Viral communities in a pH>10 serpentinite-like environment: insight into diversity and potential roles in modulating the microbiomes by bioactive vitamin B9 synthesis.

Viral communities exist in a variety of ecosystems and play significant roles in mediating biogeochemical processes, whereas viruses inhabiting strongly alkaline geochemical systems remain underexplored. In this study, the viral diversity, potential functionalities, and virus-host interactions in a strongly alkaline environment (pH = 10.4-12.4) exposed to the leachates derived from the serpentinization-like reactions of smelting slags were investigated. The viral populations (e.g., Herelleviridae, Queuovirinae, and Inoviridae) were closely associated with the dominating prokaryotic hosts (e.g., Meiothermus, Trueperaceae, and Serpentinomonas) in this ultrabasic environment. Auxiliary metabolic genes (AMGs) suggested that viruses may enhance hosts' fitness by facilitating cofactor biosynthesis, hydrogen metabolism, and carbon cycling. To evaluate the activity of synthesis of essential cofactor vitamin B9 by the viruses, a viral folA (vfolA) gene encoding dihydrofolate reductase (DHFR) was introduced into a thymidine-auxotrophic strain Escherichia coli MG1655 ΔfolA mutant, which restored the growth of the latter in the absence of thymidine. Notably, the homologs of the validated vDHFR were globally distributed in the viromes across various ecosystems. The present study sheds new light on the unique viral communities in hyperalkaline ecosystems and their potential beneficial impacts on the coexisting microbial consortia by supplying essential cofactors. IMPORTANCE: This study presents a comprehensive investigation into the diversity, potential functionalities, and virus-microbe interactions in an artificially induced strongly alkaline environment. Functional validation of the detected viral folA genes encoding dihydrofolate reductase substantiated the synthesis of essential cofactors by viruses, which may be ubiquitous, considering the broad distribution of the viral genes associated with folate cycling.

Field aging slows down biochar-mediated soil carbon dioxide emissions.

Biochar is widely used due to its potential in direct or indirect soil carbon sequestration. However, there is a lack of comprehensive studies on the changes in the physicochemical properties of biochar after long-term application in different types of soils and the effects on CO2 emissions. In this study, paddy soil and fluvisol were selected as typical acidic and alkaline soils. Rice biochar (RB) and maize biochar (MB) were incorporated into paddy soil and fluvisol for one year, and characterizations (e.g., SEM-EDS, FTIR, 3D-EEM, and TG-DTG) of pristine and aged biochars were analyzed. Incubation experiments were conducted to assess the impact of aged biochar on CO2 emissions from paddy soil and fluvisol. Results indicated consistent trends in the physicochemical properties of biochar after one year of aging in both acidic and alkaline soils. Aged biochars exhibited significant structural degradation, increased specific surface area, and increased oxygen-containing functional groups. The DOM fluorescence intensity of biochar decreased and the thermal stability increased after aging. Compared to pristine biochar, aged biochar promoted soil carbon sequestration, resulting in varied reductions in cumulative CO2 emissions from paddy soil and fluvisol in the short term. Spearman's correlation coefficient analysis and PCA loading plot revealed that field-aged biochar primarily influenced CO2 emissions from soil and carbon sequestration by reducing biochar DOC release and bioavailability of DOM, while enhancing the humification of biochar DOM. These findings suggest that aged biochar favors soil carbon sequestration in the short term, both in acidic and alkaline soils.

Contrasting effects of iron oxides on soil organic carbon accumulation in paddy and upland fields under long-term fertilization.

Active iron oxides, especially poorly crystalline forms, benefit soil organic carbon (SOC) accumulation via directly bounding and indirectly promoting aggregation. However, it remains unclear on the impacts of active iron oxides on SOC accumulation in paddy and upland soils under long-term fertilization regimes. Here, we attempted to clarify the underlying mechanisms of amorphous (FeO) and organically complexed (FeP) iron oxides mediating SOC accumulation in paddy and upland soils based on two long-term fertilization experiments (both including no fertilization [CK]; chemical nitrogen, phosphorus and potassium [NPK] and NPK plus manure [NPKM] treatments). Results showed that compared to upland soil, Fe-bound organic carbon (Fe-bound OC) content in paddy soil, occupying 21-30% of SOC, was 77% higher on average, due to larger amounts of FeO (+31%) and FeP (+224%). The FeO and FeP were positively related to mean weight diameter (MWD) of soil aggregates across paddy and upland soils. Compared to NPK treatment, NPKM treatment strongly increased FeO (+41%), FeP (+60%) and associated Fe-bound OC (+19%) in paddy soil, and increased FeO (+17%) and FeP (+25%) while decreasing Fe-bound OC (-9%) in upland soil. These combined findings indicated the importance of poorly crystalline iron oxides facilitating Fe-bound OC formation and its contribution to SOC accumulation in paddy soil rather than upland soil. Moreover, long-term manure amendment could enhance SOC accumulation by increasing Fe-bound OC and aggregation stability in paddy soil and enhancing physical protection in upland soil, largely attributed to increased poorly crystalline iron oxides. Overall, these results highlight the potential mechanisms through which active iron oxides regulate SOC accumulation and guide fertilization management in paddy and upland soils.

Effects of Microplastics on Soil Carbon Mineralization: The Crucial Role of Oxygen Dynamics and Electron Transfer.

Although our understanding of the effects of microplastics on the dynamics of soil organic matter (SOM) has considerably advanced in recent years, the fundamental mechanisms remain unclear. In this study, we examine the effects of polyethylene and poly(lactic acid) microplastics on SOM processes via mineralization incubation. Accordingly, we evaluated the changes in carbon dioxide (CO2) and methane (CH4) production. An O2 planar optical sensor was used to detect the temporal behavior of dissolved O2 during incubation to determine the microscale oxygen heterogeneity caused by microplastics. Additionally, the changes in soil dissolved organic matter (DOM) were evaluated using a combination of spectroscopic approaches and ultrahigh-resolution mass spectrometry. Microplastics increased cumulative CO2 emissions by 160-613%, whereas CH4 emissions dropped by 45-503%, which may be attributed to the oxygenated porous habitats surrounding microplastics. Conventional and biodegradable microplastics changed the quantities of soil dissolved organic carbon. In the microplastic treatments, DOM with more polar groups was detected, suggesting a higher level of electron transport. In addition, there was a positive correlation between the carbon concentration, electron-donating ability, and CO2 emission. These findings suggest that microplastics may facilitate the mineralization of SOM by modifying O2 microenvironments, DOM concentration, and DOM electron transport capability. Accordingly, this study provides new insights into the impact of microplastics on soil carbon dynamics.

Inducing Inorganic Carbon Accrual in Subsoil through Biochar Application on Calcareous Topsoil.

Biochar amendments add persistent organic carbon to soil and can stabilize rhizodeposits and existing soil organic carbon (SOC), but effects of biochar on subsoil carbon stocks have been overlooked. We quantified changes in soil inorganic carbon (SIC) and SOC to 2 m depth 10 years after biochar application to calcareous soil. The total soil carbon (i.e., existing SOC, SIC, and biochar-C) increased by 71, 182, and 210% for B30, B60, and B90, respectively. Biochar application at 30, 60, and 90 t ha-1 rates significantly increased SIC by 10, 38, and 68 t ha-1, respectively, with accumulation mainly occurring in the subsoil (below 1 m). This huge increase of SIC (mainly CaCO3) is ∼100 times larger than the inorganic carbon present in the added biochar (0.3, 0.6, or 0.9 t ha-1). The benzene polycarboxylic acid method showed that the biochar-amended soil contained more black carbon particles (6.8 times higher than control soil) in the depth of 1.4-1.6 m, which provided the direct quantitative evidence for biochar migration into subsoil after a decade. Spectral and energy spectrum analysis also showed an obvious biochar structure in the biochar-amended subsoil, accompanied by a Ca/Mg carbonate cluster, which provided further evidence for downward migration of biochar after a decade. To explain SIC accumulation in subsoil with biochar amendment, the interacting mechanisms are proposed: (1) biochar amendment significantly increases subsoil pH (0.3-0.5 units) 10 years after biochar application, thus forming a favorable pH environment in the subsoil to precipitate HCO3-; and (2) the transported biochar in subsoil can act as nuclei to precipitate SIC. Biochar amendment enhanced SIC by up to 80%; thus, the effects on carbon stocks in subsoil must be understood to inform strategies for carbon dioxide removal through biochar application. Our study provided critical knowledge on the impact of biochar application to topsoil on carbon stocks in subsoil in the long term.

The forgotten impacts of plastic contamination on terrestrial micro- and mesofauna: A call for research.

Microplastics (MP) and nanoplastics (NP) contamination of the terrestrial environment is a growing concern worldwide and is thought to impact soil biota, particularly the micro and mesofauna community, by various processes that may contribute to global change in terrestrial systems. Soils act as a long-term sink for MP, accumulating these contaminants and increasing their adverse impacts on soil ecosystems. Consequently, the whole terrestrial ecosystem is impacted by microplastic pollution, which also threatens human health by their potential transfer to the soil food web. In general, the ingestion of MP in different concentrations by soil micro and mesofauna can adversely affect their development and reproduction, impacting terrestrial ecosystems. MP in soil moves horizontally and vertically because of the movement of soil organisms and the disturbance caused by plants. However, the effects of MP on terrestrial micro-and mesofauna are largely overlooked. Here, we give the most recent information on the forgotten impacts of MP contamination of soil on microfauna and mesofauna communities (protists, tardigrades, soil rotifers, nematodes, collembola and mites). More than 50 studies focused on the impact of MP on these organisms between 1990 and 2022 have been reviewed. In general, plastic pollution does not directly affect the survival of organisms, except under co-contaminated plastics that can increase adverse effects (e.g. tire-tread particles on springtails). Besides, they can have adverse effects at oxidative stress and reduced reproduction (protists, nematodes, potworms, springtails or mites). It was observed that micro and mesofauna could act as passive plastic transporters, as shown for springtails or mites. Finally, this review discusses how soil micro- and mesofauna play a key role in facilitating the (bio-)degradation and movement of MP and NP through soil systems and, therefore, the potential transfer to soil depths. More research should be focused on plastic mixtures, community level and long-term experiments.

Prognosis of laparoscopic surgery for colorectal cancer in middle-aged patients.

Background: The prognosis of middle-aged patients with colorectal cancer (CRC) treated by laparoscopic resection (LR) is unclear. This study aimed to evaluate the survival outcomes of LR compared with open resection (OR) for middle-aged patients with CRC. Patients and Methods: This retrospective cohort study used the data from a database of all consecutive colorectal resections performed between January 2009 and December 2017. Propensity score matching (PSM) was performed to handle the selection bias based on age, gender, body mass index, tumour location, AJCC stage and admission year. Univariate and multivariate COX regression model was used to identify risk factors of overall survival (OS) and disease-free survival (DFS). Results: After PSM, 154 patients were included in each group. Compared with the OR group in the total cohort, there were better survival outcomes in the LR group for 5-year OS and 5-year DFS (both P < 0.001). These differences were observed for Stage II and III diseases and for all CRC, irrespective of location. The multivariate analysis showed that tumour ≥5 cm (hazard ratio [HR] = 1.750, 95% confidence interval [CI]: 1.026-2.986, P = 0.040), Stage III (HR = 14.092, 95% CI: 1.894-104.848, P = 0.010) and LR (HR = 0.300, 95% CI: 0.160-0.560, P < 0.001) were independently associated with OS. Pre-operative carcinoembryonic antigen ≥5 ng/ml (HR = 3.954, 95% CI: 1.363-11.473, P = 0.011), Stage III (HR = 6.206, 95% CI: 1.470-26.200, P = 0.013) and LR (HR = 0.341, 95% CI: 0.178-0.653, P = 0.001) were independently associated with DFS. Conclusions: In middle-aged patients with CRC, LR achieves better survival than OR. Complications are similar, except for less blood loss and shorter post-surgical hospital stay with LR.

Goethite modified biochar simultaneously mitigates the arsenic and cadmium accumulation in paddy rice (Oryza sativa) L.

Cadmium (Cd) and arsenic (As) contamination of paddy soils is a serious global issue because of the opposite geochemical behavior of Cd and As in paddy soils. Rice plant (Oryza sativa L.) cultivation in Cd- and As- contaminated paddy soil is regarded as one of the main dietary cause of Cd and As entry in human beings. This study aimed to determine the impact of goethite-modified biochar (GB) on bioavailability of both Cd and As in Cd- and As- polluted paddy soil. Contrary to control and biochar (BC) amendments, the application of GB amendments significantly impeded the accumulation of both Cd and As in rice plants. The results confirmed an obvious reduction in Cd and As content of rice grains by 85% and 77%, respectively after soil supplementation with GB 2% amendment. BC 3% application minimized the Cd uptake by 59% in the rice grains as compared to the control but exhibited a little impact on As accumulation in rice grains. Sequential extraction results displayed an increase in immobile Cd and As fractions of the soil by decreasing the bioavailable fractions of both elements after GB treatments. Fe-plaque formation on the root surfaces was significantly variable (P Ë‚ 0.05) among all the amendments. GB 2% treatment significantly increased the Fe content (10 g kg-1) of root Fe-plaque by 48%, which ultimately enhanced the sequestration of Cd and As by Fe-plaque and minimized the transport of Cd and As in rice plants. Moreover, GB treatments significantly changed the relative abundance of the microbial community in the rice rhizosphere and minimized the metal(loid)s mobility in the soil. The relative abundance of Acidobacteria, Firmicutes and Verrucomicrobia increased with GB 2% treatment while those of Bacteroidetes and Choloroflexi decreased. Our findings confirmed improvement in the rice grains quality regarding enhanced amino acid contents with GB application. Overall, the results of this study demonstrated that GB amendment simultaneously alleviated the Cd and As concentrations in edible parts of rice plant and provided a new valuable method to protect the public health by effectively remediating the co-occurrence of Cd and As in paddy soils.

State-of-the-art of research progress on adsorptive removal of fluoride-contaminated water using biochar-based materials: Practical feasibility through reusability and column transport studies.

Fluoride (F-) is one of the essential elements found in soil and water released from geogenic sources and several anthropogenic activities. Fluoride causes fluorosis, dental and skeletal growth problems, teeth mottling, and neurological damage due to prolonged consumption, affecting millions worldwide. Adsorption is an extensively implemented technique in water and wastewater treatment for fluoride, with significant potential due to efficiency, cost-effectiveness, ease of operation, and reusability. This review highlights the current state of knowledge for fluoride adsorption using biochar-based materials and the limitations of biochar for fluoride-contaminated groundwater and industrial wastewater treatment. Biochar materials have shown significant adsorption capacities for fluoride under the influence of low pH, biochar dose, initial concentration, temperature, and co-existing ions. Modified biochar possesses various functional groups (-OH, -CC, -C-O, -CONH, -C-OH, X-OH), in which enhanced hydroxyl (-OH) groups onto the surface plays a significant role in fluoride adsorption via electrostatic attraction and ion exchange. Regeneration and reusability of biochar sorbents need to be performed to a greater extent to improve removal efficiency and reusability in field conditions. Furthermore, the present investigation identifies the limitations of biochar materials in treating fluoride-contaminated drinking groundwater and industrial effluents. The fluoride removal using biochar-based materials at an industrial scale for understanding the practical feasibility is yet to be documented. This review work recommend the feasibility of biochar-based materials in column studies for fluoride remediation in the future.

Removal of hexavalent chromium via biochar-based adsorbents: State-of-the-art, challenges, and future perspectives.

Chromium originates from geogenic and extensive anthropogenic activities and significantly impacts natural ecosystems and human health. Various methods have been applied to remove hexavalent chromium (Cr(VI)) from aquatic environmental matrices, including adsorption via different adsorbents, which is considered to be the most common and low-cost approach. Biochar materials have been recognized as renewable carbon sorbents, pyrolyzed from various biomass at different temperatures under limited/no oxygen conditions for heavy metals remediation. This review summarizes the sources, chemical speciation & toxicity of Cr(VI) ions, and raw and modified biochar applications for Cr(VI) remediation from various contaminated matrices. Mechanistic understanding of Cr(VI) adsorption using different biochar-based materials through batch and saturated column adsorption experiments is documented. Electrostatic interaction and ion exchange dominate the Cr(VI) adsorption onto the biochar materials in acidic pH media. Cr(VI) ions tend to break down as HCrO4-, CrO42-, and Cr2O72- ions in aqueous solutions. At low pH (∼1-4), the availability of HCrO4- ions attributes the electrostatic forces of attraction due to the available functional groups such as -NH4+, -COOH, and -OH2+, which encourages higher adsorption of Cr(VI). Equilibrium isotherm, kinetic, and thermodynamic models help to understand Cr(VI)-biochar interactions and their adsorption mechanism. The adsorption studies of Cr(VI) are summarized through the fixed-bed saturated column experiments and Cr-contaminated real groundwater analysis using biochar-based sorbents for practical applicability. This review highlights the significant challenges in biochar-based material applications as green, renewable, and cost-effective adsorbents for the remediation of Cr(VI). Further recommendations and future scope for the implications of advanced novel biochar materials for Cr(VI) removal and other heavy metals are elegantly discussed.

Role of nonspherical DLVO and capillary forces in the transport of 2D delaminated Ti3C2Tx MXene in saturated and unsaturated porous media.

The transport and retention of two-dimensional (2D) nanomaterials, such as graphene oxide, in porous media have attracted lots of attention. However, previous studies often simplified these 2D colloids as equivalent spheres for numerical simulations, which ignored the influence of particle shape on colloid retention at multiple interfaces. In this study, a novel 2D nanomaterial delaminated Ti3C2Tx (d-Ti3C2Tx) was adopted to fill this knowledge gap. Comprehensive analyses of the 2D colloid retention mechanisms were conducted based on colloid characterization, saturated and unsaturated column experiments, reactive transport modeling, 2D-based DLVO and nonspherical capillary energy simulations. Results show that d-Ti3C2Tx mobility in both saturated and unsaturated conditions enhanced with the increase in pH and decrease in ionic strength. The DLVO interaction energy of d-Ti3C2Tx at the sand-water-interface (SWI) decreased with the orientation angle of the colloidal major axis to the sand surface from 0° to 90°. The primary mechanism under saturated flow conditions was the irreversible attachment in the deep secondary minimum at the SWI with the major axis of d-Ti3C2Tx parallel to the sand surface. The attachment in the primary minimum at 0° was impossible due to the extremely high energy barrier, and the attachment in the primary and secondary minimum at other orientation angles were negligible. d-Ti3C2Tx only experienced repulsive electrostatic force when approaching the air-water-interface (AWI) no matter the particle orientation. The detaching capillary potential energy was 3 orders of magnitude larger than the attractive DLVO interaction energy of the SWI in the secondary minimum at 0°, suggesting that the capillary force-induced irreversible attachment at the AWI was the primary mechanism under unsaturated flow conditions. This study shows that the DLVO and capillary potential energies were significantly dependent on the particle-interface orientation and colloidal shape. A simplification of 2D colloids as spheres is not recommended.

Ferrihydrite Transformation Impacted by Coprecipitation of Phytic Acid.

Phytic acid is a common phosphate monoester that is present in soils due to the deposition of plant-derived materials. Thus far, its interaction with dissolved Fe and Fe minerals has not been as extensively investigated as phosphate, although it is expected be highly reactive due to its multiple phosphate functional groups. In this study, the effects of phytic acid on the formation of iron oxyhydroxide was investigated at near neutral pH as a function of the phytic acid/Fe ratio (0.05-0.5) and aging time using zeta potential measurements, X-ray diffraction, Fe K-edge X-ray absorption spectroscopy, and scanning electron transmission spectroscopy. It was found that an iron(III) phytate-like precipitate was formed when the phytic acid/Fe ratio was as low as 0.05. On increasing the ratio to 0.5, the quantity of iron(III) phytate-like precipitate increased to ∼60% in the ferrihydrite background. Interestingly, 10 month aging at 22 °C or hydrothermal treatment at 70 °C for 60 h did not transform the background ferrihydrite into goethite or hematite, suggesting the adsorbed phytic acid played an important role in inhibiting the transformation of ferrihydrite. The adsorption and incorporation of phytic acid into the Fe(III)O6 polymers should be useful in understanding the complex phosphorus, iron, and hard acid chemistry in a terrestrial environment.

Gender aspects of survival after abdominoperineal resection for low rectal cancer: a retrospective study.

PURPOSE: The difference in prognosis between genders after abdominoperineal resection (APR) for low rectal cancer (LRC) is unclear. This study aimed to compare survival outcomes between genders in patients with LRC who underwent curative APR. METHODS: This retrospective cohort study used a database of consecutive colorectal resections. Patients who received curative APR with LRC were grouped according to their gender. Female patients were frequency-matched 1:1 on American Joint Committee on Cancer (AJCC) stage to male patients. Overall survival (OS), disease-free survival (DFS), and their independent risk factors were examined. RESULTS: A total of 140 patients with APR for LRC were included after matching: 70 (50.0%) males and 70 (50.0%) females. No significant differences were found between the groups in terms of age, operation methods, AJCC stage, and adjuvant therapy (all P > 0.05). Median follow-up was 39 (range: 3-128) months. Male gender was independently associated with worse OS (adjusted hazard ratio [HR] = 2.755, 95% CI: 1.507-5.038, P = 0.001) and worse DFS (adjusted HR = 2.440, 95% CI: 1.254-4.746, P = 0.009). Subgroup analysis revealed that female patients with stage III disease had better OS (P = 0.001) and DFS (P < 0.001) than male patients. CONCLUSION: Gender affects survival after a curative APR for LRC. Compared with females, male patients with LRC after curative APR had worse prognosis, especially for stage III disease.

Chemical Aging Changed Aggregation Kinetics and Transport of Biochar Colloids.

Little is known about aggregation and transport behaviors of aged biochar colloids in the terrestrial environment. This study investigated aggregation kinetics and transport of biochar colloids from aged (HNO3 treatment) and pristine pinewood biochars pyrolyzed at 300 and 600 °C (PB300 and PB600) in NaCl and CaCl2 solutions. In NaCl solutions, critical coagulation concentrations (CCCs) of aged PB300 and PB600 colloids (540 mM and 327 mM) were much greater than the CCCs of pristine biochar colloids (300 mM and 182 mM). This is likely due to substantial increase of negatively charged oxygen-containing functional groups (primarily carboxyl) on aged biochar surfaces. Intriguingly, in CaCl2 solutions the CCCs of the aged PB300 and PB600 colloids decreased to 25.2 mM and 32.1 mM from 58.6 mM and 41.7 mM for the pristine colloids, respectively. This probably resulted from greater surface charge neutralization and Ca2+ bridging for the aged biochar colloids. In salt solutions (e.g., 10 and 50 mM NaCl and 1 and 10 mM CaCl2), the aged biochar colloids showed higher mobility in porous media than the pristine biochar colloids. This study demonstrated that pristine and aged biochar colloids were stable in the solutions with environmentally relevant ionic strength, and the aging process might substantially increase their mobility in the subsurface.

Kinetics and Mechanisms of Protein Adsorption and Conformational Change on Hematite Particles.

Adsorption kinetics and conformational changes of a model protein, bovine serum albumin (BSA, 0.1, 0.5, or 1.0 g/L), on the surface of hematite (α-Fe2O3) particles in 39 ± 9, 68 ± 9, and 103 ± 8 nm, respectively, were measured using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. As the particle size increases, the amount of adsorbed BSA decreases, but the loss in the helical structure of adsorbed BSA increases due to the stronger interaction forces between adsorbed BSA and the larger particles. On 39 or 68 nm hematite particles, refolding of adsorbed BSA can be induced by protein-protein interactions, when the protein surface coverage exceeds certain critical values. Two-dimensional correlation spectroscopy (2D-COS) analysis of time-dependent ATR-FTIR spectra indicate that the increase in the amount of adsorbed BSA occurs prior to the loss in the BSA helical structure in the initial stage of adsorption processes, whereas an opposite sequence of the changes to BSA conformation and surface coverage is observed during the subsequent refolding processes. Desorption experiments show that replacing the protein solution with water can quench the refolding, but not the unfolding, of adsorbed BSA. A kinetic model was proposed to quantitatively describe the interplay of adsorption kinetics and conformational change, as well as the effects of particle size and initial protein concentration on the rate constants of elementary steps in protein adsorption onto a mineral surface.

Contributions of Nanoscale Roughness to Anomalous Colloid Retention and Stability Behavior.

All natural surfaces exhibit nanoscale roughness (NR) and chemical heterogeneity (CH) to some extent. Expressions were developed to determine the mean interaction energy between a colloid and a solid-water interface, as well as for colloid-colloid interactions, when both surfaces contain binary NR and CH. The influence of heterogeneity type, roughness parameters, solution ionic strength (IS), mean zeta potential, and colloid size on predicted interaction energy profiles was then investigated. The role of CH was enhanced on smooth surfaces with larger amounts of CH, especially for smaller colloids and higher IS. However, predicted interaction energy profiles were mainly dominated by NR, which tended to lower the energy barrier height and the magnitudes of both the secondary and primary minima, especially when the roughness fraction was small. This dramatically increased the relative importance of primary to secondary minima interactions on net electrostatically unfavorable surfaces, especially when roughness occurred on both surfaces and for conditions that produced small energy barriers (e.g., higher IS, lower pH, lower magnitudes in the zeta potential, and for smaller colloid sizes) on smooth surfaces. The combined influence of roughness and Born repulsion frequently produced a shallow primary minimum that was susceptible to diffusive removal by random variations in kinetic energy, even under electrostatically favorable conditions. Calculations using measured zeta potentials and hypothetical roughness properties demonstrated that roughness provided a viable alternative explanation for many experimental deviations that have previously been attributed to electrosteric repulsion (e.g., a decrease in colloid retention with an increase in solution IS; reversible colloid retention under favorable conditions; and diminished colloid retention and enhanced colloid stability due to adsorbed surfactants, polymers, and/or humic materials).

Photocatalytic reduction of triclosan on Au-Cu2O nanowire arrays as plasmonic photocatalysts under visible light irradiation.

Triclosan (TCS) is a potential threat to the environment and human health. Photocatalysis can be used to degrade TCS, but the photocatalytic efficiency is usually limited by the photoabsorptivity and photostability of the photocatalyst. In addition, some toxic by-products might also be generated during photocatalytic processes. In this study, we prepared Au-coated Cu2O nanowire arrays (Au-Cu2O NWAs) by beam sputtering Au onto Cu2O nanowires grown from a Cu foil. We found that photocatalytic degradation of TCS under visible light (420 nm < λ < 780 nm) irradiation and Au-Cu2O NWAs had several advantages. Au-Cu2O NWAs had good photoabsorptivity, high photostability (negligible activity loss after 16 runs), excellent photocatalytic activity (47.6 times faster than that of Cu2O), and low yield of dichlorodibenzo-dioxins/dichlorohydroxydibenzofurans. The degradation intermediates were identified as chlorophenoxyphenol, phenoxyphenol, chlorophenol, catechol, phenol, benzoquinone, and lower volatile acids. We developed the degradation pathway of TCS which follows electron reduction and then oxidation by reactive oxygen species. The mechanism was developed and strengthened using the radical trapping and other measurements. The unusual mechanism and photostability of Au-Cu2O NWAs were attributed to the Au/Cu2O/Cu "sandwich"-like structure. This structure yields a sustained and steady internal electric field, raises the conduction band of Cu2O, reinforces the reductive activity of the photo-generated electrons, and eliminates the photo-generated holes that are responsible for the photo-etching of Cu2O.

Effect of subgrid heterogeneity on scaling geochemical and biogeochemical reactions: a case of U(VI) desorption.

The effect of subgrid heterogeneity in sediment properties on the rate of uranyl[U(VI)] desorption was investigated using a sediment collected from the U.S. Department of Energy Hanford site. The sediment was sieved into 7 grain size fractions that each exhibited different U(VI) desorption properties. Six columns were assembled using the sediment with its grain size fractions arranged in different spatial configurations to mimic subgrid heterogeneity in reactive transport properties. The apparent rate of U(VI) desorption varied significantly in the columns. Those columns with sediment structures leading to preferential transport had much lower rates of U(VI) desorption than those with relatively homogeneous transport. Modeling analysis indicated that the U(VI) desorption model and parameters characterized from well-mixed reactors significantly overpredicted the measured U(VI) desorption in the columns with preferential transport. A dual domain model, which operationally separates reactive transport properties into two subgrid domains, improved the predictions significantly. A similar effect of subgrid heterogeneity, albeit to a lesser degree, was observed for denitrification, which also occurred in the columns. The results imply that subgrid heterogeneity is an important consideration in extrapolating reaction rates from the laboratory to field.

Investigation of U(VI) adsorption in quartz-chlorite mineral mixtures.

A batch and cryogenic laser-induced time-resolved luminescence spectroscopy investigation of U(VI) adsorbed on quartz-chlorite mixtures with variable mass ratios have been performed under field-relevant uranium concentrations (5×10(-7) M and 5×10(-6) M) in pH 8.1 synthetic groundwater. The U(VI) adsorption Kd values steadily increased as the mass fraction of chlorite increased, indicating preferential sorption to chlorite. For all mineral mixtures, U(VI) adsorption Kd values were lower than that calculated from the assumption of component additivity possibly caused by surface modifications stemming from chlorite dissolution; The largest deviation occurred when the mass fractions of the two minerals were equal. U(VI) adsorbed on quartz and chlorite displayed characteristic individual luminescence spectra that were not affected by mineral mixing. The spectra of U(VI) adsorbed within the mixtures could be simulated by one surface U(VI) species on quartz and two on chlorite. The luminescence intensity decreased in a nonlinear manner as the adsorbed U(VI) concentration increased with increasing chlorite mass fraction-likely due to ill-defined luminescence quenching by both structural Fe/Cr in chlorite, and trace amounts of solubilized and reprecipitated Fe/Cr in the aqueous phase. However, the fractional spectral intensities of U(VI) adsorbed on quartz and chlorite followed the same trend of fractional adsorbed U(VI) concentration in each mineral phase with approximate linear correlations, offering a method to estimate of U(VI) concentration distribution between the mineral components with luminescence spectroscopy.

Effect of coupled physical and chemical heterogeneity on the transport of pristine and aged pyrogenic carbon colloids in unsaturated porous media.

Due to extensive application and recurrent wildfires, an increasing number of pyrogenic carbon (PyC) colloids are present in the environment, experiencing processes of environmental aging. Subsurface environments are typically heterogeneous in unsaturated conditions, which may affect the transport of PyC colloids. This study focused on the transport of both pristine and aged PyC colloids in physically (clean coarse and fine sand) and physicochemically (iron oxides-coated coarse and clean fine sand) heterogeneous porous media at three different water saturations (100 %, 70 %, and 40 %). In physically heterogeneous porous media, the decrease in water saturation from 100 % to 40 % led to a shift in the main water flow from the clean coarse sand to the clean fine sand domain, resulting in a continuous decrease in the transport of PyC colloids. In physicochemically heterogeneous porous media, the primary water flow shifted from the iron oxides-coated coarse sand to the clean fine sand domain, resulting in an initial increase and subsequent decrease in PyC colloid transport. Aging enhanced the transport of PyC colloids, attributed to the increasingly negative and hydrophilic surface. Retention profiles revealed substantial PyC colloid retention at the interface between coarse and fine sand domains. The release of retained PyC colloids exhibited two peaks at 100 % and 70 % water saturations, along with a single peak at 40 % water saturation. Additionally, the increased irreversible retention was observed at lower water saturation. This study underscores the significance of water content, environmental aging, and heterogeneity in PyC colloid transport. It provides essential insights into the environmental fate of PyC colloids in natural field conditions.