minerals Article Rutile Mineral Chemistry and Zr-in-Rutile Thermometry in Provenance Study of Albian (Uppermost Lower Cretaceous) Terrigenous Quartz Sands and Sandstones in Southern Extra-Carpathian Poland Jakub Kotowski * , Krzysztof Nejbert and Danuta Olszewska-Nejbert Faculty of Geology, University of Warsaw, Zwirki˙ i Wigury 93, 02-089 Warszawa, Poland; [email protected] (K.N.); [email protected] (D.O.-N.) * Correspondence: [email protected] Abstract: The geochemistry of detrital rutile grains, which are extremely resistant to weathering, was used in a provenance study of the transgressive Albian quartz sands in the southern part of extra-Carpathian Poland. Rutile grains were sampled from eight outcrops and four boreholes located on the Miechów, Szydłowiec, and Puławy Segments. The crystallization temperatures of the rutile grains, calculated using a Zr-in-rutile geothermometer, allowed for the division of the study area into three parts: western, central, and eastern. The western group of samples, located in the Citation: Kotowski, J.; Nejbert, K.; Miechów Segment, is characterized by a polymodal distribution of rutile crystallization temperatures ◦ ◦ ◦ Olszewska-Nejbert, D. Rutile Mineral (700–800 C; 550–600 C, and c. 900 C) with a significant predominance of high-temperature forms, Chemistry and Zr-in-Rutile and with a clear prevalence of metapelitic over metamafic rutile. The eastern group of samples, Thermometry in Provenance Study of corresponding to the Lublin Area, is monomodal and their crystallization temperatures peak at Albian (Uppermost Lower 550–600 ◦C. The contents of metapelitic to metamafic rutile in the study area are comparable. The Cretaceous) Terrigenous Quartz central group of rutile samples with bimodal distribution (550–600 ◦C and 850–950 ◦C) most likely Sands and Sandstones in Southern represents a mixing zone, with a visible influence from the western and, to a lesser extent, the eastern Extra-Carpathian Poland. Minerals group. The most probable source area for the western and the central groups seems to be granulite 2021, 11, 553. and high-temperature eclogite facies rocks from the Bohemian Massif. The most probable source area https://doi.org/10.3390/ for the eastern group of rutiles seems to be amphibolites and low temperature eclogite facies rocks, min11060553 probably derived from the southern part of the Baltic Shield. Academic Editor: José Francisco Molina Keywords: heavy mineral analysis; trace elements; Lower Cretaceous; provenance; mature sediment; longshore current; Bohemian Massif; Baltic Shield Received: 30 March 2021 Accepted: 19 May 2021 Published: 23 May 2021 1. Introduction Publisher’s Note: MDPI stays neutral The uppermost Early Cretaceous (Middle and Late Albian, c. 110.8–100.5 Ma) and with regard to jurisdictional claims in Late Cretaceous epicontinental basin in Poland, called the Polish Basin, was part of the published maps and institutional affil- vast Central European Basin System (CEBS, Figure1)[ 1]. The CEBS developed after iations. the Variscan orogeny (c. 300 Ma) and extended from the North Sea to Poland [2]. The processes that took place in the CEBS from the Permian to the Palaeogene were successive marine transgressions and regressions with the dominant characteristics of shallow shelf sea sedimentation. In the late Jurassic, a significant uplift of Precambrian and Variscan Copyright: © 2021 by the authors. structures was reported, e.g., [2,3] including SW Poland. After the Neo-Cimmerian tectonic Licensee MDPI, Basel, Switzerland. phase, during the Earliest Cretaceous, the sea-level was low [4] and large land areas This article is an open access article of extra-Alpine Europe had been elevated [5]. Sedimentation in the Polish Basin was distributed under the terms and restricted to the narrow Mid-Polish Trough, including terrestrial and shallow shelf facies. conditions of the Creative Commons Additionally, the epicontinental Polish basin was isolated from the Tethys Sea during most Attribution (CC BY) license (https:// of the Early Cretaceous [6–8]. In the Middle and Late Albian (latest Early Cretaceous) in creativecommons.org/licenses/by/ the Polish Basin, as in everywhere in Europe, a significant eustatic marine transgression 4.0/). Minerals 2021, 11, 553. https://doi.org/10.3390/min11060553 https://www.mdpi.com/journal/minerals Minerals 2021, 11, 553 2 of 28 Minerals 2021, 11, 553 2 of 27 in the Polish Basin, as in everywhere in Europe, a significant eustatic marine transgression began [9–11]. [9–11]. The The sea sea transgressed transgressed from from the the we westst and and merged merged with with the theRussian Russian sea seain the in eastthe east[9]. The [9]. detrital The detrital material material came, came, most probably, most probably, from nearby from nearby uplifted uplifted areas. The areas. source The areassource (Figure areas ( Figure1) could1 ) have could been have (i) been the (i)Bohemi the Bohemianan Massif Massif S and S SW and of SW the of study the study area; area; (ii) the(ii) theUkrainian Ukrainian Shield Shield [5,9,12]; [5,9,12 (iii)]; (iii) a ahypothetical hypothetical Holy Holy Cross Cross Mountain—Dobruja Mountain—Dobruja Land (HCMDL) [13], [13], also called the Krukienic Island [14]; [14]; or (iv) the crystalline basement of the southernsouthern part part of the Baltic Shield. Quartz Quartz as as a main component of the Albian sands has littlelittle diagnosticdiagnostic significancesignificance in in determining determining its provenance.its provenance. Therefore, Therefore, the analysis the analysis of heavy of heavyminerals minerals seems toseems be a to promising be a promising approach approach in provenance in provenance studies ofstudies these mineralogicallyof these miner- alogicallymature sediments mature sediments [15–19]. [15–19]. Figure 1. Albian palaeogeography of epicontinental sea and adjacent western Tethys of Europe with simplified distribu- Figure 1. Albian palaeogeography of epicontinental sea and adjacent western Tethys of Europe with simplified distribution tion of facies (modified from [5,20]); 1—land areas; 2—deltaic, coastal, and shallow marine clastic facies (sands and con- of facies (modified from [5,20]); 1—land areas; 2—deltaic, coastal, and shallow marine clastic facies (sands and conglomerates, glomerates, sands and shales); 3—shallow-marine facies (sands, marls, carbonate marls, marly carbonates, carbonates); 4—mainlysands and shallow-carbonate shales); 3—shallow-marine marine facies facies (marly (sands, carbonates, marls, carbonate carbonates, marls, chalk, marly white carbonates, chalk, carbonate carbonates); shales); 4—mainly 5—active foldshallow-carbonate belts, high relief; marine 6—marine facies (marlycarbonates; carbonates, 7—deeper carbonates, marine chalk,clastics white (sand chalk, and carbonateshales); 8—deeper shales);5—active marine carbonates fold belts, (withhighrelief; sands6—marine and shales); carbonates; 9—carbonates 7—deeper and sands; marine 10—deeper clastics (sand marine and facies shales); (sands 8—deeper and shales marine, shales); carbonates 11—deeper (with marine sands shaleand shales); facies from 9—carbonates a rift area; and 12—area sands; 10—deeperof the study; marine HCMDL—hypothetic facies (sands and Holy shales, Cross shales); Mountains—Dobruja 11—deeper marine Land; shale ?—no facies precisefrom a riftdata area; for 12—areathe southern of the edge study; of the HCMDL—hypothetic HCMDL. Holy Cross Mountains—Dobruja Land; ?—no precise data for the southern edge of the HCMDL. Recently, the majority of provenance studies of sedimentary rocks containing clastic materialRecently, have been the majority based on of the provenance composition studies of heavy of sedimentary minerals [15,21,22]. rocks containing The develop- clastic mentmaterial of EPMA have beentechniques based has on themade composition it possible to of carry heavy out minerals relatively [15 inexpensive,,21,22]. The rapid, devel- andopment widely of EPMAaccessible techniques analyses hasof trace made elements it possible in heavy to carry minerals. out relatively This has inexpensive,contributed rapid, and widely accessible analyses of trace elements in heavy minerals. This has con- Minerals 2021, 11, 553 3 of 27 tributed to the use of heavy minerals in provenance analyses of siliciclastic deposits and the determination of the host rocks and source areas in many places around the world [23–25]. Rutile, apart from zircon and tourmaline, is classified as a heavy mineral extremely resistant to weathering [24] and is very common in clastic sediments, including quartz arenite. Despite this, rutile is rarely used in provenance analyses of clastic material. It is, however, an especially useful mineral in pure quartz arenites, which are characterized by high ZTR (zircon-tourmaline-rutile) index, low quantity, and low diversity of heavy minerals [18,26,27]. However, it is interesting because rutile composition can be used as a tool in provenance studies [28–30]. The advancement of analytical techniques led to the recognition of a relationship between the crystallization temperature and Zr content in rutile [31,32]. This in turn allowed the calibration of the Zr-in-rutile (ZIR) geothermometer, which can also be quite widely used in determining the provenance of detrital rutile [28,29,31,33,34]. The aims of this paper are as follows: (1) to comment on the physical properties of rutile as an important factor influencing the mode of preservation of rutile in detrital settings; (2) to report on the chemical composition