Document N2vDbz64rr5273MJwy2e4JVww
CHEMICAL SAFETY REPORT
PROVIDED AS COMMENT TO THE PUBLIC CONSULTATION ON THE REACH RESTRICTION PROPOSAL ON PER- AND POLYFLUOROALKYL
SUBSTANCES (PFAS)
Public
Submitted by: Maschinenfabrik Kaspar Walter GmbH & Co. KG
Date:
15 September 2023
Substance:
and
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CHEMICAL SAFETY REPORT
Table of Contents
Table of Tables ....................................................................................................2 Table of Figures ...................................................................................................3 Abbreviations ......................................................................................................4
1 Scope of this report .....................................................................................5 2 Product characteristics..................................................................................6 3 Lifecycle stages ...........................................................................................7
3.1 Use of wetting agent in chromium plating ..................................................7 3.1.1 Tonnage overview and substance concentration..................................8 3.1.2 Workplace exposure .......................................................................9 3.1.3 Exhaust air emissions ................................................................... 11 3.1.4 Wastewater emissions .................................................................. 12 3.1.5 Degradation studies...................................................................... 12 3.1.6 Carry over .................................................................................. 14
3.2 End of life ........................................................................................... 15 3.2.1 Incineration................................................................................. 15 3.2.2 Landfilling ................................................................................... 15 3.2.3 Recycling .................................................................................... 15
3.3 Summary ............................................................................................ 15 4 Safety Data Sheet...................................................................................... 17
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Table of Tables
Table 1: Substance identity
6
Table 2: Physicochemical properties of the mixture
6
Table 3: Tonnage of products containing
sold in the EEA
8
Table 4. Potential emission of the full market.
to air for K.Walter's current market share and for 12
Table 5: Proportion of CrO3, Cr(VI) and scrubber wash water
measured in the electrolyte and in the 12
Table 6: Degradation Studies - Measurements of PFAS present in four different conditions 14
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Table of Figures
Figure 1: K.Walter electroplating unit SlimLine .........................................................8
Figure 2: Computer rendered example of the automatic loading and plating process, following six consecutive steps............................................................................. 10
Figure 3: Reservoir of the plating unit where the chromium electrolyte and the wetting agent are contained ........................................................................................... 11
Figure 4: Material flow analysis of PFAS (
) in the hard Chrome plating process . 16
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Abbreviations
AoA CSR DU EU
Analysis of Alternatives Chemical Safety Report Downstream user European Union
LEV PFAS PFBA PFBS PFHxA PFHxS PFOA PFOS PFPeA PFNA PFPeA PFPeS PFHpA PFDeA PFHpS PFOSA
REACH
SEA WWTP
Local exhaust ventilation Per- and polyfluoroalkyl substances Perfluorobutanoic acid Perfluorobutanesulfonic acid Perfluorohexanoic acid Perfluorohexanesulfonic acid Perfluorooctanoic acid Perfluorooctanesulfonic acid Perfluoropentanoic acid Perfluorononanoate, perfluorononanoic acid Perfluoropentanoate, perfluoropentanoic acid Perfluoropentane sulfonate, perfluoropentane sulfonic acid Perfluoroheptanoate, perfluoroheptanoic acid Perfluorodecanoic acid Perfluoroheptane sulfonate, perfluoroheptane sulfonic acid Perfluorooctane sulfonamide Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 18 December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) Socio-Economic Analysis Wastewater Treatment Plant
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1 SCOPE OF THIS REPORT
Maschinenfabrik Kaspar Walter GmbH & Co. KG ("K.Walter") is a manufacturer of plating equipment for gravure and embossing cylinders manufacturing and supplies customerspecific complete plating equipment (plating lines) for different segments: printing for packaging, printing for decorative, printing for publication and embossing. The core part of such plating systems is the device for the application of a chromium trioxide-based functional chrome coating on the printing cylinders further called `electroplating unit'.
K. Walter manufactures and sells the galvanic machines/systems where the chrome plating
of cylinders takes place, but the company itself does not perform functional chrome plating
of cylinders as a commercial activity. Additionally, they supply their downstream users
(DUs) with adequate wetting agents required to minimize any potential worker's exposure
to Cr(VI) and environmental releases during the electroplating process. The most effective
wetting agents used, contain PFAS (i.e.,
). K.Walter aims to
phase out the use of PFAS containing wetting agents among their DUs in association with
the substitution of Cr(VI). As PFAS-free alternatives currently available in the market are
not considered adequate, an earlier substitution (i.e., before substitution of Cr(VI)) is not
technically or economically feasible.
This Chemical Safety Report ("CSR") is part of K.Walter's derogation submission from the PFAS1 Annex XV REACH2 Report ("PFAS REACH Restriction Proposal"). The derogation submission also consists of an Analysis of Alternatives ("AoA")/Socio-economic analysis ("SEA") provided separately.
This document will provide information on:
i. The identity of the substance within the wetting agent & its degradation products ii. A description of the application as part of the hard chrome plating process iii. Details on the conditions of use and disposal iv. Details on the emissions during the use and end of life stages
With this information submitted as comment to the public consultation on the PFAS
restriction proposal, K.Walter aims for the reconsideration of derogation v. [hard chrome
plating until 6.5 years after EiF]. According to the substitution plan described in the
AfA, the phase out of CrO3 and
at K. Walter's DUs is expected to be completed
end of 2032. For K. Walter's
use, this translates to a required derogation timeline
of 7.5 years (calculated from the expected EiF in mid-2025). However, since ECHA's
restriction proposal only foresees 5(+1.5) year and 12(+1.5) year derogation options, K.
Walter needs to request the 12-year derogation to cover the required time for substitution.
1 Per- and polyfluoroalkyl substances 2 Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 18 December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals
5
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2 PRODUCT CHARACTERISTICS
The wetting agent sold by K.Walter is supplied by a contracted formulator and contains
The identity of both PFAS substances is described in Table 1. Additionally, physicochemical properties of the mixture are shown in Table 2. Table 1: Substance identity
Chemical name EC number CAS number Other names
Molecular formula Structural formula 3
Table 2: Physicochemical properties of the mixture
Property Physical state Color pH Boiling point Density Flammability Melting point Water solubility
Description of key information Liquid Light yellow Acidic 100 C 1.002 g/cm3 Non-combustible 0C Fully miscible
Source Safety data sheet (cf. section 4)
Moreover, it is important to point out that the concentration of the
in the wetting
agent is at least 50 times smaller as compared to the
. For this reason, in the
following sections, information will only be provided for the
.
3 Source: Toronto Research Chemicals <https://www.trc-canada.com/product-detail/?B516300>; <https://www.trccanada.com/product-detail/?T007805>
6
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3 LIFECYCLE STAGES
The life cycle stages where potential emissions of
may be generated are the use
stage and the end-of-life stage. Both stages along with the potential emissions will be
briefly described in section 3.1 and summarized in section 3.2.
K.Walter has 60% of the market share for rotogravure in the EEA. The sections below will describe the potential PFAS emissions of the downstream users (DU) covered under K.Walter and will be extrapolated to cover the whole market (100 %).
3.1 Use of wetting agent in chromium plating
K.Walter provides electroplating units (see Figure 1) for the functional chrome plating of cylinders applied for rotogravure printing or embossing.
Rotogravure printing is a printing technique based on the transfer of fluid ink from engravings on a printing cylinder to the surface of a substrate, or the material to be printed. Rotogravure is used primarily for long printing runs in applications such as foils, packaging, catalogues, inserts, flyers, gift-wrap, and labels, among many others, achieving fine and clear images. Embossing is a process by which a relief is created on a substrate, usually paper, by means of a gravure cylinder. This technique is used for giving a 3D texture to the embossed surface for both decorative and functional purposes. Examples for this are chocolate packaging where printed sections are raised to match prints or drawings on the package or specific surface pattern that provides anti slip properties to the surface.
Even though these processes and their end products are different, the process of Cr(VI) plating of the cylinders is the same:
The production of gravure and embossing cylinders starts with the degreasing of steel or Copper cylinders, followed by copper plating and finishing. The printing pattern is then embedded into the copper coating through either engraving or laser imaging. Regardless of the method applied, the cylinders are then degreased and finally plated with chromium in a 20-minute step carried out in the closed electroplating unit. Following a finishing step, the cylinders are ready for printing. For embossing cylinders chromium could also applied directly on steel.
HelioChrome Wetting Agent FF (FF = foam-free) is added to the chrome electrolyte within the electroplating unit to lower the surface tension of the bath, reducing the formation of aerosol during electrolysis. If the product is applied in the correct concentrations, a reduction of the surface tension form over 70 mN/m to less than 30 mN/m can be achieved. Low surface tension ensures small gas bubbles, less aerosol and a minimum of airborne hexavalent Chromium.
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Figure 1: K.Walter electroplating unit SlimLine
3.1.1 Tonnage overview and substance concentration
K.Walter offers three products containing different concentrations of
:
HelioChrome Wetting Agent FF, HelioChrome Rapid EC and HelioChrome Rapid ER.
The main product, HelioChrome Wetting Agent FF, contains
at a concentration
of <3% (w/w)4. This product is added as an additive to the other two products, which are
ready-to-use formulations of chromic acid for the automatic dosing of the plating units. In
Table 3 the average annual tonnage (2020-2022) of
within products sold in the
EEA is shown. As this value corresponds to K.Walter's 60% market share, an estimation
of the tonnage for the full market is provided.
Table 3: Tonnage of products containing
sold in the EEA
Concentration of (%)
in products
HelioChromeWetting Agent FF HelioChrome Rapid EC HelioChrome Rapid ER
<3% w/w <0.1% w/w <0.1% w/w
Total tonnage of pure products sold (kg/a)
in
in the EEA by K.Walter (60%)
78 kg/year
in the EEA for the full market (100%)
130 kg/year
The recommended concentration of
within the plating bath electrolyte solution is
is the commonly used constituent for PFAS based wetting agents offered
for the application in chromium trioxide based functional metal plating.
4 The concentration of
in the wetting agent is at least 50 times smaller than the concentration of
.
8
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3.1.2 Workplace exposure
The chrome plating process in a K.Walter electroplating unit is designed for automatic and
unstaffed chrome plating of rotogravure cylinders. The design of the units is such that no
contact with CrO3 solution is possible during loading/unloading takes place. The CrO3
solution is situated in an enclosed basin below the main tank and is only pumped up to
the main tank when the plating process is started, and the unit is closed. After the plating
process is finished, the solution flows back into the basin and the cylinder is rinsed with
water before the unit is opened again for unloading. The rinsing water is collected in the
lower basin of the electroplating unit together with the CrO3 solution. The evaporation of
liquid during the electroplating process (temperatures between 60-70C) is compensated
by the additional volume from the rinsing step. Thereby, the solution in the basin does not
overflow and the level remains relatively constant. Therefore, any potential for exposure
towards CrO3 or
contained in the electrolyte solution is low.
Additionally, the loading and unloading of the electroplating unit is performed via an automated or manual crane, which minimizes the exposure potential. The crane is controlled either fully automatically according to a pre-defined program or manually via a remote control. In Figure 2, the plating process is depicted exemplarily.
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Figure 2: Computer rendered example of the automatic loading and plating process, following six consecutive steps
(1) the cylinder is picked up (2) and transported to the electroplating unit (3). The cylinder crane lowers the cylinder (4) and the electroplating unit opens. The cylinder is automatically clamped (5). Before the plating process begins, the opening of the electroplating unit is closed (6).
The wetting agent is normally dosed indirectly via the ready-to-use products HelioChrome
Rapid EC or HelioChrome ER in the ideal concentration (
), which means
that the wetting agent is consumed comparable to chromium trioxide and other additives.
This mixture is dosed by small pumps controlled automatically by the plating unit.
Additional wetting agent (i.e., provided as HelioChrome Wetting Agent FF) is only added
to the plating unit after analyzing the surface tension of the baths and is dosed manually
by the operator if it exceeds 40 mN/m. This can be necessary as
degrades over
time and the ideal concentration must be renewed to achieve optimal performance.
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CHEMICAL SAFETY REPORT With the use of a measuring cup, the operator adds the wetting agent into the reservoir of the plating unit, containing the chromium electrolyte. The frequency of the dosing varies from monthly to yearly.
Figure 3: Reservoir of the plating unit where the chromium electrolyte and the wetting agent are contained
3.1.3 Exhaust air emissions
The electroplating units are equipped with fixed capturing hoods. Exhaust air is passed through wet scrubbers according to best available techniques. The installation of a wet scrubber is assumed as standard industry practice to reduce emissions. The water from the wet scrubber is redirected into the process cycle during standard operation. No air emission measurements for PFAS were available, however an estimation of the emissions is provided below. To reflect an estimation of the emissions of PFAS to the air, the release rate of 0.083%, calculated for CrVI for the purpose of authorization was used5. For the purpose of this assessment, it is assumed that the behavior of PFAS is similar to CrVI and that the scrubber's efficiency is the same.
5 https://echa.europa.eu/applications-for-authorisation-previous-consultations/-/substancerev/62905/del/200/col/synonymDynamicField_1512/type/asc/pre/2/view (last accessed on 14.09.2023)
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Based on the yearly tonnage of 78 kg of
in products sold, a value of 0.065 kg of
is released per year via air emissions. This value represents K.Walter's market
share of 60%.
Moreover, considering that K.Walter is not the only supplier of PFAS-containing wetting
agents, the value estimated should be extrapolated to cover the full market (~130 kg of
). The potential amount of
considering the estimated tonnage for the full
market is 0.108 kg/year (See the overview in Table 4). Considering that ~ 205 plating
units are currently operated, the average emission of one plating unit is up to 0.52 g/a.
Table 4. Potential emission of and for the full market.
K.Walter (60%) Full market (100%)
to air for K.Walter's current market share
emissions (kg/year) 0.065 kg/year 0.108 kg/year
Please note again that the estimation of
air emissions is based on the scrubber
efficiency derived for CrO3/Cr(VI) reduction. Even though this value may not reflect the
exact conditions, the proportion of Cr(VI) and PFAS observed in the wash water of the
scrubber are in a comparable order of magnitude (3 % of Cr(VI) versus 17 % of PFAS; cf.
Table 5). It cannot be determined whether the difference is caused by the different
physico-chemical properties or a difference in scrubber efficiency. In our opinion,
additional measurements are required to determine the extent of potential PFAS
emissions. K.Walter is supportive of such regulatory measures, if proposed, as the
necessity for a more targeted regulation is emphasized. Based on measured data,
additional abatement technologies to minimize potential emissions may be installed.
Table 5: Proportion of CrO3, Cr(VI) and in the scrubber wash water
measured in the electrolyte and
Concentration in electrolyte (Max)
Concentration in wash water
CrO3
CrVI 1)
PFAS 2) (
)
1) Values obtained by multiplying the CrO3 concentration by 0.52.
2) Degradation products are not included.
Proportion ending up in wash water
3% 3% 17%
3.1.4 Wastewater emissions
During the chrome plating of cylinders, no wastewater is produced. Any liquids remain within the system as closed loop. When the chromium solution needs to be replaced (e.g., due to the accumulation of impurities), it is pumped into an IBC and disposed of as hazardous waste via external service providers.
3.1.5 Degradation studies
In May 2023, studies were carried out by K.Walter to investigate potential degradation
products of
within the electrolyte. These studies were also performed to
understand the need to re-apply the wetting agent to the baths.
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Based on the measurements, we assume that the degradation of PFAS to short-chain molecules and finally to the individual substances is the main reason for the loss of
in our plating units.
Fourteen (14) different PFAS were considered in this study: PFOS, PFOA, PFNA, PFHxS,
PFBA, PFBS, PFPeS, PFPeA, PFHxA, PFHpA, PFDeA, PFHpS, PFOSA,
. PFAS
mentioned before were measure in different conditions:
o In a chrome plating unit without additional wetting agent (unused, ready-to-use electrolyte)
o In a chrome plating unit with 5ml/L of wetting agent6 (unused, ready-to-use electrolyte + additional wetting agent)
o In 2 chrome plating units with wetting agent, running for many years at a DU site (in equilibrium).
The results showed that through operation of the plating units,
degrades into
shorter-chain perfluorocarboxylic acids, mainly PFOS, PFOA, PFHxS, PFBS, PFPeS, PFHxA
and PFHpA, with PFBS being the predominant degradation product. Results are shown in
Table 6. As
is the main active substance for the modification of the required
surface tension of the electrolyte its degradation must be compensated by regular re-
dosing as described under section 3.1.2. Considering the substance diversity of PFAS,
further decomposition products may be formed. The detectability of these substances in
the electrolyte matrix with very high metal concentrations is only given for the few PFAS
substances mentioned.
6 5 ml/L of wetting agent leads to the lowest surface tension
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Table 6: Degradation Studies - Measurements of PFAS present in four different conditions
Cr(VI) bath without
additional wetting agent
(g/L)
Cr(VI) bath with 5 mL/L of
wetting agent
(g/L)
Bath 1 (g/L)
Bath 2 (g/L)
PFOS
0
0
162
13.6
PFOA
0
0
0
14.1
PFNA
0
0
0
0
PFHxS
0
0
9.28
2.16
PFBA
0
0
0
0
PFBS
0
0
13,500
2,550
PFPeA
0
0
0
0
PFPeS
0
0
22.7
4.85
PFHxA
0
0
0.762
0.535
PFHpA
0
0
1.22
0.799
PFDeA
0
0
0
0
PFHpS
0
0
0
0
PFOSA
0
0
0
0
3.1.6 Carry over
In the subsequent process of chrome plating, a small amount of PFAS is dragged out into the polishing machine. The concentration of PFAS in polishing water is 1.4 ppb. This water then enters the evaporator system or wastewater treatment, which treats the rinsing water for the entire system. The concentrate containing PFAS is collected and then incinerated. The purified water then has a concentration of only 0.03 ppb PFAS. The closed loop design of the coating systems ensures very low emissions to subsequent process steps.
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3.2 End of life
The waste generated in the end-of-life phase through the disposal of the PFAS containing electrolyte is expected to be produced after around 12 years of use. ~100% of the PFAS containing electrolyte is considered to be disposed as hazardous waste and assumed to be incinerated.
3.2.1 Incineration
As outlined above, the electrolyte solution containing
respectively its degradation
products is considered to be disposed of as hazardous waste via incineration. K.Walter
estimates that the electrolyte needs to be exchanged once every twelve years. The volume
of one electroplating unit ranges between
L with a target concentration of
of
. This amounts to
kg of PFAS waste once the electrolyte
needs to be exchanged.
A total of 205 plating units are operated by 102 DUs within EEA. In the last 3 years the electrolyte of 25 plating units was exchanged. This means that the electrolyte of around 8.3 plating units is exchanged per year, resulting in an annual PFAS waste tonnage of 1.16 kg and is assumed to be disposed of as hazardous waste, which is incinerated.
As stated in the restriction proposal7 (Section 1.1.5.5), the efficiency of incineration depends on numerous conditions and a complete destruction (100%) of PFAS is not expected. However, please note that the values above represent a worst-case scenario. While it is acknowledged that a small proportion of PFAS may be emitted from incineration, it would not be adequate to assume that the total waste fraction is released to the environment.
3.2.2 Landfilling
No PFAS containing waste from the use-phase is expected to end up in landfills, as all waste is considered to be incinerated.
3.2.3 Recycling
No PFAS containing waste from the use-phase is expected to go into recycling processes. Although it would be technically possible to recover PFAS it is too much effort to separate it from the other substances contained in the electrolyte solution to be economically feasible.
3.3 Summary
An overview of the material flow of PFAS (
) in the different stages of the plating
process is shown in Figure 4. As mentioned in the sections above, the PFAS-containing
wetting agent used by the rotogravure market in the EEA contains around ~130 kg of
. During the use phase of the wetting agent and based on the full tonnage, a
7 https://echa.europa.eu/documents/10162/f605d4b5-7c17-7414-8823-b49b9fd43aea (last accessed 14.09.2023)
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potential amount of 0.108 kg/year of
are estimated to be released via air
emissions from the plating process. This means that for each plating unit, a potential
emission of 0.52 g/year of
may be expected. Regarding the end-of-life phase, the
electrolyte containing the wetting agent has a useful life of around 12 years. This accounts
for an estimated amount of 1.16 kg of
which are disposed of via incineration every
year.
Figure 4: Material flow analysis of PFAS ( process
) in the hard Chrome plating
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4 SAFETY DATA SHEET
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3
K.WALTER
P_ATING AND 'ROCESSES
'ersion number: GHS 1.0
Safety Data Sheet
according to Regulation (EC) No. 1907/2006 (REACH), amended by 2020/878/EL
HelioChrome Wetting Agent FF
Date of compilation: 2022-09-2(
ECTION 1: Identification of the substance/mixture and of the company/undertaking
1.1 Product identifier
Trade name Registration number (REACH)
HelioChrome Wetting Agent FF not relevant (mixture)
1.2 Relevant identified uses of the substance or mixture and uses advised against
Relevant identified uses
Metal surface treatment product Industrial use
1.3 Details of the supplier of the safety data sheet
Maschinenfabrik Kaspar Walter GmbH & Co. KG Konrad-Zuse-Bogen 18 82152 Krailling Germany
Telephone: (+49) 089-78596-0 Telefax: (+49) 089-78596-111 e-mail: sales@kwalter.de Website: www.kwalter.de
e-mail (competent person)
1.4 Emergency telephone number
Emergency information service WF Gendorf . Telephone. +49 (0) 8679 7 - 2222. Telefax.
sales@kwalter.de
(0)89-19240 (24h 17d ( de I en)
. This number is only for transport emergencies.
ECTION 2: Hazards identification
2.1 Classification of the substance or mixture Classification according to Regulation (EC) No 1272/2008 (CLP)
This mixture does not meet the criteria for classification in accordance with Regulation No 1272/2008/EC.
2.2 Label elements Labelling according to Regulation (EC) No 1272/2008 (CLP)
not required
2.3 Other hazards
of no significance
ECTION 3: Composition/information on ingredients
3.1 Substances
Not relevant (mixture)
3.2 Mixtures Description of the mixture This product does not meet the criteria for classification in any hazard class according to GHS.
EU: en
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