature reduction techniques and conventional machine learning (ML) algorithms in determining nitrate concentration levels. Two features reduction techniques, linear discriminant analysis (LDA) and principal component analysis (PCA), and seven ML algorithms, for example, k-nearest neighbors (KNN), support vector machine, decision trees, naïve bayes, random forest (RF), gradient boosting, and extreme gradient boosting, were evaluated using a high-dimensional spectroscopic dataset containing measured nitrate-nitrite mixed solution absorbance data. Despite the limited and uneven number of samples per class, this study demonstrated that PCA outperformed LDA on the high-dimensional spectroscopic dataset. The classification accuracy of ML algorithms combined with PCA ranged from 92.7% to 99.8%, whereas the classification accuracy of ML algorithms combined with LDA ranged from 80.7% to 87.6%. The PCA with the RF algorithm exhibited the best performance with 99.8% accuracy.
Azolla pinnata R.Br. growth performance experiments in different water sources were conducted from May until July 2011 at Aquaculture Research Station, Puchong, Malaysia. Four types of water sources (waste water, drain water, paddy field water and distilled water) each with different nutrient contents were used to grow and evaluate the growth performance of A. pinnata. Four water sources with different nutrient contents; waste, drain, paddy and distilled water as control were used to evaluate the growth performance of A. pinnata. Generally, irrespective of the types of water sources there were increased in plant biomass from the initial biomass (e.g., after the first week; lowest 25.2% in distilled water to highest 133.3% in drain water) and the corresponding daily growth rate (3.61% in distilled water to 19.04% in drain water). The increased in biomass although fluctuated with time was consistently higher in drain water compared to increased in biomass for other water sources. Of the four water sources, drain water with relatively higher nitrate concentration (0.035 +/- 0.003 mg L(-l)) and nitrite (0.044 +/- 0.005 mg L(-1)) and with the available phosphate (0.032 +/- 0.006 mg L(-1)) initially provided the most favourable conditions for Azolla growth and propagation. Based on BVSTEP analysis (PRIMER v5), the results indicated that a combination of more than one nutrient or multiple nutrient contents explained the observed increased in biomass of A. pinnata grown in the different water sources.
A significant breakthrough and progress have been made in the study of the kinetics of microbial transformation in sewers under aerobic and under changing aerobic/anaerobic conditions. Fundamental knowledge on anoxic kinetics of wastewater is still lacking, so it is not now possible to apply an integrated approach to municipal wastewater treatment incorporating sewer networks as a bio-chemical reactor. This paper presents the results of studies on determining half saturation constants for nitrate, KNO3, and nitrite, KNO2, in raw wastewater. The average values of KNO3 and KNO2, determined from experiments conducted on 7 different wastewater samples were found to be 0.76 gNO3-N/m3 and 0.33 gNO2-N/m3 respectively.
Increased use of nitrogenous (N) fertilizers in agriculture has significantly altered the global N-cycle because they release nitrogenous gases of environmental concerns. The emission of nitrous oxide (N2O) contributes to the global greenhouse gas accumulation and the stratospheric ozone depletion. In addition, it causes nitrate leaching problem deteriorating ground water quality. The nitrate toxicity has been reported in a number of studies showing the health hazards like methemoglobinemia in infants and is a potent cause of cancer. Despite these evident negative environmental as well as health impacts, consumption of N fertilizer cannot be reduced in view of the food security for the teeming growing world population. Various agronomic and genetic modifications have been practiced to tackle this problem. Some agronomic techniques adopted include split application of N, use of slow-release fertilizers, nitrification inhibitors and encouraging the use of organic manure over chemical fertilizers. As a matter of fact, the use of chemical means to remediate nitrate from the environment is very difficult and costly. Particularly, removal of nitrate from water is difficult task because it is chemically non-reactive in dilute aqueous solutions. Hence, the use of biological means for nitrate remediation offers a promising strategy to minimize the ill effects of nitrates and nitrites. One of the important goals to reduce N-fertilizer application can be effectively achieved by choosing N-efficient genotypes. This will ensure the optimum uptake of applied N in a balanced manner and exploring the molecular mechanisms for their uptake as well as metabolism in assimilatory pathways. The objectives of this paper are to evaluate the interrelations which exist in the terrestrial ecosystems between the plant type and characteristics of nutrient uptake and analyze the global consumption and demand for fertilizer nitrogen in relation to cereal production, evaluate the various methods used to determine nitrogen use efficincy (NUE), determine NUE for the major cereals grown across large agroclimatic regions, determine the key factors that control NUE, and finally analyze various strategies available to improve the use efficiency of fertilizer nitrogen.
Stormwater runoff is a leading cause of nitrogen (N) transport to water bodies and hence one means of water quality deterioration. Stormwater runoff was monitored in an urban residential catchment (drainage area: 3.89 hectares) in Florida, United States to investigate the concentrations, forms, and sources of N. Runoff samples were collected over 22 storm events (May to September 2016) at the end of a stormwater pipe that delivers runoff from the catchment to the stormwater pond. Various N forms such as ammonium (NH4-N), nitrate (NOx-N), dissolved organic nitrogen (DON), and particulate organic nitrogen (PON) were determined and isotopic characterization tools were used to infer sources of NO3-N and PON in collected runoff samples. The DON was the dominant N form in runoff (47%) followed by PON (22%), NOx-N (17%), and NH4-N (14%). Three N forms (NOx-N, NH4-N, and PON) were positively correlated with total rainfall and antecedent dry period, suggesting longer dry periods and higher rainfall amounts are significant drivers for transport of these N forms. Whereas DON was positively correlated to only rainfall intensity indicating that higher intensity rain may flush out DON from soils and cause leaching of DON from particulates present in the residential catchment. We discovered, using stable isotopes of NO3-, a shifting pattern of NO3- sources from atmospheric deposition to inorganic N fertilizers in events with higher and longer duration of rainfall. The stable isotopes of PON confirmed that plant material (oak detritus, grass clippings) were the primary sources of PON in stormwater runoff. Our results demonstrate that practices targeting both inorganic and organic N are needed to control N transport from residential catchments to receiving waters.
The identification of nitrogen sources and cycling processes is critical to the management of nitrogen pollution. Here, we used both stable (δ15N-NO3-, δ18O-NO3-, δ15N-NH4+) and radiogenic (222Rn) isotopes together with nitrogen concentrations to evaluate the relative importance of point (i.e. sewage) and diffuse sources (i.e. agricultural-derived NO3- from groundwater, drains and creeks) in driving nitrogen dynamic in a shallow coastal embayment, Port Phillip Bay (PPB) in Victoria, Australia. This study is an exemplar of nitrogen-limited coastal systems around the world where nitrogen contamination is prevalent and where constraining it may be challenging. In addition to surrounding land use, we found that the distributions of NO3- and NH4+ in the bay were closely linked to the presence of drift algae. Highest NO3- and NH4+ concentrations were 315 μmol L-1 and 2140 μmol L-1, respectively. Based on the isotopic signatures of NO3- (δ15N: 0.17 to 21‰; δ18O: 3 to 26‰) and NH4+ (δ15N: 30 to 39‰) in PPB, the high nitrogen concentrations were attributed to three major sources which varied between winter and summer; (1) nitrified sewage effluent and drift algae derived NH4+ mainly during winter, (2) NO3- mixture from atmospheric deposition, drains and creeks predominantly observed during summer and (3) groundwater and sewage derived NO3- during both surveys. The isotopic composition of NO3- also suggested the removal of agriculture-derived NO3- through denitrification was prevalent during transport. This study highlights the role of terrestrial-coastal interactions on nitrogen dynamics and illustrates the importance of submarine groundwater discharge as a prominent pathway of diffuse NO3- inputs. Quantifying the relative contributions of multiple NO3- input pathways, however, require more extensive efforts and is an important avenue for future research.
Nitrate reductase inhibitor is usually found in the roots of rice plants (Oryza sativa L. cv MR7), but it was also produced in the shoots of aging plants. The inhibitor was inducible in the shoot of rice seedlings by dark, minus-nitrate or plus-ammonium treatments. There appears to be a general involvement of the inhibitor in the control of nitrate assimilation in the plant.
CaCu3Ti4O12 was synthesized starting from a solution of TiO2 to which Ca and Cu nitrates were added. Due to the differences in the solubilities of the Ca, Cu and Ti, initial variations from ideal stoichiometry and a high solution pH was necessary to obtain stoichiometric CaCu3Ti4O12 precipitates. As precipitated samples were amorphous with CuO phases observed after drying of the precipitates at 300 oC. CaCu3Ti4O12 phases were observed after heat treatment at 1000 oC. XRD studies show the presence of CuO and TiO2 in addition to the CaCu3Ti4O12 for non stoichiometric samples. Observations under the SEM show the presence of Cu rich and Ti rich phases in addition to the CaCu3Ti4O12.
Cu-doped ZnO nanorods were synthesized by sol-gel method using zinc nitrate tetrahydrate, methenamine and cupric acetate monohydrate as precursors. The as-synthesized ZnO nanorods have a twin-rod structure. The polar (002) surface of ZnO nanorods, which could be either negatively charge (O-terminated) or positively charged (Zn- terminated), was responsible for the formation of twin-rod structure. The results showed that the size, aspect ratio, crystallinity and c-lattice parameter of Cu doped ZnO nanorods decreased with increasing of Cu dopant concentration. In fact, the presence of Cu retarded the growth of ZnO nanorods in its preferred growth direction, i.e. (0001). The XPS analysis indicates that Cu ions were oxidized (Cu2+) and substituted into the ZnO lattice at the Zn2+ site. The presence of Cu reduced the optical bandgap of ZnO from 3.34 eV (undoped ZnO nanorods) to 3.31 eV (20 mol% Cu doped ZnO). Besides, it induced a visible PL emission at 2.97 eV, which could be related to the transition of electrons from conduction band (Ec) to Cu acceptor energy level (Ev + 0.45 eV) radiatively.
The adsorption of methyl orange dye from aqueous solution onto penta-bismuth hepta-oxide nitrate, Bi(5)O(7)NO(3), synthesized by precipitation method, was studied in a batch adsorption system. The effects of operation parameters such as adsorbent dose, initial dye concentration, pH and temperature were investigated. The adsorption equilibrium and mechanism of adsorption was evaluated by Langmuir and Freundlich isotherm and different kinetic models, respectively. The results indicate that adsorption is highly dependent on all operation parameters. At optimum conditions, the adsorption capacity was found to be 18.9 mg/g. The adsorption data fits well with the Langmuir isotherm model indicating monolayer coverage of adsorbate molecules on the surface of Bi(5)O(7)NO(3). The kinetic studies show that the adsorption process is a second-order kinetic reaction. Although intra-particle diffusion limits the rate of adsorption, the multi-linearity plot of intra-particle model shows the importance of both film and intra-particle diffusion as the rate-limiting steps of the dye removal. Thermodynamic parameters show that the adsorption process is endothermic, spontaneous and favourable at high temperature.
Fourier transform infrared (FTIR) spectroscopy studies of poly(vinyl alcohol) (PVA), and chitosan polymer blend doped with ammonium nitrate (NH(4)NO(3)) salt and plasticized with ethylene carbonate (EC) have been performed with emphasis on the shift of the carboxamide, amine and hydroxyl bands. 1% acetic acid solution was used as the solvent. It is observed from the chitosan film spectrum that evidence of polymer-solvent interaction can be observed from the shifting of the carboxamide band at 1660 cm(-1) and the amine band at 1591 cm(-1) to 1650 and 1557 cm(-1) respectively and the shift of the hydroxyl band from 3377 to 3354 cm(-1). The hydroxyl band in the spectrum of PVA powder is observed at 3354 cm(-1) and is observed at 3343 cm(-1) in the spectrum of the PVA film. On addition of NH(4)NO(3) up to 30 wt.%, the carboxamide, amine and hydroxyl bands shifted from 1650, 1557 and 3354 cm(-1) to 1642, 1541 and 3348 cm(-1) indicating that the chitosan has complexed with the salt. In the PVA-NH(4)NO(3) spectrum, the hydroxyl band has shifted from 3343 to 3272 cm(-1) on addition of salt from 10 to 30 wt.%. EC acts as a plasticizing agent since there is no shift in the bands as observed in the spectrum of PVA-chitosan-EC films. The mechanism of ion migration is proposed for the plasticized and unplasticized PVA-chitosan-NH(4)NO(3) systems. In the spectrum of PVA-chitosan-NH(4)NO(3)-EC complex, the doublet CO stretching in EC is observed in the vicinity 1800 and 1700. This indicates that there is some interaction between the salt and EC.
A detailed study on the solution chemistry of red soil in South China is presented. Data are collected from two simulated column-leaching experiments with an improved setup to evaluate the effects of atmospheric N deposition (ADN) composition and ADN flux on agricultural soil acidification using a (15)N tracer technique and an in situ soil solution sampler. The results show that solution pH values decline regardless of the increase of the NH4(+)/NO3(-) ratio in the ADN composition or ADN flux, while exchangeable Al(3+), Ca(2+), Mg(2+), and K(+) concentrations increase at different soil depths (20, 40, and 60 cm). Compared with the control, ADN (60 kg per ha per year N, NH4(+)/NO3(-) ratio of 2 : 1) decreases solution pH values, increases solution concentrations of NO3(-)-N, Al(3+), Ca(2+) and Mg(2+) at the middle and lower soil depths, and promotes their removal. NH4(+)-N was not detected in red soil solutions of all the three soil layers, which might be attributed to effects of nitrification, absorption and fixation in farmland red soil. Some of the NO3(-)-N concentrations at 40-60 cm soil depth exceed the safe drinking level of 10 mg L(-1), especially when the ADN flux is beyond 60 kg ha(-1) N. These features are critical for understanding the ADN agro-ecological effects, and for future assessment of ecological critical loads of ADN in red soil farmlands.
The photo-degradation of nutrients in stormwater in photocatalytic reactor wet detention pond using nano titanium dioxide (TiO2) in concrete was investigated in a scale model as a new stormwater treatment method. Degradation of phosphate and nitrate in the presence of nano-TiO2 under natural ultra violet (UV) from tropical sunlight was monitored for 3 weeks compared with normal ponds. Two types of cement, including ordinary Portland and white cement mixed with TiO2 nano powder, were used as a thin cover to surround the body of the pond. Experiments with and without the catalyst were carried out for comparison and control. Average Anatase diameter of 25 nm and Rutile 100 nm nano particles were applied at three different mixtures of 3, 10 and 30% weight. The amounts of algae available orthophosphate and nitrate, which cause eutrophication in the ponds, were measured during the tests. Results revealed that the utilization of 3% up to 30% weight nano-TiO2 can improve stormwater outflow quality by up to 25% after 48 h and 57% after 3 weeks compared with the control sample in normal conditions with average nutrient (phosphate and nitrate) removal of 4% after 48 h and 10% after 3 weeks.
Use of cheap, N-rich, and environmentally benign legume green manures to correct N deficiency in infertile soils is a very attractive option in the humid tropics. Understanding the influence of management and climate on their effectiveness, and quantifying their contribution to crop productivity, is therefore crucial for technology adoption and adaptation. Mineral N buildup and the contribution to N uptake in maize were studied in an Ultisol amended with fresh Gliricidia leaves. Net mineral N accumulation was compared in mulched and incorporated treatments in a field incubation study. The 15 N isotope dilution technique was used to quantify N supplied to maize by Gliricidia leaves in an alley cropping. Mineral N accumulation was slow, but was much greater after incorporation than after mulching. Also, N buildup was always higher in the topsoil (0 to 10 cm) than in the subsoil (10 to 20 cm). More NO3-N was leached than NH4-N, and the effect was greater in the incorporated treatment. Surface-applied Gliricidia leaves significantly increased N uptake by maize, and supplied >30% of the total N in the stover and >20% of that in the corn grain, even in the presence of hedgerows. Thus Gliricidia leaf mulch has immense potential to improve productivity in tropical soils.
The sewer is an integral part of the urban wastewater system: the sewer, the wastewater treatment plant and the local receiving waters. The sewer is a reactor for microbial changes of the wastewater during transport, affecting the quality of the wastewater and thereby the successive treatment processes or receiving water impacts during combined sewer overflows. This paper presents the results of studies on anoxic processes, namely denitrification, in the bulk water phase of wastewater as it occurs in sewers. Experiments conducted on 12 different wastewater samples have shown that the denitrification process in the bulk wastewater can be simplified by the reduction of nitrate to nitrogen with significant accumulation of nitrite in the water phase. Utilization of nitrate was observed not to be limited by nitrate for concentrations above 5 gNO3-N/m3. The denitrification rates, under conditions of excess substrate and electron acceptor, were found to be in the range of 0.8-2.0 g NO3-N/(m3h). A discussion on the interaction of the sewer processes and the effects on a downstream located wastewater treatment plant (WWTP) is provided.
Co-application of biochar and biosolids to soil has potential to mitigate N leaching due to physical and chemical properties of biochar. Changes in N cycling pathways in soil induced by co-application of biological amendments could further mitigate N loss, but this is largely unexplored. The aim of this study was to determine whether co-application of a biochar and a modified biosolids product to three pasture soils differing in texture could alter the relative abundance of N cycling genes in soil sown with subterranean clover. The biosolids product contained lime and clay and increased subterranean clover shoot biomass in parallel with increases in soil pH and soil nitrate. Its co-application with biochar similarly increased plant growth and soil pH with a marked reduction in nitrate in two coarse textured soils but not in a clayey soil. While application of the biosolids product altered in silico predicted N cycling functional genes, there was no additional change when applied to soil in combination with biochar. This supports the conclusion that co-application of the biochar and biosolids product used here has potential to mitigate loss of N in coarse textured soils due to N adsoption by the biochar and independently of microbial N pathways.