Net. Geophys Vol. 7, No.3, pp. 389-406, 1983 308693 ssc07.00 Pinte in Great Britain All hs resend CConyiht 1985 Pergamon Press Lid Elemental Composition and Nuclear Parameters of Some Common Sedimentary Minerals MICHAEL M. HERRONS and ABIGAIL MATTESON ‘Sehlumberger-Doll Research, Old Quarry Road, Ridgefield, CT 06877-4108, US.A (Received 28 Apri 1993) [Abstract Mjor and trce clement chemistry has been used to investigate eitical characteristics of 89 ‘specimens of 15 minerals that are commonly found in sedimentary rock. For kaolinite, Na”, Mg and ‘Ca?* are exchangeable cations while other elements are esentilly no-exchangeable, The compositional ‘aablity of most minerals seen tobe quite low (even fr clay minerals) which bodes wel for resolving the mineralogy of formations from down-hole elemental data. Nuclear parameters such asthe photocletre absorption oss section, natural gamma-ray activity, thermal neutron absorption cross section and neutron porosities calculated from chemical analyses of minerals often exceed values calculated using simple chemical formule. INTRODUCTION Recent advances in wireline technology and interpretation have made it possible to obtain in situ concentration logs for at leat ten of the chemical elements present in earth formations: Al, Si, Ca, Fe, §, Ti, K, Th, U, Gd and Mg (Hertzog et al, 1989). One application of such elemental logs is. the calculation of mineral abundances using elemental concentration logs and the composition of constituent normative minerals (Herron, 1986; Wendlandt and Bhuyan, 1990; Herron and Herron, 1990; Harvey et al, 1990; Hunter er al, 1991), There is therefore interest in the most representative ‘chemical composition, and uniformity of that composition, for minerals which are commonly found in sedimentary environments that may contain hydrocarbons. The need for additional compositional data is especially acute for clay minerals in the kaolinite, illite, smectite and chlorite groups. The clay minerals exert a significant impact on many oilfield activitie but their major, as well as minor and trace, elemental composition is not well characterized and is believed to be quite variable (Weaver and Pollard , 1973; Weaver, 1989) In addition to elemental concentration logs, many other logging measurements, such as those based on the natural gamma-ray activity, thermal neutron porosity, photoelectric factor and thermal neutron capture cross section (referred to as ¥ or sigma) are essentially determined by composite elemental concentrations of the formation. Previously, nuclear parameters have been calculated from the chemical formulae of minerals (Edmundson and Raymer, 1979; Ellis et al, 1988). Such formulae treat the composition as a stall set of elements that are important by weight and ignore ‘minor or trace elements. Some of these minor or trace elements significantly influence logging measurements in spite of their low concentrations. To this end, it is important to know whether the elements analyzed are part of the mineral lattice in the form of isomorphous substitution or whether they reside at cation exchange sites. If the latter, then the chemical analysis may reflect the composition of the fluids that have interacted with the clay rather than the intrinsic chemical properties of the mincral itself. If the assumption is correct, then there may be no validity to nuclear parameters calculated from the total chemical composition. * Author for correspondence. 3a MICHAEL M. HERRON and ABIGAIL MATTESON SAMPLES AND ANALYTICAL METHODS, The suite of mineral standards analyzed to date (Appendix) includes quartz, plagioclase, orthoctase, tmicrocline, calcite, dolomite, muscovite, biotite, opal-A, siderite and the clay minerals kaolinite, ilite, smectite, glauconite and chlorite. The mineral standards were obtained from the Natural Science Establishment, Inc, Rochester, NY, U.S.A. (Wards), the Source Clay Mineral Repository {SCMR) of the University of Missouri, Yale University, and many individual donations. We sought to obtain pure minerals for sedimentary formations, but in some cases this was difficult to do, especially for the clay minerals. In a few cases, we have separated the <2ym size fraction as a simple purification step. ‘The kaolinite samples are from Georgia and Tanganyika and span most of the observed range in degree of lattice disorder as measured by Hinckley indices (Hinckley, 1963) ranging between 03 ‘and 1.4, The ilites are from Illinois and Silver Hill, Montana (see Hower and Mowatt, 1966). The smectites include the two major types found in sedimentary formations, Cheto and Wyoming. Three chlorite samples from collections were of metamorphic organic and are labeled mCh. Two samples represent the 2-20 um and <2,im diameter fraction from deep Gulf of Mexico core samples from the Tuscaloosa Formation that are >95% chlorite, according to x-ray diffraction analysis. There is one sedimentary glauconite sample, two metamorphic muscovite micas and one metamorphic biotite mica Of the K-rich feldspars, two are predominantly microctine and four are primarily orthoclase. All exhibit some albite exsolution when viewed in thin section, Three Na-rich plagioclase feldspars were analyzed, Two fallin the albite classification and the third is oligoclase, Four Ca-rich plagioclase feldspars were included, two anorthites, one labradorite and one bytownite. Two quartz crystal samples were analyzed, one from Arkansas and one from Brazil. The quartz and feldspar samples are of igneous origin. There is one sample of diatomaceous earth that has been further characterized as being primarily opal-A. There are 24 calcite and aragonite samples culled from a larger sample set according to the level of impurities in the chemical analysis. There are 14 dolomite samples that were similarly selected from a larger sample set according to the nearness of the chemical composition to the stoichiometric dolomite formula. Most of the calcite and dolomite samples are of sedimentary origin, There are also two siderite samples. These mineral standards were analyzed for most, if not all, of the following elements: Hi (as H,0"), Li, Be, B, C (as organic carbon and CO,), Na, Mg, Al, Si, P, S, K, Ca, So, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, AS, Se, Rb, Sr, ¥, Zr, Nb, Sn, Sb, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Pb, Bi, Th and U. The suite of elements has varied slightly during. the course of these analyses and so is not constant for all mineral standards. Occasionally one or more elements were not analyzed due to insufficient sample. Concentrations were determined by 4 variety of analytical techniques including flame, graphite furnace, and induction-coupled plasma ‘atomic absorption spectrometry, instrumental neutron activation analysis, induction-coupled plasma mass spectrometry, x-ray fluorescence, and wet chemical techniques at X-ray Assay Laboratories in Don Mills, Ontario. A second set of kaolinite samples from Brindley et al. (1986) labeled 1, Il, II, TV, V and English were analyzed by neutron activation analysis at Atomic Energy of Canada, Ltd. A more complete analysis of these samples was not possible due to lack of sample. Exchangeable cations from these samples were then replaced by NH and the samples were re-analyzed at the same facility. NUCLEAR PARAMETER CALCULATION ‘The array of major, minor, and trace elements measured in this study is larger than is commonly ‘measured on pure mineral phases and includes virtually all of the potentially significant elements related to nuclear logging. Therefore, we have undertaken to calculate some of the more importantMineral chemistry and nucleae parameters 35 nuclear parameters using the measured elemental compositions of the mineral standards. The total natural j-ray response of a given formation, GRyew» depends on the porosity, d. and the j-ray response of the minerals comprising the matrix, GR... If the fluid has no )-ray activity, then GR aoa =(1 —OIGR as a) It is the matrix natural y-ray intensity value that can be calculated from chemical data such as is given in this report, because all fluids are removed prior to analysis. Ellis (1987, pp. 187-190) deseribes the value of GRyuy for @ rock as a linear combination of the °U, ?9°Th and °K ‘concentrations. The coefficients depend upon the specific measurement tool configuration and upon the assumption of isotopic equilibrium, but for one tool the relationship can be approximated as: GR =4TH+8U 416K e where Th is the thorium concentration in ppm, U is the uranium concentration in ppm, and K is the potassium concentration in weight percent. Equation (2) was used to derive GRyuy values. The remaining nuclear parameters were calculated using the SNUPAR program (McKeon and Scott, 1988), The thermal neutron capture cross section of the dry rock, matrix sigma (Enudy is given by: 6022955 Ena M 8 where p is the mineral mass density, M is the mineral molecular weight, n, are the atomic number densities and o, are the microscopic thermal neutron cross sections for the individual elements. ‘The densities of the mineral standards were not measured as part of this study: the densities used were those from Ellis et al. (1988) as given in Appendix C. For most minerals, the structural water, designated HO”, was used for the hydrogen concentration. In the case of smectites, the loss on. ignition was taken as a better and more representative measure of the total of structural water plus interlayer water and was used in the SNUPAR calculations. The photoelectric factor, P, was calculated from: “ EnZiry EnZ where Z; is the atomic number and r, is proportional to the elemental photoelectric absorption cross section per lcton and is defined zy : e *) ° The units of P, are barns per electron or photoelectric units (p.e.u., Apparent thermal and epithermal porosities and hydrogen indices of the minerals were calculated from the slowing-down lengths and migration lengths as described by McKeon and Scott (1988). The epithermal neutron porosity is specific to the tool configuration but is largely dependent upon. the hydrogen content of the formation; the thermal neutron porosity is additionally affected by the rest of the thermal neutron capture cross section, E. EXCHANGEABILITY OF CATIONS IN BRINDLEY KAOLINITES For nuclear parameters calculated from chemical data to be reliable, the question of whether trace elements can be exchanged on clay surfaces should be considered. If trace elements are ‘In the oll industry the response of spectrometers for measuring natural radioactivity i calibrated in a cased hole in a special test formation ofthe American Petroleum Institute. The response of spectrometers is often refered to in terms of| “GR”. The value of GR inthe APL formation is defined as 200 API units fom 13pm of Uranivm, 24 ppm of Th and 4% of K386 MICHAEL M. HERRON and ABIGAIL MATTESON exchangeable, then the clay composition can be a function of the last fluid to contact the clay rather than an inherent property of the clay itsell. We examined the exchangeability of major and trace elements in a set of well characterized kaolinite clay minerals (Brindley et al, 1986) “The chemical composition of the Brindley kaolinite samples before and after exchangeable cations ‘were replaced with NH{ are compared in Table I and in Fig. 1. Figure 1 shows a comparison of the “before” and “after” exchange for six of the elements measured: Ca, V, La, Sm, Th and U. For each ‘graph there is a line representing the Il line for no exchange and a dotted line representing the “Table 1, Ratio of elemental concentrations in kaolinite samples after cation exchange t that prior fo exchange Element Ratio Element Ratio. Flement Ratio on 000 100 as 092 (ost ts om O86 Fe ioe c os ass Mn 098 100 Mg oss a8? co 105098 Sm ost 099) Ne os O67 Dy os) 095 se 098 099) K os? as Eu 09 093 Th 10s 099) Ti oo 4.00 ut ror 092 v 090098 sb 090 09s la 097098 v 09710) * Correlation coetcent. E 2 ° Zeno Before (rrm) Fie. Chemical composition of selected clements in kaliites described in Brinley eal (1986). Ordinate and abscissa values are concentrations before and ater exchangeable cations have been replaced by NZ ‘spectively, In each instance, the solid line represents no exchange and the dotted line represents the reeresion that passes through the origin: Th; U; La; SM: Ca; V.Mineral chemistry and nuclear parameters 37 least squares line that intersects the origin. The slope of the dotted line and correlation coefficient is given for all elements analyzed by neutron activation in Table 1. Ca?* cations show complete replacement, while Na” and Mg?* are partially replaced. For the remaining elements, generally 5% or less is exchangeable (Table 1). “These results show that & major fraction of the trace element population in kaolinite clay minerals, with a wide range of internal order (Brindley er al, 1986) is not exchangeable and indicates that the trace element content of clays is not as variable as has often been supposed (e.g. Brownlow, 1979, p.297). Since only about 5% of the total trace element content was exchangeable in the Brindley kaolinites, it can be suggested that these trace elements may largely exist in isomorphous substitution in octahedral or tetrahedral sites replacing the major cations Al and Si. They may, of ‘course, have started as adsorbed cations and eventually diffused into the lattice. It is interesting to note that if thorium at a nominal concentration of 20pm is completely isomorphously substituting for octahedral Al at a concentration of 20%, only one in about 86,000 Al atoms would be replaced by Th. This level will be difficult to detect by direct observation, These elements may also exist in other residences such as in insoluble oxide or hydroxide compounds. Similar exchangeability studies should be conducted on trace elements in other clay minerals, Further evidence that the trace element content of some clay minerals may be related to structure rather than to surface adsorption is evident in Fig. 2, where the thorium and lanthanum concentrations of the kaolinite samples are plotted. The data naturally cluster into three groups: according to the degree of internal order as measured by the Hinckley Index. The four group samples with a hinckley Index over 1.4 have high and nearly identical Th/La ratios of about 4. ‘The Group II and English samples which have Hinckley Indices slightly greater than 1 show a ‘Th/La ratio of about 1. Finally, the poorly-ordered kaolinites with Hinckley Indices <0.5 have significantly lower Th/La ratios at about 0.25. These results indicate that at least some of the trace clement content may meaningfully relate to the degree of structural order in kaolinites. AVERAGE COMPOSITION AND CALCULATED NUCLEAR PARAMETERS The chemical analysis and the calculated nuclear parameters are detailed in the appendices for each mineral standard. Table 2 gives the mean and standard deviation for major elements and some trace elements that are measurable with geochemical logs and the element boron which can, perturb thermal neutron measurements (Hertzog et al, 1989). Mineral formulae listed in this section are from Ellis et al. (1988) and form the basis of their nuclear parameter computations. Computed nuclear parameters from these chemical analyses and as derived from the chemical formulae (Ellis et al, 1988) are given in Tables 3 and 4. a 30 “ Jo oe 8S a Fig, 2 Th and La inthe Brindley kaolinite, Beter ordered kaolintes with a higher Hinckley Index have higher Th/La ratios.MICHAEL M. HERRON and ABIGAIL MATTESON 388 1 vo 50 #0 iy oz 8 rs es 1 66 £0 cr 80 v0 st <9 £0 50 zo £0 zo 50 sz se tur zo 0 10 10 too zo <0 90 100 100 100 seo ry st ve + 60 co a 10 10 ro a 60 vw so e so so so ro ro zo 10 to so ro eo ro si zo $51 ss 80 st oz ssi 0 06 fo 96 60 1 so S01 so oe 09 v0 ot Yt v0 oot ro i bo 00 00 00 0 eu se ov 9 9 ro 00 car 90 oe tie @ arson w wl 6 sede a fo ausspis mwotser (so an @ cauend oN? I9UhyMineral chemistry and nuclear parameters 389 ‘Table 3. Mean and standard deviation of tay, and the P, ofthe standard mineral samples. Ako shown are the values ‘of and the valcs ofp, obtained using the ehemical formula (Elis eta 198) Computed ‘Computed Formula Computed Formula Mineral GR, Siam Siam,” » Pe (No. spe ari rea eal i) (eu) Kaolinite 108 201 1308 2 9 ) 2 21 02 ile 160 406 1674 40 303 i 7 56 02 Soectte 16s 200 S34 29 Lot “i 1 23 as Chloe, at 6 437 ana 8 12365 6 3 18 2 Chionite, Sed uu sos ans 18 12365 e B as on Giawconite 130 196 2089 0 an 0 Mascovite 0 953 1706 40 240 2 ° 347 tu Biotite sa 3509 70 870 a K-Feldspar m 133 Ise aa 26 6 1 2s a6 Na Plagoclase 5 na 168 2 68 8 6 25 02 Ca-Plagioclase ' 94 18 30 AB 6 1 BR 02 Quartz 1 4a 43s 19 at a 1 on oo Ops ” 26 526 as us a alee " mu 708 sa 508 es) 8 a os Dolomite 5 69 47 a an aay) 5 33 08 Siderite 6 si 2m 186 1409 a 5 oS ise a. (1988, + Pes barn electron. {Montmorillonite no interlayer water §Fe-chlort Analyses for some of these sedimentary minerals conform closely to the common chemical formulae with only a few tenths of percent major element impurities. For these minerals, trace , corresponds to 21.3% Ca and 129% Mg: measured averages are 21.6% Ca and 123% Mg. The higher-than-expected Ca concentration most likely represents a slight contamination with a purer CaCO, phase. These minerals also have nuclear parameters close to the values derived simply from the chemical formulae. The computed matrix 7-ray signal averages about 10 API units for the calcite30 [MICHAEL M. HERRON and ABIGAIL MATTESON ‘Table Mean and standard deviation of thermal neutron porosity (TNPH)and epithermal ENPH) neutron porosities of the mineral standard samples. Also shown are the values caleulated by Elis al (1988 from mineral formulae Computed Formula Compuied Formula Mineral TNPH* TNPHY ENDI (No samples) Gs unites As unis Us units) Kaolinite 450 sr a3 78 o 32 9 lite mar 1s 16 nr 6 28 26 Smectite 28 nse a 60 Clore all 2482 > 60" oo 6 Chloe, Se, D482 > poor a Glaveonite at ns Bz a Muscovite >208 16s 107 ba a 32 Biotite u 18s s2 ba a K-Feldspar 08 =u -10 ats 6 06 0s Ne-Plagoclase os -13 -08 10 8 os 02 Ca Plagiociase 08 -16 07 13 ® 04 04 Quartz 18 =24 08 2 03 04 Opal 8s w a 3 o Calcite 02 00 00 a0 25) 03 a Dolomite 13 os a7 " «a 1 0 Siderite 184 ne a 63 a 13 6s * Thermal newton porosity {Ellis et a (1988, {}Epithermal neutron porosity {Limestone equivalent units, Montmorillonite-no interlayer water, *Fechlore {}THigh level of thermal neuron absorbers render calculation meaningless. and dolomite due to sporadic uranium impurities. The thermal and epithermal porosities are close to the values computed from the formula except for dolomite where the thermal porosity is high by 1 porosity init (pu). ‘The two siderite (FeCO,) samples show some major element contamination from Si, Al, Na, Ca, and especially Mg. This suggests some contamination with aluminosilicates such as quartz and feldspars or clay minerals and some more significant carbonate substitution, The computed y-ray and sigma matrix are close to the values predicted from the formula. The value of P, should be lower than the formula value due to dilution of the heave Fe atoms with lighter atoms. However, ‘one of the siderites had over 7000 ppm Pb as an impurity and this increased the average P, to 18.6 photoelectric units, 27% above the predicted value of 14.69 p..us thermal and epithermal porosities are higher than the formula-derived values by 5.5 and 48p.u,‘Mineral chemistry and nuclear parameters x Plagioclase feldspar minerals are more complicated and seem, commonly, to occur intermediate in composition between the Na (albite, NaAlSi,0,) and Ca (Anorthite, Ca,A1,$iz0,) end-members. Potassium is a small impurity in the Na-tich feldspars while Fe and Mg are impurities in the Ca-tich feldspars. Boron is commonly found at 10-30 ppm in each of the plagioclase standards. As 1 result of these impurities the value of ¥ for a matrix of Na-rich feldspars is 49% above values computed for the albite formula. The value of E for the Ca-rich feldspars is 27% greater than ‘computed from the anorthite formula. The P, derived from the chemistry of the Ca-rich plagioclases is essentially the same as that derived from the formula; for Na-rich plagioclases the chemically-derived-value is 0.4p.e.u. higher. Thermal and epithermal neutron porosities are 02-08 p.u. higher than values computed from the formulae. Potassium feldspar minerals in our group are always significantly different in composition from those corresponding to the formula, KAISisO,. According to the formula, the potassium concentration should be 14.05% while our standards (both the microcline and orthoclase varieties) average 10.2% K with a standard deviation of only 0.6% K. Smith (1974, pp.33-S5) found similar values in his survey of feldspar chemistry. Pittman (1979) also found that sedimentary K-feldspars generally contained only about 10% K and that purer phases were observed only in recrystallization rims, Albite is the major substituting mineral in both studies. The low potassium concentration in the K-feldspar standards could present a problem in comparisons of chemically-derived mineralogy if the impure K-feldspars are used as standards. K-feldspar concentrations derived assuming the K concentration of the standard is 14.05% will be about 29% lower than if an end-member concentration of 10% K is used. The chemically-derived mineralogy will also be about 29% lower than values determined from ancillary studies such as x-ray diffraction if the impure K-feldspars are used as standards. The computed value of & is similar to the value derived from the formula due to about 20 ppm boron and the computed P, is close to that derived from the formula. Thermal ‘and epithermal neutron porosities are both 0.Sp.u. higher than computed from the formula, The ‘computed y-ray is about 60 API units lower than if the potassium concentration were 1405%, ‘The opal (SiO,-nl1,0) sample had some major-element impurities of Al, Fe, Ca, Mg, K and Na that probably reflects clay mineral contamination at the time of deposition. The HzO” content of 4.2% is consistent with the formula if n=0.16, but some of the crystalline water may also come from the clay contamination. The trace elements Th, U, Gd and B also showed significant values above those expected from the chemical formula, but the values are higher than the clays might contribute. The impurities give opal a significant natural ;-ray intensity of 79 API units whereas the formula would predict zero. The value of E for the matrix is computed at 22.6 capture units®, more than a factor of 4 greater than predicted from the formula and largely due to the boron. Correspondingly, the thermal neutron porosity is 6.6p.u. higher than calculated using the formula for which the epithermal porosity is 14 p.u. higher. Finally, the P, of the opal is 43% greater than predicted from the composition, “The muscovite (K Al;Si,0, (OH) samples show slightly higher concentrations of Fe and lower ‘concentrations of Al, K and H,O* compared to those predicted by the formula. The concentrations of the trace elements Th, U and Gd were all very low in these samples, but the boron content, {450 ppm, is similar to values reported for illite which has incorporated boron from sea water in @ inarine environment. The computed y-ray activity for muscovite averages 130 API units. As result of the Fe contamination, the computed value of P, is 67% above the 2.4pe.u. derived from the formula. The high boron content gives these muscovites an average value for & for the matrix of 95 capture units compared to the value of 17,06. using the formula, The thermal neutron porosity is 43 pu, greater than obtained using the formula, but the epithermal value is 2.7p.u. lower. ‘The lone biotite (K(Mg, Fe) AISi,O,o(OH),) sample lies slightly to the Fe-rich side of midway in composition between the Fe and Mgend-members. The measured HO” of 1.1% is low compared TA “capture unit” is 10 em reflecting the average formation macroscopic thermal neutron absorption cros-section| per eubie centimeterm MicHAEL M. HERRON and ABlGAIL. MarTESON to the formula value of 39% for the intermediate composition biotite. The trace elements Th, U, Gd and B are all significant for non-clay minerals, but low compared to the values in clays: our biotite has a sizable Ti content of 1.48%. The biotite has a 7-ray of 127 API units. The computed sigma is higher than the value computed by Ellis er al. (1988) by 54%, while the chemistry-derived is lower than the formula value by 20%. The thermal and epithermal neutron values are both lower than values derived from the formula, due primarily to the low HO” The kaolinite [Al,Si,O, o(OH)s] samples in our study contain a slight Fe content and a significant 1.1% impurity. The trace elements Th, U, Gd and B are all about one order of magnitude larger than for most of the non-clay minerals and show relatively small standard deviations. The kaolinites span a large range of degrees of internal order with Hinckley indices ranging from 0.3 to 14. The H,0* content, according to the formula, is 13.95% compared to the measured 12.9% H,O* and 142% loss on ignition. The computed y-ray is 104-+22,API units, The trace elements produced a matrix value of ¥ of 20. whichis 54% greater than the value computed from the formula alone. The value of P, from measured chemisty is 2.1 pew, and 41% greater than the 149 pe. obtained by using the formula, Thermal porosities average the same as those computed from the formulae while the epthermal values are lower by 9%. There are six illite (Ko,4(Al, Feo, 2M&p,2Sis.«Alp g)O,o(OH),) samples. These have a low iron content (4.8+0.9%) compared to some recent analyses of sedimentary illites: 6.9% in Irish Sea illtes (Macci etal, 1990), 7.6% iniltes from Utah (Wendlandt and Bhuyan, 1990) and 8% from Analysis of mineralogical and chemical data from Venezuela and California (Herron and Herron, 1990), The fraction <2 pm of Fithian it is enriched in iron (64 w1%) relative to the bulk sample (46%) and this is inline with the Fe content in the <2,um fraction of Fithian illite reported by Gaudette etal (1965), Weaver suggests thatthe illts with an iron content between that of low Feillte and glauconite may be authigenic. The Fe content of many ilits in the literature is much lower (Gaudette eral, 1965; Kossovskaya and Drits, 1970; Ireland etal, 1983; Srodon etal, 1986, Nadeau and Bain, 1986; Weaver, 1989, p.43}, no low-Fe ilites were in our sample set. The Th concentration is slighty less than that of the kaolinites while the U and Gd concentrations are about the same asin the kaolinite, The boron concentrations average 160 ppm. This may not be representative ofilites deposited in marine conditions where values closer to S00 ppm are apparently ‘mote common, although there is controversy over the significance of boron in clays and shales (Shaw and Bugry, 1966; Reynolds, 1972) The jay of the ites averages 160 API units with @ relatively low standard deviation of 37API. The chemically-derived matrix sigma is 40.6 capture units and 143% higher than the value using the formula of Ellis et al. (1988) This is largely due to the Fe and B concentrations, a boron concentration of 500 ppm would inerease the matrix sigma to 81.7 capture unis. The matrix P, is calculated from the chemistry at 40peu. compared to 303 pew. from the chemical formula. Due to the impurities, the epthermal neutron porosity is about I p.v, higher than computed from the formula The single glauconite [Ka (Fey Al, s\Sis Aly 3)O,o(OH),] sample has 15.5% Fe compared to 9.6% according to the given formula The Al concentration is correspondingly reduced 10 44% from a formula-value of 13.3%. This glauconite has significant Th, U and Gu at the few ppm level and a very high 500 ppm B. This level isin accord with the “marin iit” level discussed above This glauconite has aj-ray of 150API units similar to that of lite. The computed matrix sigma is 89.6cu, and more than a factor 4 greater than the formula-derived value of 2089. The greater the Fe concentration in the glauconite than that derived using the chemical formula results in a computed valve for P. of 6.7 compated tothe value of 479 obtained using the chemical formula, Theepithermal porosity from chemical composition is 7 pu greater than obtained using the formula: the thermal neutron absorbers ender the thermal neutron porosity computation meaningles. The eight smecttes [Nap y(Ah, Mo Sis, KOH), in our grouping include the two major varieties of montmorillonite (Weaver, 1989 Cheto [Xx Al, s4F,o9MBys4NSis Aloo} (OH);]: and Wyoming [Xo s4(Al;.72F.09Mo,015)Sia,o64le.04)0 (OH), ]Mineral chemistry and nuclear parameters v3 In these formulations, X represents an exchangeable cation, The HO averages 58% and corresponds to smectite with no interlayer water. Hydrated smecttes typically have 24 wt% adsorbed water (Grim, 1968, p.266) and this is partially reflected in the higher loss on ignition of 16.1% Which was assumed to be the HO content; itis likely that the smectites were not fully hydrated “The average Th concentration of 26 ppm is the highest of any clay group and the U concentration of 7.1 ppm is also highest. The Gd concentration of & ppm is also high, but the B concentration is ‘a modest 21 ppm. The y-ray of smectites is 168API, similar to that of ilite, The matrix sigma averages 200 capture units, compared to 834cu. for montmorillonite without an interlayer of water and 13.97¢.u. for montmorillonite with 16% adsorbed HO (mont-4H,0), The matrix value for P., computed from chemical analyses, is 2.9, compared to 1.63 for dry montmorillonite and 1.49 for mont:4H,O. The neutron porosities calculated from the chemical analysis confirm that the smectites were not fully hydrated, The epithermal porosity of 17.8p.u, lies between the formula-derived 12.6p.u. for dehydrated smectite and 50.0 pau, for fully hydrated smectite. Chiorite [Mg, Fe),AINSisAI)O ,(OH),] exists as mixtures of Mg-rich and Fe-rich end members. ‘Two of the metamorphic (mChl) chlorites inthis study were very Fe-tich and one was more Mg-tich. The two sedimentary chlorites are from the deep Tuscaloosa formation and are size fractionated from sandstone cores. The iron-rich metamorphic chlorites average 26.6% Fe; the sedimentary chlorites average 16.4% Fe, and the Mgcrich chlorite still contains 17.8% Fe. The computed -ray is lower than for the other clays, averaging $6 API forall chorites and 111 API or the sedimentary hlorites. The matrix sigma values average 43.7 cu, for all chlorites and $0.5¢.u. for the sedimentary chlorite are similar to the 47.77c., calculated for the Fe-rich end-member. The values of P, for the chemically-derived chlorites are significantly lower than the 12.36 p..u. derived from the chemical formula, Neutron porosities for the Fe-rich chlorite are given as simply greater than 60p.u. (Ellis tal, 1988) and the sedimentary chlorite values of 42.9 p.u, for epithermal and 48.2p.u. for thermal neutron porosity are consistent with the lower Fe content of these standards. SUMMARY Chemical formulae are shorthand representations of the chemical compositions of minerals, Many ‘minerals regularly contain significant amounts of minor and trace elements which are not represented in the chemical formulae but which give rise to logging parameters that differ significantly from the values derived from using the chemical formulae alone. This effect is largest for micas and clay minerals and lowest for quartz, calcite and dolomite. If differences in chemical content reflect impurities in the standard mineral samples, these differences would be expected to show some random relationship to the host chemistry. This is seen in concentrations with large relative standard deviations. However, it is frequently observed, that the trace chemical content is not a random process as reflected in low relative standard deviations. This may be due to substitution at a trace level for major elements in the crystal structure. In any event, the trace element concentrations should not be ignored in modeling the nuclear properties of sedimentary minerals ‘The low standard deviations in clay mineral composition bode well for the solution of mineralogy from downhole clemental data. This applies not only to the major elements but also to the trace elements Th, U and Gd which can be measured in boreholes. Much of the reported variability in clay mineral composition can be attributed to impurities such as swelling layers in illites (Srodon. et al, 1986) or to the existence of wo mineral types such as well-ordered and poorly-ordered Kaolinites (Brindley et al, 1986). The latter may present an opportunity in the future to discriminate between authigenic and detrital phases from downhole elemental data In the case of the kaolinite samples which were examined in detail, about 95% of the trace element assemblage is not exchangeable in a normal cation exchange procedure, This implies that the trace elements exist in mineral defects or substitute for major elements in the mineral lattice, ‘The Th/La ratio shows some correlation with the degree of internal order measured by the Hinckley Index again indicating that the trace element composition is related to the structural order.304 [MICHAEL M. HERRON and ARIGAIL MATTESON Potassium feldspars contained only about 10% K instead of the 14,05 K derived from the chemical formula. If such feldspars are used as mineral standards in, for example, x-ray diffraction analysis, chemically-derived K-feldspar concentrations can be expected to be about 29% lower than XRD-derived concentrations. We are actively soliciting mineral standards to expand this data base. Acknowledgements—D. MeKeon modified the SNUPAR code to enable the computations to be made with many ‘ements. Elis ofeed valuable insight into these computations. We thank M. Supp forthe sample handling. Herron land J: Schweitzer made many valuable suggestion tothe manwscrip. REFERENCES Brindley G. W., Kao C.-C, Harrison JL, Lipsias M. and Raythatha R, (1986) Relation between structural disorder and other characterises of kalinites and dickits. Clays Clay Minerals 3429-289, Brownlow A. H. (1979) Geochemistry. Prentice-Hall, Englewood Cliff, Ni Edmundsen H. and Raymer LL (1979) Radioactive logging parameters for common minerals. SPH/LA 20th Anna Logging ‘Simp. Paper O. Tulsa, Oka, June Eis D. V. 1987) Well Lagging for Earth Sein, Elsevier, New York Elis D, Howard J, Flaum C. McKeon D. Scott H. Serra O. and Simmons G, (1988) Mineral lo and acoustic, Technical Ree. 36, 38-53, GaudetteHLE, Eades JL and Grim R..(1965) The nature of Grim RF (1968) Clay Mineralogy. MeGraw-Hil, New York Harvey PK. Bristow J. Fand Lovell M.A. (1990) Mineral transforms and downhole gsochemical measurements Scientific Drilling 1, 163-176 Herron M. M. (1986) Mineralogy from geochemical well logging. Clays Clay Minerals 34, 204-213 Herron M. ME and Herron S. L. (1990) Geological applications of geochemical wel logging. In Geological Applications of Wireline Logs (Eds. Hurst A. Lovell M, A. and Morton A. C), Geological Society Special Publication 48, pp 165-175, London. Hertz R, Colson L., Seeman B, O'Brien M. Scott H. McKeon D Wrsight P, Grau J, Ellis D, Schweitzer J. and Herron M. (1989) Geochemical logging with spectrometry tools. SPE Formation val 4, 153-162 Hinekley D. N. (1963) Variability in“erystalinty” values among the kaolin deposits of the coustal pin of Georgia and South Carolina, Clays Clay Minerals 13, 229-235 Hower. and MowaitT-C.(1966)The mineralogy ofilites and mxed-ayerlte montmorilonts. Am. Mineral 1, 825-854 Hunter W. A. Dodman C, HarantyoT.S. Micaus B. and North R (1991) Revs and applications of geochemical loging. uri Feld, Riau Provence, sumatea. Proceedings Iadovesian Petroleum Association. Twentieth Annual Contention, Jk October 1991 lWeland B. 1, Curis C.D. and Whiteman J. A. (1983) Compositional variation within some glauconites and iltes and implications for their stability and origins. Sedlmentloyy 30, 169-786, Kossovskaya AG, and DritsV. A. (1970) The variability of micaceous minerals in sedimentary rocks. Sedimentology 1S, 83-101 Macchi L. Curtis C.D, Levison A., Woodward K. and Hughes C.R. (1990) Chemistry, morphology. and dstribstion of tes from Morcambe Gas Feld, Irish Se, offshore United Kingdom. Am. soc. Petrol. Geo, Ball 74, 296-308. MeKeon D.C. and Scott H, D. (1988) SNUPAR—A nuclear purameter code for nuclear geophysics applizations Nucl Geophys. 2218-230, Nadeau P. H. and Bain D.C. (1986) Composition of some smetites and diagenetic ite clays and implications for their ‘origin. Clays Clay Minerals 34, 455-464, Pitman E.D. (1979) Porosity. diagenesis and productive capability of sandstone reservoirs. In Aspects of Diayeness (Eds Scholle P. A. and Schluger P. R.} Society of Economie Paleontlogists and mineralogists Special Publcation 26 P.165-168, Tulsa, OK. Reynolds RC. (1972) Boron: cement and geochemisty. In The Enesclopedia of Geochemistry and Emironmental Sciences (Ed. R. W. Farbrdge, pp. 86-90. Dowden. Hutchinson and Ross, Stroudsbure, PA. ‘Shaw D.M. and Bugry R.(1966) A review of boron sedimentary geochemistry in relation to new analyses of some Noth “American sles, Can. J. Eurth Sc 349-63, Smith 1. ¥. (1974) Fldipar Mineral 2; Chica and Testural Properties. Springer-Vetlag, New York. Srodon J, Morgan J.D, Eslinger . V. Ebor D.D. an Kasinger MR (1986) Chemisty oilte smectite and endsmember ‘lite. Clays Clay Minerals 34. 368-378 Weaver C-E, (1989) Clays, Mus and Shales. Fever, Amsterdam, Weaver C.E. and Pollard L. D. (1973) The Chemivrs of Clav Minerals. Ehevet, New Vork, Wendlandt R.F. and Bhuyan K. (1990) Estimation of mineralogy and thology from geochemical log measurements Am Asoc. Petrol. Geo. Bul. 74, 837-856, i parameters: Nuclear te Clays Clay Minerale Proc Nal Conf. 13th Pro, 33-48,