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Sodium silicate

Sodium silicate, also known as water glass or liquid glass, is a versatile composed of (Na₂O) and (SiO₂), with a general of Na₂O · x SiO₂ where x is the molar ratio of SiO₂ to Na₂O (typically 1.5–3.3 for commercial grades, e.g., around 3.22 for some). It typically appears as a colorless, viscous or a white to grayish-white solid, exhibiting strong alkaline properties with a of 11–13 in solution due to its ionic nature. This is highly soluble in , forming stable colloidal solutions, and is valued for its , , and buffering capabilities across numerous industries. Industrial production of sodium silicate primarily involves the high-temperature fusion of silica sand (SiO₂) with soda ash (Na₂CO₃) in a at approximately 1,100–1,300°C, yielding a solid that is then dissolved in hot water under pressure to produce the liquid form. Alternative hydrothermal methods react caustic soda (NaOH) with silica sources like or waste cullet in an at elevated temperatures and pressures, offering a more energy-efficient route for certain ratios. The resulting product can be adjusted for specific SiO₂/Na₂O ratios, influencing its viscosity, density (typically 1.3–1.5 g/cm³), and reactivity. Sodium silicate serves as a key ingredient in detergents and cleaning agents, where it acts as a to soften , prevent soil redeposition, and stabilize enzymes. In and refractories, it functions as a for cements, mortars, and fireproof coatings, enhancing durability and heat resistance in applications like molds and acid-resistant linings. Additional uses include for inhibition, aids, and iron sequestration; paper production as a surface agent; and adhesives for , , and textiles. Its role in , rod coatings, and even organic agriculture as a and floatant underscores its broad utility.

Overview

Definition and forms

Sodium silicate is an composed of (Na₂O) and silica (SiO₂), primarily represented by the Na₂SiO₃, though it exists commercially as a range of mixtures with the general composition Na₂O · nSiO₂, where n typically varies from 1 to 3.75. This variability in the silica-to-soda ratio allows for tailored properties in industrial applications, with the compound acting as a where serves as the to sodium. The term "water glass" originates from the material's characteristic glassy appearance, forming a vitreous solid upon drying or solidification of its solutions. Sodium silicate is available in several common forms to suit different uses: liquid solutions, often viscous syrups with 20-50% solids content dissolved in ; powdered solids, such as or hydrated metasilicates; and granular solids, typically produced by crushing fused lumps. Commercial grades of sodium silicate are primarily distinguished by their SiO₂/Na₂O weight ratio, which influences , , and reactivity; ratios below 2.85:1 are classified as alkaline, while those above are . For example, grades like Type N have ratios around 3.2:1, with typical densities of 1.3-1.5 g/cm³ and viscosities ranging from 100-500 centipoise (cps), making them suitable for applications requiring slower dissolution. Quick-dissolving variants feature modified ratios or formulations for faster solubilization in water. These grades are standardized by manufacturers to ensure consistency in properties like specific gravity and solids content.

Nomenclature

Sodium silicate is the generic term for a series of compounds composed of (Na₂O) and (SiO₂) in varying proportions, often represented by the general formula (Na₂O)_x · (SiO₂)_y. Common names for these compounds include water glass, liquid glass, and soluble glass, reflecting their glassy appearance in solid form and solubility in water. The systematic IUPAC distinguishes specific forms based on structure; for example, the metasilicate Na₂SiO₃ is named disodium metasilicate or disodium dioxido(oxo), while the Na₄SiO₄ is termed tetrasodium or tetrasodium . Other variants, such as polysilicates with higher silica content, are designated as sodium polysilicates. Compositions are frequently denoted by the molar of SiO₂ to Na₂O (often symbolized as "n" or ""), such as a 2.0 expressed as Na₂O · 2SiO₂. This influences descriptive ; for instance, products with ratios below approximately 2.85 are classified as alkaline sodium silicates, whereas those with higher ratios are known as neutral grades, and high-silica variants may be referred to as soda.

History

Discovery and early uses

The formation of alkali silicates as a soluble substance was first reported around 1640 by Flemish chemist , who obtained it by melting silica (sand) with excess caustic potash, serving as an early analog to sodium silicate through the reaction of silica with an alkali. The first deliberate preparation of sodium silicate occurred in 1818, when German mineralogist Johann Nepomuk von Fuchs fused soda ash () with silica to produce a water-soluble form of the compound. In the late , sodium silicate saw initial applications as a for eggs, where immersion in its solution formed a thin protective on the shells to inhibit bacterial penetration and extend freshness. During the , conducted demonstrations highlighting the material's notable in —contrasting with ordinary —and its glass-like and when dried, sparking interest in its potential beyond settings.

Industrial development

The industrial production of sodium silicate, often referred to as water glass, began to take shape in the mid-19th century following early scientific advancements in . In the 1850s, the first commercial manufacturing plants were established in and the , marking the transition from laboratory experiments to large-scale operations. These plants capitalized on processes developed by Johann Nepomuk von Fuchs in the 1820s, who had pioneered the production of soluble silicates in , enabling the synthesis of sodium silicate from silica and soda ash under heat. By the late , production expanded significantly to support emerging applications in materials, , and adhesives. Key innovations included patents for using sodium silicate as a in artificial stone and compositions; for instance, inventor Ransome secured patents in the 1860s for processes combining sodium silicate with and calcium chloride to produce durable cast stone blocks, which gained popularity as cost-effective alternatives to natural stone in building projects. This period saw the establishment of major producers, such as the Quartz Company (later PQ Corporation), founded in 1831 by Elkinton and beginning commercial sodium silicate production in 1861 to supply soap manufacturers, evolving into a leading global supplier by the early 1900s. The 20th century witnessed explosive growth in sodium silicate output, driven by post-World War II industrial expansion in consumer goods and infrastructure. Demand surged for its roles in detergents as a builder to enhance cleaning efficiency and in for inhibition and , aligning with the rise of synthetic detergents and municipal water systems in the 1950s and 1960s. By 2000, global production had reached approximately 3-4 million metric tons annually. Production continued to grow in the , reaching about 8.4 million metric tons as of 2025, reflecting its status as a high-volume chemical essential to modern industry.

Structure and properties

Molecular structure

Sodium silicate is an ionic compound composed of sodium cations (Na⁺) and polymeric anions derived from -oxygen tetrahedra. The anions vary depending on the specific form: for example, orthosilicates feature discrete [SiO₄]⁴⁻ units, while metasilicates exhibit chain-like [SiO₃]²⁻ structures where atoms are linked via bridging oxygen atoms. In solid state, sodium silicate predominantly exists as an amorphous due to its network-forming nature, but certain hydrates adopt crystalline forms, such as the nonahydrate Na₂SiO₃·9H₂O ( V). The , denoted by n in the general (Na₂O)·n(SiO₂), determines the anionic architecture: low n values (e.g., n=0.5 for ) result in isolated SiO₄ , whereas higher n (e.g., n=1 for metasilicate) leads to infinite linear chains or layered sheets connected by Si-O-Si bridges, enhancing the structural connectivity. Raman and () spectroscopy confirm the presence of these Si-O-Si linkages in sodium silicate structures. Raman spectra display characteristic bands near 1050–1200 cm⁻¹ attributed to symmetric stretching of bridging Si-O-Si bonds in the polymeric network, while ²⁹Si reveals distinct chemical shifts for Qⁿ species (where n=0–4 indicates the number of bridging oxygens per ), supporting the tetrahedral coordination and extent.

Physical properties

Sodium silicate exists in various forms, including solids, hydrated crystals, and aqueous solutions, each exhibiting distinct physical characteristics. In its form, sodium silicate appears as a white to grayish-white or flakes, often with a glassy due to its amorphous nature. Aqueous solutions are typically colorless and transparent, though they can become cloudy or viscous at higher concentrations. The of is 2.61 g/cm³. For common commercial aqueous solutions containing around 40% sodium silicate, the ranges from 1.3 to 1.5 g/cm³ at , varying with the SiO₂ to Na₂O ratio and exact concentration. These densities influence handling and application in industrial processes. The of pure Na₂SiO₃ is around 1089°C, though this value can vary slightly with the degree of and specific composition; hydrated forms decompose or soften at lower temperatures rather than melting sharply. Sodium silicate is highly soluble in , with exceeding 20 g/100 mL at 25°C for the metasilicate form, allowing for concentrated solutions up to 40% by weight at . These solutions form strongly alkaline mixtures with values typically between 11 and 13. It is insoluble in alcohols and most organic solvents. The of aqueous sodium silicate solutions varies significantly with concentration, SiO₂:Na₂O , and , ranging from about 10 for dilute solutions to over 1000 for concentrated ones at 20°C. For instance, a 40% with a ratio of 3.22 may exhibit viscosities of 25 to 2500 mPa·s, making it suitable for applications requiring flow control. This property arises partly from polymeric silicate anions in , as noted in structural analyses.

Chemical properties

Sodium silicate displays pronounced when dissolved in water, arising from its to generate ions and ions, thereby elevating the of the solution. This behavior stems from the partial of the anion, represented approximately by the equation \ce{Na2SiO3 + H2O ⇌ 2NaOH + H2SiO3}, where (\ce{H2SiO3}) forms alongside , though the reaction is more accurately described as an involving polymeric species and \ce{OH-}. The extent of hydrolysis depends on the SiO₂:Na₂O ratio, with lower ratios yielding more alkaline solutions due to greater availability of \ce{Na+} ions. In reactions with acids, sodium silicate neutralizes the acid while precipitating , which often gels upon standing. A representative example is its interaction with : \ce{Na2SiO3 + 2HCl -> 2NaCl + H2SiO3}, producing a white as \ce{H2SiO3} polymerizes and dehydrates to form hydrated silica. This reaction proceeds vigorously with strong acids, generating heat and potentially violent effervescence, but is less intense with weaker acids like acetic acid. Sodium silicate shows resistance to dilute acids under neutral or alkaline conditions but is susceptible to (HF), which dissolves the silicate framework by forming soluble (\ce{SiF4}). Thermally, sodium silicate remains stable at ambient temperatures but decomposes at elevated heat, typically above 600°C, to yield and : \ce{Na2SiO3 -> Na2O + SiO2}. This decomposition is endothermic and contributes to its use in high-temperature applications, though hydrated forms lose prior to oxide formation. Additionally, sodium silicate exhibits complexing ability, binding polyvalent metal ions in solution through or precipitation of metal silicates, which can facilitate formation under controlled and temperature. For instance, it captures ions like Ca²⁺ or Mg²⁺ by releasing Na⁺, forming stable complexes. In terms of oxidation states, sodium maintains +1 and silicon +4 in \ce{Na2SiO3}, rendering the compound inert to processes under standard conditions.

Production

Furnace process

The furnace process represents the primary industrial method for manufacturing sodium silicate through the thermal fusion of silica sand (SiO₂) and (Na₂CO₃) in a high-temperature , typically operating between 1000°C and 1400°C. This approach yields a solid glassy material known as cullet, which is later dissolved to produce liquid sodium silicate solutions with varying SiO₂/Na₂O ratios. The process is favored for its straightforward use of abundant raw materials and ability to produce consistent, high-quality output suitable for bulk production. The core reaction for a 1:1 ratio is Na₂CO₃ + SiO₂ → Na₂SiO₃ + CO₂, though the SiO₂ proportion is increased to achieve higher SiO₂/Na₂O (up to 3.2:1) in the final product by adjusting the raw material blend. Raw materials are precisely mixed in Na₂CO₃:SiO₂ ranging from 1:2 to 1:3.5 to tailor the silicate composition. The blend is then charged into rotary or furnaces, where it melts into a . Upon completion of the fusion, the melt is rapidly quenched—often by pouring onto water-cooled rollers or into —to solidify into cullet fragments. These solids are fed into steam-heated autoclaves for under (typically 8-10 and 140-180°C), yielding a clear liquid sodium silicate solution that is filtered for final use. Key advantages of the furnace process include its capacity for high-purity output due to minimal impurities in the starting materials and excellent scalability for solid silicate production in large facilities. Conversion efficiencies reach 90-95%, minimizing waste, while the method's energy requirements are approximately 5.9 GJ per metric ton in standard industrial setups. This technique has been a staple in large-scale plants since the mid-19th century, enabling widespread commercialization.

Precipitation process

The precipitation process for sodium silicate production encompasses secondary wet-chemical methods at lower temperatures, often utilizing industrial byproducts or alternative silica sources. A prominent variant involves hydrothermal treatment of silica-rich byproducts, such as (a byproduct of metal production) or rice husk ash (an agricultural waste), with caustic soda (NaOH) solution at temperatures of 150–200°C and pressures around 0.7–1.5 . The silica in these materials reacts with NaOH to form soluble sodium silicate, which is subsequently filtered from undissolved residues and concentrated. This process achieves silica extraction efficiencies of 70–90% depending on ash pretreatment and conditions, producing a liquid sodium silicate suitable for direct use. These methods offer key advantages, including effective utilization of waste streams to minimize disposal and , as well as lower energy requirements compared to processes. They are particularly suited for high-purity liquid sodium silicates with SiO₂/Na₂O ratios adjustable from 2:1 to 3.5:1, ideal for specialized applications. However, production remains on a smaller scale (typically <10,000 tons/year per facility) and is heavily dependent on byproduct supply from sectors like agriculture or metallurgy, limiting widespread adoption. These approaches gained traction post-1950s amid growing emphasis on sustainable chemical , with hydrothermal variants from agricultural wastes emerging prominently in the late 20th and early 21st centuries.

Applications

Construction and repair

Sodium silicate serves as an accelerator in concrete mixtures, typically added at 1-2% by weight of cement to expedite the setting process through the formation of and (C-S-H) that enhances early hydration. This addition promotes rapid strength development, making it suitable for applications requiring quick curing, such as and repair works. In soil stabilization, sodium silicate is injected into sandy soils to form a durable silicate cement, a technique pioneered in the Joosten process since the 1920s for reinforcing foundations and preventing subsidence. The solution reacts with to create an insoluble gel that binds soil particles, improving load-bearing capacity in loose formations. For repair applications, sodium silicate seals cracks in concrete by reacting with atmospheric CO₂ and available to form , effectively filling voids and restoring integrity, particularly in historic building restoration where minimal intervention is preferred. Sodium silicate is also mixed with other silicates, such as potassium or lithium variants, to produce intumescent coatings applied to steel structures for fireproofing, where it expands under heat to form a protective insulating barrier. Early innovations include German patents from the 1880s, such as the 1886 Jeziorsky patent, which described silicate-based mortars for filling voids and creating air-setting refractory compositions in construction.

Adhesives and sealants

Sodium silicate serves as a versatile binder in adhesive formulations due to its ability to form an irreversible gel upon exposure to acids or carbon dioxide (CO₂), which creates a strong, durable bond particularly effective on porous surfaces like paper and wood. This gelation mechanism involves the polymerization of silicate ions, resulting in a silica network that adheres firmly by penetrating and hardening within substrate pores. The process is triggered by acidification, which neutralizes the alkaline solution and promotes silica precipitation, or by CO₂ absorption, leading to the formation of sodium carbonate and a solid silicate matrix. In adhesive applications, sodium silicate solutions, typically at concentrations of 20-50% solids, are widely used for bonding cardboard boxes, laminating paper, and assembling wood products, often blended with fillers such as starch to enhance viscosity and cost-effectiveness. These adhesives provide rapid setting times and strong initial tack, making them ideal for high-speed manufacturing of corrugated board and cartons, where they account for a significant portion of low-cost bonding needs. For wood bonding, the silicate's penetration into fibers ensures robust shear strength, though it is most prevalent in non-structural applications like furniture assembly. As a sealant, sodium silicate is employed in pipe joint compounds and boiler repairs, where it reacts to form a hard, impermeable silicate matrix that withstands thermal stress and prevents leaks. In these formulations, the gel hardens upon contact with moisture or CO₂ in the environment, creating a flexible yet durable barrier suitable for high-temperature plumbing and exhaust systems. To improve water resistance, sodium silicate is commonly blended with polymers such as polyvinyl acetate (PVA) or fine powders like zinc oxide, which cross-link the silicate structure and reduce moisture sensitivity in demanding environments. Historically, sodium silicate emerged as one of the first commercial adhesives in the mid-19th century, with production ramping up in the 1850s for applications like paper bonding, including early uses in bookbinding and cartridge production. By the 1890s, it gained prominence in corrugated box manufacturing, revolutionizing packaging adhesives and contributing to an estimated global consumption of around 1-2 million tons annually in adhesive sectors today, with packaging representing a major share.

Water treatment and detergents

Sodium silicate serves as a coagulant aid in water treatment processes, particularly in flocculation, where it is added at dosages typically ranging from 0.5 to 4 mg/L (0.5–4 ppm) to enhance the formation of durable silica-based flocs that capture suspended particles and organic matter, thereby improving turbidity removal in municipal and industrial plants. This application, utilizing activated silica derived from sodium silicate, has been employed since the 1930s to strengthen flocs and facilitate better settling and filtration efficiency. In the process, the silicate ions contribute to floc aggregation, aiding the removal of colloidal impurities and reducing overall treatment costs in coagulation systems paired with primary coagulants like alum or iron salts. In detergent formulations, sodium silicate functions as a corrosion inhibitor, often incorporated at 5–10% by weight alongside phosphates to protect metal surfaces in washing equipment from alkaline degradation. It precipitates divalent cations such as Ca²⁺ and Mg²⁺ as finely divided calcium silicate, preventing the formation of adherent scales and deposits that impair cleaning performance, with particular importance in automatic dishwashers where hard water can lead to filming on glassware and buildup in machine components. This precipitation mechanism enhances detergent efficacy by maintaining water softness and supporting the dispersion of soils during the wash cycle. As a pH buffer in boiler water treatment, sodium silicate helps maintain alkalinity in the range of pH 10–11, which inhibits acid corrosion of metal surfaces by promoting protective oxide layers and ensuring silica remains soluble to avoid scaling. This buffering action stabilizes the boiler environment, reducing the risk of localized pitting and extending equipment life in high-pressure steam systems. Following environmental regulations in the 1970s that restricted phosphates due to eutrophication concerns, sodium silicate emerged as a key phosphate replacement in detergents, providing similar builder functions without contributing to waterway pollution. Globally, its use in water treatment and detergents accounts for approximately 3 million tons annually as of 2024. A representative reaction in scale prevention involves the silicate anion reacting with calcium ions: \ce{SiO3^2- + Ca^2+ -> CaSiO3 v}, forming an insoluble precipitate that removes hardness-causing ions from solution.

Foundry and ceramics

Sodium silicate serves as a key in the production of cores, where it is typically incorporated at 3-5% by weight into sand mixtures to form molds and cores. The hardens through CO₂ gassing, which reacts with the silicate to create a strong, inorganic silicate bond that withstands the thermal stresses of . This process enables the creation of complex internal shapes in castings, such as those required for engine blocks or intricate machinery components, offering precision and structural integrity without the need for resins. In refractories, sodium silicate is utilized in the formulation of firebricks and pottery glazes due to its ability to provide resistance and enhance bonding. When mixed with alumina, it contributes to high-temperature stability, allowing refractories to endure environments up to 1400°C while maintaining mechanical strength and resistance to . These properties make it suitable for applications in industrial furnaces and where durability under corrosive and high-heat conditions is essential. In , sodium silicate functions as a deflocculant in clay slips, reducing and improving flow during by neutralizing particle charges for more uniform dispersion. This facilitates the of thin-walled or detailed forms, enhancing efficiency in mold filling and reducing defects like cracking or uneven thickness. The use of sodium silicate in and ceramics offers advantages such as low cost and the absence of volatile compounds (VOCs), making it an environmentally preferable alternative to traditional organic binders. No-bake systems, introduced in the , employ esters as catalysts to enable self-setting molds, providing rapid curing and improved collapsibility for easier sand reclamation post-. Global consumption in foundries remains significant, supporting widespread adoption in operations.

Food, medicine, and miscellaneous uses

Sodium silicate is approved by the U.S. (FDA) as a (GRAS) substance for use as an anticaking or free-flow agent, drying agent, , and processing aid in various foods, particularly in powdered products where it prevents clumping by absorbing . Historically, solutions of sodium silicate, known as water glass, were used to preserve eggs for several months by sealing their porous shells against bacterial entry and loss, a method popular before widespread but now largely obsolete due to modern storage techniques. It also finds use in certain dental cements, where it contributes to pulp protection by forming a barrier that supports and prevents further irritation in vital therapies. In , sodium silicate acts as a surface agent to improve strength, printability, and resistance to and oils, enhancing the quality of writing and papers. For , it is used in rod coatings to bind fluxes and provide arc stability during . In organic agriculture, sodium silicate serves as an approved and floatant to control pests and diseases on crops, such as in and , by creating a physical barrier on surfaces. Among miscellaneous uses, sodium silicate solutions are employed in educational demonstrations to create "crystal gardens," where metal salts like chloride are added to the solution, resulting in colorful silicate crystal formations that illustrate and reactions for students. In firearm maintenance, it serves as a component in some bore cleaners to dissolve lead and residues from gun barrels, aiding in residue removal without damaging metal surfaces. For textiles, sodium silicate acts as a and pH in processes with reactive dyes, enhancing color stability and penetration into fibers during hand- applications. In hobby and educational contexts, sodium silicate is used to demonstrate by mixing it with alcohols or acids to form bouncy gels or putty-like materials, providing hands-on insight into silicate chemistry. On a small scale, it provides passive fireproofing for wood or fabric by coating surfaces to form an layer that resists ignition and flame spread, suitable for DIY projects like treating shop tables or items. Regulatory limits restrict its direct use to levels not exceeding , with GRAS status applying specifically to approved concentrations below 2% in formulations like syrups or washes.

Safety and environmental impact

Health and safety considerations

Sodium silicate, particularly in solution form, acts as a mild to severe depending on concentration and duration, primarily due to its high with a typically ranging from 11 to 13. Direct contact with can cause burns or irritation, manifesting as redness, pain, and potential blistering, while eye may lead to severe damage including corneal burns and vision impairment. Inhalation of dust or aerosolized mist from sodium silicate can irritate the , causing coughing, , and of the upper airways. Acute oral is low, with an LD50 greater than 2,000 mg/kg in rats, indicating it is not highly poisonous if ingested in small amounts but can still cause gastrointestinal burns. Safe handling of sodium silicate requires the use of (PPE), including chemical-resistant gloves, safety goggles or face shields, and protective clothing to prevent skin and . Respiratory protection, such as a or , is recommended when handling dry forms or in poorly ventilated areas to avoid hazards. Storage should occur in cool, dry locations in tightly sealed containers to minimize exposure to in the air, which can trigger gelation and reduce product stability; temperatures below freezing should be avoided to prevent separation. Spills should be neutralized with a mild like dilute acetic acid before cleanup to reduce . Occupational exposure limits for sodium silicate dust follow general standards, with no specific OSHA PEL; it is often regulated under nuisance dust limits of 15 mg/m³ (total dust) and 5 mg/m³ (respirable fraction) as an 8-hour , or the amorphous silica PEL of (80 mg/m³)/(%SiO₂) for total dust. exposure primarily poses risks rather than systemic effects, and unlike crystalline silica, amorphous forms in sodium silicate do not contribute to due to their non-fibrogenic structure. Monitoring and , such as local exhaust , are essential in workplaces involving dry powders or spraying. In case of , measures emphasize immediate : for , remove contaminated clothing and flush the affected area with copious amounts of for at least 15 minutes, followed by neutralization with dilute if residual persists; seek medical attention for severe burns. Eye requires flushing with or saline for 15-20 minutes while holding eyelids open, with immediate professional evaluation. For , move the individual to fresh air and provide oxygen if breathing is difficult; respiratory support may be needed. calls for rinsing the and seeking urgent medical care without inducing vomiting to avoid further esophageal damage. Under REACH regulations, sodium silicate is classified as causing severe skin burns (Skin Corr. 1, H314), serious eye damage (Eye Dam. 1, H318), and may cause respiratory irritation (STOT SE 3, H335), but it is not listed as a or as of 2025. Classifications vary by concentration and SiO₂:Na₂O molar ratio (typically 1.5–4.0), as noted in 2025 USDA assessments. These classifications guide labeling and risk management in the , emphasizing preventive measures over exposure. In the United States, it falls under OSHA's Hazard Communication Standard without specific carcinogenicity designation.

Environmental effects

Sodium silicate, also known as water glass, exhibits favorable biodegradability in environments due to the natural occurrence of ions in water bodies. Upon dilution and exposure to environmental conditions, it hydrolyzes into harmless silica and sodium ions, with silica integrating into natural biogeochemical cycles without long-term accumulation. Studies indicate low to organisms such as and , with LC50 values typically exceeding 300 mg/L. Despite its biodegradability, sodium silicate effluents present potential risks related to and water quality alterations. The high of sodium silicate solutions (typically 11-12) can elevate stream pH levels upon discharge, potentially disrupting microbial communities and aquatic ecosystems if not neutralized. Additionally, the sodium component may contribute to increased in receiving waters, exacerbating stress on salinity-sensitive organisms in coastal or arid regions. While silicates are essential s for diatoms, elevated local concentrations from emissions could alter nutrient ratios like N:Si and P:Si, influencing composition and potentially promoting non-diatom blooms. Effective waste management practices enhance the environmental of sodium silicate. Residual sodium silicate can be recycled into by converting waste glass cullet into sodium silicate solutions via hydrothermal or processes, reducing the need for virgin raw materials and diverting waste from . In landfill disposal, solidified sodium silicate behaves as an inert material with minimal potential, though dust control measures are essential to prevent airborne particulate exposure during handling. The production and use of sodium silicate demonstrate a relatively low compared to alternatives like , with emissions estimated at approximately 1.07 tons of CO₂ equivalent per ton produced via conventional methods. Sustainability efforts have advanced since 2010 through the adoption of biomass-derived silica sources, such as rice husk ash, which provide renewable feedstocks for sodium silicate synthesis and reduce reliance on energy-intensive . These biobased routes further lower by up to 50% in some processes while promoting principles. Regulatory frameworks address sodium silicate's environmental impacts, particularly in management. The U.S. Environmental Protection Agency (EPA) mandates adjustment for industrial effluents containing sodium silicate to maintain discharge limits between 6.0 and 9.0, preventing alkalinity-related harm to aquatic systems. In detergents, sodium silicate serves as a biodegradable alternative to phosphates, aligning with EPA Safer Choice standards and reducing risks from runoff.

References

  1. [1]
    Sodium Silicate | Na2O3Si | CID 23266 - PubChem - NIH
    Concentrated aqueous solutions used as a glue. Sodium silicate is an inorganic sodium salt having silicate as the counterion. It contains a silicate ion.
  2. [2]
    [PDF] Sodium Silicate - Agricultural Marketing Service
    Mar 28, 2011 · Chemical Properties of Sodium Silicate: 65. 66. Chemical or Physical. Property. Value. Color. Colorless or white to grayish-white; also greenish ...
  3. [3]
    Sodium silicate: Introduction, Production, Uses and Health Hazards
    Aug 2, 2024 · Sodium silicate is an inorganic sodium salt. It is also known as sodium metasilicate or water glass. Its chemical formula is usually (Na2O)x-SiO2 (Na2SiO3).
  4. [4]
    Sodium Silicate - Production and Uses - ChemicalBook
    Nov 26, 2019 · Sodium silicate can be produced by dissolving silica in molten sodium carbonate. It can also be produced in a reactor, by treating a mixture of ...Missing: method | Show results with:method
  5. [5]
    Production of sodium silicate powder from waste glass cullet for ...
    Hydrothermal methods involve heating of the glass in an alkaline solution. · Thermochemical or fusion methods involve mixing glass and NaOH powders and heating ...
  6. [6]
    [PDF] Water Treatment Chemical Supply Chain Profile - Sodium Silicate
    Sodium silicate is used directly in water treatment as a component of activated silica coagulant aids, for corrosion control, and for iron and manganese ...
  7. [7]
    Sodium Silicate Adhesives - Types, Uses, Formula and Solution
    Sep 24, 2021 · Cements made with sodium silicates are used for lining and laying refractory units, preparing foundry molds and cores, laying brick in sulfite ...
  8. [8]
    [PDF] 2025 Limited Scope Technical Report | Sodium Silicate | Crops
    Jan 21, 2025 · 81 Use as a floating agent for fruit and fiber in organic production. 82 Sodium silicate is used as a floating agent for tree fruit, especially ...
  9. [9]
    Properties of Sodium silicate – (Na 2 O) x ·SiO 2 - BYJU'S
    Sodium silicates are used primarily in detergents, paper, water treatment, and construction materials. One of the greatest uses of sodium silicate solutions is ...<|control11|><|separator|>
  10. [10]
    Water glass | Silicate Chemistry, Uses & Properties - Britannica
    Sep 17, 2025 · Water glass, a compound containing sodium oxide (Na 2 O) and silica (silicon dioxide, SiO 2 ) that forms a glassy solid with the very useful property of being ...Missing: appearance | Show results with:appearance
  11. [11]
    [PDF] Sodium Silicate - DCMSME
    Dry, powdered sodium silicates may be produced by taking liquors of proper specific gravity and forcing them through a very fine opening into a solidification ...<|control11|><|separator|>
  12. [12]
  13. [13]
    Sodium Silicate Powder | Tooma Minerals Co
    Dec 5, 2020 · The ratio can vary between 1:2 and 3.75:1.[1] Grades with ratio below 2.85:1 are termed alkaline. Those with a higher SiO2:Na2O ratio are ...
  14. [14]
  15. [15]
  16. [16]
    Sodium silicate | 1344-09-8 - ChemicalBook
    Apr 29, 2025 · Sodium silicate is the common name for a compound sodium metasilicate, Na2SiO3, and is also referred to as liquid glass. ... Sodium silicate is ...
  17. [17]
    disodium metasilicate - the NIST WebBook
    disodium metasilicate · Formula: Na2O3Si · Molecular weight: 122.0632 · IUPAC Standard InChI: InChI=1S/2Na.O3Si/c;;1-4(2)3/q2*+1;-2. Copy · IUPAC Standard InChIKey: ...
  18. [18]
    Sodium silicate with a molar ratio SiO2:Na2O ≤ 1.6 - EPA
    Name: Sodium silicate with a molar ratio SiO2:Na2O ≤ 1.6; CAS Number: 1344-09-8; Synonyms: Sodium silicate, Sodium sesquisilicate; Approval number: Does not ...Missing: nomenclature | Show results with:nomenclature
  19. [19]
    US3821119A - Silicated soda ash - Google Patents
    The amount of such a silicate employed will be within the range of from 30-55 percent of the combined aqueous silicate/soda ... sodium silicate or sodium ...
  20. [20]
    SODIUM SILICATE MOD 3 - Ataman Kimya
    ... silicates were made by Basil Valentine in 1520, and by Agricola in 1550. Around 1640, Jean Baptist van Helmont reported the formation of alkali silicates as ...
  21. [21]
  22. [22]
    Applications of Sodium Silicate in Detergents - آب شیشه زرین
    History of Sodium Silicate Use in Detergent Production​​ In the late 19th century, sodium silicate was noted for its unique chemical and physical properties and ...
  23. [23]
    Soluble Silicates
    His work in the 1820's paved the way for a number of companies to begin commercial manufacture of silicates in the both Europe and North America in the 1850's.Missing: production milestones plants Germany
  24. [24]
    The history of sodium silicate - Ingessil
    Some sources report that they could already have been produced by the ancient Egyptians over 5000 years ago through the fusion of silica sand and natural soda ...
  25. [25]
    Our History – PQ Corp.
    1861. Elkinton's began manufacturing sodium silicate or “waterglass”, which became a rosin replacement during the Civil War.
  26. [26]
    [PDF] SOLUBLE SILICATES - OECD Existing Chemicals Database
    The worldwide production volume is approximately 3-4 million metric tons per year. In the year 2000, ca. 770,000 metric tons of sodium ...
  27. [27]
    Sodium Silicate
    **Summary of Sodium Silicate (CID 23266) from PubChem:**
  28. [28]
    [PDF] Structural studies of silicate glasses and melts-applications and ...
    Raman spectra of crystalline tetrahedral silica polymorphs show two groups of bands centered near 1050 and 1200 cm-'. (Bates, 1972; Etchepare, 1972; McMillan et ...
  29. [29]
    Sodium Metasilicate Anhydrous | AMERICAN ELEMENTS ®
    Sodium Metasilicate Anhydrous qualified commercial & research quantity preferred supplier. Buy ... Density, 2.4 g/cm3. Solubility in H2O, N/A. pH, 12.6. Exact ...
  30. [30]
    Sodium Silicate Solution (40 -42 Be/Technical), Fisher Chemical 1 L
    4–8 day delivery 30-day returnsSpecific Gravity, 1.38 to 1.42 (at 25°C) ; Viscosity, 20-400 mPa/s at 20°C ; pH, 11.2 ; Quantity, 1 L ; Physical Form, Liquid.
  31. [31]
    6834-92-0(Sodium metasilicate) Product Description - ChemicalBook
    Sodium metasilicate Property ; Melting point: 1089°C ; Density, 2.4 ; refractive index, nD25 (glass) 1.520 ; solubility, soluble in cold H2O; reachot H2O; insoluble ...
  32. [32]
    [PDF] SAFETY DATA SHEET sodium metasilicate, anhydrous - Silmaco
    Dec 15, 2022 · Causes severe skin burns and eye damage. May cause respiratory irritation. Respiratory or skin sensitisation sodium metasilicate, anhydrous.
  33. [33]
    sodium metasilicate (anhydrous) - PubChem
    sodium metasilicate (anhydrous) chemical information summary ... 3.1.4 Density. 2.6 g/cm³. ILO-WHO International Chemical Safety Cards ...
  34. [34]
    The Viscosity Properties of Sodium Silicate Solutions
    Nov 27, 2007 · Static results show that viscosity increases monotonously with concentration varying from 15 to 55%, decreases with temperature rising from 15 to 70 °C.
  35. [35]
  36. [36]
    Na2SiO3 + H2O = NaOH + H2SiO3 - Chemical Equation Balancer
    Word Equation. Sodium Metasilicate + Water = Sodium Hydroxide + Metasilicic Acid. Na2SiO3 + H2O = NaOH + H2SiO3 is a Double Displacement (Metathesis) ...
  37. [37]
    A comprehensive study on the gelation process of silica gels from ...
    The chemical reaction of sulphuric acid with sodium silicate in aqueous solution results in the formation of silica (SiO2), sodium sulphate (Na2SO4) and water.<|separator|>
  38. [38]
    Thermal studies on sodium silicate hydrates. IV ... - ScienceDirect.com
    Thus, sodium silicate can be formed and it has been reported to degrade at higher temperatures (>600 °C) (Felsche et al., 1985).
  39. [39]
    Silicate as a Versatile Matrix for the Aqueous Synthesis of Metal ...
    Dec 18, 2021 · The addition of metals to the oligomeric sodium metasilicate in water results in insoluble metal silicate complexes that form nanoparticles, ...
  40. [40]
    Functions of sodium silicate - Ingessil
    Ion-exchange action: sodium silicate loses sodium ions and captures polyvalent metals ions. This explains the soothing properties of sodium silicate on hard ...
  41. [41]
    Production process of sodium silicate - Ingessil
    Sodium silicate in aqueous solution can be produced through two main and distinct processes: - Melting process and subsequent dissolution; - Hydrothermal ...
  42. [42]
    Products – PQ Corp.
    PQ provides silicate in various forms including solid glass, hydrous powders and ready-for-use liquids. Our liquid sodium silicate is the core building block ...Missing: Q | Show results with:Q
  43. [43]
    Sodium Silicate Project Profile - Edit | PDF - Scribd
    Rating 5.0 (2) The desired sodium silicate is obtained by varying the ratio of the raw materials charged as well as the working up of proper solution. b) Raw Material for ...
  44. [44]
    Crown incident radiant heat flux measurements in an industrial ...
    ... energy consumption of 5.9 GJ/ton are ... Investigation and experimental measurement of an industrial melting furnace used to produce sodium silicate.
  45. [45]
    Sodium Silicate: An Overview of History, Applications and Modern ...
    The German chemist Jöns Jacob Berzelius first described sodium silicate in 1824 and pointed out that it had unique properties. However, it was not until the end ...
  46. [46]
    Precipitating sandy aluminium hydroxide from sodium aluminate ...
    The precipitation of aluminium hydroxide is promoted by bubbling carbon dioxide gas into the supersaturated sodium aluminate solution, i.e., the carbonation ...
  47. [47]
    CA2571354A1 - Precipitation of silica in a bayer process
    In the Bayer process for the production of alumina, problems are caused by silica dissolving in the caustic liquor. This silica arises from the presence of ...
  48. [48]
    Hydrothermal synthesis of sodium silicate from rice husk ash
    This paper presents comprehensive results of syntheses of alternative sodium silicates (SSs) from rice husk ash (RHA) using a hydrothermal process.
  49. [49]
    Hydrothermal synthesis of sodium silicate from rice husk ash
    This paper presents comprehensive results of syntheses of alternative sodium silicates (SSs) from rice husk ash (RHA) using a hydrothermal process. The effect ...Missing: caustic | Show results with:caustic
  50. [50]
    Energy and CO2 emission assessments of alkali-activated concrete ...
    On the other hand, the required energy for the production of sodium silicate (48% solid) is approximately 5.371 ​GJ/t (Fawer et al., 1999).
  51. [51]
    Cement Slurry Accelerators Mechanism & Chemistry - Drilling Manual
    Apr 22, 2021 · Sodium silicate reacts with Ca2+ ions in the aqueous phase of the cement ... The normal dosage is 1–2% BWOC. Calcium formate accelerates ...
  52. [52]
    Effect of sodium silicate on Portland cement/calcium aluminate ...
    Mar 29, 2019 · In this investigation, sodium silicate (SS) was mixed into rich-water (RW) materials consisting of Portland cement, calcium aluminate cement and gypsum for ...
  53. [53]
    (PDF) Effect of Sodium Silicate on Hardening Property on Concrete
    Apr 15, 2020 · The literature study depicts that there is a considerable amount of decrease in strength is observed when sodium silicate is added to concrete.
  54. [54]
    From Chemical Gardens to Chemobrionics - ACS Publications
    Jul 15, 2015 · Classical chemical garden formed by the addition of cobalt, copper, iron, nickel, and zinc salts to a sodium silicate solution. The image ...
  55. [55]
    [PDF] SODIUM SILICATE STABILIZATION OF SOILS: A REVIEW OF THE ...
    This report consists of an annotated bibliography and summary review of the important literature on the use of sodium silicates in soil stabilization.Missing: 1920s | Show results with:1920s
  56. [56]
    Sealing of cracks in cement using microencapsulated sodium silicate
    Jul 15, 2016 · Sodium silicate reacts with the calcium hydroxide in hydrated cement paste to form calcium-silicate-hydrate gel that fills cracks.
  57. [57]
    URI research on self-healing concrete yields cost-effective system to ...
    May 25, 2010 · The sodium silicate reacts with the calcium hydroxide naturally present in the concrete to form a calcium-silica-hydrate product to heal the ...
  58. [58]
    Intumescent Silicate Coatings with the Addition of Alkali-Activated ...
    May 10, 2022 · Fireproof inorganic coatings based on sodium silicate solution with intumescent additions were prepared and tested to assess their ability to limit the ...
  59. [59]
    [PDF] CHEMICAL GROUTS FOR SOILS: VOL. I - AVAILABLE MATERIALS
    In 1886, for the first time, a German patent. (JEZIORSKY) recommended ... sodium silicate. Following an exchange of bases, a sol is formed of calcium ...
  60. [60]
    A review of sodium silicate solutions: Structure, gelation, and syneresis
    Knowledge of sodium silicate solution, also known as waterglass, dates back to at least the period of the early Roman Empire. Pliny the Elder (Gaius Plinius ...
  61. [61]
    [PDF] Part XIII: Silicate CO - Sand Binder Systems
    First is "gelation" in which sodium silicate and water react with CO2 gas to form a mixture of sodium carbonate and silica gel along with water. The CO2 and ...
  62. [62]
    Sodium Silicate - an overview | ScienceDirect Topics
    Sodium silicate is an alkaline activator, also called "water glass", used in grouts, and is a compound with the formula Na2xSiO2+x.
  63. [63]
    Sodium Silicate Liquid - Chemical Store Inc.
    Sodium silicate is a clear, odourless, viscous liquid. It has a molar ratio of 3.27 and a total solids content of 36.8%.Missing: Giese | Show results with:Giese
  64. [64]
    [PDF] Mastics, Coatings, Adhesives and Sealants - Foster Products
    Used as flashing to seal boiler settings to prevent air infiltration. ... A sodium silicate-based adhesive of exceptional strength. Non-flammable wet ...
  65. [65]
  66. [66]
    A Short History of the Manufacture of Soluble Silicates in the United ...
    The story of the industry began with a German professor, Johann Nepomuk von Fuchs of the German University of Landshut.
  67. [67]
    Sodium Silicate Market Report | Forecast [2034] - Industry Research
    Detergent applications account for approximately 42% of global consumption, while adhesives and paper processing contribute 19% and 14%, respectively. The Asia- ...
  68. [68]
    water treatment - coagulation-flocculation typical reagents
    Coagulation and flocculation reagents are simple or polymerised mineral salts, and organic, natural or artificial polymers.<|separator|>
  69. [69]
    Coagulant Aid - an overview | ScienceDirect Topics
    Coagulant aids enhance flocculation by improving settling and durability of flocs in water treatment, often used with aluminum or iron coagulants.
  70. [70]
    Utilization of a low cost agro-residue for production of coagulant aids ...
    Activated silica has been used as a flocculants since the 1930s to strengthen flocs and reduce the potential of deterioration.
  71. [71]
    [PDF] Lesson 4: Coagulation and Flocculation
    The end product of a well-regulated coagulation/flocculation process is water in which the majority of the turbidity has been collected into floc, clumps of ...
  72. [72]
    [PDF] Silicated Soaps, Part 2, Application at Inorganic Surfaces.
    Metal polishing compositions often contain soluble silicates.92 A deter- gent composition which does not harden and inhibits rusting is suitable for.
  73. [73]
    [PDF] AUTOMATIC DISHWASHER DETERGENTS - PCC SE
    Sequestring/Dispersing agents – responsible for scale build-up prevention as well as reducing calcium and magnesium ions by chelating or dispersing mechanism.
  74. [74]
    ACUSOL™ 588G Polyphosphate and Silicate Scale Inhibitor - Dow
    ACUSOL™ 588G is a scale inhibitor for laundry and dishwashing detergents, reducing mineral buildup and residue, and controlling silicate scales.
  75. [75]
    High Quality Boiler Feedwater from Hard Water | GWI
    Nov 1, 2019 · The pH of the treated water is then increased to 10-11. This ... The high pH ensures silica solubility (>1500 ppm) to avoid scale ...
  76. [76]
    [PDF] Association of Water Technologies – Technical Manual
    Corrosion inhibiting programs are designed to maintain this pH by a buffering effect, or by the control of alkalinity breakdown in the boiler.
  77. [77]
    Phosphate Phaseout Is Opportunity For Chemical Suppliers - C&EN
    Jan 25, 2010 · Accused of contributing to eutrophication in lakes and rivers, phosphates were eliminated from laundry detergents in the early 1970s.Missing: post- regulations
  78. [78]
    Sodium Silicate Market Size - Share & Analysis Report 2030
    Oct 22, 2025 · The Sodium Silicate Market is expected to reach 8.39 million tons in 2025 and grow at a CAGR of 4.87% to reach 10.64 million tons by 2030.
  79. [79]
    How does sodium silicate react with calcium hydroxide? - Quora
    May 1, 2019 · Sodium silicate Na2SiO3 is soluble in water. Ca2+ ions from the sparingly soluble Ca(OH)2 readily replace the sodium ions Na+ to produce calcium Silicate CaSiO ...
  80. [80]
    Sodium Silicate Binders for Green Sand Metalcasting Foundry
    Dec 16, 2016 · Hill and Griffith Sodium Silicate Binders are formulated with water based solutions of Sodium Silicates and collapsibility agents.
  81. [81]
    Experimental Study of Inorganic Foundry Sand Binders for Mold and ...
    Oct 8, 2022 · Some modified sodium silicate binders have already been successfully used in the production of cores with complex geometries that are used ...
  82. [82]
    Physical-chemistry study of sodium silicate as a foundry sand binder
    Colloidal chemistry is a tool in developing the physics and chemistry of sodium silicate as a foundry binder.
  83. [83]
    The brief introduction of Sodium silicate - ChemicalBook
    Apr 3, 2024 · Sodium silicate is the common name for a compound sodium metasilicate, Na2SiO3, and is also referred to as liquid glass.Missing: IUPAC historical<|control11|><|separator|>
  84. [84]
    Recent advances in silica-alumina refractory: A review - ScienceDirect
    The cold crushing strength increases as temperature increased to 1400 °C and with increasing binder content. This study indicates that lithomargic clay under ...
  85. [85]
    The method of producing refractory materials with powdered sodium ...
    Sodium silicate is also used in the production of refractory materials for ceramic furnaces. These materials have high resistance to thermal shocks and increase ...<|control11|><|separator|>
  86. [86]
    Sodium Silicate | Trinity Ceramic
    In stockSodium silicate is commonly used in ceramics as a deflocculant in casting slip by neutralizing the charges of particles in the slip, allowing for more even ...
  87. [87]
    [PDF] No-Bake - ASK Chemicals
    The two part binder is made-up of a water-base sodium silicate resin, as well as a liquid ester catalyst. The water-based resin is what helps provide such ...
  88. [88]
    Michael J.Lessiter, Ezra L.Kotzin: Timeline of Casting Technology
    1970 - The sodium-silicate/ester catalyzed nobake binder system is introduced for cores/molds. 1970s - Digital codes are developed to simulate solidification ...
  89. [89]
    sodium silicate - cfsanappsexternal.fda.gov
    ... GRAS status of flavoring substances. The FEMA number is provided here as a reference to FEMA's GRAS assessments. The GRAS Pub. No. is the FEMA GRAS ...
  90. [90]
    The Waterglass method of egg preservation - Lake Country Museum
    Oct 13, 2017 · The sodium silicate solution would turn cloudy and seal the eggs, protecting them from bacterial attack. To cook with these eggs, one simply ...
  91. [91]
    US3017324A - Antacid composition - Google Patents
    German Patent No. 941,864 describes an antacid composition composed of mixed coprecipitated aluminum and magnesium hydroxy silicates prepared from sodium ...
  92. [92]
    A new translucent cement for dentistry | British Dental Journal - Nature
    Oct 28, 2022 · The normal dental silicate cement powder, used for combining with phosphoric acid solutions, is prepared by fusing mixtures of quartz, alumina, ...
  93. [93]
    A chemical garden | Chem 13 News Magazine | University of Waterloo
    This experiment was done by Glauber about 1650. Dissolve 190 g of sodium silicate (water glass) in 190 cm 3 of distilled water.
  94. [94]
    How do you tell if a barrel is leaded? - SASS Wire Forum
    Feb 4, 2011 · Dog, twice a year I give the firearms a 'deep' cleaning using Astonish Oven and Cookware Cleaner. ... * Sodium Silicate. * Glycerin. * Perfume. * ...
  95. [95]
    Textile | Silmaco
    Dye fixation: our sodium silicates are used as an alkaline buffering agent to keep reactive dyes stable. Bleach stabilisation: peroxides, used for bleaching, ...
  96. [96]
    [PDF] Bouncing Polymers
    In this experiment, sodium silicate (Na2SiO3) is dissolved in water (H2O). At this point, the solution becomes basic because sodium silicate creates sodium ...
  97. [97]
  98. [98]
    Subpart B—Listing of Specific Substances Affirmed as GRAS - eCFR
    The affirmation of this ingredient as generally recognized as safe (GRAS) as a direct human food ingredient is based upon the following current good ...
  99. [99]
  100. [100]
    [PDF] Product Stewardship Summary Liquid Sodium Silicates - Oxy
    Feb 13, 2013 · Sodium silicate is not in a molecular structure that can cause silicosis. ... If there is any risk of liquid silicate splashing in the eyes, ...
  101. [101]
  102. [102]
    [PDF] Safety Data Sheet Sodium Silicate Solution WARNING
    Emergency and First Aid Procedures. Inhalation: In case of accident by inhalation: remove casualty to fresh air and keep at rest.
  103. [103]
    Emission, Fate and Effects of Soluble Silicates (Waterglass) in the ...
    This paper aims to assess the impact of waterglass on the aquatic environment in Western Europe. The emission to surface waters from the four most relevant ...Introduction · Methods · Results and Discussion · Acknowledgment
  104. [104]
    (PDF) Conversion of waste glasses into sodium silicate solutions
    Aug 6, 2025 · In this study, hydrothermal and fusion methods used to prepare sodium silicate solution from waste glasses.
  105. [105]
    [PDF] False Values on CO2 Emission for Geopolymer Cement/Concrete ...
    See Table 2 below. The CO2 emissions for the two major sodium silicates discussed in this paper are: - 1,066 kg/tonne (approx. 1,000 kg/t) for the glass sodium ...
  106. [106]
    Biobased Silicon and Biobased Silica: Two Production Routes ...
    Jun 29, 2023 · In 2022 more than 3 million tons of SiMG were produced while demand was substantially higher (3.5–3.75 million tons) leading to 300 % price ...
  107. [107]
    U.S. Liquid Sodium Silicate Market | Industry Report, 2033
    Growth is propelled by a rising shift toward phosphate-free and biodegradable detergent systems aligned with U.S. Environmental Protection Agency (EPA) Safer ...