User:Taylormryan/sandbox

*Material in this sandbox have been inserted into three separate existing Wikipedia pages: Nail polish, Dibutyl phthalate, and Toluene toxicity. Headings and sub-headings are included in this sandbox like they are in each of the existing Wikipedia pages they belong to.*

Nail polish

Environmental safety

Regulation and environmental concerns

As previously mentioned, nail polish is a household hazardous waste (HHW) that should not be disposed of in the trash, but must be disposed of properly. Nail polish is a HHW primarily because it contains dibutyl phthalate, toluene, and formaldehyde, otherwise known as the "toxic trio." In the United States, there are an estimated 117 million nail polish users. Dibutyl phthalate has been studied extensively and is proven to be an endocrine disruptor, as well as a compound that can decrease birth weight, decrease survival of newborns, reduce sperm count, and also promote testicular atrophy. The photochemical oxidation of toluene contributes to tropospheric ozone and secondary organic aerosol (SOA) formation, which has been reported to have effects on air quality, human health, and the climate.

Dibutyl phthalate

Environmental relevance

Fundamental environmental chemistry

Dibutyl phthalate (DBP) is one of the six phthalic acid esters found on the Priority Pollutant List, which consists of specified chemical pollutants regulated by the United States Environmental Protection Agency (EPA) . Chemically, phthalate esters are diesters of ophthalmic anhydride; their plasticizing properties can be advantageous for use in cosmetics, fragrances, insect repellants, upholstery, and more. Typically, phthalate esters such as dibutyl phthalate are not covalently bound to the polymer of the plastic they are adhered to and therefore, can easily leach out of that component (i.e. nail polish) and into municipal waters . Overall, DBP can be released into each sector of the environment—water, soil, and air—via leaching, microbial degradation, and photocatalytic oxidation. As water percolates throughout landfill sediment, DBP is leached into the surrounding environment . However, due to the fact that DBP holds a density less than that of water, a thin surface film forms at the air-water interface. Analyses of DBP's octanol-water partition coefficient using high pressure liquid chromatography has concluded on several values that represent the compound’s hydrophobicity. Moreover, the constant can be utilized to define DBP’s ability to partition in animal lipids, sediment, and soil organic matter .

Octanol-Water Partition Coefficient (Log Kow)
Dibutyl Phthalate	4.11	4.31	4.46

Dissolved organic carbon

DBP is a hydrophobic compound that has a low solubility in water. However, different interactions with dissolved organic carbon (DOC) can have solubilizing effects on DBP and increase its mobility in places it is commonly found, such as in landfills . DOC is known to increase DBP’s water solubility by interacting in two ways: by changing the equilibrium distribution of the solute (DBP) and by direct interaction with DBP. In the first interaction, DBP’s sorption coefficient is lowered when partially water-miscible substances change the equilibrium distribution of DBP between its solid and liquid phase. These partially water-miscible substances are typically alcohols and are also known as cosolvents. The result of this is an increase in DBP’s mobility, but this interaction requires high concentrations of DBP to take place. Increased solubility of DBP is more likely to occur by the second interaction which involves a direct interaction between DBP and other organic compounds. DBP becomes more polar and water soluble after interaction with these typically polar organic compounds found in landfills. DBP can then bind to DOC in a partition-like interaction where the hydrophobic moeitities of DBP and DOC bind each other in a micelle-like structure within an amphiphilic macromolecule. Studies have shown that in some landfill leachates, 85% of phthalate esters are found in their solubilized form due to DOC .

Hydrolysis of DBP

DBP and other phthalates found in landfills are known to undergo both acid and base catalyzed hydrolysis. Xenobiotic substances like DBP are commonly degraded by hydrolysis reactions . Metal ions, anions, and organic materials can all serve as catalysts for these acid- or base-catalyzed hydrolysis reactions. In both the acid- and base-catalyzed reactions, DBP is first hydrolyzed to a monoester form that contains a carboxylic acid, and 1-butanol is released. The monoester is then hydrolyzed to form phthalic acid, and a second 1-butanol is released. The overall reaction requires two molecules of H₂O and either a base or acid working as the catalyst. This hydrolysis reaction is both pH and temperature dependent in landfills. It occurs readily in the deeper layers of landfills, where temperatures are high and acidic or basic conditions are prevalent. In addition, the reactants tend to mimic their gas-phase structure in these deeper layers, which decreases steric effects during this ester hydrolysis. However, the rate of this reaction is negligible at the surface of landfills due to low temperatures and neutral pH conditions. At pH 7, esters tend to be less electrophilic and less susceptible to hydrolysis . This is one of the primary reasons why DBP concentrations can be elevated on or near the surface of landfills relative to the deeper layers. These elevated concentrations create a cause for concern due to the possibility of the chemical leaching into the surrounding environment.

Acid/Base Catalyzed Hydrolysis of DBP

Photocatalytic degradation of DBP

DBP can also be photochemically degraded with the help of titanium dioxide (TiO₂) .

TiO₂ + hv > 5.13 x 10^-19 J ${\ce {->}}$ TiO₂(e^-_cb/h⁺_vb) ${\ce {->}}$ e^-_cb + h⁺_vb (1)

h⁺_vb + OH^- (or H₂O)_surface ${\ce {->}}$ ^•OH(+H⁺) (2)

e^-_cb + O₂ ${\ce {->}}$ ^•O2^•− + H⁺ ${\ce {->}}$ ^•OOH (3)

TiO₂ first absorbs UV light at wavelengths below 3.87 x 10^-7 m (or with an energy greater than 5.13 x 10^-19 J). This reaction produces electron-hole pairs which will react independently. The conduction band electrons (e^-_cb) react with dioxygen molecules to produce a superoxide radical anion, ^·O₂^·-. The superoxide radical anion is then protonated to form a hydroperoxide radical (^·OOH). The holes (h⁺) can react with either hydroxyl ions (OH^-) or surface water found on the TiO₂ particulate to produce a hydroxyl radical (^·OH) and a hydrogen ion (H⁺). Once the hydroxyl radical and hydroperoxide radical are generated, they can attack either the aromatic ring or one of the aliphatic side chains of DBP. There is currently no way of determining the preference a radical has to attack either site, making the reaction more complex. Depending on where the radical attack occurs, and which radical is responsible for the attack, a number of intermediates can be formed. The complex group of intermediates are also subject to radical attacks, which forms acetaldehyde, acetic acid, or formic acid. These aliphatic intermediates can then be attacked by either radical, resulting in slow CO₂ mineralization and water formation. However, the TiO₂ mediated photochemical degradation of DBP occurs at an almost negligible rate in landfills. This is due to other existing organic compounds, such as acetone, that are commonly found in landfills at higher concentrations than DBP . These existing organic compounds compete with DBP for the attack by a radical such as the two mentioned above. This too can lead to increased concentrations of DBP found on or near the surface of landfills that leach into the surrounding environment.

Titanium Oxide Mediated Photocatalytic Degradation of DBP

DBP leaching

From the surface film, DBP has a very small tendency to volatilize into the atmosphere due to a vapor pressure of 2.67 x 10^-3 Pa and a Henry’s Law constant of 8.83 x 10^-7 atm-m³/mol . Rainfall transfers phthalate esters in the atmosphere to fresh water, and their accumulation here causes their wide distribution in rivers and lakes. The partitioning behavior of DBP characterizes the ability of the compound to separate from the air, which is a process catalyzed by washout. Either rain or snow is responsible for the process. The washout ratio (W) defines the ratio of chemical concentrations in rain or snow to that in air as defined by the following equation:

W = (1-f) W_v + f W_p = (1-f) RT/H + f W_p

where W_v is the vapor washout ratio, RT/H is the reciprocal of Henry’s Law constant, W_p is the particle scavenging coefficient, and f is the fraction of chemical on the particulate. Dibutyl phthalate displays a washout ratio (W) of 2.8 x 10^-4 with a f of 0.014. Studies have indicated that DBP functions by a “temperature-dependent phenomena” whereby it is in the colder winter months that the vapor pressure of the compound is reduced sufficiently in order to produce an efficient washout ratio. Moreover, because of the hydrophobicity of phthalate esters, their chemical composition permits their sorption into soil and sediment among other environmental components . Upon release into the environment, dibutyl phthalate is able to interact with environmental media in ways that change their chemical behavior .

Agencies have begun to delve into implementing affordable and resourceful methods of treating water supplies to decrease the concentration of the plasticizer components in rivers and lakes. First, adsorption to remove organic compounds has been extensively researched by the EPA whereby activated carbon is used to treat water consumed by humans. Another method under current investigation is the biological avenue which utilizes populations of microorganisms to degrade the esters. For example, Enterobacter species can biodegrade municipal solid waste—where the DBP concentration can be observed at 1500 ppm—with a half-life of 1.04 x 10⁵ seconds. In comparison, the same species can break down 100% of dimethyl phthalate after a span of six days. However, this treatment method varies significantly depending on temperature, anaerobic and aerobic conditions, and more .

Toluene toxicity

Environmental relevance

Fundamental environmental chemistry

Toluene, also known as methylbenzene, is one of the three chemicals that make up the "toxic trio" commonly found in nail polish. It has a relatively high vapor pressure of 3.79 x 10³ Pa at 298.15 K and is a volatile liquid at room temperature . It rapidly volatizes into the air and therefore is classified as a volatile organic compound. The path of toluene from disposed nail polish to the atmosphere is a relatively simple one due to its volatile nature. Once in a landfill, toluene can enter the soil and water in surrounding areas. From here, it will then readily evaporate into the atmosphere. However, the rate at which volatilization occurs depends on the conditions of the soil, such as temperature, humidity, and soil type. Once vapor phase toluene is free in the atmosphere, it is subject to react with photochemically-produced hydroxyl radicals, nitrate radicals, and ozone molecules .

Toluene and photochemically-produced hydroxyl radicals

Hydroxyl radicals are formed via a two-step reaction (reactions 1 and 2). The first step is the photolysis of gaseous ozone which employs solar energy and results in diatomic oxygen gas and an oxygen atom in its excited state. The electronically excited oxygen atom has sufficient excitation energy to now react with water vapor, producing hydroxyl radicals .

Reaction (1):   O₃ + hv ${\ce {->}}$ O(¹D) + O₂

Reaction (2):   O(¹D) + H₂O ${\ce {->}}$ 2OH^•

The initial reaction of toluene with a hydroxyl radical includes direct OH addition to the ortho position of the benzene ring and results in an ortho OH-toluene adduct (also known as methylhydroxycyclohexadienyl radical). The adduct subsequently reacts with atmospheric O₂ via three possible pathways, however, the third will not be discussed as it has been proven to be thermodynamically and kinetically inhibited. The first pathway, upon reaction with O₂, forms a primary organic peroxy radical (RO₂) via O₂ addition. The second pathway, upon reaction with O₂, forms the phenolic compound O-cresol and hydroperoxy radicals (HO₂) via hydrogen abstraction .

Both RO₂ (reaction 3) and HO₂ (reaction 4) products generated react with nitric oxide (NO) to form nitrogen dioxide (NO₂) which subsequently undergoes photodissociation to produce ground-state oxygen atoms that recombine with molecular oxygen to produce tropospheric ozone (reactions 5 and 6) . Tropospheric ozone, also known as “bad” ozone, functions as an air pollutant that is harmful to humans and vegetation, the main ingredient in smog, and a greenhouse gas . In terms of ozone formed from toluene oxidation, the RO₂ pathway contributes 65% and the HO₂ pathway contributes 18% .

Reaction (3):   RO₂ + NO ${\ce {->}}$ RO + NO₂

Reaction (4):   HO₂ + NO ${\ce {->}}$ OH + NO₂

Reaction (5):   NO₂ + hv ${\ce {->}}$ NO + O^·

Reaction (6):   O^· + O₂ + M ${\ce {->}}$ O₃ + M

Toluene and nitrate radicals

Nitrate radicals are formed when anthropogenic NO₂ gas, commonly emitted by industrial sources, reacts with atmospheric ozone (reaction 7). Nitrate radicals are known as a “night-time oxidizer” as its nighttime concentration is nearly twice the concentration of the hydroxyl radical during the daytime .

Reaction (7):   NO₂ + O₃ ${\ce {->}}$ NO₃^• + O₂

Nitrate radicals oxidize toluene either by the abstraction of the alpha-hydrogen atom, shown on top, or by the transfer of an electron, shown on bottom. These reactions result in nitric acid (HNO₃) and nitrate (NO₃^-) (i.e. a strong acid and its conjugate base) .

Nitric acid exists in the atmosphere in its gas phase and can react with gaseous ammonia to form particulate or aerosol nitrate. Nitric acid is highly corrosive, and if concentrated in the environment, it can react rapidly with other natural or anthropogenic environmental compounds. These reactions can occur so rapidly that they result in a chemical fire or explosion . Nitrate is highly soluble in the environment which enables the compound to easily move with soil water towards plant roots and to inhabit surface water and ground water. The pollution of bodies of water with excess nitrate from the atmosphere may lead to hypoxia. The compound promotes rapid algae growth, which then results in reduced oxygen water levels making it difficult for marine species to survive .

See also

• Nail polish