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1.
Small ; 20(13): e2307236, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-37974471

RESUMO

Bimetallic metal-organic frameworks (MOFs) are promising nanomaterials whose reactivity towards biomolecules remains challenging due to issues related to synthesis, stability, control over metal oxidation state, phase purity, and atomic level characterization. Here, these shortcomings are rationally addressed through development of a synthesis of mixed metal Zr/Ce-MOFs in aqueous environment, overcoming significant hurdles in the development of MOF nanozymes, sufficiently stable on biologically relevant conditions. Specifically, a green and safe synthesis of Zr/Ce-MOF-808 is reported in water/acetic acid mixture which affords remarkably water-stable materials with reliable nanozymatic reactivity, including MOFs with a high Ce content previously reported to be unstable in water. The new materials outperform analogous bimetallic MOF nanozymes, showcasing that rational synthesis modifications could impart outstanding improvements. Further, atomic-level characterization by X-ray Absorption Fine Structure (XAFS) and X-ray Diffraction (XRD) confirmed superior nanozymes arise from differences in the synthetic method, which results in aqueous stable materials, and Ce incorporation, which perturbs the ligand exchange dynamics of the material, and could ultimately be used to fine tune the intrinsic MOF reactivity. Similar rational strategies which leverage metals in a synergistic manner should enable other water-stable bimetallic MOF nanozymes able to surpass existing ones, laying the path for varied biotechnological applications.


Assuntos
Estruturas Metalorgânicas , Nanoestruturas , Ácido Acético , Biotecnologia , Água
2.
Microsc Microanal ; 30(2): 236-252, 2024 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-38447180

RESUMO

Modern analytical tools, from microfocus X-ray diffraction (XRD) to electron microscopy-based microtexture measurements, offer exciting possibilities of diffraction-based multiscale residual strain measurements. The different techniques differ in scale and resolution, but may also yield significantly different strain values. This study, for example, clearly established that high-resolution electron backscattered diffraction (HR-EBSD) and high-resolution transmission Kikuchi diffraction (HR-TKD) [sensitive to changes in interplanar angle (Δθθ)], provide quantitatively higher residual strains than micro-Laue XRD and transmission electron microscope (TEM) based precession electron diffraction (PED) [sensitive to changes in interplanar spacing (Δdd)]. Even after correcting key known factors affecting the accuracy of HR-EBSD strain measurements, a scaling factor of ∼1.57 (between HR-EBSD and micro-Laue) emerged. We have then conducted "virtual" experiments by systematically deforming an ideal lattice by either changing an interplanar angle (α) or a lattice parameter (a). The patterns were kinematically and dynamically simulated, and corresponding strains were measured by HR-EBSD. These strains showed consistently higher values for lattice(s) distorted by α, than those altered by a. The differences in strain measurements were further emphasized by mapping identical location with HR-TKD and TEM-PED. These measurements exhibited different spatial resolution, but when scaled (with ∼1.57) provided similar lattice distortions numerically.

3.
Small ; 19(25): e2300759, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36919820

RESUMO

SiOx anode has a more durable cycle life than Si, being considered competitive to replace the conventional graphite. SiOx usually serves as composites with carbon to achieve more extended cycle life. However, the carbon microstructure dependent Li-ion storage behaviors in SiOx /C anode have received insufficient attention. Herein, this work demonstrates that the disorder of carbon can determine the ratio of inter- and intragranular Li-ion diffusions. The resulted variation of platform characteristics will result in different compatibility when matching SiOx . Rational disorder induced intergranular diffusion can benefit phase transition of SiOx /C, benefiting the electrochemical performance. Through a series of quantitative calculations and in situ X-ray diffraction characterizations, this work proposes the rational strategy for the future optimization, thus achieving preferable performance of SiOx /C anode.

4.
Small ; 19(28): e2301731, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37173815

RESUMO

The commercialization of high-energy Li-metal batteries is impeded by Li dendrites formed during electrochemical cycling and the safety hazards it causes. Here, a novel porous copper current collector that can effectively mitigate the dendritic growth of Li is reported. This porous Cu foil is fabricated via a simple two-step electrochemical process, where Cu-Zn alloy is electrodeposited on commercial copper foil and then Zn is electrochemically dissolved to form a 3D porous structure of Cu. The 3D porous Cu layers on average have a thickness of ≈14 um and porosity of ≈72%. This current collector can effectively suppress Li dendrites in cells cycled with a high areal capacity of 10 mAh cm-2 and under a high current density of 10 mA cm-2 . This electrochemical fabrication method is facile and scalable for mass production. Results of advanced in situ synchrotron X-ray diffraction reveal the phase evolution of the electrochemical deposition and dealloying processes.

5.
Small ; 19(38): e2301770, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37222115

RESUMO

Aqueous zinc batteries (ZIBs) have attracted considerable attention in recent years because of their high safety and eco-friendly features. Numerous studies have shown that adding Mn2+ salts to ZnSO4 electrolytes enhanced overall energy densities and extended the cycling life of Zn/MnO2 batteries. It is commonly believed that Mn2+ additives in the electrolyte inhibit the dissolution of MnO2 cathode. To better understand the role of Mn2+ electrolyte additives, the ZIB using a Co3 O4 cathode instead of MnO2 in 0.3 m MnSO4 + 3 m ZnSO4 electrolyte is built to avoid interference from MnO2 cathode. As expected, the Zn/Co3 O4 battery exhibits electrochemical characteristics nearly identical to those of Zn/MnO2 batteries. Operando synchrotron X-ray diffraction (XRD), ex situ X-ray absorption spectroscopy (XAS), and electrochemical analyses are carried out to determine the reaction mechanism and pathway. This work demonstrates that the electrochemical reaction occurring at cathode involves a reversible Mn2+ /MnO2 deposition/dissolution process, while a chemical reaction of Zn2+ /Zn4 SO4 (OH)6 ∙5H2 O deposition/dissolution is involved during part of the charge/discharge cycle due to the change in the electrolyte environment. The reversible Zn2+ /Zn4 SO4 (OH)6 ∙5H2 O reaction contributes no capacity and lowers the diffusion kinetics of the Mn2+ /MnO2 reaction, which prevents the operation of ZIBs at high current densities.

6.
Int J Mol Sci ; 24(7)2023 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-37047764

RESUMO

The postmortem interval (PMI) is difficult to estimate in later stages of decomposition. There is therefore a need to develop reliable methodologies to estimate late PMI. This study aims to assess whether there is a correlation between changes in the mineral composition of human teeth and the estimation of PMI. X-ray diffraction (XRD) and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy techniques were performed to address this challenge. Forty healthy human teeth obtained from odontological clinics were stored at different times (0, 10, 25, 50 years; N = 10/group). XRD and ATR-FTIR parameters related to the structure and composition of teeth were studied. Our results showed that the crystallinity index, crystal size index, mineral-to-organic matrix ratio (M/M) and carbonate/phosphate ratio (C/P) had the strongest association with PMI. For larger PMIs, there was a significant increase in crystallinity, crystal size and M/M ratio, while the C/P ratio showed a specific decrease with increasing PMI. According to our results, the parameters of crystallinity, crystal size, M/M ratio and C/P ratio can be considered highly accurate in determining a PMI of 10 years of data; crystallinity and mineral maturity can be considered useful in determining a PMI of 25 years; and crystallinity and mineral maturity can be considered highly accurate in determining a PMI of 50 years. A particular XRD index was identified as the most suitable parameter to estimate PMI: crystallinity. The joint use of XRD and ATR-FTIR analyses could be a promising alternative for dating human teeth.


Assuntos
Mudanças Depois da Morte , Humanos , Análise de Fourier , Difração de Raios X , Autopsia , Espectroscopia de Infravermelho com Transformada de Fourier/métodos
7.
Environ Geochem Health ; 45(8): 6471-6493, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37326777

RESUMO

The geochemistry of fly ash produced from the combustion of coal at thermal power plants presents a significant challenge for disposal and environmental impact due to its complex mineralogical and elemental composition. The objective of this study was to investigate the mineralogical and elemental distribution of thirty lignite samples from the Barmer Basin using advanced techniques such as X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS). XRD analysis revealed the presence of minerals such as haematite (Fe2O3), nepheline, anhydrite, magnesite, andalusite, spinel and anatase. Other minor minerals included albite, siderite, periclase, calcite, mayenite, hauyne, pyrite, cristobalite, quartz, nosean and kaolinite. XRF analysis demonstrated that the most abundant elements in the Barmer Basin lignite ash were iron oxide (Fe2O3), sulphur oxide (SO3), calcium oxide (CaO), and quartz (SiO2) followed by minor traces of toxic oxides (SrO, V2O5, NiO, Cr2O3, Co2O3, CuO) that are known to have adverse effects on human health and the environment. The rare earth element (REE) composition showed higher concentrations of Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc at the Giral and lower concentrations at Sonari mine. The Barmer lignites recorded higher concentration of trace elements such as V, Cr, Co, Ni, Cu and Sr while lower concentration of Rb, Cs, Ba, Pb, As, Th and U were observed within optimal range. The study findings revealed the predominant mineral concentration, elemental makeup, trace elements and rare earth elements associated with lignite reserves in the Barmer Basin.


Assuntos
Metais Terras Raras , Oligoelementos , Humanos , Oligoelementos/análise , Carvão Mineral/análise , Dióxido de Silício/análise , Quartzo/análise , Índia , Minerais/análise , Metais Terras Raras/análise
8.
Small ; 18(29): e2202151, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35748132

RESUMO

Li3 V2 (PO4 )3 (LVP) is a promising cathode material for lithium-ion batteries, especially when used in a wide temperature range, due to its high intrinsic ionic mobility and theoretical capacity. Herein, Ru- and Cl-codoped Li3 V2 (PO4 )3 (LVP-Rux -Cl3 x ) coated with/without a nitrogen-doped carbon (NC) layer are synthesized. Among them, the optimized sample (LVP-Ru0.05 -Cl0.15 @NC) delivers remarkable performances at both room temperature and extreme temperatures (-40, 25, and 60 °C), indicating temperature adaptability. It achieves intriguing capacities (49 mAh g-1 at -40 °C, 128 mAh g-1 at 25 °C, and 123 mAh g-1 at 60 °C, all at 0.5 C), long cycle life (94% capacity retention after 2000 cycles at 25 °C and 5 C), and high-rate capabilities (up to 20 C). The structural evolution features and capacity loss mechanisms of LVP-Ru0.05 -Cl0.15 @NC are further investigated using in situ X-ray diffraction (XRD) at different temperatures (-10, 25, and 60 °C) during redox reactions. Theoretical calculations elucidate that Ru- and Cl-codoping can greatly improve the intrinsic diffusion coefficient of LVP by reducing its bandgap energy and lowering the energy barrier of lithium-ion diffusion. In "all-weather" conditions, the dual-element co-doping strategy is critical for increasing electrochemical performance.

9.
Molecules ; 27(15)2022 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-35956771

RESUMO

Clay is found in some countries all over the world. It usually has low compressive strength and cannot be used as a bearing material for subgrade soil. In this paper, the influence of basicity on a metakaolin-based polymer binder to improve clay was studied. The effects of the molar concentration of the alkali activator, different concentration of the metakaolin-based geopolymer and curing time on unconfined compressive strength were studied. The alkali activator-to-ash ratio was maintained at 0.7. The percentage of metakaolin added to the soil relative to metakaolin and soil mixture was 6%, 8%, 10% and 12%. The sodium hydroxide concentrations are 2M, 4M, 6M and 8M. Unconfined compressive strength (UCS) was tested on days 3, 7, 14 and 28, respectively. Compared with original clay, the results show that the unconfined compressive strength increases with the increase in metakaolin content and molar concentration of NaOH. The maximum compressive strength of the sample with NaOH concentration of 8M and percentage of 12% was 4109 kN on the 28th day, which is about 112% higher than that of the original clay. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) results showed that the cementing compound covered the clay particles due to the reaction of the geopolymer with the clay, resulting in the formation of adhesive particles. The main purpose of this study is to verify the effectiveness and stability of metakaolin-based geopolymer binder polymerization under normal temperature and a strong alkali environment. The results can provide parameters for the application and promotion of metakaolin-based geopolymers in soil improvement engineering.

10.
J Food Sci Technol ; 59(7): 2867-2874, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35734127

RESUMO

Characteristics of sugar crystals are important for developing set-syrup due to their contribution to the desired mouth feel when consumed. Two types of set-syrup (i.e. seeds with and without) were developed by storing the syrup at -20, 4 and 15 °C. The melting temperatures (onset and peak), and enthalpy of set-syrup without seeds (SN) were 30.2 °C, 74.6 °C and 42.2 kJ/kg respectively. In the case of SN, enthalpy decreased with the decrease of crystallization temperature (P < 0.05), while there was insignificant change in the case of set-syrup with seeds (SW) (P > 0.05). Polarized Light Microscopy (PLM) images showed that finer crystals were formed in the cases of set-syrups (i.e. SN and SW) as the storage temperature was decreased. X-ray diffraction (XRD) analysis showed the formation of different polymorphic sugar crystals. Crystallization temperatures at 4 and -20 °C can be used to produce finer crystals with varied polymorphic characteristics.

11.
Anal Biochem ; 612: 113970, 2021 01 01.
Artigo em Inglês | MEDLINE | ID: mdl-32961250

RESUMO

Gold nanoparticles (AuNPs) are gaining a lot of attention in recent decades from researchers due to their unique optoelectronic properties and their significance in the field of biomedicine. Keeping this in view, our research work was designed to investigate gold nanoparticles obtained by using a fungal endophytic strain Chaetomium globosum, isolated from Vitex negundo which showed significant activity on enzyme inhibition. In the present study, the fungal isolate C. globosum was characterized using HPLC and LC-MS. A novel compound Catechin was matched with standard Catechin. Further, the endophyte C. globosum extract was utilized to synthesize gold nanoparticles (CgAuNPs) which was analysed by UV-visible spectroscopy. The CgAuNPs exhibited wine red color and the absorption peak appeared at 542 nm confirming the formation of the AuNPs. Further, Fourier Transmission Infrared Spectroscopy (FTIR) was performed to confirm the various functional groups present in mycosynthesized CgAuNPs. FTIR analysis demonstrated the presence of amines, flavonoids, as well as the presence of amide I linkage which possibly reduces Au+ to Au0. The synthesized CgAuNPs exhibited potential cytotoxicity against HeLa cells in a dose dependent manner. Further, CgAuNPs demonstrated significant anti-inflammatory activity. Overall, the present work provides insights into the design of nano delivery and may be applied for clinical studies in future.


Assuntos
Anti-Inflamatórios/química , Anti-Inflamatórios/farmacologia , Chaetomium/química , Endófitos/química , Ouro/química , Nanopartículas Metálicas/química , Ácido Acético/toxicidade , Animais , Anti-Inflamatórios/síntese química , Anti-Inflamatórios/uso terapêutico , Comportamento Animal/efeitos dos fármacos , Carragenina/toxicidade , Catequina/química , Catequina/farmacologia , Catequina/uso terapêutico , Chaetomium/metabolismo , Ciclo-Oxigenase 2/efeitos dos fármacos , Modelos Animais de Doenças , Edema/induzido quimicamente , Edema/tratamento farmacológico , Edema/patologia , Endófitos/isolamento & purificação , Endófitos/metabolismo , Feminino , Células HeLa , Humanos , Concentração de Íons de Hidrogênio , Inflamação/induzido quimicamente , Inflamação/tratamento farmacológico , Inflamação/patologia , Lipoxigenase/efeitos dos fármacos , Masculino , Nanopartículas Metálicas/uso terapêutico , Nanopartículas Metálicas/ultraestrutura , Camundongos , Folhas de Planta/química , Vitex/química , Vitex/metabolismo , Xantina Oxidase/antagonistas & inibidores , Xantina Oxidase/efeitos dos fármacos
12.
Bioprocess Biosyst Eng ; 44(4): 759-768, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33420818

RESUMO

Microbial fuel cells (MFCs) have significant interest in the research community due to their ability to generate electricity from biodegradable organic matters. Anode materials and their morphological structures play a crucial role in the formation of electroactive biofilms that enable the direct electron transfer. In this work, modified electrodes with nanomaterials, such as multiwalled carbon nanotubes (MWCNTs), reduced graphene oxide (rGO), Al2O3/rGO or MnO2/MWCNTs nanocomposites were synthesized, characterized and utilized to support the growth of electrochemically active biofilms. The MFC's performance is optimized using anode-respiring strains isolated from biofilm-anode surface, while the adjusted operation is conducted with the consortium of (Enterobacter sp.). Besides the formation of matured biofilm on its surface, MnO2/MWCNTs nanocomposite produced the highest electrical potential outputs (710 mV) combined with the highest power density (372 mW/m2). Thus, a correlation between the anode nanostructured materials and the progression of the electrochemically active biofilms formation is presented, allowing new thoughts for enhancing the MFC's performance for potential applications ranging from wastewater treatment to power sources.


Assuntos
Materiais Biocompatíveis/química , Fontes de Energia Bioelétrica , Eletrodos , Nanotubos de Carbono/química , Biofilmes , Eletricidade , Transporte de Elétrons , Desenho de Equipamento , Grafite , Compostos de Manganês , Teste de Materiais , Nanoestruturas , Óxidos , Purificação da Água/instrumentação , Difração de Raios X
13.
Sensors (Basel) ; 21(17)2021 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-34502631

RESUMO

We conducted experiments on SnO2 thin layers to determine the dependencies between the stoichiometry, electrochemical properties, and structure. This study focused on features such as the film structure, working temperature, layer chemistry, and atmosphere composition, which play a crucial role in the oxygen sensor operation. We tested two kinds of resistive SnO2 layers, which had different grain dimensions, thicknesses, and morphologies. Gas-sensing layers fabricated by two methods, a rheotaxial growth and thermal oxidation (RGTO) process and DC reactive magnetron sputtering, were examined in this work. The crystalline structure of SnO2 films synthesized by both methods was characterized using XRD, and the crystallite size was determined from XRD and AFM measurements. Chemical characterization was carried out using X-ray photoelectron (XPS) and Auger electron (AES) spectroscopy for the surface and the near-surface film region (in-depth profiles). We investigated the layer resistance for different oxygen concentrations within a range of 1-4%, in a nitrogen atmosphere. Additionally, resistance measurements within a temperature range of 423-623 K were analyzed. We assumed a flat grain geometry in theoretical modeling for comparing the results of measurements with the calculated results.

14.
Small ; 16(26): e2000504, 2020 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32510849

RESUMO

Transition metal chalcogenides have received great attention as promising anode candidates for sodium-ion batteries (SIBs). However, the undesirable cyclic life and inferior rate capability still restrict their practical applications. The design of micro-nano hierarchitectures is considered as a possible strategy to facilitate the electrochemical reaction kinetics and strengthen the electrode structure stability upon repeated Na+ insertion/extraction. Herein, urchin-like Fe3 Se4 hierarchitectures are successfully prepared and developed as a novel anode material for SIBs. Impressively, the as-prepared urchin-like Fe3 Se4 can present an ultrahigh rate capacity of 200.2 mAh g-1 at 30 A g-1 and a prominent capacity retention of 99.9% over 1000 cycles at 1 A g-1 , meanwhile, a respectable initial coulombic efficiency of ≈100% is achieved. Through the conjunct study of in situ X-ray diffraction, ex situ X-ray absorption near-edge structure spectroscopy, as well as cyclic voltammetry curves, it is intriguing to reveal that the phase transformation from monoclinic to amorphous structure accompanied by the pseudocapacitive Na+ storage behavior accounts for the superior electrochemical performance. When paired with the Na3 V2 (PO4 )3 cathode materials, the assembled full cell enables high energy density and decent cyclic stability, demonstrating potential practical feasibility of the present urchin-like Fe3 Se4 anode.

15.
Molecules ; 25(10)2020 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-32466174

RESUMO

Results of a detailed structural characterization of nominally pure and doped single crystals of scheelite, eulytin, and perovskite families obtained by melt methods were considered and analyzed. The influence of growth and post-growth annealing conditions on actual compositions of crystals is shown. The reasons for the coloration of the crystals are explained. A change in crystal symmetry due to crystal-chemical and growth reasons is considered. The use of structural analysis and X-ray absorption spectroscopy is substantiated to reveal the role of activator ions in the formation of statistical and local structures, respectively. A relationship between the distribution of activator ions over crystallographic sites and photoluminescent parameters of materials is established, which allows selecting optimal systems for the application. The combined results of studying single-crystal compounds of other classes (huntite, sillenite, whitlockite, garnet, tetragonal bronzes) allow formulating and summarizing structural effects that appeared in the systems and caused by various factors and, in many cases, due to the local environment of cations. A principal difference in the structural behavior of solid solutions and doped compounds is shown. The methodology developed for single-crystal samples of complex compositions can be recommended for the systematic structural studies of functional materials of different compositions.


Assuntos
Compostos de Cálcio/química , Fosfatos de Cálcio/química , Cristalização/métodos , Óxidos/química , Titânio/química , Luminescência , Modelos Químicos , Espectroscopia por Absorção de Raios X , Difração de Raios X
16.
J Mater Res ; 34(3): 465-473, 2019 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33776202

RESUMO

Cerium oxide Nanoparticles (CNPs) are of significant interest to the scientific community due to their wide spread applications in a variety of fields. It is proposed that size dependent variations in the extent of Ce3+ and Ce4+ oxidation states of cerium in CNPs determines the performance of CNPs in application environments. To obtain greater molecular and structural understanding of chemical state transformations previously reported for ceria ≈ 3 nm nanoparticles (CNPs) in response to changing ambient conditions, microXRD and Raman measurements were carried out for various solution conditions. The particles were observed to undergo a reversible transformation from a defective ceria structure to a non-ceria amorphous oxy-hydroxide/peroxide phase in response to the addition of 30% hydrogen peroxide. For CNPs made up of ~8 nm crystallites, a partial transformation was observed and no transformation was observed for CNPs made up of ~ 40 nm crystallites. This observation of differences in size dependent transition behavior may help explain the benefits of using smaller CNPs in applications requiring regenerative behavior.

17.
J Food Sci Technol ; 56(1): 187-199, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30728560

RESUMO

Komal chawal, meaning soft rice, produced by brown rice parboiling of a low amylose rice variety chokuwa, was studied for its physical, physico-chemical, morphological and structural characteristics. The product was produced by soaking the brown rice at 60 °C for 90 min, followed by steaming and air drying to 12.0% (wb). The two steaming conditions used were: (1) open-steaming at atmospheric pressure for 20 min and (2) pressure-steaming at 1 atm (gauge) for 10 min. The three different drying temperatures used were 40, 50 and 60 °C. When soaked in water at 60 °C for 20 min the product attained a hardness value of cooked rice. The extent of changes in the kernel and flour properties as compared to the raw form were affected by the severity of the steaming condition and drying air temperature. The pressure steamed samples exhibited virtually persistent growth in paste viscosity in the profiles obtained from the rapid viscosity analyzer. X-ray diffraction analysis of flours revealed a loss of A-type pattern and formation of feeble peaks of A + V-type mixed patterns in steam-treated samples. Scanning electron photomicrographs showed the loss of the polygonal shape by starch granules during processing. The values of rehydration ratio, equilibrium moisture content for rehydration, sediment volume, extent of color change as denoted by total color difference, and the percent head rice yield were higher in pressure steamed komal chawal samples.

18.
J Occup Environ Hyg ; 15(10): 743-754, 2018 10.
Artigo em Inglês | MEDLINE | ID: mdl-29985762

RESUMO

Evaluation and control of respirable crystalline silica (RCS) exposures are critical components of an effective mine industrial hygiene program. To provide more timely exposure data in the field, an end-of-shift Fourier transform infrared (FT-IR) spectrometry method has been developed for evaluation of direct-on-filter RCS. The present study aimed to apply this FT-IR method using field samples collected in three Northwestern U.S. metal/nonmetal mines and compare the results to traditional laboratory X-ray diffraction analysis (XRD). Seventy-five dust samples were analyzed using both methods. Samples for each mine were split in half by random assignment, with half used to create a calibration factor for the FT-IR analysis and half used to apply the calibration. Nonparametric correlational and two-sample comparative tests were used to assess the strength of association and the level of agreement between the two methods. Strong, positive correlations were observed between FT-IR and XRD RCS concentrations, with Spearman rank correlation coefficients ranging between 0.84 and 0.97. The mean RCS concentrations determined through FT-IR analysis were lower than through XRD analysis, with mean differences ranging from -4 to -133 ug/m3 and mean percent errors ranging from 12% to 28%. There was a statistically significant improvement in the level of agreement between log FT-IR and log XRD RCS concentrations following calibration at two of the three mines, with mean differences of -0.03 (p = 0.002) and -0.02 (p = 0.044) in the log scale. The reduction in mean difference following calibration at the other mine was not statistically significant (mean log scale difference = -0.05, p = 0.215), but the differences between FT-IR and XRD were not significantly different without calibration (mean log scale difference = -0.07, p = 0.534). The results indicate that mine-specific calibration factors can improve the level of agreement between RCS concentrations determined via a field-based, end-of-shift FT-IR method in metal/non-metal mines as compared to traditional XRD analysis.


Assuntos
Poluentes Ocupacionais do Ar/análise , Dióxido de Silício/análise , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Difração de Raios X/métodos , Calibragem , Monitoramento Ambiental/métodos , Filtração/métodos , Mineração , Noroeste dos Estados Unidos
19.
Sci Justice ; 58(2): 138-144, 2018 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-29526265

RESUMO

Soil traces are useful as forensic evidences because they frequently adhere to individuals and objects associated with crimes and can place or discard a suspect at/from a crime scene. Soil is a mixture of organic and inorganic components and among them soil clay contains signatures that make it reliable as forensic evidence. In this study, we hypothesized that soils can be forensically distinguished through the analysis of their clay fraction alone, and that samples of the same soil type can be consistently distinguished according to the distance they were collected from each other. To test these hypotheses 16 Oxisol samples were collected at distances of between 2m and 1.000m, and 16 Inceptisol samples were collected at distances of between 2m and 300m from each other. Clay fractions were extracted from soil samples and analyzed for hyperspectral color reflectance (HSI), X-ray diffraction crystallographic (XRD), and for contents of iron oxides, kaolinite and gibbsite. The dataset was submitted to multivariate analysis and results were from 65% to 100% effective to distinguish between samples from the two soil types. Both soil types could be consistently distinguished for forensic purposes according to the distance that samples were collected from each other: 1000m for Oxisol and 10m for Inceptisol. Clay color and XRD analysis were the most effective techniques to distinguish clay samples, and Inceptisol samples were more easily distinguished than Oxisol samples. Soil forensics seems a promising field for soil scientists as soil clay can be useful as forensic evidence by using routine analytical techniques from soil science.

20.
J Environ Sci Health B ; 52(5): 291-297, 2017 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-28277083

RESUMO

This study was undertaken to determine the impact of the organic complex concentration on the adsorption of herbicide (acetochlor) at the surface of the organic modified montmorillonite. In this work, natural montmorillonite from Bogovina (Boljevac municipality, Serbia) was used for organic modification. Cation-exchange capacity of this montmorillonite was determined using a methylene blue method (86 mmol/100 g of clay). Montmorillonite has been modified first with NaCl and then with hexadecyltrimethylammonium bromide (HDTMA-bromide) organic complex. Saturation of cation exchange capacity (CEC) was 50%, 100%, and 150%. Changes in the properties of the inorganic and organic montmorillonite have been examined using the X-ray diffraction, Fourier transform infrared spectroscopy, and batch equilibrium method. Montmorillonite modified with HDTMA-bromide demonstrated higher uptake of the herbicide, compared to the inorganic montmorillonite. Comparing the values Freundlich coefficients in batch equilibrium method, it can be seen that the adsorption of acetochlor decreased in the series: 0.5 CEC HM > 1 CEC HM > 1.5 CEC HM > NaM.


Assuntos
Bentonita/química , Herbicidas/química , Toluidinas/química , Adsorção , Silicatos de Alumínio/química , Cetrimônio , Compostos de Cetrimônio/química , Argila , Poluentes Ambientais/química , Azul de Metileno/química , Sérvia , Espectroscopia de Infravermelho com Transformada de Fourier , Difração de Raios X
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