Peroxyacetyl nitrate (PAN), an eye irritant, is produced by:

We begin by recalling the chemistry of various atmospheric pollution phenomena. Classical smog (also called London smog) is a mixture of smoke, fog, $$\text{SO}_2$$ and other coal-burning products formed in a cool, humid environment. It mainly contains reducing agents such as $$\text{SO}_2$$ and soot, but it does not involve significant photochemical reactions.

Acid rain is produced when acidic oxides such as $$\text{SO}_2$$ and $$\text{NO}_x$$ dissolve in atmospheric moisture to give $$\text{H}_2\text{SO}_4$$ and $$\text{HNO}_3$$, which later fall with rain. Although $$\text{NO}_x$$ species are present, the specific eye-irritating compound peroxyacetyl nitrate (abbreviated as PAN) is not generated in this process.

Organic waste decomposition yields methane and other simple organic molecules under anaerobic conditions, but again, no high-energy sunlight-driven reactions occur, so PAN is not formed here either.

Now we focus on photochemical smog, which develops in large, sunny cities where high concentrations of unburned hydrocarbons (denoted generally as $$\text{RH}$$) and oxides of nitrogen (collectively labeled $$\text{NO}_x$$) are present. Intense sunlight provides the energy for a series of free-radical reactions. The key steps (written schematically) are:

$$ \text{NO}_2 \;\xrightarrow{h\nu}\; \text{NO} + O \qquad(\text{photodissociation}) $$

$$ O + O_2 \;\longrightarrow\; O_3 $$

Unburned hydrocarbons or aldehydes in the air, symbolized by $$\text{RCHO}$$, react with the radicals and ozone to form acyl radicals:

$$ \text{RCHO} + \cdot OH \;\longrightarrow\; \text{RC(O)\cdot} + H_2O $$

These acyl radicals then combine with molecular oxygen and $$\text{NO}_2$$ to give peroxyacetyl nitrate:

$$ \text{RC(O)\cdot} + O_2 + NO_2 \;\longrightarrow\; \text{RC(O)OONO}_2 \;(\text{PAN}) $$

The compound $$\text{RC(O)OONO}_2$$, when $$R = CH_3$$, is specifically peroxyacetyl nitrate, $$\text{CH}_3\text{COOONO}_2$$, a powerful lachrymator (eye irritant) and respiratory hazard. Because this entire sequence relies on sunlight (photo) and involves oxidizing agents like ozone, it is classified under photochemical smog.

So, among the given choices, only the atmosphere of photochemical smog provides the sunlight, hydrocarbons and $$\text{NO}_x$$ needed to synthesize peroxyacetyl nitrate.

Hence, the correct answer is Option D.