Organic Geochemistry 45 (2012) 717

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Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem

Polycyclic aromatic hydrocarbons (PAHs) in lake sediments record historic re

events: Validation using HPLC-uorescence detection
Elizabeth H. Denis a,1, Jaime L. Toney a,2, Rafael Tarozo a, R. Scott Anderson b, Lydia D. Roach c,
Yongsong Huang a,
a
b
c

Brown University, Department of Geological Sciences, 324 Brook St., Box 1846, Providence, RI 02912, USA
Northern Arizona University, School of Earth Sciences & Environmental Sustainability, Box 5694, Flagstaff, AZ 86011, USA
Scripps Institution of Oceanography UCSD, Department of Geosciences, Mail Code 0208, 9500 Gilman Dr., La Jolla, CA 92093-0208, USA

a r t i c l e

i n f o

Article history:
Received 29 April 2011
Received in revised form 11 January 2012
Accepted 13 January 2012
Available online 24 January 2012

a b s t r a c t
Understanding the natural mechanisms that control re occurrence in terrigenous ecosystems requires
long and continuous records of past res. Proxies, such as sedimentary charcoal and tree-ring re scars,
have temporal or spatial limitations and do not directly detect re intensity. We show in this study that
polycyclic aromatic hydrocarbons (PAHs) produced during wildres record local re events and re
intensity. We demonstrate that high performance liquid chromatography with uorescence detector
(HPLC-FLD) is superior to gas chromatographymass spectrometry (GCMS) for detecting the low concentrations of sedimentary PAHs derived from natural res. The HPLC-FLD is at least twice as sensitive
as the GCMS in selective ion monitoring (SIM) mode for parent PAHs and ve times as sensitive for
retene. The annual samples extracted from varved sediments from Swamp Lake in Yosemite National
Park, California are compared with the observational re history record and show that PAH uxes record
res within 0.5 km of the lake. The low molecular weight (LMW) PAHs (e.g., uoranthene, pyrene and
benz[a]anthracene) are the best recorders of re, whereas the high molecular weight (HMW) PAHs likely
record re intensity. PAHs appear to resolve some of the issues inherent to other re proxies, such as secondary deposition of charcoal. This study advances our understanding of how PAHs can be used as markers for re events and poses new questions regarding the distribution of these compounds in the
environment.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Understanding wildres is exceedingly important in the context
of global climate change because res have direct effects on global
carbon storage, atmospheric chemistry (input of CO2, CH4, NOx)
and ecosystem diversity (Gill and Bradstock, 1995; van der Werf
et al., 2004). Even in the best-case global warming scenarios, re
frequency is expected to increase (Scholze et al., 2006; Westerling
et al., 2006). While wildres are important globally, increases in
spatial extent, damage and management costs associated with res
have already been observed in the US over the past decade. In particular, 2006 set the record for the largest area burned in US history
and cost the US Federal Agency over $2 billion (Costs of Wildre
Suppression, 2007; National Interagency Coordination Center,

Corresponding author. Tel.: +1 401 863 3822; fax: +1 401 863 2058.
E-mail addresses: edenis@psu.edu (E.H. Denis), Jaime.Toney@glasgow.ac.uk (J.L.
Toney), Rafael_Tarozo@brown.edu (R. Tarozo), scott.anderson@nau.edu (R. Scott
Anderson), lroach@ucsd.edu (L.D. Roach), Yongsong_Huang@brown.edu (Y. Huang).
1
Present address: Department of Geosciences, The Pennsylvania State University,
Deike Building, University Park, PA 16802, USA.
2
Co-rst author.
0146-6380/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2012.01.005

2008). Understanding the natural mechanisms (e.g., climate) that

control re occurrence in terrigenous ecosystems requires continuous records of past res over hundreds and thousands of years.
Anthropogenic activities such as re suppression have left few natural re ecosystems in many regions of the US, so land managers
rely on reconstructions of re history to restore natural ecosystems
and to understand how climate inuences natural re regimes.
The most common methods for reconstructing re history include sedimentary charcoal counts and tree-ring re scar analysis.
These methods have advanced the understanding of re frequency,
re extent and the timing of past res in relation to mechanisms
that control re, such as climate (Clark, 1990; Niklasson and
Drakenberg, 2001; Whitlock and Larsen, 2001; Whitlock and
Anderson, 2003; Prichard et al., 2009; Margolis and Balmat,
2009). Each method, however, has spatial and temporal limitations
and does not directly detect re intensity. Sedimentary charcoal
analysis is a time intensive procedure that can require up to 5 cc
of sediment collected consecutively along the core depending on
the charcoal concentration (Whitlock and Larsen, 2001). For traditional lake coring techniques with a square rod piston corer (5 cm
diameter), this necessitates using up to a quarter of the core material. Physical processes of charcoal deposition and degradation can

E.H. Denis et al. / Organic Geochemistry 45 (2012) 717

Fig. 1. (A) GIS map of Yosemite National Park (YOSE) boundary. The white dot is Swamp Lake. Dark gray marks the area burned by 1996 res and light gray by 1968 res,
2 years with res within 1 km of the lake. (B) United States Map with YOSE marked in California. Adapted from the web image on the John A. Dutton e-Education Institute
website, (https://www.e-education.psu.edu/les/geosc10/image/Textbook%20images/Unit%207/map_Yosemite.gif, accessed 2 March 2010).

affect re history interpretations. Secondary deposition of charcoal

can lead to ambiguous results, as it is possible for charcoal from a
single event to be transported into the lake up to several years later
(Whitlock and Larsen, 2001; Whitlock and Anderson, 2003). Treering re scar analysis, on the other hand, requires a large population of trees to ensure continuity and to capture all events. Temporally, re scars are limited to the age of the trees, or in some cases
to stumps or downed logs.
Pyrogenic polycyclic aromatic hydrocarbons (PAHs) are produced during the combustion of plant material, such as fossil fuels
or organic material during forest res, and are predominantly unbranched, mostly 36 ring PAHs (Ramdahl, 1983; Page et al., 1999;
Yunker et al., 2002; McGrath et al., 2003; Yang et al., 2007). Preliminary work shows that the concentration of pyrogenic PAHs increases in sediments following forest res and pyrogenic PAHs
are distinguishable from petrogenic PAHs, which are petroleum
based and often have a branched or substituted structure (Page
et al., 1999). A few extant studies use PAHs as indicators of re
in the paleorecord in Triassic, Jurassic or Cretaceous age sediments,
often in conjunction with charcoal or pollen analysis (Venkatesan
and Dahl, 1989; Killops and Massoud, 1992; Arinobu et al., 1999;
Marynowki et al., 2007; Marynowski and Simoneit, 2009; van de
Schootbrugge et al., 2009; Marynowski et al., 2011). While some
studies show that the ratios of specic PAHs, such as anthracene
to anthracene plus phenanthrene (An/(An + Phe)), indicate
whether the source of PAHs is petrogenic or pyrogenic (Yunker
et al., 2002; van de Schootbrugge et al., 2009), validation of PAHs
as a re marker through comparison with historical re events
has not been undertaken. Therefore, additional studies are necessary to determine the relationship between sedimentary PAHs
and known re events to evaluate how PAHs record the re events.
Sedimentary PAHs have several characteristics that make them
attractive re indicators, including: (1) a high resistance to diagenesis (Johnsen et al., 2005), which may help improve the temporal
constraints on tree-ring analysis; (2) a structure related to the temperature of the burn event with a more condensed structure
(increasing number of rings) related to a higher burn temperature
(McGrath et al., 2003), which could provide information on re
intensity; and (3) production during a broader temperature range
than charcoal (charcoal: 200600 C, PAHs: 200900 C or hotter)
(Conedera et al., 2009; Lu et al., 2009), which could help to record
higher temperature events than those recorded by charcoal. In
addition to these important characteristics, PAHs can be quantied

accurately with modern, automated analytical instruments, which

means that PAHs possibly could be correlated with re parameters
such as re proximity to depositional basin, total area burned and
re intensity. As aerosols, PAHs potentially can provide a more regional record of re while individual PAH distributions can provide
information about the type of material that was combusted (Burns
et al., 1997; Yang et al., 2007; Lu et al., 2009).
The main concern with using pyrogenic PAHs as re markers is
the limit of detection on instruments because PAHs are typically
studied as pollutants in much higher concentrations than those
produced naturally by forest res (Notar et al., 2001; Liu et al.,
2007; Oros et al., 2007). In high concentrations, PAHs are easily detected using gas chromatographymass spectrometry (GCMS)
(Burns et al., 1997; Gabos et al., 2001). However, high performance
liquid chromatography with uorescence detector (HPLC-FLD) selects for and detects PAHs at much greater sensitivities. The
HPLC-FLDs selectivity and sensitivity is particularly important for
detecting and quantifying PAHs from high resolution records where
only a small volume of sediment is available. Vergnoux et al. (2011)
report PAH analysis by HPLC-FLD from near surface soils. However,
there is so far no report of using HPLC-FLD to analyze PAHs in aquatic sediment cores to reconstruct natural res at longer time scales.
In this study, we assess the use of known pyrogenic PAHs as an
indicator of local and regional re events and as a recorder of re
intensity using freeze core samples that were collected from
Swamp Lake, Yosemite National Park (YOSE), California, US
(Fig. 1). Because we have found PAHs that are below the detection
limit of GCMS with our sampling sizes, we develop a new method
for PAH measurement by HPLC-FLD. Our comparison of the sedimentary PAH patterns with the well documented re history record (since 1930) of YOSE indicates high delity of PAHs as re
markers. We apply the newly developed PAH marker to a second
core that extends from 1325 to 1432, and use the PAH concentrations to infer re events adjacent to the lake.

2. Methods
2.1. Site description
Swamp Lake is located at 1554 m elevation in the northwest
corner of Yosemite National Park, California (37.57N, 119.49W)
(Fig. 1). This site was chosen for its isolated location, which reduces

E.H. Denis et al. / Organic Geochemistry 45 (2012) 717

the risk of PAH input from sources other than forest res. The surface area of Swamp Lake is about 8 hectares and its maximum
depth is 20 m with no inlet and only a shallow, marshy outlet
(Smith and Anderson, 1992). The forest surrounding the lake is
dominated by white r (Abies concolor), black oak (Quercus kelloggii), incense cedar (Calocedrus decurrens) and ponderosa (Pinus
ponderosa), Jeffrey (Pinus jeffreyi) and sugar (Pinus lambertiana)
pines (Smith and Anderson, 1992).
From 1891 until 1968, re management at YOSE consisted of
total re suppression. After 1968, the park performed prescribed
burns to restore near natural conditions (van Wagtendonk and Lutz,
2007). YOSE is an advantageous site for this study because the National Park Service (NPS) has kept detailed geographic information
system (GIS) records including area burned and location on all res
that have occurred in the park since 1930 (http://www.nps.gov/gis/
data_info/park_gisdata/ca.htm, accessed 18 September 2009).
2.2. Sample collection
Two freeze cores were collected by Lydia Roach in October 2006
(Core SL0601T) and September 2007 (Core SL0708) from Swamp
Lake. The 22 cm SL0601T core contains the surface sediments.
The 62 cm SL0708 core was collected from about 49 cm below
the lake oor as inferred from visual correlation with other freeze
cores. Both cores are varved (Roach and Cayan, 2007; Cayan and
Charles, 2010).

were separated by Lydia Roach in the laboratory of Alex Sessions,

California Institute of Technology, using the solid phase extraction
procedure and elution schedule described in Sessions et al. (1999).
Briey, 8 ml glass syringe barrels were packed with 0.5 g of stationary phase bulk packing material (Supelco Discovery DSCNH2). The elution scheme was: F1 n-hexanes (4 ml), F2 4:1
n-hexanes:DCM (7 ml), F3 9:1 DCM:acetone (7 ml), F4 2% formic acid in DCM (8 ml). PAHs were captured in the F1 and F2 fractions. Samples were blown down with caution under a gentle
stream of nitrogen, just until samples were dry.
F1 and F2 fractions from 71 depth levels from SL0601T and F2
fractions from 37 depth levels from SL0708 were prepared for
and analyzed with reverse phase, high performance liquid chromatography. Each sample was dissolved in 1.0 ml of acetonitrile
(ACN), shaken vigorously by hand and sonicated for 40 s. There
was no change in chromatography when a sample was dissolved
in 20% water and 80% ACN, so 100% ACN was used to allow for easier evaporation. Each sample was ltered (NIOSH, 1998; Ramalhosa et al., 2009) with a syringe lter (Whatman 4 mm Single Use
Filter, 0.45 lm PTFE membrane) to a 2 ml vial. Samples were
refrigerated at 5 C and brought to room temperature before any
preparation or analysis. Prior to injection on GCMS samples were
blown down with caution under a gentle stream of nitrogen, just
until dry, before being dissolved in DCM for GCMS analysis.

2.5. HPLC method development and sample analysis

2.3. Sediment sampling and age control
The SL0601T core and the lower portion of the SL0708 core
(36.562 cm) were sampled in a 20 C cold room with a razor
blade at 13 mm intervals, with care taken to follow annual laminations. For age control, the presence of annual laminations in the
SL0601T core was conrmed through microscopic inspection of
thin sections and counting of layers following a distinct charcoal
band deposited in 1996 during the massive Ackerson Fire in YOSE.
Lightdark couplets were consistent with a characteristic seasonal
cycle of lakes in this region, where diatoms blooms (light couplet)
occur in the spring and fall, while terrigenous material (dark couplet) is washed into the lake by winter and early spring runoff. The
SL0601T core was dated by varve counting on high resolution digital images backwards from the sediment water interface. The
chronology for the SL0708 core was calculated by determining
the sedimentation rate through linear interpolation between
1872 and 1350 (based on xed dates for an earthquake and a tephra layer). Comparison of tephra geochemistry with that from a
library of previously analyzed tephra samples conrmed that the
tephra layer was likely generated from the eruption of the Mono
Craters in the mid 1300s. Sieh and Bursik (1986) used radiocarbon
dating, dendrochronology and stratigraphy to determine an upper
limit of 1368 for this eruption, which they constrained to have occurred within a few months to 2 years after the latest eruption of
the Inyo craters. This Inyo eruption was dated at 1350 using dendrochronology and death dates (Millar et al., 2006). The SL0708
chronology was independently veried by varve counting.
SL0601T core samples date from 18982006, while the estimated
chronology for SL0708 is 13251432.
2.4. Organic geochemical sample preparation
Freeze dried sediment samples used for extraction range from
0.010.3 g (weighed accurately to the fourth decimal point or
0.1 mg). Samples were transferred into Teon extraction vessels
and extracted in 20 ml of 9:1 (v:v) dichloromethane(DCM):methanol at 100 C in a Mars Express microwave assisted, solvent extraction system (Mars 5, CEM corp.) for 30 min with stirring. Samples

The HPLC-FLD analyses were performed with an Agilent 1200

series chromatograph with a binary pump interfaced to a diode array detector (DAD) and uorescence detector in series and an autosampler. A method for DAD was developed with a 24 PAH standard
mix (Quebec Ministry of Environment PAH Mix, H-QME-01) to assess the separation and elution order of the PAH compounds. Once
the compounds were identied on DAD, the method was developed
on FLD to optimize the signal for each compound while maintaining
a suitable chromatogram. Note that the PAH acenaphthylene does
not uoresce, but could be quantied by DAD in future studies.
The original HPLC conditions were developed based on the Agilent
method (Henderson et al., 2008). The FLD conguration was developed based on previously published studies of PAHs in sediments
using HPLC-FLD (Liu et al., 2007; Meire et al., 2008; Salgueiro-Rey
et al., 2009). For the FLD, if too many excitation and emittance
wavelengths were applied in a short time period, a staircase baseline tended to develop. The peaks and their retention times were
identied with the standard. The PMT (photomultiplier tube) gain
on the FLD settings was adjusted to obtain the highest peak signal,
while maintaining a Gaussian shape. Retention time for each PAH
between runs was very consistent (<2% deviation) and was used
to identify individual PAH peaks for the samples. Two methods
were developed because the original column was later replaced
with a new column with different specications (Table 1).
The data acquisition and analysis on the HPLC-FLD was done
with ChemStation for LC 3Dsystems software (Rev. B.04.01SP1
[647]). An external calibration curve was developed for each compound, using the 16 PAH standard mixture solution from AccuStandard, M-610-QC. The external calibration for retene was
based on an individual compound standard (SigmaAldrich, Technical grade) since retene was not a part of the mixed PAH standard.
The calibration curves for all compounds were constructed in
duplicate with relative standard deviation <3%. The abundances
of the selected compounds were calculated by comparisons of peak
areas on the calibration curve with the peak areas of the individual
PAHs obtained from the HPLC-FLD chromatograms. Peak identication was carried out by comparison of retention times with
standards.

10

E.H. Denis et al. / Organic Geochemistry 45 (2012) 717

Table 1
HPLC-FLD method conditions. Analyses for the F2 samples of SL0601T and SL0708 were performed according to Method 1 conditions. The SL0601T F1 samples were analyzed
using Method 2, which was developed subsequently using a new column with different specications.
Method 1

Method 2
Zorbax Eclipse PAH 2.1  100 mm, 3.5 lm
Time
Ex
Em
4
224
330
8
276
330
9.7
250
368
11.55
270
470
12.75
240
386
14.5
270
390
22
300
470
0.420 ml/min
A = Water; B = Acetonitrile
Time (min)
%B
Flow
0
40
0.42
0.53
40
0.42
19.85
100
0.42
21
100
0.5
26
100
0.5
27
100
0.42
28
40
0.42
Stop time = 30.00
25.0 C
5.00 ll
SL0601T and SL0708 F2s

Column:
FLD settings:
Zero all baselines

Flow:
Mobile phase:
Gradient:

Temp.:
Injection:
Samples:

PMT
12
12
12
15
14
15
15

Column:
FLD settings:
Zero all baselines

Flow:
Mobile phase:
Gradient:

Temp.:
Injection:
Samples:

Analyses for the F2 samples of SL0601T and SL0708 were performed according to Method 1 conditions in Table 1. The
SL0601T F1 samples were analyzed using Method 2, which was
developed subsequently with different specications (Table 1).
The two methods were similar and optimized the signal for each

Zorbax Eclipse PAH 2.1  50 mm, 1.8 lm

Time
Ex
Em
0
224
330
3.4
276
330
4.7
250
368
5.8
270
470
6.26
240
386
7.5
270
390
9.1
255
420
11.7
300
470
0.417 ml/min
A = Water; B = Acetonitrile
Time (min)
%B
Flow
0
45
0.417
10
100
0.417
15
100
0.417
16
100
0.3
21
100
0.3
22
45
0.417
Stop time = 22.00
25.0 C
5.00 ll
SL0601T F1s

PMT
12
12
12
15
14
15
15
15

compound while maintaining a suitable chromatogram (Fig. 2).

Coelution of PAH isomers on HPLC is possible in real samples despite our use of authentic standards, though such coelution does
not affect our interpretations. Although the F1 fraction for SL0708
was not available for analysis, the analysis of the F1 samples from

300
260

180
140

7
2

10

100
60

14

13

20
-20

12

220

LU

11

Time (min)

10

15
12

Fig. 2. Chromatograms of 16-PAH standard on HPLC-FLD. (A) Method 1 for SL0601T and SL0708 F2 samples. (B) Method 2 for SL0601T F1 samples. A different column was
used in each method (see Table 1), but the two methods are similar and equally appropriate for PAH analysis. The 16 commonly analyzed PAHs are: (1) naphthalene, (2)
acenaphthene, (3) uorene, (4) phenanthrene, (5) anthracene, (6) uoranthene, (7) pyrene, (8) benz[a]anthracene, (9) chrysene, (10) benzo[b]uoranthene, (11)
benzo[k]uoranthene, (12) benzo[a]pyrene, (13) dibenz[a,h]anthracene, (14) benzo[ghi]perylene, (15) indeno[1,2,3-cd]pyrene; acenaphthylene does not uoresce, but elutes
after naphthalene. Retene, which elutes after chrysene, was not part of this 16-PAH standard mixture solution, but was quantied in the samples based on a separate retene
standard.

E.H. Denis et al. / Organic Geochemistry 45 (2012) 717

11

Fig. 3. RLMW and RHMW PAH ux through time compared with charcoal, re, and precipitation for core SL0601T. Note that PAH ux is on a logarithmic scale. The low
molecular weight PAHs summed were uoranthene, pyrene and benz[a]anthracene. The high molecular weight PAHs summed were dibenz[a,h]anthracene,
benzo[ghi]perylene and indeno[1,2,3-cd]pyrene. The National Park Service re records extend from 19302005 AD and there is no observational re history before 1930
AD. The charcoal record is from R. Scott Anderson (unpublished results).

this time period would likely provide a more complete picture of total PAH concentration, especially for the LMW (low molecular
weight) three and four ring PAHs, which were found in this fraction
from the SL0601T core. We can, however, make robust conclusions
based on F2 only, because (1) the three PAHs we summed for the
HMW (high molecular weight) total did not elute in the F1 fraction
and the F1 fraction only provided additional LMW data and (2) the
F1 fraction helped to slightly accentuate how LMW PAHs record
res near the lake. Thus, the F2 fraction alone provides sufcient
information to make assertions of past res. Note that because indeno[1,2,3-cd]pyrene (IP) and benzo[ghi]perylene (Bghi) were only
found in the F2 fraction and not the F1 fraction, the IP/(IP + Bghi) ratio can still be utilized to indicate biomass and petroleum combustion even if only F2 samples are analyzed.
2.6. GCMS analyses
In order to conrm the main compounds identied by HPLCFLD, GCMS analyses were performed using an Agilent 6890 series
gas chromatograph with a split/splitless injector and an autosampler interfaced to an Agilent 5973N (quadrupole mass analyzer)
mass spectrometer on selected samples that contain relatively high
concentrations of PAHs. Prior to injection on GCMS samples at
room temperature were blown down with caution under a gentle
stream of nitrogen, just until dry, before being dissolved in DCM
for GCMS analysis. Separation of the compounds was achieved
using a fused silica capillary column (HP-5MS, 30 m  0.25 mm

i.d.  0.25 lm lm thickness) and injecting 1 ll. The oven temperature was programmed from 60 C (isothermal for 1 min) to 100 C
at 15 C/min, then to 310 C at 6 C/min. The nal temperature was
held for 15 min. The carrier gas was helium at 1.0 ml/min. The MSD
transfer line heater temperature was kept at 300 C. The ion source
was kept at 230 C and quadrupole mass analyzer at 150 C. The
mass spectrometer was operated in the electron impact mode at
70 eV ionization energy. Mass spectra were recorded in full scan
mode at 50500 Da. Also, mass spectra were obtained in selective
ion monitoring (SIM) mode to improve instrument sensitivity for
low concentration compounds (mass/charge ratio m/z 165 and
166 for uorene, m/z 178 for phenanthrene and anthracene, m/z
202 for uoranthene and pyrene, m/z 219 and 234 for retene, m/z
228 for benz[a]anthracene and chrysene, m/z 252 and 253 for
benzo[b]uoranthene, benzo[k]uoranthene, and benzo[a]pyrene,
m/z 276 and 277 for benzo[ghi]perylene, m/z 276 and 278 for indeno[1,2,3-cd]pyrene, and m/z 278 and 279 for dibenz[a,h]anthracene. MSD ChemStation software (ver. E. 02.00.493) was used for
data acquisition and analysis. The PAHs were identied by matching the retention times and fragmentation proles against corresponding standards and those in the NIST/EPA/NIH Mass Spectra
Library version 2.0d.
2.7. Climate data
The NPS Fire History for YOSE from 19302008 was acquired
from the NPS Data Store online (http://www.nps.gov/gis/data_in-

12

E.H. Denis et al. / Organic Geochemistry 45 (2012) 717

fo/park_gisdata/ca.htm, accessed 18 September 2009). The records

include total area burned, longitude and latitude, re dates and
other relevant information for all res in that time span, although
not all res have equally detailed records. Using ArcGIS, a 200 cell
distance raster was created to calculate the distance from the center of a re to the Swamp Lake centroid (37.57N, 119.49W). Annual data were manually separated and viewed as yearly GIS maps
for analysis of re characteristics and occurrences. From these data
the number of res per year and the total area burned per year
were determined. The maximum, minimum and average distance
from Swamp Lake and area burned were calculated for each year
(Table S1). A year in which a re occurred within 2 km of the lake
was dubbed a re year. Precipitation data for YOSE was retrieved
from the NOAA.gov site (http://www.wrh.noaa.gov/hnx/coop/
ynphdqtr.htm, accessed 4 December 2009).
2.8. Charcoal analyses
The charcoal count record for Swamp Lake (Fig. 3) was based on
macroscopic analyses of charcoal (Anderson et al., unpublished results). Samples for charcoal analysis were taken at 0.5 cm intervals.
Each sample was deocculated in a solution of 10% Na(PO3)3 (sodium hexametaphosphate) for 25 days, then wet sieved through
250 and 125 lm screens. Charcoal particles >100 lm reect occurrence of local res because particles of this size do not travel far
from their source (Whitlock and Anderson, 2003). Charcoal particles were counted and tallied using a dissecting microscope at
50 magnication. Charcoal identication was determined based
on particle color, texture and size as follows: (1) particle was completely black; (2) particle exhibited cellular structure; and (3) particle size was >125 lm. Incompletely burned particles, not
exclusively black in color, were not tallied.
3. Results
3.1. Fire history data
From 19302005, as recorded by the NPS, there were ve res
within 0.5 km of Swamp Lake, six res between 0.51 km and 11
res between 12 km. In 1996 there was a very large re that
burned around the full perimeter of Swamp Lake (Fig. 1). Based
on the NPS records, the number of res/year in YOSE has increased
from 19302005. The total area burned per year in YOSE has increased since 1930, with an average area burned per year of
14.7 km2 between 1930 and 2005 and 28.3 km2 since 1970 (Fig. 3).
3.2. HPLC-FLD versus GCMS for PAH analyses
To optimize identication and quantication of sedimentary
PAHs, we compared the use of HPLC-FLD to that of GCMS. The
HPLC-FLD was more sensitive to PAHs than the GCMS in full scan
mode or SIM mode. For example, for the GCMS in full scan mode,
only retene was detected and no other PAHs for the 2001 sample.
On the HPLC-FLD, the retene peak was very high (500 LU) and 10
other known PAHs were detected and quantied. By comparing

injection mass and the signal/noise ratio, the HPLC-FLD was about
60 times more sensitive to retene than GCMS in full scan mode
and about ve times more sensitive than GCMS in SIM mode (limit of detection (LOD) for retene: GCMS full scan 250 pg/ll, GC
MS SIM 40 pg/ll and HPLC-FLD 8 pg/ll). The concentrations of
other PAHs in the samples were much lower than retene. For other
PAHs the HPLC-FLD tended to be at least twice as sensitive as the
GCMS in SIM mode (e.g., Table 2).
3.3. Sediment samples
PAHs were detected only in the rst (F1 n-hexanes) and second fractions (F2 4:1 n-hexanes:DCM) of the four fractions collected. Pyrene, chrysene, retene and benzo[a]pyrene were
detected in almost all of the F1 fractions; phenanthrene, anthracene and uoranthene were detected in most of the F1 fractions,
while uorene was only detected in some and naphthalene and
acenaphthene were only detected in a few samples. Benz[a]anthracene, dibenz[a,h]anthracene, benzo[ghi]perylene and indeno[1,2,3cd]pyrene were not detected in the rst fraction.
In the second fraction, phenanthrene, uoranthene, pyrene,
chrysene, retene, benzo[b]uoranthene, benzo[k]uoranthene,
benzo[ghi]perylene and indeno[1,2,3-cd]pyrene were detected in
almost all of the samples, benz[a]anthracene, benzo[a]pyrene and
dibenz[a,h]anthracene were detected in most samples and naphthalene, acenaphthene, uorene and anthracene were only detected in some of the samples (Table S2). Approximately 3845%
of the concentrations of LMW PAHs (e.g., phenanthrene, uoranthene, pyrene and chrysene) are found in the F1 fraction and the rest
in the F2 fraction.
3.4. PAH data analysis
Unless otherwise noted, further data discussion of the SL0601T
samples combines the concentrations of compounds found in the
F1 and F2 fractions as determined by HPLC-FLD. The PAH uxes
in the SL0601T samples varied in relation to re events (Fig. 3).
All PAHs had a distinct, high peak in ux in 1967 (Table S2). The
LMW PAHs had a distinct, high peak in 1996, as well. Less distinct
peaks in PAHs occurred in 1953 and 1988. In these 4 years res occurred within 0.5 km of the lake. Some years with res within 2 km
of the lake are recorded with peaks in PAH ux (e.g., 1958). Individual PAH concentrations have varied over time in relation to re
parameters such as re proximity, area burned, and number of
res per year and are discussed below.
The core SL0708 samples had several peaks in PAH concentration through time (Fig. 4). Because a constant sedimentation rate
was estimated for this time period, the concentrations were not
converted to ux. At 1394, both uoranthene and pyrene had high

Table 2
Limit of detection (LOD) instrument comparison.

Compound

HPLC-FLD (pg/ll)

GCMS SIM modea (pg/ll)

Fluoranthene
Pyrene
Benz[a]anthracene
Dibenz[a,h]anthracene
Benzo[ghi]perylene
Indeno[1,2,3-cd]pyrene

0.5
0.5
0.5
2.5
0.5
2.5

1
1
5
5
1
1

Forsberg et al. (2011).

Fig. 4. RLMW and RHMW PAH concentrations from core SL0708 through time.
Note that PAH concentrations are on a logarithmic scale and from the F2 fraction
only. The low and high molecular weight PAHs summed are the same as in Fig. 3.

13

E.H. Denis et al. / Organic Geochemistry 45 (2012) 717

support that the core samples have a pyrogenic signature and indicates that the PAHs were from plant combustion (i.e. forest res).

peaks in concentration. Other periods with peaks in PAH concentrations occurred at about 1341, 1359, 1378, 1401, 1420 and
1432. The SL0601T F2 samples were three to ve times more concentrated than the SL0708 F2 samples for all PAHs except for
benzo[k]uoranthene. Retene, however, was on average 17 times
more concentrated in the SL0601T F2 samples than the SL0708
F2 samples.

4. Discussion
4.1. HPLC-FLD analysis
The HPLC-FLD is more sensitive and has greater selectivity for
detection of sedimentary pyrogenic PAHs than the GCMS. Based
on the signal/noise ratio for retene, the sensitivity of HPLC-FLD is
about 60 times greater than GCMS in full scan mode and 5 times
greater than GCMS in SIM mode. Due to low concentrations other
PAHs were not detected by GCMS in full scan mode; however, the
HPLC-FLD was at least twice as sensitive as the GCMS in SIM
mode for most other PAHs (Table 2). The HPLC-FLD method developed in this study allowed us to detect and quantify 16 known
PAHs in a single run (Table 1 and Fig. 2). Other PAHs were present
in these samples, which once identied, could be quantied and
provide more information in the future. The HPLC-FLD is more
selective than GCMS, even in SIM mode, because the HPLC-FLD
only detects compounds that uoresce (in sediments, those are primarily PAHs).
The high sensitivity and selectivity of the HPLC-FLD is important for assessing how PAHs record re because pyrogenic PAH
concentrations tend to be much lower than pollutant PAHs. In
addition, constructing a nearly annual record required using very
little sediment per sample. In the SL0601T core, for example, yearly
horizons were 0.3 cm thick, and on average, 80 mg dry mass of
sediment was extracted per sample. Thus, it was not possible to

3.5. PAH ratios indicate a pyrogenic source

Previous studies have used ratios between different PAHs to assess whether the PAH source was petrogenic or pyrogenic and to
distinguish between combustion source types. Yunker et al.
(2002) show that PAH samples with an An/(An + Phe) ratio >0.10
are associated with pyrogenic sources. This ratio was >0.10 for all
SL0601T samples in which both PAHs were detected and for all
but one sample for SL0708 (Fig. 5). The indeno[1,2,3-cd]pyrene to
indeno[1,2,3-cd]pyrene plus benzo[ghi]perylene (IP/(IP + Bghi)) ratio is used to further distinguish combustion sources: high ratios
(>0.50) indicate grass, wood or coal combustion, intermediate ratios (0.200.50) indicate liquid fossil fuel combustion and low ratios (<0.20) indicate petroleum sources (Yunker et al., 2002)
(Fig. 5). All SL0708 samples and all but one sample for SL0601T
had IP/(IP + Bghi) ratios >0.50, which is characteristic of wood combustion. In addition, Yan et al. (2005) and Kuo et al. (2011) use the
retene to retene plus chrysene (Ret/(Ret + Chr)) ratio to distinguish
between petroleum/coal combustion (0.150.50) and softwood
combustion (>0.80). All SL0601T samples and all but one sample
for SL0708 had Ret/(Ret + Chr) ratios >0.75. All of these ratios
1

0.9

An/An + Phe

0.8
0.7
0.6

Combustion

0.5
0.4
0.3
0.2
0.1
0
1895

Petroleum

1915

1935

1955

1975

1995

1405

1415

Year
Year (SL0708 Core)
1325
1

1345

1365

1385

0.9

IP/IP + Bghi

0.8

Grass, Wood
& Coal
Combustion

0.7
0.6
0.5
0.4

1952

Petroleum
Combustion

0.3
0.2
0.1
0
1895

SL0601T Core
SL0708 Core

1915

1935

1955

1975

Petroleum

1995

Year (SL0601T Core)

Fig. 5. PAH ratios for cores through time. (A) Anthracene to anthracene plus phenanthrene (An/(An + Phe)) ratio, (B) Indeno[1,2,3-cd]pyrene to indeno[1,2,3-cd]pyrene plus
benzo[ghi]perylene (IP/(IP + Bghi)) ratio. Source thresholds are based on Yunker et al. (2002). All SL0708 samples, except one, had An/(An + Phe) ratios >0.10, which indicate a
pyrogenic source. Core SL0708 was not included on the plot, because the F1 fraction for SL0708 was not available for analysis and the ratios may not be comparable to
SL0601T. Note that because IP and Bghi were only found in the F2 fraction and not the F1 fraction, the IP/(IP + Bghi) ratio can still be utilized to indicate biomass and
petroleum combustion even if only F2 samples are analyzed.

14

E.H. Denis et al. / Organic Geochemistry 45 (2012) 717

use a greater injection volume because the total injection was limited by the amount of sample available.
4.2. PAH relationship to known re events
The 16 PAHs detected and quantied in the SL0601T samples
from 19302005 show that PAHs do record res within 0.5 km of
the lake with increased LMW PAH uxes (Fig. 3). During data analysis we assessed the correlation of individual PAHs and several
PAH ratios with the known re events and found that the LMW
PAH ux best captured the known res. We chose to use the ux
rather than concentration of PAHs because ux takes into account
the annual sedimentation rate and a high sedimentation rate might
otherwise dilute the apparent concentration of PAHs in a given
sample. Increased concentrations of PAHs do occur during known
res events, however, the PAH ux provides a more accurate relationship to known re events.
The LMW and HMW PAHs show different signals. Of the LMW
PAHs, uoranthene, pyrene and benz[a]anthracene showed the
most distinct peaks during known re events, especially those
nearest the lake (wihtin 0.5 km) as indicated by high peaks in ux
for the 1996 and 1967 re events (Table S2). We chose to sum
these three LMW PAHs to represent LMW PAHs based on empirical
evidence of correspondence to known re events and because
these PAHs were quantiable in the majority of samples. The
sum of these three PAHs correlated the best with known re
events, as opposed to a sum of all the LMW PAHs studied, for
example. However, because previous studies show that combustion of different organic material (e.g. wood types) can have different PAH proles (Yang et al., 2007), we suggest that more research
is necessary from individual sites to determine what pyrogenic
PAHs are the best indicators of re in different forest regimes.
Although these three PAHs were the best recorders for res adjacent to the lake, the other PAHs provide useful information by
amplifying key re events. For example, the 1967 re is recorded
by a distinct peak in ux for all the PAHs (Table S2). The pervasive
pattern among many PAHs highlights the occurrence of a single re
event and may be more accurate than relying on a single compound. We chose to sum three HMW PAHs, dibenz[a,h]anthracene,
benzo[ghi]perylene and indeno[1,2,3-cd]pyrene, based on empirical evidence of correspondence to known re events and because
these three PAHs were quantiable in the majority of samples, in
order to compare LMW and HMW PAH signals (Fig. 3).
Of the ve re events within 0.5 km of Swamp Lake since 1930,
the 1996 and 1967 res were recorded by distinct peaks in LMW
PAH ux. The HMW PAHs recorded the 1967 re, but did not detect
the 1996 re. All of the individual PAHs had a distinct peak in ux
in 1967. We hypothesize that the different response of LMW and
HMW PAHs may be attributed to differences in burn temperature.
HMW PAHs with a greater number of rings require higher burn
temperatures (McGrath et al., 2003); therefore, the lack of HMW
PAHs in the sedimentary record during the 1996 re may indicate
that the event was not hot enough to produce as many HMW PAHs.
The peaks in LMW PAH ux associated with the 1996 and 1967
res are distinct and suggest that PAHs do not have secondary
deposition in the years following these res. If there was secondary
PAH deposition, we would expect to see broad peaks in ux or tailing of peaks. Therefore, based on these re years, it is possible that
PAHs could resolve ambiguity resulting from secondary deposition
of charcoal particles that can occur up to several years following a
re (Whitlock and Larsen, 2001).
The three other re events within 0.5 km of the lake were in
1988, 1953 and 1944; in 1953 there were actually two res that
burned within this distance. The peaks in ux for 1988 and 1953
were not as high as those for the 1967 and 1996 (Fig. 3). The
1944 re is only evident in retene (Table S2). This re may not have

been recorded with a high amplitude peak if the transport mechanisms reduced the amount of PAHs reaching the lake sediments
(e.g., unfavorable wind direction or transport of the PAHs in the re
plume up and away from the burn area).
Several res occurred within 1 and 2 km of the lake in the late
1930s, early 1960s, and late 1970s. Peaks in LMW or HMW PAH
ux are not as discernable during these times, which suggests that
PAHs primarily detect res that are within 0.5 km of the lake site.
We evaluated whether variations in individual and combined PAH
uxes through time may relate to other re parameters, such as total area burned, the number of res burned per year, or annual precipitation. On average, 51 res occurred annually from 1930 to
2005, with a maximum of 146 res during 1987. The PAH uxes
best detect those res within 0.5 km and show little relationship
to more distant re parameters.
Notably, increased annual precipitation values occur during
most re years except 1988 and 1944. The converse is not true;
not all increased annual precipitation years have res within
0.5 km of the lake. Rainfall associated with re events may help
scavenge PAH particles from the atmosphere and increase the likelihood of deposition in the lake. Although runoff is a possible
means of transport, it is not the sole or main means of transport
of PAHs to the lake because otherwise we would expect both an increase in PAHs after every high rainfall year and secondary deposition of PAHs, similar to charcoal (Whitlock and Larsen, 2001),
several years after a re event, both of which are not the case.
Rather, there is a distinct and sharp peak in PAHs for both 1967
and 1996 re years, which suggests stream transport is not a major
contributor. If stream contributed to the majority of PAHs, we
would expect there to be a hump or large tail after the 1996 and
1967 re events. If enhanced rainfall increases the likelihood of
deposition in the lake, the low rainfall in 1944 may explain the lack
of increase in PAH ux for the 1944 re.
4.3. Comparison of PAH record to charcoal
PAH uxes were analyzed from 18981929, years that predate
the NPS re records for YOSE. A charcoal inferred re record from
Swamp Lake shows that between 1910 and 1925 there were two
peaks in sedimentary charcoal (Anderson et al., unpublished results; Fig. 3). Two peaks also occur in LMW PAH ux during this
time, specically at 1908 and 1917. In addition, the period from
about 19201930, which predates the NPS re records, had consistently high LMW PAH uxes that correspond to elevated charcoal
levels, as well and may reect increased res within a 0.5 km of
the lake. The precipitation record for YOSE does not have annual
resolution at this time, so it is difcult to assess the impact of rainfall on charcoal and PAH deposition. A small peak in the charcoal
record also recorded the 1953 re, but there was no charcoal peak
associated with the 1967 re, which was a prominent peak in the
LMW PAH ux. One possibility is that the 1967 re did not occur in
the drainage basin of Swamp Lake and thus charcoal was not
deposited in the lake, but the PAHs as aerosols did reach the lake.
The charcoal record at least partially corroborates the PAH record;
however, because the PAHs did record the 1967 re that did not
appear in the charcoal record, PAHs could complement existing re
reconstructions and help provide a more complete picture of re
history for a given site. These data demonstrate that PAH ux records local re events (within 0.5 km) and demonstrate that PAHs
can serve as indicators of re within the paleorecord.
4.4. Detection of res from the fourteenth and fteenth centuries
In this section, we build upon the relationship established
above to suggest the occurrence of unknown res in the 14th
and 15th centuries. We analyzed the LMW and HMW PAHs in a

E.H. Denis et al. / Organic Geochemistry 45 (2012) 717

core from Swamp Lake that extends from 13251432. We interpret

the peaks in LMW PAH concentration at 1341, 1359, 1378, 1394,
1401, 1420 and 1432 as re events within 0.5 km of Swamp Lake
(Fig. 4). While the res we interpret as occurring in 1341, 1359,
1378, 1401, 1420, and 1432 were accompanied by a peak in
HMW PAH concentration, the interpreted re event peak at 1394
has no corresponding peak in HMW PAHs. Like the 1996 re event,
the 1394 re event appears to have burned at a lower temperature
and produced few or no HMW PAHs. The re years inferred from
the LMW PAH concentrations occurred at 20 year intervals, except the 1401 re. This is consistent with the re return interval
for the dominant montane vegetation type, inferred from pollen
around Swamp Lake at the time (Smith and Anderson, 1992). The
re return interval for montane forests ranges from 1540 years,
with an average of 27 years, based on a study conducted in Sequoia
National Park, CA (Knapp et al., 2005; Knapp and Keeley, 2006).
This re return interval is consistent with the interval between inferred re events from our PAH record from about 13251432.
4.5. Source of PAHs
The An/(An + Phe), IP/(IP + Bghi), and Ret/(Ret + Chr) ratios indicate that for both cores the dominant PAH source was from plant
combustion and PAHs are recording forest res. Samples with a
An/(An + Phe) ratio >0.10 are associated with pyrogenic sources
(Yunker et al., 2002). For SL0601T, all samples in which both phenanthrene and anthracene were detected have a pyrogenic signature
(Fig. 5). For SL0708, only one sample had a ratio lower than the
0.10 threshold, which may be due to incomplete data since the
F1 samples were not analyzed. Anthracene and phenanthrene were
both found in abundance in the F1 samples of SL0601T.
For IP/(IP + Bghi), high ratios (>0.50) indicate grass, wood, or
coal combustion, intermediate ratios (0.200.50) indicate liquid
fossil fuel combustion, and low ratios (<0.20) indicate petroleum
sources (Yunker et al., 2002) (Fig. 5). All SL0708 samples and all
but one sample for SL0601T (sample year 1954 ratio was 0.46)
had IP/(IP + Bghi) ratios >0.50, which is characteristic of wood combustion. IP and Bghi were only found in F2 fraction and not F1 fraction, so the IP/(IP + Bghi) ratio supports wood combustion for both
cores, regardless of F1 data.
Yan et al. (2005) and Kuo et al. (2011) use the retene to retene
plus chrysene (Ret/(Ret + Chr)) ratio to distinguish between petroleum/coal combustion (0.150.50) and softwood combustion
(>0.80). The Ret/(Ret + Chr) ratios were >0.75 for all SL0601T samples and all but one sample from SL0708, which may be due to
incomplete data since the F1 samples were not analyzed. The
Ret/(Ret + Chr) ratios, as well as the high ux of retene compared
to other PAHs, support soft wood combustion as the dominant
source of PAHs to the lake. All three of these ratios are consistent
with the core samples having a pyrogenic signature and indicating
that the PAHs were from plant combustion (i.e. forest res).
Retene recorded the 1967 re very clearly and was much more
abundant throughout both cores compared to other PAHs
(Table S2). Because retene is related to the combustion of coniferous wood (Ramdahl, 1983), in future work retene should be investigated in more detail, especially for regions with conifers as an
important part of the vegetation history. Comparison of PAH proles in sediments after wildres in a variety of vegetation settings
could help to discern how the burning of different vegetation affects
the relative distribution of PAHs (Burns et al., 1997; Lu et al., 2009).
5. Conclusions
Previous studies of PAHs in sediments often used GCMS (e.g.,
Burns et al., 1997; Gabos et al., 2001; Notar et al., 2001; Kuo

15

et al., 2011), but the HPLC-FLDs selectivity for and sensitivity to

PAHs make it an ideal detector for analyzing low concentrations
of natural PAHs produced by regional res, especially at nearly annual resolution where sampling material is limited. In the SL0601T
core, for example, on average 80 mg dry mass of sediment was extracted per sample. The sensitivity of the HPLC-FLD to retene was
about 60 times greater than the GCMS in full scan mode and ve
times greater than the GCMS in SIM mode.
Based on a comparison of the YOSE re records with the PAH
samples from 19302005, LMW PAH ux records res within
0.5 km of the lake. Of the ve re events within 0.5 km of the lake
in YOSE since 1930, the 1967 and 1996 res were recorded the best
with distinct peaks in PAH ux for all PAHs in 1967 and all LMW
PAHs in 1996. That only LMW PAHs recorded the 1996 re suggests that this re burned at a lower temperature, so it did not produce as many HMW PAHs. Fluoranthene, pyrene and
benz[a]anthracene were the best recorders of re, but patterns
from many PAHs in combination emphasized the occurrence of a
re event. The relationship among rainfall, re years and PAH ux
suggest that rainfall during the re season may help scavenge
PAHs from the atmosphere and aid in their deposition into the lake.
Two peaks in PAH ux occurred at about 1908 and 1917 and
were likely two re events that contributed to the high charcoal
counts during that time. The 1953 re was also recorded slightly
in the charcoal record, but the 1967 re, which was very well recorded by PAHs was not recorded by this charcoal record. That
the 1996 and 1967 res were recorded with such distinct peaks
in PAH ux suggests that PAHs do not have secondary deposition
in the years following a re. Future work should include paired
studies of sedimentary PAHs and sedimentary charcoal to determine if PAHs can resolve the issue of secondary deposition of charcoal particles. The An/(An + Phe), IP/(IP + Bghi), and Ret/(Ret + Chr)
ratios indicate that for both cores the dominant PAH source was
from plant combustion and that PAHs are recording forest res.
Thus, PAHs can serve as indicators of res farther in the past.
We infer that several res occurred within 0.5 km of Swamp
Lake between 1325 and 1432. Around 1394, both uoranthene
and pyrene had high peaks in concentration, which strongly suggests a re nearby the lake, possibly a low temperature burn as
indicated by the lack of peak in HMW PAHs. In addition, there
may have been nearby res around 1341, 1359, 1378, 1401, 1420
and 1432. This interval between re events is consistent with the
re return interval for montane forests, which was the dominant
vegetation type at this time (Smith and Anderson, 1992; Knapp
et al., 2005; Knapp and Keeley, 2006; Anderson et al., unpublished
results).
By capturing distinct events, PAHs may provide details for more
complete paleore reconstructions. Further analysis of PAH uxes
in relation to re parameters such as re proximity, burn temperature, vegetation type burned, area burned and the number of res
per year is necessary to facilitate the correlation of these parameters with PAHs. By comparing PAH uxes with known re events
we can determine how PAHs record regional re in the paleorecord.
Acknowledgements
This work could not have been achieved without the support
and help of many individuals. Reviews by A. Vergnoux and an
anonymous referee substantially improved this manuscript. We
thank Dan Cayan and Jane Teranes for assistance with core collection, Alex Sessions for use of his laboratory for sample preparation,
the Limnological Research Center at the University of Minnesota
where the cores were processed, Lynn Carlson for GIS assistance,
and Jan and Kent van Wagtendonk for directions to National Park
Service re records. This research was supported by NSF062325
and EAR-0902805 to Yongsong Huang, and a grant from the

16

E.H. Denis et al. / Organic Geochemistry 45 (2012) 717

Yosemite Association to R. Scott Anderson. Laboratory of Paleoecology Contribution 137.

Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.orggeochem.2012.01.005.
Associate Editor Mark Yunker
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