EPA-660/3-74-022
August 1973
Ecological Research Series
An Investigation of Ion Removal
From Water and Wastewater
Office of Research and Development
U.S. Environmental Protection Agency
Washington. D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
U. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ECOLOGICAL
RESEARCH series. This series describes research
on the effects of pollution on humans, plant and
animal species, and materials. Problems are
assessed for their long- and short-term
influences. Investigations include formation,
transport, and pathway studies to determine the
fate of pollutants and their effects. This work
provides the technical basis for setting standards
to minimize undesirable changes in living
organisms in the aquatic, terrestrial and
atmospheric environments.
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EPA-660/3-7^-022
August 1973
AN INVESTIGATION OF ION REMOVAL
PROM WATER AND WASTEWATER
By
R. J. Starkey, Jr.
M. E. Kub
A. E. Sinks
K. K. Jain
Contract No. 68-01-090U
Program Element 1BA031
Roap/Task 21 AJE 26
Project Officer
Thomas E. Maloney
U.S. Environmental Protection Agency
National Environmental Research Center
Corvallis, Oregon 97330
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20**60
For sale by the Superintendent o! Documents, U.S. Government Printing Office, Washington, D.C. 20(02 • Price $1.95
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EPA REVIEW NOTICE
This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Environ-
mental Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
ii
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ABSTRACT
Three standardized techniques (capillary membrane dialysis, alumina
adsorption, alum/polyelectrolyte coagulation) have been compared under
laboratory conditions to determine their relative effectiveness in
removing a broad spectrum of nutrients, cations, and anions from
freshly collected samples of stream water and wastewater effluent
(secondary and tertiary).
Of these alumina adsorption was highly effective in removal of phos-
phorus, inorganic carbon, as well as most cations with concomitant
reduction of specific conductance and hardness. High Kjeldahl and
ammonia nitrogen removal efficiencies of alumina were only observed
in samples of wastewater in which pre-treatment concentrations were
relatively high. Dissolved solids content and pH of alumina treated
samples were consistently observed to increase.
Dialysis occupied an intermediate position in respect to cation
removal, but produced results equivalent to alumina adsorption in
respect to inorganic carbon. Failure to significantly reduce organic
carbon concentrations were attributed to its association with macro-
molecules having a molecular weight greater than 5000 (the cutoff of
the cellulose membrane under consideration). Superiority of dialysis
in removal of sodium, potassium, chloride, nitrate-nitrite, boron, and
dissolved solids is reported. The latter is of particular interest as
it provides an interesting method of investigating the effects of
toxicants in stream water and wastewater effluent which could compound
the problem of analyzing algal assay data.
Alum/polyelectrolyte (Betz #1150) proved to be effective in removing
phosphorus from all waters tested, but was highly ineffective in
respect to all other parameters tested. Coagulated samples were shown
to contain potassium and sulfate in excess of controls and increased
conductance.
iii
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CONTENTS
PAGE
Abstract m
List of Figures v
List of Tables viii
SECTION
I. Conclusions 1
II. Recommendations 7
III. Introduction 9
IV. Purpose & Need of the Study 10
V. Experimental Procedures 14
VI. Discussion 35
VII. Acknowledgements 35
VIII. References 87
IX. Appendices 39
iv
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FIGURES
NO. PAGE
1. Idealized Method of Preparing Basal Medium for Bottle 13
Algal Assay Procedure
2. Schuylkill River Basin: French Creek, Valley Creek, 16
and Trout Run Sampling Sites
3. General Scheme for Processing of Water and Wastewater 18
Samples
4. Variable Speed Mixer Assembly Employed in Standardized 22
Coagulation of Water and Wastewater with Alum (Aluminum
Potassium Sulfate) and Polyelectrolyte (Betz #1150).
5. Capillary Membrane Dialyzer Assembly 23
6. Cross Section of Capillary Membrane Dialyzer Showing 24
Relative Position of Membranes to Jacket with Flowing
Dialysis Medium
7. Capillary Membrane Dialyzer and Ancillary Equipment 25
8. Capillary Membrane Dialyzer - Pre-dialysis Purging of 27
Sy s tern
9. Capillary Membrane Dialyzer - Operational Mode 30
10. Alumina Column Suitable for Batch Treatment of 0.45^ 31
Filtered Water and Wastewater
11. Carbon Profile of Water Collected from Valley Creek 38
(April 1973) Before and After Processing
12. Carbon Profile of Phoenixville Secondary Wastewater 39
Effluent (Collected March 1973) Before and After
Processing
13. Carbon Profile of Phoenixville Secondary Wastewater 40
Effluent (Collected April 1973) Before and After
Processing
14. Carbon Profile of Phoenixville Secondary Wastewater 41
Effluent (Collected May 1973) Before and After
Processing
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FIGURES (CONTINUED)
NO. PAGE
15. Carbon Profile of Hatfield Tertiary Wastewater Effluent 42
(Collected April 1973) Before and After Processing
16. Carbon Profile of Hatfield Tertiary Wastewater Effluent 43
(Collected May 1973) Before and After Processing
17. Carbon Profile of Hatfield Tertiary Vastewater Effluent 44
(Collected July 1973) Before and After Processing
18. Phosphorus Profile of Phoenixville Secondary Wastewater 56
Effluent and Hatfield Tertiary Wastewater Effluent
Before and After Processing
19. Phosphorus Profile of Valley Creek Water (Collected April 57
1973) Before and After Processing
20. Phosphorus Profile of French Creek Water (Collected April 58
1973) Before and After Processing
21. Phosphorus Profile of Trout Run Water (Collected April 59
1973) Before and After Processing
22. Comparative Nitrogen Profile (Kjeldahl and Ammonia) of 61
Phoenixville Secondary Wastewater Effluent (Collected
March and May 1973)
23. Nitrogen Profile of Valley Creek Water (Collected April 62
1973) Before and After Processing
24. Comparative Nitrate-Nitrite Profiles of French Creek 63
Water Samples Before and After Processing
25. Comparative Calcium Profiles of Water (Valley Creek, 65
French Creek, Trout Run) and Wastewater Effluent
(Phoenixville Secondary and Hatfield Tertiary) Before
and After Processing
26. Comparative Magnesium Profiles of Water (Valley Creek, 66
French Creek, Trout Run) Before and After Processing
27. Comparative Magnesium Profiles of Phoenixville 67
Secondary Wastewater Effluent and Hatfield Tertiary
Wastewater Effluent Before and After Processing
vi
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FIGURES (CONTINUED)
NO. PAGE
28. Comparative Boron Profiles of Water (Valley Creek, 68
Creek, Trout Run) and Wastewater Effluent (Phoenixville
and Hatfield) Before and After Treatment
29. Comparative Sodium Profiles of Water (Valley Creek, 69
French Creek, Trout Run) and Wastewater Effluent
(Phoenixville and Hatfield) Before and After Treatment
30. Comparative Sulfate Profiles of Water (Valley Creek, 70
French Creek, Trout Run) and Wastewater Effluent
(Phoenixville and Hatfield) Before and After Processing
31. Comparative Specifice Conductance Profiles of Water 73
(Valley Creek French Creek, Trout Run) and Wastewater
Effluent (Phoenixville Secondary and Hatfield Tertiary)
Before and After Processing
32. Comparative Hardness (EDTA) Profiles of Water (Valley 74
Creek, French Creek, Trout Run) and Wastewater Effluent
(Phoenixville and Hatfield) Before and After Processing
33. Comparative Total Alkalinity Profiles of Water (Valley 75
Creek, French Creek, Trout Run) and Wastewater Effluent
(Phoenixville and Hatfield) Before and After Processing
34. Dissolved Solids Profiles of Phoenixville Secondary 76
Wastewater Effluent (Collected March, April, May 1973)
Befoer and After Processing
35. Dissolved Solids Profiles of Hatfield Tertiary Wastewater 77
Effluent (Collected April, May, July 1973) Before and
After Processing
36. Dissolved Solids Profiles of Trout Run Water (Collected 78
January, April, May 1973) Before and After Processing
37. Dissolved Solids Profiles of French Creek Water (Collected 79
January, March, April, May 1973) Before and After
Processing
38. Dissolved Solids Profiles of Valley Creek Water (Collected 80
January, March, April, May 1973) Before and After Processing
vii
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TABLES
NO. PAGE
1. Comparison of Macro and Micro Nutrients of Synthetic 12
Algal Assay Medium with Those Typically Found in Trout
Run, French Creek, and Valley Creek of the Schuylkill
River Basin and Effluents of the Phoenixville (Secondary)
and Hatfield (Tertiary), Pennsylvania Wastewater
Treatment Plants
2. Stream Sampling Sites 15
3. Specifications of Wastewater Treatment Plants 17
4. Preservation of Filtered and Unfiltered Samples 20
5. Alumina Column Components and Specifications 29
6. Summary of Analytical Methods 32
7. Summary of Analytical Standards 35
8. Summary of Water and Wastewater Effluent Treated by 37
Alumina Adsorption; Capillary Membrane Dialysis; and
Coagulation with Alum/Polyelectrolyte
9. Comparative Concentrations of Phosphorous in Raw Stream 46
Water and Wastewater Prior to Treatment
10. Summary of Phosphorus Treatment Efficencies for Water 47
and Wastewater
11. Summary of Total Phosphate Phosphorus Removed by 0.45 « 48
Filtration of Stream Water and Wastewater Effluent
12. Comparative Concentrations of Kjeldahl, Ammonia, and 50
Nitrate-Nitrite Nitrogen in Raw Stream Water and
Wastewater Prior to Treatment
13. Summary of Nitrogen Treatment Efficencies for Water and 51
Wastewater
14. Summary of Kjeldahl Nitrogen Removed by 0.45 Filtration 52
of Stream Water and Wastewater Effluent
15. Summary of Cation Treatment Efficencies for Water and 53-54
Wastewater
viii
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TABLES (CONTINUED)
NO. PAGE
16. Summary of Boron Removed by 0.45jn Filtration of Stream 55
Water and Wastewater Effluent
17. Summary of Hydrogen Ion Changes Following Treatment of 82
Stream Water and Wastewater
18. Summary of Total Solids in Raw Stream Water Prior to 83
Filtration
19. Summary of Dissolved Solids Treatment Efficencies for 84
Water and Wastewater
ix
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SECTION I
CONCLUSIONS
Water and wastewater effluent can be processed in the laboratory after
0.45 fj. filtration to compare the effectiveness of capillary membrane
dialysis; alumina adsorption; and coagulation in removing nutrients,
cations, and anions as well as modifying parameters as specific conduc-
tance, total alkalinity, pH, and dissolved solids.
With minor exceptions coagulation with alum (aluminum potassium sulfate)
plus a polyelectrolyte (Betz #1150) was generally ineffective except for
the removal of high concentrations of phosphorus. Alum contributed
sulfate and potassium to samples in excess of control values; and in-
creased conductivity, hardness, and total alkalinity in most cases.
Alumina adsorption and dialysis demonstrated equivalent efficiency in
removing total carbon from water and wastewater (86% and 817., respec-
tively), whereas the alum/polyectrolyte (Betz #1150) was only 137.
effective.
The total carbon content of all waters consisted primarily of an
inorganic fraction which is attributed to carbonate carbon derived from
salts of calcium, magnesium, and sodium. Evidence for this is based on
a reduction in the concentration of these cations and total alkalinity
which parallel inorganic carbon removal.
Organic carbon removal was limited in all cases, although it is con-
cluded that coagulation was the least effective on a qualitative basis.
Failure of dialysis to remove greater concentrations of organic carbon
is attributed to their association with macromolecules, i.e., > 5000 MW,
which are excluded by the cellulose membrane under consideration.
Phosphorus (soluble) was most efficiently removed by alumina adsorption
and to a lesser extent by coagulation. Of the three methods dialysis
was the most unreliable.
With minor exceptions alumina contributed nitrogen to stream water
samples. This is due to organic and inorganic nitrogen being loosely
bound to alumina and readily eluted by addition of subsequent samples
to the column.
With higher concentrations of Kjeldahl nitrogen, as found in the
Phoenixvilie wastewater effluent (15-29 ppm), alumina successfully
removed 92-977. and dialysis 84-9CK,. For the same waters treatment by
coagulation resulted in values exceeding controls to a maximum removal
of 407.. The same trend was seen with ammonia nitrogen.
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Calcium and magnesium were removed from all waters by alumina adsorption
in the range of 95-99% and 92-99%, respectively. In comparison dialysis
removed 36-85% calcium and 33-81% of magnesium. Variable results occur-
red with coagulation ranging from concentrations exceeding controls to a
maximum of 53%.
Alumina adsorption removed 75-92% of potassium from stream water and 90-
98% from wastewater effluent. In comparison dialysis removed 28-90%
from stream water and 50-85% from wastewater.
Boron was most effectively reduced by dialysis and to a lesser extent by
alumina adsorption. Coagulation produced highly variable results and
was generally unreliable.
Alumina removal of silicon from wastewater effluent fell in the range of
91-98% whereas dialysis did not exceed 49-76%.
Dialysis was the method of choice for removing sodium; alumina and
coagulation produced highly variable results.
Of the anions tested sulfate was effectively removed by alumina (4-99%)
and to a lesser extent by dialysis (11-73%). Coagulation, as previously
alluded to was ineffective. Dialysis was superior for removal of
chloride ions (as high as 84% with stream water and 88% for treatment
plant effluent); coagulation and alumina demonstrated second and third
level activity, respectively.
Dialysis was particularly effective in reducing specific conductance
(82% in stream and 757* wastewater samples). In contrast this parameter
was generally elevated following alumina or coagulation treatment.
Hardness was most efficiently reduced by alumina (96-997.) and to a
lesser extent by dialysis (23-81%). Coagulation more often than not
increased hardness.
Total alkalinity reduction by dialysis reached 71-89% in stream water
and 62-81% in wastewater effluent. In comparison this ranged from 6-25%
and 6-35%, respectively, in waters treated by coagulation. Alumina
occupied an intermediate position with values exceeding controls to a
maximum reduction of 84% recorded.
Hydrogen ion concentration dropped in all cases following dialysis and
to a lesser extent after coagulation. In contrast the pH of alumina
treated samples increased due to the alkaline condition of the column.
Dissolved solids were most effectively removed by dialysis (71-757. with
Phoenixvilie samples and 42-67% for those from the Hatfield plant).
Alumina contributed to the dissolved solids loading of many samples as
a result of early breakthrough of less tenaciously bound species.
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Coagulation was found to be very unpredictable and for the most part
increased dissolved solids above control values.
Dialysis provides a method of experimentally treating waters to remove
nutrients, cations, and anions without actively introducing other
chemicals. It is furthermore suggested that dialysis with capillary
membranes having cutoffs at different molecular weights would provide
an interesting approach to investigating potentially toxic materials in
stream water and wastewater effluents which could influence the bottle
algal assay.
Of the three methods evaluated coagulation appears to be the most
practical route for developing a basal medium for the algal assay as
long as the elevation of sulfate, hardness, potassium, and conductivity
do not interfere with the addition of incremental quantities of phos-
phorus containing salts. Solubilization would have to be carefully
monitored to preclude precipitation or adsorption of a fine precipitate
to suspended particles. Similarly potential changes in pH and/or
buffering capacity must be considered in relation to the test alga if
growth dynamics are to be suitably interpreted for a given sample of
test water. This can only be determined experimentally if the coagula-
tion method of preparing a basal medium is to be considered for routine
assessment of the eutrophication process or monitoring a waste treat-
ment plant effluent.
Based upon this study capillary membrane dialysis occupies an inter-
mediate position regarding the complexity of reconstituting treated
waters, although its main utility appears to be as a tool in investi-
gating the role of high molecular weight dissolved solids on the assay
system. As alluded to previously one of the most important factors in
favor of dialysis is its passive nature, i.e., it does not add any con-
stituents to the test waters as reported for coagulation and alumina
adsorption treatment.
Alumina adbsorption per se_ is analogous to a "shot gun" approach in
that a broad spectrum of materials are removed with phosphorus being
the most notable, but is also associated with concurrent increase of
pH, sodium, and dissolved solids. Reconstitution of such waters would
be very time consuming if all but the limiting nitrient of choice were
to be brought back to their original concentration without precipita-
tion and/or complexing. Furthermore, based on the propensity of acti-
vated alumina for metals it would be particularly difficult to recon-
stitute trace metals. The latter would be especially true if the con-
centration was near the limit of resolution for atomic adsorption
spectrophotometry.
The suitability of each method in preparing a basal medium is summarized
as follows:
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METHOD
ADVANTAGE
DISADVANTAGE
RECOMMENDATIONS
COAGULATION WITH ALUM
POLYELECTROLYTE (BETZ #1150)
1. Minimizes
removal of
cat ions/anions
and nutrients
other than
phosphorous.
1. Relatively
slow ( 50
minutes to
prepare sample).
2. Contributes
sulfate,
potassium,
dissolved solids
to water.
3. Phosphorus
removal
efficiency
< alumina,
adsorption >
dialysis.
1. Investigate
increase of
sulfate etc. on
assay system.
2. Determine how
easily
incremental of
phosphorous can
be added to
treated waters.
3. Compare response
of test alga in
coagulated/
reconstituted
(phosphorus)
waters with
equivalent
inocula in
synthetic
medium.
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METHOD
ALUMINA ADSORPTION
ADVANTAGE
1. Highly efficient
removal of
phosphorus .
2. Very fast:
1-2 liters
treated in
10 mins.
DISADVANTAGE
1. Removes broad
spectrum of
cat ions /anions .
2. Reconstitution
complicated by
problems of
solubility/
complexing.
3. Removal of
trace metals
which may be
difficult to
confirm.
RECOMMENDATIONS
1. Give very low
priority to this
method for
preparation of
basal medium
unless problems
of reconstitution/
analytical work
load can be
overcome.
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METHOD
CAPILLARY MEMBRANE DIALYSIS
ADVANTAGE
1. Cellules acetate
membranes
significantly
reduced dissolved
solids 5000 MW.
2. Occupies a
relative
intermediate
position between
coagulation and
alumina
adsorption in
regard to cation/
anion/ nutrient
removal .
3. Method is strictly
passive: does not
add anything to
treated waters.
DISADVANTAGE
1. Test waters must
be prefiltered
to preclude
clogging
membranes .
2. Waters would be
difficult to
reconstitute.
3. Precipitation/
complex ing
incremental
addition of P
source must be
precluded.
RECOMMENDATIONS
1. Versatility of
method can only
be exploited
by evaluating
different types
of membranes and
molecular weight
cutoffs.
2. Emphasis should
be placed on
using membranes
to investigate
toxicants in
dissolved solids
which could
stimulate or
supress growth
of the test alga
in natural and
synthetic media.
3. Other parameters
to be investigated
in-depth include
temporal and
pressure optima
definition.
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SECTION II
RECOMMENDATIONS
Based on the significant reduction of dissolved solids ( ~ 5000 MW)
achieved with capillary membrane dialysis it is recommended that
advanced studies be conducted to determine the effect of removing high
and low molecular weight fractions prior to bottle test algal assay.
This would aid in confirming the presence of trace toxicants in test
waters which could have an adverse effect on the test alga and com-
pound the problem of assay data analysis and interpretation per se_.
The proposed study would include assaying natural (secondary and
tertiary effluents) and synthetic waters before and after dialysis with
membranes having molecular weight cutoffs of 200, 5,000, and 30,000.
Each assay would be accompanied by comprehensive chemical analysis (pre
and post dialysis) with reconstitution of test waters as required.
The following details a work statement and program schedule for the
proposed study.
Task 1 - Obtain Candidate Dialysis Membranes of Molecular Weight Cutoff
(A) 200
(B) 5,000
(C) 30,000
Task 2 - Prepare Chemically Defined Medium
(A) Prepare chemically defined medium as used by the Eutrophica-
tion Branch, Environmental Protection Agency, Corvallis,
Oregon, for the bottle algal assay. Determine "standard"
growth response of S.capricornutum Printz with this medium to
establish control curves.
(B) Dialyzed (pre-analyzed) chemically defined medium to deter-
mine fractions removed by capillary membranes having a mole-
cular weight cutoff of 200, 5,000, and 30,000.
(C) Based on chemical analyses of dialyzed samples prepared in (B)
each is to be reconstituted, i.e., as determined by differ-
ence analysis, and assayed against undialyzed chemically
defined medium.
Task 3 - Algal Assay of Secondary and Tertiary Wastewater Effluent
(A) Ten samples each are to be obtained on different dates from
the following treatment plants:
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1. Phoenixville - Secondary
2. HatfieId - Tertiary
(B) Each is to be processed, analyzed and assayed as follows:
1. Pre-dialysis analysis (following 0.45/1 filtration)
2. Pre-dialysis algal assay
3. Dialysis:
(a) Molecular weight cutoff: 200
(b) Molecular weight cutoff: 5,000
(c) Molecular weight cutoff: 30,000
4. Post dialysis analysis of waters dialyzed according to 3.
5. Reconstitution of dialyzed waters based on different
analysis.
6. Algal assay of dialyzed (reconstituted) samples.
Task 4 - Algal Assay of Secondary^and Tertiary Wastewater Effluent
Spiked with Low and High Molecular Weight Toxicants
Task 3 is to be repeated except that an additional set of samples is to
be spiked with known concentrations of low and high molecular weight
toxicants to verify the efficacy of dialysis on removing these from test
waters.
Choice of toxicants is to be mutually agreed upon by the EPA Project
Officer and General Electric Company Program Manager.
Task J> - Data Reduction and Analysis
(A) A Fortran IV program is to be written to expedite analytical
calculations and correlation studies.
(B) Data is to be analyzed to determine the significance of low
and high molecular weight fractions in test waters in influ-
encing the standard algal bottle assay.
Task 6 - Deliverabies
The following deliverabies are to be made to the Eutrophication Branch,
Environmental Protection Agency, National Environmental Research Center,
Corvallis, Oregon;
(A) 11 Monthly status reporta.
(B) Oral report of program status at conclusion of 6th month.
(C) Final report two months following completion of contract.
Schedule
Study is to be conducted over a 12 month period exclusive of the final
report.
8
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SECTION III
INTRODUCTION
This report provides a detailed account of all work carried out from
1 July 1972 to 1 July 1973 under Contract #68-01-0904, granted to the
General Electric Company, Re-Entry and Environmental Systems Division,
Philadelphia, Pennsylvania, by the U.S. Environmental Protection Agency,
National Environmental Research Center, Corvallis, Oregon.
The primary objective of the program was to evaluate three methods
(capillary membrane dialysis, coagulation, alumina adsorption) for
selectively removing nutrients, cations, and anions from water and
wastewater. A comparison of a biological system with physico-chemical
techniques was originally proposed, but was abandoned with concurrence
of the Project Officer in favor of using alum in combination with a
polyelectrolyte based on its use in the tertiary treatment facility of
the U.S. Environmental Protection Agency at Ely, Minnesota.
The organization of this report discusses the basic rationale for con-
ducting the study; equipment and methods used in the treatment of water
derived from three streams in the Schuylkill River basin and effluents
of two waste treatment (1 secondary and 1 tertiary) plants; analytical
methodology; and data reduction and analysis.
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SECTION IV
PURPOSE AND NEED OP THE STUDY
1234
Development of a standarized algal assay ' ' ' has provided a practical
means of Investigating and solving problems related to eutrophication.
Based on established procedures the growth of a test alga as Selenastrum
caprlcornutum Printz in a sterile synthetic nutrient medium is compared
with growth of an equivalent inoculum in a sterile sample of test water
under identical conditions of incubation and illumination. The slope of
the standard curve is compared with that of the unknown to assess the
eutrophication problem in a given body of water or provide an index of
the effectiveness of treatment methods.
This has created a problem in data analysis since the aforementioned
synthetic medium per se_ contains macro- and micro-nutrients, including
trace metals, which may be deficient in some test waters and/or in
excessive concentrations in others (Table 1). Thus, differences in the
slope of the unknown assay curve in comparison to the standard may not
only be due to a limiting nutrient such as phosphorus, but a compound
effect attributed to stimulation or repression of metabolic processes by
other chemicals which cannot be readily compensated for from one assay
to another. In addition, waters to be evaluated may also contain high
concentrations of dissolved solids (low and high molecular weight),
including organic5 and inorganic toxicants, which are capable of influ-
encing assay results by virtue of algicidal or algistatic activity.
A potential approach to solving the problem has been suggested by the
Eutrophication Branch, National Environmental Research Center, Corvallia,
Oregon, in which the synthetic assay medium^ is substituted with a basal
medium prepared from an aliquot of the test water (Figure 1), In this
scheme the freshly collected water is chilled (4°C) to retard microbial
growth, vac cum filtered through an unlined 0.45/j membrane filter,
divided into two containers, and autoclaves at 15 psig for 30 minutes.
One container is stored at 4°C in the dark until required for the assay
and the other processed to produce a basal medium. The optimum method
would allow nutrients, cations, and anions to be removed individually or
collectively without altering the percentage composition of the other
constituents. Treated water would be analyzed to confirm the concentra-
tion of nutrients removed and sub-divided, for example, into four equal
volumes. Incremental concentrations of the nutrients removed would be
added to three of the containers from sterile stock solutions of each
nutrient prepared from reagent grade chemicals. The fourth container
would serve as a blank but would have its volume suitably adjusted with
sterile,distilled water.
Each container of the reconstituted medium and blank plus two of the
test samples would be inoculated with IcP/ml Selenastrum caprlcornutum
10
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Frintz, or other appropriate test organisms, incubated, and processed
according to standard assay procedures^.
It is the intent of this study to investigate the feasibility of methods
which would be suitable for selectively removing nutrients, cations,
and anions, individually or collectively from water and wastewater for
the purpose of preparing a basal algal assay medium.
11
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Table 1
Comparison of Macro- «nd Micro Nutrients of Synthetic Algal Assay Median With Those Typically Found in Trout Run
French Creek, Valley Creek, of the Schuylkill River Basin and Effluents of the Phoenlxvllle (Secondary) and
Hatfleld (Tertiary), Pennsylvania Waste Treat»ent Plants.
CONSTITUENT
Mtcronutrtenu
M>3>N
Total I04-P
Hi
8
C- Inorganic
0*
Ha
K
Nicrcmutrlents
a
Hn
Zo
Co
Cu
Mo
T*
Nutrients, Minerals, Phyalco-Cheaiical
Paraasteri Not Specified for Synthetic
Ned lias
Silica
«o4
aoj-ii
HH3-N
KJeldahl M
Specific Conductance***
Total Alkalinity
Cl
Total Solid*
Dissolved Solids
Total Carbon
Organic Carbon
Hardness OTA
CONCENTRATION PARTS PER MILLION ~
swnnmc MEDIUM
4.2
0.186
2. 904
1.911
2.143
1.202
11.001
0.469
0.03246
1.115
0,01569
0.00035
0.00004
0.00287
0.03305
.....
TROUT
RUN
1.91
0.009
15.5
23
35
5.4
1.76
0.06
0.05
0.04
0.1
0.1
**
0.1
0.06
18.1
0.004
0.13
0.40
340
93.4
**
186
**
27.5
4.5
115.4
FRENCH
CREEK
1.47
0.029
**
7.3
17.5
10.1
1.5
0.11
0.05
0.02
0.1
0.1
**
0.1
5.24
33.5
0.008
0.07
0.27
220
26.9
**
130
132
11.1
3.8
48.0
VALLEY
CREEK
2.23
0.159
19.5
! BELOW UNI
26.8
62
15.7
2.1
0.18
0.05
0.02
0.1
0.1
**
0.1
0.56
34.2
0.012
0.03
0.28
500
146
**
350
463
33.6
6.8
16B
PHOENIXVILLE
0.19
7.9
12.0
)ER SO^ -
43.2
80
66
16
0.86
0.05
0.08
0.1
0.1
**
0.28
6.42
119
0.087
22.8
31.4
825
177
**
406
650
65.3
22.1
156
HATFIELD
0.05
0.216
9.2
50.8
87
60
14
0.90
0.05
0.04
0.1
0.1
**
0.1
3.16
357
0.10S
64,7
70.2
1530
213
**
666
668
72.6
21.8
261
* Baa Appendices I.(All strea* and plant effluents collected April 1973)
** lot tested.
*** Expressed as ft afcos/ca.
12
-------
Figure 1
Idealized Method of Preparing Basal Medium for Bottle Algal Assay Procedure
FRESHLY COLLECTED
WATER SAMPLE
(NO PRESERVATIVES)
I PREFERABLE I
I TO PROCESS |
l_ IMMEDIATELY I
STORE IN DARK AT 4°C
NO LONGER THAN 2 HOURS
FILTER 0.45 U MEMBRANE
SAMPLE FOR
BASAL MEDIUM
I SAMPLE FOR
AUTOCLAVE AT
15 PS1C FOR
30 MINUTES
DIVIDE INTO
FOUR ALIQUOTS
ANALYZE
NUTRIENT/ION
PROFILE
I AUTOCLAVE AT '
I 15 PSIG I
|_30 MINUTES I
RE-ANALYZE -
CONFIRM
NUTRIENTS/ION
REMOVAL
I STORE AT 4°cl
I FOR ASSAY I
"WARM TO~I
I 25°C I
#1
BLANK
WOCULATE
103 CELLS/ML
• eapricornututn
ntCU!
ATE!
*2
RECONSTITUTE
NUTRIENTS/ IONS
0.1
INOCULATE
103 CELLS /ML
s eaprieornutun
INCUBATE
1
« j | #4
RECONSTITUTE j i RECONSTITUTE
NUTRIENTS/ IONS i j NUTRIENTS/ IONS
i.o ! ! 10.0
INOCULATE ~| | INOCULATE
103 CELLS/ML i! 103 CELLS/ML
S. CAPRICORNUTUM i i S. CAPRICORNUTUM
INCUBA1
CONSTRUCT
STANDARD
CURVE
l] i INCUBATE 1
1
I DIVIDE INTO I
I_THREE_ALI2UOTS J
1 INOCULATE ' ' INOCULATE
103 CELLS/ML ' 103 CELLS/ML \
. S. CAPRI- I . S. CAPRI- ; ' S.
INOCULATE •.
103 CELLS/MI.:
. u • \4n& ix i~ , . ** • CArKI ~ t
|_CORNUJUM _ J |_CORNUTUM _ _j ,_ CORNUTITM_ _|
1
(INfiUBATEj '_ INCUBATE
I COMPARE SLOPE -
I WITH i
I STANDARD3 |
13
-------
SECTION V
EXPERIMENTAL PROCEDURES
DERIVATION OF WATER SAMPLES
Three streams (Trout Run, Valley Creek, and French Creek) in the
Schuylkill River Basin of Southeastern Pennsylvania were selected for
this study based upon a preliminary survey of physico-chemical char-
acteristics; accessibility; and proximity to the laboratory. Sampling
sites are documented in Table 2 and identified on a map of the river
basin (Figure 2).
DERIVATION OF WASTEWATER SAMPLES
Effluents were collected from a secondary (Phoenixville, Pennsylvania)
and a tertiary6 (Hatfield Township, Pennsylvania Municipal Authority
Advanced Waste Treatment Facility) treatment plant. Data pertinent to
these are summarized in Table 3. Selection was based upon the avail-
ability of secondary and tertiary effluents within a convenient distance
of the laboratory to minimize delays in analyzing and processing samples
(Figure 2).
COLLECTION AND PROCESSING OF SAMPLES PRIOR TO TREATMENT
Samples for a given experimental run were collected in four (4) liter
Cubitainers(R) (Hedwin Corporation, Baltimore, Maryland) equipped with
polypropylene closures at each of the stream sites within 45 minutes -
.1 hour and immediately returned to the laboratory. Plant effluents
were also collected in the same type of container but on an independent
schedule to preclude a backlog of analytical work or conflict with other
programs.
Samples were recovered from stream or effluents with a 900 ml (Tri-
pour(R)) disposable beaker and transferred to the CubitainerW. Care
was taken to insure complete filling and elimination of dead space
prior to sealing with the closure. Each container was appropriately
identified with the location, date, and time of collection.
Temperature adjustment to ~ 4°C was initiated at the collection site by
placing the containers in an insulated chest containing water ice.
SAMPLE FILTRATION
Upon receipt at the laboratory approximately half of the sample (5-6
liters) collected at each site was vacuum filtered through a plate (no
grids) 0.45jj membrane filter (Millipore Corporation, Bedford, Mass.)
into a two liter flask which had previously been washed (without
14
-------
Table 2
Stream Sampling Sites
-
STREAM
French Creek
Valley Creek
Trout Run
LOCATION
Rapps Bridge
Covered Bridge
Thomas Road
15
-------
LUZERNE COUNTY
NORTHUMBERLAND
r
PENNSYLVANIA X
SCHUVLKILL
RIVER BASM I
LOCATION MAP
DAUPHIN
COUNTY
NEW JERSEY
SCALE IN MLES
NEW JERSEY
Figure 2i Schuylkill River Hasin; FretvcVv Creek, Valley Creek, and Trout Run sampling sites.
-------
Figure 2. Schuylklll River Basin: French Creek, Valley Creek, and Trout Run sampling sites,
(Continued)
-------
Table 3
Specifications of Waste Treatment Plants
PLANT
Phoenixville, Pa.
Hat fie Id Township
Municipal Authority
Advanced Waste ,
Treatment Facility
DRAINAGE
BASIN
Schuylkill
River
Delaware
River
RECEIVING
WATERS
Schuylkill
River
Neshaminy
Creek
TYPE
Secondary
Tertiary
RATED
CAPACITY
6 mgd
3.6 mgd
TREATMENT MODE SUMMARY
Primary +
Trickling Filter +
Activated Sludge
Lime Treatment Raw Sewage
at pH 9.5-10.5
Solids Recirculation to Primary
to Conserve Chemicals
Combined Bio-Oxidation &
Nitrification
Mixed Media Filtration
-------
Figure 3
General Scheme For Proc««stnp, and Analygic of Hatar and Uas'.ewaLer Samples
I ALUMINA ~l
rCAPItLARY~l
I MEMBRANE
I COAGULATION 1
WITH ALUM +
REPORT AS
"FILTERED1
| ~ ~ LDIALYS IS J
_[_
Ij^ZRJ
L__ _L___
SERVED) (PRESERVED! UN
("STORE AT"
I 4°C IN 1
1 DARK _ J
PRESERVED
POLYELECTRO-
LWTB |
T
.J..
PRESERVED
TSTORE AT "I
1 4°C IN 1
1 HARK j
.[
(UNTRE
CONT
1
IUNPRESERVED
I ANALYZE |
IDWEDIATELYI
(ANALYZED
I ACCORDING
, TO PRE-
' DETERMINED
'.SCHEDULE _
ANALYZE
IMMEDIATELY |
(ANALYZED
| ACCORDING |
TO PRE- i
1 DETERMINED
I_3CHEDUL£ I
rSTORE AT 1
I 4°C IN I
L»«K _ j
" ~
I ANALYZE
(IKMEDIATELYI , ACCORDIMG i
, TO PRE- '
1 DETERMINED >
I_S£HEDU18 |
TREPORT AS I
I AUIMIKA I
L IWATEE J
t REPORT AS |
, CAPILLARY |
MEMBRANE ,
1 DIALYSIS
I TREATED I
I RETORT AS~ ~l
I COAGULATION I
I TREATED j
SIE TABU HO.
18
-------
phosphate containing soaps), rinsed three times in deionized water, and
dried at 100°C in a convection oven. Filters were operated with and
without the benfit of glass-fiber pre-filters and replaced as flow
rates diminished due to the accumulation of solids. Filtrates were
added to previously unused CubitainersOO, sealed, identified, stored
in the dark at 4°C, or processed according to the flow chart outlined
in Figure 3.
SAMPLE PRESERVATION
In all cases raw samples (unfiltered) and filtrates were further sub-
divided into two and three aliquots, respectively. One sample in each
category (Ai-A2 in Figure 3) was designated as being "unpreserved" and
given priority for immediate analysis to minimize changes in concentra-
tions of labile constituents. A second unpreserved filtered sample
(Figure 3 BI) was immediately sub-divided into three additional portions
for treatment by alumina adsorption; capillary membrane dialysis; and
coagulation.
Samples (A2 and 83) to be "preserved" were similarly sub-divided into
smaller containers; identified; and treated with specific preservatives
prepared from reagent grade chemicals according to standard U.S.
Environmental Protection Agency procedures^ (Table 4). These were
stored in the dark at 4°C and analyzed within the recommended holding
period.
Although mercuric chloride was a suitable preservative for nitrogen
analysis, including Kjeldahl and nitrate/nitrite, it was found to inter-
fere with low level phosphorus analyses. For this reason phosphorus was
included among the test parameters of "unpreserved samples" (filtered
and unfiltered) analyzed within a short period of being received in the
laboratory. Samples for boron and silica analysis were preserved with
suIfuric acid and those for metal cations with nitric acid.
EQUIPMENT AND METHODS OF TREATMENT
Equipment and methods for treatment of membrane filtered samples of
water and wastewater by coagulation, capillary membrane dialysis, and
alumina adsorption are to be described.
Requirements for filtered samples have been dictated by the capillary
membrane system since particles > 10fi (see Appendix II) can be trapped
and result in the development of a pressure differential. For this
reason the decision was made to standardize all treatment processes by
using membrane filtered samples.
19
-------
Table 4
Preservation of Filtered and Unfiltered Samples *
•X>*A>
ELEMENT
Metal Cations
Nitrogen (All
Forms)
Boron
Silicon
PRESERVATIVE *"
HN03
HgCl2
H2S04
H2S04
CONCENTRATION
5 ml/ liter
40 rag/ liter
at 4°C
2 ml/ liter
2 ml/ liter
MAXIMUM HOLDING
PERIOD BEFORE ANALYSIS
6 months
7 days
7 days
7 days
REFERENCE
Methods for Chemical Analy-
sis of Water & Wastes, U. S
EPA
ibid, P3.
-
-
All samples stored/ preserved in Cubitainers^equipped with polypropylene closures.
^Reagent Grade
-------
(A) Coagulation
Water Samples -
A 0.8 liter sample was added to a 1 liter beaker and mixed at 100 rpm
with a Phipps-Bird* variable speed mixer (Figure 4). To this was added
20 ppm reagent grade alum (aluminum potassium sulfate) to achieve a
final concentration of 100 ppm. Mixing was continued for 15 minutes and
Betz #1150** pplyelectrolyte was added to produce a total concentration
of 2 ppm. After 2 minutes the mixing speed was reduced to 20 rpm for 2
minutes and turned off. The mixture was allowed to settle for 30 min-
utes and vacuum filtered (0.45^, membrane filter) into a clean (phos-
phate free) 2 liter side-arm flask. This was transferred to a
Cubitainer(R), identified, and processed according to the flow diagram
in Figure 3.
Wastewater Samples -
These were treated in the same was as water samples per se_ except that
100 ppm of alum and 2 ppm of Betz #1150 polyelectrolyte were used
instead of the values cited above.
(B) Capillary Membrane Dialysis
A Dow+ Miniplant DialyzerW equipped with cellulose capillary membranes
was used in this part of the study {Figure 5). The unit as such has a
nominal surface area of 15 x 10^ cnr and a molecular weight cutoff of
~5,000 (manufacturer's specifications).
This was mounted in a universal clamp attached to a ring stand adjacent
to ancillary equipment (Figure 7). Gum rubber tubing of convenient
lengths was attached to the dialysis chamber at connectors A, B, C and
D in Figure 5. "A" represents the influent to the capillary membranes
and "B" their effluent. "C" is the influent to the jacket and "D" the
effluent. Relationship between the membranes and the jacket per se_ can
be more readily visualized by the compartmentalized diagram in Figure 6.
The arrow on the side of the chamber (Figures 5 and 6) represents the
direction of flow in the fibers. Those in the jacket (Figure 6) depicts
the counterflow of the dialysis medium from "C" to "D".
Tubing attached to the membrane and jacket influent lines are fed
through a two-channel finger pump (P) (Zero Max Model 14+) and terminate
* Phipps-Bird, Inc., Richmond, Virginia
** Betz Laboratories, Trevose, Pennsylvania
+ Dow Chemical Company, Midland, Michigan.
£ The Zero Max Company, Minneapolis, Minnesota
21
-------
N3
Figure 4. Variable speed mixer assembly employed in standardized coagulation of water and wastewater
with alum (aluminum potassium sulfate) and polyelectrolyte (Betz #1150).
-------
LC
Figure 5. Capillary membrane dialysis assembly: A) Membrane influent (arrow indicates
direction of flow); B) Membrane effluent; C) Dialysis medium influent;
D) Dialysis medium effluent.
-------
tntnnnn tn nnn-Trrfl.L
Figure 6. Cross section of capillary membrane dialyzer showing relative positions of
membranes to jacket with flowing dialysis medium: A) Membrane influent (arrow
indicates direction of flow); B) Membrane effluent; C) Dialysis medium influent;
D) Dialysis medium effluent; J) Jacket containing dialysis medium (arrow indicates
direction of counter flow).
-------
Figure 7. Capillary membrane dialyzer and ancillary equipment: CMD) Capillary membrane
dialyzer; A) Membrane influent; B) Membrane influent; C) Dialysis medium influent
to jacket; D) Dialysis medium effluent from jacket; LF) Line filters; S) Sample
reservoir: DM) Dialysis medium reservoir; P) Pump; T) Timer; 0) Timer over ride
switch
-------
in the sample and dialysis medium (DM) reservoirs, respectively (Figure
7). Polypropylene nipples are attached to the ends of the tubing to
insure positioning on the bottom of each of the containers.
Influent lines were originally equipped with 25ram (0.45^) filters
(Figure 7-LF) to protect the membranes and jacket from particulates;
but can be eliminated as long as samples are pre-filtered and the
dialysis medium is limited to freshly collected deionized water.
The effluent line from the membranes (Figure 7-B) also terminates in the
sample reservoir whereas the jacket effluent (D) is discharged directly
into the laboratory waste treatment system.
A universal timer* is employed to control the dialysis period by turning
the pump off following a pre-determined period of operation. It is
equipped with a manual override switch (Figure 7-0) which facilitates
priming, or can be used for shutting down the system if an emergency
arises.
jPre-Dialysis Procedures
Flushing of Preservative from System - Since the capillary mem-
branes are composed of cellulose acetate, they are vulnerable to attack
by cellulose degrading microorganisms. For this reason it is necessary
to flush the membranes and jacket between each use cycle with 2.5%
formaldehyde. As a pre-dialysis requirement, this must be removed by
purging the entire system with deionized water.
The dialyzer is set-up as diagramed in Figure 8 with the influent lines
for the membranes (A) and jacket (C) feeding from a Cubitainer(^)
containing freshly collected deionized water (DW). Effluent lines B and
D discharged directly into the laboratory waste treatment system.
Approximately 4 liters are pumped through each compartment at a flow
rate of approximately 60 ml/minute.
Purping of System with Sample - The membrane influent line (A) is
removed with the dionized water (DW) reservoir while continuing to pump
until the membranes are displaced with air and effluent is no longer
discharged from line (B).
At this point, the influent pick-up (line A) is placed into a Cubitainer^)
containing 1.5 liters of sample (Figure 9-S), and the membranes purged
until bubbles are no longer observed to be discharged.
* Dimco-Gray Company, Dayton, Ohio
26
-------
ro
-o
IIOAC
^••^•M
60
Hz
E
CMD
Figure 8. Capillary Membrane Dialyzer: Pre-dialysis purging of system to remove preservative: CMD)
Capillary membrane dialyzer; A) Membrane influent; B) Membrane effluent; C) Dialysis
medium influent to jacket; D) Dialysis medium effluent from jacket; DW) Deionized water
(dialysis medium) reservoir; PL) Pump channel for dialyzer jacket; ?2) Pump channel for
capillary membranes; T) Timer; 0) Timer over ride switch; D) Drain to laboratory waste
collection system; Capillary membrane circuit; Jacket circuit;
Timer control circuit.
-------
Pumping is continued until the first 100 ml is collected in a graduated
cylinder and discarded. The pump is turned off at the override switch
(0) and the membrane effluent line (B) is inserted into the sample
container (Figure 9-S). Thus, a closed circuit is established in which
the sample is recirculated through the membranes during the test period.
Sample Dialysis - The dialysis medium (deionized water) reservoir
is filled and the timer is set to operate for 45 minutes in the auto-
matic mode. Dialysis medium effluent is continuously discarded as
indicated in Figure 9. Flow rates in both channels were maintained at
60 ml/minute in all experiments.
At the conclusion of the dialysis period the sample pick-up is removed
from the reservoir and the pump is operated until the effluent line (B)
is no longer discharging. The sample container is now sealed, appro-
priately labeled, and transferred to the analytical laboratory for post-
treatment analysis (Figure 3).
Prior to processing the next sample the membranes are eluted with two
liters of deionized water while maintaining flow in the jacket. This
is followed, as described above, with the pre-dialysis step of purging.
(C) Alumina Adsorption Column
A column was prepared from commercially available interchangeable
components (Table 5). This consisted of a 50 x 1200mm Pyrex(R)
chromatographic column threaded at both ends and connected with
gasketed nylon couplings to an addition funnel and TeflonCR) stopcocked
bottom drip to prevent packing material from being discharged with the
column effluent.
The assembled column was supported with four universal clamps projecting
from a frame of vertical rods which was securely fastened to two paral-
lel pipes running along the back wall of the laboratory (Figure 10).
Two additional rods were attached to the bottom of the frame and were
adjusted to protect the bottom drip from accidental blows when the
column was not in use.
A Big-Jack™' was positioned beneath the bottom drip as a means of
conveniently adjusting the height of various sized receiving vessels.
Aluminum Column Charging
Alumina** (aluminum oxide), grade F-l (Lot 2139), 28-48 mesh, was
re-screened to obtain a product ranging from 30-60 mesh. This was
* Precision Scientific Company, Division of GCA Corporation,
** Alcoa, Bauxite, Arkansas
28
-------
Table 5
Alumina Column Components and Specifications
COMPONENT
Addition Funnel
Chroma tographic Column
Couplings, Nylon
Adapter-Bottom Drip
Filter Disc, Type B
Float
SPECIFICATION
Pyrex(R)
4 Liter Capacity
(50 mm Threaded End)
Pyrex(R)
50 x 1200 mm
50 mm
PyrexW
50 mm with 1:5
Teflon Stopcock
Polyethylene,
50 mm
Polyethylene,
50 mm
NO.
REQUIRED
1
1
2
1
1
1
CATALOG NO.
5822 - Code 20
5820 - Code 56
5840- - Code 20
5835-B - 'Code 20
5847 - Code 20
5849 - Code 20
* Ace Glass Company, Vineland, New Jersey 08360
29
-------
110 VAC
i
60 Hz-
OJ
o
&:
PL-B
IDR
CMD
Figure 9. Capillary Membrane Dialyzer: Operational Mode: CMD) Capillary Membrane dialyzer; A)
Membrane influent; B) Membrane effluent; C) Dialysis medium influent to jacket; D) Dialysis
medium effluent from jacket; DW) Deionized water (dialysis medium) reservoir; Pi) Pump
channel for dialyzer jacket; P£) Pump channel for capillary membranes; S) Sample reservoir;
DR) Drain to laboratory waste collection system; T) Timer; 0) Timer over ride switch;
Capillary membrane circuit; Jacket circuit; Timer control
circuit.
-------
Figure 10. Alumina column suitable for batch treatment of 0.45JJ.
water and wastewater samples.
31
-------
Table 6
Sunnary of Analytical Methods
JNVTRIENTS
Carbon, organic (dissolved)
Carbon, organic (total)
Nitrogan, tassonia
Nitrogen, total
Phosphorus, total
Phosphorus, dltaolvad
Phosphate, orthq
Phosphate, ortho (dissolved)
Phosphorus, hydrolyiable
Phoaohorua. hvdrolwabU (dlMolved)
SH2
SM2
EPA1
EPA!
EPA1
EPA1
EPA1
EPA1
EPA1
EPA1
CATIONS
Calcium (Ca)
Potass luai (K)
Magnesium (Hg)
Sodluat (Ma)
Coppar (Cu)
Zinc (Za)
Iron (Pa)
Manganese (Ni)
Cobalt (Co)
Boron (1)
Silicon (81)
EPA1
EPA1
EPA1
EPA1
EPA1
EPA1
EPA1
EPA1
PE3
SM2
EPA1.
ANIONS
Sulfata (806)
Sulflta (803)
Nltrata (M03)
Mitrlta (N02)
Chlorlda (Cl~)
EPA1
SH2
EPA1
EPA1
EPA1
Combuition/IR
Conbuatlon/lR
Dl«tlll«tlon, Procedure
KJ«ldahl
Pertulfate Digestion
Per»ulf«te Digest Ion
Direct Colorinetric
Direct Colorlmetrlc
Sulfurlc Acid Hydrolysis
Sulfurlc Acid Hvdrolvtls
Atonic Absorption
Atonic Absorption
Atomic Absorption
Atonic Absorption
Atomic Absorption
Atonic Absorption
Atomic Absorption
Atonic Absorption
Atomic Absorption
CurcuDin or Carmine
Slliconolybdate Color
Turbidlmetrlc
Iodide- Iodine
Bruclne Sulfata
Dlazotizatlon
Mercuric Nitrate
p. 257
p. 257
p. 134
p. 149
p. 263
p. 263
p. 263
p. 263
p. 263
D. 263
P. 102
p. US
p. 112
p. 118
p. 106
p. 120
p. 108
p. 114
p. 69
o. 273
p. 286
p. 337
p. 170
p. 195
P. 29
K^(HUMtOUS ANALYSES
pR
Conductivity
Total Dissolved Solids
total Soll«s
Hardness (Carbonate/Bicarbonate)
Total Alkalinity
EPAl
Sll
EPA1
EPA1
EPA1
BPAl
•PA1 "Methods for Chemical Analysis of Water and Naataa", Bnvlronwn
Analytical Quality Control Laboratory, Cincinnati, Ohio, (1971)
SM* "Standard Nathoda for tna bMlnatlon of Uatar and Waatavatar",
Electron* trie
Uheatatone Bridge
CraviMtric, 180°C
Gravimetric, 105°C
EDTA Tltratlon
Electros* trie
p. 230
p. 323
p. 275
p. 280
P. 76
P^6
tal Protection Agency, Water Quality Office.
APHA, AWWA, WPCF, ed. 1),
American Public
"Analytical Methods for Atomic Absorption SpactrophotosMtry", Parkin Elver Corporation, Nor walk
Connecticut, (1966).
-------
slurred a minimum of 3X in deionized water and decanted to remove fines.
The product was dried to constant weight at 100°C. Approximately 1800
grams was added to the column through the addition funnel with gentle
agitation, immediately wetted by drop wise addition of deionized water
(stopcock closed) until completely covered, and gradually drained with
continued addition of water. This allowed the individual alumina
particles to uniformly pack while minimizing problems of channeling.
The alumina, although previously unused, was treated with calcium
hydroxide (Ca(OH)2) and sodium hydroxide (NaOH) by conventional tech-
niques to remove any phosphorus which may have been present?. Following
this procedure the column was washed with 5 volumes of deionized water
and retained in the alkaline form throughout the study.
Approximately 1.6 liters of water was required to completely cover the
alumina in the column. Upon draining a total of 765 ml could be
collected while leaving 835 ml physically in contact with the alumina
surface. This could be displaced by dilution following further addi-
tion of water and drainage. As such this provided the rationale for
the treatment of individual samples.
Alumina Treatment of Samples
The following procedure was employed to treat individual filtered
samples:
(1) Completely drain column.
(2) Add 3 liters of deionized water.
(3) Drain 500 ml to displace possible entrapped air bubbles.
(4) Allow to stand 45 minutes and completely drain.
(5) Add 3 liters of sample to column; repeat step 4 and discard.
(6) Add 2 liters of sample to column, drain, collect, identify
and analyze.
(7) Add 3 liters of deionized water to column; allow to stand
until ready for processing of next sample.
It was considered that potential contamination of consecutive samples
was an inherent problem associated with this method of treatment; but
could in part be overcome by adapting a standardized procedure.
Analytical Methodology
Replicate analysis of unfiltered and filtered samples for each para-
meter was conducted according to current U.S. Environmental Protection
Agency8 or Standard Methods9 Procedures unless otherwise specified
(Table 6).
Standards
Standards for nutrients as outlined in Table 7 were prepared on the day
33
-------
of use by dissolving appropriate quantities of reagent grade chemicals
in pretested distilled water to provide 1000 ppm stock solutions.
Aliquots were subsequently diluted to prepare 3-4 concentrations of
working standards in volumetric flasks. Standard curves were con-
structed with replicate analysis at each concentration to insure
reproducibility. Further analysis of standards was conducted periodi-
cally during a given test period, i.e., one working day, as both a
check on precision and to correct instrument drift.
Nutrients
In the case of low level phosphorus and nitrogen (Kjeldahl, ammonia,
nitrate/nitrite) analysis, standards were tested on a more frequent
basis to confirm stability and validity of test data. It should be
pointed out that delays must be minimized between the time a sample
is collected and analysis for nutrients is initiated if preservatives
are to be eliminated. As previously discussed, this is highly desir-
able in the case of phosphorus analysis where preservatives are sus-
pect^d of interfering with the colorimetric reactions. An alternate
procedure would involve freezing filtered and unfiltered samples,
but should only be considered if analytical services are not readily
available.
Cations
All samples analyzed for specific cations by atomic absorption spectro-
photome try8,9,10 were preserved with nitric acid. Sulfuric acid was
employed for those to be tested for silica and boron. Working stand-
ards for metal cations were conveniently prepared from 1000 ppm commer-
cially available stock solutions (Table 7).
Anions
Anions given priority for analysis included nitrate and nitrite which
were also processed without benefit of preservatives. Refrigerated
samples (filtered and unfiltered) were analyzed for sulfate and
chloride within a week following collection. Those intended for
analyses of sulfite content were cooled to 4°C. in the field and
analyzed the same day. Although originally specified as an analytical
parameter for this program sulfide was eliminated due to the large
number of variables influencing its analysis^.
Miscellaneous Analysis
Of the miscellaneous analyses pH and conductivity were determined
immediately before and after filtration; alkalinity and solids (total
and dissolved), were set up from refrigerated samples within 24 hours
of collection. Standards and their derivation are summarized in
Table 7.
34
-------
TabU 7
MO
1
Z
3
4
5
6
7
8
9
1
2
3
4
5
6
7
8
9
10
11
1
2
3
4
•5
1
2
3
4
5
6
HOTRiniTS
Carbon, total
Carbon, organic
Carbon, Inorganic
Nitrogen, aaaonla
Nitrogen, total
Nitrogen, nitrite/
nitrate
Phosphorus,
Hydrolyzable
Phosphorus, total
Phospba t« , or too
C&TIORS
CalciuB (Ca)
Potassluai (K)
Msgnesluai (Mg)
Sodium (Ha)
Copper (Cu)
Zinc (Zn)
Manganese (Ma)
Cobalt (Co)
Iron (Fe)
Boron (B)
Silicon (Si}
AN IONS
Sulfate (S04)
Sulfite (S03)
Nitrate (NOj)
Nitrite (N02)
Chloride 1C1)
MISCELLANEOUS
Conductivity
Total Dlss. Solids
Total Solids
Total Alkalinity
Hardness (Carbon-
ate/Bicarbonate)
P«
STANDARD
See #2 and #3
PotaseiuB Hydrogen Phthalat*
Sodlua Carbonate
Sodlun Bicarbonate
AasKraluB Chloride
AanonluB Chloride
Sodlias Nitrite,
Potassluai Hitrate
Mono Basic Potassium Phosphate
Mono Basic Potesalun Phosphate
Mono Basic Potassium Phosphate
Calcium Carbonate/Dilute Nitric Acid
Potassium Chloride/ Dis til led Hater
Magnesium Metal/Dilute Nitric Acid
Sodiun Bicarbonate/Dilute Nitric
Acid
Copper Oxide/Dilute Nitric Acid
Zinc Oxide/Dilute Nitric Acid
Manganese Metal/Dilute Nitric Acid
Cobalt Metal/Dilute Nitric Acid
Ferric Chloride/Distilled Hater
Boric Acid/Distilled Water
Sodiun Silicate/Distilled Water
Sulfuric Acid
See Nutrients *6
See Nutrients #6
Sodium Chloride
Sodium Chloride
Calcium Carbonate
pH 4.0 Buffer Concentrate
pH 7,0 Buffer Concentrate
pH 10.0 Buffer Concentrate
SOORCK/CATALOC NOMBIK
—
Piaher Scientific Co. P-243
" 8-263
" S-233
" A-661
" A-661
8-347
S-383
P-382
" P-382
P-382
Fisher Scientific Co. So-C-191
" So-P-351
So-M-51
So-S-139
' So-C-194
So-Z-13
So-M-81
1 So-C-193
So-I-124
1 So-B-155
1 So-S-465
Fisher Scientific Co. So-A-200
11
-
-
Fisher Scientific Co. S-271
Fisher Scientific Co. S-271
-
-
Fisher Scientific Co. C-65
" So-B-99
" So-B-109
" So-B-141
MBTBOD OF PtBPARATIOM
.
Heigh, Dissolve, Dilute
Distilled Ha tar
II
II
It
II
II
II
II
II
It
Decimal Dilutions/Distilled Water
II
It
It
II
II
11
II
II
It
"
D*eitMl Dilutions/Diatilled Water
-
-
Weigh/DIssolve/Dilut*
Weigh, Dissolve/Dilute Dis. Water
-
-
Weigh, Dissolve/Dilute Dis. Water
11
Dilute Distilled Water
11
11
STORAGE
TEMPERATURE
°C
.
.
-
.
.
.
-
.
.
-
Store Stock Sol'n
Only/4°C
n
n
"
it
n
n
"
11
"
Store Stuck Sol'n
Only/4°C
-
-
-
4°C
-
-
-
-
Concentrated 4°C
M
ii
FREQUENCY OF
PREPARATION
.
Daily
11
M
II
it
It
II
II
fl
II
Working Stds. /Daily
"
it
n
"
n
11
n
n
"
11
Working Stds. /Daily
-
-
Working Stds. /Daily
Weekly
-
-
Daily
11
Weekly
11
II
-------
SECTION VI
DISCUSSION
Raw data as reported for all samples have been conveniently transposed
into five tables (Appendix 1A-1E) representing each of the water
(Valley Creek, French Greek, Trout Run) and wastewater effluent
(Fhoenixville and Hatfield) collection sites to compare analytical data
before (unfiltered and filtered) and after treatment (alumina absorp-
tion, capillary membrane dialysis, coagulation).
Data representing individual parameters have been plotted as composite
curves (Figures 11-33) to graphically depict comparative treatment
effectiveness for samples collected from the same source at different
times or stream water and treatment plant effluents collected within
the same time span. Each graph has been prepared by plotting values
for untreated samples (unfiltered designated as "U"; filtered as "P")
and following treatment by alumina adsorption ("A"); capillary membrane
dialysis ("D"); and coagulation ("C").
Although not amendable to statistical analysis as a result of the
limited sampling, this provides an interesting insight into the rela-
tive merits and efficiency of each method of treatment. The range of
percentage reduction AR) for each parameter is summarized in Table 8
and is derived from the AR's reported in Appendix 1A to IE, These
were determined by utilizing data for filtered/untreated samples as
baseline values and calculating the percentage reduction for each
method of treatment. In some cases it will be seen that no changes have
been detected following treatment (as indicated by "0" in Table 8), or
in others where as increase (+) has occurred above the untreated
control value. In most cases this occurs either because a specific
treatment process contributes ions to treated waters e.g., excess of
sulfate observed in water and wastewater treated with alum (aluminum
potassium sulfate) or a lack in sensitivity of certain analytical
methods for detecting a change at relatively low concentrations.
TOTAL CARBON
Alumina absorption and dialysis demonstrated equivalent efficiency in
reducing the total carbon content of water and wastewater. Maximum
efficiency determined for all treated waters was 867. and 817., respec-
tively. In constrast, treatment with polyelectrolyte (Betz #1150) and
alum (aluminum potassium sulfate) failed to reduce total carbon by more
than 13%. Total carbon removal, as seen by inspection of Figures 11-
17, can primarily be attributed to the inorganic fraction.
INORGANIC CARBON
Dialysis and alumina adsorption produce comparable results in removal
36
-------
T»hle8
i Jfratramtar Effluent TroUd by AJumlm AdaorpUon; OpilUry M«mr**n»
And Coagulation wtth AJam/Ebfretectrolyto
MO.
1
2
3
4
5
«
7
8
9
10
1
2
3
4
5
6
7
8
9
10
1
2
3
1
2
3
4
PARAMETER
Total Carbon
Organic Carbon
Inorganic Carbon
Total Phosphate P
HjdroJjnmbk>PHo«.P
Phoatfcate -Ortho
XJeJdahlE Nitrogen
Ammonia Nitrogen
Nitrate Nitrogen
Nttrtte Nitrogen
Ca
M*
Zn
K
Na
B
8t
CO
Ca
Fe
803
S04
Cl
Specific Conductance
Hardness-EDTA
Alkalinity -Total
Dissolved Solids
STREAM WATER
FRENCH CKKEK
Ahimtaa
>«**
+-40
+ -50
25-30
85-96
75-92
66-90
+
+
+ -37
+ -«0
95-98
96-98
V
75-92
+
50-80
97-98
U
U
U
U
4-99
0-12
+ -0
96-99
"
+
Dlar/aia
33-50
+ -17
62-70
+ -75
+ -90
+ -60
0-75
+ -70
86-95
0-60
46-80
50-80
U
28-78
67-79
50-88
75-79
U
U
U
U
11-57
8-78
58-67
23-81
74-75
55-56
Coagulation
9-13
4-7
14-25
71-96
75-90
60-90
+ -0
+ -0
0-X3
+ -60
+ -5
+ - 20
U
+
+ -6
0-50
3-27
U
U
U
U
+
+ - 12
+ - 6
+ -27
22-25
+ - 4.3
Alumina
55-63
+ - 55
45-79
50-70
0
0-80
+ -25
+ -50
+ -S3
0
>99
98-99
U
85-90
4-
0-93
60-98
U
U
U
U
23-99
+ -57
+ -30
>99
+ - 30
+
TROUT RUM
Dlalyals
41-73
+ -77
67-71
+ -60
+ -70
+ -60
0-50
0-50
77-2
+ -70
42-78
61-81
U
80-85
8-83
66-80
74-82
U
U
U
U
19-50
72-84
71-77
57-68
71-77
15-92
Coagulation
7-13
20-44
0-8
+ -0
+ -0
+ -80
+ -86
0-50
+ -45
+ -70
3-5
0-9
U
+
+ - 0
0-60
5-60
0
U
U
U
+
+ - 47
5-6
+ - 3
0-6
+ - 15
VALLEY CREEK
Alumina
51-86
0-91
53-66
33-75
50-90
75-93
+ -0
+ -0
0-39
0-50
>99
95-99
U
85-90
+
0-96
25-98
V
U
U
U
84-97
0-26
2-64
>99
34-84
19-28
Dlalyaii
62-81
+ -75
63-84
+ -66
+ - 66
+ -66
0-66
0-40
84-99
0-96
69-85
76-84
U
50-90
80-94
70-90
69-80
U
U
U
U
44-73
12-82
72-82
70-86
74-89
51-80
Coagulation
+ -6
+ -0
0-20
0-75
0-90
0-80
+ -«3
+
4-9
0-50
+ -4
+ -4
U
+
0
0-50
0-23
U
U
U
U
+
0-56
+ - 2
+ -4
6-8
1-37
WASTE WATER EFFLUENT
PHOENDCVIL1E
Atamlna
72-81
13-57
89-98
>99
>99
>99
92-97
>99
0-50
U ***
>99
98-99
U
70-98
21-27
80-88
»l-98
U
U
U
U
94-99
+
48-58
>99
70-93
21-51
DlalyatB
50-78
+ -80
76-81
50-62
50-62
o-«e
84-90
71-94
0-70
50-87
65-69
66-69
U
76-85
77-80
58-87
72-76
U
U
U
U
54-65
81-b7
68-75
60-67
73-81
71-74
Coagulation
9-22
0-36
34-50
62-85
62-63
66-96
+ - 40
0-38
+ -50
+ -12
12-27
0-16
U
+
0-1.7
0 + -
+ -33-4
U
U
U
U
4
+ -36
4
5-7
11-22
+ -50
HATFEEID
Alumina
70-74
0-40
41-90
83-98
75-98
96-98
+ .82
+ -89
0-6
0-4
98-99
92-96
U
+ -96
+ •- 3
72-88
96-98
U
U
U
U
86-98
+ -0
33-62
97-99
72-80
18-52
Diab/sis
68-73
+ -35
59-80
24-58
35-62
40-60
+ -7
+ -82
60-93
56-90
36-70
33-72
U
50-75
48-75
72-90
49-73
U
U
U
U
28-02
28-88
38-74
40-64
62-81
34-67
PflflKM Jfltlflll
3-7
+ -20
5-13
50-96
63-75
80-96
t-I2
+ -90
0-6
0-4
1-53
0-4
U
10-19
1-12
11-50
3-16
U
U
U
1
1
U
+ - 0.6
1-17
+ -4
- '5
a-53
+ - 0. 1
* % reduction ta treated waters compared to untreated (filtered) control ; ** + - concentration greater than untreated (filtered) control ; *** U - concentration unchanged from untreated (filtered) contro
-------
45
35
30
25
20
15
10
CARBON -
VALLEY CREEK #3
TOTAL CAR BON
INORGANIC CARBON
ORGANIC CARBON
U
Figure 11. Carbon profile of water collected from Valley Greek (April
1973) before and after processing. Legend; (U) unfiltered;
(F) filtered; (A) alumina adsorption; (D) dialyzed; (C)
coagulated.
38
-------
80
70
g
30
20
10
CARBON
PHOENIXVILLEfl
MARCH 1973
TOTAL CAR BON
INORGANIC CARBON
ORGANIC CARBON
U
Figure 12. Carbon profile of Phoenixville secondary wastewater effluent
(collected March 1973) before and after processing: (U)
Unfiltered; (F) filtered; (A) alumina adsorption; (D) dialyzed;
(C) coagulated.
39
-------
70
CARBON
PHOENIXVILLE #2
APRIL 1973
S 5
3
i
gj 40
I
30
20
10
U
TOTAL CARBON
INORGANIC
CARBON
ORGANIC CAR BON
-stewater
«
tered;
Md after
(D)
40
-------
90
70
60
50
20
10
CARBON
PHOENIXVILLE #3-
MAY 1973
TOTAL CAR BON
INORGANIC CARBON
ORGAN 1C CARBON
U
Figure 14. Carbon profile of Phoenixville secondary wastewater effluent
(collected May 1973) before and after processing: (U) Unfiltered;
(P) filtered; (A) alumina adsorpiton; (D) dialyzed; (C)
coagulated.
41
-------
70
60
50
40
30
20
10
'••it
CARBON
HATFIELD#I -APRIL 1973
TOTAL CARBON
INORGANIC CARBON
ORGANIC CARBON
U
Figure 15. Carbon profile of Hatficld tertiary wastewater effluent
(collected April 1973) before and after processing: (U)
Unfiltered; (F) filtered; (A) alumina adsorption; (D) dialyzed;
(C) coagulated.
42
-------
90
70
50
*
20
CARbON
HATFIELD *2 - MAY 1973
TOTAL CAR BON
INORGANIC CARBON
ORGANIC CARBON
IT
Figure 16. Carbon profile of Hatfield tertiary wastewater effluent
(collected May 1973) before and after processing: (U)
Unfiltered; (F) Filtered; (A) alumina adsorption; (D) dialyzed;
(C) coagulate.
43
-------
90
70
60
50
40
30
20
10
CARBON
HATFi£LD#3-JULY!973
TOTAL CAR BON
y INORGANIC CARBON
.#
ORGANIC CARBON
U
Figure 17. Carbon profile of Hatfield tertiary wastewater effluent
(collected July 1973) before end after processing: (u)
Unfiltered; (F) Filtered; (A) alumina adsorption; (D) dialysis;
(C) coagulation.
44
-------
of inorganic carbon from stream water and wastewater effluent, although
alumina appears to be slightly superior (Figures 11-17). Based on the
similar effectiveness of alumina and dialysis in reducing sodium
(Figure 29), calcium (Figure 25), magnesium (Figures 26 and 27), and
total alkalinity (Figure 33) levels of treated waters, it is highly
suggestive that inorganic carbon is mainly derived from sodium carbonate
(Na2C03), sodium bicarbonate (NaHCC^), magnesium carbonate (MgCC^) and
calcium carbonate (
Further reduction of the inorganic content by dialysis could be anti-
cipated by extending the dialyzing period from the standard forty-five
minutes used in this study to 1.5-3 hours.
Coagulation, of the three methods similarly is the least efficient when
it is considered that 100 ppm of alum (aluminum potassium sulfate) was
used to treat wastewater samples and 20 ppm for those derived from
streams. This may be attributable to the overall differences in
physico-chemical characteristics of water from such diverse sources as
reflected by variations in total and dissolved solids (Figures 34-38)
and specific conductance (Figure 31).
TOTAL ORGANIC CARBON
Removal of total organic carbon (TOG) by alumina, dialysis, and coagula-
tion presents a relatively inconsistent pattern, however, it is con-
cluded that coagulation was the least efficient on a qualitative basis.
It is speculated that more of the organic carbon associated with macro -
molecules could have been removed by dialysis if membranes exhibiting
a higher molecular weight cutoff (i.e., ~ 5000) had been used for these
studies. In this case, extension of the dialysis period could not be
expected to enhance organic carbon removal due to their association
with macromolecules which are excluded by the cellulose membrane under
consideration.
PHOSPHORUS
Differences in profiles of total phosphate phosphorus, hydro lyzable
phosphate phosphorus , and ortho-phosphate for all waters before and
after treatment are outlined in the Appendix LA-IE. Raw stream water
and wastewater values for all parameters are shown in Table 9.
Treatment efficiencies per se_ are summarized in Table 10 were found to
be a function of the initial concentration as outlined in Table 9.
Alumina provides a highly effective method of treatment ( 99%) for all
species of phosphorus in effluent of the Phoenix vi lie (secondary) plant
but fell to the 75-98% level for water from the Hatfield facility; 75-
96% for French Creek; 50-93% for Valley Creek; and 0-80% for Trout Run.
45
-------
Table 9
Comparative Concentrations of Phosphorus in Raw Stream
Water and Waste water Effluent Prior to Treatment
SOURCE
French Creek
Trout Run
Valley Creek
Phoenixville (Secondary)
Hatfield (Tertiary)
RANGE - PPM
TOTAL PO4
P
.03 - 0.6
.01 - .02
.03 - .16
8
.21 - .64
HYDRO-
LYZABLE PO4
P
.04 - .06
.01 - .02
.03 - .07
7-8
.20 - .63
ORTHO
PHOSPHATE
.03 - .04
.01
.02 - .04
3-7
.09 - .53
46
-------
Table 10
Summary of Phosphorus Treatment Efficiencies for Water & Wastewater
SOURCE
FRENCH
CREEK
VALLEY
CREEK
TROUT
RUN
HATFEELD
PHOENIXVILLE
PARAMETER
Total P04 - P
Hydrolyzable PO4 - P
Ortho-Phosphate
Total PO4 - P
Hydrolyzable PO4- P
Ortho-Phosphate
Total PO4 - P
Hydrolyzable PO4- P
Ortho-Phosphate
Total PO4 - P
Hydrolyzable PO4- P
Ortho-Phosphate
Total PO4 - P
Hydrolyzable PO4- P
Ortho-Phosphate
RANGE OF % REDUCTION FOLLOWING:
ALUMINA ADSORPTION
75 - 96
75 - 92
80 - 90
50 - 75
66 - 90
75 - 93
>50 - 70
0
0-80
83 - 98
75-98
92 - 98
99
99
99
CAPILLARY DIALYSIS
+ - 75
+ - 90
+ - 66
+ - 66
+ - 66
50 - 66
+ - 60
+ - 70
+ - 0
24-58
35 - 62
40 •- 60
50 - 62
50 - 62
0-66
COAGULATION
75 - >90
75 - 90
60 - 90
0-75
0-90
0-50
+ - 0
+ - 0
70 - 80
50 - 62
68 - 75
80 - 96
62 - 85
62 - 83
66 - 96
+ = Exceeds Control Value; 0 = Unchanged.
-------
Table 11
Summary of Total Phosphate Phosphorus Removed
By 0.45tf Filtration of Stream Water & Wastewater Effluent
SOURCE
FRENCH
CREEK
TROUT
RUN
VALLEY
CREEK
PHOENIX VILLE
HATFIELD
SAMPLE NO.
1
2
3
4
1
2
3
1
2
3
4
1
2
3
1
2
3
UNFILTERED
0.6
0.04
0.03
0.05
0.02
0.01
0.02
0.05
0.03
0.16
0.03
8
8
8
0.22
0.21
0.64
PPM
FILTERED
0.05
0.04
0.07
0.05
0.01
0.01
0.02
0.04
0.03
0.03
0.02
8
8
7
0.12
0.16
0.53
REMOVED
0.55
0
+ .04
0
.01
0
0
.01
0
.13
.01
0
0
1
.08
.05
.11
• -~
48
-------
By comparison, alum/polyelectrolyte coagulation removed 62-96% of
phosphorus from Phoenixville waters; 50-80% from Hatfield; and 60-907.
from French Creek. Valley Creek produced more variable results with
removal of 0-90% for all samples tested; and Trout Run data ranging
from values exceeding controls to as high as 80%.
Of the three methods dialysis provided to be the most unreliable under
the test conditions outlined in Section V. With Phoenixville effluent
overall phosphorus reduction ranged from 0-667. and Hatfield 24-60%.
For raw stream waters containing lower concentrations of phosphorus,
dialysis was highly unpredictable with post-treatment values frequently
exceeding that of controls (Table 10).
Inspection of Figures 18-21 and Table 11 reveal the relatively low
levels of phosphorus removed by 0.45fi filtration. In one case in-
volving stream water (Figure 20), an increase in phosphorus was found
after filtration and can only be rationalized by the presence of a
phosphorus contaminant in the vacuum filtration flask.
NITROGEN
Profiles for all waters included Kjeldahl, ammonia, and nitrate/nitrite
nitrogen analysis. Baseline values (i.e., unfiltred) for raw stream
water and wastewater effluent are outlined in Table 12. With exception
of the Hatfield tertiary plant which was experiencing operational prob-
lems only moderate fluctuations were observed over a 6-month period.
The most notable difference between the two types of waters was the
relatively high concentration of nitrates in stream water and nitrite
levels of the Hatfield (tertiary) effluent (Table 12).
Effectiveness of the three methods of treatment under consideration for
removing nitrogen are more demonstrable in treatment plant effluents
(Figure 22) than for stream samples (Figure 23) where baseline values
are relatively low (See Appendix 1A-1E and Table 13). With minor
exceptions alumina contributed nitrogen to stream water, thereby re-
sulting in concentrations greater than control values. Several explana-
tions for this phenomena may be considered. It was first thought that
microbial contamination of the column had occurred, but was highly
unlikely since all water was being filtered through a 0.48 membrane
filter immediately prior to treatment. A more plausible explanation
suggests that organic and inorganic nitrogen are loosely bound to
alumina, and are readily eluted by addition of subsequent samples to
the column. In such a case water containing relatively low levels of
nitrogen could elute a sufficient quantity in a single pass of the
column to exceed pre-treatment analysis values.
KJELDAHL NITROGEN
Review of data before and after 0.45jj filtration reveals Kjeldahl nitrogen of
49
-------
Table 12
Comparative Concentrations of Kjeldahl, Ammonia, And
Nitrate-Nitrite Nitrogen in Raw Stream Water
And Wastewater Prior To Treatment
SOURCE
FRENCH CREEK
TROUT RUN
VALLEY CREEK
PHOENIX VILLE
(SECONDARY)
HATFIELD
(TERTIARY)
RANGE - PPM NITROGEN
KJELDAHL
0.2 - 1.5
0.1 - 0.4
0.1 - 0.2
22 - 29
0.1 - 70.2
AMMONIA
0.1 - 0.6
0.1
0.03 -0.1
15 - 23
0.1 - 64.7
NITRATE
1.5 - 2.4
2.0 - 2.3
2.2 - 2.5
0.1 - 0.2
0.1 - 1.7
NITRITE
0.004 -0.02
0.004 - 0.01
0.01 - 0.02
0.01 - 0.09
0.1 - 4.4
50
-------
Table 13
Summary of Nitrogen Treatment Efficiencies for Water & Wastewater
SOURCE
FRENCH
CREEK
VALLEY
CREEK
TROUT RUN
HATFIELD
(TERTIARY)
PHOENIXVILLE
(SECONDARY)
PARAMETER
Kjeliahl - N
Ammonia - N
Nitrate - N
Nitrite - N
Kjeliahl - N
Ammonia - N
Nitrate - N
Nitrite - N
Kjeldahl - N
Ammonia - N
Nitrate - N
Nitrite - N
Kjeldahl - N
Ammonia - N
Nitrate - N
Nitrite - N
Kjeldahl - N
Ammonia - N
Nitrate - N
Nitrite - N
RANGE OF % REDUCTION FOLLOWING:
ALUMINA ADSORPTION
+
+
+ - 37
+ - 60
+ - 0
+ - 0
0-39
0-50
+ - 25
+ - 50
+ - 83
0
+ - 82
+ - 89
0-6
0-4
92 - 97
97-99
+ - 50
0
CAPILLARY DIALYSIS
0-75
+ - 70
86 - 95
0-80
0-66
0-60
84 - 91
80 - 95
+ - 50
0-50
77 - 81
+ - 70
+ - 7
+ - 82
60 - 93
56 - 90
84 - 90
71-94
0-70
50 - 80
COAGULATION
+ - 0
+ - 0
0-23
+ - 0
0-33
+
4-9
0-50
+ - 66
0-50
+ - 44
+ - 70
+ - 12
+ - 90
0-6
0-4
+ - 40
0-38
+ - 50
+ - 12
+ = Exceeds Control ; 0 = Equals Control.
-------
Table 14
Summary of Kjeldahl Nitrogen Removed By
0.45^i Filtration of Stream Water & Wastewater Effluent
SOURCE
FRENCH
CREEK
TROUT
RUN
VALLEY
CREEK
HATFIELD
(TERTIARY)
PHOENIX VILLE
(SECONDARY)
SAMPLE NO.
1
2
3
4
1
2
3
1
2
3
4
1
2
3
1
2
3
UNFILTERED
0.2
0.2
0.3
1.5
0.3
0.4
0.1
0.2
0.2
0.3
0.1
70.2
0.1
1.8
29
37
22
PPM
FILTERED
0.2
0.1
0.3
0.8
0.4
0.3
0.2
0.2
0.2
0.3
0.1
57.0
0.1
1.3
25
29
20
REMOVED
0
0.1
0
0.7
+ 0.1
0.1
+ 0.1
0
0
0
0
13.2
0
0.5
4
8
2
52
-------
Table 15
Summary of Cation Treatment Efficiencies for Water & Wastewater
SOURCE
FRENCH
CREEK
TROUT RUN
VALLEY
CREEK
PARAMETER
Ca
Mg
K
B
Si
Na
Ca
Mg
K
B
Si
Na
Ca
Mg
K
B
Si
Na
RANGE OF % REDUCTION FOLLOWING :
ALUMINA ADSORPTION
95 - 98
96 - 98
75 - 92
50 - 80
97-98
+
99
98 - 99
85 - 90
0-93
60 - 98
-f
99
95 - 99
85 - 90
0-96
25 - 98
+
CAPILLARY DIALYSIS
46 - 80
50 - 72
28 - 76
50 - 88
75 - 79
67 - 79
42 - 78
61 - 81
80 - 85
66 - 80
74 - 82
8-83
69 - 85
76 - 80
50 - 90
70 - 83
69 - 80
62 - 94
COAGULATION
+ - 5
+ - 20
+
0-16
3-27
+ - 6
3-5
0-9
+
0-60
5-14
+ - 0
+ - 14
+ -
+
+ - 50
+ - 23
0
in
+ = Exceed Control Value; 0 = No change.
-------
Table 15 (Cont'd)
Summary of Cation Treatment Efficiencies for Water & Wastewater
SOURCE
PHOENIXVILLE
(SECONDARY)
HATFIELD
(TERTIARY)
PARAMETER
Ca
Mg
K
B
Si
Na
Ca
Mg
K
B
Si
Na
RANGE OF % REDUCTION FOLLOWING:
ALUMINA ADSORPTION
99
98 - 99
70 - 98
80 - 88
91 - 98
+ - 27
98 - 99
92 - 99
+ - 96
72 - 88
96 - as
+ - 3
CAPILLARY DIALYSIS
66 - 69
66 - 69
76 - 85
58 - 87
72 - T6
77 - 80
36 - 70
33 - 72
50 - 75
72 - 90
49 - 73
48 - 75
COAGULATION
+ - 27
0-16
+
+ - 0
+ - 33
0-1
1-53
0-4
+
11 - 50
3-16
4-12
in
+ = Exceed Control Value; 0 =No change
-------
Table 16
Summary of Boron Removed by 0.45 pi Filtration
Of Stream Water & Waste water Effluent
SOURCE
FRENCH
CREEK
TROUT
RUN
VALLEY
CREEK
PHOENKVILLE
(SECONDARY)
HATFIELD
(TERTIARY)
SAMPLE NO.
1
2
3
4
1
2
3
1
2
3
4
1
2
3
1
2
3
PPM
UNFILTERED
0.1
0.1
0.1
0.2
0.1
0.1
0,3
0.2
0.2
0.2
0.6
0.6
0.9
2.2
0.9
2.0
1.0
FILTERED
0.08
0.1
0.09
0.2
0.1
0.1
0.3
0.1
0.2
0.1
0.6
0.5
0.8
1.7
0.9
1.8
1.0
REMOVED
.02
0
.01
0
0
0
0
0.1
0
0.1
0
0.1
0.1
0.5
0
0.2
0
55
-------
10.0
5.0
1.0
0.5
g
d
0.1
0.05
0.01
0.005
0.001
PHOSPHORUS -
HATFIELD/PHOENIXVILLEI3
HYDRO-
LYZABLE
TOTAL
ORTHO
PHOENIXVILLE
TOTAL
HYDROH
LYZABLE
ORTHO
HATFIELD
Figure 18. Phosphorus profile of Phoenixville secondary wastewater
effluent and HatfieId tertiary wastewater effluent before
and after processing. Legend: (U) unfiltered; (F) filtered;
(A) alumina adsorption; (D) dialysis; (C) coagulation.
56
-------
.01
PHOSPHORUS -
VALLEY I 3
HYDROLYZABLE
.001
Figure 19. Phosphorus profile of Valley Creek water (collected April
1973) before and after processing. Legend: (U) unfiltered;
(F) filtered; (A) alumina adsorption; (D) dialysis; (C)
coagulation.
57
-------
.U6
.09
.06
,05
.04
.03
.02
g.o,
.009
g.008
.007
.005
.004
.003
.002
HYDROLYZABLE
FRENCH CREEK #3
ORTHO
D
Figure 20. Phosphorus profile of French Creek water (collected April
1973) before and after processing. Legend: (U) unfiltered;
(F) filtered; (A) alumina adsorpiton; (D) dialysis; (C)
coagulation.
58
-------
.05
.04
.03
.02
.01
g.009
S.008
1.007
.006
.004
.003
.002
.001
PHOSPHORUS -
TROUT RUN #3
ORTHO
4 HYDROLYZABLE
1^0
/TJOTAL
U
D
C
Figure 21. Phosphorus profile of Trout Run water (collected April
1973) before and after processing. Legend: (U) unfiltered;
(F) filtered; (A) alumina adsorption; (D) dialysis;
(G) coagulation.
59
-------
stream waters to be primarily soluble with minor exceptions (Table 14).
Increases observed after filtration in two cases can tentatively be
attributed to contaminated glassware, membrane filters (no conclusive
proof is available), or possibly technique. As previously alluded to
operational problems at Hatfield can account for the relatively high
concentration of Kjeldahl nitrogen determined in Sample #1 of Appendix
IE wherease Samples #2 and #3 reflect more realistic values expected
for this type of treatment plant.
The Phoenixville secondary treatment effluent in contrast exhibited a
pattern of 10-20% insoluable -Kjeldahl nitrogen (Table 14).
The efficacy of alumina adsorption and dialysis in removal of Kjeldahl
is more obvious in cases where baseline values are consistently high
(Table 13 and Figure 22) as reflected in the Phoenixville data.
Coagulation, conversely, produced more erratic results and generally
was the least effective in the removal of total nitrogen.
AMMONIA NITROGEN
The same pattern was repeated for ammonia nitrogen with alumina removing
92-977. and dialysis 84-907. in 0.45p filtered Phoenixville effluent.
Dialysis appeared to be more effective when lower baseline values were
detected but are erratic as can be seen by inspection of Table 13.
Coagulation removed 0-387. of Phoenixville ammonia nitrogen and was
generally inconsistent with all waters.
NITRATE-NITRITE NITROGEN
Of the three processes, dialysis with minor exceptions, was the most
consistent in removal of nitrate nitrogen. This can more readily be
observed in stream water where nitrate levels were 10 times higher
than in that of the secondary and tertiary treatment plants (Table 12).
Dialysis was also the most effective means of removing nitrite ions
(56-907. at Hatfield and 50-807. at Phoenixville) where baseline values
were reported to be .01-.09 and 0.1-4.4 ppm, respectively (Tables 12-
13). By comparison nitrite removal from stream water fluctuated to a
greater extent but can be accounted for by the low concentrations found
in French Creek and Trout Run (.01-.004 and .02-.004 ppm, respectively)
(Table 12).
Further studies are required to elucidate the effectiveness of dialysis
in removal of nitrate-nitrite ions, particularly in low concentrations,
but based on the limited experiments it is suggested to be more effec-
tive than alumina adsorption or coagulation (Figure 24).
CATIONS
A clear cut picture of the relative effectiveness of alumina adsorption
60
-------
3
2
K)
i
0.1
NITROGEN
PHOENIXVILLE
KJELOAHL (MARCH)
AMMONIA (MARCH)
KJELDAHL (MAY)
AMMONIA (MAY)
U
Figure 22. Comparative nitrogen profile (KJeldahl and ammonia) of
Phoenlxville aecondary wastewater effluent (collected March
and May 1973) before and after processing. Legend: (U)
unfittered; (F) filtered; (A) alumina adsorption; (D)
dialysis; (C) coagulation.
61
-------
1.0
0.1
g
d
S
E.
0.01
a ooi
NITROGEN
VALLEY 13
NITRATE
,..„...-• KJELDAHL
•• IIIIIIBMI IT
A NITRITE
U
D
Figure 23. Nitrogen profile of Valley Creek water (collected April
1973) before and after processing. Legend: (U) unfiltered;
(F) filtered; (A) alumina adsorption; (D) dialysis;
(C) coagulation.
62
-------
I
NITROGEN-
FRENCH CREEK
1.0
I 0.1
fl!
I
.01
JANUARY
MARCH NITRATE
APRIL
MAY
APRIL NITRITE
JANUARY
U
Figure 24. Comparative nitrate-nitrate prifiles of French Creek water
samples before and after processing. Legend: (U) unfiltered;
(F) filtered; (A) alumina adsorption; (D) dialysis; (C)
coagulation.
63
-------
capillary membrane dialysis, and coagulation evolves in the review of
cation data.
CALCIUM AND MAGNESIUM
Calcium and magnesium were removed from all waters by alumina adsorption
in the range of 95-99% and 92-997., respectively (Table 15 and Figures
25-27). In comparison dialysis removed 36-85% of calcium and 33-81% of
magnesium.
Coagulation with alum and the polyelectrolyte showed a high degree of
variation with calcium ranging from concentrations exceeding control
values to a maximum of 53%. Magnesium removal efficiency also varied
from values exceeding that of controls to a high of 20% (Table 15).
POTASSIUM
Alumina adsorption accounted for potassium reduction of 75-92% in
stream water and 70-98% in wastewater effluent. Capillary dialysis
removed 28-90% of this cation from stream samples and 50-85% from waste-
water. In all instances potassium derived from the aluminum potassium
sulfate appeared in treated samples in concentrations greater than
controIs.
BORON
Boron was of interest in this study since it is an essential element for
plant growth, but in excess concentrations can have a deleterious effect
on the growth at levels exceeding 2 ppm^. Baseline values following
0.45^ filtration ranged from 0.08 to 0.6 ppm for stream water arid 0.5-
1.8 ppm in wastewater effluent. The boron content of raw stream water
was most generally soluble with a maximum of 0.1 ppm being removed by
filtration. Wastewater effluent contained a maximum of 0.5 ppm of in-
soluble material at Phoenixville and 0.2 ppm at Hatfield (Table 16).
Alumina adsorption removed 50-80% of boron from French Creek waters and
0-93% and 0-96% from Trout Run and Valley Creek, respectively. Eighty-
eight percent was removed from Phoenixville effluent and 72-88% from
Hatfield.
Dialysis proved to be slightly better in removing 50-88% from all
stream samples and 58-90% from wastewater. It is likely that this
method could have removed more boron by extension of the dialysis
period.
Coagulation produced highly variable results with boron removal effi-
ciencies ranging from greater than control values to a maximum of 60%
with stream water and 50% with wastewater.
64
-------
CALCIUM-3
70
60
1 50
d
« «
30
20
10
VALLEY ....in...
HATFIELD
PHOENIXVILLE-
TROUT RUN
FRENCH CREEK
U
Figure 25. Comparative calcium profiles of water (Valley Creek, French
Creek, Trout Run) and wastewater effluent (Phoenixville
secondary and Hatfleld tertiary) before and after processing.
Legend: (U) unfiltered; (F) filtered; (A) alumina adsorption;
(C) coagulation.
65
-------
I
MAGNESIUM
APRIL 1973
10
1.0
0.1
VALLEY
TROUT RUN
FRENCH CREEK
U
Figure 26. Comparative magnesium profile of water (collected April
1973) from French Creek, Trout Run, and Valley Creek
before and after processing.
66
-------
MAGNESIUM-
APRILI973
10
I
QJ
PHOENIXVILLE
^HATFIELD
U
D
C
Figure 27. Comparative magnesium profile of Phoenixville (secondary)
and Hatfield (tertiary) wastewater effluents (collected
April 1973) before and after processing.
67
-------
1.0
o
i
s
£
oc
HATFIELD
PHOENIXVILLE * \
ai
.01
BORON-
APRIL 1973
u
VALLEY CREEK
FRENCH CREEK
TROUT CREEK
A
c
Figure 28. Comparative boron profile of stream water (French Creek,
Valley Creek, Trout Run) and wastewater effluent (Phoenixville
secondary and Hatfield tertiary collected April 1973) before
and after processing.
68
-------
e
g
10
SODIUM -
APRIL 1973
PHOEWXVILLE
HATFIELD
0.
VALLEY CREEK
FRENCH CREEK
TROUT CREEK
U
D
Figure 29. Comparative sodium profiles of stream water (French Creek,
Valley Creek, Trout Run) and wastewater effluent (Phoenixville
secondary and Hatfield tertiary collected April 1973)
before and after processing.
69
-------
SULFATC - 3
o
3
9
400
350
HATFIELD
%c PHOENIXVILLE
VALLEY CREEK
FRENCH CREEK
TROUT RUN
Figure 30. Comparative sulfate profiles of water (Valley Creek, French
Creek, Trout Run) and wastewater effluent (Phoenixville
secondary and Hatfield tertiary) before and after processing.
Legend: (U) unfiltered; (F) filtered; (A) alumina adsorption-
(C) coagulation. '
70
-------
SILICA
Silica removal by alumina adsorption from stream water ranged from 97-
98% at French Creek, 60-98% at Trout Run, and 25-98% at Valley Creek.
For all wastewater this is shown to be in the 91-98 percentile. Overall
efficiency of dialysis, in comparison, was 69-80X. for stream water and
49-76% for wastewater.
SODIUM
The sodium content of all stream water samples exceeded that of con-
trols. In wastewater effluent this ranged from concentrations exceeding
untreated controls to a maximum of 277» at Fhoenixville and 3% at
Hatfield. This appears to be, as previously discussed, due to sodium
from caustic (NaOH) originally used to prepare the column (Figure 29).
Dialysis removed 8-94% from all stream water and 77-80% from wastewater
samples. Coagulation treated samples usually showed sodium values
higher than controls, and in no instance was more than 12% effective
(Table 15).
MISCELLANEOUS CATIONS
Zinc, cobalt, copper, and iron were reported in all samples at or near
their detection limit by atomic absorption spectrophotometry. This
precluded further analysis of the candidate treatment processes in
removing these species from test waters.
ANIONS
Sulfate was effectively removed by alumina adsorption 4-99%; dialysis
removed 11-737.; whereas coagulation was completely ineffective.
Coagulated samples in fact contained an excess of sulfate, which as
discussed for potassium, can be attributed to the use of alum (see
Figure 25).
Dialysis was superior for removal of chloride (as high as 847. with
stream water and 887o for treatment plant effluent) with alumina and
coagulation demonstrating second and third level activity, respectively.
Sulfite could not be satisfactorily evaluated due to the concentration
in all samples approaching the minimum detection limit.
MISCELLANEOUS ANALYTICAL PARAMETERS
Specific Conductance
Dialysis was particularly effective in.lowering specific conductance
(maximum of 82% in stream and 75% in wastewater samples). Alumina
71
-------
generally increased conductance, although in a few cases it was moder-
ately reduced. Increases are probably due to loosely bound species for
which the alumina has a low capacity and are readily eluted from the
column matrix once breakthrough levels are reached (Figure 31).
Conductance increased in all'samples treated with the polyelectrolyte-
alum combination. This is also attributed to the alum dissociation and
the ionic concentration increasing from failure of all of the coagulant
to be involved in floe generation. In all probability this may be
minimized by pH optimization, but was not considered in conjunction
with the subject study.
Hardness
Reduction in hardness achieved by alumina adsorption characteristically
paralleled calcium and magnesium concentrations at the 96-99% level
(Figures 25-27). In the case of dialysis hardness fell 23-817. below
values for untreated controls. Coagulated samples more frequently
increased hardness, although it was reduced in a few cases not more
than 6%.
Total Alkalinity
Alkalinity was consistently reduced by dialysis 71-89% in stream water
and 62-81% in wastewater effluent (Figure 33). By comparison the
alkalinity of alumina treated stream water ranged from values exceeding
controls to a maximum reduction of 84%. Treated effluent was more uni-
form with total alkalinity 70-93% less than controls. The disparity is
due to the low initial alkalinity of stream waters (~ 25-150 ppm) and
the higher concentration found in effluents (~ 176-255 ppm) compounded
by the alkaline nature of the column. Coagulation accounted for a
reduction of alkalinity in stream water and effluents of 6-25% and 6-
53%, respectively.
pH
Hydrogen ion concentration of stream and watewater effluent before and
after 0.45p filtration and treatment by each of the methods under con-
sideration are summarized in Table 17.
Differences between unfiltered and filtered samples are generally
attributable to varying concentrations of total and dissolved solids
(Tables 18 & 19) and their individual buffering capacity.
Changes in hydrogen ion concentration occurred most dramatically in
alumina treated samples with water and wastewater shifting from baseline
values of pH 6.80-8.95 to pH 7.76-10.96. The pH of all samples dropped
following dialysis, and to a lesser extent following coagulation. In a
72
-------
1600
1400
SPECIFIC CONDUCTANCE
#3
HATFIELD
PHOENIXVILLE
IIIIIIMIIHIIIlHllllflii,,,,
TROUT RUN
FRENCH CREEK
VALLEY CREEK
200
Figure 31. Comparative specific conductance profiles of water (Valley
Greek, French Creek, Trout Run) and wastewater effluent
(Fhoenixville secondary and Hatfield tertiary) before and
after processing. Legend: (U) unfiltered; (F) filtered;
(A) alumina adsorption; (C) coagulation.
73
-------
HATFIELD
HARDNESS
VALLEY CREEK
150
100
PHOENIXVILLE
TROUT RUN
50
FRENCH CREEK
Figure 32. Comparative hardness (EDTA) profiles of water (Valley
Creek, French Creek, Trout Run) and wastewater effluent
(Phoenixville secondary and Hatfield tertiary) before and
after processing. Legend: (U) unfiltered; (F) filtered;
(A) alumina adsorption; (C) coagulation.
74
-------
no
TOTAL ALKALINITY -
APRIL 1973
HATFIELD
PHOENIXVILLE
VALLEY CREEK
TROUT RUN
FRENCH CREEK
U
D
Figure 33. Comparative total alkalinity profiles of water (Valley
Creek, French Creek, Trout Run) and wastewater effluent
(Phoenixville and Hatfield) before and after processing.
75
-------
450
400
350
300
250
^200
150
100
50
DiSCOLVED SOLIDS -
PHOENiXVILLE
F
A
D
C
Figure 34. Dissolved solids profiles of Phoenixville secondary wastewater
effluent (collected Match, April, May 1973) before and
after processing. Legend: (F) filtered; (A) alumina adsorption-
(D) dialysis; (C) coagulation.
76
-------
800
700
600
500
400
300
200
100
DISSOLVED SOLIDS -
HATFIELD
APRIL
MAY
JULY
Figure 35. Dissolved solids profiles of Hatfield tertiary wastewater
effluent (collected April, May, July 1973) before and after
processing Legend: (F) filtered; (A) alumina adsorption;
(D) dialysis; (C) coagulation.
77
-------
SCO
450
400
350
300
o
id
250
200
150
100
50
DISSaVEDSaiDS
TROUT RUN
JANUARY
APRIL
C
Figure 36. Dissolved solids profiles of Trout Run water (collected
January, April, May 1973) before and after processing.
Legend: (P) filtered; (A) alumina adsorption; (D) dialysis;
(C) coagulation.
78
-------
500
450
400
350
300
s
DISSOLVED SOLIDS -
FRENCH CREEK
g 250
200
150
100
50
APRIL
Figure 37. Dissolved solids profiles of French Creek water (collected
January, March, April, May 1973) before and after processing.
Legend: (F) filtered; (A) alumina adsorption; (D) dialysis;
(C) coagulation.
79
-------
500
450
4)0
350
|300
=i
I
£250
200
150
100
50
DISSOLVED SOLIDS -
VALLEY CREEK
JANUARY
MARCH
APRIL
Figure 38. Dissolved solids profiles of Valley Creek water (collected
January, March, April, May 1973) before and after processing.
Legend: (F) filtered; (A) alumina adsorption; (D) dialysis;
(C) coagulation.
80
-------
few cases a rise in pH occurred with coagulation and is probably due to
differences in buffer capacity of specific samples.
Dissolved Solids
Dissolved solids burden of 0.45^ filtered water ranged from 418-688
ppm at Hatfield; 150-497 at Phoenixville; 299-463 ppm at Valley Creek;
191-252 ppm at Trout Run; and 131-183 ppm at French Creek (Table 18).
Dialysis achieved 62-797<> reduction of dissolved solids at French Creek;
15-92% at Trout Bun; and 51-80% with Valley Creek samples. Of waste -
water effluents treated 71-747. removal occurred with Phoenixville
samples and 42-677. for those from the Hatfield plant.
In comparison dissolved solids content of alumina treated stream waters
either exceeded control values or exhibited a maximum of 287. removal.
This efficiency increased to 18-527. with wastewater effluent in which
the control values of untreated samples were considerably higher than
those found in streams. Again the alumina is suspected of contributing
to the dissolved solids levels when early "breakthrough" occurs with the
less tenaciously bound species. Coagulation is also unpredictable in
controlling dissolved solids, but for the most part increases concentra-
tions considerably above control levels.
It was of interest to plot data for all samples of water and wastewater
treated in Figures 35-38. Here can be seen the dramatic reduction of
dissolved solids as well as the retention of higher molecular weight
species, i.e., > MM 5000. This is quite notable in effluent derived
from the tertiary facility (Hatfield) where the dissolved solids re-
tained after dialysis are present in concentrations of ~ 250-275 ppm;
those from the secondary plant (Phoenixville) range from ~ 50-751 of
dissolved solids following dialysis (Figure 32); whereas Valley Creek
demonstrated greater scatter in the same time span (January-May 1973)
of ~ 50-210 ppm (Figure 33). Trout Run data is also in the same
range except for the relatively low efficiency (157.) achieved following
dialysis of the May samples. No other explanation can be made for this
discrepancy other than an unknown variation in technique or mix-up in
This data, although preliminary in nature, suggests the retention of
jnacromolecules and/or complexes which could influence algal assays by
stimulatory or inhibitory effects on the test organism and compound the
problem of comparing assay data from different waters with controls
propagated on a chemically defined medium. In all likelihood we may not
have completely removed the < 5000 MW fraction in the forty-five minute
dialysis period, although this can only be confirmed in studies where
serial samples are taken and analyzed to determine when the dissolved
solid8 curve plateaus. An advanced study would also use a series of
81
-------
Table 17
Summary of Hydrogen Ion Changes Following Treatment of
Stream Water and Wastewater
SOURCE
FRENCH
CREEK
TROUT RUN
VALLEY
CREEK
PHOENIX-
VILLE
(Secondary)
HATFIELD
SAMPLE
NO.
1
2
3
4
1
2
3
1
2
3
4
1
2
3
1
2
3
UNFILTERED
6.92
6.89
7.65
-
8.51
7.60
7.00
9.08
8.35
7.61
7.72
7.95
7.84
8.10
7.98
PH
FILTERED
7.14
7.30
6.80
8.20
8.64
8.35
8.25
8.95
8.30
8.77
8.40
8.05
7.68
8.05
7.76
7.95
7.89
ApH
+ .38
.09
+ .55
-
.16
.65
+ 1.3
.31
+ .05
.44
.04
+.1
.08
.15
0
ALUMINA
ADSORPTION
10.57
10.96
10.22
10.05
10.29
10.54
10.20
11.25
7.75
10.22
9.70
10.96
9.28
9.25
9.73
9.65
9.45
DIALYSIS
6.49
7.00
6.60
6.40
7.31
6.83
7.30
7.14
7.02
6.89
6.95
7.85
7.30
7.85
7.39
6.75
7.81
COAGULATION
6.92
7.30
6.60
6.85
8.10
7.62
7.65
8.38
11.09
8.38
8.10
7.78
7.76
7.90
7.81
7.85
8.70
oo
to
-------
Table 18
Summary of Total Solids in Raw Stream Water
Prior to Filtration
SOURCE
FRENCH CREEK
TROUT RUN
VALLEY CREEK
PHOENIX VILLE
HATFIELD
SAMPLE
1
2
3
4
1
2
3
1
2
3
1
2
3
1
2
3
PPM
TOTAL SOLIDS
181
145
130
148
179
186
217
340
350
520
340
406
715
666
490
433
83
-------
Table 19
Summary of Dissolved Solids Treatment Efficiencies for Water and Wastewater
SOURCE
FRENCH
CREEK
TROUT
RUN
VALLEY
CREEK
PHOENIX-
VILLE
HATFIELD
SAMPLE
1
2
3
4
1
2
3
1
2
3
4
1
2
3
1
2
3
PPM
DISSOLVED
SOLIDS IN
FI LTERED
SAMPLES
183
131
132
140
252
191
236
344
299
308
463
497
421
150
668
449
418
% REDUCTION FOLLOWING:
ALUMINA ADSORPTION
+
+
+
+
+
+
+
28
19
23
19
21
39
51
52
18
18
CAPI LLAR Y DI ALYSI S
79
59
47
62
92
62
15
67
59
80
51
71
73
74
67
34
42
COAGULATION
+
+
2
43
+
+
15
+
1.4
4.3
37
+
50
23
0.1
+
+
— Exceeds Control Value.
-------
membranes with different molecular weight cutoffs, e.g., 200-30,000,
to identify fraction which could have the most deleterious effect on
algal assay test organisms. This could furthermore be tested with
stream and wastewater effluents with and without the addition of
organic and inorganic compounds of varying molecular weight.
Residual organics in water-supply sources or domestic sewage are
generally determined on a gross basis in terms of BOD, GOD, or TOG
and CCE-CAE, respectively5. In 1970 the A.D. Little Company documented
all the organic compounds, which had been found or were suspected of
being in freshwater, to survey their toxicological characteristics. Of
496 compounds reported in the survey only 66 have been identified^
Rosen et al detected 77 compounds in primary effluent (of which 18 were
identified) and 38 compounds in the secondary effluent of municipal
sewage with high resolution anion-exchange chromatography. This study
further suggested that other compounds were being synthesized during
secondary treatment^.
13
Fractionation of organics in secondary effluents by Rebhun and Manka
revealed >50% to be humic substances (humic, fulvic, and hymatho-
melanic acid) with fulvic acid per se_ being the predominant species.
The remainder consisted of ~ 8.3% ether extractables,~ 13.9% anionic
detergents; ~ 11.5% carbohydrates; ~ 22.4% proteins; and ~ 1.7% tanins.
A recent investigation of organics in the Charles River, Boston, by gas
chromatography/mass spectrometry techniques detected the presence of
normal alkanes (0^5 to £31), alkyl naphthalenes, alkyl anthracenes or
phenanthrenes, pyrene fluoranthene, dibutyl phthalate, and di (2-
ethylhexyl) phthalate. Although the effects of many of these materials
in trace concentrations on the algal assay are unknown, it is highly
suggestive that their potential presence must be taken into considera-
tion in analyses of assay data and development of advanced methods for
preparing a basal assay medium.
85
-------
SECTION VII
ACKNOWLEDGEMENTS
Personnel of the General Electric Company's Biological and Chemical
Sciences Laboratory who participated in this study were Roland J.
Starkey, Jr., Mary E. Kub, Albert E. Binks, and Karolesh K. Jain.
Secretarial services were supplied by (Mrs.) Linda Koutsonikas and
(Mrs.) Madeline Sowers. The U.S. Environmental Protection Agency
Project Officer was Thomas E. Maloney.
Cooperation of personnel at the Phoenixvilla and HatfieId waste
treatment facilities expedited collection and processing of effluent
samples. Without their help this study would not have been possible.
86
-------
SECTION VIII
REFERENCES
1. Joint Industry/Government Task Force on Eutrophication.
Provisional Algal Assay Procedure. Joint Industry/Government Task
Force, New York (1969).
2. National Eutrophication Research Program. Algal Assay Procedure
Bottle Test, pp. 82, August (1971).
3. Weiss, C.M. and R.W. Helms. Provisional Algal Assay Procedure -
The Inter-Laboratory Precision Test, Department of Environmental
Sciences and Engineering, School of Public Health, University of
North Carolina at Chapel Hill, October (1971).
4. Maloney, T.E., W.E. Miller, and N.L. Blind. Use of Algal Assays
in Studying Eutrophication Problems. Presented at the Inter-
national Association of Water Pollution Research, Jerusalem,
June 18-24 (1972).
5. Ongerth, H.J., D.P. Spath, and A.E. Greenberg. Public Health
Aspects of Organics in Water, J.A.W.W.A., 65_, 495-498 (1973).
6. Gaines, F.R. and C.E. Hartley. Advanced Waste Treatment in
Hatfield Township, Hatfield Township (Pennsylvania) Municipal
Authority (1972).
7. Ames, L.L., Jr. Research to Develop and Demonstrate a Mobile
Plant for Removal of Soluble Phosphorus by Adsorption on Alumina
Columns, U.S. Department of the Interior, Federal Water Pollution
Control Administration, Cincinnati, Ohio (1970).
8. U.S. Environmental Protection Agency. Methods for Chemical
Analysis of Water and Wastes. National Environmental Research
Center, Analytical Quality Control Laboratory, Cincinnati, Ohio
(1971).
9. American Public Health Association. Standard Methods for the
Examination of Water and Wastewater. APHA, AWWA, WPCF, ed 13,
New York (1971).
10. Perkin-Elmer Corporation. Analytical Methods for Atomic Absorption
Spectrophotometry. Norwalk, Connecticut (1968).
11, A.D. Little Co., Water Quality Criteria Data Book; Organic Chemical
Pollution of Fresh Water. Vol. 1, Water Pollution Research Series,
EPA 18010 DPU 12/TO (1970).
87
-------
12. Rosen, A.A., S. Katz, W.W. Pitt, Jr., and C.D. Scott. The Deter-
mination of Stable Organic Compounds in Waste Effluents at Micro-
gram per Liter Levels by Automatic High Resolution Ion Exchange
Chromatography. Water Research, £, 1029 (1972).
13. Rebhum, M. and J. Manka. Classifications of Organics in Secondary
Effluents, ES&T, 5., (7), 606-609 (1971).
14. Hites, R.A. and K. Biemarn. Water Pollution: Organic Compounds
in the Charles River, Boston. Science, 178 (4057), 158-160 (1972).
88
-------
APPENDIX I
I-A. Comparative Analysis of Stream Water Before and After Treatment
by Alumina Adsorption, Capillary Membrane Dialysis, and Coagula-
tion: French Creek.
I-B. Comparative Analysis of Stream Water Before and After Treatment
by Alumina Adsorption, Capillary Membrane Dialysis, and Coagula-
tion: Trout Bun.
I-C. Comparative Analysis of Stream Water Before and After Treatment
by Alumina Adsorption, Capillary Membrane Dialysis, and Coagula-
t ion: Valley Creek.
I-D. Comparative Analysis of Stream Water Before and After Treatment
by Alumina Adsorption, Capillary Membrane Dialysis, and Coagula-
t ion: Phoenixville Secondary Treatment Plant.
I-E. Comparative Analysis of Stream Water Before and After Treatment
by Alumina Adsorption, Capillary Membrane Dialysis, and Coagula-
tion: HatfieId Tertiary Treatment Plant.
89
-------
COMPARATIVE
APPENDIX I-IA
ANALYSIS OF STREAM WATER BEFORE AND AFTER TREATMENT BY
AU2MJNA.
ADSORPTION: ftA?ITf1llfflY ^Kttflftfjtf. DIALYSIS: AND COAGULATION:
FRENCH CREEK
CLASS
NUTRIENTS
ANALYSIS
TOTAL
CARBON
ORGANIC
CARBON
INORGANIC
CARBON
TOTAL P04 -
P
HYDROLYZ-
ABLE PO. -
P
PHOSPHATE
ORTHQ
KJELDAHL
NITROGEN
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
5
11
11
19
1
6
4
8
4
5
1
11
0.6
0.04
0.03
0.05
0.06
0.04
0.03
0.04
0.03
0.03
0.03
0.04
0.2
0.2
0.3
1.5
FILTERED
10
10
12
15
2
6
5
5
8
4
7
10
0.05
0.04
0.07
0.05
0.04
0.04
0.05
0.05
0.01
0.03
0.06
0.05
0.2
0.1
0.3
0.8
TREATED
ALUMINA
12
6
8
10
6
3
3
3
6
3
5
7
0.002
0.01
0.01
<0.005
0.01
0.01
0.004
< 0.005
< 0.002
0.01
0.002
< 0. 005
0.4
5.2
0.5
1.3
%
AR*
^.
40
33.4
33.4
+
50
40
40
25
25
28.6
30
96
75
85.8
>90
75
75
92
>90
80
66.7
96,7
90
+
+
-r
+
CAPILLARY
MEMBRANE
DIALYSIS
5
6
8
9
2
5
5
6
3
1
3
3
0.06
0.01
0.03
0.02
0.05
0.004
0.03
0.02
0.04
0.01
0.03
0.02
0.2
0.1
0.2
0.2
%
AR*
50
40
33.4
40.0
0
17
0
4.
62.5
75.0
57.2
70
+
75
57.2
60
+
90
40
60
•*-
66.7
50
60
0
0
33.4
75
COAGULATION :
ALUM POLY-
ELECTROLYTE
10
9
11
13
4
7
5
5
6
3
6
8
0.002
0.01
0.02
< 0.005
0.01
0.01
0.02
< 0.005
Q. 004
0.01
O.ftl
O OOfi
0.2
0.5
0.3
0.8
%
AR*
0
10
8.4
h 14
+
-t-
0
o
25
25
14.3
20
J?6
75
71.5
>90
15
75
60
90
-------
APPETOHX l-IA
COMPARATIVE AKALTESIS OF STREAM WATER BEFORE AND AFTER TREATMENT BY
ALUMINA
MV.MTOANE DIALYSIS; AND COAGULATION!
FRENCH CREEK
CLASS
NUTRIENTS
CATIONS
ANAI/XSIS
AMMONIA
NITROGEN
NITRATE
NITROGEN
NITRITE
NITROGEN
Ca
Mg
Zn
K
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY-
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APR^L.
MAY
JANUARY
MARCH
APRIL
Y»v
JANUARY
MARCH
APRIL
MAY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
0.1
0.1
0.1
0.6
2.3
1.6
1.5
2.4
0.01
0.004
0.01
0.02
_
30
18
16
-
13
_
7
-
<0.02
0.04
_
1.2
1.5
1.9
FILTERED
0.1
0.1
0.1
0.04
2.2
1.4
1.3
2.4
0.01
0.004
0.01
0.01
20
17
17
15
5
7
6
6
<0.04
<0.02
<0.02
1.4
1.2
1.4
1.7
TREATED
ALUMINA
0.2
5.0
0.3
2.3
1.6
1.3
1.5
0.004
0.01
0.01
0.01
<1
<0.2
<0.2
<0.2
0.1
<0.1
<0.2
<0.2
<0.04
<0.02
<0.02
0.2
0.3
0.1
0.3
%
AR*
-t-
+
+
+
+
-t-
0
37.5
60
+
0
0
>95
98.9
98.9
98.7
98
98.6
96.7
96.7
85. 8
75.0
92.9
82.4
CAPILLARY
MEMBRANE
DIALYSIS
0.1
0.1
0.03
0.2
0.3
0.1
0.1
0.1
0.002
0.003
< 0.002
0.01
4
8
6
8
1.4
1.4
3.0
3.0
<0.04
<0.02
<0.02
1.0
0.3
0.3
0.4
%
AR*
0
0
70
+
86.4
92.9
92.4
95.9
80
25
80
0
80
53
64.8
46.7
72
80
50
50
28.6
75
78.6
76.5
COAGULATION :
ALUM POLY-
ELECTROLYTE
0.1
0.4
0.1
0.2
2.0
1.4
1.0
2.1
0.004
0.02
0.01
0.01
20
19
16
15
4
7
?'
6
<0.04
<0.02
<0.02
3.5
3.6
3.5
3.5
%
AR*
0
4
0
+
9.1
0
23.1
12.5
60
-t-
0
0
0
4-
5.9
0
20
0
H-
0
-f
-t-
-f
-!-
* Expressed as % reduction of filtered samples. 4 Value of treated sample exceeds that of filtered control. t Values reported are nea- limit of sensitivity for tea
-------
APPENDIX I-IA
COMPARATIVE ANALYSE OF STREAM WATER BEFORE AND AFTER TREATMENT BY
AMTMfflA ADflORPTlOK; CAPIfoLAR/y MTMPfiftWf DIALYSIS; AND COAGULATION:
FRENCH CREEK
CLASS
CATIONS
ANIONS
ANALYSIS
Na
B
Si
Co
Cu
Fe
S03
NO.
1
2
3
4
1
2
3
4
1
2
3
4
}.
2
3
4
1
2
3
4
1
2
3
4
1
2
MONTH
SAMPLE
COLLECTED
JANUARY
MARCH
APRTT,
MAY
JANUARY
MARCH
APRTL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARfTH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
J4AY
JANUARY
MARCH
3 f APRIL
4 1 MAY
TEST COMDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
_
10.7
10.1
11.2
• .1
0.1
0.11
0.2
—
6.9
5.2
16.0
.
,-0.05
<:0. l
<0.3
_
<0.05
<0. 1
<0.02
-
0.3
<0.1
0.7
<2
<2
<2
<2
FILTERED
7.1
10.7
10.4
11.2
0.08
0.1
0.09
0.2
7.9
6.9
7.1
15.0
<0.05
<0.05
<0.1
<0.3
0.02
<0.05
<0.1
<0.02
<0.02
<0.1
<0.1
<0.1
<2
<2
<2
<2
TREATED
ALUMINA
58
52
31.5
32
0.02
0.02
0.03
0.1
0.1
0.11
0.2
0.24
<0.05
<0.05
<0.1
<0.3
<0.02
<0.05
<0.1
<0.02
<0.02
<0.1
<0.1
<0.1
<2
<2
<2
<2
%
AR*
+
+
+
+
75
80
66.7
50
98.7
98.4
97.1
98.4
CAPILLARY
MEMBRANE
DIALYSIS
1.9
2.2
6.3
2.7
0.04
0.02
0.01
0.1
1.6
1.5
1.5
3.74
<0.05
<0.05
<0.1
<0.3
<0.02
<0.05
<0. 1
<0.02
<0.02
<0.1
<0.1
<0.1
<2
<2
<2
<2
%
AR*
73.3
79.5
67
75.9
50
80
88.9
50
79.8
78.3
78.9
75.1
COAGULATION :
ALUM POLY-
ELECTROLYTE
7.1
11
10.2
10.5
0.04
0.1
0.05
0.2
7.6
5.0
6.7
14.1
<0.05
<0.05
<0.1
<0.3
<0.02
<0.05
<0.1
<0. 02
<0.02
<0.1
<0.1
<0.1
<2
<2
<2
<2
%
A R»
0
+
1.9
6.3
50
0
IrP 7
0
3.8
27.6
5.7
6.0
Expressed as % reduction of filtered samples. + Value of treated sample exceeds that of filtered control.
t Values reported are near limit of sensitivity for tts.
-------
APPENDIX MA
CXMPARMT/E ASALY8S OF OTKEAM. WKTER BEFORE AND AFTER TREATMENT BY
ALUMTOA AD80RPTICM-. CAPITJ^y
DIALYSIS: AND COAGULATKM-.
FRENCH CREEK
CLASS
ANION8
ALYSES
2
<
to
D
O
W
S5
MISCELLA
ANALYSIS
so4
ca
PH
SPECIFIC
CONDUCTANCE
HARDNESS
EDTA
AT If AT TNTTV
TOTAL
TOTAL
SOLIDS
NO.
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
MARCH
APRTt
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRTT,
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
_
32
34
33
7
IS
11
12
_
6.92
6.89
7.65
-
192
220
187
_
58
48
58
_
28
27
28
181
145
130
148
FILTERED
24
30
26
33
8
14
10
11
7.14
7.30
6.80
8.20
175
193
225
190
42
57
59
38
24
27
26
27
_
_
-
-
TREATED
ALUMINA
23
3
2
0.1
7
13
10
12
10.57
10.96
10.22
10.05
495
320
345
190
<1
<2
<0.2
<1
129
87
63
87
_
_
-
%
6R*
4.2
90
92.4
99.7
12.5
7.2
0
8.4
_
^
_
^
+
+
+
0
>97.6
>96.5
>99.6
>97-4
-t-
•*.
+
-t
_
_
_
-
CAPILLARY
MEMBRANE
DIALYSIS
18
23
23
14
3
3
3
1
6.49
7.00
6.60
6.40
67
81
73
82
14
43
11
29
6
7
7
7
_
-
-
-
%
6R»
25
23.4
11.6
57.6
57.2
78.6
70
8.4
_
_
_
_
61.8
58.1
67.6
56.9
66.7
24.6
81.4
23.7
75
74.1
73.1
74.1
_
-
_
-
COAGULATION :
ALUM POLY-
ELECTROLYTE
39
40
43
40
7
15
10
11
6.92
7.30
6.60
6.85
181
202
190
190
37
53
43
55
18
21
19
21
_
-
-
-
%
6 R*
-f
4-
-f
-f
12.5
•f
0
0
-
_
_
_
4
+
15.6
0
12
7.1
27.1
^.
25
22.3
27
22.3
-
-
_
-
* Expressed as % reduction of filtered samples. ^ Value of treated sample exceeds that of filtered control.
t Values reported are near limit of sensitivity for tee
-------
APPENDIX I-IA
COMPARATIVE ANALYSIS OF STREAM WATER BEFORE AND AFTER TREATMENT BY
ADSORPTION:
DIALYSIS: AND COAGULATION:
FRENCH CREEK
CLASS
•
ANALYSIS
DISSOLVED
SOLIDS
NO.
1
2
3
4
1
2
3
4
1
2
3
4
J.
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
MARCH
APRIL
MAY
-
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
_
_
_
-
FILTERED
183
131
132
140
TREATED
ALUMINA
535
241
254
450
%
AH*
+
+
4-
+
CAPILLARY
MEMBRANE
DIALYSIS
79
59
47
62
%
AR*
56.9
55
64.4
57.8
COAGULATION :
ALUM POLY-
ELECTROLYTE
184
143
129
134
%
A R*
+
j.
2.3
43
!
* Expressed as % reduction at filtered samples. - Value of treated sample exceeds fliat of filtered control.
t Values reported are near limit of sensitivity for tesi
-------
APPENDIX I-IB
COMP&RMTVE ASAL-ffilS OF STREAM WKTER BEFORE AND AFTER TREATMENT BY
ALUMINA ADSORPTION:
yiEM,™fMT. DIALYSIS; AND COAGULATION:
TROUT RUN
CLASS
NUTRIENTS
ANALYSIS
TOTAL
CARBON
ORGANIC
CARBON
INORGANIC
CARBON
TOTAL PO4-
P
HVDROLYZ-
ABLE PO4 -
P
PHOSPHATE
ORTHQ
KJELDAHL
NITROGEN
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
APRIL
MAY
JANUARY
APRIL
MAY
JANUARY
APRTT,
MAY
JANUARY
APRIL
MAY
JANUARY
APRIL
MAY
JANUARY
APRIL
MAY
JANUARY
APRIL
MAY
TEST CONDITION/CONCENTRATION 50
0
0
0
80
60
0
25
+
+
CAPILLARY
MEMBRANE
DIALYSIS
8
17
15
2
9
5
6
7
10
0.3
0.004
<0.01
0.3
0,003
<0.01
0.102
0.004
<0.01
0.2
0.2
0.2
%
A R*
73.4
41.4
60.6
77.8
+
28.6
71.5
70.9
67.8
+
60
>50
+
70
0
-t-
60
0
50
33.4
0
COAGULATION
ALUM POLY-
ELECTROLYTE
26
26
35
5
4
5
21
22
30
0.01
0.01
0.04
0.01
0.01
0.04
< 0.002
0.02
0.003
0.3
0.1
0.7
%
AR*
13.4
10.4
7.9
44.5
20
28.6
0
&.1
3.3
0
0
+
0
-
+
80
+
70
25
66.7
+
* Expressed as <2 reduction of filtered samples.
Value of treated sample exceeds that of filtered control.
t Values reported are near limit of sensitivity for tes
-------
APPENDIX I-IB
COMPARATIVE ANALYSIS OF STREAM WATER BEFORE AND AFTER TREATMENT BY
ALUMMA ADSORPTION: CAPTU^RY MJEMBRAMF DIALYSIS: AND COAGULATION:
JRQUT RUN
CLASS
DO
H
2
U
t— 1
«
EH
D
S5
••^••iHM
W
2
0
1— I
H
<
U
ANALYSIS
AMMONIA
NITROGEN
NITRATE
NITROGEN
NITRITE
NITROGEN
Ca
Mg
K
Na
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
APRIL
MAV
JANUARY
APRIL.
MAY
JANUARY
APRIL
MAV
JANUARY
APRIL
MAY
JANUARY
APRIL
MAY
JANUARY
APRIL
MAV
JANUARY
APRIL
MAY
,
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
0.1
0.1
0.1
2.3
2.5
2.0
0.01
0.004
0.01
_
34
35
-
12
16
-
2
2
-
8
5
FILTERED
0.2
0.1
0.1
2.2
2.6
1.8
0.01
0.004
0.01
32
34
35
11
11
13
2
2
2
6
6
5
TREATED
ALUMINA
0.1
0.6
2.9
2.2
2.7
0.3
0.01
0.004
0.01
<0.2
<0.2
<0.2
0.1
<0.2
<0.2
0.2
0.1
0.3
71
33
41
%
AR*
50
+
+
0
+
83.4
0
0
0
>99.4
>99.4
>99.5
99.1
98.2
99.5
90
95
85
+
+
+
CAPILLARY
MEMBRANE
DIALYSIS
0.1
0.1
0.1
0.4
0.5
0.4
20.0
<0.002
0.003
7
10
20
2
4
5
0.4
0.3
0.3
1
5
1
%
AR*
50
Q
0
81.9
80.8
77.8
+
50
70
78.2
70.6
42.9
81.9
63.7
61.6
80
85
85
83.4
16.7
8
COAGULATION :
ALUM POLT-
ELECTROLYTE
0.1
0.1
0.1
2.4
2.1
1.0
0.003
0.01
0.01
31
33
33
11
10
12
4
4
4
6
6
6
%
AR*
50
0
0
+
19.3
44.5
70
+
0
3.2
3 1
5.8
0
9.1
7.7
+
+
-I-
0
0
+
Expressed as % reduction of filtered samples.
Value of treated sample exceeds that of filtered control.
t Values reported are near limit of sensitivity 101 tes.
-------
APTONDH MB
COMPARATIVE ANALYSIS OF STREAM WATER BEFORE AND AFTER TREATMENT BY
ALUMINA ADSORPTION: CAPILLARY
AMD COAGULATIOH!
TROUT RON
CLASS
CATIONS
ANIONS
ANALYSIS
B
St
Co
Ctt
Zn
Fe
SOg
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
APRIL
MAY
JANUARY
A PUTT.
WAV
JANUARY
APRIL
MAY
JANUARY
APRIL,
MAY
JANUARY
APRIL.
MAY
JANUARY
APRIL
MAy
JANUARY
APRIL
MAY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
ONFILTERED
0.1
0.1
0.3
3.5
0.1
7.5
-
<.01
<0.3
_
<0.1
^0.02
—
0.04
<0.02
-
<0.1
0.1
<0.2
<0.2
<0.2
FILTERED
0.1
0.1
0.3
3.4
0.1
7.5
<0.05
<0.1
<0.3
0.02
<0.1
<0.02
<0.04
0.03
<0.02
<0.02
<0.1
<0.1
<0.2
<0.2
<0.2
TREATED
ALUMINA
0.1
0.04
< 0. 02
0.2
0.04
0.1
<0.05
<0.1
<0.3
0.02
<0.1
<0.02
<0.04
<0.02
<0.02
<0.02
<0. 1
<0.1
<0.2
<0.2
<0.2
%
AR*
0
60
>93.4
94.2
60
98.7
CAPILLARY
MEMBRANE
DIALYSIS
0.02
0.02
0.1
0.6
0.02
1.9
<0.05
<0.1
<0.3
0.02
<0.1
<0.02
<0.04
0.03
<0.02
0.02
<0.1
<0.1
<0.2
<0.2
<0.2
%
AR*
80
80
66.7
•
82.4
80
74.7
COAGULATION :
ALUM POLY-
ELECTROLYTE
0.1
0.04
0.2
2.9
0.04
7.1
•^0.05
<0.1
<0.3
0.02
<0.1
<0.02
•^0.04
0.02
<0.02
0.02
<0.1
<0.1
<0.2
<0.2
-------
APPENDIX i-m
COMPARATIVE ANALYSIS OF STREAM WATER BEFORE AND AFTER TREATMENT BY
DIALYSIS; AND COAGULATION:
ALUMTPA ADSORPTION: CAPILLARY
TROUT RUN
CLASS
TO
55
O
M
5S
•<
MISCELLANEOUS ANALYSES
ANALYSIS
so4
Cl
pH
SPECIFIC
CONDUCTANCE
HARDNESS -
EOT A
ALKALINITY
TOTAL
TOTAL
SOLIDS
NO.
1
2
a
.4
i
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
APRIL.
MAY
JANUARY
ATJRTT.
MAY
JANUARY
APRIL
MAY
JANUARY
APRIL
MAY
JANUARY
APRIL
MAY
JANUARY
APRIL
MAY
JANUARY
APRIL
MAY
l
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
«-
18
21
21
11
11
-
8.51
7.60
.
93
102
-
115
121
_
93
102
179
186
217
FILTERED
21
20
18
19
11
10
8.64
8.35
8.25
98
93
102
112
113
120
98
93
102
-
-
-
TREATED
ALUMINA
16
3
0.1
8
11
11
10.79
10.54
10.20
137
65
81
<1
<0.2
<1
137
65
81
-
-
-
%
AR*
23.9
85
99.5
57.9
0
-1-
-
_
_
+
30.2
20.6
>99. 1
>99.8
>99. 1
+
30.2
20.6
-
-
-
CAPILLARY
MEMBRANE
DIALYSIS
17
10
9
3
2
3
7.31
6.83
7.30
22
23
29
48
31
38
22
23
29
-
-
-
%
iR*
19.1
50
50
84.3
81.9
72. S
-
-
«.
77.6
75.3
71.6
57.2
72.6
68.4
77.6
75.3
71.6
-
-
-
COAGULATION :
ALUM POLY-
ELECTROLYTE
33
30
28
10
11
n
8.10
7.62
7.65
93
87
95
129
109
119
93
87
95
-
-
-
%
AR*
-(•
4-
Jf
47.4
0
J_
-
_
_
5.2
6.5
6.9
+
3.6
0,9
5.2
. 6.,5. ,_
6.9
-
-
-
\o
oo
* Expressed as ~ reduction ol filtered r.-»rrt>]"7. - Vsliss <>f treif&i simnle exceeds that of filtered control.
t Values repoi-ted are «ie« limit of senpttlvlty f^r test
-------
APPENDIX MB
COMPARATIVE ANALYSE 0¥ STREAM T1ATER BEFORE AND AFTER TREATMEKT BY
ALUMINA ADSORPTION; CAPIUARY MEMBRANE DIALYSIS; AND COAGULATION:
TROUT RUN
CLASS
MISC.
ANALYSES
ANALYSIS
DISSOLVED
SOLIDS
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
AFRIT,
MAY
-
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
_
^
-
FILTERED
252
191
236
TREATED
ALUMINA
502
287
410
%
flR*
+
+
+
CAPILLARY
MEMBRANE
DIALYSIS
40
71
200
%
&R*
92.1
62.9
15.3
COAGULATION :
ALUM POLY-
ELECTROLYTE
254
200
199
%
i R*
+
-1-
15.7
Expressed as % reduction of filtered samples.
Value of treated sample exceeds that of filtered control.
t Values reported are near limit ot sensitivity for tesl
-------
APPENDIX I-IC
COMPARATIX'E ANALYSIS OF STREAM WATER BEFORE AND AFTER TREATMENT BY
ADSORPTION; CAPILLARY MEMffRANE DIALYSIS': AMP COAUULATUJHT—
VALLEY CREEK
CLASS
NUTRIENTS
ANALYSIS
TOTAL
CARBON
ORGANIC
CARBON
INORGANIC
CARBON
TOTAL PO4 -
P
H YDROLYZ-
ABLE PO4 -
P
PHOSPHATE
ORTHO
KJEIDAHL
NITROGEN
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
MARCH
APRIL
MAY
JANUARY
MARra
A.PRTT,
MAY
.TAMTT AR V
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
43
44
34
45
7
12
7
5
.Ifi
32
27
40
0.05
0.03
0.16
0.03
0.05
0.03
0.07
0.03
0.04
0.02
0.03
0.03
0.2
0.2
0.3
0.1
FILTERED
43
43
41
48
4
11
4
*
30
32
37
44
0.04
0.03
0.03
0.02
0.04
0.03
0.03
0.02
0.03
0.02
0.03
0.02
P-2
0.2
0.3
0.1
TREATED
ALUMINA
21
6
9
7
3
1
4
1
ift
5
5
6
0.01
0.02
0.01
<0.01
0.004
0.010
0.010
< 0.010
<0.002
<0.002
0.002
<0.005
0.2
1.9
1.0
0.4
%
AR*
51.2
86.1
78.1
85.5
25
91
0
75
53 A
84.4
86.5
86.4
7B
33.4
66.7
>50.0
90
66.7
66.7
>50
>93.4
>90
93.4
>75
0
+
+
+
CAPILLARY
MEMBRANE
DIALYSIS
11
8
13
18
1
3
7
2
in
5
6
16
n.na
0.02
0.01
0.01
0.09
0.02
0.01
0.01
0.04
0.01
0.01
... 0.01
0.1
0.2
0.1
0.1
%
AR*
74.5
81.4
68.3
62.5
75
72.8
+
50
74.4.
84-4
83.8
63.7
J»
33.4
66.7
50
+
33.4
66.7
50
+
50
66.7
SO
50
0
66.7
0
COAGULATION :
ALUM POLY-
ELECTROLYTE
43
45
39
45
4
14
4
10
aa
31
35
35
n Al
0.02
0. i)3
0.01
0.004
0^02
0.03
0.01
0.006
0.01
0.03
0.01
0.2
0.6
0.2
0.6
%
AR*
0
+
4.9
6.3
0
+
0
+
0
3.2
5,5
20. S
75
33 14
0
50
90
33.4
0
50
_SQ
50
0
50
0 ,,,,
33.4
Expressed as % reduction of filtered samples.
Value of treated sample exceeds that of filtered control.
t Values reported are near limit of sensitivity for tee
-------
APPENDIX I-C
COMPARATIVE ANALYSES OF STREAM WATER BEFORE AND AFTER TREATMENT BY
ALUM1NA ADSORPTION: CAPILLARY MEMBRANE DIALYSIS: AND COAGULATION:
VALLEY CREEK
CLASS
NUTRIENTS
to
2
O
t-t
H
<
0
ANALYSIS
AMMONIA
NITROGEN
NITRATE
NITROGEN
NITRITE
NITROGEN
Ca
Mg
Zn
K
NO.
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
MARCH
A PUTT.
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
0.1
0.1
0.03
0.04
2.5
2.4
2.2
_
0.02
0.02
0.01
L 0.02
_
74
62
33
-
50
20
21
_
<0.02
<0.02
<0.02
2
2
2
FILTERED
0.1
0.2
0.04
0.10
2.5
2.3
2.2
„_
0.02
0.02
0.01
0.02
40
40
63
36
20
25
17
10
<0.04
<0.02
<0r02
^0.02
2
2
2
2
TREATED
ALUMINA
0.1
1.8
1.2
0.4
2.5
1.4
2.0
_
0.01
0.02
0.01
0.02
<0.2
0.2
<0.2
<0.2
0.1
<0.1
<0.2
<0.2
<0.04
<0.02
<0.02
.-0.02
0.2
0.2
0.2
0.3
£
A R*
0
>
+
+
0
39.2
9.1
50
0
0
0
>99. 5
99.5
>99.0
->99. 5
95.5
>99.6
;>98.9
>98
90
90
90
85
CAPILLARY
MEMBRANE
DIALYSIS
0.04
0.10
0.03
0.10
0.4
0.02
0.2
_
0.004
< 0.001
< 0.002
0.02
8
10
9
11
4
4
4
5
<0.04
<0.02
<0.02
<0.02
1.0
0.2
0.2
1.0
t'
an*
GO
50
•25
0
84
39. 1
91
80
or.
80
0
80
75
8.r..8
69. r>
80
84
76.5
50
90
90
50
COAGULATION :
ALUM POLY-
ELECTHOLYTK
0.2
0.6
0.2
o.e
^.4
•2. 1
•>. a
_
'J.Ol
0.02
0.0]
O.U2
41!
•12
Tvi
38
21)
2;l
21
21
o
0
0
0
!
,
1-1.. :
i
0
4
f
i
t
i
i
i
Expressed as % reduction of filtered samples.
Value of treated sample exceeds that of filtered control.
t Values reported arc near limit of sensitivity for tc:
-------
APPENDIX 1-C
COMPARATIVE ANALYSIS OF STREAM WAITER BEFORE AND AFTER TREATMENT BY
ALUMINA ADSORPTION: CAPILLARY MF-MWftN? P^LYSIS: AND COAGULATION?
VALLEY CREEK
CLASS
CATIONS
ANIONS
ANALYSIS
Na
B
Si
Co
Cu
Fe
so3
NO.
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRTT,
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAV
JANUARY
MARCH
APKTT.
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
_
18
16
17
0.2
0.2
0.2
0.6
3.3
2.3
1.0
6.0
_
<0.05
<0. 1
-------
APPENDIX I-C
COMPARATIVE ANALYSIS OF STREAM WATER BEFORE AW) AFTER TKEA™*F"ST BY
ALUM1MA ADSORPTION f-**>TI.l.ABY MEMBRANE DIALYSIS; AND COAGULATION;
VALLEY CREEK
CLASS
ANIONS
ALYSES
NEOUS AH
1ISECELLA
Z
ANALYSIS
^4
Cl
PH
SPECIFIC
CONDUCTANCE
HARDNESS
EDTA
ALKALINITY
TOTAL
TOTAL
SOLIDS
NO.
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
MARCH
^•PRTT.
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APHTT.
MAY
JANUARY
M.ARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
JANUARY
MARCH
APRIL
MAY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
-
31
34
33
29
30
_
29
—
7.00
9. OS
8.35
490
500
490
„
206
168
176
-
168
146
153
348
340
350
520
FILTERED
38
30
34
34
29
30
_
29
8.95
_ S,3p
8.77
8.40
505
495
480
485
192
_
177
178
168
165
146
151
-
-
-
-
TREATED
ALUMINA
6
<1
3
«1
24
22
_
29
11.25
7,75
10.22
9,79
495
290
405
175
<1
<2
<0.2
<1
111
61
74
24
-
-
-
-
%
AH*
84,3
>96.7
90
>97.1
17.3
26.7
0
_
_
—
2
41,5
15.7
64
>99.5
_
>99.8
>99.4
34
63.1
49.4
84.2
-
-
-
-
CAPILLARY
MEMBRANE
DIALYSIS
17
12
8
15
6.5
3.6
5.0
7.14
7.02
6.39
6.95
140
78
83
150
44
31
24
53
35
17
20
38
-
-
-
-
%
a R*
44,7
60
73.4
55.9
77.6
12
82.8
—
^
w
72.3
84.3
82.8
69.1
77.1
H
86.5
L_70-3
79.2
89.7
J6.4
74.9
-
-
-
-
COAGULATION :
ALUM POLY-
ELECTROLYTE
44
40
41
41
12.5
30. Q
28. Q
8.38
11.09
8.38
8.10
495
487
480
482
183
205
169
173
154
154
137
139
-
-
-
-
1
an*
+
+
4-
56.9
0
3. a
.
2
1 7
L +
0.7
4.7
^
-t-
2.0
3.4
6.7
6.2
8,0
-
-
-
-
* Expressed as % reduction of filtered samples.
Value of treated sample exceeds that of filtered control.
t Values reported are near limit of sensitivity for test
-------
APPENDIX I-C
COMPARATIVE ANALYSIS OF STREAM WATER BEFORE AM? AFTER TREATMENT BY
; AND COAGULATION:
VALLEY CREEK
CLASS
MISC.
ANALYSES
ANALYSIS
DISSOLVED
SOLIDS
HO.
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
JANUARY
MARCH
APRIL
MAY
1
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
.
_
_
_
FILTERED
344
299
308
463
TREATED
ALUMINA
478
242
236
375
%
AR*
2fl 1
19-1
23.4
19 1
CAPILLARY
MEMBRANE
DIALYSIS
iia
120
59
224
%
AS*
67.2
59.9
80.9
51.7
COAGULATION :
ALUM POLY-
ELECTROLYTE
372
2<>S
295
292
%
4 R*
.(.
1 4
4.3
37
Expressed a» % reduction of filtered samples.
Value of treated sample exceeds (hat of filtered control.
t Values reported are uear limit of sensitivity for tes
-------
A.WEWHX H>
COMPARATIVE AHALT8K OF WA8TEWATER EFFLUENT BEFORE AFTER TREATMENT BY
ALUMINA ADSORPTION-. CAPILLABV MBM^ANE DIALTOKS: AND COAGULATION;
PHOENIXVILLE
_
CLASS
NUTRIENTS
ANALYSES
TOTAL
CARBON
ORGANIC
CARBON
INORGANIC
CARBON
TOTAL P04 -
P
HYDROLYZ-
ABLE PO4 -
P
PHOSPHATE
ORTHO
KJELDAHL
NlTKUGEN
NO.
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
TEST CONDmON/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
87
65
84
27
22
25
60
43
59
8
8
8
8
8
7
7
7
3
29
31
22
FILTERED
71
57
75
15
tt
19
56
43
56
8
8
7
8
8
6
6
6
3
25
29
20
TREATED
ALUMINA
14
16
14
13
12
8
1
4
6
0.02
0.05
0.03
0.02
0.04
0.03
0.02
0.03
0.03
0.6
2.0
1.6
%
AR*
80.3
72.0
81.4
13.4
14.3
57.9
98,3
90.7
89.3
99.7
99.3
99.5
99.7
99.5
99.5
99.6
99.5
99.0
97.6
93.2
92.0
CAPILLARY
MEMBRANE
DIALYSIS
15
22
37
3
14
24
12
8
13
4
3
3
4
3
3
3
2
3
4
-
2
%
AR*
78
61.5
50.7
80.0
0
•f
78.6
81.4
76.8
50.0
62.5
57.2
50.0
62.5
50.0
50.0
66.7
0
84
-
90
COAGULATION :
ALUM POLY-
ELECTROLYTE
64
48
58
14
14
12
50
34
46
3
2
1
3
2
1
2
2
0.1
26
26
12
%
A R*
9.9
15.8
22.7
6.7
0
36.9
10. f.
21.0
17.9
62.5
75.0
85. S
62. T,
75.0
83.4
66.6
66.7
96.7
-*-
10.4
40.0
o
in
Expressed as % reduction of filtered samples. + Value of treated sample exceeds that of filtered control.
t Values reported are near limit of sensitivity for tes
-------
coyi
PARATTVE ANALYSIS
APPENDIX I-D
VATER EFFLUENT BEFORE AFTER TREATMENT BY
PHOENgVILLE
CLASS
NUTRIENTS
CATIONS
ANALYSIS
AMMONIA
NITROGEN
NITRATE
NITROGEN
NITRITE
NITROGEN
Ca
Mg
Zn
K
-
NO.
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
1
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
15
23
21
0.1
0.1
0.2
0.01
0.09
0.03
120
80
50
27
12
13
0.07
0.08
0.2
21
16
1.7
FILTERED
14
22
18
0,1
0.1
0.2
0.01
0.08
0.02
67
52
33
15
12
13
0.03
0.05
0.02
21
15
17
TREATED
ALUMINA
0.3
0.4
0.1
0.1
0.2
0.1
0.01
0.08
0.02
<0.2
<0.2
<0.2
<0.1
<0.2
-------
COMPARATIVE ANALTOB OF WASTEWATER EFYIAIEKT BEFORE AFTER TREATMENT BY
ALUMINA ADSORPTION: CAPILLARY MEMBRANE DIAI/HgS: AND COAGULATION:
PHOENKVILLE
CLASS
CATIONS
ANIONS
ANALYSIS
Na
B
S
CO
Cu
Fe
303
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
i '• f
4
MONTH
SAMPLE
COLLECTED
MARCH
APRIL
JtfAY
MARCH
APRIL
MAY
MARCH
APRIL.
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
APRIL
MAY
MARCH
APRIL
MAY
i
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
80
66
77
0.6
0.9
2.2
7.0
6.4
12.0
<0.05
<0.1
<0.3
<0.1
<0.1
0.03
<0. 1
0.4
<2
<2
<2
FILTERED
77
61
78
0.5
0.8
1.7
6.0
S.3
11.0
<0.05
<0. 1
<0.3
<0.1
<0. 1
<0.02
<0. 1
<0. 10
<2
<2
<2
TREATED
ALUMINA
81
48
57
0.1
0.1
0.2
0.1
0.2
1.0
<0.05
<0.1
<0.3
<0.1
<0.1
<0.02
<0.1
<0.10
<2
<2
<2
%
AR*
+
21.4
27.0
80.0
87.5
88.3
98.4
96.3
91
CAPILLARY
MEMBRANE
DIALYSIS
15
14
18
0.2
0.1
0.7
1.4
1.2
3.0
*0.05
<0.1
<0,3
<0. 1
<0.1
<0.02
<0.1
<0.10
<2
<2
<2
%
AR*
80.6
77.1
77.0
60.0
87.5
58.9
76.7
77.4
72.8
/
COAGULATION :
ALUM POLY-
ELECTROLYTE
77
60
77
0.6
0.8
2.0
4.0
5 5
16.0
<-0.05
<0 1
<0.3
<0.1
<0.1
<0.02
<0.1
<0.10
<2
<2
<2
%
AR*
0
1.7
1.3
•t-
0
+
33.4
4_
•f
* Expressed as % reduction of filtered samples. + Value of treated sample exceeds that of filtered control.
Values reported are near limit of sensitivity for tes
-------
APPENDIX I-D
STEWATER EFFLUENT
ATJIMINA
ADSORPTION: CA1
PHOENDCVILLE
DIALYSIS: AND COt
!
CLASS
CO
2
O
MISCELLANEOUS ANALYSES AN
ANALYSIS
S04
a
PH
SPECIFIC
CONDUCTANCE
HARDNESS -
EDTA
ALKALINITY -
TOTAL
TOTAL
SOLIDS
NO.
1
Z
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLIJ5CTED
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
MARCH
APRIL
MAY
I
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
133
119
112
63
63
72
7.61
7.72
7.95
1000
825
890
191
121
156
260
177
211
340
406
715
FILTERED
122
113
102
63
56
71
8.05
7.68
8.05
1020
815
860
188
120
157
255
176
207
-
-
-
TREATED
ALUMINA
8
6
0.4
64
59
80
10.96
9.78
9.25
495
420
360
<2
<0.2
<1.0
75
38
13
-
-
-
%
AR*
99.3
94.7
99.6
+
±
+
_
_
._
51.5
48.5
58.2
>98.9
>99.8
99.3
70.6
78.5
93.8
-
_
-
CAPILLARY
MEMBRANE
DIALYSIS
55
49
35
12
7
13
7.85
7.30
7.85
250
195
275
62
38
62
69
32
53
-
_
-
%
AR*
54.9
56.7
65.7
81
ft? 1
81.7
_
_
_
75.5
76.1
6JJ.
67.1
68.4
60.6
73.0
81.9
74.4
_
-
-
COAGULATION :
ALUM POLY-
ELECTROLYTE
169
154
173
64
VJ
45
7.78
7.76
7.90
1040
820
880
177
116
146
226
137
161
_
-
-
%
AR*
+
-J-
jf-
4.
36.7
„
.
.
+
-+
-f-
5.9
3.4
7.1
11.4
21.6
22.3
_
_
_
* Expressed as % reduction at filtered samples.
Value at treated sample exceeds that at filtered control.
t Values reported are near limit of sensitivity for tea
-------
COMPARATIVE ANALYSE OF WASTEWATER EFFLUENT BEFORE AFTER TREATMENT BY
AL.yMTW.ft ADSORPTION: CAPIt'T'/>pY MEMBRANE DIALYSIS: AND COAGULATION:
PHOENCCVILLE
CLASS
MISC.
ANALYSES
ANALYSIS
DISSOLVED
SOLIDS
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
MARCH
APRIL
MAY
TEST
UNTREATED
UNFILTERED
_
_
-
FILTERED
497
421
150
CONDITION/CONCENTRATION (PART PER MILLION)
TREATED
ALUMINA
390
257
317
%
AH*
21.6
39.0
51.3
CAPILLARY
MEMBRANE
DIALYSIS
144
114
167
%
AH*
71.1
73.0
74.4
COAGULATION :
ALUM POLY-
ELECTROLYTE
512
209
496
%
AR*
50.4
23 7
* Expressed as % reduction of filtered samples. + Value of treated sample exceeds (hat of filtered control.
t Values reported are near limit of sensitivity for test
-------
APPENDIX I-E
COMPARATIVE ANALYSIS OF WASTEWATER EFFLUENT BEFORE AFTER TREATMENT BY
ALUMINA ADSORPTION: CAPILLARY MFMWANE DIALYSIS: AND COAGULATION:
HATFEEU
CLASS
NUTRIENTS
ANALYSIS
TOTAL
CARBON
ORGANIC
CARBON
INORGANIC
CARBON
TOTAL PO4 -
P
HYDROLYZ-
ABLE PO4 -
P
PHOSPHATE
ORTHQ
KJELDAHL
NITROGEN
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JJW
APRIL
MAY
JULY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNPILTERED
73
57
26
22
21
5
51
36
21
0.22
0.21
0.64
0.20
0.20
0.63
0.09
0.17
0.53
70.2
0.1
1.8
FILTERED
72
46
27
20
10
5
52
36
22
0.12
0.16
0.53
0.08
0.16
0.54
0.05
0.14
0.50
57.0
0.1
1.3
TREATED
ALUMINA
19
12
H
14
6
5
5
6
3
0.02
0.01
0.01
0.02
0.01
0.01
0.002
0.01
0.01
10.0
-
1.7
%
AB«
73.7
74.0
70.4
30.0
40.0
0
90.4
83.4
41.7
83.4
93.8
98.2
75.0
93.8
98.2
96.0
92.9
98.0
82.5
-
+
CAPILLARY
MEMBRANE
DIALYSIS
23
22
18
13
9
9
10
13
9 j
0.05
0.09
0.4
0.03
0.09
0.35
0.02
0.08
0.30
-
0.2
1.2
%
6 R*
68.1
52.2
73 4-
35.0
10.0
+
80.8
63.9
59. 1
58.4
43.8
24.6
62.5
43.8
35.2
60.0
42.9
40.0
-
+
7.7
COAGULATION :
ALUM POLY-
ELECTROLYTE
67
29
2fi
1R
8
7
49
21
19
0.06
<0.005
0.2
0.02
<0.01
0.17
0.01 __,
<0.005
0.1
50.2
0.5
1.3
%
A R*
7.0
37 0
1 »
in n
20.0
+
5.8
41.7
13 7
50.0
>96.9
62.3
75. C
:>93. 8
68.6
80.0
> 96.5
80.0
12.0
+
0
* Expressed as % reduction of filtered samples.
Value of treated sample exceeds that of filtered control.
t Values reported are near limit of sensitivity for test
-------
APPENDIX 1-E
COMPARATIVE ANALYSIS OF WASTEWATER EFFLUENT BEFORE AFTER TREATMENT BY
ALUMMA ADSORPTION: HAPTT.TA^y ^f^ANE DIALYfflS; AMD COAGULATION:
HATFIELD
CLASS
NUTRIENTS
CO
S5
o
E-i
<:
0
ANALYSIS
AMMONIA
NITROGEN
NITRATE
NITROGEN
NITRITE
NITROGEN
Ca
Mg
zn
K
NO.
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
64.7
0.1
0.1
0.1
1.7
0.4
0.1
4.1
4.4
87
90
55
9
22
14
0.04
0.16
0.02
14
6
9
FILTERED
52.2
0.1
0.1
0.1
1.6
0.3
0.1
4.3
4.4
58
47
57
6
22
14
0.03
0.02
0.02
8
6
8
TREATED
ALUMINA
S.7
4.4
0 7
0.1
1.5
0.3
0.1
4.1
4.2
<0.2
<0.2
1
<0.2
<0.2
1
«fO OS
0.02
0.02
0.3
16
11
%
AR*
89.1
+
-f-
0
B.3
0
0
4.7
4.6
>99.6
>99.5
98.2
>96.7
>99. 1
92.9
t
t
t
96.3
+
+
CAPILLARY
MEMBRANE
DIALYSIS
9.0
0.1
0 2
0.04
<0. 1
0.1
0.01
1.1
1.9
37
14
31
4
6
8
0.03
0.04
0.02
2
2
4
%
AR*
82.8
0
+
60.0
>93.ft
66.7
90.0
74.5
56.9
36.3
70.3
45.7
33.4
72.8
42.9
t
t
t
75.0
66.7
50,0
COAGULATION
ALUM POLY-
ELECTKOLYTE
47.0
0 2
n i
0 1
1.5
0.3
0.1
4.1
4.3
57
22
55
6
21
14
0.03
0.03
0.02
11
19
10
%
AR*
90.0
-t-
0
o
6.3
0
0
4.7
2.3
1.8
53.2
3.6
0
4.6
0
t
t
t
+
+
+
* Expressed as % reduction of filtered samples. + Value of treated sample exceeds that of filtered control.
t Values reported are Rear limit of sensitivity for test
-------
APPENDIX I-E
COMPARATIVE ANALVSB OF WA8TEWATER EFFLUENT BEFORE AFTER TREATMENT BY
ATJIMTMA AnsnqpTICM! fltW^T/iyy ^fl^ANE DIALTOIS: AND COAGULATION:
HATFIELD
CLASS
CATIONS
ANIONS
ANALYSIS
Na
B
Si
Co
Cu
Fe
SOg
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2 I
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
fULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
60
53
58
0.9
2.0
1.0
3.2
12.0
8.7
<0.1
<0.3
0.05
<0.1
<0.02
0.02
<0.1
-------
ASPEWHX.VE
COMPARATIVE AKALYSS OF WASTEWATER
BCTQRE AFTER TREATMENT BY
ALUMNA ADSORPTION: CAPILLARY
HATFIELD
DIALYgSi AHD COAGULATION:
CLASS
ANIONS
ALYSES
MISCELLANEOUS AN
.
ANALYSIS
so4
Cl
PH
SPECIFIC
CONDUCTANCE
HARDNESS -
EDTA
ALKALINITY
TOTAL
TOTAL
SOLIDS
NO.
1
2
3
.4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
APRIL
MAY
.TTTT.V
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
APRIL
MAY
JULY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED | TREATED
UNFILTERED
357
151
118
80
57
60
7.84
8.10
7,98
1530
790
652
261
255
180
213
114
292
666
490
433
FILTERED 1 ALUMINA
352
148
118
76
60
56
7.76
7.95
7.89
1500
790
660
256
256
178
209
114
215
-
-
-
4.8
0.4
2.3
77
62
56
9.73
9.65
9.45
560
380
610
<0.2
<1
4
43
32
42
-
-
%
AH*
86.4
99.7
98.1
+
+
0
-
-
_
62.7
51.9
33.0
an A
99.6
97.7
79.5
72
80.5
CAPILLARY
MEMBRANE
DIALYSIS
131
80
85
9
16
40
7.39
6.75
7.81
390
340
409
92
113
106
38
43
62
-
-
-
%
AR»
62.8
46.0
28.0
88.2
73.4
28.6
-
_
_
74
57
38.1
64.1
55.9
40.5
81.9
62.3
71.2
COAGULATION .
ALUM POLY-
ELECTROLYTE
350
191
122
63
57
55
7.81
7.85
8.70
1430
790
661
242
244
180
195
66
101
-
-
-
5
A R*
0.6
+
• +
17.2
5.0
1.8
-
_
_
4.7
0
+
5.5
4.7
-f
6.7
42.2
53.1
* Expressed as % reduction of filtered samples.
Value of treated sample exceeds that of filtered control.
t Values reported are near limit of sensitivity for test
-------
APPENDIX I-E
COMPARATIVE ANALYSIS OF WASTEWATER EFFLUENT BEFORE AFTER TREATMENT BY
ALUMINA ADSORPTION: CAPILLARY MEMBRANE DTALYSIS; AND COAGULATION:
HATFIELD
CLASS
MISC.
ANALYSES
ANALYSIS
DISSOLVED
SOLIDS
HO.
1
2
3
.4
1
2
3
4
1
2
3
4
J
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
MONTH
SAMPLE
COLLECTED
APRIL
MAY
JULY
TEST CONDITION/CONCENTRATION (PART PER MILLION)
UNTREATED
UNFILTERED
_
_
—
FILTERED
668
499
418
TREATED
ALUMINA
318
407
340
%
AR*
52.4
18.5
18.7
CAPILLARY
MEMBRANE
DIALYSIS
216
225
241
%
AR*
67.7
34
42.4
COAGULATION :
ALUM POLY-
ELECTROLYTE
667
526
427
%
A R*
0.1
+
+
* Expressed as % reduction of filtered samples. + Value of treated sample exceeds (hat of filtered control.
t Values reported are near limit of sensitivity for tes
-------
APPENDIX II
CAPILLARY MEMBRANE SPECIFICATIONS AND OPERATING CONDITIONS*
Composition
Temperature
Particle Size
Viscosity
Pressure and
Vacuum
Chemical
Stability
Cleaning
Cellulose
Cellulose Fibers - 0 to 60°C
Avoid processing fluids containing particles larger
than 10 .
Solutions as viscous as 59% sucrose in water at 0°C
have been processed on the outside of the fibers
and solutions as viscous as 43% sucrose in water at
0°C have been processed by flow through the fiber
themselves.
The devices should never be operated at a pressure
differential greater than 600 mm Hg between the
inside and outside of the fibers. If this differ-
ential is exceeded either by applying excess
pressure or vacuum, the fibers may collapse and
become permanently damaged.
Cellulose fibers have a normal operating range of
pH 1-12. Contact with cellulose producing
organisms, enzymes with cellulose activity and
aromatic or chlorinated hydrocarbons should be
avoided. Cellulose fibers are resistant to
methanol, ethanol, isopropanol, 50% formamide in
water, phosphate buffer at pH 8.0, 1M guanidine HC1
and 6M urea.
Fibers can be cleaned of protein by soaking in an
enzyme presoak or enzyme detergent.
If the fibers become clogged, they normally can be
cleaned by an overnight backflush with water, in
the reverse direction of flow, using a pressure of
5 psi (0.3 atm).
* Dow Chemical Company, Midland, Michigan.
115
-------
Storage To avoid possible bacterial degradation the fibers
should be stored in a 1.5% formalin solution.
Special Do not allow fibers to dry out once they have been
Precautions wet. Rinse immediately after use and store as
described above.
Avoid touching the fibers. This is the most contnon
cause of damage.
116
-------
SELECTED WATER 1. Report No.
RESOURCES ABSTRACTS EPA-660/3-7U-022
INPUT TRANSACTION FORM
2.
3. Accession No.
4. Title
An Investigation of Ion Removal from Water
and Wastewater
5. Report Date
August 1973
6.
7.
Author R. J. Starkey, Jr., M. E. Kub,
A. E. Binks, and K. K. Jain
8. Performing Organization
Report No.
9. Organization General Electric Company
Re-entry & Environ. Systems Div.
Philadelphia, Pennsylvania 19101
10. Project No.
EPA-68-01-0904
12. Sponsoring Organization U. S. Environmental
Protection Agency, NERC, Corvallis, Oregon
11. Contract / Grant No.
15. Supplementary Notes
13. Type of Rpt. & Period Covered
7-1-72 to 7-1-73
16. Abstract
Three standardized techniques (capillary membrane dialysis, alumina adsorption,
alum/ polyelectrolyte coagulation) have been compared under laboratory conditions
to determine their relative effectiveness in removing a broad spectrum of nutrients
cations, and anions from freshly collected samples of stream water and wastewater
effluent (secondary and tertiary).
Of these alumina adsorption was highly effective in removal of phosphorus,
inorganic carbon, as well as most cations with concomitant reduction of specific
conductance and hardness. High Kjeldahl and ammonia nitrogen removal efficencies
of alumina were only observed in samples of wastewater in which pre-treatment
concentrations were relatively high. Dissolved solids content and pH of alumina
treated samples were consistently observed to increase.
Dialysis occupied an intermediate position in respect to cation removal, but
produced results equivalent to alumina adsorption in respect to inorganic carbon.
Failure to significantly reduce organic carbon concentrations was attributed to
its association with macromolecules having a molecular weight greater than 5000
(the cutoff of the cellulose membrane under consideration). Superiority of dialysis
in removal of sodium, potassiu, chloride, nitrate-nitrte, boron, and dissolved
solids is reported. Coagulation was effective in removing phosphorus from all watei
hnf. wflfl highly Ineffective in respect to all other parameters tested.
17a. Descriptors
Capillary membrane dialysis, alumina adsorption, coagulation, water, wastewater,
algal bottle assay, macromolecules
17b. Identifiers
Nitrogen, carbon, phosphorus, cations, anions, dissolved solids, total solids,
specific conductance, hardness, pH, alum, polyelectrolyte
J7c. COWRR Field & Group
18. Availability
19. Security Class.
(Report)
20. Security Class.
(Page)
Abstractor
21. No. of Pages
22. Price
Send to:
Water Resources Scientific Information
Center, U. S. Department of fee Interior
Washington. D. C.
Institution
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