RESUMEN

BACKGROUND: Preclinical Alzheimer's disease is increasingly studied in clinical trials. Although safety signals are routinely monitored in clinical trial populations with Alzheimer's disease, it can be challenging to identify new safety signals against background rates of age-related medical comorbidities. OBJECTIVES: To report detailed safety data from a cognitively unimpaired older population with evidence of elevated cerebral amyloid levels on amyloid positron emission tomography in the placebo arm of a Phase 3 clinical trial. DESIGN: Phase 3, 4.5-year, multicenter, placebo-controlled trial. SETTING: Placebo data from the Anti-Amyloid Treatment in Asymptomatic Alzheimer's Disease (A4) study. PARTICIPANTS: Enrolled participants were aged 65-85 years with a global Clinical Dementia Rating score of 0, a Mini-Mental State Examination score of 25-30, a Wechsler Memory Scale Logical Memory IIa (delayed recall) score of 6-18, and elevated brain amyloid levels on 18F-florbetapir positron emission tomography. MEASUREMENTS: Study participants who received placebo were followed up with post-baseline safety measures. Assessments included review of concomitant medication and adverse events, the Columbia Suicide Severity Rating Scale, electrocardiograms, and neuroimaging (brain magnetic resonance imaging). RESULTS: In total, 591 study participants (mean age [standard deviation] 71.9 [5.0] years) were assigned to and received placebo in the A4 study, and were followed up to 240 weeks. Participants were primarily White (93.9%) and from the United States (86.8%); 60.4% were women. The most common serious adverse events (incidence rate per 100 person-years) were pneumonia (incidence rate=0.4; 95% confidence interval=0.2-0.7) and atrial fibrillation (incidence rate=0.4; 95% confidence interval=0.2-0.7). The most common treatment-emergent adverse events were upper respiratory tract infection (incidence rate=10.9; 95% confidence interval=9.4-12.5), fall (incidence rate=7.7; 95% confidence interval=6.6-9.0), and nasopharyngitis (incidence rate=5.8; 95% confidence interval=4.8-6.9). The most common ischemia-related findings on magnetic resonance imaging were subcortical infarction (incidence rate=1.4; 95% confidence interval=1.0-2.0) and acute ischemia (incidence rate=0.6; 95% confidence interval=0.3-1.0). Emergent amyloid-related imaging abnormalities with hemosiderin deposition occurred in 32.8% of participants who received placebo; the primary factor associated with these events during the post-baseline period was the number of microhemorrhages at baseline (odds ratio=349.9; 95% confidence interval=247.6-494.4; adjusted p<0.001). CONCLUSION: Safety findings in the placebo-treated group from the A4 study provide a robust characterization of expected safety in a clinical trial population with preclinical Alzheimer's disease. These results may provide context in planning future studies and safety evaluations during ongoing blinded studies in preclinical Alzheimer's disease.

Asunto(s)

Enfermedad de Alzheimer , Compuestos de Anilina , Tomografía de Emisión de Positrones , Humanos , Anciano , Femenino , Masculino , Anciano de 80 o más Años , Compuestos de Anilina/uso terapéutico , Compuestos de Anilina/efectos adversos , Enfermedad de Alzheimer/tratamiento farmacológico , Enfermedad de Alzheimer/diagnóstico por imagen , Encéfalo/diagnóstico por imagen , Encéfalo/metabolismo , Glicoles de Etileno , Método Doble Ciego , Péptidos beta-Amiloides/metabolismo

RESUMEN

Arsenic (As)-bearing Fe(III) precipitate groundwater treatment sludge has traditionally been viewed by the water sector as a disposal issue rather than a resource opportunity, partly due to assumptions of the low value of As. However, As has now been classified as a Critical Raw Material (CRM) in many regions, providing new incentives to recover As and other useful components of the sludge, such as phosphate (P) and the reactive hydrous ferric oxide (HFO) sorbent. Here, we investigate alkali extraction to separate As from a variety of field and synthetic As-bearing HFO sludges, which is a critical first step to enable sludge upcycling. We found that As extraction was most effective using NaOH, with the As extraction efficiency increasing up to >99% with increasing NaOH concentrations (0.01, 0.1, and 1 M). Extraction with Na2CO3 and Ca(OH)2 was ineffective (<5%). Extraction time (hour, day, week) played a secondary role in As release but tended to be important at lower NaOH concentrations. Little difference in As extraction efficiency was observed for several key variables, including sludge aging time (50 days) and cosorbed oxyanions (e.g., Si, P). However, the presence of ∼10 mass% calcite decreased As release from field and synthetic sludges considerably (<70% As extracted). Concomitant with As release, alkali extraction promoted crystallization of poorly ordered HFO and decreased particle specific surface area, with structural modifications increasing with NaOH concentration and extraction time. Taken together, these results provide essential information to inform and optimize the design of resource recovery methods for As-bearing treatment sludge.

Asunto(s)

Álcalis , Arsénico , Agua Subterránea , Aguas del Alcantarillado , Aguas del Alcantarillado/química , Agua Subterránea/química , Álcalis/química , Contaminantes Químicos del Agua/química , Purificación del Agua/métodos , Compuestos Férricos/química

RESUMEN

Long-term consumption of groundwater containing elevated levels of arsenic (As) can have severe health consequences, including cancer. To effectively remove As, conventional treatment technologies require expensive chemical oxidants to oxidise neutral arsenite (As(III)) in groundwater to negatively charged arsenate (As(V)), which is more easily removed. Rapid sand filter beds used in conventional aeration-filtration to treat anaerobic groundwater can naturally oxidise As(III) through biological processes but require an additional step to remove the generated As(V), adding complexity and cost. This study introduces a novel approach where As(V), produced through biological As(III) oxidation in a sand filter, is effectively removed within the same filter by embedding and operating an iron electrocoagulation (FeEC) system inside the filter. Operating FeEC within the biological filter achieved higher As(III) removal (81 %) compared to operating FeEC in the filter supernatant (67 %). This performance was similar to an analogous embedded-FeEC system treating As(V)-contaminated water (85 %), confirming the benefits of incorporating FeEC in a biological bed for comparable As(III) and As(V) removal. However, operating FeEC in the sand matrix consumed more energy (14 Wh/m3) compared to FeEC operated in a water matrix (7 Wh/m3). The efficiency of As removal increased and energy requirements decreased in such embedded-FeEC systems by deep-bed infiltration of Fe(III)-precipitates, which can be controlled by adjusting flow rate and pH. This study is one of the first to demonstrate the feasibility of embedding FeEC systems in sand filters for groundwater arsenic removal. Such systems capitalise on biological As(III) oxidation in aeration-filtration, effectively eliminating As(V) within the same setup without the need for chemicals or major modifications.

Asunto(s)

Arsénico , Agua Potable , Agua Subterránea , Contaminantes Químicos del Agua , Purificación del Agua , Compuestos Férricos , Arsénico/análisis , Contaminantes Químicos del Agua/análisis , Agua Potable/análisis , Electrocoagulación

RESUMEN

A growing body of work examines the direct and indirect effects of climate change on ecosystems, typically by using manipulative experiments at a single site or performing meta-analyses across many independent experiments. However, results from single-site studies tend to have limited generality. Although meta-analytic approaches can help overcome this by exploring trends across sites, the inherent limitations in combining disparate datasets from independent approaches remain a major challenge. In this paper, we present a globally distributed experimental network that can be used to disentangle the direct and indirect effects of climate change. We discuss how natural gradients, experimental approaches, and statistical techniques can be combined to best inform predictions about responses to climate change, and we present a globally distributed experiment that utilizes natural environmental gradients to better understand long-term community and ecosystem responses to environmental change. The warming and (species) removal in mountains (WaRM) network employs experimental warming and plant species removals at high- and low-elevation sites in a factorial design to examine the combined and relative effects of climatic warming and the loss of dominant species on community structure and ecosystem function, both above- and belowground. The experimental design of the network allows for increasingly common statistical approaches to further elucidate the direct and indirect effects of warming. We argue that combining ecological observations and experiments along gradients is a powerful approach to make stronger predictions of how ecosystems will function in a warming world as species are lost, or gained, in local communities.

RESUMEN

Groundwater contaminated with arsenic (As) must be treated prior to drinking, as human exposure to As at toxic levels can cause various diseases including cancer. Conventional aeration-filtration applied to anaerobic arsenite (As(III)) contaminated groundwater can remove As(III) by co-oxidizing native iron (Fe(II)) and As(III) with oxygen (O2). However, the As(III) removal efficiency of conventional aeration can be low, in part, because of incomplete As(III) oxidation to readily-sorbed arsenate (As(V)). In this work, we investigated a new approach to enhance As(III) co-removal with native Fe(II) by the anaerobic addition of hydrogen peroxide (H2O2) prior to aeration. Experiments were performed to co-oxidize Fe(II) and As(III) with H2O2 (anaerobically), O2 (aerobically), and by sequentially adding of H2O2 and O2. Aqueous As(III) and As(V) measurements after the reaction were coupled with solid-phase speciation by Fe and As K-edge X-ray absorption spectroscopy (XAS). We found that complete anaerobic oxidation of 100 µM Fe(II) with 100 µM H2O2 resulted in co-removal of 95% of 7 µM As(III) compared to 44% with 8.0-9.0 mg/L dissolved O2. Furthermore, we found that with 100 µM Fe(II), the initial Fe(II):H2O2 ratio was a critical parameter to remove 7 µM As(III) to below the 10 µg/L (0.13 µM) WHO guideline, where ratios of 1:4 (mol:mol) Fe(II):H2O2 led to As(III) removal matching that of 7 µM As(V). The improved As(III) removal with H2O2 was found to occur partly because of the well-established enhanced efficiency of As(III) oxidation in Fe(II)+H2O2 systems relatively to Fe(II)+O2 systems. However, the XAS results unambiguously demonstrated that a large factor in the improved As(III) removal was also due to a systematic decrease in crystallinity, and thus increase in specific surface area, of the generated Fe(III) (oxyhydr)oxides from lepidocrocite in the Fe(II)+O2 system to poorly-ordered Fe(III) precipitates in the Fe(II)+H2O2 system. The combined roles of H2O2 (enhanced As(III) oxidation and structural modification) can be easily overlooked when only aqueous species are measured, but this dual impact must be considered for accurate predictions of As removal in groundwater treatment.

Asunto(s)

Arsénico , Arsenitos , Agua Subterránea , Contaminantes Químicos del Agua , Arseniatos , Arsénico/química , Arsenitos/química , Compuestos Férricos/química , Compuestos Ferrosos/química , Agua Subterránea/química , Humanos , Peróxido de Hidrógeno/química , Hierro/química , Oxidación-Reducción , Óxidos/química , Oxígeno , Contaminantes Químicos del Agua/química

RESUMEN

Plant diversity has a positive influence on the number of ecosystem functions maintained simultaneously by a community, or multifunctionality. While the presence of multiple trophic levels beyond plants, or trophic complexity, affects individual functions, the effect of trophic complexity on the diversity-multifunctionality relationship is less well known. To address this issue, we tested whether the independent or simultaneous manipulation of both plant diversity and trophic complexity impacted multifunctionality using a mesocosm experiment from Cedar Creek, Minnesota, USA. Our analyses revealed that neither plant diversity nor trophic complexity had significant effects on single functions, but trophic complexity altered the diversity-multifunctionality relationship in two key ways: It lowered the maximum strength of the diversity-multifunctionality effect, and it shifted the relationship between increasing diversity and multifunctionality from positive to negative at lower function thresholds. Our findings highlight the importance to account for interactions with higher trophic levels, as they can alter the biodiversity effect on multifunctionality.

RESUMEN

Manganese oxide-coated sand can oxidize electron-rich organic contaminants, but after extended exposure to contaminated water its reactivity decreases. To assess the potential for regenerating geomedia, we measured the ability of passivated manganese-oxide coated sand to oxidize bisphenol A after treatment with oxidants, acid, or methanol. Among the regenerants studied, KMnO4, HOCl, HOBr, and pH 2 or 3 HCl solutions raised the average oxidation state of the Mn, but only HOCl and HOBr restored the reactivity of passivated geomedia to levels comparable to those of the virgin manganese-oxide coated sand. Treatment with HCl restored about one third of the reactivity of the material, likely due to dissolution of reduced Mn. Mn K-edge X-ray absorption spectroscopy data indicated that the reactive manganese oxide phases present in virgin geomedia and geomedia regenerated with HOCl or HOBr had nanocrystalline cryptomelane-like structures and diminished Mn(III) abundance relative to the passivated geomedia. KMnO4-regenerated geomedia also had less Mn(III), but it exhibited less reactivity with bisphenol A because regeneration produced a structure with characteristics of δ-MnO2. The results imply that manganese oxide reactivity depends on both oxidation state and crystal structure; the most effective chemical regenerants oxidize Mn(III) to Mn(IV) oxides exhibiting nanocrystalline, cryptomelane-like forms.

Asunto(s)

Compuestos de Manganeso , Óxidos , Manganeso , Minerales , Oxidación-Reducción , Arena

RESUMEN

Arsenic (As) is a toxic element present in many (ground)water sources in the world. Most conventional As removal techniques require pre-oxidation of the neutral arsenite (As(III)) species to the negatively charged arsenate (As(V)) oxyanion to optimize As removal and minimize chemical use. In this work, a novel, continuous-flow As removal system was developed that combines biological As(III) oxidation by bacteria with Fe electrocoagulation (EC), an Fe(0)-based electrochemical technology that generates reactive Fe(III) precipitates to bind As. The bio-integrated FeEC system (bio-FeEC) showed effective oxidation and removal of 150 µg/L As(III), without the need of chemicals. To remove As to below the WHO guideline of 10 µg/L, 10 times lower charge dosage was required for the bio-FeEC system compared to conventional FeEC. This lower Fe dosage requirement reduced sludge production and energy consumption. The As(III) oxidizing biomass was found to consist of bacteria belonging to Comamonadaceae, Rhodobacteraceae and Acidovorax, which are capable of oxidizing As(III) and are common in drinking water biofilms. Characterization of the As-laden Fe solids by X-ray absorption spectroscopy indicated that both bio-FeEC and conventional FeEC produced solids consistent with a mixture of lepidocrocite and 2-line ferrihydrite. Arsenic bound to the solids was dominantly As(V), but a slightly higher fraction of As(V) was detected in the bio-FeEC solids compared to the conventional FeEC.

Asunto(s)

Arsénico , Productos Biológicos , Agua Subterránea , Contaminantes Químicos del Agua , Purificación del Agua , Electrocoagulación , Compuestos Férricos , Hierro , Oxidación-Reducción

RESUMEN

Effective arsenic (As) removal from groundwater is a pressing need in view of increasingly stringent As drinking water limits in some US states and European countries. In this study, we compared the addition of weak (O2), intermediate (NaOCl), and strong (KMnO4) groundwater oxidants on the fate of As during As(III), Fe(II), and Mn(II) co-oxidation. Experiments were performed with 50 µg/L As(III), 5 mg/L Fe(II), and 0.5 mg/L Mn(II) in solutions containing relevant groundwater ions, with the reaction products characterized by As K-edge X-ray absorption spectroscopy (XAS). Adding O2 by aeration was the least effective method, unable to decrease As to below 10 µg/L, which was attributed to inefficient As(III) oxidation. Dosing NaOCl (55 µM) consistently removed As to <10 µg/L (and often <5 µg/L). The As K-edge XAS data of the NaOCl samples indicated complete As(III) oxidation and As(V) sorption to coprecipitated hydrous ferric oxide (HFO) in the binuclear, bridging (2C) complex. The most effective As removal was observed with KMnO4 (40 µM), which completely oxidized As(III) and yielded residual As concentrations that were less than (by as much as 50%) or equal to the NaOCl experiments. Furthermore, the average As-metal bond length of the KMnO4 solids (RAs-Fe/Mn = 3.24 ± 0.02 Å) was systematically shorter than the NaOCl solids (RAs-Fe/Mn = 3.29 ± 0.02 Å), consistent with As(V) sorption to both MnO2 and HFO. These findings can be used to optimize groundwater As treatment to meet relevant drinking water guidelines, while considering the As uptake mode and characteristics of the particle suspension (i.e., colloidal stability and filterability).

Asunto(s)

Arsénico , Agua Subterránea , Contaminantes Químicos del Agua , Purificación del Agua , Adsorción , Europa (Continente) , Compuestos Férricos , Compuestos Ferrosos , Compuestos de Manganeso , Oxidación-Reducción

RESUMEN

Sorption of nutrients such as phosphate (P) and silicate (Si) by ferric iron (oxyhydr)oxides (FeOx) modulates nutrient mobility and alters the structure and reactivity of the FeOx. We investigated the impact of these interactions on FeOx transformations using a novel approach with samplers containing synthetic FeOx embedded in diffusive hydrogels. The FeOx were prepared by Fe(III) hydrolysis and Fe(II) oxidation, in the absence and presence of P or Si. Coprecipitation of P or Si during synthesis altered the structure of Fe precipitates and, in the case of Fe(II) oxidation, lepidocrocite was (partly) substituted by poorly ordered FeOx. The pure and P- or Si-bearing FeOx were deployed in (i) freshwater sediment rich in dissolved Fe(II) and P and (ii) marine sediment with sulfidic pore water. Iron(II)-catalyzed crystallization of poorly ordered FeOx was negligible, likely due to surface passivation by adsorption of dissolved P. Reaction with dissolved sulfide was modulated by diffusion limitations and therefore the extent of sulfidation was the lowest for poorly ordered FeOx with high reactivity toward sulfide that created temporary, local sulfide depletion (Fh < Lp). We show that coprecipitation-induced changes in the FeOx structure affect coupled iron-nutrient cycling in aquatic ecosystems. The gel-based method enriches our geochemical toolbox by enabling detailed characterization of target phases under natural conditions.

Asunto(s)

Compuestos Férricos , Hierro , Ecosistema , Oxidación-Reducción , Óxidos , Fosfatos , Silicatos

RESUMEN

Millions of people are exposed to toxic levels of dissolved arsenic in groundwater used for drinking. Iron electrocoagulation (FeEC) has been demonstrated as an effective technology to remove arsenic at an affordable price. However, FeEC requires long operating times (∼hours) to remove dissolved arsenic due to inherent kinetics limitations. Air cathode Assisted Iron Electrocoagulation (ACAIE) overcomes this limitation by cathodically generating H2O2 in situ. In ACAIE operation, rapid oxidation of Fe(II) and complete oxidation and removal of As(III) are achieved. We compare FeEC and ACAIE for removing As(III) from an initial concentration of 1464 µg/L, aiming for a final concentration of less than 4 µg/L. We demonstrate that at short electrolysis times (0.5 min), i.e., high charge dosage rates (1200 C/L/min), ACAIE consistently outperformed FeEC in bringing arsenic levels to less than WHO-MCL of 10 µg/L. Using XRD and XAS data, we conclusively show that poor arsenic removal in FeEC arises from incomplete As(III) oxidation, ineffective Fe(II) oxidation and the formation of Fe(II-III) (hydr)oxides at short electrolysis times (<20 min). Finally, we report successful ACAIE performance (retention time 19 s) in removing dissolved arsenic from contaminated groundwater in rural California.

Asunto(s)

Arsénico , Agua Subterránea , Contaminantes Químicos del Agua , Purificación del Agua , Electrocoagulación , Peróxido de Hidrógeno , Hierro , Oxidación-Reducción

RESUMEN

Iron electrocoagulation (Fe-EC) is an effective technology to remove arsenic (As) from groundwater used for drinking. A commonly noted limitation of Fe-EC is fouling or passivation of electrode surfaces via rust accumulation over long-term use. In this study, we examined the effect of removing electrode surface layers on the performance of a large-scale (10,000 L/d capacity) Fe-EC plant in West Bengal, India. We also characterized the layers formed on the electrodes in active use for over 2 years at this plant. The electrode surfaces developed three distinct horizontal sections of layers that consisted of different minerals: calcite, Fe(III) precipitates and magnetite near the top, magnetite in the middle, and Fe(III) precipitates and magnetite near the bottom. The interior of all surface layers adjacent to the Fe(0) metal was dominated by magnetite. We determined the impact of surface layer removal by mechanical abrasion on Fe-EC performance by measuring solution composition (As, Fe, P, Si, Mn, Ca, pH, DO) and electrochemical parameters (total cell voltage and electrode interface potentials) during electrolysis. After electrode cleaning, the Fe concentration in the bulk solution increased substantially from 15.2 to 41.5 mg/L. This higher Fe concentration led to increased removal of a number of solutes. For As, the concentration reached below the 10 µg/L WHO MCL more rapidly and with less total Fe consumed (i.e. less electrical energy) after cleaning (128.4 µg/L As removed per kWh) compared to before cleaning (72.9 µg/L As removed per kWh). Similarly, the removal of P and Si improved after cleaning by 0.3 mg/L/kWh and 1.1 mg/L/kWh, respectively. Our results show that mechanically removing the surface layers that accumulate on electrodes over extended periods of Fe-EC operation can restore Fe-EC system efficiency (concentration of solute removed/kWh delivered). Since Fe release into the bulk solution substantially increased upon electrode cleaning, our results also suggest that routine electrode maintenance can ensure robust and reliable Fe-EC performance over year-long timescales.

Asunto(s)

Arsénico , Agua Subterránea , Contaminantes Químicos del Agua , Purificación del Agua , Electrocoagulación , Electrodos , India , Hierro

RESUMEN

Warming-induced nutrient enrichment in the Arctic may lead to shifts in leaf-level physiological properties and processes with potential consequences for plant community dynamics and ecosystem function. To explore the physiological responses of Arctic tundra vegetation to increasing nutrient availability, we examined how a set of leaf nutrient and physiological characteristics of eight plant species (representing four plant functional groups) respond to a gradient of experimental nitrogen (N) and phosphorus (P) enrichment. Specifically, we examined a set of chlorophyll fluorescence measures related to photosynthetic efficiency, performance and stress, and two leaf nutrient traits (leaf %C and %N), across an experimental nutrient gradient at the Arctic Long Term Ecological Research site, located in the northern foothills of the Brooks Range, Alaska. In addition, we explicitly assessed the direct relationships between chlorophyll fluorescence and leaf %N. We found significant differences in physiological and nutrient traits between species and plant functional groups, and we found that species within one functional group (deciduous shrubs) have significantly greater leaf %N at high levels of nutrient addition. In addition, we found positive, saturating relationships between leaf %N and chlorophyll fluorescence measures across all species. Our results highlight species-specific differences in leaf nutrient traits and physiology in this ecosystem. In particular, the effects of a gradient of nutrient enrichment were most prominent in deciduous plant species, the plant functional group known to be increasing in relative abundance with warming in this ecosystem.

Asunto(s)

Ecosistema , Tundra , Alaska , Regiones Árticas , Nutrientes

RESUMEN

OBJECTIVE: To define the relationship between urology relative value units (RVUs) and measures of surgical complexity and physician workload. Secondary objectives include: (1) identifying procedures with outlying RVU values for their measures of surgical complexity and workload; and (2) calculating projected RVU values for these procedures. METHODS: We obtained surgical case data for 71 urology current procedural terminology (CPT) codes from the 2017 American College of Surgeons National Surgical Quality Improvement Program (NSQIP) database. Pearson correlation coefficients were calculated to measure the association between mean total work RVU and operative time, length of hospital stay, serious adverse events, readmissions, and mortality. We developed a multivariable regression model to predict mean total work RVU from these measures. Studentized residuals were used to identify outlying CPT codes for both bivariable and multivariable regression models, and empirically derived RVU values from complexity and work effort metrics were estimated. RESULTS: We analyzed 71 urology CPT codes encompassing 55,068 cases. RVUs correlated well with median length of hospital stay (R = 0.81), median operative time (R = 0.92), serious adverse events (R = 0.83), and readmissions (R = 0.74). RVUs were poorly correlated with mortality (R = 0.34). Outlying procedures identified using the multivariable model were retroperitoneal lymph node dissection (projected +21.09 RVUs), laparoscopic ureteroneocystotomy (projected -12.34 RVUs), and cystectomy with bilateral pelvic lymphadenectomy (projected +9.37 RVUs). CONCLUSION: Urology work RVUs correlate more with operative time than other measures of surgical complexity and physician workload. There exist several significant outlying procedures for various work measures. Incorporating objective work data may improve RVU assignments in the future.

Asunto(s)

Eficiencia , Tempo Operativo , Médicos , Complicaciones Posoperatorias , Enfermedades Urológicas , Procedimientos Quirúrgicos Urológicos , Carga de Trabajo/estadística & datos numéricos , Current Procedural Terminology , Mortalidad Hospitalaria , Humanos , Modelos Logísticos , Gravedad del Paciente , Readmisión del Paciente/estadística & datos numéricos , Médicos/organización & administración , Médicos/estadística & datos numéricos , Complicaciones Posoperatorias/epidemiología , Complicaciones Posoperatorias/etiología , Complicaciones Posoperatorias/prevención & control , Mejoramiento de la Calidad , Escalas de Valor Relativo , Estados Unidos , Enfermedades Urológicas/epidemiología , Enfermedades Urológicas/cirugía , Procedimientos Quirúrgicos Urológicos/efectos adversos , Procedimientos Quirúrgicos Urológicos/métodos , Procedimientos Quirúrgicos Urológicos/mortalidad , Procedimientos Quirúrgicos Urológicos/estadística & datos numéricos , Urología/métodos , Urología/normas

RESUMEN

"Green rust" (GR), a redox-active Fe(II)-Fe(III) layered double hydroxide, is a potential environmentally relevant mineral substrate for arsenic (As) sequestration in reduced, subsurface environments. GR phases have high As uptake capacities at circum-neutral pH conditions, but the exact interaction mechanism between the GR phases and As species is still poorly understood. Here, we documented the bonding and interaction mechanisms between GR sulfate and As species [As(III) and As(V)] under anoxic and circum-neutral pH conditions through scanning transmission electron microscopy (STEM) coupled with energy-dispersive X-ray (EDX) spectroscopy and combined it with synchrotron-based X-ray total scattering, pair distribution function (PDF) analysis, and As K-edge X-ray absorption spectroscopy (XAS). Our highly spatially resolved STEM-EDX data revealed that the preferred adsorption sites of both As(III) and As(V) are at GR crystal edges. Combining this data with differential PDF and XAS allowed us to conclude that As adsorption occurs primarily as bidentate binuclear (2C) inner-sphere surface complexes. In the As(III)-reacted GR sulfate, no secondary Fe-As phases were observed. However, authigenic parasymplesite (ferrous arsenate nanophase), exhibiting a threadlike morphology, formed in the As(V)-reacted GR sulfate and acts as an additional immobilization pathway for As(V) (∼87% of immobilized As). We demonstrate that only by combining high-resolution STEM imaging and EDX mapping with the bulk (differential) PDF and extended X-ray absorption fine structure (EXAFS) data can one truly determine the de facto As binding nature on GR surfaces. More importantly, these new insights into As-GR interaction mechanisms highlight the impact of GR phases on As sequestration in anoxic subsurface environments.

Asunto(s)

Arsénico , Adsorción , Compuestos Férricos , Sulfatos , Espectroscopía de Absorción de Rayos X

RESUMEN

In this work, we combined macroscopic measurements of precipitate aggregation and chemical composition (Mn/Fe solids ratio) with Fe and Mn K-edge X-ray absorption spectroscopy to investigate the solids formed by co-oxidation of Fe(II) and Mn(II) with O2, MnO4, and HOCl in the presence of groundwater ions. In the absence of the strongly sorbing oxyanions, phosphate (P) and silicate (Si), and calcium (Ca), O2 and HOCl produced suspensions that aggregated rapidly, whereas co-oxidation of Fe(II) and Mn(II) by MnO4 generated colloidally stable suspensions. The aggregation of all suspensions decreased in P and Si solutions, but Ca counteracted these oxyanion effects. The speciation of oxidized Fe and Mn in the absence of P and Si also depended on the oxidant, with O2 producing Mn(III)-incorporated lepidocrocite (Mn/Fe = 0.01-0.02 mol/mol), HOCl producing Mn(III)-incorporated hydrous ferric oxide (HFO) (Mn/Fe = 0.08 mol/mol), and MnO4 producing poorly-ordered MnO2 and HFO (Mn/Fe > 0.5 mol/mol). In general, the presence of P and Si decreased the crystallinity of the Fe(III) phase and increased the Mn/Fe solids ratio, which was found by Mn K-edge XAS analysis to be due to an increase in surface-bound Mn(II). By contrast, Ca decreased the Mn/Fe solids ratio and decreased the fraction of Mn(II) associated with the solids, suggesting that Ca and Mn(II) compete for sorption sites. Based on these results, we discuss strategies to optimize the design (i.e. filter bed operation and chemical dosing) of water treatment plants that aim to remove Fe(II) and Mn(II) by co-oxidation.

Asunto(s)

Arsénico , Agua Subterránea , Compuestos Férricos , Compuestos Ferrosos , Compuestos de Manganeso , Oxidación-Reducción , Óxidos

RESUMEN

Iron (oxyhydr)oxides (FeOx) control retention of dissolved nutrients and contaminants in aquatic systems. However, FeOx structure and reactivity is dependent on adsorption and incorporation of such dissolved species, particularly oxyanions such as phosphate and silicate. These interactions affect the fate of nutrients and metal(loids), especially in perturbed aquatic environments such as eutrophic coastal systems and environments impacted by acid mine drainage. Altered FeOx reactivity impacts sedimentary nutrient retention capacity and, eventually, ecosystem trophic state. Here, we explore the influence of phosphate (P) and silicate (Si) on FeOx structure and reactivity. Synthetic, poorly crystalline FeOx with adsorbed and coprecipitated phosphate or silicate at low but environmentally relevant P/Fe or Si/Fe ratios (0.02-0.1 mol mol-1) was prepared by base titration of Fe(III) solutions. Structural characteristics of FeOx were investigated by X-ray diffraction, synchrotron-based X-ray absorption spectroscopy and high-energy X-ray scattering. Reactivity of FeOx was assessed by kinetic dissolution experiments under acidic (dilute HCl, pH 2) and circum-neutral reducing (bicarbonate-buffered ascorbic acid, pH 7.8, Eh ∼ -300 mV) conditions. At these loadings, phosphate and silicate coprecipitation had only slight impact on local and intermediate-ranged FeOx structure, but significantly enhanced the dissolution rate of FeOx. Conversely, phosphate and silicate adsorption at similar loadings resulted in particle surface passivation and decreased FeOx dissolution rates. These findings indicate that varying nutrient loadings and different interaction mechanisms between anions and FeOx (adsorption versus coprecipitation) can influence the broader biogeochemical functioning of aquatic ecosystems by impacting the structure and reactivity of FeOx.

Asunto(s)

Ecosistema , Contaminantes Ambientales/química , Compuestos Férricos/química , Fosfatos/química , Silicatos/química , Contaminantes Químicos del Agua/química , Adsorción , Contaminantes Ambientales/análisis , Cinética , Fosfatos/análisis , Silicatos/análisis , Solubilidad , Contaminantes Químicos del Agua/análisis

RESUMEN

Iron-electrocoagulation is a promising contaminant (e.g. arsenic) removal technology that is based on electrochemical Fe(II) production from steel electrodes and subsequent transport of Fe(II) to the bulk solution, where contaminant removal occurs. Although Fe-electrocoagulation systems have been shown to effectively remove contaminants in extended field trials, the efficiency of field systems can be lower than in laboratory studies. One hypothesis for this disparity is that the Faradaic efficiency of short-term laboratory experiments is higher than field systems operated over extended periods. The Faradaic efficiency is a pivotal performance indicator that we define as the measured Fe dosage normalized by the theoretical Fe dosage calculated by Faraday's law. In this work, we investigated the Faradaic efficiency in laboratory experiments for up to 35 operating cycles (>2 months) with varied Fe(0) anode purity, charge dosage rate, and electrolyte composition. Our results showed that the Faradaic efficiency decreased continuously during repeated operation under typical field conditions (charge dosage rate = 4 C/L/min, synthetic groundwater) regardless of the Fe(0) anode purity, leading to a Faradaic efficiency ≈ 0.6 after 2 months. By contrast, increasing the charge dosage rate to ≥15 C/L/min produced a Faradaic efficiency >0.85 over the entire experiment for both Fe(0) anode purities. Electrolyte solutions free of oxyanions also resulted in sustained Faradaic efficiency >0.85, regardless of the charge dosage rate. Our results confirm a previously proposed relationship between low Faradaic efficiency and the formation of macroscopic electrode surface layers, which consist of Fe (oxyhydr)oxides on the anode and a mixture of Fe (oxyhydr)oxides and calcite on the cathode. Based on these results, we discuss potential strategies to maintain a high Faradaic efficiency during Fe-electrocoagulation field treatment.

Asunto(s)

Agua Subterránea , Contaminantes Químicos del Agua , Purificación del Agua , Electrocoagulación , Electrodos , Hierro

RESUMEN

In this study, concrete stabilization is adopted to sustainably manage hazardous arsenic-iron sludge near the vicinity of a community-based arsenic water treatment plant for potential use as material for local construction. The strength and workability of the sludge mixed with fresh concrete were investigated to determine the suitability of the concrete mixture for building materials. We found that over 25% sludge (with respect to cement weight) can be incorporated safely into different grades of concrete (M15 and M20). Structural characterization of the concrete mixtures by Fe and As K-edge X-ray absorption spectroscopy indicated a structural transformation of Fe in the sludge from a hydrous ferric oxide to a less ordered phase consistent with Fe siliceous hydrogarnet. Differences in the As K-edge XAS data of samples before and after stabilization in concrete were interpreted as a decrease in As-Fe coordination after concrete stabilization in favor of As-Ca coordination. The leaching of arsenic in the stabilized concrete was examined by the Toxicity Characteristics Leaching Procedure (TCLP) and found to produce < 15 µg/L As, even at the highest sludge mixture fraction (40% sludge with respect to cement weight). The formation of calcite in concrete stabilized arsenic sludge, which was detected by X-ray diffraction (XRD), contributes to the low leachability of arsenic in the sludge for a variety of reasons, including decreasing pore size. In addition, the formation of poorly soluble calcium arsenates can also be responsible for the low mobility of arsenic. Overall concrete stabilization of arsenic-iron sludge can be an effective pre-treatment to safe landfill disposal and, when the arsenic-iron sludge is mixed in specific proportions to achieve desired strength, we propose this concrete can be used locally in nearby construction.

Asunto(s)

Arsénico , Materiales de Construcción , Hierro , Aguas del Alcantarillado , Instalaciones de Eliminación de Residuos