The paleolimnologist\u27s guide to compound-specific stable isotope analysis – An introduction to principles and applications of CSIA for Quaternary lake sediments

the stable isotope composition of key chemical elements for life on Earth (e.g., carbon, hydrogen, nitrogen, oxygen, sulfur) tracks changes in fluxes and turnover of these elements in the biogeosphere. Over the past 15–20 years, the potential to measure these isotopic compositions for individual, source-specific organic molecules (biomarkers) and to link them to a range of environmental conditions and processes has been unlocked and amplified by increasingly sensitive, affordable and wide-spread analytical technology. Paleoenvironmental research has seen enormous step-changes in our understanding of past ecosystem dynamics. Vital to these paradigm shifts is the need for well-constrained modern and recent analogues. Through increased understanding of these environments and their biological pathways we can successfully unravel past climatic changes and associated ecosystem adaption. With this review, we aim to introduce scientists working in the field of Quaternary paleolimnology to the tools that compound-specific isotope analysis (CSIA) provides for the gain of information on biogeochemical conditions in ancient environments. We provide information on fundamental principles and applications of novel and established CSIA applications based on the carbon, hydrogen, nitrogen, oxygen and sulfur isotopic composition of biomarkers. While biosynthesis, sources and associated isotope fractionation patterns of compounds such as n-alkanes are relatively well-constrained, new applications emerge from the increasing use of functionalized alkyl lipids, steroids, hopanoids, isoprenoids, GDGTs, pigments or cellulose. Biosynthesis and fractionation are not always fully understood. However, although analytical challenges remain, the future potential of deeper insights into ecosystem dynamics from the study of these compounds is also emerging

The environmental and evolutionary history of Lake Ohrid (FYROM/Albania). Interim results from the SCOPSCO deep drilling project

This study reviews and synthesises existing information generated within the SCOPSCO (Scientific Collaboration on Past Speciation Conditions in Lake Ohrid) deep drilling project. The four main aims of the project are to infer (i) the age and origin of Lake Ohrid (Former Yugoslav Republic of Macedonia/Republic of Albania), (ii) its regional seismotectonic history, (iii) volcanic activity and climate change in the central northern Mediterranean region, and (iv) the influence of major geological events on the evolution of its endemic species. The Ohrid basin formed by transtension during the Miocene, opened during the Pliocene and Pleistocene, and the lake established de novo in the still relatively narrow valley between 1.9 and 1.3 Ma. The lake history is recorded in a 584 m long sediment sequence, which was recovered within the framework of the International Continental Scientific Drilling Program (ICDP) from the central part (DEEP site) of the lake in spring 2013. To date, 54 tephra and cryptotephra horizons have been found in the upper 460 m of this sequence. Tephrochronology and tuning biogeochemical proxy data to orbital parameters revealed that the upper 247.8 m represent the last 637 kyr. The multi-proxy data set covering these 637 kyr indicates long- term variability. Some proxies show a change from generally cooler and wetter to drier and warmer glacial and interglacial periods around 300 ka. Short-term environmental change caused, for example, by tephra deposition or the climatic impact of millennial-scale Dansgaard–Oeschger and Heinrich events are superimposed on the long-term trends. Evolutionary studies on the extant fauna indicate that Lake Ohrid was not a refugial area for regional freshwater animals. This differs from the surrounding catchment, where the mountainous setting with relatively high water availability provided a refuge for temperate and montane trees during the relatively cold and dry glacial periods. Although Lake Ohrid experienced significant environmental change over the last 637 kyr, preliminary molecular data from extant microgastropod species do not indicate significant changes in diversification rate during this period. The reasons for this constant rate remain largely unknown, but a possible lack of environ- mentally induced extinction events in Lake Ohrid and/or the high resilience of the ecosystems may have played a role

Improved end-member characterisation of modern organic matter pools in the Ohrid Basin (Albania, Macedonia) and evaluation of new palaeoenvironmental proxies

We present elemental, lipid biomarker and, in the supplement, compound-specific isotope (δ13C, δ2H) data for soils and leaf litter collected in the catchment of Lake Ohrid (Albania, Macedonia), as well as macrophytes, particulate organic matter and sediments from the lake itself. Lake Ohrid provides an outstanding archive of continental environmen- tal change of at least 1.2 million years and the purpose of our study is to ground truth organic geochemical proxies that we developed in order to study past changes in the terres- trial biome. We show that soils dominate the lipid signal of the lake sediments rather than the vegetation or aquatic biomass. There is a strong imprint of suberin monomers on the composition of total lipid extracts and chain-length distri- butions of n-alkanoic acids, n-alcohols, ω-hydroxy acids and α, ω-dicarboxylic acids. Our end-member survey identifies that ratios of mid-chain length suberin-derived to long-chain length cuticular-derived alkyl compounds as well as their av- erage chain length distributions can be used as new molecular proxies of organic matter sources to the lake. We tested these for the 8.2 ka event, a pronounced and widespread Holocene climate fluctuation. In SE Europe climate became drier and cooler in response to the event, as is clearly recognisable in the carbonate and organic carbon records of Lake Ohrid sed- iments. Our new proxies indicate biome modification in re- sponse to hydrological changes, identifying two phases of in- creased soil organic matter (OM) supply, first from soils with moderately degraded OM and then from more degraded soils. Our study demonstrates that geochemical fingerprinting of terrestrial OM should focus on the main lipid sources, rather than the living biomass. Both can exhibit climate-controlled variability, but are generally not identical

A 27cal ka biomarker-based record of ecosystem changes from lacustrine sediments of the Chihuahua Desert of Mexico

Hydroclimate variation of the northwest Mexico during the late Pleistocene and Holocene is an active area of debate, with uncertainty in the nature and sources of precipitation. Previous research has inferred the influences of winter storms, summer monsoonal rain and autumn tropical cyclones. The impacts on regional and local ecosystems, however, are not well constrained. Here, we investigate the response of lacustrine and terrestrial habitats of the Santiaguillo Basin in the Chihuahua Desert (Mexico) to hydrological changes occurring since the late last glacial. Biomarkers from the sediments reflect variable input of organic matter (OM) from algal and bacterial biomass, aquatic microfauna and surrounding vegetation, revealing distinct stages of ecosystem adaption over the last 27 cal ka. Based on previously published and new data, we show that a perennial productive lake was present during the late glacial and it persisted until 17.5 cal ka BP. Coinciding with Heinrich event 1, OM supply from deteriorating wetland soils may have been caused by early dry conditions. Further phases of increasing aridity and a shrinking water body drove changing OM quality and biomarker composition during the early and mid-Holocene. A pronounced shift in biomarker distributions at 4 cal ka BP suggests that the supply of plant litter from resinous trees and grasses increased, likely reflecting the establishment of modern vegetation. Our results illustrate the potential of biomarker applications in the area, adding to the evidence of hydroclimate variability and enabling reconstructions of local ecosystem dynamics

Temperature Driven Membrane Lipid Adaptation in Glacial Psychrophilic Bacteria

Bacteria inhabiting non-polar glaciers are exposed to large variations in temperature, which significantly affects the fluidity of bacterial cell membranes. In order to maintain normal functions of the cell membranes, psychrophilic bacteria adapt by changing the composition of cell membrane fatty acids. However, information on the exact pattern of cell membrane adaptability in non-polar low-temperature habitats is scarce. In the present study, 42 bacterial strains were isolated from the Ghulmet, Ghulkin, and Hopar glaciers of the Hunza Valley in the Karakoram Mountain Range, Pakistan and their cell membrane fatty acid distributions studied, using gas chromatography/mass spectrometry (GC-MS) for the analysis of fatty acid methyl esters (FAMEs) liberated by acid-catalyzed methanolysis. Furthermore, Gram-negative and Gram-positive groups were grown under different temperature settings (5, 15, 25, and 35°C) in order to determine the effect of temperature on cell membrane (CM) fatty acid distribution. The analyses identified the major groups of cell membrane fatty acids (FA) as straight-chain monounsaturated fatty acids (n-MUFAs) and branched fatty acids (br-FAs), accounting for more than 70% of the fatty acids analyzed. The distribution of br-FAs and n-FAs in bacterial cell membranes was significantly affected by temperature, with the level of br-FAs decreasing relative to n-FAs with increasing temperature. Notably, the production of polyunsaturated fatty acids (PUFAs) was only seen at lower temperatures. This study contributes to understanding, for the first time, the role of br-FAs in the maintenance of cell membrane fluidity of bacteria inhabiting non-polar habitats.</p

The paleolimnologist's guide to compound-specific stable isotope analysis - An introduction to principles and applications of CSIA for quaternary lake sediments

The stable isotope composition of key chemical elements for life on Earth (e.g., carbon, hydrogen, nitrogen, oxygen, sulfur) tracks changes in fluxes and turnover of these elements in the biogeosphere. Over the past 15-20 years, the potential to measure these isotopic compositions for individual, source-specific organic molecules (biomarkers) and to link them to a range of environmental conditions and processes has been unlocked and amplified by increasingly sensitive, affordable and wide-spread analytical technology. Paleoenvironmental research has seen enormous step-changes in our understanding of past ecosystem dynamics. Vital to these paradigm shifts is the need for well-constrained modern and recent analogues. Through increased understanding of these environments and their biological pathways we can successfully unravel past climatic changes and associated ecosystem adaption. With this review, we aim to introduce scientists working in the field of Quaternary paleolimnology to the tools that compound-specific isotope analysis (CSIA) provides for the gain of information on biogeochemical conditions in ancient environments. We provide information on fundamental principles and applications of novel and established CSIA applications based on the carbon, hydrogen, nitrogen, oxygen and sulfur isotopic composition of biomarkers. While biosynthesis, sources and associated isotope fractionation patterns of compounds such as n-alkanes are relatively well-constrained, new applications emerge from the increasing use of functionalized alkyl lipids, steroids, hopanoids, isoprenoids, GDGTs, pigments or cellulose. Biosynthesis and fractionation are not always fully understood

Pollen-based temperature and precipitation changes in the Ohrid Basin (western Balkans) between 160 and 70 ka

Our study aims to reconstruct climate changes that occurred at Lake Ohrid (south-western Balkan Peninsula), the oldest extant lake in Europe, between 160 and 70 ka (covering part of marine isotope stage 6, MIS 6; all of MIS 5; and the beginning of MIS 4). A multi-method approach, including the “Modern Analog Technique” and the “Weighted Averaging Partial Least-Squares Regression”, is applied to the high-resolution pollen sequence of the DEEP site, collected from the central part of Lake Ohrid, to provide quantitative estimates of climate and bioclimate parameters. This allows us to document climatic change during the key periods of MIS 6 and MIS 5 in southern Europe, a region where accurate climate reconstructions are still lacking for this time interval.Our results for the penultimate glacial show cold and dry conditions, while the onset of the “last interglacial” is characterized by wet and warm conditions, with temperatures higher than today (by ca. 2 ∘C). The Eemian also shows the well-known climatic tri-partition in the Balkans, with an initial pre-temperate phase of abrupt warming (128–121 ka), a central temperate phase with decreasing temperatures associated with wet conditions (121–118 ka), followed by a post-temperate phase of progressive change towards cold and dry conditions (118–112 ka).After the Eemian, an alternation of four warm/wet periods with cold/dry ones, likely related to the succession of Greenland stadials and cold events known from the North Atlantic, occurred. The observed pattern is also consistent with hydrological and isotopic data from the central Mediterranean.The Lake Ohrid climate reconstruction shows greater similarity with climate patterns inferred from northern European pollen records than with southern European ones, which is probably due to its intermediate position and the mountainous setting. However, this hypothesis needs further testing as very few climate reconstructions are available for southern Europe for this key time period

COVID‐19 and protected areas: Impacts, conflicts, and possible management solutions

Abstract: During the first wave of the COVID‐19 pandemic, management authorities of numerous Protected Areas (PAs) had to discourage visitors from accessing them in order to reduce the virus transmission rate and protect local communities. This resulted in social–ecological impacts and added another layer of complexity to managing PAs. This paper presents the results of a survey in Snowdonia National Park capturing the views of over 700 local residents on the impacts of COVID‐19 restrictions and possible scenarios and tools for managing tourist numbers. Lower visitor numbers were seen in a broadly positive way by a significant number of respondents while benefit sharing issues from tourism also emerged. Most preferred options to manage overcrowding were restricting access to certain paths, the development of mobile applications to alert people to overcrowding and reporting irresponsible behavior. Our findings are useful for PA managers and local communities currently developing post‐COVID‐19 recovery strategies

On the sedimentological origin of down-core variations of bulk sedimentary nitrogen isotope ratios

Author Posting. © American Geophysical Union, 2005. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 20 (2005): PA2009, doi:10.1029/2004PA001081.The bulk sedimentary nitrogen isotopic composition of two cores from nearby sites on the northern slope of the South China Sea (Site 17940 and Ocean Drilling Program (ODP) Site 1144) differs by up to >2‰ during the last glacial period. Given their close proximity, both core sites are located in the same biogeographic zone and nutrient regime, and it is thus unlikely that this offset is due to a true gradient in surface ocean conditions. In an attempt to resolve this offset, we have investigated the possible effects of two sedimentological parameters that can affect bulk sedimentary δ15N, namely, the variable contribution of inorganic N to bulk N in the sediment and the grain-size dependence of bulk δ15N. We find that neither effect, singly or in combination, is sufficient to explain the significant δ15N offset between the two down-core records. By elimination the most likely explanation for the observed discrepancy is a different origin of both the organic and inorganic nitrogen at each site. This study adds to the growing body of evidence highlighting the complex nature and origin of the sedimentary components in sediment drifts, such as ODP Site 1144.Funding from NSERC Canada (to S.E.C. and M.K.) and NSF (OCE-0214365 and OCE-0318371 to M.J.H. and OCE-0327405 to T.I.E.) is gratefully acknowledged, as well as Woods Hole Oceanographic Institution Postdoctoral Fellowships (M.K. and G.M.), the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry (M.J.H.), and a Geological Society of America student research grant (M.K.)

Deep drilling reveals massive shifts in evolutionary dynamics after formation of ancient ecosystem

The scarcity of high-resolution empirical data directly tracking diversity over time limits our understanding of speciation and extinction dynamics and the drivers of rate changes. Here, we analyze a continuous species-level fossil record of endemic diatoms from ancient Lake Ohrid, along with environmental and climate indicator time series since lake formation 1.36 million years (Ma) ago. We show that speciation and extinction rates nearly simultaneously decreased in the environmentally dynamic phase after ecosystem formation and stabilized after deep-water conditions established in Lake Ohrid. As the lake deepens, we also see a switch in the macroevolutionary trade-off, resulting in a transition from a volatile assemblage of short-lived endemic species to a stable community of long-lived species. Our results emphasize the importance of the interplay between environmental/climate change, ecosystem stability, and environmental limits to diversity for diversification processes. The study also provides a new understanding of evolutionary dynamics in long-lived ecosystems