Differential Adsorption of Dissolved Organic Matter and Phosphorus on Clay Mineral in Water-Sediment System.

Lake sediments connection to the biogeochemical cycling of phosphorus (P) and carbon (C) influences streamwater quality. However, it is unclear whether and how the type of sediment controls P and C cycling in water. Here, the adsorption behavior of montmorillonite (Mt) with different interlayer cations (Na+, Ca2+, or Fe3+) on dissolved organic matter (DOM) and P was investigated to understand the role of Mt in regulating the organic carbon-to-phosphate (OC/P) ratio within freshwater systems. The adsorption capacity of Fe-Mt for P was 3.2-fold higher than that of Ca-Mt, while it was 1/3 lower for DOM. This dissimilarity in adsorption led to an increased OC/P in Fe-Mt-dominated water and a decreased OC/P in Ca-Mt-dominated water. Moreover, an in situ atomic force microscope and high-resolution mass spectrometry revealed molecular fractionation mechanisms and adsorptive processes. It was observed that DOM inhibited the nucleation and crystallization processes of P on the Mt surface, and P affected the binding energy of DOM on Mt through competitive adsorption, thereby governing the interfacial P/DOM dynamics on Mt substrates at a molecular level. These findings have important implications for water quality management, by highlighting the role of clay minerals as nutrient sinks and providing new strategies for controlling P and C dynamics in freshwater systems.

Physical Phenomena Governing Mineral Morphogenesis in Molluscan Nacre.

Mollusks, as well as many other living organisms, have the ability to shape mineral crystals into unconventional morphologies and to assemble them into complex functional mineral-organic structures, an observation that inspired tremendous research efforts in scientific and technological domains. Despite these, a biochemical toolkit that accounts for the formation of the vast variety of the observed mineral morphologies cannot be identified yet. Herein, phase-field modeling of molluscan nacre formation, an intensively studied biomineralization process, is used to identify key physical parameters that govern mineral morphogenesis. Manipulating such parameters, various nacre properties ranging from the morphology of a single mineral building block to that of the entire nacreous assembly are reproduced. The results support the hypothesis that the control over mineral morphogenesis in mineralized tissues happens via regulating the physico-chemical environment, in which biomineralization occurs: the organic content manipulates the geometric and thermodynamic boundary conditions, which in turn, determine the process of growth and the form of the biomineral phase. The approach developed here has the potential of providing explicit guidelines for the morphogenetic control of synthetically formed composite materials.

Layered Clay Minerals in Cancer Therapy: Recent Progress and Prospects.

Cancer is one of the deadliest diseases, and current treatment regimens suffer from limited efficacy, nonspecific toxicity, and chemoresistance. With the advantages of good biocompatibility, large specific surface area, excellent cation exchange capacity, and easy availability, clay minerals have been receiving ever-increasing interests in cancer treatment. They can act as carriers to reduce the toxic side effects of chemotherapeutic drugs, and some of their own properties can kill cancer cells, etc. Compared with other morphologies clays, layered clay minerals (LCM) have attracted more and more attention due to adjustable interlayer spacing, easier ion exchange, and stronger adsorption capacity. In this review, the structure, classification, physicochemical properties, and functionalization methods of LCM are summarized. The state-of-the-art progress of LCM in antitumor therapy is systematically described, with emphasis on the application of montmorillonite, kaolinite, and vermiculite. Furthermore, the property-function relationships of LCM are comprehensively illustrated to reveal the design principles of clay-based antitumor systems. Finally, foreseeable challenges and outlook in this field are discussed.

Binding of Cd(II) to birnessite and fulvic acid organo-mineral composites and controls on Cd(II) availability.

Manganese oxide minerals (MnOs) are major controls on cadmium (Cd) mobility and fate in the environment. However, MnOs are commonly coated with natural organic matter (OM), and the role of this coating in the retention and availability of harmful metals remains unclear. Herein, organo-mineral composites were synthesized using birnessite (BS) and fulvic acid (FA), during coprecipitation with BS and adsorption to preformed BS with two organic carbon (OC) loadings. The performance and underlying mechanism of Cd(II) adsorption by resulting BS-FA composites were explored. Consequently, FA interactions with BS at environmentally representative (5 wt% OC) increase Cd(II) adsorption capacity by 15.05-37.39% (qm = 156.5-186.9 mg g-1), attributing to the enhanced dispersion of BS particles by coexisting FA led to significant increases in specific surface area (219.1-254.8 m2 g-1). Nevertheless, Cd(II) adsorption was notably inhibited at a high OC level (15 wt%). This might have derived from the supplementation of FA decreased pore diffusion rate and generated Mn(II/III) competition for vacancy sites. The dominant Cd(II) adsorption mechanism was precipitation with minerals (Cd(OH)2), and complexation with Mn-O groups and acid oxygen-containing functional groups of FA. In organic ligand extractions, the exchange Cd content decreased by 5.63-7.93% with low OC coating (5 wt%), but increased to 33.13-38.97% at a high OC level (15 wt%). These findings help better understand the environmental behavior of Cd under the interactions of OM and Mn minerals, and provide a theoretical basis for organo-mineral composite remediation of Cd-contaminated water and soil.

Advances in the Synthesis and Analysis of Biologically Active Phosphometabolites.

Phosphorus-containing metabolites cover a large molecular diversity and represent an important domain of small molecules which are highly relevant for life and represent essential interfaces between biology and chemistry, between the biological and abiotic world. The large but not unlimited amount of phosphate minerals on our planet is a key resource for living organisms on our planet, while the accumulation of phosphorus-containing waste is associated with negative effects on ecosystems. Therefore, resource-efficient and circular processes receive increasing attention from different perspectives, from local and regional levels to national and global levels. The molecular and sustainability aspects of a global phosphorus cycle have become of much interest for addressing the phosphorus biochemical flow as a high-risk planetary boundary. Knowledge of balancing the natural phosphorus cycle and the further elucidation of metabolic pathways involving phosphorus is crucial. This requires not only the development of effective new methods for practical discovery, identification, and high-information content analysis, but also for practical synthesis of phosphorus-containing metabolites, for example as standards, as substrates or products of enzymatic reactions, or for discovering novel biological functions. The purpose of this article is to review the advances which have been achieved in the synthesis and analysis of phosphorus-containing metabolites which are biologically active.

Resolving the Chemical Formula of Nesquehonite via NMR Crystallography, DFT Computation, and Complementary Neutron Diffraction.

Nesquehonite is a magnesium carbonate mineral relevant to carbon sequestration envisioned for carbon capture and storage of CO2 . Its chemical formula remains controversial today, assigned as either a hydrated magnesium carbonate [MgCO3 ⋅ 3H2 O], or a hydroxy- hydrated- magnesium bicarbonate [Mg(HCO3 )OH ⋅ 2H2 O]. The resolution of this controversy is central to understanding this material's thermodynamic, phase, and chemical behavior. In an NMR crystallography study, using rotational-echo double-resonance 13 C{1 H} (REDOR), 13 C-1 H distances are determined with precision, and the combination of 13 C static NMR lineshapes and density functional theory (DFT) calculations are used to model different H atomic coordinates. [MgCO3 ⋅ 3H2 O] is found to be accurate, and evidence from neutron powder diffraction bolsters these assignments. Refined H positions can help understand how H-bonding stabilizes this structure against dehydration to MgCO3 . More broadly, these results illustrate the power of NMR crystallography as a technique for resolving questions where X-ray diffraction is inconclusive.

Transformation of hazardous sacred incense sticks ash waste into less toxic product by sequential approach prior to their disposal into the water bodies.

Incense sticks ash is one of the most unexplored by-products generated at religious places and houses obtained after the combustion of incense sticks. Every year, tonnes of incense sticks ash is produced at religious places in India which are disposed of into the rivers and water bodies. The presence of heavy metals and high content of alkali metals challenges a potential threat to the living organism after the disposal in the river. The leaching of heavy metals and alkali metals may lead to water pollution. Besides this, incense sticks also have a high amount of calcium, silica, alumina, and ferrous along with traces of rutile and other oxides either in crystalline or amorphous phases. The incense sticks ash, heavy metals, and alkali metals can be extracted by water, mineral acids, and alkali. Ferrous can be extracted by magnetic separation, while calcium by HCl, alumina by sulfuric acid treatment, and silica by strong hydroxides like NaOH. The recovery of such elements by using acids and bases will eliminate their toxic heavy metals at the same time recovering major value-added minerals from it. Here, in the present research work, the effect on the elemental composition, morphology, crystallinity, and size of incense sticks ash particles was observed by extracting ferrous, followed by extraction of calcium by HCl and alumina by H2SO4 at 90-95 °C for 90 min. The final residue was treated with 4 M NaOH, in order to extract leachable silica at 90 °C for 90 min along with continuous stirring. The transformation of various minerals phases and microstructures of incense sticks ash (ISA) and other residues during ferrous, extraction, calcium, and alumina and silica extraction was studied using Fourier transform infrared (FTIR), dynamic light scattering (DLS), X-ray fluorescence (XRF), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and inductively coupled plasma-optical emission spectroscopy (ICP-OES). DLS was used for analyzing the size during the experiments while FTIR helped in the confirmation of the formation of new products during the treatments. From the various instrumental analyses, it was found that the toxic metals present in the initial incense sticks ash got eliminated. Besides this, the major alkali metals, i.e., Ca and Mg, got reduced during these successive treatments. Initially, there were mainly irregular shaped, micron-sized particles that were dominant in the incense sticks ash particles. Besides this, there were plenty of carbon particles left unburned during combustion. In the final residue, nanosized flowers shaped along with cuboidal micron-sized particles were dominant. present in If, such sequential techniques will be applied by the industries based on recycling of incense sticks ash, then not only the solid waste pollution will be reduced but also numerous value-added minerals like ferrous, silica, alumina calcium oxides and carbonates can be recovered from such waste. The value-added minerals could act as an economical and sustainable source of adsorbent for wastewater treatment in future.

Unusual uranium biomineralization induced by green algae: Behavior investigation and mechanism probe.

As a biosorbent, algae are frequently used for the biotreatment or bioremediation of water contaminated by heavy metal or radionuclides. However, it is unclear that whether or not the biomineralization of these metal or radionuclides can be induced by algae in the process of bioremediation and what the mechanism is. In this work, Ankistrodsemus sp. has been used to treat the uranium-contaminated water, and more than 98% of uranium in the solution can be removed by the alga, when the initial uranium concentration ranges from 10 to 80 mg/L. Especially, an unusual phenomenon of algae-induced uranium biomineralization has been found in the process of uranium bioremediation and its mineralization mechanism has been explored by multiple approaches. It is worth noticing that the biomineralization of uranium induced by Ankistrodsemus sp. is significantly affected by contact time and pH. Uranium is captured rapidly on the cell surface via complexation with the carboxylate radical, amino and amide groups of the microalgae cells, which provides nucleation sites for the precipitation of insoluble minerals. Uranium stimulates Ankistrodsemus sp. to metabolize potassium ions (K+), which may endow algae with the ability to biomineralize uranium into the rose-like compreignacite (K2[(UO2)6O4(OH)6]•8H2O). As the time increased, the amorphous gradually converted into compreignacite crystals and a large number of crystals would expand over both inside and outside the cells. To the best of our knowledge, this is the first investigated microalgae with a time-dependent uranium biomineralization ability and superior tolerance to uranium. This work validates that Ankistrodsemus sp. is a promising alga for the treatment of uranium-contaminated wastewater.

Effect of humic acid derived from leonardite on the redistribution of uranium fractions in soil.

Humic acids (HAs) are complex organic substances with abundant functional groups (e.g., carboxyl, phenolic-OH, etc.). They are commonly distributed in the soil environment and exert a double-edged sword effect in controlling the migration and transformation of uranium. However, the effects of HAs on dynamic processes associated with uranium transformation are still unclear. In this study, we used HAs derived from leonardite (L-HA) and commercial HA (C-HA) as exogenous organic matter and C-HA as the reference. UO2, UO3, and UO2(NO3)2 were used as the sources of U to explore the fractionations of uranium in the soil. We also studied the behavior of the HA. The incubation experiments were designed to investigate the effects of HA on the soil pH, uranium fraction transformation, dynamic behavior of exchangeable, weak acid, and labile uranium. The observations were made for one month. The results showed that soil pH decreased for L-HA but increased for C-HA. Under these conditions, uranium tended to transform into an inactive fraction. The dynamic behavior of exchangeable, weak acid, and labile uranium varied with the sources of HA and uranium. This study highlighted that HA could affect soil pH and the dynamic redistribution of U fractions. The results suggest that the sources of HA and U should be considered when using HA as the remediation material for uranium-contaminated soils.

Marine phosphate availability and the chemical origins of life on Earth.

Prebiotic systems chemistry suggests that high phosphate concentrations were necessary to synthesise molecular building blocks and sustain primitive cellular systems. However, current understanding of mineral solubility predicts negligible phosphate concentrations for most natural waters, yet the role of Fe2+, ubiquitous on early Earth, is poorly quantified. Here we determine the solubility of Fe(II)-phosphate in synthetic seawater as a function of pH and ionic strength, integrate these observations into a thermodynamic model that predicts phosphate concentrations across a range of aquatic conditions, and validate these predictions against modern anoxic sediment pore waters. Experiments and models show that Fe2+ significantly increases the solubility of all phosphate minerals in anoxic systems, suggesting that Hadean and Archean seawater featured phosphate concentrations ~103-104 times higher than currently estimated. This suggests that seawater readily met the phosphorus requirements of emergent cellular systems and early microbial life, perhaps fueling primary production during the advent of oxygenic photosynthesis.

Trends and Technological Advancements in the Possible Food Applications of Spirulina and Their Health Benefits: A Review.

Spirulina is a kind of blue-green algae (BGA) that is multicellular, filamentous, and prokaryotic. It is also known as a cyanobacterium. It is classified within the phylum known as blue-green algae. Despite the fact that it includes a high concentration of nutrients, such as proteins, vitamins, minerals, and fatty acids-in particular, the necessary omega-3 fatty acids and omega-6 fatty acids-the percentage of total fat and cholesterol that can be found in these algae is substantially lower when compared to other food sources. This is the case even if the percentage of total fat that can be found in these algae is also significantly lower. In addition to this, spirulina has a high concentration of bioactive compounds, such as phenols, phycocyanin pigment, and polysaccharides, which all take part in a number of biological activities, such as antioxidant and anti-inflammatory activity. As a result of this, spirulina has found its way into the formulation of a great number of medicinal foods, functional foods, and nutritional supplements. Therefore, this article makes an effort to shed light on spirulina, its nutritional value as a result of its chemical composition, and its applications to some food product formulations, such as dairy products, snacks, cookies, and pasta, that are necessary at an industrial level in the food industry all over the world. In addition, this article supports the idea of incorporating it into the food sector, both from a nutritional and health perspective, as it offers numerous advantages.

Fibrous Clays in Dermopharmaceutical and Cosmetic Applications: Traditional and Emerging Perspectives.

Functionalization of natural clay minerals for high value-added pharmaceutical and cosmetic applications receives significant research attention worldwide attributable to a rising demand and ongoing search for green, efficient, economically sustainable and ecofriendly geomaterials. Fibrous clays, i.e. palygorskite and sepiolite, are naturally-occurring hydrated magnesium aluminum silicate clay minerals with 2:1 layer-chain microstructure and one-dimensional nanofibrous morphology. Due to their unique structural, textural and compatibility features, over the past decade, fibrous clays and their organic modified derivatives are increasingly used in the dermopharmaceutical and cosmetic fields as excipients, active agents or nanocarriers to develop novel skin delivery systems or to modify drug release profile for enhanced health effects. This comprehensive review presents the up-to-date information on fibrous clays used in topically-applied products for therapeutic and cosmetic purposes with the focus on their performance-related structural characteristics and the underlying mechanisms. The recent advancement of fibrous clay-based skin delivery systems was summarized in wide range of applications including pelotherapy, wound healing, antimicrobial action, coloration and UV protection. An overview of the commonly used topically-applied dosage forms (powders, hydrogels, films, peloids and Pickering emulsion) as well as the toxicological aspects was also included, which might provide guidance to the design and development of fibrous clay-based skin delivery systems.

The effect of iron oxide types on the photochemical transformation of organic phosphorus in water.

Iron oxides play an important role in the transport and transformation of organic phosphorus in aquatic environments. However, the effect of different types of iron oxide on the environmental fate of organic phosphorus has remained unclear. In this study, the photodegradation of the organic phosphorus compound adenosine triphosphate (ATP) via the activity of crystalline (goethite) and amorphous (ferrihydrite) iron oxides was investigated. It was found that ATP was photodegraded by goethite, resulting in the release of dissolved inorganic phosphate under simulated sunlight irradiation. The concentration of ATP on goethite decreased by 75% after 6 h of simulated sunlight irradiation, while the concentration of ATP on ferrihydrite decreased by only 22%. ATR-FTIR spectroscopy revealed that the intensity of the peaks for the P-O and PO stretching vibrations in the goethite-ATP complex decreased significantly more after simulated sunlight irradiation than did those for the ferrihydrite treatment. Combined with the higher TOC/TOC0 values for the goethite treatment, the results indicate that a more vigorous photochemical reaction took place in the presence of goethite than with ferrihydrite. Reactive oxygen species analysis also showed that hydroxyl and superoxide anion radicals were generated when goethite was exposed to simulated sunlight irradiation, while ferrihydrite did not exhibit this ability. Overall, this study highlights that the type of iron oxide is an important factor in the transformation of organic phosphorus in aquatic environments.

Selective adsorption of various phosphorus species coexistence in water-soluble ammonium polyphosphate on goethite: Experimental investigation and molecular dynamics simulation.

The geochemical processes of polyphosphates (poly-Ps) are important for phosphorus (P) management and environmental protection. Water-soluble ammonium polyphosphate (APP) containing various P species has been increasingly used as an alternative P-fertilizer. The various P species coexistence and the chelation of poly-Ps with mental would trigger the P's competitive adsorption and affect the APP's adsorption intensity on goethite, compared to single orthophosphate (P1). P adsorption behaviors of APP1 with two P species and APP2 with seven P species on goethite were investigated via batch experiments in comparison to the traditional P-fertilizer of mono-ammonium phosphate (MAP). Coadsorption of P1 and pyrophosphate (P2) on goethite was investigated by molecular dynamics (MD) simulation. The more Fe3+ dissolved from goethite as a bridge due to the chelation of poly-Ps in APP and contributed to the stronger APP adsorption on goethite compared with MAP. Ion chromatography and spectral analysis showed P1 and P2 in APP were mainly adsorbed by goethite via mainly forming bidentate complexes. The goethite preferentially adsorbed P1 at lower APP concentration but increased the poly-Ps' adsorption at higher APP concentration. MD simulation showed that electrostatic interaction and hydrogen bonds played a key role in water-phosphates-goethite systems. The P1 pre-adsorbed on goethite could be replaced by P2 at high P2 concentration. The results develop new insights regarding the selective adsorption of various P species coexistence in goethite-rich environments.

Effects of mineral species and petroleum components on thermal desorption behavior of petroleum-contaminated soil.

Thermal desorption (TD) behavior of high-concentration petroleum-contaminated soil (PCS) is affected by soil composition, especially inorganic minerals. In this study, the TD behavior of petroleum-contaminated quartz (original mineral) and kaoline (clay mineral) were compared with those of pure petroleum (Petro-free); their "saturate, aromatic, resin, and asphaltenes" (SARA) fractions were investigated using thermogravimetry and differential thermogravimetry (TG-DTG). The modelling of the petroleum removal kinetics was also analyzed to provide insights into the mechanism. The results revealed that the limiting factor controlling the desorption of petroleum from quartz (Petro-Qtz) and kaoline (Petro-Kln) is the minerals, which increased the effective TD temperature by 200 °C and decreased TD efficiency by 2%. Compared to Petro-Qtz, Petro-Kln showed a lower desorption efficiency of 5% and the process was accomplished at a higher temperature of 100 °C. The investigation on SARA fractions indicated that polar fractions (i.e., aromatics, resins, and asphaltenes) were strongly captured by the minerals. The increment of the TD temperature of petroleum (resins-160 °C > aromatics-20 °C > saturates-5 °C) increased with the polarity of petroleum components. These results could be validated by thermogravimetry-gas chromatography/mass spectroscopy (TG-GC/MS) through the delayed desorption of naphthalene and acenaphthene. Furthermore, the increment of the TD temperature of SARA fractions on kaoline was higher than those on quartz. This makes sense because the kaoline decreased the diffusion of hydrocarbons due to its porosity features and higher specific surface area (kaoline 5.3300 m2 g-1, quartz 0.1153 m2 g-1). In addition, the analysis of the desorption kinetic models showed that the observed hysteresis was related to the diffusion barrier caused by chemisorption (n＜1). In consequence, the Petro-Kln showed a lower desorption efficiency, a slower desorption, and as a result, a higher energy consumption (0.476 kW h) for thermal remediation than Petro-Qtz (0.238 kW h).

Exploring the effects of substrate mineral fines on oil translocation in the shoreline environment: Experimental analysis, numerical simulation, and implications for spill response.

Mineral fines act a pivotal part in determining the fate and behavior of oil. In this study, the infiltrations of oil emulsion in simulated sediments and natural shoreline sediments were investigated using a fixed bed experiment. Oil infiltration process was simulated based on fixed-bed dispersion model. The role of mineral fines in oil release was explored using simulated and natural sediments. Although mineral fines exhibited a higher affinity for oil, it was found that increasing fines fractions decreased the flow rate of oil emulsion, thereby decreasing the oil retention in the sediment column. In terms of oil release from the sediment, the highest level of oil mass was observed in the oil-mineral flocculation phase compared to the water column and the water surface compartments. Compared to light crude oil, the release of engine oil from sediment was less. The effects of mineral fines on oil infiltration and release were also confirmed by using natural shoreline sediments. Results of our detailed field studies also showed that current shoreline classification datasets do not characterize the presence and fraction of mineral fines at a level of detail required to accurately predict the significance of oil translocation following spill incidents.

Understanding Necrosol pedogenetical processes in post-Roman burials developed on dunes sands.

In Archaeology much emphasis is dedicated to bone preservation, but less attention is paid to the burial soil (i.e., Necrosol), despite its crucial role in governing the geochemical environment. The interaction between human remains and sediments starts after inhumation, leading to bidirectional physico-chemical changes. To approach these complex, bidirectional processes, we sampled at high resolution (n = 46) two post-Roman wooden coffin burials (one single and another double), and the coeval paleosol (n = 20; nearby pedo-sedimentary sequence). The samples were analysed for physical (grain size, colour) and chemical (pH; LOI; elemental composition: FTIR-ATR, XRF, C, N) properties. Principal component analysis enabled to identify five main pedogenetical processes: decalcification, melanization, acidification, neoformation of secondary minerals (i.e., clays) and enrichment in phosphorus. Melanization, acidification and phosphorous enrichment seem to be convergent processes in Necrosols-irrespective of the parent material. Decalcification may be restricted to carbonate containing soil/sediments. Despite not mentioned in previous research, clay formation might also be an overall process. Compared to the local, coeval paleosol, pedogenesis in the studied burial soils was low (double burial) to moderate (single burial). Our results also emphasize the need to study the finer soil fractions, as they provide clues both on soil formation and bone diagenesis.

Extracellular polymeric substance induces biogenesis of vivianite under inorganic phosphate-free conditions.

Vivianite is often found in reducing environments rich in iron and phosphorus from organic debris degradation or phosphorus mineral dissolution. The formation of vivianite is essential to the geochemical cycling of phosphorus and iron elements in natural environments. In this study, extracellular polymeric substances (EPS) were selected as the source of phosphorus. Microcosm experiments were conducted to test the evolution of mineralogy during the reduction of polyferric sulfate flocs (PFS) by Shewanella oneidensis MR-1 (S. oneidensis MR-1) at EPS concentrations of 0, 0.03, and 0.3 g/L. Vivianite was found to be the secondary mineral in EPS treatment when there was no phosphate in the media. The EPS DNA served as the phosphorus source and DNA-supplied phosphate could induce the formation of vivianite. EPS impedes PFS aggregation, contains redox proteins and stores electron shuttle, and thus greatly promotes the formation of minerals and enhances the reduction of Fe(III). At EPS concentration of 0, 0.03, and 0.3 g/L, the produced HCl-extractable Fe(II) was 107.9, 111.0, and 115.2 mg/L, respectively. However, when the microcosms remained unstirred, vivianite can be formed without the addition of EPS. In unstirred systems, the EPS secreted by S. oneidensis MR-1 could agglomerate at some areas, resulting in the formation of vivianite in the proximity of microbial cells. It was found that vivianite can be generated biogenetically by S. oneidensis MR-1 strain and EPS may play a key role in iron reduction and concentrating phosphorus in the oligotrophic ecosystems where quiescent conditions prevail.

Chemical and Reactive Transport Processes Associated with Hydraulic Fracturing of Unconventional Oil/Gas Shales.

Hydraulic fracturing of unconventional oil/gas shales has changed the energy landscape of the U.S. Recovery of hydrocarbons from tight, hydraulically fractured shales is a highly inefficient process, with estimated recoveries of <25% for natural gas and <5% for oil. This review focuses on the complex chemical interactions of additives in hydraulic fracturing fluid (HFF) with minerals and organic matter in oil/gas shales. These interactions are intended to increase hydrocarbon recovery by increasing porosities and permeabilities of tight shales. However, fluid-shale interactions result in the dissolution of shale minerals and the release and transport of chemical components. They also result in mineral precipitation in the shale matrix, which can reduce permeability, porosity, and hydrocarbon recovery. Competition between mineral dissolution and mineral precipitation processes influences the amounts of oil and gas recovered. We review the temporal/spatial origins and distribution of unconventional oil/gas shales from mudstones and shales, followed by discussion of their global and U.S. distributions and compositional differences from different U.S. sedimentary basins. We discuss the major types of chemical additives in HFF with their intended purposes, including drilling muds. Fracture distribution, porosity, permeability, and the identity and molecular-level speciation of minerals and organic matter in oil/gas shales throughout the hydraulic fracturing process are discussed. Also discussed are analysis methods used in characterizing oil/gas shales before and after hydraulic fracturing, including permeametry and porosimetry measurements, X-ray diffraction/Rietveld refinement, X-ray computed tomography, scanning/transmission electron microscopy, and laboratory- and synchrotron-based imaging/spectroscopic methods. Reactive transport and spatial scaling are discussed in some detail in order to relate fundamental molecular-scale processes to fluid transport. Our review concludes with a discussion of potential environmental impacts of hydraulic fracturing and important knowledge gaps that must be bridged to achieve improved mechanistic understanding of fluid transport in oil/gas shales.

Geochemical Modeling of Celestite (SrSO4) Precipitation and Reactive Transport in Shales.

Celestite (SrSO4) precipitation is a prevalent example of secondary sulfate mineral scaling issues in hydraulic fracturing systems, particularly in basins where large concentrations of naturally occurring strontium are present. Here, we present a validated and flexible geochemical model capable of predicting celestite formation under such unconventional environments. Simulations were built using CrunchFlow and guided by experimental data derived from batch reactors. These data allowed the constraint of key kinetic and thermodynamic parameters for celestite precipitation under relevant synthetic hydraulic fracturing fluid conditions. Effects of ionic strength, saturation index, and the presence of additives were considered in the combined experimental and modeling construction. This geochemical model was then expanded into a more complex system where interactions between hydraulic fracturing fluids and shale rocks were allowed to occur subject to diffusive transport. We find that the carbonate content of a given shale and the presence of persulfate breaker in the system strongly impact the location and extent of celestite formation. The results of this study provide a novel multicomponent reactive transport model that may be used to guide future experimental design in the pursuit of celestite and other sulfate mineral scale mitigation under extreme conditions typical of hydraulic fracturing in shale formations.