Dr Wes Fraser

Sporomorphs (pollen and spores) are a mainstay of research into past vegetation, and increasingly sporomorph chemistry is being used as a palaeoecological tool. To make extant sporomorphs directly comparable to fossil specimens, fresh material is processed to remove labile compounds and isolate the sporopollenin wall. A range of processing approaches are currently in use, but the chemistries produced by these different techniques have not yet been compared across a range of taxa. It is therefore not clear how they compare in terms of efficiently isolating sporopollenin without changing its chemical structure, and what impact they have on relative chemical similarities and differences among taxa (i.e. whether more closely related species will always appear chemically more similar, regardless of how they have been processed). Here, we test this by applying five different processing approaches to sporomorphs from 15 taxa from across the vascular plant phylogeny. We show that each approach has its own idiosyncrasies in terms of impacts on sporomorph chemistry. For the most part a common pattern of among-taxon chemical variability is uncovered, and a phylogenetic signal within sporopollenin chemistry is supported. Working with spectral derivatives generally increases agreement among the different processing approaches, but decreases the strength of the phylogenetic signal. No one processing approach is ideal, and the choice of which to use is likely to depend on the goal of the study, the type and quantity of material being processed, and the laboratory facilities available for processing.

Land plants can adjust the concentration of protective UV-B-absorbing compounds (UACs) in the outer wall of their reproductive propagules in response to ambient UV-B flux. To infer changes in UV-B-radiation flux at the Earth’s surface during the end-Permian mass extinction, we analyze UAC abundances in ca. 800 pollen grains from an independently-dated Permian-Triassic boundary section in Tibet. Our data reveal an excursion in UACs that coincide with a spike in mercury concentration and a negative carbon-isotope excursion in the latest Permian deposits, suggesting a close temporal link between large-scale volcanic eruptions, global carbon- and mercury-cycle perturbations, and ozone-layer disruption. Because enhanced UV-B radiation can exacerbate the environmental deterioration induced by massive magmatism, ozone depletion is considered a compelling ecological driver for the terrestrial mass extinction.

Lithium (Li) isotopes are a tracer of silicate weathering processes, but how they react to different components of organic and plant-assisted weathering is poorly known. To examine the effect of organic acids compared to a strong mineral acid (HCl) on Li isotope behaviour, basalt-water weathering experiments were amended with different organic acids (glycine, malic acid, cinnamic acid, and humic acid; 0.01 M). The presence of the different acids significantly affects the behaviour of dissolved elemental concentrations (such as Mg, Fe, and Al), both by increasing primary rock dissolution and hindering rates of secondary mineral formation. However, the behaviour of Li isotopes appears unaffected, with all experiments following an almost identical trend of δ7Li versus Li/Na. This observation was consistent with a single fractionation factor during the uptake of Li into secondary minerals, yet both calculated saturation states and leaching experiments on the reacted solids indicated that Li was removed into multiple phases, suggesting that the bulk combined fractionation factor barely varied. Of the Li lost from solution in the organic experiments, we estimated that on average 76% went into neoformed clays, 16% into oxides/oxyhydroxides, and 10% into the exchangeable fraction. The fractionations observed for each phase were Δ7Liexch-soln = −12.7 ± 1.7‰, Δ7Liox-soln = −26.7 ± 0.4‰, and Δ7Liclay-soln = −21.6 ± 3.3‰. These fractionations were identical, within error, to those from experiments with organic-free water, implying that the Li isotope behaviour was unaffected by the presence of organic acids in the weathering reaction. This result has interesting consequences for the interpretation of Li isotopes in terms of plant-assisted weathering and the geological record of terrestrialisation. In particular, it appears to imply that seawater Li isotope records can be expected to resolve the integrated effect of plants on weathering fluxes or weathering congruence, rather than being sensitive to specific organic-mediated weathering mechanisms.

Sporopollenin is a highly resistant biopolymer that forms the outer wall of pollen and spores (sporomorphs). Recent research into sporopollenin chemistry has opened up a range of new avenues for palynological research, including chemotaxonomic classification of morphologically cryptic taxa. However, there have been limited attempts to directly integrate extant and fossil sporopollenin chemical data. Of particular importance is the impact of sample processing to isolate sporopollenin from fresh sporomorphs, and the extent of chemical changes that occur once sporomorphs enter the geological record. Here, we explore these issues using Fourier transform infrared (FTIR) microspectroscopy data from extant and fossil grass, Nitraria (a steppe plant), and conifer pollen. We show a 98% classification success rate at subfamily level with extant grass pollen, demonstrating a strong taxonomic signature in isolated sporopollenin. However, we also reveal substantial chemical differences between extant and fossil sporopollenin, which can be tied to both early diagenetic changes acting on the sporomorphs and chemical derivates of sample processing. Our results demonstrate that directly integrating extant and late Quaternary chemical data should be tractable as long as comparable sample processing routines are maintained. Consistent differences between extant and deeper time sporomorphs, however, suggests that classifying fossil specimens using extant training sets will be challenging. Further work is therefore required to understand and simulate the effects of diagenetic processes on sporopollenin chemistry.

Solar ultraviolet-B (UV-B) irradiance that reaches the Earth’s surface acts as a biotic stressor and has the potential to modify ecological and environmental functioning. The challenges of reconstructing ultraviolent (UV) irradiance prior to the satellite era mean that there is uncertainty over long-term surface UV-B patterns, especially in relation to variations in solar activity over centennial and millennial timescales. Here, we reconstruct surface UV-B irradiance over the last 650 years using a novel UV-B proxy based on the chemical signature of pollen grains. We demonstrate a statistically significant positive relationship between the abundance of UV-B absorbing compounds in Pinus pollen and modelled solar UV-B irradiance. These results show that trends in surface UV-B follow the overall solar activity pattern over centennial timescales, and that variations in solar output are the dominant control on surface level UV-B flux, rather than solar modulated changes in ozone thickness. The Pinus biochemical response demonstrated here confirms the potential for solar activity driven surface UV-B variations to impact upon terrestrial biotas and environments over long timescales.

Solar ultraviolet-B (UV-B) irradiance that reaches the Earth’s surface acts as a biotic stressor and has the potential to modify ecological and environmental functioning. The challenges of reconstructing ultraviolent (UV) irradiance prior to the satellite era mean that there is uncertainty over long-term surface UV-B patterns, especially in relation to variations in solar activity over centennial and millennial timescales. Here, we reconstruct surface UV-B irradiance over the last 650 years using a novel UV-B proxy based on the chemical signature of pollen grains. We demonstrate a statistically significant positive relationship between the abundance of UV-B absorbing compounds in Pinus pollen and modelled solar UV-B irradiance. These results show that trends in surface UV-B follow the overall solar activity pattern over centennial timescales, and that variations in solar output are the dominant control on surface level UV-B flux, rather than solar modulated changes in ozone thickness. The Pinus biochemical response demonstrated here confirms the potential for solar activity driven surface UV-B variations to impact upon terrestrial biotas and environments over long timescales.

Cuticles have been a key part of palaeobotanical research since the mid-19th Century. Recently, cuticular research has moved beyond morphological traits to incorporate the chemical signature of modern and fossil cuticles, with the aim of using this as a taxonomic and classification tool. For this approach to work, cuticle chemistry would have to maintain a strong taxonomic signal, with a limited input from the ambient environment in which the plant grew. Here, we use attenuated total reflectance Fourier Transform infrared (ATR-FTIR) spectroscopy to analyse leaf cuticles from Ginkgo biloba plants grown in experimentally enhanced CO2 conditions, to test for the impact of changing CO2 regimes on cuticle chemistry. We find limited evidence for an impact of CO2 on the chemical signature of Ginkgo cuticles, with more pronounced differences demonstrated between the abaxial (lower leaf surface) and adaxial (upper leaf surface) cuticles. These findings support the use of chemotaxonomy for plant cuticular remains across geological timescales, and the concomitant large-scale variations in CO2 concentrations.

The grass family (Poaceae) is one of the most economically important plant groups in the world today. In particular many major food crops, including rice, wheat, maize, rye, barley, oats and millet, are grasses that were 15 domesticated from wild progenitors during the Holocene. Archaeological evidence has provided key information on domestication pathways of different grass lineages through time and space. However, the most abundant empirical archive of floral change – the pollen record – has been underused for reconstructing grass domestication patterns, because of the challenges of classifying grass pollen grains based on their morphology alone. Here, we test the potential of a novel approach for pollen classification based on the chemical signature of the pollen grains, measured using Fourier Transform 20 infrared (FTIR) microspectroscopy. We use a dataset of eight domesticated and wild grass species, classified using k-nearest neighbour classification coupled with leave one out cross validation. We demonstrate a 95% classification success rate on training data, and an 82% classification success rate on validation data. This result shows that FTIR spectroscopy can provide enhanced taxonomic resolution enabling species level assignment from pollen. This will enable the full testing of the timing and drivers of domestication and agriculture through the Holocene.

Silicate weathering is the primary control of atmospheric CO2 concentrations on multiple timescales. However, tracing this process has proven difficult. Lithium isotopes are a promising tracer of silicate weathering. This study has reacted basalt sand with natural river water for ~9 months in closed experiments, in order to examine the behaviour of Li isotopes during weathering. Aqueous Li concentrations decrease by a factor of ~10 with time, and δ7Li increases by ~19‰, implying that Li is being taken up into secondary phases that prefer 6Li. Mass balance using various selective leaches of the exchangeable and secondary mineral fractions suggest that ~12–16% of Li is adsorbed, and the remainder is removed into neoformed secondary minerals. The exchangeable fractionation factors have a Δ7Liexch-soln = −11.6 to −11.9‰, while the secondary minerals impose Δ7Lisecmin-soln = −22.5 to −23.9‰. Overall the experiment can be modelled with a Rayleigh fractionation factor of α = 0.991, similar to that found for natural basaltic rivers. The mobility of Li relative to the carbon-cycle-critical cations of Ca and Mg changes with time, but rapidly evolves within one month to remarkably similar mobilities amongst these three elements. This evolution shows a linear relationship with δ7Li (largely due to a co-variation between aqueous [Li] and δ7Li), suggesting that Li isotopes have the potential to be used as a tracer of Ca and Mg mobility during basaltic weathering, and ultimately CO2 drawdown.

How pollen moves within and between ecosystems affects factors such as the genetic structure of populations, how resilient they are to environmental change, and the amount and nature of pollen preserved in the sedimentary record. We set artificial pollen traps in two 100 m by 100 m vegetation plots, one in a wet evergreen forest, and one in a moist semideciduous forest in Ghana, West Africa. Five traps from each plot were counted annually from 2011 to 2014, to examine spatial and temporal variation in the pollen rain of the most abundant taxa shared between pollen and vegetation assemblages. Samples from the wet evergreen plot exhibited high variability within years, with the dominant pollen types changing between samples, and many pollen taxa being over-represented relative to their parent plant abundance in some traps whilst being entirely absent from others. The most abundant plant taxa of the wet evergreen plot (Drypetes and Cynometra) do, however, constitute major components of the pollen rain. There is less variation between samples from the moist semi-deciduous plot spatially, as it is dominated by Celtis, which typically comprises >70% of the pollen assemblages. We conclude that pollen rain in these tropical ecosystems is highly heterogeneous, and suggest that pollen assemblages obtained by trapping are susceptible to small-scale variations in forest structure. Conversely, this may mean that current recommendations of more than three years of trapping in tropical systems may be too high, and that space could substitute for time in modern tropical pollen trapping.

Zero tillage management of agricultural soils has potential for enhancing soil carbon (C) storage and reducing greenhouse gas emissions. However, the mechanisms which control carbon (C) sequestration in soil in response to zero tillage are not well understood. The aim of this study was to investigate the links between zero tillage practices and the functioning of the soil microbial community with regards to C cycling, testing the hypothesis that zero tillage enhances biological functioning in soil with positive implications for C sequestration. Specifically, we determined microbial respiration rates, enzyme activities, carbon source utilization and the functional chemistry of the soil organic matter in temperate well drained soils that had been zero tilled for seven years against annually tilled soils. Zero tilled soils contained 9% more soil C, 30% higher microbial biomass C than tilled soil and an increased presence of aromatic functional groups indicating greater preservation of recalcitrant C. Greater CO2 emission and higher respirational quotients were observed from tilled soils compared to zero tilled soils while microbial biomass was 30% greater in zero tilled soils indicating a more efficient functioning of the microbial community under zero tillage practice. Furthermore, microbial enzyme activities of dehydrogenase, cellulase, xylanase, β-glucosidase, phenol oxidase and peroxidase were higher in zero tilled soils. Considering zero tillage enhanced both microbial functioning and C storage in soil, we suggest that it offers significant promise to improve soil health and support mitigation measures against climate change.

The original report that plants emit methane (CH4) under aerobic conditions caused much debate and controversy. Critics questioned experimental techniques, possible mechanisms for CH4 production and the nature of estimating global emissions. Several studies have now confirmed that aerobic CH4 emissions can be detected from plant foliage but the extent of the phenomenon in plants and the precise mechanisms and precursors involved remain uncertain. In this study, we investigated the role of environmentally realistic levels of ultraviolet (UV) radiation in causing the emission of CH4 and other gases from foliage obtained from a wide variety of plant types. We related our measured emissions to the foliar content of methyl esters and lignin and to the epidermal UV absorbance of the species investigated. Our data demonstrate that the terrestrial vegetation foliage sampled did emit CH4, with a range in emissions of 0.6–31.8 ng CH4 g−1 leaf DW h−1, which compares favourably with the original reports of experimental work. In addition to CH4 emissions, our data show that carbon monoxide, ethene and propane are also emitted under UV stress but we detected no significant emissions of carbon dioxide or ethane.

The nesting habits of ants play an important role in structuring ant populations. They vary from monodomy, a colony occupies a single nest, via polydomy, a colony occupies multiple adjacent nests, to supercoloniality, a colony spans over large territories comprising dozen to thousands nests without having any boundaries. The population structure of the desert ant Cataglyphis niger, previously considered to form supercolonies, was studied using genetic, chemical, and behavioral tools in plots of 50 × 50 m at two distinct populations. At the Palmahim site, the plot comprised 15 nests that according to the genetic analysis constituted three colonies. Likewise at the Rishon Leziyyon site 14 nests constituted 5 genetic colonies. In both sites, both chemical analysis and the behavioral (aggression) tests confirmed the colony genetic architecture. The behavioral tests also revealed that aggression between colonies within a population was higher than that exhibited between colonies of different populations, suggesting the occurrence of the “nasty neighbor” phenomenon. In contrast to supercolony structure previously reported in another population of this species, the presently studied populations were composed of polydomous colonies. However, both the genetic and chemical data revealed that the inter-colonial differences between sites were larger than those within site, suggesting some within-site population viscosity. Thus, C. niger exhibits flexible nesting characteristics, from polydomy to supercoloniality, and can be considered at the brink of supercoloniality. We attribute the differences in population structure among sites to the intensity of intraspecific competition.

Sporomorphs (pollen and spores) have an outer wall composed of sporopollenin. Sporopollenin chemistry contains both a signature of ambient ultraviolet-B flux and taxonomic information, but it is currently unknown how sensitive this is to standard palynological processing techniques. Oxidation in particular is known to cause physical degradation to sporomorphs, and it is expected that this should have a concordant impact on sporopollenin chemistry. Here, we test this by experimentally oxidizing Lycopodium (clubmoss) spores using two common oxidation techniques: acetolysis and nitric acid. We also carry out acetolysis on eight angiosperm (flowering plant) taxa to test the generality of our results. Using Fourier Transform infrared (FTIR) spectroscopy, we find that acetolysis removes labile, non-fossilizable components of sporomorphs, but has a limited impact upon the chemistry of sporopollenin under normal processing durations. Nitric acid is more aggressive and does break down sporopollenin and reorganize its chemical structure, but when limited to short treatments (i.e. ≤10 min) at room temperature sporomorphs still contain most of the original chemical signal. These findings suggest that when used carefully oxidation does not adversely affect sporopollenin chemistry, and that palaeoclimatic and taxonomic signatures contained within the sporomorph wall are recoverable from standard palynological preparations.

The biopolymer sporopollenin present in the spore/pollen walls of all land plants is regarded as one of the most recalcitrant biomacromolecules (biopolymers), providing protection against a range of abiotic stresses. This long-term stability is demonstrated by the near-ubiquitous presence of pollen and spores in the fossil record with spores providing the first evidence for the colonization of the land.Here, we report for the first time chemical analyses of geologically unaltered sporopollenin from Pennsylvanian (c. 310million yr before present (MyBP)) cave deposits.Our data show that Pennsylvanian Lycophyta megaspore sporopollenin has a strong chemical resemblance to extant relatives and indicates that a co-polymer model of sporopollenin formation is the most likely configuration.Broader comparison indicates that extant sporopollenin structure is similar across widely spaced phylogenetic groups and suggests land plant sporopollenin structure has remained stable since embryophytes invaded land.

Current attempts to develop a proxy for Earth's surface ultraviolet-B (UV-B) flux focus on the organic chemistry of pollen and spores because their constituent biopolymer, sporopollenin, contains UV-B absorbing pigments whose relative abundance may respond to the ambient UV-B flux. Fourier transform infrared (FTIR) microspectroscopy provides a useful tool for rapidly determining the pigment content of spores. In this paper, we use FTIR to detect a chemical response of spore wall UV-B absorbing pigments that corresponds with levels of shade beneath the canopy of a high-latitude Swedish birch forest. A 27% reduction in UV-B flux beneath the canopy leads to a significant (p