Iron-doped carbon nanotubes with magnetic enhanced Fe(VI) degradation of arsanilic acid and inorganic arsenic: Role of intermediate iron species and electron transfer.

Arsanilic acid (p-AsA), a prevalently used feed additive, is frequently detected in environment posing a great threat to humans. Potassium ferrate (Fe(VI)) was an efficient way to tackle arsenic contamination under acid and neutral conditions. However, Fe(VI) showed a noneffective removal of p-AsA under alkaline conditions due to its oxidation capacity attenuation. Herein, a magnetic iron-doped carbon nanotubes (F-CNT) was successfully prepared and further catalyzed Fe(VI) to remove p-AsA and total As species. The Fe(VI)/F-CNT system showed an excellent capability to oxidize p-AsA and adsorb total As species over an environment-related pH range of 6-9. The high-valent iron intermediates Fe(V)/Fe(IV) and the mediated electron-transfer played a significant part in the degradation of p-AsA according to the probes/scavengers experiments and galvanic oxidation process. Moreover, the situ formed iron hydroxide oxide and F-CNT significantly improved the adsorption capacity for total As species. The electron-donating groups (semiquinone and hydroquinone) and high graphitization of F-CNT were responsible for activating Fe(VI) based on the analysis of X-ray photoelectron spectroscopy (XPS). Density functional theory calculations and the detected degradation products both indicated that the amino group and the C-As bond of p-AsA were main reactive sites. Notably, Fe(VI)/F-CNT system was resistant to the interference from Cl-, SO42-, and HCO3-, and could effectively remove p-AsA and total As species even in the presence of complex water matrix. In summary, this work proposed an efficient method to use Fe(VI) for degrading pollutants under alkaline conditions and explore a new technology for livestock wastewater advanced treatment.

Photodegradation of para-arsanilic acid mediated by photolysis of iron(III) oxalate complexes.

Organic arsenicals are important environment pollutants due to wide use in livestock and toxicity of degradation products. In this work we report about the efficient photodegradation of the p-arsanilic acid (p-ASA) and its decomposition products in the Fe(III)-oxalate assisted approach under nature-relevant conditions. At neutral pH under near-visible UV irradiation the Fe(III) oxalate complexes generate the primary oxidizing intermediate, OH radical (the quantum yield of ϕOH âˆ¼ 0.06), which rapidly reacts with p-ASA with high rate constant, (8.6 ± 0.5) × 109 M-1s-1. Subsequent radical reactions result in the complete photooxidation of both p-ASA and basic aromatic photoproducts with the predominant formation of inorganic arsenic species, mainly As(V), under optimal conditions. Comparing with the direct UV photolysis, the presented Fe(III)-oxalate mediated degradation of p-ASA has several advantages: higher efficiency at low p-ASA concentration and complete degradation of organic arsenic by-products without use of short-wavelength UV radiation. The obtained results illustrate that the Fe(III)-oxalate complexes are promising natural photosensitizers for the removal of arsenic pollutants from contaminated waters.

Arsanilic acid modified superparamagnetic iron oxide nanoparticles for Purification of alkaline phosphatase from hen's egg yolk.

Recent studies of magnetic carrier technology have focused on its applications in separation and purification technologies, due to easy separation of the target from the reaction medium by applying an external magnetic field. In the present study, Fe3O4 superparamagnetic nanoparticles were prepared to utilize a chemical co-precipitation method, then the surfaces of the nanoparticles were modified with arsanilic acid derivatives which were used as the specific nanocarriers for the affinity purification of alkaline phosphatase from the hen's egg yolk. The six different types of magnetic nanocarriers with varied lengths of the linkers were obtained. All samples were characterized step by step and validated using FTIR, SEM, EDX, VSM and XRD analysis methods As the results were shown, the use of inflexible tags with long linkers on the surface of the nanocarrier could lead to better results for separation of alkaline phosphatase from the hen's egg yolk with 76.2% recovery and 1361.7-fold purification. The molecular weight of the purified alkaline phosphatase was estimated to be 68kDa by SDS-PAGE. The results of this study showed that the novel magnetic nanocarriers were capable of purifying alkaline phosphatase in a practically time and cost effective way.

Density functional theory calculations on the complexation of p-arsanilic acid with hydrated iron oxide clusters: structures, reaction energies, and transition states.

Aromatic organoarsenicals, such as p-arsanilic acid (pAsA), are still used today as feed additives in the poultry and swine industries in developing countries. Through the application of contaminated litter as a fertilizer, these compounds enter the environment and interact with reactive soil components such as iron and aluminum oxides. Little is known about these surface interactions at the molecular level. We report density functional theory (DFT) calculations on the energies, optimal geometries, and vibrational frequencies for hydrated pAsA/iron oxide complexes, as well as changes in Gibbs free energy, enthalpy, and entropy for various types of ligand exchange reactions leading to both inner- and outer-sphere complexes. Similar calculations using arsenate are also shown for comparison, along with activation barriers and transition state geometries between inner-sphere complexes. Minimum energy calculations show that the formation of inner- and outer-sphere pAsA/iron oxide complexes is thermodynamically favorable, with the monodentate mononuclear complexes being the most favorable. Interatomic As-Fe distances are calculated to be between 3.3 and 3.5 Å for inner-sphere complexes and between 5.2 and 5.6 Å for outer-sphere complexes. In addition, transition state calculations show that activation energies greater than 23 kJ/mol are required to form the bidentate binuclear pAsA/iron oxide complexes, and that formation of arsenate bidentate binuclear complexes is thermodynamically -rather than kinetically- driven. Desorption thermodynamics using phosphate ions show that reactions are most favorable using HPO4(2-) species. The significance of our results for the overall surface complexation mechanism of pAsA and arsenate is discussed.

Surface adsorption of organoarsenic roxarsone and arsanilic acid on iron and aluminum oxides.

Aromatic organoarsenicals roxarsone (ROX) and p-arsanilic acid (ASA) are common feed additives for livestock and could be released into the environment via animal manure and agricultural runoff. To evaluate their environmental fate, the adsorption behavior of ROX and ASA was investigated with two common soil metal oxides, goethite (FeOOH) and aluminum oxide (Al(2)O(3)), under different reactant loading, water pH and competing ion conditions. ROX and ASA exhibit essentially identical adsorption characteristics. FeOOH and Al(2)O(3) exhibit similar adsorption trends for both organoarsenicals; however, the adsorption efficiency on the surface site basis was about three times lower for Al(2)O(3) than for FeOOH. The adsorption reaction is favorable at neutral and acidic pH. Phosphate and natural organic matter significantly interfere with aromatic arsenical adsorption on both metal oxides, whereas sulfate and nitrate do not. Pre-adsorbed aromatic arsenicals can be quickly but not completely displaced by phosphate, indicating that ion exchange is not the only mechanism governing the adsorption process. The adsorption envelope was successfully modeled by a diffuse double layer surface complexation model, identifying the critical role of di-anionic organoarsenic species in the adsorption. Results of this research can help predict and control the mobility of aromatic arsenicals in the environment.

Synthesis of a fluorescently labeled compound for the detection of arsenic-induced apoptotic HL60 cells.

Arsenic compounds have shown medical usefulness since they proved to be effective in causing complete remission of acute promyelocytic leukemia. In this work we obtained a fluorescently labeled arsenic compound that can be used with current fluorescence techniques for basic and applied research, focused on arsenic-induced apoptosis studies. This compound is an arsanilic acid bearing a covalently linked FITC that was chemically synthesized and characterized by fluorescence, UV-Vis, mass and FTIR spectrometry. In addition, we assessed its apoptotic activity as well as its fluorescent labeling properties in HL60 cell line as a leukemia cell model through flow cytometry. We obtained a compound with a 1:1 FITC:arsenic ratio and a 595 m/z, confirming its structure by FTIR. This compound proved to be useful at inducing apoptosis in the leukemia cell model and labeling this apoptotic cell population, in such a way that the highest FITC fluorescence correlated with the highest arsenic amount.

In situ ATR-FTIR and surface complexation modeling studies on the adsorption of dimethylarsinic acid and p-arsanilic acid on iron-(oxyhydr)oxides.

Arsenic is an element that exists naturally in many rocks and minerals around the world. It also accumulates in petroleum, shale, oil sands, and coal deposits as a result of biogeochemical processes, and it has been found in fly ash from the combustion of solid biofuels. Arsenic compounds in their organic and inorganic forms pose both a health and an environmental risk, and continue to be a challenge to the energy industry. The environmental fate and removal technologies of arsenic compounds are controlled to a large extent by their surface interactions with inorganic and organic adsorbents. We report thermodynamic binding constants, K(binding), from applying the triple-layer surface complexation model to adsorption isotherm and pH envelope data for dimethylarsinic acid (DMA) and p-arsanilic acid (p-AsA) on hematite and goethite. Ligand exchange reactions were constructed based on the interpretation of ATR-FTIR spectra of DMA and p-AsA surface complexes. Surface coverage of adsorbates was quantified in situ from the spectral component at 840 cm(-1). The best fit to the DMA adsorption data was obtained using outer-sphere complex formation, whereas for p-AsA, the best fit was obtained using two monodentate inner-sphere surface complexes. The significance of the results is discussed in relation to improving modeling tools used by environmental regulators and the energy sector for optimum control of arsenic content in fuels.

ATR-FTIR studies on the nature of surface complexes and desorption efficiency of p-arsanilic acid on iron (oxyhydr)oxides.

The fate of organoarsenicals introduced to the environment through the application of arsenic-contaminated manure has attracted considerable attention after the recent implementation of the latest maximum contaminant level (MCL) of total arsenic in drinking water by the U.S. Environmental Protection Agency (EPA). We report herein detailed spectroscopic analysis of the surface structure of p-arsanilic acid (p-AsA) adsorbed on Fe-(oxyhydr)oxides using attenuated total internal reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Spectra of p-AsA(ads) were collected in situ as a function of pH and ionic strength and using D20 at 298 K in flow mode. Results indicate the formation of inner-sphere complexes, which are likely monodentate and become protonated under acidic pH(D). We also examined the desorption efficiency of p-AsA(ads) due to flowing electrolyte and phosphate solutions as low as 0.1 mol/m3 (3 ppm P) by collecting ATR-FTIR spectra as a function of time. Our results suggest that aqueous phosphate is an efficient desorbing anion of p-AsA(ads), which has implications on its bioavailability and mobility in geochemical environments.

Adsorption thermodynamics of p-arsanilic acid on iron (oxyhydr)oxides: in-situ ATR-FTIR studies.

The organoarsenical p-arsanilic acid (p-AsA) is used in the U.S. poultry industry as a feed additive and its structure resembles one of the stable biodegradation products of Roxarsone (ROX) in anaerobic environments. With the implementation of recent EPA MCL of total arsenic in drinking water (10 ppb), thereareconcernsaboutthefate of organoarsenicals introduced to the environment through the application of arsenic-contaminated manure. We report herein, for the first time, the thermodynamics of p-AsA binding to Fe-(oxyhydr)oxides using ATR-FTIR. ATR-FTIR spectra were used to quantify surface coverage of p-AsA, p-AsA(ads), by analyzing the broadband assigned to v(As-O) at 837 cm(-1). Adsorption isotherms were measured in situ at 298 K and pH 7 in the concentration range 1 microM to 40 mM. Values of Keq were obtained from Langmuir model fits and they range from 1411 to 3228 M(-1). We also determined the maximum adsorption capacities of Fe-(oxyhydr)oxides to p-AsA, and they range from 1.9 x 10(13) to 2.6 x 10(13) molecules/cm2. Our results suggest that p-AsA is more mobile than methylated and inorganic forms of arsenic and that the transport of nanoparticles with p-AsA(ads) might play a role in its mobility in geochemical environments.