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Worldwide, the anoxic, organic-rich sediments col-lectively referred to as �black shales� are know to bean important sink for oceanic uranium. There have beenestimates that suggest that as much as 20% of theannual fluvial input of U into the world�s oceans may bebound in such organic-rich strata [1]. Adsorption of Uonto organic matter has been suggested as an essen-tial preconcentration step in the formation of many sedi-mentary ore deposits. However, the bio-geochemicalprocesses by which U is incorporated into these sedi-ments are still not clearly understood. The redox con-ditions and kinetics at the sediment-water interface, theamount of organic material present, fluid-mineral andmineral-mineral reactions are all known to play impor-tant roles in how U is incorporated [1,2,3].

Here we present microbeam synchrotron x-ray fluo-rescence, diffraction, and XANES analyses frombeamline X26A at the NSLS on a single thin-section ofa Jurassic fish coprolite from a black-shale horizon incentral Connecticut (ca. 198 million years old). Copro-lites are fossilized fecal material and, as such, clearlycontained organic material at one time. These coproli-tes, now preserved as phosphatic material, are unusualin that they have very high levels of uranium, often inexcess of 600 ppm. This provides an opportunity toevaluate the mineral and organic interactions that haveresulted in the partitioning of U into these coprolites.This study also demonstrates the unique microbeamcapabilities of the X26A beamline for near simultaneousevaluation of major and trace element compositionsusing synchrotron x-ray fluorescence (XRF), elemen-tal speciation using fluorescence mode x-ray absorp-tion near-edge spectroscopy (XANES), and mineral-ogy using micro x-ray diffraction (XRD) of geologic andenvironmental samples at spatial resolutions of ~10µm.

Geology and Mineralogy:The Shuttle Meadow Formation was deposited as

rift-basin sediments and is the lowermost Jurassic sedi-mentary unit of the Hartford Basin in southern Con-necticut. Although siliciclastic alluvial sediments domi-nate the formation, it�s lowermost section contains asingle black shale horizon that is believed to representthe deposition of sediment in an offshore lake environ-

ment. This black shale contains abundant, fully articu-lated fish fossils (genus Semionotus, Redfieldius,Diplurus) and their associated coprolites. Now pre-served as phosphatic minerals, the original organicmaterial in these coprolites provided a nucleation sitefor HPO4

-, resulting in the precipitation of phosphate.During early diagenesis, phosphatization begins beforethe complete decay of organic material and additionalHPO4

- may be introduced by the decay of fish debris(fish teeth and bones composed of hydroxyapatite)contained within the coprolite.

Figure 1 shows two photomicrographs of thin-sec-tions that were made through the coprolite that we dis-cuss in this study. In this discussion, we will focus onthis one particular sample because of its well-preservedoptical zoning. Figure 1a shows the coprolite sectionthat was analyzed at X26A. The coprolite is the darkblack, layered material in the image and is surroundedby matrix minerals of the host shale (the fine, gray lay-ers on the margin). The labeled points on the imageshow where the discussed analyses were taken (seefigure caption). Figure 1b is a photomicrograph of asecond section through this same coprolite. This sec-tion was heated at 450°C for 4 days. As a result of thisheating the coprolite has turned from opaque black tolight brown, accentuating many of the internal struc-tural details that were not visible before. The change incolor and opacity are likely the result of pyrolization oforganic matter in the section, indirectly showing thatthese coprolites still contain organics. The layering inthe coprolite most likely reflects variability in either com-position (mineralogic or organic) or grain size, or both.

Analyses were conducted on 300 µm thick polishedsections of coprolite mounted on glass with epoxy. Theincident beam was tuned to the U LIII binding energyusing our Si(111) channel-cut monochromator. This 350µm collimated monochromatic beam is then focusedto 10 µm in diameter using our system of Rh coatedKirckpatrick-Baez mirrors [4]. XRF compositional dataand fluorescence mode XANES were collected usinga Canberra SL30165 Si(Li) detector. Elemental abun-dances were calculated using a modified version ofNRLXRF [5], designed for �standard-less� analysis ofXRF spectra obtained with monochromatic radiation.

Uranium Behavior in Jurassic Fish Coprolites: CombinedMicrobeam Synchrotron X-Ray Fluorescence, Diffraction,and XANES Analysis

A. Lanzirotti1, M. Becker2, G.N. Hanson2, and S.R. Sutton1

1University of Chicago, 2State University of New York-Stony Brook

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This standard-less approach uses an internal referenceelement, in this case the Ca concentration in the hy-droxyapatite that composes the coprolite (fixed by sto-ichiometry), and computes relative sensitivities usingthe prediction capabilities of NRLXRF. U XANES datawere collected in fluorescence mode by scanning themonochromator through the U LIII binding energy.XANES energy calibrations are based on analysis ofUO2 and UO3 standards and are plotted relative to theU LIII absorption edge of 17,166 eV, normalized to pho-ton flux monitored by an upstream ion chamber. Everythird XANES spectrum collected was a re-analysis ofthe UO2 standard to monitor for energy drifts due pri-marily to monochromator heating with time. Any suchdrifts were then corrected. Microbeam XRD data were

Figure 1: a) Photomicrograph of the Jurassic fish coprolite(fossilized fecal material) analyzed in this study. The samplenumbers �002, 010, 012, 028, 031, 033, 036, and 037� aresynchrotron microbeam XRD analyses discussed in the text.Sample numbers �X18, and X27� are XANES analyses dis-cussed in the text. The spot labeled �XRF� is the XRF spec-tra shown as an inset in Figure 4. b) Photomicrograph of aseparate section of this coprolite that was heated at 450°Cfor four days.

collected using a Brucker SMART CCD system in re-flection mode geometry. The wavelength of the inci-dent beam during the diffraction analyses was kept at0.7976 Å. Because of the small spot size of the inci-dent beam relative to the grain size of the minerals inthe section, the intensity of diffraction peaks can bestrongly affected by grain size and the preferred orien-tation of minerals in thin section. The more coarselycrystalline the material is, the greater the divergencefrom a typical powder pattern.

Microbeam XRD Results:Quantitative identification of mineralogy in shales

is often difficult because of the cryptocrystalline char-acter of the minerals. Accurate determinations by opti-cal petrography are often impossible and compositionalanalysis by electron beam microanalysis usually onlyindirectly identifies the mineral. Synchrotron microbeamXRD provides a unique method by which to quantita-tively identify such minerals in-situ and provides con-clusive results when coupled with simultaneous XRFmeasurements. Figure 2 shows a series of XRD pat-terns collected on the coprolite section shown in Fig-ure 1a. The inset images show representative CCDdiffraction patterns from each group of analyses. Thefigure on the left, labeled �Matrix,� shows four diffrac-tion patterns collected on matrix phases at spots 002and 010, well within the surrounding matrix, and 012and 028, in the matrix but adjacent to the coproliteboundary. Note that although the patterns are �spotty,�they are still good powder patterns, consistent with anaverage grain size much smaller than the diameter ofthe incident beam (~10 µm). Also shown are diffractionpatterns for quartz (red) and dolomite (blue). The XRDdata are consistent with the mineralogy of the matrixbeing dominated by these two phases. This is a bitunusual for black-shales, which typically have higherclay contents and less carbonate. The plot on the right,labeled �Coprolite,� shows four XRD patterns collectedwithin the coprolite itself. Analyses 031 and 036 arewithin the darker bands and analyses 033 and 037 arein the lighter colored bands. The majority of the diffrac-tion peaks can be accounted for by the minerals hy-droxyapatite (orange) and dolomite (blue). Note thatthere is little difference between the diffraction patternsfrom dark and light colored bands, suggesting little dif-ference in bulk mineralogy between these zones. Nodistinct U bearing minerals such as uraninites are iden-tifiable. It is important to note, however, that in ourpresent mode of operation differences in organic con-tent would not be detected.

Microbeam XRF Results:Figure 3 shows a set of four XRF compositional

maps of the coprolite shown in Figure 1a. A typical XRF

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Figure 2: Intensity vs. 2-theta microbeam x-ray diffraction patterns for selected points in the matrix (left) and coprolite (right)shown in Figure 1a. Also superimposed are diffraction patterns for dolomite (blue), quartz (red), and hydroxyapatite (orange).The inset figures show representative Brucker CCD diffractometer patterns for each group of analyses, 002 for the matrixand 031 for the coprolite.

Figure 3: Synchrotron microbeam XRF compositional maps of the coprolite shown in Figure 1a. Ca is shown in normalizedcounts for the Ca Kα fluorescence peak, Sr, Y, and U are in ppm.

2 - 51 Science Highlights

energy dispersive spectrum is shown as an inset in Fig-ure 4. The map for Ca is shown in normalized countson the Ca Ka peak while the other three maps are inppm. The Ca map shows that although the Ca fluores-cence in the coprolite is generally uniform, there aresome variations that correlate with the optical varia-tions seen in thin section. The XRD results suggestthis is not a result of mineralogic variability betweenbands. It is possible, however, that such variations couldbe accounted for by variability (type or abundance) inthe organic matter between bands. Sr2+ and Y3+ bothcommonly substitute for Ca in the apatite structure,since they have similar ionic radii and charge, althoughY incorporation usually requires coupled substitutionof ionic complexes, such as SiO4 for PO4, to maintaincharge balance. In the compositional mapping, thereis a clear correlation of Sr and Y abundance with Caand with the optical zoning in the coprolite. The U XRFcompositional map shows that U abundance through-out the coprolite is high (~600 ppm average) relative to

the matrix and that the U displays compositional zon-ing that correlates with the optical zoning in the hy-droxyapatite. U is also known to be a common traceelement in apatite and is often used for U238 fission trackdating of geologic materials. How U is incorporated intothe apatite structure is still debated (and dependant onit�s oxidation state), but in most models U (most likelyas 4+, ionic radius of 0.97 Å) substitutes for Ca 2+ (ionicradius of 0.99 Å) in its 7- and 9-fold coordinated sites,with some coupled substitution to account for chargebalance. Thus, it should mimic the behavior of Y. Whatthe XRF analyses demonstrate, however, is that the Uabundance in this coprolite (~400-1000 ppm) is in-versely correlated with Ca, Sr, and Y.

XANES Results:Figure 4 shows two representative XANES spec-

tra collected from the coprolite. Although there is somevariability in edge position, particularly for analyseswithin 100 µm of the coprolite edge, the XANES spec-

Figure 4: U LIII XANES spectra for the UO2 and UO3 standards and two selected points in thecoprolite (X18, and X27 in Figure 1a). Spectra are normalized to their respective edge steps.

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tra throughout most of the coprolite is very similar tothe two spectra shown here. Analysis X18 is midway tothe center of the coprolite in a high U band and analy-sis X27 is from the U rich center of the coprolite. Theseanalyses are superimposed with XANES spectra of ourUO2 and UO3 standards. Although structure and matrixeffects may have the potential to produce an edge shift,it is clear that relative to the UO2 standard, the relativeXANES edge energies of these analyses are shiftedtowards higher energy. Additionally, these spectra havea small post-edge multiple resonance peak similar tothe �shoulder� typically observed in U(VI) XANES spec-tra [2]. It is thus likely that much of the U in this particu-lar sample is oxidized and dominated by U(VI).

Although it is no surprise that a black-shale suchas that preserved in the Shuttle Meadow formation orthe phosphates contained within it are high in U, themicrobeam analyses at X26A provide interesting in-sights into the geochemistry of U incorporation in suchsediments. It is clear from the XRF energy dispersiveanalyses that the coprolites themselves are the domi-nant U bearing material in these sections. The micro-beam XRD data show that the primary mineralogic dif-ference between matrix and coprolite is the presenceof hydroxyapatite. It would seem logical to concludethat early phosphotization of the coprolite provided asite for U incorporation into the apatite structure. How-ever, the XRF compositional mapping shows an inversecorrelation between U (which should substitute for Ca)and other trace element constituents such as Sr and Ythat are known to substitute for Ca in apatite. It is likelythat the high U abundances may reflect complexationof U with the organic matter in the coprolite close to thetime of diagenesis of the sediment under anoxic condi-tions. Bacterial sulphate reduction can then releasedissolved HCO3

-, HPO4-, and NH4

+ and provide a nucle-ation site for HPO4

-, resulting in the precipitation of phos-phate. In such a scenario the U abundance is controlledprimarily by the abundance of organic C, rather thanthe abundance of phosphate. What is then difficult toexplain is why the XANES analyses suggest the pres-ence of oxidized U in these samples. Black-shales areknown to form beneath oxygen depleted bottom wa-ters and to be rich in organic C, which could be as-sumed to favor chemical and/or biological reduction ofU during sedimentation. In this case, later oxidation ofthe U is needed to explain the speciation we observein these coprolites today. Such reactions could be re-lated to later lithification of the sediment. However, somestudies have shown that in some sediments depositedunder reducing conditions often the first U solids to pre-cipitate are predominantly U(VI) [2]. Duff et al. wereable to demonstrate that even under low Eh conditionsreaction kinetics often still favor the precipitation of U(VI)solids. Although at this time these questions cannot be

quantitatively evaluated, future EXAFS and FTIR analy-ses may provide better insights into how U is bound inthese unique samples. But the observation that muchof the uranium may potentially be bound to organicmatter is consistent with other recent studies of black-shales that have found that despite the presence ofpotential U-rich diagenetic phases such as apatite andmonazite, most of the U is associated with non-extract-able diagenetic components such as organics [6].

Aknowledgements:This research was funded by grant

DOEFG0292ER14244 to S. Sutton andDERO294ER14449 to G. Hanson and W. Meyers. Themicrodiffraction studies are a collaborative effort be-tween A. Lanzirotti and John Parise (SUNY Stony Brook,Geosciences) to promote advances in environmentalmicrodiffraction studies at X26A. The installation of theBruker CCD facility at the NSLS was supported by theNSF through grant EAR-9724501/Stony Brook to JohnParise.

References:[1] C.E. Barnes and J.K. Cochran, �Geochemistry of Uranium

in Black Sea Sediments,� Deep-Sea Research, 38, p.S1237-S1254, 1991.

[2] M.C. Duff et al., �The chemistry of Uranium in EvaporationPond Sediment in the San Joaquin Valley, California,USA, using X-ray Fluorescence and XANES Techniques,�Geochimica et Cosmochimica Acta, 61, p.73-81, 1997.

[3] D.R. Lovely et al., �Microbial Uranium Reduction,� Nature,350, p.413-416, 1991.

[4] P. J. Eng, M. Newville, M.L. Rivers, and S.R. Sutton, �Dy-namically figured Kirkpatrick Baez micro-focusing optics,�in X-Ray Microfocusing: Applications and Technique, I.McNulty, ed., Proceedings SPIE, 3449, p. 145, 1998.

[5] J.W. Criss, �NRLXRF, A FORTRAN Program for X-RayFluorescence Analysis,� Naval Research Laboratory,Washinghton, D.C., 1977.

[6] S.M. Lev, S.M. McLennan, AND G.N. Hanson, �Late Di-agenetic Redistribution of Uranium and Disturbance ofthe U-Pb Whole Rock Isotope System in a Black Shale,�Journ. Of Sedimentary Research, 70, 2000.

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Evaluating Heterogeneous Reactivity at the Mineral-WaterInterface from Sectoral Zoning of REEs, Sr and Y in FluoriteJ. Rakovan1, S. Bosze1, and A. Lanzirotti2

1Miami University, Oxford, OH, 2University of Chicago-CARS

One of the hallmarks of mineral surface reactivityis its heterogeneous nature. Not only do different min-erals behave in strikingly different fashions, but alsowithin the confines of a single mineral�s surface, reac-tivity can vary significantly. A fundamental insight gainedfrom mineral surface studies is that a bulk atomic sitewithin a crystal may have multiple, distinctly differentsurface representations, the presence of which leadsto heterogeneous reactivity at the mineral-water or min-eral-melt interface (Reeder and Rakovan 1999). Oneof the most significant geochemical processes that takeplace at these interfaces is crystal growth.

During crystal growth, minor or trace amounts ofsubstituent elements may become incorporated in regu-lar atomic sites within the crystal. Because trace ele-ments are sensitive indicators of geologic processes,trace element geochemistry has formed the basis formany studies. Applications include the interpretation ofpetrogenesis, hydrothermal mineralization, water qualityand history, and geochronology. Essential to such stud-ies is knowledge of the partitioning of specific trace el-ements between different phases in a system. Manycomplex variables affect the partitioning of trace ele-ments into minerals during crystal growth. Recently,numerous authors have demonstrated the role of sur-face structure on the partitioning of elements into crys-tals (Paquette and Reeder, 1995, 1995; Northrup andReeder 1994; Rakovan and Reeder 1994, 1996;Rakovan et al. 1997; Bosze and Rakovan, 1999; Boszeand Rakovan in prep.). We are continuing our studiesof the role of crystal surface structure in heterogeneousreactivity of minerals, specifically addressing differen-tial adsorption and incorporation of trace metals intothe mineral fluorite. Here the differential incorporationof REEs, Y and Sr into fluorite is being used as a probeof the structural differences between nonequivalent sur-face sites.

Fluorite crystals from several important hydrother-mal mineral deposits, including the Hansonburg Min-ing District, Bingham, NM (Taggart et al. 1989) and theLong Lake fluorite deposit, St. Laurence fluorite dis-trict, NY (Richards and Robinson 2000), are being stud-ied. Crystals from these deposits exhibit multiple, sym-metrically nonequivalent crystal forms (Figure 1a). Theconcentration and distribution of the trace elementswithin oriented sections of single crystals are measuredby spatially resolved synchrotron X-ray fluorescencemicroanalysis line and area scans.

Standard X-ray fluorescence experiments at X26Ahave involved the use of energy dispersive (EDS) de-tectors. Because of the small separation amongst thenumerous L fluorescence lines of the REE series, wave-length-dispersive detection is necessary to resolve andquantify individual REE distributions. The increasedenergy resolution of WDS, 3 eV to 25 eV (FWHM) formost elements, allows for detection of individual REEs.A Microspec WDX-3PC wavelength-dispersive spec-trometer is used with a LiF (200) crystal to analyze theREE Lα1 and Lβ1 lines. Data are collected using a whitesynchrotron beam collimated to an incident size be-tween 8 and 100 µm, depending on the spatial resolu-tion necessary to resolve individual sectors (volumesof the crystal that grew by incorporation of growth unitsor adatoms onto a specific crystal face). Comparisonof the peak to background ratios shows that the effec-tive sensitivity, or the minimum detection limit, of theWDS spectrometer is comparable to that of the EDSfor the REEs. Figure 2 compares SXRFMA data col-lected on the same sample using EDS and WDS. Esti-mated relative precisions for the elements consideredhere are approximately 1%.

SXRFMA line and area scans show that Sr, Y, andREE compositional differences exist for coeval portionsof symmetrically nonequivalent sectors in the fluoritesstudied (Figures 1 a and b and 3). Such intracrystallineheterogeneities are known as sectoral zoning (SZ). Therelationship of sectors to crystal faces suggests thatthese heterogeneities formed during crystal growth. Twodistinct mechanisms for SZ have been identified; dif-ferences in the growth rate of nonequivalent crystalfaces, and the presence of distinctly different sites ofincorporation (on the nonequivalent crystal faces). Theinternal morphology (concentric zoning and sectorshape) of these samples revealed bycathodoluminescence indicates roughly equivalentgrowth rates of many of the crystal faces associatedwith the sector zoning. Hence, growth rate anisotropyis not the cause of SZ in these samples.

It is hypothesized that differences in the surfacestructure of these different crystal faces on fluorite, spe-cifically the structure of sites of incorporation on differ-ent faces, lead to different affinities for the trace ele-ments studies, and hence differential incorporation.

Long Lake fluorites exhibit {100} and {111} crystalfaces. Figure 1b,c shows the differential distribution ofGd between |111| and |100| sectors associated with

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Figure 2. Synchrotron X-ray fluorescence microanalysis (SXRFMA) data collected by EDS (dotted line) and WDS (solid line)from an apatite from Llallagua, Bolivia. Figure modified from Rakovan et al. (2001).

Figure 1. Zoning of Gd between |111| and |100| sectors of fluorite from Long Lake, NY. a) Schematic showing ideal 3Ddistribution of cube |100| and octahedral |111| sectors (internal morphology) within a cubooctahedral crystal. b) Schematic ofthin section taken from crystal in figure 1a. Double arrow indicates the position of an X-ray fluorescence line scan takenbetween two symmetrically nonequivalent sectors. c) Plot of the concentration of Gd (ppm) along the line scan indicated in b.Figure modified from Bosze and Rakovan (in Rev).

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Figure 3. Sectoral zoning of Sr and Y in fluorite from Bingham, NM. The image on the left is an optical photomicrograph of asection cut through a single crystal of fluorite. Color zoning shows the internal morphology is comprised of |111|, |110| and|100| sectors. The top-right figure is a plot of the concentration of Sr (brighter colors represent higher concentration) for anarea scan indicated by the yellow dashed line in the photomicrograph. The bottom-right figure is a plot of the concentrationof Y (brighter colors represent higher concentration) for the same scan. Figure modified from Bosze and Rakovan (in Rev).

these faces. Fluorites from Bingham, NM are unique inthat they exhibit six symmetrically different sectors, withas many as four in any one single crystal. Sectoral zon-ing of Sr, Y and REEs is found amongst all of the ex-hibited sectors. Figure 3 shows sectoral zoning of Srand Y among |111|, |110| and |100| sectors of a Binghamfluorite. Sr is enriched in the |110| sector relative to |111|and |100|, while Y is preferentially incorporated into the|111| sector.

The presence of sectoral zoning in fluorite demon-strates non-equilibrium incorporation and indicates that

factors such as growth mechanism and surface struc-ture are important in partitioning. Sectoral zoning notonly demonstrates that mechanistic factors play a rolein partitioning, but also that partition coefficient, Kd

, val-ues for a given mineral-fluid system are not unique.Rather, the Kd may differ for structurally distinct regionsof a crystal surface.

The observed partitioning differences betweennonequivalent sectors are being used to constrain mod-els of the atomic structure of the fluorite surface. Thusgiving us a better understanding of the nature of the

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mineral-water interface and the mechanisms of differ-ential incorporation during crystal growth.Acknowledgments:

This work has been supported by NSF grant EAR-9814691.

References:S. Bosze and J. Rakovan, � Surface Controlled Heteroge-

neous Incorporation of REE, Sr and Y in Fluorite�. An-nual Geological Society of America meeting, Abstractswith program. p. A-358, 1999.

S. Bosze and J. Rakovan, �Surface Controlled Non-Equilib-rium Incorporation of the Rare Earth Elements in Fluo-rite from Long Lake, N.Y. and Bingham, N.M.� In prep.

P.A. Northrup and R.J. Reeder, �Evidence for the importanceof growth-surface structure to trace element incorpora-tion in topaz� American Mineralogist, 79, 1167-1175,1994.

J. Paquette and R.J. Reeder, �Relationship between surfacestructure growth mechanism, and trace element incor-poration in calcite� Geochimica et Cosmochimica Acta,59, 735-749, 1995.

J. Rakovan, M. Newville and S. Sutton (2001) �Wavelengthdispersive XANES of heterovalent Eu in Llallagua apa-tite� American Mineralogist, in press.

J. Rakovan and R.J. Reeder, � Differential incorporation oftrace elements and dissymmetrization in apatite: The roleof surface structure during growth� American Mineralo-gist, 79, 892-903, 1994.

J. Rakovan and R.J. Reeder, �Intracrystalline rare earth ele-ment distributions in apatite: Surface structural influenceson incorporation during growth� Geochimica etCosmochimica Acta, 60, 4435-4445, 1996.

J. Rakovan, D.K. McDaniel, and R.J. Reeder �Use of sur-face-controlled REE sectoral zoning in apatite fromLlallagua, Bolivia, to determine a single-crystal Sm-Ndage� Earth and Planetary Science Letters, 146, 329-336,1997.

R.J. Reeder and J. Rakovan, �Surface structural controls ontrace element incorporation during crystal growth� InGrowth, Dissolution and Pattern-formation inGeosystems, B. Jamtveit and P. Meakin (eds.) p. 143-162. Kluwer Academic Publishers, 1999.

P.R. Richards and G.W. Robinson, �Mineralogy of the calcite-fluorite veins near Long Lake, New York� MineralogicalRecord, 31, 413-422, 2000.

J.E. Taggart Jr., A. Rosenzweig, and E.E. Foord, �TheHansonburg District, Bingham, New Mexico� Mineralogi-cal Record, 20, 31-46, 1989.