MSDS Citric Acid Monohydrate

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Safety Data Sheet

according to 1907/2006/EC, Article 31
Printing date 05.01.2017 Version number 1 Revision: 05.01.2017
SECTION 1: Identification of the substance/mixture and of the company/undertaking

1.1 Product identifier
Trade name: Citric Acid Anhydrous
Monohydrate
CAS number:
5949-29-1
77-92-9
EC number:
201-069-1
REACH registration number: 01-2119457026-42-0020
1.2 Relevant identified uses of the substance or mixture and uses advised against
Application of the substance / the preparation:
Intermediate
Formulation
Detergents and cleaning products
Agricultural applications
Personal care products
Paper industry
Construction products
Polymers and plastics
Oil industry
Textile industry
Paints and coatings
Photography products
Laboratory reagents
Water treatment
Treatment of metal surfaces
Medical devices
1.3 Details of the supplier of the safety data sheet
Manufacturer/Supplier:
RZBC (JUXIAN) CO., LTD.
NO. 209, LAIYANG ROAD (WEST SIDE OF NORTH CHENGYANG ROAD),
JUXIAN ECONOMIC DEVELOPMENT ZONE, RIZHAO CITY, SHANDONG PROVINCE CHINA
Tel: 0086 633 2163576
Fax: 0086 633 2163500
E-mail: [email protected]
Further information obtainable from:
B-Lands Consulting
WTC, 5 Place Robert Schuman, BP 1516
38025 Grenoble, FRANCE
Tel: +33 476 295 869
Fax: +33 476 295 870
Email: [email protected]
www.reachteam.eu
1.4 Emergency telephone number(s):
NHS Direct: 111 (England and Scotland), 0845 46 47 (Wales).
National Poisons Information Service (NPIS): 0344 892 0111 (healthcare professionals only).
Ireland - National Poisons Information Centre: 01 837 9964 or 01 809 2566 (healthcare professionals only).
SECTION 2: Hazards identification
2.1 Classification of the substance or mixture
Classification according to Regulation (EC) No 1272/2008
Eye Irrit. 2 H319 Causes serious eye irritation.
2.2 Label elements
Labelling according to Regulation (EC) No 1272/2008:
The substance is classified and labelled according to the CLP regulation.
(Contd. on page 2)
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Monohydrate
(Contd. of page 1)
Hazard pictograms:
GHS07
Signal word: Warning

Hazard statements:
H319 Causes serious eye irritation.
Precautionary statements:
P264 Wash thoroughly after handling.
P280 Wear protective gloves/protective clothing/eye protection/face protection.
P305+P351+P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if
present and easy to do. Continue rinsing.
P337+P313 If eye irritation persists: Get medical advice/attention.
2.3 Other hazards
Results of PBT and vPvB assessment
PBT: No PBT.
vPvB: No vPvB.
SECTION 3: Composition/information on ingredients
3.1 Substances
CAS Number. Description.
5949-29-1
77-92-9 Citric
Citric Acid
Acid Monohydrate
Anhydrous
Identification number(s)
EC number: 201-069-1
SECTION 4: First aid measures
4.1 Description of first aid measures
After inhalation: Move patient to fresh air, if symptoms persist consult a doctor.
After skin contact: If skin irritation continues, consult a doctor.
After eye contact:
Rinse opened eye for several minutes under running water. If symptoms persist, consult a doctor.
After swallowing:
Rinse out mouth and then drink plenty of water.
Do not induce vomiting; call for medical help immediately.
4.2 Most important symptoms and effects, both acute and delayed
Serious eye damage/eye irritation: Eye Irrit. 2
4.3 Indication of any immediate medical attention and special treatment needed
No further relevant information available.
SECTION 5: Firefighting measures
5.1 Extinguishing media
Suitable extinguishing agents:
CO2, powder or water spray. Fight larger fires with water spray or alcohol resistant foam.
5.2 Special hazards arising from the substance or mixture
Carbon dioxide (CO2)
Carbon monoxide (CO)
(Contd. on page 3)
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Safety Data Sheet

Monohydrate
(Contd. of page 2)
5.3 Advice for firefighters
Protective equipment:
Wear fully protective suit.
Wear self-contained respiratory protective device.
SECTION 6: Accidental release measures
6.1 Personal precautions, protective equipment and emergency procedures
Use personal protective equipment.
Ensure adequate ventilation.
Wear eye protection .Avoid contact with skin and eyes.
6.2 Environmental precautions
Do not allow to enter sewers/ surface or ground water.
No special measures required.
Prevent further leakage or spillage if safe to do so.
6.3 Methods and material for containment and cleaning up
Send for recovery or disposal in suitable receptacles.
Retrieve the product by mechanical means.
Dispose contaminated material as waste according to item 13.
Pick up and transfer to properly labelled containers. After cleaning, flush away traces with water.
6.4 Reference to other sections
See Section 7 for information on safe handling.
See Section 8 for information on personal protection equipment.
See Section 13 for disposal information.
SECTION 7: Handling and storage
7.1 Precautions for safe handling
Avoid breathing vapours.
Do not get in eyes, on skin, or on clothing.
Use only in well ventilated areas.
Provide suction extractors if dust is formed.
Do not inhale dust / smoke / mist.
Information about fire - and explosion protection: No special measures required.
7.2 Conditions for safe storage, including any incompatibilities
Requirements to be met by storerooms and receptacles:
Store in a cool and dry place.
Provide ventilation for receptacles.
Store only in the original receptacle.
Information about storage in one common storage facility: Store away from oxidising agents.
Further information about storage conditions: Keep container tightly sealed.
7.3 Specific end use(s): No further relevant information available.
SECTION 8: Exposure controls/personal protection
8.1 Control parameters
Ingredients with limit values that require monitoring at the workplace: Not required.
PNECs
PNEC 0.44 mg/L (Water (Freshwater))
0.044 mg/L (Water (Marine Water))
>1000 mg/L (Sewage Treatment Plant (STP))
PNEC 3.46 mg/kg sedim. dw (Sediment (Marine Water))
34.6 mg/kg sedim. dw (Sediment (Freshwater))
(Contd. on page 4)
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Monohydrate
(Contd. of page 3)
PNEC 33.1 mg/kg soil dw (Soil)
Additional information: The lists valid during the making were used as basis.
8.2 Exposure controls
Personal protective equipment
General protective and hygienic measures:
Do not eat, drink, smoke or sniff while working.
Keep away from foodstuffs, beverages and feed.
Immediately remove all soiled and contaminated clothing
Wash hands before breaks and at the end of work.
Avoid contact with the eyes.
Avoid contact with the eyes and skin.
Respiratory protection: Suitable respiratory protective device recommended.
Protection of hands:
The glove material has to be impermeable and resistant to the product/ the substance/ the preparation.
Due to missing tests no recommendation to the glove material can be given for the product/the preparation/
the chemical mixture.
Select the glove material based on a consideration of the penetration times, rates of diffusion and the
degradation.
Material of gloves:
Rubber, PVC or neoprene gloves recommended.
The selection of the suitable gloves does not only depend on the material, but also on further marks of
quality and varies from manufacturer to manufacturer.
Penetration time of glove material:
The determined penetration times according to EN 374 part III are not performed under practical
conditions. Therefore a maximum wearing time, which corresponds to 50% of the penetration time, is
recommended.
The exact break through time must be determined by the manufacturer of the protective gloves.
Eye protection:
Tightly sealed goggles (EN 166).
Body protection: Protective work clothing.

SECTION 9: Physical and chemical properties
9.1 Information on basic physical and chemical properties
General Information
Appearance:
Form: Solid.
Crystalline
Colour: White.
Odour: Odourless.
Odour threshold: Not determined.
pH-value (100 g/l) : 1.7
Melting point/Melting range: 153 °C
Boiling point/Boiling range: Decomposes before boiling
Flash point: Not applicable.
Flammability (solid, gaseous): Product is not flammable.
(Contd. on page 5)
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Monohydrate
(Contd. of page 4)
Ignition temperature: Not applicable.
Decomposition temperature: Not determined.
Danger of explosion: Product does not present an explosion hazard.
Explosion limits:
Lower: Not determined.
Upper: Not determined.
Oxidising properties None.
Vapour pressure at 25 °C: 2.21*10-6 Pa
Density: Not determined.
Relative density at 20 °C 1.665
Vapour density Not applicable.
Evaporation rate Not applicable.
Solubility in / Miscibility with
Water at 20 °C: 590 g/l
Alcohols: Partly soluble.
Partition coefficient (n-octanol/water): -0.2 to -1.8 log POW
Viscosity:
Dynamic: Not applicable.
Kinematic: Not applicable.
9.2 Other information No further relevant information available.
SECTION 10: Stability and reactivity
10.1 Reactivity No data available.
10.2 Chemical stability
Thermal decomposition / conditions to be avoided:
Stable up to melting point.
Keep away from heat and direct sunlight.
10.3 Possibility of hazardous reactions Reacts with alkali (lyes).
10.4 Conditions to avoid Strong oxidizing agents.
10.5 Incompatible materials
Protect from moisture.
Avoid strong oxidants, strong alkalis and strong acids.
Sodium nitrite, potassium nitrite
10.6 Hazardous decomposition products
Carbon dioxide
Carbon monoxide
SECTION 11: Toxicological information
11.1 Information on toxicological effects
Acute toxicity Based on available data, the classification criteria are not met.
LD/LC50 values:
Oral LD50 5400 mg/Kg bw (Mouse) (OECD 401)
Dermal LD50 >2000 mg/Kg bw (Rat) (OECD 402)
Primary irritant effect:
Skin corrosion/irritation: Based on available data, the classification criteria are not met.
(Contd. on page 6)
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Monohydrate
(Contd. of page 5)
Serious eye damage/irritation:
Causes serious eye irritation.
Respiratory or skin sensitisation: Based on available data, the classification criteria are not met.
CMR effects (carcinogenity, mutagenicity and toxicity for reproduction):
Germ cell mutagenicity: Based on available data, the classification criteria are not met.
Carcinogenicity: Based on available data, the classification criteria are not met.
Reproductive toxicity: Based on available data, the classification criteria are not met.
STOT-single exposure: Based on available data, the classification criteria are not met.
STOT-repeated exposure: Based on available data, the classification criteria are not met.
Aspiration hazard: Based on available data, the classification criteria are not met.
SECTION 12: Ecological information
12.1 Toxicity
Aquatic toxicity:
LC50/48h 440 mg/L (Fish) (OECD 203)
NOEC 425 mg/L (Algae)
LC50/24h 1535 mg/L (Daphnia Magna)
12.2 Persistence and degradability Easily biodegradable

12.3 Bioaccumulative potential Does not accumulate in organisms.
12.4 Mobility in soil pKa: 3.13, 4.76 and 6.4 at 25 °C
Additional environmental information:
General notes:
Water hazard class 1 (German Regulation) (Self-assessment): slightly hazardous for water
Do not allow undiluted product or large quantities of it to reach ground water, water course or sewage
system.
12.5 Results of PBT and vPvB assessment
PBT: No PBT.
vPvB: No vPvB.
12.6 Other adverse effects No further relevant information available.
SECTION 13: Disposal considerations
13.1 Waste treatment methods
Recommendation: Do not allow product to reach sewage system.
Uncleaned packaging:
Recommendation:
Disposal must be made according to official regulations.
Packaging that may not be cleansed must be disposed of in the same manner as the product.
SECTION 14: Transport information
14.1 UN Number
ADR, ADN, IMDG, IATA Not applicable.
14.2 UN proper shipping name
ADR, ADN, IMDG, IATA Not applicable.
14.3 Transport hazard class(es)
ADR, ADN, IMDG, IATA
Class Not applicable.
14.4 Packing group
ADR, IMDG, IATA Not applicable.
(Contd. on page 7)
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Monohydrate
(Contd. of page 6)
14.5 Environmental hazards
Marine pollutant: No
14.6 Special precautions for user Not applicable.
14.7 Transport in bulk according to Annex II
of MARPOL 73/78 and the IBC Code Not applicable.
SECTION 15: Regulatory information
15.1 Safety, health and environmental regulations/legislation specific for the substance or
mixture
This safety data sheet complies with the requirements of Regulation (EC) No. 1907/2006.
15.2 Chemical safety assessment A Chemical Safety Assessment has been carried out.
SECTION 16: Other information
This information is based on our present knowledge. However, this shall not constitute a guarantee for any
specific product features and shall not establish a legally valid contractual relationship.
Abbreviations and acronyms:
ADR: Accord européen sur le transport des marchandises dangereuses par Route (European Agreement concerning the
International Carriage of Dangerous Goods by Road)
IMDG: International Maritime Code for Dangerous Goods
IATA: International Air Transport Association
GHS: Globally Harmonised System of Classification and Labelling of Chemicals
EINECS: European Inventory of Existing Commercial Chemical Substances
CAS: Chemical Abstracts Service (division of the American Chemical Society)
PNEC: Predicted No-Effect Concentration (REACH)
LC50: Lethal concentration, 50 percent
LD50: Lethal dose, 50 percent
Eye Irrit. 2: Serious eye damage/eye irritation – Category 2
43.0
Annexes I. Exposure scenarios
M1 – Manufacturing
IU1 – Industrial use as chemical intermediate
IU2 – Formulation into preparations at industrial site
IU3 – Industrial, professional and consumer use in personal care
IU4 – Industrial, professional and consumer use in cleaning products
IU5 – Industrial use in production of paper
IU6 – Industrial, professional and consumer use in construction products
IU7 – Industrial use in production of polymers and plastics
IU8 – Industrial use in the oil industry
IU9 – Industrial use in the textile industry
IU10 – Industrial, professional and consumer use in paints and coatings
IU11 – Professional and consumer use in photography
IU12 – Industrial use in laboratory reagents
IU13 – Industrial use in water treatment
IU14 – Industrial use in treatment of metal surfaces
IU15 – Industrial, professional and consumer use in agricultural applications
IU16 – Industrial and consumer use in medical devices
Citrates Consortium 1 FINAL VERSION JULY 2010

9.1 ES1: Production of citric acid
9.1.1 Exposure scenario
9.1.1.1 Description of activities and processes covered in the exposure scenario
Citric acid production is largely by microbiological fermentation of molasses and sugar

solutions. Extraction from lemon juice or chemical synthesis is possible but rarely used.
Dilute citric acid from filtered fermentation broths is precipitated as practically insoluble
calcium citrate by addition of calcium hydroxide. The calcium citrate is then reacted with
sulfuric acid to form citric acid and calcium sulphate.
In a typical process for the production of citrate salts, citric acid is dissolved in deionised
water. Addition of a source of the other ion results in conversion of citric acid to its salt. The
salt is separated by evaporation and centrifugation, then dried, sieved and bagged.
A generic approach to production is used, based on a maximum site size of 10,000 tonnes per
year. Such a site can produce citric acid or its salts. Only the tonnage destined for REACH-
relevant applications is considered; material manufactured for uses that are exempt from
REACH, such as food and pharmaceuticals, are not included.
Manufacture takes place at industrial sites in batch or continuous processes with limited
opportunities for exposure (PROCS 1, 2, 3, 4). Loading/unloading operations at dedicated
facilities (PROC8b) are also covered by the scenario.
9.1.1.2 Operational conditions related to frequency, duration and amount of use
Table 9.3: Duration, frequency and amount

Information type Data field Explanation
Used amount of substance per day 30 tonnes

Duration of exposure per day at >4 hours (all PROCs) REACH default used as a worst-case;
workplace [for one worker] actual exposure times may be
significantly less.
Frequency of exposure at workplace Once per day
[for one worker]
Annual amount used per site 10,000 tonnes
Emission days per site 350
9.1.1.3 Operational conditions and risk management measures related to product

characteristics
There is a risk of dust explosion, particularly for fine powder grades. Therefore, build-up of
dust is avoided and precautionary measures against electrostatic discharge are taken. LEV and
respiratory protection are used in areas where workers may come into contact with dust.

Table 9.4: Characteristics of the substance or preparation
Physical state Solid. Various powder

and crystalline grades are
available.
Risk management measures related to Precautions against dust See text
the design of product explosion and irritation
caused by dust
inhalation.
9.1.1.4 Operational conditions related to available dilution capacity and

characteristics of exposed humans
Table 9.5: Operational conditions related to respiration and skin contact

Respiration volume under conditions 10 m3/d Default for workers, light activity
of use
Area of skin contact with the ECETOC TRA default:

substance under conditions of use
240 cm2 PROC 1: palm of one hand
480 cm2 PROC 2: palms of both hands
240 cm2 PROC 3: palm of one hand
480 cm2 PROC4: palms of both hands
480 cm2 PROC8b: palms of both hands
Body weight 70 kg Default
Environmental surroundings characteristics

Dilution factor: 40 (default for large industrial site).
9.1.1.5 Other operational conditions of use
No measured data are available for releases of citric acid to air and waste water for the generic
production site. Releases are therefore estimated on the basis of other information.
Releases to air
Due to the very low vapour pressure of the key intermediates and of citric acid itself, losses to
air are considered to be zero.
Releases to waste water
The key production stage is the precipitation of calcium citrate. This substance is of low
solubility, although a small quantity of citric acid could remain dissolved, a fraction of
0.0001, or 2.86 kg/d over 350 days.

There could be losses during handling and packaging processes, but when around 30 tonnes
per day are handled these processes are highly automated. It can be anticipated that occasional
spillages can occur due to small levels of leakage, amounting to at most 1 kg per day passing
to aqueous waste.
The total passing to aqueous waste water is 3.86 kg/d.

Table 9.6: Technical fate of substance and losses from process/use to waste, waste water and
air
Fraction of applied amount lost from 0 kg/kg See text
process/use to waste gas
Fraction of applied amount lost from 0.0001 kg/kg See text
process/use to waste water
9.1.1.6 Risk management measures
Table 9.7 summarises the risk management measures in place during production of citric acid.
Processes take place under controlled conditions with opportunities for manual handling
minimised. Good working practices such as minimisation of splashes and spills, avoidance of
contact with the substance or contaminated objects, regular cleaning of equipment and work
area, good personal hygiene, staff training and management/supervision are in place.
Table 9.7: Risk management measures for industrial site

Containment and local exhaust ventilation

Containment plus good work Yes
practice required
Local exhaust ventilation required Yes Typical practice of chemical
plus good work practise industry. Not applicable for
PROC1.
Personal protective equipment (PPE)
Skin protection Protective gloves
Eye protection Safety glasses
Respiratory protection Dust mask. In case of open
handling of larger quantities
or accidental release:
particle mask or respirator
with independent air supply
Clothing Working clothing worn.
Other risk management measures related to workers
N/A
Risk management measures related to environmental emissions from industrial sites
Onsite pre-treatment of waste water Yes Neutralisation
Resulting fraction of initially On-site biological waste treatment
applied amount in waste water is expected to remove a high
released from site to the external proportion of citric acid, as the

sewage system substance is highly biodegradable.

Air emission abatement No measured data
Resulting fraction of applied amount No measured data
in waste gas released to
environment
Onsite waste treatment No measured data Secondary biological treatment
Fraction of initially applied amount
sent to external waste treatment.
This is the sum of direct losses from
processes to waste, and the residues
from onsite waste water and waste
gas treatment. No measured data
Municipal or other type of external
waste water treatment None None
Effluent (of the waste water
treatment plant) discharge rate 1 x 107 l/d Default for a large industrial site
Recovery of sludge for agriculture Dried sludge may be sold as an
or horticulture Yes approved agricultural fertiliser
9.1.1.7 Waste related measures
Solid wastes may be disposed of via landfill or incineration, or are recycled outside of the
process. Dried sludge from on-site waste water treatment plants may be sold as approved
agricultural fertiliser.
Details of the treatment of aqueous waste vary at different sites but as a minimum, wastes are
neutralised and the effluent treated in on- or off-site secondary biological treatment plants
prior to discharge.
Waste gases are not generated.
9.1.2 Exposure estimation
9.1.2.1 Workers exposure
9.1.2.1.1 Acute/Short term exposure
Workers at the production site are routinely involved with the same tasks, therefore it is more
appropriate to consider long-term exposure, and short-term exposure is not quantified.

9.1.2.1.2 Long-term exposure
Table 9.9 gives a summary of the long-term exposure values for PROCs 1, 2, 3, 4 and 8b,
based on the ECETOC TRA model. Defaults for duration of exposure (>4 hours) and use of
LEV (no for PROC 1, yes for PROCs 2, 3, 4, 8b) have been used. It has been assumed that
respiratory protection is not used; where this is not the case, actual exposure may be much
lower. Durations of exposure may also be less than 4 hours and in this case the following
modifications factors can be applied: 0.6 for 1-4 hours, 0.2 for 15 mins to 1 hour, 0.1 for <15
mins.
Inhalation exposure
Based on the vapour pressure (negligibly low) and physical state (aqueous solution), aqueous
formulations of citrates fall into the ‘minimal’ availability band (ECETOC 2009), and the
potential for exposure is minimal to low (ECETOC 2009). Inhalation exposure for aqueous
products is expected to be negligible as citric acid and its salts are extremely involatile with
vapour pressures <10-5 Pa and negligibly small Henry’s Law constants, indicating there is no
potential for exposure via vapour.
The exceptions are where there is a possibility for inhalatory exposure via spray mists. In
addition, use of dusty powder forms of citric acid and citrate salts may result in inhalation
exposure.
Citric acid is a solid and during production, it may be handled in solid form. Citric acid is
available in a range of particle size grades, from granular to fine powders. Therefore, a worst
case scenario is that the substances are very dusty. This is defined as ‘high fugacity’ in the
ECETOC TRA worker model. This is considered as worst case scenario for workers
exposure.
Dermal exposure
Dermal uptake of citrate is expected to be minimal as it is extremely hydrophilic with a very

low octanol-water partition coefficient (-1.8 to -0.12). The USEPA DERMWIN model allows
for uptake from aqueous solution to be calculated on the basis of a proportion of the worst-
case calculated by ECETOC TRA. This approach is indicated in the ECETOC (2004).
A worst-case estimate for the uptake fraction from aqueous solution has been calculated as
0.006 (see Section 5.1); actual uptake is expected be much less. The dermal exposure
estimated using ECETOC TRA and presented in Table 9.8 may be multiplied by this factor to
obtain a worst-case estimate of the dermal exposure. Dermal uptake of solid citrates is
expected to be negligible and is not considered.

Table 9.8: Dermal exposure estimates (based on ECETOC TRA model)
Exposure Process Description LEV Dermal Predicted Exposed Dermal
scenario category present? exposure? exposure skin exposure
(µg/cm2/day) surface
area (mg/kg/day)a
(cm2)
Industrial PROC1 Use in closed Nob Yes 100 240 0.3

use process, no
likelihood of
exposure
PROC2 Use in closed, Yes Yes 20 480 0.14

continuous
process with
occasional
controlled
exposure (e.g.
sampling)
PROC3 Use in closed Yes Yes 10 240 0.03

batch process
(synthesis or
formulation)
PROC4 Use in batch Yes Yes 100 480 0.69

and other
process
(synthesis)
where
opportunity for
exposure arises
PROC8b Transfer Yes Yes 100 480 0.69

from/to large
vessels
(dedicated)
a) Calculated assuming a default bodyweight of 70 kg for worker. b) In the ECETOC TRA model, LEV is not
considered relevant for PROC1.

Table 9.9: Inhalation exposure estimates (based on ECETOC TRA model)
Exposure Process Description LEV LEV Predicted Predicted Inhalation

scenario category present? efficiency exposure (ppm) exposure (mg/m3)c exposure
(mg/kg/day)d
Industrial use PROC1 Use in closed process, no likelihood of Nob - 0.001 0.01 0.001
exposure
PROC2 Use in closed, continuous process with Yes 90% 0.01 0.1 0.01
occasional controlled exposure (e.g.
sampling)
PROC3 Use in closed batch process (synthesis or Yes 90% 0.01 0.1 0.01
formulation)
PROC4 Use in batch and other process (synthesis) Yes 90% 0.31 2.5 0.36
where opportunity for exposure arises
PROC8b Transfer from/to large vessels(dedicated) Yes 95% 0.16 1.25 0.18
b) In the ECETOC TRA model, LEV is not considered relevant for PROC1. c) Results are calculated as mg/m3 for solids and ppm for non-solids d) Calculated assuming a default bodyweight of
70 kg for workers and a default respiratory volume of 10 m3, light activity, for an 8 hour work shift

Table 9.10: Summary of long-term exposure concentration to workers
Routes of exposure Concentrations Justification
Dermal local
ECETOC TRA prediction for PROC8b, multiplied by an uptake
exposure 0.6
factor of 0.006.
(in µg/cm2)
Dermal systemic
exposure 0.004
factor of 0.006.
(in mg/kg bw/d)
Inhalation exposure
(in mg/m3)/8h 2.5 ECETOC TRA prediction for PROC8b
workday
Inhalation exposure
(in mg/kg/d)/8h 0.36 ECETOC TRA prediction for PROC8b
workday
9.1.2.2 Consumer exposure
Consumer exposure is not applicable to chemical manufacturing.
9.1.2.3 Indirect exposure of humans via the environment (oral)
Exposure of humans to citric acid via the environment is not significant, as the substance is
readily biodegradable.
9.1.2.3.1 Environmental exposure
9.1.2.3.2 Environmental releases
Predicted environmental release estimates have been used for releases during production. No
measured data are available for the concentration of citric acid in any environmental
compartment. The releases have been estimated using the exposure scenario for production
(section 9.1.1.2 and 9.1.1.6) and Predicted Environmental Concentrations have been
determined using EUSES 2.1.1. The EUSES program implements the environmental exposure
models described in REACH Technical Guidance Chapter R16. Default model parameters
have been used unless stated below.
The basis of local and regional production tonnages is to consider the sizes of the largest sites
in the EU relative to the total tonnage as follows:
Production volume in EU: 100 000 tonnes
Regional tonnage: 10 000 tonnes
Fraction of main local source: 1
Local tonnage: 29 tonnes per day
Number of days: 350

The contribution of local releases to the regional concentration has been considered using the
appropriate calculation in EUSES 2.1.1.
Table 9.11 shows the Predicted Environmental Concentrations. Due to the ready-
biodegradability of citric acid it has not been considered necessary to define a PEC in STP.
The low log Kow and ready biodegradability indicate that bioaccumulation is not a concern for
citric acid. Therefore, the assessment of secondary poisoning is not considered.
Table 9.11: Summary of Predicted Exposure Concentrations

PEC unit
AIR
Annual average local PEC in air (total) 3.50 x 10-16 [mg m-3]
WATER, SEDIMENT
Local PEC in surface water during emission episode (dissolved) 0.0153 [mg l-1]
Annual average local PEC in surface water (dissolved) 0.0153 [mg l-1]
Local PEC in fresh-water sediment during emission episode 0.261 [mg kg wwt-1]
Local PEC in seawater during emission episode (dissolved) 1.80 x 10-3 [mg l-1]
Annual average local PEC in seawater (dissolved) 1.78 x 10-3 [mg l-1]
Local PEC in marine sediment during emission episode 0.0307 [mg kg wwt-1]
SOIL, GROUNDWATER
Local PEC in agric. soil (total) averaged over 30 days 0.0227 [mg kg wwt-1]
Local PEC in agric. soil (total) averaged over 180 days 7.43 x 10-3 [mg kg wwt-1]
Local PEC in grassland (total) averaged over 180 days 2.97 x 10-3 [mg kg wwt-1]
Local PEC in pore water of agricultural soil 1.12 x 10-4 [mg l-1]
Local PEC in pore water of grassland 4.48 x 10-5 [mg l-1]
Local PEC in groundwater under agricultural soil 1.12 x 10-4 [mg l-1]
The EUSES model uses the Simple Treat sewage treatment model to predict the fate of a
substance in the STP, based on the physicochemical and biodegradation properties. For citric
acid, SimpleTreat predicts the following:
1.4 % to water:
0 % to air:
2.2 % to sludge:
96.4 % degraded.

The biodegradation rates used in the SIMPLETREAT model have been set up to be ten times
faster than the default value for a readily degradable substance as a realistic way of modelling
the substance being an essential metabolite.
Sludge from WWTPs may be spread on agricultural soil.
The dilution factor of 900 and 1000 (in the receiving water) have been applied for fresh water
and marine water respectively, as there is no information on specific hydrodynamic
conditions.

9.2 ES2: Use of citric acid as a chemical intermediate
This scenario covers the use of citric acid as a chemical intermediate in the synthesis of other
chemicals, such as citrate salts and esters. Only use at downstream user sites is considered
here; intermediate use at producer sites is covered by ES1.
Chemical synthesis takes place at industrial sites in batch or continuous processes with
limited opportunities for exposure (PROCS 1, 2, 3, 4). Loading/unloading operations at
dedicated facilities (PROC8b) are also covered by the scenario.

Used amount of substance per day 10,000 kg/d Generic information

Duration of exposure per day at >4 hours (all PROCs) REACH default used as a worst case;
workplace [for one worker] actually exposure times may be
significantly less
Frequency of exposure at workplace Once per day In situations where the duration of
[for one worker] exposure is lower, frequency of
exposure may be higher
Annual amount used per site 3,000 tpa Generic information
Emission days per site 300 d/y REACH default number of days for
high volumes

characteristics
Physical state Solid. Various powder and

crystalline grades are available.
Risk management measures related Precautions against dust See text
to the design of product explosion and irritation caused
by dust inhalation.


Respiration volume under 10 m3/d Default for workers, light activity

conditions of use
substance under conditions of use 2
240 cm PROC1: palm of one hand
2
480 cm PROC2: palms of both hands
2
240 cm PROC3: palm of one hand
2
480 cm PROC4: palms of both hands
480 cm2 PROC8b: palms of both hands
Body weight 70 kg Default
No measured data are available for releases to air and waste water during the processing of
citric acid as an intermediate. Releases are therefore estimated on the basis of information in
the public domain.
Releases to air
Due to the very low vapour pressure of the key intermediates and of citric acid itself, losses to
air are considered to be zero.
Releases to water
The REACH ERC 6A (Industrial use of intermediate) release default estimates to waste water
is 2%.
The default TGD (TGD ESD part IV) release rate from processing of synthetic intermediate is
0.7% by weight for a wet process and 0% for a dry (water-free) process. Processing of citric
acid is a wet-process. On-site waste water treatment at the plant (e.g. activated carbon,
precipitation and so on) is already included in the emission factors.
The default loss of 70 kg/d (EU TGD 0.7% default) from the processing of 30 t/d of citric
acid is not considered to be realistic. Realistic losses to waste water from the processing of
citric acid at a typical industrial site are expected to come from:
• Substance washout from ventilation systems

• Minor routine spillages

• Occasional equipment loss/leakages
Given that a solid is precipitated efficiently it is considered that 7 kg/d is a more realistic
estimate.
Citric acid is highly degradable and on-site waste water treatment is expected to mean that
little of the substance is released to the wider environment.
It can be assumed that this process will be taking place at a large industrial site with waste
water passing to a larger-than-default WWTP with a flow rate of 10,000 m3/day.
air
Fraction of applied amount lost 0 kg/kg See text

from process/use to waste gas
Fraction of applied amount lost 0.007 kg/kg See text
from process/use to waste water

Table 9.16 summarises the risk management measures in place during use of citric acid as a
chemical intermediate. Process take place under controlled conditions with opportunities for
manual handling minimised. Good working practices such as minimisation of splashes and
spills, avoidance of contact with the substance or contaminated objects, regular cleaning of
equipment and work area, good personal hygiene, staff training and management/supervision
are in place.

Containment plus good work Yes
practice required
Local exhaust ventilation required Yes Typical practice of chemical
plus good work practise industry. Not applicable for
PROC1.
Respiratory protection Dust mask.
In case of open handling of
larger quantities or accidental
release: particle mask or
respirator with independent air
supply

N/A
environment
treatment plant) discharge rate 1x 107 l/d Default for a large industrial site
process. Dried sludge from on-site waste water treatment plants may be sold as approved
agricultural fertiliser.
prior to discharge.
Workers at the production site are routinely involved with the same tasks, therefore it is more

Table 9.17 gives a summary of the long-term exposure values for PROCs 1, 2, 3, 4 and 8b,
based on the ECETOC TRA model. Defaults for duration of exposure (>4 hours) and use of
LEV (no for PROC 1, yes for PROCs 2, 3, 4, 8b) have been used. As a worst case, it has been
assumed that respiratory protection is not used; where this is not the case, actual exposure
may be much lower. Durations of exposure may also be less than 4 hours and in this case the
following modifications factors can be applied: 0.6 for 1-4 hours, 0.2 for 15 mins to 1 hour,
0.1 for <15 mins.
Inhalation exposure
exposure.
Citric acid is a solid and during use as an intermediate, it may be handled in solid form. Citric
acid is available in a range of particle size grades, from granular to fine powders. Therefore, a
worst case scenario is that the substances are very dusty. This is defined as ‘high fugacity’ in
the ECETOC TRA worker model. This is considered as worse case scenario for workers
exposure.
Dermal exposure

estimated using ECETOC TRA and presented in Table 9.17 may be multiplied by this factor
to obtain a worst-case estimate of the dermal exposure. Dermal uptake of solid citrates is

CHEMICAL SAFETY REPORT – [SUBSTANCE NAME] PART B
Table 9.17: Dermal exposure estimates (based on ECETOC TRA model)

Exposure Process Description LEV Dermal Predicted exposure Exposed skin Dermal
scenario category present? exposure? (µg/cm2/day) surface area (cm2) exposure
(mg/kg/day)a
Industrial use PROC1 Use in closed process, no likelihood of Nob Yes 100 240 0.3
exposure
PROC2 Use in closed, continuous process with Yes Yes 20 480 0.14
sampling)
PROC3 Use in closed batch process (synthesis or Yes Yes 10 240 0.03
formulation)
PROC4 Use in batch and other process (synthesis) Yes Yes 100 480 0.69
PROC8b Transfer from/to large vessels (dedicated) Yes Yes 100 480 0.69
a) Calculated assuming a default bodyweight of 70 kg for worker

b) In the ECETOC TRA model, LEV is not considered relevant for PROC1.

CHEMICAL SAFETY REPORT – [SUBSTANCE NAME] PART B
Table 9.18: Inhalation exposure estimates (based on ECETOC TRA model)

Exposure Process Description LEV LEV Predicted Predicted Inhalation
scenario category present? efficiency exposure (ppm) exposure (mg/m3)c exposure
(mg/kg/day)d
Industrial use PROC1 Use in closed process, no likelihood of Nob - 0.001 0.01 0.001
exposure
PROC2 Use in closed, continuous process with Yes 90% 0.01 0.1 0.01
sampling)
PROC3 Use in closed batch process (synthesis or Yes 90% 0.01 0.1 0.01
formulation)
PROC4 Use in batch and other process (synthesis) Yes 90% 0.31 2.5 0.36
PROC8b Transfer from/to large vessels(dedicated) Yes 95% 0.16 1.25 0.18
b) In the ECETOC TRA model, LEV is not considered relevant for PROC1.
c) Results are calculated as mg/m3 for solids and ppm for non-solids
d) Calculated assuming a default bodyweight of 70 kg for workers and a default respiratory volume of 10 m3, light activity, for an 8 hour work shift

Dermal local
exposure 0.6
factor of 0.006.
(in µg/cm2)
Dermal systemic
exposure 0.004
factor of 0.006.
(in mg/kg bw/d)
Inhalation exposure
(in mg/m3)/8h 2.5 ECETOC TRA prediction for PROC8b
workday
Inhalation exposure
(in mg/kg/d)/8h 0.36 ECETOC TRA prediction for PROC8b
workday
Consumer exposure is not applicable to use of citric acid as an intermediate.
There is no significant exposure of humans to citric acid via the environment, as the substance
is readily biodegradable.
9.2.2.4 Environmental exposure
Predicted environmental release estimates have been used for releases during intermediate
use. The releases have been estimated using the exposure scenario for intermediate use
(section 9.2.1.2 and 9.2.1.6) and Predicted Environmental Concentrations have been
determined using EUSES 2.1.1. The EUSES program implements the environmental exposure
models described in REACH Technical Guidance Chapter R16. Default model parameters
have been used with the following exceptions:
Dilution factor: 40 (large industrial site).
WWTP flow rate: 10,000 m3/d (large industrial site).
Application volume in EU: 12000 tonnes
Regional tonnage: 3000 tonnes

Fraction of main local source: 1
Number of days: 300
PEC unit
AIR
Annual average local PEC in air (total) 5.45 x 10-16 [mg m-3]
WATER, SEDIMENT
Local PEC in seawater during emission episode (dissolved) 0.0084 [mg l-1]
Annual average local PEC in seawater (dissolved) 0.00716 [mg l-1]
SOIL, GROUNDWATER
Local PEC in grassland (total) averaged over 180 days 0.00539 [mg kg wwt-1]
Local PEC in pore water of agricultural soil 0.000203 [mg l-1]
Local PEC in pore water of grassland 0.0000813 [mg l-1]
Local PEC in groundwater under agricultural soil 0.000203 [mg l-1]
No measured data are available for the concentration of citric acid in sewage treatment plants
(STP). The concentration has been estimated using a waste water treatment plant flow rate of
10000 m3/d and a dilution factor of 40 (Section 9.2.1.6) in EUSES 2.1.1.
12.7 % to water:
6 * 10-11% to air:
0.017 % to sludge:

87.3 % degraded.
conditions. No measured data are available for the concentration of citric acid due to its use as
a chemical intermediate in the aquatic pelagic compartment.

9.3 ES3: Formulation of citric acid into preparations
The primary uses of citric acid are described in the exposure scenarios 2-17. However,
formulation is a general process needed in many industries and Exposure Scenario 3 covers
the major uses in addition to the possibility of minor uses which require an industrial
formulation stage.
The formulation of cleaning products is the largest application and can be taken as the worst
case for the environmental exposure assessment, and this ES is expressed in terms of cleaning
products but is applicable more generally.
The following processes have been identified as being associated with formulation of citric
acid. Other processes may also be used but the processes listed are considered to include the
worst-case scenarios.
PROC1: Use in closed process, no likelihood of exposure
PROC2: Use in closed, continuous process with occasional controlled exposure
PROC3: Use in closed batch process (synthesis or formulation)
PROC4: Use in batch and other process (synthesis) where opportunity for exposure arises
PROC5: Mixing or blending in batch processes for formulation of preparations and articles
(multistage and/or significant contact); Industrial setting.
PROC7: Industrial spraying
PROC8: Transfer of substance or preparation from/to vessels/large containers; Industrial

setting. This may be at non-dedicated (PROC8a) or dedicated (PROC8b) facilities
depending on the situation, and may relate to both neat substance and preparations.
PROC9: Transfer of substance or of preparation into small containers (dedicated filling line,
including weighing); Industrial setting.
PROC13: Treatment of articles by dipping and pouring
PROC14: Production of preparations or articles by tabletting, compression, extrusion,

pelletisation
PROC15: Use of laboratory reagents in small scale laboratories
PROC19: Hand-mixing with intimate contact (only PPE available)

Operational conditions related to frequency, duration and amount of use
Used amount of substance per day 6000 tonnes

Duration of exposure per day at >4 hours (all PROCs) For some applications/setting
workplace [for one worker] exposure times may be significantly
less
Frequency of exposure at Once per day For some applications/settings with
workplace [for one worker] shorter duration exposures, multiple
exposures may occur in a single day
Annual amount used per site 20 tonnes
Emission days per site 300 days

characteristics

Physical state Solid. Various powder and

crystalline grades are
available.
The substance may also be

handled as part of, usually
aqueous-based, formulations.
Risk management measures Precautions against dust See text

related to the design of product explosion and irritation
caused by dust inhalation.


Respiration volume under 10 m3/d Default worker respiration rate for
conditions of use light activity

substance under conditions of use
240 cm2 PROC1, 13, 15: palm of 1 hand
2
480 cm PROC2, 4, 5, 8b, 9, 13 and 14: palms
of both hands
PROC8a: 2 hands
960 cm2
PROC7: 2 hands, forearms
1500 cm2
PROC19: 2 hands
1980 cm2
Body weight 10 m3/d Default worker respiration rate for
light activity
The citrates used in the formulation of products are generally solids which may be mixed with
other solids or dissolved in aqueous solution. There is some potential for airborne release of
citric acid (or citrate) particulates on charging (transfer, dosing) to the process equipment
used, especially if containment is not good. However, the most likely release will be to waste
water via clean out or spillage.
Tables 9.32 and 9.33 show the default emission factors from the EU TGD (EU TDG Parts II
and IV, EC 2003a,b) and REACH Environmental Release Categories (ERC), for emissions to
water and air respectively, during the formulation of personal care (based on cosmetics)
products.
Table 9.24: Releases to waste water for formulation

Source REACH ERC2 TGD Part IV Table 2 , Table A
2#
Fraction to waste water 0.02 0.0009
Table 9.25: Releases to air for formulation

Source REACH ERC2 TGD Part IV Table 2 , Table A TGD Part IV Table 2 , Table
2# A 2#
(Formulation of liquid (Formulation of

products) others/unknown products)
Fraction to air 0.025 0.00002 0.0002

The B Tables presented in the EU TGD (EC, 2003c) show the number of emission days for
the formulation of personal care products at a tonnage of 1000 tpa and above as 300 days (EU
TGD Table B2.3), while the REACH guidance for exposure estimation (R16) specifies 100
days for 100 – 2000 tpa and 300 days for greater than 2000 tpa of formulated products.
Detergents manufacturing facilities either treat effluents in on-site waste water treatment
plants followed by discharge to sewers, or discharge effluents directly to the municipal waste
water treatment system. Most facilities, however, discharge gaseous emissions directly to the
atmosphere, with a few incorporating filtration. Therefore the values from the TGD are
considered to be a realistic worst-case, especially given the low volatility of citric acid.
Taking the HERA figure of approx. 100 000 tpa [HERA, 2005] for total use of citrates in
detergents, and realistic values of 10% formulated in a single region, and 60% of that at a
single location, gives a volume of 6,000 tpa citrates formulated at a single location.
For this generic site, the daily loss rate to waste water is
6000 t x 1000 kg/t x 0.0009 / 300 d = 18 kg/d.
The tonnage to be covered is now 150 000 tpa, but the site size is retained. The loss rate is
considered to be a reasonable worst case for a large site. At smaller formulation sites the
amount handled per day would be lower and the controls could be less, but overall rates per
day would be similar.
air.

Fraction of applied amount lost from 0.0025 See text
Fraction of applied amount lost from 0.0005 See text
Table 9.27: Risk management measures for industrial site .

Containment plus good work practice Yes General good hygiene and
required housekeeping
Local exhaust ventilation required plus Yes Typical practice of chemical industry.
good work practise

N/A
Onsite pre-treatment of waste water Yes Removal of solids in settling tanks
Resulting fraction of initially applied No measured data
amount in waste water released from
site to the external sewage system
Resulting fraction of applied amount in No measured data See text
waste gas released to environment
Onsite waste treatment No Worst-case assumption as no specific
information available.
Fraction of initially applied amount sent No measured data
to external waste treatment. This is the
sum of direct losses from processes to
waste, and the residues from onsite
waste water and waste gas treatment.
Municipal or other type of external Yes Typical practise in the chemical
waste water treatment industry
Effluent (of the waste water treatment 1 * 107 L/d Default for a large industrial site.
plant) discharge rate
Recovery of sludge for agriculture or Yes Worst-case assumption as no specific
horticulture information available.
process. Dried sludge from on-site waste water treatment plants may be spread on agricultural
land.
prior to discharge.
Workers in industrial settings are routinely involved with the same tasks, therefore it is more

Table 9.28 gives a summary of the long-term exposure values for PROCs 1, 2, 3, 4, 5, 7, 8a,
8b, 9, 13, 14, 15, 19, based on the ECETOC TRA model. Defaults for duration of exposure
(>4 hours) and use of LEV (no for PROC 1, yes for all other PROCs) have been used. It has
been assumed that respiratory protection is not used; where this is not the case, actual
exposure may be much lower. Durations of exposure may also be less than 4 hours and in this
case the following modifications factors can be applied: 0.6 for 1-4 hours, 0.2 for 15 mins to 1
hour, 0.1 for <15 mins. The concentration in the formulation is assumed to be >25%;
reductions in the exposures may be applied for formulations with a lower percentage citrate
(*0.6 for 5-25%, *0.2 for 1-5% and *0.1 for <1%).
Inhalation exposure
exposure.
The substances may be handled as a solid during some stages of the formulation process. The
citrates are available in a range of different grades, form fine powders to granular material.
Therefore, for most PROCs the substance is considered as a solid with high fugacity as this
represents a worst cases scenario. The exception is PROCs 13 (Treatment of articles by
dipping and pouring) and 19 (Hand-mixing with intimate contact) which are only expected to
take place with already formulated product; the fugacity is assumed to be low.
Dermal exposure

estimated using ECETOC TRA and presented in Table 9.7 may be multiplied by this factor to
obtain a worst-case estimate of the dermal exposure. Dermal uptake of solid citrates is

Table 9.28: Dermal exposure estimates (based on ECETOC TRA model) for formulation
Life cycle Process Description Fugacity LEV Dermal Predicted Exposed skin Dermal
stage categor present? exposure? exposure surface area exposure
y (µg/cm2/day) (cm2)
(mg/kg/day)a
Industrial use PROC1 Use in closed process, no likelihood of High Nob Yes 100 240 0.34
exposure
Industrial use PROC2 Use in closed, continuous process with High Yes Yes 20 480 0.14
sampling)
Industrial use PROC3 Use in closed batch process (synthesis or High Yes Yes 10 240 0.034
formulation)
Industrial use PROC4 Use in batch and other process (synthesis) High Yes Yes 100 480 0.69
Industrial use PROC5 Mixing or blending in batch processes High Yes Yes 200 480 1.37
(multistage and/or significant contact)
Industrial use PROC7 Industrial spraying High Yes Yes 200 1500 4.29
Industrial use PROC8 Transfer from/to large vessels (non- High Yes Yes 100 960 1.37
a dedicated).
Industrial use PROC8 Transfer from/to large vessels (dedicated) High Yes Yes 100 480 0.69
b
Industrial use PROC9 Transfer to small containers High Yes Yes 100 480 0.69
Industrial use PROC1 Treatment of articles by dipping and Low Yes Yes 100 480 0.69
3 pouring
Industrial use PROC1 Production of preparations or articles by High Yes Yes 50 480 0.34
4 tabletting, compression, extrusion,
pelletisation

Life cycle Process Description Fugacity LEV Dermal Predicted Exposed skin Dermal
stage categor present? exposure? exposure surface area exposure
y (µg/cm2/day) (cm2)
(mg/kg/day)a
Industrial use PROC1 Use of laboratory reagents in small scale High Yes Yes 10 240 0.034
5 laboratories
Industrial use PROC1 Hand-mixing with intimate contact (only Low Yes Yes 500 1980 14.1
9 PPE available
(a) Calculated assuming a default bodyweight of 70 kg for workers
Table 9.29: Inhalation exposure estimates (based on ECETOC TRA model) for formulation
Life cycle Process Description Fugacity LEV LEV Predicted Predicted Inhalation
stage categor present? efficienc exposure (ppm) exposure exposure
y y (mg/m3)b (mg/kg/day)c
Industrial use PROC1 Use in closed process, no likelihood of High Nob n/a 0.0013 0.01 0.0014
exposure
Industrial use PROC2 Use in closed, continuous process with High Yes 90% 0.0125 0.1 0.014
sampling)
Industrial use PROC3 Use in closed batch process (synthesis or High Yes 90% 0.0125 0.1 0.014
formulation)
Industrial use PROC4 Use in batch and other process (synthesis) High Yes 90% 0.31 2.5 0.36
Industrial use PROC5 Mixing or blending in batch processes High Yes 90% 0.31 2.5 0.36
Industrial use PROC7 Industrial spraying High Yes 90% 1.25 10 1.43
Industrial use PROC8 Transfer from/to large vessels (non- High Yes 90% 0.63 5 0.71
a dedicated)

Life cycle Process Description Fugacity LEV LEV Predicted Predicted Inhalation
stage categor present? efficienc exposure (ppm) exposure exposure
y y (mg/m3)b (mg/kg/day)c
Industrial use PROC8 Transfer from/to large vessels (dedicated) High Yes 90% 0.31 2.5 0.36
b
Industrial use PROC9 Transfer to small containers High Yes 90% 0.25 2 0.29
Industrial use PROC1 Treatment of articles by dipping and Low Yes 90% 0.0013 0.01 0.0014
3 pouring
Industrial use PROC1 Production of preparations or articles by High Yes 90% 0.13 1 0.14
4 tabletting, compression, extrusion,
pelletisation
Industrial use PROC1 Use of laboratory reagents in small scale High Yes 90% 0.063 0.5 0.071
5 laboratories
Industrial use PROC1 Hand-mixing with intimate contact (only Low Yes 90% 0.0063 0.05 0.0071
9 PPE available
b) Results are calculated as mg/m3 for solids and ppm for non-solids
c) Calculated assuming a default bodyweight of 70 kg for workers and a default respiratory volume of 10 m3, light activity, for an 8 hour work shift

Dermal local
ECETOC TRA prediction for PROC19, multiplied by an uptake
exposure 3
factor of 0.006.
(in µg/cm2)
Dermal systemic
exposure 0.08
factor of 0.006.
(in mg/kg bw/d)
Inhalation exposure
(in mg/m3)/8h 10 ECETOC TRA prediction for PROC7
workday
Inhalation exposure
(in mg/kg/d)/8h 1.43 ECETOC TRA prediction for PROC7
workday
There is no consumer exposure associated with industrial formulation.
There is no exposure of humans to the substance via the environment.
Predicted environmental release estimates have been used for releases during formulation.
The releases have been estimated using the exposure scenario for formulation (section 9.3.1.2
and 9.3.1.6) and Predicted Environmental Concentrations have been determined using EUSES
2.1.1.
The EUSES program implements the environmental exposure models described in REACH
Technical Guidance Chapter R16. Default model parameters have been used with the
following exceptions:
Dilution factor: 40 (large industrial site).
WWTP flow rate: 10,000 m3/d (large industrial site).
The basis of local and regional tonnages is to consider the sizes of the largest sites in the EU
relative to the total tonnage as follows:
Application volume in EU: 150000 tonnes

Fraction of main local source: 0.4
Number of days: 300
PEC unit
AIR
Annual average local PEC in air (total) 1.4 x 10-15 [mg.m-3]
WATER, SEDIMENT
Local PEC in seawater during emission episode (dissolved) 0.0194 [mg l-1]
Annual average local PEC in seawater (dissolved) 0.0162 [mg l-1]
SOIL, GROUNDWATER
Local PEC in grassland (total) averaged over 180 days 0.0139 [mg kg wwt-1]
(STP). The concentration has been estimated using a waste water treatment plant flow rate of
10,000 m3/d (Section 9.3.1.6) in EUSES 2.1.1.
12.7 % to water:
6 * 10-11% to air:

0.017 % to sludge:
87.3 % degraded.
Estimated local exposure concentrations for freshwater and marine water have been based on
the exposure scenario for production (Sections 9.1.1.2 and 9.1.1.6) and EUSES 2.1.1 model
output. The dilution factor of 10 (in the receiving water) has been applied. No measured data
are available for the concentration of citric acid in the aquatic pelagic compartment.

9.4 ES4: Personal care use
Personal care use is treated as exempt from REACH in respect of human health. Formulation
is covered by ES3.
Citric acid and its salts are used in a wide range of personal care products, including:
• Shampoos and conditioners

• Astringent lotions
• Bubble baths
• Creams and lotions
• Facial cleaners
• Feminine hygiene products
• Permanent wave neutraliser
• Propellants for aerosol-type dispensers
• Toothpastes
• Mouth rinses
• Body wash/cleanser
• Hair colour and bleaching
• Moisturisers
• Hand soaps
• Nail polish
• Anti-aging products
In these products, citrates act as clarifying agents, water softeners, buffers, foam boosters and
stabilizers, complexing agents (for example to stabilize the formulation by chelating metal
ions and preventing discoloration and decomposition).
The EU TGD A-Table A4.1 gives the releases of cosmetics to air and wastewater as 0 and
100% respectively. This seems reasonable, given that citrates are non-volatile and highly
water soluble. It is also in agreement with Colipa’s assessment of the fate of non-volatile
components of cosmetics (Colipa 2008).
The TGD defaults and REACH environmental release category (ERC8a) assume that if a
substance is used widely across the EU, the fraction of the production volume used in the
standard EU Region is 10%. For cosmetics, the fraction of the main local source
(fmainsource) is 0.0005 (HERA, 2005, page 27). This is equivalent to saying that use in a
region is evenly distributed. The number of days of use is 365 per year. Therefore, for 7500
tpa of citric acid in personal care products used widely across the EU, the estimated release of
citric acid to a particular default-sized local waste water treatment plant is at most:
7 500 000 kg/y x 0.1 x 0.0005 / 365 d/y = 1.03 kg/d

air.

No risk management measures are possible for personal care use in respect of the
environment.
Predicted Environmental Concentrations have been determined using EUSES 2.1.1. The
EUSES program implements the environmental exposure models described in REACH
Technical Guidance Chapter R16. Default model parameters have been used with the
Production volume in EU: 7,500,000 tonnes
Regional tonnage: 750,000 tonnes
Local tonnage: 1.03 tonnes per day
Number of days: 365
appropriate calculation in EUSES 2.1.1. Table 9.33 shows the Predicted Environmental
Concentrations. Due to the ready-biodegradability of citric acid it has not been considered
necessary to define a PEC. The low log Kow and ready biodegradability indicate that
bioaccumulation is not a concern for citric acid. Therefore, the assessment of secondary
poisoning is not considered further

PEC unit
AIR

PEC unit

WATER, SEDIMENT
Local PEC in surface water during emission episode (dissolved) 1.59 x 10-2 [mg l-1]
Annual average local PEC in surface water (dissolved) 1.59 x 10-2 [mg l-1]
Local PEC in fresh-water sediment during emission episode 2.71 x 10-1 [mg kg wwt-1]
Local PEC in marine sediment during emission episode 2.53 x 10-2 [mg kg wwt-1]
SOIL, GROUNDWATER
12.6 % to water:
0.112 % to air:
0.0154 % to sludge:
87.3 % degraded.
conditions.
There is no direct release to the terrestrial compartment on a local scale as biosludge from on-
site waste water treatment is disposed of via incineration or landfill. However, due to use of
municipal WWTP by some EU production sites, spreading of sludge on agricultural soil is
included as a reasonable worst case.

9.5 ES5: Use of citric acid in cleaning products
Following the REACH descriptor system, the following product types are covered by this
generic scenario:
• Washing and cleaning products (PC35): Detergents, fabric washing, dish cleaning and
surface cleaning products;
• Automotive care products (PC06).
As some products combine the task of cleaning and polishing, making it difficult to make a
clear distinction between types of products, the following product type may also be relevant:
• Polishes and Wax Blends (PC31).
This scenario covers the use of citric acid as an ingredient in detergent, cleaning and other
household products used in industrial, professional and consumer settings. Formulation of
citric acid into such products is covered by ES3.
The generic EU tonnage is considered to be 100 000 tonnes per year.
Industrial use
Activities during industrial use of cleaning and maintenance products are usually
characterised by a frequency of once in 5 days for cleaning or laundry products; and 480
times in 1 day for vehicle cleaning products (e.g. aeroplane and train cleaners) [AISE, 2009].
While industrial cleaning products are used indoors, without local exhaust ventilation; vehicle
cleaning products are used outdoors. The relevant PROCs for the activities considered for
workers exposure are:
PROC2: Use in closed, continuous process with occasional controlled exposure.
PROC4: Use in batch and other process (synthesis) where opportunity for exposure arises.
PROC7: Industrial spraying
PROC8: Transfer of substance or preparation from/to vessels/large containers; Industrial

setting. This may be at non-dedicated (PROC8a) or dedicated (PROC8b) facilities
depending on the situation, and may relate to both neat substance and preparations.
PROC9: Transfer of substance of preparation into small containers (dedicated filling line,

PROC10: Roller application or brushing. This describes activities such as application of
surface cleaning products using wet wipes, use of polishes and vehicle cleaning
products
PROCs 7, 8, 9, 10 and 13 are quantified as these are considered to cover the worst-case for
exposures.
No modifying factors have been taken into account for the initial assessment, other than
presence or absence of Local Exhaust Ventilation. Possible refinements that would lower that
actual exposure include modification for concentration in preparations and modification for
duration of exposure.
The substances are solid but are mostly used in an aqueous-based solution. Therefore,
fugacity is low, except where aerosol mists may be generated (PROC7).
Professional use
Activities during professional use of cleaning and maintenance products vary depending on
the application. Duration of 15 minutes per application and 30 minutes per application
appears to be worse case scenarios for laundry and vehicle cleaning products respectively
[AISE, 2009]). The relevant PROCs for the activities considered for workers exposure are:
PROC1: Use in closed process, no likelihood of exposure
PROC4: Use in batch and other process (synthesis) where opportunity for exposure arises
PROC8a: Transfer of substance or preparation from/to vessels/large containers at a non-

dedicated facility.
PROC9: Transfer of substance of preparation into small containers (dedicated filling line,
PROC10: Roller application or brushing. This describes activities such as application of

surface cleaning products using wet wipes, use of polishes and vehicle cleaning
products
PROC11: Non-industrial spraying
PROC19: Hand-mixing with intimate contact and only PPE available
PROCs 8a, 9, 10, 11, and 19 are quantified as these are considered to be the most common
and represent the worst-case for exposures.
No modifying factors have been taken into account for the initial assessment, other than
presence or absence of Local Exhaust Ventilation. Possible refinements that would lower that
actual exposure include modification for concentration in preparations and modification for

duration of exposure. Duration of exposure of 15 minutes – 1 hour gives a modification factor
of 0.2.
fugacity is low, except where the product is an aerosol or spray (PROC11).
Consumer use
Processes carried out during consumer use of detergent and cleaning products containing
citric acid are expected to be similar to those outlined above for professional use. Professional
use is considered to represent a worst-case for exposure because durations and frequencies of
exposure will be greater.

Used amount of substance per day 200,000 kg/d Generic information

Duration of exposure per day at >4 hours (all PROCs) For some applications/setting
workplace [for one worker] exposure times may be
significantly less
Frequency of exposure at workplace Once per day For some applications/settings
[for one worker] with shorter duration exposures,
multiple exposures may occur in a
single day
Annual amount used per site 10 kg/d 0.00005 (10% in region, plus
0.0005 fraction of main local
source from HERA)
Emission days per site 365 d/y Default for ERC8

characteristics
Citric acid used in cleaning and detergent applications is part of a preparation. Products may
be liquids, pastes, creams, or aerosols; the concentration of citrate used in these applications
varies. The HERA risk assessment for household cleaning products gives the following
figures:
• laundry detergents 0-10% • laundry additives 0-55%

• fabric conditioners <1% • machine/hand dishwashing detergents 0-45%
• surface cleaners 0-30% • toilet cleaners 0-7%.

Physical state Part of a preparation; may be

liquid or solid.
Risk management measures related The pH of liquid formulations is
to the design of product controlled.
Solid products are granular and
thus exposure to dust is not
expected.


Respiration volume under 10 m3/d Default for workers, light activity
conditions of use
substance under conditions of use 2
480 cm PROC5:
1500 cm2 PROC7:
2
960 cm PROC8a:
2
480 cm PROC8b:
2
480 cm PROC9
2
960 cm PROC10
1500 cm2 PROC11
2
480 cm PROC13
2
1980 cm PROC19
Body weight 70 kg Default for workers
Table 9.37: Operational conditions related to respiration, skin contact and ingestion for the
general public
Skin contact area 960 cm2 ConsExpo default

Mouth contact area - Not applicable – no oral exposure
3
Respiration volume under 26 m Default:
conditions of use
Light activity 26 m3/24 h
20m3 ; exchange per hour 0.6 h- ConsExpo defaults
1
Room size and ventilation rate
Body weight 65 kg Default adult bodyweight

Dilution factor: 10 (default).

No measured data are available for releases to air and waste water during the use of citric acid
in cleaning products. Releases are therefore estimated on the basis of information in the
public domain.
Citric acid and citrates are used in a variety of cleaning products but generally in aqueous
solution. The most likely release route will, therefore, be to waste water via rinsing to drain
in-use, spillage, clean out or discharge of cleaning baths or liquors. Indeed, releases to waste
water can be assumed to be 100%, since all the citric acid/citrate will eventually be washed to
drain. This may be an overestimate since it does not allow for any of the substance to be
either released to air (extremely unlikely) during the process or to adsorb to a surface on
drying or to a cleaning implement (e.g., cloth) which may be landfilled.
The release of citrates from use in cleaning products in industrial, professional and consumer
use can be estimated. The TGD defaults and REACH environmental release category
(ERC8a) assume that if a substance is used widely across the EU, the fraction of the
production volume used in the standard EU Region is 10%. For cleaning products, the
fraction of the regional tonnage discharging to a particular waste water treatment plant can be
estimated as 0.0005 (HERA, 2005). The number of days of use is 365 per year. Therefore, for
100,000 tpa of citric acid in cleaning products used widely across the EU, the estimated
release of citrates to a particular default-sized local waste water treatment plant is at most:
100,000,000 kg/y x 0.1 x 0.0005 / 365 d/y = 13.7 kg/d
= (Amount of citrates used in cleaning products per year x fraction to water x fraction in the
region x fraction of main local source) / number of days per year
The research carried out by the HERA project was thorough and accepted by the EU
authorities as valid.
air

from process/use to waste gas
from process/use to waste water
Table 9.39 summarises the risk management measures in place during use of citric acid at
industrial sites.

Containment plus good work Yes General good hygiene and

practice required housekeeping
Local exhaust ventilation required No
plus good work practise
N/A
environment
treatment plant) discharge rate 2000000 l/d Default for a standard WWTP
At industrial sites, solid wastes may be disposed of via landfill or incineration, or are recycled
outside of the process. Dried sludge from on-site waste water treatment plants may be sold as
approved agricultural fertiliser. Details of the treatment of aqueous waste vary at different
sites but as a minimum, wastes are neutralised and the effluent treated in on- or off-site
secondary biological treatment plants prior to discharge. Waste gases are not generated.
In consumer and professional use, waste water passes to municipal WWTPs. Sludge may be
spread on agricultural land.

9.5.2.1 Workers exposure – industrial settings
Workers in industrial settings are routinely involved with the same tasks, therefore it is more
Table 9.40 and 9.41 give a summary of the long-term exposure values for PROCs 7, 8 and 9,
based on the ECETOC TRA model. The default for duration of exposure (>4 hours) has been
used and it has been assumed that LEV and respiratory protection are not present. The
exception to this is PROC7 (industrial spraying) where it is assumed that LEV is present.
Where the worst-case defaults do not apply, actual exposure may be much lower. In
particular, actual durations of exposure may be much less than 4 hours; in this case the
following modification factors can be applied: 0.6 for 1-4 hours, 0.2 for 15 mins to 1 hour, 0.1
for <15 mins. The concentration in the formulation is assumed to be >25%; reductions in the
exposures may be applied for formulations with a lower percentage citrate: *0.6 for 5-25%,
*0.2 for 1-5% and *0.1 for <1%.
Inhalation exposure
exposure.
fugacity is low, except where aerosol mists may be formed (PROC7).
Dermal exposure

0.006 (see Section 5.1); actual uptake may be much less. The dermal exposures estimated
using ECETOC TRA and presented in Table 9.40 may be multiplied by this factor to obtain a

worst-case estimate of the dermal exposure. Dermal uptake of solid citrates is expected to be
negligible and is not considered.

Table 9.40 Dermal exposure estimates (based on ECETOC TRA model) for cleaning and maintenance
Life cycle stage Process Description Fugacity LEV Dermal Predicted Exposed skin Dermal exposure
category present? exposure? exposure surface area (cm2)
(µg/cm2/day) (mg/kg/day)a
Industrial use PROC8a Transfer from/to large vessels (non-dedicated) Low No Yes 1000 960 13.7
Industrial use PROC8b Transfer from/to large vessels(dedicated) Low No Yes 1000 480 6.9
Industrial use PROC9 Transfer to small containers Low No Yes 1000 480 6.9
Industrial use PROC7 Industrial spraying High Yes Yes 100 1500 2.14
Industrial use PROC10 Roller application or brushing Low No Yes 2000 960 27.4
Industrial use PROC13 Dipping or pouring Low No Yes 2000 480 13.7
Table 9.41 Inhalation exposure estimates (based on ECETOC TRA model) for cleaning and maintenance products
Life cycle stage Process Description Fugacity LEV LEV Predicted Predicted Inhalation exposure
category present? efficiency exposure (ppm) exposure (mg/m3)b (mg/kg/day)c
Industrial use PROC8a Transfer from/to large vessels (non-dedicated) Low No n/a 0.063 0.5 0.07
Industrial use PROC8b Transfer from/to large vessels (dedicated) Low No n/a 0.012 0.1 0.014
Industrial use PROC9 Transfer to small containers Low No n/a 0.012 0.1 0.01
Industrial use PROC7 Spraying in industrial settings and applications High Yes 95% 0.63 5 0.71
Industrial use PROC10 Roller application or brushing Low No n/a 0.063 0.5 0.07
Industrial use PROC13 Dipping or pouring Low No n/a 0.012 0.1 0.014

Dermal local
ECETOC TRA prediction for PROC10; multiplied by a dermal
exposure 12
uptake factor of 0.006.
(in µg/cm2)
Dermal systemic
ECETOC TRA prediction for PROC10; multiplied by a dermal
exposure 0.16
uptake factor of 0.006.
(in mg/kg bw/d)
Inhalation exposure
(in mg/m3)/8h 5 ECETOC TRA prediction for PROC7
workday
Inhalation exposure
(in mg/kg/d)/8h 0.71 ECETOC TRA prediction for PROC7
workday
9.5.2.2 Consumer/professional exposure
It is expected that both workers and consumers will make use of cleaning products on a
routine basis. Therefore, only long-term exposure is discussed. This is considered to cover the
worst-case for professional and consumer exposure.
Table 9.40 and 9.41 give a summary of the long-term exposure values for PROCs 8a, 9, 10,
11 and 19, based on the ECETOC TRA model. The default for duration of exposure (>4
hours) has been used and it has been assumed that LEV and respiratory protection are not
present. Where this is not the case, actual exposure may be much lower. In particular, actual
durations of exposure may be much less than 4 hours; in this case the following modification
factors can be applied: 0.6 for 1-4 hours, 0.2 for 15 mins to 1 hour, 0.1 for <15 mins. The
concentration in the formulation is assumed to be >25%; reductions in the exposures may be
applied for formulations with a lower percentage citrate: *0.6 for 5-25%, *0.2 for 1-5% and
*0.1 for <1%.
Inhalation exposure
exposure.

The citrates are solid but are mostly used in an aqueous-based solution in cleaning
applications. Formation of aerosol mists is not expected in consumer or professional
applications. Consumer products in wide-spread use which are solids are granular and,
therefore, significant exposure to dusts is not expected. The substances are considered to be
low fugacity for all calculations.
Dermal exposure

estimated using ECETOC TRA and presented in Table 9.43 may be multiplied by this factor
to obtain a worst-case estimate of the dermal exposure. Dermal uptake of solid citrates is
The highest exposure in Table 9.43 is predicted to be associated with PROC19, intimate hand-
mixing. The dermal exposure after correction for uptake fraction is 141 * 0.006 = 0.8
mg/kg/d. However, the duration of exposure for this type of process is expected to be
considerably lower than the default >4 h on which the estimate is based. Duration of exposure
of 1 h over the course of a day is considered to be a realistic worst-case, therefore, the
corrected exposure is 0.16 mg/kg/d.
The second highest predicted exposure in Table 9.43 is associated with PROC11, non-
industrial spraying. It is possible that this time of process could have a longer duration of
exposure; therefore, no duration of exposure modification is applied. The estimated exposure
after correction for uptake fraction is 107 * 0.006 = 0.6 mg/kg/d.

Table 9.43 Dermal exposure estimates (based on ECETOC TRA model) for cleaning and maintenance
Life cycle stage Process Description Fugacity LEV Dermal Predicted Exposed skin Dermal exposure
category present? exposure? exposure surface area (cm2)
(µg/cm2/day) (mg/kg/day)a
Professional use PROC8a Transfer from/to large vessels (non-dedicated) Low No Yes 1000 960 13.7
Professional use PROC9 Transfer to small containers Low No Yes 1000 480 6.86
Professional use PROC10 Roller application or brushing Low No Yes 2000 960 27.4
Professional use PROC11 Non-industrial spraying Low No Yes 5000 1500 107
Professional use PROC19 Intimate hand mixing Low No Yes 5000 1980 141
Table 9.44 Inhalation exposure estimates (based on ECETOC TRA model) for cleaning and maintenance products
Life cycle stage Process Description Fugacity LEV LEV Predicted Predicted Inhalation exposure
category present? efficiency exposure (ppm) exposure (mg/m3)b (mg/kg/day)c
Professional use PROC8a Transfer from/to large vessels (non-dedicated) Low No N/A 0.06 0.5 0.07
Professional use PROC9 Transfer to small containers Low No N/A 0.06 0.5 0.07
Professional use PROC10 Roller application or brushing Low No N/A 0.06 0.5 0.07
Professional use PROC11 Non-industrial spraying Low No N/A 0.125 1 0.14
Professional use PROC19 Intimate hand mixing Low No N/A 0.06 0.5 0.07

Dermal local
exposure 30
factor of 0.006
(in µg/cm2)
Dermal systemic
exposure 0.6
factor of 0.006
(in mg/kg bw/d)
Inhalation exposure
(in mg/m3)/8h 1 ECETOC TRA prediction for PROC
workday
Inhalation exposure
(in mg/kg/d)/8h 0.14 ECETOC TRA prediction for PROC
workday
For the purposes of estimating releases to the environment, industrial, professional and
consumer uses are equivalent and are covered together in the following sections. Predicted
environmental release estimates have been used for releases resulting from use of cleaning
products containing citric acid. The releases have been estimated using the exposure scenario
for this use (section 9.4.1.2 and 9.4.1.6) and Predicted Environmental Concentrations have
been determined using EUSES 2.1.1. The EUSES program implements the environmental
exposure models described in REACH Technical Guidance Chapter R16. Default model
parameters have been used.
Application volume in EU: 100 000 tonnes
Regional tonnage: 10 000 tonnes
Number of days: 365 (consistent with the default)

PEC unit
AIR
WATER, SEDIMENT
Local PEC in marine sediment during emission episode 4.05 x10-2 [mg kg wwt-1]
SOIL, GROUNDWATER
No definitive measured data are available for the concentration of citric acid in sewage
treatment plants (STP). A source to which reliability could not be assigned gives a
concentration of citrate in raw sewage of up to 10 mg/l (OECD SIDS). This concentration will
arise from both natural and man-made sources of citrate.
The concentration in sewage treatment plants due to use of cleaning products containing citric
acid has been estimated using a default waste water treatment plant flow rate of 2000 m3/d
and a dilution factor of 10 (Section 9.2.1.6) in EUSES 2.1.1.
12.7 % to water:
6 * 10-11% to air:
0.017 % to sludge:
87.3 % degraded.

The percentage degraded is the default for a readily biodegradable substance; actual
degradation of citric acid may be higher.
An alternative approach to calculating the concentration in sewage sludge was used by HERA
in their risk assessment of citric acid and salts in household cleaning products. 20% of the
total production tonnage of 500,000 tonnes per annum was assumed to be used in wide
dispersive technical applications (the bulk of the tonnage being used in the food and
pharmaceutical industries). Based on a population figure of approx. 470 million people and a
per capita water consumption of 200 l/day, a raw waste water concentration of 2.9 mg/l was
calculated (HERA 2005).
For the present risk assessment, the EUSES value of 5.1 mg/l is used to represent a worst-
case, although it is likely to be very conservative.
output. The default dilution factors of 10 and 100 (in the receiving water) have been applied
for fresh water and marine water respectively, as there is no information on specific
hydrodynamic conditions.
Measured background concentrations in surface waters range from <0.04 to 0.2 mg/l in river
water and 0.025-0.145 mg/l in Atlantic coast seawater (OECD SIDS). These concentrations
will result from both man-made and natural sources. The measured data provides a useful
comparison with the predicted levels but are not considered sufficiently robust for use in the
risk characterisation. In addition, it is not possible to separate the contributions from different
sources. Therefore, the estimated PECs are used in the remainder of the exposure assessment.
Exposure concentrations in soil and groundwater are estimated (on a regional basis) based on
EUSES 2.1.1. No measured data on concentrations due to this use are available. Sewage
sludge from waste water treatment plants may be spread on agricultural soil.
The Predicted Exposure Concentration (PEC) of citric acid in the atmosphere is estimated
based on EUSES 2.1.1. No measured data are available.

9.6 ES6: Use in paper
Following the REACH descriptor system, the following product type is covered by this
generic scenario: Paper and board dye, finishing and impregnation products: including
bleaches and other processing aids (PC26).
Citric acid is used in the cleaning of papermaking machines and to prevent build up of
deposits. It is added to the pulp slurry prior to bleaching to control paper staining by
sequestering metal ions. Cleaning applications are covered under another exposure scenario;
this document covers use of citrate as a processing aid in the paper-making industry.
This generic scenario makes use of the following documents:
• OECD Emission Scenario Documents on Kraft, Non-Integrated and Recovered Pulp

Mills.
This covers the use of citrate as a process aid in the paper-making industry. It is possible that
a small amount of citrate is incorporated into the finished paper products. However, it is
considered that the amount of citrate that ends up in articles and could be released (resulting
in consumer exposure) is likely to be negligible.
The amount of citric acid believed to be used in this application is at most 1000 tpa. The
industrial use per site is unknown. However, a default approach would be to consider 10
paper mills in a single region, operating over 300 days per year. The substance is not mixed
into pulp, but is applied to machinery. A loss of 2% is a realistic maximum.
This gives a daily release of
100 t x 1000 kg/t x 0.02 / 300 d = 6.7 kg/d
For the environment, the amounts passing to waste are very likely to be less than those from
the ES 1-5. Therefore there is no need to complete an exposure assessment at a local scale
with full details of PEC values etc.
However, a regional release of 67 kg/d to waste water will be added to the model.
For human health worker exposure at paper mills will be to aqueous formulations for which
no hazard has been identified. In addition, relevant exposures have been calculated for life
cycle stages with higher exposures. Therefore no attempt at quantification will be made nor is
needed.

9.7 ES7: Use in construction
generic scenario: PC10 (Building and construction preparations not covered elsewhere).
The following substances are used in construction materials: citric acid and trisodium citrate.
Citrates can be used to retard the setting rate of cement and reduce the amount of water
needed. They may therefore be added to concrete, mortar, plaster and render formulations.
The concentration in these products is generally low (<1%).
This document provides an environmental generic exposure scenario for substances used in
construction materials. This generic scenario makes use of the following documents:
• EU Technical Guidance Document (TGD) emission scenario document.

• REACH Technical Guidance.
The amount of citric acid believed to be used in this application is at most 1500 tpa. The
industrial use per site is unknown, but should be considered as a widely dispersed use. In the
worst case a release of the entire tonnage to the region could be included, i.e. 1500 tpa. Of
this, part will be released to industrial soil (90%) and part to waste water (10%).
A regional release of 150 x 1000/365 = 411 kg/d to waste water will be added to the model,
and 3699 kg/d to industrial soil will be included.
For human health worker exposure at construction sites will be to aqueous formulations for
which no hazard has been identified. In addition, relevant exposures have been calculated for
life cycle stages with higher exposures. Therefore no attempt at quantification will be made
nor is needed.

9.8 Use in polymers and plastics
Following the REACH descriptor system [ECHA, 2009], the sectors of use (SU) covered by
this generic scenario are:
SU11 (Manufacture of rubber products) and
SU12 (Manufacture of plastics products, including compounding and conversion).
Applications encompass the following product categories (PC):
PC32: Polymer Preparations and Compounds.
Polyolefin foams are used for a variety of applications such as automotive, construction, food
packaging, sport and leisure, and many other industrial and consumer uses. They usually have
a high strength to weight ratio and are manufactured in a variety of processes and in low
density (25 - 250 kg/m3) or high density (250 - 700 kg/m3) versions, or even in densities as
low as 16 kg/m3 for polystyrene. All current extrusion processes involve the following steps:
melting, mixing with blowing agents, cooling of melt, expansion and degassing/aging. The
steps in this process can be realized in different configurations of equipment, e.g., with long
single-screw extruders, twin-screw extruders, or tandem extruder lines.
The choice of chemical or physical blowing agents depends on the foam density to be reached
(e.g. the foam application) and influences the necessary foaming equipment and the costs of
the foamed materials. High-density thermoplastic foams based on, e.g., polypropylene or
polystyrene, may be produced using blowing agents which decompose to generate gas which
is soluble in the melt but which is released as the pressure is reduced (e.g., by passing through
a dye) to produce a foam. The foaming process is complex but involves bubble nucleation
followed by bubble growth.
One example of a commercially used chemical foaming agent is based on citric acid (or
monosodium citrate) in combination with sodium carbonate or (sodium bicarbonate) in a
weight ratio of between about 1:1 and about 5:1 respectively [US 5,302,455]. The citric
acid/sodium bicarbonate system decomposes at 160 – 210°C to release 120 cm3/g of CO2.
[Karger-Kocsis, 1999; Brydson, 1999; Holmberg, 2002]
Both citric acid (or citrate salt) and (bi)carbonate may be surface-treated with, for example, a
fatty acid ester to make them compatible with the polyolefin. A concentrated master batch of
the formulated foaming agent in polymer at loading levels of from about 5% to about 50%
actives may then be prepared. The master batch is added to the polymer melt which is to be
foamed such that the blowing agents are at 0.1 to 2.0% active levels in the final formulation
[US 5,302,455 and refs. therein].
By-products of this reaction are mono-, di-, and/or trisodium citrate, in combination with
other sodium salts, which will still be present within the foamed polymer. These residues are
typically present at around 50 wt.% of the initial foaming agent formulation, which is
equivalent to <1 wt.% of the total foamed polymer in most cases [RAPRA, 2004].

There is some potential for airborne release of citric acid (or citrate) particulates in preparing
the mix of ingredients and on charging (transfer, dosing) to the extruder or other process
equipment used, especially if containment is not good. Ultimately all particulates will be removed
or settle and losses will be to solid waste or to waste water as a result of wash down. Material
remaining in packaging (bags) is assumed to go to solid waste from the plastics processing site [OECD
2004].
The OECD Plastics Additives ESD gives the following figures for loss from raw materials handling
for powders of particle size <40 μm (losses for smaller particle sizes are smaller):
Fhandling, water = (0.1+ 0.5) = 0.6% to solid waste/water
Fhandling, air = 0%
Fhandling, waste = 1.0% to solid waste as residue in bags
Losses for compounding for powders of particle size <40 μm are as follows:
Fcompounding, water = 0.05%
Fcompounding, air = 0%
Losses from conversion, service life and disposal for chemical blowing agents are considered to be
zero as the additive is destroyed during the conversion process.
Thus, for 200 tpa of citrates used in plastics applications, assumed to be used at 10 sites
across Europe, the local losses to water air and solid waste are:
The REACH defaults for ERC6d are for the production on 300 days per year if the tonnage of
the product is >5000 tpa [ECHA, 2009]. Citrate is present at <1% in plastics applications (see
Section 2.1.1), therefore, the total production volume is approx. 100,000 tpa. Therefore, the
maximum daily releases are as follows:
Water: 20 t x 1000 kg/t x (0.0065) / 300 = 0.43 kg/d
Air: 0
For the environment, the amounts passing to waste are very likely to be less than those from
the ES 1-5. Therefore there is no need to complete an exposure assessment at a local scale
with full details of PEC values etc.
However, a regional release of 0.35 kg/d to waste water will be added to the model, and
similarly 3.18 kg/d to the continental scale.
For human health worker exposure at construction sites will be to aqueous formulations for
nor is needed.

9.9 ES9: Use in the oil industry
SU2a Mining (without offshore industries)
SU2b (Offshore industries)
PC20: Products such as ph-regulators, flocculants, precipitants, neutralization agents,

other unspecific
In the oil industry, citric acid is often used for oil-well acidizing to prevent the formation of
insoluble gels of iron hydroxide [APAC]. Oil well acidizing is the term used for the
application of hot hydrochloric acid (200-300°F; 93-149°C) to remove tough wellbore scale
[McGraw-Hill].
Oxidation reactions, which occur in wells injected with HCl, cause formation of insoluble
iron hydroxide gels [APAC]. The pumping operations are thus interrupted by these gels, and
hence, citric acid is added to complex the iron, thus preventing gel formation [APAC].
Oil producing well formations can become plugged with acid soluble minerals and restrict
fluid flow and reduce oil production [Gewanter, Herman L. et al]. Production can be increased
by forcing acid down the well formations to dissolve the minerals [Gewanter, Herman L. et
al]. The acids readily dissolve the iron and iron containing compounds from the well casing
and the formation [Gewanter, Herman L. et al]. However, water and carbonates will neutralize
the acid in the formation, which allows for the re-precipitation of the iron to ferric hydroxide
above a pH of 2.2. [Gewanter, Herman L. et al]. Certain chemicals must be added at this point
to maintain it in a soluble state [Gewanter, Herman L. et al].
Control of the re-precipitation of iron and the pH, as the acid is spent, can be achieved by the
sequestration by organic chelants and the reduction to soluble ferrous iron [Gewanter,
Herman L. et al]. Citric acid is a useful organic chelant and is used for this purpose
[Gewanter, Herman L. et al]. Other chelants may include gluconic acid, the tetrasodium salt
of ethylenediaminetetraacetic acid (EDTA), and the trisodium salt of nitrilotriacetic acid
(NTA) [Gewanter, Herman L. et al].
This is a widely dispersed use but in the worst case it can be envisaged that the entire tonnage
could pass to surface marine water. This equates to
100 t x 1000 kg/t /365 = 274 kg/d to the regional surface water
900 t x 1000 kg/t /365 = 2740 kg/d to the continental surface water

For human health worker exposure at oil production sites will be to aqueous formulations for
nor is needed.
9.10 Use in textiles
SU5 (Manufacture of textiles, leather, fur) and
SU10 (Formulation [mixing] of preparations and/or re-packaging).
PC20: Products such as pH-regulators, flocculants, precipitants, neutralization agents;
PC23: Leather tanning, dye, finishing, impregnation and care products; and
PC34: Textile dyes, finishing and impregnating products.
The OECD Emission Scenario Document on the Textile Finishing Industry [OECD, 2004A]
describes the textile industry as “one of the largest and most complicated industrial chains in
manufacturing industry”. The industry is dominated by small and medium-sized companies,
working in three main sectors: clothing, home furnishings and industrial.
Activity in the textile finishing industry is distributed across the EU, but (within the EU-15)
the dominant Member State is Italy, accounting for around 36% of production, followed by
German (approx. 13%), France (approx. 12%), the UK and Spain (approx. 10% each). The
overall market for textiles, including yarn production and carpets, is also dominated by Italy,
with around a 30% market share (EC, 2002). Similarly, for leather, the most important
producer and transformer in Europe is Italy (84% of all companies), followed by Spain
[OECD, 2004B].
Within the textile and leather finishing industries, citric acid and related salts may be used in a
wide variety of applications. However, these uses may be summarized (albeit with some
overlap) as being based on either acidity (and pH regulation) or ability to complex metal ions.
Examples of applications where these are important are:
• Curing catalyst for treatments such as easy-care resins
• Acidification of flame-retardant treating baths
• Sequestering of alkaline earth or transition metal ions to prevent interference in dyeing

and other processes.
Potential exposure to humans and especially the environment is dependent on the intended
function of the substance, as well as the substrates and processes used. Functional finishing

agents and other chemically reactive substances are intended to be consumed during use,
therefore the amount released is related to efficiency of the process. On the other hand, non-
reacting substances (e.g. processing aids) are not consumed and will ultimately be lost to air
or waste water, depending on their function and physicochemical properties. In virtually all
cases, it is expected that citric acid or citrate salts, as process aids, will be lost to waste water.
The annual tonnage of 300 t is considered to be used at 40% in the region. The largest site is
estimated to use around 6 tpa. If all passed to waste water this is:
6 t x 1000 kg/t / 300 = 20 kg/d.
For human health worker exposure at textile production sites will be to aqueous formulations
for which no hazard has been identified. In addition, relevant exposures have been calculated
for life cycle stages with higher exposures. Therefore no attempt at quantification will be
made nor is needed.
No measured data are available for releases of citric acid to air and waste water from textile
production sites. Releases are therefore estimated on the basis of information in the public
domain.
Releases to air
As the citrates are solids with high water solubility, losses to air are considered to be
negligible.
Releases to waste water
Citric acid and citrates are used in textile and leather treatment in aqueous solution. The most
likely release route will be to waste water via spillage, clean out and discharge of spent
treatment baths and liquors recovered in handling fabrics after treatment. Indeed, releases to
waste water can be assumed to be 100%, since all the citric acid/citrate may be washed to
drain.
air

Table 9.48 summarises the risk management measures in place during production of citric
acid.

P

Resulting fraction of initially applied On-site biological waste treatment
amount in waste water released from (where present) is expected to remove
site to the external sewage system a high proportion of citric acid, as the
substance is highly biodegradable.
However, on-site biological waste
treatment is not assumed as it is not
known that this is always present.
Resulting fraction of applied amount No waste gases
in waste gas released to environment
Onsite waste treatment No measured data Secondary biological treatment may be
present but this is not assumed in the
scenario
Fraction of initially applied amount No measured data
sent to external waste treatment. This
is the sum of direct losses from
from onsite waste water and waste gas
treatment.
Municipal or other type of external None None
waste water treatment
Effluent (of the waste water treatment 2000000 l/d Default for a standard WWTP
plant) discharge rate
Recovery of sludge for agriculture or Yes
horticulture
At industrial sites, solid wastes may be disposed of via landfill or incineration, or are recycled
outside of the process. Dried sludge from on-site waste water treatment plants may be sold as
approved agricultural fertiliser. Details of the treatment of aqueous waste vary at different
sites but as a minimum, wastes are neutralised and the effluent treated in on- or off-site
secondary biological treatment plants prior to discharge. Waste gases are not generated.
In consumer and professional use, waste water passes to municipal WWTPs. Sludge may be
spread on agricultural land.
Predicted environmental release estimates have been used for releases during production. The
releases have been estimated using the exposure scenario for use in textiles (section 9.1.1.2

and 9.1.1.6) and Predicted Environmental Concentrations have been determined using EUSES
2.1.1. The EUSES program implements the environmental exposure models described in
REACH Technical Guidance Chapter R16. Default model parameters have been used with the
Production volume in EU: 300 tonnes
Local tonnage: 0.02 tonnes per day
Number of days: 300
PEC unit
AIR
WATER, SEDIMENT
SOIL, GROUNDWATER
Local PEC in pore water of agricultural soil 2.91x 10-3 [mg l-1]

9.10.2.1.2 Exposure concentration in sewage treatment plants (STP)
(STP). The concentration of the citrate has been estimated using EUSES 2.1.1. The EUSES
model uses the Simple Treat sewage treatment model to predict the fate of a substance in the
STP, based on the physicochemical and biodegradation properties. For citric acid,
SimpleTreat predicts the following:
12.6 % to water:
0.112 % to air:
0.0154 % to sludge:
87.3 % degraded.
output.
Estimated predicted exposure concentrations in freshwater and marine sediment are based on
EUSES 2.1.1. No measured data are available.
Exposure concentrations in soil and groundwater are estimated (on a regional basis) based on
EUSES 2.1.1. No measured data are available.
The Predicted Exposure Concentration (PEC) of citric acid in the atmosphere is estimated
based on EUSES 2.1.1. No measured data are available.

9.11 ES11: Use in paints and coatings
Following the REACH descriptor system [ECHA, 2009], one sector of use (SU) covered by
this generic scenario is:
SU10: (Formulation [mixing] of preparations and/or re-packaging).
However, use of paints and coatings is ubiquitous, encompassing several SUs, e.g.:
SU3: Industrial Manufacturing (all);
SU17: General manufacturing, e.g. machinery, equipment, vehicles, other transport

equipment;
SU18: Manufacture of furniture;
SU19: Building and construction work;
SU21: Private households (= general public = consumers);
SU22: Public domain (administration, education, entertainment, services, craftsmen).

Applications covered by this generic scenario encompass the following product categories
(PC):
PC9: Coatings and Paints, Fillers, Putties, Thinners.
The term “coatings” as used here describes any material that can be applied to a surface as a
thin continuous, layer (film). This includes paints, lacquers or varnishes. Such coatings are
used in a wide range of application to protect surfaces from corrosion and other
environmental effects, provide decorative effects and improve inherent performance
properties. Film formation can be a physical process, where solvents evaporate from solutions
or melted substances solidify, or a chemical process involving reactions between reactive
groups in binders [OECD, 2007].
The application of a coating to a surface can be by manual use of brush/roller, spraying

systems, and dip or roll coating systems [OECD, 2007]. The type and constituent composition
of the coating product are based on the substrate, intended use, service environment and the
desired role of coating. Decorative coatings cover the use of paints applied to buildings, their
trim and fittings and for decorative and protective purposes by both professionals and the
general public. All decorative coatings are supplied as liquid materials [OECD, 2007].
Titanium dioxide (TiO2) is the most important inorganic pigment in terms of quantity. The
world production in 2000 amounted to nearly 4 million tonnes per year. Titanium dioxide
white inorganic pigments are used primarily in the production of paints, printing inks, paper
and plastic products. Titanium dioxide is of outstanding importance as a white pigment
because of its scattering properties, its chemical stability, and lack of toxicity [BREF, 2007].
The following application should be taken as representative rather than the sole example of
where and why citric acid or citrates may be used within the coatings industry.

In the paint industry citric acid and citrate salts are used to retard the settling of titanium
dioxide, the most common pigment used in paints and other coatings [APAC, 2009]. Thus,
shipping of titanium dioxide as an aqueous slurry has advantages in handling and storage
space versus shipping as a fine solid. Although titanium dioxide particles will initially
disperse in water, they separate rapidly and in a short time will form a hard-packed sediment
which is virtually impossible to re-disperse. The presence of ions such as calcium or iron
causes flocculation which exacerbates the problem. In the early 1970s, it was discovered that
addition of 0.04 – 0.4% citric acid or tartaric acid or their simple salts (sodium, potassium,
ammonium) substantially retarded the settling and packing of titanium dioxide particles in
aqueous dispersions [US 3,663,284].
At least a portion of the citric acid added to aid shipment of the pigment is likely to still be
present during formulation of the paint. Indeed, it is possible that further additions are made
to allow re-dispersion of pigment in the final paint formulation.
Formulation
A paint factory formulating 10000 tpa of formulated paint could need around 10000 x 0.001 =
10 tpa of citric acid. Paint formulation is a widespread activity and this estimate is consistent
with a total market size of 300 tpa.
It is taken that the regional tonnage is 40 tpa.
Assuming a worst case of 2% handling loss this is a local release of 200 kg per year. Such a
wastage rate is less than for scenarios considered earlier and there is no need to calculate local
exposures. The releases will be added as regional and continental losses to waste water:
Regional = 200 x (40/10) / 365 = 2.2 kg/d
Continental 2.2 x (260/40) = 14.3 kg/d
Use
The coating process used by both professionals and consumers is typically by brush or roller
application. For releases to waste water during consumer use, the OECD Emission Scenario
Document for coatings assumes that an estimated 1% of the volatile fraction of the coating
will be lost as brush residues and then end up in the sewer. The same fraction (1%) of the
volatile fraction is assumed to be lost during professional use, but this is properly disposed
and does not end up in the sewer [OECD, 2007].
Therefore the amount of citric acid in the application passing to waste is estimated to be
widely dispersed:
Regional wastewater:
0.1 x 300 tpa x 1000 kg/t x 0.01 /365 = 0.82 kg/d

Continental wastewater:
0.9 x 300 tpa x 1000 kg/t x 0.01 /365 = 7.40 kg/d
Therefore, for simplicity, for this application area, the totals are:
2.2 + 0.82 = 3.0 kg/d
14.3 + 7.4 = 21.7 kg/d
For human health worker exposure at paint production sites will be to aqueous formulations
for which no hazard has been identified. In addition, relevant exposures have been calculated
for life cycle stages with higher exposures. Therefore no attempt at quantification will be
made nor is needed.

9.12 ES12: Use in photography
Following the REACH descriptor system [ECHA, 2009] the following sectors of use are
covered by this scenario:
SU21 Professional uses
SU22 Consumer uses
The relevant product category is PC30: Photochemicals.
Citric acid is one of a range of complexing agents used in photography to control the effects
of calcium and magnesium hardness, and to keep iron soluble in solution as part of redox
processes.
Due to the rapid growth of digital photography, use of chemicals in film processing is now
limited almost entirely to a small number of professional providers. The chemicals used are
collected by photochemical companies in order to recover silver and disposal to drain does
not take place.
Citrate may also be used as a stop bath in professional or consumer settings as part of the
process for the manual development of photographic film. Releases to the environment from
this application are insignificant compared to those from considered in other exposure
scenarios (cleaning products for example).
Therefore this scenario need not be considered further in respect of the environment.
For human health, the processes applied during both professional and consumer uses are:
PROC 9 Transfer of substance or preparation into small containers (dedicated filling line,
including weighing)
PROC 5 Mixing or blending in batch processes for formulation of preparations and articles
PROC 13 Treatment of articles by dipping and pouring

9.13 Use as a laboratory reagent
Following the REACH descriptor system [ECHA, 2009] the following sector of use is
covered by this scenario: SU3 Industrial uses
The relevant product category is PC21 Laboratory chemicals
Citric acid may be used at low levels within laboratories. Exposures will take place but under
highly controlled conditions. Therefore this scenario need not be considered further for
human health or the environment.

9.14 Use in water treatment
This scenario covers use in smaller-scale circulating water treatment in industrial settings,
which typically use high substance concentration at low discharges and would usually have a
waste water treatment plant (WWTP) in place. The degradability of citric acid in power
station cooling systems makes in not suitable for such purposes.
The tonnage of 1000 tpa is an estimate.
REACH Guidance R.12 describe Sectors of use, Product Categories generic Environmental
Release Categories (ERCs) that can be linked to the lifecycle and use pattern of substances.
The REACH descriptors relevant to the use of citrates in water treatment products are as
follows:
Sectors of use:
Main user groups:
SU3: Industrial manufacturing (all)
End user groups:
SU10: Formulation of preparations
Chemical product category:
PC20: Products such as pH-regulators, flocculants, precipitants, neutralisation agents, other

unspecific
PC37: Water treatment chemicals
Environmental release categories
ERC2: Formulation of preparations
ERC4: Industrial use of processing aids
Industrial cooling systems can be categorized by their design and by using water as coolants.
The exchange of heat between process medium and coolant is enhanced by heat exchangers.
From the heat exchangers the coolant transports the heat into the environment.
Usage of water treatments containing citrates would be continuous for the correct functioning
of the cooling water system. Re-loading may be needed more or less frequently, for open and
closed cooling water systems respectively, to refresh the system.

The worst-case for the local environment is to assume treatment of a large industrial plant,
open cooling system, which requires the use of large volumes of a high concentration product
on a continuous basis and involves the direct release of blow down effluent to the river or
receiving water.
In open recirculating systems, alkaline conditions (pH of 8-9), in combination with organic
complexing agents are effective against corrosion and scaling. Most currently used corrosion
programmes are based on phosphates, and zinc is added if water conditions require this.
Typical concentrations of scale control agents (polyphosphates, phosphonates, polyacrylates,

copolymers and ter-polymers) range from 2 to 20 mg/l, as active compound. Hardness
stabilisers prevent the formation of crystals and are used in recirculating systems, but rarely or
never in once-through systems. Citrates may be used to enhance the performance of the other
additives.
In most downstream uses treatment chemicals are applied in water-based processes. The final
concentration in the water used in scale inhibition is typically from less than 1 to 10 ppm.
Depending on the exact nature of the process, the complexing agents may remain present in
the aqueous effluent and the discharge streams. These streams will be treated on the user’s
site, discharged to sewer systems or discharged to waterways (wide dispersive use).
Given the low volatility and the high water solubility of the substances, direct releases to air
and soil can be considered negligible.
The OECD Emission Scenario Document for Water Treatment discusses scenarios that are
relevant for open cooling systems. It refers to the possibility of loss of treated cooling water
from the system through process of drift (the spray (plume) produced from the top of an
evaporative cooling tower); windage (physical loss of water from a cooling tower caused by
draught of air or wind); or bleed/purge/blowdown (water deliberately removed from a cooling
system to control the concentration factor of dissolved solids). Depending on the type of drift
and mist elimination equipment fitted, these losses may be small. For the UK, a loss of 0.01%
of the recirculation rate in the system is suggested. Given the chemical properties of citrates,
it can be assumed that the entire release is via water and not volatilised. It is assumed that
traps on the site will collect the majority of the windage loss. In the UK approximately half of
the bleed/purge discharges are to sewer and the remainder are to estuaries or to sea (though
these would be treated before discharge). Blow down losses can be considered to be on a
continuous basis. Overall, it is assumed that citrates released to waste water for treatment
equivalent to that associated with a municipal WWTP. Many installations will be situated
next to much larger rivers than the default size.
In the UK, the capacity of 50% of installed base cooling towers is in the range of 22.7 m3 and
227 m3 (OECD, 2004). The water circulation rate of a typical open cooling system (with
capacity of 100 m3), for an industrial plant, is assumed to be 350 m3/h (3.5 times the
capacity). The blowdown of open cooling systems is related to the rate of evaporation (1% of
the circulation rate) and the concentration cycle, which is the ratio (typically 3) of the
maximum concentration of dissolved solids in the recirculating water to the concentration in
the make up water (OECD, 2004).
For the purpose of this calculation, a scaling inhibitor product with an active content of citrate
at 25% is assumed.

Therefore, for a blowdown of 1.75 m3/h from an open cooling system; the estimated release
of citrates to water is
0.25 x 20 mg/l x 1.75 m3/h x 1000 l/m3 x 24 h/d x 10-6 kg/mg
= 0.44 kg/day.
This is lower than ES considered above and there is therefore no need to develop the scenario
further.
In the nature of the use it must be assumed that all the citric acid used in water treatment
could pass to waste water. Therefore:
0.1 x 1000 tpa x 1000 kg/t /365 = 274 kg/d
0.9 x 1000 tpa x 1000 kg/t x /365 = 2470 kg/d
For human health worker exposure at industrial sites will be to aqueous formulations for
nor is needed.

9.15 ES15: Use in metal surface treatment
Citric acid may be used as a complexing agent during metal surface treatment operations.
This includes cleaning, brightening and passivation of fabricated stainless steel components,
and other metal components, cleaning of circuit boards prior to soldering, and metal cleaning
or chemical polishing for the surface treatment of aluminium, copper and other metals. The
following applications should be taken as representative rather than the sole example of where
and why citric acid or citrates may be used in the treatment of metal surfaces. Some industries
using citric acid include fasteners, medical devices, semi-conductors, automotive and
aerospace.
Passivation: Citric acid may be used in stainless steel passivation to remove iron from the
surface of the stainless steel and prevent later corrosion. After thorough cleaning, the stainless
steel part is immersed in a passivating acid bath. Any one of three approaches can be used:
nitric acid passivation, nitric acid with sodium dichromate passivation and citric acid
passivation. Which approach to use depends on the grade of stainless steel and prescribed
acceptance criteria. When citric acid passivation is used, typical solutions range from 4 to
10% citric acid by weight.
Electroless plating: Plating describes the coating of surfaces with metals, either through an
electrolysis or electroless plating processes. Electroless plating is also known as
‘autocatalytic’ plating; deposition of the metal starts on metal nuclei such as palladium and
continues autocatalytically. Electroless plating is favoured over electrolysis for most
component production (EA 2009).
There are usually three stages in the electroless plating process: de-smearing, activation and
electroless copper plating. The plating solution has a copper content of 2 – 5 g/l, with sodium
hydroxide (15 – 20 g/l), complexing agents (10 – 15 g/l) or tartrates (5 – 10 g/l) and reducing
agents, such as formaldehyde (3 – 5 g/l). The process solution lifetime is limited by the build-
up of reaction products and is proportional to the rate of throughput of components (EA
2009). Citrate may be used as a complexing agent.
Electroless plating involves the large-scale use of water in both providing the medium for the
process itself and for the subsequent rinsing and washing of components. There is a degree of
recycling of rinse water through use to top-up the plating tanks, but there is ultimately loss
through carry-over on components. Spent fluids can only be topped up a limited number of
times before the media needs replacing. Water-soluble waste is discharged in waste water for
basic on-site treatment (settling and pH adjustment) before discharge to municipal treatment
works, controlled by local discharge consent agreements (EA 2009).
The use of citrate in metal-surface treatment is estimated as approx. 1000 tpa. Therefore,
environmental releases are not dissimilar to those discussed in the cleaning scenario (ES5) but
on a much smaller scale. Therefore, it is not considered necessary to further assess
environmental exposure.
For workers, exposures are not expected to be greater than those discussed in other industrial
use scenarios. The basic risk management measures discussed for these scenarios are
considered sufficient to ensure safe use. Human health exposure is not discussed further.

9.16 ES16: Use in agriculture
generic scenario: PC12 Fertilizers and PC22 Lawn and Garden Preparations, including
fertilizers.
Citrate complexes of iron, copper, magnesium, manganese and zinc are used to correct soil
deficiencies of these minerals because they are soluble in water at normal soil pH. The soluble
citrate complex promotes the transfer of the metal nutrient into the plant's root or leaf system.
The biodegradability of citric acid is important for this application (APAC 2009).
One common method for making fertilisers involves dissolving metal sulfates in water and
citric acid followed by neutralization with ammonia. This process may be carried out in an
industrial setting as part of the formulation of solid or liquid fertilisers/plant feeds. In this
case, citric acid is an intermediate and it is the metal-citrate or ammonium citrate that must be
considered for the professional or consumer use of fertilisers/plant feeds. Magnesium citrate
may be used in this context. Alternatively, mixing of fertilisers may take place on farms. In
this case, exposure may be to solid or liquid citric acid or metal-citrate (including sodium
citrate).
Citrates may also be present as dispersant/scale inhibiting agents, i.e. adjuvants in the
preparation. Evidence from other applications in which citrate is acting as a scale control
agent/dispersant suggests that citrate may be present at very low levels in the formulation,
perhaps approx. 1-20 ppm.
In any of the above cases, marketed products may be solid (granules or pellets) or solution.
Processes used may include transfer, loading, mixing, rolling/brushing and spraying.
Plant feeds containing citrates may also be used in professional or consumer settings. The
products may be liquids or granules and may be sprayed or poured.
Citrates may also be used in plant protection products and in animal feed; however, these
applications fall outside the scope of REACH.
The amount of citric acid believed to be used in this application is at most 1500 tpa. The use
per site is unknown, but this should be considered as a widely dispersed use. In the worst case
a release of the entire tonnage to the region could be included, i.e. 1500 tpa. Of this, part will
be released to agricultural soil (90%) and part to waste water (10%).
A regional release of 150 x 1000/365 = 411 kg/d to waste water will be added to the model,
and 3699 kg/d to soil will be included.
For human health worker exposure will be to aqueous formulations for which no hazard has
been identified. In addition, relevant exposures have been calculated for life cycle stages with
higher exposures. Therefore no attempt at quantification will be made nor is needed.

9.17 Use in medical devices
Citrates may be used in medical devices, for example, citrate is added to human blood to
prevent coagulation. The whole blood collection process is a closed process as sterility must
be maintained. Procedures are carried out by trained personnel in a controlled environment.
Therefore, exposures from this use are expected to be minimal and the scenario is not
considered further for human health or the environment.

9.18 Regional exposure concentrations
Table 9.50 shows the predicted regional exposure concentrations calculated from the sum of
the regional PECs for each exposure scenario. Bioaccumulation is not of concern for this
substance, so regional concentrations in the food chain are not assessed.
Table 9.50: Regional exposure concentrations
Predicted regional Measured regional Explanation / source of measured data
Exposure exposure
Concentrations concentrations
value unit value unit

Freshwater 1.52 x mg/l No data The value represents the sum of the regional
10-2 PECs calculated by EUSES 2.1.1
Marine water 1.41-3 mg/l No data The value represents the sum of the regional
PECs calculated by EUSES 2.1.1
Freshwater 3.32 x mg/kg No data The value represents the sum of the regional
sediments 10-1 d.w. PECs calculated by EUSES 2.1.1
Marine 2.60 x mg/l No data The value represents the sum of the regional
sediments 10-2 PECs calculated by EUSES 2.1.1
Agricultural 3.19 x mg/kg No data The value represents the sum of the regional
soil 10-3 wwt PECs calculated by EUSES 2.1.1
Grassland 7.47 x mg/kg No data The value represents the sum of the regional
10-12 wwt PECs calculated by EUSES 2.1.1
Air 1.24 x (mg/m3 No data The value represents the sum of the regional
10-19 ) PECs calculated by EUSES 2.1.1

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Safety Data Sheet

SECTION 1: Identification of the substance/mixture and of the company/undertaking

Trade name: Citric Acid Anhydrous

Signal word: Warning

Trade name: Citric Acid Anhydrous

Trade name: Citric Acid Anhydrous

Tightly sealed goggles (EN 166).

Body protection: Protective work clothing.

Trade name: Citric Acid Anhydrous

Trade name: Citric Acid Anhydrous

12.2 Persistence and degradability Easily biodegradable

Trade name: Citric Acid Anhydrous

Citrates Consortium 1 FINAL VERSION JULY 2010

9.1.1 Exposure scenario

9.1.1.1 Description of activities and processes covered in the exposure scenario

Citric acid production is largely by microbiological fermentation of molasses and sugar

9.1.1.2 Operational conditions related to frequency, duration and amount of use

Table 9.3: Duration, frequency and amount

Used amount of substance per day 30 tonnes

9.1.1.3 Operational conditions and risk management measures related to product

Citrates Consortium 2 FINAL VERSION JULY 2010

Physical state Solid. Various powder

9.1.1.4 Operational conditions related to available dilution capacity and

Table 9.5: Operational conditions related to respiration and skin contact

Area of skin contact with the ECETOC TRA default:

480 cm2 PROC 2: palms of both hands

240 cm2 PROC 3: palm of one hand

480 cm2 PROC4: palms of both hands

480 cm2 PROC8b: palms of both hands

Body weight 70 kg Default

Environmental surroundings characteristics

9.1.1.5 Other operational conditions of use

Releases to waste water

Citrates Consortium 3 FINAL VERSION JULY 2010

The total passing to aqueous waste water is 3.86 kg/d.

9.1.1.6 Risk management measures

Table 9.7: Risk management measures for industrial site

Containment and local exhaust ventilation

Citrates Consortium 4 FINAL VERSION JULY 2010

sewage system substance is highly biodegradable.

9.1.1.7 Waste related measures

Waste gases are not generated.

9.1.2 Exposure estimation

9.1.2.1 Workers exposure

9.1.2.1.1 Acute/Short term exposure

Citrates Consortium 5 FINAL VERSION JULY 2010

Dermal uptake of citrate is expected to be minimal as it is extremely hydrophilic with a very

Citrates Consortium 6 FINAL VERSION JULY 2010

Industrial PROC1 Use in closed Nob Yes 100 240 0.3

PROC2 Use in closed, Yes Yes 20 480 0.14

PROC3 Use in closed Yes Yes 10 240 0.03

PROC4 Use in batch Yes Yes 100 480 0.69

PROC8b Transfer Yes Yes 100 480 0.69

Citrates Consortium 7 FINAL VERSION JULY 2010

Exposure Process Description LEV LEV Predicted Predicted Inhalation

Citrates Consortium 8 FINAL VERSION JULY 2010

9.1.2.2 Consumer exposure

Consumer exposure is not applicable to chemical manufacturing.