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Methanediol

Methanediol is an organic compound with the chemical formula CH₂(OH)₂, representing the simplest geminal diol formed by the addition of water to formaldehyde.^[1]^[2] In aqueous solutions, formaldehyde exists predominantly as methanediol due to the favorable hydration equilibrium, particularly at temperatures below 200 °C, where the diol form outweighs the carbonyl by a significant margin.^[3]^[4] Despite its thermodynamic instability in the gas phase, where it readily dehydrates back to formaldehyde, methanediol has been successfully synthesized and detected through low-temperature ice processing and sublimation, highlighting its relevance in atmospheric volatile organic chemistry and potential presence in interstellar grain mantles at temperatures under 100 K.^[2]^[5] This compound's structural properties, including a preferred trans conformation for stability, have been elucidated through ab initio calculations, underscoring its role as a key intermediate in oxidation pathways from methanol to formic acid.^[6]

Chemical Identity and Properties

Molecular Structure and Nomenclature

Methanediol has the molecular formula CH₄O₂ and features a tetrahedral carbon atom at the center, singly bonded to two hydrogen atoms and two hydroxyl (-OH) groups.^[1] This configuration classifies it as a geminal diol, where both hydroxyl groups are attached to the same carbon atom, distinguishing it from vicinal diols with adjacent hydroxyls.^[1] The molecule's structure arises from the hydration of formaldehyde (H₂C=O), forming H₂C(OH)₂ through nucleophilic addition across the carbonyl bond.^[7] The IUPAC systematic name for the compound is methanediol, derived from the parent hydrocarbon methane with substitution by two hydroxy functional groups.^[1] ^[8] Alternative names include methylene glycol and formaldehyde monohydrate, reflecting its relation to formaldehyde and its hydrated form.^[1] In chemical nomenclature, it exemplifies the general class of aldehyde hydrates, though methanediol is the simplest such species.^[7] The CAS registry number is 463-57-0.^[9]

Physical and Thermodynamic Properties

Methanediol exists primarily in equilibrium with formaldehyde and water, rendering isolation of the pure compound challenging; consequently, experimental physical properties are limited, and most available data derive from computational predictions or extrapolations. Predicted values indicate a colorless liquid state at standard conditions, with a density of approximately 1.20 g/cm³. The estimated boiling point is 194 °C at 760 mmHg, accompanied by a low vapor pressure of 0.121 mmHg at 25 °C, consistent with its high polarity and hydrogen-bonding capability. Flash point estimates are around 100 °C, underscoring potential reactivity under heating.^[10]^[11]^[12] Thermodynamic properties have been derived from high-level ab initio calculations benchmarked against experimental data. The standard enthalpy of formation (Δ_f H°_{298}) for gaseous methanediol is -382.16 ± 0.94 kJ/mol, reflecting its relative stability in the gas phase compared to dissociated formaldehyde and water, though the equilibrium favors dehydration at ambient temperatures. At 0 K, Δ_f H° is -369.01 ± 0.94 kJ/mol. These values stem from Active Thermochemical Tables (ATcT), which integrate quantum chemical computations with thermochemical networks for accuracy. Spectroscopic data, including vibrational frequencies and rotational constants, support these findings but confirm methanediol's instability above ~100 K in isolation.^[13]^[14]^[15]

Chemical Stability and Hydration Equilibrium

Methanediol exists in reversible equilibrium with formaldehyde and water via the hydration reaction: H₂C=O + H₂O ⇌ H₂C(OH)₂. In aqueous solution at 298 K, this equilibrium strongly favors the diol form, with the ratio [H₂C(OH)₂]ₐq/[H₂C=O]ₐq measured at approximately 2,200, indicating that over 99% of dissolved formaldehyde exists as methanediol under dilute conditions.^[16] This preference arises from the relatively low steric hindrance in formaldehyde compared to higher aldehydes or ketones, allowing effective stabilization of the gem-diol by hydrogen bonding with solvent water.^[17] The equilibrium constant decreases with increasing temperature, shifting toward the carbonyl form; for instance, in hot water above 373 K, the solvent effect diminishes, reducing methanediol formation due to weakened hydration stabilization.^[3] Kinetic studies yield a hydration rate constant of kₕ ≈ 2.04 × 10⁵ exp(-2936/T) s⁻¹, while the reverse dehydration is slower, enabling observable persistence of methanediol in solution despite its thermodynamic instability relative to free formaldehyde and water.^[18] In the gas phase, methanediol exhibits sufficient kinetic stability for isolation and detection, as demonstrated by its synthesis via reaction of diazomethane with water, with decomposition barriers calculated at around 20-30 kcal/mol via concerted proton transfer mechanisms.^[19] Theoretical analyses confirm that unimolecular decomposition proceeds through a transition state involving intramolecular proton shift from one hydroxyl to the adjacent oxygen, yielding formaldehyde-water complexes, though explicit water molecules or ions can lower activation energies in catalyzed pathways.^[4] Overall, methanediol's instability manifests primarily under conditions promoting dehydration, such as elevated temperatures or low water activity, underscoring its role as a transient species in both laboratory and environmental contexts.^[2]

Synthesis and Preparation

Laboratory Methods

Methanediol is prepared in the laboratory primarily through the hydration of formaldehyde in aqueous solution, where formaldehyde (HCHO) equilibrates with water to form CH₂(OH)₂ according to the reaction HCHO + H₂O ⇌ CH₂(OH)₂.^[4] This equilibrium constant favors the diol form substantially, with a hydration constant K_hyd ≈ 2 × 10³ at 20°C, resulting in over 99% conversion to methanediol in dilute solutions (<1 M).^[4] Practically, aqueous formaldehyde solutions are generated by depolymerizing paraformaldehyde under reflux in water or by dissolving commercial formalin (37% formaldehyde in water, stabilized with methanol) and distilling to remove methanol if needed.^[20] To isolate or generate gaseous methanediol for spectroscopic or reaction studies, vapors are produced by controlled evaporation of these aqueous solutions under reduced pressure or mild heating, minimizing dehydration back to formaldehyde.^[20] This method yields detectable CH₂(OH)₂ in the gas phase, confirmed via mass spectrometry and rotational spectroscopy, though the molecule's thermal instability requires low temperatures (e.g., <0°C) and rapid transfer to avoid decomposition.^[20] Alternative approaches involve homogeneous catalysis, such as ruthenium complexes converting methanol to formaldehyde hydrate via oxidase enzymes, but these are less common for routine preparation due to complexity.^[21] Purified methanediol solutions can be concentrated by cooling or adjusting pH to shift equilibrium, but attempts to isolate solid or pure liquid forms fail due to rapid dehydration and polymerization to polyoxymethylene glycols.^[4] Laboratory handling emphasizes dilute conditions to suppress side reactions like cannizzaro disproportionation in alkaline media.^[22]

Astrophysical and Low-Temperature Synthesis

Methanediol has been synthesized in laboratory simulations of astrophysical conditions by irradiating low-temperature ices composed of methanol (CH₃OH) and molecular oxygen (O₂) with energetic electrons, replicating the effects of cosmic rays on interstellar dust grains. In experiments conducted at approximately 5 K, such processing leads to the formation of methanediol through sequential addition of hydrogen and hydroxyl groups to formaldehyde intermediates, with subsequent warm-up and sublimation enabling its identification in the gas phase via infrared spectroscopy. This method, reported in 2021, marks the first confirmed preparation of isolated gaseous methanediol, yielding characteristic vibrational bands at 3700–3500 cm⁻¹ (O–H stretches) and 1100–1000 cm⁻¹ (C–O stretches).^[2]^[23] These low-temperature syntheses underscore methanediol's potential as a transient intermediate in interstellar chemistry, where it may form within icy mantles on dust particles exposed to ionizing radiation, facilitating pathways to more complex polyols and prebiotic molecules without requiring gas-phase reactions. Quantum chemical modeling supports that barrierless ion-molecule reactions involving protonated hydroxymethyl (CH₂OH⁺) and water can produce methanediol in dense molecular clouds, with subsequent neutralization yielding the neutral species. While direct detection in the interstellar medium remains elusive due to its high reactivity and tendency to dehydrate, the lab-derived spectra predict observable rotational transitions in the 100–500 GHz range, amenable to submillimeter telescopes like ALMA.^[5]^[24] In non-astrophysical low-temperature contexts, methanediol emerges from the hydration of formaldehyde in aqueous solutions cooled below 0 °C, though equilibrium favors dissociation above -20 °C; cryogenic trapping stabilizes it for spectroscopic study. Energetic processing of pure water-formaldehyde ices at 10–20 K similarly generates methanediol via radical recombination, but yields are lower without oxygen co-reactants, emphasizing the role of oxidative environments in efficient synthesis. These techniques highlight methanediol's instability at ambient conditions, confining its persistence to extreme cold.^[2]^[25]

Natural Occurrence

Interstellar and Astrophysical Contexts

Methanediol (CH₂(OH)₂) is thermodynamically stable at temperatures below 100 K, corresponding to the conditions prevalent in interstellar grain mantles, where it may form via the hydration of formaldehyde (H₂CO) on icy surfaces.^[15] Theoretical quantum chemical calculations indicate that gas-phase methanediol can convert to formaldehyde and water through a submerged barrier, but this process is kinetically hindered at low temperatures, favoring persistence in dense molecular clouds.^[26] As a key intermediate in interstellar chemistry, methanediol participates in pathways leading to complex organic molecules, including reactions with hydroxymethyl cations (CH₂OH⁺) that contribute to the synthesis of species like dihydroxycarbene and higher alcohols observed in star-forming regions.^[5] Computational studies have predicted its rotational and vibrational spectroscopic parameters, facilitating potential radio and infrared detection efforts in the interstellar medium (ISM), though no confirmed astronomical observations exist as of 2023.^[27]^[28] In astrophysical models of hot cores and protostellar envelopes, methanediol is implicated in the ice-phase chemistry of formaldehyde-rich environments, potentially desorbing as gas during warm-up phases but remaining elusive due to rapid dehydration upon heating above 100 K.^[29] Its role underscores the importance of geminal diols in bridging simple aldehydes to prebiotic organics in cold cosmic ices.^[5]

Terrestrial Aqueous Environments

In terrestrial aqueous environments, including rivers, lakes, and groundwater, methanediol exists predominantly as the hydrated form of formaldehyde via the reversible reaction HCHO + H₂O ⇌ CH₂(OH)₂, governed by an equilibrium constant K_hyd ≈ 2 × 10³ M⁻¹ at 25°C, which ensures >99% hydration at environmental concentrations below 10⁻⁴ M and neutral pH.^[18] This equilibrium establishes rapidly, with hydration reaching 90% completion in milliseconds, and methanediol often oligomerizes further into poly(oxymethylene) glycols (e.g., HO(CH₂O)ₙH, n=2–8) at higher total formaldehyde levels.^[30] Sources of formaldehyde leading to methanediol formation include atmospheric wet deposition from photochemical oxidation of methane and other hydrocarbons, in situ microbial breakdown of natural organic matter, and terrestrial runoff carrying plant-derived or anthropogenic emissions.^[31] In unpolluted surface waters, total formaldehyde concentrations (free plus hydrated forms) typically range from <1 μg/L to 10 μg/L, with raw water surveys reporting 1–25 μg/L before treatment influences.^[31] ^[32] For example, measurements in the North Saskatchewan River yielded up to 9.0 μg/L, reflecting natural variability from organic decomposition.^[32] Methanediol persistence is limited by rapid aerobic biodegradation (half-lives of 24–168 hours in surface waters) and abiotic oxidation, preventing significant accumulation except in low-oxygen or polluted settings where levels may transiently exceed 20 μg/L total formaldehyde equivalent.^[30] In groundwater, concentrations are generally lower (<1–5 μg/L in pristine aquifers) due to dilution and sorption, though contamination from industrial leachate can elevate them locally to 10–20 μg/L.^[33] These low ambient levels underscore methanediol's transient role in aqueous biogeochemistry rather than as a stable environmental reservoir.^[30]

Applications and Uses

Role in Formaldehyde Solutions

In aqueous formaldehyde solutions, methanediol predominates due to the hydration equilibrium CH₂O + H₂O ⇌ CH₂(OH)₂, which strongly favors the diol form under ambient conditions.^[34] The equilibrium constant for hydration, K_h ≈ e^(3769/T - 5.494) where T is in Kelvin, yields values around 10³ at room temperature, resulting in only trace amounts of free formaldehyde (typically <1% in dilute solutions) and the majority existing as methanediol or its oligomeric hemiacetals.^[35] This shift is entropy-driven and enhanced by water's solvent effects, which stabilize the hydrated species more at lower temperatures.^[3] Commercial formaldehyde solutions, such as 37-40% w/w formalin used in preservation and disinfection, consist primarily of methanediol as the stabilized species, improving solubility beyond that of anhydrous formaldehyde (which polymerizes readily).^[36] The hydration reduces the concentration of reactive monomeric aldehyde, mitigating unwanted side reactions like polymerization, though additional stabilizers (e.g., 10-15% methanol) are incorporated to further inhibit paraformaldehyde formation.^[36] In these solutions, methanediol serves as a dynamic reservoir, slowly releasing formaldehyde via dehydration for biocidal or cross-linking applications in histology and embalming.^[34] The equilibrium's reversibility enables precise control in industrial processes, but heating or dilution can shift it toward free formaldehyde, influencing reaction kinetics.^[35] Spectroscopic methods, including ¹H NMR, confirm methanediol's dominance by quantifying the low free aldehyde fraction without isotopic labeling.^[37]

Use in Cosmetics as Methylene Glycol

Methylene glycol, also known as methanediol, serves as a key ingredient in certain cosmetic products, particularly nail hardeners and hair-smoothing treatments, where it acts as a protein cross-linking agent. In nail applications, it bonds with the keratin in fingernails, increasing hardness and reducing brittleness, with formulations historically containing up to 5% methylene glycol.^[38]^[39] In hair products, it is incorporated into keratin treatments that, when heated during application (typically at temperatures exceeding 180°C), decompose to release formaldehyde gas, enabling semi-permanent straightening by forming methylene bridges between polypeptide chains.^[40]^[41] The Cosmetic Ingredient Review (CIR) Expert Panel assessed methylene glycol's safety in 2013, concluding it safe for use in cosmetics when formulated to limit free formaldehyde to minimal effective levels, such as below 0.074% in nail hardeners and 0.1-0.2% as a preservative, based on exposure data showing negligible systemic absorption and irritation risks under controlled conditions.^[42]^[43] However, regulatory frameworks differ: the U.S. FDA has issued warnings since 2011 about hair-smoothing products containing methylene glycol due to airborne formaldehyde emissions during use, which can exceed OSHA workplace limits (0.75 ppm) and cause respiratory irritation, eye damage, and skin sensitization, prompting voluntary reformulations or recalls in cases of mislabeling.^[40]^[44] In the European Union, formaldehyde and methylene glycol are prohibited outright in finished cosmetic products under Annex II of Regulation (EC) No 1223/2009 (entries 1577 and 1579, effective since amendments in 2019), though prior allowances for up to 0.2% free formaldehyde equivalent as a preservative were permitted before stricter equivalence rulings deemed methylene glycol a direct formaldehyde source.^[38]^[45] Debates center on chemical equivalence, with regulators like the EU's Scientific Committee on Consumer Safety (SCCS) asserting in 2011 that methylene glycol in aqueous solutions equilibrates with formaldehyde via hydration-dehydration, rendering it functionally identical for toxicity assessments, despite industry arguments for distinct risk profiles at low concentrations.^[46] Empirical data from vapor studies confirm rapid formaldehyde release from methylene glycol under heat or acidic conditions typical in cosmetic applications, supporting calls for labeling transparency and ventilation requirements in professional settings.^[41] Consumer exposure risks include allergic contact dermatitis, with patch test data indicating sensitization rates up to 4% in formaldehyde-exposed populations, though CIR reviews found no evidence of carcinogenicity from cosmetic uses at approved levels.^[43]^[42]

Safety, Toxicology, and Health Effects

Toxicological Profile

Methanediol, also known as methylene glycol, demonstrates toxicity primarily through its rapid equilibrium with formaldehyde in biological and aqueous environments, where it decomposes to release the more reactive aldehyde species responsible for adverse effects.^[46] This equilibrium implies that methanediol lacks independent toxicological mechanisms beyond those of formaldehyde, with no evidence of unique metabolites or pathways contributing to harm.^[46] Formaldehyde, classified by the International Agency for Research on Cancer (IARC) as a Group 1 human carcinogen based on sufficient evidence of nasopharyngeal cancer from occupational inhalation exposures exceeding 1 ppm, induces DNA-protein crosslinks and genotoxic damage at sites of first contact, such as nasal epithelium.^[47] Systemic circulation of intact methanediol is negligible due to its instability, limiting distant organ effects but amplifying local irritation and mutagenicity where formaldehyde is generated.^[48] Acute oral toxicity data for methylene glycol solutions indicate moderate hazard levels, with reported LD₅₀ values of 5,682 mg/kg in rats and 7,300 mg/kg in mice, reflecting lower potency compared to anhydrous formaldehyde (LD₅₀ ~800 mg/kg in rats) due to hydration and dilution effects. Inhalation LC₅₀ for formaldehyde equivalents in aqueous forms approaches 16,000 ppm over 6 hours in rats, causing severe respiratory irritation, pulmonary edema, and death at high concentrations.^[49] Dermal exposure to concentrated solutions results in corrosive irritation, with formaldehyde releasers like methanediol penetrating skin barriers to cause protein denaturation and sensitization, evidenced by allergic contact dermatitis in 1-2% of exposed individuals in patch testing studies.^[43] Ocular exposure induces immediate lacrimation, conjunctival damage, and potential corneal opacity, mirroring formaldehyde's irritant profile at concentrations above 0.1%.^[43] Chronic low-level exposure via inhalation or dermal routes, as in occupational or cosmetic applications, primarily manifests as mucous membrane irritation, with threshold limit values set at 0.3-0.75 ppm for formaldehyde to prevent sensory effects.^[49] Genotoxicity arises from formaldehyde's ability to form DNA adducts, confirmed in vitro and in rodent nasal tissues, though human leukemia associations remain contested due to lack of consistent bone marrow dosimetry and negative findings in recent meta-analyses.^[50] In cosmetic contexts, such as nail hardeners or hair treatments containing up to 5% methylene glycol, the Cosmetic Ingredient Review (CIR) Expert Panel concluded safety when free formaldehyde does not exceed 0.1-0.2%, based on margin-of-safety calculations exceeding 100 for sensitization and irritation endpoints.^[43] However, regulatory bodies like the FDA have proposed bans on formaldehyde-releasing straighteners due to elevated cancer risks from heated vapor emissions, highlighting discrepancies between industry assessments and precautionary interpretations of IARC data.^[51] Reproductive and developmental toxicity is not distinctly attributed to methanediol beyond general formaldehyde effects, with no specific teratogenic data isolated from equilibrium dynamics.^[43]

Exposure Routes and Risk Assessment

Primary exposure to methanediol, also known as methylene glycol, occurs through dermal contact in cosmetic applications, particularly nail hardeners (containing 0.8%–3.5% methylene glycol, equivalent to 0.5%–2.2% formaldehyde) and hair-smoothing products (up to <5% methylene glycol).^[43] In professional salon environments, inhalation represents a significant route during product application, as heating (e.g., blow-drying or flat-ironing) promotes dehydration to formaldehyde vapor, with measured concentrations ranging from 0.074 ppm to 1.88 ppm, occasionally exceeding occupational limits like the ACGIH ceiling of 0.3 ppm.^[43] Ingestion is not a primary consumer route but may occur accidentally via contaminated hands or products, though data on oral exposure specifically for methanediol are limited and derive from formaldehyde solution studies.^[43] Risk assessment evaluates methanediol's hazards through its equilibrium with formaldehyde, which drives irritancy, sensitization, and potential carcinogenicity, though full toxicological equivalence is debated due to incomplete dehydration under typical conditions (e.g., <50% conversion from 37% formalin at 400°F).^[46] Dermal risks include irritation and allergic contact dermatitis at formaldehyde equivalents >0.2%, with human reports of burning and redness from nail hardeners; sensitization potential is concentration-dependent, affecting susceptible individuals.^[43] Inhalation risks encompass acute respiratory and ocular irritation at levels above 0.1–1 ppm, with chronic high exposures (≥6 ppm in animal models) linked to nasopharyngeal cancer via local mucosal effects rather than systemic distribution, as hydrated forms like methanediol exhibit limited absorption and rapid local reactivity.^[43] ^[52] The Cosmetic Ingredient Review (CIR) Expert Panel concludes methanediol is safe in cosmetics at ≤0.2% formaldehyde equivalents, with nail hardeners deemed safe up to 5% under precautions (e.g., avoiding skin contact and ensuring ventilation), but unsafe in aerosolized or high-heat hair products due to excessive vapor release.^[43] No evidence supports systemic reproductive or genotoxic effects at cosmetic exposure levels, with animal data requiring doses >5 ppm for malformations; human epidemiology shows weak associations at occupational exposures.^[43] Overall, risks are mitigated by formulation limits and use guidelines, prioritizing local irritancy over remote carcinogenesis, though individual sensitivity and poor ventilation amplify hazards.^[43]

Regulatory Framework and Controversies

Historical Regulations

In the 1980s, regulatory assessments of formaldehyde, of which methanediol (methylene glycol) is the hydrated form, began addressing its use in cosmetics. The Cosmetic Ingredient Review (CIR) Expert Panel's initial 1984 safety assessment concluded that formaldehyde was safe as a preservative in cosmetics provided free formaldehyde concentrations did not exceed 0.2%, influencing subsequent voluntary industry standards in the United States.^[53] This threshold accounted for methanediol's equilibrium with formaldehyde in aqueous solutions, though specific distinctions between the compounds were not yet emphasized. By the early 2000s, the use of methanediol in keratin-based hair smoothing products, marketed as "formaldehyde-free" alternatives, prompted scrutiny due to its thermal decomposition releasing formaldehyde gas. In 2010, the U.S. Food and Drug Administration (FDA) issued public warnings about such products after receiving consumer complaints of adverse effects like respiratory irritation and scalp burns, confirming laboratory tests on brands like Brazilian Blowout detected methylene glycol converting to formaldehyde upon heating.^[40] The FDA advised against their use in salons, highlighting occupational exposure risks, but stopped short of a federal ban, deferring to voluntary compliance.^[54] In 2011, the CIR revisited formaldehyde and methylene glycol, affirming general safety at or below 0.2% free formaldehyde equivalent but deeming them unsafe for hair-smoothing applications due to elevated emission levels during processing.^[43] Concurrently, the European Commission's Scientific Committee on Consumer Safety (SCCS) evaluated hair straightening products in 2012, concluding that methylene glycol must be regarded as chemically equivalent to formaldehyde under cosmetic use conditions, subjecting it to existing formaldehyde restrictions in Regulation (EC) No 1223/2009, including labeling requirements for concentrations exceeding 0.05% in ready-for-use products.^[55] These assessments underscored methanediol's role as a formaldehyde releaser, aligning regulations with toxicological equivalence rather than nominal ingredient labeling.

Recent Developments and Debates on Equivalence to Formaldehyde

In aqueous solutions, methanediol (also known as methylene glycol) exists in chemical equilibrium with formaldehyde, where the hydration reaction \ce{CH2O + H2O ⇌ CH2(OH)2} favors the diol form at concentrations below approximately 30% but still permits dissociation to release free formaldehyde, particularly under heat, pH changes, or biological conditions.^[46] This equilibrium underpins debates on their equivalence, with some regulators and toxicologists asserting chemical and toxicological interchangeability due to the rapid interconversion and shared reactivity of the carbonyl group in formaldehyde.^[56] However, critics, including analyses from industry-affiliated researchers, contend that strict equivalence overlooks differences in stability and behavior; for instance, concentrated formalin solutions (predominantly methanediol) do not exhibit identical vapor-phase release or dermal penetration rates as anhydrous formaldehyde, suggesting methanediol lacks inherent toxicity beyond trace free formaldehyde.^[57] The Cosmetic Ingredient Review (CIR) Expert Panel, in its 2013 amended safety assessment, evaluated formaldehyde and methylene glycol as functionally equivalent for cosmetic use, deeming both safe at concentrations not exceeding 0.2% free formaldehyde equivalents to mitigate irritation and sensitization risks, based on dermal absorption data and no observed adverse effects in patch tests up to those limits.^[43] This stance has faced pushback in toxicological literature, where arguments emphasize that methanediol's polymeric forms (e.g., paraformaldehyde in solution) may polymerize rather than fully depolymerize to monomeric formaldehyde in vivo, potentially reducing bioavailable exposure compared to direct formaldehyde dosing; such views cite equilibrium constants showing less than 1% free formaldehyde in typical cosmetic formulations.^[46] No major peer-reviewed studies post-2020 have resolved this, but the debate persists in regulatory contexts, with equivalence often assumed for precautionary risk assessments despite calls for compound-specific kinetics.^[56] Regulatory developments since 2020 have increasingly treated methanediol as a formaldehyde releaser, implying practical equivalence in hazard profiles. The U.S. EPA's 2024 draft Toxic Substances Control Act (TSCA) risk evaluation identified chronic formaldehyde exposure—including from hydrated releasers like methylene glycol in adhesives and textiles—as posing unreasonable risks to pulmonary function and immune sensitization, prompting proposed restrictions under TSCA authority effective by 2025.^[58] In cosmetics, Washington's Toxics-Free Cosmetics Act, enforced from January 1, 2025, bans formaldehyde and 24 releasers (including quaternium-15, which generates methylene glycol), with full prohibition on releasers by 2027, driven by cancer and reproductive toxicity data from formaldehyde metabolism.^[59] ^[60] The FDA, in February 2025, advanced plans to propose banning formaldehyde and releasers in hair-smoothing products, citing emission data showing up to 0.1% free formaldehyde release from "formaldehyde-free" methylene glycol formulations during application.^[61] These actions reflect a consensus shift toward regulating releasers equivalently to free formaldehyde, prioritizing endogenous conversion risks over formulation distinctions, though industry groups argue this overlooks exposure modeling showing sub-threshold releases in diluted products.^[62] As of October 2025, no federal U.S. outright ban exists, but state-level measures and EPA rulemaking signal escalating scrutiny, with debates centering on whether equilibrium dynamics justify distinct labeling or if precautionary equivalence better protects against underreported emissions.^[63]

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The reaction rate of the hydration of formaldehyde is obtained from the measured, chemically enhanced absorption rate of formaldehyde gas into water in a ...Missing: methanediol | Show results with:methanediol
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Review and environmental footprint assessment of various formalin ...
Dec 1, 2022 · ... formalin as the major product in aqueous solution. For the formalin to stabilise, methanediol (CH4O2) was formed as the main product in the ...Review And Environmental... · 2.1. Formalin Synthesis Via... · 2.1. 1. Formalin Produced...
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Quantification of Monomeric Formaldehyde in Aqueous Solutions by ...
Jun 29, 2025 · We show here that the amount of monomeric formaldehyde in aqueous solutions can be determined without the use of deuterated water by 1H NMR ...Missing: methanediol | Show results with:methanediol
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Formaldehyde (Methylene Glycol) - Cosmetics Info
Formaldehyde and methylene glycol are listed in the Annex II list of substances prohibited in cosmetics products (Entries 1577 and 1579) and may not be used in ...
[39]
Amended Safety Assessment of Formaldehyde and Methylene ...
The CIR Expert Panel concluded that formaldehyde and methylene glycol are safe for use in cosmetics when formulated to ensure use at the minimal effective ...
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Hair Smoothing Products That Release Formaldehyde When Heated
Oct 15, 2024 · These products often contain formaldehyde, also known as formalin and methylene glycol. When the solution is heated, the formaldehyde in the products is ...
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[PDF] in hair straighteners METHYLENE GLYCOL
Methylene glycol is an ingredient used in some hair-straightening products. It is formed by the reac- tion of formaldehyde with water.
[42]
Amended safety assessment of formaldehyde and methylene glycol ...
Formaldehyde and methylene glycol may be used safely in cosmetics if established limits are not exceeded and are safe for use in nail hardeners.
[43]
Amended Safety Assessment of Formaldehyde and Methylene ...
Formaldehyde and methylene glycol may be used safely in cosmetics if established limits are not exceeded and are safe for use in nail hardeners.
[44]
https://www.osha.gov/hair-salons/products
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[PDF] amending Annexes II, III and V to Regulation (EC) No 1 - EUR-Lex
May 23, 2019 · Regulation are safe for use in cosmetics under certain conditions. ... Methanediol; methylene glycol. 463-57-0. 207-339-5. 1580. Cymoxanil (ISO); ...
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Formaldehyde and methylene glycol equivalence - ScienceDirect.com
Certain physical properties of MG and FA help determine the likelihood of inhalation exposures under varying use conditions. In particular, this becomes an ...
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[PDF] Formaldehyde - IARC Publications
Formaldehyde is carcinogenic to humans (Group 1). There ... In aqueous solution, formaldehyde is converted mostly to oligomers of its diol form methanediol ...
[48]
Distribution of DNA Adducts Caused by Inhaled Formaldehyde Is ...
Inhaled formaldehyde is classified as a known human and animal carcinogen, causing nasopharyngeal cancer. Additionally, limited epidemiological evidence for ...
[49]
https://www.osha.gov/laws-regs/regulations/standardnumber/1910/1910.1048AppA
[50]
Six years after the NRC review of EPA's Draft IRIS Toxicological ...
New findings are consistently negative, and integration of all available evidence challenges the earlier conclusions that formaldehyde causes leukemia.
[51]
FDA May Ban Hair Straighteners With Formaldehyde Over Cancer ...
Oct 24, 2023 · The FDA has proposed banning hair straightening products containing formaldehyde, a known human carcinogen. The cancer-causing effects of ...
[52]
Systemic Health Effects - - NCBI - NIH
Thus, systemic responses are unlikely to arise from the direct delivery of formaldehyde (or its hydrated form methanediol) to a distant site in the body.
[53]
[PDF] BLUE Formaldehyde/Methylene Glycol CIR EXPERT PANEL ...
Aug 26, 2011 · At the June meeting, the Panel issued a revised tentative amended safety assessment for formaldehyde and methylene glycol with the conclusion ...<|separator|>
[54]
https://www.osha.gov/hair-salons/time-line
[55]
[PDF] Scientific Committee on Consumer Safety SCCS
Sep 18, 2012 · Methylene glycol (CAS 463-57-0; EC 207-339-5), or hydrated formaldehyde is formed upon dissolution of formaldehyde in water and exists in ...
[56]
Formaldehyde and methylene glycol equivalence - PubMed
A review of relevant literature demonstrates that methylene glycol has no inherent toxicity apart from whatever concentration of formaldehyde that might be ...
[57]
(PDF) Formaldehyde and Methylene Glycol Equivalence
Aug 10, 2025 · Formaldehyde and Methylene Glycol Equivalence: Critical Assessment of Chemical and Toxicological Aspects. April 2014; Regulatory Toxicology ...<|control11|><|separator|>
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Increasing Regulatory Scrutiny of Formaldehyde Under TSCA | HUB
Nov 1, 2024 · The EPA 2024 Draft TSCA Assessment found that chronic exposure to formaldehyde may result in reduced pulmonary function, increased asthma ...
[59]
Washington moves to restrict cancer-causing chemicals in cosmetics
Aug 28, 2025 · Since Jan. 1, 2025, the Toxics-Free Cosmetics Act restricts the use of formaldehyde and other toxic chemicals intentionally added to cosmetics ...
[60]
New Rule Prohibits the Use of Formaldehyde Releasers in ... - SGS
Sep 16, 2025 · The State of Washington restricts 25 formaldehyde-releasing chemicals in cosmetics, effective 2027.
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FDA's plan to propose ban on formaldehyde in hair-straightening ...
Feb 11, 2025 · A plan for the US Food and Drug Administration to propose banning formaldehyde and certain formaldehyde-releasing chemicals from being used ...
[62]
Fight over formaldehyde safety continues - C&EN
Jan 3, 2025 · The findings set the stage for new restrictions or bans on formaldehyde uses that fall under the Toxic Substances Control Act (TSCA) and ...
[63]
EPA Seeks Small Entity Representatives for Formaldehyde and ...
Aug 8, 2025 · The panels will focus on Toxic Substances Control Act (TSCA) regulations for formaldehyde and asbestos. Why: Formaldehyde is used in: Resins ...