Chemical conversion of nitrate and nitrite to nitrous oxide for nitrogen and oxygen isotopic analysis in freshwater and seawater

We present a novel method for nitrogen and oxygen natural isotopic abundance analysis of nitrate and nitrite of seawater and freshwater at environmental concentrations. The method involves the reduction of nitrate to nitrite using spongy cadmium with further reduction to nitrous oxide using sodium azide in an acetic acid buffer. For separate nitrite analysis, the cadmium reduction step is simply bypassed. Nitrous oxide is purged from the water sample and trapped cryogenically using an automated system with subsequent release into a gas chromatography column. The isolated nitrous oxide is then analyzed on a continuous flow isotope ratio mass spectrometer via an open split. This paper describes the basic protocol and reaction conditions required to obtain reproducible natural abundance level nitrogen and oxygen isotopic ratios from nitrate, nitrite, or both, and the results obtained to support these conclusions. A standard deviation less than 0.2 per thousand for nitrogen and 0.5 per thousand for oxygen was found for nitrate samples ranging in concentration from 40 to 0.5 microM (better for nitrite), with a blank of 2 nmol for 50-mL samples. Nitrogen and oxygen isotopic fractionation and oxygen atom exchange were consistent within each batch of analysis. There was no interference from any seawater matrixes. Only one other method published to date can measure the nitrate oxygen isotopic abundance in seawater and none that do so for nitrite alone in the presence of nitrate. This method may prove to be simpler, faster, and obtain isotopic information for lower concentrations of nitrate and nitrite than other methods.     

Triple oxygen isotope analysis of nitrate using the denitrifier method and thermal decomposition of N2O

Interaction with ozone transfers its anomalous (non-mass-dependent) 17O enrichment to atmospheric nitrogen oxides and nitrate. The 17O anomaly (Delta17O) in nitrate can be used to identify atmospheric nitrate inputs into terrestrial and aquatic environments as well as to study the role of ozone in the atmosphere's reactive nitrogen cycle. We report here on an online method for analysis of the 17O anomaly, using a strain of denitrifiers to convert nitrate to N2O, which decomposes quantitatively to N2 and O2 in a gold furnace at 800 degrees C, followed by gas chromatographic separation and isotope analysis of O2. This method requires approximately 50 nmol of nitrate, 2-3 orders of magnitude less than previous offline thermal decomposition methods to achieve a similar analytical precision of 0.5 per thousand for Delta17O. There is no significant memory effect, but calibration via nitrate or N2O reference materials is required for scale normalization. The N2O decomposition method is shown to be well-suited for nitrate analysis in freshwater and seawater samples from various environments.     

Determination of the total oxygen isotopic composition of nitrate and the calibration of a delta 17O nitrate reference material

A thermal decomposition method was developed and tested for the simultaneous determination of delta 18O and delta 17O in nitrate. The thermal decomposition of AgNO3 allows for the rapid and accurate determination of 18O/ 16O and 17O/16O isotopic ratios with a precision of +/- 1.5 per thousand for delta 18O and +/- 0.11 per thousand for delta 17O (delta 17O = delta 17O - 0.52 x delta 18O). The international nitrate isotope reference material IAEA-NO3 yielded a delta 18O value of +23.6 per thousand and delta 17O of -0.2 per thousand, consistent with normal terrestrial mass-dependent isotopic ratios. In contrast, a large sample of NaNO3 from the Atacama Desert, Chile, was found to have delta 17O = 21.56 +/- 0.11 per thousand and delta 18O = 54.9 +/- 1.5 per thousand, demonstrating a substantial mass-independent isotopic composition consistent with the proposed atmospheric origin of the desert nitrate. It is suggested that this sample (designated USGS-35) can be used to generate other gases (CO2, CO, N2O, O2) with the same delta 17O to serve as measurement references for a variety of applications involving mass-independent isotopic compositions in environmental studies.     

Technical updates to the bacterial method for nitrate isotopic analyses

The bacterial conversion of aqueous nitrate (NO(3)(-)) to nitrous oxide (N(2)O) for isotopic analysis has found widespread use since its introduction (Sigman, D. M.; Casciotti, K. L.; Andreani, M.; Galanter, M.; Bo?hlke, J. K. Anal. Chem.2001, 73, 4145-4153; Casciotti, K. L.; Sigman, D. M.; Galanter Hastings, M.; Bo?hlke, J. K.; Hilkert, A. Anal. Chem.2002, 74, 4905-4912). The bacterial strain Pseudomonas aureofaciens (ATTC no. 13985) was shown to convert NO(3)(-) to N(2)O while retaining both N and O isotopic signatures, and automation of the isotopic analysis of N(2)O greatly increased the throughput of the method (Casciotti, K. L.; Sigman, D. M.; Galanter Hastings, M.; Bo?hlke, J. K.; Hilkert, A. Anal. Chem.2002, 74, 4905-4912). Continued development of the denitrifier method has led to increased precision and throughput of NO(3)(-) isotopic analysis. Presented here are several recent procedural modifications and the demonstration of their effectiveness.     

硝酸银电位滴定法测定外加剂中氯离子含量的不确定评定

依据JJF 1059-1999测量不确定度评定与表示,从试剂纯度、摩尔质量、电子天平称量、容量瓶、滴定管、移液管、酸度计、重复性测试等影响因素引入的不确定度分量,对以硝酸银溶液用电位滴定法测定外加剂中氯离子含量进行不确定度评估。分析了测定过程中不确定度来源,量化不确定度分量,求出了合成不确定度和扩展不确定度,给出了测定结果的表示式为(5.43±0.30)%,k=2。     

Precise determination of mass-dependent variations in the isotopic composition of molybdenum using MC-ICPMS

We present an analytical approach for the precise determination of mass-dependent differences in the isotopic composition of Mo between samples and reference standards using multiple-collector magnetic sector inductively coupled plasma mass spectrometry (MC-ICPMS). Either Zr or Ru "element spikes" are employed to correct for instrumental mass bias. Differences in 95Mo/97Mo can be determined to a precision of +/-0.2%o (+2sigma) using 1-10 microg of Mo. Similar precision is possible for other ratios after correction for isobaric interferences from either spike element. This approach facilitates study of mass-dependent variations in the isotopic composition of Mo in nature and in materials produced by laboratory processes. We observe fractionation of Mo isotopes of approximately 1.5%o/amu during ion-exchange chromatography in the laboratory and a shift of approximately 0.3%o/amu between natural MoS2 and a laboratory standard.     

Development and validation of a method to determine the boron isotopic composition of crop plants

We present a comprehensive chemical and mass spectrometric method to determine boron isotopic compositions of plant tissue. The method including dry ashing, a three-step ion chromatographic boron-matrix separation, and (11)B/(10)B isotope ratio determinations using the Cs(2)BO(2)(+) graphite technique has been validated using certified reference and quality control materials. The developed method is capable to determine δ(11)B values in plant tissue down to boron concentrations of 1 mg/kg with an expanded uncertainty of ≤1.7‰ (k = 2). The determined δ(11)B values reveal an enormous isotopic range of boron in plant tissues covering three-quarters of the natural terrestrial occurring variation in the boron isotopic composition. As the local environment and anthropogenic activity mainly control the boron intake of plants, the boron isotopic composition of plants can be used for food provenance studies.     

Measurement of oxygen recombination rate constants by the piezoelectric method

The piezoelectric method is used to measure pressure in a gas flow within a nozzle, measurement results are compared with calculation, and values of the oxygen atom recombination rate constant are obtained for the temperature range 1680–3250°K.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 53, No. 3, pp. 437–441, September, 1987.     

Evidence of a systematic deviation of the isotopic composition of neon from commercial sources compared with its isotopic composition in air

Results are reported of a study concerning the variation in isotopic composition of a limited number of neon samples of commercial origin and the resulting influence on the temperature of the triple point of this element. All seven neon samples investigated were found to contain more 22Ne than neon in air, and the amount fraction of 22Ne varied by as much as 0.2% from sample to sample. This variation corresponds to a range of triple-point temperatures (Ttp) of more than 200 microK, much larger than the state-of-the-art uncertainty in the realization of this phase transition for metrological purposes. Deviations in the amount fractions of 21Ne were irrelevant, as far as their effect on T(tp) is concerned, though they may have relevance to other isotope studies. Ratios of amounts of neon isotopes at IRMM-Geel were obtained using the same measurement procedures, and instrumentation developed in the framework of the redetermination of the Avogadro constant and all significant sources of uncertainty were taken into account. The repeatability of the ion current ratio measurements on individual samples was 5 x 10(-5) relative. All uncertainty statements are made following the ISO/BIPM Guide to the Expression of Uncertainty in Measurements. Whereas these results proved unexpected, a more comprehensive study will follow incorporating a much wider range of samples of commercial origin.     

Absolute isotopic composition and atomic weight of commercial zinc using inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry is introduced as a method for determining the absolute isotopic composition of zinc. The high ionization efficiency and time-independent characteristics of the mass spectrometry permit the absolute isotopic composition of high ionization potential elements. The mass discrimination of the instrument is calibrated by synthetic isotope mixtures prepared from highly enriched isotopes of zinc. The resulting isotope ratios yield atomic percents of 64Zn, 49.188 +/- 0.030; 66Zn, 27.792 +/- 0.041; 67Zn, 4.041 +/- 0.009; 68Zn, 18.378 +/- 0.050; and 70Zn, 0.600 +/- 0.003. This isotopic composition is different from those of conventional mass spectrometric measurements. Their differences depend on the mass differences about 0.8-1.2%/amu with enhancement of heavier isotopes. The atomic weight calculated from our isotopic composition is 65.3756 +/- 0.0040. The obtained atomic weight is fully consistent with that of a precise coulometric measurement in contrast to the previous mass spectrometric measurements. An isotopic variation of commercial zinc reagents has been investigated. A mass-dependent fractionation of 0.12%/amu is observed in a high-purity metal zinc, NIST-SRM 682, among five reagents. This mass dependence is probably inherited through their purification process.     

Measurement of low oxygen concentrations by phosphorescencelifetime using optical fibers

In this paper, a relatively simple, low-cost industrial prototype for measuring low oxygen concentrations in gaseous medium based on phosphorescence lifetime of Al-Ferron in sol-gel probe is presented. The main advantages over other techniques are an excellent sensitivity, precision, selectivity, response time, and facility of maintenance. Fiber optics is used to guide the light. This fact allows one to reach difficult places and to make the measurements from a distance. The design of the system and best ways to maximize the emission maximizing the excitation light from the light source, the optimal distance from the optical fibers to the chemical sensor, and a simple method to filter the response are discussed and verified with the prototype developed. The system allows the detection of oxygen concentrations of 0.005%     

Measurement of displacement and vibration by using the oblique ray method

An optical system that can measure vibrations and displacements is developed by using the oblique ray method. By employing a single convex lens that plays both roles of sending and receiving the beams that are reflected by the target surface, the optical measurement system became compact and reliable. A position-sensitive detector is used to measure the position change of the beam spot on the target surface. The resolution of the optical system can be controlled by changing the optical magnitude of the objective lens and is designed to be less than 0.1 microm for the developed system.     

The growth of non-stoichiometric apatites using the constant composition method

The kinetics of the crystal growth of calcium-deficient hydroxyapatites with different stoichiometry (Ca₅-(HPO₄)(PO₄)₃-(OH)₁-) have been investigated at 37°C using the constant composition method. The growth was performed in solutions supersaturated only with respect to Ca₅(PO₄)₃(OH) (HAp) by inoculating with well-characterized seed crystals. The stoichiometry of the grown apatites was consistent with values of 00.185. The deviation from HAp stoichiometry of the growing apatite increased with increasing supersaturation degree (S). The constant composition method also provides relevant information about the solubility behaviour of the growing phase with a definite composition. From the decrease of the normalized growth rate j with decreasing S, an estimate could be made of the composition of the solution for which the growth ceases. The determined solubility product of the grown apatite (4.28×10^-54 M⁹) was higher than the value obtained by the equilibration of the seed material. The results were interpreted on the basis of differences in crystal lattice perfection.This paper was accepted for publication after the 1995 Conference of the European Society of Biomaterials, Oporto, Portugal, 10–13 September.     

Measurement of region-specific nitrate levels of the posterior chamber of the rat eye using low-flow push-pull perfusion

The determination of the presence of nitric oxide metabolites in the rat vitreous cavity in a regioselective manner is complicated by the size and shape of the eye as well as the diffusivity of the molecule and its metabolites. In this work, in vivo low-flow push-pull perfusion sampling was utilized with a rapid capillary electrophoretic assay to monitor levels of the major NO metabolite, nitrate, at the vitreoretinal interface (VRI) of normal and aged rat models. The sampling probe tips were placed in three different positions in the posterior chamber through a 29-gauge guide needle. Sampling was performed along the VRI over the optic nerve head and regions peripheral to the optic nerve head. Additionally, samples were collected from the middle vitreous region to compare to VRI sampling. A significant (P < 0.05) difference in the perfusate nitrate concentration was observed in each location, which may be due to the source of NO production or the clearance mechanism of the molecule from the vitreous cavity. Infusion of L-NAME with physiological saline led to a significant decrease (35%) in the observed nitrate level. LFPPP was then utilized to observe nitrate levels after an average of 4.5 months of aging. A 3-fold increase in the mean level of nitrate over the optic nerve head was observed in mature animals compared to younger control animals. Precise measurement of NO metabolites along the VRI may provide insights into the function of NO in maintaining homeostatic conditions and the molecular changes at the diseased retina.     

Measurement of crack-profiles using AC field measurement method

The alternating current field measurement technique has been employed in the present study to predict cracks of different profiles. Profiles used included surface thumb-nail cracks of semi-circular, semi-elliptical, asymmetrical and rectangular shape with aspect ratios ranging from 2 to 10. From the potential ratios measured experimentally, a numerical approach was employed to compute the crack profiles. Crack profiles were also computed from theoretical potential profiles obtained using boundary element method. The present study shows that with high aspect ratios, the crack profiles predicted using theoretical data bore great resemblance to that of the actual. The underpredictions at the centre-line position of the cracks were small. Using experimentally measured potentials with 1-dimensional interpretation, all predicted profiles showed an under estimation of the actual. The errors appeared generally lower for the narrower plate and decreased with increase in aspect ratio. Pseudo-random errors were introduced to the theoretical potentials to simulate measurement errors that may occur in practice, to improve the error handling capability of the computer programme designed for the study. In addition, a smoothing technique was also applied to improve the accuracy of the crack profile prediction. By freezing some of the distant potential field, a significant computer processing time reduction of 25–35% has been achieved.     

The removal of nitrate by nanoscale iron particles produced using the sodium borohydride method

This study was conducted to investigate removal of nitrate by nanoscale zero-valent iron (ZVI) particles in aqueous solution. ZVI particles was produced from wasted acid that is by-products of a pickling line at a steel work. The reaction activity of ZVI particles was evaluated through decomposition experiments of NO3-N aqueous solution. Addition of a larger amount of ZVI particles resulted in a higher decomposition rate. ZVI particles showed higher decomposition efficiencies than commercially purchased ZVI particles at all pH values. Both ZVIs showed a higher decomposition rate at a lower pH. Virtually no decomposition reaction was observed at pH of 4 or higher for purchased ZVI. The ZVI particles produced directly from wasted acid by the sodium borohydride method were not easy to handle because they were very small (10-200 nm) and were oxidized easily in the air.     

Effect of dissolved oxygen concentration on nitrate removal from groundwater using a denitrifying submerged filter

A unidirectional submerged filter system was employed to purify groundwater contaminated with nitrate by biological denitrification. The influence of the concentration of dissolved oxygen (DO) in the process was tested using ethanol, methanol and sucrose as carbon sources. Inorganic-nitrogen removal, growth of the biofilm, platable denitrifying bacteria and nitrate reducing bacteria in biofilm were studied. With regard to the type of electron donor used, the presence of oxygen decreased the removal efficiency of inorganic nitrogen and caused an increase of nitrite concentration in the treated water. These negative effects depended on utilised carbon source. Biological denitrification with alcohols such as ethanol and methanol was less affected by DO than with sucrose. The development of the biofilm was also influenced by the DO concentration as excess O₂ caused reduced biofilm growth. These biofilms developed in oxygen presence had a smaller bacterial density and a lower denitrifying bacteria versus nitrate reducing bacteria ratio, which led to an unfavorable inorganic nitrogen removal and presence of nitrite in the treated water. All these effects are more pronounced when sucrose is used as carbon source.