551 research outputs found
The quantitative determination of H and C in cordierite from FTIR + SIMS
No full textCordierite, a microporous mineral stable under geological conditions spanning from the amphibolite facies to UHT metamorphism, is able to incorporate significant H2O and CO2 within its structural channels. As the volatile content of cordierite significantly affects its stability and phase relationships (Harley et al. 2002), their quantitative evaluation is crucial in studies where cordierite is used as a P-T tracer. We present here a calibration for the spectroscopic microanalysis of hydrogen and carbon in cordierite, by combining SIMS and FTIR. The sample used for this study is a transparent single-crystal extracted from a partially melted metapelitic enclave at El Hoyazo (SE Spain). Two fragments were oriented // (010) and (001), doubly polished to 140 μm and analysed using polarized IR radiation. The spectra show that in the examined sample the H2O molecules are oriented with the H...H vector // a (type I water). The absorptions observed in the C-O stretching region can be assigned to both CO2 and CO molecules oriented // a; the spectra also show the presence of 13C in the sample. H and C contents of the cordierite have been measured by SIMS using secondary ion ratios of 1H/28Si and 12C/28Si, under operating conditions of 8 nA and 10 kV for the primary beam of O- ions, 4500 V for the secondary beam, and ion ratios measured at an energy offset of 75 V. The resulting H and C contents allow calibration of the following molar absorption coefficients for H and C in cordierite: H2Oε = 200 ± 40 L/(mol∙cm) linear or H2Oεi = 1500 ± 300 L/(mol∙cm-2) integrated; CO2ε = 800 ± 250 L/(mol∙cm) linear or CO2εi = 11000 ± 4000 l/(mol∙cm-2) integrated.
Harley SL, Thompson P, Hensen BJ and Buick IS (2002) J. Metam. Geol., 20, 71-86
Eriope orlandoi Harley 2023, sp. nov.
No full text<p> <b>Eriope orlandoi</b> <i>Harley</i>, <i>sp. nov</i>. (Figures 1 & 2).</p> <p> Type:— BRAZIL. Bahia: Rio de Contas, ao norte da cidade, na beira da estrada antigamente chamada a Estrada de Ouro, nos arredores da Serra Molhada, 13º 32’ 03” S, 41º 48’ 41” W. alt. 1127 m, campo rupestre, 17 Aug. 2021, (fl.), <i>R.M. Harley & O. Santos</i> 58773 (holotype HUEFS [barcode: 263595]); isotypes RB, SPF).</p> <p> <b>Diagnosis:—</b> <i>Eriope orlandoi</i> is morphologically similar to <i>E. crassifolia</i> Benth., with which it shares the small, ± imbricate, coriaceous and rigid leaves. However, <i>E. orlandoi</i> is much more robust, up to 1 m or more tall, usually with a stout, very woody main stem and a much-branched crown of leaves, while <i>E. crassifolia</i> is a shorter, less branched plant, to c. 60 cm. The leaves of <i>E. orlandoi</i> are with a lamina 0.7–1.3 × 0.7–1.4 cm, rotund and with apex rounded or minutely apiculate, in <i>E. crassifolia</i> the lamina is 0.7–1.0 (1.2) × 0.3–0.4 cm, lanceolate to narrowly ovate, with apex acute. Flowers with fruiting calyx in <i>E. orlandoi</i> to 9 mm long, in <i>E. crassifolia</i> 6–7 mm long. Both species are endemic to the Chapada Diamantina, but while <i>E. orlandoi</i> occur in the Serra das Almas area, <i>E. crassifolia</i> occurs c. 60–80 km to the east of <i>E. orlandoi</i>, in the Serra do Sincorá. Another species, which occurs at high altitudes in Rio de Contas and is sometimes confused with the latter, is <i>E</i>. <i>anamariae</i> Harley. This species can easily be distinguished from <i>E. orlandoi,</i> as the leaves have much longer petioles, at least 3 mm long or usually much more, (usually sessile or up to 2 mm in <i>E</i>. <i>orlandoi</i>).</p> <p> <b>Description:—</b> Shrub to 1 m tall, much branched with very woody, spreading branches, main stems erect, leafless below, with an often rather dense crown of leaves above. Stems usually 1.6–2.0 cm in diameter near the base or rarely in older specimens up to 3.0 cm. with bark brownish grey and longitudinally striate. Younger stems very leafy, with slender semi-setose hairs, especially below and near the nodes, with numerous short, patent hairs. Leaves strongly coriaceous and rigid, spreading to ascending and then weakly imbricate, longer than internodes, petiole 1–2 mm long, with lamina 0.7–1.3 × 0.7–1.4 cm, ± rotund, base weakly cordate, apex rounded or minutely apiculate, margin yellowish, slightly translucent, with teeth very small, acute and thickened, adaxial surface often slightly concave dark green, weakly rugose, with nerves ± impressed, often slightly scabrid with scattered, short, erect hairs, abaxial paler green, nerves reticulate, weakly prominulous, thickened, incrassate, sparsely pilose and with many small, stalked glands. Inflorescence a branched pseudo-raceme of 1-flowered cymes with bracts caducous, branches usually rather short. Axis of the inflorescence with slender spreading, white hairs c. 0.6 mm long, longer and denser at the nodes. Flowers ± remote, with bracts dark usually caducous, pedicels up to c. 3 mm long, slender, spreading or often slightly reflexed; calyx at anthesis c. 3 mm long, greenish-yellow or often slightly blackish, tube c. 1.5–2 mm long, turbinate, with dense, sessile and short-stalked often yellow glands and very short, patent hairs, with or without a pair of slender, linear bracteoles at its base, lobes unequal, c. 2 mm long, widely spreading, broadly deltoid to almost cordate, apiculate, fruiting calyx with pedicel slightly deflexed and with dense white indumentum in throat; corolla dark bluish violet, up to c. 1 cm long, 2-lipped, corolla-tube with basal portion c. 2 mm long, narrowly cylindrical, white, glabrous, abruptly widening above and becoming hairy and pale violet-blue, posterior lip 2-lobed, externally hairy, internally with throat paler, with a white area, usually two-lobed from base, elsewhere deep violaceous with darker longitudinal lines; stamens with filaments white, densely covered with white hairs, anthers yellow, with yellow pollen, style purplish, glabrous. Gynoecium with stylopodium at base of style. Nutlets c. 2.5 × 1.8 mm, broadly ellipsoid and flattened with rotund apex, very dark brown, with very slightly rugose surface, on internal surface at base, with two elongate white, dehiscence scars. Nutlets mucilaginous when wet. (Fruiting material taken from <i>Harley 58824</i>).</p> <p> <b>Distribution and Habitat</b>:—The types of <i>Eriope orlandoi</i> were collected in Southwestern Bahia, in open, flat areas of campo rupestre in sandy soil, often with quartzite grit and near rock outcrops between 1100 and 1430 m altitude. However, the very first collection of this species was made by the author in 1996, under the collection number of Hortênsia Bautista. At that time the collection was considered a possible new species related to <i>Eriope crassifolia</i>, although no further action was taken. So far, we have found only two other populations, although with a substantial number of individuals, especially in that close to the Estrada de Ouro.</p> <p> <b>Phenology</b>:—Flowering was noted especially between March to September, but in some years due to extensive drought, flowering and fruiting did not occur, or was delayed. Fruiting in 2021 occurred extensively in October, and good fruiting material, from almost the same locality as the holotype can be seen in <i>Harley et al. 58824</i>.</p> <p> <b>Conservation Status</b>:—Only a few populations have so far been found, occurring not more than about 12 km apart. As the area of campo rupestre is extensive, much of it has yet to be explored. The main threats to the plants are the increase in cultivation in some areas, especially near Betancourt, although the plants seem to prefer very sandy and stony areas which are mainly unsuitable for cultivation. The population found below the Serra Molhada seems to be restricted to the roadside. However, further exploration of the serra may reveal further populations, as there are still areas that need to be visited, as often happens for plant species with little known, or small size or difficult to identify (e.g. Perrino <i>et al.</i> 2022, Wagensommer <i>et al.</i> 2017). I therefore consider the species as Data Deficient.</p> <p> <b>Etymology:—</b> The epithet honours our local guide, Orlando Santos, whose perspicacity at finding interesting plant species, resulted in the collection of this new species. Originally, he brought me a branch with old fruits, which I immediately recognized as a new species. We subsequently visited the plant on numerous occasions, returning to the populations to make observations over two years at different times of the year.</p> <p> <b>Additional material examined (paratypes):—</b> BRAZIL. Bahia: Rio de Contas; Fazendola, 23° 26’ 57” S, 41° 52 10” W, alt. 1110 m, 16 Nov. 1996, <i>H.P Bautista, Harley, Hind & Roque PCD 4374</i> (CEPEC, HUEFS, K, SPF); Distrito de Mato Grosso, próximo a comunidade Betancourt, 13˚25’56.5” S, 41˚50’52.2” W, alt. 1415 m, 09 Jan. 2018, <i>Harley & Santos 58219</i> (HUEFS); Distrito de Mato Grosso, na trilha para o Pico do Itobira, 13˚22’55”S, 41˚53’34”W, alt. 1412 m, 16 Oct. 2018, <i>Harley et al. 58236</i> (HUEFS); 13˚ 22’55”S, 41˚53’34”W, alt. 1412 m, 16 Oct. 2018, <i>Harley et al. 58238</i> (HUEFS); Proximidades de Betancourt, trilha para o Pico de Itobira, 13º25’52.1” S, 41º50’51.2” W, alt. 1402 m, 27 May 2019, <i>Harley & Giulietti 58395</i> (HUEFS); Bitencourt, na trilha para o Pico de Itobira, 13°25’57.5”S, 41°50’53”W, alt. 1404 m, 22 Nov. 2019, <i>Harley et al. 58460</i> (HUEFS); Estrada de Ouro, Mar. 2020, <i>Santos in Harley 58644</i> (HUEFS); Estrada de Ouro, na base da Serra do Molhado, 13°32’03”S, 41°48’41”W, alt. 1127 m, 21 Oct. 2020, <i>Santos in Harley 58666</i> (HUEFS); ao norte de Rio de Contas, na beira da estrada antigamente chamada de Estrada de Ouro, nos arredores da Serra Molhada, 18 Mar. 2021, <i>Harley</i> & <i>Santos 58689</i> (HUEFS); same locality, in campo rupestre, <i>Harley et al. 58700</i>, 19 May 2021 (HUEFS); Nearby locality, in gerais, 13º 32’ 48” S, 41º 48’ 30” W, alt. 1138 m, 29 Oct. 2021, <i>Harley & Santos 58824</i> (HUEFS).</p>Published as part of <i>Harley, Raymond Mervyn, 2023, A new species Eriope orlandoi (Lamiaceae) from the Chapada Diamantina of Bahia, Brazil, pp. 71-76 in Phytotaxa 591 (1)</i> on pages 72-75, DOI: 10.11646/phytotaxa.591.1.7, <a href="http://zenodo.org/record/7784286">http://zenodo.org/record/7784286</a>
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The quantitative analysis of H2O and CO2 in cordierite using single-crystal polarized-light FTIR microspectroscopy
No full textCordierite is a unique case of a microporous mineral stable under geological conditions spanning from the amphibolite facies to UHT metamorphism to crustal anatexis (Harley et al., 2002; Bertoldi et al., 2004). Because of its structural channels, it is able to trap H2O and CO2 (Armbruster and Bloss, 1980), and for this reason the analysis of the volatile constituents of cordierite may help constraining the geological conditions and the composition of coexisting fluids during its formation (Vry et al., 1990; Harley et al., 2002). It follows that the quantitative evaluation of the channel constituents is crucial in petrologic studies. We address here this point by studying, using a multidisciplinary approach, a set of cordierite samples from different occurrence and with different H2O/CO2 content. The aim of the study was a calibration of reliable absorption coefficients to be used for the quantitative microanalysis of H2O and CO2 in cordierite based on single-crystal polarized-light FTIR spectroscopy. The specimens were fully characterized by a combination of techniques including optical microscopy, single-crystal X-ray diffraction, EMP (electron micro probe), SIMS (secondary ion mass spectrometry), and FTIR spectroscopy. All cordierites are orthorhombic Ccmm; the 2Vα optic axis angle is linearly related to the CO2 content. According to the EMP data, the Si:Al ratio is always close to 5:4; XMg ranges from 76.31 to 96.63 and additional octahedral constituents occur in very weak amounts. Extraframework K and Ca are negligible, while Na may reach values as high as 0.84 apfu. SIM spectrometry shows H2O up to 1.52 and CO2 up to 1.11 wt%. Optically transparent single-crystals were oriented using a spindle-stage and examined under polarized light. On the basis of the literature data and the polarizing behaviour, the observed bands were assigned to water molecules in two different orientations and to CO2 molecules in the structural channels. The spectra also show the presence of 13C and 18O, and weak amounts of CO in the samples. FTIR imaging done using the novel FPA detector system clearly shows that at a m-scale the distribution of H and C in this mineral may be significantly inhomogeneous, and this must be taken into account when collecting analytical data for petrological purposes. This feature is probably less important for carbon molecules than it is for H2O, whose distribution within the crystal can be strongly affected by the geological history of the mineral after its formation.
Armbruster, T. e Bloss, F. D. (1982) Am. Min., 67, 284-91.
Bertoldi, C., Proyer, A., Garbe-Schönberg, D., Behrens, H., Dachs, E. (2004) Lithos 78, 389-409.
Harley, S.L., Thompson, P., Hensen, B.J., Buick, I.S. (2002) J Metam Geol 20, 71-86.
Vry, J.K., Brown, P.E., Valley, J.V. (1990) Am Min 75, 71-88
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FTIR microspectroscopy and SIMS study of water-poor cordierite from El Hoyazo, Spain: Application to mineral and melt devolatilization
No full textThis paper reports the microchemical and microspectroscopic FTIR study of cordierite from a partially melted graphite-bearing granulitic enclave within the dacitic lava dome of El Hoyazo (SE Spain). Optically transparent single-crystals, hand picked from the rock, were oriented using X-ray diffraction and studied by Fourier-transform infrared (FTIR). Single-crystal FTIR spectroscopy shows that the examined cordierite is CO(2)-rich and almost H(2)O-free. Two weak and sharp peaks are observed at 3708 and 3595 cm(-1), respectively, which are strongly polarised for E // a. These peaks are assigned to combination modes of CO(2). Very weak bands due to H(2)O molecules oriented with the H. H vector // c (type I water) are occasionally observed in certain zones of the grains, associated with absorptions due to hydrated inclusions of alteration products. The very intense bands observed in the 2600-2000 cm(-1) region are assigned to CO(2) molecules oriented // a; the spectra also show the presence of (13)C and (18)O, and weak amounts of CO in the sample. Microspectrometric mapping shows that the distribution of C is relatively homogeneous, whereas that of H(2)O is complicated by a very broad absorption extending from 3700 to 3100 cm(-1). High-resolution FTIR imaging, done using a focal-plane array of detectors, shows that this broad absorption is associated with microfractures. SIMS analyses give an average concentration of H(2)O=0.033 +/- 0.007 wt.% and CO(2)=0.21 +/- 0.07wt.%. On the basis of these data, molar absorption coefficients can be calibrated for CO(2): epsilon(iCO2) (integrated)= 11,000 +/- 4000 l/(mol cm(-2)) and epsilon(lCO2) (linear)= 800 +/- 250 l/(mol cm(-1)). Due to the extremely low amount of H(2)O and its inhomogeneous distribution, calibration of absorption epsilon(H2O) coefficients is unreliable. The very low H(2)O contents in the El Hoyazo cordierite indicate continued mineral-melt volatile exchange during decompression from similar to 5 kbar to significantly shallower levels. (C) 2009 Elsevier B.V. All rights reserved
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