Page: 1 / 46

Date of issue: Jun 1996

Revision: 01.06.2015
Version: 06

MATERIAL SAFETY DATA SHEET

SODIUM HYDROXIDE

1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING

1.1. Product identifier
Trade name: SODIUM HYDROXIDE
Chemical name: Sodium hydroxide
CAS number: 1310-73-2
EC number: 215-185-5
INDEX number: 011-002-00-6
Registration number: 01-2119457892-27-0044
1.2. Relevant identified uses of the For neutralization and regeneration in chemical, processing industry and pulp
substance or mixture and and paper industry.
uses advised against:
1.3. Details of the supplier of the TKI Hrastnik d.d.
safety data sheet: Za Savo 6
1430 Hrastnik
Slovenia
Phone.: +386 (0)3 56 43 702
Fax: +386 (0)3 56 44 048
E-mail: tki@tki.si
Homepage: http://www.tki.si
1.4. Emergency telephone Call national poison centre or doctor.
number: Additional information: +386 (0)3 56 43 702.

2. HAZARDS IDENTIFICATION:
2.1. Classification of the
substance or mixture
Classification in accordance Met. Corr. 1
with Regulation (EC) No H314
1272/2008: H290
Hazard statements – see chapter 16.

Adverse physicochemical, The reaction between the Sodium hydroxide and acids is vigorous and
human health and exothermic. In contact with metals is corrosive. High pH - corrosive.
environmental effects: Severe irritations and burns on skin and injury on eyes and mucous
membranes. Dangerous if swallowed.
In larger quantities it is dangerous to the environment due to increase in pH.
2.2. Label elements
Hazard pictograms:

Signal word: Dangerous

Hazard statements: H314: Causes severe skin burns and eye damage.
H290: May be corrosive to metal.
 TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 2 / 46

Precautionary statements:
P260: Avoid breathing dust/fume/gas/mist/vapours/spray
P280: Wear protective gloves/protective clothing/eye protective/face protective
P303 + P361 + P353: IF ON SKIN (or hair): Remove/Take off all
Contaminated clothing. Rinse skin with water/shower.
P305 + P351 + P338: IF IN EYES: rinse cautiously with water for several
minutes.
Remove contact lenses, if present and easy to do. Continue rinsing.
P310: Call POISON CENTER or doctor/physician

2.3. Other hazards: /

3. COMPOSITION/INFORMATION ON INGREDIENTS:
3.1. Substances
Hazard
Conc. Classificatio
Component Reg. No. EC No. CAS No. INDEX No. statement
(%) n
s
01- H314
Skin Corr. 1A
Sodim Hydroxide 2119457892- 215-185-5 1310-73-2 011-002-00-6 30 -50 Met. Corr. 1 H290
27-0044
Hazard statements – see chapter 16.

4. FIRST AID MEASURES:

4.1. Description of first aid
measures:
General measures: Avoid further contact with the substance and immediately remove clothing
soiled by product. Contaminated clothing should be washed before reuse.
Inhalation: Not necessary
Skin contact: Immediately wash with plenty of water. Obtain medical attention.
Eye contact: Rinse opened eyes with plenty of water and seek medical advice.
Ingestion: Drink plenty of water. Do not induce vomiting! Seek medical advice.
4.2. Most important symptoms and
effects, both acute and
delayed:
4.3. Indication of any immediate Use appropriate personal protective equipment. See item 8. Wear protective
medical attention and special clothing. Safety showers and eyewash facilities should be provided.
treatment needed: Inform doctor of the causes of damage and if possible show the label or safety
data sheet.

5. FIREFIGHTING MEASURES:
5.1. Extinguishing media
Suitable extinguishing media: The product itself is not flammable; take extinguishing action appropriate to the
fire in the surroundings.
Extinguishing media which Not known.
shall not be used for safety
reasons:
5.2. Special hazards arising from In contact with some metals (Eg. Al) sodium hydroxide reacts to liberate highly
the substance or mixture: flammable hydrogen gas. In the event of a fire be careful on the strong alkaline
reactive solution.
 TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 3 / 46

5.3. Advice for firefighters: Approved self-contained breathing apparatus and full protective clothing

6. ACCIDENTAL RELEASE MEASURES

6.1. Personal precautions,
protective equipment and
emergency procedures
For non-emergency Wear protective equipment. See item 8. Keep unprotected people away.
personnel:
For emergency responders:
6.2. Environmental precautions: Do not allow to enter sewers/surface or ground water.
6.3. Methods and material for Absorb the spill with inert liquid – binding material (sand, dry soil, clay or
containment and cleaning up: universal binders). Pick up mechanically. Dispose contaminated material as
waste according to item 13. After removal wash spill area with plenty of water.
6.4. Reference to other sections:

7. HANDLING AND STORAGE

7.1. Precautions for safe
handling
Recommendations: Employer staff to safe manage with the chemical. Handle with care. When
handling product use appropriate personal protective equipment. See item 8.
Advice on general Ensure a clean working environment. While working do not eat and drink. After
occupational hygiene: work, wash your hands, undress and wash contaminated clothing.
7.2. Conditions for safe storage, In closed containers at a temperature more than +10 o. Provide ventilation.
including any Packaging must be of a material resistant to bases.
incompatibilities: Overfill prevention devices for containers and prevention devices for spills into
the environment.
Incompatible materials: Acids, halogenated organic compounds, light metals
such as: Al, Mg, Sn, Zn.
7.3. Specific end use(s): /

8. EXPOSURE CONTROLS/PERSONAL PROTECTION

8.1. Control parameters: MV in the workplace for Sodium Hydroxide is 2 (I)mg/m3.
8.2. Exposure controls
Appropriate engineering Ventilation of rooms.
controls:
Individual protection
measures
Eye/face protection: Personal eye protection – SIST EN 166:2002
Skin protection: Protective clothing against liquid chemicals – SIST EN 13034:2005, safety
footwear – SIST EN ISO 20345:2012
Hand protection: Protective gloves against chemicals and microorganisms – SIST EN 374
Respiratory protection: Not necessary.
Thermal hazards:
Other:
Environmental exposure Implement measures to protect the environment.
controls:
 TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 4 / 46

9. PHYSICAL AND CHEMICAL PROPERTIES

9.1. Information on basic physical
and chemical properties:
Appearance: Colourless viscous liquid.
Odour: Odourless.
Odour threshold:
pH: 14 (30-50% solution)
Melting point/freezing point: 12 oC
Initial boiling point and boiling 143 oC
range:
Flash point: Not flammable.
Evaporation rate:
Flammability (solid, gas): Not flammable.
Upper/lower flammability or
explosive limits:
Vapour pressure: ca. 60 mmHg (50% solution, 82 oC)
Relative density: 1,3 g/cm3 - 1,5 g/cm3 (20 oC)
Solubility(ies): Fully miscible.
Partition coefficient: n- No data available
octanol/water:
Auto-ignition temperature: Not self igniting.
Decomposition temperature:
Viscosity:
Explosive properties: Not explosive.
Oxidising properties: Not oxiditative.
9.2. Other information:

10. STABILITY AND REACTIVITY

10.1. Reactivity:
10.2. Chemical stability:
10.3. Possibility of hazardous
reactions:
10.4. Conditions to avoid: Do not mix with acids uncontrolled. Reacts with CO2 from the air and form sodium
carbonate.
10.5. Incompatible materials: Acids, halogenated organic compounds, light metals such as: Al, Mg, Sn, Zn.
10.6. Hazardous decomposition Sodium oxide, hydrogen, in contact with those metals.
products:

11. TOXICOLOGICAL INFORMATION

11.1. Information on toxicological
effects:
Acute toxicity:
Skin corrosion/irritation:
Serious eye damage/irritation:
 TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 5 / 46

Respiratory or skin No data available

sensitisation:
Germ cell mutagenicity: No data available
Carcinogenicity: No data available
Reproductive toxicity: No data available
STOT-single exposure:
STOT-repeated exposure:
Aspiration hazard:
Information on likely routes of
exposure:
Inhalation: /
Ingestion: Burning on mouth and stomach.
Skin contact: Corrosive and irritating to the skin.
Eye contact: Causes burns, danger to go blind.
Symptoms related to the
physical, chemical and
toxicological characteristics:
Delayed and immediate effects Slippery surface of the skin, corrosion, burn eyes, pain.
as well as chronic effects from
short and long-term exposure:
Other information:

12. ECOLOGICAL INFORMATION

12.1. Toxicity: Toxicity to aquatic organisms:
LC0 = 157 mg/l, LC50 = 189 mg/l, LC100 = 200 mg/l;
Above 20 mg / l is toxic to fish.
In case of spills of large quantities of the product the possible impact on the
environment is increase the pH.

12.2. Persistence and No data available.

degradability:
12.3. Bioaccumulative potential: No data available.
12.4. Mobility in soil: The possibility of spills in the environment.
12.5. Results of PBT and vPvB
assessment:
12.6. Other adverse effects: Possibility of formation of chlorine cloud

13. DISPOSAL CONSIDERATIONS

13.1. Waste treatment methods
Disposal of the substance or
preparation:
Disposal must be made according to official regulations.
Disposal of the
contaminated packaging:
Disposal must be made according to official regulations.
 TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 6 / 46

14. TRANSPORT INFORMATION

14.1. UN number: UN 1824
14.2. UN proper shipping name: SODIUM HYDROXIDE, solution
14.3. Transport hazard class(es): 8
14.4. Packing group: II
14.5. Environmental hazards:
14.6. Special precautions for user:
14.7. Transport in bulk according
to Annex II of MARPOL73/78
and the IBC Code:

15. REGULATORY INFORMATION

15.1. Safety, health and Regulation (EC) No 1907/2006, Regulation (EC) No 1272/2008
environmental
regulations/legislation
specific for the substance or
mixture:
15.2. Chemical safety
assessment:

16. OTHER INFORMATION

List of hazard statements and/or
precautionary statements:

H314 Causes severe skin burns and eye damage

H290 May be corrosive to metal

Abbreviations and acronyms: Skin. Corr. 1A: skin corrosion/irritation, category 1A.
Met. Corr. 1: a substance or mixture is corrosive to the metal, category 1
STOT: specific target organ toxicity
PBT: persistent, bioaccumulative and toxic
vPvB: very persistent and very bioaccumulative
Training advice: Workers must be trained in safe handling of the chemical in accordance with
current legislation on health and safety at work and in the field of chemicals.
Additional information: Obtain additional information on the telephone number listed in Chapter 1.
Sources: Safety data sheet TKI Hrastnik for Sodium Hydroxide solution in Slovenian
language (Date of issue 01.06.2015).
Information, which has been Material Safety Data Sheet has been changed at all points in order to comply
added, deleted or revised: with current legislation (amendment of Annex II to Regulation 1907/2006
(REACH) and Regulation 1272/2008 (CLP)).

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.
Appendix of this MSDS are exposure scenarios for Sodium hydroxide.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 7 / 46

ANNEX: Exposure assessment

The exposure scenarios are organised in 4 main scenarios:

 Manufacturing of liquid NaOH

 Manufacturing of solid NaOH

 Industrial and professional use of NaOH

 Consumer use of NaOH

The overview of exposure scenarios and coverage of substance life cycle can be found in Table 1.
The exposure assessment is primarily based on the exposure assessment of the EU RAR for NaOH
(2007). The RAR (2007) and the information collected at that time was used as starting basis for this
dossier. When available, new data and information was added to the dossier.

Table 1 Overview on exposure scenarios and coverage of substance life cycle

Number and title Manu- Prepa- Industrial Consumer Article Waste

facture ration and/or wide use service stage
making disperse use life
ES1: Manufacturing of X
liquid NaOH
ES2: Manufacturing of X
solid NaOH
ES3: Industrial and X X
professional use of
NaOH
ES4: Consumer use of X
NaOH

Note on accidental exposure

Since accidental exposure is normally excluded from an EU chemical safety assessment and
accidental exposure is considered in the EU RAR (2007; section 4.1.1.3.2, pages 59-62), accidental
exposure will not be further assessed in this dossier. However, the risk management measures for
consumers, identified in the NaOH risk reduction strategy (EU RRS, 2008) are included in the dossier.

Exposure Scenario 1: Manufacturing of liquid NaOH

In the EU RAR (2007), the required information related with occupational exposure at the production
sites was collected through a questionnaire, developed by Euro Chlor in cooperation with the
Rapporteur Member State. In the questionnaire the following issues were addressed: type of products
(solid/liquid), number of workers, estimation of exposure based on tasks, exposure measurements and
accidental exposure. The questionnaires were sent by Euro Chlor to 97% of the European chlorine
production sites (a total of 86). A total number of 36 production sites (42%) responded to the
questionnaire and based on these data a detailed report has been prepared (Euro Chlor, 2004c).

Exposure scenario
Short title of the exposure scenario

SU 3, 8: Manufacture of bulk, large-scale substances

PROC 1, 2, 3, 4, 8, 9: use in (closed) continuous or batch process with no likelihood of exposure or

TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 8 / 46

where opportunity for exposure arises (industrial setting), including charging, discharging, sampling
and maintenance

PC and AC not applicable for this ES

Description of activities and processes covered in the exposure scenario

NaOH is produced commercially by an electrolytic process. Brine, prepared from sodium chloride, is
electrolyzed in either a mercury cell, diaphragm cell or membrane cell. The coproducts are chlorine
and hydrogen. In the mercury cell process, a sodium-mercury amalgam is formed in the cell. The
amalgam is sent to a decomposer where it is reacted with water to form liquid NaOH, hydrogen and
free mercury. The free mercury is returned to the electrolytic cell. The resulting NaOH solution is then
stored in storage tanks as a 50% solution. The solution is shipped in tank trucks, tank cars or barges.
In the membrane process, a solution of approximately 30% in strength is formed in the cell. The
solution is then sent to evaporators, which concentrate it to a strength of 50% by removing the
appropriate amount of water. The resulting NaOH solution is stored in storage tanks prior to shipment.
The diaphragm process is very similar to the membrane process except that a solution of only 10-12%
is formed in the cell. Therefore, additional evaporation is required to reach the commercialised
concentration of 50%. The anhydrous forms of NaOH are obtained through further concentration of
50% NaOH.

Operational conditions

The amount used per worker varies from activity to activity. In the EU RAR (2007), the amount of
product sampled ranged between 0.1 and 15 litres. The responses with the highest quantities were
“15”, “2.2”, “2”, “3x1” and “few litres per day”. The remaining respondents replied that an amount of
less than 1 kg was sampled.

The duration considered for this exposure scenario is a full working shift (8h/day) and 200 days/year.
For sampling the “task duration in minutes per day” ranged between 1 and 600 minutes and the
average duration was 71 minutes.

From the questionnaire and the EU RAR (2007), it can be concluded that nearly all production sites
manufacture liquid NaOH with a concentration of about 50%. For 36% of the sites also other liquid
products (between 10 and 75%) are manufactured with concentrations which were in general lower
than 50%.

Risk management measures

Risk management measures related to workers

The risk management measures related to workers are summarized in Table 2. A distinction is made
between measures that are required or compulsory and measures that indicate good practice.

Because sodium hydroxide is corrosive, the risk management measures for human health should
focus on the prevention of direct contact with the substance. For this reason automated and closed
systems should preferably be used for industrial and professional uses of sodium hydroxide.
Respiratory protection is needed when aerosols of sodium hydroxide can be formed. Due to the
corrosive properties appropriate skin and eye protection is required.

Table 2 Risk management measures related to workers

Information type Data field Explanation

Good practice: replacing, where Situation at the time of the EU RAR
appropriated, manual processes by (2007): The confinement was in
automated and/or closed processes. general “semi closed” (18 sites). In
This would avoid irritating mists and the remaining cases the
Containment plus good subsequent potential splashes (EU RRS, confinement was “open” (6 sites) or
work practice required 2008): “totally closed” (9 sites).
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 9 / 46

Information type Data field Explanation

 Use closed systems or covering of
open containers (e.g. screens) (good
practice)
 Transport over pipes, technical
barrel filling/emptying of barrel with
automatic systems (suction pumps
etc.) (good practice)
 Use of pliers, grip arms with long
handles with manual use “to avoid
direct contact and exposure by
splashes (no working over one’s
head)” (good practice)
To improve air quality and avoid
potential respiratory track irritation
in working areas
Local exhaust ventilation Situation at the time of the EU RAR
required plus good work Local exhaust ventilation is not required (2007): Only five sites had “local
practise but good practice. exhaust ventilation”.
To improve air quality and avoid
potential respiratory track irritation
in working areas.
Situation at the time of the EU RAR
(2007): General ventilation was
present for 26 sites, while 5 sites
had no “general ventilation” during
General ventilation is good practice sampling. Four sites had neither
unless local exhaust ventilation is “general ventilation” nor “local
General ventilation present exhaust ventilation”.
 Respiratory protection: In case of
dust or aerosol formation: use
respiratory protection with approved
filter (P2) (required)
 Hand protection: impervious
chemical resistant protective gloves
(required)
o material: butyl-rubber, PVC,
polychloroprene with natural
latex liner, material
thickness: 0.5 mm,
breakthrough time: > 480
min
o material: nitrile-rubber,
fluorinated rubber, material Situation at the time of the EU RAR
thickness: 0.35-0.4 mm, (2007): In nearly all cases no PPE
breakthrough time: > 480 was used to protect against
Personal protection inhalation, but in all cases the skin
min
equipment (PPE) and eyes were protected (e.g.
required under regular  Eye protection: chemical resistant safety glasses, full face mask,
working conditions goggles must be worn. If splashes gloves, special clothes).
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 10 / 46

Information type Data field Explanation

are likely to occur, wear tightly fitting
safety goggles, face –shield
(required)
 Wear suitable protective clothing,
aprons, shield and suits, if splashes
are likely to occur, wear: rubber or
plastic boots, rubber or plastic boots
(required)
Next measures are required (from EU
RRS, 2008):
 workers in the risky
process/areas identified should
be trained a) to avoid to work
without respiratory protection
and b) to understand the
corrosive properties and,
especially, the respiratory
inhalation effects of sodium
Other risk management hydroxide and c) to follow the
measures related to safer procedures instructed by
workers. For example: the employer (EU RRS, 2008).
Particular training
systems,  the employer has also to
monitoring/reporting or ascertain that the required PPE
auditing systems,
is available and used according
specific control
to instructions
guidance.

Risk management measures related to environment

Risk management measures related to the environment aim to avoid discharging NaOH solutions into
municipal wastewater or to surface water, in case such discharges are expected to cause significant
pH changes. Regular control of the pH value during introduction into open waters is required. In
general discharges should be carried out such that pH changes in receiving surface waters are
minimised. In general most aquatic organisms can tolerate pH values in the range of 6-9. This is also
reflected in the description of standard OECD tests with aquatic organisms.

Waste related measures

Liquid NaOH waste should be reused or discharged to the industrial wastewater and further
neutralized if needed (see risk management measures related to environment).

Exposure estimation
Workers exposure

NaOH is a corrosive substance. For the handling of corrosive substances and formulations, immediate
dermal contacts occur only occasionally and it is assumed that repeated daily dermal exposure can be
neglected. Therefore according to the NaOH EU RAR (2007), dermal exposure to pure NaOH will not
be assessed. Repeated dermal exposure cannot be neglected for these substances and formulations.
Ocular exposure is possible due to hand-eye contact but this is not quantified.

NaOH is not expected to be systemically available in the body under normal handling and use
conditions and therefore systemic effects of NaOH after dermal or inhalation exposure are not
expected to occur.
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Due to the low vapour pressure of NaOH, the atmospheric concentration of NaOH based on
vaporisation from the liquid will be very low. Although the exposure to a vapour of NaOH is estimated
to be very low, the task related data can not be used to predict the exposure to aerosols (mists). An
overview of the estimated and measured exposure concentrations can be found in Table 3.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 12 / 46

Table 3 Exposure concentrations for workers

Estimated
Measured exposure
Exposure Explanation / source of measured
concentrations
Routes of Concentrations data
exposure Value unit Value unit
Not
Dermal exposure Not available
available
From EU RAR (2007)
Range: 0.02 – 0.5 mg/m³
AM: 0.14 mg/m³
Truck loading of liquid
STAT measurement, N=17, 2002; 2003
From EU RAR (2007)
Range: 0.29 – 0.37 mg/m³
AM: 0.33 mg/m³
Liquid, other task
Spot measurement, N=5, 2003
From EU RAR (2007)
Inhalation
AM: <0.26 mg/m³ Liquid, other task
exposure STAT measurement, N=20, 2002
From EU RAR (2007)
Range: 0.05 – 0.18 mg/m³ *
AM: 0.01* mg/m³
Liquid, pearls, close to installation
STAT measurement, N=109, 2002
From EU RAR (2007)
0.02 (typical) mg/m Drumming liquid NaOH
0.04 (RWC) ³ Typical and reasonable worst case
exposure level
STAT Stationary Air Sample
Spot Short term stationary sample
N Amount of measurements
AM Arithmetic mean
* These values are considered not to be correct. A mean value can’t be lower than the
range.

Measured data

In the EU RAR (2007), atmospheric exposure measurements are available for 6 production sites from
4 different countries (Czech Republic, Poland, Spain and United Kingdom). In all cases the
concentrations were lower than 2 mg/m 3 (see Table 3). Most NaOH production sites replied that the
OEL was 2 mg/m3 in their country. The data of the production site in Spain are based on
measurements of the sodium content, which were performed according to a norm of the National
Institute for Worker Safety and Hygiene (NTP-63 of 1983). For this production site the sampling
duration was 6-8 hours. Other sites reported that the measurements were based on a Polish standard
method, a colorimetric method or on atomic absorption spectroscopy. The sampling duration was
unknown for these sites.

Modelled data

The ECHA guidance on information requirements proposes ECETOC TRA as the preferred Tier 1 tool.
ECETOC TRA is based on a modified version of EASE. EASE was the preferred model under the New
& Existing Substances Directive. EASE is known to overpredict exposures in many cases. The reason
for this is considered to be the fact that EASE relies upon historical exposure data from enforcement
activities in known problem areas, rather than the typical/normal operations that are required for more
routine risk assessment. For this reason the values from the output from EASE were reviewed and
modified accordingly in the ECETOC TRA. Both the EASE predictions (from EU RAR, 2007) and
ECETOC TRA approaches were considered here.

Inhalation exposure to vapour due to drumming is estimated in the EU RAR (2007) with EASE 2.0.
The exposure range is estimated 0 – 0.17 mg/m3 (0 – 0.1 ppm, 20°C), assuming very low vapour
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 13 / 46

pressure, no aerosol formation and non-dispersive use. Typical exposure is estimated as 0.085 mg/m 3
(middle value of range). The reasonable worst-case exposure is estimated as 0.17 mg/m 3 (upper
value of range) assuming no aerosol formation and non-dispersive use with dilution ventilation.
Following the questionnaire, it is assumed that in the present industry LEV is not generally available.
Presence of LEV will not influence the exposure range in this estimation. Assuming a NaOH
concentration of 50% the typical exposure is estimated to be 0.04 mg/m 3 and the reasonable worst
case exposure is estimated to 0.085 mg/m 3. Frequency of exposure for drumming is estimated to be
up to 200 days per year with a duration of up to 4 hours/day, while the number of workers involved is
estimated to be up to 50 (expert judgment). Assuming 4 hours of handling and zero exposure during
the remainder of the working day, 8-hour TWA typical exposure is estimated as 0.02 mg/m 3 and an 8-
hour TWA reasonable worst case exposure is estimated as 0.04 mg/m 3.

Inhalation exposure to vapour or aerosols due to all PROCs is estimated in the ECETOC TRA and the
inhalation exposure is 0.1 ppm (0.17 mg/m 3), assuming very low vapour pressure, exposure duration
of more than 4 hours/day and no local exhaust ventilation or respiratory equipment.

Summary of the exposure values

Only one single value will be used for risk characterisation. A summary of exposure concentration for
workers is given in Table 4.

Table 4 Summary of exposure concentration for workers

Routes of
exposure Concentrations Justification

Negligible From EU RAR (2007): NaOH products with a concentration > 2% are
corrosive, therefore effective control measures are in place to prevent
dermal exposure. Furthermore protective clothing and gloves are
Dermal exposure considered to be used consistently when handling corrosive substances.
(in mg/cm2) Production companies report the use of protective gloves, suits and
boots while handling pure NaOH. Repeated daily dermal exposure to
commercial product is therefore considered negligible. Dilutions of
NaOH containing < 2% are not produced at the production sites.

0.33 From EU RAR (2007): For drumming liquid NaOH the modelled data are
Inhalation underestimated by EASE in comparison with the measured data.
exposure Because there is a relatively large number of measured data, these will
(in mg/m3) be used for risk characterisation. The value 0.33 mg/m 3 is taken as
reasonable worst case level and 0.14 mg/m 3 is taken as typical exposure
level.

Indirect exposure of humans via the environment (oral)

Indirect exposure to humans, for example through the uptake of drinking water, is not relevant for
NaOH. Any potential for exposure to NaOH due to environmental releases will only have relrevance at
the local scale. Any pH effect of local releases will be neutralised in the receiving water at the regional
scale. Therefore indirect exposure of humans via the environment (oral) is not relevant in the case of
NaOH (EU RAR, 2007).

Environmental exposure

As stated in the EU RAR on NaOH (2007), the risk assessment for the environment is only relevant for
the aquatic environment, when applicable including STPs/WWTPs, as emissions of NaOH in the
different life-cycle stages (production and use) mainly apply to (waste) water. The aquatic effect and
risk assessment will only deal with the effect on organisms/ecosystems due to possible pH changes
related to OH- discharges, as the toxicity of the Na+ ion is expected to be insignificant compared to the
(potential) pH effect. Only the local scale will be addressed, including sewage treatment plants (STPs)
or waste water treatment plants (WWTPs) when applicable, both for production and industrial use. Any
effects that might occur would be expected to take place on a local scale. Therefore it was decided not
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 14 / 46

meaningful to include the regional and continental scale in this risk assessment. Furthermore, the high
water solubility and very low vapour pressure indicate that NaOH will be found predominantly in water.
Significant emissions or exposure to air are not expected due to the very low vapour pressure of
NaOH. Significant emissions or exposure to the terrestrial environment are not expected either. The
sludge application route is not relevant for the emission to agricultural soil, as sorption of NaOH to
particulate matter will not occur in STPs/WWTPs.

The exposure assessment for the aquatic environment will only deal with the possible pH changes in
STP effluent and surface water related to the OH- discharges at the local scale.

Environmental releases

The production of NaOH can potentially result in an aquatic emission and locally increase the sodium
concentration and pH in the aquatic environment. When the pH is not neutralised, the discharge of
effluent from NaOH production sites may cause an increase in pH in the receiving water. The pH of
effluents is normally measured very frequently and can be neutralised easily. The production capacity
and the applied processes for all sites in the EU are presented in Napaka! Vira sklicevanja ni bilo
ogoče najti..

Since the exposure assessment focussed on possible pH changes in the local aquatic environment,
industry collected actual data on pH values in effluent and receiving surface waters at NaOH
production sites for the purpose of the EU RAR (2007), based on the results of a questionnaire that
was sent to a broad cross section of NaOH producers in the EU via Euro Chlor, representing 97% of
NaOH production capacity in the enlarged Europe (Euro Chlor, 2004b). The results of this
questionnaire (Euro Chlor, 2004c) provided effluent and receiving water data for 43 out of 84
production sites. The sites are anonymised by numbers which do not correspond to the numbers in
Napaka! Vira sklicevanja ni bilo mogoče najti.. The 43 responding production sites are from 15
ifferent EU countries with a wide geographical spread. The respondents include 34 sites in the old EU
member states, 6 sites in the new EU member states, 2 in Norway and 1 in Switzerland (Euro Chlor,
2004c). The three major NaOH production processes, i.e. membrane, diaphragm and mercury
process, were well represented among the respondents to the questionnaire. The production
capacities of the sites that responded represented a very broad range from several tens of ktonne/year
up to several hundreds of ktonne/year (Euro Chlor, 2004b).

The questionnaire revealed that 11 sites do not have effluents which are discharged to the
environment. On these specific sites the waste water can be completely recycled due to the specific
on-site process conditions. The results also showed that out of 43 sites reporting, 31 sites neutralize
their effluent before discharging into the receiving water. A total of 32 sites reported to be legally
obliged to neutralize their effluent and 6 sites, which do not have effluents, did not respond to this
question. However, 5 sites reported not to have such legal requirements, while 2 of these 5 sites
reported actually to neutralize their effluents. One site (site 30) reports a legal obligation to neutralize
but they do not adapt their pH, because the pH range of their effluent is already within a narrow range
close to neutral.

According to Euro Chlor (2004c), many sites reported pH values for wastewater sub-streams instead
of final effluents, even though they are included as ‘effluent data’ This was concluded from the fact
that many sites reported broad ranges of pH values, but also indicated that final effluents were
neutralised before discharging and from some subsequent checks with respondents. Substreams are
normally combined with other wastewater sub-streams on the site before they are finally discharged
into the receiving water. Therefore, the first two columns of Table 5 on effluents are the most important
with respect to the potential pH effect on receiving waters.

A total number of 36 production sites, including 2 sites (no. 17 and 30) that do not discharge their
effluent into the environment, i.e. sewer or receiving water, reported measured pH values of the
effluent. Of these 36 sites, 19 sites reported pH values within the range of 6-9 (range of lowest pH to
highest pH), 7 sites reported pH values within the range of 5-10 and 10 sites reported pH values
outside the range of 5-10. Most importantly, all but one of the sites that discharge effluent into the
environment reported to neutralise their effluent before discharge. Only one site (no. 15) reporting a
very wide effluent pH rang of 3.0-11.6 and stated not to neutralise its effluent before discharge. After
contacting this site it became clear that the reported pH values for this site represented measurements
in the wastewater sub-stream, immediately after leaving the production unit. Depending on the
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 15 / 46

process conditions this can have the listed extreme values, which reportedly only last for 10-15
minutes because the wastewater sub-stream is then combined with other wastewater sub-streams at
the site and the pH becomes circumneutral. Thereafter the final effluent (i.e. the combined wastewater
sub-streams) enters a municipal sewage treatment plant before it is discharged into the receiving
water. This site is not legally obliged to neutralise its effluent before discharge (Euro Chlor, 2004c). As
all further sites that reported a high difference between the lowest and highest pH of the effluent also
reported to neutralise their effluent, it can be assumed that for these sites the pH values are also for
wastewater sub-streams (that are combined with other sub-streams before neutralisation of the final
effluent) and not for the final effluents that are discharged into the environment. The results from the
questionnaire, reported for 43 out of 84 production sites, demonstrate that the pH of waste water
discharges is controlled and that generally proper regulations are in place.

Table 5 Effluent and receiving water data for NaOH producers in the EU (Euro Chlor, 2004c)
(From EU RAR, 2007)

Exposure concentration in waste water treatment plants (WWTP)

Waste water from NaOH production sites is coming from the salt electrolyses and is an inorganic
wastewater stream. For this reason it is not feasible to treat it biologically. Therefore wastewater
streams from NaOH production sites will normally not be treated in biological waste water treatment
plants (WWTPs). NaOH may be used beneficially, however, for pH control of acid wastewater streams
that are treated in biological WWTP’s (EU RAR, 2007).
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 16 / 46

Exposure concentration in aquatic pelagic compartment

If emitted to surface water, sorption to particulate matter and sediment will be negligible. An addition of
NaOH to surface water may increase the pH, depending on the buffer capacity of the water. The
higher the buffer capacity of the water, the lower the effect on pH will be. In general the buffer capacity
preventing shifts in acidity or alkalinity in natural waters is regulated by the equilibrium between carbon
dioxide (CO2), the bicarbonate ion (HCO3-) and the carbonate ion (CO32-):

CO2 + H2O <-> HCO3- + H+ (pKa1 = 6.35)

HCO3- <-> CO32- + H+ (pKa2 = 10.33)

If the pH is < 6, un-ionised CO2 is the predominant species and the first equilibrium reaction is most
important for the buffer capacity. At pH values of 6-10 the bicarbonate ion (HCO3-) is the predominant
species and at pH values > 10 the carbonate ion (CO32-) is the predominant species. In the majority of
natural waters the pH values are between 6 and 10, thus the bicarbonate concentration and the
second equilibrium reaction are most important for the buffer capacity (Rand, 1995; De Groot et al.,
2002; OECD, 2002). UNEP (1995) reported the bicarbonate concentration for a total number of 77
rivers in North-America, South-America, Asia, Africa, Europe and Oceania. The 10th–percentile, mean
and 90th-percentile concentrations were 20, 106 and 195 mg/l, respectively (OECD, 2002). To
underline the importance of the bicarbonate concentration for the buffer capacity in natural waters,
Table 6 summarises the concentration of NaOH needed to increase the pH from an initial pH of 8.25-
8.35 to a value of 9.0, 10.0, 11.0 and 12.0 at different bicarbonate concentrations. The data of Table 6
are based on calculations but were confirmed by experimental titrations of bicarbonate (HCO 3-)
concentrations of 20, 106 and 195 mg/l, respectively, in purified water. The difference between the
calculated and measured NaOH concentration needed to obtain a certain pH value was always < 30%
(De Groot et al., 2002; OECD, 2002). The data in Table 6 for distilled water are from OECD (2002).

The alkalinity, defined as the acid-neutralising (i.e. proton accepting) capacity of the water, thus the
quality and quantity of constituents in water that result in a shift in the pH toward the alkaline site of
neutrality, is determined for > 99% by the concentrations of bicarbonate (HCO 3-), carbonate (CO32-)
and hydroxide (OH-) (Rand, 1995), with bicarbonate being the predominant species at pH values in the
range of 6-10 (see also above). Hydroxide is only relevant in alkaline waters. Thus, the data in Table 6
are useful to estimate pH increases in natural waters (most of them having a pH value of 7-8), if data
on NaOH additions and bicarbonate concentrations are available. The alkalinity is determined from
acid/base titration or can be calculated from the calcium concentration, as follows (De Schampelaere
et al., 2003; Heijerick et al., 2003):

Log (alkalinity in eq/l) = - 0.2877 + 0.8038 Log (Ca in eq/l)

Table 6 Concentration of NaOH (mg/l) needed to increase the pH to values of 9.0, 10.0, 11.0 and
12.0 (De Groot et al., 2002; OECD, 2002)

Based on the neutralized environmental releases and the fate in the aquatic compartment described
above, there is no environmental impact on the receiving surface water.

Exposure concentration in sediments

TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 17 / 46

The sediment compartment is not included in this CSA, because it is not considered relevant for
NaOH. If emitted to the aquatic compartment, sorption to sediment particles will be negligible (EU
RAR, 2007).

Exposure concentrations in soil and groundwater

The terrestrial compartment is not included in this CSA, because it is not considered relevant for
NaOH. With respect to the fate of NaOH in soil the following information is available. If emitted to soil,
sorption to soil particles will be negligible. Depending on the buffer capacity of the soil, OH - will be
neutralised in the soil pore water or the pH may increase (EU RAR, 2007).

Atmospheric compartment

The air compartment is not included in this CSA because it is considered not relevant for NaOH. With
respect to the fate of NaOH in air the following information is available from EU RAR (2007). If emitted
to air as an aerosol in water, NaOH will be rapidly neutralised as a result of its reaction with CO2 (or
other acids), as follows:

NaOH + CO2  HCO3- + Na+

Subsequently, the salts (e.g. sodium (bi)carbonate) will be washed out from the air (US EPA, 1989;
OECD, 2002). Thus, atmospheric emissions of neutralised NaOH will largely end up in soil and water.
Based on a NaOH concentration of 50% in the aerosol droplets, the atmospheric half-life of NaOH was
estimated at 13 seconds. Based on model calculations, this degradation rate results in only 0.4% of
the NaOH emitted to air remaining in the air at a point 200 metres from the emission point (U.S. EPA,
1988; 1989).

Exposure concentration relevant for the food chain (Secondary poisoning)

Bioaccumulation in organisms is not relevant for NaOH. Therefore, there is no need to perform a risk
assessment for secondary poisoning (EU RAR, 2007).

Exposure Scenario 2: Manufacturing of solid NaOH

Exposure scenario
Short title of the exposure scenario

SU 3, 8: Manufacture of bulk, large scale substances

PROC 1, 2, 3, 4, 8, 9: use in (closed) continuous or batch process with no likelihood of exposure or

where opportunity for exposure arises (industrial setting), including charging, discharging, sampling
and maintenance

PC and AC not applicable for this ES

Description of activities, processes and operational conditions covered in the exposure

scenario

The processes and activities for solid NaOH include the processes and activities for liquid NaOH (see
section 0). Solid NaOH results when molten NaOH, from which all the water has been evaporated, is
allowed to cool and solidify. Flake NaOH is made by passing molten NaOH over cooled flaking rolls to
form flakes of uniform thickness. The flakes can be milled and screened into several crystalline
products with controlled particle size. The manufacture of NaOH beads involves feeding molten liquor
into a prilling tower under carefully controlled operating conditions, producing a spherical bead
(OxyChem, 2000).

Flakes can be packed in bags (25 or 50 kg). Micro pearls are packed in bags, bulk bags (500 or 1,000
kg) but it is also delivered in bulk (by road). Cast is delivered in metallic drums (e.g. 400 kg). However,
it should be realised that other packaging forms could exist.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 18 / 46

Solid NaOH (flakes, pearls or cast) is produced at 23% of the production sites. The shifts can be 12
hrs/day (40 hours/week).

Risk management measures

Risk management measures related to workers

Relevant risk management measures related to workers are described in section 0.

Risk management measures related to environment

Relevant risk management measures related to environment are described in section 9.1.1.4.2.

Waste related measures

There is no solid waste of NaOH. Liquid NaOH waste should be reused or discharged to the industrial
wastewater and further neutralized if needed (see risk management measures related to
environment).

Exposure estimation
Workers exposure

NaOH is a corrosive substance. For the handling of corrosive substances and formulations, immediate
dermal contacts occur only occasionally and it is assumed that repeated daily dermal exposure can be
neglected. Therefore according to the NaOH EU RAR (2007), dermal exposure to pure NaOH will not
be assessed. Repeated dermal exposure cannot be neglected for these substances and formulations.

NaOH is not expected to be systemically available in the body under normal handling and use
conditions and therefore systemic effects of NaOH after dermal or inhalation exposure are not
expected to occur.

An overview of the estimated and measured exposure concentrations for inhalation can be found in
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 19 / 46

Table 7.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 20 / 46

Table 7 Exposure concentrations to workers

Estimated
Measured exposure
Exposure Explanation / source of measured
concentrations
Routes of Concentrations data
exposure Value unit Value unit
From EU RAR (2007):
Range: 0.1 – 1.8 mg/m³
AM: 0.84 mg/m³
Drumming/Bagging of liquid, cast, pellets
PAS measurement, N=10, 2003
From EU RAR (2007):
Range: 0.01 – 0.27 mg/m³
AM: 0.09 mg/m³
Drumming/Bagging of liquid, cast, pearls
PAS measurement, N=12, 2003
From EU RAR (2007):
Inhalation
Range: 0.01 – 0.1 mg/m³
exposure AM: 0.05 mg/m³
Drumming of liquid, cast, pearls
STAT measurement, N=20, 2003
New industry data:
Pelletization belt: Range: 0.03 – 0.51
AM: 0.11
mg/m3 mg/m3
90P: 0.269
Filling: Range: 0.11 – 0.38 mg/m3
PAS, More details, see text
Maximum EASE and ECETOC TRA
2.5 mg/m3
simulations
PAS Personal Air Sample
STAT Stationary Air Sample
N Amount of measurements
AM Arithmetic mean
* These values are considered not to be correct. A mean value can’t be lower than the
range.

Measured data

In the EU RAR (2007), atmospheric exposure measurements are available for 6 production sites from
4 different countries (Czech Republic, Poland, Spain and United Kingdom). In all cases the
concentrations were lower than 2 mg/m 3 (see Table 14). Most NaOH production sites replied that the
OEL was 2 mg/m3 in their country. One operation with the possibility of exposure is sampling. It is
assumed that all the measurement at drumming/bagging was done with solid NaOH. The data of the
production site in Spain are based on measurements of the sodium content, which were performed
according to a norm of the National Institute for Worker Safety and Hygiene (NTP-63 of 1983). For this
production site the sampling duration was 6-8 hours. Other sites reported that the measurements were
based on a Polish standard method, a colorimetric method or on atomic absorption spectroscopy. The
sampling duration was unknown for these sites. In one company, significant higher exposures were
observed.

A new data set was gathered from an open system with local exhaust ventilation. Sampling was done
with air pump, flow going thorough the filter. NaOH is dissolved in with water and excess of HCl. The
rest of HCl is titrated with KOH. Indicator is methylred. This analytical method is compliant with NIOSH
7401. The exposure time was 340 or 505 minutes. These relate to a 8 and 12 hour shift respectively.
The exposure was zero during the remaining time of the shift. Measurements were done during one
shift. The number of workers is 3 per shift and the amount of substance handled: 7 ton per shift. The
size of packing is 25-1000 kg. The process was an open system and had local ventilation installed (20
m3/hour). No respiratory protection was used. The ECHA guidance on information requirements R.14
suggests to take the 75th percentile for large databases and the 90th percentile for smaller databases.
Therefore, the 90th percentile of 0.269 mg/m 3 was selected as a reasonable worst-case estimate. Also
note that no respiratory tract effects were observed among the workers.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 21 / 46

Modelled data

Considering the particle size distribution (more than 90% larger than 100 μm) of the substance other
assumptions than the default assumptions “production and processing of powders” were used in the
EU RAR (2007) to estimate inhalation exposure to dust with EASE 2.0. Typical exposure is estimated
to be 0-1 mg/m3, assuming low dust technique in the presence of LEV. The reasonable worst case
exposure is estimated to be 0-5 mg/m3, assuming the absence of LEV. Frequency of exposure for
drumming is estimated to be up to 200 days per year with a duration of up to 4 hours/day, while the
number of workers involved is estimated to be up to 50 (expert judgement). Assuming 4 hours of
handling and zero exposure during the remainder of the working day, 8-hour TWA typical exposure is
estimated as 0 – 0.5 mg/m3 and the 8-hour TWA reasonable worst case exposure is estimated as 0 –
2.5 mg/m3.

Considering low dustiness, no LEV and no respiratory protection, ECETOC TRA predicts inhalative
exposure of 0.01 mg/m3 for PROC 1 and PROC 2, 0.1 mg/m3 for PROC 3 and PROC 9, 0.5 mg/m 3 for
PROC 4 and PROC 8a. Following the EU RAR (2007) by assuming 4 hours of handling and zero
exposure during the remainder of the working day, 8-hour TWA typical exposure is estimated as 0 –
0.5 mg/m3 and the 8-hour TWA reasonable worst case exposure is estimated as 0 – 2.5 mg/m3.

Summary of the exposure values

The summary of exposure concentrations to workers, taken forward to risk characterization is given in
Table 8.

Table 8 Summary of exposure concentration to workers

Routes of
exposure Concentrations Justification

Negligible From EU RAR (2007): NaOH products with a concentration > 2% are
corrosive, therefore effective control measures are in place to prevent
dermal exposure. Furthermore protective clothing and gloves are
Dermal exposure considered to be used consistently when handling corrosive substances.
(in mg/cm2) Production companies report the use of protective gloves, suits and
boots while handling pure NaOH. Repeated daily dermal exposure to
commercial product is therefore considered negligible. Dilutions of
NaOH containing < 2% are not possible for solid NaOH.

Inhalation 0.269
exposure Highest exposures are measured at the drumming/bagging place and
(in mg/m3) therefore these values are taken to the risk characterisation.

Indirect exposure of humans via the environment (oral)

Indirect exposure to humans, for example through the uptake of drinking water, is not relevant for
NaOH. Any potential for exposure to NaOH due to environmental releases will only have relrevance at
the local scale. Any pH effect of local releases will be neutralised in the receiving water at the regional
scale. Therefore indirect exposure of humans via the environment (oral) is not relevant in the case of
NaOH (EU RAR, 2007).

Environmental exposure

Sodium hydroxide will rapidly dissolve and dissociate in water when released to water. The
environmental exposure assessment for solid sodium hydroxide is consequently the same as for liquid
sodium hydroxide. The reader is referred to section 0.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 22 / 46

Exposure Scenario 3: Industrial and professional use of NaOH

To collect the required information related with occupational exposure when using NaOH for the
purpose of the EU RAR (2007), a questionnaire has been developed by Euro Chlor in cooperation with
the Rapporteur Member State Portugal. In September 2004 questionnaires have been sent by e-mail
to:

 The Confederation of European Paper Industries (CEPI). They have forwarded the questionnaires
to their members (paper producing companies which use NaOH).

 Five different contact persons from Euro Chlor member companies (NaOH producers). Afterwards
each producer of NaOH has sent the questionnaire to 20 customers (in most cases end users of
NaOH).

The responses were analysed and the results reported by Euro Chlor (2005).

A total number of 58 replies were received, originating from about 10 different EU member states. The
majority (59%) originated from the pulp and paper industry and and therefore the data for this sector
can be considered as highly representative for the situation in Europe. For the pulp and paper industry
one questionnaire was received from Germany (National Federation), which represented the common
practice in this country.

The response from other industry customers was less but still covered a broad range of applications of
NaOH. A total of 17 questionnaires (29%) were received from the chemical industry (e.g. production of
crop protection chemicals, organic pigments, epoxy resins). The remaining 7 questionnaires were
received from steel industry, textile industry, rubber production, food industry, metal industry,
aluminium industry and distribution. This shows that 23 end users of NaOH replied, while one
distributor completed the questionnaire. In most cases the NaOH was used as a reactant during the
manufacturing/production of chemicals. In a few other cases it was used for neutralisation (steel
industry, rubber production), cleaning and water treatment (food industry) or for extraction (aluminium
industry).

Exposure scenario
Short title of the exposure scenario

Sodium hydroxide could be used according to the following process categories (PROC):

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 (multistage and/or significant contact)
PROC8a/b Transfer of chemicals from/to vessels/large containers at (non)dedicated facilities
PROC9 Transfer of chemicals into small containers (dedicated filling line)
PROC10 Roller application or brushing
PROC11 Non industrial spraying
PROC13 Treatment of articles by dipping and pouring
PROC15 Use of laboratory reagents in small scale laboratories
The process categories mentioned above are assumed to be the most important ones but other
process categories could also be possible (PROC 1 – 27).

Sodium hydroxide can be used in many different chemical product categories (PC). It can be used for
example as an adsorbent (PC2), metal surface treatment product (PC14), non-metal-surface treatment
product (PC15), intermediate (PC19), pH regulator (PC20), laboratory chemical (PC21), cleaning
product (PC35), water softener (PC36), water treatment chemical (PC37) or extraction agent.
However, it could potentially also be used in other chemical product categories (PC 0 – 40).

Because sodium hydroxide has so many uses and is used so widely it can potentially be used in all
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 23 / 46

sectors of use (SU) described by the use descriptor system (SU 1-24). NaOH is used for different
purposes in a variety of industrial sectors. The sector with the largest use of NaOH is the production of
other chemicals, both organics (30%) and inorganics (13%). Other uses are in the sectors pulp and
paper industry (12%), aluminium and metal industry (7%), food industry (3%), water treatment (3%)
and textile (3%). The remainder is used in the production of soaps, mineral oils, bleach, phosphates,
cellulose, rubber and others (Euro Chlor, 2009). The sector of use 21 is considered in Exposure
Scenario 4.

Although sodium hydroxide can be used during the manufacturing process of articles, the substance is
not expected to be present in the article. The article categories (AC) do not seem applicable for
sodium hydroxide.

To assess the environmental exposure of substances environmental release categories (ERC) have
been developed for REACH. For sodium hydroxide the following environmental release categories
could be applicable:

ERC1 Manufacture of substances

ERC2 Formulation of preparations
ERC4 Industrial use of processing aids in processes and products, not becoming part of articles
ERC6A Industrial use resulting in manufacture of another substance (use of intermediates)
ERC6B Industrial use of reactive processing aids
ERC7 Industrial use of substances in closed systems
ERC8A Wide dispersive indoor use of processing aids in open systems
ERC8B Wide dispersive indoor use of reactive substances in open systems
ERC8D Wide dispersive outdoor use of processing aids in open systems
ERC9A Wide dispersive indoor use of substances in closed systems

The environmental release categories mentioned above are assumed to be the most important ones
but other industrial environmental release categories could also be possible (ERC 1 – 12). The wide-
dispersive uses are considered in Exposure Scenario 4.

Description of activities, processes and operational conditions covered in the exposure

scenario

Typcial uses for NaOH solids are: dilution in water, dilution in methanol (biodiesel industry) and solids
as drain unblockers. Typical uses for liquid NaOH are given below.

Production of chemicals

NaOH is used for the production of organic and inorganic chemicals which end up in a broad variety of
end products (Euro Chlor, 2009). At the production sites of organic and inorganic chemicals, NaOH is
used as pH stabiliser or as reactant for synthesis of other chemicals. In all cases NaOH must be
added to a reaction vessel and will react after which no NaOH is left. In some plants NaOH is recycled
to the process.

Formulation of chemicals

Occupational exposure can occur during production of formulations. Especially during loading and
mixing a higher exposure can be expected. High exposures can occur during the production process
of the cleaning products, when loading concentrated NaOH, which typically involves pumping or
pouring a fluid from a barrel or a drum into a process vessel. Inhalation exposure during loading may
take place due to vapours or aerosols formed when the barrel or drum is opened and when adding the
product to the process. NaOH will be diluted after loading into a tank.

Production and whitening of paper pulp

The major applications of NaOH in the paper and pulp industry are pH regulation, pulping, bleaching
reactant, cleaning agent, water treatment for steam production and demineralisation (Euro Chlor,
2005). Paper and pulp mills produce acid effluents and NaOH is used in waste water treatment for
neutralisation, for example of strongly acidic condensate from vaporation of spent liquor. No surplus
NaOH is discharged to the WWTP and/or in the receiving water (Euro Chlor, 2005). Other examples of
pulp and paper processes using NaOH are:
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 24 / 46

 Kraft pulping, which is full chemical pulping with NaOH and Na2S, pH above 12, 800 kPa (120 psi).
Modern kraft pulping is usually carried out in a continuous digester often lined with stainless steel
and exposure to NaOH is then expected to be minimised. The temperature of the digester is
raised slowly to approximately 170°C and held at that level for approximately 3 to 4 hours. The
pulp is screened to remove uncooked wood, washed to remove the spent cooking mixture, and
send either to the bleach plant or to the pulp machine. At the end of the process step, sodium
hydroxide is reformed in the recausticizing plant (EOHS, 2001).

 The so-called extended delignification, which are techniques to remove more lignin prior to
bleaching. NaOH and heat act to break complex bonds in the lignin to make them soluble in water
or volatile. NaOH and heat also break bonds in the cellulose reducing strength and yield. To do
this, wood pulp and chemicals (NaOH, Na2S) are cooked together in a pressure vessel (digester)
which can be operated on a batch or continuous basis. In case of batch filling the digester is filled
through a top opening. This can cause exposure to the used chemicals.

 The bleaching process in the so-called alkali extraction where the organic acids and alcohols react
with the NaOH to form organic sodium compounds and water. These organic substances dissolve
in water. Here NaOH is used to create a high pH to optimise the bleaching process. NaOH is not
the bleaching agent. The purpose of the bleaching is to remove lignin without damaging the
cellulose.

 Waste paper recycling: adding water, NaOH, and heat repulps recycled material. The pulp is then
used to make a finished paper product on a paper machine in the same manner as in a virgin
paper mill.

Production of aluminium and other metals

NaOH is used in the treatment of bauxite, from which alumina, the basis of aluminium, is extracted.
Aluminium is produced from bauxite by the Bayer process. Mixed with steam and a (strong) NaOH
solution, alumina in the bauxite forms a concentrated sodium aluminate solution leaving undissolved
impurities. The conditions to extract the monohydrate alumina are about 250°C and a pressure of
about 3,500 kPa (Queensland Alumina Limited, 2004)). At the end of the process NaOH is returned to
the start and used again. Relatively high inhalation exposure to NaOH is expected to be caused during
the mixing of bauxite with NaOH and steam due to the high temperatures and high concentrations of
NaOH. In the stage of surface treatment of aluminium finished products, NaOH is used for pickling
(Euro Chlor, 2005).

Food industry

NaOH can be used for a large number of applications in the food industry. In the food production
sector, NaOH is regularly used for (Euro Chlor, 2005):

 washing and cleaning of bottles, processes and equipment;

 chemical peeling/shelling of fruits and vegetables;

 modification of starch;

 preparation of carboxyl methyl cellulose;

 preparation of salts such as sodium citrate and sodium acetate.

Water treatment

NaOH is widely used in the treatment of water. In sewage treatment stations, NaOH allows the
neutralisation of effluent and a reduction in the hardness of water. In industry, NaOH allows the
regeneration of ion exchange resins. NaOH is currently used in water treatment with various
objectives:
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 25 / 46

 control of the water hardness;

 regulation of the pH of water;

 neutralisation of effluent before the water is discharged;

 regeneration of ion exchange resins;

 elimination of heavy metal ions by precipitation.

NaOH is also used for the cleaning of combustion or incineration flues. Among the technologies used,
the washing of gases in a scrubber using alkaline solutions is a process offered by a large number of
engineering companies. The concentrations of NaOH solutions used vary according to the application,
the level of performance to be achieved, financial situation, etc. The level of scrubbing performance of
this technology allows reductions in acid components (HCl, SO 2, etc.) and in heavy metals (Hg, Cd,
etc.) to comply with the requirements of international and national standards (Euro Chlor, 2004a,
2005).

Production of textiles

Besides natural materials such as wool, cotton or linen, synthetic fibres are extensively used by the
textile industry. Cellulose textiles, obtained by the viscose process (rayon, spun rayon) have a
significant market share. At present (2004) annual world production of cellulose textiles easily exceeds
3 million tonnes. Their manufacture consumes considerable tonnages of NaOH, were 600 kg of NaOH
is needed to produce a tonne of cellulose fibres. The function of NaOH in the production of cellulose is
unknown. NaOH is also used as general processing aid such as neutralisation.

In the viscose process, cellulose derived from wood pulp is steeped in a sodium hydroxide solution
(20-25%), and the excess liquid is squeezed out by compression to form alkali cellulose. Impurities are
removed and, after being torn into shreds similar to white crumbs that are allowed to age for several
days at controlled temperature, the shredded alkali cellulose is transferred into another tank were it is
treated with carbon disulphide to form cellulose xanthate. These are dissolved in diluted sodium
hydroxide to form a viscous orange liquid called viscose. The acids and alkalis used in the process are
fairly dilute, but there is always danger from the preparing of the proper dilutions and splashes into the
eyes. The alkaline crumbs produced during the shredding may irritate workers’ hand and eyes. The
major part of the sodium hydroxide used in the textile industry is used in the mercerization, bleaching,
scouring and washing of cotton.

Other industrial uses

NaOH is further applied in various other industrial sectors such as in production of surfactants, soaps,
mineral oils, bleach, phosphates, cellulose and rubber (Euro Chlor, 2009). In most of these
applications NaOH also serves as a process aid, such as neutralisation.

Professional end use of formulated products

NaOH is used during the production phase of various cleaning products although in most case the
amounts in the end products are limited. The NaOH used will interact with other ingredients in acid-
base reactions and thus practically no free NaOH is left in the final product. Product categorization for
professional cleaning products with remaining free NaOH after formulation can be found in the table
below.

Product type ‘free NaOH’ pH range Remarks concerning

content RMM/OC

Floor strippers <10% >13

Oven cleaners 5-20% >13

TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 26 / 46

Floor degreasers <5% >12.5

Drain openers <30% >13

Dish washing products 5-30% >13 (concentrated product)

Interior heavy duty cleaners <5% >12.5

Professional oven cleaners

Oven cleaners are strong degreasers and they are suitable for removing dirt stuck on ovens, grills, etc.
Oven cleaners contain strong alkaline ingredients. Strong alkali is necessary to remove burned-on
soils. There are trigger sprays and spray cans. When using a spray can, foam is formed on the target
area. After spraying, the oven door is closed and the foam has to soak 30 minutes. Then the oven is
wiped clean with a wet cloth or sponge and one has to rinse frequently. The maximum content of
sodium hydroxide in a spray can is 10%. The product is either a gel, which leads to large droplets

to less aerosol.

The frequency of application is 1 event per day and the duration is 10 minutes per event. Spraying into
cold oven, with potential exposure to hands and arms. One can spray up to 1g product per second, by
hand-held ready-to-use trigger spray or foam sprayer.

Professional floor strippers

Floor strippers in the I&I (Industrial and Institutional) area are not used neat. The highly alkaline
products are dosed 15-20% and per 10 m2 1-2 L stripper solution is brought onto the floor with a single
disc machine. Usually 10-15 min acting time are necessary between laying down and scrubbing the
floor. Afterwards the stripper/polish mixture is removed by a fat vacuum cleaner.

Drain cleaners

Drain openers open slow running and obstructed drains by dissolving and by loosening grease and
organic waste. There are different kinds of drain openers, products containing either sodium hydroxide
or sulphuric acid. Liquid drain openers have a maximum NaOH content of 30%. The use of liquid drain
openers is comparable with the dosing of liquid cleaners. The drain opener must be dosed slowly
down the drain. Pellets, which can also be use for opening the drain, have contents up to 100%. The
drain opener must be dosed slowly down the drain. One has to wait at least 15 minutes so that the
drain opener can clear the blockage.

Professional hair straightening products

Several hair straightening products used by professional hairdressers contain a certain amount of
NaOH. Hair straightening products, containing more than 2% of NaOH, are applied to the hair with a
brush and after a period of interaction with the hair the product is rinsed out with water. For estimating
worker exposure no relevant inhalation exposure is expected because of the low volatility and the lack
of aerosol formation. Dermal exposure is only relevant when concentrations of NaOH are below 2%,
which probably will occur when the product is rinsed out of the hair. Above 2% the product will be
corrosive which means control measures are expected to prevent dermal exposure. The exposure is
therefore expected to occur mainly when the hairdresser decided to do a final rinsing step after the
first rinsing is done.

Risk management measures

Risk management measures related to industrial workers

The risk management measures related to industrial workers can be found in Table 9. This table
applies to both liquid and solid NaOH containing products at concentration > 2%. Because sodium
hydroxide is corrosive, the risk management measures for human health should focus on the
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 27 / 46

prevention of direct contact with the substance. For this reason automated and closed systems should
preferably be used for industrial uses of sodium hydroxide. Respiratory protection is needed when
aerosols of sodium hydroxide can be formed. Due to the corrosive properties appropriate skin and eye
protection is required.

Table 9 Risk management measures releated to workers

Information type Data field Explanation

Situation at the time of the EU RAR

(2007) for pulp and paper industry:
Almost all plants (97%) indicated having
an automated closed system. Still 50%
indicated that handling with NaOH still
Good practice: replacing, where
occurs during (re)filling of
appropriated, manual processes by
tanks/containers, cleaning, maintenance,
automated and/or closed processes.
unloading lorries, adding reactant,
This would avoid irritating mists,
emptying drums or bags and sampling
sprayings and subsequent potential
(average of 4 workers per plant).
splashes (EU RRS, 2008):
 Use closed systems or covering of Situation at the time of the EU RAR
open containers (e.g. screens) (2007) for chemical industry: Highest
inhalation exposure is expected to occur
(good practice) by loading NaOH from tanker to process
 Transport over pipes, technical vessel. Most of the industries use a
closed and/or automated process and
barrel filling/emptying of barrel with
liquid 50% NaOH.
automatic systems (suction pumps
etc.) (good practice) Situation at the time of the EU RAR
(2007) for textile industry: Exposure to
 Use of pliers, grip arms with long NaOH can occur when steeping
handles with manual use “to avoid woodpulp and during dissolving cellulose
Containment plus direct contact and exposure by xanthate. Most of the industries use a
good work practice splashes (no working over one’s closed and/or automated process. The
required head)” (good practice) NaOH will not be sprayed.

To improve air quality and avoid potential

respiratory track irritation in working
areas.
Situation at the time of the EU RAR
Local exhaust (2007): a total of 8 of 22 customers (36%)
ventilation required replied that they used local exhaust
plus good work Local exhaust ventilation is not ventilation when they handle NaOH on
practise required but good practice. their site.

General ventilation is good practice To improve air quality and avoid potential
unless local exhaust ventilation is respiratory track irritation in working
General ventilation present areas.
Situation at the time of the EU RAR
(2007): the questionnaire indicated that
 Respiratory protection: In case of twentynine percent of the customers
dust or aerosol formation (e.g. replied that inhalation exposure was
spraying): use respiratory possible, while 71% answered that skin
protection with approved filter (P2) exposure was possible and finally 75%
Personal protection (required) replied that eye exposure was possible.
equipment (PPE) In most cases no PPE was used to
required under  Hand protection: impervious prevent inhalation. To prevent skin
regular working chemical resistant protective gloves exposure, 46% of the respondents
conditions (required) reported that gloves were used, while
25% reported that special clothes were
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 28 / 46

Information type Data field Explanation

o material: butyl-rubber, used and finally 29% replied that no PPE

PVC, polychloroprene with was used. To prevent eye exposure 67%
natural latex liner, material of the customers answered that safety
glasses or a full facemask was used and
thickness: 0.5 mm,
the remaining customers replied in most
breakthrough time: > 480 cases that no PPE was used (Euro Chlor,
min 2005).
o material: nitrile-rubber,
fluorinated rubber, material
thickness: 0.35-0.4 mm,
breakthrough time: > 480
min
 If splashes are likely to occur, wear
tightly fitting chemical resistant
safety goggles, face–shield
(required)
 if splashes are likely to occur, wear
suitable protective clothing, aprons,
shield and suits, rubber or plastic
boots, rubber or plastic boots
(required)
Next measures are required (from EU
RRS, 2008):
 workers in the risky process/areas
identified should be trained a) to
avoid to work without respiratory
protection and b) to understand the
corrosive properties and,
Other risk especially, the respiratory
management inhalation effects of sodium
measures related to
hydroxide and c) to follow the safer
workers. For
example: Particular procedures instructed by the
training systems, employer (EU RRS, 2008).
monitoring/reporting
or auditing systems,  the employer has also to ascertain
specific control that the required PPE is available
guidance. and used according to instructions

 High viscosity adjustment with aids

Measures related to (good practice)
the design of
product (other than  Delivery only as barrel commodity
concentration) and/or in the tank car (good
related to workers practice)
to avoid splashes
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 29 / 46

Risk management measures related to professional workers

Because sodium hydroxide is corrosive, the risk management measures for human health should
focus on the prevention of direct contact with the substance. For this reason automated and closed
systems should preferably be used for professional uses of sodium hydroxide. Since automated,
closed systems and local exhaust ventilation may be less feasible to implement, product related
design measures that prevent direct eye/skin contact with NaOH and prevent formation of aerosols
and splashes are more important next to the personal protective equipment measures.

Product related design measures are required. These include specific dispensers and pumps etc
specifically designed to prevent splashes/spills/exposure to occur.

Table 10 gives an overview of the personal protective equipment recommendations. Based on the
NaOH concentration in the preparation, a different degree of restriction is proposed.

Table 10 Personal protective equipment releated to professional workers

NaOH NaOH NaOH

concentration in concentration concentration
product > 2% in product in product <
between 0.5% 0.5%
and 2%

Respiratory protection: In case of dust or compulsory good practice No

aerosol formation (e.g. spraying): use
respiratory protection with approved filter
(P2)

Hand protection: In case of potential dermal compulsory good practice No

contact: use impervious chemical resistant
protective gloves
Protective clothing: If splashes are likely to compulsory good practice No
occur, wear suitable protective clothing,
aprons, shield and suits, rubber or plastic
boots, rubber or plastic boots

Eye protection: If splashes are likely to compulsory good practice No

occur, wear tightly fitting chemical resistant
safety goggles, face –shield

Risk management measures related to environment

Relevant risk management measures related to environment are described in section 9.1.1.4.2.

Waste related measures

There is no solid waste of NaOH. Liquid NaOH waste should be reused or discharged to the industrial
wastewater and further neutralized if needed (see risk management measures related to
environment).

Exposure estimation
Workers exposure

NaOH is a corrosive substance. For the handling of corrosive substances and formulations, immediate
dermal contacts occur only occasionally and it is assumed that repeated daily dermal exposure can be
neglected. Therefore according to the EU RAR (2007), dermal exposure to pure NaOH will not be
assessed. Repeated dermal exposure cannot be neglected for these substances and formulations.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 30 / 46

Relevant populations potentially exposed to generally corrosive products are workers in the chemical
industry, aluminium industry and paper industry. Also textile workers and cleaners may have more or
less direct contact with (diluted) NaOH.

NaOH is not expected to be systemically available in the body under normal handling and use
conditions and therefore systemic effects of NaOH after dermal or inhalation exposure are not
expected to occur.

Measured exposure concentrations

The measured exposure concentrations to workers are summarized in Table 11.

Table 11 Long-term exposure concentrations to workers (measured exposure concentrations)

Measured exposure
Routes of concentrations Explanation / source of measured data
exposure Value unit
From EU RAR (2007): end use of formulated products
Personal + area sampling, sample time: 250-364 min,
locations: mechanic, table outside cleaning room, sidewall
<0.11 mg/m3
on electrical box, centre on unused equipment, black wall
on tool cart (Burton et al., 2000)
From EU RAR (2007): industrial use in pulp and paper
Locations: woodplant, pulping, bleach/chem.preparation,
<0.5/16* mg/m3 machine room, recover and recaust, Number: 2-12,
Duration: >8 hours, TWA (Kennedy et al., 1991)
Locations: pulping, refining, etc. of stock,
0.001-
mg/m3 paper/paperboard machine, de-inking of waste paper,
0.70
TWA, total number: 5, number of detects: 1-5, Range:
0.001 – 1.2 mg/m3) (Korhonen et al., 2004)
From EU RAR (2007): aluminium industry
Data from 1997-1999, Locations: during caustic wash,
sand trap dump (at operator location, caustic wash recycle
tank, screw conveyor new building, overflow tank old
building, decanter, filter wach at hoist control, over caustic
tank ground floor, drum filters/normal operating, drum
0.033-1.1
filters/normal operating, on ground in front of filter, on
2.40*** mg/m³ AM
workbench on filter, 1st floor at filter drain valve, 1st floor
5.80**
by conveyor belt, over Launder gate during caustic wash,
Inhalation 4.70***
over precipitation tank, caustic wash, operator location,
exposure descaling launder gates, caustic wash filling Primary B
tank, sample on top of tank, adjacent to cyclones during
normal processing
Medium: impinger/filter, 22 sample points with 1-5
repititions, t= 5-117 min
New literature: aluminium industry
Refinery 2, Maintenance, N=19, Range: 0.02-4 mg/m3, 4
0.2 mg/m3 GM
hour TWA (Musk et al., 2000)
Refinery 3, Maintenance, N=8, Range: 0.05-0.6 mg/m3, 4
0.17 mg/m3 GM
hour TWA (Musk et al., 2000)
Refinery 3, Digestion, N=6, Range: 0.05-0.6 mg/m3, 15 min
0.11 mg/m3 GM
sample (Musk et al., 2000)
Refinery 2, Clarification, N=27, Range: 0.1-2.3 mg/m3, 4
0.46 mg/m3 GM
hour TWA (Musk et al., 2000)
Refinery 3, Clarification, N=9, Range: 0.05-1.1 mg/m3, 4
0.09 mg/m3 GM
hour TWA (Musk et al., 2000)
Refinery 1, Precipitation, N=19, Range: 0.1-0.8 mg/m3, 4
0.34 mg/m3 GM
hour TWA (Musk et al., 2000)
Refinery 3, Calcination or shipping, N=18, Range: 0.05-0.9
0.19 mg/m3 GM
mg/m3, 15 min TWA (Musk et al., 2000)
Refinery 2, Descale, N=11, Range: 0.1-1 mg/m3, 4 hour
0.56 mg/m3 GM
TWA (Musk et al., 2000)
Refinery 3, Descale, N=12, Range: 0.05-3.5 mg/m3, 15 min
0.4 mg/m3 GM
TWA (Musk et al., 2000)
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 31 / 46

Measured exposure
Routes of concentrations Explanation / source of measured data
exposure Value unit
New data from aluminium industry:
year: 2001, location = digestion, N=18, duration= 8 hours,
0.006 mg/m³ AM
range TWA= 0.002 – 0.024 mg/m3
year: 2001, location = filtration, N=19, duration= 8 hours,
0.021 mg/m³ AM
range TWA= 0.005 – 0.081 mg/m3
year: 2001, location = precipitation, N=11, duration= 8
0.017 mg/m³ AM
hours, range TWA= 0.003 – 0.072 mg/m3
year: 2001, total, N=48, duration= 8 hours, range TWA=
0.014 mg/m³ AM
0.002 – 0.081 mg/m3
From EU RAR (2007): textile industry
Mercerization, Bleaching , Washing , Mixing and
1.7-6.8 mg/m³ AM
concentration , 1-13, Storage , workers exposed, N=8-86
* A single high reading because of upset conditions at the slaker/causticizer
** Sample known to be contaminated as no steam/mist came in contact with sampler during
sampling; samples was taken up-wind of steam source due to prevailing wind conditions
*** Samples were taken in very wet steam/ mist clouds; problems with pumps cutting out and
pumps flooding were recorded

End use of formulated products

In April 1998, a health hazard evaluation concerning the cleaning, overhauling and repair of aircraft
lavatory tanks and hardware was conducted at one company. The main purpose was to study the
potential exposure to infectious micro-organisms but also some measurements of NaOH exposure
were conducted (Burton et al., 2000). NaOH was a component in the soaps and cleaning agents used
in the cleaning room. One personal breathing zone and four area samples (three inside and one
outside the lavatory cleaning room) were collected. The samples were analysed for alkaline dust and
mist by acid-base titration according to NIOSH Method 7401. Following Burton et al. (2000) the results
were expected to be low since little spraying of the soap was done on the day of the monitoring.
Because the exact exposure level is unknown, these measurements are not taken to the risk
characterization (EU RAR, 2007).

Pulp and paper industry

In 1988 measurements were conducted in a paper mill (Kennedy et al., 1991). A total of 28 area
samples were taken at different locations with a minimum measurement time of 8 hours (see Table
11). It is unclear how measurements were collected. None of the measurements exceeded the
detection level. All measured areas where exposed for over 8 hours to a NaOH concentration below
0.5 mg/m3.

In an international epidemiological study of workers exposure to chemical agents in the pulp and
paper industry a database with a total of 3873 measurements were analysed (Korhonen et al., 2004).
Most of the measurements were from 1980 to 1994 and from a total 12 countries. A total of 15
measurements were conducted to NaOH (see Table 11). Two measurements during pulping stock and
one measurement at the paperboard machine were exceeding the detection limit. When de-inking
waste paper all measurements were exceeding the detection limit with an AM of 0.70 mg/m 3 (range
0.30 – 1.20 mg/m3). The duration of the measurements was more than one hour, but the exact
duration was unclear. It was not clear from the article which tasks were conducted during the
measurements. These measurements reflect the old situation where the proper risk management
measures were not sufficiently taken into account. Following Table 9, the following RMMs are
recommended: 1) to use closed systems as much as possible, 2) to use LEV where appropriate and 3)
to use RPE in case of splashes or aerosol formation.

Alumina industry

At company A static measurements were conducted in 1997 and 1999 to “caustic mist” during
production of aluminum. In Table 11, a summary is given of these measurements. Measurements
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 32 / 46

were conducted to caustic mist with a 37 mm, 0.8 μm, MCEF, membrane filter with a cellulose backup
pad in a closed face 3 piece cassette or with a SKC midget impinger containing ultra pure water. All
measurements performed (see Table 11) are worst-case area samples and many of the locations
selected for sampling were ones where high concentrations were expected. The arithmetic mean of all
measurements is 0.39 mg/m3 with a range 0.033-1.1 mg/m3 (excluding measurements in accidental
situations with failing equipment). Mean measurement time is 57 min. Because operators are not
routinely present at the measured locations it is assumed that total present time during a day is the
same as the approximate mean measurement time (1 hour). Expecting an 8-hour working day with an
exposure of 1.1 mg/m3 for 1 hour and zero exposure during the rest of the day gives a full shift
reasonable worst case exposure level of 0.14 mg/m3. The short-term reasonable worst-case value is
estimated as 1.1 mg/m3. Expecting an 8-hour working day with an exposure of 0.39 mg/m 3 for 1 hour
and zero exposure rest of the day gives a full shift typical exposure level of 0.05 mg/m 3. The short-
term typical exposure value is estimated as 0.39 mg/m3 (EU RAR, 2007).

Musk et al. (2000) provides occupational exposure data of caustic mist for three alumina refineries in
Western Australia. The sample duration is 15 minutes and 4 hour time weight averages. The activities
covered are maintenance, digestion, clarification, precipitation, calcination or shipping and descale.

In another study (Fritschi et al., 2001) the results for exposure to caustic mist were qualitatively
presented and therefore not suitable for the risk assessment.

These measurements above reflect the old situation where the proper risk management measures
were not sufficiently taken into account. Following Table 9, the following RMMs are recommended: 1)
to use closed systems as much as possible, 2) to use LEV where appropriate and 3) to use RPE in
case of splashes or aerosol formation.

More recent data were collected from the aluminum industry covering various activities (digestion,
filtration, precipitation). Multiple samples were collected during the full shift. The maximum observed
concentration is 0.021 mg/m 3. This value will be further considered for risk characterization.

Textile industry

In 1981 measurements were conducted at different textile producing companies in Finland (Nousiainen
et al., 1981). A total of 198 area samples were taken at different locations for a whole shift duration (see
Table 11). During the measurements the fixed apparatus was positioned so that the best possible
approximate values of the worker exposure would be obtained, without disturbing normal work routines.
The distance from the outer edge of the mercerization, leaching or washing machine was 1 m and the
sampling height from the floor or work platform was 1-5 m. The measurements were made at the front,
middle and back part of each mercerization machine. The contents measured at the middle were often
highest because the solution was hot there. For bleaching the measurements were likewise made at
different points of the machine. Most measurements were conducted during mercerisation and bleaching
and the number of workers possibly exposed is, in comparison with other locations, high. These
measurements are out of date and they do not describe a worst case situation, they describe the textile
industry 30 years ago. Following Table 9, the following RMMs are recommended: 1) to use closed
systems as much as possible, 2) to use LEV where appropriate and 3) to use RPE in case of splashes
or aerosol formation. So therefore, these RMMs should be used to avoid inhalation exposure. The use
of NaOH in today’s textile industry is mostly in closed system without exposure of the workers (see
example pictures of Figure 2). In those cases where there is still open use, there is no relevant exposure
because this would not be a spraying process but a dipping process without aerosol formation. An open
use measurement for KOH which is very similar to NaOH (the cleaning of machinery which implies
possible exposure) showed less than 0.06 mg/m3 and this was the detection limit.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 33 / 46

Figure 1: The use of NaOH in today’s textile industry is in closed system without exposure of
the workers (left: Distribution NaOH, middle; Storage of NaOH, right: Use of NaOH (dying))

Estimated exposure concentrations

The estimated exposure concentrations to workers reported in the EU RAR (2007) are summarized in
Table 12.

Table 12 Long-term exposure concentrations to workers (estimated exposure concentrations)

Estimated
Exposure
Explanation / source of measured data
Routes of Concentrations
exposure value unit
Various dermal exposure estimates were calculated in the EU RAR
0.42-84 mg/d
Dermal (2007) using EASE for following scenarios: end use of liquid oven
exposure cleaner, end use of spray oven cleaner, end use of hair straightening
products and use in textile industry.
From EU RAR (2007): formulation of NaOH containing products
Adding liquid NaOH (T = 20°C) to a process (vapour pressure very low,
Typical: no aerosol formed, LEV present, use pattern non dispersive use), EASE
0.04 mg/m3 predicts a typical inhalation exposure of 0-0.17 mg/m3 (0 – 0.1 ppm).
RWC: Assuming NaOH concentration of 50% a typical exposure value of 0.04
0.08 mg/m3 mg/m3 (0.025 ppm) is estimated (half of range 0 – 0.05 ppm). Estimating
the reasonable worst-case exposure gives a value of 0.08 mg/m3 (0.05
ppm, upper value of the range).
Inhalatio From EU RAR (2007): end use of liquid oven cleaner
n
EASE estimates (assuming very low vapour pressure, no aerosol formed,
exposure
direct handling, non-dispersive use) 0 - 0.17 mg/m3 (0 – 0.1 ppm) for
typical inhalation exposure. Assuming dilution of 1:50 (oven cleaner is not
used purely) and NaOH concentration of 7.5% (mean concentration
negligible
NaOH) typical inhalation value is estimated (by taken the mean value of
the range) as 1.3 . 10-4 mg/m3 (0.02 . 0.075 . 0.085). A reasonable worst
case inhalation exposure is estimated by taking the upper range value
which gives an estimation of 2.6 . 10-4 mg/m3 (0.02 . 0.075 . 0.17). Both,
typical and worst case estimates, can be considered to be negligible.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 34 / 46

Estimated
Exposure
Explanation / source of measured data
Routes of Concentrations
exposure value unit
From EU RAR (2007): end use of spray oven cleaner
NaOH is a non-volatile substance and therefore EASE is not suitable for
estimating inhalation exposure occurred by spraying. The EU RAR (2007)
refers to a model derived by De Pater et al. (1999) to estimate inhalation
exposure to non-volatile substances during spraying. This model is based
on measured exposure levels to polyisocyanates in spray coating and is
also considered to be relevant for spray cleaning. Model:

0.13 mg/m3

Assuming a NaOH concentration of 3% (mean concentration of NaOH in

spray) Cs is 0.03. Because the measured exposure to non-volatiles and
the percentage non-volatile substances are unknown, the estimates for
spray painting are used as indicative values: Em = 10 mg/m 3 and Cm =
0.3. This results in an estimated inhalation exposure of 1 mg/m 3 (10 .
0.03/0.3). If spraying occurs 1 hour/day and rest of the day no exposure
is assumed, a reasonable worst case of 0.13 mg/m 3 is estimated.
From EU RAR (2007): EASE simulation for chemical industry,
industrial use in pulp and paper and for aluminium industry:
Typical: Adding liquid NaOH (T = 20°C) to a process (vapour pressure very low,
0.04 mg/m3 no aerosol formed, use pattern non dispersive use) EASE predicts a
RWC: typical inhalation exposure of 0 – 0.17 mg/m3 (0 – 0.1 ppm). Assuming
0.08 mg/m3 NaOH concentration of 50% a typical exposure value of 0.04 mg/m3
(0.025 ppm) is estimated (half of range 0 – 0.05 ppm). For estimating the
reasonable worst case exposure 0.08 mg/m3 (0.05 ppm, upper value of
the range) is taken.
From EU RAR (2007): for textile industry
Steeping cellulose in sodium hydroxide solution can be compared with
mixing. In this case cellulose will be added to sodium hydroxide. When
0 – 0.043 mg/m3 assuming a closed system with vapour pressure very low, no aerosol
formed and use pattern non-dispersive, EASE predicts a value of 0 – 0.17
mg/m3 (0 – 0.1 ppm). If a concentration of 25% NaOH is used, the range
will become 0 – 0.043 mg/m3.

The estimated inhalation exposure concentrations to workers according to the ECETOC TRA tool are
summarized in Table 12. It was assumed that there is no local exhaust ventilation and no respiratory
protection unless specified otherwise. The duration of exposure was set at more than 4 hours per day
as a worst-case assumption. And professional use was specified where relevant as a worst-case
assumption. For the solid, the low dustiness class was selected because NaOH is very hydroscopic.
Only the most relevant PROCs were considered in the assessment.

There is no need to quantitatively derive dermal exposure estimations because a DNEL for dermal
exposure was not derived.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 35 / 46

Table 13 Long-term inhalation exposure concentrations to workers (estimated exposure

concentrations)

PROC PROC description Liquid (mg/m3) Solid (mg/m3)

PROC 1 Use in closed process, no likelihood of exposure 0.17 0.01
PROC 2 Use in closed, continuous process with 0. 17 0.01
occasional controlled exposure (e.g. sampling)
PROC 3 Use in closed batch process (synthesis or 0.17 0.1
formulation)
PROC 4 Use in batch and other process (synthesis) 0.17 0.2 (with LEV)
where opportunity for exposure arises
PROC 5 Mixing or blending in batch processes for 0.17 0.2 (with LEV)
formulation of preparations and articles
(multistage and/or significant contact)
PROC 7 Spraying in industrial settings and applications 0.17 Not applicable
PROC Transfer of substance or preparation 0.17 0.5
8a/b (charging/discharging) from/to vessels/large
containers at non dedicated or dedicated
facilities
PROC 9 Transfer of substance or preparation into small 0.17 0.5
containers (dedicated filling line, including
weighing)
PROC10 Roller application or brushing of adhesiveand 0.17 0.5
other coating
PROC11 Spraying outside industrial settings or 0.17 0.2 (with LEV)
applications
PROC13 Treatment of articles by dipping and pouring 0.17 0.5
PROC14 Production of preparations or articles by 0.17 0.2 (with LEV)
tabletting, compression, extrusion, pelettisation
PROC15 Use a laboratory reagent 0.17 0.1
PROC19 Hand-mixing with intimate contact and only PPE 0.17 0.5
available.
PROC23 Open processing and transfer operations (with 0.17 0.4 (with LEV
minerals) at elevated temperature and RPE(90%))
PROC24 High (mechanical) energy work-up of 0.17 0.5 (with LEV
substances bound in materials and/or articles and RPE(90%))
PROC 26 was considered to mainly applicable to metals industry. Handling of inorganic substances is
assumed to be included in the existing PROCs assessed.

Inhalation exposure during loading may take place due to vapours or aerosols formed when the barrel
or drum is opened and when adding the product to the process. NaOH will be diluted after loading into
a tank.

Summary of the exposure values

The summary of exposure concentrations to workers, taken forward to risk characterization, is given in
Table 14.

Table 14 Summary of exposure concentration to workers

Routes of
exposure Concentrations Justification

84 mg/d From EU RAR (2007): NaOH products with a concentration > 2% are
Dermal corrosive, therefore effective control measures are expected to be in place
exposure to prevent dermal exposure. Furthermore protective clothing and gloves are
(in mg/cm2) considered to be used consistently when handling corrosive substances.
Production companies report the use of protective gloves, suits and boots
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 36 / 46

Routes of
exposure Concentrations Justification

while handling pure NaOH. Repeated daily dermal exposure to the pure
substance is therefore considered negligible.

Dilutions of NaOH containing less than 2% of the substance do not have

corrosive properties. For this concentration a dermal exposure value is
estimated.

A reasonable worst case exposure of 84 mg/day will be taken to risk

characterisation for handling concentrations < 2% NaOH.

In the EU RAR (2007): following values were selected for risk

charcterisation:

1 Pulp and paper industry: 0.08 mg/m 3

< 1 mg/m3
2 De-inking waste paper: 1.20 mg/m 3

3 Aluminium: 0.14 mg/m3. Short-term value: 1.1 mg/m3

Inhalation 4 Textile: 3.4 mg/m3
exposure
(in mg/m3) 5 Chemical industry: 0.08 mg/m 3

Most measurements reflect an outdated situation where the proper risk

management measures were not sufficiently taken into account. Following
Table 9, the following RMMs are recommended: 1) to use closed systems
as much as possible, 2) to use LEV where appropriate and 3) to use RPE
in case of splashes or aerosol formation. Applying an RMM efficiency rate
of more than 90% would decrease the exposure concentrations up to a level
below 1 mg/m3.

Indirect exposure of humans via the environment (oral)

Indirect exposure to humans, for example through the uptake of drinking water, is not relevant for
NaOH. Any potential for exposure to NaOH due to environmental releases will only have relrevance at
the local scale. Any pH effect of local releases will be neutralised in the receiving water at the regional
scale. Therefore indirect exposure of humans via the environment (oral) is not relevant in the case of
NaOH (EU RAR, 2007).

Environmental exposure

As stated in the EU RAR on NaOH (2007), the risk assessment for the environment will focus solely
on the aquatic environment, when applicable including STPs/WWTPs, as the emissions of NaOH in
the different life-cycle stages (production and use) mainly apply to (waste) water. The aquatic effect
and risk assessment will only deal with the effect on organisms/ecosystems due to possible pH
changes related to OH- discharges, as the toxicity of the Na+ ion is expected to be insignificant
compared to the (potential) pH effect. Only the local scale will be addressed, including sewage
treatment plants (STPs) or waste water treatment plants (WWTPs) when applicable, both for
production and industrial use. Any effects that might occur would be expected to take place on a local
scale and therefore it was decided as not meaningful to include the regional or continental scale in this
risk assessment. Furthermore, the high water solubility and very low vapour pressure indicate that
NaOH will be found predominantly in water. Significant emissions to air are not expected due to the
very low vapour pressure of NaOH. Significant emissions to the terrestrial environment are not
expected either. The sludge application route is not relevant for the emission to agricultural soil, as no
sorption of NaOH to particulate matter will occur in STPs/WWTPs.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 37 / 46

The exposure assessment for the aquatic environment will only deal with the possible pH changes in
STP effluent and surface water related to the OH- discharges at the local scale.

Environmental releases

To estimate the environmental releases from the uses of NaOH a questionnaire was organised by
Euro Chlor, in cooperation with the Portuguese and Dutch authorities, focussing on the major
downstream uses (EU RAR, 2007). Because the exposure assessment focussed on possible pH
changes in the local aquatic environment, data were requested on the pH control at user sites. Based
on the experience with the results from the questionnaire to producers (see Section 9.1) it was
envisaged that the pH of discharges would also be strictly controlled by the industry involved, often in
response to local requirements. Therefore, the environmental part of the questionnaire was simplified
in agreement with the rapporteur, asking the following two questions: ‘does your final waste water
which is discharged to the receiving water still contain NaOH?’ and ‘if yes: what do you do to prevent
an impact from NaOH discharge’? The results of the user questionnaire have been reported in detail in
Euro Chlor (2005).

The paper and pulp industry was addressed via CEPI, the Confederation of the European Paper
Industries and received 34 replies. For the paper and pulp industry one questionnaire was received
from Germany (National Federation), which represented the common practice in this country.

Other industries were approached via five large producers of NaOH who each sent out a questionnaire
to 20 of their customers, in nearly all cases end users of NaOH. A reply had been received from 24
customers, representing a response of 24%. From these 24 customers, 8 responses were received
from Spain. The other customers were located in Belgium, France, Germany, The Netherlands and
United Kingdom. The majority originated from the chemical industry (17 replies). One reply was
received from the steel industry, textile industry, rubber production, distribution, food industry, metal
industry and aluminium industry. In one case a distributor completed the questionnaire, which is not an
end user of NaOH.

For the pulp and paper industry the average amount of NaOH used per day was 14 tonnes (range
from 0.005 – 160 tonnes), while the remaining end users used an average amount of 24 tonnes/day
(range from 1.5 – 110 tonnes). For the paper and pulp sector 32 respondents answered that the final
wastewater did not contain NaOH, but in two cases it did. For these cases it was stated that the impact
was controlled. For the 23 other end users questioned (excluding the distributor), 21 indicated to have
no NaOH in the final effluent. For two sites, from the chemical industry, the final effluent contained
NaOH. For these sites it is not specifically known if they neutralised their effluent. Normally, local
procedures are in place to prevent discharges outside the range required by authorities, such as
recycling, mixing with other streams for neutralisation or discharge to a WWTP when that is
considered favourable.

The results from the questionnaires for the use sites demonstrate that in most cases the final effluents
did not contain NaOH anymore. Usually, the pH of waste water discharges is controlled and almost
always proper regulations are in place. Nevertheless, for some use sites, emitting their effluents to the
environment, it cannot be excluded that they do not neutralise their effluents and have no legal
obligation to neutralise.

As stated above, the emissions of NaOH mainly apply to (waste) water. Furthermore, the high water
solubility and very low vapour pressure indicate that NaOH will be found predominantly in water. In
water (including soil or sediment pore water), NaOH is present as the sodium ion (Na+) and hydroxyl
ion (OH-), as solid NaOH rapidly dissolves and subsequently dissociates in water.

Exposure concentration in waste water treatment plants (WWTP)

Referring to the RMMs related to the environment to avoid discharging NaOH solutions into municipal
wastewater unless neutralization is carried out, the pH of the influent of a municipal wastewater
treatment plant is neutral and therefore, there is no exposure to the biological activity.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 38 / 46

Exposure concentration in aquatic pelagic compartment

The exposure concentration in aquatic pelagic compartment is similar to the assessment done in ES 1
(see section 0).

Exposure concentration in sediments

The exposure concentration in sediment compartment is similar to the assessment done in ES 1 (see
section 0).

Exposure concentrations in soil and groundwater

The exposure concentration in soil and groundwater compartment is similar to the assessment done in
ES 1 (see section 0).

Atmospheric compartment

The exposure concentration in atmospheric compartment is similar to the assessment done in ES 1

(see section 0).

Exposure concentration relevant for the food chain (Secondary poisoning)

The exposure concentration relevanty for the food chain is similar to the assessment done in ES 1
(see section 0).

Exposure Scenario 4: Consumer use of NaOH

Exposure scenario
Short title of the exposure scenario

SU21: private households

PROC not applicable for this ES

PC 20, 35, 39 (neutralisation agents, cleaning products, cosmetics, personal care products). The other
PCs are not explicitly considered in this exposure scenario. However, NaOH can also be used in other
PCs in low concentrations e.g. PC3 (up to 0.01%), PC8 (up to 0.1%), PC28 and PC31 (up to 0.002%)
but it can be used also in the remaining product categories (PC 0-40).

AC not applicable for this ES

Description of activities, processes and operational conditions covered in the exposure

scenario

NaOH (up to 100%) is also used by consumers. It is used at home for drain and pipe cleaning, wood
treatment and it also used to make soap at home (Keskin et al., 1991; Hansen et al., 1991; Kavin et
al., 1996). NaOH is also used in batteries and in oven-cleaner pads (Vilogi et al., 1985). Following
uses are briefly described:

Floor strip products

Floor strippers are used to remove old protective layers. The maximum content of sodium hydroxide in
floor strippers is 10%. For stripping the floor of the living room, 550 g of the product is needed for an
area of 22 m2. This is done with the undiluted product. The product is sprinkled on a cloth and is
manually rubbed on the floor.

Hair straighteners

The maximum content of sodium hydroxide in hair straighteners for use by the general public is 2%
(EU Cosmetics Directive). Sodium hydroxide as a caustic type of chemical will actually soften hair
fibres. It will also cause the hair to swell at the same time. As the sodium hydroxide solution is applied
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 39 / 46

of the hair, it penetrates into the cortical layer and breaks the cross-bonds. The cortical layer is
actually the middle of inner layer of the hair shaft that provides the strength, elasticity and shape of the
curly hair.

Oven cleaners

Oven cleaners are strong degreasers and they are suitable for removing dirt stuck on ovens, grills, etc.
Oven cleaners contain strong alkaline ingredients. Strong alkali is necessary to remove burned-on
soils. There are trigger sprays and spray cans. When using a spray can, foam is formed on the target
area. After spraying, the oven door is closed and the foam has to soak 30 minutes. Then the oven is
wiped clean with a wet cloth or sponge and one has to rinse frequently. The maximum content of
sodium hydroxide in a spray can is 5%. For the purpose of the exposure calculations, the product is
assumed to contain 0.83% NaOH (which is 2.5% of a 33% aqueous NaOH solution). The product is a
milky-white gelatinous liquid. Formulation as a gel leads to large droplets upon spraying (100% >10
um). The frequency of application is 1 event per day and the duration is 2 minutes per event. Spraying
into cold oven, with potential exposure to hands and arms. One can spray up to 1 g product per
second, by hand-held ready-to-use trigger spray.

Drain openers

Drain openers open slow running and obstructed drains by dissolving and by loosening grease and
organic waste. There are different kinds of drain openers, products containing either sodium hydroxide
or sulphuric acid. Liquid drain openers have a maximum NaOH content of 30%. The use of liquid drain
openers is comparable with the dosing of liquid cleaners. The drain opener must be dosed slowly
down the drain. Pellets, which can also be use for opening the drain, have contents up to 100%. The
drain opener must be dosed slowly down the drain. One has to wait at least 15 minutes so that the
drain opener can clear the blockage.

Other cleaning products

NaOH is used during the production phase of various cleaning products although in most case the
amounts are low and NaOH additions are mainly for pH adjustment. The amounts used will interact
with other ingredients in acid-base reactions and thus practically no NaOH is left in the final consumer
product. However, hypochlorite products may contain 0.25-0.45% of NaOH in the final formulation.
Some toilet cleaners may contain up to 1.1% and certain soaps contain up to 0.5% of NaOH in the
final formulation.

Consumer use, service life and waste stage of NaOH in batteries

Aqueous sodium hydroxide is employed as the electrolyte in alkaline batteries based on nickel-
cadmium and manganese dioxide-zinc. Even though potassium hydroxide is preferred over sodium
hydroxide, NaOH can still be present in the alkaline batteries, but here this substance is strictly
confined in the battery screening and doesn’t come in contact with the consumer.

The industrial and professional uses of NaOH in batteries (incl. recycling operations) are covered
under Exposure Scenario 3. This ES focuses on the consumer use, the service life and the end-of-life
stage of NaOH in batteries. Given that batteries are sealed articles and that NaOH involved in their
maintenance is not intended for direct release exposure to and emission from NaOH in these life-cycle
stages should be minimal.
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 40 / 46

Risk management measures

Risk management measures related to consumers (all except batteries)

The risk management measures related to consumers are mainly related to prevent accidents.

Measured related to the design of the product

 It is required to use resistant labelling-package to avoid its auto-damage and loss of the label
integrity, under normal use and storage of the product. The lack of quality of the package
provokes the physical loss of information on hazards and use instructions.

 It is required that household chemicals, containing sodium hydroxide for more than 2%, which
may be accessible to children should be provided with a child-resistant fastening (currently
applied) and a tactile warning of danger (Adaptation to Technical Progress of the Directive
1999/45/EC, annex IV, Part A and Article 15(2) of Directive 67/548 in the case of, respectively,
dangerous preparations and substances intended for domestic use). This would prevent
accidents by children and other sensitive groups of society.

 It is required that improved use instructions, and product information should always be
provided to the consumers. This clearly can efficiently reduce the risk of misuse. For reducing
the number of accidents in which (young) children or elderly people are involved, it should be
advisable to use these products in the absence of children or other potential sensitive groups.
To prevent improper use of sodium hydroxide, instructions for use should contain a warning
against dangerous mixtures

 It is advisable to deliver only in very viscous preparations

 It is advisable to delivery only in small amounts

Instructions addressed to consumers

 Keep out of reach of children.

 Do not apply product into ventilator openings or slots.

PPE required under regular conditions of consumer use

NaOH NaOH NaOH

concentration in concentration concentration
product > 2% in product in product <
between 0.5% 0.5%
and 2%

Respiratory protection: In case of dust or required good practice no

aerosol formation (e.g. spraying): use
respiratory protection with approved filter
(P2)

Hand protection: In case of potential dermal required good practice no

contact: use impervious chemical resistant
protective gloves
Eye protection: If splashes are likely to required good practice no
occur, wear tightly fitting goggles, face –
shield

Risk management measures related to consumers (batteries)

TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 41 / 46

Measured related to the design of the product: It is required to use completely sealed articles with a
long service life maintenance.

Risk management measures related to environment

There are no specific risk management measures related to environment.

Waste related measures

This material and its container must be disposed of in a safe way (e.g. by returning to a public
recycling facility). If container is empty, trash as regular muncipal waste.

Batteries should be recycled as much as possible (e.g. by returning to a public recycling facility).
Recovery of NaOH from alkaline batteries includes emptying the electrolyte, collection and
neutralization with sulphuric acid and carbon dioxide. The occupational exposure related to these
steps is considered in the exposure scenario on industrial and professional use of NaOH.

Exposure estimation
Consumer exposure

For consumer exposure it is important to stress, that sodium hydroxide exposure is an external
exposure. Contact with tissue and water will give sodium and hydroxide ions. These ions are
abundantly available in the body.

A significant amount of sodium is taken up via the food because the normal uptake of sodium via food
is 3.1-6.0 g/day according to Fodor et al. (1999). In the NaOH EU RAR (2007), external exposure
concentrations in mg/kg were calculated and compared with the sodium intake via food to see whether
this is a relevant exposure route. Several scenarios were assessed: floor strippers, hair straighteners,
oven cleaners and drain openers. Overall, it was concluded that the sodium uptake due to the use
NaOH containing products is neglibible compared to the daily dietary intake of sodium ions (EU RAR,
2007). The effect of sodium intake is not further considered in this sodium hydroxide dossier.

Since accidental exposure is normally excluded from an EU chemical safety assessment and
accidental exposure is considered in the EU RAR (2007, Section 4.1.3.2, pages 59-62), accidental
exposure will not be further assessed in this dossier. However, the risk management measures for
consumers, identified in the NaOH risk reduction strategy (EU RRS, 2008) are included in the dossier.

Acute/Short term exposure

Acute/short term exposure was assessed only for the most critical use: use of NaOH in a spray oven
cleaner

Inhalation exposure to NaOH in the oven cleaner was estimated using different modelling approaches:

1) ConsExpo software (version 4.1, http://www.consexpo.nl; Proud’homme de Lodder et al.,

2006): default product: oven cleaner (application: spraying), default values apply to trigger
spray

2) SprayExpo (Koch et al., 2004): release pattern: wall area (surrogate for the use assessed
here)
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 42 / 46

Conditions of use and input parameters

The conditions of use were given by the manufacturer of the product as shown in the following table.
This table only lists specific values and their rationale but does not include the default values used in
the different models:

Parameter Value

Package 375 ml trigger spray

Amount used 120 g 1

Spray duration 120 sec 1

Calculated mass generation rate 1 g/sec 1

Distance nozzle to face 0.5 m

Distance nozzle to oven wall 0.3 m

Weight fraction compound 0.025 (2.5% ingredient (33% NaOH) assumed to be

relevant for possible irritation)

Median of the particle size distribution 273 µm 1 (mean of three measurements for one
package; lowest value from three different
packages tested)

Coefficient of variation (fraction) of the 1.15 1 (see text)

median

Maximum particle size 670 µm (estimated from graphical droplet size

distribution)

Room volume 15 m3 2

Air exchange 2.5/h (ConsExpo default, also used for SprayExpo)

Inhalation cut-off diameter 670 µm (set to maximum value of the distribution

since exposure at the nose is estimated)

1 These data deviate from the default values of the models, see text for details. SprayExpo
requires a minimum spray duration of 300 seconds. In order to retain the total amount used of
120 g, the mass generation rate in this model was reduced.
2This is the default value from ConsExpo for a kitchen. The room size in SprayExpo (lowest
possible room height: 3 m) was adapted to result in an identical room value.

The product-specific data slightly differ from the ones used in ConsExpo 4.1 (Proud’homme de Lodder
et al., 2006). These authors report a mass generation rate of 0.78 g/sec for general oven cleaners.
The value taken here is somewhat higher but still lower than the value of 1.28 g/sec given by the same
authors for an anti-grease cleaning trigger spray.

The particle size distribution was taken from product-specific measurements. Three different packages
of the product were tested with three measurements for each package. In addition, measurements
were performed with distances of 10 and 20 cm, respectively, between nozzle and laser beam. For the
exposure assessment, the 10 cm distance trials were taken and the lowest value (mean of three
measurements) was chosen.

The respective distribution is described by (rounded to 3 significant figures):

 a 10th percentile of 103 µm

TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 43 / 46

 a 50th percentile of 273 µm

 a 90th percentile of 314 µm

Under the assumption of a lognormal distribution (Proud’homme de Lodder et al., 2006), the software
@risk (version 4.5.2, Pallisade Corporation, 2002) was used to define a “product-specific distribution”
with the following values:

 Median = 273 µm

 10th percentile: 104 µm

 μ = ln(GM) (corresponds to ln(median)) = ln(273) = 5.61

 δ = ln(GSD) = 0.75

leading to a standard deviation of 314 and a C.V. of (314/273 =) 1,15 (the latter is required for
ConsExpo software). The @risk software also allows deriving the percentages representing defined
size classes (which are required for SprayExpo modelling).

See Annex for detailed results of the modelling with both models. Please note: a concentration of
2.5% (of 33% NaOH in water) was used in the modelling exercises. Results therefore were divided by
3 to derive the results as shown in Table 15.

Other exposure estimates

The EU Risk Assessment Report (2007) on sodium hydroxide estimates occupational exposure to
NaOH from the use of oven cleaners. The estimate is based on an assumed exposure concentration
of 10 mg/m3 for aerosols. This value is derived from experiences with spray painting. With a
concentration of 3% NaOH and 30% non-volatile substances in the oven cleaner a short-term
inhalation exposure (during spraying) of 1 mg/m 3 was estimated.

Accordingly, with a NaOH concentration in the product of 0.83% (this product) an inhalation exposure
concentration of 0.3 mg/m3 would result.

Modelling results

Results for the different modelling approaches are shown in Table 15. An ingredient concentration of
2.5% (with the ingredient being 33% NaOH in water) was used in the modelling exercises. Therefore,
modelling results as given in the Annex were divided by 3 to arrive at results for pure NaOH.

Table 15 Acute exposure concentrations to consumers

Measured expo-
Routes Estimated Exposure
sure concentra-
of Concentrations
tions Explanation / source of measured data
exposur
e
value unit Value Unit

0.012 (mean) * mg/m3

ConsExpo 4.1: Spraying for 2 minutes,
0.33 (peak concen-
60 minutes exposure period
Inhalatio tration)
n
SprayExpo: mean for spraying period (5
exposure 1.6 mg/m3
minutes)

0.3 mg/m3 According to EU RAR, 2007

* 0.012 mg/m3 represents the mean for a total exposure period of 60 minutes, as calculated by
ConsExpo and includes 58 minutes without application. As here the mean concentration during
application is sought, the peak concentration (0.33 mg/m 3) is used as a conservative estimate of the
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 44 / 46

average concentration.

Summary of the short-term exposure values

Table 16 Summary of acute exposure concentrations to consumers

Routes of exposure Concentrations Justification

Oral exposure
Not applicable
(in mg/kg bw/d)

Dermal local exposure

Not applicable
(in mg/cm2)

Dermal systemic exposure

Not applicable
(in mg/kg bw/d)

Inhalation exposure
0.3 to 1.6 See modelling results above
(in mg/m3)

Long-term exposure

Exposure to oven cleaner spray is restricted to few minutes per event with up to 1 event per day (worst
case assumption, in practice a lower frequency of approx. once per week is reasonable). Therefore,
no long-term exposure has to be considered.

NaOH is not expected to be systemically available in the body under normal handling and use
conditions and therefore systemic effects of NaOH after dermal or inhalation exposure are not
expected to occur.

If the recommended RMMs are respected, local exposure through inhalation will not be higher
compared to inhalation exposures in ES3. Therefore, the consumer exposure through inhalation is not
further quantitatively assessed.

Consumer exposure to NaOH in batteries is zero because batteries are sealed articles with a long
service life maintenance.

Indirect exposure of humans via the environment (oral)

Indirect exposure to humans, for example through the uptake of drinking water, is not relevant for
NaOH. Any potential for exposure to NaOH due to environmental releases will only be relevant at the
local scale. And any pH effect of local releases will be neutralised in the receiving water at the regional
scale. Therefore indirect exposure of humans via the environment (oral) is not relevant in the case of
NaOH (EU RAR, 2007).

Environmental exposure

Consumer uses relates to already diluted products which will further be neutralized quickly in the
sewer, well before reaching a WWTP or surface water.

Regional exposure concentrations

Any effects that might occur would be expected to take place on a local scale and therefore it was
decided as not meaningful to include the regional or continental scale in this risk assessment (EU
RAR, 2007). Predicted environmental concentrations (PECs) can not be calculated. Only a summary
of measured levels is provided (EU RAR, 2007).

The emissions of NaOH during production and use mainly apply to the aquatic environment. For
sodium, other anthropogenic sources are for instance mining and the use of road salt (sodium
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 45 / 46

chloride). In water (including pore water of sediment and soil), NaOH dissociates into the sodium ion
(Na+) and hydroxyl ion (OH-), both having a wide natural occurrence.

Freshwater (surface waters)

The concentration of hydroxyl ions (OH-) in the environment has been determined very extensively via
pH measurements. Geochemical, hydrological and/or biological processes mainly determine the pH of
an aquatic ecosystem. The pH is an important parameter of aquatic ecosystems and it is a standard
parameter of water quality monitoring programs. The most important freshwater aquatic ecosystems of
the world revealed average annual pH values between 6.5 and 8.3 but lower and higher values have
been measured in other aquatic ecosystems. In aquatic ecosystems with dissolved organic acids a pH
of less than 4.0 has been measured, while in waters with a high chlorophyll content the bicarbonate
assimilation can result in pH values of higher than 9.0 at midday (OECD, 2002, from UNEP 1995).

Also sodium (Na+) has been measured extensively in freshwater aquatic ecosystems. For example,
the 10th-percentile, mean and 90th-percentile concentrations for a total number of 75 rivers in North-
America, South-America, Asia, Africa, Europe and Oceania were 1.5, 28 and 68 mg/l, respectively
(OECD, 2002, from UNEP, 1995).

For European freshwaters, there are extensive databases on physico-chemical properties, including
pH, hardness (calculated from the measured calcium and magnesium concentration), alkalinity
(determined by acid/base titration or calculated from the calcium concentration, see further Section
3.1.3.2) and sodium concentration. In the framework of the EU Risk Asessment Report on Zn Metal
(The Netherlands, 2004), data on physico-chemical properties of freshwaters in individual European
countries and the combined data for freshwaters in European countries were collected and reported by
De Schampelaere et al. (2003) and Heijerick et al. (2003). The combined European data for the above
physico-chemical properties, all relevant for pH changes, are summarised in Table 17. The data in this
table are based on 1991-1996 data for 411 European locations, extracted from the ‘GEMS/Water
database’ (Global Environmental Monitoring System) that is mainly aimed on the large river systems.
A correlation analysis on the data from all 411 locations indicate that all parameters listed in Table 17
are positively correlated, i.e. an increased pH is associated with increased concentrations of Ca, Mg
and Na and increased hardness and alkalinity (De Schampelaere et al., 2003; Heijerick et al., 2003).

The variation in the above physico-chemical properties of the large river systems in different European
countries is rather small, with exception of some areas in the Nordic countries (Denmark, Sweden,
Norway and Finland) which are characterised by ‘soft water’ conditions, i.e. a hardness <24 mg
CaCO3/l and low pH. For example, in Sweden the 50th percentile value for hardness is 15 mg
CaCO3/l, which is 10-times lower than that for whole Europe. In Sweden the 50th percentile value for
pH is just below 7, which is about 1 pH unit lower than that for whole Europe (De Schampelaere et al.,
2003; Heijerick et al., 2003; The Netherlands, 2004).

Data on pH (and for some sites data on alkalinity) in surface waters, receiving effluent of NaOH
producers, are given in Table 17. In all but 3 of the receiving waters for which pH values are available,
the pH values are within the range of 6.5-8.5. These waters include freshwater (rivers) and seawater;
each of these waters have a more narrow range of pH values, usually within one pH unit (most waters:
pH range of 7.0 to 8.0). Thus, in most receiving waters the pH values are in the range that is expected
in most EU waters (see Table 17). In one river the pH ranged from 6.5-9.0 and in two waters there was
an even wider range of pH values, viz. 4.2-9.2 in a lake and 4.5-10.0 in another, unspecified water
type. There is no data on sodium concentrations in the receiving waters at the NaOH production sites
(a question on the sodium content was not included in the questionnaire).
TKI Hrastnik, d.d. Material Safety Data Sheet: SODIUM HYDROXIDE Page: 46 / 46

Table 17 Physico-chemical properties of European freshwaters (De Schampelaere et al., 2003; Heijerick
et al., 2003) (From EU RAR, 2007)

Seawater
In over 97% of the seawater in the world, the salinity (the amount of dissolved inorganic constituents),
is 35% (promille, in g/kg), but can be lower1. The major constituents of seawater at 35 0/00 are Cl-
(19.35 g/kg), Na+ (10.77 g/kg), SO42- (2.71 g/kg), Mg2+ (1.29 g/kg), Ca2+ (0.41 g/kg), K+ (0.40 g/kg) and
HCO3- (0.142 g/kg, being the carbonate alkalinity expressed as though it were all HCO3-, as this is the
dominant species in seawater; the concentrations of CO 2 and CO32- in seawater are very low
compared to that of HCO3-) (Stumm et al., 1981).

The pH of seawater (ocean water) is normally 8.0-8.3, which is very similar to the 80th to 95th
percentile values in European freshwaters (8.0-8.2, Table 17). The total range of pH values reported
for seawater is 7.5-9.5 (Caldeira et al., 1999) and data from several sources on the internet). The
sodium (Na) concentration in seawater (10,770 mg/kg, equivalent to 10,450 mg/l) is 115-times higher
than the 95th percentile value in European freshwaters (90 mg/l). The bicarbonate (HCO 3-)
concentration in seawater (142 mg/kg, equivalent to 137 mg/l) is between the mean HCO 3-
concentration (106 mg/l) and the 90th percentile HCO3- concentration (195 mg/l) in European
freshwaters, indicating a relatively high buffer capacity in seawater. The total hardness of seawater
(6,100 mg/l, as CaCO3, calculated from the Ca and Mg concentration) is 17-times higher than the 95th
percentile value in EU freshwaters, due to the much higher Ca and especially Mg concentration in
seawater compared to freshwater.

1Commonly use classification of watertypes based on salinity: seawater: salinity >20 o/oo, brackish water: salinity
5-20 o/oo, freshwater: salinity < 5 o/oo