Simultaneous determination of dissolved organic nitrogen, nitrite, nitrate and ammonia using size exclusion chromatography coupled with nitrogen detector

Accurate quantification of dissolved organic nitrogen (DON) has been a challenge due to the cumulative analytical errors in the conventional method via subtracting dissolved inorganic nitrogen species (DIN) from total dissolved nitrogen (TDN). Size exclusion chromatography coupled with an organic nitrogen detector (SEC-OND) has been developed as a direct method for quantification and characterization of DON. However, the applications of SEC-OND method still subject to poor separations between DON and DIN species and unsatisfied N recoveries of macromolecules. In this study, we packed a series of SEC columns with different lengths and resin materials for separation of different N species and designed an independent vacuum ultraviolet (VUV) oxidation device for complete oxidation converting N species to nitrate. To guarantee sufficient N recoveries, the operation conditions were optimized as oxidation time ≥ 30 min, injection mass (sample concentration × injection volume) < 1000 µL × mg-N/L for macromolecular proteins, and neutral pH mobile eluent. The dissolved O₂ concentration in SEC mobile phase determined the upper limit of VUV oxidation at a specific oxidation time. Compared to conventional HW50S column (20 × 250 mm), HW40S column (20 × 350 mm) with mobile phase comprising of 1.5 g/L Na₂HPO₄·2H₂O + 2.5 g/L KH₂PO₄ (pH = 6.85) could achieve a better separation of DON, nitrite, nitrate, and ammonia. When applied to river water, lake water, wastewater effluent, groundwater, and landfill leachate, the SEC-OND method could quantify DON as well as DIN species accurately and conveniently even the DIN/TDN ratio reached 0.98.     

电极流动分析仪的研制和应用

采用固定电极测试状态的方法，将流动技术引入到离子电极直接电位分析法中，设计并试制了电极流动分析仪。配用市售硝酸根电极、钠电极、氟电极、氯电极和氨电极进行了环境样品的测定。结果表明，电极流动分析仪法的分析速度比直接电位法提高２－３倍，变异系数，２．９％－５．０％之间，回收率在９０％－１０５％之间；直接电位法变异系数在２．３％－６．７％之间，加收率在９０％－１０９％之间。     

Differential N uptake by maize cultivars and soil nitrate dynamics under N fertilization in West Africa

Nitrate is prone to leaching in the sandy soils of the West African moist savannas. Better management of nitrogen (N) resources and maize cultivars with enhanced genetic capacity to capture and utilize soil and fertilizer N are strategies that could improve N-use efficiency. In two field experiments conducted at Zaria, northern Nigeria, five maize (Zea mays L.) cultivars planted early in the season were assessed under various N levels for differences in N uptake, soil N dynamics, and related N losses. Cultivar TZB-SR accumulated more N in the aboveground plant parts in both years than the other cultivars. All, except the semi-prolific late (SPL) variety, met about 50–60% of their N demand by the time of silking (64–69 DAP). In both years, SPL had the greatest capacity to take up N during the grain filling period, and it had the highest grain-N concentration and the least apparent N loss through leaching in the second year. There were no significant differences in soil N dynamics among cultivars in both years. At harvest, the residual N in the upper 90 cm of the profile under all the cultivars ranged from 56 to 72 kg ha⁻¹ in the first year and from 73 to 83 kg ha⁻¹ in the second year. Apparent N loss from 0 to 90 cm soil profile through leaching ranged from 35 to 122 kg ha⁻¹ in both years. N application significantly increased N uptake by more than 30% at all sampling dates in the second year of the experiment, but had no effect on apparent N loss. Results indicate that the use of maize cultivars with high N uptake capacity during the grain filling period when maximum leaching losses occur could enhance N recovery and may be effective in reducing leaching losses of mineral N in the moist savanna soils.     

Catalytic reduction for water treatment

Treating water contaminants via heterogeneously catalyzed reduction reaction is a subject of growing interest due to its good activity and superior selectivity compared to conventional technology, yielding products that are non-toxic or substantially less toxic. This article reviews the application of catalytic reduction as a progressive approach to treat different types of contaminants in water, which covers hydrodehalogenation for wastewater treatment and hydrogenation of nitrate/nitrite for groundwater remediation. For hydrodehalogenation, an overview of the existing treatment technologies is provided with an assessment of the advantages of catalytic reduction over the conventional methodologies. Catalyst design for feasible catalytic reactions is considered with a critical analysis of the pertinent literature. For hydrogenation, hydrogenation of nitrate/nitrite contaminants in water is mainly focused. Several important nitrate reduction catalysts are discussed relating to their preparation method and catalytic performance. In addition, novel approach of catalytic reduction using in situ synthesized H₂ evolved from water splitting reaction is illustrated. Finally, the challenges and perspective for the extensive application of catalytic reduction technology in water treatment are discussed. This review provides key information to our community to apply catalytic reduction approach for water treatment.

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Nitrate removal and extracellular polymeric substances of autohydrogenotrophic bacteria under various pH and hydrogen flow rates

In recent years there has been an increasing interest in the use of autohydrogenotrophic bacteria to treat nitrate from wastewater. However, our knowledge about the characteristics of extracellular polymeric substances (EPS) releasing by these activities is not yet very advanced. This study aimed to investigate the change in EPS compositions under various pH values and hydrogen flow rates, taking into consideration nitrogen removal. Results showed that pH 7.5 and a hydrogen flow rate of 90 mL/min were the optimal operating conditions, resulting in 100% nitrogen removal after 6 hr of operation. Soluble and bound polysaccharides decreased, while bound proteins increased with increasing pH. Polysaccharides increased with increasing hydrogen flow rate. No significant change of bound proteins was observed at various hydrogen flow rates.     

Spatial and temporal variations in groundwater nitrate at an intensive dairy farm in south-east Ireland: Insights from stable isotope data

Achievement of at least “good ecological status” in all waterbodies under the EU Water Framework Directive by 2015 will in some cases be a challenge. The twin challenge is to manage expectations of policy makers for such waterbodies as to a realistic length of time required for improvement in water quality. Hence, understanding the source, transformation processes and residence time of nitrate in a hydrological system is an essential part of meeting such challenges. On a dairy farm with 24 shallow groundwater wells, the dual isotopic composition of nitrate (δ¹⁵N and δ¹⁸O) was used to clarify nitrate sources, to assess spatial and temporal variability in nitrate concentrations and to determine if and where denitrification was occurring. Vertical travel time was estimated to correlate nitrate concentrations with management practices. Organically derived nitrogen was the predominant source contributing to groundwater nitrate concentrations. Denitrification was identified as prevalent within specific regions of the study site. The distinct low temporal variability in the isotopic data suggests constancy among nitrate sources and processes over time across the study site. Vertical travel times of up to 3 years were estimated on site indicating the influence of recent management practices on nitrate concentrations. Very slow horizontal migration of groundwater (decades) indicates a legacy of older management practices. Stable isotope techniques, together with an understanding of time lag, provide an extra mechanism to test the efficacy of monitoring and mitigation programmes.     

Quantification of nitrate leaching from German forest ecosystems by use of a process oriented biogeochemical model

Simulations with the process oriented Forest-DNDC model showed reasonable to good agreement with observations of soil water contents of different soil layers, annual amounts of seepage water and approximated rates of nitrate leaching at 79 sites across Germany. Following site evaluation, Forest-DNDC was coupled to a GIS to assess nitrate leaching from German forest ecosystems for the year 2000. At national scale leaching rates varied in a range of 0–>80 kg NO₃–N ha⁻¹ yr⁻¹ (mean 5.5 kg NO₃–N ha⁻¹ yr⁻¹). A comparison of regional simulations with the results of a nitrate inventory study for Bavaria showed that measured and simulated percentages for different nitrate leaching classes (0–5 kg N ha⁻¹ yr⁻¹:66% vs. 74%, 5–15 kg N ha⁻¹ yr⁻¹:20% vs. 20%, >15 kg N ha⁻¹ yr⁻¹:14% vs. 6%) were in good agreement. Mean nitrate concentrations in seepage water ranged between 0 and 23 mg NO₃–N l⁻¹.     

Olive oil mill wastewater for soil nitrogen and carbon conservation

In this work the application of two levels of N fertilizer (NH₄NO₃) dissolved in water or olive oil mill wastewater (OOMW) diluted 10 or 20 times in water, has been studied in relation to the properties of two soils (Loam and Silt-Clay-Loam). Also, the effect of irrigation water bubbled with CO₂ (Dissolved Inorganic Carbon, DIC) was studied. Nitrate N, ammonium N, total N, organic C (OC), and CaCO₃ contents were determined in the soil as well as pH, electrical conductivity (EC), oxidation–reduction potential (ORP), and absorbance at 250 and 360 nm.     

Characterizing sources of nitrate leaching from an irrigated dairy farm in Merced County, California

Dairy farms comprise a complex landscape of groundwater pollution sources. The objective of our work is to develop a method to quantify nitrate leaching to shallow groundwater from different management units at dairy farms. Total nitrate loads are determined by the sequential calibration of a sub-regional scale and a farm-scale three-dimensional groundwater flow and transport model using observations at different spatial scales. These observations include local measurements of groundwater heads and nitrate concentrations in an extensive monitoring well network, providing data at a scale of a few meters and measurements of discharge rates and nitrate concentrations in a tile-drain network, providing data integrated across multiple farms. The various measurement scales are different from the spatial scales of the calibration parameters, which are the recharge and nitrogen leaching rates from individual management units. The calibration procedure offers a conceptual framework for using field measurements at different spatial scales to estimate recharge N concentrations at the management unit scale. It provides a map of spatially varying dairy farming impact on groundwater nitrogen. The method is applied to a dairy farm located in a relatively vulnerable hydrogeologic region in California. Potential sources within the dairy farm are divided into three categories, representing different manure management units: animal exercise yards and feeding areas (corrals), liquid manure holding ponds, and manure irrigated forage fields. Estimated average nitrogen leaching is 872 kg/ha/year, 807 kg/ha/year and 486 kg/ha/year for corrals, ponds and fields respectively. Results are applied to evaluate the accuracy of nitrogen mass balances often used by regulatory agencies to assess groundwater impacts. Calibrated leaching rates compare favorably to field and farm scale nitrogen mass balances. These data and interpretations provide a basis for developing improved management strategies.     

Ammonium,Nitrate and Nitrite Nitrogen and Nitrate Reductase Enzyme Activity in Groundnut (Arachis hypogaea L.) Fields After Diazinon,Imidacloprid and Lindane Treatments

Impacts of diazinon (O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate), imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] and lindane (1,2,3,4,5.6-hexachlorocyclohexane) treatments on ammonium, nitrate, and nitrite nitrogen and nitrate reductase enzyme activities were determined in groundnut (Arachis hypogaea L.) field for three consecutive years (1997 to 1999). Diazinon was applied for both seed- and soil-treatments but imidacloprid and lindane were used for seed treatments only at recommended rates. Diazinon residues persisted for 60 days in both the cases. Average half-lives (t_1/2) of diazinon were found 29.3 and 34.8 days respectively in seed and soil treatments. In diazinon seed treatment, NH₄ ⁺, NO₃ ^?, and NO₂ ^? nitrogen and nitrate reductase activity were not affected. Whereas, diazinon soil treatment indicated significant increase in NH₄ ⁺-N in a 1-day sample, which continued until 90 days. Some declines in NO₃ ^?N were found from 15 to 60 days. Along with this decline, significant increases in NO₂ ^?N and nitrate reductase activity were found between 1 and 30 days. Imidacloprid and lindane persisted for 90 and 120 days with average half-lives (t_1/2) of 40.9 and 53.3 days, respectively. Within 90 days, imidacloprid residues lost by 73.17% to 82.49% while such losses for lindane residues were found 78.19% to 79.86 % within 120 days. In imidacloprid seed-treated field, stimulation of NO₃ ^?N and the decline in NH₄ ⁺NO₂ ^?-N and nitrate reductase enzyme activity were observed between 15 to 90 days. However, lindane seed treatment indicated significant increases in NH₄ ⁺-N, NO₂ ^?-N and nitrate reductase activity and some adverse effects on NO₃ ^?N between 15 and 90 days.