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Rob Hale, Professor
Department of Aquatic Health Sciences Virginia Institute of Marine Science
The College of William & Mary [email protected]
1
Birds, bugs & babies (& some fish too)
- Role of plastics & flame retardant additives in chemical contamination issues
Beekeepers concerned about aerial pesticide spraying for mosquitos
The Virginian-Pilot October 7, 2013 A long-standing Air Force Reserve policy says its pilots can't fly mosquito missions after dark for safety reasons. So the reserve's C-130s trundle off the runway at Langley Air Force Base as early as two hours before sunset. Beekeepers protect their honeybees by corking up hives the night before to keep their foragers contained. Wild bees, however, don't get the news. They're caught out in the open as naled - a nerve agent for insects - drifts down in droplets so fine they can only be seen with a microscope.
Science. 1978; 200(4343):785-7. Another flame retardant, tris-(1,3-dichloro-2-propyl)-phosphate, and its expected metabolites are mutagens. Gold MD, Blum A, Ames BN.
Abstract
A flame retardant used in children's sleepwear, tris-(1,3-dichloro-2-propyl)phosphate (Fyrol FR2) is a mutagen in the Salmonella-mammalian tissue homogenate test after it has been activated by mouse or rat liver homogenate. The expected enzymatic hydrolysis product, 1,3-dichloro-2-propanol, is similarly a mutagen after activation by liver homogenate. A proposed metabolite of the flame retardant, 1,3-dichloro-2-propanone, is a potent mutagen. A flame retardant with similar structure, tris-(2,3-dibromopropyl)phosphate (tris-BP), was shown previously to be a mutagen, to cause sterility in animals, to be a carcinogen, and to be absorbed through human skin. Sleepwear treated with tris-BP, Fyrol FR2, and other chemical additives was being sold in late 1977.
TDCPP
Hidden Hazards tested 20 popular new foam baby products for toxic flame retardants
linked to serious health problems, including TDCPP, TCPP, TCEP & Firemaster 550.
The tests showed that 85% of the products tested (17 of 20) contained at least one of
these.
http://www.womensvoices.org/issues/fact-sheets/hidden-hazards-in-the-nursery/
Today
4
2000 Virginia Tributaries Fish Monitoring Project
DEQ collected from VA tribs
VIMS analyzes organics & metals
VDH issues Health Advisories
~20% of VA sites: flame retardant PBDEs >1000 ppb (lipid wt)
Highest PBDE fish level in the world! Polybrominated diphenyl ether flame retardants in Virginia
freshwater fishes (USA). Hale et al. 2001. Environ. Sci. Technol. 35:4585.
Similar structures
209 congeners
5
48 ppm: carp @ mouth of Hyco Creek
linked to upstream (20 km) NC wastewater trt plant
receiving discharges from auto fabrics manufacturer
Flame retardant additives used in plastics Often contain Br or Cl or PO4
Do Temporal and Geographical Patterns of HBCD and PBDE Flame Retardants in U.S. Fish Reflect Evolving Industrial Usage? Da Chen et al. Environ. Sci. Technol., 2011, 45 (19), pp 8254–8261
7
Advice: business man to Dustin Hoffman
The Graduate 1967
“…just want to say one word to you… one word...Plastics”
8
Global plastic production grew 500% over 30 years
Plastics in the Environment
9
Nature | News December 2014
Mystery of the Missing Ocean Plastic
We’re throwing away more & more plastic.
If it’s not ending up in the open Atlantic,
where is it going?
Tsunami debris
…new Science study, reported >5 million
metric tons of plastic waste enters the
oceans from land each year, & may be as
high as 13 million tons.
Feb 13, 2015 by Sci-News.com
Could “missing” ocean plastic be due to our measurement approach?
What is found depends on:
Where we look?
Beaches & water surface
What we look for?
pieces>1 mm
Microplastics in the Marine Environment: A Review of the Methods
Used for Identification and Quantification. Environ. Sci. Technol. 2012,
46, 3060−3075.
http://newsimg.bbc.co.uk/media/images/44518000/gif/_44518180_gyre_midway_203.gif
Effects of Plastics in the Environment
Wildlife Entanglement
Mega-plastic ingestion
https://vimeo.com/25563376
13
Great Barrier Reef corals eat
micro-plastics
February 24, 2015
ARC Centre of Excellence in Coral Reef
Studies
Researchers in Australia have found that
corals commonly found on the Great Barrier
Reef eat micro-plastic pollution.
"Corals are non-selective feeders and our
results show that they can consume
microplastics when the plastics are present in
seawater..”
The plastic was found deep inside the coral
polyp wrapped in digestive tissue, raising
concerns that it might impede the corals
ability to digest its normal food.
Credit: Mia Hoogenboom
14
Many types of plastics Polypropylene (PP) Food containers, appliances, car fenders
(bumpers), plastic pressure pipe systems. Polystyrene (PS)
Packaging foam, food containers, disposable cups, plates, cutlery, CD and cassette boxes.
High impact polystyrene (HIPS) Fridge liners, food packaging, vending cups.
Acrylonitrile butadiene styrene (ABS) Electronic equipment cases (e.g., computer
monitors, printers, keyboards), drainage pipe. Polyethylene terephthalate (PET)
Carbonated drinks bottles, jars, plastic film, microwavable packaging.
Polyester (PES) Fibers, textiles.
Polyamides (PA) (Nylons) Fibers, toothbrush bristles, fishing line, under-
the-hood car engine moldings. Polyvinyl chloride (PVC)
Plumbing pipes and guttering, shower curtains, window frames, flooring.
Polyurethanes (PU) Cushioning foams, thermal insulation foams,
surface coatings, printing rollers. (Currently 6th or 7th most commonly used plastic material, for instance the most commonly used plastic found in cars).
Polycarbonate (PC) Compact discs, eyeglasses, riot shields, security
windows, traffic lights, lenses. Polyvinylidene chloride (PVDC) (Saran)
Food packaging. Polyethylene (PE)
Wide range of inexpensive uses including supermarket bags, plastic bottles.
Polycarbonate/Acrylonitrile Butadiene Styrene (PC/ABS)
A blend of PC and ABS that creates a stronger plastic. Used in car interior and exterior parts, and mobile phone bodies.
High MW polymers
-petroleum-based
-Consists of repeating “monomer” units
-Residual monomers?
-Additives to modify properties
-F (plastic composition & purpose)
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Plastics - injection molding
Additives - 1000s
Flame retardants (FRs)
~10% by weight
Antimicrobials Antioxidants Antistatic Agents Blowing Agents External Lubricants Fillers/Extenders Fragrances Heat Stabilisers Impact Modifiers Internal Lubricants Light Stabilisers Pigments Plasticisers Process Aids Reinforcements
nurdles
16
Flame Retardant (FR) Life Cycle
FRs released during: FR manufacture?
Polymer incorporation? FRs added at % levels
Additive composition complex & uncertain
During polymer product useful life? Indoor dust studies
Following product disposal, destruction? Accelerated during polymer weathering
Recycling of products?
17
Plastics eventually weather into microplastics
Vulnerability varies by plastic type
• Photolysis
• Chemical/microbial attack
• Abrasion
• Burning
Surface area increases
• Leaching, degradation, sorption
Science News
Plastics (polystyrene) In Oceans Decompose, Release Hazardous Chemicals, Surprising New Study Says
Aug. 20, 2009
Hard Plastics Decompose in Oceans, Releasing Endocrine Disruptor BPA
Mar. 24, 2010
Polyurethane foam
E-waste
Fibers
Aqueous leaching of additives from polymers
Additives & plastic types diverse Surface area f(particle size)
Weathering: alter chemical composition, particle size
Leaching fluids diverse Surface & ground waters
Landfill leachates
Saliva, digestive fluids
Water properties pH, temp, salinity,
organic content…
18
Current project: NOAA Marine Debris Program “Influence of a suite of environmentally relevant conditions on PBT
leaching from, and sorption to, marine microplastic debris”
19
1) Leaching of PBT additives and compositional monomers from four
polymer classes (PUF, PE, EPS, PVC) by waters with selected
environmentally relevant characteristics (i.e. T, salinity, DOC). The
impact of polymer particle size (10, 100, 1000 µm) and pre-weathering will
also be assessed;
2) Sorption from water of two PBT mixtures to model polymers (PE &
PVC). The influence of particle size and biofouling on sorption will also
be studied.
incubator
Microplastics + sand
Water
reservoir Water eluent for
analysis, tox
experiments…
20
Hydrophobics sorb to plastics - increase organismal exposure via
ingestion of such plastics?
Teuton et al. 2007. Potential for Plastics to Transport Hydrophobic Contaminants. Environ. Sci. Technol. 41: 7759–7764
Luellen & Shea. 2003. Semipermeable membrane devices accumulate conserved ratios of sterane and hopane petroleum biomarkers. Chemosphere 53: 705-713
Brown et al. 2008. Ingested Microscopic Plastic Translocates to the Circulatory System of the Mussel, Mytilus edulis (L.). Environ. Sci. Technol., 2008, 42 (13), pp 5026–5031
21
Human indoor exposure
Plastic-related chemicals accumulate in house dust Hand to mouth ingestion
Inhalation
Dermal contact
Umbilical cord transfer
Breast milk
PBDEs in sludge
22
Indoor dust: BFRs from plastic fragments?
Webster et al. 2009. Identifying Transfer Mechanisms and Sources of Decabromodiphenyl Ether (BDE 209) in Indoor Environments Using Environmental Forensic Microscopy. Environ. Sci. Technol 43:3067–3072
Chemical imaging: Raman microscopy
23
Polybrominated diphenyl ethers in peregrine falcon (Falco peregrinus) eggs
from the Northeastern U.S. Chen et al. 2008. Environ. Sci. Technol. 42:7594-
7600.
Polybrominated diphenyl ether flame retardants in Chesapeake Bay region
peregrine falcon eggs: urban/rural trends. Potter et al. 2009. Environ.
Toxicol. Chem. 28:973-981.
?
Substantial BDE153 & BDE209
“Nonbioavailable” BDE209 available to terrestrial raptors
PBB from the mid-1970s
Sewage sludge “biosolids”
~7 million dry tons of wastewater treatment sludge generated annually
50% land applied
NO regulation or measurement of organic pollutants – “we banned all the bad ones in the 1970s”
24
Figure 4. PBDE congener contributions in 2004–2007 Chicago-derived biosolids versus their predicted distribution based on 2001 North American PBDE demand and published commercial mixture compositions.(19) BDE-209 (right inset) is shown separately due to its large contribution.
Polybrominated Diphenyl Ethers in U.S. Sewage Sludges and Biosolids: Temporal and Geographical Trends and Uptake by Corn Following Land Application. Hale et al. 2012. Environ. Sci. Technol., 46 (4), 2055–2063
25
Exploratory research PBDEs in sludge-exposed soil invertebrates? Hypotheses
Soils receiving historical sludge amendments will be enriched relative to reference (clean) site
Soils & earthworm PBDE burdens will be uniform
PBDEs in sludge-amended soils will be accumulated according to ecological relationships
?
Trophic Relationships—Manure- vs. Sludge-applied site C & N isotope patterns
Manure Sludge
C4
C3
Diet
Tro
ph
ic l
eve
l
You are what you eat!
PCA Results—% of Total ΣPenta-BDEs
millipedes
DE-71 BDE47
BDE100
BDE99
BDE154
BDE153
-3
-1
1
3
-5 -3 -1 1 3 5 7
PC 2
(31.3
8 %
)
PC 1 (57.38 %)
Earthworms
Ground beetles
June beetle larvae
Firefly Larvae
Woodlice
Soil Crickets
June beetle adults
Weathered sludge
Big Picture… -Exposure pattern varies by species -Soil contact controlling Worms highest levels Spiders & grasshoppers low PBDEs -Worm/predatory ground beetle overlap -June beetle adults distinct from larvae. Adults offsite transfer? = 590-740 ug per individual
soil
Wang et al. 2010. Residues of Polybrominated Diphenyl Ethers in Honeys from Different Geographic Regions. J. Agric. Food Chem. 58, 3495-3501.
50 honey samples
Average profiles of 27 PBDE congeners (pg/g ww) in
the honey samples labeled from developed countries.
av concns ± std dev and concn ranges (pg/g ww)
developed countries
(n = 21)
developing
countries (n = 15)
background
regions (n = 14)
PBDE
congeners mean range mean range mean range
BDE-209 1170 ±
860 180−3360
3390 ±
2820 550−9260
450 ±
320 nd−1170
PBDE 4 2620 ±
1870 630−7520
810 ±
4802 230−1920
360 ±
140 100−600
PBDE26 5950 ±
2820 2720−10550
1870 ±
670 1030−3470
640 ±
170 300−850
B Sum concentrations of BDE-47, -49, -138 and -153.
C Sum concentrations of the 26 PBDEs except BDE-209.
Customer Matt Westfall says Rigid Insulation is his secret weapon when building
beehives. He puts a sheet of insulation in the top cover of the hive and that, he
says, helps keep the hive warm enough to survive a cold winter. Matt, we
appreciate your business and your insights!
HBCD flame retardant used in expanded polystyrene 0.5-1.5% by wt
Countdown begins for HBCD phase-out Global Business Briefing, January 2015 The amendment for listing HBCD as a prohibited substance under the Stockholm Convention on Persistent Organic Pollutants (POPs) entered into force on 26 November. HBCD is manufactured in Europe, the US and Asia. The US has not signed up to the treaty…there is a 5-year exemption for in expanded or extruded polystyrene (EPS/XPS) foam in building insulation
Recycling
Series 850 - Ecological Effects Test Guidelines http://www.epa.gov/ocspp/pubs/frs/publications/Test_Guidelines/series850.htm The FINAL guidelines on this page are part of a series of test guidelines that have been developed by the Office of Chemical Safety and Pollution Prevention (OCSPP) for use in the testing of pesticides and toxic substances, and the development of test data for submission to the Agency.Group C – Terrestrial Beneficial Insects, Invertebrates, and Soil and Wastewater Microorganisms 850.3020 - Honey Bee Acute Contact Toxicity Test (June 2012) 850.3030 - Honey Bee Toxicity of Residues on Foliage (June 2012) 850.3040 - Field Testing for Pollinators (June 2012)
Tox tests related the bees
Questions?
more