Tourmaline as a petrogenetic indicator mineral: an example from the staurolite-grade metapelites of NW Maine

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1 American Mineralgist, Vlume 70, pages 1-15, 1985 Turmaline as a petrgenetic indicatr mineral: an example frm the staurlite-grade metapelites f NW Maine Dnnnnn J. HeNnyr Lunar and Planetary Institute 3303 NASA Rad l, Hustn, Texas ex Cnenr-ns V. Gurrrr Department f Gelgical Sciences University f Maine, Orn, Maine Abstract Turmaline, a mineral ften verlked in petrlgic studies, is shwn t be a useful petrgenetic indicatr mineral. Despite the large number f pssible substitutins in turmaline, generalizatins relating turmaline cmpsitin and rck type are made. Based n available literature data, distinct regins are defined within Al-Fe(tt)-Mg and Ca- Fe(tt)-Mg diagrams fr turmaline frm different rck types. As an example f the utility f turmaline in petrlgic studies, the accessry turmaline frm staurlite-grade pelitic schists frm NW Maine is investigated. These turmaline grains typically display three general styles f chemical zning: (1) a lack f zning, (2) a cntinuus cre-t-rim znatin attributed t grwth during prgressive metamrphism, and (3) a znatin marked by a distinct discntinuity apparently representing detrital turmaline grains surrunded by metamrphic turmaline vergrwths. All f the samples in this study cntain si-, Al-, and Ti-saturating phases (quartz, staurlite, and ilmenite, respectively). Cnsequently, the substitutinal cmplexities f turmaline in equilibrium with the matrix are minimized. Systematic element partitining suggests that chemical equilibrium has been attained amng the rims f the turmaline grains and matrix minerals. Turmaline rims have the highest Mg/Fe and Na./Ca ratis f any f the phases in the metapelites. The cmpsitins f turmaline cres that are presumed t be detrital in rigin are ptically and chemically distinct frm their turmaline vergrwths. In the Al-Fe(ttl Mg and Ca-Fe(ttfMg diagrams, the cmpsitins f the detrital cres fall in the fields f rck types that are cmmnly fund in the presumed surce regin fr the pelitic sediments. Intrductin Turmaline is a very cmmn accessry mineral fund in many rck types and terrains. It ccurs in many clastic sedimentary rcks as a chemically- and mechanicallyresistant heavy mineral (Krynine, 1946; Pettiihn et al., 1973), but als develps authigenically during the late stages f diagenesis (Awasthi, 196l; Ricketts, 1978; Gautier,1979; Mader, 1980). Turmaline is fund in metamrphic rcks with a wide range f bulk cmpsitins and develps at virtually all grades f metamrphism. In additin, granitid intrusive rcks and their assciated aplites, pegmatites, and hydrthermal aureles cmmnly cntain significant amunts f turmaline. Neverthe- 'Present address: Arc Oil and Gas Cmpany, 2300 Plan Parkway, Plan, Texas x/85/0 I I $ less, studies n the relatinship between the cmpsitinal variatins f turmaline and its petrlgic significance are relatively scarce. As such, turmaline has apparently becme a "frgtten" mineral in terms f its use as a petrgenetic indicatr. This paper describes sme f the crystallgraphic and chemical aspects f turmaline which prvide a basis fr systematic petrlgic studies f turmaline. Additinally, sme generalizatins are made cncerning the relatinships between turmaline cmpsitin and rck type (based n data frm the literature). Furthermre, t illustrate the usefulness f turmaline studies, the cmpsitinal variatins f turmaline in staurlite-grade pelitic schists frm nrthwestern Maine are investigated. These turmalines are examined t determine such factrs as their chemical znatin patterns, their apprach t chemical equilibrium, and their relative element partitining

2 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGENETIC INDICATOR with cexisting phases. These data.ue used t make inferences cncerning the rigin f turmaline in these metasediments and the develpment f the chemical zning patterns in the turmaline. General aspects f turmaline mineral chemistry Turmaline is a cmplex brsilicate mineral with a general frmula f XYl(BO3)3Si6Or8(OH)+. It has tw types f ctahedral sites: the Z site and a slightly larger, mre distrted Y site (Dnnay and Bartn, 1972; Rsenberg and Fit, 1979). The Z site is typically ccupied by Al but significant amunts f Fe2*, Fe3+, Ti, Mg, Cr, and V3+ can replace Al (Bartn, 1969; Tsang et al., l97l; Grelkva et al., 1978; Fit and Rsenberg, 1979; Krvushkin et al : Nuber and Schmetzer. 1979: Burns. 1982). The larger Y site tlerates extensive and diverse substitutins invlving mnvalent, divalent, trivalent, and quadrivalent catins (Frndel etal.,1966; Hermn et al., 1973 ; Frtier and Dnnay, 1975 ; Fit and Rsenberg, 1979). The X site usually cntains Na but may als accmmdate variable amunts f Ca, Mg, and vacancies (Fit and Rsenberg, 1977). Brn is in regular triangular crdinatin and has n apparent substituents (Tsang and Ghse, 1973; Pvndra, l98l). Sme Al can substitute fr Si in the tetrahedral site (Fit and Rsenbery, 1979). Finally, in the hydrxyl site F- r 02- can substitute fr OH- (Nemec, 1968; Fit and Rsenberg, 1977). Because f the large amunt f ptential substitutin, turmaline is usually cnsidered in terms f its cmmn end-member cmpnents (Table 1). T a great extent, mst natural turmalines belng t tw cmpletely miscible slid slutin series: schrl-dravite and schrl-elbaite. Hwever, an apparent miscibility gap exists between Table l. Cmmn turmaline end members End nember Sc hrl Dravi te Tsi l iasite E'l bai te Uvite Liddicati te Alkal i-defect tumal i ne P rtn - deficient tumal i ne Buergeri te Ferridravite Fmu'l a Hare2',ltu{B, ),siib(h )4 NaMgrAlU(80,)rSi60r8(0H)4 NaMn.Al -(80^).Si-0. ^ (0H). J O J J O ld q Na(Li,Al )3A16{803)3Si60tg(0H)4 CauS3(r'19A1 5) (B03)3si60tB(0H )4 Ca(Li,A1 )ra1 )3Si6018(0H )4 U(803 al 2t t tr (y' 2,y" )Al6{803)3si6018(0H)4 Hav3*rlt u {a,),sie02z (H) ruare3*rlt u{a, ),sirrrr NaM93Fe3+6(BO3 )3Si60t8(OH )4 *y2* und y3+ lgpresent any divalent r trivalent catin, respectively, in the Y s'ite. Cnsequently, the actual end member will depend n the catin chsen fr the Y site. Table 2. Imprtant substitutinal schemes and exchange cmpnents in turmaline Site substitutins (1)Fe-y - Hgy (2) Nay + A1? = Car + llgt - uvite substituti6n (3) Na1 + A1y = CaI + Fe2+y (4) Na, + Al, = 1tn* *,"2+, (5) Nar + Aiy = Cax + Liy I iddicatite substltutin (6) Mgv'SiT = Aly + Alr tsihemaks substitutiil (7) Nar + llgr = Al, + trrr* al Ial l-dilfect substitiitin (8) l,lgv.0h- = Alv+02 al dmlnbuergeritd substltutin 2+-1+r- (9)Fe-"+911 = Fe-v+0- buerierite substltutln (llj) Atz = (Fe3t,c13*,v3+)z (1t) ltlg, + 25i, = Ti, + 2Al, (12) 2Fe2+y = Liv + Alv elbaiie substltutii (13) 0H = F Exchange cmpnents l,lafe, CaMaNa,Al, CallaNa.Al, tlq-tla.al, CaLiNa,Al, Al.l,,lq,Si, AlNa,t4q, Alf.lq 'H ' n-l FeAl,. CrAl,. VA!, TiAl.$a,Si., LiAlFe " FOH, Ihe subscripts represent the alkali site(x), the tw ctahedral sites (Y and Z), and the tet.ahedral site(t) in the general structural frmul a. Ihis symbl represents a vacdncy in the X site. dravite and elbaite (Deer et al., 1962). Fr this reasn, turmalines are typically described in terms f their psitin in the elbaite-schrl series r in the schrldravite series. Nnetheless, there can be cnsiderable deviatin frm cmpsitins describable by these end member cmpnents alne. In sme turmalines there are significant amunts f the uvite cmpnent (cf. Dunn et al., 1977b). Mst natural turmalines als cntain signifi cant amunts f the alkali-free and prtn-deficient turmaline cmpnents (Fit and Rsenberg, 1977; Rsenberg and Fit, 1979).ln additin, the tsiliasite cmpnent can be imprtant in turmalines which are predminantly in the elbaite-schrl slid slutin series (Slivk, 1959). Finally, thse turmalines cntaining significant amunts f Fe3+ will have appreciable buergerite and/r ferridravite cmpnents (Frndel et al., 1966; Jnes et al. l98l). Substitutins in turmaline can take place as hmvalent catin exchanges n a single site (such as Mg fr Fez* in the Y site) r as hetervalent cupled substitutins ver several sites (such as the cupled uvite substitutin (Ca-Mg fr Na-Al) invlving the X and Z sites). Sme f the mst imprtant substitutinal schemes that can give rise t the cmmnly bserved turmaline cmpsitins are cmpiled in Table 2. Alternatively, each

3 HENRY AND GUIDOTTI: TOI]RMALINE AS A PETROGENETIC INDICATOR f these substitutins can be expressed in terms f their crrespnding exchange cmpnents (cf. Thmpsn, 1982). Such a frmalism is useful because all f the cmpsitinal variatins in turmaline can be taken int accunt by selecting an end-member (additive) cmpnent and intrducing the apprpriate exchange cmpnents (Thmpsn et al., 1982). The cmplex chemical variability f turmaline and its relatin t cexisting phases can ptentially make turmaline an indicatr f the lcal envirnment in which it frmed. With careful cnsideratin f the rck system, changes in turmaline cmpsitin can be related t such factrs as the bulk cmpsitin f the hst rck, the cmpsitin f cexisting minerals, and the p-t-fz cnditins. In fact, because turmaline is s mechanically and chemically stable, each turmaline grain can ptentially prvide imprtant infrmatin n the histry f the rck in which it is fund. Turmaline cmpsitin versus rck type Despite the large number f permissable substitutins, sme generalizatins can be made abut the relatinship between turmaline cmpsitin and the hst rck type. As is apparent frm Table 2, fur f the mst imprtant substituent elements are Al, Ca, Fe, and Mg. A review f available literature (see Appendix l) shws that if turmaline cmpsitins frm varius rck types are pltted n Al-Fe(tt)-Mg and Ca-Fe(ttFMg ternary diagrams, several distinct regins can be defined fr turmalines frm different rck types (Figs. I and 2). Sme imprecisin in lcating bundaries between rck types results frm turmaline analyses which were perfrmed n mineral separates representing the bulk cmpsitin f turmalines (ften zned r cntaining undetected mineral inclusins (cf. Dunn, 1977)). In additin, in zned turmalines with cmplex histries, the cmpsitin f the turmaline in equilibrium with the cexisting minerals may be nly a small vlume f the ttal turmaline grain. Cnsequently, care must be taken in evaluating the turmaline cmpsitin in equilibrium with the matrix minerals. These types f diagrams are useful fr the fllwing reasns: (l) The pltting parameters aie easily btainable frm micrprbe analyses. (2) There is n reliance n a Alkali-free Dravite tt Schrl Buergerite a' ai' t.t 6 f a a f aa a ti^^ ) 1, 1 'rt i 8 a AlrFe(tt)r AlrMgr Fig. l. Al-Fe(ttlMg diagram (in mlecular prprtins) fr turmalines frm varius rck types. Fe(tt) represents the ttal Fe in the turmaline. Several end members are pltted fr reference. This diagram is divided int regins that define the cmpsitinal range fturmalines frm different rck types. The rck types represented are (the values in brackets being the number fdata pints used t define the field): (l) Li-rich granitid pegmatites and aplites tl06l (O), (2) Li-pr granitids and their assciated pegmatites and aplites tgel (O), (3) Fe3+-rich quartz-turmaline rcks (hydrthermally altered granites) t7l (O), (4) Metapelites and metapsammites cexisting with an Al-saturating phase [21] (n), (5) Metapelites and metapsammites nt cexisting with an Alsaturating phase [45] (f), (6) Fe3*-rich quartz-turmaline rcks, calc-silicate rcks, and metapelites t38l (a), (7) Lw-Ca metaultramafics and Cr,V-rich metasediments t23l (A), and (8) Metacarbnates and meta-pyrxenites [55] (A). Nte the verlap f fields 4 and 5 with field 7.

4 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGENETIC I NDICATOR Liddicatite \ s Schrl Buergerite Fe(tt),( ^ 6; 8 a,{t l-b. 3 'i.5 I t!l Mg Dravite Fig. 2. Ca-Fe(ttFMg diagram (mlecular prprtins) fr turmaline frm varius rck types. Several f the cmmn end members are pltted fr reference. The rck types defined by the fields in this diagram are smewhat diferent than thse in Figure l. These fields are (the number fdata pints are given in the brackets): (l) Li-rich granitid pegmatites and aplites tl28l (O), (2) Li-pr granitids and assciated pegmatites and aplites (O), (3) Ca-rich metapelites, metapsammites, and calc-silicate rcks t36l (tr), (4) Ca-pr metapelites, metapsammites, and quartz-turmaline rcks [69](l), (5) Metacarbnates t5al (A), and (6) Metaultramafics ll41 ( ). Nte the verlap f field 4 with field 6. I! 4t particular structural frmula nrmalizatin scheme. (3) The variatins f the data n this diagram represent the cumulative efect f several substitutins. (4) These catins cver cmpsitins and substitutins that are likely t be fund in the the turmalines f cmmn rck types. (5) Sme inferences can be made abut catins which cannt be directly measured n the micrprbe. Fr instance, due t its charge cupling with Al in the Y site, Li can be assumed t be present in significant amunts in the Al-rich turmalines in regin I f Figure 1. In additin, the presence fsubstantial amunts ffe3* can be inferred if the turmaline cmpsitin falls belw the schrl-dravite line i.e. Fe3* is a likely majr substituent f Al in the Z site assuming there is als nt a substantial uvite cmpnent (Frndel et al., 1966; Bartn, 1969; Hermn et al i Dunn et al bl. Walenta and Dunn, 1979). There are als disadvantages t these types f diagrams. (l) They d nt directly take int accunt catins such as V, Cr; r Mn which can be fund in significant quantities in sme turmalines. Nnetheless, the presence f sme f these catins in turmaline can be used as an additinal discriminating factr fr certain rck types. (2) Thse turmalines develped due t hydrthermal alteratin f a pre-existing rck r pegmatite vein injectin can ften be difficult t systematize accrding t this scheme because they partially-t-cmpletely take n the chemical characteristics f the hst rck. In sme cases this may prduce apparently anmalus turmaline cmpsitins accrding t the defined regins. Hwever, even these turmalines can ptentially give sme infrmatin abut the nature f the prtlith (Benjamin, 1969; Fieremans and Paepe, 19E2). Fr example, hydrthermal turmaline in a rck which was riginally a rhylite will be mre enriched in irn than hydrthermal turmaline frm a rck which was riginally a metasediment (Black, l97l; Hlgate, 1977). If the defined fields are valid, then knwledge f the cmpsitin f a turmaline frm an unknwn surce shuld permit a reasnable evaluatin f the riginal rck type in which it frmed. Clearly, many mre detailed micrprbe analyses frm different rck types are required t refine these diagrams. Turmaline frm staurlite-grade schists' NW Maine Gelgic setting Turmaline is present in trace amunts in mst f the metasediments frm the Silurian Rangeley and Perry

5 HENRY AND GUIDOTTI: TOT]RMALINE AS A PETROGENETIC INDICATOR Muntain Frmatins and the Ordivician Greenvale Cve and Quimby Frmatins f the Rangeley quadrangle f nrthwestern Maine (see Fig. I f Guidtti, 1974). ln general, these frmatins are cmpsed f interbedded metapelite, feldspathic metasandstne, plymictic metacnglmerate, and calc-silicate (Mench and Zartman, 1976). They are part f a series f units in the Merrimack synclinrium, a majr nrtheast-trending tectnic feature that reflects the Lwer Devnian Acadian rgen in the nrthern Appalachians (Osberg, 1978). The metamrphic histry f the study area is cmplex with at least three episdes f Devnian reginal metamrphism, tw distinct defrmatins, and subsequent relatively minr defrmatinal events (Mench and, Zariman, 1976; Hldaway et al., 1982). Textural and chemical evidence, hwever, suggests that verall equilibrium was attained in the pelitic schists during the final reginal metamrphic event (Guidtti, 1970, 1974; Henry, l98l). The turmalines discussed belw are in graphite-bearing pelitic schists cllected frm a small area (mst samples frm a ne km2 area) within the staurlite zne. Cnsideratin f this spatially-restricted series f samples permits evaluatin f the element partitining systemaiics under nearly isthermal (T = 'C) and isbaric (P = kbar) cnditins (Henry, l98l). Petrgraphy Turmaline is fund as a euhedral, rd-shaped, accessry mineral (trace t 2%) that is usually disseminated thrughut the metapelites. Higher cncentratins f turmaline are ften fund in very mica-rich layers. Grains up t 400 pm in diameter have been nted but the typical size f a turmaline grain (perpendicular t the c- axis) is apprximately 50 pm. Turmaline has been bserved as an inclusin phase in mst f the ther minerals and, as such, apparently represents a relict detrital and/r early-frmed metamrphic mineral. Turmaline grains are typically zned with black t blue-green cres, frequently with numerus quartz inclusins. The rims are yellw-brwn in pyrrhtite-rich rcks r green-blue in pyrrhtite-pr rcks. The clr change frm the cre t rim may be gradatinal r invlve sharp ptical discntinuities (Fig. 3). Sme turmaline grains shwing these ptical discntinuities have irregular cres vergrwn by euhedral rims whereas thers have bth euhedral cres and rims. Similar textural relatins have been previusly ascribed t the secndary grwth f metamrphic turmaline n detrital turmaline fragments (Wadhawan and Rnwal, 1977; Zen, l98l). Optically unzned turmaline grains frequently cexist with strngly-zned turmaline grains in the same sample. In sme cases this may be the cnsequence f the cut thrugh different turmaline grains. These textural relatins suggest that there must have been sme vergrwth n preexisting turmaline as well as nucleatin and grwth f new turmaline during the metamrphism. Fig. 3. Example f a turmaline with discntinuus ptical zning. A micrprbe traverse was dne alng sectin A-A'(see Fie.4). All f the samples cnsidered in this study cntain Al-, Si-, and Ti-saturating phases (staurlite, quartz, and ilmenite, respectively) (cf. Thmpsn, 1972; Thmpsn et al., 1977). Because these phases cntain essentially fixed cntents fal, Si, and Ti, respectively, the cexisting phases are buffered t high (thugh nt necessarily maximum), nearly cnstant levels f these elements under fixed pressure and temperature cnditins. Three different assemblages are utilized (all cntaining quartz + muscvite + plagiclase (Anr-Anzz) + ilmenite + turmaline + apatite + graphite + pynhtite): (1) staurlite + bitite + garnet + chlrite, (2) staurlite + bitite + chlrite, and (3) staurlite + bitite + crdierite. The presence f graphite in the pelitic schists is indicative f relatively lw /2 cnditins. Calculatins f metamrphic fluid cmpsitins indicate that the /z is slightly higher than the QFM buffer and has relatively little variatin in different samples (Henry, l98l; Henry and Guidtti, 1981). These samples d, hwever, cntain variable amunts f pyrrhtite and the sulfide-silicate interactins have a marked effect in prducing a range f Mg/Fe ratis in turmaline as well as in ther ferrmagnesian minerals in the samples (Henry and Guidtti, 1981, 1982). In limiting mineral assemblagesuch as thse given abve the amunt f chemical variatin in turmaline due t lcal differences in bulk cmpsitin is minimized. The cexistence f an Al-saturating phase (staurlite) with bitite and plagiclase necessitates that the tschermaks (6), alkali-defect (7), and aluminbuergerite (8) substitutins (see Table 2) invlving Al must be held at nearly fixed levels in the turmaline rims. In additin, because Al is buffered and there is a lw and relatively small range in plagiclase cmpsitins, there is nt likely t be an appreciable amunt f uvite (2) substitutin. The presence f ilmenite als buffers substitutin (l l) t cnstant

6 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGENETIC INDICATOR levels. The lw and nearly unifrm/2 cnditins inferred frm the presence f graphite and frm fluid phase calculatins suggest that the buergerite substitutin (9) will als tend t be minr. The absence f significant amunts f Fe3+, Ct'*, and V3* in the turmalines implies that substitutin (10) is als nt imprtant. Finally, since turmalines in the schrl-dravite series with even small amunts f the dravite cmpnent have very little Li (Fit and Rsenberg, 1977; Wilsn and Lng, 1983), the liddicatite (5) and elbaite (12) substitutins are als minimal. Under these cnditins nly substitutin (1) and, t a lesser extent, substitutins (3),(4), and (13) are ptentially variable substitutins in the turmaline in equilibrium with the matrix phases. As a cnsequence, the turmaline substitutinal cmplexities have becme cnsiderably simplified. In terms f exchange cmpnents this reduces the number f independently variable cmpnents in turmaline t MgFe-1, CaMgNa-1Al-1, and Mg2Na-1Al-1, and FOH-1. The range f Mg/Fe ratis in these minerals prduced by the sulfide-silicate interactins make it especially useful t investigate the variatin f the MgFe-1 cmpnent under nearly cnstant P-T cnditins. Analytical techniques Electrn micrprbe analyses f turmaline and the cexisting minerals in the pelitic schists were perfrmed n a three-channel ARL-EMx electrn micrprbe at the University f Wiscnsin-Madisn. Anhydrus xides and simple silicates were used as prbe standards. Analyses were perfrmed utilizing the general techniques f Bence and Albee (1968) with the alpha crrectins factrs f Albee and Ray (1970). Replicate analyses f secndary mineral standards prvided a measure f the magnitude f the errr assciated with the analytical precisin (Henry, l98l). Fr example, the relative uncertainty in the precisin f the Mg/Fe ratis f bitite is -+0.5V. These analytical uncertainties are taken int accunt in evaluating the chemical zning and element partitining data. Analysis f turmaline requires sme additinal cnsideratins. First, the fine-grained nature and the strng chemical zning made it necessary t btain the analysis n as small an area as pssible. As such the beam was tightly fcussed t a l-3 g.m spt. Repeated analysis n a single spt shwed little variatin with time. Cnsequently, there appears t be minimal B-lss due t vlatilizatin under the electrn beam. Secnd, B, Li, and H cannt be directly measured n the prbe. Hwever, inasmuch as brn is the nly catin t be expected in regular triangular crdinatin (Tsang and Ghse, 1973) it is assumed that there are 3 brn atms in the structural frmula and the weight percent f B2O3 necessary t prduce the 3 brn atms was calculated fr each analysis. Since the amunt f H2O is still nt knwn, the structural frmula is calculated n the basis f 29 xygens. This tacitly assumes that there is full ccupancy f 4 hydrxyl anins in the hydrxyl site. Thse turmalines that cntain an appreciable amunt f trivalent catins in the Y site r F in the hydrxyl site will cntain less than 4 hydrxyl anins. Nnetheless this apprach prvides a reasnable starting pint with which t bserve substitutinal trends. Analytical results Chemical zning. The turmalines in the metapelites display three types f chemical znatin: (l) apparently hmgeneus cmpsitinal patterns (relatively rare), (2) a cntinuus cre-t-rim zning where Al, Mg, and Ca increase as Fe, Na, Si, and typically Ti decrease (mst cmmn), and (3) a discntinuus zning prfile ften marked by steep cncentratin gradients and n systematic cre-t-rim zning patterns (cmmn). Representative micrprbe analyses f varius prtins f the zned turmalines are presented in Table 3. The rim-t-rim cmpsitinal prfile f Figure 4 acrss a turmaline grain cntaining an ptically-discntinuus cre is an example f the cmplex zning patterns that ften develp in type (3) turmaline grains. Frm the rim tward the cre there is an verall cntinuus cmpsitinal zning pattern such that Fe and Si increase as Mg and Al decrease until the ptically distinct cre is encuntered. Near the bundary f the ptical discntinuity there is a strng cncentratin gradient in which Al decreases abruptly as Fe, Ti, Na, and Si increase. At the center f the cre there is, in fact, nt enugh Al t fill the Z site. Because the Ca and Mg d nt increase significantly, the mst likely substitutin is ne in which Fe3+ substitutes fr Al in the Z site. Clearly this ptically distinct cre frmed in an envirnment which was different frm the envirnment in which the uter prtin f the grain equilibrated. The uter cntinuus zning may represent the metamrphic zning develped during prgressive metamrphism and pssibly later mdified smewhat by diffusin. Since the ptically distinct cre fragments are nt necessarily in the center f the turmaline grains (as in Fig. 3) zning prfiles may appear very different fr grains even in the same sample. Cnsider the rim-t-rim cmpsitinal prfiles acrss a pair f turmaline grains that are cut perpendicular t the c-axis (Fig. 5). Grain l, a type (2) turmaline grain displaying cntinuus ptical zning, has a prfile that is typical f cntinuusly-zned turmalines. In cntrast, grain 2, a type (3) turmaline grain with a dark-brwn cre, displays a chemical zning pattern that features a marked cre-t-rim decrease in Fe, Ca, and Ti and an increase in Mg and Al. The mst significant difference is that the Ca cre-rim zning pattern is in the ppsite directin in the tw grains. The cre f grain 2 must have riginated in a different envirnment (rprvenance) than the cre fgrain 1. Despite the different zning patterns in the interir fthe crystals, the rim cmpsitins f bth grains are essentially the same. This suggests that the utermst prtin f the turmaline apprached chemical equilibrium with the matrix minerals at the P-I cnditins f metamrphism.

7 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGENETIC INDICATOR Table 3. Representative micrprbe analyses f turmaline frm NW Maine a9-66 c15-56 tttt/4 rim cre cre Bzg si02 Al 203 T i02 Fe0 l'1n0 Ms Ca0 Nar Ke Ttal ?1 Ar t , I f,/ r r.vf ? 0.29? J u.i! t t.02 r I.56 r./ l l , Structural frmula n the basis f 29 xygens B ? nnn si Alt n n?l Alz Alv tl te l.l n l'lg Y Ttal n??? I ? I , I I I I L l ? Ca Na K X Ttal urig.?84 'Cre cnpsitin ln an area disdlaying cntinuus zning. ncre cmpsitin in an area dislaying discntinuus zning, ***The Height percent f 8203 is calculated assuning 3 brn atms in the structural fnnula. Turmaline rim relatins. A mre quantitative evaluatin f the apprach t equilibrium by the turmaline rims can be made by cnsidering the element partitining between the turmaline rims and the matrix minerals. Plts f the Mg/Fe ratis f the turmaline rims versus the cexisting bitites (Fie. 6) and chlrites (Fig. 7) shw that there is systematic element partitining fr these catins. Na-Ca partitining between turmaline rims and plagiclase is als regular (Fig. 8). These systematic relatins suggest that the turmaline rims have clsely apprached equilibrium with the matrix phases. The partitin cefrcients fr turmaline rims and varius matrix phases are given in Table 4. The high values f the partitin cefficients demnstrate that the turmaline rims have the highest Me/Fe and Na/Ca ratis f any f the phases in the metapelites. Based n these bservatins, then, the Mg/Fe ratis in the minerals in the staurlite-grade pelitic schists prceed as fllws: turmaline rim > crdierite > chlrite > bitite ) staurlite > garnet > ilmenite. As demnstrated in Figures 6-8 turmaline rim cmpsitins shw a significant range in the Mg/Fe and Na/Ca

8 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGENETIC INDICATOR.E 22 E E 20 G) d c x N, c -9 6 a F t '- lt = 16 l$'1.980! a Mg/Fe Bitite Fig. 6. Mg-Fe partitining between bitite and cexisting turmaline rims. The uncertainties due t analytical precisin are shwn by the hrizntal and vertical bars. Fig. 4. Quantitative micrprbe traverse acrss an ptically discntinuusly zned turmaline (sectin A-A' in Fig. 3). The catins are calculated n the basis f 29 xygen and 3 brn atms in the structural frmula. Based n replicate analyses, analytical uncertainties are typically less than 0.01 catin units. E a),6 c x 6l c.9 6 ratis. Hwever, a survey f the rim cmpsitins indicates that the amunts f Si, Al, and Ti are relatively cnstant (Table 5). If the cmpsitins f the turmaline rims are pltted n an Al-Fe(tt)-Mg diagram (Fig. 9) the data cluster n a line f nearly cnstant Al. The se data fall well within the field which has been defined fr metapelites with a cexisting Al-saturating phase. This bservatin supprts the cntentin that the saturating Al-, Si-, and Ti-phases maintain these catins at cnstant levels in the turmaline rims at the cnstant P-T cnditins f these rcks. A similar trend is fund if the turmaline rim cmpsitins are pltted n a Ca-Fe(ttFMg diagram (Fig. l0). The slightly varying Ca values reflect the restricted plagiclase cmpsitin. A general indicatin f the amunt f dehydrxylatin in the turmaline rims can be gained by cnsidering the average rim cmpsitins. If the average turmaline rim.e E E= l! = Fig. 5. Micrprbe traverses acrss tw turmaline grains fund within I mm f ne anther. The grains shw different styles fzning. Despite the differences in the internal zning the cmpsitins at the rims are essentially the same. llglf Chlrlt Fig. 7. Mg-Fe partitining between chlrite and cexisting turmaline rims.

9 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGENETIC INDICATOR Table 5. Variatin in turmaline rim cmpsitins "E E t F 6 6 z q I 6.t c 34s678 fz /"..1.' /. Kp-t.582!0.120 Na/Ca plaglclase Fig. E. Na-Ca partitining between plagiclase and cexisting turmaline rims. frmula is calculated n the basis f 29 xygen and 3 brn atms the ttal number f catins in the Y site is (t0.021); implying vacancies in the Y site. Nnetheless structural determinatins f turmalines have nt indicated that there are any Y site vacancies in turmalines f the schrl-dravite series (Dnnay and Bartn, 1972; Fit and Rsenberg, 1977; Rsenberg and Fit, 1979). If, hwever, it is assumed that there is full Y site ccupancy (i.e., n Y site vacancies) and charge balance is maintained by lss f a prtn frm the hydrxyl site, an average turmaline rim cmpsitin can be recalculated (Table 5). This calculatin shws that ll.sv f the hydrxyl in the hydrxyl site wuld be replaced by xygen. This value represents the minimum amunt f dehydrxylatin since there will be additinal prtn lss if any f the Y site irn is trivalent r if Mg substitutes fr Na in the X site. The significant amunt f dehydrxylatin which is implied by this calculatin is cnsistent with the prbable invlvement f an aluminbuergerite substitutin in the turmaline rims. In additin. there are als vacancies in the X site reflecting a significant amunt f alkali defect substitutin. Table 4. Partitin cefficients fr turmaline rims and cexisting matrix phases Element pair l', 9-Fe M9-Fe Mg-Fe Mg-Fe Mg-Fe Na-Ca Mineral pair tu rna I i ne- bi t i te turmal ine-chlrite tuflnal i ne-garnet turma I i ne- crd'i eri te tu rma I i ne- stau rl i te K^U l. e86 ( ) 1.728(0.082 ) l 3.94 ( 0.72 ) r.236(0.068 ) 10.29(1.2s) turrnaline-plagiclase 1.582(0.120) * KD=(Mg/Fe)tu./(Ms/Fe)0..,," r (Na/Ca)ru./(Na/ca)pla9. **The estimated standard deviatins are givefl in parentheses. I'19/Fe l,lalca 5I Alt Alz Alv Ti fy TX I r t (. egg )* (r.190) ( ) (0.035) (0.035 ) ( ) 0.093(0.028) (.zt )** (0.014) The estimated standard deviatln is given in parentheses. **Ar"""g" tumaline rim fmula (n the basis f 29 xygen and 3 brn atms) : ( tia"ca*. rtu ) ( MgrF"zTl. sal 0. ltz tr. rgg )Al s. ( si s. gzgal. l t ) ( 803 ) ( 30rg 0H3.9zF. gg ) w= x= y= z= Average tunnallne rim fmula (n the basis f 3 brn atcms and a full ccupancy f 3 catlns in the Y slte): (Na*, car,g. ru, ) ( Mgr,Fez,Ti 0,09tAl. czl )Al. ( 5t s. gg+a1. r ) ( 803 )3018( Hg. +agf. gg ) w'= x'=0, y'=1.430-r.779 2'= Turmaline cre relatins. The range, mean, and standard deviatin f cmpsitins f the cntinuusly- and discntinuusly-zned cres are given in Table 6. As evidenced by the large range and standard deviatins, bth types fcres shw cnsiderably mre cmpsitinal variatin than the crrespnding rim cmpsitins. Despite the increased cmpsitinal variability the cntinuusly-zned (type (2)) cres have several distinct cmpsitinal trends relative t the rims: (l) the Mg/Fe ratis are lwer and the Na/Ca ratis are higher in these cres, (2) Si appraches the full six catins f the tetrahedral site and, cnversely, tetrahedral Al appraches zer, (3) ttal Al decreases slightly. (4) Ti usually decreases. These relatinships are illustrated qualitatively by the psitins f the cntinuusly-zned cres relative t the field f the rims in the Al-Fe(tt)-Mg diagram (Fig. 9) and Ca-Fe(tt)-Mg diagram (Fig. l0). These data suggest that frm the cre t the rim there is a cntinuus increase in the MgFe-r, AlzMg-rSi-r, CaMgNa- r Si-2, &rd TiAlzMg- r Si-2 cmpnents. These cmpnents prbably increased during prgrade grwth f the turmaline in the pelitic schists. These changes are analgus t the cmpsitinal changes bserved in

10 t0 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGEN ETIC I NDICATOR AI Alkali-free Dravite Schrl AluqFe(tt)r. Al5sMg5q Fig. 9. Al-Fe(tt)-Mg diagram fr turmaline cre and rim cmpsitins frm NW Maine. Mst f the data cluster alng a line f nearly cnstant Al cntent. The cmpsitins fthe turmaline cres are divided int the cntinuusly-zned cres (O) and the fur varieties fdiscntinuusly-zned cres as described in the text: variety l (A); variety 2 (I); variety 3 (V); and variety 4 (O). The dashed line represents the field encmpassed by the turmaline rim cmpsitins. The numbers in the fields crrespnding t ptential surce rck types are defined in Fig. l. bitite, muscvite, and plagiclase frm pelitic schists which increase in grade frm garnet t staurlite grade (Guidtti and Sassi, 1976; Guidtti et al., 1977; Guidtti, r978). Cre cmpsitins frm discntinuusly-zned (type (3)) turmalines are extremely variable and shw n relatin between the Mg/Fe and Na/Ca ratis and the cmpsitins f the cexisting matrix minerals. This type f cre can be gruped int fur brad cmpsitinal categries. Variety I has relatively high Fe cntents usually with an excess f catins in the Y site and deficiency inthez site. This implies that there is prbably a significant amunt f ferric irn substituting fr Al. In additin, there is an increase in Ti but a decrease in X site vacancies relative t their rims. Variety 2, a less abundant type, is characterized by high Ca and Ti cntents and typically high Mg/Fe ratis. It als has an Al deficiency in the Z site which is mst likely due t a substantial uvite substitutin. Variety 3, bserved in a single grain, has a very lw Mg/Fe rati but relatively high Al levels. Variety 4, bserved in a single grain, is very aluminus with lwer Ca and Ti cntents and higher MgiFe ratis relative t its nm. If it is assumed that the discntinuus cres are detrital in rigin, the chemistry f these discntinuusly-zned cres allws sme cnstraints t be placed n the pssible surce rcks. In Figures 9 and 10, the variety I cres fall in the fields that suggesthe turmaline cre frmed in relatively Fe3+-rich metapelites r metapsammites (prbably with n graphite present) nt cntaining an Alsaturating phase. The higher Ti cntents imply that they frmed at a diferent P,T cnditin and/r with a different Ti-saturating phase (such as rutile). The calcic and magnesian variety 2 cres fall in fields that suggest an envirnment which may be fund in carbnate-bearing metapelites and metapsammites. The variety 3 cre has a cmpsitin which falls well within the Li-pr granitid field suggesting it was detritus frm a granitid plutn. Finally, the aluminus variety 4 cre was prbably derived frm a pelitic schist which cexisted with relatively magnesian phases as well as an Al-saturating phase. The sedimentary surce regin fr the metapelites in the Rangeley quadrangle is presumed t be the Cambr- Ordivician strata f the Smerset Geanticline (Cady, 1968, 1969; Mench, 1973) which cntains relatively xidized hrizns f metapelites, metaquartzites, and metacarbnates as well as a few granitic plutns. These rck types are gd candidates fr surce rcks f the detrital turmaline fragments. Krynine (1946) has nted that since turmaline is extremely resistant t abrasin, it is cmmn t find that even in a single sedimentary basin, due t mixing frm several surce areas, there may be a

11 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGENETIC INDICATOR Ca Ca B ue rge Dravite Fetttl Mg Fig. 10. Ca-Fe(ttFMg diagram fr turmaline cre and rim cmpsitins frm NW Maine. The rim cmpsitins plt in a narrw band at nearly cnstant Ca cntent. The symbls fr the cre data are given in Fig. 9. The dashed line represents the utline fthe field encmpassed by the turmaline rim cmpsitins. The numbers in the fields crrespnding t ptential surce rck types are defined in Fig. 2. cllectin f turmaline grains f varius types. Thus even in a small area turmaline detritus frm several surce regins may be expected. These data suggest that detrital cres frm turmaline may prvide infrmatin n the prvenance f the sediments which predate metamrphism. Dev elp me nt f t urmaline during metamrphis m In the staurlite-grade pelitic schists f NW Maine, turmaline is dispersed thrughut the rcks and there is n evidence that its develpment is due t externallyderived, B-rich fluids. The turmaline must have been part f the riginal pelitic sediment and/r must have prgressively develped during metamrphism f the pelites. In mst cmmn metasediments the bulk f the brn is carried in the turmaline cntained in the rcks (Ethier and Campbell, 1977). Hwever, the surce f the brn in many sediments is smewhat prblematic. In carse clastic, sedimentary rcks turmaline has ften been bserved as a mechanically-resistant detrital mineral (Pettijhn et al., 1973). In cntrast, in fine-grained, argillaceus sedimentary rcks that are ften relatively rich in brn (Ethier and Campbell, 1977), the bulk f the brn cannt be cntained exclusivelv in the detrital turmaline grains. Instead, brn apparently (1) was in slutin in sea water and held by adsrptin nt the surface fclay minerals (especially illite), (2) substituted fr silicn in the tetrahedral sites f the clav minerals r fr carbn in Table 6. Variatin in turmaline cre cmpsitins cnti nuusly-zned cres w19lfe ,365(0.219) Na/ca ,73( si** Alr 5.gg r3(.5) i6 Ar z ( ) lv Ti ,055(0.021) F (0.038) ty 2.8r8-? ( ) E (0.048) Di scnti nuusly-zned cres (0.681) (5.911) s r(0.069) s.934(0.267) , (0.057) (0.05r) ,041(0.208) r(0.067) The estinated standard deviatins are given in Darentheses. --lhe structural fmula is ca'lculated n the basis f 29 xygen and 3 brn atns

12 l2 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGENETIC INDICATOR dlmite, r (3) was redistributed as a result f pstdepsitinal mvement f a brn-rich fluid (Stubican and Ry, 1962; Eager and Spears, 1966; Lerman, 1966) Cdy, 197 ; Abraham et al., 1972; Wadhawan and Rnwal, 1977; Ricketts, 1978; Slack, 1982). Cnsequently brn can be cncentrated in sediments by several mechanisms. The fllwing scenari is prpsed fr the develpment f turmaline during metamrphism f the pelitic sediments f NW Maine. With an increase in temperature the brn is released frm the clays and made available t interstitial fluids t react with the cexisting aluminsilicate minerals in the sediment t frm turmaline. This is initially reflected in the develpment f authigenic turmaline during the late stages f diagenesis frming as vergrwths n detrital turmaline grains and/r as newly-develped turmaline crystals. With a further increase in temperature, mre f the brn released frms additinal turmaline that armrs the preexisting cres. Thus, any detrital cre tends t be preserved by the turmaline vergrwths. At high grades f metamrphism, the turmaline grains tend t becme mre chemically hmgeneus. Fr instance, Frey (1969) nted that with increase in grade frm greenschist t amphiblite facies turmaline in metapelites has an increasingly greater prprtin f metamrphic vergrwth t detrital cre. The develpment f metamrphic vergrwths gives a mechanism that can prduce the type (3) zning patterns. Since the chemical zning mimics the cmpsitinal evlutins f the matrix minerals, the cntinuusly-zned turmaline (type (2)) prbably develped during prgressive metamrphism whereas the unzned type (l) turmaline cre prbably develped at nearly cnstant P,T cnditins. Cnclusins The investigatin f the chemical characteristics f accessry turmaline in staurlite grade metapelitic schists frm NW Maine demnstrates that turmaline can be a useful petrgenetic indicatr mineral. The rims f the turmaline grains appear t be in chemical equilibrium with the matrix minerals and have high regular partitin cefficients between turmaline rims and matrix minerals. Hwever, care must be exercised in cmparing partitin cefficients in rcks frm different regins t thse f this study. It must be certain that the rim f the turmaline is used fr element partitining and that cmpsitinal cmplexities in turmaline are minimized by cnsidering turmalines cexisting with the apprpriate saturating phases. The refractry nature f the turmaline is reflected in the strng zning patterns and detrital cres that apparently have nt undergne substantial chemical changes despite being subjected t staurlite-grade metamrphism. Cnsequently, by cnsidering the nature f the chemical zning, turmalines can be extremely useful prbes int the histry f the rcks in which they are fund. Finally, it is urged that turmaline becme a mineral that is rutinely cnsidered and carefully analyzed during any petrlgic study. As mre infrmatin becmes available, its utility and limitatins t petrgenesis will becme mre apparent. Acknwledgments This study was dne in partial fulfillment f the requirements fr the degree f Dctr f Philsphy at the University f Wiscnsin-Madisn (D.J.H.). Financial supprt came frm NSF Grants EAR and EAR-79-O2597 (C.V.G.). A prtin f the research was dne while D.J.H. held a Natinal Research Cuncil Pstdctral Fellwship at NASA-Jhnsn Space Center. The research was cmpleted while D.J.H. was a Visiting Research Scientist at the Lunar and Planetary Institute which is perated by the Universities Space Research Assciatin under Cntract N. NASW-3389 with NASA. We thank B. L. Dutrw and S. C. Bergman fr critical reviews and very useful cmments n an earlier versin f the manuscript. E. D. Ghent, J. M. Rice, and M. J. Hldaway are thanked fr their jurnal reviews. This paper is Lunar and Planetary Institute Cntributin N. 52E. References Abraham, K., Mielke, H., and Pvndra, P. (1972) On the enrichment f turmaline in metamrphic sediments f the Arzberg Series, W. Germany (NE Bavaria). Neues Jahrbuch fiir Mineralgie, Mnatshefte, Abraham, K. and Schreyer, W. (1973) Petrlgy f a femrginus hrnfels frm Riekensgluck, Harz Muntains, Germany. Cntributins t Mineralgy and Petrlgy, 40, Ackermand, D. and Mrteani, G. (1977) The chemistry f the garnets, chlrite, bitite, and turmaline in the Steinkgel Schist (Salzburg, Austria): the gelgical histry f the central Eastem Alps. Neues Jahrbuch Gelgische und Palentlgie, Abhandlungen, 154, Albee, A. L. and Ray, L. (1970) Crrectin factrs fr electrn prbe micranalysis f silicates, xides, carbnates, phsphates, and sulfates. Analytical Chemistry, 42, Awasthi, N. (1961) Authigenic turmaline and zircn in the Vindhyan frmatins f Sne Valley, Mizapur District, Uttar Pradesh, India. Jurnal f Sedimentary Petrlgy, 31, Babu, S. K. (1970) Mineralgy f achrite (clurless turmafine), frm a pegmatite near Ajmer. 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13 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGENETIC INDICATOR t3 Buska, V., Pvndra, P., and Lisy, E. (1973) Uvite frm Hnusta, Czechslavakia. Acta Universitatis Carlinae-Gelgica,3, Bwman, H. L. (1902) Occurrence f minerals at Haddam Neck, Cnnecticutt, USA. Mineralgical Magazine, 13, 108-lll. Bradley, J. E. S. and Bradley, O. (1953) Observatins n the cluring f pink and green zned turmaline. Mineralgical Magazine, 30, 26-3E. Bridge, P. J., Daniels, J. L. and Pryce, M. W. (1977) The dravite crystal bnanza f Yinnietharra, Westem Australia. Mineral Recrd Bruce, E. L. (1917) Magnesian turmaline frm Renfrew, Ontari. Mineralgical Magazine, 18, Burns, R. G. (1982) The blackness fschrl: Fe2*-Fe3* electrn delcalizatin in turmalines. Transactins f the American Gephysical Unin, 63, Cady, W. H. (1968) Tectnic setting and mechanism f the Tacnic slide. American Jurnal f Science, 266, Cady, W. H. (1969) Reginal tectnic synthesis f nrthwestern New England and adjacent Quebec. 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(1979) Preliminary reprt f authigenic, euhedral turmaline crystals in a prductive gas reservir f the Tiger Ridge Field, nrth-central Mntana. Jurnal f Sedimentary Petrlgy, 49, 9ll-916. Grelikva, N. V., Perfil'yev, Yu. D., and Bubeshkin, A. M. (1978) Mctssbauer data n distributin f Fe ins in turmaline. Internatinal Gelgy Review, 20, Guidtti, C. V. (1970) Metamrphic petrlgy, mineralgy, and plymetamrphism in a prtin f NW Maine. In G. M. Bne, Ed., The Rangeley Lakes-Dead River Basin Regin, Westem Maine, New England Intercllegiate Gelgical Cnference Guidebk B-2. l-29. Guidtti, C. V. (1974) Transitin frm staurlite t sillimanite zne Rangeley quadrangle, Maine. Gelgical Sciety f America Bulletin Guidtti, C. V. (1978) Cmpsitinal variatin f muscvite in medium- t high-grade metapelites f nrthwestern Maine. American Mineralgist, 63, 87E-884. Guidtti, C. V., Cheney, J. T., and Guggenheim, S. (1977) Distributin f titanium between cexisting muscvite and bitite in pelitic schists frm nrthwestern Maine. American Mineralgist, 62, Guidtti, C. V. and Sassi, F. P. (1976) Muscvite as a petrgenetic indicatr mineral in pelitic schists. Neues Jahrbuch ftir Mineralgie, Abhandlungen, 127, Henry, D. J. (1981) Sulfide-silicate relatins f the staurlite grade pelitic schists, Rangeley Quadrangle, Maine. Ph.D. dissertatin, University f Wiscnsin-Madisn. Henry, D. J. and Guidtti, C. V. (l9el) Implicatins f the sulfide-silicate interactins in staurlite grade metapelites in NW Maine. Transactins f the American Gephysical Unin, 62,435. Henry, D. J. and Guidtti, C. V. (1982) Sulfide-silicate-fluid interactins in metapelitic rcks: intemal vs. external cntrl. Gelgical Assciatin f Canada and Mineralgical Assciatin fcanada Prgram with Abstracts, 7, 55. Hermn, E., Simkin, D. J., Dnnay, G., and Muir, W. B. (1973) The distributin f Fe2* and Fe3* in irn-bearing turmalines: a Mdssbauer study. Tschermaks Mineralgische und Petrgraphische Mitteilungen, 19, Hldaway, M. J., Guidtti, C. V., Nvak, J. M., and Henry, W. E. (1982) Plymetamrphism in medium- t high-grade pelitic metamrphic rcks west-central Maine. Bulletin f the Celgical Sciety f America, 93, Hlgate, N. (1977) Turmaline frm amphiblized gabbr at

14 l4 HENRY AND GUIDOTTI: TOURMALINE AS A PETROGENETIC INDICATOR Hanter Hill, Radnrshire. Mineralgical Magazine, 41, Hutchen, I., Gunter, A. E., and Lecheminant, A. N. (1977) Serendibite frm Penrhyn Grup marble, Melville Peninsula, District f Franklin. Canadian Mineralgist, 15, l0e-l12. Jan, M. Q., Kempe, D. R. C., and Symes, R. F. (1972) A chrmian turmaline frm Swat, West Pakistan. Mineralgical Magazine, 38, Jedwab, J. (1962) Turmaline zinifere dan une pegmatite de Muike (Cng). Bulletin de la Sciete Belge de Gelgie, 71, Jnes, B. G., Carr, P. F., and Cndliffe, E. (1981) Ferrian turmaline frm Bungnia, New Suth Wales. Jurnal f the Gelgical Sciety faustralia, 28, Kitahara, J. (1966) On dravite (Mg-turmaline) frm the Hirse mine, Tttri Prefecture. Jurnal f the Japanese Assciatin f Mineralgists Petrlgists, and Ecnmic Gelgists, 56, Krvushkin, V. V., Kuzmin, V. L., and Belv, V. F. (1979) M<issbauer studies f structural features in turmaline f varius geneses. Physics and Chemistry f Minerals, 4, Kramer, H. and Allen, R. D. (1954) Analyses and indices f refractin f turmaline frm fault guge near Barstw, San Bernadin Cunty, Califrnia. American Mineralgist, 39, Krynine, P. D. (1946) The turmaline grup in sediments. Jurnal f Gelgy, 54, Leckebusch, R. (1978) Chemical cmpsitin and clur f turmalines frm Darre Pech (Nuristan, Afganistan). Neues Jahrbuch fiir Mineralgie, Abhandlungen, 133, Lerman, A. (1966) Brn in clays and estimatin f palesalinities. Sedimentlgy, 6, MacRae, N. D. and Kullerud, G. (1972) Preliminary investigatin f almandine-sulfur-water at 700'C and I kb. Canadian Mineralgist, ll, Mader, D. (1980) Turmaline authigenesis in carbnate-rck breccias frm the upper Bunter f the nrthern Triev Bay; western Eifel, Aufschluss Manning, D. A. C. (1982) Chemical and mrphlgical variatin in turmalines frm the Hub Kapng bathlith f peninsular Thailand. Mineralgical Magazine, 45, Mench, R. H. (1973) Dwn-basin fault-fld tectnics in western Maine with cmparisn t the Tacnic Klippe. In K. A. DeJng and R. Schlten, Eds., Gravity and Tectnics. p Interscience, New Yrk. Mench, R. H. and Zartman, R. E. (1976) Chrnlgy and styles f multiple defrmatin, plutnism, and plymetamrphism in the Merrimack Synclinrium f western Maine. In P. C. Lyns and A. H. Brwnlw, Eds., Studies in New England Gelgy, Gelgical Sciety f America Memir 146, Mukherjee, S. (1969) The chrme-turmaline frm Nausahi, Kenjhar District, Orissa. Quarterly Jurnal f the Gelgical Mining and Metallurgical Sciety f India, 40, ll Neiva, A. M. R. (1974) Gechemistry f turmaline (schrlite) frm granites, aplites and pegmatites frm nrthern Prtugal. Gechimica et Csmchimica Acta, Nemec, D. (1968) Flurine in turmalines. Cntributins t Mineralgy and Petrlgy, 20, Nvak, F. and Zak, L. (1970) Dravite asbests frm Chlavetice. Acta Universtitatis Carlinae-Gelgica, l, Nuber, B. and Schmetzer, K. (1979) I'he lattice psitin f Ct'* in turmaline; structural refinement f a chrmium-rich Mg- Al-turmaline. Neues Jahrbuch firr Mineralgie, Abhandlungen, 137, Ontev, D. O. (1956) On the cmpsrtin f certain re-frming turmalines. Transactins f the lnstitute fr the Gelgy f Ore-depsits, Petrgraphy, Mineralgy, and Gechemistry, 3, Osberg, P. H. (197E) Synthesis fthe gelgy fthe nrtheastern Appalachians, USA. Gelgical Survey f Canada, Paper 78-13, Otrshchenk, V. D., Dusmatv, V. 'D., Khrvat, V. A., Akramv, M. B., Mrzv, S. A., Otrshchenk, L. A., Khalilv, M. Kh., Khlpv, N. P., Vingradv, O. A., Kudryavtsev, A. S., Kabanva, L. K., and Sushchinskiy, L. S. (1972) Turmalines in Tien Shan and the Pamirs, Sviet Central Asia. Internatinal Gelgy Review, 14, ll73-ll8l. Pagliani, G. (1949) La turmalina di Beura. Atti della Scieta Italiana di Scienze Naturali e del Muse Civic di Stria Naturale di Milan l-198. Peltla, 8., Vurelainen, Y., and Hakli, T. A. (1968) A chrmian turmaline frm Outkumpu, Finland. Bulletin f the Gelgical Sciety f Finland, 40, Pettijhn, F. J., Ptter, P. E. and Siever, R. (1973) Sand and Sandstnes. Springer-Verlag, New Yrk. Pvndra, P. (1981) The crystal chemistry f turmalines f the schrl-dravite series Acta Universitatis Carlinae-Gelgica, Pwer, G. M. (1968) Chemical variatin in turmalines frm Suth-West England. Mineralgical Magazine, 36, Raheim, A. (1977) Petrlgy f the Strathgrdn area, western Tasmania: Sia*-cntent f phengite mica as a mnitr f metamrphic grade. Jurnal f the Gelgical Sciety f Australia Rath, R. and Puchelt, H. (1957) Indiglith vn Usaks. Neues Jahrbuch fiir Mineralgie, Mnatshefte, Rath, R. and Puchelt, H. (1959) Dravit vn Guverneur. Neues Jahrbuch fiir Mineralgie, Mnatshefte, Ricketts, B. D. (197E) Authigenic turmaline frm the Middle Precambrian Belcheger grup, Nrthwest Territries, Canada. Bulletin f Canadian Petrleum Gelgy, 26, Rsenberg, P. E. and Fit, F. F. Jr. (1979) Synthesis and characterizatin f alkali-free turmaline. American Mineralgist,64, le0-1e6. Sahama, Th. G., vn Knrring, O., and Trns, R. (1979) On turmaline. Liths Sandrea, A. (1949) Surune variety de turmaline sd-manganesifere dans des filns de pegmatite des envirn des Rscf. Cmptes Rendus Hebdmdaires des Seances de I'Academie des Sciences, Paris, 228, Schmetzer, K., Nuber, B., and Abraham, K. (1979) Crystal chemistry f magnesium-rich turmalines. Neues Jahrbuch fiir Mineralgie, Abhandlungen, 136, Schreyer, W., Abraham, K., and Kulke, H. (1980) Natural sdium phlgpite with ptassium phlgpite and sdian aluminian talc in a metamrphic evaprite sequence frm Derrag, Tell Atlas, Algeria. Cntributins t Mineralgy and Petrlgy,74, Schreyer, W., Werding, G. and Abraham, K. (1981) Crundumfuchsite rcks in greenstne belts f suthern Africa: petrlgy, gechemistry, and pssible rigin. Jurnal f Petrlgy, 22,191-23r. Serdyuchenk, D. P. (1976) Archean turmaline-bearing and

15 HENRY AND GUIDOTTI: TOT]RMALINE AS A PETROGENETIC INDICATOR 15 ther metasedimentary gneisses f the Azv regin, as related Wadhawan, S. K. and Rnwal, G. S. (1977) Genetic significance f turmaline assciated with sulphide mineralizatin at t their palegegraphic envirnment f frmatin. Dklady, Academy f Sciences fthe USSR, Earth Sciences Sectins, Zawar area, Udaipur, Rajasthan, India. Neues Jahrbuch fiir Mineralgie, Mnatshefte, Slack, J. F. (1982) Turmaline in Appalachian-Calednian massive sulphide depsits and its explratin significance. Tran- f the turmaline grup frm Blivia. American Mineralgist, Walenta, K. and Dunn, P. I. (1977) Ferridravite, a new mineral sactins/sectin B f the Institutin f Mining and Metallurgy, 64, , B8l-B87. Wang, S. and Xue-yen, H. (1966) A new variety f dravite and its Slivk, M. N. (1959) Manganese turmalines. Mineralgichesky signifi cance in mineralgy. Kexue Tngba, 17, sbrnik, Lvvskg gelgcheskg bshchestva, 13, 139- Williams, G. A. (1891) Minerals frm Maryland. Mineralgical 148. Magazine,9,247. Snetsinger, K. G. (1966) Barium-vanadium muscvite and vanadium turmaline frm Maripsa Cunty, Califrnia. American lithium in sme Crnish minerals: in micrprbe measure- Wilsn, G. C. and Lng, J. V. P. (19E3) The distributin f Mineralgist, 51, ments. Mineralgical Magazine, 47, l9l-199. Staatz, M. H., Murata, K. J., and Glass, J. J. (1955) Variatin f Zen, E. (1981) Metamrphic mineral assemblages f slightly cmpsitin and physical prperties f turmaline with its calcic pelitic rcks in and arund the Tacnic Allchthn, psitin in the pegmatit. American Mineralgist,40, 789-8M. suthwestern Massachusetts and adjacent Cnnecticut and Stubican, V. and Ry, R. (1962) Brn substitutin in synthetic New Yrk. United States Gelgical Survey Prfessinal micas and clays. American Mineralgist, 47, Paper, ll13, l-128. Thmpsn, A. 8., Lyttle, P. T., and Thmpsn, J. B. (1977) Mineral reactins and A-Na-K and A-F-M facies types in the Manuscript received, Octber 3, 1983; Gassetts schist, Vermnt. American Jurnal f Science acceptedfr publicatin, September 18, l9a. ll24-lt5t. Thmpsn, J. B., Jr. (1972) Oxides and sulfides in reginal metamrphism f pelitic schists. Prceedings f the 24th Appendix I Intematinal Gelgical Cngress, Mntreal, Sectin 10, 27- Surce papers fr turmaline analyses 35. Thmpsn, J. B., Jr. (1982) Cmpsitin space: an algebraic and Turmaline cmpsitinal data used t define the fields in the gemetric apprach. In J. M. Ferry, Ed., Characterizatin f Al-Fe(ttFMg and Ca-Fe(tt)-Mg diagrams were taken frm: Metamrphism thrugh Mineral Equilibria. Reviews in Mineralgy, 10, l-31. Celh, 1948; Pagliani, 1949; Sandrea, 1949; Bradley and Williams, l89l; Bwman, 1902; Bruce, l9l7; du Rietz, 1935; Thmpsn, J. B., Jr., Laird, J., and Thmpsn, A. B. (1982) Bradley, 1952; Kramer and Allen, 1954; Staatz et al., 1955; Reactins in amphiblite, greenschist and blueschist. Jurnal Ontev, 1956; Rath and Puchelt, 1957,1959; Slivk, 1959; Deer fpetrlgy,23, l-27. et ai., 1962: Jedwab, 1962; El-Hinnawi and Hfmann, 1966; Tsang, T. and Ghse, S. (1973) Nuclear magnetic resnance f Frndel et al., 1966; Kitahara, 1966; Snetsinger,1966; Wang and rh, 7Li, ttb, t'n" and 27Al in turmaline (elbaite). American Xue-yen, 1966; Peltla et al., 1968; Pwer, 1968; Mukherjee, Mineraf gist, 58, ; Babu, 1970; Nvak and Zak,1970; vn Knrring, 1970; Tsang, T., Thrpe, A. N., and Dnnay, G. (1971) Magnetic Otrschenk et al., l97l; Tsang et al., l97l; Abraham et al., susceptibility and triangular exchange cupling in the turmaline mineral grup. Jumal f the Physics and Chemistry f Kullerud, 1972; Abraham and Schreyer, 1973; Buska et al., 1972; Dnnay and Bartn, 1972; Jan et al., 1972;' MacRae and Slids,32, l44l-r ; Neiva, 1974; Frtier and Dnnay, 1975; Chaudry and vn Knrring, O. (1970) Mineralgical and gechemical aspects Hwie, 1976; Serdyuchenk, 1976; Ackermand and Mrteani, f pegmatites frm rgenic belts f equatrial and suthern 1977; Bridge et al.,1977; Dunn, 1977; Dunn et al. 1977a, 1977b; Africa. In Cliffrd, T. N. and Gass, L G., Eds., African Ethier and Campbell, 1977;Hl9ate, 1977; Hutchen et al.,1977; Magmatism and Tectnics, p Oliver and Byd, Raheim, 1977; Frd and Mills, 1978; Grelikva et al., 1978; Edinburgh. Leckebusch, 1978; Fit and Rsenberg, 1979; Sahama et al., Vrana, S. (1979) A plymetamrphic assemblage f grandidierite, krnerupine, Ti-rich dumrtierite, turmaline, sillimanite, 1979; Schreyer et al., 1980, l98l; Pvndra, 1981; Jnes et al., 1979; Schmetzer et al., 1979; Yrana, 1979; Walenta and Dunn, and garnet. Neues Jahrbuch fiir Mineralgie, Mnatshefte, ; Manning, 1982; Baker and de Grt, 1983; Wilsn and JJ. Lng, 1983; Henry (unpublished data).

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