Integration of groundwater vulnerability with contaminants transport modeling in unsaturated zone, case study El-Sharqia, Egypt.

Nowadays, irrigation uses large amount of marginal wastewater due to continuous decline in fresh water supply. As a consequence, using this wastewater for different purposes can cause some adverse environmental impacts. Anthropogenic activities such as septic tanks, sewage ponds, and polluted drains have large influence on deterioration of shallow groundwater aquifers. So, construction of many wastewater treatment plants in these areas is mandatory to control and mitigate this deterioration. Groundwater vulnerability assessment maps and contamination simulation in unsaturated zone can be beneficial in understanding contaminants pathways and groundwater quality evolution. This work is mainly focused on aquifer vulnerability assessment to pollution and the role of vadose zone in attenuation of contaminants transport through it prior to groundwater seepage. Therefore, about 56 drainage and groundwater samples were collected and analyzed for potentially toxic elements. The most vulnerable sector was determined using GOD method revealing that central parts of the study area are the most threatened zones with some scattered sporadic zone of sensitivity to pollution and this was verified through the zonation of Pb, Fe, and Mn spatial concentrations. The leakage of these elements through the unsaturated zone was further simulated using HYDRUS-1D model for the next 10-year period to determine the extent of the pollution plumes and maximum concentration of these elements that percolate to the groundwater directly. The concentration of Fe, Pb, and Mn at the end of the simulation reached low concentrations at the bottom layer of the unsaturated zone.

Construction, application and validation of a new algorithm for determining light nonaqueous-phase liquid fluxes in unsaturated zones.

An analytical algorithm coupling free-phase migration, precipitation, and natural attenuation through volatilization and biodegradation (FPVB) was developed to calculate the flux of light nonaqueous-phase liquid (LNAPL) leaking from unsaturated zone to groundwater. Sandbox and soil column experiments were performed to identify the LNAPL migration characteristics and states to provide data to establish and verify FPVB algorithm. For free-phase migration, the Kinematic Oily Pollutant Transport (KOPT) model was used to determine LNAPL movement velocity and leakage time. The correlations of water saturation, residual LNAPL saturation and the cumulative dissolution ratio of residual LNAPL were described using an empirical formula for the precipitation leaching process. Equations for diesel volatilization kinetics and first order degradation were used to describe the natural attenuation processes. Coupling the algorithms for the different stages gave the final FPVB algorithm. The FPVB algorithm was used to describe the pollution situation at a real site, and the results were consistent with the actual situation. The FPVB algorithm could be used to quickly assess the scale and degree of pollution with little information on the parameters for the actual LNAPL leakage event.

A comparison of measured and predicted diffusion coefficients applied to sand and silt sized acid mine drainage materials.

Determining the rate at which Acid Mine Drainage (AMD) sulfide oxidation occurs in mining waste products is a central requirement for safe and sustainable long term design of storages, including tails storage facilities, ore stockpiles and waste rock dumps. Inappropriate design can result in AMD acidification, mobilisation of heavy metals and pollution of ground and surface waters. The use of soil gas (oxygen) transport modelling to model AMD based sulfide oxidation and potential acidity loads is widespread, but diffusion coefficients used for modelling are based on existing diffusion coefficient models derived for natural and agricultural soils. Mining wastes are often well sorted due to mineral processing, and differences in soil structure and porosity can impact on diffusion coefficient behaviour compared to natural soils. This study compares a variety of approaches to estimate the diffusion coefficient and compare these results to measured values for comparison and analysis. A diffusion column apparatus is used to compare diffusion coefficient models from the literature with test results from the laboratory in several mining derived AMD materials. The results of the comparison indicate that laboratory testing of diffusion provides more accurate estimation of soil gas diffusion coefficients in mine materials. The use of diffusion coefficient safety factor approaches are explored as possible alternatives, if measurement of mine material matrix soil gas diffusion coefficient is not possible.

Investigation of 3H, 99Tc, and 90Sr transport in fractured rock and the effects of fracture-filling/coating material at LILW disposal facility.

Batch adsorption, batch diffusion, and flow-through column experiments were conducted using groundwater and fractured rock collected in unsaturated zone to increase our understanding of sorption and transport behavior of radionuclides. Increasing Kd values were observed in the sequence 90Sr, 99Tc, and 3H regardless of the geological media tested. For all sorbing radionuclides, Kd values for the fracture-filling/coating material were observed to be higher than those for without fracture-filling/coating material regardless of the groundwater. These higher Kd values are the result of zeolite mineral in filling/coating material of fractured rock. The batch diffusion and flow-through column experiments were also conducted using the same fractured rock sample, and the results of diffusion and column experiments showed similar trend of radionuclide sorption and transport to sorption experiment. In this study, sorption Kd of radionuclide was determined and used to increase our understanding of radionuclide retardation through fracture-filling/coating materials.

Nitrogen removal efficiencies and pathways from unsaturated and saturated zones in a laboratory-scale vertical flow constructed wetland.

A laboratory-scale vertical flow constructed wetland system was designed and monitored to compare nitrogen removal rates and pathways from both saturated and unsaturated zones under a hydraulic loading rate and influent total nitrogen concentration of 1.5 m3/m2.d and 508 mg/L respectively. Weekly measurements of the concentrations of nitrogen compounds, chemical oxygen demand, temperature, dissolved oxygen, oxidation-reduction potential, and hydrogen ion concentration were taken throughout the study. At the end of the experiments, PCR analysis of 16S rRNA gene sequencing was performed to identify microbial communities in the unsaturated and saturated parts of the system. The nitrogen compounds were removed from the system after 182 days, with similar total nitrogen removal efficiencies (94% and 93%) for the unsaturated and saturated zones respectively. Heterotrophic nitrification/aerobic denitrification was the major pathway responsible for the removal of nitrogen compounds. Adsorption into the gravel bed also contributed to ammonium removal. Proteobacteria were the dominant bacterial strains involved in nitrogen transformation and accounted for 80% of the total bacteria in the unsaturated zone and 60% in the saturated zone. With little difference in the concentration removal efficiencies of the unsaturated and saturated zones, a more effective design would be an entirely saturated wetland as the total mass removal of nitrogen depends on the water volume stored, which at full saturation in this design was seven times greater per unit wetland volume than the unsaturated zone.

Geophysical and hydrological data assimilation to monitor water content dynamics in the rocky unsaturated zone.

In recent years, geophysics is increasingly used to study the flow and transport processes in the vadose zone. Particularly, when the vadose zone is made up of rocks, it is difficult to install sensors in the subsurface to measure hydrological state variables directly. In these cases, the electrical resistivity tomography (ERT) represents a useful tool to monitor the hydrodynamics of the infiltration and to estimate hydraulic parameters and state variables, such as hydraulic conductivity and water content. We propose an integrated approach aimed at predicting water content dynamics in calcarenite, a sedimentary carbonatic porous rock. The uncoupled hydrogeophysical approach proposed consists in 4D ERT monitoring conducted during an infiltrometer test under falling head conditions. Capacitance probes were installed to measure water content at different depths to validate the estimations derived from ERT. A numerical procedure, based on a data assimilation technique, was accomplished by combining the model (i.e., Richards' equation) with the observations in order to provide reliable water content estimations. We have used a new data assimilation method that is easy to implement, based on the ensemble Kalman filter coupled with Brownian bridges. This approach is particularly suitable for strongly non-linear models, such as Richards' equation, in order to take into account both the model uncertainty and the observation errors. The proposed data assimilation approach was tested for the first time on field data. A reasonable agreement was found between observations and predictions confirming the ability of the integrated approach to predict water content dynamics in the rocky subsoil.

Modeling interactions between saturated and un-saturated zones by Hydrus-1D in semi-arid regions (plain of Kairouan, Central Tunisia).

In semi-arid areas like the Kairouan region, salinization has become an increasing concern because of the constant irrigation with saline water and over use of groundwater resources, soils, and aquifers. In this study, a methodology has been developed to evaluate groundwater contamination risk based on the unsaturated zone hydraulic properties. Two soil profiles with different ranges of salinity, one located in the north of the plain and another one in the south of plain (each 30 m deep) and both characterized by direct recharge of the aquifer, were chosen. Simulations were conducted with Hydrus-1D code using measured precipitation data for the period 1998-2003 and calculated evapotranspiration for both chosen profiles. Four combinations of initial conditions of water content and salt concentration were used for the simulation process in order to find the best match between simulated and measured values. The success of the calibration of Hydrus-1D allowed the investigation of some scenarios in order to assess the contamination risk under different natural conditions. The aquifer risk contamination is related to the natural conditions where it increased while facing climate change and temperature increase and decreased in the presence of a clay layer. Hydrus-1D was a useful tool to predict the groundwater level and quality in the case of a direct recharge and in the absence of any information related to the soil layers except for the texture.

Evaluation of a horizontal permeable reactive barrier for preventing upward diffusion of volatile organic compounds through the unsaturated zone.

Permeable reactive barriers are commonly used to treat contaminant plumes in the saturated zone. However, no known applications of horizontal permeable reactive barriers (HPRBs) exist for oxidizing volatile organic compounds (VOCs) in the unsaturated zone. In this study, laboratory column experiments were carried out to investigate the ability of a HPRB containing solid potassium permanganate, to oxidize the vapors of trichloroethylene (TCE), toluene, and ethanol migrating upward from a contaminated saturated zone. Results revealed that an increase in initial water saturation and HPRB thickness strongly affected the removal efficiency of the HPRB. Installing the HPRB relatively close to the water table was more effective due to the high background water content and enhanced diffusion of protons and/or hydroxides away from the HPRB. Inserting the HPRB far above the water table caused rapid changes in pH within the HPRB, leading to lower oxidation rates. The pH effects were included in a reactive transport model, which successfully simulated the TCE and toluene experimental observations. Simulations for ethanol were not affected by pH due to condensation of water during ethanol oxidation, which caused some dilution in the HRPB.

Per- and polyfluoroalkyl substances (PFAS) as contaminants in groundwater resources - A comprehensive review of subsurface transport processes.

Per- and polyfluorinated alkyl substances (PFAS) are persistent contaminants in the environment. An increased awareness of adverse health effects related to PFAS has further led to stricter regulations for several of these substances in e.g. drinking water in many countries. Groundwater constitutes an important source of raw water for drinking water production. A thorough understanding of PFAS subsurface fate and transport mechanisms leading to contamination of groundwater resources is therefore essential for management of raw water resources. A review of scientific literature on the subject of processes affecting subsurface PFAS fate and transport was carried out. This article compiles the current knowledge of such processes, mainly focusing on perfluoroalkyl acids (PFAA), in soil- and groundwater systems. Further, a compilation of data on transport parameters such as solubility and distribution coefficients, as well as, insight gained and conclusions drawn from the reviewed material are presented. As the use of certain fire-fighting foams has been identified as the major source of groundwater contamination in many countries, research related to this type of pollution source has been given extra focus. Uptake of PFAS in biota is outside the scope of this review. The review showed a large spread in the magnitude of distribution coefficients and solubility for individual PFAS. Also, it is clear that the influence of multiple factors makes site-specific evaluation of distribution coefficients valuable. This article aims at giving the reader a comprehensive overview of the subject, and providing a base for further work.

Understanding petroleum vapor fate and transport through high resolution analysis of two distinct vapor plumes.

No field study has provided a detailed characterization of the molecular composition and spatial distribution of a vadose zone plume of petroleum volatile organic compounds (VOCs), which is critical to improve the current understanding of petroleum VOC transport and fate. This is study reports a high-resolution analysis of two distinct vapor plumes emanating from two different light non-aqueous phase liquid (LNAPL) sources (an aliphatic-rich LNAPL for Zone #1vs an aromatic-rich LNAPL for Zone #2) at a large petrochemical site. Although deep soil vapor signatures were similar to the source zone LNAPL signatures, the composition of the shallow soil vapors reflected preferential attenuation of certain hydrocarbons over others during upward transport in the vadose zone. Between deeper and shallower soil gas samples, attenuation of aromatics was observed under all conditions, but important differences were observed in attenuation to aliphatic compound classes. Attenuation of all aliphatic compounds was observed under aerobic conditions but little attenuation of any aliphatics was observed under anoxic conditions without methane. In contrast, under methanogenic conditions, paraffins attenuated more than isoparaffins and naphthenes. These results suggest that isoparafins and naphthenes may present more of a vapor intrusion risk than benzene or other aromatic hydrocarbons commonly considered to be petroleum vapor intrusion risk drivers. While the overall vapor composition changed significantly within the vadose zone, diagnostic ratios of relatively recalcitrant alkylcyclopentanes were preserved in shallow soil vapor samples. These alkylcyclopentanes may be useful for distinguishing between petroleum vapor intrusion and other sources of petroleum VOCs detected in indoor air.

Polydimethylsiloxane dialysis passive sampler monitoring of chlorinated solvent contaminated sites - A field study.

The complexity of the subsurface contaminated by chlorinated solvents such as trichloroethylene (TCE) makes it challenging to gain a complete understanding of contamination distribution and establish a conceptual site model (CSM). High-resolution vertical contaminant concentration profiling across both the unsaturated zone and the saturated aquifer is desirable for mapping the distribution of contamination. A Fick's law-based polydimethylsiloxane (PDMS) dialysis passive sampler was developed and evaluated on a field scale for its potential application. This study tests the passive sampler at two TCE contaminated sites, and the sampling results were compared with the results from different sampling methods based on the relative percent difference. The PDMS dialysis passive sampler obtained more representative soil gas concentrations in the unsaturated zone than a portable monitoring and sampling device, which caused soil gas flow disturbance by soil gas pumping during sample collection. In the saturated aquifer sampling, the results obtained by the PDMS dialysis passive sampler correlated well with those obtained by a commercial polyethylene passive diffusion bag, and exhibited higher sensitivity under low TCE concentration conditions. Furthermore, the PDMS dialysis passive samplers were densely deployed inside each monitoring well at multiple depths, at two sites, to achieve high-resolution monitoring across the unsaturated zone and saturated aquifer. Based on the PDMS dialysis sampler data, a more comprehensive three-dimensional CSM was systematically established.

Exploration of the nitrogen contamination from sewers exfiltration to the unsaturated zone by modeling.

Numerous elements, such as the degree of sewer degeneration, hydraulics, and geological conditions, influence the extent to which sewage pollutes the unsaturated zones of urban. The present study discussed the influence of sewer exfiltration on the urban unsaturated zone, using nitrogen from domestic sewage as a representative contaminant in combination with experiments, literature studies, modeling and sensitivity analysis. The study shows that soils with high sand content exhibit high permeability and strong nitrification capacity, and groundwater is more susceptible to contamination with nitrate. In contrast, the nitrogen in the clay texture or wet soils has short migration distances and a weak nitrification capacity. However, under such conditions, the accumulation of nitrogen can last for more than 10 years, and there is a possible threat of groundwater contamination due to the detection difficulty. The presence of sewer exfiltration and the damage degree of a sewer can be determined by the ammonium concentration at 1-2 m near the pipe or nitrate above the water table. The sensitivity analysis revealed that all parameters impact the nitrogen concentration in the unsaturated zone to varying degrees, four of which are the primary parameters: defect area, exfiltration flux, saturated water content and first-order response constant. In addition, changes in environmental conditions significantly influence the boundaries of the pollution plume, especially the horizontal. The research data collected in this paper will not only allow for a rigorous assessment of the study scenarios but will also provide data support for other researchers.

Numerical modeling to assess the effect of soil texture on transport and attenuation of petroleum hydrocarbons in unsaturated zone.

Soil texture in the unsaturated zone is a critical factor affecting the transport, accumulation, and attenuation rate of petroleum hydrocarbons (PHCs) in unsaturated conditions. The scope of this study is to investigate the soil texture impact on the fate of PHCs in unsaturated zones. The main objective is to formulate a coupled flow and multicomponent transport model for simulating the PHC plumes in various soil textures. Zeroth spatial moment (ZSM) of simulated PHC plumes is estimated to quantify the transient effect of soil textures on the dissolved PHC mass in the system. A BTEX (benzene, toluene, ethylbenzene, and xylene) spill is considered at the source zone for modeling. Simulations are carried out for clay, sand, and loam textures. The outcome of the study suggests that the infiltration rate in the unsaturated zone is minimal in clay texture. Wetting front depths and BTEX source depletion rates are found to be in the following order: clay < loam < sand. The migration depth of BTEX components in the sand texture is approximately twice the depth for clay and loam after 50 days. An increment in the BTEX source zone length by twofold enhances the dissolved BTEX mass in the unsaturated system by approximately 33% in all soil textures. Overall, the modeling and sensitivity studies conclude that the soil texture, vertical dispersivity, source zone length and composition, sorption characteristics, and volatility critically affect the depth and extent of BTEX migration in unsaturated zones.

Transport and natural attenuation of benzene vapor from a point source in the vadose zone.

The vadose zone is a very dynamic and active environment that directly affects natural attenuation and vapor intrusion of volatile organic compounds (VOCs). Therefore, it is important to understand the fate and transport of VOCs in the vadose zone. A column experiment combined with model study was conducted to investigate the influence of soil type, vadose zone thickness, and soil moisture content on benzene vapor transport and natural attenuation in the vadose zone. Vapor-phase biodegradation and volatilization to atmosphere for benzene are two main natural attenuation mechanism in the vadose zone. Our data showed that biodegradation in black soil is the main natural attenuation mechanism (82.8%) while volatilization is the main natural attenuation mechanism in quartz sand, floodplain soil, lateritic red earth and yellow earth (>71.9%). The R-UNSAT model-predicted soil gas concentration profile and flux were close with four soil column data except for yellow earth. Increasing the vadose zone thickness and soil moisture content significantly reduced the volatilization contribution while increased biodegradation contribution. The volatilization loss decreased from 89.3% to 45.8% when the vadose zone thickness increased from 30 cm to 150 cm. The volatilization loss decreased from 71.9% to 10.1% when the soil moisture content increased from 6.4% to 25.4%. Overall, this study provided valuable insights into clarifying the roles of soil type, moisture, and other environmental conditions in vadose zone natural attenuation mechanism and vapor concentration.

Impact of climate change on groundwater recharge in shallow young glacial aquifers in northern Poland.

We investigated the influence of climate change in the period 1951-2020 on shallow aquifers in the Brda and Wda outwash plains (Pomeranian Region, Northern Poland). There was a significant temperature rise (0.3 °C/10 years), which accelerated after 1980 (0.66 °C/10 years). Precipitation became increasingly irregular - extremely rainy years occurred right after or before extremely dry years, and intensive rainfall events became more frequent after 2000. The groundwater level decreased over the last 20 years, even though the average annual precipitation was higher than in the previous 50 years. We carried out numerical simulations of water flow in representative soil profiles for the years 1970-2020 using the HYDRUS-1D model, developed and calibrated during our earlier work at an experimental site in the Brda outwash plain (Gumula-Kawecka et al., 2022). We used a relationship between the water head and flux at the bottom of the soil profiles (the third-type boundary condition) to reproduce groundwater table fluctuations caused by recharge variability in time. The calculated daily recharge showed a decreasing linear trend for the last 20 years (0.05-0.06 mm d-1/10 years), and dropping trends in water table level and soil water content in the entire profile of vadose zone. Field tracer experiments were performed to estimate impact of extremely rain events on water flux in vadose zone. The results suggest that tracer travel times are strongly determined by water content in the unsaturated zone which is determined by precipitation amount in span of weeks, rather than extremely high precipitation events.

Integrated approach to unsaturated zone characterization as it relates to burial practices and its impact on the immediate environment.

Improper sitting positioning of cemeteries in Nigeria is mostly responsible for groundwater pollution. Poor water quality may lead to some communicable diseases in most rural and urban areas of the southwestern part of Nigeria. The environmental impact of cemeteries close to residential areas within the Edunabon metropolis, southwestern part of Nigeria, was assessed. The research is aimed to understand the impact (if any) of the cemetery on the quality of water and soil within the vicinity and to investigate the suitability of soil materials underlying the cemetery as a special lining material. An integrated approach using geotechnical characterization, vertical electrical sounding and groundwater quality assessment was used in the present study. The geotechnical test involved six bulk undisturbed soil samples taken from two borrow pits within the cemetery. Index property tests (grain size distribution, specific gravity, natural moisture content, and Atterberg limits), engineering property tests (compaction test), X-ray diffraction, and X-ray fluorescence tests were carried out on the soil samples with their porosities and permeability estimated according to BS 1377. The majority of the study area is a wetland with a topography that descends into a gaining stream around 10 m from the cemetery. The soil of the cemetery is made up of coarse-grained porous lateritic soil, clay, and silt (0.22-3.88 percent), with a significant amount of gravel/sand (73.50-83.96 percent). Except in the control well, water analysis revealed a high total coliform concentration of 14-89 and a total hardness of 86-380 mg/L. When compared to the World Health Organization (WHO) drinking water standard and the Nigerian drinking water standard, the majority of cation concentrations were greater than the safe limits. The depth to contamination correlates to the depth of the aquifer in the research region, according to the results of electrical resistivity. Because of the narrow unsaturated zone, the study found that the position of the cemetery has a high risk of environmental impact on its near vicinity.

Tracing Sulfate Source and Transformation in the Groundwater of the Linhuan Coal Mining Area, Huaibei Coalfield, China.

Mining activities cause surface sulfate enrichment, which has negative impacts on human health and ecosystems. These high concentrations of sulfate may enter groundwater through the unsaturated zone (UZ), threatening groundwater quality. Therefore, we combined hydrochemical and dual isotopic analyses of sulfate in surface water, soil water and groundwater with evaluations of the UZ to identify the groundwater sulfate source and transformation in the coal mining area. Soil profile samples were collected near gangue heaps (UZ-1, UZ-2) and the mean sulfate concentrations of the UZ-1 profile and UZ-2 profile were 35.4 mg/L and 69.63 mg/L, respectively. The shallow groundwater sulfate was mainly from dissolution of evaporite, sulfide oxidation and sewage. Different sulfate contaminated areas showed different characteristics of sulfate sources. The sulfate source to groundwater near the coal gangue heaps was sulfide oxidation. The groundwater sulfate near the gangue heaps and industrial park compound contamination area was mainly derived from industrial and domestic sewage and sulfide oxidation. In addition, the role of bacterial sulfate reduction (BSR) in the groundwater was not obvious. This research result is of great significance for promoting the safe mining of coal resources and sustainable utilization of groundwater in the Huaibei coal mining area and other coal mining areas in China.

Nitrogen and sulfamethoxazole removal in a partially saturated vertical flow constructed wetland treating synthetic mariculture wastewater.

This study investigated the removal of nitrogen and sulfamethoxazole (SMX), and the microbial communities in a partially saturated vertical flow constructed wetland (PS-VFCW) fed with synthetic mariculture wastewater operated at different saturated zone depths (SZDs), i.e. 51, 70, and 60 cm. Removal efficiencies were 99.8%-100.0% for COD, 34.1%-100.0% for NH4+-N, 67.8%-97.3% for total inorganic nitrogen (TIN), and 29.8%-57.2% for SMX. Excellent nitrification performance was achieved at the SZDs of 51 and 60 cm. Denitrification performed well at 70 and 60 cm SZDs. The highest TIN removal efficiency (97.3%) was achieved as the SZD was 60 cm. SMX removal was significantly influenced by SZD and was promoted by higher SZD. The removal of organics, nitrogen, and SMX mainly occurred in the unsaturated zone. Ammonia-oxidizing bacteria, nitrite-oxidizing bacteria, denitrifying bacteria, and SMX-degrading bacteria were detected in the unsaturated and saturated zones, and showed an increasing trend in abundance along the depth.

Continuous VOCs Monitoring in Saturated and Unsaturated Zones Using Thermal Desorber and Gas Chromatography: System Development and Field Application.

Subsurface VOC monitoring has been mainly based on manual sampling, transport, and analysis, which would require a sufficient amount of samples to ensure data accuracy and reliability, and additional costs to ensure sample quality. Therefore, a continuous on-site monitoring system is desirable for accurate measurement and subsequent risk assessment. In this study, benzene, toluene, ethylbenzene, and xylene (BTEX) were continuously monitored by the system based on a thermal desorber (TD) and gas chromatography (GC) in an oil-contaminated site that consisted of saturated and unsaturated zones. For the saturated zone, fully automated groundwater sampling and purging processes were performed, and the gasified samples were applied to the TD-GC system. For the unsaturated zone, the gaseous sample in the site was directly applied to the TD-GC system. After verifying the accuracy and precision of the monitoring system, the continuous monitoring system was successfully operated for more than a month in the field. The monitoring system used in this study is applicable to other sites for continuous monitoring, thus providing a scientific background for advanced risk assessment and policy development.