ABSTRACT
BACKGROUND: Nitrite (NO2-) and nitrate (NO3-) can be produced in the distribution systems of chloraminated drinking water due to the nitrification of ammonia. The most applied inorganic chloramine for this purpose, namely monochloramine (NH2Cl), is also released into aquatic environments from water treatment plants' effluent and within industrial waste streams. Within the treatment process, the continuous monitoring of disinfectant levels is necessary to limit the harmful disinfectant by-product (DBP) formation. Currently, NH2Cl can interfere with nutrient analysis in water samples, and there are no analytical techniques available for the simultaneous analysis of NH2Cl, NO2-, and NO3-. RESULTS: A green analytical method based on mixed-mode ion chromatography, specifically ion exchange and ion exclusion modes, was developed for the simultaneous separation and detection of NH2Cl, NO2-, and NO3-. The separation was achieved using a Dionex IonPac AG15 column guard column and a step gradient elution involving deionized water and 120.0 mM NaCl. The method was developed using a benchtop HPLC with a custom-made multi-wavelength UV absorbance detector with a 50-mm flow cell to enable the sensitive detection of NH2Cl, NO2-, and NO3- at 240 nm, 220 nm, and 215 nm, respectively. The developed method was then transferred to a portable ion chromatography (IC) system, the Aquamonitrix analyser. The total run time was less than 10 min for both systems. The benchtop HPLC method had a limit of detection (LOD) of 0.07 µg mL-1 as Cl2 for NH2Cl, 0.01 µg mL-1 for NO2-, and 0.03 µg mL-1 for NO3-. The LODs obtained using the portable Aquamonitrix analyser were found to be 0.36 µg mL-1 as Cl2, 0.02 µg mL-1, and 0.11 µg mL-1 for NH2Cl, NO2-, and NO3-, respectively. Excellent linearity (r ≥ 0.9999) was achieved using the portable analyser over the studied concentration ranges. The developed system was applied to the analysis of spiked municipal drinking water samples and showed excellent repeatability for the three analytes at three different concentration levels (RSD of triplicate recovery experiments ≤ 1.9 %). Moreover, the variation in retention time was negligible for the three target analytes with RSD ≤ 0.8 % over 12 runs. SIGNIFICANCE: We are reporting the first ion chromatographic method for the simultaneous separation and detection of NH2Cl, NO2-, and NO3- in water samples. The monitoring of NH2Cl, NO2-, and NO3- is critical for the determination of disinfectant dosing, water quality, and nitrification status. The developed method can be applied using a benchtop HPLC or via the portable automated IC system to monitor for the three target compounds analysis in water treatment plants.
ABSTRACT
BACKGROUND: The on-site and simultaneous determination of anionic nitrite (NO2-) and nitrate (NO3-), and cationic ammonium (NH4+), in industrial and natural waters, presents a significant analytical challenge. Toward this end, herein a 3D-printed micro-reactor with an integrated heater chip was designed and optimised for the post-column colorimetric detection of NH4+ using a modified Berthelot reaction. The system was integrated within a portable and field deployable ion chromatograph (Aquamonitrix) designed to separate and detect NO2- and NO3-, but here enabled with dual LED-based absorbance detectors, with the aim to provide the first system capable of simultaneous determination of both anions and NH4+ in industrial and natural waters. RESULTS: Incorporating a 0.750 mm I.D. 3D-printed serpentine-based microchannel for sample-reagent mixing and heating, the resultant micro-reactor had a total reactor channel length of 1.26 m, which provided for a reaction time of 1.42 min based upon a total flow rate of 0.27 mL min-1, within a 40 mm2 printed area. The colorimetric reaction was performed within the micro-reactor, which was then coupled to a dedicated 660 nm LED-based absorbance detector. By rapidly delivering a reactor temperature of 70 °C in just 40 s, the optimal conditions to improve reaction kinetics were achieved to provide for limits of detection of 0.1 mg L-1 for NH4+, based upon an injection volume of just 10 µL. Linearity for NH4+ was observed over the range 0-50 mg L-1, n = 3, R2 = 0.9987. The reactor was found to deliver excellent reproducibility when included as a post-column reactor within the Aquamonitrix analyser, with an overall relative standard deviation below 1.2 % for peak height and 0.3 % for peak residence time, based upon 6 repeat injections. SIGNIFICANCE: The printed post-column reactor assembly was integrated into a commercial portable ion chromatograph developed for the separation and detection of NO2- and NO3-, thus providing a fully automated system for the remote and simultaneous analysis of NO2-, NO3-, and NH4+ in natural and industrial waters. The fully automated system was deployed externally within a greenhouse facility to demonstrate this capability.
ABSTRACT
Real-time monitoring of nitrite and nitrate is crucial for maintaining soil health and promoting plant growth. In this study, a portable ion-chromatograph (IC, Aquamonitrix) analyser, coupled with a field-applicable ultrasonic-assisted extraction method, was utilised for in-field determination of nitrate and nitrite in soils. This is the first application of this type of analyser to soil nutrients. On-site analysis of soil from a local sports field showed 94.8 ± 4.3 µg g-1 nitrate, with LODs of 32.0 µg g-1 for nitrate and 5.4 µg g-1 for nitrite. The results were in close agreement with those obtained using a conventional lab-based IC. Relative standard deviations (%RSDs) for soil analysis using Aquamonitrix were consistently below 10%. The obtained average recoveries of samples spiked with nitrite were 100% and 104% for the portable IC and conventional IC, respectively. Furthermore, to assess the suitability of portable IC for samples with high organic matter content, various natural organic fertilisers were extracted and analysed. The results showed 16.2 ± 0.7 µg g-1 nitrite and 28.5 ± 5.6 µg g-1 nitrate in sheep manure samples with LODs of 2.0 µg g-1 for nitrite and 12.0 µg g-1 for nitrate. The portable IC system was further demonstrated via real-time on-site analysis of soil pore-water acquired using a portable battery-based ceramic pore-water sampler. A continuous increase in nitrate concentration over time was observed (from 80 to 148 µg mL-1) in the soil pore-water in a vegetable garden four days after heavy rain. Unlike conventionally sampled natural waters, 7-day storage of the studied pore water samples revealed no changes in nitrate concentrations. An average of 558 ± 51 µg mL-1 nitrate was detected in the soil pore-water samples analysed on a spinach farm, immediately after irrigation.
ABSTRACT
The monosaccharide anhydrides levoglucosan, mannosan, and galactosan are known as 'fire sugars' as they are powerful proxies used to trace fire events. Despite their increasing use, their application is not completely understood, especially in the context of tracing past fire events using sediment samples. There are many uncertainties about fire sugar formation, partitioning, transport, complexation, and stability along all stages of the source-to-sink pathway. While these uncertainties exist, the efficacy of fire sugars as fire tracers remains limited. This study compared high-resolution fire sugar fluxes in freshwater sediment cores to known fire records in Tasmania, Australia. Past fire events correlated with fire sugar flux increases down-core, with the magnitude of the flux inversely proportional to the distance of the fires from the study site. For the first time, fire sugar ratios (levoglucosan/mannosan, L/M) in aerosols were compared with those in sediments from the same time-period. The L/M ratio in surface sediments (1.42-2.58) were significantly lower than in corresponding aerosols (5.08-15.62). We propose two hypotheses that may explain the lower average L/M of sediments. Firstly, the degradation rate of levoglucosan is higher than mannosan in the water column, sediment-water interface, and/or sediment. Secondly, the L/M ratio of non-atmospheric emissions during fires may be lower than that of atmospheric emissions from the same fire. Due to the uncertainties about transport partitioning (atmospheric versus non-atmospheric emissions) and fire sugar degradation along all stages of the source-to-sink pathway, we advise caution when inferring vegetation type (e.g. softwood, hardwood, or grasses) based purely on fire sugar ratios in sediments (e.g. L/M ratio). Future investigations are required to increase the efficacy of fire sugars as a complimentary, or standalone, fire tracer in sediments.