[show abstract][hide abstract] ABSTRACT: The Arctic is warming twice as fast as the rest of the globe and undergoing shifts in ecological disturbance regimes. These changes threaten to destabilize vast permafrost carbon reservoirs and are potential positive feedbacks to global climate change. To predict the consequences of continued arctic warming we must develop a baseline for past climate variability and its associated feedbacks using proxy records from geological archives. The goal of this research was to develop and apply two lacustrine organic geochemical proxies (alkenones and polycyclic aromatic hydrocarbons) in northeastern Alaska (NE AK) to better understand the region's climate and fire history. To develop alkenone paleothermometry in NE AK we applied our new method for alkenone analysis which uses a poly(trifluoropropylmethylsiloxane) stationary phase with gas chromatography-flame ionization detection (GC-FID). The method separated 16 alkenones from NE AK lakes and revealed 4 novel alkenones that went undetected with traditional methods. Analysis of water column particulates revealed that several indices of alkenone unsaturation were well correlated with in situ lake water temperature, allowing for a robust U K
2014 Geological Society of America Northeastern Section Meeting, Lancaster, PA; 03/2014
[show abstract][hide abstract] ABSTRACT: Plants using the C4 (Hatch-Slack) photosynthetic pathway are key for global food production and account for ca 25% of terrestrial primary productivity, mostly in relatively warm, dry regions. The discovery of modern naturally-occurring C4 plant species at elevations up to 4500 m in Tibet and 3000 m in Africa and South America, however, suggests that C4 plants are present in a wider range of environments than previously thought. Environmental conditions on the Tibetan Plateau, including high irradiance, rainfall focused in summer, and saline soils, can favor C4 plants by offsetting the deleterious effects of low growing season temperature. We present evidence based on leaf wax carbon isotope ratios from Lake Qinghai that C4 plants accounted for 50% of terrestrial primary productivity on the northeastern Tibetan Plateau throughout the Lateglacial and early Holocene. Despite cold conditions, C4 plants flourished due to a combination of factors, including maximum summer insolation, pCO2 ca 250 ppmv, and sufficient summer precipitation. The modern C3 plant-dominated ecosystem around Lake Qinghai was established ca 6 thousand years ago as pCO2 increased and summer temperature and precipitation decreased. C4 plants were also intermittently abundant during the Last Glacial period; we propose that C4 plants contributed a significant portion of local primary productivity by colonizing the exposed, saline Qinghai Lake bed during low stands. Our results contrast with state-of-the-art ecosystem models that simulate <0.5% C4 plant abundance on the Tibetan Plateau in modern and past environments. The past abundance of C4 plants on the Tibetan Plateau suggests a wider temperature range for C4 plants than can be inferred from modern distributions and model simulations, and provides paleoecological evidence to support recent findings that C4 plant evolution and distribution was determined by a combination of climatic and environmental factors (temperature, irradiance, precipitation amount and seasonality, and soil salinity). Moreover, this finding highlights the exceptional sensitivity of high-elevation ecosystems to environmental change, and provides critical benchmarks for ecosystem model validation.
[show abstract][hide abstract] ABSTRACT: Glacial and early Holocene-age sediments from lakes on Mt. Kenya have documented strong responses of montane hydrology, ecosystems, and carbon cycling to past changes in temperature and atmospheric CO2 concentrations. However, little is known about climate and ecosystem variations on Mt. Kenya during the Common Era (the past ~ 2,000 years), despite mounting evidence for significant climate changes in the East African lowlands during the past millennium and recent observations of alpine glacier retreat in the East African highlands. We present a new, high-resolution record of the hydrogen and carbon isotopic composition of terrestrial plant wax compounds (δDwax, δ13Cwax) preserved in the sediments of Sacred Lake from 200C.E. to the end of the 20th century. We find that Mt. Kenya’s climate was highly variable during the past 1800 years. Droughts at Sacred Lake around ~ 200C.E., 700C.E., and 1100C.E. align with similar droughts in central Kenya and Uganda/Congo, indicating that failures of both the Indian and Atlantic monsoons caused widespread drought throughout equatorial East Africa during the early Common Era. In contrast, dry and wet periods at Sacred Lake during the past 500 years show meridional and zonal contrasts with other sites in East Africa, suggesting strong spatial heterogeneity, possibly due to independent waxing and waning of the Atlantic and Indian monsoons. Pronounced drying after ~ 1870C.E. suggests that the current dry phase observed at Sacred Lake may have begun prior to the 20th century, around the time when the retreat of Mt. Kenya’s glaciers was first observed by European explorers. Mt. Kenya’s vegetation responded strongly to these recent climate changes, highlighting the particular sensitivity of tropical montane climate and ecosystems to regional and global climate patterns, and underscoring the critical need to understand potential impacts of future climate change scenarios on this highly sensitive region.
[show abstract][hide abstract] ABSTRACT: The origin of homochirality and its role in the development of life on Earth are among the most intriguing questions in science. It has been suggested that carbonaceous chondrites seeded primitive Earth with the initial organic compounds necessary for the origin of life. One of the strongest pieces of evidence supporting this theory is that certain amino acids in carbonaceous chondrites display a significant L-enantiomeric excess (ee), similar to those use by terrestrial. Analyses of ee in meteoritic molecules other than amino acids would shed more light on the origins of homochirality. In this study we investigated the stereochemistry of two groups of compounds: 1) free monocarboxylic acids (MCAs) from CM2 meteorites LON 94101 and Murchison; and 2) the aliphatic side chains present in the insoluble organic matter (IOM) and extracted in the form of monocarboxylic acids (MCAs) from EET 87770 (CR2) and Orgueil (CI1). Contrary to the well-known ee observed for amino acids in meteorites, we found that meteoritic branched free and IOM-derived MCAs with 5–8 carbon atoms are essentially racemic. The racemic nature of these compounds is used to discuss the possible influence of ultraviolet circularly polarized light (UVCPL) and aqueous alterations on the parent body on chirality observed in in carbonaceous chondrites.
Geochimica et Cosmochimica Acta 01/2014; · 3.88 Impact Factor
[show abstract][hide abstract] ABSTRACT: Leaf wax hydrogen isotope proxies have been widely used to reconstruct past hydrological changes. However, published reconstructions have given little consideration for the potentially variable hydrogen isotopic fractionation relative to precipitation (εwax-p) under different climate and environmental settings. Chief among various potential factors controlling fractionation is relative humidity, which is known to strongly affect oxygen isotopic ratios of plant cellulose, but its effect on hydrogen isotopic fractionation of leaf waxes is still ambiguous. Analyses of lake surface sediments and individual modern plants have provided valuable information on the variability of εwax-p, but both approaches have significant limitations. Here, we present an alternative method to obtain the integrated, time-resolved ecosystem-level εwax-p values, by analyzing modern aerosol samples collected weekly from arid (Arizona lowlands) and humid subtropical (Atlanta, Georgia) environments during the main growth season. Because aerosol samples mainly reflect regional leaf wax resources, the extreme contrast in the hydroclimate and associated vegetation assemblages between our study sites allows us to rigorously assess the impact of relative humidity and associated vegetation assemblages on leaf wax hydrogen isotopic fractionation. We show there is only minor difference (mostly <10 ‰) in the mean εwax-p values in the two endmember environments. One possible explanation is that the positive isotopic effects of low relative humidity are offset by progressive replacement of trees with grasses that have a more negative apparent fractionation. Our results represent an important step toward quantitative interpretation of leaf wax hydrogen isotopic records.
[show abstract][hide abstract] ABSTRACT: Two commonly used proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) are the TEX86 paleothermometer for sea-surface temperature reconstructions and the BIT index for reconstructing soil organic matter input to the ocean. An initial round-robin study of two sediment extracts, in which fifteen laboratories participated, showed relatively consistent TEX86 values (reproducibility ±3-4 °C when translated to temperature) but a large spread in BIT measurements (reproducibility ±0.41 on a scale of 0 to 1). Here we report results of a second round-robin study with thirty-five laboratories in which three sediments, one sediment extract and two mixtures of pure, isolated GDGTs were analyzed. The results for TEX86 and BIT index showed improvement compared to the previous round-robin study. The reproducibility, indicating interlaboratory variation, of TEX86 values ranged from 1.3-3.0 °C when translated to temperature. These results are similar to those of other temperature proxies used in paleoceanography. Comparison of the results obtained from one of the three sediments showed that TEX86 and BIT indices are not significantly affected by interlaboratory differences in sediment extraction techniques. BIT values of the sediments and extracts were at the extremes of the index with values close to 0 or 1, and showed good reproducibility (ranging from 0.013 to 0.042). However, the measured BIT values for the two GDGT mixtures, with known molar ratios of crenarchaeol and branched GDGTs, had intermediate BIT values and showed poor reproducibility and a large overestimation of the 'true' (i.e., molar-based) BIT index. The latter is likely due to, amongst other factors, the higher mass spectrometric response of branched GDGTs compared to crenarchaeol, which also varies among mass spectrometers. Correction for this different mass spectrometric response showed a considerable improvement in the reproducibility of BIT index measurements among laboratories, as well as a substantially improved estimation of molar-based BIT values. This suggests that standard mixtures should be used in order to obtain consistent, and molar-based, BIT values.
[show abstract][hide abstract] ABSTRACT: a b s t r a c t Long chain alkenones (LCAs) have played a central role in reconstructing paleo-sea surface temperature throughout much of the world oceans. The standard method for LCA separation and quantification uti-lizes gas chromatography (GC) with a non-polar column and flame ionization detection (FID). The method has remained nearly unchanged since the debut of alkenone paleothermometry over three decades ago. The conventional stationary phase used [poly(dimethylsiloxane)] is adequate for calculation of the U K0 37 index for most marine samples, but performs poorly in the separation of methyl and ethyl C 38 LCAs and fails to separate certain lacustrine LCAs, including structural isomers featuring differing double bond and carbonyl positions. Here, we demonstrate major improvements in the selectivity and resolution of numerous LCAs using a mid-polarity, dipole selective poly(trifluoropropylmethylsiloxane) GC stationary phase with FID. Various columns featuring this phase achieved baseline resolution of all C 38 LCAs in a marine sediment and Emiliania huxleyi culture samples, improving peak resolution of C 38 LCAs by > 350%. Such dipole selective stationary phases also reveal novel tri-unsaturated isomeric LCAs in lacustrine samples, for which we provide the first report and preliminary characterization. We conduct a thorough evaluation of LCA retention behavior on poly(trifluoropropylmethylsiloxane) and poly(dimethylsiloxane) columns and report an optimal range of operating conditions for both phases.
[show abstract][hide abstract] ABSTRACT: Omega-3 polyunsaturated fatty acids (ω-3 PUFAs) have become increasingly popular in dietary supplements worldwide and global demand for higher purity ω-3 PUFAs in clinical applications has been rising rapidly in the recent years. Traditional methods for isolating ω-3 PUFAs however, generally require multiple, cumbersome steps to obtain high purity (>95%) products. In this study, we report an efficient liquid chromatography method for purifying individual omega-3 fatty acid ethyl esters (FAEEs), eicosapentaenoic acid (EPA, C20:5) and docosahexaenoic acid (DHA, C22:6), at >95% purity using a silver(I)-mercaptopropyl stationary phase, otherwise known as silver-thiolate chromatographic material (AgTCM). We demonstrate the key variables controlling separation of FAEEs with a silver(I)-thiolate stationary phase and examine important similarities and differences between silver-thiolate and silver-ion chromatography in regards to the separation mechanism taking place. We demonstrate the separation behavior of FAEEs under various conditions such as mobile phase composition, flow rate and sample injection amount. Purification of EPA and DHA was carried out on an analytical and semi-preparative scale and the resulting purity was determined by GC-FID. We report high attainable purity for EPA (>95%) and DHA (>99%) from a single isocratic separation of fish oil FAEEs within 5-10min using a mobile phase of heptane/acetone (95:5, % v/v).
Journal of chromatography. A 08/2013; · 4.19 Impact Factor
[show abstract][hide abstract] ABSTRACT: The domains of the ancient polities D’MT and Aksum in the Horn of Africa’s highlands are a superior natural system for evaluating roles of environmental change on the rise and fall of civilizations. To compare environmental changes of the times of the two polities, we analyzed stable hydrogen isotopic ratios (δD) of land-plant derived fatty acids (n-C26–30) and other proxies from soil sequences spanning the Holocene from the region. Three results suggest that trends in δD values unambiguously reflect changes in rainfall. First, increases in δD coincide with dry periods inferred from studies of eastern African lakes. Second, changes in δD values were parallel among sections during overlapping time intervals. Third, consideration of vegetation history did not alter directions of trends in δD values over time. By unambiguously recording precipitation, the δD values also enhanced interpretations of proxies that are affected by both climate and land clearing.Both D’MT (ca 2750–2350 cal y BP) and the Aksumite (ca 2100–1250 cal y BP) rose during wetter intervals of the drier part of the Holocene (after ca 6000 cal y BP). Analyses of charred matter indicated that fire had been a common agent of land clearing in all sites. The influence of climate on fire varied, however. Prior to the emergence of D’MT, δD values were correlated with C4:C3 plant ratios estimated from δ13C values. There are no C4 trees and precipitation may have been the main influence on canopy openness. After ca 4300 cal y BP, there was no significant relationship between δD and C4:C3 plant ratios suggesting that factors such as fire influenced canopy openness regardless of climate. Furthermore, the impact of land clearance differed between sites and between D’MT and the Aksumite’s times. In one site, the interval from 3550 cal y BP to the decline of D’MT had several anomalies that suggested dramatic increases in thermal severity of fire and human impact. Among these were a large contribution of charred matter to a high% total organic carbon that low hydrogen and oxygen indices suggest was severely altered by other factors than humification. These results support hypotheses about the rise of civilizations being favored by specific climatic conditions but suggest that patterns of land clearing differed during the declines of D’MT and the Aksumite.
Geochimica et Cosmochimica Acta 06/2013; 111:140-161. · 3.88 Impact Factor
[show abstract][hide abstract] ABSTRACT: Silver(I) and copper(I) are known to form reversible complexes with π bonds, which have been exploited in LC for separating unsaturated organic compounds. Prominent examples include the use of AgNO3 -impregnated silica gel in LC, and the use of copper(I) salts for selective extraction of alkenes from hydrocarbon mixtures. The Dewar-Chatt-Duncanson model is often invoked to explain the interaction between Ag(I), Cu(I), and π bonds. However, it is unclear if such a reversible interaction is directly related to their d(10) outer electronic configurations. Particularly, Au(I) has not been reported to separate olefins with different numbers of double bonds in LC. Also, there has not been a systematic comparison of the liquid chromatographic properties of other d(10) transition metal salts (e.g., Zn(II), Cd(II)), making it difficult to fully understand the observed reversible interactions of Ag(I) and Cu(I) with π bonds. We demonstrate for the first time, that silica gel impregnated with all three Group 11 transition metals with 1+ oxidation state strongly and similarly retain olefin compounds in LC, while transition metals from Groups 10 and 12 do not. We also tested a range of functionalized silica gels to improve the stability of Cu(I) and Au(I) ions on the surface of the silica. This article is protected by copyright. All rights reserved.
Journal of Separation Science 06/2013; · 2.59 Impact Factor
[show abstract][hide abstract] ABSTRACT: Long chain alkenones (LCAs) are a class of di-, tri-, and tetra-unsaturated ketone biomarkers that have long been employed to reconstruct paleo-sea surface temperatures via the UK37 and UK'37 indices (1). Increasingly, researchers are investigating LCAs in lacustrine settings for their potential to produce continental paleoclimate records (2-4) and recent studies have provided quantitative LCA temperature records from arctic lakes (5-6). These efforts highlight lacustrine LCA paleothermometry as an effective tool for arctic paleolimnologists and they encourage further exploration of the proxy in high latitude lakes. In this study, we report the discovery of novel tri-unsaturated LCAs in the water column and surface sediments of lakes in Northeastern Alaska (NE AK). In June of 2012, we obtained water column samples and accompanying physical and chemical data from Toolik Lake (68.3°N, 149.36°E) and two neighboring lakes, E5 and F2. LCAs were present in all three lakes throughout the sampling period that began during isothermal spring mixing and persisted for three weeks through the onset of thermal stratification. Traditional gas chromatographic (GC) analyses yielded an unresolved mixture of tri-unsaturated LCAs, but novel GC techniques provided unprecedented separation and revealed that the 37-, 38-and 39-carbon homologs are composed of two positional isomers. Tentative structural identifications of the new compounds are proposed here. Analysis of LCAs from the sediments of Lake BrayaSø, Greenland—the site of a recent 6 kyr LCA temperature record (5)—reveal remarkably similar LCA profiles that include the tri-unsaturated isomers. LCAs extracted from a culture of the predominant marine haptophyte algae,Emiliana huxleyii, and from surface sediments of lower latitude lakes in North America and China, revealed no tri-unsaturated isomers using the same GC methods. Our findings suggest that these compounds are produced by a common high-latitude adapted haptophyte. The discovery of novel LCAs in Greenland and Alaska necessitates an investigation of these compounds and their correlations with temperature and environmental parameters. Many
43rd International Arctic Workshop, Amherst, MA, USA; 03/2013
[show abstract][hide abstract] ABSTRACT: Modern precipitation in Indonesia is strongly correlated to variations
in the Asian/Australasian monsoons, the Walker circulation, and
migrations of the Intertropical Convergence Zone (ITCZ), but controls on
multidecadal to millennial rainfall variations are less clear. We
present a new, high-resolution, precipitation proxy reconstruction from
Lake Lading (8°S, 113°E), Java, from 850 Common Era (C.E.) to
present, based on the δD of terrestrial plant waxes. We find that
rainfall has steadily increased in Java over the past millennium. This
increase persists into the twentieth century despite evidence from other
tropical proxy records for a northward ITCZ migration during the last
two centuries, which should introduce drier conditions to Java. Aspects
of this long-term increase in rainfall resemble records from the
Northern Hemisphere, tropical Indo-Pacific, suggesting that
strengthening Walker circulation played an important role in this
long-term increase in rainfall and decrease in the δD of
precipitation, while ITCZ variations may have been important to climate
variations on multidecadal to centennial timescales.
Geophysical Research Letters 01/2013; 40(2):386-391. · 3.98 Impact Factor
[show abstract][hide abstract] ABSTRACT: Compound specific hydrogen and carbon isotopic ratios of higher plant leaf waxes have been extensively used in paleoclimate and paleoenvironmental reconstructions. However, studies so far have focused on the comparison of leaf wax isotopic differences in bulk leaf samples between different plant species. We sampled three different varieties of tall grasses (Miscanthus sinensis) in six segments from base to tip and determined hydrogen and carbon isotopic ratios of leaf waxes, as well as hydrogen and oxygen isotopic ratios of leaf water samples. We found an increasing, base-to-tip hydrogen isotopic gradient along the grass blades that can probably be attributed to active leaf wax regeneration over the growth season. Carbon isotopic ratios, on the other hand, show opposite trends to hydrogen isotopic ratios along the grass blades, which may reflect different photosynthetic efficiencies at different blade locales.
[show abstract][hide abstract] ABSTRACT: We report the use of silver-thiolate chromatographic material (AgTCM) as a stable material for use in TLC. The AgTCM stationary phase operates under the same principles as silver-ion chromatography, separating compounds by degree of unsaturation; however, the AgTCM stationary phase shows considerable advantages over Ag-TLC in terms of light stability and shelf lifetime. We demonstrate the light stability of the AgTCM-TLC and its application for separations based on the degrees of unsaturation using fatty acid methyl esters (FAMEs) and polycyclic aromatic hydrocarbons (PAHs).
Journal of chromatography. A 06/2012; 1251:240-3. · 4.19 Impact Factor
[show abstract][hide abstract] ABSTRACT: Separation of organic compounds containing various numbers of double bonds (DB) can be readily achieved by using silver ion impregnated silica gel, often called silver-ion or argentation chromatography. However, the practical application of silver-ion liquid chromatography in analytical and preparative separations has been limited by the concerns about the stability and mobility of silver ions and the widespread use of reversed phase high performance liquid chromatography. Silver covalently anchored onto the thiol moiety of mercaptopropyl modified silica gel has been tested for the separation of polycyclic aromatic hydrocarbons by ring numbers, but has never been shown to separate mixtures of alkenes having different number of double bonds. We report here that silver-thiolate chromatographic material (AgTCM; including, but not limited to, silver(I) mercaptopropyl silica gel) is also highly efficient in liquid chromatographic separation of alkane/alkenes differing by one double bond. AgTCM displays exceptionally high selectivity for unsaturated compounds and high stability under extended heat and light exposure, while silver is virtually immobile during solvent elution. Compared to ionic silver, silver-thiolate interacts with double bonds less strongly, allowing AgTCM to efficiently separate olefins using less polar (and often less viscous and lower cost) solvents. The interaction energy between silver and ethylene is calculated using established computational methods and the results are in full agreement with our experimental results. Importantly, the exceptional stability of AgTCM gives rise to much higher compound recovery than conventional silver-ion silica gel during the chromatographic elution. Our results pave the way for the development of novel covalently bonded, transition metal-containing chromatographic materials.
Journal of chromatography. A 04/2012; 1240:83-9. · 4.19 Impact Factor
[show abstract][hide abstract] ABSTRACT: We show that the characterization of mono-, di- and triglycerols can be readily accomplished by high performance liquid chromatography (HPLC) with silver(I)-mercaptopropyl modified silica gel, or silver thiolate chromatographic material (AgTCM), which can be used with evaporative light scattering detection (ELSD) or atmospheric pressure chemical ionization mass spectroscopy (APCI-MS). Separation of triglycerols varying by degrees of unsaturation and cis/trans configuration in common oil samples can be achieved using a simple linear gradient of hexane and acetone. In addition to double bonds, AgTCM also displays major selectivity for compounds with different levels of polarity, allowing for efficient separation between mono-, di- and triglycerols. In comparison to conventional reversed phase columns, AgTCM produces simple chromatograms for rapid assessment of degrees of unsaturation and the amount of trans fats in triglycerides, which are central issues to food quality determination. In comparison to previous silver-ion based HPLC separations, AgTCM-HPLC based column offers greatly enhanced stability, inertness, durability, and reproducibility allowing routine coupling of the HPLC with a mass spectrometer for detection.
Journal of chromatography. A 04/2012; 1240:90-5. · 4.19 Impact Factor
[show abstract][hide abstract] ABSTRACT: 1] Dramatic hydrological fluctuations strongly impact human society, but the driving mechanisms for these changes are unclear. One suggested driver is solar variability, but supporting paleoclimate evidence is lacking. Therefore, long, continuous, high-resolution records from strategic locations are crucial for resolving the scientific debate regarding sensi-tivity of climate to solar forcing. We present a 6800–year, decadally-resolved biomarker and multidecadally-resolved hydrogen isotope record of hydroclimate from a coastal Maine peatland, The Great Heath (TGH). Regional moisture balance responds strongly and consistently to solar forcing at centennial to millennial timescales, with solar minima con-current with wet conditions. We propose that the Arctic/ North Atlantic Oscillation (AO/NAO) can amplify small solar fluctuations, producing the reconstructed hydrological variations. The Sun may be entering a weak phase, analogous to the Maunder minimum, which could lead to more frequent flooding in the northeastern US at this multidecadal timescale. Citation: Nichols, J. E., and Y. Huang (2012), Hydroclimate of the northeastern United States is highly sensitive to solar forcing, Geophys. Res. Lett., 39, L04707, doi:10.1029/2011GL050720.
Geophysical Research Letters 02/2012; 39(4):L04707. · 3.98 Impact Factor
[show abstract][hide abstract] ABSTRACT: a b s t r a c t Understanding the natural mechanisms that control fire occurrence in terrigenous ecosystems requires long and continuous records of past fires. Proxies, such as sedimentary charcoal and tree-ring fire scars, have temporal or spatial limitations and do not directly detect fire intensity. We show in this study that polycyclic aromatic hydrocarbons (PAHs) produced during wildfires record local fire events and fire intensity. We demonstrate that high performance liquid chromatography with fluorescence detector (HPLC-FLD) is superior to gas chromatography–mass spectrometry (GC–MS) for detecting the low con-centrations of sedimentary PAHs derived from natural fires. The HPLC-FLD is at least twice as sensitive as the GC–MS in selective ion monitoring (SIM) mode for parent PAHs and five 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 fire history record and show that PAH fluxes record fires within 0.5 km of the lake. The low molecular weight (LMW) PAHs (e.g., fluoranthene, pyrene and benz[a]anthracene) are the best recorders of fire, whereas the high molecular weight (HMW) PAHs likely record fire intensity. PAHs appear to resolve some of the issues inherent to other fire proxies, such as sec-ondary deposition of charcoal. This study advances our understanding of how PAHs can be used as mark-ers for fire events and poses new questions regarding the distribution of these compounds in the environment.