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Biometals : An International Journal on... Feb 2018Anthropogenic sources of arsenic poses and creates unintentional toxico-pathological concerns to humans in many parts of the world. The understanding of toxicity of this... (Review)
Review
Anthropogenic sources of arsenic poses and creates unintentional toxico-pathological concerns to humans in many parts of the world. The understanding of toxicity of this metalloid, which shares properties of both metal and non-metal is principally structured on speciation types and holy grail of toxicity prevention. Visible symptoms of arsenic toxicity include nausea, vomiting, diarrhea and abdominal pain. In this review, we focused on the dermal cell stress caused by trivalent arsenic trioxide and pentavalent arsanilic acid. Deciphering the molecular events involved during arsenic toxicity and signaling cascade interaction is key in arsenicosis prevention. FoxO1 and FoxO2 transcription factors, members of the Forkhead/Fox family, play important roles in this aspect. Like Foxo family proteins, ATM/CHK signaling junction also plays important role in DNA nuclear factor guided cellular development. This review will summarize and discuss current knowledge about the interplay of these pathways in arsenic induced dermal pathogenesis.
Topics: Arsanilic Acid; Arsenic Poisoning; Arsenic Trioxide; Arsenicals; Ataxia Telangiectasia Mutated Proteins; Forkhead Box Protein O1; Humans; Oxidative Stress; Oxides; Protein Isoforms; Proto-Oncogene Proteins pp60(c-src); Signal Transduction; Skin; Transcriptional Activation
PubMed: 29143154
DOI: 10.1007/s10534-017-0065-3 -
NeuroImage Feb 2021Unilateral damage to the inner ear results in an acute vestibular syndrome, which is compensated within days to weeks due to adaptive cerebral plasticity. This process,...
Unilateral damage to the inner ear results in an acute vestibular syndrome, which is compensated within days to weeks due to adaptive cerebral plasticity. This process, called central vestibular compensation (VC), involves a wide range of functional and structural mechanisms at the cellular and network level. The short-term dynamics of whole-brain functional network recruitment and recalibration during VC has not been depicted in vivo. The purpose of this study was to investigate the interplay of separate and distinct brain regions and in vivo networks in the course of VC by sequential [F]-FDG-PET-based statistical and graph theoretical analysis with the aim of revealing the metabolic connectome before and 1, 3, 7, and 15 days post unilateral labyrinthectomy (UL) in the rat. Temporal changes in metabolic brain connectivity were determined by Pearson's correlation (|r| > 0.5, p < 0.001) of regional cerebral glucose metabolism (rCGM) in 57 segmented brain regions. Metabolic connectivity analysis was compared to univariate voxel-wise statistical analysis of rCGM over time and to behavioral scores of static and dynamic sensorimotor recovery. Univariate statistical analysis revealed an ipsilesional relative rCGM decrease (compared to baseline) and a contralesional rCGM increase in vestibular and limbic networks and an increase in bilateral cerebellar and sensorimotor networks. Quantitative analysis of the metabolic connections showed a maximal increase from baseline to day 3 post UL (interhemispheric: 2-fold, ipsilesional: 3-fold, contralesional: 12-fold) and a gradual decline until day 15 post UL, which paralleled the dynamics of vestibular symptoms. In graph theoretical analysis, an increase in connectivity occurred especially within brain regions associated with brainstem-cerebellar and thalamocortical vestibular networks and cortical sensorimotor networks. At the symptom peak (day 3 post UL), brain networks were found to be organized in large ensembles of distinct and highly connected hubs of brain regions, which separated again with progressing VC. Thus, we found rapid changes in network organization at the subcortical and cortical level and in both hemispheres, which may indicate an initial functional substitution of vestibular loss and subsequent recalibration and reorganization of sensorimotor networks during VC.
Topics: Adaptation, Physiological; Animals; Arsanilic Acid; Brain; Connectome; Fluorodeoxyglucose F18; Glucose; Locomotion; Neural Pathways; Neuronal Plasticity; Nystagmus, Pathologic; Positron-Emission Tomography; Postural Balance; Radiopharmaceuticals; Rats; Vestibular Diseases; Vestibule, Labyrinth
PubMed: 33249212
DOI: 10.1016/j.neuroimage.2020.117588 -
Water Research Jun 2020As a common animal feed additive, p-arsanilic acid (p-AsA) is thought to be excreted with little uptake and unchanged chemical structure, threatening the environment by...
As a common animal feed additive, p-arsanilic acid (p-AsA) is thought to be excreted with little uptake and unchanged chemical structure, threatening the environment by potentially releasing more toxic inorganic arsenic. We herein investigated the removal of arsenic by in situ formed ferric (oxyhydr)oxides with the promotion of p-AsA degradation in Fe(II)/peroxydisulfate (PDS) system. Results showed that under acid conditions, p-AsA degraded very quickly and over 99% of p-AsA (5 μM) was degraded within 10 min at the optimal dosage of Fe(II) (100 μM) and PDS (150 μM) at pH 3, while less than 66.4% of arsenic was removed at pH 3-5. Higher pH (3-7) would inhibit the degradation of p-AsA but promote the arsenic removal. At pH 6-7, over 98.5% of total arsenic was removed, while the degradation efficiency of p-AsA was lower than 52.4%. HPLC-ICP-MS results indicated that the arsenic group was cleaved from p-AsA in the form of As(III) and then rapidly oxidized to As(V). FTIR and XPS analysis indicated that both As(V) products and residual p-AsA were bonded to ferric (oxyhydr)oxides via hydroxyl groups. Common cations (e.g., Na, Ca, Mg) and anions such as Cl, SO, CO had no significant influence on arsenic removal, while SiO, PO and HA inhibited the removal of total arsenic, mainly by affecting the zeta potential of iron particles. In summary, the Fe(II)/PDS process, as an efficient method for partial oxidation and simultaneous adsorption of p-AsA under near-neutral conditions, is expected to control the potential environmental risks of p-AsA.
Topics: Adsorption; Animals; Arsanilic Acid; Arsenic; Ferric Compounds; Ferrous Compounds; Hydrogen-Ion Concentration; Iron; Oxidation-Reduction; Water Pollutants, Chemical
PubMed: 32283433
DOI: 10.1016/j.watres.2020.115752 -
ACS Applied Materials & Interfaces Dec 2020It is very significant that functional porous metal-organic frameworks are used to manufacture hierarchical components to achieve cascading functions that cannot be...
It is very significant that functional porous metal-organic frameworks are used to manufacture hierarchical components to achieve cascading functions that cannot be achieved by a single-layer metal-organic framework (MOF). Here, we report two cases of novel MOFs constructed by the same ligand, - and - (Htpt = 5-[4(1-1,2,4-triazol-1-yl)]phenyl-2-tetrazole), and prepared a --- by a layer-by-layer approach ignoring the lattice mismatch problem. The first - layer is grown on an oriented CuO nanostructured array by a "one-pot" approach. The aligned second - layer can be deposited using liquid-phase epitaxy. Notably, the prepared --- combines adsorption and fluorescence sensing, which exhibited significant adsorption for CrO (203.25 mg g) as typical highly poisonous ions with a fluorescence quenching response. Hence, based on the oxidation-reduction between CrO and -arsanilic acid (-ASA), the --- ability to adsorb CrO could be used to design "on-off-on" mode fluorescence probes to detect -ASA with high sensitivity (limit of detection (LOD) = 0.0556 μg L). -ASA can be degraded into highly toxic inorganic arsenic compounds in the natural environment and has received widespread attention. Therefore, the integration of adsorption and fluorescence properties makes the --- a feasible multifunctional material for pollution control and detection.
PubMed: 33345540
DOI: 10.1021/acsami.0c17875 -
Environmental Science & Technology Aug 2016Microbes play a critical role in the global arsenic biogeocycle. Most studies have focused on redox cycling of inorganic arsenic in bacteria and archaea. The parallel...
Microbes play a critical role in the global arsenic biogeocycle. Most studies have focused on redox cycling of inorganic arsenic in bacteria and archaea. The parallel cycles of organoarsenical biotransformations are less well characterized. Here we describe organoarsenical biotransformations in the environmental microbe Shewanella putrefaciens. Under aerobic growth conditions, S. putrefaciens reduced the herbicide MSMA (methylarsenate or MAs(V)) to methylarsenite (MAs(III)). Even though it does not contain an arsI gene, which encodes the ArsI C-As lyase, S. putrefaciens demethylated MAs(III) to As(III). It cleaved the C-As bond in aromatic arsenicals such as the trivalent forms of the antimicrobial agents roxarsone (Rox(III)), nitarsone (Nit(III)) and phenylarsenite (PhAs(III)), which have been used as growth promoters for poultry and swine. S. putrefaciens thiolated methylated arsenicals, converting MAs(V) into the more toxic metabolite monomethyl monothioarsenate (MMMTAs(V)), and transformed dimethylarsenate (DMAs(V)) into dimethylmonothioarsenate (DMMTAs(V)). It also reduced the nitro groups of Nit(V), forming p-aminophenyl arsenate (p-arsanilic acid or p-AsA(V)), and Rox(III), forming 3-amino-4-hydroxybenzylarsonate (3A4HBzAs(V)). Elucidation of organoarsenical biotransformations by S. putrefaciens provides a holistic appreciation of how these environmental pollutants are degraded.
Topics: Animals; Arsenic; Arsenicals; Biotransformation; Cacodylic Acid; Roxarsone; Shewanella putrefaciens; Swine
PubMed: 27366920
DOI: 10.1021/acs.est.6b00235 -
Environment International Feb 2015Arsenic contamination in groundwater has endangered the health and safety of millions of people around the world. One less studied mechanism for arsenic introduction... (Review)
Review
Arsenic contamination in groundwater has endangered the health and safety of millions of people around the world. One less studied mechanism for arsenic introduction into the environment is the use of organoarsenicals in animal feed. Four organoarsenicals are commonly employed as feed additives: arsanilic acid, carbarsone, nitarsone, and roxarsone. Organoarsenicals are composed of a phenylarsonic acid molecule with substituted functional groups. This review documents the use of organoarsenicals in the poultry industry, reports analytical methods available for quantifying organic arsenic, discusses the fate and transport of organoarsenicals in environmental systems, and identifies toxicological concerns associated with these chemicals. In reviewing the literature on organoarsenicals, several research needs were highlighted: advanced analytical instrumentation that allows for identification and quantification of organoarsenical degradation products; a greater research emphasis on arsanilic acid, carbarsone, and nitarsone; identification of degradation pathways, products, and kinetics; and testing/development of agricultural wastewater and solid treatment technologies for organoarsenical-laden waste.
Topics: Animals; Arsenic; Floors and Floorcoverings; Groundwater; Housing, Animal; Poultry; Water Pollutants, Chemical
PubMed: 25461415
DOI: 10.1016/j.envint.2014.10.022 -
Water Research Feb 2016Although banned in some developed countries, p-arsanilic acid (p-ASA) is still used widely as a feed additive for swine production in many countries. With little uptake...
Although banned in some developed countries, p-arsanilic acid (p-ASA) is still used widely as a feed additive for swine production in many countries. With little uptake and transformation in animal bodies, nearly all the p-ASA administered to animals is excreted chemically unchanged in animal wastes, which can subsequently release the more toxic inorganic arsenic species upon degradation in the environment. For safe disposal of the animal wastes laden with p-ASA, we proposed a method of leaching the highly water-soluble p-ASA out of the manure first, followed by treatment of the leachate using the Fenton process to achieve fast oxidation of p-ASA and removal of the inorganic arsenic species released (predominantly arsenate) from solution simultaneously. The effects of solution pH, dosages of H2O2 and Fe(2+), and the presence of dissolved organic matter (DOM) on the treatment efficiency were systematically investigated. Under the optimum treatment conditions (0.53 mmol L(-1) Fe(2+), 2.12 mmol L(-1) H2O2, and initial pH of 3.0), p-ASA (10 mg-As L(-1)) could be completely oxidized to As(V) within 30 min in pure water and 4 natural water samples, and at the final pH of 4.0, the residual arsenic levels in solution phase were as low as 1.1 and 20.1-43.4 μg L(-1) in the two types of water matrixes, respectively. The presence of humic acid significantly retarded the oxidation of p-ASA by scavenging HO, and inhibited the As(V) removal through competitive adsorption on ferric hydroxide. Due to the high contents of DOM in the swine manure leachate samples (TOC at ∼500 mg L(-1)), much higher dosages of Fe(2+) (10.0 mmol L(-1)) and H2O2 (40.0 mmol L(-1)) and a longer treatment time (120 min) were required to achieve near complete oxidation of p-ASA (98.0%), while maintaining the levels of residual arsenic in the solution at <70.0 μg L(-1). The degradation pathway of p-ASA in the Fenton process was proposed based on the major degradation products detected. Together, the results demonstrate that the Fenton process is promising as an efficient, robust, and low-cost treatment method for controlling the risk of p-ASA in the animal wastes generated at factory farms.
Topics: Adsorption; Animals; Arsanilic Acid; Arsenic; Humic Substances; Hydrogen Peroxide; Hydrogen-Ion Concentration; Iron; Manure; Organic Chemicals; Oxidation-Reduction; Sus scrofa; Waste Disposal, Fluid
PubMed: 26638133
DOI: 10.1016/j.watres.2015.11.037 -
Environmental Science and Pollution... Nov 2015The paper presents the kinetics and proposed pathways photodegradation and photooxidation of p-arsanilic acid, in a neutral environment by ozone and hydrogen peroxide....
The paper presents the kinetics and proposed pathways photodegradation and photooxidation of p-arsanilic acid, in a neutral environment by ozone and hydrogen peroxide. The results showed that in a neutral environment, photoozonation process was characterized by the highest decomposition rate constant (k) (k = 31.8 × 10(-3) min(-1)). The rate constants decreased in the order UV/O3 > O3 > UV/H2O2 > H2O2 > UV. It was also found that under pH = 7, decomposition of p-arsanilic acid leads mainly to the formation of aniline, which undergoes secondary reactions. Intermediate products of oxidation and photooxidation by hydrogen peroxide like nitrobenzene, nitrophenol, azobenzenes, and phenylazophenol were identified depending on processes. However, in the photodegradation process, formation of nitrasone as a reaction product of p-arsanilic acid with oxygen in the singlet state was observed. In the case of ozonation and photoozonation, in addition, aniline formation of carboxylic acids was observed.
Topics: Arsanilic Acid; Hydrogen Peroxide; Hydrogen-Ion Concentration; Oxidation-Reduction; Ozone; Photolysis; Water
PubMed: 26109222
DOI: 10.1007/s11356-015-4890-z -
The Science of the Total Environment Jan 2024Although banned in some countries, p-arsanilic acid (ASA) is still widely used as feed additive in poultry production. As a result, ASA is usually released into the...
Although banned in some countries, p-arsanilic acid (ASA) is still widely used as feed additive in poultry production. As a result, ASA is usually released into the aquatic environment without any treatments. Although ASA exhibits low toxicity, it can be transformed into highly toxic aromatic amines and inorganic arsenic species (As (V) as HAsO and HAsO) under natural environmental conditions. Hence, it is necessary to develop efficient technologies for its removal or degradation. In this contribution, electrochemical advanced oxidation technology with boron-doped diamond (BDD) had been initially used to degrade ASA pollutants. A five-level central composite rotatable design (CCRD) was implemented to optimize the various influencing factors involved, among applied current density, NaCl concentration, NaSO concentration and NaHCO concentration on the oxidation efficiency; the latter was assessed in terms of ASA degradation percentage. The results obtained highlighted the unique and important roles of electrolytes during the electrolytic oxidations. Meanwhile, the major degradation byproducts detected were also strongly dependent on the electrolyte adopted. In particular, several oligomer byproducts with novel structures were initially identified in BDD-treated ASA solutions. Two different electrochemical transformation pathways of ASA on BDD anode were thus proposed. This study demonstrated the effectiveness of BDD technology in the degradation of ASA, as well as the potential minor risk of its application in actual ASA wastewater treatment.
PubMed: 37797755
DOI: 10.1016/j.scitotenv.2023.167538 -
Materials (Basel, Switzerland) Dec 2023As a kind of emerging contaminant, organoarsenic compounds have drawn wide concern because of their considerable solubilities in water, and the highly toxic inorganic...
As a kind of emerging contaminant, organoarsenic compounds have drawn wide concern because of their considerable solubilities in water, and the highly toxic inorganic arsenic species formed during their biotic and abiotic degradation in the natural environment. Thus, the effective removal and studying of the adsorption mechanism of organoarsenic compounds are of significant urgency. In this work, MnFeO and MnFeO/graphene were prepared through a facile solvothermal method. From the results of the Transmission Electron Microscope (TEM) characterization, it can be found that MnFeO nanoparticles were uniformly distributed on the surface of the graphene. And the specific surface area of the MnFeO/graphene was about 146.39 m g, much higher than that of the MnFeO (86.15 m g). The interactions between organoarsenic compounds and adsorbents were conducted to study their adsorption behavior and mechanism. The maximum adsorption capacities of MnFeO/graphene towards p-arsanilic acid (p-ASA) and roxarsone (ROX) were calculated to be 22.75 and 30.59 mg g. Additionally, the ionic strength, negative ions, and humus were introduced to investigate the adsorption performance of organoarsenic compounds. Electrostatic adsorption and surface complexation are the primary adsorption mechanisms on account of X-ray photoelectron spectroscopy (XPS) and the Fourier-transform infrared spectroscopy (FT-IR) analysis. This research extends the knowledge into studying the interaction between organoarsenic species and hybrid nanomaterials in the natural environment.
PubMed: 38138778
DOI: 10.3390/ma16247636