Showing posts with label UV. Show all posts
Showing posts with label UV. Show all posts

Tuesday, February 4, 2014

Photochromic Blast from the Past

While digging through some old ACS party favors, I came across this wallet card, which I obtained at an ACS "Kids in Chemistry" event ca. 2001.  A check-in with Mr. Google brings back this 2004 Celebrating Chemistry outreach pamphlet, where the PULS (Photochromic Ultraviolet Light Sensor) card helps budding chemists understand the virtue of UV-blocking sunscreens.

What's missing for us big kids? An explanation of the inner workings of the cards' photochromic dye!

Does anyone with long-toothed ACS volunteer experience happen to know the answer? When did these cards hit the scene? Who manufactured them? What dyes were used? Are they still in use for outreach today?




Saturday, October 20, 2012

Goodness Gracious, Great Balls of...Sunscreen?

Actual AP headline yesterday: "Banana Boat recalls sunscreen due to fire risk." CNN, ever one for a scare, upped the ante with their headline: "Sunscreen could burst into flames on skin." (emphasis mine). Did I miss the part when sunscreen formulators started including white phosphorus in the mix?!?

Kidding aside, I'm not talking about "toxic chemicals" here; sunscreen already occupies a special place at Just Like Cooking due to the clouds of chemophobia swirling around it. The fire risk appears to involve two factors: engineering and consumer usage. An Energizer Holdings* corporate spokesman said the canister spray valve applies too much product, which leads to longer-than-average drying times. The exacerbating factor? Customers suffering burns engaged in barbecuing and welding immediately after application.

Well, what is so flammable about spray-on sunscreen, anyway? The ingredients list shows all the usual suspects: UV blockers, vitamins, surfactants, and polymers - none of which are particularly flammable. Two components catch my eye, though: isobutane and SD Alcohol 40. One commonly finds isobutane, the simplest branched hydrocarbon, in refrigeration coils and aerosol products. It could certainly ignite, but high volatility means that most of it flies away mere seconds after you spray it on. SD Alcohol 40**, however, is almost straight ethanol, and makes up a large portion of the overall spray. It would also fit the bill for physical properties: boils at 173 deg F, vapor pressure 40x lower than isobutane. A fog of ethanol slowly evaporating from your arms certainly invites ignition.

*Fast fact: Did you know Energizer Holdings owned Banana Boat? I didn't. They also apparently make shaving creams and tampons. Huh.

**The Code of Federal Regulations (CFR) actually tightly regulates specially denatured (SD) alcohols for use in lotions, oils, creams, and sprays. Here's the page for blend "40." I was rather surprised to find out that sunscreen actually contains trace amounts of complex alkaloids: quassin, brucine. The bitter taste and side effects discourage drinking SD-40 for recreation.

Sunday, May 20, 2012

Sunscreen Chemophobia: Oxybenzone

(I wrote this for participation in the 2012 'Toxic Chemicals' Blog Carnival, over at ScienceGeist)


This 'suit' wants to sneak more chemicals into your sunscreen!
Source: EWG 'Hall of Shame'
Courtesy of Mother Jones and the Environmental Working Group (EWG), we can all breathe a bit easier. The eco-conscious nonprofit organizations have just released their recommendations for summer sunscreens. Unsurprisingly, the Top 20 are cut from the same cloth; words such as "natural," "clear," "garden," and "organic" abound. Ingredients, too: ~20% or so of 'micronized' (>100 nm) zinc oxide, some titanium dioxide for good measure . . .and just about every fruit oil, tea extract, or skin moisturizer you can think of.

Actually, I found myself much more drawn to the 'Hall of Shame.' These sunscreen outlaws represent all the nefarious tricks #BigChem might play on an unsuspecting public - sneaking in oxybenzone, "nano-zinc," and retinyl palmitate (synthetic Vitamin A) to make a buck off naive customers. I won't weigh in on the last two ingredients, but oxybenzone certainly caught my eye.

Oxybenzone, also called benzophenone-3, finds its way into sunscreen, lipstick, lotions, paints, and polymers. According to the Merck Index, it was first prepared over a century ago (1906), and patents from the 1950s show a simple one-step prep, Friedel-Crafts acylation of benzoyl chloride, which forms the new C-C bond between the "left" aromatic ring and the C=O group. Oxybenzone actually absorbs UV light over a wide swath of the spectrum, from 280-320 nm, meaning it offers sun protection from both UV-A and UV-B.

oxybenzone
The EWG calls oxybenzone a "hormone-disrupting chemical." Like bisphenol A (BPA), another well-reported and contentious molecule, oxybenzone contains a free phenol group, and two aromatic rings linked by a central carbon bridge. These atomic features tend to crop up in compounds that mimic estrogens in the body.

Well, does oxybenzone pose endocrine risks? Where could you find that info, anyway?

I started where I usually do: TOXNET, the U.S. National Library of Medicine reference database. Oxybenzone triggers six references from the Developmental Toxin (DART) literature, which cover 18 years of studies on fish, mice, and cell cultures. I also checked PubMed, grabbed a 1992 National Toxicology Program (NTP) oxybenzone report, and the 2008 European Commission SCCP recommendations for consumer exposure.

What do the data show? At the highest doses - 50,000 ppm - all animals develop liver, kidney, and reproductive organ damage. But the dose makes the poison, and as you feed (oral) or rub on (dermal) less compound, the side effects fall off rapidly. No teratogenicity (fetal harm), no mutagenicity (DNA errors), and no unexplained deaths. The scientists did observe indications of "moderate reproductive toxicity," but, again, these showed up in the highest-dose groups. To replicate these effects in humans, you'd have to literally eat spoonfuls of the compound (For ongoing oxybenzone studies, see: NTP, CDC).

The European Union, exemplars for cautious chemical regulation, provide a convenient calculation for human exposure: for a standard 60 kg (132 lb) person, given skin absorption, sunscreen concentration (6% oxybenzone), and average application at 18 g (just over half an ounce), exposure = 1.78 mg / kg / body weight / day. That's ~2 ppm, fully 500 times less than the lowest doses currently testing at the NTP (see above). The 2008 EU panel assigns oxybenzone a Margin of Safety of 112; compounds above 100 generally meet their benchmark for safe use.

Delicious cup of low-dose,
 bioactive compounds
Source: Green Tea Health
But, hormones influence body chemistry at miniscule doses, right? And, these sunscreen compounds are ubiquitous! How can we be absolutely certain that they aren't toxic? Well, I'll counter with a simple observation: herbal, plant, and seed extracts - like the shea butter, aloe juice, camellia seed oil, jojoba, calendula, papaya, plantain leaf, starflower seed, linseed oil, green tea extract, olive oil, plankton, avocado oil, primrose oil, and bark extracts found in the "alternative" sunscreens - have just as many, if not more bioactive compounds!

For chemophobic consumers, the general (albeit, flawed) reasoning seems to go something like this:
Many small, aromatic, heteroatom-containing molecules may be endocrine disruptors.
Industrial companies produce many such chemical compounds.
Therefore, many "industrial" chemicals cause health problems.
Magically, however, this logical logjam clears if you mention "natural," "organic," or "chemical-free" formulations. I suspect the reasoning goes:
Many small, aromatic, heteroatom-containing molecules may be endocrine disruptors.
Natural product extracts contain dozens of compounds, some unknown, many untested.
But, since they're from plant extracts, they're probably safe.
Would consumer impressions of oxybenzone change if it were. . .a natural plant extract? Good news: it is.

That's right, the compound occurs naturally in various flower pigments, which chemically trained eyes might have detected in the "resorcinol-like" framework. To stretch the metaphor, given the eased FDA rules regarding dietary supplements, I wonder if one could employ this tactic to produce a "natural, plant-based sunscreen" that still contains oxybenzone!

Happy summer, everyone! Think clearly, ask questions, and challenge assumptions. And, wherever you buy it from, remember to always wear your sunscreen.

For a different perspective on EWG's sunscreen data, head over to Science-Based Medicine