.■• LIBRARY OF THE UNIVERSITY OF ILLINOIS AT URBANA-CHAMPAICN ©28 l£65o no. 51- 52. ENGINEERING The person charging this material is re- sponsible for its return on or before the Latest Date stamped below. Theft, mutilation and underlining of books are reasons for disciplinary action and may result in dismissal from the University. UNIVERSITY OF ILLINOIS LIBRARY AT URBANA-CHAMPAIGN CONFERENCE jANtt^^ NOV 2 0CT3' jNTERUBRARf N0V19 MAR 2 FEB. 2 4 urn 1975 fat* LOAN 1978 hDiiarios HEC1D SEP t 5 WTD L161— O-1096 LOAN COPY ^ c. CIVIL ENGINEERING STUDIES ft- SANITARY ENGINEERING SERIES NO. 52 c OXYGEN RELATIONSHIPS IN SMALL STREAMS CO Be M CO 2? CJ pip in ES£™ N « "BRARY ■ » a. wiy of Illinois VRBMA, ILLINOIS 61801 By JOHN H. AUSTIN FRANK W. SOLLO Supported By FEDERAL WATER POLLUTION CONTROL ADMINISTRATION DEPARTMENT OF INTERIOR RESEARCH GRANT WP 01020 DEPARTMENT OF CIVIL ENGINEERING UNIVERSITY OF ILLINOIS URBANA, ILLINOIS JUNE, 1969 CIVIL ENGINEERING STUDIES Sanitary Engineering Series No. 52 OXYGEN RELATIONSHIPS IN SMALL STREAMS by John H. Austin Frank W. Sol lo Supported by Federal Water Pollution Control Administration Department of the Interior Research Grant WP 01020 Department of Civil Engineering University of Illinois Urbana, 1 1 1 inoi s June 1969 ABSTRACT The relative importance of atmospheric reaeration, photo- synthesis, biological oxidation, and benthal oxygen demand was ex- amined in a small polluted stream. Reaeration measurements were made by evaluating the decay of an added deficit and results compared with those obtained from various predictive equations. Photosynthesis and benthal oxygen demand were important factors in the oxygen balance. Equipment for measuring photosynthet ic oxygen production and benthal oxygen demand is described. A procedure for measuring reaera- tion is described. Contains 156 references. 1 1 Digitized by the Internet Archive in 2013 http://archive.org/details/oxygenrelationsh52aust ACKNOWLEDGEMENT This project has been supported primarily by the Federal Water Pollution Control Administration, Department of the Interior through Research Grant WP 01020. Support was also obtained from the National Science Foundation through NSF GY 2541, and the United States Public Health Service through Traineeship EH68-616. The following persons assisted with various phases of the project. CONSULTANTS R.S. Engelbrecht, Prof, of Sanitary Engineering, Dept. of Civil Engr. R.W. Larimore, Aquatic Biologist, Illinois State Natural History Survey T.E. Larson, Asst. Chief and Head, Chemistry Section, Illinois State Water Survey STAFF OF ILLINOIS STATE WATER SURVEY H.F. Mueller, Research Associate L.D. Resek, Research Assistant GRADUATE STUDENTS W.U. Brigham J. S. Jai n M.E. Leifer J.C. Hovious L.C. Diaz A.L. Roeske UNDERGRADUATE STUDENTS M.E. Leifer J.C. Hovious EMPLOYEES R. Endecavageh S. Porter J.E. Matherly J.M. Anderson G. Antipa S. Messman T. Duckett D. Thompson S. Dunn J. Hovious 1 1 1 OXYGEN RELATIONSHIPS IN SMALL STREAMS ABSTRACT H ACKNOWLEDGEMENT iii LIST OF TABLES vii LIST OF FIGURES ix CHAPTER I. INTRODUCTION 1 PRIOR RESEARCH 1 NEED FOR INVESTIGATION 3 SCOPE OF RESEARCH ** Reaeration 5 Photosynthet ic Production and Benthal Demand • '^ Biological 20 II. LOCATION OF PROJECT ^ DESCRIPTION OF THE DRAINAGE BASIN 24 SAMPLING STATIONS 2 7 III. METHODS 30 INSTRUMENTATION DEVELOPMENT 30 Gaging Stations 30 Dissolved Oxygen Meters 30 Signal Adapter 31 ANALYTICAL TECHNIQUES 33 Physical Methods 33 Chemical Methods 33 Biological Methods 36 IV IV. FIELD SURVEYS 4l SURVEYS OVER ENTIRE STREAM 4l MASS BALANCE STUDIES *+l V. REAERATION STUDIES ^7 REAERATION COEFFICIENT MEASUREMENT THEORY ^7 REAERATION COEFFICIENT FIELD MEASUREMENTS 5^ COMPUTATIONS USING PREDICTION EQUATIONS 59 RESULTS 61 DISCUSSION 67 CONCLUSIONS 71 VI. PHOTOSYNTHETIC OXYGEN PRODUCTION AND BENTHAL OXYGEN DEMAND 73 CONSTRUCTION OF CHAMBERS 73 RESULTS AND DISCUSSION 83 DISCUSSION OF PROBLEMS IN ANALYZING SMALL STREAMS . . 89 CONCLUSIONS 90 VII. BIOLOGIC STUDIES 91 INTRODUCTION 91 AUFWUCHS 91 PLANKTON, PARTICULATE AND DISSOLVED ORGANIC MATERIAL 106 BENTHOS 112 SYRTON 115 FISH 118 CONCLUSIONS 120 REFERENCES 122 APPENDICES 133 I. HYDROGRAPHS 13*t II. RESULTS OF FIELD SURVEYS 152 III. RESULTS OF MASS BALANCE STUDIES 1 58 IV. RESULTS OF REAERATION STUDY 175 V. RESULTS OF PHOTOSYNTHETIC OXYGEN PRODUCTION AND BENTHAL OXYGEN DEMAND STUDIES 180 VI. DEFINITION OF SYMBOLS 189 VI LIST OF TABLES Page 1. CI imatological Data for the Year June 1967 to June 1968 at Urbana, Champaign County, Illinois 26 2. Station Mileages 28 3. Mean Measured k Values Vs. Predicted Values 62 k. Summary of Data from Four Chambers 87 5- Mean Biomass of Abundant Taxa in the Benthos at the Four Biological Sampling Stations in the Saline Ditch- Salt Fork System, June 1 967 to June I968 113 6. Mean Biomass of Abundant Taxa in the Syrton at the Four Biological Sampling Stations in the Saline Ditch- Salt Fork System, June 1967 to June 1968 116 7o Results of Stream Survey of 11 March 1968 153 8. Results of Stream Survey of 27 June 1968 155 9- Results of Stream Survey of 17 July I968 I56 10. Summary Sheet 14-15 August 1968 2k Hour Stream Survey Station SB 5 159 11. Summary Sheet 14-15 August 1968 24 Hour Stream Survey Station SB 6 160 12. Summary Sheet 21-22 August 1968 2k Hour Stream Survey Station SB 5 161 13- Summary Sheet 21-22 August 1968 2k Hour Stream Survey Station SB 6 162 ]k. Summary Sheet 28-29 August I968 2k Hour Stream Survey Station SB 5 163 15. Summary Sheet 28-29 August I968 2k Hour Stream Survey Station SB 6 164 16. Summary Sheet 4-5 September I968 2k Hour Stream Survey Station SB 5 1 65 17* Summary Sheet 4-5 September I968 2k Hour Stream Survey Station SB 6 166 vi 1 18. Stream Cross Sections I76 19. Results of Reaeration Rate Measurements for 13 Aug. 1968 I77 20. Results of Reaeration Measurements for 20 Aug. 1968 I78 21. Results of Reaeration Measurements for 3 Sept. 1968 I79 22. Oxygen Production and Respiration in Benthos and Overlying Water, Station SB 5» 21-22 Aug. 1968 181 23. Oxygen Production and Respiration in Benthos and Overlying Water, Station SB 5, 28-29 Aug. 1968 182 2k. Oxygen Production and Respiration in Benthos and Overlying Water, Station SB 5> k-5 Sept. 1968 183 25« Oxygen Production and Respiration in Benthos and Overlying Water 184 26. Rank Order of Data for Four Chambers Station SB 5> July 26-September 5, 1968 185 27- Data for Four Chambers by Position Station SB 5, August 21-September 5, 1968 186 28. Rank Order of Data for Four Chambers by Day Station SB 5 1 87 vi 1 1 LIST OF FIGURES Page 1. Stream Discharges Above and Below Treatment Plant on 6 September 1967 13 2. Location of Project and Sampling Stations 25 3<> Five Place DO Meter 32 4. Flow Chamber with Recorder and Signal Adapter 43 5. DO Depletion Measured in Flow Chamber .... 45 60 Dissolved Oxygen Profile During Dosing 50 7. Oxygen Uptake with Time from _I_n Situ Benthic Measurements 55 8. Sulfite Dosing Equipment 56 9- Location of Dosing Points and Sampling Stations 58 10. Channel Cross Sections 60 11. Measured Vs. Predicted k Values 63 12. Measured Vs. Predicted k Values 64 13. Measured Vs. Predicted k Values 65 14. Measured Vs. Predicted k Values 66 15- Effect of Activated Sludge Effluent on Reaeration Laboratory Tests 70 16. Details of Plankton Chambers <,.. . ..»<..<. 74 17. Details of Benthic Chambers » 75 18. Benthic Chambers with Multiplace DO Meter 76 19. Light Transmission of Half Inch Clear Plexiglass 78 20. Toxicity Test 79 21. Oxygen Uptake Curves of Light and Dark Plankton Chambers-Both in Darkness 81 IX 22. Oxygen Uptake Curves of Light and Dark Benthic Chambers- Both in Dark Conditions 82 23* Weight Per Unit Area and Caloric Value Per Unit Weight of Biweekly Accumulations (13 June I967 to 28 May 1 968) on Glass Slides from Station SB 2, Saline Ditch, Champaign County, Illinois 92 2k. Weight Per Unit Area and Caloric Value Per Unit Weight of Biweekly Accumulations (13 June 1 967 to 28 May 1968) on Glass Slides from Station SB 8, Saline Ditch, Champaign County, Illinois 93 25. Weight Per Unit Area and Caloric Value Per Unit Weight of Biweekly Accumulations (13 June I967 to 28 May I968) on Glass Slides from Station SF 3A Salt Fork, Champaign County, Illinois 9k 26. Weight Per Unit Area and Caloric Value Per Unit Weight of Biweekly Accumulations (13 June 1 967 to 28 May I968) on Glass Slides from Station SF 10 Salt Fork, Champaign County, Illinois 95 27- Net Production of Aufwuchs as Indicated by Biweekly Accumulations (13 June 1 967 to 28 May 1968) on Glass Slides from Four Stations on the Saline Ditch-Salt Fork System, Champaign County, Illinois 97 28. Changes in Water Temperature from June 19&7 to June 1968 at Four Stations in the Saline Ditch-Salt Fork System 99 29. Changes in Weight and Caloric Value Per Unit Area of Accrued Material on Glass Slides from 11 June 1968 to 5 August 1968 from Station SB 2, Saline Ditch, Champaign County, Illinois 100 30. Changes in Weight and Caloric Value Per Unit Area of Accrued Material on Glass Slides from 11 June I968 to 5 August 1968 from Station SB 8 Saline Ditch, Champaign County, Illinois 101 31. Changes in Weight and Caloric Value Per Unit Area of Accrued Material on Glass Slides from 11 June 19&8 to 5 August 1968 from Station SF 3A Salt Fork, Champaign County, Illinois 102 32. Changes in Weight and Caloric Value Per Unit Area of Accrued Material on Glass Slides from 11 June 1 968 to 5 August 1968 from Station SF 10 Salt Fork, Champaign County, Illinois 103 33. Changes in Net Production of Aufwuchs on Glass Slides from 11 June 1968 to 5 August 1 968 from Four Stations on the Saline Ditch-Salt Fork System, Champaign County, Illinois 105 34. Caloric Values of Dissolved and Particulate Organic Material from June 1967 to June I968 at Station 1 Saline Ditch, Champaign County, Illinois . . 107 35- Caloric Values of Dissolved and Particulate Organic Material from June 1967 to June 1968 at Station 2 Saline Ditch, Champaign County, Illinois 108 36. Caloric Values of Dissolved and Particulate Organic Material from June 19&7 to June 1 968 at Station 3 Salt Fork, Champaign County, Illinois 109 37' Caloric Values of Dissolved and Particulate Organic Material from June I967 to June I968 at Station 4 Salt Fork, Champaign County, II 1 inois ..... 110 38. Hydrograph for Station SB 1, July 1 967 135 39. Hydrograph for Station SB 1, Aug. 1967 136 40. Hydrograph for Station SB 1, Sept. 1 967 137 41. Hydrograph for Station SB 1, July 1 968 138 42. Hydrograph for Station SB 1, Aug. 1 968 139 43. Hydrograph for Station SB 1, Sept. 1 968 140 44. Hydrograph for Station SB 6, July 1967 . . . l4l 45. Hydrograph for Station SB 6, Aug. 1 967 1^2 46. Hydrograph for Station SB 6, Sept. 1967 1^3 hi. Hydrograph for Station SB 6, July 1 968 144 48. Hydrograph for Station SB 6, Aug. I968 % . . . . 145 49. Hydrograph for Station SB 6, Sept. 1968 146 50. Hydrograph for Station SF 10, July 1967 1^7 XI 51. Hydrograph for Station SF 10, Aug. 1967 1^8 52. Hydrograph for Station SF 10, Sept. 1 967 1^9 53. Hydrograph for Station SF 10, July 1968 150 5k. Hydrograph for Station SF 10, Aug. 1968 151 55- Station SB 5, 2k Hour Study, 14-15 Aug. 1968 I67 56. Station SB 6, 2k Hour Survey, 14-15 Aug. I968 168 57- Station SB 5, 2k Hour Survey, 21-22 Aug. I968 169 58. Station SB 6, 2k Hour Survey, 21-22 Aug. 1 968 170 59- Station SB 5, 2k Hour Survey, 28-29 Aug. 1968 171 60. Station SB 6, 2k Hour Survey, 28-29 Aug. 1 968 172 61. Station SB 5, 2k Hour Survey, k-5 Sept. I968 173 62. Station SB 6, 2k Hour Survey, k-5 Sept. 1 968 ]Jk xi 1 CHAPTER I INTRODUCTION PRIOR RESEARCH The basic equation which is widely used for the prediction of oxygen relationships in streams is based on the work of Streeter and Phelps (1925) • This equation was developed from investigations on the Ohio River, a large sluggish stream. The investigators cautioned would-be users of the equation that its application to other streams might be unwise where factors other than those considered in their own investigations were important. Nevertheless, the Streeter-Phel ps equa- tion has been used with or without slight modification since its presen- tation to the sanitary engineering profession. Streeter (1935 a,b; 19^9) continued to use the equation and suggested modifications to ex- tend its applicability. Since the early work of Streeter and Phelps, Velz and co- workers have been important contributors to the science of stream in- vestigations. In an early paper, Velz (1939) discussed the basic fac- tors to be considered in deoxygenat ion and reaeration of streams. In later papers (Velz, 19^+7 and 19^9) he discussed the importance of ben- thic demand, algae and nitrification. Velz and Gannon (196^) summarized much of their previous work and Wezernak and Gannon (I968) suggested a method for evaluation of nitrification in stream investigation. In recent years Dobbins and O'Connor have made significant contributions to the mathematical relationships involved in DO predic- tions. Their early article (O'Connor and Dobbins, 1956) developed a prediction equation for reaeration in natural streams. Dobbins (196A-) discussed the importance for considering longitudinal dispersion, removal of BOD by sedimentation, resuspension of benthic material, and plant res- piration and photosynthesis. O'Connor (1967) and O'Connor and DiToro (1968) have further expanded earlier models to include diurnal variations in the sag equation. Camp ( 1 965) verified the importance of sedimenta- tion and photosynthesis in some rivers when making DO predictions. Li (1962) extended the Streeter-Phel ps equation to include the effect of variation of volume and velocity of flow from section to section. O'Connell and Thomas (1965) suggested a method to take photosynthesis and respiration by benthic algae into account in the DO prediction equation. A great deal of effort has been put forth by the TVA group in looking at a statistical approach to the oxygen relationships in rivers. The major aspects of their work were reviewed by Churchill (195^), Churchill and Buckingham (1956), Churchill, Buckingham and Elmore (1962), and Churchill, Elmore and Buckingham (1964). Most of the effort related to delineating the important para- meters of the oxygen sag equation have been generated from studies on large rivers. Only a few investigators have concerned themselves with oxygen relationships in small streams. Kittrell and Kochtitzky (19^7) pointed out the similarities and differences between shallow turbulent streams and a large sluggish river like the Ohio River. These authors as well as Camp (1965) suggested that BOD removal by sedimentation and photosynthetic oxygen production might be major factors in the oxygen balance of streams with flows in the range of 600 to 2000 cfs. Exten- sive work on the oxygen relationships in small streams (2 to 100 cfs) has been carried out in Great Britain. Pertinent references are Gameson, Truesdale and Downing (1955), Gameson and Truesdale (1959) > Edwards, Owens and Gibbs (1961) , Owens and Edwards (1963) , Owens, Edwards and Gibbs (1964), Edwards (1964), Edwards and Rolley (1965), and Owens (1965)- This series of articles considers the importance of sedimentation, benthal demand, respiration and photosynthesis, diurnal variations, and reaeration, and discusses predictive equations to take these parameters into account. NEED FOR INVESTIGATION The above discussion indicates that the majority of the work concerned with oxygen relationships in streams in the United States has dealt with large streams and emphasis has been placed on biological oxidation as the demand and atmospheric reaeration as the source of oxygen. In recent years more emphasis has been placed on the influence of sedimentation, benthal oxygen demand, and photosynthesis. Many municipal and industrial wastewater treatment plants discharge to small streams where the wastewater discharge is the major flow during the critical period of the late summer. Even with extensive biological treatment the residual BOD may severely tax the oxygen re- sources of the stream. Since many communities in our nation are faced with such circumstances, it appears mandatory that the profession ex- amine in more detail the parameters which will assist in determining the assimilative capacity of a stream. One way to predict the assimilative capacity of a stream is to use a mathematical model such as the Streeter-Phel ps equation or one of the more recent modifications of it. However, as the previous dis- cussion has indicated, this is extremely difficult for small streams. This report examines two fundamental inputs to the oxygen sag equation, namely the applicability of existing relationships for calculating the reaeration coefficient, and methods for measuring photosynthet ic oxygen production and benthal oxygen demand. SCOPE OF RESEARCH In this investigation it was proposed to make detailed studies of various parameters which were considered to have an important bearing on a predictive model for the oxygen relationships in a small stream. The factors to be studied were atmospheric reaeration, photosynthesis and respiration by free floating and attached aquatic growths, biologi- cal oxidation of soluble and suspended matter, benthic oxygen demand, and sedimentation and resuspension of benthal material. Each parameter was to be studied independently insofar as was possible and its contribu- tion to the gross oxygen concentration in the reach determined. The in- fluence of organic load on the stream, flow, velocity, depth, temperature and light were to be determined. Several reaches of the stream were to be studied and detailed mass balances for oxygen made. During the first year the effort was directed toward the con- struction of the gaging stations and the design of various pieces of equipment for photosynthetic and benthal oxygen demand studies, and flow chambers for laboratory studies. This equipment was built and tested and modified as required. The critical flow periods of the stream, i.e. flow conditions such that the wastewater treatment plant effluent made up 50 percent or more of the stream flow, occurred during the months of June to Sep- tember. Thus, the majority of the field work was carried out at these times. The second year of the project was devoted to perfecting the experimental equipment and initiating detailed studies in the field. As will be explained later, the weather conditions during the second summer's work were not conducive to obtaining information on low flow conditions. Greater than normal rainfall and flood conditions not only prevented field work but also denuded the stream bottom so that the usual benthic deposits and attached growths did not develop to a sufficient extent to make meaningful measurements. Late in the second year it was learned that the project would not be funded for continued field studies for a third year. Thus, the detailed mass balance studies in the field could not be accomplished. However, three major aspects of the project were begun and considerable progress made. These were the reaeration investigations, photosynthetic oxygen production and benthal oxygen demand investigations, and biologic investigations. Reaeration Several equations have been advanced to predict the changes in the dissolved oxygen profile caused by the addition of a biodegradable waste. Whether the simple two term oxygen sag equation proposed by Streeter and Phelps (1925) or one of the more sophisticated versions such as those of Camp (1963) or O'Connor ( 1 967) is used, it is necessary to evaluate several rate constants. The most important single factor acting to restore oxygen to an unsaturated water is atmospheric reaeration. The accurate determina- tion of the rate of flow of oxygen into water is therefore extremely important in the development of an equation which will truly predict stream oxygen concentration. Under steady conditions oxygen dissolves in water at an air-water interface at a rate proportional to the dif- ference between the actual dissolved oxygen concentration, C, and the saturation oxygen concentration, C , as s £ =K(C s -C) The constant of proportionality, K, is termed the reaeration coefficient. K is dependent upon the degree of surface mixing and the temperature existing in the water. It is also influenced by the presence of surface active agents. Many attempts have been made to correlate the reaeration coefficient with easily measurable physical or hydraulic properties of natural streams. In addition to their oxygen sag equation, Streeter and Phelps (1925) derived an equation to predict Ohio River reaeration (K, base e) in terms of H, the average depth; V, the mean velocity; and c and n, "constants which depend in part on the channel slope and irregularity." The combination was w n H The equation is not generally useful since it requires evaluation of the constants c and n for each stream reach. Gameson, Truesdale and Downing (1955) measured reaeration co- efficients on a small unpolluted stream (1.5-2 mgd) and reported the effects of addition of known concentrations of surface active agents — anionic detergents. The work provided an interesting method of measure- ment of reaeration capacity but did not advance any equations to relate K to measurable stream parameters. O'Connor and Dobins (1956) have theoretically developed two reaeration prediction equations. For conditions of nonisotropic turbu- lence (pronounced velocity gradients) the following formula was developed: i F e while for conditions of isotropic turbulence (D F V)" 2 k = — L 2.31 H 3/2 in which k = reaeration coefficient, base 10 i Dp = liquid film diffusion coefficient, a function of temperature S = energy gradient H = average depth of flow V = average velocity Isotropic flow was defined as that existing at a Chezy coefficient, Ch, greater than 17 and nonisotropic flow as that existing at a lower Ch. The authors used measured reaeration rate values from both deep slow moving and shallow turbulent streams to support their prediction equations. Measured k values were determined by solving the St reeter-Phel ps oxygen sag equation for k ? . Stream reaches were selected so that effects of factors other than biochemical oxygen demand and atmospheric reaeration wou 1 d be minima 1 . O'Connor (1958) used the equation for isotropic turbulence to estimate k for cases of nonisotropic turbulence, the difference being considered insignificant in practical cases. Substituting the liquid film diffusion coefficient at 20°C and converting to inverse days yields k = 5-616 V 1/2 H" 3/2 The range of measured values was as follows: k - day" 1 0.018 - k.8 velocity - fps 0.32 - 4.20 depth - ft 0.9 - 37 Gameson and Truesdale (1959) measured the rate of surface re- aeration in a clear stream and in one receiving the effluent from a wastewater treatment plant. Typical values of oxygen exchange coeffi- cients for all types of waters were tabulated. The authors published neither prediction equations nor checks of prediction equations derived by others. Edwards, Owens, and Gibbs (1961) have experimented with both clear streams and those containing wastewater effluent. Their work pro- vides methods of correcting reaeration coefficients for variable plant respiration and ground water inflow. Churchill, Elmore, and Buckingham (1962) performed a dimensional analysis of atmospheric reaeration and used the results of extensive field experimentation to develop the prediction equation k- 5.026 v ° • *9 H - 1.673 where V = mean velocity H = mean depth The authors also proposed other equations which included energy slope, resistance coefficient, and Reynolds number. These latter equations were said to be no better and more complex than the one given above. The oxygen uptake of waters discharged from the hypolimnion of reser- voirs was used to measure k. The waters contained little or no bio- chemical oxygen demand. Corrections were made for the effects of photosynthetic plants. The authors also suggested a correction for the effects of pollution in determining values of reaeration rate. The range of the mean measured values was as follows: k - day" 1 0.225 - 5-558 discharges - cfs 952 - 17,270 velocity - fps 1 .85 - 5-00 depth - ft 2.12 - 11.41 Krenkel and Orlob (1963) have related atmospheric reaeration to the longitudinal mixing coefficient, D. , in an artificial channel. The following prediction equation was derived empirically: k at, 20°C = 1.138 x 10~ 5 D 1 _ 1 * 321 H~ 2 ' 32 where D = longitudinal mixing coefficient H = depth The value of D was obtained by analysis of flow through curves of tracers. Owens, Edwards, and Gibbs (1964) have incorporated the work of Gameson et aj_. (1955) and that of Churchill et_ aj_. (1962) with studies of their own to check existing prediction equations. The best agree- ment was with the equation presented by O'Connor and Dobbins (1956) except in shallow fast moving streams. Two equations were proposed to predict k: k=9.4 V °- 6 7H-'- 85 for V = 0.1 - 5-0 fps and H = 0.4 - 11.0 ft and k- 10.. V°- 73 H-'- 75 for V = 0.1 - 1.8 fps and H = 0.4 - 2.4 ft Reaeration rates were measured by the disturbed equilibrium method used by Gameson e_t a_l_. (1955) and modified by Edwards et al_. (1964). Measure- ments were made for the most part in streams without organic pollution. The range of measured values was as follows: k - day" 1 0.31 - 57-5 discharge - cfs 1.50 - 36.20 velocity - fps 0.13-1 .83 depth - ft 0.34 - 2.44 Langbein and Durum (1967) have combined the field data of O'Connor and Dobbins and that of Churchill et a_]_. with the laboratory data of Krenkel and Orlob to develop the relation 10 -1 .33 k = 3-3 V H ' ° 5 The authors also showed a decrease in the reaeration coefficient in the downstream direction. Tsivoglou e_t aj_. ( I965 , 1 968) have measured atmospheric re- aeration using inert gases with a radioactive tracer. The investigators have established in the laboratory (Tsivoglou et_ aj_. , 1965) that the re- aeration coefficient is proportional to the transfer rate of inert gases They used this for field measurements of reaeration coefficients (Tsivoglou e_t aj_. , 1 968) . The method requires extensive equipment and release of radioactive substances. Isaacs and Maag (I968) have used the data of Churchill et a 1 . (1962) to relate the coefficient of reaeration to channel geometry and surface velocity as k = 2.98 $ ^ sv H 3/2 where $ and $ are dimensionless variables which account for the effects s v of channel geometry and surface velocity respectively and V and H are as above. For natural streams the authors found average values of $ = 1.05 3 s and $ = 1.16, v Most studies investigating the relations between k and measur- able stream parameters have been carried out on large streams or streams free of organic pollution. The Saline Branch of the Salt Fork, where the investigation was performed, is quite different from the streams on which the prediction equations for k have been devised. The stream re- ceives the effluent from the Champaign-Urbana Sanitary District which, 11 during critical periods, provides over 30 percent of the total stream flow (Fig. 1). The wastewater plant provides split biological treat- ment by the activated sludge and trickling filter processes. Typical plant effluents consist of 13 to 20 cfs flow with typical BOD concen- trations from 10 to 60 mg/1 and suspended solids of 20 to 70 mg/1 . Stream depths are relatively shallow (0.5 - 2.5 ft) between the treat- ment plant and the junction with the Salt Fork. Velocities during low flow periods average between 0.5 and 1.5 fps. The oxygen profile existing within the stream is greatly in- fluenced by biological factors other than bacterial respiration. Dur- ing algal blooms diurnal variations from 18 to less than 1 mg/1 have been observed. Measurements of benthic oxygen uptakes at a distance 2 6 miles below the waste outfall indicate rates of up to 8 gm/m -day. Due to the dissimilarities between the stream under study and those used to derive the equations and the variety of prediction equa- tions available, a study was undertaken to determine which, if any, of the equations would yield an accurate estimate of k. The equations selected for study were that of O'Connor and Dobbins (1956) for iso- tropic turbulence, that of Churchill e_t aj_. (1962), that of Owens et al , (196^) for low velocities and shallow depths, and that of Langbein and Durum (1967)- The equations are summarized below in the form used for computation: O'Connor and Dobbins k = 5.616 V 1/2 H" 3/2 12 r>4 — o> 00 — i-» — co xr> — *f co 1 1 1 1 1 1 II i , a V*- ; >6.3 miles downstream 1 ; i i i i i i i i ^-Upstream of waste treatment plant 1 1 1 1 1 1 1 1 \ i i i i i i i / i _ o — o> 00 _ r» to m co co 00 X. Ui I- O- IJLI CO CO z o I- z o 00 + K 2 D - K 1 L where C = concentration of dissolved oxygen in water, mg/1 t = time, hr P = photosynthetic oxygenation, — - — n • mq/1 R = respiration, — •** — r hr D = oxygen deficit = C - C, mg/1 15 where C = saturation oxygen concentration for a given temperature L = ultimate BOD load, mg/1 k„ = reaeration constant, hr k, = BOD constant, hr k, , L, and D were obtained by standard techniques and k_ by the O'Connor and Dobbins (1956) reaeration formula. When the equation was solved, the values for P and R and the resulting curve were very close to those obtained from the chamber data. The authors' conclusion (Thomas and O'Connell, 1965? and O'Connell and Thomas, 1 966) was that the algae do significantly affect the diurnal variation of oxygen con- centration in the Truckee River, but the contribution of oxygen can best be considered as an extra source and cannot be considered when determining allowable pollution loads on a stream. Downing (1967) points out that while large algae growths can give a very high peak value for DO in the day, their respiration at night can also dangerously lower the DO below normal night-time levels. In a discussion of O'Connell and Thomas' work, Symons (1966) introduced chambers that had been built of clear and opaque plexiglass which were used to study photosynthesis and respiration in reservoirs and lakes. These chambers were a significant improvement on the light- dark bottle technique, more closely representing the bodies of water in which they were used. Recently, much more lab work has been carried out with the benthos of streams. Among these investigations is one by Oldaker et al . (1968), which involved a lab study to determine the variability of the 16 rate of biochemical assimilation in the benthos and the effect of sedi- ment depth on oxygen uptake. The samples used were bottom sediments from the Merrimack River in Massachusetts. The authors conclusions were that k, (benthic rate coefficient) varied with the age of the sedi- ment and decreased with an increase in sediment depth up to 10 cm. Above 15 cm in depth, no change in ki was observed. Only the first 15 cm of sediment significantly affect the oxygen uptake. Nitrification appeared significant in these sediments, especially in shallow depths of sediment. McDonnell and Hall (1967) > working on a mildly polluted, highly eutrophic stream and studying the benthos in the lab, investi- gated the effects of oxygen concentration, temperature, and the charac- ter of the biologic community on the benthic oxygen demand. The authors found that oxygen uptake rates increased with increase in the initial oxygen concentration of the overlying water up to a concentration of 8 mg/1 . They suggested that this effect may have been due to signifi- cant populations of macroinvertebrates. A table given by the authors representing their work and that of others, dramatically illustrates that those sediments, whose oxygen uptake is dependent on oxygen concen- tration of the overlying water, probably contain significant macroin- ertebrates. They found, as might be expected, that an increase in temperature increases the uptake rate of oxygen. The authors state that the oxygen uptake rate is independent of sample depth with their sediments, but their data shows an increase in rate with depth. In another lab study by Davison and Hanes (1969), an attempt was made to determine why the discrepancies in reports about the effect of sludge depth on oxygen uptake existed. An artificial sludge consisting 17 v of dried de-inking process sludge and BOD dilution water was used. Fresh wastewater was used as seed in BOD dilution water for the over- lying water. The conclusions were that the uptake rate increased with increasing depth on freshly deposited cellulosic material. However, after the deposits were allowed to compact, uptake was generally inde- pendent of depth. Thus, the authors conclude discrepancies are due to disturbances of the deposits during observations. In summary, it can be noted that these works indicate that photosynthesis and benthal oxygen demand must be considered in assess- ing the assimilative capacity of polluted streams. To measure the photosynthetic effects in the stream under investigation, it was felt that the standard light-dark bottle tech- nique would not be suitable. Many investigators have spoken of its limitations. Among those, Symons (1966) gives four major restrictions. Briefly, they are: 1) an unnaturally high surface area-to-volume ratio, 2) the waiting time for significant DO changes, 3) the total lack of mixing, and k) the handling of water to fill the bottles. In a literature review by Gates (1963) > the importance of stirring is shown to manifest itself in three ways. First, the algal cells are kept in a more or less uniform suspension, whereas they might settle out without it. Second, moving water provides the algae with a constant supply of fresh nutrients and carries away algal waste. Third, all algal cells are exposed to the same light conditions, having periods of high and low intensity exposure dependent on where they are in the 18 suspension. Of course, all three of these criteria are met naturally by any stream flowing with sufficient mixing velocity, so any technique that does not meet them while studying algae is automatically in error. Even by 1956, Odum had said, "The light-dark bottle method for measuring gross primary production of the community ... is seldom applicable in flowing waters because much of the community is benthic and heterogeneous rather than planktonic. Furthermore, any measurement made without the normal turbulent flow may be questioned on the grounds that production is a function of current flow. The upstream-downstream measurement of ? , CO., and other properties is apparently the chief method available for the study of metabolism of flowing water communi- ties." Hopefully, there are now other methods. One of the limitations of benthic investigations in the past has been the lack of suitable equipment for lab or field work. The chambers built by O'Connell and Thomas (1965) seem to have great poten- tial for solving the problem and measuring benthal activity. The chambers described in this investigation are modeled after those of O'Connell and Thomas. O'Connell and Weeks (1966) developed a benthic respirometer which could isolate an area of stream, keep the interior water mixed with a submersible pump, and provide continuous or grab sampling for DO determinations. The inside volume was A-8.5 liters. Stay et al. (1967) developed three plexiglass chambers which could vary in height. One was closed and clear to investigate photosynthesis. One was closed and opaque to study respiration. The last was open to the atmosphere, though identical to the other two in every other way. Continuous 19 stirring, and continuous DO monitoring were provided. Artificial sub- strates were left in the stream until covered with natural growth, and then the plastic chambers were put over them- Benthic and planktonic oxygenation and respiration could be observed as well as atmospheric reaeration. Symons 1 chambers were designed so that a relatively undis- turbed sample of reservoir water could be trapped in situ . A battery powered motor provided constant stirring, and DO probes were used to monitor continuously the oxygen concentrations in the chambers as well as outside in the reservoir. The work carried out by Symons ( 1 966) with his aforementioned chambers suggested modifications of O'Connell and Thomas 1 chambers that resulted in the chambers constructed for this study. Biological The hydrosphere of Illinois is decidedly slanted toward flow- ing waters. As a result, limnological studies in Illinois have been directed largely to the lotic series (Kofoid, 1903? 1 908 ; Forbes and Richardson, 1913, 1919: Richardson, 1921a, 1921b, 1928; Eddy, 1931; Mills, Starrett, and Bellrose, 1 966) . The streams of Champaign County, Illinois, have received prob- ably as intensive and prolonged study as those in any area of comparable size in the New World (Larimore and Smith, 1963). Of these streams the Salt Fork of the Vermilion River and its tributaries, because of their proximity to the Urbana campus of the University of Illinois and to the Illinois Natural History Survey, have been the subject of much of this study. Most of this work concerned itself with the fish populations of 20 these streams (Forbes, 1 907 > 1909; Forbes and Richardson, 1908; Thompson and Hunt, 1930; O'Connell, 1935; Larimore, 1952, 1961; Larimore, Pickering, and Durham, 1952; Larimore, Childers, and Heckrotte, 1959; and Larimore and Smith, 1963. Papers concerning the insect fauna of the Salt Fork in- clude McNeill (1891), Malloch (1915), Alexander (1925), Frison (1929, 1935, 1937, 19^2), Hebard (193^), Ross (19^), and Burks (1953). The Mollusca have been considered by Zetek (1918), Baker (1922a, 1922b), Van Cleave (19^0), Matteson and Dexter (1965), and Parmalee ( 1 967) . Lesser works deal with annelids (Smith, 1915) and fresh water sponges (Smith, 1921). The pollution of the Salt Fork has been considered by Shelford (1917) and Alexander (1925)- Ranalli and Scheidegger ( 1 968) include the Salt Fork in their study of the development of river nets. Larimore and Smith (1963) and Roeske (1969) considered the chemistry of the Salt Fork system. Current investigations of the Salt Fork are being conducted by various individuals at the University of Illinois. These areas range from geomorphology to the macroinvertebrates and protozoa. The Illinois Natural History Survey is continuing its investigations of the Salt Fork biota. The macroinvertebrates, especially the chirono- midae, and the fishes are receiving much of this attention. Many small streams in the midwest flow through agricultural land and receive effluents from domestic wastewater treatment plants. The resulting pollution is coming more and more under the scrutiny of the public and of the scientific society. Increased emphasis on water- based recreation will focus more attention to the problem of reclaiming these water resources. 21 Considering the small polluted stream as a generally occurring phenomenon, an intensive study of one such stream, including physical, chemical, and biological aspects, would provide information useful in a wide variety of cases. The Salt Fork of the Vermilion River is consid- ered to be a representative "polluted small stream." The large number of earlier studies of this stream provide an unique opportunity for the investigator. Extensive background data reflect changes in stream qual- ity through the years and are available for comparison with current findings. Any study related to water supply or water pollution should include a consideration of aquatic organisms. Significant contribu- tions have been made in the areas of Aufwuchs , plankton, benthos, syrton, and fish population studies. Generally, however, it is not realistic to isolate a particular segment of the biota and consider it as representative of the whole. It is the study of the total aquatic biota that tells one most about water conditions. To date there have been no studies in which the entire stream community has been examined. Partial community analysis is generally the rule. Minckley (1963) presents one of the most complete studies of the aquatic environment to date and includes both producer and macro- consumer groups concurrently. Microconsumers have yet to be studied thoroughly in the aquatic ecosystem. This study of oxygen relations in small streams included a biological sampling program to supplement concurrent physical and chemi- cal sampling. Biological parameters measured include both producers and macroconsumers. The composition and production rates of the Aufwuchs 22 and the composition of the dissolved and particulate organic material (including plankters), syrton, benthos, and fish populations were mea- sured. These communities and the abiotic components of the aquatic ecosystem are interrelated and are related to the al lochthonous pollu- tants entering the stream. As such, they relate to the total picture of stream conditions, including oxygen. 23 CHAPTER II LOCATION OF PROJECT DESCRIPTION OF THE DRAINAGE BASIN The Salt Fork of the Vermilion River-arises in east Champaign County, Illinois, at an altitude of 800 ft above sea level (Fig. 2). It flows toward the southeast and joins the Middle Fork of the Vermilion River southwest of Danville, Vermilion County, Illinois. The Vermilion River joins the Wabash River near the Illinois-Indiana state line. The waters of the Wabash reach the Gulf of Mexico via the Ohio-Mississippi River System. At least three major ice sheets are known to have entered Champaign County (Maxey and Smith, 1959) but the effects of the more recent Wisconsin ice sheet, approximately 18,000 years ago, obscure those of the much older Illinoian and Kansan stages (Larimore and Smith, 1963)- The entire county is overlaid with a mantle of glacial till, 200 to 330 ft thick (Maxey and Smith, 1959). Most of the glacial till is covered with a layer of loess of varying thickness up to 30 ft (Fehrenbacher, 1959). The discharge from the Rantoul municipal wastewater treatment plant enters the Upper Salt Fork Drainage Ditch. Waste discharge from Chanute Air Force Base enters the stream approximately two miles below the Rantoul outfall. Effluent from the Urbana-Champaign municipal waste- water treatment plant enters the Saline Branch on the northeast edge of the city of Urbana. Diffuse sources of wastewater, largely untreated, enter the stream from other communities located within its drainage basin. Silt and nutrients enter the stream in runoff from agricultural 2k u_ — ^ > CO "— — O _c 1 — Q. Lt_ Q) co / Ll i/l co O 1_ -) 0) CTv \v ST ■M LL. *~ co \v z: CO CO r *r LL. co r~^ rsi ' u. cr\ u_ co LL. CO CO ^5 land and may contribute substantially to the quality of the water (Roeske, 1969). Champaign County has a temperate continental -type climate and is far from the modifying influences of large bodies of water. The annual mean temperature is 1 1 . 1 °C . Normal annual precipitation amounts to 92.3 cm, 59 percent of which occurs during the warmer half of the year. Changnon (1959) presents a detailed summary of weather conditions of the Champaign County area. CI imatological conditions during the field portion of the pro- ject were not typical. The average temperature was below that recorded for the years 1889-1962. Both the average monthly precipitation and the total precipitation during the study period exceeded the 73-year averages. CI imatological conditions prevailing during the field por- tion of this study appear in Table 1. Figures 38 to 5^ in the Appendix indicate the flow at three locations (Fig. 2) in the drainage basin for 3 summer months. TABLE I CLIMATOLOGICAL DATA FOR THE YEAR JUNE, 1967 TO JUNE, 1968 AT URBANA, CHAMPAIGN COUNTY, ILLINOIS 3 CI imatological Parameter Average Daily Maximum Temperature (°C) Average Daily Minimum Temperature (°C) Average Daily Mean Temperature (°C) Average Monthly Precipitation (cm) Total Precipitation (cm) Time Perioc i June, 1967 to June, 1968 1889-1962 16. 5 17-6 5.9 6.4 11.3 12.0 9.^5 7-^7 113-4 99-64 Adapted from Illinois State Water Survey weather summaries for Urbana 26 SAMPLING STATIONS Figure 2 shows the study area and indicates the positions of stations used throughout the investigation. Table 2 summarizes the mileage between stations and the mileage from several reference points. All stations were located at easily accessible locations, either at road crossings of the stream or at places where a road closely paralleled the stream. Easily accessible locations facilitated the use of a wide variety of equipment during various phases of the study. 27 TABLE 2 STATION MILEAGES Mi les f 1 rom Junction of Miles Between Miles Below Sal ine Branch and Station Stations Treatment Plant Salt Fork River SB 1 0.00 -0.1 10.15 SB 1A 1.05 1.05 9-10 SB 2 0.20 1.25 8.90 SB 3 1.12 2.37 7.78 SB 4 1-73 4.10 6.05 SB 5 1.00 5.10 5.05 SB 6 1.20 6.30 3.85 SB 7 1 .20 7.50 2.65 SB 8 0.55 8.05 2.10 Junction 2.10 10.15 0.00 USF 1 0.00 - 14.12 USF 2 0.92 - 13.20 USF 3 0.26 - 12.94 USF 4 1 .04 - 11.90 USF 5 0.90 - 11.00 USF 6 0.75 - 10.25 USF 7 1 .06 - 9-19 USF 8 0.79 - 8.40 USF 9 0.42 - 7.98 USF 10 0.76 - 7-22 USF 11 1.18 - 6.04 USF 12 0.92 - 5.12 USF 13 1.00 - 4.12 USF 14 1.24 - 2.88 USF 15 1.62 - 1.26 USF 16 0.50 - 0.76 28 TABLE 2 (Continued) STATION MILEAGES Miles from Junction of Miles Between Miles Below Sal ine Branch and Station Stations Treatment Plant Salt Fork River SF 1 0.00 10.43 0.28 SF 2 1.50 11.93 1.78 SF 3 1.80 13-73 3-58 SF 3A 1.40 15.13 4.98 SF 4 1.60 16.73 6.58 SF 5 1 .96 18.69 8.54 SF 6 3.22 21 .91 11.76 SF 7 1.78 23.69 13.54 SF 8 2.81 26.50 16.35 SF 9 2.09 28.59 18.44 SF 10 1.48 30.07 19.92 SF 11 3-05 33-12 22.97 SF 12 1-35, 34.47 24.32 SF 13 1.59 36.06 25.91 SF 14 1.08 37-14 26.99 SF 15 6.83 43-97 33.82 SF 16 3.96 47.93 37.78 29 CHAPTER III METHODS INSTRUMENTATION DEVELOPMENT Gaging Stations Four gaging stations were installed so that adequate flow data would be available for all aspects of the investigation. An existing concrete broad-crested weir installation at the Urbana- Champaign Sanitary District Plant was reactivated (Station SB 1, Fig. 1). Since it was anticipated that a great deal of effort would be made in the vicinity of Stations SB 5 and SB 6, it was decided to install a control section at Station SB 6. In addition, gaging sta- tions were installed at Stations SF 4 and SF 10 which were located in other reaches of the stream where it was anticipated that detailed investigations would be carried out. A contract was entered into with the U. S. Geological Survey for the construction, operation, and maintenance of the stations. Periodic calibrations were made at each station so that a rating curve could be kept current. Recording devices were placed at Stations SB 1, SF 6 and SF 10. A wire weight gage was placed at SF k because it was felt that the added expense of constructing a control section and in- stalling and maintaining a recorder was not warranted. Hydrographs for the low flow study periods of 1967 anc ' 1968 for the three stations with recorders are shown in Figs. 38 to 5^ in Appendix I. Dissolved Oxygen Meters The dissolved oxygen measurements were made with a Clark- type membrane-covered polarographic electrode. Commercial oxygen Product of the Yellow Springs Instrument Company, Yellow Springs, Ohio. 30 meters (Models 51 and $k, YSl) and similar type meters manufactured in our own shops were used through the field and laboratory investigations One DO probe was reserved as a standard probe and used only for calibration of the other probes used in the investigations. It was carefully calibrated by the Winkler method and its calibration frequently checked. The calibration curves for the other probes were prepared by comparison with the standard probe. This method facili- tated quick and accurate calibration of the many DO probes used during the investigation. During the design of experiments for photosynthetic oxygen production and benthic oxygen demand it was evident that the investi- gation would be greatly facilitated if a multiple input DO meter was available. Such a meter was designed and built which would receive the inputs from 5 thermistors and 5 DO probes. Figure 3 is a schemat- ic diagram of the meter. It was used in conjunction with the chambers used for measurement of photosynthetic oxygen production and benthal oxygen demand. Signal Adapter In order to carry out continuous monitoring of temperature and DO in the flow chambers it was necessary to design and construct a signal adapter to receive the signal from the h DO probes and the h thermistors and then modify or amplify the signal for transmission to a chart recorder. Each signal was sensed for 3 minutes, once every 30 minutes. The adapter also produced two calibration signals per cycle to verify the proper functioning of the electronic circuitry and to facilitate identification of the various signals. 31 ooooo o o ooo l-Z *S fD OJ c > "O o o rjj — • ~ XI > — 4-* ft) — QJ o u T3 m in "D fO in C 03 ■« dJ i/l "D cn >- Z3 — • O X O C h- o U_ D 3' ANALYTICAL TECHNIQUES During a number of phases of the investigation it was neces- sary to collect a large number of samples and make as many as a dozen different analyses on each sample over a short period of time. It was not possible to store the samples for several of the analyses as the characteristics of the sample might change during storage. To facili- tate the handling and processing of the samples in an efficient a man- ner as possible, a short manual was prepared with directions for the speedy processing of samples, yet achieving the desired degree of ac- curacy in the result. Standard Methods, 12th ed. (APHA, 1965) was used for all analytical procedures except as noted below. Physical Methods Specific conductivity measurements were made with a Beckman RA-2A conductivity meter. Most measurements were taken in the field. However, during winter several samples were returned to the laboratory for measurement. The water temperature of these samples was maintained below 5°C during transit and was brought up to room temperature (approx. 25°C) prior to conductivity measurement. For samples measured in the laboratory, water temperature was taken with a partial immersion mercury bulb thermometer immediately prior to conductivity measurement. Total dissolved solids were computed from water temperature and specific con- ductance values. Chemical Methods Inhibition of nitrification in the BOD test. In order to Product of Beckman Instruments, Cedar Grove, New Jersey, 33 differentiate between the carbonaceous and nitrogenous BOD, the allyl- thiourea (ATU) method of Wood and Morris ( 1 966) was used. The standard BOD procedure was used except that 0.15 ml of a stock ATU solution (500 mg ATU per liter of solution) was added to each BOD bottle before the sample was placed in the bottle. Ammonia nitrogen . The Standard Methods procedure was used except that the color developed after 10 minutes of ness lerizat ion was read on a Bausch and Lamb Spectronic 20 at 415 mu.. Nitrate nitrogen . A modified form of the chromotropic acid procedure described by West and Ramachandran (1966) was used. The original procedure called for a purified form of the disodium salt of 1 ,8-dihydroxy-3 , 6-naphthalene disulfonic acid. However, it was found that the technical grade material was suitable, without purifi- cation. The chromotropic acid solution was prepared by placing 0.200 mg of the technical grade acid in 200 ml of concentrated sulfuric acid. The stock nitrate solution was prepared by dissolving 0.7218 g anhydrous potassium nitrate, KN0,, and diluting to one liter with distilled water. This gave a solution containing 100 mg/1 of nitrate nitrogen. One hun- dred ml of the stock nitrate solution was then diluted to one liter with distilled water and used for the nitrate standards. One ml of this solution contained 0.01 mg of nitrate nitrogen. The sulfite-urea antimony sulfate and sulfuric acid solutions were used as described by West and Ramachandran. The modified procedure used was as follows. 1. Pipet into a dry 25 ml volumetric flask 5-0 ml of sample or Eastman Organic Chemicals, technical grade. lh an appropriate amount to give an absorbance of less than 0.4. If less than a 5-0 ml sample is taken, make up to 5-0 ml with distilled deionized water. 2. Set a blank of 5-0 ml distilled deionized water. 3. Add 2 drops of sulfite-urea solution (20 drops ~ 1 ml). 4. Place flask in a tray of cold water 10-20°C and add 4.0 ml antimony sulfate solution. 5- Swi rl to mix. 6. After 4 min, add 2 ml chronotropic acid and swirl to mix. 7« Cool in tray for an additional 3 min. 8. Add concentrated H SO. to the 25 ml mark. 9. Stopper the flask and mix by inverting 4 times. 10. Allow the solution to stand for 45 min at room temperature. 11. Finally adjust volume to the 25 ml mark with concentrated H 9 S0. . Mix gently to avoid bubbles. 12. Transfer gently to avoid bubbles to \ in. cuvette and read absorbance at 420 mp, 15 min or more after final adjustment. Use the blank to set absorbance at 0. Phosphorus . The glassware used for the phosphorus determination was kept separate from the other glassware and only used for this deter- mination. The glassware was carefully cleaned after each use. For total phosphate the method of Gales, Julian and Kroner (19&6) was used. The bismuth catalyzed method for total orthophosphate, total inorganic (ortho and poly) phosphate and soluble inorganic (ortho and poly) phosphate was used (Robertson, i960 and Hickey, 1964). 35 Biological Methods Surface water samples were collected and returned to the lab- oratory for analysis of the dissolved and suspended organic material. Samples were passed through a Sedgewick-Raf ter funnel containing a 1 cm column of 60-120 mesh silica sand supported on a 200 meshes-per-inch nylon bolting cloth screen. Replicate 50 ml samples of filtered water were subjected to oxidation by the dichromate method described by Maciolek (1962) . Four benthic samples were secured from each station on each 2 collecting day with a six inch square Ekman dredge (0.02 m ). Samples were taken from randomly selected points within the stations. As the water depth was seldom more than 1 m the dredge was operated manually. In this way the operator was able to determine if the jaws of the dredge had closed properly before removing the dredge from the bottom. This method proved satisfactory even for coarse gravel substrates. Benthic collections taken from fine sand or silt substrates were screened with a series of three graded sieves in the manner de- scribed by Welch (19^8). Those organisms retained by a 30 meshes-per- inch sieve (aperature size approximately 750\i) were preserved immediately in 70 percent ethanol . Benthic collections from coarse sand and gravel were transferred directly from the dredge to one gallon plastic pails and returned to the laboratory. Benthic organisms were "floated" from the substrate material with a strong sodium chloride solution. Carbon tetrachloride (Whitehouse and Lewis, 1966), magnesium sulfate (Ladell, 1936; Beak, 1938), sodium chloride (Lyman, 19^3), and sucrose (Caverness and Jensen, 1955; Anderson, 1959) have been used 36 successfully for separation by flotation. Whitehouse and Lewis ( 1 966) reported 99-6 percent recovery of organisms by the flotation technique. Sodium chloride was used in this study because of its low cost and lack of an offensive odor. Sucrose also met these criteria but left the flo- tation equipment "sticky." Each coarse sand or gravel sample was floated several times. The saline solution was decanted through a 30 meshes-per-inch sieve after each flotation and the retained organisms were preserved in 70 percent ethanol . The sand or gravel residue from each sample was ex- amined periodically to insure complete removal of organisms. Flotation did not prove satisfactory for samples containing large amounts of or- ganic detritus as this material floated along with the benthic organisms, Collections of the syrton (drift) were made with a #^71 Nitex cloth net suspended from a one foot square brass frame. Construction and use of this net was described by Fishman (1968). Pore size of the net was A-71u.. Drift collections from the top foot of the water column were taken for time intervals varying from 15 to 60 minutes. The shorter time intervals were necessary during periods of high water when the stream carried large amounts of al lochthonous detritus which quickly clogged the net. All drift collections were preserved immediately with 70 percent ethanol . Plankton samples were secured from surface water samples returned to the laboratory for that purpose. These samples were main- tained at, or slightly below, stream water temperature during transit. Product of Tobler, Ernst, and Traber, New York. 37 The sand filtration method described in Standard Methods (APHA, 1965) was used to concentrate plankton samples. Moderate suction was used to hasten filtration. This method has a maximum pore diameter Sk\i (Welch, 1 9^+8) , but the effective pore size can be much less depending upon the packing of the sand and the degree of clogging of the filter bed during use. Three 1 liter samples were taken from each station. One sample was preserved for the identification and enumeration of orga- nisms. Two samples were subjected to dichromate oxidation (Maciolek, 1962) for caloric value determinations. Aufwuchs collections were made by suspending pre-weighed microscope slides in the stream and allowing time for the development of the Aufwuchs community. Slides were numbered consecutively to aid in later analyses. Methods for the collection of Aufwuchs with arti- ficial substrates have been adequately described (Nielson, 1953; Cooke, 1956; Sladeckova, 1962). Peters (1959) demonstrated that artificial substrates were not selective and supported the same Aufwuch s organisms as natural substrates. Slides were suspended vertically in plastic microscope boxes from which the top and bottom had been cut away. Vertical suspension proved an effective means of avoiding silt accumulation. King and Ball (1966) reported greater loss of material from horizontal than vertical surfaces upon removal from the water. They attributed this to algae growing on accumulated silt which was washed from the slides upon re- moval from the water. Castenholz (I960) felt that horizontal placement was better than vertical placement since horizontally placed substrates 38 accumulated greater weights of material. King and Ball ( 1 966) demon- strated that this greater weight was due to silt deposition and found no significant differences (at the 0.05 level) in accrual of Aufwuchs organisms between vertical and horizontal substrates. Two series of Aufwuchs collections were made. In the first series, nine slides were placed in the stream at each station on the first collecting day of the study year. On each subsequent visit the slides from the stream were replaced with new slides. Three of the slides from the stream were preserved in 70 percent ethanol . These slides were retained for identification and enumeration of orga- nisms. The remaining six slides were air dried in the field and re- turned to the laboratory. These slides were later oven dried at 98-103°C, weighted and subjected to dichromate oxidation (Maciolek, 1962) Butcher (19^6) and Blum (1957) indicated that a two week sampling period may be insufficient for development of a climax or per- manent Aufwuchs community. For this reason a second series of Aufwuchs collections were made to provide information regarding the rate of accrual of material and the succession of species which takes place during community development. In this series of collections a large number of pre-weighed, numbered microscope slides were suspended ver- tically in the stream at each station by means of the plastic micro- scope slide boxes described above. The slides were placed in the stream on 11 June 1968. Three slides from each station were removed from the stream on each of 16 visits from 12 June 1 968 to 10 August 1968. The intervals between visits varied from one day to 5 days with the shortest interval occurring during the early portions of the study. 39 The air-dried slides were returned to the laboratory and treated in the same manner as the slides from the two-week interval series of Aufwuchs col lections. The Illinois Natural History Survey has extensive records of fish distribution from the Salt Fork. These records are based on an- nual sampling during autumn from numerous stations within the drainage basin. The collecting stations of this study are included in the Survey's fish sampling stations. Because of the dirth of fishes within the study area, fishes were not collected on a biweekly basis. Rather, fi.sh collections were limited to the autumn samplings. Two series of autumn fish collections were included in this study. They were conducted from 28 August to 1 September 1967, and 26 to 30 August 1968. Collections were made using a 20 ft by k ft minnow seine having a 3/8 inch mesh (stretched). Seining was continued at a station until diminishing returns indicated that further sampling would be unprofitable. Fishes were preserved in 15 percent formalin and returned to the laboratory for identification and enumeration. 40 CHAPTER IV FIELD SURVEYS SURVEYS OVER ENTIRE STREAM At various times during the investigation samples were col- lected at selected stations throughout the entire study area and a variety of analyses performed in order to characterize the stream at that particular time. As many as ]k stations were studied at one time. Samples were collected over as short a time interval as possible, usually within four hours. Temperature, pH and DO were measured in the field. The samples were returned to the lab and the remaining analyses carried out as quickly as possible. These field surveys were carried out in order to character- ize the stream at the time of the survey. The information obtained was used to assist in the design of the more detailed studies for other phases of the investigation. Tables 7 through 9 in Appendix II give the results for these field studies. MASS BALANCE STUDIES The basic purpose of this investigation was to define the importance of the various oxygen sources and demands by detailed mass balance studies of various sections of the stream. The parameters that were to be studied included atmospheric reaeration (Chap. V), photosyn- thesis (Chap. VI), biological oxidation (Chap. VI), sedimentation, ben- thal deposits (Chap. VI), and aquatic growths (Chap. VI). Each individ- ual factor was to be evaluated separately in order to determine its con- tribution to the gross change in oxygen concentration through the section under study. Chapters V and VI describe much of the detail of these in- vestigations. The first years effort was applied toward the development of methods and equipment as described in Chapters III, V, VI, and VII. During the second year an attempt was made to begin the mass balance studies. One phase of this was directed at both field and lab- oratory studies of benthic oxygen demand. A flow chamber for the study of the oxygen demand and production of the benthal deposits was con- structed and evaluated. Refinements were made in the design and three additional chambers were constructed. Two flow chambers were of clear plastic and two of opaque plastic. Trays which had been placed in the stream and allowed to come to equilibrium with the stream benthos were transferred directly to the flow chambers, one clear and one opaque. Duplicate chambers without benthic material were used to correct for oxygen production or demand in the liquid medium. From the results with the four chambers it should be possible to determine benthic oxygen demand, for the particular sample examined, and its oxygen production under a particular condition of light, temperature, etc. Thus, under controlled laboratory conditions, further information could be obtained on the reaches under study. Figure 4 shows one of the flow chambers. The chamber is com- plete with pump, flow meter, and dissolved oxygen (DO) and temperature probes in the system. The temperature and DO were recorded as described below. The recorder adapter is shown on the right and the recorder on the left. The liquid flows through the constant temperature bath below the flow chamber. Continuous monitoring of the temperature and DO in the flow chamber is accomplished with thermistors and DO probes. The signals hi FIGURE k. FLOW CHAMBER WITH RECORDER AND SIGNAL ADAPTER from the two sensors in each flow chamber were amplified or modified in the adapter designed and constructed especially for this purpose, which transmits each signal to the recorder for 3 minutes. The flow rate was measured with an orifice meter. A collaps- ible container in each system allowed for the withdrawal of samples at any time for analysis of any physical, chemical or biological parameters of interest in the circulating supernatant. Figure 5 shows a typical curve obtained from a chamber oper- ated without light. Only limited data was obtained from these flow chambers be- fore the research phase of the project was terminated in September 1 968 - However, plans have been made to continue this phase of the study with funds from other sources. In mid-June 19,68, plans were made to begin the detailed mass balance studies. As can be seen from the hydrographs in Figs. 38 through 5^ of Appendix I the runoff during the summer of 1 968 was much greater than usual. In addition, several heavy storms, in particular the one of 16 July I968 almost completely denuded the stream of benthic deposits and attached aquatic growths. Thus, the high water during the early part of the summer plus the extremely high runoff during several storms prevented the appearance of the extensive sludge deposits, heavy attached aquatic growths and the extremes of DO (less than 1 to 18 mg/1) that had been experienced in previous years. It was not possible to begin de- tailed mass balance studies until mid-August, and then only in the Saline Branch (SB 5 and SB 6). The flow remained so high in the Salt Fork that the usually degraded conditions did not occur during the summer of I968. kk CM _ o - 00 jC _ - ■°^^^ n UPSTREAM „ — Estimated - -CM ' a^o—'CWv^ • c - - - i " . ^^ 5.0 E o o 4.0 3.0 1600 1600 1630 Time - Hours 1 r DOWNSTREAM (C - C')dt X 1630 Time - Hours FIGURE 6. DISSOLVED OXYGEN PROFILE DURING DOSING 50 1700 1700 before and after the passage of the added deficit the concentration which would have existed without the sulfite addition may be estimated, The mass of oxygen, M, lost to the sulfite is M = Jq(C - C')dt integrated over the interval during which C was not equal to C ' . As the water which received the sulfite moves downstream, the excess oxygen deficit is reduced. The change between upstream and downstream points 1 and 2 is then AM = M 1 - M 2 =JQ 1 (C 1 - Cpdt -Jq 2 (C 2 - C 2 )dt, It may be seen that, for constant streamflow with time and at the two points, the change in oxygen depletion is simply the flow multiplied by the difference in areas between the C and C curves (Fig. 6), and a proportionality factor. As the water with the increased deficit moves downstream the quantity of oxygen entering the stream due to reaeration is increased due to the increased deficit. The change in oxygen mass flowrate is given by Vol A 4r = K Vol AD dt where Vol = volume of water dc A-jt = change in rate of oxygen uptake due to increased deficit K = reaeration coefficient, base e AD = change in oxygen deficit due to sulfite addition 51 The mass of oxygen entering the water as it flows through a reach is then -Jk Vo Through Reach 1 AOdt Assuming that K and Q. are constant through the reach and replacing Vol by QT (flow and time of flow through the reach) yields S = KQ. I (C - C')dt Through Reach If the change in the increased deficit is not too large then it may be approximated by the average of point integrals of concentration with time at the upstream and downstream ends of the reach. Using the pre- vious notation j(C - C')dt + |(C - Cl)dt. S = KQT (J— ! ] - r t—± 1 —) where 1 and 2 indicate upstream and downstream ends of the reach respec- tively. The only effect of the sodium sulfite addition is to change the dissolved oxygen concentration in the water. If it can be shown that atmospheric reaeration is the only oxygen source or sink affected by the change in concentration then the change in the oxygen equivalent of the sulfite depleted water is caused solely by atmospheric reaeration, e.g. S = AM. Solving yields r r r , ,' (C - C')dt + (C - C Jdt- q{ J (C ] - Cj)dt - J (c 2 - C^)dt} =: kqt|- — ! ! l l - — ) 52 or K-l JCC] - c/ l) dt -J/ C 2 - C 2 )dt j(C ] - cj)dt + J'(C 2 - C^dt Methods of measuring k which require reaeration or reaeration and biochemical oxygen demand as the only factors affecting the oxygen profile cannot be used in the Saline Branch as the assumptions are not satisfied. Longitudinal dispersion within the stream prohibits use of the disturbed equilibrium method as proposed by Gameson e_t aj_. ( 1 955) - Consequently, the modified disturbed equilibrium method (Gameson and Truesdale, 1959) was used. A literature survey was made to justify the assumption that no significant oxygen demand other than reaeration is dependent upon oxygen concentration. The factors investigated were utilization of bio- chemical oxygen demand, respiration of rooted aquatic plants, respira- tion of stream benthos, and nitrification. Literature studies indicate that rate of oxygen consumption of aerobic bacteria is independent of oxygen concentration above 1 mg/1 (Zobel 1 and Stadler, 19^+0; Eckenfelder and O'Connor, 1961). Care was taken to keep the oxygen concentration above 1 mg/1 during the tests to maintain constant respiration. Owens and Maris (\36k) have indicated that the respiration rate of rooted aquatic plants is dependent upon oxygen concentration to approximately 16 mg/1. To avoid corrections for changing respiration the test reaches were selected in areas such that the growth of rooted aquatics was negligible. The effect of oxygen concentration upon the respiration of the 53 benthic community seems to be dependent on the community under study. Baity (1938), Fair et aj_. (19^1 a, b, c) and Hanes and Davison ( 1 968) have indicated the rate of oxygen uptake for sludges to be independent of the oxygen concentration in the supernatant water. Studies on sludges containing significant macro-invertebrate populations by Knowles, Edwards, and Briggs (1962), Edwards and Rolley (1965), and McDonnell and Hall (1967) indicate dependence upon oxygen concentration. Leifer (1969) made in situ measurements of benthic oxygen uptake rates in the Saline Branch immediately upstream of the site of this study. A typical dis- solved oxygen versus time curve is shown in Fig. 7 • The linear decrease of oxygen concentration with time indicates a rate independent of con- centration. On the basis of these experimental data the benthic res- piration rate was said to be independent of oxygen concentration. Oxygen consumption by nitrification is another process which may have a rate dependent upon oxygen concentration at low concentrations. Analysis of stream samples indicated that the majority of the nitrifica- tion was completed prior to arrival of the water at the test section. REAERATION COEFFICIENT FIELD MEASUREMENTS In order to create the increased oxygen deficit needed for the measurements a catalyzed sodium sulfite solution was added to the stream. The sulfite solution was mixed in a 50 gal drum using a submersible pump to provide stirring. The solution was then pumped into a flow divider in which the cobalt catalyst was added, and discharged at three points across the stream to obtain uniform distribution (Fig. 8). Cobalt was fed in sufficient quantity to keep the concentration in the stream at 5h t 1 1 1 1 1 1 1 1 r en E en X -o I 3 2 - J I photosynthesis J I L J I 1 1 1 2 3 Time - Hours FIGURE 7. OXYGEN UPTAKE WITH TIME FROM IN SITU BENTHIC MEASUREMENTS 55 3 3 (T v> Q 0) •»- O «♦- o» 3 O in X E Q LiJ o or ■+- hi > o o (/> o 3 z LU a. i— i LU to o Q 3 CO oo LLl o£ Z5 CJJ 56 0.5 mg/1 > to insure complete oxidation of the sulfite as indicated by both Edwards e_t a_l_. (1961) and laboratory studies of deaeration time conducted as a part of this investigation. The increased oxygen defi- cit caused by the sodium sulfite was roughly one half of its stoichio- metric equivalent of oxygen as indicated by a mass balance between the added sulfite and the oxygen concentration measured at the first station 500 ft downstream. The reduction was due to reaction with the air dur- ing mixing and dosing, reaeration in the .500 ft section, and impurities. The dissolved oxygen concentration and temperature were mea- sured at points 500, 1000, 1500, and 2000 ft downstream from the point of sulfite addition. Figure 9 shows the location of the dosing points and sampling stations. At each station the midpoint of the stream flow was found using velocity measurements and the temperature and dissolved oxygen concentrations were measured in the center of each half. No attempt was made to obtain a vertical profile as the stream was shallow and well mixed. Measurements were made at 5 min intervals when sulfite was not being added and at 2 min intervals during dosing. All measurements were made using YSI dissolved oxygen probes and locally constructed meters. To compute reaeration rates the dissolved oxygen versus time readings were plotted and the oxygen concentrations which would have existed without addition of the sulfite were estimated. The area be- tween the C and C curves was then determined using a planimeter and the time of flow between the stations calculated from the center of the leading edge of each depression curve. Hydrographs from the gaging station were used to determine flow and to insure measurements were 57 CO CD O O CD 2? CO H- O O 0> E I O 0> *" I I cm ro CO c o ~ O 0> <* O CM CM IO I . - c "° io o 5? S ® CM ■*> -Q CO V 1 I i : e i s |£ CO CO o Q_ >P IT) O «■ CM a v o 2100 ft downstream of SB 5 2700 ft downstream of SB 5 I 10 I I 20 30 Width - ft 40 FIGURE 10. CHANNEL CROSS SECTIONS 60 through time of the sulfite depleted water and the distance between measuring stations. The k values were then computed using the predic- tion equations as presented above. RESULTS By combining the reaches as shown in Fig. 3, it was possible to obtain a maximum of data with a minimum of manpower and equipment. Sulfite was added four times for each flow at which k was measured. Table 3 gives the arithmetic mean of the measured values adjusted to 20°C and the k values computed from the four prediction equations. A graphic comparison of the computed versus measured k values is given in Fig. 11 to 14. The data of this study is presented with the data used to derive the particular prediction equation. The dashed line in Fig. 11 to 14 indicate a measure of scatter between the individual measurements made in this study and the particular prediction equation, The measure is defined as a d N - 3 where d. = 1 n m. - In p. i l l .th r , m. = i measurement of k i p. = predicted k for i measurement N = number of measurements The measure of scatter, a ,, is similar to the standard error of estimate, d s , computed for data about its regression line. In this case the data 61 TABLE 3 MEAN MEASURED k VALUES VS. PREDICTED VALUES Measured k _ ] Computed k ■ . -1 - day O'Connor & Churchi 1 1 Owens Langbein & Reach day Dobbins et al . et a]_. Durum 5-10 21.0 7-63 8.16 15-3 5-19 5-15 12.2 7.39 7-78 14.6 4.97 5-20 14.4 7.87 8.60 15-7 5.43 10-15 8.60 7.15 7.40 13-9 4.75 10-20 13.4 8.00 8.88 16.4 5.60 15-20 16.1 8.77 10.2 18.6 6.34 29-3^ 21.2 15.0 17.9 33.8 9-94 34-39 6.57 11.0 11.9 23-2 6.82 39-44 16.3 5.80 5.24 10.6 3-31 29-39 13.3 13.0 14.9 28.6 8.38 29-44 14.1 11.1 12.4 24.0 7-09 34-44 12.9 8.50 8.78 17-3 5.16 5-10 24.2 16.8 15.6 34.8 7-92 5-20 13.8 20.1 20.0 44.1 9.75 5-15 14.0 20.2 19.9 44.1 9.70 62 30 r i 1 — i — | — i i i 1 1 i — i | i i i i i 7- ' m • / • l V* • / 10 6 O / / / / .5 - o / QP o. .2 "8 O— Churchi 1 1 et a_^. • — Data of this study J L J I 1 I l x J I i i I .1 .5 1 2 k - Predicted 10 30 FIGURE 11. MEASURED VS PREDICTED k VALUES 63 30 10 2 - .5 i 1 — i — | i i i i | 7 r .2 .1 / <~0 / / / VO / / r%yo / / / o ^ ° ~ ' °/ o 6>°/ / / / ° / o O — O'Connor and Dobbins • — Data of this study A I L ''■'I 1 I I 1 I I 1 .2 .5 1 2 5 k - Predicted 10 30 FIGURE 12. MEASURED VS PREDICTED k VALUES 64 50 11 i i 20 10 ■D 0) !_ in 0) ■* 1 .5 1 1 1 — | l I I I 7 — i — r / / / ° OD / / cP /qP& • / / / / o / • / / / ° / / / / • / / • / / / / / / / / / o ° / / / / o / / o, /<*> / / o o / o/ / ° / / / / / / / / / / / / .2 - O — Owens e_t al . • — Data of this study -^ 1 I I I ' ' J I i ■ ■ ■ 1 .2 .5 1 2 5 k - Predicted 10 2 50 FIGURE 13- MEASURED VS PREDICTED k VALUES 65 100 50 1 1 1 1 I I I ! 1/1 I J* 20 10 O — Langbein and Durum • — Date of this study J I I J i ''I 5 10 20 k - Predicted 50 100 FIGURE ]k. MEASURED VS PREDICTED k VALUES 66 (m.'s) had no part in the determination of the regression lines which were obtained from the prediction equation of other authors. One less degree of freedom (N - 3) was used to allow for the computation about a line independent of the measured data. The result will be a conserva- tive estimate of a ,. For large N and additional data which conform to the regression line as well as the data used in its derivation, o will approach s . The region within which the log of the measured value of k may be expected to lie is then defined by In p + a , . The mean deviation, d, between the measured and predicted k's was also computed for each equation as N N The magnitude of d indicates the average deviation from the predicted line and the sign indicates the direction of the deviation. A tabula- tion of data and computations is presented in Appendix IV. DISCUSSION The reaeration rates measured in this study are significantly larger than those used in deriving the prediction equations of O'Connor and Dobbins (1956) and Churchill et aj_. (1962). The standard error of estimate, s , for the 509 points forming the basis of the Churchill et a was + 0.236. The measure of scatter from this study was + 0.272. It is not to be expected that subsequent measurements will have the same fit 67 to an equation as the measurements upon which the equation is based. The difference in fit between the s of the original study and that of this study and the scatter measured in this study is approximately 9 percent. The d value computed for the Churchill e_t a[. equation indi- cates the mean measured value is 125 percent of the predicted value. The equation is then conservative in small streams; that is, it would usually predict a reaeration rate less than that which would be measured. If waste assimilative capacity were estimated using the k given by Churchill and all other factors were determined correctly the stream should contain more dissolved oxygen than predicted. The measure of scatter with respect to the equation of O'Connor and Dobbins (1956) was + 0.281 which is greater than that obtained for the equation of Churchill. No computation of s was made for the data of O'Connor and Dobbins as it was not known which values were individual measurements and which were averages of measurements. As no s is avail- 3 e able for the original data no comparison of fits can be made. The equa- tion is again conservative as the average measured values are 126 percent of the predicted k values. The equation of Owens et a]_. (1964) is based on k values within the range of those of this study. The measure of scatter computed for the data of this experiment was + 0.332. No s was computed for the data of Owens et_ a_]_. The average measured k values tend to be smaller (64 percent) than those predicted by the Owens e_t aj_. equation. It was thought that the measured k's might be smaller due to the presence of wastewater in the stream. It is generally conceded that the effect of wastewater is to lower the reaeration rate compared to that for pure 68 water (O'Connor, 19&0; Downing, Melbourne, and Bruce, 1957)- The magni- tude of wastewater effects was determined by recirculation of a constant volume of oxygen depleted water in an open vessel at constant temperature while monitoring the oxygen uptake. The saturation oxygen concentration and k were determined by a least squares fit of the oxygen concentration data to the first order gas transfer equation. Tests on deionized water and water from upstream of the wastewater plant indicated that the mea- sured rates were reproducible and that a disinfectant (Roccal, 100 mg/1) added to inhibit biochemical respiration had no effect on reaeration. Rates were then measured for stream water only and stream water plus 10, 25j 50, and 75 percent activated sludge effluent. Problems were en- countered in tests with high effluent concentrations, as deoxygenation by nitrogen stripping resulted in excessive foaming while sulfite de- oxygenation progressed at prohibitively slow rates, possibly due to complexation of the cobalt catalyst. If the foam was not removed the rate of oxygen uptake was up to 150 percent of the rate without the foam. Limited results of tests in which foam was removed are presented in Fig. 15- The tests show a decrease in rate of only h percent at waste concentrations of greater than 25 percent. Although problems were encountered in the tests they indicate that the presence of wastewater did not have a major effect on surface reaeration. The prediction equation of Langbein and Durum (19&7) resulted in the largest scatter of the four equations studied, cr = + 0.^18. The values of k from the artificial channel studies of Krenkel and Orlob (1962) were used as a basis for large reaeration rates in the derivation of the equation. Owens, et aj_. (1964) have indicated the 69 co 1- CO UJ 1- >- a: o o 00 l- < a: o CO z o y- UJ !_ 3 1- Irt z (0 UJ 3 -j ■M LL. c u_ a) LU o i_ UJ a) CJ o_ O -J o CO -d- o < 1- o LA C£ C3 VO CM 00 \0 70 rates observed in the artificial channels of Krenkel and Orlob and British Water Pollution Research Laboratory to be less than would be predicted from an equation based on in-stream data. An equation based on artificial channel data would result in predicted values lower than those observed in an actual stream, which is the case of this study. The measured values were on the average 217 percent of those predicted by the equation of Langbein and Durum. CONCLUSIONS Conclusions which may be drawn from this study are as follows: 1. The prediction equation of Churchill e_t a_l_. provides the best fit to the k values measured in this study. The scatter of the values measured in this study is 9 percent greater than that for the data used to derive the equation. 2. The O'Connor and Dobbins equation yields the second best fit. The scatter for this equation is 1.6 percent greater than that for the Churchill e_t a_j_. equation. 3. The k values measured in this study have a smaller average deviation from the prediction equation of Churchill e_t a_l_. and O'Connor and Dobbins than from the others considered. 4. The Owens ejt a_l_. and Langbein and Durum equations provide progressively larger spreads and average deviations between the measure- ments of this study and computed values. 5. The fact that measured values were lower than those pre- dicted by the Owens e_t a_l_. equation was not explained by effects of wastewater on aeration. 6. The low predictions of the Langbein and Durum equation 71 may be due to the use of artificial channel studies as a basis for large k values. 7. The Churchill e_t aj_. , O'Connor and Dobbins, and Langbein and Durum equations provide conservative estimates of k. 8. If viewed with respect to the data from which they were derived, the prediction equations actually present a mean value and probability range rather than a single k value. 9. There is a basis for using the Churchill e_t aj_. and O'Connor and Dobbins equations on shallow streams carrying an organic load. 72 CHAPTER VI PHOTOSYNTHETIC OXYGEN PRODUCTION AND BENTHAL OXYGEN DEMAND CONSTRUCTION OF CHAMBERS Four chambers were built, two to study phytoplankton and other microorganisms suspended in the water and two to study benthic activity. One of each set was clear and the other opaque. Figures 16 and 17 illustrate the details of the benthic and the plankton cham- bers. Figure 18 is a picture of the benthic chambers with the multi- place DO meter. The chambers were constructed from either half-inch clear or opaque "G" plexiglass. Their volume was 20 liters with a bottom area 2 (within the octagon) of 0.131 m and an internal height of 15-2 cm. The octagon shape minimized dead corners, while only the inlet and outlet glass ells, a thermistor, a DO probe, and a rubber stopper for the air bleed hole were present to interfere with the flow. The plank- ton chambers were completely glued with the only access for cleaning being through a five inch hole in the bottom (see Fig. 16). The ben- thic chambers were also completely glued with access through their open bottoms. Submersible pumps, attached to a heavy \ inch aluminum plate were placed next to the chambers in the stream to keep the water well mixed in the chambers as well as to provide the velocity required by the DO probe. Various preliminary tests were made to be sure that the "Product of Zeno Plastics Co., Gardena, Calif., Model A-l(Bl80) 150 gph. 73 Plan View | l£" diameter Thermi stors , ells He J— 3/' J " diam. DO probe I 3/'!" diam, a i r bleed in 2 6*' 16- 15/16" -IP" H« 1 — r rz VD ] — Plug """J maPSB 11 1 1 It 1 1 / n f ft « rn S i de V i ew HCN FIGURE 16. DETAILS OF PLANKTON CHAMBERS 1^ Plan V i ew r^ 1^" diameter Thermistors, ells *-© 3/4" diam. DO probe Jn 3/4" diam. air bleed 6i" H 16-15/16' -IcM 1 V© o CN4 -In i_ ' i i Side View -In i r^P o o o o o o i FIGURE 17. DETAILS OF BENTHIC CHAMBERS 75 / FIGURE 18. BENTHIC CHAMBERS WITH MULTIPLACE DO METER chambers were adequately designed and would not interfere with biolog- ical processes taking place within them. Light transmission tests were run on the clear plexiglass (reference-air). Algae metabolize most effectively within a given range of visible light - 400 mp to 750 mp - and transmission is 90 percent or better in this range (Fig. 19) • Field tests using a surface deck light meter in conjunction with a similar underwater light meter showed the plexiglass to have little or no effect on the transmission of light. A toxicity test was run on the various components of the system. Equal amounts of BOD dilution water were placed in three sys- tems. In one the water was circulated through each pump with its tub- ing and glass ells, in the second the water was left standing in each chamber, and in the control the water was left standing in a glass bottle, all for about 2k hours. Seven BOD bottles were filled from each system after organisms had been added. These were al 1 incubated at 20°C, and bottles from each were analyzed for DO at 2, k, and 5 days. Figure 20 illustrates that there were no toxicity problems since oxygen uptake was higher in all other systems than it was for the con- trol. Personal correspondence with Dr. 0. L. Pierson (1968) of Rohm and Haas Company, maker of the plexiglass used, indicated that plexi- glass contains nothing toxic and has been used in equipment for some very delicate processes. No specific test was made to analyze the mixing characteristics "Submarine Photometer manufactured by Fred Schueler. Two Weston photronic cells were used, one for underwater and one for above water, with sensi- . . . . . £ k\i amps tivities of tt j, • f t-candle 77 CO CO < C3 X UJ < £ 2 CD e a) > oo CO < —I CT\ 3 CD uo; ssjujsuejx 78 >■ (TJ O oo LU X o o CNJ UJ Z> l/6ui 'ua6Axo p^AiossjQ 79 in the chambers. Observations during the studies indicated that the phytoplankton remained in suspension, but the benthos remained relative- ly undisturbed. The entire mass of water appeared to be in movement, indicating that there were no dead spots. To say that the clear-opaque chambers of either set were com- parable, it was necessary to show that they would run identically under the same conditions. In the lab this was shown to be true for the plank- ton chambers (Fig. 21) using stream water. This was also shown true in the field for the benthic chambers where low light and high turbidity in the stream offered matching conditions for both chambers (Fig. 22). After consultation with various people at the Taft Center in Cincinnati, including Symons and Thomas, it was felt that two hour runs were desirable in that this was long enough to give significant results, yet short enough to be representative of the stream. DO probes and thermistors from all the chambers were connected to a field switch which provided continuous current to all thermistors and probes. Read- ings could thus be made easily and quickly, and continuous monitoring was possible of DO and temperature. The handling of the water was minimal with the benthic cham- bers. Due to their open bottoms, they were simply set carefully and slowly over the benthos so that benthos and overlying water were gen- erally undisturbed. The cutting edges were then slowly forced into the benthos to isolate a bottom section and volume of water. The surface area to volume ratio (S/V) of the chambers is 2 3 about 0.24 cm /cm . That of the 300 ml bottles generally used in light- 2 3 dark bottle studies is 0.85 cm /cm . A rough calculation on the section 80 o oo LU 2 XL cc < O CO I t/1 CC < o o I- ^c ■z. < _l < Q Q < Ll_ o to LU CC o ic < LU CJ >- X o CM LU CC => C3 \£> -3" CM l/6ai ' u36Axq psA[oss[a 81 CO z o o o i^ cc < Q O £30 CO C£ LU CQ < O CC < Q O < I- CD o CO LU > a: ■=} o < >- X o CM CM CC =5 O 1/6uj 'ua6AxQ p9A[oss|Q 82 2 3 of interest in the stream gave an S/V = : 0.04 cm /cm . The assumption was made that the stream bottom was smooth. If actual conditions were accounted for, the stream S/V would be closer to that of the chambers. The four chambers have the following advantages over the light- dark bottle technique: 1. The plankton chambers can be used for both lab and field runs without alterations. 2. The plankton chambers can more accurately measure plankton activity than the light-dark bottle technique. 3- Benthic algae with benthos can be studied with the benthic chambers. k. Benthos other than benthic algae can be studied with judicial placement of the benthic chambers. 5. All chambers closely simulate what is occurring in the actual, free flowing stream. RESULTS AND DISCUSSION The Saline Branch, during the period of interest, was shallow and clear, and contained sufficient nutrients for algal growth. However, it was almost devoid of phytoplankton. In the summer of 1967 a thick growth of benthic algae covered the stream bottom, but in the summer of 1968 this heavy growth did not occur. The major algal genera as observed on July 26, 1968, were Spirogyra near the banks and Closterium as the predominant bottom form. The common aquatic plant was El odea . Chironomids and tubificids largely made up the macroinvertebrates of the benthos, especially in the sludge 83 deposits near the banks. In general, the heavy algal growths were a species of C ladophora . Three major field runs were made involving a 2k hour study on the stream as described earlier. The raw data gathered from these runs and some miscellaneous runs can be found in Tables 23 to 26 in the Appendix V. A total rank analysis as well as a position and a day-by-day analysis of the raw data can also be found in the Appendix V in Tables 27 to 29- The tremendous ranges of values for all the chambers are in- dicative of the problems faced when analyzing a small stream and the factors affecting it. These ranges illustrate the effect of the many variables which influence such a stream. However, the average values for each chamber do suggest several important relationships. First, the benthos had a much greater influence on the oxygen level of this stream than did the plankton. Subtracting the effect of the overlying water, the following ratios can be obtained: LB - LP _ -1.21 - (-0.15) _ -1.06 LP -0.15 -0.05 where LB = oxygen production or utilization rate in light benthic chamber and LP = oxygen production or utilization rate in light plankton chamber, and DB - DP = -3.69 - (-0.73) _ -2.96 _ k DP ~ -0.73 ~ -0.73 8k where DB = oxygen production or utilization rate in dark benthic chamber and DP = oxygen production or utilization rate in dark plankton chamber. These ratios indicate the effect of the benthos, which has often been ignored in the past. Of course, these ratios are only valid for a par- ticular section of a particular shallow stream when stream depth is equal to depth in the chambers. Nevertheless, the benthos should not be ignored in any stream without establishing its contribution to the oxygen balance. Second, the average values of oxygen uptake for the four cham- bers rank in magnitude according to the order that would be expected. The benthos under respiring (dark) conditions showed the greatest up- 2 take of -3-69 gm/m /day. The second greatest uptake was in the benthos under light conditions, though it has far less than that of the dark 2 conditions. The value of -1.21 gm/m /day illustrates that at this point the respiration processes override photosynthetic oxygenation (P) . Yet P is quite considerable as noted by the difference between LB and DB 2 of +2.48 gm/m /day. Thus, the benthic algae during daylight hours seemed to significantly contribute to keeping the DO higher in the stream. The plankton chambers showed much less uptake than the ben- thic and showed how few plankton were in this stretch of stream. How- ever, the LP uptake is considerably less than that of the DP, and again planktonic algae help to keep the DO higher in the daylight (P = +0.58 2 gm/m /day) . 85 Of course, the same algae which maintain the DO level in the daytime help to lower it at night. Thus, heavy growths of algae in this stream have been responsible for DO ' s as high as 18 mg/1 during daylight, but at night the stream approached zero DO. Downing (19&7) graphically portrays this point. It would seem that if benthic and planktonic algae are ever to be considered an asset to the DO of a stream relative to its assimilative capacity, then wastewater treat- ment plant effluent discharge may have to be timed according to the downstream algal cycle of production of oxygen. It can be seen in Table 4 that some of the values in the position analysis are supported by very little data, and, therefore, it is difficult to make a reliable analysis. The LB values showed the effect of the sludge buildup on the north and south banks, while a heavy growth of Cladophora caused the plus value at midstream. The DB values showed a fairly uniform uptake across the first three posi- tions. The high uptake at 3A stream and the north bank is hard to explain. The main flow of the stream was on this side, and there was a heavy growth of the aquatic plant Elodea along the north bank. How- ever, due to rocks it was generally impossible to place the chambers over the Elodea , and the DB should not be affected by stream flow or light conditions. Perhaps a slightly different bottom sediment was present, but this has not reflected in the LB values. More data would probably even out these values. The DP values were fairly uniform, indicating the uniform mixing of the stream, while the LP values reflect- ed different light conditions when the values were obtained. Although the data obtained was very limited, it is nevertheless 86 to cc UJ CO 21 < ZC O cn zd u_ J- 2: LU cc _J u. CD < < 1— 1— < >- cc < T3 E cn o -o o T3 C 03 CD 03 C en X o -Q E 03 in >-| ra c < 03 O -C co CN1 00 CTv J- vO nO — • y ^ CN1 ^—s J" 1 • 00 • NO • PA • J" | O *■- ' J- ^ O ' O CPi 1 cn CO nO r-> cn NO r-~- 1 CN »— v CNJ •— - CNJ ^^ I s *. CO • -d" • CTi • -d- • CN 1 *•— - + OA ■>— • 1 ' 1 CO M- 00 vO CNJ NO — p— 1 r^-—s Cn O , v 00 1 — • NO • « — • LA • CNJ 1 — ' CM *— ' " CO sz -3" no 4-J ^ r->-^^ Cn i- c • CNI • O 03 CNJ — CNI ■Z. DO 1 1 E 03 J" to E I 03 -a (D J- cn > < —- CNI O to CD 1 1 1 LA. CO -4- CNJ + 00 LA o + CNI CO cn — no cn • CNI OA — vO -J- — OA — r^vo • CN O — ' I o +j o -3- cn + o ■M LA CA CO CO Q NO O O CN o CA 4-> o r-. + O o + 03 CD _C 4-> CO CO • rH u a E c O • rH O 03 !_ >- 03 4-J -C c 03 4-1 -O • »-t 5 CO cn <4- C O S >- >- c O -0 !_ T3 • i-l to _c D 03 3 T3 OJ LO O 0) O 03 1 — r— < — CD CD 0) O O O !_ 4-> O- — 03 00 CO .c -z. > NO NO CO cn 1 1 NO • i-H II ■ — CO 1 ■— CN 1 CNJ 1 1 >- 03 z 00 CO en Q ■> — cn jC • i-H • — 1 cn 03 !_ CD > 03 (13 U C QJ l_ 0) o •rH 4-J 03 C - 10 O 4-J o x: a. 87 possible to demonstrate how it might be used in mass balance calculations for oxygen. The difference in measurements of the two plankton chambers (LP - DP) represents the oxygen production (P ) of the plankton. The difference in measurements of the two benthic chambers (LB - DB) repre- sents the gross oxygen production of the benthos and of the plankton (P, + P ). If P is subtracted from this value, then the oxygen pro- duction by the benthos (P, ) is found. The difference in measurements of the two dark chambers (DB - DP) represents the oxygen required for respiration (R ) by the benthos. The dark plankton chamber (DP) rep- resents the oxygen required for respiration (R ) by the plankton. The following calculations based on average values from Table 4 and Table 27 yield: P b = (LB - DB) -(LP - DP) = -1.21 + 3-69 + 0.15 - 0.73 = +1-90 gm/m 2 /day R, = DB - DP = -3-69 + 0.73 = -2.96 gm/m 2 /day b P = LP - DP = -0.04 + 0.20 = +0.16 mg/l/hr r = DP = -0.20 mg/l/hr P Assuming a stream section with similar benthic characteristics and an average depth of one foot with equal light and temperature condi- tions, the following calculations could be made: 2 2 2 Net benthic effect = P, + R, = 1-90 - 2.96 = -1.06 gm/m /day b b 2 Since a water depth of 1 ft is equivalent to 305 liters/m , then 1.06 gm/m 2 /day x 1 day x 1000 mg = _ 0#lZ+ mg/1/hr 305 1/m 2k hr gm 88 Net plankton effect = LP = -0.04 mg/l/hr Total net effect = -0.]k - 0.04 = -0.18 mg/l/hr The value -0.18 mg/l/hr represents the total effect of the benthos and plankton on the oxygen concentration of stream water through a given stream section under given conditions. Any change in depth or conditions would affect this value. In a deep stream several measurements at different depths would have to be averaged for the photosynthetic effect. DISCUSSION OF PROBLEMS IN ANALYZING SMALL STREAMS During a walk through a 6300 foot section of the Saline Branch; the following variables were noted; 1. Changing light conditions - the overhanging trees and tur- bidity of the water limits the light reaching algae and aquatic plants throughout this stretch. 2. Changing depth - this stream ranged from 2 in. to 2 ft. 3. Different plant life - the algae and Elodea were in no way spread in an even, estimable manner. The species of algae present varied from one area to another as well. k. Bottom conditions - various areas were dominated by gravel, silty-sand, or sludge banks. Some areas had mixtures. 5. Flow conditions - changing flows and velocities affect all organisms and especially the establishment of benthic algae. 6. Varying wastewater treatment plant discharges - in conjunc- tion with (5) above, this factor controls nutrient concentra- tions and largely determines which organisms are present. 89 From the above, the complexity of this stream is obvious. There are probably many other factors that might be added to this list. CONCLUSIONS The following conclusions can be made based on this study: 1. The benthos can have a significant effect on the DO of a smal 1 stream. 2. Phytoplankton did not have a great effect on the oxygen balance of this stream during this study. 3- The chambers presented herein provide one means of ob- taining more accurate information concerning those factors which affect the DO of a stream. The few results obtained with these chambers vary widely, but the data indicate proper trends and it appears that the equipment used in this study could provide a meaningful evaluation of the demands and contributions of the benthos and phytoplankton. 90 CHAPTER VII BIOLOGIC STUDIES INTRODUCTION A regular series of 26 biweekly physical, chemical, and biological collections were made from the four collecting stations in the Saline Ditch-Salt Fork system. The study year extended from 13 June 1967 to 28 May 1968. Supplemental collections of the Aufwuchs community were made from these same stations during the summer of 1968. Two series of fish collections were made during the course of the study. These collections were made during late August and early September of 1 967 and 1968. The stations visited included the four collecting stations of this study, all of the Salt Fork system collecting stations of Forbes and Richardson (1908), Thompson and Hunt (1930), and Larimore and Smith (1963) > and such additional stations as were deemed necessary for adequate coverage of the drainage basin. AUFWUCHS Collections of Aufwuchs materials were treated in a manner to provide information regarding the weight and caloric value per unit area, caloric value per unit weight, and the net rate of production, as weight and gram-calories per unit area per day, of the accrued materials. Qualitative information regarding the composition of the biota were also obtained. The series of 26 collections of two-week accumulations of Aufwuchs provides information regarding aspection in the Aufwuchs com- munity. Figures 23 to 26 indicate seasonal changes in the weight of material which is attached to a unit area of substrate. These data 91 CVJ E -o en E (0 Week FIGURE 23. WEIGHT PER UNIT AREA AND CALORIC VALUE PER UNIT WEIGHT OF BIWEEKLY ACCUMULATIONS (13 JUNE 1967 TO 28 MAY 1968) ON GLASS SLIDES FROM STATION SB 2, SALINE DITCH, CHAMPAIGN COUNTY, ILLINOIS 92 E E CL CD ••H 3 5000 2000 - 1000 - 500 - 200 - 100 - 50 - 20 - 10 - 2 - - 6 E ID U -. k 2 U O o - 2 FIGURE 24. WEIGHT PER UNIT AREA AND CALORIC VALUE PER UNIT WEIGHT OF BIWEEKLY ACCUMULATIONS (13 JUNE I967 TO 28 MAY 1968) ON GLASS SLIDES FROM STATION SB 8, SALINE DITCH, CHAMPAIGN COUNTY, ILLINOIS 93 5000 - 2000 - 1000 - eg E <0 0) < 4) a ••H !5 - 6 - 4 CD E <0 o a) > O - 2 FIGURE 25. WEIGHT PER UNIT AREA AND CALORIC VALUE PER UNIT WEIGHT OF BIWEEKLY ACCUMULATIONS (13 JUNE 1967 TO 28 MAY 1968) ON GLASS SLIDES FROM STATION SF 3A SALT FORK, CHAMPAIGN COUNTY, ILLINOIS 3k 5000 2000 1000 E ■D E 0) < Q. en 3 V 4 = C7> E CT) <0 10 15 Week 20 25 FIGURE 26. WEIGHT PER UNIT AREA AND CALORIC VALUE PER UNIT WEIGHT OF BIWEEKLY ACCUMULATIONS (13 JUNE 1967 TO 28 MAY 1968) ON GLASS SLIDES FROM STATION SF 10 SALT FORK, CHAMPAIGN COUNTY, ILLINOIS 95 indicate maximum accrual during winter and early spring. Relatively high populations continue through summer. Populations begin declining during late summer and reach minimal values during late fall and early winter. Newcombe (1950) reported similar seasonal changes in the weight of accrued materials on artificial substrates in Sodon Lake, Michigan, but he found maximum populations continuing to early fall. Others (Butcher, 19^+6; Knight and Ball, 1962) also indicate maximal standing crops during summer, but these studies indicate minimal standing crops during winter and spring. It should be pointed out, however, that these other studies (Butcher, 19^6; Newcombe, 1950; Knight and Ball, 1962) were not conducted in polluted waters and values obtained were consid- erably lower than those reported here. Newcombe (1950), for example, 2 found maximal values approaching 20 mg/dm /10 days. Results of the 2 present study indicate values ranging from 100 to 1000 mg/dm for a similar period of exposure. Figures 23 to 26 indicate an inverse relationship between the weight of attachment materials per unit area of substrate and the caloric value of these attachment materials. Figure 26 most clearly indicates this relationship. It has been suggested (C. I. Weber, per- sonal communication) that the high weights are caused by silt and clay depositing upon the substrate. This would cause weight increases in caloric value. In fact, silting of the substrate might result in lower accruals of photosynthetic materials, hence lower caloric values. Butcher ( 1 946) and Mclntire (1966) report larger standing crops in fast currents where siltation was minimal. Figure 27 represents seasonal changes in the net production 96 16 - ]k - 12 -o 1 o> CD > 10 - 8 - 6 - k - 2 - Week FIGURE 27. NET PRODUCTION OF AUFWUCHS AS INDICATED BY BIWEEKLY ACCUMULATIONS (13 JUNE 1967 TO 28 MAY 1968) ON GLASS SLIDES FROM FOUR STATIONS ON THE SALINE DITCH- SALT FORK SYSTEM, CHAMPAIGN COUNTY, ILLINOIS 97 of Aufwuchs from Stations SB 2, SB 8, SF 3A, and SF 10. These data in- dicate increased production in the more polluted reaches of the stream. Butcher (19^+7) reports low population of attached algae immediately be- low a source of pollution with peak populations occurring eight miles downstream. This peak was followed by a gradual decline in standing crop, presumably reflecting a decrease in the nutrient content of the water. Figure 27 also indicates irregular fluctuations in net pro- duction at the more polluted stations while at the relatively clean- water Station SF 10, net production follows the annual temperature cycle (Fig. 28). Butcher (19^+6) suggests such irregular fluctuations are due to quickly changing environmental factors such as those expected below a wastewater treatment plant outfall. The second series of Aufwuchs collections from 11 June 1968 to 5 August 1968 provide information regarding the rate of accrual of material and the succession of species which takes place during community development. Figures 29 to 32 indicate that the weight and caloric value of the attached materials increase proportionally. Stations SB 2, SB 8, and SF 3A (Figs. 29-31) indicate that maximum community development is completed in two weeks. This corresponds to the time interval used in the biweekly series of Aufwuchs collections. Butcher (19^+6), Cooke (1956), and Blum (1957) indicate that a two-week exposure period may preclude the development of a climax or permanent community. Mclntire ( 1 966) states that fast currents retarded initial attachment for periods up to three weeks. Kavern, Wilhm, and Van Dyne (1966) represent standing crops by a sigmoid curve which reaches an upper asymtote after two months. 98 Weeks FIGURE 28. CHANGES IN WATER TEMPERATURE FROM JUNE 1967 TO JUNE 1968 AT FOUR STATIONS IN THE SALINE DITCH-SALT FORK SYSTEM 99 5000 - 2000 - E ■o "^ V •«-■ L. 200 o ^— ID <_> T3 C 100 ID CM E XI CO 50 E «D 4) l_ < a) a. en a) 3 20 -' 10 - 5 - 2 - 20 30 Day of study FIGURE 29- CHANGES IN WEIGHT AND CALORIC VALUE PER UNIT AREA OF ACCRUED MATERIAL ON GLASS SLIDES FROM 11 JUNE 1968 TO 5 AUGUST 1968 FROM STATION SB 2, SALINE DITCH, CHAMPAIGN COUNTY, ILLINOIS 100 5000 - CM 2000 E -D ^ pa (D U 1000 CD a> 3 "55 500 > u •«H L. o !_ < •M •»i C ID 20 l_ E CD 0) < •r-l Q. 3 100 - 50 - 20 10 - 2 - 10 FIGURE 31. 2 30 Day of Study 40 50 CHANGES IN WEIGHT AND CALORIC VALUE PER UNIT AREA OF ACCRUED MATERIAL ON GLASS SLIDES FROM 11 JUNE 1968 TO 5 AUGUST 1968 FROM STATION SF 3A, SALT FORK, CHAMPAIGN COUNTY, ILLINOIS 102 E cn a) 3 > 1_ o O "O c E ■o \ cn E <0 i_ < 0) cn ••H 0) 3 5000 - 2000 - 1000 - 30 40 Day of Study 50 FIGURE 32. CHANGES IN WEIGHT AND CALORIC VALUE PER UNIT AREA OF ACCRUED MATERIAL ON GLASS SLIDES FROM 11 JUNE 1968 TO 5 AUGUST 1968 FROM STATION SF 10, SALT FORK, CHAMPAIGN COUNTY, ILLINOIS 103 Sladeckova (1962), however, states that a two-week exposure is sufficient for all organisms except hydra, bryozoa, and sponges. Station SF 10 accumulations (Fig. 32), from the clean-water portions of the stream, did not reach an asymptote after a 35-day exposure period. Tampering with the sampler prevented longer exposures at this station. Stabilization of the Aufwuchs community, the upper asymtote, occurs when production is equalled by sloughing (King and Ball, 1 966) , or by sloughing and grazing (Kevern, Wilhm, and Van Dyne, 1 966) . Mclntire (1966) found that sloughing rate increased with time of exposure and with increased water velocities. It is suggested that the fluctuations appear- ing in Figs. 29 to 32 are due primarily to sloughing, although some grazing organisms, notably chironomid larvae and Physa , were often col- lected. It is noted that sloughing did not occur prior to 20 days of exposure and it is therefore not considered a factor affecting the stand- ing crops measured in the biweekly collecting series. Figure 33 indicates changes in the net rates of production over the 50-day exposure. Stations SB 2 and SB 8 in the more polluted portions of the stream, show extreme fluctuations in production rates and much higher rates of production than found at Stations SF 3A and SF 10. Highly variable stream conditions below the wastewater treatment plant outfall are thought to be responsible for the extreme fluctuations (Butcher, 19^6). Higher nutrient levels at Stations SB 2 and SB 8 could account for higher rates of production at these stations. Data regarding the composition of the Aufwuchs indicate a shift from a heterotrophic community to an autotrophic one as one moves 104 30 - 25 - (0 u I ot 20 - - 15 " 03 10 5 - r - i i — i i — I r i i r- / WSta. SB 2 — / A \ - / /'» \ > \ / / ^ \ / / \ \ / / \ \ ^ m / ' » \ / ' v \ / / . \ \ / ' v \ I \ \ / ' v \ / / \ \ ' J x \ I ' Sta x \ -\ ['^SB 8 \ \ ', / \ \ '/ v \ // \ \ i ' / \ \ / / V \ / / \ \ ' / \ \ ■ ' \ \ \ - \ ' J \ \ / ~ \ f >* \ \ '\^ v V f ^^*"* , *^—i -lllll- ^ / ^■Sta. SF 10 • — ..^ i i i i* • •■I _i j — 1 10 15 20 25 30 Day of Study 35 40 kS 50 FIGURE 33. CHANGES IN NET PRODUCTION OF AUFWUCHS ON GLASS SLIDES FROM 11 JUNE 1968 TO 5 AUGUST 1968 FROM FOUR STATIONS ON THE SALINE DITCH-SALT FORK SYSTEM, CHAMPAIGN COUNTY, ILLINOIS ]05 downstream away from the Urbana wastewater treatment plant outfall. Station SB 2 produced a population rich in stalked ciliates, primarily Episty 1 is and Carchesium . Downstream these organisms were replaced by diatoms, including species of Cocconeis , Navicula , Suri rel la , and Nitzchia , and filamentous algae ( Spi rogyra and C ladophora ) . The accrual study indicated that colonization in the "cleanwater" portions of the stream proceeded from small diatoms to large diatoms to filamentous green algae. Community development was more addition of species rather than succession. This was also noted by Butcher (19^6, 19^7) and Mclntire (1966). During the later stages of community develop- ment chironomid larvae and physid snails frequently became established on Aufwuchs slides. It is not felt that these "grazers" significantly affected the biomass of the epiflora. PLANKTON, PARTICULATE AND DISSOLVED ORGANIC MATERIAL Figures 2>k to 37 illustrate changes in the caloric values of the dissolved and particulate (including the plankton) organic material from four stations in the Saline Ditch-Salt Fork System, Champaign County, Illinois, from June 1967 to June 1968. The distinction between "dissolved" and "particulate" has often been unclear and generally has varied with the investigator. Birge and Juday (193^) employed a Foerst continuous plankton centrifuge. This method was reported to retain 95 percent of the particulate material larger than bacteria, and 25 to 50 percent of the latter. They defined "dissolved" as anything not removed from the water by this centrif ugat ion. Filtration techniques were employed by Slater (195^) who used 106 (TJ U I D1 <0 O 5000 - 2000 - 1000 - 500 ~ 200 100 - 50 - 20 - 10 - 5 - 2 - FIGURE Ik. CALORIC VALUES OF DISSOLVED AND PARTICULATE ORGANIC MATERIAL FROM JUNE 1967 TO JUNE 1968 AT STATION 1 SALINE DITCH, CHAMPAIGN COUNTY, ILLINOIS 107 5000 2000 u i en (0 1000 500 200 100 50 20 10 h \ |l Disso lved J. 10 15 Week 20 25 FIGURE 35. CALORIC VALUES OF DISSOLVED AND PARTICULATE ORGANIC MATERIAL FROM JUNE I967 TO JUNE 1968 AT STATION 2 SALINE DITCH, CHAMPAIGN COUNTY, ILLINOIS 108 5000 2000 1000 o i O 500 200 - 100 50 - 20 10 1 5 Week 20 25 FIGURE 36. CALORIC VALUES OF DISSOLVED AND PARTICULATE ORGANIC MATERIAL FROM JUNE 1967 TO JUNE 1968 AT STATION 3 SALT FORK, CHAMPAIGN COUNTY, ILLINOIS 109 5000 - 2000 - 1000 - 500 - rc o FIGURE 37- CALORIC VALUES OF DISSOLVED AND PARTICULATE ORGANIC MATERIAL FROM JUNE 1967 TO JUNE 1968 AT STATION k SALT FORK, CHAMPAIGN COUNTY, ILLINOIS 110 No. 2 Whatman filter paper to retain plankters and particulate material in the water. More recently membrane filter techniques have utilized pore sizes down to 0.45m. (Copeland, Minter, and Dorris, 19&4) to remove particulate material. The sand filtration technique in this study yields a maximum pore size of 64u.. Actual pore size is much smaller (Welch, 1948). Material passing through the filter bed and membrane are considered here to be dissolved. Retained material includes both the plankton and the particulate matter. Figures 34 to 37 indicate that dissolved organic matter is generally maximal at Station SB 2 and decreases progressively downstream. These decreases are thought to be the result of the joint effects of sedimentation, utilization by the biota, and direct oxidation in the water column. Sludge banks in the upper portions of the stream attest to the importance of sedimentation as a removal, although the rate was not measured. Utilization by the biota is discussed by Pearsall (1932), Slater ( 1 95^+) > and Cushing (1964). Slater (1954) presents an extensive review of dissolved nutrient utilization, especially by protozoans. Direct oxidation is indicated by low dissolved oxygen values in the upper reaches of the stream (Table 9) • Little correlation was found between the caloric values of the dissolved and the particulate organic matter. Birge and Juday (1934) indicated that this was due to the fact that factors other than dissolved substances were involved in regulating the abundance of particulate mate- rial. Cushing (1964) found significant correlations in only four of 80 samples. Ill Both of the above studies dealt with essentially lentic plank- ton populations as their "particulate" component. Microscopic examina- tion of Salt Fork collections indicated only a few diatoms and algal filaments in the water column. As these forms were abundant in the Aufwuchs it is felt that they represented dislodged individuals from an otherwise attached community. The bulk of the particulate matter was primarily a 1 lochthonous in origin and was derived almost entirely from the wastewater treatment plant effluent. Figures 3^- to 37 indicated that high values for particu- late matter corresponded to low stream discharge (Figs. 38 to 5^ in Appendix I) . This suggests a constant level of inflow with the resulting concentration being determined by the amount of dilution water available in the stream. Seasonal variations normally associated with planktonic populations (Birge and Juday, 193^) were not obtained. BENTHOS Baker (1926) and Ludwig (1932) discuss the relation between benthos and water pollution. One generally expects two trends with re- gard to aquatic communities in polluted and nonpol luted reaches of a stream (Gaufin and Tarzwell, 1 955) - Species diversity is lower but the numbers of individuals of each are higher in polluted areas. These trends are best seen in the results of the benthic collections of this study. Table 5 summarizes the most abundant groups at each of the four biological sampling stations. Table 5 indicates a poorly developed benthic fauna at Station SB 2. It must be stressed that this table represents the cumulative results of the study. At any one time the bulk of the population 112 TABLE 5 MEAN BIOMASS OF ABUNDANT TAXA IN THE BENTHOS AT THE FOUR BIOLOGICAL SAMPLING STATIONS IN THE SALINE DITCH-SALT FORK SYSTEM JUNE 1967 TO JUNE 1968 2 Mean Biomass in mg/m of Various Taxa at Station Taxa SB 2 SB 8 SF 3A SF 10 Tubificidae 38,290 51,010 41,200 2,916 Chironomidae 3,890 4,220 550 830 Physidae 1,990 465 310 42 Hirudinea 166 310 290 20 Ceratopogonidae 2 3 20 Simu 1 i idae Asel 1 idae Amphipoda 3 3 Corixidae 4 24 Hydropsychidae 3 Mean Total Biomass 44,300 57,015 42,780 4,800 38,290 51 ,010 41,200 3,890 4 ,220 550 1,990 465 310 166 310 290 2 3 5 2 250 3 113 consisted mainly of three taxa, the Tubif icidae, Chironomidae and Physidae. The tubificids were primarily Limnodri lus ; however, Tubif ex was also encountered. A group of five species of Chironomidae was taken from Station SB 2. Since chironomid taxonomy is often based on adult characters, these species, usually taken as adults or pupae, still await determination. All of the Physidae were Physa gyrina . Station SB 8 provided the most diverse populations of benthic organisms. Population densities were extremely high (Table 5). Tubificid 2 populations alone often exceeded 170 g/m . Allen (1951) reported maximal 2 values of 30 g/m for the entire benthic community. The diversity of biota at Station SB 8 is thought to be a result of the diversity of habitats available. Substrates included mud, sand, and gravel. Although overall water quality increased down- stream from Station SB 8, species diversity did not increase. Gersbacher (1937) and Eggleton (1939) noted the importance of a stable substrate in developing extensive benthic communities. The occurrence of various clean-water forms at Station SF 10 (Caenidae, Elmidae and Hydropsychidae) attest to the improvement of water qual ity. Fish predation has been shown to exert an effect on the benthic community (Hayne and Ball, 1956). It is not thought to be of importance in the Salt Fork due to the relatively low fish densities encountered. Various measures of benthic productivity have been made (Allen, 1951; Hayne and Ball, 1956; and Mann, 1964). These measures indicate annual turnover ranging from 1.7 to 15 times the standing crop at any one time. From this it can be seen that benthic production may be very high, 114 2 at times exceeding 2 kg/m . The relationship between the benthos and the syrton will be discussed in the following section. SYRTON The fact that macroinvertebrates within a stream community are often carried passively with the current has been known for a long time. Dendy (19^) , however, was the first to recognize this as a natural phenomenon. The term "syrton" was first proposed by Berner (1951) • He described the syrton as being "a heterogeneous, macroscopic group of living and dead organisms including all of the aquatic and ter- restrial insects, other invertebrates, and the small fishes being carried by the current on or below the surface of the water." The diurnal cycle of syrton biomass as related to light in- tensity has been discussed by Waters (1961, 1962a, 1962b, 1965), Anderson (1966) and Fishman (I968) . Most studies of syrton (Berner, 1951; Waters, 1961, 1962a, 1965; and Elliot and Minshall, I968), however, imply that the syrton composition reflects that of the benthos both qualitatively and quanti- tavely. Waters (1962a) even proposes that syrton studies be used to pro- vide population data regarding benthic organisms. Berner (1951) did note that annelids dropped in abundance from 21.5 percent in the benthos to 0.5 percent in the syrton. Elliot and Minshall (1968) found dipterans more abundant in the benthos than in the drift. When the results of syrton collections made in this study (Table 6) are compared with the results of the benthic collections (Table 5) , several facts immediately become apparent. 115 TABLE 6 MEAN BIOMASS OF ABUNDANT TAXA IN THE SYRTON AT THE FOUR BIOLOGICAL SAMPLING STATIONS IN THE SALINE DITCH-SALT FORK SYSTEM JUNE 1967 TO JUNE 1968 3 Mean Biomass in mg/m of Various Taxa at Station Taxa SB 2 SB 8 SF 3A SF 10 Chi ronomidae 470 8 + + Psychodidae kO + Tubificidae 2 9 + + Physidae 3 Ceratopogonidae + Simuliidae + + Copepoda + + Cladocera + + Asellidae + + Corixidae + + Amphipoda + Mean Total Biomass 550 20 <5 <5 A + indicates less than 1 mg/m . 116 In the benthic collections, tubificids made up the bulk of the biomass (approaching 90 percent). In the syrton, however, tubificids are almost absent. Mollusca are also lacking or poorly represented in the syrton. The sessile nature or heavy shells of these organisms prob- ably precludes their existence in the syrton. The Hirudinea were not taken in syrton collections although they were well represented in the benthos (Table 5). This is surprising since many are active swimmers and are likely to be in the water column. The most abundant group in the syrton at most stations were the Chi ronomidae. Whereas benthic collections yielded mainly larval forms, syrton collections were fairly evenly divided between larvae and pupae. Adults were often encountered in considerable numbers. It ap- pears as if pupating forms leave the benthos and drift along in the syrton. Emergence of the adult then takes place at the water's surface. The syrton period represents an intermediate habitat between benthic and aerial existence. This period conceivably serves as a dispersal mechanism. Elliot and Minshall ( 1 968) also report many emerging Diptera in the syrton. Notable is the occurrence of considerable numbers of Psychodidae in the syrton from more polluted portions of the stream (Table 6). These organisms were almost wanting in the benthos (Table 5). The bulk of the psychodids were Psychoda al ternata . Occasional ly a £. cinera was taken but only rarely. Psychodids are not normally associated with streams. Large numbers, however, are known to live in trickling filters in waste- water treatment plants (Headlee and Beckwith, 1918). The fact that these organisms decrease in abundance downstream from the treatment plant 117 and are generally in the syrton rather than in the benthos suggests that they enter the stream from the trickling filter effluent. Reduc- tions in numbers downstream are attributed mainly to emergence of adults, although some predation may also occur. Although it is not reflected in Table 6, large numbers of ter- restrial insects were taken in syrton collections. Species composition was very diverse and numbers of a given species were too low to be rep- resented in a table giving mean values for the entire study. Berner (1951) noted the presence of terrestrial organisms and included them in his definition of syrton. Elliot and Minshall (1968) noted that the terrestrial component of the syrton was only important during spring and summer months. The present study indicated high densities of ter- restrial organisms during late spring, summer, and early autumn. The importance of this al lochthonous material to the aquatic community was well noted by Berner (1951) who found that terrestrial organisms com- posed 45 percent of the weight of stomach contents of fishes. FISH A large amount of data regarding the fish populations of the Salt Fork is in the files of the Illinois Natural History Survey. In- tensive sampling in 1899 by Forbes and Richardson (1908), in 1928 and 1929 by Thompson and Hunt (1930), and again in 1959 and i960 by Larimore and Smith (1963) has resulted in three major publications which illustrate many changes in the fish populations and relate these changes to the socio-economic development of the drainage basin. Collecting stations visited in this study correspond to the 118 kl used by Thompson and Hunt (1930) and Larimore and Smith (1963)- Thirty-three stations were visited in 1967 and 29 were visited in 1968. Twenty-four species of fishes were collected in 1 967 and 27 were collected in I968. The bulk of these collections agree with the existing distributional data. Several notable exceptions should be pointed out, however. Larimore and Smith (1963) list Carpiodes carpio (River carp- sucker) as hypothetical ly occurring in the Champaign County portions of the Salt Fork. It was known to exist in the Vermilion County portions of the stream. Collections in 1 967 included £. carpio from five stations widely distributed within Champaign County. The 1968 collections added another two stations to this list. Pimephales promelas (Fathead minnow) was not listed from the Salt Fork by Larimore and Smith (1963). The 1967 and I968 collections show this species from eight Salt Fork stations. Again, this species is known from downstream areas (Larimore, Pickering, and Durham, 1952). A single specimen of Lebistes reticulatus (Guppy) represents the only record of this species from Illinois waters (Philip W. Smith, personal communication). It doubtless represents a released or escaped aquarium fish. Of the 66 species of fishes previously reported from the Champaign County portions of the Salt Fork, 51 new distributional rec- ords were among the I967 and 1968 collections. Of particular note are Dorosoma cepedianum (Gizzard shad), six new records all in the main stream; Etheostoma spectabile (Orangethroat darter), six new records from small tributaries; and Notropis chrysocephalus (Striped shiner), 119 eight new records from small tributaries. In regard to the possible effects of changes in water quality, 1967 and 1968 collections yielded few fishes, if any, in the Salt Fork and Saline Ditch below the Rantoul and Champaign-Urbana wastewater treat- ment plants, respectively. Earlier studies indicated a gradual decline in fishes in these streams (Larimore and Smith, 1963). Data obtained in the present study indicate that this decline has continued. CONCLUSIONS 2 1. Aufwuchs accumulations from 100 to 1000 mg/dm are pro- duced in a two-week period. 2. Aufwuchs collections indicate an inverse relationship between the weight of attachment materials per unit area of substrate and the caloric value of these materials. 3. Production of Aufwuchs is higher in the more polluted reaches of the stream. k. The dissolved organic component of the water decreases progressively downstream from the wastewater treatment plant outfall. 5. The bulk of the particulate organic component of the water is derived from al lochthonous sources. 6. Species diversity in the benthos increased progressively downstream from the wastewater treatment plant outfall. 7. Syrton collections are not representative of benthic com- munities. Tubificidae, Physidae, and Hirudinea are poorly represented in the syrton while Chironomidae pupae and Psychodidae are more abundant there. 120 8. Fish collections indicate that Dorosoma cepedianum , Etheostoma spectabi 1e , and Notropis chrysocepha lus have expanded their distribution within Champaign County, Illinois 9- Carpiodes carpio and Pimephales promelas col lections are the first records of these species from Champaign County, Illinois. 10. 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HYDROGRAPH FOR STATION SB 1, AUG. 1967 136 100 i i r I I I | I I I I | I I I I | I I I l | I I I I 90 80 70 — 60 50 — ko 30 20 10 I I I 1 I I I l I l I I I I I I I I I I I I I I I I I I I I 10 15 Date 20 25 30 FIGURE 40. HYDROGRAPH FOR STATION SB 1, SEPT. 1967 137 500 I 1 | I I I I | I I I I | I I I I | I I I I | I I I I | I 450 400 350 300 250 — -C 200 150 100 50 nl I I I I I I I I I I I I I » I I I I I I I I I I I I I I » I 10 15 Date 20 25 30 FIGURE 41. HYDROGRAPH FOR STATION SB 1, JULY 1968 138 500 450 I I I ,[ I I 1 I | I I I I 1 I I I I | I I I I | I I I I | 1 ,1200 cfs F 400 350 300 <*- u 4) l_ « » . I i i i i I i i i i I i i i i I i i i i I'iTI 10 15 Date 20 25 30 FIGURE 42. HYDROGRAPH FOR STATION SB 1, AUG. 1968 139 500 I I I | I I I I | I I I I | I I I I | I I I I | I I I I | I 450 400 350 300 ? 250 TO o 200 150 100 50 o Li '■'■'■'■'■*- '''■»■' 10 15 Date 20 25 30 FIGURE 43. HYDROGRAPH FOR STATION SB 1, SEPT. 1968 140 00 I I I I I I I I I I I I I I I I I I I I I I I I I I I I I 90 80 70 — 60 _ 50 kO — 30 20 10 — nl I I I I I I I I I I I I I I I I I I I I I I I I I I I I 1 I 10 15 Date 20 25 30 FIGURE 44. HYDROGRAPH FOR STATION SB 6, JULY 1967 141 00 I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I 90 80 70 60 50 ko 30 20 • • » * 10 I I I I I I I I I I I I I I I I I I I I I I I 1 I I I I I I 10 15 Date 20 25 30 FIGURE 45. HYDROGRAPH FOR STATION SB 6, AUG. 1967 142 00 I I I I I I I I I I I I I I I I I I I I I I I I I I I I I 90 — 80 70 60 50 40 30 20 10 I I I I I I I I I I I I I I I I I I I I I I I I I I I 1 I I I 10 15 Date 20 25 30 FIGURE 46. HYDROGRAPH FOR STATION SB 6, SEPT. 1967 143 500 I I I | I I I I | I I I I | I56O cf I I I I I I I I I I I I I I 450 400 350 300 250 200 150 100 50 1 1 1 1 I 1 1 1 » I 1 1 1 1 I I I I I I I I I I I I I 10 1 5 Date 20 25 J -M" FIGURE 47. HYDROGRAPH FOR STATION SB 6, JULY 1968 500 | I I I I | I I I %000 cfs I I | I I I I | I I I I | I I I I | I 450 400 350 300 — CO CD l_ (0 -C o 250 200 150 - 100 — 50 I I I I » I I I I I I I I I l l 1 » I » 1 l » I I » I I I I 10 15 Date 20 25 30 FIGURE 48. HYDROGRAPH FOR STATION SB 6, AUG. 1968 145 500 450 400 350 — 300 — in 4- o 1000 cfs 450 400 350 300 250 200 50 I I I I I I i i i I i I i I I i i 1 5 10 15 i i I i i i i I i i i i I i 20 25 30 Date FIGURE 5*+. HYDROGRAPH FOR STATION SF 10, AUG. 1968 151 APPENDIX II Results of Field Surveys 152 o ^ CD CT1 E Q 1 — — (N J" -3- i — o CA O LA -d- co O ■* — O en ca CO vO CO J" vo co CM CO CA cr» E CA CM CM CA CM ■J- CM *~ -o CD Irt 1 — > "D r— ra . — •r-* ^ -d- LA LA -4- CM -3- CO r— J" r»« r^. 4-1 o i— en CA vO CO CTv r>- CA CM 3 CA i— CO o l/> O E ca •J" -d- -3" J- -d" -3" J" J- CA 1- 10 CO CO < CO vO en 3Z O < LL. o Z3 CO cc \- co u. o CO I- — J CO LU 4-J I/) ■■H (0 ca c o .^ — o — \ ro ro en o -* E 0) "O O cn — E _c o o \ q cn E X CA vO CA CM O -3- IA CO LA VO vO -4" vO LAvO LACA vO vO vO O VO J" CO O CO -3- CA ^- O CM CM CM CM r— F— CM CM >— CM CM CM CM CM CM CM csi CA LA CO CA LA CO CA LA CO — CM CA LA CA 1^- CA 1^ CA vO CA vO CM CA CA — — J" CA CA CM -4- CO LA CA LA LA J" CO 1^. -d- — vO r^ VO r^ 00 r-^ r^. CA CM J- CM J- o LA O O CM CM VO CA CO — O O 00 r->« r-^ r-^ -d- O O CO LA LA la vO vO vO vO \D CO CM CO CO CA CA -0 CD LA LA CO O O O CM LA O O LA — +J J" J" ■— CA LA LA r— ■— -d" -d- O Q. CD E CO CO CA CA CA CA O O O — ro O O O O O O CO vO < — — — CM vO CO m co co co co co CO CO CO CO CO z> — CA LA — — CO CO CO CO CO 153 c o — o E 03 O o . o O O o o O O o o O o >+- o O O o o O O o O o o c o o O o o r^ o o o o -* o o rA o O o o CM o o -d- CA ■— CM fA CM ca CA CTl CA ca r^. CM CM ca J- J- CM . O O O o o O o O O o o 1/) o O o o o O o O O o o — T3 c o o LU _i CO < I- 00 vD CA O cc < >- LU > CC wo co < LU CC \- co CO co LU CC CD E in J- O a. v> 03 in D !_ o XL a. in o s: o_ 4-> i- o o I- c en O O CO c cr E to 03 c CD cr O O ■M O I CA O I CM O CA CD O o o o — o o CTi — O O O 00 o o LA O vO CTi O O J" o o oo o o o o o o r*s -j- o CM — -d- — CM — CM — oo r»«. rs. — — o LA o o 00 00 LA CM O LA CA CM CM CM VO CA CM LA O CA o -4- J- — — CM — — — CM ca CM CA CA CA CM LA 00 CA O O LA O CA N 00 00 CM CM CM CM 00 LA LA LA O — CA O — LA LA CA CA CA CA LA — CA -3" O 00 -3- 00 o — o CA vO r-«. -J- vO CM — o -4- 00 oo LA CM LA 00 00 00 LA — -d" CM -Cf -d" VO LA O D O O O CA LA O 00 CA v£> OO CA -J" N OO 00 m s vo r>» vd -j- 1^. vO LA -Cf CO vO CM — CA o CA o — — — o — — o 00 oo LA LA CM O o LALA-3--J--J--d-J- LALAvO LA r— CA 00 CM VO LA vO vO vD r»s \£> o o o o o o o LA c o v£» • rH < 1— o vO 4-> F— *— CM \D 00 »— CA LA *— i— 03 Ll. 4-» QQ CO CO CO CO co u_ li_ Li_ Ll. Ll_ CO to to CO CO CO Z3 co CO CO CO CO 15*f oo UJ _i CQ < 1- co vD >- LU to \- co co h- co UJ en III -d- o Q_ I/) CO I/) D — O cr -c E Q. 10 O -C D_ l_ O t/1 ro c CD o 4-> I CA O O LA r-. o 1 CM la CO -d- LA O • — CM ca CA O CD O E O V Q CD E 05 \D CA -d" -d" CO — CA v£> -d-J-J-vOvOvO LAOO OCOMD — • -d" r~- LA P^. \D VO LA CM O O CA CA CA CA CA o O o O LA O o O CA O CA LA O O oo CA O o CA o o O o VO — CM — CM — — — — O o — CM CM CM 2 5 LA o CA 00 00 CA LA LA a\ CM OO CA -Cf CA ■— CA • — CM CM CA CA CA CA CM ■4" CM O LA NX) CA LA r^ CM CA -d" CACM CMvOCACACAr^COO CM CM -d" CA CT> 0O CA CM — 00 -d" co o LA CA LA CO CA LA CA v£> CA CM CA CM — -d- O CM CM O O vO CO CA -d" LA — vOvO LA LA VO \£5 vO vO LA LA LA LA LA VjD LA LA oo LA en LA CA LA LA LA LA VO LA VO LA LA CM LA LA LA O LA LA LA LA LA LA LA LA LA LA LA LA VO VO r-~ r^ p^ o o o o CM O ■4 O LA LA LA LA O o LA CA o LA o o LA O CM O CA O LA LA CA CA CA CA -d- -d- -d- -4" LA LA LA LA LA vO c O vO • |H i— o LA +J »— CM LA vO oo i— CM CA 4" LA r^ *— i— CO LI- 4-1 CO CQ CO CQ CQ CO LL, Ll. LL. Li_ LL. LC Ll. LL. CO CO CO CO CO CO ZD co CO CO CO CO co CO CO 155 00 vD Cn cn LU -J < >- LU cc co < LU h- co Ll_ O CO H- _J z> to LU o en oq E O CD o E XI .— > X — CO — -iH ' — 4-J O — D1 O i/l O E t— CO •h m rr\ c o • rH — O — \ fU <0 Cn O -* E XI O en o o \ q cn E Q) a. +j E o (0 E ro CO co CO o CO CO ^o o CM CO vO o — -d- LT\ CM CNJ O CO CTv J- co -d" co co Cn O — -d" fO vfl vD 4 CO v£) CO vO LA -d" CO -d" o co r-. vo LA CM -d- vO LT\ J- CO la ■ — ' — vi> 00 — — CO vo co co -d- -d- -d- -d- -d- O LTV J- -d- -cr MD cn cn CO — — -3- vo o co r^ r-*. vo -d- m n- m cm r>^ r--» ltv cm — CO r~- O CO J- co cn r^ cn cn r^ -d" CO J- i — CO LA -d" LA CM CO co CO co -d- CO CO O •4- CO CM >— CM CM CM CM CM CM CM CM CM ■ — ' — CM CM CO vO CM CM — LA CM — O cn CO cn CO CO CO co LA O LA r^ CM CO CO CM CM CM CO v£> -d - Ocov£> o -d - -d" -d"- O CO r^ co cn oo cnoo laoo r*. co oo o o — LA LA vO LA LA O CO CO -d - cn r^ r^- -d - cmvOvo cn vo ■ — -d" vo CO CM J- -d- CM CM CO CM CM CM CM LA CM LA CM LA >^0 CM CM 2 "> • O «4- LA J" vO LA O — o CM co CO CM CO o o co -d" LA O LA LA O O CM — O CO O O LA LA LA O — -d- oo o 00 o 00 o 00 o cn o cn cn o o cn o cn cn o o o o — — cn CM LA J- -d"-d" LA CO LA v£> LACM CO -d" LA — O LA LA 00 LA LA CO O 1^ 00 CM LA CM c o MD • fH t— o CO vo +J <— CM J" vO CO i— co LA p^. •— » — ■ — nj Li_ +j CO CQ 0Q CQ CQ CO Lu Lu Lu Lu Lu Lu Lu CO CO CO CO CO CO Z3 CO co CO CO CO CO CO 156 00 vO CA -o C • i-i +J C o u ca CD < I- O >- LU > an CO < UJ o CO CO LU en "H E o o o O O O o o o o o O O o o o o o o o O o o o o o O o o o *— o o o O o o o o o O o o o CO \ o o o O o la o o o CM LA CM LA o • oa CA o ca o v ca -J- CM V V 0) o I — CM CM CM 00 CM • — Ll_ c ■M C =5 O 1— o O O O o o O o O O O o o CJ F o O O O o o O o O O O o o " v - CNI O o O o -cr O o o v£> O o vO JO O , — -3" o o o r-. oo o o _ O oa , — ■i-j c LA CM o 00 vO CM CM o CM J" 1— o ' — CM ' — ' — 00 CM • o O O O O O O O O O O O O 1 — M- F c CM O O o O CA O O O OO 00 CM CM o -3" CA CM ■ — O MD CA r— CA V o o LA CM r^ -d- CA CA CM CM o ■ — "~ ■ CM z. . O O o o O O O O O O o o O 0_ CO X. CO CM O o o O CA O O O CA CA CM LA !_ -d- CA o o O \0 CA ■— CA ■ — CM o_ LA CM CA CA CM CM CA CM J- CM CM CD E in -3- o D_ {/) ro ui l_ O -C O. if) O CD o o l- c • CD . — S_ o o CO c o o -3- oo vO o CM o o o LA CA CA CM LA O O CM LA -J" LA O O ca -4" J" J" CM CM CO O LA vO — — O O O LA LA O CO VO vO LA LA LA ca LA CA CA CA -3" CA O — — O — 00 O CM CM oo LA LA 0O 0O -d - la r»~ LA LA v£> ctv o r-. LA CM CA CA CA CM — O O — CM O O vO CA LA v£» CM O O 0O — oo vO -cr oo O OO -4" CM — — O — CA CA — — o LA O LA CA CA 00 LA LA LA O o LA O O o o O O LA 1 CA -4-, r>^ r-^ CA MD r^ LA O vO vD CA LA r>~ O a- z. oo vO LA LA LA -cr LA vO LA J- P^ CA 00 E l/l ro 1 CM oo CA CA CO vO LA CA vO O o P^ CM o O CA LA O 1 — i — CM OO OO r^ \o CA LA i— c z. 0) o O f— ■ — r— O O o o o O O o CJ o 1_ i-H CA r^ CA z x: \£> CA CA CM 00 MD MD CA CO r— J" 00 r^ z. CM O LA vr> vO 1 — J- CA o MD vO -3" o c o vO "rH 1^ o CA VO +J i^ CM J- v£) co F— CA LA r^ r— ■ — ■ — CO u_ ■t-J oo CO 0Q CO CO CO u_ u_ U- u_ u_ u_ u_ CO CO CO CO CO CO 3 CO CO co CO CO CO CO 157 APPENDIX III Results of Mass Balance Studies 158 00 < LA co CO < h- co >- LU > a: CO < LU CH \- co a: 4" CM CO CA 1- co ■=> o < LA 4" LU LU IE CO > < cn] E Q O CD I cn w O D l. O +-> c c L0 o D -0 o s_ 0) to U E ii -4 O Q_ ro !_ o _c ci- in o .c •M s_ O — cn ■M O O c cn E in c cn O i ca o I CM O ca cn l. O o cn (^COvO OvO N0O 000 N r-^ ca o ^— o la co o — r-- CA CAOO CM vO oooJ- rv(T\ -t^OOON MD 00 CA CM CA la M3 r-~ J - CA LA O LA la I s * r~~. r-. ca tANOOOCO 0\ O CM CM CA CA CA-4" CA-4 -4 r — tpon cm r^~ — o co CO LA CA — vO CA CA CA O vO O CO O CAOO CA CO vO CA LA CO CA CA — CM CM CM CM CA -4 CO — MD CM CO CM 4" CA O CM iavd rvNoo CA la vO CA ca O — LA P-. O VD CM vO LA CA — 4" CA — O — ca o r^ ca LA CA -3" -4" CA CO LA 4" CA CM I--.CO CA O — CA-4 -4 -Cf -4" N NNNO -4 CM — — O 4" 4" 4" 4" la la4"lalala -4 -4 la la la O O LA CA O O — CM v£> vO CA O CO CO CO vO CO O O CA CM CM CM CM CM O CO O O O CAOO CA O CA CM CM CM CM CM CA r^co LA CA CM CM CA CA CA oocoNm oo r^ ca ca r^. CA CA CA CA CA CA O CM O CM VO CAOO O 00 — — — CM CM O O CM 00 O O 4" CM CM CM CM CM 4" CM LA CM CM — CA CA CA LA CM O CM O CA CA CA 4" CA LA LA LA CM CA CA CA — CA LA 4" O O ' 4 CM O O LA r^ LA vO CA — O — O LA CA CM ■ — ■ — ■ — CMCM CMCMCMCMCA O O O CO -4 O O O CO CM ca o o co r-* — O O CA LA CA CA CA CA CA LA O CM CM O CM LA VO VO O 4" 4" -4 4- vO vO CO — 4" 4" 4" 4" LA LA 4" 4" 4" 4" 4" CA4" CO LA CA LA LA LA VO vO 4- 4- -4 4" ca CA O CA O CO vOvo mtA4 CA CA CA CA CA v£> LA — CM VO ■4" 4- 4" 4" ca O O O O O CM O O CM KO r^4" vo — ca O O O O O -4" CM O v£> vO vO 4" O CA LA O O O O O VO O O O O r^ o co co cm o o o o o o o o o o CM\D44 M CM CM CM CM CM NOOCO-t CM CA CA — CA CM CM CA CA 4" VD00 O 4- r^co CA4" CA CM CA o o o o O CAOO O CA CM CA CA CA O O O O O CM CO vO P^ CA N0OOO O LA LA CAOO CA CM MD LA CM CM CM — O — CO M3 MD CA CA CA LA vO LA 0O 00 O vO CM -4 OCMOvX) CAVOMDOOCA O CA-4 — J- 4- 4" -4 NOvDOO CM O LA CA 4- 4- 4- ca 00 O LA LA VO CM CM 00 CM CA CA CM o Ninoo O LA CM — CA CA CA CA N40vD ca cm 4" 4" o o o o o o o o 4" 0O vO cm CA CA CA CA O O CM LA r— r— O — O O O — ca4" r^ o r-> o la o ■— — O CA LA r»» CM CM O 4" — VO 4" LA LA LA -4 LA O O O O — O O O CA — CM CA4" LA LA LA 4" 4" CA O O O O O O O O O O CM — CM CM ca4- o — r^ ca4" — — o CA CA CA CA CA CM CM — — — NN J-COJ- CO CM CA CM VO CA — 00 CA-4" LA CO ON - N- o o o o o O O O O CA VO NOO (T\0 — CM CA-4 — — — — — CM CMCMCMCMO CM CA CA CA CM O O O O O O O O O O CM CA-4" LA VO O O O O O CM CA CA 4" 4^ LA O O O O O O CA O O O O O r->. CA O — CM CA O O — — — — 159 00 < vO CO I- < h- co >- LU > a: to co -4 CM 00 vO CA CO CJ3 Z> < LTV I 4" Ui CO >- cc < E Q O OQ I CD l/l O ZJ 1- O +-> C •rt ft) c in o D X) o l_ (L> 03 U O (U C71 E Hi -4 O CL Irt 03 l/) D S_ o .c Q. (/) O O fO s_ 4-> O O c i co o -. •— CM CA 4" • — i — CNOO NLACO lAro O — CO tOOONO O — CO CM Cj" 4" O OCOCO CTi — CO CPv O vo co r->-4 vo -J (M vO co ro VO CMCO M CT\ cm co r-~ — CM CM CA CM CM CM CO (N 4" LA LA CM vO 00 — CA - O NLA^D CO CO — CA CA CT\cn4' r^LA M^MNN COOOOOOCA LAvO J" LA LA r^. J - vo -J- -4 CM CM O CM CA CAvO CM LA vO CM CM -4" vO oo-3-CALno -d-CAocAr^. LALAOOvD'— LAvD - CA — — IS(T>0 - LACALACACM -J- CM -4 CA CM CM CM CAOO 00 ■J- J" — CO 00 CA4" CA4 - LA 4" -4 4" CA4" 4" 4" -4 LA vO CA O O CM CO — CAvO LA LA O CM LA CA CM vOvjJ NOCO o o vo oo o o -d- r«^ r-. la LA LA CAOO <— CM O vO vO O 00 CA — — O CM CM CM LA O O 00 CA CM O O 00 — CM CM CM CM CM O 00 LA O CO tALAMvO-t CM CM CM CA CM J" CM O CO CM LAvO O CA — CA CA CA CA CA O CM CM LA CO 4" vO vO 4" 00 (ArA4'-t4' CM CM r-» O CM CO O CM CM 00 CM CM CM — CM O O O O CO LA4- CM 4" CA r-* NOOO CA O — CAOO — O LA — CA CM CM CM CM CM CO vO vO -4 CO CA — — CM LA CM CM 0A CA CA LA CM vO CM CA CA CA CA CA CA caJ-J - 4 rA 4" CA r-^ CA LA O 4" LA -4 LA CA J" -4" — CA — CM 1^ LA CA vO CA CM 4" CA — — CM CM CM -4 -4 — CO LA N NLAtAN LA vO 0O CTv O CM CM CM CM CA CAOO LA0O O — CA — CA LA — ca — r^oo CA CM CA CM CM O LA LA O LA O CM CM CA CM j- j- j- 4- j- j-j-r^-4-J- -4 J- J" -4 CA J" J" -4 J" CA CA CO CO vO 00 LA LA LA LA LA CA vO LA CA CA LAvO NNN CT\vO IANJ- vO vO vO LA LA VO (A0O00 LA LA LA -3" -4 4" CA CA CA CA CA vO — CA vO ' — J- LA LA LA vO O O O O O CM vO CO CM 4" — LA00 CAOO O O O O O 4 4-vflvO O OCO LA-4 o o o o o o o o o o 000 NvOvO o o o o o o o o o o O CM CM CM -4 o o o o o o o o o o CO O CO -4 CM CM — CA CA CA cn CO J" CM CA CA4" vO vO O O o t— ■ — i — ■ — ■ — -4 CM CA CA CA O O O O O CM CA — 00 vO CA CM CM CM CM O O O O 0O4 lA-t -4 CA4" O vO -4 r^ — — r-^ vO vO CM vO CM LA LA CA LA LA — CM CM — — vo vo o o r>-« CM CA CM CM O — CM CM CM CM LA 00 CA CM — CM CM O CA CM CA CM CA CM O O O O 4 cnrnN — — O CM 00 O CM CA O O CM 00 CA CA -4 4" LA LA -4 O O O O O O O O CA O CM CA-4 LAvO 4" -4 4" CA CA O O O O O O O O O O r-^co ca o — — — — CM CM CA CA CA CA CA O O O O O O O O CA O CM CA -4 — CM CM CM CM O O CA CA CA CA CM O O O O O O O O O CA (A4 lavO N o o o o o CA CA CA CA4 - o o o o o o o o o o CA O ■ — CM CA 160 00 < en CO < >- LU > CC co < LU CC \- co CC CM 00 Cn CO C3 < CM CM CM LU LU >- CC < cr E O CO CO ■M o en to O 3 v£> O r~- CO i- O O CM o o +J c • • 1 i 1 • rH a) o o o o C I/) O 3 XI O s_ a) co o o co in -3- O Q- +J O — Ci tn fO i_ (D 4-J o o c in h- 1—1 3 S_ O _c o. 01 . — O CO _c ■M Q_ o i ca O cr F 1 CM O z z i/) (D C 0) CO cr x: O z en j_ o o "V. Q cn E J" M3 OO CA i— J- la ca •— vO J- co la Cn-d" J-NNO00 NvDO (MvD v£> O CO O CM CO MD CO CM r- CM J" -d" -d" M3 v£> LA J" CP\ LA LA LA-d" -d" — CA -d" -d - -d" -d" y£> r»«. O ON- o o o -d" co la r^. cm — — — co \x> co vo -d- CA CA J" — LA VO IANN N CO MD CA CA CTv CO LA — M3 LA CA^O O CX\ LA O O O O CTi vO O LA LA OOrONO LA CM J" -d" -J" VO VO LA -3- cn LA LA LA -d - CA CA-d" -d" J" J" CM LA LA CO LA O00 00 NM CM LACO LA LA VO LA-d" (^ — O O O O -d" O O CO — CM LA O LA O O CO CM CO O CO VO LA LA LAvO O -d" LA LA LA LA CM — CO CA NOO o cr\(T\ CM CO LA LA LA — -d" N — O co r>- vr> r^. \r> O O LA -J" -d" O O — CM CM LA VO VO CO VO O O LA O O la vo oo cn la VO v£l VO LA vO CM cn LA 1^00 r^ cn cn cnoo — 00 CA cm r^ N iv^D vD vD LA 0O 00 CM LA LALAvDvD N O 00 LA LA r-- 00 LAvO LA-d" CM CM CM CM CA o la o cn CM oo cm o envo -d" — CM -Cf O CA -d" -d" -d" -d" CM — — CA O CA CM CM CM CA LA O CM LA N N00 LAO r^ o — cn — LA O CM LA cm -d" cm cm cn CA CA CA CA CA 1^. LA LA N LA NNN0O N rv la r^ en cm la vO v£» vO v£> — o — LA 00 O 00 vOvOJ- LA4 CM O -Cf CM O — — — O O CM CnCO CM CA LA4-J--4-J- o o o o o o o o o o CM 00 CM — LA O O O O O O O O O O — en j- co o o o o o o o o o o o CM 0O vO M3 J" o o o o o o o o o o v£> J" 00 CM -d - vD LALALA-J VO 04 LA — o o — -d" CA-d" LA vX> SNOOO-Cf — r— — CM CM O \D vO v£> v£> \X> vO v£> vO "vO ^O O 00 CM — CM — CM O O J" v£> -d" — CM O CM CM 00 O O O O — VO CM LA vO cn cm lavo cn -d- -d- vo o oo CT\CM ISN4 enco r»->x> oo CA r— CA oo LA r>» r»»oo oo en J" J" LA LA ^t O O O LA O O O — LA CM — CM CA CA LA -d" -d" CM CM — O O O O O — — O O O \fl NCAO - — — — CM CM LA O O O O — O O O O CM CA-d" — CM CM CM CM O O O O O O O — O O O O rAj - LAvO N o o o o o MD -J" CM O CM -X -d - \j0 vX) -d- -d- -d- cn cn o J- J- o — -3- — o o o r^ LA CM v£) NCArA' — -d-.d-.d--d- -d- en o oo vo -d- o CM r^. i^ r~>. vo o -d- O LA O CO rwx) CM LA LA O CA O CM CM -d" CA CA CA (M NO vX) 00 LA — O — MD O -d - v£) -d" LA LA LA O O O O O O O O ovod-d- v£> v£> MD LA J- oo -d- -d- CM — CM O O -vDvD vD NvD iv CM CA CA -d" O O O O O O O O oo en o — o o — — 161 00 < vD CO CO < I- co >■ LU > en CO LU cc co cc zc J- CM CO CA CO Z> < CM CM I CM LU LU ZE CO > < CD l/> cr O Z> F i_ o 4-J c Q • r-l \- HH 3 1_ o JZ a. o p— O fO x: 4-J Q_ o to c O o Q LA CM CM O -Cf vD vD CM -3" CA O r-» la r-, en — la CO cm r-» -d - en en J- r-» — — -CT CM v£> vD N4 - r-^-d- LT\ CM O CO CA -Cf J" LA -CT -t^O I — VDCOJ" — en o la O O PA CM ca r-. — cm O CM CA -4" o o o o MOO NINO CA CM ■— r^. CM O — CM O P^ CA — (M vO CM VO CM CA CA CA -d~ -J" — r- CA — CA — I • I • • o o o CM — O CA O O CAOO CO O CA -d" -C}- -3" J" CA vo r^ ca — o CM vO — — LA o o o o o oo ^o ca r^. — J" r^ — co o ca ca CA -3" -3" -3" -3" -J-LALAVOCOJ" -d-CACACA-J- CA-4" CA-Cf CA CA IAON4N CM CA r^ CM CA LA LA LA O O -3" CO CA .— O CO CA O O LA LA O LA-Cj" CO — M3 O O J" -4" O LA O IA4-\D J - N LA LA LA LA LA O CA CAOO CM CA — — r^ P-. LAvO CA O CAOO r^-J - vOvDvD o cAvO r^ P»~ LA CA CA^O LA-j- LA o o la r^-z|- OO LA O VO CA vO vo r — ■ i — r — vo -4- oo o o co o CA CM 00 LA LA LA -4" VO LA LA LA o o vO o r^ LAvO 00 CO 0O CO LAMNNO CM v£> \£> LA J" v£> CM O vo vo vo r^ r — r-- CA CM CA CA O CM CA CM CM CM O r^. LA LA CM LA CA r*» O CA CM vD CA vO O CA vO CO CM CM CA CA-4" VO -3" CA CM CA o CA caoo r>v LA — oo CM -3" CA r^. o o oo o o 00 O LA O O LA cm co vo o r^ LA O — O CA r^ LA CM O LA LA 0O (MvOO PsN r^ — la o r^ 00 00 OO CA CA — — — CM CM — -d" CA CM OvDOO CAOO vO vO LA -4" — CM CM CM — — — — — — — O O O LA-J- r-- r»- r^. vo vo CO MD CM 00 -4" J - LA LA LA LA LA P^ o o o o o o o o o o l-» LA CA O LA o o o o o o o o o o o o -d-vOOOvOCOCO o o o o o o o o o o CM VO -4" CM 00 o o o o o o o o o o o o CM O vO o o oo LAOO LTlLAN CA LA-J- — CM CM LA — O J" CA O — CA CA CM J- CA CA CA-4" -4" vOvo rvvi3 la V0^D vOvO LA4 - CM CM CM vO CM O CM CM — CM CM CA OOOCOvOvO — — O — CM -J- *X> vO CM O 00 O O — CM -4" CA 0O — CA CA r^ CM CA CM CM CM O CA CM O J" -3" I-*. r^ r--oo co oo r^-4" 4" — — md CO CO CM LA CA LA CA4" -3" 4" LA 4" 4" CA CM CM — r— .— — — — O LA O LA O — — — LA CM •— CM CA CA LA O O O LA LA LA — . — J" vO P^ CA O — CM — — — CM CM CM o o o o o O O CM O O — CM CA J" LA o o o o o i — ■— CM CM CM CA o o o o o o o o o o o o vo r^co ca o — o o o o — — 162 00 < LA CD to < r- to >- LU > cc ■n to < LU CC \- 10 cc J- CM OO MD to cn CM I cx> CM LU LU x: to >- < E Q O DO CJ1 1/) O =J 1- O 4-1 C I c in O =J -o O s_ a) 03 u o 03 en E in 03 c o I CA| O rA| X cn s_ o o ^ E O (M vD ro N MD ur\ — la cn Cn CT\ LA CA-4 r-v. r--. vo r- vo O CM CM -4" -4" r-. 00 r»» cn ex) vO -4" NM Cn O 00 CX) 00 CA — IS 00 00 OO I — LA o (T\md la- camd is isco no cm cno O ■ — 1 — CM' — O ' — O ' — CM — CM' — Mro CA CA CM CM CM CA \£> LA Cn CM — — O O CA O 00 VO MD CA O CM 0O O c^00vO\D NvO LALA(^ CA CM O LA -4" LA VO VO LA LA CM CM LA LA MD vO VO LA VO LA O LA CM OA MD vO vO -4 O .c i_ O vO 00 O O O lAOSNrO O LA J" 0O O CTvvO — O CA LA cn O O O cm -4" cn vo cn OOOOO CA LA LA cn cn O O -4" O -4 LA 00 s_ CD E 00 Cn Cn CT\ Cn 00 ISOO Cn Cn 0O NvOvO^O is is ismd md rwOvD ir\ Phosphorus as PO, 03 4-J O cn i_ O 1— 1 03 4-J h- MD 00 Cn-j" O LA \D CA LA CA O VO LAO O t\| CT\0 (Tlifl LA O LA-4" is is — LA -4" -J" LA LA CM — — CM CM O LA cn-4 rs 00 00 00 0^1 CTi O CM O 00 is rs is is 000 00 NtT\ 00 n md is LA O 0O LA LA s, is is rs is LA J- N O LAID ^3 vO vD CM LA O OO la — cn CM PA CM LA — LA MD 00 CM CA CM CM CM LA-4" CM cn O CM CM CM CM 00 cn LAoo cm CM CM O LA O VO — -4 — CM O O LA O LA o cn cn o o 00 — — LA LA IS CM CA CM OO LANNN LA O cn o O LA cn cn o LA O CM — — — O CO 00 LA CM LAO-J-OOJ- is cn md la la LA o 00 -4/ -4" md o o LA o -4- OOOOO cn ca ca cn — OOOOO OOOOO -J" -J" LA OOOOO — LA O O LA LA vO O OOOO ca is cn cn md CM CM CM CM CM 4-Noroo -J -CO VO CM j- J- J- J- o O O CM CM -J" vO 04"-tv0 CA -4" CM CM CA 00 vO MD MD CM — — — — is is — cn — — ^f rs-4 MD 00 O CM O vO vO vO O O O CM O O O O O vO J- o 00 — 00 J- vO O O O — CM O 00 rs md rsco o -4- -J- cn la md r^- cn ca ca vDOOvDJ- O o cn la md 00 O OO 00 LAOO cn la o o cn MD vO ca MD rs cn CA CA -4" — cn cn rs MD vO vO LA v£) OOOOO OOOOO CM CA-4" LA vO LA-4" CA CM CM OOOOO OOOOO iscomo- — — — CM CM OOOOO OOOOO CM CA ^t — CM CM CM CM O O OOOOO OOOOO Pf\4" LAvD N OOOOO CM CM -4" LA OOOO OOOO 00 cn o — 00 — — 163 CD < NO CO to < >- UJ > r> CO < LU C£. h- co J" CM 00 vO CA CO CA CM I 00 CM LU T. CO >- cc < cr E Q O cn id O 3 s- O +J c •.-I CD t c if) o => JO o 1_ Q) to u o H3 II J" o D_ • r— CD in fD 1_ CO ■M o O c l/l l- 1— 1 3 1_ o -C Q. i/l 1— O (D -C ■M Q_ O ex E in LA O NO LA O o rvcn-co — r-« LA-d" CA CO NO LA LA LA O LA NO -d" CA CA CM LA -d" CO CTlOOOOCO N CA CA CA N CA J" LPj LA LA LA LA CA LA O LA MCO O CAN cm ca ca ca -d" NO LA LA LA LA LA LA 00 O LA O CM CM CA CA CA CM -d - LA LA LA -d" LA O O O O O LA LA r^ CO NN»XI vO co rv n n\o CO nO NO no CACO -J" CA O NO r--. CA -d" N ca r-. LA-d" O O CA O O O CA — CM — LA O ■ — -d" CA CA nO r-» la I s - CA oo 00 LA LA O CO NNNN 00 O O CA CM LA NO r->- so no no oo CA O nO 00 00 O O LA CM 0O CO CM CM CM CM — vDOCO-N CM CA CM CM CM O CA CA LA N CM CM o o o O O O O O O O CA CM LA CM CMAvD N CA O CM CA NO NO CO CM CM O O O -d- -d- -d- r-. CA LA o oco-- o CO o CO — — — O rONO NO CM CM CM O 00 O NO OO 00 O oo ca r- r^. ca 00 LA CA LA CA vOCO N\OvO CA CO — -d - LA no la no no r-~ -d" CA — CA n r-- no oo O CA CA CA CA o o o o o -d" no -d" -d" cm NO — LA — — — CM CM CM CM NO CA00 -d" — — CM — — — o o o o o O CM O NO -d- O — O — CM o o o o o oo o o o -d - i— CM CM CM CM o o o o -d- no oo oo CM — O O o o o no — O O O NO CM ca N nO J" CO — O — LA CA NO O O O CO 00 O O O — NO CM J- J- O r-.co — la — O O CM o o — CA CA CA CM ■ — CA CA00 CA CA NO CM CM CM N l-». CA — 00 CACO — CM CO NO O O O — O O no -d - no n I s - CA 00 CA NO NO NO LA LA o o o o o — — o o o CA-d" LAND N -d" CA CA CM CM O O O O O o o o o o CO CA O — CM — ■ — CM CM CM o o o o o o o o o o CA -d" ■ — CM CA CM CM O O O O O O O O O O O O O -d - land r-. co o o o o o CM LA-d - LA o o o o o o o o CA O — CM o — — — 164 vD 00 < LA 00 CO < I- co >- LU o co < LU CC I- co -d- CM ex) MD CA LU CO LU h- Q_ LU CO LA I LU ZC CO >- < oi E Q O CO en E in -d- o Q_ (/) CO (/) S_ o SZ Q_ 10 O I CJ) ui O 3 L. O +-> C •rH 0) I O Z3 -O O s_ a) (D U O CO O -C +-> 1_ o — CH ro s- 4-> O O C cr E ro c 0) cr O o \ o en E CM CM vD OOJ- — -d" oo J- oo O v£) O O vO i — CA MD MD MD O CO MD O j" cn r^ — \D ISNISN O O vO -3" 0O oo -J- oo oo la -d- J- -3- r-* — cm — cm NMD l^-OO v£> vD 0O -Ct" LA0O NIA O OvOCO CM -J" CM \i) N-- MD MD LA — CO O -Cf MD MD O0 o o o --T O 0(T> vxj r-» r^ i--md — — o — o MD O CM 00 O CA CM CA -3" -d" -t CM CO O 00 J - CA LA MD J" J" CA-d" LA-d" CM MD -J" MD J" CM r-^ O LA CM O CM — O MD -3" CM MD 00 MD MD CA O MD 00 CA O O ca O CA CM O O CM -d - CM CA MD MD 4vD N r^vOr^CACA O ca -3" ca — OOOlalala r^r^-MDMDMD f^\vO vD OOOOO _ _ r- ,— ^. — oooo ooooo ooo -3" CA-d" 0A00 OCALACACA CA ^O 00 CA CO LACMOOCMO CAMD0O LA LA LA MD MD r^vOLALA-4" CACACMCMCM CACACMCACA CA CA -^ OOOOO OOOOO OOOOO OOOOO OOO CM CA O N CM 4 0(M NO CM-t 0O O J" -t O N Cx| N NvO CM — O — CA OA OOCOCACAO — CM CM CM CM CMCMCMCM— — — — CA O CM CM O O MD CA CA-d" CM J-^OOvOtO oo -J- CA CM CO CA-Cf r^-MD ca o r^-vXD -d" 00 - LU > a: o CO < LU h- co or jz -d- CM 00 vD CTi or LU CO 2: LU a. LU CO Ln -3- I- LU LU in CO >- < cr E Q O CD CT) l/l O =3 v- O 4-> C •r- 1 (L> c 1/1 3 X) O L. 0) 03 U CJ> 03 _ s_ \ CD E 111 -d- o_ • 1— 03 1/) 03 s_ 03 +J O c 1/3 1- 1—1 3 !_ O .C O. 1/) 1 — O 03 s: 4-J a. O E 1/1 03 c » V0vX) N O-t LA CT\ LA — 0O CM 00 0O O O O CM CO O CM O OA CM — CM OA O OvO ncoj- VO M NCM N OA CM CM CM J" 4"CO OvDvD -3" I-- O O OA CM CM O _ CM CM OO CM O 00 CM VO v£3 -Cf CX\CO OA M3 '—CM -J" LA LA LA LA LA VO VO v£» -J" vO la v£> vO vO LA r^. -J" -J - LA vO LA — — en cr> o — — 00^- O CM -J- oa -J" — cm cr> r^. NNvO vD Ln \£> 0O OOOOO OO -d - O LA CA LA 00 cnoo 00 — — — 0O — vO en cnoo 00 r-^ o o 00 vo 00 CO VO OA CAOO CM CO -j- J- J- -J- J- LAVO OOOO — CM CM O 00 O — — o o o OOOOO 00 00 J- vX> o oAoo 00 r^oo OOOOO o LA CO O CM VO OOOOO o o cn cm o CM CM -3" — I--- CM 0O CM — — CM — — O vO-tCO\OCO — 00 r-~ cnoo 00 r-»oo O O LA v£> — P». CM Cn la -3- cnoo vo OCM-d" 0O O v£> CXi LA CMCM CM' — 0A •— CM ' — ' — ' — OA ' — OA CM 0O vO CO vOvDJ- LAin OA 0A CM 0A LA lAvD Nfv.O CM CM CM LA LA O OA OA CA 0A OA OOOOO O O O — O M -t lAvO is OA CM O O O O LA O O O O CM 0O O — CM CA — CM CM CM CM OOOOO OOOOO CM O O — — — — CAOO (N ro-J OOO OOO O — CM OA-Cf OOOOO lAvO NOO CA O — CM OOOOO _ _ _ 166 en E a o on o J- X _L 10 M 2 4 Time of Day 10 10 9 8 7 \ O) E h z • 1- 5 O \ cr\ X z 4 \ 1 CM o z 3 1 PO o z 2 t r 1 r t r t 1 r 10 M 2 Time of Day 8 10 FIGURE 55. STATION SB 5, 24 HOUR STUDY, 14-15 AUG. 1968 167 U) E o o CD o a 10 M 2 k Time of Day 8 10 E I en t_ o z I CM o o Time of Day FIGURE 56. STATION SB 6, 2k HOUR SURVEY, 14-15 AUG. 1968 168 E Q O CO o 10 M 2 4 Time of Day 10 N E en o I .CM o z o "T" 1 1 r i i i i 1 1 1 1 10 B - 9 - 8 / NH 3 - 7 X») x^^^. - 6 0^ V 5 4 "^a JO - 3 Organic N - 2 _1_ " < 7ff -^no" j \ J* V \ /^ III! \ / tH f— ^ 1*1 1 1 1 1 1 n 4 *r i ♦t " i 2 4 68 10M 246 8 10 N Time of Day FIGURE 57- STATION SB 5, 24 HOUR SURVEY, 21-22 AUG. 1968 169 E a o CD o o 14 12 10 8 6 2 t 1 r t 1 r 1 r Flow Total BOD ' ' I I I L ♦ • -4 J L -40 -30 20 N 2 4 68 10M2468 10N Time of Day E . i_ o C*"\ o z -V. o N2468 10M246 8 10N Time of Day FIGURE 58. STATION SB 6, 2k HOUR SURVEY, 21-22 AUG. 1968 170 C 10 D1 E o o CO — o Q 10 M 2 ^ V 6" Time of Day 10 N CD £ CD L. o I CM o I CO O 10 M 2 Time of Day FIGURE 59. STATION SB 5, 24 HOUR SURVEY, 28-29 AUG. 1968 171 l*+ 17 ^ E 10 o o 8 CO \ o o 6 h t 1 1 r i r Flow' Total BOD 10 M 2 k Time of Day 10 N 30 20 » -.10 i Ll_ - en E en L. o o z 10 9 8 7 6 5 3 2 T 1 - — I 1 r t 1 r Organic - N 10 M 2 k 6 8 10 N Time of Day FIGURE 60. STATION SB 6, 2k HOUR SURVEY, 28-29 AUG. 1968 172 30 25 I 20 15 10 en E en E o o CO o Q 14 - 12 10 - 8 - I 1 1 1 t— T -l — i 1 ■ 1 1 r - - A - Total BOD *» - "" 1 — L«*Q^sl — L-"0"""^-- \ [Tl^J I / J3 \A\ /•> M "Carbonaceous > BOD a Nitrogenous BOD o \® LJ0 i i 1 i \ v/q D0 r i i 10 M 2 k Time of Day 10 N en E cn i_ o I CM o I CO o z FIGURE 61 Time of Day STATION SB 5, 24 HOUR SURVEY, 4-5 SEPT. 1968 173 cn E E Q O CO O o 14 h 12 10 8 6 4 2 T i i r- -i — r t i i t — -I — — r - - Flow - - Total BOD n pi — - J3 R / \ / \ R / \ / i — i -T*T rn \A \ R - -El <2^Carbonaceous > u\^>^^\l \xnfc - vA-^r" ■A^a B0D /Vk_A^ y v^\ d ° * v*-* e i II 1 1 3 Nitrogenous BOD pr -J i_ 10 M Time of Day 10 -130 20 10 E u o I CM O o FIGURE 62. STATION SB 6, 24 HOUR SURVEY, 4-5 SEPT. 1 968 174 01 £ APPENDIX IV Results of Reaeration Study 175 TABLE 18 STREAM CROSS SECTIONS Distance Downstream ft F 1 ow A rea Surface Width Average Depth ft 2 ft ft 22.5 46 0.49 52.5 35 1.50 3^.5 42 0.82 37-5 45 0.83 38.5 44 0.87 29-0 46 0.63 36.0 42 0.85 52.0 39 1.33 39.0 42 0.93 46.0 39 1.18 46.5 39 1.19 21.5 40 0.54 32.0 42 0.76 36.0 41 0.88 32.0 37 0.36 43.5 40 1.09 39-5 40 0.99 56.5 44 1.28 30.0 48 0.62 29-5 41 0.72 42.5 41 1.04 42.5 37 1.15 300 600 900 1200 1500 1800 2100 2400 2700 3000 3300 3600 3900 4200 4500 4800 5100 5400 5700 6000 6300 a Measurements made at intervals of 300 ft in a downstream direction from the county road bridge 5.1 miles below the waste treatment plant Streamflow = 26.5 cfs 176 TABLE 19 RESULTS OF REAERATION RATE MEASUREMENTS FOR 13 AUG. 1968° k at Stream Reach Flow Time Temperature Temperature k at 20°C k Mean mm hr -1 hr -1 day -1 5-10 5-15 5-20 10-15 10-20 7 22.1 1.24 1.18 21.0 6 23-5 • 525 .484 5 23.9 1.00 • 920 5 24.3 1.01 • 919 12 23.6 .464 .426 12.2 12 24.0 .650 • 592 18 23.1 .769 .714 ]k.k 17 23.5 .534 .490 7 24.2 .397 • 358 8.60 12 23.4 .871 .803 13.4 12 23.9 • 349 .318 15-20 23.6 730 670 16.1 Streamf low = 54.0 cfs 177 TABLE 20 RESULTS OF REAERATION MEASUREMENTS FOR 20 AUG. 1968' k at Stream Reach Flow Time Temperature Temperature k at 20°C k Mean min °C hr" 1 hr" 1 , -1 day 29-34 6 29.2 .564 .463 9.94 6 29-4 1.01 .808 5 29.4 1.75 1 .40 5 29.2 1.08 .868 34-39 5 29-2 .420 .337 6.82 6 29-4 .194 • 155 7 29.4 .222 .178 7 29.2 .530 .426 39-44 12 29.2 1.10 .883 3.31 11 29.3 .903 • 721 10 29.2 .734 .590 10 29-0 .660 • 532 29-39 11 29.2 • 499 .444 8.38 12 29.2 .599 • .481 12 29.2 .859 .686 12 29.1 • 755 .608 29-44 23 29-2 • 794 .638 7.09 23 29.4 • 725 .581 24 29.2 • 715 .574 22 29-2 • 699 .562 34-44 17 29-3 .894 .716 5.16 17 29.4 .651 .522 17 29-4 • 521 .420 17 29.2 .599 .482 Streamflow = 35 - 5 cfs 178 TABLE 21 RESULTS OF REAERATION MEASUREMENTS FOR 3 SEPT. 1968' k at Stream Reach Flow Time Temperature Temperature k at 20°C k Mean min hr hr -1 day -1 5-10 5-20 5-15 10 24.8 1.345 1.199 10 25.2 1.065 .941 9 25.2 1.055 .886 19 25.2 .704 .622 17 25.2 .604 .534 19 25.0 .681 .604 19 25.3 • 756 .666 17 25.4 .539 .478 7-92 9.75 9-70 Streamflow = 16. 8 cfs 179 APPENDIX V Results of Photosynthetic Oxygen Production and Benthal Oxygen Demand Studies 180 C\J CNI < Q < CO 00 O vO h- — ■z. 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