Determination of (Nitrate + Nitrite )‐N in alkaline permanganate solutions

Abstract

The quantitative reduction of nitrate in an acid medium with reduced Fe was applied to the alkaline permanganate solution used to absorb NO and NO₂ evolved from soils during denitrification reactions. The method involves addition of H₂SO₄ to acidify the solution and ensure oxidation of nitrite to nitrate, and treatment with reduced Fe at 100°C to reduce nitrate to ammonium. The solution is made alkaline with NaOH and ammonium determined by standard distillation procedures. It is simple and precise, and applicable to nitrogen isotope ratio analysis of NO and NO₂ evolved from soils.     

Rapid and Inexpensive Steam Distillation Method for Routine Analysis of Inorganic Nitrogen in Alkaline Calcareous Soils

Determination of inorganic nitrogen (N) in soil is important in making N fertilizer recommendations for crops. To find a rapid, reliable, and economical method for the estimation of inorganic N in alkaline calcareous soils of Pakistan, three steam distillation methods were compared using soils varying in ammonium (NH₄) and nitrate (NO₃) N contents and other physicochemical properties. In the standard method, the soil sample is shaken with 2 N potassium chloride (KCl) for 1 h, and the extract is then analyzed by steam distillation. In the other two methods, the soil sample is distilled directly with either 2 N KCl or distilled/deionized water. Based on the results of the present work, a method that involves steam distillation with only distilled/deionized water and that requires half the quantity of magnesium oxide (MgO) of the standard method has been proposed, as all the three methods yielded identical results for NH₄- and NO₃-N contents. Being economical, the proposed method for inorganic N estimation by direct distillation of soil with distilled/deionized water deserves consideration for adoption by soil-testing laboratories.     

Evaluation of methods for soil inorganic nitrogen analysis

Abstract

This study determined the effects of soil preservation methods on inorganic nitrogen (N) analysis and evaluated methods of soil inorganic N analysis. Soils were preserved by oven‐drying at 55'C, air‐drying at 27°C, and freezing at ‐ 7°C. Inorganic N results were compared with initial N levels prior to imposing preservation treatments. Soil preservation effects on ammonium‐nitrogen (NH₄ ⁺‐N) were not consistent across soil types. Soil nitrate‐nitrogen (NO₃ ^‐‐N) levels after air‐drying and freezing compared most favorably with initial levels indicating that both are acceptable methods of soil inorganic‐N preservation. Levels of NH₄ ⁺‐N averaged across soils were 3.9 mg/kg for steam distillation, 4.2 mg/kg for sodium salicylate‐hypochlorite, and 3.7 mg/kg for indophenol blue. When compared with steam distillation averaged across soils, NO₃ ^‐‐N for cadmium‐copper (Cd‐Cu) reduction was 4 mg/kg greater, followed by nitrate electrode at 3 mg/kg, and salicylic acid at 2 mg/kg. Recovery of added N ranged from 83.3 to 94.8% for the NH4+‐N methods and from 74.8 to 112.4% for the NO₃ ^‐‐N methods with the nitrate electrode averaging 98.3%.     

Evaluation of methods for nitrogen‐15 analysis of inorganic nitrogen in soil extracts: I. Steam‐distillation methods

Abstract

A study was conducted to evaluate conventional steam‐distillation techniques for N‐isotope analysis of inorganic forms of N in soil extracts. Extracts obtained with 2 M KCl from 10 diverse soils were treated with: (i) (¹⁵NH₄)₂SO₄ and KNO₃, (ii) (NH₄)₂SO₄ and K¹⁵NO₃, or (iii) KNO₃and Na¹⁵NO₂. Steam distillations were performed sequentially to determine NH₄ ⁺‐N and NO₃ ^‐‐N, and were also carried out to determine (NO₃ ^‐ + NO₂ ^‐)‐N or (NH₄ ⁺ + NO₃ ^‐ + NO₂ ^‐)‐N; a pretreatment with sulfamic acid was used to determine NO₃ ^‐‐N in the presence of NO₂ ^‐‐N. Recovery of added N ranged from 95 to 102%. Significant isotopic contamination was observed in sequential distillation of unlabeled NO₃ ^‐‐N following labeled NH₄ ⁺‐N; otherwise, analyses for ¹⁵N were usually within 1% of the values calculated by isotope‐dilution equations.     

Soil nitrate and ammonium variation with area and date sampled

Abstract

Soil nitrate test reports are being used more widely for making nitrogen fertilizer recommendations. Seldom does the literature refer to the ammonium concentration in the soil. Seemingly, an assumption is made that the level is insignificant or a constant. Selected soils upon which both NO₃‐N and NH₄‐Nwere analyzed were surveyed to determine the degree of variation that is found in routine soil samples from different situations. Our 134 sets of data were divided into groups by area (state) and date (month sampled). Group means and standard deviations, medians, coefficient of variations (C.V.), and ranges were determined for soil nitrate nitrogen (NO₃‐N), ammonium‐nitrogen (NH4‐N), sum of NO₃‐N + NH₄‐N (Sum N), % of N found as NO₃‐N, and ratio of NH₄‐N/ NO₃‐N.

Values varied widely with date of sampling within areas as well as among areas. Observed values ranged as follows: NO₃‐N from 2 to 83 ppm, NH₄‐N from 4 to 30 ppm, sum of N from 9 to 91 ppm, % of N as NO₃‐N from 15 to 91% and NH₄‐N/NO₃‐N ratio from 0.1 to 5.5. C.V.’s ranged from 10 to 133% and were highest for NO₃‐N and NH₄‐N/NO₃‐N ratios and lowest for NH₄‐N and % NO₃‐N data.

The survey data suggests that nitrogen fertilizer recommendations could be improved if the NH₄‐N were considered along with the NO₃‐N levels for predicting response to nitrogen fertilization. A method for determining both soil NO₃‐N and NH₄‐N from a single extract is described.     

Growth,Nutrition, and Photosynthetic Response of Black Walnut to Varying Nitrogen Sources and Rates

ABSTRACT

Black walnut (Juglans nigra L.) half-sib 1+0 seedlings were exponentially fertilized with ammonium (NH₄ ⁺) as ammonium sulfate [(NH₄)₂SO₄], nitrate (NO₃ ^?) as sodium nitrate (NaNO₃), or a mixed nitrogen (N) source as ammonium nitrate (NH₄NO₃) at the rate of 0, 800, or 1600 mg N plant^?1 and grown for three months. One month following the final fertilization, N concentration, growth, and photosynthetic characteristics were assessed. Compared with unfertilized seedlings, N addition increased plant component N content, chlorophyll content, and photosynthetic gas exchange. Net photosynthesis ranged from 2.45 to 4.84 μmol m^?2 s^?1 for lower leaves but varied from 5.95 to 9.06 μmol m^?2 s^?1 for upper leaves. Plants responded more favorably to NH₄NO₃ than sole NH₄ ⁺ or NO₃ ^? fertilizers. These results suggest that N fertilization can be used to promote net photosynthesis as well as increase N storage in black walnut seedlings. The NH₄NO₃ appears to be the preferred N source to promote black walnut growth and physiology.     

Effect of nitrate addition on efficient use of ammonium sulfate fertilizer on corn under saline conditions. I. Pot experiment

Abstract

Plant growth in saline soils is regulated by the availability of nitrogen (N). High soil nitrate (NO₃)‐N can lead to poor water quality. Many workers think that NO₃‐N as a source for N can contribute to better plant growth in saline soils. The purpose of this work was to determine the necessity of NO₃‐N and the ratio of NO₃/ammonium (NH₄) in the N fertilizer which gives higher productivity of the biomass yield of corn. Corn (Zea mays L.) plants (Var. LG11) were grown under saline soil conditions (8.5 dS m^‐1), soils taken from the Euphrates valley (ACSAO Research Station) at Deir‐Ez‐Zor, east of Syria, from the surface layer of soil (0–25 cm). Five levels of N were applied in two forms, ammonium sulfate [¹⁵(NH₄)₂SO₄] with enrichment (1.5% a) as the NH₄‐N form and calcium nitrate [Ca(NO₃)₂] as the NO₃‐N form, besides fixed amounts of phosphorus (P) and potassium (K) for all N treatments. The corn plants were harvested at the flowering stage (56 days old), oven dried, weighed, and analyzed for total N and ¹⁵N recovery. The results indicated that the dry matter weight for treatments which received a combination of NH₄‐N and NO₃‐N gave higher dry matter yield than a single treatment of one source of N. But, NO₃‐N was more effective in improving yield than NH₄‐N. Nitrogen recoveries on the basis of added and absorbed N derived from fertilizer were significantly more affected by NO₃‐N than NH₄‐N.     

Nitrate‐nitrogen determination—a critical review

Abstract

This paper reviews the published methods of nitrate‐nitrogen (NO₃‐N) determination with the objective to assess their applicability to soil and plant tissue anarysis. The methods are separated into three categories on the basis of the analytical approach utilized for NO₃‐N determination. Strengths and weaknesses of the methods are discussed. The first analytical approach utilitizes direct measurement of NO₃‐N by the following methods: (a) colorimetric (after a color producing reaction with NO₃‐N), (b) potentiometric, (c) absorption of UV radiation by NO₃‐N in a complex matrix, (d) transnitration of salicylic acid, and (e) chromatographic (separation and measurement of NO₃‐N) methods. The second approach is based on the reduction of NO₃‐N to nitrite‐nitrogen (NO₂‐N), ammonium‐nitrogen (NH₄‐N), or nitric oxide and measurement of the reduction product. When NO₃‐N is reduced to NO₂‐N, the measurement may be achieved by (a) colorimetric, (b) fluorimetric, (c) coulometric, and (d) catalytic kinetic methods. When NO₃‐N is reduced to NH₄‐N, the measurement is done by (a) colorimetric (after a color producing reaction with NH₄), (b) potentiometric, (c) steam distillation, and (d) gas diffussion conductimetric methods. A chemiluminescence detection method is utilized when NO₃‐N is reduced to nitric oxide. The third approach determines NO₃‐N concentration by measuring the change in the concentration of the chemical species that react with NO₃‐N and form a complex.     

Use of diffusion for automated nttrogen‐15 analysis of soil extracts

Abstract

Studies to evaluate the use of diffusion for automated ¹⁵N analysis of inorganic N in soil extracts showed that serious error can arise from use of the Devarda's alloy recommended for steam distillations and that the error can be avoided by using a commercial product of higher purity. These studies showed that serious error can also arise when NO₃ ^‐‐N is diffused following NH₄ ⁺‐N and that separate diffusions should be performed for NH₄ ⁺‐N and (NH₄ ⁺ + NO₃‐)‐N. Other work demonstrated that the plastic specimen containers employed for diffusion can be reused if acid‐washed, that diffusions can be performed using either light or heavy MgO without ignition to decompose carbonate, and that labeled NO₂‐is completely removed from soil extracts by treatment with sulfamic acid before diffusion. A comparison of ¹⁵N analyses by steam distillation and diffusion using extracts from two soils revealed better agreement for the soil having a lower content of organic matter. Substantial differences in analyses by the two techniques for the soil having a higher organic‐matter content were attributed to enzymatic conversions of inorganic N during the 6‐d diffusion period.     

Colorimetric interference and recovery of adsorbed ions from ion exchange resins

Abstract

Analytical interference in the colorimetric determinations of ammonium and nitrate was examined in various KCl extracts of several ion exchange resins. No analytical interference was found in the colorimetric NO₃ ^‐‐N determination in any extract of any resin. However, a mixed‐bed (cation + anion) exchange resin extract substantially affected the colorimetric determination of NH₄ ^‐ ‐N. Recovery of adsorbed ammonium and nitrate from ion exchange resins was also studied as a function of KCl extractant strength and number of extractions. The recovery of adsorbed NO₃ ^‐‐N in the first extraction increased with increasing KCl concentration, with a 2 M solution recovering about 80%. However, a 1 M KCl solution gave the greatest recovery of ammonium‐N, recovering about 75–80% of the adsorbed ammonium. The second extraction with the same concentration of KCl solution was greater with the 0.5 and 2.0 M than with the 1 M solution so that total NH₄ ⁺‐N recovery after two extractions was about the same for all three KCl concentrations. The recovery of resin‐adsorbed NH₄ ⁺‐N and NO₃ ^‐‐N appeared independent of their concentrations on the resins.     

Comparison of chemical methods of assessing potentially available organic nitrogen in soil

Abstract

We recently developed two rapid and precise chemical methods of assessing potentially available organic N in soils. One method involves determination of the ammonia‐N produced by steam distillation of the soil sample with pH 11.2 phosphate‐borate buffer solution for 8 min. The other involves determination of the ammonium‐N produced by treatment of the soil sample with 2M KCl solution at 100°C for 4 hours. Studies using 33 Brazilian soils showed that the results obtained by these methods were highly correlated with those obtained by anaerobic and aerobic incubation methods of assessing potentially available organic N in soil.

The two methods were further evaluated by applying them to 30 Iowa soils and by comparing their results and those obtained by other chemical methods with the results of the incubation methods considered to be the best laboratory methods currently available for assessment of potentially available organic N in soil. The chemical methods used included the acid KMnO₄ method, the alkaline KMnO₄ method, the CaCl₂‐autoclave method, and the NaHCO₃ UV method. The incubation methods used involved determination of the ammonium‐N produced by incubation of the soil sample under anaerobic conditions for 1 week or determination of the (ammonium + nitrate + nitrite)‐N produced by incubation of the sample under aerobic conditions for 2 and 12 weeks. The data obtained showed that the results of the two chemical methods evaluated were highly correlated with those obtained by the incubation techniques used for comparison and that the correlations observed with these two methods were higher than those observed with the previously proposed chemical methods. It is concluded that these two rapid and simple methods are the best chemical methods thus far developed for laboratory assessment of potentially available organic N in soil.     

Tomato growth and mineral composition as influenced by nitrogen form and light intensity

Abstract

Tomato plants were grown in sand culture with NH⁺ ₄, and NO^? ₃, forms of N and three levels of light. Plants supplied with NH⁺ ₄, nutrition under high light intensity had symptoms of stunting, leaf roll, wilting, interveinal chlorosis of the older leaves, and one third the dry weight of N0₃‐fed plants. In contrast, growth of plants receiving NH⁺ ₄, nutrition under shade appeared normal although dry weight was reduced. NH₄‐N nutrition suppressed K, Ca and Mg accumulation in tissues and increased P contents as compared to NO₃‐N nutrition.     

Boron toxicity in kiwifruit plants (Actinidia deliciosa), treated with nitrate,ammonium, and a mixture of both

The objective of this research was to study the effects of nitrogen (N) forms (NO₃^–, 2.6 mM; NH₄⁺, 2.6 mM; NO₃^–, 1 mM + NH₄⁺, 1.6 mM) on the growth and mineral composition of kiwifruit plants exposed to three boron (B) levels (0.025, 0.1, 0.3 mM). The kiwifruit plants were grown in a 1:1 sand : perlite mixture and irrigated daily with nutrient solutions. Shoot height, mean shoot dry weight, the number of leaves, mean leaf dry weight, and N concentration of NH₄‐treated plants were significantly higher compared to the NO₃^– treatment at all B levels. The concentration of 0.3 mM B significantly reduced shoot height for all N treatments. Boron toxicity symptoms appeared 14 days after starting the experiment, when plants were treated with 0.1 and/or 0.3 mM B. The nitrate supply reduced the B concentration of roots, but B levels of different leaf parts were hardly affected by the N form. Furthermore, the NH₄‐N form significantly reduced the Mg concentration of the leaves.     

Available Nitrogen for Corn and Winter Cereal in Spanish Soils Measured by Electro‐ultrafiltration,Calcium Chloride,and Incubation Methods

Abstract

Comparison of methods is necessary to develop a quick and reliable test that can be used to determine soil‐available nitrogen (N) in an attempt to increase the efficiency of N fertilizers and reduce losses. The objectives of this research were to compare the fractions extracted by the calcium chloride (CaCl₂) and the electro‐ultrafiltration (EUF) methods and to correlate them to the mineralization rate (k) obtained from a 112‐d incubation of 61 soil samples. Thirty‐five soil samples were collected from cornfields and 26 from winter cereal fields. Subsamples were either aerobically incubated to calculate k or extracted by the EUF and CaCl₂ methods to identify three fractions: nitrate (NO₃ ^?)‐N, ammonium (NH₄ ⁺)‐N, and Norg‐N. The Norg‐N extracted by both methods was larger in soils from cornfields than in soils from winter cereal fields. In samples from cornfields, the Norg‐N fraction obtained by the EUF method was correlated to the Norg‐N measured by the CaCl₂ method (r=0.46). Soil N content was related to k in samples from cornfields (r=0.40) but not in samples from winter cereal fields. Also, k was correlated to inorganic N content extracted by both chemical methods. The CaCl₂ method was a reliable alternative for laboratories to determine soil‐available N for corn but not for winter cereal.     

Ammonium,nitrite, and nitrate nitrogen levels in the soil under blight‐affected and healthy citrus trees

Abstract

Ammonium, nitrite, and nitrate nitrogen levels in the root zone of blight‐affected and healthy trees in a 35‐year‐old commercial orange grove were monitored at 30‐day intervals for 2 years. There was essentially no difference in NH₄‐N and NO₂‐N; however, at four sampling dates and overall, the NO₃‐N level was slightly higher under healthy trees.     

Deep‐freezing pretreatment and time of extraction of soil samples for inorganic nitrogen determination

Abstract

Soil samples for inorganic nitrogen (N) determination are usually deep‐frozen to prevent microbial transformations of N between sampling and analysis. For analysis, frozen soils are thawed, which may also lead to transformations of N. A specially manufactured mill for grinding frozen soil was tested to minimize these transformations. Whether the time of extraction of the samples could be extended to 20 hr to better accomondate routine work and to make the clay aggregates to disperse better during extraction was also investigated. Freezing of the samples did not produce different results to fresh soils from ammonium nitrogen (NH₄ ⁺‐N) or nitrate nitrogen (NO₃ ^‐‐N) determination. Thawing of the samples increased the concentration of NO₃ ^‐‐N in the extracts and grinding increased that of NH₄ ⁺‐N. When either thawing or grinding was applied, the total inorganic nitrogen concentration was about the same. Thawing of the ground samples increased concentrations of NO₃’‐N and NH₄ ⁺‐N in the extracts. Extending the time of extraction from 0.5 or 1 hr to 20 hr increased the concentration of NH₄ ⁺‐N in the extracts, while NO₃ ^‐‐N content was also increased slightly. It was concluded that sample pretreatment may cause serious errors in the determination of inorganic N even by methods which have proven most successful to prevent microbial transformations of nitrogen, unless the soils are extracted immediately after sampling. The period of extraction should not exceed two hours.     

Development of a New Soil Extractant for Simultaneous Phosphorus,Ammonium, and Nitrate Analysis

Abstract

A new soil extractant (H³A) with the ability to extract NH₄, NO₃, and P from soil was developed and tested against 32 soils, which varied greatly in clay content, organic carbon (C), and soil pH. The extractant (H³A) eliminates the need for separate phosphorus (P) extractants for acid and calcareous soils and maintains the extract pH, on average, within one unit of the soil pH. The extractant is composed of organic root exudates, lithium citrate, and two synthetic chelators (DTPA, EDTA). The new soil extractant was tested against Mehlich 3, Olsen, and water for extractable P, and 1 M KCl and water‐extractable NH₄ and NO₂/NO₃. The pH of the extractant after adding soil, shaking, and filtration was measured for each soil sample (5 extractants×2 reps×32 soils=320 samples) and was shown to be highly influential on extractable P but has no effect on extractable NH₄ or NO₂/NO₃. H³A was highly correlated with soil‐extractable inorganic N (NH₄, NO₂/NO₃) from both water (r=0.98) and 1 M KCl (r=0.97), as well as being significantly correlated with water (r=0.71), Mehlich 3 (r=0.83), and Olsen (r=0.84) for extractable P.     

Growth and Accumulation of Nitrogen and Potassium in Flue‐Cured Tobacco as Affected by Calcium Nitrate and Ammonium Nitrate

The process of biomass, nitrogen (N), and potassium (K) accumulation over time as affected by N forms is poorly understood. The objective of this study was to identify the effects of N form on growth as well as on N and K nutrition of flue‐cured tobacco plants (Nicotiana tobaccum L.). The plants were grown in a greenhouse with pots of soil for 117 days after 200 days of preculture. Three treatments (calcium nitrate [Ca(NO₃)₂], ammonium nitrate (NH₄NO₃), and ammonium nitrate plus straw (NH₄NO₃ + straw)) were used. The results showed that there were no significant differences in shoot dry mass of tobacco among the three treatments during the entire growth stage except at 30 and 117 days after transplanting. At these two growth stages, shoot biomass with the Ca(NO₃)₂ treatment was significantly less than that with NH₄NO₃ with or without straw. The NH₄NO₃ + straw plants had more mature leaves and greater leaf dry weight than the other two treatments. At an early stage (before 66 days), N concentration of Ca(NO₃)₂‐fed plants was less than with the other two treatments. The leaf K concentration and shoot K content of NH₄NO₃ and NH₄NO₃ + straw plants were more than with the Ca(NO₃)₂ treatment before maturity. Also, K concentration in mature leaves with these two treatments was greater than with Ca(NO₃)₂ treatment. All these results indicated that NH₄NO₃ application had benefits to the maturity and K accumulation in leaves of tobacco.     

An inverse abundance approach to separate soil nitrogen pools and gaseous nitrogen fluxes into fractions related to ammonium,nitrate and soil organic nitrogen

The soil nitrogen (N) cycle exhibits a variety of complex biochemical reactions in which N species such as NO₂⁻, NO and N₂O are produced and consumed by co‐existing processes that respond differently to the local environmental conditions. Key to understanding the soil N cycle in its full complexity is the development and application of methods that allow a quantification of individual pathways and processes that are responsible for the build‐up and/or emission of N compounds. Triplet ¹⁵N tracer experiments (TTE) have been developed and applied to allow a source‐related quantification of N species such as NO₂⁻, and N₂O by different biochemical pathways (e.g. ammonia oxidation and nitrate reduction) that are related to multiple N sources (NH₄⁺, NO₃⁻ and N_org). An analysis of a TTE requires the application of either a numerical or analytical model. Because of the ease of application it is desirable to use analytical models. However, available analytical solutions suffer from serious drawbacks concerning the quantification of N fluxes related to soil organic N. In this paper we describe the development and application of a new inverse abundance approach (IAA) to analyse a TTE. Theoretical and experimental data sets of soil N₂O release were analysed by the new method. The IAA was also applied to an already existing data set to identify fractions of the soil nitrite pool related to NH₄⁺, NO₃⁻ and N_org. We show that the IAA provides a reliable and comprehensive data evaluation of a TTE.     

Effect of ammonium sulfate pretreatment on ammonia volatilization after urea fertilization

Abstract

Urea applications to soil are subject to loss by ammonia (NH₃) volatilization, unless incorporated. It has been proposed that this loss can be reduced by stimulating populations of soil nitrifiers by an ammonium sulfate [(NH₄)₂SO₄] pretreatment two to four weeks before urea application. The objective of this laboratory trial was to evaluate this concept with five diverse soils, two North American Mollisols and three South American Oxisols. The soils were incubated untreated for two weeks, followed by pretreatment with 0 or 5 kg nitrogen (N) ha^‐1 as (NH₄)₂SO₄, on a soil surface area basis. After another two weeks of incubation, the soils were treated with the equivalent of 0 or 50 kg N ha^‐1 as urea. Ammonia loss was estimated after trapping into phosphoric acid (H₃PO₄). Ammonium sulfate pretreatment reduced NH₃ loss with the two Mollisols and a sandy Oxisol and increased the recovery of the urea application as mineral [ammonium (NH₄ ⁺) + nitrate (NO₃ ^‐)] N in these soils. Little NH₃ loss was detected from the two clay Oxisols, and (NH₄)₂SO₄pretreatment did not influence NH₃ loss or recovery of urea as mineral N. An example of a cropping system where this concept may have utility is discussed.