Carme Huguet

An interlaboratory study of TEX86 and BIT analysis using high‐performance liquid chromatography–mass spectrometry

Recently, two new proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) were proposed, i.e., the TEX86 proxy for sea surface temperature reconstructions and the BIT index for reconstructing soil organic matter input to the ocean. In this study, fifteen laboratories participated in a round robin study of two sediment extracts with a range of TEX86 and BIT values to test the analytical reproducibility and repeatability in analyzing these proxies. For TEX86 the repeatability, indicating intralaboratory variation, was 0.028 and 0.017 for the two sediment extracts or +/-1-2°C when translated to temperature. The reproducibility, indicating among-laboratory variation, of TEX86 measurements was substantially higher, i.e., 0.050 and 0.067 or +/-3-4°C when translated to temperature. The latter values are higher than those obtained in round robin studies of Mg/Ca and U37 k paleothermometers, suggesting the need to primarily improve compatibility between labs. The repeatability of BIT measurements for the sediment with substantial amounts of soil organic matter input was relatively small, 0.029, but reproducibility was large, 0.410. This large variance could not be attributed to specific equipment used or a particular data treatment. We suggest that this may be caused by the large difference in the molecular weight in the GDGTs used in the BIT index, i.e., crenarchaeol versus the branched GDGTs. Potentially, this difference gives rise to variable responses in the different mass spectrometers used. Calibration using authentic standards is needed to establish compatibility between labs performing BIT measurements.

Distribution of Intact and Core Membrane Lipids of Archaeal Glycerol Dialkyl Glycerol Tetraethers among Size-Fractionated Particulate Organic Matter in Hood Canal, Puget Sound

ABSTRACT There is great interest in the membrane lipids of archaea (glycerol dialkyl glycerol tetraethers [GDGTs]) as tracers of archaeal biomass because of their utility as paleoproxies and because of the biogeochemical importance of archaea. While core GDGTs (formed by hydrolysis of polar head groups of intact GDGTs after cell death) are appropriate for paleostudies, they have also been used to trace archaeal populations. Also, despite the small size (0.2 by 0.7 μm) of cultivated marine archaea, 0.7-μm glass-fiber filters (GFFs) are typically used to collect GDGTs from natural waters. We quantified both core and intact GDGTs in free-living (0.2- to 0.7-μm), suspended (0.7- to 60-μm), and aggregate (>60-μm) particle size fractions in Puget Sound (Washington State). On average, the free-living fraction contained 36% of total GDGTs, 90% of which were intact. The intermediate-size fraction contained 62% of GDGTs, and 29% of these were intact. The aggregate fraction contained 2% of the total GDGT pool, and 29% of these were intact. Our results demonstrate that intact GDGTs are largely in the free-living fraction. Because only intact GDGTs are present in living cells, protocols that target this size fraction and analyze the intact GDGT pool are necessary to track living populations in marine waters. Core GDGT enrichment in larger-size fractions indicates that archaeal biomass may quickly become attached or entrained in particles once the archaea are dead or dying. While the concentrations of the two pools were generally not correlated, the similar sizes of the core and intact GDGT pools suggest that core GDGTs are removed from the water column on timescales similar to those of cell replication, on timescales of days to weeks.

A method for upscaling soil parameters for use in a dynamic modelling assessment of water quality in the Pyrenees

Dynamic modelling of hydrochemistry is a valuable tool to study and predict the recovery of surface waters from acidification, and to assess the effects of confounding factors (such as delayed soil response and changing climate) that cause hysteresis during reversal from acidification. The availability of soil data is often a limitation for the regional application of dynamic models. Here we present a method to upscale site-specific soil properties to a regional scale in order to circumvent that problem. The method proposed for upscaling relied on multiple regression models between soil properties and a suite of environmental variables used as predictors. Soil measurements were made during a field survey in 13 catchments in the Pyrenees (NW Spain). The environmental variables were derived from mapped or remotely sensed topographic, lithological, land-cover, and climatic information. Regression models were then used to model soil parameters, which were supplied as input for the biogeochemical model MAGIC (Model for Acidification of Groundwater In Catchments) in order to reconstruct the history of acidification in Pyrenean lakes and forecast the recovery under a scenario of reduced acid deposition. The resulting simulations were then compared with model runs using field measurements as input parameters. These comparisons showed that regional averages for the key water and soil chemistry variables were suitably reproduced when using the modelled parameters. Simulations of water chemistry at the catchment scale also showed good results, whereas simulated soil parameters reflected uncertainty in the initial modelled estimates.