Evaluation of spore wall chemistry as a novel biochemical proxy for UV·B radiation

The stratospheric ozone layer provides protection for Earth's land-based organisms against harmful ultraviolet (UV) radiation, but the past century has seen the ozone layer compromised as a result of human activity, resulting in commensurate variations in surface UV -B flux. Despite the importance of UV radiation to the well-being of life, reliable records of surface UV-B flux only exist for a short period of time (20-30 years). In order to gain a deeper understanding of the behaviour of ozone and UV-B flux in the past, an alternative method of determining UV-B is required. Changes in spore chemistry have been proposed as a palaeo-monitor of UV-B flux, which can then be related to stratospheric ozone abundance. By employing the rapid and inexpensive technique of FTIR microspectroscopy to investigate changes in spore chemistry, a large dataset spanning seven different spatial and temporal UV regimes has been generated in order to evaluate the feasibility of routine usage of a spore-based UV-B proxy. Exploring contemporary samples grown under controlled UV conditions and spores preserved in historical archives reveals that modem-day and recent spore chemistry show a positive relationship with known and calculated UV-B flux, with additional environmental factors such as cloudiness and vegetation canopy cover superimposed on these results. Examination of fossil spores obtained from sediments and experimentally matured specimens provides an insight into the chemical changes that occur in organic matter after incorporation into sediments, even under mild burial conditions. This thesis explores the potential of spore chemistry to act as a proxy monitor of past UV-B flux and is the first concerted attempt at applying FTIR spectroscopy to the investigation of spore chemistry in this way

Ginkgo leaf cuticle chemistry across changing pCO2 regimes

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 impact of oxidation on spore and pollen chemistry

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

Spectroscopy and thermal modelling of the first interstellar object 1I/2017 U1 ‘Oumuamua

During the formation and evolution of the Solar System, significant numbers of cometary and asteroidal bodies were ejected into interstellar space. It is reasonable to expect that the same happened for planetary systems other than our own. Detection of such interstellar objects would allow us to probe the planetesimal formation processes around other stars, possibly together with the effects of long-term exposure to the interstellar medium. 1I/2017 U1 ‘Oumuamua is the first known interstellar object, discovered by the Pan-STARRS1 telescope in October 2017. The discovery epoch photometry implies a highly elongated body with radii of ~ 200 × 20 m when a comet-like geometric albedo of 0.04 is assumed. The observable interstellar object population is expected to be dominated by comet-like bodies in agreement with our spectra, yet the reported inactivity of 'Oumuamua implies a lack of surface ice. Here, we report spectroscopic characterization of ‘Oumuamua, finding it to be variable with time but similar to organically rich surfaces found in the outer Solar System. We show that this is consistent with predictions of an insulating mantle produced by long-term cosmic ray exposure. An internal icy composition cannot therefore be ruled out by the lack of activity, even though ‘Oumuamua passed within 0.25 au of the Sun

TRIPPy: Trailed Image Photometry in Python

Photometry of moving sources typically suffers from reduced signal-to-noise (SNR) or flux measurements biased to incorrect low values through the use of circular apertures. To address this issue we present the software package, TRIPPy: TRailed Image Photometry in Python. TRIPPy introduces the pill aperture, which is the natural extension of the circular aperture appropriate for linearly trailed sources. The pill shape is a rectangle with two semicircular end-caps, and is described by three parameters, the trail length and angle, and the radius. The TRIPPy software package also includes a new technique to generate accurate model point-spread functions (PSF) and trailed point-spread functions (TSF) from stationary background sources in sidereally tracked images. The TSF is merely the convolution of the model PSF, which consists of a moffat profile, and super sampled lookup table. From the TSF, accurate pill aperture corrections can be estimated as a function of pill radius with a accuracy of 10 millimags for highly trailed sources. Analogous to the use of small circular apertures and associated aperture corrections, small radius pill apertures can be used to preserve signal-to-noise of low flux sources, with appropriate aperture correction applied to provide an accurate, unbiased flux measurement at all SNR.Comment: 8 Figures, 11 Pages, Accepted to the Astronomical Journa

Palaeoproxies: botanical monitors and recorders of atmospheric change

The integration of plant and Earth sciences offers the opportunity to develop and test palaeobotanical monitors and recorders (palaeoproxies) of past atmospheric change that are understood from a mechanistic perspective, with the underpinning responses being identified and understood at the genetic level. This review highlights how this approach has been used to deliver two distinct palaeoproxies. The first is based on the negative relationship between stomata (breathing pores found on the leaf surface) and atmospheric CO2 concentration; the second is based on tracking chemical changes seen in the composition of pollen and spores to reconstruct changes in the flux of UV-B radiation on the Earth's surface and from this infer changes in stratospheric processes linked to the eruption and emplacement of Large Igneous Provinces. Here, we highlight the potential of integrating a new rapid, inexpensive chemical analysis technique with existing, robust palynological methods, opening the door to a deeper understanding of past environments via the palaeobiological record. A look to the future suggests a combined solar radiation–CO2 concentration approach could be readily applied across the geological record

Proxy reconstruction of ultraviolet-B irradiance at the Earth’s surface, and its relationship with solar activity and ozone thickness

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

Chemotaxonomy as a tool for interpreting the cryptic diversity of Poaceae pollen

The uniform morphology of different species of Poaceae (grass) pollen means that identification to below family level using light microscopy is extremely challenging. Poor taxonomic resolution reduces recoverable information from the grass pollen record, for example, species diversity and environmental preferences cannot be extracted. Recent research suggests Fourier Transform Infra-red Spectroscopy (FTIR) can be used to identify pollen grains based on their chemical composition. Here, we present a study of twelve species from eight subfamilies of Poaceae, selected from across the phylogeny but from a relatively constrained geographical area (tropical West Africa) to assess the feasibility of using this chemical method for identification within the Poaceae family. We assess several spectral processing methods and use K-nearest neighbour (k-nn) analyses, with a leave-one-out cross-validation, to generate identification success rates at different taxonomic levels. We demonstrate we can identify grass pollen grains to subfamily level with an 80% success rate. Our success in identifying Poaceae to subfamily level using FTIR provides an opportunity to generate high taxonomic resolution datasets in research areas such as palaeoecology, forensics, and melissopalynology quickly and at a relatively low cost

Col-OSSOS: Colors of the Interstellar Planetesimal 1I/`Oumuamua

The recent discovery by Pan-STARRS1 of 1I/2017 U1 (`Oumuamua), on an unbound and hyperbolic orbit, offers a rare opportunity to explore the planetary formation processes of other stars, and the effect of the interstellar environment on a planetesimal surface. 1I/`Oumuamua's close encounter with the inner Solar System in 2017 October was a unique chance to make observations matching those used to characterize the small-body populations of our own Solar System. We present near-simultaneous g$^\prime$, r$^\prime$, and J photometry and colors of 1I/`Oumuamua from the 8.1-m Frederick C. Gillett Gemini North Telescope, and $gri$ photometry from the 4.2 m William Herschel Telescope. Our g$^\prime$r$^\prime$J observations are directly comparable to those from the high-precision Colours of the Outer Solar System Origins Survey (Col-OSSOS), which offer unique diagnostic information for distinguishing between outer Solar System surfaces. The J-band data also provide the highest signal-to-noise measurements made of 1I/`Oumuamua in the near-infrared. Substantial, correlated near-infrared and optical variability is present, with the same trend in both near-infrared and optical. Our observations are consistent with 1I/`Oumuamua rotating with a double-peaked period of $8.10 \pm 0.42$ hours and being a highly elongated body with an axial ratio of at least 5.3:1, implying that it has significant internal cohesion. The color of the first interstellar planetesimal is at the neutral end of the range of Solar System $g-r$ and $r-J$ solar-reflectance colors: it is like that of some dynamically excited objects in the Kuiper belt and the less-red Jupiter Trojans.Comment: Accepted to ApJ