EPA Report No.
                                         January 1994
CADMIUM AND CHROMIUM RECOVERY FROM
       ELECTROPLATING RINSEWATERS
                        by

  Arun R. Gavaskar, Robert F. Olfenbuttel, and Jody A. Jones
                      Battelle
                Columbus, Ohio 43201
               Contract No. 68-CO-0003
               Work Assignment No. 3-36
                    Project Officer

                     Lisa Brown
Waste Minimization, Destruction, and Disposal Research Division
          Risk Reduction Engineering Laboratory
                Cincinnati, Ohio 45268
      RISK REDUCTION ENGINEERING LABORATORY
        OFFICE OF RESEARCH AND DEVELOPMENT
      U.S. ENVIRONMENTAL PROTECTION AGENCY
              CINCINNATI, OHIO 45268
                                            } Printed on Recycled Paper

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                                           NOTICE                                i
                                                                                  f

         This material has been funded wholly or in part by the U.S. Environmental Protection Agency
(EPA) under Contract No. 68-CO-0003 to Battelle. It has been subjected to the Agency's peer and
administrative review and approved for publication as an EPA document.  Approval does not Dignify that
the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency or
Battelle; nor does mention of trade names or commercial products constitute endorsement or
recommendation for use.

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                                         FOREWORD

         Today's rapidly developing and changing technologies and industrial products and
practices frequently carry with them the increased generation of materials that, if improperly dealt
with, can threaten both public health and the environment.  The U.S. Environmental Protection
Agency (EPA) is charged by Congress with protecting the Nation's land, air, and water resources.
Under a mandate of national environmental laws, the agency strives to formulate and implement
actions leading to a compatible balance between human activities  and the ability of natural systems
to support and nurture life. These laws direct the EPA to perform research to define our
environmental problems, measure the impacts, and search for solutions.
         The Risk Reduction Engineering Laboratory is responsible for planning,  implementing, and
managing research, development, and demonstration  programs to  provide an authoritative,
defensible engineering basis in support of the policies, programs, and regulations of the EPA with
respect to drinking water, wastewater, pesticides, toxic substances, solid and hazardous wastes,
Superfund-related activities, and pollution prevention.  This publication is one of the products of
that research and provides a vital communication link between the researcher and the user
community.
         Passage of the Pollution Prevention Act of 1990 marked a strong change in the U.S.
policies concerning the generation of hazardous and nonhazardous wastes. This bill implements the
national objective of pollution prevention by establishing a source reduction program at the EPA and
by assisting States in  providing information and technical assistance regarding source reduction.  In
support of the emphasis on pollution prevention, the "Waste Reduction Innovative Technology
Evaluation (WRITE)  Program" has been designed to identify, evaluate, and/or demonstrate new
ideas and technologies that lead to waste reduction. The WRITE Program emphasizes  source
reduction and on-site recycling. These methods reduce or eliminate transportation, handling,
treatment, and disposal of hazardous materials in the environment. The technology evaluation
project discussed in this report emphasizes the study and development of methods to reduce
waste.

                                                   E. Timothy Oppelt, Director
                                                   Risk Reduction Engineering Laboratory
                                             III

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                                         ABSTRACT

        This evaluation addresses the product quality, pollution prevention, and economic issues
involved in the use of ion exchange to recover cadmium and chromium from electroplating rinse-
waters.  Test results showed that the water returned to the rinse after ion exchange was of
acceptable quality.  On the cadmium  line, the ion exchange resin was regenerated with sodium
                                                                                 I
hydroxide solution and the regenerant was subjected to electrolytic metal recovery to recover.
cadmium for reuse in the plating bath. On the chromium line, the ion exchange resin was! regener-
ated with sodium hydroxide solution and the regenerant was passed through a cation exchange
resin in an effort to  recover chromic acid. However, due to excess sodium hydroxide in the
regenerant, chromic acid could not be recovered with the amount of resin used. The pollution
prevention potential of ion exchange on the cadmium and chromium rinsewater is good, especially
if further testing  establishes good recovery of chromic acid. Payback  periods of 1 year ort the
cadmium ion exchange and 8 years on the chromium system are projected.
        This report was submitted in  partial fulfillment of Contract Number 68-CO-0003,  Work
Assignment 3-36, under the sponsorship of the U.S. Environmental Protection Agency. This report
covers the period from May 1,  1991 to January 31, 1994,  and work was completed as of
January 31, 1994.                                                                :
                                            IV

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                                      CONTENTS


Notice .  .	. . .  .	    jj
Foreword  . .	   jjj
Abstract	   iv
Figures	   vj
Tables	   vi
Acknowledgments 	,	-....-	  	   vii

SECTION 1: Project Description	    1
     Project Objectives	». .    2
     Description of the Site	    2
     Description of the Technology	    3
     Summary of Approach .	    3
         Product Quality Evaluation	    6
         Pollution Prevention Evaluation		    6
         Economic Evaluation	 .	    7

SECTION 2: Product Quality Evaluation		    8
     On-site Testing  . . . .	    8
     Analytical Testing Results	   10
     Product Quality Assessment		  14

SECTION 3: Pollution Prevention Potential	  16
     Waste Volume Reduction	  16
     Pollutant Reduction	  18
     Pollution  Prevention Potential Assessment  	  19

SECTION 4: Economic Evaluation	  20
     Major Operating Costs	 .  20
     Capital Costs	  23
     Fleturn on Investment	  23

SECTION 5: Quality Assurance		 .  25
     On-site Testing	  25
     Laboratory Analysis	  26
     Limitations and Qualifications		;  27

SECTION 6: Conclusions and Discussion		  28

SECTION 7: References	 .  30

APPENDIX A:  EMR Operation for Cadmium Recovery from Regenerant	 .  31
APPENDIX B:  Wastewater  Treatment Costs	  32
APPENDIX C:  Economic Analysis of Cadmium Rinsewater Ion Exchange	'.....'	  34
APPENDIX D:  Economic Analysis of Chromium Rinsewater Ion Exchange	  38

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                                 CONTENTS (Continued)
APPENDIX E:  Standard Analytical Methods for Rinsewater Analysis
APPENDIX F:  Completeness	
43
44
                                       FIGURES
Number
     1   Ion Exchange Recovery of Cadmium from Plating Rinsewater .  .	;        4
     2   Ion Exchange Recovery of Chromium fromjPlating Rinsewater	.:	  5

                                            I

                                       TABLES


   1    Cadmium Rinsewater Test Samples	    9
   2    Chromium Rinsewater Test Samples	}.  . .'  10
   3    Cadmium Rinsewater Analysis	   ;      -\ 1
   4    Statistical Significance for Cadmium Evaluation  	:...'.'  13
   5    Chromium Rinsewater Analysis	I.  . . .  is
   6    Statistical Significance for Chromium Evaluation	       15
   7    Fresh Rinsewater Flow Rates  	                  -\ 7
   8    Waste Volume Reduction	 .       17
   9    Operating Costs Comparison for Cadmium System  	       21
  10    Operating Costs Comparison for Chromium System	  22
  11    Precision Data for Rinsewater Characterization	  26
  12    Accuracy Data for Rinsewater Characterization	       27
                                         VI

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                                   ACKNOWLEDGMENTS

         The U.S. Environmental Agency and Battelle wish to thank Sumner Kaufman of ESSAR
Environmental Services (consultant to the Connecticut Hazardous Waste Management Service),
who located the technology and site for this project, encouraged its inclusion in the WRITE
Program, and provided support during the evaluation. The authors also appreciate the efforts of
Jack Healy and Keith Bienkowski of The Torrington Company for their time, input, and support
during the evaluation.  George Riccucci, of Plating Services Company, is also acknowledged for his
support on this project.
                                           VII

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                                         SECTION 1
                                   PROJECT DESCRIPTION

         This study, performed under the U.S. Environmental Protection Agency's (EPA) Waste
Reduction and Innovative Technology Evaluation (WRITE) Program, was a cooperative effort among
EPA's Risk Reduction Engineering Laboratory (RREL), Connecticut Hazardous Waste Management
Service (CHWMS), and Torrington Company. The objective of the WRITE Program is to evaluate,
in a typical workplace environment, examples of prototype or innovative commercial technologies
that have potential for reducing waste.  In general, for each technology to be evaluated, three
issues should be addressed.
         First, it must be determined whether the technology is effective.  Since waste reduction
technologies usually involve recycling or reusing materials, or using substitute materials or tech-
niques,  it is important to verify that the quality of the recycled  product is satisfactory for the
                                                                           . , l
intended purpose.  Second, it must be demonstrated that using the technology has a measurable
positive effect on reducing waste. Third, the economics of the new technology  must be quantified
and compared with the economics of the existing technology.  It should be clear, however, that
improved economics  is not the only criterion for the use of the new technology.  There may be
justifications other than saving money that would encourage adoption of new operating
approaches. Nonetheless, information about the economic implications of any such potential
change  is important.
         This evaluation addresses the issues involved in using an ion  exchange technology for
recovering cadmium and chromium from electroplating rinsewater. The ion exchange system used
in this study was manufactured  by CTEO Tek, Inc.* and supplied by Plating Services, Inc.*  Other
ion exchange units and technologies (with varying capabilities) applicable to the same wastestream
(electroplating rinsewaters) are also commercially available.
        Mention of trade names and products does not constitute endorsement for use.
                                             1

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PROJECT OBJECTIVES

         The goal of this study was to evaluate a technology that could be used to recover
cadmium and chromium from electroplating rinsewaters.  This study had the following critical
objectives:                                                                        I
         «    Evaluate the rinsewater quality to demonstrate the effectiveness of the ion
              exchange unit                                                       r
         «    Evaluate the pollution prevention potential of this technology
         •    Evaluate the cost of ion exchange versus the cost of former practice      '
              (disposal).
DESCRIPTION OF THE SITE

         The site for testing this new technology was The Torrington Company's Standard Plant
located in Torrington, Connecticut. The Torrington Company is one of the world's leading broad-
line bearing manufacturers. Production volume exceeds hundreds of thousands of assemblies per
day. Many parts are highly precision crafted.  The cadmium line processes 250,000 IDS of parts
per year.  The chromium line processes 350,000 Ibs of parts per year. The Standard Plant has
been cited in the past by the Connecticut Department of Environmental Protection (CDEP):for
violating  its municipal wastewater discharge permit.. One reason for the violation was the! presence
of plating chemicals in the wastewater and sludge.  '                                   i
         In order to alleviate the non-compliance problem and delist the sludge, Torrington first did
an in-house assessment of the cadmium plating line and its corresponding discharge quantities.
Next, various methods for recovering metals and cyanide from plating  rinse water were investi-
gated.  A reverse osmosis unit was tested in-house on a trial basis, but the system performance
was found to be unsatisfactory and the unit was removed.  Since then, a combination of ion
exchange and electrolytic metal recovery (EMR) are being evaluated on the cadmium line.  ;The full-
scale ion exchange unit was installed in. May 1992 and is operating satisfactorily.  A pilot  ion
exchange unit is being tested on the chromium line  in preparation for full-scale installation.
Although ion exchange is an established method for metal ions removal in the metal finishing
industry, Torrington used a cautious approach to develop operating parameters specific to Its plant.

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 DESCRIPTION OF THE TECHNOLOGY
                                        -'.j.,-          '"•-•> "  f-.L-.-
          Figure 1 shows the cadmium ion exchange system configuration.  Counter flow rinsing
 and discharge of rinsewaters to waste treatment was the original practice.  Eventually, a closed
 loop system which recirculates the rinsewater continuously through the ion exchange was
 established.  Currently, rinse water from Rinse 1  tank is continuously drawn into the ion exchange
 column. The water is first passed through a filter to prevent suspended solids from contacting the
 resin.  The anionic resin captures  a cadmium-cyanide complex.  The ion exchange column contains
 2 cu ft (94 Ibs) of anionic resin, the capacity of which  is 2.5 Ibs of cadmium per cu ft of resin.  The
 water  is then returned to Rinse 2  tank. An emergency bypass valve allows this water to be
 discharged to waste in the event that cadmium or cyanide levels are found to be too high.  Some
 fresh make-up water is added daily to the tanks to compensate for water dragout on the
 workpiece.
         The resin is periodically  regenerated with a 15 to 20% NaOH solution. The resulting
 regenerant is taken to the EMR unit, where cadmium is recovered on the cathode and returned to
 the plating tank.  Some cyanide is destroyed by decomposition  in the EMR process.  Both cadmium
 and  cyanide are on EPA's 33/50 list of target chemicals.
         Figure 2 shows the chromium system configuration.  The primary ion exchange resin is
 anionic to remove hexavalent chrome. The full-scale unit is estimated  to contain 3 cu ft (14 Ibs) of
 anionic resin, with a capacity of 3 Ibs of hexavalent chromium per cu.ft. of resin.  In the future, a
 cationic resin component will be added to the primary resin to remove  any trivalent chrome  that
 may be present in the rinsewater.  The anionic resin is  periodically regenerated with a 15 to 20%
 NaOH solution and the resulting solution (sodium  chromate) is run through a secondary (cationic)
 exchange  unit, which should convert the regenerant back to chromic acid and return it to the
 plating tank.  In the secondary resin,  sodium  ions in sodium chromate are substituted with
 hydrogen ions.  Chromium is on EPA's 33/50 list  of target chemicals.
SUMMARY OF APPROACH

         Quality Assurance Project Plans (QAPPs) prepared at the beginning of this study (Battelle
1992a & b) describe the detailed approach and scientific rationale used to evaluate the ion
exchange system.  The evaluation covered product quality, pollution prevention, and economics of
the process.

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Product Quality Evaluation                                                          •

         The objective of this part of the evaluation was to show that the water that is processed
through the ion exchange system is clean enough for use as rinsewater in the cadmium or|chro-
mium plating lines. Contaminant-free rinsewater ensures a good workpiece finish. The approach
was to collect three samples each of the rinsewater before and after passing through the ion
exchange system.  These samples were analyzed in the laboratory to evaluate the removal of
contaminants.  Batches of rinsewater (one batch for cadmium  and one for chromium) were also
spiked with plating bath solution to  elevate contaminant levels (cadmium or chromium). The spiked
rinsewater was then run through the ion exchange  in order to test the limits of the unit.  Because
rinsewater was continuously circulated through the ion exchange system throughout the  day, three
samples of the rinsewater — one each at the beginning, middle, and end of a shift — were taken to
ensure that water quality remained relatively steady over time.                          :

Pollution Prevention Evaluation                                                      '
                                                                                  i
         The pollution prevention potential of the technology was evaluated by estimating the
amount  of cadmium or chromium removed per year from the rinsewater that would otherwise have
gone to  waste.  This was calculated based on (a) the cadmium and  cyanide (or chromium) :concen-
trations  in time-averaged samples of the rinsewater collected during testing and (b) the annual
water usage in the rinse tanks before ion exchange was installed.                       I
         The ability to recover the cadmium and chromium in  forms that can be reused inline
plating bath was also evaluated.  The metals on the ion exchange resin were recovered during the
regeneration of the resin. In the case of cadmium,  the regenerant was passed through the, resin
and treated using electrolytic metal  recovery (EMR) to recover  the cadmium. Samples  of the regen-
erant were collected immediately before and after the EMR operation in order to see how much
cadmium was being recovered by EMR. During the on-site testing visit, the resin had not
reached the point of exhaustion, and had not been  regenerated. Torrington conducted the
regeneration and EMR operations and collected the samples at a later date.
         In the case of chromium, the regenerant was run through  the secondary (cation)
exchange resin to recover chromic acid, and pH of  the regenerant was monitored.        I

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Economic Evaluation
              The economic evaluation took into account the capital and operating costs of the ion
exchange technology. The cost of operating the ion exchange units was compared with the costs
of wastewater treatment and disposal prior to installation of the new technology.

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                                        SECTION 2
                              PRODUCT QUALITY EVALUATION

         The objective of the product quality evaluation was to show that ion exchange removes
the contaminants present in rinsewater so that the water can be returned to the rinsing tanks and
reused.                                                                          '
ON-SITE TESTING

         Table 1  describes the on-site testing conducted on the cadmium line at Torringtoh.  As
each of three barrels of parts (workpiece) was dipped into Rinse 1 tank, a sample of rinsewater was
collected from Rinse 1 tank to represent "before" conditions (samples CD-X1-B1 to CD^X1-B3).
For the 1 min that the barrel  is dipped in the tank, the concentration of contaminants washed off
the parts is expected to reach maximum levels. Therefore, a continuous 1-min composite; sample
was drawn from Rinse 1 tank after a 5-sec delay for mixing following the immersion of each barrel.
                                                                                 i
The rinse tank dimensions are not much larger than the  dimensions of the barrel; thus, distribution
of contaminants throughout the tank is quick.                                        '
         Corresponding to each "before" sample, a  1-min continuous "after" sample (samples
CD-X1-A1 to CD-X1-A3)  was collected from a sampling port installed immediately after the ion
exchange resin.  The "after"  sample was collected from this port instead of from Rinse 2 tank to
get an estimate of the best water quality achievable by  the ion exchange.  The start of the "after"
sample collection was delayed by 7 sec (from the start  of the "before" sample) to allow the
rinsewater drawn from Rinse 1 tank to circulate through the ion exchange to the sample port. This
delay was previously determined based on the time it took  water from the tank to start flowing out
of the sample port after the ion exchange pump was first switched on.                  :
         In order to test the performance of the ion exchange system at higher-than-normal levels,
a 5-gal batch of rinsewater from Rinse 1 was spiked with approximately 100 mL of liquid from the
                                                                                 I
plating bath (representing higher dragout of contaminants).  One spot sample each of the 'spiked
rinsewater was collected  both before  (CD-XS-B1) and after (CD-XS-A1) passing it through the ion
exchange.                                                                        ;

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                       TABLE 1.  CADMIUM RINSEWATER TEST SAMPLES
Water
Sample No.
CD-X1-B1
CD-X1-B2
CD-X1-B3
CD-X1-A1
CD-X1-A2
CD-X1-A3
CD-XS-B1
CD-XS-A1
CD-R1-B1
CD-R1-B2
CD-R1-B3
CD-R2-B1
CD-R2-B2
CD-R2-B3
CD-X30-B1
CD-FB-1
Sample Description
Before ion-x
Before ion-x
Before ion-x
After ion-x,
After ion-x,
After ion-x.
, Run 1
, Run 2
, Run 3
Run 1
Run 2
Run 3
Spike, before ion-x
Spike, after ion-x
9:00am
12:30pm
4:OQpm
9:00am
12:30pm
4:00pm
Before ion-x
Field blank




Sample
Location
Rinse 1 Tank
Rinse 1 Tank
Rinse 1 Tank
Ion-x outlet
Ion-x outlet
Ion-x outlet
Collection tank
Ion-x outlet
Rinse 1 Tank
Rinse 1 Tank
Rinse 1 Tank
Rinse 2 Tank
Rinse 2 Tank
Rinse 2 Tank
Rinse 1 Tank
Tap water
Sample Type
1 min,
1 min,
1 min.
1 min,
1 min,
1 min.
spot
spot
spot
spot
spot
spot
spot
spot
30 min
spot
continuous
continuous
continuous
continuous .
continuous
continuous



continuous

         Three spot samples each were collected from Rinse 1  (CD-R1-B1 to CD-R1-B3) and
 Rinse .2 (CD-R2-B1 to CD-R2-B3) to represent the beginning, middle, and end of the first shift. The
 objective was to see how water quality in the rinse tanks varies throughout the day as the water is
 circulated continuously through the ion exchange unit.
         In addition, a 30-minute continuous "before" composite sample was also collected from
 Rinse 1 tank to estimate the average loading on the ion exchange system.  This additional sample
 was collected  because the 1-min continuous composites described earlier were designed to capture
 maximum concentrations when the barrel is in the rinse, not average concentrations over a pro-
 longed period of operation that includes the time periods in between successive barrels. Barrels are
 brought for rinsing intermittently.  During the 30 min of this sample, 3 barrels were processed
through the rinses (1 min in each tank  for each barrel).  A field blank consisting of a sample of the
fresh city tap water used to supply the rinse tanks was collected to ensure that there were no
contributions of contaminants from extraneous sources, as well as to  provide a basis of comparison
for evaluating cadmium and chromium  removal from the rinsewater.
         Table 2  describes similar testing conducted on the chromium system.  This includes
"before" and "after" 1-min samples, a spike sample, a 30-min continuous "before" composite
(CR-X2-B1), and a field blank.  Three spot samples (at the beginning, middle, and  end of the  shift)

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                    TABLE 2. CHROMIUM RINSEWATER TEST SAMPLES
Water
Sample No.
CR-X1-B1
CR-X1-B2
CR-X1-B3
CR-X1-A1
CR-X1-A2
CR-X1-A3
CR-XS-B1
CR-XS-A2
CR-X2-B1
CR-CX-A2
CR-FB-1 lal
Sample
Description
Before ion-x
Before ion-x
Before ion-x
After ion-x
After ion-x
After ion-x
Spike, before ion-x
Spike, after ion-x
Before ion-x
Regenerant
Field blank
Sample
; Location
Rinse 1 Tank
Rinse 1 Tank
Rinse 1 Tank
Ion-x outlet
Ion-x outlet
Ion-x outlet
Collection tank
Ion-x outlet
Rinse 1 Tank
Collection tank
Tap water
Sample Type
1 min, continuous
1 min, continuous
1 min, continuous
1 min, continuous
1 min, continuous
1 min, continuous
spot
spot
30 min, continuous
spot
spot
               (a) Same source of water as on the cadmium line. Only one blank collected for
                  both cadmium and chromium lines.
from each of the two rinse tanks were planned, just as in the cadmium rinsewater testing; but none
were collected. This was because only a pilot system had been installed at Torrington at, the time
of testing.  This system did not have enough resin to operate for the full shift. Therefore^ the
evolving water quality of the rinse tanks as the day progressed could not be monitored.
         Samples collected for the cadmium and chromium systems were  sent to an independent
laboratory (Zande Environmental Services, Inc.  in Columbus, Ohio) for analysis. The results of the
                                                                                F
laboratory analyses are described below.
ANALYTICAL TESTING RESULTS
         Table 3 describes the results of the laboratory analysis of the cadmium rinsewater
samples.  Before ion exchange, the rinsewater showed maximum levels of 7.28 mg/L cadmium and
35.60 mg/L of cyanide (CD-X1-B1), but levels tended to vary with each run. Most of the cadmium
                                                                                i
and cyanide were removed after ion exchange — in some cases, below detection levels. The
average loading on the ion exchange over a 30-min period was found to be 4.31 mg/L of cadmium
and 17.6  mg/L of cyanide (CD-X30-B1).  The pH of the rinsewater remained steady at alkaline
levels throughout the testing. The field blank (tap water) showed very low levels of measured
contaminants, indicating that there was no extraneous contribution to the results.      •
                                            10

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          When cadmium and cyanide levels in the rinsewater were artificially elevated to|38.7 and
 117 mg/L, respectively (CD-XS-B1), the ion exchange reduced these to 3.69 and 14.6 mg/L,
 respectively (CD-XS-A1). This indicates that, at above-normal contaminant levels, the ion
 exchange system still removes most of the cadmium and cyanide, but is a little less effective.  For
 these high initial levels, longer residence time in the resin or several passes through the resin would
 be required to regain the same degree of removal.  However, such high levels are unlikely to be
 reached during normal operation.                                                    :
          The results of the spot samples taken at the beginning, middle, and end of a shift showed
 that contaminant levels rose steadily during the day. However, at the end of the shift, concentra-
 tions were still too low to be of  any concern.  This indicates that the continuous operation of the
 ion exchange system effectively controls the accumulation of contaminants  to within acceptable
 levels.
          Table 4 shows the averages calculated for the 1-min "before" and "after" samples
 (samples beginning with CD-X1-) collected  during the three runs. A t-test was performed based on
 the averages and standard deviations of the data. Although, strictly speaking, a t-test  may not be
 applicable because of the difference in variances between the "before" and "after" cases, ;it helps
 to highlight significant increases and decreases in the data. Differences between the "befpre" and
 "after"  samples were  examined  at the 95% significance level. Suspended solids levels w6re very
 low in  both "before" and "after" samples.  Cadmium, cyanide, and iron in the rinsewater showed
                                                                                   |
 significant decreases in concentration after ion exchange.  Overall dissolved solids  levels also
 showed a significant decrease after ion exchange, indicating a decline in dissolved  mass leVels.
 Interestingly, conductivity did not show any significant change after ion exchange, indicating that
 the current-carrying capacity of the rinsewater did not change. During ion exchange, heavier ions
 (cadmium, iron, etc.) transfer to the resin and lighter sodium ions are transferred to the water.
 Thus, dissolved  mass  in the water decreases, whereas conductivity remains relatively constant.
 Small amounts of fresh make-up water are  added to the rinsewater from time to time to compen-
 sate for water loss due to evaporation and dragout with the parts; this also helps control  I
 conductivity.                                                                 •      j
         Table 5 describes the results of the laboratory analysis of the chromium rinsewater
 samples.  Before ion exchange, the chromic acid contamination in the rinsewater lowered the pH  to
 between 4.41 and 4.83.  After ion exchange, the rinsewater pH was slightly alkaline (9.31 to
 9.45) because chromate ions (and any other contaminant anions) had been substituted with
 hydroxide ions.  The alkaline pH in the rinse tanks was neutralized by the chromic acid  residue on
the parts (workpiece).  When chromium levels in the rinsewater were artificially elevated to
 33.6 ppm (CR-XS-B1), the ion exchange reduced it to an acceptable level.

                                             12!                                  \

-------








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         Table 6 shows the averages calculated for the 1-min "before" and "after" samples
                                                                                  I  ,
{samples beginning with CR-X1-) collected during the three runs. A t-test was performed based on
the averages and standard deviations of the data. Differences between the "before" andinafter"
samples were examined at the 95% significance level.  Suspended solids levels in the "before"
samples were relatively high, but were significantly reduced by the cartridge filter installed before
the resin tank.  Iron and total chromium levels decreased significantly after ion exchange.;  Iron
removal may be due either to removal of ferrous suspended particles on the cartridge filter or to
deposition of complexed iron on the resin. As in thfe cadmium tests, dissolved solids mass
decreased significantly, whereas conductivity (current-carrying capacity) remained relatively
constant after ion exchange.  This is due to the heavier chromates in the rinsewater being replaced
with lighter hydroxide ions.
PRODUCT QUALITY ASSESSMENT                                           .      I

         On the cadmium line, the full scale ion exchange system effectively reduced contami-
nants in the ion exchange discharge to levels comparable to those in the fresh tap water blank.
Dissolved solids and conductivity in the recycled rinsewater were slightly higher than in the field
{tap water) blank, but typical of those found in the rinse tanks during continuous production.  A.
conductivity sensor monitored the conductivity in  Rinse 2 tank.  Fresh water could have been
introduced if conductivity became too high.  Fresh water was also added periodically to make up
                                                                                  i
for dragout losses.  The flow rate of 5 gal/min through the ion exchange unit (containing 94 Ibs of
resin with a total capacity of 5 Ibs of cadmium) appears sufficient to maintain contaminarits at
acceptable levels throughout the day under normal processing.  A conductivity sensor in Rinse 2
tank monitored ion build-up in the rinsewater. The small volume of fresh make-up water was
added periodically primarily to compensate for dragout losses, not to lower conductivity.
         In the three months following this testing, Torrington has not noticed any decline in the
quality of the parts processed through the cadmium rinse.  For this testing, the rinsewater on the
chromium line was processed through a pilot unit  «  1 gal/min).  Contaminant levels were reduced
significantly by ion exchange, to levels slightly above those found in the tap water blank.!
Torrington plans to further reduce total chromium  concentrations in the rinsewater by adding a
cation resin to remove any trivalent chrome in the rinsewater.
                                             14

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-------
                                         SECTION 3
                             POLLUTION PREVENTION POTENTIAL
         The pollution prevention potential of the ion exchange technology was evaluated in terms
of waste volume reduction and pollutant reduction.  Waste volume reduction addressed the gross
wastestream (e.g., Ibs of wastewater treatment sludge) and environmental resources expended
during disposal (e.g., landfill space). Pollutant reduction addressed the specific pollutants |in the
wastestream (e.g., chromium in the sludge).                                         ',     .  •
WASTE VOLUME REDUCTION

         Table 7, which is based on Torrington's plant records, shows the fresh water flow rates
through the rinses before installing the ion exchange system (counter flow rinse only) and after
installing the ion exchange system. On the cadmium line, without ion exchange, Torringtoh was
maintaining 3 gal/min flow through Rinse 2, which overflowed into Rinse 1.  An additional !5 gal/min
of fresh water was also run through Rinse 1.  On the chromium line, without a full-scale ion
exchange system, Torrington ran a counter flow of 1  gal/min through Rinse 2, which overflowed
into Rinse 1.  Rinse 1 also had an independent supply of 1 gal/min. These continuous flows
generated large amounts of wastewater that had to be treated on-site. With the ion exchange
system on the cadmium line, Torrington required only 50 gal/day (for 2 shifts, or 16 hr of operation)
to make up for dragout losses.  A similar make-up amount is expected on the chromium line.
         The wastewater generated each year by the rinsing operation is shown in Table 8.  These
annual numbers are based on the flow rates in Table  7 and an annual operating time of 16' hr/day
(2 shifts), 5 days/week, and 50 weeks/yr.  These numbers are typical of the influent volumes to
Torrington's on-site treatment plant.  By using ion exchange, wastewater as a wastestream
requiring treatment is virtually eliminated.
         The ion exchange operation generated small volumes of other wastestreams,  namely,
spent filters and the regenerant. On the cadmium line, Torrington changed the filter cartridge once
in two months. On the chromium line, the cartridge change is expected to occur more frequently,
possibly once a month.                                                            ,
                                            16

-------
                          TABLE 7.  FRESH RINSEWATER FLOW RATES
Rinsewater
Cadmium System
Rinse 1
Rinse 2
Chromium System
Rinse 1
Rinse 2
Flow
Without
Ion Exchange"1'

5 gal/min
3 gal/min

1 gal/min
1 gal/min
Rate"1
With
Ion Exchange'0'

0
50 gal/day

0
50 gal/day
                    (a)   With or without ion exchange, water from Rinse 2 overflows into
                         Rinse 1.
                    (b)   Continuous flow 16 hr per day as per Torrington's normal operating
                         schedule.
                    (c)   Intermittent flow; make-up water daily average measured by
                         Torrington.
          On the cadmium line, the resin is scheduled to be regenerated about once a month when

the line is operating at full capacity. Each regeneration consists of 8 gal of 50% NaOH in 12 gal of

water, plus an additional 35 gal of water for rinsing the column (55 gal/regeneration, or 660 gal of

regenerant/yr).  The regenerant will be subjected to electrolytic metal recovery (EMR) to recover
cadmium, and the rest will be sent to the on-site wastewater treatment plant.
                            TABLE 8.  WASTE VOLUME REDUCTION
                     Without Ion Exchange                   With Ion Exchange

                                     Amount                              Amount;
                   Waste          Generated per         Waste         Generated per
                 Description           year""	     Description           year""

               Cadmium System

                 Wastewater       1,920,000 gal       Wastewater           0 gal
                                                       Regenerant          660 gal
                                                     Filter cartridges           6

              Chromium System

                 Wastewater     .  480,000 gal        Wastewater           0 gal
                                                       Regenerant          840 gal
                                                     Filter cartridges          12   ,

             (a) Based on Table 7 values at 16 hr/day, 5 days/week, 50 weeks/yr.
             (b) Based on pilot tests conducted by Torrington and resin capacity.


                                               17

-------
         The full-scale chromium ion exchange unit is expected to generate 70 gal of regenerarit
 {20 gal of 50% NaOH in 50 gal of water) once a month, for a total of 840 gal of regenerant. The
 regenerant will be passed through a cation exchange resin to convert sodium chromate to: chromic
 acid.
POLLUTANT REDUCTION                                                         I

         The pollutants of interest on the cadmium line are cadmium and cyanide. Without ion
exchange, the cadmium in the rinsewater is lost to wastewater. This wastewater is sent to the
                                                                                 I
on-site wastewater treatment plant. In a steel cyanide treatment tank, the wastewater is treated
using chlorine gas, sodium hypochlorite, calcium  hypochlorite, and sodium hydroxide to oxidize the
cyanide. The wastewater then flows by gravity to another tank for neutralization.  The cadmium
and other metals form hydroxides that settle in the clarifier as sludge. This sludge is hauled off site
for disposal.  The treated water is  discharged to the municipal sewer under a permit.
         The average cadmium and cyanide concentrations in the wastewater when the cadmium
line is operating at full capacity are 4.31 and  17.60 mg/L, respectively (see Table  3, samp'le
CD-X30-B1). Without ion exchange, the annual generation of wastewater at full capacity :is
1,920,000 gal (Table 8). Therefore, approximately 69 Ibs of cadmium and 281 Ibs of  cyaiiide are
lost annually. With ion exchange,  most of the cadmium and cyanide are captured  on the resin,
which is regenerated with NaOH.  The regenerant is then subjected to EMR.  At the time of the
on-site visit, the resin on the full-scale system was not yet exhausted (and had not been regener-
                                                                                 i
ated) due to reduced operation on  the cadmium line at Torrington during that period. HoWever,
Torrington later regenerated the resin  and demonstrated good recovery of cadmium by ElvjR on the
cathode (see Appendix A). During the EMR operation, some of the cyanide also decomposed. The
cathode (with the plated cadmium) in the EMR operation was then transferred to the cadmium
plating tank, where it functions as a cadmium anode. The rest of the regenerant was then  sent to
the wastewater treatment plant.                   !
         On the chromium line, without ion exchange, the rinse wastewater is sent to a fiberglass
tank, where it is mixed with sodium metabisulfite and sulfuric acid to reduce the hexavalent
chrome to trivalent chrome. The wastewater is then sent to another tank for neutralization.  Here
                                                                                 !
the trivalent chrome forms a hydroxide that settles in the clarifier as sludge.  The sludge is  hauled
offsite for disposal and the treated water is discharged to the municipal sewer under a  permit.
         The average chromium concentration in the rinse wastewater when the chromium line is
operating at full capacity is 19.9 mg/L (Table  5, sample CR-X2-B1). Without ion exchange,

                                            18

-------
 480,000 gal of wastewater is generated^ peryear at full capacity {Table 8). Therefore,
 approximately 80 Ibs of chromium is lost annually. WitrTion exchange, most of the chromium is
 captured on the resin, which is regenerated with NaOH.  The regenerant is then passed through a
 cation exchange resin to convert sodium chromate to chromic acid. When this recovery was
 performed during the pilot unit testing, the final regenerant liquid still showed a PH of 13.08.
 Other parameters measured in the final regenerant were total chromium (14.6 mg/L), iron
 (0.28 mg/L), dissolved solids (14,111 mg/L), conductivity (68,800,/mhos/cm), suspended solids
 (2 mg/L), and sodium (7,010 mg/L).  This indicates that sodium chromate had not been converted
 to chromic acid, in  which case the pH would have been much  lower. This may be due to the fact
 that (a) an excess of NaOH was used to regenerate the resin and/or (b) there was insufficient resin
 to exchange all the sodium in the regenerant.  Further testing is required to determine the feasibility
 of the chromic acid recovery process.
 POLLUTION PREVENTION POTENTIAL ASSESSMENT

          By using ion exchange, large volumes of water are prevented from going to waste.  This
 water (an important resource) can be reused as a rinse on the cadmium and chromium lines. Virtu-
 ally eliminating the wastewater stream also eliminates the hazardous sludge (containing cadmium or
 chromium) that must be handled, transported, and disposed.  Cadmium and chromium are hazard-
 ous chemicals on EPA's Toxics Release Inventory.  Both metals are also on the list of 17 priority pol-
 lutants targeted in the EPA Administrator's 33/50 Program for 50%  reduction in releases by 1995.
         With ion exchange, small volumes of regenerant and a few spent filter cartridges are
 generated that eventually have to be treated or disposed. The quantities of regenerant and filters
 are, however, much smaller than the volumes of wastewater and sludge generated when ion
 exchange is not used.
         On the cadmium line, most of the cadmium that deposits on the resin can be recovered
 and reused in the plating bath.  Some of the cyanide on the resin is  destroyed during cadmium
 recovery (EMR) and the rest is destroyed in the on-site treatment plant.  Therefore, cyanide is not a
 recoverable resource.
         On the chromium line, further testing is necessary to determine the feasibility of recover-
ing chromic acid for reuse in the plating bath.
                                            19

-------
                                        SECTION 4                              !

                                 ECONOMIC EVALUATION                        !


         The economic evaluation involves a comparison of the costs of the ion exchange

operation versus the former practice (counterflow rinse).                              !
MAJOR OPERATING COSTS


         Both cadmium and chromium lines are assumed to operate at full capacity for 16 hr/day,

5 days/week, and 50 weeks per year.  Based on Torrington's plant records. Table 9 summarizes

the major annual operating costs for the cadmium rinsewater line with and without ion exchange.

Without ion exchange, the operating  costs involved are for fresh water usage and wastewater

treatment.  Fresh water (city supply)  at Torrington costs $0.70 per 1000 gal.  The annual usage of

water is 1,920,000 gal (Table 8).  Most of this water ends  up as wastewater. Wastewater

treatment costs for the cadmium line were based on an average cost of $22 per 1000 gal, of

wastewater, which includes cost of treatment chemicals, sludge disposal, municipal sewer

discharge fee, and  treatment plant labor (see Appendix B).                            ;

         With ion  exchange, the operating costs in Table 9 were based on the following:


         «    Fresh water requirement of 50 gal/day (make up) at $0.70/1000 gal.

         •    Energy costs were based on continuous operation of the ion exchange
              0.5  hp circulation pump over a year and an EMR consumption of 6 kW hr
              for each regeneration  (12 regenerations per year); electricity costs
              $0.075/kW-hr at Torrington.                                         |

         •    Labor cost was based on 0.5 hr of operator involvement per day during
              normal operation, plus 4 hr operator time during each regeneration
              (12  regenerations per  year). The average labor rate for the system
              operators is $7/hr.

         •    Routine maintenance costs were based on replacement of the filter       \
              cartridge ($5 each,  six times per year), replacement of EMR anode plates \
              ($30 each, one per year) and EMR cathode plates ($30 each, 12 per year),
              and maintenance labor of 24 hr/yr at  $7/hr).                           ;
                                            20

-------
             TABLE 9. OPERATING COSTS COMPARISO^ FOR CADMIUM SYSTEM
Item
Without Ion Exchange
Freshwater
Wastewater treatment

With Ion Exchange
Freshwater
Chemicals (50% NaOH)
Energy
Labor
Routine maintenance
- filter cartridges
- EMR anode plates
- EMR cathode plates
- labor
Waste Disposal
- regenerant
- filters

Amount
used
per year

1 ,920,000 gal
1,920,000 gal


12,500 gal
96 gal
1 564 kW hr
173 hr

6
1
12
24 hr

660 gal
6

Unit
cost

$ 0.70/1 000 gal
$ 22/1 000 gal
Total

$0.70/1 000 gal
$1.50/gal
$0.075/kW hr
$7/hr

$5
$30
$30
$7/hr

$22/1 000 gal
$400/36 units
Total
Total Annual
Cost

$ 1,344
$42,240
$43,584

$9
$144
$117
$1,211

$30
$30
$360
$168

$15
$67
$2,151
              Waste disposal costs due to ion exchange were based on regenerant
              disposal (660 gal/yr by on-site wastewater treatment at $22/1000 gal) and
              disposal of spent filter cartridges (6 per year, off-site disposal at $400 per
              36 filters).
         As Table 9 depicts, operating costs for ion exchange recovery are much lower than those
for counter flow rinse alone. The main cost saving is the reduction in wastewater treatment costs.
In addition to operating cost savings, the recovered cadmium has value because it is reused in the
plating bath as a cadmium anode.  The cost of cadmium anodes is approximately $15/Ib.  For the
69 Ibs/yr of cadmium that is deposited on the ion exchange resin, the resulting value recovered  is
approximately $1,036/yr.
         Based on Torrington's plant records. Table 10 summarizes the major operating costs for
the chromium rinsewater line with and without ion exchange.  Without ion exchange, the operating
costs involved are for fresh water usage and wastewater treatment.  Fresh water (city supply) at
Torrington costs $0.70 per 1000 gal. The annual water usage is 720,000 gal (Table 8).  Most of
this water ends up as wastewater.  Wastewater treatment costs for the cadmium line were based
                                            21

-------
            TABLE 10. OPERATING COSTS COMPARISON FOR CHROMIUM SYSTEM
      Item
Amount
 used
per year
Unit
cost
Total Annual
   Cost
      Without Ion Exchange

         Freshwater                  480,000 gal
         Wastewater treatment        480,000 gal
      With Ion Exchange

         Freshwater                   12,500 gal
         Chemicals (50% NaOH)         240 gal
         Energy                      1492 kW hr
         Labor                         149hr

         Routine maintenance
          - filters                         12
          - labor                         24

         Waste Disposal
          - regenerant                   840 gal
          - filters                         6
                  $ 0.70/1000 gal
                   $ 15/1000 gal
                          Total
                  $0.70/1000 gal
                    $1.50/gal
                   0.075/kW hr
                      $7/hr
                       $5
                      $7/hr
                   $15/1000 gal
                   $400/36 units
                          Total
                   $ 336
                  $7,200
                  $7,5i36
                      :$9
                    $112
                  $1,043


                     $60
                    $168
                                                                              $1,832
on an average cost of $15 per 1000 gal of wastewater, which includes cost of treatment
chemicals, sludge disposal, municipal sewer discharge fee, and treatment plant labor (see
Appendix B).                                                                      '

         With ion exchange, the operating costs in Table 9 were based on the following: i


         •    Fresh water requirement of 50 gal/day (make up) at $0.70/1000 gal.      >
                                                                                  i
         »    Energy costs were based on continuous  operation of the ion exchange     j
              0.5 hp  circulation pump over a year; electricity costs $0.075/kW hr at     '
              Torrington.                 •       '.                                  ':
                                                                                  i
         •    Labor cost was based on 0.5 hr of operator involvement per day during
              normal  operation, plus 2 hr operator time during each regeneration
              (12 regenerations per year). The average labor rate  for the system        i
              operators is $7/hr.                                                    '

         •    Routine maintenance costs were base'd on replacement of the filter cartridge
              ($5 each, six times per year) and maintenance labor of 24 hr/yr at $7/hr).   •

         •    Waste disposal costs due to ion exchange were based on regenerant      ;
              disposal (840 gal/yr by on-site wastewater treatment at $15/1000 gal) and
              disposal of spent filter cartridges (6 per year, off-site disposal at $400 per
              36 filters).
                                             22

-------
          As shown in Table 10, operating costs for ion exchange recovery are much lower than
 those for counter current rinse alone.  The main cost saving is the reduction in wastewater
 treatment costs. In addition to operating cost savings, the chromium deposited on the ion
 exchange resin has value if it can be successfully recovered as chromic acid.  The cost of chromic
 acid is approximately $2.50/|b. Approximately 80 Ibs/yr of chromium metal is deposited on the ion
 exchange resin. This corresponds to about 154 Ibs of chromic acid  (CrO3). However, further
 testing is required to establish the feasibility of chromic acid recovery from the chromium in the
 regenerant.
 CAPITAL COSTS

          According to Torrington's plant records, the purchase price of the cadmium ion exchange
 system was $8,100 (including ion exchange resin column, pumps, and collection tanks). The EMR
 equipment price was $4,125 (including rectifier, pump, anodes, cathodes, and solution tank).
 Installation cost at Torrington,  including materials (piping, etc.) and labor, was approximately
 $3,500. To approximate the cost of in-house pilot testing used to determine specifications for the
 individual plant, $5,000 was added to  this figure.
         The purchase price of the chromium ion exchange system (based on vendor information)
 is estimated to  be $8,200 (including ion exchange resin column, pumps, and tanks).  Installation
 cost at Torrington is expected to be  $3,500,  including materials (piping, etc.) and labor. The
 approximate cost of $5,000 for in-house testing is also added for this unit.
RETURN ON INVESTMENT

         A rough estimate of the payback period can be obtained by the following formula:

                    Payback, yrs = .	capital cost	
                                  operating cost savings + recovery value

         For the cadmium ion exchange system, total capital costs are $20,725 (purchase price,
pilot testing, and installation), savings in annual operating costs are $41,433 (difference in total
operating costs between "with" and "without" ion exchange as per Table 9), and the recycled
cadmium value is  $1,036.  This gives a payback period of less than a year.
                                            23

-------
         For the chromium system, the estimated total capital costs are $16,700 (purchase price,
pilot testing and installation) and savings in operating costs are $5,704 (see Table 10).  Because
chromic acid recovery from the regenerant is yet to be established, no recycled chromium value is
assumed. This results in a payback period of approximately 3 years.
         The difference in payback periods between the ion exchange systems on the cadmium
and chromium lines is primarily because,  under former practice (without ion exchange), the water
flow rate through the cadmium rinse tanks was much higher than in the chromium tanks. In
addition, the unit cost of wastewater treatment for the cadmium rinsewater was also higher than
that for chromium rinsewater.  Because the operating costs for both cadmium and chromium ion
exchange systems are similar, there is a greater annual operating cost savings for the cadpiium
line.                                                                            .  !
         The above payback period estimation is  a 'simple calculation  that does not take into
account such factors as cost of capital, inflation, etc. A more complete economic analysis is
presented in Appendix C  (cadmium line) and Appendix D (chromium line).  The worksheets provided
in the Facility Pollution Prevention Guide (U.S. EPA, 1992)  were used  for the calculations.  Based
on a detailed economic analysis, the cadmium ion exchange system still  shows a payback period of
less than 1 year.  On the chromium line, a positive return on investment (ROD occurs in year five
(break-even point on the original capital investment).  If a cost of capital of 15% is to be recovered,
however, the payback period is 8 yrs (ROI >  15%).                                  :
                                            24

-------
                                          SECTION 5
                                    QUALITY ASSURANCE
          Quality Assurance Project Plans (QAPP) were prepared and approved by EPA before
 testing began (Battelle, 1992a and b).  This QAPP contains a detailed design for conducting this
 study.  The experimental design, field testing procedures, and laboratory analytical procedures are
 covered. The QA objectives outlined in this QAPP are discussed below.
 ON-SITE TESTING

          On-site testing for the cadmium ion exchange system was conducted as planned, except
 for the EMR test.  Because the full scale system was installed a few days before on-site testing and
 because the workload on Torrington's cadmium line was somewhat reduced, the resin had not
 reached exhaustion and could not be regenerated during the on-site visit.  However, Torrington
 subsequently performed the regeneration of the resin and EMR to demonstrate the recovery of
 cadmium in a reusable form.  The resulting data are presented in Appendix A.
         On-site testing  for the chromium system was affected by the fact that a full-scale system
 was not installed in time  for testing.  A pilot system that had enough capacity to run for an hour
 was tested instead.  Samples from the two rinse tanks that were planned to be collected in the
 morning, afternoon, and evening to monitor rinsewater quality over the entire day could not be
 collected.  In the pilot unit, the regenerant could not be isolated between the primary'ion  (anion)
 exchange column and the auxiliary cation exchange column.  Hence, a regenerant sample before
 cation  exchange could not be obtained. Only the final regenerant sample after cation exchange
 was obtained.  Figures 1  and 2 in Section 1 have  been slightly modified (from those in the QAPP)
to eliminate the collection tank from the loop.  In both cases, the regenerant goes directly to the
next step.
        All other samples  were collected as planned. The 2-hr continuous composite was
changed to a 30-min composite because of the reduced scale of operation, and because the racks
were being processed continuously rather than every 2 hr.
                                            25

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LABORATORY ANALYSIS                                                          ;

         Appendix E lists the standard methods used for analyzing each parameter.  Analysis was
performed as planned on the cadmium and chromium samples collected.  Holding time for! pH,
which had been  set at 2 days, was exceeded by a day; however, this is not expected to have any
significant effect on the results because the samples were on ice and pH of rinsewater is fairly
stable.                                            __,.,                             i  .
         The  precision and accuracy of the analyses are listed in Tables 11 and 12, respectively.
The regular sample and  duplicate values listed in this table are based on pre-made dilutionis of the
original samples  prepared by the analytical laboratory.  Table 11  also gives the detection limits for
each parameter.  All laboratory blanks had very low or undetected values. Precision of the total
dissolved solids  analysis for the chromium system was slightly out of range (>25%).  However,
there was a wide enough difference (statistically) between the dissolved solids results for the
"before" and "after" samples for this to be of any consequence.  Sodium in the field blank
(CR-FB-1) was measured at 2.63 mg/L. Sodium analysis was intended to be indicative of
conversion of  sodium chromate to chromic acid.  However, because a regenerant sample bould  not
be isolated before  cation exchange, only the final regenerant was analyzed. The resulting sodium


             TABLE 11. PRECISION DATA FOR RINSEWATER  CHARACTERIZATION
Parameter
Cadmium Study
Cadmium
Cyanide
Iron
PH
Conductivity
TDS
TSS
Chromium Study
Chromium
Sodium
Iron
pH
Conductivity
TDS
TSS
Sample
No.

CD-R1-B2
CD-R1-B3
CD-R1-B3
CR-X1-B3
CR-X1-B3
CR-X1-B3
CR-X1-B3

CR-X1-B2
CR-CX-A1
CR-X1-B2
CR-X1-B2
CR-X1-B2
CR-X1-B2
CR-X1-B2
Regular
Sample""

941
247
410
11.48
936
205
<1

728
28.04
855
4.67
104
99
8
Duplicate'"1

982
256 :
408
11.48
940 ;
202
<1

733
32.76
852
4.70
104 •
98
6
Precision
(% RPD)

4.3
3.6
-0.5
0.0
0.4
- 1 .5
0.0

0.7
1 5.5
-0.4
0.6
0.0
-1.0
-28.6
Detection Limit

10ug/L
10ug/L
50 ug/L
0.01 S.U.
1 .00 //mhos/cm
1 mg/L
0.1 mg/L

20/jg/L
0.5 mg/L
50 //g/L
0.01 S.U.
1 .00 //mhos/cm
1 mg/L
0.1 mg/L
i
Laboratory
Blanks'31
,
<10
<10
<;50
5.35
2.45
<1
4
i
<20
<0.5
<50
5.35
! 2.45
<1
4
   (a) Units of measurement for each parameter are given in the "Detection Limit" column.
                                             26

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                TABLE 12. ACCURACY DATA FOR RINSEWATER CHARACTERIZATION
Parameter
Cadmium Study
Cadmium
Cyanide
Iron
Chromium Study
Chromium
Sodium
Iron
Sample No.

CD-R1-B2
CD-R1-B3
CD-R1-B3

CR-X1-B2
CX-CX-A1
CR-X1-B2
Regular
, Sample
(ug/L)

941
109.8
410

728
28,040
855
Matrix
Spike Level
(ug/L)

1 ,000
300
1,000

1,000
5,000
1,000
Matrix Spike
Measured
(ug/L)

1,953
422.3
1,317

1,693
32,760
1,972
Accuracy %
Recovery

101
104
91

97
94
112
concentration is discussed in Section 3 under the heading "Pollutant Reduction."  Based on the above
discussion, completeness percentages are listed in Appendix F.
LIMITATIONS AND QUALIFICATIONS

             Based on the above QA data, the results of the on-site and laboratory testing on the cadmium
line can be considered a valid basis for drawing conclusions about product quality, pollution prevention
potential, and economics.  Economic and waste reduction information was obtained from Torrington's
plant records over the past year.
             On the chromium line, water quality in the rinse tanks could not be monitored over a period
of one day of operation because of the small resin size. However, the contaminant removal in the
chromium rinsewater samples actually collected follows the same pattern as in the cadmium samples.
Given the chromium removal in the "after" samples exiting the ion exchange, it is expected that an
appropriately sized ion exchange system would maintain good water quality in the rinse tanks.  The
unresolved issue in the pollution prevention evaluation on the chromium system is the feasibility of
recovering chromic acid that can be returned to the plating bath. The on-site tests were unable to recover
the chromium as chromic acid. More tests need to be performed to prevent chromium loss through the
regenerant.  Economically however, there is sufficient data to show that, even  without the final recovery
of chromium as chromic acid, the system results in cost savings for the user.
                                               27

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                                        SECTION 6                               j
                                                                                 l
                              CONCLUSIONS AND DISCUSSION                    '

         The evaluation showed that rinsewater on both the cadmium and chromium lines at
Torrington Company can be reused after subjecting the water to filtration and ion exchange to
remove impurities. Large volumes of water are thus prevented from going to waste.  Disposal of
large amounts of hazardous metals sludge in the environment is also prevented. The sidestreams
from ion exchange are negligible compared to the wastewater and sludge wastestreams generated
in the absence of ion exchange. The ion exchange resin can be regenerated with sodium 'hydrox-
ide.  On the cadmium line, the regenerant  can be subjected to EMR and the cadmium  recovered on
the cathode. This electrode, with  the deposited cadmium, is then inserted in the plating tank as a
cadmium anode.  In this way, a hazardous pollutant, cadmium, is reused. On the chromium line,
further testing is necessary to establish the feasibility of recovering chromium as chromic 'acid for
reuse in the bath.
         Without ion exchange, the rinsewater is subjected to an expensive wastewater treatment
process. The cost of operating the ion exchange unit is more than offset by the savings in waste-
water treatment costs and by the value of the recovered product. On the cadmium line, this cost
saving and recovery value result in a payback period of less  than a year for the ion exchahge sys-
tem.  On the chromium line, even without considering  any recovered metal value, the wastewater
treatment cost saving alone offsets the operating costs of the ion exchange,  affording a payback
period of eight years. The large difference in payback  periods on the cadmium and chromium lines
Is due to rinsewater consumption (without ion exchange) of the cadmium line being much  greater
than that of the chromium line.  With ion exchange, the resulting savings are greater for the
cadmium line.
         In addition to  the direct economic benefits, the ion exchange system also reduces the
potential liability of Torrington Company as a potentially responsible party (PRP) by virtually
eliminating the risk involved during off-site transport and disposal of hazardous sludge. Torrington
is also testing other means of pollution prevention (not part of this evaluation) on the cadmium and
chromium electroplating lines.  To  remove carbonates from the plating tank and increase bath life, a
chiller has been installed on the cadmium line.  The EMR unit evaluated in this study is also being
tested for removing cadmium from the dragout tank water.  A scrubber is being installed on the
                                            28

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chromium line to capture chromium mists over the plating tank.  The scrubber liquid is then passed
through a separate ion exchange column to recover the chromium.
                                          29

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                                       SECTIO;N 7
                                       REFERENCES
Battelle.  Quality Assurance Project Plan (QAPP) for Cadmium Recovery from Electroplating
Rinsewater by ton Exchange.  Columbus, Ohio, 1992a.

Battelle.  Quality Assurance Project Plan (QAPP) for Chromium Recovery from Electroplating
Rinsewater by Ion Exchange.  Columbus, Ohio, 1992b.
                                                                               i
U.S. Environmental Protection Agency (EPA). Facility Pollution Prevention Guide.
EPA/600/R-92/088, May 1992.                                                   |
                                           30

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                                       APPENDIX A
                                   EMR TEST RESULTS

         Regenerant used was 8 gal of 50% NaOH in 12 gal of water.  After regeneration, the
column was rinsed with 35 gal of water, to give a total regenerant volume of 55 gal. This 55 gal
was analyzed to contain 2.5 ppm cadmium and 400 ppm cyanide. Fifteen gal of water from the
dragout (still rinse) tank was added to the regenerant.  This dragout water contained 2000 ppm of
cyanide and 250 ppm of cadmium,  and was added to the regenerant before performing the EMR
operation. The dragout water represents an additional wastestream that Torrington is trying to
minimize.
         The EMR used 4 volts, 40 amps in a 36-hr operation.  The final regenerant solution (after
EMR) contained only 13 ppm of cadmium, indicating that most of the cadmium had been recovered
on the cathode. Some cyanide decomposed during the EMR operation, to a level of 1100 ppm.
The exact mechanism of cyanide destruction by EMR  is not known.
                                           31

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                                       APPENDIX B
                                              I                                  '
                            WASTEWATER TREATMENT COSTS


         The wastewater treatment costs for the waste rinsewater on the cadmium line are based

on the following plant information over the past year:                                 ;


         «   Annual wastewater influent from theicadmium rinse is  1,920,000 gal/yr based on
             continuous production of 16hr/day, 5 days/week, and 50 weeks/yr

         •   Chemical usage based on
             - 172,000 Ibs/yr of 25% NaOH at $0.09/lb                            i
             - 3,660 gal/yr of 50% NaOH at $1.50/gal
             - 11 tons/yr of chlorine gas at $550/ton cylinder                        ;
             - 5000 gal/yr of sodium hypochlorite at $0.58/gal                       ;
             - 1500 Ibs/yr of calcium hypochlorite at  $1.11/lb                       ,

         «   Labor cost of 2 hr/day of operating time at $7/hr.

         «   Municipal sewer discharge fee of $1,47/1000 gal of treated water

         •   Sludge disposal cost based on 21,000 Ibs/yr of cadmium sludge hauled away at
             $0.20/lb.                                                           i


This gives an average cost of cadmium wastewater treatment of $22/1000 gal.

             Wastewater treatment  costs for waste rinsewater on the chromium line were based

on the following plant information over the last one year:
                                              i                                  *

         «   Annual wastewater influent of 2,205,000 gal/yr. This influent consists not only of
             rinsewater from the chromium plating line, but also of rinsewater from the '<
             chromating line.  However, all calculations are finally converted to a unit cost
             ($/1,000 gal), which then applies to the 480,000 gal/yr from the chromium plating
             rinsewater line.

         •   Chemical costs are based on:                                        ;
             - 7,200 gal/yr of 30% sulfuric acid at $0.78/gal                        '.
             - 21,000 Ibs/yr of sodium metabisulfite at  $0.25/lb
             - 1,000 gal/yr of 50% sodium hydroxide at $1.50/gal

         •   Labor  costs based on 2 hr/day of operating time at  $7/hr
                                            32

-------
         •    Municipal sewer discharge fee of $1.47/1,000 gal of treated water
         •    84,000 Ibs/yr of chromium sludge hauled away at $0.20/lb.

Therefore, the average wastewater treatment cost on the chromium rinsewater line is
approximately $15/1,000 gal.
                                           33

-------

-------
                                         APPENDIX C

              ECONOMIC ANALYSIS OF CADMIUM RINSEWATER ION EXCHANGE


         A more detailed economic analysis than the one presented in Section 4 of this report is

described here.  Worksheets provided in the Facility Pollution Prevention Guide (U.S. EPA 1992)

were used for the calculations.  In addition to the cadmium rinsewater data listed in Section 4, the
following values were used:


         H    Capital Cost (Table C-1)
              -  Total equipment cost of $12,225 (including ion exchange and EMR) plus
                10% tax
              -  Total installation costs of $3,500 in Section 4 were broken down into
                $1,500 for materials and $2,000 for installation (labor)
              -  Plant engineering and contractor engineering costs were $3,000 and
                $2,000 based on the pilot ion exchange unit leasing and testing that
                was conducted prior to  full-scale installation
              -  Contingency costs of 5% of fixed capital (i.e, sum of all the above)
              -  Working capital based on 1 month's cost of water, energy, and  filters
                cost from Section 4
              -  100% equity (i.e., no loan taken)
              -  Depreciation  period of 10 yrs
              -  Income tax rate of 34%
              -  Escalation (inflation) rate of 5%  -
              -  Cost of capital of 15%

        "    Table C-2 describes increased revenue, increased operating costs,  reduced
             waste disposal  costs of ion exchange (entered as positive numbers).
              Decreased revenue, decreased operating costs, and increased waste
             disposal costs due to ion exchange entered as negative values denoted by
             parentheses around the number).
             - Cadmium recovery value of $1,036/yr
             r Increase in utilities costs based on electricity and water consumption
               from Section  4
             - Reduction in disposal costs based on wastewater (including sludge),
               regenerant, and filters treatment/disposal costs
             - Increase in operating labor based on Section 4 data
             - Increase in operating supplies based on NaOH required for regeneration
             - Increase in maintenance  costs based on labor and materials as in Section 4
             - Supervision costs are 10 % of O&M labor
             - Overhead costs are a percentage of O&M labor and supervision
                                            34

-------
Table C-3 shows the revenues (recovered value) and operating savings resulting from use of ion
exchange for the first three years.  Table C-4 shows the return on investment (ROI).  In the first
year, the ROI exceeds  15%, which is the cost of capital (see Table C-1). Therefore, the payback
period is less than 1 year.                       >                                  ;
                TABLE C-1.  CAPITAL COSTS FOR CADMIUM ION EXCHANGE
INPUT
CAPITAL COST

Capital Cost
Equipment
Materials
Installation
Plant Engineering
Contractor/Engineering
Permitting Costs
Contingency
Working Capital
Start-up Costs

% Equity
% Debt
Interest Rate on Debt, %
Debt Repayment years

Depreciation period
Income Tax Rate, %

Escalation Rates, %

Cost of Capital

$13,448
$1,500
$2,000
$3,000
$2,000
$0
$1,000
$45
$2,000

100%
0%
10.00%
0

10
34.00%

5.0%

15.00%
OUTPUT
CAPITAL REQUIREMENT |
Construction Year

Capital Expenditures
Equipment
Materials
Installation
Plant Engineering
Contractor/Engineering
Permitting Costs
Contingency
Start-up Costs
Depreciable Capital
Working Capital
Subtotal
Interest on Debt
Total Capital Requirement

Equity Investment
Debt Principal
Interest on Debt
Total Financing
1
j,

$13,448
$1 ,500
$2,000
$3,000
$2,000
$0
$1,000
$2,000
$24,948
$45
$24,993
$0
$24,993
I
I
$24,993
$0
$0
$24,993
- ;
                                            35

-------
TABLE C-2.  OPERATING COSTS FOR CADMIUM ION EXCHANGE
Operating Cost/Revenue , "
Marketable By— products
Cadmium
Total $/yr.

Utilities
Electric
Water
Total $/yr.

Raw Materials
Chemicals
Water
Total

Decreased Waste Disposal
Water treatment
Ion— X regenerant
Ion -X filters . • .
I ransportation, $
Storage Drums $
Total Disposal $

$1,036
$1,036


$117
($1 ,335'
($1,218'


$0
$0
$0


$42,240
'($15]
($671
$0
$0
$42,158





















Operating Labor
Operator hrs
Wage rate, $/hr.
Total $/yr.

Operating Supplies
Chemicals

Maintenance Costs
Labor
Materials


Supervision
(% of O&M Labor)

Overhead Costs

173
$7.00
$1,211


$144


$168
$420



10.0%


(% of O&M Labor + Supervision}
Plant Overhead
Home Office
Labor Burden
25 0%
20.0%
28.0%
TABLE C-3. OPERATING SAVINGS USING CADMIUM ION EXCHANGE
REVENUE AND COST FACTORS-CADMIUM STUDY
Operating Year Number
Escalation Factor

INCREASED REVENUES
Increased Production
Marketable By— products
Annual Revenue


1.000






1
1.050


$0
$1 ,088
$1 ,088

2
1.103


$0
$1,142
$1,142

3
1.158


$0
$1,199
$1,199

OPERATING SAVINGS (Numbers in parentheses indicate net expense) :
Raw Materials
Disposal Costs
Maintenance Labor
Maintenance Supplies
Operating Labor
Operating Supplies
Utilities
Supervision
Labor Burden
Plant Overhead
Home Office Overhead
Total Operating Savings












$0
$44,266
C$176'
($441
($1,272
($151
$1 ,279
($145'
($446'
($398'
($319'
$42,197
$0
$46,479
($185)
($463)
($1 ,335)
($159)
$1,343
($152)
• ($468)
($418)
($334)
$44,307
$0
$48,803
($194)
($486)
($1,402)
($167)
$1,410
($160)
($492)
($439)
($351)
$46,522
                       36

-------
TABLE C-4. RETURN ON INVESTMENT FOR THE CADMIUM ION EXCHANGE SYSTEM
RETURN ON INVESTMENT-CADMIUM STUDY ;
Construction Year
Operating Year

Book Value
Depreciation (by straight- lin
Depreciation (by double DB
Depreciation

Cash Flows

Construction Year
Operating Year

Revenues
+ Operating Savings
Net Revenues
— Depreciation
Taxable Income
— Income Tax •
Profit after Tax
+ Depreciation
After-Tax Cash Flow

Cash Flow for ROI
Net Present Value
Return on Investment
i

1
$24,948
3)


'•


1




r



i



($24,993)
($24,993]


1

$19,958
$2,495
$4,990
$4,990




1

$1 ,088
$42,197
$43,285
$4,990
$38,295
$13,020
$25,275
$4,990
$30,265

$30,265
$1,324
21 .09%

2

$15,967
$2,495
$3,992
$3,992




2

$1,142
$44,307
$45,449
$3,992
$41 ,458
$14,096
$27,362
$3,992
$31 ,354

$31 ,354
$25,032
87.87%

3

$12,773
$2,495
$3,193
$3.193




3

$1,199
$46,522
$47,722
$3,193
$44,528
$15,140
$29,389
$3,193
$32,582

$32,582
$46,455
110.25%
                               37;

-------
                                        APPENDIX D

              ECONOMIC ANALYSIS OF CHROMIUM RINSEWATER ION EXCHANGE


         A more detailed economic analysis than the one presented in Section 4 of this report is

described here. Worksheets provided in the Facility Pollution Prevention Guide (U.S. EPA 1992)

were used for the calculations.  In addition to the chromium rinsewater data listed in Section 4, the
following values were used:


         •     Capital Cost (Table D-1)

              -  Total equipment cost of $8,200 plus 10% tax
              -  Total installation costs of $3,500 in Section 4 were broken down into
                $1,500 for materials and $2,000 for installation (labor)
              -  Plant engineering and contractor engineering costs were $3,000 and
                $2,000 based on the pilot ion  exchange unit leasing and testing that
                was conducted prior to full-scale installation
              -  Contingency costs of 5% of fixed capital (i.e, sum of all the above)
              - Working capital based on 1 month's cost of water, energy, and filters
               cost from Section 4
              -  100% equity (i.e., no loan taken)
              -  Depreciation period of 10 yrs
              - Income tax rate of 34%
              - Escalation (inflation) rate of 5%
              - Cost of capital of 15%


         •     Table D-2 describes increased revenue, increased operating costs, reduced waste
              disposal costs of ion exchange (entered as positive numbers). Decreased revenue,
              decreased operating costs, and increased waste disposal costs due to ion exchange
              entered as negative values denoted by parentheses around the number).

              - Cadmium recovery value of $1,036/yr
              - Increase in utilities costs based on electricity and water consumption
               from Section 4
              - Reduction in disposal costs based on wastewater (including sludge),
               regenerant, and filters treatment/disposal costs
              - Increase in operating labor based on Section 4 data
              - Increase in operating supplies based on NaOH required for regeneration
              - Increase in maintenance costs  based on labor and  materials as in Section 4
             - Supervision costs are 10% of O&M labor
              - Overhead costs are a percentage of O&M labor and supervision
                                            38

-------
Table D-3 shows the revenues (recovered value) and operating savings resulting from use of ion
exchange for the first three years. Table D-4 shows the return on investment (ROI).  In the eighth
year, the ROI exceeds 15%, which is the cost of capital (see Table D-1).  Therefore, the payback
period is approximately 8 years.
               TABLE D-1. CAPITAL COSTS FOR CHROMIUM ION EXCHANGE
INPUT
CAPITAL COST

Capital Cost
Equipment
Materials
Installation
Plant Engineering
Contractor/Engineering
Permitting Costs
Contingency
Working Capital
Start-up Costs

% Equity
% Debt
Interest Rate on Debt, %
Debt Repayment, years

Depreciation period-
income Tax Rate, %

Escalation Rates, %

Cost of Capital

$9,000
$1,500
$2,000
- $3,000
$2,000
$0
$875
$15
$1,750

100%
0%
1 0.00%
0

10
34.00% i

5.0%

15.00%
OUTPUT :
CAPITAL REQUIREMENT
Construction Year '

Capjtal Expenditures
Equipment
Materials
Installation
Plant Engineering
Contractor/Engineering
Permitting Costs
Contingency
Start-up Costs
Depreciable Capital
Working Capital
Subtotal
Interest on Debt
Total Capital Requirement

Equity Investment
Debt Principal
Interest on Debt
Total Financing
: 1
«

$9,000
$1,500
$2,000
$3,000
$2,000
$0
$875
$1,750
$20,125
$15
$20,140
$0
$20,140
'
$20,140
$0
$0
$20,-140
• ' l
                                           39

-------
TABLE D-2.  OPERATING COSTS FOR CHROMIUM ION EXCHANGE
Operating Cost/Revenue
Marketable By— products
Chromium
Total $/yr.

Utilities
Electric
Water
Total $/yr.

Raw Materials
Chemicals
Water
Total '
,
Decreased Waste Disposal
Water treatment
Ion— X regenerant
Ion -X filters
Transportation, $
Storage Drums $
Total Disposal $

$0
$0


$112
($327
($215


$0
$0
$0


$7,200
($131
($67]
$0
$0
$7,120





















Operating Labor
Operator hrs
Wage rate, $/hr.
Total $/yr.

Operating Supplies
Chemicals

Maintenance Costs
Labor
Materials


Supervision
(% of O&M Labor)

Overhead Costs

149
$7.00
$1,043


$360


$168
$60



10.0%


(% of O&M Labor + Supervision)
Plant Overhead
Home Office
Labor Burden
25.0%
20.0%
28.0%
                       40

-------
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                      APPENDIX E
STANDARD ANALYTICAL METHODS FOR RINSEWATER ANALYSIS
    Analyte
    Cadmium
    Chromium
    Iron
    Cyanide
    pH
    Total dissolved solids
    Total suspended solids
    Sodium
    Conductivity
     Standard
EPA 3010, EPA 6010
EPA 3010, EPA 6010
EPA 3010, EPA 6010
    EPA 335.3
    EPA 150.1
    EPA 160.1
    EPA 160.2
EPA 3010, EPA 6010
    EPA 120.1
                           43i

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                                       APPENDIX F

                                     COMPLETENESS
         Sampling completeness is the percentage of samples actually collected out of those
proposed in the QAPP.  Analytical completeness is the percentage of valid results obtained from
the collected samples. Tables F-1 and F-2 list the sampling and analytical completeness for the
samples on the cadmium and chromium lines respectively.  Wherever completeness was less than
100%, the impact is discussed in Section 5 of this report.
                                           44

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           TABLE F-1. COMPLETENESS FOR CADMIUM ION EXCHANGE SAMPLES
                                 Sampling Completeness (%)/Analytical Completeness (%)
Sample Category
                    Conductivity     TSS
          TDS     Cadmium    Cyanide
           PH
             Iron
"Before" and "after"
ion-x samples

Baseline (beginning,
middle, and end of
day)

Spikes "before" and
"after" ion-x

Regenerant "before"
and "after" EMR

Field blank
                      100/100    100/100   100/100   100/100   100/100   100/0""  i  100/100


                      100/100    100/100   100/100   100/100   100/100   100/0(a)  i  100/100
                        NRW
                        NR
NR        NR     100/100   100/100     NR'   ;.    NR
NR        NR      100/100   100/100     NR         NR
                      100/100    100/100  100/100   100/100   100/100   100/0(al  i  100/100

(a) Holding time for pH exceeded by a day.
(b) NR = not required.
           TABLE F-2.  COMPLETENESS FOR CHROMIUM ION EXCHANGE SAMPLES
                                Sampling Completeness (%)/Analytical Completeness (%)
Sample Category     Chromium     pH     Conductivity     TSS
                                                                 TDS"
                                        Iron
                  Sodium
"Before" and "after"    100/100   100/100
ion-x samples

Baseline (beginning,      0/0       0/0
middle, and end of
day)*1

Spikes "before" and    100/100      NR
"after" ion-x

Regenerant(cl          50/100    50/100
"before" and "after"
EMR
                                          100/100    100/100    100/0
                                            0/0'
                                            NR
                                            NR
                   0/0       0/0
                    NR
NR
                    NR       50/0
100/100  |    NR


  0/0        NR



   NR        NR


50/100    50/100
Field blank
                    100/100   100/100    100/100    100/100    100/0   100/100   100/100
(a) Precision for TDS was slightly out of range.
(b) No baseline samples were collected because the capacity of the resin was too small.
(c) Regenerant "before" cation-x could not be isolated for collection.
                                             45

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