Youre standing on it!

Coal-tar-based pavement sealcoat:

Environmental and human-health overview

May 30, 2015

for
USGS New York Water Science Center
1
NAWQA: Contaminant
Trends in Lake Sediment
http://tx.usgs.gov/coring/index.html

Upward trend
No trend
Downward trend

2
Van Metre et al., 2005, Env. Sci. Technol.
The first clue: City of Austin measures
high PAH in stream sediment

PAHs >1,500
mg/kg in some
small drainages
in residential
areas
4
Polycyclic aromatic hydrocarbons (PAHs) are
ubiquitous in the urban environment

5
 PAHs in urban sources
All concentrations in mg/kg (means of as many as 6 studies)

Fresh asphalt 1.5 Pavement Sealcoat

Weathered asphalt 3
Fresh motor oil 4 Asphalt Based
Brake particles 16 ~ 50
Road dust 24
Tire particles 86 Coal-tar-based
Diesel engine 102
Gasoline engine 370
~70,000
Used motor oil 440

6
 Used
motor oil

Coal-tar
sealcoat

=
 Coal-tar-based sealcoat use
85 million gallons per
year in US (per
industry1)
170 mi2, or 110,000
acres covered in US

1Hogue, C. Chem. Eng. News, 2007

Contaminants in sealcoat are mobile

9
Sealed pavement dust
Total PAH (mg/kg)
5.2
<13 570 1,300
3,400
3,200
2.1 3,200
Unsealed pavement dust
3,000 8.5
<8.6 24
Asphalt Coal tar 47 30
21
0.83

54

10
Van Metre et al., 2009, Env. Sci. Technol.
Sealcoat PAH transport pathways

11
Mahler et al., 2012, Env. Sci. Technol.
 Lake Anne
2,095 people/km
SPAH 17.0 mg/kg

Decker Lake
2,090 people/km
Environmental Forensics: PAH fingerprints
0.25 Coal

Lake Anne
0.2

0.15
r=0.60
Fraction

0.1 0.25

CT dust
0.05
0.2
Lake Anne
0
0.15
12 PAHs
r=0.94
Chry
Anth

Fraction
BgP
BaA

BbF

BeP
BaP
BkF
Phe

Pyr
Flu

IP

0.25 0.1
Gas vehicle
3 ring 4 ring 5-6 ring
Lake Anne
0.2 0.05

0.15
r=0.68
Fraction

Chry
Anth
12 PAHs

BgP
BaA

BbF

BeP
BaP
BkF
Phe

Pyr
0.1

Flu

IP
0.05

0
12 PAHs 13
Chry
Anth

BgP
BaA

BbF

BeP
BaP
BkF
Phe

Pyr
Flu

IP
PAH sources to U.S. urban lakes

Probable Effect
Concentration

Van Metre and Mahler, 2010, Sci. Total Environ. 14

PAH trends in new urban lakes
16
 PAH concentrations in Lady Bird Lake:
Before and after the ban
12
2006 ban on
coal-tar-based
SPAH16 (milligrams per kilogram)

sealcoat in
10
Austin, Tex.

TWN.1
LBL.4
6
LBL.1
LBL.2
Surficial bottom sediment
4 Series6

2
58%
decrease
0
1950 1960 1970 1980 1990 2000 2010 2020
Estimated date of sediment deposition

Van Metre and Mahler, 2014, Environ. Sci. Technol. 17

 Effects on aquatic biota

Bommarito et al., 2010, Ecotoxicology

Bommarito et al., 2010, Chemosphere
Bryer et al., 2010, Environ. Poll.
Bryer et al., 2006, Ecotoxicology
Scoggins et al., 2007, J. NABS

18
Fish kill, 17 July 2010
Hodges Creek, North Carolina

https://www.youtube.com/watch?v=G5_QJIBYg5c
 Sealcoat application to test plot
Acute toxicity
Pimephales promelas
(fathead minnow)
Ceriodaphnia dubia
(water flea)

Effects on DNA
DNA damage
Repair capacity impairment

20
 PAH and azaarene concentrations in runoff
Mostly acridine and carbazole
1,000

800

PAH 600
2+3 ring PAH
concentration
(mg/L) 400 4+5+6
ring PAH
Azaarenes

200

0
0 1 10 100 1000
Days after application

21
Mahler et al., Env. Poll., 2014
Exposure protocol: Columbia
Environmental Research Center
Four replicates per treatment
(100% and 10% runoff)
10 individuals per replicate
48-h exposure
Ceriodaphnia dubia
Record mortality every 12 hours
Remove surviving organisms to
control water for 48-h recovery
Expose 2 of the 4 replicates to 4 h
UVR
UVB: 7.5 W/cm2
UVA: 454 W/cm2
Record survival every 12 hours for 48
Pimephales promelas
hours
22
Some PAHs are phototoxic
Photomodified
chemical

energy transfer to
EXCITED STATE PAH
oxygen

Radical oxygen
species (ROS)

GROUND STATE PAH

23
Mortality, Ceriodaphnia
Runoff from unsealed asphalt
pavement
100

80

60
Mortality,
in percent
40

20

0
No UV UV
 Mortality, Ceriodaphnia
Runoff from coal-tar-based
sealcoated pavement

48-hour exposure to runoff 48-hr recovery, 4-hr UV exposure

100 100
100%
Mortality, in percent

mortality
80 80
Sample
strength
60 60
100%
10%
40 40

20 20
toxic
threshold
0 0
0.2 1 2 3 7 36 64 111 0.2 1 2 3 7 36 64 111
Sample collection time, in days after Sample collection time, in days after
sealcoat application sealcoat application
25
Mortality, Pimephales promelas
Runoff from unsealed
asphalt pavement

100

80

60
Mortality,
in percent
40

20

0
No UV UV
 Mortality, Pimpephales promelas
Runoff from coal-tar-based sealcoated
pavement

48-hour exposure to runoff 48-hour recovery, w/4-hr UV exposure

Mortality, in percent

100 100

80 80
Sample
strength
60 60
100%
10%
40 40

20 20

0 0
0.2 1 2 3 7 36 64 111 0.2 1 2 3 7 36 64 111
Sample collection time, in days after Sample collection time, in days after
sealcoat application sealcoat application

27
Mahler et al., 2015, Environ. Sci. Technol.
 Effects on cell DNA
Collaboration with ENTPE, Lyon, France
Used RTL-W1 fish liver cell line
Investigated two endpoints
DNA damage: strand breaks and alkylated bases
DNA repair capacity
Determined by comet assay

No strand
breaks, DNA
- + Smaller broken DNA
pieces move more
moves as one rapidly: comet tail
piece

28
 DNA damage measured by the Fpg-
modified comet assay Types of DNA
damage tested

10% runoff
More
damage

1% runoff

Less * = significantly
damage different from
control
Control 5h 26 h 7d 36 d

Sample collection time Kienzler et al., 2015, Sci Total 29

Environ.
 Base excision repair capacity

10% runoff
More
repair

Less * = significantly
repair Control 26 h 36 d different from
control
Sample collection time
30
Photos from Jupiter Images and Corbis Images, Inc.
23 ground-floor apartments
Austin, Tex.: 23 ground-floor apartments
sampled
Median SPAH16 [mg/g]
n=12 n=11

5.1 129

9.0 4,760

Mahler et al. , 2010, Env. Sci. & Technol.

Sealcoat and pre-school ingestion of PAHs
Baby aspirin =0.081 g

B2-PAH dose 250

(ng B2-PAH/kg
body CT
sealcoat
weight/day) 200

150
Photo courtesy of CLEARCorps Durham, NC

100

50 CT
sealcoat no
no sealcoat
sealcoat
0
Dietary Non-dietary ingestion, Non-dietary ingestion,
ingestion low house-dust high house-dust
ingestion (0.027 g/d) ingestion (0.101 g/d)

35
Williams et al., 2012, Environ. Poll.
 Coal-tar sealcoat contributes to a 38-fold
increase in excess lifetime cancer risk
(central tendency)
1.20E-04
1:10,000
1.00E-04

8.00E-05
Excess Lifetime
Cancer Risk soil
associated with non- 6.00E-05
dietary ingestion of house dust
house dust and soil
4.00E-05

2.00E-05

0.00E+00
Urban background CT sealed

Williams et al., 2012, Env. Sci. Technol. 36

What are effects on
air quality?
37
 Measuring volatilization
We used paired high volume air samplers to measure PAH
volatilization from sealcoated pavement

Ambient air
1.25 m

Gradient used to
estimate flux

0.03 m Surface air layer

38
Fluxes (releases) from in-use CT-sealed lots

Flux = 1.4 mg/m2 h Flux = 88 mg/m2 h

Unsealed Coal-tar
asphalt sealed

39
Van Metre et al., 2012, Chemosphere
 Air trends after application
Flux 50000
50,000 45000 day-night
40000
SPAH8 flux (ug/m2 h)

40,000 regression R2=0.95

35000
measured flux
SPAH8 (ug/m2 h)
30,000
30000
20,000 25000
10,000 20000
15000
0
0 100 200 10000
300 400 SPAH ~2.5 g/m2
time (days) 5000
0
0 5 10 15 20
time (days)
Van Metre et al., Chemosphere, 2012

40
Van Metre et al., 2012, Atm. Environ.
Total PAH emissions during drying
Annual coal-tar sealcoat use 374 million L
Area covered ~440 km2
Total PAH emitted during drying 2.5 g/m2
SPAH8 emissions/yr ~1,000 Mg
SPAH16 vehicle emissions, 2010 840 Mg*

* Shen et al., 2011 41

Sealcoat PAH transport pathways

42
Mahler et al., 2012, Env. Sci. Technol.
 Summary of concentrations
CT affected / non-CT affected
Sealcoat products 66,000 / 50 [mg/kg]
Pavement dust 2,548 / 7 [mg/kg]
Runoff particles 3500 / 54 [mg/kg]
Runoff, unfiltered water 61.5 / 3.5 [mg/L]
BMP sediment 646 / 2 [mg/kg]
Lake sediment 33 / 0.4 [mg/kg]
Particles on tires 1,380 / 3 [mg/kg]
Soil 105 / 2 [mg/kg]
House dust 129 / 5 [mg/kg]
Air (1.28 m, 1.6 hr) 5,680 / 26 [ng/m3]
43
Summarized and averaged from Mahler et al., ES&T, 2012
PAHs and Coal-Tar-Based Pavement Sealant
http://tx.usgs.gov/sealcoat.html

Barbara Mahler, bjmahler@usgs.gov

(512) 927-3566
Peter Van Metre, pcvanmet@usgs.gov
(512) 927-3506
References cited in this presentation
Van Metre, P.C., Mahler, B.J., Wilson, J.T. 2009. PAHs underfoot:
Contaminated dust from coal-tar sealcoated pavement is
widespread in the United States. Env. Sci. Technol., 43:20-25.
Mahler, B.J., Van Metre, P.C., Crane, J.L., Watts, A.W., Scoggins, M.,
Williams, E.S. 2012. Coal-tar-based pavement sealcoat and PAHs:
Implications for the environment, human health, and stormwater
management. Env. Sci. Technol., 56:3039-3045.
Van Metre, P.C., Mahler, B.J. 2010. Contribution of PAHs from coal-
tar pavement sealcoat and other sources to 40 U.S. lakes. Sci. Total
Environ. 409:334-344.
Mahler, B.J., Van Metre, P.C., and Foreman, W.T. 2014.
Concentrations of polycyclic aromatic hydrocarbons (PAHs) and
azaarenes in runoff from coal-tar- and asphalt-sealcoated
pavement. Environ. Pollut. 188:81-87.

45
References, cont.
Mahler, B. J.; Ingersoll, C. G.; Van Metre, P. C.; Kunz, J. L.;
Little, E. E., Acute toxicity of runoff from sealcoated
pavement to Ceriodaphnia dubia and Pimephales
promelas. Environ. Sci. Technol. 2015.
Kienzler, A.; Mahler, B. J.; Van Metre, P. C.; Schweigert,
N.; Devaux, A.; Bony, S., Exposure to runoff from coal-
tar-sealed pavement induces genotoxicity and
impairment of DNA repair capacity in the RTL-W1 fish
liver cell line. Sci. Total Environ. 2015, 520, (1), 73-80

46
References cont.
Bommarito, T., Sparling, D.W., Halbrook, R.S. 2010. Toxicity of coal-
tar pavement sealants and ultraviolet radiation to Ambystoma
maculatum. Ecotoxicol. 19: 1147-1156.
Bommarito, T., Sparling, D.W., Halbrook, R.S. 2010. Toxicity of
coaltar and asphalt sealants to eastern newts, Notophthalmus
viridescens. Chemosphere 81: 187-193.
Bryer, P.J., Scoggins, M., McClintock, N.L. 2010. Coal-tar based
pavement sealant toxicity to freshwater macroinvertebrates.
Environ. Poll. 158: 1932-1937.
Bryer, P.J., Elliott, J.N., Willingham, E.J. 2006. The effects of coal tar
based pavement sealer on amphibian development and
metamorphosis. Ecotoxicol. 15: 241-247.
Scoggins, M., McClintock, N., Gosselink, L., Bryer, P. 2007.
Occurrence of polycyclic aromatic hydrocarbons below coal-tar-
sealed parking lots and effects on stream benthic
macroinvertebrate communities. J. NABS 26: 694-707.
47
References cont.
Mahler, B.J., Van Metre, P.C., Wilson, J.T., Musgrove, M., Burbank,
T.L., Ennis, T.E., Bashara, T.J. 2010. Coal-tar-based parking lot
sealcoat: An unrecognized source of PAH to settled house dust.
Environ. Sci. Technol. 44: 894-900.
Williams, E.S., Mahler, B.J., Van Metre, P.C. 2012. Coal-tar pavement
sealants may significantly increase children's PAH exposures.
Environ. Poll. 164: 40-41.
Williams, E.S., Mahler, B.J., Van Metre, P.C. 2012. Cancer risk from
incidental ingestion exposures to PAHs associated with coal-tar-
sealed pavement. Environ. Sci. Technol. 47:1101-1109.
Van Metre, P.C., Majewski, M.S., Mahler, B.J., Foreman, W.T., Braun,
C.L., Wilson, J.T., Burbank, T. 2012. PAH volatilization following
application of coal-tar-based pavement sealant. Atmosphere.
Environ. 51: 108-115.

48
References cont.
Shen, H., Tao, S., Wang, R., et al. 2011. Global time trends in PAH
emissions from motor vehicles. Atmos. Environ. 45: 2067-2073.
Van Metre, P.C., Majewski, M.S., Mahler, B.J., Foreman, W.T., Braun,
C.L., Wilson, J.T., Burbank, T., 2012. Volatilization of polycyclic
aromatic hydrocarbons from coal-tar-sealed pavement.
Chemosphere 88: 1-7.
Van Metre, P.C., Majewski, M.S., Mahler, B.J., Foreman, W.T., Braun,
C.L., Wilson, J.T., Burbank, T., 2012. PAH volatilization following
application of coal-tar-based pavement sealant. Atmospheric
Environment 51: 108-115.
Van Metre, P.C., and Mahler, B.J., 2014. PAH concentrations in lake
sediment decline following ban on coal-tar-based pavement
sealants in Austin, Texas. Environ. Sci. Technol. 2014, 48, 7222-
7228.

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