LC-MS analysis of nitroguanidine compounds by catalytic reduction using palladium modified graphitic carbon nitride catalyst.

The analysis of compounds of the nitroguanidine family at trace level poses an analytical challenge. Nitroguanidine, 1-methyl-3-nitroguanidine, and 1-methyl-3-nitro-1-nitrosoguanidine, which are addressed in this article, have low lipophilicity, with log(Kow) equal to -0.89, - 0.84, and 0.68, respectively, and as such are not amenable for preconcentration from water. Liquid-liquid extraction and SPE fail to concentrate them from water and it is also not possible to extract them by ion exchange resin even after a pH change. Nitroguanidine and 1-methyl-3-nitroguanidine nitramines are explosives of growing use and thereby growing environmental concern due to lower detonation sensitivity compared to RDX. A sensitive method for the determination of nitroguanidine, 1-methyl-3-nitroguanidine, and 1-methyl-3-nitroso-1-nitroguanidine by reduction to the respective amines and subsequent hydrophobization by derivatization with 4-nitrobenzaldehyde followed by LC-ESI-MS analysis is described. Reduction by sodium borohydride using palladium modified graphitic carbon nitride (Pd/g-C3N4) provided improved sensitivity compared to the traditional palladium modified activated carbon due to the lower adsorption of the reduction products on the carbon nitride substrate. The limit of detection of the method was 10 ng L-1 for nitroguanidine, and repeated analyses of spiked effluents and contaminated spring water gave relative standard deviations of 8.8% and 6.5%, respectively. The findings illuminate the great promise of Pd/g-C3N4 as a reduction catalyst for the determination of challenging hydrophilic organic contaminants.

Modeling sewage leakage and transport in carbonate aquifer using carbamazepine as an indicator.

The Western Mountain Aquifer (Yarkon-Taninim) of Israel is one of the country's major water resources and partially flows through a karst system. During late winter 2013, maintenance actions were performed on a central sewage pipe that caused sewage to leak into the creek located in the study area. Carbamazepine (CBZ) was used as an indicator for the presence of sewage in the groundwater. The research goal was to develop a mathematical model for quantifying flow and contaminant transport processes in the karst/fractured-porous unsaturated zone and groundwater system. The model was used to simulate CBZ transport during and after an observed sewage leakage event. A quasi-3D dual permeability numerical model represents the 'vadose zone - aquifer' system, by a series of 1D vertical flow and transport equations solved in a variably-saturated zone and by 3D-saturated flow and transport equation in groundwater. The results of simulation showed that after the leakage stopped, significant amounts of CBZ were retained in the porous matrix of the unsaturated zone below the creek. Water redistribution and slow recharge during the dry summer season contributed to a continuous supply of CBZ to the groundwater in the vicinity of the creek and hundreds of meters downstream.

Sensitive Analysis of Nitroguanidine in Aqueous and Soil Matrices by LC-MS.

Nitroguanidine, a widely used nitramine explosive, is an environmental contaminant that is refractory, persistent, highly mobile in soils and aquifers, and yet under-researched. Nitroguanidine determination in water and soil poses an analytical challenge due its high hydrophilicity, low volatility, charge neutrality over a wide pH range, and low proton affinity which results in low electrospray interface (ESI)-MS sensitivity. A sensitive method for the determination of nitroguanidine in aqueous and soil matrices was developed. The method is based on reduction by zinc in acidic solution, hydrophobization by derivatization, preconcentration on C18 cartridge, and LC-MS quantification. The demonstrated limit of detection (LOD) reaches 5 ng/L and 22 ng/g in water and soil, respectively. Analysis of a contaminated site demonstrates that it is possible to map a contamination plume that extends over 1 km from the source of the contamination.

Puddles - A trigger for heterogeneous chemical influx into the unsaturated zone.

Spatial heterogeneity in the chemical concentration of interstitial water in the vadose zone was previously observed under apparently homogeneous surface conditions on two leveled fields sprinkler irrigated with treated sewage effluents on the phreatic Coastal Plain aquifer of Israel. This phenomenon greatly hampers the monitoring of groundwater quality. In this study we report on the presence of puddles of different size and shape that were sporadically observed in these fields. Temporal variability noted in the concentration of treated sewage effluents components in the puddles were considered to be related to evapotranspiration and degradation. For example: increases in the electrical conductivity (up to 1.32 mS/cm), and in the concentrations of chloride (up to 521 mg/L), dissolved organic carbon (up to 28.4 mg/L), and carbamazepine (up to 780 ng/L) and decreases in the concentrations of nitrate (up to 20.1mg/L) and caffeine (3,396 ng/L). Variable trends in concentration were observed for sulfamethoxazole, venlafaxine, 10-hydroxy-10,11-dihydrocarbamazepine and o-desmethylvenlafaxine. The presence of puddles was not necessarily related to areas with high irrigation water input. It is postulated that the continuous chemical variability in the puddles, whose location and size are also variable, determine a heterogeneous influx of solutes into the soil and subsequently into the vadose zone.

Quantitative evaluation of tracers for quantification of wastewater contamination of potable water sources.

Quantitative criteria for selection of tracers for assessment of mixing of wastewater and pristine water are proposed and evaluated for leakage from a wastewater effluent recharge system to nearby pristine water wells and the dilution of the effluents in a reclamation well by pristine water from the surrounding aquifer. Two molecular tracers were compared: carbamazepine, an organic drug whose refractory behavior was evaluated on-site, and chloride, a widely used conservative tracer. The mixing ratios and the corresponding uncertainty levels in their calculation were evaluated using actual field data. Uncertainty level analysis illuminates the effects of the analytical errors in the determination of trace micropollutants on one hand and the high level of chloride in the background on the other. Uncertainty level calculations revealed that chloride is a somewhat better tracer for the estimation of the dilution of wastewater by flow from a pristine aquifer, whereas carbamazepine is a much better tracer for the calculation of wastewater contamination of nearby drinking water wells. Surprisingly, we show that even when carbamazepine degrades to a large and unknown extent, it can still be used to estimate accurately the probability that a site is contaminated by a wastewater stream.