a copy to be downloaded by an individual for the purpose of research and
private study only. The thesis may not be reproduced elsewhere without
the permission of the Author.
DEVELOPMENT AND EVALUATION OF METHODOLOGY FOR THE CHARACTERISATION OF EFFLUENT DISCHARGES
A thesis presented in partial fulfilment of the requirements for the degree of
MASTER OF PHILOSOPHY
James Grainger Cooke 1977
(in Soil Science) at
Massey University
ABSTRACT
The establishment of a meaningful framework within which to apply management decisions concerning the present and any future water
quality standards requires that data on the composition of effluents and their impact on receiving waters be available. The collection of these data requires the application of methodology which will allow for an adequate characterisation of the effluent discharge. Previous work, and the results of a questionnaire sent to Regional Water Boards, indicated an acute need for methodological guidelines to be established with respect to the sampling and analysis of effluen~ discharges. This study is concerned with the development and evaluation of methodology for the characterisation of: (i) a municipal sewage effluent, (ii) a freezing works effluent, and (iii) a dairy shed effluent, in terms of the currently used criteria of water quality, and phosphorus and nitrogen forms.
To determine the best preservative treatment for nitrogen and phosphorus forms in filtered and unfiltered samples of sewage and freezing works effluents, two preservative illnendments (mercuric chloride and N-Serve) plus one control (unamended) were tested in combination with three storage temperatures (room, 4C, -lOC) over a 30-day storage period. No one preservative treatment was ideal for all N and P forms studied for both effluents. In general, however, i t was concluded that:
(i) -lOC was the best storage temperature for dissolved inorganic phosphorus and dissolved ammonium nitrogen but was unsuitable for analyses involving particulates
(total ammonium nitrogen, total Kjeldahl nitrogen) or organics (dissolved Kjeldahl nitrogen, total Kjeildahl nitrogen) for which refrigeration at 4C was the best storage temperature, and
(ii) No preservative amendment was necessary for sewage effluent samples provided samples were stored at 4C
iii
or -lOC (as appropriate); however, even with temperature control the addition of 50 mg HgC1
2 i-1 of effluent greatly assisted in the preservation of N and P forms in freezing works effluent.
The survival of indicator bacteria (total coliforms, faecal coliforms, and faecal streptococci) in samples of each of the three effluents was investigated. Membrane filtrations commenced within 30 min. of sample collection and after 3, 6, 9, 12 and 24 hours storage at room temperature and 4C. The results indicated that samples of the effluents under consideration could be stored for up to 6-9 hours at 4C before appreciable changes in their indicator bacterial composition became apparent.
Monitoring studies were carried out on each of the effluent
discharges. Sampling was from 1 to 3 days duration at intervals of not greater than 2 hours. Each effluent was characterised in terms of N and P forms, indicator bacteria, oxygen-demand parameters, solids, and pH. In addition UV absorbance at 250 run and absorbance at the
dominant 'visible' absorbance peak was determined on filtered samples, Correlation coefficients of up to i).98 between absorbance at 250 nm and a variety of organic or organically-related parameters indicated that UV absorbance at this wavelength could be a monitoring aid for effluent surveillance programmes.
Time- and flow-based variations in flow, and concentration and loading of analytical parameters in the effluent disch.:i.rges were discussed in terms of possible factors affecting the determination of sampling frequency. A computer integration method and probability plots were used to determine the sampling frequency needed to characterise concentration and loading of analytical parameters in effluents to within prescribed limits of accuracy.
ACKNOWLEDGEMENTS
The author wishes to make grateful acknowledgement to the following:
My supervisors, Professor Keith Syers and Mr. Russell Tillman, for suggesting the topic of the thesis, and guiding its development and final presentation.
Dr. Neil Macgregor for his helpful discussions and suggestions on microbiological aspects of the thesis.
Mr. Geoff Mills for providing technical assistance during the dairy shed effluent sampling runs.
The laboratory and treatment plant staff of Longburn Freezing Company and Palmerston North City Council for their cooperation in obtaining flow data and allowing access to the sampling sites.
Mrs. Eileen Hartstone and Mr. Bob Fry for their patience and skill at typing and draughting, respectively.
V
TABLE OF CONTENTS
Page ABSTRACT
ACKNOWLEDGEMENTS
ii iv
TABLE OF CONTENTS LIST OF FIGURES LIST OF TABLES LIST OF APPENDICES
V
X
xii xv
CHAPTER 1 CHAPTER 2
CHAPTER 3
INTRODUCTION
MONITORING OF EFFLUENT DISCHARGES IN NEW ZEALAND A SURVEY OF REGIONAL WATER BOARDS
2.1 Introduction
2.2 Effluent discharge types 2.3 Sampling of effluents 2.4 Assessment of loading 2.5 Analytical capabilities
2.6 Preservation of effluent samples 2.7 Future needs
MATERIALS AND ANALYTICAL METHODS
1
6 6 6 8 9 10 11
12 14
3.1 Materials 14
3 .1.1 Sewage effluent 14
3.1.2 Dairy shed effluent 16
3.1.3 Freezing works effluent 16
3.2 Analytical methods 19
3.2.1 Solids 19
3.2.2 pH 19
3. 2. 3 Indicator bacteria 19
3.2.4 Oxygen-demand parameters and dissolved oxygen 19 3.2.5 Nitrogen and phosphorus forms 20 3.2.6 UV and 'visible' absorbance 21
CHAPTER 4
CHAPTER 5
CHAPTER 6
PRESERVATION OF NITROGEN AND PHOSPHORUS FORMS IN EFFLUENT SAMPLES
4.1 Introduction
4.2 Review of literature 4.3 Materials and methods 4.4 Results and discussion 4.4.1 Initial characterisation
4.4.2 Behaviour of control treatments 1. Dissolved inorganic phosphorus 2. Ammonium-nitrogen
3. Nitrate-nitrogen 4. Kjeldahl-nitrogen
4.4.3 Effect of preservative treatments 1. Dissolved inorganic phosphorus 2. Ammoniwn-nitrogen
3. Nitrate-nitrogen 4. Kjeldahl-nitrogen
4.5 General discussion and recommendations 4.5.1 Dissolved inorganic phosphorus
4.5.2 Nitrogen forms 4.5.3 Recommendations
GROWTH AND DIE-OFF PATTERNS OF INDICATOR BACTERIA IN EFFLUENT SAMPLES
5.1 Introduction
5.2 Review of literature 5.3 Materials and methods 5.4 Results and discussion
5.5 General discussion and recommendations
CHARACTERISATION OF EFFLUENT DISCHARGES 6.1 Introduction
6.2 Review of literature 6.2.1 Sewage effluent
Page
23 23 24
27 29 29 29 29 30 33 33
34 34 37 40 40 46 46 47 48
51 51 52 55 57 63
65 65 66 66
1. Effluent sources 66
2. Effluent volumes 66
3. Solids and pH 67
4. Bacteriological parameters 67 5. Organics and oxygen-demand parameters 60
6. Trace elements 69
7. Nitrogen and phosphorus forms 70
vii
Page
6.2.2 Dairy and beef cattle effluent 72
1. Effluent sources 72
2. Effluent volwnes 73
3. Sol ids and pH 75
4. Bacteriological parameters 76 5. Organics and oxygen-demand parameters 76
6. Trace elements 77
7. Nitrogen and phosphorus forms 77
6.2.3 Freezing works effluent 78
1. Effluent sources 78
2. Effluent volwnes 79
3. Solids and pH 79
4. Bacteriological parameters 80 5. Organics and oxygen-demand parameters 80
6. Trace elements 81
7. Nitrogen and phosphorus forms 81 6.3 Materials and Methods
6.3.1 Sampling
83 83 83 86 86 86 86 87 87 87 88 90
90 90 93 93 94 96 98 98 98 99 6.3.2 Computation
6.4 Results and Discussion 6.4.1 Sewage effluent
1. Effluent sources 2. Effluent volume 3. Solids and pH
4. Bacteriological parameters 5. Oxygen-demand parameters 6. Nitrogen and phosphorus forms 6.4.2 Dairy shed effluent
1. Effluent sources 2. Effluent volume 3. Solids and pH
4. Bacteriological parameters 5. Oxygen-demand parameters 6. Nitrogen and phosphorus forms 6.4.3 Freezing works effluent
l. Effluent sources 2. Effluent volume 3. Solids and pH
CHAPTER 7
4. Bacteriological parameters 5. Oxygen-demand parameters 6. Nitrogen and phosphorus forms 6.4.4 Colour and ultra-violet absorbance
1. Identificat ion of absorbance peaks 2. Correlations between 'colour' and
UV absorbance and other analytical parameters
I. Sewage effluent II. Dairy shed effluent III. Freezing works effluent
IV. Combined effluents 6.5 General Discussion
6.5.1 Effluent composition
6.5.2 Evaluation of oxygen-demand parameters and faecal indicator bacteria for the characterisation of effluent discharges 1. Oxygen-demand
2. FC:FS ratio for differentiation between
Page 99 99 101 101 101
105
105 105 110 110 113 113
114
114
human and non-human faecal pollution 115 sources
6. 5. 3 Use of visible and UV absorbance a.s an index of pollutional parameters in effluents
EVALUATION CF SAMPLING FREQUENCY REQUIRED TO CHARACTERISE EFFLUENTS
7.1 Introduction
7.2 Review of l i terature 7.3 Methods
7.3.1 Computer integration of estimation of loads
7.3.2 Use of statistical distributions for estimation of sampling frequency needed to determine summary statistics
7.4 Resul ts and discussion
7.4.1 Factors affecting the determination of sampling frequency
117
119 119 120 126
126
129
129
129
1. Hydrological 129
2. Time·-based variations in concentration
and load of analytical parameters 131
SUMMARY APPENDICES BIBLIOGRAPHY
7.4.2 Determination of sampling frequency 1. Computer integration for estimation
of loads
2. Use of statistical distributions to
ix
Page 140
140 determine summary measures of effluent 145 quality
7.5 General discussion 152
154 156 167
Figure
3-1
3-2
4-1 4-2
4-3
4-4
4-5
4-6 4-7
LIST OF FIGURES
Flow diagram of the Palmerston North Sewage Treatment Plant
Plan of effluent disposal area, No.4 dairy unit, Massey University
Effect of control treatments on concentrations of N and P forms in effluent samples
Effect of preservative treatments on DIP concentrations in effluent samples
Effect of preservative treatments on NH4-N concentrations in sewage effluent samples Effect of preservative treatments on NH4-N
concentrations in freezing works effluent samples Effect of preservative treatments on DN03-N
concentrations in effluent samples
Effect of preservat ive treatments on TKN and DKN concentrations in sewage effluent samples
Effect of preservative treatments on TKN and DKN concentrations in freezing works effluent samples 5-1 Growth of total coliform bacteria in effluent
samples held at room temperature and 4C 5-2
5-3
5-4
6-1 6-2
6-3
6-4 6-5
Growth of faecal coliform bacteria in effluent samples held at room temperature and 4C
Growth of faecal streptococci in effluent samples held at room temperature and 4C Faecal coliform/faecal streptococci ratio in effluent samples held at room temperature and 4C Relationship between BOD5 and COD in municipal sewage (A) and dairy shed (B) effluents
Comparison of mean concentrations of total P, and percentages of P forms occurring in effluent discharges
Comparison of mean concentrations of total N, and percentages of N forms occurring in effluent discharges
Typical scans of effluent samples using 1 cm silica cells
Identification of visible absorbance peaks in freezing works and dairy shed effluents using 4 cm cells
Page
15 17 31 35
38
39
41
43
44
58
59
61 62 89
91
92
103
104
Figure
6-6 Relationship between A250run and COD in sewage effluent samples (combined sampling runs) 6-7 Relationship between A250nm and TS(A), TKN(B),
and BODs(C) in combined dairy shed effluent
6-8 7-1
7-2
7-3
7-4
7-5
7-6
7-7
sampling runs
Relationship between A250run and DKN(A) and TS(B) in freezing works effluent samples
Typical hydrographs of the municipal sewage (A), freezing works (B), and dairy shed {C) effluent discharges
Variation in pH(A), DIP and TP concentration (B), and DIP and TP load (C) in sewage effluent sampled on 9-10 August, 1976
Variation in BODs and COD load (A), TC, FC, and FS concentration (B), and TC, FC, and FS load (C) in sewage effluent sampled on 23 June, 1976 Variation in TP and TDP concentration (A), TI<N and NH,.-N concentration (B), and TOP and TKN load (C), in freezing works effluent sampled on 24 March, 1976
Variation in TC and FC concentration (A), and load (B) in freezing works effluent sampled on 11-12 November, 1976
Variation in DIP and PTn concentration (A), TKN and NH4-N concentration (B), and DIP and TI<N load (C) in dairy shed effluent sampled on 29-30 November, 1976
Variation in 'I'C and FC concentration (A and C) and load (B) in dairy shed effluent sampled on 16-17 September (A and B) and 29-30 November (C), 1976 7-8 Probability plots of TP(A), TKN(B), and TP(C)
concentrations from dairy shed, municipal sewage, and freezing works effluent sampling runs,
xi Page
107
111 112
130
132
134
135
137
138
139
respectively 146
7-9
7-10
Probability plots of COD(A and B) and TS
concentrations from dairy shed, municipal sewage, . and freezing works effluent sampling runs,
respectively
Probability plots of TC(A) and FC(B) concentrations from municipal sewage and dairy shed effluent
sampling runs, respectively
148
149
LIST OF TABLES
Table
2-1 Sununary of major effluent discharges administered by Regional Water Boards
4-1 Forms of nitrogen and phosphorus monitored during preservation experiment
4-2 Initial characterisation of the municipal sewage effluent and freezing works effluent used to evaluate preservation techniques
4-3 Average absolute percent variation (AAV) with respect to initial value of N and P forms in municipal sewage and freezing works effluent over a 30-day storage period under varying preservative treatments
4-4 Storage treatments appropriate for the long-term (30 days) preservation of N and P forms in effluent samples
5-1 Mean doubling time, G, (in the 12 hours after collection) of indicator bacterial groups in effluent samples stored at room temperature and 4C
6-1 Volume of sewage produced per head of population in 24 hours
6-2 Range of trace element concentrations reported in some municipal sewage effluents
6-3 Quantities of manure produced by dairy and beef cattle in one day
6-4 Hog unit equivalents
6-5 Trace element composition of two South Island freezing works effluents
6-6 Concentrations of N and P forms in meatworks wastewaters 6-7 Description, duration, analytical parameters, and number
of samples taken in each sampling run
6-8 Order of priority for determination of analytical parameters in a sampling run
6-9 Major industries discharging into the Palmerston North sewage system
Page
7
27
29
36
49
57
67
71
75 79
81 82
84
85
86
Table
6-10 Concentration of indicator bacteria in Palmerston North sewage effluent
6-11 Concentration of BODs and COD in Palmerston North sewage effluent
6-12 Concentration of N and P forms in Palmerston North sewage effluent
6-13 Volume of effluent exported from No.4 Dairy Unit effluent disposal area in 24 hours
6-14 Concentration and load of total solids in dairy shed effluent
6-15 Concentration and load of indicator bacterial groups in dairy shed effluent
6-16 Concentration and load of BODs and COD in dairy shed effluent
6-17 Concentration and load of N and P forms in dairy shed effluent
6-18 Number of lambs, sheep, cattle, and pigs slaughtered at Longburn on effluent sampling days
6-19 Cor..centration and load of solid fractions in freezing works effluent
6-20 Concentration and load of indicator bacterial groups in freezing works effluent
6-21 Concentration and load of BODs and COD in freezing works effluent
6-22 Concentration and load of N and P forms in freezing works effluent
6-23 Correlation coefficients between A
2~
0 and various ,., nm
analytical parameters in sewage effluent
6-24 Correlation coefficients for A250 and A671 with various analytical parameters in fflriry shed ~fluent 6-25 Correlation coefficients for A250 and A413 with
various analytical parameters in Freezing woQ~s effluent 6-26 Correlation coefficients for A250 with selected
analytical parameters in combined~ffluent files 7-1 Values of k for given confidence levels
7-2 Values o f f for given percentiles
7-3 Number of samples to establish result with precision (p) at required confidence level
xiii
Page
87
88
90
93
93
95
95
97
98
100
100
100
102
106
108
108
llO
128 128
128
Table 7-4
7-5
7-6
7-7
7-8
Total load of N and P forms and total solids leaving Palmerston North Sewage Treabnent Plant from 9.8.76 1100 to 11.8.76 1100 as estimated using various sampling intervals
Total load of N and P forms leaving effluent treabnent plant of Longburn Freezing Co. Ltd. from 23.3.76 1000 to 26.3.76 1000 as estimated using various sampling intervals
Total load of solids, COD, and N and P forms leaving the weir, No.4 Dairy Unit, between 16.9.76 0500 and 17.9.76 0500 as estimated using various sampling intervals
Total load of solids and N and P forms leaving the weir, No.4 Dairy Unit, between 29.11.76 1200 and 30.11.76 1200 as estimated using various sampling intervals
Estimated sampling frequencies needed to characterise the arithmetic mean concentration of chemical and microbiological parameters in effluent discharges
Page
141
14 2
143
144
150
LIST OF APPENDICES *
xv
Appendix Page
*
1 2-1
2-2
2-3
Survey on monitoring of effluent discharges
Effect of storage treatments and time of storage on the dissolved inorganic phosphorus concentration of effluent samples
Effect of storage treatments and time of storage on the dissolved ammonium nitrogen concentration of effluent samples
Effect of storage treatments and time of storage on the total ammonium nitrogen concentration of
effluent samples
2-4 Effect of storage treatments and time of storage on the dissolved nitrate nitrogen concentration of 2-5
2-6
3
4
effluent samples
Effect of storage treatments and time of storage on the dissolved Kjeldahl-nitrogen concentration of effluent samples
Effect of storage treatments and time of storage on
the total Kjeldahl-nitrogen concentration of effluent samples
Growth characteristics of bacterial groups in effluent samples stored at room temperature and 4C for 24 hours
Rainfall recorded at Palmerston North (Massey University) on effluent sampling days
Due to space considerations, appendices for effluent monitoring runs are not included, These data are stored on a computer tape file and are available on request from the Department of Soil Science.
156
159
160
161
162
163
164
165
166
