70-15,159 WOOD, Warren W., 1937GEOCHEMISTRY OF GROUND WATER OF THE SAGINAW FORMATION IN THE UPPER GRAND RIVER BASIN, MICHIGAN. Michigan State University, Ph.D., 1969 Geology U niversity Microfilms. Inc., A nn Arbor, M ichigan GEOCHEMISTRY OP GROUND WATER OP THE SAGINAW FORMATION IN THE UPPER GRAND RIVER BASIN, MICHIGAN By Warren W. Wood A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Geology 1969 PLEASE NOTE: Some pages have small and indistinct type. Filmed as received. University Microfilms ABSTRACT GEOCHEMISTRY OF GROUND WATER OF THE SAGINAW FORMATION IN THE UPPER GRAND RIVER BASIN, MICHIGAN By Warren W . Wood The Saginaw Formation of Pennsylvanian age serves as 3/ a potable water aquifer over 2,500 square miles in the Grand River basin, Michigan. This formation of sandstone, shale, limestone and coal is overlain in most of the basin by several hundred feet of glacial material of Pleistocene age. The ground water hydrology of the system is one of recharge by local precipitation through the overlying glacial drift. Dissolved solids in the ground water of the Saginaw Formation are evaluated as to the most Important source. Glacial drift and soils are found to contribute more dis solved solids to the ground water of the Saginaw Formation than atmospheric precipitation, migration of water from other formations, or solution of minerals from the Saginaw Formation. Sodium is the only major chemical constituent that exhibited a coherent concentration distribution within the Saginaw Formation. Other constituents failed to yield Warren W. Wood concentration trends. Dissolved solids within the Saginaw Formation were found to be lower than that of the recharg ing water of the glacial drift. Zones of high concen tration of dissolved solids are found locally in the overlying glacial drift through which the recharge to the Saginaw Formation passes. Ahion exchange, mineral p re cipitation, ultrafiltration, fossil water and selected recharge areas were considered in explaining the difference in dissolved solids between the Saginaw Formation and the overlying glacial drift. It is hypothesized, that by a process of reverse osmosis and ultrafiltration shale members of the Saginaw Formation filter out certain ions. This hypothesis explains many factors associated with the distribution of dissolved solids. Equilibrium calculations were performed using the common carbonates, sulfate and Iron minerals. Siderite was found to be the Iron mineral most likely in equilibrium with the ground water. Carbonates of calclte and dolomite were, In general, in equilibrium with the ground water while the sulfates of gypsum and anhydrite were greatly undersaturated. ACKNOWLEDGMENTS I wish to thank Dr. Samuel B. Romberger, my thesis advisor, who gave freely of his time in many discussions and also provided many chemical analyses from a concurrent study. I also wish to thank my colleagues Mr. Kenneth E. Vanlier and Mr. Gerth E. Hendrickson of the U. S. Geologi cal Survey who have been particularly helpful in discussions of new concepts as they have developed in the course of the study. Drs. Paul Jones, William Back and Bruce B. Hanshaw, also of the U. S. Geological Survey, gave helpful sugges tions on the ion distribution section of the thesis. I wish also to thank members of my thesis guidance committee, Drs. Robert Ehrlich, William Hinze, Harold Stonehouse and James Trow, who critically reviewed the manuscript. Thanks also go to Mr. Gary C. Huffman of the U. S. Geological Survey who wrote the computer program for the statistical analyses used in this study and the National Science Foundation who provided one-half hour of computer time. ii TABLE OP CONTENTS Page ACKNOWLEDGMENTS ........................................ 11 LIST OP T A B L E S ........................................ V LIST OP FIGURES .......................... INTRODUCTION ........................................... Purpose and Scope ................................. Previous Studies. . . . Methods of Investigation ........................... GEOLOGY OP THE SAGINAW FORMATION vi 1 1 3 4 .................... 8 Introduction ........................................ Regional Setting. . . . . . . . . . . . Occurrence and Type Locality....................... Thickness and L i m i t s .............................. Llthology . . . . . . . . . . . . . . 8 8 9 10 12 GEOHYDROLOGY ........................................... 17 Introduction ........................................ Regional Setting.................................... 17 17 GEOCHEMISTRY OP GROUND WATER IN THE SAGINAW FORMATION 24 Type and Concentration of Major I o n s ............. Source of Dissolved Solids in Ground Water . . . 24 24 Atmospheric Precipitation....................... Soil and Glacial Material....................... Saginaw Formation .............................. Stratlgraphlcally Lower Formations............. Dissolved Solids Budget ....................... 24 25 34 36 42 ill Page Dissolved Solids Distribution . . . . . . . *4*4 Areal T r e n d s ..................................... Vertical D i s t r i bu t i o n ........................... Explanation of Observed Distribution. . *4*4 *48 . 53 Pre-Pleistocene age water ............... Selected areas of r e c h a r g e ............. Anion e x c h a n g e ........................... Mineral reduction ........................ Reverse osmosis and ultrafiltration . . 53 5*4 5*4 55 55 Mineral E q u i l i b r i a............... . T h e o r y ........................................ • . Data A n a l y s i s .................................. SUMMARY AND CONCLUSIONS 63 63 68 .............................. 76 BIBLIOGRAPHY............................................ 80 A P P E N D I X ............................................... 85 iv LIST OP TABLES Table 1. Page Physical Properties of Clay from the Saginaw Formation at the Grand Ledge Quarry . . . 14 2. Sources of Dissolved Solids in Ground Water . 26 3. Statistical Comparison of Chemical Parameters of Water at High Stream Plow with Low Stream P l o w .................................. 33 Chemical Analyses of Water from the Michigan and Marshall Formation .................... 37 Statistical Comparison of Chemical Parameters of Water from Glacial Drift and Low Stream Plow with the Saginaw Formation . . . . 50 Statistical Comparison of Chemical Parameter of Water from Glacial Drift with the Saginaw Formation ........................... 51 Statistical Comparison of Chemical Parameter of Water from Wells Cased in Sandstone . with Those Cased in Shale of the Saginaw F o r m a t i o n ..................................... 62 A - l . Chemical Analyses of Ground W a t e r .............. 85 A —2 • Chemical Analyses of Stream W a t e r .............. 94 A - 3 • A Comparison of K SD and Kiap for Gypsum, Anhydrite, Calcite, Aragonite, Dolomite and S lderlte.................................. 97 4. 5. 6. 7. LIST OF FIGURES Figure 1. 2. 3. 4. Page Map Showing Generalized Topography and Location of the Grand River Basin . . . . 2 Map Showing Location of Wells Sampled and Extent of the Grand River Group and Saginaw Formation ..................................... 5 Map Showing Thickness of the Saginaw For mation ....................... 11 Map Showing Potentiometric Surface of the Saginaw Formation ............. . . . . 20 5. Hypothetical Section of Grand River Basin Showing Potential Distribution and Two Dimensional Patterns of Major Ground Water F l o w ................................... 23 6. Map Showing Location of Stream Sampling Sites 7. Water Analysis Diagram for Selected Paleozoic Formations in Michigan...................... 33 8. Map Showing Distribution of Chloride in the Saginaw Formation Near an Abandoned Brine Well in the City of Lansing Sf.4N.,R.2W . . . 9. Map Showing Distribution of Sodium in the Water of the Saginaw F o r m a t i o n ............ 46 10. Diagram Showing Process by Which Dissolved Solids are Controlled by Hydrology and Geology.......................................60 11. Graph Showing Solubility of Iron in Relation to pH and Eh at 11°C and 1 Atmosphere Pressure. Total Dissolved Sulfur 10-3 m, Bicarbonate Species 10-2.5 m ............. vi 31 40 71 Figure 12. Page Graph Showing Change in Specific Conductance of Well Water with Time, on Exposure to the A t m o s p h e r e ................ vii 75 i INTRODUCTION Purpose and Scope This thesis describes the distribution, source and mineral equilibria of the major chemical constituents in water of the Saginaw Formation in the Upper Grand River basin of Michigan. This study is an attempt to integrate the major dissolved constituents of ground water with the geology and flow system of a major aquifer system. The ultimate purpose of this thesis Is to describe the manner in which the geochemical system functions within the aquifer system. Information of this type is essential to understanding the physical hydrology and utility of the aquifer. The Saginaw Formation in the Upper Grand River basin was selected for this hydrogeochemical study because the geology and hydrology are relatively well known. Addi tionally, there are numerous wells tapping the aquifer which are suitable for water quality sampling, and at least one major outcrop area exists for the collection of rock samples. The area of investigation is near the center of the Lower Peninsula of Michigan (Figure 1). It comprises all of Clinton and Ingham Counties and parts of Eatop, Living ston, Ionia, Gratiot, Montcalm, and Shiawassee Counties— F i g u r e 1 .— Map showing generalized topography and location of the Qrand River basin. 3 an area of about 3,000 square miles. The topography of the basin is given in Figure 1 and the stream network in Figure 6. The Saginaw Formation is utilized as an aquifer throughout its extent in the Upper Qrand River basin. The aquifer is used most extensively in the Lansing Metropoli tan area, where approximately 30 millions gallons per day (mgd) are presently being pumped (Giroux and Huffman, 1967). Total pumping from the aquifer in the study area, including industrial, agriculture, and domestic supplies is estimated at 45 mgd. This thesis is concerned with only one aquifer of the many in the Michigan Basin. However, the aquifer system is typical of many in the glaciated north central United States and the relationships observed for this particular hydrologic system should have, with modification, appli cation to other hydrologic systems. Previous Studies Geology and hydrology of the Saginaw Formation, in the Grand River basin, have been studied by many workers because of its importance as an aquifer in the Lansing Metropolitan area. Geology of the Saginaw Formation, including the area in the Upper Grand River basin has been described in detail by Kelly (1936). A study of the geology in the Lansing area was made by Mencenberg (1963). Hydrology of the Saginaw Formation in the Lansing area has been studied by Stuart (1945), Firouzian (1963), and ** most recently by Wheeler (1967) and Vanlier and Wheeler (1968) by means of a resistive capacitive electric analog model. A report by Vanlier (196*0 contains a general dis cussion of the geology, hydrology and water quality of the area of Clinton, Eaton, and Ingham Counties which are further treated in more detail by Vanlier, Wood and Brunett (1969). Hydrology, chemical quality of surface water, and water use of the Upper Grand River basin has been discussed by the Water Resources Commission of Michigan (1961). There have been no previous studies of the geochemistry of the ground water of the Saginaw Formation. Methods of Investigation Location and llthologic description of wells were obtained from the files of the Michigan Geologic Survey and the U. S. Geological Survey. Wells were selected for areal coverage, age of formation penetrated, topographic region, and hydrology. As a result of a recent Michigan Drilling Act (Public Act 29** of 1965)* which requires drillers to submit a record of all water wells drilled with their description, much of the data used herein are from wells less than 2 years old. Samples collected for this study (Figure 2, Table A— 1) were analyzed by the Water Analysis Laboratory, Department of Geology, Michigan State University. Concen trations of calcium, magnesium and iron were determined by atomic absorption spectrometry on samples acidified shortly CIINtoW ICNIi E X PL A N A T IO N M r ! Figure 2.--Map showing location of wells sampled and extent of the Qrand River Group and Saginaw Formation. 6 after collection. Acidification was necessary to maintain the carbonate and iron minerals in solution at atmospheric conditions. Sodium and potassium were determined by flame photometer from the same acidified samples. Chloride was determined by the merculric nitrate method (American Public Health Association and others, 1965), and sulfate by the turbidimetric method using a Hach colorimeter (Hach Chemi cal Company, Ames, Iowa). Bicarbonate was determined at the time of collection, by colorimetric methods, during the early part of the study, and later a potentiometrie method was used. The pH was also determined at the time of collection using a standard combination glass electrode and pH meter. Many samples were collected through pressure tanks and associated plumbing in domestic wells. To insure a fresh sample, the water was pumped for five minutes after the pump started or until the temperature of water re flected aquifer temperature or about 11°C. Previously, published chemical analyses were obtained from the Michigan Department of Health and the U. S. Geological Survey. Analyses from these sources were used only if a description of the geologic formation was available. Analyses per formed by the U. S. Geological Survey were made at Columbus Ohio, and follow analytical methods given in Rainwater and Thatcher (i9 6 0 ). Analyses performed by the Michigan Depart ment of Health were made at Lansing and follow procedures given by the American Public Health Association and others (1965). 7 Analyses were considered to be complete If all the major constituents in the water were determined. Results of complete analyses expressed in this study balanced within 5 per cent, that is the total cations expressed as milliequivalents per liter (meq/1) are within 5 per cent of the total anions also expressed as meq/1. Because ionic solutions must be electrically neutral, the number of equivalents of cations must equal that of the anions. The unit meq/1 is the valance of the ion divided by its molecular weight times its concentration in milligrams per liter. This balance insures that all major constitu ents have been determined and also provides a check on the analytical procedures used. The quality of partial analyses depends upon the reputation of the laboratory and the methods of analyses. Partial analyses used in thiB study are only from the sources listed above. Results of analyses are reported in milligrams per liter (mg/1) for all parameters except pH and specific conductance. The pH is reported in standard pH units (negative logarithm of the hydrogen ion activity) and specific conductance in mlcromohs per centimeter at 25°C. The unit milligrams per liter can be considered numerically equal to parts per million (ppm) in the analyses used in this report because of the dilute nature of the waters studied. t GEOLOGY OF THE SAGINAW FORMATION Introduction Material comprising an aquifer system will have a significant influence on the chemistry of the intersltual water. Geochemical process of mineral solution, precipi tation, ion exchange and ion filtration are functions of the type and distribution of the lithology of the aquifer system. Therefore, an examination of the geology is critical to the complete understanding of the hydrogeo chemical system. Regional Setting The Saginaw Formation occurs in the Michigan Basin sedimentary sequence. This sedimentary sequence contains Paleozoic age sediments approximately 14,000 feet in thick ness and a thin and scattered sequence of Mesozoic age sediments (Michigan Department of Conservation, 1964). The Michigan Basin is bordered by the Precambrian Shield on the north and northeast; on the west by the Wisconsin Arch on the southwest by the Kankakee Arch in northern Indiana and northeastern Illinois; and on the east and southeast by the Algonquin Arch in Ontario and the Findlay Arch in northern Ohio. The stratlgraphlc sequence of the basin contains sediments of all Paleozoic periods except the 8 9 Permian. These sediments are deposited In a basin which results In a series of saucer shaped beds with each for mation being smaller In areal extent than the formation on which It Is deposited (Eardley, 1962). The formations in general dip toward the center of the basin at about one degree. Paleozoic and Mesozoic formations are mantled by a layer of Pleistocene age glacial drift which ranges in thickness from a few feet to over 1,000 feet. Occurrence and Type Locality The Saginaw Formation is one of two Pennsylvanian age formations in the Michigan Basin. The other Is the Grand River group which unconformably overlies the Saginaw (Figure 2). The name Saginaw Formation was originally proposed by Lane (1901) as a replacement for the terms "JackBon” and "Coal Measures." group status by Kelly (1936). The name was elevated to It has s i n c e :been returned to formation rank by the Michigan Department of Conser vation (1964). The Saginaw Formation as used in this report Includes the Parma Foundation described by Winchell (l86l). This is necessary because it is Impossible to differentiate between the Parma and sandy facies of the Saginaw as shown in well cuttings or driller's descriptions. The type locality of the Saginaw Formation is the Saginaw Valley outside the study area; however, because there are no outcropB in the type locality and because coal mining has been abandoned, the outcrop in Eaton County 10 near the town of Grand Ledge has become the type section (Kelly, 1936). Thickness and Limits The extent of the Saginaw Formation (Figure 2) should be viewed as an approximation. The problem of defining the extent is complicated because the upper and lower sur faces are erosion surfaces. The thickness map (Figure 3) was made by subtracting the two surfaces and contouring the residual. Valleys in the pre-Saginaw surface can be readily delineated in areas where data are adequate. In the peripheral area of the Grand River Group, preservation is in low areas of the Saginaw Formation indicating erosion of the Saginaw Formation surface prior to the deposition of the Grand River Group. The combination of this erosion surface with the pre-glacial and glacial erosion results in a highly dissected surface on which to estimate thick nesses. The Howell Anticline further complicates estimates of thickness in the northeast part of the study area. The formation thins rapidly as the structure is approached and may have been involved in uplift and erosion, or the area may have been a topographic high during the deposition of the Saginaw Formation. In this part of the Michigan Basin it is extremely difficult to distinguish the sandstoneshale sequence of the Saginaw Formation from the Michigan, Marshall and Coldwater Formations on the basis of water / 11 I CUNrOM fM 41 •• M4 MM IQMW - -I •441 m EXPLANATION im. _ C « * t* a r „ i f f f# # | For Figure 3 •--Map showing thickness of the _ mation (modified after Vanlier, Wood and Brunett, 1969) I 12 well drillers logs; consequently, the extent and thickness of the formation here Is uncertain. Llthology The Saginaw Formation Is similar In composition to other Pennsylvanian age deposits of the Eastern Interior Basins in Illinois and Pennsylvania. It Is composed of numerous beds of shale, sandstone, slltstone, coals and occasional limestone. Most of the lithologic types are non-persistent as Individual members and cannot be traced over extensive distances. However, Kelly (1936) believes that at least one limestone member, which he calls the Vern Limestone, is recognizable over a large area. The sandstones are lenticular, often ending abruptly against shale, and are usually less than 20 feet thick. However, In the Lansing Metropolitan area there are 300 feet of sandstone In a formation thickness of about 400 feet. The sandstones are composed of very fine quartz grains and contain abundant light colored mica as an accessory mineral. The dominant colors reported in drillers logs are light buff and dark grey. Kelly (1936) found tourmaline and zircon the most common heavy mi n e r a l s. In addition to inorganic material there are fossil plant fragments in the sandstone outcrop at Grand Ledge and probably throughout the basin. The cementing agents from samples collected at the Grand Ledge outcrop are silica and 13 and calcium carbonate. The pore space Is very small In the samples examined by the author. The shales of the Saginaw Formation, like the sand stones, are not persistent over great distances and appear to have been truncated by channel sands In many Instances. The term shale Is used In a broad sense and Includes every lithologic type the driller does not consider sandstone, coal or limestone. The latter three lithologic types are easily recognized in drilling. The shale designation In cludes shale, siltstone and underclay. The colors recorded are black, blue, brown, buff, gray and white. Black or dark gray is the most often recorded color. Results of examination of the clay fraction (less than 2 microns) from two samples collected at a Grand Ledge quarry are given below. These analyses were performed by Mr. Bailey and Mr. Chazen of the Department of Geology, Michigan State University. The clay fraction was removed from the shale by mechanical disaggregation. Carbonates were removed using a sodium acetate buffer adjusted with acetic acid to a pH of 5. Organic matter was removed by using hydrogen peroxide and free iron oxides were removed by the sodium citrate sodium dltheonlte method. The clay sized fraction was obtained by use of sedimentation cylinder. The fraction obtained was then subjected to analyses indicated in Table 1. In addition, infrared, x-ray TABLE 1.— Physical properties of clay from the Saginaw Formation at the Grand Ledge quarry. Sample Number A B Lithologic description and looation Black oolored fissil shale collected near bottom of a new shale pit Light brown colored siltstone to shale collected near top of quarry wall Speoifio surface area, in square meters glycol method I II Cation exohange capacity oa/mff meq/100 gr I II Cation exohange oapaoity K/NHlf meq/100 gr I II Ave 326 I II 76.6 60.8 Ave 67.7 I II 80.5 50.5 6* 40 Ave 52 I II tz 35* 295 395 326 Ave 365 Ave 65.5 Ave *8 4 15 diffraction and differential thermal analysis were performed on the sample. The results of these investigations com bined with the physical properties (Table 1) indicate the following percentage and type of clay minerals present. B 59% Kaolinite 42$ Kaolinite 30J6 Illlte 46$ Illite 11$ Vermiculite 12$ Vermiculite trace of quartz and chlorite trace of plagioclase and quartz The underclays are very light in color at the out crop and according to Kelly (1936) contain irregular nodules of iron carbonate. Because underclays are seldom recorded in drillers logs as distinct units it is diffi cult to determine the extent of the facies. Presumably they would be found beneath coal zones. Coal provided the early impetus to study the Saginaw Formation, however, this is not a common lithologic type in the study area. Because of its color and physical properties it is easily recognized in drilling. Its absence in drillers records is thought to be an indication that coal beds are not abundant in the study area. Limestone is commonly recorded in drillers l o g s . However, its thickness is small, usually less than 2 feet, and several different beds are often recorded in a single well. Because limestones are extremely resistant to 16 drilling even though they are thin, they are recorded by moBt drillers and probably gives a positive bias to the amount of limestone recorded in the logs. As mentioned previously, Kelly (1936) believed that at least one of these limestones is extensively distributed. QEOHYDROLOQY Introduction Source, distribution and movement of water within the aquifer system affect the water chemistry. To evaluate the type, amount, and spatial distribution of the chemical constituents it is necessary to identify the source and quantity of the water and the potentiometric distribution of the hydraulic head in the formation. Regional Setting The source of water in the Saginaw Formation in the Grand River basin is precipitation within the topographic basin. In certain instances small amounts of water are lost to or received from adjacent basins, but in general the ground-water basin corresponds very closely to the topographic divide. Precipitation on the Grand River basin above Ionia averages annually 31*12 inches (Water Resources Commission of Michigan, 1961). This value was determined by using the Thiessen method of mathematically weighing precipitation from stations In and adjacent to the basin. Stream runoff for the same area, based on sixteen years of record averages 7.63 inches annually (U. S. Geological Survey, 1968). 17 The difference, 23.^9 18 Inches, Is the average annual lost to evapotransplratlon. The precipitation and runoff data are based on a slightly smaller area than that used In this study. However, they do represent the hydrologic conditions of the study area accurately. The Grand River at Ionia had 7.05 inches of runoff for the water year 1966 (U. S. Geological Survey, 1967). Because this value closely approximates the long term average of 7.63 inches, it was separated Into its com ponents of overland and ground-water runoff by graphical methods (Wisler and Brater, 1949). This was done In order to delineate the relative contribution of ground water to the total annual flow. For this particular year it was found that 58 per cent of the total flow, or *1.09 inches was derived from ground water sources. The area of the drainage basin at Ionia is 2,840 square miles, thus, a total of 0.30 cfsm (cubic feet per second per square mile) is ground-water runo f f . This value Is considered to be representative of the average ground water contribution to streamflow In the area. However, because of the size of the basin, precipitation may have occurred during periods which were assumed to be at base flow, consequently this figure of 0.30 afsm may be higher than the true value. Many pumping tests Indicate that the sandstone in the Saginaw Formation has a relatively constant permeability of approximately 100 gpd per sq. ft. (gallons per day per square foot). The permeability of the shale is much lower and more variable, ranging from 0.01 to 1.0 gpd per sq. ft. Pumping tests also indicate that the Saginaw Formation acts as a leaky artesian system over most of the study area. An average value of the leakage between the glacial drift and the Saginaw Formation was found by Wheeler (1967) to be approximately 0.0012 gpd per sq. ft. under existing head conditions. This value represented the leakage in the Lansing Metropolitan area prior to the extensive pumping development and is used here as an average value of the system throughout the study area. Assuming steady-state ground-water conditions over most of the basin, with the exception of Lansing Metro politan area, recharge to the formation will equal the discharge from the formation of 0.0012 gpd per sq. ft., or 0.051 cfsm. This amount would be the contribution from the Saginaw Formation to streams from each square mile in the basin. However, only about 90 per cent of the area is underlain by the S a g i n a w ,Formation, which, when accounted for, reduces the contribution from the formation to approximately .046 cfsm. Comparing this to the total ground-water runoff of 0.30 cfsm, the ratio is about 7 to 1. That is about 1/7 of the water in a stream under base flow conditions Is from the Saginaw Formation. Most of the remaining water is from the overlying glacial drift. t The potentiometric surface of the Saginaw Formation (Figure 4) is a smoothed reflection of the surface t 20 «♦» EXPLANATION - — > f%$-------- --- •* !« * i t * M * tM frtv l Figure 4.— Map showing potentlometrlc surface of the Saginaw Formation (modified after Vanller, Wood and Brunett* 1969). 21 topography. This further substantiates that there is a hydrologic connection between the overlying glacial material and the Saginaw Formation. In the Lansing Metropolitan area, however, the potentiometric surface of the Saginaw Formation is greatly depressed as the result of large amounts of ground water having been with drawn and no longer reflects natural conditions. The Bayport Formation, which directly underlies the Saginaw Formation in most of the study area, is a dense limestone approximately 40 feet thick. This formation effectively acts as a baBe to the flow system and prevents the passage of large quantities of water from moving either into the Saginaw Formation from below or from the Saginaw into the lower formations. This contention is aupported by the shape of the potentiometric surface of the Saginaw, which is controlled by the local surface topography and not by movement of water into or out of the underlying formations. The Bayport Formation usually transmits only small quantities of water where it is used as an aquifer. However, its quality as an aquifer is dependent on its geologic position. It has a greater permeability where it subcrops directly beneath the glacial draft than where it is capped by the Saginaw Formation. This condition is probably due to preglacial solution channels and fracturing due to load reduction as the Saginaw Formation was eroded. The presence of major faults or fractures in the Bayport Formation would certainly affect its ability 22 to transmit water. It Is therefore possible that In cer tain areas water moves in relatively large quantities through this formation. In summary, precipitation falling upon the basin recharges to and discharges from the Saginaw Formation through the glacial drift in a series of small flow systems (Figure 5). The patterns of flow of ground water result from the topography, formation thickness, contrasts in permeability, and basin size (Toth, 1963; Freeze and Witherspoon, 1966, 1967, and 1968). The Bayport Formation acts as a base to the system, minimizing flow into the system from below and retarding flow from the Saginaw Formation into the lower formations. LEVEL GLACIAL *00 E X P L A N A T IO N FEET ABOVE SEA 1000 Major geologic boundaries 200 • • • • • • « » « • • VERTICAL EXAGGERATI OH X 70 Equal potential lines Flow lifies Figure 5.— Hypothetical section of the Grand River basin showing potential distribution and two dimensional patterns of major ground water flow. IV} u> GEOCHEMISTRY OP GROUND WATER IN THE SAGINAW FORMATION Type and Concentration of Major Ions Water in the Saginaw Formation is a calciummagneslum-bicarbonate type; that is, calcium and magnesium ions constitute more than 50 per cent of the cations, and bicarbonate constitutes more than 50 per cent of the anions expressed as milliequivalents. Sodium, silica, chloride, and sulfate are four other major ions found in the water. These seven substances constitute over 98 per cent of the dissolved solids in all the samples examined. Iron and potassium are ubiquitous in the ground water of the Saginaw Formation but never exceed 1 per cent of the total dissolved solids. Nitrate concentrations greater than 2 mg/1 are seldom found In the Saginaw Formation. Nitrate In glacial drift wells is usually associated with sewage or agricul tural pollution and Is not a result of nitrate minerals in the aquifer. Source of Dissolved Solids In Ground Water Atmospheric Precipitation Determining the source of dissolved solids in ground .water Is essential in demonstrating the relationship 24 25: between chemical character of the water, hydrology and geology. Because local precipitation is the source of w&ter in the aquifer, several samples of rain water were collected by the author and analyzed for common ions (Table 2). Results of these analyses and others collected in North Carolina and southeastern Virginia (Fisher, 1968), Kentucky (Hendrickson and Krieger, 1964), and northern Sierra Nevada (Feth, Rogers and Roberson, 1964) indicate, that in relation to the total dissolved solids in the Saginaw Formation, very small amounts are contributed by precipitation to the ground water. As a result of evapor ation and transpiration, which removes about 85 per cent of the precipitation that does not run directly off the ground, the concentration of dissolved solids contributed to the ground water is about seven times greater than the analyses indicate. Even with this increase in concen tration due to evapotranspiration, precipitation cannot account for the magnitude of concentration observed for most of the major ions. Chloride is the only major ion for which precipitation may be a significant source. Continuous analyses of stream and precipitation data would be necessary to establish this relationship. Soil and Qlaoial Material The next source of dissolved solids, when viewed within the hydrologic framework, is the soil and glacial debris on which the precipitation falls. To evaluate TABLE 2.— Sources of dissolved solids in ground water. Local Number 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Sample Description hco3 so4 Cl Specific conduct ance Hardness p« Non-car0a*"B bonate pH Rain water June 23, 1968 East Lansing, Mich. 7 3.5 .8 <50 10 0 5.8 Rain water June 27, 1968 East Lansing, Mich. 5 2.0 .9 <50 10 0 5.3 265 124 0 8.1 Soil and glacial material SW 1/4 sec. 19, T.4n .,R.1W. 154 10 Glacial drift NW 1/4 sec. 12, T.3N.,R.1E. 114 11 4.0 225 98 4 7.6 Soil NW 1/4 sec. 12, T.3N..R.1E. 181 14 5.0 320 160 12 7.5 Fine sand and silt SW 1/4 sec. 18, T.4N.,R.2E. 86 19 225 94 24 8.1 Soil SW 1/4 sec. 25, T.4N.,R.1W. 482 14 6.0 750 390 0 8.0 24 4.0 105 30 22 6.8 1400 1100 1076 7.7 110 33 29 6.7 Light brown shale from Grand Ledge quarry 115 mesh 3/8” Black shale from Grand Ledge quarry 115 mesh Sandstone from Grand Ledge quarry 115 mesh 3/8" 9.3 30 5.4 1020 21 10 22 68 8.0 4 27 these materials as a source of dissolved solids, a laboratory experiment was designed In which the change In dissolved solids In water were measured after It had been In contact with the soil-glacial material. Five hundred grams of representative soil-glacial material from five localities were dried at room temperature placed in plastic cylinders. (23°C) and The material was not sorted by size, nor was any attempt made to preserve original packing or structure. Five hundred ml (milliliters) of distilled deionized water in equilibrium with the atmos phere were shaken with the sample, stoppered, except for a small air vent, and allowed to stand 5 to 7 days. The water was then filtered through a filter paper and funnel attached to the cylinder. The water slurry acted as a natural filter, giving a clear, usually colorless, filtrate. The filtrate was analyzed by the same methodB used for well water. Water obtained from these leaching experiments (Table 2) was, in general, similar to that observed in the Saginaw Formation and glacial drift wells (Table A - l ) . Much of the calcium and sulfate in the glacial debris and derived soil material results from the solution of gypsum (CaSOjj * 2H20) and/or anhydrite (CaSO^). These minerals were probably derived from the Michigan Formation and are irregularly distributed in the glacial deposits. The Michigan Formation, which is a commercial source of gypsum in the Michigan basin (Martin, 1936) subcrops in the 28 northeastern part of the basin and lies in the path of the last glacial advance in the area (Leverett and Taylor, 1915). That the sulfate ions are derived from sulfate minerals rather than by oxidation of sulfide minerals can be ascertained by comparison of values of non-carbonate hardness with the sulfate values shown in Table A-l and Table 2. Most analyses show an approximate one-to-one relationship between sulfate and non-carbonate hardness. This indicates that the sulfate was originally associated with CaSOjj or MgSO^ because, non-carbonate hardness, as the name implies, results from calcium and magnesium from sources other than carbonates. Possible minor sources of non-carbonate hardness are nitrates which contain calcium or magnesium and chlorides as CaCl2 or MgClg which may be present in very small quantities. However, the chloride ion concentration is generally related to the sodium ion concentration in this water and consequently does not contribute to the non-carbonate hardness. If sulfides were oxidized and brought into solution the resulting water would contain no calcium or magnesium from this source and consequently no non-carbonate hardness. The major source of calcium, magnesium and bi carbonate is from the reaction of carbonic acid, which is the result of the solution of carbon dioxide (C02 ) in water (H20), with limestone (CaCO^) and dolomite C a M g C C O ^ ^ 29 or magnesium rich limestone. The reactions are summarized by the eq u a t i o n s : C 0 2 + HgO CaC03 + H 2C 0 3 = Ca2+ + 2 H C 0 3« c o 2 + h 2o 4* CaMg(C03 )2 + H 2C03 * Ca2+ + M g 2+ + 3 HCC>3- Carbon dioxide may be ten to twenty times atmospheric value in the soil due to plant respiration and decaying organic material (Boynton and Reuther, 1938). Soil carbon dioxide concentration and mineral equilibria are probably the controlling factors in the amount of carbonate di s solved in this environment as there is an abundance of carbonaceous material in the glacial drift in the study area (Johnsgard et aJL., 19^2; Veatch et_ a l ., 19^1). Chloride and sodium ions are derived from solution of halite (NaCl) which, like the sulfate minerals, was probably incorporated in the surficial deposits by the glacier. As mentioned earlier, some of the chloride and sodium may come from precipitation. The relatively small amounts of chloride compared to sulfate ions may reflect greater solubility of the chloride and its removal shortly after deposition, or a lower initial concentration in the 30 drift. Sodium 1 b also obtained by ion exchange with calcium from certain clay minerals present in the glacial drift. In addition to leaching studies, evidence for a sollglaclal debris origin for the dissolved solids can be obtained from evaluation of high water runoff in the streams. During periods of high stream-flow, water is derived primarily from surface runoff and only a small percentage is derived from ground-water d i s c h a r g e . Over land runoff has been in contact only with the upper soil horizons and usually for a short period of time, seldom exceeding a week. Therefore, chemical analysis of stream water under these conditions compared to that of base flow conditions, which is entirely ground water, indicates the relative effects of soil horizons on water quality. In order to compare the stream water In the two types of flow conditions, statistical analyses, of previously published chemical data from streams (Table A-2), were performed using the ”t M test of mean comparison. of the sampling sites is given in Figure 6. Location These sites were selected to avoid known sources of industrial and municipal waste disposal and to give a wide geographic distribution within the basin. The major chemical param eters were found, by single classification analysis of variance technique, not to vary 'significantly between major sub-basins of the Grand River basin (Table A-2). Chemical data for each parameter were separated into class intervals, arrayed and plotted on normal probability paper 31 iHucwrcvii jf-iU U EXPLANATION Figure 6.— Map showing location of stream sampling sites. i 32 to check for normal distribution. The data were then subjected to an f,P ” test at the 5 per cent level of signifi cance to determine if the ratio of the standard deviations were acceptable for use in comparison of the means. If the "F" test indicated suitable ratios, the average of each parameter under high-flow was compared to the average of the corresponding parameter under low-flow by means of the "t” test. A 5 per cent level of significance was chosen and a "t” was calculated using the following formula: / CSP]^C(1/N1 ) + (1/N2 )] where 3T * average value of samples from populations 1, 2 t “ statistic N ■ number of samples from populations 1, 2 SP 2 « pooled mean square. The calculated value of "tlf was compared to standard tables (Dixon and Massey* 1957) at the indicated level of signifi cance to determine the acceptance or rejection of the hypothesis. The data are summarized in Table 3. These statistical analyses indicate that bicarbonate and sodium ions have higher concentrations in streams during base flow than during periods of overland runoff. The remainder of the major chemical parameters* including II II Low flow h *1 Hi*h flow S1 sr *2 s2 V s2 e H to 0*H u t 0 a
A 0
4> St
O -P
•HQ©
§
*
Calculated
h
0
44*
H
Aooept hypothesis
of equal variance
"F" test at
level of signlf•
TABLE 3. Statistical comparison of chemical parameters of water at high stream
flow with low stream flow.
^
•P° -0
OH O
g?9
-P
eviss
0 to
OPH
vel of slgnlf.
Mj O w H
a
34.2
40.30
.836
yes
6.37
yes
yes
3.72
yes
Number of samples
Average value of the samples
Standard deviation of the samples
Calculated statistlo
1.10
.775
V
yes
w4
o
c1%
C
1
•p
i
rjl
.
O
>cept hypothec
? $% level of
ignlfloanee
i
l
s2
Q
Si/S2
Wells in
Saginaw Formation
CM
Wells In
glacial drift and
low flow stream
xx
sx
»1
i
Chealoal
parameters
TABLE 5.--Statistical comparison of chemical parameters of water from glacial drift
and low stream flow with the Saginaw Formation.
< 4 0
.116 yes
46
Ca
42
M
&
2.09
•PW**«
P.O *H
OHO
yes
*1>*2
2.45
yes
.857
yes
Sl>^2
1.48
yes
11.13
.728
yes
17.4
.805
yes
.397
no
Wells in
Saginaw Formation
n2
s2 Si/S2
x2
1.67
2.23
235
85.1
18.74
223
79.8
21.87
42
29.1
8.10
229
27.6
Na
42
12,7
14.02
218
14.3
K
42
.91
206
HCO3
50 360
SO4
49
Cl
SOit/Cl
N
3
S
t
2.69
2.29
70.2
CM
CM
Wheret
1.68
1.39
41.7
32.05
241
34.2
40.30
47
8.6
15.3
245
6.1
11.10
47
10.2
11.48
221
8.7
10.75
=
■
=
=
376
66.1
Number of samples
Average value of the samples
Standard deviation of the samples
Calculated statistic
1.34
Xl>X2
"t"
Calculated
Fe
Hypothesis of
means
"t« test
Wells in
glacial drift
Xl
Si
»1
ID
•H
n v*
Aooept hypothesis
of equal variance
"F" test at 5%
level of signif.
Chemical
parameter
TABLE 6.— Statistical comparison of chemical parameter of water from glacial drift
with the Saginaw Formation.
•
0
J3
•p h
0 © 0e
>»c a
X H O
0O -P*rt5>
< ata
.866
no
-.7^7
no
yes
*1<^2
-1.49
yes
yes
* i >32
1.32
yes
1.37
yes
Xl>X2
1.37
yes
1.06
yes
Xl=X2
1.06
.795
.857 yes
t
52
sulfate-chloride ratio are the same In both formations.
The variance of the potassium concentration was too large
for comparison.
Iron, calcium, sulfate and chloride con
centrations are greater In the glacial drift while bi
carbonate Is less.
Differences in concentrations of major ions between
glacial drift wells and wells in the Saginaw Formation can
be observed in individual analyses by comparing wells
02N03E14CBA and 02N03E14CBAB1, 05N02W27CCAB1 and
05N02W27CCAD1, 06N02W29BAAA1 and 06N02W29BAAA2, and
07N02W15CBAA1 and 07N02W15CBAB1
(Table A-l).
These are
pairs of wells drilled adjacent to each other; one well of
each pair is in glacial drift, the other is in a rock for
mation.
In every case, the water obtained from the glacial
drift well contains greater concentration of major ions
than does the well finished in rock.
The hydraulic head,
based upon topographic relief, in all of these paired wells
indicate the water is moving from the glacial drift into
the consolidated rock formation.
Difference in concentration of certain chemical
parameters between the glacial drift and the Saginaw For
mation is perplexing.
It was demonstrated that the soil
and glacial material were the source of most of the major
ions in the water and that hydrologlcally the Saginaw
Formation is recharged by water from the glacial drift.
It might be assumed that the water in the Saginaw Formation
would be equally mineralized.
It might be of a different
*
53
chemical type of water through ion exchange or solution of
soluble salts, but it would not be expected to be lower in
most dissolved species than the recharging water.
Most of
the differences in water chemistry between the formations,
that cannot be explained, exist in the sulfate and chloride
concentrations and the apparent concentration of some ions
in water from many wells in the glacial drift.
Differences
in iron, calcium, sodium and bicarbonate concentrations
could be explained by cation exchange in varying degrees,
but the fact that sulfate and chloride concentrations are
lower in water from the Saginaw Formation yet remain in
the same ratio as in water from the glacial drift is
unusual.
Explanation of Observed
Distribution
Pre-Pleistocene age w a t e r .— Several possibilities
exist that may explain the differences between the water
chemistry in the two formations.
Water from the Saginaw
Formation may not be of Pleistocene agej but rather it may
be water remaining in the formation from a period before
the glacial cover.
The hydrology does not support this
hypothesis, but the water has not been dated by radiometric
techniques.
The potentiometrlc surface of the Saginaw
Formation follows the present land surface, indicating that
recharge and discharge are presently taking place.
Addi
tionally, Wheeler (1 967) demonstrated that the Saginaw
5M
system in the Lansing area before extensive pumping was in
dynamic equilibrium, with recharge equalling discharge.
Prom these considerations it seems very unlikely that the
water is of pre-Pleistocene a g e .
Selected areas of r e c h a r g e .— Another possibility is,
that water is recharged to the Saginaw Formation at the
outcrops and in zones where the glacial drift is composed
of coarse sand and gravels which contain few chloride or
sulfate minerals.
Again this hypothesis is not compatible
with the hydrology of the system.
The potentlometric sur
face conforms to the topographic surface, showing recharge
is taking place over the entire area and not in selected
areas.
Also, the amount of outcrop area, or area covered
by permeable "clean” sand and gravel, is very small
(Johnsgard et_ aJL., 19*12; Veatch ejt a l ., 19**1) and totally
insufficient for supplying the observed discharge.
Anion e x c h a n g e .— A hypothesis of anion exchange could
explain the lower concentrations but there 1 b little experi
mental evidence to support i t .
This mechanism would remove
sulfate and chloride and replace it with some other anion,
presumably bicarbonate.
Prom analogy with cation exchange
it would be expected that there would be a greater ex
change of either sulfate or chloride, yet the ratio remains
the same in both formations.
The clay minerals have nega
tive surfaces, as suggested by cation exchange which would
seem to preclude anion exchange in this Bystem.
i
Also this
55
process does not account for the concentrating effects of
Ions observed In water from many glacial drift wells.
Mineral reduction.— Sulfate could be removed from
water by reduction to a sulfide mineral, if the redox
potential were sufficiently low.
Reduction probably occurs
in small areas in the aquifer as hydrogen sulfide gas is
detected in the wells occasionally and pyrite is observed
in the coal beds in the Grand Ledge outcrop.
However,
redox potential is higher (more positive) in most of the
aquifer than that required for pyrite formation.
This is
suggested in the section on mineral equilibrium.
The most
convincing evidence that sulfate reduction is not a major
cause of lower sulfate concentration in the Saginaw For
mation is that the sulfate-chloride ratio remains the same
in both formations and no mechanism for the parallel de
crease in chloride is available under these conditions.
Also this hypothesis does not explain the ion-concentrating
effects observed in water from many glacial wells.
Reverse osmosis and ultrafiltration.— The best
explanation for the differences in water quality between
the two formations and the apparent concentration effect in
water from wells in glacial material involves a hypothesis
that parts of the Saginaw Formation filter out certain ions
as the water passes through them.
It has been demonstrated
that shales act as semlpermeable membranes; that is, they
allow the water to move through them but retard some of
the dissolved solids in the water.
An early mention of
56
membrane properties of natural geologic material was given
by Wyllle (1948).
Kemper (1961) demonstrated that osmotic
pressure will occur on the high salt side of a clay m em
brane.
McKelvey and Milne (1962) demonstrated reverse
osmosis could occur In a natural clay sample as did Kemper
and Maasland (1964).
That Is, the application of pressure
to one side of a salt solution-clay membrane system results
in salt removal and an Increase in concentration on the
high pressure side of the membrane.
The process of reverse
osmosis, using synthetic membranes, Is one of several
methods under investigation for desalination of water
(Howe, 1966).
Breedehoeft et_ al.
(1963) used the concept of ultra
filtration to explain the origin of brines in the Illinois
basin.
Graf et_ al.
(1966) applied essentially the same
concept, with some biological functions added, to explain
the origin of the brines in the Michigan and Illinois
basins.
Jones (1968) explains the abnormal fluid pressure
and relatively fresh water in some Neogene deposits in the
Gulf of Mexico by a modification of this process.
There are several types of forces that can operate on
a solution of dissolved solids separated by a semlpermeable
membrane.
Chemical or normal osmosis, which depends upon
different activities on either side of a semlpermeable
membrane, resulting in a mass transfer of water from the
side of higher activity to the side of lower activity.
Movement will continue until sufficient pressure (osmotic
57
pressure) is built up to prevent further transfer of water.
Electroosmosis is a system in which the charged ionic
species are driven by electrical potential through a semipermeable membrane which retards some species while letting
others pass through.
The transfer of certain species will
continue until the potential build up by the ions equals
the potential applied across the membrane plus the chemical
osmotic pressure that will develop as soon as a concen
tration gradient exists.
Thermoosmotic systems operate
when dissolved solids are separated by a semlpermeable
membrane with a temperature gradient across the membrane.
The side with the greatest temperature will lose water to
the lower temperature side but not certain ionic species.
This process will continue until a chemical gradient of
sufficient force is established that will cause the reaction
to stop.
The fourth process is one of gravity or reverse
osmosis, that is, water is transmitted through a membrane
by gravitational forces and the membrane retards the passage
of certain ions.
The transfer of water through the membrane
will continue until the concentration of ions on the high
potential side Increases to the point where chemical osmosis
would counter the driving force and all flow would stop.
Reverse osmosis could occur in a natural or in an artificial
recharge e n v i r o n m e n t .
To determine if the hydraulic gradient observed
between the glacial drift and the Saginaw Formation was
.larger than the osmotic pressure generated by the activity
58
difference between the formations, calculations of osmotic
pressure were made using an approximation to the v a n ft Hoff
law
n2 R T
where
it = osmotic pressure
R = gas constant
T * absolute temperature
n 2 “ number of moles difference across the
V
membrane
** volume of solution.
This approximation is probably valid because of the dilute
solutions involved in this study.
With an assumed differ
ence in activity of 0.0001 moles which is typical for this
system,
the osmotic pressure is 0.08 feet,
the hydraulic head in the glacial drift is
that is where
0.08 feet higher
than the Saginaw Formation, flow and ion filtering can
occur.
This small osmotic pressure is exceeded over most
of the recharge area.
Assuming 0.01 moles difference,
which may exist at an interface where the dissolved solids
have increased, the head necessary to overcome the osmotic
pressure is one hundred times greater or 8 feet.
This
head difference is exceeded in many areas of the basin,
however, in each area of investigation it is necessary to
obtain detailed chemical analyses and hydraulic head data
in order to determine if reverse osmosis is occurring.
59
The operation of reverse osmosis In the Saginaw
Formation is Illustrated in Figure 10.
Many observations
on ion distribution in the Saginaw ground-water system are
included in this illustration.
The soluble salts are
leached from the glacial drift and filter out on shale
lense.
The water above the lense becomes concentrated in
the ions removed by filtration.
Wells in this zone yield
water high in dissolved solids.
Comments by local drillers, that water quality is
superior when wells are drilled using the hydraulic rotary
methods of drilling instead of the cable tool method, are
explained by assuming that the casing is cemented in the
formation deeper and more securely with the rotary method.
This difference in casing techniques could explain why
wells 200 feet apart which have overlapping cones of de
pression and obtain water from the same depth yield water
of different quality.
Wells from the Saginaw Formation
yielding the higher mineralized water have either poor
casing cementing or are cased in a fractured rock that
lets drift water directly into the well bore without bene
fit of ion filtering.
This situation is emphasized in a
recharge area where concentration of dissolved solids have
built up over years of recharge.
Highly mineralized water
may then seep into the well drilled in this environment.
The sudden deterioration in water quality repoi’ted by some
owners is explained in assuming that the casing has rusted,
letting water from the glacial drift into the well. .
■ A T E R I N S T R E A MS
M I X T U R E O F MATER
Z O N E S O F C O N C E H T R A T E O AND U N C O N C E N T R A T E D
DISSOLVED S O L I O S .
CT\
O
glacial
drift
\ W \ W W \ v
JO K E OF CONCENTRATED
\\\\\\\\\V\\\N
DISSOLVED S O L ID S v
\'N
SA6JNAV
FORMATION
RATER IS F IL T E R E D : DISSOLVED SOLIDS
A R E C O N C E N T R A T E D I N AMO O I R E C T L T
ABOVE F I L T R A T I O N LAYER
ZONE OF FILTERED WATER
Figure 10.— Diagram showing process by which dissolved solids
are concentrated by hydrology and geology.
61
The effects on chemical quality of water by different
drilling methods was compared by the "t" test.
No statisti
cally significant difference between drilling methods was
observed.
It is probable, however, that casing techniques
vary with individual drillers and obscures the true effect
of drilling methods and consequently casing techniques.
The effect of recharge and discharge as illustrated in
Figure 10 also affects the chemical quality.
However, J.t
was assumed that each drilling method was affected equally.
Using the "t" test, wells cased the first 20 feet in
sandstone were compared to wells cased the first 20 feet
in shale.
It was observed (Table 7) that sulfate, chloride
and magnesium concentrations were greater in wells cased
in sandstone than in shale and that calcium, sodium and
bicarbonate were the same in both llthologlc types.
Iron,
potassium, and the sulfate/chloride ratio varies too much
to obtain a valid comparison of means.
Results of this
statistical analysis further suggests that the shale in
the formation act as the ion filter.
The concept of reverse osmosis explains why the
analysis of stream water is different from that of the
Saginaw Formation yet the sulfate/chloride ratio remains
the same.
It also explains why the black shale in the
leaching experiment yielded the high value of sulfate and
chloride.
In this environment near the bottom of a freshly
dug pit from which the samples were taken for the leaching
experiments, the hydraulic gradient is and has been for a
TABLE 7.— Statistical comparison of chemical parameter of water from wells cased in
sandstone with those cased in shale of the Saginaw Formation.
CD 0
HO
•
0 0 Vi
©0>fcrt
£«H>nss Vi
P h (0 O
O 0PH
00 0 -P
HOQ
u
j?HpVi
Saginaw Formation
Wells cased
wens cased
in shale
in sandstone
—
sr
*2
r2
^2
68
Mg
2.07
no
75.2
22.51
68
25.1
8.40
15.24
62
15.4
17.51
1.32
64
69
79.3
19.44
66
69
28.3
8.24
Na
67
12.1
K
66
HCO3
73 380
64.10
71 384
SO4
73
39.09
72
Cl
73
4.30
4.84
71
SOjf/Cl
65
9.32
6.08
62
Where *
2*00
35.2
1.09
3.27
2.31
0 Vi
O O
P
£
p
£ H
s
0
H
0
O
H
0
O
P H O
000
>*©3
Pi OH
©H 0
o
to
OP H
<00
yes
1.15
no
.981
yes
2.26
yes
yes
-1.16
no
.571
no
Xj>X2
60.70
1.06
yes
- .432
no
36.2?
1.08
yes
1.48
yes
3.03
3.81
1.27
yes
Xf*X2
1.74
yes
8.65
11.81
no
—
25.8
N = Number of samples
X = Average value of the samples
S = Standard deviation of the samples
.515
O
H
PW^Vi
00
3
Ca
1.02
2.11
1.53
t
.=*■
70
000
0 00 0 0 P
P 3 ©
£ 0
Pi C P H P 0 *
00 0 O P
O * > Pc *
OVifaO
< 0* H
VO
00
.
Fe
sl/s2
•
H 0
0P
O0
0|
Js aJ
O A
0
•
4
2.0
0
2.0
12
6.4
1.5
1.6
—
2.0
5.C
1.2
.3
278
450
530
466
450
298
384
246
340
540
440
368
400
574
604
307
270
376
323
350
430
420
352
370
196
282
318
330
276
296
a
710
589
297
503
750
640
590
580
793
938
513
450
540
530
540
700
600
520
520
317
472
500
510
450
450
35
100
80
50
200
i
x
180
1
1
75
90
80
100
25;,
3
1
»
11
35
A0
60
25
AD
60
70
115
30
70
60
TO
3
3
1
3
3
3
3
3
3
1
1
3
3
3
3
TABLE A-2.— continued
s
3
ii
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Sopt 19,1963
July 11,1967
JUdo 28,1968
Oct 5,1964
Sopt 2,1159
Doc.17,1959
Apr
I960
July 7,1960
JUly 11,1967
Jtoo 28,1968
O ct.5,1964
4.01
B
8
1 J3
8
8
8
B
B
8
.08
B
2
—
—
—
—
15
7
4.5
9.0
—
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1.63
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2.12
3.96
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2.81
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3.73
1.36
4.12
4.96
5.00
2.65
8.99
1.28
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TABLE A-3.— continued
00
On
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