HEALTH & SAFETY GENERAL INFORMATION
[ Health & Safety ] - [ General Information ] - [ Safety Data Sheets ]
This section provides access to a library of HS&E information developed to provide practical guidance and advice to our customers. The content covers a wide range of topics including environmental controls over manufacturing processes, chemical hazards, fire, selection of personal protective equipment, and environmental considerations relating to used or waste product. This information reflects the most up to date opinion on HS&E issues relevant to a diverse product range distributed to a global market.
If you are looking for Safety Data Sheets (Known as SDS or MSDS) click HERE to go to the Safety Data Sheet selection page.
Health Safety & Environmental Management System
Health, Safety & Environmental Policies
Environmental Protection Policy
Health Safety & Environmental Achievements
Mobberley site Environmental Facts
How Photographic Chemicals can Enter Your Body
How Photographic Chemicals can Affect Your Body
How Exposure to Photographic Chemicals can be Controlled
Pregnant and Breast Feeding Women
Special Hazards - Hydroquinone
Special Hazards – Sulphur Dioxide
Information on Safety Data Sheets
Availability of Safety Data Sheets
Safety Data Sheets – A Simple User Guide and Glossary
Health & Safety Information for Coated Products
Media Safety Data Sheet (Article Information Sheet)
The Fire Classification and Burning Characteristics of ILFORD Photo Media
Fire Classifications of ILFORD Photo Media
Burning Characteristics of ILFORD Photo Media
Chemicals and Processing Solutions
Waste Disposal and Septic Tank Systems
Health Safety & Environmental Management System
HARMAN technology Ltd has a fully integrated health safety and environmental management system. All issues ranging from product design and the operation of the manufacturing processes, to marketing and the packaging and labelling of individual products are within the remit of the Health Safety and Environment Management Committee (HSEMC). The HSEMC meets at Mobberley 10 times per year.
The Mobberley operations unit is accredited to ISO9001:2000. The Health Safety & Environmental Management System is operated as a parallel system using the management principles of ISO9001.
Health and safety performance on the Mobberley manufacturing site has been recognised since 1985 by the Royal Society for the Prevention of Accidents with the presentation of numerous awards. In March 2006 HARMAN technology Ltd won the RoSPA Order of Distinction in recognition of 15 consecutive RoSPA Gold Awards between the years 1990 to 2005.
Health, Safety & Environmental Policies
HARMAN technology Ltd has developed and approved 4 key policies that underpin the Company’s approach to managing health, safety and environmental issues.
These set the objectives for and lead the development and delivery of programs for ensuring the:
- Occupational health & safety of the workplace in our manufacturing establishments
- Minimisation of the environmental impact of products and manufacturing processes
- Optimisation of effectiveness in energy conservation and efficient utilisation of raw materials in manufacturing
- Compliance of products with relevant HS&E legislation in each country into which our products are sold
These provide for:
- Prioritising health, safety and the environment in all operations
- Taking health and safety and the environment into account in development and design
- Health and safety and environmental monitoring
- Training employees in their health, safety and environmental responsibilities
- Research to improve health, safety and the environment
- Communication on matters of health, safety and the environment
- Participation with public policies on health, safety and the environment
- Energy efficiency and conservation
HARMAN technology Ltd also has additional programmes which go beyond these eight principles. Of course the company's factories and products conform to all local regulations and codes of practice in countries where HARMAN technology Ltd has a manufacturing or sales presence. However, HARMAN technology Ltd also puts a considerable amount of research effort into reducing the environmental impact of its products in ways that are not yet covered by legislation. HARMAN technology Ltd believes that environmental improvement and conservation are the routine responsibility of any business.
The excellence of HARMAN technology Ltd imaging products continues to make us leaders in quality, while maintaining productivity and efficiency for our customers. Today it is possible to reproduce with our products all the beauty and nuance of a breathtaking landscape, or capture the full spectrum of natural tones. At the same time, HARMAN technology Ltd is acutely aware that the original beauty in life, from which these images come, must be protected.
It is the policy of HARMAN technology Ltd to achieve high standards of health and safety which contribute to business performance and at the same time meet its responsibilities to people in a way which fulfils both the spirit and the letter of the law. (The Health and Safety at Work Act, 1974, and the Management of Health and Safety at Work Regulations 1998).
We will:-
Develop an appropriate organisational structure and a culture which supports risk assessment and risk control and secures the full participation of all members of the organisation. We will set legal requirements as the minimum acceptable level of achievement
- Consult with employee representatives to promote and develop measures to ensure the health and safety of all employees
- Support safety quality initiatives aimed at continuous improvements
- Appoint competent people to help with the implementation of the Health and Safety arrangements
- Provide information, instruction and training to all those working on our premises
The Company recognises that the promotion of health and safety at work is an essential function of good management. All levels of management and supervision must bear in mind that their responsibilities in this field rank equally with their responsibilities in others. The Company requires that every manager and supervisor should use their best endeavours to ensure compliance with the Company's objectives.
Phil Harris, Director, Health, Safety and Environmental Protection
Environmental Protection Policy
It is the policy of HARMAN technology Ltd to take all reasonable measures to protect the environment from any adverse effects that its activities might have.
We will:
- Take all reasonable measures in the design, construction, operation and maintenance of our plant, equipment and facilities to reduce any adverse effects which our operations might have upon the environment;
- Devote as much attention and effort to preventing pollution and safe guarding environmental matters in all our activities as to matters of economy and productivity;
- Identify and investigate environmental matters in a professional manner, with assistance from professional advisors when necessary;
- Provide the necessary instructions, equipment and training to enable our employees to carry out their duties in an environmentally safe manner;
- Make every effort, commensurate with the most recent scientific knowledge available, to ensure that our products will not have untoward effects on the environment.
- We will maintain an environmental protection organisation which will seek continuous improvement, develop and administer methods and procedures and co-ordinate all efforts to secure fulfilment of this policy.
Phil Harris, Director, Health, Safety and Environmental Protection
It is the policy of HARMAN technology Ltd to act responsibly and to take all necessary measures to protect the customer and the environment by ensuring that its products are safe and comply with the appropriate health, safety and environmental legislation in each country into which these products are sold.
We will:
- Maintain an awareness of and ensure compliance with international product, health, safety and environmental regulations and requirements.
- Take necessary measures in the design, manufacture and marketing of our products to protect the environment and prevent personal injury.
- Identify responsibilities and accountabilities for the management and implementation of policies designed to ensure product safety.
- Provide the necessary instructions, equipment and training to enable our employees to carry out their duties consistently with this policy.
- Maintain an organisation which will develop and administer methods and procedures and co-ordinate the efforts required to secure fulfilment of this policy.
Howard Hopwood, Director, Marketing and Business Development
It is the policy of HARMAN technology Ltd to maintain throughout our operations a commitment to energy conservation.
We will:
- Take full account of energy resources, and use these efficiently and economically, reflecting best industry practice, thereby contributing to an improved environment.
- Ensure good management of energy resources in all our manufacturing and administrative areas.
- Ensure all staff and suppliers are involved in the energy saving process and understand energy saving techniques in the context of the business.
- Assess the likely effects of planned projects and operations on energy utilisation and consequently their environmental impact.
- Set performance targets and report to employees how well those targets have been met.
Phil Harris, Director, Health, Safety and Environmental Protection
Health Safety & Environmental Achievements
The last three decades have seen an aggressive programme to eliminate components with questionable hazards by replacing these with substitutes proven to be ecologically safe. Also, the quantity of raw materials needed have been reduced and/or replaced by recycled ones. More than 60% of the silver used in our film and paper production comes from recycling. All packaging material is based on recycled or recyclable products, and we actively try to reduce the amount of packaging that we use.
The volume of chemistry needed for our processes has been reduced by up to 50% depending on the process, and water consumption has been reduced by as much as 90%. The Mobberley production site is regulated and licensed to operate to strict environmental standards and is equipped with sophisticated effluent treatment plant,heat exchangers, silver recovery and other environmental protection equipment.
HARMAN technology Ltd does not and never has tested any chemical product on animals. Nor do we use animals in any other capacity. Wherever possible, HARMAN technology Ltd uses existing, well characterized chemicals since this allows us to make use of existing and available toxicology data. In those very rare cases where animal test data is required to be produced to comply with national and international laws, this data will only be commissioned from accredited test laboratories. Such testing is only commissioned as a last resort, when all alternative sources of data have been exhausted and in these cases only the minimum amount of testing is done to meet with national and international regulations.
Mobberley Site Environmental Facts
The HARMAN technology manufacturing plant at Mobberley in the UK is situated in the Cheshire countryside. As a consequence we have made, and will continue to make, as required, significant investments in order to minimise waste and prevent pollution of the local environments.
VOC (solvent) emissions to the air are controlled by the Local Authority under LAPPC permit. Emulsion making and small scale chemical manufacturing activities are controlled by the Environment Agency under IPPC permit. We also have our own on site effluent treatment plant and its emissions are controlled and monitored by the local sewage undertaking. Facts:
- Mobberley produces four different types of liquid waste, each waste stream has it’s own dedicated drainage system
- All the site drains are mapped and labelled to increase awareness in the event of a spillage
- In the event of a major incident, the flow of surface water leaving the site can be stopped and contained
- An incident response team is available on 24 hour call out
- Waste management audits are reported monthly and annually
Traditional photography is unimaginable without the use of chemical solutions. In a crowded world it is important to keep hazardous chemicals separate from the environment. Therefore, during recent years, around the world environmental legislation as well as workplace health and safety regulations have become more stringent.
Our improved understanding of the impact of individual chemicals on the environment has allowed HARMAN technology Ltd to consistently make improvements to reduce the effects of our products and wastes. This has included the replacement of the chemicals of most concern as well as a reduction in the volume produced by our processes. HARMAN technology Ltd products are famous for the highest quality in all aspects, and this includes workplace and environmental safety.
Photo processing chemistry has not only to be judged in terms of its effects on man through possible exposure in the workplace (see How can photographic chemicals enter and affect your body), but also in terms of its effects on the environment when it becomes waste. The main influence in estimating environmental effects depends upon the method of disposal. Waste chemistry entering a natural waterway can be more harmful to the environment than a solution properly disposed of by a waste handling company. Today responsible photo laboratory owners either treat their waste before disposal or have it hauled away by a licensed waste disposal company. However, wash water from photo processors, which contains very small amounts of photo chemicals carried over from the processing tanks, can usually be discharged to the sewer. This must of course be checked with your local utility provider
All these chemicals entering the sewer have to be judged concerning their biodegradability (ease of being destroyed or broken down in the environment) and toxicity (hazard posed to the environment). Fortunately, most photographic chemicals are non-toxic or easily biodegradable and therefore pose no problem for the environment. Micro-organisms, growing in waste water treatment facilities or in rivers and lakes easily take care of them. The critical question to ask is: are there any toxic, non-degradable compounds in HARMAN technology Ltd processes which have the potential to pass via wash water through the waste water treatment plant and to harm the living environment in rivers and lakes? Clearly the answer to this question is no! But let's have a look at some of the current issues:
Silver is present in very small amounts in developer and in moderate quantities (3-8 g/l) in fixer. Therefore some silver gets into the waste from the wash after fixing. Silver from a photographic process leaves the system as a non-toxic complex of thiosulphate. The binding of silver to thiosulphate is extremely strong and prevents the release of free silver ions (the toxic form of silver). Silver thiosulphate is rapidly transformed in waste water treatment plants to non-toxic silver sulphide which will not change further and is insoluble and therefore precipitates as sludge.
Hydroquinone is the main active ingredient in black and white developer solutions. In dilute solutions hydroquinone decomposes in minutes. In most cases hydroquinone levels are already below the detection limit at the entrance to the water purification plant. If not, they are easily handled by the plant. However, in the past some water treatment plants have considered hydroquinone as being comparable to phenols (slowly degradable chemicals, which have a similar chemical structure to hydroquinone). The main problem of phenols is their ability to react with chlorine and form hazardous non-degradable compounds. Hydroquinone does not react in this way and any restrictions by water treatment plants based on such comparisions are not justified.
Rapid fixers contain ammonium thiosulphate. As the name implies, this a source of ammonium ion. Ammonium ion enters natural waterways by the ton from farming and domestic waste water, (these account for over 80% of the nitrogen added to the environment). It is not toxic and functions as a fertiliser, leading to algae growth in lakes and rivers. However this is an unwanted effect which makes the control of ammonia an environmental concern. Ammonium ion is biodegradable, so if wash water from your processor is delivered to a modern water treatment plant, it will be fully broken down to nitrate and then to nitrogen.
EDTA is widely used as a chemical (sequestering agent) that can bind to ions such as iron, calcium, etc. and render them inactive. EDTA is not biodegradable and is not removed from waste water by water treatment plants. EDTA has been removed from all HARMAN technology Ltd products.
Boric acid and its salts (borates) are used in some HARMAN technology Ltd film developers and Hypam fixer as a pH buffer. Boric acid or borate entering a river or a water purification plant partly precipitates as calcium borate. In nature, borates are found in many different minerals. However, it is known, that dissolved borates in high concentration show some toxicity on plants. The borate level in HARMAN technology Ltd working strength chemicals is low and presents no environmental hazard.
In common with all chemical products, HARMAN technology Ltd photographic processing chemicals may be hazardous to health in many different ways. However provided that these are used according to the instructions and common sense working methods and standards of hygiene are observed the risk to health associated with these chemicals will be adequately controlled.
How Photographic Chemicals can Enter Your Body
Inhalation or breathing.
Inhalation is the main route by which fumes, dusts, mists, aerosols and gases enter the body, making good ventilation a high priority. Exposure to irritant chemicals that would not affect most people may provoke an asthma attack in a person who already has asthma. For example, low levels of the gas sulphur dioxide can be produced by some HARMAN technology Ltd processes. Most individuals would be unaffected but asthmatics may need greater ventilation to avoid adverse affects.
Swallowing or ingestion.
Ingestion is normally only a problem when someone eats, drinks or smokes in the laboratory or darkroom. Therefore, take all possible measures to avoid contaminating food or drink with chemicals. Do not store photochemicals with foodstuffs or in containers previously used for storing foods. DO NOT EAT, DRINK OR SMOKE IN THE LABORATORY OR DARKROOM.
Personal hygiene is also important because hands can transfer chemicals to foods or cigarettes. If you accidentally swallow a small quantity of one of HARMAN technology Ltd's working solutions, do not panic, you will have enough time to take the first aid measures described in the safety data sheet or on the product label. Always keep all chemicals - household, garden or photographic - out of the reach of children.
In the case of accidental ingestion, it is not recommended to induce vomiting, especially in the case of ingestion of acids or alkalis. They would be corrosive twice; going down and coming up again. Milk should not be considered as an antidote because it may dissolve chemicals which are otherwise insoluble in water and make them available for the body which can actually increase the harm they cause to the body.
Eye contact.
The eye is a very sensitive organ and chemicals can very easily enter the eye from splashes. No HARMAN technology Ltd product is classified ‘Corrosive’ however, if corrosive chemicals are used and the eyes are splashed, irritation or even more serious damage may result. In every case immediately rinse the eyes with running water for several minutes and consult your local doctor or hospital straight away.
Eyes are easily protected by wearing safety glasses. This simple precaution is very effective in preventing eye damage.
How Photographic Chemicals can Affect Your Body
There is no easy way to predict what affect any given chemical of relatively low toxicity, such as those used in photo-processing, will have on an individual. Everyone responds to chemicals differently, based on the following factors:
- The physical state of the chemical. Air-borne chemicals are more easily inhaled and absorbed into the body than the same chemical in a solid or liquid form.
- The route of exposure to the chemical. Entry into the body via the lungs is a more direct path than through the skin.
- Individual susceptibility. People will react differently to a given chemical substance.
- The work environment. Adequate ventilation ensures minimal exposure to fumes and dusts, and good housekeeping reduces accidental contact.
- The time of exposure of the chemical substance. Generally, increased exposure results in increased risk.
- The amount of chemical the individual has been exposed to.
It is usual to distinguish between those effects of chemical exposure that are categorised as acute effects and those which are chronic effects. There is no hard boundary for the division. Generally acute effects are those which are immediately apparent and occur within a short period (hours or days) of exposure and are often reversible when the exposure is removed; while chronic effects are those that may not become apparent until after repeated or long term (months or years) of often low level exposure and these may not be reversible.
In either case, it is important to recognise the warning signs of exposure at the earliest stage possible.
Irritation
Some chemicals can cause irritation when absorbed through the skin. Symptoms of skin irritation include dryness, flaking, and cracking of the skin. Irritation is an acute effect and can be largely prevented using hand creams and protective gloves.
Chemicals can also cause irritation when inhaled into the lungs examples include sulphur dioxide gas which may be released in small quantities during processing, and the dust of powder developers, released during solution making. Exposure by inhalation must be avoided by ensuring adequate ventilation.
Burning
Some concentrated photochemical solutions contain strong acids (eg acetic acid) or alkalis (eg sodium hydroxide) at concentrations sufficient for them to become corrosive. These will always be labelled ‘Corrosive'. Undiluted these can cause chemical burns to the skin and eyes. The damage caused can be serious eg tissue loss and permanent eg blindness. Usually, the user dilutes these concentrates to prepare working solutions which are less corrosive. If affected by spills or splashes, immediately wash the affected area with plenty of water to prevent or limit any damage.
Sensitising
An individual using a chemical may become sensitised by repeated contact with it. Subsequently, even a tiny amount may cause an allergic reaction. A doctor may be able to identify if the affect is a skin irritation or a true allergic reaction. It is important to determine the cause of irritated skin conditions as there are many causes other than photographic chemicals. It may help your doctor if, before visiting him, you make a list of chemical products you handled at home and at work over the few days before the symptoms appeared (include such products as washing powders, household bleaches, dishwasher cleaners and gardening chemicals).
Hydroquinone is considered to be a sensitiser, although the effect is seen in very few cases.
Toxicity
Like other harmful effects, the toxicity of a chemical should be viewed in terms of both its acute and chronic effects. The acute toxicity is the measure of harm arising from a short term exposure to a fixed dose of the substance. This is expressed through the use of the warnings ‘Toxic’, ‘Harmful’ and ‘Irritant’. Most HARMAN technology Ltd liquid developers are now classified as Harmful following the EU reclassification of hydroquinone from July 2000.
The chronic or long term consequences of exposure to chemicals are more difficult to identify and measure, but most people quite rightly recognise that irreversible birth defects and cancer are possible consequences of such exposure and thus the mutagenicity, teratogenicity and carcinogenicity of chemicals are matters of great importance. Many chemicals can produce some evidence of these effects in animals. Where this is the case, details should be found on relevant safety data sheets.
HARMAN technology Ltd products do not use any chemical that is known to cause damage to the unborn child or the reproductive system or cause genetic damage or cancer in humans.
Physical and Other Hazards
As well as through their direct health effects, some chemicals can present other dangers to users through their chemical or physical properties. They may be oxidising substances, they may be radioactive, flammable or explosive. No HARMAN technology Ltd photographic chemical product contains sufficient amounts of any components that would require the use of anything other than those acute and chronic health warnings previously discussed.
For comparative information, other more hazardous classifications such as corrosive, flammable or highly toxic are associated with quite common household chemicals. eg Dishwasher cleaners, household bleaches, garden weed killers, solvents and paint strippers can all present, in comparison more serious risks to health.
How Exposure to Photographic Chemicals can be Controlled
Protective clothing and good ventilation are the most effective ways to ensure safe handling of chemicals.
Eye protection
Wear chemical splash goggles, safety glasses or visor when working directly with solid or liquid chemicals. An eye wash station should be available in the work room. This could simply be a container filled with fresh or sterile water.
Skin protection
When handling chemicals use gloves whenever possible. Tongs can be used instead of your fingers or hands to agitate solutions or transfer prints or negatives. If hands must be immersed in processing or other chemical solution eg when draining, cleaning and refilling processing equipment, wear protective gloves of special materials such as neoprene, latex/neoprene, or butyl rubber, especially when the product is labelled corrosive or harmful. Always rinse the gloves with water after contact with chemicals. If you wash your hands frequently a barrier cream may be useful in preventing them becoming too dry and flaky.
Respiratory protection
When extraction systems cannot sufficiently reduce levels of chemical fumes and dusts in workroom air then further protection must be used. When handling powdered chemicals we recommend the use of a dust mask. If large quantities of liquid chemistry are spilled, especially if several kinds are mixed together, complete breathing apparatus may be needed.
Ventilation
All darkrooms or processing rooms need some kind of forced ventilation. This could simply be a fan mounted through an outside wall or it could be a special ventilation system for a machine or a room depending on circumstances. However, processing rooms vary widely in size and in the types of chemicals used in them. Therefore recommendations for ventilation can only be rough guidelines. In general, 10-15 air changes per hour will produce a safe working environment.
The best way to avoid having problems with any chemical products is to keep in mind certain important rules for handling chemicals safely and carefully. Here are some safe working practices that should be followed when working with photographic chemicals.
- Read the Material Safety Data Sheet (MSDS) and Product Label for each chemical in your process, when working with it for the first time.
- Wear safety glasses and gloves when handling and mixing chemicals.
- Use tongs to agitate solutions and transfer prints and negatives between open dishes and tanks.
- Identify incompatible chemicals from information on MSDSs, for example which ones react violently and/or release fumes when mixed. Do not mix acids or bleach baths with developers or fixers - sulphur dioxide gas will be given off which can cause breathing discomfort, especially for asthmatics.
- Dispose of chemicals carefully. Chemicals poured down the drain can react to form dangerous gases. Flushing the drain with running water will remove this hazard. Most photographic chemicals must be disposed of as hazardous wastes. It is often illegal to pour them down the drain or discard them with ordinary waste water. Consult your local waste authority for further advice.
- Do not eat, drink or smoke in any area where chemicals are handled, stored or used.
- Wash your hands after using chemicals.
- If you spill a chemical, on the floor or inside the processor, clean it up as soon as you can.
- Keep the work area clean and tidy.
- Mixing of working solution chemistry from bulk chemicals may require additional protective clothing such as gloves and safety glasses, that may not be necessary when using the working-strength solutions.
Pregnant and Breast Feeding Women
Pregnancy should not be equated with ill-health but as a part of everyday life.
Protection of health and safety in respect of pregnant women can be adequately addressed by applying existing health and safety management procedures in the relevant areas. Many women work whilst they are pregnant and may return to work whilst they are still breast-feeding. However, some hazards in the workplace may affect the health and safety of new and expectant mothers and conditions considered acceptable in work situations may no longer be so during pregnancy.
To identify potential hazards a risk assessment should be undertaken which should consider the likelihood of any potential hazard that may be present to cause harm. Although this document refers to potential risks from exposure to photochemicals it should be recognised that other risks may be present, such as repeated or heavy lifting, working at heights or in tight situations. With specific reference to chemical agents and pregnancy or breast-feeding, those with the following risk phrases require appropriate controls to be in place to control risk.
R40 - Possible risk of irreversible effects
R45 - May cause cancer
R46 - May cause heritable genetic damage
R49 - May cause cancer by inhalation
R61 - May cause harm to the unborn child
R63 - Possible risk of harm to the unborn child
R64 - May cause harm to breastfed babies
With regard to photographic chemicals it is unlikely that substances with these risk phrases will be used. The label on the chemical and the safety data sheet will indicate the hazards and risk phrases. Some chemicals with risk phrase R40 are used, an example is hydroquinone. From a risk assessment standpoint, provided all necessary control measures are in place then pregnant women should be able to continue to work safely with photochemical products.
Special Hazards - Hydroquinone
Hydroquinone was discovered in 1880 and has been used in ILFORD photographic chemical products for over 100 years. It is the main photographic developing agent for most black and white processes. It is used throughout the photographic industry.
Other uses include:
- in the cosmetics industry in skin-lightening creams.
- as an antioxidant in the manufacture of rubber.
- as a polymerisation inhibitor in the chemical industry
Hydroquinone occurs naturally in:
- wheat products (e.g. bread and cereals)
- fruits (eg pears and blueberries/bilberries) and vegetables (e.g. broccoli and asparagus)
- coffee and tea
- some beers
- red wine
- a number of insects
Only 2 human hazards have been identified;
- Skin irritation, with possible risk of sensitisation (although the effect is seen in very few cases)
- Eye discoloration, with possible impaired vision in cases of extreme exposure (high levels of hydroquinone dust over several years).
Absorption through human skin is slow, so liquids pose a low risk, especially since wearing protective gloves prevents skin contact.
Powder products, which can become airborne and be breathed in to the body directly, are a greater risk. Good ventilation is essential when handling powders. Dust masks are required and breathing apparatus may be necessary if the dust becomes airborne during mixing.
Hydroquinone is a substance for which the hazardous properties have been agreed by a committee of experts and it is subject to a common hazard classification throughout the EU. This classification is reflected throughout HARMAN technology Ltd’s product labelling and safety data sheets. This EU classification is:
Carcinogen Category 3: R40 Ltd evidence of a carcinogenic effect
Mutagen Category 3: R68 Possible risk of irreversible effects
Harmful: R22 Harmful if swallowed
Irritant: R41 Risk of serious damage to eyes, R43 May cause sensitisation by skin contact
Dangerous for the Environment: R50 Very toxic to aquatic organisms
This classification is based on some evidence of cancer in animals only and on some evidence of damage to genetic material in animals only. There has been an inconclusive debate for many years about the long term effects of exposure to hydroquinone. There is no evidence, despite over 100 years of use, that any person has ever developed a cancer that can be categorically linked with exposure to hydroquinone. Indeed, in human studies, such as those of workers handling hydroquinone regularly (during the manufacture of photographic chemical products or use in photographic processing laboratories) the rate of cancer was slightly lower than for the general population.
In practice, this means that most developers are now classified as Harmful and have the risk phrase "Possible risk of irreversible effects". This may appear to be over-cautious but it reflects the latest improvements in awareness around the health and safety of chemicals.
Hydroquinone environmental facts:
- it has a low vapour pressure and reasonable solubility in water which means that it does not readily evaporate into the air from working solutions or waste streams from processes.
- rapidly biodegrades in sewage treatment processes
- it is toxic to fish, etc.
- bacteria, yeasts and fungi in soils and sewage sludges can all use hydroquinone as a source of carbon
Special Hazards – Sulphur Dioxide
Sulphur dioxide (SO2) is quite a common gas:
- it is used as a preservative in foods and wines
- it is produced in small quantities when you light a match.
- it results from the burning of coal, oil, vehicle fuel, etc.
- it also responsible for acid rain.
In the USA it is estimated that 500,000 workers are potentially exposed to sulphur dioxide, encountered in many industrial processes, from the manufacture of steel and bricks for buildings to chemical plants.
Small quantities of sulphur dioxide may be produced when processing black and white materials. As material is passed from the developer into an acid stop bath, traces of sulphite carried over may react to give sulphur dioxide gas.
This sulphur dioxide is very soluble in water and processing solutions, so it is mostly absorbed by the processing bath, as well as by the standard exhaust filters of processing machines. Properly maintained processing machines in well ventilated rooms will produce a levels of sulphur dioxide below the level at which it becomes a hazard or affects the user.
If you accidentally mix an acid with developer or fixer, larger amounts of sulphur dioxide will be generated:
- Leave the room immediately and go out into the fresh air
- Wait until no more gas is formed, then open windows and doors to flush fresh air into the room
- Dispose of the mixed solutions carefully
- Use a licensed waste disposal company if local regulations prevent discharge of waste to the drains
- Recent evidence has shown that much lower levels of sulphur dioxide than previously thought to be of concern can affect asthmatics. If problems do arise then further ventilation and extraction should be installed. In extreme cases it may be necessary to move the person affected away from this work area
The hazards associated with each product are calculated from those of the individual chemicals contained in each HARMAN technology Ltd product.
The primary means of communicating information about the hazards of any product is through the product label and packaging. When a product may be harmful, HARMAN technology Ltd prints a warning on the label of the bottle or pack. The process for determining and communicating chemical hazard information is internationally regulated and HARMAN technology Ltd goes to great lengths to ensure that our products meet the local regulatory requirements in each market into which they are sold.
Always read the label before using any chemical product for the first time.
The secondary means of communicating chemical hazard (and other) information is through the (Material) Safety Data Sheet (MSDS or just SDS). Manufacturers of hazardous preparations are required to produce and make freely available MSDSs for each of those products. HARMAN technology Ltd produces MSDSs for all of their chemical range (regardless of hazard or need) and all of these are freely available for download from this web site.
A typical label on an HARMAN technology Ltd product may contain
- a graphic or symbolic warning of danger
- a warning word: eg corrosive, or irritant
- risk statements (R-phrases): eg causes burns, irritating to skin and eyes
- safety statements (S-phrases): eg avoid contact with skin, keep out of reach of children
- a tactile warning (an embossed or raised triangle) added to the bottle labels and cartons of corrosive or harmful products which are used in the home
- national labeling information, e.g. waste phrases, waste numbers, product registration numbers, poison class
- information to aid recycling of the packaging, eg the so-called Green Dot symbol on products sold for home use
The label may also give information about the concentration of any ingredient that gives rise to the hazardous properties of a preparation. This is usually given as a range (eg 1-5%) or as a limit (eg >15%) rather than a precise value.
Information on Safety Data Sheets
HARMAN technology Ltd Safety data sheets (MSDSs or SDSs) provide detailed and extensive information to assist our customers in identifying the hazards of and ensuring suitable storage, use and disposal of our formulated products.
The information is organised and presented in the 16 section format that is required under EU Directive.
Through the MSDS, we attempt to provide all the essential facts relating to safe practice. However, these may still not contain all of the details you are looking for. If you require further information on any aspect of safety relating to the use of photographic chemicals, please refer to other HARMAN technology Ltd web site HS&E pages or contact, during working hours, the HARMAN technology Ltd’s distributor or sales office nearest to you.
Availability of Safety Data Sheets
MSDSs are produced for every HARMAN technology Ltd photochemical product, even for those products which are not classified as hazardous (under EU rules) and for which there is no legal requirement.
These are produced in 11 different language variants English, Spanish, Danish, German, French, Italian, Dutch, Portuguese, Finish, Swedish and Norwegian plus a US English variant in the ANSI format. All of these are available without restriction from the HARMAN technology Ltd web.
MSDSs are not produced for any coated product, or for any of those other products which are considered to be ‘articles’, and as such do not need an MSDS. Health and safety information that is appropriate for these products is included in their technical data sheets.
Safety Data Sheets – A Simple User Guide and Glossary
All HARMAN technology Ltd MSDSs have 16 sections. (In the US, sections 2 & 3 are exchanged). This explanation relates to the 16 section EU format.
Section 1
This section contains basic information to identify the preparation, the supplier and a contact address for further information in the event of an emergency.
Wherever possible the name and address of the local supplier/distributor has been given. In the case of those single language MSDSs that address multi regional markets (eg the French language MSDS which as well as it’s intended EU market (France) is also intended to cover markets in other EU countries (Belgium), non-EU countries (Switzerland), and N America (Canada), this means there may be several distributors identified.
In the event that additional information is required above and beyond that contained in the MSDS a local contact person is identified (with contact details). This is the person to whom questions about the MSDS content should be addressed. These people are not expected to provide 24 hr emergency response, but they may reasonably be expected to give a quick reply to queries made during normal working hours
Where the facilities exist, a 24 emergency contact person (or telephone number) is provided.
In an emergency, for example, if a chemical has been accidentally swallowed or splashed into eyes. You should go to your doctor or your local hospital. Make sure you take the bottle of photographic chemical with you to show the doctor the health and safety information on the label. Take the MSDS along as well, if you have one. The doctor may be able to obtain further toxicological details on the product concerned from the poison information centre of your country. Most countries now have such a national poison center, eg. Every European country has, or will soon have such a centre working 24 hours a day ready to help with such problems.
Section 2
This section identifies ingredients in the preparation. Section 2 does not necessarily give a complete breakdown of any product. It only identifies those components which
- are required to be notified by law
- which contribute to the overall chemical hazard classification of the preparation
- or (for example in the case of water), make a ‘significant;’ contribution to the total make up of the preparation
CAS-No - this is Chemical Abstracts Service Registry Number - A unique number assigned to individual chemicals that is used and recognised world wide.
EC No – this is the number by which the substance has been registered in the European Inventory of Existing Chemical Substances (EINECS).
All chemicals used by HARMAN technology Ltd are registered on TSCA (USA), the DSL (Canada) and EINECS/ELINCS (Europe).
Section 11 & 12
These sections contain information about how toxic are the chemicals that were used to make the preparation to animals, fish, etc. and the environment.
LD50 - result of acute toxicity tests on animals. We generally quote data for rats since this is the most widely available. A figure of less than 2000 mg/kg is considered to be hazardous. The lower the number, the more hazardous the chemical.
LC50 - results of acute toxicity tests for fish
IC50 - Immobilisation concentration of daphnia - toxicity data for aquatic life
COD - Chemical Oxygen Demand, an indication of the amount of oxygen that a chemical product would consume in the environment, such as in rivers and lakes. This has an effect on fish and plants, etc. The larger the number, the greater the possible effect on the environment. The relatively small quantities from modern photographic processes and the dilution effect from waste treatment plants, etc., generally renders this effect unimportant for photographic chemicals compared to agricultural chemicals running off fields directly into any rivers or streams, for example.
Section 8
WEL - Workplace Exposure Limits are limits for the concentration of chemicals in the working atmosphere. The concerns here are with dusts and volatile chemicals. In the UK, workplace exposure limits are set by the HSE in a document called EH40. In 2005, the confusing units of measure (OES - Occupational Exposure Standard, and OEL – Occupational Exposure Limits) were replaced by the single WEL. The HARMAN technology Ltd MSDSs have been updated with this new unit of measure.
Where exposure limits are set, these are either quoted as short term (15min), long term (8hrs) or maximum values.
MAK Value - German list of maximum airborne contaminants - German language sheets only
PEL - Permissible exposure level (the term used in the USA)
Section 14
This section gives information about the hazards during transport associated with any given product. In
addition to some similarities with the workplace health and safety bottle label information, corrosion to the metals steel and aluminium are also included here. The chemical in the product giving rise to the transport classification is always stated on the outer transport packaging.
ADR - International carriage of dangerous goods by road
IATA AND ICAO - The organisations and regulations that control the carriage of dangerous goods by air
IMDG - International maritime dangerous goods code for transport by sea
RID - International carriage of dangerous goods by rail
UN NO - United Nations transport code number (used world-wide). These are assigned to single chemicals or groups of chemicals. They are therefore not necessarily unique to a particular chemical.
U.S. DOT - United States Department of Transport
Section 15
DSL - Domestic substances list. The register of chemicals for Canada
NOHSC - National Occupational Health and Safety Commission, Australia
OSHA - Occupational Safety and Health Administration, USA
SARA - Emergency Planning and Community Right-to-Know Act for the USA. This is designed to improve local emergency response capabilities towards hazardous materials and provide the public with information about hazardous chemicals in their community.
TSCA - Toxic Substances Control Act. The register of chemicals for the USA
WHMIS - Workplace Hazardous Materials Information System, Canada
Health & Safety Information for Coated Products
Media Safety Data Sheet (Article Information Sheet)
HARMAN technology black and white photographic films and papers are articles. These are not regarded as a health or environmental hazard under current legislation; these are not subject to the legislation that regulates the supply of dangerous substances and preparations. Safety Data Sheets (MSDSs/SDSs) are not required for the supply of these products nor are these products classified as hazardous for transportation (by any means).
However, HARMAN technology recognises that information such as that which would be expected to be found in a typical Safety Data Sheet is often required by customers. These pages present such information as is available, under the broad categories of composition, toxicity, fire hazards and waste. Information on storage and usage will be found in the technical information that ships with the products.
HARMAN media products are produced by aqueous coating onto various types of film and paper base (opaque or transparent). Black and white films (35mm and 120/220 formats) are coated onto cellulose triacetate. Sheet and other film formats are coated onto polyester (PET). All HARMAN film bases comply with ISO 543:1990. Black and white papers use either baryta (FB) or polyethylene resin coated paper (RC) base.
The bases are then coated with a thin layer(s) of aqueous, light-sensitive silver halide dispersed in gelatin. The base typically comprises 80% to 90% by weight of the total.
HARMAN technology Ltd’s coated film and paper products have not been tested for toxicity. However, on the basis of what we know about what goes into them and how they are made and information that has been published within the imaging industry about similar products, we have no reason to believe that either processed or unprocessed films and papers have any particular toxicity, or indeed represents any hazard that is significantly different to the properties of the media upon which they are coated.
The Fire Classification and Burning Characteristics of HARMAN technology Ltd Media
The purpose of this page is to provide information to guide customers who have specific performance criteria that must be met, to make a product choice that best meets their requirements, and also to provide information to those customers who may have specific information requirements.
The combustibility of HARMAN technology Ltd media products are considered in general terms. The topic of fire classification and how it relates to these products is discussed, and the burning characteristics of HARMAN technology Ltd media are described.
It contains mostly generalised information applicable to the entire HARMAN technology Ltd product range but some limited information applies to specific product categories. It contains no specific data relating to individual products. For individual product data refer to the product technical information/specification.
Under normal conditions, no HARMAN technology Ltd media product is considered to be flammable. i.e. They are not inherently capable of producing a flame, either spontaneously, or with a low energy initiator such as a spark.
All the media which HARMAN technology Ltd supply for producing images, be they photo or digital (inkjet) are combustible. i.e. They will burn when exposed to a sufficient flame and may continue to burn when the initiating flame is removed. Under extreme conditions of very high temperature and when initiated by a direct source of heat, (such as may exist in an existing fire), then the media will char and may develop a flame.
Thus no HARMAN technology Ltd media product is considered to be capable of starting a fire, but they will all be damaged by a fire and they will to a variable extent when subjected to the conditions within a fire, sustain or propagate the flame.
The measurement of this variable capacity to sustain or propagate a flame is called 'Fire Classification'.
Largely driven by the need to ensure that 'safe' materials are used in the building construction industry, and developed and approved independently by many different national standards organisations, there are many different test methods which can lead to a classification for the burning characteristics of different materials. There are also regulations which specify what types of materials (or that materials with specific burning characteristics) may be used in different applications.
Except for ANSI/ISO 543:1990 which was developed by the photo industry and details test protocols and specifications for the base materials which have to be met in order for predominantly silver halide materials to be classed as 'safety film', there are no standards which explicitly address the issue of classification of the burning characteristics of imaging/display media. The choice of test protocols and the classification of these products can be a complex process. (Further complicated by the fact that the US, Canada, Australia and all the Western European states have their own (different) test methods and standards).
Within the European Union there has been a harmonisation of test protocols. This has been achieved during the implementation of the Construction Products Directive (89/106/EEC) and this has also given rise to new combustibility and burning characterisation test methods. Among these there are tests which are clearly more appropriate for testing display media.
The new, harmonised (EU) classification set out in EN 13501-1 adopts a single Euro classification scale ranging from A indicating non-combustible through G, indicating rapid burning to F indicating not-tested. This is based upon testing in the most appropriate of several new test protocols, among which the one which is most appropriate for these media is EN ISO 11925-2.
EN ISO 11925-2 is a test of ignitability when subject to direct impingement of a small flame for a fixed period of time to a vertically mounted sample. It includes a measure of the likelihood of any burning drops that fall from the material to spread a fire.
Euro classification is now accepted throughout the EU and is now the most appropriate route for testing these media. Euro classification is an alternative to those diverse national tests described for example, in the UK in standards such as BS 476:1997 and BS 5438 & BS 5867 (the standard for the classification of building materials, and standards for fire resistance of textiles and fabrics; and in France, in NF P 92501-7 (the standard for evaluating the burning behaviour of fabrics which gives rise to the M0-M5, classifications)
Fire Classifications of HARMAN technology Ltd Media
For all of those HARMAN technology Ltd products (mono, colour and inkjet) which are coated on triacetate or polyester base, the base meets the requirements of ANSI/ISO 543:1990 for classification of the product as 'Safety Film'. This means that these are difficult to ignite (after being kept for more than 10 minutes at 300oC), they are slow burning (a 0.08mm thick and 300mm long sample burns for more than 45 seconds), and they contain less than 0.4% nitrogen.
Many HARMAN technology Ltd media are coated on alternative bases (paper, resin coated paper, vinyl and some fabrics). Few of these media have been tested to EN ISO 11925-2. The current classification for nearly all HARMAN technology Ltd media products under EN 13501-1is therefore Euro classification F (not tested).
No HARMAN technology Ltd media product is constructed from materials which are inert to fire, and thus no product is expected to be classified 'non-combustible' (A) in the Euro classification. Consideration of the materials used in the production of display media and a knowledge of their known or expected burning characteristics leads us to conclude that if they were tested, all of these media would fall into the Euro classification combustible classes B, C, D or E.
Burning Characteristics of HARMAN technology Ltd Media
Generally, and for all HARMAN technology Ltd media products, when these are burned in a hot fire with plenty of oxygen (e.g. in an incinerator) these will be completely consumed to produce largely, water and carbon dioxide, together with small amounts of nitrogen oxides and ash. Under these conditions no harmful substances are produced during combustion.
In a cooler fire, with insufficient oxygen with consequent incomplete combustion, all media products will burn slowly and produce a noxious smoke.
The burning characteristics of HARMAN technology Ltd media are largely those of the substrate base material but this is influenced by the presence of the coated layers that are introduced during their conversion into imaging materials, and by any processes that are subsequently used to reveal, modify or stabilise the image. The burning characteristics of the different bases used are:-
Products Coated on Triacetate Base
Most of the HARMAN technology Ltd range of monochrome films comprise a thin layer of silver halide dispersed in gelatin coated onto cellulose triacetate base. Cellulose triacetate meets the requirements of ANSI/ISO 543:1990. It starts to melt at 230oC. In a fire the melting behaviour of triacetate base is a significant factor. Unless these products are mounted onto a rigid and inert support, then they tend to melt away from a flame and this invalidates the application of many of the older fire test protocols. Once it is alight, triacetate can burn vigorously and drop flaming droplets. The coatings applied to photographic products based on triacetate do not significantly affect the burning behaviour of the base but these may contribute to the production of a greater diversity of noxious gases during incomplete combustion.
Products Coated on Polyester Base
A small number of HARMAN technology Ltd monochrome films are coated onto polyester (PET). PET (polyethylene terephthalate) starts to melt at 255-260 oC (at which temperature it starts to decompose) and has a flash point of 440oC. In a fire the softening and melting behaviour of the polyester base is a significant factor. Unless these products are mounted onto a rigid and inert support, then they tend to melt away from a flame and this invalidates the application of many of the older fire test protocols. Once it is alight, PET can burn vigorously and drop flaming droplets. The coatings applied during manufacture of HARMAN technology Ltd film and display products do not significantly effect the burning behaviour, but they may contribute to the production of a greater diversity of noxious gases during incomplete combustion. In general, polyester films are slower burning than triacetate. In a flame spread test the rate of flame spread along a 25.4 mm wide strip of 0.05mm thick PET base was 250-300 mm/min.
Products Coated on Paper Base
Plain paper is used in the manufacture of many HARMAN technology Ltd imaging media. Paper is easily ignited, (the ignition temperature is about 230oC). The burning characteristics of paper are strongly influenced by the paper thickness (thin papers burn faster). The presence of the coated layers can also significantly affect the burning characteristics. Photographic papers coated with a thin layer of gelatin are not significantly different to the uncoated base, but HARMAN technology Ltd nano-pororous media have surface coatings that make them more difficult to ignite, and they burn more slowly than uncoated base.
Products Coated on RC Paper Base
Resin coated paper base is used as the substrate for many imaging media. The resin layer (a thin surface coating of polythene, usually on both sides), imparts robustness and water resistance. In general, RC coated papers are slower burning than the uncoated base.
Products Coated on Textile/Fabric Bases
The nature of the base material used in manufacture of imaging media is now quite diverse, and some media are produced with vinyl, canvas and other fabric bases. Because there is no general requirement for the burning characteristics of these to be tested there is very little data. In general it is to be expected that the burning characteristics of these media will correspond closely to those of the base materials.
Mounting and Lamination
Whether imaging media are mounted onto boards for display purposes, framed behind glass, lacquered for surface protection or combined with other media in any lamination or other surface treatment, then the affect of these processes on the burning characteristics of the image should be considered.
Where it exists, specific data that relates to the fire classification and burning characteristics of specific HARMAN technology Ltd Media is to be found in the product technical information or specification data files. This information is not supplied in Safety Data Sheets. If it is appropriate because there is a specific legislative requirement or a clear business need, then HARMAN technology Ltd will work with our customers to identify more specific requirements for burning characteristics test data. Where it is appropriate we will also seek certification of conformance to any fire standard.
Not withstanding any specific local regulations, HARMAN technology Ltd films and papers should not be considered to be hazardous. When these become waste, these can be disposed of safely in municipal or industrial landfill, or by incineration.
Although HARMAN technology Ltd films and papers can be safely disposed of in these ways, depending on the quantities involved, and especially if you have particularly large quantities to dispose of, it may be worth investigating recycling and silver recovery options.
Chemicals and Processing Solutions
Today, photographic processing technology and environmental care are inseparable. Treatment of waste effluents from processing has become an important issue in good laboratory practice. There are a wide variety of waste treatment systems.
Waste volumes differ between sources. Amateur and home users in the UK should dispose of small amounts of used photographic processing solutions by dilution with plenty of water and washing them down the drain. Do not mix solutions. It is not advisable to dispose of photographic chemicals to a septic tank.
Larger users, professional and commercial operations operate under fast changing and often local legislation. Many authorities prohibit disposal of used chemistry to the sewer. It is usually unacceptable for economic and environmental reasons to dispose of used tank solutions as waste water. This has led to many developments aimed at minimising waste. Tank solutions now use lower concentrations of chemistry and lower replenishment rates. Fixer desilvering which used to be justified solely on the value of the silver collected now also has the additional justification of lowering the levels of silver in waste to avoid punitive pollution charges and fines. Other processing solutions can easily be collected, neutralised and treated by a specialised contractor. Waste handling companies offer collection schemes which guarantee environmentally sound treatment of photochemical waste. Furthermore, your laboratory has different options to reduce the amount of waste - and as a result to reduce costs. The kind of additional treatment that is appropriate will of course depend on your special situation, but these include:
- Separate collection of tank overflow: Developer and fixer overflow have to be collected separately to allow further treatment.
- Fixer overflow contains a moderate amount of silver. Desilvering can either be done by yourself or by a photo waste collector, who will usually refund most of the value of the silver. Many desilvering systems are on the market but not all show the same efficiency. For reasons of economy electrolytic desilvering units are usually the best choice.
- Equipment for reducing volumes of waste solutions: Special equipment is available to reduce waste volumes (evaporation, distillation). Lowering the amount of water yields a smaller amount of more concentrated waste. Before investing in such equipment contact your local waste collector. In many cases a disposal charge is not only based on volume but also on concentration. By concentrating, waste can also become more hazardous and consequently more expensive to dispose of.
- Wash water: Depending on local legislation disposal to the drain may be allowed or restricted to a maximum volume or concentration. From the fixing solution a small amount of silver is transported into wash water. Desilvering is possible using a metal exchange (iron) cartridge or an ion exchange column.
The substances present in effluent generated by the processing of photographic materials vary according to the processes involved. It is therefore important that the user monitors the waste and reduces levels of hazardous components by pre-treatment in order to meet with local regulations. Care should be taken to ensure that no effluent generated from photographic chemical waste is allowed to enter open streams, watercourses or lakes without suitable treatment and approval from the local Utility service provider.
Waste Disposal and Septic Tank Systems
HARMAN technology Ltd does not recommend the disposal of photographic wastes using septic tank systems because this can affect their efficient operation. Septic tank systems are generally designed for domestic waste treatment in rural areas where mains drainage is not available. While they can and do cope with small quantities of household chemicals, it is best to avoid adding chemicals to them. It should also be borne in mind that the liquid run-off from a septic tank could carry contaminants into the environment.
However, it does depend on the size, design, sitting of the system and sensitivity of the local environment, as well as the volume of photo waste compared to other wastes going through the system. In all cases of doubt contact your local Utility service provider for detailed advice.
Alternative waste disposal options for darkroom workers whose property is connected to septic tank systems include:
- Using a licensed waste disposal company
- Contacting your local public (municipal) waste company. These sometimes operate their own waste collection and disposal services.
Some solutions used in photographic or graphics processing are highly acidic or alkaline. The acidity (or alkalinity) of a solution can be expressed in terms of its pH value, with pH <7 being acidic and solutions with pH >7 alkaline. Local water companies set control limits on pH values, (usually between pH 5.5 and pH 10.0), within which discharged effluents must comply. ILFORD Photo developers, for black and white are generally in the range pH 8-10.5. These solutions should be neutralised before disposal. Neutralisation can be effected by adding developer TO fixer whilst stirring. It is best to have slightly more developer than fixer. Silver should be removed from fixers prior to this mixing to avoid difficulties in recovery. Always do such operations in well ventilated areas and wear the appropriate safety equipment.
The oxygen demand (COD, BOD) of an effluent characterises the chemistry content and its degradability. A high COD (chemical oxygen demand) or BOD (biological oxygen demand) value means a high concentration of chemicals. Used tank solutions contain a high concentration of biodegradable chemicals and therefore have high COD and BOD values. Because of a possible impact on the environment through removal of oxygen, they are not recommended for disposal directly to drains. Photographic wash water CODs are low enough to be safely handled by your water treatment plant.
In many areas photo labs need a permit to discharge to sewers. It is important that water treatment plants know what quantities of chemicals are present in waste and from what kind of users they have been produced. Applying for a permit to discharge helps the water treatment plant to run its process in optimal conditions. Contact your Local Trade Effluent Regulator to see if a permit is required.
The recovery of silver is one method of treatment that should be considered essential not only from an environmental point of view but for the protection of a valuable resource.
Silver can be recovered from processing solutions by a variety of methods, three of which are covered below:
Metal exchange is the cheapest form of silver recovery available, and is suited to the small volume users on a tight budget.
The method involves exchange of metal, usually iron in the form of steel wool, with silver releasing the iron into the wash water. Steel wool however is not very efficient because over a period of time it breaks down, collapses and the silver deposited becomes a sludge. The wash water also appears brown from the waste iron produced, which is not only unsightly but is also restricted in some areas. Several manufacturers market cartridges or drums packed with steel wool for silver recovery. HARMAN technology Ltd testing has found this method to be very successful at keeping silver levels at around 20ppm, but not below 5ppm on a reliable basis Cartridges containing finely-divided iron are the most efficient. If two of these are used one after another it should be possible to reach silver levels under 5ppm. For black and white processes it is an inefficient method for wash water alone - the steel wool rapidly rusts - but for waste containing fixer (which prevents the steel wool from rusting) it works well.
This method is more expensive than metal exchange. It is only used for removing low concentrations of silver from waste, eg from wash water; fix waste is too concentrated in silver for this method to be used.
The ion exchange system, suitable for all sizes of business, involves passing wash water through a bed of ion exchange resin to enable the silver to exchange sites with the resin. The resin needs to be regenerated after prolonged use to prepare the ion-exchange sites for further silver recovery.
Once the resin has become saturated with silver it must be sent to a refinery for silver recovery. Commercial units claim to desilver down to 0.5ppm.
This can be the most efficient method and is less expensive than ion exchange. Some commercial units can remove silver from waste fixer and from combined fix/wash water from a level of 6.5g/l silver down to 3ppm (meeting the silver limit in many parts of the world). However, many units would be unable to decrease silver levels below 50ppm. Ion exchange or metal exchange of the liquid residue from the unit would then be needed to reduce the silver to an acceptable level.
The method involves electroplating silver onto a cathode, usually made of stainless steel. The silver, of up to 98% purity, can be scraped off at intervals. Historically, equipment has not been able to avoid breaking down the fixer (sulphiding) when the silver concentration becomes very low. Breakdown of the fixer leads to silver sulphide being deposited on the cathode which impairs further silver recovery. Hazardous hydrogen sulphide gas (bad eggs smell) can also be given off if electrolysis is too vigorous.
In electrolytic silver recovery systems, two types of electrode may be used, the stationary electrode or the rotating electrode. In a unit employing a stationary electrode, agitation of the solution to enable even desilvering of fixer is achieved by recirculating pumps. Without agitation, a fixer solution would end up with the area nearest the cathode becoming desilvered and the areas furthest away left unelectrolysed. A further disadvantage would be that the solution nearest the cathode would eventually degrade to silver sulphide and hydrogen sulphide.
In units using the rotating electrode, the cathode rotates via a central pivot, causing even desilvering of fixer. In such desilvering units there are moving parts involved which can wear out and this is sometimes seen as a disadvantage.
There are two ways of desilvering fix - either batch wise or continuously (as in recycling).
Batch wise desilvering of exhausted fixer involves vigorous electrolysis to remove as much silver as possible in the shortest possible time without decomposing the fixer.
The use of fixer recycling equipment can reduce replenishment rates by up to 75% and give savings on chemicals and waste disposal. These savings are achievable using normal fixers, such as ILFORD 2000RT, or HYPAM just by using the extra capacity that we have built into the products to give you a very tolerant product.
Continuous desilvering, (in-line desilvering coupled with fixer recycling), involves gentle electrolysis to maintain silver at a constant level without affecting fixer activity. Fixer recycling requires monitoring of thiosulphate and sulphite concentrations because these are affected by electrolysis and will decompose.
If you use recycling you will need to control your processes much more carefully than is otherwise required. It is suggested that you try using the 50% level to start with.
Please note that fixer recycling is very dependent on the equipment that is used, the way it is set up and the careful monitoring of the process in order for it to be successful. If not operated properly, film and print stability can be affected. You may not see an effect immediately but your customers may see problems arising after weeks or months.
Hydroquinone (present in virtually all developers for black & white photography decomposes irreversibly with time to form oxidation products, making the scope for developer recycling small. The combination of reduced replenishment rates (which is the aim of all manufacturers) and developer recycling increases the tendency for a brown sludge to form in the processor tank. HARMAN technology Ltd does not recommend the recycling of developers for photographic processing systems.
Wash water is a business cost twice over - once coming into your premises and again as a waste leaving your processing area. In addition, if you are using heated water the cost of heating can be high too.
The cost of buying water can be high, (typically around £1.00/m3 or per 1000 litres) 2006), particularly if you are on a meter and you have processing machines running continuously. ILFORD machines typically use water at a rate of 4 litres per minute (240 litres an hour).
Wash water recycling is best suited to the larger user, and has obvious advantages in those countries where effluent disposal is very carefully controlled or restricted. The advantages of this system are:
- Silver recovery by ion exchange of the 10% or more silver lost from photo processing wash water; claims of 90% efficiency are made depending of system used.
- Large quantities of water used for photo processing can be reused, a saving of 66% on mains water consumption (and water plant treatment costs).
- The wash water returning to the processor is at a higher temperature than tap water and can result in energy savings of over 45% by not having to heat up the wash water.
- Elimination of trace quantities of heavy metals, pollutants, and removal of silver down to less than 0.5ppm levels.
Wash water recycling is not suitable for the small user, but as regulatory controls tighten and the need for vigilance over what goes down the drain increases, recycling will become more popular and economic for larger users.
Wash water contains contamination from 2 sources - the film or paper and the fixer tank, which is always before it in the process. The chemicals that are carried over from the fixer are the most important ones for calculations of levels of chemicals in wash water. The chemicals from the film or paper, by this stage in the process, are so small that they can effectively be ignored.
So how much and what is carried over from the fixer tank into the wash tank?
Silver is the main contaminant and the level will depend on a number of things. Throughput (amount of material processed each day) determines the silver load going into the fixer.
The fixer replenishment rate determines the resulting silver level in the fixer tank, in the absence of fixer recycling. If the replenishment rate is halved the silver level in the fixer will double. This in turn means that twice the amount of silver will transfer into the wash water tank.
It is important to control the silver level in fixers because if it rises too high it will slow fixing down so much that problems with print or negative stability will result.
An example of the amount of fixer carried over with ILFORD black and white processing machines is between 20 and 40ml for each square metre of paper processed.
For ILFORD black and white processing machines a typical silver level in wash water is a few parts per million (ppm).
In actual fact the calculation of silver in the wash tank is not simple. It depends on the water flow rate and the amount of silver that has already been carried into the wash tank. For example, doubling the wash water flow rate will halve the amount of silver in the wash tank.
If 50% wash water recycling is used the silver level will be doubled. Consequently, it may be necessary to ensure that your system is capable of removing some of this silver. For working with such low levels of silver an ion exchange resin system will probably be required. These can reduce the silver level and when the resin cartridge is exhausted the silver can be recovered.
Evaporation is not widely used. It is particularly important for those users who are required to pay for disposal of all wastes, including wash waters. However, the highly concentrated waste may be classified as 'Toxic Waste' by the disposal company (and its licensing authorities) under the local waste regulations. This method should therefore only be used after seeking advice.
There are two types of evaporators available, atmospheric or vacuum.
Atmospheric
These consist of an evaporation pot incorporating a heating element and a thermostat. The temperature in the pot is kept below 60°C to avoid unwanted emissions. These evaporators vent the water vapour produced into the atmosphere through an exhaust pipe. This can be fitted with a charcoal scrubber to clean up the exhaust vapour. This type of evaporator is relatively cheap and easy to operate but consideration must be given to the type of exhaust vapours produced, such as ammonia, and the amount of energy needed to evaporate the waste liquids. Use with caution because of the potential exhaust gas hazard.
Vacuum and distillation
These types of evaporator have a vacuum source as well as an evaporation chamber. Some are heated electrically but others use waste heat generated from the cooling coil to save energy. A vacuum source means that evaporation occurs at a lower temperature and reduces the tendency for noxious gases to be produced. The solid waste or liquid slurry end product can be sent away for disposal whilst the pure liquid distillate can often go down the drain or be used to make up new fixer; it should not be used to make up developer or developer replenisher solutions.
Paper
Fibre based papers require washing in running water at 18°C to 24°C for 60 minutes (double weight) or 30 minutes (single weight). Washing times should be extended if the water temperature is much lower than this range.
The amount of water required can be considerably reduced, through the use of ILFORD GALERIE WASHAID and print permanence enhanced through the use of the ILFORD optimum permanence sequence. For example, for double weight MULTIGRADE IV FB an 85% saving on water consumption can be achieved using this sequence
ILFORD optimum permanence sequence
Fixing - ILFORD HYPAM (1+4), intermittent agitation, (do not use hardener) 1 minute
First Wash - Good supply of fresh, running water 5 minute
Rinse - WASHAID intermittent agitation 10 minute
Final Wash - Good supply of fresh, running water 5 minute
Processing conditions: 18-24°C including wash water
Film
Where a non-hardening fixer, such as HYPAM, has been used, washing the film in running water for 5-10 minutes at a temperature within 5°C of the processing temperature is required.
For spiral tank use, when a non-hardening fixer has been used, the following method of washing is recommended which uses less water yet still gives negatives of archival permanence.
- Process the film in a spiral tank.
- Fix it using ILFORD HYPAM fixer.
- After fixation, fill the tank with water at the same temperature as the processing solutions, and invert it five times.
- Drain the water away and refill. Invert the tank ten times.
- Drain and refill it for the third time and invert the tank twenty times. Drain the water away.
A final rinse in water to which a few drops of ILFORD ILFOTOL wetting agent has been added will aid rapid and uniform drying.
Using this sequence will result in water savings of over 85% compared with using continuous running water.
Use of Hardener
Hardeners should only be used in fixers to prevent mechanical damage of films and reduce drying times in processing machines. They should not be used for black and white paper processes. When used with black and white film products the washing time must be increased considerably to ensure complete washing.
Incomplete washing will produce prints or negatives that will degrade with time.