The heterogeneous coprecipitation of nanocrystals with metals on substrates plays a significant role in both natural and engineered systems. Due to the small dimensions and thereby the large specific surface area, nanocrystal coprecipitation with metals, which is ubiquitous in natural settings, exerts drastic effects on the biogeochemical cycling of metals on the earth’s crust. Meanwhile, the controlled synthesis of nanocrystals with metal doping to achieve tunable size/composition enables their broad applications as adsorbents and catalysts in many engineered settings. Despite their importance, complex interactions among aqueous ions/polymers, nanocrystals, substrates, and metals are far from being well-understood, leaving the controlling mechanisms for nanocrystal formation with metals on substrates uncovered. In this Account, we discuss our systematic investigation over the past 10 years of the heterogeneous formation of representative nanocrystals with metals on typical substrates. We chose Fe(OH)3 and BaSO4 as representative nanocrystals. Mechanisms for varied metal coprecipitation were also investigated for both types of nanocrystals (i.e., Fe, Al, Cr, Cu, and Pb)(OH)3 and (Ba, Sr)(SO4, SeO4, and SeO3)). Bare SiO2 and Al2O3, as well as those coated with varied organics, were selected as geologically or synthetically representative substrates. Through the integration of state-of-the-art nanoscale interfacial characterization techniques with theoretical calculations, the complex interactions during nanocrystal formation at interfaces were probed and the controlling mechanisms were identified. For BaSO4 and Fe(OH)3 formation on substrates, the local supersaturation levels near substrates were controlled by Ba2+ adsorption and the electrostatic attraction of Fe(OH)3 monomer/polymer to substrates, respectively. Meanwhile, substrate hydrophobicity controlled the interfacial energy for the nucleation of both nanocrystals on (in)organic substrates. Metal ions’ (i.e., Cr/Al/Cu/Pb) hydrolysis constants and substrates’ dielectric constants controlled metal ion adsorption onto substrates, which altered the surface charges of substrates, thus controlling heterogeneous Fe(OH)3 nanocrystal formation on substrates by electrostatic interactions. The sizes and compositions of heterogeneous (Fe, Cr)(OH)3 and (Ba, Sr)(SO4, SeO4, SeO3) formed on substrates were found to be distinct from those of homogeneous precipitates formed in solution. The substrate (de)protonation could alter the local solution’s pH and the substrates’ surface charge; substrates could also adsorb cations, affecting local Fe/Cr/Ba/Sr ion concentrations at solid–water interfaces, thus controlling the amount/size/composition of nanocrystals by tuning their nucleation/growth/deposition on substrates. From slightly supersaturated solution, homogeneous coprecipitates of microsized (Ba, Sr)(SO4, SeO4, SeO3) formed through growth, with little Sr/Se(VI) incorporation due to higher solubilities of SrSO4 and BaSeO4 over BaSO4. While cation enrichment near substrates made the local solution highly supersaturated, nanosized coprecipitates formed on substrates through nucleation, with more Sr/Se(VI) incorporation due to lower interfacial energies of SrSO4 and BaSeO4 over BaSO4. The new insights gained advanced our understanding of the biogeochemical cycling of varied elements at solid–water interfaces and of the controlled synthesis of functional nanocrystals.

Molybdenum (Mo) is an essential nutrient for almost all organisms. However, at high concentrations, it can be toxic to animals and plants. This study investigated the interactions of Mo(VI) with iron oxyhydroxides during ferrihydrite bioreduction in the presence of Fe(III)-reducing Geobacter sulfurreducens. Here, we showed that Mo concentration controlled ferrihydrite phase transformation, leading to Mo release. With the biotic reduction of ferrihydrite and Fe(II) production, Mo(VI) reduction and Mo(IV)O2 formation were observed for the first time, which further immobilized Mo after surface adsorption of Mo(VI). At low Mo levels (Mo/Fe molar ratios of 1–2%), sufficient Fe(II) adsorption onto ferrihydrite resulted in its transformation into magnetite nanoparticles (>80%, ∼25 nm), which catalyzed the reduction of Mo(VI) to form Mo(IV)O2 and immobilized Mo. Contrastingly, at high Mo concentrations (Mo/Fe molar ratios of 5–10%), Mo(VI)O42– adsorption onto ferrihydrite limited Fe(II) adsorption; subsequently, less magnetite (<8–12%) formed while more goethite (∼30–50%, width and length >15 and 100 nm, respectively) and siderite (∼20–30%, width and length >100 and 200 nm, respectively) with larger particle sizes formed instead, causing Mo(VI) release due to lower Mo adsorption. This study provides a comprehensive understanding of the interaction mechanisms among Geobacter sulfurreducens, Mo(VI), and iron oxyhydroxides, enabling predictions and controls of long-term Mo mobility and Fe mineral transformation under a variety of biogeochemical scenarios.

The aggregation behavior of ferrihydrite nanoparticles (FNPs) can control the fate of associated aqueous contaminants, trace elements, and organic compounds. However, FNP aggregation is difficult to predict in the presence of organic matter (OM), given the heterogeneity in the OM properties. Five model OMs based on (poly)acrylic acid (PAA or AA) and polyethylene glycol with or without terminal carboxyl groups (PEG or PEGbis, respectively) were chosen to probe the influence of key OM properties─specifically, carboxyl richness and molecular weight (MW)─and the dominant mechanisms by which they influence OM adsorption onto FNPs and the resulting aggregation. For OMs with similar MWs, those with a higher carboxyl richness adsorbed more extensively onto FNPs: PAA2k > PEGbis > PEG. Meanwhile, for OMs with the same carboxyl richness, higher MW OMs adsorbed more: PAA25k > PAA2k > AA. Furthermore, the subsequent aggregation of FNPs was largely controlled by the adsorbed mass. OMs with negligible adsorption (i.e., PEG and AA) did not change the aggregation behavior of FNPs. For OMs with low carboxyl richness (PEGbis), accelerated aggregation occurred through a bridging effect with low adsorbed mass. For OMs with high carboxyl richness (PAA2k and PAA25k), aggregation was accelerated at moderate adsorbed OM masses by patch-charge attraction and was inhibited with high adsorbed OM mass due to steric repulsion. This study provided new insights into understanding and predicting the transport and fate of FNPs and natural organic matter (NOM) in natural environments with various NOM compositions.

ron/chromium hydroxide coprecipitation controls the fate and transport of toxic chromium (Cr) in many natural and engineered systems. Organic coatings on soil and engineered surfaces are ubiquitous; however, mechanistic controls of these organic coatings over Fe/Cr hydroxide coprecipitation are poorly understood. Here, Fe/Cr hydroxide coprecipitation was conducted on model organic coatings of humic acid (HA), sodium alginate (SA), and bovine serum albumin (BSA). The organics bonded with SiO2 through ligand exchange with carboxyl (–COOH), and the adsorbed amounts and pKa values of –COOH controlled surface charges of coatings. The adsorbed organic films also had different complexation capacities with Fe/Cr ions and Fe/Cr hydroxide particles, resulting in significant differences in both the amount (on HA > SA(–COOH) ≫ BSA(–NH2)) and composition (Cr/Fe molar ratio: on BSA(–NH2) ≫ HA > SA(–COOH)) of heterogeneous precipitates. Negatively charged –COOH attracted more Fe ions and oligomers of hydrolyzed Fe/Cr species and subsequently promoted heterogeneous precipitation of Fe/Cr hydroxide nanoparticles. Organic coatings containing –NH2 were positively charged at acidic pH because of the high pKa value of the functional group, limiting cation adsorption and formation of coprecipitates. Meanwhile, the higher local pH near the –NH2 coatings promoted the formation of Cr(OH)3. This study advances fundamental understanding of heterogeneous Fe/Cr hydroxide coprecipitation on organics, which is essential for successful Cr remediation and removal in both natural and engineered settings, as well as the synthesis of Cr-doped iron (oxy)hydroxides for material applications.

Mineral scale refers to the hard inorganic solids nucleated on substrates or deposited from the aqueous phase. The formation and deposition of barium sulfate and strontium sulfate in various industries, such as water treatment and oilfield operations, can significantly impact facility operations, posing serious threats. Machine learning (ML) approaches have been adopted recently in scale threat predictions to address the limitations of conventional scaling prediction models. However, there are few reports on collecting sulfate mineral scaling data, employing ML methods for data analysis, and evaluating the modeling results to gain deeper insights of sulfate mineral scaling process and to improve the accuracy of sulfate scaling threat prediction. Despite comprehensive experimental studies, the literature does not provide adequate guidance for identifying the influence on the solubility of barium sulfate and strontium sulfate under different aqueous environments and actual operating conditions. To this end, this study collected 1600 experimental datasets of barium/strontium sulfate from the literature to construct and evaluate the reliability and versatility of a ML-based model for sulfate solubility calculations. Single neural networks, hybrid neural networks, and optimization algorithms were employed to build solubility prediction models for barium sulfate and strontium sulfate across a wide range of temperatures, pressures, and different ions. The model's applicability in predicting sulfate scaling threats in various actual operating environments demonstrated its broad usability, consistent with its actual performance. This study marks the first stride towards constructing a reliable model for identifying the scaling trends of barium sulfate and strontium sulfate across various operating conditions, underscoring the importance of developing robust and accurate prediction models to address challenges in various industrial systems.

he simultaneous precipitation of (Fe, Cr)(OH)3 nanoparticles in solution (homogeneous) and on soil surfaces (heterogeneous), which controls Cr transport in soil and aquatic systems, was quantified for the first time in the presence of model surfaces, i.e., bare and natural organic matter (NOM)-coated SiO2 and Al2O3. Various characterization techniques were combined to explore the surface-ion-precipitate interactions and the controlling mechanisms. (Fe, Cr)(OH)3 accumulation on negatively charged SiO2 was mainly governed by electrostatic interactions between hydrolyzed ion species or homogeneous (Fe, Cr)(OH)3 and surfaces. The elevated pH through protonation of Al2O3 surface hydroxyls resulted in higher Cr/Fe ratios in both homogeneous and heterogeneous coprecipitates. Due to ignorable NOM adsorption onto SiO2, the amounts of (Fe, Cr)(OH)3 precipitates on bare/NOM-SiO2 were similar; contrarily, attributed to favored NOM adsorption onto Al2O3 and consequently carboxyl association with metal ions or (Fe, Cr)(OH)3 nanoparticles, remarkably more heterogeneous precipitates harvested on NOM-Al2O3 than bare-Al2O3. With the same solution supersaturation, the total amounts of homogeneous and heterogeneous precipitates were similar irrespective of the substrate type. With lower pH, decreased electrostatic forces between substrates and precipitates shifted (Fe, Cr)(OH)3 distribution from heterogeneous to homogeneous phases. The quantitative knowledge of (Fe, Cr)(OH)3 distribution and the controlling mechanisms can assist in better Cr sequestration in natural and engineered settings.

The poor colloidal stability of magnetite nanoparticles (MNPs) limits their mobility and application, so various organic coatings (OCs) were applied to MNPs. Here, a comparative study on the colloidal stability of MNPs coated with acetic (HAc) and polyacrylic acids (PAA) was conducted under varied pH (5.0–9.0) in the presence of different concentrations of cations and anions, as well as humic acid (HA). Comparing the effects of various cations and anions, the stability of both HAc/PAA-MNPs followed the order: Na+ > Ca2+and PO43− > SO42− > Cl−, which could be explained by their adsorption behaviors onto HAc/PAA-MNPs and the resulting surface charge changes. Under all conditions even with more anion adsorption onto HAc-MNPs (0.14–22.56 mg/g) than onto PAA-MNPs (0.04–18.34 mg/g), PAA-MNPs were more negatively charged than HAc-MNPs, as PAA has a lower pHIEP (2.6 ± 0.1) than that of HAc (3.7 ± 0.1). Neither the HAc nor PAA coatings were displaced by phosphate even at considerably high phosphate concentration. Compared with HAc-MNPs, the stability of PAA-MNPs was greatly improved under all studied conditions, which could be due to both stronger electrostatic and additional steric repulsion forces among PAA-MNPs. Besides, under all conditions, Derjaguin-Landau-Verwey-Overbeek (DLVO) explained well the aggregation kinetic of HAc-MNPs; while extended DLVO (EDLVO) successfully predict that of PAA-MNPs, indicating steric forces among PAA-MNPs. The aggregation of HAc/PAA-MNPs was all inhibited in varied electrolyte solutions by HA (2 mg C/L) addition. This study suggested that carboxyl coatings with higher molecular weights and pKa values could stabilize MNPs better due to stronger electrostatic and additional steric repulsion. However, in the presence of HA, these two forces were mainly controlled by adsorbed HA instead of the organic pre-coatings on MNPs.

Phosphate addition is commonly applied to remediate lead contaminated sites via the formation of lead phosphate particles with low solubility. However, the effects of natural organic matter (NOM) with different properties, as well as the contributions of specific interactions (particle-particle, particle-NOM, and NOM-NOM) in enhanced stabilization or flocculation of the particles, are not currently well understood. This study investigates the influence of two aquatic NOM and two soil or coal humic acid (HA) extracts on the aggregation behavior of lead phosphate particles and explores the controlling mechanisms. All types of NOM induced disaggregation and steric stabilization of the particles in the presence of Na+ (100 mM) or low (1 mM) Ca2+ concentrations, as well as at low NOM concentrations (1 mgC/L). However, for the soil and coal HA, a threshold at NOM concentrations of 10 mgC/L and high (3 mM) Ca2+ concentrations was observed where bridging flocculation (rather than steric stabilization) occurred. In situ attenuated total reflectance – Fourier transform infrared characterization confirmed adsorption of the soil and coal humic acid extracts (10 mgC/L) onto the surface of the lead phosphate particles in 3 mM Ca2+, whereas dynamic and static light scattering demonstrated extensive HA flocculation that dominated the overall scattered light intensities. These results imply that the accelerated aggregation was induced by a combination of HA adsorption and bridging flocculation by Ca2+. Overall, this research demonstrates that the type of NOM is critical to predict the colloidal stability of lead phosphate particles. Aquatic NOM stabilized the particles under all conditions evaluated, but soil or coal HA with higher molecular weight and aromaticity showed highly variable stabilization or flocculation behavior depending on the HA and Ca2+ concentrations available to adsorb to the particles and participate in bridging. These results provide new mechanistic insights on particle stabilization or destabilization by NOM.

More than two billion people worldwide have suffered thyroid disorders from either iodine deficiency or excess. By creating the national map of groundwater iodine throughout China, we reveal the spatial responses of diverse health risks to iodine in continental groundwater. Greater non-carcinogenic risks relevant to lower iodine more likely occur in the areas of higher altitude, while those associated with high groundwater iodine are concentrated in the areas suffered from transgressions enhanced by land over-use and intensive anthropogenic overexploitation. The potential roles of groundwater iodine species are also explored: iodide might be associated with subclinical hypothyroidism particularly in higher iodine regions, whereas iodate impacts on thyroid risks in presence of universal salt iodization exhibit high uncertainties in lower iodine regions. This implies that accurate iodine supply depending on spatial heterogeneity and dietary iodine structure optimization are highly needed to mitigate thyroid risks in iodine-deficient and -excess areas globally.

Magnetite nanoparticles (MNPs) with varied organic coatings (OCs) which improved their stability have broad environmental applications. However, the adsorbed amounts and layer thickness of varied OCs onto MNPs during the synthesis were generally not or poorly characterized, and their interactions with natural organic matter (NOM) were still in progress. In this study, acetic (HAc), citric (CA), and polyacrylic acid (PAA) were selected as model OCs, the adsorption behaviors of OCs on MNPs were characterized under varied aqueous C/Fe ratios, and the aggregation behaviors of MNPs with varied OCs (OC-MNPs) at neutral pH (7.0 ± 0.2) with NaCl (5–800 mM) in the presence/absence of NOM were systematically investigated. Under low aqueous C/Fe ratio, the adsorbed amounts of model OCs as –COOH/Fe ratio followed the order: CA ≈ PAA >> HAc. With high aqueous C/Fe ratio, the maximum adsorbed masses of OC-MNPs were similar. The adsorbed layer thicknesses of OC-MNPs were thoroughly characterized using three different methods, all showing that the adsorbed layer of PAA was thicker than that of CA and HAc. Derjaguin–Landau–Verwey–Overbeek (DLVO) and extended DLVO (EDLVO) calculations showed that electrostatic and van der Waals forces were dominant for CA-MNPs and HAc-MNPs stabilization; while steric repulsion played major roles in stabilizing PAA-MNPs, probably due to a thicker PAA layer. In the presence of NOM, stability behaviors of all OC-MNPs were similar, ascribing to the much greater amounts of NOM adsorbed than the OCs, causing greater steric repulsion. This study provides new mechanistic insights which could help better understand the effects of varied OCs on MNPs' colloidal stability.

Coprecipitation of selenium oxyanions with barite is a facile way to sequester Se in the environments. However, the chemical composition of Se-barite coprecipitates usually deviates from that predicted from thermodynamic calculations. This discrepancy was resolved by considering variations in nucleation and growth rates controlled by ion–mineral interactions, solubility, and interfacial energy. For homogeneous precipitation, ∼10% of sulfate, higher than thermodynamic predictions (<0.3%), was substituted by Se(IV) or Se(VI) oxyanion, which was attributed to adsorption-induced entrapment during crystal growth. For heterogeneous precipitation, thiol- and carboxylic-based organic films, utilized as model interfaces to mimic the natural organic-abundant environments, further enhanced the sequestration of Se(VI) oxyanions (up to 41–92%) with barite. Such enhancement was kinetically driven by increased nucleation rates of selenate-rich barite having a lower interfacial energy than pure barite. In contrast, only small amounts of Se(IV) oxyanions (∼1%) were detected in heterogeneous coprecipitates mainly due to a lower saturation index of BaSeO3 and deprotonation degree of Se(IV) oxyanion at pH 5.6. These roles of nanoscale mineralization mechanisms observed during composition selection of Se-barite could mark important steps toward the remediation of contaminants through coprecipitation.

Phosphate addition is commonly applied as an effective method to remediate lead contaminated sites via formation of low solubility lead phosphate solids. However, subsequent transport of the lead phosphate particles may impact the effectiveness of this remediation strategy. Hence, this study investigates the mechanisms involved in the aggregation of lead phosphate particles and their deposition in sand columns as a function of typical water chemistry parameters. Clean bed filtration theory was evaluated to predict the particle deposition behavior, using Derjaguin–Landau–Verwey–Overbeek (DLVO) theory to estimate particle-substrate interactions. The observed particle deposition was not predictable from the primary energy barrier in clean bed filtration models, even in simple monovalent background electrolyte (NaNO3), because weak deposition in a secondary energy minimum prevailed even at low ionic strength, and ripening occurred at ionic strengths of 12.5 mM or higher. For aged (aggregated) suspensions, straining also occurred at 12.5 mM or higher. Aggregation and deposition were further enhanced at low total P/Pb ratios (i.e., P/Pb = 1) and in the presence of divalent cations, such as Ca2+ (≥ 0.2 mM), which resulted in less negative particle surface potentials and weaker electrostatic repulsion forces. However, the presence of 5 mg C/L of humic acid induced strong steric or electrosteric repulsion, which hindered particle aggregation and deposition even in the presence of Ca2+. This study demonstrates the importance of myriad mechanisms in lead phosphate deposition and provides useful information for controlling water chemistry in phosphate applications for lead remediation.

Sulfate scaling, as insoluble inorganic sulfate deposits, can cause serious operational problems in various industries, such as blockage of membrane pores and subsurface media and impairment of equipment functionality. There is limited article to bridge sulfate formation mechanisms with field scaling control practice. This article reviews the molecular-level interfacial reactions and thermodynamic basis controlling homogeneous and heterogeneous sulfate mineral nucleation and growth through classical and non-classical pathways. Common sulfate scaling control strategies were also reviewed, including pretreatment, chemical inhibition and surface modification. Furthermore, efforts were made to link the fundamental theories with industrial scale control practices. Effects of common inhibitors on different steps of sulfate formation pathways (i.e., ion pair and cluster formation, nucleation, and growth) were thoroughly discussed. Surface modifications to industrial facilities and membrane units were clarified as controlling either the deposition of homogeneous precipitates or the heterogeneous nucleation. Future research directions in terms of optimizing sulfate chemical inhibitor design and improving surface modifications are also discussed. This article aims to keep the readers abreast of the latest development in mechanistic understanding and control strategies of sulfate scale formation and to bridge knowledge developed in interfacial chemistry with engineering practice.

Iron hydroxides are important scavengers for dissolved chromium (Cr) via coprecipitation processes; however, the influences of organic matter (OM) on Cr sequestration in Fe/Cr-OM ternary systems and the stability of the coprecipitates are not well understood. Here, Fe/Cr-OM coprecipitation was conducted at pH 3, and Cr hydroxide was undersaturated. Acetic acid (HAc), poly(acrylic acid) (PAA), and Suwannee River natural organic matter (SRNOM) were selected as model OMs, which showed different complexation capabilities with Fe/Cr ions and Fe/Cr hydroxide particles. HAc had no significant effect on the coprecipitation, as the monodentate carboxyl ligand in HAc did not favor complexation with dissolved Fe/Cr ions or Fe/Cr hydroxide nanoparticles. Contrarily, PAA and SRNOM with polydentate carboxyl ligand had strong complexation with Fe/Cr ions and Fe/Cr hydroxide nanoparticles, leading to significant amounts of PAA/SRNOM sequestered in the coprecipitates, which caused the structural disorder and fast aggregation of the coprecipitates. In comparison with that of PAA, preferential complexation of Cr ions with SRNOM resulted in higher Cr/Fe ratios in the coprecipitates. This study advances the fundamental understanding of Fe/Cr-OM coprecipitation and mechanisms controlling the composition and stability of the coprecipitates, which is essential for successful Cr remediation and removal in both natural and engineered settings.

Prior mineral scaling investigations mainly studied the effects of membrane surface properties rather than on the mineral properties and their impact on membrane permeability. In our study, mass, crystal growth orientation, and crystallinity of mineral precipitates on membranes, as well as their effects on membrane permeability have been investigated. Gypsum scaling tests on bare and bovine serum albumin (BSA)-conditioned membranes were conducted under different saturation indices. Results show that a longer scaling period was required for BSA-conditioned membranes to reach the same membrane permeate flux decline as bare membranes. Though the final reduced permeability was the same for both two membranes, the masses of the mineral precipitates on BSA-conditioned membranes were around two times more than those on bare membranes. Further mineral characterizations confirmed that different permeability decay rates of both types of the membrane were attributed to the differences in growth orientations rather than amounts of gypsum precipitates. Moreover, BSA-conditioned layers with high carboxylic density and specific molecular structure could stabilize bassanite and disrupt the oriented growth to inhibit the formation of needle-like gypsum crystals as observed on bare membranes, thus resulting in lower surface coverage with scales on membranes and alleviating the detrimental scaling effect on membrane permeability.

Reverse osmosis (RO) membranes are prone to fouling, which increases the cost of operation and decreases water recovery. In this study, a commercial membrane (ESPA2) was coated with an antiscaling material, i.e. polyacrylic acid (PAA), and an antimicrobial material, i.e. graphene oxide (GO), to reduce biofouling and scaling. Bare and modified membranes with polydopamine (ESPA2-PD), as a control, GO (ESPA2-GO), GO and PAA (ESPA2-GO-PAA), and PAA (ESPA2-PAA) were tested for their antiscaling and antibiofouling properties. ESPA2-GO and ESPA2-GO-PAA had the best performance. The latter showed  15% and 10% increase in normalized water flux compared to ESPA2 in mineral scaling and biofouling tests, respectively. This improvement can be attributed to the decrease in surface charge and the increase in hydrophilicity of membrane surface by both GO and PAA coating. Moreover, the antimicrobial characteristic of GO played a crucial role in reducing biofouling and PAA slightly enhanced antiscaling property when coated on ESPA2 but it did not improve the antibiofouling property. These results highlight the importance of antimicrobial property of the coating for biofouling prevention and show antiscaling materials can be effective not only as an additive to the feed but also as a coating on the membrane to reduce scaling.

The identification and characterization of lead-bearing and associated minerals in scales on lead pipes are essential to understanding and predicting the mobilization of lead into drinking water. Despite its long-recognized usefulness in the unambiguous identification of crystalline and amorphous solids, distinguishing between polymorphic phases, and rapid and non-destructive analysis on the micrometer spatial scale, the Raman spectroscopy (RS) technique has been applied only occasionally in the analysis of scales in lead service lines (LSLs). This article illustrates multiple applications of RS not just for the identification of phases, but also compositional and structural characterization of scale materials in harvested lead pipes and experimental pipe-loop/recirculation systems. RS is shown to be a sensitive monitor of these characteristics through analyses on cross-sections of lead pipes, raw interior pipe walls, particulates captured in filters, and scrapings from pipes. RS proves to be especially sensitive to the state of crystallinity of scale phases (important to their solubility) and to the specific chemistry of phases precipitated upon the introduction of orthophosphate to the water system. It can be used effectively alone as well as in conjunction with more standard analytical techniques. By means of fiber-optic probes, RS has potential for in situ, real-time analysis within water-filled pipes.

espite successful modeling of graphene as a 0.34-nm-thick optical film synthesized by exfoliation or chemical vapor deposition (CVD), graphene-induced shift of surface-plasmon resonance (SPR) of gold films has remained controversial. Here we report the resolution of this controversy by developing a clean CVD graphene transfer method and extending Maxwell-Garnett effective-medium theory (EMT) to two-dimensional (2D) materials. A SPR shift of 0.24° is obtained and it agrees well with 2D EMT in which wrinkled graphene is treated as a 3-nm graphene/air layered composite, in agreement with the average roughness measured by atomic force microscopy. Because the anisotropic built-in boundary condition of 2D EMT is compatible with graphene's optical anisotropy, graphene can be modeled as a film thicker than 0.34 nm without changing its optical property; however, its actual roughness, i.e., effective thickness, will significantly alter its response to strong out-of-plane fields, leading to a larger SPR shift.

Reverse osmosis (RO) technology is promising in the sustainable production of fresh water. However, expansion of RO use has been hindered by membrane fouling, mainly inorganic fouling known as scaling. Although membrane mineral scaling by chemical means have been investigated extensively, mineral scaling triggered by microbial activity has been largely neglected. In this study, the simultaneous biomineralization of CaCO3 and CaSO4 in the presence of three different microbial communities from fresh water, wastewater, and seawater was investigated. In the presence of either 13 or 79 mM of Ca2+ and SO42- in the media, the fresh water microbial community produced calcite/vaterite and vaterite/gypsum, respectively; the wastewater community produced vaterite and vaterite/gypsum, respectively; and the seawater community produced aragonite in both conditions. The results showed that the concentration of salts and the microbial composition influence the types of precipitates produced. The mechanisms of crystal formation of CaCO3 and gypsum by these communities were also investigated by determining the need for metabolic active cells, the effect of a calcium channel blocker, and the presence of extracellular polymeric substances (EPS). The results showed that metabolically active cells can lead to production of EPS and formation of Ca2+ gradient along the cells through calcium channels, which will trigger formation of biominerals. The prevention of biomineralization by these consortia was also investigated with two common polymeric RO antiscalants, i.e. polyacrylic acid (PAA) and polymaleic acid (PMA). Results showed that these antiscalants do not prevent the formation of the bio-precipitates suggesting that novel approaches to prevent biomineralization in RO systems still needs to be investigated.

Ferrihydrite nanoparticles (Fh NPs) are ubiquitous in natural environments. However, their colloidal stability, and fate and transport behavior are difficult to predict in the presence of heterogeneous natural organic matter (NOM) mixtures. Here, we investigated the adsorption and aggregation behavior of Fh NPs exposed to NOM fractions with different molecular weights (MW). The NOM fraction with MW < 3 kDa destabilized the NPs, resulting in accelerated aggregation even at high C/Fe mass ratios, whereas higher MW NOM fractions imparted better colloidal stability with increasing MW and C/Fe ratio. Despite differences in the functional group composition of the bulk (dissolved) NOM fractions, all NOM fractions produced similar adsorbed layer compositions on the NPs, suggesting minimal contribution of chemical properties to the distinctive aggregation behavior. Rather, the higher adsorbed mass and larger size of the higher MW fractions were key factors in stabilizing the NPs through steric repulsion, whereas the lowest MW fraction had low adsorbed mass and was unable to counter electrostatic patch-charge attraction when the NPs are positively charged. This mechanistic understanding helps us predict the transport and fate of Fh NPs and the associated contaminants in natural environments with varying NOM compositions.