Flow injection catalytic spectrophotometric simultaneous determination of nitrite and nitrate

A new flow injection catalytic spectrophotometric method is proposed for the simultaneous determination of nitrite and nitrate based on the catalytic effect of nitrite on the redox reaction between crystal violet and potassium bromate in phosphoric acid medium and nitrate being on-line reduced to nitrite with a cadmium-coated zinc reduction column. The redox reaction is monitored spectrophotometrically by measuring the decrease in the absorbance of crystal violet at the maximum absorption wavelength of 610 nm. A technique of inserting a reduction column into sampling loop is adopted and the flow injection system produces a signal with a shoulder. The height of shoulder in the ascending part of the peak corresponds to the nitrite concentration and the maximum of the peak corresponds to nitrate plus nitrite. The detection limits are 0.3 ng ml⁻¹ for nitrite and 1.0 ng ml⁻¹ for the nitrate. Up to 32 samples can be analyzed per hour with a relative standard deviation of less than 2%. The method has been successfully applied for the simultaneous determination of nitrite and nitrate in natural waters.     

A model to predict the steady-state concentration of hydroxyl radicals in the surface layer of natural waters

A model was developed to predict the steady-state [*OH] in the surface layer of natural waters as a function of nitrate, inorganic carbon (IC) and dissolved organic matter (DOM). The parameter values were studied in the range detected in shallow high-mountain lakes, to which the model results are most relevant. Calculations indicate that [*OH] increases with increasing nitrate and decreasing IC, and conditions are also identified where [*OH] is directly proportional, inversely proportional or independent of DOM. Based on the model results it is possible to predict the half-life time, due to reaction with *OH, of given dissolved compounds, including organic pollutants, from the water composition data.     

Formation of hydroxyl radical from the photolysis of frozen hydrogen peroxide

Hydrogen peroxide (HOOH) in ice and snow is an important chemical tracer for the oxidative capacities of past atmospheres. However, photolysis in ice and snow will destroy HOOH and form the hydroxyl radical (*OH), which can react with snowpack trace species. Reactions of *OH in snow and ice will affect the composition of both the overlying atmosphere (e.g., by the release of volatile species such as formaldehyde to the boundary layer) and the snow and ice (e.g., by the *OH-mediated destruction of trace organics). To help understand these impacts, we have measured the quantum yield of *OH from the photolysis of HOOH on ice. Our measured quantum yields (Phi(HOOH --> *OH)) are independent of ionic strength, pH, and wavelength, but are dependent upon temperature. This temperature dependence for both solution and ice data is best described by the relationship ln(Phi(HOOH --> *OH)) = -(684 +/- 17)(1/T) + (2.27 +/- 0.064) (where errors represent 1 standard error). The corresponding activation energy (Ea) for HOOH (5.7 kJ mol(-1)) is much smaller than that for nitrate photolysis, indicating that the photochemistry of HOOH is less affected by changes in temperature. Using our measured quantum yields, we calculate that the photolytic lifetimes of HOOH in surface snow grains under midday, summer solstice sunlight are approximately 140 h at representative sites on the Greenland and Antarctic ice sheets. In addition, our calculations reveal that the majority of *OH radicals formed on polar snow grains are from HOOH photolysis, while nitrate photolysis is only a minor contributor. Similarly, HOOH appears to be much more important than nitrate as a photochemical source of *OH on cirrus ice clouds, where reactions of the photochemically formed hydroxyl radical could lead to the release of oxygenated volatile organic compounds to the upper troposphere.     

Development and intercalibration of ultraviolet solar actinometers

Ultraviolet (UV) sunlight actinometers were developed based on the photolysis of nitrate and nitrite. Photon exposures ( i.e. time-integrated irradiances) were quantified from the photochemical production of salicylic acid (SA) or p -hydroxybenzoic acid (pHBA) formed by the reaction of the hydroxyl radical with benzoic acid. The solar response bandwidth for the nitrate actinometer in quartz tubing was 322 ± 11 nm during the Spring of 1999, while the response bandwidth of the Mylar D-filtered nitrite actinometer was 355 ± 25 nm. Intercomparisons of the nitrate and nitrite actinometers with a Smithsonian Environmental Research Center SR-18 scanning UV-B radiometer (SERC SR-18) and an Optronics OL-754 spectroradiometer (OL-754) were performed during the summer of 1998, and the winter and spring of 1999. Photon exposures determined by the nitrate actinometer were in excellent agreement with the SERC SR-18, with a slope (95% confidence interval [CI]) of 0.98 ± 0.01 based on SA production and 0.94 ± 0.02 based on pHBA production. Excellent agreement was also found between the nitrite actinometer and the OL-754, with a slope (95% CI) of 1.00 ± 0.01 using SA production and 1.00 ± 0.02 using pHBA production. These actinometers are well suited for use in the water column and are sufficiently sensitive to determine photon exposures below the 0.1% UV light-level.     

Flow Injection Biamperometric Determination of Nitrite and Nitrate

Abstract

A simple and efficient FIA method was used with good results to determine nitrite in residual waters and nitrate in natural waters. Nitrite determination is based on the reaction with iodide occurring in acidic medium and biamperometric detection of the formed iodine at two platinum electrodes polarised at a potential of 100 mV. Nitrate is similarly determined after its previous reduction to nitrite in a cadmium column. The method does not need the solution deaeration. However, the calibration graphs present two regions of linearity owing to the catalytic effect of the dissolved oxygen on the iodide oxidation by nitrite.     

Flow-injection determination of inorganic forms of nitrogen by gas diffusion and conductimetry

A flow-injection—conductimetric method was applied to the determination of ammonia, nitrate and nitrite at concentrations down to 5, 20 and 20 ng ml^?1, respectively. Ammonia was determined by merging the injected sample with an alkaline solution (NaOHEDTA) and passing the mixture through a diffusion cell. The ammonia released was collected by a flowing stream of deionized water that passed through a conductance flow cell. Nitrate and nitrite concentrations were determined after reduction to ammonia in alkaline medium using a column filled with metallic zinc. The ammonia produced was then measured as described above. About 60 samples per hour can be processed with a relative standard deviation of about 1%. Satisfactory agreement was observed between results for ammonia in samples of natural water and nitrate in tap and mineral water determined by the proposed method and by standard spectrophotometric procedures. Speciation can be achieved by adding sulphanilic acid to remove nitrite from the sample and determining the ammonia without the use of the column.     

Fluorimetric determination of nitrate in natural waters with 3-amino-1,5-naphthalenedisulphonic acid in a flow-injection system

A rapid, sensitive and precise flow-injection method for the determination of nitrate in natural waters is presented. Nitrate is first reduced in a copperized cadmium column to nitrite, which reacts with 3-amino-1,5-naphthalenedisulphonic acid to form the azoic acid. This acid forms a fluorescent salt in alkaline medium. The injecton rate is about 30 h^?1, the relative standard deviation for 10 injections of 2 × 10^?5 M nitrate is 0.8%, and the detection limit (S/N = 3)_is 1 × 10^?8 M nitrate.     

Flow-injection analysis of nitrate by reduction to nitrite and gas-phase molecular absorption spectrometry

Two flow-injection manifolds have been investigated for the determination of nitrate. These manifolds are based on the reduction of nitrate to nitrite and determination of nitrite by gas-phase molecular absorption spectrophotometry. Nitrate sample solution (300 microL) which is injected to the flow line, is reduced to nitrite by reaction with hydrazine or passage through the on-line copperized cadmium (Cd-Cu) reduction column. The nitrite produced reacts with a stream of hydrochloric acid and the evolved gases are purged into the stream of O2 carrier gas. The gaseous phase is separated from the liquid phase using a gas-liquid separator and then swept into a flow-through cell which has been positioned in the cell compartment of an UV-visible spectrophotometer. The absorbance of the gaseous phase is measured at 204.7 nm. A linear relationship was obtained between the intensity of absorption signals and concentration of nitrate when Cd-Cu reduction method was used, but a logarithmic relationship was obtained when the hydrazine reduction method was used. By use of the Cd-Cu reduction method, up to 330 microg of nitrate was determined. The limit of detection was 2.97 microg nitrate and the relative standard deviations for the determination of 12.0, 30.0 and 150 microg nitrate were 3.32, 3.87 and 3.6%, respectively. Maximum sampling rate was approximately 30 samples per hour. The Cd-Cu reduction method was applied to the determination of nitrate and the simultaneous determination of nitrate and nitrite in meat products, vegetables, urine, and a water sample.     

Determination of hydroxyl radical photoproduction rates in natural waters.

The photochemical formation rates of hydroxyl radicals (OH radicals) in river water and seawater were determined by a simple, rapid and sensitive benzene probe method, in which phenol formed by the reaction between benzene and photochemically-generated OH radicals was analyzed by on-line preconcentration HPLC. The OH radical formation rates from well-known OH radical sources, such as nitrate, nitrite and hydrogen peroxide, were in good agreement with those reported previously. River water samples containing high concentrations of nitrate and nitrite were found to show high OH radical formation rates. Ten to 80% of the OH radical formation in river water and seawater was due to the photolysis of nitrate and nitrite, but OH radical formation from hydrogen peroxide was negligible. The OH radical formation from unknown sources other than nitrate, nitrite and hydrogen peroxide was strongly correlated to the amount of fluorescent matter.     

Flow-injection catalytic spectrophotometric determination of nitrite using the redox reaction between naphthol green B and potassium bromate

A flow injection catalytic spectrophotometric method is proposed for the determination of nitrite based on its catalytic effect on the redox reaction between naphthol green B and potassium bromate in phosphoric acid medium. The reaction is monitored spectrophotometrically by measuring the decrease in absorbance of naphthol green B at the maximum absorption wavelength of 722 nm. The detection limit is 0.5 ng cm(-3) in a sample volume of 90 mm(3). Up to 50 samples can be analyzed per hour with a relative precision of ca. 2%. The method is free from most interferences, especially from large amounts of nitrate. The procedure was successfully applied to the determination of trace nitrite in natural waters.     

Simultaneous spectrophotometric determination of nitrite and nitrate by flow-injection analysis

An automatic direct spectrophotometric method for the simultaneous determination of nitrite and nitrate by flow-injection analysis has been developed. Nitrite reacts with 3-nitroaniline in the presence of hydrochloric acid (0.96-1.8 M HCl or pH 0.5-0.7) to form a diazonium cation, which is subsequently coupled with N-(1-naphthyl)-ethylenediamine dihydrochloride to form a stable purple azo dye, the absorbance of which is measured at 535 nm. Nitrate is reduced on-line to nitrite in a copper-coated cadmium column which is then treated with azo dye reagent and the absorbance due to the sum of nitrite and nitrate is measured; nitrate is determined from the difference in absorbance values. A copper column incorporated into the reaction manifold before the copperised cadmium column not only improves the long-term accuracy, but also extends the life time of the copperised cadmium column. Various analytical parameters, such as effect of acidity (pH), flow rate, sample size, dispersion coefficient, time, temperature, reagent concentration and interfering species, were studied. The calibration graphs were rectilinear for 0.1-3.5 mug ml(-1) of NO(3) and 10 ng ml(-1)-2.2mug ml(-1) of NO(2). The method is successfully applied to some food samples (meat, flour and cheese), environmental waters (inland and surface), beer and soil samples. Up to 30 samples can be analysed per hour with a relative precision of approximately 0.1-2%.     

Simultaneous determination of nitrite and nitrate in dew, rain, snow and lake water samples by ion-pair high-performance liquid chromatography

A simple, fast, sensitive and accurate reversed-phase ion-pair HPLC method for simultaneous determination of nitrite and nitrate in atmospheric liquids and lake waters has been developed. Separations were accomplished in less than 10 min using a reversed-phase C₁₈ column (150 mm × 2.00 mm i.d., 5 μm particle size) with a mobile phase containing 83% 3.0 mM ion-interaction reagent tetrabutylammonium hydroxide (TBA-OH) and 2.0 mM sodium phosphate buffer at pH 3.9 and 17% acetonitrile (flow rate, 0.4 mL/min). UV light absorption responses at 205 nm were linear over a wide concentration range from 100 μg/mL to the detection limits of 10 μg/L for nitrite and 5 μg/L nitrate. Quantitation was carried out by the peak area method. The relative standard deviation for the analysis of nitrite and nitrate was less than 3.0%. This method was applied for the simultaneous determination of nitrite and nitrate in dew, rain, snow and lake water samples collected in southeast Massachusetts. Nitrate was found being present at 4.79-5.99 μg/mL in dew, 1.20-2.63 μg/mL in rain, 0.32-0.60 μg/mL in snow and 0.12-0.23 μg/mL in lake water. Nitrite was only a minor species in dew (0.62-0.83 μg/mL), rain (<0.005-0.14 μg/mL), snow (0.021-0.032 μg/mL) and lake water (0.12-0.16 μg/mL). High levels of nitrite and nitrate observed in dew water droplets may constitute an important source of hydroxyl radicals in the sunny early morning.     

Vibrational spectroscopic study of the nitrate containing hydrotalcite mbobomkulite

Raman spectroscopy has been used to study the nitrate hydrotalcite mbobomkulite NiAl2(OH)16(NO3).4H2O. Mbobomkulite along with hydrombobomkulite and sveite are known as 'cave' minerals as these hydrotalcites are only found in caves. Two types of nitrate anion are observed using Raman spectroscopy namely free or non-hydrogen bonded nitrate and nitrate hydrogen bonded to the interlayer water and to the 'brucite-like' hydroxyl surface. Two bands are observed in the Raman spectrum of Ni-mbobomkulite at 3576 and 3647 cm(-1) with an intensity ratio of 3.36/7.37 and are attributed to the Ni3OH and Al3OH stretching vibrations. The observation of multiple water stretching vibrations implies that there are different types of water present in the hydrotalcite structure. Such types of water would result from different hydrogen bond structures.     

Modelling the occurrence and reactivity of the carbonate radical in surface freshwater

A model was developed to foresee the degradation kinetics of dissolved compounds for reaction with the carbonate radical in surface waters. It would contribute to the assessment of the environmental persistence of pollutants, therefore, allowing a better definition of the exposure of natural ecosystems and human communities to hazardous substances. The model is a function of the water chemical composition, the water column depth, and the second-order rate constant of the reaction between the relevant compound and the carbonate radical. A comparison between the reactivity of the carbonate and the hydroxyl radical shows that the latter would often play a more important role as reactive species, but the carbonate radical could prevail in carbonate-rich waters, giving the degradation of easily oxidisable molecules.     

Phenol photonitration

This paper presents some new data on nitrophenol formation from phenol under illumination, and reviews the studies performed on phenol photonitration, from its discovery in 1988 to the very recent elucidation of its reaction pathway by the authors. Recent experimental results account for the pH effect on phenol photonitration. The nitrogen sources so far investigated are nitrate and nitrite, which undergo photolysis upon absorption of near-UV light. These studies have given a relevant information on the role of both nitrate and nitrite as environmental factors. Such processes can take place both in natural waters and in atmospheric hydrometeors.     

The analysis of nitrate in environmental samples by reversed-phase HPLC

A method is presented for the analysis of nitrate in natural waters and waste water by high-performance liquid chromatography (HPLC) with a reversed-phase octadecyl column, aqueous phosphoric acid/dihydrogen phosphate mobile phase, and UV detector. The optimum nitrate concentration is 0.3 to 3 mg/L as N with linear detector response below 3 mg/L. The detection limit is 0.007 mg/L. Relative standard deviations in the optimum range are consistently less than one percent. Several potential interferences have been investigated; nitrite and organic chromophores are resolved from nitrate and do not interfere. Hexavalent chromium and sulfate are slight positive interferences, negligible at typical environmental concentrations. The method produces results in agreement with the accepted chromotropic acid method except in samples from eutrophic lakes, for which evidence is presented indicating that the chromotropic acid is inaccurate.     

Studying the photochemical fate of methyl parathion in natural waters under tropical conditions

This article discusses the degradation of methyl parathion (MP) in natural and sterilized waters. Experiments were prepared using natural waters gathered in two aquatic systems (Rio de Janeiro State, Brazil), ultra-pure water and humic water solution under different conditions (i.e. in the presence/absence of light, sterilized/no sterilize solutions). The exposition to sunlight was carried out using experimental bottles without headspace immersed in a swimming pool for temperature control. Natural waters results showed that the degradation kinetic of MP is of first order and the half-lives for lake water experiments, under direct sunlight and shade, were 4.41 and 6.89 days, respectively. The kinetic curve for MP degradation in river waters showed that there are no differences when samples were sterilized and placed (or not) under shade conditions, and the half-lives ranged from 5.37 to 2.75 days for sterilized river water/absence of sunlight and natural/presence of sunlight, respectively. Therefore, our results showed that photolysis plays, in addition to bio- and chemical degradation, an important role in the decomposition of MP in aquatic environments.     

A Model Assessment of the Occurrence and Reactivity of the Nitrating/Nitrosating Agent Nitrogen Dioxide (•NO2) in Sunlit Natural Waters

Nitrogen dioxide (^•NO₂) is produced in sunlit natural surface waters by the direct photolysis of nitrate, together with ^•OH, and upon the oxidation of nitrite by ^•OH itself. ^•NO₂ is mainly scavenged by dissolved organic matter, and here, it is shown that ^•NO₂ levels in sunlit surface waters are enhanced by high concentrations of nitrate and nitrite, and depressed by high values of the dissolved organic carbon. The dimer of nitrogen dioxide (N₂O₄) is also formed in the pathway of ^•NO₂ hydrolysis, but with a very low concentration, i.e., several orders of magnitude below ^•NO₂, and even below ^•OH. Therefore, at most, N₂O₄ would only be involved in the transformation (nitration/nitrosation) of electron-poor compounds, which would not react with ^•NO₂. Although it is known that nitrite oxidation by CO₃^•− in high-alkalinity surface waters gives a minor-to-negligible contribution to ^•NO₂ formation, it is shown here that NO₂⁻ oxidation by Br₂^•− can be a significant source of ^•NO₂ in saline waters (saltwater, brackish waters, seawater, and brines), which offsets the scavenging of ^•OH by bromide. As an example, the anti-oxidant tripeptide glutathione undergoes nitrosation by ^•NO₂ preferentially in saltwater, thanks to the inhibition of the degradation of glutathione itself by ^•OH, which is scavenged by bromide in saltwater. The enhancement of ^•NO₂ reactions in saltwater could explain the literature findings, that several phenolic nitroderivatives are formed in shallow (i.e., thoroughly sunlit) and brackish lagoons in the Rhône river delta (S. France), and that the laboratory irradiation of phenol-spiked seawater yields nitrophenols in a significant amount.     

Determination of nitrite and nitrate in Venice lagoon water by ion interaction reversed-phase liquid chromatography

Ion interaction reversed-phase liquid chromatography with octylammonium orthophosphate as the interacting reagent and a reversed-phase C₁₈ column was applied to the identification and determination of nitrite and nitrate in Venice lagoon water. Interference by the high chloride concentration was systematically studied and the results obtained with different column packings were compared. With spectrophotometric detection at 230 nm, nitrite at 0.005 mg 1^?1 can be detected and determined even in the presence of 0.70 M chloride. The dependence of the retention time of nitrite on the chloride concentration was studied for two reversed-phase columns with different packings. Concentrations of 0.30 ± 0.05 mg 1^?1 of nitrite and 0.20 ± 0.05 mg 1^?1 of nitrate were found in Venice lagoon water.     

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.