5:: ,_:_,_._=_: , A 22::5.3.3.52! . I y C .s. o ., \ ‘-‘ , u .. 1 a. \s o _.0 u w . _ ‘ 1...... “.3 ohu. . \ \ 71 - ll. 1 . .- .‘. I» . v o..\ \ .o “11‘ .“wb . I ,0.» . m. o _ Q 3 .i .s '.w. . .b This is to certify that the thesis entitled A Study of the Relationship Between pH, Exchange- able Calcium, Percent Base Saturation, and Lime Requirement in Some Michigan Soils presented by Neil F. Shimp has been accepted towards fulfillment of the requirements for Mam degree in __S.Qil_.Snie me e # Major professor Date May 2. 1951 0-169 A STUDY or m RELATIONSHIP 13mm pH. momemu mama. PERCENT BASE SATURATION, AND LIME REQUIREMENT IN SOME MICHIGAN SOILS By NEIL F. 83111? W A THESIS Submitted to the School of Graduate Studies of Michigen state Cellege of Agriculture end.Applied Science in pertiel fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Soil Science 1951 THESIS ACINOWLDEGMENTS The author would like to express his sincere appreciation fer the assistance and advice given hime by Dr. Kirk Iavten during the course of this investigatien and in the preparation of the nanuscript. He is also indebted to Dr. L. ll. Turk fer his constructive criticism of the manuscript. The writer acknewledges the helpful suggestions and coopera- tion given to hin by Dr. J. Q. Lynd and by his fellow graduate students. ‘255884 CONTENTS Intreductien........... Review of L1terature . . . . . . . Experimental lhterials and lietheds Experimental........... Discussion............ 8nmry.............. Biblicmpwo...oo..... Page 13 36 38 to LIST OF TABLES Tables Pas- 1. The Location. Depth of Sampling and Texture of 3011 Types U8“ 0 e e e e e o e e e e e o e o e e e 8 2. The Rolationship Between Soil pH and Cation Exchange Capacity. Percent Base Saturation. and Exchangeable Oalciun in Bone Michigan Soils . . . . . . . . . . 1h 3. Determination of Line Requiruent by Weedruff “tthOOOOOOCoooeooeeeeeee 16 A. Effect of Addition of Line on pH of Sblected Seils 18 5. Lime Requirement Values of inchigan Soils by Three “(rematchmulmtmueeeoeeeeeeee 23 6. llechanical Analyses of 15 Selected Soils am; the W4rometerfleth“.....-..........o 31 LIST OF PIGURES Pigures Page 1. Apnreximate Locations of Soils Used . . . . . . . 10 2. Exchangeable Hydrogen Vs. Lime Requirement Carbonatellethod o..............20 3e pH VI. 0‘003 Adm (8.1”t0d 8011‘) e e o e- o o e 21 2;. pH Vs. Percent Base Saturation . . . . . . . . . 2h 6! 50 pH VI. kahangeab'le cdcilIDe e: e e e o e e e e e 6. pH Vs. Lime Requirement (Ioodruff Method) . . . . 27 7. Percent Base Saturation Vs. Line Requirement (‘l'oodruff Method) . OOOOOOOOOOOOOO 28 8. Relationship Beheen kchange Capacity. Percent Base Saturation. and Lime Requirement (he Methods) ...................29 9. Exchangeable Calcium Vs. Lime Requirement «Omuffmth“)oeeoeeeeeeeeeoe 32 to. Base kchange Ca acity Vs. Lime Requirement (WOWfbthOd oeeeoeeeeeeoeee 33 11. The Percent Clay in the Soil as Cmared to Lime Requironntbyr'omthdaoee-ooeeeeeo 3h. l A STUDY or THE RELATIONSHIP BETWEEN pH. EXCHANGEABLE enema, A PERCENT BASE SATURATION. AND LIRE REQUIREMENT Ill SOME MICHIGAN SOILS INTRODUCTION In soils there are certain general relationships between pH. exchangeable calcium. percent base saturation. and lime requirement which have been examined by a number of investigators (13. 1h. 16. 18. 22. 25). However. there is a need for more information concerning the specific aspects of these relationships in Hichigan soils. One of the most important of these for successful crop production is the correction and control of soil reaction. This -i-ediately brings up the problem of lime requirement or the amount of lime which met be added to bring the soil to a desired pH value. In the past the most simple of the chemical methods for estinting lime requirement has been the determination of soil reaction. Bowover. on soils of varying cation exchange capacities it is almost impossible to base accurate liming values on the hydrogen ion concentration alone. Per example it is commonly known that two soils having the same pH may require considerably different amounts of line. This variance is largely due to differences in clay md organic utter contents of soils. Likewise. since the percent base saturation is a soil property which is not directly related to the buffering capacity. it would seem that this characteristic would also be limited as a measure of lime require- ment. Since soil pH alone has proven unsatisfactory as an accurate measure of the needs of lime for soils. other chemical methods have been proposed over a period of years. flany of these procedures are ' based on sound chemical principles and give accurate values for line requirement. Such methods attempt to take into consideration pH. base exchange capacity. and percent base saturation when determining lime requirement of soils. . It is the purpose of this work to stuw some of the relation- ships between pH. percent base saturation. exchangeable calcium. and lime requirement and to compare several methods for the determination of lime requirement. REVIET OP LITERATURE In order to study the problem of the need for lime in lichiytn soils. it is necessary to review the methods for lime requirement as well as the relationships bet-men percent base saturation. lime require- ment and pH. According to Pooch and Bradfield (21). line requirement methods my be listed under the following headings: (a) determinatien of exchangeable hydrogen; (b) rapid determination of the lime requirement; (c) determination of soil reaction; (d) determination of exchangeable calcium and degree of calcium saturation; and (e) determination of readily soluble aluminum. iron and manpnese. Practically all the rapid methods in determining lime requirement involve the determination of exchangeable hydrogen. The first group of methods to be considered involve the titration of acid soils with a base. Veitch as reported by Truog (27). was one of the first to propose titrating the soil to a phencphthalein endpoint with lime water. This naturally ave high results. Bray and Delta]: (3) used a solution of KCL to replace the hydrogen ions and then titrated the extract with M03 using bPeme thymol blue as an indicator. It has been pointed out. however. (20) that pH values of sodium are higher than those of equivalent amounts of calcium. In the methods using potentiometric titration of the soil. Pierre and Worley (23) have shown that the pl! of soils in the laboratory are higher than those in the field when equivalent amounts of line are added. To correct this they introduced a liming factor of 1.5. Run (7) also found that additions of a solution of Ca(OH)2 to the soil gave higher pH readings than did additions of CaCO3 as measured by the glass electrode. Hardy and Lewis (8) developed a method involving titration of the soil with Ca(OH)2 in the presence of CaC12 to pH 7.0a. Peech (20) has shown that the presence of CaClz will produce lower pH values even though the equivalence point is unchanged. 1 second type of method for line requirement is a single extraction. Here the exchmgeable hydrogen is extracted with a salt solution and the extract titrated with a base. Peech (20) has pointed out that extraction with 1303. as proposed by Hopkins (27). e..- not give complete replacement of exchangeable Wdrogen. He has also shown that the use of calcium acetate. as first given by Jones (27). tends to give low results on heavier soils because calcium acetate solution is strongly buffered at too low a pH value to effect complete replace- ment of exchangeable hydrogen. 1 better suited method would seem to be one using a buffer of p-nitrophenol and lime water which is Schofield's (22;) method. The p-nitrephenol is partially neutralized with the Ca(OH)2 and is strongly buffered at pH 7.00. Upon addition of the buffer to an acid soil a measurable amount of the calcium is taken up. Innes and Birch (10) have shown that this method gives low results as compared with the Bradfield and Allison method (1) or lehlich's method (12). The method of Bradfield and Allison (1) uses a buffer of “#01 - .011! with respect anon. This is strongly buffered at pH 740. ' The difference in titration values before and after addition of the buffer to the soil gives the values for exchangeable hydrogen. liehlich's (12) method makes use of barium chloride-triethanelamine buffer. This procedure is essentially the some as that of Bradfield and Allison with the buffer replacing the exchangeable hydrogen. Both the Bradfield and Allison and Mehlich methods have been shown to compare favorably (10). Brown (5) by using normal ammonium acetate and pH determinations developed a simple means of determining lime requirement. By titrating the ammonium acetate with an acid. the number of milliliters added are plotted against pH depression. Then. by adding the amcniunr acetate to the soil. the m.e. of hydrogen in the soil can be read directly from the pH depression caused by the addition of the soil to the buffer. The pH changes in the buffer are small. however. and extreme accuracy must be exercised (20). The most recent method for determination of lime requirement in the buffer group is the Weedruff procedure (28). In this method the buffer consists of a mixture of p-nitrophenel. calcium acetate and ugnesium oxide. which is used to adjust the pH to exactly 7.00. The buffer is compounded so that when mixed with the soil each 0.1 pH unit that the buffer pH is depressed is equivalent to one m.e. of exchangeable hydrogen per 100 gm. of soil or 1000 pounds of M03 per acre. Two methods involving color intensity have been used to some extent. The earliest is Comber‘s (6) which uses an alcoholic solution of potassium-thiocyanate to develop a red color with the soluble iron. The more acid a soil is the more intense will be the red color due to soluble iron. This method is mch tee empirical because of other factors besides pH that influence the solubility of iron in the soil (20). Sieling (25) has developed a colorimetric lime determining method using copper. A solution of cupric acetate - acetic acid is added to the soil sample. The amount of copper left in solution is measured by adding NB‘OH which gvies a deep blue color. This method has been called sufficiently accurate for practical purposes by Lucas (11). However. in his comparisons with other methods it is not always in complete agreement. There has also been considerable work done on the inter- relationships betwoen pH. percent base saturation. and line requirment. Hissink (9) was the first to designate the term percent base saturation and point out its importance. Bray and DeTurk (3) did not find a close relationship between pH and.percent base saturation in Illinois soils. Below 6G1 saturation of the soil's exchange capacity there was very little correlation. However. above this point a better correlation was observed. Pierre and Scarseth (22) found that soils of the same reaction may vary considerably in their percentage base saturation. Ibrgan (l6). Peech (18) and bhlich (13. 11;) have all found similar results. These investigators have found a direct relation between pH and percent base saturation. However. it is not a close correlation. lbhlich (13.1h) has attributed this variation of percentage saturation at the same pH value to differences in the exchange complex. He has stated.that the base unsaturatien -- pH relationship is a specific expression of the nature of the base exchange complex present and is therefore not in- fluenced by exchange capacity or buffer activity. .iccording to Sieling (25). indications are that. in general. soils of higher exchange capacity require greater quantities of lime for neutralisation than do soils of low exchange capacity at the same initial pH. Incas (ll) has found an excellent correlation between lhne requirement and cation exchange capacity. EXPERIMENTAL MATERIALS AND METHODS The soils used in this experiment ranged in texture from sandy soils to clay soils and were taken from twenty-three different counties in llichigan. The majority of those were in the southern half of the lower peninsula. The soils studied. together with their texture. depth. and location by county are given in Table 1.. The approximate loo tions are shown on the map in Figure 1. All soils were air dried and screened through a 20 mesh sieve before using. ANALYTICAL METHODS Determination of pH -- a 1:1 soil-water ratio was used with a lo m.eample of soil. The soil suspensions were stirred at intervals during a 15 minute period and the pH values. measured with a Bookman pH meter. Determination of base exchange capacities -- the anionium acetate method. as outlined by Peech (19). was employed. In this method a I0 gm. sample of soil was extracted with l. pH 7.0 amniun acetate. and leached with 9.5% ethyl alcohol. and the ammonia displaced by sodium. The ammonia was then nesslerised and readings made on a photoelectric colorimeter. Determination of total bases -- the method given by Bray and Fillhite (2) was used. The ammonium acetate leachate from the base . exchange capacity procedure was divided exactly in half. we aliquot of leachate was used in the determination of total bases. while the 8 TABLE 1 THE LOCATION, DEPTH OF SAIvIPLDVG AND TEXTURE OF SOIL TYPES USED ‘s'Si'f fiction Depth No. Sgi_1r Type County of Mich, or Layer 1 A Hancelona Sandy Loam Kalkaska 6-31. inch 2 Bellfontaine Sandy Loam Case 8-18 inch 3 Plainfield Sandy Loam Cass 6-22 inch 1. Wales Sand Benzie 0-6 inch 5 riainricid Sandy Loam Cass 0-6 inch 6 Bellfontaine Sandy Loam Cass 7-11. inch 7 Homeland. Sandy Loam Kallcaska 0-6 inch 8 Kaikaehe Sand Dennis 6-21. inch 9 Bollfontaine Sandy Loam Case 0-? inch 10 Warsaw Loam Kalamasoo Surface 11 Fox Sandy Loam St. J oseph Surface 12 Bellfonatine Loam Kalamazoo Surface 13 Plainfield Sandy Loam St. Joseph Surface ll. Hillsdale Sandy Loam Inghu Surface 15 Plainfield Sandy Loam Clinton Surface 16 Wauko sha Sandy Loam St. Joseph Surface 6A8 Fox Loam Branch Subsoil 7A8 Pox ieam St . Joseph Subsoil ioiS Miami Clay Calhoun Subsoil BIAS Arenac Sand Saginaw Subsoil 75AS Napanee Clay Macomh Subsoil. 3013 Macomb Fine Sandy Loam Saginaw Surface 101AS Oceans Subsoil Kent Silt Loam 9 TABLE 1 - Cont'd. THE LOCATION, DEPTH OF SAMPLING AND TEXTURE OF SOIL TYPES USED "s71? . . Weaticn Fepth No. ngiLTxge County of Mich. ~ or Layer 71AS Miami Loam ' Lapeer Surface 59AS Iccheiia Silt Lean Isabella Surface 15AS Berrien Sand Lenawee Surface 21AS Miami Clay Loam Clinton Sub soil 97AS Isabella Clay Ottawa theci1 MS Billedale Loam Branch Subsoil 2A8 Hilledale Loam Hillsdale Subsoil MAS Conover Silt Loam Lenawec Subsoil 98AS Berrien Sand Ottawa Surface IOOAS Kent 01w Oceans. Subsoil. lB Conover Loam Calhoun Surface 53AS Napanee Silt Loam Sanilac Subsoil 26AS Brady Sandy Loam Ingham Surface 3A3 Hillsdale Loam Branch Surface 96113 Conover Loam Imis Surface AZAS Colana Sand Livingston Surface 5A3 Fox Loam Branch Subsoil 1A3 Ccnover Loam Calhoun Subeoil 27AS Colcma Lem Send Inng Surface 8As Mimi Silt Loam Cass Subsoil. 89AS Onaway Loam Alcona Surface 10 FIG. 1 APPROXIMATE LOCATIONS OP SOILS USED 44K: .5 UPERIOR mucuro ‘ I H QNTONAGON .7 l- ' 1-: I 81‘. RAGA rj L.- _L_ .4 605m I MARQUET TE I“ “I ImcxmsflJ (momma j .—" I— 8 i I LUCE ALGER l SCHOOLCRAF'T _ . _ 1— [— DELTA .1 IRON I J‘!" \ -_..r‘I .’/' 9W \\ i LEELANAU \\ I 1 . 09 \ \- (7 [EELMWJ BEVIE MANISTEE! WEXFORD I -_l _I.. LAKE ”r- MASON ._ II_... 1W“ NEMGO — I uusxacoij OTTAWA' I KENT e l .... .L. ALLEGAN I LAKE I———+‘ lass seamen. e 6—- QwvomII fl .1- 'OSCLOLA! CLARE IGl-ADW' ' MECOSTAi ISABE I 5" _. _ . I— ‘1_ .1..- J...— CHIPPEWA WI lam —- -I masoue ISLE _1._. MONT mouucvl— 1—'—Ir—' [— _ r1 ANTRIM - OTSEGO ——-—1—. mssauxiiaoscomouI OGEMAW l I _...u._ _1'_LT-L_ meme 1 “I'm MIDLANOI— —l _.J— MONTCALM —I:WIOTI ”GINA“, —!—'."I— I IONIA | CLINTON Isnuwm ..I._I_i_-I-_. BARRY I EATON _Lj..L.fi L’! VANBUREN IKALAMAZOO! CALHOUN I JACKSON IWASHTgNAwi mm: 9L... v 11'! iiJOSEPHI. ammo "mama! Lemma: [MONROE l .1... —‘.—- . -i-—-—-L.. l mesa i mcum Iuvmcsmul _t ALPENA GRAND lumswcmwronu oscooal ALCONA ITRAVERSEI. . I iIOSCO mean I; '—l r" "I OAKLAND. mo“ I ‘k 11 other portion was required for the determination of exchangeable calcium. Dotormimtion of exchangeable calcium -- The above mentioned aliquot of ammonium acetate leonhato vac used for the determination of exchangeable calcium. It In evaporated to a volume below 100 ml. and brougxt back to a 100 m1. volume with dictilled mater. The flame photometer uood vac a Perkin-Elmer flame photometer. model 521. The procedure followed mac that outlined by l’cth and Prince (26). Ibthodo for Determination of Lime Requirement - . l- Calcium carbonate method - additicno of precipitated M03 were made to 100 gm.oamploo of coil. 0n light textured ecile theoo additiono more ndo at ratoo varying from 1000 to 8000 pounds per acre. 0n the heavier ocilo the application" of 0.003 ranged from 2000 poundo to 12000 poundo per acre. Thooo ocilo were incubated in a moiot condition for three: months. After incubation the ocilo were air dried and the pH moaourod. 2- llethod of Bradi’ield and Allioon (l) - l'ooogram oampleo of coil more thoroughly mixed with 100 ml of ammonium chloride butter oolution. The buffer conoioto of l ammonium chloride - .01 l with roopect to ammonium hydroxide and with a pH of 7.1;. The mixture of coil and buffer was allowed to etand for one hour and filtered. Twenty-five ‘millilitoro at the filtrate were then titrated with .01 I m. uoing methyl rod ao an indicator. A blank of twenty-five millilitoro of buffor oolution vac titrated to the can. end point and 12 exchangeable Wdrogon measured by difference between the two titration values. 3- loedruff buffer method (28) - Veodruff's buffer solution consists of a mixture of 8 go. of p-nitrophenol. ho gm. of calcium acetate. and 0.62 gm. of upesium oxide per liter of solution. It is adjusted to exactly pH 7.00 with 1&0 or dilute mm as required. 'ron gm. soil samples were mixed mith 20 ml of buffer solution and allowed to stand for 30 minutes. A p]! determination was then made on the sample. Prom this pH reading the lime requirement was determined by observing how much the addition of the soil to the buffer hd lowered its pH value. This is called the pH depression. The buffer is so compounded that when mixed with the soil each 0.1 pH depression below pH 7.0 is oquivalont to one m.e. of hydrogen or to 1000 pounds of Ga003 per acre. h- Bouyoucos Hydrometer lethod (it) - This method was used for the mechanical analyses of selected soils. In this most recent method. as outlined by Bcuyoucos. a dispensing agent of sodium hexamotophosphate is used and only We readings taken, no seconds and two hours. Other stops in the procedure are. in general. the same as have been in practice for a. number of years in making mechanical analyses vith the hydrometer. 13 EXPER DENTAL For each soil the pH. cation exchange capacity. percent base saturation. and exchangeable calcium was determined accnrding to the methods previously given. These basic soil chemical data are presented in Table 2. The values for the determination of lime requirement by the Woodruff method for all soils are given in table 3 along with the pH depression. In Table I; is listed the increments of Ca003 in pounds per acre added to 15 selected soils. some fine and some coarse textured. Six treatments were carried out for each soil. The additions of line for both light and heavy soils are given along with the pH value. recorded after a three months moist incubation period. with that particular increment. from these data the limo requirement value was considered to be the increment of CaOOB which brought the soil sample closest to a pH of 7.0. By using the limo requirement data obtained with the carbonate method and plotting. them against exchangeable lwdrogon obtained by the difference between the cation exchange capacity and total base content of the soils. a definite relationship was found. This is shown in Fig. 2 where it is observed that the lime requirement increases regularly with the exchangeable hydrogen in the soil. 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H . . H - - . . U . _ . . . w -I.I.-T-I- -I III--1?- ..- . ._ .. _ . H .V m . . . . . . . . . I II.II II I H . > V M _ . _ . . I I I v I I».- - -I- I I . a . _ . .I . . I”- ... -III .- . . . » . _ . p I . .l.\1. ... .. I . _ F A. . . - . 4 Av . . . ‘- . r # .. . . _ fl _. . . . d I . h 4 . . g w. . vIILIIIIL .IIILIIIIIHIIIIT A . . A . . _ H I lizw-I-I. A III .QI I i I I I II ..4-IIfi II . . H .. . a _ . . I O IIILIII oII IIIIbV I I I 1H g _ * . . V. . _- -I.I V- --. V . . _ M h I: -I--- V. - - - - H . _ u . V. . - . fl . . . H . ._ w I. F1 . h H - _ . . * . 4 U - - . _ rI . . u . - - . .-. I. I I ATII .I III-I1 . > I .. u . . _ .— H . W ...II I ......I‘III.I Io I«.IIII-I: - ...- . . . . . . . V -:--I-::- - . . . . V . . . _ III! ¢-III¢I..IAYIII.4I I “-III .. . . . .. H n . . _ k ...o- 4 I-IIII. .II.I.’ L. . . . . v _. . . II. II ...-III.-1IIII1I.II+ -.--JIII v.1-I . . . ¢ . . _. . ~ _ . B- “ II A u‘II-IIV.II ~.00II VII-IIIHIIII.Y-IIIIHII . . .. .. . . . n V . _ .. m . H IIIATIPI I I1 .. . - .. V _ . . V H . H V _ - _ . N...-VII. . V . V . V . p a “ _ L . a . IIILII IO-IIIIIII I . I I II - II ..I . m . o h . A _ . a a . _ I - LIIII II . k . . . II - v I I II IIIIJ-I-IIWI ”- -I - I IN- - V . ~93. D m-Hmddwongénwvfim _ d? m . . . H . . I.-.-I-. V :.TII -I.V.II--V..-.-_+-III . M . . “.. P.CF . . - ¢ . V In-.IuaIvuIa.”IIIIAI.anoII-Ilv.wllb.- I.«. Y .I . . . U f --.-It...- VVI.VIII-fit-.-V.I-.V.M-.-I.-.I-V-- V H V D g _ . . . ... . . . V .. _ . . _I . .-I - V II . . _. .M . n .. M . .. u . .. . . I + m A .. * . h. . II>.II. L . . H. N IF u I 26 given p8 velue. euch ee 5.5 in Pig. 1;. the percent beee eeturetion ney renge from as low ee 15% to ee high ea 75% for e number of different ecile. Pig. 5 dete of pH end exchengeeble celcium were plotted to eee if e definite relation enxiete betIeen theee two soil prepertiee. Prone the ecetter diegren it 12. doubtful whether there is e reletieng By oxenining enly the left hend portien of Pig. 5. the pH ie neted. to increeee with deoreeeing celoiun. This is Just the opposite of whet one night expect. However. by cleee exeninetien it ie eeen thet the ecile with higher pH weluee end lower exchengeeble celciun contente here reletively low cetion exchenge cepec itiee end therefere do not require e lerge eneunt of celciun fer complete eeturetion. lltheugh thie obeerwetien is net borne out tee well in fig. 5. it ie eupheeized beceuse later figuree chew e einiler reletionehip to e much greater degree. By compering pH with Voedruff line requirement vqluee in Pig. 6. e definite reletionehip ie neted; ee pH decreeeee line requirnent increeeee. Although thie cerreletion ie greeter then thet between pH end percent beee eeturetien. the fect reneine that the peinte on the diegren ere still: widely ecettered. Since there is e cloeer cerreletien between Ioedruff line requirement end pH then is exhibited betnen pH end percent beee eeturetien. it ie only logicel thet there eheuld be e rather leeee reletionehip between Woodruff line requirement end percent bece eeturetion. These dete ere shown in Pig. 7. There is e noderete decreeee in percent beee eetureticn with en increeeed line requirement ooww ooow comm coda oowm mom . A _ A ._ W H gamma omanflnmmw Iwmwaum 3 “Hum. Sum... 1:... I I _L I I I I I I I I I I I I I I I I I I I I I I . I I I I I #M I I I L f I I I I I I I l I I MM} 44 I IIIIIII:;-IM ..-”.MII—a ...... A I I I I I I r; MM_. “-..—‘4 . ....-.———.. e < .1 .-- M .. PI _ . _ _ u M _ _ n _ v ,e1.:M - -- . .-M I e-- ,M.-._ I ..- .--- - -. . -mr --. .v . - . - A- . 4.--- - M- -- M , _ M M M _ . _ M . M .. . M A _ U . . M _ M e.” _ A . M IIIIIIM I I II|+ IIIIIII IMIII... IIIIR II IIII II I IIIIII+IIII|II LT! IIIIIIL IIIIIIILI I.I. 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M M . 4.1 A III I -Mv I . - A M M . M “- IMMIIII MII . M w M M M M. . . M 4.- . F A M. A . A- .- IA A - . A - A. A A F A .I. -AM . . M - I- . - ..... I; - .- I O _ O - .- A A .. A i A . . A - _ A A.-. -. A .--A.-:A A ICI IMI AH - - I. M . A A “ M A - . - I I- -I .-.--.fI-II . . . MA. A - I M. LIIILI- AI I.. M M . . . A M M M f . H M . . M M M A _ . . IIM .III. III-IIIJIIAII ArIIIIrI IM 4 . M M H M I In. I I -I MI: I o I II . I II - .. .. I I . M M _ . M M - _ IIWI quIAIIIII-TII L1 H M . M .I M -I-M..-I I - - . MIL-I- .. M A M . . i 00 . A .. . -. I M M M M A M M . . . . - II -M-- ---..I.I-A . A . - M . . M M I .- I- A - A . . M . . A M _ MI- -I-M-. . . - IAI-o-I A MEI-.---..- _ . M M M M M M .I MI I I. M M M . M M I _ M . _ A ._ . IA I I I - O . -w- M . M. . . . M . . M MA M A O H M M - - I III I . - - -..-I? M - -Ii. . . , - . .A . . . I .- .I . . M M M M - . -I II MI- I- . .-..-- A- M _ _ . M . t M MC.» M 90 A . _ A . A . A A M ... -A.. .II - .- -..-2*.- --I. - .A Ip-I- - M . A3 . M . _ IIMII ILIII - . _ A M. M .I _ I O M M ....... . -- -II . III. M.- LIA-I- . . .A . A. - A.--.A- .A A .A s L. -A IIM-II- II M M A. M. M M M . _ . M u I I HITIIA HI A MVP A M . . . IIlrfIIILII vIII-ItM III‘IIIIrII. III. _ .M .. . L . M . M .M - M I A M A _ M M MIIAH-II..- .---I.- -. M; --- .;:--M .- L M . A . . AH . . AI _ A . A M A A A . I-I-I Ao- - .---o..-A---AAT- -- - -I I; A8 A H M r . A .F . M _ A M . M M M A _ M III .Wflq. Io II fi-II I I I I M .M M _ _ 4 I. IA . - M H M A M A ..J -M. -.AITIHIILII- A M A . . . A M A. M M M1 - O . I. - - A I . MI .- M I: --I II.-I....I-- ..-; .III-flv. -I I...- ILI..- M . M . M A M _ . M- I. rH my . . . M M _ A A.- - 1M:-.A . :I- M21: .IIL- -f A A. .. M H _ ,0 III - . .A A . .. AM A A -.- -- MI? I. -.--I -- I III . M . A M M . A .- .M I I M, _.I w _ A M A _ A . . . A . A A I III - I . . ..... .W - 4MII II . II II .II. AII I. I c IIIIM ._ M M M M . M . M M M H» A A A . _ . M w- I--. - A . . . . . M . _ A. . . . _ . _ M .-.-I-I- - - ..... 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Pig. 8 has been included to explain why a definte correlation betseen percent base saturation and line requirement should not be expected. In this graph two different mthcds of line requirement. Bradfield and Allison. and Weedruff. are plotted against percent base saturatien. Both lime requirement methods in Fig. 8 show the line requirement nines to be higher for the soil with a greater exchange capacity. even though the percent base saturatien nlues are nearly equal. A similar relationship was previously shun in Fig. 3 betseen pH and line requirflent. hchangeable calcium and line requirement velues are plotted in Pig. 9. In this diagram exchangeable calcium is definitely shown to increase with an increasing requirement fer line by the seils. Once again. as in Pig. 5.. this relationship might net be expected. A reasonable explanatien is that soils which have higher line require- .nents (and higher calciun contents) have larger exchange capacities. hen though the calciun content is relatively high. it requires censiderably nere, line te saturate the exchange complex et a soil with a high saturation capacity than it does with a low capacity. hen these ebeemtions it weuld seen plausahle to conclude that determinatien of exchangeable calcium is a peer indicater fer line requirenent of soils. The ilportent effect of catien exchange capacity en line requirement is illustrated in Fig. 10. A relatively constant increase 31 .von: no: 395.... .3 on c apogee .23 com .603 0353 .3 8a a... .333“? 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III-..-.. . . _ E .39 _ I .- I 1. . . H . ... 4.. I 4. . .. . ... ...-14.-..-- 1... I. _. .. .9 om m ._E: 2 6E . .- _ -. . I. .. . . . . III-711----.. . . . _. _ . . 4 .w 4 I ...-4. . 4 _ 4 -4 m .4 , -.I-.I.- ...1...I.II- I. -.-I .....IH-II. II “II. .. .H .. . . 4 4 . . . 4 _ . II. . . + . H .4 35 in line requirement as calculated by the method of Weedrufi' is accompanied by an increase in bass exchange capacity. All relationships thus far would seem to indicate that cation exchange capacity is one of the predominating factors in determining line requirement for soils. 1! this is true. then some relationship between percent clay and line requirement should be expected. In table 6 is presented the nechanical analyses for 15 selected soils obtained using the Beuyoucos hydroneter nethod. The percentage of clay for each of these soils has been plotted against line requirement as calculated by toodrui'f's method and the method or Bradtield and Allison in Fig. 11. The relationship in both cases is only fair. since in all cases line requirement does not increase sith percent clay. Indications are then. that percent clay should be used in compaction with other soil properties such as organic matter content in order to he of value as a line requirement indicater. 36 DISCUSSION From the foregoing experimental work. the factors influencing lime requirement determinations are seen to be numerous. To choose any one of these (such as exchangeable hydrogen) as a basis for line requirement is very likely to involve some approximations. This becomes evident when results of the three methods. used in this study for obtaining lime requirement values in soils. are compared. Since they are not in close agreement. it is evident that there are factors either in the soil or in the methods themselves which are not being evaluated correctly or in the same manner. It is possible. then. that one source for variance in results when determining lime requirement by various methods is the extraction or exchangeable hydrogen. Bradi'iold and Allison's buffer solution. at a pH of 7.1;. might be expected to extract more of the total exchangeable hydrogen than would the ammonium acetate or Voodruft's buffer at a pH of 7.0. Ioodrui‘i‘ (28) has stated that for soils at low base exchange capacity his method for evaluating lime requrment may be as much as #33 below the actual requirement of the soil. By using the carbonate lime requirement method as a standard,this investigatien did not reveal Weedruff's method to give results below that or the carbonate method with any more consistency en 11¢: textured soils than on soils of heavy texture. There were no indications that the Veedrui‘i' method was subject to any more error than the other methods compared with it. This along with the fact that it is the simplest and nest rapid method of 37 any used in this investigation should serve to emphasise its value as a chemical test for lime requirement. The relationship betseen pH and percentage base saturation. which has been considered previously in this work. has been given attention by Dhlich (13.11;). He has stated that the pH - base saturation relationship varies for different soils because of differ- ences in the predominating exchange complex in the soils. 31s results have shown that the pH - percentage base saturation is too imperfect fer the soils studied to permit its use as a single factor for lime requirement values. However. the relationship is fairly constant on all soils with the same exchange complex or soils of a specific soil type. The results of this investigation tend to corroborate his work. 38 SUMMARY The objective of this. investigation was to study some of the relationships between pH. exchangeable calcium. percent base saturation. and lime requirement in some Michigan soils. The soils used were gathered from a number of different counties in the lower peninsula of mchigan. The above mentioned chemical soil properties were determined for all soils used and the relationships were shown by plotting them in a series of graphs. Three methods were used for the determination of lime requirement and thenresults compared. lechanical analyses of selected soils were completed to show the effect of clay on the lime requirement of soils. is a result of these studies the following statements can be nude: 1. pH alone does not give an accurate liming value for soils of widely varying textures and exchange capacities. 2. The quantitative determination of exchangeable twdrogen is probably the best known method for determining lime requirement. since it correlated more closely with the lime requirement when compared to the other soil chemical properties studied. 3. The methods for determining lime requirement compared as 4 _ _ 4_!.._. 5. Im— A_ r “ follows: The Bradfield and Allison method gave consistently higher results than did the Weedruff method. h. The pH - percentage base saturation relationship is too 3 39 imperfect to permit its use as a single factor in lime requirement deter: inat ions . 5. Lime requirement as calculated by the Weedruff method exhibits a close relationship to the soil pH. 6. There exists only a very limited correlation between lime requirement. as calculated by the Woodruff method. and percent base saturation of the soil. In general. soils of higher exchange capacity require greater quantities of line for neutralization than do soils of low exchange capacity at the same initial percentage base saturation. 7. The determination of exchangeable calcium in soils is a poor test for lime roquirsnent. since exchangeable calcium. in general. increases with increasing lime requirement. 8. There is a close relationship betwoen total base exchange capacity and lime requirement in soils when considering soils of similar pH. 9. The Woodruff buffer method for determining limo requirement was the simplest and most rapid method used to determine lime require- ment in this study. The results obtained by the Woodruff method compared with the carbonate method as well as did the method of Bradfield and Allison. l. 2. 3. A. 5. 6. 7. 8. 9. 10. 11. 12‘. no BIBLIOGRAPHY Bradfield. I. and Allison. W. B. 1933 Criteria of base saturation in soils. Trans. Second Comm. and Alhli Subcomn. Internat'l. Soc. Soil Sci. A: 63-79 Bray. 3.3.. and Willhite. P. 1!. 1929 The determination of total replaceable bases in soils. Ind. Eng. Chem. Mo Id 13 IMo - _ "J -. and DoTurk. 32.3. 1931 field method for line requirement of soils. Soil Sci. 32: 329-3“. Bouyoucos. G. J. 1951 A recalibration of the Wdrometer method for making mechanical analysis of soil. Mich. Agri. kp. Sat. Unpublished data. Brown. 1.0. 1923 A rapid method of determining exchangeable hydrogen and total exchangeable bases of soils. Soil Sci. .56: 353.357 comber. I. l. 1920 A qualitative test for sour soils. Jour. of Wis 8°10 108 “2042‘s Dunn. L. B. 191.3 Lime requirement determinations of soils by means of titration curves. Soil Sci. 56: Sal-351. Eardy. P.. and Lewis. A. E. 1929 A rapid electrometric method for measuring limo requirement of soils. Jour. of Agri. Sci. 19: 17-25. Hissink. D. J. 1925 Base exchange in soils. General views. Trans. Farady Sec. 20: 551-566. Innes. R. P.. and Birch. B. I. 19115 A comparison of four methods for the estimation of exchangeable hydrogen content of soils. Jour. of Agri. Sci. 35: 236-238. Lucas. I. B. 191.2 Reliability of lime requirement claculations based on the rapid copper method for exchange capacity. 8°11 3°10 8000 Cf he PNOo 7| 362-367e liehlich. A. 1938 Use of triethanelamine acetate-barium Wdroxide buffer for the determination of some base exchange properties “d 1110 "quira.nto SO11 8°10 Soc. ho P700. 3. 162-1660 13. 1h. 15. 16. 17. 18. 19. 21. 22. 1.1 __ —-——:___ —. 1941 Base unsaturation and pH in relation to soil type. Soil Sci. Soc. of Am. Proc. 6: -=- - __- - . 191.2 The significance of percentage base saturation and pH in relation to soil differences. Soil Sci. Soc. of Am. Proc. 7: 167-173. =_-- —— —————— . 1942 Base saturation and pH in relation to lining and nutrient conservation of soil. Soil Sci. Soc. of Aflo PTOOe 78 353-361o llargan. I. f. 1939 Base exchange capacity and related characteristics of Connecticut soils. Soil Sci. Soc. of Am. Proc. 11.: lbs-M9. Parker. 1‘. I. 1929 Determination of exchangeable Wdrogen in soil. J.uro .fu‘lo 80°o Agrcn. 293 1030-1039o Peech. M. 1939 chemical studies on soils from florida citrus groves. Fla. Agr. Exp. Sta. Bul. 31.0: 1.50. __ _— - . 191:5 Determination of exchangeable cations and exchange capacity of soils -- rapid nichrometheds utilising centrifuge and spectrophotometer. Soil Sci. 59: 25-38. -------...-------, 191:8 Chemical methods for assessing soil fertility. Diagnostic techniques for soils and crops. The American Potash Institute. Iashingten. D.C. pp. 1-52. — w — - ----- . and Bradfield. R. l9h8 Chemical methods for estimating lime needs of soils. Soil Sci. 65: 35-55. Pierre. I. H. and Scarseth. G. D. 1931 Determination of the percentage base saturation of soils and its value in different soils of definite pH values. Soil Sci. 31399-1111.. -— - - 2. and l’erloy. S. 1.. 1928 The buffer method and determination of exchangeable hydrogen for estimating the amounts of lime required to bring soils to definite pl! values. Soil 8°1o 26' 263-325o Schofield. R. I. 1933 Rapid methods of examining soils. 11 The use of p-nitrophenol for assessing lime status. Jour. Agri. 8°1e 238 252-25ho Sieling. D. H. 1942 The relation of base exchange capacity exchangeably hydrogen and soil reaction to the lime requirement of lhssachusetts soils. lhss. Agr. Exp. Sta. Bul. 388: 32. #2 26. Toth. S. J. and Prince. A. 1.. 191:9 Estimation of Cation exchange capacity and exchangeable Ca. K. and Na contents of soils by flame photometer techniques. Soil Sci. 67: 1.39-1.45. 27. Truog. E. 1938 Soil acidity and liming. U. S. Dept. Agri. Yearbook 1938: 563-580. 28. Woodruff. C. 11. 191r8 Testing soils for line requirement by means of a buffered solution and the glass electrode. Soil 3°1o 668 5343s l I I II I l l I' I I l