Sea ice in the Arctic; tributaries to rivers in China; snow in the Alps; water 1,000 meters below the surface of the ocean; freshly fallen rain water; polar bear blood; fillets of bluegill from rivers in Minnesota and North Carolina; human blood, breast milk, and umbilical cords its a varied list from across the planet, and in all of these places, ecosystems, and organisms, scientists have detected perfluorinated chemicals.
The bonds in these manmade chemicals are among the strongest in organic chemistry, and that stability lends great durability and waterproofing to surfaces, including much of today’s outdoor gear.
Durable water repellent (DWR) has been compared to fish scales and peach fuzz initially, very repellent, but scrub hard enough, and the scales and fuzz flake off. The compounds resiliency means it lasts in the environment and spreads, accumulating in organisms and ecosystems. Governments around the world, including the U.S., are increasingly asking chemical companies to stop producing these chemicals and their precursors. Though they havent tested as harmful for humans yet, some estimates suggest that allowing these chemicals to build up for, say, 30 years could be problematic.
Outdoor gear manufacturers have been working to replace perfluorooctanoic acid (PFOA), a so-called long-chain PFC in DWR, with short-chain PFCs that provide durability and water resistance but dont last as long in the environment.
That has fed a hurried, holy-grail-like search for alternatives with most outdoor brands pledging that their clothing will be entirely free of the long-chain chemicals by 2016.
Many companies are choosing to update their DWR to the short-chain chemistry, which is less durable. This is not something consumers want to hear: That new jacket it isnt as good as your old one. Several outdoor companies found that preliminary tests with short-chain chemistries failed to meet the standards consumers demand. Getting the new chemistry ready before bans recommended by governments roll out has presented a challenge.
The longer the chains are, the better theyre going to repel water and oil, and the converse when theyre shorter, said Matt Dwyer, director of materials, innovation, and development for Patagonia. The whole industry is going to have to deal with this change in performance as they get rid of these long-chain chemistries.
More Than Just DWR
PFOAs, the chemicals inherent to producing DWR-treated gear, are in a family of chemicals called fluoropolymers, which have been produced by chemical manufacturers for more than half a century. They are used to treat myriad materials carpet, paint, nonstick cookware, food contact paper, and outdoor apparel to increase fire resistance and oil, stain, grease, and water repellency. In 2004, the total demand for fluoropolymers was 50,000 to 100,000 tons, the U.S. Environmental Protection Agency said in its 2009 action plan on long-chain perfluorinated chemicals. About 10 percent of those chemicals are used for apparel.
The European Union has identified these chemicals as cause for concern, Norway has banned them, and the EPA asked major chemical companies to commit to eliminating C8-based fluorotelomers including PFOA as well as PFOA precursors by no later than 2015.
The Band-Aid is getting ripped off for everybody, Dwyer said. It wont even be legal to make this stuff, let alone buy it and put it in your product, and some countries wont even let it on the shelves of their stores. We really ramped up our effort, knowing that this deadline was going to happen, because it affects the way we buy, the performance we expect. It could affect the shade and how the material takes and retains dye, as well as the handfeel of the material.
The Quest for a Replacement
Initial samples of the PFOA-free materials were crunchy, like a piece of paper, Dwyer said, and the water repellency wasnt so great, but more recent chemistries show just a slight decrease in beading.
Patagonias fall 2015 garments are nearly free of those long-chain chemistries, and spring 2016 will be entirely free, he said. Whats next is tough to know.
Is somebody going to come out and now say [the short-chain] C6 is bad? Maybe, I dont know, he said.
Going entirely free of these chemistries, Dwyer said, would come with performance compromises.
Fluorine is a great element for the science behind water repellency and by switching chemistries, you give up some of the performance of that, whether its durability to abrasion, and detergents or being able to launder it, Dwyer said.
Gore-Tex announced in January 2014 that it had eliminated long-chain perfluorocarbons from its ubiquitously used fabrics and moved to short-chain chemicals.
The biggest challenge certainly with a new DWR is the durability of the water repellency, said Bernhard Kiehl, leader of the Gore-Tex Fabrics Division sustainability team.
One finding for retailers to pass on to consumers: washing and tumble-drying waterproof garments increases their life and brings back the water repellency to the original level of performance. That kind of care is of increasing importance with the short-chain chemistry, Kiehl said. But those care requirements are also part of the environmental impacts.
If a poor DWR performance leads to more frequent washing and reproofing, that comes with a footprint, and so you have to balance what materials you are choosing, he said. We know that basically whatever we do comes with a footprint, so from a sustainability perspective, the work never stops.
Gore-Tex screens all the chemistry out there fluorinated and non-fluorinated technologies and based on that, Kiehl said, the short-chain fluorinated materials are the best available. The durable water repellency of non-fluorinated offerings hasnt held up in field tests.
A New Path
British outdoor brand Montane has set the ambitious goal of moving clothing to short-chain C6 chemistries for now, and going entirely free of those chemistries by 2020, said brand director Paul Cosgrove.
In terms of the performance of C6, in a lot of instances actually weve been sort of pleasantly surprised about the performance, Cosgrove said. Its still not the ideal solution its still a chain chemical, and we would love to get away from it as well. Montane has been putting pressure on its suppliers, he said, and the hope is to soon see a breakthrough. Along the way, chemistry may not be the only thing new.
It may start to change the nature of some of the product designs that we might see in the future, Cosgrove said, mentioning wicking mesh liners and different membranes. There are certain things you can do in terms of apparel design to improve water repellency.
Nikwax after-care waterproofing and its parent apparel company, Paramo, are entirely free of these chemistries, and have been for years.
When we were developing our waterproofing technology, the owner looked into them and just made the decision then and there that there was too much of a risk, said Heidi Allen, marketing director for Nikwax. We make our own waterproof, breathable apparel line thats totally fluorocarbon-free, so there is a way to do it. Paramo gear is not yet available in the United States.
While outdoor apparel thats brought into the home fully assembled might shed a certain level of PFOA, Nikwax comes in liquid form with a higher risk of exposure for consumers.
As far as the switch to C6, Allen said, its just not enough. Basically, we dont believe that C6 chains are safe. They do biodegrade into a slightly different acid but that has not proven to be safe for humans, she said.
German company Sympatex Technologies, which produces materials for clothing, footwear, accessories and technical applications it touts as 100 percent wind- and waterproof in addition to being 100 percent recyclable, has also released a PFOA-free line.
PFOA has long been stringently limited by Bluesign Technologies, and while the manufacturing certification group acknowledges short-chain alternatives may be necessary for now, it suggests using them only when absolutely necessary.
How PFOA finds its way into human blood isnt yet fully understood. Elevated blood levels have been found near areas of known manufacturing releases into waterways, and filters cannot remove it from drinking water. But the presence of PFOA in blood samples was taken nationwide, the EPA said, indicating other exposure pathways. Carpet and nonstick cookware are some likely sources, and indoor dust has been found to contain PFCs. Rainwater may also be coating home gardens in PFCs. These chemicals are also finding their way to the oceans, which have been suggested as the final resting place for these acids. Once there, they will continue to pose a threat to marine life and contribute to the acidification levels of oceans.