Dr. Contreras-Quintana, Sergio

The n-alkyl leaf waxes of the temperate forest of South America are poorly studied, despite being a bio-geographically isolated forest spanning wide environmental conditions. To evaluate whether local species adaptation and environmental changes influence the n-alkyl leaf wax composition, we measured the molecular abundance and distribution of n-alkyl leaf waxes (n-alkanoic acids, n-alkanes and n-alka-nols) of three dominant native species from southern temperate forest in South America. We surveyed Araucaria araucana (n = 9), Nothofagus dombeyi (n = 17) and Chusquea sp. (n = 21) at different elevations. The relationship of n-alkyl leaf wax abundance and distribution with elevation is not significant in any species, except for n-alkane ACL (average chain length) in Chusquea sp. Significant correlations are found for n-alkanoic acid abundance with precipitation and aridity in Chusquea sp. and n-alkane abundance and ACL with temperature in A. araucana. These data suggest a species-specific response to environmental variables. The main similarity in the three species is a higher abundance of n-alkanoic acids (>60%) relative to other n-alkyl leaf waxes. Only n-alkanols are not correlated to any environmental variable, and neither ACL nor C max overlap among species. These results suggest n-alkanols as a potential chemotaxo-nomic indicator at a lower taxonomic level in the region.

The study of fatty acid biomarkers in trophic structures at sub-polar latitudes is fundamental in describing energy fluxes across ecosystems characterized by complex inter-specific interactions. Due to the presence of certain essential fatty acids obtained exclusively from predator–prey interactions, fatty acid biomarkers are widely used to identify trophic interactions. This study analyzed fatty acid compositions in three species inhabiting a relatively pristine Patagonian fjord. This fjord is geographically difficult to access, so there are very little sampling opportunities, biological and oceanographic information. In the three species collected (Ctenodiscus australis (Loven in Lütken 1871) (Echinodermata, Asteroidea, Ctenodiscidae); Munida gregaria (Fabricius 1793) (Arthropoda, Malacostraca, Munididae); Eleginops maclovinus (Cuvier 1830) (Chordata, Actinopterygii, Eleginopsidae)) along this remote area were evaluated their fatty acid trophic markers as a tool to differentiate dietary components and dietary habits. The study reported significant differences in the amount of saturated fatty acids (SFA), monounsaturated fatty acids (MUFA), and polyunsaturated fatty acids (PUFA), with the highest concentrations of all fatty acids in M. gregaria. The last suggests that M. gregaria is considered as a good quality food source or biological component that might support the fjord trophic web in the Southern Hemisphere. The results describe diet compositions in sampled species, and differences among species for fatty acid compositions and proportions. This provides an initial basis for future modeling or projecting how benthic ecosystems of fjords and Patagonian channels respond to food intake, particularly in environments associated with glacial systems characterized by a low phytoplankton biomass and greater sensitivity to climate variability.

Leaf cuticular waxes are one of the most important environment-plant interaction structural systems that enable desert plants to withstand extreme climatic conditions. We present a long chain n-alkyl lipids study in fresh plant leaves and rodent palaeomiddens collected along an elevational gradient in the south-central Atacama Desert of Chile, covering six different vegetation belts: Steppe (4500-4000 m asl), Puna (4000-3300 m asl), pre-Puna (3300-2400 m asl), Absolute Desert (2400-1000 m asl) and Coastal Desert (1000-0 m asl). The 28 rodent palaeomiddens analyzed from Quebrada Incahuasi (25.6 °S, 3600 m asl) span the last 17,000 years. Modern-day distribution of long-chain n-alkanes and n-alkanoic acids varies among the dominant plant associations of the Atacama Desert. These plants show a species-specific chemotaxonomy linked to the climatic conditions. Furthermore, differences in average chain length (ACL) and carbon preference index (CPI) suggest that these plant communities are highly adapted to extreme environmental conditions. The sum of leaf wax n-alkanes was highest under wet conditions, while n-alkanoic acids (between n-C24 and n-C28) increased with hyperaridity. Similarly, analysis of n-alkane time series from palaeomiddens showed that the greatest changes in leaf wax n-alkane distributions (ACL and CPI) corresponded to the greatest increases in moisture during the Central Andean Pluvial Event (CAPE; between 18 and 9 ka cal BP) and the Late Holocene. The shift in the palaeomidden n-alkane distributions is corroborated by the relative abundance of rainfall-dependent extra-local taxa. This is the first study to report leaf wax content obtained from ancient rodent middens, and shows promising results as a robust hydroclimate proxy for the Atacama Desert region.

African climate is generally considered to have evolved towards progressively drier conditions over the past few million years, with increased variability as glacial–interglacial change intensified worldwide1,2,3. Palaeoclimate records derived mainly from northern Africa exhibit a 100,000-year (eccentricity) cycle overprinted on a pronounced 20,000-year (precession) beat, driven by orbital forcing of summer insolation, global ice volume and long-lived atmospheric greenhouse gases4. Here we present a 1.3-million-year-long climate history from the Lake Malawi basin (10°–14° S in eastern Africa), which displays strong 100,000-year (eccentricity) cycles of temperature and rainfall following the Mid-Pleistocene Transition around 900,000 years ago. Interglacial periods were relatively warm and moist, while ice ages were cool and dry. The Malawi record shows limited evidence for precessional variability, which we attribute to the opposing effects of austral summer insolation and the temporal/spatial pattern of sea surface temperature in the Indian Ocean. The temperature history of the Malawi basin, at least for the past 500,000 years, strongly resembles past changes in atmospheric carbon dioxide and terrigenous dust flux in the tropical Pacific Ocean, but not in global ice volume. Climate in this sector of eastern Africa (unlike northern Africa) evolved from a predominantly arid environment with high-frequency variability to generally wetter conditions with more prolonged wet and dry intervals.

Paleolimnological studies in western South America, where meteorological stations are scarce, are critical to obtain more realistic and reliable regional reconstructions of past climate and environmental changes, including vegetation and water budget variability. However, climate and environmental geochemical indicators must be tested before they can be applied with confidence. Here we present a survey of lacustrine surface sediment (core top, 0 to ~1 cm) biogeochemical proxies (total organic carbon [TOC], total nitrogen [TN], carbon/nitrogen ratio [C/N ratio] and bulk organic δ13C and total δ15N) from a suite of 72 lakes spanning the transition from a Mediterranean climate with a patchwork of cultivated vegetation, pastureland, and conifers in central Chile to a rainy temperate climate dominated by broadleaf deciduous and evergreen forest further south. Sedimentary data are compared to the latitudinal and orographic climatic trends of the region based on the climatology (precipitation and temperature) produced with Climate Forecast System Reanalysis (CFSR) data and the modern Southern Hemisphere Westerly Winds (SWW) location. The geochemical data show inflection points at ~42°S latitude and ~1500 m elevation that are likely related to the northern limit of influence of the SWW and elevation of the snow line, respectively. Overall the organic proxies were able to mimic climatic trends (Mean Annual Precipitation [MAP] and temperature [MAT]), indicating that they are a useful tool to be included in paleoclimatological reconstruction of the region.

Southern South America is the only large landmass that extends through the core of the Southern Westerly Winds (SWW), controlling hydrological and ecosystem variability in the region. In fact, the vegetation along the west coast changes from Temperate and Valdivian Rain Forest to the North Patagonian Evergreen Forest (ca. 42°S) due to the latitudinal influence of the SWW. Climate is an important driver of organic matter accumulation in lakes, hence changes in vegetation would be recorded in lacustrine sedimentary archives. This study evaluated leaf waxes contained in lake surface sediments as indicators of climate change along the west coast of southern South America, providing a biogeochemical dataset for ongoing and future (paleo)climate and environmental research. The fatty acid and n-alkane sediment leaf wax datasets are compared with latitudinal, orographic, and climatic (Mean Annual air Temperature [MAT] & Precipitation [MAP]) trends extracted from a monthly gridded reanalysis product of the Climate Forecast System Reanalysis. Fatty acids are more abundant than n-alkanes, with high abundances characterizing the transition between seasonal and year-round precipitation along the coast (ca. 42°S). The abundance of both leaf wax groups increases with MAP, suggesting precipitation as the main control on sedimentary leaf wax delivery to the lake sediments in the study area. The Carbon Preference Index (CPI) of the two groups show opposite trends, but both highlight the climate transition at ca. 42°S, and have a linear relationship with MAP. The opposite significant trends between n-alkane CPI and fatty acid CPI with MAP are interpreted as higher n-alkane production at much higher precipitation because leaf wax fatty acids are the precursors of n-alkanes. Hence, past periods during which these leaf waxes show opposite trends in CPI might be interpreted as a precipitation change, especially if additional information such as pollen, diatoms, chironomids and stable isotopes is available.

PBDEs (10 congeners) were analyzed using GC–MS in superficial sediments and organisms of the Concepción Bay after the 2010 Tsunami. From all congeners analyzed PBDE-47, -99, -100 and -209 were the most frequently detected. Concentrations (ng g1 d.w.) in sediments for RPBDE-47, -99, -100 were low (0.02–0.09). However, PBDE-209 showed significantly higher values 20 ng g1 d.w. This result were 10 times lower than those reported in a previous study of the 2010 Tsunami. The high result might be influenced by the massive urban debris dragged by the 2010 Tsunami. In organisms, concentrations of PBDE-47, -99, -100 (0.4 ng g1 d.w.) were higher than those found in sediments (0.04 ng g1 d.w.). Differences in PBDE pattern were also observed between different levels of the trophic food chain (primary and secondary consumers). This is the first attempt to assess the current status of Concepción Bay after the 2010 Tsunami.

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are a family of bacterial lipids which have emerged over time as robust temperature and pH paleoproxies in continental settings. Nevertheless, it was previously shown that other parameters than temperature and pH, such as soil moisture, thermal regime or vegetation can also influence the relative distribution of brGDGTs in soils and peats. This can explain a large part of the residual scatter in the global brGDGT calibrations with mean annual air temperature (MAAT) and pH in these settings. Despite improvements in brGDGT analytical methods and development of refined models, the root-mean-square error (RMSE) associated with global calibrations between brGDGT distribution and MAAT in soils and peats remains high ( 5 °C). The aim of the present study was to develop a new global terrestrial brGDGT temperature calibration from a worldwide extended dataset (i.e. 775 soil and peat samples, i.e. 112 samples added to the previously available global calibration) using a machine learning algorithm. Statistical analyses highlighted five clusters with different effects of potential confounding factors in addition to MAAT on the relative abundances of brGDGTs. The results also revealed the limitations of using a single index and a simple linear regression model to capture the response of brGDGTs to temperature changes. A new improved calibration based on a random forest algorithm was thus proposed, the so called random Forest Regression for PaleOMAAT using brGDGTs (FROG). This multi-factorial and non-parametric model allows to overcome the use of a single index, and to be more representative of the environmental complexity by taking into account the non-linear relationships between MAAT and the relative abundances of the individual brGDGTs. The FROG model represents a refined brGDGT temperature calibration (R2 = 0.8; RMSE = 4.01 °C) for soils and peats, more robust and accurate than previous global soil calibrations while being proposed on an extended dataset. This novel improved calibra- tion was further applied and validated on two paleo archives covering the last 110 kyr and the Pliocene, respectively.

Climate variability during Pleistocene glacial/interglacial transitions is well documented in marine and ice-sheet isotopic records, but terrestrial records showing the continental response to these transitions are scarce, especially for earlier in the Pleistocene. Cyclic intervals of warm interglacial and cold glacial conditions preserved in terrestrial records such as lake sediments provide opportunities to probe the biosphere's response to climate change. In this study, we track climate and plant type changes, specifically the presence of C3 and C4 plants, using the abundance and δ13C signatures of leaf waxes in paleolacustrine sediments from Valles Caldera in New Mexico. Through these changes, weassess there sponse of vegetation to climate variability in southwestern North America through two mid-Pleistocene glacial/interglacial transitions (Marine Isotope Stage [MIS] 14/13 and 12/11). Leaf wax data show that the C3 forest taxa were dominant through the entire record whereas C4 plants, better adapted to warm conditions and competitive under water stress, are favored during warming and extended arid periods during interglacials. The δ13C signature in leaf wax n-alkanes suggests that C4 plants persisted in the water shed throughout the interglacials and that some summer rainfall (which is required to support C4 grasses) was maintained even during prolonged dry periods. The abundance and carbon isotope composition of leaf waxes together with new MBT/CBT (methylation index of branched tetraethers/cyclization index of branched tetraethers) temperature data confirm warmer and more arid conditions during MIS 13 than during MIS 11, in spite of relatively low greenhouse gas concentrations during MIS 13. This suggests that variations in incoming solar radiation have played a major role in regulating the surface temperature, regional hydrological systems and vegetation in southwestern North America, likely through changes in the North American Monsoon coupled with variations in the location of the mid-latitude westerlies.

The Northern Patagonia coast, characterized by an intricate interaction among terrestrial and marine systems such as Reloncaví Estuarine System (RES), present highly productive marine and aquaculture activities, having a significant socio-economic importance in Chile. Understanding the composition of Organic Matter (OM) in aquatic ecosystems is crucial for elucidating biogeochemical processes, and the use of lipid biomarkers, has proven valuable in identifying OM sources. This study investigates the relationship between phytoplankton biomass indicators, including phytoplankton abundance, chlorophyll-a, and sterol molecules synthesized in high percentages by phytoplankton cells, also known as phytoplankton-derived sterols at the RES. The RES encompasses the Reloncaví Fjord (RF) and the Reloncaví Sound (RS) and exhibits a high influenced by oceanic waters and freshwater discharge from rivers Spatio-temporal sampling was conducted during the austral spring, summer and winter expeditions of 2018 and 2019, at two sites in RS and RF mouth (RFm). Our findings reveal higher sterol concentration at RFm than RS. Notably, high sterol concentrations during austral summer season coinciding with increased phytoplankton abundances. Furthermore, higher concentrations of terrestrial-derived sterols such as β-sitosterol (C29Δ5) and stigmasterol (C29Δ5,22), at RFm site suggested an input of OM from the inner RF. Phytoplankton-derived sterols such as 24-methylenecholesterol (C28Δ5,24(28)) provide a reliable estimate of total diatom abundance at both sites (RFm and RS), though they showed a lower relationship with taxonomic subroups and phytoplankton classes in our study area. Hence, phytoplankton-derived sterols can be considered reliable diatom biomarkers, particularly in the RS, where the primary source of OM is predominantly marine, and even with high sterol degradation values at RES. Our study highlights the importance of interpreting changes in sterol abundances as phytoplankton community shifts. To avoid misinterpretation, it is essential to incorporate direct phytoplankton counts in elucidating the complex biosynthetic sources of sterols within the water column.