Introduction
The collection of processing tank overflows and subsequent regeneration of solutions for
reuse can reduce the quantity of chemicals discharged by between 40 and 90%,
depending on the solution. In addition to process and product modifications that have
resulted in the use of fewer processing solutions, lower concentrations of chemicals in the
solutions, and reduced replenishment rates [114], regeneration and reuse have
significantly decreased the quantity of chemicals discarded from large photographic
processing operations. The following section discusses the considerations that impact
regeneration and reuse techniques for color developer solutions, desilvered fixers and
bleach-fixes, and bleaches.
Whether or not a specific processing solution can be regenerated and/or reused
depends on a number of factors. First, reuse requires that the reclaimed solution is or can
be made photographically acceptable. That is, sensitometric measurements, generated
from photographic test materials processed with the reclaimed solution, must meet
specific quality standards.
Secondly, the practicality of regeneration techniques will depend on the size of the
photographic processing operation and the consumption rate of the solutions. If
sophisticated equipment and techniques are required, a small photoprocessing operation
will most likely not have the technical expertise or be able to afford the capital
expenditure needed to regenerate certain solutions.
In most photographic processes, fresh replenisher is added to each solution tank at a
predetermined, fixed rate while the exposed product moves through the process, to
maintain a certain minimal concentration of each required chemical in the processing
solution. However, individual chemical constituents may be depleted at varying rates due
to differences in exposure, size, or photographic characteristics of the photographic films
or papers, differences in the rate they are fed through the process, effects of oxidation or
carry-in of other solutions, and so on. While the replenisher formula attempts to correct
for this as well as possible to maintain a chemical balance, the need to discard unwanted
byproducts means that overflows from processing tanks will still contain large quantities
of good chemicals that can potentially be reused. The exact techniques chosen for
regeneration depend on the balance of unwanted vs. wanted components and their
chemical nature.
Efforts by Eastman Kodak Company and other manufacturers have resulted in
alternate options for specific photoprocessing solutions that use low replenishment rates.
These produce much of the environmental benefit that can be realized by regeneration.
Medium-to-large photoprocessing facilities are urged to explore the costs vs. benefits of
these options for their own particular situation.
Bleach Regeneration
As previously described, bleaches contain oxidizing agents that oxidize metallic silver to
silver ion. Today most photographic processing bleaches use the selective oxidizing
ability of ferric iron in a chelated form, often as an iron EDTA complex [122]. Other
bleaching agents include iron PDTA, ferricyanide, and persulfate. Iron PDTA has
replaced iron EDTA in some bleach formulations as a more environmentally acceptable
bleaching agent because it is more active; therefore, less is needed to obtain efficient
conversion from metallic silver to silver halide in films [123,124].
Iron EDTA and iron PDTA bleaches used in color negative film and some color paper
processes are usually regenerated in large photo labs. In most instances, the bleach
overflow is collected and the ferrous ion oxidized to ferric by simple aeration, then make-
up chemicals are added to bring the solution back to replenisher strength [125].
In the case of persulfate bleach, the overflow is simply restored to replenisher strength
by running chemical analyses followed by specific chemical additions. Many persulfate
bleaches require an activator or accelerator bath preceding the bleach. Often, the
accelerator bath itself may also be reused by collecting the overflow solution and
bringing it back to replenisher strength, through specific chemical additions.
Regeneration is attractive to many photofinishing laboratories as a cost-saving
measure, and in most cases it will significantly reduce the amount of iron, chelating
agent, and COD discharged to the environment.
Ferricyanide Bleach Management. Although most modern processes use alternative
bleaches, ferricyanide is still the bleaching agent of choice for a few older processes such
as the Kodachrome and Ektachrome Aerial film processes, and in some instances as an
option in the Eastman Color motion picture processes. Ferricyanide bleaches underwent
intensive study over the years for the development of regeneration and management
methods.
In ferricyanide bleaches, ferricyanide ion is the oxidizing agent, which becomes
reduced to ferrocyanide upon use. Together, these ions and related forms of the iron
cyanide complex are known as hexacyanoferrates. The concentrations of
hexacyanoferrates in an effluent can be minimized by a combination of reliable
regeneration methods for the bleach overflow and recovery techniques for the fixer and
wash waters.
Ferricyanide Bleach Regeneration. Ferricyanide bleach regeneration requires
collecting the overflow and treating it with a strong oxidizing agent. Options include
persulfate, peroxide, bromine, ozone, and electrolysis [126]. When persulfate (once the
oxidant of choice) is used [127], the specific gravity of the solution may build up due to
the formation of sulfate byproduct. Eventually, after several regeneration cycles, the
sulfate concentration can grow high enough to reduce bleaching activity. This is usually
remedied by discarding between 5 and 10% of the overflow. In lieu of hauling away all
of the excess bleach, a precipitation technique can be used to prevent the wasted material
from entering the sewer (see subsequent section, Ferrocyanide Precipitation and
Recovery). Note that this same chemical recovery technique can be used to remove
ferrocyanide from a fixing bath, when a fixer instead of a water wash step follows the
bleach.
An alternative bleach oxidant to persulfate is ozone [128,129]. The use of ozone
requires a fairly significant capital investment in equipment, and safeguards to minimize
risk to personnel because ozone is a toxic and unstable gas. However, the specific gravity
build-up problem attributable to persulfate is eliminated (see previous subsection,
Ozone).
Another technique having many of the advantages of ozone without the risk of a toxic
gas is electrolytic bleach regeneration [130]. Ferrocyanide is oxidized to ferricyanide at
the anode of an electrolytic cell. Because of the reduction reaction that occurs
simultaneously at the cathode, the cell must be divided by some type of semipermeable
membrane. Also, since some hydrogen is produced at the cathode, reliable exhaust
ventilation is required. Commercial units are available (see previous subsection, Electro-
oxidation). This is the most widely used method today.
Recovery of Hexacyanoferrate from Washwater. In some cases, it may be necessary to
remove hexacyanoferrates from washwaters following a bleach or fixer. Because the
complexes will be very diluted, it is not feasible to use precipitation techniques. Two
options have been tried to concentrate these salts and allow them to be recovered:
Methods Introduction
Certain chemicals can be recovered individually from waste solutions even when the
overall solution can no longer be salvaged. Often these are primary ingredients of a spent
processing bath; in other situations, they may be foreign ingredients carried in from a
preceding tank. Occasionally, it may be technically possible and economical to purify
them in the laboratory and reuse them directly in a process. Other times the recovery may
be done simply to extract a waste material that cannot be discharged to a sewer and
isolate it for separate disposal.
Coupler Recovery
In the Kodachrome film process, cyan, magenta, and yellow couplers are present in the
three separate color developer solutions. (In all other processes, they are incorporated in
individual layers within the color film or paper.) The Kodachrome couplers are all
soluble in an alkaline solution but will precipitate at neutral or acid pH. Therefore,
recovery becomes simple. The developer overflows are individually collected, pH is
lowered (usually with sodium bisulfate, dilute sulfuric or acetic acid or carbon dioxide
gas), and the precipitated coupler is then removed by centrifuging or filtration and dried
for storage. When needed, the dried coupler can be resolubilized in alkali (usually
preceded by a grinding or homogenizing step to make mixing easier) and reused.
Analytical facilities are required for this technique [135].
Ferrocyanide Precipitation and Recovery
Although ferricyanide and ferrocyanide (together hexacyanoferrates) have relatively low
toxicities, to the degree that they are even used as ingredients in foods [5,6], they can be
of concern because they have the capability of being degraded very slowly (often a matter
of months) through photolysis, especially by strong sunlight, to form low concentrations
of free cyanide [11]. Therefore, the discharge of hexacyanoferrate from a
photoprocessing operation must be controlled. Any overflow concentrates that cannot be
regenerated and reused, and sometimes washes or fixers containing hexacyanoferrate,
should be treated. A very effective technique has been developed for removing
hexacyanoferrate complexes from an effluent by precipitation [72]. The ferricyanide in
solution is reduced to ferrocyanide by the addition of dithionite or a similar reducing
agent. The ferrocyanide is then precipitated by adding ferrous sulfate, to form insoluble
ferrous ferrocyanide; this technique is generally used to recover ferrocyanide from either
fixers or washes following bleaches. The precipitate is removed by filtration or
centrifuging.
After washing off by-product salts, the precipitate can sometimes be reused in new
bleach solutions by redissolving in alkali and reoxidizing it, although this latter method is
usually economically feasible only for a very large production operation having good
analytical capabilities [73].
Chromium Precipitation
As previously stated, chromium is a relatively rare metal in todays photographic
processing laboratories, although it is used in a few black and white reversal bleaches as
well as some process system cleaners. When a dichromate bleach is mixed with other
processing solutions that are alkaline, and with solutions containing reducing agents such
6+ 3+
as thiosulfate and sulfite, the Cr is reduced to Cr and precipitated as chromium
hydroxide or other insoluble particulate matter. The chromium 3+ precipitate is then
removed during primary or secondary clarification at the wastewater treatment plant as a
component of the sludge.
If necessary, because of sewer code discharge limits, chromium can be recovered from
solution in the processing laboratory by precipitation. This is done by collecting the
chromiumbearing overflow in tanks and reducing hexavalent chromium to the trivalent
state by adding bisulfite or dithionite. The chromium is then precipitated as an
amphoteric chromium hydroxide solid by adjusting the solution to pH 8 with an alkaline
material such as dilute sodium hydroxide. This sludge can then be removed by settling
and decantation, filtration, or similar techniques. The chromium hydroxide sludge will
need to be managed according to applicable Federal or State waste management
regulations.
Phosphate Recovery
During the 1970s there was great public pressure to remove phosphates from many
discharge sources, primarily household detergents but including industrial wastes,
because of the general absence of adequate municipal treatment facilities and the
resulting eutrophication of streams. At that time, great effort was put into reformulating
photographic solutions to exclude phosphates. Only small quantities remain today,
generally as sequestrants to prevent calcium in hard water from sludging or crystallizing
in process solutions and damaging emulsions, or for buffering high-pH developers. These
levels are generally so low that no pretreatment would be required by the average
laboratory that discharges to a POTW.
However, should phosphate removal be required because of particularly stringent
discharge limitations, it can readily be precipitated by various agents, particularly lime
(calcium hydroxide) or alum (potassium aluminum sulfate). Unfortunately, the resulting
precipitate is a sticky mass resembling toothpaste or milk of magnesia, from which it is
difficult to extract water. Successful ways of handling and dewatering this sludge include
evaporation, filtration on a vacuum belt filter or in a filter press, or drying of the solution
[72].
6.5.3 Conservation
A number of techniques can be applied in a photoprocessing laboratory to help reduce
chemical discharges to the sewer. These methods include the use of squeegees, careful
maintenance of replenishment rates, use of holding tanks and floating lids, and washwater
conservation.
Squeegees
Squeegees are used to reduce the carry-over of processing solutions and washes. Both
environmental and economic benefits result from their use. When properly installed and
maintained, they can reduce carryover by 75% or more. This reduction can mean, in turn,
that replenishment rates will be lowered significantly and regeneration efficiencies
optimized. Squeegees are usually installed after all washes in a processing machine, and
before and after all solutions being regenerated. Specifications for recommended
placement of squeegees should be checked for each particular process to reduce
carryover, minimize water spots, and prevent emulsion damage.
Squeegees exist as many different types, including wiper blades, vacuum squeegees,
wringer-slinger, air squeegees, and so on [136139]. The type to be used will depend on
the photographic product being processed, the particular solution tank (e.g., some of the
most flexible synthetic rubber squeegees used on downstream tanks could not survive the
relatively harsh alkaline environment of the developer tank), the kind of processing
machine, and the level of technical expertise available in the laboratory for installation
and maintenance.
Replenishment Rates
The replenishment rate required for adequate processing of a photographic product will
depend on many factors including the following: the nature of the photographic product,
speed at which it is being transported through the machine, temperature of the solution
(especially for developers), concentration of chemicals in the replenisher solution, rate of
build-up of seasoning products in the solution, design of the machine (certain
configurations introduce more air into the solution during operation than others), and the
overall utilization (i.e., running vs. standby time) of the processing machine.
Photographic product manufacturers will provide specifications for replenishment rates
required for a particular product under varying processing conditions. An adequate safety
factor is built into these recommendations. It is important that a processing laboratory use
the recommended rates. Although too low a rate could cause adverse photographic
results, too high a rate will result in a waste of chemicals and money. Therefore, all
processing laboratories should periodically check and adjust processing solution
replenishment rates.
Floating Lids
The use of floating lids on solution storage tanks will help reduce the aerial oxidation of
easily oxidized chemicals, as well as evaporation. As the solution level drops, the lid
stays in contact with the solution surface to eliminate any air space. It also safeguards
against airborne dust and dirt and accidental contamination by other laboratory chemicals
and materials. It helps protect the quality of the processed materials, helps extend
solution life, and thus lessens the dumping of stored solutions gone bad. All these
factors play important roles in the environmental as well as economic health of a
laboratory.
Washwater Conservation
Washwater conservation can be important for many reasons, including water shortages in
some locations, energy and fee savings associated with reduced water consumption, and
hydraulic limitations and/or discharge fees imposed on effluent discharged to municipal
sewer systems [140]. A laboratory can conserve water in several ways. These include
simple steps such as checking water supply equipment for leaks, using recommended
wash rates, and running washwater only during actual processing.
Several methods can also be applied to reuse washwaters. Reverse osmosis and other
membrane separation techniques have been chosen in a few instances, but their use is not
widespread because of cost, maintenance, membrane life, and operational problems that
to date remain largely unresolved.
Perhaps the most commonly practiced methods of reducing water use involve ion
exchange. A process such as the former PACEX water recycling system incorporated
ionexchange technology together with filtration and bacterial control to remove
contaminants [71]. In such a process, an anion-exchange resin removes silver thiosulfate
complex from solution. An oxidizing agent subsequently oxidizes residual thiosulfate to
sulfate and a biocide minimizes biological growth. A filter removes unwanted sediment.
Depending on the process, reduction in washwater usage from 5080% may be possible.
This method not only conserves water and recovers silver but also provides energy
savings by minimizing the quantity of fresh water that needs to be heated. Other
manufacturers have announced similar water reclamation systems in the past.
Washwater reuse raises several technical concerns. In each case where such a system
may be considered, the reputation and track record of the manufacturer should be
checked. Some water savers simply filter and pump water back to the processing
machine; however, the same result may be achievable merely by lowering the water input
rate. Some more sophisticated water recirculation devices are available (especially for x-
ray or graphic arts processes) that keep track of the amount of photographic material
processed and sound an alarm after a predetermined amount is reached, indicating that
the water should be changed.
On a number of occasions during the past century, magnetic or other mechanical
water treatment devices that do not consume either energy or chemicals have been
offered to the public, allegedly to purify water or stop the growth of microorganisms, but
reportedly without any true scientific basis for making such claims [141145]. We are not
aware of any instance where these have been proven effective in a photographic
laboratory.
The photoprocessing laboratory has the responsibility of ensuring that any recycling
device operates properly and is constantly monitored for chemical build-up, such that the
quality and storage life of processed films and papers do not suffer. Improper operation
may damage the customers photographic product. Also, washwater reuse will cause the
effluents discharged from the photoprocessing laboratory to be more concentrated.
Although the total chemical loading will not be higher, higher concentrations could result
in exceeding the sewer code.
In 1981, the EPA published a Guidance Document for the Control of Water Pollution
in the Photographic Processing Industry. In its conclusions, the report states, the
agency does not recommend the use of concentration-based limitations for controlling
pollutants at facilities in the industry [7]. The report goes on to state that limits based on
concentration tend to discourage water use reductions, whereas the agency encourages
the reduction of wastewater quantities by various water-saving controls. Unfortunately,
this recommendation has been largely ignored, and because discharge monitoring is more
difficult by other methods, most municipalities continue to use concentration-based
limitations. Therefore, before installing washwater conservation or reuse equipment, it is
important to check its potential effect on the laboratorys continued ability to use the
municipal sewer system.
Summary
As a final comment, the management of any chemical waste discharges, including
photographic processing wastes, is a constantly shifting target, both because of evolving
regulations as well as advances in photography and waste treatment technology.
Consultation with manufacturers of photographic products and reliable engineering and
legal sources should be sought by any laboratory considering the appropriate, up-to-date
management of its particular waste stream.