SUPPLEMENTARY MATERIALS
Part 1: the Map, list of PAH analyzed and results of Fl/(Fl+Py)
Figure S1: Google map of the sampling site (the Lake in Central Park, Manhattan Island, NYC)
Table S1 Identified and quantified PAH compounds used in this study, their abbreviations, and
nominal molecular masses. The compounds denoted with * are EPA PAHs, the sum of all 16 EPA
PAHs are calculated as PAH. TPAH is the sum of all the PAH compounds shown in this table.
Compounds
mass
Compounds
*Naphthalene
Biphenyl
*Acenaphthylene
Abbrev
.
Na
Bph
Acy
128
154
152
*Acenaphthene
Dibenzofuran
*Fluorene
Ace
DBFu
F
154
168
166
Dibenzo(b,d)thiophene
*Phenanthrene
*Anthracene
4H-cyclopenda
[def]phenanthrene
2-Phenylnaphthalene
*Fluoranthene
DBT
Pa
A
4HCP
184
178
178
190
Benzo[ghi]fluoranthene
Benzo[c]phenanthrene
Tetramethyloctahydrochrysenes
*Benzo[a]anthracene
*Chrysene+Triphenylene
Trimethyltetrahydrochrysenes
*Benzo[b]fluoranthene
*Benzo[k]fluoranthene
Benzo[a]fluoranthene
Benzo[e]pyrene
2PN
Fl
204
202
*Benzo[a]pyrene
Perylene
Abbrev.
mass
BghiF
BcP
C48HChy
226
228
292
BaA
Chy
C34HChy
228
228
274
BbF
BkF
BaF
BeP
252
252
252
252
BaP
Per
252
252
*Pyrene
Benzonaphthofurans
Retene
1,2-Benzofluorene
2,3-Benzofluorene
Benzo(b)naphthothiophenes
Alkylated series
C1-C4 Naphthalene
Py
202
BNFu
Ret
12BF
23BF
BNTH
218
234
216
216
234
C1-C4
Na
C1-C3
C1-C3
Phenanthrene/Anthracene
P/A
C1-C2 Fluoranthene/Pyrene C1-C2
F/P
C1-C2 Benzo[a]anthracene/ C1-C2
Chrysene
B/C
Indeno[7,1,2,3-cdef]
Chrysene +
Dibenzo(aj)anthracene
*Indeno[1,2,3-cd]pyrene
Picene
*Dibenzo[ah]anthracene
*Benzo[ghi]perylene
Anthrarene
IC+DjA 276+278
142,156, C1-C2
170,184 Dibenzo(b,d)thiophene
192,206, C1 PAHs with mass 252
220
216,230
C1-C2 198,212
DBT
C1 m252
266
IP
Pi
DA
Bghi
AA
276
278
278
276
276
242,256
Source analysis results by Fl/(Fl+Py)
The flow chat (Figure S2) illustrates the procedure used to calculate PAH sources from combustion of
softwood, petroleum, and coal using diagnostic ratios. Ret/(Ret+Chy) was used first to compute the
contribution of softwood combustion given the coal and petroleum combustion have the same
Ret/(Ret+Chy) ratios, then 1,7/( 1,7+2,6-DMP) and Fl/(Fl+Py) was used, separately, to obtain an
independent estimate of coal and petroleum combustion. The results of Fl/(Fl+Py) (Figure S3) are
quite consistent with the results by 1,7/(1,7+2,6) with coal dominance prior to 1920, and a gradual
decrease from about 1920 to the 1960s. Petroleum combustion has dominated since then. The similar
results of Fl/(Fl+Py) and 1,7/(1,7+2,6) partitioning demonstrate the soundness of this method.
Figure S2: Flow chat showing the procedure using diagnostic ratios to calculate PAH sources from
combustion of softwood, petroleum, and coal (need a flow chat to replace the
Figure S3: The source apportionment results by Ret/(Ret+Chy) and Fl/(Fl+Py)
Part 2: Limited effects of municipal solid waste incineration on PAH fluxes.
Our previous studies have suggested that municipal solid waste incineration can substantially affect
fluxes of heavy metals, saturated hydrocarbons, and black carbon in the period from 1930 to 1970
(Chillrud et al., 1999; Louchouarn et al., 2007; Walsh et al., 2001). However, PAH flux appears not to
be largely affected by MSW incineration evidenced as the absence of two peaks around 1940 and
1960. Jay et al. (1995) found that MSW incineration produces a large amount of saturated
hydrocarbons but insignificant high molecular PAHs (Jay & Stieglitz, 1995). If we assume that the
ratio of total saturated hydrocarbons (SHs) to pyrene (Py), which is around 12, 000 in the MSW
emission, is their ratio in sediments and all SHs in sediments are from MSW incineration, Py from this
source in the section 26-28 cm (~1943 ) was about 5% of the total Py. But as we know in 1940s,
petroleum combustion, which also produces large amount of SHs, is also an important SH sources.
This suggests that SHs from MSW should be less than this assumption, and accordingly Py from
incineration would be less than 5%.
The calculation method used above is only a rough evaluation and should not be regarded as a
quantitative estimate because the ratios of SHs/Py from MSW incineration can be vary with
incineration temperature and the type of waste combusted..
Part 3: Historical data on Combustion-Related Energy Consumption in New York
State; 1850 to 2005
By Monica C. Blount, Melody L. Berds, Dana Esposito and Richard F. Bopp
Rensselaer Polytechnic Institute
Data available from the US Department of Energy and the analysis of Gschwandtner et al. (1985) for
the USEPA were used to construct Figures S4 through S8, quantitative estimates of the major fuel
types used in combustion in the State of New York between 1850 and 2005. Although natural gas
combustion is an insignificant source of PAH emissions compared to wood, coal, and petroleum, it was
included (Figure S7) to complete the representation of combustion-related energy consumption.
Yearly data from 1960 through 2005 were taken from the USDOE website (http://www.eia.doe.gov/emeu/states/state.html?q_state_a=ny&q_state=NEW%20YORK
The data from Gschwandtner et al. (1985) were state by state estimates reported for every fifth year
from 1900 to 1980 plus 1978 providing some overlap between the two datasets which, as expected,
were in excellent agreement. Unfortunately, in the document we obtained from NTIS, the page
containing NY state fuel consumption from 1900-1945 appeared twice while the page for 1950-1980
was omitted. We contacted the NTIS librarian, and the 1950-1980 NYS energy consumption data was
apparently not in any of their file copies of the report. We tried contacting the authors, but were not
able to retrieve the missing data. Consequently, we “reconstructed” the energy consumption data for
NYS from 1950-1980 using the estimates of historic NYS emissions of sulfur and nitrogen oxides and
fuel-specific emissions factors, both of which were taken from the same report.
Data from 1850 to 1900 were based on “every fifth year” estimates of Total US wood and coal
consumption reported on the USDOE website. For wood, the Total US estimates were multiplied by
0.0386 the ratio employed in Gschwandtner et al. (1985) for estimating NYS wood consumption from
1905 through 1945. For coal, the Total US estimates were multiplied by 0.048, based on the ratios
calculated from the data in Gschwandtner et al. (1985) that ranged from about 0.043 to 0.054 between
1900 and 1945.
Questions concerning additional details of our data manipulations and compilation can be addressed to
Richard Bopp (boppr@rpi.edu).
Figure S4. The history of wood consumption in NYS. The two categories, both quite significant, are
industrial and residential.
Figure S5. The history of coal (anthracite + bituminous + coke) consumption in NYS. Throughout
most of the period, use was dominated by anthracite and bituminous. Coke comprised about 3% of
total coal use around 1900, increasing to about 15% by the 1940s. Since the 1940s, as total coal use
declined, the contribution from coke has averaged about 25%.
Figure S6. The history of petroleum consumption in NYS. In addition to Gasoline, as shown on the
plot, Total Petroleum combustion includes significant contributions from other distillates (fuel oil and
kerosene, e.g.) and residual (bunker type) oil.
Figure S7. The history of natural gas consumption in NYS. Based on PAH emission factors from the
USEPA website, natural gas combustion is not a significant source of PAHs.
Figure S8. The history of consumption of the major fuels in NYS that have contributed significantly
to emissions of PAHs to the atmosphere.
REFERENCES
Chillrud, S.N., Bopp, R.F., Simpson, H.J., Ross, J.M., Shuster, E.L., Chaky, D.A., Walsh, D.C., Choy,
C.C., Tolley, L.R., Yarme, A., (1999) Twentieth Century Atmospheric Metal Fluxes into
Central Park Lake, New York City. Environmental Science & Technology, 33(5), 657-662.
Gschwandtner, G., Gschwandtner, K., Eldridge, (1985) HISTORIC EMISSIONS OF SULFUR AND
NITROGEN-OXIDES IN THE UNITED-STATES FROM 1900 TO 1980. Volume II. Data.
NTIS PB85-191203; EPA-600/7-85-009B, April 1985.
Jay, K., Stieglitz, L., (1995) Identification and quantification of volatile organic components in
emissions of waste incineration plants. Chemosphere, 30(7), 1249-1260.
Louchouarn, P., Chillrud, S.N., Houel, S., Yan, B.Z., Chaky, D., Rumpel, C., Largeau, C., Bardoux,
G., Walsh, D., Bopp, R.F., (2007) Elemental and molecular evidence of soot- and char-derived
black carbon inputs to New York City's atmosphere during the 20th century. Environmental
Science & Technology, 41(1), 82-87.
Walsh, D.C., Chillrud, S.N., Simpson, H.J., Bopp, R.F., (2001) Refuse incinerator particulate emissons
and combustion residues for New York City during 20th century. Environmental Science &
Technology, 35, 2441-2447.