Radiokrypton unveils dual moisture sources of a deep desert aquifer.

In arid regions, groundwater is a vital resource that can also provide a long-term record of the regional water cycle. However, the use of groundwater as a paleoclimate proxy has been limited by the complex hydrology and the lack of appropriate chronometers to determine the recharge time without complication. Applying 81Kr, a long-lived radioisotope tracer, we investigate the paleohydroclimate and subsurface water storage properties of the Nubian Sandstone Aquifer in the Negev Desert, Israel. Based on the spatial distributions of stable isotopes and the abundance of 81Kr, we resolve subsurface mixing and identify two distinct moisture sources of the recharge: one recent (<38 ky ago) from the Mediterranean and the other 361 ± 30 ky ago from the tropical Atlantic, both of which occurred under conditions of low orbital eccentricity comparable to that of the present. The recent recharge provided by the moisture from Mediterranean cyclones can be attributed to the southward shift of the storm track during the Last Glacial Maximum, and the earlier recharge can be attributed to moisture from the Atlantic delivered as tropical plumes under a climate colder than the present. Furthermore, the residence time of the latter reveals that tectonically active terrain can store groundwater for an unexpectedly long period, likely due to strongly attenuated groundwater flow across the fault zones. With this tracer, groundwater can now serve as a direct record of paleoprecipitation over land and of subsurface water storage from the mid-Pleistocene and onward.

Isolation and characterization of RDX-degrading Rhodococcus species from a contaminated aquifer.

Groundwater contamination by the explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a global problem. Israel's coastal aquifer was contaminated with RDX. This aquifer is mostly aerobic and we therefore sought aerobic bacteria that might be involved in natural attenuation of the compound in the aquifer. RDX-degrading bacteria were captured by passively sampling the indigenous bacteria onto sterile sediments placed within sampling boreholes. Aerobic RDX biodegradation potential was detected in the sediments sampled from different locations along the plume. RDX degradation with the native sampled consortium was accompanied by 4-nitro-2,4-diazabutanal formation. Two bacterial strains of the genus Rhodococcus were isolated from the sediments and identified as aerobic RDX degraders. The xplA gene encoding the cytochrome P450 enzyme was partially (~500 bp) sequenced from both isolates. The obtained DNA sequences had 99% identity with corresponding gene fragments of previously isolated RDX-degrading Rhodococcus strains. RDX degradation by both strains was prevented by 200 µM of the cytochrome P450 inhibitor metyrapone, suggesting that cytochrome P450 indeed mediates the initial step in RDX degradation. RDX biodegradation activity by the T7 isolate was inhibited in the presence of nitrate or ammonium concentrations above 1.6 and 5.5 mM, respectively (100 mg l(-1)) while the T9N isolate's activity was retarded only by ammonium concentrations above 5.5 mM. This study shows that bacteria from the genus Rhodococcus, potentially degrade RDX in the saturated zone as well, following the same aerobic degradation pathway defined for other Rhodococcus species. RDX-degrading activity by the Rhodococcus species isolate T9N may have important implications for the bioremediation of nitrate-rich RDX-contaminated aquifers.

Controls on the 36Cl/Cl input ratio of paleo-groundwater in arid environments: New evidence from 81Kr/Kr data.

Measurements of the long-lived 81Kr and 36Cl radioisotopes in groundwater from the Negev Desert (Israel) were used to assess the 36Cl/Cl input ratios and Cl- contents for paleorecharge into the Nubian Sandstone Aquifer (NSA). The reconstructed Cl- content of the recharge flux was on the order of 300-400 mg/L. An initial 36Cl/Cl ratio of 50 × 10-15 was assessed for the groundwater replenishment in the Negev Desert since the late Pleistocene, in agreement with the 36Cl/Cl ratios in recent local rainwater. This is despite possible changes in the climatic conditions and the 36Cl production rates in the atmosphere over this timeframe. This similarity in values is explained by the major role played by the erosion and weathering of near-surface materials in the desert environment that dominate the hydrochemistry of rains, floods, and the consequent groundwater recharge. Spatial variation in the reconstructed initial 36Cl/Cl ratio is accounted for by the differences in the mineral aerosol sources for specific recharge areas of the NSA. Accordingly, regional variations in the 36Cl/Cl input in groundwater reservoirs surrounding the Mediterranean Sea indicate various processes that govern the 36Cl/Cl system. Finally, the results of this study highlight the great advantage of integrating 81Kr age information in evaluating the initial 36Cl/Cl and Cl- input, which is essential for the calibration of 36Cl radioisotope as an available long-term dating tool for a given basin.

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.

Dilution tests in a low-permeability fractured aquifer: matrix diffusion effect.

A point dilution test is commonly used in single-borehole tracer experiments designed to determine the Darcy velocity of a formation. This method is based on the concept that, in a borehole, a tracer's concentration declines as a consequence of the water flux. Based on theoretical simulations and field observations, this study indicates that for low-permeability, yet highly porous fractured formations, the common practice of excluding the effect of diffusive mass flux between the dissolved tracer within the borehole and the surrounding matrix may lead to significant errors in the assessment of the Darcy velocity. This conclusion was confirmed by a model adapted to simulate experimental data collected from a tracer test performed in a vertical, large-diameter (25-cm) borehole drilled along a subvertical fracture intersecting a chalk formation.

Evaluation of soil flushing potential for clean-up of desert soil contaminated by industrial wastewater.

The flushing potential of a desert loess soil contaminated by the flame retardant Tetrabromobisphenol A (TBBPA), chloride (Cl(-)) and bromide (Br(-)) was studied in undisturbed laboratory column experiments (20 cm diameter, 45 cm long) and a small field plot (2 x 2 m). While the soluble inorganic ions (Cl(-) and Br(-)) were efficiently flushed from the soil profile after less than three pore volumes (PV) of water, about 50% of the initial amount of TBBPA in the soil was also flushed, despite its hydrophobic nature. TBBPA leaching was made possible due to a significant increase in the pH of the soil solution from 7.5 to 9, which increased TBBPA aqueous solubility. The remaining TBBPA mass in the soil was not mobilized from its initial location in the topsoil due to the decrease in pH at this horizon. In situ soil flushing demonstrated that this method is a feasible treatment for reducing soil contamination at this site.

Retardation of organo-bromides in a fractured chalk aquitard.

This study investigates the mechanisms controlling the distribution of 3-bromo-2,2-bis(bromomethyl)propanol (TBNPA) and 2,2-bis(bromomethyl)propan-1,3-diol (DBNPG) in a fractured chalk aquitard. An extensive monitoring program showed a systematic decrease in the TBNPA/DBNPG ratio with distance from the contamination source. Sorption of TBNPA on the white and/or gray chalks comprising the aquitard is approximately one order of magnitude greater than that of DBNPG. This results in more efficient removal of TBNPA from the fracture into the porous matrix and thus decreases the TBNPA/DBNPG ratio in the fracture water. Mathematical modeling of solute transport in the fracture domain illustrates the probable importance of sorption in controlling the spatial variation in TBNPA and DBNPG ratio.

Impact of microbial activity on the hydraulic properties of fractured chalk.

The impact of microbial activity on fractured chalk transmissivity was investigated on a laboratory scale. Long-term experiments were conducted on six fractured chalk cores (20 cm diameter, 23-44 cm long) containing a single natural fracture embedded in a porous matrix. Biodegradation experiments were conducted under various conditions, including several substrate and oxygen concentrations and flow rates. 2,4,6-Tribromophenol (TBP) was used as a model contaminant (substrate). TBP biodegradation efficiency depended mainly on the amount of oxygen. However, under constant oxygen concentration at the core inlet, elevating the flow rates increased the removal rate of TBP. Transmissivity reduction was clearly related to TBP removal rate, following an initial slow decline and a further sharp decrease with time. The fracture's transmissivity was reduced by as much as 97% relative to the initial value, with no leveling off of the clogging process. For the most extreme cases, reductions of 262 and 157 microm in the equivalent hydraulic apertures were recorded for fractures with initial apertures of 495 and 207 microm, respectively. The reductions in fracture transmissivity occurred primarily because of clogging by bacterial cells and extracellular polymeric substances (EPS) produced by the bacteria. Most of the biodegradation activity was concentrated near the fracture inlet, where the most suitable biodegradation conditions (nutrients and oxygen) prevailed, suggesting that the clogging had occurred in that vicinity. The clogging must have changed the structure of the fracture void, thereby reducing the active volume participating in flow and transport processes. This phenomenon caused accelerated transport of non-reactive tracers and doubled the fracture's dispersivity under constant flow rates.

Two-dimensional distribution of microbial activity and flow patterns within naturally fractured chalk.

The two-dimensional distribution of flow patterns and their dynamic change due to microbial activity were investigated in naturally fractured chalk cores. Long-term biodegradation experiments were conducted in two cores ( approximately 20 cm diameter, 31 and 44 cm long), intersected by a natural fracture. 2,4,6-tribromophenol (TBP) was used as a model contaminant and as the sole carbon source for aerobic microbial activity. The transmissivity of the fractures was continuously reduced due to biomass accumulation in the fracture concurrent with TBP biodegradation. From multi-tracer experiments conducted prior to and following the microbial activity, it was found that biomass accumulation causes redistribution of the preferential flow channels. Zones of slow flow near the fracture inlet were clogged, thus further diverting the flow through zones of fast flow, which were also partially clogged. Quantitative evaluation of biodegradation and bacterial counts supported the results of the multi-tracer tests, indicating that most of the bacterial activity occurs close to the inlet. The changing flow patterns, which control the nutrient supply, resulted in variations in the concentrations of the chemical constituents (TBP, bromide and oxygen), used as indicators of biodegradation.

Correlating fracture trends and hydraulic head using semivariogram cloud analysis.

Fracture trends (defined as kilometer-scale linear features interpolated between field observations of fractures along their strikes) often have a dominant orientation. Finding a correlation between this orientation and hydraulic data could shed light on their hydraulic influence. A significant correlation between head residuals from first-order regional drift and the orientation of 2- to 4-km-long fracture trends was found in a study site in the Negev, Israel, using the semivariogram cloud analysis. Correlation of head residuals rather than the head itself implies that the orientation of the fracture trends controls the anisotropy and heterogeneity at this scale, mainly because the fracture trends define the orientation of blocks, which differ in their hydraulic properties. Preferential transmissive pathways are probably shorter than the full extent of the fracture trends, causing a relatively high head difference along the trends on the 2- to 4-km scale. Fracture trend density and additional data from short-range hydraulic tests helped characterize two blocks separated by a fault zone. The identification of hydraulic features on a kilometer scale is necessary for better modeling of regional ground water flow and transport. Hydraulic tests at this scale are not feasible, thereby rendering combined analyses of head and structural data, such as the one presented here, essential.

Isotopes as tracers in a contaminated fractured chalk aquitard.

Clusters of industrial plants often generate contaminant plumes with several potential sources. Prevention of further pollution and designing suitable remedial measures require identification of the contributing source among all potential ones and the sorting of currently active sources from historical ones. In the study area, an industrial complex in the Negev desert, Israel, contaminants could not serve as indicators for the contamination sources because of their extensive spatial distribution across the site. However, stable isotopes of oxygen, hydrogen and sulfur, as well as tritium, proved to be efficient tools for this task. The isotopic characterization of the potential end members provided the criteria for constraining a contaminating source when several alternative sources appeared viable. The isotopic fractionation of oxygen and hydrogen isotopes could be tied to the various disposal phases of the industrial wastewater. The three case studies presented here confirm the important role of isotopes as tracers in contaminated sites.

Particle transport in unsaturated fractured chalk under arid conditions.

A series of field and laboratory experiments were conducted to study the mechanisms of particle detachment and transport from fractures in vadose chalk. Experiments of intermittent flow events along fracture surfaces were carried out in the laboratory. In the field, water was percolated from land surface via a discrete fracture into a compartmental sampler installed inside a horizontal corehole located I m below the surface. The mass, size distribution, and composition of the particles drained from the fracture voids were examined along with flow rates and salt dissolution. Two boreholes penetrating the underlying saturated zone were sampled and analyzed for colloidal concentration and composition. Most of the particle and solute release at the drained effluents occurred during the first several hours of flow, but erratic pulses of particles were still observed after long periods of time. Most of the detached particles had a mean diameter of >2 microm, while the mobile colloidal phase in the groundwater had a mean diameter of approximately 1 microm. Mineralogical composition of the groundwater colloids and the particles detached from the upper vadose fracture were similar. Laboratory observations demonstrated the importance of the existence of a coating layer, made of weathered particles and salts, on particle detachment. The results of this study suggest that: (1) particle detachment causes flow-rate variability in the unsaturated fracture; (2) the mechanisms of particle detachment and salt dissolution within the fracture are linked: and (3) although most of the detached particles are large and likely to accumulate inside fractures, some colloidal particles also eroded from the fracture void and are likely to be transported to the groundwater.

Characterization of the hydraulic properties of fractures in chalk.

The fracture systems intersecting Eocene chalk formations in the Negev desert, Israel, and their hydraulic properties were characterized using a variety of geologic and hydrologic techniques. These included identification of the prevailing directions of fracture systems in outcrops, in cores retrieved from inclined coreholes, in coreholes using video logs, and in trenches. The orientation and inclination of these fracture systems were determined, and evidence of ground water flow on the fracture surfaces was described and ranked. Their hydraulic conductivity was determined through slug and pumping tests performed at discrete intervals. Temperature, electrical conductivity, caliper, gamma and heat-pulse logs were conducted in the same coreholes. The results from the logs, tests, and core descriptions were compared to identify reliable and cost-effective tools for investigating the hydraulic characteristics of fracture systems. We concluded that in the study area: (1) fracture mapping in outcrops and coreholes (including downhole video and caliper logs) must be supplemented by hydraulic testing of the mapped fracture sets in the coreholes; (2) inclined coreholes provide information regarding the orientation of the hydraulically active fracture systems that cannot be obtained from vertical boreholes; (3) hydraulic testing of unpacked holes provides a reasonable estimate of the maximum hydraulic conductivity; and (4) the hydraulic conductivity distribution with depth is log normal and all significant ground water flow takes place within the upper 25 m.

Progressive development of water resources in the Middle East for sustainable water supply in a period of climate change.

The history of the Middle East has been influenced by past global climatic changes. Warm periods caused droughts, resulting in desertification, migration and war. Cold periods were humid and brought prosperity and agricultural settlement to the desert fringes. The forecast based on this correlation is that the present global warming will cause the drying up of the Middle East. As in the past, this negative impact should be mitigated by using the groundwater resources stored from past wetter times. This will involve deep drilling, pumping and modern irrigation methods within the framework of a new policy of 'progressive development', which will entail the use of currently undeveloped natural water resources beyond that of present water replenishment. While the use of the one-time groundwater reserves is taking place, a master long-term comprehensive progressive development plan for the Middle East will be prepared. This plan will include the step-by-step development of other water resources such as treated effluents, desalinated brackish groundwater and desalination of seawater.

Greywater reuse for irrigation: effect on soil properties.

A controlled study of the effect of greywater (GW) irrigation on soil properties was conducted. Containers of sand, loam and loess soils were planted with lettuce, and irrigated with fresh water, raw artificial GW or treated artificial GW. Greywater was treated using a recirculating vertical-flow constructed wetland. Soil samples were collected every 10 days for the 40-day duration of the study, and plant growth was measured. Soils were analysed for physicochemical and biological parameters to determine changes caused by the different treatments. It was demonstrated that raw artificial GW significantly increased the development of hydrophobicity in the sand and loam soils, as determined by water droplet penetration time. No significant changes were observed for the loess soil under all treatments. Observed hydrophobicity was correlated with increased oil and grease and surfactant concentrations in the soil. Zeta (zeta) potential of the soils was measured to determine changes in the soil particle surface properties as a result of GW irrigation. A significant change in zeta-potential (less negative) was observed in the raw artificial GW-irrigated sand, whereas no difference was observed in the loam or loess. Soils irrigated with fresh water or treated GW exhibited no increase in hydrophobicity. Fecal coliform bacteria were absent or <10 CFU g(-1) in soils irrigated with fresh water or treated GW, but at least 1 order of magnitude higher in raw artificial GW irrigated soils. Only in the last sampling event and only for the loess soil was plant growth significantly higher for fresh water irrigated vs. raw or treated GW irrigated soils. This study demonstrates that treated GW can be effectively irrigated without detrimental effects on soil or plant growth; however, raw GW may significantly change soil properties that can impact the movement of water in soil and the transport of contaminants in the vadose zone.

Chemical degradation of 2,2-bis(bromomethyl)propan-1,3-diol (DBNPG) in alkaline conditions.

The mechanism and kinetics of the spontaneous decomposition of 2,2-bis(bromomethyl)propan-1,3-diol (DBNPG) and its decomposition daughter products were determined in aqueous solution at a temperatures range between 30 and 70 degrees C and pH from 7.0 to 9.5. DBNPG decomposition in basic aqueous solutions involves release of bromide ions through a sequential formation of 3-bromomethyl-3-hydroxymethyloxetane (BMHMO) and 2,6-dioxaspiro[3.3]heptane (DOH). DBNPG decomposition into BMHMO is a two-stage reaction. The first stage is an acid/base equilibrium, in which an alkoxide is formed. In the second stage, DBNPG predominantly undergoes an intramolecular nucleophilic substitution to form the BMHMO. The transformation rate increases with the pH and the energy barrier for the degradation is 98 kJ mol(-1). Good agreement was found between the rate coefficients derived from variations in the organic molecules concentrations and those determined from the changes in the Br(-) concentration. DBNPG is one of the most abundant pollutants in a studied polluted aquitard underneath industrial park in the northern Negev, Israel, and together with its by-products pose an environmental hazard. DBNPG half-life is estimated to be about 65 years. This implies that high concentrations of DBNPG will persist in the aquifer long after the elimination of all its sources.

Quantifying RDX biodegradation in groundwater using delta15N isotope analysis.

Isotope analysis was used to examine the extent of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) biodegradation in groundwater along a ca. 1.35-km contamination plume. Biodegradation was proposed as a natural attenuating remediation method for the contaminated aquifer. By isotope analysis of RDX, the extent of biodegradation was found to reach up to 99.5% of the initial mass at a distance of 1.15-1.35km down gradient from the contamination sources. A range of first-order biodegradation rates was calculated based on the degradation extents, with average half-life values ranging between 4.4 and 12.8years for RDX biodegradation in the upper 15m of the aquifer, assuming purely aerobic biodegradation, and between 10.9 and 31.2years, assuming purely anaerobic biodegradation. Based on the geochemical data, an aerobic biodegradation pathway was suggested as the dominant attenuation process at the site. The calculated biodegradation rate was correlated with depth, showing decreasing degradation rates in deeper groundwater layers. Exceptionally low first-order kinetic constants were found in a borehole penetrating the bottom of the aquifer, with half life ranging between 85.0 to 161.5years, assuming purely aerobic biodegradation, and between 207.5 and 394.3years, assuming purely anaerobic biodegradation. The study showed that stable isotope fractionation analysis is a suitable tool to detect biodegradation of RDX in the environment. Our findings clearly indicated that RDX is naturally biodegraded in the contaminated aquifer. To the best of our knowledge, this is the first reported use of RDX isotope analysis to quantify its biodegradation in contaminated aquifers.

Metabolism of the explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in a contaminated vadose zone.

The aim of this study was to explore biodegradation potential of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in a deep contaminated unsaturated zone over Israel's coastal aquifer. While anaerobic biodegradation potential was observed throughout the profile down to the water table at a depth of 45 m, aerobic biodegradation was limited to the surface of the unsaturated zone. Traces of nitroso-RDX intermediates were detected in the soil samples, indicating possible in situ activity. Polymerase chain reaction and denaturing gradient gel electrophoresis analysis revealed that the microbial population in the soil consisted of protobacteria, but no known RDX degraders were detected. However, a 16S rRNA gene sequence most similar to Sphingomonas sp. was detected at all depths. Biodegradation rates were faster in the surface (0 and 1m) versus deeper soil samples (22 and 45 m) and were not affected under anaerobic conditions by the presence of nitrate, indicating a concurrent reduction of both compounds. RDX half-life in the surface soil was mostly dependent on carbon content and to lesser extent on soil moisture. Biomineralization of RDX to CO(2) was confirmed by incubating surface soil with (14)C-labeled RDX. An aerobic RDX-degrading bacterium, identified as Gordonia sp., was isolated from the soil: it degraded RDX aerobically and produced 4-nitro-2,4-diazabutanal. This study, the first to explore RDX biodegradation in the deep vadoze zone, indicates biodegradation potential throughout the profile, which is likely to support natural attenuation.

Compound-specific isotope analysis of RDX and stable isotope fractionation during aerobic and anaerobic biodegradation.

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a common contaminant at explosives production sites. Here, we report on the use of compound-specific isotope analysis of RDX to obtain delta(15)N and delta(18)O enrichment factors during biodegradation in batch cultures. A new preparation method has been developed based on RDX purification using thin-layer chromatography. RDX is then subjected to an elemental analyzer coupled with an isotope-ratio mass spectrometer (EA-IRMS). The precision of the method shows standard deviations of 0.13% per hundred and 1.18% per hundred for delta(15)N and delta(18)O, respectively, whereas the accuracy of the method has been checked routinely, adhering to external standards. The method was applied to RDX samples subjected to biodegradation under aerobic or anaerobic conditions. Enrichment factors under aerobic conditions were -2.1% per hundred and -1.7% per hundred for delta(15)N and delta(18)O, respectively, and under anaerobic conditions, -5.0% per hundred and -5.3% per hundred for delta(15)N and delta(18)O, respectively. The results of this study provide a tool for monitoring natural attenuation of RDX in a contaminated environment.

Biodegradation of 2,4,6-tribromophenol during transport in fractured chalk.

The effect of physicochemical conditions (residence time, oxygen concentrations, and chalk characteristics) on the biodegradation of 2,4,6-tribromophenol (TBP) during transport was investigated in low-permeability fractured-chalk cores. Long-term (approximately 600 d) biodegradation experiments were conducted in two cores (approximately 21 cm diameter, 31 and 44 cm long, respectively), intersected by a natural fracture. TBP was used as a model contaminant and as the sole carbon source for aerobic microbial activity. Bacterial isolates were recovered and identified by both Biolog identification kit and 16S rDNA sequences from batch enrichment cultures. One of the strains, with 98% similarity (based on the 16S rDNA data) to Achromobacter xylosoxidans, was shown to have the ability to degrade TBP in the presence of chalk. The decrease in TBP concentration along the fracture due to biodegradation was not affected by reducing the residence time from 49 to 8 min. In contrast, adding oxygen to the water at the inlet and increasing the flow rates improved TBP removal. Although the matrix pore-size distribution limits microbial activity to the fracture void, the chalk appears to provide an excellent environment for biodegradation activity. Approximately 90% of TBP removal occurred within 10 cm of the TBP source, indicating that in-situ bioremediation can be used to remove organic contaminants in low-permeability fractured rocks if nutrient-delivery pathways within the aquifer are secured.