Combining charcoal sediment and molecular markers to infer a Holocene fire history in the Maya Lowlands of Petén, Guatemala

Abstract Vegetation changes in the Maya Lowlands during the Holocene are a result of changing climate conditions, solely anthropogenic activities, or interactions of both factors. As a consequence, it is difficult to assess how tropical ecosystems will cope with projected changes in precipitation and land-use intensification over the next decades. We investigated the role of fire during the Holocene by combining macroscopic charcoal and the molecular fire proxies levoglucosan, mannosan and galactosan. Combining these two different fire proxies allows a more robust understanding of the complex history of fire regimes at different spatial scales during the Holocene. In order to infer changes in past biomass burning, we analysed a lake sediment core from Lake Peten Itza, Guatemala, and compared our results with millennial-scale vegetation and climate change available in the area. We detected three periods of high fire activity during the Holocene: 9500–6000 cal yr BP, 3700 cal yr BP and 2700 cal yr BP. We attribute the first maximum mostly to climate conditions and the last maximum to human activities. The rapid change between burned vegetation types at the 3700 cal yr BP fire maximum may result from human activity

Multi-biomarker analysis of sediments for paleoclimate research

Lacustrine sedimentary cores provide continuous records of large-scale and local environmental modifications, intelligible thanks to specific organic markers that accumulated in these archives during past millennia. In order to improve our knowledge on ecosystem changes due to biomass burning events and human presence during the Holocene, an effective analytical method to detect organic compounds contained in sediment samples is needed. We used Accelerated Solvent Extraction (ASE) technique followed by analysis with gas and liquid chromatographers coupled with mass spectrometers (GC-MS, IC-MS). The extraction of the molecules of interest from the sediments is made with a mixture of DCM:MeOH 9:1 v/v and it is followed by a 3 steps purification with silica gel columns. The first fraction is eluted with HEX:DCM 9:1 v/v and contains n-alkanes, indicators of vegetation, and polycyclic aromatic hydrocarbons (PAHs) as combustion proxies. Then, a second fraction is eluted with DCM and derivatized with the silylation process, in order to get the faecal sterols and stanols (FeSts), indicators of past human and grazing animals presence. These two fractions are analysed with the GC-MS technique. The third and last fraction is eluted with MeOH and contains the monosaccharide anhydrides (MAs), specific indicators of vegetation burning processes, which are analysed with IC-MS. Internal standards labelled C13 are used for the quantification and procedural blanks are extracted every batch of 12 samples. The method may undergo variations, on the basis of the complex sediment matrices which not always lend itself to the same kind of treatment. However, the technique was applied in different lakes from different continents and the obtained results, compared with historical and climate literature data, seem to demonstrate the potentiality of the method as a resourceful instrument to reconstruct past burning events and human-ecosystem interactions

Fire, vegetation and Holocene climate in the south-eastern Tibetan Plateau: a multi-biomarker reconstruction from Paru Co

The fire history of the Tibetan Plateau over centennial to millennial timescales is still unknown. Recent ice core studies reconstruct fire history over the past few decades but do not extend through the Holocene. Lacustrine sedimentary cores, however, provide continuous records of large-scale and local environmental modifications due to their accumulation of specific organic molecular markers throughout the past millennia. In order to reconstruct Holocene fire events and vegetation changes occurring on the south-eastern Tibetan Plateau and the surrounding areas, we improved and integrated previous analytical methods. The multi-proxy procedure was applied to samples retrieved from Paru Co, a small lake located in the Nyainqentanglha Mountains (29°47'45.6"N; 92°21'07.2"E; 4845m a.s.l.). The investigated biomarkers include n-alkanes as indicators of vegetation, polycyclic aromatic hydrocarbons (PAHs) as combustion proxies, faecal sterols and stanols (FeSts) as indicators of the presence of humans or grazing animals and finally monosaccharide anhydrides (MAs) as specific markers of vegetation burning processes. Relatively high concentrations of both MAs and PAHs demonstrate intense local biomass burning activity during the early Holocene (10.9–10.7calky BP), which correspond to a drier climate following deglaciation. High concentrations of MAs but not PAHs between 10.7–9calky BP suggest a period of regional biomass burning followed by a decreasing fire trend through the mid-late Holocene. This fire history is consistent with local vegetation changes reconstructed from both n-alkanes and regional pollen records, where vegetation types depend on the centennial-scale intensity of monsoon precipitation. FeSts were below detection limits for most of the samples, suggesting limited direct human influences on fire regime and vegetation changes in the lake's catchment. Climate is the main influence on fire activity recorded in Paru Co over millennial timescales, where biomass burning fluctuates in response to alternating warm/humid and cool/dry periods

Late Holocene records of fire and human presence in New Zealand

New Zealand, and the South Island in particular, can be considered an excellent test site for the study of the early impact of humans on the environment for two main reasons: the Polynesian settlement occurred only about 700-800 y BP and resulted in abrupt and huge landscape modifications. Burning forest for land clearance impacted dramatically on an ecosystem that was not adapted to fire, changing the composition of the vegetation as documented by sedimentary charcoal and pollen records. Although charcoal data give incontrovertible evidence of some unprecedented fire events right after the arrival of the Maori, its significance as a tracer for local and anthropogenic fire events has been questioned, stressing the need for new markers to confirm and complete the information about human presence and its effective impact. In the present work, faecal sterols and polycyclic aromatic hydrocarbons (PAHs) were individuated as suitable molecular markers and analyzed by GC-MS in a sediment core from Lake Kirkpatrick, located in the Lake Wakatipu catchment at 570 m a.s.l. in the South Island of New Zealand. Coprostanol accounts for about 60% of total sterol content in human faeces, being much less relevant in animal dejections. Together with its degradation product epi-coprostanol, it is well conserved in sedimentary archives and can be highly useful in paleoenvironmental reconstructions of human settlements. PAHs are produced in relevant amounts by combustion in conditions of oxygen depletion, and diagnostic ratios (DR) between specific molecules can be used for inferring fuel and sources. The charcoal record for Lake Kirkpatrick shows major fire episodes around AD 1350, confirmed by corresponding high levels of PAHs ascribable to biomass burning (as further evidenced by DR) at c. AD 1350. Moreover, the same trend is observed also in the fluxes of coprostanol and epi-coprostanol, whose sum results in two peaks at c. AD 1346 and 1351. This finding confirms not only the massive presence of humans in the area and the large use of fire at the time, but also complements and refines the reconstructions enabled by charcoal analysis

Fire in ice: two millennia of boreal forest fire history from the Greenland NEEM ice core

Biomass burning is a major source of greenhouse gases and influences regional to global climate. Pre-industrial fire-history records from black carbon, charcoal and other proxies provide baseline estimates of biomass burning at local to global scales spanning millennia, and are thus use- ful to examine the role of fire in the carbon cycle and climate system. Here we use the specific biomarker levo- glucosan together with black carbon and ammonium concen- trations from the North Greenland Eemian (NEEM) ice cores ◦◦ (77.49 N, 51.2 W; 2480ma.s.l) over the past 2000 years to infer changes in boreal fire activity. Increases in boreal fire activity over the periods 1000–1300 CE and decreases during 700–900 CE coincide with high-latitude NH temper- ature changes. Levoglucosan concentrations in the NEEM ice cores peak between 1500 and 1700 CE, and most levo- glucosan spikes coincide with the most extensive central and northern Asian droughts of the past millennium. Many of these multi-annual droughts are caused by Asian mon- soon failures, thus suggesting a connection between low- and high-latitude climate processes. North America is a primary source of biomass burning aerosols due to its relative prox- imity to the Greenland Ice Cap. During major fire events, however, isotopic analyses of dust, back trajectories and links with levoglucosan peaks and regional drought reconstruc- tions suggest that Siberia is also an important source of py- rogenic aerosols to Greenland

Levoglucosan and phenols in Antarctic marine, coastal and plateau aerosols

Due to its isolated location, Antarctica is a natural laboratory for studying atmospheric aerosols and pollution in remote areas. Here, we determined levoglucosan and phenolic compounds (PCs) at diverse Antarctic sites: on the plateau, a coastal station and during an oceanographic cruise. Levoglucosan and PCs reached the Antarctic plateau where they were observed in accumulation mode aerosols (with median levoglucosan concentrations of 6.4 pgm(-3) and 4.1 pgm(-3), and median PC concentrations of 15.0 pgm(-3) and 7.3 pgm(-3)). Aged aerosols arrived at the coastal site through katabatic circulation with the majority of the levoglucosan mass distributed on larger particulates (24.8 pgm(-3)), while PCs were present in fine particles (34.0 pgm(-3)). The low levoglucosan/PC ratios in Antarctic aerosols suggest that biomass burning aerosols only had regional, rather than local, sources. General acid/aldehyde ratios were lower at the coastal site than on the plateau. Levoglucosan and PCs determined during the oceanographic cruise were 37.6 pgm(-3) and 58.5 pgm(-3) respectively. Unlike levoglucosan, which can only be produced by biomass burning, PCs have both biomass burning and other sources. Our comparisons of these two types of compounds across a range of Antarctic marine, coastal, and plateau sites demonstrate that local marine sources dominate Antarctic PC concentrations. (C) 2015 Elsevier B.V. All rights reserved

Age of the Mt. Ortles ice cores, the Tyrolean Iceman and glaciation of the highest summit of South Tyrol since the Northern Hemisphere Climatic Optimum

In 2011 four ice cores were extracted from the summit of Alto dell'Ortles (3859 m), the highest glacier of South Tyrol in the Italian Alps. This drilling site is located only 37 km southwest from where the Tyrolean Iceman, similar to 5.3 kyrs old, was discovered emerging from the ablating ice field of Tisenjoch (3210 m, near the Italian-Austrian border) in 1991. The excellent preservation of this mummy suggested that the Tyrolean Iceman was continuously embedded in prehistoric ice and that additional ancient ice was likely preserved elsewhere in South Tyrol. Dating of the ice cores from Alto dell'Ortles based on Pb-210, tritium, beta activity and C-14 determinations, combined with an empirical model (COPRA), provides evidence for a chronologically ordered ice stratigraphy from the modern glacier surface down to the bottom ice layers with an age of similar to 7 kyrs, which confirms the hypothesis. Our results indicate that the drilling site has continuously been glaciated on frozen bedrock since similar to 7 kyrs BP. Absence of older ice on the highest glacier of South Tyrol is consistent with the removal of basal ice from bedrock during the Northern Hemisphere Climatic Optimum (6-9 kyrs BP), the warmest interval in the European Alps during the Holocene. Borehole inclinometric measurements of the current glacier flow combined with surface ground penetration radar (GPR) measurements indicate that, due to the sustained atmospheric warming since the 1980s, an acceleration of the glacier Alto dell'Ortles flow has just recently begun. Given the stratigraphic-chronological continuity of the Mt. Ortles cores over millennia, it can be argued that this behaviour has been unprecedented at this location since the Northern Hemisphere Climatic Optimum

Temporal variations of perfluoroalkyl substances and polybrominated diphenyl ethers in alpine snow

The occurrence and temporal variation of 18 perfluoroalkyl substances (PFASs) and 8 polybrominated diphenyl ethers (PBDEs) in the European Alps was investigated in a 10 m shallow firn core from Colle Gnifetti in the Monte RosaMassif (4455mabove sea level). The firn core encompasses the years 1997e2007. Firn core sections were analyzed by liquid chromatographyetandem mass spectrometry (PFASs) and gas chromatographyemass spectrometry (PBDEs). We detected 12 PFASs and 8 PBDEs in the firn samples. Perfluorobutanoic acid (PFBA; 0.3e1.8 ng L1) and perfluorooctanoic acid (PFOA; 0.2e0.6 ng L1) were the major PFASs while BDE 99 (<MQLe4.5 ng L1) and BDE 47 (n.d.e2.6 ng L1) were the major PBDEs. This study demonstrates the occurrence of PFASs and PBDEs in the European Alps and provides the first evidence that PFASs compositions may be changing to PFBA-dominated composition

Speciation analysis of iodine and bromine at picogram-per-gram levels in polar ice

Iodine and bromine species participate in key atmospheric reactions including the formation of cloud con- densation nuclei and ozone depletion. We present a novel method coupling a high-performance liquid chromatogra- phy with ion chromatography and inductively coupled plas- ma mass spectrometry, which allows the determination of iodine (I) and bromine (Br) species (IO3−, I−, Br−, BrO3−) at the picogram-per-gram levels presents in Antarctic ice. Chromatographic separation was achieved using an ION- PAC® AS16 Analytical Column with NaOH as eluent. Detection limits for I and Br species were 5 to 9 pg g−1 with an uncertainty of less than 2.5% for all considered species. Inorganic iodine and bromine species have been determined in Antarctic ice core samples, with concentrations close to the detection limits for iodine species, and approximately 150 pg g−1 for Br−. Although iodate (IO3−) is the most abundant iodine species in the atmosphere, only the much rarer iodide (I−) species was present in Antarctic Holocene ice. Bromine was found to be present in Antarctic ice as Br−