Activated Carbon Application Simultaneously Alleviates Paddy Soil Arsenic Mobilization and Carbon Emission by Decreasing Porewater Dissolved Organic Matter.

Flooding of paddy fields during the rice growing season enhances arsenic (As) mobilization and greenhouse gas (e.g., methane) emissions. In this study, an adsorbent for dissolved organic matter (DOM), namely, activated carbon (AC), was applied to an arsenic-contaminated paddy soil. The capacity for simultaneously alleviating soil carbon emissions and As accumulation in rice grains was explored. Soil microcosm incubations and 2-year pot experimental results indicated that AC amendment significantly decreased porewater DOM, Fe(III) reduction/Fe2+ release, and As release. More importantly, soil carbon dioxide and methane emissions were mitigated in anoxic microcosm incubations. Porewater DOM of pot experiments mainly consisted of humic-like fluorophores with a molecular structure of lignins and tannins, which could mediate microbial reduction of Fe(III) (oxyhydr)oxides. Soil microcosm incubation experiments cospiking with a carbon source and AC further consolidated that DOM electron shuttling and microbial carbon source functions were crucial for soil Fe(III) reduction, thus driving paddy soil As release and carbon emission. Additionally, the application of AC alleviated rice grain dimethylarsenate accumulation over 2 years. Our results highlight the importance of microbial extracellular electron transfer in driving paddy soil anaerobic respiration and decreasing porewater DOM in simultaneously remediating As contamination and mitigating methane emission in paddy fields.

Positive and negative impacts of flue gas desulfurization (FGD) gypsum on water quality.

Flue gas desulfurization (FGD) gypsum, a by-product of carbon-based energy sources, has typically been incorporated as a component of concrete mixes and wallboard and beneficially used as an agricultural amendment to enhance terrestrial crop production and improve the quality of runoff. These various uses for the by-product aid in reducing the amount that is ultimately landfilled. Limited studies have investigated its benefits when used directly in aquatic settings, such as ponds and lakes, to increase hardness and potentially mitigate eutrophication. A 36-day field mesocosm experiment tested a larger range of FGD gypsum concentrations (500-2000 mg/L) than those previously tested in the literature to investigate its desired and potentially undesired impacts on water quality, including the algal community. High FGD gypsum concentrations, 1000 and 2000 mg/L, were found to have more undesired impacts than the 500 mg/L treatment, including an initial spike in cyanobacteria, a decrease in total zooplankton abundance, and an increase in certain trace metals in the highest treatment. Ultimately, the 500 mg/L FGD gypsum treatment was found to have fewer undesired impacts while still resulting in significant desired effects, including those on hardness and pH, as well as moderate reductions in algal abundance. This experiment provides a better understanding of the effects of FGD gypsum when directly used in an aquatic setting, determines an optimal dose for future field experiments, and helps provide the groundwork for developing an upper threshold on FGD gypsum so as to not have the negative effects outweigh the positive.

Ionic Strength-Dependent Attachment of Pseudomonas aeruginosa PAO1 on Graphene Oxide Surfaces.

Graphene oxide (GO) is a widely used antimicrobial and antibiofouling material in surface modification. Although the antibacterial mechanisms of GO have been thoroughly elucidated, the dynamics of bacterial attachment on GO surfaces under environmentally relevant conditions remain largely unknown. In this study, quartz crystal microbalance with dissipation monitoring (QCM-D) was used to examine the dynamic attachment processes of a model organism Pseudomonas aeruginosa PAO1 onto GO surface under different ionic strengths (1-600 mM NaCl). Our results show the highest bacterial attachment at moderate ionic strengths (200-400 mM). The quantitative model of QCM-D reveals that the enhanced bacterial attachment is attributed to the higher contact area between bacterial cells and GO surface. The extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory and atomic force microscopy (AFM) analysis were employed to reveal the mechanisms of the bacteria-GO interactions under different ionic strengths. The strong electrostatic and steric repulsion at low ionic strengths (1-100 mM) was found to hinder the bacteria-GO interaction, while the limited polymer bridging caused by the collapse of biopolymer layers reduced cell attachment at a high ionic strength (600 mM). These findings advance our understanding of the ionic strength-dependent bacteria-GO interaction and provide implications to further improve the antibiofouling performance of GO-modified surfaces.

A mechanistic study of ciprofloxacin adsorption by goethite in the presence of silver and titanium dioxide nanoparticles.

The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO2NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO2NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO2NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO2NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO2NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO2NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.

Interactions of extracellular DNA with aromatized biochar and protection against degradation by DNase I.

With increasing environmental application, biochar (BC) will inevitably interact with and impact environmental behaviors of widely distributed extracellular DNA (eDNA), which however still remains to be studied. Herein, the adsorption/desorption and the degradation by nucleases of eDNA on three aromatized BCs pyrolyzed at 700 °C were firstly investigated. The results show that the eDNA was irreversibly adsorbed by aromatized BCs and the pseudo-second-order and Freundlich models accurately described the adsorption process. Increasing solution ionic strength or decreasing pH below 5.0 significantly increased the eDNA adsorption on BCs. However, increasing pH from 5.0 to 10.0 faintly decreased eDNA adsorption. Electrostatic interaction, Ca ion bridge interaction, and π-π interaction between eDNA and BC could dominate the eDNA adsorption, while ligand exchange and hydrophobic interactions were minor contributors. The presence of BCs provided a certain protection to eDNA against degradation by DNase I. BC-bound eDNA could be partly degraded by nuclease, while BC-bound nuclease completely lost its degradability. These findings are of fundamental significance for the potential application of biochar in eDNA dissemination management and evaluating the environmental fate of eDNA.

Elucidating the Role of Sulfide on the Stability of Ferrihydrite Colloids under Anoxic Conditions.

While the reaction mechanisms between ferrihydrite and sulfide are well-documented, the role of redox reactions on the particle-particle stability of ferrihydrite colloids is largely overlooked. Such reactions are critical for a number of (bio)geochemical processes governing ferrihydrite-based colloid processing and their associated role in nutrient and contaminant subsurface dynamics. Taking a fundamental colloid chemistry approach, along with a complementary suite of characterization techniques, here, we explore the stability mechanisms of ferrihydrite colloids over a wide range of environmentally relevant sulfide concentrations at pH 6.0. Results show that sulfide lowered the stability of both ferrihydrite colloids in a concentration-dependent fashion. At lower sulfide concentrations (15.6-62.5 µM), ferrihydrite colloids are apparently stable, but their critical coagulation concentration (CCC) in NaCl linearly decreases with increasing sulfide concentration. This is attributed to the formation of negatively charged elemental sulfur (S(0)) nanoparticles on the surfaces of positively charged ferrihydrite, intensifying the electrostatic attractions between oppositely charged regions on adjacent ferrihydrite surfaces. Further increasing sulfide concentration generates more S(0) attaching to the ferrihydrite surface. This results in effective surface charge neutralization and then subsequent charge reversal, leading to extensive aggregation of ferrihydrite (core) colloids. Interestingly, for the ferrihydrite colloids with higher hydrodynamic diameter, aggregation rates linearly decreases with increasing sulfide concentration from 156.3 to 312.5 µM, which is likely due to the formation of substantial amounts of negatively charged S(0) and FeS. Findings highlight the significance of sulfidation products in controlling the stability of ferrihydrite colloids in sulfidic environments.

Next-Generation Multifunctional Carbon-Metal Nanohybrids for Energy and Environmental Applications.

Nanotechnology has unprecedentedly revolutionized human societies over the past decades and will continue to advance our broad societal goals in the coming decades. The research, development, and particularly the application of engineered nanomaterials have shifted the focus from "less efficient" single-component nanomaterials toward "superior-performance", next-generation multifunctional nanohybrids. Carbon nanomaterials (e.g., carbon nanotubes, graphene family nanomaterials, carbon dots, and graphitic carbon nitride) and metal/metal oxide nanoparticles (e.g., Ag, Au, CdS, Cu2O, MoS2, TiO2, and ZnO) combinations are the most commonly pursued nanohybrids (carbon-metal nanohybrids; CMNHs), which exhibit appealing properties and promising multifunctionalities for addressing multiple complex challenges faced by humanity at the critical energy-water-environment (EWE) nexus. In this frontier review, we first highlight the altered and newly emerging properties (e.g., electronic and optical attributes, particle size, shape, morphology, crystallinity, dimensionality, carbon/metal ratio, and hybridization mode) of CMNHs that are distinct from those of their parent component materials. We then illustrate how these important newly emerging properties and functions of CMNHs direct their performances at the EWE nexus including energy harvesting (e.g., H2O splitting and CO2 conversion), water treatment (e.g., contaminant removal and membrane technology), and environmental sensing and in situ nanoremediation. This review concludes with identifications of critical knowledge gaps and future research directions for maximizing the benefits of next-generation multifunctional CMNHs at the EWE nexus and beyond.

Evaluation of the colloidal stability and adsorption performance of reduced graphene oxide-elemental silver/magnetite nanohybrids for selected toxic heavy metals in aqueous solutions.

Reduced graphene oxide (rGO) hybridized with magnetite and/or elemental silver (rGO/magnetite, rGO/silver, and rGO/magnetite/silver) nanoparticles were evaluated as potential adsorbents for toxic heavy metal ions (Cd (II), Ni(II), Zn(II), Co(II), Pb(II), and Cu(II)). Although the deposition of iron oxide and silver nanoparticles on the rGO nanosheets played an inhibitory role in metal ion adsorption, the metal adsorption efficiency by the nanohybrids (NHs) was still higher than that reported for many other sorbents (e.g., activated biochar, commercial resins, and nanosized hydrated Zr(IV) oxide particles). X-ray photoelectron spectroscopy analyses revealed that complexation with deprotonated adsorbents and cation exchange was an important mechanism for Cd(II) ion removal by the rGO and NHs. Competitive adsorption tests using multi metals showed that the adsorption affinity of metal ions on the rGO and its NHs follows the order (Cu(II), Zn(II)) > Ni(II) > Co(II) > (Pb(II), Cd(II)), which is similar to the order observed for single-metal adsorption experiments. These results can be explained by the destabilization abilities of the rGO and NHs, as well as the ionic radii of the considered metal ions. Our findings demonstrate the feasibility of using rGO-based NHs as highly efficient adsorbents for heavy metal removal from water.

Modeling the Transport of the "New-Horizon" Reduced Graphene Oxide-Metal Oxide Nanohybrids in Water-Saturated Porous Media.

Little is known about the fate and transport of the "new-horizon" multifunctional nanohybrids in the environment. Saturated sand-packed column experiments ( n = 66) were therefore performed to investigate the transport and retention of reduced graphene oxide (RGO)-metal oxide (Fe3O4, TiO2, and ZnO) nanohybrids under environmentally relevant conditions (mono- and divalent electrolytes and natural organic matter). Classical colloid science principles (Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and colloid filtration theory (CFT)) and mathematical models based on the one-dimensional convection-dispersion equation were employed to describe and predict the mobility of RGO-Fe3O4, RGO-TiO2, and RGO-ZnO nanohybrids in porous media. Results indicate that the mobility of the three nanohybrids under varying experimental conditions is overall explainable by DLVO theory and CFT. Numerical simulations suggest that the one-site kinetic retention model (OSKRM) considering both time- and depth-dependent retention accurately approximated the breakthrough curves (BTCs) and retention profiles (RPs) of the nanohybrids concurrently; whereas, others (e.g., two-site retention model) failed to capture the BTCs and/or RPs. This is primarily because blocking BTCs and exponential/hyperexponential/uniform RPs occurred, which is within the framework of OSKRM featuring time- (for kinetic Langmuirian blocking) and depth-dependent (for exponential/hyperexponential/uniform) retention kinetics. Employing fitted parameters (maximum solid-phase retention capacity: Smax = 0.0406-3.06 cm3/g; and first-order attachment rate coefficient: ka = 0.133-20.6 min-1) extracted from the OSKRM and environmentally representative physical variables (flow velocity (0.00441-4.41 cm/min), porosity (0.24-0.54), and grain size (210-810 µm)) as initial input conditions, the long-distance transport scenarios (in 500 cm long sand columns) of the three nanohybrids were predicted via forward simulation. Our findings address the existing knowledge gap regarding the impact of physicochemical factors on the transport of the next-generation, multifunctional RGO-metal oxide nanohybrids in the subsurface.

Carboxymethylcellulose Mediates the Transport of Carbon Nanotube-Magnetite Nanohybrid Aggregates in Water-Saturated Porous Media.

Carbon-metal oxide nanohybrids (NHs) are increasingly recognized as the next-generation, promising group of nanomaterials for solving emerging environmental issues and challenges. This research, for the first time, systematically explored the transport and retention of carbon nanotube-magnetite (CNT-Fe3O4) NH aggregates in water-saturated porous media under environmentally relevant conditions. A macromolecule modifier, carboxymethylcellulose (CMC), was employed to stabilize the NHs. Our results show that transport of the magnetic CNT-Fe3O4 NHs was lower than that of nonmagnetic CNT due to larger hydrodynamic sizes of NHs (induced by magnetic attraction) and size-dependent retention in porous media. Classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory can explain the mobility of NHs under varying experimental conditions. However, in contrast with colloid filtration theory, a novel transport feature-an initial lower and a following sharp-higher peaks occurred frequently in the NHs' breakthrough curves. The magnitude and location of both transport peaks varied with different experimental conditions, due to the interplay between variability of fluid viscosity and size-selective retention of the NHs. Promisingly, the estimated maximum transport distance of NHs ranged between ∼0.38 and 46 m, supporting the feasibility of employing the magnetically recyclable CNT-Fe3O4 NHs for in situ nanoremediation of contaminated soil, aquifer, and groundwater.

Impact of Redox Reactions on Colloid Transport in Saturated Porous Media: An Example of Ferrihydrite Colloids Transport in the Presence of Sulfide.

Transport of colloids in the subsurface is an important environmental process with most research interests centered on the transport in chemically stable conditions. While colloids can be formed under dynamic redox conditions, the impact of redox reactions on their transport is largely overlooked. Taking the redox reactions between ferrihydrite colloids and sulfide as an example, we investigated how and to what extent the redox reactions modulated the transport of ferrihydrite colloids in anoxic sand columns over a range of environmentally relevant conditions. Our results reveal that the presence of sulfide (7.8-46.9 µM) significantly decreased the breakthrough of ferrihydrite colloids in the sand column. The estimated travel distance of ferrihydrite colloids in the absence of sulfide was nearly 7-fold larger than that in the presence of 46.9 µM sulfide. The reduced breakthrough was primarily attributed to the reductive dissolution of ferrihydrite colloids by sulfide in parallel with formation of elemental sulfur (S(0)) particles from sulfide oxidation. Reductive dissolution decreased the total mass of ferrihydrite colloids, while the negatively charged S(0) decreased the overall zeta potential of ferrihydrite colloids by attaching onto their surfaces and thus enhanced their retention in the sand. Our findings provide novel insights into the critical role of redox reactions on the transport of redox-sensitive colloids in saturated porous media.

Evaluation of water quality in surface water and shallow groundwater: a case study of a rare earth mining area in southern Jiangxi Province, China.

This study was conducted to evaluate the quality of surface water and shallow groundwater near a rare earth mining area in southern Jiangxi Province, China. Water samples from paddy fields, ponds, streams, wells, and springs were collected and analyzed. The results showed that water bodies were characterized by low pH and high concentrations of total nitrogen (total N), ammonium nitrogen (NH4 (+)-N), manganese (Mn), and rare earth elements (REEs), which was likely due to residual chemicals in the soil after mining activity. A comparison with the surface water standard (State Environmental Protection Administration & General Administration of Quality Supervision, Inspection and Quarantine of China GB3838, 2002) and drinking water sanitary standard (Ministry of Health & National Standardization Management Committee of China GB5749, 2006) of China revealed that 88 % of pond and stream water samples investigated were unsuitable for agricultural use and aquaculture water supply, and 50 % of well and spring water samples were unsuitable for drinking water. Moreover, significant cerium (Ce) negative and heavy REEs enrichment was observed after the data were normalized to the Post-Archean Australian Shales (PAAS). Principal component analysis indicated that the mining activity had a more significant impact on local water quality than terrace field farming and poultry breeding activities. Moreover, greater risk of water pollution and adverse effects on local residents' health was observed with closer proximity to mining sites. Overall, these findings indicate that effective measures to prevent contamination of surrounding water bodies from the effects of mining activity are needed.

Effect of Size-Selective Retention on the Cotransport of Hydroxyapatite and Goethite Nanoparticles in Saturated Porous Media.

Attributable to their nanoscale size and slow phosphorus (P) release kinetics, hydroxyapatite nanoparticles (HANPs) are increasingly advocated as a promising P nanofertilizer. Additionally, HANPs have been extensively used to remediate soils, groundwater, and nuclear wastewaters contaminated with metals and radionuclides. Increasing application of HANPs for agronomic and environmental advantages will expedite their dissemination in subsurface environments. Because the biogeochemical cycling of P is intimately coupled with iron, it is anticipated that HANPs and released P from HANPs interact with iron oxides, particularly naturally occurring goethite nanoparticles (GNPs) because of their nanoscale size and high reactivity toward P. Here, we investigated the cotransport and retention of HANPs and GNPs in water-saturated sand columns under environmentally relevant transport conditions (pH and natural organic matter type and concentration). Our results indicated that the "size-selective retention", i.e., preferential retention of larger particles near the column inlet and elution of smaller particles occurred during cotransport of HANPs and GNPs, and the cotransport of both NPs is highly sensitive to solution chemistry that determines NPs dissolution, homo- and heteroaggregation, and co- and competitive-retention. These findings have important insights into application of HANPs as a promising P nanofertilizer and an in situ amendment for contaminated site remediation.

Electrocatalytic miRNA detection using cobalt porphyrin-modified reduced graphene oxide.

Metalated porphyrins have been described to bind nucleic acids. Additionally, cobalt porphyrins present catalytic properties towards oxygen reduction. In this work, a carboxylic acid-functionalized cobalt porphyrin was physisorbed on reduced graphene oxide, then immobilized on glassy carbon electrodes. The carboxylic groups were used to covalently graft amino-terminated oligonucleotide probes which are complementary to a short microRNA target. It was shown that the catalytic oxygen electroreduction on cobalt porphyrin increases upon hybridization of miRNA strand ("signal-on" response). Current changes are amplified compared to non-catalytic amperometric system. Apart from oxygen, no added reagent is necessary. A limit of detection in the sub-nanomolar range was reached. This approach has never been described in the literature.

Cr(VI) removal during cotransport of nano-iron-particles combined with iron sulfides in groundwater: Effects of D. vulgaris and S. putrefaciens.

Iron-based materials such as nanoscale zerovalent iron (nZVI) are effective candidates to in situ remediate hexachromium (Cr(VI))-contaminated groundwater. The anaerobic bacteria could influence the remediation efficiency of Cr(VI) during its cotransport with nZVI in porous media. To address this issue, the present study investigated the adsorption and reduction of Cr(VI) during its cotransport with green tea (GT) modified nZVI (nZVI@GT) and iron sulfides (FeS and FeS2) in the presence of D. vulgaris or S. putrefaciens in water-saturated sand columns. Experimental results showed that the nZVI@GT preferred to heteroaggregate with FeS2 rather than FeS, forming nZVI@GT-FeS2 heteroaggregates. Although the presence of D. vulgaris further induced nZVI@GT-FeS2 heteroaggregates to form larger clusters, it pronouncedly improved the dissolution of FeS and FeS2 for more Cr(VI) reduction associated with lower Cr(VI) flux through sand. In contrast, S. putrefaciens could promote the dispersion of the heteroaggregates of nZVI@GT-FeS2 and the homoaggregates of nZVI@GT or FeS by adsorption on the extracellular polymeric substances, leading to the improved transport of Fe-based materials for a much higher Cr(VI) immobilization in sand media. Overall, our study provides the essential perspectives into a chem-biological remediation technique through the synergistic removal of Cr(VI) by nZVI@GT and FeS in contaminated groundwater. ENVIRONMENTAL IMPLICATION: The green-synthesized nano-zero-valent iron particles (nZVI@GT) using plant extracts (or iron sulfides) have been used for in situ remediation of Cr(VI) contaminated groundwater. Nevertheless, the removal of Cr(VI) (including Cr(VI) adsorption and Cr(III) generation) could be influenced by the anaerobic bacteria governing the transport of engineered nanoparticles in groundwater. This study aims to reveal the inherent mechanisms of D. vulgaris and S. putrefaciens governing the cotransport of nZVI@GT combined with FeS (or FeS2) to further influence the Cr(VI) removal in simulated complex groundwater media. Our findings provides a chemical and biological synergistic remediation strategy for nZVI@GT application in Cr(VI)-contaminated groundwater.

Biochar and surfactant synergistically enhanced PFAS destruction in UV/sulfite system at neutral pH.

The UV/sulfite-based advanced reduction process (ARP) emerges as an effective strategy to combat per- and polyfluoroalkyl substances (PFAS) pollution in water. Yet, the UV/sulfite-ARP typically operates at highly alkaline conditions (e.g., pH > 9 or even higher) since the generated reductive radicals for PFAS degradation can be quickly sequestered by protons (H+). To overcome the associated challenges, we prototyped a biochar-surfactant-system (BSS) to synergistically enhance PFAS sorption and degradation by UV/sulfite-ARP. The degradation and defluorination efficiencies of perfluorooctanoic acid (PFOA) depended on solution pH, and concentrations of surfactant (cetyltrimethylammonium bromide; CTAB), sulfite, and biochar. At high pH (8-10), adding biochar and BSS showed no or even small inhibitory effect on PFOA degradation, since the degradation efficiencies were already high enough that cannot be differentiated. However, at acidic and neutral pH (6-7), an evident enhancement of PFOA degradation and defluorination efficiencies occurred. This is due to the synergies between biochar and CTAB that create favorable microenvironments for enhanced PFOA sorption and deeper destruction by prolonging the longevity of reductive radicals (e.g., SO3•-), which is less affected by ambient pH conditions. The performance of UV/sulfite/BSS was further optimized and used for the degradation of four PFAS. At the optimal experimental condition, the UV/sulfite/BSS system can completely degrade PFOA with >30% defluorination efficiency for up to five continuous cycles (n = 5). Overall, our BSS provides a cost-effective and sustainable technique to effectively degrade PFAS in water under environmentally relevant pH conditions. The BSS-enabled ARP technique can be easily tied into PFAS treatment train technology (e.g., advanced oxidation process) for more efficient and deeper defluorination of various PFAS in water.

Antagonistic effects of humic acid and iron oxyhydroxide grain-coating on biochar nanoparticle transport in saturated sand.

Biochar land application may result in multiple agronomic and environmental benefits (e.g., carbon sequestration, improving soil quality, and immobilizing environmental contaminants). However, our understanding of biochar particle transport is largely unknown in natural environments with significant heterogeneity in solid (e.g., patches of iron oxyhydroxide coating) and solution chemistry (e.g., the presence of natural organic matter), which represents a critical knowledge gap in assessing the environmental impact of biochar land application. Transport and retention kinetics of nanoparticles (NPs) from wheat straw biochars produced at two pyrolysis temperatures (i.e., 350 and 550 °C) were investigated in water-saturated sand columns at environmentally relevant concentrations of dissolved humic acid (HA, 0, 1, 5, and 10 mg L(-1)) and fractional surface coverage of iron oxyhydroxide coatings on sand grains (ω, 0.16, 0.28, and 0.40). Transport of biochar NPs increased with increasing HA concentration, largely because of enhanced repulsive interaction energy between biochar NPs and sand grains. Conversely, transport of biochar NPs decreased significantly with increasing ω due to enhanced electrostatic attraction between negatively charged biochar NPs and positively charged iron oxyhydroxides. At a given ω of 0.28, biochar NPs were less retained with increasing HA concentration due to increased electrosteric repulsion between biochar NPs and sand grains. Experimental breakthrough curves and retention profiles were well described using a two-site kinetic retention model that accounted for Langmuirian blocking or random sequential adsorption at one site. Consistent with the blocking effect, the often observed flat retention profiles stemmed from decreased retention rate and/or maximum retention capacity at a higher HA concentration or smaller ω. The antagonistic effects of HA and iron oxyhydroxide grain-coating imparted on the mobility of biochar NPs suggest that biochar colloid transport potential will be dependent on competitive influences exerted by a number of environmental factors (e.g., natural organic matter and metal oxides).

Transport of biochar particles in saturated granular media: effects of pyrolysis temperature and particle size.

Land application of biochar is increasingly being considered for potential agronomic and environmental benefits, e.g., enhancing carbon sequestration, nutrient retention, water holding capacity, and crop productivity; and reducing greenhouse gas emissions and bioavailability of environmental contaminants. However, little is known about the transport of biochar particles in the aqueous environment, which represents a critical knowledge gap because biochar particles can facilitate the transport of adsorbed contaminants. In this study, column experiments were conducted to investigate biochar particle transport and retention in water-saturated quartz sand. Specific factors considered included biochar feedstocks (wheat straw and pine needle), pyrolysis temperature (350 and 550 °C), and particle size (micrometer-particle (MP) and nanoparticle (NP)). Greater mobility was observed for the biochars of lower pyrolysis temperatures and smaller particle sizes. Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) calculations that considered measured zeta potentials and Lewis acid-base interactions were used to better understand the influence of pyrolysis temperature on biochars particle transport. Most biochars exhibited attractive acid-base interactions that impeded their transport, whereas the biochar with the greatest mobility had repulsive acid-base interaction. Nonetheless, greater retention of the MPs than that of the NPs was in contrast with the XDLVO predictions. Straining and biochar surface charge heterogeneity were found to enhance the retention of biochar MPs, but played an insignificant role in the biochar NP retention. Experimental breakthrough curves and retention profiles were well-described using a two-site kinetic retention model that accounted for depth-dependent retention at one site. Modeled first-order retention coefficients on both sites 1 and 2 increased with increasing pyrolysis temperature and particle size.

Sorptive removal of phosphorus by flue gas desulfurization gypsum in batch and column systems.

Phosphorus (P) over-loading is often a central topic due to its linkage to harmful algal blooms (HABs) and its importance in wastewater treatment that has fueled immediate remediation attempts to reduce P loading from point (e.g., wastewater) and nonpoint sources (e.g., fertilizers). Conventional remediation techniques (e.g., filtration) are often expensive, ineffective, and difficult to implement at large scales. The flue gas desulfurization (FGD) gypsum produced as an energy plant waste byproduct has recently been advocated as a physiochemical remediation strategy for P through sorptive removal. However, limited research is available on the practical applications of FGD gypsum for P removal from water. Herein, batch sorption experiments were performed to investigate the sorptive removal efficiency of P by FGD gypsum under environmentally relevant P concentrations (0.01-0.25 mM). In parallel, fixed-bed column experiments packed with FGD gypsum were performed using elevated P concentrations (0.1-1.0 mM) to understand the scalability of FGD gypsum for large-scale practical applications. During batch experiments, P sorption equilibrium was reached within 24 h that includes an initially fast step (via boundary layer diffusion), followed by a slow rate-determining step (via intraparticle diffusion). P sorption kinetics followed the pseudo second-order kinetics, indicating chemisorption. P sorption at equilibrium can be simulated by both the Freundlich and Langmuir sorption isotherms. The Langmuir sorption isotherm yielded a maximum sorption capacity (Qmax) of 36.1 mM kg-1. The fixed-bed column experimental results showed that sorption rate depends on the applied flow rate, irrespective of the tested P concentrations. Our findings can be extrapolated to evaluate the feasibility and scalability of FGD gypsum in removing P to counteract P runoff and mitigate HABs and P-loaded wastewater.

Effects of particle size and pyrolytic temperature of biochar on the transformation behavior of antibiotic resistance genes.

Rampant use of antibiotics has caused a rapid dissemination of antibiotic resistance genes (ARGs) in environment, posing great threats to ecosystems and human health. Applying biochar (BC) in natural systems to combat the spread of ARGs arises as an attention-grabbing solution. Unfortunately, the effectiveness of BC is still unmanageable due to the incomprehensive knowledge over correlations between BC properties and extracellular ARGs transformation. To pinpoint the crucial factors, we primarily explored transformation behaviors of plasmid-mediated ARGs exposed to BC (in suspensions or extraction solutions), adsorption capacities of ARGs on BC, and growth inhibition of E. coli imposed by BC. Specifically, the effects of BC properties including particle size (large-particulate 150 µm and colloidal 0.45-2 µm) and pyrolytic temperature (300, 400, 500, 600, and 700 °C) on the ARGs transformation were emphasized. Results showed that both large-particulate BC and colloidal BC, irrespective of their pyrolytic temperature, would induce significant inhibitory effects on the ARGs transformation, while the BC extraction solutions showed little effect except BC pyrolyzed at 300 °C. Correlation analysis uncovered that the inhibition effect of BC on ARGs transformation was tightly correlated with its adsorption capacity towards plasmid. Accordingly, greater inhibitory effects from those BCs with higher pyrolytic temperatures and smaller particle sizes mainly originated from their greater adsorption capacities. Intriguingly, E. coli was unable to ingest the plasmid adsorbed on BC, which led to ARGs blocked outside the cell membrane, although this inhibitory effect was partially affected by survival inhibition of BC on E. coli. Particularly, significant plasmid aggregation could occur in the extraction solution of large-particulate BC pyrolyzed at 300 °C, leading to a significant inhibition of ARGs transformation. Overall, our findings complete the insufficient understanding over the effects of BC on ARGs transformation behavior, and potentially provide new insights to scientific communities in mitigating ARGs spreading.