Barite Precipitation Research Articles

Pretreatment of brackish water reverse osmosis (BWRO) concentrate to enhance water recovery in inland desalination plants by direct contact membrane distillation (DCMD)

Inland brackish water desalination plants typically rely on reverse osmosis (RO) for the production of drinking water. However, the usual water recovery in these plants (i.e., 50–75%) results in fairly large quantities of the reject (concentrate) stream that needs to be disposed at considerable cost and with significant adverse environmental impacts. Membrane distillation (MD) offers a unique opportunity to improve the performance of these brackish water reverse osmosis (BWRO) plants by recovering additional clean permeate and reducing the volume of concentrate for disposal. In this study, barite precipitation was utilized to remove about 4000 mg/L of sulfate from actual BWRO concentrate to prevent interference with MD operation. The effect of barium concentration and mixing condition was evaluated for its impact on the removal of sulfate as the key ingredient of inorganic scales that would form in BWRO concentrate with increased water recovery. The pre-treated BWRO concentrate was used as feed in direct contact membrane distillation (DCMD) system operated at 60 °C to achieve at least 85% water recovery. The impact of concentration polarization on the performance of MD explored in a system operated at 80 °C revealed a potential for amorphous silica fouling of the membrane.

A fibre-optical method for monitoring barite precipitation at high pressure/high temperature conditions

Monitoring and controlling of mineral precipitation is a major challenge in several industry segments such as oil and gas or geothermal energy. Especially at elevated pressures, temperatures, and salinities, these reactions are poorly understood and difficult to predict. Real-time monitoring under such conditions, however, is crucial for reduction or prevention of scaling as well as for process modelling. In this study, a novel fibre-optical method for monitoring the barite precipitation process at high pressures and high temperatures was developed and tested. The applicability of a fibre-optical sensor was demonstrated and kinetic data derived from experiments using synthetic fluids that were oversaturated with barite. The ionic strength was varied between 0 and 5 mol/l NaCl to simulate geothermal brines typically found in deep sedimentary reservoirs. Experiments were performed at 25 and 150 °C. For the studied variations it was found that the ionic strength had a strong impact on the barite precipitation rate whereas temperature had only a minor influence. The kinetic rate constants were decreasing with increasing salinity ranging from 9 to 0.4 l‧mol−1‧s−1 at 25 °C and from 8.6 to 0.66 l‧mol−1‧s−1 at 150 °C.

Characterizing mineralization on low carbon steel exposed to aerated and degassed synthetic hydraulic fracture fluids

This study investigates the mineralization occurring at the interface between injected hydraulic fracturing fluids and steel production casing during the shut-in period of unconventional shale wells. Mild steel coupons were reacted with synthetic hydraulic fracturing fluids with varying base fluid and dissolved gas concentrations. Experiments were carried out in an autoclave system set at 50 °C and 2000 PSI for 2 and 14 days. Physical and mineralogical changes to the steel coupons’ surface were characterized using an FEI Quanta 600 field emission gun (FEG) scanning electron microscope (SEM) and a PANalytical XPert Pro diffractometer. Barite precipitation occurred ubiquitously during the first 48 h in all experimental scenarios. Sulfate radicals created from degradation and reduction of ammonium persulfate breakers facilitate barite formation. Concomitant barite and corrosion related precipitates on the sample surfaces suggest iron hydroxy salts act as nucleation sites for mineral scale growth. These results suggest hydraulic fracturing fluids may have deleterious effects on the wellbore before production of the well begins.

Micro-continuum approach for mineral precipitation

Rates and extents of mineral precipitation in porous media are difficult to predict, in part because laboratory experiments are problematic. It is similarly challenging to implement numerical methods that model this process due to the need to dynamically evolve the interface of solid material. We developed a multiphase solver that implements a micro-continuum simulation approach based on the Darcy–Brinkman–Stokes equation to study mineral precipitation. We used the volume-of-fluid technique in sharp interface implementation to capture the propagation of the solid mineral surface. Additionally, we utilize an adaptive mesh refinement method to improve the resolution of near interface simulation domain dynamically. The developed solver was validated against both analytical solution and Arbitrary Lagrangian–Eulerian approach to ensure its accuracy on simulating the propagation of the solid interface. The precipitation of barite (BaSO4) was chosen as a model system to test the solver using variety of simulation parameters: different geometrical constraints, flow conditions, reaction rate and ion diffusion. The growth of a single barite crystal was simulated to demonstrate the solver’s capability to capture the crystal face specific directional growth.

The role of sulfate-, alkali-, and halogen-rich fluids in mobilization and mineralization of rare earth elements: Insights from bulk fluid compositions in the Mianning–Dechang carbonatite-related REE belt, southwestern China

Carbonatites host the world's most important rare earth element (REE) resources. The origins of REE mineralization in carbonatite-related deposits, particularly the role of hydrothermal fluids in REE mobilization and mineralization, remain enigmatic. The Cenozoic Mianning–Dechang REE belt in eastern Tibet is one of the largest REE production regions worldwide, and is an ideal area for investigating REE mineralization. Geological investigations and fluid inclusion studies suggest that ore fluids in this belt evolved from hydrothermal stage I (fenitization at high temperatures of ~480 °C) to hydrothermal stage II (calcite, quartz, barite, and fluorite crystallization at temperatures of 300–350 °C and salinities of ~20 wt% NaCl equiv.), and then to the REE mineralization stage (temperatures of ~200 °C and low salinities of ~9 wt% NaCl equiv.). The bulk fluid compositions demonstrate that the ore fluids contained significant amounts of alkalis (up to 5 wt% Na + K), halogens (up to 12 wt% Cl; up to 7 wt% F), sulfate (>2 wt% SO42−), Ba (>1123 ppm), Sr (>1120 ppm), and REEs (>5 wt%). Chondrite-normalized REE patterns of these fluids are light REE-enriched and exhibit moderate depletion in Eu ([Eu/Eu⁎]CN = 0.85 ± 0.08), similar to the carbonatites and nordmarkites. These fluid characteristics and plots of Rb/Na vs. K/Na and Mn vs. Na suggest that the ore fluids in the Mianning–Dechang REE belt were derived from a late-stage alkaline–carbonatitic magma. High concentrations of Cl−, F−, SO42−, and REEs, and the absence of REE fluoride (REEF3) and fluorite (CaF2), suggest that the ore fluids in hydrothermal stage I were a high-temperature, SO42−-rich (>2 wt%), and acidic fluid system (pH < 3.5). In this system, chloride REE complexes were predominant over fluoride and sulfate REE complexes, which resulted in efficient transport of REEs. Sulfate species were predominant in hydrothermal stage II at temperatures of 260–350 °C and a pH between 3.5 and 5.2. The higher pH and fluid cooling from hydrothermal stage I to hydrothermal stage II caused an increase in F−, which in turn lowered fluid REE concentrations, owing to the formation of REE-rich fluorite. This suggests that F− was a depositional ligand in hydrothermal stage II. Continued fluid cooling (~200 °C) and increasing pH (~6), combined with the precipitation of barite and fluorite in the REE mineralization stage, destabilized the REE complexes because of the decreasing concentrations of SO42−, Cl−, and F−, which thus led to widespread REE deposition. A review of different-sized deposits in the Mianning–Dechang REE belt indicates that appreciable amounts of SO42−, Cl−, REEs, CO2, and particularly F− and alkalis in fluids, along with a high fluid exsolution temperature, represent the ideal conditions for potential REE mineralization in a carbonatite-related setting.

Elevated radium levels in Nubian Aquifer groundwater of Northeastern Africa

The Nubian Sandstone Aquifer System in Northeast Africa and the Middle East is a huge water resource of inestimable value to the population. However, natural radioactivity impairs groundwater quality throughout the aquifer posing a radiological health risk to millions of people. Here we present measurements of radium isotopes in Nubian Aquifer groundwater from population centers in the Western Desert of Egypt. Groundwater has 226Ra and 228Ra activities ranging from 0.01 to 2.11 and 0.03 to 2.31 Bq/L, respectively. Most activities (combined 226Ra + 228Ra) exceed U.S. EPA drinking water standards. The estimated annual radiation doses associated with ingestion of water having the highest measured Ra activities are up to 138 and 14 times the WHO-recommended maxima for infants and adults, respectively. Dissolved Ra activities are positively correlated with barium and negatively correlated with sulfate, while barite is approximately saturated. In contrast, Ra is uncorrelated with salinity. These observations indicate the dominant geochemical mechanisms controlling dissolved Ra activity may be barite precipitation and sulfate reduction, along with input from alpha-recoil and dissolution of aquifer minerals and loss by radioactive decay. Radium mitigation measures should be adopted for water quality management where Nubian Aquifer groundwater is produced for agricultural and domestic consumption.

Characterisation of fluid flow conditions and paths in the Buntsandstein Gp. sandstones reservoirs, Upper Rhine Graben

Deeply buried sandstone reservoirs are targeted in the Upper Rhine Graben (URG) for geothermal and hydrocarbon resources. These reservoirs are affected by a convective heat flow along fault zones and have a complex diagenetic and deformation history recorded in their paragenetic sequence. Here, the focus is made on siderite and barite cementation characterisation, which trace paleo geothermal circulations within the fracture network affecting the Buntsandstein Gp. sandstones. A double approach on geochemistry and fracture network features is used to characterise fluid-flow episodes in the rift basin and on its shoulders. Barite sulphur isotopic signature suggests a common source for all the locations. However, Rare Earth Elements distribution patterns, oxygen isotopic ratios, and fluid inclusion study suggest two distinct flow regimes for fluids associated with barite precipitation along the shoulders and at depth in the middle of the graben. The barite has a higher content in total REE and contains non-saline fluid inclusions on the graben shoulders, suggesting that fluid circulations within the border faults interact with sulphate rich layers and precipitate at temperature above 150 °C. In deep-seated samples from the central part of the basin, barite fluid inclusions show a wide range of salinities, suggesting a higher contribution of sedimentary brines and precipitation at lower temperatures (&lt; 150 °C). According to their REE signature, these barite mineralisations are associated with siderite and apatite with a diagenetic source. A conceptual model for fluid circulation within the basin is built from this new dataset. Fast and deep down- and up-flows occur along the major border faults, locally leaching evaporitic horizons. A part of the infiltrated meteoric waters reaches the centre of the basin, where it then mixes with the brines in sedimentary. This new characterisation of fluid pathways in the targeted reservoir brings insights into geothermal circulation compartmentalisation at the basin scale.

Characterizing Pore-Scale Geochemical Alterations in Eagle Ford and Barnett Shale from Exposure to Hydraulic Fracturing Fluid and CO2/H2O

As demand increases for an affordable energy source that is tied to an environmental obligation to reduce greenhouse gas emissions and water usage, there is a growing consideration in shale production utilizing processes such as (1) enhancing hydrocarbon recovery via carbon dioxide (CO2) flooding, (2) using CO2 as a fracturing agent to minimize water use, and (3) storing CO2 in depleted shale formations to mitigate emissions to the atmosphere. Understanding the geochemical reactions and alterations that occur as shale is exposed to fluids and CO2 is necessary to develop and optimize each of these processes for field applications. Although the majority of shale formations are stimulated using a traditional fracturing fluid, some may be fractured using CO2 or other nontraditional means. We examine the effect the fracturing fluid has on shale and how it behaves with secondary exposure to dry CO2 or CO2-saturated water using in situ Fourier transform infrared (FTIR) spectroscopy, feature relocation scanning electron microscopy (SEM), and surface area and pore size analysis using volumetric gas sorption. These techniques were performed on Eagle Ford and Barnett shale samples that were exposed to the fracturing fluid and unexposed (as received). Shales that have been exposed to the traditional fracturing fluid experienced two reaction fronts. The first reaction front was formed during exposure to the fracturing fluid (pH of ∼1.4). A secondary reaction front was formed as a result of CO2-saturated fluid exposure in the form of carbonic acid (pH ∼ 5.6). These two different reaction mechanisms drove multiple dissolution and precipitation cycles which altered petrophysical properties of the shale and could lead to a significant impact on flow pathways. FTIR spectroscopy showed that equilibration of carbonate dissolution and precipitation cycles could take as long as 35 days. Samples exposed to the fracturing fluid showed significantly less carbonate reactivity compared to those exposed to water. Pore size analysis results indicate that exposure to the fracturing fluid blocked small nanopores (0.7–10 nm) reducing BET surface area and total pore volume. SEM results show barite precipitated heavily during exposure to the fracturing fluid. It appeared that carbonic acid was able to extract sulfur from organic matter to form gypsum evaporites. The mineralogical (barite precipitation and calcite dissolution/precipitation) and pore-scale alterations observed in these samples may lead to enhancement of flow pathways for injected CO2 or produced hydrocarbons.

Barite Scale Formation and Injectivity Loss Models for Geothermal Systems

Barite scales in geothermal installations are a highly unwanted effect of circulating deep saline fluids. They build up in the reservoir if supersaturated fluids are re-injected, leading to irreversible loss of injectivity. A model is presented for calculating the total expected barite precipitation. To determine the related injectivity decline over time, the spatial precipitation distribution in the subsurface near the injection well is assessed by modelling barite growth kinetics in a radially diverging Darcy flow domain. Flow and reservoir properties as well as fluid chemistry are chosen to represent reservoirs subject to geothermal exploration located in the North German Basin (NGB) and the Upper Rhine Graben (URG) in Germany. Fluids encountered at similar depths are hotter in the URG, while they are more saline in the NGB. The associated scaling amount normalised to flow rate is similar for both regions. The predicted injectivity decline after 10 years, on the other hand, is far greater for the NGB (64%) compared to the URG (24%), due to the temperature- and salinity-dependent precipitation rate. The systems in the NGB are at higher risk. Finally, a lightweight score is developed for approximating the injectivity loss using the Damköhler number, flow rate and total barite scaling potential. This formula can be easily applied to geothermal installations without running complex reactive transport simulations.

Barite Precipitation on Suspended Organic Matter in the Mesopelagic Zone

Mechanisms underlying barite precipitation in seawater and the precise depths of barite precipitation in the water column have been debated for decades. Here we present a detailed study of water column barite distribution in the mesopelagic zone at diverse stations in the open ocean by analyzing samples collected using multiple unit large volume in-situ filtration systems in the Pacific, Atlantic and Indian oceans. Our results demonstrate that barite is an organo-mineral particularly abundant at intermediate depths throughout the world’s ocean regardless of saturation state with respect to barite. This is confirming the notion of precipitation at depths of intense organic matter mineralization. Our observations further support the link between barite formation and microbial activity, demonstrated by the association of barite particles with organic matter aggregates and with extracellular polymeric substances (EPS). Evidence for microbial mediation is consistent with previous experimental work showing that in bacterial biofilms Ba binds to phosphate groups on cell surfaces and within EPS. This organo-accumulation promotes high concentrations of Ba leading to saturated microenvironments and nucleation sites favoring precipitation. The distribution of Ba isotopes in the water column and in particulate matter is also consistent with the proposed precipitation mechanism.

Barium isotopes in mid-ocean ridge hydrothermal vent fluids: A source of isotopically heavy Ba to the ocean

Mid-ocean ridge (MOR) hydrothermal vent fluids are enriched with dissolved barium, but due to barite (BaSO4) precipitation during mixing between Ba-bearing vent fluids and SO4-bearing seawater, the magnitude of hydrothermal Ba input to the ocean remains uncertain. Deep-ocean Ba isotopes show evidence for non-conservative behavior, which might be explained by input of isotopically heavy hydrothermal Ba. In this study we present the first Ba isotope data in mid-ocean ridge hydrothermal vent fluids and particles from systems on the Mid-Atlantic Ridge (Rainbow 36°N and TAG 26°N), the East Pacific Rise (EPR9–10°N and 13°N) and the Juan de Fuca Ridge (MEF and ASHES). The vent fluids display a wide range of dissolved Ba concentrations from 0.43 to 97.9 μmol/kg and δ138/134Ba values from −0.26 to +0.91‰, but are modified relative to initial composition due to precipitation of barite. Calculated endmember vent fluid δ138/134Ba values, prior to barite precipitation, are between −0.17 and +0.09‰, consistent with the values observed in oceanic basalts and pelagic sediments. Water-rock interaction at depth in the oceanic crust appears to occur without Ba isotope fractionation. During subsequent venting and mixing with seawater, barite precipitation preferentially removes isotopically light Ba from vent fluids with a fractionation factor of Δ138/134Bahyd-barite-fluid = −0.35 ± 0.10‰ (2SE, n = 2). Based on knowledge of barite saturation and isotope fractionation during precipitation, the effective hydrothermal Ba component that mixes with seawater after barite precipitation has completed can be calculated: δ138/134Bahyd = +1.7 ± 0.7‰ (2SD). This value is isotopically heavier than deep ocean waters and may explain the observed non-conservative of Ba isotopes in deep waters. These new constraints on hydrothermal Ba compositions enable the hydrothermal input of Ba to Atlantic deep waters to be assessed at ≈3–9% of the observed Ba. Barium isotopes might be used as a tracer to reconstruct the history of hydrothermal Ba inputs and seawater SO4 concentrations in the past.

Equilibrium barium isotope fractionation between minerals and aqueous solution from first-principles calculations

Barium isotopes could be a novel tracer in low-temperature geochemical processes such as the Ba cycle in rivers and oceans. Equilibrium Ba isotope fractionation between Ba-hosting minerals and aqueous solution is of great importance for the applications of Ba isotopes in geochemistry, but it remains poorly constrained. In this study, we performed first-principles calculations based on the density functional theory (DFT) to determine the equilibrium Ba isotope fractionation between minerals and aqueous solution (103lnαmineral-Ba_aq of 137Ba/134Ba). The structural properties of aqueous Ba2+ are well predicted by the first-principles molecular dynamics (FPMD) simulation and 121 snapshots are extracted from FPMD trajectories to estimate the reduced partition function ratio (β factor or 103lnβ of 137Ba/134Ba) of aqueous Ba2+. The 103lnβ decreases in the sequence of aragonite > calcite > aqueous Ba2+ ∼ witherite > barite. The β factor is dominantly determined by the force constant, which is affected by both the average BaO bond length and the coordination number.Our results show that 103lnαaragonite-Ba_aq and 103lnαwitherite-Ba_aq are 0.36‰ and −0.02‰ at 300 K, respectively, consistent with results of experimental studies at equilibrium. The depletion of heavy Ba isotopes observed in natural corals relative to seawater suggests that kinetic effects play an important role in Ba isotope fractionation during coral growth. The 103lnαbarite-Ba_aq is only −0.17‰ at 300 K, indicating limited Ba isotope fractionation caused by the Ba removal stemmed from inorganic barite precipitation. Overall, the equilibrium Ba isotope fractionation factors between minerals and aqueous Ba2+ calculated in this study provide a guideline for the applications of Ba isotopes in low-temperature geochemistry.

Predicting the potential for mineral scale precipitation in unconventional reservoirs due to fluid-rock and fluid mixing geochemical reactions

Mineral precipitation within hydraulically fractured shale may affect fluid flow pathways and impact long-term hydrocarbon production. The ability to predict geochemical reactions causing problematic mineral precipitation will lead to active reservoir management strategies for improving production. Using the Marcellus Shale as a case study, laboratory experiments and reaction path modeling were applied to determine which reactions occur during hydraulic fracturing, shut-in, flowback, and production timeframes. Experimental results indicate that contact between fracturing fluid and shale will result in dissolution of primary minerals (carbonates, quartz, feldspars, kaolinite, chlorite, pyrite) and secondary mineral precipitation over time periods of less than one week. Precipitation of secondary carbonates, barite, iron oxides, feldspars, amorphous silica and clay is likely to occur within the reservoir during shut in and early flowback due to mixing between fracturing fluid and reservoir brine as based on modeling saturation indices using experimental fluid data. Reaction path modeling corroborates the dissolution and precipitation reactions observed experimentally. Comparison of the results to injected and produced waters from a Marcellus Shale well pad in Greene County, PA, USA, shows that the mineral reactions occur during the hydraulic fracturing, shut in, and early flowback periods. The results presented here demonstrate the value in applying experimental approaches to identify mineral precipitation/dissolution reactions that may significantly impact reservoir performance. The good agreement between geochemical models and experimental results provides confidence that numerical models can be applied to screen the potential fluid-mineral and fluid-mixing reactions in unconventional reservoirs that result in undesired mineral scale precipitation.

Sulfate precipitation in produced water from Marcellus Shale for the control of naturally occurring radioactive material

Produced water (PW) generated during unconventional oil and gas extraction is characterized by very high total dissolved solids (TDS) that mainly consist of alkali and alkaline earth metals. Dominant PW management strategy (i.e., injection in Class II disposal wells) is scrutinized by regulatory agencies, and the public and PW treatment that enables high water and salt recovery (i.e., evaporation/crystallization) is being considered as an alternative. Produced water generated in the Marcellus Shale play also contains very high levels of Naturally Occurring Radioactive Material (NORM) in the form of Ra-226 and Ra-228, which is one of the key impediments for the recovery of high-quality salts. This study was designed to evaluate the efficiency of Ra-226 removal using co- and post-precipitation with barium sulfate to enable advanced PW treatment processes. High Sr/Ba molar ratios in PW lead to relatively low Ba2+ and Ra2+ removal, and Ba2+ concentration adjustment is necessary to achieve required treatment standards (i.e., [Ba2+] < 10 mg/L and [Ra2+] < 50 pCi/L). Seeding the reactor with barium sulfate enhanced Ba2+ and Ra2+ removal through induced heterogeneous precipitation of barite. However, it was necessary to simultaneously adjust the Sr/Ba ratio and barite level to achieve treatment requirements while maintaining reasonable detention time in the reactor (i.e., <30 min) and minimizing sludge production. Experimental and modeling results revealed that low Ba2+ and Ra2+ effluent concentrations, with minimized sludge production, can be achieved only when the barium sulfate saturation index was above 4.7, Sr/Ba molar ratio was below 2 and there was at least 25 g/L of barite “seed” in the system. This study provides useful guidelines for centralized wastewater treatment facilities in shale plays and serves to optimize pretreatment of produced water to enable recovery of valuable resources (i.e., clean water and usable salts).

Metals Coprecipitation with Barite: Nano-XRF Observation of Enhanced Strontium Incorporation.

Coprecipitation can be an effective treatment method for the removal of environmentally relevant metals from industrial wastewaters such as produced waters from the oil and gas industry. The precipitation of barite, BaSO4, through the addition of sulfate removes barium while coprecipitating strontium and other alkaline earth metals even when these are present at concentrations below their solubility limit. Among other analytical methods, X-ray fluorescence (XRF) nanospectroscopy at the Hard X-ray Nanoprobe (HXN) beamline at the National Synchrotron Light Source II (NSLS-II) was used to quantify Sr incorporation into barite. Thermodynamic modeling of (Ba,Sr)SO4 solid solutions was done using solid solution—aqueous solution (SS-AS) theory. The quantitative, high-resolution nano-XRF data show clearly that the Sr content in (Ba,Sr)SO4 solid solutions varies widely among particles and even within a single particle. We observed substantial Sr incorporation that is far larger than thermodynamic models predict, likely indicating the formation of metastable solid solutions. We also observed that increasing barite supersaturation of the aqueous phase led to increased Sr incorporation, as predicted by available kinetic models. These results suggest that coprecipitation offers significant potential for designing treatment systems for aqueous metals' removal in desired metastable compositions. Solution conditions may be optimized to enhance the incorporation of Sr by increasing sulfate addition such that the barite saturation index remains above ∼3 or by increasing the aqueous Sr to Ba ratio.

Combination of MRI and SEM to Assess Changes in the Chemical Properties and Permeability of Porous Media due to Barite Precipitation

The understanding of the dissolution and precipitation of minerals and its impact on the transport of fluids in porous media is essential for various subsurface applications, including shale gas production using hydraulic fracturing (“fracking”), CO2 sequestration, or geothermal energy extraction. In this work, we conducted a flow through column experiment to investigate the effect of barite precipitation following the dissolution of celestine and consequential permeability changes. These processes were assessed by a combination of 3D non-invasive magnetic resonance imaging, scanning electron microscopy, and conventional permeability measurements. The formation of barite overgrowths on the surface of celestine manifested in a reduced transverse relaxation time due to its higher magnetic susceptibility compared to the original celestine. Two empirical nuclear magnetic resonance (NMR) porosity–permeability relations could successfully predict the observed changes in permeability by the change in the transverse relaxation times and porosity. Based on the observation that the advancement of the reaction front follows the square root of time, and micro-continuum reactive transport modelling of the solid/fluid interface, it can be inferred that the mineral overgrowth is porous and allows the diffusion of solutes, thus affecting the mineral reactivity in the system. Our current investigation indicates that the porosity of the newly formed precipitate and consequently its diffusion properties depend on the supersaturation in solution that prevails during precipitation.

An exploratory data analysis approach for assessing the sources and distribution of naturally occurring contaminants (F, Ba, Mn, As) in groundwater from southern Quebec (Canada)

The presence of naturally occurring contaminants in groundwater is a public health concern in rural areas of northeastern North America, where public and private wells are important sources of drinking water. In southern Quebec (Canada), inorganic groundwater chemistry data have been recently collected following standard procedures in several regional hydrogeological projects implemented by the government of Quebec. In this study, a groundwater chemistry database was compiled from 16 regional projects altogether covering an area of approximately 100,000 km2. The database includes information on water supply infrastructures, geological settings, hydrogeological conditions and inorganic water chemistry for 2369 water samples. Samples were mostly collected from private domestic wells, and to a lesser extent from municipal and observation wells. The data revealed that fluoride, barium, manganese and arsenic are the most common elements exceeding Canadian drinking water guidelines. Exploratory data analysis techniques were applied to selected subsets of data to gain insight into the sources and distribution of these hazardous groundwater contaminants. These exploratory methods include graphical data analysis (maps, Piper and empirical cumulative distribution function plots), multivariate compositional data analysis (clustering and correlation analysis) and geochemical modeling (saturation index calculations). The results suggest that fluoride, barium, manganese and arsenic are all derived from natural sources. Elevated fluoride concentrations are mainly associated with dilute Ca–Na–HCO3 bedrock groundwaters from granitic areas (Grenville Province), and more geochemically evolved Na–HCO3 to Na–HCO3–Cl bedrock groundwaters from shale areas (St. Lawrence Platform). High-F groundwaters are generally characterized by low Ca concentrations (<30 mg/L) and alkaline pH (pH > 8), suggesting that F is mainly controlled by fluorite (CaF2) precipitation and anion exchange with OH−. Barium is present at elevated concentrations in mineralized Ca–Na–HCO3, Na–HCO3 to Na–HCO3–Cl waters from bedrock aquifers of the St. Lawrence Lowlands. These groundwaters are mainly chemically evolved, strongly reducing waters occurring in confined aquifers and near major faults, which appear to correspond to discharge areas for deep regional flow. High Ba concentrations are generally associated with very low SO4 concentrations (< 5 mg/L) resulting from sulfate reduction, suggesting a solubility control of Ba through barite (BaSO4) precipitation. Most high manganese concentrations occur in less chemically evolved, near-neutral Ca–HCO3 groundwaters from both granular and bedrock aquifers, particularly those associated with metasedimentary and metavolcanic lithologies (Superior Province, St. Lawrence Platform and Appalachian Province). The results suggest that dissolved Mn concentrations are limited by the precipitation of Mn carbonates under alkaline conditions, but increase under reducing conditions owing to the dissolution of Fe–Mn oxyhydroxides. Elevated arsenic concentrations were mostly found in Ca-(Na–Mg)–HCO3 bedrock groundwaters of the Superior and Appalachian Provinces. As-rich groundwaters are associated with the presence of As-bearing sulfides in weakly metamorphosed sedimentary rocks (shale, slate, phyllite) and hydrothermally altered rocks. Most high As concentrations do not appear to be directly derived from sulfide oxidation, but rather from secondary sources, in particular through the reductive dissolution of As-rich Fe–Mn oxyhydroxides. This work shows that the combination of graphical, multivariate statistical and geochemical modeling techniques is a powerful approach to explore large hydrochemical datasets. It also reveals the benefits of using multivariate compositional data analysis instead of classical approaches based on raw data and log-ratios for groundwater chemistry data. Compositional data analysis techniques improved the detection of multivariate outliers, the cluster reliability in cluster analysis, and removed the spurious positive correlation between hydrochemical variables associated with total mineralization.

Active growth of non-hydrothermal subaqueous and subaerial barite (BaSO4) speleothems in Lechuguilla Cave (New Mexico, USA)

Barite (BaSO4) speleothems have been reported from caves around the globe and interpreted to have chiefly formed in phreatic, hypogene, hydrothermal settings. Here we report two contrasting types of barite speleothems (bluish tabular crystals in a shallow pool and actively dripping greenish stalactites), which today form at lower temperatures in the non-hydrothermal and vadose environment of Lechuguilla Cave, New Mexico, USA. Scanning electron microscopy analysis, along with energy- and wavelength-dispersive X-ray spectroscopy (EDS, WDS), as well as X-ray diffraction (XRD), characterize the habit and chemical composition as barite. Fractionation of the minor element calcium is related to growth along different crystal faces whereas variations in strontium concentration are mirrored in blue color zoning of the pool crystals. Two possible modes of non-hydrothermal barite precipitation are discussed: (1) intense evaporation driven by thermal atmospheric convection cells or (2) mixing of barium-rich, sulfate-poor water with water rich in sulfate. Both processes, in isolation or in combination, lead to supersaturation and could explain formation of the investigated barite speleothems. Observations of three types of microbes on the pool barite crystals showing evidence of incrustation raises the question whether there is a potential involvement of microbial activity in the temperate barite precipitation in Lechuguilla Cave.

Metal partitioning after in situ filtration at deep-sea vents of the Lucky Strike hydrothermal field (EMSO-Azores, Mid-Atlantic Ridge, 37°N)

Metal partitioning between the dissolved and particulate phases is still poorly constrained within the early mixing of hydrothermal fluids and deep seawater. In this study, in situ filtration has been used to collect early buoyant plume fluids. This has provided the unique opportunity to reassess precisely metal partitioning along the mixing gradient by limiting chemical exchange processes between the dissolved (<0.45 μm) and particulate (>0.45 μm) phases during sampling. We report on the partitioning of three major metals (Fe, Cu, Zn) in the early buoyant plume of six black and clear smokers from the Lucky Strike hydrothermal field (37°N, MAR; EMSO-Azores deep sea observatory). We show that chemical changes are limited in the warmest part of the plume [50–150°C, dMn > 40 μM; dilution factor (DF) of ~1–10 by NADW] as metal partitioning displays a chemical signature similar to the end-member one. However, as the dilution ratio between the hydrothermal fluid and North-Atlantic Deep-water (NADW) increases (4–50°C, dMn < 40 μM; DF of 10–100 by NADW), metal partitioning is affected by different precipitation and oxidation processes. Molar ratios normalized to Fe in the particles highlight the onset of Fe oxides formation, the precipitation of barite and the decreasing contribution of sulfide minerals (mainly Cu–Fe sulfides and sphalerite/wurtzite) along with fluid dilution.

Seasonal riverine barium isotopic variation in the middle Yellow River: Sources and fractionation

Barium (Ba) isotopes have been used to trace water mass mixing and export productivity in the oceans. However, the sources, isotopic signature and seasonal variation of dissolved Ba in large rivers remain poorly constrained. In order to improve our understanding of sources and fractionation of riverine Ba isotopes at the continental scale, weekly sampling of river water was carried out in the middle Yellow River over the full hydrological year of 2013. Dissolved Ba was mainly sourced from silicate dissolution, whose flux was correlated with physical erosion rate in this arid to semi-arid basin, largely covered by loess. More than half of the annual dissolved Ba flux was transported during the monsoon season (June to mid-September), in particular during a storm event period (accounting for 4% of the annual dissolved Ba flux in 4 days). The dissolved Ba isotopic composition (δ138Barw) ranged from +0.17‰ to +0.46‰, all higher than δ138Ba of loess (0.00 ± 0.04‰). The seasonal variation in δ138Barw is best explained via an adsorption model of light Ba isotopes onto solids in the river, which is sensitive to erosion of loess, in particular during the storm event and the spring-time ice melting intervals, with a potential role of barite precipitation in groundwater during the dry seasons. With one to three orders of magnitude higher particulate matter fluxes during the monsoon seasons in rivers such as the Yellow River, desorption of Ba could result an unaccounted strong variation of Ba concentration and isotopic composition in coastal environments, which further study requires.