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Silicone is it toxic?  RSS feed

 
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I am wondering what people think about silicon? Is it toxic? Should I avoid using it?
 
pollinator
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I sure wouldn't want to eat it or mix it into my drinking water.
 
pollinator
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If it were pure silicone it might be, but evidently it contains very toxic oils as well as fillers, which we don't know what they are, and, of course, colorings. See this for a full run-down on things you might want to be concerned about: http://lifeyourway.net/is-silicone-bakeware-really-safe/
 
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Silicone-gel breast implants have been associated with a myriad of autoimmune and connective tissue disorders by anecdotal reports and small observational series. To date, no prospective epidemiologic studies have been done to substantiate these observations, but an increasing body of literature is being developed and older studies are being recognized that point to immunotoxic or inflammatory effects of these breast implant components. The development of disease due to implants would depend on the interaction of genetic host factors so that only a few patients would potentially be at risk. Based on the example of other chemically mediated disorders, such as scleroderma in association with silica exposure, latency periods of more than 30 years before disease develops may be possible. *



I'm sure that in the 30 years it takes to find out the answer to the question, there will be a steady stream of excuse makers, correlation-is-not-causation prattlers, "skeptics", apologists, and advertisments telling us that the answer is definitively "no".

The first of these will occur shortly when a post will point out that the silicone in bakeware is different from the silicone in breast implants.



* West J Med. May 1995; 162(5): 418–425
 
Sam Barber
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Well the bake wear is what I am wondering about.
 
John Elliott
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Sam Barber wrote:Well the bake wear is what I am wondering about.



Well then to expand my snarky previous answer, I will outline some ways to minimize the "toxic gick" that could be associated with using it:

-- Soak it in a dilute solution of bleach overnight (1 tablespoon of vinegar in a quart of water). Bleach is a strong oxidizing agent and will oxidize any errant molecules you would rather not be eating.

-- Then bake it a couple of times by itself. If you cycle it to high temperature and let it cool off, then any residuals that could be in the manufacturing process will be driven off and not into your food.

These should be part of a conscientious manufacturing process to passivate the silicone before selling it to the public, but as we all know, these are also more processing steps that could cut into profits. I wouldn't be so sure that the Chinese factory that turns these out is that conscientious.
 
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And dare I broach the subject of mooncups? How bad are they likely to be?
 
pollinator
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Burra
I am fairly sure Mooncups are no danger to Sam

David
 
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Well, I must admit I was thinking more of myself...

But there may be others who'd like to know!

Are they likely to be made of out 'safe' silicone?
 
David Livingston
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I would suggest Mooncups are safer than implants or cooking utensils as you are in no danger of ingesting the stuff

David
 
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now I am curious about mooncups as well. I own one and usually don't use it but I do sometimes.
 
Sam Barber
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I don't like were this conversation went...
 
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Sam Barber wrote:I don't like were this conversation went...



Uncomfortable turn for us guys, but very valid concern--if it is toxic while at room temps, that is about the most effective (worst) way to get it into a person's bloodstream. Important to me, as I want my wife to outlive me.

I see the silicone itself to be fairly benign, better than most plastics but I see two very big potential problems--the colorants and the mold release agents used. Both of those could include really toxic gick; shouldn't but could.

We use silicone pot holders, spatulas, etc. We use silicone baking pans as molds for soap, but don't actually bake with them. We don't bake with aluminum, either, if we can help it and use parchment when we have to.

 
Meryt Helmer
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some, maybe most of the brands of silicone menstrual cups are supposed to be medical grade and they are generally not colorful. i don't know what color silicone is without any color added though. hmm
 
master steward
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Bakeware: it would be good to get comparisons to aluminum or stainless steel bakeware. I am also curious about what might happen at temperatures that are too high.

mooncups: I think it would be good to compare to "organic" tampons and pads. Plus the "party in your pants" stuff, or even the simpler "cotton cloth" approach. But I think the mooncup stuff would also need to cover the general approach - are there any risks in keeping something like that in your vagina for several days per month for years and years and years. Could that much contact turn out to be an irritant that leads to cancer?

food storage: we have some glass and silicone food storage container. i like the idea that we are not using plastic.

For all of these and the many other uses, I think I would like to hear from some chemists that are passionate about avoiding toxins discuss the known issues and the concerns-that-are-not-yet-known.

 
Meryt Helmer
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Paul I was once reading a forum that had a section on menstrual cups and someone on their had been boiling hers to disinfect it and forgot about it, apparently the entire thing turned into ash and it got all over her kitchen. her family was very unhappy about it understandably.
 
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I would second Paul's response, and look to Scientist's/Chemists with a bent for look closely at "toxins" in byproduct, side effect, and general product degradation. We as a species have become very inventive to mask, and contain our living of life without truly considering the long term effects, or asking the question..."is this really that much better than not doing anything or using something more natural.

Regards,

j.
 
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So the FDA says that there is safe 'food grade' silicone and the NSF backs that up. They use it a lot in medical implants too. Aquarium silicone seal seems to be everyone's fail-safe.

Problem is, I don't trust the FDA or the NSF as there is quite a lobby behind the chemical industry.

As an architect, we know that the sealant is not a good thing in the uncured state, you are supposed to use precautions when mixing and applying and cleaning. Curing typically releases gick to the atmosphere (use in well ventilated space) but miraculously is safe for use after it has cured. Thus far no one has died from long-term exposure but that's what they said about Asbestos, Uncoated Aluminum Cookware, Pickles, Bacon and Cigarettes when I was young too!

I will keep digging, but I think the party line is going to be "Sure it's safe".

No "marked harmful effects on organisms in the environment" have been noted for silicones. They are nonbiodegradable but are absorbed by solids in waste water treatment facilities. Degradation is catalyzed by various clays.
- Hans-Heinrich Moretto, Manfred Schulze, Gebhard Wagner (2005) "Silicones" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim. doi:10.1002/14356007.a24_057
 
gardener
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Thanks for the dip into chemistry-land.
Very interesting about degradation catalysed by clays.
I agree that aquarium seal smells nasty. But you do have to admit that a lot of sensitive tropical fish live in aquariums sealed with it. So you can see their point; fish don't tolerate the chlorine we do in our drinking water, but they can live with a little bit of silicone off-gas or dissolved solutes or whatever.

From a low-level scan of Wikipedia, there also appear to be different types of silicone polymers.
Some of which use elements that I'm comfortable with. (I know simple, inorganic chemistry, but not much organic, so I tend to go with brute element analysis as a first step. Elements which can theoretically biodegrade seem safer than those that don't. I know that organic compounds can also be very toxic, I just don't know which ones are most dangerous, so I am a bit more lost there.).
But there are some silicone polymers that are made with chlorine, and polymers with chlorine are one category of organic compounds that ring warning bells for me. They tend to gum up living beings pretty good.

So there should be literature that distinguishes between different types of silicones. Maybe that's an important component in the 'food-grade' designation.
Product info should also give this - you can request an MSDS for any item that might be used in a workplace, and most places put a reasonable amount of info in there to be able to suss out which products they are using. Others don't ("a proprietary compound of X and Y").
...

For the OP's question about baking and cooking, I prefer materials of known chemistry that I can understand.

Cast iron does this for me - if I cook with acid in it, I get extra iron in the food. Ok with me.
If I cook with oils, it polymerizes to a 'mars black' form of iron, and makes it non-stick. OK with me. (Mars black is not on the short list of pigments known to kill artists, or puppies, or anything like that. And while over-cooked polymerized cooking oils are not great for you, there are a lot worse things in the world.)
If I wash it with soap or alkaline cleansers, I lose the non-stick, but I can re-make it again. I might get some detergent effects in the remaining non-stick if I don't rinse. All pretty much normal levels of household hazard. OK with me.

Glass is also pretty much OK with me. I use glass jars for long-term food storage, and put hot foods into them (if they are Mason or tempered glass).
I think I might prefer unglazed terra-cotta, for routine cookware, if it's chemical exposure we're worried about. Even if it's harder to clean than glass.
(Glass is clear, but that doesn't tell you what's in it. Lots of things like lead can be included in clear glass. Not usually anymore, but still, I think glassware is uppity and pretending to be purer than it is. Bake-safe glass also has that little trick of lasting for years despite chips and scratches, then suddenly exploding. Also nobody knows whether to call it a 'fluid' or a 'non-crystalline solid.' It is devious, glassware. Watch it closely. Especially if the cat is nearby.)

Glazed ceramic and terra-cotta - usually OK with me. Must be marked 'food safe,' and I prefer muted oxide colors over glossy or bright ones, especially for interior linings. I think most food-safe glazed pottery is at least as safe as glass. But because cracked pottery can still be used, I take care not to let it soak in things or get gunky. A stained cracked ceramic dish may have weird stuff living in the crack; might be time to retire it, or just sanitize it (boiling water / dishwasher) routinely. Pottery usually safer than metal or plastic, however, for chemical exposure.
Mended pottery is usually now a pottery-polymer composite. I don't mend hot-dish pottery (mugs etc) because I don't trust the polymers to stay out of solution when heated.

Glazed ceramic / enameled steel are also pretty much OK with me, as long as the interior colors are inert ones like white or rust-red. (I don't trust some of the blues, greens, and other bright pigments in contact with food. And if they are using something other than glass as the enamel base, I don't want to know about it. So baked enamel on cast-iron or steel cookware is usually OK with me.)

Stainless steel is mostly OK with me. It has some metals I don't like, but the stainless, chemical-resistant alloy means they mostly don't escape into the food that much.

Copper is mostly OK with me. Although toxic in large amounts, it's not very reactive, and does some nice things to certain foods like egg whites. I don't think I'm getting much copper in my diet regardless of cooking with one copper pan occasionally. Also copper and brass water jugs kill pathogens with 1 day of water storage, which is pretty cool, if a little alarming because that means it's effectively a pesticide of some kind.

Aluminum is not entirely OK with me. Though its lightweight, it's a very reactive metal, meaning it will leap into my food at the least trace of acid. I see pitting over time on aluminum pans; it's also soft, and can be scratched up by cleaning, meaning you expose more aluminum to be oxidized or dissolved in acidic foods.
There was also that urban legend about the link to Altzheimers, which is a disease that has occurred in my family, and I don't want to increase my risk factors. However, aluminum in its oxidized state is one of the most common minerals on our planet, and we are pretty well adapted to deal with it. So, could be OK with you.

Plastic is not entirely OK with me. I do use it to store and transport cold foods. But I notice that it stains with red sauce, and don't want it leaching anything into that same red sauce. Reports are that plasticizers get into foods much more easily if it's greasy or oily foods, so I tend to put those things in glass, or at least cool them before putting them in plastic and then not store them very long.
Natural rubber is OK with me, but does not work for some friends (allergies). So, like walnut oil and peanut oil, it is one of those lovely things with lots of uses that I still don't keep around that much.

Non-stick is not OK with me. It doesn't work, doesn't last, can't be scrubbed easily, and it has that 'new car smell' that says weird polymers. I don't buy it, and hand-me-down pans often get re-purposed to storage bins if their non-stick shows any sign of degrading.

Silicone seems like plastic, which seems like a weird thing to bake with. So I probably would not buy silicone bakeware. I do have silicone hot pads, and spatulas, and do not have a problem with silicone lids on containers.

...
When would silicone and plastics be OK with me?
I suspect these materials will be safer if well cleaned, and used with cold foods. (I have a silicone ice tray for star-shaped ice cubes; don't use it often, but it doesn't freak me out either.)

Body temperature is warmer, and there is the possibility of long-term exposure transmitting chemicals into fatty tissues and cell walls (fat-like structures). Embedding or carrying things in the body in thin-skinned mucus membrane areas seems risky. But on the other hand, I spend hours typing on plastic keyboards and wiping my nose. Which is pretty gross now that I think about it (the nose wiping more than the plastic).
I have never felt compelled to analyze the polymer content of my keyboard, or the paints that my wrists rest on beside it. We use silicone pads for ergonomic keyboards, too, and I suspect the health benefits (avoiding wrist damage) outweigh any possible 30-years-down-the-line uptick in some undisclosed risk factor, for most people. So it may also be a matter of pick-your-battles.
(I do not personally favor stuffing anything plastic into my body, anywhere. I don't even like wearing noseplugs, though I will tolerate earplugs to avoid pain. This seems as much a matter of personal preference as anything else. I will wear safety glasses for a lot longer than some friends, who are comfortable with the nose plugs but don't like glasses. And like that. I would be happy to discuss more gory details with the ladies in private.)

Very hot uses will make chemicals move and change faster, so baking in any polymer, or the machine oils on cast iron or stainless steel, would be relatively high exposure. As with microwaves, baking in any plastic is likely to maximize the release of any plasticizers, or stray polymers, or mold-release, or whatever might be there.
So when I get a new cookpan, I want to pull out as much plasticizer and mold-release compound and machine oil as possible, before cooking in it.
Stainless steel always gets washed with hot water and detergent, to remove machine oil. Cast-iron gets scrubbed, and then sometimes baked to cook any residual grease (with a secondhand deep-fryer that had rancid gummy oils, I scrubbed it and then baked it until it stopped smoking to get rid of the rancid gels).

Inhaling volatile polymers sounds a lot more risky than eating them, and probably on par with having them injected/ surgically implanted.
So if I consider heat-treating the pan to avoid eating the gunk, I want to make sure I am not breathing the gunk. Whatever gunk there might be.

If your oven is vented, you could put the bakeware on a 400 degree baking cycle (stay well below its rated temperature, for an empty pan), and vent the volatiles out of the house.
If your oven isn't vented, keep the temp below smoke point for any materials used, or rig up temporary ventilation. If you can smell anything, vent the house.
If you do this on a rainy day you will limit your contribution to air pollution; don't do it on a day with local smog warnings.

Before/during the bake-in cycles:
I like the dilute bleach approach. Though vinegar is not always reliable to cut greasy polymers. Something like an alkaline scrub (baking soda or non-chlorine bleach), or hydrogen peroxide, might break down/extract any factory oils faster than vinegar. You could do both, on separate cycles, to be sure. I would be tempted to heat the pan with a vinegar bath in it, then heat it again with a baking-soda rubdown.

I also like the idea of greasing up the pan with used fryer oil, or whatever food-grade grease you can spare, and then heating it for a while, before wiping off and repeating.
Anything that gets pulled out by oils, should get pulled out by the sacrificial oils. Repeat two or three times with various combinations.
Wash the residue off with a strong detergent, and you should be a lot cleaner than you started.

I would, off the cuff, guess that exposure from a factory-new product is about 10 or 100 times worse than a slightly-used object.
So by pre-treating with all manner of likely food chemicals (acids, alkali, oils, maybe also a grease-and-flour treatment for starches), you are taking that initial exposure away and lowering the subsequent doses.

After years of use, a decaying, older object would increase the exposure rate again.
Any time a plastic polymer appears to change in texture, color (bleached out), stiffness (getting more/less flexible), or break down in any apparent way, that tells me it's not reliably inert. I don't want active polymer-decay products in my food, no do I want them breaking during use. So I would retire any plastic foodware that shows signs of aging (scratched-up, colors changed, over-heated, sun-bleached, etc).
...

Why do silicone products need mold-release? Aren't they flexible enough to come right off the molds? Or are these harder versions?

It could also be that if it's a two-part polymer system, the stuff on the outside of the casting is not a mold release, but unreacted polymer, or a combination of unreacted polymer and a mold-release gel or powder. All excellent things not to have in your food.

I do think that our lives are pretty safe, overall, these days. The number of people not dying of cholera, typhoid, pneumonia, starvation, freezing to death, annoying their violent neighbors, house fires, factory fires, lynchings, civil war, and the like, adds up to billions. (Plenty of people do still die of these things, but not nearly as many as survive them all.) Which means that worrying over the potential toxicity of a new polymer is a pretty low-key life decision.

If you like the pretty colors, go for it.
You are far more likely to be slowly poisoned or quickly eliminated by your car, or by doing anything while intoxicated.

If you are concerned about the big picture, fate of our world, and industrial pollution, bake less and eat more home-grown salad (no wrappers nor shipping nor storage power nor cooking energy).
Spinning it in a silicone salad-spinner, if they make those, seems pretty harmless too.

-Erica
 
Erica Wisner
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also:
I have someone in the house with poor circulation in his foot, and crutches that knock things off counters. Which means shards of broken glass around the kitchen might happen more often here, and carry a higher risk of serious infection, than for other people. Also, he is a phenomenal cook, and more so when he is not frustrated with himself for knocking breakable things off counters.
I also sometimes get low-blood-sugar shakes when preparing breakfast in the morning, and am not a particularly tidy housekeeper. So altogether we are maybe more prone to breaking cookware than some other people.
And my cat has knocked handles off at least 3 ceramic mugs this winter, but they don't tend to splinter as badly as glass. I foiled his latest attempt by using my stainless travel mug at my desk.

Non-shattering plastic or metal containers thus have some safety value for us, as for households with children or diabetics.

We didn't mention wood, either, which is a material I love for any practical cooking purpose.
Stainless, aluminum, and nonstick pans are lighter-weight than cast iron, and I definitely know people who are limited in their ability to move a large cast-iron griddle or deep-fryer around. Physical hazards and fire hazards are serious too.

Does silicone bakeware seem to answer some real, practical concerns you have with other bakeware?

I do think FDA approval might be an OK minimum standard to say, this is acceptable because other factors likely outweigh toxicity concerns. It's not the FDA's job to pick only the best things in an imperfect world - it's their job to assess whether new things meet a minimum safety standard that matches what people have been content to knowingly expose themselves to in the past. A few aphids in the broccoli are not going to hurt anyone. Their assessment is roughly on that level for 'safe' or 'pure' ingredients. There are plenty of traditional methods, like fermented foods or raw juices, that have a hard time passing FDA standards. Many of the same people who scrupulously avoid plastics love fermented foods. Ultimately, you pick your poisons.

You can make a choice that works for you, it doesn't have to be 100% perfect for everybody.

-Erica


 
Erica Wisner
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Here's a note from the Wikipedia article about the synthesis of silicone:

Silica (silicon dioxide), common in sandstone, beach sand, and similar natural materials, is the initial material from which silicones are produced. Silicones are synthesized from chlorosilanes, tetraethoxysilane, and related compounds.

In producing polydimethylsiloxane, the starting material is dimethyldichlorosilane, which reacts with water as follows:

n Si(CH3)2Cl2 + n H2O → [Si(CH3)2O]n + 2n HCl

The polymerization typically produces linear chains capped with Si-Cl or Si-OH (silanol) groups. Under different conditions the polymer is a cyclic, not a chain.[1]

For consumer applications such as caulks silyl acetates are used instead of silyl chlorides. The hydrolysis of the acetates produce the less dangerous acetic acid (the acid found in vinegar) as the reaction product of a much slower curing process. This chemistry is used in many consumer applications, such as silicone caulk and adhesives.

Branches or cross-links in the polymer chain can be introduced by using silane precursors with more acid-forming groups and fewer methyl groups, such as methyltrichlorosilane. Ideally, each molecule of such a compound becomes a branch point. This process can be used to produce hard silicone resins. Similarly, precursors with three methyl groups can be used to limit molecular weight, since each such molecule has only one reactive site and so forms the end of a siloxane chain. Modern silicone resins are generally made using tetraethoxysilane, which reacts in a more mild and controllable manner than chlorosilanes.

http://en.wikipedia.org/wiki/Silicone

It's certainly not the same thing as silicon.
It is like sand, in the same way that aluminum, stainless steel, or leaded glass are like sand. It contains some of the same elements, but in very different structures with different properties.

I would evaluate it on its own merits as a plastic, and not assume that any two 'silicone' objects are equally safe or hazardous.

I don't know whether 'consumer' applications includes the bakeware and cookware categories, or whether these are considered 'industrial' synthesis. (Silicone caulks are used by the consumer in their reactive state, while silicone spatulas could be manufactured in a controlled setting and turned over to consumers once 'inert.') But I bet they have more stringent toxicity controls that lubricants or firestopping products.

-Erica
 
pollinator
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Have not yet purchased any more silicone cookware than 2 spatulas, but have had concerns about them..guess that might be why I haven't gotten any YET..and may not..Was thinking of those for over glass bowls in the microwave, the covers..but haven't gotten those either.

I do use silicone caulk occasionally in building projects however
 
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I have often wondered the same thing myself. When we first attempted to remove teflon and plastic from our kitchen, we had several silicone baking pans and spatulas. Switching to all cast iron for stovetop cooking fixed the spatula issue since metal spatulas work much better in cast. The bakeware we eventually ditched for a cast iron dutch oven, cast pizza pan, pyrex bread pan as well as casseroles, and baking stones for other stuff. The only thing we still use occasionally is a non-stick muffin pan, but I'm always on the lookout for a cast one of those as well.

We currently use silicone or cloth trivets and silicone gloves for removing hot objects. My wife does use a silicone cup, so that is definitely of interest to us, especially since she has a family history of cervical issues…

I will be following this thread closely to be sure.
 
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