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1.
Anal Chem ; 94(11): 4576-4583, 2022 03 22.
Artigo em Inglês | MEDLINE | ID: mdl-35262341

RESUMO

Anthropogenic and climatic perturbations redistribute arsenic (As), antimony (Sb), and selenium (Se) within the environment. The speciation characteristics of these elements determine their behavior and biogeochemical cycling, but these redox-sensitive species are challenging to capture, with few methods able to harmonize measurements across the whole plant-soil-ecosystem continuum. In this study, we developed a novel diffusive gradient in thin films (DGT) method based on aminopropyl and mercaptopropyl bi-functionalized mesoporous silica spheres (AMBS) to achieve in-situ, simultaneous, and selective quantification of AsIII, SbIII, and SeIV, three typical/toxic but difficult to measure inorganic species. When used for environmental monitoring within a river catchment, AMBS-DGT exhibited stable/accurate predictions of these species despite varying water chemistries (ionic strength 0.01-200 mmol L-1 NO3-, pH 5-9 for AsIII and SbIII, and pH 5-7.5 for SeIV). Furthermore, river deployments also showed that time-averaged species concentrations by AMBS-DGT were reproducible compared with high-frequency sampling and measurement by high performance liquid chromatography coupled with inductively coupled plasma mass spectroscopy. When AMBS-DGT was used for sub-mm scale chemical imaging of soil solute fluxes, the method resolved concomitant redox-constrained spatial patterns of AsIII, SbIII, and SeIV associated with root O2 penetration within anaerobic soil. Improved capabilities for measurement of compartment interfaces and microniche features are critical alongside the measurement of larger-scale hydrological processes that dictate the fine-scale effects, with the AMBS-DGT achieving this for AsIII, SbIII, and SeIV.


Assuntos
Arsênio , Selênio , Arsênio/análise , Ecossistema , Monitoramento Ambiental/métodos , Água Doce/análise , Selênio/química , Solo/química
2.
Med Teach ; : 1-5, 2022 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-35815424

RESUMO

Effective mentorship is widely believed to be an important factor in career satisfaction and advancement. Adequate mentorship has been linked to perceived institutional support, research productivity, and protects against burnout. Despite these facts, less than half of junior faculty in academic medicine feel as if they have adequate mentorship. Given that the current landscape in academic medicine has a paucity of available mentors, both in rank and representation for true dyadic mentorship, junior faculty clinician educators may need mentorship and paths to sponsorship. The importance of peer networks has become increasingly recognized, and some institutions have begun to use peer mentoring as a means of addressing mentorship and sponsorship needs. This model can potentially circumvent some of the main barriers to mentorship by providing protected time, ameliorating power differentials, creating an environment where members have shared goals, and mitigating the need for senior faculty mentorship. The following are twelve tips to create and maintain a successful peer mentoring group for junior faculty clinician educators in academic medicine which can serve to complement the dyadic mentorship model.

3.
J Gen Intern Med ; 36(6): 1568-1575, 2021 06.
Artigo em Inglês | MEDLINE | ID: mdl-33532957

RESUMO

BACKGROUND: Safely and effectively discharging a patient from the hospital requires working within a multidisciplinary team. However, little is known about how perceptions of responsibility among the team impact discharge communication practices. OBJECTIVE: Our study attempts to understand residents' perceptions of who is primarily responsible for discharge education, how these perceptions affect their own reported communication with patients, and how residents envision improving multidisciplinary communication around discharges. DESIGN: A multi-institutional cross-sectional survey. PARTICIPANTS: Internal medicine (IM) residents from seven US residency programs at academic medical centers were invited to participate between March and May 2019, via email of an electronic link to the survey. MAIN MEASURES: Data collected included resident perception of who on the multidisciplinary team is primarily responsible for discharge communication, their own reported discharge communication practices, and open-ended comments on ways discharge multidisciplinary team communication could be improved. KEY RESULTS: Of the 613 resident responses (63% response rate), 35% reported they were unsure which member of the multidisciplinary team is primarily responsible for discharge education. Residents who believed it was either the intern's or the resident's primary responsibility had 4.28 (95% CI, 2.51-7.30) and 3.01 (95% CI, 1.66-5.71) times the odds, respectively, of reporting doing discharge communication practices frequently compared to those who were not sure who was primarily responsible. To improve multidisciplinary discharge communication, residents called for the following among team members: (1) clarifying roles and responsibilities for communication with patients, (2) setting expectations for communication among multidisciplinary team members, and (3) redefining culture around discharges. CONCLUSIONS: Residents report a lack of understanding of who is responsible for discharge education. This diffusion of ownership impacts how much residents invest in patient education, with more perceived responsibility associated with more frequent discharge communication.


Assuntos
Internato e Residência , Alta do Paciente , Comunicação , Estudos Transversais , Escolaridade , Hospitais , Humanos
4.
Environ Sci Technol ; 55(11): 7344-7354, 2021 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-33730498

RESUMO

Land application of biochar, the product of organic waste carbonization, can improve soil fertility as well as sequester carbon to mitigate climate change. In addition, biochar can greatly influence the bioavailability of toxic trace elements (TTEs) in soils resulting from its large internal surface areas, abundance in organic carbon, and ability to modify soil pH. Most research to date employs batch leaching tests to predict how biochar addition impacts TTE bioavailability, but these ex situ tests rarely considered the rhizospheric effect which might offset or intensify the changes induced by organic residue addition. This is especially so in rice rhizospheres because of strong clines in localized redox conditions. In this study, we adopted in situ high-resolution (HR) diffusive gradients in thin films (DGT) as well as rhizo-bag porewater sampling experiments to depict an overall picture of the difference in TTE (As, Cd, Cu, Ni, and Pb) bioavailability between the rice rhizosphere and bulk soils during land application of biochar. Porewater sampling experiments revealed that biochar additions stimulated TTE release due to the increase of dissolved organic carbon (DOC) and H+ concentrations. In the rhizosphere, although biochar still promoted As, Cd, and Ni release into porewaters, the rhizospheric effect was one of dampening/reduction compared with the bulk soil. When we focused on the localized changes of TTE bioavailability in the rhizosphere using an in situ HR-DGT approach, on the contrary, flux maxima of Cd, Cu, and Ni occurred near/on the root surface, and hot spots of As can be observed at peripheries of the rooting zone, which demonstrated the high heterogeneity and complexity of the rhizosphere's influence on TTE bioavailability.


Assuntos
Oryza , Poluentes do Solo , Oligoelementos , Disponibilidade Biológica , Carvão Vegetal , Solo , Poluentes do Solo/análise
5.
Environ Sci Technol ; 55(19): 13082-13092, 2021 10 05.
Artigo em Inglês | MEDLINE | ID: mdl-34554745

RESUMO

Resolving chemical/biological drivers of P behavior around lowland/flooded rice roots remains a challenge because of the heterogeneity of the plant-soil interactions, compounded by sampling and analytical constraints. High-spatial-resolution (sub-mm) visualization enables these processes to be isolated, characterized, and deciphered. Here, three advanced soil imaging systems, diffusive gradients in thin-film technique coupled with laser ablation-ICPMS (DGT-LA-ICPMS), O2 planar optode, and soil zymography, were integrated. This trio of approaches was then applied to a rice life cycle study to quantify solute-P supply, through two dimensions, in situ, and low-disturbance high-resolution (HR) chemical imaging. This allowed mechanisms of P release to be delineated by O2, Fe, and phosphatase activity mapping at the same scale. HR-DGT revealed P depletion around both living and dead rice roots but with highly spatially variable Fe/P ratios (∼0.2-12.0) which aligned with changing redox conditions and root activities. Partnering of HR-DGT and soil zymography revealed concurrent P depletion and phosphatase hotspots in the rhizosphere and detritusphere zones (Mantel: 0.610-0.810, p < 0.01). This close affinity between these responses (Pearson correlation: -0.265 to -0.660, p < 0.01) cross-validates the measurements and reaffirms that P depletion stimulates phosphatase activity and Porg mineralization. The µ-scale biogeochemical landscape of rice rhizospheres and detritusphere, as documented here, needs greater consideration when implementing interventions to improve sustainable P nutrition.


Assuntos
Oryza , Poluentes do Solo , Fósforo , Raízes de Plantas/química , Rizosfera , Solo , Poluentes do Solo/análise
6.
Blood Purif ; 50(4-5): 595-601, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-33445176

RESUMO

The COVID-19 pandemic has resulted in an avalanche of information, much of it false or misleading. Social media posts with misleading or dangerous opinions and analyses are often amplified by celebrities and social media influencers; these posts have contributed substantially to this avalanche of information. An emerging force in this information infodemic is public physicians, doctors who view a public presence as a large segment of their mission. These physicians bring authority and real-world experience to the COVID-19 discussion. To investigate the role of public physicians, we interviewed a convenience cohort of physicians who have played a role in the infodemic. We asked the physicians about how their roles have changed, how their audience has changed, what role politics plays, and how they address misinformation. The physicians noted increased audience size with an increased focus on the pandemic. Most avoided confronting politics, but others found it unavoidable or that even if they tried to avoide it, it would be brought up by their audience. The physicians felt that confronting and correcting misinformation was a core part of their mission. Public physicians on social media are a new occurrence and are an important part of fighting online misinformation.


Assuntos
COVID-19 , Educação em Saúde , Educadores em Saúde , Pandemias , Papel do Médico , SARS-CoV-2 , Mídias Sociais , Atitude do Pessoal de Saúde , Comunicação , Humanos , Disseminação de Informação , Comportamento de Busca de Informação , Meios de Comunicação de Massa , Política
7.
Anal Chem ; 92(5): 3581-3588, 2020 03 03.
Artigo em Inglês | MEDLINE | ID: mdl-31916433

RESUMO

In situ monitoring of Sb speciation improves the understanding of Sb biogeochemistry and toxicity in ecosystems. Precise measurement of Sb is a challenge due to its instability of oxidation and ultratrace concentration. The development of simple and reliable methods specific to SbIII measurement is not only appealing but essential for implementing regulations. Here, we present an in situ speciation analysis method for SbIII, using the diffusive gradients in thin films (DGT) technique, combined with mercapto-functionalized SBA-15 mesoporous silica nanoparticles (MSBA). Laboratory performance tests confirmed MSBA-DGT uptake was independent of pH (4-9) and ionic strength (0.1-200 mmol L-1). DGT devices equipped with MSBA-based binding gels showed a theoretically linear accumulation of SbIII and exhibited a high capacity for SbIII at 65 µg/gel disc, with negligible accumulation of SbV over a 72 h deployment. Compared with commercial 3-mercaptopropyl-functionalized silica (MFS), the nanosized MSBA facilitate its even distribution in the binding gels. Furthermore, the good selectivity and high homogeneity of the MSBA gel enabled it to be applied in a rice rhizosphere in conjunction with AgI gel to investigate the effects of sulfur application on the SbIII solubility. In summary, the newly developed MSBA-DGT provides a selective measurement of SbIII, showing potential for environmental monitoring and further application in understanding the biogeochemical process of Sb.


Assuntos
Antimônio/análise , Dióxido de Silício/química , Solo/química , Difusão , Porosidade
8.
Environ Sci Technol ; 54(6): 3138-3147, 2020 03 17.
Artigo em Inglês | MEDLINE | ID: mdl-31968168

RESUMO

Behavior of trace elements in flooded/lowland rice soils is controlled by root-zone iron oxidation. Insoluble iron species bind/capture toxic elements, i.e., arsenic. However, it was recently observed that within this territory of arsenic immobilization lies a zone of prolific iron release, accompanied by a significant flux of arsenic in close proximity to rice root apices. Questions still remain on how common this phenomenon is and whether the chemical imaging approaches or soils/cultivars used influence this event. Here, three types of ultrathin/high-resolution diffusive gradient in thin films (DGT) substrates were integrated with oxygen planar optodes in a multilayer system, providing two-dimensional mapping of solute fluxes. The three DGT approaches revealed a consistent/overlapping spatial distribution with localized flux maxima for arsenic, which occurred in all experiments, concomitant with iron mobilization. Soil/porewater microsampling within the rhizosphere revealed no significant elevation in the solid phase's total iron and arsenic concentrations between aerobic and anaerobic zones. Contrary to arsenic, phosphorus bioavailability was shown to decrease in the arsenic/iron flux maxima. Rice roots, in addition to their role in nutrient acquisition, also perform a key sensory function. Flux maxima represent a significant departure from the chemical conditions of the bulk/field environment, but our observations of a complete rhizosphere reveal a mixed mode of root-soil interactions.


Assuntos
Arsênio , Oryza , Poluentes do Solo , Rizosfera , Solo
9.
Anal Chem ; 91(2): 1344-1352, 2019 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-30560662

RESUMO

Thallium (Tl) has been identified as a priority contaminant because of its severe toxic effects. Exact measurement of Tl is a challenge because it is difficult to avoid altering the element's chemical speciation during sampling, transport, and storage. In situ measurement may be a good choice. Based on the in situ technique of diffusive gradients in thin films (DGT), new DGT devices equipped with novel laboratory-synthesized manganese oxide (δ-MnO2) binding gels were developed and systematically validated for the measurement of Tl, including Tl(I) and Tl(III) species, in water. Comparison between Chelex binding gel and δ-MnO2 gel on the uptake kinetics of Tl demonstrated that δ-MnO2 binding gels could adsorb Tl rapidly and effectively. Removal of Tl from the δ-MnO2 gels was achieved by use of 1 mol·L-1 oxalic acid, yielding elution efficiencies of 1.0 for Tl(I) and 0.86 for TI(III). Theoretical responses from DGT devices loaded with δ-MnO2 gel (δ-MnO2-DGT) were obtained irrespective of pH (4-9) and ionic strength (0.1-200 mmol·L-1 NaNO3). δ-MnO2-DGT showed good potential for long-term monitoring of Tl due to its high adsorption capacity of 27.1 µg·cm-2 and the stable performance of δ-MnO2 binding gel kept in solution, containing only 10 mmol·L-1 NaNO3, for at least 117 days. Field deployment trials confirmed that δ-MnO2-DGT can accurately measure the time-averaged concentrations of Tl in fluvial watercourses. In summary, the newly developed δ-MnO2-DGT technique shows potential for environmental monitoring and biogeochemical investigation of Tl in waters.


Assuntos
Géis/química , Compostos de Manganês/química , Óxidos/química , Rios/química , Tálio/análise , Poluentes Químicos da Água/análise , Adsorção , Difusão , Concentração de Íons de Hidrogênio , Cinética , Limite de Detecção , Espectrometria de Massas/métodos , Concentração Osmolar
10.
Environ Sci Technol ; 53(13): 7288-7295, 2019 07 02.
Artigo em Inglês | MEDLINE | ID: mdl-31187619

RESUMO

The speciation of arsenic in wet and dry deposition are ambiguously described in current literature. Presented here is a 2 year study quantifying arsenic species in atmospheric deposition collected daily from an E. Atlantic coastal, semirural site, with comparative urban locations. Inorganic arsenic (Asi) was the principal form of arsenic in wet deposition, with a mean concentration of 0.54 µmol/m3. Trimethylarsine oxide (TMAO) was found to be the dominant form of organic arsenic, determined as above the LoD in 33% of wet deposition samples with a mean concentration of 0.12 µmol/m3. Comparison with codeposited trace elements and prevailing weather trajectories indicated that both anthropogenic and marine sources contribute to atmospheric deposition. Analysis of dry deposition revealed it to be a less significant input to the land-surface for Asi, contributing 32% of that deposited by wet deposition. Dry deposition had a larger proportion of Asi than that found in wet deposition, with TMAO making up only 12% of the sum of species. In comparison, urban sites showed large spatial and temporal variations in organic arsenic deposition, indicating that local sources of methylated species may be likely and that further understanding of biogenic arsine evolution and degradation are required to adequately assess the atmospheric arsenic burden and subsequent contribution to terrestrial ecosystems.


Assuntos
Poluentes Atmosféricos , Arsênio , Oligoelementos , Ecossistema , Monitoramento Ambiental , Tempo (Meteorologia)
11.
Environ Sci Technol ; 52(7): 3968-3974, 2018 04 03.
Artigo em Inglês | MEDLINE | ID: mdl-29505707

RESUMO

Marine sources of arsenic to the atmosphere are normally dismissed as minor. Here we show that arsenic can be biovolatilized from seawater, and that biovolatilzation is based on organic arsenic species present in the seawater. Even though inorganic arsenic is in great excess in seawaters, it is trimethylarsine (TMA) that is the primary biovolatilized product, with dimethylarsine (DMA) also observed if dimethylarsinic acid (DMAA) is spiked into seawaters. With respect to budgets, 0.04% of the total arsenic in the seawater was biovolatilized over a 2-week incubation period. To test the environmental significance of this finding, wet deposition was analyzed for arsenic species at coastal locations, one of which was the origin of the seawater. It was found that the oxidized product of TMA, trimethylarsine oxide (TMAO), and to a less extent DMAA were widely present. When outputs for arsines (0.9 nmol/m2/d) from seawater and inputs from wet deposition (0.3-0.5 nmol/m2/d) were compared, they were of the same order of magnitude. These findings provide impetus to reexamining the global arsenic cycle, as there is now a need to determine the flux of arsines from the ocean to the atmosphere.


Assuntos
Arsênio , Arsenicais , Atmosfera , Ácido Cacodílico , Água do Mar
12.
Environ Sci Technol ; 52(21): 12098-12107, 2018 11 06.
Artigo em Inglês | MEDLINE | ID: mdl-30247023

RESUMO

A method using miniaturized arrayed DGT-probes (PADDI) for high-frequency in situ sampling with LA-ICPMS and CID analysis was developed to measure the field-scale heterogeneity of trace-element bioavailability. Robust calibrations (R2 > 0.99) combined with high-sensitivity (LOD = 0.35 ng cm-2), multielemental detection, and short measurement times were achieved using a new LA-ICPMS microDGT analysis. In the studied paddy-site (size: ∼2500 m2), total element concentrations across the field were approximately uniform (R.S.D. < 10%), but bioavailability was shown to vary significantly as determined from 864 microgel measurements housed within 72 PADDI arrays. Porewater As measurements were unable to differentiate the top/rhizosphere and bulk/deeper-soil layers. However, dynamic sampling with DGT revealed significant differences. Heterogeneity behaviors varied greatly between the different elements. Arsenic bioavailability was stable laterally across the field, but varied with depth, which was in contrast to the trends for Pb. Fe/S(-II) change was bidirectional, differing horizontally and vertically throughout the field. The heterogeneity in Pb bioavailability, due to the high frequency of hotspot maxima that were discretely dispersed across the paddy, proved the most difficult to simulate requiring the greatest number of probe deployments to determine a reliable field-average. The DGT-PADDI system provides a new characterization of infield trends for improved trace-inorganics' management in agricultural wetlands.


Assuntos
Arsênio , Oryza , Poluentes do Solo , Disponibilidade Biológica , Ferro , Solo , Enxofre
13.
Environ Sci Technol ; 52(24): 14140-14148, 2018 12 18.
Artigo em Inglês | MEDLINE | ID: mdl-30431268

RESUMO

The speciation of selenium (Se) controls its fate and behavior, determining both its biological and environmental activities. However, in situ monitoring of SeIV presents a significant challenge due to its sensitivity to redox change. A novel diffusive gradients in thin films (DGT) technique containing mercapto-, amino-bifunctionalized SBA15 mesoporous silica nanoparticles was developed and evaluated in a series of laboratory and field deployment tests. The SBA-DGT exhibited a linear accumulation of SeIV ( r2 > 0.997) over a 72 h deployment, with negligible accumulation of SeVI(<5%). Consistent prediction of SeIV occurred within ionic strength and pH ranges of 0.1-200 mmol L-1 and 3.6-8, respectively. Limits of detection of the SBA-DGT were 0.03 µg SeIV L-1, which is suitable for natural waters. Moreover, the properties of the bifunctionalized SBA15 enable it to be fabricated within ultrathin (0.05 mm) gel layers for use in conjunction with O2 planar optode imaging. This new sandwich sensor technology with SBA-DGT was validated by mapping the two-dimensional distribution of SeIV and oxygen simultaneously in rice rhizospheres. This study shows that SBA-DGT provides a selective measurement of SeIV in situ, demonstrating its potential for both environmental monitoring and as a research tool for improving our understanding of Se biogeochemical processes.


Assuntos
Nanopartículas , Selênio , Monitoramento Ambiental , Dióxido de Silício , Solo
14.
Anal Chem ; 89(2): 1178-1184, 2017 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-27936613

RESUMO

Nitrate (NO3-N), the main plant/microbial nitrogen source, has a fast turnover in soil driven by species transformation (nitrification/denitrification) and phyto/microbiota assimilation. The technique of diffusive gradients in thin films (DGT) is capable of a robust, low disturbance measurement of NO3-N but has not been implemented due to the absence of a binding layer suitable for deployment in soils. In this study, a new styrene divinylbenzene-based absorbent with amine functional groups (SIR-100-HP) was cast into an agarose gel support. The NO3-N ion selectivity of the SIR-100-HP/agarose binding layer was retained in the presence of high multivalent ion concentrations and was used successfully to acquire in situ NO3-N measurements in bulk soil. The kinetics of binding and the maximum binding capacity were determined. The total capacity of the DGT containing the SIR-100-HP/agarose binding phase was 667 µg of NO3-N. The performance of DGT was not affected by varying pH (3-8) or ionic strength (0-0.018 mol L-1), while anion competition effects at concentrations reflecting those in common agricultural soils were found to be negligible. Complete elution (100% efficiency) of NO3-N from the binding phase was achieved using a solution of 5% NaCl. This technique was validated in three contrasting soils. CDGT measurements were in excellent agreement with pore water NO3-N values. Two-dimensional NO3-N mapping of a profile of flooded rice paddy soil demonstrated the potential of this novel methodology for improved characterization of in situ N speciation for further understanding of bioavailability and biogeochemical processes of NO3-N in soils.


Assuntos
Resinas de Troca Aniônica/química , Nitratos/análise , Solo/química , Estireno/química , Compostos de Vinila/química , Adsorção , Agricultura , Difusão , Monitoramento Ambiental/métodos , Cinética , Concentração Osmolar , Sefarose/química
15.
Environ Sci Technol ; 51(21): 12210-12218, 2017 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-28977751

RESUMO

For arsenic speciation, the inputs for wet deposition are not well understood. Here we demonstrate that trimethylarsine oxide (TMAO) and inorganic arsenic are the dominant species in monsoonal wet deposition in the summer Indian subcontinent, Bangladesh, with inorganic arsenic dominating, accounting for ∼80% of total arsenic in this medium. Lower concentrations of both species were found in monsoonal wet deposition in the winter Indian subcontinent, Sri Lanka. The only other species present was dimethylarsinic acid (DMAA), but this was usually below limits of detection (LoD). We hypothesize that TMAO and inorganic arsenic in monsoonal wet deposition are predominantly of marine origin. For TMAO, the potential source is the atmospheric oxidation of marine derived trimethylarsine. For inorganic arsenic, our evidence suggests entrainment of water column inorganic arsenic into atmospheric particulates. These conclusions are based on weather trajectory analysis and on the strong correlations with known wet deposition marine derived elements: boron, iodine, and selenium. The finding that TMAO and inorganic arsenic are widely present and elevated in monsoonal wet deposition identifies major knowledge gaps that need to be addressed regarding the understanding of arsenic's global cycle.


Assuntos
Arsênio , Arsenicais , Bangladesh , Ácido Cacodílico , Sri Lanka
16.
Environ Sci Technol ; 49(6): 3653-61, 2015 Mar 17.
Artigo em Inglês | MEDLINE | ID: mdl-25655234

RESUMO

Water-sediment exchange is a fundamental component of oxyanion cycling in the environment. Yet, many of the (im)mobilization processes overlay complex spatial and temporal redox regimes that occur within millimeters of the interface. Only a few methods exist that can reliably capture these porewater fluxes, with the most popular being high-resolution diffusive gradients in thin films (HR-DGT). However, functionality of HR-DGT is restricted by the availability of suitable analyte binding agents within the sampler, which must be simple to cast and homogeneously distributed in the binding layer, exhibit adequate sorption capacities, be resistive to chemical change, and possess a very fine particle size (≤10 µm). A novel binding layer was synthesized to meet these requirements by in situ precipitation of zirconia into a precast hydrogel. The particle diameter≤0.2 µm of zirconia in this precipitated gel was uniform and at least 50-times smaller than the conventional molding approach. Further, this gel had superior binding and stability characteristics compared with the commonly used ferrihydrite HR-DGT technique and could be easily fabricated as an ultrathin gel (60 µm) for simultaneous oxygen imaging in conjunction with planar-optodes. Chemical imaging of anion and oxygen fluxes using the new sampler were evaluated on Lake Taihu sediments.


Assuntos
Ânions/análise , Precipitação Química , Sedimentos Geológicos/química , Imageamento Tridimensional , Oxigênio/análise , Poluentes Químicos da Água/análise , Água/química , Zircônio/química , Difusão , Meio Ambiente , Géis , Concentração de Íons de Hidrogênio , Cinética , Concentração Osmolar , Espectrofotometria Atômica , Fatores de Tempo
17.
Anal Chem ; 86(6): 3060-7, 2014 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-24528281

RESUMO

A high-capacity diffusive gradients in thin films (DGT) technique has been developed for measurement of total dissolved inorganic arsenic (As) using a long shelf life binding gel layer containing hydrous zirconium oxide (Zr-oxide). Both As(III) and As(V) were rapidly accumulated in the Zr-oxide gel and could be quantitatively recovered by elution using 1.0 M NaOH for freshwater or a mixture of 1.0 M NaOH and 1.0 M H2O2 for seawater. DGT uptake of As(III) and As(V) increased linearly with deployment time and was independent of pH (2.0-9.1), ionic strength (0.01-750 mM), the coexistence of phosphate (0.25-10 mg P L(-1)), and the aging of the Zr-oxide gel up to 24 months after production. The capacities of the Zr-oxide DGT were 159 µg As(III) and 434 µg As(V) per device for freshwater and 94 µg As(III) and 152 µg As(V) per device for seawater. These values were 5-29 times and 3-19 times more than those reported for the commonly used ferrihydrite and Metsorb DGTs, respectively. Deployments of the Zr-oxide DGT in As-spiked synthetic seawater provided accurate measurements of total dissolved inorganic As over the 96 h deployment, whereas ferrihydrite and Metsorb DGTs only measured the concentrations accurately up to 24 and 48 h, respectively. Deployments in soils showed that the Zr-oxide DGT was a reliable and robust tool, even for soil samples heavily polluted with As. In contrast, As in these soils was underestimated by ferrihydrite and Metsorb DGTs due to insufficient effective capacities, which were likely suppressed by the competing effects of phosphate.

18.
Environ Sci Technol ; 48(15): 8498-506, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24967508

RESUMO

In wetland-adapted plants, such as rice, it is typically root apexes, sites of rapid entry for water/nutrients, where radial oxygen losses (ROLs) are highest. Nutrient/toxic metal uptake therefore largely occurs through oxidized zones and pH microgradients. However, the processes controlling the acquisition of trace elements in rice have been difficult to explore experimentally because of a lack of techniques for simultaneously measuring labile trace elements and O2/pH. Here, we use new diffusive gradients in thin films (DGT)/planar optode sandwich sensors deployed in situ on rice roots to demonstrate a new geochemical niche of greatly enhanced As, Pb, and Fe(II) mobilization into solution immediately adjacent to the root tips characterized by O2 enrichment and low pH. Fe(II) mobilization was congruent to that of the peripheral edge of the aerobic root zone, demonstrating that the Fe(II) mobilization maximum only developed in a narrow O2 range as the oxidation front penetrates the reducing soil. The Fe flux to the DGT resin at the root apexes was 3-fold higher than the anaerobic bulk soil and 27 times greater than the aerobic rooting zone. These results provide new evidence for the importance of coupled diffusion and oxidation of Fe in modulating trace metal solubilization, dispersion, and plant uptake.


Assuntos
Arsênio/análise , Ferro/análise , Chumbo/análise , Oryza , Raízes de Plantas , Poluentes do Solo/análise , Difusão , Concentração de Íons de Hidrogênio , Oxirredução , Oxigênio
20.
Environ Geochem Health ; 35(3): 379-90, 2013 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-23149722

RESUMO

Compared to other cereals, rice has particular strong As accumulation. Therefore, it is very important to understand As uptake and translocation among different genotypes. A field study in Chenzhou city, Hunan province of China, was employed to evaluate the effect of arsenic-contaminated soil on uptake and distribution in 34 genotypes of rice (including unpolished rice, husk, shoot, and root). The soil As concentrations ranged from 52.49 to 83.86 mg kg(-1), with mean As concentration 64.44 mg kg(-1). The mean As concentrations in rice plant tissues were different among the 34 rice genotypes. The highest As concentrations were accumulated in rice root (196.27-385.98 mg kg(-1) dry weight), while the lowest was in unpolished rice (0.31-0.52 mg kg(-1) dry weight). The distribution of As in rice tissue and paddy soil are as follows root ≫ soil > shoot > husk > unpolished rice. The ranges of concentrations of inorganic As in all of unpolished rice were from 0.26 to 0.52 mg kg(-1) dry weight. In particular, the percentage of inorganic As in the total As was more than 67 %, indicating that the inorganic As was the predominant species in unpolished rice. The daily dietary intakes of inorganic As in unpolished rice ranged from 0.10 to 0.21 mg for an adult, and from 0.075 to 0.15 mg for a child. Comparison with tolerable daily intakes established by FAO/WHO, inorganic As in most of unpolished rice samples exceeded the recommended intake values. The 34 genotypes of rice were classified into four clusters using a criteria value of rescaled distance between 5 and 10. Among the 34 genotypes, the genotypes II you 416 (II416) with the lowest enrichment of As and the lowest daily dietary intakes of inorganic As could be selected as the main cultivar in As-contaminated field.


Assuntos
Arsênio/química , Oryza/química , Poluentes do Solo/química , Adulto , Arsênio/análise , Arsênio/metabolismo , Criança , China , Monitoramento Ambiental/métodos , Genótipo , Humanos , Nível de Efeito Adverso não Observado , Oryza/genética , Solo/química , Poluentes do Solo/análise , Poluentes do Solo/metabolismo
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