Reflections on the 6th International Symposium on Flame Retardants

A little bit too keen, I was the first one into the conference hall.

A little bit too keen, I was the first one into the conference hall at the Sir Francis Drake Hotel

As I mentioned in my previous post, I was recently in San Francisco for the 6th International Symposium on Flame Retardants. California is a fitting host for a conference on flame retardants, as their unique flammability standard, TB-117, has likely contributed to the ubiquitous contamination of humans and the environment with brominated flame retardants (BFRs), specifically the polybrominated diphenyl ethers (PBDEs). Research has shown repeatedly that PBDEs are environmentally persistent, capable of bioaccumulating in organisms, and potentially toxic. As a result of these facts, PBDEs have been banned in several jurisdictions, and industry has agreed to a voluntary phase-out. This has led replacement chemicals being used in place of the PBDEs. These replacements are less well studied than traditional BFRs, and given that they can be structurally and functionally very dissimilar there is a need for new measurement methodologies and descriptions of their environmental fate and biological activity. The efficacy of flame retardants, which are designed to increase public safety, has also recently been called to question. At this symposium the most current state of the science for flame retardants was presented, and below I highlight some of the interesting research from the various sessions.

Analytical Methods

Studying BFRs often comes with certain analytical challenges. BFRs are tricky to analyze, and given their widespread use, they have become ubiquitous, background contaminants, often showing up in blank laboratory samples. One way to minimize background contamination is to automate and contain the entire extraction procedure. Philip Bassignani of Fluid Management Systems, presented Validating multiple matrix analysis of PBDEs using pressurized liquid extraction and multi-column clean-up, where he showcased the available technology for incorporating Pressurized Liquid Extraction (PLE) and automated multi-column Clean-up as a sample prep procedures, thereby reducing many of the problems associated with traditional manual approaches, and saving loads of time. It was a very cool talk, and made me really wish that this type of instrument was available during my research.

Another problem that was touched upon in this session was the lack of analytical standards for many of these emerging flame retardants. Standards are needed so the identity of a compound can be verified. This is particularly tricky when you are not even sure what you are looking for. Such is the case when you are trying to determine what degradation products, metabolites, or unknown compounds may be in a sample. Mehran Alaee of Environment Canada presented the work Post target determination of brominated flame retardants and related compounds in American Eels captured in Eastern Canada, which was somewhat of an environmental detective story, where they were able to deduce the structure of several unknown contaminants in samples of Eel. This is accomplished by gaining an accurate mass for the unknown compound from the time of flight mass spectrometer, and then determining the possible combination of atoms that could result in that mass, then determining whether the mass spectra of that possible combination fits with the observed spectra in the sample. It is like trying to solve a puzzle, without knowing what the picture is supposed to be.

Measurements in Abiotic Media

Once the methods are developed for analyzing these flame retardants (again not an easy task), next you can go out an measure them in real samples. Rob Letcher of Environment Canada presented the paper Comparative photolytic debromination of decabromodiphenyl ether, decabromodiphenyl ethane, and tetradecabromodiphenoxybenzene flame retardants and environmental considerations, in which he highlights some of the measurements of new and relatively huge BFRs, and some of the pathways by which they can be transformed into more toxic compounds.

Measurements in Biota

In addition to measuring flame retardants in environmental samples like, air, dust, water, and sediment, it is also important to monitor these compounds in biota. The uptake of compounds from the environment into biota is known as bioaccumulation, and if the accumulation is great enough, this can result in toxic effects. Roxana Sühring of Helmholtz-Zentrum Geesthacht, Institute of Coastal Research presented work on the accumulation of flame retardants in two different species of eel, throughout their lifecycles, From glass to silver eel – brominated flame retardants and Dechloranes in European and American eels. The work was very interesting, largely in part because of the unique life-history traits of eels (future post), and the varying susceptibility to contaminants and contaminant profile during their life cycle.

Toxicology

One of the reasons for concern over flame retardants is due to their toxicity. Flame retardants tend to not be acutely toxic, but rather demonstrate a chronic toxicity, often mediated through endocrine system, as several flame retardants have structural similarities to hormones, particularly the thyroid hormones. David Volz of the University of South Carolina presented some very compelling evidence Aryl phosphate esters within a major penta-BDE replacement product induce cardiotoxicity in developing zebrafish embryos: potential role of the aryl hydrocarbon receptor, that demonstrated that some flame retardants are exerting their toxicity through the aryl hydrocarbon receptor; the toxicity of 2,3,7,8-tetrachlorodibenzo-p-dioxin is also mediated through this receptor.

Epidemiology

Regrettably I missed this session as I was discussing my posters with other researchers over lunch and things went long. However, the talk Associations between maternal serum PBDEs and fetal thyroid hormones: Results from the Chemicals, Health and Pregnancy (CHirP) study, looked really cool.

Exposure Pathways

Before there can be toxicity, there must be exposure. This session showed many ways (mainly dust and food) which we are being exposed to these compounds, but two of the talks were about unique occupational exposures. The first, by Anna Strid of Stockholm University looked at Exposure to brominated flame retardants during maintenance work in aircrafts. Airplanes are loaded with flame retardants, and that is probably a good thing, but continuous workplace exposure can become an issue for pilots, flight attendants, and mechanics. Another interesting and overlooked group in terms of high levels of occupational exposure, are gymnasts. Courtney Carignan of Boston University School of Public Health presented work on Gymnast exposure to flame retardants, given that much of gymnastic equipment is foam, which contains high concentration of flame retardants, levels in the air, dust and gymnasts were elevated. The work presented was just the preliminary findings and there is much more to be done, but this was really cool and will be something to keep an eye on.

Policy

The symposium concluded with talks related to how all the research that has been done can change or influence policy. One of the first challenges that will need to be addressed is to get everyone talking the same language. Andreas Rydén of Stockholm University presented A novel abbreviation standard for organobromine, organochlorine and organophosphorus flame retardants, to help get everyone on the same page, which means I will have to change all my references to TBBPA-DBPE, BEHTBP, and EHTeBB in my papers to TBBPA-BDBPE, BEH-TEB, and EH-TBB, respectively. The symposium ended with a panel discussion, which focused on whether there is a need for these flame retardants in various consumer products (e.g., insulation, couches, children’s toys and products), and the current regulatory system for flame retardants which is highly stove-piped (e.g., EPA, California Bureau of Home Furnishings, Department of Toxic Substances Control all have interests and regulations relating to flame retardants) and largely ineffective.  There was a comment from the audience that flame retardants (and other chemicals in consumer products, (e.g., PFCs, musks, nanoparticles) should be regulated just as food, drugs, and pesticides are currently. One comment that really struck me is that scientists are spending lots of time and money (often public funds), to just determine what substances are in the products we are exposed to everyday. Recently, there has been lots of excellent work by researches focused on determining what is in our couches, knowledge that industry has, but does not share because of its proprietary nature. This just seems so backwards to me.

Overall it was a great symposium filled with an almost overwhelming amount of interesting research and discourse. Flame retardants are going to be an environmental and human health issue for a long time, and forums like this symposium are crucial for helping researchers gain insights and share ideas.

The Trouble with Toys

In a quasi-related follow-up to the previous article, this season of buying toys, can become quite stressful while trying to navigate the perils of toy safety, as seen in the video below.

Many toys have health risks including, chocking, strangulation, suffocation, being too loud, having sharp edges, tearing through intestines because of magnets, or may have toxic chemicals in them. Fortunately, the World Against Toys Causing Harm (W.A.T.C.H.), has since 1973 released the annual 10 Worst Toys list to help keep you away from any troubles this holiday season. The US Public Interest Research Group also produces a consumer report on the Trouble in Toyland. Both reports note that toys made of plastics with stabilizing or softening agents will often contain phthalates, toys with electronic components will likely have some flame retardants in them, and others will have metals, such as lead, mercury, cadmium, or chromium (+6). While the exposure (which is key for toxicity) to these compounds is very small, and the effects of some of the chemicals are not that harmful, sometimes it doesn’t hurt to place it safe, especially when it comes to thinking of the children.

But how will the girl be able to color the green frog with these Princess crayons?

While there may be some physical risks from the actual toys, there is also the chance that the toy you get will have have some unintended, psychological effects. Consider toys that are gendered, which really have no business being gendered, like crayons, or Lego, or science kits! Check out this Swedish Toy Catalog which has girls and boys playing together, regardless of the toy. Recently, George Stroumboulopoulos wondered why aren’t there more girls in engineering? And suggested that they need better toys, like the GoldieBlox: The Engineering Toy for Girls.

So take some careful consideration when planning your gifts this season, because they are no doubt loaded with risks be they physical or psychological, but these gender neutral, STEM minded crayons look like an awesome and safe gift.

With these labels you can color that frog a nice Barium Nitrate Ba(NO3)2 Flame, instead of having no green at all.

SETAC Presentations on the Canadian Oil Sands

  1. The 33rd Annual Meeting of the North American Chapter of the Society of Environmental Toxicology and Chemistry (SETAC) is currently underway in Long Beach, California. I wasn’t able to attend SETAC this year, but fortunately for me Naomi Lubick has been tweeting some of the highlights from the conference,
  2. nlubick
    Infrastructure for sewage and wastewater treatment is aging, and could end up making things worse if ignored: leaking poop! #sfei #setac2012

    Mon, Nov 12 2012 10:42:38
  3. nlubick
    Cesium 137 radiation: twice as much from food in Chiba prefecture vs Fukushima city. Air delivered more Cs-137 in the city. #setac2012

    Tue, Nov 13 2012 15:16:20
  4. nlubick
    Hideshige Takada, plastic pellets expert: flame retardants go from plastics into shearwater seabirds in the middle of the Pacific #setac2012

    Wed, Nov 14 2012 09:05:41
  5. But it has been one session that she tweeted about, which revolves around The Canadian Oil Sands, that has been getting quite a bit of attention.
  6. nlubick
    #EnvironmentCanada confirms levels from David Schindler’s lab’s PNAS ppr: #TarSands pollutants in snow near #oilsands operations. #setac2012

    Wed, Nov 14 2012 10:49:54
  7. The paper that she is referring was authored by Erin Kelly (can be found here), examined the concentrations of priority pollutants (Sb, As, Be, Cd, Cr, Cu, Pb, Hg, Ni, Se, Ag, Tl, and Zn) in snowpack and water from the areas surrounding the Alberta oil sands development. One of the main findings of their paper was that within 50 km of upgrading facilities, 11 400 metric tons of airborne particulates were deposited during 4 months of snowfall. The majority of those particulates consisted of oil sands bitumen, some priority pollutants and polyaromatic compounds, and the particulate elements decline in concentration more rapidly with distance from development, than do those dissolved elements. The study by Kelly et al. got lots of attention and resulted in a press conference where David Schindler waved around a fish found in the Athabasca River which was deformed and had tumors. He attributed the deformities in the fish to the oil sands operations in Fort McMurray, and warned of potential health effects for members of the surrounding communities. Largely as a result of the work of Kelly and Schindler, Environment Canada began an intensive monitoring campaign in the area. The results of their studies are now being shared.
  8. CBCQuirks
    Federal scientists uncover evidence that oilsands contaminants travel further than expected http://www.montrealgazette.com/news/national/Federal scientists uncover evidence that oilsands/7542747/story.html

    Wed, Nov 14 2012 07:19:11
  9. This is referring to the work of Jane Kirk et al. of Environment Canada, whose findings confirmed those of Kelly et al., but also found that the loadings extended further than previously reported. Kirk et al. collected snowpack samples from ~90 sites located 0-200 km from the major bitumen upgrading facilities to determine the atmospheric contaminant loadings into the Athabasca River. They found all 13 of the priority pollutants that Kelly et al. looked at, and noted that the loadings were 1.5 to 13 times greater at sites within 50 km of the upgraders, compared to those sites that were further than 50 km away. They also noted that particulate bound methyl mercury (MeHg) increased exponentially with proximity to the upgraders. The presence and concentration of MeHg is troubling as it is a very bioaccumulative substance that is also quite toxic.
  10. ecojustice_ca
    Snow near oilsands contains toxic substances, CBC reports. http://www.cbc.ca/video/watch/News/Canada/Calgary/ID=2304420832 #oilsands Please ReTweet

    Wed, Nov 14 2012 06:21:12
  11. A related study, presented by Derek Muir (Environment Canada), found that concentrations of total PAHs in lake sediments surrounding the oil sands development were 2.5 to 23 times greater than there were pre-1960 background levels. Muir commented that the footprint of deposition is potentially larger than anticipated, and that the rising levels of PAHs in sediments seems to parallel the development of the oil sands industry.
  12. EcoRational
    Hey #Alberta: Lakes & food chain full of PAHs & mercury. Is this to be your legacy? http://bit.ly/QdHHpA #SETAC #abpoli #tarsands #oilsands

    Wed, Nov 14 2012 09:25:48
  13. BCLaraby
    Defunding in 3,2,1: Fed scientists uncover evidence that oilsands contaminants travel further than expected http://www.calgaryherald.com/life/Federal scientists uncover evidence that oilsands contaminants/7542920/story.html #cdnpoli

    Wed, Nov 14 2012 11:32:02
  14. But it is worth noting that the concentrations of the PAHs in the lake sediments (with the exception of the lake closest to the oil sands development) are below guideline limits, in fact, they are similar to concentrations observed around urban areas. These concentrations are are not yet great enough that they are considered toxic to aquatic life.
  15. nlubick
    Still relatively low concentrations of PAHs from oil operations. #TarSands #EnvironmentCanada #setac2012

    Wed, Nov 14 2012 11:52:55
  16. Interestingly, results presented by Joanne Parrott (Environment Canada), found that melted snow (amended with essential salts to mimic the ionic composition of the Athabasca River) from near the oil sands mining and refining areas were toxic to larval fathead minnows from 25 to 100% strength.
  17. nlubick
    “The snow was toxic” to fathead minnow larvae near stacks but clean far away. What happens to melt? #EnvironmentCanada #TarSands #setac2012

    Wed, Nov 14 2012 10:53:51
  18. However, once the snow melt water was diluted with water from the Athabasca River it was no longer toxic to the minnows.
  19. nlubick
    Dilution is the solution? Athabasca River water is “NOT TOXIC” (#EnvironmentCanada emphasis). Meltwater is ok for fish #setac2012 #TarSands

    Wed, Nov 14 2012 10:56:22
  20. These results are being presented at a conference and I am largely gathering information about the work being presented through the SETAC Abstract book and the tweets and updates from colleagues. This is by no means the ideal way of getting information, but it does represent how most people would be exposed to science news, and while it is cool that it is happening, it is still lacking. Reading a full peer reviewed paper gives much more information and a more complete story to help interpret the results. Unfortunately, that format is largely unavailable to the public (both as it is written and physically as a paper), and as such we have to rely on newspaper articles and press releases which are often incomplete and can be misleading. Hopefully once the results presented at the SETAC conference get published, there will be a renewed discussion of their significance and they will help inform the future development of the Canadian oil sands.

Frankenfoodie Friday

A different spin on the usual Foodie Friday post, today I wanted to summarize the fallout of a recent study in the journal of Food and Chemical Toxicology titled Long term toxicity of a Roundup herbicide and a Roundup-tolerant genetically modified maize. The study claims to be the first long-term (two years) study into the health impact of a genetically modified (GM) tolerant maize crop, and the herbicide Roundup in Sprague-Dawley rats. Before I get into the results, just some quick background information of GM maize, Roundup, and Sprague-Dawley rats. GM maize is corn which has been genetically modified to withstand spraying with glyphosate, the active ingredient in Roundup, and is said to be a Roundup Ready crop. The goal of Roundup Ready crops is to allow the crop to be sprayed without being damaged, while surrounding weeds are destroyed. Roundup, or more specifically glyphosate, is one of the most commonly used herbicides in the agricultural and cosmetic-use industries. Sprague-Dawley rats are commonly used organisms in laboratory studies partly because of its calm demeanor and ease of handling. The average life-span of a Sprague-Dawley rat can range between 193-1100 days, during which time up to 57% of females can expect to develop tumors on a normal diet, and up to 80% of those on a fat-rich diet can expect to develop mammary tumors. This strain of rat is particularly prone to developing tumors, particularly when fed an unrestricted diet.

Back to the paper, the authors chose a 2 year duration for the study, as they were interested in the chronic effects of this diet and noted that “no regulatory authority requests mandatory chronic animal feeding studies to be performed for edible GM crops“, and that currently, approval is based on a 90-day feeding trial. They carried out their study on 10 groups, each group containing 10 male and 10 female rats. 3 groups were exposed to Roundup Ready corn (NK603) with three different proportions (11, 22, and 33%) of the corn incorporated into their diet. 3 groups were exposed to Roundup Ready corn which had been sprayed with Roundup in the field, with the same proportions in the diet as with the Roundup Ready corn alone. 3 groups were exposed to Roundup alone via their drinking water at three different concentrations of glyphosate; 50 ng/L (1.1×10-8% Roundup), 400 mg/kg (0.09% Roundup), and 2.25 g/L (0.5% Roundup) [note: the discrepancy between units is from the original paper]. This leaves only 1 control group (10 males and 10 females), which received a diet made up of 33% non-GM corn and plain drinking water. The authors took blood and urine samples and performed histological analysis of the rats’ principal organs at the end of the trial.

The authors found that in all treated groups, there were 2 – 3 times more deaths amongst the females compared to the controls by the end of the experiment. Females developed fatal mammary tumors and pituitary disorders, and males suffered liver damage, developed kidney and skin tumors and problems with their digestive system. The majority of tumors were only detected from 18 months onwards. The largest tumors were five times more frequent in females than in males and 93% were mammary tumors.These results were highlighted by very graphic photos.

Rats, and their paired mammary glands, from the treated groups, noticeably absent is the control group.

The authors conclude that the biochemical disturbances and physiological failures in the rats are the result of Roundup Ready Corn and Roundup alone. The conclusions of this paper got picked up by a lot of media outlets, where it was quickly reported that Major study proves cancer dangers of GM food, or that GM corn linked to early death in new study, or as the Daily Mail put it, Cancer row over GM foods as study says it did THIS to rats…and can cause organ damage and early death in humans.

However, it didn’t take long for other scientists to speak up about the results (the following links do a much better job than I could at describing the failings of the article, so click through for the full story). The Science Media Centre collected the opinions of many scientists regarding the findings and interpretation of the paper. NewScientist does a great job of clearly summing up the problems with the paper, in a very concise and easy to follow manner, with helpful supporting links. SciCurious gives a great technical takedown of the study at The Crux. Forbes contributor Tim Worstall calls the study rubbish, noting that every research animal in the US has been eating GM food for well over a decade, all without a catastrophic collapse of the population. One of the most scathing and insightful reviews (read: takedown) of the paper comes from Michael Grayer, who blows a gasket while describing the many failings and shortcomings of the paper, which are quickly summarized as very small sample size in the control group (10 animals), many different experimental groups, opaque and non-declared statistical methods, emotionally distressing/manipulative photos of rats, and a fairly apparent conflict of interest that goes undeclared by the lead author.

The conflict of interest of the lead author is a bit troubling as the issue of GM crops is very political, and becoming less about science. Forbes has a great article, Monsanto’s GM Corn and Cancer in Rats: Real Scientists Deeply Unimpressed. Politics, Not Science Perhaps? which highlights the political back story and interests behind this paper, its authors, and funding group. The timing of this paper, and the heated discussion surrounding it, coincides with California Proposition 37, Mandatory Labeling of Genetically Engineered Food initiative which will be on the November 6th ballot. Prop 37 would require all genetically engineered foods in California to be labeled. Gary Ruskin, campaign manager of the Yes on Proposition 37 effort, is using the study to “underscore the importance of giving California families the right to know whether our food is genetically engineered and to decide for ourselves whether we want to gamble with our health by eating GMO foods.”  The findings of the study have also found their way into the promotional material for Yes on Prop 37, which will no doubt serve to muddy up the debate.

Aside from getting people talking about GM crops, this paper is also serving a greater purpose. Understanding Uncertainty gives an excellent breakdown of the flawed statistics used in the paper, but it is able to find a silver lining, noting that it provides a fine case study for teaching a statistics class about poor design, analysis and reporting. This paper and the ensuing reaction is another great example of the need for critical reading, and reporting, of scientific articles.

Looks like the paper mentioned above is going to be retracted, which is great news, but I somehow doubt the retraction will get as much press or feature on The Dr. Oz Show, as the original publication did.

Update: June 26th 2014

Looks like the paper mentioned above has been re-published, with very little changes and without peer review, in a different journal. Once again the scientific community is criticizing their results and ethics of the authors. The Genetic Literacy Project has complied an excellent list of reactions to this new development.

Animal ABC’s in ET&C

A is for Animals: The following is a list of animals that have some relation to ecology (E), toxicology (T), or chemistry (C).

B is for Bats (E): White-nose syndrome is wreaking havoc on bat populations across the US and Canada. This emergent disease (caused by the fungus Geomyces destructans) attacks bats during the hibernation season, depositing white fluff on their muzzles and rousing them from their torpor, causing them to burn through fat stores. Recently conservationists created a bat hibernaculum, or artificial bat cave in the hopes of maintaining a healthy population of bats.

C is for the Common Carp (E): This non-native (to North America), fish species is decimating habitat and local fish populations in the Mississippi and Illinois Rivers and the Great Lakes, and creating a political and environmental dilemma.

The workhorse of aquatic toxicology, Daphnia magna

D is for Daphnia (T): Perhaps one of the most commonly used test organisms in biological and toxicological studies, Dapnia is a microcrustacean commonly referred to as a water flea. It is a versatile model organism, with life-history traits that make it amendable to field and laboratory studies, where investigations have included fundamental mechanisms of inheritance and development, cellular function, physiological systems, immunity response, disease, macromolecular structure/function relationships, toxicity assays, and the genetic basis of complex phenotypic traits. Because of its importance, it was the first crustacean to have its genome sequenced.

E is for Echidna (E): Echidnas are one of those weird Australian animals, they are mammals, yet they lay eggs, they are covered in pointy hedgehog-like spines and have a long snout, with the sticky tongue of an anteater. Also the males have a four headed penis.

F is for Fruitfly (T): The fruitfly (specifically Drosophila melanogaster) has been heavily used genetics research and is a common model organism in developmental biology. Below is an amazing video of the development of the fly embryo in real time!

G is for Guam (E): See S for the rest of the ecological cautionary tale, but needless to say I don’t think I will be going to Guam any time soon.

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