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1.
Food Microbiol ; 124: 104609, 2024 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-39244361

RESUMO

Fino Sherry wine undergoes biological aging carried out by a velum of flor yeast within a traditional dynamic system known as "criaderas and solera". The complex microbiota of biofilm-forming Saccharomyces cerevisiae strains play a crucial role in shaping the distinctive organoleptic profile of these types of wines. For this reason, the aim of this study is to analyze the changes produced by different flor yeast strains in the volatilome and the aminogram of different wines from the criaderas and solera system during biological aging in the laboratory, simulating a flor yeast velum condition at different stages of the system. Results suggest that each strain metabolizes wine differently, finding that depending on the wine, some strains are better suited for the process than others. In addition, it is found that the content of biogenic amines in Fino Sherry wines, previously attributed to malolactic bacteria, varies according to the yeast strain metabolizing the wine, suggesting that flor yeast could be used to modify biogenic amines content during biological aging. Results indicate that the use of selected flor yeast starters in biological aging may be of interest to modulate some parameters during Fino Sherry wine aging.


Assuntos
Fermentação , Saccharomyces cerevisiae , Compostos Orgânicos Voláteis , Vinho , Vinho/análise , Vinho/microbiologia , Saccharomyces cerevisiae/metabolismo , Saccharomyces cerevisiae/crescimento & desenvolvimento , Compostos Orgânicos Voláteis/metabolismo , Compostos Orgânicos Voláteis/análise , Compostos de Nitrogênio/metabolismo , Aminas Biogênicas/metabolismo , Aminas Biogênicas/análise
2.
Int J Mol Sci ; 25(15)2024 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-39125751

RESUMO

Bilirubin plays a key role in early diagnosis, prognosis, and prevention of liver diseases. Unconjugated bilirubin (UCB) requires conversion to a water-soluble form through liver glucuronidation, producing monoglucuronide (BMG) or diglucuronide bilirubin (BDG) for bile excretion. This study aimed to assess the roles of bilirubin's molecular species-UCB, BMG, and BDG-in diagnosing and understanding the pathogenesis of liver cirrhosis in patients with acute-on-chronic liver failure (ACLF), compensated liver cirrhosis (LC) patients, and healthy individuals. The study included patients with ACLF and compensated LC of diverse etiologies, along with healthy controls. We collected laboratory and clinical data to determine the severity and assess mortality. We extracted bilirubin from serum samples to measure UCB, BMG, and BDG using liquid chromatography-mass spectrometry (LC-MS). The quantification of bilirubin was performed by monitoring the mass charge (m/z) ratio. Of the 74 patients assessed, 45 had ACLF, 11 had LC, and 18 were healthy individuals. Among ACLF patients, the levels of molecular species of bilirubin were UCB 19.69 µmol/L, BMG 47.71 µmol/L, and BDG 2.120 µmol/L. For compensated cirrhosis patients, the levels were UCB 11.29 µmol/L, BMG 1.49 µmol/L, and BDG 0.055 µmol/L, and in healthy individuals, the levels were UCB 6.42 µmol/L, BMG 0.52 µmol/L, and BDG 0.028 µmol/L. The study revealed marked elevations in the bilirubin species in individuals with ACLF compared to those with compensated cirrhosis and healthy controls, underscoring the progression of liver dysfunction. The correlation of BMG and BDG levels with commonly used inflammatory markers suggests a relationship between bilirubin metabolism and systemic inflammation in ACLF.


Assuntos
Insuficiência Hepática Crônica Agudizada , Bilirrubina , Cirrose Hepática , Humanos , Insuficiência Hepática Crônica Agudizada/metabolismo , Insuficiência Hepática Crônica Agudizada/sangue , Insuficiência Hepática Crônica Agudizada/etiologia , Bilirrubina/metabolismo , Bilirrubina/sangue , Feminino , Masculino , Pessoa de Meia-Idade , Adulto , Cirrose Hepática/metabolismo , Cirrose Hepática/sangue , Cirrose Hepática/complicações , Biomarcadores/sangue , Idoso , Estudos de Casos e Controles , Prognóstico , Cromatografia Líquida
3.
Nat Mater ; 21(11): 1290-1297, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-36280703

RESUMO

Stable catalysts are essential to address energy and environmental challenges, especially for applications in harsh environments (for example, high temperature, oxidizing atmosphere and steam). In such conditions, supported metal catalysts deactivate due to sintering-a process where initially small nanoparticles grow into larger ones with reduced active surface area-but strategies to stabilize them can lead to decreased performance. Here we report stable catalysts prepared through the encapsulation of platinum nanoparticles inside an alumina framework, which was formed by depositing an alumina precursor within a separately prepared porous organic framework impregnated with platinum nanoparticles. These catalysts do not sinter at 800 °C in the presence of oxygen and steam, conditions in which conventional catalysts sinter to a large extent, while showing similar reaction rates. Extending this approach to Pd-Pt bimetallic catalysts led to the small particle size being maintained at temperatures as high as 1,100 °C in air and 10% steam. This strategy can be broadly applied to other metal and metal oxides for applications where sintering is a major cause of material deactivation.


Assuntos
Nanopartículas Metálicas , Platina , Temperatura , Vapor , Óxido de Alumínio
4.
Environ Sci Technol ; 2023 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-36633549

RESUMO

Increased periods of bottom water anoxia in deep temperate lakes due to decreasing frequency and depth of water column mixing in a warming climate may result in the reductive dissolution of iron minerals and increased flux of nutrients from the sediment into the water column. Here, we assessed the sediment properties and reactivities under depleted oxygen concentrations of Lake Tahoe, a deep ultraoligotrophic lake in the Sierra Nevada mountain range. Using whole-core incubation experiments, we found that a decrease in dissolved oxygen concentration in the top 2 cm of the sediment resulted in an extension of the microbial iron reduction zone from below 4.5 to below 1.5 cm depth. Concentrations of reactive iron generally decreased with sediment depth, and microbial iron reduction seemingly ceased as concentrations of Fe(II) approximated concentrations of reactive iron. These findings suggest that microorganisms preferentially utilized reactive iron and/or iron minerals became less reactive due to mineral transformation and surface passivation. The estimated release of iron mineral-associated phosphorus is not expected to change Lake Tahoe's trophic state but will likely contribute to increased phytoplankton productivity if mixed into surface waters.

5.
Food Microbiol ; 116: 104366, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37689427

RESUMO

Sherry wines are film wines produced in the Jerez-Xérès-Sherry and Montilla-Moriles regions in southern Spain which require an aging process under flor biofilms, known as "biological aging". The presence of mites in Sherry wine wineries has been reported and associated with improved wine volatile properties. This work analyzes the microbial diversity in flor biofilms and mites in Sherry wine wineries using Matrix-Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) and ITS/gene amplification. Two mite species, Carpoglyphus lactis and Tyrophagus putrescentiae, were spotted in the sampled winery and 32 microorganism species were identified in their exoskeleton or surrounding biofilms. To our knowledge, 26 of these species were never described before in sherry wine environments. We hypothesized that mites feed on the flor biofilms as well as another type of biofilm located in barrel cracks, known by winemakers as "natas" (cream in English). These non-studied biofilms showed the highest microbiome diversity among all samples (followed by C. lactis spotted nearby) thus, representing a niche of microorganisms with potential biotechnological interest. Besides mites, Drosophila flies were spotted in the sampling areas. The role of flies and mites as vectors that transport microorganisms among different niches (i.e., flor biofilms and natas) is discussed.


Assuntos
Ácaros , Vinho , Animais , Biofilmes , Biotecnologia , Alimentos
6.
World J Microbiol Biotechnol ; 39(10): 271, 2023 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-37541980

RESUMO

Sherry wine is a pale-yellowish dry wine produced in Southern-Spain which features are mainly due to biological aging when the metabolism of biofilm-forming yeasts (flor yeasts) consumes ethanol (and other non-fermentable carbon sources) from a previous alcoholic fermentation, and produces volatile compounds such as acetaldehyde. To start aging and maintain the wine stability, a high alcohol content is required, which is achieved by the previous fermentation or by adding ethanol (fortification). Here, an alternative method is proposed which aims to produce a more economic, distinctive Sherry wine without fortification. For this, a flor yeast has been pre-acclimatized to glycerol consumption against ethanol, and later confined in a fungal-based immobilization system known as "microbial biocapsules", to facilitate its inoculum. Once aged, the wines produced using biocapsules and free yeasts (the conventional method) exhibited chemical differences in terms of acidity and volatile concentrations. These differences were evaluated positively by a sensory panel. Pre-acclimatization of flor yeasts to glycerol consumption was not successful but when cells were immobilized in fungal pellets, ethanol consumption was lower. We believe that immobilization of flor yeasts in microbial biocapsules is an economic technique that can be used to produce high quality differentiated Sherry wines.


Assuntos
Saccharomyces cerevisiae , Vinho , Saccharomyces cerevisiae/metabolismo , Vinho/microbiologia , Glicerol/metabolismo , Acetaldeído/análise , Acetaldeído/metabolismo , Etanol/metabolismo , Fermentação
7.
Environ Sci Technol ; 56(23): 16822-16830, 2022 12 06.
Artigo em Inglês | MEDLINE | ID: mdl-36351078

RESUMO

Arsenic (As)-bearing water treatment residuals (WTRs) from household sand filters are usually disposed on top of floodplain soils and may act as a secondary As contamination source. We hypothesized that open disposal of these filter-sands to soils will facilitate As release under reducing conditions. To quantify the mobilization risk of As, we incubated the filter-sand, the soil, and a mixture of the filter-sand and soil in anoxic artificial rainwater and followed the dynamics of reactive Fe and As in aqueous, solid, and colloidal phases. Microbially mediated Fe(III)/As(V) reduction led to the mobilization of 0.1-4% of the total As into solution with the highest As released from the mixture microcosms equaling 210 µg/L. Due to the filter-sand and soil interaction, Mössbauer and X-ray absorption spectroscopies indicated that up to 10% Fe(III) and 32% As(V) were reduced in the mixture microcosm. Additionally, the mass concentrations of colloidal Fe and As analyzed by single-particle ICP-MS decreased by 77-100% compared to the onset of reducing conditions with the highest decrease observed in the mixture setups (>95%). Overall, our study suggests that (i) soil provides bioavailable components (e.g., organic matter) that promote As mobilization via microbial reduction of As-bearing Fe(III) (oxyhydr)oxides and (ii) As mobilization as colloids is important especially right after the onset of reducing conditions but its importance decreases over time.


Assuntos
Arsênio , Purificação da Água , Arsênio/metabolismo , Compostos Férricos , Oxirredução , Solo
8.
Environ Res ; 204(Pt D): 112355, 2022 03.
Artigo em Inglês | MEDLINE | ID: mdl-34774504

RESUMO

Studies have established associations between environmental and occupational manganese (Mn) exposure and executive and motor function deficits in children, adolescents, and adults. These health risks from elevated Mn exposure underscore the need for effective exposure biomarkers to improve exposure classification and help detect/diagnose Mn-related impairments. Here, neonate rats were orally exposed to 0, 25, or 50 mg Mn/kg/day during early life (PND 1-21) or lifelong through âˆ¼ PND 500 to determine the relationship between oral Mn exposure and blood, brain, and bone Mn levels over the lifespan, whether Mn accumulates in bone, and whether elevated bone Mn altered the local atomic and mineral structure of bone, or its biomechanical properties. Additionally, we assessed levels of bone Mn compared to bone lead (Pb) in aged humans (age 41-91) living in regions impacted by historic industrial ferromanganese activity. The animal studies show that blood, brain, and bone Mn levels naturally decrease across the lifespan without elevated Mn exposure. With elevated exposure, bone Mn levels were strongly associated with blood Mn levels, bone Mn was more sensitive to elevated exposures than blood or brain Mn, and Mn did not accumulate with lifelong elevated exposure. Elevated early life Mn exposure caused some changes in bone mineral properties, including altered local atomic structure of hydroxyapatite, along with some biomechanical changes in bone stiffness in weanlings or young adult animals. In aged humans, blood Mn ranged from 5.4 to 23.5 ng/mL; bone Mn was universally low, and decreased with age, but did not vary based on sex or female parity history. Unlike Pb, bone Mn showed no evidence of accumulation over the lifespan, and may not be a biomarker of cumulative long-term exposure. Thus, bone may be a useful biomarker of recent ongoing Mn exposure in humans, and may be a relatively minor target of elevated exposure.


Assuntos
Manganês , Exposição Ocupacional , Animais , Biomarcadores , Encéfalo , Feminino , Longevidade , Manganês/análise , Ratos
9.
Sensors (Basel) ; 22(19)2022 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-36236782

RESUMO

Drowning is a major health issue worldwide. The World Health Organization's global report on drowning states that the highest rates of drowning deaths occur among children aged 1-4 years, followed by children aged 5-9 years. Young children can drown silently in as little as 25 s, even in the shallow end or in a baby pool. The report also identifies that the main risk factor for children drowning is the lack of or inadequate supervision. Therefore, in this paper, we propose a novel 5G and beyond child drowning prevention system based on deep learning that detects and classifies distractions of inattentive parents or caregivers and alerts them to focus on active child supervision in swimming pools. In this proposal, we have generated our own dataset, which consists of images of parents/caregivers watching the children or being distracted. The proposed model can successfully perform a seven-class classification with very high accuracies (98%, 94%, and 90% for each model, respectively). ResNet-50, compared with the other models, performs better classifications for most classes.


Assuntos
Aprendizado Profundo , Afogamento , Piscinas , Cuidadores , Criança , Pré-Escolar , Afogamento/prevenção & controle , Humanos , Lactente , Pais , Natação
10.
Saudi Pharm J ; 30(7): 906-917, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35903521

RESUMO

Midazolam (MDZ) is a short-acting benzodiazepine that is widely used to induce and maintain general anesthesia during diagnostic and therapeutic procedures in pediatric patients due to its sedative properties. The aim of this study was to perform a systematic review without a meta-analysis to identify scientific articles and clinical assays concerning MDZ-induced sedation for a pediatric surgery approach. One hundred and twenty-eight results were obtained. After critical reading, 37 articles were eliminated, yielding 91 publications. Additional items were identified, and the final review was performed with a total of 106 publications. In conclusion, to use MDZ accurately, individual patient characteristics, the base disease state, comorbidities, the treatment burden and other drugs with possible pharmacological interactions or adverse reactions must be considered to avoid direct alterations in the pharmacokinetics and pharmacodynamics of MDZ to obtain the desired effects and avoid overdosing in the pediatric population.

11.
Environ Sci Technol ; 55(23): 16246-16256, 2021 12 07.
Artigo em Inglês | MEDLINE | ID: mdl-34797046

RESUMO

We investigated interfacial reactions of U(VI) in the presence of Suwannee River natural organic matter (NOM) at acidic and neutral pH. Laboratory batch experiments show that the adsorption and precipitation of U(VI) in the presence of NOM occur at pH 2 and pH 4, while the aqueous complexation of U by dissolved organic matter is favored at pH 7, preventing its precipitation. Spectroscopic analyses indicate that U(VI) is mainly adsorbed to the particulate organic matter at pH 4. However, U(VI)-bearing ultrafine to nanocrystalline solids were identified at pH 4 by electron microscopy. This study shows the promotion of U(VI) precipitation by NOM at low pH which may be relevant to the formation of mineralized deposits, radioactive waste repositories, wetlands, and other U- and organic-rich environmental systems.


Assuntos
Resíduos Radioativos , Urânio , Adsorção , Matéria Orgânica Dissolvida , Concentração de Íons de Hidrogênio , Urânio/análise
12.
BMC Pulm Med ; 21(1): 265, 2021 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-34399724

RESUMO

PURPOSE: The objective of the present study is to describe the clinical, diagnostic, radiological and therapeutic aspects of osteoarticular tuberculosis (OATB) in patients in a tertiary pediatric hospital, to know if the diagnosis of OATB in pediatrics is a challenge due to its insidious clinical presentation. METHODS: A retrospective, descriptive study of the cases of Tuberculosis (TB) in children was carried out. A total of 159 cases met the condition for the analysis. RESULTS: The most frequent TB modality was extrapulmonary in 85%. Out of this, only 29% was OATB. The mean age was 4.9 years (range 8 months-16 years). Eighty-six per cent of cases received Bacille Calmette-Guérin (BCG) vaccination at birth. Median time of symptoms prior to diagnosis was 8 months. Microbiological confirmation was achieved only in five cases, with a high sensitivity to the antimicrobial treatment. Mycobacterium bovis BCG strain Tokio 172 was confirmed in three cases. Mortality rate was 0% during the time of study CONCLUSION: Our study describes the epidemiological characteristics of OATB cases in Mexican children. This data revealed a high prevalence of bone and joint TB infection. Pediatric OATB should be considered in cases with lytic bone lesions, fever and local pain. In countries with BCG immunization program, M. bovis should not be forgotten as an etiological agent. The low detection rate with one technique approach highlights the urgent need for more sensitive test to diagnose OATB in children.


Assuntos
Tuberculose Osteoarticular/diagnóstico , Tuberculose Osteoarticular/terapia , Adolescente , Criança , Pré-Escolar , Feminino , Humanos , Lactente , Masculino , Encaminhamento e Consulta , Estudos Retrospectivos , Centros de Atenção Terciária , Fatores de Tempo
13.
J Clin Pharm Ther ; 46(3): 633-639, 2021 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-33638195

RESUMO

WHAT IS KNOWN AND OBJECTIVE: Midazolam is a drug that is metabolized by cytochrome P450 (CYP450) enzymes, particularly CYP3A4 and CYP3A5. The presence of single-nucleotide polymorphisms (SNPs) in the genes encoding these enzymes, such as CYP3A4*1B which is associated with low enzyme expression and activity and CYP3A5*3, has been associated with decrease in enzymatic activity and reduced drug clearance, with potential effects on drug levels and/or toxicity. The present study was conducted to determine the frequencies of the allelic variants of the CYP3A4 (rs2740574) and CYP3A5 (rs776746) genes and their effects on the plasma levels and clearance of intravenous midazolam in critically ill Mexican paediatric patients. METHODS: Seventy-two DNA samples were genotyped by real-time PCR with TaqMan probes. Plasma midazolam levels were determined at 3 and 24 h post infusion by high-performance liquid chromatography. RESULTS AND DISCUSSION: The allelic variant rs776746 (CYP3A5*3) was associated with high midazolam plasma levels; the median concentration in patients with the normal genotype (CC) <0.01 ng/ml (Q25 0.01-Q75 196.09), whereas patients with the allelic variant (TT+TC) had a median midazolam concentration of 320.3 ng/ml (Q25 37.51-Q75 529.51), p = 0.001. The median pharmacokinetic clearance rates were 0.10 L/kg/h (Q25 0.01-Q75 0.34) in patients with the allelic variant (TT+TC) and 0.03 L/kg/h (Q25 0.002-Q75 0.13) in patients with the normal genotype (CC), p = 0.042. WHAT IS NEW AND CONCLUSION: This is the first study that reports the frequency of the rs776746 polymorphism in critically ill paediatric patients, which is relevant, since carriers of the *1 allele synthesizing a functional enzyme may need higher doses to achieve adequate sedation. Our results show that compared with carriers of the normal allele, patients with the CYP3A5*3 allelic variant (rs776746) had increased plasma midazolam levels at 3 h after infusion discontinuation (320.3 ng/ml) and greater clearance (0.10 L/kg/h) of the drug.


Assuntos
Citocromo P-450 CYP3A/genética , Hipnóticos e Sedativos/farmacocinética , Midazolam/farmacocinética , Adolescente , Criança , Pré-Escolar , Estado Terminal , Feminino , Genótipo , Meia-Vida , Humanos , Lactente , Masculino , Taxa de Depuração Metabólica , México , Fenótipo , Polimorfismo de Nucleotídeo Único
14.
J Am Chem Soc ; 142(51): 21243-21248, 2020 12 23.
Artigo em Inglês | MEDLINE | ID: mdl-33315385

RESUMO

Electrically conductive metal-organic frameworks (cMOFs) have become a topic of intense interest in recent years because of their great potential in electrochemical energy storage, electrocatalysis, and sensing applications. Most of the cMOFs reported hitherto are 2D structures, and 3D cMOFs remain rare. Herein we report FeTHQ, a 3D cMOF synthesized from tetrahydroxy-1,4-quinone (THQ) and iron(II) sulfate salt. FeTHQ exhibited a conductivity of 3.3 ± 0.55 mS cm-1 at 300 K, which is high for 3D cMOFs. The conductivity of FeTHQ is valence-dependent. A higher conductivity was measured with the as-prepared FeTHQ than with the air-oxidized and sodium naphthalenide-reduced samples.


Assuntos
Condutividade Elétrica , Estruturas Metalorgânicas/química , Quinonas/química , Eletroquímica , Ferro/química , Modelos Moleculares , Oxirredução
15.
Biomarkers ; 25(4): 331-340, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32279544

RESUMO

Context: Ifosfamide (IFA) is an effective antineoplastic for solid tumours in children, although it is associated with high levels of systemic toxicity and causes death in some cases. Objective: The aim of this study was to determine whether the presence of certain allelic variants of genes CYP2B6, CYP2C9, CYP3A4 and CYP3A5 increases the risk of toxicity in children with solid tumours treated with ifosfamide.Materials and methods: A total of 131 DNA samples were genotyped by real-time polymerase chain reaction (RT-PCR) using TaqMan probes. Toxicity was assessed using WHO criteria, and survival analysis was performed using Kaplan-Meier curves.Results: The rs3745274 allelic variant in CYP2B6 was associated with haematological toxicity, affecting neutrophils; CYP3A4 variant rs2740574 was also associated with toxicity, affecting both leukocytes and neutrophils. Additionally, the CYP3A5 gene variant rs776746 was found to affect haemoglobin.Conclusions: Our results show that allelic variants rs3745274 (CYP2B6), rs2740574 (CYP34) and rs776746 (CYP3A5) increase the risk for high haematological toxicity.Clinical trial registration: 068/2013.


Assuntos
Citocromo P-450 CYP2B6/genética , Citocromo P-450 CYP2C9/genética , Citocromo P-450 CYP3A/genética , Neoplasias/tratamento farmacológico , Adolescente , Alelos , Criança , Pré-Escolar , Intervalo Livre de Doença , Feminino , Frequência do Gene , Genótipo , Humanos , Ifosfamida/administração & dosagem , Ifosfamida/efeitos adversos , Lactente , Estimativa de Kaplan-Meier , Masculino , Neoplasias/genética , Neoplasias/patologia
16.
Environ Sci Technol ; 54(11): 6682-6692, 2020 06 02.
Artigo em Inglês | MEDLINE | ID: mdl-32347724

RESUMO

Reduced sulfur (S) has a contrasting role in the fate of arsenic (As) in peatlands. Sulfur bridges provide efficient binding of As to organic carbon (C), but the formation of aqueous As-S species, so-called thioarsenates, leads to a low to no sorption tendency to organic C functional groups. Here, we studied how pH changes the role of reduced S in desorption and retention of presorbed As in model peat. Control desorption experiments without S addition revealed that As was mobilized, predominantly as arsenite, in all treatments with relative mobilization increasing with pH (4.5 < 7.0 < 8.5). Addition of sulfide or polysulfide caused substantial As retention at acidic conditions but significantly enhanced As desorption compared to controls at neutral to alkaline pH. Thioarsenates dominated As speciation at pH 7.0 and 8.5 (maximum, 79%) and remained in solution without (re)sorption to peat. Predominance of arsenite in control experiments and no evidence of surface-bound thioarsenates at pH 7.0 suggest mobilization to proceed via arsenite desorption, reaction with dissolved or surface-bound reduced S, and formation of thioarsenates. Our results suggest that natural or management-related increases in pH or increases in reduced S in near-neutral pH environments can turn organic matter from an As sink into a source.


Assuntos
Arsênio , Arseniatos , Concentração de Íons de Hidrogênio , Solo , Enxofre
17.
Environ Sci Technol ; 54(15): 9445-9453, 2020 08 04.
Artigo em Inglês | MEDLINE | ID: mdl-32633952

RESUMO

Natural organic matter (NOM) is known to affect the microbial reduction and transformation of ferrihydrite, but its implication toward cadmium (Cd) associated with ferrihydrite is not well-known. Here, we investigated how Cd is redistributed when ferrihydrite undergoes microbial reduction in the presence of NOM. Incubation with Geobacter sulfurreducens showed that both the rate and the extent of reduction of Cd-loaded ferrihydrite were enhanced by increasing concentrations of NOM (i.e., C/Fe ratio). Without NOM, only 3-4% of Fe(III) was reduced, but around 61% of preadsorbed Cd was released into solution due to ferrihydrite transformation to lepidocrocite. At high C/Fe ratio (1.6), more than 35% of Fe(III) was reduced, as NOM can facilitate bioreduction by working as an electron shuttle and decreased aggregate size, but only a negligible amount of Cd was released into solution, thus decreasing Cd toxicity and prolonging microbial Fe(III) reduction. No ferrihydrite transformation was observed at high C/Fe ratios using Mössbauer spectroscopy and X-ray diffraction, and X-ray absorption spectroscopy indicated the proportion of Cd-OM bond increased after microbial reduction. This study shows that the presence of NOM leads to less mobilization of Cd under reducing condition possibly by inhibiting ferrihydrite transformation and recapturing Cd through Cd-OM bond.


Assuntos
Cádmio , Compostos Férricos , Geobacter , Ferro , Minerais , Oxirredução
18.
Environ Sci Technol ; 54(7): 3979-3987, 2020 04 07.
Artigo em Inglês | MEDLINE | ID: mdl-32176846

RESUMO

Natural or anthropogenic processes can increase the concentration of uranium (U) and arsenic (As) above the maximum contaminant levels in water sources. Bicarbonate and calcium (Ca) can have major impacts on U speciation and can affect the reactivity between U and As. We therefore investigated the reactivity of aqueous U and As mixtures with bicarbonate and Ca for acidic and neutral pH conditions. In experiments performed with 1 mM U and As mixtures, 10 mM Ca, and without added bicarbonate (pCO2 = 3.5), aqueous U decreased to <0.25 mM at pH 3 and 7. Aqueous As decreased the most at pH 3 (∼0.125 mM). Experiments initiated with 0.005 mM As and U showed similar trends. X-ray spectroscopy (i.e., XAS and EDX) and diffraction indicated that U-As-Ca- and U-Ca-bearing solids resemble uranospinite [Ca(UO2)2(AsO4)2·10H2O] and becquerelite [Ca(UO2)6O4(OH)6·8(H2O)]. These findings suggest that U-As-Ca-bearing solids formed in mixed solutions are stable at pH 3. However, the dissolution of U-As-Ca and U-Ca-bearing solids at pH 7 was observed in reactors containing 10 mM bicarbonate and Ca, suggesting a kinetic reaction of aqueous uranyl-calcium-carbonate complexation. Our study provides new insights regarding U and As mobilization for risk assessment and remediation strategies.


Assuntos
Arsênio , Urânio , Bicarbonatos , Cálcio , Concentração de Íons de Hidrogênio
19.
Environ Sci Technol ; 54(6): 3237-3244, 2020 03 17.
Artigo em Inglês | MEDLINE | ID: mdl-32069033

RESUMO

Groundwater contamination by As from natural and anthropogenic sources is a worldwide concern. Redox heterogeneities over space and time are common and can influence the molecular-level speciation of As, and thus, As release/retention but are largely unexplored. Here, we present results from a dual-domain column experiment, with natural organic-rich, fine-grained, and sulfidic sediments embedded as lenses (referred to as "reducing lenses") within natural aquifer sand. We show that redox interfaces in sulfur-rich, alkaline aquifers may release concerning levels of As, even when sediment As concentration is low (<2 mg/kg), due to the formation of mobile thioarsenates at aqueous sulfide/Fe molar ratios <1. In our experiments, this behavior occurred in the aquifer sand between reducing lenses and was attributed to the spreading of sulfidic conditions and subsequent Fe reductive dissolution. In contrast, inside reducing lenses (and some locations in the aquifer) the aqueous sulfide/Fe molar ratios exceeded 1 and aqueous sulfide/As molar ratios exceeded 100, which partitioned As(III)-S to the solid phase (associated with organics or as realgar (As4S4)). These results highlight the importance of thioarsenates in natural sediments and indicate that redox interfaces and sediment heterogeneities could locally degrade groundwater quality, even in aquifers with unconcerning solid-phase As concentrations.


Assuntos
Arsênio , Água Subterrânea , Poluentes Químicos da Água , Sedimentos Geológicos , Oxirredução
20.
J Am Chem Soc ; 141(49): 19404-19414, 2019 12 11.
Artigo em Inglês | MEDLINE | ID: mdl-31794205

RESUMO

A major chemical challenge facing implementation of 225Ac in targeted alpha therapy-an emerging technology that has potential for treatment of disease-is identifying an 225Ac chelator that is compatible with in vivo applications. It is unclear how to tailor a chelator for Ac binding because Ac coordination chemistry is poorly defined. Most Ac chemistry is inferred from radiochemical experiments carried out on microscopic scales. Of the few Ac compounds that have been characterized spectroscopically, success has only been reported for simple inorganic ligands. Toward advancing understanding in Ac chelation chemistry, we have developed a method for characterizing Ac complexes that contain highly complex chelating agents using small quantities (µg) of 227Ac. We successfully characterized the chelation of Ac3+ by DOTP8- using EXAFS, NMR, and DFT techniques. To develop confidence and credibility in the Ac results, comparisons with +3 cations (Am, Cm, and La) that could be handled on the mg scale were carried out. We discovered that all M3+ cations (M = Ac, Am, Cm, La) were completely encapsulated within the binding pocket of the DOTP8- macrocycle. The computational results highlighted the stability of the M(DOTP)5- complexes.


Assuntos
Actínio/química , Amerício/química , Quelantes/química , Complexos de Coordenação/síntese química , Cúrio/química , Lantânio/química , Compostos Organofosforados/química , Compostos Radiofarmacêuticos/síntese química , Complexos de Coordenação/química , Ligantes , Estrutura Molecular , Compostos Radiofarmacêuticos/química
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