A critical review of contaminant removal by conventional and emerging media for urban stormwater treatment in the United States.

Stormwater is a major component of the urban water cycle contributing to street flooding and high runoff volumes in urban areas, and elevated contaminant concentrations in receiving waters from contact with impervious surfaces. Engineers and city planners are investing in best management practices to reduce runoff volume and to potentially capture and use urban stormwater. However, these current approaches result in moderate to low contaminant removal efficiencies for certain classes of contaminants (e.g., particles, nutrients, and some metals). This review describes options and opportunities to augment existing stormwater infrastructure with conventional and emerging reactive media to improve contaminant removal. This critical analysis characterizes media physicochemical properties and mechanisms contributing to contaminant removal, describes possible candidates for new engineered media, highlights lab and field studies investigating stormwater media contaminant removal, and identifies possible limitations and knowledge gaps in media implementation. Following this analysis, information is provided regarding factors that may contribute to or adversely impact urban stormwater treatment by media. The review closes with insights into additional research directions and important information necessary for safe and effective urban stormwater treatment using media.

Polymer-clay composite geomedia for sorptive removal of trace organic compounds and metals in urban stormwater.

Functionalized polymer-clay composites were developed and characterized as engineered geomedia for trace contaminant removal during infiltration of urban runoff. Montmorillonite clays were functionalized with either poly(diallyldimethylammonium) chloride (PDADMAC) or poly(4-vinylpyridine-co-styrene) (PVPcoS) to enhance organic compound sorption using a simple, scalable synthesis method. Seven representative trace organic compounds and six trace metals were employed to assess the performance of the polymer-clay composites relative to biochar (i.e., an adsorbent proposed for similar purposes) in batch sorption and column studies under simulated stormwater conditions. Contaminant and geomedia electrostatic and hydrophobic interactions, and the presence of natural organic matter (NOM) affected sorption. In batch studies, polymer-clay composites exhibited similar performance to biochar for perfluoroalkyl substance removal, but had lower affinity for polar pesticides and tris(2-chloroethyl) phosphate. Oxyanion removal was greatest for positively-charged PDADMAC-clay composites (particularly Cr[VI]), while PVPcoS-clay composites removed over 95% of Ni, Cd, and Cu. NOM decreased removal of all organic compounds, but increased trace metal removal on clay composites due to sorption of NOM-complexed metals. Polymer-clay composite-amended columns best removed oxyanions, while biochar-amended columns exhibited superior removal for all trace organics. At 3 wt% geomedia-sand loading, clay composites exhibited significantly higher saturated hydraulic conductivity than biochar, which is advantageous when clogging is a concern or when rapid infiltration is needed. Under typical urban stormwater conditions, the clay composites will remove contaminants for at least 20-30 years before regeneration or replacement is needed.

Supramolecular self-assembly of bacteriochlorophyll c molecules in aerosolized droplets to synthesize biomimetic chlorosomes.

The unique properties of chlorosomes, arising out of the self-assembled bateriochlorophyll (BChl) c structure, have made them attractive for use in solar cells. In this work, we have demonstrated the self-assembly of BChl c in aerosolized droplets to mimic naturally occurring chlorosomes. We compare two different methods for self-assembly of BChl c, one using a single-solvent and the other using two-solvents, and demonstrate the superiority of the two-solvent method. Results show that the self-assembled BChl c sprayed at different concentrations resulted in a varying red shift of 69-75 nm in absorption spectrum compared to the solution, which has peak at 668 nm corresponding to the monomeric BChl c. The sample fluoresces at 780 nm indicating a quality of self-assembly comparable to that observed in naturally occurring chlorosomes. In order to mimic chlorosomes, solution containing BChl c, BChl a, lipids and carotenes in same proportion as in chlorosomes is sprayed. The resulting self-assembly has an absorption peak at 750 nm, shifted by 82 nm compared to that of monomers and the fluorescence peak at 790 nm. Thus in presence of lipids and carotenes, both the absorption and fluorescence peaks are red shifted. Further, using grazing incidence small angle X-ray scattering (GISAXS), we characterized the deposited films, and the 2D X-ray scattering patterns of sample clearly indicate the distinct lamellar structure as present in chlorosomes. The results of this work provide new insights into self-assembly in aerosolized droplets, which can be used for assembling a wide range of molecules.

Antiscaling efficacy of CaCO3 and CaSO4 on polyethylene glycol (PEG)-modified reverse osmosis membranes in the presence of humic acid: interplay of membrane surface properties and water chemistry.

Mineral scaling persists in many water treatment processes. More specifically, it can significantly reduce the efficacy of aromatic polyamide (PA) membranes during reverse osmosis (RO) water treatment. Previous studies have integrated hydrophilic materials, such as polyethylene glycol (PEG), onto RO membranes to combat scaling from generally hydrophobic feed water constituents; however, there are still outstanding knowledge gaps regarding the interplay of the modified membrane surface chemistry and the water chemistry in complex RO feed waters. In this work, we have investigated the mechanisms of hydrophilic PEG-grafted PA membranes in reducing mineral scaling from calcium carbonate (CaCO3) and calcium sulfate (CaSO4) in the presence of humic acid (HA). Based on surface and solution analyses, we found that colloidal formation was significantly reduced on PA-PEG surfaces in systems without HA. When HA was introduced, CaCO3 scaling was reduced on both virgin and PA-PEG membrane surfaces; while, interestingly, synergistic PEG-HA-CaSO4 interactions increased CaSO4 colloidal formation on PA-PEG membranes. Promoted CaSO4 formation results from a high negative surface charge near the PEG-modified membrane surface when HA and SO42- are present, attracting more Ca2+ to form CaSO4. The results of this work provide new information about colloidal formation at water-membrane interfaces for designing better PEG and PEG-based scale-resistant desalination membranes.

Hydrophilic, bactericidal nanoheater-enabled reverse osmosis membranes to improve fouling resistance.

Polyamide (PA) semipermeable membranes typically used for reverse osmosis water treatment processes are prone to fouling, which reduces the amount and quality of water produced. By synergistically coupling the photothermal and bactericidal properties of graphene oxide (GO) nanosheets, gold nanostars (AuNS), and hydrophilic polyethylene glycol (PEG) on PA reverse osmosis membrane surfaces, we have dramatically improved fouling resistance of these membranes. Batch fouling experiments from three classes of fouling are presented: mineral scaling (CaCO3 and CaSO4), organic fouling (humic acid), and biofouling (Escherichia coli). Systematic analyses and a variety of complementary techniques were used to elucidate fouling resistance mechanisms from each layer of modification on the membrane surface. Both mineral scaling and organic fouling were significantly reduced in PA-GO-AuNS-PEG membranes compared to other membranes. The PA-GO-AuNS-PEG membrane was also effective in killing all near-surface bacteria compared to PA membranes. In the PA-GO-AuNS-PEG membrane, the GO nanosheets act as templates for in situ AuNS growth, which then facilitated localized heating upon irradiation by an 808 nm laser inactivating bacteria on the membrane surface. Furthermore, AuNS in the membrane assisted PEG in preventing mineral scaling on the membrane surface. In flow-through flux and foulant rejection tests, PA-GO-AuNS-PEG membranes performed better than PA membranes in the presence of CaSO4 and humic acid model foulants. Therefore, the newly suggested membrane surface modifications will not only reduce fouling from RO feeds, but can improve overall membrane performance. Our innovative membrane design reported in this study can significantly extend the lifetime and water treatment efficacy of reverse osmosis membranes to alleviate escalating global water shortage from rising energy demands.

Enhanced Colloidal Stability of CeO2 Nanoparticles by Ferrous Ions: Adsorption, Redox Reaction, and Surface Precipitation.

Due to the toxicity of cerium oxide (CeO2) nanoparticles (NPs), a better understanding of the redox reaction-induced surface property changes of CeO2 NPs and their transport in natural and engineered aqueous systems is needed. This study investigates the impact of redox reactions with ferrous ions (Fe2+) on the colloidal stability of CeO2 NPs. We demonstrated that under anaerobic conditions, suspended CeO2 NPs in a 3 mM FeCl2 solution at pH 4.8 were much more stable against sedimentation than those in the absence of Fe2+. Redox reactions between CeO2 NPs and Fe2+ lead to the formation of 6-line ferrihydrite on the CeO2 surfaces, which enhanced the colloidal stability by increasing the zeta potential and hydrophilicity of CeO2 NPs. These redox reactions can affect the toxicity of CeO2 NPs by increasing cerium dissolution, and by creating new Fe(III) (hydr)oxide reactive surface layers. Thus, these findings have significant implications for elucidating the phase transformation and transport of redox reactive NPs in the environment.

Measurement of sub-2 nm clusters of pristine and composite metal oxides during nanomaterial synthesis in flame aerosol reactors.

Measuring stable clusters to understand particle inception will aid the synthesis of well-controlled nanoparticles via gas-phase aerosol routes. Using a Half Mini differential mobility analyzer, the presence of monomers, dimers, trimers, and tetramers was detected for the first time in a flame aerosol reactor during the synthesis of pristine TiO2 and TiO2/SiO2 nanocomposites. Atomic force microscopy confirmed the presence and the size of sub-2 nm clusters. The detection of these clusters elucidated the initial stages of particle formation during combustion synthesis and supported previous hypotheses that collisional growth from stable monomers of metal oxides is the first step of particle growth.

Na+, Ca2+, and Mg2+ in brines affect supercritical CO2-brine-biotite interactions: ion exchange, biotite dissolution, and illite precipitation.

For sustainable geologic CO(2) sequestration (GCS), a better understanding of the effects of brine cation compositions on mica dissolution, surface morphological change, and secondary mineral precipitation under saline hydrothermal conditions is needed. Batch dissolution experiments were conducted with biotite under conditions relevant to GCS sites (55-95 °C and 102 atm CO(2)). One molar NaCl, 0.4 M MgCl(2), or 0.4 M CaCl(2) solutions were used to mimic different brine compositions, and deionized water was used for comparison. Faster ion exchange reactions (Na(+)-K(+), Mg(2+)-K(+), and Ca(2+)-K(+)) occurred in these salt solutions than in water (H(+)-K(+)). The ion exchange reactions affected bump, bulge, and crack formation on the biotite basal plane, as well as the release of biotite framework ions. In these salt solutions, numerous illite fibers precipitated after reaction for only 3 h at 95 °C. Interestingly, in slow illite precipitation processes, oriented aggregation of hexagonal nanoparticles forming the fibrous illite was observed. These results provide new information for understanding scCO(2)-brine-mica interactions in saline aquifers with different brine cation compositions, which can be useful for GCS as well as other subsurface projects.

Effects of formation conditions on the physicochemical properties, aggregation, and phase transformation of iron oxide nanoparticles.

In this work, hematite transformation from a precursor 6-line ferrihydrite phase was investigated by systematically altering the forced hydrolysis hematite synthesis. Specifically, we used a combination of in situ and ex situ characterization techniques to examine the effects of varying the Fe(III) injection rates and cooling methods on the hematite and 6-line ferrihydrite nanoparticle size, isoelectric point, mineral phase, and aggregation. Finally, As(V) adsorption experiments were performed to determine how the two iron oxide phases existed in the reaction system. Nanoparticle synthesis thermodynamics and kinetics were found to control the extent of distinct 6-line ferrihydrite phases in the iron oxide nanoparticle solutions, as well as the particle size and isoelectric point. Conversion of 6-line ferrihydrite to hematite was greatly influenced by the degree of aggregation (determined by synthesis conditions) during drying. As(V) adsorption experiments revealed that 6-line ferrihydrite and hematite exist as a linear combination of two separate phases. These results provide unique information regarding how in situ iron oxide nanoparticle properties can direct their ex situ behavior.

Formation of iron(III) (hydr)oxides on polyaspartate- and alginate-coated substrates: effects of coating hydrophilicity and functional group.

To better understand the transport of contaminants in aqueous environments, we need more accurate information about heterogeneous and homogeneous nucleation of iron(III) hydroxide nanoparticles in the presence of organics. We combined synchrotron-based grazing incidence small-angle X-ray scattering (GISAXS) and SAXS and other nanoparticle and substrate surface characterization techniques to observe iron(III) (hydr)oxide [10⁻4 M Fe(NO3)3 in 10 mM NaNO3] precipitation on quartz and on polyaspartate- and alginate-coated glass substrates and in solution (pH = 3.7 ± 0.2). Polyaspartate was determined to be the most negatively charged substrate and quartz the least; however, after 2 h, total nanoparticle volume calculations--from GISAXS--indicate that positively charged precipitation on quartz is twice that of alginate and 10 times higher than on polyaspartate, implying that electrostatics do not govern iron(III) (hydr)oxide nucleation. On the basis of contact angle measurements and surface characterization, we concluded that the degree of hydrophilicity may control heterogeneous nucleation on quartz and organic-coated substrates. The arrangement of functional groups at the substrate surface (--OH and --COOH) may also contribute. These results provide new information for elucidating the effects of polymeric organic substrate coatings on the size, volume, and location of nucleating iron hydroxides, which will help predict nanoparticle interactions in natural and engineered systems.

Biotite-brine interactions under acidic hydrothermal conditions: fibrous illite, goethite, and kaolinite formation and biotite surface cracking.

To ensure safe and efficient geologic CO(2) sequestration (GCS), it is crucial to have a better understanding of CO(2)-brine-rock interactions under GCS conditions. In this work, using biotite (K(Mg,Fe)(3)AlSi(3)O(10)(OH,F)(2)) as a model clay mineral, brine-biotite interactions were studied under conditions relevant to GCS sites (95 °C, 102 atm CO(2), and 1 M NaCl solution). After reaction for 3-17 h, fast growth of fibrous illite on flat basal planes of biotite was observed. After 22-70 h reaction, the biotite basal surface cracked, resulting in illite detaching from the surface. Later on (96-120 h), the cracked surface layer was released into solution, thus the inner layer was exposed as a renewed flat basal surface. The cracking and detachment of the biotite surface layer increased the surface area in contact with solution and accelerated biotite dissolution. On biotite edge surfaces, Al-substituted goethite and kaolinite precipitated. In control experiments with water under the same temperature and pressure, neither macroscopic fibrous illite nor cracks were observed. This work provides unique information on biotite-brine interaction under acidic hydrothermal conditions.

Effects of salinity and the extent of water on supercritical CO2-induced phlogopite dissolution and secondary mineral formation.

To ensure the viability of geologic CO2 sequestration (GCS), we need a holistic understanding of reactions at supercritical CO2 (scCO2)-saline water-rock interfaces and the environmental factors affecting these interactions. This research investigated the effects of salinity and the extent of water on the dissolution and surface morphological changes of phlogopite [KMg2.87Si3.07Al1.23O10(F,OH)2], a model clay mineral in potential GCS sites. Salinity enhanced the dissolution of phlogopite and affected the location, shape, size, and phase of secondary minerals. In low salinity solutions, nanoscale particles of secondary minerals formed much faster, and there were more nanoparticles than in high salinity solutions. The effect of water extent was investigated by comparing scCO2-H2O(g)-phlogopite and scCO2-H2O(l)-phlogopite interactions. Experimental results suggested that the presence of a thin water film adsorbed on the phlogopite surface caused the formation of dissolution pits and a surface coating of secondary mineral phases that could change the physical properties of rocks. These results provide new information for understanding reactions at scCO2-saline water-rock interfaces in deep saline aquifers and will help design secure and environmentally sustainable CO2 sequestration projects.

Dissolution and precipitation of clay minerals under geologic CO2 sequestration conditions: CO2-brine-phlogopite interactions.

To ensure efficiency and sustainability of geologic CO2 sequestration (GCS), a better understanding of the geochemical reactions at CO2-water-rock interfaces is needed. In this work, both fluid/solid chemistry analysis and interfacial topographic studies were conducted to investigate the dissolution/precipitation on phlogopite (KMg3Si3AlO10(F,OH)2) surfaces under GCS conditions (368 K, 102 atm) in 1 M NaCl. Phlogopite served as a model for clay minerals in potential GCS sites. During the reaction, dissolution of phlogopite was the predominant process. Although the bulk solution was not supersaturated with respect to potential secondary mineral phases, interestingly, nanoscale precipitates formed. Atomic force microcopy (AFM) was utilized to record the evolution of the size, shape, and location of the nanoparticles. Nanoparticles first appeared on the edges of dissolution pits and then relocated to other areas as particles aggregated. Amorphous silica and kaolinite were identified as the secondary mineral phases, and qualitative and quantitative analysis of morphological changes due to phlogopite dissolution and secondary mineral precipitation are presented. The results provide new information on the evolution of morphological changes at CO2-water-clay mineral interfaces and offer implications for understanding alterations in porosity, permeability, and wettability of pre-existing rocks in GCS sites.