Potentials of single nucleotide polymorphisms and genetic diversity studies at HSP90AB1 gene in Nigerian White Fulani, Muturu, and N'Dama cattle breeds.

The study was aimed at genetic characterization of Nigerian breeds of Muturu, N'Dama, and White Fulani cattle breeds at heat shock protein 90AB1 locus. Also, the goal of the study was to detect the presence of single nucleotide polymorphisms (SNPs) at HSP90AB1 locus and consequently recommend them as bio-markers for thermo-tolerance potentials in Nigerian cattle breeds when exposed to assaults of thermal conditions/heat shock of tropical environment. Based on the previously published potentials of this candidate gene to lower assaults of thermal conditions/heat shock such as heat stress, the detected SNPs of HSP90AB1 within the population of the Nigerian cattle in this study will be recommended for population-based screening with a view to genetically improving those zebu cattle breeds that are more vulnerable to heat shock and assaults of thermal conditions. Total number of 200 blood samples were randomly collected from White Fulani (84 samples), Muturu (73 samples), and N'Dama (43 samples) breeds of cattle. Out of these, 20 DNA samples were randomly selected from each of the three cattle breeds and were used for DNA extraction and downstream analyses to further confirm findings of previous study, hence the goal of our study. DNA was extracted from the blood samples using the Zymo-bead DNA extraction kit and DNA sequencing of our samples was performed. A total number of 9 SNPs (within exons 5-6 coding regions) and 11 SNPs (within exons 12-13 coding regions) were detected at HSP90AB1 locus using the codon code aligner software. ARLEQUIN 2.0001 software was used to estimate the basic population genetic statistics while the DnaSP version 5.10.01 was used to estimate the genetic diversity indices. This study detected new SNPs (polymorphic sites) at HSP90AB1 locus within the DNAs of Nigerian White Fulani (WF), Muturu (MU), and N'Dama (ND) breeds of cattle. Within exons 5-6 coding regions, the N'Dama (ND) cattle breed had the highest for number of SNPs (5) and genetic diversity indices while White Fulani (WF) and Muturu (MU) had the least (2) number of SNPs each. Within exons 12-13 coding regions, WF had the highest numbers of SNPs (7) and genetic diversity indices while MU had the least number of SNPs (1) and genetic diversity indices. Some of the detected SNPs at HSP90AB1 locus were shared among the three breeds, suggesting that these three Nigerian cattle breeds showed shared ancestral alleles and lineage. Our study further revealed that HSP90AB1 is highly polymorphic/variable and diverse among the three Nigerian cattle breeds examined. Based on the previously documented thermo-tolerance potentials of members of HSP90 sub-family including the findings of our study, we hypothesize therefore that the presence of SNPs of HSP90AB1 within the DNAs of these three breeds of Nigerian cattle (WF, ND, and MU) may confer them thermo-tolerance potentials for thermal assault conditions and heat shock of the tropics at HSP90AB1 locus. Therefore, the detected SNPs can be recommended as bio-markers to improve the thermo-tolerance potentials of Nigerian breeds of zebu cattle raised under the challenges of heat shock for better adaptation and survival.

Aging of Copper Nanoparticles in the Marine Environment Regulates Toxicity for a Coastal Phytoplankton Species.

Environmental conditions in aquatic ecosystems transform toxic chemicals over time, influencing their bioavailability and toxicity. Using an environmentally relevant methodology, we tested how exposure to seawater for 1-15 weeks influenced the accumulation and toxicity of copper nanoparticles (nano-Cu) in a marine phytoplankton species. Nano-Cu rapidly agglomerated in seawater and then decreased in size due to Cu dissolution. Dissolution rates declined during weeks 1-4 and remained low until 15 weeks, when the large agglomerates that had formed began to rapidly dissolve again. Marine phytoplankton species were exposed for 5-day periods to nano-Cu aged from 1 to 15 weeks at concentrations from 0.01 to 20 ppm. Toxicity to phytoplankton, measured as change in population growth rate, decreased significantly with particle aging from 0 to 4 weeks but increased substantially in the 15-week treatment due apparently to elevated Cu dissolution of reagglomerated particles. Results indicate that the transformation, fate, and toxicity of nano-Cu in marine ecosystems are influenced by a highly dynamic physicochemical aging process.

A randomized controlled trial of 12 hours versus 24 hours urinary catheter removal following uncomplicated caesarean section in Ekiti State, Nigeria.

Catheter-associated urinary tract infection (CA-UTI) is one of the common nosocomial infection. Minimizing the length of stay of indwelling urinary catheter has been reported as a key strategy in reducing the rate of the infection. This study compared the incidence of significant bacteriuria in patients who had removal of their urinary catheter in 12 hours compared to those removed after 24 hours following uncomplicated caesarean section. A total of 140 women were randomized into two groups of either 12-hour catheter removal (group A) or 24-hour catheter removal (group B) post-caesarean section. The socio-demographic characteristics, pre-operative and post-operative urine microscopy, culture and sensitivity, time of first ambulation, length of hospital stay and the cost of treatment for all the participants were analyzed using SPSS version 21. P value was set at 0.05. results showed the overall incidence of catheter associated significant bacteriuria was 26.3% in this study while participants in group A (20.9%) had lower incidence of microscopic bacteriuria compared to those in group B (31.8%) though not statistically significant [OR= 1.8: 95%CI (0.8-3.9); p=0.1]. The mean time of first ambulation was statistically lower in group A compared to group B (16.2 ± 7.7 hours versus 24.8 ± 4.3 hours, p<0.001 respectively). The socio-demographic characteristics, incidence of urinary retention, mean length of hospital stay and cost of treatment did not differ significantly between the groups, p >0.05. The study demonstrated that catheter removal at 12 hours post uncomplicated caesarean section can enhance early ambulation and reduce the incidence of post-operative microscopic bacteria. ClinicalTrials.gov identifier PACTR201912777385309.

Multisectoral intervention on food security in complex emergencies: a discourse on regional resilience praxis in Northeast Nigeria.

Sustainable livelihood as an enabler of food security can be constrained by climate variability and violent conflicts, with dire consequences in regions with crude adaptation practices. The effects of such 'complex emergency crises' on food production and livelihoods in Northeast Nigeria impair human security and resilience, particularly, in the Boko Haram ravaged Borno, Yobe and Adamawa states, and the adjoining Lake Chad region. This study examines the efficacy of multisectoral interventions on food security and resilience in Northeast Nigeria, using the Sustainable Livelihoods Approach. Its thematic analysis of qualitative data was supported by the Cadre Harmonisé (CH) regional report of acute food insecurity assessment in the Sahel. It reveals that due to less collaborative and disjointed implementation of multi-stakeholder interventions across critical sectors, the humanitarian, food, and livelihood interventions marginally improve food security and resilience in the region. It recommends that livelihood outcomes and sustainability of the regional resource base be prioritised through diversification of food production, development aid and a holistic regional stabilisation programme. The impact of these mechanisms on agribusiness transformation and long-term food security in northeast Nigeria are significant for adaptation and sustainable livelihood in complex emergencies.

Secondary technical resectability of colorectal cancer liver metastases after chemotherapy with or without selective internal radiotherapy in the randomized SIRFLOX trial.

BACKGROUND: Secondary resection of initially unresectable colorectal cancer liver metastases (CRLM) can prolong survival. The added value of selective internal radiotherapy (SIRT) to downsize lesions for resection is not known. This study evaluated the change in technical resectability of CRLM with the addition of SIRT to FOLFOX-based chemotherapy. METHODS: Baseline and follow-up hepatic imaging of patients who received modified FOLFOX (mFOLFOX6: fluorouracil, leucovorin, oxaliplatin) chemotherapy with or without bevacizumab (control arm) versus mFOLFOX6 (with or without bevacizumab) plus SIRT using yttrium-90 resin microspheres (SIRT arm) in the phase III SIRFLOX trial were reviewed by three or five (of 14) expert hepatopancreatobiliary surgeons for resectability. Reviewers were blinded to one another, treatment assignment, extrahepatic disease status, and information on clinical and scanning time points. Technical resectability was defined as at least 60 per cent of reviewers (3 of 5, or 2 of 3) assessing a patient's liver metastases as surgically removable. RESULTS: Some 472 patients were evaluable (SIRT, 244; control, 228). There was no significant baseline difference in the proportion of technically resectable liver metastases between SIRT (29, 11·9 per cent) and control (25, 11·0 per cent) arms (P = 0·775). At follow-up, significantly more patients in both arms were deemed technically resectable compared with baseline: 159 of 472 (33·7 per cent) versus 54 of 472 (11·4 per cent) respectively (P = 0·001). More patients were resectable in the SIRT than in the control arm: 93 of 244 (38·1 per cent) versus 66 of 228 (28·9 per cent) respectively (P < 0·001). CONCLUSION: Adding SIRT to chemotherapy may improve the resectability of unresectable CRLM.

ANTECEDENTES: La resección secundaria de metástasis hepáticas de cáncer colorrectal (colorectal cancer liver metastases, CRLM) inicialmente irresecables puede prolongar la supervivencia. Se desconoce el valor añadido de la radioterapia interna selectiva (selective internal radiation therapy, SIRT). Este estudio evaluó el cambio en la resecabilidad técnica de las CRLM secundario a la adición de SIRT a una quimioterapia tipo FOLFOX. MÉTODOS: Las pruebas de radioimagen basales y durante el seguimiento de pacientes tratados con un régimen FOLFOX modificado (mFOLFOX6: fluorouracilo, leucovorina, oxaliplatino) ± bevacizumab (grupo control) versus mFOLFOX6 (± bevacizumab) más SIRT usando microesferas de resina de yttrium-90, en el ensayo de fase III SIRFLOX, fueron revisadas por 3-5 (de 14) cirujanos expertos hepatobiliares para determinar la resecabilidad. Los expertos efectuaron la revisión de forma ciega unos respecto a otros en relación con la asignación al tratamiento, estado de la enfermedad extra-hepática y situación clínica en el momento del estudio radiológico. La resecabilidad técnica se definió como ≥ 60% de revisores evaluando las metástasis del paciente como quirúrgicamente resecables. RESULTADOS: Fueron evaluables un total de 472 pacientes (control, n = 228; SIRT, n = 244). No hubo diferencias significativas basales en la proporción de metástasis hepáticas técnicamente resecables entre SIRT (29/244; 11,9%) y el grupo control (25/228; 11,0%: P = 0,775). Durante el seguimiento y en ambos brazos de tratamiento, un número significativamente mayor de pacientes se consideraron técnicamente resecables en comparación con la situación basal (54/472 (11,4%) basal y 159/472 (33,7%) al seguimiento). Hubo más pacientes resecables en el grupo SIRT que en el control (93/244 (38,1%) y 66/228 (28,9%); P < 0,001, respectivamente). CONCLUSIÓN: La adición de SIRT a la quimioterapia puede mejorar la resecabilidad de las CRLM irresecables.

Fate and Transformation of Graphene Oxide in Estuarine and Marine Waters.

The possibility of graphene oxide (GO) exposure to the environment has spurred several studies investigating the fate of this nanoparticle (NP). However, there is currently little or no data on the fate of GO in estuarine and marine waters. This study investigated the aggregation, sedimentation, and transformation of GO in saline waters, considering the roles of salinity (0-50 ‰), light (visible light and solar irradiation), and aging, among others. The attachment efficiency of GO reached unity at 1.33 ‰. The sedimentation rate of GO increased with salinity up to 10 ‰ after which it decreased due to formation of ramified GO agglomerates and media density. On the basis of the sedimentation rate determined at 30 ‰ (0.121 m/d), the residence time of GO agglomerates in the euphotic zone of typical open oceans will exceed 500 days. Aging in the presence of visible light increased the relative abundance of the GO's aromatic (C-C/C=C) fraction, reducing the NP. Reduction of GO in visible light was confirmed via UV-vis and Raman spectroscopic techniques. Reduction of GO was faster under solar irradiation. This study demonstrates that when introduced into saline waters, GO will undergo a range of transformations affecting its fate and potential effects to aquatic organisms.

Detection and Quantification of Graphene-Family Nanomaterials in the Environment.

An increase in production of commercial products containing graphene-family nanomaterials (GFNs) has led to concern over their release into the environment. The fate and potential ecotoxicological effects of GFNs in the environment are currently unclear, partially due to the limited analytical methods for GFN measurements. In this review, the unique properties of GFNs that are useful for their detection and quantification are discussed. The capacity of several classes of techniques to identify and/or quantify GFNs in different environmental matrices (water, soil, sediment, and organisms), after environmental transformations, and after release from a polymer matrix of a product is evaluated. Extraction and strategies to combine methods for more accurate discrimination of GFNs from environmental interferences as well as from other carbonaceous nanomaterials are recommended. Overall, a comprehensive review of the techniques available to detect and quantify GFNs are systematically presented to inform the state of the science, guide researchers in their selection of the best technique for the system under investigation, and enable further development of GFN metrology in environmental matrices. Two case studies are described to provide practical examples of choosing which techniques to utilize for detection or quantification of GFNs in specific scenarios. Because the available quantitative techniques are somewhat limited, more research is required to distinguish GFNs from other carbonaceous materials and improve the accuracy and detection limits of GFNs at more environmentally relevant concentrations.

Metabolomics Reveals Cu(OH)2 Nanopesticide-Activated Anti-oxidative Pathways and Decreased Beneficial Antioxidants in Spinach Leaves.

While the use of nanopesticides in modern agriculture continues to increase, their effects on crop plants are still poorly understood. Here, 4 week old spinach plants grown in an artificial medium were exposed via foliar spray to Cu(OH)2 nanopesticide (0.18 and 18 mg/plant) or Cu ions (0.15 and 15 mg/plant) for 7 days. A gas chromatography-time-of-flight-mass spectrometry metabolomics approach was applied to assess metabolic alterations induced by Cu(OH)2 nanopesticide in spinach leaves. Exposure to Cu(OH)2 nanopesticide and copper ions induced alterations in the metabolite profiles of spinach leaves. Compared to the control, exposure to 18 mg of Cu(OH)2 nanopesticide induced significant reduction (29-85%) in antioxidant or defense-associated metabolites including ascorbic acid, α-tocopherol, threonic acid, ß-sitosterol, 4-hydroxybutyric acid, ferulic acid, and total phenolics. The metabolic pathway for ascorbate and aldarate was disturbed in all exposed spinach plants (nanopesticide and Cu2+). Cu2+ is responsible for the reduction in antioxidants and perturbation of the ascorbate and aldarate metabolism. However, nitrogen metabolism perturbation was nanopesticide-specific. Spinach biomass and photosynthetic pigments were not altered, indicating that metabolomics can be a rapid and sensitive tool for the detection og earlier nanopesticide effects. Consumption of antioxidants during the antioxidant defense process resulted in reduction of the nutritional value of exposed spinach.

Interactions between Algal Extracellular Polymeric Substances and Commercial TiO2 Nanoparticles in Aqueous Media.

The implications of engineered nanomaterials (ENMs) in the environment are often investigated using pristine particles. However, there are several biogenic and geogenic materials in natural waters that interact with and modify the surface of ENMs, thereby influencing their fate and effects. Here we studied the influence of soluble extracellular polymeric substances (sEPS) produced by freshwater and marine algae on the surface properties and fate of three commercial TiO2 nanoparticles (nTiO2) with different coatings. Adsorption of sEPS by the various nTiO2 is dependent on particle surface area, intrinsic nTiO2 surface charge, and hydrophobicity. Interactions between sEPS and nTiO2 were driven by electrostatic interactions and chemical bonding (bridge-coordination) between the COO- group of sEPS and nTiO2. Charge reversal of positively charged nTiO2 was observed at pH 7 in the presence of 0.5 mg-C/L sEPS. In addition, the critical coagulation concentration (CCC) of nTiO2 increased in the presence of sEPS-from both freshwater and marine sources. CCC of all nTiO2 increased as sEPS concentrations increased. This study shows that naturally occurring sEPS can modify the surface properties and fate of nTiO2 in natural waters, and should be accounted for when predicting the fate and effects of engineered nanomaterials in the environment.

Metabolomics to Detect Response of Lettuce (Lactuca sativa) to Cu(OH)2 Nanopesticides: Oxidative Stress Response and Detoxification Mechanisms.

There has been an increasing influx of nanopesticides into agriculture in recent years. Understanding the interaction between nanopesticides and edible plants is crucial in evaluating the potential impact of nanotechnology on the environment and agriculture. Here we exposed lettuce plants to Cu(OH)2 nanopesticides (1050-2100 mg/L) through foliar spray for one month. Inductively coupled plasma-mass spectrometry (ICP-MS) results indicate that 97-99% (1353-2501 mg/kg) of copper was sequestered in the leaves and only a small percentage (1-3%) (17.5-56.9 mg/kg) was translocated to root tissues through phloem loading. Gas chromatography-time-of-flight mass spectrometry (GC-TOF-MS) based metabolomics combined with partial least squares-discriminant analysis (PLS-DA) multivariate analysis revealed that Cu(OH)2 nanopesticides altered metabolite levels of lettuce leaves. Tricarboxylic (TCA) cycle and a number of amino acid-related biological pathways were disturbed. Some antioxidant levels (cis-caffeic acid, chlorogenic acid, 3,4-dihydroxycinnamic acid, dehydroascorbic acid) were significantly decreased compared to the control, indicating that oxidative stress and a defense response occurred. Nicotianamine, a copper chelator, increased by 12-27 fold compared to the control, which may represent a detoxification mechanism. The up-regulation of polyamines (spermidine and putrescine) and potassium may mitigate oxidative stress and enhance tolerance. The data presented here provide a molecular-scale perspective on the response of plants to copper nanopesticides.

Influence of Phytoplankton on Fate and Effects of Modified Zerovalent Iron Nanoparticles.

Nanoscale zerovalent iron (nZVI) and its derivatives hold promise for remediation of several pollutants but their environmental implications are not completely clear. In this study, the physicochemical properties and aggregation kinetics of sulfide/silica-modified nZVI (FeSSi) were compared in algal media in which Chlamydomonas reinhardtii had been cultured for 1, 2, or 11 days in order to elicit the effects of organic matter produced by the freshwater algae. Furthermore, transformation of FeSSi particles were investigated in C. reinhardtii cultures in exponential (1-d) and slowing growth (11-d) phases while monitoring the response of algae. We found evidence for steric stabilization of FeSSi by algal organic matter, which led to a decrease in the particles' attachment efficiency. Transformation of FeSSi was slower in 11-d cultures as determined via inductively coupled plasma and X-ray analyses. High concentrations of FeSSi caused a lag in algal growth, and reduction in steady state population size, especially in cultures in exponential phase. The different outcomes are well described by a dynamic model describing algal growth, organic carbon production, and FeSSi transformations. This study shows that feedback from algae may play important roles in the environmental implications of engineered nanomaterials.

(1)H NMR and GC-MS Based Metabolomics Reveal Defense and Detoxification Mechanism of Cucumber Plant under Nano-Cu Stress.

Because copper nanoparticles are being increasingly used in agriculture as pesticides, it is important to assess their potential implications for agriculture. Concerns have been raised about the bioaccumulation of nano-Cu and their toxicity to crop plants. Here, the response of cucumber plants in hydroponic culture at early development stages to two concentrations of nano-Cu (10 and 20 mg/L) was evaluated by proton nuclear magnetic resonance spectroscopy ((1)H NMR) and gas chromatography-mass spectrometry (GC-MS) based metabolomics. Changes in mineral nutrient metabolism induced by nano-Cu were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Results showed that nano-Cu at both concentrations interferes with the uptake of a number of micro- and macro-nutrients, such as Na, P, S, Mo, Zn, and Fe. Metabolomics data revealed that nano-Cu at both levels triggered significant metabolic changes in cucumber leaves and root exudates. The root exudate metabolic changes revealed an active defense mechanism against nano-Cu stress: up-regulation of amino acids to sequester/exclude Cu/nano-Cu; down-regulation of citric acid to reduce the mobilization of Cu ions; ascorbic acid up-regulation to combat reactive oxygen species; and up-regulation of phenolic compounds to improve antioxidant system. Thus, we demonstrate that nontargeted (1)H NMR and GC-MS based metabolomics can successfully identify physiological responses induced by nanoparticles. Root exudates metabolomics revealed important detoxification mechanisms.

Aggregation, dissolution, and transformation of copper nanoparticles in natural waters.

Time-dependent aggregation, sedimentation, dissolution, and transformation of three copper-based engineered nanomaterials (ENMs) of varied properties were measured in eight natural and artificial waters. Nano-Cu and Cu(OH)2 aggregated rapidly to >10(3) nm while the aggregate size of nano-CuO averaged between 250 and 400 nm. Aggregate size for both nano-Cu and nano-CuO showed a positive correlation with ionic strength with a few exceptions. Aggregate size did not correlate well with sedimentation rate, suggesting sedimentation was influenced by other factors. Controlling factors in sedimentation rates varied by particle: Cu(OH)2 particles remained stable in all waters but groundwater, nano-Cu was generally unstable except in waters with high organic content, and nano-CuO was stabilized by the presence of phosphate, which reversed surface charge polarity at concentrations as low as 0.1 mg PO4(3-) L(-1). Dissolution generally correlated with pH, although in saline waters, dissolved copper formed insoluble complexes. Nano-Cu was rapidly oxidized, resulting in dissolution immediately followed by the formation of precipitates. These results suggest factors including phosphate, carbonate, and ENM oxidation state may be key in determining Cu ENM behavior in natural waters.

Influence of extracellular polymeric substances on the long-term fate, dissolution, and speciation of copper-based nanoparticles.

The influence of phytoplankton-derived soluble extracellular polymeric substances (EPS), pH, and ionic strength (IS) on the dissolution, speciation, and stability of nano-CuO, nano-Cu, and Kocide (a micron sized Cu(OH)2-based fungicide) was investigated over 90 days. EPS improved the stability of commercial copper-based nanoparticles (CBNPs) in most conditions, in addition to influencing their dissolution. The dissolution rate was pH 4≫pH 7>pH 11. The presence of EPS correlated with higher dissolved Cu at pH 7 and 11, and lower dissolved Cu at pH 4. More dissolution was observed at higher IS (NaCl) due to complexation with Cl-. Dissolution of nano-CuO at pH 7 increased from 0.93% after 90 days (without EPS) to 2.01% (with 5 mg-C EPS/L) at 10 mM IS. Nano-CuO dissolved even more (2.42%) when IS was increased to 100 mM NaCl (with EPS). The ratio of free-Cu2+/total dissolved Cu decreased in the presence of EPS, or as pH and/or IS increased. On a Cu mass basis, Kocide had the highest dissolved and suspended Cu at pH 7. However, dissolution of nano-Cu resulted in a higher fraction of free Cu2+, which may make nano-Cu more toxic to pelagic organisms.

Effects of TiO2 and Ag nanoparticles on polyhydroxybutyrate biosynthesis by activated sludge bacteria.

Manufactured nanomaterials (MNMs) are increasingly incorporated into consumer products that are disposed into sewage. In wastewater treatment, MNMs adsorb to activated sludge biomass where they may impact biological wastewater treatment performance, including nutrient removal. Here, we studied MNM effects on bacterial polyhydroxyalkanoate (PHA), specifically polyhydroxybutyrate (PHB), biosynthesis because of its importance to enhanced biological phosphorus (P) removal (EBPR). Activated sludge was sampled from an anoxic selector of a municipal wastewater treatment plant (WWTP), and PHB-containing bacteria were concentrated by density gradient centrifugation. After starvation to decrease intracellular PHB stores, bacteria were nutritionally augmented to promote PHB biosynthesis while being exposed to either MNMs (TiO2 or Ag) or to Ag salts (each at a concentration of 5 mg L(-1)). Cellular PHB concentration and PhyloChip community composition were analyzed. The final bacterial community composition differed from activated sludge, demonstrating that laboratory enrichment was selective. Still, PHB was synthesized to near-activated sludge levels. Ag salts altered final bacterial communities, although MNMs did not. PHB biosynthesis was diminished with Ag (salt or MNMs), indicating the potential for Ag-MNMs to physiologically impact EBPR through the effects of dissolved Ag ions on PHB producers.

Adsorption of PFAS onto secondary microplastics: A mechanistic study.

Microplastics (MPs) are abundant in aquatic systems. The ecological risks of MPs may arise from their physical features, chemical properties, and/or their ability to concentrate and transport other contaminants, such as per- and polyfluoroalkyl substances (PFAS). PFAS have been extracted from MPs found in natural waters. Still, there needs to be a mechanistic investigation of the effect of PFAS chemistry and water physicochemical properties on how PFAS partition onto secondary MPs. Here, we studied the influence of pH, natural organic matter (NOM), ionic strength, and temperature on the adsorption of PFAS on MPs generated from PET water bottles. The adsorption of PFAS to the MPs was thermodynamically spontaneous at 25 °C, based on Gibb's free energy (ΔG = -16 to -23 kJ/mol), primarily due to increased entropy after adsorption. Adsorption reached equilibrium within 7-9 h. Hence, PFAS will partition to the surface of secondary PET MPs within hours in fresh and saline waters. Natural organic matter decreased the capacity of secondary PET MPs for PFAS through electrosteric repulsion, while higher ionic strength favored PFAS adsorption by decreasing electrostatic repulsion. Increased pH increased electrostatic repulsion, which negated PFAS adsorption. The study provides fundamental information for developing models to predict interactions between secondary MPs and PFAS.

PFAS release from the subsurface and capillary fringe during managed aquifer recharge.

Managed aquifer recharge (MAR) is a sustainable way of harvesting groundwater in water-stressed urbanized areas, where reclaimed wastewater or stormwater is applied on a large basin to infiltrate water into the groundwater aquifer naturally. This process could rapidly fluctuate the water table and move the capillary fringe boundary, and the change in flow dynamic and associated geochemical changes could trigger the release of sequestered pollutants, including per- and polyfluoroalkyl substances (PFAS), also known as 'forever chemicals', from the subsurface and capillary fringe. Yet, the potential of PFAS release from the subsurface and capillary zone during recharge events when the water table rapidly fluctuates has not been evaluated. This study uses laboratory column experiments to simulate PFAS release from pre-contaminated subsurface and capillary fringe during groundwater table fluctuation. The results reveal that the groundwater level fluctuations during MAR increased the release of perfluorobutanesulfonic acid (PFBS) and perfluorooctanesulfonic acid (PFOS) from the capillary fringe, but the fraction released depended on PFAS type and their association with soil colloids. A higher proportion of PFOS in column effluent was found to be associated with particles, while a greater portion of released PFBS was in a free or dissolved state. The direction of water table fluctuation did not affect the release of PFAS in this study. A lack of change in the concentration of bromide, a conservative tracer, during flow interruption, indicates that diffusion of PFAS through reconnected pores during water table rise had an insignificant effect on PFAS release. Overall, this study provides insights into how PFAS can be released from the subsurface and capillary fringe during managed aquifer recharge when the groundwater level is expected to fluctuate quickly.

Dissolvable sodium alginate-based antibacterial wound dressing patches: Design, characterization, and in vitro biological studies.

The treatment of infected wounds in patients with highly sensitive skin is challenging. Some of the available wound dressings cause further skin tear and bleeding upon removal thereby hindering the healing process. In this study, dissolvable antibacterial wound dressing patches loaded with cephalexin monohydrate were prepared from different amounts of sodium alginate (SA) and carboxymethyl cellulose (CMC) by the solvent casting evaporation technique. The patches displayed good tensile strength (3.83-13.83 MPa), appropriate thickness (0.09 to 0.31 mm) and good flexibility (74-98 %) suitable for the skin. The patches displayed good biodegradability and low moisture uptake suitable to prevent microbial invasion on the wound dressings upon storage. The release profile of the drug from the patches was sustained in the range of 47-80 % for 48 h, revealing their capability to inhibit bacterial infection. The biological assay showed that the patches did not induce cytotoxic effects on HaCaT cells, revealing good biocompatibility. The antimicrobial effect of the patches on the different strains of bacteria used in the study was significant. The cell migration (66.7-74.3 %) to the scratched gap was promising revealing the patches' capability to promote wound closure. The results obtained show that the wound dressings are potential materials for the treatment of infected wounds.

Perfluorooctanoic acid dominates the molecular-level effects of a mixture of equal masses of perfluorooctanoic acid and perfluorooctane sulfonic acid in earthworm.

Per- and polyfluoroalkyl substances (PFAS) are an important class of emerging contaminants in the environment. Most studies on the impact of PFAS mixtures considered phenotypic endpoints, which may not adequately reflect the sublethal effects on organisms. To fill this knowledge gap, we investigated the subchronic impact of environmentally relevant concentrations of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS)-as individual compounds and a mixture (PFOS+PFOA)-on earthworm (Eisenia fetida), using phenotypic and molecular endpoints. PFAS decreased the survival (12.2-16.3%), biomass (9.0-9.8%), and reproduction (15.6-19.8%) of E. fetida after 28 d of exposure. The bioaccumulation of PFOS after 28 d increased (from 2790.7 ng/g-dw to 5224.9 ng/g-dw) while that of PFOA decreased (from 780.2 ng/g-dw to 280.5 ng/g-dw) when E. fetida was exposed to the mixture compared to the individual compounds. These bioaccumulation trends were partly attributed to changes in the soil distribution coefficient (Kd) of PFOS and PFOA when present in the mixture. Eighty percent of the (p and FDR < 0.05) altered metabolites after 28 d were similarly perturbed by both PFOA and PFOS+PFOA. The pathways dysregulated are related to the metabolism of amino acids, energy, and sulfur. We showed that PFOA dominates the molecular-level impact of the binary PFAS mixture.

Nanomaterials as catalysts for CO2 transformation into value-added products: A review.

Carbon dioxide (CO2) is the most important greenhouse gas (GHG), accounting for 76% of all GHG emissions. The atmospheric CO2 concentration has increased from 280 ppm in the pre-industrial era to about 418 ppm, and is projected to reach 570 ppm by the end of the 21st century. In addition to reducing CO2 emissions from anthropogenic activities, strategies to adequately address climate change must include CO2 capture. To promote circular economy, captured CO2 should be converted to value-added materials such as fuels and other chemical feedstock. Due to their tunable chemistry (which allows them to be selective) and high surface area (which allows them to be efficient), engineered nanomaterials are promising for CO2 capturing and/or transformation. This work critically reviewed the application of nanomaterials for the transformation of CO2 into various fuels, like formic acid, carbon monoxide, methanol, and ethanol. We discussed the literature on the use of metal-based nanomaterials, inorganic/organic nanocomposites, as well as other routes suitable for CO2 conversion such as the electrochemical, non-thermal plasma, and hydrogenation routes. The characteristics, steps, mechanisms, and challenges associated with the different transformation technologies were also discussed. Finally, we presented a section on the outlook of the field, which includes recommendations for how to continue to advance the use of nanotechnology for conversion of CO2 to fuels.