Instead, as my dog leaped into the back porch after his brief pre-dawn potty break in the yard, I thought it was just some new form of particularly odious flatulence. This dog often has gas, and I had not yet had coffee. However, as I bent down to wipe his feet and the odor increased sharply in its intensity, I realized that my dog wasn't directly responsible for the stench. He seemed unconcerned, but he loves stinky odors, and the spray had missed his face.
There had been strong sulfurous fumes in the back yard for the previous week. It was almost March, and the skunks were stirring, looking for food and for love after winter. They are not shy about wandering around outside our house, although because they are normally strictly nocturnal we almost never see them. Skunks will spray predators that threaten them, but a female skunk will also spray persistent males bent on mating if she's really just not in the mood. Skunks aim quite well, so I suspected that my dog had interrupted an unhappy love affair and been splattered by the consequences.
Striped skunk, Mephitis mephitis. Photo: NPS
Skunks are born blind and helpless, but their glands contain musk by the end of their first week, and they are capable of spraying at the age of 17 days, more than two weeks before their eyes open for the first time. Researchers found that young skunks were more likely than adults to spray than to run, hide, or charge. I found no reliable reports of how long it takes for a skunk to refill its glands after a full discharge. Presumably it takes some energy and time, because skunks give plenty of warning before firing, and don't seem willing to use all of their supply in a single encounter unless they must.
Striped skunks. Image from http://wdfw.wa.gov/living/skunks.html
Elements of the chemical composition of the spray were described as early as 1862 by German chemists, and a fellow German named Dr. O. Low did his best to continue the inquiry during an expedition to Texas in 1872. Low commented on the abundant opportunity to collect skunks and their musk during his travels, but his companions objected so vigorously to the ensuing odor that he was forced to abandon his efforts. He was further stymied from studying his few skimpy samples by colleagues and students in the college at which he worked "when the whole college rose in revolt, shouting 'A skunk, a skunk is here!' I had to abandon the investigation."
A more thorough treatment of the chemical elements of skunk spray was published in 1896 by Thomas Aldrich of Johns Hopkins University, who managed to obtain the glands of a number of skunks collected in Maine. “I have been more fortunate than my predecessors in being surrounded by those who, for the cause of science, would endure even the odor of a skunk in close proximity,” Aldrich wrote.
Aldrich found that the fluid’s vapors were highly flammable and gave off sulfur dioxide when burned. He also discovered that even humans can sense the presence of these compounds at concentrations of ten parts per billion. This is equivalent to tasting a pinch of salt distributed across one ton of potato chips.
Spotted skunk, Spirogale gracilis
Image from http://wdfw.wa.gov/living/skunks.html
The composition of the musk is astonishing. Over 150 compounds containing sulfur have been isolated. Even more interestingly, each species of skunk has its own chemical signature. The striped skunk’s musk contains seven major volatile compounds, including three thiols, three thioacetate derivatives, and an alkaloid compound, 2-methylquinoline, which is also used in pharmaceuticals including anti-malarial drugs.
The recurring skunky smell of a previously sprayed dog who seemed odor-free until the dry fur is dampened results from the reaction between water and one of the thioacetate derivatives remaining in the fur, creating one of the more volatile and smelly thiol compounds. I found nothing in the literature regarding that first stench of burning rubber, but the odor had morphed into the sickening, familiar sulfur smell by breakfast time. The highly volatile chemicals responsible for the first overwhelming impression must have already begun breaking down in the presence of water and oxygen in the air.
To get rid of the odor, the thiols need to be converted to other, less objectionable chemicals. Exposure to oxygen will lead to their conversion to sulfonic acids. Tomato juice or other acids do not accomplish this critical piece of chemistry, although a properly prepared solution of hydrogen peroxide will do the trick. Regarding the well-established folklore regarding tomato juice, the authors of the book Land Mammals of Oregon commented, "Don’t waste good tomato juice- add a little vodka and drink it; it won’t reduce the odor, but the odor won’t bother you so much!”
I didn't have any tomato juice or vodka on hand, only a bottle of doggy shampoo. I went to work at once, and by dawn, the dog was still stinking with sulfur, but now had undertones of green tea and lavender. At least he was clean. Fortunately, olfactory fatigue had set in, and we stopped noticing the stench unless we left the house for a while.
I'm not sure my dog has learned his lesson. I'll pay more attention to the atmosphere of early morning next year, making sure that no bad love is in the air before flinging open the door. Or at least, I'll make coffee first.
Aldrich, Thomas B. 1896. A chemical study of the secretion of the anal glands of Mephitis mephitica (common skunk), with remarks on the physiological properties of this secretion. Journal of Experimental Medicine 1:323-340.
Anderson, K. K., D. T. Bernstein, R. L. Caret, and L. J. Romanczyk, Jr. 1982. Chemical constituents of the defensive secretion of the striped skunk (Mephitis mephitis). Tetrahedron 38:1965-1970.
Medill, S.A., A. Renard, and S. Larivie. 2001. Onogeny of antipredator behavior in striped skunks, Mephitis mephitis. Ethology, Ecology & Evolution 23(1):41-48.
Verts, B. J., and L. N. Carraway. 1998. Land Mammals of Oregon. University of California Press, Berkeley, California.
Wood, W. F. 1989. New components in defensive secretion of the striped skunk, Mephitis mephitis. Journal of Chemical Ecology 16:2057-2065.
Wood, W. F. 1999. The history of skunk defensive secretion research. Chemical educator 4:44-50.
Wood, W. F., B. G. Sollers, G. A. Dragoo, and J. W. Dragoo. 2002. Volatile components in defensive spray of the hooded skunk, Mephitis macroura. Journal of Chemical Ecology 28:1865-1870.