PB90-195389
PERFORMANCE EVALUATION AT A LONG-TERM
LAND TREATMENT SITE
PROCESSING
U.S. ENVIRONMENT PROTECTION AGENCY
ADA, OK
                              BF IIH1EBEE
                              NTIS

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                                    EPA/600/1-90/006
                                    April  1990
 PERFORMANCE EVALUATION  AT A LONG-TERM
   FOOD PROCESSING LAND TREATMENT SITE
                        by

          Dante J. Tedaldi and Raymond C. Loehr
   Environmental and Water Resources Engineering Program
             Department of Civil Engineering
             The University of Texas at Austin
                  Austin, TX  78712
                    Prepared for

                 Dynamac Corporation


              Contract  No. 68-01-7266
               Work Assignment Manager
                   Bert E. Bledsoe
             Activities and Assistance Division
      Robert S. Kerr Environmental Research Laboratory
                   Ada, OK 74820
ROBERT S. KERR ENVIRONMENTAL RESEARCH LABORATORY
       OFFICE OF RESEARCH AND DEVELOPMENT
       U.S. ENVIRONMENTAL PROTECTION AGENCY
                   ADA, OK 74820

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                                    TECHNICAL REPORT DATA
                             (Please read Instructions on the reverse before completing)
1. REPORT NO.
   EPA/600/1-90/006
                               2.
              3. RECIPIENT'S ACCESSION NO.
                             C  .r '-, r>
IB 90
                                        /IS
4. TITLE AND SUBTITLE
 PERFORMANCE  EVALUATION AT A LONG-TERM FOOD PROCESSING
 LAND TREATMENT SITE
                                                              5. REPORT DATE
              6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
                                                             8. PERFORMING ORGANIZATION REPORT NO.
 Dante  0.  Tedaldi  and Raymond C. Loehr
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 Environmental  and Water Resources Engineering Program
 The University of Texas at Austin
 Austin,  TX   78712
              10. PROGRAM ELEMENT NO.

                 ABWD1A
              11. CONTRACT/GRANT NO.
                                                                 68-01-7266
12. SPONSORING AGENCY NAME AND ADDRESS
   Robert  S. Kerr  Environmental Research Laboratory- Ada
   U.S.  Environmental  Protection Agency
   P. 0. Box 1198
   Ada,  OK 74820
              13. TYPE OF REPORT AND PERIOD COVERED
              Final Report  (9/87  -  3/90-)
              14. SPONSORING AGENCY CODE
                  EPA/600/15
15. SUPPLEMENTARY NOTES
  Project  Officer:   Bert E. Bledsoe
      FTS:  743-2324
16. ABSTRACT  ....     _ . .  .
       Trie objective of this project was  to  determine the performance of a  fullscale,
  operating overland flow land  (OFL) treatment  system treating nonhazardous waste.
  Performance was evaluated in  terms of treatment of the applied waste and  the environ-
  mental  impact of the system,  particularly  surface and ground water quality as well  as
  soils accumulation.  The major conclusions  were:  The long-term operation and perform-
  ance  data indicated that the  OLF system  consistently achieved a very high level of
  treatment and pollutant removal, from a  surface discharge standpoint.  With respect
  to  a  control  area, located at the OLF site  but  not subjected to wastewater application
  or  impacts, the accumulation  of organic  carbon, potassium, zinc, and nickel in  the
  soil  at wastewater application areas was evident, as well as the apparent leach of
  calcium, sodium,  sulfate.  Neither accumulation nor leaching of chromium, magnesium,
  and chloride  were evident.  Although the accumulation of zinc and nickel was evident,
  the cumulative soil concentrations were  well  below EPA recommended limits, and  several
  hundred years of continued site use may.be  expected at present loading rates.
  Groundwater below the OLF site was moderately saline due to the presence of sodium,
  calcium, magnesium, chloride, and sulfate.  No  purgeable or extractable organics were
  detected.   Geochemical  data indicates the enhanced dissolution and leaching of  naturally
  present soil  minerals is  due  to the infiltration of large volumes of treated wastewater.
17.
                                 KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                                b.lDENTIFIERS/OPEN ENDED TERMS
                            c. COSATI Field/Group
18. DISTRIBUTION STATEMENT

        RELEASE  TO THE PUBLIC
19. SECURITY CLASS (This Report!
      UNCLASSIFIED
                                                                            21. NO. OP PAGES
                                                20. SECURITY CLASS (This page:

                                                     UNCLASSIFIED
                                                                            22. PRICE
EPA Form 2220-1 (Rv. 4-77)   PREVIOUS EDITION is OBSOLETE

                                             1

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                         NOTICE
The information in this document has been funded wholly or in part by
the United States Environmental Protection Agency through Contract
68-01-7266 to the Dynamac Corporation and through a sub-contract
(Task 100) from Dynamac Corporation to the University of Texas at
Austin. It has been subjected to the Agency's peer and administrative
review, and it has been approved for publication as an EPA document.
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.

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                                 FOREWORD

     EPA is charged by Congress to protect the Nation's land, air, and water systems. Under
a mandate  of national environmental laws focused on air and water quality, solid waste
management, and the control of toxic substances,  pesticides, noise, and  radiation,  the
Agency strives to formulate and implement actions which lead to a compatible balance
between human activities and the ability of natural systems to support and nurture life.
     The Robert S. Kerr  Environmental Research Laboratory is the Agency's center of
expertise for investigation  of the soil and subsurface environment. Personnel at the Labo-
ratory are responsible for management of research programs to: (a) determine the fate,
transport and transformation rates of pollutants in the soil, the unsaturated and saturated
zones of the subsurface environment; (b) define the processes to be used in characterizing
the soil and subsurface environment as a receptor of pollutants; (c) develop techniques for
predicting the effects of pollutants on ground water, soil, and indigenous organisms; and (d)
define and demonstrate the applicability and limitations of using natural processes,  indige-
nous to the soil and subsurface environment, for the protection of this resource.
     The Resource Conservation and Recovery Act (RCRA) amendments of 1984 requires
the U.S. Environmental Protection Agency (EPA) to assess the adequacy of current federal
programs to protect human health  and the environment from mismanagement of non-
hazardous and unlisted hazardous wastes, which were developed under Subtitle D.  The
major objective of this project was to determine the performance of a full-scale operating
land treatment system treating non-hazardous waste.  Performance was to be evaluated in
terms of treatment of the applied waste and the environmental impact of the system, par-
ticularly, surface and groundwater quality as well as soils  accumulation
                            Clinton W. Hall
                            Director
                            Robert S. Kerr Environmental Research Laboratory
                                       in

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                                 ABSTRACT
     The objective of this project was to determine the performance of a full-scale, operating
overland flow land (OLF) treatment system treating non-hazardous waste. Performance was
evaluated in terms of treatment of the applied waste and the environmental impact of the
system, particularly surface and groundwater quality. Performance data were obtained from
the Campbell Soup (Texas), Inc. OLF system in Paris TX, which has been in operation for
over 24-years.  Field samples of  soil, wastewater, OLF runoff, and groundwater collected
during the project and long-term process records maintained by Campbell Soup were used
as part of the evaluation.
     The major conclusions were:
1.   The long-term operation and performance data indicated that the OLF system con-
     sistently achieved a very high level of treatment and pollutant removal, from a surface
     discharge standpoint. Mass and concentration  removals of BOD5, COD,  TOC, and
     TSS have been consistently high with mean individual pollutant removals >92% (mass
     basis) and >93% (concentration basis). Total nitrogen removals were between 84 and
     89%.  Effluent mass discharges have remained well within the regulatory  limitations
     for suspended solids and BOD5 over the 24 years that the site has been in  operation.
2.   With respect to a control area, located at the OLF site but not subjected to wastewater
     application or impacts, the accumulation of organic carbon, potassium, zinc, and nickel
     in the soil at wastewater application areas was evident, as well as the apparent leach
     of calcium, sodium, sulfate. Neither accumulation nor leaching of chromium, magne-
     sium, and chloride were evident.
3.   Although  the accumulation  of zinc and nickel was evident, the cumulative soil con-
     centrations (200 kg/ha and 85 kg/ha) were well below EPA recommended limits (1,120
     kg/ha and 560 kg/ha) and several hundred years of continued site use may be expected
     at present average loading rates (3 kg/d and 0.2 kg/d).
                                       IV

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4.   The OLF site is underlain by several meters of a heavy inorganic clay (Bonham For-
     mation).  A semi-confined aquifer, partially confined from above by the Bonham For-
     mation clays and  slowly recharged by  downward leakage through the Bonham
     Formation exits below the OLF site.  The aquifer is confined from below by the dense,
     fissile shale of the Eagle Ford Group.
5.   Groundwater below the OLF site was moderately saline due to the presence of sodium,
     calcium, magnesium, chloride, and sulfate. No purgeable or extractable organics were
     detected.
6.   Ionic ratios of major ions in groundwater collected from lysimeters at the OLF site in
     1968 exhibited excellent agreement with comparable ionic ratios for samples collected
     between 1987-1989.  The pattern of ionic composition with relatively small changes in
     tonic ratios suggested a trend toward the dissolution and concentration of naturally
     present minerals (in the soil) in the relatively slow moving groundwater.
7.   Geochemical data  indicated  that  sulfate-chloride  facies were  dominant for the
     groundwater collected at 3 monitoring wells at the OLF site and for the lysimeter data
     collected in 1968.  The similarity of ionic ratios and hydrochemical facies with an
     increase in groundwater constituent concentrations over 20 years strongly suggested
     a pattern of geochemical evolution due to the enhanced dissolution and leaching of
     naturally  present soil minerals  due to the infiltration of large volumes of  treated
     wastewater.

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                          CONTENTS

FOREWORD	iii

ABSTRACT	iv

CONTENTS	vii

FIGURES	xi

TABLES	xiii

NOMENCLATURE	xv

ACKNOWLEDGEMENTS	xvi

CHAPTER 1. INTRODUCTION	1
   BACKGROUND	1
   OBJECTIVES	1
   FIELD LOCATION AND STUDY AREA	2
   RESPONSIBILITIES	4

CHAPTER 2. CONCLUSIONS	6

CHAPTER 3. GENERAL MATERIALS AND METHODS	10
   INTRODUCTION	10
   ANALYTICAL METHODS	11
     Dissolved Oxygen (DO)	11
     Biochemical Oxygen Demand (BOD)	11
     Chemical Oxygen Demand (COD)	11
     Total Organic Carbon (TOC)	12
     Metals	12
     Residue	13
     Alkalinity	13
     Ammonia	13
     Anions	14
    Preceding page blank
                               VII

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     Soil Organic Carbon	14
     Purgeable Organics	14
     Base/Neutral Extractables	15
     Specific Conductivity and pH	..:	15
     Cation Exchange Capacity (CEC)	15
  STATISTICAL ANALYSES	16
     Test for Normality	16
     Student's t-test	17
     Analysis of Variance	17
       One-way ANOVA	18
       Two-way ANOVA	18

CHAPTER 4. TREATMENT SYSTEM DESCRIPTION	20
  INTRODUCTION	20
  FACILITY BACKGROUND	20
  SOLID AND LIQUID WASTE DISPOSAL	25
  SPRAY SITE	30
  FLOW CONTRIBUTIONS TO SMITH CREEK	32
  REGULATORY MONITORING REQUIREMENTS	34

CHAPTER 5. RAW WASTE CHARACTERISTICS	35
  PREVIOUSLY PUBLISHED DATA	35
  UNPUBLISHED PLANT RECORDS	36
  WASTEWATER MASS LOADING	44
  CONCLUSIONS	48

CHAPTER 6. TREATMENT SYSTEM DISCHARGE CHARACTERISTICS	49
  SMITH CREEK WATER QUALITY	49
  PERMIT COMPLIANCE	53
  PRECIPITATION AND ITS EFFECT ON PROCESS PERFORMANCE	55
  SYSTEM MASS BALANCES	58
  CONCLUSIONS	59
                               VIII

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CHAPTER?. SOILS	61
   INTRODUCTION	61
   MATERIALS AND METHODS	61
     Soil Core Sampling	61
   RESULTS	65
     Organic Carbon	65
     pH and Cation Exchange Capacity	69
     Total Metal	71
     Water Soluble Anions	80
   SUMMARY	83
   SOIL METAL RETENTION CORRELATIONS	84
   METAL ACCUMULATION AND ITS EFFECT ON SITE LIFE	86
   CONCLUSIONS	88

CHAPTERS. HYDROGEOLOGY	89
   INTRODUCTION	89
   GENERAL GEOLOGY	89
     Geologic History	89
        Paleozoic	90
        Cretaceous	91
        Tertiary and Quaternary	91
     Stratigraphy	91
     Lithology and Groundwater Potential	93
        Blossom Sand Formation - Austin Group	93
        Bonham Formation - Austin Group	95
        Eagle Ford Group	97
   MATERIALS AND METHODS	99
     Monitoring Well Installation	99
     Sampling of Monitoring Wells	100
     Slug Tests on Monitoring Wells	101
     Well Casing and Water Level Survey	103
   RESULTS	103
                                  IX

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     Groundwater Hydrology	103
       Water Level Analysis	103
       Slug Tests	106
  CONCLUSIONS	107

CHAPTERS. GROUNDWATER:
           QUALITY, RECHARGE, AND GEOCHEMISTRY	109
  INTRODUCTION	109
  GROUNDWATER QUALITY DATA	109
  DATA ANALYSIS AND DISCUSSION	118
     Background Water Quality	118
     Groundwater Seepage Quantities	119
     Hydrochemical Facies	121
     Major-Ion Aqueous Geochemistry	123
     Geochemical Evolution of Groundwater	126
     Summary of the Conceptual Model for Groundwater Recharge	130
  SUMMARY	133

CHAPTER 10. GLOSSARY OF TERMS	135

CHAPTER 11. CONVERSION FACTORS: METRIC TO U.S. UNITS	140
REFERENCES	141
APPENDIX A. WELL CONSTRUCTION DATA	143
APPENDIX B. GROUNDWATER CONSTITUENTS ANALYZED	147
APPENDIX C. SLUG TEST RESULTS	151

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                                 FIGURES

4-1  General Location Map: Paris.Texas	 21
4-2  Site Plan: Campbell Soup (Texas), Inc	22
4-3  Expansions of the Paris, Texas System	24
4-4  Flow Diagram of Waste Processing and Land Treatment System	 27
4-5  Solid Waste Disposal Site Locations	29
4-6  Idealized Overland Flow Slope	30
4-7  Schematic of a Typical OLF Treatment Spray Line and One Sprinkler	32
4-8  General Location Map: Campbell Soup Plant 	 33
5-1  Raw Wastewater Flow Rate, 1977-1988	37
5-2  BOD5Loadof Raw Wastewater, 1977-1988 	 38
5-3  TSSLoadof Raw Wastewater. 1977-1988 	 38
5-4  Monthly Mean Flow Rate: Screened Raw Wastewater	40
5-5  Monthly Mean BODS Concentration	40
5-6  Monthly Mean COD Concentration	41
5-7  Monthly Mean TSS Concentration	 41
5-8  Monthly Mean Chloride Concentration	42
5-9  Monthly Mean Sulfate Concentration  	42
6-1  Flow Rate of Smith Creek: 1974-1988 	49
6-2  BOD-5 Concentration in Smith Creek: 1974-1988 	 50
6-3  COD Concentration in Smith Creek: 1974-1988  	 50
6-4  TSS Concentration in Smith Creek: 1974-1988 	51
6-5  VSS Concentration in Smith Creek: 1974-1988	 51
6-6  Chloride Concentration in Smith Creek: 1974-1988	 52
6-7  Sulfate Concentration in Smith Creek: 1974-1988	 52
6-8  BOD-5 Load in Smith Creek: 1974-1988	54
6-9  TSS Load in Smith Creek: 1974-1988	 54
                                     x i

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6-10 15-year Mean Monthly Waste Loading in Smith Creek and Precipitation 	56
7-1 Location Map of Soil Sample Collection Areas	  62
7-2 Auger Bit and Core Recovery Device	63
7-3 Core Extruding and Paring Apparatus	64
7-4 Core Sample Compositing Sequence  	65
7-5 Control Area Composite Core Samples: Percent Organic Carbon	66
7-6 E-32 Spray Line Composite Core Samples: Percent Organic Carbon	  66
7-7 Y-16 Spray Line Composite Core Samples: Percent Organic Carbon	67
7-8 G-4 Spray  Line Composite Core Samples: Percent Organic Carbon	  67
7-9 Leaching of Calcium From Soil in Wastewater Application Areas	  76
7-10 Leaching  of Sodium From Soil in Wastewater Application Areas	  78
7-11 Leaching  of Sulfate From Soil in Wastewater Application Areas	  83
8-1 Index Map of Major Structural Features of the East Texas Basin	  90
8-2 Geologic Outcrop Map: North-Central Texas	94
8-3 Map of Aquifers in North-Central Texas	96
8-4 Formations within the Eagle Ford Group	98
8-5 Monitoring Well and Boring Location Map	  99
8-6 Geologic Cross Section Between MW-1 and MW-3	  105
9-1 Calcium Concentration MW-1:1987-1989  	  114
9-2 Magnesium Concentration MW-1:1987-1989	  114
9-3 Sodium Concentration MW-1:1987-1989 	  115
9-4 Trilinear Diagram Classification of Anion and Cation Fades	  122
9-5 Scholler Diagram: Mean Values From 1987-1989	  124
9-6 Scholler Diagram: Long-term Groundwater Quality	  125
9-7 Conceptual Model of the Groundwater Recharge	  131
                                     xi i

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                                  TABLES

3-1  Summary of Sample Analyses Performed	 10
4-1  Solid Waste Identification and Disposition	 28
4-2 Smith Creek Limitations and Monitoring Requirements 	 34
5-1  Raw Wastewater Characteristics	 35
5-1  ANOVA of Raw Wastewater Flow and Concentrtaions	 37
5-2 Sump Wastewater Characteristics, Period: 1977-1988	39
5-3 Total Metals Concentrations in Screened Raw Wastewater	 43
5-4 Wastewater Loading to OLF Site, Period: 1977-1988	 44
5-5 Confidence Intervals, Sump Concentrations, Period: 1977-1988	 45
5-6 Comparison of Selected Sump Wastewater Characteristics	 46
5-7 Total Metals in Screened Raw Wastewater	47
6-1 Concentrations in Smith Creek:  1974-1988	 53
6-2 Effluent Loads in Smith Creek	 55
6-3 Runoff Concentrations During Wet and Dry Conditions	 57
6-4 Mass Balance Results for the Paris, Texas OLF Site	59
7-1 Q-Method Test Results for Organic Carbon: Location 	 68
7-2 pH and CEC Values: Composite Soil Cores	 70
7-3 Q-Method Test Results for CEC: Location	 70
7-4 Metals Examined in Soil Core Samples  	 71
7-5 Soil Metal Concentrations: Means and Standard Deviations 	 72
7-6 Q-Method Test Results for Potassium	 74
7-7 Q-Method Test Results for Calcium 	 75
7-8 Q-Method Test Results for Magnesium	 76
7-9 Q-Method Test Results for Sodium	77
7-10  Q-Method Test Results for Zinc	 78
7-11  Q-Method Test Results for Nickel	 79
                                     XI I I

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7-12 Q-Method Test Results for Chromium	80
7-13 Chloride and Sulfate Pore Water Concentrations	 81
7-14 Q-Method Test Results for Sulfate	81
7-15 Q-Method Test Results for Chloride	 82
7-16 Statistical Summary of Soil Characteristics	 83
7-17 Soil Metal Correlation: Linear Regression and ANOVA Results 	 85
7-18 Assumptions Used for the Calculation of Metal Accumulation	87
7-19 Calculation of Metal Accumulation and Site Life Expectancy	 88
8-1 Stratigraphic Units and Geologic Time Scale	 92
8-2 Ground Surface and Water Level Elevations 	 103
8-3 Slug Test Results for Confined and Unconfined Aquifers 	 107
9-1 Groundwater Constituents Detected at MW-1:1987 Through 1989 	 111
9-2 Groundwater Constituents Detected at MW-2:1987 Through 1989 	 112
9-3 Groundwater Constituents Detected at MW-3:1988 Through 1989 	 113
9-4 Groundwater Monitoring Well Data (MW-1 & MW-2) ANOVA Test Results .... 116
9-5 Groundwater Quality at Campbell Soup Site: Mean Values	 117
9-6 Lysimeter Data: 1-Meter Below Ground Surface, April 1968	 119
                                     X IV

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                           NOMENCLATURE
Symbol         Description                                Dimensions

  A             area                                              L2
  a             statistical level of significance
  C,            calculated ionic concentration                       M/L3
  C^           measured ionic concentration                       M/L3
  C,            well configuration shape factor
  JF           F-statistic value, i and j degrees of freedom
  f(x)           normal distribution function
  j,^           hydraulic gradient                                  L/L

  k             hydraulic conductivity                              L/T
  L             well screen length                                   L
  \i             population mean
  it             3.14286
  q             groundwater seepage rate                          L3/T
  r             well radius                                         L
  r2            square of correlation coefficient
  R             well screen radius
  a             population standard deviation
  S,            groundwater drawdown                              L
  tz             time to drawdown                                   T
  WH,           mass of extraction fluid                              M
  Ww           mass of soil water                                   M
  x             sample value
  x            independent variable
  Y            dependent variable

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                    ACKNOWLEDGEMENTS
     This project  has been an exemplary cooperative effort between: (a) the U.S. Envi-
ronmental Protection Agency (EPA), particularly individuals at the Robert S. Kerr Environ-
mental Research Laboratory (RSKERL), Ada, Oklahoma; (b) the Campbell Soup Company
and; (c) the Environmental and Water Resources Engineering Program of the University of
Texas at Austin (EWRE-UT). This report represents the hard work, interest and dedication
of the many individuals who have assisted in the project.  The contribution of the following
individuals deserves specific recognition and is gratefully recognized and greatly appreciated:
              Campbell Soup Company
                   Dr. Osman Aly       Gus Harris
                   Bob Coleman        Arthur Lay
                   Lou C. Gilde         Charles H. Neeley
              RSKERL
                   Bert Bledsoe         Monty Frazier
                   Don Clark           H. George Keeler
                   Mike Cook           Lowell Leach
                   Dan Draper
              EWRE-UT
                   David Erickson       Kapil Sabharwal
                   Nadine Gordon       Gerald Shaw
                   Frank Hulsey        Karen Spaniel
                   Daniel Kelmar
     Supportforthe project was provided by acontractfromEPAto the Dynamac Corporation
and a sub-contract from Dynamac to EWRE-UT. The assistance and cooperation of the
following Dynamac personnel who helped facilitate the project also is appreciated:
                   George E. Parris     Lewis A. Waters
                   Bruce W. Beach      Robin K. Roth
                                  XVI

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                                 CHAPTER 1
                               INTRODUCTION
BACKGROUND
     The Resource Conservation and Recovery Act (RCRA) amendments of 1984 requires
the U.S. Environmental Protection Agency (EPA) to assess the adequacy of current federal
programs to protect human health and the environment from mismanagement of non-
hazardous and unlisted hazardous wastes.  Because the land disposal options of concern
for listed  hazardous wastes  include landfills,  land  treatment,  waste piles, surface
impoundments and salt domes, the EPA evaluation of RCRA Subtitle D unlisted wastes
includes these options. As a result, information is needed to support EPA activities related
to the evaluation of Subtitle  D wastes.
     The EPA Office of Solid Waste (OSW) has assessed the extent of land disposal for
Subtitle D industrial wastes. The assessment indicated that at least 145 million metric tons
of industrial non-hazardous waste (35% of all such waste) are managed by on-site landfills,
surface impoundments and land application. The OSW assessment also indicated significant
missing information, especially data related to the performance achieved when such disposal
options are used.  Much of the available data were over 10 years old and little information
existed on the impact that such operating land disposal options have on human health and
the environment.
OBJECTIVES
     The major objective of this project was to determine the performance of a full-scale,
operating land treatment system treating  non-hazardous waste.  Performance was to be
evaluated in terms of treatment of the applied waste and the environmental impact of the
system, particularly surface and groundwater quality. Performance data was to be obtained
from a land treatment system that had been operating for an extended period of time. Equally
important was the cooperation of a company that: (a) had comprehensive, long-term data
about the characteristics of the wastes that have been applied, (b) was able to identify the

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application rates that have been used and the acreage to which these wastes were applied,
and (c) would permit the existing data to be analyzed and additional wastewater, soil,
groundwater and vegetative samples to be taken.
FIELD LOCATION AND STUDY AREA
     The Campbell Soup (Texas) Inc. OLF treatment system located in Paris, Texas was
utilized for all research described in this report.  The following provides a brief summary of
the Campbell Soup plant and OLF system and the logic why this system was chosen for
evaluation. A complete description of the plant and system is presented in Chapter 4.
     The plant processes about one billion cans of soup per year and employs about 1,600
people. The site has about 364 hectares (700 ac*) that are being used for the land treatment
of vegetable processing wastewater by the OLF method. About 16,000 cubic meters/day
(4.25 mgd) are handled in this manner. Only the vegetable processing and can preparation
wastewaters are applied to the site. All sanitary wastewaters from the plant are discharged
to the Paris, Texas, municipal wastewater treatment plant.  In addition,  all stormwater and
can cooling water are handled separately and discharged to surface streams.
     The size of the land treatment system has increased over the years. The original site
consisted of 120 ha (300 ac). Three expansions have occurred: each of approximately 80
ha (200 ac). The expansions resulted in a total of 365 ha (900 ac) being included in the OLF
system.  Not all of  the site is available for wastewater treatment; over 485 ha (1,200 ac)
comprise the entire site.
     The original fields have have been in operation the longest, since the 1960's. The
second set of fields began to be used in the early 1970's and in the late 1970's the third set
of fields began to be used. This allowed the opportunity to evaluate soils that have received
wastes for different time periods.
' Conversion factors relating metric and U.S. units are presented in Chapter 11.

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     About 1.5-cm (hydraulic application rate) of wastewater are applied to the wetted
acreage each day. Prior to application, the wastewater is screened to remove large solids,
and grease is skimmed.  The plant and the land treatment site operate all year. No storage
is used. The wastewater is pumped directly from a 375-cubic meter sump (100,000-gallon)
and is applied by spray headers that have a spray radii of 30-m (150-ft). The overland flow
slopes are about 55-m (170-ft) in length.
     The soils at site are clays and sandy, clay loams. A semi-confined aquifer exists below
the site.  Depth to this aquifer varies between 5-m and 10-m (15 to 30-ft).
     The vegetation on the land treatment site is Reed canary grass and tall fescue. The
crop is harvested two to three times per year and used as forage in the local area.
     The logic for choosing this site  for this evaluation was as follows. The Paris, Texas site
was evaluated in considerable detail in the late 1960's. The early research focused on the
surface hydrology and treatment performance of the system. These early studies served as
sources of basic information and as "background" data.  In addition, many of the Campbell
Soup personnel and the RSKERL personnel who were involved in the earlier research were
still active and were able to participate in this project. Thus, considerable "historical memory*
and knowledge about the plant, available data and the operation of the OLF system was
available to the project.
     Another important feature was that the initial OLF acreage has been used for over 20
years.  Other acreage has been used for shorter periods of time. This allowed the opportunity
to evaluate soils that have received  wastes for different periods of time.
     Most importantly, Campbell Soup agreed to cooperate as actively as possible in the
study, to assist with the sampling that was performed and to provide the available historical
operational and other data. This included available wastewater characteristic data, effluent
monitoring data and weather data. The wastewater data represented the material from the
sump and therefore the  characteristics actually applied to  the site.  Such  data had been

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collected approximately once per month for 10-years.  In addition, effluent monitoring data
have been collected three times a week for 10-years and daily climatological data covering
a 15-year period were available.
RESPONSIBILITIES
     The project was a cooperative effort between: (a) the Robert S. Kerr Environmental
Research Laboratory (RSKERL),  U.S. Environmental  Protection  Agency  (EPA), Ada,
Oklahoma, (b) the Campbell Soup Company, and (c) the Environmental and Water Resources
Program, The University of Texas (EWRE-UT).  The general activities of the cooperating
organizations were as indicated below.
RSKERL
     o provided technical overview of the project
     o assisted in locating a suitable site for the effort
     o helped plan the field components of the study
     o provided personnel and equipment to collect soil cores, perform a site resistivity
         survey, install groundwater monitoring wells and collect groundwater samples
         for analyses.
     o analyzed selected samples for metals, organics and specific non-conventional
         pollutants.
Campbell Soup Company
     After considering possible sites, an excellent one was found. The site is the overland
flow (OLF) land treatment facility at the Campbell Soup (Texas), Inc. plant in Paris, Texas.
A detailed description of the plant and system is provided in Chapter 4 and a summary of
the plant and system  is presented later in this chapter. Campbell Soup:
     o provided details about the plant and land treatment system since they were con-
         structed in 1964.
     o provided historical data on the characteristics of the effluent from the land treatment
         system
     o provided historical characteristics  of the wastewater applied to the land treatment
         system
     o provided estimates of crop yields over the years
     o provided precipitation data collected at the site
     o assisted in numerous aspects of the field work conducted during the study

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EWRE-UT

     o obtained the field samples of soil, groundwater, wastewater. and runoff that were
         part of the project
     o analyzed these samples for conventional, non-conventional and other pollutants and
         chemicals
     o statistically analyzed historical data of precipitation, wastewater loading and effluent
         quality for trends and compared these data to data obtained during the project
         sampling
     o interpreted available data in terms of performance and environmental impact
     o related performance  to initial design and recognized land treatment design rela-
         tionships
     o obtained information about the regional and local hydrogeology
     o prepared final and interim reports

     The cooperative effort worked extremely well.  In addition to the activities identified

above, participants from the  organizations met yearly (April, 1987; June 1988; and June,

1989) to plan the project components, to review data as they became available, to discuss

the implications of the data, and to initiate project modifications as needed to enhance the

effort. Frequent telephone calls between the participants also occurred to facilitate the project

activities and to plan specific efforts. Without this exemplary cooperation by all parties, the

project activities  and the extent of this report would not have been as comprehensive.

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                                 CHAPTER 2
                               CONCLUSIONS
     The major objective of this project was to determine the performance of a full-scale,
operating land treatment system treating non-hazardous waste. Performance was evaluated
in terms of treatment of the applied waste and environmental impact of the system, particularly
surface and groundwater quality. Performance data were obtained from the Campbell Soup
(Texas) Inc. OLF system in Paris, Texas. The Paris, Texas land treatment has been in
operation for over 24-years. The cooperation of the Campbell Soup Company was instru-
mental to the success of the project. Campbell Soup (Texas) Inc. provided: (a) long-term
data about the characteristics of the wastes that have been applied, (b) records of application
rates that have been used and the acreage to which these wastes were applied, and (c)
permitted the existing data to be analyzed and additional wastewater, soil, groundwater and
vegetative samples to be taken.
RAW WASTE CHARACTERISTICS
1.   Over a ten-year period between 1977 and 1988 the main characteristics (BOD5, COD,
     chlorides, sulfates and solids mass loadings) of the raw wastewater exhibited normal
     distributions.
2.   Statistical comparison of raw wastewater quality between recent and old data indicated
     long-term consistency with respect to flow and pollutant concentrations.
3.   Individual metal loadings were variable over a 12-month period.
LAND TREATMENT SYSTEM PERFORMANCE
4.   Seasonally heavy precipitation (>7.5 cm/month) resulted in small increases in TSS
     mass discharges (200 kg/d to 500 kg/d) within Smith Creek. These increases were well
     below regulatory mass loading limitations (values) and no statistically significant cor-
     relation (p < 0.05) was found between the TSS loading and precipitation.

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5.   Because land treatment slope solids discharges were unaffected by heavy precipitation,
     it appeared that small increases in TSS loading in Smith Creek during periods of heavy
     precipitation were due to upstream (off-site) sources.
6.   The long-term operation and performance data indicated that the system consistently
     achieved a very high level of treatment, from a surface discharge standpoint. In-stream
     concentrations of BOD6, COD, TOC and  TSS indicated that mean removals were
     greater than 93%. Total nitrogen removals were between 84 and 89%.  Effluent mass
     discharges have remained well within the  regulatory limitations for solids and BOD5
     over the past 24  years. Percent removals (mass basis) for BOD5, COD, TOC and TSS
     have been consistently high (>92%) over the 24-year life of the site.
SOILS
7.   With respect to the control area, accumulation of organic carbon, potassium, zinc and
     nickel in the soil at the wastewater application areas was evident, as well as leaching
     of calcium, sodium, and sulfate.  Neither accumulation  nor leaching  of chromium,
     magnesium,  and chloride was evident.
8.   Although the accumulation of zinc and nickel was evident, the rate of accumulation
     was so small that several hundred years of continued site use may be expected at
     present loading  rates.
HYDROGEOLOGY
9.   The results of the hydrogeologic investigation indicated that an aquifer exists below
     the OLF site. The data suggested that the aquifer was semi-confined.
10.  The results indicated that the erosional contact between the lower confining unit (Eagle
     Ford Group)  and the aquifer (Bonham Formation within the Austin Group) may  serve
     as a significant transmission zone for groundwater within the relatively impermeable
     clays of the Bonham Formation. Measured hydraulic conductivity values (average k
     between 10"4 and 10'3 cm/s) within the erosional contact zone between the Eagle Ford
     and Austin Groups  were substantially greater than typical values for unweathered
     marine clay and  shale (k between 10'11 and l

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11.  Groundwater level data indicated that the general flow direction was to the north-west
     with a hydraulic gradient of approximately 0.004 m/m.
GROUNDWATER QUALITY
12.  Twenty six groundwater samples collected from three monitoring wells between 1987
     and 1989 were analyzed. The waters were moderately saline (IDS between 7,000 and
     13,000 mg/L) due to the presence of Na*. Ca2*, Mg2*, Cr, and SO42".  No purgable or
     extractable organics were detected.
13.  Statistical analysis of the groundwater data indicated that, for the major ions present,
     groundwater quality at each well remained  uniform over the three-year period of
     sampling. Statistically significant differences (p = 0.05) in water quality (including
     calcium, magnesium, manganese, sodium, and sulfate) between the well locations
     were found.
14.  State records indicated that no well casings in Lamar County were screened within the
     contact zone of the Austin Chalk-Eagle Ford Groups. In addition, no springs which
     issued from the Bonham Formation were identified within Lamar County or any adjacent
     counties.
15.  The major-ion  chemistries (expressed as ionic ratios) of the groundwater samples
     collected from  the confined aquifer were similar at all three monitoring wells.  The
     major-ion composition data suggested the groundwater below the site have undergone
     similar patterns of geochemical evolution.
16.  Ionic ratios of major ions in groundwater data collected from  lysimeters at the site in
     1968 closely agreed with comparable ionic ratios for more recent samples (1987-1988).
     The pattern of increasing ionic compostion with relatively small changes in ionic ratios
     strongly suggested a trend towards the concentration of dissolved  minerals in the
     relatively slow moving groundwater.
17.  The geochemical data  indicated  that sulfate-chloride  facies  were dominant for
     groundwater at all three monitoring wells (MW-1, MW-2 and MW-3) and for the lysimeter

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     data collected in 1968. Thus, the similarity of water quality among well locations as
     well as the similarity in the pattern of geochemical evolution over the past 24-years
     were strongly suggested.
18.  The moderately saline aquifer below the OLF site was apparently the result of the
     enhanced leaching of naturally present, soluble soil minerals due to the infiltration of
     large volumes (based on estimated percolation rates) of treated wastewater over the
     past 24-years.

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                              CHAPTER 3
                 GENERAL MATERIALS AND METHODS
INTRODUCTION
    Samples of soil, groundwater, effluent and raw wastewater were collected at the Paris,
Texas site. The data were used in the evaluation of the long-term performance of the OLF
system and its effects on the environment.
    Table 3-1 is a summary of the analyses performed and the media (soil, groundwater,
wastewater) from which the samples were collected.
         TABLE 3-1. SUMMARY OF SAMPLE ANALYSES PERFORMED
Analysis
COD or %OC
BOD,
TOC
NH,-N
NO,-N
NO,-N
Chloride
Sulfata
TSS
VSS
IDS
pH
Conductivity
Alkalinity
Dissolved O,
Metals
CEC
Volatile
organics
Base/neutral
extractables
Soil
X





mm*
il'-i;:.:,1-':*;



X
X


X
X


Groundwater

X
X
X
X
X
X
X


X
X
X
X

X

X
X
S;:Wastewaterlx;
X
X
X
X
X
X
X
X
X
X

X
X

X
X



                                  10

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ANALYTICAL METHODS
Dissolved Oxvaen (DPI
     Dissolved oxygen (DO) levels in natural and wastewaters depend on the physical,
chemical, and biochemical activities in the water body. The membrane electrode procedure"1
was used for all DO analyses. A YSI Model 58 DO meter and stirring electrode were used
for the measurements.  The probe was calibrated daily according to the manufacturers
instructions.
Biochemical Oxygen Demand (BOD)
     The five-day biochemical oxygen demand (BOD6) determination is an empirical test in
which standardized  laboratory procedures are  used to determine the relative oxygen
requirements of wastewaters and effluents. The test measures the oxygen required for the
biochemical degradation of organic material (carbonaceous demand) and the oxygen used
to oxidize inorganic matter such as suit ides and ferrous iron.
     Method 507(1) was followed for the determination of BOD5 of samples collected at the
Paris, Texas site. Samples were collected in 1-L plastic cubitaners and stored on ice until
analysis. The maximum storage time for the samples prior to analysis (48-hrs) was within
EPA regulatory limits'1'.  Samples were not seeded. However, nitrification inhibitor (Nitrifi-
cation Inhibitor 2533, Hach Chemical Co.) was added.
     Each sample was prepared at three different dilutions, with a minimum of two replicates
at each dilution.  Initial and final dissolved oxygen (DO) concentrations were determined
using the membrane electrode technique, method 421 F(1). A YSI Model 58 dissolved oxygen
meter and stirring electrode were used for the measurements.  The probe was calibrated
daily according to the manufacturer's instructions.
Chemical Oxygen Demand (COD)
     The chemical oxygen demand (COD) is a measure of the oxygen equivalent of the
organic matter content of a sample that is susceptible to oxidation by a strong chemical
oxidant.
                                      11

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     The Twistube COD method was used. This method has been shown to be equivalent
to the standard COD method. The prepared reagents (in twistubes) and block heater were
purchased from O.I. Corporation. A Beckman Model Lambda 3 spectrophotometer operated
at a wavelength of 430 nm was used for the analysis of the digested samples.  Standards
within the sample concentration range and blanks were prepared and analyzed in duplicate
daily. Standards were prepared from potassium hydrogen phthalate as described in method
508A(1). Each sample was analyzed singly with 20 percent of the daily sample load analyzed
in duplicate.
Total Organic Carbon (TOG)
     Total organic carbon (TOC) is independent of the oxidation state of the organic matter
and does not measure organically bound elements such as nitrogen and hydrogen that can
contribute to the oxygen demand measured by BOD5 and COD.
     TOC was determined by the combustion-infrared method according to method 505(1>.
A Beckman model 915B TOC Analyzer was used for the analyses.  Standard curves for
inorganic and total carbon were prepared daily from appropriate standards.  Daily blanks
were run for the determination of background correction factors. Individual samples, blanks,
and standards were injected a minimum of three times per analysis per channel (TC/IC) and
the mean response value was used for the determination of the TOC value.
Metals
     Total metals and water soluble metals were determined by inductively coupled argon
plasma (ICP) spectroscopy. Soil and water samples analyzed fortotal metals were extracted
and prepared according to SW 846 Method 3010(3) Water soluble soil extracts were prepared
in 1:5 (by weight) soil to water (ASTM Type II)  mixtures and tumbled overnight, Method
10-2.3.2*4'. The 1:5 solution was centriiuged, and the supernatant analyzed directly by ICP.
     The majority of the soil and water ICP metal analyses were performed at the RSKERL
in Ada, Oklahoma.  Additional analyses were performed at UT-Austin.  The analytical pro-
cedures for each ICP unit were similar and are described below.
                                      12

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     A minimum of three standards for each metal were used for each calibration. Operating
standards were prepared from laboratory grade 1,000 mg/L standards and diluted to
appropriate concentrations with ASTM Type II water. The standards were stored in solutions
acidified with nitric acid at a pH of less than 2.  Based upon the sample matrix, appropriate
internal standards were used.  Each soil sample was extracted and analyzed in triplicate.
Spikes and blanks of the extracts were run at a minimum of  10% (each) of the daily sample
load.
Residue
     The term "residue" refers to solid matter suspended or dissolved inwaterorwastewater.
Water and wastewater samples collected at the Paris, Texas site were analyzed for total
suspended solids (TSS) and volatile suspended solids (VSS) according to methods 209D
and 209E respectively01. Each sample was analyzed singly with a minimum of 20% of the
daily sample load run in duplicate.
     Total dissolved solids (TDS) content  of groundwater samples  was determined
according to to method 209C(1>. Each sample was run in duplicate.
Alkalinity
     Alkalinity of a water is its quantitative capacity to react with a strong acid to designated
pH.  Alkalinity of  many surface and groundwaters is primarily a function of carbonate,
bicarbonate, and  hydroxide content;  however, other substances such  as borates and
phosphates can affect alkalinity values.
     Method 403' was followed for the determination of total alkalinity values for ground-
water samples.  Values were reported as alkalinity, mg CaCCVL to pH 4.5.
Ammonia
     Ammonia was analyzed for according to method 417E(1>. An Orion Model 701A digital
IONALYZER* and an Orion ammonia-selective electrode were used.  Operating standards
covering the concentrations of  1,000,100,10,1 and 0.1 mg NH3-N/L were prepared daily
and used to calibrate the electrode prior to each use.
                                       13

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Anlons
     Water soluble soil extracts (as described in the Metals subsection), water and waste-
water samples were analyzed for nitrate, nitrite, chloride, sulfate and phosphate by ion
chromatography'5'.  A Dionex Model 10 ion chromatagraph with standard strength eluent
(0.003 M NaHCO3,0.0024 M Na2C03) was used. Operating standards were prepared weekly
and analyzed daily according to the manufacturer's instructions. Duplicate samples were
run on 10% of the daily samples.
Soil Organic Carbon
     Carbon is the chief element present in soil organic matter, comprising from 48 to 58%
of the total weight. Thus, soil organic carbon can be estimated through the measurement
of loss upon ignition SSf/C multiplied by a factor of roughly 0.5. However, the proportion of
carbon in soil organic matter is highly variable for a range of soils, and thus any constant
factor selected is an approximation at best. Therefore, it is most appropriate to analytically
determine and report the actual organic carbon content of soil rather than convert from organic
matter measurements.
     The modified Mebius procedure, method 29-3.5.3.1(4) was used for the determination
of soil organic carbon percentage.  The Mebius procedure is similar to the COD test in that
it involves rapid chemical oxidation through the application of heat and the use of potassium
dichromate. Each soil sample was run in duplicate and mean values and standard deviations
of the soil organic carbon percentages.were reported.
Puraeable  Oraanlcs
     Gas chromatography/mass spectroscopy, Method 8240(3) was used for the detemi-
nation of volatile organic compounds in groundwater samples. The Purge-and-Trap method
(Method 5030(3)) was used to purge the volatile components of the groundwater prior to
analysis. The volatile components were separated via the gas chromatograph and detected
using a mass spectrometer which provided both qualitative and quantitative information. The
analyses were performed by EPA at the RSKERL in Ada, Oklahoma.
                                       14

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Base/Neutral Extractables
     Base/neutral extractable organic compounds were determined by gas chromatogra-
phy/mass spectroscopy,  Method 8270.(3)  The analyses were performed by EPA at the
RSKERL in Ada, Oklahoma.
Specific Conductivity and pH
     Specific conductance is a numerical expression of the ability of an aqueous solution
to carry an electrical current. This ability depends on the presence of ions, their total con-
centration, mobility, valence, and relative concentrations, and on the temperature of mea-
surement.
     A self-contained  Lab-Line" Model MC-1,  Mark V conductivity meter was used to
measure aqueous conductivity according to SW-846 Method 9050*3'. Aqueous samples were
measured directly without prior preparation. Soil samples were prepared in 1:5 (by weight)!
soil to water (ASTM Type II) mixtures and tumbled overnight, method 10-2.3.2(4>. The 1:5
solution was centrifuged, the conductivity of the supernatant was measured directly.
Duplicates were run on 10% of the daily samples.
     pH is a measure of the hydrogen ion concentration of an  aqueous sample. The
electrometric measurement method, SW 846 Method 9040(3>, was used for pH determination.
An Orion Model 701A digital IONALYZER* and an Orion pH electrode were used.
     Aqueous samples were analyzed directly without prior preparation. Soil samples were
prepared in 1:1 (by weight) soil-water pastes, method 10-2.3.2<4>, mixed for 30 minutes, and
measured directly.
Cation Exchange Capacity (CEC)
     The cation exchange capacity (CEC) of a colloidal material is defined as the excess of
counter ions in the zone adjacent to the charged surface or layer which can be exchanged
for other cations'61.  The adsorbed cations, including Na*, K*. H*. Mg2*, Ca2*, and Al3*, are
not an intergral part of the colloidal crystal lattice structure and can be replaced or exchanged
                                       is

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with other cations in the soil solution.  The cation exchange phenomenon  is of great
importance in the soil, as it affects the retention and release of nutrients and other salts, as
well as the f loccuiation-dispersion processes of soil colloids.
     The CEC values were determined according to Method 9081 of SW 84613'- Duplicates
were run at the rate of 10% of the daily sample load.  The CEC was expressed as the number
of milliequivalents of cations that were exchanged in a sample with a dry mass of 100-g.
STATISTICAL ANALYSES
Test for Normality
     Many parametric statistical tests conducted during this research were based  on the
assumption that the universe from which the sample was drawn was normally distributed.
When samples have a normal distribution, parametric tests have a lower occurrence of Type
II error (rejecting the null hypothesis of equal means when it is, in fact, true) and are thus
more sensitive than nonparametric tests, at any given level of significance. In contrast, when
the data are not normally distributed, nonparametric tests (distribution-free tests) are pre-
ferred over parametric tests, as the latter have a higher probability of Type I error (accepting
a false null hypothesis).  It was therefore important, when possible, to test the assumption
of normality.
     Normality was tested by the following method. The sample data were transformed into
standard normal distribution values, and the normal distribution values were divided by the
mean to obtain normal scores'71. The normal distribution values were given by the probability
density function:
                             ...
                            /(x)=

where:
                   JT= pi
                   x = sample value,
                   o= standard deviation, and
                   H= mean.
                                       16

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     The normal values were calculated using equation 3-1 by using sample values and the
long-term values of the mean and standard deviation.
     The normal scores of the data were computed and then the individual sample values
were regressed (linear regression) against these corresponding, calculated normal scores.
Thus, the sample values were regressed against the normal score values.  The correlation
(r) of the normal scores with the sample values was calculated. The correlation coefficient
is a  measure of the closeness  of relationship between two variables-more exactly, the
closeness of the linear relationship. The square of r can be described approximately as the
estimated proportion of the variance of Y that can be attributed to its linear regression on X,
while (1-r2) is the proportion free from X.  Thus, at r a 0.9 (r2= 0.81), about 80% of the
variation in Y can be attributed to its linear regression on X.  In other words, 20% of the
variation in Y cannot be explained by the regression on X. For the sample data, large values
of the square of the correlation coefficient r1 indicated that regression was statistically sig-
nificant and thus, the data distribution closely followed a normal distribution'8'.
Student's t-test
     The student's t-distribution was used to develop confidence intervals about mean values
and test for differences between  pairs of data when the data fit a normal distribution, but the
population standard deviations were unknown, no matter what the sample size was.  For all
statistical tests comparisons conducted as part of this research, the probability (p) of a Type
I error was specified as p  0.05, i.e., there was a 1 in 20 chance  of accepting the null
hypothesis of equal means, when in fact, the means were different.
Analysis of Variance
     The ANOVA test can be described as a statistical method for comparing 2 or more
populations or treatments. It can be used fortesting hypotheses involving two or more means.
The null hypothesis of equal means is tested through application of the F-test. ANOVA was
used when simple pairwise analysis techniques (such as the paired t-test) were inadequate
                                        17

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due the complexity of the data sets. ANOVA techniques were used to decide whether the
differences among sample means were large enough to imply that the corresponding pop-
ulation means were different.
One-way ANOVA
     In the application of one-way ANOVA, random samples drawn from different popula-
tions were are divided into different groups or treatments based upon specific experimental
conditions. The ANOVA test was then performed with the means and variances from each
treatment. The test was used to identify differences between means when more than 2
treatments or conditions were specified, with an independent variable held fixed. Forexample,
one-way ANOVA was used to decide whether groundwater quality (i.e. the concentration of
individual ions, the fixed variables) varied between 3 monitoring wells (the treatments).
     The ANOVA test can be described as a statistical method for comparing two or more
populations ortreatments. It can be used fortesting hypotheses involving two or more means.
The null hypothesis of equal means is tested through application of the F-test.  For the raw
wastewater metals data, each sample collection date was considered as an individual
treatment and the mean concentration value (calculated from duplicate samples) of each
individual metal ion was from each treatment was tested by ANOVA to determine if the
concentration of the metal ion remained constant over time.
     When statistical differences were found (as indicated by an F-statistic which exceeded
the critical F-statistic) differences between the means were tested using the Q-test method18'.
Two-way ANOVA
     The ANOVA2 test was used (as opposed to the one-way ANOVA test) when two dis-
crete, independent variables were involved; for example, location and depth. When applied
to the soil data, the ANOVA2 test included data from all sampling locations and all depths.
Thus, all data collected were used to draw conclusions regarding soil trends.
     The ANOVA2 test can be used to assess the impact of interaction between the two
independent variables. The significance of the interaction, with respect to the two independent
variables, must be evaluated before conclusions are drawn. The ANOVA2 test is unaffected
                                      18

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by significant interaction if at least one of the independent variables is at a random level.
However, if both variables are fixed, and interaction is significant, no conclusions can be
drawn regarding the significance of the two variables. The decision as to whether a variable
is at a fixed or random level is based on practical considerations. For the Paris, TX data,
both fixed and random variables were specified in the application of ANOVA2; therefore, it
was appropriate to test for signficance between treatments even  when interaction effects
were significant.
                                        19

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                                 CHAPTER 4
                    TREATMENT SYSTEM DESCRIPTION
INTRODUCTION
     The following section provides a physical description of the Campbell Soup (Texas)
Inc. site, its history of construction and operation, an accounting of wastes produced at the
plant and the methods for their disposal, and a description of the regulatory monitoring
requirements for the discharge from the system.
FACILITY BACKGROUND
     The Campbell Soup (Texas)  Inc., Paris, Texas plant, located in  Lamar County in
northeast Texas (Figure 4-1), is a heat process canning facility which produces about one
billion cans of soup per year.
      Heat processed soups, spaghetti products, V-8 juice, and pork and beans are produced
at the plant. Raw material is brought to the facility by road freight and rail. The plant operates
year-round, 24-hours per day, with the exception of a 2-week shutdown (for maintenance
and cleaning) in early June.
     The complete plant site encompasses over 550 hectares;  however, only about 40
hectares are actually occupied by the plant and associated grounds and roads.  Of the
remaining acreage, approximately 364 hectares are used for wastewater application, with
the balance left as pasture. A site plan is provided in Figure 4-2.
     Approximately 1,600 people are employed at the plant, which operates on a system of
three-8 hour work shifts, beginning with the 7 AM to 3 PM shift. The first  shift includes 800
people, 500 on the second shift and 300 on the third shift. A separate work crew of 7 people
is entirely responsible for the operation and maintenance of the land treatment system. Five
employees are assigned to the first shift and one person to each shift thereafter. The activities
of this latter group include the monitoring of raw wastewater and  effluent quality, sprinkler
and pressure line repair, access road maintenance, and pretreatment equipment and pump
inspections.
                                      20

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Figure 4-1. General Location Map: Paris.Texas
     The Paris, Texas OLF treatment  system is located over ground which had been
abandoned in the early part of this century due to poor cotton farming management practices
which resulted in depletion of soil nutrients and severe erosion"1.  Prior to the initiation of
land treatment operations, the land was cleared of trees, brush, grasses and erosion features
and graded to form uniform slopes and terraces for treatment purposes.
                                       21

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                                                                                    Lake Crook
                                  BORING A       Smith Creek
                                                                                  Creek Monitoring j
                                                                                         Station  !
                    scale
                    meter*
                                           9     Qroundwcur monitoring well.
                                           A      Soil boring
Figure 4-2.    Site Plan: Campbell Soup (Texas), Inc. The terms E-32, Y-16, G-4, B-13.
              W-5 and CONTROL indicate the locations where detailed site investigations
              were performed.

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     Overland flow land treatment operations began at the site in November 1964. At that
time, the mean daily wastewater flow was approximatley 16,000 cubic meters/day.  In the
late 1960's and early 1970's, the Campbell Soup Company anticipated significant expansion
of processing operations at the Paris, Texas plant and consequently increased the size of
the OLF system. The anticipated processing expansions, however, never occurred and plant
output in terms of product and wastewater flow has remained constant. Thus, the addition
of OLF capacity (wetted acreage) resulted in progressive reductions in the actual wastewater
application rate (volume of wastewater applied per unit area). The effects of the additional
treatment capacity on wastewater loading are discussed in Chapter 5.
      The overland flow system reached its present size of approximately 365 ha after three
successive expansions over the past 25 years. The original application system (constructed
in 1964) consisted of  120 ha.  Three additions in 1966, 1971, and 1975  (Figure 4-3) of
approximately 80 ha each have resulted in the present system.
     Soil characteristics at three spray lines (Y-16, G-4, and E-32) were studied in detail.
The terminology "spray line" refers to a discrete application area to which wastewater was
pumped to through a single distribution pipe (line). The alpha-numeric distribution piping
identification system used by Campbell Soup service personel was used throughout this
report to maintain continuity with previously  published literature.  Soil characteristics at a
control area which had never received wastewater were also examined.
     The Y-16 and G-4 lines were  part of the original system and first received wastewater
on November 30,1964.  The E-32 line, part of the third expansion in  1975, has received
wastewater since 1978.  These three spray lines were chosen for detailed study because
the differences in their ages provided a means to evaluate the effects of OLF on soil char-
acteristics over time.  The B-13 line and the W-5 line were used to assess treatment slope
runoff characteristics.
                                       23

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                                                                       Land not used for
                                                                       wait* traatmant.
                  meters
Figure 4-3. Expansions of the Paris. Texas System

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SOLID AND LIQUID WASTE DISPOSAL
     Between 1,900 and 3,800 m3/d of can cooling water is discharged directly into a runoff
collection channel which flows into Smith Creek at the south end of the site (Figure 4-2). The
cooling water temperature range is between 40 and 60C. Within the period from January
through December of 1987,44 samples were collected from the cooling water discharge.
The mean cooling water quality values were: COD = 40 mg/L, BODS 6 mg/L, TSS = 10
mg/L. The cooling water input to Smith Creek does not result in a significant degree of dilution
of the OLF system runoff because OLF system discharge and cooling water quality are very
similar.
     Stormwater runoff from plant buildings, parking  lots, and associated grounds was
discharged into effluent collection channels that flowed directly to Smith Creek (Figure 4-2).
Sanitary wastewater produced at the plant was sent directly to the City of Paris municipal
treatment system.
     All cans were made from sheet metal which was cut and formed at the plant. The cans
were made of steel and tin.  Some cans were soldered with tin, others were welded. Damaged
cans and scrap metal were sold back to the vendor and recycled. Paper labels were printed
offsite and glued  onto cans at the plant.
     The can forming areas were washed down once daily with solvents, detergent and
water.  The solution was collected  and used for energy recovery in a boiler. There was no
discharge of this  solution into the wastewater treatment system.
     Freight loading areas at the rear (north end) of plant were washed down on occasion
with detergent and water.  The wash water was discharged to the north storm sewer drain
(Figure 4-2) and was not released into the wastewater treatment system.
     Cooling tower blowdown water was discharged continuously into the north storm sewer
drain at the rate of 3.0-m3/d. The median pH of this wastewater stream was 7.8. Zinc was
added to the cooling tower water to maintain a residual concentration of 0.5 mg/L zinc.  A
0.05 mg/L free chlorine residual was maintained  in the cooling tower water through the
addition of HTH (a commercially available biocide).
                                       25

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     Inside the processing plant, two separate collection systems directed grease waste-
water and vegetable wastewater by gravity to an adjacent building which housed pretreat-
ment, pumping and control equipment.
     The grease wastewater traveled through a gravity grease separator in which non-
miscible oils, fats, and grease were skimmed off of the water surface.  The grease was
temporarily stored on-site in 210-L drums. Approximately 360-L of grease was collected each
day. The drums were periodically removed by a local rendering company. The skimmed
grease wastewater was combined with the vegetable wastewater and directed through four
rotating drum screens (No. 10 mesh) where  large vegetable solids were removed and
conveyed to a large hopper and dumpster.  The accumulated vegetable solids (22,700 kg/d)
were hauled to a municipal solid waste landfill 4-5 times per day.
     The screened wastewater discharged to a 375-m3 sump. A mechanical grit lift system
periodically removed inert material from the bottom of the sump.  Turbulence, due to the
short residence time in the sump (approximately one-half hour) and coarse aeration, kept
most of the remaining wastewater solids in suspension.
     The wastewater level  in the sump was automatically maintained by a liquid level
controller which progressively activate a maximum of six high-pressure turbine pumps as
required. As each pump started, it activated a clock timer.  This, in turn, opened the valves
in the spray fields that were preprogrammed to that pump. The valves were operated
pneumatically. There were four clocks, with three dedicated to 8-hr shifts and the fourth as
a variable rate backup mechanism for sump relief  when flow exceeded the capacity of a
preprogrammed spray line assignment during any one shift.
     A flow diagram of the daily disposition of the principal solid and liquid  wastewater
streams at the Paris, Texas site is provided in Figure 4-4.
                                       26

-------
                 VEGETABLE WASTE
                 GREASE WASTE
                       GREASE SEPARATOR
         GREASE KETTLES
       HOPPER FOR SOLID WASTES
       TRANSPORT TO MUNICIPAL
       SANITARY LANDFILL.
    | ROTARY SCREENS!
    ooo-
                          WASTEWATER SUMP
                 CREEK
 OVERLAND FLOW       ^_

TREATMENT FIELDS  ^^.

             CREEK
                        SMITH CREEK
                                   CREEK MONITORING STATION
                                   (BOD, COO, pH, TSS, TEMP., FLOW)
Figure 4-4. Flow Diagram of Waste Processing and Land Treatment System
                                 27

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      Campbell Soup, Inc.  possessed a Texas Water Commission  (TWC) Solid Waste

Registration Number (# 30453) for the management of solid waste on- and off-site.  The

registration was not a permit to dispose of waste. The registration number provided access

to data stored by the TWC pertaining to solid waste generated at the site.  The Paris, Texas

plant produced four specific solid waste streams as identified in Table 4-1.

           TABLE 4-1. SOLID WASTE IDENTIFICATION AND DISPOSITION
Waste No.
1
2
3
4
Description
solvents, spent
plant refuse,
general misc.
food wastes/scrap
asbestos insulation
Class
IH
II
II
I
TWC Code
910100*
279760
280010
179390
Disposition
on-site/secondary
use1
off-site2
on-site3
off-site4
     +   EPA hazardous waste number: F001.  Description as per 40 CFR Part 261; Hazardous Waste Man-
         agement System; Identification and Listing of Hazardous Wastes, U.S.EPA, The following spent
         halogenated solvents used in degreasing: tetrachlorethylene, trichloroethylene.  methylene chloride,
         1.1,1-trichlorethane, carbon tetrachloride, and chlorinated flurocarbons; and sludges from the recovery
         of these solvents in degreasing operations.*

      1 Used for energy recovery in a boiler on-site.
      1 Disposed of in municipal/non-hazardous waste landfill off-site.
      1 Disposed of in unlined trenches on-site.
      4 Disposed of off-site in approved hazardous waste facility.


     Waste  No. 3  (food wastes/scrap) consisted of "bad product",  i.e., canned or bottled

soups and sauces which did not meet Campbell Soup's quality standards. These packaged

products were buried onsite in shallow trenches (about 3-m deep). Three solid waste disposal

(burial) areas for these wastes were located at the Paris, Texas OLF site (Figure 4-5).
                                          28

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to

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SPRAY SITE
     In this overland flow (OLF) land treatment process, the screened wastewater was
applied to the top portion of graded, vegetated slopes. Treatment occurs as the applied
wastewater interacts with the soil, vegetation, and biological surfaces. Physical, chemical,
and biological reactions remove most of the contaminants. Treated effluent was collected at
the bottom of each slope. The graded clay soils were relatively impermeable and this results
in the major portion of the applied wastewater exiting the system in the form of surface runoff.
The runoff was collected in ditches or channels at the tail end of the treatment slopes, and
was discharged to an adjacent surface water body. Some fraction of the applied wastewater
was lost to deep percolation and evapotranspiration.  A schematic of a typical installation is
illustrated in Figure 4-6.
                      "         I   I   I
                      LICATION)	|
                         - ^~  - I    K   I
                       > *    CWADrtTDAfclODIC
   WASTEWATER APPLICATION
(SURFACE OR SPRINKLER APPLICATION)
                            "EVAPOTRANSPIRATION
 GRASS COVER CROP
                                                                          SLOPE 2-8%
                                               GRASS AND VEGETATIVE LITTER

                                                     SURFACE RUNOFF'
                                                          EFFLUENT COLLECTION CHANNEL
                                    VEGETATIVE THATCH AND
                                    BIOLOGICAL SLIME LAYER
Figure 4-6. Idealized Overland Flow Slope
                                        30

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     On the initial 80 ha at the Paris Texas site, slopes were formed into 1 to 4 ha watersheds
following the natural lay of the land, with slope lengths in excess of 75-m. The slopes range
from 2 to 8%.  Experience gained from the intial years of OLF operation indicated that greater
land-use efficiency could be attained without a degradation in treatment performance by
forming 0.4 to 1.6 ha watersheds with slope lengths of approximately 55-m. This improved
design was used in the three successive expansions.
     The wastewater was  distributed to the slopes via 40-cm force mains which feed the
10-cm  spray line laterals. The lateral lines operate between 270 and 500 kPa and supply
the impact sprinklers (80-mm nozzle diameter) which discharge about 76 L/min (maximum
rate) each.  Each spray line included about 8 to 10 sprinklers, spaced about 21 -m apart. The
sprinklers had a full circle spray pattern with a 15-m radii. In general, the treatment slopes
were 55-m  in total length, with the spray header lines located about 15-m downslope from
the top of the slope. Thus, the sprinklers were located about 40-m from the collection ditch
at the tail end of the treatment slope. This is illustrated in Figure 4-7.
     The vegetation on the slopes was reed canary grass and tall fescue, with reed canary
being dominant within the spray radii. Outside of the spray pattern, tall fescue, and some
coastal Bermuda grass and Dallas grass flourished. These grasses (reed canary and tall
fescue) are cool season varieties and are highly water tolerant. Each irrigated hectare yielded
approximately 7 to 9 metric tons of hay annually.  Typically, the hay  was harvested and
removed twice a year (July and October) by an outside contractor. However, during unusually
wet years, site conditions limited vehicle access and mobility.  Under these circumstances,
as the  weather permitted, the hay was shredded on the treatment slopes and left in-place
with no baling or removal.
                                        31

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                                                           10-cm SPRAY LINE
                                                           LATERAL
                     RUNOFF COLLECTION DITCH
Figure 4-7. Schematic of a Typical OLF Treatment Spray Line and One Sprinkler
     Wastewaterwas applied to each slope for 8-hr per day. Typically, quasi-steady-state
discharges (i.e., relatively constant overland flow discharge from the tail end of the slope)
occurred between 4 and 8 hours after the initiation of wastewater application. The breadth
of this range was due to variation in soil moisture, which differed due to frequency of appli-
cation, duration of previous applications, climatological variation and transpiration.
FLOW CONTRIBUTIONS TO SMITH CREEK
     The treated wastewater (effluent) traveled through a multitude of drainage channels to
a central stream (Smith Creek). This creek would be ephemeral without the year-round
addition of effluent. During storm  events,  surface runoff from streets and fields near the
north-end  of the City of  Paris contributed to the flow of Smith Creek.  The combined flow of
treated wastewater, on- and off-site stormwater discharges, and can cooling water in Smith
Creek eventually flowed into the Red River, which corresponds to the Texas/Oklahoma state
line (Figure 4-8, General Location Map: Campbell Soup Plant).
                                       32

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                                                            10  kilometers
Figure 4-8. General Location Map: Campbell Soup Plant
                                      33

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     Water quality of the combined flows in Smith Creek was monitored at an automated
sampling station, in accordance with SPDES and NPDES requirements, at the point where
the creek exited the property (Figure 4-2).  A Parshall flume (maximum capacity 49,205 m3/d)
was used to measure the combined discharge in Smith Creek at this point.
REGULATORY MONITORING REQUIREMENTS
     Federal and State regulatory discharge limitations for the combined flows in Smith
Creek have been established for BODsand TSS mass discharges and flow. The limitations
imposed by the State of Texas and the Federal government were identical with respect to
effluent characteristics, discharge limitations, and monitoring requirements. Permit conditions
(5-year permits) are presented in Table 4-2.
   TABLE 4-2. SMITH CREEK LIMITATIONS AND MONITORING REQUIREMENTS
Effluent
Characteristic
TSS, kg/d
BODSl kg/d
Flow, m3/d
Temperature, C
Dally Ave.
Max. Limit
2,270
606
37,850
32.2
"Dally Max.
Limit
3,696
986
49,205
35
Sample
Frequency
Three/wk
Three/wk
Continuous
Six/day
Sample
Type
24-hr comp.
24-hr comp.
Record
In Situ
     Additional limitations included: (a) the pH of the combined flows at the monitoring station
shall not be less than 6.0 nor greater than 9.0,  and shall be monitored by grab samples
once-per-day; (b) there shall be no discharge of floating solids or visible foam in other than
trace amounts; and (c) when the flow of Smith Creek exceeds the monitoring capacity of the
Parshall flume, 49,205 m3/d, no limitations within the permit apply except for the requirement
that a BOD5 of 20 mg/L never be exceeded as measured at the flume.
     A comparison between regulatory  limitations and actual long-term effluent quality is
provided in Chapter 5.
                                     34

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                                 CHAPTER 5
                  RAW WASTEWATER CHARACTERISTICS
     The following section presents long-term raw wastewater characteristics at the Paris,
Texas plant.  The data were collected by Campbell Soup personnel and UT and EPA
researchers. The data were used to establish long-term operating trends and to calculate
the land treatment system mass loadings and removal efficiencies.
PREVIOUSLY PUBLISHED DATA
     Comprehensive records of raw waste characteristics prior to 1977 were not available.
Mean values (from the 1960's) for several parameters of interest were available from early
studies at the site. The data are presented in Table 5-1 as published.
   TABLE 5-1. RAW WASTEWATER CHARACTERISTICS: MEAN ANNUAL VALUES
Parameter
Flow (m3/d)
BODS
TSS
Total-P
Total-N
1973*
15,140
616
263
7.6
17.4
19686
13,626
492
181*
8.5
18.8
I968m-:i
11.355
572
245
7.4
28.5
          All values in units of mg/L, except flow.
          Gilde. Isra'Vrhornthwaite. 1969"*;"Thomas,etal, 1970"";fVSS.
     No information was available as to the statistical confidence of these mean values or
the number of samples analyzed and the method of collection. Although 3 separate sources
are referenced in Table 5-1, the Thornthwaite report00' served as the primary source of data
for the 2 other reports referenced. The reason for discrepancies between values for identical
parameters is not clear,  but may lie in each author's method of data summarization. The
experimental data collection period ran for 12 months between May 1968 and April 1969.
Because these data are the only sources of raw waste characteristics from the late 1960's,
they served as a means to evaluate the long-term consistency of the applied wastewater.
                                      35

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UNPUBLISHED PLANT RECORDS
     Comprehensive records of raw waste characteristics and flow have been maintained
since 1977. These records, covering the period between 1977 and 1988, were made available
by Campbell Soup for this research.  Composite samples were collected from the sump
several times each month (2 to 3 composite samples) and typically were analyzed for BODS,
COD, oil and grease, TSS, VSS, chloride, and sulfate. Flow, pH, and pumping pressure
were continuously monitored at the sump and these data are stored by a microcomputer
which also served as the automated control for the wastewaster distribution system.  Up-
to-date daily and long-term reports could be generated from data stored in the microcomputer.
These data have been summarized as part of this project and are presented in this section.
     Plots of the cumulative raw data indicated that waste characteristics and mass loading
were relatively constant over the 10-year period of record. Application rates (wetted area
basis) have varied substantially over the 24-years of operation (Chapter 4); however, the
actual mass loadings of principal waste constituents have remained constant. It is important
to note that application rate is a function of volume applied, duration of application and width
of application slope, while mass loading rate is a function of wastewaterf low rate and pollutant
concentration in the raw wastewater; therefore, the two values are do not necessarily vary
congruently.
     Water conservation practices instituted at the plant in 1983 apparently resulted in a
slight decrease in raw wastewater flow.  Although the flow apparently decreased and con-
centrations of of BODS and TSS remained constant, there was no apparent reduction of BOD5
and TSS mass  loads (Figures  5-1, 5-2 and 5-3).  The flow data and BODS and TSS
concentration data were tested for normality and for differences between mean values (by
one-way ANOVA) before and after the start of water conservation practices in 1983 (Table
5-2). The results indicated that the flow data and BOD5 and TSS concentration data could
be described by a normal distribution. There was no statistical difference in the BOD5 and
TSS concentration data between the 2 time periods tested (1977-1982 and 1983-1988);
however, there was a difference in the mean flow values between the 2 time periods.
                                      36

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            Table 5-2. ANOVA of Raw Wastewater Flow and Concentrations
Descriptive
Statistic
Normal*
Distribution r2
1977-1982
Mean and Standard
Deviation
1983-1988
Mean and Standard
Deviation
Statistical Difference**
Between 1977-1982
and 1983-1988?
Calculated
F-statistic
Critical
F-statistic
Flow
(m'/d)
90.8
16,96011,475
14,163 5,000
YES
'eeF- 10.35
4.01
BOD,

-------
        180 -i	
        170 -
        180 -
        ISO -
        140 -
        130 -
        120 -
        110 -
        100 -
         90 -
         80 -
         70 -
         80 -
         50 -
         40 -
         30 -
         20 -
         10 -
         0 -J""
           1977
D O
    a
    a
                  1878   1978    1980    1981    1982    1983
                                         Tim* (month/yv)
                                                          1984    1985    1986    1987
Figure 5-2. BOD5 Load of Raw Wastewater, 1977-1988
        60
        50 -
        40 -
        30H
        20 -
          1977    1978    1979   I960    1981    1982    1983    1984   1985    1986    1987
                                        Tlnw (month/year)
Figure 5-3. TSS Load of Raw Wastewater, 1977-1988
                                             38

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     The sump wastewater characteristics for the ten year period between 1977 and 1988
are summarized in Table 5-3.  All parameters, with the exception of chloride which was
log-normally distributed, fit a normal distribution.
               TABLE 5-3.  SUMP WASTEWATER CHARACTERISTICS*
                           PERIOD: 1977-1988
Wastewater
Parameters
Flow (m3/d)
BOD5
COD
Oil/Grease
TSS
VSS
cr
so4-
NhV-N
Org-N
NOa-N
NO2-N
Total-P
Mean
16,100
550
1,190
125
425
370
66
40
0.7
27
0.33
0.03
6
Standard
Dev.
3,410
210
520
80
210
200
47
20
0.5
9
0.48
0.02
3
NO. Of
Data Pts.
58
80
78
75
80
74
78
78
11
10
10
10
10
            * All values in mg/L unless otherwise noted.
     The characteristics of the raw waste remained relatively constant over the 10-year
period of data collection, regardless of year (see Figures 5-1 through 5-3), month or season.
To illustrate this, mean values and standard deviations for the monthly data from the 10-year
period were calculated for flow, BOD, COD, TSS, chlorides, and sulfates.  Plots of these
representative  parameters illustrated the long-term stability of wastewater flow and con-
centrations (Figure 5-4 through 5-9).
                                       39

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    30
      Flow (cubic m/d) Thousands
    26-
    20-
    16-
    10-
       11
    \
                    II
                              only on* data point -
                               available
       JAN FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DEC
                     Month (1977-1987)
Figure 5-4. Monthly Mean Flow Rate: Screened Raw Wastewater
  1600
  1260
  1000-
  760-
  600-
  260
      BOD-5 (mg/L)
                                       x
I
li
i
I
      JAN FEB MAR APR MAY JUN JUL AUQ SEP OCT NOV DEC
                   Month (1977-1987)
Figure 5-5. Monthly Mean BOD5 Concentration
                            40

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  3500

  3000

  2600

  2000-

  1600-

  1000

   500
       COD (mg/L)
                     TMOMlOx/ I
                     otvunoHv ~W
\
I'll
       JAN FEB MAR APR MAY JUN JUL AUQ SEP OCT NOV DEC
                    Month (1977-1987)
Figure 5-6. Monthly Mean COD Concentration
  1200
      TSS  (mg/L)
  1000-
   800
   600-
   400
   200
                                    	XI
                                    Mvunens. *
ll
I
I
       JAN FEB MAR APR MAY JUN JUL AUQ SEP OCT NOV DEC
                    Month (1977-1987)
Figure 5-7. Monthly Mean TSS Concentration
                             41

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   260
       CHLORIDE (mg/L)
   226-

   200

   176 H

   160

   126-

   100-

    76-

    60

    26 H
                                      
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     The monthly summary data did not exhibit any short-term or long-term trends, i.e.,
monthly or seasonally. This can be attributed to the fact the the plant processes material
year-round with essentially no variation in raw material and product quality.
     The assessment of the possible accumulation and migration of applied metals per-
formed as part of this study (Chapter 6) required a suitable database of raw wastewater
metals concentrations. Because Campbell Soup (Texas), Inc. did not monitor metals in its
raw waste, a sampling program was inititated for a period of 10 months (August 88 - May
89).  A total of twelve time weighted composite samples were collected by Campbell Soup
plant personnel from the screened wastewater in the sump. The acidified samples (pH < 2
with HNO3)  were sent to the Robert S. Kerr Environmental Research Laboratory in Ada,
Oklahoma for analysis.  Cobalt, molybdenum, copper, chromium, nickel, silver, lithium,
vanadium, barium, and boron were detected at or below 0.01 mg/l; cadmium and beryllium
were not detected at 0.003 mg/l; and arsenic and selenium were not detected at 0.03  mg/L.
These values were quantification limits and were determined by instrument (ICP) sensistivity,
sample dilution, and matrix interference. A summarization of the data for detected metals
is presented in Table 5-4.
                 TABLE 5-4. TOTAL METALS CONCENTRATIONS
                            IN SCREENED RAW WASTEWATER
i Wastewater
i Parameters
Sodium
Potassium
Calcium
Magnesium
Iron
Manganese
Aluminum
Zinc
Strontium
Mean*
47.4
24.1
45.1
4.01
0.71
0.04
0.72
0.17
0.19
Standard
Deviation*
15.9
12.1
23.8
1.36
0.41
0.03
0.63
0.11
0.08
                  * Concentration units. mg/L
                                      43

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WASTEWATER MASS LOADING
     Wastewater constituent mass loadings were calculated from the long-term data. Only
paired data sets (i.e., paired daily flow and concentration data) were used to calculate the
loading rates for conventional pollutants (i.e., excluding metals).  Because metal concen-
tations and flow data were not paired,  mean sump values  of metal concentration and
wastewater flow (16,100 cubic m/d) were used to estimate metal loading rates. The results
are tabulated below (Table 5-5).
      TABLE 5-5. WASTEWATER LOADING TO OLF SITE*, PERIOD: 1977-1988
Wastewater
Parameters
BODS
COD
Oil/Grease
TSS
VSS
cr
so*2-
NH/-N
Org-N
NO3-N
NO2-N
Total-P
Sodium
Potassium
Calcium
Magnesium
Iron
Manganese
Aluminum
Zinc
Strontium
Mean
kg/d
8,950
19,600
2,170
7,085
6,330
1,060
633
13
480
6
0.4
91
760
390
725
65
11
1
12
3
3
Standard
Dev., kg/d
4,100
9,555
1.345
3,730
3,640
780
320
9
178
10
0.2
39
255
195
380
22
7
1
10
2
1
NO. Of
Data Pts.
53
55
52
52
51
55
56
7
7
7
7
7
12
12
12
12
12
12
12
12
12
               Based on sump wastewater characteristics
               and volume pumped.
                                     44

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     For the raw wastewater, major parameters of interest, for which sufficient loading rate
data were available (i.e., COD, BODS, TSS, chloride and sulfate) were tested for normality.
The long-term data for BOOS, COD, TSS, chloride and sulfate exhibited a high degree of
agreement with their normal scores. The r2 values were 0.91, 0.94, 0.96, 0.91, and 0.84,
respectively.  Therefore, the assumption of normality for the raw waste characteristics was
valid.
     Because of the demonstrated constancy of the raw wastewater flow and quality,
long-term mean values  (with associated 95-percent confidence intervals about the mean)
have been used throughout the remainder of this report for the calculation of mass balances
and land treatment system loadings.
     Confidence intervals calculated for the raw waste characteristics during the period
between 1977 and 1988 have been summarized and the results are presented in Table 5-6.
            TABLE 5-6.  CONFIDENCE INTERVALS. SUMP
                        CONCENTRATIONS, PERIOD: 1977-1988
Wastewater
Parameters
Flow (m3/d)
BOD5
COD
Oil/Grease
TSS
VSS
Chloride
Sulfate
Ammonia-N
Organic-N
Nitrate-N
Nitrite-N
Total-P
Mean*
16,100
550
1,190
125
425
370
66
40
0.7
27
0.33
0.03
6
95-Percent
Confidence
Interval
15,220-16,880
500 - 600
1,075-1,300
110-145
380 - 470
325-415
55-76
35-45
0.4-1.1
21 -34
(see note)**
0.02 - 0.05
4-8
                   All values in mg/L unless otherwise noted.
                   Reliable confidence interval could be calculated with
                   available data because the standard deviation value
                   was greater than the mean.
                                       45

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     The early data (Table 5-1) were compared to more recent data (Table 5-2) and the
results are presented in Table 5-7.
               TABLE 5-7.  COMPARISON OF SELECTED SUMP
                           WASTEWATER CHARACTERISTICS*
Parameter
Flow (m3/d)
BOD5
TSS
Total-P
Total-N
1973**
15,140
616
263
7.6
17.4
1969**
13,626
492
181*
8.5
18.8
1970**
11,355
572
245
7.4
28.5
95% Confidence
Interval (1977-1988)
1 5,220 
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(calculated from duplicate samples) of each individual metal ion was from each treatment
was tested by ANOVA to determine if the concentration of the metal ion remained constant
over time.
     The ANOVA testing indicated that at the 5-percent level of significance, other than for
calcium, there was statistically significant variation in mean individual metal concentrations
in the raw waste over the 12 month study period (Table 5-8). Because the variation- in the
mean concentration value for each metal was statistically significant, the range of individual
values provided by the 95-percent confidence intervals were substituted for mean metal
concentrations. The use of concentration ranges provided a statistically sound base for the
calculation of individual metal loading rates (Table 5-4) and estimates of probable long-term
surface accumulations. These aspects are discussed in detail in Chapter 7.
          TABLE 5-8. TOTAL METALS IN SCREENED RAW WASTEWATER
Wastewater
Parameters
Sodium
Potassium
Calcium
Magnesium
Iron
Manganese
Aluminum
Zinc
Strontium
Mean,
mg/L
47.4
24.1
45.1
4.01
0.71
0.04
0.72
0.17
0.19
95-Percent
Confidence
Interval, mg/L
37.3 - 57.5
16.5-31.8
29.9 - 60.3
3.15-4.88
0.45 - 0.97
0.03 - 0.06
0.32-1.12
0.10-0.23
0.13-0.25
ANOVA
Results*
"2F-81
112F  143
112F-18.5
112F = 454
112F . 302
112F = N/A
112F - 742
102F - 468
92F o N/A
             *  At 5% level of significance, critical F values are:
                ",F = 19.40. ",F = 19.39. and %F = 19.38.
           N/A  Not applicable, ANOVA could not be conducted with available data because the
                pooled standard deviation values were equal to zero; i.e., for replicate samples.
                identical concentration values were measured.
                Cobalt Molybdenum. Copper. Chromium. Nickel. Silver. Lithium. Vanadium,
                Barium, and Boron were detected at or below 0.01 mg/L; Cadmium and Beryllium
                were not detected at 0.003 mg/l; and Arsenic and Selenium were not detected
                at 0.03 mg/L
                                         47

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CONCLUSIONS
     The main characteristics (BOD5, COD, chlorides, sulfates and solids mass loadings)
of the raw wastewater exhibited normal distributions over a ten-year period (1977-1988) and
this facilitated the use of conventional statistical analysis techniques. Statistical comparison
of raw wastewater quality between recent and old data indicated a high degree of long-term
consistency with respect to flow and pollutant concentrations.
     The results of the metal specific sampling program indicated that metal loadings of
individual sampling days were variable over the sampling period. Because of this variability,
95-percent confidence intervals about the mean (concentration basis) were used to calculate
loading ranges for  individual metals.  The calculated ranges for individual metals loading
provided a basis for the assessment of soil metal accumulation with respect to applied load.
The effect of metal  accumulation on site life expectancy is discussed in Chapter 7.
                                       48

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                                 CHAPTER 6
           TREATMENT SYSTEM DISCHARGE CHARACTERISTICS
     The following section describes the long-term quality of the treated wastewater which
discharged from the OLF slopes as well as the quality of the combined flows in Smith Creek.
     The performance of overland flow land treatment sites is typically measured by the
quality of the runoff or final downstream water. This aspect is discussed in the following
section. Performance may also be related to the effect of land treatment operations on other
environmental receptors or media, such as soil or groundwater.  The performance of the
Paris, TX system with respect to these media is evaluated in Chapters 7 and 8.
SMITH CREEK WATER QUALITY
     At the monitoring station on Smith Creek (Figure 4-2). water quality and flow rate of
the combined flows in Smith Creek were stable with relatively small annual variations over
the 15-year period for which records were provided by Campbell Soup. Plots of the in-stream
waste constituent concentrations over time are presented in Figures 6-1 through 6-7.
        so -
  .
 i1
 i
a         a
    a
                                       a
                                     aff
                                     2t
         JAN-74     JAN-78    OAN-78    JAN4O     JAN43
                                    ManttVYMf

Figure 6-1. Flow Rate of Smith Creek: 1974-1988
                                                     JAN44
                                                              JAN-B8
                                                                       JAN-M
                                     49

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         40
         39 -
         30 -
         29 -
         20 -
         19 -
         10 -
          9 -
                                                                   aa    a
          JAN-74
                     JAN-76
                               JAN-78
                                          JAN-80
                                                     JAN-82
                                                               JAN-84      JAN-86
                                                                                    JAN-88
                                           MomtVYMT
 Figure 6-2. BQD-5 Concentration in Smith Creek: 1974-1988
180
170 -
180 -
190 -
140 -
130 -
120 -
110 -
100 -
 00 -
 80 -
 70 -
 80 -
 90 -
 40 -
 30 -
 20 -
 10 -
                                                                    
                                                                             rm O
          JAN-74     JAN-78      JAN-78      JAN40      JAN-82
                                           Montli/Y*r
Figure 6-3. COD Concentration in Smith Creek: 1974-1988
                                                               JAN-84
                                                                         JAN-S6
                                                                                    JAN-88
                                             so

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ISO -
170 -
160 -
130 -
140 -
130 -
120 -
110 -
i 100 -
1 *>-
 80-
70 -
60 -
SO -
40 -
30 -
20 -
10 -
0 -
JAN




OD

D

 O
Q
a
O Q
of o
0% o*  o
 tf^b 0Q?)V aQ%* SDO 0Q a 2*a a* Q0 DQa^
a   a o dff
-74 JAN-76 JAN-78 JAN-80 JAN-82 JAN-84 JAN-86 JAN
                                        MomfWr
Figure 6-4. TSS Concentration in Smith Creek: 1974-1988
      100


       90 -


       80 -


       70 -


       60 -


       50 -


       40 -


       30 -


       20 -


       10 -
OD
              aaa
                                       ff
      a a a
       a  a
                     Q
        JAN-74
                  JAN-76
                            JAN-78
                                      JAN40
                                                JAN-82
                                                          JAN-84
                                                                    JAN-86
                                                                              JAN-88
Figure 6-5. VSS Concentration in Smith Creek: 1974-1988
                                          51

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       200
       190 -
       180 -
       170 -
       ieo -
       150 -
       14O -
       130 -
       120 -
       110 -
       100 -
        ao -
        80 -
        70 -
        60 -
        so -
        40 -
        30 -
        20 -
        10 -
a
a
Da  a  a
     a    a
                 a
                 Oj
                                                   a     a
                                                  a
                                                   a    
                                                    cP
         JAN-74
                   JAN-78
                              JAN-78
                                        JAN-80
                                         Month/Year
                                                  JAN-82
                                                             JAN-84
                                                                       JAN-88
                                                                                  JAN-88
Figure 6-6. Chloride Concentration in Smith Creek: 1974-1988









J
a











190 -
180 -
170 -
180 -
150 -

140 -
130 -
120 -
110 -
10O -
90 -
80 -
70 -
60 -
50 -
40 -

30 -

20 -
10 -





a OD

a


a a
a

a o =P
a a^q, ao  QjjP * d^V6 a f^
m R-PdlS'l^'nJ^D1 m O Ty ff^JP _D Q  QL
TJC. a ''"Th aa^ On D ^^ 1V O O "

 a  a
a a

JAN-74 JAN-78 JAN-78 JAN-80 JAN-82 JAN-84 JAN-88 JAN
MontlVYwu-
Figure 6-7. Sulfate Concentration in Smith Creek: 1974-1988
                                            52

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     A summary, for the period 1974 through 1988, of the collective in-stream concentration
data is presented in Table 6-1. The water quality data were obtained from samples collected
at the downstream monitoring station, and are representative of the combined flow of Smith
Creek, can cooling water, precipitation and the treated wastewater discharges.
           TABLE 6-1. CONCENTRATIONS* IN SMITH CREEK: 1974-1988
Parameter
Flow (nyd)
BOD5
COD
Chloride
Sulfate
TSS
VSS
Mean
16,650
5
46
55
48
33
17
Standard
Deviation
5,680
4
19
54
28
43
42
No. Of
Data Points
174
189
188
188
186
189
175
                 *   All values in units of mg/L, except flow.
PERMIT COMPLIANCE
     Because Federal and State regulatory limitations have been established for flow, BOD5
and TSS loads discharged from the Paris, Texas site, an evaluation of the degree of com-
pliance within these limits serves as a convenient and the most common measure of system
performance. Discharge limitations governing Smith Creek water quality were listed in Table
4-2.
     Plots of the daily average waste loading values (monthly means) over the period
between 1974 and 1988 indicated that the quality of the combined discharge in Smith Creek
was continuously well below regulatory limits. Plots of BODS and TSS loading illustrate this
exemplary permit compliance (Figures 6-8 and 6-9).
                                      53

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        1.0





        0.9 -





        0.8 -





        0.7 -
 Jl
        0.6
        as -





        0.4 -





        0.3 -





        0.2 -





        0.1 -
        0.0
                     DAILY AVERAGE LIMFT - 606 kgrd
          JAN-74
                     JAN-76
                                JAN-78
                                           JAN-SO
                                                      JAN-82
                                                                 JAN44       JAN-86      JAN-B8
Figure 6-8. BOD-5 Load in Smith Creek: 1974-1988
        4.0
i!
-t
        3.8 -







        3.0 -







        2.9 -







        2.0 -







        1.3 -








        1.0 -







        0.5 -
        0.0
                      DAILY AVERAGE LIMIT - 2.270 tiQMt
          JAN-74      JAN-76
                                JAN-78      JAN-80      JAN-82      JAN-84       JAN-86      JAN-88



                                             MomtVYr
Figure 6-9. TSS Load in Smith Creek: 1974-1988
                                               54

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     The calculation of the mean load values (daily average) excluded flood events, i.e.,
events when the combined flow in the creek exceeded 49,205 m3/d, the design limit of the
in-stream Parshal! flume.  This method for the calculation of daily averages was established
in the NPDES and SPDES permits.
     Confidence intervals about the mean load were calculated for BODS, TSS, AND VSS.
The results are presented in Table 6-2.  The long-term data indicate that the quality of the
combined flows of wastewater effluent and ephemeral flow in Smith Creek was consistently
well below regulatory limits, with little departure from mean values.
                 TABLE 6-2. EFFLUENT LOADS* IN SMITH CREEK
Parameter
BOD5
TSS
VSS
Mean
80
445
190
95% Confidence
Interval
71 
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     3.00
                                                                       20.0
     0.00
        JAN  FEB MAR APR  MAY JUN  JUL AUG  SEP OCT  NOV  DEC
                               Month (1974-1987)
Figure 6-10.15-year Mean Monthly Waste Loading in Smith Creek and Precipitation
     The mean ratio for 81 data points (for the period 1977-1988) of TSS to VSS concen-
trations  in the raw waste was approximately 1.15.  Linear regression of TSS against VSS
resulted in an r2 value of 0.92, with the  regression equation: TSS,mg/L - 43.2 + (1.01 x
VSS,mg/L). A plot of the residuals (observed minus fined values! rom the regression equation)
against  VSS indicates that the residuals were random, indicative of  a highly significant
correlation between VSS and TSS. Thus, it appeared that in the applied wastewater load,
TSS were almost entirely VSS, and that there was a high degree of confidence in the rela-
tionship between the two parameters.
     In-stream TSS loading patterns appear to have followed precipitation patterns, (Figure
6-10) with little effect on BOD or VSS loadings. However, linear regression analysis of these
data indicated that there was no statistically significant linear correlation between TSS loading
and precipitation.  The correlation coefficient of the regression of TSS load (kg/d) against
                                       56

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precipitation (cm/month) was r2 0.17. Regression of TSS load against VSS load resulted
in an r2 value of 0.22. Thus, there was no significant linear relationship between TSS and
VSS or TSS and precipitation for the in-stream solids data.
     Although seasonal increases in precipitation appeared to result in small increases in
TSS, the relationship between the two was not statistically significant. Regression of VSS
load against precipitation resulted in an r2 value of 0.02. Thus, VSS loads did not respond
to precipitation. In addition, stream  flow exhibited no correlation with TSS load, r2= 0.01.
     The small increases in TSS loading during Spring and Fall (Figure 6-10) have been
attributed to inorganic material which washed off streets, culverts, and gulleys and into Smith
Creek upstream of the land treatment site  during these wet seasons.  The inorganic material
in the urban runoff would then combine with the dilute effluent from the treatment site, resulting
in small increases in TSS. However, because the release and in-stream dilution of  these
mass discharges may have  been quite variable, depending on a multitude of possible con-
ditions upstream and at the site, the correlation between the two was low.  Because  the
source  of the solids was  upstream  and the  sampling point was several kilometers
downstream, "cause and effect" type correlations were low.
     Runoff from the treatment slopes,  even during heavy storm events did not contain
significant quantities of TSS.  During  a storm event in May, 1989 over 2.5-cm of rain fell
within 12 hours. Samples of the slope runoff collected during this storm showed no increase
in either TSS or VSS.  End-of-slope runoff samples were collected from two slopes at the
site (W-5 line and B-13 line, Figure 4-2).  Runoff concentrations are listed in Table 6-3.
  TABLE 6-3. RUNOFF CONCENTRATIONS* DURING WET* AND DRY** CONDITIONS
Location
B-13
W-5
TSS !
3 (6)
10 (29)

3 (4)
5 (15)
              *  All values in units of mg/L
              *  Samples collected May 17,1989 during a storm of 2.5-cm of precipi-
                tation in 12-hr period.
             **  Values in parenthesis are samples collected April 18, 1989, no pre-
                cipitation within 72-hrs of sample collection, values within parentheses.
                                        57

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     The long-term data indicate that process performance, as measured by BODS, VSS
and TSS loads, remained relatively unaffected by preciptiation and seasonal variations.
SYSTEM MASS BALANCES
     Mass balances were made  around the Paris, Texas land  treatment utilizing the
upstream and downstream (Smith Creek) flow and concentration data; and raw waste flow
and concentration data supplied by  Campbell Soup.   For the 10-year period for which
comprehensive records existed, there were 36 individual days-of-record for which there
existed complete data sets (i.e., data set composed of: upstream and downstream flow rate
and concentrations, and raw waste flow rate and concentrations) required for the calculation
of mass balances.
     With the exception of the month of May, each month was represented by at least one
complete data set. The data, however, were collected on individual days and thus, may not
be representative  of monthly conditions.  Because  no  monthly or seasonal trends were
observed for either raw wastewater loading or in-stream loading in Smith Creek (see above
for discussion), the daily data were  used for the mass balance calculations.
     Since the actual land treatment site runoff was not measured, an assumption of the
applied wastewater that was discharged as runoff was needed. It has been shown that the
runoff percentage  at the Paris, Texas site varied seasonally, between 44 and 72  percent;
with 60% as the mean'101.  In addition, variation in application rate, wetted acreage and soil
properties could have also affected the runoff percentage. Therefore, it was assumed that
a value of 60% was a suitable estimate for the percentage of runoff flow. As a result, the
concentration values shown in Table 6-4 are not exact, but are estimates which provide an
approximation of the overall system performance.
     The calculated values are presented in Table 6-4, along with measured values (samples
collected from the  runoff collection ditches) reported  by Gilde(9).
                                       58

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     TABLE 6-4. MASS BALANCE RESULTS FOR THE PARIS, TEXAS OLF SITE
Parameters
Runoff concentration (mg/Ll
1977-1988 (calculated)'
1969 (measured?
Concentration change (%)
1977-19881
19694
Mass removed (%)'
1977-1988
1969
BOD,

6
9

98
99

99
99
COO

43
NA

96
NA

98
NA
TOC

15
23

95
NA

97
NA
TSS

32
16

93
94

94
98
T-N

2
3

89
84

96
92
  1     Mean values based on mass balance calculation results.
  *     Measured values reported by Glide"1.
  1     Mean values based on paired daily data: raw waste and runoff concentrations.
  4     Single values based on single values reported for raw waste and runoff concentrations'7'.
  '     Values based on loading rates calculated from flow and concentration data.
     The data in Table 6-4 indicated that mass removal and concentration change per-
centages for all parameters were generally in excess of 90-percent. These removals were
at the high end of efficiencies reported by Martel(13) for several other OLF land treatment
sites. Martel'13' reported removal efficiencies (concentration change) observed at 8 OLF
sites in the US: ammonia removal between 60 and 99%, TSS removal between 87 and 95%,
and BODS removal between 90 and 99%.
     The data from 1969 show excellent agreement with the estimated values from the
1977-1988 period.  Thus, it appears that process performance remained  relatively stable
and a high degree of efficiency was maintained over the entire 24-year life of the system.
CONCLUSIONS
     Seasonally heavy precipitation produced small  increases in  TSS mass discharges
within Smith Creek.  These increases, however, were well below regulatory mass loading
limitations and no statistically significant correlation (p  0.05) was found between the TSS
loading and precipitation. Since solids discharges from the OLF slopes were unaffected by
                                       59

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heavy precipitation, the small increases in TSS loading in Smith Creek may have been due
to upstream (off-site) sources.  Thus, the small increases in TSS mass discharges were
probably not due to the OLF system.
     The long-term operation and performance data collected at the Paris, Texas OLP land
treatment site indicated that the system consistently achieved a very high level of treatment,
from a surface discharge standpoint.  In-stream concentrations of BODS, COD, TOC and
TSS indicated that mean removals were greater than 93%. Total nitrogen removals were
between 84 and 89%.  Effluent mass discharges remained well within the regulatory lim-
itations for solids and BOO over the past 24 years. Percent removals (mass basis) for BOD5,
COD, TOC  and TSS were consistently high (>92%) over the 24-year life of the site.
                                      60

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                                  CHAPTER 7
                                     SOILS
INTRODUCTION
     The long-term application of wastewater can impact a variety of soil properties which
in turn can affect crop maintenance, quality, and site-life. These properties include soil
permeablity, cation exchange capacity, metal content, and organic carbon content.  The
following section describes the results of research conducted with soil samples collected
from the Paris, Texas site between 1987 and 1989. Samples were collected  at specific
wastewater application areas and at one location on-site which  had not been subjected to
wastewater application. The soil properties within this "control" area provided a comparative
measure for the evaluation of the long-term impacts of wastewater application on soils within
the treatment area. In addition, where appropriate data were available, direct comparisons
of soil properties were made between recently collected samples and previously published
results for the Paris, Texas site.
MATERIALS AND METHODS
Soil Core Sampling
     A total of 20, shallow depth (1.5-m) soil cores were collected from the three waste
application slopes and the control area (Figure 7-1), that is, 5 cores per collection area. The
number of core samples and the collection pattern was selected by UT and EPA researchers
to provide soil samples which were repesentative within the time and analytical constraints
of the project. Two, deeper soil cores (7.5-m and 5.5-m) were collected from the control area
and the G-4 area during the installation of groundwater monitoring wells. These two cores
extended from the ground surface to the confined aquifer.   Details of the installation,
development and sampling of the monitoring wells are given in Section 8.
                                       61

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                                                                                                                    Lake Crook
o>
IV)
                                                            BORING A    /Smith Creek
                                                                                                                 Creek Monitoring |

                                                                                                                         Station  !
G-4 line I        I w-5 Un


           SUMP/SCREENING BUILDING


             STORMWATER DISCHARGE
                              Campbell Soup Plant
                                                                    Legend:

                                                                       9       Groundwiter monitoring well.

                                                                               Soil boring
                                             scale

                                            meters
                     Figure 7-1. Location Map of Soil Sample Collection Areas

-------
     Soil core samples were collected with the aid of a Central Mining Equipment rotating
hollow stem auger (10-cm diameter). A core barrel sampler was used to recover undisturbed
core material. Five shallow cores were collected from randomly selected locations within
the spray pattern at each sample location (i.e., at G-4, Y-16, E-32, and at random from the
control area).
     After the drilling equipment was readied, the soil surface was lightly scraped to remove
any vegetation. A Kimwipe* was placed on the soil surface to identify the true top end of
the soil core after removal. The auger bit was lowered on the tissue and soil from the first
15-cm was cored and recovered. The auger bit and core recovery equipment are depicted
in Figure 7-2.
                   Cor* Retainer    Cor* Barr*l       Adaptor
                      - Hta*d T**th

Figure 7-2. Auger Bit and Core Recovery Device
     Cores recovered from 15-cm to 150-cm were pared to a diameter of approximately
6-cm. Samples recovered from the top 15-cm were not pared due to the loose, granular
structure of the soil.  Paring consisted of hydraulically extruding the core through a 6-cm
diameter circular  paring cone welded to stainless steel plate.   The paring  apparatus is
illustrated in Figure 7-2. The cores were placed in split 6.4-cm diameter PVC pipe.  The
cores were logged in the field by a geologist.
                                       63

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                                              D   (D
                                     Cor* Barrel    Extruding Block
                   A*ptlc
Hydr*uHc
Cyttndw
Figure 7-3. Core Extruding and Paring Apparatus
     Upon completion of the logging, cores were split in half with a stainless steel laboratory
spatula. Each complete core was divided into five sections, 0 to 15-cm, 15 to 30-cm, 30 to
61 cm, 61  to 107-cm, 107 to 152-cm. The selection of these intervals was based upon the
expectation that the greatest accumulations of contaminants would be near the surface and
therefore, the core sample intervals were smaller near the surface.  One-half of each split
section was placed in a glass mason jar, the mouths of which were covered with aluminum
foil and then sealed with screw caps. Jars were labelled according to sample location and
core section depth. Samples were packed on ice in the field, transported to UT-Austin and
stored at 4C until analyzed.
     Core samples were composited after arrival at UT-Austin.  The samples were mixed
by hand in a large porcelain bowl with a stainless steel spatula. For each study location (the
G-4, E-32, Y-16, and control areas), approximately 5 equal masses of soil from each depth
interval from each of the five cores were composited. The compositing process reduced
the number of samples  scheduled for analysis from 100 to a final total of 20. The original,
unmixed core samples were retained and stored at 4C. A flow diagram for the compositing
sequence  is given in Figure 7-4.
                                       64

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                   SAMPLE COLLECTION AREA
                 (i.e. G-4, E-32. Y-16 and CONTROL)
         I
rn
     FIVE INDIVIDUAL CORE SAMPLES (Each 1.5-m in length)
                 I	I	I	I
                          COMPOSITE CORE SAMPLE
^MM




0-1 5 c
15-30
30-60
61-107
107-15
Figure 7-4. Core Sample Compositing Sequence
RESULTS
    The composited core samples were subjected to a variety of analyses to aid in the
evaluation of the effects of long-term land treatment on soil characteristics.  The results of
these analyses are presented in this section.
Organic Carbon
    Composite soil core samples from the G-4, Y-16, E-32 and control areas (Figure 7-1)
were analyzed for organic carbon as described in Section 3. Each sample was analyzed in
duplicate. Mean values and standard deviations at five different depth intervals for each
sampling area were plotted (Figures 7-5 through 7-8).
                                65

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Depth, cm

       0-16


     16- 30


     30 - 61


     61 - 107


    107 - 162
                                                 fTANOAMO OCVIATOM -
             0      0.6       1        1.6       2       2.5
                           Soil Organic Carbon, %
Figure 7-5. Control Area Composite Core Samples: Percent Organic Carbon
Depth, cm
       o -
      16-30
      30-61
     61 - 107
    107 - 162
                                                      I
                                                 STANDARD OBVUTMN -
             0       0.6       1        1.6       2       2.6       3
                           Soil Organic Carbon, %
Figure 7-6. E-32 Spray Line Composite Core Samples: Percent Organic Carbon
                                    66

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Depth, cm

       0-15


      15 - 30


      30 -61


     61 - 107


    107 - 152
                                  STANDARD DEVIATION -
              0       0.5       1       1.5       2      2.5
                            Soil  Organic Carbon, %
Figure 7-7. Y-16 Spray Line Composite Core Samples: Percent Organic Carbon
Depth, cm
       0-16
      16 -30
      30-61
     61 - 107
    107 - 152

                                                  STANDARD DEVIATION -
                     0.5
                       1.5
2.5
                           Soil Organic Carbon, %
Figure 7-8. G-4 Spray Line Composite Core Samples: Percent Organic Carbon
                                    67

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     The organic carbon data were subjected to two way analysis of variance (ANOVA2) to
test hypotheses of equality of the means with respect to location and depth. The ANOVA2
results are valid for all locations and all depths, with a 11n 20 chance of error, at a 5% level
of significance.
     For the Paris, TX situation, identical depth intervals were used at all locations; and
thus, depth was considered a fixed variable. Because the sample collection locations were:
selected randomly from the hundreds of spray lines at the site, location was considered a
random variable. Thus, it was appropriate to test the significance of depth and location even
when interaction effects were significant.
     The organic carbon data were arranged in a matrix, grouped by location (the three
spray lines and the control area) and depth (five depth intervals). Each location/depth interval
contained three replicate analyses.  Where significant differences (at the 5% level of sig-
nificance) between the means were found to exist, the possible differences were examined
and identified. The Q-method(8)was used to examine the possibility of differences between
the means (as a function of depth, location or both). The results of the ANOVA2 and Q-method
testing are presented in Table 7-1.
TABLE 7-1. Q-METHOD TEST RESULTS FOR ORGANIC CARBON: LOCATION
Location
Mean, %
Control
0.27 a
G-4 Line
0.52 b
E-32 Line
0.71 c
Y-16 Line
1.00d
Depth, cm
Mean, %
Oto15
1.72 a
15 to 30
0.61 b
30 to 61
0.34 c
61 to 107
0.26 C
107 to 152
0.32 c
At a given location/depth, concentration values followed by the same letter are not
significantly different at the 5% level.
Location was significant at 5% level. *nF = 58.6, critical *WF = 3.10.
Depth was significant at 5% level, 4WF = 146, critical 4MF  2.87.
Interaction was significant at 5% level, "gJF * 19.79, critical KF <= 2.12.

     Recalling that at the time of sample collection the E-32 line had been in operation for
10-years and the  Y-16 and G-4 lines for 23-years data from these areas can be used to
                                        68

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assess the effect of the length of time (number of years) of application on soil properties.
The ANOVA2 and Q-method test results indicated that the organic carbon percentage was
significantly different at each location, with no two locations being statistically similar.  If it is
assumed that the initial soil organic carbon concentration at all three wastewater application
areas was roughly equivalent, and that the operation of the land treatment system resulted
in the addition of organic matter to the soil surface, it followed that the oldest application
areas would possess a greater amount of soil organic  carbon than the  more recently
developed  areas.  Although the soil in wastewater application areas showed a definite
increase in organic carbon content as a result of wastewater application, the distribution of
mean organic carbon content did not  follow the expected trend. The reason for this may be
due to differences in harvesting  practices at the locations over the years, variations in the
application rates at the different lines,  differences in the initial soil organic carbon percentage
prior to wastewater application,  or differences in soil texture or properties which serve to
retain the organic carbon on the  soil surface.
      The organic carbon percentage followed the trend of high values at the surface (0 to
15-cm and  15 to 30-cm) which decreased to a statistically uniform concentration after 30-cm
of depth. Assuming that that original organic carbon percentage at each location was near
or equal to  the value measured at the control area these results indicated that deposition of
organic matter at the site was variable with no apparent correlation between organic carbon
accumulation and time. Surface accumulations of organic carbon at the waste application
areas were significantly greater than  that measured at the control area.
pH and Cation Exchange Capacity
     Cation Exchange Capacity (CEC) and pH values for the composite soil core samples
were measured as described in  Chapter 3. CEC is normally expressed as the number of
milliequivalents of cations that can be exchanged in a sample with a dry mass of 100-g(6>.
                                        69

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     The measured pH and CEC values are tabulated in Table 7-2.
            TABLE 7-2. pH AND CEC VALUES: COMPOSITE SOIL CORES
Location
Depth, cm
0-15
15-30
30-61
61-107
107-152
Control
pH/CEC*
6.56/32
4.86/37
4.65/42
5.27/48
5.55/45
G-4
pH/CEC*
5.84/17
5.04/25
4.87/55
5.08/51
6.06/20
Y-16
pH / CEC*
5.67/51
5.85/53
5.50/55
6.56/66
6.80/61
E-32
pH/CEC*
5.65/59
5.11/65
6.10/57
6.64 / 49
7.16/56
            * CEC in units of meq/100-g of dry soil.
     The CEC data were tested by ANOVA2 and no significant difference (p  0.05) between
the means was found with respect to depth. However, there was a significant difference with
respect to location. The location data were tested using the Q-method(8) (Table 7-3).
TABLE 7-3. Q-METHOD TEST RESULTS FOR CEC: LOCATION
Location
Mean, mg/kg
Control
40.8 a
G-4 Line
33.6 a
E-32 Line
57.2 b
Y-16 Line
57.2 b
At a given location, concentration values followed by the same letter are not
significantly different at the 5% level.
Location was significant at 5% level, a,,F - 6.96, critical *,,F = 3.49.
     The CEC values were statistically uniform with depth at each location; however, the
mean values at lines E-32 and Y-16 were statistically different from those at the control area
and the G-4 line. The CEC value represents the ultimate ability of the soil clay mineral fraction
to replace cation  adsorbed on the surface with cations in the  surrounding soil solution.
Because the CEC test is a measure of the ultimate, theoretical exchange ability of the clay
and not the in-situ exchange capacity remaining after equilibration with soil pore water, no
valid comparisons can be made between CEC and length of time of site usage.
                                       70

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     The principal utility of CEC data is as an aid in the evaluation of the potential for cation
accumulation and/or migration through soil. The application of CEC data to this end is
described later in this Chapter.
     Generally, it is unacceptable to calculate mean pH values based on the hydrogen ion
concentration. Averaging the non-conservative quantity [H*] yields erroneously low mean
pH values.114' Because of this, statistical evaluation of the pH data was not performed.  On
a qualitative basis, however, inspection of the pH data indicated that the  soil pH  range
extended from acidic to neutral (4.65 to  7.16), with the distribution skewed to the  acidic
condition. An examination of the relation between soil solution pH and soil metal retardation
capacity is presented later in this Chapter.
Total Metals
     The composite core samples were analyzed in triplicate for the total metals noted in
Table 7-4. Based on the characteristics of the  applied wastewater and typical soils,  it was
anticipated that these 24 metals would be present in trace or greater concentrations in the
soil. Of the 24 metals analyzed for, the data from zinc, chromium, nickel, potassium,  mag-
nesium, sodium, and calcium were subjected to further examination and statistical analysis.
These seven metals were selected because of their  presence  and relative magnitude of
concentrations in both the raw wastewater and soil.  Samples from each location and depth
were analyzed in triplicate, mean concentrations and standard deviation values are provided
in Table 7-5.
             TABLE 7-4. METALS EXAMINED IN SOIL CORE SAMPLES
Magnesium
Iron
Manganese
Lead
Nickel
Arsenic
Selenium
Cadmium
Sodium
Potassium
Cobalt
Lithium
Molybdenum
Barium
Boron
Titanium
Beryllium
Copper
Strontium
Aluminum
Vanadium
Calcium
Chromium
Zinc
                                       71

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TABLE 7-5. SOIL METAL CONCENTRATIONS: MEANS AND STANDARD DEVIATIONS
Depth interval
Oto 15-cm
15to30-cm
30 to 61 -cm
61 to 107-cm
107to152-cm
Total calcium concentration In soil, mg/kg dry weight*
Control
4,220  489
3,027 477
10,800**
30,36719,717
32,333 18,939
G-4 line
1,357 97
1,680 291
2,967 266
5,557 1,521
4,825  530
E-32 line
6,390 1,1 61
6,380 347
6,483  765
16,467 1,955
12,533 666
Y-16 line
4,280 2,81 8
4,625  601
4,970  252
8,333 843
6,960 3,1 68
Depth Interval
Oto 15-cm
15to30-cm
30 to 61 -cm
61 to 107-cm
107to152-cm
Total chromium concentration In soil, mg/kg dry weight* 
Control
21 9
25 2
17**
22 13
173
G-4 line
20 5
28 7
29 2
29 6
38 10
E-32 line
21 2
24 7
23 7
173
19 1
Y-16llne
26 2
303
21 10
21 5
2911
Depth Interval
Oto 15-cm
15to30-cm
30 to 61 -cm
61 to 107-cm
107to152-cm
Total magnesium concentration in soil, mg/kg dry weight*
Control
1,071 257
1,597 192
1,760+*
2,067 290
2,327 283
G-4 line
423 34
1,350 31 6
2,1 26 120
2,487 380
3,470 721
E-32 line
2,440 337
3,273 186
3,250  690
2,913 301
3,1 60 283
Y-16llne
2,430 1,050
2,388  325
1,473 403
2,047 404
2,235 955
    Notes are explained at the end of the table.
                                 72

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                         TABLE7-5. (Continued)
Depth Interval
Oto 15-cm
15to30-cm
30 to 61 -cm
61 to 107-cm
107to152-cm
Total nickel concentration In soil, mg/kg dry weight* 1 i
Control
113
11 2
25**
12 5
92
G-4 line
82
104
145
19 2
336
E-32llne
25 5
30 2
36 12
24 2
22 1
Y-16 line 1
187
162
21 3
175
22 + 0
Depth Interval
Oto 15-cm
15to30-cm
30 to 61 -cm
61 to 107-cm
107to152-cm
Total potassium concentration In soil, mg/kg dry weight! I
Control
608 44
768 167
558**
719 173
920  52
G-4;llne-t?^;
454 23
1,111 611
987 186
1,082 267
2,000 863
E-32llne
1,687 336
2,243  609
2,067 887
1,830 251
1,970 697
Y-16 line
1,650 660
1,085 78
588 43
875  255
1,066 246
Depth Interval
Oto 15-cm
15to30-cm
30 to 61 -cm
61 to 107-cm
107to152-cm
Total sodium concentration in soli, mg/kg dry weight* i
Control
267 122
479 142
1,140**
2,573 61 2
3,1 57 759
G-4 line
138  53
456 150
1,122 223
1,417 196
1,645 770
E-32 line
518 147
578 447
1,184 258
1,277 334
1,31 4 424
Y-16 line
670  384
526 139
795 127
991  205
782 171
Notes are explained at the end of the table.
                                   73

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                               TABLE 7-5.  (Continued)
Depth Interval
Oto15-cm
15 to 30-cm
30 to 61 -cm
61 to 107-cm
107to152-cm
Total zinc concentration In soil, mg/kg dry weight*
Control
38 14
29 5
25**
31 8
29 3
G-4 line
574
29 7
41 9
387
674
E-32 line
67 22
564
62  14
77 + 24
633
Y-16 line
74 21
350
41 16
355
585
 *  Each composite soil sample analyzed in triplicate.
 **  Replicate samples (extracts) lost, single sample analyzed from control area at this depth
     The soil concentration data for these metals were subjected to ANOVA2 testing. The
testing indicated that, for all seven metals, with the exceptions of potassium and chromium
over depth, there was a statistically significant difference between the means with respect
to both depth and location.  The data were further analyzed by the Q-method(8) and the results
for each metal are given in Table 7-6.
TABLE 7-6. Q-METHOD TEST RESULTS FOR POTASSIUM
Location
Mean, mg/kg
Control
715 a
G-4 Line
1,127 b
E-32 Line
1,126b
Y-16Llne
1,489b
Depth, cm
Mean, mg/kg
Oto15
1,100 a
15 to 30
1,302 a
30 to 61
1,050 a
61 to 107
1,126 a
107 to 152
1,489 a
At a given location/depth concentration values followed by the same letter are not
significantly different at the 5% level.
Location was significant at 5% level, JoF => 25.7, critical '^F = 2.84.
Depth was not significant at 5% level, 4F = 2.41, critical 4MF = 2.61.
Interaction was significant at 5% level, 1IMF = 2.42, critical "MF = 2.00.
     The results indicated that potassium soil concentrations were similar in all three waste
application areas; however, the mean concentrations were different (higher) than those found
                                          74

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at the control area.  The  soil potassium levels  in the application areas indicated that
wastewater application resulted in an increase in potassium in the soil. However, the increase
did not appear to be dependent upon the cumulative length of time the spray lines were
operational. Potassium concentrations were uniform with depth.
TABLE 7-7. Q-METHOD TEST RESULTS FOR CALCIUM
Location
Mean, mg/kg
Control
16,1498
G-4 Line
3,277 b
E-32 Line
9,651 c d
Y-16Llne
5,834 b d
Depth, cm
Mean, mg/kg
OtolS
4,062 a
15 to 30
3,928 a
30 to 61
6,305 a
61 to 107
15.181 b
10710152
14,163 b
At a given location/depth, concentration values followed by the same letter are not
significantly different at the 5% level.
Location was significant at 5% level, '^F - 19.7, critical JWF - 2.84.
Depth was significant at 5% level, 4MF - 15.3, critical 4MF = 2.61.
Interaction was significant at 5% level, <2MF = 4.53, critical I2F = 2.00.
     The calcium data (Table 7-7) indicated that calcium concentrations were lower at the
application areas than the control area. With respect to time, the mean soil calcium con-
centration values were lower at the older areas than at the younger area (and the control).
Calcium  concentration increased with  depth at all locations.  These data indicated that
leaching of calcium from the top 1.5-m of soil occurred at the wastewater application areas,
and the leaching was apparently time dependent. That is, 23-years of wastewater application
resulted  in more calcium leached than the amount leached in 10-years. A possible mech-
anism for the apparent leaching is discussed in Chapter 9.
     Mean soil concentration values of calcium at the 4 study locations were plotted (Figure
7-9) to illustrate the leaching trend with  respect to the unleached soil at the control area.
                                         75

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    Depth, em
          0-16
         15-30 -
         30-81
        61-107 -
       107-162 -
     E-32 LINE
     Y- LINE
     0-4 LINE
-B-  CONTROL
                 ''/////////////7/////S//A
                               10            20            30
                         Mean Soil Concentration, mg/kg (1,000'a)
Rgure 7-9. Leaching of Calcium From Soil In Wastewater Application Areas
TABLE 7-8. Q-METHOD TEST RESULTS FOR MAGNESIUM
Location
Mean, mg/kg
Control
1,7648
G-4Llne
1,971 a
E-32Une
2,981 b
Y-16Une
2,113 a
Depth, cm
Mean, mg/kg
OtolS
1,591 a
15 to 30
2,150 b
30 to 61
2,153 b
61 to 107
2,378 be
107 to 152
2,765 C
At a given location/depth, concentration values followed by the same tetter an not
significantly different at the 5% level.
Location was significant at 5% level, aF  25.2. critical 'F - 2.84.
Depth was significant at 5% level. 4MP -12.8. critical *JF . 2.61.
Interaction was significant at 5% level. Vs 6.44. critical nJF  2.00.
                                        76

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     Mean magnesium values did not vary significantly by location, with the exception of
the higher values at the E-32 line. Mean magnesium concentration values increased with
depth at all locations.
TABLE 7-9. Q-METHOD TEST RESULTS FOR SODIUM
Location
Mean, mg/kg
Control
1,523 a
G-4 Line
956 b
E-32 Line
1,026b
Y-16Llne
789 b
Depth, cm
Mean, mg/kg
Oto15
3998
15 to 30
588 a
30 to 61
1,060b
61 to 107
1.539C
107 tO 152
1,7830
At a given location/depth, concentration values followed by the same letter are not
significantly different at the 5% level.
Location was significant at 5% level, ]MF = 14.0, critical 9MF = 2.64.
Depth was significant at 5% level, 4WF = 39.7, critical 44(IF = 2.61.
Interaction was significant at 5% level, "MF = 7.42, critical 12F > 2.00.
     Mean sodium concentrations were similar in all three waste application areas, but less
than that at the control area. The sodium concentrations increased gradually with depth at
all four locations. Although the sodium values at the wastewater application areas were less
than those at the control area, there was no statistical difference between wastewater
application areas, regardless of cumulative time of usage. These data indicate that leaching
of sodium from the top 1.5-m of soil occurred in all three wastewater application areas. Mean
values of soil sodium concentration have been plotted (Figure 7-10) to illustrate the leaching
trend.
                                         77

-------
  Depth, cm
         0-16 -
        16-30 -
        30-61
       61-107 -
      107-162  -
               0            1.000          2,000         3,000
                             Mean Soil Concentration (mg/kg)

Figure 7-10.  Leaching of Sodium From Soil in Wastewater Application Areas
4,000
TABLE 7-10. Q-METHOD TEST RESULTS FOR ZINC
Location
Mean, mg/kg
Control
30 a
G-4 Line
47 b
E-32 Line
65 c
Y-1 6 Line
48bd
Depth, cm
Mean, mg/kg
01015
59 a c
15 to 30
37 b
30 to 61
43 b
61 to 107
45 be
107 to 152
54 C
At a given location/depth, concentration values followed by the same tetter are not
significantly different at the 5% level.
Location was significant at 5% level, **F - 24.5, critical ',F - 2.84.
Depth was significant at 5% level, 4MF - 7.61, critical V - 2.61.
Interaction was significant at 5% level, "F - 2.42, critical "F - 2.00.
                                         78

-------
     The geatest mean zinc values were found at the youngest application area, contrary
to the predicted trend, but similar to that observed for magnesium. Mean zinc concentrations
at all wastewater application areas, however, were greater than those at the control area.
These data indicate that wastewater application resulted in accumulation of zinc throughout
the soil profile.  The data also indicate that, for the 5 depths examined, zinc concentrations
were greatest at the surface and the lowest (107 to 152-cm) depth.
TABLE 7-11. Q-METHOD TEST RESULTS FOR NICKEL
Location
Mean, mg/kg
Control
I4a
G-4 Line
I7ab
E-32 Line
27 c
Y-16 Line
19 b
Depth, cm
Mean, mg/kg
Oto15
I6a
15 to 30
I7a
30 to 61
24 c
61 to 107
18ab
107 to 152
21 be
At a given location/depth, concentration values followed by the same letter are not
significantly different at the 5% level.
Location was significant at 5% level, JF = 30.7, critical 3MF = 2.84.
Depth was significant at 5% level. 4MF = 8.66, critical 4MF - 2.61.
Interaction was significant at 5% level, "^F = 7.52, critical "^F = 2.00.

     Nickel concentrations at the Y-16 and E-32 areas were greater than those at the control
area.  The greatest nickel concentrations were at the E-32 line contrary to the predicted
time-dependent trend, but, similar to that observed for zinc and magnesium.
                                         79

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TABLE 7-12. Q-METHOD TEST RESULTS FOR CHROMIUM
Location
Mean, rag/kg
Control
21 a
G-4 Line
29 b
E-32 Line
21 a
Y-16 Line
25 a b
Depth, cm
Mean, mg/kg
Oto15
22 a
15 to 30
27 a
30 to 61
23 a
61 to 107
22 a
107 to 152
26 a
At a given location/depth, concentration values followed by the same letter are not
significantly different at the 5% level.
Location was significant at 5% level, aMF = 6.95, critical 'WF = 2.84.
Depth was not significant at 5% level, *MF -  1.79. critical 4MF = 2.61.
Interaction was not significant at 5% level, 12MF = 1.64. critical '^F = 2.00.
     Chromium concentrations did not vary with depth. Mean chromium values were greatest
at the G-4 and Y-16 lines; however, only the chromium concentrations at the G-4 line were
statistically different from the control.
Water Soluble Anlons
     Water soluble extract anion concentrations of chloride and sulf ate were measured. The
laboratory-measured ion concentrations were less than those existing in the soil due to the
dilution of the concentration by the extracting solution. In order to estimate the concentration
of each chemical species existing in the soil, c,, at the time of sample collection, the measured
concentration, cm, was multiplied by the  inverse of the dilution factor as follows:
                                                                               (7-1)

W^ is the weight of the extracting solution and Ww is the weight of the water in the soil at the
time of collection. The concentration, c,, represents the total concentration of the chemical
species in the soil assuming the extraction solution is 100 percent efficient and complexation
and precipitation of the dissolved species does not occur115'.
                                         80

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     Pore water concentrations were calculated using the water soluble extract data col-
lected for sulfate and chloride. The calculated values are presented below (Table 7-13).
     TABLE 7-13.  CHLORIDE AND SULFATE PORE WATER CONCENTRATIONS*
Depth, cm
0-15
15-30
30-61
61 -107
107-152
Control
65
(10,962)
65
(8,381)
300
(24,242)
1,059
(26,428)
1,531
(26,059)
G-4
590
(2,660)
275
(2,543)
278
(1.494)
1,481
(11,778)
704
(3,500)
E-32
115
(911) .
166
(775)
330
(11,325)
398
(13,248)
426
(10,124)
Y-16
295
(1,526)
300
(832)
588
(1,393)
604
(8,935)
700
(6,395)
            +    Concentration in units of mg/L Chloride values
                 followed by sulfate values in parenthesis.

     The data for each ion were subjected to ANOVA2 analysis with respect to depth and

location. The Q-test results are given in Tables 7-14 and 7-15.


TABLE 7-14. Q-METHOD TEST RESULTS FOR SULFATE
Location
Mean, mg/L
Control
19,214 a
G-4 Line
4,395 b
E-32 Line
7,277 b
Y-16 Line
3,81 7 b
Depth, cm
Mean, mg/L
Oto15
4,015 a
15 to 30
3,133 a
30 to 61
9,61 5 b
61 to 107
15,097 b
107 to 152
11,519b
At a given location/depth, concentration values followed by the same letter are not
significantly different at the 5% level.
Location was significant at 5% level, 1I2F = 18.8, critical J12F = 3.49.
Depth was significant at 5% level, 418F = 7.47, critical *if = 3.26.
                                        81

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TABLE 7-15. Q-METHOD TEST RESULTS FOR CHLORIDE
Location
Mean, mg/L
Control
604 a
G-4 Line
666 a
E-32 Line
287 a
Y-16 Line
497 a
Depth, cm
Mean, mg/L
Oto15
266 a
15 to 30
202 a
30 to 61
374 a
61 to 107
885 b
107 to 152
840 b
At a given location/depth, concentration values followed by the same letter are not
significantly different at the 5% level.
Location was not significant at 5% level, 3,aF . 1.34, critical J12F  3.49.
Depth was significant at 5% level. *,2F - 4.09. critical 4,,F - 3.26..
     Calculated mean suit ate pore water concentrations at the three waste application areas
were statistically similar; however, they were substantially less than the mean value at the
control area. Thus, although leaching appears to have occured, the process was apparently
not a direct function of cumulative time of leaching. The results indicate that leaching of
sulfate from the top 1.5-m of soil in the wastewater application areas has occurred. The
leaching trend is illustrated in Figure 7-11, mean values of sulfate were plotted.  Mean sulfate
concentrations increased gradually with depth at all locations.
     The ANOVA2 and Q-test indicated that mean calculated pore water chloride con-
centrations, with respect to location, were  not  statistically different.  However, chloride
concentrations exhibited the trend of increasing with depth at all locations.
                                         82

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  Dpth, cm

        0-16

       16-30  -

       30-61

       61-107

      107-162
Y////////////////////A
'///////////////////A
                 	1	1	1	1	1	
              0        6        10       16       20       26       SO
                       Pore Wfctor Concentration mg/L (tOOO's)
Figure 7-11. Leaching of Sulfate From Soil in Wastewater Application Areas
SUMMARY
     The results of the statistical analyses presented in the proceeding section have been
summarized in Table 7-15 to highlight the major points.
        TABLE 7-16. STATISTICAL SUMMARY OF SOIL CHARACTERISTICS
Soil
Component
%OC
Potassium
Calcium
Magnesium
Sodium
Zinc
Nickel
Chromium
Sulfate
Chloride
Was Accumulation
Significant? ?; :?:
YES, an lines
YES. an lines
NO
YES. E-32 only
NO
YES. an lines
YES, ad lines
NO
NO
NO
Was Accumulation
KTlme Dependent?
NO
NO
N/A
NO
N/A
NO
NO
N/A
N/A
N/A
Was Leaching
Significant?
NO
NO
YES. al ines
NO
YES, aJ lines
POSSIBLY
POSSIBLY
NO
YES. alines
POSSIBLY
WasLMOhlng
Tim* Dependent?
N/A
N/A
YES
N/A
NO
N/A
N/A
N/A
NO
NO
          N/A  Not applicable.
                                    63

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SOIL METAL RETENTION CORRELATIONS
     Mean values from alt locations and all depths for soil properties and ion concentrations
at the wastewater application areas and the control area were tested for correlation through
linear regression analysis.  A total of 15 data points per variable (i.e., CEC, pH, organic
carbon fraction, and soil zinc, nickel and chromium concentration) were used in the correlation
analysis. The correlation analysis was performed to aid in the assessment of the ability of
soil at the OLF site to immobilize cations.
     The correlation coefficient, r, was calculated and ANOVA was performed for the linear
regression of Yon X, where /represents the dependent variable (soil metal concentration)
and X represents the independent variable  (either %OC, pH, or CEC). The independent
variables were selected for the regression analysis because they are often used(16>(17> as an
indicator of the ability of a soil to immobilize metals.   The one-way ANOVA test of the
regression  analysis provided a quantitative means of assessing the significance of the
regression. F-statistic values were calculated and evaluated at the 5% level  of significance.
Correlation coefficient values, r, were calculated to determine the direction of the slope of
the regression line; i.e., positive r  (slope) values indicated that Xand /increased together,
negative values indicated that increases in X resulted in decreases in Y.
     USEPA guidance documents"6"171 recommend soil pH and CEC as relative measures
of the potential for the retention of metals of major concern (Pb, Zn, Cu, Ni, Cd) on agricultural
land. The guidelines are rough estimates and are not suitable for all metals. For example,
EPA recommends that soil pH be maintained at 6.5 or greater to minimize metal solubilities.
Soil pH, however, may vary significantly with depth at a given location, making uniform
predictions impossible.  This situation was present at the Paris, TX site (Table 7-2), where
pH was found to vary between acidic (pH=5) to neutral (pH=7).  Also, pH can change dra-
matically due to acidification resulting from increased nitrification and stimulation of naturally
occurring organic acids. Based on the characteristics of the applied wastewater and the
                                       84

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expected chemical and biological transforamtions which are expected to take place at an
OLF site, increased acidification may occur at the soil surface and at greater depths.  In
addition, the solubility of many metal complexes can increase at pH values greater than 6.5.
     Of the 7 metals studied in detail, 3 metals (zinc, chromium, and nickel) were selected
for the regression analyses. These heavy metals were selected because their presence is
often a concern at land treatment sites and their retention by soil has been reported1181'171 to
be affected by the independent variables described above. The results of the linear regression
and ANOVA testing are given in fable 7-17.
          TABLE 7-17.  SOIL METAL CORRELATION: LINEAR REGRESSION*
                        AND ANOVA RESULTS
Dependent
Variable*
Zinc

Nickel

Chromium

Independent
Variable
PH*
%OC
CEC"
PH*
%oc
CEC"
PH*
%OC
CEC**
Correlation
Coefficient, r
- 0.456
+ 0.304
- 0.023
-0.167
-0.196
+ 0.298
+ 0.048
- 0.085
- 0.402
Regression
F-statlstlc**
3.42
1.33
0.01
0.37
0.52
1.27
0.03
0.10
2.50
Was Regression
Significant? ;
NO
NO
NO
NO
NO
NO
NO
NO
NO
        *  Data from all three wastewater application areas and all depths
          were used in the regression analysis.
        '  Soil metal concentration value in units of mg/kg.
       "  Critical 1,,F = 4.67.
        *  Hydrogen ion concentration, mole/L used. i.e.. antilog of negative pH value.
       **  CEC in units of meq per 100-g dry soil.
     Several authors'181'191 have shown CEC and pH as  unlikely to be reliable guides for
predicting heavy metal mobility in heterogeneous soils.  The data in Table 7-17 indicate that
f orchromium, nickel and zinc, there was no significant linear correlation between the variables
listed. In addition, the slopes of the regression lines exhibited no trends and appeared to be
random. The lack of correlation may indicate that existing guidelines for metal immobilization
                                        85

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are invalid; however, the relatively low soil metal concentrations, small concentration dif-
ferences between locations (no order of magnitude differences), variability of the data with
depth, the metal complex present, as well as effects due to analytical variation all have an
affect on the resolution of the linear regression.
     Thus, the data appearto support the assertion'18"19' that pH and CEC (as well as organic
carbon content) may not be reliable indicators of the ability of the soil to immobilize metals.
These results, however, are valid only for the concentration ranges found at the site.
METAL ACCUMULATION AND ITS EFFECT ON SITE LIFE
     It appears that the long-term metal loading rates (Table 5-4) resulted in the accumulation
of potassium, magnesium, zinc, and nickel in the soil at the wastewater application areas.
The location (site age) specific metals data, however, did not exhibit accumulation trends
which would suggest dependence upon the cumulative time of operation, pH, percent organic
carbon,  or cation exchange capacity.  Because of the apparent random pattern of accu-
mulation, metal accumulation predictions were not location specific and could have  been
applied to the entire site area.
     Although accumulation occurred, the resulting concentrations of zinc and nickel were
well below action levels recommended by U.S.EPA(16>(17). In general, zinc and nickel will be
toxic to crops before their concentration in plant tissues reaches a level that poses a problem
to forage animals or  human health.  Although this guideline is useful, calculation of the
expected site life provided a meaningful value. The calculations were based upon estimates
of long-term metal (Zn and Ni) loading rate ranges, present wetted acreage, EPA recom-
mended cumulative limits'16"171, and the most conservative assumption that 100% of the
applied metals were retained by the soil. Because potassium and magnesium accumulations
do not represent a potential land management concern, these elements were not considered
in the calculation of site life.
     The assumptions made for the calculation of soil metal accumulation rates are  pres-
ented in Table 7-18. The reasoning or data sources used to make the assumptions also are
provided (see Comments column Table 7-18).
                                       86

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        TABLE 7-18.  ASSUMPTIONS USED FOR THE CALCULATION
                    OF METAL ACCUMULATION
Variable
Operating period
Wetted Acreage
Initial Soil Metal
Concentration
Soil Density
Wastewater
Application Rate
Applied Wastewater
Metal
Concentration
Mean Applied Metal
Load and Standard
Deviation, kg/d
Depth of Metal
Accumulation In
the Soil Profile
Percentage Retained
EPA Recommended'16"17*
Soil Metal Limits
Assumption
350 days/year
364 hectare
Zinc: 65mg/kg
Nickel: 27 mg/kg
2.00 g/cm3
16,100 m3/d
Zinc: 0.17mg/L
Nickel: 0.01 mg/L
Zn: 3.0  2.0 kg/d
Ni: 0.2  0.2 kg/d
Top15-cm
100%
Zinc: 1,1 20 kg/ha
Nickel: 560 kg/ha
Comments
2 week shutdown/year.
1989 site size.
Maximum mean values
from field data.
Estimated value.
Based on long-term
data in Table 5-2.
Zinc value from
Table 5-2. Nickel
value estimated.
Zinc values from
Table 5-4. Nickel
values estimated.
Assuming that most
accumulation occurs
at the surface.
Most conservative case
Assuming pH > 6.5 and
CEC>15meq/100-g.
     The results of the metal accumulation calculations are presented in Table  7-19.
Although metal accumulation occurred and may be expected to continue, at current metal
loading rates, the accumulation of zinc and nickel will not affect site life. These results are
valid for mean loading estimates plus and minus one standard deviation.
                                     87

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              TABLE 7-19. CALCULATION OF METAL ACCUMULATION
                          AND SITE LIFE EXPECTANCY
Results
Initial Soil
Metal Load, 1987
Corrected Soil Metal
Limits*
Site Life Expectancy:
Mean Value
Low Value
High Value
Zinc
200 kg/ha
920 kg/ha

320 years
1,000 years
190 years
Nickel
85 kg/ha
475 kg/ha

2,470 years
indefinite
1 ,240 years
            *   Corrected limit value = [EPA recommended value] - [initial metal load].
CONCLUSIONS
     Several statistically significant trends were discerned for the total metal soil concen-
tration data and the calculated pore water concentrations.  With respect to the control area,
accumulation of organic carbon, potassium, magnesium, zinc, and nickel in the soil at the
wastewater application areas was evident, as well as leaching of calcium, sodium, and sulfate
and possibly chloride, zinc, and nickel. Neither accumulation nor leaching of chromium was
evident.
     Although  the accumulation of zinc and nickel was evident, the accumulation was so
small that several hundred years of continued site use may be expected at present loading
rates before the cumulative zinc and nickel soil concentrations would approach action levels
recommended by EPA for agricultural lands.
                                      68

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                                 CHAPTER 8
                              HYDROGEOLOGY
INTRODUCTION
     A comprehensive review of the literature related to the hydrogeology of north-central
Texas, which includes Lamar County in which Paris, Texas is located, was made.  The
geologic information was utilized  during the assessment of the potential for groundwater
occurrence at the Paris, Texas site.
     The data in the literature indicated that the probability of groundwater existing in
recoverable quantities at the Campbell's site was very low. A number of deep borings,
however, were made, both on- and off-site to assess the actual conditions at the site. Three
groundwater monitoring wells were installed and sampled approximately quarterly between
1987 and 1989.
      A complete description of regional hydrogeology and the results of the groundwater
sampling program are provided in this chapter.
GENERAL GEOLOGY
Geologic History
     The present structural attitude and stratigraphic succession of geologic formations in
north-central Texas resulted from a a sequence of events in geologic time. A continuing
cycle of advance and  retreat of ancient seas resulted in periods of sediment accumulation
alternating with periods of erosion. Subsequent structural deformation altered the attitude
of the strata. Nonmarine deposition of sediment by streams and other water bodies completed
the depositional sequence.  An index map of major structural features of the East Texas
basin is provided in Figure 8-1.
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                         Oklahoma
                                                           Arkansas
Figure 8-1. Index Map of Major Structural Features of the East Texas Basin
Paleozoic
     During most of the Paleozic era, a sedimentary basin existed throughout much of central
and north-central Texas which received sediments that resulted in the formation of sandstone,
limestone, and carbonaceous shales.  Sediments were deposited in this basin until late
Pennsylvanian time when the Llano Uplift and the Ouachita Fold Belt (Figure 8-1) caused a
regional tilting to the west and faulting in the immediate uplift area.  During Permian time,
the basin shifted to the west and only the northwest corner continued to receive sediments.
The rest of the basin (inclusive of Lamar County) underwent extensive erosion120'.
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Cretaceous
     During the Triassic and Jurassic Periods of the early Mesozoic era, withdrawal of the
seas from the north-central Texas area along with subsidence in the Gulf Coast embayment
led to a reversal of drainage direction.  By the close of Jurassic time, Paleozoic rocks had
been  reduced to an almost flat-featureless  plain upon  which  marine sediments were
deposited along an oscillating shoreline during the Cretaceous period.
     Two major invasions of the seas during the Cretaceous period are represented by the
Comanche and Gulf Series (rocks formed during the Cretacous period). During late Creta-
ceous (Gulf Series), a general uplift occurred to the west and the seas withdrew gulfward
covering only the eastern portion north-central Texas'20'.
Tertiary and Quaternary
     At the close of the Cretaceous period, noted by uplifting to the west and subsidence
of the coastal area, sediments of the Tertiary and Quaternary age were deposited. The
repeated transgression and regression of the sea resulted in  an  alternating sequence of
marine and continental deposits.  Throughout Tertiary time, except for minor periods of
subsidence, the land surface was eroded and modified by streams.  During Quaternary time,
the streams deposited alluvial sediments. The older sediments are represented by terrace
deposits above the alluvial valleys of present streams'201.
Stratigraphy
     Stratigraphic units that  supply fresh to slightly saline water  to wells in north-central
Texas range from Paleozoic  to Recent. However, the most important water bearing for-
mations are of Cretaceous age. The Stratigraphic units of North-Central Texas are listed in
Table 8-1.
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TABLE 8-1. STRATIGRAPHIC UNITS AND GEOLOGIC TIME SCALE
En

Cenoioic
MMOIOiC
Paleozoic
SyiMm




Cretaceous

Series
Recent
Pleistocene
Eocene
Palaocene
Gulf
Comanche

Group


WilCOX
Midway


Taylor
Auitin
Eagle Ford
Woodbine
Wathita
Fredericksburg
Trinity

Stratigraphic uniti
Alluvium
Fluviatile terrace deposit!


Kemp Clay
Corsicana Mart
Naeatoch Sand
Merlbrook Marl
Pecan Gap Chalk
Wolfe City  Ozan Formations
Gober Chalk
8 rownttown Marl 
8 lowom Sand
Bonham Formation


Grayton Marl  Mainttreet Limettone
Pawpaw Formation - Weno Limeitone
Fort Worth  Duck Creek
Kiamichi Formation
Edwardt Limestone
Comanche Peak Formation
Walnut Formation
Oenton Clay
Goodland
Limestone

 Paluxy Formation
Forme^n ^ G'-n Rose Forme.lon
' Twin Mountains Formation
1
Paleoioic rocks undifferentieted
                       92

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     The Cretaceous System is composed of two series, Gulf and Comanche, and each is
divided into groups. The Gulf Series is divided into the following five groups: Navarro, Taylor,
Austin, Eagle Ford, and Woodbine. The Comanche Series is divided into the following three
groups: Washita, Fredericksburg, and Trinity.
     The Taylor, Austin, and  Eagle Ford  groups outcrop in Lamar County (Figure 8-2,
Geologic Outcrop Map: North-Central Texas).- The Austin and Eagle Ford groups were of
particular interest to this study because groundwater monitoring wells at the Paris, Texas
site were completed within them. Stratigraphic units within the Austin formation which outcrop
at the Paris, Texas site include the Blossom Sand and the Bonham Formation.
     Eagle Ford rocks unconformably overlie (evidenced by the  break  in the normal
depositional sequence) the Woodbine strata along the margins of the East Texas basin. The
Eagle Ford Group is overlain by the Austin Group in all portions of the basin. Throughout
the basin, this contact is believed to be unconformable(21>.
Lltholopv and Groundwater Potential
Blossom Sand Formation  Austin Group
     The Blossom Sand of the Austin Group crops out in central Fannin, Lamar, and Red
River Counties in north-central Texas. The strike (bedding plane as it intersects the horizontal)
of the outcrop is east-west. The dip (the angle that a planar feature makes with the horizontal)
of the Blossom Sand is to the south averaging about 16.1 m/km.
     The Blossom Sand consists of a brown to light gray, unconsolidated, calcareous, fer-
ruginous, glauconite fine to medium quartz sand interbedded with sandy clay  and chalky
marl.  Most of the formation contains impermeable sandy clay or marl and chalk, with only
about 25 percent sand.
     The Blossom thickens southward downdip and eastward along the strike. Thickness
varies from 6 to 76-m thinning westward.   Individual beds, for the most part extend over
several square kilometers.
                                       93

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                           10
                 kltOITMtWS
                                     CRETACEOUS
        Alluvium
r*^^  Navarre Group
I/   /I  Taylor Group
PS^ ^H  Austin Group
\ff  /A  Eagle Ford Group
^1  Woodbine Group
Figure 8-2. Geologic Outcrop Map: North-Central Texas
                                        94

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     The principal source of recharge to the Blossom Sand is precipitation on the outcrop.
The outcrop ranges in width from about 2.5-km near its western end in central Fannin County
to about 10-km in central Red River County.  Much of the outcrop in Red River County is
covered by a mantle of thin high-level terrace deposits, which in places forms an excellent
recharge facility for the Blossom Sand1221.
     Water moves southward in the Blossom Sand from the recharge areas:on4he outcrop
to points of discharge.  The rate of movement is not known, but is expected to be very slow.
Water is discharged from the Blossom by pumping from wells and by natural means, such
as seepage into other formations in the subsurface, especially along the Luling-Mexia-Talco
fault system (Figure 8-1).
     The occurrence of useable quality water in the Blossom Sand is generally limited to
the  Red River basin and the northern part of the Sulfur  River basin  (Figure 8-3, Map of
Aquifers in North-Central Texas).  In general, groundwater from the Blossom Sand is fairly
high in dissolved solids content (100 to 3,000 mg/L), high in sodium bicarbonate,  and is
soft*20'.
Bonham Formation -  Austin Group
     The Bonham Formation of the Austin Group outcrops in central Fannin,  Lamar and
Red River Counties in north-central Texas.  On the outcrop, the contact between the upper
Eagle Ford and lower Austin (Bonham Formation) is usually considered unconformable. The
nature of this unconformity in the subsurface, however, is not well known. The inferred hiatus
(break or interruption in the continuity of a stratigraphic record) associated with the Eagle
Ford-Austin unconformity appears to diminish towards the  north-central portions  of the
basin121'.
     The contact between the Bonham Formation and the  Eagle Ford Group is an erosional
surface with the upper surface of the Eagle Ford apparently eroded. 
                                       95

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                                 ALLUVIUM (FLOODPUUN)
              Blank VM Indicates
              bckdanaquMw.
Figure 8-3. Map of Aquifers in North-Central Texas
                                         96

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     The Bonham Formation consists of greenish gray to yellowish gray clay and marl, which
becomes progressively more sandy to the east of Lamar County. Marine megafossils are
common in the Bonham. A glauconite clay bed is found near the middle of the formation.
     As with the Blossom sand, the Bonham formation strikes east-west and dips south to
the Gulf. Thickness varies from 12 to 152-m thinning westward. The Bonham Formation is
not known to yield useable water to wells in the north-central area.
Eagle Ford Group
     The Eagle Ford Group  of east Texas is a shale-dominated sequence  containing
localized deltaic (characterized by a delta) marine sands and consists predominantly of dark,
bluish-gray, bituminous, laminated clays. The  Eagle Ford varies  in thickness from 60 to
275-m.  It is thickest near the center of the basin and thins towards the southern and eastern
margins of the basin. The Eagle Ford also thins eastward along the northern outcrop. While
the dominant lithology is shale, the section contains interbeds of sandstone, limestone, and
bentonite.  Marine megafossils are common121'.
     The Eagle Ford Group of the East Texas basin can be subdivided into four formations:
the Tarrant, the Britton, the Arcadia Park,  and the Sub-Clarksville Sand (Figure 8-4, For-
mations within the Eagle Ford Group)*21'.  These formations  are  mud-dominated with an
increasing sand content upward in the section.
     The Tarrant consists of  interbedded  sandstone and shale, which records the initial
transgression of the Eaglefordian seas. The Britton consists of finely laminated highly organic
clays which characterize Eagle Ford rocks of east Texas.
     The Arcadia Park sediments are more clastic (shale) dominated and consist of 30 to
60-m of gray to dark gray,  fissile (easily split),  calcareous, mudstone with thin laminae of
siltstone, sandstone, and fragmental limestone. In the northern outcrop region of the Eagle
Ford Group, the Arcadia Park Formation is overlain by the Sub-Clarksville Formation of the
Upper Eagle Ford strata (Figure 8-4).  While the contact between the two is lithologically
abrupt, it is conformable in  nature'23'.
                                       97

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                                           AUSTIN GROUP
                                        EAGLE FORD GROUP
                                           WOODBINE
Figure 8-4. Formations within the Eagle Ford Group
     The Sub-Clarksville is the sand-dominated, upper-most unit of the Eagle Ford Group
in the East Texas basin.  Along the northern outcrop belt of the Eagle Ford Group the
Sub-Clarksville is sub-divided into two members, a lower Bells Sandstone Member, and an
upper Maribel Shale Member*21'.  The Bells Sandstone consists of gray to brown weathering
quartz sandstone. The Maribel Shale consists of medium to dark gray laminated shale with
silty partings, and thins eastward along the northern outcrop as the Bells thickens.  The
Maribel grades upward into a 1.5-m limestone bed that marks the top of the Eagle Ford
Group.
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     The Eagle Ford Group is not considered a significant source of groundwater; however,
shallow wells completed within the Eagle Ford in Lamar County yield small quantities of
useable quality water*0*.
MATERIALS AND METHODS
Monitoring Well Installation
     Three monitoring wells were installed at at the Paris, Texas OLF site for collection of
groundwater samples, waterlevel measurement data, and hydraulic conductivity testing (slug
tests).
     The location of each well is indicated in Figure 8-5. A total of 2 open boreholes and 3
stainless steel cased wells were installed between 1987 and 1989.  Installation and con-
struction details were identical for all 3 wells and individual well logs and construction details
are provided in Appendix A.
                                                                  Lit* Crook
Figure 8-5. Monitoring Well and Boring Location Map
                                       99

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     The wells were drilled with a Central Mining Equipment hollow stem rotary auger.
Generally, a solid core barrel was used during the drilling of MW-3.  Core barrel samples,
however, were collected from selected depths to monitor strata changes.  A core barrel
sampler was used exclusively during the installation of MW-1 and M W-2 in order to recover
the full length of the bored soil (see Appendix A for details).
     The wells were drilled to the depth at which the Austin-Eagle Ford contact was reached,
between 5 and 8-m from the ground surface,. Although three wells were installed, five deep
borings were actually completed.  Two borings were made to depths in excess of 10-m
(several meters deeper than the geologic contact). No evidence of groundwaterwas found
at these two locations, and the boreholes were backfilled with cuttings and then abandoned
(Figure 8-5). At each successful! borehole (MW-1 through MW-3), groundwater was found
near or at the erosional contact between the Maribel Shale of the Eagle Ford Group and the
Bonham Formation of the overlying Austin Group.  The wells were screened within this zone.
     The wells were cased with 5-cm diameter stainless steel (10-cm borehole diameter)
and each was  screened with a  1.5-m length  (5-cm diameter) section of 0.25-mm slotted
Johnson stainless steel screen. Washed sand was used for the filter pack and the sand filter
extended between 0.3 and 0.6-m above and below the screen. The screen and filter pack
were sealed off from the top of the casing with approximately 0.3-m of bentonite pellets. The
annular space above the bentonite seal was packed with cuttings and the ground surface
was sealed to a depth of approximately 1-m with  Portland cement.  Stainless steel locking
caps were welded onto the top section of each monitoring well prior to installation and
sampling.
Sampling of Monitoring Wells
     Monitoring wells MW-1, M W-2 were sampled approximately twice yearly between 1987
and 1989 to identify the quality  of groundwater at the Campbell Soup site. A total of 22
samples were collected on six dates at MW-1  and MW-2, i.e., 11  samples per well. A total
of four samples were collected at MW-3 during 1988 and 1989.
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     Prior to sampling, each well was pumped until either three casing volumes had been
removed or until each had been pumped dry several times. The wells were purged through
Teflon tubing with a vacuum lift pump. Samples were collected by lowering a 3.8-cm diameter
Teflon bailer into each well. The bailer was rinsed with distilled water between collections
at different wells.
     Each groundwater sample was analyzed for 20 purgeable organic compounds (volatile
organics), 85 base/neutral extractables, 24 metals, TOO, ammonia, nitrate-nitrite, chlorides,
sulfates, dissolved solids, alkalinity and pH.  The latter two were determined in the field. A
complete listing of the compounds and ions which were examined is provided in Appendix
B.
     Samples collected for volatile organic analyses were placed in borosilicate glass serum
bottles,  sealed, inverted and stored on ice in coolers. Samples for metals analyses were
placed in 3.8-L brown, glass jugs and acidified to a pH of 2 with concentrated nitric acid.
Samples scheduled for TOC, ammonia, and nitrate-nitrite analyses were placed in 1-L plastic
cubitaners and acidified with 2-mL of concentrated sulfuric acid.  All samples were collected
in duplicate and placed on ice in coolers during transfer to RSKERL and UT-Austin labora-
tories, where the groundwater analyses were performed.
Slug Tests on Monitoring Wells
     Slug tests were performed on two of the monitoring wells (MW-1 and M W-3) to measure
the hydraulic conductivity of the water bearing zone around the well screens at the Austin-
Eagle Ford contact. MW-2 was not tested because damage to the casing prevented the
insertion of the slug testing equipment into the well.  The slug test results were used to
estimate the spatial variation of hydraulic conductivity within the Eagle Ford Formation-Austin
Chalk contact at the Campbell Soup site. Combining the resulting hydraulic conductivity
values with the porosity of the aquifer and slopes of the piezometric surface permited the
prediction of pore water velocities and, hence, the rate of movement of groundwater con-
taminants.
                                       101

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     The slug test involved "instantaneously" lowering (or raising) the water level in a well
and measuring the water-level recovery through time. This technique was originally devel-
oped by Hvorslev124' and has since been  expanded  to include  a variety of field situa-
tjons<26)(28)(27)(28). Although the results of this method are not precise*291 it is generally considered
appropriate  as  a means of  estimating  the  order of magnitude of  field  hydraulic
conductivity00"281.
     Several assumptions must be met for the method to be valid: (a) the change in water
level in the well must be "instantaneous", so that no cone of depression is created around
the well; this is necessary because the mathematical development of the slug test method*24'.
treats the head in the formation as a constant, and (b) flow to the well must be according to
Darcy's Law.  The well must be constructed so that neither the screen nor the filter pack
inhibit or significantly enhance groundwater movement. Thus, a clogged screen or filter pack
would renderthe well inappropriate for slug testing. In addition, the well cannot be developed
to such an extent that a zone of increased permeability is developed around the well screen.
     In performance of slug tests, the water level in the well is rapidly changed by removing
water with a pump, bailer, or solid weight. The water level is then repeatedly measured at
recorded times as recovery begins. Drawdowns are then normalized by dividing by the initial
(maximum) drawdown. The  normalized drawdowns are plotted versus time  on a semilo-
garithmic scale; drawdowns are plotted on the logarithmic scale. Two values of drawdown
on the linear portion of the curve and their corresponding time values are read from the graph
and then substituted into the appropriate solution (based on well configuration) for the cal-
culation of the hydraulic conductivity1261.
     Slug tests were performed on MW-1 and MW-3 on July 18,1989. Standing water was
rapidly removed from the wells with a 3.8-cm diameter 1 -L capacity PVC bailer. At the time
when inflow equalled outflow (due to bailing) or the well was bailed dry, the slug test was
begun. A stopwatch and a vinyl survey tape was used to measure the time dependent rate
of water level  rise.  Each well was tested at least three times. The slug test results are listed
in Appendix C.
                                       102

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Well Casing and Water Level Elevation Survey
     A topographic survey was made at the site to identify the elevation and location of all
monitoring wells and borings made at the Campbell Soup site. The data were used to
determine groundwaterflow directions and construct geologic cross sections of the site. The
elevation survey was conducted by EPA personnel using standard survey practices.
RESULTS
Groundwater Hydrology
Water Level Analysis
     Water level elevations were measured in the 3 monitoring wells on two dates in 1989.
The water level measurements and ground surface elevations from July 18,1989 and August
24,1989 presented in Table 8-2.
        TABLE 8-2. GROUND SURFACE AND WATER LEVEL ELEVATIONS*
Location
MW-1
MW-2
MW-3
Ground Surface
Elevation
152.26
152.65
142.51
Water Level,
Potentlometrlc
Surface**
151.73/151.73
151.06/152.06
141.75/142.68
Austin-
Eagle Ford
Contact
148.01
147.90
135.37
           *  All elevations in units of meters above mean sea level.
           **  July 18,1989 / August 24.1989 measurements.
     The flow direction of the groundwater below the Cambell Soup site was determined
using these water level elevations. The general direction of flow in the aquifer was from the
south to the north-west. The linear distance between MW-1 and MW-3 was 2,330-m; 200-m
between MW-1 and MW-2; and 2,170-m between MW-2 and MW-3. Based on these data
the hydralic gradient between MW-1 and MW-3 was calculated as 0.0039 m/m, and 0.0048
between MW-2 and MW-3.
     A geologic cross section (Figure 8-6) of the subsurface between MW-1 and MW-3 was
constructed using the data presented in Table 8-2 and the well logs (Appendix A). Because
the elevation data represent only three locations over a linear  surface distance of over
                                     103

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2,000-m, it was necessary to extrapolate a large part of the surface and subsurface contours
between MW-2 and MW-3. The extrapolation was based on observations noted during the
field investigations.  The survey results indicate that although the regional dip of the
Austin-Eagle Ford contact is to the south-east, the local dip is to the north-west. The difference
in dip may be due to localized faulting or folding of the strata.
     A rigorous analysis (including pumping tests and water level measurements at clustered
piezometers) to determine the type of aquifer (i.e., confined, semi-confined, or unconfined
aquifer) at the site was not conducted.  However, based upon the available data, it was
concluded that the aquifer could best be described as a either a semi-confined aquifer or a
watertable aquifer. Because the limited aquifer data exhibited characteristics of both of these
systems it was not possible to definitively identify the aquifer type.
     Drilling logs indicated that the overlying clay of the Bonham Formation was heavily
fractured along the horizontal plane, thus it is possible that water may be transmitted relatively
rapidly through these fractures in the less permeable clay and marl of the Bonham Formation
to the highly permeable weathered contact zone between the Austin and Eagle Ford Groups.
Therefore, although the entire soil system may be near or at saturation (i.e., a water table
aquifer would exist) a well screened within the Bonham clay may not produce appreciable
quantities of water unless the screen were to penetrate fractures which transmit significant
quantities of groundwater. During well drilling no water was observed in the boreholes of
MW-1, MW-2 and MW-3 until the contact zone was reached, at which point water rushed
into the borehole and rose above or to within approximately a meter of the ground surface.
Thus, upon initial inspection of field data, it may appearthat the aquifer is confined. However,
because of the high storativity and low transmissivity of the Bonham clays it is possible that
a semi-confined aquifer exists at the site. These results were further supported by tensio-
menter and neutron probe soil moisture measurements made  at the site in 1968(8) which
indicated that soil below the site was continously near saturation.
                                        104

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   160 -r
    150 - -
    140- -
    130 *-
              South
          MW-1  MW-2
                                           EAGLE FORD GROUP        Wwhrd contact ton*
            L*Q*nd:
             MW      GroundwiMr monitoring vrall.

              ElcvMlon In m*tr *bov* mnn  |vl
0        250       500
                                                                 eal* nwMr*
                                                                                                    North
                                                                                                         MW-3
Figure 8-6. Geologic Cross Section Between MW-1 and MW-3

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Slug Tests
      For the slug test analyses, the applicable well configuration equations'25'were taken
for three possible cases.  A cased well in a confined aquifer with (a) a partially penetrating
well screen and, (b) a fully penetrating screen and, (c) a cased well with a partially penetrating
screen in an unconfined aquifer. The appropriate equations forthe partially penetrating case
are:
Partially penetrating well screen: confined aquifer
                                   c.afe-0  \s2
where:
                             /c - hydraulic conductivity, L/T
                             TC - pi, dimensionless
                              tm well radius, L
                             R m screen radius, L
                             t, m time, T
                             S, m drawdown at t,, L
                             C. - shape factor, dimensionless
with:
                           L -   screen length, L.
     A complete listing of slug test data is provided in Appendix C. The calculated hydraulic
conductivity for MW-1 (jfc = 1.5 x 10~* cm/sec) was an order of magnitude less than for MW-3
(jfc - 3.5 xKX3 cm/sec).
     Because the type of aquifer and the exact location of the water zone (with respect to
the well screen) was not known, the slug test calculations were performed forthe two alternate
cases of (a) a fully penetrating screen in a confined aquifer and, (b) a water table aquifer.
These additional calculations were necessary to test the sensitivity of the calculated hydraulic
conductivity to well configuration and  aquifer type. The appropriate  equations and their
application are described by Cedergren'26'. The results indicated that the calculated hydraulic
                                        106

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conductivity was within the same order of magnitude, regardless of whether the screen was
fully or partially penetrating or in an unconfined or confined aquifer. The results of the cal-
culations are summarized in Table 8-3.
              TABLE 8-3.  SLUG TEST RESULTS FOR CONFINED
                          AND UNCONFINED AQUIFERS
Well No.
MW-t
MW-1
MW-3
MW-3
Assumed Screen
Geometry
Partially penetrating*
Fully penetrating**
Partially penetrating*
Fully penetrating**
Hydraulic
Conductivity (cm/s)
1.5x10-*
2.3x10-*
3.5 x10'3
5.5X10"3
                *  Confined and unconfirmed aquifer conditions
                **  Confined aquifer conditions only
     Calculated hydraulic conductivity values for the partially penetrating confined case and
the unconfined case were identical.  The calculated hydraulic conductivity values foe all
cases were substantially greater than typical values for unweathered marine clay and shale
(k between 10"11 and 10^cm/s). The calculated values, however, were well within the range
of hydraulic conductivities reported for fractured igneous and metamorphic rocks as well as
clean sand (k between 10^ and lO^cm/s)'61.
     These results indicate that fractures in the Mirabel Shale and sandy laminae  at the
weathered contact zone between the Eagle Ford Group and the Austin Chalk represent a
path for the rapid movement of groundwater at the Paris, Texas site.
CONCLUSIONS
     The Paris, Texas area is underlain by hundreds of meters of sediments laid down from
the Paleozoic through the Quarternary eras. A continuing cycle of advance and retreat of
ancient seas resulted in periods of sediment accumulation alternating with periods of erosion.
The Austin Chalk Group outcrops at the Campbell Soup (Texas) Inc. OLF site. The Bonham
Formation, within the Austin Group, is a heavy clay with marl, about 6 to 15-m thick at the
                                       107

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site. The Bonham Formation is underlain by the Eagle Ford Group. The Eagle Ford Group
is composed primarily of dark, fissile shale. The contact between the Eagle Ford and Austin
Groups is characterized by an erosional surface and is unconformable.
     The results of the hydrogeologic investigation indicated that an aquifer exists below
the OLF site.  Data limitations prevented the definitive classification of the aquifer, i.e., either
semi-confined, confined orunconf ined. The available data, however, suggest that the aquifer
                                                i
is semi-confined and that the erosional contact between the Eagle Ford and the Austin Groups
may serve as a  significant  transmission zone for groundwater within the relatively
impermeable clays of the Bonham Formation.
     Groundwater level data indicate that the general flow direction was to the north-west
with a hydraulic gradient of approximately 0.004 m/m.  Measured hydraulic conductivity
values within this zone (k between 10"* and 10'3 cm/s) were substantially greater than typical
values for unweathered marine clay and shale (k between 10'" and lO^cm/s).  However,
the calculated values were well within the range of hydraulic  conductivities  reported for
fractured rocks as well as for clean sand (k between 10"4 and 10"3 cm/s)(6>.
     These results indicate that fractures in the  Mirabel Shale and sandy laminae at the
weathered contact zone between the Eagle Ford Group and the Austin Chalk represent a
path for the relatively rapid movement of groundwater at the Paris, Texas site.
                                        108

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                                CHAPTER 9
      GROUNDWATER: QUALITY, RECHARGE, AND GEOCHEMISTRY
INTRODUCTION
     The assessment of the long-term effects of OLF treatment on groundwater quality
required the collection of "background" and possibly "impacted" groundwater samples. This
section presents groundwater quality data collected at the Paris, Texas OLF site between
1987 and 1989.
GROUNDWATER QUALITY DATA
     Monitoring wells M W-1, M W-2 were sampled approximately twice yearly between 1987
and 1989 to identify the quality of groundwater located within the erosional contact of the
Austin and Eagle Ford  Groups at the Campbell Soup site. A description of the monitoring
well installation is given in Chapter 8. A total of 22 samples were analyzed.  The samples
were collected on six dates at MW-1 and MW-2, i.e., 11 samples per well. A total of four
samples from MW-3 were analyzed.  The samples were  analyzed for the constituents
summarized in Table 3-1. A detailed list of the constituents is provided in Appendix B.
     With the exception of the samples collected on 6/17/87, all samples were analyzed in
duplicate; i.e., one sample was filtered through a 0.45 micron filter while the other was not
filtered prior to analysis. The samples were filtered to remove clay particles which can become
suspended in the groundwater during  the process  of sample collection. The inadvertent
suspension of clay particles may result in the increase in the concentrations of clay con-
stituents such as aluminum, iron, and magnesium and any chemicals sorted to the clay, in
the unfiltered, digested sample over the filtered, digested sample.
     The groundwater monitoring data  for constituents detected in the three wells are
presented in Tables 9-1, 9-2, and 9-3. No extractable organic compounds and purgeable
organic compounds (as listed in Appendix B) were detected in the groundwater from any of
the wells at any time.  Therefore, these  constituents were not  included in the Tables 9-1
through 9-3.
                                      109

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     Based on the general classification of Winslow and Kister1', the groundwater samples
from all three wells were moderate to very saline, with IDS values between 7,000 and 13,000
mg/L. The salinity was primarily due to the presence of the following dissolved ions: chloride,
sulfate, sodium, calcium, and magnesium.
     TOO values were low (<10 mg/L) at all wells and this condition  is typical for a
groundwater which has not be subjected to contamination by organic material.
     Water samples were collected at MW-1 and MW-2 on the following dates: June 11,
1987; June 17,1987; September 3,1987; June 1, 1988; November 1,1988; and April 4,
1989.  Groundwater data from MW-1 (over time) for the major cations present (calcium,
magnesium and sodium) with standard deviations are presented in Figures 9-1 through 9-3.
The figures illustrate the consistency of the groundwater quality at MW-1. Similar trends for
these constituents were observed at MW-2. Means and standard deviation values  for the
major anions  present (chloride and sulfate)  could not  be calculated  because duplicate
analyses for these constituents were not performed.
     Two samples were collected at MW-3 on November 1,1988 and April  5,1989; con-
sequently, insufficient data existed to analyze the data with respect to time for that well.
     The data from MW-1 and MW-2 were tested by one-way analysis of variance (ANOVA)
to determine if the means with respect to sampling date and location were representative of
long-term and location water quality. Mean values were desired to provide a rapid  means
for comparison of water quality between locations.
                                       110

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                 TABLE 9-1. GROUNDWATER CONSTIUENTS DETECTED* AT MW-1:1987 THROUGH 1989
|; ^Constituent
Inorganic Cations
Aluminum
Barium
Boron
Calcium
Chromium
Cobalt
Iron
Lithium
Magnesium
Manganese
Nickel
Potassium
Sodium
Strontium
Thallium
Titanium
Zinc
Inorganic Anions
Chloride
Sulfate
Additional Analyses
Alkalinity
Ammonia
NOj-NCyN
pH
TOG
6/11/87* 6/11/87** 6/17/87*

24
0.24
2.6
400
0.03
0.01
20
0.34
240
0.60
0.01
8.7
2.600
9.8
0.02
0.6
0.03

2.419
5,025

600
1.0
<0.05
NA
14

0.4
0.07
1.8
450
<0.02
<0.02
0.4
0.42
250
0.52
<0.02
9.7
2.700
12
<0.05
<0.2
0.41
-
NA
NA

NA
NA
NA
NA
NA

8.2
0.10
2.7
400
<0.01
0.01
6.6
0.35
230
0.58
0.01
7.6
2,900
9.7
0.03
0.2
<0.01

2.200
5,075

660
0.9
0.3
NA
<2
9/3/87*

0.4
0.03
2.6
530
<0.01
0.01
2.5
0.38
280
0.72
<0.01
6.7
3.300
11
<0.02
<0.1
<0.01

2.334
5.740

600
1.0
<0.05
7.2
NA
9/3/87*

<0.1
0.02
2.3
510
<0.01
0.01
1.9
0.36
260
0.68
<0.01
6.4
3.000
11
<0.02
<0.1
<0.01

NA
NA

NA
NA
NA
NA
NA
6/1/88*

0.96
0.02
0.55
485
0.02
<0.01
3.22
0.23
335
0.42
0.05
5.3
3.510
11.6
<0.02
<0.1
0.01

2,200
6.360

640
0.7
<0.05
6.89
2.6
6/1/88**

<0.1
0.02
0.59
499
<0.01
<0.01
1.88
0.29
340
0.42
0.05
5.52
3,690
11.7
<0.02
<0.1
<0.01

NA
NA

NA
NA
NA
NA
NA
11/1/88* 11/1/88**

6.44
0.09
2.89
464
0.11
0.01
10.0
0.37
173
0.52
0.03
10.05
2.420
9.16
0.06
0.29
0.01

1.600
4.140

580
NA
NA
NA
NA

<0.1
0.01
2.99
468
<0.01
0.01
1.90
0.37
174
0.53
0.02
9.95
2.240
9.11
0.07
0.11
0.03

NA
NA

NA
NA
NA
NA
NA
4/5/89*

5.64
0.07
2.10
491
0.07
0.01
7.13
0.44
250
0.39
0.04
8.58
2,490
10.4
0.02
0.29
0.01

NA
NA

NA
NA
NA
NA
NA
4/S/89!*|

6.44
0.09
2.89
464
0.11
0.01
0.49
0.42
241
0.38
0.04
8.00
2.550
10.1
0.04
<0.1
<0.01

NA
NA

NA
NA
NA
NA
NA
  '    All values in units of mg/L except pH, and alkalinity in mg/L as CaCO,.
  *    Sample was not filtered prior to analysis.
 ~    Sample was filtered through 0.45 micron filter prior to analysis.
NA    Not analyzed.

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           TABLE 9-2.  GROUNDWATER CONSTITUENTS DETECTED* AT MW-2:1987 THROUGH 1989
Constituent
Inorganic Cations
Aluminum
Barium
Boron
Calcium
Chromium
Cobalt
Iron
Lithium
Magnesium
Manganese
Nickel
Potassium
Sodium
Strontium
Thallium
Titanium
Zinc
Inorganic Anions
Chloride
Sulfate
Additional Analyses
Alkalinity
Ammonia
NOj-NOz-N
pH
TOC
6/11/87*

3.3
0.06
1.0
520
<0.01
<0.01
2.5
0.70
110
1.6
0.01
8.6
1.700
11
0.03
0.1
<0.01

1.629
3.450

NA
NA
NA
NA
NA
6/11/87**

<0.1
0.05
1.0
520
<0.01
0.01
<0.1
0.69
110
1.6
0.01
8.2
1.700
11
<0.02
<0.1
0.21

NA
NA

NA
NA
NA
NA
NA
6/17/87*

2.0
0.04
1.1
520
<0.01
0.01
1.7
0.63
110
1.7
0.01
7.7
1.700
11
0.03
0.1
<0.01

1,479
3.425

NA
0.5
0.3
6.9
<2.0
9/3/8T

0.2
0.03
1.0
600
<0.01
0.01
0.3
0.80
130
1.9
0.03
8.3
2,100
12
<0.02
<0.1
<0.01

1.523
3.510

NA
1.0
<0.05
7.02
<2.0
9/3/87**

<0.1
0.03
1.3
570
<0.01
0.02
0.2
0.53
120
2.2
0.02
7.4
2,000
11
<0.02
<0.1
<0.01

NA
NA

NA
NA
NA
NA
NA
6/1/88*

0.63
0.04
0.58
516
0.03
0.01
1.21
0.87
126
1.91
0.02
7.16
2.110
12.9
<0.02
<0.1
0.03

1.500
3.500

NA
0.4
<0.05
6.82
5.0
6/1/88**

<0.1
0.04
0.57
521
<0.01
0.01
0.27
0.77
127
1.93
0.02
8.06
1,990
12.6
<0.02
<0.1
0.02

NA
NA

NA
NA
NA
NA
NA
11/1/88*

1.44
0.02
1.22
503
<0.01
0.01
2.53
0.58
110
1.75
0.03
10.9
1.750
11.4
0.06
0.20
0.01

2.450
3,320

650
1.40
<0.05
6.97
4.7
11/1/88**

<0.1
0.01
1.32
515
<0.01
0.01
0.36
0.58
111
0.36
0.02
11.2
1.950
11.4
0.09
0.12
0.01

NA
NA

NA
NA.
NA
NA
NA
4/5/89*

4.68
0.04
0.92
504
0.02
0.01
4.41
0.85
125
1.72
0.04
11.2
1,740
12.1
0.02
0.26
0.01

NA
NA

NA
NA
NA
NA
NA
4/5/89**

<0.1
0.01
0.89
499
<0.01
0.01
0.15
0.66
113
1.66
0.03
10.12
1,790
10.9
0.06
<0.1
0.01

NA
NA

NA
NA
NA
NA
NA
NA
All values in units of mg/L except pH, and alkalinity in mg/L as CaCO,.
Sample was not filtered prior to analysis.
Sample was filtered through 0.45 micron filter prior to analysis.
Not analyzed.

-------
    TABLE 9-3.  GROUNDWATER CONSTITUENTS DETECTED*
                AT MW-3:1988 THROUGH 1989
Constituent
Inorganic Cations
Aluminum
Barium
Boron
Calcium
Chromium
Cobalt
Iron
Lithium
Magnesium
Manganese
Nickel
Potassium
Sodium
Strontium
Thallium
Titanium
Zinc
Inorganic Anions
Chloride
Sulfate
Additional Analyses
Alkalinity
Ammonia
N03-NO2-N
PH
TOC
11/1/88* ;

10.2
0.03
1.49
491
<0.01
0.23
4.51
0.77
140
4.00
0.35
15.2
1,240
8.31
0.06
0.13
1.92

1,200
3,100

34
0.40
<0.05
4.9
6.7
;;11/1/88**lf:;

9.51
0.02
1.53
505
<0.01
0.23
4.12
0.77
141
4.11
0.35
15.0
1.420
8.49
0.11
0.12
1.51

NA
NA

NA
NA
NA
NA
NA
4/5/89*

12.3
0.01
1.68
494
<0.01
0.24
4.32
0.95
152
4.28
0.35
16.0
1,280
9.14
0.03
<0.1
1.47

NA
NA

NA
NA
NA
5.4
NA
'y";:4/5/89**.::;:;

11.5
<0.01
<0.03
512
<0.01
0.25
4.32
0.07
153
4.40
0.35
15.2
1,350
<0.01
0.07
<0.1
1.54

NA
NA

NA
NA
NA
NA
NA
  * All values in units of mg/L except pH, and alkalinity as mg/l CaCO3.
  * Sample was not filtered prior to analysis.
 ** Sample was filtered through 0.45 micron filter prior to analysis.
NA Not analyzed.
                               113

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  600
  500
  400
  300
  200
   100
      Concentration, mg/L
                                              iTAMOAHO x^ I
          1
         6/11/87     9/3/87      6/1/88      11/1/88      4/6/89
                     Date of Sample Collection
Figure 9-1. Calcium Concentration MW-1:1987-1989
      Concentration, mg/L
  400

  360

  300

  260

  200

  160

  100

   60
  OCVUTION

          1
I
         6/11/87     9/3/87      6/1/88      11/1/88
                     Date of Sample Collection
Figure 9-2. Magnesium Concentration MW-1:1987-1989
           4/6/89
                                 114

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  4000
  3000
  2000
   1000
        Concentration, mg/L
                                                  (TANOAHDx
                                                  OCVUTWN--
WAN
           6/11/87      9/3/87       6/1/88      11/1/88
                        Date of Sample Collection
 Figure 9-3. Sodium Concentration MW-1:1987-1989
4/6/89
     The ANOVA tests were applied to potassium, calcium, magnesium, manganese,
 sodium, chloride, and sulfate groundwater concentration data. These ions were selected for
 ANOVA analyses because: (a) they represented the major cations and anions present in
 groundwater as well as soil, (b) soil data indicated that leaching of several of these ions may
 have occurred, and (c) duplicate samples of these ions, with the exception of chloride  and
, sulfate analyses, were available from 5 of the 6 sampling events.
     Analysis of the soil data indicated that nickel and zinc had accumulated in the waste-
 water appliction areas. Therefore, the groundwater data was examined to determine if there
 was any effect on water quality due to the presence of these two metals in the surface soil
 at the site. Nickel and zinc concentrations in all samples collected at MW-1 and MW-2 were
 near or below instrument detection limits (0.01 mg/L). However, significantly greater con-
 centrations of zinc (mean = 1.61 mg/L) and nickel (mean = 0.35 mg/L) were  detected in all
                                      115

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4 samples from MW-3.  The higher zinc and nickel concentrations at MW-3 may have been
due to increased solublization of these elements in the groundwater because of the low pH
(4.9) in the vicinity of the well.
     Because of error inherent in sample measurement when the concentration is near the
instrument detection limit, the nickel and zinc data were excluded from the ANOVA test. The
results of the ANOVA testing (p <, 0.05) on the calcium, magnesium, manganese, potassium,
sodium, chloride, and sulfate data collected at MW-1 and MW-2 are given in Table 9-4. Data
from MW-3 were not included due to the  limited size of the data set available for that well.
           TABLE 9-4. GROUNDWATER MONITORING WELL DATA
                      (MW-1 & MW-2) ANOVA* TEST RESULTS
Constituent
Calcium
Magnesium
Manganese
Potassium
Sodium
Chloride
Sulfate
Well Location
'iaF = 9.75
118F = 35.8
118F = 50.8
not significant
118F - 38.3
not significant
16F = 15.22
Collection Date
not significant
not significant
not significant
415F=10
not significant
not significant
not significant
                     Critical F values: 415F = 3.06;',,F = 4.41;
                      '15F = 4.54;',F = 5.99
     The ANOVA testing indicated that, with respect to location, statistically significant
differences between the means were present. However, for all metals and anions tested by
ANOVA, with exception of potassium, there was no statistical difference in groundwater
quality over the time period of study (June 1987 through April 1989).  Thus, mean
concentration values at each location (with respect to time) of groundwater quality indicies
were suitable for use in comparisons and summarization.
     Because insufficient data were available to test for equality of the mean concentration
values measured at MW-3 it was assumed that water quality indicators at MW-3 followed
the same trends (with respect to location and sampling period) as at MW-1 and MW-2.
                                      116

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Therefore, mean values were calculated for the data obtained at MW-3. Likewise, mean
values were calculated for nickel and zinc (for MW-1, MW-2, and MW-3) although the data
were deemed inappropriate for ANOVA testing.
     The mean values were adequate for simple, rapid comparisons of water quality between
the wells.  A summary of the groundwater monitoring data (mean values) for all three wells
is given in Table 9-5.
          TABLE 9-5.  GROUNDWATER QUALITY* AT CAMPBELL SOUP
                     SITE: MEAN* VALUES AND STANDARD DEVIATION
Constituent
Calcium
Magnesium
Manganese
Nickel
Potassium
Sodium
Zinc
Chloride
Sulfate
Alkalinity
as CaCO3
TOC
pH~
MW-1
472  42
247165
0.5210.11
0.03 1 0.02
7.911.7
2,870 1 452
0.02 1 0.01
2,1511322
5,2681834
610142
<10
6.9 - 7.2
MW-2
525 1 32
129138
1.7910.18
0.03 1 0.02
8.811.55
2,0261415
0.02 1 0.01
1,8561440
3,441 1 76
65517
<10
6.8 - 7.0
MW-3
496 1 6.5
169 1 49
4.2010.18
0.35 1 0.0
13.513.7
1,6231623
1.6110.21
1,200*
3.100*
27110
NA
4.9 - 5.4
             *  All units in mg/L, except pH.
             '  Mean values in boldface, standard deviation in standard type.
             "  Single analysis performed.
             **  Range provided for pH.
                                      117

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DATA ANALYSIS AND DISCUSSION
Background Water Quality
     Water quality data obtained from wells near the Campbell Soup plant and screened
within the same aquifer and geologic formation can be used as a measure of "background"
groundwater quality. However, inspection of well records for Lamar County120' indicated that
there were no wells within the immediate vicinity of the Paris, Texas area (as well as the
entire County) which were screened within the Austin Chalk-Eagle Ford Group contact. The
absence of wells at the contact may be attributed to the low probability of obtaining useable
quantities of water from the contact zone (Chapter 8).
     The presence of springs within the Bonham clay near the site and the quality of the
spring waters can provide an indication of water quality which may be expected from wells
screened within the Bonham Formation. However, field reconnaissance conducted as part
of this study  and an examination of records of springs in Lamar County and adjacent
Counties'321 indicated that no springs discharged from the Bonham clays at or near the site.
Most springs in Lamar County discharged from the Blossom sand and the Woodbine For-
mations. The spring waters were classified as sodium bicarbonate type, usually fresh, soft
to moderately hard, and of neutral pH.138' These findings indicated that spring water quality
in the area could not be used as an indicator of background groundwater quality at the OLF
site because  the springs do not develop within nor do they discharge from the Bonham
Formation.
     Research conducted at the Paris, Texas OLF site in 1968 included an examination of
soil water quality at several wastewater application locations.'10' The ground water samples
were obtained from ceramic, porous cup lysimeters set at  approximately 1 -m below the
ground surface. Lysimeters were located in the G-section of the system along lines which,
at the time of sample collection (April 1968), had received wastewater for 2-years (G-11) and
4-years (G-4). The lysimeter data are presented in Table 9-6.
                                       118

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     Because MW-2 was also located along the G-4 wastewater spray line, the lysimeter
data from 1968 were used in direct comparisons of groundwater quality after 2, 4, and
24-years of wastewater application. The comparison is presented in the following subsection.
               TABLE 9-6.  LYSIMETER DATA*: 1-METER BELOW
                           GROUND SURFACE. APRIL 1968
Constituent
Calcium
Magnesium
Potassium
Sodium
Chloride
Sulfate
Alkalinity
as CaCO3
pH*
G-4 line**
88
20
1.4
257
190
570
60
6.7
G-11 line***
24
2
0.6
30
69
25 .
30
6.0
                       *  All units in mg/L, except pH.
                      **  4-years of wastewater application at collection.
                      ***  2-years of wastewater application at collection.

Groundwater Seepage Quantities
      Darcy's law can be used to estimate seepage (aquifer recharge) through saturated and
unsaturated soils if the hydraulic gradient, hydraulic conductivity, and wetted area are known
or can be estimated with reasonable accuracy. Darcy's law is commonly stated as:
                                        q = kiA                              (9-1)
with q equal to the quantity of seepage, k the hydraulic conductivity, i the hydraulic gradient,
dh/dl (change in hydraulic head/change in length) and A, the cross sectional area.
      The groundwater recharge process  at the Paris, Texas OLF site can be conceptually
described using Darcy's law as follows. Approximately 365 ha (3,650,000 m2) were irrigated
at the OLF site. Previous research at the site'101 indicated that the saturated surface and
moist subsurface clay soils had a hydraulic conductivity of approximately 10"6 cm/sec. If it
                                        119

-------
is also assumed that (a) the depth of penetration of saturation, /, just equals the hydraulic
head, A, that is forcing water downward into the soil and (b) capillarity is neglected, then the
hydraulic gradient, i, is equal to unity.  Hence, for the assumed conditions and applying
Darcy's law, the soil at the wastewater application areas can accept approximately 3,150
nrrVd, or 20% of the mean daily applied flow of 16,000 m3/d. This calculated  infiltration
percentage agrees with the mean estimated infiltration percentage (20%) reported in earlier
studies at the Paris, Texas site'101.
      If it is assumed that wastewatei application occurs 350 days per year and the infiltration
rate remains constant, over 1,104,000 m3/yr (292 million gallons) of water would theoretically
seep through the clay soil at the site over a one-year period. Over the course of 24-years,
this could result in the addition of over  26,500,000  m3 (7 billion gallons) of water to the
subsurface.  In addition, the simple application of Darcy's law indicates that water would
move vertically downward through the saturated clays at a rate of approximately 1-m per
year.
      Using a daily recharge rate of 3,150 m3/d, a simple calculation was made to estimate
the time in years required to saturate the  clay underlying the OLF site, and thus, develop an
aquifer where one did not exist previously. The calculations were made with the following
assumptions: (a) annual recharge = 1,104,000 nvVyr, (b) mean saturated thickness of 7-m.
(c) wetted surface area of 365-ha and, (d) and an effective porosity of 0.35.  The effective
porosity is the fraction of the total volume of clay that consists of interconnected pores. The
effective porosity corresponds to the volume of void space which must be filled with water
to establish saturated conditions. The selection of 365-ha represented the most conservative
scenario because in the 1960's and early 1970's less than half of the 365-ha were used for
wastewater application, yet the volume of water applied and presumably subject to recharge
was about the same (i.e., annual recharge = 1,104,000 rrvVyr). The mean saturated thickness
of  7-m  represented the case in which  the semi-confined  aquifer  located at  the Austin
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Chalk-Eagle Ford contact (approximate aquifer thickness < 1-m) would be slowly recharged
due to high porewater pressures in the overlying clay of the Bonham Formation, which would
be near or at saturation.
     Based on these assumptions, a semi-confined aquifer would be formed after 8 years
of wastewater application.  The aquifer would be semi-confined from above by clays near
or at saturation with a uniform thickness of 7-m. The selection of a more conservative value
of the effective porosity (n. = 0.1), would result in the development of an aquifer after only 2
years of wastewater application.  Although several simplifying assumptions were made to
proceed with the calculations, the results indicated that the estimated recharge of treated
wastewater to the subsurface would be more than sufficient to develop and maintain (within
a relatively short period of time) saturated  conditions in the upper confining unit and a
semi-confined aquifer below the entire OLF site.
Hydrochemlcal Fades
     Hydrochemical facies are distinct zones that have cation and anion concentrations
describable within defined composition categories'6'. The definition of a composition category
is commonly based on the subdivisions  of a trilinear diagram (Figure 9-4).  The trilinear
diagram represents a percentage plotting of cations and anion concentrations (meq/L) in
separate triangles.
      Hydrochemical facies are used to describe bodies of groundwater in an aquifer which
differ in chemical composition133'. The facies are a function of the lithology, solution kinetics
and flow patterns of the aquifer. Hydrochemical facies can provide a simple and rapid means
of identifying different  waters at one or  many locations.   Using this system (Figure 9-4),
suit ale-chloride facies were dominant for  groundwater collected at all three monitoring wells
(MW-1, MW-2 and MW-3) and at the G-4 lysimeter (in 1968).
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                                                          dominant

                                                          v  tVPe  /
                                                           \      /
                                                 Bicarbonate \    /  Chloride
                 Ca
              CATIONS
   Cl

ANIONS
Figure 9-4. Trilinear Diagram Classification of Anion and Cation Fades
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     The use of hydrochemical facies provided further evidence of the similarity of water
quality and geochemical evolution between the water samples collected at the three moni-
toring wells and the G-4 line lysimeter. The results suggest that groundwater characteristics
below the  site are the result of the dissolution of naturally present soluble minerals which
contain sulfate and chloride as the predominant ions. These ions would be expected in the
Bonham clays based upon the geologic history of the site (Chapter 7) and the results of the
soil core sample analyses (Chapter 8).
Ma|or-lon Aqueous Geochemistry
     Schoeller diagrams provide a convenient means for the visual inspection of chemical
data from groundwater samples.  The Schoeller semi-logarithmic plot permits the  total
concentration (milliequivalents/L) of major cations and anions of several water samples to
be represented on a single graph  in which major groupings or trends in the data can be
discerned visually'6'. The ionic composition lines for mean concentrations (meq/L) of calcium,
magnesium, sodium and potassium, chloride, sulfate  and bicarbonate in  groundwater
samples collected from all three wells (MW-1, MW-2, and MW-3) are plotted in Figure 9-5.
Mean values were  used because, as described above, there was no statistically significant
difference in the mean concentration values of these major ions overtime at each well.
     Bicarbonate values were calculated using ionic concentration data for the major con-
stituents with the relationship:
           (Na+) + (Mg2*) + (Cat*) = (HCOj) + (SO*) + (CD                        (9-2)
where ( ) represent units of milliequivalents per liter.
     The similarity among the ionic composition lines on the Schoeller plot suggested a
"match" between  the  water  at the three  wells.  These  results indicate  that although
groundwater quality varied among the three locations, the waters have apparently undergone
similar patterns of geochemical evolution.  Further, the results suggest a weak trend of greater
ionic concentration at the south end and oldest area of the site (MW-1) with respect to water
quality at the north edge of the site (MW-3).
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        Concentration, meq/L
    1000 rr
     100 =
                                         Cl
8O4      HCO3
Figure 9-5. Schoeller Diagram: Mean Values From 1987-1989
     The G-4 lysimeter water quality data collected in 1968 have been summarized in a
Schoeller diagram (Figure 9-6) along with the mean values of samples collected at MW-2
(located in the G-section of the OLF site).
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      1000
       100
        10
           Concentration, meq/L
                                     24-year* of application
                              4-yeara of application
                               2-yvara of application
                                        Q-4   -B- Lylmter 0-11
       0.01
                                                     8O4
HCO3
Figure 9-6. Schoeller Diagram: Long-term Groundwater Quality
     The data in Figure 9-6 indicate a trend of increased ionic concentrations at the OLF
site over time, specifically, below the G-4 line.  The similarity in ionic ratios (composition)
suggest an apparent "match" between the more recent groundwater data collected at M W-2
and the older data from the lysimeter at G-4.  These results strongly suggest that over a long
period of time (i.e.,  24-years), groundwater may have evolved from a relatively dilute to a
more concentrated solution.
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Geochemlcal Evolution of Groundwater
     The Bonham Formation is composed of clays and marls of marine origin (Chapter 8).
The porosity of clays and marls is often very high, sometimes exceeding 50%, with very fine
and numerous pores that provide an enormous area of contact between water and rock.
Although many clays are commonly rated as impermeable and water movement through
them is very slow, their colloidal nature and the fineness of their pores permit clays and marls
to retain large quantities of water as well as salts (chlorides and sulfates) by adsorption,
either by the sediments during deposition or from connate sea water (i.e., water trapped in
the clays at the time they were deposited).
     A high NaCI content in groundwater does not necessarily indicate connate water, but
may simply mean that there has been salt concentration in stagnant groundwater by (a)
dissolution of soil minerals or, (b) evapotranspiration of salts in the applied wastewater.  The
evapotranspirative concentration of salts in the applied wastewater cannot  produce  a
groundwater with the quality found at the OLF site.  Based on the evapotranspiration rates
measured at the s'rte(10), the concentration of Cl'in the applied wastewater (Table 5-2), and
a mean application rate of 16,000 m3/d, evapotranspiration alone could only result  in a
groundwater Cl~ concentration in the range of 100 to 200 mg/L. The lysimeter data (Table
9-6) collected from the root zone support these calculations.
     The evapotranspirative concentration trend is demonstrated by the data in Table 7-13,
The data indicate that leaching of Cl', most likely due to limited infiltration of precipitation,
has removed Cl' from the upper soil surface in the control area. However, significantly higher
concentrations (between 115 and 590 mg/L) of Cl'were measured in surface soil (0 to 30-cm
depth) at the the wastewater application areas with respect to the control area (65 mg/L).
This pattern may be explained by the evapotranspiration of salts in the applied wastewater
by the very dense vegetation at the application areas.
     Because  evapotranspiration at the OLF site is insufficient to produce the measured
concentations of salts in the groundwater, it appears that the dissolution of naturally present
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minerals may be the primary source of groundwater salinity.  Therefore, this subsection
includes a discussion of mineral dissolution as the most probable mechanism for the geo-
chemical evolution of groundwater below the OLF site.
     The development of groundwater quality below the Campbell Soup QLF can be con-
ceptualized as follows.  After the start of OLF wastewater application, some fraction of the
treated effluent would infiltrate the soil.  Due to the negligible hydraulic gradient of the water
table (0.0043 m/m) and the relatively low hydraulic conductivity of the  Bonham Formation
clays (k = 10"6 cm/s), the infiltrated water would tend to remain in the pore spaces or move
laterally very slowly. The most rapid transmission of water would occur through the highly
permeable weathered contact zone, soil macropores, and fractures in the clays of the Bonham
Formation.
     Based on the application of Darcy's law to the water level data (mean hydraulic gradient
of 0.0043 m/m), an assumed effective  porosity of 0.35, and slug test data (*  between 10'3
and 10~* cm/s) presented previously, the groundwater would travel horizontally at a velocity
in the range of 0.4 to 4-m/yr. Thus, groundwater which had infiltrated through the soil to the
weathered contact zone at the start of wastewater applications in 1964 would have moved
laterally a maximum distance of less than 100-m in the 24-years that the site has been in
operation.  Because of these low groundwater velocities in the aquifer  at the OLF site, sta-
tionary groundwater would tend to continually dissolve and eventually approach equilibrium
with naturally present  minerals in the surrounding clays.  Therefore, with time the ionic
concentration of the groundwater would tend to increase. This trend  is suggested by the
data presented in Figure 9-6. A more rigorous description of the theoretical basis for this
proposed mechanism for the geochemical development of brackish groundwater below the
OLF system is presented in the the following discussion.
      From a geochemical viewpoint, the development of a slightly saline aquifer at the Paris,
Texas site can be explained in terms of mineral availability and mineral  solubility.  There are
several soluble sedimentary minerals  that release S042' or CI" upon dissolution. Gypsum
(CaSO4 -2H2O) and anhydrite (CaSO4) are the most common of the sulfate bearing minerals.
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Highly soluble chloride minerals such as halite (NaCI) and sylvtte (KCI) often occur as salt
strata originally deposited during evaporation of closed or restricted marine basins several
million years ago. Chloride minerals of sedimentary origin dissolve rapidly in water.  Labo-
ratory analyses of soil samples collected at the OLF site as well as the geologic history of
the region confirm the deposition and current presence of these minerals in the Bonham
Formation.
     The relatively high ionic concentrations of  sodium,  chloride,  and sulfate in the
groundwater at the OLF site can be described as the end result of a number of interrelated
geochemical processes.  The four principal geochemical processes are represented by the
reactions:
           CaSO4 2H20 -Cat* + SOf + 2H20                                   (9-3)
       Co2* + 2Na(adsorbed) => 2Ncf + Ca(adsorbed)                               (9-4)
            CaC03 + H2C03 -2Ccf" + 2HCO,'                                   (9-5)
                   NaCl-4Na* + Cr                                           (9-6)
where (adsorbed) denotes cations adsorbed on clays. The dissolution and precipitation of
gypsum (CaSO4  2H2O)  represents significant mechanisms for the addition or removal of
salinity from the groundwater at the OLF site. Because gypsum deposits typically contain
magnesium, the dissolution of gypsum will also result in an increase in the concentration of
magnesium in groundwater. Although the dissolution and precipitation of gypsum involve
equimolar  concentrations of  CaSO4  2H2O (equation 9-3), calcium concentrations in
groundwater are usually less than that of sulfate since calcium may replace exchangeable
sodium (equation 9-4) or magnesium on the soil or precipitate as CaCO3 (equation 9-5).<34)
     The exchange of calcium for sodium on the clays of the Bonham Formation is repre-
sented by equation 9-4.  The equilibrium for equation 9-3 is far to the right as long as there
is appreciable Na*on the exchange sites of the clays. Equation 9-3 will proceed to the right
as long as the activity product [Caz*][SO42~] is less than the equilibrium constant for gypsum
and as long as gypsum  is available for dissolution.'61 The removal of Ca2*from solution by
exchange with Na*causes the groundwaterto become or remain undersaturated with respect
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to gypsum, thereby enabling gypsum dissolution to continue. Thus, the influx of Ca2*derived
from the dissolution of gypsum causes increased Na* (and Mg2*) concentrations as the cation
exchange reactions adjust to maintain equilibrium. The increased Ca2+ concentrations also
cause the solubility product of calcite to be exceeded  and drive equation 9-5 to the left
resulting in the precipitation of calcite. The precipitation of calcite would cause a  loss of Ca2*
and HCCV, and dissolution of more gypsum. Because the HCO3'content in groundwater is
primarily derived from soil zone CO2 and from dissolution of calcite and dolomite, the removal
of HCO3'due to precipitation of calcite would result in a decrease in groundwater buffering
capacity and with this decrease, the increased probability of a trend towards decreasing pH.
Given enough time, a state of equilibrium may be reached and groundwater HCO3"  con-
centrations would eventually rise as HCO3" equilibrated with atmospheric CO2.
     Because the clay deposits of the Bonham Formation have had the opportunity to contain
marine water, the presence of chloride in the soil at the OLF site in not unexpected.  The
repeated transgression of ancient seas (Chapters) in north-central Texas provided conditions
suitable for the deposition of sediments which could entrap saline water (connate water).
Flushing of the Bonham Formation by rainfall is negligible due to the low  permeability of the
clays and the lack of significant quantities of precipitation. The lack of deep percolation would
permit chloride in the soil to remain near the land surface after millions of years of potential
flushing. With the initiation of land treatment operations, excess quantities of water beyond
the crop requirements have been supplied. The excess water can percolate down through
the clay and dissolve the ancient chloride deposits.
     Only a very small amount of  chloride need be present in the clay for  relatively high
concentrations to develop in the groundwater.  Because chloride generally does participate
in chemical or biological reactions within the groundwater systems, it is often considered to
be a conservative substance.  As such, once dissolution of NaCI occurs,  CI" will remain in
solution, unaffected by precipitation, ion exchange, or biochemical degradation.  At  equi-
librium, the soil pore water concentration of CI- is the same concentration (per unit volume)
as the soil concentration of CI'.  Analysis of unleached soil samples collected from the control
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area (Table 7-13) indicated that the soil pore water Cl" concentration within the unsaturated
zone of the Bonham clay was roughly equivalent to the mean Cl" content of the groundwater.
Thus, it appears probable that the natural mineral content of the Bonham Formation contains
enough Cfto produce the Crconcentraion found in the groundwater at the site.
     The groundwater monitoring data collected at MW-1, MW-2, and MW-3 support the
proceeding  discussion of the development aqueous geochemistry at below the Campbell
Soup OLF site. Water samples collected from the older areas (i.e., areas with over 24-years
of wastewater application) have had a correspondingly long period of time to progress towards
aqueous geochemical equilibrium; therefore, the relatively high concentrations of Na*, SO42',
Ct, and HCO3" measured in groundwater samples collected at MW-1 and MW-2 can be
expected. However, in the newer areas near MW-3, groundwater has had significantly less
time (<10-years)  to equilibrate with clay minerals and atmospheric CO2.  Thus, the ionic
concentrations of the major cations  at MW-3 are expected to be slightly less than those at
MW-1 and MW-2. The field data (Table 9-1, 9-2, and 9-3) support this prediction, and the
low concentration of HCO3' in  the water at  MW-3 provide further evidence of the relatively
recent recharge of treated wasetwater and the development of the groundwater chemistry
at the site.
Summary of the Conceptual Model for Groundwater Recharge
     Based on the findings of the hydrogeologic study, a conceptual model of the devel-
opment and recharge of an semi-confined aquifer below the site was developed (Figure 9-7).
In this study, the aquifer system below the OLF site was conceptualized as having one primary
flow system, through fractures and along the erosional contact with slow recharge through
the pore spaces of the Bonham Formation clays.  These flow systems exist in the heavy,
inorganic clay and marl of the Bonham Formation (a unit of the Austin Chalk Group), and
are confined from below by the relatively impermeable Maribel Shale, the upper part of the
Eagle Ford Group.
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               RECHARGE
Wastewater Application
   Precipitation
RECHARGE
           POTENTIOMETRIC SURFACE
           OF CONFINED AQUIFER
                   Ephemeral Stream
                 BONHAM FORMATION - upper confining unit (vertical leakage)
           EROSIONAL CONTACT (CONFINED AQUIFER)

                          MARIBEL SHALE - lower confining unit
                                                                            \
                                                                              AUSTIN
                                                                              GROUP
                                                                            \
                                               EAGLE FORD
                                               GROUP
Figure 9-7. Conceptual Model of the Groundwater Recharge

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     As shown in Figure 9-7, the aquifer is recharged slowly by water (mostly treated
wastewater with some precipitation) moving vertically downward through pore spaces and
fractures within the Bonham Formation. Within the aquifer, the principal zone of high hydraulic
conductivity is located at the erosional contact between the Austin and Eagle Ford Groups.
Preferential flow within fractures and macropores may represent a secondary pathway for
the transmission of groundwater.
     The evapotranspirative concentration of salts in the deep percolate may result in above
"background" accumulations of salts at the soil surface, even though leaching would continue
to occur. The combined effects of mineral dissolution and evapotranspiration would result
in increases in the salinity of the porewater. As a result of the lack deep percolation (due to
low precipitation and the low hydraulic conductivity of the clays), readily soluble minerals had
remained in the soil until the initiation of OLF operations.  Water moving down through the
soil will leach these naturally present, highly soluble minerals from the Bonham Formation.
     In addition, the application and subsequent infiltration of large volumes of wastewater
may result in the development of new solution channels as well as the enlargement of existing
channels. These channels can act as conduits for the seepage of large volumes of water
through the subsurface.
     Due to the negligible dip of the lower confining unit (Eagle Ford Group) and the relatively
flat regional surface topography in the area, a negligible hydraulic gradient would result.
Because of the small hydraulic gradient and the low hydraulic conductivity of the  Bonham
Formation within the pore spaces and along fractures, infiltrated water would tend to remain
relatively stationary once a unit area reaches saturation. Thus, the stationary water would
dissolve  and remove minerals from the surrounding clay until the water moved on or the
soil-water system reached a point of stability (chemical equilibrium). The rate of groundwater
movement in the Bonham Formation over the entire area of the OLF site is expected to be
uniformly low. Therefore, groundwater quality within the Bonham Formation at the OLF site
would tend to be similar. However, groundwater quality at different locations are not expected
to be of identical quality because of the extremely slow rate of flushing.  Localized concen-
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trations of specific minerals, such as gypsum or sodium chloride, may result in nonuniform
concentrations of these constituents in the groundwater within the Bonham Formation. This
mechanism of groundwater recharge and mineral dissolution is hypothesized to have resulted
in the development of moderately saline aquifer below the OLF site.
     Assuming water table conditions, Smith Creek would penetrate the surface of the
aquifer at topographically low regions of the OLF site. These low areas may also correspond
to groundwater discharge areas. However, it is not expected that significant discharge to
the Smith Creek would occur due to the low hydraulic conductivity of the saturated Bonham
Formation clays. These  predictions are supported by the fact that long-term water quality
monitoring data collected at the Smith Creek monitoring station (Chapter 6) did not indicate
elevated concentrations of sodium, calcium, suit ate, and chloride in the Creek. Thus, because
groundwater discharge as baseflow is predicted to be  negligible and there are no springs
within the vicinity of the  OLF site nor are there pumped wells screened within the  aquifer,
the major mechanism for aquifer discharge is unknown. However, due to the relatively low
hydraulic conductivity of the Bonham Formation, groundwater would tend to travel at such
a slow rate that the discharge would be difficult to identify either visually or by influences on
the chemical quality of receiving water bodies. In addition to surface discharge as baseflow
and springs, the groundwater may discharge by seepage into Lake Crook, to the north, or
by discharge into other formations in the subsurface along faulting planes and fracures.
SUMMARY
     Twenty six groundwater samples collected from three monitoring wells (MW-1, MW-2
and MW-3) between 1987 and 1989 were analyzed for the constituents listed in Appendix
B.  In general, the water was moderately saline and no purgable and extractable organics
were detected. Statistical analysis (ANOVA at p < 0.05)  of the data indicated that, for the
major ions present, groundwaterquality at each well remained uniform over the 3-year period
of sampling. However,  statistically significant differences in groundwater quality between
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the well locations were found.  The consistency of groundwater quality at each location
permitted the use of mean values for comparisons between wells and for the graphical
presentation of data.
     State records indicated that no wells in Lamar County were screened within the Austin
Chalk-Eagle Ford Group.  In addition, no springs which issued from the Bonham Formation
were identified within Lamar County or any adjacent counties.
     Several graphical techniques were used to visually examine the similarity in water
quality among the three monitoring well locations and the lysimeter data. Schoeller plots of
major-ion concentrations  indicated  that water collected from  all three monitoring wells
exhibited similar ionic composition ratios. These waters appeared to have undergone similar
paths of geochemical evolution with a trend towards increasing ionic concentration from the
north edge of the OLF site to the south  edge. This trend is in agreement with the relative
length of time that the north (<10-years) and south (>20-years) areas have been in operation.
Ionic ratios of major ions in groundwater data collected from lysimeters at the site in 1968
exhibited excellent agreement with comparable ionic ratios for  more recent samples from
MW-2 (1987-1988). The pattern of increasing ionic compostion with relatively small changes
in ionic ratios strongly suggested a trend towards the concentration of dissolved minerals in
the relatively slow moving groundwater.
     The geochemical data indicated that sulfate-chloride facies were dominant for
groundwater at all three monitoring wells (MW-1, MW-2 and MW-3) and for the lysimeter
data collected in 1968.  Thus, the similarity of water quality among well locations as well as
the similarity in the pattern of geochemical evolution over the past 24-years was strongly
suggested.
     The infiltration of treated wastewater, development of water-table aquifer, the disso-
lution of soluble minerals from the soil and resultant effects on the quality of groundwater
below the site were strongly suggested by the groundwater geochemical data, soil data, the
expected rate of infiltration, field hydraulic conductivity and water level measurements, and
the magnitude of the volume of wastewater applied.
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                                 CHAPTER 10

                            GLOSSARY OF TERMS
Absorption
Taking up, incorporation, or assimilation, as of liquids in solids or of gases in liquids.
Adsorption
Adhesion of gas molecules, or of ions or molecules in solution to the surface of solid bodies
with which they are in contact.
Alluvium
Detrital deposits made by streams on river beds and flood plains; esp. a deposit of silt or
silty clay laid down during a time of flood. The term applies to deposits of recent origin. It
does not include subaqueous sediments of seas and lakes.
Aqulclude
A body of rock that will absorb water slowly but will not transmit it fast enough to supply a
well or spring.
Aquifer
A body of rock that is sufficiently permeable to conduct groundwater and to yield economically
significant quantities of water to wells and springs.
Aquitard
A confining bed that retards but does not prevent the flow of water to or from an adjacent
aquifer; a leaky confining bed.  It does not readily yield water to wells or springs, but may
serve as a storage unit for groundwater.
Aragonlte
An orthorhombic mineral. CaCO3. trimorphous with calcite and vaterfte.  It occurs in beds of
gypsum and iron ore, and in shallow marine banks, an in pearls and some shells.
Barlte
An orthorhombic mineral, BaSO4, with a specific gravity of 4.5 It is the principal ore of barium.
Baseflow
That part of stream discharge from groundwater seeping into the stream.
Calcite
A common rock forming  mineral, CaCO3. Commonly white or gray, it has perfect rhombo-
hedral cleavage and reacts readily with  cold dilute hydrochloric acid.  Calcite is the chief
constituent of limestone and most marble.
Celestlte
An orthorhombic mineral, SrSO4. The principal ore of strontium.
Clastic
Pertaining to a rock or sediment composed principally of fragments derived from pre-existing
rocks or minerals and transported some distance from their place of origin; also said of  the
texture of such a rock.
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Common-Ion effect
The decrease in solubility of a salt dissolved in water already containing some of the ions of
the salt.
Confined aquifer
A aquifer bounded above  and below by impermeable beds, or by beds of distinctly lower
permeablity than that of the aquifer itself; an aquifer containing confined groundwater.
Confined groundwater
Groundwaterthat is under suffcient pressure to rise above the level at which it is encountered
in a well; it may or may not flow to or above the ground surface.  Its upper surface is the
bottom of an impermeable bed.
Connate water
Water entrapped in the interstices of a sedimentary rock at the time the rock was deposited.
Darcy's law
An equation that can be used to calculate the quantity and velocity of water moving through
a porous media.
Deltaic
Pertaining to or characterized by a delta; e.g. "deltaic  sedimentation.
Dlaspore
A gray or yellowish orthorhombic mineral, AIO(OH), dimorphous with boehmite, It is found
in bauxite deposites.
Dip
The angle that a stratum or any planar feature makes with the horizontal, measured per-
pendicular to the strike and in the vertical plane.
Discharge area
An area in which there are upward components of hydraulic head in an aquifer. Groundwater
is flowing toward the surface in a discharge area and may escape as a spring, seep, or
baseflow or by evaporation and transpiration                	
Dolomite
A common rock forming mineral, CaMg(CO3)2. Part of the magnesium may be  replaced ny
ferrous iron. Dolomite is light colored and has perfect rhombohedral cleavage. Most dolomite
is associated and often interbedded with limestone.
Effective porosity
The percent of the total volume of a given mass of soil or rock that consists of interconnecting
voids.
Electromagnetic survey
A geophysical  method employing the generation of electromagnetic waves at the earth's
surface; when the waves impinge on a conducting formation (such as saline groundwater or
an ore body) at depth they induce currents that are the source of new waves radiated from
the conductors and detected by instruments at the surface.
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Ephemeral stream
A stream or portion of a stream which flows briefly in direct response to precipitation in the
immediate vicinity, and  whose channel is at all times above the water table.
Evaporite
One of the sediments which are deposited from aqueous solution as a result of extensive or
total evaporation. Examples include anhydrite, rock salt, various nitrates and borates.
Evapotransplratlon
That portion of the precipitation returned to the airthrough evaporation and plant transpiration.
Fissile
Capable of splitting easily along closely spaced parallel planes, e.g. bedding in shale.
Glauconite
A green mineral closely  related to the micas and essentially a hydrous potassium iron silicate.
It is common in sedimentary rocks from Cambrian to the present. It is an indicator of very
slow sedimentation.
Gypsum
A widely distributed mineral consisting of hydrous calcium sulfate: CaSCy 2H2O.  It is the
commonest sulfate mineral, and is frequently associated with halite and anhydrite in evap-
orites, forming thick, extensive beds.
Hiatus
A break or interruption  in the continuity of a stratigraphic record, such as the absence of
rocks that would normally be present in a sequence but were never deposited.
Humlc acid
Black acidic organic matter extracted from soils, low rank coals, and other decayed plant
substances by alkalis.  It is insoluble in acids and organic solvents.
Hydraulic conductivity
The rate at which water flows in m/d through a cross section of one square meter under a
unit hydraulic gradient.
Ion exchange
A process by which an ion in a mineral lattice is replaced by another ion that was present in
solution.
Inorganic
Pertaining or relating to a compound that contains no carbon.
Lamina
The thinnest recognizable layer in a sediment or sedimentary rock, differing from other layers
in color, composition, or particle size; and commonly 0.05 to 1.00 mm thick.
Lithology
The description of rocks on the basis of such a characteristics as color, mineralogic com-
position, and grain size.
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Marl
A term loosely applied to a variety of materials, mostly unconsolidated earthy deposits chiefly
consisting of an intimate mixture of clay and calcium carbonate,  usually including shell
fragments and sometimes glauconite. It is formed under marine and especially freshwater
conditions.
Megafosstls
Fossils that are large enough to be seen with the unaided eye.
Neutron probe log
A radioactivity log that indicates the intensity of radiation produced  when rocks or soil in a
borehole are bombarded by neutrons. It indicates the presence of fluids.
Perched groundwater
Unconfined  groundwater separated from the underlying main body  of groundwater  by
unsaturated rock.
Pore space
The volume between mineral grains in a porous medium.
Potentlometrlc surface
An imaginary surface representing the total head of groundwater and defined by the level to
which water will rise in a well.
Recharge area
An area in which there are downward components of hydraulic head in an aquifer. Infiltration
moves downward into the deeper parts of an aquifer in a recharge area.
Saturated zone
The zone in which the voids in the rock or soil are filled with water at a pressure greater than
atmospheric. The water table is at the top of the saturated zone in an unconfined aquifer
Secondary porosity
The porosity developed in a rock after its deposition or emplacement, through such processes
as solution or fracturing.
Semlconflned aquifer
An aquifer confined by a low-permeability layer that permits water to slowly flow through it.
During pumping of the aquifer, recharge to the aquifer can occur across the confining layer.
Also known as a leaky confined aquifer.
Series
A chronostratigraphic unit next in rank below system and above stage; the rocks formed
during an epoch of geologic time.
Shale
A fine-grained detrital sedimentary rock, formed by the compaction  of clay, silt, or mud.  It
has a finely  laminated structure,  which gives it fissility along which the rock splits readily,
especially on the weathered surfaces.
Solubility product
The equilibrium constant that decribes a  solution of a slightly soluble salt in water.
                                       138

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Strike
The direction taken by a structural surface, e.g. a bedding or fault plane as it intersects the
horizontal.
Transgression
The spread of the sea over land areas; also, any change that brings offshore, deep-water
environments to areas formerly occupied by nearshore, shallow-water condtions.
Unconformable
Said of strata that do not succeed the underlying rocks in immediate order of age or in parallel
position.
Unsaturated zone
The zone between the land surface and the watertable. It includes the root zone, intermediate
zone, and capillary fringe. The pore spaces contain water at less than atmospheric pressure,
as well as air and other gases.  Also called the zone of aeration and the vadose zone.
Watertable
The surface of an unconfined aquifer or confining bed at which the pore water pressure is
atmospheric.
Weathering
The destructive processes by which rocks are changed on exposure to atmospheric agents
at or near the earth's surface, with little or no transport of the loosened or altered material.
Well, fully penetrating
A well drilled to the bottom of an aquifer, constructed in such a way that it withdraws water
from the entire thickness of the aquifer.
Well, partially penetrating
A well constructed in such a way that it draws water directly from a fractional part of the total
thickness of the  aquifer. The fractional part may be located at the top or the bottom or
anywhere in between in the aquifer.
                                       139

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                       CHAPTER 11



                   CONVERSION FACTORS
METRIC TO U.S. UNITS
Metric Name
centimeter
cubic meter

degrees Celsius

gram
hectare
kilogram
kilometer


liter

metric ton

meter

kiloNewtons per
square meter,
kilo Pascal
Symbol
cm
m3

C

g
ha
kg
km


L

t

m

kN/m2,
kPa
Multiplier
0.3937
264.17
35.31
1.8(C)+32

0.0022
2.4711
2.205
0.6214
3,281
1,094
0.0353
0.2642
1.10
2205
3.2808
39.37
1.4498X10'1
Symbol
in.
gal
ft3
F

Ib
ac
Ib
mi
ft
yd
ft3
gal
ton
Ib
ft
in
Ib/in2,
psi
U.S. Name
inch
gallons
cubic feet
degrees
Fahrenheit
pound
acre
pound
mile
feet
yard
cubic foot
gallon
ton (short)
pounds
foot
inch
pounds per
square inch
                           140

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                               REFERENCES

1. Standard Methods for the Examination of Water and Wastewater. (1985) Am. Pub-
lic Health Assoc., Washinton, D.C.

2. Messenger, A.L. (1981) "Comparison of Sealed Digestion Chamber and Standard
Method COD Tests." Journal of the Water Pollution Control Federation, 53(2):232-236.

3. U.S. Environmental Protection Agency. (1986) Test Methods for Evaluating Solid
Waste. SW-846, Volumes 1-4 (Third Edition). National Technical Information Service,
Springfield, VA.

4. Methods of Soil Analysis, Part 2. (1982) Edited by A.L. Page, R.H. Miller and D.R.
Keeney.  Second Edition. American Society of Agronomy, Inc. and Soil Science Society of
America, Inc.

5. Tabatabai, M.A. and W.A. Dick. (1983) "Simultaneous Determination of Nitrate, Chlo-
ride, Sulfate and Phosphate in Natural Waters by Ion Chromatography." Journal of Envi-
ronmental Quality, 12:209.

6. Freeze, R.A. and J.A. Cherry (1979) Groundwater. Prentice-Hall, Inc.  Englewood
Cliffs, NJ, 128.

7. Minitab, Inc. (1985) Minitab Statistical Software (Release 6.1.1) State College. PA.
8. Snedecor, G.W. and W.G. Cochran. (1980) Statistical Methods. (Seventh Edition).
Iowa State University Press, Ames, Iowa.

9. Gilde, L.C. (1973)  "Land Treatment of Food Processing Wastewaters." Journal of the
Irrigation and Drainage Division, ASCE. IR 3:339-352.

10. Thornthwaite, C.W. (1969) "An Evaluation of Cannery Waste Disposal by Overland
Flow Spray Irrigation." Publications in Climatology, Vol. XXII, No.2.

11. Thomas, R.E., Law, J.P. Jr. and C.C. Harlin. (1970) "Hydrology of Spray-Runoff
Wastewater Treatment." Journal of the Irrigation and Drainage Division, ASCE. IR
3:289-298.
12. de Figueiredo, R.F., Smith, R.G. and E.D. Schroeder. (1984) "Rainfall and Overland
Flow Performance."  Journal of Environmetal Engineering, ASCE. 110(3):678-694.

13. Martel, C.J., Jenkins, T.F., Diener, C.J. and  P.L Butler. (1982) "Development of a
Rational Design Procedure for Overland Flow Systems." CRREL Report  82-2. U.S. Army
Corps of Engineers, Hanover, NH.

14. Liliestrand, H.M. (1985)  "Average Rainwater pH, Concepts of Atmospheric Acidity, and
Buffering in Open Systems." Atmospheric Environment, 19(3):487-499.

15. Shakelford, C.D.  (1988) Diffusion of Inorganic Chemical Wastes In Compacted
Clay.  Ph.D. Dissertation, The University  of Texas at Austin.

16. U.S. Environmental Protection Agency. (1983) Process Design Manual for Land
Treatement of Municipal Wastewater.  USEPA 625/1-81-013, Center for Environmental
Research Information, Cincinnati,  OH.

17. U.S. Environmental Protection Agency. (1983) Process Design Manual: Land  Appli-
cation of Municipal  Sludge. USEPA 625/1-83-016, Center for Environmental Research
Information, Cincinnati, OH.

18. Harter, R.D. (1979) "Adsorption of Copper and Lead by Ap and B2 Horizons in Several
Northeastern United States  Soils." Journal of the Soil Science Society of America,
43:679-683.

19. Korte, N.E., Skopp, J., Fuller, W.H., Niebla,  E.E. and B.A. Alesii. (1976) "Trace Ele-
ment Movement in Soils: Influence of Soil Physical and Chemical Properties." Soil Sci-
ence, 123:350-359.
                                      141

-------
20. Nordstrom, P.L. (1982) "Occurrence, Availability, and Chemical Quality of Ground
Water in the Cretaceous Aquifers of North-Central Texas" Vol. 1-2, Report 269, Texas
Department of Water Resources, Austin, TX.

21. Suries, M.A. Jr. (1987) "Stratigraphy of the Eagle Ford Group (Upper Cretaceous) and
Its Source-Rock Potential in the East-Texas Basin." Baylor Geological Studies, Bulletin
No. 45, Baylor University, Waco, TX.

22. Baker, E.T. Jr., Long, AT. Jr., Reeves, R.D. and L A. Wood (1963) "Reconnaissance
Investigation of the Ground-Water Resources of the Red River, Sulphur River, and
Cypress Creek Basins, Texas." Bulletin 6306, Texas Water Commision, Austin, Texas.

23. McNulty, C.L. (1965) "Lithology of the Eagle Ford-Austin Contact in Northeast Texas."
Texas Journal of Science, 48:46-53.
24. Hvorslev, M.J. (1951) "Time Lag and Soil Permeability in Ground-Water Observa-
tions." Bulletin No. 36, Waterways Experiment Station, Corps of Engineers, Vicksburg,
MS.
25. Naval Facilities Engineering Command (NAVFAC). (1971) Design Manual - Soil
Mechanics, Foundations, and Earth Structures. Chapter 4. Field tests and Measure-
ments. Dept of the Navy, Alexandria, VA.
26. Cedergren, H.R. (1989) Seepage, Drainage, and Flow Nets 3rd Edition, John Wiley
& Sons, N.Y., NY.

27. Bouwer, H. and R.C. Rice. (1976) "A Slug Test for Determining Hydraulic Conductivity
of Unconfined Aquifers with Completely or Partially Penetrating Wells." Water Resources
Research 12(3).
28. Bouwer, H. (1989) "The Bouwer and Rice Slug Test - An Update." Ground Water,
27(3):304-309.
29. Cooper  H.H, Bredehooeft and I.S.  Papadapoulous. (1967) "Response of a Finite-
Diameter Well to an Instantaneous Charge of Water." Water Resources Research 3(1).

30. Thompson, D.B. (1987) "A Microcomputer Program for Interpreting Time-Lag Perme-
ability Tests." Ground Water. 25(2).

31. Winslow. A.G. and L.R. Kister. Jr. (1956) "Saline-Water Resources of Texas." U.S.
Geological Survey Water Supply Paper, 1365.

32. Brune, G. (1981) Springs of Texas Volume 1. Branch-Smith, Fort Worth, Texas.
33. Fetter, C.W., Jr. (1980) Applied Hydrogeology. C.E. Merrill Publishing Company,
Columbus, OH, 337-338.
34. Oster, J.D. and K.K. Tanji. (1985) "Chemical Reactions Within The Root Zone Of Arid
Soils." Journal of Irrigation and Drainage Engineering. 11:3,207-217.
                                      142

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      APPENDIX A
WELL CONSTRUCTION DATA
          143

-------
                     WELL CONSTRUCTION DATA
                       UNIVERSITY OF TEXAS AT AUSTIN
                   ENVIRONMENTAL ENGINEERING PROGRAM
Client: U.S.EPA
Job No.: 68-01 -7266
Well Use: Monitoring
Site: Paris, Texas
Well No.: MW-1
Page 1 of 1
Drilling Summary

Total Depth: 5.49-m
Borehole Diameter: 10.2-cm
Rig Type: CME Rotary Auger
Elevation (MSL)
Land Surface: 152.26-m
Drillers: U.S.EPA Ada. OK
Bit(s): Hollow Stem
Top of Casing: 152.64-m
Water Level: 151.73-m
Well Design

Casing MateriahStainless Steel
              316
Screen MateriahStainless Steel
              316
Slot Size: 0.025-cm
Seals Material: Bentonite
Filter Material: Washed Sand
Grout: Portland Cement
Surface Casing/Cap:Stainless Steel
Diameter: 5.1-cm
Length: 3.28-m
Diameter. 5.1-cm
Length:  1.52-m
Setting: 149.36 to 147.84-m
Setting: 149.67 to 149.97-m
Setting: 146.77 to 149.67-m
Setting: 152.26 to 151.34-m
Setting: 152.26 to 152.64-m
Well Development:
Method: Vacuum lift system
Remarks: No forced flushing, after
development, well produced about
19-L of water per hour.
a
o
ac
o
z
                                CEMENT
BACKFILL

Bentonite
       SAND
a.
O
ac
o

I
                                                             EAGLE FORD
                                                             SHALE
                                    144

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                     WELL CONSTRUCTION DATA
                       UNIVERSITY OF TEXAS AT AUSTIN
                   ENVIRONMENTAL ENGINEERING PROGRAM
Client: U.S.EPA
Job No.: 68-01 -7266
Well Use: Monitoring
Site: Paris. Texas
Well No.: MW-2
Page 1 of 1
Drilling Summary

Total Depth: 7.53-m
Borehole Diameter: 10.2-cm
Rig Type: CME Rotary Auger
Elevation (MSL)
Land Surface: 152.65-m
Drillers: U.S.EPA Ada. OK
Brt(s): Hollow Stem
Top of Casing: 153.08-m
Water Level: 152.06-m
Well Design

Casing MateriakStainless Steel
              316
Screen MateriakStainless Steel
              316
Slot Size: 0.025-cm
Seals Material: Bentonrte
Filter Material: Washed Sand
Grout: Portland Cement
Surface Casing/Cap:Stainless Steel
Diameter: 5.1-cm
Length: 6.13-m
Diameter 5.1-cm
Length:  1.52-m
Setting: 146.95 to 145.45-m
Setting: 147.55 to 147.25-m
Setting: 147.25 to 145.15-m
Setting: 152.65 to 151.75-m
Setting: 152.65 to 153.08-m
Well Development:
Method: Vacuum lift system
Remarks: No forced flushing, after
development, well produced 19-L of
water per hour.
O
oc
O
I
                                CEMENT
     BACKFILL
     Bentonrte
                                            &
                                            8
                                            oc
                                            O
                               EAGLE FORD
                               SHALE
                                   145

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                      WELL CONSTRUCTION DATA
                        UNIVERSITY OF TEXAS AT AUSTIN
                   ENVIRONMENTAL ENGINEERING PROGRAM
Client: U.S.EPA
Job No.: 68-01 -7266
Well Use: Monitoring
Site: Paris, Texas
Well No.: MW-3
Page 1 of 1
Drilling Summary

Total Depth: 7.82-m
Borehole Diameter: 10.2-cm
Rig Type: CME Rotary Auger
Elevation (MSL)
Land Surface: 142.51-m
Drillers: U.S.EPA Ada, OK
Bit(s): Hollow Stem
Top of Casing: 142.71-m
Water Level: 142.68-m
Well Design

Casing MateriakStainless Steel
              316
Screen MateriakStainless Steel
              316
Slot Size: 0.025-cm
Seals Material: Bentonite
Filter Material: Washed Sand
Grout: Portland Cement
Surface Casing/Cap:Stainless Steel
Diameter 5.1-cm
Length: 5.84-m
Diameter: 5.1-cm
Length:  1.52-m
Setting: 136.71 to 135.20-m
Setting: 137.48 to 137.18-m
Setting: 137.18 to 134.89-m
Setting: 142.51 to 141.61-m
Setting: 142.51 to 142.71-m
Well Development:
Method: Vacuum lift system
Remarks: No forced flushing, after
development, well produced 19-L of
water in 4 minutes.
2
O
z

                                                                CEMENT
     BACKFILL
     Bentonite
            CO
                                            O
                                            DC
                                            O
                              EAGLE FORD
                              SHALE
                                    146

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                              APPENDIX B
           GROUNDWATER CONSTIUENTS ANALYZED
Inorganic Cations
Aluminum
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Nickel
Potassium
Silver
Selenium
Sodium
Strontium
Thallium
Titanium
Vanadium
Zinc
Extractable Organic Com-
pounds
n-Nitrosodimethylamine
Phenanthrenel ,2-Di-
phenylhydrazine/azobenzene
Benzidine
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1.2-dichlorobenzene
Hexachloroethene
bis(2-Chloroisopropyl)ether
bis(2-Chloroethyl)ether
n-Nitrosodi-n-propylamine
Nitrobenzene
Hexachlorobutadiene
1,2,4-TrichIoro benzene
Naphthalene
bis(2-Chloroethoxy)methane
Isophorone
Hexachlorocyclopentadiene
(HCCP)
2-Chloronaphthalene
Acenaphthlene
Acenaphthene
Dimethyl phthalate
2,4-Dinitrotolulene
2,6-Dinitrotolulene
4-Chlorophenyl phenyl ether
Fluorene
Oiethyl phthlate
n-Nitrosodiphenylamine
Hexachlorobenzene (HCB)
                                      147

-------
4-Bromophenyl phenyl ether
Anthracene
Di-n-butylphthlate
Fluoranthene
Pyrene
Benzyl butyl phthlate
Bis(2-ethylhexyl)phthlate
Benzo(a)anthracene
Chrysene
3,3'-Dichlobenzidine
Oi-n-octylphthlate
Benzo(b and/or k)fluoranthene
Benzo-a-pyrenelndeno (1,2,3-cd)
pyrene
Dibenzo(a,h)anthracene
Benzo(ghi)perylene
2-Chlorophenol
2-Nitrophenol
Phenol2,4-Dimethylphenol
2.4-Dichlorophenol
2,4,6-Trichlorophenol
4-Chloro-3-methylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
Pentachlorophenol
4-Nitrophenol
Miscellaneous Extractable
Orpanlcs
Hexanoic acid
Heptanoic acid
Octanoic acid
Decanal
Nonanoic acid
Decanoic acid
Dodecanoic acid
Tetradecanoic acid
Tridecanoic acid
Pentadecanoic acid
Hexadecanoic acid
Octadecanoic acidl-
Hexadecanol. acetate
n,n-Diethyl-3-methyl-benzamide
C3-Benzene
Heptanal
9-Hexadecenoic acid
Dichlorbenzene (3 isomers)
Benzothiazote
(1.V-Biphenyl]-2-ol
Isobutyl stearate
Isobutyl palmitate
Hexadecanol
3-(1-Methyl-2-pyrolidinyl)-pyridine

Puraeable Organic Compounds
Methylene chloride
1,1-Dichloroethene
1,1-Dichloroethane
trans-1,2-Dichloroethene
Chloroform
1,2-Dichloroethane
1,1,1-Trichloroethane
Carbon tetrachloride
Bromodichlormethane
Trichloroethene
Benzene
Bibromochloromethane
1,1,2-Trichloroethane
Bromoform
                                          148

-------
Tetrachloroethane
Tolulene
Chlorobenzene
Ethyl benzene
m-Xylene
o & p-Xylene (mixed)
Inorganic Anlona
Chloride
Ortho-phosphate phosphorous
Sulfate
NO,-NO2-N
Additional Analyses
Conductivity
Alkalinity
Ammonia
PH
TOC
                                         149

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      APPENDIX C


     SLUG TEST RESULTS
Distance to top
of casing, ft-ln.   Elapsed time, sec
SLUG TEST No. 1
2' 9"
2' 3.5"
2' 2"
1'9"
rr
1'5"
1'4"
1*3"
1'2"
1'1"
SLUG TEST No. 2
4'1"
3' 6"
2'8"
2' 4"
2' 2.5"
V9"
1'7"
1'6"
MW-3 7-18-89
0.0
20
30
40
50
60
70
80
90
100
MW-3 7-18-89
0.0
10
30
40
50
60
70
80
           150

-------
Distance to top
of casing, ft-ln.   Elapsed time, sec
SLUG TEST No. 3
3' 4"
31 7.5"
3' 2.5"
2' 8.5"
2' 6"
21 4.5"
2'1.5"
2' 0.5"
ra-
re"
rs"
1*4"
1'3"
SLUG TEST No. 4
4' 6"
4'0"
3' 6"
3'3"
3'0"
2' 6.5"
2'5"
2' 3"
2*1"
2'0"
1'8"
1'6"
1'5"
V4
MW-3 7-18-89
5
15
25
33
42
50
58
65
80
90
100
110
120
MW-3 7-18-89
0
11
18 -
24
34
40
50
57
60
70
80
90
100
110
              151

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Distance to top
of casing, tt-ln. Elapsed time, sec
SLUG TEST No. 5
9'1"
8*7"
8' 4"
fi'2"
8'0"
7'8"
T 6"
7' 4.5"
7-4 
SLUG TEST No. 6
9' 6"
9' 4"
9*2"
9'0"
8'8"
8' 6"
8' 4"
8' 2"
8'0"
7' 8"
MW-2 7-18-89
0
50
90
120
150
180
210
240
270
MW-2 7-18-89
0
20
40
70
115
150
195
250
305
375
152

-------