Mechanism of Microbial Degradation of Slow-Release Fertilizers

Methyleneureas are condensation products of urea and formaldehyde of different molecular mass and solubility; they are used in large amounts both as resins, binders, and insulating materials for industrial applications, as well as a slow-release nitrogen fertilizer for greens, lawns, or in bioremediation processes. In the present study, the microbial breakdown of these products was investigated. The nitrogen was released as ammonia and urea, and the formaldehyde released immediately oxidized via formiate to carbon dioxide. The enzymatic mechanism of metabolization of methyleneureas was studied in microorganisms isolated from soil, which were able to use these compounds as the sole source of nitrogen for growth. A strain of the Gram-negative bacterium Ralstonia paucula (formerly Alcaligenes sp. CDC group IVc-2) completely degraded methylenediurea and dimethylenetriurea to urea, ammonia, formaldehyde, and carbon dioxide. The enzyme initiating this degradation (methylenediurease) was purified and turned out to be different from the previously described enzyme from Ochrobactrum anthropi with regard to its regulation of expression and physicobiochemical properties. Fungal degradation of methyleneureas may occur via the formation of organic acids, thus leading to a nonenzymatic degradation of methyleneureas, which are unstable under acidic conditions.     

Metal mobilization from municipal solid waste incineration bottom ash through metal complexation with organic and inorganic ligands

As a first step in the development of ligand-assisted removal of heavy metals from municipal solid waste incineration bottom ash under alkaline conditions, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, urea, and mixtures of ammonium salts and urea were examined to find which ligands could promote the leachability of elements, including heavy metals, and which elements could be mobilized through complexation. Ammonium citrate promoted the mobilization of Cr, Cu, Mn, P, Sb, and especially Fe. Ammonium nitrate accelerated Mg leachability significantly. Under the conditions used in this study, counter anions seemed to contribute mainly to the complexation. When a mixture of ammonium citrate and urea was utilized, a coexistence effect appeared on Fe mobilization. Although the correlation analysis of leaching test results showed a strong correlation among Cr, Cu, Fe, Mn, and P, X-ray diffraction analysis partially supported the correlation between Fe and Mn only.     

A chemox treatment for urea‐ and ammonium‐contaminated groundwater

In a pilot project performed at a fertilizer manufacturing facility, a one‐step chemical oxidation technique successfully treated urea‐ and ammonium‐contaminated groundwater. The oxidation reaction occurred in an 1,100‐gallon batch reactor. The contaminated inflow was buffered by the metered addition of sodium bicarbonate solution and subsequently treated with sodium hypochlorite in an 8:1 weight ratio of Cl₂:N. In an instantaneous reaction, the urea and ammo‐nium‐N were completely oxidized to nitrogen gas that was vented to the atmosphere during mixing. The pH of the reactor discharge was ?6.5. Sodium sulfite was used to reduce residual hypochlorite in the reactor effluent to chloride to provide process water with characteristics suitable for discharge. Oxidation rates were similar with different strengths of hypochlorite; however, a 5 to 6 percent sodium hypochlorite (as Cl₂) solution was the most stable. © 2005 Wiley Periodicals, Inc.     

Transformations of nitrogen at the interface between the topsoil and an impervious clay subsoil

Much work has been done on gaseous emissions and leaching of nitrogenous compounds from whole soil profiles and also from soil surface measurements which are assumed to be mainly due to topsoil activity. In soils with an impervious clay subsoil, the boundary between the topsoil and subsoil may provide an interface for microbial activity, including N transformations. In this study, we investigated movement and transformations of two reactive N species (nitrate and urea) at the subsoil interface using a series of replicate, intact soil blocks, under two contrasting watering regimes. We measured fluxes in both liquid and gaseous phases and demonstrated that nitrate reaching the subsoil interface does not necessarily leach into water systems, but may denitrify immediately and could, therefore, add to atmospheric pollution through N₂O production. On the other hand, ammonium reaching the subsoil interface either directly, or after mineralization, appears to be more mobile than expected and has the potential to pollute watercourses.     

Transformations of nitrogen at the interface between the topsoil and an impervious clay subsoil

Much work has been done on gaseous emissions and leaching of nitrogenous compounds from whole soil profiles and also from soil surface measurements which are assumed to be mainly due to topsoil activity. In soils with an impervious clay subsoil, the boundary between the topsoil and subsoil may provide an interface for microbial activity, including N transformations. In this study, we investigated movement and transformations of two reactive N species (nitrate and urea) at the subsoil interface using a series of replicate, intact soil blocks, under two contrasting watering regimes. We measured fluxes in both liquid and gaseous phases and demonstrated that nitrate reaching the subsoil interface does not necessarily leach into water systems, but may denitrify immediately and could, therefore, add to atmospheric pollution through N₂O production. On the other hand, ammonium reaching the subsoil interface either directly, or after mineralization, appears to be more mobile than expected and has the potential to pollute watercourses.     

Two-stage Sequential Electrochemical Treatment of Nitrate Brine Wastes

Nitrates in concentrated brines can be electrochemically reduced in the cathodic chamber of a split-cell electrochemical reactor with formation of ammonium (and small amounts of nitrite). Fortunately, ammonium may be electrochemically oxidized to nitrogen gas in the anodic reaction chamber if a coupled sequential process is used. The presence of chloride in the brine waste is an important consideration in oxidative electrochemical processes, however, because it cycles through oxidized and reduced states at the electrode surfaces and in the bulk solution. Electrochemical oxidation converts chloride ions to “active chlorine” species with additional oxidizing capability (chlorine, hypochlorous acid and hypochlorite – essentially bleach), as well as to chlorates, depending on the reaction conditions. The production of these active species improves treatment performance in the ammonium oxidation phase since oxidation is no longer limited to the electrode surface. However, the process must be engineered to minimize loss of process efficiency due to parasitic side reactions (chloramines and chlorate). In this study, two-stage batch electrolysis was conducted using a three-electrode (copper anode, platinum-coated titanium cathode, silver/silver chloride reference) electrochemical cell, with the anodic and cathodic chambers separated by a Nafion 117 membrane. Treatment of nitrate and ammonium was tested with and without the presence of chloride in the waste. No significant difference was observed in cathodic nitrate reduction with chloride present or absent. However, the presence of chloride in the solution favored overall soluble nitrogen elimination upon oxidation. Increasing applied current increased production of undesirable byproducts (especially chlorate).     

Influence of Some Chelators on the Phytoextraction Ability of Sunflower (Helianthus annuus) for Nickel‐Contaminated Soil

Chelation and complexation of nickel were evaluated as practical ways to solubilize, detoxify, and enhance nickel accumulation by plants. Sunflower (Helianthus annuus) was selected as a potential nickel accumulator in two selected soils with different textures and nickel‐contamination levels. To enhance metal phytoextraction, ammonium nitrate and organic chelators (EDTA and citric acid) were added to soils in pots at rates of 0, 5, 10, and 20 mmol/kg. The pot experiments were run for eight weeks. The highest nickel uptake was obtained in plants grown on clayey soil, and the lowest uptake was observed in sandy soil. Citric acid was the most effective chelator of nickel metals that could enhance nickel accumulation in the sunflower shoots. The ammonium nitrate application showed a low effect on metal translocation into the sunflower shoots. © 2014 Wiley Periodicals, Inc.     

Nitrate Remediation: The Importance of the Advanced Nitrogen Cycle in Remedy Selection

Nitrate has become an increased regulatory concern due to gradual deterioration of surface and groundwater quality primarily related to widespread fertilizer use. Remediation of nitrate is a relatively straightforward process; however, nitrate impacts to groundwater are often a symptom of a sustained source from another nitrogen form (e.g., ammonia, ammonium nitrate, urea), analogous to how nonaqueous phase liquid can serve as a long‐term source of volatile organic compounds in groundwater. Understanding the various nitrogen transformation reactions when selecting, implementing, or documenting a remedy associated with nitrate is therefore critical to successfully reaching remedial endpoints. Case studies are presented that highlight in situ remedial successes with nitrogen‐impacted groundwater and discuss the key considerations that should be factored into remedy application. ©2015 Wiley Periodicals, Inc.     

Impact of Cathode Conditions on Coupled Electrochemical Treatment of Nitrate Brine Concentrates

Simulated concentrated nitrate brine waste was treated in a two-stage electrolysis process, where reduction of nitrate in a cathodic chamber was coupled with oxidation of ammonium (produced in the previous stage) in an anodic chamber. The influence of operating conditions such as applied potential, electrolyte composition, and initial concentration on conversion of nitrate to ammonium in the cathodic chamber was investigated. The effects of chloride and current density on the two-stage treatment process were also examined. More negative potential at the cathode (?2.0 vs. ?1.7 and ?1.5 V) and higher current density (33 vs. 22 and 13.9 mA/cm²) favored ammonium as the product of nitrate reduction at a copper cathode and increased the overall amount of nitrate conversion. Faster reduction was seen when nitrate concentration was lower (0.01 vs. 0.02 N), but total mass conversion of nitrate in the same time period was higher for 0.02 N. The reduction of nitrate was not sensitive to sulfate or chloride concentration in the ranges studied (0–2 and 1–1.5 mg/L, respectively), but the oxidation of ammonium was noticeably higher when chloride was present. Only small amounts of ammonium and nitrate remained in the second-stage effluent after coupled treatment.     

Nitrogen mineralization and nitrate leaching of a sandy soil amended with different organic wastes.

Organic wastes can be recycled as a source of plant nutrients, enhancing crop production by improving soil quality. However, the study of the dynamic of soil nutrient, especially the N dynamic, after soil application of any organic material is vital for assessing a correct and effective use of the material, minimizing the losses of nitrate in leachates and avoiding the negative environmental effects that it may cause in groundwater. To estimate the effect of three organic materials, a municipal solid waste compost (MWC), a non-composted paper mill sludge (PS), and an agroforest compost (AC) on the N dynamic of a sandy soil two experiments were carried out: an incubation experiment and a column experiment. The incubation experiment was conducted to estimate the N mineralization rate of the different soil-amendment mixtures. The soil was mixed with the organic amendments at a rate equivalent to 50,000 kg ha(-1) and incubated during 40 weeks at constant moisture content (70% of its water-holding capacity) and temperature (28 degrees C) under aerobic conditions. Organic amendment-soil samples showed an immobilization of N during the first weeks, which was more noticeable and longer in the case of PS-treated soil compared to the other two amendments due to its high C/N ratio. After this immobilization stage, a positive mineralization was observed for all treatment, especially in MWC treated soil. Contemporaneously a 1-year column (19 cm diameter and 60 cm height) experiment was carried out to estimate the nitrate losses from the soil amended with the same organic materials. Amendments were mixed with the top soil (0-15 cm) at a rate equivalent to 50,000 kg ha(-1). The columns were periodically irrigated simulating rainfall in the area of study, receiving in total 415 mm of water, and the water draining was collected during the experimental period and analysed for NO3-N. At the end of the experimental period NO3-N content in soil columns at three depths (0-20, 20-35 and 35-50 cm) was determined. The nitrate concentration in drainage water confirmed the results obtained in the incubation experiment: nitrate leaching was higher in soil treated with MWC due to its higher N-mineralization rate. Nevertheless, the nitrate losses represented a low amount compared with the total nitrogen added to soil. No clear signs of water-draining contamination were observed during the first year after the application of AC and PS; however, the nitrate leaching in soil treated with MWC slightly exceeded the limit allowed for the Drinking Water Directive 98/83/CE.     

The GANE Roof Project: The impact of reduced N & S deposition and experimental warming in an acid grassland

A field-based system used to quantify the response of acid grassland to reduced atmospheric nitrogen and sulphur deposition, and to investigate the effects of elevated soil temperature on acid grassland development is described. The system is based on 12 retractable roofs, covering undisturbed experimental plots of acid grassland and three controls. Nine roofs are used to exclude natural precipitation and three roofs used to retain emitted IR radiation at night. An irrigation system has been developed to simulate natural precipitation, allowing for the application of specific treatment regimes of ambient, reduced nitrogen and reduced nitrogen/sulphur deposition beneath the nine rain exclusion plots. Plant, soil parameters, leachate chemistry and gaseous fluxes are being monitored and initial results on soil water chemistry are described. Warming appeared to enhance nitrate concentrations in soil water but this was not sustained beyond the first year of treatment. In contrast, the deposition reduction treatments decreased soil water nitrate concentrations within a few weeks of reducing deposition. This was not observed for other solutes such as sulphate or ammonium suggesting a more direct link between deposition of nitrate and leaching losses.     

The GANE Roof Project: The impact of reduced N & S deposition and experimental warming in an acid grassland

A field-based system used to quantify the response of acid grassland to reduced atmospheric nitrogen and sulphur deposition, and to investigate the effects of elevated soil temperature on acid grassland development is described. The system is based on 12 retractable roofs, covering undisturbed experimental plots of acid grassland and three controls. Nine roofs are used to exclude natural precipitation and three roofs used to retain emitted IR radiation at night. An irrigation system has been developed to simulate natural precipitation, allowing for the application of specific treatment regimes of ambient, reduced nitrogen and reduced nitrogen/sulphur deposition beneath the nine rain exclusion plots. Plant, soil parameters, leachate chemistry and gaseous fluxes are being monitored and initial results on soil water chemistry are described. Warming appeared to enhance nitrate concentrations in soil water but this was not sustained beyond the first year of treatment. In contrast, the deposition reduction treatments decreased soil water nitrate concentrations within a few weeks of reducing deposition. This was not observed for other solutes such as sulphate or ammonium suggesting a more direct link between deposition of nitrate and leaching losses.     

Microbial nitrogen transformation potential in surface run-off leachate from a tropical landfill

Ammonium is one of the major toxic compounds and a critical long-term pollutant in landfill leachate. Leachate from the Jatibarang landfill in Semarang, Indonesia, contains ammonium in concentrations ranging from 376 to 929 mg N L⁻¹. The objective of this study was to determine seasonal variation in the potential for organic nitrogen ammonification, aerobic nitrification, anaerobic nitrate reduction and anaerobic ammonium oxidation (anammox) at this landfilling site. Seasonal samples from leachate collection treatment ponds were used as an inoculum to feed synthetic media to determine potential rates of nitrogen transformations. Aerobic ammonium oxidation potential (<0.06 mg N L⁻¹ h⁻¹) was more than a hundred times lower than the anaerobic nitrogen transformation processes and organic nitrogen ammonification, which were of the same order of magnitude. Anaerobic nitrate oxidation did not proceed beyond nitrite; isolates grown with nitrate as electron acceptor did not degrade nitrite further. Effects of season were only observed for aerobic nitrification and anammox, and were relatively minor: rates were up to three times higher in the dry season. To completely remove the excess ammonium from the leachate, we propose a two-stage treatment system to be implemented. Aeration in the first leachate pond would strongly contribute to aerobic ammonium oxidation to nitrate by providing the currently missing oxygen in the anaerobic leachate and allowing for the growth of ammonium oxidisers. In the second pond the remaining ammonium and produced nitrate can be converted by a combination of nitrate reduction to nitrite and anammox. Such optimization of microbial nitrogen transformations can contribute to alleviating the ammonium discharge to surface water draining the landfill.     

Release Characteristics of Nutrients from Polymer-coated Compound Controlled Release Fertilizers

Reliable information regarding release characteristics of nutrients from a polymer-coated controlled release fertilizer (CRF) is essential for beneficial agronomic and environmental results. Significant knowledge regarding nitrogen release from polymer-coated urea was gained while the information regarding the release of the different nutrients contained in polymer-coated compound N–P–K CRF remains limited. An experiment in which major factors affecting the differential release of nutrients from two coated compound CRF was performed in free water, water saturated sand and sand at field capacity. In general, nitrate release was the fastest, followed by ammonium and potassium whereas phosphate was significantly slower, with a rate of linear release in free water 45–70% slower than that of nitrate. Little differences were obtained for the lag periods of nitrate, ammonium and potassium release (2–10 days) under the experimental conditions, whereas for P they were one order of magnitude larger. The main factor slowing the release was assumed to be the lower solubility of ions with P being the least soluble. Release into free water was, expectedly, somewhat faster than that into saturated sand and significantly faster as compared to sand at field capacity and particularly so for P. Raising the temperature from 20 °C to 40 °C increased the rate of linear release of the different nutrients. The energy of activation, EA_rel, estimated for the linear release, of the different nutrients, was narrow ranging between 37 to 46 (KJ mol⁻¹) whereas the mean values obtained for the two CRF, differing by 50% in coating thickness, was non-significant. However, EA_rel was significantly different in different media. The complex effect of temperature on the lag period and nutrient interactions during release deserve further investigation.     

Vegetative remediation process offers advantages over traditional pump-and-treat technologies

The use of bioremediation technologies to clean up contaminated soil and groundwater is increasingly winning favor over more costly and often ineffective mechanical approaches. One new type of bioremediation process, known as TreeMediation^TM, uses trees and other vegetation to remediate soil by acting as a natural pump to extract and remediate contaminated groundwater in aquifers less than 30 feet deep. This article describes this innovative treatment method, shows its advantages over traditional pump and-treat techniques, and explains how TreeMediation is being used to extract nitrate and ammonium contamination from an aquifer in New Jersey.     

Accumulation of pollutant nitrogen in calcareous and acidic grasslands: Evidence from N flux and 15N tracer studies

Semi-natural calcareous and acidic grasslands are known to be sensitive to increased atmospheric N deposition. However, the fate of pollutant N within these systems is unknown. This paper reports on the first studies to determine the fate of added N within a calcareous and an acidic grassland subject to long-term simulated enhanced N deposition. Intact soil/turf cores were removed from field plots treated for six years with enhanced N deposition (ambient +0, +35 and +140 kg N ha^?1 year^?1). Cores were inserted into lysimeters and output fluxes of N were monitored in detail. Complete N budgets—calculated from the N flux data—showed considerable accumulation of N within the treated grasslands, up to 76% and 38% of pollutant N in the calcareous and acidic grasslands respectively. In the second study, the short-term (21 day) fate of pollutant N was determined by tracing ¹⁵N labelled ammonium nitrate (+35 kg N ha^?1 year^?1) though the acidic and calcareous lysimeters into plant, soil and leachate pools. Up to 91% and 59% of ¹⁵N was recovered in soils and vegetation of the calcareous and acidic grasslands respectively, with negligible amounts recovered in soil extractable ammonium and nitrate (<0.3%) and in leachate (<0.02%). This rapid short-term immobilisation of pollutant N supports the long-term accumulation of the element calculated from the N flux study.     

Accumulation of pollutant nitrogen in calcareous and acidic grasslands: Evidence from N flux and 15N tracer studies

Semi-natural calcareous and acidic grasslands are known to be sensitive to increased atmospheric N deposition. However, the fate of pollutant N within these systems is unknown. This paper reports on the first studies to determine the fate of added N within a calcareous and an acidic grassland subject to long-term simulated enhanced N deposition. Intact soil/turf cores were removed from field plots treated for six years with enhanced N deposition (ambient +0, +35 and +140 kg N ha^–1 year^–1). Cores were inserted into lysimeters and output fluxes of N were monitored in detail. Complete N budgets—calculated from the N flux data—showed considerable accumulation of N within the treated grasslands, up to 76% and 38% of pollutant N in the calcareous and acidic grasslands respectively. In the second study, the short-term (21 day) fate of pollutant N was determined by tracing ¹⁵N labelled ammonium nitrate (+35 kg N ha^–1 year^–1) though the acidic and calcareous lysimeters into plant, soil and leachate pools. Up to 91% and 59% of ¹⁵N was recovered in soils and vegetation of the calcareous and acidic grasslands respectively, with negligible amounts recovered in soil extractable ammonium and nitrate (<0.3%) and in leachate (<0.02%). This rapid short-term immobilisation of pollutant N supports the long-term accumulation of the element calculated from the N flux study.     

Nitrate and nitrite injection during municipal solid waste anaerobic biodegradation

Nitrified leachate recirculation has been proposed as a promising strategy for sustainable landfill management. In four test reactors, nitrate or nitrite was added (250 mg N-NO(x)(-)L(-1)) during municipal solid waste biodegradation. Nitrogen-oxides reduction reactions were monitored. Denitrification was the main nitrogen reducing reaction observed. On one hand, during the acidogenic waste degradation phase, as high amounts of volatile fatty acids (VFA) were present, nitrogen-oxides reductions were interpreted as heterotrophic denitrifications. On the other hand, denitrification reactions occurring during the late methanogenic phase were accompanied by sulphate productions and, as VFA were not detected, it was probably an autotrophic reaction. Denitrification inhibition was observed once. Ammonium concentration increased suggesting the occurrence of a dissimilatory nitrate reduction to ammonium (DNRA). Statistical treatment of analytical data revealed that only H(2)S concentration had a significant negative effect on N(2) production in our system. NO production was observed once when nitrite was injected during the acidogenic phase resulting in a total waste degradation inhibition. These results indicate that the consequences of nitrified leachate recirculation in full-scale landfills need to be carefully examined especially during the acidogenic phase or in the presence of waste containing high quantities of sulphur.     

Winter and Spring Thaw Measurements of N2O,NO and NOx Fluxes using a Micrometeorological Method

The impact of nitrogen fertilizers on gaseous emissions duringwinter and spring-thaw is not well understood and was the objective of this research. Using a micrometeorological method,N₂O, NO and NO_x fluxes from ryegrass were measured from November 1997 to March 1998. Three different mineralfertilizers were applied in November: urea (U), slow-release urea(SRU) and ammonium nitrate (AN). N₂O emissions during the winter were small, increasing significantly in March. Total losses of N₂O-N were significantly higher from SRU and U plots, with winter N₂O emissions accounting for 50% of annual losses. Nitric oxide fluxes from all plots weresmall during the measurement period (<0.9 ng N m^-2 s^-1). The NO fluxes from U and AN fertilized plots were significantly higher than from SRU and control plots. NO₂ fluxes were always negative (–6 ng N m^-2 s^-1)indicating deposition, but decreased to –2 ng N m^-2s^-1 when snow was present on the soil surface. Our resultsindicate that the form of inorganic N applied has an effect on NO+ N₂O emissions but not on NO₂ fluxes.Sponsored by CAPES – Brasília, Brazil     

Evaluation of Solvita compost stability and maturity tests for assessment of quality of end-products from mixed latrine style compost toilets

It is challenging and expensive to monitor and test decentralized composting toilet systems, yet critical to prevent the mismanagement of potentially harmful and pathogenic end-product. Recent studies indicate that mixed latrine composting toilets can be inhibited by high ammonia content, a product of urea hydrolysis. Urine-diverting vermicomposting toilets are better able to accomplish the goals of remote site human waste management by facilitating the consumption of fecal matter by earthworms, which are highly sensitive to ammonia. The reliability of Solvita® compost stability and maturity tests were evaluated as a means of determining feedstock suitability for vermicomposting (ammonia) and end-product stability/completeness (carbon dioxide). A significant linear regression between Solvita® ammonia and free ammonia gas was found. Solvita® ranking of maturity did not correspond to ranking assigned by ammonium:nitrate standards. Solvita® ammonia values 4 and 5 contained ammonia levels below earthworm toxicity limits in 80% and 100% of samples respectively indicative of their use in evaluating feedstock suitability for vermicomposting. Solvita® stability tests did not correlate with carbon dioxide evolution tests nor ranking of stability by the same test, presumably due to in situ inhibition of decomposition and microbial respiration by ammonia which were reported by the Solvita® CO₂ test as having high stability values.