Chemical Safety Report

CHEMICAL SAFETY REPORT

16. Mar.2016

Substance Name: Sodium dichromate EC Number: 234-190-3 CAS Number: 10588-01-9, 7789-12-0

Applicants's Identity: Ilario Ormezzano SAI SpA

Note 1: This document is the chemical safety report for the substance sodium dichromate. This CSR has largely been generated automatically from the technical dossier by using the CSR plugin for IUCLID. The plugin has automatically generated headings for several (sub-)chapters, for which there is no content. This can have several reasons. The respective data can be not available and/or not applicable for scientific reasons and/or not formally required for this substance/dossier. For editorial reasons, the empty sections are not always maintained and an individual reason is not given.

Note 2: This CSR is a part of a documentation of Application for Authorisation and contains two (2) site specific Exposure Scenario and related risk characterisation for 11 industrial dyeing sites and one chemical terminal site, all located in Biella area in Piemonte, Italy. EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

Part B 9. EXPOSURE ASSESSMENT (and related risk characterisation) 9.0 Introduction

This exposure assessment will be part of an application for authorisation and therefore the assessment is focused mainly on the Annex XIV properties ((Carcinogenic (category 1B) and Mutagenic (category 1B))). However, the assessment of environmental exposure and subsequent assessment of man via the environment has also been carried out to elucidate exposure levels of the general population. The substance, sodium dichromate (CAS 10588-01-9, EINECS 234-190-3) is manufactured outside the EU. The imported sodium dichromate is repackaged by the chemical supplier Ilario Ormezzano SAI Spa (IO Spa) in Biella and used in the textile industry in the Piemonte area in northern Italy. Sodium dichromate is subsequently only used by workers, working in the industrial settings in the textile dyeing industry. A certain fraction of the applied amount of chromium added to the process in the form sodium dichromate leaves the dyeing sites with the products in the Cr (III) oxidation state as a chemically bound complex of wool,Cr (III) and dye. Chromium (VI) does not enter the final products in detectable quantities.

9.0.1 Overview of uses and Exposure Scenarios

Tonnage information: Consumed tonnage of sodium dichromate dihydrate solution is currently at ca. 75-80 t/a level at the sites (range 65-130 t/year between the years). The physical state of the imported substance is water solution. The 61% solution is made outside the EU from solid dichromate dihydrate (CAS 7789-12-0) (298 g/mol). The imported water solution contains 61 % anhydrous sodium dichromate (262 g/mol) by weight (percentage calculated for the anhydrous salt)). Anhydrous sodium dichromate contains 39.7 % wt. active chromium (VI) and consequently the 61% water solution 24.2 % active chromium (VI) by weight (242 g/kg).

In the labels of the containers the information of sodium dichromate content is often given as: “45-46 % CrO3“ instead of a direct reference to the dichromate salt. The following table lists the site specific contributing environmental exposure scenario (ECS) and worker exposure scenarios (WCS) and tonnage assessed together with the PROC/ERC cathegorisation. The annual use tonnage varies between the years. The fixed 80 t/a consumption volume of 61% solution for dyeing used here in the exposure assessment represents rather well the use figures for the years 2014-2015, but depending on years the use volume can be higher or lower. The annual tonnages in Use 1 and Use 2 are different because Ilario Ormezzano, as a distributor, has larger storage capacity than the volume of Sodium dichromate they sell to their customers in a year. The amount they sell to their client varies yearly.

Table 1. Overview of exposure scenarios and contributing scenarios Identifiers ES Titles of exposure scenarios and the related contributing scenarios Tonnage *) identifiers (tonnes per year) Use 1 ES1 Repackaging of Sodium dichromate to be supplied as a mordant in the dyeing of wool as sliver and/or yarn with dark colours in industrial settings F1 ECS1 Storage, re-packaging and transportation of 61% sodium dichromate (ERC 130 2)

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 2 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

Identifiers ES Titles of exposure scenarios and the related contributing scenarios Tonnage *) identifiers (tonnes per year) F1 WCS1 Unloading and re-packing of 61% sodium dichromate (PROC 8b, 9, 28) 130 Use 2 ES2 Use of Sodium dichromate as a mordant in the dyeing of wool as sliver and/or yarn with dark colours in industrial settings IW1 ECS1 Use of dichromate in textile dyeing industry (ERC5) 80 (of 61 % soln.) IW1 WCS1 Use of chromium (VI) as a mordant in dyeing process (PROC3, PROC5, 80 (of 61 PROC13) % soln.) IW1 WCS2 Maintenance and management of dichromate at the dyeing plants (PROC 80 (of 61 8a, 28) % soln.) *) Manufacture: M-#, Formulation: F-#, Industrial end use at site: IW-#, Professional end use: PW-#, Consumer end use: C-#, Service life (by workers in industrial site): SL-IW-#, Service life (by professional workers): SL-PW-#, Service life (by consumers): SL-C-#.)

The “brief general description of the identified use(s)” i.e. the use description PROC/ERC codes applied here follow the most recent and updated CSR guidance R.12 ver 3.0 (ECHA, Dec. 2015).

9.0.2 Introduction to the assessment

9.0.2.1 Environment

Scope and type of assessment: The site specific exposure scenarios generated are intended to be part of an application for authorisation. Sodi- um dichromate is a carcinogenic substance and consequently the main focus is to assess and demonstrate the safe use of the substance in relation carcinogenicity within humans, the Annex XIV property of the substance. Therefore, detailed assessment and quantification of ecotoxicological risks has limited application. The im- portance of the environmental assessment lies with the predicted (or measured) environmental concentrations of chromium in different environmental compartments on a localised scale, since these PECs might have influence on the exposure of the general populations to Cr (VI) via the environment. The assessment for the environment has been performed quantitatively for the compartments most relevant for man exposed indirectly through the environment. Release of chromium (VI), from any source, is expected to be reduced to chromium (III) under normal environmental conditions, resulting in the impacts of chromium (VI) being limited to the area around the source of release. However, the possible wider background emissions of chromium from other similar sites (dyeing) are considered in a regional assessment. All the sites under this evaluation are located relatively close to each other in a same geographic area (inside a 200 km x 200 km region). The environmental concentrations of Cr estimated in this assessment are local and regional ones (Clocal & Cre- gional) and the assessment is based on the added risk which these may present. The added risk approach means that only the anthropogenic local released amount of the Cr (VI) substance from known sources is relevant for the effects assessment and the background concentrations (natural and/or historic pollution) are ignored. Modelling It is preferential in the environmental exposure assessment to use measured data instead of modelled data, though certain data gaps, e.g. concentrations of chromium in relation to indirect human exposure via the environment, can be reasonably filled by modelling. The predicted environmental concentrations of chromium in different environmental compartments and in foodstuffs at local and regional scale have been modelled using EUSES 2.1 model. Basic substance specific parameters used in the modelling are presented in Annex 1. OECD Emission Scenario Documents (ESDs) describe the sources, production processes, pathways and use patterns. ESDs aim to quantify the emissions of a chemical into water, air, soil and/or solid waste. There are two ESDs available which can be used as supportive sources of information in the estimation of emissions from the

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 3 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9 chemical supply chain of Sodium dichromate in industrial use as a mordant in dyeing of wool. These documents are: Transport and Storage of Chemicals (2009) (ENV/JM/MONO(2009)26) and Emission Scenario Document (ESD) on the Use of Textile Dyes (ENV/JM/MONO(2015)50).

Risk characterisation The risk characterisation for the environment is not required in this application for authorisation and if it is made qualitatively or quantitatively, it is primarily made for illustrative purposes and supporting information for the analysis of alternatives part of the AfA. Risk characterisation may show that general release level and also the environmental risks regarding releases of chromium to the local environment are under control at the assessed sites. The scope of exposure assessment and type of risk characterisation for the environment is described in the following table based on the hazard conclusions. The Predicted No Effect Concentration (PNEC) values are adopt- ed from the EU risk assessment of chromates (ECB 2005).

Table 2. Type of risk characterisation for the environment Protection target Type of risk characterisation Hazard conclusion (PNECs) Freshwater Quantitative assessment not required Cr (VI) 3.4 μg/l (ECB 2005) Cr (III) 4.7 μg/l (ECB 2005) Sediment (freshwater) Quantitative assessment not required Cr (VI) 0.15 mg/kg (wet weight) (ECB 2005) Cr (III) 31 mg/kg (wet weight) (ECB 2005)

Sewage treatment plant Quantitative assessment not required Cr (VI) PNECSTP = 0.21 mg/l (ECB 2005) Air Quantitative assessment not required No hazard data available Agricultural soil Quantitative assessment not required PNEC for Cr (VI) in soil has not been determined. All chromium in soil is considered to be in the form of chromium (III). Predator Quantitative assessment not required 17 mg Cr (VI)/kg food

Comments on assessment approach: The initial environmental assessment applies ERC2 release category for storage, re-packaging and transportation and ERC 5 release category for the actual use in dyeing. However, measured data on environmental exposure, in terms of released volumes and/or environmental concentrations, have been used as far as possible. This means that concentrations of Cr in the environment (PECs) has been measured/estimated for the compartments/medium based on true release data or based on known OC/RMM conditions at the sites. Site specific information proved that the initial ERC 5 emission fractions to estimate emissions to the environment results in an unrealistic worst-case assessment for sodium dichromate. Based on all available detailed information, there are only very limited releases of Cr (VI) to the environment. Intrinsic properties of aqueous dichromate solutions, in combination with the way the solutions are stored and used in dyeing limits the releases to local air effectively to a very low level. For all of the sites, programs for monitoring environmental release to the aquatic environment are in place to control releases of chromates. Transformation reactions of Cr (VI/III) in the environment Chromium (III) species dominate in nature, with high levels of chromium (VI) species generally only found as a result of man-made pollution. Although chromium (VI) is thermodynamically stable under oxidising conditions, the kinetics of reduction to chromium (III) under certain conditions can be slow. The environmental fate processes, mainly the oxidation-reduction reactions of Cr (VI) need to be known to evaluate certain environmental and indirect human risks of Cr (VI). This has already been evaluated in relation to the risk assessment in the EU

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 4 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9 risk assessment report on chromates (ECB 2005). For risk assessment purposes, after literature review, it was assumed that for acidic (or neutral, where high concentrations of reductants for chromium (VI) exist) soils, sediments and waters, chromium (VI) will be rapidly reduced to chromium (III). Under less favourable conditions, e.g. alkaline conditions (~pH >8) and/or neutral conditions, where low concentrations of reductants for chromium (VI) exist, it will be assumed that the rate of reduction of chromium (VI) to chromium (III) is slow, with a long half-life of around 1 year. Such conditions are found in seawater, where a pH of around 8 is typical. Adsorption-desorption behaviour Overall, chromium (VI) anions can be considered to be mobile in sediments in the environment, except possibly under highly acidic conditions. Chromium (III) appears to be much more strongly adsorbed to soils and sediments than chromium (VI). At pH >5 chromium (III) is known to precipitate out of solution as the insoluble hydroxide, often in conjunction with iron. The adsorption of chromium (III) onto soil follows the pattern typical of cationic metals, it increases with increasing pH and organic matter content of the soil, while decreasing when other competing (metal) cations are present. The following partition coefficients (in m3/m3 form) derived in ECB (2005) for chromium (VI) under acidic conditions is used in this assessment: Ksusp-water = 500 m3/m3, Ksed-water = 500 m3/m3, Ksoil-water = 75 m3/m3. Bioaccumulation of Cr (VI) The available data indicates that the bioconcentration factor for chromium (VI) in fish is low at around 1 l/kg. Once in the organism, reduction of chromium (VI) to chromium (III) appears to occur, resulting in an accumula- tion of total chromium in the organisms by a factor of approximately 100 times the original concentration in water. Uptake of chromium (III) directly from water is likely to be very low due to the limited water solubility and strong adsorption to sediment under most conditions found in the environment. High BCFs of up to around 9,100 l/kg (dry weight basis) for chromium (VI) and 2,800 l/kg (dry weight basis) for chromium (III) have been determined in mussels with BCFs of around 500 l/kg (on a cell dry weight basis) for chromium (VI) and 12,000-130,000 l/kg (on a cell dry weight basis) for chromium (III) having been determined in algae. It is possible that once taken up by the organism, chromium (VI) is reduced to chromium (III) in the tissues, resulting in a build up of chromium (III) and hence would overestimate the true bioconcentration factor for chromium (VI). Transfer of chromium via the alga ⇒ bivalve, and sediment ⇒ bivalve food chains appears to be relatively low (ECB 2005). Fate and existence of Cr in air Inorganic chromium (VI) compounds have very low volatility at ambient and moderately elevated (< 200 °C) processing temperature. If released to air Cr (VI) is normally found in the atmosphere associated with aerosols or particle matter. In the atmosphere, chromium (VI) can be reduced to chromium (III) if suitable reductants are present however, it is likely that in most situations, chromium (VI) will be relatively stable under the conditions present in the atmosphere. The chromium present on particle matter and in aerosols can be transported to land surfaces via wet and dry deposition.

9.0.2.2 Man via environment

Scope and type of assessment:

The scope of exposure assessment and type of risk characterisation required for man via the environment are described in the following table based on the reported hazard conclusions. Table 3. Type of risk characterisation required for man via the environment Route of exposure and type of Type of risk characterisation Hazard conclusion effects Inhalation: Systemic Long Term Quantitative (cancer) 29 x 10-3 per µg Cr (VI)/m3 Oral: Systemic Long Term Quantitative (cancer) 8 x 10-4 per µg Cr (VI)/kg bw/day

Comments on assessment approach:

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 5 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

The focus in this exposure assessment for the general population is carcinogenicity risk caused by indirect exposure to Cr (VI) via the environment. Typically indirect exposure of Cr (VI) to humans via the environment may occur via air, the drinking water, inhalation and/or ingestion of contaminated dust in the air or through longer routes from food (fish, crops, meat and milk). This assessment aims to estimate the human daily intake levels and makes use of appropriate local and regional environmental concentrations, as appropriate. The concentrations have been calculated by using the Euses model as already described in the previous chapters (9.0.2.1). In the case of chromium (VI), the man via environment assessment has limited focus, since chromium (VI) is reduced to more stable (III) oxidation state once it is released to the environment. The reduction may take place relatively quickly in most fresh water aquatic environments, even if a detailed transformation rate is always dependent on local conditions. In addition the bioaccumulation potential of chromium is low. Therefore, the relevancy of exposure assessment to the general population via food is not regarded as being significant. Mod- elled concentrations in foodstuff give some indication of Cr levels for risk characterisation purposes. Exposure via drinking water and air may be relevant and the assessment relies primarily on measured Cr (tot) and secondarily on modelled Cr (VI) concentrations. Chromium (VI) has a harmonised classification for CMR properties. Cancer and mutagenicity endpoints have been studied relatively well and non-threshold mode of action has been recognised for carcinogenicity. The dataset/information on reproductive toxicity is more limited and it is not completely clear what is the mode of action of Cr (VI) in reproductive toxicity. However, it is assumed in the risk characterisation that carcinogenicity is the most sensitive endpoint of the three CMR properties. Therefore, the other risks are assumed to be under control if risk levels for carcinogenicity are at levels of low concern. Cancer risk- dose response for general population For the risk characterisation a preliminary reference dose response relationship for carcinogenicity, has been given for general population and workers by ECHA/RAC. Lung cancer risk: For the general population the inhalative linear dose response relation of excess lifetime lung cancer mortality risk estimate is 29 x 10-3 per µg Cr (VI)/m3. This estimate is based on an exposure for 70 years, 24h/day, every day. Intestinal cancer risk: For the general population an linear excess lifetime intestinal cancer risk = 8 x 10-4 per µg Cr (VI)/kg bw/day has been given. The estimate is based on an exposure for 70 years (24h/day, every day) and an 89-year life expectancy. To estimate intestinal exposure from intake of inhalable, but non-respirable particles, the exposure to Cr (VI) can be converted into oral doses by applying the standard human resting breathing rate of 0.8 m3/hr and the standard average human body weight default value of 60 kg.

9.0.2.3 Workers

Scope and type of assessment: The scope of exposure assessment and type of risk characterisation required for workers are described in the following table based on the hazard conclusions presented.

Table 4. Type of risk characterisation required for workers Route Type of effect Type of risk Hazard conclusion characterisation Systemic Long Term Quantitative (cancer) 1μg/m3 (Cr (VI)) results in 4 x 10-3 excess lung cancer lifetime risk, linear extrapolation to higher or lower concentrations Inhalation Systemic Acute Qualitative Acute Tox. 2 *) Local Long Term Qualitative Resp. Sens. 1 *) Local Acute Qualitative Corrosivity, Resp. Sens. 1) *

Dermal Systemic Long Term Qualitative *)

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 6 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

Route Type of effect Type of risk Hazard conclusion characterisation Systemic Acute Qualitative *) Local Long Term Qualitative *) Local Acute Qualitative corrosivity, Skin Corr. 1B *)

Eye Local Qualitative corrosivity *)

*) For most of the dermal and inhalation route endpoints qualitative assessment applies. The relevant critical effects are local and systemic effects, i.e. corrosivity, irritation and carcinogenicity. Sodium dichromate has the harmonized classification Ox. Sol. 2 Carc. 1B Muta. 1B Repr. 1B Acute Tox. 2 * Acute Tox. 3 * Acute Tox. 4 * STOT RE 1 Skin Corr. 1B Resp. Sens. 1 Skin Sens. 1 Aquatic Acute 1 Aquatic Chronic 1 (ref: CLP ATP 3). Lung cancer is the most sensitive effects in humans and also the main driver in setting OC/RMM and the low limits of exposure. Therefore, the operational conditions, engineering controls and personal protective equipment will minimize inhalation/dermal exposure and be sufficient to protect from all other acute and/or systemic effects.

Comments on assessment approach related to toxicological hazard: The focus in the worker exposure assessment is to clarify the occupational exposure in relation to the carcinogenicity properties of Cr (VI) at the eleven industrial sites. The number of potentially most exposed workers involved in the dyeing process and process control is between 5 to 25 per a site. The sites run in 2-3 shifts (7.5-8 hr/shift).

Table 5. Average number of workers at the dyeing sites Site Workers in dyeing hall Total number of Type of the company (operators included) employees at the company

D1 12 400 Manufacturer/Dyer

D2 25 400 Manufacturer/Dyer

D3 9 320 Manufacturer/Dyer

D4 12 22 Dyer

D5 5 8 Dyer

D6 10 28 Dyer

D7 10 37 Dyer

D8 10 95 Dyer

D9 10 24 Dyer

D10 10 28 Dyer

D11 12 156 Dyer

Total 125

A quantitative assessment was carried out for long term systemic hazards via inhalation and skin. On-site measured exposure information is used as far as possible. Risk assessments for the inhalation route should, as a default, use the fraction of inhalable, but not respirable, particles (E(I)-E(R)). The risk arising from exposure to

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 7 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9 this fraction will be assessed assuming exposure via the gastro-intestinal tract and thus using the risk estimates for that exposure route (ECHA 2012). In the case of these eleven dyeing companies, where the all measured Cr (VI) concentrations are low and there are no handling of dry dichromate salts at any of the sites, since the substance is always delivered and handled in water solutions.

The hazard level for qualitative assessment is assigned based on the classification of the substance. The assign- ment rules are described in section E.3.4.4 of part E of the Guidance on Information Requirement and Chemical Safety Assessment. The hazard level determines the risk management strategy to be described in the exposure scenarios. Sensitiser for skin and respiratory organs are properties that require sufficient skin and respiratory protection whenever there is possibility of direct contact with Cr (VI). Reproductive toxicity and mutagenicity are known and classified properties of sodium dichromate. The NOAEL levels for fertility and development toxicity of Cr (VI) compounds has been observed at relatively high levels (at mg/kg/d level). Current exposure concentrations in the exposure scenarios are at low μg/kg bw/day level, which means that risks of the toxicity to fertility and reproduction are expected to be adequately controlled in the current uses if the exposure is at that low level and the risk characterisation for repro effects are not made quantitatively. Cr (VI) compounds have the potential to induce both somatic and germ cell mutations. The consequences of mutagenicity can be severe, however, based on the results of the epidemiological studies of workers exposed by inhalation to Cr (VI) compounds and on results of long-term oral carcinogenicity studies in animals, it is known that mutagenicity of Cr (VI) compounds is mostly linked with oncogenic transformation of epithelial cells in lungs and in the intestine leading to lung or intestinal cancer. Taking that into account, the focus of the assessment on the risks related to the carcinogenicity, which also includes risks related to the mutagenicity. Cancer risk - dose response for workers A reference dose response relationship for carcinogenicity of hexavalent chromium substances has been provided by ECHA/RAC. The reference dose response relationships proposed by ECHA are only based on carcinogenicity arising from the Cr (VI) ion. Inhalation route: For workers a linear dose response relation of excess lifetime lung cancer risk has been given: 1μg/m3 (Cr (VI)) results in 4 x 10-3 excess lung cancer lifetime risk. This relationship is an excess lifetime (up to age 89) lung cancer risk estimates for workers exposed at different 8h-Time Weighted Average concentrations of Cr (VI) for 40 years. Intestinal cancer risk estimates for workers has also been given by RAC. An excess lifetime intestinal cancer risk = 3.3 x 10-4 per µg Cr (VI)/kg bw/day, based on a 40 year working life (8h/day, 5 days/week), the following risk estimates are used: Exposure to inhalable, non-respirable particles is first converted into oral doses by applying the standard worker breathing rate of 1.25 m3/hour, 8h per day, and the standard worker body weight default value of 70 kg. It is assumed that there is 100% retention of particles that are inhaled (the gastro-intestinal absorption is not 100% and is reflected in the oral risk estimates).

Worker exposure: Measured data

In general, chromium is not known to generate gases (at NTP) and intrinsic volatilization behavior of dissolved chromic acid/dichromate anion from the aqueous process solutions is expected to be zero or extremely low. Neither the operational conditions in tightly closed dyeing baths raise concerns regarding chromium in the air.

Chromium in workplace air measurement results are available for most of the sites (static and personal sampling). In addition, there are also biomonitoring results available (chromium in urine determinations). Results for these measurements are given in connection of worker contributing scenario(s) and in the Annex 4 of this CSR.

Exposure modeling In addition to measured data, modeling tools are used to estimate worker exposure. Exposure assessment tool for metals and inorganic substances MEASE (1.0.2.01) (EBRC Consulting GmbH 2010) and Targetted risk Assessment TRA v. 3.10 (ECETOC 2014) and Advanced Reach Tool (ART 1.5, http://www.advancedreachtool.com) exposure assessment tools are used following recommendations of CSA

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 8 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

R.14 guidance for metals and inorganic substances.

Comments on assessment approach related to physicochemical hazard:

Sodium dichromate is a hazardous chemical and physical chemical hazard properties meet the criteria to be classified it as “oxidative solids” (Ox. Sol. 2 ). Concentrated water solutions have the same classification as the solid.

The reactivity of diluted chromates under controlled conditions in textile industry dyeing process use does not pose any specific physicochemical hazards that should be considered separately in the exposure scenario. How- ever, it is important that dichromate solutions are not let to dry. The oxidative hazard is not relevant for the reduced Cr (III) reaction product.

General information on risk management related to toxicological hazard:

For substances categorised as having a high hazard profile (i.e. category 1A and 1B carcinogens) a very high level of containment, appropriate PPE together with automatic dosing/feeding to the process are recommended in occupational settings in order to avoid exposure. Therefore, in this ES the use of protective and relevant PPEs are always seen as a default in tasks where the substance is handled manually or where the potential for exposure is high. The contact is not possible with the concentrated solution, e.g. during transferring solution from containers to others. The pattern of use for this substance is non-dispersive, only certain groups of trained workers are handling the material (transfer and couple containers to dedicated equipment). Transfer of sodium dichromate water mixtures i.e. charging at the chemical terminal (ES1) and coupling, discharging, decoupling of containers at dyeing companies (ES2) takes always place at dedicated facilities applying engineering controls which are specifically designed for that purpose. Therefore the contact level would be none or accidental only. For most workers the use is always non-direct and with a contact level of diluted process solutions at most would be incidental or none. Properly designed gloves and safety goggles should be used to minimize the dermal exposure as the substance is sensitising and may be corrosive (depending on conditions). Respiratory Protection Equipments (RPE) are normally used by the operators transferring and coupling/uncoupling the sodium dichromate containers.

General information on risk management related to physicochemical hazard:

The dichromate solution containers are stored in original packages (in 600-1000 kg IBC containers or 25-50 kg plastic containers) in locked reagent store shelter in most cases outsides, but also insides. No other chemicals are normally stored in close vicinity of the chromate solutions, but this does not completely hold true in all of the dyeing sites.

Health hazards may be involved in use/storage of sodium dichromate with incompatible substances. The substance is classified for oxidising properties. Chromium may undergo vigorous redox reactions from its +VI oxidation state to the +III oxidation state. Vigorous oxidative reactions may take place if the substance is mixed with incompatible materials. The maximum amount of sodium dichromate stored at the chemical supplier site is 30 t and at the downstream user sites from 0.3 t to 4.8 t at a time.

An Internal Emergency Plan is available for the chemical supplier site (latest updates; Rapporto di sicurezza (19.Dec 2014), Event Tree Analysis (19.Dec 2014)) in compliance with legislation on chemical accidents (e.g. the Seveso directive and Italian law n°105/2015 – according to the Directive 2012/18/UE) for critical situations in which sodium dichromate may be involved in (leaks, spillages, fire, explosion, etc) and supplied to the authorities to enable them to draw up external emergency plans. Every downstream textile dyeing site puts in place a “Specific emergency plan” which includes identification of the most likely emergency situations. Considering the closed circuit use of the product, every site is prepared in advance to the following emergency situation: • Spills/releases during unloading from vehicle and positioning of dichromate containers • Spills/releases during transfer from containers to storage tank • Spills/releases in automatic chemical dosing system

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 9 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

Specific operational instructions and safety procedures are available, including the reduction method of Cr VI to trivalent chromium Cr (III).

9.0.2.4 Consumers

Scope and type of assessment: The substance is entirely used in industrial installations under strictly controlled conditions. There is no consumer exposure, since Cr (VI) is reduced to Cr (III) in the process. The amount of non-bound Cr (III) in wool is also at low level (< 3 mg/kg wool) and Cr (VI) does not end up in the final products (yarn, fabric) and consequently not to consumer market in detectable amounts (< 0.5 mg/kg wool). The concentration of chromium Cr (VI) bound to products is monitored by sector specific method (ISO 105-E04). Consequently, there is no need to take consumer exposure assessment into consideration.

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 10 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

9.1 Exposure scenario 1: Repackaging of Sodium Dichromate as a mordant in the dyeing of wool as sliver and/or yarn with dark colours in an industrial setting Description of the activities and technical processes covered in the exposure scenario: Market sector: PC34: Textile dyes, and impregnating products Sector of use: SU10: Formulation Article categories: Environment contributing scenario(s): ECS1: Handling and storage of large volumes of sodium dichromate 61% solution, ERC 2 (Formulation) Worker contributing scenario(s): WCS1: Unloading and repackaging of concentrated sodium dichromate solution PROC 8b (Transfer of substance or mixture), PROC 28 (Maintenance and cleaning) Subsequent service life exposure scenario(s): 0 Exposure scenario(s) of the uses leading to the inclusion of the substance into the article(s): 0

Explanation on the approach taken for the ES: Transportation of 61 % sodium dichromate solution takes place from Genova harbor terminal to Ilario Ormez- zano SAI Spa, in Biella by trucks as ADR transportation in ISO tanks 25 000 kg at a time about five (5) times per year. The whole process of unloading the tanks of the truck to on-site storage tanks (1 worker involved + truck driver) takes about 120-180 minutes. Before the emptying operation starts a 0.2 liter sample is taken from the product from the top opening of the truck’s ISO tank (this is regarded as the most dangerous process done by terminal workers, from dichromate’s point of view). The sample is checked immediately for density and aspect at the on-site laboratory. After passing the quality check the ISO tank is connected to on-site connectors and the product is pumped to the two storage tanks (15 m3 fixed roof stainless steel tanks outsides). The total time needed for the emptying operation is 60-120 minutes at a time. There are in total seven (7) trained operators permitted for the truck unloading task and anyone of them may act as a responsible operator for the emptying process.

Table 6. Number of workers at the site Site Overall number of Overall number of Overall number of Total number of workers handling workers handling workers handling employees dichromate, truck dichromate at the chemicals at the drivers included terminal terminal

Chemical suppli- 11 7 18 53 er

Repackaging

The repackaging is performed by seven trained IO Spa workers and the sodium dichromate solution (61%) is supplied to downstream users in sealed containers ranging in size from 25 Kg – 2 tonnes. The purpose of this repackaging is to supply sodium dichromate in manageable quantities to the downstream users. Repackaging is carried out about 80 times/year by one worker at a time and the task takes about 15-90 minutes.

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 11 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

Delivery Trasportation of filled IBC containers to customer sites, in total four truck drivers are involved. Loading of 61% solution into customers consumption/storage or exchange empty ICB container(s) to full one(s) (task time 15-90 min). A short description of tasks at the terminal site and expected exposure potential to dichromate is given in table below.

Table 7. Short description of tasks and expected worker exposure potential Task Short description of tasks related to Na2Cr2O7 use Process Exposure category potential to Cr (VI)

Transportation: Sodium dichromate solution is transported by 1 PROC 1 No exposure ex- trucks in ISO tanks (ADR transportation) pected Unloading to on-site stainless steel tanks 2 PROC 8b Low to Medium Storage of substance: Sodium dichromate solution is stored in 3 PROC 1 No exposure ex- tanks outsides pected Repackaging to smaller Intermediate Bulk Containers (customer 4 PROC 8b Low - Medium- containers) High (WCS1) Transportation: Sodium dichromate solution is transported in IBC 5 PROC 1 Low containers in the terminal area and road transportation to customers by trucks

Unload of IBC container to customer tank or change empty IBCs 6 PROC 8b Low - Medium- to filled containers. High (WCS1) Maintenance and cleaning, Maintenance/servicing work of 7 PROC28 Medium – High equipment: checking and cleaning of IBC tanks and the emission (WCS1) control equipment

9.1.1 Environmental contributing scenario 1- Handling and storage of large volumes of sodium dichromate 61% solution

The sodium dichromate solution is unloaded, stored and repackaged at Ilario Ormezzano SAI Spa, chemical terminal site in Biella. Storage take place in two fixed roof steel tanks outsides, loaded about five (5) times per year about 25 t at a time. The two large storage tanks (15 m3) are situated on a containment basin. The basin has no connections to sewer. Any liquid in the basin needs to be pumped out, collected in appropriate containers and disposed off via a licensed company.

Waste water treatment The terminal site has an on-site WWTP entirely for their own use (batch type operation, capacity 90 m3). The system consists of a collection tank for the waste water, collected from three separate sewer lines. First the pH is neutralized and flocculant (aluminium chloride) is added. In the next phase, after two sedimentation tanks, the overflow waste water is passed filterpresses where the rest of precipitates are separated. Water is then collected to a second 25 m3 storage tank. From time to time, after lab. analysis of the content (not carried out for every batch), the tank is emptied through sewer system to an external STP. The final recipient for the waste water is the Cervo river.

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 12 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

Release control to air Potential emission sources to air are tank losses from displacement during filling and breathing during ambient temperature changes. Losses are depending on vapour pressure of the substances in the tank. So- dium dichromate is in ionized form in the solution and intrinsinc tendency to evaporate from water solutions is very low. Under equilibrium conditions water predominates in the gas phase and in practice only water evaporates. The situation changes somewhat if mechanical energy is brought to the solution (eg. strong mixing of the liquid). Abatement of non-ducted emissions is more difficult to handle. These may be for instace working losses and breathing losses of small IBC containers (when not captured and ducted) and losses during handling operations (e.g. filling of small containers); equipment leaks from pump and valve seals, connectors and other piping items. However, due to the properties of sodium dichromate, these diffuse emissions is expected not to air but enter rather to waste water and to on-site sewer/ WWTP system.

9.1.1.1 Conditions of use Product (article) characteristics . Sodium dichromate 61% solution in water . Low volatility oxidising liquid (mp. -40°C, bp. 117 °C, density 1.68 kg/dm3 (at 20°C) vp. 20 hPa (at 20°C)) . Stored and handled at ambient temperature Amount used, frequency and duration of use (or from service life) . 130 000 kg/a, delivered 5-6 times/year from import harbour . Delivered further to downstream users throughout the year on demand Technical and organisational conditions and measures . Unloading and storage substance in 2 x 15 000 liter fixed roof steel tanks at the on-site chemical terminal . Repackaging the solution to 25-1000 liter UN/ADR complient plastic intermediate bulk containers (IBCs) . Transfer by forklift truck to on-site storage area . Loading by forklift truck to road truck and transportation to downstream customers . Return the empty IBCe back to the chemical teminal . Technical condition checks of IBCs (if not accepted the defect containers are discharged after washing) Conditions and measures related to sewage treatment plant . Waste waters are treated in on-site abiotic batch type waste water treatment plant (capacity 90 m3) . Unit operations at the WWTP are: flocculation, sedimentation, filtration . After on site treatment the waste waters are led to external sewer system and further to external STP . Effluent max concentrations Cr (VI) < 0.02 mg/l, Cr tot < 4 mg/l. Conditions and measures related to treatment of waste (including article waste) . Contaminated chromate solutions are discharged to the on-site WWTP treatment . Defect containers are wasted Other conditions affecting environmental exposure . Emissions of chromates to air from handling and tank storage will be abated by a sodiumbisulfite filled reducing scrubber system before exhaust gases are emitted (Cr (VI) is absorbed and reduced to Cr (III)). . Rainwaters and spillages from the terminal pavement areas are drained to the on-site WWTP Additional good practice advice. Obligations according to Article 37(4) of REACH do not apply . Regularly recurring assessment of the conformity of the storage tank installation and its components according to stipulations made by the authorities. . Regularly check containers, piping, fittings, joint sealings, pumps as well as the safety devices (leak indicators, overfill prevention devices, containment areas) and precautionary technical measures (e.g. sealed surfaces in the unloading/refilling area). . Keep up-to-date the operating instructions and checking rules including service warnings, alarms and action plans as well as appropriate auxiliaries for incidents or accidents causing damage.

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 13 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

9.1.1.2 Releases

Releases to water: Maximum chromium concentration limits for waste water from the batch WWTP are set by the external WWTP operator. The allowed maximum chromium content for Cr (VI) < 0.02 mg/l and for Cr tot 4 mg/l. The IO Spa has been able to operate within these release limits. There are no detailed information available of the released amounts of chromium. A calculation can be made based on the assumption that one batch is released a day and the calculated maximum release of Crtot would be 36.5 kg/year and Cr (VI) 0.182 kg/year.

Releases to air Default emission factor to air for ERC2 (formulation) for sodium dichromate water solution is 0.003. In any conditions, gaseous releases from the tank, due to ambient temperature changes, are treated in the in-line connected scrubber. Tank vents are connected to a reductive wet scrubber (Specifications: reductive wet sodium bisulphite unit, flow capacity 2000 m3/h (0°C, 0.1MPa)), material: polyethylene, height of emssion point: 8.4 m, stack diameter: 12 cm.). The efficiency of wet scrubbers is normally > 99 % and true emissions from tank storage to air is believed to be extremely low/negligible. Scrubber outlet stack emission concentration of chromium has been measured < 0.1 µg/m3 demonstrated that the scrubber was operating properly. Measured concentration of Cr (tot) in air at the unloading platform is < 0.1 µg/m3 (static sampling).

Table 8. Local releases to the environment Release Release factor estimation Explanation / Justification method Water Initial release factor: 2% Site specific data Final release factor: 0.18% Local release rates: 0.1 kg/day Cr (tot) Explanation / Justification: Release calculated based on waste water flow rates and Cr (tot) permission limits in the effluents. Air Industry sector specific release Initial release factor: 0.3% (ERC 2 - No RMM) factors Final release factor: < 0.03 % (fugitive emissions) Local release rate: 0.016 kg/day Explanation / Justification: the final factor may still be an overestinmation, sodium dichromate is not volatile and all processes take place at ambient temperature. Soil Site specific data Final release factor: 0% Explanation / Justification: site specific information No direct releases to soil (asphalted/sewered area)

Releases to waste

Any chromium (VI) containing waste generated is disposed of according to local regulations and permissions and follows the guidelines laid down in the EU legislation on waste and pollution prevention. The amount of chromium (VI) containing waste in loading/unloading and storage operations is low at the site. At normal operation, there is no package waste generated, since all IBC containers are reusable. During repackagin/refilling dichromate containers, there is no need to wash the IBCs and small 50 l drums, since they all are used only for sodium dichromate. The small amount of product left inside is mixed with the new product. Therefore there is no waste generation or it is minimal in refilling IBCs. In the case there were some dilute washing waters generated, that can be treated in the on site WWTP (this release included in waste water emissions).

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 14 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

There is no maintenance of the IBC containers. In case of IBCs are damaged they are disposed off. The method of disposing follows the following steps: 1) Container is washed with sodium bisulphite solution, emptying, 2) Flushing with caustic soda solution, emptying, 3) Rinsing with water, emptying, 4) Disposed off by a licenced waste management company Solid waste: WWTP sludge: < 10 t to 40 t per year. The sludge is wasted by external authorized waste management company (waste code: CER 190 814). Protective gloves, RPE filters and comparable materials are collected in a specific dedicated waste container and from time to time disposed off through a licensed waste management company.

9.1.1.3 Exposure and risks for the environment and man via the environment

Transportation and storage of concentrated sodium dichromate solution is well under control. Releases to the environment are at a very low level. The chemical terminal site of the supplier is located in larger industrial area. There are no people permanently living in the area and the nearest apartments are located > 1 km distance from the terminal where sodium dichromate is handled at ambient temperature with dedicated equipment. Local environmental risks are not considered further under this scenario. All downstream user sites and the chemical terminal are located in the same region. The local and regional risks for the general population is estimated under the downstream use exposure scenario 2, (Chapter 9.2.0.3 and in Annex 3. Indirect human exposure via the environment).

9.1.2 Worker contributing scenario 1, Unloading and repackaging of concentrated sodium dichromate solution

9.1.2.1 Conditions of use Method Product (article) characteristics . Sodium dichromate 61% aqueous solution in ambient temperature Site-spec. Amount used (or contained in articles), frequency and duration of use/exposure . 130 t a year, weekly activities, unloading and repackaging outdoors, transfer of containers and Site-spec preparations for transportation Technical and organisational conditions and measures . Dedicated equipments in unloading trucks to terminal tanks Site-spec . Dedicated equipments in repackaging plastic IBC containers (1000 l) and small plastic containers (50 l). . In line exhaust ventilation and reductive scrubber in filling line

INSTRUCTION FOR Charge discharge vehicles under Normal Operating Conditions (outsides) . Step 1. The tank truck driver arrives at office logistics with all personal identification documents, the vehicle and the product. . Step 2. It is taken note of the correct documentation and correspondence with orders issued by purchasing department. . Step 3. If the step 2. has been passed, the documentation of the supplier is delivered to the driver and all the internal documentation relating the safety and conduct to be maintained at the plant. . The plant operator responsible for charge/discharge operations call the vehicle to Zone 21, with three copies of the transportation documents, one for the driver, one for laboratory and one for the operator. . Step 4. Checking the documents. If the documentation is not in line with the material ordered,

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 15 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

Method a decision is made to reject the delivery of the product. . Step 5. If step 3 & 4. are passed, the operator allows the vehicle to enter to the Zone 21, being careful not to cross the grids intended to collect any chemical leakage. Engine of the truck must be stopped and the vehicle secured by placing wedge blocks in front and behind the tyres. It is verified that the driver has all necessary PPEs. . Step 6. The operator takes a product sample (0.2 l) and delivers it to the laboratory, with two copies of the transport documents, for checking quality conformity and specifications of the product with the laboratory tests. . Step 7. If the previous stage is not passed properly, the operator must stop all other operations and call warehouse manager or the maintenance manager to perform all evaluations necessary in order to clarify the anomalies observed. Otherwise the product distribution is ceased. . Step 8. If the stage 6. is passed properly, the laboratory distributes approved and signed transport document to the operator. The operator returns to the Zone 21 and he must check the chemical level in the tank to make sure that there is sufficient space in the tank for the intended amount of chemical to load. . Operator closes the main valve into position “C” in the cockpit (next to the grid) to catch exhaust emissions and spills from the loading operation. . Step 9. After passing properly the stage 8: o the operator checks if the safety conditions established in stage 5 are still operational, o open the cap of the tank piping (next to the pump) o check the condition of hoses and connections o connect the chemical outlet hose to chemical pump connection o check carefully all the connections o start the scrubber to control exhaust gases escaping the tank during filling o position a movable safety basin under the truck tank connections o open the chemical pump inlet valve o slowly open the drain valve of the vehicle and ensure proper flow of liquid from the vehicle tank to the pump and from the pump to the storage tank monitoring particularly any leaks. Visually check all connections before proceeding to the next step. Any anomalities must be reported immediately to the plant manager or the chemical store manager. . Step 10. If the check list under the stage 9 has been passed properly, it is possible to start the vehicle pump to discharge vehicle tank to the on-site storage tank. . Step 11. If the check list under the stage 9 has NOT been passed properly, the responsible discharge operator must stop all operations in progress and have to call the chemical store manager or maintenance manager. . Step 12. After the chemical discharge has ended as intended, the responsible operator has to turn off the pump and close the connection valves: o disconnect the hose between storage tank and the vehicle tank o gives permission to vehicle driver to move the truck into parking of the logistics office to get acceptance to leave the site o the operator checks if there are any chemical leaks for cleaning and closes the main valve to “A” position in the underground well. Step 13. If the stages 12 or 13 do not positive result, the operator shall call supervisor, chemical store manager or maintenance manager as relevant. Conditions and measures related to personal protection, hygiene and health evaluation . Skin and body protection: Protective suit (washable or disposable overalls), safety boots, Site-spec chemical goggles or face shield, chemically resistant gloves (Nitrile rubber, chloroprene rubber, butyl rubber or other suitable gloves, complying with the requirements of EN 374 (break- through time: 480 min); Specific activity training in relation to use and maintenance of the gloves must be provided) [Effectiveness Dermal: 95%] . RPE (APF 20, Halfmask or full face mask with ABEK1 filter or higher) is needed in unloading IBC containers to consumption tanks of the customers if non-dedicated filling equipments are used. . RPE (APF20, Halfmask or full face mask with ABEK1 filter or higher) is always available for the workers. RPE is not needed in unloading/repackaging at the terminal site when dedicated filling line is applied.

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 16 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

Method Other conditions affecting workers exposure . Work under a high standard of personal hygiene. Wash hands and face before breaks. Site-spec . Training of employees on how to safely work with the substance, incl. how to use the necessary personal protection equipment. . If an operator comes in contact with the sodium dichromate he/she has to change clothes and take a shower as soon as possible (all sites have emergency showers near the area in which the drivers load/unload the IBC or the tanks of dichromate). . The employees who are allowed to handle sodium dichromate are authorized to handle the substance. Work instructions and risk analysis covering e.g. the operating instructions and action in case of spilling are available for the personnel. Additional good practice advice. Obligations according to Article 37(4) of REACH do not apply . Work under a high standard of personal hygiene. Wash hands and face before breaks. When Site-spec using the product, do not eat, drink or smoke.

9.1.2.2 Exposure and risks for workers

Measurements: Measurements of chromium (VI) in the working place air at the unloading/repackaging area are done every three years and biomonitoring once a year. In most recent studies the exposure has been measured by stationary (1 times) and portable collectors (2 times) and biomonitoring chromium in urine samples (17 times in the year 2015). The results for the static and personal sampler measurements from the year 2015 are below: 1. Cr (VI) < 0.1 µg/m3 (stationary, 47 mm PVC filter, porosity 5µm, 2000 l sample) (15. Oct 2015, 09.20 – 11.55 (155 min.)) 2. Cr (VI) < 0.4 µg/m3 (breathing zone portable/personal, 25 mm PVC filter, porosity 5µm, 451 ltr. sample) (time: 15.Oct. 2015, 09.05 – 12.45 (220 min)). Tasks: Filling IBCs 3. Cr (VI) <0.4 µg/m3 (breathing zone portable/personal, 25 mm PVC filter, porosity 5µm, 434 ltr. sample) (15. Oct. 2015, 09.15 – 11.50 (155 min)) Tasks: Taking chromate liquid samples & sample gravi- metric lab. analysis and other laboratory work. The location where the static sampling (1.) took place is in the chemical storage area where the chemical trucks unload their tanks and where IBC containers are refilled (picture 1 in Annex 5.).

During unloading and repackaging the following PPEs are in use. Protective full face shield, cloves and protective overalls are always in use. A RPE mask ABEK1 is available, but not always used by the worker carrying out these tasks outdoors. One worker at a time and in total seven (7) workers could be exposed through the breathed air in these unloading/loading tasks.

Biomonitoring results

Biomonitoring results (n=17) from the year 2015 is presented below for the chemical terminal site.

Table 9. Statistical results of Cr in urine levels for the terminal site 2015 Number of measurements (n=17) Maximum 90 th perc. Median Geom. 25th mean perc. Results in μmol/mol creatinine 1.70 1.00 0.28 0.24 0.14 3 Exp. converted to μg/m (Cr(VI) in air) 2.1 1.25 0.34 0.30 0.18

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 17 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

More detailed data on the biomonitoring studies and other workplace measurements are presented in Annex 4.

Modelling exposure Charging/discharging of sodium-dichromate solution has been assigned the PROC 8b category, which means: Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities. The description of 8b and the on-site conditions are expected to match well with each other. Exposure concentrations and modelled values together with estimation of excess lifetime cancer risk is presented in table below. The cancer risk is estimated by TWA Cr (VI) exposure concentration 1 μg/m3 increases lung cancer risk in EU workers by a factor 4 x10-3 based on a 40 year working life (8h/day, 5 days/week).

Table 10. Exposure concentrations and risks for worker Route of exposure and type of Exposure concentration Risk characterisation, effects excess lung cancer risk Inhalation, systemic, long-term, < 0.1 µg/m3 (TWA8, stationary sampling) < 4 * 10-4 measured Inhalation, systemic, long-term, <0.4 µg/m3 (TWA8, personal measured) < 1.6 * 10-3 measured Inhalation, systemic, long-term, < 1 µg/m3 (TWA8, 60-240 min task, RPE APF10) < 4 *10-3 modelled (MEASE) unload- (4 µg/m3 (TWA8, 60-240 min task, no RPE) ing/repackaging PROC8b Dermal, systemic, long-term, Dermal load, 0.009 mg/day, RPE in use nd. (MEASE) unload/repack PROC8b Eye, local Combined routes, systemic, 1.25 µg/m3 (TWA8, measured, 90 th percentile, 5*10-3 (excess lung can- long-term, biomonitoring results converted to concentration in air) cer risk)

Remarks on exposure data:

There are some exposure measurements available from the chemical supplier site. These results show low exposure to Cr (VI) in the breathed air.

Biomonitoring results may be seen representative for combined route of exposure (oral, inhal, skin). Same conclusions, low exposure through combined routes can be drawn from the biomonitoring results from the year 2015. Overall the biomonitoring results are at low level and the highest converted value responds no more than 2.1 μg/m3 (Cr (VI) in air) exposure level and the 90th percentile 1.25 µg/m3. The measured concentrations in the working place air seem to be in line with the modelled results. The dedicated equipments outdoors for unloading/loading operations, LEV attached to the filling line fittings and purifica- tion of gases (online reductive wash unit), together with the use of appropriate PPE to limit exposure is at a high level at the site. The measured exposure levels of Cr (VI) in the breathing zone and in the vicinity of the dichromate tank during unloading/loading of containers are low. Conclusion on risk characterisation: Based on the information available risk to workers for this contributing worker scenario can be considered to be controlled to a risk level of < 5*10-3 when applying the current risks management measures and PPEs outlined in this contributing worker exposure scenario.

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 18 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

9.2 Exposure scenario 2: Use of Sodium Dichromate as a mordant in the dyeing of wool as sliver and/or yarn with dark colours in industrial settings

Market sector: PC34: Textile dyes, and impregnating products Sector of use: SU5: Manufacture of textiles Article categories: Environment contributing scenario(s): ECS2: Use of dichromate as a mordant in textile dyeing industry ERC 5 Worker contributing scenario(s): WCS1: Use of chromium (VI) as a mordant in dyeing process, PROC 1, 3, 15, 19 WCS2: Maintenance and management of dichromate solution at the dyeing plants, PROC 8b, 9, 28 Subsequent service life exposure scenario(s): 0 Exposure scenario(s) of the uses leading to the inclusion of the substance into the article(s): 0

Operational conditions:

Wool dyeing in batch mode

The dyeing takes place in batch mode operation in completely closed dyeing baths normally made of stainless steel. It takes 4-5 hours per batch to complete. Filling of the dyeing bath (reactor vessel) with proper amount of wool (sliver or yarn) may take place manually, or with the aid of tackle or completely automatically. The volume of the smallest baths is about 30 liters and the largest ca. 7000 liters. One site may typically have 10-20 baths and the most typical size is about 1000-2000 liters. In general, the baths are sturdy made and most of them can be pressurized and are therefore subject to regular inspections.

Afterchrome process All the 11 dyeing sites apply the afterchrome process in which wool and the dye is applied first and the wool fibre is then chromed in a separate step. Sodium dichromate is used as a mordant in fixation of chrome dyes to the wool fibre. During the dyeing processes with chrome dyes, Cr VI is reduced to Cr III in properly controlled process. Simplified process stages after filling the bath and closing it:

1) Ordinary dyeing with acid dyes (ca. 80% of chromium dyes are of azo type) 2) “Chromating” phase (at 90°C ca. 10 – 30 min, 1-2% chromate by weight/wool weight) 3) Reduction phase with thiosulphate solution (ca. 30 min) 4) Sampling, colour compliance is checked (oper. manually or remotely, this step is not always necessary) 5) Washing/flushing processes, (eg. detergents and pH adjustment needed depending on the applied dye and fibres)

When applied to tops, the dyed material often undergoes further washing with ammonia and soap at a temperature between 30 and 75 °C in order to guarantee a deeper cleaning of the fibres. Adjustment of pH is made by

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 19 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9 remortely operated additions of formic or acetic acid and ammonia. The dyeing and chromating processes are carried out in closed baths whereas the exhausted dyeing baths are drained through pipes which ensure their transport to the company’s and /or cooperative depuration WWTP/STP system.

After steps (1-5) the reactor is opened and the dyed materials are moved to the next phase of the manufacturing process (drying, storage etc.). For opening and emptying the reactors, both manual and automatic mechanisms are in use.

Chromating phase

Dichromate use volume/mass wool is relatively small with a 1% - 2.5% chromate solution. Dichromate water solution (61%) contains 24.2% chromium and therefore 1%-2.5% of the solution is equal to 0.24%- 0.60% Cr demand per kg wool by weight (2400 - 6000 mg Cr per 1kg wool).) Chromium is added to the dye bath as sodium dichromate. In solution the chroming species present vary accord- 2- ing to pH, with the dichromate anion Cr2O7 predominating at pH between 3 and 7. Although it is the chromium (VI) anion is initially used, the dye complex is formed with chromium (III), formed by the action of reducing groups in the fibre itself is with Cr (III). Strong acids have an activating effect on this process, thiosulphate is used to enhance the degree of conversion of Cr (VI) to Cr (III).

Closed process

Even if the process works in “batch” mode taking 4-5 hours, the actual procedure in the batch reactor is contin- uous in nature, so that all process stages are automated, preprogrammable and remotely controlled. There is no need for any manual interventions after closure of the reactor until opening it after the process is complete. Sometimes sampling is needed before flushing/washing steps. The temperature range during the process ranges from 95 °C (dyeing) to ca. 40 °C (flushing). The dyeing process takes place in acidic solution (pH 3.5-5) and ammonia is used in pH adjustment during the washing stage.

Chemical dosing A closed circuit dosing system is equipped with a consumption tank, (into which the chemical supplier let the liquid chemical agent flow); The consumption tank is positioned in such a way so as to ensure conveyance of any accidental release to the depuration plant and to prevent its drying. The dosing systems are also equipped with precise volumetric weighing system and automatic distribution to the dyeing devices by means of a piping network. Workers normally never touch the sodium dichromate solution, so PPE are used only in case of emergency or in case of a fault in the automatic system. In the rare event that the quantity of sodium dichromate to be used is so small that the automatic dosing system cannot be employed (dyeing of minimum quantities or lab tests), all the operations shall be carried out with the aid of personal protection devices like nitril gloves, glasses, mask.

Time scales of chrome use at the dyeing sites The companies use chromium as a mordant for dark colours. Some of the sites produce these specific shades continuously 260 days/year, but others less than 50 days per year.

Handling of concentrated dichromate solution Handling of concentrated dichromate solutions is a short term activity (WCS2). The remotely controlled chrome use in dyeing baths only accounts for up to ca. 10-15 minutes per batch. Transferring and charging dichromate solution to the automated dosing system takes place few times per year only and in a highly controlled way to minimize worker and environmental exposure.

Waste

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 20 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

Any chromium containing waste generated is disposed of according to local regulations and permissions and follows the guidelines laid down in the EU legislation on waste and pollution prevention. The principle that generation of waste is prevented in accordance with EU waste legislation (Waste Framework Directive 2008/98/EC) is followed. Where waste is generated, hazardous waste is managed in accordance with the following waste hierarchy and applied in priority order (in line with the WFD): 1) Prevention 2) Preparing for re-use 3) Recycling or, where that is technically and economically impossible 4) Disposal. The amount of chromium (VI) containing waste collected during cleaning and maintenance or other operations is low at all of the sites. Non contaminated chromate liquids are circulated back to process use. Dilute chromate liquids can be treated at the on-site STP like normal process waters. More concentrated liquids can be pre- treated by reducing Cr (VI) to a less hazardous Cr (III) hydroxide precipitate. The residues are disposed of as hazardous waste.

Explanation on the approach taken for the ES:

A short description of tasks at the dyeing site and expected exposure potential to dichromate is given in table below.

Table 11. Short description of tasks and expected exposure potential Task Short description of tasks related to Na2Cr2O7 use Process Exposure category potential to Cr (VI)

Transportation and unloading: Sodium dichromate solution is 1 PROC 8b Low-Medium transported in IBC containers (25-1000 kg) and changed to empty WCS2 containers or unloaded in on-site consumption tanks Storage of substance: Dichromate solution is stored in plastic IBC 2 PROC 1 No exposure ex- containers in dedicated area inside or outside, or in separate pected chemical consumption tanks. Transfering containers and coupling sodium-dichromate solution 3 PROC9 Medium to high to the process line WCS2 Process operator remotely controll of dichromate feeding to closed 4 PROC1 Low - WCS1 process Loading dyeing machines (tops, cone, fabrics) manual or 5 PROC19 Low - WCS1 automated task

Weighing dyes (no chromates present) 6 PROC9 No exposure expected Dyeing process stage (dye in acidic solution, 90-95 °C) 7 PROC3 Low- WCS1 Chromating stage (initially added ca. 240-600 mg/l Cr (VI) at 1:10 8 PROC3 Low- WCS1 wool/water ratio by wt.)

Reducing stage (conversion of Cr (VI) to Cr (III) with 9 PROC3 Low- WCS1 thiosulphate)

Sampling (checking color shade) 10 PROC9 Medium - WCS1 Flushing/washing with water (automatic) 11 PROC3 Low- WCS1 Unloading dyeing machines (tops, cone, fabrics) manual or 12 PROC19 Medium (manual automated task task) - WCS1

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Low (automated tasks) - WCS1 Maintenance and cleaning, Maintenance/servicing work of 13 PROC28 Medium – High equipment: maintenance of tanks, and chemical feeding WCS2 equipment Cleaning of tanks, removal and disposal of aggregated precipitates 14 PROC 8a Low-Medium WCS2 Small scale laboratory testing of dyes 15 PROC 15 Low – WCS1

9.2.1 Environmental contributing scenario 2- Use of dichromate as a mordant in textile dyeing industry (ERC 5)

Releases to the environment and related RMM‘s Sodium dichromate solution (61 % wt.) is stored in its original package in the reagent store at the industrial area of each dyeing site. The substance is used in closed batch process (initially ERC 5 - Use at industrial site leading to inclusion into/onto article). Potential release of the substance from other sources than the process use itself is possible only during filling/changing of the automatic dosing containers or in the case of equipment breackage. Environmental releases of sodium dichromate solution resulting from the use in the dyeing process is minimal to the air and significant to the waste water. The main proportion of applied chromium is first reduced to Cr (III) form and washed and flushed at the end of the batch process. The aqueous process waste streams are collected in on-site biological waste water treatment plants. All sites follow environmental monitoring programs. The effluent from the STP is sampled and analysed for Cr(VI) and Crtot even daily at some of the sites. The effluents are discharged to rivers or further to external treatment in larger industrial Waste Water Treatment Plants.

9.2.1.1 Conditions of use Product (article) characteristics . Sodium dichromate solution 61 % at ambient temperature . Sodium dichromate dilute (0.2-1%) solution in closed wool dyeing baths at elevated temperature (85-95 °C) Amount used, frequency and duration of use (or from service life) . On-site storage from 100 kg to 5000 kg. . Amounts in actual use: 1-2.5 % of the wool material to be dyed (few kg per a batch) . From daily use to once per week . Duration: 10-15 min in a 3-5 hr process Technical and organisational conditions and measures . Storage in dedicated area in plastic IBC containers and/or in stainless steel consumption tanks . Feeding to process through pipelines steered by remotely operated atomated system . Closed process reactors . Reduction of Cr (VI) to Cr (III) inside the closed process by wool material and intentionally added reductants . Cr (III) is chemically bound to wool fibres and dyes and excess Cr (III/VI) is flushed to waste water Conditions and measures related to sewage treatment plant . Waste waters are distributed to on-site sewage treatment plants (STP) . STP processes include oxidative/reductive phases, average residence time 24 hr. . Release of Cr in STP effluents follow local permissions Conditions and measures related to treatment of waste (including article waste)

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. Any hazardous Cr (VI) waste generated is treated off site by authorised contractors . Secondary waste are treated off site as hazardous waste. Hazardous wastes from onsite risk management measures and solid or liquid wastes from use, cleaning and maintenance processes should be disposed of separately to authorised hazardous waste treatment plants or hazardous waste landfills. . Type of external treatment aiming at final disposal of the waste: The sludge is wasted under controlled conditions following local permissions and EU waste regulations. . Fraction of substance disposed of as secondary waste < 0.1% wt (estimate < 50 kg Cr per site). Other conditions affecting environmental exposure . Chromium VI is effectively transfornmed to Cr (III) by chemical transformation to solid chrome oxide/hydroxides (Cr (III). . The purpose in the dyeng process is to get Cr (VI) transformed effectively to Cr (III) which is benefical also in the view of decreasing of hazardous emissions . Due to intrinsic properties of the substance and processing conditions, emissions to air is extremely low/negligible Additional good practice advice. Obligations according to Article 37(4) of REACH do not apply . Training of the operators on how to safely work with the substance and optimize the process conditions to minimise releases

9.2.1.2 Releases

Together with existing site specific information on measured releases, there are also several information sources available on process specific release data and on environmental releases from the textile industry sector in general. One versatile information source is the Reference Document on Best Available Techniques for the Textiles Industry (BREF 2003). The document describes typical emissions generated in dyeing processes and more specifically also the chrome dyeing processes.

As a general note the BREF document summarises dyeing processes as follows (pg. 77). ”Most of the emissions are emissions to water. Due to the low vapour pressure of the substances in the dye bath, emissions to air are generally not significant and can be regarded more as problems related to the workplace atmosphere (fugitive emissions from dosing/dispensing chemicals and dyeing processes in “open” machines).”

OECD emission scenario document (OECD 2004) estimates the potential of emissions to air from dyeing processes in the following way: “Procedures like decanting, dispensing, dosing, measuring and weighing as well as pre-treatment and dyeing processes in „open“ machines (esp. when machines are loaded or unloaded) are of specific interest concerning fugitive emissions.” The existing information from the eleven sites under this evaluation supports the description given in the BREF and OECD documents. In batch dyeing washing and rinsing operations after dyeing and addition of dichromate cause discontinuous, low-concentration emission of applied chemicals (Cr included) to waste water at the end of each cycle. Emissions of trivalent chromium in the waste water can be minimised, but cannot be totally avoided. According to literature, an emission factor of 50 mg chromium per kg of wool treated is achieved, which corre- sponds to a chromium concentration of 5 mg/l in the spent chroming bath when a 1:10 liquor ratio is used (BREF 2003). Regarding emissions to air, all these sites apply completely closed dyeing machines and therefore there are not fugitive emissions from these air tightly closed reactors. Fugitive emissions from dichromate dosing and storage systems remains as the only relevant and rather theoretical source of chromium to process hall air and further via ventilation to the environment. Measurements from the workplace air supports a conclusion that emissions of Cr (VI) from the equipment to air is negligible from the environmental point of view. The Annex 2 of this CSR “Local releases of chromium to the environment” summarises measured data and estimates of Cr releases to the environment from the sites. For comparison and in parallel to the application of measured site specific data, environmental releases has been determined based on the consumed tonnage of chromates and the initial environmental release categories (ERC). For the environmental assessment industrial categories and use types are chosen to best suit the description of

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 23 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9 the industry sector and uses of sodium dichromate and emission defaults are those specified by the ECHA Guid- ance on information requirements and chemical safety assessment: Chapter R.16: Environmental Exposure Estimation. Parameters used in modelling exercises are presented in Annex 1.

Surface Water: Based on information from literature and site specific release data, emission factor for chromium use has been estimated in the wool afterchrome dyeing. The range of release factors to waste water of initially applied chromium is in the range < 1 % - 5% and typically in the range 2-4%. Details of the release data is in Annex 2.

Air: An estimate of chromium release to air from chromium use at the dyeing sites is based on TGD default emission scenario tables as follows. Usage: Industrial use in dyeing of wool, Industry category: 13 Textile processing industry, Use category: Colouring agent, Batch dyeing, metal complex, Emission tables: A1.3. (specific uses) B 1.6 General table. The emission factor to air is: 3* 10-4 (i.e. 0.03% of Cr use released to local air). This emission factor is used in indirect human exposure assessment for the sites for the general population. Soil: Normal operation of the two dyeing sites does not have any direct releases of chromium to soil or ground water. Rare exceptions could occur e.g. container leaks and accidents during on-site chemical transportation/unloading operations. The default TGD emission factor for release to industrial soil is: 1* 10 -4 which mean that 0.01 % of applied total amount of sodium dichromate solutions would be lost to local soil.

Table 12. Local releases to the environment Release Release factor estimation Explanation / Justification method Water Initial release factor: nd...% Site specific data Final release factor: 4 % Local release rates: <100-1000 g chromium/day Explanation / Justification: Release factor is calculated based on waste water flow rates and Cr (tot) release and use rates of the sites Air Industry sector specific release Initial release factor: 3* 10-4 factor (estimated loss of particu- Final release factor: 0.03 % late material to atmosphere) Local release rate: ca 10 g chromium/day Explanation / Justification: The final factor is default TGD emission factor for textile industry sector, emission calculated based on annual use of Cr (VI) per each site. Soil Site specific data Initial release factor: 0 % Final release factor: 0.01% Local release rate: Explanation / Justification: No known direct releases to soil or ground water from normal operation. The final factor is default TGD emission factor for the textile industry sector.

Releases to waste Process waste The dyeing process does, in practise, not generate Cr (VI) containing solid waste. Cr (VI) is consumed in the process and bound to fibres as Cr (III) and any excess chromium remains in the solution in reduced Cr (III) oxidation state. A small fraction of the initially applied amount of Cr enters to sludge of the waste water treatment plants. In practice chromium in sludge is already reduced to Cr (III), sludge which is sent to external waste treatment in accordance with local regulations. Except the sludge, it is difficult to estimate quantitatively the amount of chromium (VI) containing waste, but it hardly exceeds 30 kg per site a year.

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Secondary waste Secondary waste means here other than process waste. In general, the use of sodium dichromate in dyeing sites generates very low amounts of Cr (VI) containing packaging waste or other solid or liquid waste. The substance is used as a water solution and the containers are recycled back to the supplier for refilling. Residues of dichromate solution may still be in the containers, but this small amount returns back to the refilling site of the chemical supplier. Release factor to waste from the process: not determined Release factor to waste from on site treatment: not determined

9.2.1.3 Exposure and risks for the environment and man via the environment

The assessment is based on measured site specific data in combination with modelled exposure data. Justifica- tions for specific selections made in the assessment and approach taken in the iteration phase has been given in Annex 2. Local releases of chromium to the environment and Annex 3. Indirect human exposure via the environment.

Table 13. Modelled exposure concentrations and risks for general population Estimation target Exposure concentration Risk characterisation Excess cancer risk Man via Environment - Inha- lation Air local, modelled 2.0 *10-3 µg/m3 (100m from source) 5.8 * 10-4 (lung cancer) Air local, modelled 0.54 * 10-3 µg/m3 (500m from source) 1.5 * 10-5 (lung cancer) Air regional, modelled 1.16 * 10-8 ng/m3 3.3 * 10-13 (lung cancer) Man via Environment - Oral Estimated Daily dose local 8.6 *10-3 µg/kg/d local 6.9 * 10-6 (intestinal cancer) Estimated Daily dose, regional 9.5 *10 -5 µg/kg/d. 7.6 * 10-8 (intestinal cancer)

Lung cancer risk: For the general population inhalative linear dose response relation of excess lifetime lung cancer mortality risk estimate 29 x 10-3 per µg Cr (VI)/m3. This estimate is based on an exposure of 70 years, 24h/day, every day. Intestinal cancer risk: For the general population linear excess lifetime intestinal cancer risk = 8 x 10-4 per µg Cr (VI)/kg bw/day. The estimate is based on an exposure for 70 years (24h/day, every day) and an 89-year life expectancy. Further and more detailed information is given in Annex 3 on the calculated man via environment concentrations of Cr (VI) in food, drinking water and air and the contribution/fractions of these different sources in build- ing up the estimated daily dose.

In summary the estimated lung and intestinal cancer risks for the general population local are: Lung cancer risk via inhalation route (500 m from point source): 1.5 * 10-5 Intestinal cancer risk via oral route: 6.9 * 10-6

Remarks on man via the environment from local contribution

The estimated local concentrations in air have significant uncertainties, since emissions to air and concentrations in air has not been verified by measurements. Anyway, the estimated concentrations in air are low and it is also unclear what would be the actual ratio between the Cr (VI)/Cr (III) species if Crtotal would have been determined.

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Background chromium concentrations in air For comparison to the calculated on-site concentrations, general background levels of chromium can be given. Generally, worldwide chromium (total) concentrations in air are in the range of 10-50 ng/m3 in urban areas, with lower levels (annual means <10 ng/m3) found in rural areas. Most of the chromium in air is associated with the particle phase (Bencko, 1985) (Merian et al. 2004).

Conclusion on risk characterisation: It can be concluded that risk levels for human health are at levels of low concern at < 1 * 10 -5 level at the local and at < 1 * 10-7 level at the regional level.

9.2.2 Worker contributing scenario 1, Use of chromium (VI) as a mordant in dyeing process (PROC 1, 3, 15,19)

2- 2- This contributing worker scenario covers the actual use of dichromate (Cr2O7 - ions and/or CrO4 - ions) in dyeing textiles. The operational conditions and the applied risk management measures are described in the next chapters.

9.2.2.1 Conditions of use

Method Product (article) characteristics . Concentrated (61%) sodium dichromate is used within a closed chemical dosing system Site- . Dilute sodium dichromate solution (200-600 mg/l Cr) is used in batch reactor in acidic solution spec (pH 3.5-5.0) at elevated temperature (85-95 °C) (wool/water ratio 1:10 – 1:15 by weight or higher) . Reduction of Cr (VI) to Cr (III) in closed process applying thiosulphate solution Amount used (or contained in articles), frequency and duration of use/exposure . About 80 t of concentrated (61%) dichromate solution is used regionally per year (20 t Cr (VI) Site- representing the years 2014-2015) (the range of use has been 65-130 t/a) spec . About 1000-30 000 kg concentrated solution is used annually per dyeing site . About 10-100 kg conc. solution/ i.e. 2.5-25 kg Cr (VI) is used per site per day in 50-260 days/year . About 95% of all Cr used is contained in dyed articles in non-toxic Cr (III) form Technical and organisational conditions and measures . Use in closed reactor baths Site- . Automatic programmable remotely operated process control and chemical dosing spec . Test laboratory conditions: In manual use of sodium dichromate in test laboratory, all necessary PPEs are in use in handling dichromate Conditions and measures related to personal protection, hygiene and health evaluation . No contact with chromium dichromate solutions Site- . No direct contact with any process liquids spec . Small scale laboratory testing of dyes is comparable to general laboratory work in industry Other conditions affecting workers exposure . Training: employees are trained on how to safely work with the substance, incl. how to use the Site- necessary personal protection equipment. spec Additional good practice advice. Obligations according to Article 37(4) of REACH do not apply . Work under a high standard of personal hygiene. Wash hands and face before breaks. When using the product, do not eat, drink or smoke.

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9.2.2.2 Exposure and risks for workers

Measurements:

The concentration of Cr (VI) in the process hall air has been measured during normal operational conditions of most of the dyeing sites. Chromium has not been detected in any of the measurements.

The main focus in systematic occupational Cr (VI) exposure measurements at the sites has been in biomonitoring studies. Therefore results for biomonitoring is relatively complete for some of the sites. In these studies Cr in urine has been sampled and analysed at least annually for dyeing workers (for details see Annex 4). Modelled exposure estimates are used as supportive information together with the measured values to make conclusions on the worker exposure and excess cancer risk levels.

Static and personal sampling Measurements of chromium (III/VI) in the working place air of the dyeing halls have been carried out at several sites. The results have shown that there are no measurable concentrations of Cr (VI) in the air, all results are below the detection limits Cr (VI) < 0.1 µg/m3 (stationary) and Cr (VI) <0.4 µg/m3 (breathing zone portable/personal). Low concentrations in air have been one of the reasons that focus in occupational exposure monitoring has been put on biological monitoring and on Cr in urine measurements. Biomonitoring covers better all the combined exposure routes via inhalation, skin and oral.

Biological monitoring

Biological monitoring may be seen as early detection of increased exposure in individuals (eg. poor work methods) or workers carrying out same tasks (poor OCs). Measurements of chromium levels in urine has been select- ed as the most suitable method in monitoring worker exposure at the dyeing sites. The table below summarises the pooled biomonitoring results for the dyeing sites for the years 2011-2016 (n=280). The dataset presented here is regarded as a representative set of data for the downstream user sites. In the second row of the table a conversion is made to extrapolate from the biological results the concentrations of Cr in air which would during an 8 hr work shift elevate urine Cr levels to equal levels as that measured. The converted results are clearly higher than what has, in reality, been measured in workplace air at the sites.

Table 14. Statistical results of Cr in urine [μmol/mol creatinine] levels from a dyeing site 2011-2015 Number of measurements (n=280) 90 th perc. Median Geom. 25th perc. mean Combined results Cr μg/l in urine 1.51 0.30 0.26 0.13 Results in μmol/mol creatinine 3.0 0.60 0.52 0.26 3 Exp. converted to μg/m (Cr(VI) in air) 3.8 0.75 0.65 0.32 The more detailed data on the biomonitoring studies and other workplace measurements are presented in Annex 4.

The biomonitoring results from the dyeing sites have been given in units μg/l Cr in urine “creatinine corrected”. The relationship 1 µmol Cr/mol creatinine = 0.5 μg/L Cr in urine (“creatinine corrected”) is applied. The con- versions of biomonitoring results to Cr μg/m3 in air are made based on information that chromium concentration 0.5 μg/m3 is known to generate a Cr level of 0.4 μmol/mol creatinine (0.2 μg Cr /l) in urine (see Annex 4).

Exposure concentrations and modelled values together with estimation of excess lifetime cancer risk is presented in table below. The cancer risk is estimated by TWA Cr (VI) exposure concentration 1 μg/m3 increases lung cancer risk in EU workers by a factor 4 x10-3 based on a 40 year working life (8h/day, 5 days/week).

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Table 15. Exposure concentrations and risks for worker Route of exposure and type of Exposure concentration Risk effects characterisation, excess lung cancer risk Inhalation, systemic, long-term < 0.1 µg/m3 Cr (VI) measured, static sampling (n= ) < 4 * 10-4 Inhalation, systemic, long-term < 0.4 µg/m3 Cr (VI) measured, personal sampling (n= ) < 1.6 * 10-3 Inhalation, systemic, long-term < 1 µg/m3 Cr (VI) TWA8, good general ventilation, No < 4 * 10-3 modelled, PROC3, MEASE RPE, 1-5% Cr solution, 95°C (1.02) Inhalation, systemic, long-term < 0.001 µg/m3 Cr (VI) TWA8, good general ventilation, < 4 * 10-6 modelled, ART (1.5) No RPE, 0.1% Cr solution, 95°C Dermal, systemic, long-term, 1 µg/kg/d protective gloves, good general ventilation, 1- nd. modelled, PROC3, MEASE 5% Cr solution, 95°C (1.02) Combined routes, systemic, 0.75 µg/m3 (TWA8) Cr (tot) median (n=280, biomoni- 3 * 10-3 long-term (extrapolated from toring results, conversion to Cr in air) biomonitoring results)

The cancer risk relationship used is an excess lifetime (up to age 89) lung cancer risk estimates for workers exposed at different 8h-Time Weighted Average concentrations of Cr (VI) for 40 years.

Remarks on exposure data:

In general the exposure levels observed in the static, personal and biological studies may be regarded low and the exposure is well controlled, more or less at the same level as in workplaces where chromium (VI) is not used intentionally in any processes (HSE 2013). The modelled MEASE and ART results of the Cr concentration in workplace air also support the low < 1 µg/m3 measured values.

The static and personal sampling from breathing zone exposure measurements from workplace air at the dyeing sites show low concentrations, systemically all below the detection limits (<0.1 µg/m3/ <0.4 µg/m3) Cr (tot) in workplace air.

Biomonitoring has been the preferred method in exposure monitoring at the sites. The exposure levels observed in the reported biomonitoring studies from dyeing are low and has also been converted to represent workplace air respirable chromium concentrations. These converted Cr µg/m3 values has been used, together with direct air measurements, in the risk characterization.

The converted concentrations (extrapolation from biomonitoring studies to µg/m3 in air) are at a range from 0.32 µg/m3, median 0.75 µg/m3 to 3.8 µg/m3(90th perc.). What is noticeable is that in any of the measurements such concentrations have not been detected in air at the dyeing sites.

Based on the static/personal data and if exposure occurred via inhalation alone then the biomonitoring results would have been even lower, at the same level as for non-exposed populations. This indicates that a significant proportion of exposure occurs via other routes, either via dermal absorption after handling of dyed materials and/or ingestion of small dyed inhalable but non-respirable wool fiber particles. It must be noticed that if the route of administration to the body is as it is expected here (partly dermal/oral from dyed materials) the exposure is predominantly to Cr (III) and not to Cr (VI). The biomonitoring results, chromium in urine, do not make it possible to make any firm quantitative conclusions whether the actual exposure was to Cr (III) or Cr (VI). However, in this case it is likely that exposure is mainly to Cr (III) for those workers who are involved in handling the freshly dyed materials. In comparison, the maintenance workers, because the nature of their work, may have higher potential to be exposed to easily absorbed and soluble Cr (VI) -ions.

In a wider scope, the observed low levels of chromium in urine of the dyeing site workers can be compared to findings from other sectors of industries and general population. In comparison to the HSE data from UK, the

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 28 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9 results obtained from the dyeing site shows that chromium exposure levels are only slightly elevated in comparison to non-exposed population, but clearly below the average industrial levels. Even the highest measured chromium urine concentration (13.4 μmol/mol creatinine) of dyeing workers remain to the same level as 90th percentiles observed in electroplaters (12.9 μmol/mol creatinine), which is industry applying high amounts of chromium in their semi-open warm process baths. The 90th percentile exposure value for the four dyeing sites is at about the same level as median for non-chromium workers in UK. The non-chromium workers means here tasks and industries where chromium is not intentionally used in processes.

Conclusion on risk characterisation: Based on the information available risk to workers for this contributing worker scenario can be considered to be -3 controlled to a risk level of < 3 *10 excess lung cancer lifetime risk. Biomonitoring results (Crtot in urine) have been used in exposure assessment and risk characterisation and therefore the effect of exposure to Cr (III) may have significant effect on overall results.

9.2.3 Worker contributing scenario 2, Maintenance and management of dichromate solution at the dyeing plants (PROC 8b, 9, 28)

Maintenance in dyeing sector

In general all the dyeing machines that work under pressure are subject to EU PED-directive/national legislation and periodical controls. The other dyeing machines are subjected to the normal internal control performed by the dyeing sector maintenance workers (1 person always in the hall at minimum). These periodical maintenance tasks are carried in a controlled way (to empty and clean baths) and exposure to chromates is not expected.

The chemical dosing system is verified by on-site maintenance workers, but the presceduled maintenance is normally performed by outsourced professional workers (authorised by the system manufacturer company).

The controls on the dichromate solution tank and other chemical tanks may be performed by on-site specialised maintenance worker. The controls in the WWTP may also need a specialised maintenance worker. The waste air ventilation systems are subject to periodical maintenance normally done by the on-site maintenance workers.

The scrubbers for acidic and basic and other vapours (eg. hydrogen peroxide) coming out from the tanks are controlled by on-site maintenance worker.

Standard operations in handling of sodium dichromate at the dyeing sites

The chemical supplier delivers sodium dichromate (61%) liquid to dyeing sites in 25 kg-1000 kg plastic containers. All the containers are located on a plastic or stainless steel pallet. The pallet of small (25 kg) containers works at the same time also as a safety drain basin (property of the dyeing sites).

If the dyeing site has a larger ( > 1000 l) dedicated dichromate tank the truck driver may, under supervision of process operator, pump the content of the IBC containers to these larger on-site tanks. Alternatively supplier leaves the IBCs to the chemical storage location of the dyeing site. The IBC containers are property of the chemical supplier. Condition checks of the containers is the responsibility of the chemical supplier.

From time to time, small containers are moved from the locked chemical storage area by the on-site operators and emptied by electric pump to the consumption tank of the on-site dichromate feed system.

Containers are unloaded using a forklift truck and “parked” in a place suitable to ensure containment of the whole sodium dichromate and the conveyance of any accidental releases to a depuration system and to prevent them from drying. Moreover, accidental release measures are provided in order to reduce Cr (VI) to Cr (III).

In case of need the closed container is picked, transported to the dosing system and placed so as to guarantee its

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 29 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9 conveyance of accidental releases to the depuration system. Cr conveyance takes place through a channel containing water, which serves to prevent the solution from drying and from generating an inhaling fraction. The connection to the closed circuit automatic dosing system takes place through graft and by gravity or through pumping. The whole operation is completely carried by in-house staff, a very limited number of suitably trained operators accordingly protected and equipped with all necessary PPEs, which operate in accordance with specific procedures on the use of dichromate.

The 1000 kg IBC containers are used as a consumption tanks at some of the sites. IBCs may be moved by the supplier (truck driver) straight to the location where empty IBC container(s) is substituted by full container(s). Trained on-site operator makes the couplings to joint the container properly to the on-site dichromate feed system. All sites have completely closed and dedicated automated chemical feeding system for the 61% sodium dichromate solution.

9.2.3.1 Conditions of use Method Product (article) characteristics . Concentrated dichromate solution in containers, consumption tanks, dosing system Site-spec. . Diluted dichromate solution in process equipments and in waste streams Amount used (or contained in articles), frequency and duration of use/exposure . Transfer of 25-1000 kg containers, weekly or monthly Site-spec . During maintenance variable amounts and concentrations of Cr solutions . Prescheduled maintenance of chemical dosing instruments, 0.3-1 times a year (0.3-1 times a year, 1-2 workers) Technical and organisational conditions and measures . Outdoors, transfers and coupling of containers to chemical dosing system Site-spec . Indoors transfers and coupling of containers at normal room temperature, good general ventilation . Prescheduled maintenance of chemical dosing instruments, Conditions and measures related to personal protection, hygiene and health evaluation . Skin and body protection: Protective suit (washable or disposable overalls), safety boots, Site-spec chemical goggles or face shield, chemically resistant gloves (Nitrile rubber, chloroprene rubber, butyl rubber or other suitable gloves, complying with the requirements of EN 374 (break- through time: 480 min); Specific activity training in relation to use and maintenance of the gloves must be provided) [Effectiveness Dermal: 95%] . Unloading of chromate IBCs to other containers or in making couplings: RPE halfmask ABEK1 . Precheduled/corrective maintenance, PPE and additionally RPE is always used when potential to exposure arise: halfmask ABEK1 . Work under a high standard of personal hygiene. Wash hands and face before breaks. Other conditions affecting workers exposure . Any spills of dichromate must be cleaned off (flushed/reduced) and prevented them from dry- Site-spec ing or spreading and contaminating the working area and equipments . Training of employees on how to safely work with the substance, incl. how to use the necessary personal protection equipment. . If an operator comes in contact with the sodium dichromate he/she has to change clothes and take a shower as soon as possible. . The employees who are allowed to handle sodium dichromate are authorized to handle the substance. Work instructions and risk analysis covering e.g. the operating instructions and action in case of spilling are available for the personnel. . The operators have always access to written work instruction documents on handling of rea- gents . The operative personnel and the operators in charge of ordinary and extraordinary maintenance are kept informed and trained on the risks connected with the presence of sodium dichromate;

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Method training takes place periodically and training programs are specifically updated Additional good practice advice. Obligations according to Article 37(4) of REACH do not apply . Periodical biomonitoring of worker exposure Site-spec

9.2.3.2 Exposure and risks for workers

Measurements: Static sampling: Concentrations of Cr (VI) in process hall air has been monitored by static sampling methods. Concentrations have been below the detection limits < 0.1 µg/m3.

Biomonitoring studies: A very limited number of biomonitoring results specifically for maintenance workers having their tasks in dyeing premises is currently available (n=4, person=1) for this WCS2 exposure assessment. As a comparison there are results from other maintenance workers/welders from the same company (n=9, person=4). Table below summaries the results.

Table 16. Biomonitoring study results for maintenance workers Cr in urine Tasks number of number of range of re- persons measure- sults [Cr µg/l] ments Maintenance in dyeing area 1 4 0.02 - 1.46 Exposure conversion to μg/m3 0.05 - 3.6 Maintenance welder (not in dyeing dep.) 4 9 0.09 - 0.93 Exposure conversion to μg/m3 0.22 - 2.3

Conversion of biomonitoring results are made based on information that chromium concentration 0.5 μg/m3 is known to generate a Cr level of 0.4 μmol/mol creatinine (0.2 μg Cr /l) in urine (see Annex 4). It is know that welders of stainless steel are exposed to ionic chromium species (Cr (III/VI)). The group of maintenance workers, welders from same company, but not often working at the dyeing department, is presented here together with the one maintenance worker nominated and working daily at the dyeing department (obviously not welding or welding rarely there).

Modelling the exposure Handling of sodium-dichromate solution has been assigned the PROC 8b category, which means: Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities. The description of 8b and the conditions at the dyeing sites are expected to match well with each other in transferring and unloading/coupling dichromate containers. In general, maintenance task include occasions where potential for exposure to Cr cannot be anticipated well in advance. Therefore an attitude in using PPEs/RPEs should be precautional (be prepared in advance for high exposure situation).

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Table 17. Exposure concentrations and risks for worker, maintenance Route of exposure and type of Exposure concentration Risk characterisation effects Inhalation, systemic, long-term, < 1 µg/m3 (TWA8) indoors in process hall, out- excess lung cancer risk measured doors, normal operating conditions, measured < 4 *10-3 Inhalation, systemic, long-term, measured Inhalation, systemic, acute Inhalation, local, long-term, 1 µg/m3, (TWA 8) PROC 8a, task 60-240 min, excess lung cancer risk modelled liquid (> 25% Cr (VI) direct handling, contact level 4 *10-3 (exposure is rare, extensive, RPE 95%, (MEASE 1.02) (daily Dose 1-2 d/year or more sel- 0.17 µg/kg (bw)/d) dom) Eye, local Combined routes, systemic, 0.05 - 3.6 μg/m3 (TWA8) (converted from biomon- 2 *10-4 – 1.4*10-2 long-term, biomonitoring itoring results to Cr in air)

Remarks on exposure data:

Maintenance work may typically contain tasks which can lead to significant exposure, since pipe joints and sealed containers sometimes need to be opened and liquids inside may rinse out and should be captured in a controlled way. However, only in corrective maintenance, after equipment faults, these difficult operating conditions may occur e.g. in correcting the chemical feeding system. In normal prescheduled maintenance at the dyeing sites the working conditions are well anticipable and the selection of all PPEs accordingly.

Use of skin/eye protection is always required – due to corrosive, irritant, sensitising and toxic properties of chromic acid and chromate solutions. Therefore quantitative assessment of dermal exposure or exposure to eyes is not regarded relevant. Use of skin protection is always recommended, even if hand protection requirements may sometimes be difficult to comply with due to the nature of some of the maintenance work (in assembly of very small parts).

Conclusion on risk characterisation: Based on the information available risk to workers for this contributing worker scenario can be considered to be controlled to a risk level of 2 *10-4 – 1.4*10-2. It has to be noted that the biomonitoring dataset for maintenance tasks is very limited, only four measurements.

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10. RISK CHARACTERISATION RELATED TO COMBINED EXPOSURE

Risk characterisation for combined exposure is relevant in situations where 1) the same person is exposed to the same substance in the same setting via different routes of entry and via the environment. Combined time weighted one full shift exposure estimation is also relevant in all those cases where 2) the same person is carrying out different contributing sub scenario tasks during a same work shift.

In the first case combined risk characterisation can be performed by combining the current risk levels derived for the local population to the risk levels derived for workers. The combined exposure is relevant for persons living in the communities located close to the electroplating plant and at the same time being workers at the dyeing plant or chemical supplier terminal site. The estimated man via the environment exposure levels at the Biella area are so low, that in practice they have no influence on the occupational exposure levels of the dyeing workers.

In the second case, worker exposure arsing from different tasks can be summed up. At the dyeing sites workers are involved in WCS1. For the WCS2 the summing is not that reasonable, since exposure in different WCS2 maintenance tasks are so heterogenous group of various tasks that cannot be easily splitted and summed up with other contributing sub scenarios. The maintenance of process equipment is carried out by specialised personnel and not by the WCS1 dyeing workers. The number of potentially exposed workers is given in table below.

Table 18. The number of workers potentially exposed at the dyeing sites and chemical terminal site WCS1 WCS2 All workers working at Maintenance at the dye- the estimated sites ing sites/process hall

USE 1, TERMINAL SITE 7

USE 2, DYEING 125 *) 15

*) All workers working in the dyeing hall

The worker exposure levels for the formulation (Use 1) and dyeing (Use 2) and the number of exposed workers and the excess lung cancer risks are presented in Table 19 and 20 below. Table 20 lists also the risk levels estimated for the general population.

Use 1

Repackaging of Sodium dichromate to be supplied as a mordant in the dyeing of wool as sliver and/or yarn with dark colours in industrial settings.

Table 19. Summary of estimated cancer risk levels for different scenarios Exposed group Excess lung cancer risk Number of workers Duration of exposure Worker WCS1 5*10-3 7 8 hr /220 d

Use 2

Sodium dichromate as a mordant in the dyeing of wool as sliver and/or yarn with dark colours in industrial settings.

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 33 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

Table 20. Summary of estimated cancer risk levels for different scenarios and populations Exposed group Excess lung cancer risk Excess intestinal cancer Duration of exposure risk Worker WCS1, dyeing < 1 * 10-4 - 3*10-3 8 hr/220 d/a Worker WCS2, maintenance 2* 10-4 - 1.4*10-2 1 hr/20 d/a (estimate) General population, local 1.5 * 10-5 6.9 * 10-6 General population, regional 3.3 * 10-13 7.6 * 10-8

Uncertainty Analysis

Regarding the site specific exposure estimates, current worker exposure and releases of chromium into the local environment are known rather well at the downstream user dyeing sites and at the chemical terminal site. Measured worker exposure data is not available for all of the sites. The basic dyeing techniques used at all of the sites are similar and therefore the dataset available is regarded sufficient to make conclusions. In addition, because of good on-site data, modelling of worker exposure and associated typical uncertainties in using the modelled results, has only a very small and comparative/supporting role only.

The highest uncertainty in the worker exposure estimates is accociated in the speciation of chromium. It is not always known if the oxidation state of chromium is Cr(VI) or Cr(III) in that moment when worker is exposed (via the air, skin or oral route). In those tasks where concentrated sodium dichromate is handled the oxidation state is (VI). In the actual processing use and the following processes/tasks the oxidation state is normally Cr (III).

Because the oxidation state is not always known, the realistic worst cas approach has been taken and assumed chromium to be at (VI) oxidation state. This may lead to owerestimation of the cancer risk levels.

This same uncertainty in oxidation state is also assciated in the use of biomonitoring study results, since the chromium in urine levels do not make distinction between Cr (III)/(VI) species. This may also lead to owerestimation of the cancer risks. It is recognised here, in this exposure assessment, that extrapolation of Cr in urine biomonitoring results to Cr in air levels (µg/m3) and making lung cancer risk levels based on these chromium Cr(VI) (µg/m3) concentrations leads also to at least slightly owerestimated cancer risk levels.

As a final conclusion, the site specific exposure assessments can be finalised since unacceptable or significantly high uncertainties have not been identified in the exposure data and the reliability of the measured exposure data is regarded reliable and clearly meets the general quality criteria set for sampling and analysis of occupational exposure data and environmental release data.

Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 34 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

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Ilario Ormezzano SAI Spa CHEMICAL SAFETY REPORT 35 EC number: Sodium dichromate CAS number: 234-190-3 10588-01-9

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List of Abbreviations ADR transportation - European Agreement concerning the International Carriage of Dangerous Goods by Road B Bioaccumulation BCF Bioconcentration Factor BMF Biomagnification Factor bw body weight CAS Chemical Abstract Services Cr (III) Trivalent chromium Cr (VI) Hexavalent chromium CMR Carcinogenic, Mutagenic and toxic to Reproduction CNS Central Nervous System COD Chemical Oxygen Demand CT50 Clearance Time, elimination or depuration expressed as half-life DFI daily food intake DT50 Degradation half-life or period required for 50 percent dissipation / degradation EbC50 Effect Concentration measured as 50% reduction in biomass growth in algae tests EC10 Effect Concentration measured as 10% effect EC50 median Effect Concentration ECHA European Chemicals Agency ECVAM European Centre for the Validation of Alternative Methods ErC50 Effect Concentration measured as 50% reduction in growth rate in algae tests ESD Emission Scenario Document EUSES European Union System for the Evaluation of Substances P Persistent PBT Persistent, Bioaccumulative and Toxic PEC Predicted Environmental Concentration PNEC Predicted No Effect Concentration PPE Personal Protective Equipment RPE Respiratory protection equipment QSAR (Quantitative) Structure-Activity Relationship SAR Structure-Activity Relationships SSD Species Sensitivity Distribution STP Sewage Treatment Plant UC Use Category vB very Bioaccumulative vP very Persistent vPvB very Persistent and very Bioaccumulative WWTP Waste water treatment plant

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