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Arsenic acid

Arsenic acid (H₃AsO₄) is an inorganic arsenic oxoacid and a triprotic acid in which a central arsenic atom in the +5 oxidation state is bonded to three hydroxy groups and one oxo group.^[1] It typically exists as a clear, colorless aqueous solution, though the anhydrous solid form appears as white, translucent, deliquescent crystals.^[2] With a molecular weight of 141.94 g/mol, arsenic acid has a melting point of 35.5 °C and decomposes upon heating at around 160 °C, releasing toxic and corrosive fumes of arsenic oxides.^[2] It exhibits high solubility in water (approximately 167 g/L at 20 °C) and in ethanol, while acting as a strong oxidizing agent that reacts violently with reducing materials and metals to produce highly toxic arsine gas.^[3]^[2] Its density is about 2.5 g/cm³, and it is noncombustible but corrosive to metals.^[2] Arsenic acid has been employed industrially as a wood preservative for non-food applications, a desiccant in agriculture (particularly for cotton and non-cropped areas), and a biocide to control pests such as gypsy moths, invasive plants, and rats.^[3] Additional uses include as a finishing agent for glass and metals, and as a reagent in the synthesis of organoarsenic compounds and certain pesticides, herbicides, fungicides, and algicides.^[2] Due to environmental and health concerns, however, its applications have been significantly restricted; it is now obsolete and not approved for use in the European Union or Great Britain under regulations like EC 1107/2009.^[3] As a pentavalent arsenic compound, arsenic acid is extremely toxic by ingestion, inhalation, and skin contact, with an acute oral LD₅₀ of 48 mg/kg in mammals, and it is classified as a Group 1 carcinogen by the International Agency for Research on Cancer.^[3] Exposure can lead to severe symptoms including gastrointestinal distress, muscle weakness, neurotoxicity, reproductive and developmental effects, and long-term risks of skin, lung, and bladder cancers.^[3] It poses moderate ecotoxicological risks, with LC₅₀ values of 53.1 mg/L for fish and 6.5 mg/L for Daphnia, and is highly persistent in the environment due to limited degradation.^[3]

General Information

Nomenclature

Arsenic acid is the common name for the inorganic compound systematically designated as arsoric acid according to IUPAC nomenclature.^[4]^[1] This naming reflects its status as an oxyacid of arsenic in its highest oxidation state. The term "arsenic acid" derives from the element arsenic, whose name originates from the Persian word zarnikh, referring to the yellow pigment orpiment (arsenic trisulfide), later adapted through Greek arsenikon and Latin arsenicum.^[5] The suffix "acid" denotes its acidic oxyacid nature, distinguishing it from related forms such as meta-arsenic acid (HAsO₃) and pyroarsenic acid (H₄As₂O₇), which represent condensed or dehydrated variants.^[6] Other synonyms include orthoarsenic acid, emphasizing its orthofomic structure; trihydrogen arsenate, highlighting the three ionizable hydrogen atoms; and trade names like Desiccant L-10 and Zotox, used in applications such as herbicides and desiccants.^[7]^[8] The compound is identified by CAS number 7778-39-4 and EC number 231-901-9 in chemical registries.^[4]^[1]

Natural Occurrence

Arsenic acid predominates in oxygenated (oxic) surface and groundwaters where the pentavalent arsenic (AsV) form is stable, while in anoxic conditions it reduces to trivalent arsenite (AsIII). Arsenic acid (H₃AsO₄) and its dissociated forms, such as the arsenate ion (AsO₄³⁻), arise naturally through the oxidative weathering of arsenic-containing sulfide minerals, primarily arsenopyrite (FeAsS), found in mineral deposits and rock formations. This process occurs in aerobic environments where exposure to oxygen and water mobilizes arsenic from primary sulfides into secondary forms, including arsenate, which predominates in oxygenated groundwater and soils. Such natural mobilization is common in sedimentary basins and volcanic terrains, where geochemical interactions with iron oxides and other minerals facilitate the release.^[9]^[10] In regions with significant natural arsenic enrichment, groundwater concentrations of total arsenic can reach elevated levels, typically ranging from 0.5 to 5 mg/L in severely affected areas. The speciation depends on redox conditions, with arsenate predominant in oxic environments and arsenite in anoxic ones.^[11] For instance, in the alluvial aquifers of Bangladesh under reducing conditions, levels often span 0.1 to 4.7 mg/L primarily as arsenite due to reductive dissolution of arsenic-bearing iron oxides, while in the volcanic-influenced groundwater of Argentina's Pampa plains, concentrations vary from 0.5 to over 5 mg/L in shallow aquifers, predominantly as arsenate from oxidative weathering.^[9]^[11]^[12] These occurrences highlight arsenic acid's environmental presence as a geogenic contaminant rather than a stable mineral phase. Biologically, arsenic acid plays a limited role in microbial metabolism, where certain extremophilic bacteria and archaea, such as haloarchaea in high-arsenic environments, utilize arsenate as an electron acceptor in anaerobic respiration or oxidize arsenite for energy generation. However, this involvement is niche and ancient, primarily serving detoxification or chemolithotrophic purposes in arsenic-rich habitats, with arsenic overall functioning more as a toxic pollutant than an essential compound in broader ecosystems. Natural exposure through these sources contributes to health risks like chronic arsenicism, though detailed toxicological effects are addressed elsewhere.^[13]^[14]

Physical and Chemical Properties

Physical Properties

Arsenic acid is typically observed as white, translucent, hygroscopic crystals in its solid form or as a clear, colorless aqueous solution.^[1]^[15]^[8] The compound has a molar mass of 141.944 g/mol.^[15] Its density is approximately 2.2–2.5 g/cm³ for the solid (hemihydrate).^[15]^[2] Arsenic acid melts at 35 °C and, upon heating above 160 °C, loses water to form arsenic pentoxide.^[15] The material exhibits high solubility in water, reaching 302 g/L at 12.5 °C, and is also soluble in ethanol and glycerol.^[15]^[16] Due to its pronounced hygroscopic nature, arsenic acid absorbs atmospheric moisture readily, resulting in deliquescence and the formation of a solution.^[8]^[17] This hygroscopic behavior is influenced by the polar molecular structure, which facilitates strong interactions with water molecules.^[15]

Chemical Properties

Arsenic acid (H₃AsO₄) is a triprotic acid, capable of donating three protons in aqueous solution through stepwise dissociation. The acid dissociation constants are characterized by pKₐ values of 2.19 for the first proton, 6.94 for the second, and 11.50 for the third, indicating moderate strength for the initial dissociation and progressively weaker acidity for subsequent steps.^[1] The dissociation equilibria are as follows:

\mathrm{H_3AsO_4 + H_2O \rightleftharpoons H_2AsO_4^- + H_3O^+}

\mathrm{H_2AsO_4^- + H_2O \rightleftharpoons HAsO_4^{2-} + H_3O^+}

\mathrm{HAsO_4^{2-} + H_2O \rightleftharpoons AsO_4^{3-} + H_3O^+}

These values reflect the compound's behavior as a moderately strong acid at low pH, facilitating its role in various chemical environments.^[1]^[18] In terms of stability, arsenic acid decomposes upon heating, primarily losing water to form arsenic pentoxide (As₂O₅). This thermal dehydration highlights its hydrated nature and limits its use in high-temperature applications. Additionally, arsenic acid acts as an oxidizing agent under acidic conditions, with a standard reduction potential (E°) of approximately 0.56 V for the half-reaction H₃AsO₄ + 2H⁺ + 2e⁻ → HAsO₂ + 2H₂O, enabling it to oxidize species such as iodide to iodine.^[19]^[18] In dilute aqueous solutions, arsenic acid predominantly exists in the hydrated form AsO(OH)₃, which is equivalent to H₃AsO₄. Its speciation is highly pH-dependent, shifting from the neutral H₃AsO₄ species at pH below 2, to the dihydrogen arsenate anion H₂AsO₄⁻ between pH 2 and 7, hydrogen arsenate HAsO₄²⁻ from pH 7 to 11, and fully deprotonated arsenate AsO₄³⁻ above pH 11. This pH-driven speciation influences its reactivity and interactions in solution, enhanced by its high solubility in water.^[1]

Molecular Structure

Geometry and Bonding

Arsenic acid has the molecular formula H₃AsO₄, which can also be represented as AsO(OH)₃ to emphasize its structure as an oxyacid with three hydroxyl groups attached to the central arsenic atom.^[1] The molecule adopts a tetrahedral geometry around the central arsenic atom, with idealized C_{3v} symmetry in its monomeric form.^[20] This arrangement features one As=O double bond and three As–OH single bonds, resulting in As–O bond lengths ranging from 1.639(2) Å for the double bond to 1.704(2) Å for the single bonds, with a mean value of 1.680(2) Å; the O–H bond lengths are approximately 0.96 Å. Arsenic exists in the +5 oxidation state, consistent with its coordination to four oxygen atoms in this highly oxidized form.^[20] The As–O bonds exhibit polar covalent character with partial ionic contributions due to the electronegativity difference between arsenic and oxygen, contributing to the molecule's acidity.^[21] In the solid state, extensive hydrogen bonding networks form between the hydroxyl groups of adjacent molecules, linking the tetrahedral units into a three-dimensional structure.^[20] The geometry and bonding of arsenic acid closely resemble those of phosphoric acid (H₃PO₄), another group 15 oxyacid, but the As–O bonds are longer by approximately 0.2 Å owing to the larger atomic radius of arsenic compared to phosphorus.^[22]

Spectroscopic Characteristics

Infrared (IR) spectroscopy of arsenic acid (H₃AsO₄) reveals characteristic absorption bands associated with its vibrational modes. The As–O stretching vibrations appear in the region around 900 cm⁻¹, reflecting the tetrahedral coordination of the arsenic atom, while the broad O–H stretching band is observed near 3000 cm⁻¹ due to hydrogen bonding in the protonated oxyanions.^[21] Raman spectroscopy complements IR data by providing insights into the symmetric modes of arsenic acid. The spectra exhibit bands that confirm the tetrahedral symmetry of the AsO₄ unit, with prominent As–O symmetric stretching modes around 800–900 cm⁻¹ and lower-frequency bending modes near 400–500 cm⁻¹. These features are consistent across protonated forms in solution and solid state.^[21] Nuclear magnetic resonance (NMR) spectroscopy offers valuable information on the proton and arsenic environments in arsenic acid. In ¹H NMR, the OH protons display a broad signal due to rapid exchange and hydrogen bonding, typically in the 10–12 ppm range relative to TMS. For ⁷⁵As NMR, the chemical shift in acidic aqueous solutions is approximately 0 ppm (referenced to external standards like NaAsF₆), indicative of the tetrahedral As(V) coordination with minimal deshielding from protonation.^[23]^[24] Ultraviolet-visible (UV-Vis) spectroscopy of arsenic acid shows absorption primarily below 250 nm, attributed to ligand-to-metal charge transfer transitions within the AsO₄ moiety. A strong band around 200 nm arises from O → As charge transfer, with no significant visible absorption, consistent with the colorless nature of the compound. X-ray crystallography provides definitive structural confirmation for crystalline arsenic acid, revealing a distorted tetrahedral geometry around the central As atom. Average As–O bond lengths are approximately 1.68 Å for the triply protonated form, with O–As–O angles close to the ideal 109.5° but slightly varied due to intramolecular hydrogen bonding. These measurements validate the spectroscopic inferences of tetrahedral symmetry.^[20]

Synthesis and Preparation

Industrial Methods

Arsenic acid is primarily produced industrially through the oxidation of arsenic trioxide (As₂O₃) using concentrated nitric acid, a process that generates dinitrogen trioxide as a byproduct. The reaction proceeds as follows:

\ce{As2O3 + 2 HNO3 + 2 H2O -> 2 H3AsO4 + N2O3}

This method leverages arsenic trioxide derived from the smelting of ores containing arsenic sulfides, such as those associated with copper and lead production.^[18]^[17] An alternative industrial route involves the hydration of arsenic pentoxide (As₂O₅), which is first obtained by roasting arsenic-bearing ores like arsenopyrite under controlled oxidative conditions to achieve the higher oxidation state. The resulting As₂O₅ is then hydrolyzed with water to yield arsenic acid, providing a pathway when nitric acid oxidation is less feasible due to supply or environmental constraints.^[19]^[25] Industrial processes for both methods typically achieve arsenic acid purities exceeding 95%, with final products often reaching 99% or higher through crystallization and filtration steps tailored for commercial applications. Byproducts such as nitrogen oxides from the nitric acid oxidation are captured and treated using wet scrubbing systems to mitigate emissions, ensuring compliance with environmental standards in production facilities.^[1]^[26] Global annual production of arsenic acid is on the order of thousands of metric tons, predominantly in China, which dominates arsenic compound manufacturing, and to a lesser extent in Europe, where output supports specialized uses like wood preservatives.^[27]^[28]

Laboratory Methods

Laboratory methods for preparing arsenic acid (H₃AsO₄) in research settings typically involve controlled oxidation of elemental arsenic or arsenic(III) compounds under mild conditions to achieve high purity on a small scale. These techniques prioritize safety and precision, often adapting principles from larger-scale oxidations but using equipment like fume hoods and precise dosing for gram quantities.^[29] One effective route for high-purity arsenic acid starts with ozone oxidation of elemental arsenic to arsenic pentoxide, followed by hydration in water. Ozone serves as a strong oxidant to convert metallic arsenic to the As(V) form (4 As + 5 O₃ → 2 As₂O₅ + 5 O₂), minimizing impurities from side reactions. The As₂O₅ is then dissolved in water to yield H₃AsO₄. This method is particularly suited for laboratory use due to its clean stoichiometry, though it requires careful control of ozone to avoid excess gas handling.^[30] Wet oxidation methods offer an alternative, employing elemental arsenic or arsenic trioxide (As₂O₃) reacted with hydrogen peroxide (H₂O₂) in acidic solution. For instance, As₂O₃ can be oxidized by H₂O₂ in sulfuric acid medium, where the peroxide decomposes to generate hydroxyl radicals that facilitate the conversion to H₃AsO₄, achieving efficient transformation of As(III) to As(V). These processes build on broader oxidation principles but are scaled down for benchtop reactors.^[31]^[32] Following synthesis, purification of arsenic acid commonly involves recrystallization from hot water, exploiting its solubility differences to separate impurities, or distillation under reduced pressure to isolate the pure liquid form without decomposition. Recrystallization entails dissolving the crude product in minimal boiling water and cooling slowly to form colorless crystals, while vacuum distillation at around 100–150°C under 10–20 mmHg pressure yields a concentrated, high-purity distillate suitable for analytical use.^[33] All laboratory preparations must be conducted in a well-ventilated fume hood due to the high toxicity of arsenic compounds, which can cause severe respiratory and systemic effects upon inhalation or skin contact; personal protective equipment including gloves, goggles, and respirators is essential. Typical yields for these methods range from 80–90%, depending on reactant purity and reaction control, ensuring sufficient material for research without excessive waste.^[34]^[35]

Chemical Reactions

Acid-Base Reactions

Arsenic acid (H₃AsO₄) acts as a triprotic acid in reactions with bases, undergoing stepwise proton transfer to yield a series of arsenate salts classified as primary, secondary, and tertiary based on the degree of deprotonation. Reaction with one equivalent of sodium hydroxide produces the primary salt sodium dihydrogen arsenate (NaH₂AsO₄), while two equivalents yield the secondary salt disodium hydrogen arsenate (Na₂HAsO₄), and three equivalents form the tertiary salt trisodium arsenate (Na₃AsO₄). These salts are typically prepared by neutralization of arsenic acid solutions and exhibit varying solubilities, with the tertiary salt being highly soluble in water.^[36] The broad distribution of its dissociation constants enables arsenic acid and its salts to function effectively in buffer systems across a wide pH range from approximately 2 to 12, leveraging the first, second, and third pKa values of 2.24, 6.96, and 11.50, respectively. In such buffers, the conjugate acid-base pairs (e.g., H₃AsO₄/H₂AsO₄⁻ for acidic conditions or HAsO₄²⁻/AsO₄³⁻ for basic conditions) resist pH changes upon addition of small amounts of acid or base. Equilibrium speciation diagrams for arsenate systems depict the pH-dependent predominance of species—H₃AsO₄ below pH 2, H₂AsO₄⁻ between pH 3 and 7, HAsO₄²⁻ from pH 8 to 11, and AsO₄³⁻ above pH 12—highlighting the versatility for applications requiring stable pH control.^[37] Beyond simple salt formation, arsenic acid participates in acid-base complexation with metal cations, particularly in analytical contexts where protonated arsenate ligands coordinate to metals. These complexes are relevant in environmental and geochemical analyses for understanding arsenate-metal interactions in solution.^[38]

Redox Reactions

Arsenic acid (H₃AsO₄) serves as an oxidizing agent in redox reactions due to the +5 oxidation state of arsenic, which can be reduced to the +3 state in arsenious acid (H₃AsO₃). One common reduction pathway involves sulfur dioxide (SO₂), which reduces arsenic acid to arsenious acid in aqueous solution, forming sulfuric acid as a byproduct:

\text{H}_3\text{AsO}_4 + \text{SO}_2 + \text{H}_2\text{O} \rightarrow \text{H}_3\text{AsO}_3 + \text{H}_2\text{SO}_4

This reaction is utilized in analytical chemistry and wastewater treatment to convert pentavalent arsenic to a less mobile form.^[39] Arsenic acid is also reduced by iodide ions in acidic media, liberating iodine:

\text{H}_3\text{AsO}_4 + 2\text{I}^- + 2\text{H}^+ \rightarrow \text{H}_3\text{AsO}_3 + \text{I}_2 + \text{H}_2\text{O}

This iodide-based reduction is reversible and employed in iodometric titrations for quantifying arsenic species.^[40]^[41] Arsenic acid can be further reduced by active metals such as zinc or aluminum in acidic conditions to produce highly toxic arsine gas (AsH₃). For example:

\text{H}_3\text{AsO}_4 + 3\text{Zn} + 9\text{H}^+ \rightarrow \text{AsH}_3 + 3\text{Zn}^{2+} + 3\text{H}_2\text{O}

This reaction underscores the need for caution in handling arsenic acid near reducing metals.^[42] The standard reduction potential for the As(V)/As(III) couple, corresponding to the half-reaction

\text{H}_3\text{AsO}_4 + 2\text{H}^+ + 2\text{e}^- \rightleftharpoons \text{H}_3\text{AsO}_3 + \text{H}_2\text{O},

is +0.56 V, indicating moderate oxidizing strength suitable for electrochemical sensors and batteries involving arsenic redox couples.^[43]

Applications

Industrial Uses

Arsenic acid plays a significant role in wood preservation through its incorporation into chromated copper arsenate (CCA), a waterborne preservative formulation that protects timber against fungal decay, insect infestation, and marine borers. CCA is produced by combining arsenic acid (typically at 75% concentration) with chromic acid and copper sulfate, resulting in a mixture where arsenic provides the primary biocide action. This treatment process involves impregnating wood under pressure at low pH (1.6–2.5), allowing deep penetration for long-term durability. Historically, CCA-treated wood was extensively used in industrial settings, including utility poles, railroad ties, and highway structures, accounting for over 90% of arsenic compound consumption in the late 20th century.^[44]^[45]^[46] Arsenic production, much of which supported wood preservation including CCA post-WWII, peaked in the U.S. at 24,878 metric tons (arsenic content) in 1944 before later declining due to regulatory restrictions. CCA consumption itself peaked in the late 20th century. In response to environmental and health concerns, manufacturers voluntarily phased out CCA for most residential uses in the United States by December 31, 2003, reducing overall application by approximately 85%. As of 2025, CCA remains permitted for specific industrial applications, such as pressure-treated wood for commercial construction, agricultural posts, and coastal infrastructure, where alternatives are less effective. While phased out in many regions, limited global use continues in some countries, though substitutes like alkaline copper quat (ACQ) are increasingly adopted.^[46]^[47]^[48] In glass and ceramics manufacturing, arsenic acid acts as a multifunctional additive for decolorizing, clarifying, and fining the melt. As a decolorizer, it oxidizes iron impurities to colorless ferric states, while its clarifying role involves releasing dissolved gases to improve transparency and reduce bubbles, essential for optical and specialty glasses. Concentrations typically range from 0.3 wt% to 1.5 wt% arsenic oxides (derived from arsenic acid or trioxide), with higher levels up to 1.5% in opal or art glasses for enhanced homogeneity. Arsenic acid is preferred in liquid form for precise dosing in batch formulations, though its use has diminished in some regions due to substitution with antimony or cerium compounds.^[49]^[50]^[51] For metal finishing and electronics, arsenic acid functions as an etching agent, particularly in semiconductor processing. It selectively etches silicon nitride films at elevated temperatures, offering etch rates up to twice as fast as phosphoric acid while minimizing undercutting of underlying layers. This application is critical in fabricating microelectronic devices, such as integrated circuits, where precise material removal is required. Additionally, arsenic acid is used in surface passivation of III-V semiconductors like indium phosphide, forming protective oxide layers to prevent degradation during alloy production or device assembly. Its role in alloy hardening, such as strengthening lead grids in batteries, stems from controlled arsenic incorporation via acid-derived salts.^[52]^[53]^[54]

Agricultural and Other Uses

Arsenic acid has historically served as a key precursor in the synthesis of arsenical pesticides, particularly lead arsenate and calcium arsenate, which were widely applied for crop protection against insects such as the codling moth in orchards.^[55] These compounds were extensively used from the late 19th century through the mid-20th century, with lead arsenate being the dominant formulation until safer alternatives emerged.^[56] However, due to their high toxicity and environmental persistence, both lead arsenate and calcium arsenate were banned for agricultural use in the United States by the 1980s, with lead arsenate specifically prohibited in 1988.^[57] Similar restrictions were implemented in many other countries, effectively phasing out these applications to mitigate risks to human health and ecosystems.^[58] In the realm of biocides, arsenic acid and its derivatives have been employed in leather tanning processes to preserve hides and prevent microbial degradation during unhairing and curing stages.^[59] Historically, arsenical compounds acted as effective preservatives in this industry, enhancing durability while controlling bacterial growth.^[60] Additionally, arsenic-based substances, including forms derived from arsenic acid, functioned as mordants in textile dyeing to fix colors onto fabrics, improving fastness and vibrancy in natural dye processes.^[61] These uses, prevalent in earlier industrial practices, have largely been discontinued in favor of less hazardous alternatives owing to regulatory pressures and toxicity concerns.^[62] Beyond agriculture and biocides, arsenic acid finds application as a reagent in the production of certain dyestuffs, where it facilitates chemical reactions essential for color synthesis in industrial formulations.^[63] In analytical chemistry, it is a component in the preparation of the arsenomolybdate reagent, used for colorimetric determination of substances like phosphates and reducing sugars in biochemical assays.^[64] Furthermore, arsenic acid has been utilized as a desiccant in cotton harvesting to dry plant tissues and promote defoliation, aiding mechanical picking in regions like the southern United States.^[65] Today, such desiccant applications are restricted and monitored closely. Due to stringent international regulations stemming from arsenic's carcinogenic and toxic properties, current uses of arsenic acid are confined primarily to non-food, non-agricultural sectors, with agricultural applications prohibited in most jurisdictions to prevent contamination of soil, water, and food chains.^[66] These limitations reflect ongoing efforts to balance historical utility against significant health and environmental risks.^[67]

Health, Safety, and Environmental Impact

Toxicity and Health Effects

Arsenic acid, as an inorganic arsenic compound, exhibits high acute toxicity primarily through its pentavalent arsenic (As(V)) form, which is rapidly absorbed and metabolized in the body. In animal studies, the oral LD50 for arsenic acid is reported as 48 mg/kg in rats, indicating severe toxicity at relatively low doses. Acute exposure in humans and animals leads to rapid onset of gastrointestinal symptoms, including severe nausea, vomiting, abdominal pain, and profuse watery diarrhea often described as "rice water" stools, which can result in dehydration and electrolyte imbalances. These effects progress to cardiovascular complications such as hypotension, tachycardia, and potential collapse due to fluid loss and direct myocardial toxicity.^[1]^[68]^[69] Chronic exposure to arsenic acid and other inorganic arsenic compounds is associated with a range of non-cancer health effects, including characteristic skin lesions such as hyperpigmentation, hyperkeratosis, and skin cancers, as well as peripheral neuropathy manifesting as numbness, tingling, and weakness in extremities. Long-term ingestion or inhalation also increases the risk of cancers, particularly in the lungs, bladder, skin, kidney, and liver, with inorganic arsenic classified as a Group 1 carcinogen (carcinogenic to humans) by the International Agency for Research on Cancer based on sufficient evidence from epidemiological studies. These effects are observed in populations exposed through contaminated water or occupational settings, with no apparent threshold for carcinogenicity.^[69]^[70] The primary mechanism of toxicity for arsenic acid involves its uptake as As(V), which mimics phosphate and enters cells via phosphate transporters, followed by intracellular reduction to trivalent arsenic (As(III)) by enzymes such as arsenate reductase. The more reactive As(III) then binds to sulfhydryl (-SH) groups in critical enzymes, including pyruvate dehydrogenase and alpha-ketoglutarate dehydrogenase, thereby inhibiting key metabolic pathways like the citric acid cycle and oxidative phosphorylation, leading to energy depletion and oxidative stress. This bioaccumulation of As(III) exacerbates toxicity, as it forms stable complexes with glutathione and other thiols, impairing cellular detoxification and promoting genotoxicity through DNA damage and chromosomal aberrations.^[71]^[72] Exposure to arsenic acid occurs mainly through ingestion (e.g., contaminated water or food), inhalation of dust or aerosols in industrial settings, and to a lesser extent dermal absorption, with gastrointestinal uptake being the most efficient route at over 90% bioavailability. The World Health Organization states there is no safe threshold for arsenic exposure, as even low levels can contribute to cumulative health risks over time, emphasizing the need for minimization in all routes.^[69]

Environmental Fate and Regulations

Arsenic acid is highly persistent in the environment, with default modeled soil half-lives on the order of hundreds of thousands of years, though site-specific factors such as pH, redox conditions, organic matter content, and microbial activity can influence its mobility, transformation, and bioavailability.^[73] It readily leaches into groundwater due to its high solubility, particularly in acidic or oxygenated conditions, facilitating its transport from contaminated sites to aquifers.^[74] Microbes play a key role in its biotransformation, converting arsenate forms like arsenic acid to volatile methylarsines through methylation processes, which can lead to atmospheric release and broader dispersal.^[75] Ecologically, arsenic acid is highly toxic to aquatic organisms, with 96-hour LC50 values for fish such as rainbow trout (Oncorhynchus mykiss) around 53.1 mg/L in acute exposure tests, disrupting gill function and ion regulation.^[3] It bioaccumulates in aquatic food chains, transferring from water and sediments to algae, invertebrates, and higher trophic levels like fish, where it can concentrate in tissues and exacerbate toxicity through biomagnification in some systems.^[76] Regulatory measures address arsenic acid's environmental risks through strict limits on its release and use. The U.S. Environmental Protection Agency (EPA) enforces a maximum contaminant level of 10 parts per billion (ppb) for arsenic in drinking water to mitigate groundwater contamination.^[77] In the European Union, REACH classifies arsenic acid as a substance of very high concern, imposing restrictions on its manufacture, placement on the market, and use in mixtures exceeding certain thresholds to prevent environmental release.^[78] Additionally, the voluntary phase-out of chromated copper arsenate (CCA) wood preservatives, which contain arsenic acid derivatives, prohibited their use in consumer products like decks and playgrounds starting in 2004 to reduce leaching into soil and water.^[48] Remediation strategies for arsenic acid-contaminated environments include phytoremediation using hyperaccumulating ferns such as Pteris vittata, which can extract and concentrate arsenic from soil into their fronds for harvest and disposal.^[79] Chemical precipitation methods, often involving ferric chloride or lime to form insoluble arsenate precipitates, effectively remove arsenic from wastewater and groundwater at contaminated sites.^[80]

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https://myneni.princeton.edu/sites/g/files/toruqf1721/files/media/myneni-1998-06-geca.pdf
[22]
[PDF] Experimental and theoretical vibrational spectroscopic evaluation of ...
Jun 22, 1998 · This study evaluates arsenate coordination using vibrational spectroscopy, finding its symmetry distorted and affected by protonation, and its ...
[23]
(75As) Arsenic NMR
Properties of 75As ; Chemical shift range, 660 ppm, from -291 to 369 ; Frequency ratio (Ξ), 17.122614% ; Reference compound, 0.5 M NaAsF6 in CD3CN ; Linewidth of ...
[24]
Arsenic-75 nuclear magnetic resonance: study of the interaction of ...
The 75As line broadening effects and the proton ligand shifts observed indicate that complexation of arsenate by ribose, mannose, glucose, ethanol, ethylene ...
[25]
The Role of Arsenic in the Mining Industry
Arsenic also can be obtained from copper, gold, and lead smelter flue dust as well as from roasting arsenopyrite, the most abundant arsenic mineral.
[26]
Clearing the Air: Our NOx Scrubbing Solution for Koppers
Sep 28, 2023 · They are byproducts of various industrial processes, in this case, stemming from an arsenic acid reactor used in the production of wood ...
[27]
[PDF] Arsenic | 2021 Minerals Yearbook - USGS Publications Warehouse
Apr 24, 2025 · as2O3 was used primarily to produce arsenic acid used in the formulation of chromated copper arsenate (cca), a pesticide and preservative used ...Missing: pentoxide | Show results with:pentoxide
[28]
Arsenic: 2025 World Market Review and Forecast to 2034
China has been keeping leading position in arsenic trioxide production in global market; world arsenic market is foreseen to go down, tighter environmental ...
[29]
Oxidation of As(III) to As(V) using ozone microbubbles - ScienceDirect
In this work, oxidation of more toxic As(III) to less toxic As(V) was studied in a pilot-plant by using ozone microbubbles.
[30]
https://melscience.com/US-en/articles/oxidation-states-arsenic/
[31]
Purification of crude As2O3 recovered from antimony smelting ...
In this study, a combined process of acidic oxidation leaching and SO2 reduction was proposed to purify crude As2O3 recovered from antimony smelting ...Missing: recrystallization distillation
[32]
Conventional oxidation treatments for the removal of arsenic with ...
The arsenic oxidation yields were excellent with potassium permanganate, very good with hypochlorite and low with monochloramine.
[33]
Method for preparing arsenic trioxide by using arsenic sulfide waste ...
... acid solution; reducing the arsenic acid solution into arsenous acid with lower solubility by sulfur dioxide gas, distilling the reaction solution under reduced ...
[34]
https://www.osha.gov/laws-regs/regulations/standardnumber/1910/1910.1018
[35]
https://wwwn.cdc.gov/TSP/PHS/PHS.aspx?phsid=18&toxid=3
[36]
Monosodium arsenate | AsH2NaO4 | CID 23677060 - PubChem - NIH
Sodium dihydrogen arsenate is an inorganic sodium salt that is the monosodium salt of arsenic acid. It has a role as a carcinogenic agent.
[37]
Inorganic Acids and Bases - pKa Values - The Engineering ToolBox
... pKa of phenols, alcohols and carboxylic acids and acid and base pH indicators ... Arsenic acid, H3AsO4, 2.26, 6.76, 11.29. Phosphoric acid, H3PO4, 2.16, 7.21 ...
[38]
[PDF] Review of Arsenic Removal Technologies for Contaminated ...
Most arsenic treatments fall into four process categories: ion exchange, membrane process, adsorption, or chemical precipitation. Ion-exchange treatments are ...<|control11|><|separator|>
[39]
SO2 + H3AsO4 + H2O = H3AsO3 + H2SO4 - Chemical Equation ...
Word Equation. Sulfur Dioxide + Arsenic Acid + Water = Arsenous Acid + Sulfuric Acid. One mole of Sulfur Dioxide [SO2] , one mole of Arsenic Acid [H3AsO4] ...
[40]
https://pubs.acs.org/doi/pdf/10.1021/j150042a001
[41]
Page 39 - Pharmaceutical Analytical Chemistry II - Pharm D- 02-06 ...
... H3AsO4 + 2I− + 2H+ H3AsO3 + I2 + H2O - Starch ... → equivalent amount of glucose) St. I2 + 2OH ... 2- Due to starch Aqueous starch suspension ...
[42]
[PDF] Standard Reduction Potentials at 25 C - Chem21Labs
Standard Reduction Potentials at 25°C. Half-Reaction. E° (V). Ag. +. (aq) + e ... H3AsO4 (aq) + 2H. +. (aq) + 2e. - → H3AsO3(aq) + H2O (l). +0.559. Ba. 2+. (aq) + ...
[43]
Chromated Copper Arsenate - an overview | ScienceDirect Topics
Chromated copper arsenate (CCA) is defined as a chemical preservative ... arsenic acid (USDA, 1980). During the treatment process, CCA, at pH 1.6–2.5 ...
[44]
[PDF] ARSENIC - USGS.gov
Arsenic metal also was used as an antifriction additive for bearings, to harden lead shot, and in clip-on wheel weights. Arsenic compounds were used in.
[45]
Response to Requests to Cancel Certain Chromated Copper ...
Apr 9, 2003 · Effective December 31, 2003, this product may only be used (1) for formulation of the following end-use wood preservative products: ammoniacal ...
[46]
[PDF] arsenic.pdf - USGS Publications Warehouse
Minor amounts of arsenic were also used in glass, in wood preservatives, in medi- cines, and in lead shot and copper alloys. The use of arsenic in glass ...Missing: ceramics etching
[47]
Exposures in the Glass Manufacturing Industry - NCBI
In acid polishing, the glass may be submerged in a mixture of hydrofluoric and concentrated sulfuric acids or in other acids; hydrofluoric acid is also used for ...Missing: preservation | Show results with:preservation
[48]
Inorganic Arsenic Emissions From Glass Manufacturing Plants ...
A second function of arsenic in glass is to act as a decolorizing ... One manufacturer has indicated that it now uses only liquid arsenic acid for their glass ...
[49]
[PDF] Arsenic April 2021 - U.S. Environmental Protection Agency
for this purpose in industrial applications. (1). • The use of arsenic in agricultural or commercial pesticide applications has been restricted and is most ...
[50]
US3871931A - Method for selectively etching silicon nitride - Google ...
Etching of silicon nitride with a hot solution of arsenic acid is faster than the conventionally-employed phosphoric acid, and has the additional advantage ...
[51]
Arsenic passivation of inP surface for metal ... - AIP Publishing
(ii) Etch in a H3As04 solution (arsenic acid 80%) for 5 min in darkness at room temperature, 12 followed by a riMe in deionized water. The surface ...
[52]
[PDF] TOXICOLOGICAL PROFILE FOR ARSENIC
High-purity arsenic (99.9999%) is used by the electronics industry for gallium-arsenide semiconductors for telecommunications, solar cells, and space research ( ...
[53]
[PDF] Lead Isotopic Compositions of Common Arsenical Pesticides Used ...
The three most commonly used compounds in New England (lead arsenate-acid form, calcium arsenate, and sodium arsenate) have similar isotopic compositions and ...<|control11|><|separator|>
[54]
Arsenic Exposure and Toxicology: A Historical Perspective - PMC
Arsenic has a long history of use as a homicidal agent, but in the past 100 years arsenic, has been used as a pesticide, a chemotherapeutic agent and a ...
[55]
An assessment of the amounts of arsenical pesticides used ...
Citation Excerpt : Calcium arsenate and lead arsenate were used extensively up to the 1950s, mostly on orchard soils to combat the codling moth. At peak, ...
[56]
Lead isotopic compositions of common arsenical pesticides used in ...
Lead arsenate was probably the most heavily used of the arsenical pesticides until it was banned in 1988. Other metal-arsenic pesticides were also used but in ...
[57]
The truth, the whole truth, and nothing but the truth
May 25, 2022 · The paper suggests that arsenic is used in leather finishes but, if it is found in tanneries today, it is more likely as an insecticide such as ...
[58]
Velvet Antler Technologies's post - Facebook
May 1, 2025 · Arsenic was historically used in leather tanning, particularly in the unhairing and preserving processes, but is no longer used in major leather production.
[59]
A recent (2009–2021) perspective on sustainable color and textile ...
A mordant is a chemical substance used to bind dyestuffs on fabrics by forming a coordination complex with the dyestuffs, which then affixes to the fibers ( ...
[60]
Heavy metals in leathers, artificial leathers, and textiles in the ...
Mar 24, 2022 · The article presents research findings on the content of arsenic, cadmium, chromium, copper, lead, and zinc in extracts from leathers, artificial leathers
[61]
Arsenic Acid - an overview | ScienceDirect Topics
Arsenic acid (H₃AsO₄) is a chemical compound that has been used in agriculture, specifically as a defoliant for cotton, and is associated with the ...
[62]
Determination of Glucose by a Modification of Somogyi-Nelson ...
The arsenomolybdate reagent which was developed by Nelson1) in 1944 has been, and is still being, widely used as the chromogenic reagent for the quantitative.<|control11|><|separator|>
[63]
Distribution of Arsenic in the Environment - NCBI - NIH
It aids in the formation of glass and is a fining agent for removing gases, an oxidizing–reducing agent, and a decolorizing agent. ... Arsenic acid: Arsenic acid ...
[64]
Arsenic | Public Health Statement | ATSDR - CDC
Studies in animals show that most simple organic arsenic compounds (such as methyl and dimethyl compounds) are less toxic than the inorganic forms. In animals, ...
[65]
ARSENIC AND ARSENIC COMPOUNDS - NCBI - NIH
Mining, smelting of non-ferrous metals and burning of fossil fuels are the major anthropogenic sources of arsenic contamination of air, water, and soil ( ...Missing: reliable | Show results with:reliable
[66]
Arsenic Toxicity - StatPearls - NCBI Bookshelf - NIH
Jun 12, 2023 · Arsenate (pentavalent arsenic) may replace phosphate in several reactions. Arsenate has a similar structure and similar properties to phosphate.
[67]
Arsenic - World Health Organization (WHO)
Dec 7, 2022 · Arsenic is naturally present at high levels in the groundwater of several countries. Arsenic is highly toxic in its inorganic form.
[68]
Health Effects of Chronic Arsenic Exposure - PMC - NIH
Arsenic has been confirmed as a human carcinogen that can induce skin, lung, and bladder cancer. There are also reports of its significant association to liver ...
[69]
Arsenic Toxicity: Background, Pathophysiology, Etiology
Oct 21, 2025 · Trivalent arsenic inhibits numerous other cellular enzymes through sulfhydryl group binding. Trivalent arsenic inhibits cellular glucose ...
[70]
Arsenic toxicity: sources, pathophysiology and mechanism - PMC
Arsenic toxicity inhibits the cellular respiration and mitochondrial energy production by deactivation of important enzymes of Kreb's cycle or by inhibition of ...
[71]
[PDF] Appendix G - Chemical Specific Soil Half Lives - OEHHA
Metals and other elements for which this soil half-life applies include arsenic, beryllium, cadmium, chromium (VI), lead and mercury. Hexavalent chromium (CrVI) ...
[72]
Evaluation of Long-Term Leaching of Arsenic from Arsenic ... - MDPI
Arsenic in the soil can leach into groundwater and contaminate drinking water, posing a serious risk to human health. Various methods have been employed to ...
[73]
Microbial Arsenic Methylation in Soil and Uptake and Metabolism of ...
Dec 10, 2019 · Microbial arsenic methylation can produce volatile TMAs(III), which will be rapidly oxidized into TMAs(V)O in the atmosphere, thus decreasing ...
[74]
[PDF] Arsenic - 1984 - U.S. Environmental Protection Agency
Little is known about the mechanisms of arsenic toxicity co aquatic organisms; however, arsenic readily forms stable bonds to sulfur and carbon in organic ...
[75]
Bioaccumulation, Biotransformation and Trophic Transfer of Arsenic ...
This article has been reviewed the bioaccumulation, biotransformation, and trophic transfer of arsenic in marine and freshwater food chain.
[76]
Drinking Water Arsenic Rule History | US EPA
On January 22, 2001, EPA adopted a new standard for arsenic in drinking water of 0.01 mg/l or 10 parts per billion (ppb), replacing the old standard of 50 ppb.
[77]
Arsenic acid - Substance Information - ECHA - European Union
The substance identifiers displayed in the InfoCard are the best available substance name, EC number, CAS number and/or the molecular and structural formulas.<|control11|><|separator|>
[78]
Chromated Arsenicals (CCA) | US EPA
Dec 26, 2024 · In December 2003, chromated arsenicals manufacturers voluntarily discontinued manufacturing chromated arsenicals-treated wood products for ...
[79]
Phytoremediation of arsenic and lead in contaminated soil using ...
Chinese Brake ferns (Pteris vittata) were used to extract arsenic. On average, fern shoot arsenic concentrations were as high as 20 times the soil arsenic ...
[80]
Removal of arsenic from drinking water by chemical precipitation
A dynamic mathematical model was developed for removal of arsenic from drinking water by chemical coagulation-precipitation and was validated experimentally.