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.

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.

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.

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.

Spatial variation of soil phosphorus in the water level fluctuation zone of the Three Gorges Reservoir: Coupling effects of elevation and artificial restoration.

The water level fluctuation zone (WLFZ) is a distinctive and important component of the reservoir ecosystem. Due to periodic inundation, the fraction, spatial distribution, and chemical reactivity of soil phosphorus (P) within the WLFZ can potentially impact the loading of P into reservoir waters. However, a detailed study of this subject is lacking. In this study, the soil P in the WLFZ of the Three Gorges Reservoir, China, was examined using a combination of chemical sequential extraction, 31P NMR, and adsorption experiments. The results of chemical sequential extraction showed that HCl-Pi constituted the largest P pool among all P forms, with a mean concentration of 338 mg/kg. The content of HCl-Pi decreased significantly toward the dam, while the content of Res-P decreased in the opposite direction. The highest contents of most P forms and total P were observed at an elevation of 160 m. 31P NMR measurements showed that NaOH-EDTA Pi detectable in WLFZ soils at 145 m, 160 m, and 175 m elevation consisted mainly of orthophosphate and pyrophosphate, while NaOH-EDTA Po contained phosphate monoesters and phosphate diesters, accounting for 1.4 % to 46.2 % of NaOH-EDTA TP. Adsorption experiments showed that soil P in the WLFZ was a potential P source for reservoir waters, with chemisorption being the dominant mechanism of P sequestration. The adsorption equilibrium concentration of WLFZ soil was lower at higher elevations (>170 m) compared to lower elevations (<150 m), exhibiting a decrease in the average maximum adsorption from 271 mg/kg to 192 mg/kg. Statistical analysis suggested that Ca and Fe content, particle size, elevation, and artificial restoration were key factors affecting the fraction and content of soil P in the WLFZ. Our findings contribute to an improved understanding of the behavior of soil P in the WLFZ of large reservoirs and its potential contribution to the reservoir waters.

Long-term missing role of small colloids and nanoparticles on the loading and speciation of phosphorus in catfish aquaculture ponds in west Alabama.

Increasing loading of phosphorus (P) into freshwater systems is deemed as one of the key drivers triggering harmful algal blooms (HABs). However, conventional water quality monitoring of P normally uses the operational cutoff (e.g., 450-nm filter membrane) to separate particulate and dissolved phases (entities passing through the 450-nm membrane are regarded as dissolved phase), which completely neglects the roles of small colloids (450-100 nm) and nanoparticles (100-1 nm). Herein, a new particle size separation approach was used to separate water samples collected from catfish aquaculture ponds in west Alabama into six size fractions: large particles (>1000 nm), large colloids (1000-450 nm), small colloids (450-100 nm), large nanoparticles (100-50 nm), small nanoparticles (50-1 nm), and the truly dissolved phase (<1 nm). The speciation and concentration of P in these six size fractions were then investigated using Hedley's sequential extraction method. The new particle size separation results showed that particle loading (mass) followed the order: >1000 nm, 450-100 nm, 1000-450 nm, 100-50 nm, and 50-1 nm. This is mainly due to the abundance of large-sized (>1000 nm) zooplankton and phytoplankton such as algae and cyanobacteria in the catfish aquaculture ponds. Importantly, the small colloid (450-100 nm) and nanoparticle (100-1 nm) size fractions, which were previously regarded as the dissolved phase using the 450-nm membrane filtration operation, accounted for ∼41.8% of the total particle mass. The Hedley's sequential extraction results showed that sodium hydroxide (NaOH)-extracted P represented the largest P pool, followed by water (H2O)- and sodium bicarbonate (NaHCO3)-extracted P pools. Smaller particles exhibited a higher loading of P due to their large surface areas. These new findings suggest that the new particle size separation approach needs to be adopted for future water quality monitoring and mitigation of HABs in freshwater ecosystems.

Application of two-dimension, high-resolution evidences to reveal the biogeochemical process patterns of trace metals in reservoir sediments.

Pollutions of trace metals (TMs) in reservoirs are blooming due to TMs were trapped efficiently in reservoir sediments by dams. Despite the mobilization of TMs in sediments have been well-documented, the patterns of biogeochemical processes occurred in sediments remain poorly understanding. Herein, a deep reservoir was selected to investigate the patterns of TMs biogeochemical processes in sediments by using high-resolution ZrO-Chelex-AgI diffusive gradient in thin films technique (HR-ZCA DGT) and the laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). 2-dimension high-resolution (2D-HR) images showed significant differential spatial enrichment of TMs (V, Mn, Fe, Co, Zn and Sb) in sediments, indicating strong heterogeneity in sediments. Correlations of TMs within microniches (diameter < 1 mm) in horizontal were usually different even contrast with that in vertical profile, suggesting distinct biogeochemical process patterns occurred in vertical vs. in horizontal. Further analyses from 2D-HR images showed the distributions of TMs in microniches reflected their mobilization that was driven by microenvironmental conditions. In contrast, distributions in sediment vertical profile recorded the diagenesis in different deposition depth. The diagenesis in sediment vertical is continuously accumulated by the discrete, microniches mobilization of TMs in horizontal. Collectively, our findings evidenced that 2D-HR data is an update complement to 1-dimension data for better interpret the biogeochemical process patterns of TMs in sediments, that have implication for water management to metals pollution in reservoir ecosystems.

Suspended phosphorus sustains algal blooms in a dissolved phosphorus-depleted lake.

The expansion of algal bloom in surface waters is a global problem in the freshwater ecosystem. Differential reactivity of organic phosphorus (Po) compounds from organic debris, suspended particulate matter (SPM), and sediment towards hydrolysis can dictate the extent of supply often limited inorganic P (Pi) for algal growth, thereby controlling the extent of bloom. Here, we combined solution P-31 nuclear magnetic resonance (31P NMR), sequential extraction, enzymatic hydrolysis, and 16S rRNA measurements to characterize speciation and biogeochemical cycling of P in Lake Erhai, China. Lower ratios of diester-P/monoester-P in SPM in January (mean 0.09) and July (0.14) than that in April (0.29) reflected the higher degree of diester-P remineralization in cold and warm months. Both H2O-Pi and Po were significantly higher in SPM (mean 1580 mg ·kg-1 and 1618 mg ·kg-1) than those in sediment (mean 8 mg ·kg-1 and 387 mg ·kg-1). In addition, results from enzymatic hydrolysis experiments demonstrated that 61% Po in SPM and 58% in sediment in the H2O, NaHCO3, and NaOH extracts could be hydrolyzed. These results suggested that H2O-Pi and Po from SPM were the primarily bioavailable P sources for algae. Changes of Pi contents (particularly H2O-Pi) in algae and alkaline phosphatase activity (APA) during the observation periods were likely to be controlled by the strategies of P uptake and utilization of algae. P remobilization/remineralization from SPM likely resulted from algae and bacteria (e.g., Pseudomonas). Collectively, these results provide important insights that SPM P could sustain the algal blooms even if the dissolved P was depleted in the water column.

Global warming induces the succession of photosynthetic microbial communities in a glacial lake on the Tibetan Plateau.

As an important freshwater resource in the Qinghai-Tibet Plateau, glacial lakes are being immensely affected by global warming. Due to the lack of long-term monitoring data, the processes and driving mechanisms of the water ecology of these glacial lakes in a rapidly changing climate are poorly understood. This study, for the first time, reconstructed changes in water temperature and photosynthetic microbial communities over the past 200 years in Lake Basomtso, a glacial lake on the southeastern Tibetan Plateau. Temperatures were reconstructed using a paleotemperature proxy based on branched glycerol dialkyl glycerol tetraethers (brGDGTs), the cell membrane lipids of some bacteria, and photosynthetic microbial communities were determined by high-throughput DNA sequencing. The reconstructed mean annual air temperature (MAAT) at Lake Basomtso varied between 6.9 and 8.3 °C over the past 200 years, with a rapid warming rate of 0.25 °C /10 yrs after 1950s. Carbon isotope of sediment and n-alkane analyses indicate that ≥95% of the organic matter in Lake Basomtso is derived from a mixture of terrestrial C3 plants and endogenous organic matter inputs, and the proportion of endogenous organic matter in the sediments has gradually increased since the 1960s. The sedimentary DNA analyses of the sediment core reveal that Chloracea is the most dominant prokaryotic photosynthetic microbial group (84.5%) over the past 200 years. However, the relative abundance of Cyanobacteria has increased from ≤6.8% before the 1960s to 15.5% nowadays, suggesting that warmer temperatures favor the growth of Cyanobacteria in glacial lakes. Among eukaryotic photosynthetic microorganisms, the Chlorophyceae have been gradually replaced by Dinoflagellata and Diatomacae since the 1980s, although the Chlorophyceae still had the highest average relative abundance overall (30-40%). The Pb isotopic composition, together with the total phosphorous concentration, implies that human activity exerted a minimal impact on Lake Basomtso over the past 200 yrs. However, the synchronous fluctuations of total organic carbon (TOC), total nitrogen (TN), and metal elements in sediments suggest that temperature appears to have a strong influence on nutrient input to Lake Basomtso by controlling glacial erosion. Global warming and the concurrent increase in glacial meltwater are two main factors driving changes in nutrient inputs from terrestrial sources which, in turn, increases the lake productivity, and changes microbial community composition. Our findings demonstrate the sensitive response of glacial lake ecology to global warming. It is necessary to strengthen the monitoring and research of glacial lake ecology on the Tibetan plateau, so as to more scientifically and accurately understand the response process and mechanism of the glacial lake ecosystem under global warming.

Mechanistic understanding of perfluorooctane sulfonate (PFOS) sorption by biochars.

Biochar has recently emerged as a cost-effective solution to combat per- and polyfluoroalkyl substances (PFAS) pollution in water, but mechanistic understanding of which physicochemical properties of biochars dictate PFAS sorptive removal from water remains elusive. Herein, 15 biochars were pyrolyzed from five feedstocks (corn, Douglas fir, eucalyptus, poplar, and switchgrass) at three pyrolysis temperatures (500, 700, and 900 °C) to investigate their removal efficiencies and mechanisms of perfluorooctane sulfonate (PFOS) from water. A commercial biochar was also included for comparison. Biochar physiochemical properties, including elemental composition, pH, specific surface area (SSA), pore structure, hydrophobicity, surface charge, surface functional groups, and crystalline structure were systematically characterized. Batch sorption data showed that the Douglas fir 900 biochar (Douglas fir and 900 are the feedstock type and pyrolysis temperature, respectively; this naming rule applies to other biochars), poplar 900 biochar, and commercial biochar can remove over 95% of PFOS from water. Structural equation model (SEM) was used to elucidate which biochar properties affect PFOS sorption. Interestingly, biochar pore diameter was identified as the most critical factor controlling PFOS removal, but pore diameter/pore volume ratio, SSA, pyrolysis temperature, hydrophobicity, and elemental composition all played variable roles. Hypothetically, biochars with small pore diameters and large pore volumes had a narrow yet deep pore structure that traps PFOS molecules inside once already sorbed, resulting in an enhanced PFOS sorption. Biochars with small pore diameter, low nitrogen content, and high pyrolysis temperature were also favorable for enhanced PFOS sorption. Our findings advance the knowledge of using biochars with optimized properties to remove PFOS and possibly other similar PFAS compounds from water.

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.

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.

Activating soil nitrification by co-application of peanut straw biochar and organic fertilizer in a rare earth mining soil.

The intensive mining activities to extract rare earth elements from ion-adsorption rare earth deposits have introduced massive amounts of ammonium into the tailing soils in southern China. Compared to the ubiquitous soil nitrification in cropland, forest, and grassland soils, however, there is no feasible strategy to alleviate the ammonium contamination in tailing soil. Herein, the feasibility to remove ammonium by adding ammonium adsorbents (e.g., biochar, activated carbon, and zeolite), alkaline materials, and organic fertilizer to the rare earth mining soil was explored. The amendment of rice straw biochar, activated carbon, or zeolite in combination with CaCO3 and organic fertilizer showed no significant effect on ammonium removal due to their limited capacity to elevate soil pH. However, the co-application of peanut straw biochar (PSBC), CaCO3, and organic fertilizer activated both the ammonia volatilization and soil nitrification processes. Specifically, the three components functioned as follows: organic fertilizer supplied active ammonia-oxidizing bacteria (AOB); PSBC stimulated AOB proliferation by elevating soil pH above 7.75; CaCO3 ameliorated soil acidity and reduced the lag time for activating soil nitrification. The soil ammonium removal and nitrate accumulation rates were positively correlated to the acid neutralization capacity of PSBC prepared at 400 °C-800 °C. The qPCR and microbial community analysis results indicated that Nitrosomonas europaea was the dominant AOB that was responsible for enhanced soil nitrification. Our findings pave the way for developing cost-effective strategies to remediate ammonium contamination in rare earth mining soils.

Linking pyrogenic carbon redox property to arsenite oxidation: Impact of N-doping and pyrolysis temperature.

Pyrogenic carbon-mediated arsenite (As(III)) oxidation shows great potential as a prerequisite for the efficient removal of arsenic in groundwater. Herein, the critical role of N-containing functional groups in low and high-temperature prepared pyrogenic carbons for mediating As(III) oxidation was systemically explored from an electrochemistry perspective. The pyrogenic carbon electron donating capacity and area-normalized specific capacitance were the key parameters explained the As(III) oxidation kinetics mediated by low electrical conductive 500 °C biomass-derived pyrogenic carbons (N contents of 0.36-7.72 wt%, R2 = 0.87, p < 0.001) and high electrical conductive 800 °C pyrogenic carbons (N contents of 1.00-8.00 wt%, R2 = 0.99, p < 0.001), respectively. The production of H2O2 from the reaction between electron donating phenol groups or semiquinone radicals and oxygen, and the direct electron transfer between semiquinone radicals and As(III) contributed to these pyrogenic carbons mediated As(III) oxidation. While the electron accepting quinone, pyridinic-N, and pyrrolic-N groups did not significantly contribute to the 500 °C pyrogenic carbons mediated As(III) oxidation, the direct electron conduction by these functional groups was responsible for the facilitated As(III) oxidation by the 800 °C pyrogenic carbons. Furthermore, the pyridinic-N and pyrrolic-N groups showed higher electron conduction efficiency than that of the quinone groups. The findings help to develop robust pyrogenic carbons for As(III) contaminated groundwater treatment.

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.

Facilitated transport of microplastics and nonylphenol in porous media with variations in physicochemical heterogeneity.

Nonylphenol (Noph) has garnered worldwide concern as a typical endocrine disruptor due to its toxicity, estrogenic properties, and widespread contamination. To better elucidate the interaction of Noph with ubiquitously existing microplastics (MPs) and the potential interdependence of their transport behaviors, batch adsorption and column experiments were conducted, paired with mathematical modeling. Compared with sand, MPs and soil colloids show stronger adsorption affinity for Noph due to the formation of hydrogen bonding and the larger numbers of interaction sites that are available on solid surfaces. Limited amount of soil-colloid coating on sand grains significantly influenced transport behaviors and the sensitivity to solution chemistry. These coatings led to a monotonic increase in Noph retention and a nonmonotonic MPs retention in single systems because of the altered physicochemical properties. The mobility of both MPs and Noph was enhanced when they coexisted, resulting from their association, increased electrostatic repulsion, and competition on retention sites. Limited release of MPs and Noph (under reduced ionic strength (IS) and increased pH) indicated strong interactions in irreversible retention. The retention and release of Noph were independent of IS and solution pH. A one-site model with a blocking term and a two-site kinetic model well described the transport of MPs and Noph, respectively. Our findings highlight the essential roles of coexisting MPs and Noph on their transport behaviors, depending on their concentrations, IS, and physicochemical properties of the porous media. The new knowledge from this study refreshes our understanding of the co-transport of MPs and organic contaminants such as Noph in the subsurface.

Nano-enabled pesticides for sustainable agriculture and global food security.

Achieving sustainable agricultural productivity and global food security are two of the biggest challenges of the new millennium. Addressing these challenges requires innovative technologies that can uplift global food production, while minimizing collateral environmental damage and preserving the resilience of agroecosystems against a rapidly changing climate. Nanomaterials with the ability to encapsulate and deliver pesticidal active ingredients (AIs) in a responsive (for example, controlled, targeted and synchronized) manner offer new opportunities to increase pesticidal efficacy and efficiency when compared with conventional pesticides. Here, we provide a comprehensive analysis of the key properties of nanopesticides in controlling agricultural pests for crop enhancement compared with their non-nanoscale analogues. Our analysis shows that when compared with non-nanoscale pesticides, the overall efficacy of nanopesticides against target organisms is 31.5% higher, including an 18.9% increased efficacy in field trials. Notably, the toxicity of nanopesticides toward non-target organisms is 43.1% lower, highlighting a decrease in collateral damage to the environment. The premature loss of AIs prior to reaching target organisms is reduced by 41.4%, paired with a 22.1% lower leaching potential of AIs in soils. Nanopesticides also render other benefits, including enhanced foliar adhesion, improved crop yield and quality, and a responsive nanoscale delivery platform of AIs to mitigate various pressing biotic and abiotic stresses (for example, heat, drought and salinity). Nonetheless, the uncertainties associated with the adverse effects of some nanopesticides are not well-understood, requiring further investigations. Overall, our findings show that nanopesticides are potentially more efficient, sustainable and resilient with lower adverse environmental impacts than their conventional analogues. These benefits, if harnessed appropriately, can promote higher crop yields and thus contribute towards sustainable agriculture and global food security.

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.

Transport and retention patterns of fragmental microplastics in saturated and unsaturated porous media: A real-time pore-scale visualization.

The environmental behaviors of microplastics (MPs) have garnered ever-increasing attention globally. To overcome the limitations of commonly used "black box", a real-time pore-scale visualization system including microscope, charge coupled device (CCD) microscope camera, and flow cell (connected with pump and sample collector) was used to unravel the transport and retention mechanisms of fragmental microplastics (FMPs) in saturated and unsaturated porous media. The breakthrough curves (BTCs) of effluent concentrations from the flow cells were used to quantitatively analyze FMPs transport. The videos gathered from different transport scenarios indicated that FMPs can move along with the bulk flow in porous media, but also move around the sand surfaces via sliding, rolling, and saltating patterns. The FMPs were retained in porous media mainly via deposition and straining in saturated porous media. Interestingly, little FMPs were captured by the air-water interface in unsaturated conditions. The mobility of FMPs varied with environmental factors, which became lower at higher solution ionic strength (IS), smaller grain size, and lower water content in porous media. Flow rate barely affected the transport of FMPs under 0.1 mM IS with the mass recovery rate ranging between 65.8 and 67.5%, but significantly enhanced FMPs mobility under 10 mM IS through reducing the moving rate. The IS and grain size showed a more significant effect on the transport of FMPs in unsaturated porous media. Our findings, for the first time, visually deciphered the transport and retention patterns of MPs with fragmental shapes on pore-scale, expanding our current knowledge of the fate and transport of more realistic MPs in the environment.

Critical review of microplastics removal from the environment.

Globally, microplastics pollution has become a serious environmental threat due to their multitude sources, widespread occurrence, persistence, and adverse effects to ecosystem and the human health. Addressing this multifaceted threat requires innovative technologies that can efficiently remove microplastics from the environment. In this review, we first overviewed the source, occurrence, and potential adverse impacts of microplastics to human health. We then identified promising technologies for microplastics removal, including physical, chemical, and biological approaches. A detailed analysis of the advantages and limitations of different techniques was provided. We concluded this review with the current challenges and future research priorities, which will guide us through the path addressing microplastics contamination.