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River networks connect terrestrial and marine ecosystems through transport of pollutants and nutrients. Lakes represent discontinuities within these river networks, which can be important biogeochemical hotspots, introducing substantial changes to the aquatic environment. Nitrogen is a key macronutrient that can potentially limit or co-limit primary production, but the processes that determine the fate of nitrogen during transport through river-lake networks are poorly understood. We studied three river systems and their lake discontinuities, spanning a range of trophic states and average water residence times, to understand the changes introduced to riverine nitrogen biogeochemistry by lake discontinuities. In-lake processes noticeably altered the concentration and speciation of nitrogen. Annually, lakes reduced up to 44% of nitrate compared to main inflow concentrations, while there was large variability in nitrate dynamics seasonally. The drawdown in surface nitrate concentrations resulted at times in phytoplankton co-limitation by nitrogen in-lake, as well as in the downstream river, where altered nitrogen patterns could persist for several kilometers. However, lakes occasionally subsidized N to downstream rivers as ammonium or dissolved organic nitrogen. Assimilation of nitrate in lake surface waters was one of the dominant processes impacting nitrogen availability; however, stable isotope data revealed an unexpected contribution of nitrification on nitrogen cycling in the epilimnion throughout the year and across trophic gradients. These changes in nitrogen concentration, as well as speciation introduced by lake discontinuities have potentially important consequences for the composition and metabolism of communities in downstream rivers and contribute to our fundamental understanding of freshwater processes.

Wildfires affect 40% of the earth's terrestrial biome, but much of our knowledge of wildfire activity is limited to the satellite era. Improved understanding of past fires is necessary to better forecast how fire regimes might change with future climate change, to understand ecosystem resilience to fire, and to improve data‐model comparisons. Environmental proxy archives can extend our knowledge of past fire activity. Speleothems, naturally occurring cave formations, are widely used in paleoenvironmental research as they are absolutely dateable, occur on every ice‐free continent, and include multiple proxies. Recently, speleothems have been shown to record past fire events (Argiriadis et al., 2019, https://doi.org/10.1021/acs.analchem.9b00767; McDonough et al., 2022, https://doi.org/10.1016/j.gca.2022.03.020; Homann et al., 2022, https://doi.org/10.1038/s41467-022-34950-x). Here we present a review of this emerging application in speleothem paleoenvironmental science. We give a concise overview of fire regimes and common paleofire proxies, describe past attempts to use stalagmites to investigate paleofire, and describe the physical basis through which speleothems can record past fires. We then describe the ideal speleothem sample for paleofire research and offer a summary of applicable laboratory and statistical methods. Finally, we present four case studies from southwest Australia which: (a) explore the geochemistry of ash leachates, (b) detail how sulfate isotopes may be a proxy for post fire ecological recovery, (c) demonstrate how a catastrophic paleofire was linked to changes in climate and land management, and (d) investigate whether deep caves can record past fire events. We conclude the paper by outlining future research directions for paleofire applications.

Sulphate-reducing bacteria (SRB) and magnetotactic bacteria (MTB) are two special groups of prokaryotes that emerged early in Earth's history. These extremotolerant bacterial groups have rarely been identified or studied within cave and karst environments, especially hyperalkaline cave systems (pH > 9), such as Poole's Cavern in Derbyshire, England. In this study, we identify the sulphate-reducing MTB Desulfovibrio magneticus, within this hyperalkaline cave system. It appears to survive in a diverse range of environments including soil, stalactites and cave sediments. Additionally, we identify various extremotolerant SRB in similar Poole's Cavern environments. We show that these SRB and MTB can move successfully into subsurface environments and adapt concomitantly to the anomalous pH, saline, and relatively nutrient-poor conditions found in Poole's Cavern. These findings are significant to our understanding of microorganisms on early Earth because it is believed, but not proven, that underground environments might have been hot spots for early microbial life. We expect that these early bacteria would have been able to adopt similar adaptation strategies, transferring and acclimatizing to underground environments, in ways comparable to the SRB and MTB identified in this study.

Caves are complex ecosystems with various microbial habitats. Understanding the individual community structures in the key source environments (soils, waters) and those in the sinks (speleothems, cave muds) can help elucidate the extent to which in-cave communities are a function of their source communities, or if they can successfully adapt and diversify locally. Here, we assess the network of microbial communities existing within a unique British cave system. Poole's Cavern is characterized by alkalinity or even hyperalkalinity (pH > 9) in its drip waters, creating a series of challenging ecological niches for microbes to survive. Samples of soil, drip water, speleothem, and cave sediment were collected for chemical characterization, cell culture assays and DNA sequencing analysis. We show that microbial abundance and diversity were highest in the soils proximal to the cave, and the microbiotas of the hyperalkaline cave chamber were less abundant and less diverse than the cave chamber with lower pH. Proteobacteria and Planctomycetota were the most prevalent bacterial phyla throughout the cave system irrespective of pH, indicating their members are comparatively more metabolically versatile. Predicted essential metabolic pathways were still dominant within all sampling sites, and microorganisms were shown to be capable of utilizing various inorganic or simple organic compounds to survive. Interestingly, co-occurrence between Poole's samples was limited, never demonstrating more than 50% similarity. This work highlights the diversity of microbial communities within this extreme environment and the development of microbial niches which reflects the adaptation strategy of microorganisms under alkaline-hyperalkaline conditions.

Palaeoclimate records from northern Iberia are becoming increasingly sought after as this region is one of the most southerly terrestrial locations in Europe to have its climate dictated principally by the North Atlantic. Terrestrial records therefore have the potential to offer insights into changing oceanic and atmospheric circulation in the wider North Atlantic region. Cave speleothems offer one of the most promising archives from northern Iberia due to their wide geographic distribution and potential for accurately dated climate reconstruction. Cueva de Asiul, situated in Cantabria (N. Iberia; 43°19'0.63''N, 3°35'28.32''W; 285 m.a.s.l) within the Matienzo karst depression is one such site that offers the potential for palaeoclimate reconstructions. Here we present three years of climate and cave monitoring from Cueva de Asiul, giving detailed insight into local meteorology, hydrology and cave ventilation dynamics. In doing so, this paper presents a background to high resolution, Holocene duration speleothem records which have been extracted from this cave. Annual average cave temperatures are +13.7ºC, with a maximum range of 1ºC, reflecting the seasonality of external air temperature (average external temperature +13.8°C). Cave ventilation is controlled by changes in external air temperature and variations in external air pressure during low pressure events. Local rainfall measurements show an average of 1400 mm/year with the majority of rainfall occurring during the winter, with periods of water excess between October and April. Speleothem drip rates are characterised by summer lows and a rapid transition to higher rates at the onset of the winter season. Stable isotope analysis (δ18O, δ2H) indicate that aquifer water is derived predominantly from the previous year’s rainfall and the rainfall feeding the karst system is controlled by a strong amount effect. Speleothems from this site are potentially suited to preserving extended records of rainfall amount in no

The increasing carbon dioxide (CO2) concentration in the atmosphere in combination with climatic changes throughout the last century are likely to have had a profound effect on the physiology of trees: altering the carbon and water fluxes passing through the stomatal pores. However, the magnitude and spatial patterns of such changes in natural forests remain highly uncertain. Here, stable carbon isotope ratios from a network of 35 tree-ring sites located across Europe are investigated to determine the intrinsic water-use efficiency (iWUE), the ratio of photosynthesis to stomatal conductance from 1901 to 2000. The results were compared with simulations of a dynamic vegetation model (LPX-Bern 1.0) that integrates numerous ecosystem and land-atmosphere exchange processes in a theoretical framework. The spatial pattern of tree-ring derived iWUE of the investigated coniferous and deciduous species and the model results agreed significantly with a clear south-to-north gradient, as well as a general increase in iWUE over the 20th century. The magnitude of the iWUE increase was not spatially uniform, with the strongest increase observed and modelled for temperate forests in Central Europe, a region where summer soil-water availability decreased over the last century. We were able to demonstrate that the combined effects of increasing CO2 and climate change leading to soil drying have resulted in an accelerated increase in iWUE. These findings will help to reduce uncertainties in the land surface schemes of global climate models, where vegetation-climate feedbacks are currently still poorly constrained by observational data., AuthorCount:31

RATIONALE The organic content of speleothem calcite is a well-recognized component of their chemical composition. To date, the techniques for interpretation of this material include UV fluorescence, FTIR spectroscopy and biomarker analysis using gas chromatography/mass spectroscopy (GC/MS). However, investigation of the minute concentrations of molecules in speleothems demands careful sampling and laboratory controls. METHODS To be certain extracted molecules were encapsulated at the time of speleothem growth and do not represent contamination, we submitted three pieces of speleothem calcite to a rigorous extraction procedure. Based on sequential digestion and analysis by GC/MS, we measured concentration profiles of individual compounds with increasing distance from sample surfaces. RESULTS Declining concentrations toward interior extracts identified cholesterol, phthalates, and n-alkanes as surface contaminants. In contrast, iodo organic compounds had homogeneous concentration profiles and were also significantly above laboratory background levels, consistent with an indigenous origin. However, further laboratory testing demonstrated that iodo organics were produced by the reaction of iodine derived from the speleothem with solvent additives and other impurities of the extraction procedure. Sitosterol and some fatty acids demonstrated distributions which were probably indigenous to the speleothem archive, thus recording environmental conditions commensurate with time of growth. CONCLUSIONS We do not aim to provide an environmental interpretation of extracted molecules, but highlight the caution necessary before doing so. We ultimately establish a framework for differentiating between organic constituents that are introduced to the speleothems during storage, handling and as artifacts of extraction, and those encapsulated in situ at the time of growth.

Monitoring in Ingleborough Show Cave (N. Yorkshire, UK) reveals the influence of tourism and cave management techniques on different parameters of the cave atmosphere. Exploratory aerosol monitoring identified a 0.015 +/- 0.03 mg/m(3) (approximate to 70%) reduction in airborne particulates within the first 75 meters of cave passage and two major aerosol sources within this artificially ventilated show cave. Autogenic aerosol production was identified close to active stream ways (increases of

There is a shortage of archives of sulfur that can be used to investigate industrial orvolcanic pollution in terrestrial catchments, but the role of S as a nutrient, coupled with sparse published evidence, suggests that trees are promising targets. We focused on two conifer species (Picea abies (L.) Karst and Abies alba Miller) from an Alpine site in NE Italy. Bulk analyses of Abies demonstrate that S concentrations were higher in the second half of the 20th century but with some high outliers possibly reflecting particulate impurities. X-ray synchrotron analyses confirmed the observed time trend, which is similar to that of a nearby stalagmite, and reflects an atmospheric pollution record mediated by storage in the soil and ecosystem. S and P were found to be localized in the inner cell wall (ca. 2 microm wide), local thickenings of which probably account for some outlying high values of S in synchrotron studies. S occurs as a mixture of oxidation states (0 to +0.5, +2, +5, and +6) which are consistent in space and time. The results indicate that wood older than a few years contains archive-quality S but that robust conclusions require multiple replicate analyses.

Determination of annual lamination provides important additional constraints to radiometric dates on speleothems, both for dating the duration of specific growth intervals and optimizing growth models. In the absence of visible laminae, however, speleothem age models are reliant upon curve fitting through discretely dated points and are therefore inherently more uncertain than annual chronologies from laminae. Given that the impact of seasonality on speleothems is expected to be strong enough to generate an annual pulse in trace element chemistry regardless of whether or not visible or fluorescent growth laminae are visible, we demonstrate the potential for deriving high-resolution stalagmite chronologies from non-laminated samples using annual chemical variations in stalagmites from two Alpine caves (Obir, Austria and Ernesto, NE Italy). Trace element data were obtained by ion microprobe analyses for H, P, Mg, Na, Sr and Ba and the annual signal was sought using spectral and wavelet analysis. An automated chemical peak-counting software tool was developed in Matlab©. It counts significant peaks using criteria of 1) minimum amplitude in relation to the local standard deviation of signal variation and 2) minimum separation between peaks. Verification of the tool using visibly-laminated samples suggests the software is a reliable and accurate method of chronology building, with hit ratios greater than 0.93 and less than 0.75% false alarm occurrences. Used in conjunction with other dating methods such as radiocarbon, U-Th and sulphur peak dating, the automated chemical laminae chronology-building approach would provide a more meaningful alternative to simple age-depth curve fitting for non-laminated samples.

We combine surface and cave climate monitoring with multiple stalagmite parameters to help understand and calibrate the climate records contained within stalagmites from a region with strong rainfall seasonality. Two actively growing stalagmites from Ethiopia were analysed in order to investigate the climate signal contained within d18O and growth rate parameters. The d18O and growth rate of the two stalagmites give different responses to surface climate due to variations in the climate signal transfer. Both stalagmites (Merc-1 and Asfa-3) have a climate response that is seasonal; however this signal is subsequently smoothed by the mixing of event and storage water within the aquifer. Merc-1 responds more to high frequency (‘event’) climate, due to a greater ratio of event to storage water in this sample, whereas Asfa-3 responds more to low frequency (‘storage’) climate. In addition, different parameters respond to different seasons. For example, stalagmite Asfa-3, from greater depth from the surface and with a slow drip rate, has a growth rate that responds to the amount of summer rain. In contrast, Merc-1, closer to the surface and with a faster drip rate, exhibits no clear response to surface climate, probably due to a more complex climate signal transfer. d18O response varies with stalagmite due to the interplay between rainfall forcing factors (amount, seasonality) and disequilibrium kinetics, with opposing correlations between seasonal rainfall and d18O between the samples. Our results demonstrate that analysis of seasonal climate forcing, and transfer functions reflecting the mixing of event and storage water, may be the most appropriate approach to develop of transfer functions appropriate for highresolution, stalagmite climate reconstruction.

This paper describes detailed budgets of water, Cl), dissolved Si and both inorganic and organic forms of nitrogen and phosphorus for two small glacier basins in Arctic Svalbard (Midre Love´nbreen and AustreBrøggerbreen). Rates of nutrient deposition are modest, dominated by inorganic nitrogen and episodically enhanced by extreme events. Hence deposition rates are also variable, ranging from 20 to 72 kg NO3-N km)2 a)1 and 10–37 kg NH4-N km)2 a)1 over just two consecutive years. Deposition of dissolved organic and particulate forms of nitrogen (DONand PN respectively) also appears significant and therefore requires further investigation (3–8 kg DONN km)2 and 7–26 kg PN-N km)2 during winter – no summer data are available). Evidence for microbially mediated nutrient cycling within the glacial system is clear in the nutrient budgets, as is the release of large phosphorus, Si and organic/particulate nitrogen fluxes by subglacial erosion. The latter is entirely dependent upon the presence of subglacial drainage, promoting silicate mineral dissolution and the erosion of largely unweathered apatite. The large DON and PN fluxes are surprising and may relate to young organic nitrogen associated with microbial life within the glaciers. This is because wide spread assimilation of NH4 + and perhaps even nitrification occurs on the glacier surface, most likely within abundant cryoconite holes. Further microbial activity also occurs at the glacier bed, where denitrification and sulphate reduction is now known to take place. Thus a two component ‘glacial ecosystem’ is proposed that is highly sensitive to climate change.

This paper examines the water budget and surface energy balance of a Svalbard glacier (midre Lovénbreen) over a 6 year period (1997-2002). Fresh-water yields are found to lie between 1.1 and 1.5 m a−1 and reflect variable amounts of glacier ice ablation (0.27 ± 0.15 m a−1) and more consistent amounts of snowmelt and summer precipitation (0.40 ± 0.10 and 0.49 ± 0.12 m respectively). Between 24% and 36% of the annual runoff is thought to pass through a subglacial drainage system. Although the site is heavily influenced by stable maritime air masses during the summer, surface melting is achieved largely by net shortwave radiation fluxes (74-100% of ablation). Water budget analysis shows that the annual runoff yields may be strongly influenced by water storage within the glacial system. Storage can occur over the winter period and force the early development of the subglacial drainage system during the following summer. Thus annual water fluxes from this glacier cannot be estimated from glacial mass-balance data alone and there is a need to assess the implications of overwinter storage for our understanding of glacial dynamics, annual fluvial process rates and mixing processes in Svalbard's fjords.