Rob Hale, Professor

Department of Aquatic Health Sciences Virginia Institute of Marine Science

The College of William & Mary hale@vims.edu

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.

11

Dominated by small particles

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)

15

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