Measurement of nitrate and chlorate in swimming pool water by capillary zone electrophoresis

Capillary zone electrophoresis (CZE) of nitrate and chlorate in swimming pool water are described. Nitrate and chlorate were determined simultaneously with an indirect detection method in an electrolyte containing 10 mM chromate and 0.1 mM cetyltrimethylammonium bromide (CTAB). Where chloride concentration was so high that nitrate could not be determined satisfactorily because of interference, a direct detection technology was developed in which 10 mM sulfate and 0.1 mM CTAB were used as the buffer. The wavelength for indirect detection was 254 nm and 214 nm for direct detection. Relative standard deviations of the quantification of nitrate and chlorate in real samples were below 6%. The detection limits were 7 mug ml(-1) for chlorate, and 4 mug ml(-1) (indirect detection) and 0.4 mug ml(-1) (direct detection) for nitrate.     

Determination of chlorine containing species in explosive residues using chip-based isotachophoresis

A new method has been developed to allow the determination of the chlorate, chloride and perchlorate anions in inorganic explosive residues to be made using isotachophoresis (ITP). To enable a good separation of these species to be achieved the method involves the use of two complexing agents. Indium(III) is used to allow the determination of chloride whilst using nitrate as the leading ion and alpha-cyclodextrin is used to allow the separation of chlorate and perchlorate. Separations were carried out using a miniaturised poly(methyl methacrylate) (PMMA) separation device. The method was applied to analysing both model samples and actual inorganic explosive containing residue samples. Successful determinations of these samples were achieved with no interference from other anions typically found in inorganic explosive residues. Limits of detection (LOD) for the species of interest were calculated to be 0.80 mg l(-1) for chloride, 1.75 mg l(-1) for chlorate and 1.40 mg l(-1) for perchlorate.     

Improvement of capillary zone electrophoresis sensitivity with artificial seawater as the background electrolyte utilizing transient isotachophoresis for the determination of nitrate and nitrate ions in seawater

We describe capillary zone electrophoresis (CZE) with transient isotachophoresis (ITP) for the determination of low concentrations of nitrite and nitrate ions in seawater. Bromide-free artificial seawater was adopted as background electrolyte (BGE) to eliminate the interference of high concentrations of salts in seawater. To reverse the electroosmotic flow (EOF), 3 mM cetyltrimethylammonium chloride (CTAC) was added to the BGE. High concentrations of chlorate were added to sample solutions as the terminating ion to generate the ITP process before the CZE separation. In general, the stacking effect increased with increasing amounts of chlorate injected into the capillary. The limits of detection (LODs) for nitrite and nitrate were 0.063 and 0.033 mg/L when the chlorate concentration was 600 and 200 mM, respectively; these were half of those obtained by CZE without the transient ITP. The LODs were obtained at a signal to noise ratio (S/N) of 3. The relative standard deviations (RSD, n = 10) of the peak areas for these ions were 3.2 and 2.9%. The RSDs of peak heights for these ions were 1.6 and 2.1%. The RSDs of migration times for these ions were 0.67 and 0.46%.     

Interferences in the determination of total nitrogen in natural waters by photo-oxidation to nitrate-nitrite mixture

The method proposed by Armstrong, Williams and Strickland for the photo-oxidation of total nitrogen in sea-water to nitrate and nitrite has been studied in some detail, to extend its use to fresh and brackish waters, applying a more accurate method for the determination of the reaction products. Variables influencing the yield of nitrate and nitrite are irradiation time, pH and type of buffer, kind of nitrogen compound and its concentration, and the concentrations of oxygen, carbon dioxide, organic matter and salts, especially bromides, even at the low concentrations found in brackish waters. All these variables interact in a rather complicated way. Interferences from halides, organic matter and carbon dioxide are considerably reduced by ensuring that the pH is kept at 8.5-9 during the irradiation. Because pure solutions of many substances give quantitative yields (> or = 98%) in the pH-range 7-9 usually recommended, whereas others require lower pH for maximal oxidation, a method has been developed involving photo-oxidation first at pH 2.1 and then at pH 8.5-9. In the absence of interfering concentrations of halides the relative increase in yield by an initial irradiation at low pH is especially large (10-36%) for proteins, organic nitrogen in fresh waters, uric acid and urea. A comparison is made between determination of total nitrogen in some natural waters by using photo-oxidation and by a Kjeldahl method modified to give total nitrogen. By making use of the optimal conditions presented in this paper, a negative error of less than 8% is expected in the determination of total nitrogen in fresh waters. For saline waters the error will probably be larger, at least at a high ratio of organic to inorganic nitrogen.     

A chlorate ion-selective electrode based on a poly(vinyl chloride)-matrix membrane

An electrode has been prepared, consisting of a PVC membrane containing Corning 477316 nitrate liquid ion-exchanger in the chlorate form, which responds to chlorate ions. It has a faster response (1-2 sec) and lower limit of detection (3 x 10(-5)M) than the nitrate electrode for chlorate determination. Selectivity coefficients for the electrode towards several other ions have been measured.     

High-performance ion chromatography assessment of inorganic and organic nitrogen fractions in potatoes

A new high-performance ion chromatography assay for organic and inorganic nitrogen analysis has been proposed and examined. In the devised protocol, inorganic sample constituents were measured after ultrasonically assisted water extraction. The amine and amide nitrogen content was assessed after modified Kjeldahl digestion and determined as NH₄⁺, and the total nitrogen content was quantified as NO₃⁻ after microwave-facilitated digestion. Finally, the nitro, azo, azoxy nitrogen was calculated by comparison of the total nitrogen content and all measured nitrogen species. The detection limits of the measured ions were 2.0, 0.82 and 0.17 mg L⁻¹ for nitrate, nitrite and ammonium, respectively. For samples of potatoes, the average shares of the nitrogen species found in the total nitrogen content were: 0.83% of nitrate nitrogen, <0.03% of nitrite nitrogen, 2.1% of ammonium nitrogen, 71% of nitro, azo, azoxy nitrogen, and 26% of amine, amide nitrogen. We expect the method to be applicable to different vegetable samples. The quality of the results obtained was verified by analyzing certified reference material and comparing to another analytical method.     

Simultaneous determination of bromide, nitrite and nitrate ions in seawater by capillary zone electrophoresis using artificial seawater as the carrier solution

We describe capillary zone electrophoresis (CZE) for the simultaneous determination of bromide, nitrite and nitrate ions in seawater. Artificial seawater was adopted as the carrier solution to eliminate the interference of high concentrations of salts in seawater. The artificial seawater was free from bromide ion to enable the determination of bromide ion in a sample solution. For the purpose of reversing the electroosmotic flow (EOF), 3 mM cetyltrimethylammonium chloride (CTAC) was added to the carrier solution. A 100 microm ID (inside diameter) capillary was used to extend the optical path length. The limits of detection (LODs) for bromide, nitrite, and nitrate ions were 0.46, 0.072, and 0.042 mg/L (as nitrogen), respectively. The LODs were obtained at a signal to noise ratio (S/N) of 3. The values of the relative standard deviation (RSD) of peak area for these ions were 1.1, 1.5, and 0.97%. The RSDs of migration time for these ions were 0.61, 0.69, and 0.66%. Artificial seawater samples containing various concentrations of bromide, nitrite, and nitrate ions were analyzed by the method. The error was less than +/-12% even if the concentration ratio of bromide ion to nitrite or nitrate ion was 20-240. The proposed method was applied to the determination of bromide, nitrite, and nitrate ions in seawater samples taken from the surface and the seabed. These ions in other environmental waters such as river water and rainwater samples were also determined by ion chromatography (IC) as well as this method.     

等离子体发射光谱法测定碳化硅中的游离总硅含量

针对分光光度法测定游离总硅含量受干扰因素多、测试数据不稳定的缺点,探讨了采用ICP-AES法测定碳化硅中游离总硅含量。采用行星球磨仪对碳化硅样品进行研磨,以硝酸钠、硝酸、氢氟酸作溶剂,采用微波消解法处理样品。选择212．412nm特征谱线并以其强度U）与对应的硅浓度（c）建立校准曲线,硅的质量浓度在10-100μg／mL范围内与特征谱线强度呈良好的线性关系,线性方程为I=233．76c＋86．94,线性相关系数间．997,检出限为0．027μg／mL。测定结果的相对标准偏差为1．35％～2．79%（n=6）。加标回收率为97．6％～108．0％。该法测定碳化硅中游离总硅含量是可行的。     

Sequential injection system for on-line analysis of total nitrogen with UV-mineralization

An automatic method for the determination of total nitrogen in wastewater by sequential injection analysis and mineralization with UV radiation has been developed. The method is based on the mineralization of the samples with sodium persulphate in basic medium under UV radiation. Small volumes of sample and reagents are firstly aspirated into a single channel and then propelled by flow reversal to the UV reactor and then to the detector. The organic and inorganic nitrogen compounds are oxidized to nitrate that is then measured at 226 nm. The sequential injection procedure has been optimized and the factors affecting the efficiency of the oxidation have been studied with a number of test substances with different chemical structures and properties. Solutions in the concentration range 1-56 g l⁻¹ of nitrogen can be analyzed with the described procedure. The sample rate is of 30-40 samples h⁻¹. The LOD is 0.6 mg l⁻¹ N and the reproducibility is 1.8% (28 mg l⁻¹ N). Organic carbon in the form of glucose was added to a number of test solutions to study the potential interference of organic matter.The method was compared with the Kjeldahl digestion method by analyzing 15 wastewater samples with both methods. The nitrate and nitrite content of the non-oxidized samples were subtracted from the corresponding nitrogen content determined after photo-oxidation and the value compared with the Kjeldahl nitrogen content.     

总氮测定过程中空白吸光值偏高的原因分析

使用HJ 636-2012测定水质总氮时,空白吸光值往往偏高。为了寻找最佳的实验条件,使用多元线性回归模型定性评价过硫酸钾和氢氧化钠的纯度、实验用水、碱性过硫酸钾溶液的存放时间、消解条件、冷却时间、消解器皿等因素对空白吸光值的重要性。结果表明:过硫酸钾纯度对空白吸光值影响最显著。为了保证总氮空白吸光值小于0.030,测定总氮时应优先使用经过2~3次重结晶的过硫酸钾以及优级纯的氢氧化钠,碱性过硫酸钾溶液应现配现用;建议消解时间30 min,消解温度123℃,自然冷却时间1.5 h;实验应优先使用超纯水或无氨水;使用哈希消解管代替25 mL比色管。     

Organic interferences and their elimination in the 2,4-xylenol spectrophotometric method for nitrate

The 2,4-xylenol spectrophotometric method for nitrate involves formation of 6-nitro-2,4-xylenol, which is steam-distilled into an ammonia—water—isopropanol mixture. The yellow color of the ammonium salt of 6-nitro-2,4-xylenol is measured at 455 nm. A detailed study of the possible interferences from 123 representative organic compounds is described; 61 compounds interfered (when present in amounts of 0.1 g in the original sample). The interfering compounds can be classified according to their mode of interference: (1) compounds that are readily nitrated or oxidized by nitrate in the sulfuric acid medium used cause low results; (2) compounds containing the ONO₂ group that hydrolyze to nitrate cause high results; (3) compounds that steam-distil to produce colored solutions; (4) compounds that steam-distil to produce turbid solutions; (5) compounds that hydrolyze, either in water or sulfuric acid solution, to produce inorganic ions or compounds (e.g. Cl^-, S^2-, and H₂O₂) that repress the color development. Three procedures are described for the elimination of the interferences: (1) oxidation of the organic compound with permanganate, reduction of the excess of permanganate with hydrogen peroxide, and destruction of the peroxide by boiling in the presence of Fe(III) catalyst (this is unsuitable for organic compounds containing nitrogen, as there is invariably some oxidation to nitrate); (2) extraction of interfering organic compounds with methyl isobutyl ketone; (3) precipitation—adsorption method involving treatment with zinc sulfate and sufficient sodium hydroxide to precipitate most of the zinc as zinc hydroxide, addition of 3 g of activated carbon, digestion at 55–65°C for 20 min. cooling, dilution, and filtration. Method (3) is applicable to all organic compounds tested except formaldehyde. The amount of organic compound used to test the methods was normally 0.25 g in the solution being treated.     

Elucidation of nitrate reduction pathways in anaerobic bioreactors using a stable isotope approach

Leachate recirculation allows an increase of moisture content and the enhancement of the anaerobic digestion of wastes in landfill. Since there is no ammonia elimination process in landfill when leachate is recirculated, NH(4) (+) may accumulate. One strategy for NH(4) (+) removal is to treat aerobically the leachate outside the landfill to convert NH(4) (+) into NO(3) (-). When nitrified leachate is recirculated, denitrification should occur in the waste. We have previously shown that wastes have a large capacity to convert nitrate into N(2). Nevertheless, in some cases we observed nitrate reduction without gaseous nitrogen production. Using a stepwise multiple regression models, H(2)S concentration was the unique parameter found to have a negative effect on N(2) production. We then suspected that dissimilatory nitrate reduction to ammonium (DNRA) occurred in the presence of H(2)S. In order to verify this hypothesis, (15)N nitrate injections were performed into microcosms containing different H(2)S concentrations. The ammonium (15)N enrichment was measured using an elemental analyser coupled to an isotope ratio mass spectrometer. In the two microcosms containing the highest H(2)S concentrations, the ammonium was (15)N enriched and at the end of the experiment all the added nitrate was converted into ammonium. For the two microcosms containing the lowest H(2)S concentrations, no (15)N enrichment of ammonium was observed. This isotopic approach has allowed us to demonstrate that, in the presence of significant concentrations of H(2)S, denitrification is replaced by DNRA.     

SI-traceable certification of the amount content of cadium below the ng g(-1) level in blood samples by isotope dilution ICP-MS applied as a primary method of measurement

The development and implementation of a method for the certification of cadmium in blood samples at low ng g(-1) and sub ng g(-1) levels is described. The analytical procedure is based on inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) applied as a primary method of measurement. Two different sample digestion methods, an optimized microwave digestion procedure using HNO3 and H2O2 as oxidizing agents and a high-pressure asher digestion procedure, were developed and compared. The very high salt content of the digests and the high molybdenum content, which can cause oxide-based interferences with the Cd isotopes, were reduced by a chromatographic matrix separation step using an anion-exchange resin. All isotope ratio measurements were performed by a quadrupole ICP-MS equipped with an ultrasonic nebulizer with membrane desolvator. This sample introduction set-up was used to increase sensitivity and minimize the formation of oxides (less MoO+ interference with the Cd isotopes). Because of the very low Cd concentrations in the samples and the resulting need to minimize the procedural blank as much as possible, all sample-processing steps were performed in a clean room environment. Detection limits of 0.005 ng g(-1) Cd were achieved using sample weights of 2.7 g. The method described was used to recertify the cadmium content of three different blood reference materials from the Community Bureau of Reference (BCR) of the European Commission (BCR-194, BCR-195, BCR- 196). Cadmium concentrations ranged between approximately 0.2 ng g(-1) and approximately 12 ng g(-1). For these materials, SI-traceable certified values including total uncertainty budgets according to ISO and Eurachem guidelines were established.     

上游水库水体中氨氮、亚硝酸盐氮、硝酸盐氮、总氮的测定和关系探究

采用紫外分光光度法测定上游水库固定监测点位近两年采集样品的总氮、硝酸盐氮、氨氮、亚硝酸盐氮含量.对测试结果进行分析比较,探讨了上游水库水中总氮、硝酸盐氮、氨氮、亚硝酸盐氮的关系,从而为上游水库水质数据分析和综合评价提供一定参考.     

Determination of total phosphorus and nitrogen in turbid waters by oxidation with alkaline potassium peroxodisulfate and low pressure microwave digestion, autoclave heating or the use of closed vessels in a hot water bath: comparison with Kjeldahl digestion

The evaluation of the use of alkaline peroxodisulfate digestion with low pressure microwave, autoclave or hot water bath heating for the determination of total phosphorus and nitrogen in turbid lake and river waters is described. The efficiency of these digestion procedures were compared to a Kjeldahl digestion procedure with sulphuric acid-potassium sulfate and copper sulfate. The final solution before digestion was 0.045 M in potassium peroxodisulfate and 0.04 M in sodium hydroxide. Procedures were evaluated by the analysis of suspensions of two reference materials, National Institute of Environmental Science, Japan, no. 3 Chlorella and no. 2 pond sediment and natural turbid waters. Best recoveries of phosphorus and nitrogen by microwave heating were obtained when solutions were digested at 95 °C for 40 min. Quantitative recoveries of phosphorus from Chlorella suspensions up to 1000 mg/l were obtained by all three heating procedures, but incomplete recoveries of nitrogen occurred above 20 mg N/l in the digested sample. Good recoveries of phosphorus and nitrogen from suspended sediment suspensions were obtained only from solutions containing <150 mg/l of suspended sediments. Recoveries of phosphorus from phosphorus compounds containing COP and CP bonds added to distilled water were quantitative (94-113%) except for polyphosphates (microwave, 34±8; autoclave, 114±6; water bath, 96±4) and aluminium phosphate (8-23%). Recoveries of nitrogen compounds containing CN bonds added to distilled water were quantitative (94-96%). The analysis of a range of natural turbid water samples by alkaline peroxodisulfate and microwave, autoclave and water bath heating gave similar total phosphorus and nitrogen results. All procedures using alkaline peroxodisulfate underestimate phosphorus concentrations at high suspended sediment concentrations (>150 mg/l) and are only suitable for the analysis of very turbid samples when the turbidity is due to organic matter (algal cells, plant detritus). Underestimation of nitrogen occurs when samples contain more than 20 mg N/l.     

Simultaneous electrochemical determination of nitrate and nitrite in aqueous solution using Ag-doped zeolite-expanded graphite-epoxy electrode

In this work a new electrochemical sensor based on an Ag-doped zeolite-expanded graphite-epoxy composite electrode (AgZEGE) was evaluated as a novel alternative for the simultaneous quantitative determination of nitrate and nitrite in aqueous solutions. Cyclic voltammetry was used to characterize the electrochemical behavior of the electrode in the presence of individual or mixtures of nitrate and nitrite anions in 0.1 M Na₂SO₄ supporting electrolyte. Linear dependences of current versus nitrate and nitrite concentrations were obtained for the concentration ranges of 1-10 mM for nitrate and 0.1-1 mM for nitrite using cyclic voltammetry (CV), chronoamperometry (CA), and multiple-pulsed amperometry (MPA) procedures. The comparative assessment of the electrochemical behavior of the individual anions and mixtures of anions on this modified electrode allowed determining the working conditions for the simultaneous detection of the nitrite and nitrate anions. Applying MPA allowed enhancement of the sensitivity for direct and indirect nitrate detection and also for nitrite detection. The proposed sensor was applied in tap water samples spiked with known nitrate and nitrite concentrations and the results were in agreement with those obtained by a comparative spectrophotometric method. This work demonstrates that using multiple-pulse amperometry with the Ag-doped zeolite-expanded graphite-epoxy composite electrode provides a real opportunity for the simultaneous detection of nitrite and nitrate in aqueous solutions.     

Determination of monovalent inorganic anions in high-ionic-strength samples by electrostatic ion chromatography with suppressed conductometric detection

A new ion chromatographic (IC) system has been established by using micelles of 3-(N,N-dimethylmyristylammonio)propanesulfonate (Zwittergent 3-14) loaded onto a reversed-phase packed column as the separation column with an electronic rotary switching valve packed-bed suppressor for conductometric detection of inorganic anions. An aqueous H3BO3-Na2B4O7 solution has been demonstrated to be the most desirable eluent for this IC system. The relationship between retention time and the concentration of the borate eluent was determined for a series of model anionic analytes and this relationship was found to be opposite to that exhibited in a conventional anion-exchange IC system. The rapid elution and complete separation of monovalent inorganic anions were obtained by initially using a high-concentration borate solution as the eluent for a short-period, and then switching to a lower-concentration borate eluent to complete the separation. Detection limits for nitrite, bromide, nitrate, and chlorate were 0.85, 0.88, 0.95 and 4.8 microM, respectively, when a 7.0 mM Na2B4O7 eluent was used. Moreover, the ability to directly detect these monovalent anions in samples containing high concentrations of sulfate and/or chloride ions provided a major advantage of this approach.     

Determination of Lead in Lipstick by Direct Solid Sampling High-Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry: Comparison of Two Digestion Methods

A new analytical procedure for the determination of lead in lipstick has been developed using direct solid sampling high resolution continuum source graphite furnace atomic absorption spectrometry (SS HR CS GFAAS). The performance of this method has been compared to acid digestion methods for sample preparation, with or without hydrofluoric acid (HF) with inductively coupled plasma mass spectrometry (ICP-MS) detection. Good reliability was obtained for all three methods; the results obtained for certified reference materials with concentrations between 1 and 20 ppm were in agreement with the certified values. However, for materials with complex matrices, such as pearl or Ca-Na borosilicate, only ICP-MS with HF sample digestion or AAS with direct solid sampling allowed complete recovery of lead. To avoid the use of hazardous acids, the development of SS HR CS GFAAS is an interesting alternative. With the AAS method, a characteristic mass of 13.2 pg of lead was obtained, and the limit of detection was 0.005 µg/g. The performance of the method was evaluated by determining lead in lipstick. The use of the solid sampling technique constitutes a good alternative for accurate and rapid determination of lead content in lipstick and cosmetic raw materials, with a suitable limit of detection and a reduced risk of contamination or of analyte loss. Another alternative would be to use ICP-MS determination in conjunction with microwave-assisted acid digestion without the use of HF, which implies accepting a quantification of “nearly total” lead, closer to a “bio-extractible” fraction.     

determination of Carbon,Nitrogen and Sulfur in Soils,Sediments and Wastes: A Comparative Study

Abstract

The determination of low levels (< 1 %) of total carbon and nitrogen in soils, sediments and solid wastes is made fast using an automated elemental NCS analyzer (Carlo Erba NA-1500). The recoveries of total N obtained were similar with either the elemental analyzer or the Kjeldahl digestion method used. The recoveries and precision of the TC, TOC data were better and more predictable using the elemental analyzer than the wet digestion procedure used in this study. Acid pre-treatment prior TOC determinations using the NCS analyzer resulted in lower total N recoveries. The determination of S in the same materials using this analyzer is not recommended due to low recoveries and poor precision.     

Characterization of urease derived from Citrullus lanatus (watermelon) seeds to estimate total Kjeldahl nitrogen in human urine

A urease extract prepared by decanting liquid from a suspension of finely ground Citrullus lanatus (watermelon) seeds was characterized and applied to dilute urine samples to demonstrate a low-cost field method to estimate total Kjeldahl nitrogen (TKN) concentrations in human urine. The extract exhibited a Michaelis-Menten constant, K_m, of 3.00 mM urea and a specific activity of up to 12.2 U/mg protein at an optimum pH of 8.1. A statistical F-test on 54 samples demonstrated that TKN can be estimated as the total ammonium-nitrogen recovered upon addition of urease in dilute fresh and stale urine samples. The total ammonium-nitrogen in urine samples determined after treatment with watermelon seed urease was consistent with that determined using traditional acid digestion techniques. The extract retained 85% of its initial capacity after three months of refrigeration. The effectiveness of this method to assay nitrogen in unbuffered urine samples will be useful in nitrogen analyses in nutrient recovery and urine or slurry storage contexts. Accordingly, this study is useful in understanding the kinetics of a plant-derived urease acting in dilute urine.