09v..- -QOMM—“-o“\!0-. SEASONAL VARIABILITY OF pH AND LIME . REQUIREMENT IN SEVERAL SOUTHERN MICHIGAN ‘ SOILS WHEN MEASURED IN DIFFERENT WAYS Thesis for the Degree of M. S. MICHIGAN STATE UNIVERSITY JOHNNIE B. COLLINS 1967 IIIIIIIII IIZIIIIIILIIIII II III I I III; I III I L ,3 R .4 R y Michigal, Statc University SEASONAL VARIABILITY OF pH AND LIME REQUIREKEKT IN SEVERAL SOUTHERN MICHIGAN SOILS WHEN MEASURED IN DIFFEREN WAYS By Johnnie B. Collins A Thesis Submitted to - Michigan State University in partial fulfillment of the requirements for the degree of Master of Science Department of Soil Science i967 ' LIZ-U .— : -u.‘— ABSTRACT SEASONAL VARIABILITY 0F pH AND LIME REQUIREMENT IN SEVERAL SOUTHERN MICHIGAN SOILS WHEN MEASURED IN DIFFERENT WAYS By Johnnie B. Collins The variability of soil pH and lime requirement was investigated from May through September. 1966. at nineteen soil sites representing thirteen southern Michigan soil series. The experimental errors in pH determinations were also studied. To be reasonably certain of a significant difference between individual soil pH measurements a variation greater than 10.3 pH is necessary. However. when mean soil pH values of a representative number of observations are compared. dif- fgrenoes greater than 30.15 pH unit are likely significant. On the average. during the wetter portion of the sea- son. the air dry and oven dry soil pH values (measured in water) were approximately 0.5 and 0.8 pH unit lower. respec- tively. than the corresponding field moist pH values. How- ever. during the drier portion of the season. differences between the average pH values measured at the three moisture conditions were less than 0.1 pH unit and non-significant. ‘Ihere were also no significant differences between the averages of the air dry and oven dry soil pH values measured during the season. The field moist soil pH values measured in water showed the maximum seasonal variability and the air dry soil pH's measured in 1.0NKCl showed the least seasonal variability. The field moist pH's measured in water showed a maximum var- iation of 1.6 pH units and an average variation of 0.8 pH unit during the season. Similarly. the air dry soil pH's measured in 1.0NKC1 showed a maximum variation of 1.0 pH unit and an average variation of less than 0.2 pH unit during the season. The field moist soil pH values measured in water were positively and highly correlated‘with organic matter content. This is probably due to the combined effect of the relation- ships of organic matter content to field moisture content. and field moisture content to electrical conductivity. The seasonal variability of the air dry pH's measured in water were negatively and highly correlated with electrical conduc- tivity of the samples. Most of the soil sites exhibited no seasonal variability of air dry pH's when measured in 1.0NK01. This indicates that soluble salts are probably responsible for most of the observed seasonal variations in soil pH values. On the average. the 0.01hCaCl2 and 1.0NKCl salt solu- tions lowered the air dry soil pH's measured in water approx- imately 0.6 and 1.0 pH unit. respectively. Regardless of method of determination. seasonal varia- bility of lime requirement was observed on eleven of the nineteen so the eleven earlier pan shoued a 1 nineteen soil sites. Using air dry samples. only four of the eleven sites exhibited a lime requirement during the earlier part of the season. but each of the eleven sites showed a lime requirement during mid-summer. SEASONAL VARIABILITY OF pH AND LIME REQUIREMENT IN SEVERAL SOUTHERN MICHIGAN SOILS WHEN MEASURED IN DIFFERENT WAIS By Johnnie B. Collins AN ABSTRACT OF A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Soil Science 1967 .H .env '-n¢ Fr... .2. ACI-Il-I C L'fLEDGI-IEI-I T Sincere gratitude is expressed to Dr. E. P. Nhiteside. the author's major professor. for introducing the author to the problem studied herein. His infinite patience. under- standing. unfailing guidance and constant supervision have been very much appreciated. -——.-—_ 9. a, .- The author wishes to thank Dr. C. E. Cress. Mrs. N. Galuzzi and Dr. E. C. Doll for their guidance in preparing data for the computer and interpreting the same. He is N also indebted to staff members of the Soil Testing Labor- atory. especially to hr. 0. Pierce. for the use of instru- ments. His sincere appreciation goes to Dr. B. G. Ellis. Dr. H. D. Foth. Dr. R. E. Lucas. Dr. J. C. Shickluna and Mr. R. White for helpful suggestions during the course of this in- vestigation. Many thanks are extended to professors and fellow graduate students of the Soil Science Department for pro- viding a wonderful environment in which to conduct this study. The writer gratefully acknowledges the Graduate ASSisrtantship provided him by Michigan State University en- ablidrg him to pursue and complete this study. ii Tv-I tn TABLE OF CONTEB INTRODUCTIOIq O O O O O O O O 0 LITERATURE REVIEW . . . . . . Introduction . . . . . Seasonal Variations of soil pH Causes of seasonal variations in soil pH Influence of salt content Influence of drying, moisture content TS of sample or rainfall Influence of soil water ratio Influence of CO2 pressure in the atmos- phere. e e e e o 0 Influence of plants and relation of pH to base saturation Influence of absorbed aluminum . Influence of organic matter. Influence of time interval between preparation and pH measurements Comparison of various colorimetric methods for pH measurements . . Accuracy of glass electrode measurements EXPERIMENTAL PROCEDURE . . . . Location of sites . . . . Collection of samples . Preparation of samples PHETHODS OF ANALYSIS . . . . . Soil reaction . . . . . . Cation exchange capacity. Total exchangeable metallic Electrical conductivity . Organic matter content . Lime requirement . . . . -REK3ULTS AND DISCUSSION . . . . Evaluation of the experimental errors in the measurement of soil pH with the glass eleCtrOde o e e e e e 0 iii 0 O O O O O eeemee Page \TU‘I 4? two) \O H 10 IO 11 ll ll 12 15 15 18 19 20 20 20 21 21 21 22 22 Variability of pH measurements made on standard laboratory check samples during the season . . . . . . . . . . Effects of different operators and different pH meters on the variabil— ity of the pH's of five air dry soil samples 0 o o o o o o o o o o o o o o Reproducibility of soil pH measurements made in H20, in 0.01MCaC12 and in 1.0NKC1 by one operator using one pH meter on the same day . . . . . . . . Variability of soil pH values measured in 0.01MCaCl with one pH meter by one operator on wo different dates . . . Variability of field moist pH values within each of the nineteen soil sites Summary . . . . . . . . . . . . . . . . Influence of moisture conditions and sus- pending media on seasonal variability of SOilpHvalueS.............. Influence of moisture condition on sea- sonal variability of soil pH values measured in water and in 0.01MCaC12 with the glass electrode . . . . . Comparison of the variability of the air dry pH‘s of soil samples collect- ed from May through September when measured in H O, in 0.01MCaC12 and in 1.0NKC1 with %he glass electrode . . Comparison of the seasonal variability of field moist and air dry soil pH values measured with the Truog kit and with the glass electrode . . . . summaryooooooooooooooo. Several Factors influencing the seasonal variability of soil pH values . . . . . . Seasonal variability of lime requirement . . iSUMMARY AND CONCLUSIONS . . . . . . . . . . . . . LIST OF REFEREIJCES O O O O O O O O O O O O O O 0 APPENDIX 0 O O O O O O O I O O 0 O O O O O O O 0 iv Page 22 26 28 3o 33 33 34 37 39 41 #2 48 51 56 63 I is 9. m. o O o o o c C a C o . c o u u o o u o o o a a o a o c o o u a o n o o a o o o 1 a a o o c 9 a o o a u o o u o c o a o u a o o c n o w o c p LIST OF TABLES Table l. 2. 7. 8A. 8B. 11). Location Of pIOtS O O I O O O O O O O O O O 0 Texture, degree of erosion, percent slope, direction of lepe. crOp or vegetation and natural drainage of the 19 sites used in this study . . . . . . . . . . . . . . . . . "Known pH values" and variability of pH measurements made on standard laboratory check samples from May to October . . . . . Analysis of variance for a three way analysis (5 soils, 3 Operators, 3 suspending media) . Summary of the variability in the pH's of five air dry soil samples measured in water, in OoOlD’ICflClZ and in loONKCl o o o o o o o o 0 Variations in the pH's of the composite and single core samples collected in the initial. sampling or eaCh plot. 0 o o o o o o o o o 0 Soil reaction measured at three moisture con— ditions and in several suspending media for each site on each sampling date . . . . . . Field moisture percentage, total exchangeable metallic cations, electrical conductivity and organic matter content measured during the season'for each soil site. . . . . . . . Cation exchange capacity of each site, and the base saturation percentages and exchange acidities of each site determined during the seasonoooooooooooooo00000 Significant simple correlations between sea- sonal variability of soil pH and field moisture percentage, base saturation per- centage, electrical conductivity and or- ganic matter content . . . . . . . . . . . . Seasonal variability of lime requirement (Tons/acre) determined by the pH plus tex- ture, S.M.P. buffer and exchange acidity' methods as determined on air dry samples from 11 of the sites representing 9 soils. . Page 16 17 27 29 32 63 64 65 46 66 K! v-27. F."- ' , _- 2. Va Se LIST OF FIGURES FIGURE Page 1. Variability of pH measurements made on sev- eral standard laboratory check samples from May through OCtOber e e o e o e o o e 0 2n 2. Comparison of pH values of all the air dry samples from the 19 sites measured in 0.01MCaC12 on two dates 0 e o o e o e e o e 31 3. Average pH's of ten soil sites measured at three moisture conditions and in two sus- pending media from May through September . . 36 h. Variability of air dry pH's of ten soil sites measured in three suspending media from May throughSeptember 000.00.000.00 38 5. Comparison of average field moist and air dry pH values of nineteen soil sites measured with the Truog kit and in water with the glass electrode from June through September . . . #0 6. Variability of the air dry pH's of five soil sites measured during the season . . . . . . an 7. Seasonal variability of average lime require- ment determined by three methods . . . . . . 50 vi Perhaps medium for 1 A activity". *3 1 are closely I Detemf Operations u of son pfi v Sideration C measured p}; the soil in 11011 of the This. in °rder 1 WNW 01 teen Site ”88151. am to 9.1 of 8011 1 In differEr Wire 00: field 1m mints. INTRODUCTION Perhaps the most important chemical test of a soil as a medium for plant growth is its pH value or "hydrogen ion activity“. The solubility and availability of many nutrients are closely related to soil pH. Determination of pH is one of the easiest and quickest operations used in soil chemical analysis. However, the use of soil pH values as expressions of acidity involve the con- sideration of several factors: In the first place. does the measured pH value give a true expression of the acidity of the soil in the field? Secondly, how variable is the reac- tion of the soil in the field throughout the year? Thirdly, how do the magnitudes of seasonal variations compare to the experimental errors encountered in pH determinations. This study was conducted from May to September, 1966, in.order to investigate: the seasonal variability of the acidity of the plow layers of thirteen soil series at nine- teen sites in Southern Michigan, to observe several of the INJssible factors influencing the apparent seasonal variations, EHM1 to evaluate the experimental errors in the determinations 01‘ soil pH. In evaluating the experimental errors, the effects of different operators. different pH meters and different times were considered. Consideration was given to the effect of fielxi moist, air dry and oven dry samples on the pH measure- ments. Also, the pH's of the air dry samples collected during the season 1 LONKCI sob two salt 30' was also g1 at the f 011 media: fie water and 1 T0 ‘m tion, elee saturation W of to In a tent was d McLean-Sm 8011 text: the season were measured in water. in 0.01MCaC12 and in 1.0NKCl solutions in order to determine the effects of the two salt solutions on the pH measurements.- Special attention was also given to the variability of soil pH values measured at the following moisture conditions and in two suspending media: field moist in water and in 0.01MCaClz; air dry in water and in 0.01MCaC12; and oven dry in water and in 0.01MCaC12. To help understand the seasonal variation in soil reac- tion, electrical conductivity (or salt content), percent base saturation. field moisture content, and organic matter con— tent of the soil samples were investigated. In addition, the seasonal variation of the lime require- ment was determined and compared by the following methods: McLean-Shoemaker—Pratt buffer, exchange acidity, and pH plus soil texture. m— ww— m 2 "v -—-——a pH i the hydrog my be di‘ electrode colorimet' 9.31.1“. or in Platin “Inf. of QIECtI‘Ode up to 8. 5 and hydro Ution. I tion that aluminum or the so hitable change 1:1 It ‘ “153,59, “031 the I consider a‘: LITERATURE REVIEW Introduction pH is commonly defined as the negative logarithm of the hydrogen ion activity. Methods for determining soil pH may be divided into two groups: electrometric (hydrogen electrode, quinhydrone electrode and glass electrode) and colorimetric. The hydrogen electrode (5.25) measures the e.m.f. of the equilibrium between gaseous hydrogen dispersed in platinum black and hydrogen ions in solution against the e.m.f. of a standard calomel half cell. The quinhydrone electrode (5) is based on the principle that for pH values ‘up to 8.5. the oxidation-reduction potential between quinone and hydroquinone depends on the hydrogen ion activity in sol- 'ution. The glass electrode (30) evolved from the observa- tion that the potential between membranes of certain low- aluminum glasses and a solution is closely related to the pH of the solution. The colorimetric methods (22) makes use of suitable dyes or acid-base indicators, the colors of which Change with the hydrogen ion activity. Seasonal;iagiations of Soil pH It has frequently been observed (6.7.9.18.31.33.37,#1. “5.53.59.75.78.79,82,87) that pH values of soil samples taken from the same site at different times during the year show considersmde variations. Studies of seasonal variation in -3... soil react ical test micronutri is also on tion Syste at the fa: l/‘x soil reaction are of much practical importance where this chem- ical test is used to determine the fertilizer (particularly micronutrients) and lime requirement of soils. Soil reaction is also one of the criteria used in the new soil classifica- tion system (7th Approximation) to classify certain soils at the family level, and it has very commonly been a criterion for differentiation among soil series. Therefore. an inves- tigation of seasonal variations in soil reaction should be very useful. Causes of seasonal Variations in_pH Many investigations (6.7.9.18,31,#3,44,h5,53,78,79,82) have also been conducted in an attempt to ascertain why soil reaction fluctuates during the year, and to determine the mag- :nitude of the apparent variation. A large number of inves- tigators (18,h3,h#,53,78,82) have reported an increase in soil acidity during the summer months. In some instances (#3,#4, 78) a.variation during the year of as much as 1.0 pH unit has been reported. Lrflgence of salt content JBaNer (6) attributed the increase in soil acidity dur- ing tkue summer months to the accumulation of soluble salts. Others (33,53,59,66,87) have reported similar findings. Puri,I§t2 a1. (59) and Schofield, et. a1. (66) pointed out that "natural none-saline" soils contain varying amounts of Salts: aund that soil pH is altered appreciably in the presence of even 3 that a c':: contact t tamed by it? from of even small quantities of neutral salts. Yuan (87) found that a change in pH resulted when the soil was brought into contact with a salt solution, and that the change was accom- panied by the liberation of exchangeable and hydrolytic acid- ity from exchangeable hydrogen and aluminum. As pointed out by Olson (53), probably one of the important factors respon— sible for an increase in acidity during the late spring or early summer is the relative high concentration of salts in the soil solution following the application of fertilizers. This conclusion is contrary to the results of Bell. et2 al. (7) who found that fertilizers had no effect on seasonal changes in soil pH. Influence of drying, moisture content of samples or rainfall The effects of drying and moisture content on variation Of‘soil reaction.have been the subjects of many investigations (3,6,16,19,28,4l,51.52.64). Olson (53) determined the acidity CH1 the same sample but at different moisture contents, and (Hancluded that soil moisture may have an appreciable effect CHI soil pH. Chapman, et. a1. (19) found that at moisture Cinntents corresponding to the moisture equivalent, stable ireadings may be obtained provided the electrodes are well covered with the moist soil. They also found that constant euui consistent readings may be obtained with the soil at or Heal? the "sticky point," and that differences in moisture content in this general range had but little effect on the .- . , ik’hn sue e .. Slass elec and that t are charac 3028. (13315 he. alkaline (3) Tepor 011 and at 10001:. ”Home: dry p3 VE 1°“? p3 dry gimp. Variable pH values. McGeorge (51) employed the spear type electrode and concluded that it yields values that truly reflect the acidity under any and all growing conditions, and that the readings are accurate and can be closely duplicated. Davis (28) pointed out that attempts to measure soil pH with the glass electrode below the moisture equivalent are undesirable and that there is no acceptable evidence that air dry soils are characteristically more acid or more alkaline than moist soils. Burgess (16) pointed out that both air drying and oven drying had little or no effect on acid soils but that drying talkaline soils rendered them somewhat less alkaline. Arrhenius (:3) reported the effect of drying on the pH of an alkaline £3011 and found that neither air drying nor drying in an oven sat lOO°F brought about any change in pH values. Huberty (41) cwonducted an experiment to determine the suitability of oven clrw'pH values as expressions of soil acidity. He obtained lxower pH values with the oven dry samples than with the air (irw'samples and observed that the oven dry pH's were no more variable than the air dry pH's. Rost (64) et. a1. studied 14% soils develOped from glacial and loessial materials and found that all but one beBCame more acid upon air drying. Therefore. they concluded tfluit the only reliable indication of conditions existing in the :field are obtained when pH's are determined on field moist Samples 0 Severe fluctuations Van Der Pea; alternating that the tr: 1315 wet 2r: 0f “Sh arr; deserted Si filament Pi ‘mit {‘01 8.0151 soils‘ mt Ulrika tion: and rainfall w Several investigators (6.53.82) have related seasonal fluctuations in soil pH values to variations in rainfall. Van Der Paauw (82) attributed fluctuations in soil pH to alternating periods of low and high rainfall. He observed that the trend of pH corresponds fairly closely to alternat- ing wet and dry periods: it gradually increases in periods of high and decreases in periods of low rainfall. Baver (6) observed similar trends in soil pH at the Ohio Agricultural Experiment Station and he reported variations of 0.6 to 0.7 pH unit for alkaline soils and as much as 0.9 pH unit for acid soils. Olson (53) observed no effect of rainfall on pH but indicated that if factors such as temperature, evapora- tion, and others could be kept constant it is possible that rainfall would have a decided influence on soil acidity. Influence of soil water ratio There has been little agreement among different inves- ti4§ators (2, 10.19.35.4l,50,57,65,70.76) as to the prOper 1%It10 of soil to water that should be uSed in preparation of the: soil suspension for pH measurements. Several investigators (159.41.76) agree that the increase in pH upon dilution from the! "sticky point" to a soil-to-water ratio of 1:5 may be Over 1.0 pH unit. ' Pierre (5?) found that the hydrogen activity of some Soilds were not affected by changing the soil-water ratio from 1:2 tn) 1:50. Further, those soils that showed a change in pH no longer set were leached nlticant the varying fro: no consiste: soils using varied from on 1:]. as 5 Chang be depende: Arrhenius With 3 mm 33ml 801] 1.500 Wert i“Crease, for soil- found the ratios be On that a S 1930, th 5°Clety rattic as a 1:1 I‘a vanOus (1:1) 84”. -8- no longer showed such differences after the soluble salts were leached out. Sharp and Hoagland (25) reported no sig- nificant differences in the pH's of soils at soil-water ratios varying from 1:2 to 1:500. GilleSpie and Hurst (35) found no consistent differences in the hydrOgen ion activity of soils using soil-water ratios of 1:1 and 1:2. His results varied from a minus 0.15 to a plus 0.25 of a pH unit, based on 1:1 as a standard. Changes in soil pH with different soil—water ratios may be dependent on organic matter content, as pointed out by Arrhenius (2). This investigator found but little change with a humus rich soil, but a change of 0.9 pH unit with a sandy soil (low in organic matter), when ratios of 1:2.5 and 1:500 were compared. McGeorge (50) pointed out that the increase in soil pH with different dilutions is most rapid :for soil-water ratios below 1:10. Likewise. Bradfield (10) :found that the increase in pH is most rapid for soil-water ratios below 1:8. 0n the basis of the above reports it became apparent tkuat a standard soil-water ratio was needed. Therefore, in 19.30. the soil reaction committee of the International Society of Soil Science (38) adapted a 1:2{5,,soil-w'ater raizio as the standard. However. several states have adepted a 1.:1 ratio (55), and various investigators have adopted V8”Pious ratios.' The procedures used here for pH's in water (1:1) and in 0.01MCaC12(1:2) are those recommended Jointly by the America”. “testing and malysls Par Influence of Severe effect of it and that it the atmosp‘o 7.0. Real tlvlty of t by lncreasl t° ten per: soils is sj m that w, nent Chang ‘50“ dioxid of “1108.11 arithm of pa °r Suc': Partial p: or the Dr: 1 .n wtiter. Tee “wiles. the American Society of Agronomy and the American Society of Testing and Materials in Agronomy No. 9, Methods of Soil Analysis Part 2. 1965. Influence of 002_pressure in the atmosphere Several investigators (39.57.61.85) agree that the effect of increased carbon dioxide is to decrease soil pH, and that its effect at the partial pressure prevailing in the atmosphere is very small in soils having pH values below 7.0. Hoagland, et, a1. (39) found that the hydrogen ion ac- tivity of the suspension of acid soils is not markedly affected by increasing the carbon dioxide content of the suspension up to ten percent, but that the acidity of a slightly aklaline soils is slightly increased by such treatment. They pointed out that when the original conditions are restored no perma- nent change in soil reaction could be attributed to the car- bon dioxide. Whitney and Gardner (85) found that the pH 01’ calcareous soils is a straight-line function of the log- arithm of the carbon dioxide pressure and concluded that the PH of such soils, measured after equilibration with known PaJVtial pressures of 002, should give a better indication of the probable pH range in the field than the pH measured in Water. In the U.S. salinity laboratory (61). the pH measurements are ordinarily made after equilibration of the s°11With the carbon dioxide pressure of the atmosphere, regalxiless of the soil to water ratio used. Influence o It he. changes in cotiller dur tween pH at vestlgatior relations‘n fair-1y con widely bet Saturation latlons‘n'l; “65311558 t of the so] kaolimti of the co latlonshi It 2"),(10’46 hen Con- -10- Influence of plants and relation of pH to base saturation It has been reported that plants may influence seasonal changes in soil reaction by removing bases from the exchange complex during the growing season (75). Relationships be- tween pH and base saturation have been the subject of many in- vestigations (48,#9,58,72). Morgan (52) pointed out that the relationship between pH and percent base saturation may be fairly constant within a soil type. but that it may vary widely between soil types. Mehlich (H8,h9) studied the base saturation and pH relationships and concluded that this re- lationship is almost solely influenced by the nature of the exchange complex. For montmorillonitic soils base saturation of the complex at pH 7.0 is practically complete; whereas for ikaolinitic soils at the same pH value only 50 to 80 percent of the colloids are base saturated. The base saturation re- lationships are very useful in classifying soils in the new soil classification system (7th Approximation). Influence of absorbed aluminum It has been reported by several investigators (13.20, 2&,40,#6.62.63,67.70,80,83) that in very acid soils aluminum «contributes to soil acidity. 0n the breakdown of clay, alum- 1num.contributes to soil acidity. 0n the breakdown of clay, EiLuminum is released and absorbed on the exchange complex. The hydrolysis of aluminum results in the formation of hydIWIxy-aluminum ions and hydrogen ions, thereby increasing the apparent soil acidity. niluence < Seve: studied to. soils in r eluded the Orsmic ac Slightly : T 9‘ H in: iueRCe \ mi 3.8 mum?) t)“: Values he -11- Influence of organic matter Several investigators (1.12.15.34.68,69.7u,8h) have studied the organic matter content and organic acids of soils in relation to variations in soil reaction. They con- cluded that the organic matter acts as a buffer. whereas the organic acids accumulated underanaerobic conditions may slightly influence soil acidity. Influence of time interval between preparation and pH measurements The time interval between preparing the suspension and .making the determination in relation to changes in soil pH ‘values has been the subject of several investigations (4,29. _SO). Working with alkaline soils, McGeorge (50) concluded tunat the pH decreases with an increase in the time interval. (Zontrary to the above. Bailey (A) used boiled distilled vmater, a 1:2 and l:# soil-water ratio, field moist and air (irw'samples. and concluded that the pH of the suSpension was rust affected by the length of time the water was in contact trith the soil sample. Bailey's conclusion was substantially 1J1 agreement with the results of Dean and Walker (29). Skunparisons of Various colorimetric methods for pH measurements At the present time. the colorimetric method for pH de- 'terndnation is primarily confined to field test kits. Mason .Et.efl4 (47) compared several pH fieldldts based on their cost, accuracy and adaptability for rapid use. They found that the reproducibility of pH values as indicated by the several field 0T»:- ' - —- —- lun— kits were Operator, as aqueou however, on reasur 31‘. attet; thus mini (:29 8.201: D ',h- -12- kits were influenced by the following: (1) experience of Operator, (2) purity of chemicals and prOper adjustment of pH, (3) cleanliness, (4) contamination, (5) and manipulation of soil extract. In moSt colorimetric techniques. the pH of an aqueous soil extract is usually measured. Woodruff (8h), liowever, has recently prOposed a colorimetric method based ¢Dn measurement of the pH of a 0.01MCa012 extract of soil in zan attempt to fix the salt concentration of the soil and 'thus minimize the variation in soil pH due to fluctuation in “the amount of soluble salts. Accuracy of glass electrode measurements At present. the glass electrode is the most extensive— 13r used electrometric method for pH determinations. It is stuxndard equipment in most laboratories and it may be line ox"battery Operated. The reproducibility of pH values with the glass elec- tnxxie has been the subject of several investigations (19,23, 25.5#.55,59,60,66). Chapman, et. a1. (19) found that read- ings with the glass electrode were stable. constant and con- sistent at moisture contents corresponding to the moisture equivalent and/or the sticky point; providing the electrodes Were well covered with the moist soil and there was good contact. They reported a maximum variation of 0.08 pH unit With a loam soil, and a range of O.# pH unit with a clay loam soil at the above moisture content. EOE! a me uS‘ia“ lower 210* '4 Pu Values F1 (D p) '1 'A -13- However, soil pH measurements with the glass electrode are usually made in dilute suspensions rather than at the lower moisture contents. Coleman, et. a1. (25) observed that ij values obtained for a stirred soil suSpension was lower than that of the supernatant liquid and that the pH value Ineasured when the electrodes were pressed into the sediments *were still lower. He concluded that the measured e.m.f. which is interpreted in terms of pH includes two terms, the activity «of hydrogen ions and a junction potential, and that potentio- Inetric measurements of the pH of soil suspensions or pastes czannot be entirely attributed to soil acidity. For twelve CLifferent soils they reported that the pH of the suspensions were 0.1 to 0.9 pH units lower and the pH of the sediments wexre 0.5 to 1.7 pH units lower, than the pH of the supernatant liquid. Peech. et. al. (55) pointed out that the error due to the: junction potential when both the glass and calomel elec- trmxies are immersed in the flocculated soil suspension should not exceed 0.25 pH unit. They indicated that the error may be avoided in flocculated soil suspensions by placing the salt bridge or the conventional type calomel electrode in the Clear supernatant liquid and the glass electrode in the sedi- ments or partly settled suspension. Schofield. et. al. (66) preposed the measurement of pH in a 0.01MCa012 solution.) They indicated that the error due to the Junction potential could thus be minimized because 8°11 suspensions are flocculated in 0.01MCaClZ. Also. they pointed on ution over equivalent solution c tent. Th: indepeme Saline so Cla pmential the clear the 9ND] ionic Sat: Mar. Ea- sonal Va (59). 1 immem -14- pointed out that the pH in 0.01MCaC12 is independent of dil- ution over a wide range, and that 0.01MCa012 is approximately equivalent to the total electrolyte concentration of the soil solution of a non—saline soil at optimum field moisture con- tent. Therefore the observed pH in 0.01MCa012 should be :1ndependent of the initial amount of salts present in non- saline soils. Clark (23) found that the errors due to the junction 1>otential were not eliminated by placing the K01 bridge in 1:he clear supernatant liquid. However, he indicated that tune errors are essentially eliminated by insuring that the icnnic strength of the salt in solution is less than 0.005 molar. Many European workers have attempted to minimize sea- scnial variations in soil pH values by measuring pH in IN KCl (59). They have indicated that pH values in lN KCl are less influenced by changes in biological and meteorological condi- tions and thus reflect a.more intrinsic characteristic of the soil than the soil pH measured in water, as is commonly done in the United States. were mine] {Laughton drainage . M811 to p Sal{files m tion of 6 “2112889 ’ Lhfi zaps. F] vll‘e, n? Tin) -15- EXPERIMENTAL PROCEDURE Location of Sites This study was initiated in May, 1966, using thirteen soil series and nineteen sites. All of the series and sites were mineral soils except one which was an organic soil (Houghton muck).l The texture of the surface, and the natural drainage of the soils varied from clay loam to sand and from well to poorly drained, reSpectively. The pH's of air dry samples measured in water varied from 5.2 to 8.0. The loca- tion of each site is given in Table l, and the texture, natural drainage, degree of erosion, percent lepe, direction of slope, vegetation or crop, and area studied at each site are given in Table 2. The general soil areas were located by the use of soil maps. From these areas. plots with uniform t0pography, tex- ture, natural drainage, vegetation or crop, color of surface and pH were selected. The sites selected were not close to gravel roads, dead furrows, lime or manure piles, or burned muck areas. \0 Q hELOC 1" 1 D r‘ “E“ g (f' *1] Tab]. 6 l c Ceresco No. 1 Ceresco No. 2 Colwood No. l Colwood No. 2 Chelsea* Hillsdale No. l Hillsdale No. 2 Houghton Lapeer Nekoosa No. l Nekoosa No. 2 Oakville Pewamo No. l Pewamo No. 2 Plainfield Spinks No. l Spinks No. 2 St. Clair -15- Location of plots County Clinton Ingham Ingham Clinton Clinton Clinton Ingham Ingham Clinton Ingham Clinton Clinton Ingham Clinton Clinton Shiawassee Ingham Clinton Clinton “Formerly called Graycalm. to Northern Michigan Two. -. Hatertown Meridian Meridian U3 SD .th (15 ath Victor Leslie Meridian Bath Meridian Bath Bath Meridian Watertown Eagle Woodhull Meridian Bath Dallas Graycalm is now restricted Table'l. Continued Erectional Section, Sectionl Township ard Range NE %, sw 3 NW % Sec. 6. T5N, 33w RN 3, NW i, NW i, Sec. 36, TQM, BIN rs i, NE 1. NE 1. Sec. 35. Tux, Bid 7* 54 WP '7‘ o] Sec. 22. TEN, le If .1 E3 NJ E3 'r t o H ‘ 4 [41 .t 'u u 1'“ ”up. . See. 23. TSN, le SE %. Kw i, sw ;, Sec. 31, T36N, RlN NE 1. SE ;. NW i, Sec. 24, TlN, Riv sw i, RE i, 5v i, Sec. 30, Tux, Riv NE i, Ne g. NE 2, Sec. in, T5N, Riv sw i. 54 i, NE &, Sec. 19. Thu, 32w KB }, RE i. N? 1. Sec. 22, T5N, le SE i. SE ;. sq 3. Sec. 2n, T5N. , Riv hi 3, Lw {. DE ;, Sec. 22. Tun, Rlfl L4 2, NW &, *w 1, Sec. 6. T5K, 33w sw ;, Sb %, YE ;. Sec. 1, T5N, Run U) [*1 N" (I) re h.- .5": 2.. 4:. IL: Sec. 20, T7N. 313 See. 30, TAN, RIM m 2, NH H (4 [=1 er Ce 2. wk SE %. SE ;. :3 1, Sec. 2n, T5N, BIN See. 4, T7N, Raw 0) hi we U) H ,z In 03 2: if 3011 Site HA I ~-\ 1.. 3 3 \1 &" ‘ V..E§tc: ,- N .n .i AM fi- A; W,. .1; ‘1‘ ‘ q nun Pad ‘ ,L .J .‘ *‘ .0 \ V. 1- \v I A h 3 o O 0 mm .c: 6 Z . .. .m .r hu. ‘Cu C. W .e m K x . 2. V f Di '1 b t ‘ ' '\ t ‘ C O I a ‘ .ru a .I 1‘ ¥Un H: «‘0 I Table 2. Soil Site Blount Ceresco No Ceresco No Colwood No Colwood No Chelsea -17- Texture, degree of erosion, percent slope, direction of lepe, crop or vegetation and natural drainage of the 19 sites used in the study. Hillsdale No. Hillsdale Houghton Lapeer Nekoosa No Nekoosa No Oakville Pewamo No. Pewamo No. Plainfield Spinks No. Spinks No. St. Clair J H Texture Degree of (Surface) Erosion (1) Clay Loam Slight (0) . 1 Sandy Loam None (0) . 2 Sandy Loam none (1) . 1 Loam Slight (1) . 2 Loam Slight (1) Sand Slight (1) Sandy Loam Sli‘ht (1 No. Sandy Loam Slight (0 Iviuck None (1) Sandy Loam Slight (1) . 1 Sand Slight (1) . 2 Sand Slight (1) Sand Slight (l) 1 Clay Loam Slight (1) 2 Clay Loam Slight 2 Sand moderate (l) 1 Loamy Sand Slight (l) 2 Loamy Sand Sliwht 1 Clay Loam Slight 0 “cl (3 (b :1» wk b Is- as d" \ bl b»: (vi (U I D> l 131'. a; 53' I 6" :1» I be I b:- o'k (N ‘65; 654. U" l tr! I 655‘ \ 0“ {r- \ :} 0“ a»: mv mv (NV O\v‘(\) v N V (\Vf‘o V_(\) V‘h) V (\J VmVG\V N VN VN V N V (\3 VI\) V 6K m ‘ek (D ‘64. cfk ("H I m wAWA‘wAwAOAOAw/xOAOAOAOAWAwr-‘OAOAOAOAOAOA "ex I i c ' C i N . I f . I. - LP: a.“ m. «r . . 5 v v .u 4 .fi , £1 .5 A . J. ‘4 ”A ‘L «O . .. .‘J. WV RU .I . N4 Aw ~\.U 3AM fib 441w . 1.11.06. . .I.,- 1Fir§1 A. 4’ u I . v .+ i. . . «A . A s a . 0 3 Aug AD 1.) 301‘.“ Direction of Slang Southern Southern Southern South Western Southern South Western South western Southern Southern Southern South western Southern South western South western Southern South western South western Southern Southern Table 2. CrOp or Vegetation Corn Grass Grass Grass Grass Grass Alfalfa Grass Sod Grass Grass Grass Pasture Corn Alfalfa Grass Alfalfa Corn Alfalfa Cont inued Natural Draina;§ Imperfect* Imperfect Imperfect Poor Poor Well well Well Poor Nell Imperfect Imperfect well Poor Poor Well Well Well Well Area of Plot to 50 5o 30 to 100 60 to 100 to no 30 30 100 100 30 so so no ft. ft. ft. ft. ft. ft. ft. ft. ft. ft. ft. ft. ft. ft. ft. ft. ft. ft. ft. 50 ft. 50 ft. 60 ft. so ft. 50 ft. 100 ft. so ft. 60 ft. zoo ft. 50 ft. 100 ft. 100 ft. 80 ft. zoo ft. zoo ft. 70 ft. 80 ft. ’40 ft. 60 ft. * "Imperfectly drained" and "somewhat poorly drained" are synonymous expressions of the natural drainage conditions of a soil. ___,-,__.,_,..-. .. . -18- Collection of samples Uniformity of the pH at each site was ascertained by the variability of pH among six individual cores and a composite sample which consisted of 20 cores. The six individual cores were 3 inches in diameter and extended to a depth of 6 to 8 inches (the plow depth). The 20 cores of the composite sample were one inch in diameter and extended to a depth of 6 to 8 inches. The six cores were collected by dividing each plot into six equal parts and taking a core from the center of each of the six parts. The 20 cores of the composite sample for each site were taken according to Extension Bulletin E-498 of the Cooperative Extension Service of Michigan State Univer— sity (2}). Two sub-samples were taken from each of the six individual cores and from the composite sample, and the pH's were determined with the glass electrode in a 1:1 soil- water suspension, Table 3. After the sites or plots were located and established, the plow layer or upper 6 to 8 inches of each-plot was sampled about the fifteenth of each month. Ten of the sites were sampled from May through September the other sites were sampled from June through September. One composite sample was collected from each plot each month in the same way the first composite sample of each plot was collected. =19.- Preparation of samples The composite samples were well mixed in a plastic pail. After uniform mixing, a sub-sample was taken from the original sample of each site and placed in a plastic bag. After the sub-sample from each site was brought into the lab- oratory, part of it was refrigerated at about 40°F. until the field moist pH's could be determined and the remainder was placed on a laboratory bench and allowed to air dry. The samples were covered with wrapping paper, while air drying, in order to prevent contamination by dust particles. Deter- minations of pH on the air dry samples were made after three or four weeks of air drying. The pH of the field moist sam- ples were determined from one to three days after collection of the samples. A portion of the field moist sample from each plot was dried in an oven for 2h hours, at approximately 100-1100F, and the pH's of these oven dried samples were also determined. -20- METHODS OF ANALYSIS All samples were crushed and sieved through a two mill- imeter screen prior to analysis, and all determinations were run in duplicate, except where otherwise indicated. Soil reaction The hydrogen ion activity was determined with a Beckman Zeromatic pH meter and with the Hellige-Truog colorimetric kit at the following moisture statuses: field moist, air dry, and oven dry. All pH measurements made with the glass electrode were on samples with the soil water ratios as indicated, on a weight basis. Glass electrode pH's of the oven dry and field moist samples were measured in a 1:1 soil -H20 suspension and in a 1:2 soil - 0.01MCaCl2 suspension. The hydrogen ion activities of the air dry samples were also measured in a 1:2 soil - IUWKCl suspension, in addition to the above two suspensions. {Noe suspensions were each allowed to equilibrate for fifteen mixnxtes with several intermittent stirrings. Cation exchange capacity The cation exchange capacities were determined by sat- urating the exchange complex with sodium ions (1N NaAc, at':.pH8.2) and replacing the sodium ion with ammonium ions (1N NHuAc) (443). The sodium in dilute solution was determined with a Colezar I 0f soil l-il .— electri¢ PEech ( an the -21- Coleman flame photometer, and expressed as m.e./100 grams of soil. Total exchangeable metallic cations The total exchangeable bases were determined by the titration method as described by Bray and Willhite (42). Electrical conductivity The total soluble salt content was estimated by the electrical conductivity method as described by Greweling and Peach (36). A Solu—Bridge soil tester (Model RD—l5) was used and the specific conductance was expressed as mhos x 10‘5/cm. Organic matter content Total organic matter was determined by the ignition and 'weight loss method as described by Mitchell (#2). Lime requirement Lime requirement was evaluated by the following three methods: 1. Shoemaker, et. al.. buffer method (73). 2. pH - Texture method (77). , 3. Exchange acidity - determined by difference be— tween cation exchange capacity and total exchange- able metahlic cations. The lime requirements as determined by the above three me thods were compared . 'J_ We"? at r' with. «m: - - -22- RESULTS AND DISCUSSION Evaluation of the errors encountered in the measurements of soilqu with the glass electrode To evaluate the errors in soil pH measurements with the glass electrode, consideration was given to: (l) the varia- bility of the pH's of several standard laboratory check sam- ples measured repeatedly during the period of this study, (2) the effects of different operators, different pH meters and different times on the pH's of five air dry soil samples, and the reproducibility of soil pH measurements made on these air dry samples: in water, in 0.01MCaC12 and in 1.0NKC1, (3) the variations in duplicate pH measurements made on com- posite field moist samples from each of the 19 sites, com- ‘pared to the variability of duplicate measurements made on six core samples from each of these sites. ‘Variability of pH measurements made on standard laboratggy check samples during the season pH values of the check samples used in this investiga- ‘tion.were each measured several times during this study from bury to October and approximately on the same dates that the Ifli’s of the nineteen soil sites were measured. In addition, these pH measurements were not always made by the same 0p- erator and the measurements were not always made with the samuang meter on the different dates. -23- Variability of pH values measured during this study for each of three of the standard check samples are illus— trated in Figure 1. Check sample No. 1 has the highest pH value and it showed the least variability. pH values of this check sample fluctuated only 0.1 pH unit from time to time during this study. The maximum and minimum pH values for each of the other two check samples were observ— ed during the earlier and latter part of this study, re- spectively, Figure 1. Differences between the maximum and minimum pH values for each check sample were 0.3 pH unit or less. Variations of the pH's of the other three check samples were comparable and similar to the variations, as illustrated in Figure l, of check samples number 2 and 6. The standard deviations of the means for the indi- vidual check samples ranged from a low of 0.07 to a high of 0.22 pH unit (Table 3). The combined standard error of the difference between the "known mean pH values and the measured mean pH values was i 0.075. Twice this value will Judge significance at the 0.05 probability level. By this criterion none of the measured mean pH values of the check samples differed significantly from their known pH 'values. However, it is interesting that all the observed means were less than the known values: on the average this ciifference was 0.09 pH unit. It is concluded that differ- ences between mean soil pH values of a group of represen- -24- Figure 1. Variability of pH measurements made on several air dry standard laboratory check samples from May through October. 'L7r °--w ° ° \/ Sample . o NoJ '16- 6.|' 613- , “//// Sampm No6 519" :E: C‘- 5.8 - .___. SJ /////> 5.0- ° . \\\\\ Sampm .\\\\\ N012 4.9’ IWT 0—0 4.8- J I I 4 May June July Aug Sept Oct Time -25- Table 3. "Known pH Values" and variability of pH measurements made on standard laboratory check samples from May to October, 1966. Number Sample "Known mean of pH Means and standard Number pH Values" measur- deviations of pH ments measurements 1 7.75 13 7.68 i 0.07 2 5.05 12 4.94 i.0-17 3 6.0 10 5.94 i.0°22 4 5.9 10 5.75 i 0.17 5 5.7 9 5.68 i_0.l6 6 6.05 5 5.90 i 0.14 -26- tative observations may be significant when the differences are greater than 3; 0.15 pH unit. Effects Of different Operators and different pH meters on the variability of the_pH's of :five air dry soil samples The pH's Of one air dry sample from each of five of the nineteen soil sites used in this study were measured repeatedly to evaluate various possible sources of exper- imental errors in the pH measurements. The textures of these five seaples ranged from loamy sand to clay loam, and their reaction, measured in water. ranged from a pH value of 6.0 to a pH value Of 7.4. Three Operators measured the pH's of the five soil samples with one pH meter on the same day in the following suspending media: water, 0.01MCa012 and 1.0NKC1. A three 1 way analysis of variance (5 soils. 3 Operators. and 3 sus- pending media) was performed on the data: soils and media were considered fixed and Operators random in that analysis, Table 4. Significant differences were found for all main effects and a soil by media interaction. Table 4. There- fore. the variability Of soil pH measurements made by dif- ferent Operators must be considered in studies Of this type. -27.. Table 4. Analysis of variance for a three way analysis (5 soils, 3 Operators, 3 sus- pending media). Source of Degrees of Means Variance Freedom Squared_ Soil 4 1.96** Operator 2 0.13** Soil X Operator 8 0.01 Suspending media 2 3.62** Soil X Suspending Media 8 0.04* Operator X Suspending 4 0.01 Media Error 16 . 0.01 ** Significant at probability less than 0.01 '* Significant at probability less than 0.05 The pH's of the five soil samples were measured in the three suspending media by one Operator using two dif- ferent pH meters on the same day. The maximum average dif- ference between the two pH meters was 0.06 pH unit, Table 5. This is not a significant difference. Thus it appears that variations in pH measurements made under these conditions with the different pH meters are not important. Reproducibility of soiltpH measurements made in 320, in 0.0130381; andwin 1.01KCl by one operator usipg one_pH meter on the same day. One operator employed the same pH meter and made ten pH measurements on each of the five soil samples at hourly intervals on one day. On the average the standard deviations of the measurements made in water, in 0.01MCaClZ and in 1.0NKC1 were :0.08, :0.07. and i0.08 pH unit respectively. ‘Table 5. It is concluded that there are no significant dif- ferences in the reproducibility of soil pH values measured in the three suspending media. This conclusion is con- trary to the prOposal of Schofield et. al. (66) who indicated that soil pH measurements made on air dry samples in 0.01MCaC12 are more reproducible than measurements made in water. How- ever, the possibility remains that seasonal variations in 3011 Pfii's may be less in 0.OlI'=ICaCl2 than in water even though :individlial determinations are no more reproducible. Table 5. Summary of the variability in the pH's of five air dry soil samples measured in water, in 0.01KCaCl2 and in 1.01KC1. Suspending Hedia Standard deviation(s) Standard error of the mean (SE) Kean pH for each gperator O\O\O\ O\\J\CO (DOC (1) (2) (3) . 10.11 pH unit 10.03 pH unit Bean pH Of each meter 10.04 pH unit 10.01 pH unit 0.01MCaC12 Standard deviation(s) Standard error of the mean (S?) (l) 6.44 (2) 6.22 (3) 6-30 10.12 pH unit 10.03 pH unit 10.03 pH unit 10.01 pH unit 1.0NK01 Standard deviation(s) Standard error of the mean (Sr) (1) 5.74 (2) 5.62 (3) 5.78 10.08 pH unit 10.02 pH unit 10.04 pH unit 10.01 pH unit Table 5. Continued Fean, standard deviation(s) and standard error 13;) of the mean of ten replicationsfor each of 5 soils Dean pH S SE (1) 6.20 10.08 pH unit 10.025 pH unit (2) 7.36 10.05 pH unit 10.016 pH unit (3) 6.95 10.09 pH unit 10.028 p1 unit (4) 6.20 10.09 pH unit 10.028 pH unit (5) 6.61 10.07 pH unit 10.022 p3 unit (1) 5.79 i0.09 pH unit 10.028 pH unit (2) 6.97 :0.06 pH unit 10.019 pH unit (3) 6.67 10.05 pH unit 10.016 pH unit (4) 5.78 10.08 pH unit 10.025 pH unit (5) 6.30 10.08 pH unit 10.025 pH unit (1) 5.40 10.08 pH unit 10.025 pH unit (2) 6.70 10.08 pH unit 10.025 pH unit (3) 6.20 10.09 pH unit 10.028 pH unit (4) 5.28 10.03 pH unit 10.025 pH unit (5) 5.75 10.06 pH Unit 10.019 pH unit -30- Variability of soilka values measured in 0.01MCaCl2 with one pH meter by one Operator on two different dates. The pH's of all theeflrdry samples from each of the nineteen soil sites used in this study were measured in 0.01MCaC12 on two different dates. The regression of March 21 values on April 13 values was calculated (Figure 2): y = 0.04 + 0.99x. The standard error of the estimates equals 0.15 pH unit. To Judge what may be a real difference between soil pH measurements, twice the standard error of the estimate was employed or 0.30 pH units. This will judge significance at approximately the 0.05 probability level. Variability of field moist pH values within each of the nineteen soil sites. pH values of the first composite sample collected and each of the six single core samples collected from 1/6 of each plot are presented in Table 6. These pH values were zneasured in water with one pH meter. by one operator on the snmne day. The determination standard deviation for the sites ranged from a low of 0.096 to a high of 0.169 pH unit, and kar the combined analysis it was 0.138 pH unit. Thus we con- olluie that the determination variability is consistent from site to site. The individual F statistics for testing the variability among cores within each plot were all non-sig- nificant. In fact, the F tests deviated only slightly from 31.0. From this we can conclude that the variability in the pH measurements of a particular soil site is due mainly to determination rather than to sampling. pH (ApnII3,I967) -31- Figure 2. Comparison of pH values of all the air dry samples from the 19 sites measured in 0.01MCa012 on two dates. oé’ . ' Q '75 .§® (g? )(///// / ‘3 - ‘\ 7.0 o / oo//Q' y° %/ /.,o a. oo / x6 9 (3.5 V / /:a/. /°/4f 3'0 0/ / / 6.()" ,/: .39,/ o/o 00/ A o /e/ /é / :2 5.5 - 4"; //;;;/ y=004+wi99(X) / 9/5/ ° // '9 , :i: ' 5.0 _ / / S 0.|5pH unit 00 / /o o”! /o flat/O'l/ 4. 5 ' / o 0;" 1 / / 1 / 4 O I l 1 1 L l J 4.5 5.0 5.5 6.0 6.5 7.0 7.5 pH (March 2|, I967) Table 6. Variations in the pH's of the composite and single core samples collected in the initial sampling of each plot Field hoist pH values - 1:1 SoilnHQO Ratio, py Weight Composite Single Cores (3 in. in diameter) Soil Site 14mgi? §§Od§2§iiéry Ko.l No.2 Ko.3 9— Blount 7.0 7.2 7.2 7.0 7.1 6.9 7.2 7.0 Ceresco No.1 7.9 8.1 8.0 8.2 8.0 7.8 8.2 8.0 Ceresco NO.2 7.9 7.7 8.0 8.1 7.6 7.8 8.0 7.8 Colwood No.1 8.0 8.2 8.2 8.2 8.0 8.3 8.0 8.2 Colwood No.2 8.0 7.8 7.6 7.8 7.9 7.6 7.8 7.8 Chelsea 5.8 5.6 5.9 5.6 5.6 5.6 5.8 5.6 Hillsdale No.1 6.7 6.9 6.5 6.7 6.6 6.7 6.6 6.8 Hillsdale No.2 6.2 6.2 6.3 6.0 6.2 6.4 6.3 6.1 Houghton 6.9 7.0 7.1 7.1 7.1 6.9 7.2 7.0 Laper 7.4 7.4 7.3 7.3 7.3 7.5 7.3 7.4 Nekoosa No.1 6.8 7.0 6.9 6.7 6.9 7.2 6.8 ’.8 Nekoosa No.2 7.7 7.9 7.6 7.8 7.9 7.7 7.7 7.6 Oakville 6.4 6.3 6.2 6.4 6.3 6.1 6.4 6.2 Pewamo NO. 1 7.5 7.5 7.4 7.6 7.7 7.5 7.6 7.4 Pewamo No. 2 7.5 7.3 7.4 7.4 7.6 7.4 7.6 7.6 Plainfield 6.0 6.3 6.1 6.3 6.2 6.0 6.3 6.1 Spinks No. l 6.4 6.7 6.8 6.6 6.6 6.4 6.7 6.7 Spinks No. 2 6.6 6.8 6.6 6.6 6.7 6.5 6.9 6.7 Edt. Clair 7.5 7.5 7.4 7.6 7.7 7.5 7.4 7.6 -323- Table 6. Continued .No.4 No.5 ' No.6 Heans and Determination 7.2 7.2 6.9 7.2 7.1 7.1 Standgfg9D1768154ns (SD) 8.1 8.0 8.0 7.8 7.9 7.9 7.99 1 0.122 7.9 7.7 7.7 7.8 7.8 8.0 7.84 1 0.185 8.2 7.9 8.3 8.1 7.9 8.1 8.11 1 0.155 7.8 7.6 7.8 7.6 7.9 7.7 7.76 1 0.144 5.7 5.9 5.7 5.6 5.6 5.6 5.68 1 0.125 6.5 6.5 6.7 6.5' 6.8 6.6 6.65 1 0.122 6.3 6.3 6.1 6.1 6.4 6.2 6.22 1 0.122 7.0 6.9 7.0 6.8 7.1 7.1 7.01 1 0.099 7.4 7.2 7.3 7.3 7.4 7.5 7.35 i 0.096 7.1 6.9 6.9 6.7 7.1 6.9 6.91 1 0.144 7.6 7.7 7.7 7.9 7.7 7.6 7.72 1 0.104 6.4- 6.2 6.5 6.3 6.3 6.1 6.31 1 0.122 '7.6 7.6 7.5 7.3 7.5 7.3 7.50 1 0.119 7.5 7.7 7.7 7.5 7.5 7.3 7.50:0-119 (5.0 6.3 6.3 6.0 6.0 6.1 6.14 1 0.169 6.4 6.5 .6-7 6.5 6.7 6.7 6.601O.127 5.5 6.7 6.7 6.9 6.9 6.7 6.70 1 0.131 7.65 7.6 7.7 7.5 7.4 7.5 7.54 1 0.110 Combined SD 00138 -33... Summary On the basis of the above. it is evident that pH mea- surements made on a particular soil sample varied when mea- sured under the different conditions stated above (Tables 3, 4, 5 and 6 and Figures 1, 2). The greatest variations of soil pH values occurred under those conditions where measure- ments were not always made with the same pH meter and by the same Operator on the same date, Table 3. However, in most instances the standard deviations of pH values measured on the same soil samples under the various conditions were ap- proximately 1 0.15 pH unit or less (Tables 3, 4, 5 and 6 and Figure 2). Therefore, a variation of 10.3 pH unit is considered necessary to be certain of a probable significant difference 'between individual soil pH measurements. This range of var- iability satisfactorily includes the errors encountered in the individual measurements of the pH's of the soils used 111 this study. However, when mean soil pH values of a group of Inapresentative observations are compared than differences greater than 10.15 pH unit may be significant, Table 3. Influence of moisture conditions and suspending media on seasonal varia— bility of soil pH values Data on soil pH's determined at two moisture conditions witfli the Truog kit, and at three moisture conditions and in -34- several suspending media with the glass electrode are pre- sented in Table 7 in the Appendix. for each of the sites on each sampling date. Statistical deductions for these data are presented in Figures 3. 4 and 5. Ten of the nineteen soil sites used in this study were sampled for five months. May through September. and the other sites were sampled for four months. June through September. 0n the nine sites sampled for only four times the seasonal trends were similar to those of the other ten sites during that period. Inf1uence of mo1sture condition on seasonal vaziabilitv Of soil pH values measured in water and in 0.0MCaC12 with the_glass electgode The field moist soil pH data showed a continuous decrease in values as the season progressed. Figure 3. Because of the lower pH's observed on the standard laboratory samples below 3 H 6.5 after August 15. as shown in Figure 1. the pH readings on the field moist and oven dry samples measured in H20 were corrected by adding 0.1 pH units to the September readings that were below pH 6. 5. Soil pH values measured at this moisture condition in water and in 0.01MCaClz were 0.81 and 0.1V? pH units lower. respectively. at the end of the season. 1J1 September than at the beginning of the season. in May. (n1 the other hand. the air dry and oven soil pH values tended to show a cyclic seasonal trend. Differences between average soil pH values at the three -35- moisture conditions were 0.08 pH unit or less in both water and 0.01MCaC12 at the end of the season. Figure 3. These differences are not significant. However. differences be- tween soil pH values measured at the three moisture condi- tions are significant at certain times during the earlier part of the season. The calculated L.S.D. at the 5% level is equal to 0.1 pH unit. Figure 3. This calculation was based on a site by time by moisture condition interaction. During this period. the air dry and oven dry soil pH values measured in water were as much as 0.55 and 0.88 pH units lower than the corresponding field moist pH values. respectively. Figure 3A.. Similarly. the air dry and oven dry soil pH's measured in 0.01MCaCl2 were as much as 0.28 and 0.34 pH units lower than the corresponding field moist pH values. respectively. Figure 3B. During the season, there were no consistent significant differences between the air dry and oven dry soil pH values :measured in either of the two suspending media. Figure 3. Chi the average. the oven dry soil pH values were less than (3.1 pH unit lower than the air dry soil pH values measured 111 either water or 0.01MCaC12. The average of the 0.01MCaC12 pfli's were lower than the mean pH values measured in water at tine following moisture conditions by the following amounts: field moist; 0.85 pH unit; air dry: 0.60 pH unit; and oven dry; 0.61 pH unit. -35- Figure 3. Average pH's of ten soil sites measured at 7.0 6.8 6.6 6.4- I 6.2 6.0 5.8 5.6 5.4 three moisture conditions and in two sus- pending media from May through September. PFieId moist H654)” °\ 7 A)pHSintbO _ . I 1.3.0.05 7A” dry o/0 (e. we .\ Oven dry \:\: é: -m.2me° Field moist\ (5. 79)¢° P 7:\° B) pHs in "Airdry / \ O.O|MC0C|2 l' (570”, /°8\\O\ -0ven dry 0 /8 \ __(5.63)¢ §g *- 4} mean pH value May June July Aug Sepi Time _37_ Comparison of the variability of the air dry pH's of soil samples collected from May through September when measured in H20. in 0.01MCaC12 and in_110NKCl with the glass electrode. The average air dry soil pH values measured in water. in 0.01MCa012 and in 1.0NKC1 showed a cyclic seasonal trend in the pH's of the ten sites studied for five months. Figure 4. The May pH values were lower, on the average. than the June pH values for the ten sites. The average pH values measured in water were the high— est at all times during the season and the 1.0NK01 pH's were lowest for the entire season. On the average. pH's measured in 0.01MCa012 and in 1.0NKCl were approximately 0.6 and 1.0 pH units lower. respectively. than pH's measured in water. How— ever. the 0.01MCaCl2 pH's were 0.5 pH lower than the water pH's at the more alkaline and of the pH scale and 0.8 pH unit lower at the more acid end of the pH scale. Similarly the 1.0NKCl pH's were 0.9 and 1.1 pH units lower than the water pH's at the more alkaline and acid ends of the pH scale. re- spectively. There were no significant differences between the sea- sonal variability of the average air dry pH values measured in water and in 0.01MCaC12. Figure 4. This is contrary to the proposal of Schofield et. a1 (66) who have indicated that air dry soil pH values measured in 0.01MCaC12 show less sea- sonal variability than the corresponding pH values measured in water. However. the 0.01MCaC12 solution did reduce the Figure he 6.8 6.6 6.4 6.2 6.0 255.8 5.6 5.4 5.2 5.0 ~38- Variability of air dry pH's of ten soil sites measured in three suspend- ing media from May through September. \< H20 y 646 (0.077)X (6.3l la><° 0.0|M \\ COCIZ \>. y=5.85-(0.076) x 0 (5.70) “/0.\\ (5.3l)‘:f y=5.34"(0.0|9)X a mean pH value I l l l l J May June July Aug Sepl Time -39- seasonal variability of field moist pH values compared to those measured in water. Figure 3. The field moist soil pH values measured in water and in 0.01MCaCl2 were 0.81 and O.h7 pH units lower at the end of the season (September) than at the beginning of the season (May). respectively. pH values measured in 1.0NKCl showed the least seasonal variability. Figure h. This is in agreement with the find— ings of many EurOpean workers who have reported that soil pH values measured in 1.0NKCl are less influenced by changes in biological and meteorological conditions and reflect a more intrinsic characteristic of the soil than soil pH values measured in water (59). gemeerison of the seasonel variability of field moist and air dgy soil p§_yalues measured with the Truog kit and with the glass electrode On the nineteen soil sites sampled four times. the field moist and air dry soil pH values determined with the Truog .kit showed seasonal trends similar to those of the correspond- ing pH values measured with the glass electrode. Figure 5. On.the average. air drying lowered the field moist soil pH 'values determined with the Truog kit approximately 0.3 pH ‘unit during the season. The Truog kit showed less seasonal 'variability in pH's. on the average. than the glass electrode. particularly on field moist soil samples. On the average. differences between the field moist soil.pfliva1ues measured in water with the Truog kit and with ‘17! Figure 5. 7.0 6.8- 6.6 6.4 6.8 6.6 3; 6.4 5.2 -uo- Comparison of average field moist and air dry pH values of nineteen soil sites measured with the Truog Kit and in water with the glass elec- trode from June through September. A) Field Moist pH's \/ . \\ T . o ruog klt “° (6.85)“ O \ Glass Electrode ° (6.70)” a mean pH value I I 1 June July Aug Sept 8) Air Dry pH's 0 \\\\\‘° Truog kH \0/0 (6.58)“ / o____..—o Glass Electrode (6.42)it a mean pH value I 1 J June July Aug Sept Time -41- the glass electrode increased as the season progressed to a maximum difference of approximately 0.3 pH unit at the end of the season, Figure 5A. Figure 5B shows that the air dry soil pH values measured with the Truog kit during the sea— son were approximately 0.2 pH unit higher, on the average, than the corresponding pH values measured in water with the 3 glass electrode. The air dry pH values showed an upward trend in September with the Truog and glass electrode methods, in- dicating a cyclic trend back toward the higher pH values early . l in the season. Summary Regardless of suspending media, the field moist soil pH’s showed a steady decrease in values as the season pro- gressed, and the ovaidry and air dry pH's showed a cyclic seasonal trend, Figures 3 and H. However, it is apparent that soil pH measurements are influenced by the moisture condition of the sample and the suspending media. At the beginning of the season, in May, the oven dry pfli's measured in water were as much as 0.88 pH unit lower than the corresponding field moist pH values. Differences between the mean of the air dry and oven dry pH values measured in ‘wateI'eum.in 0.01MCaC12 were not significant. At the end of time season, there were also no significant differences between pfli'values measured at the three moisture conditions in water or 111 0.01MCaC12, Figure 3. -u2_ Field moist pH values measured in 0.01MCaCl2 showed less seasonal variability than the corresponding pH's measured in water. However, the oven dry and air dry pH's measured in O.OlMCaC12 were Just as variable as the corresponding pH's measured in water, Figure 3. The air dry pH's measured in 1.0NKC1 showed less seasonal variability than the corres- h ponding pH's in water or in 0.01MCaC1 Figure h. 2' The 0.01MCaC12 pH's were lower than the mean pH values measured in water at the following moisture conditions by ,5 u the following amounts: Field moist, 0.85 pH unit; and oven k dry, 0.61 pH unit. The air dry pH's measured in 0.01MCaCl2 and in 1.0NKC1 were 0.6 and 1.0 pH unit lower, respectively, than the corresponding pH's measured in water, Figure b. On the average the field moist pH values determined with the Truog kit were as much as 0.3 pH unit higher than the correSponding pH values measured in water with the glass electrode at the end of the season, in September, Figure 5A. However, on the average, the air dry pH's determined with the Truog kit were 0.2 pH unit higher than the pH values measured in water with the glass electrode, Figure 5B. Several factors influencing the seasonal variability of soil_pH values The field moist pH values, measured in water, of all the nineteen soil sites studied showed seasonal variability (Table 7), as illustrated in Figure 3 for the ten sites. However, only mar-Lu a -43- fourteen of the sites showed seasonal variability of soil pH when the air dry pH's measured in water were considered, Table 7. Variations of the pH's of the other five sites (Chelsea, Hillsdale No. 2, Houghton, Oakville and Pewamo No. 1) measured during the season fell within the range of the experimental error, i 0.3 pH unit, deduced in this study. ? Even though differences between the pH values for each of 2 these five sites measured during the season were not signif- E icant, it appears that there may be a seasonal trend similar 2 L to that illustrated in Figure h, as shown in Figure 6. Seasonal variations of the field moist pH values meas- ured in water ranged from 0.5 pH unit for Chelsea to 1.6 pH unit for Pewamo No. 1, Table 7. The seasonal variations of the corresponding air dry soil pH values ranged from 0.5 pH unit for Nekoosa No. l to 0.9 pH unit for Pewamo No. 1, Table 7. Tohelp explain these seasonal variations in soil pH measurements the field moisture content, the total exchange- able metallic cations, the electrical conductivity and the organic matter content were determined on each sample col- lected from each site during the season. These data for each site and for each month are presented in Table 8 in the appendix. In addition, the cation exchange capacity of each site was determined on one of the samples from each site. The Figure 6 e 6.2 5.8 -4n- Variability of the air dry pH's of five soil sites measured dur- ing the season. I l 1 June July Aug Sept Time -45- percent base saturation and the exchange acidity were cal— culated using the cation exchange capacities and the ex— changeable metallic cations. It was assumed that there were no changes in the cation exchange capacity of each site during the season. The cation exchange capacity, the calculated percent base saturation and the calculated ex- change acidity for each site are shown in Table 8B in the appendix. Statistical analyses of these data were made under the supervision of Dr. C. E. Cress in the Crop Science De- partment with the assistance of Mrs. N. Galuzzi and the Com- puter Laboratory. The resulting significant correlations between the pH's and these soil prOperties are shown in Table 9. Electrical conductivity and organic matter percentage were negatively and positively correlated, respectively,with soil pH's, Table 9. The negative correlation shows that the increase in electrical conductivity, due probably to the presence of soluble salts, is associated with decreases in soil pH values. There is also a significant increase in field moist soil pH's with an increase in the moisture per- centage. These two relationships may thus be direct corollaries of increasing the salt concentrations and diluting their in- fluences on soil pH's, respectively. -46- Table 9 Significant simple correlations between_sea- sonal variability of soil pH and field moisture percentage, base saturation percentage, elec- trical conductivity and organic matter content. Correlation of field moist pH's measured in water with: Field mOiSture percentage eoeeeeeooeeeeoe r Base saturation percentage eeoeeeeeeeeeee r Electrical COHdUCtiVity eeeeeeeeeeeeeeeee r Organic matter content eeeeeeeeeeeeeeeeee r Base saturation and organic matter percentages ........................... r Correlation of air dry pH's measured in water with: Ease saturation percentage .............. r EleCtrical condu0t1v1ty eeeeeoeeeeeeeoeee r Organic matter content eeeeeeoeeeeeeeeeee r Correlation of field moisture percentage with: EleCtrical condUCtiVity eeeeoaeeeeeoeeeoe r Organic matter percentage eeeeeeoeeeeeoee r *Significant at 5% level +0.285* +0.493* -0.336* +0.592* +0.638* “—1- r-' w. -47- Seasonal variations of electrical conductivity and or- ganic matter content were highly correlated with field mois- ture percentage, Table 9. This helps to explain why organic matter gave the highest correlation between seasonal varia- bility of the field moist soil pH values and the lowest cor- relation between the seasonal variability of theedr dry soil pH values. This is due to the fact that organic matter in- fluences the amount of moisture present at the field moist condition and to the dilution effect of increased moisture on the soluble salts present. The relatively low correlation between seasonal var- iability of soil pH values and percent base saturation may be partially due to the presence of soluble salts which will be counted in the exchangeable cations but will tend to decrease rather than increase the pH. However, the air dry pH's of eight of the sites (Blount, Ceresco No. l, Colwood No. 2, Hillsdale No. l. Nekoosa No. l, Pewamo No.1, Plainfield and Spinks No. 2) also showed seasonal variability when measured in 0.01MCaClé, Table 7. Two of the sites, Blount and Hills- dale No. 1, showed seasonal variability even when measured in 1.0NKC1, Table 7. These indicate that other factors besides electrical conductivity are responsible for the observed variations in the measured pH values of some soils. However electrical conductivity, believed to be largely a reflection of salt content, is responsible for most of the seasonal -48— variability of the pH's of most of the soil sites used in this study. It was assumed that there were no significant season- al variations in the cation exchange capacities. However, there were variations of as much as ten percent, in the or- ganic matter percentages during the season. Therefore, it is possible that the cation exchange capacities also varied seasonally. Seasonal variability of the cation exchange capacities may partially account for the relatively low cor- r” ‘* “a“ :;_:..;'_:v relation between seasonal variations of soil pH values and the base saturation percentages, as calculated in this study. Seasonal variability of lime requirement The variation of lime requirement was evaluated on air dry samples collected from eleven sites by the following three methods: pH plus texture, SMP or buffer and exchange acidity. Lime requirement was determined on all air dry soil samples with pH values less than 6.5 when measured in ‘water with the glass electrode. These data are presented in TableJED and the variations of the average lime requirements for four months (June through September) are illustrated in Figure 7. On the average, the pH plus texture method showed the maximum seasnnal variability of lime requirement, which was approximately 1.0 ton per acre, Figure 7. The maximum average -49- variations in lime requirements by the buffer method during the season were more comparable to but greater than those in the exchange acidity method, Figure 7. The pH plus tex- ture and S.M.P. buffer methods showed a cyclic seasonal trend in lime requirement, with the maximum in mid-summer (July), Figure 7. Contrary to these the lime requirement evaluated T} by the exchange acidity method tended to fluctuateless during i the season. Seven of the eleven soil sites with evident lime re- :5 . 3‘ quirement had zero lime requirement at the beginning of the season or in May, Table 10. However, each of the eleven sites exhibited maximum lime requirement in July or in August. The maximum difference in lime requirement evaluated by the pH plus texture method was 2.5 tons per acre for Hillsdale No. 2. Similarly, the maximum difference in lime requirement determined by the S.M.P. buffer method was 2.3 tons per acre for Pewamo No. 1. However, the maximum seasonal difference in lime requirement for any soil studied was with use of the exchange acidity method on samples collected from Pewamo No. 1. Here the lime requirement varied from 0.0 early in the season to 4 tons per acre in July, Table 10. Thus, it is concluded that the seasnnal variability of lime requirement should be considered when lime recommenda- tions are made. -50- Figure 7. Seasonal variability of average lime requirement determined by three methods. \o s M P Buffer L4 - /°\ opH plus Texture l.2r |,o - cfExchange Acidity r / 0.8 - ° 0 0.6- Average Lime Requirement- Tons/acre. I J June July Aug Sept Time -51- SUMMARY AND CONCLUSIONS A study of the seasonal variability of the pH's and lime requirements of several soils in Southern Michigan was con- ducted. The experimental errors in pH determinations were evaluated. Results of chemical and physical soil analyses were studied and correlations of those results with pH dif- ferences were calculated to determine the relationship of several soil prOperties to the seasonal variability of soil pH values. The results of this study are summarized as follows: 1. To be reasonably certain of a significant dif- ference between individual soil pH values, a varia— tion greater than i 0.3 pH unit is necessary. How- ever, when mean soil pH values of a representative number of observations are compared, differences greater than i 0.15 pH unit are likely significant. 2. Field moist soil pH values measured in water usually showed marked seasonal variability. A maximum vari- ation of 1.6 pH units was observed, and the average seasonal variation was approximately 0.8 pH unit. The highest and lowest pH values were early in the season and at the end of the season, respectively. The correlation between organic matter content and season variability of these pH values was the high- est of the correlations with the soil factors studied. This is probably due to the combined ‘7ZLJ a. -52- effects of the relationships of organic matter content to field moisture content, and field moisture content to electrical conductivity. On the average, during the wetter portion of the season, the air dry and oven dry pH values measured ‘- . +- in water were approximately 0.5 and 0.8 pH unit lower, respectively, than the corresponding field ‘Md —-- moist pH values. During the drier part of the season, differences between average pH values ‘rn— .. .—‘—-I~« .hk- V‘ .s . measured at the three moisture conditions were less than 0.1 pH unit and non-significant. Air dry and oven dry pH values measured on samples collected during the drier portion of the season may be better expressions of the pH in the field than the corresponding pH values measured on samples collected during the wetter part of the season. Therefore, when soil pH values are in- terpreted for various purposes the moisture con- ditions and the time of collection of the soil samples should be considered. Only four of eleven soil sites exhibited a lime requirement during the early part of the season, based on air dry samples, but each of the eleven sites showed a lime requirement during the middle of the summer. A maximum seasonal variation of 4 tons per acre was observed for an individual site, -53.. using the exchangeable hydrogen method for lime requirement. Therefore, the time of sampling and the method for estimating lime requirement are factors that should be considered in making lime requirements recommendations. The relative magnitude of the seasonal variability of soil pH values, measured in both water and in 0.01MCaC12, at the three moisture conditions is as follows: field moist>oven dry "1 air dry. Drying soil samples in an oven facilitates the time and space necessary for drying. Therefore, it appears that oven dry soil samples are best adapted for routine pH determinations. On the average, 0.01MCaC12 and 1.0NKC1 lowered air dry soil pH values measured in water approximately 0.6 and 1.0 pH unit, respectively. The relative order for the seasonal variability of air dry pH's measured in the three suspending media is as follows: H20) 0.01MCaClZ> 1.0NKC1. However, for some soils the 0.01MCaC12 pH's were just as variable as the pH's measured in water. Field moist soil pH values determined with the TruOg kit showed less seasonal variability than the corresponding pH values measured in water with the glass electrode. However, on the average, the Truog pH values were higher than the pH values 444! 9.’ -54- measured in water with the glass electrode. 0n the average field moist and air dry soil pH values determined with the Truog kit were not more than 0.3 and 0.2 pH unit higher, respectively, than the corresponding glass electrode pH values. The Truog kit is also well adapted for field work, especially soil survey. Therefore, the Truog kit, as it is commonly used by soil surveyors in Michigan, appears to be a satisfactory field kit for pH determinations. Soil pH values measured in 1.0NKC1 were the least variable during the season and appeared to reflect an intrinsic characteristic of the soil. There- fore, these pH values may be very useful in reseasch work and soil classification, especially in classi- fying soils at the family level in the 7th approx- imation. These pH values may also aid in making lime requirement recommendations that are rela- tively free of seasonal influences. Seasonal variability of air dry soil pH values measured in water were negatively and highly cor- related with electrical conductivity of the samples. Also, most of the soil sites exhibited no seasonal variability of soil pH values when measured in 1.0NKC1. This indicates that soluble salts are probably responsible for most of the observed 10. -55- seasonal variability of soil pH values. However, two of the nineteen soil sites showed seasonal variations even when measured in 1.0NKC1, so soluble salts cannot explain all of the seasonal variations in pH's. Further study is needed to determine what and how other soil properties influence the seasonal variability of soil pH values and lime require- ments of soils. a7 .“4‘. .. ———.‘—~ .n'. ‘ry m. . .-.. m. .p‘. —- u..— 10. 11. 12. LIST OF BEFEEENCES Alexander. Martin. Introduction to Soil Microbiology. John Wiley and Sons, Inc.. New York, 1967. Arrhenius, 0. Hydrogen ion concentration, soil pro- perties and growth of higher plants. Ark. 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APPENDIX .63_ Table 7 Soil reaction measured at three moisture conditions and in several suspending media for each site on each sampling date May sampling Field Moist pH's Soil Truog Glass Electrode Site Kit H20 0.01MCaCl2 Blount 6.7 6.8 7.2 7.2 6.4 4.4 Ceresco(No.l) 7.8 8.0 8.0 8.0 7.0 7.0 Hillsda1e(No.1) 6.8 6.7 6.7 6.7 5.5 5.5 Houghton 6.7 6.7 7.1 7.1 6.3 6.3 Lapeer 6.6 6.7 7.5 7.5 6.5 6.5 Nekoosa(no.1) 6.8 6.9 7.1 7.1 6.3 6.3 Oakville 5.9 5.7 6.5 6.5 5.1 5.1 Pewamo(No.1) 6.7 6.7 7.4 7.4 6.5 6.6 Plainfield 5.5 5.4 6.0 6.0 4.8 4.9 Spinks(No.1) 5.8 5.8 6.7 6.7 5.5 5.5 Air Dry pH's it Truog Glass Electrode Kit H20 0.01MCaC12 . 1.0NKC1 Blount 6.6 6.6 6.6 6.0 6.0 5.1 5.1 Ceresco(No.1) 8.0 8.0 7.5 7.0 6.9 6.3 6.4 Hillsdale(No.1) 6.0 6.0 6.0 5.3 5.3 4.9 5.0 Houghton 6.8 6.8 6.6 6.0 5.9 5.6 5.7 Lapeer 7.0 7.0 7.2 6.3 6.3 6.0 6.0 Nekoosa(No.1) 6.4 6.4 6.7 6.1 6.1 5.6 5.6 Oakville 5.5 5.6 5.9 4.8 4.8 4.3 4.2 Pewamo(No.1) 6.7 6.5 6.9 6.3 6.3 5.5 5.5 Plainfield . 5.5 5.5 5.5 4.5 4.5 4.2 4.3 Spinks(no.1) 6.0 6.0 5.8 5.2 5.2 4.8 4.9 Oven Dry pH's H20 Glass EleCtrOdeO.01MCaC12 Blount 6.2 6.2 5.7 5.7 Ceresco(No.l) 7.0 6.9 6.5 6.5 Hillsdale(No.l) 5.8 5.7 5.2 5.2 Houghton 6.1 6.2 5.9 5.9 Lapeer 6.7 6.7 6.0 6.0 Nekoosa(No.1) 6.5 6.5 5.8 5.8 Oakville 5.4 5.5 4.8 4.7 Pewamo(No.1) 6.6 6.6 6.0 6.0 Plainfield 5.1 5.1 4.5 4.5 Spinks(No.1) 5.8 5.8 5.1 5.2 ’ J n u - ._(_.__ ‘ Electrode Glass £29 A ( Continued LA 1:0 11'01 in r ... so“ U Truog hit June Table 7. O \4 oil Sit r: L.) . ... In ‘fif... m an .Iv , .r. k ..w... I." .. 2609.88.51. _16.0/5_5_5 67566 .5...5_ .6/6 _6/0 _c../— 0 6O OPUS/0:4 129~168 955573 6 75664 55.666.64.664 556 $0709176205J282956586 7.:00 700 756/0 771776 77566 7 10 J20/7/0 20538 28 56 576 n/8 n/.OO 756/0 777m/C 7756/0. 7 loo-449:2.UOO-521nw2/nw4/6U- O O O O O O O O O O O O 788 77566 m/6/0 76 n/.-75/nw/0 _0nunY4n40(426120:2211123:¥4n(u. 78 96 775/06 776 76 77566/0 1.2 1212 .. 12 .onu 112 112 a... TAN cc 0000 06 ..d.. NNNN ee KN ooloor lln eNNeNLi ooddaaao aal i a tcoooeddtrssloofssl nSSOOSSSheooimmnmxc ueewwlllaeoowaairr orrllellupkktwwaii. leeoohit;:e€eweelppt BCCCCCHHHLVANOPPPSOQQH 1. OI‘IQCI 0.01LCaC12 £29 Truog Kit —— Air Dry_pH's 0143-42018u25nw4560924 666664 54 56 570.4 5.).44 55 1522110851313370023 e e o o e e e . (6636/0A84.Dn-KioyDAY4.D<¥4rD