Millennial-Scale Climate and Human Drivers of Environmental Change and Fire Activity in a Dry, Mixed-Conifer Forest of Northwestern Montana

Warm summer temperatures and longer fire seasons are promoting larger, and in some cases, more fires that are severe in low- and mid-elevation, dry mixed-conifer forests of the Northern Rocky Mountains (NRM). Long-term historical fire conditions and human influence on past fire activity are not well understood for these topographically and biophysically heterogeneous forests. We developed reconstructions of millennial-scale fire activity, vegetation change, and human presence at Black Lake, a small closed-basin lake on the Flathead Indian Reservation in the Mission Valley, Northwestern Montana, United States. Fossil pollen, charcoal, and biomarkers associated with human presence were used to evaluate the interaction between climate variability, fire activity, vegetation change and human activity for the past 7000 years. Comparisons among multiple proxies suggest climate variability acted as the primary control on fire activity and vegetation change from the early Holocene until the late Holocene when records suggest fire activity and climate variability decoupled. Specific biomarkers (5β-stanols including coprostanol and epi-coprostanol) associated with human presence indicate humans were present within the Black Lake watershed for thousands of years, although the inferred intensity of human presence is highly variable. A strong relationship between climate variability and fire activity during the early and mid-Holocene weakens during the last few thousand years, suggesting possible increased influence of humans in mediating fire activity in recent millennia, and/or a shift in the interaction between the distribution and abundance of woody fuel and fire severity. Human-set fires during the cooler and wetter late Holocene may have been aimed at maintaining important cultural resources associated with the heterogeneous mosaic of mixed conifer forests within the Black Lake watershed. The paleoenvironmental reconstruction at Black Lake corroborates archeological records that show humans were present within the Black Lake watershed for over 7000 years. Further research is needed to evaluate the evidence for this continuous presence and the possible role that people played in shaping fire regimes and vegetation within low- to mid-elevation mixed-conifer ecosystems of the NRM

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

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

Rapid Characterization of Oxygen-Evolving Electrocatalyst Spot Arrays by the Substrate Generation/Tip Collection Mode of Scanning Electrochemical Microscopy with Decreased O-2 Diffusion Layer Overlap

A simple approach for the screening of oxygen evolution reaction (OER) electrocatalyst arrays by scanning electrochemical microscopy (SECM) in the substrate generation/tip collection (SG/TC) mode is described. The methodology is based on the application of a series (9-10 replicates) of double-potential steps to a catalytically active substrate electrode, which is switched between potentials where it displays OER activity and inactivity. With an SECM tip coaligned to a given electrocatalyst spot, the dual potential step is applied for a relatively short time in order to restrict the growth of the resulting O2 diffusion layer. The SECM is then able to measure the O2 produced while the potential sequence prevents the overlap of the diffusion layer from neighboring spots. With this approach, each spot of material in an array of Ir:Sn oxide compositions (disk shaped, about 150 μm radius) was examined independently at a constant distance. The method was tested for a series of oxygen evolution catalysts made of SnO2-IrO2 mixtures, with compositions varying between Ir:Sn 100:0 to Ir:Sn 0:100. Optimal conditions for avoiding overlapping of the diffusion profiles generated at each spot of the substrate were evaluated by digital simulation. The results obtained for the activity of SnO2-IrO2 mixtures using this new technique were validated by comparison to reported results using SECM and other technique

Calibration and assessment of electrochemical low-cost sensors in remote alpine harsh environments

This work presents results from an original open-source low-cost sensor (LCS) system developed to measure tropospheric O3 in a remote high altitude alpine site. Our study was conducted at the Col Margherita Observatory (2543 m above sea level), in the Italian Eastern Alps. The sensor system mounts three commercial low-cost O3/NO2 sensors that have been calibrated before field deployment against a laboratory standard (Thermo Scientific; 49i-PS), calibrated against the standard reference photometer no. 15 calibration scale of the World Meteorological Organization (WMO). Intra- and intercomparison between the sensors and a reference instrument (Thermo Scientific; 49c) have been conducted for 7 months from May to December 2018. The sensors required an individual calibration, both in laboratory and in the field. The sensor's dependence on the environmental meteorological variables has been considered and discussed. We showed that it is possible to reduce the bias of one LCS by using the average coefficient values of another LCS working in tandem, suggesting a way forward for the development of remote field calibration techniques. We showed that it is possible reconstruct the environmental ozone concentration during the loss of reference instrument data in situations caused by power outages. The evaluation of the analytical performances of this sensing system provides a limit of detection (LOD) 0.8, bias >3.5 ppb and ±8.5 at 95 % confidence. This first implementation of a LCS system in an alpine remote location demonstrated how to obtain valuable data from a low-cost instrument in a remote environment, opening new perspectives for the adoption of low-cost sensor networks in atmospheric sciences.publishedVersio

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

Simple and clear evidence for positive feedback limitation by bipolar behavior during scanning electrochemical microscopy of unbiased conductors

On the basis of an experimentally validated simple theoretical model, it is demonstrated unambiguously that when an unbiased conductor is probed by a scanning electrochemical tip (scanning electrochemical microscopy, SECM), it performs as a bipolar electrode. Though already envisioned in most recent SECM theories, this phenomenon is generally overlooked in SECM experimental investigations. However, as is shown here, this may alter significantly positive feedback measurements when the probed conductor is not much larger than the ti

On the use of mercury-coated tips in scanning electrochemical microscopy to investigate galvanic corrosion processes involving zinc and iron. R.M. Souto, Y. González-García, D. Battistel, S. Daniele. Corrosion Science, 55, 401-406 (2012) doi: 10.1016/j.corsci.2011.11.003

Corrosion Science, 55, 401-406 (2012) doi: 10.1016/j.corsci.2011.11.003The corrosion processes that take place in an iron-zinc galvanic pair exposed to a chloride solution were investigated by scanning electrochemical microscopy (SECM) using a mercury-coated platinum microelectrode as SECM tip. Both the release of zinc ions and the consumption of dissolved oxygen that occur in separate sites at the iron-zinc galvanic pair were monitored. Zinc ions quantification could be performed by stripping the zinc metal collected at the Hg-coated tip using linear sweep voltammetr

Tibetan Plateau lacustrine sediments as paleofire archives

Biomass burning as a natural process producing greenhouse gases may influence both regional and global climate, and it has become of planetary concern due to anthropogenic activities (Simoneit, 2000; Hopmans et al., 2012; Zennaro et al., 2014). The present work gives information about past fire events in the Tibetan Plateau and helps to increase the understanding of the interaction between Holocene's climate and fire activity. Tibetan Plateau is located in Asia, which is known to be the Earth's largest and most populated continent, and its extension is approximately 1,000 km north to south and 2,500 km east to west, with an average elevation exceeding 4,500 m. We reconstructed biomass burning events of the last 10,500 years recorded in sediments collected from lake Paru Co (4,845 m above sea level), a small moraine dammed lake located on the South-Eastern Tibetan Plateau. Sediment samples were extracted using accelerate solvent extraction and different organic molecular proxies were analysed by GC-MS and IC-MS. We used monosaccharide anhydrides, levoglucosan and its isomers and polycyclic aromatic hydrocarbons as proxies for biomass burning. These are specific molecular markers originated from the pyrolysis of cellulose showing significant fire events and indicating changes in burned fuel. The relationship between this multi-proxy approach and climatic, meteorological and charcoal data allows the reconstruction and contextualization of past fire events and suggests a correspondence between dry climate period and presence of more intense fire events, especially in the Early Holocene