Document ID: EPA-HQ-OW-2003-0074-0633
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2003-12-24T05:00Z

Preliminary
Data
Summary
for
the
Photoprocessing
Industry
United
States
Environmental
Protection
Agency
Office
of
Water
Engineering
and
Analysis
Division
401
M
Street,
S.
W.
Washington,
D.
C.
20460
i
Table
of
Contents
List
of
Tables
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List
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Figures
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Acknowledgments
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iv
1.
Executive
Summary
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1
2.
Introduction
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3
3.
Regulation
of
Photoprocessing
Wastewaters
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5
3.1
Existing
Effluent
Guidelines
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5
3.2
Local
Limits
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6
3.3
Regulatory
Drivers
and
Barriers
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9
4.
Photoprocessing
Industry
Profile
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11
4.1
Photoprocessing
Industry
Overview
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11
4.2
Photoprocessing
Volume
and
Revenue:
Amateur
Market
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15
4.3
Production
of
Photosensitive
Papers
and
Films
and
Photoprocessing
Equipment
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19
4.4
New
Technologies
in
Photography:
Advanced
Photo
System
and
Digital
Imaging
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20
5.
Description
of
Photoprocessing
Operations
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22
5.1
Process
Descriptions
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22
5.2
Manual
and
Automated
Systems
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26
6.
Water
Use
and
Wastewater
Sources
and
Characterization
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29
6.1
Introduction
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29
6.2
Total
Process
Water
Use
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30
6.3
Developer
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33
6.4
Bleach
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36
6.5
Fix
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39
6.6
Bleach­
Fix
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39
6.7
Wash
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41
6.8
Stabilizers
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41
6.9
Total
National
Photoprocessing
Discharge
Flow
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42
7.
Control
and
Treatment
Technologies
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44
7.1
Introduction
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ii
7.2
Source
Reduction
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44
7.3
Silver
Recovery
Considerations
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46
7.4
Silver
Recovery
from
Fixer
Solution
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48
7.5
Silver
Recovery
from
Rinse
Water
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52
7.6
Color
Developer
Reuse
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54
7.7
Ferricyanide
Recovery
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54
7.8
Rinse
Water
Use:
Reduction
and
Recycling
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56
7.9
Implementation
of
Control
Technologies
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58
7.10
Control
and
Treatment
Issues
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59
8.
Environmental
Assessment
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8.1
Introduction
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61
8.2
Pollutants
Found
in
Photoprocessing
Effluent
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61
8.3
Toxic
Weighting
Factor
Analysis
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65
8.4
Loads
Associated
with
Photoprocessing
Effluent
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66
8.5
Qualitative
Environmental
Impact
of
Photoprocessing
Effluent
Constituents
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68
8.6
Toxicity
and
Speciation
of
Silver
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70
References
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74
Appendix
A.
Calculation
of
Total
United
States
Surface
Area
of
Photographic
Film
and
Paper
Developed
for
Amateur
Market
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77
List
of
Tables
Table
4.1
Number
of
Photoprocessing
Facilities
by
Type
for
Phoenix,
Arizona
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12
Table
4.2
Number
of
Photoprocessing
Establishments
by
SIC
Code,
1996
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13
Table
4.3
Photographic
Use
of
Silver,
1993
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14
Table
4.4
1994
Photoprocessing
Total
Exposures
by
Film
Format
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16
Table
4.5
1994
Photoprocessing
Total
Exposures
by
Film
Type
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16
Table
4.6
1993
and
1994
Market
Share
of
Photoprocessing
by
Retail
Channel
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17
Table
4.7
1993
and
1994
Market
Share
of
Photoprocessing
by
Retail
Channel
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18
Table
4.8
Characteristics
of
Amateur
Film
Processing
Labs
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18
Table
6.1
Aqueous
Wastes
from
Photoprocessing
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.
.
30
Table
6.2
Estimated
Wastestream
Volumes
for
Various
Photoprocessors
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
32
Table
6.3
Photoprocessing
Combined
Wastestream
Effluent
Characteristics
.
.
.
.
.
.
.
.
.
.
.
.
.
.
33
Table
6.4
Color
Developer
Untreated
Wastestream
Pollutant
Amounts
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
35
Table
6.5
EDTA
Bleach
Untreated
Wastestream
Pollutant
Amounts
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
37
Table
6.6
Ferricyanide
Bleach
Untreated
Wastestream
Pollutant
Amounts
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
38
Table
6.7
Bleach­
Fix
Untreated
Wastestream
Pollutant
Amounts
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
40
Table
6.8
Total
United
States
Photoprocessing
Amateur
MarketWaste
Stream
Quantity
Estimations
for
1994
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
43
iii
Table
7.1
Comparison
of
Silver
Recovery
and
Management
Systems
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
47
Table
7.2
Commercial
Photoprocessor
Environmental
Controls,
1991
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
58
Table
7.3
Silver
Concentrations
After
Silver
Recovery
(
mg/
L)
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
59
Table
8.1
Possible
Photoprocessing
Wastewater
Constituents
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
62
Table
8.2
Pollutant
Loadings
for
Direct
Discharge
Photoprocessing
Facilities,
1995
.
.
.
.
.
.
.
.
63
Table
8.3
Pollutant
Toxic
Weighting
Factors
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
66
Table
8.4
Estimated
1994
Loads
and
Toxic
Loads
for
the
Amateur
Sector
of
the
Photoprocessing
Industry
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
67
Table
8.5
Solubility
and
Solubility
Product
of
Some
Silver
Compounds/
Complexes
.
.
.
.
.
.
.
.
71
Table
8.6
Percent
Mortality
of
Fathead
Minnows
Acutely
Exposed
to
Concentrations
of
Different
Silver
Compounds
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
72
List
of
Figures
Figure
5.1
Color
Negative
Film
Process
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
23
Figure
5.2
Color
Negative
Paper
Process
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
24
Figure
5.3
Color
Reversal
Paper
Process
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
24
Figure
5.4
Black­
and­
White
Development
Process
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
26
iv
Acknowledgments
This
Preliminary
Data
Summary
was
prepared
by
James
Covington,
Joseph
Daly,
Eric
Strassler
and
Kevin
Tingley
of
the
Engineering
and
Analysis
Division
of
the
U.
S.
Environmental
Protection
Agency.
Questions
regarding
this
study
should
be
directed
to
Mr.
Daly
at
(
202)
260­
7186.
1
1.
Executive
Summary
This
Preliminary
Data
Summary
for
the
Photoprocessing
Point
Source
Category
investigates
the
state
of
the
industry
and
its
wastewaters
in
relation
to
the
existing
1976
Guidelines,
and
attempts
to
evaluate
the
relevance
of
these
guidelines
in
the
current
photoprocessing
operating
and
regulatory
environment.
The
purpose
of
this
document
is
to
provide
technical
support
towards
a
decision
of
possible
revision
of
the
1976
Photoprocessing
Effluent
Limitations
Guidelines
and
Standards.
This
study
was
conducted
to
meet
the
obligations
of
the
Environmental
Protection
Agency
(
EPA)
under
section
304(
m)
of
the
Clean
Water
Act
(
CWA),
in
accordance
with
a
consent
decree
in
Natural
Resources
Defense
Council
and
Public
Citizen,
Inc.
v.
Browner
(
D.
D.
C.
89­
2980,
January
31,
1992).

EPA
promulgated
an
Interim
Final
Rule
for
the
Photographic
Category
on
July
14,
1976,
establishing
best
practicable
control
technology
currently
available
(
BPT)
limitations
for
one
subcategory,
the
Photographic
Processing
Subcategory,
at
40
CFR
Part
459,
Subpart
A.
Facilities
falling
within
this
photoprocessing
subcategory
use
silver
halide­
sensitized
photographic
materials
to
produce
continuous
tone
black­
and­
white
or
color
negatives,
positive
transparencies,
and
prints
for
delivery
to
external
customers.
Commercial
photoprocessing
services
are
available
through
a
variety
of
retail
channels,
including
drugstores,
discount/
mass
merchandisers,
camera
stores,
mail
order,
and
stand­
alone
mini
labs.
Photoprocessing
also
plays
a
major
role
in
the
businesses
of
portrait
studios
and
motion
picture
production.
About
100,000
establishment
were
identified
in
1996
in
Dun
&
Bradstreet
under
the
commercial
photoprocessing
standard
industrial
classification
(
SIC)
codes.
Significant
photoprocessing
also
occur
as
an
ancillary
activity
within
the
health
care
profession
at
hospitals,
dentists',
doctors',
and
veterinary
offices,
and
at
noncommercial
facilities
such
as
schools,
police
departments,
and
to
serve
heavy
construction
and
transportation
needs.
Combining
all
types
of
facilities,
it
is
estimated
that
photoprocessing
operations
occur
at
350,000
to
500,000
locations
in
the
United
States.

Data
concerning
the
amount
of
film
processed
was
available
only
for
the
commercial
sector,
which
is
estimated
to
represent
44
percent
of
total
photoprocessing
volume.
For
the
commercial
sector,
it
is
reported
that
in
1994,
715.5
million
rolls
of
film
were
processed,
resulting
in
17.58
billion
exposures
and
generating
revenue
of
over
$
5.5
billion.
Over
92
percent
of
the
film
processed
was
35mm
format,
and
almost
95
percent
was
processed
as
color
prints.
Based
on
the
commercial
data,
it
is
estimated
that
in
1994,
296
million
square
feet
of
film,
and
4,120
million
square
feet
of
paper,
were
processed
in
the
United
States.
The
estimated
water
use
by
the
commercial
sector
of
this
industry
in
1994
is
2,250
million
gallons.
The
major
wastewater
constituents
of
concern,
with
1994
estimated
commercial
sector
loadings,
include
sulfates
(
2.8
million
lbs.),
ammonia
(
3
million
lbs.),
silver
(
190
thousand
lbs.),
thiosulfate,
and
cyanide.
Several
technologies
are
available
and
employed
to
either
treat
the
wastestreams,
or
as
common
in
this
industry,
recover
the
chemicals
and
metals
in
the
wastewater
for
resale
or
reuse.
Recovery
of
silver
is
almost
always
practiced
to
some
extent,
both
due
to
the
value
of
silver
and
to
comply
with
discharge
regulations.
Several
silver
recovery
technologies
are
available,
and
the
technology
2
of
choice
depends
on
installation
size
and
recovery
requirements.
The
two
most
common
methods
are
metallic
replacement
with
the
use
of
chemical
recovery
cartridges,
and
electrolytic
recovery.

None
of
the
hundreds
of
thousands
of
photoprocessing
establishments
have
discharge
permits
that
refer
to
the
existing
guidelines
found
at
40
CFR
Part
459
Subpart
A.
The
reason
facilities
are
not
covered
directly
by
the
guidelines
is
that
only
BPT
regulations
have
been
published,
which
cover
direct
dischargers.
However,
all
except
for
a
few
large
photoprocessors
discharge
to
publicly
owned
treatment
works
(
POTW),
which
requires
pretreatment
standards
for
existing
sources
(
PSES)
or
pretreatment
standards
for
new
sources
(
PSNS)
for
coverage
by
the
pretreatment
standards.
For
the
small
percent
of
facilities
that
are
direct
dischargers,
there
is
a
production
requirement
that
the
facility
process
1600
square
feet
per
day
or
more
of
photosensitive
film
and
paper.
As
a
result
of
these
factors
the
current
guidelines
are
not
applicable
to
virtually
any
photoprocessing
facilities.

With
the
lack
of
any
applicable
national
pretreatment
standards
for
photoprocessing
wastestreams,
"
local
limits"
as
developed
by
the
receiving
POTW
are
the
normal
means
of
controlling
photoprocessing
discharges.
The
local
limits
are
normally
numeric
and
concentrationbased
and
frequently
the
only
pollutant
monitored
in
the
indirect
discharge
permit
is
silver.
The
predominance
of
local
limits
to
control
photoprocessing
discharges
leads
to
a)
mainly
concentration
based
limits,
b)
variability
from
municipality
to
municipality
on
allowable
discharge
concentration,
and
c)
possible
changes
in
discharge
limits
based
on
changing
water
quality
criteria
or
water
body
loadings
goals.
EPA
has
always
encouraged
the
use
of
production­
based
rather
than
concentration­
based
limits
for
the
control
of
photoprocessing
wastewaters
to
promote
water
conservation.

There
are
questions
concerning
the
environmental
fate
and
effects
of
silver
from
photoprocessing
wastes.
Many
of
the
stringent
local
limits
are
based
on
the
highly
dissociated
and
toxic
silver
nitrate.
While
silver
nitrate
is
used
in
the
production
of
photographic
film
and
paper,
it
is
not
a
characteristic
pollutant
of
photoprocessing
wastewaters.
Rather,
silver
in
photoprocessing
wastewaters
is
characteristically
in
the
form
of
silver
thiosulfate
complex,
which
has
been
shown
to
be
about
20,000
to
40,000
times
less
toxic,
on
a
concentration
basis,
to
acutely
exposed
fathead
minnows.
The
local
limits
may
be
overly
stringent
with
regard
to
concentration
of
silver
discharged,
while
lax
on
total
mass
of
silver
or
other
pollutants,
due
to
lack
of
technical
expertise
and
resources
available
at
the
local
level.
Further
study
is
required
to
accurately
predict
the
fate
and
toxicity
of
silver
from
photoprocessing
wastestreams
after
entering
a
POTW.
3
2.
Introduction
The
purpose
of
this
Preliminary
Data
Summary
for
the
Photoprocessing
Industry
is
to
provide
information
for
determining
whether
the
existing
technology­
based
effluent
guidelines
at
40
CFR
Part
459
should
be
revised.
This
study
describes
the
size
and
demographics
of
the
industry,
photoprocessing
operations
and
the
typical
wastewaters
generated,
as
well
as
the
technologies
available
to
treat
these
wastewaters.
Total
national
pollutant
loadings
are
estimated,
and
resulting
environmental
effects
are
qualitatively
postulated.
This
information
is
presented
against
the
backdrop
of
the
existing
technology­
based
guidelines
and
the
utility
of
these
guidelines
to
the
permit
writer.

Policy
discussions
and
rankings
with
other
industries
for
selection
of
guidelines
revision
are
not
subjects
of
this
study.
However,
the
material
herein
is
a
source
of
information
for
such
future
discussions
and
rankings.

This
study
was
conducted
to
meet
EPA's
obligations
under
section
304(
m)
of
the
Clean
Water
Act,
as
implemented
through
a
consent
decree
in
Natural
Resources
Defense
Council
et
al.
v.
Browner
(
D.
D.
C.
89­
2980,
January
31,
1992)(
the
"
Consent
Decree").
Pursuant
to
the
decree,
the
Agency's
latest
biennial
plan
for
developing
new
and
revised
effluent
guidelines
was
published
on
October
7,
1996
(
61
FR
52582),
in
which
schedules
were
established
for
reviewing
existing
effluent
guidelines
and
developing
new
and/
or
revised
effluent
guidelines
for
several
industry
categories.
One
of
the
industries
selected
for
review
of
existing
effluent
guidelines
was
the
Photographic
Processing
Point
Source
Category
(
40
CFR
459).

Specifics
of
the
existing
guidelines
are
presented
in
Chapter
3.
This
discussion
explains
that
the
existing
guidelines
are
not
relevant
to
the
photoprocessing
industry,
due
to
the
lack
of
pretreatment
standards
in
an
industry
where
most
facilities
discharge
indirectly
to
a
publicly
owned
treatment
works.
Chapter
3
then
presents
how,
in
lieu
of
applicable
guidelines,
local
limits
may
be
applied.
Issues
affecting
the
environmental
performance
of
photoprocessors
are
also
outlined.

A
profile
of
the
industry
is
given
in
Chapter
4,
detailing
what
is
considered
a
"
photoprocessor,"
where
these
photoprocessors
exist,
and
their
relative
market
share.
For
certain
segments
of
the
industry,
facilities
are
primarily
engaged
in
photoprocessing,
and
these
segments
are
identified
by
their
Standard
Industrial
Classification
(
SIC)
codes.
Photoprocessing
also
occurs
as
an
ancillary
activity
in
a
myriad
of
other
public
and
private
institutions
as
well.
These
institutions
are
identified,
and
data
on
market
size
and
photoprocessing
volume
is
presented.

Chapter
5
describes
the
basic
photoprocessing
operations.
This
leads
into
the
discussion
of
wastewater
sources
and
pollutant
characterization
in
Chapter
6.
Here,
information
and
data
are
presented
in
an
attempt
to
define
the
characteristic
pollutants
of
photoprocessing
wastestreams,
and
the
volume
of
these
wastestreams.
Since
no
data
has
been
gathered
recently
by
the
EPA
to
support
the
values
presented,
the
characteristic
pollutant
list
may
not
be
accurate,
and
pollutant
4
loadings
based
on
flow
rate
and
concentration
can
only
be
estimated.
Further
study,
possibly
including
sampling
of
photoprocessing
wastewaters,
would
be
necessary
to
obtain
more
precise
loadings
values.

Chapter
7
presents
the
control
and
treatment
technologies
available
to
photoprocessors.
Silver
recovery
and
management
systems
are
explained,
as
well
as
other
practicable
recovery
methods
such
as
color
developer
reuse
and
ferricyanide
recovery.
The
economic
motive
as
well
as
regulatory
compliance
motive
for
installing
and
maintaining
such
treatment
and
recovery
systems
is
discussed.

Chapter
8
attempts
to
provide
a
qualitative
assessment
of
the
effect
of
discharging
photoprocessing
effluent
on
the
environment.
This
is
done
by
identifying
the
pollutants
in
the
wastewaters,
estimating
their
discharge
quantities,
and
assigning
toxic­
weighted
factors
to
these
pollutants
to
arrive
at
toxic­
weighted
pound­
equivalents.
This
analysis
is
followed
with
a
caveat
concerning
the
dependence
of
the
toxicity
of
silver
to
the
speciation
of
the
silver,
which
dictates
the
oxidation
state,
solubility
in
water,
and
ionic
dissociation
in
water,
of
the
silver
atom
or
molecule.

Again,
the
goal
of
this
Preliminary
Data
Summary
is
to
collate
and
put
into
perspective
the
readily
available
information
and
data
concerning
the
photoprocessing
industry.
This
study
achieves
its
purpose
in
supplying
information
relevant
to
the
existing
guidelines
in
the
current
photoprocessing
operating
and
regulatory
environment,
to
aid
in
the
decision
of
whether
or
not
to
revise
the
photoprocessing
effluent
guidelines.
5
3.
Regulation
of
Photoprocessing
Wastewaters
3.1
Existing
Effluent
Guidelines
EPA
promulgated
an
Interim
Final
Rule
for
the
Photographic
Category
on
July
14,
1976
(
41
FR
29078).
The
rule
established
best
practicable
control
technology
currently
available
(
BPT)
limitations
for
one
subcategory,
the
Photographic
Processing
Subcategory
at
40
CFR
Part
459,
Subpart
A.
The
Agency
determined
that
further
subcategorization
of
photographic
processors
was
unnecessary
due
to
the
similarity
of
pollutants
discharged
across
the
industry
and
that
the
pollutant
loadings
per
unit
of
production
among
the
studied
facilities
were
in
a
relatively
narrow
range.

Subpart
A
covers
"
point
source
discharges
resulting
from
the
development
or
printing
of
paper,
prints,
slides
negatives,
enlargements,
movie
film,
and
other
sensitized
materials
except
that
facilities
processing
150
sq.
meters
(
1600
sq.
feet)
per
day
or
less
are
not
covered."
The
scope
includes
both
commercial
and
military
facilities.
Thus
these
regulations
apply
to
facilities
that
directly
discharge
pollutants,
but
facilities
that
indirectly
discharge
to
sewer
systems
are
not
covered.

EPA
identified
the
major
sources
of
wastewater
from
the
industry
as
photo­
processing
solution
overflows
and
wash
waters.
The
rule
listed
the
known
significant
pollutants
as
pH,
total
suspended
solids
(
TSS),
biological
oxygen
demand
(
BOD),
chemical
oxygen
demand
(
COD),
cyanide
and
silver
in
various
forms.

The
technology
basis
for
the
limitations
consisted
of
electrolytic
silver
recovery
and
bleach
regeneration.
In­
plant
measures
to
reduce
silver
and
cyanide
were
included
in
the
technology
basis.
EPA
also
considered
basing
limitations
on
biological
treatment,
but
did
not
do
so
because
of
estimated
cost
impacts.

The
BPT
limitations
at
§
459.12
are
as
follows:

Parameter
Daily
Maximum
30­
day
average
(
kg
per
1,000
m2
of
product)

silver
0.14
0.07
cyanide
0.18
0.09
pH
Within
range
of
6.0
to
9.0
­­­
1The
Development
Document
contains
chapters
on
BAT,
NSPS
and
PSNS
limits,
although
the
regulations
were
never
issued.

6
While
most
BPT
regulations
also
set
limitations
for
the
conventional
parameters
BOD
and
TSS,
the
rulemaking
notice
stated
that
by
controlling
silver
and
cyanide,
BOD
and
TSS
are
effectively
co­
treated,
as
well
as
COD.

The
limitations
are
production
based,
based
on
the
surface
area
of
film
or
paper
processed.
The
EPA
determined
that
concentration
based
limitations
where
not
appropriate
for
this
industry
because
such
limitations
encouraged
high
water
use
and
discouraged
water
conservation.

In
the
July
14,
1976
notice,
the
Agency
stated
its
intent
to
publish
a
proposed
rule
covering
best
available
technology
economically
achievable
(
BAT),
new
source
performance
standards
(
NSPS),
and
pretreatment
standards
for
new
sources
(
PSNS)
for
the
industry.
Such
regulations
would
affect
facilities
that
indirectly
discharge
wastewaters.
It
also
stated
it
may
propose
regulations
for
the
exempted
smaller
facilities.
However,
these
regulations
were
never
promulgated.
1
EPA
considered
issuing
effluent
guidelines
for
other
subcategories
of
the
photographic
industry,
but
no
regulations
were
issued.
For
four
subcategories,
the
Agency
found
very
small
quantities
of
toxic
pollutants
in
the
raw
waste
load:
Diazo
Aqueous,
Diazo
Solvent,
Photographic
Chemicals,
and
Thermal
Products.
The
Silver
Halide
subcategory
also
had
small
quantities
of
toxics
in
the
raw
waste
loads,
and
most
of
the
facilities
were
direct
dischargers,
with
NPDES
permits
that
required
effective
treatment.(
EPA
1981b)

It
has
been
approximated
that
there
are
350,000
to
500,000
facilities
throughout
the
United
States
which
process
photographic
films
and
papers.(
Dufficy,
Silver
CMP)
However,
no
permits
are
issued
under
40
CFR
459
Subpart
A.
This
is
due
to
the
fact
that
almost
all
photoprocessing
facilities
are
indirect
dischargers
(
discharge
to
a
POTW),
but
only
BPT
has
been
published
which
covers
direct
discharges.
Or
if
they
are
direct
dischargers,
their
daily
production
may
fall
under
the
limit
of
1600
square
feet.
Therefore,
the
existing
regulations
are
not
of
utility
to
the
permit
writers.

3.2
Local
Limits
In
lieu
of
national
pretreatment
standards
for
the
Photographic
Processing
Subcategory,
POTWs
may
use
local
limits
and
the
general
and
specific
prohibitions
established
under
the
General
Pretreatment
Regulations
(
40
CFR
Part
403).
EPA
developed
the
General
Pretreatment
Regulations
under
the
Clean
Water
Act
(
CWA)
to
prevent
the
discharge
to
POTWs
of
pollutants
2
"
Pass
Through"
is
defined
as
"
a
discharge
which
exits
the
POTW
into
waters
of
the
United
States
in
quantities
or
concentrations
which,
alone
or
in
conjunction
with
a
discharge
or
discharges
from
other
sources,
is
a
cause
of
a
violation
of
any
requirement
of
the
POTW's
NPDES
permit
(
including
an
increase
in
the
magnitude
or
duration
of
a
violation)."
40
CFR
403.3
(
n).
"
Interference"
is
defined
as
"
a
discharge
which,
alone
or
in
conjunction
with
a
discharge
or
discharges
from
other
sources,
both:
(
1)
inhibits
or
disrupt
the
POTW,
its
treatment
processes
or
operations,
or
its
sludge
processes,
use
or
disposal;
and
(
2)
therefore
is
a
cause
of
a
violation
of
any
requirement
of
the
POTW's
NPDES
permit
(
including
and
increase
in
the
magnitude
or
duration
of
a
violation)
or
of
the
prevention
of
sludge
use
or
disposal
in
compliance
with
the
following
statutory
provisions
and
regulations
or
permits
issued
thereunder
(
or
more
stringent
state
or
local
regulations):
Section
405
of
the
Clean
Water
Act,
the
Solid
Waste
Disposal
Act
(
SWDA)
(
including
Title
II,
more
commonly
referred
to
as
the
Resource
Conservation
and
Recovery
Act
(
RCRA),
and
including
state
regulations
contained
in
any
state
sludge
management
plan
prepared
pursuant
to
Subtitle
D
of
the
SWDA),
the
Clean
Air
Act,
the
Toxic
Substances
Control
Act,
and
the
Marine
Protection,
Research
and
Sanctuaries
Act."
40
CFR
403.3
(
i).

7
which
will
interfere
with,
pass
through2,
or
which
are
otherwise
incompatible
with
the
POTW
(
CWA
§
307
(
b)(
1)).
POTWs
must
establish,
develop
and
enforce
specific
limits
to
implement
the
general
and
specific
EPA
prohibitions.
The
specific
limits
developed
by
the
POTWs
are
commonly
referred
to
as
"
local
limits"
and
are
enforceable
pretreatment
standards
under
the
Clean
Water
Act.(
§
403.5(
d))

Because,
by
definition
within
the
context
of
40
CFR
Part
403,
pollutant
Pass
Through
or
Interference
results
in
a
violation
of
the
POTW's
NPDES
permit,
the
terms
of
the
POTW's
NPDES
permit
generally
serves
as
a
guide
in
establishing
appropriate
local
limits
to
prevent
such
Pass
Through
or
Interference.
Accordingly,
the
effluent
limits,
water
quality
and
sludge
protection
conditions,
toxicity
requirements,
and
operation
and
maintenance
(
O&
M)
objectives
found
in
a
POTW's
NPDES
permit
generally
establish
the
framework
within
which
the
POTW
must
operate
in
order
to
prevent
Pass
Through
and/
or
Interference.

In
determining
the
pollutants
to
be
regulated
in
categorical
pretreatment
standards,
another
type
of
pass
through
analysis
is
performed.
This
analysis
is
based
on
the
pollutants
determined
to
be
present
in
the
wastewater
discharges
from
the
industry
and
is
not
restricted
to
only
those
pollutants
contained
in
the
POTW's
NPDES
permits.

The
General
Pretreatment
Regulations
also
recognize
that
local
limits
which
are
more
stringent
than
those
set
forth
in
the
federal
regulations
may
be
established
by
state
or
local
law.
In
addition,
POTWs
may
choose
to
impose
local
limits
which
regulate
categorical
industries
more
stringently
than
under
an
applicable
categorical
standard,
in
which
case
the
local
limits
will
supersede
the
categorical
standards
as
the
applicable
pretreatment
standards.
8
While
local
limit
development
is
required
of
POTW's
under
the
Clean
Water
Act
and
the
General
Pretreatment
Regulations,
neither
the
federal
statute
nor
the
regulations
mandate
the
type
of
local
limits
to
be
established.
Instead,
as
EPA
has
recognized
in
its
rulemakings
under
the
General
Pretreatment
Regulations,
the
establishment
of
local
limits
is
a
matter
primarily
of
local
concern
which
should
be
left
to
the
discretion
of
the
POTW.(
see
46
FR
9494,
9415,
Jan.
28,
1981,
and
52
FR
1586,
1593,
Jan.
14,
1987)
To
help
with
local
limit
development,
EPA
has
issued
the
"
Guidance
Manual
on
the
Development
and
Implementation
of
Local
Discharge
Limitations
Under
the
Pretreatment
Program."(
EPA
1987)
Through
this
guidance,
EPA
has
indicated
that
POTWs
are
to
use
site­
specific
data
to
identify
pollutants
of
concern
which
might
reasonably
be
expected
to
be
discharged
in
quantities
sufficient
to
cause
POTW
or
environmental
problems.
Once
the
pollutants
of
concern
and
the
sources
discharging
these
pollutants
have
been
identified,
the
POTW
must
select
the
most
effective
technical
approach
for
the
development
of
its
local
limits.

While
numeric
limits
have
traditionally
been
used
for
local
(
non­
categorical)
limits,
they
are
not
required
by
federal
statute
or
regulation.
One
alternative
approach
for
local
limit
development
identified
by
EPA
in
its
guidance
is
the
use
of
industrial
user
management
practice
plans.
Through
this
approach,
a
POTW
can
require
dischargers
to
develop
and
implement
management
practice
plans
covering
their
handling
of
chemicals
and
wastes.
Once
incorporated
into
local
laws
and
regulations,
these
plans
become
an
enforceable
pretreatment
requirement.

The
majority
of
the
photoprocessing
facilities
are
small
in
size
(
having
fewer
than
ten
employees),
and
typically
discharge
less
than
1,000
gallons
of
wastewater
per
day.
For
the
most
part,
these
photoprocessing
indirect
dischargers
do
not
meet
the
definition
of
a
"
Significant
Industrial
User"
(
SIU)
in
the
General
Pretreatment
Regulations
because
no
pretreatment
standards
have
been
incorporated
into
40
CFR
Part
459
and
their
discharge
of
process
wastewater
is
less
than
25,000
gallons
per
day
and/
or
5%
of
the
hydraulic
or
organic
capacity
of
the
POTW.(
§
403.3
(
t))
While
individual
photoprocessors
can
be
designated
an
SIU
by
a
POTW,
the
burden
of
demonstrating
that
an
individual
photoprocessor
"
has
a
reasonable
potential
for
adversely
affecting
the
POTW's
operation
or
for
violating
any
pretreatment
standard
or
requirement"
is
high.

3.2.1
Local
Limits
on
Silver
Silver
was
identified
as
a
"
priority
pollutant"
in
the
Clean
Water
Act
of
1977
(
CWA
307
(
a)(
1)),
following
an
earlier
listing
of
silver
as
a
drinking
water
contaminant
by
the
United
States
Public
Health
Service.
EPA
issued
water
quality
criteria
for
silver
in
1980.(
EPA
1980)
In
1987,
amendments
to
the
CWA
required
EPA
and
the
states
to
establish
water
quality
standards
and
to
set,
where
necessary,
water
quality
based
effluent
limitations
for
priority
pollutants,
including
silver,
which
were
causing
water
quality
problems
(
CWA
304(
l)).
As
a
result,
POTWs
are
beginning
to
receive
monitoring
requirements
and/
or
numerical
limitations
for
silver
in
their
NPDES
permits.
At
the
same
time,
POTWs
are
finding,
through
their
headworks
loading
analyses,
discharger
surveys
and
other
analyses,
that
much
of
the
silver
is
being
discharged
by
9
numerous
small
sources
such
as
domestic,
institutional
and
commercial
sources
which
are
more
difficult
to
control
than
photoprocessors.
When
taken
as
a
whole,
photoprocessors
have
been
found
to
be
a
major
source
of
silver.
In
most
cases,
silver
is
the
only
pollutant
in
photoprocessing
wastewaters
which
is
subject
to
local
limits.

Since
virtually
all
photoprocessors
are
not
covered
by
national
categorical
standards,
local
limits
are
the
normal
route
to
control
the
pollutants
discharged
by
photoprocessors.
In
an
attempt
to
provide
both
photographic
processors
and
POTWs
with
a
cost­
effective
alternative
to
numeric
limits
and
monitoring,
the
Silver
Council,
which
is
an
industry
association,
and
the
Association
of
Metropolitan
Sewerage
Agencies
(
AMSA)
have
developed
a
"
Code
of
Management
Practice
for
Silver
Dischargers"
(
Silver
CMP).
The
Silver
CMP
provides
recommendations
on
technology,
equipment
and
management
practices
for
controlling
silver
discharges
to
POTWs.
The
practices
recommended
vary
with
the
size
of
the
photoprocessor,
defined
by
flow
volume
of
silver­
rich
solution
and
wash
water.
Through
the
use
of
its
alternative
compliance
mechanisms,
the
Silver
CMP
encourages
use
of
pollution
prevention
technologies,
such
as
water
conservation
methods.

The
Silver
CMP
encourages
the
development
of
industry­
wide
performance
standards
for
silver
recovery
systems
that
maximize
silver
recovery
and
minimize
its
release
to
the
environment.
The
recommended
practices
are
defined
by
a
minimum
recovery
of
silver
from
silver­
rich
processing
solutions
(
e.
g.,
90
percent)
and
alternative
combinations
of
recovery
methods
that
would
achieve
those
recovery
rates.
Those
developing
the
Silver
CMP
estimate
that
compliance
with
the
recommendations
would
reduce
silver
loadings
to
POTWs
by
25
to
50
percent.
Three
municipalities
have
implemented
the
Silver
CMP:
Albuquerque,
NM;
Colorado
Springs,
CO;
and
New
York
,
NY.
Over
a
dozen
other
municipalities
are
planning
to
implement
or
have
expressed
an
interest
in
implementing
the
recommendations
of
the
Silver
CMP.
However,
data
have
not
been
provided
to
EPA
to
demonstrate
the
reductions
in
silver
and
other
pollutants
discharged
upon
implementation
of
the
Silver
CMP.
Currently
(
1996),
the
Silver
Council
and
AMSA
propose
to
jointly
conduct,
with
EPA,
a
3­
year
program
to
implement
and
measure
the
effectiveness
of
the
Silver
CMP
in
5
to
7
cities
of
various
sizes
throughout
the
United
States.

The
existence
and
acceptance
of
the
Silver
CMP,
and
the
results
of
the
Silver
CMP
demonstration
project,
will
not
necessarily
have
an
effect
on
any
future
effluent
guidelines
development
for
the
photoprocessing
industry.
In
part,
this
is
due
to
the
different
means
of
the
two
pollutant
discharge
control
ends:
single
pollutant
versus
multi­
pollutant,
and
local
evaluation
and
acceptance
versus
national
rule.

3.3
Regulatory
Drivers
and
Barriers
A
study
completed
by
the
EPA
in
1994
investigated
the
factors
influencing
the
environmental
performance
of
the
photoprocessing
industry.
The
goal
of
the
study
was
to
determine
what
factors
act
as
incentives
to
improve
environmental
performance
(
drivers)
and
what
factors
act
as
barriers
or
disincentives
to
improving
environmental
performance.
Some
of
10
the
issues
raised
in
the
report
are
outlined
below.
For
the
details
of
the
analysis
the
report
should
be
reviewed.(
EPA
1994)

The
report
notes
that
a
number
of
factors
contribute
to
the
low
local
limits
concentration
for
silver
that
are
imposed
in
many
locations.
First,
the
federal
water
quality
standard
is
based
on
the
toxicity
of
ionic
silver.
The
federal
concentration
limit
for
silver
in
aqueous
effluent
is
5
parts
of
silver
per
million
parts
of
water.
Again,
this
limit
is
based
on
tests
performed
with
silver
nitrate
in
laboratory
test
water,
which
yields
ionic
silver.
However,
silver
nitrate
is
not
a
characteristic
pollutant
of
photoprocessing
wastewater.
Rather,
silver
thiosulfate
is
the
characteristic
form
of
silver,
and
silver
thiosulfate
has
been
shown,
on
a
concentration
basis,
to
be
thousands
of
times
less
acutely
toxic
to
fathead
minnows
than
silver
nitrate.(
Dufficy)
Currently
there
are
no
reliable
analytical
procedures
to
test
for
ionic
silver,
so
that
for
the
time
being
monitoring
and
compliance
are
necessarily
based
on
total
recoverable
silver.
Also,
pretreatment
permit
limits
are
practically
always
expressed
on
a
concentration
rather
than
mass
basis,
which
discourages
adopting
water
saving
measures
such
as
"
washless"
technologies
or
otherwise
reducing
water
use.

The
report
also
notes
that
the
regulation
of
silver­
bearing
wastes
under
the
Resource
Conservation
and
Recovery
Act
(
RCRA)
increases
transportation
costs
of
some
photoprocessing
wastewaters
to
central
treatment
facilities
for
silver
recovery,
and
increases
the
burden
of
storing
wastewaters
and
shipment
off­
site
for
centralized
waste
treatment.
On
the
other
hand,
photoprocessors
can
avoid
RCRA
regulation
by
treating
and
discharging
their
wastes
in
compliance
with
Clean
Water
Act
requirements.
These
factors,
reportedly,
discourage
the
recycling
of
silver,
discourage
the
efficient
treatment
of
photoprocessing
wastewaters
in
centralized
treatment
facilities,
and
encourage
discharge
of
these
wastewaters
to
POTWs.
It
is
claimed
that
removal
of
silver
from
the
RCRA
Toxicity
Characteristic
list
would
eliminate
most
of
the
added
burden,
encouraging
increased
recycling
of
silver
and
centralized
treatment
of
photoprocessing
wastewaters.
3The
terms
"
photoprocessing,"
"
photofinishing,"
and
"
photo
developing"
are
interchangeable.
For
consistency,
the
term
"
photoprocessing"
is
used
throughout
this
report.

11
4.
Photoprocessing
Industry
Profile
4.1
Photoprocessing
Industry
Overview
The
photoprocessing
industry,
for
the
purpose
of
this
study,
consists
of
photographic
processors
using
silver
halide­
sensitized
photographic
materials
to
produce
continuous­
tone
black­
and­
white
or
color
negatives,
positive
transparencies,
and
prints
for
delivery
to
external
customers.
The
main
industrial
segments
to
which
this
study
applies
are
as
follows.
"
Photofinishing
Laboratories"
(
SIC
7384),
consists
of
facilities
primarily
engaged
in
film
developing
and
print
processing
for
the
trade
or
the
general
public.
Facilities
primarily
engaged
in
photography
for
the
general
public
are
classified
as
"
Photographic
Studios,
Portrait"
(
SIC
7221).
Included
in
this
group
are
portrait
photographers
and
school,
home,
and
transient
photographers.
Establishments
primarily
engaged
in
providing
commercial
photography
services
for
advertising
agencies,
publishers,
and
other
business
are
classified
in
"
Commercial
Photography"
(
SIC
7335),
and
those
providing
commercial
art
or
graphic
design
services
for
advertising
agencies,
publishers,
and
other
business
are
classified
as
"
Commercial
Art
and
Graphic
Design"
(
SIC
7336).
The
processing
of
motion
picture
film
falls
under
"
Services
Allied
to
Motion
Picture
Production"
(
SIC
7819).
3
In
the
industries
mentioned
above,
a
significant
portion
of
total
revenue
is
in
general
derived
through
the
processing
of
photographic
films,
slides,
and
prints.
However,
as
in
SIC
7336
and
7819,
photoprocessing
may
occur
along
with
other
significant
revenue­
generating
activities.
Photoprocessing
operations
also
occur
in
a
myriad
of
other
public
and
private
institutions,
such
as
dental
offices,
hospitals,
police
departments,
industrial
X­
ray
services,
and
schools.
As
an
example,
Table
4.1
shows
the
number
of
photoprocessing
facilities
by
type
for
Phoenix,
Arizona.
In
the
health
care
and
noncommercial
sectors,
the
processing
of
photographic
films
and
papers
is
an
ancillary
activity,
whereas
in
the
commercial
sector
it
is
the
main
activity.
12
Table
4.1
Number
of
Photoprocessing
Facilities
by
Type
for
Phoenix,
Arizona
Facility
type
Number
of
facilities
by
size
(
in
number
of
employees)

Small
(
1
to
19)
Medium
(
20
to
49)
Large
(
50
to
499)
(
More
than
500)

Health
Care
Hospitalsa
14
1
61
32
Dentists
1,422
16
1
0
Doctors
915b
122
47
2
Veterinarians
278
9
2
0
Chiropractors
515
6
0
0
Commercial
Minilabs
184
0
0
0
Photofinishers
0
5
5
0
Prof.
Labs
129
9
2
0
Motion
Picture
1
0
0
0
Microfilm
12
3
1
0
Graphic
arts
783
101
47
3
Noncommercial
Schools
0
0
5
7
Police
Dept.
4
3
18
11
Heavy
Construction.
269
57
58
4
Transportation
14
2
44
7
Fabricated
Prods.
18
5
42
10
Finance/
insurance/
real
estate
0
0
22
10
Jewelry/
silverware/
plated
ware
47
1
0
0
Facility
type
Number
of
facilities
by
size
(
in
number
of
employees)

13
a
Does
not
include
university,
college,
or
public
hospitals.
b
Include
offices
of
podiatrists,
osteopaths,
and
10%
of
all
medical
doctor
offices.
Source:
WEF
1994
Combining
all
types
of
facilities,
it
is
estimated
that
photoprocessing
operations
occur
at
350,000
to
500,000
locations
in
the
United
States.(
Dufficy,
Silver
CMP)
The
number
of
establishments
identified
under
the
commercial
photoprocessing
SIC
codes
mentioned
above
are
listed
in
Table
4.2
below.

Table
4.2
Number
of
Photoprocessing
Establishments
by
SIC
Code,
1996
Standard
Industrial
Classification
(
SIC)
SIC
Description
Number
of
Establishments
As
Primary
Business
As
Primary
or
Secondary
Business
7384
Photofinishing
Laboratories
10,430
13,171
7221
Photographic
Studios,
Portrait
27,607
32,184
7335
Commercial
Photography
14,845
18,414
7336
Commercial
Art
and
Graphic
Design
31,476
37,264
7819
Services
Allied
to
Motion
Picture
Production
7,656
9,187
Total:
92,014
110,220
Source:
Dun
&
Bradstreet
Photographic
films
and
paper
are
used
mainly
for
the
following
reasons:
a)
to
diagnose
medical
problems,
b)
to
diagnose
structural
defects
of
buildings,
bridges,
and
roads,
c)
document,
record,
and
transfer
information,
and
d)
record
personal
events
and
preserve
memories.
The
market
for
photographic
services
and
supplies
can
be
divided
into
three
major
segments:

!
Medical
applications
!
Graphic
arts,
and
!
Amateur
photography,
served
by
commercial
sector
Medical
users
include
large
hospitals
and
diagnostic
clinics,
as
well
as
doctors'
and
veterinarians'
offices.
The
largest
single
user
in
the
medical
market
is
the
Veterans
4It
has
been
reported
that
in
1995
the
Photographic
Industry
consumed
29
percent
of
total
worldwide
silver
fabrication,
for
the
production
of
photographic
film
and
paper.(
WSS
1996)

14
Administration.
The
graphic
arts
industry
consists
mainly
of
printers
who
are
partially
involved
in
photoprocessing.
These
businesses
serve
an
industrial
market
through
published
documents
and
advertising.
In
most
cases,
photography
represents
a
small
part
of
their
business
and
does
not
present
their
most
pressing
environmental
concern.
The
amateur
photography
sector
includes
all
amateur
photographic
processing,
whether
at
minilabs,
large
wholesale
laboratories,
or
mail
order
processing
labs.
These
labs
serve
individuals
taking
pictures
mainly
to
preserve
memories.

There
are
the
variations
among
the
demands
of
the
three
major
market
segments­­
medical
imaging,
graphic
arts,
and
amateur
photography.
These
requirements
affect
the
constraints
on
process
and
product
improvements:

!
The
medical
market
is
concerned
with
rapid
and
accurate
diagnosis,
and
therefore
requires
both
quality
and
speed,
as
well
as
longevity
of
the
image.

!
The
graphic
arts
market
requires
high
quality
pictures,
but
is
relatively
unconcerned
with
processing
speed.

!
The
amateur
market
tends
to
be
more
concerned
with
speed
in
processing,
but
demands
increasingly
higher
quality.

In
lieu
of
revenue
and
photoprocessing
volume
data,
the
relative
size
of
these
segments
can
be
inferred
from
information
of
silver
consumption.
Data
on
the
allocation
of
silver
for
various
photographic
uses
for
1993
are
shown
in
Table
4.3
below.
4
Table
4.3
Photographic
Use
of
Silver,
1993
Photographic
End­
Use
Silver
Demand:
U.
S.,
Japan,
and
Western
Europe
(
Million
Troy
Ounces)
Percent
of
Total
Photographic
Silver
Demand
Amateur
Picture
Taking
(
Commercial)
82
44%

Medical,
Excluding
Dental
46
25%

Graphic
Arts
41
22%

Industrial
and
Dental
17
9%

Source:
WSS
1993
15
4.2
Photoprocessing
Volume
and
Revenue:
Amateur
Market
Information
on
amateur
photoprocessing
volume
and
revenue
is
presented
below.
These
data
exclude
health
and
noncommercial
photoprocessing
because
data
were
not
available
for
these
segments.
As
shown
in
Table
4.3,
by
correspondence
to
silver
use
it
is
estimated
that
the
amateur
market
accounts
for
44
percent
of
total
photoprocessing
volume.

In
1994,
the
total
number
of
rolls
processed
was
715.5
million,
resulting
in
17.58
billion
exposures.
The
predominant
film
format
of
choice
was
35mm,
making
up
92.1
percent,
and
color
prints
were
the
most
popular
film
type,
capturing
94.7
percent,
of
exposures
processed
in
1994.
Tables
4.4
and
4.5
show
the
market
share
of
the
various
film
formats
and
film
types.(
PMA
1995)

Original
prints
are
normally
3
½
by
5
inches
or
4
by
6
inches,
and
they
can
be
either
single
prints
or
twin
prints.
Having
plateaued
at
36
percent
from
1991­
93,
4"
by
6"
print
market
share
jumped
4.5
points
in
1994,
accounting
for
40.6
percent
of
prints.
Twin
prints,
following
a
2.4
point
climb
in
1992,
and
gaining
2.7
points
in
1993,
experience
stable
market
share
in
1994,
with
46.6
percent.
Over
three­
quarters
of
photofinishing
sales
dollars
came
from
original
prints,
while
reprints
and
enlargements
accounted
for
14
percent.(
PMA
1995)

This
amateur
or
commercial
photoprocessing
occurred
through
various
retail
channels,
such
as
drugstores,
stand­
alone
mini­
labs,
and
mail­
order
processors.
The
breakdown
of
market
share
within
each
of
the
retail
channels
is
shown
in
terms
of
roll
share
in
Table
4.6,
and
in
terms
of
dollar
share
in
Table
4.7.
Years
1993
and
1994
are
provided
to
show
the
industry
trends.
As
Table
4.7
shows,
consumers
spent
$
5.5
billion
on
photoprocessing
in
1994.
In
1993,
stand­
alone
mini­
labs
had
the
highest
revenue
spot,
but
were
overtaken
by
drugstores
in
1994.
The
discount/
mass
merchandiser
channel
out
paced
gains
made
in
all
other
channels,
with
its
dollar
share
up
2.9
percentage
points.
Photoprocessors
compete
based
on
price,
quality,
convenience,
and
speed
of
processing.
The
trends
in
demand
for
amateur
photographs
are
somewhat
cyclic
and
follow
the
economic
cycles,
with
a
minimum
customer
base
below
which
demand
will
not
fall.
When
people
become
more
price
sensitive,
as
in
a
recession,
they
are
more
willing
to
sacrifice
convenience
and
speed
for
lower
prices.
(
EPA
1994)
The
characteristics
of
the
various
types
of
labs
are
summarized
in
Table
4.8.

Table
4.4
1994
Photoprocessing
Total
Exposures
by
Film
Format
Film
Format
Number
of
Exposures
(
Millions)
Percent
of
Exposures
35mm
16,190
92.1%

110/
126
1,195
6.8%

Disc
123
0.7%
Film
Format
Number
of
Exposures
(
Millions)
Percent
of
Exposures
16
Other
70
0.45%

Total
17,580
100%

Source:
PMA
1995
Table
4.5
1994
Photoprocessing
Total
Exposures
by
Film
Type
Film
Format
Number
of
Exposures
(
Millions)
Percent
of
Exposures
Color
print
16,648
94.7%

Slide
615
3.5%

Black
&
White
316
1.8%

Total
17,580
100%

Source:
PMA
1995
17
Table
4.6
1993
and
1994
Market
Share
of
Photoprocessing
by
Retail
Channel
­­­
Roll
Share­­­

Retail
Channel
Number
of
Rolls(
Millions)
Percent
Share
1993
1994
1993
1994
Drug
Store
183.8
188.9
26.5%
26.4%

Stand­
Alone
Minilab
104.3
98.4
15.0%
13.8%

Camera
Store
56.0
52.2
8.1%
7.3%

Discount/
Mass
Merchandiser
176.9
202.6
25.5%
28.3%

Supermarket
98.0
96.2
14.1%
13.4%

Mail
Order
53.1
54.8
7.7%
7.7%

Other
22.0
22.5
3.2%
3.1%

Total
694.0
715.5
100.0%
100.0%

Source:
PMA
1995
18
Table
4.7
1993
and
1994
Market
Share
of
Photoprocessing
by
Retail
Channel
­­­
Dollar
Share­­­

Retail
Channel
Retail
Dollars
(
Millions)
Percent
Share
1993
1994
1993
1994
Drug
Store
$
1,356
$
1,359
24.8%
24.5%

Stand­
Alone
Mini­
Lab
$
1,398
$
1,296
25.5%
23.4%

Camera
Store
$
734
$
699
13.4%
12.6%

Discount/
Mass
Merchandiser
$
871
$
1,039
15.9%
18.8%

Supermarket
$
649
$
653
11.9%
11.8%

Mail
Order
$
289
$
312
5.3%
5.6%

Other
$
177
$
180
3.2%
3.2%

Total
$
5,475
$
5,538
100.0%
100.0%

Source:
PMA
1995
Table
4.8
Characteristics
of
Amateur
Film
Processing
Labs
Lab
Type
Price
Quality
Processing
Speed
Minilabs
Two
to
Three
Times
Higher
than
Others
Lower
than
Others
One
Hour
Wholesale
Labs
(
Drug
Stores,
Grocery
Stores)
Medium
Equal
to
Minilabs
Two
to
Three
Days
Mail
Order
Labs
Low
High
One
Week
Source:
EPA
1994
Consolidation
is
occurring
in
the
industry,
both
from
a
manufacturing
perspective
and
from
a
processing
perspective.
Some
smaller
manufactures
have
been
absorbed
by
the
large
market
players.
In
addition,
some
manufactures
are
now
involved
in
processing.
Kodak
owns
19
approximately
half
of
Qualex
Incorporated,
which
is
the
largest
single
photo
processing
company.
Fuji
and
Konica
have
also
purchased
photo
processing
labs.
As
a
result,
the
three
largest
manufactures
are
now
also
full
or
partial
owners
of
the
three
largest
photoprocessing
chains.(
EPA
1994)

Compared
to
large
labs,
smaller
labs
have
a
limited
capital
base,
and
hence
tend
to
be
somewhat
less
sophisticated.
Industry
representatives
point
out
that
the
trend
toward
concentration
among
photoprocessing
labs
over
the
past
several
years
is
largely
a
result
of
restrictive
environmental
standards.
They
claim
that
compliance
has
become
prohibitively
expensive
for
small
operations
to
achieve.

While
stand­
alone
mini­
labs
are
listed
as
a
separate
retail
channel,
mini­
labs
are
also
found
in
all
other
retail
channels
as
well.
Industry
data
distinguish
between
retail
mini­
labs,
regardless
of
retail
channel,
versus
the
larger
wholesale,
captive,
and
mail
order
labs.
The
data
show
that
the
number
of
minilabs
has
grown
rapidly
over
the
past
decade,
from
approximately
800
in
1981
to
18,900
in
1994.
In
1994,
minilabs
were
located
in
3,100
camera
stores,
6,124
stand­
alone
minilab
outlets,
and
5,153
mass­
retail
stores.
This
indicates
a
significant
increase
in
the
number
of
minilabs
in
mass­
retail
stores.
The
number
of
mini­
labs
in
other
types
of
stores
declined
slightly
over
the
same
period.
In
1994
these
mini­
labs
processed
214.2
million
rolls,
accounting
for
30
percent
of
the
total
715.5
million
rolls,
while
the
wholesale,
captive,
and
mail
order
labs
processed
the
remaining
70
percent.
The
mini­
labs
also
proved
more
profitable,
receiving
43.8
percent,
or
$
2,426
million,
of
the
total
$
5,538
million
in
revenue
and
wholesale,
captive,
and
mail
orders
made
the
remaining
56.2
percent
or
$
3,112
million.(
PMA
1995)
Thus,
while
mini­
labs
processed
just
30
percent
of
the
rolls,
they
collected
43.8
percent
of
the
total
revenues.

4.3
Production
of
Photosensitive
Papers
and
Films
and
Photoprocessing
Equipment
The
photographic
equipment
and
supplies
industry
is
not
covered
in
this
study.
This
category
is
mentioned
here
because
of
the
interface
with
photoprocessors,
and
to
explicitly
describe
what
is
and
is
not
covered
in
this
study.

Facilities
classified
under
SIC
3861,
"
Photographic
Equipment
and
Supplies,"
produces
a
wide
variety
of
products
for
the
photoprocessing
industry,
including
photosensitive
plates,
film,
paper,
and
cloth,
photographic
chemicals,
and
photoprocessing
equipment.
While
the
photoimaging
industry
is
highly
diffuse
on
the
processor
side,
it
is
highly
concentrated
on
the
manufacturing
side.
A
Dun
&
Bradstreet
count
in
1996
indicated
974
establishments
under
SIC
3861
as
a
primary
business,
and
1,254
establishments
under
SIC
3861
as
a
primary
or
secondary
business.
Manufacturers
with
significant
operations
in
the
United
States
include:

!
Eastman
Kodak
Company
!
Polaroid
Corporation
!
3M
Corporation
20
!
Xerox
!
Ilford
(
owned
by
International
Paper)

!
Anitec
Image
(
also
owned
by
International
Paper).

Kodak
is
by
far
the
largest
U.
S.
manufacturer.
Polaroid
Corporation
is
the
second
largest
but
their
primary
film
product
is
instant
film.(
EPA
1994)

As
a
whole
these
companies
gain
more
revenue
through
the
sale
of
photographic
nondurable
goods
of
film,
paper,
and
photoprocessing
supplies,
than
through
the
sale
of
processing
equipment.
The
1992
Census
of
Manufacturers
data
shows
that
the
value
of
shipments
of
supplies
of
film
and
paper
was
$
4,545
million,
but
that
of
the
processing
equipment
was
only
$
547
million.(
EPA
1994)

Manufacturers
and
processors
have
a
close
relationship
in
this
industry.
Processors
rely
heavily
on
manufacturers
for
compliance
assistance
and
innovations
to
address
environmental
and
regulatory
concerns.
Manufacturing
is
driven
in
part
by
the
demands
placed
upon
the
processors,
both
by
regulators
and
by
the
end
consumer.
Manufacturers
supply
processing
systems
which
include
both
equipment
and
supplies
to
customers.
Photoprocessors
do
not
have
to
purchase
supplies
from
the
same
manufacturer
that
supplied
the
equipment,
but
many,
especially
the
smaller
minilabs,
often
do.
All
of
the
manufacturers
have
support
systems
to
assist
the
processors
with
operations
and
environmental
compliance.
Such
systems
include
instructional
seminars,
facility
compliance
evaluations,
and
compliance
kits.(
EPA
1994)

4.4
New
Technologies
in
Photography:
Advanced
Photo
System
and
Digital
Imaging
Two
new
technologies
are
introduced
here
because
they
may
affect
the
volume
of
photographic
film
and
paper
processed
in
the
future:
Advanced
Photo
System
(
APS)
versus
the
relative
growth
of
digital
imaging
(
DI).
APS
represents
an
evolution
of
silver
halide
technology
while
DI,
utilizing
electronic
means
of
image
capture
and
storage,
represents
a
threat.

The
APS
system
was
launched
in
April,
1996,
on
basis
of
a
new
film
format
with
a
number
of
features
designed
to
improve
and
simplify
photography.
The
most
significant
improvements
will
be
the
choice
of
three
different
print
layouts,
and
the
ability
to
select
frames
for
printing
from
an
initially
produced
sheet
of
miniature
prints
as
opposed
to
awkward
negatives.
The
new
film
cartridge
is
"
dropped"
in
for
simpler
loading,
and
adds
features
such
as
a
disk
to
store
various
types
of
film
information.
For
example,
this
information
can
be
used
by
the
cameras
to
adjust
for
lighting
conditions,
and
allows
the
film
to
be
removed
mid­
real
and
reloaded
later
on
without
accidental
double
exposure.
The
reverse
side
of
the
film
has
a
transparent
magnetic
layer
which
can
record
digital
information
to
be
used
by
the
photoprocessing
equipment.
Although
each
frame
of
film
will
capture
the
full
image
entering
through
the
lens,
the
selection
of
different
print
layouts
allows
the
processor
to
magnify
a
suitable
area
of
the
frame
to
produce
prints
with
a
range
21
of
aspect
rations.
The
film
itself
is
made
from
a
stronger
and
thinner
base
and
is
coated
with
more
advanced
emulsions.

In
terms
of
photoprocessing
volume
the
most
important
question
is
whether
the
APS
will
encourage
more
prints
to
be
made
because
of
ease
of
frame
selection
from
the
miniature
preview
prints
and
wide
range
of
print
layout
options,
or
less
prints
due
again
to
selection
from
the
miniature
previews.

Market
penetration
by
digital
photography
is
perceived
as
a
threat
to
silver
halide­
based
photography,
but
this
emerging
technology
faces
two
significant
quality
problems.
These
are
the
inferior
and
expensive
image
capture
and
the
low
quality
of
the
output
medium.
DI
would
lead
to
a
decrease
in
film
and
paper
photoprocessing
volume
because
the
film
is
replaced
by
a
semiconductor
chip
known
as
a
charge­
coupled
device.
The
photographs
are
then
downloaded
onto
computer
on
which
they
can
be
manipulated
and
printed
on
thermal
or
ink­
jet
paper.
The
quality
of
the
image
is
directly
proportional
to
the
number
of
photocell
elements
in
the
chargecoupled
device,
which
ranges
from
250,000
in
amateur
cameras
to
over
6
million
in
the
professional
market.
By
contrast,
the
average
35
mm
negative
contains
approximately
10
billion
silver­
halide
crystals.
As
of
1996
cameras
introduced
for
the
amateur
market
cost
in
the
region
of
$
1,000
and
produce
images
of
up
to
756
by
504
dots
or
pixels,
making
them
suitable
for
amateur
use
on
a
computer
screen,
but
unacceptable
for
large
prints.
However,
much
more
expensive
digital
cameras
have
become
fairly
popular
with
photojournalists,
who
can
now
send
photographs
across
the
world
via
mobile
phone
and
computer
links.
The
most
significant
impact
of
digital
photography
on
silver­
halide
photoprocessing
volume
may
come
from
the
medical
X­
ray
sector.
Some
hospitals
are
investing
heavily
in
sophisticated
computer
equipment
to
replace
the
conventional
X­
ray
light
box.(
WSS
1996)

The
effects
of
DI
on
silver
halide­
based
photoprocessing
volume
are
beginning
to
be
seen.
While
the
production
of
X­
ray
film
increased
marginally
in
1995
for
both
domestic
and
export
markets,
manufacturers
reported
that
growth
has
been
curtailed
by
digital
imaging.
In
the
graphics
art
sector,
photographic
paper
consumption
was
down
2
to
3
percent,
reportedly
because
of
the
impact
of
digital
imaging.
The
future
tends
of
DI
market
share
are,
of
course,
speculative.
However,
due
to
the
simplicity
and
lower
cost
inherent
in
silver­
halide
technology,
it
appears
that
this
traditional
technology
will
not
be
overrun
by
DI
in
many
of
the
major
photoprocessing
markets,
such
as
amateur
photography.(
WSS
1996)
22
5.
Description
of
Photoprocessing
Operations
5.1
Process
Descriptions
The
processing
of
photographic
film
and
paper
requires
the
use
of
a
number
of
chemicals
to
develop
and
produce
finished
photographic
goods.
The
waste
streams
generated
vary
widely
according
to
the
type
and
volume
of
processing.
Photoprocessing
is
dominated
by
color
print
film,
prints,
and
slides,
with
only
about
10
percent
of
the
market
involving
black­
and­
white
processing.
Because
color
processing
usually
represents
a
greater
production
volume
of
the
operations
at
a
given
location,
it
usually
generates
a
larger
waste
stream
volume.
An
increasing
portion
of
the
color
market
is
being
taken
by
mini­
labs,
which
are
automated
machines
that
occupy
little
space.
These
machines
are
the
ones
used
by
the
popular
one­
hour
developing
centers.
The
waste
stream
volume
from
most
one­
hour
developing
centers
has
been
greatly
reduced,
because
most
centers
have
converted
to
"
washless"
or
"
plumbingless"
processing,
which
does
not
use
a
conventional
wash
cycle.(
EPA
1991a)

5.1.1
Color
Processing
Film
and
paper
used
for
color
photography
consist
of
three
separate
layers
of
photosensitive
emulsion
with
intermediate
layers.
The
emulsion
layers
are
coated
on
clear
film
base
or
on
paper,
and
each
layer
is
sensitive
to
either
red,
green,
or
blue
light
due
to
the
presence
of
selective
dyes
in
the
emulsion.
Intermediate
layers
filter
out
other
wavelengths,
so
that
the
silver
halide
salts
in
each
photosensitive
layer
are
exposed
only
to
light
of
the
specific
color.
A
colorless
dye­
forming
coupler
is
present
along
with
the
silver
halide
crystals
in
each
emulsion
layer.
When
processed
in
a
color­
developing
solution,
an
image
of
"
developed
silver"
is
formed
in
each
layer.
The
exposed
silver
halide
crystals
are
reduced
to
metallic
silver,
while
simultaneously
producing
oxidized
developer
molecules.
The
oxidized
developer
reacts
with
the
dye­
forming
coupler
to
produce
a
dye
which
is
complementary
in
color
to
the
light
to
which
the
emulsion
layer
is
sensitive.
The
intensity
of
the
dye
formed
in
a
particular
portion
of
the
image
is
dependent
on
the
quantity
of
oxidized
developer,
which
is
in
turn
proportional
to
the
extent
of
exposure
in
that
area.

A
bleach
bath
renders
the
color
image
visible
by
converting
the
black
metallic
silver
image
back
to
a
silver
halide.
All
of
the
silver
on
the
film,
whether
exposed
or
not,
can
then
be
dissolved
and
removed
in
the
fixer
bath.
The
dye
is
retained
in
each
layer
of
the
film
so
that
a
negative
(
complementary)
color
image
remains.
Some
processes
combine
the
bleach
and
fix
processes
in
a
single
solution,
termed
bleach­
fix
or
"
blix."
It
is
a
common
practice
to
introduce
the
film
into
a
stabilizer
bath
after
the
fixer
solution
to
equilibrate
the
emulsion
and
increase
the
stability
of
the
dye
image
to
light.
A
schematic
diagram
of
the
color
negative
film
process
is
shown
in
Figure
5.1.(
EPA
1991a)
23
Figure
5.1
Color
Negative
Film
Process
[
INSERT
FIGURE
5.1]

Positive
color
prints
can
be
made
from
the
film
negative
recorded
by
the
camera
by
exposing
color
paper
or
other
suitable
print
medium
to
light
passed
through
the
developed
film.
The
print
medium,
which
contains
the
same
combination
of
colorsensitive
emulsion
layers
as
does
the
film,
is
then
processed
through
a
similar
sequence
of
solutions
to
obtain
the
final
print,
as
illustrated
by
Figure
5.2.(
EPA
1991a)

For
color
slides,
a
positive
color
image
is
produced
directly
on
the
film
by
reversal
processing.
The
exposed
color
film
is
first
subjected
to
black­
and­
white
processing
to
produce
a
negative
image
consisting
only
of
metallic
silver.
After
washing,
the
film
is
immersed
in
a
reversal
bath
that
renders
the
remaining
silver
salts
developable.
The
film
is
then
processed
in
a
color
developer
that
reduces
the
remaining
silver
salts
and
produces
a
positive
dye
image.
Then
a
sequence
of
bleach,
fixer,
and
wash
steps
produces
the
final
color
transparency.
Color
prints
can
be
made
directly
from
positive
slides
by
a
similar
reversal
process.
Figure
5.3
is
a
schematic
diagram
depicting
both
slide
and
reversal
print
operations.(
EPA
1991a)

Cinemagraphic
film
processing
is
similar
to
processing
of
color
print
or
slide
film.
In
commercial
operations,
a
large
number
of
copies
are
made
from
one
film.
A
print
or
"
negative
image"
film
is
used
for
the
original
exposure
and
then
used
to
make
film
copies
(
much
as
print
film
is
used
to
make
prints).
Amateur
film
processing,
which
usually
results
in
only
one
copy
of
the
film,
uses
film
much
like
slide
film
that
is
exposed
and
processed,
producing
the
positive
image
on
the
originally­
exposed
film.
24
Figure
5.2
Color
Negative
Paper
Process
Figure
5.3
Color
Reversal
Paper
Process
25
5.1.2
Black­
and­
White
Processing
The
photosensitive
medium
used
for
black­
and­
white
processing
is
an
emulsion
composed
of
a
dispersion
of
fine
silver
halide
crystals
in
a
matrix
of
gelatin.
This
emulsion
is
applied
in
a
layer
approximately
1/
1000
of
an
inch
thick
on
a
supporting
material,
either
paper
or
clear
plastic
film.
Brief
exposure
to
small
quantities
of
light
produces
a
chemical
change
in
the
silver
halide
crystals,
which
allows
the
silver
ions
in
the
exposed
crystals
to
be
converted
to
metallic
silver
at
a
faster
rate
than
in
unexposed
crystals.
By
focusing
the
light
through
the
camera
lens,
the
pattern
of
exposed
crystals
corresponds
to
the
image
from
which
light
is
reflected.
At
this
point,
the
exposed
silver
halide
crystals
are
termed
"
developable."
When
the
film
is
subsequently
immersed
in
the
developing
solution,
composed
of
an
alkaline
solution
of
organic
reducing
agents,
the
exposed
silver
halide
crystals
are
reduced
to
metallic
silver.
The
silver
is
dark
in
color
and
produces
a
negative
image.
The
most
commonly
used
developing
agents
are
metol
(
p­
methylaminophenol
sulfate)
and
hydroquinone
(
p­
dihydroxybenzene
or
1,4­
dihydroxybenzene).

The
chemistry
of
development
is
complex.
For
example,
hydroquinone
in
ordinary
sulfite­
containing
developers
(
sodium
sulfite
is
added
to
most
developers
as
a
preservative)
is
oxidized
to
a
semi­
quinone
free
radical,
and
then
reacts
with
sulfite
to
form
mono­
and
di­
sulfonates.
These
reaction
products
may
be
isolated
along
with
quinone,
sodium
sulfate
(
Na
2
SO
4),
and
many
other
compounds
associated
with
the
other
ingredients,
e.
g.,
metal,
sodium
carbonate,
and
potassium
bromide.

If
kept
in
the
developer
bath,
even
the
unexposed
silver
halide
crystals
can
be
converted
to
metallic
silver
by
the
developer
solution.
To
prevent
this,
the
action
of
the
developer
is
arrested
by
transferring
the
film
to
a
stop
bath.
The
stop
bath
is
a
weakly
acidic
solution
(
usually
acetic
acid)
which
neutralizes
any
of
the
alkaline
developer
carried
over
on
the
surface
of
the
film
or
in
the
wetted
gelatin
layer.
Following
the
stop
bath,
the
film
is
immersed
in
a
fixer
solution
that
solubilizes
and
removes
the
remaining
unreacted
silver
salts,
rendering
the
image
on
the
film
permanent.
Fixer
solution
adhering
to
the
film
must
be
removed
in
a
final
rinse
step.

The
film
now
contains
a
negative
image
of
the
scene
which
the
camera
recorded.
A
positive
print
is
prepared
by
exposing
a
photosensitive
sheet
of
paper
to
the
image
formed
when
light
is
passed
through
the
negative
image
of
the
film.
The
paper
is
then
processed
through
a
similar
set
of
operations
(
i.
e.,
developer,
stop
bath,
fixer,
and
rinse).
A
diagram
for
black­
and­
white
processing
that
applies
to
both
film
and
paper
is
shown
in
Figure
5.4.
26
Figure
5.4
Black­
and­
White
Development
Process
As
more
film
is
processed,
the
concentration
of
various
reaction
products
gradually
builds
up
in
the
developer
solution.
Silver
and
bromide
ions
removed
from
the
developed
film
accumulate
in
the
fixer
solution,
and
the
acidic
stop
bath
is
gradually
neutralized
as
the
quantity
of
alkaline
developer
carried
over
increases.
At
some
point,
these
solutions
become
unusable
and
must
be
discarded.
The
final
rinse
is
usually
conducted
in
a
continuous
flow
of
fresh
running
water.
As
a
result,
only
small
amounts
of
silver
and
other
fixer
compounds
can
he
detected
in
the
spent
rinse
water
waste
stream.

Black­
and­
white
reversal
film
processing,
used
to
create
a
positive
black­
and­
white
image
directly
on
the
film,
requires
two
development
steps
with
an
intermediate
bleach
step.
Bleach
solution
for
black­
and­
white
processing
contains
sodium
dichromate.
Spent
bleach
is
considered
a
hazardous
waste
because
of
its
chrome
content.

5.2
Manual
and
Automated
Systems
5.2.1
Manual
Systems
Manual
systems
include
tray
and
tank
processing.
These
are
often
used
for
low
volume
production
such
as
black
and
white
processing,
enlargements,
or
other
services
that
do
not
require,
or
are
not
amenable
to,
cost­
effective
automation.
While
manual
processing
wastes
can
be
significantly
reduced,
this
represents
such
a
small
volume
for
most
businesses
that
the
overall
waste
reduction
impact
may
not
be
significant.
27
The
tray
method
allows
processing
small
quantities
of
film
and
papers
with
minimum
chemical
consumption.
Sheets
of
film
or
paper
are
placed
on
the
bottom
of
the
shallow
tray
containing
solution.
The
tray
is
then
rocked
back
and
forth
manually
to
ensure
that
adequate
fresh
solution
contacts
the
emulsion
surfaces.
The
sheets
are
removed,
drained,
and
transferred
to
the
next
processing
bath.
The
duration
of
each
step
in
the
process
is
timed
according
to
a
prescribed
schedule.
Once
the
processing
is
completed,
the
solutions
are
returned
to
storage
containers
for
reuse.
With
proper
storage,
solutions
can
be
reused
until
chemically
exhausted,
as
indicated
by
test
strips.

Tanks
are
used
for
processing
large
quantities
of
film
and
paper
sheets.
This
method
is
usually
limited
to
sheets
no
larger
than
8
inches
by
10
inches.
The
sheets
are
suspended
vertically
in
the
tank
from
hangers
which
maintain
a
lateral
separation.
The
solution
level
in
each
tank
covers
the
entire
sheet.
The
solution
is
agitated
by
gentle
vertical
movement
of
the
hangers.
When
not
in
use,
the
tanks
should
be
covered
to
keep
foreign
materials
out
of
the
processing
solutions
and
to
minimize
evaporation
and
oxidation.
Oxidation
of
the
developer
solution
can
be
further
reduced
by
using
a
tight­
fitting
"
floating
lid"
of
buoyant
plastic
and
limiting
the
amount
of
time
the
solution
is
in
use.

In
addition,
strips
of
camera
film
are
often
processed
in
tanks.
The
flexible
film
strip
is
inserted
in
a
spiral
slot
in
a
reel
which
fits
into
a
cylindrical
tank.
Inserting
the
film
into
the
reel
and
loading
the
reel
into
the
tank
must
be
carried
out
in
the
dark.
Then,
in
a
lighted
area,
the
solutions
are
added,
one
at
a
time,
through
a
light­
tight
port
in
the
cap.
Following
a
prescribed
schedule,
the
tank
is
drained
and
refilled
with
the
subsequent
solutions.
During
the
final
wash
step,
the
cap
can
be
removed
to
permit
easier
washing
of
the
reels
in
the
stream
of
water.(
EPA
1991a)

5.2.2
Automated
Systems
Automated
systems
differ
primarily
by
the
means
used
to
transfer
the
film
through
the
sequence
of
solutions.
The
major
types
of
transport
systems
are
discussed
in
the
following
paragraphs.(
EPA
1991a)

Dip
and
Dunk.
The
films,
in
the
form
of
sheets,
strips,
or
short
looped
lengths,
are
clipped
to
hangers
supported
on
a
rack.
The
rack
is
removed
from
the
processing
machine
to
simplify
loading.
Once
replaced
in
the
processor,
the
rack
holding
the
film
is
advanced
by
a
gear
chain
mechanism.
As
the
rack
moves
into
position,
it
is
lowered
into
the
solution
tanks
so
that
the
film
is
completely
immersed.
Agitation
is
provided
by
vertical
movement
of
the
rack
to
ensure
continuous
contact
of
the
emulsion
surface
with
fresh
solution.
As
the
rack
continues
its
advance,
it
is
automatically
raised
from
one
bath,
allowed
to
drain,
and
lowered
into
the
subsequent
solution
or
wash
tank.
Finally
the
rack
moves
the
film
through
a
forced­
air
drying
unit.

Nip
Rollers.
A
series
of
small
cylindrical
wringers
transports
film
or
paper
through
the
sequence
of
processing
solutions.
These
rollers
provide
for
both
vertical
and
horizontal
28
movement,
and
this
method
is
suitable
for
either
strips
or
sheets.
Initially
a
leader
strip
or
sheet
is
threaded
and
pulled
through
to
a
rewind
station
situated
after
the
final
dryer
unit.
Once
the
processing
is
started,
movement
of
the
film
or
paper
through
the
solutions
is
continuous.

Belt
Systems.
The
film
or
paper
to
be
processed
is
supported
on
a
belt
which
is
conveyed
through
the
sequence
of
solutions
using
guides
and
rollers.
Where
desirable,
the
material
being
processed
can
be
transferred
from
one
belt
to
another
to
allow
for
a
greater
variety
of
strips.
Initially
a
leader
strip
or
sheet
is
treated
and
pulled
through
to
a
rewind
station
situated
after
the
final
dryer
unit.
Once
the
processing
is
started,
movement
of
the
film
or
paper
through
the
solutions
is
continuous.

High­
Speed
Roller.
Long
strips
of
film
are
mounted
on
a
flexible
support
which
is
attached
to
a
series
of
racks.
A
system
of
guides
and
immersed
rollers
conveys
the
film
through
the
solutions
to
wash
tanks.
Before
starting
up
the
processor,
a
leader
is
threaded
through
the
racks.
Generally,
the
leader
is
attached
to
the
end
of
the
film
and
is
always
left
in
place
between
processing
cycles
to
simplify
start­
up.
Lengths
of
film
to
be
processed,
or
tailing
leaders,
can
be
attached
with
tape
or
staples.
High
linear
speeds
are
possible,
resulting
in
greater
throughput
than
can
be
obtained
with
other
types
of
processors.
29
6.
Water
Use
and
Wastewater
Sources
and
Characterization
6.1
Introduction
As
exposed
photosensitive
film
or
paper
is
processed
to
develop
the
image,
it
is
passed
through
a
series
of
chemical
baths
and
washes,
as
described
in
Chapter
5.
In
brief,
the
exposed
film
is
first
subjected
to
a
reducing
agent
in
the
developer
to
form
the
latent
image.
Then,
if
the
film
being
developed
is
color
film,
bleach
is
used
to
oxidize
the
black
metallic
silver
image
back
to
an
invisible
halide,
so
as
to
reveal
the
colors
and
so
that
the
silver
can
be
removed
in
the
fix
bath.
Following,
in
the
fix,
ammonium
or
sodium
thiosulfate
solution
is
used
to
fix
the
silver
or
color
image
to
the
film
base.
In
the
ideal
case,
the
fix
solution
removes
100
percent
of
the
silver
processed
in
color
work,
and
the
60
to
80
percent
of
the
silver
in
a
black­
and­
white
picture
that
does
not
contribute
to
the
image
as
black
elemental
silver.
Finally,
one
or
more
washes
remove
any
remaining
chemicals
and
unexposed
silver.
As
film
is
passed
through
the
developer,
bleach,
and
fix,
these
solutions
are
replenished
with
new
solutions
to
maintain
their
effectiveness.
The
rate
of
replenishment
determines
the
particular
wastestream
amount
and
the
concentration
of
chemicals
in
the
wastestream.

Table
6.1
introduces
the
photoprocessing
waste
streams,
their
major
constituents,
and
associated
environmental
concerns.
Following
are
sections
which
detail
the
quantity
and
pollutant
parameters
of
the
major
photoprocessing
wastestreams:
developer,
bleach,
fix,
wash,
and
stabilizer.
30
Table
6.1
Aqueous
Wastes
from
Photoprocessing
Solution
Constituents
Environmental
Concern
Prehardeners,
Hardeners,
and
Prebaths
Organic
Chemicals
Chromium
Compounds
Oxygen
Demand
Toxic
Metals
Developers
Organic
Chemicals
Oxygen
Demand
Stop
Baths
Organic
Chemicals
Oxygen
Demand
Ferricyanide
Bleaches
Ferricyanide
Toxic
Chemical
Dichromate
Bleaches
Organic
Chemicals
Chromium
Compounds
Oxygen
Demand
Toxic
Metals
Clearing
Baths
Organic
Chemicals
Oxygen
Demand
Fixing
Baths
Organic
Chemicals
Silver
Thiocyanate
Ammonium
Compounds
Sulfur
Compounds
Oxygen
Demand
Toxic
Metals
Toxic
Chemicals
Ammonia
Possible
H
2
S
Generation
Neutralizers
Organic
Chemicals
Oxygen
Demand
Stabilizers
Phosphate
Bio­
Nutrients
Sound­
track
Fixer
or
Redeveloper
Organic
Chemical
Ammonium
Compounds
Oxygen
Demand
Ammonia
Monobaths
Organic
Chemicals
Oxygen
Demand
In
addition,
photoprocessing
solutions
may
be
acidic
or
alkaline.
Source:
EPA
1991a
6.2
Total
Process
Water
Use
Process
water
used
in
photoprocessing
consists
of
a)
film
and
paper
wash
water,
b)
solution
make­
up
water,
and
c)
area
and
equipment
wash
water.
The
largest
single
process
water
use
is
for
the
washing
of
film
and
paper
between
the
various
process
steps
and
for
final
rinse.
The
function
of
the
wash
step
is
to
clean
the
photographic
emulsion
of
constituents
which
must
be
removed
for
successful
completion
of
certain
processing
steps.
Solution
make­
up
water
is
blended
with
the
chemicals
used
in
the
processing
solutions,
which
are
generally
supplied
to
the
processor
in
the
form
of
liquid
concentrates
or
powdered
chemical
formulations,
to
provide
processing
solutions
of
working
strength.
Waterborne
wastes
are
generated
when
these
solutions
are
discarded
after
becoming
exhausted
or
when
allowed
to
overflow
during
replenishment,
as
is
31
the
common
practice.
Area
and
equipment
wash
water
is
used
for
the
washing
and
rinsing
of
solution
mixing
utensils,
storage
tanks,
and
processing
machines
for
area
washdown.

Information
on
overall
process
water
use
was
obtained
for
a
1981
EPA
guidance
document
for
the
control
of
water
pollution
in
the
photoprocessing
industry.(
EPA
1981a)
The
average
total
process
water
use
for
the
70
plants
from
which
data
were
obtained
was
found
to
be
3.85
gallons
per
square
foot
of
film
and/
or
paper
processed,
and
ranged
from
a
low
of
0.220
gal/
ft2
to
a
high
of
14
gal/
ft2.
It
was
observed
that
more
than
95
percent
of
the
process
water
use
in
each
facility
was
for
film
and
paper
washing.
The
analysis
also
indicated
that
overall
process
water
use
was
not
correlated
to
production
capacity;
both
small
and
large
facilities
showed
a
similar
range.

The
process
volumes
of
silver­
rich
and
silver­
poor
solutions
have
been
estimated
for
a
variety
of
small,
medium,
and
large
photoprocessors,
as
shown
in
Table
6.2.
In
this
table,
silverrich
solutions
include
fix,
bleach­
fix,
washless
stabilizer,
and
low­
flow
washwaters.
Silver­
poor
solutions
include
developers,
bleaches,
stop­
baths,
stabilizers
used
after
washes,
and
washwaters.

It
is
estimated
that
small
and
medium
size
photographic
processors
represent
about
90%
of
the
total
number
of
photographic
processing
facilities.
These
small
and
medium
size
facilities
include:
small
hospitals,
doctors',
dentists',
veterinarians'
and
chiropractors'
offices,
neighborhood
clinics,
schools,
portrait
studios,
minilabs,
custom
labs,
professional
processing
labs,
small
microfilm
facilities,
printers,
motion
picture
processors,
and
a
large
number
of
municipal,
state,
and
federal
facilities
where
some
in­
house
photographic
processing
is
done.
Small
facilities
typically
discharge
less
than
1,000
GPD
of
process
wastewater
and
produce
on
average
less
than
2
GPD
of
silver­
rich
solutions.
Medium
size
facilities
typically
discharge
1,000
to
10,000
GPD
of
process
wastewater
and
produce
on
average
2
to
20
GPD
of
silver­
rich
processing
solutions.
Large
photographic
processors,
representing
about
9
percent
of
all
photographic
processing
facilities,
typically
discharge
10,000
to
25,000
GPD
of
process
wastewater
and
produce
on
average
more
than
20
GPD
of
silver­
rich
processing
solution.
Significant
Industrial
Users
(
SIU)
are
facilities
using
more
than
25,000
gallons
per
day
(
GPD)
of
process
wastewater
and
having
the
ability
to
adversely
impact
the
POTW
operations
or
causing
pass­
through
of
a
regulated
chemical.
SIUs
represent
about
1
percent
of
the
total
number
of
facilities
that
process
photographic
materials.
Photographic
processing
facilities
that
could
be
SIUs
include
the
major
motion
picture
film
processors,
and
a
few
very
large
hospitals,
X­
ray
diagnostic
clinics,
printers
and
photofinishers.(
Silver
CMP)

Photoprocessing
combined
wastestream
characteristics
are
summarized
in
Table
6.3.
32
Table
6.2
Estimated
Wastestream
Volumes
for
Various
Photoprocessors
Facility
Type
­
Size
Silver­
Rich1
Solution
Volume
(
GPD)
Silver­
Poor2
Solution
Volume
(
GPD)

Dental
Office
­
Small
Dental
Office
­
Medium
Dental
Office
­
Large
0.1
0.2
0.4
5
10
20
Hospital
­
Small
Hospital
­
Medium
Hospital
­
Large
20
40
80
2,600
5,200
10,400
Medical
Professional
­
Small
Medical
Professional
­
Medium
Medical
Professional
­
Large
0.2
1.0
5
100
500
1,000
Microfilm
­
Small
Microfilm
­
Medium
Microfilm
­
Large
0.1
0.3
50
15
75
3,750
Printer/
Graphic
Art
­
Small
Printer/
Graphic
Art
­
Medium
Printer/
Graphic
Art
­
Large
1
2
20
225
450
4,500
Minilab
­
Washless
­
All
Sizes
Minilab
­
Washwater
­
All
Sizes
2.3
1.0
21
100
Photofinisher/
Professional
­
Small
Photofinisher/
Professional
­
Medium
Photofinisher/
Professional
­
Large
10
100
265
1,325
13,250
33,000
Motion
Picture
­
Small
Motion
Picture
­
Medium
Motion
Picture
­
Large
25
50
2,000
1,000
2,000
80,000
Police
Dept.
­
Small
Police
Dept.
­
Medium
Police
Dept.
­
Large
0.2
0.4
2
25
50
250
School
­
Small
School
­
Medium
School
­
Large
1
5
10
125
650
1,250
1
Silver­
Rich
solutions
include
fix,
bleach­
fix
washless
stabilizer,
and
low
flow
washwaters.
2
Silver­
poor
solutions
include
developers,
bleaches,
stop­
baths,
stabilizers
used
after
washes,
and
washwaters.
Source:
Silver
CMP
33
Table
6.3
Photoprocessing
Combined
Wastestream
Effluent
Characteristics
Pollutant
Parameter
Concentration
Range
(
mg/
L)

Conventional
Process
Washless
Process
Temperature
80
­
110
oF
<
95
oF
pH
6.5
­
9.5
units
6.5
­
9.0
units
Biochemical
Oxygen
Demand
(
5­
Day)
200
­
3,000
5,000
­
15,000
Chemical
Oxygen
Demand
400
­
5,000
10,000
­
35,000
Total
Dissolved
Solids
300
­
3,000
30,000
­
90,000
Total
Suspended
Solids
<
5
­
50
10
­
50
Ammonia
Nitogen
(
NH
3­
N)
20
­
300
6,000
­
10,000
Total
Kjeldahl
Nitrogen
(
TKN)
30
­
350
8,000
­
13,000
Thiosulfate
100
­
1,000
20,000
­
25,000
Sulfates
50
­
250
3,000
­
4,000
Silver
(
after
silver
recovery)
<
0.1
­
5
<
5
­
50
Iron
<
10
­
100
1,400
­
2,000
Zinc
<
0.75
<
2
Source:
WEF
1994
6.3
Developer
Developer
replenishment
rates
typically
range
between
5
and
30
mL/
sq
ft
for
paper
processes
and
15
and
100
mL/
sq
ft
for
film
processes.(
WEF
1994,
EPA
1981a)
Fresh
developer
solutions
typically
contain
less
than
1
percent
reducing
agent
by
weight.
For
color
developers,
the
reducing
agent
is
a
substituted
para­
phenylenediamine.
The
oxidized
para­
phenylenediamine
formed
during
development
reacts
with
another
chemical
to
form
the
image
dyes
and
remains
in
the
gelatin
layer.
For
black­
and­
white
developers,
the
reducing
agent
is
usually
hydroquinone,
a
sulfonated
hydroquinone,
or
ascorbic
acid.
The
highest
developing
agent
concentrations
are
found
in
some
high­
silver
medical
X­
ray
processes,
for
which
the
hydroquinone
concentration
can
be
as
high
as
3
percent
by
weight.
In
black­
and­
white
processing,
the
oxidized
developing
agent
remains
in
the
developer
solution.
34
The
other
major
components
of
a
developer
solution
consist
of
a
pH
buffer
(
typically
carbonate)
to
maintain
pH
in
the
range
of
9
to
11,
a
calcium
sequestrant
(
typically
ethylenediaminetetraacetic
acid
(
EDTA)
or
a
metaphosphate),
and
an
antioxidant
(
typically
sulfite
or
a
hydroxylamine).
These
compounds
are
present
in
concentrations
generally
less
than
1
percent
by
weight,
in
the
1
to
10
g/
L
range.
Developer
solutions
contain
more
than
90
percent
water
by
weight.

Because
developing
agents
oxidize
on
exposure
to
air,
the
developing
solutions
are
unstable
and
degrade
with
time.
Thus
the
reducing
agents
are
depleted
by
both
the
photoprocessing
operation
and
by
exposure
to
air.
The
oxidized
ingredients
must
be
replaced
to
maintain
consistent
results.
As
new
solution
is
added
to
the
developer
container,
an
equivalent
volume
is
discharged
from
the
processor.
This
spent
developer
solution
contains
more
than
90
percent
water,
with
a
few
grams
per
liter
inorganic
salts
(
carbonate
and
sulfate)
and
portions
of
developing
and
sulfonated
developing
agents.
Results
of
sampling
of
untreated
color
developer
waste
streams,
performed
in
1977,
are
displayed
in
Table
6.4.
35
Table
6.4
Color
Developer
Untreated
Wastestream
Pollutant
Amounts
Pollutant
Parameter
Plant
Code
Concentration
(
mg/
L)
Amount
(
lbs/
1000
ft2)

Total
Organic
Carbon
6208
6,450
­

7781
15,000
­

7781
16,700
­

Cadmium
6208
0.34
4.59
x
10­
5
7781
86
3.5
x
10­
3
7781
1.1
7.3
x
10­
5
Chromium*
6208
0.09
1.2
x
10­
5
7781
0.10
4.1
x
10­
6
7781
0.26
1.8
x
10­
5
Silver
6208
1.4
1.9
x
10­
4
7781
1.5
6.1
x
10­
5
7781
0.49
3.3
x
10­
5
Iron
6208
2.9
­

7781
2.4
­

7781
3.7
­

Lead
6208
0.25
­

7781
7.5
­

7781
0.09
­

Total
Suspended
Solids
6208
9.3
­

7781
18
­

7781
10
­

Total
Dissolved
Solids
6208
40,400
­

7781
78,400
­

7781
52,600
­
36
Source:
EPA
1981a
*
Since
this
sampling
episode
in
1977,
it
is
reported
that
the
amount
of
chromium
used
in
film
emulsion
has
been
substantially
reduced,
and
is
currently
used
only
in
the
Kodachrome
process.
(
EPA
1994)

6.4
Bleach
Bleach
replenishment
rates
vary
from
5
and
30
mL/
sq
ft
for
color
processes.(
WEF
1994,
EPA
1981a)
Bleach
solution
is
not
used
in
black­
and­
white
processing.
Bleach
solutions
contain
10
to
30
percent
iron­
EDTA
complex,
typically
the
ammonium
salt
of
ferric
EDTA
or
ferric
propylenediaminetetraacetic
acid
(
PDTA).
Ammonium
salts
are
used
because
they
are
more
soluble
and
transport
through
the
gelatin
layers
faster
than
sodium
or
potassium
salts.
Thus,
lower
concentrations
can
be
used.
The
bleach
also
contains
5
to
10
percent
acetic
acid
and
an
acetate
salt
to
buffer
the
pH
in
the
4
to
6
range,
5
to
10
percent
bromide
salt,
and
a
small
amount
(
less
than
l
percent)
of
sodium
or
potassium
nitrate,
which
is
used
to
prevent
corrosion
of
the
processing
tanks.
As
it
oxidizes
the
metallic
silver,
the
ferric
complex
is
reduced
to
ferrous
salt
and
must
be
regenerated
or
replaced.
As
this
solution
is
replenished,
the
overflow
will
contain
65
to
85
percent
water,
ferrous
and
ferric
EDTA
or
PDTA
complexes,
and
inorganic
salts
such
as
bromide,
nitrate,
and
ammonium
ion.

For
some
cinemagraphic
films,
a
bleach
containing
ferricyanide
is
used,
and
could
result
in
appreciable
concentrations
of
ferri­
and
ferrocyanide
in
the
waste
streams.
Most
cinemagraphic
processors
recover
up
to
99
percent
of
the
ferricyanide
for
reuse.
If
not
recovered,
ferrocyanide
can
eventually
be
converted
to
free
cyanide
by
sunlight
in
the
presence
of
oxygen
over
a
period
of
several
weeks,
and
is
therefore
a
waste
constituent
of
concern.(
EPA
1991a)

Results
of
sampling
of
raw
EDTA
bleach
wastestreams,
performed
in
1977,
are
displayed
in
Table
6.5,
and
those
of
raw
ferricyanide
bleach
wastestreams
are
displayed
in
Table
6.6.
37
Table
6.5
EDTA
Bleach
Untreated
Wastestream
Pollutant
Amounts
Pollutant
Parameter
Plant
Code
Concentration
(
mg/
L)
Amount
(
lbs/
1000
ft2)

Total
Organic
Carbon
2714
4550
7781
43,600
42,150
23,200
­
­
­

Cadmium
2714
4550
7781
<
0.02
0.4
0.09
<
2.3
x
10­
6
1.4
x
10­
4
3.9
x
10­
6
Chromium*
2714
4550
7781
2.0
12
3.6
2.3
x
10­
4
4.2
x
10­
3
1.6
x
10­
4
Silver
2714
4550
7781
268
233
36
0.03
0.08
0.016
Iron
2714
4550
7781
16,282
12,102
7,722
­
­
­

Lead
2714
4550
7781
<
0.02
2.0
0.14
­
­
­

Total
Suspended
Solids
2714
4550
7781
62
112
86
­
­
­

Total
Dissolved
Solids
2714
4550
7781
253,000
227,600
206,800
­
­
­

Cyanide
2714
4550
7781
­
3.1
­
­
1.1
X
10­
3
Source:
EPA
1981a
*
Since
this
sampling
episode
in
1977,
it
is
reported
that
the
amount
of
chromium
used
in
film
emulsion
has
been
substantially
reduced,
and
is
currently
used
only
in
the
Kodachrome
process.
(
EPA
1994)
38
Table
6.6
Ferricyanide
Bleach
Untreated
Wastestream
Pollutant
Amounts
Pollutant
Parameter
Plant
Code
Concentration
(
mg/
L)
Amount
(
lbs/
1000
ft2)

Total
Organic
Carbon
2714
4550
6208
13,000
30,750
8,300
­
­
­

Cadmium
2714
4550
6208
<
0.02
0.40
<
0.02
<
1.1
x
10­
5
6.7
x
10­
5
<
7.8
x
10­
7
Chromium*
2714
4550
6208
4.2
1.3
0.09
2.4
x
10­
3
2.2
x
10­
4
3.6
x
10­
6
Silver
2714
4550
6208
4.1
8
0.38
2.35
x
10­
3
1.3
x
10­
3
1.5
x
10­
5
Iron
2714
4550
6208
5,562
11,118
7,560
­
­
­

Lead
2714
4550
6208
0.22
2.0
0.42
­
­
­

Total
Suspended
Solids
2714
4550
6208
30
101
24
­
­
­

Total
Dissolved
Solids
2714
4550
6208
128,000
304,750
98,800
­
­
­

Cyanide
2714
4550
6208
15,800
50,200
14,750
9.1
20
4.75
Source:
EPA
1981a
*
Since
this
sampling
episode
in
1977,
it
is
reported
that
the
amount
of
chromium
used
in
film
emulsion
has
been
substantially
reduced,
and
is
currently
used
only
in
the
Kodachrome
process.
(
EPA
1994)
39
6.5
Fix
Fix
replenishment
rates
range
from
15
to
100
mL/
sq
ft
for
film
and
paper
processes.
Fix
solutions
contain
65
to
85
percent
water,
10
to
30
percent
ammonium
thiosulfate,
and
5
to
10
percent
sulfite
salt
that
acts
as
an
antioxidant.
Fix
solutions
are
not
stable
to
oxygen,
and
exposure
to
air
slowly
degrades
thiosulfate
to
elemental
sulfur.
As
the
fix
solution
is
used
for
processing,
it
removes
the
silver
from
the
film
or
paper
in
the
form
of
the
soluble
silver
thiosulfate
complex,
and
a
seasoned
solution
should
contain
between
1,000
and
5,000
mg/
L
silver.
As
the
fix
is
replenished,
the
overflow
is
generally
collected
for
silver
recovery.(
WEF
1994)

6.6
Bleach­
Fix
As
discussed
in
Chapter
5,
the
bleach
and
fix
solutions
necessary
for
color
processing
are
sometimes
combined
to
form
the
bleach­
fix
or
blix
solution.
Bleach­
fix
replenishment
rates
vary
from
5
to
30
mL/
sq
ft
for
color
processes.(
WEF
1994,
EPA
1981a)
The
composition
of
the
wastestream
is
that
of
the
bleach
and
fix
solutions,
as
described
above,
combined.
Results
of
sampling
of
raw
bleach­
fix
wastestreams,
performed
in
1977,
are
displayed
in
Table
6.7.
40
Table
6.7
Bleach­
Fix
Untreated
Wastestream
Pollutant
Amounts
Pollutant
Parameter
Plant
Code
Concentration
(
mg/
L)
Amount
(
lbs/
1000
ft2)

Total
Organic
Carbon
2714
4550
4550
7781
7781
43,600
33,900
47,150
41,600
50,750
­
­
­
­
­

Cadmium
2714
4550
4550
7781
7781
<
0.02
<
0.06
1.0
80
0.24
<
1.2
x
10­
6
<
7.5
x
10­
5
6.6
x
10­
5
5.1
x
10­
6
1.6
x
10­
6
Chromium
2714
4550
4550
7781
7781
0.6
5.7
6
1.3
2.9
3.6
x
10­
5
7.1
x
10­
4
3.9
x
10­
4
8.2
x
10­
5
2.0
x
10­
4
Silver
2714
4550
4550
7781
7781
2,109
2,025
1,582
4,356
2,111
0.12
0.25
0.10
0.28
0.14
Iron
2714
4550
4550
7781
7781
4,884
7,718
8,023
5,310
13,236
­
­
­
­
­

Lead
2714
4550
4550
7781
7781
0.5
1.0
1.4
22
0.7
­
­
­
­
­

Total
Suspended
Solids
2714
4550
4550
7781
7781
112
56
82
124
51
­
­
­
­
­
Pollutant
Parameter
Plant
Code
Concentration
(
mg/
L)
Amount
(
lbs/
1000
ft2)

41
Total
Dissolved
Solids
2714
4550
4550
7781
7781
205,000
195,400
209,400
292,000
306,200
­
­
­
­
­

Biological
Oxygen
Demand
2714
4550
4550
7781
7781
­
13,300
28,000
­
­
­
­
­
­
­

Nitrogen
(
As
Ammonia)
2714
4550
4550
7781
7781
­
38,000
30,000
­
­
­
­
­
­
­

Source:
EPA
1981a
6.7
Wash
Wash
waters
are
replenished
at
200
to
1000
mL/
sq
ft
for
each
wash
tank
of
the
process.
After
the
fix
or
bleach­
fix,
the
films
or
papers
are
immersed
in
a
series
of
wash
tanks
to
remove
the
silver
thiosulfate
and
other
residual
chemicals
from
the
gelatin
layers.
Therefore,
the
wash
waters
typically
contain
the
same
pollutants
as
the
fix
or
bleach­
fix,
but
at
lower
concentrations.

6.8
Stabilizers
Stabilizers
or
final
rinse
solutions
are
99
percent
water
except
for
washless
color
processes.
These
solutions
contain
a
wetting
agent
to
prevent
water
spotting
during
drying.
In
some
color
film
stabilizers,
a
small
amount
of
formaldehyde
(
less
than
0.2
percent)
is
present
to
harden
the
gelatin
layer
or
stabilize
an
image
dye.
Stabilizers
are
replenished
at
rates
between
10
and
30
mL/
sq
ft.

In
one
amateur
film
and
paper
process,
the
water
washes
are
replaced
by
a
replenished
stabilizer.
This
stabilizer
contains
citrate
salts
and
polyvinylpyrolidone
to
complex
or
react
with
the
residual
chemicals
and
provide
image
stability.
As
this
solution
is
replenished,
the
overflow
is
collected
for
silver
recovery.
While
the
image
stability
is
not
as
good
as
that
provided
by
water
washing,
it
is
reportedly
good
enough
for
most
amateur
photographers.(
WEF
1994)
42
6.9
Total
National
Photoprocessing
Discharge
Flow
Chapter
4
provides
numbers
for
the
total
rolls
processed
and
exposures
produced,
and
provides
information
on
the
size
and
quantities
of
prints
produced
from
the
resulting
negatives.
From
these
values,
and
the
surface
area
per
film
reported
in
the
literature,
it
is
possible
to
estimate
the
total
square
feet
of
film
and
paper
processed
across
the
United
States
for
the
amateur
(
commercial)
market.
Values
for
the
health
care
and
noncommercial
photoprocessing
market
segments
are
not
available,
but
it
is
estimated
that
this
amateur
market
accounts
for
44
percent
of
the
total
photoprocessing
volume.
This
estimate
derives
from
the
fact
that
the
amateur
market
accounts
for
44
percent
of
total
photographic
silver
use.
Silver
use
in
the
other
market
segments,
including
medical,
dental,
graphic
arts,
and
industrial,
was
shown
previously
in
Table
4.3.

The
detailed
calculations,
presented
in
the
Appendix,
estimate
the
total
1994
amateur
film
processed
to
be
296
million
square
feet,
and
the
total
paper
processed
to
be
4,115
million
square
feet.
From
these
results
of
the
total
film
and
paper
square
feet
processed,
the
total
flow
requirements
for
each
process
can
be
calculated
using
the
process
flow
demands
for
the
various
waste
streams
as
reported
in
sections
6.2
through
6.7
above.
The
results
are
presented
in
Table
6.8
below.
43
Table
6.8
Total
United
States
Photoprocessing
Amateur
MarketWaste
Stream
Quantity
Estimations
for
1994
Waste
Stream
Flow
Demands
Total
U.
S.
Flow1
(
Millions
of
Gallons/
Year)

Film
Paper
Film
and
Paper
Total
Process2
3.85
gal/
ft2
­
­
17,000
Developer3
paper
5
­
30
mL/
ft2
film
15
­
100
mL/
ft2
­

4.50
19.0
­
­

­

Bleach3
5
­
30
mL/
ft2
­
­
20.4
Fix3
15
­
100
mL/
ft2
­
­
67.0
Bleach­
Fix3
5
­
30
mL/
ft2
­
­
20.4
Stabilizer3
10
­
30
mL/
ft2
­
­
23.3
Wash3
200
­
1000
mL/
ft2
­
­
699/
tank
Total
Process
Calculated
as:
Developer
+
Bleach
+
Fix
+
Stabilizer
+
Three
Wash
Tanks
2,250
1.
When
given
a
flow
demand
range,
the
total
U.
S.
flow
is
calculated
using
the
average
flow
value.
2.
Flow
demand
from
reference
EPA
1981a
3.
Flow
demands
from
reference
WEF
1994
In
Table
6.8
above,
the
total
U.
S.
flow
has
been
calculated
in
two
ways:
the
single
total
process
flow
as
determined
from
the
EPA
1981a
reference,
or
the
addition
of
the
process
wastestreams
as
determined
from
the
WEF
1994
reference.
The
EPA
1981a
reference
flow
demand
leads
to
a
total
flow
about
7
½
times
greater
than
the
flow
calculated
from
the
WEF
1994
flow
demands.
Here,
the
EPA
1981a
value
is
taken
to
be
outdated
and
to
overstate
water
use,
and
the
WEF
1994
values
are
taken
to
be
more
realistic
for
the
current
operating
environment.

Two
assumptions
are
implicit
in
the
value
of
2,250
million
gallons/
year
as
an
estimate
of
the
total
U.
S.
photoprocessing
flow
requirements
for
the
amateur
market.
One
is
that
the
flow
demands
which
are
not
split
for
paper
and
film
are
applicable
to
both
paper
and
film
processing.
The
other
is
that
other
wastewaters
not
mentioned,
such
as
equipment
wash
waters,
are
negligible.
44
7.
Control
and
Treatment
Technologies
7.1
Introduction
This
chapter
on
control
and
treatment
technologies
recommended
for
photoprocessing
operations
begins
with
a
discussion
of
source
reduction
methods.
Particularly
in
the
photoprocessing
industry,
certain
management
practices
have
proven
highly
effective
in
reducing
waste
while
requiring
almost
no
investment
or
loss
in
product
quality.
Following
the
discussion
on
source
reduction,
control
and
treatment
technologies
are
presented.
In
addition
to
the
environmental
benefit
associated
with
reducing
pollutant
discharge
loadings,
the
photoprocessor
is
often
at
an
economic
advantage
to
install
and
maintain
these
technologies
due
to
the
payback
from
the
recycled
or
recovered
resources,
especially
with
regard
to
the
recovery
of
silver.

Photoprocessing
equipment
manufacturers
and
the
photoprocessors
have
a
close
working
relationship.
Manufacturers
supply
processing
systems
which
include
both
equipment
and
supplies
to
customers.
Photoprocessors
do
not
have
to
purchase
chemical
supplies
from
the
same
manufacturer
that
supplied
the
processing
equipment,
but
many,
especially
the
smaller
mini­
labs,
often
do.
Processors
rely
heavily
on
manufacturers
for
compliance
assistance
and
innovations
to
address
environmental
and
regulatory
concerns.
Manufacturing
is
driven
in
part
by
the
demands
placed
upon
the
processors,
both
by
regulators
and
by
the
end
consumer.
For
these
reasons
all
of
the
manufacturers
have
support
systems
to
assist
the
processors
with
operations
and
environmental
compliance.
Such
systems
include
instructional
seminars,
facility
compliance
evaluations,
and
compliance
kits.
By
keeping
abreast
of
changes
and
implementing
applicable
technology
improvements,
companies
can
often
take
advantage
of
the
dual
benefits
of
reduced
waste
generation
and
a
more
cost
efficient
operation.

7.2
Source
Reduction
The
following
management
practices
are
applicable
to
all
sizes
of
photoprocessing
operations
to
minimize
waste
generation.
They
require
almost
no
investment
and
have
proven
effective
in
many
businesses:

!
Control
inventories
of
processing
chemicals
so
they
are
used
before
their
expiration
dates.

!
Make
up
processing
solutions
only
in
quantities
needed
to
meet
realistic
processing
volumes.

!
Use
floating
lids
or
balls
on
developer
solution
tanks
to
prevent
loss
of
potency
through
oxidation
or
evaporation.

!
Improve
quality
control
for
all
processes
to
prevent
unnecessary
discharges.(
EPA
1991a)

Squeegees
can
be
used
in
all
manual
and
some
automated
processing
systems
to
wipe
excess
liquid
from
the
film
and
paper,
reducing
chemical
carryover
from
one
process
bath
to
the
45
next
by
75
percent
or
more.(
Kodak
1990)
Several
types
are
available,
including
wiper
blades,
air
squeegees,
vacuum
squeegees,
wringer
sling
squeegees,
and
rotary
buffer
squeegees.
Belt
turnarounds
with
soft­
core
rollers
can
be
used
for
slow
speed
transport
of
wide
films,
but
squeegees
cannot
be
used
on
rack
and
tank,
basket,
or
drum
processors.
Minimizing
chemical
contamination
of
process
baths
increases
recyclability,
enhances
the
life
of
the
process
baths,
and
reduces
the
amount
of
replenisher
chemicals
required.
Some
types
of
squeegees
may
damage
the
film
image,
if
it
has
not
fully
hardened.

Accurately
adding
and
monitoring
chemical
replenishment
of
the
process
baths
will
cut
down
chemical
waste.
Process
baths
may
be
protected
from
oxidation
by
reducing
exposure
to
air.
Some
smaller
photo
developers
store
chemicals
in
closed
plastic
containers.
Glass
marbles
are
added
to
bring
the
liquid
level
to
the
brim
each
time
liquid
is
used.
This
limits
the
volume
of
air
in
the
container,
thereby
extending
the
chemical's
useful
life.

Proper
storage
conditions
are
necessary
to
maximize
the
life
of
paper
for
color
prints.
One
writer
recommends
storing
paper
in
a
refrigerator,
if
it
will
not
be
used
for
a
few
days,
and
in
a
freezer
for
longer
storage
periods.
He
states
that
he
has
used
the
same
box
of
paper
for
years
by
freezing
it.(
Sribnick)

Material
substitution
involves
replacing
a
processing
chemical
with
an
alternate
material
that
reduces
the
quantity
of
waste
generated
or
the
degree
of
hazard
associated
with
the
waste.
Opportunities
for
this
type
of
waste
reduction
in
photoprocessing
are
limited.
Alternate
materials
may
be
unavailable,
more
expensive,
or
have
undesirable
effects
on
product
quality.

The
"
black
box"
nature
of
photoprocessing
chemistry
generally
requires
an
individual
operator
to
use
established
chemical
packages
with
few
options
for
substituting
alternate
materials.
Photochemical
manufacturers
and
suppliers
can
aid
photoprocessors,
however,
by
developing
new
processes
which
result
in
lower
volume
and
lower
toxicity
wastes.
For
example,
in
most
processes
ferricyanide
bleach
has
been
replaced
by
ferric
EDTA
(
ethylenediaminetetraacetic
acid)
complex,
resulting
in
a
less
toxic
waste
stream.(
Calif.
DHSa)

Over
the
past
20
years,
the
industry
has
significantly
reduced
the
content
of
silver
in
its
products.
The
vast
majority
of
silver
in
film
is
not
used
in
the
image
and
is
recovered
from
processing
solutions.
However,
the
nature
of
the
image
formed
determines
the
amount
of
silver
used
in
that
image;
quality
requirements
for
image
and
consistency
limit
the
potential
for
further
reduction.(
EPA
1994)

As
a
result
of
the
reduction
in
the
silver
content
in
film,
the
industry
has
also
reduced
the
amount
of
hydroquinone
in
developer.
There
is
a
direct
relationship
between
the
amount
of
silver
on
the
film
base
and
the
amount
of
hydroquinone
required
to
develop
the
image.
The
amount
of
chromium
used
in
the
film
emulsion
has
also
been
substantially
reduced,
and
is
currently
used
only
in
the
Kodachrome
process.
The
elimination
of
chromium
in
traditional
films
was
primarily
the
result
of
regulatory
demands
on
processors
to
eliminate
it
from
their
effluent.
In
contrast,
the
46
concern
about
selenium
has
arisen
only
recently
with
Xerox's
development
of
a
heat­
based
film
which
contains
this
element.
Although
Xerox
is
promoting
the
film
on
the
basis
of
its
silver­
free
nature,
many
in
the
industry
claim
that
selenium
is
far
more
toxic
than
silver,
and
that
from
an
environmental
perspective,
the
new
technology
represents
a
step
backward.(
EPA
1994)

Businesses
which
operate
in­
house
labs
have
more
flexibility
for
material
substitution,
such
as
using
non­
silver
film.
A
company
that
supplies
microfilms
of
catalogs
and
standards
to
industrial
users
has
switched
to
diazo
and
vesicular
films.
However,
it
should
be
noted
that
these
films
are
not
considered
"
archival"
and
may
not
be
acceptable
for
permanent
document
storage.

7.3
Silver
Recovery
Considerations
Metallic
silver
trades
as
a
commodity
in
units
of
Troy
ounces
(
one
Troy
ounce
equals
31.10
grams).
In
recent
years
the
price
range
has
typically
been
$
4
to
$
6
per
Troy
ounce,
although
during
the
speculative
fever
of
1980,
the
price
reached
$
50
per
Troy
ounce,
before
the
market
collapsed.
Thus,
if
the
market
price
were
$
6.00
per
ounce,
and
an
effluent
contained
31
mg/
L
silver,
the
potential
recovery
value
of
silver
would
be
0.6
cents
per
liter
or
nearly
2.4
cents
per
gallon
of
effluent.
Since
silver
recovered
from
photoprocessing
requires
further
processing,
reclaimers
will
offer
somewhat
less
than
market
price
for
the
recovered
silver.(
EPA
1991a)

The
quantity
of
silver
entering
a
processing
facility
can
be
estimated
based
on
the
number
of
rolls
processed
and
the
surface
area
of
prints
produced.
The
silver
content
in
Troy
ounces
of
several
types
of
photographic
films
and
papers,
as
well
as
the
surface
area
per
role
of
film,
is
available
in
EPA
documents.
While
the
silver
content
of
film
varies,
the
most
commonly
used
films
contain
about
25
Troy
ounces
per
1000
square
feet.
Commonly
used
papers
have
about
one
tenth
the
silver
content
of
film
per
square
foot,
at
about
2.4
Troy
ounces
per
1000
square
feet.(
EPA
1991a,
EPA
1991b)

Major
sources
of
recoverable
silver
are:
photoprocessing
solutions,
spent
rinse
water,
scrap
film,
and
scrap
printing
paper.
The
silver
in
these
materials
may
exist
as
insoluble
silver
halide,
soluble
silver
thiosulfate
complex,
silver
ion,
or
elemental
silver,
depending
on
the
type
of
process
and
the
stage
in
the
process
where
the
silver
is
being
recovered.

As
much
as
80
percent
of
the
total
silver
processed
for
black­
and­
white
positives
and
almost
100
percent
of
the
silver
processed
in
color
work
will
end
up
in
the
fixer
or
bleach­
fix
solution.
Silver
is
also
present
in
the
rinse
water
following
the
fixer
or
bleach­
fix
due
to
carry­
over.
The
amount
or
silver
in
rinse
water
is
only
a
small
fraction
of
that
in
the
fixer
or
bleach­
fix
solutions,
but
can
be
economically
recovered
when
high
volumes
of
rinse
water
are
used.
A
variety
of
equipment
types
and
sizes
are
available
for
silver
recovery.
Table
7.1
compares
silver
recovery
methods.
More
detailed
descriptions
are
given
in
Section
7.4
below.
47
Table
7.1
Comparison
of
Silver
Recovery
and
Management
Systems
System
Advantages
Limitations
Metallic
Replacement
by
Chemical
Recovery
Cartridges
(
CRCs)
Can
be
used
for
all
silver­
rich
solutions
Little
maintenance,
low
operating
costs
Low
capital
costs
Simplest
operation
Can
achieve
99%
recovery
when
2
CRC
used
in
series
Requires
metered
flow
for
consistency
Must
be
replaced
on
schedule
Tendency
to
channel
and
cause
concentrated
silver
discharge,
efficiency
diminishes
with
use
High
silver
content
in
effluent
unless
2
units
in
series
Silver
recovered
as
sludge
High
smelting
and
refining
costs
Cannot
determine
amount
of
silver
recovered
until
refined
pH
dependent
High
iron
content
in
effluent
precludes
reuse
in
photo
process
Electrolytic
(
terminal)
High
purity
silver
flake
Low
refining
costs
Can
determine
silver
recovered
Capital
costs
moderate
Can
achieve
90%
recovery
No
additional
chemicals
released,
fix
solution
can
be
recycled
Cannot
achieve
5
mg/
L
with
electrolytic
alone
Can
sulfide
if
not
properly
maintained
pH
dependent
Not
suitable
for
silver­
poor
solutions
Precipitation
Can
attain
0.1
mg
Ag+/
L
Little
operator
maintenance
Low
to
moderate
capital
costs
Silver
recovered
as
sludge
Smelting
costs
higher
than
electrolytic
Requires
ongoing
additives
Complex
operation
Operation
costs
vary
from
moderate
to
high
Potential
H2S
release
Treated
solution
cannot
be
reused
Requires
hazardous
chemicals
Evaporation/
Distillation
Reduces
wastes
up
to
90%
Virtually
zero
overflow
of
silver
High
energy
requirements
Moderate
to
high
capital
costs
Silver
recovered
as
a
sludge
Organic
contamination
buildup
Concentration
technology
­
Requires
additional
recovery
Reverse
Osmosis
Efficiently
recovers
silver
from
dilute
photoprocessing
wastestreams
Reduces
effluent
volume
significantly
No
water
treatment
chemicals
required
Also
recovers
other
chemicals
Purified
water
is
recyclable
Capital
costs
vary
significantly
Size
of
equipment
needed
to
obtain
sufficient
flow
Frequent
maintenance
of
membrane
and
pumps
Works
best
on
dilute
solutions
such
as
washwater
Large
installations
can
be
noisy
Concentration
technology
­
Requires
additional
recovery
System
Advantages
Limitations
48
Ion
Exchange
Efficiently
recovers
silver
from
dilute
photoprocessing
wastestreams
Can
attain
0.1
­
2.0
mg
Ag+/
L
Only
for
dilute
effluent
such
as
washwater
Capital
costs
vary
significantly
Biological
growth
problems
May
require
the
use
of
hazardous
chemicals
Complex
operation
Sources:
Silver
CMP,
EPA
1991a,
EPA
1994
7.4
Silver
Recovery
from
Fixer
Solution
The
most
common
methods
of
silver
recovery
from
the
fixer
and
bleach
fix
processing
solutions
are
metal
replacement,
electrolytic
recovery,
and
chemical
precipitation.
Ion
exchange
and
reverse
osmosis
are
other
methods
that
can
be
used.
However,
these
are
suitable
only
for
dilute
silver
solutions
such
as
wash
water
from
a
primary
silver
recovery
unit
which
has
been
mixed
with
wash
waters.
Some
facilities
use
a
primary
silver
recovery
unit,
which
removes
the
bulk
of
silver,
in
combination
with
a
"
tailing"
unit
to
treat
the
relatively
low
silver
concentration
effluents
from
a
primary
silver
recovery
system.
Color
developer
effluent
does
not
flow
through
a
silver
recovery
unit
because
the
silver
content
is
very
low
and
the
high
pH
developer,
if
mixed
with
other
silver­
bearing
solutions,
could
reduce
the
efficiency
of
silver
recovery
and
could
result
in
ammonia
generation.(
EPA
1991a)

A
silver
recovery
system
can
be
devoted
to
a
single
process
line
or
can
be
used
to
remove
silver
from
the
combined
fixer
from
several
process
lines
in
a
plant.
Multiple
stream
systems
are
more
typical
in
large
facilities.
Sometimes
a
separate
fixer
system
is
used
for
specialty
processing
to
reduce
the
possibility
of
inner­
process
contamination,
which
can
occur
when
desilvered
fixer
is
recycled
to
the
photo
process.

7.4.1
Metallic
Replacement
Metallic
replacement
occurs
when
a
more
electrochemically
active
solid
metal
such
as
iron,
contacts
a
solution
containing
dissolved
ions
of
a
less
electrochemically
active
metal,
such
as
silver.
The
more
active
metal
goes
into
solution
as
an
ion,
being
replaced
by
an
atom
of
the
less
active
metal
in
the
solid
matrix.
The
dissolved
silver,
which
is
present
in
the
form
of
a
thiosulfate
complex,
reacts
with
solid
metal.

Silver
ions
will
displace
many
of
the
common
metals
from
their
solid
state.
Because
of
its
economy
and
convenience,
iron
in
the
form
of
steel
wool
is
used
most
often.
Hypothetically,
zinc
and
aluminum
can
also
serve
as
replacement
metals;
however,
both
have
drawbacks.
Zinc
is
not
used
because
of
its
relative
toxicity
and
greater
cost.
Aluminum
is
not
used
because
it
simultaneously
generates
hydrogen
gas,
which
can
be
an
explosion
and
fire
hazard
if
improperly
handled.
49
Commercially
available
units
consist
of
a
steel
wool­
filled
plastic
canister
with
appropriate
connections.
These
units
are
called
chemical
recovery
cartridges
(
CRCs).
Typical
practice
is
to
feed
waste
fixer
to
a
train
of
two
CRCs
in
series.
The
first
CRC
removes
the
bulk
of
the
silver,
and
the
second
polishes
the
effluent
of
the
first.
It
also
is
a
safety
factor
if
the
first
unit
is
overloaded.
When
the
first
is
exhausted,
the
second
becomes
the
first,
and
a
fresh
unit
replaces
the
second.
One
supplier
recommends
changing
CRC
cartridges
when
the
silver
in
the
effluent
of
the
first
cartridge
reaches
25
percent
of
the
influent
concentration.(
Kodak
1980)
The
silver
concentration
in
the
effluent
from
a
single
cartridge
averages
40
to
100
mg/
L
over
the
life
of
the
system,
versus
a
range
of
0.1
to
50
mg/
L
when
two
CRCs
are
used
in
series.
Fixer
desilvered
by
this
process
cannot
be
recycled,
because
of
excessive
iron
concentration
in
the
effluent,
which
can
average
4,000
mg/
L.

For
effective
operation,
the
pH
of
the
solution
passing
through
the
metallic
replacement
unit
should
be
between
4
and
6.5.
The
optimum
is
between
5
and
5.5.
Below
pH
4,
the
dissolution
of
the
steel
wool
is
too
rapid.
Above
pH
6.5,
the
replacement
reactions
may
be
so
slow
that
silver
removal
is
incomplete.
Thus,
proper
pH
control
is
important
to
high
silver
recovery.
A
CRC
should
recover
about
85
percent
of
the
recoverable
silver
in
the
form
of
a
sludge,
which
must
be
further
processed
to
produce
pure
metallic
silver.(
Calif.
DHSa)

7.4.2
Electrolytic
Recovery
An
electrolytic
unit
can
be
used
for
a
primary
or
a
tailing
waste
stream,
and
can
be
either
batch
or
continuous.
This
silver
recovery
method
applies
a
direct
current
across
two
electrodes
in
a
silver­
bearing
solution.
Metallic
silver
deposits
on
the
cathode.
Sulfite
and
thiosulfate
are
oxidized
at
the
anode:

H
2
O
+
SO
3
­
2

SO
4
­
2
+
2e­
+
2H+
(
Anode)

SO
3
­
2
+
S
2
O
3
­
2

S
3
O
6
­
2
+
2e­
(
Anode)

Ag+
+
e­

Ag0
(
Cathode)

Approximately
1
gram
of
sodium
sulfite
is
oxidized
for
each
gram
of
silver
deposited.
Considerable
agitation
and
large
plating
surface
areas
can
achieve
good
plating
efficiency
and
silver
up
to
90­
98
percent
pure.
Lower
silver
purity
levels
usually
result
from
tailing
unit
applications
because
of
the
lower
silver
concentration
in
the
influent
solution.
The
cathodes
are
removed
periodically,
and
the
silver
metal
is
stripped
off.
An
electrolytic
system
should
recover
about
90
percent
of
the
recoverable
silver.

Care
must
be
taken
to
control
the
current
density
in
the
cell
because
high
density
can
cause
"
sulfiding."
Sulfiding
is
the
decomposition
of
thiosulfate
into
sulfide
at
the
cathode
which
contaminates
the
deposited
silver
and
reduces
recovery
efficiency.
The
higher
the
silver
50
concentration,
the
higher
the
current
density
can
be
without
sulfiding.
Therefore,
as
the
silver
is
plated
out
of
solution,
the
current
density
must
be
reduced.

7.4.3
Batch
Electrolytic
Recovery
In
batch
recovery,
overflow
fixer
from
one
or
more
process
lines
is
collected
in
a
tank.
When
sufficient
volume
is
reached,
the
waste
fixer
is
pumped
to
an
electrolytic
cell
for
silver
removal.
The
desilvered
fixer
can
be
discharged
to
a
sewer,
disposed
of
as
solid
waste,
or
reused.
If
reused,
it
is
transferred
to
a
mix
tank
where
sodium
thiosulfate
is
added
to
replenish
its
strength.

Primary
batch
system
cells
are
usually
designed
to
desilver
the
fixing
batch
at
initial
silver
concentrations
of
about
5,000
mg/
L.
The
silver
concentration
in
the
effluent
is
typically
200
to
500
mg/
L.
Effluent
of
20
to
50
mg/
L
is
possible
with
additional
treatment
time
and
careful
current
density
control.
An
electrolytic
tailing
cell
typically
achieves
the
lower
range
because
the
process
can
be
optimized
for
low
initial
silver
concentrations.

7.4.4
Continuous
Electrolytic
Recovery
The
volume
of
a
continuous
electrolytic
unit
must
be
large
enough
relative
to
the
incoming
flow
volume
to
ensure
adequate
residence
time
of
the
fixer,
so
two
or
more
units
can
be
placed
in
series
to
achieve
this.
The
continuous
flow
of
incoming
fixer
supplies
a
constant
quantity
of
silver
for
electrolytic
recovery.
As
a
result,
the
units
can
be
operated
at
a
relatively
stable
current
density.
Such
systems
can
be
automatic.
Some
units
can
sense
silver
concentration
in
solution
and
adjust
current
densities.
Usually,
continuous
flow
units
discharge
desilvered
fixer
directly
to
the
sewer.

7.4.5
Recirculating
Electrolytic
Recovery
Silver
can
also
be
removed
from
an
in­
use
fixer
solution
at
approximately
the
same
rate
it
is
added
by
film
processing,
using
a
continuously
recirculating
system.
The
recovery
cell
is
connected
"
in­
line"
as
part
of
the
recirculation
system.
This
continuous
removal
technique
has
the
particular
advantage
of
maintaining
a
relatively
low
silver
concentration
in
the
fixer
processing
solution,
which
minimizes
the
amount
of
silver
carried
out
into
the
wash
tank.
Also,
the
fixer
replenishment
rate
is
reduced,
decreasing
chemical
usage
and
discharge
quantities.
The
silver
concentration
in
the
fixer
can
be
maintained
in
the
range
of
500
to
1,000
mg/
L
without
forming
sulfide.

A
recirculating
silver
recovery
unit
receives
a
small
continuous
stream
of
fixer
from
an
in­
use
process
tank,
removes
the
silver,
then
returns
the
desilvered
fixer
to
the
photoprocessor.
51
Each
photoprocessing
unit
requires
a
separate
silver
recovery
unit.
Systems
are
available
for
treating
all
types
of
non­
bleach
fixers
that
have
circulation
pumps.
Once
installed,
the
unit
is
fully
automatic,
turning
itself
on
by
sensing
the
flow
of
fixer
through
the
electrolytic
cells.
The
cells
themselves
contain
no
moving
parts,
and
the
silver
is
harvested
every
two
to
three
months.

Desilvered
fixer
solution
can
be
reused,
whether
from
an
"
in­
line"
continuous
system
or
from
batch.
This
requires
adequate
monitoring
and
process
control
to
maintain
composition
and
protect
quality.
Some
manufacturers
have
special
electrolytic
fixers
for
this
application.
Parameters
(
pH,
silver,
and
sulfate
concentrations)
should
be
monitored
to
maintain
the
physical
and
chemical
properties
of
the
fixer
solution,
usually
through
the
addition
of
make­
up
chemicals.

7.4.6
Chemical
Precipitation
Chemical
precipitation
is
the
oldest
and
cheapest
method
for
recovery
of
silver.
It
is
widely
used
by
manufacturers
of
photographic
supplies
but
usually
not
by
photoprocessors.
The
two
primary
disadvantages
are
that
extremely
toxic
hydrogen
sulfide
gas
(
H
2
S)
can
be
evolved,
and
that
the
resulting
sludge
may
have
to
be
managed
as
a
hazardous
waste.
A
third
disadvantage
is
that
recovery
of
silver
from
the
sludge
is
more
difficult
than
with
other
methods.

Sodium
sulfide
(
Na
2
S)
causes
silver
sulfide
to
precipitate
readily
from
waste
fixer
solutions.
2Ag+
+
S­
2

Ag
2
S
Silver
sulfide
is
extremely
insoluble
with
a
solubility
product
of
10­
50.
Precipitation
must
be
carried
out
in
alkaline
media
to
avoid
the
generation
of
H
2
S.
Silver
sulfide
tends
to
form
colloidal
suspensions.
Its
very
small
particle
size
makes
filtration
difficult,
and
the
filter
cake
generated
is
extremely
dense.
However,
diatomaceous
earth
filter
aid
can
be
used
to
improve
filtration.
About
three
grams
filter
aid
are
required
for
each
gram
of
silver,
if
a
conventional
plate­
and­
frame
filter
press
is
used.(
Calif.
DHSa)

Sodium
borohydride
(
NaBH
4)
is
also
an
effective
precipitant
for
silver:

NaBH
4

Na+
+
BH
4
BH
4
+
2H
2
O
+
8Ag+

8Ag0
+
8H+
+
BO
2
The
borohydride
method
requires
significantly
more
than
the
stoichiometric
quantity
to
complete
the
reaction,
while
sodium
sulfide
precipitation
requires
use
of
very
little
excess
chemicals.
Borohydride
also
reduces
many
other
metals
such
as
cadmium,
lead,
and
mercury.(
Cook)
The
major
difference
between
the
two
processes
is
the
resulting
silver
quality.
Sodium
borohydride
produces
elemental
silver
of
96
to
98
percent
purity.
Either
method
can
reduce
silver
concentrations
to
0.1
mg/
L
in
the
fixer
waste
water.
52
The
process
mixes
the
precipitation
agent
with
the
silver
bearing
wastewater
in
a
batch
reaction
tank
equipped
with
automatic
pH
control.
When
sodium
sulfide
is
used,
the
pH
must
be
maintained
above
7
to
avoid
releasing
H
2
S.
The
optimum
pH
range
for
sodium
borohydride
precipitation
is
5.5
to
6.5.
Solid
particles
having
a
size
of
1
to
2
microns
are
formed,
and
are
allowed
to
settle
before
filtering.
Usually
solutions
reacted
with
either
sodium
sulfide
or
sodium
borohydride
are
not
reused
in
the
photographic
process.

7.5
Silver
Recovery
from
Rinse
Water
Even
with
an
efficient
fixer
solution
silver
recovery
system
and
an
effective
squeegee
on
the
fixer
tank,
up
to
10
percent
of
the
recoverable
silver
is
lost
by
carry­
over
into
the
rinse
tank.
The
silver
concentration
in
the
spent
rinse
water
is
typically
in
the
range
of
1
to
50
mg/
L,
too
low
for
economical
recovery
with
electrolytic
or
metallic
replacement
methods.
In
addition,
the
iron
by­
product
from
metallic
replacement
precludes
reuse
of
the
rinse
water,
although
some
photoprocessors
use
metallic
replacement
to
meet
municipal
sewer
effluent
limits.
Precipitation
is
uneconomical
for
rinse
water.(
Calif.
DHSa)

Two
methods
are
currently
being
used
for
effective
recovery
of
silver
from
rinse
water:
resin
ion
exchange
and
reverse
osmosis
(
RO).
A
third
method,
called
"
low
flow
prewash,"
has
been
used
in
a
few
locations
in
the
United
States.

7.5.1
Ion
Exchange
Ion
exchange
is
the
reversible
exchange
of
ions
between
a
solid
resin
and
a
liquid.
A
variety
of
weak
and
strong
anionic
resins
are
effective
in
silver
recovery.
Using
chloride
as
the
mobile
ion,
the
following
represents
the
reaction:

(
Resin)­
Cl
+
AgS
2
O
3
­

(
Resin)­
AgS
2
O
3
+
Cl­

The
silver­
thiosulfate
complex
has
a
high
affinity
for
the
resin,
making
it
difficult
to
reclaim
the
silver
and
regenerate
the
resin.
Other
problems
include
plugging
of
the
resin
by
suspended
matter,
such
as
gelatin,
but
these
have
also
been
solved
by
improved
equipment
design
and
operational
procedures.
Some
ion
exchange
units
produce
effluents
with
silver
concentrations
as
low
as
0.1
ppm,
recovering
as
much
as
98
percent
of
the
silver.(
Kodak
1990)
High­
capacity
units
can
process
as
much
as
500
gallons
per
hour.(
Calif.
DHSb)

7.5.2
Reverse
Osmosis
In
reverse
osmosis
(
RO)
techniques,
the
waste
water
stream
flows
under
pressure
over
the
surface
of
a
selectively
permeable
membrane.
Water
molecules
pass
through
the
membrane
and
53
other
constituents
are
left
behind.
The
extent
of
separation
is
determined
by
membrane
surface
chemistry
and
pore
size,
fluid
pressure,
and
waste
water
characteristics.
The
RO
unit
has
one
inlet
to
receive
the
waste
stream,
and
two
discharge
outlets.
Purified
water
(
permeate)
exits
from
one
outlet,
and
concentrated
wastewater
exits
from
the
other.
This
process
reportedly
can
recover
90
percent
of
the
silver
thiosulfate.(
Kodak
1990)
Silver
can
be
recovered
from
the
resulting
concentrate
by
conventional
silver
recovery
methods.
The
wastewater
must
be
pumped
to
high
pressure
(
about
600
psig)
before
feeding
the
RO
unit,
which
may
incur
high
energy
and
maintenance
costs.
Operating
problems
include
fouling
of
the
membrane
and
biological
growth.
Proper
maintenance
and
control
can
alleviate
these
problems.
One
plant
reported
membrane
fouling,
which
required
frequent
membrane
replacement
at
high
cost.
The
problem
was
solved
by
installing
a
sandbed
filter
upstream
of
the
RO
unit.(
Calif.
DHSa)
RO
requires
more
capital
investment
than
most
other
silver
recovery
methods,
discouraging
its
use
in
photoprocessing.
(
Kodak
1990)

7.5.2
Low
Flow
Prewash
Low
flow
prewash
involves
segmenting
the
after­
fix
wash
tank
to
perform
the
washing
in
two
stages,
with
separate
rinse
water
make­
up
and
overflow.
It
does
the
after­
fix
washing
in
two
stages.
Most
of
the
silver
carry­
over
is
washed
off
in
the
low
volume,
after­
fix
prewash
tank.
The
system
lessens
dilution
of
the
silver
carry­
over,
but
means
that
concentrations
of
fixer,
silver,
and
other
chemicals
reach
high
levels
in
the
prewash
tank
under
steady­
state
conditions.
One
problem
is
that
the
work
being
processed
may
receive
additional
fix
time
and
exposure
to
concentrated
contaminants
while
immersed
in
the
prewash.
Some
investigators
fear
that
this
may
harm
the
quality
of
the
processed
material.
Dye
stability
tests
on
color
paper
processed
using
the
prewash
system
showed
an
increase
in
yellow
stain
six
months
after
processing.
Another
problem
is
increased
maintenance
of
the
wash
tank
because
of
biological
growth,
although
this
can
be
controlled
with
biocides.(
Calif.
DHSa)

7.5.4
Silver
Recovery
from
Scrap
Scrap
film
and
paper
result
from
trimmings,
test
strips,
and
leaders.
The
silver
may
be
present
in
the
form
of
silver
salts
or
elemental
silver
from
fogged
or
developed
material.
The
processing
of
solid
materials
is
more
cumbersome
than
for
solutions,
but
there
are
a
number
of
silver
recovery
companies
in
business
that
will
buy
solid
scrap.
If
necessary,
the
silver
in
scrap
film
and
paper
can
be
removed
in
the
photo
lab
by
treating
the
material
with
a
sodium
hypochlorite
solution
to
oxidize
elemental
silver,
assuring
that
all
silver
is
in
the
form
of
salts
that
can
be
removed
by
fixing.
Some
photo
labs
collect
fixer
overflow
in
a
container
and
add
unprocessed
scrap
film
or
paper
as
it
is
generated.
Once
dissolved
in
the
fixer,
the
silver
can
be
recovered
through
the
same
silver
recovery
processes
used
by
the
lab
for
the
fixer
solutions
from
the
photoprocessors.
This
approach
can
increase
the
amount
of
silver
recovered
on
site,
but
can
54
also
be
a
bit
messy.
Digested
film
or
paper
can
be
difficult
to
handle
and
may
even
go
sour,
if
left
in
the
container
long
enough
to
be
attacked
by
bacteria.(
Calif.
DHSa)

Processed
or
unprocessed
film
can
be
soaked
in
an
agitated,
hot
solution
of
sodium
hydroxide
to
remove
the
emulsion.
The
silver
can
then
be
separated
from
the
solution
by
settling,
centrifuging
or
filtering.
If
the
film
base
is
to
be
sold
as
scrap
polymer
after
the
silver
bearing
emulsion
has
been
removed,
the
film
is
segregated
by
type
of
base.

7.6
Color
Developer
Reuse
Color
developers
which
can
be
regenerated
are
available,
allowing
the
photoprocessor
to
reduce
replenisher
purchases
about
50
percent.
One
regeneration
process
requires
the
addition
of
an
ion­
exchange
unit
to
remove
the
excess
development
by­
products
from
the
developer
overflow.
Another
process
accomplishes
the
same
objective
without
ion
exchange,
using
a
different
developer
solution.(
Kodak
1989a)

7.7
Ferricyanide
Recovery
Ferricyanide
bleaches
reduce
to
ferrocyanide
during
the
bleach
process.
The
spent
ferrocyanide
can
be
regenerated
either
electrolytically
or
chemically.
Chemical
methods
employ
either
ozone
or
persulfate.
Regenerated
ferricyanide
can
be
re­
used
in
photoprocessing.

7.7.1
Electrolytic
Regeneration
Spent
bleach
is
fed
to
an
electrolytic
cell,
where
the
following
reactions
occur:

Anode:
Primary:
2Fe(
CN)
6
­
4

2Fe(
CN)
6
­
3
+
2e­
Secondary:
4OH­

O
2
+
H
2
+
2OH­
+
2e­
55
Cathode:
Primary:
2H
2
O
+
2e­

H
2
+
2OHSecondary
Fe(
CN)
6
­
3
+
e­

2Fe(
CN)
6
­
4
The
evolution
of
hydrogen
gas
presents
a
potential
safety
hazard.(
Kodak
1990)

7.7.2
Persulfate
Regeneration
This
method
is
relatively
inexpensive
and
safe,
since
it
does
not
liberate
any
hazardous
gases.
The
reaction
is:

2Fe(
CN)
6
­
4
+
S
2
O
8
­
2

2Fe(
CN)
6
­
3
+
2SO
4
­
2
The
major
disadvantage
is
that
gradual
accumulation
of
sulfate
salt
reduces
bleaching
efficiency.(
Kodak
1990)

7.7.3
Ozone
Regeneration
Ozone
reacts
with
ferrocyanide
to
form
ferricyanide
as
follows:

2Fe(
CN)
6
­
4
+
O
3
+
H
2
O

2Fe(
CN)
6
­
3
+
2OH­
+
O
2
Hydrobromic
acid
is
also
added
to
control
pH
and
to
supply
the
bromide
ion
needed
for
the
bleach
process.
The
major
advantage
of
this
process
is
that
there
is
no
salt
buildup.
Disadvantages
include
high
initial
cost
for
the
ozone
generator
and
potential
safety
problems,
since
ozone
is
corrosive,
unstable,
and
high
reactive.
Because
of
these
disadvantages,
this
process
is
likely
to
be
used
only
by
large
labs.(
Kodak
1990)

7.7.4
Ion
Exchange
Bleach
water
containing
dilute
concentrations
of
hexacyanoferrates
(
either
ferricyanide
or
ferrocyanide)
can
be
passed
through
a
column
containing
a
weak
base
anion
exchange
resin,
which
removes
the
hexacyanoferrate.
The
resins
is
then
regenerated
with
sodium
hydroxide,
and
the
recovered
hexacyanoferrate
reacted
with
ozone
or
persulfate
to
recover
ferricyanide
as
shown
above.
Treated
effluent
from
this
process
can
contain
as
little
as
0.075
mg/
L
(
75
parts
per
billion)
hexacyanoferrate.(
Kodak
1990)
56
7.7.5
Reverse
Osmosis
Reverse
osmosis
can
remove
up
to
95
percent
of
the
salts
from
fixer
solutions,
including
nearly
all
of
the
hexacyanoferrates.
The
capital
investment
is
relatively
high,
which
has
limited
applicability
of
this
process
in
photoprocessing.(
Kodak
1990)

7.7.6
Precipitation
Fixer
overflow
can
be
treated
with
ferrous
sulfate
and
a
flocculent
to
produce
ferrous
ferrocyanide.
Then
either
sodium
or
potassium
hydroxide
is
added
to
make
the
ferrocyanide,
which
can
be
reoxidized
with
one
of
the
bleach
regeneration
techniques.
The
resulting
ferricyanide
can
be
reused
as
bleach
replenisher.

Another
method
uses
calcium
chloride
to
precipitate
the
salt
Ca(
NH
4)
2
Fe(
CN)
6.
This
method
can
reduce
ferrocyanide
concentration
of
some
color­
reversal
fixers
to
less
than
1
g/
L.
(
Kodak
1990)

7.8
Rinse
Water
Use:
Reduction
and
Recycling
To
maintain
product
quality,
many
photoprocessing
operations
use
continuous
rinse
water
flows.
The
result
is
rinse
water
waste
streams
usually
are
the
highest
volumes
of
waste
from
photoprocessors.
This
effluent
consists
primarily
of
water
with
low
concentrations
of
chemicals
from
the
carry­
over
of
the
processing
solutions.
Commercial
rinse
water
recycling
systems
are
available
for
photoprocessing
operations.
Spent
rinse
water
can
be
treated
to
restore
purity
and
recycled
for
rinsing.
A
small
portion
of
incoming
clean
water
is
added
to
the
recycled
water
stream,
and
an
equivalent
overflow
goes
to
the
sewer
drain
after
the
fixer
wash.
A
single
recycling
system
can
serve
several
photoprocessor
units.

Water
conservation
is
important
in
certain
parts
of
the
United
States
where
either
(
a)
fresh
water
is
in
short
supply
or
(
b)
local
regulations
severely
limit
or
prohibit
discharge
of
photoprocessing
effluents
to
the
sewer
system.
Some
operators
simply
shut
off
the
rinse
water
except
when
film
is
moving
through
the
processor.
However,
certain
processors
require
a
continuous
water
flow
to
maintain
temperature
control.
Many
locales
have
established
concentration­
based
limits
on
aqueous
effluents,
which
encourages
greater
rinse
water
use
for
dilution.
Photoprocessors
must
check
the
local
requirements
to
be
sure
that
reducing
water
without
proportionately
reducing
all
other
contaminants
will
not
violate
the
concentration
limit.
57
7.8.1
Countercurrent
Rinsing
Continuous
photoprocessing
trains
may
employ
a
series
of
rinse
steps,
designed
so
that
water
flows
countercurrent
to
the
process.
Thus,
fresh
water
is
fed
to
the
final
stage.
Overflow
water
then
goes
to
the
next
stage
upstream.
Of
course,
the
rinse
water
becomes
more
contaminated
in
each
succeeding
stage.
Thus,
it
may
be
economical
to
use
squeegees
to
minimize
carryover
of
contaminants
into
each
rinse
stage,
and
a
squeegee
between
the
processing
solution
and
the
first
wash
stage
is
recommended.
Otherwise,
efficiency
will
be
impaired
and
product
quality
will
degrade.

7.8.2
Plumbingless
Minilabs
Plumbingless
minilabs
use
a
proprietary
chemical
stabilizer
in
place
of
wash
water.
While
conventional
minilabs
discharge
20
to
25
gallons
of
effluent
per
roll
of
film
processed,
this
type
of
lab
discharges
less
than
0.1
gallon
of
effluent
per
roll.
Although
the
volume
of
effluent
is
greatly
reduced,
the
concentrations
of
contaminants
are
much
higher
than
for
conventional
minilabs.
Wherever
there
are
concentration
limits
on
sewer
discharges,
potential
users
should
review
this
point
with
local
authorities
if
silver
can
be
recovered
from
this
effluent
using
either
the
metallic
replacement
or
electrolytic
processes
described
above.(
Kodak
1989b)

7.8.3
Evaporation
Another
option
in
managing
waste
photographic
solutions
is
evaporation,
in
which
the
wastewaters
are
collected
and
heated
to
evaporate
all
liquids.
This
is
often
done
under
vacuum
to
reduce
the
boiling
temperature.
As
the
water
and
volatile
compounds
are
removed,
soluble
materials
remain
to
form
a
sludge.
The
sludge
is
collected
in
filter
bags,
which
can
be
sent
to
a
silver
reclaimer
for
recovery.
Evaporation
can
accommodate
operations
that
do
not
have
access
to
sewer
connections
or
waste
water
discharge.
If
the
water
vapor
is
condensed
and
recycled,
instead
of
being
vented
to
the
atmosphere,
then
this
can
be
considered
a
source
reduction
technique.

One
manufacturer
has
an
automatic
recirculating
system
in
which
aqueous
effluent
is
continuously
introduced
into
the
evaporation
chamber.
The
water
is
vaporized,
then
condensed
and
recycled
to
a
rinse
water
holding
tank.
As
the
water
evaporates,
the
solids
are
collected
in
one
of
two
5­
micron
filter
bags.
When
the
unit
senses
that
the
filter
bag
is
full,
it
switches
the
flow
to
the
other
filter
bag,
and
alerts
the
operator
to
remove
the
filled
bag.

The
advantage
of
this
approach
is
it
achieves
"
zero"
water
discharge.
Virtually
all
of
the
silver
in
the
waste
solutions
is
captured
with
the
solids.
There
are
several
disadvantages,
however.
One
is
that
volatile
organics
in
the
waste
solution
may
be
evaporated
as
well,
creating
an
air
pollution
problem.
One
evaporation
unit
has
a
charcoal
air
filter
to
capture
these
organics.
58
A
second
disadvantage
is
that
any
organics
which
condense
with
the
water
will
be
recycled
also,
causing
a
potential
buildup
of
their
concentrations
in
the
process.
Finally,
this
is
an
energy
intensive
technique
and
so
carries
associated
high
energy
costs
and
fuel­
use
environmental
effects.
(
Calif.
DHSa)

7.9
Implementation
of
Control
Technologies
As
detailed
above,
photoprocessors
practice
chemical
recovery
and
wastewater
treatment
for
both
economical
and
environmental
reasons.
The
wastewater
from
photoprocessing
operations
has
been
a
focus
of
regulation
because
of
a
number
of
parameters,
including
toxic
metals,
toxic
chemicals,
oxygen
demand,
ammonia,
and
bionutrients.
Table
7.2
below
presents
1991
data
on
the
use
of
environmental
controls
and
chemical
recovery
methods
by
commercial
photoprocessors.

Table
7.3
summarizes
the
silver
concentration
at
typical
recovery
efficiencies
for
end
of
process,
in
combination
with
low
silver
solutions,
and
in
combination
with
process
wash
waters.

Table
7.2
Commercial
Photoprocessor
Environmental
Controls,
1991
All
Specialty
Retailers
Combined
Camera
Store
with
Minilab
Stand­
Alone
Minilab
Mail
Order,
Wholesale,
and
Captive
Labs
Portrait
Studio
Firms
Percent
Operating
Silver
Recovery
Systems
96.3%
89.5%
100%
66.7%

Type
of
Silver
Recovery
System
Used:

!
electrolytic
recovery
!
steel­
wool
canister
!
ion
exchange
!
evaporation/
distillation
80.7%
45.8%
3.6%
2.4%
82.6%
48.9%
0.9%
0.9%
81.0%
43.9%
6.3%
0.3%
94.7%
57.9%
20.8%
8.3%
63.2%
36.8%
2.0%
4.1%

Percent
that
Recycle
Water
7.8%
10.2%
7.2%
40.9%
10.0%

Percent
that
Regenerate
Chemistry
25.8%
19.6%
28.6%
86.4%
22.6%

Percent
of
Firms
Visited
or
Contacted
by
State
or
Local
Water
Authority
in
1991
13.1%
25.4%
73.3%
25.0%

Source:
EPA
1994
Note:
Population
basis
for
these
values
was
unspecified
in
source
report
(
EPA
1994).
59
Table
7.3
Silver
Concentrations
After
Silver
Recovery
(
mg/
L)

Percent
Recovery
Ag
in
Silver­
Rich
After
Recovery1
When
Combined
with
Silver­
Poor2
When
Combined
with
Wash
Water3
90%

95%

99%

99.9%
200
­
800
100
­
400
20
­
80
2
­
8
100
­
400
50
­
200
10
­
40
1
­
4
10
­
40
5
­
20
1
­
4
0.1
­
0.4
Source:
Silver
CMP
1.
Silver
concentrations
after
recovery.
2.
Silver
concentrations
when
treated
silver­
rich
solutions
are
combined
with
silver­
poor
solutions.
Silver­
rich
solutions
include
fix,
bleach­
fix,
washless
stabilizer,
and
low­
flow
washwaters.
Silver­
poor
solutions
include
developers,
bleaches,
stop­
baths,
stabilizers
used
after
washes,
and
washwaters.
3.
Silver
concentrations
when
treated
silver­
rich
solutions
are
combined
with
silver­
poor
solutions
and
process
washwaters.

7.10
Control
and
Treatment
Issues
A
barrier
to
the
effective
treatment
of
photoprocessing
wastewaters
is
the
small
size
and
lack
of
technical
sophistication
of
many
of
the
photoprocessors.
Processes
to
remove
silver
and
other
pollutants
from
wastewaters
require
careful
operation
and
maintenance
to
achieve
their
design
effectiveness.
Many
photoprocessors,
especially
the
minilabs
within
drug
stores,
grocery
stores,
and
department
stores,
do
not
have
staff
with
sufficient
training
and
longevity
to
operate
this
equipment
effectively.(
EPA
1994)

High
prices
for
certain
inputs
have
encouraged
reduced
use
of
those
inputs
over
time.
In
addition
competition
based
on
product
quality
has
encouraged
some
environmental
improvements.
This
congruence
between
economic
and
environmental
goals
was
particularly
noted
with
respect
to
silver.
Past
increases
in
the
price
of
silver
encouraged
efforts
both
to
reduce
the
amount
of
silver
used
in
sensitized
products
and
to
increase
silver
recovery
and
recycling.
The
extent
to
which
silver
is
recycled
is
sensitive
to
price,
and
according
to
industry
participants
is
currently
hampered
by
the
combination
of
moderate
prices
for
silver
and
the
costs
of
complying
with
RCRA
rules.
However,
actions
taken
to
reduce
the
amount
of
silver
in
sensitized
products
also
had
the
effect
of
improving
product
quality.
According
to
industry
contacts,
competition
based
on
product
quality
has
continued
to
encourage
the
use
of
less
silver
over
time,
independent
of
fluctuations
in
the
price
of
silver.(
EPA
1994)

The
high
cost
of
replacing
photoprocessing
equipment
acts
as
an
economic
barrier
to
improved
environmental
performance.
Many
environmental
improvements
(
e.
g.,
processes
that
60
recycle
photoprocessing
chemicals)
are
embedded
in
the
photoprocessing
equipment,
and
replacement
of
existing
equipment
is
required
to
achieve
those
improvements.
Photoprocessors
are
reluctant
to
replace
equipment
before
the
end
of
its
useful
life,
especially
minilabs,
for
whom
the
capital
investment
can
be
a
substantial
burden.
While
the
equipment
replacement
cycle
acts
as
some
constraint
on
the
speed
of
environmental
improvements,
it
is
not
clear
that
is
causes
significant
delays.
The
basic
pace
of
product
and
process
improvements
results
in
a
turnover
of
photoprocessing
equipment
in
only
eight
years
on
average,
according
to
industry
experts.(
EPA
1994)

Photographic
product
users'
needs
are
also
cited
by
industry
contacts
as
a
factor
influencing
the
pace
and
extent
of
environmental
improvements.
As
described
earlier,
different
end­
use
segments
present
different
demands
that
influence
the
nature
of
the
leading
photoprocessing
chemistry
over
time.
For
example,
the
market
demand
for
one­
hour
processing
eliminates
many
opportunities
for
reducing
the
chemical
content
of
processing
packages.
If
chemicals
are
reduced,
the
film
must
remain
in
the
solution
longer,
extending
the
time
required
for
developing.
Also,
the
accuracy
an
quality
requirements
of
x­
ray
film
an
graphic
arts
film
limit
the
potential
for
alternatives
to
silver­
halide­
based
film.(
EPA
1994)
61
8.
Environmental
Assessment
8.1
Introduction
This
chapter
examines
the
effects
that
the
pollutants
discharged
from
the
photoprocessing
industry
may
have
on
human
health,
aquatic
ecosystems,
and
Publicly
Owned
Treatment
Works
(
POTWs).
First,
the
list
of
characteristic
photoprocessing
pollutants,
introduced
in
Chapter
6,
is
re­
examined.
Next,
pollutant
loads
as
reported
in
the
national
Permit
Compliance
System
(
PCS)
database
are
presented.
Total
industry
pollutant
loads
are
then
calculated
using
estimated
flows
and
pollutant
concentrations
from
Chapter
6.
A
toxic
weighting
factor
analysis
is
performed
for
the
list
of
characteristic
pollutants.
This
analysis
is
used
to
show
the
relative
toxicity
of
the
effluent
components
in
a
manner
consistent
with
the
effluent
guidelines
program.
These
toxic
weighting
factors
are
used
in
conjunction
with
the
calculated
pollutant
loads
to
estimate
industrywide
toxic
loads.

Next,
a
qualitative,
pollutant­
by­
pollutant
list
of
potential
environmental
impacts
and
fate
is
presented
for
typical
photoprocessing
effluent
constituents.
Evidence
in
the
scientific
literature
of
the
negative
environmental
effects
of
photoprocessing
wastewater
is
summarized.
The
three
areas
of
concern
explored
here
include
impacts
on
activated
sludge
treatment,
impacts
on
human
health,
and
impacts
on
aquatic
ecosystems.

A
separate
section
is
devoted
to
the
potential
impacts
and
speciation
of
silver,
which
is
the
pollutant
of
greatest
concern
in
photoprocessing
effluent.
It
is
explained
that,
although
certain
ionic
forms
of
silver
are
considerably
toxic,
especially
to
aquatic
invertebrates,
more
prevalent
compound
and
complexed
forms
of
silver
are
generally
less
toxic.

8.2
Pollutants
Found
in
Photoprocessing
Effluent
Table
8.1
lists
the
main
pollutants
mentioned
in
Chapter
6
as
possible
photoprocessing
wastewater
constituents.
Two
of
the
pollutant
parameters
(
Temperature
and
pH)
are
not
pollutants
in
the
traditional
sense
and
will
not
be
discussed
further
here.
Five
(
COD,
BOD,
TSS,
TKN
and
TDS)
are
classes
of
pollutants
and
not
individual
pollutants.
Discussion
of
health
effects,
environmental
effects,
and
POTW
treatment
for
many
of
these
pollutants
follows
the
loading
analysis
in
Section
8.4.
For
other
parameters,
health
and
environmental
effects
and
POTW
removal
data
were
not
available.
62
Table
8.1
Possible
Photoprocessing
Wastewater
Constituents
Pollutant
Parameter
Ferri­
and
Ferro­
cyanide
Temperature
Cyanide
pH
Chromium
Biochemical
Oxygen
Demand
(
BOD)*

Para­
phenylenediamene
Chemical
Oxygen
Demand
(
COD)*

Hydroquinone
Total
Dissolved
Solids
(
TDS)*

Sulfonated
Hydroquinone
Total
Suspended
Solids
(
TSS)*

Ascorbic
Acid
Ammonia
Nitrogen
(
NH
3­
N)*

Ethylenediaminetetraacetic
acid
(
EDTA)
Total
Kjeldahl
Nitrogen
(
TKN)*

Hydroxylamine
Thiosulfate*

Iron­
EDTA
Complex
Sulfates*

Propylenediaminetetraacetic
acid
(
PDTA)
Silver
(
after
silver
recovery)*

Ammonia
Thiosulfate
Iron*

Silver
Thiosulfate
Zinc*

*
Pollutants
for
which
data
are
available
to
calculate
total
annual
discharge
loads
Another
source
for
pollutant
information
for
the
photoprocessing
industry
is
the
Permit
Compliance
System
(
PCS).
PCS
is
a
computerized
information
management
system
maintained
by
EPA's
Office
of
Enforcement
and
Compliance
Assistance
(
OECA).
PCS
contains
data
on
permit
conditions
and
monitoring,
compliance,
and
enforcement
for
facilities
with
National
Pollutant
Discharge
Elimination
System
(
NPDES)
permits.
NPDES
permits
are
applicable
only
to
facilities
that
discharge
directly
to
surface
waters.
However,
some
states
also
include
data
from
facilities
that
discharge
to
groundwater
in
the
PCS
data
base,
so
these
groundwater
data
are
also
available
in
the
PCS
data
base.
Among
other
items,
PCS
records
indicate
the
pollutant
parameters
listed
in
the
permit,
and
may
also
contain
information
of
the
loadings
of
these
pollutants
discharged
in
the
facility's
wastewater.

Only
five
facilities
in
the
United
States
are
currently
permitted
and
listed
in
the
PCS
data
base
under
the
photoprocessing
SIC
codes.
The
pollutants
and
limits
in
these
permits
are
based
63
on
ground
water
controls
or
water
quality
load
allocations:
none
are
based
on
Subpart
A
of
40
CFR
Part
459.
Table
8.2
summarizes
the
pollutants
and
annual
loadings
for
these
facilities
for
1995.
Loadings
for
Facilities
1,
2,
3,
and
5
are
all
to
groundwater.
Facility
4
discharges
its
wastewaters
directly
to
surface
water.

Table
8.2
Pollutant
Loadings
for
Direct
Discharge
Photoprocessing
Facilities,
1995
Units
are
pounds
per
year,
except
flow
is
in
gallons
per
year.
"
Not
Mon."
indicates
that
pollutant
was
not
monitored
in
the
permit.

Pollutant
Facility
1
Facility
2
Facility
3
Facility
4
Facility
5
Flow
(
gallons/
yr)
1284
12090
45210
33,480,000
201,000
Fluoride,
Total
(
lbs/
yr)
0.004394
Not
Mon.
0.053113
Not
Mon.
Not
Mon.

Copper,
Total
0.001479
0.035028
0.032011
Not
Mon.
Not
Mon.

Iron,
Total
0.000589
0.660947
0.058013
Not
Mon.
0.397
Nickel,
Total
0.005958
Not
Mon.
Not
Mon.
Not
Mon.
Not
Mon.

Silver,
Total
0
0.001382
0.014938
Not
Mon.
0.044
Zinc,
Total
0.009923
Not
Mon.
0.050807
Not
Mon.
Not
Mon.

Foaming
Agents
0
Not
Mon.
0.04808
Not
Mon.
Not
Mon.

Nitrogen,
Total
Not
Mon.
0.32509
Not
Mon.
Not
Mon.
3.925
Lead,
Total
Not
Mon.
0.001888
Not
Mon.
Not
Mon.
Not
Mon.

Phenolics,
Total
Recov.
Not
Mon.
0
Not
Mon.
Not
Mon.
0
Methylene
Chloride
Not
Mon.
0
Not
Mon.
Not
Mon.
Not
Mon.

Oil
&
Grease
Not
Mon.
Not
Mon.
1.029303
0
Not
Mon.

Nitrate,
Total
as
N
Not
Mon.
Not
Mon.
1.444289
Not
Mon.
Not
Mon.

Magnesium,
Total
Not
Mon.
Not
Mon.
3.475618
Not
Mon.
Not
Mon.

Sulfate,
Total
Not
Mon.
Not
Mon.
15.86418
Not
Mon.
Not
Mon.

Iron
&
Manganese,
Total
Not
Mon.
Not
Mon.
0.061863
Not
Mon.
Not
Mon.

Boron,
Total
Not
Mon.
Not
Mon.
0.061142
Not
Mon.
Not
Mon.

Chromium,
Total
Not
Mon.
Not
Mon.
0.002772
Not
Mon.
Not
Mon.

Manganese,
Total
Not
Mon.
Not
Mon.
0.002772
Not
Mon.
Not
Mon.

Antimony,
Total
Not
Mon.
Not
Mon.
0.004927
Not
Mon.
Not
Mon.
Pollutant
Facility
1
Facility
2
Facility
3
Facility
4
Facility
5
64
Aluminum,
Total
Not
Mon.
Not
Mon.
0.030341
Not
Mon.
Not
Mon.

Nitrogen­
NH3
as
NH3
Not
Mon.
Not
Mon.
0.948351
Not
Mon.
Not
Mon.

Phenolic
Compounds
Not
Mon.
Not
Mon.
0.003318
Not
Mon.
Not
Mon.

Solids,
Total
Dissolved
Not
Mon.
Not
Mon.
115.4557
131328.1
Not
Mon.

Bromide
Not
Mon.
Not
Mon.
0.303408
Not
Mon.
Not
Mon.

BOD,
5
day
Not
Mon.
Not
Mon.
Not
Mon.
1397.108
Not
Mon.

Solids,
Total
Suspended
Not
Mon.
Not
Mon.
Not
Mon.
1229.455
Not
Mon.

Nitrogen
­
NH3
as
N
Not
Mon.
Not
Mon.
Not
Mon.
22.0743
Not
Mon.

Cyanide,
Total
Not
Mon.
Not
Mon.
Not
Mon.
5.588431
0.044
Silver,
Dissolved
Not
Mon.
Not
Mon.
Not
Mon.
0.055884
Not
Mon.

Silver,
Total
Recoverable
Not
Mon.
Not
Mon.
Not
Mon.
0.111769
Not
Mon.

Zinc,
Total
Recoverable
Not
Mon.
Not
Mon.
Not
Mon.
2.794216
Not
Mon.

Aluminum,
Total
Recoverable
Not
Mon.
Not
Mon.
Not
Mon.
27.67218
Not
Mon.

Aluminum,
Dissolved
Not
Mon.
Not
Mon.
Not
Mon.
27.94216
Not
Mon.

Cadmium,
Total
Recoverable
Not
Mon.
Not
Mon.
Not
Mon.
2.794216
Not
Mon.

Chromium,
Total
Recoverable
Not
Mon.
Not
Mon.
Not
Mon.
2.794216
Not
Mon.

Chlorine,
Total
Residual
Not
Mon.
Not
Mon.
Not
Mon.
27.94216
Not
Mon.

COD
Not
Mon.
Not
Mon.
Not
Mon.
10897.44
Not
Mon.

Acetone
Not
Mon.
Not
Mon.
Not
Mon.
Not
Mon.
0.022
This
table
shows
that
there
is
a
wide
disparity
in
the
pollutants
measured
(
permitted)
from
facility
to
facility.
The
variation
of
these
photoprocessing
pollutant
parameters
is
a
subject
for
future
investigation.
Permit
writers
also
have
chosen
to
require
measurement
of
certain
parameters
(
for
example,
silver)
by
different
means
(
total
silver,
dissolved
silver,
and
total
recoverable
silver)
at
different
facilities.
The
reported
loads
for
most
parameters
other
than
conventional
pollutants
are
below
one
pound
per
year,
which
is
very
low
compared
to
most
other
manufacturing
and
service
industries.
The
flow
values
are
relatively
low
as
well.
65
TWF

5.6
AQ

5.6
HHOO
8.3
Toxic
Weighting
Factor
Analysis
EPA's
Office
of
Water
uses
toxic
weighting
factors
(
TWFs)
to
compare
the
relative
toxicity
of
industrial
effluent
discharges.
The
toxic
weighting
factors
applied
to
the
photoprocessing
industry
are
derived
using
the
same
methodology
employed
for
other
effluent
guidelines,
but
are
based
on
updated
toxicity
information.
TWFs
are
used
to
calculate
copper­
based
pound­
equivalents,
and
are
derived
from
EPA
chronic
aquatic
life
criteria
(
or
toxic
effect
levels)
and
EPA
human
health
Ambient
Water
Quality
Criteria
(
or
toxic
effect
levels)
established
for
the
consumption
of
fish.
For
carcinogenic
substances,
the
human
health
risk
level
is
set
at
10­
5,
(
i.
e.,
protective
to
a
level
allowing
1
in
100,000
excess
cancer
cases
over
background).
Copper,
a
toxic
metal
pollutant
commonly
detected
and
removed
from
industrial
effluent,
is
selected
as
the
benchmark
(
i.
e.,
the
pollutant
to
which
others
are
compared).
EPA
has
used
copper
previously
in
TWF
calculation
for
the
cost­
effectiveness
analysis
of
effluent
guidelines.
While
the
water
quality
criterion
for
copper
has
been
revised
(
to
12.0

g/
L),
the
TWF
method
uses
the
former
criterion
(
5.6

g/
L)
to
facilitate
comparisons
with
cost­
effectiveness
values
calculated
for
other
regulations.

The
TWF
for
aquatic
life
effects
and
the
TWF
for
human
health
effects
are
added
for
pollutants
of
concern.
The
calculation
is
performed
by
dividing
the
former
copper
criterion
of
5.6

g/
L
by
the
aquatic
life
and
human
health
criteria
(
or
toxic
effect
levels)
for
each
pollutant,
expressed
as
a
concentration
in
micrograms
per
liter
(

g/
L):

Where:
TWF
=
toxic
weighting
factor
AQ
=
Chronic
aquatic
life
value
(

g/
L)
HHOO
=
Human
health
(
ingesting
organisms
only)
value
(

g/
L)

Toxic
weighting
factors
for
the
5
pollutants
for
which
loadings
are
estimated
and
toxicity
data
are
available
are
given
in
Table
8.3.
66
Table
8.3
Pollutant
Toxic
Weighting
Factors
Pollutant
TWF
Ammonia
0.0022
Sulfate
5.6
X
10­
6
Silver
47
Iron
0.0056
Zinc
0.0051
Only
one
of
the
pollutants
(
silver)
has
a
TWF
greater
than
1.0.
This
value
is
based
on
silver
nitrate,
however,
which
is
not
expected
to
exist
in
any
appreciable
concentration
in
photoprocessing
effluent,
as
described
in
section
8.6.

8.4
Loads
Associated
with
Photoprocessing
Effluent
It
is
useful
to
estimate
the
total
quantity
of
pollutants
being
discharged
by
the
entire
universe
of
facilities
of
a
certain
industrial
category
in
order
to
compare
the
relative
pollutant
constituent
releases
within
the
industry,
and
also
to
compare
these
pollutant
releases
to
those
of
other
industries.
The
total
pollutant
loading
for
the
amateur
photoprocessing
industry
can
be
calculated
from
the
flow
and
concentration
values
estimated
in
Chapter
6.
Values
for
the
other
photoprocessing
sectors
can
not
be
estimated
due
to
lack
of
processing
volume
information.
However,
it
is
estimated
that
the
amateur
photoprocessing
industry
accounts
for
44
percent
of
all
photoprocessing,
in
correspondence
to
this
segment's
silver
use
as
compared
to
all
photographic
silver
use
(
data
given
in
Table
4.3).
The
results
presented
in
Table
6.8
show
that
the
total
1994
amateur
photoprocessing
flow
is
estimated
to
be
2,250
million
gallons
per
year,
based
on
the
additive
process
flow
demands
as
reported
in
reference
WEF
1994.
The
pollutant
concentrations
found
in
the
total
combined
wastestreams,
as
presented
in
Table
6.3,
are
multiplied
by
this
flow
rate
to
calculate
loads
according
to
the
following
equation:

Load
(
lbs/
yr)
=
Mean
Concentration
(
mg/
L)
x
2,250
million
gallons
x
3.785
L/
gal
x
2.205
lbs/
kg
x
1
kg/
106
mg
Since
the
total
unweighted
load
does
not
sufficiently
describe
the
potential
environmental
impact
of
an
industry's
dicharge,
toxic
weighting
factors
as
described
above
in
Section
8.3
are
used
to
calculate
a
toxic
load,
from
the
following
equation:

Toxic
Load
(
lbs­
eq/
yr)
=
Load
(
lbs/
yr)
x
TWF
67
Table
8.4
shows
the
estimated
loads
for
each
pollutant
constituent,
and
the
toxic
loads
for
those
pollutants
which
have
a
toxic
weighting
factor.

The
table
shows
that
the
total
expected
annual
load
for
the
amateur
sector
this
industry
is
133
million
pounds
per
year,
and
that
approximately
9
million
toxic
pounds
are
discharged
annually
(
99.9
percent
of
which
are
due
to
silver,
for
which
the
given
toxic
weighting
factor
is
not
representative).
Once
again,
the
amateur
sector
is
estimated
to
account
for
44
percent
of
all
photoprocessing
volume.

Table
8.4
Estimated
1994
Loads
and
Toxic
Loads
for
the
Amateur
Sector
of
the
Photoprocessing
Industry
Pollutant
Parameter
Concentration#
Range
(
mg/
L)
Concentration
Average
(
mg/
L)
Load
(
lbs/
yr)
TWF
Toxic
Load
(
lbs­
eq/
yr)

BOD
200­
3,000
1,600
30
X
106
NA
COD
400­
5,000
2,700
51
X
106
NA
TDS
300­
3,000
1,650
31
X
106
NA
TSS
<
5­
50
27
0.51
X
106
NA
Ammonia
20­
300
160
3.0
X
106
0.0022
6,610
TKN
30­
350
190
3.6
X
106
NA
Thiosulfate
100­
1,000
550
10
X
106
NA
Sulfates
50­
250
150
2.8
X
106
5.6
X
10­
6
16
Silver
<
0.1­
5
10

0.19
X
106
47*
8,830,000
Iron
<
10­
100
55
1.0
X
106
0.0056
5,784
Zinc
<
0.75
0.75
14
X
103
0.0051
72
Total
=
133
X
106
Total
=
8,842,482
#
Values
from
reference
WEF
1994,
pg.
10.

The
value
range
<
0.1
­
5
is
low
compared
to
the
concentration
ranges
presented
in
Table
7.3,
for
95
percent
silver
recovery,
combined
wastestream
(
combined
with
wash
water),
of
5­
20
mg/
L.
The
value
of
10
mg/
L
has
been
taken
to
be
more
realistic.
*
This
value
is
for
the
pure
silver
ion
and
does
not
accurately
represent
the
actual
toxicity
of
most
silver
compounds
or
complexes
that
would
be
expected
to
exist
in
photoprocessing
wastewater.

As
a
comparison
to
the
silver
discharge
value
estimated
above
of
190,000
pounds
(
1994,
amateur),
the
total
silver
loading
before
recovery
can
be
calculated
from
the
silver
content
of
the
68
film
and
paper
used,
the
quantity
processed,
and
the
silver
wash­
out
rates.
The
silver
content
of
a
variety
of
films
and
papers,
and
the
proportions
of
these
film
and
papers
used
by
type
for
a
typical
photofinishing
facility,
are
available
in
the
literature.
Assuming
removal
of
all
silver
in
color
processing,
and
80
percent
silver
removal
in
black­
and­
white
processing,
these
values
give
the
amount
of
silver
rendered,
in
Troy
ounces
per
1000
square
feet
processed,
to
be
2.35
for
paper,
and
21.3
for
film.(
EPA
1991a,
EPA
1991b)
Multiplication
by
the
total
film
and
paper
used
for
the
U.
S.
amateur
market
allows
the
loadings
calculation
prior
to
silver
recovery:

2.35
Troy
ounces
x
4,115
x
106
ft2
paper
+
1000
ft2
paper
21.3
Troy
ounces
x
296
x
106
ft2
film
=
16
million
Troy
ounce
1000
ft2
film
or
1.1
million
pounds
silver
Thus,
an
overall
recovery
rate
of
83
percent
of
this
1.1
million
pounds
would
lead
to
the
estimated
1994
amateur
market
discharge
quantity
of
190,000
pounds.

8.5
Qualitative
Environmental
Impact
of
Photoprocessing
Effluent
Constituents
This
section
examines
the
potential
environmental
impacts
of
some
of
the
pollutants
addressed
earlier
in
this
chapter
as
being
characteristic
of
photoprocessing
wastewater.
Not
all
pollutants
are
listed
due
to
lack
of
information.
Examples
of
impacts
include:
impacts
on
human
health,
impacts
on
the
health
of
aquatic
organisms,
impacts
on
operation
of
biological
wastewater
treatment
systems,
and
aesthetics.
Removal
by
typical
activated
sludge
systems
is
also
addressed.

Ammonia
Ammonia
(
NH
3)
is
one
of
the
constituents
of
the
nitrogen
cycle.
It
is
a
concern
because
it
can
increase
oxygen
demand,
promote
eutrophication,
and,
when
converted
to
nitrate,
cause
irritation
of
the
gastrointestinal
tract.
The
toxicity
of
ammonia
to
aquatic
life
is
dependant
on
pH
and
dissolved
oxygen
level.(
EPA
1981a)
One
study
using
a
simulated
photoprocessing
waste
stream
showed
an
average
removal
of
ammonia
in
activated
sludge
reactors
of
53
percent.(
Pavlostathis)

Cadmium
Cadmium
is
an
extremely
dangerous
toxicant.
In
addition
to
being
classified
as
a
human
carcinogen,
cadmium
could
form
organic
compounds
with
mutagenic
or
teratogenic
properties.
In
addition,
conventional
water
treatment
practices
do
little
to
remove
cadmium,
and
it
has
been
found
to
accumulate
in
the
liver,
kidneys,
pancreas,
and
thyroid
of
humans
and
other
animals.
Cadmium
also
acts
synergistically
with
other
metals;
its
toxicity
is
considerably
increased
when
combined
with
copper
or
zinc.
Among
aquatic
organisms,
fish
eggs
and
larvae
and
crustaceans
appear
to
be
especially
sensitive.(
EPA
1981a)
69
Chromium
Chromium
in
industrial
wastewaters
exists
primarily
in
hexavalent
and
trivalent
states.
Both
are
hazardous
to
man
and
aquatic
life,
but
in
photoprocessing
wastewaters
the
trivalent
form,
which
is
considerably
less
toxic,
predominates.
Observed
toxic
effects
on
man
include
lung
tumors,
skin
sensitization,
corrosion
of
the
intestinal
tract,
and
inflammation
of
the
kidneys.
Lower
forms
of
aquatic
life
are
extremely
sensitive
to
chromium.
As
with
cadmium,
chromium
is
not
destroyed
when
sent
to
a
POTW,
and
it
either
partitions
to
the
biosolids
or
passes
through
the
treatment
stream.
Removal
by
activated
sludge
systems
is
estimated
to
be
84
percent.(
EPA
1981a,
EPA
1982)

Cyanide
Cyanide
is
generally
found
in
photoprocessing
effluent
in
the
form
of
ferri­
and
ferrocyanide
(
hexacyanoferrate)
ions.
These
forms
exhibit
a
low
order
of
toxicity
to
most
aquatic
species,
notable
exceptions
being
crustaceans
and
algae.
Hexacyanoferrate
ions
seem
to
cause
no
adverse
effect
on
POTW
biomass
at
typical
levels,
and
treatment
plant
removal
efficiency
was
reported
at
greater
than
60
percent.
As
mentioned
in
Chapter
6,
however,
these
ions
release
the
cyanide
ion
when
exposed
to
sunlight.
Some
of
the
cyanide
ions
will
join
with
hydrogen
ions
to
form
hydrogen
cyanide
(
HCN),
depending
on
the
pH
of
the
solution.
(
The
lower
the
pH,
the
greater
the
percentage
of
cyanide
ions
that
will
be
present
in
the
form
of
hydrogen
cyanide).
The
cyanide
ion
is
non­
accumulative
and
comparatively
non­
toxic
to
humans.
Toxicity
to
fish
is
dependent
on
pH,
temperature,
dissolved
oxygen,
and
presence
of
other
minerals
in
the
water.
It
is
generally
more
toxic
to
fish
that
it
is
to
lower
organisms.(
EPA
1981a,
EPA
1982)

Iron
Iron
is
an
essential
nutrient
for
all
forms
of
growth,
and
does
not
have
significant
toxic
impact
on
humans
at
any
reasonable
concentration.
The
presence
of
iron
in
water
may
encourage
growth
of
iron
oxidizing
bacteria,
resulting
in
formation
of
slimes
that
may
affect
aesthetic
values
of
water
bodies
or
block
pipes.
The
recommended
limit
for
iron
in
water
supplies
is
based
not
on
health
concerns
but
on
aesthetic
and
taste
considerations.(
EPA
1981a)

Lead
Lead
is
not
easily
excreted
from
the
human
body,
and
thus
accumulates
with
repeated
exposure
over
long
periods
of
time.
Possible
effects
include
lead
poisoning
(
plumbism)
and
cancer.
Lead
is
also
a
concern
among
animals.
More
farm
animals
are
poisoned
by
lead
than
by
any
other
poison.
Lead
also
causes
suffocation
of
fish.
Studies
have
shown
POTW
removal
rates
for
lead
of
greater
than
90
percent,
although
80
percent
is
more
common.
Most
of
this
is
partitioned
to
the
biosolids.(
EPA
1981a,
EPA
1982)

Silver
See
Section
8.6.

Sulfates
70
Sulfates
are
not
harmful
in
moderate
concentrations
(<
1,000
mg/
L).
They
occur
naturally
in
waters,
especially
in
the
western
United
States.
Thiosulfates
are
commonly
found
in
photoprocessing
wastewaters,
as
described
in
Chapter
6.(
EPA
1981a)
One
study
using
simulated
photoprocessing
wastewaters
found
that
about
35
percent
of
total
COD
of
the
composite
photoprocessing
wastewaters
was
thiosulfate
and
sulfite.
COD
reductions
in
the
activated
sludge
reactors
used
varied
between
84
and
96
percent,
including
the
almost­
complete
removal
of
thiosulfate
and
sulfite
(
reduced
to
sulfate).
Ammonia
removal
in
the
photoprocessing
wastewater
amended
reactors,
meanwhile,
was
lower
than
in
the
control
reactor,
possibly
indicating
inhibition
of
the
highly­
sensitive
Nitrobacter
species.(
Pavlostathis)

Oxygen
Demand
(
BOD
&
COD)
Certain
levels
of
oxygen
demand,
depending
on
the
receiving
water
body,
will
result
in
reduced
Dissolved
Oxygen
(
DO)
levels.
Aquatic
organisms
experience
stress
at
reduced
DO
levels,
both
at
the
individual
and
population
levels.
Some
fish
species
experience
delayed
hatching
of
eggs,
interference
with
food
digestion,
decreased
growth
rate,
decreased
tolerance
to
other
toxicants
(
including
cyanide
and
lead),
and
reduced
sustained
swimming
speed.
These
effects
are
usually
more
pronounced
in
livelier
species
(
such
as
trout
and
salmon).
BOD
removal
rates
by
activated
sludge
systems
are
generally
around
90
percent.(
EPA
1981a,
EPA
1982)

Total
Dissolved
Solids
(
TDS)
Dissolved
solids
include
carbonates,
chlorides
and
other
halides,
sulfates,
phosphates,
nitrates,
and
trace
substances.
Although
moderately
high
concentrations
of
TDS
do
not
have
serious
health
effects
on
humans,
drinking
water
becomes
unpalatable
when
TDS
exceeds
2,000
mg/
L.
Tolerances
of
aquatic
organisms
for
TDS
is
species
specific,
but
although
fish
can
slowly
become
acclimated
to
higher
salinities,
sudden
exposures
can
often
be
fatal.(
EPA
1981a)

Total
Suspended
Solids
(
TSS)
Suspended
solids
include
organic
(
oil,
tar,
vegetable
waste
products)
and
inorganic
(
sand,
silt)
components.
Impacts
on
aquatic
ecosystems
include
reduced
light
penetration,
which
hampers
photosynthetic
activity,
and
clogging
of
gills
and
respiratory
passages
of
organisms.
POTW
removal
of
TSS
can
be
as
high
as
90
percent.(
EPA
1981a,
EPA
1982)

8.6
Toxicity
and
Speciation
of
Silver
Silver
is
present
in
a
number
of
compound
and
complex
forms
in
photoprocessing
effluents.
The
concentrations,
solubilities,
and
toxicities
of
these
silver
compounds
are
widely
varied,
and
it
is
essential
to
have
some
understanding
of
their
interrelation
to
better
comprehend
the
possible
adverse
effect
an
effluent
may
have
on
the
environment.

The
most
common
silver
complex
found
in
photoprocessing
effluent
is
silver
thiosulfate,
or
Ag(
S
2
O
3)
2.
This
is
a
stable
complex
with
a
dissociation
constant
of
3.5
E­
14,
meaning
that
free
silver
ions
(
Ag+)
will
not
normally
exist
in
any
significant
concentration.
Silver
nitrate
(
AgNO
3)
is
71
used
extensively
in
the
production
of
photosensitive
films
and
papers,
has
the
highest
solubility
of
the
silver
salts,
and
is
classified
as
a
strong
irritant
to
skin
and
tissue.
Silver
chlorate
(
AgClO
3)
is
moderately
soluble,
and
is
toxic
when
ingested.
Silver
chloride
(
AgCl)
is
soluble
in
solutions
containing
an
excess
of
chloride
ions,
and
in
solutions
of
cyanide,
thiosulfate,
and
ammonia,
and
is
relatively
toxic.
Silver
bromide
(
AgBr)
and
silver
sulfide
(
Ag
2
S)
are
insoluble
silver
compounds
commonly
found
in
precipitate
form
in
photoprocessing
effluents.
Solubilities
and
Solubility
Products
(
K
sp)
of
select
silver
compounds
are
shown
in
Table
8.5.

Table
8.5
Solubility
and
Solubility
Product
of
Some
Silver
Compounds/
Complexes
Silver
Compound
Solubility
(
g/
L
H20
at
25o
C)
Ksp
chloride
1.9
X
10­
3
1.8
X
10­
10
chlorate
90
NA
bromide
1.3
X
10­
4
3.3
X
10­
13
nitrate
2.16
X
103
NA
sulfide
(@
20o
C)
1.4
X
10­
4
1.0
X
10­
50
The
free
ionic
form
of
silver
combines
rapidly
with
naturally­
occurring
substances
to
form
less
toxic
substances.
For
example,
silver
chloride
complexes
are
three
hundred
times
less
toxic
and
silver
sulfide
complexes
are
one
million
times
less
toxic
than
free
silver.(
Dufficy)
Table
8.6
demonstrates
this
relative
toxicity
for
fathead
minnows.
72
Table
8.6
Percent
Mortality
of
Fathead
Minnows
Acutely
Exposed
to
Concentrations
of
Different
Silver
Compounds
Silver
Compound
Mean
measured
total
silver
concentration,
mg/
L
Mean
free
silver
ion
concentration,
mg/
L
Percent
Mortality
24
h
48
h
72
h
96
h
Silver
Nitrate
0.065
0.065
100
100
100
100
0.029
0.029
80
100
100
100
0.013
0.013
5
5
5
10
0.0058
0.0058
5
5
5
5
Silver
thiosulfate
complex
a
280
0.12
X
10­
6
5
5
5
10
140
0.33
X
10­
6
0
0
0
0
70
0.80
X
10­
6
0
0
0
0
Silver
sulfide
dispersion
b
240
<
10­
11
0
0
0
0
37
<
10­
11
0
0
0
0
Silver
chloride
(
2000
ppm
Cl)
a
4.6
1.03
X
10­
4
40
40
40
40
2.0
1.01
X
10­
4
5
10
10
10
0.38
1.01
X
10­
4
0
0
0
0
Source:
Dufficy
a.
Calculated
from
the
mean
measured
free
silver
ion
activity
b.
Calculated
from
the
relationship
[
Ag+]
2[
S2]=
K
sp
=
10­
50
The
free
silver
ion
is
an
effective
bactericide,
and
thus
it
can
interfere
with
biological
treatment
systems.
However,
one
study
indicated
that
silver
thiosulfate
concentrations
of
100
mg/
L
caused
no
negative
impact
on
unacclimated
activated
sludge.
The
study
also
states
that
photoprocessing
effluent
with
a
silver
concentration
as
high
as
10
mg/
L
could
be
handled
by
a
biological
treatment
system,
and
that
the
expected
effluent
from
the
treatment
system
would
be
less
than
20
ug/
l
of
soluble
silver,
even
without
dilution
from
other
treatment
plant
inputs.
Meanwhile,
silver
nitrate
and
silver
chloride
at
concentrations
of
10
mg/
L
were
found
to
cause
inhibition
between
43
and
84
percent.(
Bard)
73
Silver
that
settles
is
removed
from
the
treatment
plant
in
the
form
of
biosolids.
There
is
currently
no
EPA
biosolids
criteria
for
silver.
POTW
biosolids
are
often
disposed
by
landspreading
or
landfilling.
Laboratory
tests
on
biosolids
containing
silver
in
concentrations
from
19
to
83,000
mg/
kg
showed
no
release
of
silver
to
the
elutriate.
Field
tests
indicated
that
silver
was
effectively
bound
up
by
the
soil.

No
evidence
could
be
found
linking
photoprocessing
effluent
to
adverse
human
health
effects.
However,
silver
compounds
can
be
absorbed
into
the
circulatory
system
and
reduced
silver
deposited
in
various
tissues
of
the
body,
possibly
resulting
in
a
permanent
greying
of
the
skin
and
mucous
membranes
known
as
argyria.
Also,
concentrations
from
0.4
­
1
mg/
L
have
been
shown
to
cause
kidney,
liver,
and
spleen
damage
in
rats.(
EPA
1981a)
Some
local
authorities
in
the
United
States
consider
silver
to
be
a
hazardous
waste
in
concentrations
greater
that
5
mg/
L,
which
is
far
less
than
some
of
the
untreated
effluent
silver
concentrations
as
documented
in
Chapter
6.(
EPA
1991a)
As
mentioned
in
Section
8.3,
several
other
constituents
in
photoprocessing
effluent
can
also
have
carcinogenic
and
systemic
health
effects
on
humans.

LC
50
concentrations
of
silver
for
a
number
of
common
aquatic
organisms
varies
between
0.004
mg
Ag/
L
and
0.2
mg
Ag/
L.(
Bard)
Other
silver
salts,
such
as
silver
chloride
and
silver
nitrate,
are
also
considerably
toxic
to
fish.
One
study
claims
that
"
anthropogenic
inputs
of
silver
from
the
Point
Loma
discharge
off
San
Diego,
CA
can
account
for
essentially
all
of
the
silver
in
coastal
waters
along
the
United
States­
Mexico
border
during
summer
conditions",
and
that
"
silver
is
one
of
the
most
toxic
elements
for
marine
invertebrates."(
Sanudo)

The
silver
thiosulfate
complex,
however,
is
considerably
less
toxic;
the
96
hour
LC
50
was
found
to
be
greater
than
250
mg
Ag/
L.
Other
work
indicated
that
a
model
laboratory
ecosystem
including
rotifers,
Daphnia,
algae,
mussels,
and
fish
remained
viable
during
the
ten
week
study
period
in
spite
of
continuous
exposure
to
silver
thiosulfate
at
concentrations
as
high
as
5
mg
Ag/
L.(
Bard)
Despite
this,
it
is
still
desirable
to
remove
as
much
silver
thiosulfate
from
the
wastestream
as
possible,
since
thiosulfate
accounts
for
a
major
portion
of
the
oxygen
demand
in
photoprocessing
effluent.(
Hendrickson)

Bioaccumulation
of
silver
in
clams
in
the
vicinity
of
the
Palo
Alto
Regional
Water
Quality
Control
Plant
(
RWQCP)
has
been
well
documented.
Silver
concentrations
in
clams
near
the
RWQCP
discharge
channel
were
found
to
be
from
6
to
55
times
the
levels
of
silver
found
in
clams
in
other
areas
of
the
San
Francisco
Bay.
After
initiating
a
silver
reduction
pilot
program,
silver
concentrations
in
the
clams
showed
a
continual
decline.
However
it
is
not
clear
if
the
original
higher
concentrations
of
silver
caused
any
negative
impacts
on
the
clams.(
WEF
1994)
74
References
Bard:
Bard,
C.
C.,
et
al,
"
Silver
in
Photoprocessing
Effluents."
Journal
of
the
Water
Pollution
Control
Federation,
Vol.
48,
1976.
pp
389­
394.

Calif.
DHSa:
California
Department
of
Health
Services,
Alternative
Technology
Section,
Toxic
Substances
Control
Division,
"
Waste
Audit
Study:
Photoprocessing
Industry,"
1989.

Calif.
DHSb:
California
Department
of
Health
Services,
Alternative
Technology
Section,
Toxic
Substances
Control
Division,
"
Reducing
California's
Metal­
Bearing
Waste
Streams,"
1989.

Cook:
Cook,
M.
M.
and
Lander,
J.
A.,
"
Use
of
sodium
borohydride
to
control
heavy
metal
discharge
in
the
photographic
industry."
Journal
of
Applied
Photographic
Engineering,
Vol.
5,
No.
3,
1979.
pp
144­
147.

Dufficy:
Dufficy,
T.
J.
et
al,
"
Silver
Discharge
Regulations
Questioned."
Water
Environment
&
Technology,
April
1993.
p.
54.

EPA
1976:
USEPA,
Office
of
Water,
Development
Document
for
Interim
Final
Effluent
Limitations
Guidelines
and
Proposed
New
Source
Performance
Standards
for
the
Photographic
Processing
Subcategory
of
the
Photographic
Point
Source
Category,
EPA
440/
1­
76/
0601,
July
1976.

EPA
1980:
USEPA,
Office
of
Water,
Ambient
Water
Quality
Criteria
for
Silver,
EPA
440/
5­
80­
071,
1980.

EPA
1981a:
USEPA,
Office
of
Water,
Guidance
Document
for
the
Control
of
Water
Pollution
in
the:
Photographic
Processing
Industry,
EPA
440/
1­
81/
082­
9,
April
1981.

EPA
1981b:
June
15,
1981
Affidavit
of
Echardt
C.
Beck,
Assistant
Administrator,
EPA,
submitted
under
Natural
Resources
Defense
Council
et.
al.
Versus
EPA,
12
ERC
1833
(
March
9,
1979)

EPA
1982:
USEPA,
Office
of
Water,
Fate
of
Priority
Pollutants
in
Publicly
Owned
Treatment
Works,
EPA
440/
1­
82/
303,
September
1982.
p
61.

EPA
1987:
USEPA,
Office
of
Water
Enforcement
and
Permits,
Guidance
Manual
on
the
Development
and
Implementation
of
Local
Discharge
Limitations
Under
the
Pretreatment
Program,
December
1987.
75
EPA
1991a:
USEPA,
Office
of
Research
and
Development,
Guides
to
Pollution
Prevention:
The
Photoprocessing
Industry,
EPA/
625/
7­
91/
012,
October
1991.

EPA
1991b:
USEPA,
Office
of
Research
and
Development,
Waste
Minimization
Opportunity
Assessment:
A
Photofinishing
Facility,
EPA/
600/
2­
91/
039,
August
1991
EPA
1994:
USEPA
Office
of
Policy,
Planning,
and
Evaluation,
Sustainable
Industry:
Promoting
Strategic
Environmental
Protection
in
the
Industrial
Sector
­
Photoimaging
Industry,
Phase
1
Report,
June
1994.

Hendrickson:
Hendrickson,
T.
N.
and
Dagon,
T.
J.;
U.
S.
Patent
3,594,157;
July
20,1971;
assigned
to
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Kodak
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Kodak
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­
Choosing
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Photofinishing
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Publication
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35,
1989.

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1989b:
Eastman
Kodak
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1989.

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1990:
Eastman
Kodak
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"
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Pavlostathis:
Pavlostathis,
S.
G.
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Jugee,
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98.

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1995:
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Research
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The
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Nov.
1995.

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Sribnick,
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Appendix
A.
Calculation
of
Total
United
States
Surface
Area
of
Photographic
Film
and
Paper
Developed
for
Amateur
Market
Values
from
Literature*
Surface
Area
per
24
Exposure
Role
(
ft2)
Rolls
Processed
1994:
715.5
million

659
million
rolls
35mm
0.440

48.7
million
rolls
110/
126
0.131

5.01
million
rolls
disc
Not
Available

2.86
million
rolls
other
Not
Available
Exposures
Processed
1994:
17.58
billion

16.65
billion
color
print

615
million
slide

316
million
black­
and­
white
Original
Print
Market
Share:
!
Single
Prints
53.4%
versus
Twin
Prints
46.6%

!
3
½
x
5
inch
59.4%
versus
4
x
6
inch
40.6%

Assumptions
and
Simplifications
!
Assume
all
rolls
of
24
exposure,
supported
by
result:
17.58
billion
exposures/
715.5
million
rolls
=
24.6
exposures/
roll
!
Based
on
information
that
photoprocessors
gain
75%
of
revenue
from
original
prints
and
14%
from
reprints
and
enlargements,
assume
that
paper
surface
area
of
reprints
and
enlargements
is
14/
75
or
18.6
%
of
original
print
area.

!
Include
back­
and­
white
photoprocessing
in
with
color,
because
while
greatly
simplifying
the
calculation
the
only
waste
steam
affected
in
these
calculations
is
bleach,
effected
by
less
than
2
percent.

*
All
values
taken
from
reference
PMA
1995,
except
surface
area
per
roll
values
from
reference
EPA
1991a.
A­
78
Calculation
of
Film
Surface
Area
35mm:
659
million
rolls
35mm
x
0.440
ft2/
roll
24
exposures
=
290
million
ft2
110/
126:
48.7
million
rolls
110/
126
x
0.131
ft2/
roll
24
exposures
=
6.37
million
ft2
Total:
296
million
ft2
Note:
Total
does
not
include
disc
and
"
other"
film
area
due
to
lack
of
surface
area/
roll
data.

Calculation
of
Print
Paper
Surface
Area
59.4%
3
½
x
5:
(
16.65
billion
+
316
million)
x
3.5"
x
5"
x
1
ft2/
144
in2
x
.594
=
1.22
billion
ft2
40.6%
4
x
6:
(
16.65
billion
+
316
million)
x
4"
x
6"
x
1
ft2/
144
in2
x
.406
=
1.15
billion
ft2
Total:
2.37
billion
ft2
Total
with
twin
prints
(
46.6%
of
exposures):
2.37
billion
ft2
x
1.466
=
3.47
billion
ft2
Total
with
reprints
and
enlargements
(
18.6%
of
original
prints):
3.47
billion
ft2
x
1.186
=
4.12
billion
ft2