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UBC Theses and Dissertations

Mineralogical and chemical studies of the Alberni clay. Osborne, V. E. 1960

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.MINERALOGICAL AND CHEMICAL STUDIES OP THE ALBERNI CLAY By V.E. OSBORNE A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OP MASTER OP SCIENCE IN AGRICULTURE i n the Department of S o i l S cience We Accept t h i s t h e s i s as conforming to the standard r e q u i r e d from candidates f o r the degree of MASTER OP SCIENCE IN AGRICULTURE THE UNIVERSITY OP BRITISH COLUMBIA A p r i l I960 In presenting t h i s t h e s i s .in p a r t i a l f u l f i l m e n t of the requirements f o r an advanced degree at the U n i v e r s i t y of B r i t i s h Columbia, I agree t h a t the L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r reference and study. I f u r t h e r agree that permission f o r extensive copying of t h i s t h e s i s f o r s c h o l a r l y purposes may be granted by the Head of my Department or by h i s r e p r e s e n t a t i v e s . I t i s understood tha t copying or p u b l i c a t i o n of t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l not be allowed without my w r i t t e n permission. The U n i v e r s i t y of B r i t i s h Columbia Vancouver 8\ Canada. i ACKNOWLEDGED NTS G r a t e f u l acknowledgement i s made to Dr. J . S . C l a r k f o r h i s constant s u p e r v i s i o n and guidance during the p e r i o d of t h i s work, and to Mr. H. H o r t i e , f o r m e r l y of the F e d e r a l S o i l Survey Department, whose advice and t e c h n i c a l a s s i s t a n c e has "been i n v a l u a b l e . The author i s i ndebted to Dr. J.E.Brydon, S o i l Research I n s t i t u t e , Canada Department of A g r i c u l t u r e , f o r h i s a s s i s t a n c e w i t h much of the m i n e r a l o g i c a l a n a l y s i s and f o r the computation of the chemical formula o f the c h l o r i t e . The author a l s o wishes to thank Dr. L.G.Harrison of the Chemistry Department, U n i v e r s i t y of B r i t i s h Columbiaa and Mr. L. F a r s t a d , Senior P e d o l o g i s t , Canada Department of A g r i c u l t u r e , f o r t h e i r h elp and a d v i c e . The author i s indebted to Dr. R.M.Thompson of the Geology Department f o r h i s help w i t h some x-ray a n a l y s i s and f o r the use of the isodynamic s e p a r a t o r . A p p r e c i a t i o n i s a l s o expressed to the M e t a l l u r g y Department and the B r i t i s h Columbia Research C o u n c i l f o r the use of x-ray equipment. The author i s p a r t i c u l a r l y t h a n k f u l f o r the f i n a n -c i a l a s s i s t a n c e r e c e i v e d from the Canada Department of A g r i c u l t u r e through E x t r a Mural Research Grant, 89 -" S t u d i e s o f C o n c r e t i o n a r y Brown S o i l s of B r i t i s h Colum-b i a " . i i TABLE OP CONTENTS Page ACKNOWLEDGEMENTS i LIST OP TABLES v LIST OP FIGURES v i i i ABSTRACT X INTRODUCTION 1 MINERALOGICAL AND CHEMICAL PROPERTIES OP ALBERNI CLAY MATERIALS AND METHODS Samples 9 X-ray and Chemical A n a l y s i s of Clay Separation of Clays 9 Chemical A n a l y s i s 10 X-ray A n a l y s i s 11 D i f f e r e n t i a l Thermal A n a l y s i s 11 C.E.C. A n a l y s i s 11 RESULTS AND DISCUSSION X-ray and Chemical A n a l y s i s of Clay 12 C a l c u l a t i o n of the S t r u c t u r a l Formula 30 Re l a t i o n s h i p With Other C h l o r i t e s 3k C a t i o n Exchange h3 i i i Page STUDIES OF CONCRETIONS M a t e r i a l s and Methods 70 R e s u l t s and D i s c u s s i o n s 72 STUDIES OF COATINGS MATERIALS & METHODS Separation and Chemical A n a l y s i s of Black Coatings 85 M i c r o s c o p i c examination and X-ray a n a l y s i s of Black Coatings 85 X-ray a n a l y s i s of S i l i c e o u s Coatings 86 RESULTS Al© DISCUSSION Black Coatings 86 S i l i c e o u s C oatings 89 SOLUBILITY RELATIONS OF IRON AND ALUMINUM IN THE ALBERNI CLAY MATERIALS AND M E T H O D S 91 RESULTS AND DISCUSSION 92 SUMMARY AND""CONCLUSIONS 107 BIBLIOGRAPHY 112 APPENDIX I C onductiometric t i t r a t i o n of 2 . 0 - 0 . 2 micron H-clay C h o r i z o n , 2 d i t h i o n i t e treatments I I Conductiometric t i t r a t i o n of 2 . 0 - 0 . 2 micron H-clay A-B Horizon, k d i t h i o n i t e treatments. i v APPENDIX (CONT'D) I I I Conductiometric t i t r a t i o n of 2 . 0 - 0 . 2 micron H-clay C h o r i z o n , k d i t h i o n i t e treatments. IV Conductiometric t i t r a t i o n of 0 . 2 mi-cron H-clay C h o r i z o n , k d i t h i o n i t e treatments. V Conductiometric t i t r a t i o n of 0 . 2 micron H-clay C h o r i z o n , 2 d i t h i o n i t e t r e a t -ments . VI Conductiometric t i t r a t i o n of 0 . 2 micron H-clay A-B h o r i z o n , 8 d i t h i o n i t e t r e a t -ments . V I I Conductiometric t i t r a t i o n of 0 . 2 H-clay A-B h o r i z o n , 1+ d i t h i o n i t e treatments. V I I I C a l c u l a t i o n showing the order of magni-tude of the magnetic d i p o l e i n t e r a c -t i o n of magnetite c r y s t a l s and f e r r o -magnetic ions i n s o l u t i o n as compared w i t h thermal energy. V LIST OF TABLES Page TABLE 1 Chemical composition of concre-t i o n s , concretionary s o i l from the A-B hor i z o n and s o i l from C, horixon (of the A l b e r n i C l a y ) . 6 TABLE 2 Percentage composition of c l a y f r a c -t i o n s of A l b e r n i Clay based on Oven Dry Y*5ght. 12 TABLE 3 X-ray d i f f r a c t i o n data from non o r i e n t e d specimens of the A l b e r n i f i n e c l a y and of cookeite (Zvyagin and Nefedov, 1954). 23 TABLE 1+ C a l c u l a t i o n of the chemical formula of the 0.2 micron f r a c t i o n of the A l b e r n i A - B h o r i z o n . 27 TABLE 5 C.E.C. of A l b e r n i c l a y s . NR^Ac method. 55 TABLE 6 C.E.C. of A l b e r n i s o i l a f t e r d i t h i o n -i t e - c i t r a t e e x t r a c t i o n NH^Ac method. 55 .TABLE 7 C.E.C. of A l b e r n i c l a y s . Conducti-metric t i t r a t i o n method. §6 TABLE 8 Cation exchange c a p a c i t y data f o r C horizon s o i l and c l a y Mn method. 56 TABLE 9 C.E.C. of A l b e r n i c l a y s (V'2.0 F e 2 + ) Mo d i f i e d NH, Ac-Acetone/Alcohol method. 57 ' 4 TABLE 10 C.E.C. of A l b e r n i c l a y s ( k/2.0 F e 3 + ) . E v a l u a t i o n of the e f f e c t i v e n e s s of p o l i c i n g the c l a y samples. Modi f i e d NH^Ac - Acetone method. 57 v v i Page TABLE 11 G.E.G. of A l b e r n i c l a y s s a t u r a t e d w i t h d i f f e r e n t c a t i o n s . M o d i f i e d NH^AG-Acetone method. TABLE 12 S t r u c t u r a l R e l a t i o n s h i p s of c l a y m i n e r a l s . TABLE 13 Chemical Formulae f o r c l a y minerals showing the l i m i t s of isomorphous s u b s t i t u t i o n of A l f o r S i found i n d i f f e r e n t samples. TABLE Ik The e f f e c t of D i t h i o n i t e - c i t r a t e e x t r a c t i o n s on the mechanical a n a l y -s i s of A l b e r n i c l a y . TABLE 15 X-ray a n a l y s i s of magnetic concre-t i o n s . TABLE 16 The Pe, A l , T i , Mn, and S i content of the d i t h i o n i t e e x t r a c t s . TABLE 17 X-ray d i f f r a c t i o n data f o r b l a c k c o a t i n g s (O.i+O amps) u s i n g Cu r a d i a -t i o n w i t h a Ni f i l t e r . TABLE 18 The Fe, Al, T i , Mn and S i content of the b l a c k c o a t i n g s . TABLE 19 "d" spacings c a l c u l a t e d from the x-ray d i f f r a c t i o n p a t t e r n of the white c o a t i n g s . TABLE 20 ( S e r i e s I) Fe c o n c e n t r a t i o n of the e x t r a c t s from s o i l / w a t e r suspensions of 1:10 reacted w i t h 0 . I n i t i a l pH ( a c i d i f i e d w i t h HC1? 3-50. TABLE 21 ( S e r i e s II) Fe c o n c e n t r a t i o n of the e x t r a c t s from s o i l t w a t e r suspensions of 1:10 r e a c t e d w i t h 1%0 i n mixture w i t h N 2 d TABLE 22 ( S e r i e s I I I ) Fe c o n c e n t r a t i o n i n the e x t r a c t s from s o i l : w a t e r suspensions of 1:10 re a c t e d w i t h 1%0 an mixture w i t h N 58 65 66 77 77 79 88 88 89 98 99 100 v i i Page TABLE 23 Fe c o n c e n t r a t i o n i n the ex-t r a c t s from s o i l 0.005MCaCl suspensions of 1:10 a c i d i f i e d w i t h HG1, and r e a c t e d with 1 ? S 0 2 i n mixture with N , and w i t h C 0 2 and N 2 ( S e r i e s I I I ) 102 TABLE 2k ( S e r i e s IV) Data from the ana-l y s i s of the e x t r a c t s from the r e a c t i o n of 1% suspensions of s o i l s p a r t i c l e s w i t h s e t t l i n g v e l o c i t i e s 20cm i n 1+ hours, i n 3.6 x 103 M C a C l 2 1 0 3 TABLE 2 5 ( S e r i e s V) Data from the analy-ses of e x t r a c t s from the r e a c -t i o n of 1% suspensions of s o i l p a r t i c l e s with s e t t l i n g v e l o c i t i e s 2 0 cm i n k hours, i n 5 . 6 0 x 1 0 3 j f l CaCl„. 10k TABLE 2 6 Data from the a n a l y s i s of s o i l : CaCl„ e x t r a c t s (1% suspensions) r e a c t e d with 0 9 i n mixture w i t h N 0 ( S e r i e s VI) 7 1 0 5 v i i i LIST OF FIGURES Page Pi g u r e I X^ray d i f f r a c t i o n p a t t e r n s of the c o a r s e and f i n e c l a y f r a c t i o n s from the 7 8 " - 8 4 " s o i l samples 3 9 P i g u r e I I X-ray d i f f r a c t i o n p a t t e r n s of the coarse and f i n e c l a y f r a c t i o n s from the 1+8 - 5 8 " s o i l samples 4 0 P i g u r e I I I X-ray d i f f r a c t i o n s p a t t e r n s of the coarse and f i n e c l a y f r a c t i o n s from the 3 £ " - 4 2 " s o i l samples 4 1 P i g u r e IV X-ray d i f f r a c t i o n p a t t e r n of the coarse c l a y f r a c t i o n from the 2 0 " -2 6 " s o i l sample 4 2 P i g u r e V X-ray d i f f r a c t i o n p a t t e r n s of the f i n e c l a y f r a c t i o n from the 2 0 " - 2 6 " s o i l sample 1+3 P i g u r e VI X-ray d i f f r a c t i o n p a t t e r n s of the coarse c l a y f r a c t i o n from the 1 " - 9 " s o i l sample. 4 4 P i g u r e VII X-ray d i f f r a c t i o n p a t t e r n s of o r i e n -ted specimens of Untreated f i n e c l a y ( 1 " - 9 " ) . 4 5 P i g u r e V I I I X-ray d i f f r a c t i o n p a t t e r n s of o r i e n -ted specimens of the A l b e r n i f i n e c l a y ( 1 " - 9 " ) f o l l o w i n g the Na c i t r a t e -N a 2 ^ 2 ° l + t r e s' f c r r i e n' t o f A g u i l e r a and J a c k s o n . ( 1 9 5 3 ) 4 6 P i g u r e IX Treated A l b e r n i c l a y run i n atmos-phere of N 4 7 P i g u r e X D i s s o l u t i o n curve of the A l b e r n i f i n e c l a y by the 0 s thaus method ( 1 9 5 8 ) ( 1 » - 9 " ) 4 8 P i g u r e XI Conductimetrie t i t r a t i o n curves f o r C.E.C. a n a l y s i s of f i n e c l a y from the i x A-B h o r i z o n s o i l which had "been e x t r a c t e d k times w i t h d i t h i o n i t e - c i t r a t e reagent P i g u r e XII Gonductimetric t i t r a t i o n curves f o r C.E.C. . a n a l y s i s of the f i n e c l a y from the C. h o r i z o n s o i l which was e x t r a c t e d twice with d i t h i o n i t e - c i t r a t e reagent. F i g u r e X I I I X-ray f l u o r e s c e n c e a n a l y s i s of C h o r i z o n and c o a t i n g s (0.25amps.). Comparison of Pe and Mn peak h e i g h t s f o r C and A-B h o r i z o n s . X ABSTRACT A study was undertaken to determine some of the chemical and m i n e r a l o g i c a l c h a r a c t e r i s t i c s of the A l b e r n i S l a y , a Vancouver I s l a n d s o i l which i s the r e p r e s e n t a t i v e of! the c o n c r e t i o n a r y Brown Group of s o i l s . Chemical analyses showed that i r o n , s i l i c a and aluminum are leached from the p r o f i l e and though c o n s i d -e r a b l e q u a n t i t i e s of these elements are p r e c i p i t a t e d on the s u r f a c e s of peds i n the deeper ho r i z o n s of the s o i l , no h o r i z o n of accumulation was formed. The r e t e n t i o n of i r o n i n the s u r f a c e h o r i z o n i n the form of f r e e i r o n oxides maintained the percentage of i r o n i n that h o r i z o n comparable w i t h the percentage i n the C h o r i z o n , and r e s u l t e d i n the f o r m a t i o n of h i g h l y s t a b l e c o n c r e t i o n s i n the A - B h o r i z o n of the s o i l . The form a t i o n of c o n c r e t i o n s seemed to have been i n f l u e n c e d by the h i g h magnetite content of the s o i l . The i n t e r a c t i o n between the p o s i t i v e l y charged surface of the magnetite p a r t i c l e s and organic anion complexes of the c a t i o n s of the f i r s t t r a n s i t i o n a l s e r i e s impeded the move-ment of these complexes through the s l o w l y permeable s o i l and p e r m i t t e d a b s o r p t i o n and p r e c i p i t a t i o n f o .form concre-t i o n s . x i The x-ray analyses of the c l a y s r e v e a l e d a weathering sequence i n which c h l o r i t e was developed, from weathered primary m i n e r a l s . The formula f o r the c h l o r i t e separated from the surface h o r i z o n c l a y s was c a l c u l a t e d and i t was found to he a d i o c t a h e d r a l A l - c h l o r i t e which had been p r e d i c t e d by Grim and by B r i n d l e y , but which had not been p r e v i o u s l y i d e n t i f i e d i n s o i l s . 1 MINERALOGICAL AND CHEMICAL STUDIES OF THE ALBERNI CLAY INTRODUCTION C o n c r e t i o n a r y Reddish Brown s o i l s have been d e s c r i b e d as o c c u r r i n g i n the E a s t e r n c o a s t a l p l a i n of Vancouver I s l a n d . S i m i l a r s o i l s occur along the Western c o a s t of Washington and Oregon (Wheeting 1 9 3 6 , W h i t t i g et a l . , 1 9 5 7 ) . These s o i l s are developed under a c y c l i c c l i m a t e of wet w i n t e r s and droughty summers and are d e r i v e d from a p a r e n t m a t e r i a l that had a b a s i c rock as i t s source. Charac-t e r i s t i c a l l y these s o i l s have a t h i n o r g a n i c s u r f a c e over-l y i n g a dark brown to r e d d i s h brown h i g h l y aggregated c l a y c o n t a i n i n g a l a r g e number of ferromagnetic c o n c r e t i o n s . The A l b e r n i s o i l s e r i e s which occupy the A l b e r n i b a s i n i n South-eastern Vancouver I s l a n d has developed on f i n e t e x t u r e d marine m a t e r i a l s d e r i v e d from b a s a l t i c r o c k s . I t i s one of the most p r o d u c t i v e f o r e s t s o i l s of B r i t i s h Columbia and has an extent of 9 , 7 0 5 acres on Vancouver I s l a n d . T h i s s e r i e s has been of great i n t e r e s t to the p e d o l o g i s t because of the d i f f i c u l t y that has been e x p e r i e n -ced i n p l a c i n g them i n the c l a s s i f i c a t i o n scheme. They were f i r s t c l a s s i f i e d as Reddish Brown and Shotty Brown P o d z o l i c s o i l s but subsequent examination i n d i c a t e d that the s o i l had many f e a t u r e s that were not commonly a s s o c i a t e d w i t h p o d z o l i c s o i l s . The morphology showed that the s o i l s had many c h a r a c t e r i s t i c s commonly a s s o c i a t e d w i t h l a t o s o l i c 2 r a t h e r than P o d z o l i c s o i l s . On t h i s "basis these s o i l s were p l a c e d i n a new g r e a t s o i l group c a l l e d the Concretionary-Brown. The A l b e r n i C l a y i s the modal member of t h i s s o i l group and has the f o l l o w i n g m o r p h o l o g i c a l and chemical c h a r a c t e r i s t i c s : ALBERNI CLAY L o c a t i o n ; 1+.2 m i l e s northwest of Port A l b e r n i on the n o r t h s i d e of highway on L o t 166. The sample s i t e i s about 100 f e e t West of an i n t e r m i t t e n t creek i n an area that has been logged. C l a s s i f i c a t i o n : C o n c r e t i o n a r y Brown (Reddish Brown) P o r e s t Parent M a t e r i a l : The s o i l s are developed on u n i f o r m c l a y l a i d down i n a l a n d l o c k e d b a s i n that was s u b j e c t e d to marine i n u n d a t i o n s . V e g e t a t i o n : The area has been logged and. may have been s l a s h burned. Present v e g e t a t i o n i s Douglas f i r , s a l a l , bracken f e r n , s o o p a l a l l i e , s p i r e a e and an o c c a s i o n a l a l d e r . Physiography The s i t e sampled i s on a 1% s l i g h t l y con-and R e l i e f : vex slope on the edge of a drainage depres s i o n i n the broad A l b e r n i b a s i n . E l e v a t i o n : Approximately 100 f e e t . Drainage: Well d r a i n e d , with moderately slow permea-~* b i l i t y and moderate r u n o f f . S t o n i n e s s : A few fragments of g r a v e l v/ere found i n the upper 2k i n c h e s . M o i s t u r e at time sampled: Moist Root D i s t r i - Roots were c o n c e n t r a t e d i n the Ah and B i r b u t i o n : h o r i z o n s (0-13") but were f a i r l y abundant to the bottom of the BC (20"). Pew r o o t s f o l l o w e d n a t u r a l c r a c k s and cleavage planes to a depth of 50 or more i n c h e s . 3 P r o f i l e D e s c r i p t i o n : C.E..C Meg/100 gm A Q 0 and. A *' 2 - 0" L i t t e r of n e e d l e s , b r a c -ken f e r n , s a l a l l eaves w i t h a t h i n (4") 5* and H l a y e r ; not sampled Ah 0 - 2" Brown to y e l l o w i s h brown (10YR 5/3.5)** dry, dark brown (7.5YR 3/2) moist c l a y . Strong medi-um to coarse g r a n u l a r S t r u c t u r e which appears to c o n s i s t l a r g e l y of worm c a s t s j f r i a b l e moist and s l i g h t l y p l a s t i c to p l a s t i c whe wet; r o o t s common pH 5.0 U.2.9 B h i r 2 - 6" Brown (7-5YR 5/k) dry, (crushed c o l o r s t r o n g brown 7.5YR 5/2) dark r e d -d i s h brown (5YE 3-5/k) moist c l a y ; weak medium to coarse sub-angular b l o c k y b r e a k i n g r e a d i l y to s t r o n g medium to coarse g r a n u l a r ; abundant s p h e r o i d a l c o n c r e -t i o n s or s h o t t y aggregates; r o o t s abundant; pH 5,0 i+l.58 B h i r 2 6 - 1 3 " Y e l l o w i s h brown (10YR 5/k) dry, brown to dark brown (7.5YR k/k) moist c l a y ; weak coarse sub-angular b l o c k y s t r u c t u r e b r e a k i n g to s t r o n g f i n e sub-angular b l o c k y or coarse g r a n u l a r ; s l i g h t l y hard when dry, f r i a b l e when moist; abun= dant c o n c r e t i o n a r y forms; lower boundary c l e a r ; p H 5.0 i+0.0 $ "Horizon de-si gna'ti'sm a c c o r d i n g to Canadian N a t i o n a l S o i l Survey Committee Report. ** C o l o r d e s i g n a t i o n s from M u n s e l l C o l o r Standards. k P r o f i l e D e s c r i p t i o n  (continued) BC 13 - 20" L i g h t y e l l o w i s h brown to p a l e brown (IOYR 5/2+)dry, brown to dark y e l l o w i s h brown (IOYR k/k) moist c l a y ; s t r o n g f i n e to medium sub-angular b l o c k y s t r u c -t u r e ; &ard when dry and f i r m when moist; r o o t s common, lower boundary c l e a r 37-75 CB 20 - 26" L i g h t y e l l o w i s h Tbr®wn (IOYR § A ) d r y ( i n t e r i o r of peds have a p a l e brown (IOYR 7/3) c o l o r ) ; v e l l o w -i s h brown (10Y1 5/k) moist c l a y ; moderate to s t r o n g medium to coarse sub-angular b l o c k y s t r u c t u r e ; hard to v e r y hard when dry; t h i n f i l m of c l a y ( c l a y s k i n s or f l o s s ) continuous on peds; few r o o t s , lower boundary g r a d u a l . pH 5.1 3k*2& O, 26 - 50" P a l e yellow (5Y 7/3) d r y y e l l o w i s h brown (10YR 5/k) to o l i v e (5Y 5/k) moist, c l a y . Strong coarse i r r e g -u l a r b l o c k y s t r u c t u r e ; v e r y hard when d r y and p l a s t i c when wet; abundant t h i n white ( S i ? ) c o a t i n g s on peds which at lower p o r t i o n (kO i n . ) g i v e way to t h i n b l a c k c o a t i n g s . Pew r o o t s along n a t u r a l cleavages; lower boundary c l e a r and d i f f u s e . 34»05 C 2 50" * P@le yellow (5.Y. 7/3) p a l e brown (IOYR 6/3) moist, c l a y ; s t r o n g coarse to v e r y coarse i r r e g u l a r p r i s m a t i c b r e a k i n g to s t r o n g coarse b l o c k y ; v e r y hard when dry and p l a s t i c when wet; almost continuous b l a c k c o a t i n g on cleavage f a c e s ( r e f e r r e d to by H.Pyles as Wad.M.No.2 x H20) r o o t s v e r y few. 6 TABLE 1 CHEMICAL COMPOSITION OP CONCRETIONS, CONCRETIONARY SOIL PROM THE A-B HORIZON, AND SOIL PROM THE C± HORIZON * Concre-t i o n s % Coneretion-ary S o i l % C Horizon 1 S o i l % LOSS on i g n i -t i o n 10.23 9.08 10.68 S i 0 2 49.43 53-32 50.09 R2°3 42.06 38.50 41.57 P e 2 0 3 11.38 10.29 12.75 A 1 2 0 3 29.58 27.16 27.92 T i 0 2 1.10 1.05 0.90 CaO 0.96 1.18 0.34 MgO 5.29 5.33 5-53 Free i r o n ( F e 2 0 3 ) 3.40 3.30 1.12 S i 0 2 / R 2 0 3 1.18 1.39 1.21 Because of the economic i n t e r e s t i n these s o i l s hy v i r t u e of t h e i r inherent f e r t i l i t y "and the i n t e r e s t aroused from the p o i n t of fundamental research, the A l h e r n i C l a y was se l e c t e d f o r study of the chemical p r o p e r t i e s of t h i s s o i l group. Recently i t has been r e a l i s e d that the presence * A n a l y s i s k i n d l y s u p p l i e d hy Mr. H.H.Hortie, Canada Department of A g r i c u l t u r e , Vancouver B.C. 7 of c h l o r i t e or c h l o r i t i c m a t e r i a l i n sedimentary s o i l s i s much more widespread than was f o r m e r l y thought (Grim, D i e t z and B r a d l e y 1949) and the A l b e r n i C l a y ( f o r which p r e l i m i n a r y i n v e s t i g a t i o n s r e v e a l e d a s t r o n g l y c h l o r i t i c i n f l u e n c e ) presented another o p p o r t u n i t y to make a study of the c o n d i t i o n s which f a c i l i t a t e i n t e r c o n v e r s i o n s between the v a r i o u s c l a y m i n e r a l s * Jackson (1959) has used the data from c l a y m i n e r a l analyses t o i n t e r p r e t pedogenesis i n the s o i l p r o -f i l e , and the p o s s i b i l i t y of I l l i t e - C h l o r i t e - M o n t m o r i l -l o n i t e t r a n s f o r m a t i o n s , both i n the s o i l and i n the l a b o r a -t o r y hap : r e c e i v e d a great d e a l of a t t e n t i o n . I t was t h e r e f o r e d e c i d e d to make a m i n e r a l o g i c a l a n a l y s e s of the c l a y f r a c t i o n s at v a r i o u s depths i n the pro-f i l e to evaluate the e f f e c t of weathering i n t h i s e n v i r o n -ment on the par e n t m a t e r i a l . I t was a l s o f e l t that study of the c o n c r e t i o n s which are so prominent i n t h i s s o i l would be p r o f i t a b l e i f such a study c o u l d g i v e i n f o r m a t i o n concerning the c o n d i -t i o n s under which movement and p r e c i p i t a t i o n of i r o n are l i k e l y to take p l a c e . The presence of f e r r u g i n o u s and f e r -romanganiferous c o n c r e t i o n s has been repo r t e d i n P o d z o l i c and L a t e r i t i c s o i l s by many authors. One of the c o n d i t i o n s which has been c o n s i s t e n t l y r e p o r t e d £S- h e i n g a s s o c i a t e d w i t h the f o r m a t i o n of c o n c r e t i o n s istfce a l t e r n a t i o n of o x i d i s i n g and r e d u c i n g c o n d i t i o n s i n the p r o f i l e . I t was 8 f e l t that by the use of s o l u b i l i t y r e l a t i o n s h i p s of i r o n and aluminum as determined by the analyses of s o i l e x t r a c t s , i t would be p o s s i b l e to apply the thermodynamic data which are a v a i l a b l e f o r i r o n and aluminum compounds to e s t a b l i s h c r i t e r i a (by a combination of the techniques employed by Lindsay et a l , 1959 and C l a r k and Peech, 1955) f o r the e x i s -tence of known compounds of i r o n and aluminum i n the A l b e r n i Clay. I t was t h e r e f o r e decided to r<§act the s o i l s under d i f f e r e n t c o n d i t i o n s of oxygen tension and measure the con-c e n t r a t i o n s of i r o n and aluminium i n the s o i l s o l u t i o n under these c o n d i t i o n s . Though the approach towards e q u i l i b r i u m i s slow i n s o i l systems, expressions i n v o l v i n g pH and pAl or pFe could give information concerning the e q u i l i b r i u m trends of these ions i n the s o i l water systems. 9 MINERALOGICAL AND CHEMICAL PROPER-TIES OP ALBERNI CLAY MATERIALS AND METHODS Samples With the o b j e c t i v e of o b t a i n i n g i n f o r m a t i o n that would c h a r a c t e r i z e the m i n e r a l o g i c a l sequence and the chem-i c a l d i f f e r e n c e s a s s o c i a t e d w i t h p r o f i l e c h a r a c t e r i s t i c s of the A l b e r n i C l a y , samples f o r s s t u d y were obtained from depths of 1" - 9 " , 20" - 2 6 " , 36" - 4 2 " , 4 8 " - 58" and 7 8 " - 84"* C o n c r e t i o n s , samples of the b l a c k c o a t i n g s which covered the cleavage s u r f a c e s of peds i n the h o r i z o n (50" +), and the s i l i c e o u s c o a t i n g s found at a depth of 26" - 5 0 " were a l s o s e l e c t e d f o r t h i s purpose. X-Ray and chemical a n a l y s i s of c l a y S e p a r a t i o n of Clays S o i l samples were ground to pass a 0.5 mm s i e v e , In a l l cases i t was p o s s i b l e to crush the s o i l aggregates so that none was r e t a i n e d on the 0.5 mm mesh s i e v e . To en-sure adequate d i s p e r s i o n , l a r g e samples of s o i l were f i r s t t r e a t e d with' hydrogen p e r o x i d e u n t i l a moderate r e a c t i o n i n d i c a t e d that r e a d i l y o x i d i z e d organic matter had been d e s t r o y e d . The f r e e i r o n was then removed by the method of A g u i l l e r a and Jackson (1953). Treatment f o r the removal of f r e e i r o n was continued u n t i l the a d d i t i o n of hydrogen 10 p e r o x i d e to the d i t h i o n i t e e x t r a c t produced l i t t l e c o l o r . The A-B h o r i z o n was e x t r a c t e d 8 times w i t h the d i t h i o n i t e -c i t r a t e reagent, the C h o r i z o n sample was e x t r a c t e d k times, and the other s o i l samples r e c e i v e d 2 e x t r a c t i o n s each. A one percent suspension of the t r e a t e d s o i l was then d i s p e r s e d by a d d i t i o n of s u f f i c i e n t 10 p e r c e n t Na^CO, to r a i s e the pH to 9 . 5 , and the f r a c t i o n l e s s than 2 . 0 microns e q u i v a l e n t s p h e r i c a l diameter was se p a r a t e d by s e d i -mentation. S e v e r a l resuspensions were made to o b t a i n maximum y i e l d of the c l a y . S e p a r a t i o n of the c l a y i n t o two f r a c t i o n s ( 2 . 0 to 0 . 2 and l e s s than 0 . 2 microns) was made w i t h the Sharpies s u p e r c e n t r i f u g e . The coarse c l a y f r a c t i o n was r e -c e n t r i f u g e d u n t i l the c e n t r i f u g a t e was f r e e from suspended p a r t i c l e s l e s s than 0 . 2 microns. The c l a y suspensions were f l o c c u l a t e d w i t h O.O^M CaClg and the supernatant s o l u t i o n was siphoned o f f . Samples intended f o r x-ray a n a l y s i s were then washed f r e e of c h l o r i d e w h ile those which were used f o r chemical a n a l y s i s were f i r s t s a t u r a t e d w i t h NH^ ions by d i s p e r s i n g the c l a y i n IN amonium acetate and then washing f r e e of s a l t s . Chemical A n a l y s i s Chemical analyses of the c l a y f r a c t i o n s f o r S i , T i , Fe, A l , Ca, and Mg were made by the method d e s c r i b e d by Robinson ( 1 9 4 5 ) , and the h y d r o f l u o r i c a c i d method of S c o t t (p.804)and a P e r k i n Elmer flame photometer were used to determine K. 11 X-ray A n a l y s i s The x - r a y d i f f r a c t i o n data were obtained w i t h F e - f i l t e r e d Co r a d i a t i o n . O r i e n t e d specimens of the Ca-s a t u r a t e d c l a y prepared hy sedimentation on g l a s s s l i d e s were i r r a d i a t e d f o l l o w i n g a i r - d r y i n g , ethylene g l y c o l treatment, and a f t e r h e a t i n g c o n s e c u t i v e l y to 3 0 0 , 4 5 0 , 500 and 700°C. D i f f e r e n t i a l Thermal Analyses D.T.A. curves were obtained w i t h equipment and o p e r a t i n g c o n d i t i o n s d e s c r i b e d by Brydon and Heystek (1958) C a t i o n exchange c a p a c i t y analyses The c a t i o n exchange c a p a c i t y values which were used, i n a l l subsequent c a l c u l a t i o n s were made by the con-d u c t i m e t r i c t i t r a t i o n method d e s c r i b e d by Warkentin ( 1 9 5 7 ) • C a t i o n exchange c a p a c i t y was a l s o determined by the ammonium a c e t a t e method (Peech et a l 1947) and by the manganese method (Jackson p.£6). Cl a y s which had been suspended i n s o l u t i o n s of PeSO, , F e C l , , MgSO, , C a C l 0 and A1C1, f o r three months were 4 3 4 2 D removed from the suspension and d r i e d . The e f f e c t of these treatments on the C.E.C. of these c l a y s was evaluated by a m o d i f i e d ammonium ac e t a t e method. In t h i s method samples of c l a y (100 to 500 mg) were s a t u r a t e d w i t h NH^ by washing s e v e r a l times w i t h IN ammonium acetate and c e n t r i f u g i n g . The excess NH^Ac was removed w i t h a l c o h o l , as i n the st a n d -a r d procedure, or w i t h acetone, and the ammonia occupying 12 exchange s i t e s was d i s t i l l e d i n t o 0.03N HgSO^. The excess H2 S°4 W a s ^^^raiei3L w i t h 0.01N sodium hydroxide. RESULTS AND DISCUSSION TABLE 2 . PERCENTAGE COMPOSITION OP CLAY FRACTIONS OP ALBERNI CLAY BASED ON OVEN DRY WEIGHT A - B H o r i z o n G. Horizon 2.0-0.2 0.2 2.0-0.2 0.2 H 20 .7.85 12.61 6.72 10.62 s i o 2 48.28 39.99 50.62 44.90 R2°3 33.15 39.13 30.71 34.01 P e 2 0 3 5.54 4.57 5.34 5.84 A1 20 3 26.90 33.52 24.28 27.06 T i 0 2 0.71 1.04 1.09 1.11 CaO 1.19 0.15 1.49 2.29 MgO 6.08 4.58 6.23 5.11 K 20 1.72 1.61 1.70 2.42 T o t a l 98.27 98.07 97.47 99.05 Si0 2/ R 2 ° 3 1.46 1.02 I.65 1.32 78" - 84" Coarse c l a y f r a c t i o n - The most promi-nent f e a t u r e shown by the x-ray d i f f r a c t i o n p a t t e r n ( P i g -ure l ) of the unheated coarse c l a y from the 78" - 84" s o i l o sample was a broad peak with d i s t i n c t maxima at 10A and at 13 o o 12A. A f t e r treatment w i t h g l y c o l the 12A peak was r e p l a c e d by a broad d i f f u s e peak which covered the r e g i o n between o 12 to 15A, The u n t r e a t e d sample a l s o showed a s e r i e s of ll+/nA°basal r e f l e c t i o n s i n which the 1 s t . and 3rd. orders O o at 1UA and 4»72A were weaker than the 2nd. and 2+th. orders at 7-1A and 3*5° A r e s p e c t i v e l y . A f t e r heat treatment at o o 500 C there was some i n t e n s i f i c a t i o n of the 10A peak. This was accompanied by c o l l a p s e of the b a s a l spacings of expan-ded l a y e r m i n e r a l s to give a d i f f r a c t i o n peak which covered a the r e g i o n between 11.2 and 11.7A. The p e r s i s t e n c e of a d i s c r e t e 10A peak, taken i n c o n j u n c t i o n w i t h the s e r i e s of lh/nA°basal r e f l e c t i o n s which are t y p i c a l of i r o n r i c h c h l o r i t e s , showed that the c l a y c o n t a i n e d d i s c r e t e i l l i t e and c h l o r i t e components, and the presence of the i n d i v i d u a l 12A peak i n the unheated sample, which s h i f t e d to g i v e a broad band of d i f f u s e r e f l e c t i o n s of low i n t e n s i t y i n d i c a t e d the presence of a randomly i n t e r -o s t r a t i f i e d mixture of 10-lij.-15A m a t e r i a l . The c o l l a p s e of t h i s m a t e r i a l a f t e r heat treatment to give spacings between O O o 11.2A to 11.7A and the i n t e n s i f i c a t i o n of the 10A peak showed that the c l a y of t h i s sample contained r e l a t i v e l y l a r g e q u a n t i t i e s of t h i s mixed l a y e r m a t e r i a l . 78" - 8k" F i n e c l a y f r a c t i o n . - The x-ray d i f f r a c -t i o n t r a c i n g ( F i g u r e l ) of the f i n e c l a y from the 78" - 8k" s o i l sample showed a broad peak w i t h a f l a t maximum rang-0 o i n g from 12.8A - 13.4A which s h i f t e d to gi v e a w e l l d e f i n e d Ik peak at 15»3A a f t e r treatment w i t h g l y c o l . The unheated sample showed very small peaks i n the reg i o n of II4A, 7*kA and 3»52A which c o u l d p o s s i b l e be co n s i d e r e d the 1 s t . , 2nd., and i+th order r e f l e c t i o n s of c h l o r i t e s i m i l a r t o those found w i t h the coarse c l a y . The 3rd order r e f l e c t i o n at k»72A and 3'52A peaks were so ve r y weak that o n l y t r a c e s of II4A. m a t e r i a l c o u l d have been p r e s e n t i n d i s c r e t e form i n t h i s sample. A f t e r h e a t i n g the sample to 500°C the 12.8 - 13.ILA peak c o l l a p s e d to gi v e a broad band of d i f f u s e r e f l e c t i o n s which were s c a t t e r e d over the r e g i o n from 10A to 13.5A. Peaks of low i n t e n s i t y were pr e s e n t i n the un-heated and the g l y c o l a t e d samples at 9.8A and 9.9A r e s p e c t -i v e l y and i n the sample which was heated to 500°C. The maxi-mum at 10A was s l i g h t l y more i n t e n s e than the other maxima at 9 . 7 A , 11.OA, 12.2A and 13.5A which together w i t h the 10A peak formed the d i f f u s e band of r e f l e c t i o n s r e s u l t i n g from the c o l l a p s e of the expanded l a y e r c l a y f r a c t i o n s . Because of the absence of d i s c r e t e 10A peaks, and of the 14/nA s e r i e s of b a s a l r e f l e c t i o n s , i l l i t e and c h l o r i t e were not cons i d e r e d to be d i s c r e t e components of t h i s c l a y sample, and the s h i f t which produced a w e l l de-f i n e d peak at 15»3A a f t e r treatment with g l y c o l showed that the expanding l a y e r m a t e r i a l was the major component of the c l a y of t h i s sample. The sample was t h e r e f o r e i d e n t i f i e d as a random mixed l a y e r assemblage of m o n t m o r i l l o n i t e -i l l i t e - c h l o r i t e i n which the m o n t m o r i l l o n i t i c c h a r a c t e r i s -15 t i c s of the c l a y predominated. 48" _ C l a y f r a c t i o n - The x-ray d i f f r a c t i o n p a t t e r n (Figure l l ) of the unheated sample of the f i n e c l a y f rom the 48" - 58" s o i l sample was dominated hy an intense and w e l l d e f i n e d peak at 12.5A which s h i f t e d a f t e r t r e a t -ment wi t h g l y c o l to a 16.OA s p a c i n g . A f t e r h e a t i n g to a temperature of 500°C the expanded l a y e r s of the c l a y c o l -l a p s e d to g i v e a s e r i e s of r e f l e c t i o n s over the r e g i o n from 9.6A to 10A - 11.1A. The peak at 9.6A was the most intense f o r t h i s s e r i e s of r e f l e c t i o n s and there was a p r o g r e s s i v e r e d u c t i o n of i n t e n s i t y on the low angle s i d e of the s e r i e s . A 10A peak of low i n t e n s i t y remained unchanged throughout a l l the treatments and on t h i s b a s i s i l l i t e was i d e n t i f i e d as a minor component of the c l a y s i n t h i s sample. The p r o -nounced s h i f t of the 12.5A peak to 16.OA a f t e r treatment w i t h g l y c o l showed that m o n t m o r i l l o n i t e was the component of the mixed, l a y e r c l a y which was r e s p o n s i b l e f o r the 12.5A peak shown by the unheated sample. I t was t h e r e f o r e con-s i d e r e d that the 12.5A peak i n d i c a t e d the presence of an i l l i t e - m o n t m o r i l l o n i t e mixed l a y e r c l a y i n p r o p o r t i o n s c l o s e l y approaching 1:1. The f a i l u r e of the expanded l a y e r m a t e r i a l to c o l l a p s e completely to 10A a f t e r heat treatment to 500°G was a t t r i b u t e d to mixed l a y e r lhA - 15A m a t e r i a l . The c l a y was t h e r e f o r e i d e n t i f i e d as a r e g u l a r i n t e r s t r a t i f i e d i l l i t e - m o n t m o r i l l o n i t e - c h l o r i t e i n which the presence of a s m a l l degree of c h l o r i t i z a t i o n had preven-16 t e d complete c o l l a p s e or expansion a f t e r the r e q u i s i t e treatments. With t h i s was a s s o c i a t e d a small amount of d i s c r e t e i l l i t e . 48" - 58" F i n e c l a y f r a c t i o n - The f i n e c l a y f r a c -t i o n separated from the 48" - 58" s o i l sample gave d i f f r a c -t i o n p a t t e r n s ( F i g u r e IT) which were e s s e n t i a l l y i d e n t i c a l w i t h the d i f f r a c t i o n p a t t e r n s f o r the coarse c l a y f r a c t i o n of the same s o i l sample. There was, however, a g r e a t e r i n -t e n s i f i c a t i o n of the 10A peak a f t e r heat treatment to 500°C' i n the f i n e c l a y f r a c t i o n than there was i n the sample of c o a r s e c l a y , and i n t e n s i f i c a t i o n of the 10A peak was accom-p a n i e d by decreased s c a t t e r i n g on the low angle s i d e of the 10A peak. The sample was t h e r e f o r e c o n s i d e r e d to c o n s i s t p r i n c i p a l l y of r e g u l a r mixed l a y e r i l l i t e - m o n t m o r i l l o n i t e -c h l o r i t e w i t h l e s s c h l o r i t e i n t e r s t r a t i f i c a t i o n than the c o a r s e c l a y f r a c t i o n , and small amounts of i l l i t e . 36" - i i 2 " Coarse c l a y f r a c t i o n - The coarse c l a y f r a c t i o n of the 36" - 42" s o i l sample gave a d i f f r a c t i o n p a t t e r n ( F i g u r e I i i f o r the unheated sample i n which the main f e a t u r e was a broad peak w i t h a maximum at 12.OA. The peak t a i l e d o f f s l o w l y on the h i g h angle s i d e of the 12.OA r e f l e c t i o n and secondary maxima of p r o g r e s s i v e l y reduced i n t e n s i t y were observed at spacings which corresponded to the i l l i t e 10A r e f l e c t i o n and the 7.1A c h l o r i t e (002 ) r e -f l e c t i o n . Other f e a t u r e s possessed by t h i s d i f f r a c t i o n t r a c i n g were two humps, one i n the 4.75A - 5»1A r e g i o n and 17 the o t h e r i n the 3*5 - 3«52A r e g i o n . A f t e r treatment w i t h g l y c o l , the 12.OA peak was r e p l a c e d hy a broad peak w i t h a f l a t maximum which extended from II+-I5.4A. Other charac-t e r i s t i c s of the t r a c i n g from the g l y c o l a t e d sample were a hump w i t h a maximum at 10A which was somewhat obscured by h i g h and low-angle s c a t t e r i n g , and peaks at 7«2A, 1+.75A and 3.51A. A f t e r the sample was heated to a temperature of 500°C, most of the l h A and a l l of the 15A m a t e r i a l c o l l a p s e d to g i v e a broad but w e l l d e f i n e d peak w i t h twin maxima at 10A and 11.5A biit a very sma l l amount of li+A m a t e r i a l r e -t a i n e d i t s spacing. The 7.1A peak was f l a t t e n e d by heat treatment to 500°G and the 4-75A and 5.OA peaks were r e -p l a c e d by a hump which extended from 4.8A. I t i s seen from the t r a c i n g s presented i n F i g u r e s II and III t h a t the d i f f r a c t i o n p a t t e r n s of the coarse c l a y f r a c t i o n s from the 1+8" - 58" and the 36" - 42" s o i l samples d i f f e r e d g r e a t l y i n many r e s p e c t s . In the d i f f r a c t i o n t r a c e s of the unheated samples of these c l a y s a d i s c r e t e c l e a n 12.5A° peak was ob t a i n e d f p r the 1+8" - 58" sample. With the 36" - 1+2" sample the maximum of the peak was at 12A° and. as the r e s u l t of a continuous s e r i e s of r e f l e c t i o n s from random i n t e r s t r a t i f i e d m a t e r i a l the peak was broadened so tha t the 7.1A c h l o r i t e 8.1+ amphibole and 10A l i t t l e peaks appeared as minor r e f l e c t i o n s superimposed on the main 12.OA peak. The second major d i f f e r e n c e was the appearance i n the 38" - 42" sample of the 14/nA b a s a l r e f l e c t i o n s which 18 showed that c h l o r i t e was present i n d i s c r e t e form i n t h i s c l a y sample. The r e c o g n i t i o n of a d i s c r e t e c h l o r i t e component i n t h i s s o i l a l s o l e d to the c o n c l u s i o n that the mixed l a y e r m a t e r i a l which was r e s p o n s i b l e f o r the broadening of the 12.OA peak and the r e d u c t i o n of i t s maximum from 12.5A (48" - 58" sample) to 12A may have been predominantly c h l o r i t i c i n n a t u r e . This c o n c l u s i o n was s u b s t a n t i a t e d by the x - r a y d i f f r a c t i o n p a t t e r n of the sample a f t e r treatment w i t h g l y c o l . The broad 14 - 15A peak of the g l y c o l a t e d 36" -42" sample showed superimposed maxima which were of about e q u a l i n t e n s i t y and which corresponded to an unchanged 14A° c h l o r i t e r e f l e c t i o n ; and a s e r i e s of r e f l e c t i o n s f rom ex-panded m a t e r i a l which ranged from 14«5 - I5.4A. The presence of d i s c r e t e c h l o r i t e i n the sample and the succeeding s e r i e s of maxima were emphasized by the presence of random i n t e r -s t r a t i f i e d m a t e r i a l which, because i t was h i g h l y c h l o r i t i -zed, showed c o m p a r a t i v e l y l i t t l e expansion. The x-ray d i f f r a c t i o n p a t t e r n of the 38" - 42" c o a r s e c l a y f r a c t i o n which had been heated to 500°C showed by the c o m p a r a t i v e l y c l e a r d e f i n i t i o n of i t s twin 10A and 11.5A maxima that d i s c r e t e 10A i l l i t e and r e g u l a r i n t e r -s t r a t i f i e d i l l i t e - c h l o r i t e were a l s o p r e s e n t i n the sample. On t h i s b a s i s the c l a y of the 36" - 4 2 " s o i l sample was i d e n t i f i e d as mixed l a y e r i l l i t e - c h l o r i t e -19 m o n t t n o r i l l o n i t e w i t h a r e g u l a r l y i n t e r s t r a t i f i e d i l l i t e -c h l o r i t e component and d i s c r e t e amounts of i l l i t e and c h l o r i t e . 36" - 4 2 " F i n e c l a y f r a c t i o n . - The x-ray d i f -f r a c t i o n p a t t e r n ( F i g u r e H l ) of the unheated sample of f i n e f r a c t i o n c l a y from the 36" - 42" s o i l sample was very s i m i l a r to that of the coarse f r a c t i o n . Continuous reflec-t i o n s from i n t e r s t r a t i f i e d 1 0 - 11+ - 15A m a t e r i a l broadened, the peak which showed a maximum at 1 2 . 2 A . The main d i f -f e r e n c e between the peaks in the 7A - - 1 0 A .regions for the two sam-p l e s , was the r e d u c t i o n of the i n t e n s i t i e s of the isecondary maxima at 7*OA and at 1 0 A , and the change i n the spacing of the maximum from 1 2 A f o r the coarse c l a y to 1 2 . 2 A f o r the f i n e c l a y sample. A f t e r g l y c o l a t i o n a d i s c r e t e 1 5 . 8 A peak was de-veloped, by the s h i f t of the 1 2 . 2 A r e f l e c t i o n to a l a r g e r s p a c i n g . The 1 5 . 8 A ° peak showed s l i g h t s c a t t e r i n g and the low i n t e n s i t y of the 11+.7A bump on the h i g h angle s i d e of the main I 5 . 8 A peak showed that there was ve r y l i t t l e g l y -c o l s t a b l e ll+A m a t e r i a l p r e s e n t i n the sample. With succes-s i v e heat treatments at h i g h e r temperatures the expanded m a t e r i a l g r a d u a l l y c o l l a p s e d and at 500°C a r a t h e r broad peak was developed which had a maximum over the r e g i o n of 9.9A - 1 0 . 3 A and a d i f f u s e hump t r a i l i n g from 1 1 . 3 to about 1 2 . 5 A ° . A ll+A peak of very low i n t e n s i t y remained a f t e r the 500°c treatment. 20 The c l a y components of t h i s f r a c t i o n appeared, from the nature of the d i f f r a c t i o n p a t t e r n s of the unheated samples, and the i n t e n s i t y and extent of the s h i f t a f t e r treatment with g l y c o l , to he i n t e r m e d i a t e i n c h a r a c t e r be-tween the c l a y s of the f i n e f r a c t i o n from the 48" - 58" s o i l sample and the coarse c l a y from the 36" - 1+2" s o i l sample. As compared w i t h the f i n e c l a y f r a c t i o n from the 48" - 58" s o i l sample there was an i n c r e a s i n g c h l o r i t e and d e c r e a s i n g m o n t m o r i l l o r i t e content i n the f i n e c l a y f r a c t i o n of the 36" - 1+2" s o i l sample and the coarse c l a y of the 36" - 42" s o i l sample contained s t i l l more c h l o r i t e and l e s s m o n t m o r i l l o n i t e than e i t h e r of the two f i n e f r a c t i o n s . 20" - 26" ( ) Coarse c l a y f r a c t i o n . - The un-heated coarse c l a y f r a c t i o n of the C^ h o r i z o n showed a d i f -f r a c t i o n p a t t e r n ( F i g u r e IV) from the unheated sample i n which the most s i g n i f i c a n t development as compared w i t h the p a t t e r n s from samples p r e v i o u s l y discussed was the c l e a r and pronounced sequence of ll+n/A b a s a l r e f l e c t i o n s . The f i r s t o rder r e f l e c t i o n was superimposed on a broad peak extending from 13.2A to I4.2A, but the 2nd, 3rd and 4th order peaks at 7.IA 0, 4.7A0 and 3«52A° were d i s t i n c t and sharp and the 2nd and 4th orders were more i n t e n s e than the 1 s t and t h i r d o r d e r s . A broad peak of low i n t e n s i t y w i t h maximum extend-i n g from 9.6A - 10A° i n d i c a t e d that there was some 10A° m a t e r i a l i n the c l a y of t h i s sample. A f t e r treatment w i t h g l y c o l , the 13»2 - 14.2A r e -21 f l e c t i o n s h i f t e d to produce a sharp peak w i t h a w e l l d e f i n e d maximum at I4.5A 0 and the h i g h orders of the lhyhA s e r i e s of b a s a l r e f l e c t i o n s a l s o s h i f t e d to s l i g h t l y l a r g e r spac-i n g s w i t h l e s s e n e d i n t e n s i t i e s f o r the 3rd and 1+th order peaks. S u c c e s s i v e heat treatments at high e r temperatures caused a gradual c o l l a p s e of expanded l a y e r minerals to smal-l e r s p acings, and i n the sample which was heated to 550°C t h i s c o l l a p s e r e s u l t e d i n a broad r e f l e c t i o n which showed, peaks of maxima of 10A, 11.3A, 11.8A and 13•5A. The 11.8A peak was the most i n t e n s e of t h i s s e r i e s ; the high e r orders of the 14/n s e r i e s were e l i m i n a t e d by h e a t i n g but the li+A peak was i n t e n s i f i e d s l i g h t l y by h e a t i n g to 700°C. On the b a s i s of the presence of s e r i e s 14/nA spacings f o r which the i n t e n s i t i e s are c h a r a c t e r i s t i c of i r o n r i c h c h l o r i t e s , and i n view of the n e g l i g i b l e expansion shown a f t e r t r e a t -ment wi t h g l y c o l . The c l a y of t h i s sample was i d e n t i f i e d as a c h l o r i t e - i l l i t e - m o n t t n o r i l l o n i t e complex w i t h predom-i n a n t l y c h l o r i t i c c h a r a c t e r i s t i c s . 2 0 " - 2 6 " F i n e c l a y f r a c t i o n . - The major com-ponent of the f i n e c l a y f r a c t i o n of the 2 0 " - 2 6 " sample was a random mixed l a y e r kO% c h l o r i t e - 60% m o n t m o r i l l o n i t e a s s o c i a t e d w i t h small amounts of d i s c r e t e c h l o r i t e , mica and m o n t m o r i l l o n i t e . The main f e a t u r e of the d i f f T a c t o m e t e r ( F i g u r e y) p a t t e r n s was a r a t h e r i n t e n s e peak at li+.lA which s h i f t e d to I 5 . 5 A a f t e r g l y c o l s a t u r a t i o n . A f t e r heat treatment t h i s peak s h i f t e d g r a d u a l l y to 1 1 . 5 A . These are 22 c h a r a c t e r i s t i c s of random mixed l a y e r c h l o r i t e - m o n t m o r i l l -o n i t e and, on comparing w i t h the a p p r o p r i a t e curves of Jonas and Brown (1959) the p r o p o r t i o n of c h l o r i t e was found to "be l\.Q%. A small 10A mica peak and weak c h l o r i t e h i g h e r o r d e r "basal spacings were shown at low temperatures. The g l y c o l treatment y i e l d e d a smal l 17A m o n t m o r i l l o n i t e peak and a small 11+A c h l o r i t e (001) peak was r e v e a l e d on heat-i n g to 550°C. 1" - 9 " Coarse c l a y f r a c t i o n . The coarse c l a y f r a c t i o n of the A - B h o r i z o n sample c o n s i s t e d of c h l o r i t e which was s t a b l e to g l y c o l and heat treatment. The d i f f T a c t -ometer p a t t e r n s (Pigure VI) of the unheated samples showed a c l e a r sequence of 14-kX b a s a l spacings i n which the 2nd and i+th order peaks were c h a r a c t e r i s t i c a l l y s t r o n g e r than the 1st and 3rd order peaks. Mica, f e l d s p a r , quartz and amphibole peaks showed that small amounts of unweathered primary m i n e r a l s p e r s i s t e d i n t h i s f r a c t i o n . 23 TABLE 3 X-RAY DIFFRACTION DATA FROM NON-ORIENTED SPECI-MENS OF THE ALBERNI FINE CLAY AND OF COOKEITE (ZVYAGIN AND NEFEDOV 1954) A l b e r n i t e Cookeite d I d I h k l 1 4 . 1 5 10 7-112 5 6 . 9 5 002 4 . 7 8 4 1 4 . 6 7 7 003 4 - 4 7 7 9 4 . 4 8 4 020 3 . 5 3 7 5 3 . 5 2 9 004 3 . 2 0 1 1 2 . 8 3 4 1 2.81 7 005 2 . 7 6 1 1 2 . 6 4 4 1 2 . 5 6 9 6 2 . 5 7 9 2 0 1 , 1 3 1 2 . 5 1 6 1 2 .51 8 202 2 . 4 4 3 2 2 . 3 8 3 3 2 . 3 2 10 006 2 . 2 6 1 1 2 . 2 2 1 OkO 2.008 2 2 . 0 2 3 007 1 . 9 7 0 1 1 . 9 6 8 135 1 .86 1 206 1 , 7 4 0 1 180 2 008 1 .714 2 1 .69 4 2 4 0 , 3 0 0 1 . 5 6 5 1 1 .538 4 009 1 . 4 9 6 3 1 .491 9 060 2k The f i n e c l a y f r a c t i o n (0.2 micron) of the A - B h o r i z o n c o n s i s t s almost e n t i r e l y of d i o c t a h e d r a l A l -c h l o r i t e . The x- r a y d i f f r a c t i o n data from a non-oriented sample of l e s s than 0,2 micron c l a y are shown i n Table k w i t h the weak quartz r e f l e c t i o n s e l i m i n a t e d . The sequence of spacings suggested a c h l o r i t e s t r u c t u r e . On the b a s i s of the (OkOO r e f l e c t i o n s , the b dimension was found to be 8.988A. When the g e o m e t r i c a l r e l a t i o n s h i p b Q= / 3 a ^ was a p p l i e d , a Q was found to be 5.189A. Normal c h l o r i t e s and a l l t r i o c -t 8 h e d r a l l a y e r s i l i c a t e s have a b Q of approximately 9.2A., whereas the b Q dimension of d i o c t a h e d r a l minerals i s near 9»0A» The measured value d i f f e r e d s i g n i f i c a n t l y from, that of the t r i o c t a h e d r a l c h l o r i t e s and i t s magnitude suggested t h a t the c h l o r i t e was d i o c t a h e d r a l . F o r comparison, the d i f f r a c t i o n data f o r c o o k e i t e , a L i A l c h l o r i t e , p u b l i s h e d by Zvyagin and Nefedov (1954) i s a l s o i n c l u d e d i n Table 3. R e f l e c t i o n s which are common to b o t h minerals have s i m i l a r s p a c i n g s , the s i g n i f i c a n c e of which w i l l be d i s c u s s e d l a t e r . O r i e n t e d specimens of the un t r e a t e d 0.2 micron c l a y f r a c t i o n a l s o showed that the major c o n s t i t u e n t was a c h l o r i t e . The sequence of 14/nA b a s a l spacings (Figure VII) d i d not chenge upon g l y c o l treatment. At hi g h e r temperatures some of the m a t e r i a l appeared to c o l l a p s e g i v i n g a band of r e f l e c t i o n s between 10 and I4A. This behaviour was s i m i l a r to that of the A l - v e r m i c u l i t e s ( R i c h and Obershain, 1955) 25 Proc.19 : 334-339) which are a l l e g e d to c o n t a i n incomplete g i b b s i t e l a y e r s i n the i n t e r l a y e r spaces. P a t t e r n s of the " t r e a t e d " c l a y are shown i n P i g -ure IX. A l l of the peaks were sharper and more i n t e n s e than i n the u n t r e a t e d sample, presumably because the s e s q u i -oxides had been removed. At h i g h temperatures there was a g r e a t e r tendency towards c o l l a p s e to 10A as compared to the broad r e f l e c t i o n band o b t a i n e d w i t h the u n t r e a t e d m a t e r i a l . T h i s i s i n t e r p r e t e d as b e i n g due to the removal of p a r t of the i n t e r - l a y e r m a t e r i a l d u r i n g the treatment. Examination f o l l o w i n g prolonged treatment w i t h b o i l i n g weak HC1 (Brydon and Heystek 1958) i n d i c a t e d the complete d e g r a d a t i o n of the 2:1 l a y e r s i l i c a t e s and the absence of k a o l i n i t e . The r e l a t i v e i n t e n s i t i e s of the f i r s t f o u r (001) r e f l e c t i o n s were d i f f e r e n t from those of normal c h l o r i t e s i n which the even orders are more inte n s e than the odd ( B r i n d l e y & G - i l l e r y 1956). I t was found that w h i l e the (003) r e f l e c t i o n was weaker than the (002) or (OO4), i n g e n e r a l , the (001) was equal to or g r e a t e r than the i n t e n -s i t y of the (002) r e f l e c t i o n . The b a s a l s p a c i n g of c h l o r i t e s has been c o r r e l a -t e d w i t h the number of A l atoms r e p l a c i n g S i i n the t e t r a -h e d r a l l a y e r ( B r i n d l e y and G i l l e r y 1956) a c c o r d i n g to the e q u a t i o n d(00l) = I4.5O - O.31 x, where x i s the number of A l atoms i n t e t r a h e d r a l p o s i t i o n . The average c Q s p a c i n g o b t a i n e d by step c o u n t i n g over the f i r s t f o u r b a s a l r e f l e c -26 t i o n s was found to be 14.19 - 0.02A. S o l u t i o n of the equa-t i o n u s i n g the measured c Q dimension gave a value of x=1.00. Thus, from the x-ray d a t a , a t e t r a h e d r a l composition of (Si.,Al) i s i n d i c a t e d f o r each u n i t c e l l . DTA p a t t e r n s of the " t r e a t e d " c l a y are shown i n P i g u r e IX.The samples run i n a i r and i n Ng b o t h showed the i n i t i a l l o s s of absorbed water at l40°C:. t a much s m a l l e r endothermic peak at 300°C,., the l o s s of the major p o r t i o n of l a t t i c e hydroxyls at 550°C. > and an exothermic peak at 910° due to the energy r e l e a s e d upon r e c r y s t a l l i z a t i o n . The 300°C f e a t u r e may be a s s o c i a t e d w i t h the l o s s of h y d r o x y l s from a p o r t i o n of the i n t e r l a y e r hydroxide, s i n c e i t was f o l l o w i n g t h i s temperature that some of the m a t e r i a l gave x-ray r e f l e c t i o n s between 10 and luA. ( P i g -ure VIJl) The main DTA peak of the decomposition of g i b b s i t e occurs at t h i s same temperature. However, s i n c e the major p o r t i o n of the lhA peak remained s t a b l e to heat to a h i g h e r temperature, i t may be suggested that o n l y p a r t of the i n t e r - l a y e r hydroxide behaves as f r e e g i b b s i t e . This be-ha v i o u r suggests an analogy w i t h b r u c i t e and t r i o c t a h e d r a l c h l o r i t e . Since f r e e b r u c i t e decomposes at 400 - 450°C as compared to a 500 - 600°G temperature when sandwiched be-tween mica l a y e r s i n c h l o r i t e (Webb and Heystek 1957) i t i s suggested that a s i m i l a r behaviour may account f o r the heat s t a b l e I4A f e a t u r e i n t h i s m a t e r i a l . T A B L E 4 C A L C U L A T I O N O F T H E C H E M I C A L F O R M U L A O F T H E 0 . 2 M I C R O N F R A C T I O N O F T H E A L B E R N I A B H O R I Z O N % o f o v e n - d r y w e i g h t E q u i v a l e n t s o r C h a r g e s / 1 0 0 gm E q u i v a l e n t s o r C h a r g e s / u n i t c e l l A t o m s / u n i t c e l l T o t a l S i 0 2 39.85 T o t a l A 1 2 0 ? 33.52 Q u a r t z S i 0 2 f=14.85 T e t r . S i 0 2 e=25.00 y=1.6642 d=11.1964 c=2.7991 T e t r . A 1 2 0 ^ 9 . 1 0.5355 a=3.6027 b=1.2009 O c t a . A 1 2 0 ^ 24.42 1.4370 9.6677 3.2226 F e 0 4.56 0.1713 1.1525 0.3842 T i 0 2 1 . 0 3 0.0516 0.3471 0 . 0 8 6 8 M g O 4.58 0.2272 1.5285 0.7643 C a O 0.15 0.0053 0.0356 0.0178 K 2 0 1 . 6 1 0.0342 0.2301 0.2301 H 2 0 13 .18 9.8433 C . E . C . 35.7 m e . 00357 =x= 2.4978 + y 0.2402 0.2402 28 T A B L E 4 ( C O N T ' D ) C A L C U L A T I O N O P T H E C H E M I C A L F O R M U L A O F T H E 0.2 M I C R O N F R A C T I O N O F A L B E R N I A B H O R I Z O N A t o m s / u n i t c e l l C h a r g e s / | u n i t c e l l N e t C h a r g e T e t r a h e d r a l l a y e r S i 2.7991 A l 1.2009 T o t a l 4.0000 -1.2009 O c t a h e d r a l l a y e r s A l F e T i M g 3.2226 0.3842 0 . 0 8 6 8 0.7643 9.6677 1.1525 0.3471 1.5285 T o t a l 4.4578 12.6958 +0.6948 E x t e r n a l c a t i o n s C a K N H 4 ( C . E . C ) 0.0178 0.2301 0.2402 0.0356 O.2301 0.2402 0.5059 +0.5059 +0 .0008 F o r m u l a ( A 13.22 P e.38 T i . O 9Mg.76^A11.20Si2.80)°10(°H)8(Ca.02K.23X.24) 29 In a d d i t i o n to the r e d u c t i o n of the exothermic hump at 3 5 0°G due to o r g a n i c matter, the sample run i n an. o atmosphere of Ng showed a s m a l l endothermic peak at 770 which was not shown hy the sample run i n a i r , and f o r which no e x p l a n a t i o n can he o f f e r e d . Normal c h l o r i t e s show t h i s double ^ h y d r a t i o n f e a t u r e i n a peak at 500 - 600° due to decomposition of b r u c i t e and a s m a l l e r peak at 700 - 800°C due to the l o s s of h y d r o x y l s from the mica p o r t i o n of the s t r u c t u r e ( C a i l l e r e and Henin 1 9 5 7 ) ' X-ray examination of the f i r e d m a t e r i a l s showed them to be a mixture of m u l l i t e and a s p i n e l of unknown v a r i e t y . Chemical Analyses The t o t a l a n a l y s i s of the NH^ - s a t u r a t e d , " t r e a t e d " c l a y i s shown i n Table .4. The most s t r i k i n g as-p e ct was the very h i g h AlgO^ content. Since the MgO value was r a t h e r low, the m a t e r i a l i s e s s e n t i a l l y an aluminum c h l o r i t e . A p o r t i o n of the SiOg o r i g i n a t e d i n the q u a r t z , d e t e c t e d by x-ray d i f f r a c t i o n . Because of the s i g n i f i c a n t KgO c o n t e n t , i t might be expected that i l l i t e or f e l d s p a r would be p r e s e n t . However, there was no c o n c l u s i v e evidence of e i t h e r on the b a s i s of x -ray data. The p o s s i b i l i t y e x i s -ted that the potassium was i n s t e a d f i x e d i n the i n t e r - l a y e r p o s i t i o n s , and i n the f o l l o w i n g c a l c u l a t i o n s , t h i s i n t e r -p r e t a t i o n i s taken as the most reasonable. The c a t i o n ex-change c a p a c i t y 3 5 . 7 me/lOOgm. was r a t h e r h i g h but i s w i t h i n the range c i t e d by Grim (1953) f o r i l l i t e and c h l o r i t e , b o t h 30 of which have r i g i d , non-expanding s t r u c t u r e s . The L i con-t e n t was checked and was found to he l e s s than 0.001 per c e n t . A n a l y s i s of the e x t r a c t o btained d u r i n g the ^a^S^O^ -c i t r a t e b u f f e r t r e a t e d sample showed i t to c o n t a i n .5.5-6 per-c e n t ' Fe2°3 5 * ° 5 p e r c e n t A 1 2 ° 3 a n d t r a c e s o f M S ° * T h e M S ° a n a l y s e s c o n f i r m the o b s e r v a t i o n from x - r a y data that there was some degradation of the c l a y d u r i n g the treatment. The f r e e i r o n oxide content as expected was h i g h and b l e a c h i n g of the sample was complete as judged by the r e d u c t i o n of the n a t u r a l reddish-brown c o l o r . C a l c u l a t i o n of the S t r u c t u r a l Formula In the c a l c u l a t i o n of the s t r u c t u r a l formula of a c h l o r i t e , i t was assumed, as i s customary, that the u n i t c e l l c o n t a i n e d 18 oxygens of which 8 are present as hydrox-y l s . The net number of n e g a t i v e charges to be balanced by m e t a l l i c c a t i o n s i s t h e r e f o r e 28. The nature of the p o r t i o n of the m a t e r i a l which p a r t i a l l y c o l l a p s e d on heat t r e a t -ment i s unknown. I t i s q u i t e p o s s i b l e that t h i s p o r t i o n would have a d e f i c i e n c y of hydroxyls i n r e l a t i o n to the i d e a l c h l o r i t e s t r u c t u r e . The assumption of 28 e q u i v a l e n t s of n e g a t i v e charge would .'then be i n e r r o r , but f o r a l l p r a c -t i c a l purposes i t was c o n s i d e r e d that t h i s would not s e r i o u s l y a f f e c t the g e n e r a l v a l i d i t y of the f i n a l s t r u c -t u r a l f o r m u l a . Before the s t r u c t u r a l formula of the c h l o r i t e c o u l d be c a l c u l a t e d , the x-ray determined quartz had to be 31 estimated. This was accomplished by determining the amount of t e t r a h e d r a l A l , by f i l l i n g the t e t r a h e d r a l l a y e r w i t h S i and then by a s s i g n i n g the remaining SiO^ as quartz or amorphous SiO^* I t has been shown above that the number of t e t r a h e d r a l A l i o n s , c a l c u l a t e d from the G Q spacing, was 1.00 per u n i t c e l l . An attempt was made to confirm the t e t r a h e d r a l A l value obtained p r e v i o u s l y by the a c i d d i s -s o l u t i o n method of Osthaus (1956). Ten 0.2 gm.samples of c l a y were t r e a t e d w i t h 30 per cent HC1 i n a b o i l i n g water b a t h f o r v a r y i n g periods of time and then analysed f o r s o l u b l e A l . When the l o g of the undissolved A l was p l o t t e d vs time (Pigure 10), the i n i t i a l p o r t i o n of the p l o t was a steep curve which l e v e l e d o f f to a s t r a i g h t l i n e at a time of 3 hours. E x t r a p o l a t i o n of t h i s s t r a i g h t l i n e to zero time gave a value of 9.1 per cent AlgO^ which was i n t e r -p r e t e d as t e t r a h e d r a l A l (Osthaus 1956). The i n i t i a l decom-p o s i t i o n was too r a p i d i n t h i s experiment to allow a pos-s i b l e separate determination of i n t e r - l a y e r and mica-layer A l . However, g e t t i n g the t e t r a h e d r a l AlgO^ content was the o b j e c t i v e and was s u f f i c i e n t f o r the c a l c u l a t i o n . The elemental analyses werereduced to charges or e q uivalents per 100 gm. (Column 2 Table 4) , and the t e t r a -h e d r a l S i 0 2 content was assigned the value of y. The sum of the charges/100 gm. ( x ) , which included the c a t i o n ex-change c a p a c i t y was 2.4978 y« Since there are 18 oxygens of which 8 are hydroxyls i n the i d e a l c h l o r i t e u n i t c e l l , 32 the number of n e g a t i v e charges balanced by m e t a l l i c c a t i o n s i s 28. The e q u i v a l e n t s of t e t r a h e d r a l Al/100 gm were conver-t e d to e q u i v a l e n t s / u n i t c e l l by m u l t i p l y i n g by a f a c t o r K = 28/x. The v a l u e s of x and y were determined as f o l l o w s u s i n g the n o t a t i o n s shown i n Table 2; a, the e q u i v a l e n t s of t e t r a h e d r a l A l / u n i t c e l l , = O.5355K; b, the atoms of A l / u n i t c e l l = a/^, c, the atoms of S i / u n i t c e l l = 4-b; d, the e q u i -v a l e n t s of S i / u n i t c e l l = 4c; y, the e q u i v a l e n t s of Si/100 gm. = d/K. These r e l a t i o n s h i p s were s o l v e d f o r x and y and i t was found that there were 1.20 t e t r a h e d r a l A l . atoms. The ex-c e s s SiOg, f , was I4 .85 per c e n t , a r a t h e r h i g h value when compared to the x -ray data but i t i s l i k e l y that some of the f r e e SiOg may have been x-amorphous. The atoms/unit c e l l of the other elements were c a l -c u l a t e d i n the same f a s h i o n as the t e t r a h e d r a l A l atoms. There was no sound way of d i s t i n g u i s h i n g between the atoms i n the m i c a - l a y e r or the i n t e r l a y e r o c t a h e d r a l p o s i t i o n s . Thus, the two l a y e r s were combined i n the f o r m u l a , as f o l -lows : ( A L 3 . 2 2 P e . 3 8 T i . 0 9 M & . 7 6 ) ( A 1 1 . 2 0 S i 2 . 8 0 ) 0 1 0 + .6958 -1.2009 ( X ) ( 0 H ) 8 ( C a > 2 K # 2 3 X > 2 i | ) + . 5 0 5 9 For comparison, when the number of t e t r a h e d r a l A l ions was set equal to 1, the c a l c u l a t e d formula was as 33 f o l l o w s : ( A 1 3 . 2 1 P e . 3 7 T i • 0 8 M S . 7 3 } ( A 1 S 1 3 ) 0 1 0 + . 5 1 7 2 -1.00 ( 0 H ) g ( C a > 0 2 K > 2 2 X > 2 3 ) 4O.J4.8i7 In t h i s case the c a l c u l a t e d S i 0 2 was 1 1 . 7 Per cent w h i l e 1 t e t r a h e d r a l A l / u n i t c e l l corresponded to 7 . 9 6 per cent A 1 2 0 3 . The formula c a l c u l a t e d from the complete a n a l y s i s (3) i n c l u d i n g a l l of the S i 0 2 was ( A 1 3 . 1 8 F e . 3 1 T i . 0 7 M g . 6 2 ) ( A 1 . 3 9 S i 3 . 6 l ) 0 1 0 - . 0 1 4 4 -.3948 ( 0 H ) 8 ( C a . 0 3 K > 9 X > 1 9 ) +.4O88 T h i s s t r u c t u r a l f ormula was c o n s i d e r e d u n s a t i s f a c t o r y f o r s e v e r a l reasons. I t does not account f o r the excess S i 0 2 n e c e s s a r y f o r the s m a l l amount of quartz p r e s e n t . I t i s un-l i k e l y that the two o c t a h e d r a l l a y e r s would have a net nega-t i v e charge, and the t e t r a h e d r a l A l of O .39 atoms/unit c e l l i s not i n accord w i t h the x-ray and chemical d a t a . I t was t h e r e f o r e , concluded that the c h l o r i t e had a composition c l o s e to that shown by equation 1 or 2 . The course of the decomposition d u r i n g the Osthaus treatment was f o l l o w e d by the examination w i t h x-ray d i f f -r a c t i o n of samples h a v i n g 15 min, 1 hour, 2 hours, and 6 3 4 hour treatments. The m a t e r i a l q u i c k l y l o s t i t s c r y s t a l l -i n i t y . Only the 15 min. sample showed c h l o r i t e f e a t u r e s . In no case was a c l e a r l y - d e f i n e d v e r m i c u l i t e - o r montmoril-l o n i t e - l i k e p roduct o b t a i n e d , hut on h e a t i n g to 500°C weak 10A and 3»33A r e f l e c t i o n s were shown by the 15 min.- and 1 hour - t r e a t e d samples. The 2 hour - and 6 hour - samples. The 2 hour - and 6 hour - samples were e s s e n t i a l l y amorphorus but both showed v e r y weak, broad, 10A f e a t u r e s upon h e a t i n g to 500°C. Thus, t h e r e may have been some p r e f e r e n t i a l decom-p o s i t i o n of the i n t e r l a y e r m a t e r i a l but there was no e v i -dence of a w e l l - o r d e r e d expanding, 2:1 l a y e r s i l i c a t e as had been found p r e v i o u s l y by s i m i l a r techniques (Brydon and Heystek 1958, B r i n d l e y and Y o u e l l 1951). R e l a t i o n s h i p w i t h Other C h l o r i t e s . Hey (1954) quotes Tschermakas d i v i d i n g c h l o r i t e s i n t o two groups; o r t h o c h l o r i t e s (Mg Fe'O^, and l e p t o c h l o r i t e s which are r i c h e r i n t r i v a l e n t ions and which o f t e n c o n t a i n c o n s i d e r a b l e f e r r i c i r o n . The l a t t e r group has been c a l l e d " o x i d i z e d c h l o r i t e s " by W i n c h e l l (Hey 1954) s i n c e they f a l l i n t o the o r t h o c h l o r i t e group i f the i r o n i s a l l computed as f e r r o u s i r o n . Hey (1954) used a d i v i s i o n s i m i l a r to Tscher-mak u s i n g the a r b i t r a y f i g u r e of 4 per cent Fe o0 as the 2 3 d i v i d i n g l i n e between the o r t h o c h l o r i t e s and o x i d i z e d c h l o r i t e s . O r c e l , C a i l l e r e and Henin (1950) have d i v i d e d the c h l o r i t e s i n t o 4 groups based on the number of S i atoms pe r u n i t c e l l . They d i d not d i s t i n g u i s h the o x i d i z e d 35 c h l o r i t e s i n t h e i r subgrouping. Brown (1955) proposed a scheme u s i n g 3 groupings : 1 . t r i o c t a h e d r a l c o n t a i n i n g o x i d i z e d and u n o x i d i z e d c h l o r i t e s , ( o r t h o - c h l o r i t e s ) 2 . d i o c t a h e d r a l c h l o r i t e s (none known) i n which both the mica and the i n t e r l a y e r sheets are d i o c t a h e d r a l j and 3« l e p t o -c h l o r i t e s , ( c o o k e i t e ) i n which one of the l a y e r s i s d i o c t a -h e d r a l , and the other i s t r i o c t a h e d r a l . The terminology i s , t h e r e f o r e , somewhat c o n f u s i n g because of the d i f f e r e n t d e f i n i t i o n s f o r the term l e p t o c h l o r i t e . B r i n d l e y and G i l l e r y (1956) r e t a i n Hey's o r i g i n a l d e f i n i t i o n of l e p t o c h l o r i t e and d e a l s w i t h the mixed types under the d i o c t a h e d r a l m i n e r a l s . B r i n d l e y and G i l l e r y (1956) have shown the theo-? r e t i c a l formula of d i o c t a h e d r a l c h l o r i t e s as A 1 ( h + § ) S i ( 4 - x ) A 1 x ° 1 0 ( ° H > 8 Since the o c t a h e d r a l l a y e r s w i l l always have x / 3 more than A l per u n i t c e l l i n order to maintain e l e c t r i c a l n e u t r a l i t y , the i d e a l s t r u c t u r e can o n l y be approximately d i o c t a h e d r a l . The unique c o n d i t i o n under which there c o u l d be e x a c t l y 4 o c t a h e d r a l atoms would r e q u i r e that the o c t a h e d r a l A l be r e -p l a c e d by t e t r a v a l e n t c a t i o n s equal tn number to the t e t r a -h e d r a l A l . I f d i v a l e n t c a t i o n s , A, are pr e s e n t the o c t a -h e d r a l firmula would be (Al^A^) and i f there are monovalent 2 c a t i o n s B, i t would be A l i B . Aluminous c h l o r i t e s would be 36 expected, t h e r e f o r e , to have more than 4 of the 6 a v a i l a b l e o c t a h e d r a l spaces f i l l e d . From Table 4, i t may be seen that the number of o c t a h e d r a l atoms was 4 . 4 6 of which 3 . 6 were t r i v a l e n t A l and Fe and O .76 were d i v a l e n t Mg. Thus the composition of the c l a y approaches the t h e o r e t i c a l member w i t h an octahe-d r a l composition of ( Al^Mg x). 2 An example of a case where monovalent c a t i o n s a r e p r e s e n t i n the o c t a h e d r a l l a y e r s i s the m i n e r a l c o o k e i t e . T h i s m i n e r a l , an a l t e r a t i o n product of l e p i d o l i t e and spod-umene has been shown (Brammall e t a l . 1937» Ginzburg 1953, Zvyagin and Nefedov 1954) to be a h i g h aluminum ( 3 0 - 4 0 % A l o 0 , ) low magnesium (O .O4 - 0.6% MgO), l i t h i u m ( l - 5% L i g ) c h l o r i t e . I t i s c h a r a c t e r i s e d by the p r o x y i n g of L i A l ^ f o r Mgg i n the c h l o r i t e s t r u c t u r e . I f one assumes A l 2 i n one o c t a h e d r a l l a y e r and L i A l g i n the o t h e r , i t i s apparent t h a t the c o o k e i t e s t r u c t u r e i s mixed d i o c t a h e d r a l and t r i o c -t a h e d r a l . The example of the mixed type which B r i n d l e y and G i l l e r y use has an aluminum ( d i o c t a h e d r a l ) mica l a y e r and a magnesium ( t r i o c t a h e d r a l ) i n t e r l a y e r so that the t o t a l o c t a h e d r a l composition i s (Mg_ A l _ ). Thus i t i s apparent t h a t there are two p o s s i b l e cases where one l a y e r has e x a c t -l y 3 c a t i o n s ; one i n which Mg and A l are b o t h major c a t i o n s and the o t h e r (Al, L i ) where A l alone i s the major c a t i o n . 37 The v a r i e t i e s most l i k e l y to he encountered i n nature and p a r t i c u l a r l y i n sediments would be those i n which the domi-nant c a t i o n s would be A l , Mg, F e 2 and F e 5 . I t i s g e n e r a l l y r e c o g n i z e d ( F o s t e r , 1956, Ross and Hendricks, 1945) that the number of o c t a h e d r a l c a t i o n s i n p h y l l i t e s i s always c l o s e to e i t h e r 2 or 3 per u n i t c e l l . In c h l o r i t e s t r u c -t u r e s , i t might be expected, t h e r e f o r e , that the o c t a h e d r a l l a y e r of the mica p o r t i o n should be p u r e , i . e . , e i t h e r d i o c t a h e d r a l or t r i o c t a h e d r a l , and any d e v i a t i o n from ex-a c t l y 2 or 3 would occur i n the i n t e r l a y e r hydroxide. T h i s c o u l d a r i s e through a mixing of g i b b s i t e - a n d b r u c i t e - t y p e hydroxide a r r a y s or through the p r o x y i n g of H^ O f o r OH i n the hydroxide s t r u c t u r e . The problem of d i s t i n g u i s h i n g d i o c t a h e d r a l , t r i -o c t a h e d r a l and mixed s t r u c t u r e s i n n a t u r a l m ixtures, may be encountered i n those cases where the s t r u c t u r a l formulae cannot be c a l c u l a t e d . I t i s g e n e r a l l y r e c o g n i z e d (Grim 1953) t h a t d i o c t a h e d r a l p h y l l i t e s have a b Q dimension of 9.0 A whereas the b Q of t r i o c t a h e d r a l s t r u c t u r e s i s about 9.2A. T h i s a r i s e s because A l i s g e n e r a l l y the major o c t a h e d r a l c a t i o n i n one case whereas i t i s Mg i n the other. Since a l l s u b s t i t u t i o n s a f f e c t the b Q dimension, equations have been developed showing the r e l a t i o n s h i p between the amount of p r o x y i n g and the b Q dimension i n i l l i t e s (Grim, B r a d l e y and Brown 1951) and m o n t m o r i l l o n i t e (MacEwen 1951). In the c h l o r i t e s t r u c t u r e , s i n c e the i n t e r l a y e r hydroxide i s bonded 38 to the m i c a - p o r t i o n through n o n - r i g i d e l e c t r o s t a t i c charges and hydrogen bonds, i t might he expected that i t would not i n f l u e n c e the b Q dimension. I f t h i s assumption i s c o r r e c t , o n l y the m i c a - l a y e r o c t a h e d r a l c a t i o n s p l u s the t e t r a h e d r a l A l would i n f l u e n c e the b Q s i z e as i n the other p h y l l i t e s . Thus c h l o r i t e s w i t h dioctahedral (Al) mica l a y e r s should g i v e an (060) near 1 .50 and w i t h t r i o c t a h e d r a l Mg, Fe mica-l a y e r s they should give an ( 0 6 0 ) around 1.53 A r e g a r d l e s s of the composition of the i n t e r - l a y e r hydroxide. Converse-l y , i t would he p o s s i b l e to e s t i m a t e from a measured (060) s p a c i n g the c h a r a c t e r of the m i c a - l a y e r , and f o r pure c h l o r i t e s to determine t h i s i n t e r l a y e r composition by d i f f e r e n c e from the t o t a l a n a l y s i s . t i o n here has 2 A l i n the o c t a h e d r a l m i c a - l a y e r and 1 A l i n the t e t r a h e d r a l l a y e r , b o t h equations (Grim et a l 1951> MacEwen 1951) g i v e a b Q of 9.03 A as compared to a measured value of 8.98A. I f a l l of the Mg, Fe, and T i are i n the o b t a i n e d w i t h the f i r s t case. The s t r u c t u r a l formula, t h e r e -f o r e , may be w r i t t e n I t i s assumed that the c h l o r i t e under i n v e s t i g a -mica l a y e r the c a l c u l a t e d b Q i s 9.115 A. The b e s t f i t i s ( M g.73 F e.37 T i.08 A 1l.2l )(OH)g •+• .5172 4- .1+817 ( A l ) 2 ( A l 1 S i 3 ) 0 l 0 ( 0 H ) 2 - 1 . 0 0 3y Figure I. X-Bay Difrraction Tracings of Alberni Clays 35 30 25 20 15 l6 5 0 2 9 40 Figure I i . X-Ray D i f f r a c t i o n Tracings of A l b e r n i Clays, 25 e GLYCOL 300° 400° 500° 2 5* GLYCOL 500" 12.5 A L B E R N I 4 8 - 5 8 < 0 Z\\ 42 Figure IV. X~Ray D i f f r a c t i o n Tracings of A l b e r n i Clay. 43 Figure V. X-Eay D i f f r a c t i o n Traoings or A l b e r n i Clay. I i i i _J 1 i • £6 S o S o to ioo i*o d . ANGSTROM UNITS 4<t Figure VI. X-Ray D i f f r a c t i o n Tracings of A l b e r n i Clay. 45 Figure T i l . X*Eay Diffraction Tracings of Alberni Clay. (untreated) ALBERNI AB 02 11 -I 1 1 — : 1 1 1 1 1 I l M l I 3 3.5 5 7 10 14 24 d - ANGSTROM UNITS 4 6 * Figure V I I I , X-Ray D i f f r a c t i o n Tracings of A l b e r n i Clay, J I 1 I I L I I I 1 11 I l _ 3 3.5 5 7 10 14 24 d ANGSTROM UNITS Figure IX. D i f f e r e n t i a l Thermogram' of A l b e r n i Clay ,run i n % and A i r , 48 Figu r e X . D i s s o l u t i o n curve of the A l b e r n i f i n e c l a y by the Osthaus method (1958). PERCENT A l 2 0 3 IN RESIDUE 30 20 10 \- TETRAHEDRAL Al 1 3 4 TIME— HOURS 49 C a t i o n Exchange. C a t i o n exchnage c a p a c i t y analyses of the c l a y s from the A - B and from the C h o r i z o n s o i l s (Table 5) which Virere made by the ammonium acetate method were not r e p r o d u c i b l e . I t was b e l i e v e d that incomplete removal of the excess NH^A c c o n t r i b u t e d not only to the v a r i a t i o n , but a l s o was the cause of the very h i g h C.E.C. values obtained f o r some of these samples. The c l a y s crackddand allowed c h a n n e l i n g of the a l c o h o l d u r i n g s u c t i o n f i l t r a t i o n , or became h i g h l y p l a s t i c and unmanageable i f a c e n t r i f u g a l t i o n technique was employed. I t i s seen from Table 6 that the C.E.C. values of s o i l from the C h o r i z o n , and of s o i l from the A - B and the C h o r i z o n s were c o n s i d e r a b l y lower than those obtained with the c l a y s and were w i t h i n the expected range. The presence of a sand and s i l t m a t r i x g r e a t l y reduced c h a n n e l i n g , and a p p a r e n t l y normal f i l t r a -t i o n proceeded throughout the whole volume of the samples so that the excess NH^Ac was removed more r e a d i l y . The f i l t r a t i o n technique remained suspect, however, s i n c e the values f o r d u p l i c a t e samples d i d not agree very c l o s e l y . The c o n d u c t r i m e t r i c t i t r a t i o n method gave r e s u l t f o r d u p l i c a t e samples which agreed c l o s e l y and the a n a l y -ses were r e p r o d u c i b l e over a p e r i o d of s e v e r a l months. The values (Table 7) o b t a i n e d by t h i s method were b e l i e v e d 50 be most c h a r a c t e r i s t i c of the c l a y s , and as p o i n t e d out, were used i n the p r e v i o u s s t r u c t u r e c a l c u l a t i o n s . There were two f e a t u r e s connected, w i t h these data that c o u l d not be r e a d i l y e x p l a i n e d . The c a t i o n exchange c a p a c i t y of the coarse c l a y f r a c t i o n s c o u l d not be obtained by t h i s method because of the u n c e r t a i n t y i n determining the slope of the i n i t i a l p o r -t i o n of the t i t r a t i o n c u rves. The i n d i c a t i o n s were, that the C.E..C values were l e s s than 5 meq/ 100 gm c l a y . Such low v a l u e s f o r the c a t i o n exchange c a p a c i t i e s of pure c l a y s are a s s o c i a t e d o n l y w i t h k a o l i n i t e which i s not a major com-ponent of hte A l b e r n i C l a y , and must have due to some e r r o r i n h e r e n t i n the technique. I t was f e l t that the l a r g e r p a r t i c l e s i z e reduced the r a t e at which exchange between c a t i o n s h e l d between the c l a y p l a t e s and the r e s i n c o u l d take p l a c e . The second f e a t u r e was the r e d u c t i o n i n C.E.C" of the f i n e c l a y f r a c t i o n s a f t e r a d d i t i o n a l d i t h i o n i t e - c i t r a t e e x t r a c t i o n s . The exchange c a p a c i t y of 65 meq/lOO gm f o r f i n e c l a y from the A-B h o r i z o n s o i l which had been e x t r a c t e d k times w i t h the d i t h i o n i t e - c i t r a t e reagent was reduced to 32 meq/lOO gm f o r the c l a y separated from the same s o i l a f t e r 8 e x t r a c t i o n s . There was a c o r r e s p o n d i n g decrease f o r the f i n e c l a y s from the C h o r i z o n . The exchange c a p a c i t y of 34 meq/ 100 gm f o r c l a y which was separated from s o i l ^ which had r e c e i v e d two e x t r a c t i o n s with d i t h i o n i t e - c i t r a t e reagent was reduced to 7 meq/ 100 gm a f t e r f o u r e x t r a c t i o n s w i t h the reagent. 51 I t was observed that the green colour of the s o i l immediately a f t e r e x t r a c t i o n became a d u l l g reenish brown a f t e r a few days and i t was thought that o x i d a t i o n of f e r r o u s i r o n which was absorbed by the c l a y during the d i t h i o n i t e e x t r a c t i o n , was resp o n s i b l e f o r the change i n c o l o u r , and f o r the b l o c k i n g of exchange s i t e s and reduc-t i o n i n c a t i o n exchange c a p a c i t y . Representative t i t r a t i o n curves are presented i n Figures XI and XII and the t i t r a -t i o n data are presented i n the Appendix. The Mn method (Jackson 195) fov c a t i o n exchange c a p a c i t y a n a l y s i s was s e l e c t e d to t e s t the the o r i e s con-ce r n i n g removal of excess s a l t and the b l o c k i n g of exchange s i t e s , not because of any p a r t i c u l a r advantage to be gained from the use of Mn as a s a t u r a t i n g i o n , but because i t was a method which allowed the use of small samples which could be washed more e f f e c t i v e l y , and because the method l e n t i t -s e l f to quick and accurate routine a n a l y s i s . In order to estimate the e f f e c t i v e n e s s of various c a t i o n s i n b l o c k i n g the exchange s i t e s of c l a y s , c l a y sam-p l e s were suspended i n O . O 5 N s o l u t i o n s of A l C l ^ , CaClg, F e C l ^ ; FeSO^ and MgSO^ f o r s e v e r a l weeks. They were then removed from the suspension and d r i e d . The Ca-clays were considered reference c l a y s f o r these analyses. In a l l sub-sequent discussions and i n the t a b l e s , the f o l l o w i n g nota-t i o n s w i l l be used: A-BI4./2.O, A - B 8 / 2 . 0 , A-BV'0 .2, A-B8/0 .2 C 2 / 2 . 0 , G 4 / 2 . O C 2 / Q . 2 Ok/0,2 52 The l e t t e r s r e f e r to the h o r i z o n from which the c l a y s were se p a r a t e d , the numeral f o l l o w i n g , r e f e r s to the number of e x t r a c t i o n s w i t h d i t h i o n i t e - c i t r a t e reagent, /2.0 and /0.2 r e f e r to the coarse and f i n e c l a y f r a c t i o n s r e s p e c t i v e l y . The n o t a t i o n s may be f o l l o w e d by the s u f f i x e s A l , Ca, Fe 2+ 24-Fe , or Mg, used to i n d i c a t e the s o l u t i o n i n which the c l a y had been suspended. It i s seen that the range of values f o r c a t i o n exchange c a p a c i t y by the Mn method (Table 8 ) are more con-s i s t e n t w i t h v a l u e s to be expected. The C.S.C. value of about 37 meg/lOOgm f o r the C h o r i z o n s o i l was c l o s e to that expected f o r the s o i l . The values f o r d u p l i c a t e samples agreed more c l o s e l y but i n an attempt to improve on the d u p l i c a t i o n found f o r the C2/2.0Fe and C2/2.0Ca samples they were again s a t u r a t e d w i t h Mn and the analyses were repeated. The r e p r o d u c i b i l i t y was not very good and i t was f e l t that i t would be a d v i s a b l e to a v o i d the use of manganese which i s s u b j e c t to o x i d a t i o n to MnO^ i n s o i l s which a l r e a d y may have an MnO^ c o n t e n t . C a t i o n exchange c a p a c i t y analyses by the m o d i f i e d NH^Ac method show that the v a l u e s obtained when the excess s a l t s are removed by washing w i t h acetone are much higher than values obtained a f t e r washing with a l c o h o l (Table 9 ) . The m o d i f i e d NH^Ae - Acetone a n a l y s i s (Table 10 ) gave r e s u l t s f o r d u p l i c a t e samples which agreed more c l o s e l y when the samples were p o l i c e d thoroughly w i t h a rubber policeman, than 53 when the samples were washed by d i r e c t i n g a strong j e t of s o l u t i o n from a wash b o t t l e i n t o the c e n t r i f u g e tubes. The analyses i n Table 11 show, however, that even though d u p l i -cate analyses of a sample agree c l o s e l y on any p a r t i c u l a r day, r e p r o d u c i b i l i t y from day to day i s poor* The various methods f o r the determination of the c a t i o n exchange c a p a c i t y of s o i l s have been assessed c h i e f -l y on the b a s i s of t h e i r e f f i c i e n c y as r o u t i n e a n a l y t i c a l procedures which are capable of g i v i n g r e p r o d u c i b l e exchange data f o r s o i l s with wide ranges of t e x t u r e , r e a c t i o n , and mineral content. The KH^Ac method has been used widely, and C«E.C. by t h i s method has been a r b i t r a r i l y defined as the value obtained by s a t u r a t i n g a s o i l w ith NH^* i o n by l e a c h i n g i t w i t h s p e c i f i e d amounts of ammonium acetate at pfr 7*0, removing the excess s a l t s , and determining the amount of adsorbed NH^ by d i s t i l l a t i o n from an a l k a l i n e NaOH-NaCl medium i n t o H^SO^. J u s t i f i c a t i o n f o r the use of t h i s method l i e s i n the f a c t that i t has found broad general a p p l c i a t i o n i n the c o r r e l a t i o n of s o i l f e r t i l i t y l e v e l s w i t h crop n u t i r t -i o n . S c h o f i e l d (1940) has shown, however, that c a t i o n exchange c a p a c i t y determina ions made wit h b.uffered s a l t s o l u t i o n s give values which are comprised of two components B The component which i s of i n t e r e s t i n t h i s i n v e s t i -g a t i o n i s that which a r i s e s from the p o s i t i v e charge d e f i c i t caused by isomorphous s u b s t i t u t i o n i n the lasers of c l a y 54 m i n e r a l s , and which i s c h a r a c t e r i s t i c of the mi n e r a l * T he second component i s "pH dependent" and i s f o r the most p a r t independent of the type of c l a y mineral involved* Grim (1953) has warned that " trustworthy determina-t i o n s of c a t i o n exchange c a p a c i t y can he accomplished only by a s k i l l e d analyst who i s aware of the fundamental causes < of the d i f f i c u l t i e s that beset the problem"*, I t i s a w e l l e s t a b l i s h e d f a c t that the major p o r t i o n of the c a t i o n ex-change c a p a c i t y of the 2:1 l a y e r s i l i c a t e s a r i s e s because of the isomorphous s u b s t i t u t i o n of t r i v a l e n t aluminum f o r qua d r i v a l e n t s i l i c o n i n the t e t r a h e d r a l l a y e r s , or of the s u b s t i t u t i o n of d i v a l e n t f o r t r i v a l e n t ions i n the o c t a -h e d r a l l a y e r s of c l a y minerals. These s u b s t i t u t i o n s cause a permanent negative charge on the s u b s t i t u t e d l a y e r s which i s balanced by the adsorption of cations on the l a y e r surfaces. The energy of adsorption of these c a t i o n s v a r i e s w i t h the s i t e and magnitude of the l a y e r charge, and the charge, s i z e , and hydration of the adsorbed c a t i o n s . Mica, which has maximum s u b s t i t u t i o n of A l f o r S i i n the t e t r a h e d r a l l a y e r , c a r r i e s the highest surface charge d e n s i t y . This i s balanced by the adsorption of K + ions between adjacent t e t r a h e d r a l l a y e r s of the 2:1 l a y e r s h e e t s s The i o n has a diameter of 2.66A0 and f i t s i n t o the c a v i -t i e s of the hexagonal network of oxygen atoms which comprise the surface of the adjacent sheets. The bonding between the E ion and the 12 oxygen atoms i s so stron g that the adjacent 55 TABLE 5 CE.C. OP ALBERNI CLAY: .( NH, Ac METHOD ) Horizon Treatments f o r removal of Pe Weight c l a y gm C .E. C . meq/100 gm Mean A - B 8 0 . 5 3 2 8 7 3 . 3 6 6 9 . 7 4 7 1 . 5 5 ti 4 0 . 7 8 7 2 3 2 4 . 3 0 3 4 9 . 6 0 3 3 7 . 4 5 C 4 1 .9922 1 1 4 . 3 0 120.2-0 117 .15 it 2 1 . 1826 1 1 5 . 9 0 1 2 4 . 60 1 2 0 . 2 5 TABLE 6 CE.C. OP ALBERNI BOIL AFTER DITHIONITE -CITRATE EXTRACTIOfljNH. Ac METHOD ) Sample Treatments f o r removal of Pe C • E • C. meq/100 gm C h o r i z o n - 3 4 . 6 0 3 3 . 81 C h o r i z o n ( t r e a t e d w i t h HOOH) - 2 5 . 4 5 2 5 . 7 2 2 5 . 4 5 C h o r i z o n 2 3 6 . 5 7 4 0 . 1 3 C h o r i z o n 4 5 8 . 1 9 5 9 . 9 6 A - B h o r i z o n 4 5 6 . 4 7 4 0 . 4 6 A - B h o r i z o n 1 8 4 1 . 6 9 3 0 . 2 9 5$ ^ TABLE 7 C.E.C. OP ALBERNI CLAYS.(CONDUCTIMETRIC T I -TRATION METHOD) Horizon Treatments removal of f o r Pe C.E.C . meg/100 gm c l a y 1 2 3 Mean A - B 4 65.01 64.82 64.92 8 32.63 32.50 31.92 32.33 C 2 32.33 36.43 34.18 34.31 4 4.75 5.11 4.47 4-78 TABLE 8" CATION EXCHANGE CAPACITY DATA POR C HORIZON S O I L AND CLAY (Mn METHOD ) Sample C 2/2.0Pe++ C 2/2.0Pe3+ C 2/2.OCa S o i l C.E.C. 1 meq/lOO gm Mean 76.4 68.6 72.5 69.4 71.7 70.6 6I.4 56.0 58.7 38.0 36.7 37.4 C.E.C.II meq/lOO gm Mean 85.6 82.5 84.I 76.2 82.4 79.3 72.6 58.7 65.7 44.6 40.6 42.6 57 TABLE 9 CE.C. OF ALBERNI CLAYS (C4/2.0Fe 2 +) (MODIFIED NB4AC-ACETONE/ALCOHOL METHOD) Acetone E t h a n o l Sample size(gm) C. E. C. meq/100 gm 0.1015 0.1030 50.75 50.75 0.0705 0.1977 l o s t 35.25 TABLE 10 C E . C . OF ALBERNI CLAYS (C4/2. 0Fe 3 t") EVALUATION OF THE EFFECTIVENESS OF . POLICING THE SAMPLES (MODIFIED NH^Ac- ACETONE METHOD } C E . C . meq/100 gm Pnl ififlfl. Not -policed C4/2.0Fe 3 44.10 44.10 58.90 53.25 TABLE 11 C E . C . OF ALBERNI CLAYS SATURATED WITH DIFFERENT CATIONS (MODIFIED NB^Ao-AOETONB METHOD) meq/100 gm.clay C.E.C. meq/100 gm C4/2.0 A l C4/2.0 Ca C4/2.0 F e 3 C4/2.0 F e 2 C4/2.0 Mg C4/0.2 A l C4/0.2 Ca C4/0.2 F e 3 C4/0.2 F e 2 C4/0.2 Mg-Oct.9th. 4a.. 15 40.15 37.50 38.60 38.60 38.60 Oct.11th. 71.90 66.30 68,05 71.20 70,50 69.80 Oct.12th 77.55 62.95 67.70 68,40 Oct.17th 62.10 62.10 Oct.24th 47.97 47.97 43.35 43.35 42.33 44.45 45.02 44.6? 46.56 46.70 C2/2.0 A l C2/2.0 Ca C2/2.0 F e 3 C2/2.0 T , 2 Fe C2/2.0 Mg C2/0.2 A l C2/0.2 Ca C2/0.2 F e 3 C2/0,2 F e 2 C2/0.2 Mg Oct.17th 37.05 37.05 35.90 35.20 34.55 34.20 38.09 33.86 35.62 31.13 0ct,24th, 44.44 44.44 53.91 47.97 47.30 47.97 48.67 48.67 44.60 43.44 Oct. 2 5 th.. 80,40 78.99 -79,34 79.69 81.11 80,40 69,12 69.12 74,76 74,06 Conductance mmhos cm -1 10' Conductance mmhos cm~ x 10 2 CO o o 0 M • \ v H 0 3 \ * 0 3 CR \ o W Conductance mmhos cm"1 x 10 ro o o o 00 o 3 o ca &! ro o 3 O 3 O H« • c+ ro CD 3 H-O • i O 3 CJ3 t o o i o o 1 II r o • • • o H1 en oa w o i o M C D !—• O 00 CD • • *<J ro ro M O 4 COP CD 3 c+ CD i o M O 6S F i g u r e X I I . Titration curves for ^ . 0.2 micron H-clay A-B horizon, 4 aithionite treatments CJ5 o e IS 5* 3 2 . ml 0.1336N NaOH 8 1 6 2 * 32. ml 0.1336N NaOH 61 sheets are c o n t r a c t e d and cannot he induced to expand by-c o n v e n t i o n a l treqtment. The r e s u l t s of many i n v e s t i g a t i o n s have shown that c l a y minerals which have been formed by the weathering of + micas have the a b i l i t y to h o l d K a n d NHj* ions i n nonexchange-a b l e or v e r y s l o w l y exchangeable form, and that; the exchange c h a r a c t e r i s t i c s of c l a y m i n e r als can var y c o n s i d e r a b l y , depending on the presence or absence of these i o n s . I t has been r e p o r t e d (Stevenson and D h a r i v a l , 1959) that i l l i t e i s p a r t i c u l a r l y e f f e c t i v e i n the f i x a t i o n of th se c a t i o n s , and to a l e s s e r e x t e n t , v e r m i c u l i t e and m o n t m o r i l l o n i t e . Grim (1953) and A l l i s o n and R o l l e r (1955) have p o i n t e d out th a t i l l i t e s which f i x potassium are degraded i l l i t e s which have been s u b j e c t e d to l e a c h i n g , and A l l i s o n and R o l l e r (1955) have p o i n t e d out that n a t u r a l i l l i t e i s non-expanded and cannot f i x p otassiunu The term " i l l i t e " i s thus seen to have been used to d e s c r i b e a c l a y m i n e r a l , which, while h a v i n g a w e l l c h a r a c t e r i s e d b a s i c s t r u c t u r e , may a l s o have minor m o d i f i c a -t i o n s which a f f e c t i t s behavior i n exchange r e a c t i o n s con-s i d e r a b l y . The name M o n t m o r i l l o n i t e has been a p p l i e d even more l o o s e l y to i n c l u d e c l a y m i n e r als which have r a t i o s of S i : A l i n t h e i r t e t r a h e d r a l l a y e r s which range from 4:0 f o r m o n t m o r i l l o n i t e to 3:1 f o r b e i d e l l i t e . Examination of the schematic r e l a t i o n s h i p s i n Tabl e 12 r e v e a l s a s i m i l a r i t y i n the b a s i c s t r u c t u r a l p a t t e r n of the c l a y m i n e r als which has suggested to many i n v e s t i -62 gators (Ross and Hendricks 1945) that i t i s p o s s i b l e to have complete gradation between c l a y mineral species depending on the extent of the isomorphous s u b s t i t u t i o n . F o s t e r (1953) has pointed out that the transforma-t i o n of I l l i t e 'to M o n t m o r i l l o n i t e i n v o l v e s more than the r e -placement of i n t e r l a y e r K + by d i v a l e n t c a t i o n s . The reduced l a y e r charge found i n Mo n t m o r i i l o n i t e s would have to be brought about by concurrent m o d i f i c a t i o n of the bas i c l a t t i c e ( c h i e f l y l e s s s u b s t i t u t i o n f o r A l f o r S i ) . The d i f f e r e n c e s i n l a y e r charge .are the b a s i c reasons f o r the d i f f e r e n c e s i n the d(00fi. ) spacings on which d i f f e r e n t i a t i o n between the c l a y mineral species by x-ray d i f f r a c t i o n analyses i s based. C a i l l e r e and Henin (1947) have performed experiments which prove that montmorillonite can be transformed i n t o i l l i t e or c h l o r i t e i f i t i s tre a t e d w i t h KOH or w i t h MgClg - MH^OH, and White (1956) has synthesised montmorillonite from i l l i t e . These experiments show that the evidence obtained from the analyses of n a t u r a l l y occuring c l a y minerals should not be considered to exclude the p o s s i b i l i t y t h a t , between the l i m i t s of isomorphous s u b s t i t u t i o n shown (Table 13) f o r re p r e s e n t a t i v e c l a y mineral s p e c i e s , there may e x i s t other ranges of s u b s t i t u t i o n where the l a y e r charge i s s u f f i c i e n t l y reduced to allow the formation of i l l i t e - v e r m i c u l i t e - b e i d e l l i t e c l a y s , and where environmental c o n d i t i o n s w i l l determine which species i s predominant. I t should be borne i n mind that c a l c u l a t i o n s of chemical formulae f o r c l a y minerals have n a t u r a l l y been made .63 most o f t e n f o r samples which are monocomponent but the c l a y s which develop i n s o i l s g e n e r a l l y c o n t a i n s u i t e s of c l a y minerals rather than a s i n g l e species. I t seems h i g h l y pro-bable that the various c l a y mineral species can be b u i l t from a s i n g l e b a s i c l a t t i c e s t r u c t u r e , and that high l a y e r charges tend to i n f l u e n c e the e q u i l i b r i u m towards the f o r -mation of clays w i t h contracted l a t t i c e s i n the presence of K + i o n , whereas the e q u i l i b r i u m i s d i r e c t e d towards the f o r -mation of f i x e d l a t t i c e c h l o r i t e s i f conditions favour ab-s o r p t i o n and p r e c i p i t a t i o n of Mg or A l hydroxides between the sheets of l a y e r s . M o n t m o r i l l o n i t e or V e r m i c u l i t e i s not l i k e l y to be a major stable c l a y species with high charge l a y e r l a t t i c e c l a y s . Clays formed i n t h i s manner are l i k e l y to have wide ranges w i t h regard to the extent and s t a b i l i t y of the i n t e r l a y e r c a t i o n s or hydroxides. Reports of expand-i n g i l l i t e s and v e r m i c u l i t e s , of c h l o r i t e s which are not completely heat s t a b l e and of random i n t e r s t r a t i f i e d c l a y s support t h i s theory s t r o n g l y . The A l b e r n i Clay was formed from m a t e r i a l which has a high degree of s u b s t i t u t i o n of A l f o r S i i n the t e t r a -hedral l a y e r of the basic l a t t i c e , the c h l o r i t e i n a l l f r a c t i o n s but the A - B / 0 . 2 c l a y has been found to be not completely heat s t a b l e , and the c l a y s u i t e s i n the various f r a c t i o n s are comprised of varying amounts of i l l i t e -c h l o r i t e - m o n t m o r i l l o n i t e . I t i s seen i n (Table 11+ that the d i t h i o n i t e - c i t r a t e reagent e x t r a c t s s i g n i f i c a n t amounts of 6i+ aluminum from the clay l a t t i c e and i t i s probable that this aluminum has been removed from p r e f e r e n t i a l planes, thus g i v i n g the clay more pronounced I l l i t i c qualities» + Fixation of NH^ may have been responsible f o r the reduction in C-E.C. observed (Table 5) with the A-B8/0..2 and Ch/0.2 samples. No explanation f o r the v a r i a t i o n i n the v/alues obtained f o r C.E.C. by other methods can be given except heterogeneity in the clay samples produced by attack on the clay mineral l a t t i c e by the extracting reagents Nearly a l l members of the c h l o r i t e group of s i l i -cate minerals are tr i o c t a h e d r a l , having divalent cations (Mg and Fe) f i l l i n g the available octahedral positions In both the mica-like sheet and the i n t e r l a y e r gibbsite sheet. Grim(l953) states, however, that some ch l o r i t e s in sediments may be dioctahedral, and Brindley (1956) has predicted the structural c h a r a c t e r i s t i c s of such minerals. There i s evidence (Rich, 1956) of l h A 0 layer s i l i c a t e s in clays which do not retain t h e i r I 4 A 0 spacing on heating as do normal c h l o r i t e s . The layers appear to contract but instead of giv i n g a 1 0 A ° collapsed spacing l i k e vermiculite, or montmor-i l l o n i t e , they show r e f l e c t i o n s intermediate between 10A° and I 4 A 0 . The f a i l u r e of these minerals to contract to the 1 0 A ° spacing has been attributed to a variable amount of d i f f i c u l t l y replaced material in the int e r l a y e r p o s i t i o n (Rich and Obenshain, 1955) 65 TABLE 12 STRUCTURAL RELATIONSHIPS OP CLAY MINERALS Montmoril-lonite Beidellite Vermiculite I l l i t e Chlorite 6 0 = 4Si 40".20H~ 6 0 = (4-x)Si.xAl 40=.20H~ 6 0 = (4-xSi).xAl 40-.20H" 6 0 = (4-x)Si.xAl 40~.20H~ 6 0 = Tetrahe-( 4 r x)Si.xAl dral 40T20H" layer (4ry)AliyMg 40~.20H (4+2x)Al 40_.20H~ 6R.4A1 40=.20H" 6RA4A1 40".20H" 6RA4A1 40T20H" Octahe-dral layer 4Si 6 0 = (4-x)Si.xAI 6 0 " (4-x)Si.xAI 6 0 = (4-x)Si.xAl 6 0 " ( V x)Si.xAl Tetrahe-60" dral layer ( C a ^ N a ) Replace-able (C^Mg+Na") Replace-able x(MgtCatx Replace-able K + Difficultly i n part 60H~ (6-2x)Mg.x Al or 4A1 60H~ Not re-placeable Inter layer 80 - 150 Preponder-antly sur-faces 80 - 150 100 -150 10 - 40 Surfaces and edges 1 0 - 4 0 Surfaces and edges C.E.C. meq/lOOg Readily expanding Readily Expanding Expanding Expanding only with drastic treatment Site of C.E.C. 1.0-0.6 1.0-0.6 1.4-0.9 1.2+ Charge/ Unit c e l l 12.2-15.4A° 12.2-15.4A° 14.2A° 10.1 A 14.2A° dbol 66 TABLE 13 LIMITS OF ISOMORPHOTJS STTB3TITTJTIQN .': IN CLAY MINERALS £S!2?L ( A 1 3 ^ : P e»38 K-.09 MS. 7 6i5i^ 8 0Al : L # 2 0)0 l u(0H) 8 »02K.23X.24' CJalorite f n« K- " T - \ Weaver(1959) 3+ 2 + i l l o n i t e B e i d e l l i t e 1,37 0.50 0 .02 0.22 3.53 0 . 4 7 n tt I l l i t e * B e i d e l l i t e 1 . 6 0 0.07 0 . U 2 0 . 3 4 3 . 60 0.39 »T tt I l l i t e 1.44 0.35 *«* 0.22 3.45 0.55 tt tt Foster ( 1 9 5 3 ) I l l i t e s A12S13A1 0 l o.(0H) 2 1.29 0.58 M 0 . 2 4 3.38 0 . 6 2 Tt tt 1.40 0.35 .** 0.86 3.40 0 . 60 tt tt 1 . 5 5 0 . 2 0 tm 0 . 2 5 3 . 50 0 . 5 0 tt tt 1.53 0 . 3 2 0.14 3 .42 0 . 5 8 tt tt 1 . 52 0 . 3 0 0.19 3 . 5 4 0 . 4 6 tt t» Montmorillon- 1.61 0.18 0 . 2 3 3.87 0 . 1 3 tt tt i t e s l . * 6 U.21 U . 3 5 3.9a U.0'7 tt ft A i 2 S i 0 l Q ( 0 H ) 2 1.^ 7 0 . 1 4 0 . 4 0 3 . 9 4 U . U 6 ft n 1 .49 0 . 1 0 0 . 4 3 a.98 0 . 02 tt ft Lav- 0.15 0 . 5 0 5 . 9 7 o.oa tt « B e i d e l l l t e s A l g S i ^ A l 0 1 0(0H] 's 1 . 0 4 0 . 4 t O 0 . 2v a. 70 0 . 3 0 tt tt 1 . 4 0 0 . 50 0.08 3.58 0 ,42 tt ft 1 . 5V 0.35 0 . 1 0 3.55 0 . 4 5 tt tt 1 .69 U.U7 est U . 2 5 3 . 54 0 . 4 6 tt it 6 7 Jackson and others (1952) have p o i n t e d out that the r e l e a s e of potassium ions from the " p r e f e r e n t i a l wea-t h e r i n g p l a n e " of a d i o c t a h e d r a l mica may proceed r e l a t i v e -l y r a p i d l y u n t i l the i n t e r l a y e r spaces became expanded. Brown (1951) suggested that as the d i o c t a h e d r a l micas were d e p l e t e d of a l k a l i s , enough i n t e r l a y e r s expand to permit i n c r e a s e i n the b a s a l spacings to be de t e c t e d by x - r a y s . The expansion may g i v e 14A, 18A w i t h 10 - 1UA. and 10 - 18A mixed l a y e r s p a c i n g s . Barshad (1954) and White (1956) have suggested t h a t i n t e r l a y e r expansion i n 2 :1 l a y e r s i l i c a t e s i s r e l a -t e d to the l a y e r charge d e n s i t y . A c r y s t a l l a t t i c e with a l a y e r charge g r e a t e r than 150 meq/lOOgm (micas) w i l l be c o n t r a c t e d ; White (1954) c a l c u l a t e d that there are c r i t i c a l v a l u e s of s u r f a c e charge d e n s i t y a s s o c i a t e d w i t h d i f f e r e n t degrees of i n t e r l a y e r expansion. Bray (1937) showed that t r a n s i t i o n from a d i o c t a -h e d r a l i l l i t e to b e i d e l l i t e by l o s s of potassium and some isomorphously s u b s t i t u t e d magnesium takes p l a c e more r a p i d l y under a c i d s o i l c o n d i t i o n s . White (1956) showed that V e r m i c u l i t e - C h l o r i t e mixture weathered to a h i g h charge d i o c t a h e d r a l montmoril-l o n i t e i n the Ag h o r i z o n of two Hiawatha s o i l s . Tamura and others (1959) found a nonexpanding 14A " V e r m i c u l i t e " expanded to 18A on removal of i n t e r l a y e r alumina and suggested that s o i l c o n d i t i o n s may e x i s t which 68 cause r e l a t i v e l y complete s t a b i l i z a t i o n of alumina i n i n t e r l a y e r p o s i t i o n s , thus forming c h l o r i t e s . Other authors have reported mixed l a y e r m i n e r a l s which e x h i b i t v a r y i n g degrees of expansion between 1L\. - 18A on g l y c o l a t i o n . The evidence shows that c o n t r a c t i o n and expan-s i o n are dependent on the s u r f a c e charge d e n s i t y of the l a y e r s w i t h some i n f l u e n c e from the s i t e of o r i g i n of the charge ( t e t r a h e d r a l or o c t a h e d r a l isomorphous s u b s t i t u t i o n ) , the number of l a y e r s which have p r e f e r e n t i a l l y weathered (10A to 11+ or 18A m a t e r i a l ) or admitted i n t e r l a y e r m a t e r i a l , (li+A V e r m i c u l i t e , 11+A C h l o r i t e ) thus p e r m i t t i n g d e t e c t i o n by x-ray d i f f r a c t i o n technique. C o n t r a c t i o n and expansion of'.. t h e ' l a y e r s are a l s o dependent on the s t a b i l i t y of the i n t e r l a y e r m a t e r i a l . The s t a b i l i t y i s i n f l u e n c e d by the magnitude of the l a y e r charge and by the nature of the i n t e r l a y i n g m a t e r i a l . The l i t e r a t u r e shows that many i n v e s t i g a t o r s have been encouraged by the p r e d i c t i o n s of Grim ( 1 9 5 3 ) and B r i n d l e y ( 1 9 5 5 ) to search f o r a 11+A c l a y m i n e r a l which would prove the theory that a l u m i n a t i o n of 2 : 1 l a y e r s i l i c a t e s c o u l d proceed to the extent of the formation of a completely s t a b l e A l - c h l o r i t e . Talvenheimo, as repo r t e d by Klages and White ( 1 9 5 7 ) while s t u d y i n g the c l a y mineral c o n s t i t u t i o n of twelve Indiana s o i l s found a 11+A mi n e r a l i n the coarse f r a c t i o n of 1 0 of them. Klages and White ( 1 9 5 7 ) 69 examined several s o i l s to f i n d a sample which contained a large proportion of II4A0 clay* The aample which he selected consisted of an aluminum clay which he described as intermediate i n character between vermiculite and c h l o r i t e , but closer to c h l o r i t e in composition than i t was to vermiculite. C h l o r i t i c clays have also been reported i n the surface horizon of three other s o i l s on Vancouver Island, Two of which were of marine o r i g i n (Thiesen, Webster and Harvard, 1959)» It i s possible that the c h l o r i t e component of these clays was s i m i l a r to that i n the Alberni Clay. In the Alberni Clay, the weathering of micas and probably hornblende in a marine environment produced an i l l i t e - M g - c h l o r i t e complex in which the f i n e f r a c t i o n altered under a post depositional environment to i l l i t e -chlorite-montmorillonite. The coarse clay f r a c t i o n , because of i n a c c e s s i b i l i t y of the b r u c i t e interlayer material was not leached completely of i t s magnesium content and remained a non stable c h l o r i t e . In the surface horizon, under the influence of an acid environment in which the brucite layer became more unstable, t r i v a l e n t aluminum, which was available in high concentration, replaced magnesium and was p r e c i p i t a t e d to form a highly stable gibbsite layer between the montmorillon i.te and chloritized-montmorillonite sheets. S t a b i l i z a t i o n of alumina i n i n t e r l a y e r positions to form a stable dioctahedral c h l o r i t e has thus been shown to have reached i t s highest ex-pression , so f a r reported, in the Alberni Clay. 70 STUDIES OP CONCRETIONS MATERIALS AND METHODS A sample of s o i l taken from the A-B horizon was screened and the fractio n s which were retained on the 0,5 mm, 2*0 mm and 5»0 mm mesh sieves were examined with a microscope under I5X and 106X magnifications * The influence of treatment f o r the removal of iron on the p a r t i c l e size d i s t r i b u t i o n i n the A-B and C horizons was evaluated by making mechanical analyses after d i t h i o n i t e - c i t r a t e extraction of the s o i l s . The e f f e c t of four and eight extractions on the s o i l from the A-B horizon, and of two and four extractions on the s o i l from the C horizon was investigatede Mechanical analysis of p a r t i c l e s 2.0 to 0.2 microns were made by the pipette method (Kilmer and Alexander, 1949), and the technique recommended b.y Baver(l956, page 60) was used f o r the determination of p a r t i c l e s with equivalent spherical diameter l e s s than 0.2 microns. Heavy mineral separation of the sand, csoarse s i l t (44 to 10 microns), f i n e s i l t (10 to 2 microns) coarse clay and f i n e clay f r a c t i o n s were made with bromoform and the heavy minerals separated from the sand f r a c t i o n were examined with the microscope (100X). 71 In order to analyze the e x t r a c t s from the t r e a t -ments f o r the removal of i r o n , these were t r e a t e d w i t h "bromine, HNO^, and H 2S0^ to o x i d i z e sulphur compounds i n low o x i d a t i o n s t a t e s , and to remove or g a n i c a c i d s and organ-i c matter. Hydrogen pero x i d e proved i n e f f e c t i v e f o r the o x i d a t i o n of o r g a n i c m a t e r i a l s owing to the presence of manganese i n the e x t r a c t s . The e x t r a c t e d S i was determined by dehydration w i t h HC1 and v o l a t i l i z a t i o n of S i P ^ w i t h h y d r o f l u o r i c a c i d ( S c o t t , 1950, p 8 O 4 ) , The Pe an a l y s e s were made by the o-phenanthroline method ( S a n d e l l , 1959,P 537) and A l was determined by the alurainon method(lindsay, Peech and C l a r k , 1959). The peroxide method ( S a n d e l l , 1959, P 870) was used f o r the de t e r m i n a t i o n of t i t a n i u m , and a n a l y s i s of Mn was made.by the p e r i o d a t e method (Sandell,1959, P 608), A l l the c o l o r i m e t r i c analyses were made with the Bausch and Lomb c o l o r i m e t e r . Samples of the c o n c r e t i o n s were ground to pass a 325 mesh s i e v e and a magnetic f r a c t i o n was separated from f r a c t i o n s which responded to c u r r e n t s of 0,20, 0.25, 0,30 0,35, and O.i+O amperes. The magnetic f r a c t i o n was s e l e c t e d f o r x-ray study. The sample was taken to Dr. R eM. Thompson of the Department of Geology who was asked to examine i t and give advice as to the most s u i t a b l e method f o r making the a n a l y s i s . Dr. Thompson undertook the a n a l y s i s and made x - r a y d i f f r a c t i o n f i l m s . o f u n o r i e n t e d powder specimens o# the sample, from which he c a l c u l a t e d "d" s p a c i n g s . He a l s o 72 examined t h i n s e c t i o n s of the c o n c r e t i o n s which had been made f o r Mr. H. H o r t i e of the F e d e r a l Department of S o i l Survey by the U n i v e r s i t y of A l b e r t a . R e s u l t s and D i s c u s s i o n The c o n c r e t i o n s i n the A l b e r n i C l a y ranged i n s i z e from l e s s than -§• mm i n diameter. The s m a l l e r s i z e s were s p h e r i c a l i n ' shape but w i t h i n c r e a s i n g s i z e the con-c r e t i o n s were elongated and i r r e g u l a r i n shape, w i t h rough e x t e r i o r s and rounded edges. The s o f t e s t were cut q u i t e e a s i l y w i t h a k n i f e , i n which case the k n i f e marks were seen over the whole i n t e r i o r s u r f a c e . As they became p r o -g r e s s i v e l y harder, k n i f e marks were seen h a l f way i n , a q u a r t e r of the way i n , and merely e n t e r i n g the outer s u r -f a c e , a f t e r which the c o n c r e t i o n s broke open w i t h a sharp c r a c k . I t was p o s s i b l e to d i v i d e the c o n c r e t i o n s i n t o three groups on the b a s i s of t h e i r i n t e r i o r macroscopic morphology. The f i r s t group was arranged i n a s e r i e s which had brown to yellowish-brown e x t e r i o r s , and i n t e r i o r s that v a r i e d i n c o l o r from dark grey through g r e y i s h brown, g r e y i s h brown p i t t e d w i t h b l a c k s p o t s , brown p i t t e d w i t h M a c k s p o t s , to brown. M i c r o s c o p i c examination r e v e a l e d that the i n t e r i o r of these c o n c r e t i o n s were p i t t e d . P i t t i n g may have r e s u l t e d from s o l u t i o n of e a s i l y weathered m a t e r i a l . M i c r o s c o p i c examination a l s o r e v e a l e d that the grey and b l a c k appearance 7 3 was caused by the aggr e g a t i o n of b l a c k g l o s s y semi-c r y s t a l l i n e m a t e r i a l , and that the brown c o l o r a t i o n was caused by cementing m a t e r i a l which was d i s p e r s e d i r r e g u l a r -l y throughout the whole c o n c r e t i o n . A fragment of a n d e s i t e which was found i n the solum had many c h a r a c t e r i s t i c s i n common wit h t h i s s e r i e s of c o n c r e t i o n s . A sample from the unweathered i n t e r i o r of t h i s rock, a second sample from the rock s e l e c t e d to show an outer r i n d of weathering which e n c l o s e d r e l a t i v e l y unweathered m a t e r i a l , a c o n c r e t i o n which on c l o s e r examination was found to be a small p i e c e ( 3 m m ) of s i m i l a r rock, and the s e r i e s of c o n c r e t i o n s showed de-grees of hardness which v a r i e d from 8 (on an a r b i t r a r y s c a l e ) f o r the rock fragments, through 5 , k, 3, and 2 f o r d i f f e r e n t i n d i v i d u a l s i n the s e r i e s of c o n c r e t i o n s . Pro-g r e s s i v e c o l o r change and p i t t i n g was a l s o observed under 100X m a g n i f i c a t i o n . There seemed to be some c o r r e l a t i o n between the r e d u c t i o n i n dark c o l o r a t i o n with decrease i n hardness and i n c r e a s e i n p i t t i n g . The second s e r i e s of con-c r e t i o n s v a r i e d from what was e v i d e n t l y y e l l o w i s h brown s o i l c o a ted w i t h a dar k e r yellowish-brown e x t e r i o r to concre-t i o n s i n which the c o l o r s of the i n t e r i o r were i n t e n s i f i e d to dark brown w i t h v a r y i n g amounts of grey s p e c k l i n g . The s p e c k l i n g was, however, on a much lower s c a l e than that observed i n the f i r s t s e r i e s . The hardness of these c o n c r e t i o n s seldom exceeded 2 . The t h i r d group of c o n c r e t i o n s showed c h a r a c t e r i s t i c s 7 4 which were a l s o present i n the other two groups. The charac-t e r i s t i c which determined t h e i r placement i n a separate catego r y was the presence of a hard, b r i t t l e , dark, sub-s u r f a c e c o a t i n g which was not shown by the other two groups. M i c r o s c o p i c examination r e v e a l e d tJie same g e n e r a l c h a r a c t e r -i s t i c of the other two groups, but v i s i b l y the c o l o r of the i n t e r i o r s was much more v a r i a b l e . The c o l o r was sometimes y e l l o w i s h brown, brownish grey or brownish grey w i t h a pur-p l i s h t i n g e . There was no obvious g r a d a t i o n i n c o l o r between the i n d i v i d u a l samples of t h i s group. Hardness of these con-c r e t i o n s ranged between 2 and 4 . Wo easy s p e c u l a t i o n concern-i n g the p r o g r e s s i v e development of one form from another was p o s s i b l e . A b o u t 1 0 percent of the c o n c r e t i o n s examined f e l l i n t o the f i r s t s e r i e s , 6 0 percent i n t o the second T; s e r i e s and 3 0 p e r c e n t i n t o the t h i r d group. In a p r e l i m i n a r y examination of 1 0 0 c o n c r e t i o n s 1 mm s e l e c t e d at random, i t was found that a l l were a t t r a c -ted by a magnet although they c o u l d not a l l be taken up by the magnet. I f the l e s s h i g h l y cemented e x t e r i o r s were r e -moved by r o l l i n g the c o n c r e t i o n s g e n t l y between the f i n g e r s and a sheet of paper, the hard c e n t r a l c ores which remained c o u l d a l l be taken up by a magnet. This pronounced degree of a t t r a c t i o n to a magnet i s a d i a g n o s t i c c r i t e r i o n used by g e o l o g i s t s f o r the d e t e c t i o n of magnetite i n rock and s o i l . I t i s seen from the Mechanical Analyses (Table 1 2 ) t h a t removal of the cementing i r o n and aluminum compounds 75 r e s u l t e d i n decrease of the percentages of sand, s i l t and coa r s e c l a y i n the A-B h o r i z o n . The f i n e c l a y content a f t e r 8 d i t h i o n i t e - c i t r a t e e x t r a c t i o n s was k2*83%. as com-pare d to 33*88% a f t e r k treatments. S u p e r f i c i a l l y , 1^%, of t h i s i n c r e a s e was at the expense of the sand f r a c t i o n ^ 6^% from the s i l t , and 1% from the coarse c l a y . I t i s more p r o b a b l e , however, t h a t cementation caused aggregation In. a l l s i z e ranges and t h a t these were reduced s i m u l t a n e o u s l y w i t h the removal of the cementing agents. In the C h o r i z o n , the sand f r a c t i o n remained constant a f t e r two and f o u r e x t r a c t i o n s . The s i l t and coarse c l a y f r a c t i o n s were both reduced to g i v e a 6% i n c r e a s e i n the f i n e c l a y f r a c t i o n a f t e r f o u r d i t h i o n i t e - c i t r a t e e x t r a c t -I o n s . Comparison of the mechanical analyses f o r the A-B3 horizon., and the C h o r i z o n s o i l s a f t e r 8 and 1+ d i t h i o n i t e -c i t r a t e e x t r a c t i o n s r e s p e c t i v e l y shows that the h i g h p e r -m e a b i l i t y of the A-B h o r i z o n was due to aggregates formed by cementation. The C h o r i z o n which i s v e r y s l o w l y permeable has a c l a y content of 52.60%, wh i l e the A-B h o r i z o n , which i s h i g h l y permeable, has a c l a y content of 71»65%» The r e l a -t i v e absence of "dust" p a r t i c l e s i n b u l k samples of the A-B h o r i z o n s o i l showed that t h i s aggregation extended i n t o the submicroscopic ranges. Examination of the sand f r a c t i o n s of the A-B and C h o r i z o n s showed that they c o n s i s t e d of two s h a r p l y d i s t i n c t components - quartz c r y s t a l s and b l a c k , s t r o n g l y 76 magnetic c r y s t a l s i n the form of octahedra, dodecahedra and o t h e r c r y s t a l forms of the i s o m e t r i c system. Separa-t i o n of the two components was made by suspending the sand f r a c t i o n i n bromoform. The coarse s i l t (kk ~ 10 micron) f r a c t i o n when suspended i n bromoform d i d not show the sharp immediate d i v i s i o n i n t o l i g h t and heavy components that was shown by the sand f r a c t i o n and b e f o r e c e n t r i f u g i n g , a h i g h per-centage of the f i n e r p a r t i c l e s which remained suspended a f t e r a s e t t l i n g time of one hour were made to s e t t l e by i n d u c i n g a g g r e g a t i o n . Aggregation of these p a r t i c l e s and demonstration of the pronounced p o l a r i t y was accomplished by p a s s i n g a s m a l l magnet o u t s i d e the w a l l s of the tube i n which they were suspended. The p a r t i c l e s were o r i e n t e d by the magnet i n t o l o n g t h i n streamers which then acquired an exceedingly h i g h s e t t l i n g v e l o c i t y . The f i n e s i l t f r a c -t i o n d i d not d i s p l a y t h i s p o l a r i t y and f u r t h e r s e t t l i n g -c o u l d not be induced. P e t r o g r a p h i c examination of t h i n s e c t i o n s of the c o n c r e t i o n s showed that they c o n s i s t e d of s o i l p a r t i c l e s cemented together by i r o n oxides but no d e f i n i t e c r y s t a l s t r u c t u r e f o r the cementing oxides was e s t a b l i s h e d . The "d" spacings c a l c u l a t e d from the x-ray d i f f -r a c t i o n p a t t e r n of the magnetic f r a c t i o n of the concre-t i o n s (Table 15) r e v e a l e d a mixed quartz-magnetite p a t t e r n w i t h some p l a g i o c l a s e f e l d s p a r . 77 TABLE Ik THE EFFECT OF DITHIONITE-CITRATE EXTRACTION ON. THE MECHANICAL ANALYSIS OF THE ALBERNI CLAY Horizom Number of E x t r a c t i o n s Sand % S i l t . % C l a y 2»0 - 0.2 u % 0.2u % A-B3 k 3*27 32.91 29*94 33*88 A-B 8 1.80 26*55 28.82 42.83 C 2 3*54 48*95 19.82 27*69 C k 3»5k 43.86 19.06 33*54 TAB3 LE 15 X-RAY ANALYSIS OF MAGNETIC CONCRETIONS d spacings c a l c u l a t e d from x-ray d i f f r a c t i o n f i l m s , and observed i n t e n s i t i e s . Card No. 9-456 P l a g i o c l a s e A.S.T.M. Value Card No. 7-322 Magnetite s Card No. 5-O49O Quartz d spacings A 0 I d spacing I A 0 d spacing I A° d spacing I A 0 4 * 2 7 3 4 . 2 6 35 4*04 2 4*02 80 3 - 7 4 1 3a74 80 3*35 1.0 3.3k i o e 3 . 2 2 4 3 . 2 0 100 2 , 9 7 3 2*97 60 2 . 5 4 8. 2 ,-53 100 2,12 1 2*097 50 1.82 3 1.817 17 1.61.6 1 1*615 60 I . 4 8 6 3 I . 4 8 5 70 78 The analyses of the d i t h i o n i t e - c i t r a t e e x t r a c t s (Table 14) show that a t o t a l of 3.1+8% Fe, 2.69 % A l , 0.005% F i 0.009% Mn and about 1% S i were removed from the A - B h o r i -zon s o i l by ei g h t treatments w i t h the d i t h i o n i t e - c i t r a t e r e -agent. The f i r s t treatment removed 80% of the Fe and A l ex-t r a c t e d by the eight treatments and the amounts of these e l e -ments found i n the e x t r a c t s decreased s t e a d i l y to a minimum value of 0.01% i n the 5th e x t r a c t . A n a l y s i s of the s i x t h ex-t r a c t showed, however, that the s i x t h treatment w i t h the d i t h i o n i t e - c i t r a t e reagent removed twice as much i r o n and 1+ times as much aluminum as the f i f t h and the amounts of Fe and A l removed by the e x t r a c t i n g reagent remained r e l a t i v e l y h i g h u n t i l the e i g h t h treatment i n which the percentage of Fe and A l removed by the reagent had again f a l l e n to 0.01%. As seen i n Table |€ the amounts of S i removed by the 1st treatment was 1+0% of the t o t a l removed by 8 treatments w i t h the d i t h i o n i t e c i t r a t e reagent. The percentage of s i l i c a found i n the f i f t h and e i g h t h e x t r a c t s were a l s o the lowest (0.0i+%) found i n any of the 7 e x t r a c t s f o r y/hich values were obtained. The r e l a t i v e l y h i g h S i Fe and A l contents of the 6th and 7th e x t r a c t s from the d i t h i o n i t e - c i t r a t e treatments could i n d i c a t e that the removal of the g i b b s i t e sheet occu-p y i n g the i n t e r l a y e r p o s i t i o n had r e s u l t e d i n i n s t a b i l i t y and breakdown of the bas i c c l a y l a t t i c e during these treatments w i t h the e x t r a c t i n g reagent. The amounts of i r o n and manganese 79 removed from s o i l samples from the C h o r i z o n were about one t h i r d and one q u a r t e r of the amounts removed from the A - B h o r i z o n s o i l samples, and the q u a n t i t i e s of aluminum and of t i t a n i u m were about one t w e n t y - f i f t h and one f i f t i e t h of the amounts e x t r a c t e d from the A - B h o r i z o n s o i l samples. The percentage s i l i c a removed from the C h o r i z o n s o i l sample was however twice as much as that removed from the A - B h o r i z o n sample. TABLE 16 THE Fk, A l , T i , Mn and S i CONTENT OF SUCCESSIVE DITHIONITE-CITRATE EXTRACTS OF ALBERNI CLAY No. of E x t r a c t i o n s 1 2 3 4 5 6 7 8 To-t a l A - B Horizon 2.90 0.33 0.10 0.09 0.01 0.02 0.02 0.01 '3.48 %A1 2.10 0.19 0.16 0.09 0 .01 0.09 O.O4 0,01 2.69 %Ti x I O 3 3.80 0.80 0.30 4.90 foMn x 10^ 8 .00 O.5O 0.30 8.80 %8i O.4O 0.80 0.16 0.20 O.Oij. l o s t 0.08 O.O4 1.00 C Horizon %Fe 0.35 0.39 0.12 0.17 1.03 %A1 0.03 0.02 0 .02 O.O4 0.11 %T1 x I O 3 0.03 0.02 0.02 O.O4 0.11 %Mn x lO 2 4 - 2.00 - - - 2.00 %S± O.I4.O O.44 O.4O 0.72 1.96 80 F e r r u g i n o u s or ferromanganiferous c o n c r e t i o n s have been found i n s o i l s which have been developed under the i n f l u e n c e of d i f f e r e n t pedogenic p r o c e s s e s and w i d e l y d i f -f e r e n t c l i m a t i c regimes. ?/heating (1936) , Winters (1938) and Dro s d o f f and N i k i f o r o f f (1940) have rep o r t e d f i n d i n g them i n the p o d z o l i c s o i l s of Western Washington, I l l i n o i s and Oregon, while Beater (194O) Bennett and A l l i s o n (1928) and Roberts have r e p o r t e d them i n the l a t e r i t i c s o i l s of N a t a l , Cuba and Puerto R i c o . I t has, t h e r e f o r e , not been p o s s i b l e to a s s o c i a t e c o n c r e t i o n s w i t h any major pedogenic process or c l i m a t i c regime s i n c e shots are found i n p o d z o l i c s o i l s as w e l l as i n l a t e r i t i c and i n temperate and t r o p i c a l c l i m a t i c zones. Winters (1938) c o n s i d e r e d that the most important f e a -t u r e s a s s o c i a t e d w i t h shot f o r m a t i o n are i n t e n s i v e and p r o l o n -ged weathering, slow removal of weathering p r o d u c t s from the p r o f i l e , and the f r e q u e n t a l t e r n a t i o n of o x i d i s i n g and reduc-i n g c o n d i t i o n s i n the s o i l . Smith, Drosdoff and N i k i f o r o f f a t t r i b u t e s the forma-t i o n of shot to the r e t e n t i o n of s o i l s o l u t i o n i n the s m a l l e s t pore spaces as the p r o c e s s of deh y d r a t i o n progresses d u r i n g the dry season. Dehydration i s f o l l o w e d by the p r e c i -p i t a t i o n of i r o n and manganese compounds on the s o i l p a r t i c l e s w i t h subsequent o x i d a t i o n of these compounds. Dro s d o f f and N i k i f o r o f f (1940) and many authors c i t e d by them, suggest that shot may be formed as the r e s u l t of m i c r o b i o l o g i c a l a c t i v i t y . Beater (1940) , commenting on c o n c r e t i o n s found i n 81 N a t a l s o i l s , expressed the o p i n i o n that the e x i s t e n c e of shot i n any p a r t i c u l a r r e g i o n c o u l d he t r a c e d to and a s s o c i a -ted with g e o l o g i c a l s o i l types. He d i d not c o n s i d e r that c o n c r e t i o n s c o u l d he d i s s o c i a t e d from the g e n e t i c p r o f i l e , and gave c o n s i d e r a t i o n not onl y to environmental c o n d i t i o n s hut a l s o to parent m a t e r i a l . The parent m a t e r i a l to which Beater r e f e r r e d c o n s i s t s of conglamerates, sandstones, g r a n i t e and r e c e n t sands, a l l i n t r u d e d by b a s a l t i c m a t e r i a l . The c o n s i s t e n t f e a t u r e s a s s o c i a t e d with shot f o r -mation a r e , r e s t r i c t e d d r a i n a g e , and a l t e r n a t e wet and dry p e r i o d s i n the s o i l p r o f i l e . During the wi n t e r months when the b u l k of p r e c i p i t a t i o n o c c u r s , the A l b e r n i c l a y i s water-logged because of the r e s t r i c t e d drainage i n the heavy tex-tured C h o r i z o n . During the summer, the s o i l g r a d u a l l y d r i e s out and i n J u l y i t i s almost completely dehydrated. During the w i n t e r months, the c o n d i t i o n s of s a t u r a t i o n with r e s t r i c -ted v e r t i c a l movement of the s o i l s o l u t i o n present s u i t a b l e c o n d i t i o n s f o r m o b i l i z a t i o n of t r a n s i t i o n metal ions by d i s -s o l v e d o r g a n i c matter and l e a f l e a c h a t e s . D r o s d o f f and N i k i f o r o f f (191+0) say of the Dayton s o i l s , "the f a c t o r s a f f e c t i o n h o r i z o n t a l m o b i l i z a t i o n apparen-t l y e x e r t a g r e a t e r i n f l u e n c e than the f a c t o r s of l e a c h i n g ? The same c o n d i t i o n s seem to be o p e r a t i v e here, i n so f a r as they a f f e c t the v e r t i c a l movement of i r o n . Examination of the data from chemical analyses presented i n Table 18 shows that there i s v e r t i c a l movement of i r o n i n the p r o f i l e 82 "but that there i s no p r e f e r e n t i a l o v e r a l l accumulation or l e a c h i n g and i n f a c t the i r o n i n the A - B and i n the C Horizons remains constant though perhaps i n d i f f e r e n t forms. One of the most s t r i k i n g f e a t u r e s of the A l b e r n i C l a y i s the i n c r e a s e i n c o n c e n t r a t i o n of magnetite p a r t i c l e s i n the coarse s i l t to sand, and rock r e s i d u e s found i n the p r o f i l e . T h e o r e t i c a l c o n s i d e r a t i o n s (Appendix V I I I ) p r e -clude the p o s t u l a t i o n of any theory i n v o l v i n g the p o s s i b i l -i t y that the i n t e r a c t i o n of paramagnetic ions i n s o l u t i o n w i t h the magnetic f i e l d of a Fe^O^ c r y s t a l i s a cause of the f o r m a t i o n of c o n c r e t i o n s . I t i s , however, h i g h l y probable the presence of magnetite c r y s t a l s and shot i n t h i s s o i l , b o t h i n s t r i k i n g l y high c o n c e n t r a t i o n s , i s not w h o l l y co-i n c i d e n t a l . Magetite i s found disseminated as an a c c e s s o r y min-e r a l i n most igieous rocks and i s commonly a s s o c i a t e d a l s o with c r y s t a l l i n e metamorphic roc k s . I t s h i g h r e s i s t a n c e to weather-i n g p l a c e s i t among the few primary m i n e r a l s most l i k e l y to be i n h e r i t e d by sedimentary rocks form the o r i g i n a l m a t e r i a l , from which they are formed. Magnetite i s , t h e r e f o r e , a com--ponent of most s o i l s whether they are formed from g r a n i t i c or b a s a l t i c m a t e r i a l ; igneous, metamorphic or sedimentary r o c k s . I t can be expected, however, that magnetite c r y s t a l s occur i n higher c o n c e n t r a t i o n s i n s o i l s formed from mafic r o c k s , than i n those formed from f e l s i c m a t e r i a l s . Most of the l i t e r a t u r e does not give enough i n f o r m a t i o n to allow 8 3 comparison of shot c o n c e n t r a t i o n i n d i f f e r e n t s o i l s on the b a s i s of the composition of parent m a t e r i a l w i t h s p e c i a l r e g a r d to i t s magnetite content* I t i s h i g h l y s u g g e s t i v e that on the occasions t h a t i n f o r m a t i o n i s gi v e n , shot are found o n l y i n the s o i l s d e r i v e d from b a s i c m a t e r i a l s . Beater ( 1940) s t a t e d that a l l h i s p arent m a t e r i a l was i n t r u d e d by b a s a l t , Sherman.Fujioka and Fujimoto (1955) and Sherman, F o s t e r and Fujimoto (1948) found numerous t i t a n i f e r o u s - f e r r u g i n o u s c o n c r e t i o n s i n the s o i l s of the Hawaiian I s l a n d s . Bothe the s o i l and the c o n c r e -t i o n s were s t r o n g l y magnetic. The s o i l s were developed from b a s a l t i c p arent m a t e r i a l , and the s o i l type i n which shot were found was s i t u a t e d i n an Intermediate p o s i t i o n on slo p e s where seepage from upper l e v e l s of high e r r a i n f a l l produced c y c l e s of w e t t i n g and d r y i n g i n the p r o f i l e , F a r s t a d (1959) found s i m i l a r c o n d i t i o n s i n A r g e n t i n a when he surveved the M i s s i o n e s t e r r i t o r y between Paraguay and B r a z i l . Two s o i l types , found i n c l o s e j u x t a p o s i t i o n , i l l u s t r a t e d i f f e r e n c e s which can develop i n two p r o f i l e s under the same c l i m a t i c regime, drainage c o n d i t i o n s , and pedogenic p r o c e s s e s where the parent m a t e r i a l s are d i f f e r e n t . The San Igna c i o and M i s s i o n e s s o i l s e r i e s are both L a t o s o l s , r e a d i l y permeable to a depth of about 200 cm where impermeable bedrock i s encountered* The San Ignacio i s developed on sand-stone and has no c o n c r e t i o n s . The Mi s s i o n e s i s developed *• P e r s o n a l Communication. 8 4 from b a s a l t which intruded the sandstone and i s s i t u a t e d on a 6 to 15 percent slope i n an intermediate p o s i t i o n s i m i l a r to that described by Sherman (1935) ' The r a i n f a l l i s evenly d i s t r i b u t e d but i s of the shower type rather than c o n t i n -uous. Seepage from higher l e v e l s occurs. Average tempera-tures of 20°C p r e v a i l . These c o n d i t i o n s provide c y c l e s of w e t t i n g and dr y i n g which are comparable i n e f f e c t i v e n e s s w i t h those of the temperate zones. They are shorter c y c l e s but more frequent and more i n t e n s i v e . The f a c t that concretions develop on the Missiones and not on the San Ignacio cannot be a t t r i b u t e d to drainage d i f f e r e n c e s or the d i f f e r e n t i a l a v a i l a b i l i t y of i r o n bearing m i n e r a l s . Both s o i l s are l a t o -s o l i c w i t h considerable i r o n accumulation through the p r o f i l e . I t seems h i g h l y probable that the occurrence of con-c r e t i o n s i n s o i l s formed from b a s i c m a t e r i a l i s in f l u e n c e d not only by the f a c t that such rocks c o n t a i n minerals which are e a s i l y weathered to re l e a s e i r o n , manganese and t i t a n i u m which form cementing compounds, but that magnetite c r y s t a l s c o n t r i b u t e to the r e t e n t i o n and eventual p r e c i p i t a t i o n of these m a t e r i a l s i n the s o i l p r o f i l e . This mechanism could be a c t i v a t e d by the i n t e r a c t i o n between the p o s i t i v e l y charged surface of the magnetite c r y s t a l s and anionic complexes of P e 2 t Pe^t M n a n d T i * T h i s theory i s sub s t a n t i a t e d by the f i n d -ings of Anderson (1956) who showed that magnetite c r y s t a l s are e f f e c t i v e i n absorbing such ions from s o l u t i o n . With r e s t r i c t e d v e r t i c a l movement of these complexes through the s o i l these a t t r a c t i v e f o r c e s have greater opportunity to exert t h e i r 85 i n f l u e n c e . STUDIES OF COATINGS METHODS AND MATERIALS Separation and Chemical A n a l y s i s of Black Coatings. The b l a c k coatings were scraped c a r e f u l l y from the surfaces of peds wi t h a t h i n blade and the scrapings were separated i n t o f r a c t i o n s which responded to magnetic cur-r e n t s s i m i l a r to those used w i t h the isodynamic separation of the c o n c r e t i o n s , A sample of the 0 . 2 5 amps, f r a c t i o n was d i s -s o l v e d i n d i l u t e HC1, f i l t e r e d , and a n a l y s i s was made of the f i l t e r e d e x t r a c t . Fe analyses were made by the O-phenanthro-l i n e method, T i was determined by the hydrogen peroxide method, A l analyses were made by the aluminon method Mn was determined by the periodate method and S i by the hydro-f l u o r i c a c i d method. A q u a l i t a t i v e a n a l y s i s f o r elements heav i e r than t i t a n i u m was also made w i t h the x-ray f l u o r e s -cence spectrograph f o r comparison w i t h s i m i l a r analyses of the s o i l from the A - B and from the C horizons. An a n a l y s i s f o r carbon was made by the F i s h e r i e s Department. Microscopic Examination and X-ray A n a l y s i s of  Black Coatings. Several samples of the f r a c t i o n s of scrapings which were obtained by isodynamic s e p a r a t i o n were examined under 15X m a g n i f i c a t i o n and they were subdivided i n t o c l a s s e s on the b a s i s of shape and c o l o r of the p a r t i c l e s . The c l a s s e s were 86 c o l l e c t e d i n spot p l a t e d e p r e s s i o n s where they were segregated and c o n c e n t r a t e d hy h a n d p i c k i n g i n d i v i d u a l s from the m i c r o s -cope stage w i t h a sharpened t o o t h p i c k wetted w i t h a l c o h o l or bemzene. When s u f f i c i e n t l y l a r g e samples of each c l a s s had been c o l l e c t e d i n t h i s manner, the samples were ground on the spot p l a t e i n a l c o h o l or benzene with an agate p e s t l e . The ground samples were r o l l e d i n t o t h i n needles w i t h f i n g e r n a i l p o l i s h , a n d x-ray analyses of the f i l m s were made u s i n g a N i t a r g e t w i t h Co f i l t r a t i o n . Prom the x-ray d i f f r a c t i o n f i l m s of these u n o r i e n t e d powder specimens, d spacings were c a l c u l a t e d and compared with indexed A.S.T.M. values f o r the d spacings of m i n e r a l s and i r o n oxide compounds. X-ray A n a l y s i s of S i l i c e o u s C o a t i n g s . X-ray d i f f r a c t i o n p a t t e r n s of the white c o a t i n g s which were c a r e f u l l y scraped from the s u r f a c e s of s o i l peds i n the 26"-50" h o r i z o n of the s o i l p r o f i l e were prepared u s i n g Mn f i l t e r e d Pe r a d i a t i o n . RESULTS AND DISCUSSION Black Coatings The chemical a n a l y s i s of the b l a c k c o a t i n g s (Table 18) showed that the movement and p r e c i p i t a t i o n of i r o n to form c o a t i n g s i n the Cg h o r i z o n of the A l b e r n i C l a y was e x t e n s i v e enough to b u i l d up a c o n c e n t r a t i o n of FegO^ i n the c o a t i n g s which was e q u i v a l e n t to the t o t a l c o n c e n t r a t i o n of -Pe20^ i n the s o i l of the A-B h o r i z o n . There was a c o n s i d e r a b l e i n -cr e a s e i n the Mn0 o content over the s o i l of e i t h e r the A-B or a ? the G- h o r i z o n . The r a t i o s of ^Q2°3 a n d lfilQ'2 t 0 A 1 2 a 3 i n t h e b l a c k coatings of 2.0 and 0.11 as compared w i t h s i m i l a r r a t i o s of 0.4 and 0 found w i t h s o i l from the A-B ho r i z o n showed that there was a greater r e l a t i v e accumulation of ferromagnetic elements i n the coatings than i n the ArB-ho r i z o n s o i l . The x-ray fluorescence spectrograms (Pigure X I I I ) show these r e l a t i o n s very g r a p h i c a l l y * They a l s o show that the coatings accumulated s l i g h t l y l a r g e r amounts of Co and NI than were present i n the s o i l . The manganese content of the s o i l from "both the A-B and the C' horizons was shown by the low peak i n t e n s i t i e s to be l e s s than 0„.1%8 Chancey(l953)* however, reported a value of 0B18% Mb i n the A-B h o r i z o n . The carbon a n a l y s i s of a sampke of bl a c k coatings showed that the organic matter content was ver y low (0,16%)» Microscopic examination of the 0.30, 0*35, and 0»ij.O amps, f r a c t i o n s of the black coatings showed that more than 60%; of the f l a k e s making up the samples were b l a c k f l a t p l a t e s w i t h g r a i n y surfaces to which va r y i n g amounts of s o i l adhered. P a r t i c l e s which had n e g l i g i b l e amounts of adhering s o i l r e f l e c t e d l i g h t d i f f e r e n t l y and were f i r s t thought to be d i f f e r e n t from the other p a r t i c l e s to which the adhering s o i l imparted a brownish hue* About 20% of the samples was represented by blocky p a r t i c l e s which s t r i k i n g l y smooth g l a s s y s u r f a c e s , and there were a few other p a r t i c l e s whcih showed a bl o c k y s t r u c -*Chancey, H.W.R., 1953. Some Chemical, P h y s i c a l and Micropedolog-i c a l Studies of Vancouver I s l a n d Shot? S o i l s . Masters t h e s i s * U n i v e r s i t y of B r i t i s h Columbia. 88 TABLE 1.7 X-RAY DIFFRACTION DATA FOR B LACK COATINGS ( 0 . 4 0 araps 8) USING Cu RADIATION WITH A N i FILTER A.S.T.M.. Card 6 - 0 5 0 2 Hematite No. A.S.T.M.Card 5 - 0 4 9 0 Quartz Nb. Sample i s p a c i n g A 0 1 d s p a c i n g A° I 0 d s p a c i n g A I 7*90 4 4 . 7 0 10 3 . 6 8 70 3 . 3 4 100 2*69 100 2 . 6 8 1 2 . 5 1 80 2 . 4 5 2 . 5 3 2 . 4 5 1 2 1 2 . 2 0 70 2 . 0 7 10 1 . 8 6 6 1 1 . 8 3 7 70 1 .691 80 1 . 6 6 4 1 1 . 6 3 4 10 TABLE 18 THE Fe, A l , T i , AND Mn CONTENT OF THE BLACK COATINGS Fe A l Mn T I S i Percentages 8.2 3.2 0.33 0.11 32.2 88(a) Figure X I I I . X ray fluorescence "analyses 'of C horizon, soil 8 coatings. Comparison of Fe and Mn peak heights for C, and A B Horizons Coatings (0.25 amps) 89 ture wich a s l i g h t l y g r a i n y s u r f a c e and a g l a s s to r e s i n o u s l u s t r e which appeared to he i n t e r m e d i a t e i n c h a r a c t e r be-tween the f l a t g r a i n y p l a t e s and the b l o c k y o b s i d i a n - l i k e p a r t i c l e s . The l e s s than 0 . 2 0 ampere f r a c t i o n s were composed of p l a t e s which were uniform i n appearance throughout the samples and were s i m i l a r to the p l a t e s d e s c r i b e d p r e v i o u s l y . The "d" spacings which were c a l c u l a t e d from x-ray d i f f r a c -t i o n p a t t e r n of u n o r i e n t e d specimens of a l l samples showed that they c o n s i s t e d p r i m a r i l y of quartz and f e l d s p a r and that they were a l l b a s i c a l l y almost i d e n t i c a l . Haematite or t u r g i t e l i n e s were d e t e c t e d i n the "d" spacings (Table XVII) of o n l y one of the samples. S i l i c e o u s Coatings. C a l c u l a t e d v a l u e s f o r the "d" spacings of specimens of the s i l i c e o u s c o a t i n g s (Table 17) which were made from the d i f f T a c t o m e t e r t r a c i n g s showed that they were composed of s i l i c a w i t h minor amounts of p l a g i o c l a s e f e l d s p a r . 90 TABLE 19 X-RAY DIFFRACTION DATA FOR WHITE COATINGS USING Fe RAD-IATION WITH A Mn FILTER A.S.T.M. A.S.T.M. Values d spacings c a l c u l a t e d from X-ray d i f f r a c t i o n f i l m s , and observed i n t e n s i t i e s Card No. 9 - 4 5 6 P l a g i o c l a s e Card No. 5-0i+90 Quartz d snacings A° I d . I spagings d spacings A° I 4 . 2 6 30 4 . 2 6 35 4 . 0 2 18 4 . 0 2 80 3 . 7 2 13 3 . 7 4 80 3 . 3 4 100 3 . 3 4 3 100 3 . 2 1 82 3 . 2 0 100 2 . 4 5 7 13 2 . 4 5 3 12 2.29 12 2.237 12 2.24 12 2.24 6 2 . 1 3 17 2 .128 9 1.98 13 1.980 13 1.82 13 1 .817 17 1 .54 12 1 .541 11 91 SOLUBILITY RELATIONS OP IRON AND ALUMINUM IN THE ALBERNI OLAY MATERIALS AND METHODS S o i l water suspensions or s o i l suspensions i n 2 to 5 x 10"-^M C a C l 2 were a c i d i f i e d w i t h HC1 and p l a c e d i n r e a c t i o n f l a s k s * A i r composed of 1% or 20$ Og i n mixture w i t h Ng, Ng and COg were bubbled through the suspensions which were maintained at 25°C i n a constant temperature b a t h s The a i r bubbled through the f l a s k s was prepared by m i x i n g Ng and atmospheric a i r i n constant p r o p o r t i o n hy the use of flowmetres equipped with sapphire b a l l s - manufactu-red by the Manostat C o r p o r a t i o n , New York, Before e n t e r i n g and a f t e r l e a v i n g the r e a c t i o n f l a s k s , a i r mixtures were pass-ed :through suspensions of composition s i m i l a r to the r e a c t i o n s uspensions. This maintained a constant vapour preassure i n the gas phase and reduced the l o s s of water-HCl from the s e r i e s of r e a c t i o n f l a s k s through which the gas mixtures were bubbled. At the end of the r e a c t i o n p e r i o d , the suspen-s i o n s were f i l t e r e d through paper and c o l l o d i a n impregnated f i l t e r paper and the f i l t e r e d e x t r a c t s were analyzed f o r Pe, A l , Ca and Mg. Pe analyses were made by the o-phenanthroline method. The A l d e t e r m i n a t i o n s were made by the aluminon method. The versenate method was used f o r the t i t r a t i o n of 92 Ca p l u s Mg and the Ca concen t r a t i o n was determined w i t h the P e r k i n Elmer flame photometer. S o i l samples from the C horizon were used as i t was f e l t that data concerning release of c a t i o n s from the s o i l could he b e t t e r evaluated i n the absence of complica-t i o n s which would a r i s e from use of the A - B horizon s o i l w i t h i t s g r e a t e r accumulation of weathered products and or-ganic matter. S o i l and s o i l p r e v i o u s l y t r e a t e d w i t h hydrogen peroxide were e x t r a c t e d w i t h d i s t i l l e d water and CaClg and the e x t r a c t s were analyzed f o r Pe and A l . Results and D i s c u s s i o n C o n s i d e r a t i o n of data from the f i r s t s e r i e s of ex-periments d i d not r e v e a l any c o n s i s t e n t trends and over the course of the experiment s e v e r a l f a c t o r s were thought to be c o n t r i b u t i n g to the e r r a t i c r e s u l t s that were obtained (Table 2 1 ) . a. F a i l u r e of the system to a t t a i n e q u i l i b r i u m because of short r e a c t i o n time and d r i f t i n g of pH towards high values during the r e a c t i o n p e r i o d . b. Incorrect c o l o r i m e t r i c analyses because of the d i f f i c u l t y i n o b t a i n i n g a b s o l u t e l y c l e a r f i l t r a t e s . c. Reversal of e q u i l i b r i u m during f i l t r a t i o n i n an a t -mosphere d i f f e r e n t from the r e a c t i o n atmosphere. d. Incomplete mixing of the sample during the r e a c t i o n . The f o l l o w i n g steps were therefore taken to e l i m i -93 nate these. To avoid these l i m i t a t i o n s i n the second s e r i e s of experiments, (Table 2 2 ) the r e a c t i o n time was lengthened and the s o i l was washed s e v e r a l times w i t h water a c i d i f i e d to pH 3 . 0 w i t h H C 1 . In the t h i r d (Table 23) and successive s e r i e s the suspensions were f i l t e r e d through c o l l o d i a n impregnated f i l -t e r paper under an atmosphere i d e n t i c a l w i t h the r e a c t i o n atmosphere. In the f o u r t h (Table 2k) snd. successive s e r i e s , the s o i l was f i r s t suspended i n water and only that p o r t i o n which had not s e t t l e d below a depth of 20 cm i n k hours was used. Bubbling of the a i r through the r e a c t i o n f l a s k s was adequate to maintain p a r t i c l e s of t h i s s i z e i n suspension. A bulk suspension was prepared i n t h i s way and washed w i t h a c i d i f i e d 3 to 5 M CaClg s o l u t i o n u n t i l the pH remained con-stant at 3 * 6 2 . With these successive m o d i f i c a t i o n s , c l e a r f i l -t r a t e s w i t h measurable concentrations of Fe andAl were ob-tained and the pli remained constant w i t h i n 0 . 0 2 p H u n i t s during the r e a c t i o n time. Data f o r s i x s e r i e s of runs are pre-sented i n Tables 21 to 25. As the washings which were necessary f o r s t a b i l i z a -t i o n of the pH were considered to produce a h i g h l y a r t i f i c i a l c o n d i t i o n under which m a t e r i a l coming i n t o s o l u t i o n was r e -moved very much f a s t e r than they would be under n a t u r a l con-d i t i o n s i n a s o i l w i t h r e s t r i c t e d drainage, the e f f e c t of the washings on the removal of i r o n was i n v e s t i g a t e d . 9k The f i l t r a t e from the washings i n S e r i e s I I I (Table 2 3 ) had i n d i c a t e d t hat d i s t i l l e d water removed some of the more s o l u b l e i r o n from the s o i l p a r t i c l e s and a d d i t -i o n a l washings w i t h a c i d i f i e d s o l u t i o n s removed f u r t h e r q u a n t i t i e s . Analyses of s o i l water (15:250) e x t r a c t s showed s u c c e s s i v e decreases i n the percentage Pe determined as the e f f e c t i v e n e s s of f i l t r a t i o n was i n c r e a s e d by use of c o l l o -d i a n impregnated f i l t e r paper. This decrease i n percentage Pe was not due to i n c r e a s e i n tr a n s m i t t a n c e of the s o l u t i o n from which suspended p a r t i c l e s may have been removed because treatment of a l l f i l t r a t e s w i t h hydrogen peroxide gave sub-s t a n t i a l i n c r e a s e s i n the amounts of i r o n d e t e c t e d on an a l y -s i s . T r e a t i n g the s o i l w i t h H^O^ p r i o r to e x t r a c t i o n w i t h water doubled the percentage Pe coming i n t o s o l u t i o n and in c r e a s e d the aluminum percentage by 800%. E x t r a c t i o n w i t h CaClg a p p a r e n t l y f l o c c u l a t e d c o l -l o i d a l i r o n which was then r e t a i n e d on the f i l t e r s . The Pe determined i n GaGl^ e x t r a c t s was s i g n i f i c a n t l y lower than that determined on the water e x t r a c t s . The i n c r e a s e s i n i r o n and aluminum a f t e r treatment w i t h hydrogen p e r o x i d e i n d i c a t e d that some very s t a b l e form of metal organic matter complex e x i s t e d i n the s o i l e x t r a c t s . These complexes must e x i s t not only i n the c o l l o i d a l s i z e range but must extend a l s o i n t o molecular dimensions s i n c e 95 they can pass through collodian impregnated f i l t e r paper. Data from these analyses are presented in Table 26.. E a r l y Russian investigators suggested the p o s s i b i l -i t y of the i n t e r a c t i o n of organic acids with sesquioxides to form soluble organo-mineral complexes which move through the s o i l and are p r e c i p i t a t e d i n the horizon. Bloomfield(1955)» (1957), Jones and Wilcox(l929), Beckwith (1955), Broadbent (1957), Hines and Barber (1957) and many other investigators have shown that organo-metal complexes exi s t i n s o i l s . Bloomfield (1955), Schnitzer and Delong (1955) demon-strated that the leachate from leaves of a wide var i e t y of tree species was e f f e c t i v e in the reduction of i r o n , and in the f o r -mation of a stable complex. Various reasons have been given f o r the p r e c i p i t a -tion of these complexes in s o i l s . Some authors suggest that the ligand i s destroyed by b a c t e r i a l action, and McKenzie iso l a t e d organisms from the s o i l which were capable of o x i d i s i n g ferrous i r o n . Kononova (1956) suggests that m o b i l i -zation and immobilization depend on the pH, the concentration of the humic material and the oxidizing-reducing conditions in a s o i l . Heintze and Loes (1948) showed that s o i l organic matter-metal compounds which are insoluble in water may be ex-tracted from a s o i l with solvents which form complexes with the metals. If metal ions of the t r a n s i t i o n series are added to these extracts, p r e c i p i t a t i o n of organo-metal compounds w i l l take place. 96 The exact nature of the l i g a n d s i s not known (Jenkinson and T i n s l e y ) and w i l l p r o b a b l y vary q u i t e w i d e l y w i t h the b a c t e r i a l metabolism, organic s u b s t r a t e , extent of orga n i c matter decomposition, and o x i d a t i o n p o t e n t i a l of the s o i l . M i s t e r s k i and Loginov (1959) r e p o r t that humic a c i d s c o n s i s t of an aromatic nucleus with h y d r o l y s a b l e p e r i p h e r a l c h a i n s and m i n e r a l elements. They a l s o reported that s o l u b l e s a l t s of humic a c i d s are coagulated by cal c i u m , i r o n , and aluminium. Young and Mortimer r e p o r t the i s o l a t i o n of humic a c i d components such as e y s t e i c , a s p a r t i c and glutamic a c i d s , s e r i n e , threonine and methionine from s o i l s . I t i s p o s s i b l e that these N - c o n t a i n i n g compounds form the p e r i p h e r a l chains r e p o r t e d by M i s t e r s k i and Loginov. I t i s p o s s i b l e to have complexes of very high s t a -b i l i t y formed i n the s o i l medium and the s t a b i l i t y of these complexes w i l l vary with the nature of the i o n and the e l e c -t r o s t a t i c f i e l d of the complexing l i g a n d . The 5d o r b i t a l s of a gaseous i o n have equal energies but i n the presence of an e l e c t r o s t a t i c f i e l d these energy l e v e l s are s p l i t . The g r e a t e r the e l e c t r o s t a t i c f i e l d , the g r e a t e r w i l l be t h i s energy o f s e p a r a t i o n . The t r a n s i t i o n metals w i t h u n f i l l e d d e l e c t r o i i s h e l l s w i l l be more s t a b l e i f the e l e c t r o n s are i n lower energy l e v e l s and they p r e f e r l i g a n d s which give l a r g e energy s e p a r a t i o n s . The e l e c t r o s t a -t i c f i e l d of o-phenanthroline >'N0 >NH, >H„0 *> COO > 0H~ 9 7 (Pearson ( 1 9 5 9 ) . In s o i l s , t h e r e f o r e , we have o r g a n i c amines and a c i d s which complex wi t h metal ions forming complexes of v a r y i n g s t a b i l i t y and those ions which are s t r o n g l y c r y s t a l f i e l d s t a b i l i s e d w i l l be slow to r e a c t . I t seems h i g h l y probable that the f o r m a t i o n of such complexes i n the A l b e r n i dominated the system b e i n g i n v e s t i g a -ted and reduced the r a t e at which the experimental c o n d i t i o n s i n f l u e n c e d the s o i l - w a t e r e q u i l i b r i a . The wide v a r i e t y of complexes p r e s e n t i n the s o i l , along w i t h slowness of the r a t e of r e a c t i o n combined to give data which were not r e p r o -d u c i b l e . The presence of an a p p r e c i a b l e p r o p o r t i o n of alumi-num i n complex forms which may be d e s t r o y e d by treatment w i l l i HgOg i s i n c o n t r a s t to the behaviour of a c i d brown p o d z o l i c s o i l s . D i f f i c u l t y w i l l o b v i o u s l y be encountered i n attempts to study the i o n i c behaviour of i r o n and aluminum i n s o i l s s i m i l a r to A l b e r n i c l a y . 98 TABLE 20 (SERIES I) PE CONCENTRATION OP THE EXTRACTS PROM SOIL/* WATER SUSPENSIONS OP 1:10 REACTED WITH 0 . INITIAL TDH (ACIDIFIED WITH HCl) 3-50 R e a c t i o n % 0 ? i n mixture P i n a l Fe time (hrs) w i t h N ? pH moles/l x 10 M4 4.22 0 48 1 4.74 0 48 4.05 0 96 4.30 0 96 4.33 0 144 3.83 0.15 144 3.83 0.29 48 20 4.33 0.05 48 4.26 0 26 4.04 0.07 96 4.40 0.04 144 3.81 0.29 TABLE 21 (SERIES II) Pe CONCENTRATION OP THE EXTRACTS PROM SOIL: WATER SUSPENSIONS OP 1:10 REACTED WITH 1%0 IN MIXTURE WITH NP f pH PH values f o r d u p l i c a t e samples Adjustments 1 A IB 2 A 2B 3A 3B 4 A 4 B 5 A 3 B 6 A 6B F i r s t 9.2.59 HOH-HCl Suspension 3.05 3.05 3.05 3.05 3.05 3.05 3.05 3.05 3.05 3 .05 3.05 3.05 Second 10.2.59 HOH-HCl Suspension 3.05 3.67 3.20 3.00 3.00 3.72 2.78 3 .05 3.10 3 .00 3 .00 2.85 Supernatant 3.62 4.06 3.80 3.65 3.63 4.30 3.30 3.55 3 .65 3.63 3.70 3.46 12.2.59 Suspension 4.13 4.57 4 .18 4.12 4.05 4.38 3.97 4.09 4 .08 4 .12 4 .17 4.02 Supernatant 4.96 4 .90 4.68 4.62 4.64 4 .80 5.46 4 .63 4 .58 4.66 4 .70 4.65 15.2.59 Suspension 4.72 4.76 4 .61 4.60 4 .61 4 .80 5.39 4 .62 4.56 4 .62 4.66 4.60 T h i r d 15.2.59 HOH-HCl Suspension 3.00 3.00 3.00 3.00 3.00 3.00 3.C4 3.02 2.98 2.98 3.02 3.01 Supernatant 3.91 4 .08 3.95 3.95 3.85 4.02 4.03 3.90 3 .90 3 .97 3.76 3.88 Suspension 3.82 4 .00 3.87 3.87 3.76 3.88 3.99 3.88 3.81 3.90 3 .85 3.84 A f t e r r e _ a c t i o n 4.89 5.00 4 .90 4 .90 4.71 4.72 4 .78 4 .82 4 .80 4 .86 4 .82 4 .82 R e a c t i o n 9^ 192 384 96 192 384 F e ^ m o l e s / l 6 , 7 0 1 8 ' ° 7 , 9 3'° 6 5 * ° 2 3 * 7 6 * 7 ° 6 * 7 ° 1 0 * 5 1 8 ' 5 2^-° X 1 0 6 1 0 0 TABLE 22 (SERIES I I I ) Pe CONCENTRATION IN THE EXTRACTS PROM SOIL:WATER SUSPENSIONS OP 1 : 1 0 REACTED WITH 1%0 OF MIXTURE WITH N^ 2 P H pH va l u e s f o r S o l u t i o n de-Adjustments d u p l i c a t e samples car}tedIFZ\nG ; moles / 1 X 1 0 l a l b 2a 2b 3a 3b & i r s t HOH Suspension 5.53 5.53 5.53 5.53 5.53 5.53 Supernatant 5.99 5.99 5.99 5.99 5.99 5.99 0.53 Second H0H-HC1 Suspension 3.30 3.30 3.50 2.50 2.50 3.00 Supernatant 3.33 2.80 2.74 2.78 2.80 3.27 0.19 T h i r d HOH Suspension 4 .70 3.57 4.32 4.40 4.39 4.50 H0H-HC1 Suspension 3.37 3.03 3.22 3.28 3.30 3.32 Supernatant 3.83 3.40 3.63 3.70 3.72 3.76 0.09 F o u r t h HOH Suspension 4.52 4.02 4.23 4.35 4.46 4.46 H0H-HC1 Suspension 2.97 3 .03 2.91 3 .07 3.05 3.08 Supernatant 3.00 3 . 0 6 2.97 3.16 3.10 3.14 0.14 A "f "h f* v T* t°— a c t i o n i*" 0 8 3- 9 2 3.99 4.26 4.09 4.11 Reaction time(hrs) 96 14  38  Fe (moles/1) o 0 0 0 - 2.5 XI0° 101 TABLE 22 (CONT'D) (SERIES I I I ) SUSPENSIONS REACTED WITH ATMOS-PHERIC AIR (20% 0 ) PH pH values f o r d u p l i c a t e samples Adjustments F i r s t H O H Suspension 5.35 5.53 5.53 5.53 5.53 5.53 Supernatant 5.99 5.99 5.99 5.99 5.99 5.99 Second H0H-HC1 Suspension 2.50 2.50 2.50 3.00 2.50 2.50 Supernatant 2.73 2.78 2.80 3.04 2.96 2.84 T h i r d HOH Suspension 4.33 4.40 4.41 4.27 4.35 4.44 H0H-HC1 Suspension 3.20 3.26 3.27 3.20 3.22 3.21 Supernatant 3.64 3.75 3.67 3.64 3.69 3.65 F o u r t h HOH Suspension 4.30 4.35 4.34 4.26 4.31 4.38 H0H-HC1 3.06 3.02 3.04 3.02 3.06 2.94 Supernatant 3.17 3.12 3.16 3.16 3.14 3.04 A f t e r R e action 4.19 4.11 4.16 4.07 4.05 4.09 Fe(moles/1) X 10 b 0 0 0 0 2.5 2.5 102 TABLE 23 Pe CONCENTRATION IN THE EXTRACTS PROM SOIL 0.005MCaCl SUSPENSIONS OP 1 : 1 0 ACIDIFIED WITH H C 1, AND REACTED WITH 1%02 IN MIXTURE WITH N , AND WITH COg and Ng. Before -Reaction A i r F e . compo- f 6 Re a c t i o n R e a c t i o n time (hrs) s i t i o n m o i e s / l x i u 3.01 3.87 384 3#>2 2.2 3.02 4.02 0.2 3.03 3.05 2C$ 02 1.5 3.03 3.74 96 N2 5.0 3.02 3.74 8.4 3.04 4.01 384 4.0 3.00 3.94 1.3 3.04 4.01 96 co2 1.3 3.02 3.96 1.8 3.05 3.80 384 0.4 103 TABLE 24 (SERIES IV) DATA PROM THE ANALYSIS OP THE EXTRACTS PROM THE REACTION OP 1% SUSPENSIONS OF SOILS PAR-TICLES WITH SETTLING VELQCITIES<20cm IN 4 HOURS, IN 3.6 x 103 M CaCl I n i t i a l pH = F i n a l pH = 3.6O = O.O4 R e a c t i o n Fe mo l e s / l A l moles/1 Mg moles/l t i m e / % 0 2 x 106 xio5 X 103 . (hrs) I n i t i a l l a . l b 2a 2b 3a 3b Suspen-s i o n 0.36 O.36 2.60 2.60 0.61 O.67 96/1 1.23 1.29 1.60 2.80 O.65 0.72 96/20 1.21 0.72 3.40 3.70 1.78 1.39 192/not 0.45 3.40 1.78 r e a c t e d 192/1 2.33 3.30 192/20 0.90 1.39 3.60 1.43 10k TABLE 25 (SERIES V ) DATA PROM THE ANALYSES OP EXTRACTS PROM THE REACTION OP 1% SUSPENSIONS OP SOIL PARTICLES WITH SETTLING VEL0CITIS<20 cm IN k HOURS, i n 5-60 X 10 3M CaCl . pH 3.60 = 0.01+ Re a c t i o n time Pe A l Mg r (hrs) /%0 mo l e s / l moles/1 moles/1 X I O 6 X10 5 X I O 3 192/20 3.36 3.30 0.17 384 not r e - 2.42 4.70 0.51 ac t e d 38U/1 2.96 2.55 4.70 4.40 0.51 0.45 384/20 3.49 2.11 4.80 4.80 0.48 0.54 576/not r e - 3.36 4.10 acted 376/1 3.14 2.69 4.40 3.70 0.51 0.51 576/20 2.24 2.69 4.70 5.00 O.56 0.81 105 TABLE 26 DATA PROM THE ANALYSES OP SOIL WATER EXTRACTS C. H o r i z o n . I 15 gm s o i l shaken w i t h 250 cc d i s t i l l e d water I I 15 gm s o i l heated on hot p l a t e w i t h 45 cc d i s t i l l e d water and e x t r a c t e d with 250 cc I I I 15 gm s o i l t r e a t e d w i t h 45 cc hydrogen peroxide on hot p l a t e and e x t r a c t e d w i t h 250 cc d i s t i l l e d water IV 15 gm s o i l e x t r a c t e d w i t h 250 cc of 0.5.N C a C l 0 at pH 6 . 0 A-B Horizon. V Same treatment as I VI Same treatment as I I VII Same treatment as I I I V I I I Same treatment as IV l a F i l t e r e d through f l u t e d f i l t e r paper l b „ „ 1 sheet c o l l o d i a n im-pregnated F.P. l c " " 2 sheets " F i l t r a t e from l c t r e a t e d w i t h HOOH '» l a " " H a F i l t e r e d through f l u t e d F.P. U b 1 sheet c o l l o d i a n im-pregnated P.P. X 1 0 b 229.4 foAl X 103 I46.O 91.7 183.5 533.4 229.4 5 8 . 3 2 . 7 0 106 TABLE 26 (CONT'D) X 10° X 10 J F i l t r a t e from l i b t r e a t e d w i t h OOOH I4I.8 " " 11a " " 566.7 I l i a F i l t e r e d through f l u t e d f i l t e r paper i+87• 9 b " " 1 sheet e o l l o d i a n im-pregnated F.P. 369.4 19.50 . c F i l t r a t e from I l l b t r e a t e d w i t h HOOH 4OO.O d » " a 11 600.0 IV a F i l t e r e d through f l u t e d F.P. 83-3 b " " e o l l o d i a n impregnated F.P. 100.1 V a F i l t e r e d through fluefced f i l t e r paper 37L0 b " " e o l l o d i a n impregnated F.P. 79.2 c F i l t r a t e from Vb t r e a t e d w i t h HOOH 116.6 Va 925.1 VI F i l t e r e d through e o l l o d i a n impregnated F.P. 166.8 VII " " " 3,336.0 V I I I '» " " 225.2 107, SUMMARY AND CONCLUSIONS Samples of s o i l which were taken from v a r i o u s depths i n the p r o f i l e of the A l b e r n i C l a y were t r e a t e d with reagent to remove the f r e e i r o n . They were then d i s p e r s e d w i t h Sodium carbonate and f r a c t i o n a t e d , by com-bined sedimentation and c e n t r i f u g a t i o n . The combinations of x-ray a n a l y s i s w i t h d i f f e r e n t i a l thermal t o t a l chem-i c a l and c a t i o n exchange c a p a c i t y analyses showed that the c l a y c o n s i s t e d of i l l i t e - c h l o r i t e - m o n t m o r i l l o n i t e assemblages i n the samples which were taken from deeper h o r i z o n s and that the c h l o r i t e content i n c r e a s e d with i n c r e a s e i n p a r t i c l e s i z e and c l o s e n e s s to the s u r f a c e . A l l samples of c l a y contained f e l d s p a r quartz and am-p h i b o l e . The chemical formula was c a l c u l a t e d f o r the f i n e c l a y f r a c t i o n from the su r f a c e h o r i z o n , and i t was found to be a doubly d i o c t a h e d r a l A l - c h l o r i t e with the a p p r o x i -mate chemical f o r m u l a ( A l j . ^ e ^ T i ^ M g ^ J C A l ^ g S i ^ g C O ^ C O H J a C C a . K 2 3 X # 2 U ) Examination of the coarse s i l t and sand f r a c -t i o n s showed that they c o n t a i n e d magnetite c r y s t a l s which were i n h e r i t e d from the parent m a t e r i a l and the rock from which the s o i l was formed. Samples of c o n c r e t i o n s were examined with the microscope d i r e c t l y , and a f t e r the p r e p a r a t i o n of t h i n 108 s e c t i o n s , x-ray a n a l y s i s was a l s o made of a magnetic f r a c t i o n of the ground c o n c r e t i o n s which had been c o l -l e c t e d w i t h the isodynamic s e p a r a t o r . The t h i n s e c t i o n s showed that c o n c r e t i o n s con-s i s t e d of s o i l p a r t i c l e s cemented together by i r o n oxides which were not i d e n t i f i e d c r y s t a l l o g r a p h i c a l l y . The d i f f r a c t i o n p a t tern, from the x-ray a n a l y s i s of the magnetic f r a c t i o n showed s t r o n g quartz and magnetite l i n e s and weaker p l a g i o c l a s e r e f l e c t i o n s . Samples of the b l a c k c o a t i n g s were scraped from the s u r f a c e s of peds i n the C 2 h o r i z o n of the s o i l and were analysed c h e m i c a l l y and by x-ray d i f f r a c t i o n . The chemical a n a l y s i s showed that the b l a c k c o a t i n g s c o n t a i n e d l a r g e r p e r c e n t a g e s of aluminium manganese and t i t a n i u m than the s o i l . The x-ray analyses showed d i f f -r a c t i o n p a t t e r n s f o r quartz and f e l d s p a r and the s t r o n g 2.53A magnetite r e f l e c t i o n . Three haematite l i n e s were r e c o g n i z e d but they were extremely weak and were not co n s i d e r e d adequate f o r a p o s i t i v e i d e n t i f i c a t i o n . Samples of the white c o a t i n g s were c o l l e c t e d from s u r f a c e s of peds i n the C h o r i z o n and were analysed by x-ray d i f f r a c t i o n . They were found to c o n s i s t of quartz w i t h a l e s s e r amount of f e l d s p a r . S o i l - w a t e r suspensions and s o i l suspension i n 2 to 3 x 10~ 3M CaClg were a c i d i f i e d and r e a c t e d w i t h a i r composed of 1% and 20%0 i n mixture with N 0 and 109 and w i t h Ng and COg. The e x t r a c t s from s o i l - w a t e r sus-pensions were f i l t e r e d w i t h paper and c o l l o d i a n impreg-nated f i l t e r paper and the f i l t r a t e s were analysed t o determine t h e i r A l and Fe contents. The r e a c t e d s o i l s showed great v a r i a b i l i t y i n the q u a n t i t i e s of Fe, A l and Mg which went i n t o s o l u t i o n d u r i n g the course of the r e a c t i o n . The analyses of the s o i l water e x t r a c t s showed higher aluminium and i r o n contents when they were f i l t e r e d w i t h paper than when they were f i l t e r e d w i t h c o l l o d i a n impregnated f i l t e r paper, and the amounts of these elements determined by a n a l y s i s i n c r e a s e d when the f i l t r a t e s were t r e a t e d w i t h hydrogen p e r o x i d e . The data from the a n a l y s i s of the s o i l - w a t e r e x t r a c t s suggested that complexes of Fe and A l wit h s o i l o r g a n i c matter dominated the r e a c t i o n systems. The presence of a wide v a r i e t y of complexes reduced the r a t e s at which experimental c o n d i t i o n s i n f l u e n c e d the s o i l - w a t e r e q u i l i b r i a and so were r e s p o n s i b l e f o r the i r r e p r o d u c i -b i l i t y of the'data. It i s concluded that the weathering of p r i -mary minerals i n the s u r f a c e h o r i z o n of the A l b e r n i C l a y r e l e a s e d i r o n , aluminium and s i l i c a , some of which were leached from the p r o f i l e , and t r a c e s of which were p r e c i p i t a t e d on the su r f a c e s of peds i n the v a r i o u s h o r i z o n s of the s o i l . There i s no h o r i z o n of se s q u i o x i d e 110 accumulation and the i r o n content of the more highly-weathered surface h o r i z o n . was not s i g n i f i c a n t l y l e s s than that of the C horizon because downward move-ment of d i s s o l v e d substances through the p r o f i l e was r e s t r i c t e d , (a) by the slow p e r m e a b i l i t y of.the C h o r i -zon, (b) the a l t e r n a t e l y wet and dry c o n d i t i o n s to which the s o i l i s subjected, and (c) the i n t e r a c t i o n between organic anion complexes of Fe and A l and the p o s i t i v e l y charged surfaces of the magnetite c r y s t a l s and hydrous oxides of i r o n which occur throughout the solum. I t i s conceivable that the occurrence of mag-n e t i t e p a r t i c l e s i n b a s a l t i c s o i l s may have an important r o l e i n the formation of ferruginous and ferromangan-i f e r o u s concretions i n s o i l s -I t i s suggested that the c h l o r i t e i n the surface horizon was f i r s t formed by the transformation of a h i g h l y micaceous c l a y to an i l l i t e - c h l o r i t e assem-blage under a marine environment. Under t h i s e n v i r o n -ment a Mg-chlorite was produced. A f t e r u p l i f t the l e a c h i n g I l l of the s o i l under a c i d c o n d i t i o n s transformed the Mg-c h l o r i t e to montmorillonite which i s s t i l l the predom-inant mineral i n the deeper horizons. The a c i d i t y of the surface horizon and i t s p e r i o d i c d e s s i c a t i o n r e s u l -ted i n the p r e c i p i t a t i o n of aluminum between tike montmor-i l l o n i t i c l a y e r s . 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Proc. 21:603-607. Drosdoff, M, and N i k i f o r o f f , C C . 1940. Iron manganese concretions i n Dayton s o i l s . S o i l S c i . 495333—345• F o s t e r , Margaret"D» 1953* The r e l a t i o n between " I l l i t e " , B e i d e l l i t e and M o n t m o r i l l o n i t e . Clays and C l a y M i n e r a l s , N a t l . Acad. S c i . Natl.Res. C o u n c i l pub. 327:386. 1956. C o r r e l a t i o n of d i o c t . K. micas on the b a s i s of t h e i r charge r e l a t i o n s . U.S.G.S. Bul l . l 0 3 6 D . Ginsburg, A.I. 1953. Cookeite, a l i t h i u l c h l o r i t e mineral. Doklady Akad. Nauk. S.S.S.R. 90:871-4. 114 Grim, R.E. 1953. Clay Mineralogy, McGraw H i l l Book Conine. Grim, R.E., Bradley, W.F., and Brown, G. 1951. The mica m i n e r a l s . Ch. V. X-ray I d e n t i f i c a t i o n s and Str u c t u r e s of Clay M i n e r a l s . The M i n e r a l o g i c a l S o c i e t y , London. Grim, R.E., and Johns, W i l l i a m D. 1953. Clays and Clay M i n e r a l s . N a t l . Acad. S c i . - N a t l . Res. Co u n c i l pub. 327-81. Grim, R.E., D i e t z , and Bradley, W.F. 1949. Clay mineral composition od some sediments from the P a c i f i c ocean of the C a l i f o r n i a coast and the Gulf of C a l i f o r n i a . Geol. Soc. Am. B u l l . 60:1785-1808. Hey, Max H. 1954* A new review of the c h l o r i t e s . Min. Mag. 30:277-292. Heintze, S.G., Loes, H., Bremner, J.M and Mann, P.J.G. 1946. Me t a l l o - o r g a n i c complses i n s o i l s . Nature 158:790-91. Hines, P.L. and Barber, S.A. 1957. C h e l a t i n g a b i l i t y of s o i l organic matter. S o i l S c i . Soc. Amer. Proc. 21: 368-373. Jackson, M.L. 1958. S o i l Chemical A n a l y s i s . P r e n t i c e H a l l Inc. Jackson, M.L., Hseung, Y., Corey, R.B., Evans, E.T. and Vanden Heuvel, R.C. 1952. Weathering sequence of c l a y s i z e minerals i n s o i l s and sediments. I I . Chemical weather-in g of l a y e r s i l i c a t e s . S o i l Soc. S c i . Amer. Proc.14: 77-81. Jackson, M.L. 1959. Frequency d i s t r i b u t d m of c l a y minerals i n major great s o i l groups as r e l a t e d to the f a c t o r s of s o i l f o r m a t i o n . Clays and Cl a y Minerals Monograph No. 2. Ea r t h Science S e r i e s . Pergamon Press.p.133-143. Jenkinson, David S and T i n s l e y , Joseph. 1959. Studies on the organic m a t e r i a l e x t r a c t e d from s o i l s and composts* I . The i s o l a t i o n and c h a r a c t e r i z a t i o n of l i g n o - p r o t e i n s from composts. J . S o i l S c i . 10:245-263. Jonas, E.C. and Brown, T.E. 1959- A n a l y s i s of i n t e r l a y e r mixtures of three c l a y mineral types by x-ray d i f f r a c t i o n . J . Sediment P e t r o l , 29:77-86. Jones, H.T. and Wilcox, J.S. 1929. Studies i n s o i l g e n e t i c s . J . Soc. Chem. Ind.(London). 48:3O4T-3O8T. 115 K i l m e r , V i c t o r J . , and Alexander, L y l e T. 1949• Methods of making mechanical analyses ofi s o i l s . S o i l S c i . 6 8 : 1 5 - 2 4 -Klages, M.G., and White, J.L. 1957* A c h l o r i t e - l i k e m i n e r a l i n Indiana s o i l s . S o i l S c i . Soc. Amer. Proc. 2 1 : 1 6 . L i n d s a y , W.L., Peach, M i c h a e l , and C l a r k , J.S. 1 9 5 9 . Determination of Aluminum Ion A c t i v i t y i n S o i l E x t r a c t s . S o i l S c i . Soc. Amer. P r o c . 2 3 : 2 6 6 - 2 6 9 . MacEwen, D.M.C. 1 9 5 1 . The M o n t m o r i l l o n i t e M i n e r a l s . Ch. IV. X-ray i d e n t i f i c a t i o n and s t r u c t u r e of c l a y m i n e r a l s . The M i n e r a l o g i c a l S o c i e t y , London. M i s t e r s k i , V. and Loginov, V. I n v e s t i g a t i o n of some ph y s i c o c h e m i c a l p r o p e r t i e s of humic a c i d s . Pochvovedenic No. 2 : 3 9 - 5 1 . O r c e l , M.J., C a i l l e r e , S . , and Henin, S. 1 9 5 0 . Novel e s s a i de c l a s s i f i c a t i o n des c h l o r i t e s . Min. Mag. 2 9 : 3 2 9 - 3 4 0 . Osthaus, Bernard. 1 9 5 6 , K i n e t i c s t u d i e s on Montmoril-l o n i t e and N o n t r o n i t e by the a c i d d i s s o l u t i o n t e c h n i a u e . Clays and C l a y M i n e r a l s , Natl.Acad. S c i . - N a t l . Res. Councl pub. 4 5 6 : 3 0 1 - 3 2 1 . Pearson, Ralph G. 1 9 5 9 . C r y s t a l f i e l d e x p l a i n s i n o r g a n i c b e h a v i o r . Chemical and E n g i n e e r i n g News, 3 7 : 7 2 - 7 6 . R i c h , C.I. 1 9 5 6 . Muscovite weathering i n a s o i l developed i n the V i r g i n i a Piedmont. C l a y s and Cl a y M i n e r a l s , N a t l . A c a d . S c i . - N a t l . Res. C o u n c i l pub.5 6 6 : 2 0 3 . R i c h , C.I., and Obenshain, S.S. 1 9 5 5 . Chem. and C l a y M i n e r a l P r o p e r t i e d of a Red-Yellow P o d z o l i c S o i l d e r i v e d from Muscovite S c h i s t . S o i l S c i . Soc. Amer. Pr o c . 19 : 3 3 4 . Robinson, W.O. 1 9 4 5 . Determinatcbn of S i , T i , A l , Mn, Ca, Mg, K, Na and S. U.S.Dept. of A g r i c . S o i l S c i . 5 9 : 7 - 1 1 . Ross, C.S., and Hendricks, S.B. 1945* M i n e r a l s of the M o n t m o r i l l o n i t e group. U . S . G . S . P r o f . Paper 2 0 5 B . S a n d e l l , E.B. 1 9 5 9 . C o l o r i m e t r i c Determination of t r a c e s of M e t a l s . 3 r d . Ed. I n t e r s c l e n c e P u b l i s h e r s , Inc., New York. 116 S c h o f i e l d , R.K. 1949• E f f e c t on pH of electisc charges c a r r i e d by c l a y p a r t i c l e s . J . S o i l Sci.1:1 S c o t t , W.W. 1950* Standard methods of Chemical A n a l y s i s . 5th E d i t i o n , V o l . I . pp.866, 883. S c h n i t z e r , M., and DeLong, W.A. 1955* I n v e s t i g a t i o n on the m o b i l i z a t i o n and t r a n s p o r t of i r o n i n f o r e s t e d s o i l s . I I . The nature of the r e a c t i o n of l e a f e x t r a c t s and l e a c h a t e s w i t h i r o n . S o i l S c i . Soc. Amer. P r o c . 19:363-8. Sherman, G.Donald, P o s t e r , Zera C, and Pujimoto. 1948. Some of the p r o p e r t i e s of the Ferruginous Humic L a t o s o l s of the Hawaiian I s l a n d s . S o i l S c i . Soc. Amer. P r o c . 13:471-476. Sherman, G.Donald, F u j i o k a , J u d i t h , and Fujimoto, G i i c h i . 1955. T i t a n i f e r o u s - P e r r u g i n o u s L a t e r i t e o f Meyer Lake, M o l o k a i , Hawaii. P a c i f i c Science 9:49. S l a u g h t e r , M., and M i l n e , I.H. 1958. The f o r m a t i o n of c h l o r i t e - l i k e s t r u c t u r e s from M o n t m o r i l l o n i t e . Presented at the Seventh N a t i o n a l Conference on Cl a y s 8nd C l a y M i n e r a l s , Washington, D.C. October. T h i e s e n , A.A., Webster, G.R., and Harvard, M.E. 1959. The occurrence of c h l o r i t e and v e r m i c u l i t e i n the c l a y f r a c t i o n of three B r i t i s h Columbia s o i l s . Can. J . S o i l S c i . 39:244-251. Tamura, T. 1958. I d e n t i f i c a t i o n of c l a y m i n e rals from a c i d s o i l s . J . S o i l S c i . 9:141-147. Tamura, Tsuneo, Hanna, P.M., Shearin, A.E. 1959* Proper-t i e s of Brown P o d z o l i c s o i l s . S o i l S c i . 87:189-197. Warkentin, B.P. 1957* Conductimetrie t i t r a t i o n of a c i d M o n t m o r i l l o n i t e suspensions. K o l l . P e i t . 153:44-46. Webb, T.L., and Heystek, H. 1957. The carbonate m i n e r a l s , Chapter X I I I . The D i f f e r e n t i a l Thermal I n v e s t i g a t i o n of C l a y s . M i n e r a l o g i c a l S o c i e t y of London. White, Joe L. 1956. Layer charge and i n t e r l a m e l l a r expansion i n a Muscovite. C l a y s and C l a y M i n e r a l s N a t l . Acad. S c i . - N a t l . R e s . C o u n c i l pub. 566:289. W h i t t i g , L.D., K i l m e r , V . J . , Roberts, R . C , and Gady, J . C 1957* C h a r a c t e r i s t i c s and genesis of Cascades and Powell S o i l s of Northwestern Oregon. S o i l S c i , Soc. Amer. Proc. 21:226-231. Zyva g i n , B.B., and Nefedov, E . I . 1954. Co o k e i t e . Doklady Akad. Nauk. S.S.S.R. 95:1305-8. APPENDIX 1 CONDUCTIOMETRIC TITRATION OP 2.0 - 0.2 MICRON H-CLAY C HORIZON 2 DITHIONITE TREATMENTS m l N a O H S p e c i f i c . c o n d u c t a n c e (25 C) mmhos X 103 0.1336N c m 1 0 33.8 37.6 0.5 20.6 24.2 0.7 20.4 0.8 20.9 1.0 23.3 1.5 24.8 2.0 24.3 26.3 3.0 27.8 28.5 4.0 32.3 5.0 34.9 36.4 6.0 42.2 41.7 W e i g h t s a m p l e ( g m ) 3.43 3.14 APPENDIX II CONDUCTIOMETRIC TITRATION OP 2.0 - 0.2 MICRON H-CLAY A-B HORIZON 4 DITHIONITE TREATMENTS Specific conductance (25 C) mmhos cm-'' X 103 1 2 0 15.9 15.4 0.5 10.6 1.0 14.9 12.0 2.0 15.9 15.5 3.0 18.5 18.5 4.0 20.7 20.7 6.0 24.3 2.48 8.0 28.8 29.4 10.0 36.4 39.0 Weight sample (gm) 10.39 13.13 ml NaOH 0.1336N APPENDIX III CONDUCTIOMETRIC TITRATION OP 2.0 - 0.2 MICRON H-CLAY C HORIZON 4 DITHIONITE TREATMENTS Specific conductance (25 C) mmhos cflT'' X 10? 1 2 0 28 .4 1 5 7 . 5 0 . 2 1 3 7 . 0 0 . 5 1 1 4 . 0 0 . 7 9 6 . 5 1 . 0 1 4 . 4 7 7 . 5 1.5 1 6 . 2 6 0 . 8 2 . 0 18 .0 5 9 . 3 2 . 1 5 9 . 0 2 . 2 5 8 . 4 2 . 3 5 8 . 2 2 . 4 5 8 . 0 2 . 5 2 0 . 3 5 7 . 5 2 . 8 5 7 . 5 3 . 0 2 2 . 8 5 8 . 4 3 . 5 2 4 . 0 5 8 . 8 4 . 0 2 6 . 3 6 1 . 6 4 . 5 3 2 . 0 6 3 . 6 5 . 0 6 6 . 5 6 . 0 7 6 . 6 7 . 0 8 9 . 7 8 . 0 118.0 9 . 0 1 5 5 . 0 ;ight sample (gm) 1 . 7 8 2 . 1 3 ml NaOH 6 . 1 0 9 3 N A P P E N D I X I V C O N D U C T I O M E T R I C T I T R A T I O N O P 0.2 M I C R O N H - C L A Y C H O R I Z O N , 4 D I T H I O N I T E T R E A T M E N T S ml NaOH Specific conductance (25 C ) mmhos cnr^x 103 pH 1 2 3 0 96.4 111.0 75.7 0.5 79.8 46.6 1.0 47.5 53.6 33.3 1.5 • 38.7 44.2 30.3 2.0 37.8 43.2 30.3 2.5 38.5 44.0 3.0 40.3 44.8 33.1 4.0 47.5 35.3 5.0 45.0 37.6 6.0 53.6 40.4 7.0 50.5 44.4 8.0 63.3 49.0 9.0 56.7 10.0 70.6 11.0 64.5 13.0 75.1 Weight sample (gm) 3.66 3.14 2.19 3.8 4.0 5.7 5.9 APPENDIX V COKDUCTIOMETRIC TITRATION OP 0.2 MICRON H-CLAY C HORIZON 2 DITHIONITE 1 TREATMENTS ml NaOH 0.1336N Specific conductance (25 C) mmhos cm~x IO 2 1 2 3 pH 1 2 0 43.2 40.8 31.5 3.8 3.2 1 33.8 33.1 23.4 2 26.1 25.9 16.1 3 19.1 19.9 11.3 4 14.7 15.4 9.7 5 13.8 15.0 9.8 6 14.0 15.0 10.3 7 15.2 15.0 5.6 5.6 7.5 11.7 8 15.3 15.2 12.3 10 16.5 15.9 15.7 12 20.4 19.2 21.2 14 26.5 24.3 25.9 16 32.0 29.3 31.5 18 36.4 33.2 20 Weight Sample 41.7 2.21 37.7 2.01 1.17 10.5 10.3 (gm) APPENDIX VT CONDUCTIOMETRIC TITRATION OP 0.2 MICRON H-CLAY A-B HORIZON, 8 DITHIONITE TREATMENTS ml NaOH S p e c i f i c conductance (25 C) ~ 0.1336N mmhos cm"1 x IO 2 P 1 2 3 1 2 3 0 92.5 1 83.2 2 77.6 3 72.9 4 66.8 5 61.8 6 56.7 7 52.6 8 48.4 9 44.0 10 40.3 11 37.0 12 34.2 13 31.9 14 29.8 15 29.8 16 30.2 17 30.4 18 30.6 19 31.0 20 31.9 21 32.8 22 23 35.3 24 25 38.8 26 28 44.2 29 46.5 30 47.6 32 52.7 33.5 55.5 34 36 37 63.O 38 39 66.6 40 68.5 Weight Sample 6.08 (gm) 93.2 38.9 31.3 8166 24.0 16.6 70.5 12.1 64.4 11.3 59.0 12.3 54.3 13.7 51.1 15.7 45.7 18.3 21.2 41.3 23.8 35.2 26.2 33.2 28.7 32.1 31.4 31.4 31.4 31.9 32.5 33.3 36.3 39.5 43.2 47.6 51.7 56.2 60.5 64.5 69.0 73.0 6.03 1.85 2.3 2.25 3.1 5.2 8.1 3.8 4.5 APPENDIX VII CONDUCTIOMETRIC TITRATION OP- 0.2 H-CLAY A-B HORIZON, 4 DITHIONITE TREATMENTS ml NaOH Specific conductance (25 C) 0 1336N mmhos cm"'' x 10^ 1 2 3 0 145.0 150.0 102.0 1 145.0 94.0 1.5 139.5 2 135.5 135.5 86.6 3 128.0 132.5 77.9 4 123.0 73.0 ft. 5 116.5 5 113.0 116.5 66.6 6 106.0 111.0 59.8 7 99.5 106.0 53.9 8 93.0 98.5 49.0 9 86.3 92.8 44.8 10 80.6 86.4 38.5 11 75.2 81.2 34.4 12 70.6 76.6 32.4 13 65.3 72.2 32.4 14 61.0 66.8 33.0 15 56.4 63.O 37.0 16 53.0 59.8 38.2 17 50.4 56.8 39.8 18 48.5 55.4 42.8 19 48.0 54.8 44.9 20 47.0 55.1 48.5 21 49.0 56.6 51.5 22 50.6 58.3 54.1 23 52.0 60.3 56.7 24 54.2 63.0 59.7 25 56.6 65.7 63.O 26 59.5 68.5 65.6 27 62.3 71.7 68.2 28. 65.5 74.6 70.6 29 67.5 77.7 72.9 30 70.5 80.5 75.2 31 73.0 83.3 32 75.3 87.4 33 78.3 34 81.0 93.0 35 83.5 97.0 36 86.5 99.3 37 89.0 38 92.5 39 94.3 40 97.4 Weight 3.59 3.65 2.52 APPENDIX VIII C a l c u l a t i o n s h o w i n g t h e o r d e r o f m a g n i t u d e o f t h e m a g n e t i c d i p o l e i n t e r a c t i o n o f m a g n e t i t e c r y s t a l s a n d f e r r o m a g n e t i c i o n s i n s o l u t i o n a s c o m p a r e d w i t h t h e r m a l e n e r g y . M a x i m u m p o s s i b l e v a l u e o f d i p o l e e n e r g y TSL^Hr/v^ i s p r o v i d e d b y t h e m a g n e t i z a t i o n o f 450 g a u s s i n a s p h e r i c a l s p e c i m e n o f r a d i u s r M g i s t h e m a g n e t i c m o m e n t o f a n i o n ( a b o u t 5 u B ) w h e r e —21 1 u B i s 9.27 x 10 e r g / g a u s s 2 —21 3 M a g n e t i c E n g r g y 8/3 vJ x 450 x 5 x 9.27 x 10 /vJ 1.7 x 10 e r g s T h e r m a l e n e r g y a t 20 C . 3/2 1.38 x 10~ l 6 x 290 6.0 x 10" 1 4 M a g n e t i c e n e r g y / T h e r m a l e n e r g y 3 x 10 * T h e s a t u r a t i o n m a g n e t i c m a m e n t o f m a g n e t i t e i s 450-476 g a u s s K a g a k u 26:360-61, 1956. 

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