Aqueous Concentrations Research Articles

Fluorite and Gibbsite Solubility Controls the Vertical Transport of Fluoride and Aluminum during Rainwater Percolation through Ashfall Deposits in La Palma (Canary Islands, Spain)

This study addresses the in situ mobility of fluoride and aluminum in two different ashfall deposits accumulated during the 2021 eruption of the Tajogaite volcano (La Palma, Canary Islands, Spain), which were exposed to contrasting conditions of ambient humidity and precipitation. We selected one site to the east of the volcanic emission center, located near the top of Cumbre Vieja Ridge and exposed to continuous humidity and rain, and another site to the west of the volcano situated in a lowland and characterized by much drier conditions. The mobility of fluoride and aluminum is markedly different at both sites, with the first sequence suggesting a downwards migration of Al and F, and the second sequence showing no sign of mobility. The migration of aluminum and fluorine results from the dissolution of different fluoride salts (mostly AlF3 and CaF2, as suggested by scanning electron microscopy) followed by vertical transport as ionic complexes (AlF3, AlF2+, AlF4−) during the percolation of rainwater through the ashfall deposits. Geochemical calculations suggest that the mobility of fluorine at neutral to alkaline conditions (pH 7.0–9.0) is likely limited by the solubility of fluorite (CaF2), whereas at slightly acidic conditions (pH < 6.5), the aqueous concentration of aluminum seems to be controlled by the solubility of gibbsite (Al(OH)3). This study demonstrates that aluminum and fluoride can be transported from volcanic ash to the underlying soil or groundwater, which is an environmental concern that should be followed in the future.

Uranium accumulation in environmentally relevant microplastics and agricultural soil at acidic and circumneutral pH

The co-occurrence of microplastics (MPs) with potentially toxic metals in the environment stresses the need to address their physicochemical interactions and the potential ecological and human health implications. Here, we investigated the reaction of aqueous U with agricultural soil and high-density polyethylene (HDPE) through the integration of batch experiments, microscopy, and spectroscopy. The aqueous initial concentration of U (100 μM) decreased between 98.6 and 99.2 % at pH 5 and between 86.2 and 98.9 % at pH 7.5 following the first half hour of reaction with 10 g of soil. In similar experimental conditions but with added HDPE, aqueous U decreased between 98.6 and 99.7 % at pH 5 and between 76.1 and 95.2 % at pH 7.5, suggesting that HDPE modified the accumulation of U in soil as a function of pH. Uranium-bearing precipitates on the cracked surface of HDPE were identified by SEM/EDS after two weeks of agitation in water at both pH 5 and 7.5. Accumulation of U on the near-surface region of reacted HDPE was confirmed by XPS. Our findings suggest that the precipitation of U was facilitated by the weathering of the surface of HDPE. These results provide insights about surface-mediated reactions of aqueous metals with MPs, contributing relevant information about the mobility of metals and MPs at co-contaminated agricultural sites.

Per- and Polyfluoroalkyl Substances in Water (2008-2022) and Fish (2015-2022) in The Netherlands: Spatiotemporal Trends, Fingerprints, Mass Discharges, Sources, and Bioaccumulation Factors.

Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative, and toxic synthetic chemicals of concern, which have been detected in nearly all environmental compartments. The present study provides a data analysis on PFAS concentrations in the Dutch inland and coastal national waters and fish sampled from 2008 to 2022 and 2015 to 2022, respectively. Although the fish database is relatively small, the water database is unique because of its temporal dimension. It appears that PFAS are omnipresent in Dutch water and fish, with relatively small spatial differences in absolute and relative concentrations (fingerprints) and few obvious temporal trends. Only perfluorooctanoic acid and perfluorooctanesulfonic acid (PFOS) aqueous concentrations in the rivers Rhine and Scheldt have substantially decreased since 2012. Still, PFOS concentrations exceed the European water quality standards at all and fish standards at many locations. Masses of PFAS entering the country and the North Sea are roughly 3.5 tonnes/year. Generally, the data suggest that most PFAS enter the Dutch aquatic environment predominantly through diffuse sources, yet several major point sources of specific PFAS were identified using fingerprints and monthly concentration profiles as identification tools. Finally, combining concentrations in fish and water, 265 bioaccumulation factors were derived, showing no statistically significant differences between freshwater and marine fish. Overall, the analysis provides new insights into PFAS bioaccumulation and spatiotemporal trends, mass discharges, and sources in The Netherlands. Environ Toxicol Chem 2024;43:965-975. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Unraveling the Mystery of Water-Induced Loess Disintegration: A Comprehensive Review of Experimental Research

Loess disintegration is a significant physicochemical and mechanical dissolution process that occurs when loess comes into contact with water. This phenomenon contributes to geological disasters such as loess cave erosion, landslides, and debris flows. The disintegration of loess can be influenced by both internal and external factors. Research on internal factors of loess disintegration has been widely recorded, but the research progress on external environmental factors that affect loess disintegration is not well summarized. This review summarizes the impacts of external water environmental factors on loess disintegration and reveals that six external water environmental factors, namely the temperature of the aqueous solution, hydrodynamic conditions, solution pH, salt concentration and type in the solution, freeze–thaw cycles, and dry–wet cycles, can significantly impact loess disintegration. Furthermore, this review delves into three key research areas in loess disintegration under the influence of these water environmental factors: experimental research on loess disintegration, the disintegration parameters used in such research and their variations, and the water–soil chemical reactions and microstructural changes during loess disintegration. It concludes that current experimental research on loess disintegration suffers from inadequate studies, with existing research associated with poor comparability and weak representativeness, and a lack of comprehensive, systematic analysis of its regularities of influence and response mechanisms from both microscopic and macroscopic perspectives. This paper can provide valuable insights for the prevention of loess geological disasters and engineering safety construction.

Roles of pH and phosphate in rare earth element biosorption with living acidophilic microalgae

The increasing demand for rare earth elements (REEs) has spurred interest in the development of recovery methods from aqueous waste streams. Acidophilic microalgae have gained attention for REE biosorption as they can withstand high concentrations of transition metals and do not require added organic carbon to grow, potentially allowing simultaneous sorption and self-replication of the sorbent. Here, we assessed the potential of Galdieria sulphuraria for REE biosorption under acidic, nutrient-replete conditions from solutions containing ≤ 15 ppm REEs. Sorption at pH 1.5–2.5 (the growth optimum of G. sulphuraria) was poor but improved up to 24-fold at pH 5.0 in phosphate-free conditions. Metabolic activity had a negative impact on REE sorption, additionally challenging the feasibility of REE biosorption under ideal growth conditions for acidophiles. We further examined the possibility of REE biosorption in the presence of phosphate for biomass growth at elevated pH (pH ≥ 2.5) by assessing aqueous La concentrations in various culture media. Three days after adding La into the media, dissolved La concentrations were up to three orders of magnitude higher than solubility predictions due to supersaturation, though LaPO4 precipitation occurred under all conditions when seed was added. We concluded that biosorption should occur separately from biomass growth to avoid REE phosphate precipitation. Furthermore, we demonstrated the importance of proper control experiments in biosorption studies to assess potential interactions between REEs and matrix ions such as phosphates.Key points• REE biosorption with G. sulphuraria increases significantly when raising pH to 5• Phosphate for biosorbent growth has to be supplied separately from biosorption• Biosorption studies have to assess potential matrix effects on REE behavior

Facile extraction of lignin-carbohydrate complexes from bamboo with formic acid aqueous solution under moderate conditions

The extraction of lignin-carbohydrate complexes (LCC) while preserving the majority of the interconnecting bonds poses a formidable challenge in characterizing the structure and exploring further applications. In this study, a straightforward approach was proposed to extract LCC from bamboo by precisely adjusting formic acid aqueous solution concentrations (70 % to 100 %) and reaction temperatures (40 to 100 °C) under normal pressure. Notably, employing a 90 % formic acid aqueous solution at 100 °C for 2 h led to an impressive LCC yield of 24.47 %. Moreover, all the LCC samples demonstrated exceptional homogeneity with a polydispersity index ≤ 1.97. Nuclear magnetic resonance analysis revealed the presence of phenyl glycosidic, benzyl ether, benzyl ester, and acetal bonds within the extracted LCC, with phenyl glycosidic bonds serving as the predominant linkages. The LCC samples displayed notable antioxidant capacity, as evidenced by their high DPPH free radical scavenging index of 1.28.

Water activity and surface tension of aqueous ammonium sulfate and D-glucose aerosol nanoparticles

Abstract. Water activity (aw) and interfacial energy or surface tension (σ) are key thermodynamic parameters to describe the hygroscopic growth of atmospheric aerosol particles and their ability to serve as cloud condensation nuclei (CCN), thus influencing the hydrological cycle and climate. Due to size effects and complex mixing states, however, these parameters are not well constrained for nanoparticles composed of organic and inorganic compounds in aqueous solution. In this study, we determined aw and σ by differential Köhler analysis (DKA) of hygroscopic growth measurement data for aerosol particles smaller than 100 nm composed of aqueous ammonium sulfate (AS), D-glucose (Gl), and their mixtures. High-precision measurements of hygroscopic growth were performed at relative humidities (denoted RH) ranging from 2.0 % to 99.6 % with a high-humidity tandem differential mobility analyzer (HHTDMA) in three complementary modes of operation: hydration, dehydration, and restructuring. The restructuring mode (hydration followed by dehydration) enabled the transformation of initially irregular particles into compact globules and the determination of mass equivalent diameters. The HHTDMA-derived growth factors complemented by DKA allows for determination of water activity and surface tension from dilute to highly supersaturated aqueous solutions that are not accessible with other methods. Thus, for mixed AS / Gl nanoparticles with mass ratios of 4:1 and 1:1, the upper limit of solute mass fraction (Xs) was 0.92 and 0.98, respectively. For pure AS and Gl, the DKA-derived aw is in good agreement with electrodynamic balance and bulk measurement data. For AS particles, our aw data also agree well with the Extended Aerosol Inorganics Model (E-AIM III) over the entire concentration range. In contrast, the UNIFAC model as a part of AIOMFAC (Zuend et al., 2011) was found to overestimate aw in aqueous Gl particles, which can be attributed to unaccounted intermolecular interactions. For mixed AS and Gl nanoparticles, we observed a non-monotonic concentration dependence of the surface tension that does not follow the predictions by modeling approaches constructed for mixed inorganic/organic systems. Thus, AS / Gl particles with a 1:1 mass ratio exhibited a strong decrease of σ with increasing solute mass fraction, a minimum value of 56.5 mN m−1 at Xs≈0.5, and a reverse trend of increasing σ at higher concentrations. We suggest that D-glucose molecules surrounded by ammonium sulfate ions tend to associate, forming non-polar aggregates, which lowers the surface tension at the air–droplet interface. We analyzed the uncertainty in the DKA-derived water activity and surface tension, related to the instrumental errors as well as to the morphology of the nanoparticles and their phase state. Our studies have shown that under optimal modes of operation of HHTDMA for moderate aqueous concentrations, the uncertainty in aw and σ does not exceed 0.2 %–0.4 % and 3 %–4 %, respectively, but it increases by an order of magnitude in the case of highly concentrated nanodroplet solutions.

Transcriptomics-Based Points of Departure for Daphnia magna Exposed to 18 Per- and Polyfluoroalkyl Substances.

Per- and polyfluoroalkyl substances (PFAS) represent a large group of contaminants of concern based on their widespread use, environmental persistence, and potential toxicity. Many traditional models for estimating toxicity, bioaccumulation, and other toxicological properties are not well suited for PFAS. Consequently, there is a need to generate hazard information for PFAS in an efficient and cost-effective manner. In the present study, Daphnia magna were exposed to multiple concentrations of 22 different PFAS for 24 h in a 96-well plate format. Following exposure, whole-body RNA was extracted and extracts, each representing five exposed individuals, were subjected to RNA sequencing. Following analytical measurements to verify PFAS exposure concentrations and quality control on processed cDNA libraries for sequencing, concentration-response modeling was applied to the data sets for 18 of the tested compounds, and the concentration at which a concerted molecular response occurred (transcriptomic point of departure; tPOD) was calculated. The tPODs, based on measured concentrations of PFAS, generally ranged from 0.03 to 0.58 µM (9.9-350 µg/L; interquartile range). In most cases, these concentrations were two orders of magnitude lower than similarly calculated tPODs for human cell lines exposed to PFAS. They were also lower than apical effect concentrations reported for seven PFAS for which some crustacean or invertebrate toxicity data were available, although there were a few exceptions. Despite being lower than most other available hazard benchmarks, D. magna tPODs were, on average, four orders of magnitude greater than the maximum aqueous concentrations of PFAS measured in Great Lakes tributaries. Overall, this high-throughput transcriptomics assay with D. magna holds promise as a component of a tiered hazard evaluation strategy employing new approach methodologies. Environ Toxicol Chem 2024;00:1-16. © 2024 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Short‐Term Arsenic Cycling in a Shallow, Polymictic Lake

AbstractArsenic (As), a harmful contaminant present in many urban lakes, can negatively impact lake ecosystem health when aqueous concentrations are elevated. We observed repeated diel oscillations in As concentrations in the bottom waters of a shallow, temperate lake during a weeklong period. In this work, we explore four mechanistic hypotheses to explain the diel As cycles based on the physical and biogeochemical processes that were investigated during the study. Despite pH being known to control diel As cycles in rivers, we determined that this mechanism was inconsistent with As dynamics observed in Lake Killarney. Instead, we found that iron and manganese concentrations oscillated simultaneously with As concentrations and that redox conditions adjacent to the lakebed likely controlled the near‐bed availability of these three elements. However, based on timescale analysis, we determined that biogeochemical processes at the sediment water interface alone could not have led to the daily oscillations in bottom water concentrations. Rather, turbulence from convective mixing was necessary to transport dissolved species. Notably, we saw that the timing and intensity of peaks in convectively driven turbulence were consistent with observed diel fluctuations in bottom water As. Our results indicate that physical mixing is key in controlling As transport and concentrations on diel timescales within shallow lakes. Understanding the daily cycling of As in shallow lakes is essential for predicting the degree to which lake biota are exposed to this contaminant. Diel oscillations in As concentrations should be considered when designing sampling methods to assess the water quality of contaminated sites.

Analytical quality by design approach for the development of high-performance liquid chromatography method for simultaneous analysis of metformin and sitagliptin in the presence of major degradation products.

An analytical quality by design-based high-performance liquid chromatography method for determining metformin (MET) and sitagliptin (SIT) in stress-degraded samples was developed and validated. The analytical target profile and risk assessment-driven critical method variables, for example, pH, % aqueous, and buffer concentration, were studied for their effect on method responses of retention time and resolution using a central composite design. The correlation regression coefficient was more than 0.8, and variables interaction was significant on method responses with curvature effect. The method operable design region afforded an aqueous range of 55%-70% and an ortho-phosphoric acid buffer of 0.1% with a pH of 3.0-4.0 as a robust region for the suitable method performance characteristics. The separation of MET and SIT from their degradants (m/z 85.0509; m/z 193.0694) on the C8 column was achieved using a mobile phase consisting of 0.1% ortho-phosphoric acid and methanol (60:40% v/v; pH 3.0). The optimized method eluted MET and SIT at 4.3±0.2 and 7.1±0.2min, respectively, with acceptable specificity and resolution. The linearity ranges of 25-250μg/mL (r2 : 0.9982) and 5-50μg/mL (r2 : 0.9989) was established for MET and SIT, respectively. The % recovery (98.81%-102.17%), precision (0.55%-1.65%), and robustness study for method variables were acceptable.

Solvent extraction of cobalt from artificial nickel sulphate solution using PC-88A organic solution as extractant

In this research, an experiment was carried out to separate cobalt from artificial nickel sulfate solution containing cobalt ions by solvent extraction method using organic solvent 2-ethythexyl phosponic acid mono-2-ethylhexyl ester (PC-88A). The experiment was carried out on a laboratory scale. The experimental variables observed included the acidity of the solution (pH), shaking time, shaking speed, and ratio of aqueous and organic (A/O) volume and concentration of PC-88A extractant. The experimental results showed that at pH 6 as much as 95.68% of cobalt could be extracted with the PC-88A.

Derivation of Transcriptomics-Based Points of Departure for 20 Per- or Polyfluoroalkyl Substances Using a Larval Fathead Minnow (Pimephales promelas) Reduced Transcriptome Assay.

Traditional toxicity testing has been unable to keep pace with the introduction of new chemicals into commerce. Consequently, there are limited or no toxicity data for many chemicals to which fish and wildlife may be exposed. Per- and polyfluoroalkyl substances (PFAS) are emblematic of this issue in that ecological hazards of most PFAS remain uncharacterized. The present study employed a high-throughput assay to identify the concentration at which 20 PFAS, with diverse properties, elicited a concerted gene expression response (termed a transcriptomics-based point of departure [tPOD]) in larval fathead minnows (Pimephales promelas; 5-6 days postfertilization) exposed for 24 h. Based on a reduced transcriptome approach that measured whole-body expression of 1832 genes, the median tPOD for the 20 PFAS tested was 10 µM. Longer-chain carboxylic acids (12-13 C-F); an eight-C-F dialcohol, N-alkyl sulfonamide; and telomer sulfonic acid were among the most potent PFAS, eliciting gene expression responses at concentrations <1 µM. With a few exceptions, larval fathead minnow tPODs were concordant with those based on whole-transcriptome response in human cell lines. However, larval fathead minnow tPODs were often greater than those for Daphnia magna exposed to the same PFAS. The tPODs overlapped concentrations at which other sublethal effects have been reported in fish (available for 10 PFAS). Nonetheless, fathead minnow tPODs were orders of magnitude higher than aqueous PFAS concentrations detected in tributaries of the North American Great Lakes, suggesting a substantial margin of safety. Overall, results broadly support the use of a fathead minnow larval transcriptomics assay to derive screening-level potency estimates for use in ecological risk-based prioritization. Environ Toxicol Chem 2024;00:1-16. © 2024 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

A Deep Insight into Perfluorooctanoic Acid Photodegradation Using Metal Ion-Exchanged Zeolites.

Treating perfluorooctanoic acid (PFOA) in an aqueous environment is problematic due to its low concentration and its high resistance to biological and chemical degradation. To tackle this challenge, combinations of pre-enrichment and photodegradation processes are promising solutions. In this work, we investigated metal ion-exchanged zeolites as adsorbents and photocatalysts for PFOA treatment. Among various transition metal ion-exchanged BEA zeolites, Fe-exchanged BEA (Fe-BEA) zeolites showed significant activity for the photodegradation of PFOA. The isolated iron species in Fe-BEA zeolite are responsible for PFOA photodegradation, whereas other iron species present from excess iron loading in the zeolite will lower its photocatalytic activity. Furthermore, it was proved via size exclusion tests using branched PFOA isomers that the photodegradation of PFOA took place on the internal surface rather than the external surface of Fe-BEA zeolite. Photodegradation of PFOA was also tested to be effective with Fe-exchanged BEA-type zeolites having various SiO2/Al2O3 ratios, but ineffective with FAU-type zeolites. The optimal Fe-BEA zeolite showed a sorption coefficient Kd of 6.0 × 105 L kg-1 at an aqueous phase PFOA concentration of 0.7 μg L-1 and a PFOA half-life of 1.8 h under UV-A irradiation. The presented study offers a deeper understanding of the use of metal ion-exchanged zeolites for photodegradation of PFOA.

Potentially compromised systemic and local lactate metabolic balance in glaucoma, which could increase retinal glucose and glutamate concentrations

To investigate the association between lactate metabolism and glaucoma, we conducted a multi-institutional cross-sectional clinical study and a retinal metabolomic analysis of mice with elevated intraocular pressure (IOP) induced by intracameral microbead injection. We compared lactate concentrations in serum and aqueous humor in age-matched 64 patients each with primary open-angle glaucoma (POAG) and cataract. Neither serum nor aqueous humor lactate concentrations differed between the two groups. Multiple regression analysis revealed that only body mass index showed a significant positive correlation with serum and aqueous humor lactate concentration in POAG patients (rs = 0.376, P = 0.002, and rs = 0.333, P = 0.007, respectively), but not in cataract patients. l-Lactic acid was one of the most abundantly detected metabolites in mouse retinas with gas chromatography and mass spectrometry, but there were no significant differences among control, 2-week, and 4-week IOP elevation groups. After 4 weeks of elevated IOP, d-glucose and l-glutamic acid ranked as the top two for a change in raised concentration, roughly sevenfold and threefold, respectively (ANOVA, P = 0.004; Tukey–Kramer, P < 0.05). Glaucoma may disrupt the systemic and intraocular lactate metabolic homeostasis, with a compensatory rise in glucose and glutamate in the retina.

Synthesis of AuNPs in microemulsion and nano-emulsion systems using aqueous extract of C. chayamansa leaves as reducing agent

This paper explores the synthesis and characterization of gold nanoparticles using various microemulsion and nano-emulsion systems. The pseudo-ternary system consists of an aqueous phase / Brij O10: 1,2-hexanediol (1:1) / castor oil; the aqueous phases include the aqueous extract of Chaya Maya (Cnidoscolus chayamansa) leaves or aqueous extract of Chaya maya leaves combined with the inorganic gold precursor. Chaya maya extract act as a reducing agent for gold (III) ions. The influence of aqueous phase content and surfactant concentration on gold nanoparticles size, morphology, and stability is investigated. Dynamic Light Scattering, Scanning Transmission Electron Microscopy, and UV-Vis spectroscopy are employed to analyze the synthesized gold nanoparticles. The sizes of the gold nanoparticles obtained were influenced by the system composition and are within the range of 19–40 nm. Results indicate that increasing the aqueous phase content generally leads to larger nanoparticle sizes, while higher surfactant concentrations yield smaller nanoparticles. A transition from microemulsion to nano-emulsion is observed at a specific aqueous phase content, marking a shift in nanoparticle size distribution and growth behavior. Additionally, microemulsion and nano-emulsion systems provide stability to gold nanoparticles, as evidenced by measured Zeta potentials indicating negatively charged surfaces conducting to colloidal stability. Also, remark that the use of organometallic precursors is no needed to obtain very good results on nanoparticle size and shape when O/W systems are used to this end. These findings highlight the potential of tailored microemulsion and nano-emulsion systems formulated with low-toxic components for controlling gold nanoparticles properties under mild conditions, contributing to the development of advanced gold nanoparticles-based materials with enhanced functionalities, with implications for diverse applications.

The Effect of Intracameral Triamcinolone Acetonide on Controlling Common Complications following Phacoemulsification in Dogs.

The intracameral injection of triamcinolone acetonide (TA) has achieved favorable clinical effects in controlling intraocular inflammatory reactions in humans after cataract surgery. However, the effect of this method remains unclear in veterinary practice. In this paper, 18 dogs with bilateral cataracts were randomly divided into three groups, with 6 dogs in each group. Phacoemulsification and intraocular lens implantation were performed on the 36 eyes of these dogs. A total of 0.1 mL of TA solution was injected into the oculus dexter (OD) anterior chambers. All oculus sinister (OS) anterior chambers of these dogs were used as controls. The results demonstrated that the corneal edema severity scores of the OD (1.5 mg TA) were lower than those of the OS from the 1st to 7th day after surgery, with a significant difference on the 3rd day after surgery (p = 0.033). The corneal edema severity scores in the OD (1.5 mg TA) were significantly lower than those in the OD (0.5 mg TA) on the 3rd day after surgery (p = 0.036). The aqueous humor protein concentration of the OD (1.5 mg TA) had a lower concentration than the OS on the 1st day after surgery (p = 0.004). Furthermore, on the 5th and 10th days, the aqueous humor protein concentration of the OD (1.5 mg TA) was lower than that of the OS (p = 0.038 and p = 0.044, respectively). The aqueous humor PGE2 concentration of the OD (1.5 mg TA) had a lower concentration than the OS on the 1st day after surgery (p = 0.026). The aqueous humor PGE2 concentrations in the OD (1.0 mg TA) and OD (1.5 mg TA) were lower compared to that in the OD (0.5 mg TA) on the 1st day after surgery (p = 0.041 and p = 0.037, respectively). It was demonstrated that TA-based treatment can be safely employed to effectively control common complications after phacoemulsification in dogs.

Anterior chamber cytokine production and postoperative macular edema in patients with diabetes undergoing FLACS.

To evaluate the effect of femtosecond laser-assisted cataract surgery (FLACS) and manual cataract surgery (MCS) on proinflammatory cytokine expression in patients with diabetes vs nondiabetic patients. Outpatient surgical center in Vaughan, Ontario, Canada. Prospective cohort study. Patients with diabetes and nondiabetic patients undergoing noncomplicated MCS or FLACS were assigned into 4 cohorts: MCS nondiabetic (n = 30), FLACS nondiabetic (n = 42), MCS diabetic (n = 40), and FLACS diabetic (n = 40). Aqueous humor inflammatory mediator concentrations were evaluated at MCS onset and after femtosecond laser treatment. The presence of cystoid macular edema, anterior chamber (AC) inflammation, central retinal thickness, macular volume, and retinal microvascular changes (through optical coherence tomography angiography) were evaluated preoperatively and on postoperative day 1, week 1, month 1 (POM1), and month 3 (POM3). Patients with diabetes receiving FLACS had a higher concentration of interleukin (IL)-7, IL-13, and interferon-induced protein-10 than MCS diabetic patients; they also demonstrated higher levels of vascular endothelial growth factor and lower levels of interferon (IFN)-γ, granulocyte colony-stimulating factor, and IFN-α2 compared with MCS nondiabetic patients. Macular volume appeared to be significantly higher in MCS diabetic vs MCS non-diabetic patients at POM1 and between FLACS diabetic vs FLACS nondiabetic patients at POM3. There were no other significant differences between the cohorts for any parameter. FLACS use in patients with diabetes demonstrated some differences in AC cytokine expression compared with non-diabetic FLACS or diabetic patients undergoing MCS; however, there was no increase in clinical inflammatory biomarkers. FLACS seems to be a safe technique to use in patients with diabetes.

Electrochemical performance and photocatalytic activity of LaOCl: Eu3+: its application in tin sensing and dye degradation

ABSTRACT A series of europium doped lanthanum oxychloride samples were prepared through solid state method which were utilized as an electrode material and also as photocatalyst. The compounds form tetragonal phase having P4/nmm space group (No. 129). The sample’s energy band-gap vary in between 4.14 and 4.35 eV. With a carbon paste electrode in a 0.1 M KOH electrolyte, Cyclic Voltammetry (CV) and Electrochemical (AC) Impedance Spectroscopy are performed. Results reveal that the sample synthesized can be an electrode material for sensing tin in alkaline medium in the concentration range of 1 to 5 mM. Also, the samples are considered to be photocatalyst for the decolourization of Rhodamine.B (Rh.B) dye in aqueous medium concentration of 10 ppm using UV light irradiation. LaOCl:Eu3+ sample as catalyst be able to degrade the Rh.B dye to an extent of 90% in 60 mins. These results demonstrated the relevance of synthesized compound for sensor and photocatalytic applications.

Pharmaceutical impacts on aerobic granular sludge morphology and potential implications for abiotic removal

The goal of this study was to investigate abiotic pharmaceutical removal and abiotic pharmaceutical effects on aerobic granular sludge morphology. For 80 days, a pharmaceutical mixture containing approximately 150 μg/L each of diclofenac, erythromycin, and gemfibrozil was fed to an aerobic granular sludge sequencing batch reactor and granule characteristics were compared with those from a control reactor. Aqueous and solid phase pharmaceutical concentrations were monitored and staining was used to assess changes in biofilm structures. Solid phase pharmaceutical concentrations were elevated over the first 12 days of dosing; however, they then dropped, indicative of desorption. The lipid content in pharmaceutical-exposed granules declined by approximately half over the dosing period, though the relative concentrations of other key biofilm components (proteins, alpha-, and beta-polysaccharides) did not change. Batch experiments were conducted to try to find an explanation for the desorption observed, but reduced solid phase pharmaceutical concentrations could not be linked with the presence of common wastewater constituents such as ammonia or phosphate. Sorption of all three compounds was modeled best by the Henry isotherm, indicating that, even at 150 μg/L, granules’ sorption site coverage was incomplete. Altogether, this study demonstrates that simplified batch systems may not accurately represent the complex abiotic processes occurring in flow-through, biotic systems.

Gallium isotope fractionation during precipitation of α-GaOOH from aqueous solution

Gallium (Ga) has two naturally-occurring stable isotopes: 69Ga (60.1%) and 71Ga (39.9%). Their isotopic ratios were employed as a potential proxy to trace the geochemical behavior of Ga and its analogue Al. Ga is also an important component of many semiconductors. When exposed to aqueous solutions, it may be dissolved and then precipitate as Ga-bearing crystals (e.g., GaOOH). Thus, the exploration of Ga isotope fractionation during α-GaOOH precipitation could be helpful for understanding geochemical behaviors of Ga and other metals (including Al and Fe) during oxyhydroxide precipitation. In this study, three series of precipitation experiments with variable initial aqueous Ga concentrations (about 9.2, 2.0, and 1.8 ppm) were carried out to determine Ga isotope fractionation factor during α-GaOOH precipitation at ∼20 °C and neutral pH as a function of time. The experimental results could be modeled using a Rayleigh precipitation process, in which fractionation factors between crystals and solution (Δ71Gasolid-solution) are between −0.28 and − 0.37‰, depending on the initial Ga concentration and type of matrix anion (Cl− vs. NO3−). This isotope fractionation is significantly smaller in magnitude than the values reported for Ga adsorption on goethite (−0.89‰) and calcite (−1.27‰). The isotope fractionation is mainly caused by the increase in GaO bond length from ∼1.84 Å in aqueous GaOH4— to ∼1.991 Å in α-GaOOH solid, with a simultaneous change of Ga coordination number from 4 to 6, although kinetic isotope fractionation may play an important role. Our study provides the first experimental evidence of significant Ga isotope fractionation during kinetic oxyhydroxide precipitation, and suggests that the measurable Ga isotope fractionation occurred at water-solid interface and during precipitations can be potentially used for tracing global geochemical cycling of Ga and its analogue Al and Fe.