Exceptional silica speleothems in a volcanic cave: A unique example of silicification and sub‐aquatic opaline stromatolite formation (Terceira,Azores)

Silica stromatolites occur in a number of modern hydrothermal environments, but their formation in caves is very rare. The silica stromatolitic speleothems of the Branca Opala cave (Terceira Island, Azores), however, provide an excellent opportunity for their study. These formations may be analogous to ancient silica stromatolites seen around the world. Petrographic, mineralogical and geochemical analyses were undertaken on the silica speleothems of the above cave, and on the silica‐tufa deposits outside it, with the aim of understanding their genesis. The possible hydrothermal origin of their silica is discussed. X‐ray diffraction analyses showed opal‐A to be the sole silica phase. Negligible ordering of this opal‐A showed ageing to be insignificant, as expected for recent silica deposits. Most of the silica speleothems examined were definable as sub‐aquatic opaline stromatolites that are not currently growing. Optical microscopy clearly revealed a lower microlaminated, an intermediate and an upper microlaminated zone within the stromatolites. Stromatolite types (I, II and III) were classified with respect to their internal structure and distribution throughout the cave. Scanning electron microscopy showed silicified bacterial filaments within the stromatolites, the silicified plant remains and the silica‐tufa deposits. Bacteria therefore played a major role in the precipitation of the opal‐A. Plasma emission/mass spectrometry showed major, minor and rare earth elements to be present in only small quantities. The rare earth elements were mainly hosted within volcanic grains. Rapid silica precipitation from highly super‐saturated water would explain the intense silicification of the plant remains found inside and outside the cave. The opaline stromatolites, the silica‐tufa deposits and the above‐mentioned intense general silicification suggest a local hydrothermal source for the silica. Indeed, these deposits strongly resemble plant‐rich silica sinter associated with low‐temperature hot spring deposits that include bacterial filaments. However, no geochemical signals that might indicate a hydrothermal origin could be found.     

Isotopic archives of sulphate in speleothems

The hemispheric impact of industrial emissions upon atmospheric sulphur loading is reflected in the sulphur depositional history recorded in cores from ice sheets. However, these do not reveal regional variations. Recently deposited speleothems are used here as archives of regional sulphur depositional history at two locations within the United Kingdom and Ireland. δ³⁴S-so₄ and δ¹⁸O-so₄ present within speleothem carbonate are measured for the first time as part of a dual isotope approach to decode the speleothem sulphur record. The largely refractory nature of δ³⁴S-so₄ under oxidising conditions enables source provenance of atmospheric SO₂, whereas the complex cycles of isotopic exchange and fractionation during incorporation of oxygen into sulphate molecules enable δ¹⁸O-so₄ signatures to yield insights into ambient environmental conditions and biogeochemical cycling in the ecosystem above the cave. δ³⁴S-so₄ values extracted from speleothem carbonate formed within Browns Folly Mine, UK, range from +3.5 to +5.5‰ and δ¹⁸O-so₄ +10.3 to +13.7‰. Both signatures lie within the range expected from sulphate deposition in industrial locations and reflect the transfer of sulphate into speleothem calcite with little fractionation. However, δ¹⁸O-so₄ signatures at Crag Cave, western Ireland, are isotopically heavier than expected and approach isotopic equilibrium with δ¹⁸O-h₂o under reducing conditions. Dual isotope analysis of δ³⁴S-so₄ and δ¹⁸O-so₄ optimises the correct identification of sulphur sources and biogeochemical cycling prior to incorporation into the speleothem record. At carefully selected cave sites where drip water flowpaths into the cave remain oxic, speleothems hold the potential to retain records of atmospheric sulphur loading at the local and regional scale.     

The (Na–Ca)amphibole–albite–chlorite–epidote–quartz geothermobarometer in the system S–A–F–M–C–N–H2O. 1. An empirical calibration

The proposed geothermobarometer is based on an empirical calibration which takes account of two equilibria involving the tremolite, edenite, pargasite and hastingsite components in amphiboles. It has applications to assemblages found in metabasic rocks of widely different chemical compositions (magnesian to Fe-rich metabasalts), and for metamorphism ranging from lower greenschist to highest amphibolite facies. Knowing the Si_(T1), Al^iv, Al^vi, Fe³⁺, Fe²⁺, Mg, Ca, Na_M4, Na_A and A vacancy in an amphibole, and the Al³⁺ and X _Mg in coexisting epidote and chlorite, it is possible to calculate two values of In K _d for this assemblage. These equilibria involve edenite-tremolite and (pargasite/hastingsite)-tremolite end-members in amphibole (the calculation program is given). For these equilibria, the isopleths (iso-values of K _d) have been calculated for 0.27 < X _Mg < 0.75 and 0 < X _Fe3+= Fe³⁺/(Fe³⁺+ Al^vi) < 0.8. It is then possible to determine pressure and temperature directly when X _Mg, X _Fe3+, In K _d for tremoliteedenite and In K _d for (pargasite/hastingsite)-tremolite are known. Application of this geothermobarometer is limited to Ca-free plagioclase assemblages, and complete P–T paths can be drawn only if all the minerals are considered together. Phase relations at successive stages of crystallization can be constrained by studying the relationships between the coexisting minerals, their zoning and the metamorphic fabrics.     

Petrology and geothermometry of retrograded Hercynian charnockites and host gneisses, Agly Massif, French Pyrenees

Abstract A Hercynian charnockite occurs within high-grade gneisses in the Agly Massif, French Pyrenees. Its thermal history has been evaluated using the Fe-Mg distribution coefticient ( K _D) between garnet and biotite. These minerals have different origins but similar compositions in the charnockites and host gneisses. In the charnockite, the Bi–Ga pairs are the retrograde products of Opx alteration. This Opx reaction with feldspar can be written. Opx + PI + Fluid 1(H₂O + Al + K + Fe + Ti) = Bi + Ga + Q + Fluid 2(H₂O + Na). The garnets are relatively Ca poor (4–2.5% grossular); they are automorphic and zoned in the gneisses and poikiloblastic in the charnockites. Both types show a retrograde rim (of few hundred microns'width) across which Fe and Mn increase as Mg decreases. The biotites show a good correlation between the octahedral cations (Ti⁴⁺+ Fe²⁺) and (Mg²⁺+ Al³⁺_VI); Ti and Fe both increase, whereas Mg and Al_VI decrease. There is an inverse linear correlation between Fe²⁺ and Mg²⁺ and the Fe/Mg ratio increases as Ti increases. The relation between Ti and K ^Ga-Bi_DFe-Mg is less clear: it seems that K _D slightly decreases as Ti increases. The equilibration temperatures of Ga–Bi pairs are discussed: the charnockite Ga-Bi pairs have equilibrated between 550°C and 600°C; whereas those of the gneisses have equilibrated between 550°C and 650°C. Two main thermal steps appear: one in the gneisses between 600-650°C and a second one in both the gneisses and the charnockites between 550°C and 600°C.     

TEM observations of several spinel-garnet assemblies: toward the rheology of the transition zone

In order to better identify the mineral phase which controls the rheology of the transition zone (between 410 and 660 km depth) transmission electron microscopy observations were made on several coexisting spinel-garnet assemblies: alkremite xenolith; pyrope-rich – MgO:1.1Al₂O₃ spinel assembly deformed at 1173K, 800 MPa in a Griggs apparatus; (Mg,Fe)₃(Al,Mg,Si)₂Si₃O₁₂ majorite – (Mg,Fe)₂SiO₄ spinel assembly synthesized in a laser heated diamond anvil cell. It was found that garnet crystals systematically remain undeformed while spinel crystals are plastically deformed. These results are in accord with the assumption that the rheology of majorite is stronger than the rheology of spinel, in the conditions of the transition zone.     

再论南京汤山直立人生存时代问题

采用国际上最先进的高精度热电离质谱测年技术,测定了南京汤山葫芦洞钙板和石笋的年龄。并根据洞穴碳酸盐相与洞穴文化堆积层的地层关系,确定南京直立人化石时代在距今50万年左右。      

A Study on the Formation of Smectite in Silica Scales Precipitated from Geothermal Water: The Effect of Magnesium

Abstract. Silica scales containing large amounts of smectite were recently found in the pipelines for geothermal water at a geothermal power plant. To elucidate the mechanism of smectite formation, seven silica scale samples were characterized by powder X-ray diffraction, chemical analysis and ²⁷A1 MAS NMR. Smectite was present in samples with MgO levels above 10 wt% and Al₂O₃ levels below 10 wt%. In ²⁷A1 MAS NMR spectra, peaks assigned to both tetrahedrally and octahedrally coordinated aluminum (Al(4) and Al(6)) were observed for Mg-rich samples, whereas a peak due to Al(4) alone appeared in Mg-poor samples. From these observation and comparison between ²⁷A1 MAS NMR spectra for synthesized precipitates of Al₂O₃-SiO₂ containing MgO and not containing MgO, it is concluded that magnesium plays an important role in the stabilization of Al(6), and results in the formation of smectite     

Determination of Rare Earth Elements and Y in Ultramafic Rocks by ICP-MS After Preconcentration Using Fe(OH)3 and Mg(OH)2 Coprecipitation

A simple and reliable method to separate rare earth elements (REE) from Mg, Fe, K, Na, Ca and Ba in ultramafic rocks has been developed, thereby concentrating their abundances. The sample (0.3 g) was digested with HF and HNO₃ in a PTFE bomb, placed in a stainless steel container and, after drying, the insoluble residue was dissolved in 6 ml of 10% v/v HNO₃. Following the addition of 50% triethanolamine and 30% m/v NaOH solution, the REE were precipitated along with Mg(OH)₂, such that the majority of Fe, K and Na in the solution could be separated by centrifuging. The precipitate was dissolved in 1 ml HNO₃ and a buffer solution of NH₄Cl/NH₄OH at pH = 9.0 was added to precipitate the REE along with any remaining Fe as Fe(OH)₃, and so achieve separation from Mg, Ca and Ba, which remained in the solution. In this way, REE could be separated from major elements and were concentrated by a factor of about 60. The recovery of REE was more than 95% using this method. Four ultramafic rock reference materials, PCC-1 (USGS), JP-1 (GSJ), DZE-1, DZE-2 (IGGE) and one new proficiency testing sample GeoPT12 (GAS Serpentinite) were analysed by ICP-MS using indium as an internal standard. The quantitation limits were about 0.02–0.2 ng g⁻¹. Smooth chondrite-normalised REE patterns were obtained with a precision for REE determination of about 2–9%.     

重庆丰都雪玉洞群洞穴现代监测与古环境研究回顾和展望

重庆丰都雪玉洞群包括羊子洞、雪玉洞和水鸣洞,西南大学的研究团队从2008年开始对雪玉洞群开展了系统的现代过程监测,以了解洞穴系统气候和环境信息的传输、转化和记录过程。通过对雪玉洞洞穴内外的大气、植被、土壤、基岩、滴水和洞穴沉积物等的动态监测,研究了碳酸盐沉积过程的水化学指标变化,揭示了现代洞穴滴水的影响因素和变化过程,以及碳酸盐沉积物对现代气候环境变化的响应,也为古气候的定量化研究提供了基础支撑。现代过程监测记录表明:雪玉洞CO₂主要来源于上覆土壤,其季节变化受降水的影响较大;在短时间尺度上受到游客旅游活动的影响明显,但幅度远远小于自然过程引起的变化。雪玉洞内次生沉积物的沉积速率具有明显的旱季、雨季特征,不同滴水点下方沉积物的沉积速率变化较大。雪玉洞群三个洞穴的石笋古环境记录研究表明,本区石笋的230Th/232Th比值较适合高精度铀系测年;部分石笋沉积速率较快,平均沉积速率达到0.25 mm·a?1,可以开展高分辨率的气候和环境变化研究。羊子洞YZ1石笋的年龄范围在116~3 ka B.P.之间（平均测年精度2σ,269年）,覆盖了整个末次冰期,δ18O和δ13C的变化曲线和东亚季风区的其他记录具有明显的一致性。同位素测试的时间分辨率平均为88年,成功记录了一些百年－千年尺度的气候突变事件,如Heinrich事件、7.2 ka事件、小冰期等。在精确年代学的基础上,雪玉洞群石笋具有重建高分辨率气候环境变化的潜力。      

40Ar-39Ar Spectra of Alunite from Phreatic Craters in the Muine Volcano, Hokkaido, Japan

Abstract. ⁴⁰Ar-³⁹Ar analyses of two alunite samples from phreatic craters in the Pliocene Muine volcano in southwest Hokkaido, Japan, were carried out. The alunite with 17.4 permil δ³⁴S_{V_CDT} value in hydrothermal breccia from the Nagaoyama crater and that with 14.3 permil δ³⁴S_{V_CDT} value in silicified andesite from the Konuma crater give total fusion ages of 1.40 ± 0.04 Ma (la uncertainty) and 1.24 ± 0.08 Ma, respectively. However, the spectra of these samples indicate they have been effected by thermal overprinting and/or the existence of excess argon. These preliminary ⁴⁰Ar-³⁹A analyses suggest that the alunite underwent multiple hydrothermal activity by magmatic gas and vapor subsequent to the main hydrothermal activity.     

Ionic association in H2O–CO2 fluids at mid-crustal conditions

The equilibrium constant, K _a, of the association reaction to form ion pairs from charged solute species in supercritical solutions can be calculated from a model based on published equations. Log K _a at constant pressure is a linear function of the inverse in the dielectric constant of the fluid times temperature. The dielectric properties of H₂O and CO₂ at supercritical pressures and temperatures can also be evaluated using the Kirkwood equation. Using Looyenga mixing rules, the dielectric constant of H₂O–CO₂ mixtures can be obtained and the change in log K _a with addition of CO₂ in aqueous solutions evaluated. These changes in log K _a with addition of CO₂ are consistent with measured changes of log K _a with addition of Ar in supercritical H₂O–Ar solutions.
Log K _a of KCl and NaCl increase to an increasing extent as the mole fraction of CO₂ increases in H₂O–CO₂ solutions. For instance, at 2 kbar and constant temperature between 400 and 600° C, log K _a of KCl increases by about two orders of magnitude whilst that of NaCl increases by over four orders of magnitude as the CO₂ mole fraction increases from 0.0 to 0.35. Such changes in log K _a will have dramatic effects on the solubility of minerals in CO₂-rich environments.     

岩溶洞穴系统SO42-、NO3-来源及其对水岩作用的影响

为揭示洞穴系统中SO₄2-和NO₃-离子来源及其对洞穴碳酸盐溶解的影响,通过对麻黄洞6个水点自2018年8月至2019年7月进行为期一个完整水文年的系统监测,对于监测结果进行综合分析.结果表明:（1）麻黄洞洞穴水水化学类型为HCO₃-Ca·Mg以及HCO₃·SO₄-Ca·Mg型;（2）通过实地调查与元素比值法综合分析可知,麻黄洞NO₃-与SO₄2-各水点来源存在一定差异,其中麻黄洞NO₃-主要源于农业活动和大气N沉降,而SO₄2-主要以农业活动、石膏溶解为主要来源,SO₄2-和NO₃-均参与了岩溶作用,加速了基岩的溶蚀,这一过程主要受离子浓度、径流大小以及补给模式影响;（3）基于水化学计量法和稳定同位素技术估算可知,SO₄2-和NO₃-洞穴水DIC的贡献为0.05~0.61,释放DIC的同时改变了水中离子浓度,对于岩溶作用形成扰动,总体呈现出旱季>雨季、滴水>裂隙水的特征.同样,由于岩溶区的复杂和不可知,在对其进行系统研究时应当注重多种方法的结合与比较,提高研究精度与可信度.      

Determination of Platinum and Palladium in Geological Samples by Inductively Coupled Plasma-Atomic Emission Spectrometry after Preconcentration with Immobilised Nanometric Titanium Dioxide

A new method has been developed for the determination of platinum and palladium based on separation and preconcentration with a microcolumn packed with nanometric TiO₂ immobilised on silica gel (immobilised nanometric TiO₂) prior to their determination by inductively coupled plasma-atomic emission spectrometry. The optimum experimental parameters for the preconcentration of Pt and Pd, such as the pH of the sample solution, its flow rate and volume, the type and concentration of eluent and interfering ions, have been investigated. Platinum and Pd could be quantitatively retained by immobilised nanometric TiO₂ in the pH range 6–8, then eluted completely with 2.0 ml of 3% m/v thiourea in 1.0 mol l⁻¹ HNO₃. The detection limits of this method for Pt and Pd were 12 and 7. 6 ng l⁻¹ with an enrichment factor of 100, and the relative standard deviations were 4.7% and 3.3% at the 10 ng ml⁻¹ level. The method has been applied for the determination of Pt and Pd in geological samples with satisfactory results.     

Pressure–temperature conditions and retrograde paths of eclogites, garnet–glaucophane rocks and schists from South Sulawesi, Indonesia

High-pressure metamorphic rocks exposed in the Bantimala area, c . 40  km north-east of Ujung Pandang, were formed as a Cretaceous subduction complex with fault-bounded slices of melange, chert, basalt, turbidite, shallow-marine sedimentary rocks and ultrabasic rocks. Eclogites, garnet–glaucophane rocks and schists of the Bantimala complex have estimated peak temperatures of T  =580–630 °C at 18  kbar and T  =590–640 °C at 24  kbar, using the garnet–clinopyroxene geothermometer. The garnet–omphacite–phengite equilibrium is used to estimate pressures. The distribution coefficient K _D1=[( X _pyr)³( X _grs)⁶/( X _di)⁶]/[(Al/Mg)_M2,wm (Al/Si)_T2,wm]³ among omphacite, garnet and phengite is a good index for metamorphic pressures. The K _D1values of the Bantimala eclogites were compared with those of eclogites with reliable P–T  estimates. This comparison suggests that peak pressures of the Bantimala eclogites were P =18–24  kbar at T  =580–640 °C. These results are consistent with the P–T  range calculated using garnet–rutile–epidote–quartz and lawsonite–omphacite–glaucophane–epidote equilibria.     

桂林洞穴滴水与现代碳酸钙δ18O记录的环境意义--以桂林七星岩NO.15支洞为例

现代洞穴动态监测的一个先决条件就是为洞穴碳酸盐(CaCO₃)沉积物-石笋的各种替代指标的解译提供可靠的依据,充分利用现代碳酸盐(CaCO₃)沉积物的各种替代指标,并与现代器测气象资料进行相互对比、并用以校正,是精确或定量解释石笋气候替代指标的关键.
经对桂林七星岩15号支洞的5个滴水点进行了长达四个水文年(2008~2011年)的大气降水、洞穴滴水、现代碳酸盐沉积物的动态监测和研究,并探讨了洞穴滴水和现代碳酸盐(CaCO₃)的δ18O与降水δ18O的相关关系.研究表明,洞穴滴水和现代碳酸盐(CaCO₃)的年平均δ18O值非常接近降水的δ18O平均值,并具有与地表降水δ18O相同的变化趋势,反映了洞穴滴水和现代碳酸盐(CaCO₃)的δ18O主要来自大气降水的δ18O,即明显受控于降水的δ18O.在4个水文年中,现代洞穴次生化学碳酸盐(CaCO₃)沉积物的δ18O值与滴水的δ18O值记录的年内(或年际)变化或多年的变化趋势基本相同,表现出明显的四高峰(δ18O低值区)四低谷(δ18O高值区)的波动变化特征,具有明显的年际、季节性变化规律,显示具有雨热同季的特点.研究结果表明洞穴滴水和洞穴现代碳酸盐(CaCO₃)沉积物的δ18O可以记录当地或洞穴上方的气候变化信号,即现代碳酸盐(CaCO₃)沉积物的δ18O主要作为夏季风强度或降雨量的替代指标.     

Dating cleavage formation in slates and phyllites with the 40Ar/39Ar laser microprobe: an example from the western New England Appalachians, USA

Determinations of the absolute age of cleavage formation can provide fundamental information about the evolution of orogenic belts. However, when applied to cleavages in slates and phyllites, conventional dating methods are complicated by problems related to mineral separation and the presence of multiple cleavage generations. In situ high-spatial-resolution ⁴⁰Ar/³⁹Ar laser microprobe geochronology and microstructural observations indicate that the age of cleavage formation in slates and phyllites can be constrained by analysing zones of tightly packed cleavage domains. Three regionally developed cleavages (S₂, S₃, and S₄) are present in the northern Taconic Allochthon of Vermont and New York. Representative samples were studied from a variety of localities where these cleavages, which are defined by white micas, are well developed. In the suite of samples, only S₃ and S₄ are expressed as domains that are sufficiently wide and spatially isolated in thin section to permit quantitative ⁴⁰Ar/³⁹Ar geochronology. Mean ⁴⁰Ar/³⁹Ar laser microprobe ages for these domains are 370.7 ± 1.0 Myr for S₃ and 345.5 ± 1.7 Myr for S₄. Because estimates of the Ar closure temperature for white micas are substantially higher than the inferred growth temperatures of the micas defining S₃ and S₄, these values are interpreted as periods since cleavage formation. This interpretation is consistent with independent geochronological constraints on the age of the Acadian orogeny in the region.     

The evolution of fluorine-rich felsic magmas: source dichotomy, magmatic convergence and the origins of topaz granite

Topaz granite is alkali-feldspar granite that contains essential albite, quartz, K-feldspar, lithium-mica, and topaz. As a group topaz granites are characterized by their extreme enrichment in F (up to 3 wt%) and a wide variety of lithophile elements. They can be subdivided into a 'low-P₂O₅ subtype' (P₂O₅ < 0.1 wt%, Al₂O₃ < 14.5 wt%, SiO₂ > 73 wt%) and a 'high-P₂O₅ subtype' (P₂O₅ > 0.4 wt%, Al₂O₃ > 14.5 wt%, SiO₂ < 73 wt%), the δ¹⁸O values of which indicate a dichotomy of source rock: the low-P₂O₅ subtype (δ¹⁸O < 10‰) having a meta-igneous protolith and the high-P₂O₅ subtype (δ¹⁸O > 10 ‰) a source with a significant component of pelitic material. The unusually high F contents enhance the efficacy of melt segregation and crystal-melt fractionation and so facilitate extreme differentiation in topaz granite magmas. Very low melt volumes restrict the bulk composition of the partial melts regardless of the nature of the source; and extreme fractionation forces them along a path of magmatic convergence, to produce a group of granitic rocks with near-minimum compositions so enriched in a variety of lithophile elements (Li, Nb, Ta, Sn) that economic mineralization often results.     

Use of Chelating Resin YPA4 Micro-Columns for the On-Line Preconcentration and Separation of Gold(III), Silver(I), Palladium(II) and Platinum(IV) in Geological and Environmental Samples and Their Determination by Inductively Coupled Plasma-Atomic Emission Spectrometry

A simple and selective method of flow injection (FI) using a micro-column packed with chelating resin YPA₄ as solid phase extractant was developed for the preconcentration and separation of trace amount of noble metals, Au(III), Ag(I), Pd(II) and Pt(IV), followed by ICP-AES determination. In HNO₃ media, the chelating resin was selective towards Au(III), Ag(I), Pd(II) and Pt(IV), and the analysed ions were readily desorbed quantitatively with 5 ml of 2.5% m/v thiourea. Effects of acidity, sample flow rate and concentration, elution solution and interfering ions on the recovery of the analytes were systematically investigated. Under optimum conditions, the adsorption capacities of YPA₄ for Au(III), Ag(I), Pd(II) and Pt(IV) were 67.2, 43.1, 64.8 and 27.6 mg per gram of resin in HNO₃ media, respectively. It was found that YPA₄ could be used for more than eight runs in HNO₃ media without loss of capacity. The proposed method was used for the determination of trace noble metals in geological and environmental samples, and the analytical results obtained were in good agreement with the recommended values.     

The muscovite-melt bathograd and low-P isograd suites in north-central Wopmay Orogen, Northwest Territories, Canada

In north-central Wopmay Orogen, syntectonic low-P(Buchan-type) suites of mineral isograds outline regional metamorphic temperature culminations that are associated, at the higher structural levels, with emplacement of early Proterozoic plutons in the west part of a deformed and eastward transported continental margin prism. The mapped isograds mark the first occurrence of biotite, staurolite, andalusite, sillimanite, sillimanite-K feldspar and K feldspar-plagioclase-quartz ± muscovite (granitic) pods in metapelites, with increasing proximity to the plutons.
Microprobe analyses and field observations have resulted in the formulation of reactions for the 'ideal'pelitic system K₂O-Na₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O-Al₂O₃-SiO₂-H₂O, to account for the various mineral assemblages of each metamorphic zone. A P-T petrogenetic grid showing erosion surface P-T curves for the northern Wopmay Orogen pelites, compiled on the basis of the mapped isograds and the inferred reaction(s) for each metamorphic zone, documents a variation in exposed metamorphic pressure ranging between 2 and 4 kbar.
The configuration of a new bathograd, based on the invariant model reaction sillimanite + K feldspar + plagioclase + biotite + quartz + vapor ± muscovite + liquid and interpolated across three metamorphic suites, is consistent with a major regional structure culmination and with independently determined pressures obtained from anorthite-grossular-quartz-Al₂SiO₅ geobarometry. The positive correlation between the configuration of the bathograd and the structural and pressure culmination points to the pressure-dependence of anatectic-granitic-pod mineral associations.