Automated system measuring triple oxygen and nitrogen isotope ratios in nitrate using the bacterial method and N2 O decomposition by microwave discharge.

RATIONALE: Triple oxygen and nitrogen isotope ratios in nitrate are powerful tools for assessing atmospheric nitrate formation pathways and their contribution to ecosystems. N2 O decomposition using microwave-induced plasma (MIP) has been used only for measurements of oxygen isotopes to date, but it is also possible to measure nitrogen isotopes during the same analytical run. METHODS: The main improvements to a previous system are (i) an automated distribution system of nitrate to the bacterial medium, (ii) N2 O separation by gas chromatography before N2 O decomposition using the MIP, (iii) use of a corundum tube for microwave discharge, and (iv) development of an automated system for isotopic measurements. Three nitrate standards with sample sizes of 60, 80, 100, and 120 nmol were measured to investigate the sample size dependence of the isotope measurements. RESULTS: The δ17 O, δ18 O, and Δ17 O values increased with increasing sample size, although the δ15 N value showed no significant size dependency. Different calibration slopes and intercepts were obtained with different sample amounts. The slopes and intercepts for the regression lines in different sample amounts were dependent on sample size, indicating that the extent of oxygen exchange is also dependent on sample size. The sample-size-dependent slopes and intercepts were fitted using natural log (ln) regression curves, and the slopes and intercepts can be estimated to apply to any sample size corrections. When using 100 nmol samples, the standard deviations of residuals from the regression lines for this system were 0.5‰, 0.3‰, and 0.1‰, respectively, for the δ18 O, Δ17 O, and δ15 N values, results that are not inferior to those from other systems using gold tube or gold wire. CONCLUSIONS: An automated system was developed to measure triple oxygen and nitrogen isotopes in nitrate using N2 O decomposition by MIP. This system enables us to measure both triple oxygen and nitrogen isotopes in nitrate with comparable precision and sample throughput (23 min per sample on average), and minimal manual treatment. Copyright © 2016 John Wiley & Sons, Ltd.

On-line triple oxygen isotope analysis of nitrous oxide using decomposition by microwave discharge.

RATIONALE: The oxygen isotope anomaly, Δ(17)O, of N2O and nitrate is useful to elucidate nitrogen oxide dynamics. The previously developed method for Δ(17)O measurement presents difficulty in maintaining optimal conditions of the gold tube for thermal decomposition of N2O to O2 and the Δ(17)O value is also sample size dependent. METHODS: Trace amounts (5-40 nmol) of N2O were decomposed quantitatively to O2 in a quartz tube by microwave discharge. The O2 was purified using gas chromatography. Triple oxygen isotopes were measured using isotope ratio mass spectrometry. Each step was connected online and was applied to the analysis of nitrate in precipitation samples collected in Yokohama, Japan. RESULTS: Precision (1σ) of Δ(17)O analysis was better than 0.26‰ when more than 20 nmol of N2O with a small Δ(17)O value (approx. 1‰) was measured. It was better than 0.76‰ when more than 60 nmol of nitrate was converted into N2O using the denitrifier method and then measured on the developed system. The obtained Δ(17)O values in precipitation samples (14.5-26.4‰) agreed with findings from previous studies. CONCLUSIONS: A novel on-line analytical method was developed to measure the triple oxygen isotopes of N2O using microwave discharge to decompose N2O. This easy-to-use method is free from conditioning of reaction devices, and is applicable to molecules other than N2O such as NO and NO2.

Experimental uncertainty assessment of meso- and microplastic concentrations in rivers based on net sampling.

Meso- and microplastics have been collected via net sampling in marine and freshwater environments, but the effect of net clogging on evaluations of their concentrations (mPC) remains uncertain. We experimentally investigated the mPC uncertainties resulting from net clogging in the Ohori and Tone-unga Rivers, typical urban rivers in Japan, throughout 16 samplings with five filtration durations in one day. The weighted mean concentration in the Ohori River was significantly lower than that in the Tone-unga River, allowing us to examine the effect of clogging in rivers with different contamination levels. The variances in both rivers consistently tended to increase with increasing filtration duration, which can be expressed by applying the integral form of the Weibull reliability function (WRF). Furthermore, application of the WRF successfully revealed the optimal filtration durations in the Ohori and Tone-unga Rivers, which depended on the plastic abundance and sample volume. Since it could be difficult to obtain the plastic contamination level in advance, our suggestion is to predict the time sustained above 85 % filtration efficiency by applying a WRF-based model. In actuality, the sustained time in the Ohori (Tone-unga) River varied between 2.6 and 6.2 min (3.2 and 7.1 min) throughout the experiment, which permitted low mPC uncertainties of 12 % and 9.5 %, respectively. If notable uncertainty exists due to a low contamination level, a net with a high open area ratio should be used to increase the filtration duration. Hence, our results emphasize the importance of considering the open area ratio of nets used for sampling in studies. Our study provides insights into the occurrence of uncertainty due to net clogging to establish a standardized methodology for meso- and microplastic monitoring in aquatic environments via net sampling and consequently contributes to improving the sampling accuracy.

Rapid analytical method for characterization and quantification of microplastics in tap water using a Fourier-transform infrared microscope.

Studies have recently focused on microplastics (MPs) in tap and drinking water. Directly comparing the results of different studies is difficult owing to the use of various methodologies. In particular, a study of particles on a part of the filter to reduce the analysis time can lead to uncertainty regarding the number of MPs in tap water. In this study, the analysis of particles on the whole filtration area using a Fourier-transform infrared (FTIR) microscope was achieved in approximately 1 h using a filtration unit with a smaller filtration area (0.13 cm2) and a large-opening (26 µm) filter. Forty-two samples collected from five countries were analyzed using this method. The concentrations of the MPs at each site ranged from 1.9 to 225 particles L-1, with a mean concentration of all samples of 39 ± 44 particles L-1. The size ranged from 19.2 µm to 4.2 mm. Fragments were the predominant shape while fibers and spheres were also observed. Based on a combination of the shape, size, and chemical composition of the MPs, we discussed their sources. The MPs could have caused contamination after processing by a water treatment plant because we detected a significant number of polyester fibers > 100 µm, which were previously detected in the air, and PVC fragments > 50 µm, which are often used in water pipes. This study proposed technical improvements to the whole filtration area technique to detect MPs in tap water.