AN ENVESHGAHQN OI? ‘E‘QTM AND EXCHANQEABLE MANGANEE AS A ExrfiEANS CF CORRELATENG ARGELLACEQ¥S SE§2\‘{§.NTS Thesis For ”me Degree 0% M. S. r“"(‘$!"’."flfa9=’ ‘mzsn-n _r 7?," 1*. first" 7 ‘15:! 2%?791"‘:‘:.‘. C! f‘- . ;< 72‘» 37721..» E l-:Lc.vu.;~.u A: UH‘Q-Lfiu uazzszuuulz L fi- 7 .9. ‘2‘ L r“ 4“ V” ‘ mowers. mun Engnam 1958 Innis LIBRARY Michigan State University AN ILJESTlfigTICR CF 32T54.§fli) u "I"; "l‘ -. _‘. .- . -‘ ¢I\DJI.‘LII\JL:‘L-L_L :L‘A-~\A:Ifi‘lu3 .‘ ‘T «,1 .\r\ ,.._ ‘ ~13 r! 41.1...) U‘.‘ ppuililigssilua ~ .'niéIJ...L..—k3£:.€ L“; 5 .1-l.'.;.‘.'l‘5 Ly Robert John irignaa A T;:;31.5 Submitted to the Callece of Science gnu Arts Michiixz state University of Agricuiture and Appiied Science in partial fulfillment of the requirements for the aegree of M {351‘ ER 0 F SCI ENCE Deggrtaent of Geoloty 1958 4’ 7’3"? ._ ;, _ / 'v- 1/ 75’ 7".) DEDICATION To my wife, Mary, and my parents, Mr. and Mrs. ln.b. Brigham, without whose financial and moral help this work could not have been completed. ACKNOWLEDGMENTS The writer wishes to express his appreciation for the help and encouragementof his major professor, Dr. H. B. Stonehouse. He is also indebted to Dr. Justin Zinn, Dr. J. H. Fisher, and the other members of the geology staff for their helpful comments and criticism. He wishes to thank the Department of Soil Science for the use of its equipment and Mr. K. Pretty, Mr. B. Allen, and.Mr. G. Uehara for their kind aid and assistance. The help of Mr. E. Carter and Mr. J. Brigham in the excavation of the samples is gratefully acknowledged. A». lid/ESTIGATION Or" TC'I‘AL Aid) eliCL‘iArausglblni .-'i.—..~.Q.ii'\s.$i:. .15 A iii-Knb‘ Cr" CCRKLJTI‘IRJ Safifillinn-Cat'LJB 55.9112;be .0 j] Rooert John brigham ff ‘7'1‘2' "" ltddlaeuql 4. This worn at enpts to grove the hypothesis that total C" minus eicnnnu sole cetion content in artillaceous sediments gives a fixed value, representative of the anoint of the cations present in the clay structare, which can he used for correlation. Total and exchangeacle man¢snese have seen ueternined colorometrically in some varveo glacial clays to see if the fixed value is constant within an individual Verve anu variaule between varves. Total manaanese content proved to be similar for the three varves analyzed while exchsnieaple nenieiese varied within as well as between varves. The differences in exchenteable hencenese are shown not to ue correlative with beCEfltflbé of clay in the sample or with the clay uinerelogy. These differences are nought to es cue to the con— tribution of usngnnese ions froa manganese tearing ninerals in the silt fraction. Rani OF CCLIimTS INTRODUCTION IdnTHOD T£I& Ry Definitions 0133 Strsctgre Ion Exchence Chemistry of Replacement "- ‘ " '7‘ u p F 4- ‘y - q‘ - p» , ,' - '. .- OLCJrrence oi hjfl JGCSU es s Replacing Effect of WeatherinL on hanganese LC- CnT l C 2. iii; Sail-LL: G PRC CEDL;ES ALD RESVLTS Coloronetric Methocs Total uvun :.nese E>zch,n elee thtflfl:88, Resin method Exchangeable Mantanese, Auaoniun Acetate Methou ) Pb Exchange v3-3C ty 0 iechanical Analysis X“ KAY Ali ALYSI 3 AUDITICKAL AAALK 315 ISCLSSICI C? 373bnT3 AhD CCLCLLSION t! l (l‘ J—‘l—J U": \x‘ W C\ C“ \r' -\] ation Exchen H C) 'e Canacity of Clay Minerals II Asounts o Exchangeable K;z;enese, Resin Method III Anodnts of Exchenieeole Manganese, Asaonium Acetate'fiethod IV Particle Size Listrisution of Saiples LIST OF FIGURES I Oltline Map of Michitan II Section of Varves III Per Cent Transmission vs. Parts Per Million Manganese IV Mechanical Analysis V x-Ray Analysis VI Differential Thernal Analysis M H W \C CD \r' \N- U 'l INTRODUCTION Correlation of sedimentary deposits is an important tool which the geologist uses often. It is seldom that he can trace a deposit visually for this is possible only where it crops out. When he is searching for oil accumu- lations, the beds with which he is dealing are almost always completely concealed by overburden making it necessary to utilize the physical characteristics of a deposit in order to recognize it from well cuttings. In addition to visual comparison, some of these characteris- tics are mineralogy, mechanical analysis, chemical analysis, micropaleontology, and geophysical measurements. Arenaceous sediments lend themselves well to mechanical analysis because the particles are easily disaggregated and are large enough to be classified as to size and mineral composition. Carbonate rocks are often correlated chemically because of the ease of putting them into solu- tion. Argillaceous sediments, because of their small particle size are more difficult to work with. For mechanical analysis they require the use of the laborious pipette method. For chemical analysis it is necessary to use the highly reactive hydrofluoric acid to put them into solution and their small particle size necessitates the use of x-ray techniques to determine the mineralogy. Differential thermal analysis is of questionable value for correlation. [U The PUPPOse of this research is to investigate a new method for the correlation of argillaceous sediments which might be nore convenient than others that have been developed. Metallic ions are adsorbed onto and may be removed from the surfaces of clay particles by the mechanisu of ion exchange. If such exchangeable ions are characteris- tic of a particular clay or shale horizon, then, by the simple procedure of renoving them and analyzing colori- metrically, correlations may be made. If, as seems more likely, however, the exchangeable ions are affected by circulating ground water, then the exchangeable ion con— tent will oe dependent on location and will not be charac- teristic of a single horizon. Moreover, total ion content, made up of exchangeable ions and fixed ions incorporated in the crystal structure, should also not be characteristic of a single horizon. By subtracting the exchangeable ion content of a particular element from the total anount of that element present a residual value or fixed ion content would be determined which was free from the effects of ion exchange. This value should more nearly represent the amount of the element which was present in the material at its formation. Since clay is commonly the weathering product of a number of different minerals, one would expect the elemental content of a clay to vary depending upon its origin. However, material from identical source areas,weathered and deposited under identical conditions, should have sinilar residual values. Therefore it seems probable that the fixed ion content of the residual could he used as a neans of correlation. This research is an investigation of the fixed ion content of some glacial clays of anown age to see whether correlation by this method is possible. METHOD For developing the procedures, it was decided that samples fron a varved glacial lame deposit would be used. Varves are the fine grained oottom seuinents of glacial lakes which occur in pairs of coarse and fine layers. (Flint; 1947, p.369) The coarse layers are tenerally silt and the fine layers clay. The advantage of using varves is two fold. Being layered they can ce traced visually to provide an absolute checa on correlation and since a varve is generally thought to represent deposition over a single season it nay be assimed that conditions of sedimentation and source material were relatively constant for a single varve. For this worn, manganese was chosen as the ion to be analyzed. A cation was desired for which the analytical procedure was fairly simple and accurate. The addition of potassium periodate (K104) to an acid solution contain- ing trace amounts of nantanese, upon heating, gives the pinK permanganate color. The intensity of the color is proportional to the concentration. The color is very stable and will persist for months. A spectrographic analysis1 was made of a sanple of the varves which showed manganese to be present in determinable amounts. 1Courtesy of Dr. E. J. Benne and 3. Bass of Agriculture Chemistry THEORY Clay as a term is difficult to define. It is used as a rocx tern to describe an "earthy, fine trained material which develops plasticity when nixed with a linited amount of water". (Grim; 1953. 9.1) It is also a particle size term describing the snallest size fraction. Its maximum size is a matter of debate. Most geologists follow the Wentworth trade scale and call any material whose particle size is less than 4 nicrons clay. Grim (195:, 9.2) believes the upper linit of clay particles should be 2 uicrons because above this size natural ma- terial fails to show clay nineral characteristics. Here clay is used as a mineral term. There are a number of minerals having a characteristic structure which usually occur in particles of less than 2 nicrons size. There are two basic strictural units which are common to most clay minerals, a silica tetrahedral layer and an octahedral layer consisting of combinations of aluminum iron or magnesium with OXYgen. Most clay ninerals are made up of combinations of these two layer types inter- spersed with sheets of water nolecules. The layer com- binations are relatively free to slip on these water sheets thus providing clay with its characteristic plasticity. Ion exchange is a property of Clays which is not present to any observable extent in the larger size fractions. It is the adsorbing of ions onto the surface of the clay where they are held in exchangeable state. They will remain there until exchanged for other ions. Exchange capacity is measured in nilliequivalents per hundred ¢rans, a nilliecuivalent Ltinc one thousandth of a ¢ran atomic weight. Cation excnande is nuch nore connon in clays than anion exchange and is better understoodg only cation exchan¢e will be considered here. There are three causes for cation exchange in Clay minerals. firiefly they are: l. Broken bonds. Broaen bonds at the eeie of the unit cell rive riSe to unsatisfied charpes. These V chartes can be satislied by the adsorbtion of an ion. 0) This type of exchan;e p euouinates in minerals such a xaolinite and hanoysite. The finer the particle size, the greater will be the number of UFOKED bonds per unit mass presented as exchan e sites. i... \— 2. Substitutions within the lattice structure. When trivalent aluminum substitutes for quadrivalent silica in the tetrahedral lattice layer, or ions of lower valence for aluminum in the octahedral layer, a net negative charge is formed. This can occur either on the basal cleavage or the edges of the plate, but it is most predominent on the flat cleavage surfaces. Grim (1955, p.133) believes that the aluminum substitution for silicon procuces such a tight bond with a cation that little further exchange taxes place. He states that re- placement of the aluminum in the octahedral layer is prObably the major substitution causing cation exchanbe capacity. Replacement is the major cause of cation ex- change capacity in montmorillonite and vermiculite. 3. The hydrogen of exoosed nydroxyls. The hydrogen of exposed hydroxyls may be available for replacement by suitable cations. This could be an important factor in the two layer types because of the exposed hydroxyls on the basal cleavage. The ranges of exchange capacity for some of the clay minerals are shown in Table I. It can be seen that the Table I Cation Exchange Capacity of Clay Minerals, In Milliequivalents per 100 Grams Kaolinite 3—15 Halloysite 2H20 S-lC Halloysite 4H20 40-50 Montmorillonite 80-150 Illite lC-QO Verniculite 100-150 Chlorite 10-40 Sepiolite-attapultite-polygorsxite 20—30 clay minerals with the highest exchanbe capacities are montmorillonite and vermiculite. These clays have an expanding lattice. Their structure is such that between each set of three layers water can penetrate. The cis- tance between the layer depends on the numcer of layers of water molecules which penetrate aha is governea by the nature of the exchange ion present. This very greatly increases the area available to exchange. However, an ion between the layers is less easily exchanteu than one on the surface. The order in which ions will replace one another varies amon5 clay minerals. Ross (quotes in Ranxasa and Sahama, lSBC) gives the following series for relative ease of replacenent in nontmorillonites: 4" 2* + -+ .+ .+ Li ortation of Mn. Another inportant factor is the p of the aeueous solution. A low pE will cause solution ane a high pH will bring acout fixation. The presence of s oliu calcium cartonate will tenu to print non-reversible precipitation of nanZanese as the cioxice. The effect of the oxication reuuction on exchangeable nanLanese in soil is shown in the following diagram: MngQ MnC2 Rec. MnC Red. Rec. Water .1 ananic "'1" Me. 11528130118 ‘ 7 Exchanceaele " ’ Soluble Cxices Cx. Oxide Ox. Ox. It can he seen that as theoxiuation state is reuuceu, the solubility of thenantanese is increases. Unuer reuucinb conuitions the ins: uole nan " nic oxice convert to the nooile uanganous state. Further reuuction eases the Mn soluble enouch to be sole to tens up exchange positions on the cla' as ionic uanganese. A snall percentage of the man 13686 is in water soluble conuition. This system is in dynamic equilicriun anu as oxication recuction condi- tions change the anount of exchangeable nanfianese will be shifted. Fujinoto and Sherman (1346) investigating manganese toxicity in soil found that auuln¢ sulfur to increase the acicity increased to a great extent the amount of exchangeable nanganese as ciu aecing organic fistter- They found that the amount of exchanteable 15 nananese coulu ce reuuce; oelow crusheu limestone. I I] COndltiOhS of is iepenient on "46‘ va soluoility. oxiustion toxic levels oy euoin 7 V sunnury, it is Seen that the cisposition of san- ese after weathering frog the pirent igneous material reuuction which LOCATIOK AND SAMPLING The varves selected for sampling are those described by Bergcuist in his paper in the 1350 procedings of the Michigan Acadeny of Science Arts and Letters. They are exposed in the bluffs along Lane Michigan at Miani Park Beach, four miles north of south Haven, Michigan (map). The bluff stands 90 feet above lake level at this point. The upper 35 feet is a bluish-trey pebsly clay till. Below this is a 36 foot section of varved sedinents which are described by Bergquist (1950) as glaciolacustrine. These in turn rest upon another till distinguishable only by position from the one above. The varves themselves differ from the typical varves in that they are extremely variable in thicaness, from a few inches to two feet for both the clay and sand layers. Bergquist (1950) states that the lack of uniformity may possibly be due to near- shore deposition of the sediments in an iceborder lake of relatively short duration. The sand layers grade upward into the clay layers in what the writer chooses to call the transitional zone. However. the separation between the sand layers and the underlying clay layers is at times sharp and other times transitional. The sand is rather fine, light yellow in color, and completely unconsolidated. The clay layer contains two zones, 3 blue zone sharply separated from an upper brown zone. The transitional zone is composed of finely interstratified silt and clay. 13 OUTLINE MAr CF MICHIGAN FiZure I Lake Superior 5.: 03 re :1 '8‘ "" (D x cs ,4 Miami Park Beach Detroito c-- --"-----‘_----- : o . I Sample site 0 The sample site is in a deep 9ully which is situated at the end of the northernmost road leudin; into Miami Para Beach. About twenty feet below the contact uetween the upper drift ane the varved sediments a sixteen feet land four feet deep trench was duZ,to expose a section of the Verves free from slope wash. The section with thiCADZSEbS and sample hampers is shown below. FiZure II SsJTlCE C5 VAAVLS & l O ._.__....___ oo‘o"L‘ -.—._.‘»~- ‘—v . . . . . ‘ . . . . Transition 1 foot O 0 Clay layers l, 2, and 3 were sampled at the eastern end of the trench, at the center of the trench, and at the western end. EnouZh of the clay layer was taxen to fill a four hundred nilliliter beaaer. Care was taxen to sanple equally the blue and brown zones. The samples were then air dried and Zround in an agate norter. fROCLLURES Ann AESbLTS COlDPlJétFlO aethous —' A colorixetric nethoe lundansntally consists Ol treatin; a solution of a substance wits a reaZent in such a way as to produce a color which is progortional in intensity to the amount of the substance in the solution. (Snell & Snell, vol. l, lu4o, ;.l} Ascoruan to the Laioert Beer Law, the anount 0; light which will be ao- soreed by a solution is directly proportional to the con- centrut on Cl the QLSOFelHC molecule This is expressed s. natheiotically by the equation log %3 = asoc where I is the intensity of light transmitted by the sanple and 10 is the intensity of lith stridinp the saaple. "as" is the absoroancy coefficient of the particular s0lute azd de- pends Ugon the anelenzth of lith, the solvent,and the ten erature. The thickness of sample throubn which the light passes is denoted by b and c is the concentration of the solute. The writer chose a wavelength which gave a naxinun absorbency coefficient for ne.¢anese, 525/5 and plotted the per cent transnission ii for a ranZe of concentration from 1 to lC ppm nantanese. A clans con- taining all the reagents but no manganese was used to calibrate the colorineter at 100 per cent transmission 10-- The resultant plot (fig. II) is a straibht line on 31-10; paper and therefore aZrees very well with the Lambert Beer Law. In deternininc the auount of lélfe III 4‘ . GOHHHHS pom mphmm OH m o w .fim ‘/ _ _ _ ._ _ _ _ c ; ouocmmnas COHHHH: non magma .m> scan-afiucuns no poam ucxsstmsueam iuss J93 lJ exchanbeahle and total nanLanese oresent in the sanples sufficient solvent was used to trin: the parts per nillion within the range of the standards. The methou used to develoo the color is that ;iven in Shell and Snell (124:, vol. II, 9.33%). It was modified oecause the concentra- tion of sulphuric acid used caused precigitation of \ calciun sill tes which clouded the solution. Calciun Q sulfate is solutle in dilute sulphuric acid tut insolucle in concentrated. When the anonnt of sulghuric acid was cut from 2 ml to 1 nl the grecipitate disatoeared. In all cases duplicated sangles were run and if they varied by gore than l ger cent transiission were redone. " Best results were Outainéd when an additional half bra- :5 .\ oi gotassiun o riodzte was added after color development A Total Manganese The procedure for the analysis of total uanganese is essentially that given in Snell and Snell (vol. II, 1945, p5383) for soils. Periodate was used for color develop- ment rather than the per sulfate nethod as recommended. Two hundred milliliters of solvent were used in developing the color. Sanples M1, M2, L3, W3, and E3 were analyzed to determine the variability between varves and that within varVes. The results are shown on the following page. infl‘llav llllllll'lliijl viiillullv '1. i 2C _ Ppm in Saiple Size 1 gran Saaple No. To Trans. Solution gpm in Sample Ml 64 2.1 420 M2 05 ' 2.2 440 M3 64 2.1 420 W? 64 2.1 420 53 65 2.2 440 Within the ligits of accuracy of the nethod there are no discernable uiflerences in total mantaneSe between or within the varves. Exchan eable Manbanese, Resin Method For deternination of the exchangeable cation content it was decided that a new method utilizing exchanée resins would be investigated. A letter of inquiry was sent to the Rohn and Haas Conpany, Resinous Products Division, regarding the use of their research grade cation exchanbe resin, anberlite IR 120. They expressed an interest in the project and sent a complimentary pound of the resin. IR 120 cation exchange resin is an artificial organic compound with high eXChante cagacity. It is conposed of sulfionic acid groups which have at their surfaces large numbers of exchange sites. These exchange oositions can be filled by any cation. However, preference is shown for ions of larger ionic size and or higher valence. If cations of lower valence and or smaller ionic size are present in sufficient concentration they will replace the 21 other cations. This sane type of reaction occurs in anion exchsr 1e ,e resins except that the exchange sites have posi- tive instead of nedative charges. These Characteristics naxe exchande resins extreaely useful thn in industry and in research. Resins are generally charéed with snail, low valence ions. When solutions cozguaining ions of hi-Cher ctrerge or larger size are passed thr O L3 ‘ ’: ms in exchange for the low valence ions with which they are saturated. The ions adsorbed in this nanner Can he recovered by flushing the resin with a high concentration U) of the charging ions. Thi is shown as stripping or eluting. The Lreater the affinity of the resin for the adsorbed ion the higher will need be the concentration of stringin; ions to eisglace it. Norually hard to segarate substances, the rare eartns for example, can be separated by placinL then on the resin and very carefully adjusting the concentration of the elutant. For the deteruination of exchangeable nanbanese, it was necessary to snow that concentration of elutant, in this case HCl, would be required to concletely remove the manganese fron the resin. Known anounts of manganese were placed on the resin and then were stripped off by Various streneth elutants. It was founa that about 10 milliequi- valents of HCl oer nilliliter of resin at a concentration of it oer cent were necessary to congletely remove the manganese. P) f\,; Tests were run to ceteruine the lenpth of tine re— quirea to glass a ¢iven anoant of manganese on the resin. Four garts per million manganese in jt’ni mater mere season with four 5C 11 portions of resin for 1C, 20, 3C, ans 4C minutes. In all four there was complete absorotion of For nost excnange worn the resin is placed in a Class coluan sue the ion tearing solutions are passed through it. The solutions can then be fOlthEQ by the elutant. To apgroxinate these concitions, three trans oi clay were Shanen vith a liter of mater. This sueaension was allowea to pass throuih a colann of resin, however, the resin Very effectively screenec out the clay. It was feared that to effectively uisgerse the clay woulo uoset the nancanese equilibriun thereb\ giving erroneous results so this method was abandoned. The next attenpt has to nix the clay and the resin directly in a snall volune of water. A {ran of sanple E3 was aided to 25 ml of resin in lCC ml of water. The nixture was shaken for an hou . After the first few shakes the corn was blown from the flasa. The identity of the gas being evolved was estaolishec as 002. A possible explaination would be that exchante releases a sufficient quantity of hydroniun ions to cause breaacown of the carbonates. After shaaine, the clay was rinsed from the resin by repeated decantations with cistilied rs.— n -’-'-.2 water. Fifty nilliliters of 3C per cent HCl was auuea anc snaxen with the resin for half an hour. This was youred off ans another 50 nl was auueu anu snaaen as before. The process was repeateu a third tine. The first, second, and thiru iecantations were analyzes se- parately and the following amounts of manganese were determined: 1 53 resin 10C ml solvent first stripping 61E trans. 2.4 ppm second stripping o9; trans. 0.6 ppm third stripping 97$ trans. 0.1 pgm Total 3.1 ppm Pros these results it was cecided that this would be the proceoure followed. Another test was naue to observe the effect of pH on exchanteaOle nanéanese. Four two bran samples of Ni were treated with .1 normal H01 to give PH'S of 7, 5. 3, and l. A fifth saaple was left at the pH of the soil, 8.7. The samples were treated as before with the excep- tion that the three strippings were boiled to cryness together. pH Per Cent Trans. ppm 8.7 44 4.0 7.0 43 4.1 5.0 43 4.1 3.0 42 4.2 1.0 41 4.3 Pt) 1 It was felt that a deternination nace at the soil pH would Le nost characteristic since 9% varies between soils. The amounts of exchanéeatle mantanese in the varveu saagles as determined cy the resin method are shown below: Table II Per Cent 1 gm clay lCC nl solvent Bangle No. Trans. 933 in sol. _;;m in clay El 61 2.4 24C 52 56 2.8 280 E: 32 9.2 320 M1 57 2.7 270 M2 57 2.7 270 M3 30 3.4 340 W1 oC' 2.5 250 W2 56 2.s 280 W3 53 3.1 310 It can Le seen fron the results that variation in the amount of exchangracle manganese within a single varve is nearly of the sane na¢nitude as the variation oetween varves. This could as due either to inadequacies in the method or to variables such as percentage of clay and tyoe of clay which affect the exchange capacity. Exchangeaole Manganese. Annonium Acetate Method An attempt has naee to chech the effectiveness of the resin nethoe by coaearing the results with those Obtained by a commonly used aethoa. Saturatin¢_the clay with a hiih concentration of cations such as ammonium or barium will exchange off the cations absoreeu on the clay. The auounts of these can then he deteraihec in the leachate. A proceaure involving the use of ahuoniun acetate is given by Schollenberger anu Simon (lye5). The samples were shaken in 256 nl of neutral l nornal aunoniun acetate for two hours. The leachate was then filtered off in a Buchner funnel and three additional 25 pl portions of aanoniua acetate were passeu through the clay cane. The acetate was eoilec off anu the resiuue analjsea as before. Table III Samples K0. Per Cent Trans. epu Soln. 22D in Clay El 57 2.8 22.4 E2 45 3.9 31.2 E3 46 3.5 50.4 Ml 45 3.? 31.2 m2 4} 4. 32.8 '3 \J“ ¢~ bl .{l H H \y-S [\J (D 2'. P U] .q R) O) N N .b W2 46 3.5 30.4 W} 39 4.0 Lu.8 1‘.) CW The anount of man anese eAcq-n.eu eJ this methoc is less than with the resin by a factor of ten. However. the F€l&‘ tive anounts are sinilar. It would ao'ear thit the resin ‘ nethoa gives results at least as v>liu as these. $- Exchange Capacity The gossibility that the Variaeility tag due to exchanLe capacity was also investigated. The anaonium saturated clay from the QPECEGQiHé ex erinent was rinsed free of excess anaonia with ethyl alcohol. The aesoreed aaaoniun ions were then forced fPOJ the exchange sites by leaching with 10 per cent KaCl. The exchange capacity was aeterained b7 Kjeleahl distillation of the auuonia and titration with .l norual hGl. The aethou is given by i.on in the reference sited acove m g' . Ll) Scholleheerger with the exception that hJeluaLl distillation was used in olace of Ness lerization. 1. Exchange Ca:acity Exgre ssed as Mec ¢lCCgL El 8.03 Ml 7.C3 W1 0.65 E2 5.36 M2 3.5} W2 5-C3 E} y.CQ M3 8.18 h} 8.25 There are definite differences in the exchange capaCity as given by this netr od but they do not seen to correlate with the exchanéeable na ganese. To pursue this line .2 f'urther it was d cided that a mechanical and glneralotical analysis of the claJ was indicated. as} $'¢;3"""fi"'3 '2’ vv‘rtjvoi Aflva-LLLLJ.‘ Cu.«J. .\LJ;,.. [0 The procedure for mechanical analysis is es entially (D iven uy Lru'neein and Pettijohn (19;;5, 9.1;} ). [\J Tenth normal souiun hygroxiue was used as a ”ispersinL a ent and the settlin. cylinders were theriostated in a C \— J 'cath at 29°C. An int resting refineaent was a jig which (1' l allowea the pipette to he hcle in glace laterally over the cylinder and then lowered snoothly into the suspension an exact measured distance. The results of the mechanical analysis are shown numerically in tanle IV and graphically in fiiure IV. The amount of clay present in each layer is seen to be fairly consistent within the layer but eoes not correlate with the anount of excha geahle uanganese as determined by either method. w . . . . so.om Re.HH mo.s ss.mfi no.0 wm H sm.o m \ o \ o 0 OJ 1. \ o 0 . so on em e «a m as p Rm am s» 0H em 0 my “H.cs sm.,fl RH.QH no.mfl mm.e me.fi mm.o as Ah... am.ww «s.ma £9.0H se.sa ao.oa mw.o we.n em Nm (\J H . ‘ IQ O o C) N x \o \ V“ H “ ‘0 \ L‘ V” sn.em we.mfi me.flfi as. \ o) s 0.. .0, .\ 0 0) \JO 0 . so am we ed an eH we ta 9e _ me o as o Hm mm.fi mm.H- a.n m.w- w.e m.e- m.mH @.mH- N.Ha m.Hw- m.me m.mm eonssz mfimsmm , \ wwqméfifl @O ZOHHDfiwflanal flNHW flqowafiém ......... >H oflnwe I! Fi;gre econodfi adv access ouam adnhadcd Headednooa apeaa 9213 uI quaoaaa K-RAX AMALISIS The use of X-rays has gained much goeularity as a means of aeteriinin; clay mineralogy. It is quite a reliable method and procedares are easy. A short explana— will saffice for an anaerstandin: of the results. Procedure The clay fraction has separated iron the silt oy repeated decantation. A measar;d gortion of the susgen- sion was eVu-OF&tbd to dryness and the residue weighed to deteraine the concentration of clay. Next a plaster Lloca acadt an inch quare and an eithth of an inch thica (I) was placed over a suction flasg. Enoach suspension was sached throa;h the Llocu to plate out about 30 milligrams of clay. Twelve nilliliters of three per cent glycerol solution were then passed throuth the bloc& in three- portions. After air dryin:.the blocx was X-rayed. A similar amount of 0.1 normal hCl solution was passed through the blocs. The blocs was heated in an oven at 110°C for two hours and X—rayed again. The oloca was then heated to 500°C for two hours and X-rayed a third time. The three X-ray tracings were stadied to determine the nineralogy. Theory Reflection of X-rays by clay minerals is goVerned by the inter—layer distances (d L the angle of reflection (2Q), anc the wavelength of the rays (A), according to Bray 's equationlfll = 2d sin e. E" oeservini the angle 29 at whicn maxindn reflection occars, and referrinr to a table (Larrish and Irmin, ljib) usint the erooer wave- len th, interlever soacin: Can ee read directly. (I 4- \u.’ Interpretation of Results As noted before nontnorillonite and verniculite are three layer minerals kith exgandin; lattices. Treatnent with glycerol Mill insert tto layers of this n terial between each set of three layers of nontnorillonite. This will enpahd the nontnorillOnite so that the distance fron the top layer oi the set to the too layer of the next incladint the glycerol layers set will ce 17.7 an;strons. If a pean occurs at this distance it is an indication of nontnorillonite. Vernicaiite hill allom only one layer of glycerol and will show a gees at l4.o angstrous interlayer distance. Mica (usually illite) and Kaolinite will not be affected ey this treatuent. Their pedhs occur at lCAO and 7A0 resdectively. Treating with potassiua and heating to 110°C drives out the interl yer QlJCcFOl frou nontaorillonite and vernicaiite and collapses the distance to 10 angstroms. If this collaose is noted it is farther indication of the presence of these ninerals. If a pban reusins at 14.3 angstron it shows the presence of Chlorite which has the sane interlzyer distance as vernicalite but is not -' f. ‘ '1 1‘ 3“ colleoeaole. I‘d \el HeatinC to BCCOC breaas down the exposed hydroxyl layer of kaolin and the disagpesrshce of this seas is an indication of the Jineral. :elow 7A0 the geaas are higher orders of the ones outlined aeove with the easestion of a v ' fl ' ‘ “-‘1 ' r~ .72 7. 9Cmt. “it: to £1431th t JQJ‘KOQ Results AJCljStS were ran on the clay and silt fractions of '_‘ . ' ~v_ \ - r‘ , “... 4. '-_‘ f .. . , ; .“ I. .,.,- ‘ ., “ll, mg, m;, N}, and L) b0 dcecI-the ll tittLC were 5-“. ssggles correlative differences. There here no differences in the reslits so only those of one s:u;le (31) will he shown here. The clay geese which occur in figure V are listed below Mlth their nose ole siLnificahce. Chlorite 1433 Yeruiculite kaolin 730 2nd order 0; 143° 5A9 and order of lCAO 4.65 )F& order of l4A3 3.5 2nd order of TA0 1 2 7, , :, ~ 1»,o quartz There is not enough of a gees at 17.730 to show the presence of nontnorillonite. The seal at 14A3 does not d1 seo'ieir 3.5.0:) heating and therefore is due to chlorite - ,s A. b not vermiculite. The pens at lCA disappears upon heatinb X-daY nNALYSIs Figure V Intensity of Ref C O 1"! 4.1 C d h H 4.) H v. m C! 14.30A 10. 00.x. 1 j 70001; g : 4.65A leotion 14.50A 10.00A O O ‘O 0* ID 9 .p - A 'U :3 I LSJX o 4-3 G 0 .G L to I: '6' o.32a -l==:::::::ac,q, D. U) 14.30A 2 P: d l‘ .l\ H 1Q. DUI; 8 4E: F! 7 o 00.7’1 g ycoratod “ I’D!!! .. {I‘l‘fiil .Xlls \v. ’l ' . ‘ ,. 1" I -’A 1;- - " ;' "' “ r‘ '- ‘ to )CC :10J1h, JlCa \giDcsolJ illite). The peel at {0A indicates kaolin out this will have to ee confirneu oy a \. -lacial lade clay which was stociee, exchanceacle in the C anianese increases generally cohhmarc anc MES not COngetelJ correlatiVe within the sane varve. This trenc is anooaious with clay content use exchante capacity. The fact that the governing exchange capacity Seen to eXert little effect on the anouht of manganese :iceec a; L] the resin acsorgtion nethoa of analvsis leoes the triter to celieve that nan- ganese oxices 'o the silt fraction or the clay contribute a larger amount of nanbanese than hoes the clay fraction. This icea is corne out o; the fact that varying the 3H (0 from e.7 to i groouced only slitht increase in exchsnte- able nancanese. The increase in exchangeable' uangsnese somewarc may possicly be explainec by iocreasinbly_reuucing coneitions with ceoth. Non~excnanseacle cation content, While not shown here to ce effective nay yet, oy further research, grove to be of value. The resaits Iron different areas groves that total anc exchangeacle nanianese eoes vary in clays. For for her more, the writer saogles he cispersec cy sheainL in crox ther free i O I] froi ice. Iiu;zainonia “fund; fill t 6D} allowini the separation of fFOJ exchan.e effects. Tots; sotiests that clay _---. , . . . 1,“ uliLJLL-C admoulud [AJ- he exchen;e sites the cl ey I'racti on , . ‘ . - r- _. _ , A . . ‘. .‘ .. ' r. I . 1 ‘ ‘r g _ ‘ 4. 5‘ --l_ :JK C_3£(CJ. SinLAlu -'- lV'C tint I eSLueAClJ. UOthI’Jc O; brie V analyzes withoat the nasaing effect of ostricitions the silt Ir ction. “I \(N 12. :IBLICQRAIHY Azlerican Society for TestinC Materials (loos) SinolatIVe Alphaeeticsl inc grilébo hanerical 47- 4 a- ’ h I ' I? I 1"... .I " 7‘ ‘. .‘ ‘ I" r- r IdeALA Ci (i'At/‘V ulill :ctl-Dn gotta- Lnisaal Cccarrence of estern ginniLan”, ragers oi cieoce, Arts, rho Letters I '-.,ichi-'Cen Ire: s, An.) Are-or. Flint, R. F., {lo+7), Glacial Geoloiy one the Ilei°tocele 54°C! gout) (Kile... she Stuns, 1.40., Itch ford. . - ,., ... ~ , - ' H Laullj 20, .10 (0, 2'1”“ 3"le'£].!1, L,- ‘_.o, (\l/fil‘} “CLLJVLOL 0L .. AJ‘L'.\-.JL-C :L“ tL-C 5.3.14.1, 30.1.4. SCLCIJUG, “14.411.113 ‘.;J'\A "ll.in: C“. 3;. 4 it; ore. __ _ \ r1 r a 'f‘. “‘ar ‘: v _a ' ', ' (L'J/I V‘LC‘.£____~'11*19-LO_F: z 3 L‘qufti‘h'diiJ. 340‘ .1 371., Inc. , Kev. Yorn. Frin'ein, W. 3., an; Eetti'ohn, F. 5., (io;;) fianual of Seeinente‘ .ry let Io rxgku,, .5 ,wl to 4-C',toi -orolts IiiCo, i‘utw Karts. ,,_:‘ ‘ ‘- ‘_ .. ,.. . ' , D ‘ ,r_ 1" , B. d... ,ki/‘J/l JL- 'v-z LOP Ar-;‘C‘L‘L J s tor Solatio n of bfctée (; versos é one 2 e1, Ihiliij' s Lrtoratories, 3W 4 .. M (195C) Seocheoistry, L.fl iVersity of Ch "0 C S‘ C) y H; F {3 U) C) o p .. PJ. C 0'5 C Sanaell, g. 3., (L,++) Colo rinetric pet er sination of Trace Metals, Interscience Puclisk-ers, Inc., New Yord Schollennerger, C. J., one Simon, R. h., (1345) "Exchan¢e Capacity and Exchsn, eacle oases, AflJODidfl Acetate Method", Soil Science, «'illi ans an; hilsins Company, Baltimore. Snell, F. 3., and Snell, C. T., (134:) Colorimetric Methocs of An lysis,‘Vol.I. L. Van Norstrsnc CO-, Inc., New Kora ,(1954) colorimetric‘flethods of Ana1781s, Vol. II, D Van NorsEranH to., no. New York m USE um afinn r ‘ ‘ ‘ UfiateW Demco-293 I l ' l A! R l l 8" I! I l L' l l I 132 Y In? I llHllNflIHH