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1.
Chemosphere ; 357: 142038, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38621486

RESUMEN

Mercury (Hg) stable isotope ratios supplemented by Hg solid speciation data were determined in soils in a former Fe-Hg mining/smelting area (Jedová hora, Czech Republic, Central Europe). The dominant Hg phase in the studied soils was found to be cinnabar (HgS). A secondary form of soil Hg(II) was represented by Hg weakly and strongly bound to mineral (micro)particles, as revealed by thermo-desorption analysis. These Hg species probably play a key role in local soil Hg processes and biogeochemical cycling. The Hg isotopic data generally showed small differences between HgS (-1.1 to -0.8‰; δ202Hg) and the soil samples (-1.4 to -0.9‰; δ202Hg), as well as limited isotopic variability within the two studied soil profiles. On the other hand, the detected negative δ202Hg shift (∼0.4‰) in organic horizons compared to mineral soils in the highly contaminated profile suggests the presence of secondary post-depositional Hg processes, such as sorption or redox changes. For the less contaminated profile, the observed Hg isotopic variation (∼0.3‰; δ202Hg) in the subsurface mineral soil compared to both overlying and underlying horizons is likely due to cyclic redox reactions associated with Hg isotopic fractionation. We assume that the adsorption of Hg(II) to secondary Fe(III)/Mn(III,IV)-oxides could be of major importance in such cases.


Asunto(s)
Monitoreo del Ambiente , Hierro , Mercurio , Minería , Contaminantes del Suelo , Suelo , Mercurio/análisis , Mercurio/química , Contaminantes del Suelo/análisis , Contaminantes del Suelo/química , Suelo/química , Monitoreo del Ambiente/métodos , República Checa , Hierro/química , Hierro/análisis , Isótopos de Mercurio/análisis , Compuestos de Mercurio
2.
Environ Sci Technol ; 58(14): 6381-6390, 2024 Apr 09.
Artículo en Inglés | MEDLINE | ID: mdl-38547454

RESUMEN

The objective of this study was to determine if U sediment concentrations in a U-contaminated wetland located within the Savannah River Site, South Carolina, were greater in the rhizosphere than in the nonrhizosphere. U concentrations were as much as 1100% greater in the rhizosphere than in the nonrhizosphere fractions; however and importantly, not all paired samples followed this trend. Iron (but not C, N, or S) concentrations were significantly enriched in the rhizosphere. XAS analyses showed that in both sediment fractions, U existed as UO22+ coordinated with iron(III)-oxides and organic matter. A key difference between the two sediment fractions was that a larger proportion of U was adsorbed to Fe(III)-oxides, not organic matter, in the rhizosphere, where significantly greater total Fe concentrations and greater proportions of ferrihydrite and goethite existed. Based on 16S rRNA analyses, most bacterial sequences in both paired samples were heterotrophs, and population differences were consistent with the generally more oxidizing conditions in the rhizosphere. Finally, U was very strongly bound to the whole (unfractionated) sediments, with an average desorption Kd value (Usediment/Uaqueous) of 3972 ± 1370 (mg-U/kg)/(mg-U/L). Together, these results indicate that the rhizosphere can greatly enrich U especially in wetland areas, where roots promote the formation of reactive Fe(III)-oxides.


Asunto(s)
Compuestos Férricos , Uranio , Humedales , Rizosfera , ARN Ribosómico 16S , Hierro , Óxidos/análisis , Oxidación-Reducción , Sedimentos Geológicos/microbiología
3.
Food Chem ; 448: 139123, 2024 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-38552461

RESUMEN

In the present work, liposomes have been used as nanocarriers in the biofortification of wheat plants with selenium (Se) through foliar application. Liposomal formulations were prepared using 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and Phospholipon®90H (P90H) (average size <100 nm), loaded with different concentrations of inorganic Se (selenite and selenate) and applied twice to the plants in the stage of vegetative growth. Liposomes enhanced Se uptake by wheat plants compared to direct application. The highest Se enrichment was achieved using the phospholipid DPPC and a concentration of 1000 µmol·L-1 of Se without affecting the biomass, chlorophylls, carotenoids, and the concentration of mineral nutrients of the plants. The chemical speciation of Se in the plants was further investigated by X-ray absorption spectroscopy (XAS). The results from XAS spectra revealed that most of the inorganic Se was transformed to organic Se and that the use of liposomes influenced the proportion of C-Se-C over C-Se-Se-C species.


Asunto(s)
Biofortificación , Liposomas , Hojas de la Planta , Selenio , Triticum , Triticum/química , Triticum/crecimiento & desarrollo , Triticum/metabolismo , Liposomas/química , Selenio/química , Selenio/metabolismo , Selenio/análisis , Hojas de la Planta/química , Hojas de la Planta/metabolismo , Hojas de la Planta/crecimiento & desarrollo , Nanopartículas/química , Portadores de Fármacos/química
4.
Environ Res ; 252(Pt 1): 118694, 2024 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-38521357

RESUMEN

The contribution of smelting of nonferrous metals to heavy metals in surface soil have become increasingly important over the past decade. In this study, the distribution of heavy metals around an abandoned mercury-bearing waste recovery enterprise were investigated. Soil (14) and plant (18) samples were collected in the surrounding area. The total concentration of heavy metals and methyl mercury content were measured by ICP-MS and HPLC-ICP-MS. The results show that the average contents of Cd, Cr, Pb, Hg and As in all soil samples are higher than the second-level values of Soil environmental quality-Risk control standard for soil contamination of development land (GB 36600-2018). Hg in the leaves ranged from 0.003 to 0.174 mg kg-1. Besides, the Pearson correlation analysis results indicate that Hg has a different environmental behavior compared to the other heavy metal under certain environmental or geographical conditions. But the mantel test statistical analysis results show that the Cr (P < 0.01), Cu, Pb, and Fe (P < 0.05) in the soil may have similar pollution sources with carbonate-bound mercury and iron-manganese oxide-bound mercury. The Hg concentrations show no correlation among plant leaves and soil, but significantly influenced by the distance and wind direction. These findings suggest that Hg in plant leaves may be derived from the deposition of atmospheric mercury from secondary mercury plant. The results will supplement those for relevant policy making for mercury-bearing waste recovery enterprises to improve urban environmental quality and human health.


Asunto(s)
Monitoreo del Ambiente , Mercurio , Metales Pesados , Contaminantes del Suelo , Contaminantes del Suelo/análisis , China , Metales Pesados/análisis , Mercurio/análisis , Suelo/química , Plantas/química , Contaminación Ambiental/análisis
5.
PhytoKeys ; 238: 281-294, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38456167

RESUMEN

Species limits in the genus Cistanche are poorly understood, despite the plants' long history of use in traditional herbal medicine and food across their range. Here we present a taxonomic account for the genus Cistanche in Iraq, where several taxa have been reported, most of them doubtfully. Using herbarium specimens, images of living material, and taxonomic literature, we found evidence of only one species occurring with certainty in Iraq: Cistanchetubulosa. We found no evidence for the occurrence of other Cistanche species in Iraq, including a putative new entity reported for the region. Our work highlights inconsistencies in the literature, and underscores the importance of examining multiple stable characters for delimiting species in the genus Cistanche.

6.
Chemosphere ; 352: 141366, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38311037

RESUMEN

The oxidation of pyrite results in the formation of a solid film passivation layer on its surface. This layer effectively hinders the direct interaction between H2O, O2, and the pyrite surface, thereby impeding the oxidation dissolution of pyrite. There are few studies on whether alumina (Al2O3), a common aluminum-containing oxide, affects the formation of a solid film passivation layer on the surface of pyrite and inhibits the oxidation dissolution of pyrite. This research investigates the impact of Al2O3 incorporation on the speciation transformation of S, Fe, and Al on the surface of pyrite during oxygen pyrite process. The oxidation of pyrite followed the "polysulfide-thiosulfate" complex oxidation pathway. When <1.5 g/L Al2O3 was introduced, it increase pyrite oxidation, whereas ≥1.5 g/L Al2O3 prevented pyrite oxidation. The process of Al2O3 dissolution results in the consumption of H+ and the subsequent release of Al3+. This, in turn, facilitates the hydrolysis of Fe3+ and Al3+ to generate a secondary mineral layer on the pyrite surface. As a result of the accumulation of S promotes the formation of polysulfide chemical (FeSn) or iron deficiency sulfide (Fe1-xS), resulting in the formation of a solid film passivation layer composed of sulfur film and secondary mineral layer. The results demonstrated that Al2O3 can promote the formation of a solid film passivation layer on the surface of pyrite, which has significant implications for controlling the oxidation dissolution process of pyrite and offers a new perspective for the source control of acid mine drainage.


Asunto(s)
Óxido de Aluminio , Hierro , Minerales , Sulfuros/metabolismo , Oxidación-Reducción , Estrés Oxidativo
7.
Sci Total Environ ; 918: 170582, 2024 Mar 25.
Artículo en Inglés | MEDLINE | ID: mdl-38309349

RESUMEN

Phosphorus (P) loss caused by the irrational use of manure organic fertilizer has become a worldwide environmental problem, which has caused a potential threat to water safety and intensified agricultural non-point source pollution. Hydrothermal carbonization is method with a low-energy consumption and high efficiency to deal with environmental problems. Application of pig manure-derived hydrochar (PMH) to soil exhibited potential of sustainable development compared with the pristine pig manure (PM). However, the effects of PMH on the distribution of P among the fractions/forms and the interaction between microorganisms and P forms and its relevance to the potential loss of P in paddy fields has not been clarified. Therefore, in this study, a soil column experiment was conducted using the untreated soil (control), and the PM, PMH1 (PMH derived at 180 °C), and PMH2 (PMH derived at 260 °C) treated soils (at the dose of 0.05 %) and rice was cultivated to investigate the effects of PM and PMH on the P fractions, mobilization, ad potential loss via the induced changes on soil microbial community after a complete growing season of rice. The trend of P utilization was evaluated by P speciation via continuous extraction and 31P NMR. The addition of PMH reduced the proportion of residual P in soil by 23.8-26.3 %, and increased the proportion of HCl-P and orthophosphate by 116.2-158.6 % and 6.1-6.8 % compared to PM. The abundance of gcd gene developed after the application of PMH2, which enhanced the mobile forms of soil P utilization via secreting gluconic acid. The network diagram analysis concluded that the changes in various P forms were mainly related to Proteobacteria, Bacteroides, Firmicutes and Acidobacteria. The results illustrated that PMH mitigate the potential risk of P loss more than PM by altering P fractions and affecting soil microbial community.


Asunto(s)
Microbiota , Oryza , Porcinos , Animales , Suelo/química , Oryza/microbiología , Estiércol , Fósforo/análisis , Fertilizantes/análisis
8.
Food Chem ; 443: 138607, 2024 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-38301552

RESUMEN

Food crops provide a good selenium (Se) source for Se-deficient populations. This study assessed how boiling affects Se concentration, speciation, and bioaccessibility in common food crops to determine human Se intake. Boiling rice resulted in an 11.9% decrease in minimum Se content, while sorghum experienced a maximum (34.9%) reduction. Boiled vegetables showed a 21% - 40% Se loss. Cereals showed notable decreases in selenomethionine (SeMet) and selenocysteine (SeCys2), while most vegetables exhibited a significant reduction in Se-methylselenocysteine (SeMeCys). Boiling significantly reduced the Se bioaccessibility in all food crops, except cabbage and potato. Cereal crops were more efficacious in meeting the recommended daily intake (RDI) of Se compared to vegetables. Rice exceeds other crops and provides up to 39.2% of the WHO/FAO-recommended target minimum daily intake of 60 µg/day. This study provides insight into a substantial dissonance between the estimated daily intake (EDI) of Se and the bioaccessible Se in both raw and boiled crops. Consequently, revising EDI standards is imperative.


Asunto(s)
Selenio , Humanos , Selenometionina/análisis , Productos Agrícolas , Grano Comestible/química , Verduras
9.
Molecules ; 29(1)2024 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-38202818

RESUMEN

Selenium-enriched yeast possesses the unique ability of transforming chemical selenium, such as sodium selenite, into a biologically active form, which mitigates its toxic effects on the human body. The transformation product of this process, selenomethionine, can be safely and effectively absorbed and utilized by the human body; hence, it has been spiked into a selenium-enriched supplement. This study employs two distinct measurement strategies to determine the selenomethionine content in two candidate reference materials, a selenium-enriched yeast powder and supplement, using both organic and inorganic mass spectrometry. The concentrations of selenomethionine in the selenium-enriched yeast were determined using HPLC-ICP-MS and HPLC- ESI-MS/MS, with mass fractions measured at 718 mg SeMet kg-1 and 715 mg SeMet kg-1, respectively. Notably, both methods yielded consistent results for the selenium supplement, with a selenomethionine mass fraction of 59 mg SeMet kg-1. Ultimately, the certified values of these candidate reference materials were determined as 716 mg kg-1 and 59 mg SeMet kg-1 with expanded uncertainties of 36 mg SeMet kg-1 (k = 2) and 5 mg SeMet kg-1 (k = 2), respectively. The development of these candidate reference materials serves as a valuable reference for diverse methods aiming to determine the value of organic selenium speciation in complex food substrates.


Asunto(s)
Saccharomyces cerevisiae , Selenio , Humanos , Selenometionina , Espectrometría de Masas en Tándem , Suplementos Dietéticos , Certificación
10.
Food Chem ; 443: 138460, 2024 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-38295566

RESUMEN

Currently, planting selenium-rich crops using inorganic selenium such as selenate and selenite is used to address human selenium deficiency problems. In this paper, besides the above two traditional inorganic selenium speciation, we chose a new organic selenium speciation of potassium selenocyanoacetate to investigate the different effects of selenium speciation on selenium absorption, selenium transformation and cadmium antagonism via foliar application. Plantingexperiments showed that the selenium content of garlic bulbs treated with organic selenium was 1.8-3.9 times higher than that of inorganic selenium. Additionally, the absorption and transformation efficiency of organic selenium in garlic was also the highest, reaching over 95 %. Importantly, it was noteworthy that the cadmium content in bulbs treated with organic selenium was significantly lower than the Chinese food safety standard (0.2 mg/kg). Hence, this study provides an efficient organic selenium speciation which is beneficial to meet human selenium requirements and ensure safe utilization of cadmium-contaminated soils.


Asunto(s)
Ajo , Selenio , Humanos , Selenio/farmacología , Cadmio , Ácido Selenioso , Antioxidantes , Ácido Selénico
11.
Anal Bioanal Chem ; 416(11): 2835-2848, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38286852

RESUMEN

This work presents the first systematic comparison of selenium (Se) speciation in plasma from cancer patients treated orally with three Se compounds (sodium selenite, SS; L-selenomethionine, SeMet; or Se-methylselenocysteine, MSC) at 400 µg/day for 28 days. The primary goal was to investigate how these chemical forms of Se affect the plasma Se distribution, aiming to identify the most effective Se compound for optimal selenoprotein expression. This was achieved using methodology based on HPLC-ICP-MS after sample preparation/fractionation approaches. Measurements of total Se in plasma samples collected before and after 4 weeks of treatment showed that median total Se levels increased significantly from 89.6 to 126.4 µg kg-1 Se (p < 0.001), particularly when SeMet was administered (190.4 µg kg-1 Se). Speciation studies showed that the most critical differences between treated and baseline samples were seen for selenoprotein P (SELENOP) and selenoalbumin after administration with MSC (p = 5.8 × 10-4) and SeMet (p = 6.8 × 10-5), respectively. Notably, selenosugar-1 was detected in all low-molecular-weight plasma fractions following treatment, particularly with MSC. Two different chromatographic approaches and spiking experiments demonstrated that about 45% of that increase in SELENOP levels (to ~ 8.8 mg L-1) with SeMet is likely due to the non-specific incorporation of SeMet into the SELENOP affinity fraction. To the authors' knowledge, this has not been reported to date. Therefore, SELENOP is probably part of both the regulated (55%) and non-regulated (45%) Se pools after SeMet administration, whereas SS and MSC mainly contribute to the regulated one.


Asunto(s)
Neoplasias , Compuestos de Selenio , Selenio , Humanos , Selenometionina , Neoplasias/tratamiento farmacológico , Biomarcadores
12.
Food Chem ; 439: 138156, 2024 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-38064828

RESUMEN

The paper presents a new analytical procedure for the determination and speciation of trace and ultratrace selenium in water, beverages, seafood, milk, and vegetables. The developed method is based on the dispersive micro-solid phase extraction with the use of new thiosemicarbazide-incorporated graphene as a solid sorbent, in combination of the total-reflection X-ray fluorescence spectrometry (TXRF). As a result, we have created an auspicious analytical tool for fast and sensitive analysis of samples with a complex matrix. Regardless of the specimen type, the method is characterized by a very low detection limit of 1.7 pg mL-1 and high precision. The developed strategy allowed us to solve common problems associated with selenium loss during the sample preparation for the TXRF measurement and also improve its performance toward the analysis of beverages and high saline/solid samples, which may even be impossible to perform using standard sample preparation procedures for a TXRF measurement.


Asunto(s)
Grafito , Selenio , Agua , Selenio/análisis , Grafito/química , Espectrometría por Rayos X/métodos , Bebidas/análisis
13.
Anal Sci ; 40(2): 309-317, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-37980326

RESUMEN

Arsenic is ranked as the first compound in the Substance Priority List 2023 by the Agency for Toxic Substances and Disease Registry (ATSDR). The most prominent entrance to the human body is through drinking water wherein the predominant species are arsenite and arsenate. The more toxic As(III) has rigorously threatened human health worldwide; hence, speciation and separation are the need of the hour. In this article, we have reported a simple method of arsenic speciation by wavelength dispersive X-ray fluorescence (WD-XRF) spectrometer. Valence to core (VtC) electronic transitions, i.e., AsKß2,5 fluorescence lines were used for arsenic speciation. This speciation study by WD-XRF entails direct measurement of activated alumina pellets containing arsenate and arsenite species adsorbed from water sample without separation of the trivalent and pentavalent species. This is the first report wherein the X-ray technique has been explored for speciation analysis of arsenic and the biggest advantage of the method lies in its applicability to direct analysis of synthesized nanotubes or other solid-phase extraction sorbents entrapping both the arsenic species. For determination of total arsenic using activated alumina as adsorbent, the most intense AsKα1,2 analytical lines were used and the instrumental limit of detection and the lower limit of quantification were 0.23 µg/L and 0.89 µg/L, respectively. For speciation, these limits were calculated to be 50 µg/L and 200 µg/L, respectively.


Asunto(s)
Arsénico , Arsenitos , Agua Potable , Humanos , Agua Potable/química , Arsénico/análisis , Arseniatos , Rayos X , Análisis Espectral , Óxido de Aluminio
14.
Plant J ; 118(1): 171-190, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38128038

RESUMEN

Sugar beet and its wild relatives share a base chromosome number of nine and similar chromosome morphologies. Yet, interspecific breeding is impeded by chromosome and sequence divergence that is still not fully understood. Since repetitive DNAs are among the fastest evolving parts of the genome, we investigated, if repeatome innovations and losses are linked to chromosomal differentiation and speciation. We traced genome and chromosome-wide evolution across 13 beet species comprising all sections of the genera Beta and Patellifolia. For this, we combined short and long read sequencing, flow cytometry, and cytogenetics to build a comprehensive framework that spans the complete scale from DNA to chromosome to genome. Genome sizes and repeat profiles reflect the separation into three gene pools with contrasting evolutionary patterns. Among all repeats, satellite DNAs harbor most genomic variability, leading to fundamentally different centromere architectures, ranging from chromosomal uniformity in Beta and Patellifolia to the formation of patchwork chromosomes in Corollinae/Nanae. We show that repetitive DNAs are causal for the genome expansions and contractions across the beet genera, providing insights into the genomic underpinnings of beet speciation. Satellite DNAs in particular vary considerably between beet genomes, leading to the evolution of distinct chromosomal setups in the three gene pools, likely contributing to the barriers in beet breeding. Thus, with their isokaryotypic chromosome sets, beet genomes present an ideal system for studying the link between repeats, genomic variability, and chromosomal differentiation and provide a theoretical fundament for understanding barriers in any crop breeding effort.


Asunto(s)
Beta vulgaris , Beta vulgaris/genética , Secuencia de Bases , ADN Satélite , Pool de Genes , Fitomejoramiento , Secuencias Repetitivas de Ácidos Nucleicos/genética , Verduras/genética , ADN , Centrómero/genética , Azúcares
15.
Environ Technol ; : 1-15, 2023 Nov 16.
Artículo en Inglés | MEDLINE | ID: mdl-37970842

RESUMEN

Sewage sludge requires effective dewatering and high nutrients retention before disposal for agricultural application. Pressurized electro-osmotic dewatering (PEOD) process with low energy consumption can effectively remove water from sludge, but the influences of PEOD process on nutrients for agricultural application still lacks in-depth research. In this study, the influences of PEOD process on nutrients for agricultural application were investigated, including organic matter, nitrogen, phosphorus, potassium and silicon contents. Layered experiments were conducted to investigate the layered variation of nutrients in sludge and to understand the potential change mechanisms. The experimental results showed that PEOD process caused small losses (<10%) of organic matter and total phosphorus (TP) in sludge, but caused 11.2-18.4% loss of total nitrogen (TN). PEOD process also caused 18.6-27.0% loss of total potassium (TK) and over 80% loss of available potassium in sludge, and could weaken the potential salt damage during the agricultural application of sludge. Furthermore, the available phosphorus content of sludge in the anode area increased significantly after the PEOD process, indicating that PEOD process could enhance the phosphorus bioavailability of sludge in the anode area. Besides, PEOD process caused a slight loss of silicon components in sludge, but improved the long-term silicon dissolution and release ability of sludge. This work could expand the knowledge about the influences of PEOD process on sludge nutrients and provide scientific guidance for the agricultural application of PEOD sludge.

16.
Int J Mol Sci ; 24(21)2023 Oct 27.
Artículo en Inglés | MEDLINE | ID: mdl-37958659

RESUMEN

Over the last four decades, vanadium compounds have been extensively studied as potential antidiabetic drugs. With the present review, we aim at presenting a general overview of the most promising compounds and the main results obtained with in vivo studies, reported from 1899-2023. The chemistry of vanadium is explored, discussing the importance of the structure and biochemistry of vanadate and the impact of its similarity with phosphate on the antidiabetic effect. The spectroscopic characterization of vanadium compounds is discussed, particularly magnetic resonance methodologies, emphasizing its relevance for understanding species activity, speciation, and interaction with biological membranes. Finally, the most relevant studies regarding the use of vanadium compounds to treat diabetes are summarized, considering both animal models and human clinical trials. An overview of the main hypotheses explaining the biological activity of these compounds is presented, particularly the most accepted pathway involving vanadium interaction with phosphatase and kinase enzymes involved in the insulin signaling cascade. From our point of view, the major discoveries regarding the pharmacological action of this family of compounds are not yet fully understood. Thus, we still believe that vanadium presents the potential to help in metabolic control and the clinical management of diabetes, either as an insulin-like drug or as an insulin adjuvant. We look forward to the next forty years of research in this field, aiming to discover a vanadium compound with the desired therapeutic properties.


Asunto(s)
Diabetes Mellitus , Compuestos de Vanadio , Animales , Humanos , Hipoglucemiantes/farmacología , Hipoglucemiantes/uso terapéutico , Hipoglucemiantes/química , Compuestos de Vanadio/farmacología , Compuestos de Vanadio/uso terapéutico , Compuestos de Vanadio/química , Vanadio/química , Diabetes Mellitus/tratamiento farmacológico , Insulina/uso terapéutico , Insulina Regular Humana/uso terapéutico
17.
Polymers (Basel) ; 15(20)2023 Oct 14.
Artículo en Inglés | MEDLINE | ID: mdl-37896326

RESUMEN

The design, characterization, and analytical application of a green optical sensor for the selective determination of Fe(II) ions is proposed. The sensor is based on the immobilization of the chromogenic reagent picolinaldehyde salicyloylhydrazone (SHPA) within a polymer inclusion membrane. To reduce solvent usage, the reagent was synthesized using a green mechanochemical procedure. The components for sensor preparation were optimized with a sequential simplex method and the optimal composition was found to be 0.59 g cellulose triacetate (base polymer), 0.04 g SHPA (chemosensor reagent), 4.9 mL dibutyl phthalate (plasticizer), and 38 mL dichloromethane (solvent). The conditions of iron analysis were also optimized resulting in pH 6 for aqueous solution, 90 min exposure time and 10 min short-term stability. The optical sensor showed a linear range from the limit of detection (0.48 µmol L-1) to 54 µmol L-1 Fe(II). The precision of the method was found to be 1.44% and 1.19% for 17.9 and 45 µmol L-1 Fe(II), respectively. The characteristics of the sensor allowed the design of a Fe(II)/Fe(III) speciation scheme. The methodology was successfully applied to the determination of iron in food preservatives, food additives, and dietary supplement. Additionally, the Fe speciation scheme was successfully applied to an agricultural fertilizer.

18.
Anal Bioanal Chem ; 415(29-30): 7175-7186, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37819434

RESUMEN

This study reports the development and validation of a new analytical method for simultaneous speciation analysis of Se and Hg in fish muscle. For this purpose, four Se species (selenite/Se(IV), selenate/Se(VI), selenomethionine/SeMet, and selenocysteine/SeCys) and two Hg species (inorganic mercury/iHg and methylmercury/MeHg) were extracted simultaneously by microwave-assisted enzymatic hydrolysis and then separated by HPLC in less than 15 min by using a column with both anion and cation exchange mechanisms and a mobile phase consisting of a mixture of methanol 5% (v/v), 45 mM HNO3, 0.015% 2-mercaptoethanol, and 1.5 mM sodium 3-mercapto-1-propanesulfonate. The separated species of Hg and Se were detected online by inductively coupled plasma-mass spectrometry (ICP-MS). The speciation analysis method was validated by means of the accuracy profile approach by carrying out three series of measurements in duplicate on three different days over a time-span of 3 weeks. The limits of quantification (LOQ) are in the range of 0.010-0.013 mg/kg wet weight (ww) for all selenium species, except for Se(IV) (0.15 mg/kg ww), while the coefficient of variation in terms of intermediate reproducibility (CVR) was < 7%. The LOQ for MeHg was 0.006 mg/kg ww, while the CVR was 3%. The method was successfully applied to the analysis of muscle samples from four different fish species: rainbow trout, tuna, swordfish, and dogfish.


Asunto(s)
Mercurio , Selenio , Animales , Cromatografía Líquida de Alta Presión/métodos , Hidrólisis , Microondas , Reproducibilidad de los Resultados , Espectrometría de Masas/métodos , Mercurio/análisis , Selenio/análisis , Peces , Atún
19.
Environ Sci Pollut Res Int ; 30(46): 103141-103152, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37682438

RESUMEN

Arsenic (As) is a naturally occurring element that is found in soil, water, and rocks. However, it can also be released into the environment through human activities. Arsenic is considered an environmental hazard because it is toxic to humans and animals and can cause serious health problems. Additionally, As-contaminated soil can limit plant growth and reduce crop yields, leading to economic losses for farmers. So, decreasing metal/metalloid solubility in soil by synthetic and organic amendments leads to better crop productivity on contaminated soils. The current study aimed to evaluate farmyard manure (FYM)-mediated changes in soil arsenic (As) behavior, and subsequent effects on achene yield of sunflower. Treatment plan comprised of two As levels, i.e., As-60 (60 mg kg-1) and As-120 (120 mg kg-1), four FYM levels (0, 20, 35, and 50 g kg-1), three textural types (sandy, loamy and clayey), and replicated thrice. Seven As fractions including water soluble-As (WS-As), labile-As (L-As), calcium-bound As (Ca-As), aluminum-bound As (Al-As), iron-bound As (Fe-As), organic-matter-bound As (OM-As), and residual-As (R-As) were determined which differed significantly (P ≤ 0.05) with FYM and soil texture. FYM supplementation decreased WS-As, L-As, Ca-As, and Al-As while increased Fe-As, OM-As, and R-As. The immobilizing effect of FYM increased with increasing its rate of application, and maximum effect was found in clayey soil. As speciation in soil also significantly (P ≤ 0.05) affected by FYM and soil texture, with a reduction in arsenate while increase in arsenite, mono-methyl arsenate, and di-methyl arsenate with increasing the rate of FYM supplementation. Bioaccumulation factor reduced with FYM addition, and highest reduction of 38.65 and 42.13% in sandy, 34.24 and 36.26% in loamy while 29.16 and 35.10% in clayey soils at As-60 and As-120, respectively, by 50 g kg-1 FYM compared with respective As treatments without FYM. As accumulation in plant parts was significantly (P ≤ 0.05) reduced by FYM with the subsequent improvement in achene yield.

20.
J Pharm Biomed Anal ; 236: 115682, 2023 Nov 30.
Artículo en Inglés | MEDLINE | ID: mdl-37660547

RESUMEN

The analysis of homeopathic medicines for the content of total inorganic As by hydride generation (HG) hyphenated with the ICP OES detection was presented. Various forms of medicaments (sugar pellets, tablets, alcohol-based drops), containing Arsenicum album or Arsenicum iodatum in several potencies (C9-200, D6-10), as well as different sample preparation approaches (wet digestion, extraction, dissolution, dilution, direct analysis) before spectrometric measurements were studied. The influence of the undecomposed sample matrix (mainly sugar and alcohol) on the HG process of As was examined in detail. Under optimal conditions found, simplified sample preparation procedures for the determination of As traces were proposed. The suitable sensitivity, the limit of detection of As < 0.1 ng g-1, the precision within 0.31-7.4 % (as RSD), and the adequate trueness (94.9-113 % as confirmed by the recovery test) were achieved. Using the species-selective HG conditions and the developed direct analysis method, the speciation of As in arsenic drops without any prior chromatographic separation of As(III) and As(V) was carried out. The applicability of the developed strategies was demonstrated by the determination of As in 13 homeopathic products available on the Polish market.

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