Current brine management strategies are based on the disposal of brine in nearby aquifers, representing a loss in potential water and mineral resources. Zero liquid discharge (ZLD) is a possible strategy to reduce brine rejection while increasing the resource recovery from desalination plants. However, ZLD substantially increases the energy consumption and carbon footprint of a desalination plant. The predominant strategy to reduce the energy consumption and carbon footprint of ZLD is through the use of a hybrid desalination technology that integrates renewable energy. Here, we built a computational thermodynamic model of the most mature electrified hybrid technology for ZLD powered by photovoltaic (PV). We examine the potential size and cost of ZLD plants in the US. This work explores the variables (geospatial and design) that most influence the levelized cost of water and the second law efficiency. There is a negative correlation between minimizing the LCOW and maximizing the second-law. And maximizing the second-law, the states that more brine produces, Texas is the location where the studied system achieves the lowest LCOW and high second-law efficiency, while California is the state where the studied system is less favorable. A multiobjective optimization study assesses the impact of considering a carbon tax in the cost of produced water and determines the best potential size for the studied plant.
Montmorillonite layer edge surfaces have pH-dependent properties, which arises from the acid–base reactivity of their surface functional groups. Edge surface acidity (with intrinsic reaction equilibrium constant, pKa) is a chemical property that is affected by crystal structure. While a cis-vacant structure predominates in natural montmorillonites, prior molecular-level studies assume a centrosymmetric trans-vacant configuration, which potentially leads to an incorrect prediction of montmorillonite acid–base surface properties. We computed intrinsic acidity constants of the surface sites of a montmorillonite layer with a cis-vacant structure using the first-principles molecular dynamics-based vertical energy gap method. We evaluated pKa values for both non-substituted and Mg-substituted layers on common edge surfaces (i.e., surfaces perpendicular to [010], [01̅0], [110], and [1̅1̅0] crystallographic directions). The functional groups ≡Si(OH), ≡Al(OH2)2/≡Al(OH)(OH2), and ≡SiO(OH)Al sites on surfaces perpendicular to [010] and [01̅0] and ≡Si(OH)U, ≡Si(OH)L, ≡Al(OH2), and ≡Al(OH2)2 on surfaces perpendicular to [110] and [1̅1̅0] determine the proton reactivity of non-substituted cis-vacant edge surfaces. Moreover, the structural OH sites on edge surfaces had extremely high pKa values, which do not show reactivity at a common pH. Meanwhile, Mg2+ substitution results in an increase in pKa values at local or adjacent sites, in which the effect is limited by the distance between the sites. A surface complexation model was built with predicted pKa values, which enabled us to predict surface properties as a function of pH and ionic strength. Edge surface charge of both trans- and cis-vacant models has little dependence on Mg2+ substitutions, but the dependence on the crystal plane orientation is strong. In particular, at pH below 7, edge surfaces are positively or negatively charged depending on their orientation. Implications of these findings on contaminant adsorption by smectites are discussed.
Perfluorooctanesulfonate (PFOS) and its alternatives, including chlorinated polyfluorinated ether sulfonates (Cl-PFESAs), are mainly detected per- and polyfluoroalkyl substances (PFAS) in human samples such as milk. However, the mechanism of their blood to milk transfer was not well studied. Here, 145 paired maternal serum and human milk samples were analyzed for six PFOS isomers and Cl-PFESAs to evaluate the transfer efficiency from maternal serum to human milk (TEHM/MS). Besides physicochemical properties, this study for the first time evaluated the influencing effects of the primary components in human milk (carbohydrate, lipid, and protein) on TEHM/MS of PFAS. No significant association was observed between TEHM/MS and the albumin binding affinity of the compounds (p = 0.601), but TEHM/MS was significantly negatively correlated with the logarithmic octanol-water partition coefficients (r2 = 0.853, p = 0.001), the logarithmic membrane-water partition coefficients (r2 = 0.679, p = 0.012), and the carbohydrate contents in human milk. The effect of carbohydrate was further confirmed using in vitro tests. The negative associations between TEHM/MS and hydrophobicity, membrane passive permeability, and the carbohydrate content in human milk consistently indicated that passive diffusion through the paracellular route might be the main transfer pathway for PFOS and Cl-PFESAs from blood to milk in humans.
Microplastics (MPs) and oil pollution are major concerns in oceans. Although their coexistence in oceans and the associated MP-oil-dispersant agglomerates (MODAs) have been reported, limited attention is given to the behavior of the co-contaminants. This study investigated MODA transport in a simulated ocean system and explored related mechanisms under various oil types, salinities, and mineral concentrations. We found that more than 90% of the heavy oil-formed MODAs stayed at the seawater surface, while the light oil-formed MODAs were widely distributed throughout the seawater column. The increased salinity promoted MODAs formed by 7 and 90 μm MPs to transport from the seawater surface to the column. This was elucidated by the Derjaguin-Landau-Verwey-Overbeek theory as more MODAs formed under higher salinities and dispersants kept them stable in the seawater column. Minerals facilitated the sinking of large MP-formed MODAs (e.g., 40 μm) as minerals were adsorbed on the MODA surface, but their impact on small MP-formed MODAs (e.g., 7 μm) was negligible. A MODA-mineral system was proposed to explain their interaction. Rubey's equation was recommended to predict the sinking velocity of MODAs. This study is the first attempt to reveal MODA transport. Findings will contribute to the model development to facilitate their environmental risk evaluation in oceans.
The association of arsenic (As) with colloidal particles could facilitate its transport to adjacent water systems or alter its availability in soil-rice systems. However, little is known about the size distribution and composition of particle-bound As in paddy soils, particularly under changing redox conditions. Here, we incubated four As-contaminated paddy soils with distinctive geochemical properties to study the mobilization of particle-bound As during soil reduction and subsequent reoxidation. Using transmission electron microscopy-energy dispersive spectroscopy and asymmetric flow field-flow fractionation, we identified organic matter (OM)-stabilized colloidal Fe, most likely in the form of (oxy)hydroxide-clay composite, as the main arsenic carriers. Specifically, colloidal As was mainly associated with two size fractions of 0.3-40 and >130 kDa. Soil reduction facilitated the release of As from both fractions, whereas reoxidation caused their rapid sedimentation, coinciding with solution Fe variations. Further quantitative analysis demonstrated that As concentrations positively correlated with both Fe and OM concentrations at nanometric scales (0.3-40 kDa) in all studied soils during reduction and reoxidation, yet the correlations are pH-dependent. This study provides a quantitative and size-resolved understanding of particle-bound As in paddy soils, highlighting the importance of nanometric Fe-OM-As interactions in paddy As geochemical cycling.
Chlorine reactions with peptide-bound amino acids form disinfection byproducts and contribute to pathogen inactivation by degrading protein structure and function. Peptide-bound lysine and arginine are two of the seven chlorine-reactive amino acids, but their reactions with chlorine are poorly characterized. Using N-acetylated lysine and arginine as models for peptide-bound amino acids and authentic small peptides, this study demonstrated conversion of the lysine side chain to mono- and dichloramines and the arginine side chain to mono-, di-, and trichloramines in ≤0.5 h. The lysine chloramines formed lysine nitrile and lysine aldehyde at ∼6% yield over ∼1 week. The arginine chloramines formed ornithine nitrile at ∼3% yield over ∼1 week but not the corresponding aldehyde. While researchers hypothesized that the protein aggregation observed during chlorination arises from covalent Schiff base cross-links between lysine aldehyde and lysine on different proteins, no evidence for Schiff base formation was observed. The rapid formation of chloramines and their slow decay indicate that they are more relevant than the aldehydes and nitriles to byproduct formation and pathogen inactivation over timescales relevant to drinking water distribution. Previous research has indicated that lysine chloramines are cytotoxic and genotoxic to human cells. The conversion of lysine and arginine cationic side chains to neutral chloramines should alter protein structure and function and enhance protein aggregation by hydrophobic interactions, contributing to pathogen inactivation.
Blood is an important reservoir for Pb storage in living organisms, and the storage of Pb in blood cells inhibits its discharge from blood. However, the mechanism and molecular targets of Pb entry and exit from blood cells have not been elucidated, which is the major barrier to reducing blood Pb levels in normal human beings. In this study, we explored the effect of Pb-binding proteins on blood Pb levels in rats at environmentally relevant concentrations (0.32 μg/g) by identifying the functions of Pb-binding proteins and validating them with inhibitors. The results showed that Pb-binding proteins in blood cells were mainly related to phagocytosis, while in plasma, they were mainly involved in the regulation of endopeptidase activity. Meanwhile, at the normal population Pb levels, endocytosis inhibitors, endopeptidase activity inhibitors, and coadministration of both can reduce the level of Pb in MEL (mouse erythroleukemia cells) cells by up to 50, 40, and 50%, respectively, while in rat blood, the reduction can reach up to 26, 13, and 32%, respectively. Collectively, these findings reveal that endocytosis increases blood Pb levels and provides a possible molecular target for Pb excretion at ambient concentrations.
Far-UVC radiation is an emerging tool for combating pathogenic microorganisms in water, but its vulnerability to water matrix components remains unclear. We herein report the critical impacts of nitrate during Far-UVC disinfection of water. Nitrate at environmentally relevant concentrations (0.5-10.0 mg-N L-1) significantly inhibits Escherichia coli inactivation by Far-UVC radiation at 222 nm, via prolonging the "lag phase" of inactivation and reducing the inactivation rate constants by 1.08-2.74 times, while it shows negligible impact on E. coli inactivation by UVC radiation at 254 nm. The inhibitory impact of nitrate on Far-UVC disinfection is attributed to its strong light-shielding effect. Although hydroxyl radicals and reactive nitrogen species are generated from Far-UVC photolysis of nitrate at high concentrations of 10-13 and ∼10-7 M, respectively, those radicals are unable to compensate for the light-shielding effect of nitrate on E. coli inactivation. Moreover, reactive nitrogen species lead to the formation of nitrogenous byproducts, which increase the genotoxicity of the water. The findings advance the fundamental photochemistry and radical chemistry of nitrate at 222 nm and provide useful insights to guide the operation of Far-UVC in treating nitrate-containing water.
