xvEPA
            United States
            Environmental Protection
            Agency
            Industrial Environmental Research
            Laboratory
            Cincinnati OH 45268
EPA-600 7-79-101
April 1979
            Research and Development
Removal of Trace
Elements from
Acid Mine
Drainage

Interagency
Energy/Environment
R&D Program
Report

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology.  Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

      1.   Environmental Health Effects Research
      2.   Environmental Protection Technology
      3.   Ecological Research
      4.   Environmental Monitoring
      5.   Socioeconomic Environmental  Studies
      6.   Scientific and Technical Assessment Reports (STAR)
      7.   Interagency Energy-Environment Research and Development
      8.   "Special" Reports
      9.   Miscellaneous Reports

This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series.  Reports in this series result from the
effort funded  under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control  technologies for energy
systems; and  integrated assessments of a wide range of energy-related environ-
mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                               EPA-600/7-79-101
                                               April  1979
REMOVAL OF TRACE ELEMENTS FROM ACID MINE DRAINAGE
                       by

      Roger C. Wilmoth and James L. Kennedy
  Industrial Environmental Research Laboratory
             Cincinnati, Ohio  45268

                      and

       Jack R. Hall and Charles W. Stuewe
               Hydroscience, Inc.
         Knoxville,  Tennessee  37919
             Contract No. 68-03-2568
                Project Officer

                Roger C. Wilmoth
  Resource Extraction and Handling Division
 Industrial Environmental Research Laboratory
           Cincinnati, Ohio  45268
  INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
       OFFICE OF RESEARCH AND DEVELOPMENT
     U. S. ENVIRONMENTAL PROTECTION AGENCY
            CINCINNATI, OHIO  45268

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                                 DISCLAIMER
     This report has been reviewed by the Industrial Environmental Research
Laboratory, U. S. Environmental Protection Agency, and approved for
publication.  Approval does not signify that the contents necessarily
reflect the views and policies of the U. S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorse-
ment or recommendation for use.
                                      11

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                                  FOREWORD


     When energy and material resources are extracted, processed, converted,
and used, the related pollutional impacts on our environment and even on our
health often require that new and increasingly more efficient pollution con-
trol methods be used.  The Industrial Environmental Research Laboratory-
Cincinnati (lERL-Ci) assists in developing and demonstrating new and improved
methodologies that will meet these needs both efficiently and economically.

     This report describes the results of studies conducted to determine the
ability of lime neutralization, reverse osmosis, and ion exchange processes
to remove ten inorganic trace elements from acid mine drainage.  Results of
this research should prove useful to both industry and regulatory agencies
having problems with any of the ten pollutants in their discharges by provid-
ing possible treatment alternatives.  For further information, please contact
the Extraction Technology Branch of the Resource Extraction and Handling
Division in Cincinnati.
                                          David G. Stephan
                                             Director
                              Industrial Environmental Research Laboratory
                                            Cincinnati
                                    iii

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                                  ABSTRACT

     Lime neutralization, reverse osmosis, and ion exchange were studied for
their effectiveness in removing mg/1 levels of ten specific trace elements
from spiked acid mine drainage under typical operating conditions.  The
specified trace elements were arsenic, boron, cadmium, chromium, copper,
mercury, nickel, phosphorus, selenium, and zinc.

     Treatment by lime neutralization was very effective in removing arsenic,
cadmium, copper, mercury, nickel, and zinc, and relatively ineffective in
removing boron and phosphorus.  Reverse osmosis was very effective in reject-
ing arsenic, cadmium, chromium, copper, nickel, and zinc, and relatively
ineffective in rejecting boron.  The two-bed (strong acid-weak base) ion
exchange system was very effective in removing all of the trace elements
except phosphorus and boron.  None of the three treatment methods was very
effective in removing phosphorus.

     Analysis for boron proved troublesome.  Use of the standard nitric acid
metals preservation methods was found to be inappropriate for samples requir-
ing boron analysis.
                                     IV

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                                 CONTENTS
Foreword	     iii
Abstract	 .      iv
Figures	      vi
Tables	     vii
Acknowledgments	      ix

     1.   Introduction 	       1
     2,   Conclusions	       5
     3.   Recommendations	       6
     4.   Treatment Studies	       7
               Background information	       7
               Trace element injection 	       7
               Sample handling analysis	       8
               Lime neutralization 	       8
               Reverse osmosis 	      20
               Ion exchange	      24
               Waste treatment and disposal	      35

References	      36
Appendices ...... 	      38

     A.   Discussion of Analytical Results 	      38
               Problems encountered	      38
               Analytical interpretation 	      39
               Review of quality assurance program  	      40
               Intralaboratory quality control program  	      40
     B.   Outline of Analytical Methods and Instrumentation.  ...      49
     C.   Individual Analytical Data	      52

Glossary	     74

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                                  FIGURES

Number                                                                 Page

  1       Schematic flow diagram for the EPA neutralization
            facility	     12

  2       The effect of pH on trace element concentration
            in the neutralization process effluent	     15

  3       Flow diagram for the 4000-gpd spiral-wound reverse
            osmosis unit	     21

  4       Schematic flow diagram of EPA 2-resin ion exchange
            unit	     26

  5       Photograph of the ion exchange installation at Crown.  .  .     27

  6       Trace element trends throughout the cation service
            cycle	     31

  7       Trace element trends throughout the anion service
            cycle	     32

  8       Conventional pollutant trends throughout the cation
            service cycle 	     33

  9       Conventional pollutant trends throughout the anion
            service cycle 	     34


A-l       Example of daily standard curve 	     42

A-2       Example of blind split analysis certificate 	     45

A-3       Example of spiked sample analysis certificate 	     46

A-4       Example of precision control chart	     47

A-5       Example of a blind standard analysis certificate	     48
                                      vi

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                                   TABLES

Number                                                                  Page

  1       Selected Mine Drainage Analyses	      3

  2       Selected Pollutants and Desired Concentrations for
            Treatability Study 	      4

  3       Summary of Optimum Removal of Trace Elements 	      5

  4       Crown Raw Water Quality During Trace Element Study ....      9

  5       Trace Element Levels in Spiked AMD 	     10

  6       Neutralization Operational Data Summaries for
            Trace Element Study	     13

  7       Summary of Lime Neutralization Water Quality
            Analyses	     14

  8       Detailed Summary of Lime Neutralization Chemical
            Analyses	     16

  9       Mean Operating Parameters for Crown Spiral-Wound
            Reverse Osmosis Study	     22

 10       Reverse Osmosis Water Quality Summary	     23

 11       General Specifications for EPA Ion Exchange Treatment
            Unit	     28

 12       Average Values for the Ion Exchange Operating
            Parameters	     29

 13       Ion Exchange Water Quality Summary 	     30

A-l       Example of Precision Data (Water Sample Analysis for
            Mercury)	     43

A-2       Example of Accuracy Data for Phosphorus	     44

B-l       Applicable Analytical Methodology	     51
                                     vii

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                            TABLES  (Continued)

Number

C-l       Trace Element Pollutant Anlayses for Lime
            Neutralization  	   52

C-2       Conventional Pollutant Chemical Analyses for Lime
            Neutralization  	   58

C-3       Material Balance  for Lime Neutralization Study 	   64

C-4       Reverse Osmosis Trace Element Analyses 	   65

C-5       Reverse Osmosis Conventional Pollutant Analyses	   67

C-6       Material Balance  for Reverse Osmosis Study 	   69

C-7       Ion Exchange Trace Element Analyses	   70

C-8       Ion Exchange Conventional Pollutant Analyses 	   72
                                   vin

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                              ACKNOWLEDGMENTS

     The cooperation and participation of the Resource Extraction and
Handling Division personnel, including Ronald D. Hill, Eugene F.  Harris,
Robert B. Scott, Harry L. Armentrout, Robert M. Michael, Daniel L. Light,
Loretta J. Davis, James L. Shaffer, Jessie R. Burdett, and Barbara A. Cappel
was important to the completion of the study.  The assistance of
Kenneth A. Crabtree of EPA Procurement Division was instrumental to the
timely completion of the research effort.

     Special thanks are extended to J. Randolph Lipscomb for his onsite
supervision of the research program.  Our appreciation is also extended to
Dr. Anna M. Yoakum and Barry Stephenson of Stewart Laboratories for their
cooperation and rapid response to the needs of the analytical program.  The
study was made possible by the assistance and cooperation of Consolidation
Coal Company.  We wish to specifically thank Dr. Gerald Barthauer, Mike
O'Brien, Ray Henderson, Mike Ryan, and Hershel Travis for their helpfulness.
                                     IX

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                                  SECTION  1

                                 INTRODUCTION

      In  recent  years,  the  U.  S.  Environmental  Protection Agency  (EPA) through
 contracts,  grants,  and in-house  research  has addressed  the problem of treating
 acid  mine drainage  (AMD) to recover water for  reuse  or  discharge  into streams.
 As part  of  this program, the  EPA established the Crown  Mine Drainage Control
 Field Site,  located near Morgantown,  West Virginia,  to  study the  treatability
 of predominately ferrous iron AMD.

      Treatment  methods for AMD involve either  neutralization and  precipitation,
 reverse  osmosis,  ion exchange, or combinations of these.  The most common
 treatment method for AMD discharges is neutralization using lime  (1-2).  By
 this  process, dissolved iron, manganese,  aluminum, and  other metal ions are
 precipitated at an  elevated pH and separated as a sludge for disposal.
 Oxidation of iron from the ferrous to ferric state and  coagulant  addition are
 used  to  improve the effluent  quality  (2).  Other alkaline materials such as
 limestone (calcium  carbonate), sodium carbonate, and sodium hydroxide can be
 used  instead of lime.

      In  addition to neutralization, reverse osmosis  and ion exchange have
 been  reported as  AMD treatment methods by the  EPA and others (3-4) .  In
 reverse  osmosis (RO),  water molecules from the AMD are  driven by  pressure
 through  semi-permeable  membranes  leaving  behind most of the dissolved salts
 as a  concentrated waste effluent  (brine).  Rejection rates of 99% of the
 salts have been reported from EPA studies on various AMD streams  (5-6).  In
 other studies,  AMD was  effectively demineralized in  the two-resin ion exchange
 pilot system in use at  the Crown  site (7).

     All these  previous EPA studies emphasized the overall applicability of
 the treatment method,  operational limitations, cost, and conventional param-
 eters of effluent quality  (3).  These parameters included iron, manganese,
 suspended solids, and  aluminum concentrations  and pH.

     The presence of trace elements in acid mine drainage (AMD) has received
 little attention  in the past;  however, recent  cognizance has prompted the
research community to address  the situation.  AMD offers a favorable medium
 for existence of  trace elements because many are acid-soluble and are leached
 from strata associated with the mining process.  Some trace elements are
on the EPA list of Priority Pollutants.

     The purpose  of this study was to determine the effectiveness of lime
neutralization,  reverse osmosis,   and ion exchange treatment processes in
removing several of the trace  elements.   The study was conducted at the EPA
Crown Field Site, where appropriate concentrations of trace elements could be

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injected into a moderately-acid AMD stream to simulate the field
situation.

     The selection of the parameters to be studied and their respective
concentrations was made on the basis of levels found in mine discharges.
Table 1 illustrates the matrix of data used in the selection.  These choices
are summarized in Table 2.  Eight of the 10 are listed by EPA as toxic sub-
stances.  For this study the 10 compounds were combined in one concentrated
bulk solution and were continuously injected into the AMD feed streams to
the neutralization, reverse osmosis, and ion exchange processes to form the
desired concentrations.  Some precipitation problems were encountered during
lab-scale concentrate preparation, necessitating substituting different
compound forms of two elements and eliminating lead from the original study
list.   Table 2 contains the final choice of compounds.

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TABLE 1.  SELECTED MINE DRAINAGE ANALYSES
                 Cmg/1)
rbllutuit Source
Iron ore
Copoer
Lead/line
Lead/cine
Gold
Sllrer
Baodte
u/«./v
PlatlDUH
Coal aining-eax(9)
Ce»l«li.l«-«an<'>>
AM><101
*•><»>
Crown AMD
CboMB L«reli

5 ?* n i?o 0 . il 1 . r " . i? 16"
3.5 2.0 1.3 2.^ on ?^nO
8.1 n.n2 ^7 *.L i..
3.0 o.o£ 2?0 i.^ 2.5 ?.f-
6 n.nP 0.2 °T n.n? l.P "."? ?5 2.1 1!-
ft 0.1 15 1.2 ?." r. • " • """ l1^
2. ft 8fl f- '\
0.5 0.03 1.01 1?0 I'1
0.01 os ]^n ^.3 -i..
.30 «30-
2.1. 13 35C
2. ft ^2 22 l.o 178 90r
2.f 2fcO 0.9 n.? 16 ^Ln
5.0 15 VTO ?OC
5-0 15 2.0 1.0 370 i.n 10 l.o C.I 5.0 n.j 300 ?. ".-10

1?0 1R 15 0.1 n.i 8.0
1^° rt«? 0.1S O.O1! 12C 0.6
l'.0 ^3 0.7
CT ^.0° 0.3 T«0 38
D" 1? p^ p-l O.c 12^n 0.9 0.1 7.3
^ *•? -^ °.'V) i.2 0.13 3^0
"T." r-3 Poo 0.8
-* n- 1.1 0.03
?e iLn 1.01 n.B 2^0 o.03
02 *,f- Q7QO 13
^ n-7 2l-no 1.5
1° C.5 0.5 3800 250
°.1 n.c 0.0 3310 23
T:" <= Wo 3000
lin ^.0 LPl 0.5 1.0 1.0 0.8 3000 1.0 0.5 1.0 5.0

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TABLE 2.  SELECTED POLLUTANTS AND DESIRED CONCENTRATION
               FOR TREATABILITY STUDY
Pollutant
Arsenic
Boron
Cadmium
Chromium
Copper
Mercury
Nickel
Phosphorus
Selenium
Zinc
Concentration, mg/1
2.0
1.0
1.0
0.4
5.0
0.5
0.5
1.0
0.8
5.0
Compound used
Arsenic pentoxide
Boric acid
Cadmium sulfate
Chromium chloride
Cupric chloride
Mercuric chloride
Nickelous sulfate
Sodium phosphate
Selenous acid
Zinc chloride

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                                  SECTION 2

                                 CONCLUSIONS

     The removal effectiveness of each of the three processes (lime
neutralization, reverse osmosis, and ion exchange) is summarized in
Table 3.  The neutralization process appeared to be the logical process
choice, because of cost, for trace material removal for all the elements
studied except boron and phosphorus.  None of the three processes was
effective on boron and phosphorus.  Although ion exchange and reverse
osmosis were slightly more effective overall than lime neutralization,
the cost of the processes and need for subsequent waste treatment offset
their slight advantage in removal effectiveness.
           TABLE 3.  SUMMARY OF OPTIMUM REMOVAL OF TRACE ELEMENTS
Trace element
Typical
influent
cone . ,
PH
Optimum effluent concentration,
Lime neutralization Reverse
7-9 range pH 10-12 range osmosis
mg/1
Ion
exchange
mg/1
Arsenic
Boron
Cadmium
Chromium
Copper
Mercury
Nickel
Phosphorus
Selenium
Zinc
2.
2.
0.
0.
6.
0.
0.
1.5
1.
6.
3
2
9
06
2
5
7
to 10
2
,3
0.
2.
0.
0.
0.
0.
0.
2.
0.
0,
04
2 e
06
04
11
01
06
3 e
.05
,11
@ pH 9
pH 7
@ pH 8
@ pH 7
8 pH 9
@ pH 8
@ pH 9
i pH 9
@ pH 7
@ pH 9
0.02
1.45
0.01
0.04
0.05
0.01
0.06
1.09
0.15
0.09
« pH
€ pH
e pH
@ pH
e PH
@ pH
9 pH
G pH
@ pH
e PH
10
12
10
12
10
9
9
12
12
12
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
01
88
006
01
01
06
01
32
11
,06
0.52
0.58
0.001
0.01
0.03
0.001
0.02
no removal
0.09
0.03

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                                 SECTION 3

                              RECOMMENDATIONS

     The apparent inability of all the processes, and specifically the
neutralization process, to remove phosphorus needs further investigation.

     Similarly, the loss of mercury in the reverse osmosis process should
be studied.

     An analytical method for determination of boron should be developed for
samples preserved with the EPA nitric acid technique.

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                                  SECTION 4

                              TREATMENT STUDIES

 BACKGROUND  INFORMATION

     Lime neutralization, reverse osmosis (RO), and ion exchange  (IE) were
 studied at  the EPA Crown Field Site to determine their effectiveness in remov-
 ing the 10  trace elements of interest.  EPA awarded a contract to Hydroscience,
 inc., a subsidiary of Dow Chemical, to provide analytical services for the
 trace element analyses and to provide technical assistance.  The processes
 had been thoroughly studied by EPA  (1-2) for removal of the conventional
 parameters  of interest in AMD (e.g., acidity, iron, manganese, aluminum,
 magnesium,  sodium, sulfate, etc.).  For this study, all processes were
 operated in the mode optimum for pollutant removal, which is not necessarily
 the optimum mode for feasibility.  The neutralization, RO, and IE systems
 were therefore not optimized for cost but functioning under conditions shown
 in previous studies to be most effective for achieving the highest effluent
 quality.


 TRACE ELEMENT INJECTION

     It was not known previous to the study if the trace elements of interest
 were naturally occurring in the AMD at the Crown pilot plant.  The Crown AMD
 was pumped  from an abandoned deep mine in the Pittsburgh coal seam, located
 approximately 85 m (280 ft) below the surface.  It was assumed that the
 trace elements would have to be added to the AMD to achieve the desired
 concentrations.  This assumption proved to be generally valid except for boron,
 phosphorus, and nickel, which were shown during the study (Table 4) to be
 present in  the raw unspiked AMD.  The background trace element levels were not
 considered  in designing the spiking system because they were unknown at the
 start of the study.

     The desired trace element concentrations were obtained in the AMD by con-
 tinuous injection via chemical metering pumps of a concentrated spiking solu-
 tion into the AMD feed line to the process being studied.  The spiking solution
was prepared in bulk amounts in a 2500-liter polyethylene tank, which was
 equipped with a mixer.   To minimize stratification, the mixer operated on a
pulsed basis, i.e., on one minute of every 10.  Continuous mixer operation
was not desirable because of excessive evaporative loss and concern for gross
 concentration changes.   The 2500-liter tank was equipped with a wooden cover
 to reduce evaporation and splashing.  Table 5 summarizes the desired level of
pollutant concentration and the actual concentrations achieved for each process
 influent.   The desired levels conformed very well to the achieved levels for
 all parameters except phosphorus, which proved to be intermittently present

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in the Crown source.  Extremely high variations  in phosphorus content were
observed in the raw AMD and remain  largely unexplained.  The phosphorus varia-
tion was prominent only during the  neutralization phase of the study when
influent values above 40 mg/1 were  observed.

     Even though the reverse osmosis and ion exchange studies were run
concurrently, the spiked feed for the two studies, as analyzed for the trace
elements, differed.  The concentrations of all elements except phosphorus
were lower in the feed for the RO study.  This was due to a small difference
in flowrates of the spiking solution from the two metering pumps.  A problem
is apparent, however, in the RO process where mercury was consistently
analyzed in the feed at about 50% of the level measured in the feed to the
IE process.  Since the RO feed sample was taken  downstream of the cartridge
filter which was downstream of the  sulfuric acid addition point, partial re-
moval by the filter of mercury as mercuric sulfate was suspected.  This is
discussed further later.

     The individual analytical data for each sample are presented in
Appendix C.

SAMPLE HANDLING ANALYSIS

     Samples from all of the treatment methods were handled in a similar
manner.  Portions of the samples were immediately analyzed on-site, without
sample preservation, for pH, acidity, alkalinity, calcium, magnesium, sodium,
ferrous iron, total iron, aluminum, manganese, suspended solids, specific
conductance and sulfate.

     The remaining samples, except  for the sludge samples, were preserved and
shipped off-site for analysis.  EPA Methods (1976) were used for all the metal
determinations.  The EPA Methods manual (12) requires sample preservation with
nitric acid; however, it was discovered part way through the lime neutraliza-
tion study that nitrates interfere  with the determination of boron and many
of the boron data were lost in this manner.  From that time forward, additional
unpreserved samples were collected  and shipped off-site for the boron analysis.
This problem is discussed in further detail in Appendix A.

LIME NEUTRALIZATION

Background

     Lime neutralization represents the Best Practical Technology (BPT) for
acid mine drainage treatment.  A schematic of the lime neutralization process
utilized at the Crown facility is shown in Figure 1.  The neutralization
system consists of two identical treatment processes that operated at 0.9-
liter/sec AMD flow each.  Twin chemical metering pumps injected 100 ml/min
each of bulk trace element solution into the separate treatment lines to
achieve the desired final concentrations shown in Table 5.  The lime neutral-
ization process investigated trace  element removal effectiveness as a function
of pH.   Two pH levels were studied  at one time.  Approximately seven days
were required to characterize a particular pH level (i.e., two days to achieve

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     TABLE 4.  CROWN RAW WATER QUALITY
DURING TRACE ELEMENT STUDY (9/19/77-10/12/77)
Parameter 	
Acidity as CaCOj
Alkalinity
Aluminum
Calcium
Iron, ferrous
Iron, total
Magnes ium
Manganese
pH
r
Sodium
Specific
conductance
Sulfate
Total dissolved
solids
Arsenic
Boron
Cadmium
Chromium
Copper
Mercury
Nickel
Phosphorus
Selenium
Zinc
Unit
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
mg/1
pH
mg/1
ymhos/cm
mg/1

mg/1
mg/1
mg/1
mg/1
mg/1
rag/1
mg/1
mg/1
rag/1
mg/1
mg/1
Mean
440
26
6.6
350
150
160
100
5.0
5.2
350
2610
2380

3350
0.014
0.61
0.0010
0.040
0.022
<0. 00021
0.191
7.89
<0.0011
0.280
Maximum
660
55
14
390
200
200
110
6.2
5.6
410
2950
2660

3640
0.03
0.9
0.002
0.10
0.04
0.0004
0.24
41.0
0.002
0.358
Standard
Minimum deviation
300
0
2.5
310
130
130
90
3.7
4.7
300
2300
2180

3110
0.01
0.3
0.001
0.02
0.01
<0.0002
0.13
0.48
<0.001
0.206
82
1 1
1 j
2r
. b
18
15
14
5ff
. 3
.46
.21
20
153
104

124
0.006
0.19
0.0002
0.019
0 .010
0.00004
0.094
in r 7
10.53
0.0003
0.037

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TABLE 5.  TRACE ELEMENT LEVELS  IN SPIKED ACID MINE DRAINAGE
                           (mg/1)
Element
Arsenic
Boron
Cadmium
Chromium
Copper
Mercury
Nickel
Phosphorus
Selenium
Zinc
Desired
level
2.0
1.0
1.0
0.4
5.0
0.5
0.5
1.0
0.8
5.0
Actual level
Lime
neutralization
1.96
2.36
0.90
0.55
5.30
0.50
0.67
9.85
0.95
5.65
achieved
Reverse
osmosis
2.29
2.01
0.83
0.54
6.18
0.28
0.74
1.50
1.17
6.25
(means)
Ion
exchange
2.47
2.38
0.95
0.63
7.27
0.72
0.86
1.47
1.34
7.44
                             10

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equilibrium and five days data collection).  The study spanned pH levels in
single pH increments between pH 7 and pH 12.  Process A was operated at
pH 11, 9, and 7 in that order while Process B was operated at pH 10, 8, and
12.  No sludge recycling was used during this study.

     A coagulant (Dowell M-144 anionic type) was injected into each flow
stream just prior to the clarifier at approximately a 5-mg/l rate to achieve
optimal clarifier performance.  Samples were taken of the raw AMD, spiked AMD
A, spiked AMD B, product A, and product B, sludge A, and sludge B.  These
samples were collected automatically by composite samplers.  Samples were
sent for analysis twice per day for a daily total of 14 separate samples from
both processes, and 168 samples from the entire neutralization study.

Results
     The operational data are summarized in Table 6 as a function of pH and
indicate normal trends except for slightly high lime usage at pH 9.  These
sorts of anomalies are not unusual for neutralization processes applied to
AMD treatment.

     Analyses for the trace elements and conventional parameters are summa-
rized as a function of pH in Table 7.  Significant removals were observed
for all elements except boron and phosphorus.  The inability to remove phos-
phorus below 1 mg/1 was very unexpected.  Phosphorus removal by lime addition
is state-of-the-art technology in tertiary sewage treatment systems.  Trace
element removal is illustrated graphically in Figure 2.  Individual sample
analyses are given in Appendix C.

     A more detailed breakdown of trace element data is presented in Table 8,
including sludge analyses.  Sludge analysis is very difficult and obtaining
accurate mass balances are even more difficult (material balances are shown in
Table C-3 of the Appendix).  Some interesting phenomena appear in the sludge
data.  For example, sludge trace element levels are significantly higher at
pH 7 than at any higher pH.  This may be partly due to the relatively low
percentage of the conventional pollutants (magnesium, iron, manganese, etc.),
which more completely precipitate at higher pH's and thus the ratio of
concentrations of trace elements to the conventional elements in the sludge
is higher.  Since conventional analyses were not made on the sludge, this
is difficult to verify.  Means of the conventional water analyses are also
summarized in Table 8.  The only conventional parameter that did not meet
or exceed current effluent guidelines standards was manganese at pH 8 and
below.
                                      11

-------
  TRACE
ELEMEHT-
IN1ECTION
    ACID MIKE

    DRAINAGE
  TRACE
 ELEMENT-
INJECTION
                   Pressure
                   Regulator
 trainer     Tuibine
             Flow
            Meier
                 I TlComposite
                 1—'sampler
     Pressure
     Regulator
        ^*3
        ®J
Strainer      Turbine
             Flow
            Meter
                                                                  PROCESS A
                                                    Reactor
                                                                                Sludge  Recycle
                                                                          Coagulant
                                                                      \nH [control        pH
                                                                  	   ,1             i
                                                                  	    •• *PJ^.**rf*"***-w-*^/****"L
                                                                                 THICKENER!
                                         •—•     \         aiunge  nBcjcie                A  *         \1/
                                       Limestont    	-i*	**—A	=>—
                                        Feeder
                                                                                                                        [    [Tap  Water
                                                 PROCESS  B
                                      Reactor
       Sludge Recycle	Dimter Valve


Coagulant
     \     pH icontrol)       pH

       	•—' /«,,„.••>-—	-'*
                                       Limestone
                                        Feeder
                                                           Sludge Recycle
                                                                                                                              TO  DEWATERIH6
                                                                                                                               AND DISPOSAL
                                                                                                                                  FACILITIES
                                             JIUU&C  nci.ji.ic                  22SVX            W    I


                                                                         Magnetic )           I fI
                                                                         CI.U. U.t..'           •—'
                                                                                       Flow  Meter'
                                                                                                       Composite
                                                                                                        Sampler
                        Figure 1.  Schematic flow diagram  for the EPA  neutralization facility.

-------
     TABLE 6.  NEUTRALIZATION OPERATIONAL DATA SUMMARIES FOR
                         TRACE ELEMENT STUDY
Item
Effluent pH
Neutralizer usage,
kg/cu ra
Neutralizer usage,
lb/1000 gal
Neutralizer usage, g/cu
m/ppm influent acidity
Cost, cents/1000 gal*
Cost, cents/cu m
Cost, cents/ 10 cu m/ppm
influent acidity
Utilization efficiency,
percent
Stoichiometric factor
(influent acidity)
Sludge to waste, % of
influent AMD
Dry solids to waste,
lb/1000 gal
Dry solids to waste,
kg/cu ra
Underflow solids,
percent
Effluent turbidity, JTU
Reactor suspended
solids, mg/1
Effluent suspended
solids, mg/1
Mean value
7.0

0.28

2.3

0.6
4.1
1.1

2.4

132

0.8

10

9.9

1.2

1.2
24

380

25
8.0

0.43

3.6

1.2
6.3
1.7

4.4

71

1.5

8.7

4.6

0.5

0.6
11

530

12
9.1

0.82

6.8

2.1
12
3.1

8.0

39

2.8

10

18

2.1

2.1
10

1130

24
10.1

0.85

7.1

1.8
12
3.3

7.0

45

2.5

9.7

8.7

1.0

1.1
7

1310

12
11.0

0.91

7.6

2.0
13
3.5

7.7

44

2.7

10

13

1.6

1.5
7

1440

15
12.1

2,63

22

5.4
39
10

21

51

7.3

14

17

2.0

1.5
3

2500

15

*Lime cost $38.58/tonne ($35.00/ton).

                                     13

-------
            TABLE 7.  SUMMARY OF LIME NEUTRALIZATION WATER
                               QUALITY ANALYSES
Typical
spiked
Parameter influent
Actual median pH
Arsenic
Boron
Cadmium
Chromium
Copper
Mercury
Nickel
P hosphorus
Selenium
Zinc
Acidity
Alkalinity
Aluminum
Calcium
Iron, ferrous
Iron, total
Magnesium
Manganese
Sodium
Specific conductance
Sulfate
Total dissolved solids
5.0
1.96
2.36
0.90
0.54
5.30
0.50
0.66
9.83
0.94
5.65
440
15
8.9
350
150
160
100
5.1
350
2600
2380
3340
Nominal
7
7.0
0.10
2.25
0.18
0.04
0.30
0.02
0.34
3.81
0.05
1.01
13
47
0.40
470
0.25
1.4
100
3.7
340
2630
2400
3310
8
7.9
0.05
-
0.06
0.07
0.16
0.01
0.18
2.67
0.06
0.23
-0-
36
0.33
460
-0-
0.65
96
2.5
340
2540
2020
3160
9
8.9
0.04
-
0.08
0.07
0.11
0.01
0.08
2.30
0.16
0.11
-0-
44
0.31
480
-0-
0.33
65
0.19
330
2430
2160
3040
pH of effluent
10
10.0
0.02
1.68
0.01
0.06
0.05
0.01
0.06
2.88
0.28
0.07
-0-
50
0.40
530
-0-
0.40
25
0.06
340
2840
2250
3160
11
10.9
0.03
1.90
0.01
0.05
0.06
0.02
0.06
3.56
0.39
0.11
-0-
90
0.40
610
-0-
0.35
5.0
0.06
340
2840
2340
3290
12
12.2
0.02
1.45
0.01
0.04
0.08
0.01
0.06
1.09
0.15
0.09
-0-
1220
0.23
970
-0-
0.05
0.06
0.05
340
5960
3230
4540
All units are mg/1 except for pH and specific conductance  (ymhos/cm)
                                     14

-------
                                                                   o.oi
                                                             12
Figure 2.  The  effect of  pH  on trace element concentration in
           neutralization  process effluent.
the
                                  15

-------
 TABLE 8.   DETAILED SUMMARY OF LIME NEUTRALIZATION
                    CHEMICAL ANALYSES
(mg/1  for  spiked feed and product, yg/g for sludge
Nominal
Parameter Sample
Arsenic Spiked feed

Product

Sludge

Boron Spiked feed

Product

Sludge

Cadmium Spiked feed

Product

Sludge

Chromium Spiked feed

Product

Sludge

Statistic
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
7
2.01
0.14
0.10
0.01
46
8.2
2.45
0.56
2.25
0.54
17
3.7
0.67
0.08
0.18
0.02
12
2.3
0.49
0.05
0.04
0.01
8.82
1.6

1
0
0
0

9




4
2
0
0
0
0
6
6
0
0
0
0
2
1
8
.97
.26
.05
.008
13
.88
_

-

.01
.17
.86
.15
.06
.01
.86
.63
.58
.07
.07
.04
.83
.79
9
1.88
0.86
0.04
0.005
29
2.71
_

-

4.74
2.41
0.86
0.19
0.08
0.16
15
2.80
0.56
0.06
0.07
0.03
5.82
0.53
pH

10
1
0
0
0

3
2
0
1
0
1
1
1
0
0
0
8
2
0
0
0
0
2
0
.75
.24
.02
.01
13
.05
.55
.21
.68
.13
.92
.12
.03
.06
.01
.01
.48
.12
.53
.08
.06
.01
.84
.62
2
0
0
0

3
2
0
1
0
5
2
1
0
0
0

1
0
0
0
0
4
0

11
.11
.18
.03
.01
23
.41
.08
.21
.90
.27
.44
.79
.30
.06
.01
.01
15
.49
.65
.06
.05
.01
.50
.54


2
0
0
0
8
4
2
0
1
0

3
0
0
0
0
3
1
0
0
0
0
1
0

12
.02
.15
.02
.004
.5
.5
.35
.60
.45
.47
12
.3
.66
.12
.01
.02
.20
.00
.46
.07
.04
.01
.67
.56
(continued)
                          16

-------
TABLE 8 (continued)
Nominal
Parameter
Copper


Mercury


Nickel


Phosphorus


Sample
Spiked feed
Product
Sludge
Spiked feed
Product
Sludge
Spiked feed
Product
Sludge
Spiked feed
Product
Sludge
Statistic
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
7
5.29
0.47
0.30
0.06
115
21
0.50
0.04
0.02
0.002
7.55
1.42
0.66
0.05
0.34
0.04
6.57
0.77
7.03
2.34
3.81
1.13
56
17
8
5.40
0.84
0.16
0.02
31
25
0.48
0.06
0.014
0.003
2.54
1.91
0.68
0.08
0.18
0.05
3.46
2.81
5.88
2.70
2.67
1.21
14
5.92
9
5.18
0.58
0.11
0.01
72
8.49
0.47
0.09
0.009
0.002
4.89
0.45
0.67
0.07
0.08
0.05
9.10
0.73
5.66
2.76
2.30
1.23
42
5.81
PH
10
4.80
0.35
0.05
0.01
31
7.81
0.47
0.02
0.009
0.003
2.03
0.53
0.63
0.03
0.06
0.01
4.16
1.02
17
16
2.88
1.64
19
3.82

11
6.15
0.18
0.06
0.03
56
6.80
0.60
0.05
0.020
0.010
3.90
0.47
0.74
0.04
0.06
0.01
7.07
0.61
17
17
3.56
2.03
34
10

12
5.00
0.73
0.08
0.03
37
44
0.47
0.02
0.010
0.006
1.78
0.76
0.61
0.09
0.06
0.01
3.11
1.96
6.55
2.49
1.09
0.46
9.04
2.69
(continued)
          17

-------
TABLE 8 (continued)
Nominal pH
Parameter
Selenium


Zinc


Acidity

Alkalinity

Aluminum

Calcium

Sample
Spiked feed
Product
Sludge
Spiked feed
Product
Sludge
Spiked feed
Product
Spiked feed
Product
Spiked feed
Product
Spiked feed
Product
Statistic
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Std. dev.
Mean
Mean
Mean
Mean
Mean
Mean
Mean
7
1.01
0.10
0.05
0.01
16
2.45
5.61
0.60
1.01
0.11
104
18
460
13
14
47
13
0.40
360
Mean 470
(continued)
8
0.95
0.18
0.06
0.02
4.08
1.85
5.66
0.70
0.23
0.03
39
28
400
0
17
36
7.7
0.33
340
460
9
0.84
0.13
0.16
0.02
9.38
1.16
5.40
0.56
0.11
0.02
84
8.14
400
0
17
44
9.0
0.31
340
480
10
0.80
0.05
0.28
0.05
2.96
0.52
5.32
0.21
0.07
0.03
38
8.32
450
0
15
50
6.6
0.40
350
530
11
1.06
0.10
0.39
0.04
4.79
0.60
6.57
0.32
0.11
0.07
64
7.68
450
0
14
90
5.4
0.40
340
610
12
1.01
0.09
0.15
0.02
3.38
1.91
5.32
1.00
0.09
0.09
26
15
490
0
14
1220
11
0.23
360
970
       18

-------
                            TABLE 8 (continued)


Parameter Sample Statistic
Iron,

ferrous Spiked feed Mean
Product Mean
Nominal pH
7 8 9 10 11 12
150 160 160 150 150 150
0.25 00000
Iron, total   Spiked feed    Mean

              Product        Mean


Magnesium     Spiked feed    Mean

              Product        Mean


Manganese     Spiked feed    Mean

              Product        Mean
Sodium
Spiked feed    Mean

Product        Mean
Specific      Spiked feed    Mean
 conductance
              Product        Mean
Sulfate
Spiked feed    Mean

Product        Mean
Total         Spiked feed    Mean
 dissolved
 solids       Product        Mean
 160   160   160   150    160    160

 1.4   0.65  0.33  0.40   0.35   0.05



 100   100   100    98     98    100

 100    96    65    25    5.0    0.06



 4.8   5.4   5.3   5.0    5.0    4.8

 3.7   2.5   0.19  0.06   0.06   0.05



 360   350   350   340    340    360

 340   340   330   340    340    340



2630  2460  2470  2730   2700   2620

2630  2540  2430  2840   2840   5960



2470  2350  2350  2170   2310   2450

2400  2020  2160  2250   2340   3230



3460  3310  3310  3330   3250   3440

3310  3160  3040  3160   3290   4540
All units are mg/1 except for pH and specific conductance  (ymhos/cm).
                                       19

-------
REVERSE OSMOSIS

     A Universal Oil  Products  (13)  spiral-wound  type  reverse  osmosis unit
 (Figure 3) with a  capacity  of  15  cu m/day  (4,000 gpd)  of  product  flow was
studied in a one-day  test.   The unit operated  at 35.15 kg/sq  cm  (500 psi)
to  achieve optimal  rejection characteristics,  at a moderate recovery rate
 (40 percent) to prevent  fouling interferences  with rejection  ability, at a
minimum 10:1 brine:product  flow ratio to prevent boundary layer precipitation
-problems, and with  sulfuric acid  injection  to  control  iron precipitation by
maintaining an influent  pH  below  3.   The osmotic pressure of  the  AMD,
measured during the study,  was 1.7  kg/sq cm (24  psi).

     Operational parameters for the study are  presented in Table  9.  Although
the system was on-stream for several days,  all of the  water samples were col-
lected on a grab-sample  basis throughout one day's operation.  Four grab-
samples were taken  per data set (i.e.,  raw  AMD,  spiked AMD, product, and
brine).  Ten sets of  samples (40  samples total)  were  collected.

     A summary of chemical  data is  presented in  Table  10.  Individual data are
presented in Appendix C.  Since reverse osmosis  product quality is not
directly related to ion  solubility,  rejection  rate or  percent removal calcula-
tions are appropriate.   As  seen in  Table 10, the rejections were  below  80
percent for boron,  mercury,  and phosphorus  and were above 90  percent for the
remainder of the trace elements.  The cellulose  acetate membrane  used in this
study (Universal Oil  Products Model  4T38) is characterized by high rejection
rates.  This is apparent  with the 99.9-percent rejection  observed on sodium,
a monovalent ion, which  is  normally rejected at  a 93-percent  rate.

     Material balances of the system are shown in Table C-6 of the Appendix
and were satisfactory (within 15-percent indicated gain or loss)  for all
elements except mercury  where 54 percent of the  indicated influent failed
to  exit the system.   It  was postulated  by Stuewe and Hall  (14) that the
mercury was precipitated  upon contact with  the sulfuric acid  pretreatment
injection and was collected on the  filters  in  front of the reverse osmosis
unit and/or on the  membranes.  Tests to investigate this  confirmed the
presence of mercury on the  filters.   No analyses were  made on the membrane.
                                     20

-------
  TRACE ELEMENT INJECTION

  J
  —IACID MINE DRAINAGE
                         f
                      H2S04
                    INJECTION
                              r-O
  10 MICRON
  CARTRIGE FILTERS

-"—PH PROBE FOR H2SO4 CONTROL
   51.15 kg/cm2
   (500 psi) max.
               REVERSE OSMOSIS UNIT
   1.2 kg/cm2
   (18 psi)
I TUBE 1 I 	

I TUBE 2 h |
T

-1


1-
TUBE 3 h- 1
1
BACK
PRESSURE (P
REGULATOR!
                                                     PRODUCT   RESTRICTING^
                                                                 VALVE
                                                                        BRINE
Figure 3.  Flow diagram for 4000-gpd spiral-wound reverse osmosis unit.

-------
        TABLE 9.  MEAN OPERATING  PARAMETERS  FOR CROWN SPIRAL-WOUND
                           REVERSE OSMOSIS STUDY
	Parameter	Value

AMD feed flow, liter/sec                                       0.65
AMD feed flow, gpm                                            10.3

Product flow, liter/sec                                        0.25
Product flow, gpm                                              3.9

Brine flow, liter/sec                                          0.40
Brine flow, gpm                                                6.4

Water recovery, percent                                       38

Feed pressure, kg/cm                                          35.50
Feed pressure, psi                                           505

Feed temperature, °C                                          15.5
Feed temperature, °F                                          60

Tube one flux, Iiters/m2/day @ 35.15 kg/cm2 and 25°C         616
Tube one flux, gal/ft2/day @ 500 psi and 77°F                 15.1

Tube two flux, Iiters/m2/day @ 35.15 kg/cm2 and 25°C         600
Tube two flux, gal/ft2/day @ 500 psi and 77°F                 14.7

Tube three flux, Iiters/m2/day @ 35.15 kg/cm2 and 25°C       587
Tube three flux, gal/ftz/day @ 500 psi and 77°F               14.4
                                     22

-------
             TABLE 10.  REVERSE OSMOSIS WATER QUALITY SUMMARY
Parameter
Arsenic
Boron
Cadmium
Chromium
Copper
Mercury
Nickel
Phosphorus
Selenium
Zinc
Spiked feed
Mean
2.29
2.01
0.83
0.54
6.18
0.28
0.74
1.50
1.17
6.25
Std.dev.
0.14
0.17
0.06
0.06
0.35
0.02
0.05
0.35
0.17
0.54
Product
Mean Std.dev.
0.01
0.88
0.006
0.01
0.01
0.06
0.01
0.32
0.11
0.06
0
0.20
0.009
0
0
0.02
0
0.13
0.01
0.04
Brine R
Mean
3.58
3.08
1.22
0.82
9.12
0.17
1.10
1.93
1.83
9.63
Std.dev.
0.30
0.29
0.13
0.12
0.95
0.02
0.12
0.42
0.15
1.15
:ejections,a
percent
99.6
56.2
99.3
98.1
99.8
78.6
98.6
78.7
90.6
99.0
pH                 2.2
Acidity           1340
Aluminum           5.0
Calcium            370
Iron, ferrous      150
Iron, total        170
Magnesium          110
Manganese          5.0
Sodium             400
Specific
  conductance     5980
Sulfate           2990
Total dissolved
  solids          4040
  2.0
130
  0.20
  0.60
 <0.10
  0.30
  0.20
  0.05
  0.30

   60
   22

   24
 3.6
2070
 7.8
 590
 230
 270
 180
 7.1
 640

8540
4610

6290
90.
96.
99.8
99.9
99.8
99.8
99.0
99.9

99.0
99.3

99.4
*A11 units are mg/1 except for pH and specific conductance(gmhos/cm)
Rejection equals feed concentration - product concentration
                              feed concentration
                           X 100.
                                     23

-------
ION EXCHANGE

     A two-resin ion exchange unit  (Figures 4 and 5) was studied for effec-
tiveness of trace element removal in a one-day test.  The ion exchange system,
which operated at a 40-liter/min  (10.5-gpm) product flow rate, was being
regenerated at high dosage rates to achieve minimum cation leakage rates.
The intended regeneration dosage for the cation column was 144 grams of
sulfuric acid per liter of resin; for the anion column, the intended dosage
was 64 grams of sodium hydroxide per liter of resin.  Six grab samples (raw
AMD, spiked AMD, cation effluent, anion effluent, cation regenerant, and
anion regenerant) were taken per data set.  While the grab sample data are
indicative of system response, they do not truly represent the integrated
flow from the system.  The choice to take grab samples rather than composites
was made because the effluent from the ion exchange system is constantly
changing in quality and it was desirable to monitor trends in addition to
overall effectiveness.  Eight sets of grab samples were taken during the
one-day study period for a total of 48 separate samples from the test.
Detailed design specifications for the two-resin unit are given in Table 11.
The two-resin system operated with a strong-acid cation resin that exchanged
H+ ions for the cations (arsenic, cadmium, chromium, etc.,) in the AMD.  The
effluent from the cation column becomes mostly sulfuric acid since the
predominant anion in the AMD is sulfate.  This solution of H S04 then enters
the weak-base resin column where the acid is sorbed by the weak-base resin.

     The actual operating parameters for the unit during the test study are
presented in Table 12.  These data were based on five regeneration cycles,
including two cycles from which water samples were collected.  The cost of
regenerant chemicals alone for this study was $9.70 per 1000 gallons,
illustrating that the unit was operated in the mode optimum for effluent
quality and not optimum for cost/effectiveness.  Regenerant utilization
efficiencies for the sulfuric acid and sodium hydroxide were 22 and 42 per-
cent respectively.

    The water quality analyses for the spiked feed and cation and anion
column effluents are summarized in Table 13 (individual data are in Appendix
C.) The cation column was not particularly effective in arsenic, boron, or
selenium removal and, interestingly, the phosphorus content in the cation
effluent was significantly higher than in the influent.

     The anion column (and its alkaline pH 10 conditions) very significantly
reduced the residual trace element concentrations as most of the elements
precipitated within the column itself at pH 10.  Arsenic and boron were not
removed, however, below 0.5 mg/1 by the process.  Additional phosphorus was
added by the anion column, although not to the degree that the cation column
increased phosphorus levels.  Some insight into the phosphorus increase
phenomenon is illustrated in Figures 6 and 7, showing the trace element
trends throughout one of the two service cycles in which samples were
collected.  Phosphorus levels from the cation column (Figure 6) dropped
sharply as the column went back on-line, indicated that the rinses following
                                      24

-------
regeneration were not long enough for effective phosphorus reduction.  The
unit operation could easily be modified to rinse longer and do a better job
on phosphorus removal; however, the improvement would not have been worth
the cost.  The phosphorus phenomenon may have been analytical error;
although, this is not felt to be the case because the data immediately looked
suspect and the phosphorus analyses were repeated.  It is more likely that
the cation backwash cycle, which uses AMD, loaded the bottom of the column
with phosphorus since backwash is accomplished upflow.  Then the downflow
regeneration was not sufficient to remove all of the phosphorus from the
bottom of the cation column.  When the column went back on-line, the
phosphorus on the resin at the bottom of the column exchanged with cations
in the AMD passing through and an increase in phosphorus was observed.
Regardless of the reason, the ion exchange system was ineffective in
phosphorus removal.

     In terms of conventional AMD parameters, the cation column effluent
dropped to pH 1.9, indicative of the exchange of H+ ions for the cations in
the raw AMD and resulting in a solution containing predominately sulfuric
acid.  Additional reductions of cations were observed in the anion column
as insoluble hydroxides formed at the pH 10 conditions and precipitated
within the resin bed.  All acidity was sorbed by the weak-base resin and
alkalinity and sodium increased because of excess NaOH, which was used as
the regenerant.  The trends of the conventional pollutants during one of the
service cycles are illustrated in Figures 8 and 9.
                                     25

-------
Sulfuric acid
Trace element injection i
¥ Acid mine drainage V





K)
&

I
To Waste
Backwash)


Backwash
1 \







CATION
EXCHANGER

4 1
1
To wa








ste
Sodium
hydroxide
1





Bac





^^^M
kw
T
1 _
T jr



ANION
EXCHANGE!

-fl1

1
To waste
(Backwash)



» (To
o waste
(Regeneration and rinses) (Regeneration and rinses )
                                                                Product
                                                             (To  pH adjustment
                                                              filtration, and
                                                              chlorination)
Figure  4. Schematic flow diagram of EPA 2-resin  ion exchange  unit.

-------
-
                     CATION
                    COLUMN
            FLOW AND WATER
 ANION          QUALITY
COLUMN    MONITORING PANEL
           Figure 5. Photograph of the ion exchange installation at Crown.

-------
TABLE 11.  GENERAL SPECIFICATIONS FOR EPA  ION EXCHANGE TREATMENT UNIT
                           (TWO-RESIN SYSTEM)
Cation exchanger
Type
Resin
Volume of resin, cu m
Approximate tank size, cm
Approximate tank area, sq m
Service flow rate, liters/min
Service flow rate, liters/min/cu m
Service flow direction
Backwash flow rate, liters/min
Backwash flow rate, liters/min/sq m
Backwash flow direction
Bed expansion during backwash, percent
Regenerant flow rate, liters/min
Regenerant flow rate, liters/min/sq m
Regenerant flow rate, liters/min/cu m
Regenerant flow direction
First rinse flow rate, liters/min
First rinse flow rate, liters/min/cu m
First rinse flow direction
Second rinse flow rate, liters/min
Second rinse flow rate, liters/min/cu m
Second flow direction
Strong acid
Duolite C-20
0.93
91 x 213
0.65
40
43
Down flow
115
180
Upf low
50
100
150
110
Downf low
100
110
Downf low
115
120
Downflow
Regenerant Sulfuric acid
Regenerant concentration, percent by weight
2
An ion exchanger
Weak base
Dowex WGR
0.54
76 x 213
0.45
40
74
Downflow
100
190
Upflow
75
40
90
74
Downflow
40
90
Downflow
100
190
Downflow
Sodium hydroxide
3 to 5
28

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TABLE 12.   AVERAGE VALUES FOR THE ION EXCHANGE OPERATING PARAMETERS

Parameter
Regenerant
Bulk regenerant cost, cents/kg
Bulk solution concentration, weight percent
Desired regenerant concentration, weight percent
Desired dosage, grams of regenerant/ liter of resin
Desired dosage, pounds of regenerant/cu ft of resin
Influent load, milligrams/liter as CaCO?
Effluent load (leakage), mi] ligrams/ liter as CaC05
Effective removal, milligrams/liter as CaCO,
Number of regeneration cycles during this test
Average actual dosage, grams of regenerant/liter
of resin
Average actual regenerant concentration, percent
by weight
Exchanger capacity, grams/ liter of resin as CaCO^
Exchanger capacity, kilograins/cu ft of resin as CaCO,
Regenerant utilization efficiency, percent
Regenerant cost, cents/cu m
Regenerant cost, cents/1000 gal
Total volume to waste, liters/regeneration
Cation
H2S04
7.72
93
2.0
144
9
2450
200
2250
5
140
2.0
30.8
13.4
22
93
350
10650
An ion
NaOH
11.0*
20
4.0
64
4
2650
0
2650
5
61
3.8
36.1
15.8
42
110
420
3200
  *Price of 50-percent concentration and diluting on-site to 20 percent
                                  29

-------
TABLE 13.  ION EXCHANGE WATER QUALITY SUMMARY
— ~ "~ "
Parameter
Arsenic
Boron
Cadmium
Chromium
Copper
Mercury
Nickel
Phosphorus
Selenium
Zinc
PH
Acidity
Alkalinity
Aluminum
Calcium
Iron, ferrous
Iron, total
Magnesium
Manganese
Sodium
Specific
conductance
Sulfate
Total dissolved
solids
Spiked feed
Mean Std.dev
2.47 0.55
2.38 0.30
0.95 0.12
0.63 0.08
7.27 0.86
0.72 0.08
0.86 0.09
1.47 0.39
1.34 0.27
7.44 0.84
4.8
500
14
5.7
350
140
160
100
3.9
380
2740
2400
3340
Cation effluent
Mean Std.dev.
1.68 0.20
2.20 0.30
0.04 0.09
0.05 0.02
0.11 0.05
0.07 0.06
0.02 0.01
8.86 8.23
1.19 0.13
0.14 0.05
1.9
2640
0
0.20
11
2.1
2.1
2.6
0.09
71
21,600
910
1000
Product
Mean
0.52
0.58
0.001
0.01
0.03
0.001
0.02
9.71
0.09
0.03
9.9
0
280
0.19
8.7
0
0.05
2.2
0.05
330
1240
580
900
(anion effluent
Std.dev.
0.58
0.58
0.001
0.01
0.03
0.003
0.02
5.54
0.14
0.02













30

-------
   10
  1.0
 0>
 E

z
o
at
t-
5 o.i
U
Z
o
 0.01
0.001
        1
1
1
1
1
1
                                                        6000    7000
0      1000     2000     3000     4000     5000
                    CUMULATIVE  FLOW, liters

Figure 6. Trace element trends throughout the cation service cycle.
                                                                   1.0
                                                                 o>
                                                                 E

                                                                 z"
                                                                 O
                                                               0.1 Z
                                                                 U
                                                                 Z
                                                                 O
                                                                 u
                                                                   0.01
                                                               0.001
                                   31

-------
    10
   1.0
a

E
O

S  o.
O
u
  0.01
0.001
              fAD/MILI
            1000    2000     3000    4000    5000

                           CUMULATIVE FLOW, liters
60007000
           10
           1.0
              o>
              E
           0.1
              oc


              Z
              ui
              U

              Z

              O
                                                                  0.01
           0.001
     Figure 7. Trace element trends throughout the anion service cycle.
                                   32

-------
1000
 100
-10
 0)
 E

z"
O
p
<

H-
z
UJ

Z
o
U1.0
  0.1
 0.01
                            -£4
                                                E

                                                z"
                                                o
                                                                      u
                                                                      Z
                                                                      o
                                                                   1.0U
                                                                   0.1
                                                                   0.01
    0       1000    2000    3000   4000     5000     6000    7000

                        CUMULATIVE FLOW, liters
  Figure 8.  Conventional pollutant trends throughout the onion service cycle.
                                   33

-------
 1000 - o
   100-
'v



o
   0.1 -
  0.01
        O-
               ACIDITY
          TOTAL OlStOlVtD SOLIDS
        O-
                        -O-
            MAONiilUM
                                                           -o
                        CUMULATIVE FLOW, liters
                                                                    1000
                                                                    100
                                                                       a
                                                                       E



                                                                      O
                                                                      ut
                                                                      u
                                                                    1.0
                                                                    0.1
                                                                    0.01
                                                               Tffoo
Figure 9.  Conventional pollutant trends throughout the cation service cycle.



                                   34

-------
WASTE TREATMENT AND DISPOSAL

     Each of the three processes studied produces a waste stream in which the
pollutant concentration is significantly higher (hopefully) than in the raw
AMD.  Lime neutralization produces a sludge, which is very low in solids (2%)
and is thus largely water.  Reverse osmosis produces a low-pH brine that
must be further treated with alkali neutralization and again produces a sludge
similar to the lime sludge above, except for increased pollutant levels.  The
waste regenerants from the cation (acid) and anion (alkaline) exchange
columns would be combined for partial neutralization and then fully neutral-
ized by the addition of the appropriate alkali reagent to precipitate the
metals, again producing a neutralization sludge similar to the first two.
Lime would probably not be used to treat the RO and IE wastes because the
increased calcium and sulfate levels would almost certainly result in heavy
gypsum formation within the neutralization system.  Most probably soda ash
or sodium hydroxide would be used.

     The effluents from the RO and IE waste neutralization would be high in
TDS and calcium, and extremely high in sodium sulfate concentrations.

     The presence of trace elements in the AMD source and their subsequent
removal by the process and eventual concentration in a neutralization sludge
adds additional concerns to the disposal of AMD sludges.  Traditionally,
AMD neutralization systems either return sludge to an abandoned area of a
deep mine or contain it in an impoundment sized for the life of the mine.
Abandonment of an impoundment after the mine ceases operation is a rarely
addressed point.  It is assumed that the pond would be drained, the sludge
spread and air dried, and the area backfilled to cover the sludge.

     The status of AMD neutralization sludge, in terms of the Resource
Conservation and Recovery Act (RCRA) and the Hazardous Waste Act, is
unresolved at this time.  The presence of high levels of trace elements will
certainly be of concern to EPA in disposal considerations.
                                       35

-------
                                  REFERENCES

 1.    Wilmoth,  Roger C.  and James L.  Kennedy.   Combination Limestone-Lime
      Treatment of Acid  Mine Drainage.   Paper  given at  the NCA/BCR Coal
      Conference and EXPO III,  Louisville,  Kentucky.   1976.

 2.    Wilmoth,  Roger C.   Limestone and  Lime Neutralization of Ferrous  Iron
      Acid  Mine Drainage.   U.  S.  Environmental Protection Agency Report
      600/2-77-101,  Cincinnati, Ohio.   1977.

 3.    Wilmoth,  Roger C.  and Robert B. Scott.   Water Recovery from Acid Mine
      Drainage.   In:   Proceedings 3rd National Conference Complete WateReuse
      Cincinnati,  Ohio.  June 1976.

 4.    Intorre,  B.,  et  al.   Treatment of Acid Mine Wastes  by  Ion  Exchange
      Resins.   In:  Proceedings National Conference  Complete  WateReuse
      April  1973.

 5.    Gulf  Environmental  Systems  Company.   Acid Mine Waste Treatment Using
      Reverse Osmosis.   U.  S. Environmental Protection Agency Report 14010 DYG
      08/71, Washington,  DC.  1971.

 6.    Wilmoth,  Roger C., Donald G. Mason, and  Mahendra Gupta.  Treatment of
      Ferrous Iron Acid Mine Drainage by Reverse Osmosis.  Paper  given at
      the Fourth Symposium  on Coal Mine Drainage Research, Pittsburgh,
      Pennsylvania.  1972.

 7.    Wilmoth, Roger C., Robert B. Scott, and  Eugene F. Harris.  Application
      of Ion Exchange to Acid Mine Drainage Treatment.  Paper given at 32nd
      Annual Purdue Industrial Waste Conference, Purdue University.  1977.

 8.    Development Document  for Interim  Final and Proposed Effluent Limitations
      Guidelines and New Source Performance Standards for the Ore Mining and
      Dressing Industry,  EPA 440/1-75-061, Washington, DC.  October 1975.

9.   Development Document  for Interim  Final Effluent Limitations Guidelines
     and New Source Performance Standards for the Coal Mining Point Source
     Category,  EPA 440/1-75-057 Group  II, Washington, DC.  October 1975.

10.   Ross,  Laurence W.  Removal of Heavy Metals from Mine Drainage by
     Precipitation, EPA Report 671/2-73-080, Washington,  DC.  September 1973.

11.   Miller, Jan D.  Removal of Dissolved Contaminants from Mine Drainage,
     EPA-R2-72-130, Washington,  DC.  December, 1972.

12.   Methods for Chemical Analysis of Water and Wastes.   EPA 625/16-74-003.
     Cincinnati, Ohio.  1974.
                                     36

-------
13.  Wilmoth, Roger C.   Applications of Reverse Osmosis to Acid Mine
     Drainage Treatment.  U. S.  Environmental Protection Agency Report
     670/2-73-100, Cincinnati, Ohio.  1973.

14.  Stuewe, C. and J.  Hall, personal communication. November 1977.

15.  Feldman, Cyrus.  Evaporation of Boron from Acid Solutions and Residues,
     Anal. Chem. 33_:1916-1920.  1961.

16.  Handbook for Analytical Quality Control in Water and Wastewater
     Laboratories.  U.  S. EPA, Analytical Quality Control Laboratory,
     Cincinnati, Ohio.   1972.
                                     37

-------
                                  APPENDIX A

                       DISCUSSION OF ANALYTICAL RESULTS


      This section (1) reviews in detail the analytical problems encountered
 during the study, (2) gives an analytical interpretation of the significance
 and trends of the data, and (3) reviews the quality assurance program and
 present examples of the reporting format and QA results developed by Stewart
 Laboratories.

 PROBLEMS ENCOUNTERED

      In the initial  stages of developing the program for preserving and
 shipping the samples from the EPA Crown site to Knoxville,  Tennessee,
 Hydroscience and their analytical subcontractor,  Stewart Laboratories,  reviewed
 the EPA methods manual (12) for tne proper preservation procedures.   The manual
 listed two techniques which were felt  to cover the compounds in this study.
 One preservation procedure was for metals and required acidification with 1-1
 nitric acid;  the other procedure was for phosphorus which required acidification
 with sulfuric  acid.   Since nitric acid is used in the digestion for total
 phosphorus analysis, it was recommended that duplicate samples, including
 a different  preservative for each,  were unnecessary and samples preserved with
 nitric would  be satisfactory.   This procedure was reviewed  with the  EPA
 personnel  during start-up,  and then the sampling  program began.  When the
 analytical program was begun by Stewart,  it  soon  became evident that nitrates
 were interfering in  the boron  methodology by giving erratic and odd  results.
 This problem occurred essentially for  the following reasons:

 1.    Lack  of experience within Hydroscience,  Stewart  Laboratories, and  the EPA
      in  analyzing for boron.

 2.    The EPA manual  did not  have  a  preservation technique for boron  or  a
      warning in  the  metals  section  not  to  preserve  samples  requiring boron
      analysis by nitric  acid addition.  The new edition  of  the  manual will
      have  such  a warning.

      The solution of the problem was first to  stop  the boron analysis on the
preserved  samples, send  small  unpreserved  samples for  subsequent boron
analysis (started on  10/5/77), and  then look at alternate analytical techniques
to detect boron in the presence of  large concentrations of nitrates.  The first
alternate analytical  technique tried was a modification of the  Feldman
method (15).  This method requires the addition of mannitol to  the sample,
reduction to a residue, and  analysis by an emission spectrographic method usine
a powder d-c arc technique.  This method gave an extremely hygroscopic residue
which was impossible to weigh accurately.  A USGS technique was tested that
                                      38

-------
called for a sulfuric acid addition to the sample followed by volume reduction
to a residue at temperatures less than 225°C.   Stewart attempted the technique
several times on standards, samples and spiked samples, but did not get
acceptable results.

     Since significant time had been expended unsuccessfully in an effort to
find an alternative technique, and funds for further such work were not avail-
able in this task, all attempts to find a way of analyzing the preserved
samples for boron were stopped.

     Later during the task, alledgedly unpreserved samples from the early lime
neutralization runs were found at the EPA Crown site.  They were sent to
Hydroscience for boron analysis.  During a quick screening for nitrates prior
to analysis, it was found that the only good samples were those taken during
the period from September 21, 1977 and September 23, 1977.  This, however, was
helpful in filling some of the boron data gaps.

     A similar problem also occurred with the sludge samples.  They were not
preserved, but the EPA digestion procedure for metals calls for a nitric-
sulfuric acid digestion.  A separate sulfuric acid digestion for boron only
was incorporated into the procedure.  At about the same time, it was realized
that Stewart Laboratories was decanting the sludge samples for analysis of
the "sludge" portion only; therefore, the retainer samples were requested and
the analyses were repeated using the total sample and the modified digestion
procedure mentioned above.

ANALYTICAL INTERPRETATION

     Since this report consists of a great deal of analytical data for metals
at the ppm and ppb levels, it is worthwhile to review the meaning of the
data and its interpretation based on detection limits of the analytical
methods utilized and the precision and accuracy data developed  in the QA
program.  It is also important  to review the types of data anomalies that
occasionally occurred.

     Three significant figures  were realistically reported for  all elements
except mercury and boron.  The  analytical method and our studies showed a
reproducible detection limit  for mercury to be 0.0002 mg/liter; therefore,
in some places, four significant figures were reported.  In  the case of boron,
only two significant figures  were reported, since the detection limit  is  0.1
mg/liter.  For the purposes of  data summaries as appear  in the  text, these
were generally rounded to  two decimal places.

     Throughout the  study  replicate samples were analyzed  as blind  splits,
and occasionally the difference encountered in these  "duplicates" was  greater
than expected  from the precision and  accuracy data.  This  variation has been
attributed to  the inability of the  analyst to obtain  a proper  sample for
analysis or  to  an error  in making  a proper "true" split.

     An unexpected result  of  this  study was that the accuracy  and  precision
data  for the sludge  samples  (containing  fine  settleable  solids) were equal
to  or  better than the  feed and product water  samples for all the  metals  in
the  study.
                                       39

-------
      In reviewing the analytical results from the reverse osmosis unit run
 it was found that mercury in the spiked AMD was consistently lower than
 expected (by approximately one-half),  which was first thought to be an
 analytical  error.  In reviewing the data and performing additional analysis,
 the analysis was  eliminated as the problem source.   A definite answer was
 not found for the data anomalies,  but  could have been due to a process
 phenomena (e.g.,  addition of sulfuric  acid with subsequent precipitation
 of mercuric sulfate,  which could have  been removed  by an RO prefilter prior
 to sampling the spiked AMD feed).

 REVIEW OF QUALITY ASSURANCE PROGRAM

      The essential and important part  of this quality assurance program was
 to provide  quality control  checks  on the instrumentation,  personnel,  and
 analytical  procedures.  Hydroscience and Stewart Laboratories used the EPA
 Handbook for Analytical Quality Control  in Water and Wastewater (16)  as  the
 minimum standard  quality  control reference.   The overall program consisted
 of the Stewart Laboratories  program outlined below,  along  with frequent  reviews
 by Hydroscience and submission  of  blank  and spiked  standards  during the  course
 of the study.

      The Analytical Quality  Control Program of Stewart  Laboratories,  Inc.
 (SLI)  consisted of four separate areas integrated into  the  total  effort; namely,
 the  intralaboratory quality  control program,  interlaboratory  studies,
 collaborative testing projects,  and external  quality control  programs  imposed
 and  administered  by Hydroscience.

 INTRALABORATORY QUALITY CONTROL  PROGRAM

      The  attainment and maintenance of the program was  the  direct  responsibility
 of the  SLI  laboratory director.  This phase  of the program was  divided into
 two  segments — a routine program  applicable to all test  procedures  and  custom
 internal  QA programs designed for  individual  contract efforts.

 Routine  Program

     The quality control procedures associated with the routine intralaboratory
program, which are applicable to all test procedures, were also applied to the
project.  This included such items as:

     a.   Deionized water was continuously monitored by a conductance method
          to assure that ASTM Type II grade reagent water was used for all
          analytical procedures.

     b.   Reference standards were NBS  or certified to meet NBS standards.

     c.   Wavelength standard curves and standard cells for spectrophoto-
          meters were  checked during the project.

     d.   Analytical balances were checked against reference weights (NBS
          Class S) on  a one-a-month schedule.
                                     40

-------
     e.   All laboratory reagents met ACS standards and were labeled
          contents, date of preparation, and expiration when applicable.

     f.   Volumetric glassware was NBS Class A.

     g.   Glassware was checked for cleanliness and for detergent removal
          prior to each analysis run.

Custom Internal Quality Control Programs

     In addition to the general program, custom internal quality control
programs are designed for individual contract efforts.  For purposes of this
project, the internal QA program included blind splits of actual samples
(replicate analyses); blind random analysis of standard reference materials;
and recovery studies with spiked samples to establish method precision and
accuracy.  One sample from each analysis lot or 15% of the samples in an
analysis lot were run as blind splits.  During the course of the project,
replicates and spikes were done on all types of samples (17 types - 7
replicates of each one).  Reference standards obtained from Environmental
Resource Associates were analyzed along with the samples.

     Representative sample bottles from the cleaning and preparation operation
were selected by Hydroscience and filled with previously tested "blank" water.
These blank control samples were analyzed by the appropriate techniques before
the final shipment of the containers to the field and were found to be free of
possible contamination or interferences.

     During the course of the project, the following types of data were
produced to check the QA program and determine the necessary statistics to
evaluate the data:

     a.   Daily standard curves.

     b.   Precision data on all parameters in all different types of samples.

     c.   Accuracy data on all parameters in all different types of samples.

     d.   Blind replicates.

     e.   Blind spikes.

     f.   Quality control charts.

     g.   Blind quality control samples.

     All of the above were reported in the five weekly reports, and examples
of each follow:
                                     41

-------
   180
   140
 E
 £
>-^
I
O
   100
<
UJ
a.
   60
Nl 1337 CURVE  A
    10-11-77
   20
                   I   I   I
                                     I   I
                    0.25
                      0.5
0.75
                             CONCENTRATION, mg/l


                   Figure A-l.  Example of daily standard curve.
                                    42

-------
TABLE A-l.  EXAMPLE OF PRECISION DATA
 (Water Sample Analyses for Mercury)
               (mg/1)
Sample
1
2
3
4
5
6
7
Average
Std.dev.
Coef. of
variation
AMD
(10-6-77)
Time: 15:00
<0.0002
<0.0002
<0.0002
<0.0002
<0.0002
<0.0002
<0.0002
<0.0002
0
0
AMD-A
(10-5-77)
Time: 8:30
0.494
0.519
0.489
0.484
0.494
0.494
0.494
0.495
0.0111
2.24
AMD product A
(10-5-77)
Time: 8:30
0.019
0.020
0.019
0.019
0.019
0.019
0.019
0.019
0.0004
2.11
                   43

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           TABLE A-2.  EXAMPLE OF ACCURACY DATA  FOR  PHOSPHORUS
                          (mg/1 for water, yg/g for sludge)





Source and spiking level
Sample
1
2
3
4
5
6
7
AMD
(10/8/77-1500)
Added 2.5 mg
P/l
9.58
9.06
10.7
9.84
8.06
10.1
7.96
AMD -A
(10/8/77-1500)
Added 2.5 mg
P/l
10.5
9.68
9.23
10.2
10.0
9.15
10.7
Product A
(10/8/77-1500)
Added 2.5 mg
P/l
4.74
4.72
5.00
4.80
5.02
5.78
5.56
Sludge A
(10/5/77—830)
Added 25.0
ug/g
71.5
74.0
75.0
76.4
79.3
73.0
73.0
Average

Percent recovery
    9.33
9.92
5.09
74.6
   9.33               9.92            5.09   „      74.6
6.84+2.50  * 99'9  7.66+2.50 * 97-6 2.80+2.5036*0  49.0+25 = 10]
                                        44

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                                  ^laboratories,  <31nc.
                5815 MIDDLEBROOK PIKE  KNOXVILLE, TENNESSEE 37921
TO:
                     CERTIFICATE  OF  ANALYSIS
Mr.  Jack Hall	
Hydroscience,  Inc.
9041 Executive Park Driye
Knoxville.  TN  37919	
DATE REPORTED:  October 12,  1977
CODE:	
ORDER  No.:	
      Sample Description:   AMD - B (10-1-77) 1500
      Concentration units  are mg/liter (ppm)
      Arsenic
      Cadmium
      Chromium
      Copper
      Mercury
      Nickel
      Selenium
      Zinc
      Phosphorus
                          Original Analysis
                                2.00
                                0.777
                                0.72
                                6.49
                                0.484
                                0.80
                                1.18
                                6.57
                                3.90
                      Blind Split
                         2.05
                         0.800
                         0.69
                         6.22
                         0.479
                         0.78
                         1.21
                         6.51
                         3.20
 Sworn to and subscribed before me this   12th
 day of October  1977	
 	-J^ -~\ ')' L  -v'•' '    --  '
          •' ^WDTARY PUBLIC
 My commission ftxpirss December 23. 1979
                                          STEWART LABORATORIES, INC.
            Figure A-2.  Example of blind split analysis certification.
                                       45

-------
                 5815 MIDDLEBROOK PIKE  KNOXVILLE, TENNESSEE 37921
                      CERTIFICATE   OF  ANALYSIS
 TO:   Hr^ajck Hall
      Hydroscience, Inc.
      9041 Executive Park Drive
      Knoxville, TN 37919
                    DATE REPORTED:  October 12.  1977
                    CODE:	
                    ORDER No.:	
      Sample Description:   AMD-B  (10-6-77) Time:  0830
      Concentration units  are mg/liter (ppm)
      Arsenic
      Cadmium
      Chromium
      Copper
      Mercury
      Nickel
      Selenium
      Zinc
      Phosphorus
Sample No.
   7324
  2.08
  0.511
  0.37
  it.27
  0.499
  0.54
  0.980
  4.45
  7.15
                                                       Cone.
                                                       Spike
2.00
0.75
0.5G
4.00
0.500
0.80
1.00
4.00
2.50
Recovery
  (%)
   96.8
   95.2
  105.
   98.9
  110.
   93.3
  104.
  101.
   92.2
Sworn to and subscribed before me this 12th
day of  October 1977	
             10TARY PUBLIC
My commission expire  December 23.  1979
                        STEWART LABORATORIES, INC.
        Figure A-3.  Example of spiked sample analysis certification.
                                       46

-------
        PRECISION CONTROL CHHRT FDR OWUUH IN 5LUDHE
•
      "'-
      *     x
     Figure  A-4.  Example of precision control chart.
                           47

-------
1
TO:

^ 5815 MIDDLEBROOK PIKE
CERTIFICATE
Mr. Jack Hall
Hydroscience, Inc.
9041 Executive Park Drive
Knoxville, TN 37919

JnratnriCS, >r. g|g
KNOXVILLE, TENNESSEE 37921 ^^^f
OF ANALYSIS
DATE REPORTED October 19, 1977
CODE:
ORDER No :


Sample Description: QC Sample (ERA Lot #1762)
Concentration units are micrograms per liter (ppb)
Analysis Certified Acceptable
Result Value Range
Sworn
day of
Arsenic 110.
Cadmium 75.
Chromium 350.
Copper 280.
Mercury 4.3
Nickel 440.
Selenium 73.
Zinc 310.
to and subscribed before me this 19th
October 1977
^••HMf, "r A-r-"''
110. 100-120.
83. 79-87.
350. 330-370.
275. 265-285.
4.4 4.2-4.6
440. 425-455.
67. 61-73.
310. 295-325.
STEWART LABORATORIES, INC.
( \ NOTMY PUBLIC ' /s %/ C^//J^_
My commission expires December 23, 1979 R L^fc:
-------
                                 APPENDIX B

              OUTLINE OF ANALYTICAL METHODS AND INSTRUMENTATION


     The analytical methods used in this project were essentially those
described in the EPA methods manual (10) and listed in Table B-l.  These
methods and the instrumentation employed are briefly reviewed below:


SAMPLE DIGESTION PROCEDURE

     There were three acid digestion procedures used (1) Boron - 50 ml of
sample was digested with 1:1 sulfuric acid; (2) Phosphorus - 50 ml of sample
was digested with 1 ml concentrated sulfuric acid and 5 ml of concentrated
nitric acid; and (3) Metals - the complete procedure outlined in the EPA
manual (10) on page 82, section 4.1.3 was followed.


ATOMIC ABSORPTION PROCEDURE - GENERAL

     The parameters including cadmium, chromium, copper, nickel, and zinc
were analyzed on an Instrumentation Laboratory  (IL) Model 151 AA/Emission
Spectrometer with automatic simultaneous background correction and recorder
output.  An air-acetylene flame with appropriate hollow cathode tubes at the
proper wavelength was used in all cases.


ATOMIC ABSORPTION PROCEDURE - HYDRIDE

     In the determination of arsenic and selenium  in all samples, an Instru-
mentation Laboratory gaseous hydride generator was used.  The gaseous hydride
is swept into an argon-hydrogen flame of an IL Model 453 AA/Emission Spectrom-
eter with dual double-beam reference optics and automatic simultaneous back-
ground correction and response recorded at 193.7 mm for arsenic and 196.0 mm
for selenium.


ATOMIC ABSORPTION - COLD VAPOR

     The IL Model 453 AA equipped with  an  IL Model 455 Flameless Atomizer was
used for the mercury analysis.  The method involves the reduction of mercury
to the elemental state and aeration from solution  into a closed cell where the
absorption of radiation at 253.7 mm by  the mercury vapor is recorded.
                                      49

-------
BORON - COLORIMETRIC

     The unpreserved sample or sample digested with sulfuric acid was passed
through a column of acidic cation-exchange resin.  This solution was
evaporated in the presence of curcumin forming a red product, rosocyanine.
The residue was the  dissolved in ethanol and read on a Beckman Model DU
Spectrophotometer at 540 mm.


TOTAL PHOSPHORUS - COLORIMETRIC

     Following persulfate digestion, all phosphorus converted to ortho-
phosphorus was reacted in an acid medium with ammonium molybdate and antimony
potassium tartrate.   This complex was then reduced to a blue-colored complex
by ascorbic acid and the color measured on a Beckman DU Spectrophotometer at
650 mm.
                                     50

-------
TABLE B-l.  APPLICABLE ANALYTICAL METHODOLOGY
Parameter
As, inorganic
B
Cd
Cr
Cu
Pb
Hg
Ni
Se
Zn
Total P
Detection Limit yg/1
10
100
2
20
10
50
0.2
20
2
5
10
Method
AA (hydride)
Colorimetric
AA
AA
AA
AA
AA (cold vapor)
AA
AA (hydride)
AA
Colorimetric
                       51

-------
TABLE C-l.   TRACE ELEMENT POLLL"
^-T AXALYSES FOR  LINE  XEUTRALI'ATIGX

 water, -Kg/g for  sludge)
Date

9-21-77
9-21-77
9-21-77
9-21-77
9-21-77
9-21-77
9-21-77
9-21-77
9-21-77
9-21-77
9-21-77
9-21-77
9-21-77
9-21-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
Time

0830
0830
0830
0830
0830
0830
0830
1500
1500
1500
1500
1500
1500
1500
0830
0830
0830
0850
0850
0830
0830
1500
1500
1500
1500
1500
1500
1500
Sar.ple

AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
As
pH
0.01
1.85
1.24
0.04
0.03
23.8
10.4
0.01
1.98
1.58
0.03
0.03
23.8
13.8
0.02
2.08
1.87
0.03
0.02
26.2
11.1
0.01
2.45
1.91
0.03
0.02
22.8
14.4
B
11 (
0.4
2 . 3
2.8
2.3
1.7
5.0
1.4
0.5
2.2
2.6
1.8
1.7
6.3
2.1
*
*
*
*
*
4.1
2.9
*
*
*
*
*
9.1
0.75
Cd
Process A]
    >
                                                                                              r*    -a
                                                                                                   -a
                                                                                              >    m
                                                                                              z    z
                                                                                              >    a
                                                                                              t—'    i-i
                                                                                              -<    x

                                                                                              HH    n
                                                                                              n
                                                                                              >

                                                                                              >

-------
                                                TABLE C-l (Continued)
On
O4
Date
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
Time
0800
0800
0800
0800
0800
0800
0800
1500
1500
1500
1500
1500
1500
1500
0800
0800
0800
0800
0800
0800
0800
1500
1500
1500
1500
1500
1500
1500
Sample
AMD
AMD -A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD -A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD -A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
As
0.01
2.17
1.78
0.01
0.01
23.6
13.6
0.01
2.21
1.89
0.03
0.02
16.5
13.1
0.01
2.10
1.78
0.02
0.02
19.2
7.30
0.01
2.07
1.96
0.03
0.02
26.6
17.5
B
0.3
1.9
2.5
1.7
1.8
1.3
0.3
0.7
1.9
2.3
1.8
1.5
9.6
3.8
*
*
*
*
*
4.3
2.1
*
*
*
*
*
3.8
2.0
Cd
<0.001
1.31
1.01
0.004
0.003
15.3
6.82
<0.001
1.22
0.938
0.013
0.010
13.5
10.7
<0.001
1.24
1.07
0.011
0.012
11.8
4.44
<0.001
1.29
1.10
0.008
0.009
13.5
9.18
Cr
0.04
0.75
0.69
0.04
0.06
4.88
3.02
0.04
0.65
0.56
0.05
0.06
3.64
3.54
0.04
0.71
0.55
0.04
0.04
3.82
1.56
0.03
0.64
0.58
0.04
0.04
4.80
3.20
Cu
0.02
6.28
4.87
0.03
0.03
56.4
32.8
0.02
5.77
4.75
0.07
0.06
46.4
40.2
0.02
6.20
5.10
0.06
0.05
45.2
16.7
0.02
6.05
5.40
0.05
0.05
60.0
37.8
Hg
<0.0002
0.600
0.464
0.010
0.005
3.93
1.96
0.0004
0.546
0.429
0.012
0.009
3.04
2.81
<0.0002
0.595
0.459
0.018
0.009
4.21
1.29
<0.0002
0.566
0.507
0.018
0.007
4.12
2.52
Ni
0.17
0.75
0.61
0.04
0.07
7.70
4.36
0.15
0.69
0.62
0.06
0.06
6.26
5.72
0.16
0.75
0.64
0.05
0.06
6.06
2.50
0.17
0.74
0.67
0.05
0.06
7.22
4.80
Se Zn
<0.001 0.293
1.04 6.72
0.715 5.26
0.368 0.084
0.261 0.049
5.04 65.0
3.08 39.8
<0.001 0.249
1.01 6.12
0.798 5.20
0.432 0.100
0.257 0.075
4.36 53.8
3.84 47.8
0.002 0.525
0.970 6.44
0.767 5.42
0.448 0.098
0.344 0.075
3.92 51.8
2.16 21.6
0.002 0.293
0.990 6.33
0.798 5.69
0.396 0.262
0.320 0.063
5.00 66.0
2.74 42.8
P
3.90
5.20
5.55
2.60
1.90
56.0
18.0
4.10
5.00
4.80
3.30
1.65
34.2
22.0
4.95
6.50
4.20
3.65
1.40
21.0
11.0
6.50
4.95
4.95
1.85
2.05
32.0
22.0
f continued")

-------
TABLE C-l (Continued)
Date Time

9-28-77 0800
9-28-77 0800
9-28-77 0800
9-28-77 0800
9-28-77 0800
9-28-77 0800
9-28-77 0800
9-28-77 1500
9-28-77 1500
9-28-77 1500
9-28-77 1500
9-28-77 1500
9-28-77 1500
9-28-77 1500
9-29-77 0830
9-29-77 0830
9-29-77 0830
9-29-77 0830
9-29-77 0830
9-29-77 0830
9-29-77 0830
9-29-77 1400
9-69-77 1400
9-29-77 1400
9-29-77 1400
9-29-77 1400
9-29-77 1400
9-29-77 1400

Sample

AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B

As
pH
0.01
1.87
2.05
0.03
0.05
26.6
11.9
0.01
1.82
1.69
0.04
0.06
27.2
9.60
0.02
1.76
1.78
0.03
0.04
27.8
37.0
0.02
1.97
1.63
0.03
0.04
29.6
8.78

9
*
*
*
*
*
3
3
*
*
*
*
*
3
3
*
*
*
*
*
2
1
*
*
*
*
*
7
4
B Cd
(Process A)
<0.001
0.950
1.04
0.019
0.071
.0 15.8
.9 6.56
<0.001
1.05
0.990
0.019
0.074
.0 19.1
.0 6.56
<0.001
1.02
1.02
0.482
0.070
.4 16.1
.8 22.8
0.002
1.06
0.917
0.019
0.067
.4 16.8
.0 5.76
Cr
vs pH 8
0.03
0.54
0.59
0.04
0.04
5.42
2.34
0.04
0.52
0.51
0.03
0.03
6.34
2.24
0.03
0.53
0.52
0.05
0,04
5.42
7.08
0.10
0.61
0.53
0.11
0.12
5.52
2.16
Cu
Hg
Ni
Se
Zn
P
(Process B)
0.02
4.71
5.05
0.09
0.14
63.8
25.4
0.02
5.10
4.90
0.10
0.16
81.4
24.2
0.01
5.00
5.00
0.10
0.14
67.6
90.0
0.04
4.96
4.32
0.12
0.15
68.8
24.2
<0.0002
0.361
0.449
0.007
0.012
4.49
1.81
<0.0002
0.449
0.444
0.008
0.012
5.60
1.86
<0.0002
0.322
0.356
0.006
0.011
4.67
6.70
<0.0002
0.504
0.479
0.006
0.010
4.44
4.06
0.16
0.59
0.61
0.07
0.21
8.26
3.04
0.17
0.65
0.62
0.06
0.20
10.2
2.60
0.21
0.69
0.71
0.05
0.05
9.40
10.3
0.19
0.68
0.60
0.06
0.19
8.78
2.60
<0.001
0.590
0.869
0.158
0.095
8.30
3.50
<0.001
0.818
0.900
0.149
0.066
9.60
3.68
<0.001
0.950
0.940
0.162
0.059
8.22
8.30
<0.001
0.833
0.658
0.128
0.043
8.48
3.80'
0.311
4.94
5.31
0.108
0.210
76.0
31.8
0.264
5.20
5.20
0.110
0.206
93.4
30.8
0.358
5.47
5.36
0.098
0.191
78.0
107.
0.355
5.29
4.97
0.098
0.197
82.2
28.8
3.35
5.05
5.75
1.85
1.25
36.2
12.2
11.1
11.5
11.6
4.70
4.40
46.2
14.0
6.20
7.50
7.15
2.05
3.40
49.6
27.4
4.35
5.35
5.15
3.65
3.45
41.0
13.6
(continued]

-------
                                           TABLE C-l  (Continued)
Cn
in
Date Time
9-30-77 0830
9-30-77 0830
9-30-77 0830
9-30-77 0830
9-30-77 0830
9-30-77 0830
9-30-77 0830
9-30-77 1500
9-30-77 1500
9-30-77 1500
9-30-77 1500
9-30-77 1500
9-30-77 1500
9-30-77 1500
10-1-77 0800
10-1-77 0800
10-1-77 0800
10-1-77 0800
10-1-77 0800
10-1-77 0800
10-1-77 0800
10-1-77 1500
10-1-77 1500
10-1-77 1500
10-1-77 1500
10-1-77 1500
10-1-77 1500
10-1-77 1500
Sample
AMD
AMD
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD -A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
As
0.01
1.95
2.15
0.04
0.40
34.4
11.3
0.01
1.77
2.06
0.04
0.04
30.0
6.04
0.01
1.95
2.42
0.04
0.05
32.0
11.5
0.03
1.93
2.00
0.04
0.04
27.4
8.14
B
*
*
*
*
*
2.1
1.4
*
*
*
*
*
5.8
6.4
*
*
*
*
*
5.9
3.8
*
*
*
*
*
8.3
7.8
Cd
<0.001
0.557
0.603
0.014
0.046
16.1
4.24
<0.001
0.777
0.777
0.014
0.053
12.3
2.88
<0.001
0.707
0.789
0.017
0.043
11.8
2.54
<0.001
0.731
0.777
0.016
0.042
11.2
3.50
Cr
0.09
0.52
0.60
0.10
0.10
6.72
3.02
0.04
0.60
0.55
0.05
0.05
6.06
1.32
0.04
0.51
0.64
0.07
0.05
5.88
2.68
0.04
0.67
0.72
0.10
0.10
5.16
1.82
Cu
0.02
4.37
4.83
0.10
0.13
86.4
24.2
0.02
6.11
6.30
0.12
0.18
76.4
10.6
0.02
5.30
6.33
0.13
0.16
70.0
29.0
0.02
5.92
6.49
0.12
0.19
62.6
19.2
Hg
<0.0002
0.553
0.553
0.009
0.014
5.32
1.62
<0.0002
0.563
0.548
0.010
0.016
5.32
0.95
<0.0002
0.533
0.499
0.012
0.018
4.53
1.96
<0.0002
0.475
0.484
0.010
0.017
4.77
1.38
Ni
0.17
0.57
0.62
0.06
0.18
10.0
2.10
0.18
0.74
0.75
0.06
0.21
9.13
1.74
0.18
0.65
0.74
0.20
0.20
8.75
3.24
0.24
0.76
0.80
0.07
0.20
8.30
2.05
Se
<0.001
0.823
0.853
0.149
0.033
10.9
3.58
<0.001
0.765
0.950
0.148
0.048
10.4
1.90
<0.001
0.931
1.21
0.210
0.071
10.7
4.44
<0.001
0.980
1.18
0.171
0.086
8.44
3.42
Zn
0.252
4.55
4.97
0.086
0.252
96.4
29.8
0.273
6.19
6.40
0.114
0.273
88.2
21.6
0.25
5.44
6.51
0.165
0.211
83.2
35.8
0.446
6.14
6.57
0.114
0.260
74.0
22.6
P
3.85
5.70
6.50
1.65
3.75
47.4
13.6
2.40
3.40
3.10
1.05
1.40
43.0
7.20
2.90
3.50
3.90
1.50
1.80
40.0
15.2
2.70
3.30
3.90
1.95
1.90
32.4
10.2
	 	 - (continued")

-------
                                           TABLE C-l (Continued)
on
O\
Date Time
10-5-77 0830
10-5-77 0830
10-5-77 0830
10-5-77 0830
10-5-77 0830
10-5-77 0830
10-5-77 0830
10-5-77 1500
10-5-77 1500
10-5-77 1500
10-5-77 1500
10-5-77 1500
10-5-77 1500
10-5-77 1500
10-6-77 0830
10-6-77 0830
10-6-77 0830
10-6-77 0830
10-6-77 0830
10-6-77 0830
10-6-77 0830
10-6-77 1500
10-6-77 1500
10-6-77 1500
10-6-77 1500
10-6-77 1500
10-6-77 1500
10-6-77 1500
Sample
AMD
AMD -A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD -A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD -A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
As
pH
0.01
2.10
1.84
0.11
0.02
50.6
16.3
0.01
1.82
2.11
0.11
0.02
55.4
13.3
0.02
1.84
2.08
0.09
0.02
42.6
2.08
0.02
1.99
2.01
0.10
0.02
50.2
9.46
B
Cd
7 (Process A)
0.6
1.8
2.0
1.5
0.8
16.3
11.8
2.0
0.7
1.8
2.1
1.0
23.5
12.1
0.5
2.2
1.7
1.8
1.4
12.6
10.9
0.8
2.8
2.7
2.5
1.9
14.8
13.1
<0.001
0.591
0.545
0.184
0.048
12.4
4.44
<0.001
0.642
0.719
0.169
0.003
13.8
4.44
0.014
0.626
0.511
0.145
0.003
8.14
1.66
<0.001
0.696
0.580
0.172
<0.001
Cr
vs pH
0.04
0.53
0.42
0.05
0.05
9.48
2.60
0.03
0.47
0.46
0.04
0.04
11.3
2.16
0.03
0.45
0.37
0.04
0.05
7.08
0.72
0.02
0.50
0.42
0.04
0.04
14.8 9.18
3.90 1.82
(continued)
Cu
Hg
Ni
Se
Zn
P
12 (Process B)
0.02
5.54
3.98
0.36
0.08
121.
42.6
0.02
5.02
5.15
0.31
0.06
145.
34.0
0.02
5.15
4.27
0.20
0.09
90.0
5.62
0.04
5.78
5.08
0.35
0.10
118.
20.4
<0.0002
0.494
0.450
0.019
0.012
7.56
2.85
0.0002
0.543
0.475
0.017
0.018
8.70
2.57
<0.0002
0.445
0.499
0.014
0.007
5.92
0.54
<0.0002
0.509
0.470
0.014
0.003
7.75
1.77
0.17
0.71
0.50
0.41
0.06
6.91
6.78
0.15
0.64
0.63
0.33
0.06
7.30
5.26
0.18
0.66
0.54
0.28
0.07
5.72
0.58
0.15
0.71
0.60
0.34
0.05
7.17
2.80
<0.001
1.05
0.833
0.054
0.136
15.2
7.00
<0.001
1.02
1.01
0.056
0.158
17.8
5.16
<0.001
0.833
0.980
0.043
0.158
12.1
0.82
<0.001
0.882
0.931
0.031
0.119
16.2
2.82
0.249
5.55
4.14
1.05
0.126
115.
53.8
0.267
5.07
5.29
0.965
0.068
131.
43.8
0.311
5.44
4.45
0.785
0.308
88.2
6.74
0.289
5.82
4.92
0.979
0.048
115.
23.4
2.15
4.75
4.75
4.10
0.45
50.0
11.0
2.70
5.40
4.30
3.50
1.50
35. 0
9.25
5.40
6.80
7.15
5.25
1.35
32.6
2.73
3.80
5.40
5.00
3.45
1.20
76.0
11.2

-------
                                        TABLE C-l  (Continued)
en
Date
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77

Time
0830
0830
0830
0830
0830
0830
0830
1500
1500
1500
1500
1500
1500
1500
0830
0830
0830
0830
0830
0830
0830
1500
1500
1500
1500
1500
1500
1500

Sample
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B
AMD
AMD-A
AMD-B
Product A
Product B
Sludge A
Sludge B

As
0.02
2.24
1.99
0.10
0.02
46.0
6.52
0.02
2.06
2.29
0.09
0.01
28.6
6.52
0.01
2.08
1.99
0.11
0.02
51.2
6.04
0.02
1.92
1.85
0.11
0.02
44.8
8.04

B
0.8
2.6
2.7
2.7
1.9
12.0
4.0
0.9
3.3
3.2
2.9
1.7
18.8
13.3
*
*
*
*
*
17.4
11.4
*
*
*
it
*
16.8
15.2

Cd
<0.001
0.603
0.591
0.193
0.004
12.8
3.16
<0.001
0.825
0.838
0.191
0.003
8.96
2.92
<0.001
0.683
0.670
0.179
0.003
12.9
2.38
<0.001
0.709
0.812
0.185
0.002
12.9
2.66

Cr
0.03
0.46
0.40
0.03
0.03
8.42
1.56
0.02
0.58
0.57
0.03
0.03
6.24
1.64
0.02
0.45
0.45
0.03
0.03
9.98
1.46
0.02
0.47
0.56
0.03
0.02
8.90
1.34

Cu
0.04
5.15
4.84
0.35
0.12
109.
142.
0.03
6.05
6.18
0.25
0.06
79.6
18.5
0.04
4.67
4.67
0.27
0.05
130.
14.8
0.01
4.92
5.74
0.29
0.04
126.
17.9

Hg
<0.0002
0.523
0.504
0.015
0.004
6.92
1.38
<0.0002
0.476
0.452
0.015
0.005
5.37
1.67
<0.0002
0.537
0.490
0.020
0.015
9.34
1.19
<0.0002
0.447
0.438
0.014
0.012
8.84
2.24

Ni
0.18
0.63
0.59
0.38
0.05
6.81
2.44
0.19
0.73
0.76
0.37
0.07
5.08
2.36
0.15
0.59
0.57
0.30
0.05
6.60
2.42
0.14
0.60
0.70
0.31
0.06
7.00
2.26

Se
<0.001
1.01
1.05
0.037
0.144
14.3
2.40
<0.001
1.07
1.07
0.040
0.176
19.8
2.78
<0.001
1.08
1.11
0.052
0.149
18.4
2.34
<0.001
1.13
1.10
0.061
0.195
17.0
3.68

Zn
0.311
5.02
4.81
1.05
0.06
106.
18.3
0.294
6.94
6.99
1.05
0.021
80.4
23.8
0.206
5.45
5.40
1.06
0.059
111.
17.8
0.249
5.55
6.58
1.14
0.032
84.6
18.8

P
3.60
5.20
5.00
3.35
1.65
60.0
8.75
6.80
10.3
8.60
2.40
0.42
46.0
10.2
6.20
10.7
11.6
5.65
0.90
70.0
9.23
6.82
7.66
6.00
2.80
1.24
75.0
10.0

     *Sample was preserved with nitric acid and analysis was not possible because of interferences.

-------
                      TABLE C-2.   CONVENTIONAL POLLUTANT CHEMICAL ANALYSES FOR LIME NEUTRALIZATION
in
00
Date Time Sample

9-19-77 0830 Raw feed
9-19-77 0830 Spiked feed A
9-19-77 0830 Spiked feed B
9-19-77 0830 Effluent A
9-19-77 0830 Effluent B
9-19-77 1SOO Raw feed
9-19-77 1500 Spiked feed A
9-19-77 1500 Spiked feed B
9-19-77 1500 Effluent A
9-19-77 1500 Effluent B
9-20-77 0830 Raw feed
9-20-77 0830 Spiked feed A
9-20-77 0830 Spiked feed B
9-20-77 0830 Effluent A
9-20-77 0830 Effluent B
9-21-77 0830 Raw feed
9-21-77 0830 Spiked feed A
9-21-77 0830 Spiked feed B
9-21-77 0830 Effluent A
9-21-77 0830 Effluent B
9-21-77 1500 Raw feed
9-21-77 1500 Spiked feed A
9-21-77 1500 Spiked feed B
9-21-77 1500 Effluent A
9-21-77 1500 Effluent B
Means R;iw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B

Cond

2850
3050
2900
2900
2880
2950
2950
2950
3000
2880
2830
2890
2S60
3250
3150
2800
2800
2800
3000
3000
2 SCO
2800
2800
2900
2900
2720
2700
2730
2840
2840
Acid
pH 11
370
430
460
0
0
470
470
470
0
0
380
370
380
0
0
460
460
460
0
0
430
430
430
0
0
450
450
450
0
0
pH
Ca
(Process A)
4.7
3.6
4.4
11.0
10.0
5.2
5.0
5.0
10.8
9.8
5.2
4.9
4.9
10.8
9.9
5.3
5.0
5.1
11.2
9.9
5.3
5.1
5.1
10.8
10.0
5.2
4.9
5.0
10.9
10.0
340
340
340
600
600
340
330
340
680
530
340
340
340
eoo
500
350
350
350
680
550
350
350
350
580
500
340
340
350
610
530
Total
Mg Fe
vs pH 10
100 155
100 160
100 160
6.9 1.7
25 1.6
100 160
95 160
96 150
7.1 1.2
25 .94
100 160
95 ISO
95 150
3.7 .16
20 .14
100 160
100 160
100 150
4.4 .12
24 .18
95 150
95 ISO
90 150
6.5 .10
25 .16
100 160
98 160
98 150
S . 0 .35
25 .40
Fe2
(Process
130
160
160
0
0
150
150
140
0
0
150
ISO
140
0
0
150
150
150
0
0
150
140
150
0
0
150
150
150
0
0
Na
B)
340
340
330
330
330
330
320
330
330
320
330
340
340
330
330
340
320
330
330
330
340
340
330
340
340
350
340
340
340
340
Al

12.0
8.4
8.0
.58
.38
8.6
6.0
6.0
.12
.16
6.4
4.2
4.2
.58
.80
7.0
4.S
5.0
.32
.40
8.6
4.6
22.
.46
.40
6.3
5.4
6.6
.40
.40
Mn S04

5.1 2190
5.2 2320
5.2 2320
.16 2380
.15 2340
4.6 2300
4.5 2180
4.5 2330
.10 2400
.10 2210
4.7 2340
4.6 2330
4.6 2330
.05 2250
.05 2050
4.8 2350
4.8 2340
4.8 2340
.05 2440
.05 2250
4.78 2350
4.6 2340
4,78 2500
.05 2400
.05 2070
S.O 2310
5.0 2310
5.0 2170
.06 2340
.06 2250
Alk

5
0
0
61
19
15
10
10
77
41
18
S
S
92
41
25
IS
20
120
80
30
20
25
80
40
23
14
15
90
50
TDS

3140
3270
3260
3320
3290
3240
3090
3240
3410
3080
3270
3250
3250
3190
2900
3300
3270
3280
3450
3150
3300
3280
3440
3330
2940
3260
3250
3330
3230
3160
Ion*
Bal

3.0
2.7
3.5
11.2
5.S
3.6
1.5
7.7
5.0
8.9
5.9
6.1
6.5
8.8
6.0
4.3
5.7
5.7
7.8
9.6
5.7
5.S
10.4
13.8
4.5





Turb.

48
51
S3
10
3.5
34
63
64
18
10
23
68
73
15
10



6
1C



10
12
35
61
63
9
7
	 ^continued! 	 . 	 	

-------
                                                          TABLE  C-2 (Continued)
Cn
Date
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-22-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-23-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
9-24-77
Tine
0830
0830
0830
0830
0830
1500
1500
1500
1500
1500
0830
0830
0830
0830
0830
1500
1500
1500
1500
1500
0830
OS30
0830
0830
0830
1500
1500
1500
1500
1500
Sample
Raw Feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Cond
2600
2600
2600
2740
2690
2800
2800
2800
3000
3000
2600
2500
2500
2400
2700
2550
2250
2750
2700
2800
2500
2450
2450
2600
2500
2600
2600
2600
2770
2720
Acid
510
510
420
0
0
550
500
500
0
0
480
480
480
0
0
360
410
450
0
0
500
520
520
0
0
400
410
420
0
0
pH Ca
5.1 340
4.8 340
4.9 340
10.8 600
9.9 520
5.2 350
5.0 350
5.0 350
10.8 660
10.0 600
5.2 370
5.1 370
5.0 370
10.8 650
9.8 540
5.5 310
5.3 310
5.3 360
11.0 540
10.0 500
5.1 320
5.1 320
5.0 340
10.9 620
9.5 510
5.4 340
5.2 330
5.3 340
10.8 540
10.5 520
Mg
90
90
90
5.8
23
100
100
100
3.7
25
100
96
98
5.0
24
110
100
110
3.0
26
100
100
100
4.0
28
110
110
100
4.7
30
Total
Fe
170
170
170
.10
.20
170
170
170
.06
.12
170
170
160
.18
.20
140
140
130
.15
1.0
160
160
160
.07
.12
150
150
140
.05
.07
Fe2
160
160
160
0
0
160
160
160
0
0
160
160
160
0
0
130
130
130
0
0
150
150
150
0
0
150
ISO
140
0
0
Na
330
330
330
330
330
350
350
350
330
330
350
340
340
3>0
330
360
360
350
340
350
350
350
350
350
370
380
370
350
370
420
Al
4.0
4.0
4.0
.18
.24
6.0
8.4
6.8
.42
.56
6.6
6.6
6.2
.05
.05
2.5
5.1
2.7
.40
.40
4.1
5.1
3.9
.54
.70
3.8
3.0
3.7
.30
.36
Nbi S04
4.8 2180
4.8 2330
4.8 2330
.05 2130
.08 20SO
4.9 2210
4.8 2330
4.9 2480
.05 2280
.05 2400
4.7 2490
4.7 2350
4.7 2345
.05 2420
.05 2370
5.1 2360
5.1 2190
5.0 2350
.05 2220
.05 2410
5.8 2350
5.9 2340
5.9 2490
.05 2410
.06 2220
5.9 2300
5.9 2340
5.9 2340
.05 2410
.05 2410
Alk
15
5
10
92
46
20
10
10
90
45
20
26
15
97
51
41
26
31
87
51
31
18
15
92
56
36
20
20
92
92
TDS
3110
3250
3260
3060
2950
3180
3310
3460
32SO
3350
3490
3320
3310
3400
3260
3280
3110
3300
3100
3290
3290
3270
3460
3380
3130
3290
3300
3320
3330
5330
Ion*
Bal Turb .
1.7
6.9
7.3
2.5 10
4.2 7.7
2.5
1.2
6.9
3.1 12
8.4 5
6.3
2.9
2.1
9.4 4.0
13.8 4.0
9.3
1.8
5.3
11.8 4.0
16.7 7.0
7.4
6.2
8.9
10.7 3.5
7.0 5.8
0.2
3.7
2.2
15.8 4.0
10.3 7.0
("continued)

-------
TABLE C-2 (Continued)
Date

9-27-77
9-27-77
9-27-77
9-27-77
9-27-77
9-27-77
9-27-77
9-27-77
9-27-77
9-27-77
9-28-77
9-28-77
9-28-77
9-28-77
9-28-77
9-23-77
9-28-77
9-28-77
9-28-77
9-28-77
9-29-77
9-29-77
9-29-77
9-2S-77
9-29-77
9-29-77
9-29-77
9-29-77
5-2S-77
9-29-77
Time

0830
0830
0830
0830
0830
1500
1500
1500
1500
1500
0830
OS30
0830
0830
0830
1500
1500
1500
1500
1500
OS30
0830
OS30
0830
0830
1500
1500
1500
1500
1500
Sample

Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Cond

2430
2450
2450
2500
2580
2550
2550
2540
2550
2620
2560
2530
2530
2500
2640
2530
2550
2580
2600
2700
2390
23SO
2380
2350
2500
2500
2SOO
2500
2450
2600
Acid pH
pH 9
390
400
410
0
0
360
380
380
0
0
350
370
370
0
0
370
370
310
0
0
380
3SO
350
0
0
380
3EO
370
0
0
(Process
5.2
5.1
5.2
9.0
7.8
5.2
5.2
5.2
8.8
8.0
5.4
5.3
5.3
S.8
7.9
5.3
5.2
5.2
8.8
8.0
S.2
S.O
5.0
9.2
8.0
5.2
5.1
5.1
9.0
7.9
Ca
A) vs
330
330
345
480
480
340
330
330
480
430
340
320
320
450
470
340
340
330
460
480
340
540
340
420
500
360
360
360
S50
510
Mg
pH
110
110
110
70
100
110
100
100
70
100
100
100
ICO
73
98
ICO
100
100
72
100
100
100
100
64
100
98
95
96
SS
90
Total 0
Fe Fe~
S (Process E
170 160
160 160
160 160
.35 0
.63 0
160 160
160 160
160 160
.28 0
.53 0
150 ISO
150 150
150 150
.37 0
.77 0
160 160
150 150
150 150
.35 0
.49 0
160 160
160 160
160 160
.51 0
.67 0
160 160
160 140
160 140
.18 0
.38 0
Na
>?
340
350
350
340
340
350
350
350
340
340
360
350
350
340
350
340
340
340
330
340
330
330
330
330
340
370
360
360
340
340
Al

6.7
19.
7.8
.38
.20
6.4
8.0
14
.26
.12
5.9
5.5
4.7
.16
.18
4.6
7.2
5.6
.16
.22
7.1
6.9
7.1
.40
.42
8.8
8.S
7.6
.42
.42
Mn 504

5.8 2350
5.9 2340
5.9 2340
.20 2210
2.6 2430
4.9 2350
5.0 2340
5.0 2340
.17 2210
2.3 2440
5.0 2350
5.2 2340
5.4 2340
.22 2210
2.4 2300
5.0 2350
4.9 2340
5.1 2340
.25 2210
2.5 2300
5.5 2360
5.6 2350
5.7 2330
,22 2210
2.8 2440
5.2 2350
5.2 2350
5.2 2350
.17 2250
2.6 2280
Alk

31
20
20
43
32
31
18
20
46
37
36
26
20
46
33
31
15
20
43
33
43
10
10
41
37
26
15
15
41
37
TDS

5310
3310
3300
3100
3360
3310
3290
3290
3100
3360
3310
32SO
3270
3070
3210
3300
3280
3230
3077
3220
3310
3280
3280
3080
3380
3350
3350
3330
3200
3220
Ion*
Bal

5.0
1.2
4.0
4.4
10.6
4.4
4.5
3.6
4.9
11.1
5.6
6.5
7.0
7.8
7.7
5.7
4.8
6.2
7.8
6.7
6.4
3.9
3.9
6.3
8.8
1.0
1.3
1.4
1.5
3.5
Turb.




10
10



10
12



13
13



10
10



10
10



7.3
10
(continued)

-------
TABLE C-2  (Continued)
Date
9-30-77
9-50-77
9-30-77
9-30-77
9-30-77
9-30-77
9-30-77
9-30-77
9-30-77
9-30-77
10-1-77
10-1-77
10-1-77
10-1-77
10-1-77
10-1-77
10-1-77
10-1-77
10-1-77
10-1-77
Means




Time Sample
0830 Raw feed
0830 Spiked feed A
0830 Spiked feed B
0830 Effluent A
0830 Effluent B
1500 Raw feed
1500 Spiked feed A
1500 Spiked feed B
1500 Effluent A
1500 Effluent B
0830 Raw feed
0830 Spiked feed A
0830 Spiked feed B
0830 Effluent A
0830 Effluent B
1500 Raw feed
1500 Spiked feed A
1500 Spiked feed B
1500 Effluent A
1500 Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Cond
2300
2350
2350
2300
2480
2440
2440
2400
2350
2530
2400
2400
2400
2300
2300
2500
2500
2500
2400
2400
2460
2470
2460
2430
2540
Acid
370
370
320
0
0
320
310
310
0
0
460
460
460
0
0
650
650
645
0
0
400
400
400
0
0
PH
5.3
5.2
S.2
9.0
7.8
5.5
5.4
5.5
8.9
7.8
5.2
5.1
5.1
8.9
7.9
4.7
4.3
4.3
9.0
7.9
5.2
5.1
5.1
8.9
7.9
Ca
360
360
360
400
380
340
340
340
500
460
350
350
350
490
450
350
350
350
480
420
350
340
340
480
460
Mg
100
100
100
60
95
95
95
95
55
90
95
95
95
60
90
110
110
110
65
100
100
100
100
64
96
Total
Fe
160
160
160
.20
.40
150
130
130
.60
.85
160
160
160
.40
1.6
200
200
200
.08
.18
160
160
160
.33
.65
Fe2
160
160
160
0
0
150
130
130
0
0
160
160
160
0
0
200
200
200
0
0
160
160
160
0
0
Na Al
370 7.8
370 7.6
370 7.2
340 .44
350 .54
360 2.8
360 2.8
360 3.8
340 .64
340 .72
350 4.6
350 4.6
350 4.6
340 .10
340 .20
300 14.
290 20
290 15
300 .22
300 .28
350 6.9
350 9.0
350 7.7
330 .31
340 .33
Mr. S04
5.3 2500
5.3 2500
5.6 2500
.18 2000
2.7 2050
5.4 2250
5.4 2250
5.4 2250
.18 2150
2.8 2200
6.2 2300
6.2 2300
6.1 2300
.20 2100
2.3 2150
4.9 2400
4.9 2400
4.9 2400
.15 2050
1.7 2050
5.3 2360
5.3 2350
5.4 2350
.19 2160
2.5 2020
Alk
26
10
13
41
37
51
31
31
46
47
15
20
20
40
30
0
0
0
50
40
29
17
17
44
36
TDS
3500
3500
3500
2800
2880
3200
3180
3180
3040
3090
3270
3270
3270
2990
3030
3380
3370
3370
2900
2870
3320
3310
3310
3040
3160
Ion*
Bal
6.7
6.1
6.3
6.1
6.0
3.0
3.5
3.3
3.0
5.9
2.1
2.3
2.3
0.9
4.6
2.7
2.0
3.2
2.7
5.5





Turb.



10
10



10
10



13
11



10
10



10
11
(continued)

-------
TABLE C-2 (Continued)
Date Time
Sample
Cond
Acid pH Ca
Total
Mg Fe
pH 7 (Process A) vs pH
10-4-77 0830
10-4-77 0830
10-4-77 0830
10-4-77 0830
10-4-77 0830
10-4-77 1500
10-4-77 1500
10-4-77 1500
10-4-77 1500
10-4-77 1500
10-5-77 0830
10-5-77 0830
10-S-77 0830
10-5-77 0830
10-5-77 0830
10-5-77 1500
10-5-77 1500
10-5-77 1500
10-5-77 1500
10-5-77 1SOO
10-6-77 0830
10-6-77 0830
10-6-77 0830
10-6-77 0830
10-6-77 0830
10-6-77 1500
10-6-77 1500
10-6-77 1500
10-6-77 1500
10-6-77 1500

Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B

2500
2500
2500
2500
6200
2500
2500
2500
2500
6600
2500
2500
2500
2500
6400
2700
2700
2700
2700
6COO
2700
2700
2700
2700
6000
2700
2700
2700
2700
6200

500
500
480
18
0
460
470
500
0
0
420
420
420
25
0
450
460
460
12
0
520
530
530
12
0
470
470
480
12
0

5.2 380
5.0 370
5.0 360
7.0 480
12.0 1050
5.3 375
5.2 365
5.3 375
7.2 485
12.0 1000
5.6 380
5.3 370
5.3 370
6.4 470
12.1 1040
5.3 380
5.1 370
5.1 360
7.0 450
12.3 860
5.0 380
4.8 360
4.8 370
6.9 500
12.2 960
5.1 380
4.9 380
4.9 370
7.0 480
12.0 900

110 160
110 160
100 160
98 1.0
.05 .05
100 150
100 150
ICO 150
98 .75
.05 .05
100 150
100 140
100 140
96 1.2
.06 .05
100 150
100 150
100 150
96 1.3
.06 .05
100 170
98 170
98 170
90 1.3
.05 .05
110 160
110 170
100 160
95 2.5
.06 .05
(continued)
Fe2
Na Al
Mn 504 Alk
IDS
Ion*
Bal
Turb.
12 (Process B)
160
160
160
0
0
150
150
150
0
0
140
140
140
0
0
150
150
150
0
0
170
170
170
0
0
150
150
150
0
0

350 8.2
350 22
350 16
330 .44
340 .16
360 7
350 22
350 19
340 .40
340 .20
370 4.0
370 18
370 18
360 .42
370 .24
370 5.6
370 14
360 8.0
350 .60
350 .46
350 8.8
350 9.0
350 8.8
340 .50
340 .40
350 8.0
350 10
350 7.8
310 .32
310 .20

4.9 2490 IS
4.8 2480 10
4.8 2480 10
3.6 2360 40
.05 3550 1290
4.9 2500 30
4.9 2490 20
4.8 2490 15
3.6 2370 50
.05 3560 1390
5.0 2510 40
4.9 2500 25
4.9 2510 25
3.6 2380 50
.05 3410 1400
4.8 2350 25
4.8 2500 15
4.8 2340 15
3.3 2370 45
.05 3230 1070
4.9 2500 10
5.0 2490 5
5.0 2490 5
3.7 2370 40
.05 3550 1220
4.7 2510 20
4.7 2490 5
4.7 2490 5
3.6 2520 35
.05 3410 1230

3500
3480
3470
3270
4940
3500
3480
3490
3290
4900
3S10
3500
3SOO
3310
4S10
3360
3500
3320
3270
4440
3500
3480
3490
3300
4850
3500
3500
3470
3410
4620

4.4
2.8
5.3
6.4
32.6
6.7
4.7
3.9
6.3
36.3
7.7
4.4
6.0
6.1
31.3
0.1
5.4
1.1
8.9
34.2
5.0
6,2
6.0
5.5
36.0
5.S
3.7
6.S
14.6
38.7




25
3.0



25
3.5



25
3.0



34
2.7



20
3.0



22
3.0


-------
                                                          TABLE C-2 (Concluded)
CM
Date
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-7-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
10-8-77
Means




Time
0830
0830
0830
0830
0830
1500
1500
1500
1500
1500
0830
0830
0830
0830
0830
1500
1500
1500
1500
1500





Sample
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Raw feed
Spiked feed A
Spiked feed B
Effluent A
Effluent B
Cond
2600
2600
2600
2600
5600
2700
2700
2700
2700
5800
2600
2700
2550
2700
5150
2600
2650
2700
2700
5600
2610
2625
2615
2630
5960
Acid
520
460
460
6
0
430
370
400
6
0
410
430
510
25
0
660
610
680
12
0
480
460
490
13
0
pH Ca
5.2 370
5.0 370
5.0 360
7.1 480
12.2 1000
5.6 340
5.4 340
5.4 340
7.1 440
12.2 1000
5.4 360
5.2 350
5.2 350
6.8 470
12.4 960
4.8 350
4.6 350
4.7 350
6.8 470
12.3 940
5.2 370
5.1 360
5.1 360
6.9 470
12.1 970
Mg
100
100
100
97
.09
100
100
100
90
.05
100
100
100
95
.05
100
100
100
95
.05
100
101
100
100
.06
Total
Fe
ISO
ISO
150
2.4
.05
130
130
130
1.1
.10
155
150
150
2.7
0
200
190
190
.05
.05
160
160
160
1.4
.05
Fe2
150
150
150
0
0
130
130
130
0
0
150
150
150
2.5
0
200
181
181
0
0
160
150
ISO
.25
0
Na Al
360 7.2
350 7.0
350 7.0
330 .40
320 .24
380 5.0
380 8.0
380 4.8
330 .28
350 .10
360 5.8
360 6.0
360 5.4
350 .40
360 .10
340 10
340 15
340 17
340 .42
340 .24
360 7.0
360 13.
360 11.2
340 .42
340 .23
Mn S04
4.52 2660
4.52 2660
4.52 2660
3.68 2690
<.05 2860
4.74 2280
4.74 2250
4.68 2260
3.70 2300
<.05 2750
4.8 2410
4.8 2410
4.8 2400
3.7 2450
.05 3000
5.1 2410
S.I 2400
5.1 2410
3.7 2250
.05 3000
4.8 2240
4.8 2470
4.8 2450
3.7 2400
.05 3230
Alk
15
10
10
40
1210
55
30
35
80
1190
15
15
13
62
1043
10
5
5
31
1158
24
13
14
47
1220
TDS
3640
3630
3630
3590
4180
3240
3210
3210
3160
4100
3390
3380
3370
3370
4320
3410
3390
3400
3160
4280
3460
3460
3440
3310
4540
Ion*
Bal Turb.
13.1
13.2
13.6
18.4 25
23.6 3.0
2.7
0.2
1.4
12.0 25
19.3 3.0
4.0
5.3
5.8
10.7 20
23.5 1.5
2.2
1.6
1.9
2.9 21
27.7 .5





         All units are mg/1 except for pH, specific conductance  (ymhos/cm), and turbidity  (FTU).
        *Ion balance expressed as percent difference between cations and anions (converted to CaCO.)

-------
TABLE C-3.  MATERIAL BALANCE FOR LIME NEUTRALIZATION STUDY
                (ratio of influent: effluent)
Nominal pH
Parameter
Arsenic
Boron
Cadmium
Chromium
Copper
Mercury
Nickel
Phosphorus
Selenium
Zinc
7
0.43
0.66
0.49
0.53
0.45
0.65
0.69
0.78
0.61
0.50
8
1.67
-
1.32
1.87
1.90
2.05
1.46
1.61
2.32
1.57
9
0.64
-
0.55
0.87
0.71
0.95
0.68
0.90
0.78
0.64
10
1.37
1.50
1.24
1.61
1.57
2.29
1.38
3.83
1.48
1.39
11
0.91
0.92
0.86
1.31
1.09
1.47
0.97
2.57
1.28
1.01
12
1.67
0.80
1.45
1.72
0.95
1.82
1.25
2.97
1.68
1.43
                                 64

-------
                                        TABLE C-4.  REVERSE OSMOSIS TRACE ELEMENT ANALYSES
                                                                  Cmg/1)
tn
Date
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
Time
0940
0940
0940
0940
1010
1010
1010
1010
1040
1040
1040
1040
1110
1110
1110
1110
1140
1140
1140
1140
1210
1210
1210
1210
1240
1240
1240
1240
Sample
Raw AMD
Spiked AMD
Product
Brine
Raw AMD
Spiked AMD
Product
Brine
Raw AMD
Spiked AMD
Product
Brine
Raw AMD
Spiked AMD
Product
Brine
Raw AMD
Spiked AMD
Product
Brine
Raw AMD
Spiked AMD
Product
Brine
Raw AMD
Spiked AMD
Product
Brine
As
0.01
2.22
0.02
3.57
0.01
2.17
0.01
3.29
0.01
2.26
0.02
3.73
0.01
2.21
0.02
3.57
0.01
2.32
0.01
3.43
0.01
2.03
0.01
4.23
0.01
2.53
0.01
3.85
B
0.4
2.2
1.0
3.0
0.5
2.0
0.8
3.1
0.4
1.9
0.6
3.2
0.5
2.0
0.7
3.5
0.4
2.1
0.9
3.2
0.6
2.1
1.0
3.2
0.6
2.1
1.0
2.9
Cd
<0.001
0.775
0.032
1.18
<0.001
0.903
0.002
1.28
<0.001
0.812
0.002
0.967
0.012
0.750
0.002
1.27
0.060
0.892
0.002
1.10
0.010
0.760
0.006
1.31
<0.001
0.887
0.002
1.41
Cr
0.02
0.54
<0.01
0.83
0.01
0.57
<0.01
0.83
0.02
0.51
0.01
0.59
0.02
0.46
<0.01
0.79
0.02
0.55
<0.01
0.65
0.01
0.47
<0.01
0.93
0.02
0.68
<0.01
0.9S
Cu
0.01
6.38
0.01
9.41
0.01
6.50
<0.01
9.48
0.01
6.18
0.01
7.26
0.02
5.68
0.02
9.66
0.01
6.59
0.02
8.30
0.01
5.78
0.01
9.69
0.01
6.38
0.01
10.6
•\
Hg
<0.0002
0.281
0.035
0.162
<0.0002
0.256
0.047
0.166
<0.0002
0.260
0.048
0.175
<0.0002
0.279
0.055
0.183
<0.0002
0.264
0.056
0.190
<0.0002
0.266
0.067
0.179
0.0003
0.247
0.072
0.152
Ni
0.13
0.77
<0.01
1.16
0.12
0.76
<0.01
1.16
0.14
0.71
<0.01
0.85
0.15
0.68
0.01
1.16
0.13
0.80
0.01
0.98
0.14
0.66
<0.01
1.19
0.13
0.81
<0.01
1.24
Se
<0.001
0.752
0.130
2.02
<0.001
1.15
0.116
1.88
<0.001
1.23
0.100
1.52
<0.001
1.07
0.090
1.71
0.002
1.31
0.111
2.00
<0.001
1.18
0.121
1.71
<0.001
1.29
0.135
1.92
Zn
0.220
6.81
0.017
11.1
0.220
7.20
0.024
10.4
0.247
6.58
0.042
7.83
0.276
6.14
0.052
10.5
0.234
6.24
0.060
8.74
0.245
5.61
0.149
10.7
0.198
5.87
0.034
10.4
P
0.48
1.54
0.28
1.80
0.46
1.50
0.12
1.84
0.48
1.70
0.30
1.82
0.98
1.50
0.18
2.20
0.80
1.54
0.56
2.02
0.54
1.16
0.32
1.72
0.74
2.02
0.26
2.96

-------
TABLE C-4.   (Continued)
Date
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
Mean
Std.dev.
Mean
Std.dev.
Mean
Std.dev.
Mean
Std.dev.
Time
1310
1310
1310
1310
1340
1340
1340
1340
1410
1410
1410
1410




Sample
Raw AMD
Spiked AMD
Product
Brine
Raw AMD
Spiked AMD
Product
Brine
Raw AMD
Spiked AMD
Product
Brine
Raw AMD
Raw AKD
Spiked AMD
Spiked AMD
Product
Product
Brine
Brine
As
0.01
2.42
0.01
3.33
0.01
2.37
0.01
3.27
0.01
2.39
0.01
3.51
0.01
(0)
-2.29
(0.14)
0.01
(0.00)
3.58
(0.30)
B Cd
0.7 <0.001
1.8 O.S97
1.0 0.004
2.8 1.26
0.7 <0.001
1.7 0.836
0.6 0.002
2.5 1.11
0.6 0.031
2.2 0.765
1.2 0.003
3.4 1.27
0.54 0.012
(0.12)(0.019)
2.01 0.828
(0.17)(0.063)
0.88 0.006
(0.20) (0.009)
3.08 1.22
(0.29)(0.13)
Cr
0.02
0.60
<0.01
0.83
0.02
0.53
<0.01
0.91
0.02
0.51
<0.01
0.87
0.02
(0.00)
0.54
(0.06)
0.01
(0.0)
0.82
(0.12)
Cu
0.01
6.44
0.02
9.33
0.01
6.23
<0.01
8.22
0.02
5.65
<0.01
9.28
0.02
(0.00)
6.18
(0.35)
0.01
(0.0)
9.12
(0.9S)
Hg
<0.0002
0.316
0.070
0.149
<0.0002
0.292
0.051
0.171
<0.0002
0.307
0.101
0.205
0.0002
(0.0)
0.277
0.023
0.060
(0.018)
0.173
(0.017)
Ni
0.16
0.78
<0.01
1.11
0.13
0.73
<0.01
1.05
0.14
0.69
<0.01
1.14
0.14
(0.01)
0.74
(0.05)
0.01
(0)
1.10
(0.12)
Se
<0.001
1.20
0.122
1.78
<0.001
1.30
0.113
1.90
<0.001
1.25
0.111
1.90
0.001
CO)
1.17
(0.17)
0.11
(0.01)
1.83
(0.15)
Zn
0.269
6.53
0.048
9.25
0.245
6.05
0.074
8.14
0.226
5. 43
0.064
9.20
0.258
(0.024)
6.25
(C.538)
C.056
(0.037)
9.63
(1.15)
P
0.80
1.98
0.46
2.00
0.96
1.04
0.30
1.44
C.76
1.02
0.46
1.54
0.700
(0.198)
1.500
(0.350)
0.324
(0.134)
1.954
(0.424)

-------
TABLE C-5.  REVERSE OSMOSIS CONVENTIONAL POLLUTANT ANALYSES
Date Time Sample
10-12-77 0940 Raw AMD
10-12-77 0940 Spiked feed
10-12-77 0940 Brine
10-12-77 0940 Product
10-12-77 1010 Raw AMD
10-12-77 1010 Spiked feed
10-12-77 1010 Brine
10-12-77 1010 Product
10-12-77 1040 Raw AMD
10-12-77 1040 Spiked feed
10-12-77 1040 Brine
10-12-77 1040 Product
10-12-77 1110 Raw AMD
10-12-77 1110 Spiked feed
10-12-77 1110 Brine
10-12-77 1110 Product
10-12-77 1140 Raw AMD
10-12-77 1140 Spiked feed
10-12-77 1140 Brine
10-12-77 1140 Product
10-12-77 1210 Raw AMD
10-12-77 1210 Spiked feed
10-12-77 1210 Brine
10-12-77 1210 Product
Cond
2800
6200
8500
78
2800
6000
8400
64
2800
6200
8600
60
2800
6000
8500
74
2800
6000
8400
64
2800
6000
8800
62
Acid
340
1420
2000
99
380
1320
1930
110
380
1340
2030
110
380
1300
2030
124
350
1300
19SO
124
360
1350
2130
110
PH
5.4
2.1
2.0
3.6
5.4
2.1
2.0
3.6
5.4
2.1
2.0
3.6
5.4
2.1
2.0
3.6
5.4
2.1
2.0
3.6
5.4
2.1
2.0
3.6
Ca Mg
370 110
370 110
600 190
.50 .16
370 110
360 110
580 180
.68 .20
360 110
360 110
590 170
.62 .20
370 110
370 120
600 190
.76 .25
370 110
370 110
590 180
.70 .24
370 110
370 110
590 180
.54 .20
Total
Fe
160
160
270
.18
160
160
260
.24
160
160
260
.24
160
160
260
.30
170
170
260
.30
170
170
270
.30
Fe2
140
140
230
0
140
140
230
0
140
140
230
0
140
140
230
0
150
140
230
0
150
150
230
0
Na
410
430
680
.22
410
410
650
.26
410
410
640
.40
420
420
630
.40
410
400
620
.40
410
400
630
.24
Al
4.8
4.8
6.6
.20
4.0
4.0
6.6
.30
5.0
4.8
6.8
.40
4.2
4.2
6.8
.20
4.4
4.4
6.4
.26
4.0
4.0
6.2
.16
Mn S04
4.9 2440
4.7 3090
6.9 4570
<.OS 9.6
4.9 2440
4.7 3090
6.9 4570
.05 12
4.9 2440
4.7 3090
6.9 4570
.05 16
5.0 2440
4.9 3090
7.1 4730
.05 22
5.0 2770
4.9 3090
7.1 4570
.05 26
5.0 2770
5.0 3090
7.1 4400
<.05 26
Alk
46
0
0
0
46
0
0
0
46
0
0
0
46
0
0
0
46
0
0
0
46
0
0
0
TDS
3500
4170
6320
10
3500
4140
6250
10
3490
4 ISO
6240
20
3500
4160
6420
20
3830
4150
6220
30
3830
4140
6070
30
Ion*
Bal
1.0
S.2
1.8
40.0
0.8
7.5
2.1
30.1
0.6
7.0
2.5
11.3
1.3
5.7
4.9
19.7
10.4
6.9
3.4
31.5
10.9
7.4
0.8
37.0
Ccontinuedj

-------
                                           TABLE C-5.   (Continued)
Date
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
Mean



Time
1240
1240
1240
1240
1310
1310
1310
1310
1340
1340
1340
1340
1410
1410
1410
1410
1440
1440
1440
1440




Sample
Raw AMD
Spiked feed
Brine
Product
Raw AMD
Spiked feed
Brine
Product
Raw AMD
Spiked feed
Brine
Product
Raw AMD
Spiked feed
Brine
Product
Raw AMD
Spiked feed
Brine
Product
Raw AMD
Blend
Brine
Product
Cond
2800
6000
8600
62
2600
5600
8400
62
2500
6000
8500
58
2500
5800
8600
58
2800
6000
8600
58
2 730
5980
8540
60
Acid
420
1280
2150
86
450
13CO
2050
190
450
1400
2060
190
450
1340
2210
120
450
1410
2160
170
400
1340
2070
130
PH
S.3
2.3
2.0
3.5
5.2
2.1
2.0
3.6
5.3
2.3
2.1
3.6
S.4
2.4
2.2
3.5
5.4
2.3
2.1
3.6
5.36
2.2
2.0
3.6
Ca
370
370
600
.65
380
380
600
.60
360
360
580
.62
350
350
580
.75
360
360
570
.56
400
365
590
.60
Kg
110
110
180
.22
110
110
180
.21
110
110
180
.23
110
110
170
.24
110
110
170
.20
110
110
180
.20
Total
Fe
170
170
280
.32
ISO
ISO
280
.32
170
170
280
.35
170
170
270
.38
170
170
270
.30
170
170
270
.30
Fe2
150
150
240
0
150
150
240
0
150
150
240
0
150
150
240
0
150
150
240
0
150
150
230
"
Ka
400
400
640
.32
410
420
640
.24
390
390
630
.36
400
400
620
.40
400
400
610
.20
400
400
640
.30
AI
5.2
5.2
7.6
.24
6.8
6.8
11
.24
6.6
6.6
11
.24
6.0
5.6
9.0
.16
4.2
4.2
7.6
.14
5.0
5.0
7.8
.20
Van
5.1
4.9
7.1
.05
5.1
5.0
7.2
.05
5.2
5.0
7.2
.05
5.1
4.9
7.3
.05
5.3
5.0
7.2
.06
5.1
50
7.1
.05
S04
2440
2900
4890
22
2600
3090
4730
26
2600
2800
4570
30
2S50
2770
4500
30
2440
2770
4570
28
2540
2990
4610
22
Alk
30
0
0
0
20
0
0
0
20
0
0
0
20
0
0
0
20
0
0
0
35
0
0
0
TDS
3490
3960
6600
20
3690
4180
6440
30
3630
3830
6250
30
3580
3800
6160
30
3480
3S1C
6200
30
3620
4040
6290
24
Ion*
&al
1.3
5 .5
7.0
6.8
1.7
4.0
4.0
34.4
6.9
4.3
3.9
41.6
5.3
5.1
5.7
30.9
0.4
2.8
6.8
41.9




All units are mg/1 except for pll, specific conductance  (nmhos/c»), and  ion balance  (expressed
as a percent difference between cations and anions as CaCO,).

-------
TABLE C-6.  MATERIAL BALANCE FOR REVERSE OSMOSIS STUDY
              (ratio of influent:  effluent)
Parameter
Arsenic
Boron
Cadmium
Chromium
Copper
Mercury
Nickel
Phosphorus
Selenium
Zinc
Acidity
Aluminum
Calcium
Iron, ferrous
Iron, total
Magnesium
Manganese
Sodium
Specific conductance
Sulfate
Total dissolved solids
Ratio
1.03
0.90
1.09
1.05
1.09
2.18
1.08
1.14
0.99
1.04
1.01
1.02
1.01
1.05
1.01
0.98
1.13
1.01
1.12
1.04
1.03
                              69

-------
TABLE C-7.  ION EXCHANGE TRACE ELEMENT ANALYSES
                   (ng/1)
Date
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
Time
1000
1000
1000
1000
1045
1045
1045
1045
1115
1115
1115
1115
1140
1140
1140
1140
1255
1311
1327
1345
1430
1435
1440
1445
1520
1520
1520
1520
Sample
Raw AMD
Spiked AMD
Cation effluent
Anion effluent
Raw AMD
Spiked AMD
Cation effluent
Anion effluent
Raw AMD
Spiked AMD
Cation effluent
Anion effluent
Raw AMD
Spiked AMD
Cation effluent
Anion effluent
Cation regener.
Cation regener.
Cation regener.
Cation regener.
Anion regener.
Anion regener.
Anion regener.
Anion regener.
Raw AMD
Spiked AMD
Cation effluent
Anion effluent
As
0.01
2.29
1.54
O.S8
0.01
2.48
1.66
0.40
0.01
2.71
1.55
0.18
0.01
3.12
1.44
0.10
2.48
2.11
1.14
1.01
1.50
0.40
0.19
2.23
0.01
2.42
1.53
1.88
B
O.S
2.1
1.9
1.3
0.5
2.1
1.7
0.2
0.3
2.1
2.1
<0.1
0.4
2.3
2.1
0.2
1.5
2.5
1.9
2.0
1.9
2.0
2.1
2.9
0.7
2.9
2.0
1.7
Cd
<0.001
0.884
0.009
<0.001
<0.001
0.884
0.010
0.001
0.001
0.922
0.009
<0.001

-------
TABLE C-7.  (Continued)
Date
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
10-12-77
Mean
Std.dev.
Mean
Std.dev.
Mean
Std.dev.
Mean
Std.dev.
Mean
Std.dev.
Mean
Std.dev.
Time
1605
1605
1605
1605
1650
1650
1650
1650
1745
1745
1745
1745
1905
1920
1935
1950
2025
2030
2035
2040






Sample
Raw AMD
Spiked AMD
Cation effluent
Anion effluent
Raw AMD
Spiked AMD
Cation effluent
Anion effluent
Raw AMD
Spiked .AMD
Cation effluent
Anion effluent
Cation regener.
Cation regener.
Cation regener.
Cation regener.
Anion regener.
Anion regener.
Anion regener.
Anion regener.
Raw AMD
Raw AMD
Spiked AMD
Spiked AMD
Cation effluent
Cation effluent
Anion effluent
Anicn effluent
Cation regener.
Cation regener.
Anion regener.
Anion regener.
As
0.02
2.50
1.84
0.63
0.03
2.96
1.89
0.31
<0.01
1.31
2.0
0.10
2.31
1.62
1.05
0.98
0.46
0.25
0.47
11.4
0.01
0.01
2.47
0.55
1.68
0.20
C.52
0.58
1.59
0.63
2.11
3.82
B
0.6
2.7
2.6
0.3
0.7
2.4
2.4
0.4
0.7
2.5
2.4
0.4
2.1
1.8
2.0
2.1
2.1
2.2
2.2
5.6
0.6
0.15
2.38
0.30
2.2
0.30
0.58
0.58
2.0
0.29
2.6
1.24
Cd
0.003
0.985
0.253
<0.001
<0.001
0.934
0.011
<0.001
<0.001
0.922
0.013
<0.001
1.87
2.28
0.909
1.11
0.080
0.035
0.003
O.001
0.001
0.00
0.945
0.119
0-042
0.085
<0.001
0.001
1.32
0.74
0.027
0.023
Cr
0.01
0.64
0.04
<0.01
0.01
0.64
0.09
<0.01
0.01
0.59
0.07
<0.01
1.21
0.86
0.35
0.33
0.10
0.04
0.05
0.08
0.02
0.012
0.63
0.077
0.05
0.019
0.01
0.01
0.61
0.45
0.06
0.02
Cu
0.04
7.68
0.09
0.03
0.02
7.16
0.06
0.01
0.02
7.26
0.10
0.01
15.5
20.5
11.0
10.1
0.30
0.11
0.09
0.10
0.03
0.016
7.27
0.861
0.11
0.052
0.03
0.026
12.7
7.0
0.16
0.07
Hg
<0.0002
0.804
0.078
0.0005
O.0002
0.804
0.108
0.0003
<0.0002
0.750
0.186
0.0005
0.366
0.122
0.259
0.337
0.100
0.013
0.013
0.063
O.OC02
-0-
0.723
0.082
0.074
0.060
0.0013
0.0027
0.237
0.108
0.05
0.057
Ni
0.15
0.88
0.01
<0.01
0.18
0.85
0.02
0.01
0.19
0.90
0.01
0.01
1.97
2.62
1.45
1.36
0.52
0.28
0.37
0.47
0.18
0.014
0.86
0.096
0.02
0.006
0.02
0.018
1.67
0.87
0.37
0.14
Se
<0.001
1.47
1.12
0.067
<0.001
1.65
1.38
0.019
<0.001
0.768
1.30
0.014
0.621
0.464
0.481
0.490
0.318
0.165
0.630
11.2
<0.001
-0-
1.34
0.27
1.19
0.13
0.088
0.14
0.593
0.19
2.00
3. SO
Zn
0.257
7.82
0.099
0.035
0.317
7.47
0.103
0.023
0.359
7.53
0.121
0.015
14.9
20.2
11.1
9.96
1.66
0.778
0.2S9
0.099
0.351
0.141
7.44
0.84
0.135
0.051
0.034
0.023
12.8
6.9
0-678
0.565
P
0.86
1.42
3.31
11.2
0.2S
1.45
4.35
1.6S
0.22
0.77
2.29
4.SO
0.95
0.37
0.50
0.76
2.02
1.49
1.23
2.69
0.74
0.40
1.47
C.39
S.86
8.23
9.71
5.54
3.13
3.50
5.39
10.7

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TABLE C-8.  ION1 EXCHANGE CONVENTIONAL POLLUTANT ANALYSES

Date Time
10-12-77 1000
10-12-77 1000
10-12-77 1000
10-12-77 1000
10-12-77 1045
10-12-77 1045
10-12-77 1045
10-12-77 1045
10-12-77 1115
10-12-77 1115
10-12-77 1115
10-12-77 1115
10-12-77 1140
10-12-77 1140
10-12-77 1140
10-12-77 1140
10-12-77 1255
1C-12-77 1311
10-12-77 1327
10-12-77 1345
10-12-77 1430
10-12-77 1435
10-12-77 1440
10-12-77 1445
10-12-77 1520
10-12-77 1520
10-12-77 1520
10-12-77 1520
Sample Cond
Raw feed 2600
Spiked feed 2600
Cation effluent 10000
Anion effluent 1400
Raw feed 2600
Spiked feed 2600
Cation effluent 10000
Anion effluent 600
Raw feed 2600
Spiked feed 2600
Cation effluent 10000
Anion effluent 380
Raw feed 2700
Spiked feed 2700
Cation effluent 9600
Anion effluent 330
Cation effluent 4200
Cation effluent 27000
Cation effluent 60000
Cation effluent 70000
Anion effluent 9000
Anion effluent 2500
Anion effluent 1600
Anion effluent 23000
Raw feed 2700
Spiked feed 3000
Cation effluent 10100
Anion effluent 5600
Acid
460
460
2600
0
430
430
2690
0
440
440
2690
0
410
430
2400
0
770
4430
19410
22270
2640
810
500
460
420
550
2790
0
PH
5.5
5.3
1.8
11
5.5
5.3
1.8
9.8
5.5
5.3
1.8
9.5
5.4
5.2
1.8
9.0
2.4
1.5
1.1
1.1
1.5
2.0
2.5
3.5
5.4
3.0
1.8
12
Ca
350
350
10
4.6
340
340
10
12
350
350
10
8.S
350
350
13
9.6
150
730
1000
700
20
35
35
45
350
350
10
.19
Mg
100
100
2.7
4.0
100
100
2.5
2.1
100
100
2.6
1.65
100
100
3.0
2.2
50
520
300
200
4.2
7.3
7.4
5.5
100
100
2.5
.06
Total
Fe
150
150
2.2
.05
150
150
2.0
.05
150
150
2.0
.05
150
150
2.6
.05
68
814
430
300
20
50
40
20
150
150
2.1
.05
Fe2
150
140
2.2
0
144
142
2.0
0
140
140
2.0
0
150
140
2.6
0
66
800
430
300
19
44
40
20
150
150
2.1
0
Na
400
400
50
400
400
400
50
170
400
400
50
100
400
400
150
80
600
2000
760
385
55
80
170
9200
380
380
50
1400
Al
4.0
4.0
.12
.12
4.0
4.0
.20
.20
4.0
4.0
.20
.20
4.2
4.2
.26
.05
3.4
40
16
10
.50
.90
.48
.60
5.2
5.2
.28
.48
Mn S04 Alk
3.7 2340 40
3.7 2330 30
.08 890 0
.05 380 560
3.8 2350 45
3.8 2330 25
.06 980 0
.05 150 250
3.9 2350 45
3.9 2330 25
.05 980 0
.05 150 200
3.9 2340 40
3.9 24SO 15
.12 1000 0
.05 200 150
2.0 1980 0
30 11400 0
8.0 14050 0
6.1 7830 0
.40 1700 0
1.0 820 0
.95 690 0
.50 18850 0
3.7 2330 25
3.7 2470 0
.08 980 0
.05 3200 390
TDS
3350
3340
960
790
3340
3320
1050
330
3350
3330
1050
260
3350
3490
1170
290
2850
15530
16570
9430
1800
1800
940
28120
3310
3450
1050
4600
Ion*
Bal
0.7
0.5
1.7
5.9
2.0
0.2
7.7
1.6
0.9
0.8
7.7
30
0.7
5.0
10.9
42
8.2
1.8
30.0
1.9
2.1
4.5
1.3
3.2
1.5
4.0
7.6
17.7
Cation
Equiv.
2460
2470
150
9CO
2440
2440
ISO
400
2460
2460
150
250
2460
2460
380
210
2040
10060
6280
4020
230
390
560
20230
2410
2410
ISO
3060
("continued"!

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                                                  TABLE C-8 (Continued)
Date Time
10-12-77 1605
10-12-77 1605
10-12-77 1605
10-12-77 1605
10-12-77 1650
10-12-77 1650
10-12-77 1650
10-12-77 1650
10-12-77 1745
10-12-77 1745
10-12-77 174S
10-12-77 1745
10-12-77 1905
10-12-77 1920
10-12-77 1935
10-12-77 1950
10-12-77 2025
10-11-77 2030
10-12-77 2035
10-12-77 2040
Mean



Sample Cond
Raw feed 2800
Spiked feed 2800
Cation effluent 11000
Anion effluent 850
Raw feed 2800
Spiked feed 2800
Cation effluent 11000
Anion effluent 380
Raw feed 2800
Spiked effluent 2800
Cation effluent 10000
Anion effluent 350
Cation effluent 12150
Cation effluent 50000
Cation effluent 64000
Cation effluent 69000
Anion effluent 2700
Anion effluent 2500
Anion effluent 17000
Anion effluent 28000
Raw feed 2700
Spiked feed 2740
Cation effluent 21580
Anion effluent 1240
Acid
460
480
2720
0
560
560
2670
0
600
620
2570
0
3160
15770
16110
16910
740
370
470
410
470
500
2640
0
pH
5.5
S.I
1.8
10
5.2
4.7
2.0
9.6
4.9
4.5
2.0
8.6
2.1
1.3
1.2
1.2
2.0
2.6
3.5
3.7
5.4
4.8
1.9
9.9
Ca
350
350
10
14
350
350
10
9
350
350
12
11
800
870
930
700
42
40
62
30
350
350
11
8.7
Mg
100
100
2.5
2.5
100
100
2.5
1.8
100
100
2.8
2.7
350
400
280
200
8.6
8.6
12
3.8
100
100
2.6
2.2
Total
Fe
170
160
2.0
.05
200
200
1.9
.05
200
200
2.0
.05
500
590
420
320
60
40
26
6.0
170
160
2.1
.05
Fe2
160
150
2.0
0
180
180
1.5
0
190
190
2.0
0
500
580
400
310
50
40
22
5.4
160
140
2.1
0
Na Al
360 5.6
350 5.6
45 .22
220 .24
350 8.8
340 8.8
45 .16
100 .06
330 10
330 10
130 .20
150 .16
1400 17
1000 20
500 13
310 10
80 1.0
510 .46
6250 .10
12000 .66
380 5.7
380 5.7
71 .20
330 .19
Mn S04 Alk
3.8 2490 25
4.0 2320 15
.12 980 0
.05 200 390
4.2 2480 10
4.2 2470 5
.08 650 0
.05 100 150
4.3 2470 8
4.3 2470 0
.12 800 0
.05 220 170
9.0 7540 0
25 10730 0
6.8 9100 0
5.8 7030 0
1.1 950 0
.94 1480 0
.88 14770 0
.38 24550 0
3.9 2390 30
3.9 2400 14
.09 910
.05 580 280
TDS
3470
3290
1040
440
5480
3470
710
210
3470
3460
950
390
10620
13640
11250
S580
1140
2080
21120
36590
3390
3340
1000
900
Ion*
Bal
4.9
1.9
8.8
11.2
4.5
4.9
5.6
2.2
5.5
4.7
1.9
8.7
0.8
12.9
9.4
3.5
6.9
5.7
9.5
2.8




Cation
Equiv .
2410
2580
140
530
2470
2450
140
250
2440
2440
320
370
7500
7220
5420
3900
420
1320
13880
26270




All  units  are  iag/1 except for pH, specific conductance (ymhos/cm), and ion balance
(expressed  as a percent difference between cations and anions as CaCO.,) .  Cation
equivalents are expressed as CaCO,.

-------
                                  GLOSSARY
ION EXCHANGE TERMINOLOGY

                                                -2     -2
anion:  A negatively charged ion  (e.g., OH~, SO    , CO   ).

cation:  A positively charged ion  (e.g., Na+, Fe+  , Al  ).

dosage rate:  Also called regeneration level, it is the amount of regenerant
     chemical (expressed as 100 percent-concentration and converted to
     calcium carbonate equivalence) per volume of resin in the ion exchange
     column.  The dosage rate is commonly expressed in grams  (of 100%
     regenerant) per liter of resin or 16/cu ft.

exchanger capacity:  The actual total of ions (expressed as CaCOj) exchanged
     during the service cycle.  This is always less than the theoretical
     capability described by the dosage rate.  Exchanger capacity is commonly
     expressed as grams (as CaC03) per liter of resin or grains/cu ft.

ion exchange:  A reversible exchange of ions between a solid and a liquid
     in which there is no substantial change in the solid.  The solid is the
     ion exchange resin.

regenerant:  A solution containing a high concentration of suitable ions used
     to convert (or regenerate) an ion exchange resin to the desired ionic
     form (e.g., ^SO  supplies H+ ions to regenerate strong-acid cation
     resins to the H+-form) .

regenerant utilization efficiency:  The ratio of regenerant chemical utilized
     as compared to the amount added to regenerate the resin, expressed as
     a percentage.  This is calculated by dividing the exchanger capacity by
     the dosage rate.

strong-acid cation resin:   A resin, which when regenerated with acid, will
     exchange hydrogen ions (H+) for cations present in the influent according
                            *
     to FeS04 + 2H+-R        .      2   .

weak-base anion resin:  A resin unable to split neutral salts but which
     absorbs free acid, according to R + P^SO, -> R-H2SO .
                                      74

-------
REVERSE OSMOSIS TERMINOLOGY

brine:  The waste solution resulting from reverse osmosis separation of an
     influent into product and brine (also called concentrate).

flux:  The rate of water permeation through the reverse osmosis  membrane,
     usually expressed in liters/sq m/day (or gal/sq ft/day)  at  a specified
     temperature and pressure.  The flux rate is strongly dependent upon
     temperature, applied pressure, and osmotic pressure.  In this report,
     the pressure specified in the net driving pressure (i.e., applied
     pressure minus osmotic pressure).

osmotic pressure:  The pressure at which the permeation rates from the brine
     side of the membrane to the product side and vice versa are in equilibrium.
     The osmotic pressure is a characteristic of the chemical composition of
     the influent and is strongly related to concentration.  When the applied
     pressure exceeds the osmotic pressure, dewatering begins.  Osmotic
     pressure is usually expressed in g/sq cm or psi.

recovery:  The percentage of the raw water fed to the reverse osmosis unit
     that results as product.

reverse osmosis:  Flow through a semipermeable membrane where the direction of
     flow is from the concentrated solution to the dilute solution.  Such a
     flow is induced by pressure applied to the concentrated solution.

salt rejection:  A measure of a membrane's ability to selectively allow pure
     water to pass through but reject the passage of impurities; a measure
     of a membrane's impermeability with respect to salts; usually expressed
     as a percentage:

          (Influent Quality - Product Quality]
                  (Influent Quality)            x 10°-
                                      75

-------
NEUTRALIZATION TERMINOLOGY

material balance:  A calculation to compare inputs and outputs of a chemical
     system using | f low in x concentration in = flow out x concentration out]

stoichiometric factor:  The ratio of amount of neutralizer required to treat
     original amount of acid present:

          Stoichiometric factor = Alkalinity added (as CaC03)
                                  Influent acidity (as
utilization efficiency:  A measure of the proportion of a neutralizer that
     reacts with the acid water as compared to the amount originally added.
     Since alkalinity imparted to the water is considered a benefit, the
     formula for utilization efficiency is:

          Utilization efficiency = Alkalinity used
                                   Alkalinity added
               therefore,

                                    [influent acidity - effluent acidity +1
          Utilization efficiency =  [Effluent alkalinity (all as CaCO^)   J
                                        Alkalinity added (as CaC03)X  °°
                                     76

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 1. REPORT NO.
 EPA-600/7-79-101
2.
                             3. RECIPIENT'S ACCESSION NO.
 4. TITLE AND SUBTITLE
 Removal  of Trace Elements from Acid  Mine Drainage
                             5. REPORT DATE
                              April  1979 issuing date
                                                           6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)
 Roger C.  Wilmoth, James L. Kennedy,  Jack R.  Hall, and
 Charles W.  Stuewe
                                                           8. PERFORMING ORGANIZATION REPORT NO.
 9. PERFORMING ORGANIZATION NAME AND ADDRESS

 Hydroscience,  Inc.
 Knoxville,  Tennessee  37919
                              10. PROGRAM ELEMENT NO.
                              11. CONTRACT/GRANT NO.

                                 68-03-2568
 12. SPONSORING AGENCY NAME AND ADDRESS
 Industrial Environmental Research  Lab.
 Office of Research and Development
 U.S. Environmental Protection Agency
 Cincinnati.  Ohio  45268
            - Cinn, OH
                              13. TYPE OF REPORT AND PERIOD COVERED
9/77 1/7
                              14.
                                  EPA/600/12
 15. SUPPLEMENTARY NOTES
 This was  a  cooperative in-house and  contract-supported research  effort.
      Lime neutralization, reverse osmosis,  and ion exchange were  studied for their
 effectiveness  in removing mg/1 levels  of  ten specific trace elements  from spiked
 acid mine drainage under typical operating  conditions.  The specified toxic materials
 were arsenic,  boron,  cadmium, chromium, copper,  mercury, nickel,  phosphorus, selenium
 and zinc.                                                                                '

      Treatment by lime neutralization  was very effective in removing arsenic, cadmium
 copper, mercury,  nickel, and zinc, and relatively ineffective in  removing boron and   '
 phosphorus.  Reverse  osmosis was very  effective  in rejecting arsenic, cadmium
 chromium, copper,  nickel, and zinc, and relatively ineffective in rejecting boron
 The two-bed  (strong acid-weak base) ion exchange system was very  effective in removing
 all of tne trace  elements  except phosphorus and boron.  None of  the three treatment
 methods was  very  effective in removing phosphorus.

      Analysis  for  boron proved troublesome.   Use of the standard  nitric  acid metals
 preservation methods  was found to be inappropriate for samples requiring boron
 analysis.
 7.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                                                                           COSATl Field/Group
 Neutralizing
 Calcium oxides
 Drainage
 Acid treatment
 Trace elements
                Reverse osmosis
                [on exchange
                 ime neutralization
                 cid mine drainage
                Toxic materials
      13B
                                              19. SECURITY CLASS (ThisReport)
                                                Unclassified
                                           21. NO. OF PAGES

                                              87
                                              20. SECURITY CLASS (Thispage)
                                                Unclassified
                                           22. PRICE
EPA Form 2220-1 (9-73)
                                          77
                                                    •frll.S. GOVERNMENT PRINTING OFFICE: 1979-457-060/1669 Region No. 5-11

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