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Pinkquartz-anew,meteoriteimpact-relatedorigin?Part1:ObservationsandfirsthypothesisofformationKordErnstson*(2018)Abstract.-Pinkquartz,nottobeconfusedwithrosequartz,isanextremelyrarecolorvariety,whichiscompletelytransparentandisonlyknownfromafewoccurrencesworldwide.Itisbelievedthatthepinkcolorisduetosmallamountsofaluminumandphosphorusthatsubstitutesilicon,andexposureofthequartztonaturalgammaradiation.SandswithadominatingproportionofpinkquartzexcavatedfromthesoilandextractedfromabreccialayerinthecraterstrewnfieldoftheChiemgaumeteoriteimpactsuggestthatnormallycolorlessquartzsandwasirradiatedduringtheimpacteventandmaypossiblybefoundatotherimpactsites.Keywords:Pinkandrosequartz,Chiemgaumeteoriteimpact,neutron-gammaradiation*****************************************************************************************FacultyofPhilosophyI,UniversityofWürzburg,Germany,kernstson@ernstson.de1IntroductionColorsfromionizingradiationisaneffectthatoccursinmanymineralsasaresultofnaturalandartificialexposure.Wellknowncoloredquartztransparentcrystalvarietiesareamethyst,citrineandsmokyquartz.Pinkquartzcrystalswerefirstdiscoveredinthe1930'sinMaine,USA,andlaterin1959inMinasGeraisinBrazil(Dake,etal.1938,Akhavan2005-2013).Inbothcasesthepinkquartzwasconsideredascommonrosequartzthatformedcrystals.OnlyrecentlypinkquartzcrystalshavebeenfoundalsointheHimalayanMountains,andpinkquartzingeneralgoesroundinesotericcirclesasso-called"healingstones".

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This"crystallinerosequartz"raisedtheinterestofmineralogistswhofounddistinctdifferencesbetweenpinkquartzandcommonrosequartz,whichisnowgenerallyaccepted(Balitskyetal.1998,Hori2001,MaschmeyerandLehmann1983,Rykart1995).Intheiropinionthepinkquartzformsinphosphorous-richpegmatiteswherefewsiliconisreplacedbyphosphorousandaluminum,andthecoloristheresultofgammarayradiationfromuranium,thoriumandpotassium-40decayintherock,whichmayaffectexistingtrapped-holecenters.Exposuretosunlight(UV)andheatingabove200°Cleadstodiscoloration.HereIreportonthediscoveryofquartzsandscomposedofadominatingfractionofpinkquartzgrainsthataresuggestedtoberelatedwiththemeanwhileestablishedChiemgaumeteoriteimpactinBavaria,SoutheastGermany.2TheChiemgauimpacteventTheChiemgauimpactstrewnfield(Schüssleretal.2005;Rappenglücketal.2009;Ernstsonetal.2010,2012;B.Rappenglücketal.2010;Liritzisetal.2010;Hiltletal.2011)discoveredintheearlynewmillenniumanddatedtotheBronzeAge/Celticeracomprisesabout100rimmedcratersscatteredinaregionofabout60kmlengthandca.30kmwidthintheverySouth-EastofGermany(Fig.1).Thecraterdiametersrangebetweenafewmetersandafewhundredmeters,amongthemLakeTüttenseewitharim-to-rimdiameterofabout600mandanextensiveejectablanket.SONARecho-soundermeasurementsshowastrikingstructureatthebottomofLakeChiemsee,whichiscompletelyuntypicalforthebottomofanice-agelake.Thestructuremeasuringabout800mx400misadoubletcraterwitharingwall.SincethecraterstrewnfieldextendsbeyondLakeChiemsee,itisplausiblethatfragmentsofthelargemeteoritehavealsofallenintoLakeChiemseeandcreatedcratersontheground(Fig.1).Theheightoftheresultingtsunamicouldexceedseveraldecameters.Clearindicationsofsuchatsunamiareprovidedbydiamictiteswithpronouncedblocklayersandcrossbedding,astheycanbefoundinvariousgravelpitsontheeasternsideofLakeChiemsee(Ernstson2016).Geologically,thecratersoccurinPleistocenemoraineandfluvio-glacialsediments.ThecratersandsurroundingareasarefeaturingheavydeformationsoftheQuaternarycobblesandboulders,abundantfusedrockmaterialsuchasimpactmeltrocksandvariousglasses,strongshockmetamorphism(planardeformationfeatures[PDFs]inquartzandfeldspar,diaplecticglassfromquartzandfeldspar),geophysical(gravity,geomagnetic,groundpenetratingradar)anomalies(Ernstsonetal.2010;NeumairandErnstson2011,Rappenglücketal.2017)andwidespreadimpact-inducedrockliquefactionfeatures(Ernstsonetal.2011,ErnstsonandNeumair2011,ErnstsonandPoßekel2017).Impactejectadepositsinacatastrophicmixturecontainpolymicticbreccias,shockedrocks,meltrocks,andartifactsfromNeolithicandBronzeAge/IronAgepeopleTheimpactissubstantiatedbytheabundantoccurrenceofmetallic,glass

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andcarbonaceousspherules,accrecionarylapilliandmicrotektites(Ernstsonetal.2012,2014).Strange,probablymeteoriticmatterintheformofironsilicideslikegupeiite,xifengite,hapkeite,naquiteandlinzhite,variouscarbideslike,e.g.,moissaniteSiCandkhamrabaevite(Ti,V,Fe)C,andcalcium-aluminum-richinclusions(CAI),mineralskrotiteanddicalciumdialuminate(Hiltletal.2011;Rappenglücketal.2014)addtothefinds.Carbonaceousspherulescontainfullerene-likestructuresandnanodiamondsthatpointtoanimpact-relatedorigin(Yangetal.2008).SuchspheruleswerefoundembeddedinthefusioncrustofcobblesfromacrateraswellasapossibleoutfallinsoilswidespreadoverEurope(Rösleretal.2005;Hoffmannetal.2006;Yangetal.,2008).Abundantfindsofglass-likecarbonfragmentswithpumicetexture,whichhasbeengiventhenamechiemite,containthecarbonallotropesdiamondandcarbyneinalargelyamorphousmatrixofmorethan90%carbon(Shumilovaetal.2018).Aformationofadirectairburstshocktransformationofthetargetvegetation(wood,peat)tocarbonmeltandvaporintheimpacteventissuggested.Physicalandarcheologicaldatingconfinestheimpacteventtohavehappenedmostprobablybetween2,200and500B.C.(Rappenglücketal.2010;Liritzisetal.2010).Theimpactorissuggestedtohavebeenaroughly1,000msizedlow-densitydisintegrated,looselyboundasteroidoradisintegratedcometinordertoaccountfortheextensivestrewnfield(Ernstsonetal.2010,Rappenglücketal.2017).

Fig.1.LocationmapforthetwopinkquartzoccurrenceswithintheroughlyellipticallyencircledChiemgaumeteoriteimpactstrewnfield.

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3ThepinkquartzplacesofdiscoveryThepinkquartzsandswerediscoveredwhensoilandrocksamplesfrominterestingimpactlocationsweresystematicallyexaminedforpotentiallyimpact-relatedmicro-particleslikeglass,metallicandcarbonspherules.Experiencedobserverscouldnotoverlooktheconcentrationofsomanypinkquartzgrains(Fig.2),especiallywhentheyusedastrongmagnettoseparatethemagneticfractionandfoundthatthepinkquartzgrainscouldalsobeseparatedbyanobviouslyslightlyenhancedsusceptibilityofthebasicallyparamagneticquartz.ThefirstsamplewasexcavatednearthevillageofMarwangnorthoftheLakeTüttenseecrater(Fig.1)duringacampaignofrecordingmagneticsusceptibilityprofilesoftheupper50cmtomapaknowndistinctpeakofenhancedmagneticsusceptibility(Fig.3),whichwasfirstmeasuredinthenorthernpartoftheimpactstrewnellipse(Hoffmannetal.2004).TheMarwangmagneticpeakisconnectedtoahorizonenrichedwithfracturedpebbles,cinderyglassandcarbonaceousspherules,whichisconsideredtorepresenttheoriginaldirectlyimpact-affectedEarthsurface.Here,anaccumulationofpinkquartzgrainsattractedattention.

Fig.2.Typicalmagneticsandfractionwithanenrichmentofpinkquartzgrains.Thedarkfractionismostlycomposedoforeandamphibolite.Fieldofview4mm.

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Fig.3.Soilmagneticsusceptibilityprofilewiththesuggestedimpactpeakandsamplingofthepinkquartzgrains.The second sample comes from the diamictic layer found during the Stöttham archeological excavation a few hundred meters apart from the shoreline of Lake Chiemsee (Fig. 1). The several decimeters thick diamictite (Fig. 4) is embedded in colluvium layers and contains brecciated and heavily corroded clasts, abundant organic material like wood, charcoal, fractured animal bones and teeth, and intermixed archeological artifacts. High-temperature signature is characterized by partly melted silica limestone, a typical rock from the Alps, and sandstone clasts with sporadically interspersed glass. Moderate shock is indicated by an abundant and strong kink banding of micas in gneiss clasts from the diamictite, and most recently the author has established strong shock metamorphism in quartz in polymictic breccias from the horizon. Millimeter-sized glass and tiny carbonaceous spherules were extracted from the diamictite mud, the pink quartz grains being an important side effect. The outcrop has in detail been described in Ernstson et al. (2012), and there is no doubt about the connection with the Chiemgau impact event. The early description as a tsunami deposit (D. Sudhaus, pers. report) has meanwhile received full support (Ernstson 2016).

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Fig.4.TheStötthamimpactcatastrophiclayerhostingpinkquartzgrains.4FormationhypothesisThehypothesisoftheformationofpinkquartzintheChiemgauimpactstrewnfieldisbasedontheoriginalexplanationofpinkcolorationbygammairradiationinpegmatites,inwhichlittlequartzsiliconwassubstitutedbyphosphorousandaluminum(see1Introduction).ThefollowingsequenceofprocessescouldhavetakenplaceintheChiemgauimpactevent(Fig.5):AhugeplasmacloudintheairburstofthecometorasteroidapproachestheEarth.-FastneutronsfromtheplasmabombardtheEarth'ssurfaceandhitexposedwater-bearingquartzsands.-Thefastneutronsarecapturedbycollisionwithhydrogennucleiandlosemostoftheirenergyduetothesamemass,tobecomesloworthermalneutrons.-Thecaptureprocessisaccompaniedbytheemissionofastronggammaradiation.-Thegammaradiationhitsmineralogically"wellprepared"quartzgrainstonowobtaintheirpinkcolor.-Immediatepost-impactsedimentationbyprobablyenormousprecipitationspreventsexposuretosunlightanddiscoloration.SomuchforaphysicalscenarioofapossibleformationofthepinkquartzgrainsintheChiemgauimpactstrewnfield,thesignificanceofwhichisdiscussedbelow.

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Fig.5.ModelofpinkquartzformationintheChiemgaumeteoriteimpactevent.Seetext.5DiscussionandConclusionsThefollowingobservationsarefulfilled:IntheChiemgauimpactcraterstrewnfieldquartzsandswereexcavatedthatcontainacertainamountofpinkquartz.Thegrainsareasclearasrockcrystalquartz.Thepinkgrainsareslightlyenhancedparamagnetic,astheycanbeseparatedfromnormalgrainswithastrongmagnet.Thispropertyhasnotyetbeenreportedforotherpinkquartz.Originallysurprisingfortheauthor,butnowunderstoodwastheobservationthatthepinkcolordisappearedafterthegrainswereexposedtodaylightforsometime,whichhasalsobeenreportedforotherpinkquartz(see1Introduction).

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Achemicalanalysisofthepinkquartzgrainsbye.g.SEMEDShasnotbeendonesofarandwillbeperformedwhennewsamplesareavailable.Thegeneralcontextwithearlierdiscoveredpinkquartz(seeabove)isgiven,takingintoaccountthedeliveryareaforthequartzsandsthatarethenearbyAlpinemountainswherequartzpegmatitesandphosphorousmineralizationarecommon.DirectobservationsofpinkquartzintheAlpsareunknown,andinviewoftheherdsofmineralcollectors,thediscoveryofthisrarevarietywouldhavebeenreported.Ontheotherhand,itcannotberuledoutthatotherrarechemicalelementsthatreplacesiliconmayalsobesusceptibletoirradiationpinkcoloring,whichmustbechecked.ThisalsoappliestotheslightlyenhancedmagneticsusceptibilityoftheChiemgaupinkquartz,andasuperparamagneticbehaviorcannotbeexcluded.ThisremindsofanunusualobservationintheChiemgauimpactstrewnfield,namelytheoccurrenceofstronglymagnetizedQuaternarylimestonecobblesandbouldersfromtheAlps,whichwereexcavated,forexample,fromthesmallerKaltenbachandMauerkirchenimpactcratersshowingmuchevidenceofimpactoverprint(NeumairandErnstson2011,ProcházkaandTrojek2017.Moreover,thelimestones,whicharenormallymagneticsterile,havedemonstrablyacquiredconsiderableferrimagnetismandassociatedsuperparamagnetism(NeumairandErnstson2011,ProcházkaandKletetschka2016).Asthelimestonecobblesandbouldersarecompletelyuntouchedattheoutside,shockmagnetizationisconsidered.Itcancurrentlybespeculatedwhethersuperparamagnetismwasshock-generatednotonlyintheotherwise"nonmagnetic"limestones,butalsointhepinkquartzgrainswithaslightlydifferentchemistrythan"normal"quartz.Thisdoesnotaffecttheirradiationhypothesisforthepinkcoloringasrelatedtoanimpactneutronbombardmentofwater-bearingquartzsandsandasecondarygammaradiation(Fig.5)postulatedfortheotherpinkquartzoccurrences.AheavyneutronbombardmentduringtheChiemgauimpacteventhasbeendiscussedbyusearlierwhenseveralradiocarbon(14C)agesfordeep-seated(2-3m)organicmatter(bones,wood)inimpactcatastrophelayers(LakeTüttenseeejectalayer;Ernstsonetal.2010)gavefartoohigh14Cvaluescorrespondingtoimpossiblemedievalandeventoday'sages.Inconclusiveradiocarbonagesarenotunknownfordatingofyoungimpacts(e.g.,Rasmussenetal.2000).Inourcaseanimpactplasmaneutronbombardmentcouldhaveinitiatedwhatnormallyhappensintheatmospheretoproducethemoreorlessconstant14Clevelastheknownbasisfortheradiocarbondating.Intheatmosphere,spallationneutronscollidewithnitrogen14Nnuclei,whichleadstoanuclearreactionandproductionoftheradioactive14C.NeutronsthatbombardtheEarth'ssurfaceinanimpacteventcouldcollidewith14Nisotopesinorganicmatter,andthesamereactionasintheatmospherecouldoccur,whichproducesexcess14Candtoday'stooyoungages.

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Inconclusion:ThereismuchevidencefromearlierinvestigationsintheChiemgauimpactstrewnfieldthathugeairburstscouldhaveplayedamajorrole(Ernstsonetal2010,Rappenglücketal.2017,Shumilovaetal.2018).Plasmaformationhasinevitablybombardedtheearth'ssurfacewithstrongneutronshowers.Fastneutroncollisionswithhydrogennucleifromwater-bearingquartzsandsproducedthegammaradiationforpinkquartzcoloring,whichisconsideredtobethecauseforthepreviouslyknownsitesofpinkquartz.ThenextstepsintheinvestigationoftheChiemgaupinkquartzwillbereportedinanarticle'sPart2.Asystematicsearchformoreoccurrencesisplannedand,withapositiveresult,adocumentationoftheirdistributioninrelationtootherimpactfeaturesinthecraterstrewnfieldandpossiblyatplacesdefinitelyoutsidethecraterfield.Pinkquartzgrainsizeswillbemeasured,wherebyapreferredsortingischecked.SEMEDSanalysesforphosphorous,aluminumorotherelementswillbeperformed.Atestofmagneticbehaviorandrock-magneticproperties,e.g.forsuperparamagnetism,areplanned.Acontrolledobservationofapossiblediscoloringindaylightmayfollow.Iftheseorotherdataareavailable,itmaybepossibletoconfirmorquestiontheimpactneutron-gammaradiationhypothesis,andasearchforpinkquartzinotherimpactstructuresmaybepromising.References Akhavan,A.C.http://www.quartzpage.de/pink.html©2005-2013(accessedJuly31,2018). Balitsky,V.S.,Makhina,I.B.,Prygov,V.I.,Mar'in,A.A.,Emel'henko,A.G.,Fritsch,E.,McClure,S.F.,Taijing,L.,DeGhionno,D.,Koivula,J.I.,Shigley,J.E.(1998).RussianSyntheticPinkQuartz.GemsandGemology:34:34-43. Bauer,F.,Hiltl,M.,Rappenglück,M.A.,Neumair,A.,&Ernstson,K.(2013).Fe2Si(Hapkeite)fromthesubsoilinthealpineforeland(SoutheastGermany):Isitassociatedwithanimpact?Meteoritics&PlanetaryScience,48(S1)(76thAnnualMeetingoftheMeteoriticalSociety),Abstract#5056. Dake,H.C.,Fleener,F.L.,Wilson,B.H.(1938).QuartzFamilyMinerals:AHandbookfortheMineralCollector,304p.,WhittleseyHouse,McGraw-HillBookCompany. Ernstson,K.(2016).Evidenceofameteoriteimpact-inducedtsunamiinlakeChiemsee(SoutheastGermany)strengthened.47thLunarandPlanetaryScienceConference,Abstract#1263. Ernstson,K.,Mayer,W.,Neumair,A.,Rappenglück,B.,Rappenglück,M.A.,Sudhaus,D.,&Zeller,K.(2010).TheChiemgaucraterstrewnfield:EvidenceofaHolocenelargeimpacteventinSoutheastBavaria,Germany.JournalofSiberianFederalUniversityEngineering&Technologies,1/3,72–103. Ernstson,K.,Mayer,W.,Neumair,A.,&Sudhaus,D.(2011).ThesinkholeenigmaintheAlpineForeland,SoutheastGermany:Evidenceofimpact-inducedrockliquefactionprocesses.CentralEuropeanJournalofGeosciences,3/4,385–397.

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Ernstson,K.,Sideris,C.,Liritzis,I.,&Neumair,A.(2012).TheChiemgaumeteoriteimpactsignatureoftheStötthamarchaeologicalsite(SoutheastGermany).MediterraneanArchaeologyandArchaeometry,12/2,249–259. Ernstson,K.,Shumilova,T.G.,Isaenko,S.I.,Neumair,A.,&Rappenglück,M.A.(2013).Frombiomasstoglassycarbonandcarbynes:Evidenceofpossiblemeteoriteimpactshockcoalificationandcar-bonization.Modernproblemsoftheoretical,experimentalandappliedmineralogy(YushkinMemorialSeminar–2013):Proceedingsofmineralogicalseminarwithinternationalparticipation(S.369–371).Syktyvkar:IGKomiSCUBRAS. Ernstson,K.,Hiltl,M.,&Neumair,A.(2014).Microtektite-likeglassesfromtheNorthernCalcareousAlps(SoutheastGermany):Evidenceofaproximalimpactejectaorigin.45thLunarandPlanetaryScienceConference,Abstract#1200. Ernstson,K.&Neumair,A.(2011),GeoelectricComplexResistivityMeasurementsofSoilLiquefactionFeaturesinQuaternarySedimentsoftheAlpineForeland,Germany,AbstractNS23A-1555presentedat2011FallMeeting,AGU,SanFrancisco,Calif.,5-9Dec. Ernstson,K.,&Poßekel,J.(2017).Meteoriteimpact„earthquake“features(Rockliquefaction,surfacewavedeformations,seismites)fromgroundpenetratingradar(GPR)andgeoelectriccomplexresistivity/inducedpolarization(IP)measurements,Chiemgau(AlpineForeland,SoutheastGermany).Abstract(EP53B-1700)presentedat2017FallMeeting,AGU,NewOrleans,LA. Hiltl,M.,Bauer,F.,Ernstson,K.,Mayer,W.,Neumair,A.,&Rappenglück,M.A.(2011).SEMandTEManalysesofmineralsxifengite,gupeiite,Fe2Si(hapkeite?),titaniumCarbide(TiC)andcubicmoissanite(SiC)fromthesubsoilintheAlpineForeland:Aretheycosmochemical?42ndLunarandPlanetaryScienceConference,Abstract#1391. Hoffmann,V.,Rösler,W.,andSchibler,I.,(2004).AnomalousmagneticsignatureoftopsoilsinBurghausenarea,SEGermany.GeophysicalResearchAbstracts,6:05041. Hoffmann,V.,Tori,M.,Funaki,M.(2006).PeculiarmagneticsignatureofFe-Silicidephasesanddia-mond/fullerenecontainingcarbonspherules.TravauxGéophysiquesXXVII-Abstractsofthe10th„CastleMeeting“–NewTrendsinGeomagnetism,Paleo,RockandEnvironmentalMagnetism,52–53. Hori,H.(2001).NomenclatureofQuartzColorVariation:PinkandRose.MineralogicalRecord:32(1). Isaenko,S.I.,Shumilova,T.G.,Ernstson,K.,Shevchuk,S.,Neumair,A.,&Rappenglück,M.(2012).CarbynesandDLCinnaturallyoccurringcarbonmatterfromtheAlpineForeland,South-EastGermany:Evidenceofaprobablenewimpactite.EuropeanMineralogicalConference,1,EMC2012–217. Liritzis,I.,Zacharias,N.,Polymeris,G.S.,Kitis,G.,Ernstson,K.,Sudhaus,D.,Neumair,A.,Mayer,W.,Rappenglück,M.A.,&Rappenglück,B.(2010).TheChiemgaumeteoriteimpactandtsunamievent(SoutheastGermany):Firstosldating.MediterraneanArchaeologyandArchaeometry10/4,17–33. Maschmeyer,G.Lehmann(1983).Atrapped-holecentercausingrosecolorationofnaturalquartz.ZeitschriftfürKristallographie,163,181-196.

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Foreland(SoutheastGermany):Formationbyanaturalcarbonizationprocess.ActaGeologicaSinica-EnglishEdition,inpress. Yang,Z.Q.,Verbeeck,J.,Schryvers,D.,Tarcea,N.,Popp,J.,&Rösler,W.(2008).TEMandRamancharacterisationofdiamondmicro-andnanostructuresincarbonspherulesfromuppersoils.Diamond&RelatedMaterials,17,937–943.