FTIR spectroscopic features of the pteridosperm Ruflorinia orlandoi and host rock (Springhill Formation, Lower Cretaceous, Argentina)
Introduction
The Springhill Formation is a well-known hydrocarbon source in the subsurface of southern Argentina and Chile. Despite the fact that the Springhill Formation deposits have a wide distribution area, the outcrops in the Santa Cruz province, Argentina, are discontinuous and comprise few locations (Carrizo and Del Fueyo, 2015). Among these, the Río Correntoso locality is characterized by having abundant plant fossil remains mainly as compressions with well-preserved cuticles. They consist of fronds, simple to pinnate leaves, leafy branches showing different degrees of branching, and scale-like leaves belonging to Pteridospermophyta, Bennetittales, Ginkgophyta, and Coniferales (Baldoni, 1977; Carrizo et al., 2014; Carrizo and Del Fueyo, 2015; Carrizo et al., 2019a; Carrizo et al., 2019b; Lafuente Diaz et al., 2019).
Cuticular studies have been especially important for the identification of different plant groups, such as the case of Pteridopspermophyta through the establishing of the first true pteridosperms known from the Springhill Formation, Ruflorinia orlandoi (Carrizo et al., 2014). Moreover, two new records including Ruflorinia sp. and Pteridosperma sp. indet. emphasize the importance of the Mesozoic ferns-like taxa in this unit (Carrizo and Del Fueyo, 2015). Ruflorinia is a foliage genus which was established by Archangelsky (1963) based on plant fossil remains from the Anfiteatro de Ticó Formation (Baqueró Group, Lower Cretaceous) in the Santa Cruz province, Argentina. From this unit, three taxa were erected: Ruflorinia sierra Archangelsky, R. pilifera Archangelsky, and R. papillosa Villar de Seoane (Archangelsky, 1963; Archangelsky, 1964; Villar de Seoane, 2000). Additionally, the cupulate organ Ktalenia circularis Archangelsky and R. sierra foliage were found to represent parts of the same frond system, thus establishing Ruflorinia as a seed fern taxon belonging to Caytoniales (Archangelsky, 1963; Taylor and Archangelsky, 1985).
On the other hand, the cuticular studies have also been focused on the chemical analysis of diagenetically altered compounds preserved in the plant fossils (Holloway, 1982; Nip et al., 1986; Tegelaar et al., 1991; Kerp, 1990; van Bergen et al., 1994; among others). Thus, a wide variety of chemical analysis techniques have been applied to plant fossil studies, including Fourier transform infrared (FTIR) spectroscopy. Over recent decades, the FTIR spectroscopy has been employed to characterize the chemical composition (presence of functional groups) of plant fossil remains mainly from coalified compressions of Devonian, Pennsylvanian, and Triassic from Canada, Czech Republic, Spain, and Brazil, among others (e.g., Pšenicka et al., 2005; D'Angelo, 2006; Zodrow et al., 2009; D'Angelo et al., 2011; Zodrow et al., 2012; Matsumura et al., 2016; Vajda et al., 2017; D'Angelo and Zodrow, 2018; D'Angelo, 2019; Jardine et al., 2019). Plant fossil compressions from Argentina have also been studied using FTIR spectroscopy analyses, such as the cases of the Dicroidium flora from the Triassic of the Mendoza province (central-western Argentina), where Johnstonia coriacea Walkom, Johnstonia stelzneriana Frenguelli, and Dicroidium odontopteroides Gothan, and some other taxa were spectroscopically studied (e.g., D'Angelo, 2006; Zodrow et al., 2009; D'Angelo et al., 2011; D'Angelo and Zodrow, 2018). Recently, the FTIR spectroscopy analyses have been focused on plant fossil remains from the Lower Cretaceous of the Santa Cruz province including the podocarp Squamastrobus tigrensis Archangelsky and Del Fueyo, and the bennettitalean Ptilophyllum micropapillosum Lafuente Diaz, Carrizo, and Del Fueyo (Lafuente Diaz et al., 2018; Lafuente Diaz et al., 2019). In this contribution, different frond parts (pinnae and rachis) of the pteridosperm Ruflorinia orlandoi Carrizo and Del Fueyo from the Springhill Formation are chemically analyzed by semi-quantitative Fourier transform infrared (FTIR) spectroscopy, in order to obtain the first chemical characterization of the mesophyll and cuticle in leaves of this Patagonian taxon. In addition, the associated coal extracted from the host rock is spectroscopically analyzed.
Section snippets
Materials
The specimens were collected by M.A. Carrizo, G.M. Del Fueyo, and M.A. Lafuente Diaz in January 2013 and February 2015 from the Springhill Formation at the Río Correntoso locality (Santa Cruz province, Argentina). The material comprises fourteen rock samples used for both micromorphological and FTIR analyses (Table 1). Additionally, three host rock samples (V1/18, V2/18, and V3/18) were collected from the same fossiliferous level where Ruflorinia orlandoi occurs at the Río Correntoso locality.
Brief characterization of Ruflorinia orlandoi fronds
The description is based on the analyses of thirteen specimens that comprise compressions of incomplete fronds with well-preserved cuticles. The megascopic and micromorphological characters are consistent with those of Ruflorinia orlandoi (Carrizo et al., 2014).
The fronds are at least bipinnate and imparipinnate up to 10.5 cm long and 4.5 cm wide (Fig. 2A and B). The main rachis is conspicuous, bearing pinnae with 6–7 pairs of pinnules; both pinnae and pinnules are alternate to sub-oppositely
Qualitative data from FTIR spectra
The presence of similar functional groups in Cp and Ct samples of R. orlandoi is mainly related to the chemical structure of the cuticle, which is present in both sample forms.
The role of the cuticle in plants consists of numerous functions such as transpiration control, exchange of gases, vapors, polar solutes and lipophilic substances (environment), water and particle repellence, radiation protection, and mechanical support, among others (e.g., Riederer, 2006). Also, the structure and
Conclusions
Foliar remains of the pteridosperm Ruflorinia orlandoi (Lower Cretaceous, Springhill Formation, Santa Cruz province, Argentina) and associated coal (V) samples are studied for the first time by semi-quantitative Fourier transform infrared (FTIR) spectroscopy. The R. orlandoi fronds FTIR analysis considers two sample forms: compressions (Cp) and cuticles (Ct). In turn, different frond parts, pinnae and rachis, are differentiated. From the FTIR spectra, belonging to Cp, Ct, and V samples,
Acknowledgments
The Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) and the Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT) partially supported this contribution by grants: CONICET PIP 2012/12 and ANPCyT PICT 528/12 and 2015-2206, respectively. We thank the two anonymous reviewers for the useful suggestions and comments which have improved the manuscript. Orlando Cárdenas is gratefully acknowledged for his technical assistance to obtain the cuticle samples for anatomical
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