Multi-tracer approach to understand nitrate contamination and groundwater-surface water interactions in the Mediterranean coastal area of Guerbes-Senhadja, Algeria.

Implementing sustainable groundwater resources management in coastal areas is challenging due to the negative impacts of anthropogenic stressors and various interactions between groundwater and surface water. This study focuses on nitrate contamination and transport via groundwater-surface water exchange in a Mediterranean coastal area (Guerbes-Senhadja region, Algeria) that is heavily affected by anthropogenic activities. A multi-tracer approach, integrating hydrogeochemical and isotopic tracers (δ2HH2O, δ18OH2O, 3H, δ15NNO3 and δ18ONO3), is combined with a Bayesian isotope mixing model (MixSIAR) to (i) elucidate the nitrate sources and their apportionments in water systems, and (ii) describe potential interactions between groundwater and surface water. Results from nitrate isotopic composition and the MixSIAR model show that nitrate concentrations mainly originate from sewage and manure sources. Nitrate derived from the sewage is attributed to urban and rural wastewater discharge, whereas nitrate derived from the manure is related to animal manure used to fertilise agricultural areas. High apportionments of nitrate-based atmospheric precipitation are identified in groundwater and surface water; a finding that is specific to this study. The multi-origin stresses combined with evidence of interactions between surface water and groundwater contribute to negatively impacting large parts of the study coastal area. The outcomes of this study are expected to contribute to sustainable management of coastal ecosystems by drawing more attention towards groundwater use and protection. Furthermore, this study may improve scientists' ability to predict the behavior of anthropogenically impacted coastal ecosystems and help decision-makers elsewhere to prepare suitable environmental strategies for other coastal ecosystems currently undergoing an early stage of groundwater resources deterioration.

Combined effects of seawater intrusion and nitrate contamination on groundwater in coastal agricultural areas: A case from the Plain of the El-Nil River (North-Eastern Algeria).

This study focuses on coastal aquifers subject to uncontrolled land use development by investigating the combined effects of seawater intrusion and nitrate contamination. The research is undertaken in a Mediterranean coastal agricultural area (Plain of the El-Nil River, Algeria), where water resources are heavily impacted by anthropogenic activities. A multi-tracer approach, integrating hydrogeochemical and isotopic tracers (δ2HH2O, δ18OH2O, δ15NNO3 and δ18ONO3), is combined with a hydrochemical facies evolution diagram, and a Bayesian isotope mixing model (MixSIAR) to assess seawater contamination with its inland intrusion, and distinguish the nitrate sources and their apportionment. Results show that seawater intrusion is circumscribed to the sector neighboring the Mediterranean Sea, with two influencing functions including classic inland intrusion through the aquifer, and upstream seawater impact through the river mouth connected to the Mediterranean Sea. Groundwater and surface water samples reveal nitrate concentrations above the natural baseline threshold, suggesting anthropogenic influence. Results from nitrate isotopic composition, NO3 and Cl concentrations, and the MixSIAR model show that nitrate concentrations chiefly originate from sewage and manure sources. Nitrate derived from the sewage is related to wastewater discharge, whereas nitrate derived from the manure is attributed to an excessive use of animal manure to fertilise agricultural areas. The dual negative impact of seawater intrusion and nitrate contamination degrades water quality over a large proportion of the study area. The outcomes of this study are expected to contribute to effective and sustainable water resources management in the Mediterranean coastal area. Furthermore, this study may improve scientists' ability to predict the combined effect of various anthropogenic stressors on coastal environments and help decision-makers elsewhere to prepare suitable environmental strategies for other regions currently undergoing an early stage of water resources deterioration.

Can groundwater sampling techniques used in monitoring wells influence methane concentrations and isotopes?

Methane concentrations and isotopic composition in groundwater are the focus of a growing number of studies. However, concerns are often expressed regarding the integrity of samples, as methane is very volatile and may partially exsolve during sample lifting in the well and transfer to sampling containers. While issues concerning bottle-filling techniques have already been documented, this paper documents a comparison of methane concentration and isotopic composition obtained with three devices commonly used to retrieve water samples from dedicated observation wells. This work lies within the framework of a larger project carried out in the Saint-Édouard area (southern Québec, Canada), whose objective was to assess the risk to shallow groundwater quality related to potential shale gas exploitation. The selected sampling devices, which were tested on ten wells during three sampling campaigns, consist of an impeller pump, a bladder pump, and disposable sampling bags (HydraSleeve). The sampling bags were used both before and after pumping, to verify the appropriateness of a no-purge approach, compared to the low-flow approach involving pumping until stabilization of field physicochemical parameters. Results show that methane concentrations obtained with the selected sampling techniques are usually similar and that there is no systematic bias related to a specific technique. Nonetheless, concentrations can sometimes vary quite significantly (up to 3.5 times) for a given well and sampling event. Methane isotopic composition obtained with all sampling techniques is very similar, except in some cases where sampling bags were used before pumping (no-purge approach), in wells where multiple groundwater sources enter the borehole.

Nitroglycerin degradation mediated by soil organic carbon under aerobic conditions.

The presence of nitroglycerin (NG) has been reported in shallow soils and pore water of several military training ranges. In this context, NG concentrations can be reduced through various natural attenuation processes, but these have not been thoroughly documented. This study aimed at investigating the role of soil organic matter (SOM) in the natural attenuation of NG, under aerobic conditions typical of shallow soils. The role of SOM in NG degradation has already been documented under anoxic conditions, and was attributed to SOM-mediated electron transfer involving different reducing agents. However, unsaturated soils are usually well-oxygenated, and it was not clear whether SOM could participate in NG degradation under these conditions. Our results from batch- and column-type experiments clearly demonstrate that in presence of dissolved organic matter (DOM) leached from a natural soil, partial NG degradation can be achieved. In presence of particulate organic matter (POM) from the same soil, complete NG degradation was achieved. Furthermore, POM caused rapid sorption of NG, which should result in NG retention in the organic matter-rich shallow horizons of the soil profile, thus promoting degradation. Based on degradation products, the reaction pathway appears to be reductive, in spite of the aerobic conditions. The relatively rapid reaction rates suggest that this process could significantly participate in the natural attenuation of NG, both on military training ranges and in contaminated soil at production facilities.

The use of alkaline hydrolysis as a novel strategy for chloroform remediation: the feasibility of using construction wastes and evaluation of carbon isotopic fractionation.

Laboratory and field-scale pilot experiments were performed to evaluate the feasibility of chloroform degradation by alkaline hydrolysis and the potential of δ(13)C values to assess this induced reaction process at contaminated sites. In batch experiments, alkaline conditions were induced by adding crushed concrete (pH 12.33 ± 0.07), a filtered concrete solution (pH 12.27 ± 0.04), a filtered cement solution (pH 12.66 ± 0.02) and a pH 12 buffer solution (pH 11.92 ± 0.11). The resulting chloroform degradation after 28 days was 94, 96, 99, and 72%, respectively. The experimental data were described using a pseudo-first-order kinetic model, resulting in pseudo-first-order rate constant values of 0.10, 0.12, 0.20, and 0.05 d(-1), respectively. Furthermore, the significant chloroform carbon isotopic fractionation associated with alkaline hydrolysis of chloroform (-53 ± 3‰) and its independence from pH in the admittedly limited tested pH range imply a great potential for the use of δ(13)C values for in situ monitoring of the efficacy of remediation approaches based on alkaline hydrolysis. The carbon isotopic fractionation obtained at the lab scale allowed the calculation of the percentage of chloroform degradation in field-scale pilot experiments where alkaline conditions were induced in two recharge water interception trenches filled with concrete-based construction wastes. A maximum of approximately 30-40% of chloroform degradation was achieved during the two studied recharge periods. Although further research is required, the treatment of chloroform in groundwater through the use of concrete-based construction wastes is proposed. This strategy would also imply the recycling of construction and demolition wastes for use in value-added applications to increase economic and environmental benefits.

Biodegradation of nitroglycerin from propellant residues on military training ranges.

Nitroglycerin (NG) is often present in soils and sometimes in pore water at antitank firing positions due to incomplete combustion of propellants. Various degradation processes can contribute to the natural attenuation of NG in soils and pore water, thus reducing the risks of groundwater contamination. However, until now these processes have been sparsely documented. This study aimed at evaluating the ability of microorganisms from a legacy firing position to degrade dissolved NG, as well as NG trapped within propellant particles. Results from the shake-flask experiments showed that the isolated culture is capable of degrading dissolved NG but not the nitrocellulose matrix of propellant particles, so that the deeply embedded NG molecules cannot be degraded. Furthermore, the results from column experiments showed that in a nutrient-poor sand, degradation of dissolved NG may not be sufficiently rapid to prevent groundwater contamination. Therefore, the results from this study indicate that, under favorable soil conditions, biodegradation can be an important natural attenuation process for NG dissolving out of fresh propellant residues. In contrast, biodegradation does not contribute to the long-term attenuation of NG within old, weathered propellant residues. Although NG in these old residues no longer poses a threat to groundwater quality, if soil clean-up of a legacy site is required, active remediation approaches should be sought.

Stable isotopes of nitrate reflect natural attenuation of propellant residues on military training ranges.

Nitroglycerin (NG) and nitrocellulose (NC) are constituents of double-base propellants used notably for firing antitank ammunitions. Nitroglycerin was detected in soil and water samples from the unsaturated zone (pore water) at an active antitank firing position, where the presence of high nitrate (NO3(-)) concentrations suggests that natural attenuation of NG is occurring. However, concentrations alone cannot assess if NG is the source of NO3(-), nor can they determine which degradation processes are involved. To address this issue, isotopic ratios (δ(15)N, δ(18)O) were measured for NO3(-) produced from NG and NC through various controlled degradation processes and compared with ratios measured in field pore water samples. Results indicate that propellant combustion and degradation mediated by soil organic carbon produced the observed NO3(-) in pore water at this site. Moreover, isotopic results are presented for NO3(-) produced through photolysis of propellant constituents, which could be a dominant process at other sites. The isotopic data presented here constitute novel information regarding a source of NO3(-) that was practically not documented before and a basis to study the contamination by energetic materials in different contexts.

Photolysis of RDX and nitroglycerin in the context of military training ranges.

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and nitroglycerin (NG) are two energetic materials commonly found in the environment on military training ranges. They are deposited on the ground in the form of solid particles, which can then dissolve in infiltration water or in surface water bodies. The objective of this study was to evaluate whether photolysis by sunlight can significantly contribute to the natural attenuation of RDX and NG (as solid particles or dissolved in surface water) at mid-northern latitudes, where training ranges of Canada and many European countries are located. Experiments conducted at 46.9°N show that both compounds are degraded by sunlight when dissolved in water, with half-lives between 1 and 120d, depending on the compound and time of year. Numerical models may be useful in predicting such photolysis rates, but the models should take into account current ozone levels, as older radiation datasets, collected before the ozone depletion observed since the late 1970s, underestimate the RDX/NG photolysis rate. For solid RDX or NG-bearing particles, photolysis is slower (half-lives of 2-4months), but the degradation rate is still rapid enough to make this process significant in a natural attenuation context. However, photolysis of NG embedded within solid propellant particles cannot proceed to completion, due to the stable nitrocellulose matrix of the propellant. Nonetheless, photolysis clearly constitutes an important attenuation mechanism that should be considered in conceptual models and included in numerical modeling efforts.

The fate and transport of nitroglycerin in the unsaturated zone at active and legacy anti-tank firing positions.

The environmental fate of nitroglycerin (NG) in the unsaturated zone was evaluated in the context of double-base propellant residue deposition at anti-tank training ranges. Fresh propellant residues were collected during live anti-tank training. Surface soils, sub-surface soils and water samples from the unsaturated zone were collected at an active anti-tank range, and at a legacy site where NG-based propellants have been used. Results show that the residues are composed of intact propellant particles, as well as small quantities of NG, dinitroglycerin (DNG) and nitrate which are rapidly dissolved by precipitation, resulting in sporadic pulses of those compounds in water from the unsaturated zone after rain/snow melt events. The dissolved NG and DNG can be progressively degraded in the unsaturated zone, releasing nitrate as an end-product. Over a period of several years, small propellant particles located at the soil surface can be carried downward through the soil pore system by infiltration water, which explains the presence of NG in sub-surface soils at the legacy site, more than 35 years after site closure. NG is no longer leached from these old particles, therefore the detection of NG in sub-surface soils does not signify that groundwater is at risk of contamination by NG.

Overestimation of nitrate and nitrite concentrations in water samples due to the presence of nitroglycerin or hexahydro-1,3,5-trinitro-1,3,5-triazine.

A large number of laboratory studies have reported nitrite (NO(2)(-)) and nitrate (NO(3)(-)) to be among the most common degradation products of the high explosives nitroglycerin (NG) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Additionally, several field studies have reported the presence of RDX or NG along with NO(3)(-) in groundwater near production plants. Most studies, however, did not specify whether their NO(2)(-) and NO(3)(-) analyses were performed on samples which also contained RDX or NG. Inconsistent NO(2)(-)/NO(3)(-) results obtained in our laboratory suggested that the presence of RDX or NG in water samples caused an overestimation of NO(2)(-) and NO(3)(-) concentrations when using two of the most common analytical methods, namely ionic chromatography and automated colorimetry. This could have important implications for mass balance calculations and for environmental decisions. This paper focused on quantifying the overestimation of NO(2)(-)/NO(3)(-) due to the presence of RDX and NG, and finding a method for extracting RDX and NG from water samples without affecting NO(2)(-)/NO(3)(-). Results showed that the overestimation can be predicted using regression coefficients; however the margin of error at the 95% confidence level was between 5 and 15%. Alternatively, a cartridge was found which retains both RDX and NG without affecting NO(2)(-)/NO(3)(-). The cartridge can be used for concentrating the RDX or NG in dilute environmental samples, while removing RDX/NG from solution to allow the interference-free analysis of NO(2)(-)/NO(3)(-). Additionally, if recovery of RDX/NG from the cartridges is not desired, the cartridges could be used for the extraction of more than one sample, thus reducing the costs.

Determination of the origin of groundwater nitrate at an air weapons range using the dual isotope approach.

Nitrate is one of the most common contaminants in shallow groundwater, and many sources may contribute to the nitrate load within an aquifer. Groundwater nitrate plumes have been detected at several ammunition production sites. However, the presence of multiple potential sources and the lack of existing isotopic data concerning explosive degradation-induced nitrate constitute a limitation when it comes to linking both types of contaminants. On military training ranges, high nitrate concentrations in groundwater were reported for the first time as part of the hydrogeological characterization of the Cold Lake Air Weapons Range (CLAWR), Alberta, Canada. Explosives degradation is thought to be the main source of nitrate contamination at CLAWR, as no other major source is present. Isotopic analyses of N and O in nitrate were performed on groundwater samples from the unconfined and confined aquifers; the dual isotopic analysis approach was used in order to increase the chances of identifying the source of nitrate. The isotopic ratios for the groundwater samples with low nitrate concentration suggested a natural origin with a strong contribution of anthropogenic atmospheric NOx. For the samples with nitrate concentration above the expected background level the isotopic ratios did not correspond to any source documented in the literature. Dissolved RDX samples were degraded in the laboratory and results showed that all reproduced degradation processes released nitrate with a strong fractionation. Laboratory isotopic values for RDX-derived NO(3)(-) produced a trend of high delta(18)O-low delta(15)N to low delta(18)O-high delta(15)N, and groundwater samples with nitrate concentrations above the expected background level appeared along this trend. Our results thus point toward a characteristic field of isotopic ratios for nitrate being derived from the degradation of RDX.

Environmental impacts of training activities at an air weapons range.

Within Canada, it has been recognized in the last decade that military training activities may have impacts on the environmental quality of training ranges. However, impacts of activities specific to Air Force Bases have not yet been intensely documented. A hydrogeological study was accomplished at the Cold Lake Air Weapons Range, Alberta, to evaluate the environmental impacts of using bombs, rockets, strafing, and open burning/open detonation (OB/OD) on the quality of soil, ground water, surface water, and lake sediments. Samples were analyzed for metals, anions, ammonium perchlorate (NH(4)ClO(4)), and energetic materials (EM). It was found that training activities did not result in measured values being exceeded on the basis of guidance values for surface water and lake sediments. Contamination by metals was mostly limited to soils, and some metals may be related to the use of bombs (Cd, Cu, Pb), strafe (Cu), and rockets (As, Ba, Cd, Cr, Cu, Fe, Ni, Pb, U, V, Zn). TNT (2,4,6-trinitrotoluene) was the main EM found in soils, while RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) was more common in ground water. Both are related to live bombing, while nitroglycerine (NG) is related to rocket use and was detected in soils only. Aluminum, nitrate, and ammonium perchlorate detected in ground water may be related to live bombing or rockets. OB/OD operations resulted in the presence of various EM in soils, and of perchlorate and nitrate in ground water. Contamination by metals and explosives in soils was localized around the targets and varied significantly in time; however, in ground water it was more constant and may persist for a period of several years after a target has been removed.