PAH
Concentrations in surface sediments, Gateway National
Recreation Area, New York, NY.,
Jamaica Bay and Sandy Hook.
Study
#:GATE-00174
-----------------------------
Permit
#:GATE-2007-SCI-0002
Principal
Investigator: Kevin Olsen
Anthropogenic
PAH distribution in the sediments found within
Gateway NPS as Determined by Thermal Extraction GC/MS
Mar
14, 2007 to Dec 31, 2008
Contact
Information:
Instrumentation
Specialist
Chemistry and Biochemistry
Support Staff
Room
359 Richardson Hall
Montclair
State University
Normal
Ave
Montclair,
NJ, 07043
973-655-4076
Subaqueous
sediment grab samples from Jamaica Bay, Staten Island and Sandy Hook
were
taken by Dr. Mark Ringenary, Natural Resources Specialist - National
Park
Service and analyzed by GC/MS at Montclair State University. The analysis was performed by Kevin
Olsen, Instrumentation Specialist-College of Science and Mathematics,
under the
guidance of Dr. Michael Kruge, professor of geochemistry, and with the
assistance of chemistry undergraduate Nicole Bujalski.
The purpose of this study has been to
map concentrations of anthropogenic polyaromatic hydrocarbons (PAH) in
the bay,
identify areas of enrichment where remedial action might be needed, and
discern
trends in PAH distribution. As the
samples are restricted to the top of sediments the results only reflect
the
most recent deposition.
The
sampling points were based on the existing water quality
monitoring sample points. After
collection the sediments were oven dried at 40c in the Gateway National
Park
laboratory. The dried sediments
were shipped to Montclair State for analysis. A
semi-qualitative version of EPA thermal extraction method
8275a was employed. Milligram
quantities of dried sediments were spiked with 5 uL of a solution
containing
deuterated naphthalene, deuterated anthracene and deuterated pyrene. The spiked sediments were then heated
under an inert atmosphere to 610c which removes organic molecules from
sediment
particles. These are swept onto
the GC column. The GC column was a
Restek 60 meter, Dimethylpolysiloxane stationary phase, 0.25 mm ID
(Restek
catalog number 13326.) The GC
temperature program began at 50c for 5 minutes and rose at a rate of 5c
per
minute until reaching 300c and holding for 25 minutes.
Gas pressure at the column head was 33
psi with a split ratio of 1 to 25.
Two mass spectrometer methods were used for the analysis, a full
scan
method for ions from m/z = 50 amu to m/z = 550 amu and a selected ion
monitoring (SIM) method.
Both
of the mass spectrometer methods had their strengths and
weaknesses. The full scan method
allows the study of numerous biomarker molecules, petroleum products,
and
sewage decomposition products. But
the full scan method was not particularly sensitive to PAH molecules,
especially those with five rings.
Many of the sediments were so rich in organic matter that low
concentration PAH peaks were often indistinguishable from the
background. The SIM method proved to be
far more
reliable in detecting PAH contaminants but did not provide data on any
other
type of compounds. All data that
is presented in this report will be identified by the type of method
used.
Only
samples for which the GC/MS data has been checked and
verified are presented in this preliminary report.
In
general, sediment quality in the New York Harbor region is
improving. However this trend
applies only to the most recently deposited material.
Deeper, and therefore older, sediments still show elevated
levels of contamination. The
results in this report would not be applicable to dredged materials or
disturbed areas.
Across
all of the sample points on Jamaica Bay, the PAH
concentrations were mostly in the low parts per million range. The highest concentrations of PAH
molecules were found in the northern and eastern portions of the bay. The lowest total PAH concentrations
were found in the area around the Rockaway Inlet. The
area nearest to Sheepshead Bay had slightly elevated concentrations
relative to the areas on the north shore of the Rockaway Peninsula from
Breezy
Point to Jacob Riis Park.
NOAA
has published sediment quality guidelines. These
guidelines list two values,
Effects Range Low (ERL) and Effects Range Median (ERM).
The ERL value is an estimate of
concentrations below which a particular contaminant is not expected to
be
toxic. Concentrations above the
ERM value are better predictors of toxicity. In
both cases, NOAA takes care to point out that ERL and ERM
values are no substitute for a formal toxicity evaluation and obviously
do not
take into account specific local conditions that may enhance or inhibit
toxicity.
About
one-third of the measured concentrations of naphthalene were
below the ERL (0.16 ppm), about 60% were between the ERL and ERM (2.1
ppm), and
the remaining 10% exceeded the ERM.
The greatest concentration was 8.79 ppm measured in sample 13a.
For
the three ring PAH molecules, acenaphthylene, acenaphthene,
fluorene, phenanthrene, and anthracene, approximately 45% of the
samples tested
below the ERL (0.44 to 0.24 ppm) while only 5% exceeded the ERM (0.5 to
1.5
ppm). About half the samples were
between the ERL and ERM.
Among
the four ring PAH molecules, fluoranthene, pyrene,
benzo[a]anthracene, and benzo[a]pyrene, only two samples exceeded the
ERM
level. These were Gateway 27 and
29 from the eastern side of Jamaica Bay.
They had pyrene concentrations of 4.2 and 3.3 ppm respectively. The ERM for pyrene is 2.6 ppm.
Less than 60% of the samples did not
exceed the ERL concentrations (0.38 to 0.67 ppm) and 40% fell between
the ERL
and ERM (2.6 to 5.1 ppm) values.
Benzo[a]pyrene
(ERL = 0.43 ppm, ERM = 1.6 ppm) and
benzo[a,h]anthracene (ERL = 0.06 ppm, ERM = 0.26 ppm)
are the only five ring PAH molecules for which NOAA has set
ERL and ERM levels. Two-thirds of
all measured values were below the ERL's, six samples tested between
the ERL
and ERM values for benzo[a]pyrene, and no samples tested above the ERM
values
for either of these molecules.
In the
short term, future work will consist of analyzing any
remaining samples collected under the existing permit, writing a more
complete
report for the Gateway NPS staff, and publishing PAH data in a
peer-reviewed
journal. Intermediate range plans
are to prepare a full report and a peer-reviewed publication that will
integrate the biomarker, petroleum, and PAH data. Long
range plans are to determine if a sediment core should
be studied and if so, from which portion of Jamaica Bay.
If the decision is made to go forward,
a permit to take this core will be sought at a future date.
Gateway
Sample Points. Unless otherwise
indicated, all samples were taken in Jamaica Bay.
PAH
Concentrations in PPM
|
Sample Point |
Mode |
Naphthalene |
|
Gateway 1 |
SIM |
0.6 |
|
Gateway 3 |
SIM |
0.37 |
|
Gateway 4 |
SIM |
1.71 |
|
Gateway 5 |
SIM |
ND |
|
Gateway 6 |
SIM |
0.03 |
|
Gateway 9 |
SIM |
0.01 |
|
Gateway 13a |
SIM |
8.79 |
|
Gateway 18 |
SIM |
0.02 |
|
Gateway 23 |
SIM |
0.34 |
|
Gateway 24 |
SIM |
1.29 |
|
Gateway 26 |
SIM |
0.07 |
|
Gateway 27 |
SIM |
0.11 |
|
Gateway 29 |
SIM |
0.18 |
|
Gateway 102 |
SIM |
1.11 |
|
Gateway NB |
SIM |
3.09 |
|
|
|
|
|
Gateway 10A (11/7) |
FULL |
2.08 |
|
Gateway 11 |
FULL |
0.2 |
|
Gateway 22 |
FULL |
0.64 |
|
|
|
|
|
Sandy Hook 3 |
FULL |
ND |
All results reported in ppm
|
Sample Point |
Mode |
Acenaphthylene |
|
Gateway 1 |
SIM |
0.23 |
|
Gateway 3 |
SIM |
0.13 |
|
Gateway 4 |
SIM |
0.17 |
|
Gateway 5 |
SIM |
0.03 |
|
Gateway 6 |
SIM |
0.02 |
|
Gateway 9 |
SIM |
0.49 |
|
Gateway 13a |
SIM |
1.19 |
|
Gateway 18 |
SIM |
0.02 |
|
Gateway 23 |
SIM |
0.28 |
|
Gateway 24 |
SIM |
1.19 |
|
Gateway 26 |
SIM |
0.35 |
|
Gateway 27 |
SIM |
0.34 |
|
Gateway 29 |
SIM |
1.51 |
|
Gateway 102 |
SIM |
0.16 |
|
Gateway NB |
SIM |
1.21 |
|
|
|
|
|
Gateway 10A (11/7) |
FULL |
2.96 |
|
Gateway 11 |
FULL |
ND |
|
Gateway 22 |
FULL |
0.13 |
|
|
|
|
|
Sandy Hook 3 |
FULL |
ND |
|
Sample Point |
Mode |
Acenaphthene |
|
Gateway 1 |
SIM |
0.07 |
|
Gateway 3 |
SIM |
0.14 |
|
Gateway 4 |
SIM |
0.14 |
|
Gateway 5 |
SIM |
ND |
|
Gateway 6 |
SIM |
ND |
|
Gateway 9 |
SIM |
0.18 |
|
Gateway 13a |
SIM |
0.19 |
|
Gateway 18 |
SIM |
0.02 |
|
Gateway 23 |
SIM |
0.06 |
|
Gateway 24 |
SIM |
0.02 |
|
Gateway 26 |
SIM |
0.06 |
|
Gateway 27 |
SIM |
0.25 |
|
Gateway 29 |
SIM |
0.37 |
|
Gateway 102 |
SIM |
ND |
|
Gateway NB |
SIM |
0.2 |
|
|
|
|
|
Gateway 10A (11/7) |
FULL |
ND |
|
Gateway 11 |
FULL |
ND |
|
Gateway 22 |
FULL |
ND |
|
|
|
|
|
Sandy Hook 3 |
FULL |
0.1 |
All results
reported in ppm
|
Sample Point |
Mode |
Fluorene |
|
Gateway 1 |
SIM |
0.07 |
|
Gateway 3 |
SIM |
0.08 |
|
Gateway 4 |
SIM |
0.22 |
|
Gateway 5 |
SIM |
0.02 |
|
Gateway 6 |
SIM |
0.01 |
|
Gateway 9 |
SIM |
0.07 |
|
Gateway 13a |
SIM |
0.16 |
|
Gateway 18 |
SIM |
0.01 |
|
Gateway 23 |
SIM |
0.05 |
|
Gateway 24 |
SIM |
0.16 |
|
Gateway 26 |
SIM |
0.47 |
|
Gateway 27 |
SIM |
0.09 |
|
Gateway 29 |
SIM |
0.12 |
|
Gateway 102 |
SIM |
0.45 |
|
Gateway NB |
SIM |
ND |
|
|
|
|
|
Gateway 10A (11/7) |
FULL |
0.44 |
|
Gateway 11 |
FULL |
ND |
|
Gateway 22 |
FULL |
ND |
|
|
|
|
|
Sandy Hook 3 |
FULL |
1.15 |
|
Sample Point |
Mode |
Fluoranthene |
|
Gateway 1 |
SIM |
0.23 |
|
Gateway 3 |
SIM |
0.33 |
|
Gateway 4 |
SIM |
0.51 |
|
Gateway 5 |
SIM |
0.05 |
|
Gateway 6 |
SIM |
0.16 |
|
Gateway 9 |
SIM |
0.8 |
|
Gateway 13a |
SIM |
1.09 |
|
Gateway 18 |
SIM |
0.07 |
|
Gateway 23 |
SIM |
0.09 |
|
Gateway 24 |
SIM |
1.24 |
|
Gateway 26 |
SIM |
1.61 |
|
Gateway 27 |
SIM |
4.53 |
|
Gateway 29 |
SIM |
3.32 |
|
Gateway 102 |
SIM |
0.49 |
|
Gateway NB |
SIM |
1.54 |
|
|
|
|
|
Gateway 10A (11/7) |
FULL |
0.78 |
|
Gateway 11 |
FULL |
0.11 |
|
Gateway 22 |
FULL |
0.15 |
|
|
|
|
|
Sandy Hook 3 |
FULL |
1.21 |
All results
reported in ppm
|
Sample Point |
Mode |
Pyrene |
|
Gateway 1 |
SIM |
0.27 |
|
Gateway 3 |
SIM |
0.35 |
|
Gateway 4 |
SIM |
0.65 |
|
Gateway 5 |
SIM |
0.27 |
|
Gateway 6 |
SIM |
0.11 |
|
Gateway 9 |
SIM |
0.93 |
|
Gateway 13a |
SIM |
1.79 |
|
Gateway 18 |
SIM |
0.09 |
|
Gateway 23 |
SIM |
0.32 |
|
Gateway 24 |
SIM |
1.14 |
|
Gateway 26 |
SIM |
1.99 |
|
Gateway 27 |
SIM |
4.23 |
|
Gateway 29 |
SIM |
3.26 |
|
Gateway 102 |
SIM |
0.58 |
|
Gateway NB |
SIM |
1.75 |
|
|
|
|
|
Gateway 10A (11/7) |
FULL |
0.68 |
|
Gateway 11 |
FULL |
0.14 |
|
Gateway 22 |
FULL |
0.11 |
|
|
|
|
|
Sandy Hook 3 |
FULL |
1.59 |
|
Sample Point |
Mode |
Benzo[a]anthracene |
|
Gateway 1 |
SIM |
0.1 |
|
Gateway 3 |
SIM |
0.08 |
|
Gateway 4 |
SIM |
0.3 |
|
Gateway 5 |
SIM |
0.08 |
|
Gateway 6 |
SIM |
0.17 |
|
Gateway 9 |
SIM |
0.18 |
|
Gateway 13a |
SIM |
0.71 |
|
Gateway 18 |
SIM |
0.01 |
|
Gateway 23 |
SIM |
0.12 |
|
Gateway 24 |
SIM |
0.63 |
|
Gateway 26 |
SIM |
1.48 |
|
Gateway 27 |
SIM |
1.23 |
|
Gateway 29 |
SIM |
1.53 |
|
Gateway 102 |
SIM |
0.25 |
|
Gateway NB |
SIM |
0.85 |
|
|
|
|
|
Gateway 10A (11/7) |
FULL |
0.33 |
|
Gateway 11 |
FULL |
ND |
|
Gateway 22 |
FULL |
ND |
|
|
|
|
|
Sandy Hook 3 |
FULL |
1.7 |
All results reported in ppm
|
Sample Point |
Mode |
Chrysene |
|
Gateway 1 |
SIM |
0.1 |
|
Gateway 3 |
SIM |
0.11 |
|
Gateway 4 |
SIM |
0.37 |
|
Gateway 5 |
SIM |
0.07 |
|
Gateway 6 |
SIM |
ND |
|
Gateway 9 |
SIM |
0.22 |
|
Gateway 13a |
SIM |
0.8 |
|
Gateway 18 |
SIM |
0.01 |
|
Gateway 23 |
SIM |
0.14 |
|
Gateway 24 |
SIM |
0.69 |
|
Gateway 26 |
SIM |
1.72 |
|
Gateway 27 |
SIM |
1.98 |
|
Gateway 29 |
SIM |
1.74 |
|
Gateway 102 |
SIM |
0.33 |
|
Gateway NB |
SIM |
1.06 |
|
|
|
|
|
Gateway 10A (11/7) |
FULL |
0.42 |
|
Gateway 11 |
FULL |
ND |
|
Gateway 22 |
FULL |
ND |
|
|
|
|
|
Sandy Hook 3 |
FULL |
0.12 |
|
Sample Point |
Mode |
Benzo[b+j]fluoranthene |
|
Gateway 1 |
SIM |
0.33 |
|
Gateway 3 |
SIM |
0.05 |
|
Gateway 4 |
SIM |
1.57 |
|
Gateway 5 |
SIM |
ND |
|
Gateway 6 |
SIM |
ND |
|
Gateway 9 |
SIM |
ND |
|
Gateway 13a |
SIM |
2.57 |
|
Gateway 18 |
SIM |
ND |
|
Gateway 23 |
SIM |
0.13 |
|
Gateway 24 |
SIM |
1.51 |
|
Gateway 26 |
SIM |
4.96 |
|
Gateway 27 |
SIM |
4.01 |
|
Gateway 29 |
SIM |
5.82 |
|
Gateway 102 |
SIM |
0.95 |
|
Gateway NB |
SIM |
4.48 |
All results reported in ppm
|
Sample Point |
Mode |
Benzo[k]fluoranthene |
|
Gateway 1 |
SIM |
0.04 |
|
Gateway 3 |
SIM |
ND |
|
Gateway 4 |
SIM |
2.25 |
|
Gateway 5 |
SIM |
ND |
|
Gateway 6 |
SIM |
ND |
|
Gateway 9 |
SIM |
ND |
|
Gateway 13a |
SIM |
0.2 |
|
Gateway 18 |
SIM |
ND |
|
Gateway 23 |
SIM |
0.02 |
|
Gateway 24 |
SIM |
0.12 |
|
Gateway 26 |
SIM |
0.25 |
|
Gateway 27 |
SIM |
0.17 |
|
Gateway 29 |
SIM |
0.12 |
|
Gateway 102 |
SIM |
0.09 |
|
Gateway NB |
SIM |
0.35 |
|
Sample Point |
Mode |
Benzo[a]pyrene |
|
Gateway 1 |
SIM |
0.12 |
|
Gateway 3 |
SIM |
ND |
|
Gateway 4 |
SIM |
0.63 |
|
Gateway 5 |
SIM |
ND |
|
Gateway 6 |
SIM |
ND |
|
Gateway 9 |
SIM |
ND |
|
Gateway 13a |
SIM |
0.78 |
|
Gateway 18 |
SIM |
ND |
|
Gateway 23 |
SIM |
0.05 |
|
Gateway 24 |
SIM |
0.17 |
|
Gateway 26 |
SIM |
0.86 |
|
Gateway 27 |
SIM |
1.21 |
|
Gateway 29 |
SIM |
0.87 |
|
Gateway 102 |
SIM |
0.26 |
|
Gateway NB |
SIM |
1.62 |
All results reported in ppm
|
Sample Point |
Mode |
Dibenzo[a,h]anthracene |
|
Gateway 1 |
SIM |
ND |
|
Gateway 3 |
SIM |
ND |
|
Gateway 4 |
SIM |
ND |
|
Gateway 5 |
SIM |
ND |
|
Gateway 6 |
SIM |
ND |
|
Gateway 9 |
SIM |
ND |
|
Gateway 13a |
SIM |
ND |
|
Gateway 18 |
SIM |
ND |
|
Gateway 23 |
SIM |
ND |
|
Gateway 24 |
SIM |
ND |
|
Gateway 26 |
SIM |
ND |
|
Gateway 27 |
SIM |
ND |
|
Gateway 29 |
SIM |
ND |
|
Gateway 102 |
SIM |
ND |
|
Gateway NB |
SIM |
ND |
|
Sample Point |
Mode |
Indino[1,2,3-cd]pyrene |
|
Gateway 1 |
SIM |
0.04 |
|
Gateway 3 |
SIM |
0.09 |
|
Gateway 4 |
SIM |
ND |
|
Gateway 5 |
SIM |
ND |
|
Gateway 6 |
SIM |
ND |
|
Gateway 9 |
SIM |
ND |
|
Gateway 13a |
SIM |
0.06 |
|
Gateway 18 |
SIM |
ND |
|
Gateway 23 |
SIM |
ND |
|
Gateway 24 |
SIM |
ND |
|
Gateway 26 |
SIM |
ND |
|
Gateway 27 |
SIM |
ND |
|
Gateway 29 |
SIM |
ND |
|
Gateway 102 |
SIM |
ND |
|
Gateway NB |
SIM |
0.23 |
All results reported in ppm
|
Sample Point |
Mode |
Benzo[g,h,I]perylene |
|
Gateway 1 |
SIM |
0.04 |
|
Gateway 3 |
SIM |
0.23 |
|
Gateway 4 |
SIM |
0.15 |
|
Gateway 5 |
SIM |
ND |
|
Gateway 6 |
SIM |
ND |
|
Gateway 9 |
SIM |
ND |
|
Gateway 13a |
SIM |
0.06 |
|
Gateway 18 |
SIM |
ND |
|
Gateway 23 |
SIM |
ND |
|
Gateway 24 |
SIM |
ND |
|
Gateway 26 |
SIM |
ND |
|
Gateway 27 |
SIM |
ND |
|
Gateway 29 |
SIM |
ND |
|
Gateway 102 |
SIM |
ND |
|
Gateway NB |
SIM |
0.13 |
|
Sample Point |
Mode |
Sum of PAH
concentations |
|
Gateway 1 |
SIM |
2.54 |
|
Gateway 3 |
SIM |
2.46 |
|
Gateway 4 |
SIM |
9.3 |
|
Gateway 5 |
SIM |
0.68 |
|
Gateway 6 |
SIM |
0.95 |
|
Gateway 9 |
SIM |
3.67 |
|
Gateway 13a |
SIM |
19.59 |
|
Gateway 18 |
SIM |
0.41 |
|
Gateway 23 |
SIM |
1.84 |
|
Gateway 24 |
SIM |
8.89 |
|
Gateway 26 |
SIM |
15.43 |
|
Gateway 27 |
SIM |
19.94 |
|
Gateway 29 |
SIM |
20.04 |
|
Gateway 102 |
SIM |
5.82 |
|
Gateway NB |
SIM |
17.35 |
|
|
|
|
|
Gateway 10A (11/7) |
FULL |
8.75 |
|
Gateway 11 |
FULL |
0.59 |
|
Gateway 22 |
FULL |
1.03 |
ALL RESULTS ARE REPORTED IN PARTS PER MILLION
References:
METHOD
8275A, Semivolatile organic compounds (PAHÕs and PCBÕs)
in soils/sludges and
solid wastes using thermal extraction/gas chromatography/mass
spectrometry
(TE/GC/MS), US EPA, 1996.
Sediment
Quality
Guidelines Developed for the National Status and Trends Program, NOAA,
June,
1999.
Special Thanks:
Joseph
Lisciandrello and Bill Drakontaidis
Field
Service Engineers, Thermo Fisher Scientific
Carolyn Witte,
Department
Secretary, Chemistry and Biochemistry, Montclair State University