Spatial and seasonal controls on dissolved organic matter composition in shallow aquifers under the rapidly developing city of Patna, India.

The distribution and composition of dissolved organic matter (DOM) affects numerous (bio)geochemical processes in environmental matrices including groundwater. This study reports the spatial and seasonal controls on the distribution of groundwater DOM under the rapidly developing city of Patna, Bihar (India). Major DOM constituents were determined from river and groundwater samples taken in both pre- and post-monsoon seasons in 2019, using excitation-emission matrix (EEM) fluorescence spectroscopy. We compared aqueous fluorescent DOM (fDOM) composition to satellite-derived land use data across the field area, testing the hypothesis that the composition of groundwater DOM, and particularly the components associated with surface-derived ingress, may be controlled, in part, by land use. In the pre-monsoon season, the prominence of tryptophan-like components likely generated from recent biological activity overwhelmed the humic-like and tyrosine-like fluorescence signals. Evidence from fluorescence data suggest groundwater in the post-monsoon season is composed of predominantly i) plant-derived matter and ii) anthropogenically influenced DOM (e.g. tryptophan-like components). Organic tracers, as well as Eh and Cl-, suggest monsoonal events mobilise surface-derived material from the unsaturated zone, causing dissolved organic carbon (DOC) of more microbial nature to infiltrate to >100 m depth. A correlation between higher protein:humic-like fluorescence and lower vegetation index (NDVI), determined from satellite-based land use data, in the post-monsoon season, indicates the ingression of wastewater-derived OM in groundwater under the urban area. Attenuated protein:humic-like fluorescence in groundwater close to the river points towards the mixing of groundwater and river water. This ingress of surface-derived OM is plausibly exacerbated by intensive groundwater pumping under these areas. Our approach to link the composition of aqueous organics with land use could easily be adapted for similar hydrogeochemical settings to determine the factors controlling groundwater DOM composition in various contexts.

The impact of phosphorus on projected Sub-Saharan Africa food security futures.

Sub-Saharan Africa must urgently improve food security. Phosphorus availability is one of the major barriers to this due to low historical agricultural use. Shared socioeconomic pathways (SSPs) indicate that only a sustainable (SSP1) or a fossil fuelled future (SSP5) can improve food security (in terms of price, availability, and risk of hunger) whilst nationalistic (SSP3) and unequal (SSP4) pathways worsen food security. Furthermore, sustainable SSP1 requires limited cropland expansion and low phosphorus use whilst the nationalistic SSP3 is as environmentally damaging as the fossil fuelled pathway. The middle of the road future (SSP2) maintains today's inadequate food security levels only by using approximately 440 million tonnes of phosphate rock. Whilst this is within the current global reserve estimates the market price alone for a commonly used fertiliser (DAP) would cost US$ 130 ± 25 billion for agriculture over the period 2020 to 2050 and the farmgate price could be two to five times higher due to additional costs (e.g. transport, taxation etc.). Thus, to improve food security, economic growth within a sustainability context (SSP1) and the avoidance of nationalist ideology (SSP3) should be prioritised.

Environmental tracers and groundwater residence time indicators reveal controls of arsenic accumulation rates beneath a rapidly developing urban area in Patna, India.

Groundwater security is a pressing environmental and societal issue, particularly due to significantly increasing stressors on water resources, including rapid urbanization and climate change. Groundwater arsenic is a major water security and public health challenge impacting millions of people in the Gangetic Basin of India and elsewhere globally. In the rapidly developing city of Patna (Bihar) in northern India, we have studied the evolution of groundwater chemistry under the city following a three-dimensional sampling framework of multi-depth wells spanning the central urban zone in close proximity to the River Ganges (Ganga) and transition into peri-urban and rural areas outside city boundaries and further away from the river. Using inorganic geochemical tracers (including arsenic, iron, manganese, nitrate, nitrite, ammonium, sulfate, sulfide and others) and residence time indicators (CFCs and SF6), we have evaluated the dominant hydrogeochemical processes occurring and spatial patterns in redox conditions across the study area. The distribution of arsenic and other redox-sensitive parameters is spatially heterogenous, and elevated arsenic in some locations is consistent with arsenic mobilization via reductive dissolution of iron hydroxides. Residence time indicators evidence modern (<~60-70 years) groundwater and suggest important vertical and lateral flow controls across the study area, including an apparent seasonal reversal in flow regimes near the urban center. An overall arsenic accumulation rate is estimated to be ~0.003 ± 0.003 µM.yr-1 (equivalent to ~0.3 ± 0.2 µg.yr-1), based on an average of CFC-11, CFC-12 and SF6-derived models, with the highest rates of arsenic accumulation observed in shallow, near-river groundwaters also exhibiting elevated concentrations of nutrients including ammonium. Our findings have implications on groundwater management in Patna and other rapidly developing cities, including potential future increased groundwater vulnerability associated with surface-derived ingress from large-scale urban abstraction or in higher permeability zones of river-groundwater connectivity.

Pore network and Darcy scale modelling of DNAPL remediation using ethanol flushing: Study of physical properties in DNAPL remediation.

Co-solvent flushing into contaminated soils is one of the most effective techniques for Dense Non-Aqueous Phase Liquid (DNAPL) remediation. In addition to the increase of DNAPL solubility, co-solvents (e.g. ethanol) can alter the viscosity and density of aqueous phase and diffusion coefficient of solute. Any changes in these parameters can change the flow behaviour and alter the upscaled DNAPL mass transfer coefficient which is a key parameter controlling soil and groundwater remediation at Darcy-scale. While numerous studies have investigated DNAPL remediation using co-solvents at the Darcy scale, pore-scale modelling of co-solvent enhanced DNAPL remediation has not been well investigated. In this work, a three-dimensional pore-network model was developed to simulate the 1,2-dichlorobenzene (DCB) remediation experiments using ethanol-water flushing solution. The model simulates the effect of changes in solubility, viscosity, density, and diffusion coefficient during co-solvent flushing of the DNAPL. The results of pore network modelling for ethanol-water flushing for the DCB remediation were also validated using the experimental data. In addition to pore-scale modelling, a continuum scale modelling (Darcy-scale) was used for the DCB remediation using ethanol-water flushing. The results of both pore network and continuum scale modelling demonstrated that the ethanol content and flushing velocity influence the interphase mass transfer and DNAPL dissolution process. The results indicated while the mass transfer coefficient decreased in the presence of ethanol, the process of NAPL remediation was improved due to the substantial increase of solubility in the presence of co-solvent. The large scale modelling showed that NAPL bank can be formed in the front of ethanol-water mixture flushing.

Fluid-Fluid Interfacial Effects in Multiphase Flow during Carbonated Waterflooding in Sandstone: Application of X-ray Microcomputed Tomography and Molecular Dynamics.

Fluid-fluid interfacial reactions in porous materials are pertinent to many engineering applications such as fuel cells, catalyst design, subsurface energy recovery (enhanced oil recovery), and CO2 storage. They have been identified to control physicochemical properties such as interfacial rheology, multiphase flow, and reaction kinetics. In recent years, engineered waterflooding has been identified as an effective way to increase hydrocarbon recovery and solid-fluid interaction has been assessed as the key mechanism. However, in this study, we demonstrated that in the absence of solid-fluid interactions (in strong hydrophilic porous media), fluid-fluid interfacial reactions can significantly affect multiphase flow and thus lead to an increased hydrocarbon recovery during engineered carbonated waterflooding. We designed a microwaterflooding system to evaluate the interfacial reactions during two phase flow with engineered carbonated waters. Given that salinity controls the amount of dissolved CO2, we injected carbonated high salinity water and carbonated low salinity water to achieve different fluid-fluid reactions. We injected the carbonated water in a sandstone with 99.5% quartz under X-ray microcomputed tomography (µCT) scanning at a resolution of 3.43 µm per pixel. Image processing shows that carbonated low salinity waterflooding can recover 8% more oil than carbonated high salinity waterflooding, while the quartz-rich sandstone remains strongly hydrophilic in both samples. A gradual CT intensity distribution indicates an interfacial phase generation between carbonated brine and crude oil during carbonated waterflooding. Therefore, we attributed the additional hydrocarbon recoveries to the fluid-fluid interfacial reactions. To understand the effects of fluid-fluid reactions on interfacial properties, we performed molecular dynamics simulations to investigate the chemical species distribution at the interface, interfacial tension (IFT) changes, and CO2 diffusion. The MD simulation results revealed a layered structure of the interface, a lower CO2 diffusion coefficient in carbonated high salinity water, a lower IFT in carbonated low salinity water, a swelling hydrocarbon phase in carbonated low salinity water, and more CO2 accumulated at the interface between the hydrocarbon phase and carbonated low salinity water. This work provides a general and fundamental understanding of the influence of fluid-fluid interactions on the interfacial properties between carbonated water and the hydrocarbon interface.

Simultaneous pressure and electro-osmosis driven flow in charged porous media: Pore-scale effects on mixing and dispersion.

Electrokinetic effects in porous media play a key role in a number of natural and industrial processes. Applications such as enhanced oil recovery, soil remediation and even drug delivery are affected by the Coulombic forces created by the solid-fluid interfacial interactions. These electrokinetic effects promote the development of non-homogenous slipping flow over charged surfaces at the pore scale, which can have a significant impact in the hydrodynamics of tight porous materials. For transport of ionic solutions in such systems (e.g. transport of low salinity water in tight oil reservoirs), combined effect of hydrodynamic transport and electrokinetic transport would be expected. While transport in pressure-driven transport will be pronounced in high permeability flow pathways, transport due to electric fields (e.g. electro-osmosis) will be more pronounced in tight pores were electrical diffuse layer is not negligible. In this work, we explored the pore-scale hydrodynamic characteristics of charged porous media using computational fluid dynamics. Different flow driving mechanisms were studied, e.g. conventional pressure driven flow, pure electro-osmosis as well as their superposition under different amounts of charged material. We then analyzed the effect of these distinct flow regimes on the transport of a passive tracer, finding how different driving mechanism result in distinct dispersion and mixing characteristics.