Sulfate de manganèse monohydraté Fiche de données de sécurité conforme au Règlement (CE) n° 453/2010 Date d'émission: 17/12/2013
Date de révision: 17/12/2013
:
Version: 0.0
SECTION 1: Identification de la substance/du mélange et de la société/l’entreprise 1.1.
Identificateur de produit
Forme du produit
: Substance
Nom de la substance
: Sulfate de manganèse monohydraté
Numéro CE
: 232-089-9
n° CAS
: 10034-96-5
Numéro d'enregistrement REACH
: 01-2119456624-35-0011
1.2.
Utilisations identifiées pertinentes de la substance ou du mélange et utilisations déconseillées
1.2.1.
Utilisations identifiées pertinentes
Catégorie d'usage principal
: Utilisation industrielle,Utilisation professionnelle,Utilisation par les consommateurs
Utilisation de la substance/mélange
: cf. Scénarios d'exposition
1.2.2.
Usages déconseillés
Titre
Descripteurs d'utilisation
X
Raison Scénarios d'exposition
Texte complet des descripteurs d'utilisation: voir section 16 1.3.
Renseignements concernant le fournisseur de la fiche de données de sécurité
ALTICHEM 4 RUE JACQUES VAUCANSON 95310 SAINT-OUEN-L'AUMÔNE - FRANCE T +33 (0)1 34 40 12 80 - F +33 (0)1 34 64 56 99
[email protected] 1.4.
Numéro d’appel d’urgence
Numéro d'urgence
: N°ORFILA: +33 (0)1 45 42 59 59
SECTION 2: Identification des dangers 2.1.
Classification de la substance ou du mélange
Classification selon le règlement (CE) N° 1272/2008 [CLP] Eye Dam. 1
H318
STOT RE 2
H373
Aquatic Chronic 2
H411
Texte complet des phrases H: voir section 16 Classification selon les directives 67/548/CEE ou 1999/45/CE Xn; R48/20/22 N; R51/53 Texte complet des phrases R: voir section 16 Effets néfastes physicochimiques, pour la santé humaine et pour l’environnement Pas d'informations complémentaires disponibles
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2.2.
Éléments d’étiquetage
Etiquetage selon le règlement (CE) N° 1272/2008 [CLP] Pictogrammes de danger (CLP)
:
Mention d'avertissement (CLP)
: Danger
Mentions de danger (CLP)
: H318 - Provoque des lésions oculaires graves H373 - Risque présumé d'effets graves pour les organes à la suite d'expositions répétées ou d'une exposition prolongée H411 - Toxique pour les organismes aquatiques, entraîne des effets néfastes à long terme
Conseils de prudence (CLP)
: P260 - Ne pas respirer les aérosols, brouillards, fumées, gaz, poussières, vapeurs P273 - Éviter le rejet dans l’environnement P280 - Porter des gants de protection, des vêtements de protection, un équipement de protection des yeux, un équipement de protection du visage P305+P351+P338 - EN CAS DE CONTACT AVEC LES YEUX: rincer avec précaution à l’eau pendant plusieurs minutes. Enlever les lentilles de contact si la victime en porte et si elles peuvent être facilement enlevées. Continuer à rincer P310 - Appeler immédiatement un CENTRE ANTIPOISON ou un médecin P501 - Éliminer le contenu/récipient conformément à la réglementation locale/régionale/nationale/internationale.
GHS05
2.3.
GHS08
GHS09
Autres dangers
Pas d'informations complémentaires disponibles
SECTION 3: Composition/informations sur les composants 3.1.
Substance
Nom
: Sulfate de manganèse monohydraté
n° CAS
: 10034-96-5
Numéro CE
: 232-089-9
Numéro index
:
Nom
Identificateur de produit
%
Classification selon la directive 67/548/CEE
Sulfate de manganèse monohydraté
(n° CAS)10034-96-5
98 - 100
Xn; R48/20/22 N; R51/53
(Numéro CE)232-089-9
(Numéro index)025-003-00-4
(N° REACH)01-2119456624-35-0011
Nom
Identificateur de produit
%
Classification selon le règlement (CE) N° 1272/2008 [CLP]
Sulfate de manganèse monohydraté
(n° CAS)10034-96-5
98 - 100
Eye Dam. 1, H318 STOT RE 2, H373 Aquatic Chronic 2, H411
(Numéro CE)232-089-9
(Numéro index)025-003-00-4
(N° REACH)01-2119456624-35-0011
Textes des phrases R et H: voir section 16 3.2.
Mélange
Non applicable
SECTION 4: Premiers secours 4.1.
Description des premiers secours
Premiers soins après inhalation
: Retirer le sujet de la zone contaminée et l'amener à l'air frais. Arrêt respiratoire: respiration artificielle ou oxygène. Appeler un médecin. Si la respiration est difficile, administrer de l'oxygène.
Premiers soins après contact avec la peau
: Enlever les vêtements contaminés. Laver abondamment à l'eau. Si les symptômes persistent, appeler un médecin.
Premiers soins après contact oculaire
: Rincer immédiatement avec beaucoup d'eau pendant 15 min. Consulter un médecin.
Premiers soins après ingestion
: Faire boire immédiatement beaucoup d'eau ou du lait. Ne jamais administrer quelque chose par la bouche à une personne inconsciente. Consulter un médecin.
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4.2.
Principaux symptômes et effets, aigus et différés
Symptômes/lésions après inhalation
: Toux. Essoufflement.
Symptômes/lésions après contact avec la peau
: Irritation de la peau. Rougeurs.
Symptômes/lésions après contact oculaire
: Rougeurs, douleur.
Symptômes/lésions après ingestion
: Douleurs abdominales. Vomissements. Nausées.
4.3.
Indication des éventuels soins médicaux immédiats et traitements particuliers nécessaires
Traitement symptomatique.
SECTION 5: Mesures de lutte contre l’incendie 5.1.
Moyens d’extinction
Moyens d'extinction appropriés 5.2.
: Non combustible. Utiliser les moyens adéquats pour combattre les incendies avoisinants.
Dangers particuliers résultant de la substance ou du mélange
Danger d'incendie
: Ininflammable.
Produits de décomposition dangereux en cas d'incendie
: libération de gaz/vapeurs toxiques et corrosifs : oxydes de soufre...
5.3.
Conseils aux pompiers
Protection en cas d'incendie
: Les pompiers doivent porter un appareil respiratoire autonome à pression positive et une tenue de feu complète. Utiliser un vêtement de protection chimiquement résistant.
SECTION 6: Mesures à prendre en cas de déversement accidentel 6.1.
Précautions individuelles, équipement de protection et procédures d’urgence
Mesures générales 6.1.1.
: Ne pas respirer les poussières/fumées/gaz/brouillards/vapeurs/aérosols. Porter un appareil de protection des yeux/du visage.
Pour les non-secouristes
Pas d'informations complémentaires disponibles 6.1.2.
Pour les secouristes
Pas d'informations complémentaires disponibles 6.2.
Précautions pour la protection de l’environnement
Éviter le rejet dans l’environnement. 6.3.
Méthodes et matériel de confinement et de nettoyage
Autres informations 6.4.
: Eliminer les matières ou résidus solides dans un centre autorisé.
Référence à d'autres sections
Pas d'informations complémentaires disponibles
SECTION 7: Manipulation et stockage 7.1.
Précautions à prendre pour une manipulation sans danger
Précautions à prendre pour une manipulation sans danger
: Ne pas respirer les Aérosols, Brouillard, fumée, Gaz, Poussières., Vapeurs. Porter un appareil de protection des yeux/du visage. Eviter le contact avec la peau, les yeux ou les vêtements. Eviter le contact répété ou prolongé avec la peau.
Mesures d'hygiène
: Ne pas boire, manger ou fumer sur le lieu de travail. Prendre une douche.
7.2.
Conditions nécessaires pour assurer la sécurité du stockage, tenant compte d’éventuelles incompatibilités
Conditions de stockage
: Entreposer dans un endroit sec et abrité afin d'éviter tout contact avec l'humidité. Protéger les récipients contre tout dommage physique.
Produits incompatibles
: Voir la section 10 consacrée aux matériaux incompatibles.
7.3.
Utilisation(s) finale(s) particulière(s)
Voir annexe.
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SECTION 8: Contrôles de l’exposition/protection individuelle 8.1.
Paramètres de contrôle
Sulfate de manganèse monohydraté(10034-96-5) France VME (mg/m³) Allemagne TRGS 900 Valeur limite au poste de travail (mg/m³) Italie - Portugal- USA ACGIH
ACGIH TWA (mg/m³)
Espagne
VLA-ED (mg/m³)
Royaume Uni
WEL TWA (mg/m³)
Pologne
NDS (mg/m³)
1 mg/m³ Mn (fumées) 0,5 mg/m³ Manganèse et composés inorganiques (en tant que Mn) 0,2 mg/m³ Manganèse et composés inorganiques (en tant que Mn) 0,2 mg/m³ Manganèse et composés inorganiques (en tant que Mn) 0,5 mg/m³ Manganèse et composés inorganiques (en tant que Mn) 0,3 mg/m³ Manganèse et composés inorganiques (en tant que Mn)
Sulfate de manganèse monohydraté(10034-96-5) DNEL/DMEL (Travailleurs) A long terme - effets systémiques, cutanée 0,00414 mg/kg de poids corporel/jour A long terme - effets systémiques, inhalation 0,2 mg/m³ DNEL/DMEL (Population générale) A long terme - effets systémiques, inhalation 0,043 mg/m³ A long terme - effets systémiques, cutanée 0,0021 mg/kg de poids corporel/jour PNEC (Eau) PNEC aqua (eau douce) 0,0128 mg/l (AF = 5) PNEC aqua (eau de mer) 0,0004 mg/l (AF = 50) PNEC aqua (intermittente, eau douce) 0,03 mg/l (AF = 100) PNEC (Sédiments) PNEC sédiments (eau douce) 0,0114 mg/kg dwt (AF = 50) PNEC sédiments (eau de mer) 0,00114 mg/kg dwt (AF = 500) PNEC (Sol) PNEC sol 25,1 mg/kg dwt Facteur d'évaluation (AF) = 10 PNEC (STP) 56 mg/l (AF = 10) PNEC station d’épuration 8.2.
Contrôles de l’exposition
Contrôles techniques appropriés
: Les mesures de contrôle d'ingénierie telles que qu'une ventilation d'extraction locale (VEL) peuvent être requises afin de contrôler l'exposition aux petites particules et à la fumée. Le contrôle de l'exposition doit être considéré.
Protection des mains
: Gants de protection.
Protection oculaire
: Lunettes de sécurité.
Protection de la peau et du corps
: Utiliser un vêtement de protection chimiquement résistant.
Protection des voies respiratoires
: Respirateur anti-poussières agréé.
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SECTION 9: Propriétés physiques et chimiques 9.1.
Informations sur les propriétés physiques et chimiques essentielles
État physique
: Solide
Apparence
: Poudre. Solide granulé.
Couleur
: blanc. rose clair.
Odeur
: inodore.
Seuil olfactif
: Aucune donnée disponible
pH
: 5-7
Vitesse d'évaporation relative (l'acétate butylique=1)
: Aucune donnée disponible
Point de fusion
: 700 °C (1292 °F)
Point de congélation
: Aucune donnée disponible
Point d'ébullition
: 850 °C (1562 °F)
Point d'éclair
: Non applicable
Température d'auto-inflammation
: Non applicable
Température de décomposition
: 850 °C (1562 °F)
Inflammabilité (solide, gaz)
: Aucune donnée disponible
Pression de la vapeur
: Non applicable
Densité relative de la vapeur à 20 °C
: Non applicable
Densité relative
: 2,95
Solubilité
: Eau: Facilement soluble Ethanol: Insoluble
Log Pow
: Non applicable
Viscosité, cinématique
: Aucune donnée disponible
Viscosité, dynamique
: Aucune donnée disponible
Propriétés explosives
: Le produit n'est pas explosif.
Propriétés comburantes
: Aucune donnée disponible
Limites d'explosivité
: Aucune donnée disponible
9.2.
Autres informations
Pas d'informations complémentaires disponibles
SECTION 10: Stabilité et réactivité 10.1.
Réactivité
Pas de réaction dangereuse connue dans les conditions normales d'emploi. 10.2.
Stabilité chimique
Stable. 10.3.
Possibilité de réactions dangereuses
Polymérisation dangereuse: Ne se produira pas. Réagit violemment avec : Agents oxydants forts. 10.4.
Conditions à éviter
Températures élevées. Humidité. 10.5.
Matières incompatibles
Agents oxydants forts. Acides forts. Aluminium. Magnésium. 10.6.
Produits de décomposition dangereux
Oxyde de manganèse. Oxydes de soufre.
SECTION 11: Informations toxicologiques 11.1.
Informations sur les effets toxicologiques
Toxicité aiguë
: Non classé En cas d'ingestion : Nausées, Vomissements, Diarrhée En cas d'inhalation : Toux, Essoufflement Toxicité chronique : L'empoisonnement au manganèse peut survenir à partir de l'absorption excessive de manganèse par inhalation. Les effets les plus notables de l'intoxication au manganèse sont les troubles du système nerveux qui peuvent survenir aussi bien tôt que six mois après l'exposition initiale. Les symptômes, qui ressemblent à la maladie de Parkinson, incluent l'apathie, somnolence, troubles du sommeil, spasmes musculaires, une paralysie et des problèmes du contrôle émotionnel; des blessures permanentes peuvent survenir si l'empoisonnement chronique au manganèse n'est pas traité.
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DL50 orale rat
2150 mg/kg bw (MnSO4) - 1470 mg/kg bw (MnCl2)
DL50 orale CL50 inhalation rat (mg/l)
2330 mg/kg bw (MnSO4) - 1330 mg/kg bw (MnCl2) - souris 4,45 mg/l/4h MnSO4 (FORME ANHYDRE) rat - mâle (LOAEC = 0,17 g/kg)
Corrosion cutanée/irritation cutanée
: Non classé
Lésions oculaires graves/irritation oculaire
: Provoque des lésions oculaires graves.
pH: 5 - 7 Provoque une sévère irritation des yeux Rougeurs, douleur pH: 5 - 7 Sensibilisation respiratoire ou cutanée
: Non classé Sensibilisant faible de la peau Rougeurs
Mutagénicité sur les cellules germinales
: Non classé
Cancérogénicité
: Non classé
Toxicité pour la reproduction
: Non classé
Toxicité spécifique pour certains organes cibles (exposition unique)
: Non classé
Toxicité spécifique pour certains organes cibles (exposition répétée)
: Risque présumé d'effets graves pour les organes à la suite d'expositions répétées ou d'une exposition prolongée.
Danger par aspiration
: Non classé
SECTION 12: Informations écologiques 12.1.
Toxicité
Ecologie - général
: Toxique pour les organismes aquatiques, entraîne des effets néfastes à long terme.
Sulfate de manganèse monohydraté(10034-96-5) CL50 poisson 1 3,17 mg/l (Mn) - 96h Oncorhynchus mykiss CL50 autres organismes aquatiques 1 130 mg/l (Mn) - 96h Agosia chrysogaster CL50 Daphnie 1 9,8 mg/l (Mn2+) - 48h CL50 autres organismes aquatiques 1 3 mg/l (Mn) - 8.6 mg/l (Mn) - 13.7 mg/l (Mn) - 48h - (soft, moderately hard and hard water) H.azteca CL50 poissons 2 49,9 mg/l (Mn) - 96h Salmo trutta CL50 autres organismes aquatiques 2 5,7 mg/l (Mn) - 48h Ceriodaphnia dubia ErC50 (algues) 61 mg/l Desmodesmus subspicatus 12.2.
Persistance et dégradabilité
Sulfate de manganèse monohydraté(10034-96-5) Persistance et dégradabilité Non applicable. 12.3.
Potentiel de bioaccumulation
Sulfate de manganèse monohydraté(10034-96-5) Log Pow Non applicable 12.4.
Mobilité dans le sol
Pas d'informations complémentaires disponibles 12.5.
Résultats des évaluations PBT et VPVB
Pas d'informations complémentaires disponibles 12.6.
Autres effets néfastes
Pas d'informations complémentaires disponibles
SECTION 13: Considérations relatives à l’élimination 13.1.
Méthodes de traitement des déchets
Méthodes de traitement des déchets
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: Ce produit et son récipient doivent être éliminés de manière sûre, conformément à la législation locale. Les récipients vides seront recyclés, réutilisés ou éliminés en suivant les règlements locaux.
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SECTION 14: Informations relatives au transport Conformément aux exigences de ADR / RID / IMDG / IATA / ADN 14.1.
Numéro ONU
N° UN (ADR)
: 3077
N° UN (IATA)
: 3077
N° UN (IMDG)
: 3077
14.2.
Nom d’expédition des Nations unies
Désignation officielle pour le transport
: MATIÈRE DANGEREUSE DU POINT DE VUE DE L'ENVIRONNEMENT, SOLIDE, N.S.A.
Désignation exacte d’expédition/Description (IATA)
: ENVIRONMENTALLY HAZARDOUS SUBSTANCE, SOLID, N.O.S.
Désignation officielle pour le transport (IMDG)
: ENVIRONMENTALLY HAZARDOUS SUBSTANCE, SOLID, N.O.S.
Description document de transport
: UN 3077 MATIÈRE DANGEREUSE DU POINT DE VUE DE L'ENVIRONNEMENT, SOLIDE, N.S.A. (Sulfate de manganèse monohydraté(10034-96-5)), 9, III, (E)
14.3.
Classe(s) de danger pour le transport
Classe (ONU)
: 9
Code de classification (ONU)
: M7
Classe (IATA)
: 9
Classe (IMDG)
: 9
Etiquettes de danger (ONU)
: 9
Etiquettes de danger (IATA)
: 9
Etiquettes de danger (IMDG)
: 9
14.4.
Groupe d’emballage
Groupe d'embllage (ONU) Groupe d'emballage (IATA) Groupe d'emballage (IMDG) 14.5.
: III : III : III
Dangers pour l'environnement
Dangereux pour l'environnement
:
Autres informations
: Pas d'informations supplémentaires disponibles.
14.6.
Précautions particulières à prendre par l’utilisateur
14.6.1.
Transport par voie terrestre
Danger n° (code Kemler)
: 90
Code de classification (ONU)
: M7
Panneaux oranges
:
Disposition spéciale (ADR)
: 274, 335, 601
Catégorie de transport (ADR)
: 3
Code de restriction concernant les tunnels
: E
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Quantités limitées (ADR)
: 5kg
Quantités exceptées (ADR)
: E1
Code EAC
: 2Z
14.6.2.
Transport maritime
Pas d'informations complémentaires disponibles 14.6.3.
Transport aérien
Pas d'informations complémentaires disponibles 14.6.4.
Transport par voie fluviale
Pas d'informations complémentaires disponibles 14.7.
Transport en vrac conformément à l’annexe II de la convention MARPOL 73/78 et au recueil IBC
Non applicable
SECTION 15: Informations réglementaires 15.1.
Réglementations/législation particulières à la substance ou au mélange en matière de sécurité, de santé et d’environnement
15.1.1.
Réglementations EU
Pas de restrictions selon l'annexe XVII de REACH Ne contient pas de substance candidate REACH
15.1.2.
Directives nationales
Pas d'informations complémentaires disponibles 15.2.
Évaluation de la sécurité chimique
Pas d'informations complémentaires disponibles
SECTION 16: Autres informations Abréviations et acronymes
: RID : Regulations concerning the International Carriage of Dangerous Goods by Rail . ADN: European Agreement concerning international carriage of Dangerous goods by Inland waterways . ADR: European Agreement concerning international carriage of Dangerous goods by Road . AF : Assessment factor. Bw: Body weight. CAS: Chemical Abstracts Service. CLP : Classification, labelling, packaging. CSR: Chemical Safety Report. BCF : Bioconcentration factor. DMEL : Derived maximum effect level . DNEL: Derivative No effect Level. EC: European Community. EC50 : Half maximal effective concentration. ELV : Emission limit values. EN: European Norm . EUH: European Hazard Statement. EWC : European Waste catalogue . IARC : International Agency for Research on Cancer. IATA: International Air Transport Association. ICAO: International Civil Aviation Organization. IMDG: International Maritime Dangerous Goods. LC50: Median lethal concentration. LD50 : Median lethal dose. NOAEL : No-observedadverse-effect-level. NOEC : No observed effect concentration. NOEL : No observed effect level. OECD : Organisation for Economic Co-operation and Development. OEL : Operator exposure level. PBT: Persistent, bioaccumulative, Toxic. PEC : Predicted effect level. PNEC: Predicted no effect concentration. REACH : EC Regulation on Registration, Evaluation and Authorisation of Chemicals (Regulation (EC) N°1907/2006 as amended). STEL : Short Term Exposure Limit. TWA : Time Weighted Average . vPvB - very Persistent, very Bioaccumulative substance.
Textes des phrases R-,H- et EUH:: Aquatic Chronic 2 Eye Dam. 1 STOT RE 2 H318 H373 H411 R48/20/22 R51/53 N Xn
Dangereux pour le milieu aquatique — Danger chronique, Catégorie 2 Lésions oculaires graves/irritation oculaire, Catégorie 1 Toxicité spécifique pour certains organes cibles — Exposition répétée, Catégorie 2 Provoque des lésions oculaires graves Risque présumé d'effets graves pour les organes à la suite d'expositions répétées ou d'une exposition prolongée Toxique pour les organismes aquatiques, entraîne des effets néfastes à long terme Nocif: risque d'effets graves pour la santé en cas d'exposition prolongée par inhalation et par ingestion Toxique pour les organismes aquatiques, peut entraîner des effets néfastes à long terme pour l'environnement aquatique Dangereux pour l'environnement Nocif
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Sulfate de manganèse monohydraté Fiche de données de sécurité conforme au Règlement (CE) n° 453/2010 AVIS DE NON RESPONSABILITÉ
Les informations contenues dans cette fiche proviennent de sources fiables. Elles sont établies sur la base de nos connaissances à la date de mise à jour indiquée. Elles ont pour but d’aider l’utilisateur et ne doivent pas être considérées comme une garantie. Les conditions ou méthodes de manutention, stockage, utilisation ou élimination du produit sont hors de notre contrôle et nous déclinons toute responsabilité en cas de perte, dommage ou frais occasionnés par ou liés à celles-ci. Toutes les substances ou mélanges peuvent présenter des dangers inconnus et doivent être utilisés avec prudence. Nous ne pouvons pas garantir que les dangers soient décrits de manière exhaustive. Cette fiche a été rédigée et doit être utilisée uniquement pour ce produit. Si le produit est utilisé en tant que composant d’un autre produit, les informations s’y trouvant peuvent ne pas être applicables. Cette fiche ne dispense, en aucun cas, l’utilisateur du produit de respecter l’ensemble des textes législatifs, réglementaires et administratifs relatifs au produit, à la sécurité, à l’hygiène et à la protection de la santé humaine et de l’environnement.
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Pure manganese sulphate monohydrate Process category (PROC)
Location
LEV
Inhalation protection Not needed Not needed Not needed
Indoors Not needed 1 – use in closed process, no likelihood for exposure outdoors Not applicable 2 – use in closed, continuous indoors 90% process with occasional outdoors Not applicable 90% controlled exposure indoors 90% Not needed 3 – Use in closed batch process (synthesis or outdoors Not applicable 90% formulation) 4 – Use in batch and other indoors 90% 95% process (synthesis) where Use advised against opportunity for exposure arises outdoors 5 – Mixing or blending in batch indoors 90% 95% processes for formulation of preparations and articles (multistage and/or significant outdoors Use advised against contact) 8a – Transfer of substance or indoors 90% 95% preparation (charging/discharging) from/to outdoors Use advised against vessels/large containers at dedicated facilities 8b – Transfer of substance or indoors 95% 90% preparation (charging/discharging) from/to vessels/large containers at outdoors Use advised against dedicated facilities 9 – Transfer of substance or indoors 90% 95% preparation into small containers (dedicated filling outdoors Use advised against line, including weighing) 14 – Production of preparations or articles by indoors 90% 90% tabletting, compression, extrusion, pelletisation 15 – Use as laboratory reagent indoors 80% 90% (industrial use) 15 – Use as laboratory reagent (professional use, e.g. indoors 80% 90% teachers) Fertilizer use – mixing of Indoors/outdoo Not needed Not needed powders with water rs Surface treatment – mixing of Indoors/outdoo powders with water Not needed Not needed rs (professionals and consumers) default value in PSD’s interpretation of the German model (BBA, 1992)
Dermal protection 80% 80% 80% 80% 80% 80% 90%
95%
95%
90%
90%
80%
80% 80% 99%* Not needed
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40% Manganese sulphate solution Process category (PROC) Location 1 – use in closed process, no likelihood for exposure 2 – use in closed, continuous process with occasional controlled exposure 3 – Use in closed batch process (synthesis or formulation) 4 – Use in batch and other process (synthesis) where opportunity for exposure arises 5 – Mixing or blending in batch processes for formulation of preparations and articles (multistage and/or significant contact) 8a – Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities 8b – Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities 9 – Transfer of substance or preparation into small containers (dedicated filling line, including weighing) 13 – Treatment of articles by dipping and pouring 15 – Use as laboratory reagent (industrial use) 15 – Use as laboratory reagent (professional use, e.g. teachers) Fertilizer use – application
LEV
Indoors outdoors indoors outdoors
Not needed Not applicable Not needed Not applicable
Inhalation protection Not needed Not needed Not needed Not needed
Dermal protection 80% 80% 80% 80%
indoors outdoors
Not needed Not applicable
Not needed Not needed
80% 80%
indoors
Not needed
Not needed
80%
outdoors
Not applicable
Not needed
80%
indoors
Not needed
Not needed
90%
outdoors
Not applicable
Not needed
90%
indoors
Not needed
Not needed
90%
outdoors
Not applicable
Not needed
90%
indoors
Not needed
Not needed
80%
outdoors
Not applicable
Not needed
80%
indoors
Not needed
Not needed
80%
outdoors
Not applicable
Not needed
80%
indoors
Not needed
Not needed
80%
indoors
Not needed
Not needed
80%
indoors
80%
Not needed
80%
outdoors
Not applicable
Not needed
gloves*, coverall, strudy footwear, face shield
Surface treatment – brushing of preparations containing up Indoors/ Not needed Not needed Not needed to 5% MnSO4 (professionals outdoors and consumers) * 99% efficacy is assumed (default value in PSD's interpretation of the German model (BBA, 1992))
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Efficacy of dermal protection (taken from solvents phrase library ) Measure Wear suitable gloves tested to EN374. Wear chemically resistant gloves (tested to EN374) in combination with ‘basic’ employee training. Wear chemically resistant gloves (tested to EN374) in combination with specific activity training. Wear chemically resistant gloves (tested to EN374) in combination with intensive management supervision controls. Wear suitable gloves (tested to EN374) and eye protection.
Efficacy (%) 80 90 95 98 80
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EC number: 232-089-9
Manganese sulphate
CAS number: 7785-87-7
9. EXPOSURE ASSESSMENT Manganese sulphate monohydrate (CAS No 10034-96-5) and aqueous manganese sulphate solutions (CAS No 778587-7) are manufactured in the EU. Manganese sulphate is used in the manufacture of fungicides (IU 1) and in the production of other manganese based compounds and as an intermediate in a wide range of processes (IU 2). In leather tanneries, it is used as a processing aid and in the treatment of industrial effluents to facilitate the oxidation of sulphides in the wastewater (IU 3). The substance is contained in printing inks and textile dyes (IU 4). If used at industrial settings, transfer of the substance and cleaning of the equipment will take place (IU 5). Manganese sulphate may be used for small scale experiments in laboratories (IU 6). Further, formulations containing manganese sulphate is used for surface treatment of wood (IU 7) and as a fertilizer by farmers (IU 8) and professional and private gardeners (IU 9).
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Manganese sulphate
x
4
2010-07-15 CSR-PI-5.2.1
x
Con sum er use
x
x
Service life (for articles)
x
x
Waste stage
Resulting life cycle stage
CHEMICAL SAFETY REPORT
x
x
8
Surface
x
x
x
x
x
End use
7
6
x
x
3
5
x
x
x
Formu lation
2
1
Manu factu re
Laboratory reagent (IU6)
Packing and cleaning (IU5)
Printing (IU4)
Manufacture of fungicides (IU1) Production of other manganese based compounds, intermediate (IU2) Leather tanning (IU3)
Manufacture
ES number
Identified uses
Table 48: Overview on exposure scenarios and coverage of substance life-cycle
EC number: 232-089-9
7
6
5
4
3
2
1
-
Linked to Identifie d Use
7, 9a, 12, 15, 21, 23, 27, 34, 36, 37, 39 7, 9a, 12, 15, 21, 23, 27, 34, 36, 37, 39 9a, 15
1, 3, 4, 5, 6, 8, 9, 10, 12, 13, 14, 19, 20 13, 18, 19
18, 34
23, 37
1, 3, 4, 5, 6, 8, 9, 10, 12, 13, 14, 19, 20
5, 6b,
5
19, 20
3, 8, 9, 12, 16
1, 2, 3, 4,
15
8a, 8b, 9
1, 2, 3, 4, 5
1, 2, 3, 4, 5
1, 2, 3, 4, 5
1, 2, 3, 4, 5
2
Not applicable 0 (fungicide)
Process category (PROC)
Product Category (PC)
10
8
Sector of Use (SU)
CAS number: 7785-87-7
4, 11
Not applicable
Not applicable
5, 6, 8
Not applicable
Not applicable
Not applicable
Article category (AC)
3, 8c,
8b
N/A
2, 5, 8b, 8c, 10b, 11b
2,8a
4, 6a, 6b
6a
1
Environ mental categor y (ERC)
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10
Fertilizer (granulate) (IU9)
2010-07-15 CSR-PI-5.2.1
9
Fertilizer (liquid) (IU8)
EC number: 232-089-9 treatment (IU7)
x
x
x
x
CHEMICAL SAFETY REPORT
x
x
Manganese sulphate
9
8
1
CAS number: 7785-87-7
12
12
5, 10, 13, 19 1, 2, 3, 4, 5, 8a, 11, 19 1, 2, 3, 4, 5, 8a, 14, 19 Not applicable
2, 11b
2,8d
11a, 10a
EC number: 232-089-9
Manganese sulphate
CAS number: 7785-87-7
Introducing remarks: In the following, the dermal exposure is calculated without taking local exhaust ventilation into account because, according the guidance for the implementation of REACH, part D, dermal exposure for situations with LEV is often underestimated by the ECETOC TRA model. The ECETOC TRA tool calculates the dermal exposure without taking gloves into account. If the workers wear gloves, the dermal exposure will be significantly reduced compared to the values predicted by the ECETOC model. In the current assessment, a reduction of the dermal exposure concentration by 80% to 95% is taken into account for activities with obligatory use of gloves. The systemic exposure (in mg/kg body weight/day) is calculated as the sum of the part of the inhalation exposure that absorbed into the body in the alveoli of the lungs (10%, Ellingsen et al (2003)), the part of the inhaled particles that will be ingested and from which substance is absorbed via the GI tract (approx. 5% based on various TK literature) and the part of the dermal exposure that may penetrate the skin (assumed as 0.0079 based on the dermal absorption study on MnCl2), i.e.:
Equation 1: Esystemic
Einhalation 0.1 ( Einhalation Einhalation 0.1) 0.05 Edermal 0.0079 , where
Esystemic
: total systemic dose received by combined exposure, resulting from performing the
Einhalation
specified activity for 8 hours (mg/kg/day) : dose received by inhalation exposure, resulting from performing the specified activity
E dermal
for 8 hours (mg/kg/day) : dose received by dermal exposure, resulting from performing the specified activity for 8 hours wearing gloves with indicated efficacy (mg/kg/day)
The inhalation exposure for workers is converted from mg/m3 to mg/kg/day by taking into account a working shift duration of 8 hours/day, an inhalation rate of 1.25 m3/hour and a body weight of 70 kg (default). For consumers, the inhalation exposure is converted from mg/m3 to mg/kg/day by taking into account 24 hours per day, an inhalation rate of 0.83 m3/hour and a body weight of 60 kg (default). Manganese is considered as the critical toxic agent. The inhalation and dermal exposure to manganese sulphate calculated with the ECETOC TRA model are recalculated to represent the exposure to manganese by applying a correction factor of 0.36 (MnSO4 has a molecular weight of 151 g/mol, Mn of 54.9 g/mol; the portion of Mn in MnSO4 is 54.9/151=0.36).
9.1. Manufacturing of the substance (SU 8; PROC 2; PC not applicable; AC not applicable) 9.1.1. ES 1: Manufacturing of the substance The scenario is meant to cover the process control, the sampling and maintenance during the manufacture of manganese sulphate. The transfer of the products at dedicated industrial facilities as well as cleaning is covered in exposure scenario 6.
Description of activities and processes covered in the exposure scenario The manufacture of manganese sulphate monohydrate (CAS No 10034-96-5) is performed in continuous, closed dry processes at elevated pressure. The final product is a powder containing more than 95% of the substance. The manufacture of aqueous manganese sulphate solutions (CAS No 778587-7) containing approximately 40 % of the substance is performed at industrial indoor or outdoor facilities in continuous, closed wet processes by sulphuric leaching of manganese carbonate. The manufactured substances (solution or powder) have to be transferred to storage or transportation containers (covered in scenario 6).
Operational conditions Manufacturing may occur on 330 to 360 days per year during 24 hours a day.
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EC number: 232-089-9
Manganese sulphate
CAS number: 7785-87-7
Risk management measures It is recommended that the workers wear appropriate gloves if there is a potential for dermal exposure. If manganese sulphate monohydrate is manufactured, LEV with ≥90% efficacy should be present if the processing equipment is placed inside a building. If the processing equipment is placed outside, the workers should wear respiratory protection with ≥90% efficacy. If 40%-manganese sulphate solutions are manufactured, no RMMs are required to ensure safe use.
Waste related measures Wet waste from the manufacturing processes should be collected/retained in a double plastic lined collecting pond on site.
9.1.2. Exposure estimation Workers exposure The workers may experience inhalation exposure to dusts during the manufacture of manganese sulphate monohydrate. No measured long-term occupational exposure concentrations are available. The long-term occupational exposure concentrations are calculated with the ECETOC TRA tool (ECETOC 2010), taking into account a high dustiness of the substance. PROC 2 (closed continuous process with occasional exposure) is used to model the manufacturing process . The maximum 8-hour time-weighted average (TWA) concentration is 1 mg/m3 when no LEV and respiratory protection is used. This corresponds to a manganese concentration of 0.36 mg/m3. During the manufacturing of aqueous manganese sulphate solutions, no inhalation exposure is expected because the vapour pressure of manganese sulphate is very low which makes evaporation of the substance very unlikely. Further, no aerosols or mists will be formed during the manufacture process. In such cases, where the vapour pressure is very low (4 h
0.2816
0.1014
2010-07-15 CSR-PI-5.2.1
CHEMICAL SAFETY REPORT
2 Outdoors no Yes (80) >4 h 0.1972 0.0710 * No reduction of dermal exposure by LEV is taken into account. ** TRA takes into account a 30% reduction of concentrations for outdoor uses due to natural ventilation
2
Dermal protection (efficacy in %)
Table 50: expoure concentrations to manganse monhydrate in ES 1
duration
2 Outdoors Yes (90) Yes (80) >4 h 0.07 0.025 * No reduction of dermal exposure by LEV is taken into account. ** TRA takes into account a 30% reduction of concentrations for outdoor uses due to natural ventilation
2
2
2
duration
Table 49: exposure concentrations to manganse monhydrate in ES 1
EC number: 232-089-9
Inhalation exposure to MnSO4 3 (mg/m ) calculated by TRA Inhalation exposure 3 to MnSO4 (mg/m ) calculated by TRA
1.371
1.371
1.371
1.371
0.5484
0.5484
0.1097
0.1097
0.0395
0.0395
0.0018
0.0024
0.0013
0.0060
0.0015
0.0082
0.0987
0.0987
0.0987
0.0987
0.274
0.274
0.274
0.274
Dermal exposure to MnSO4 , with gloves (mg/kg/day) Dermal exposure to MnSO4 , with gloves (mg/kg/day)
Derived inhalation exposure to Mn 3 (mg/m ) Derived inhalation exposure to Mn 3 (mg/m )
Derived dermal exposure to Mn, with gloves (mg/kg/day) Derived dermal exposure to Mn, with gloves (mg/kg/day)
Dermal exposure to MnSO4 * (mg/kg/day) calculated by TRA Dermal exposure to MnSO4 * (mg/kg/day) calculated by TRA
Total systemic exposure according to Equation 1 (page 102) (mg/kg/day) Total systemic exposure according to Equation 1 (page 102) (mg/kg/day)
Quick-FDS [17477-54283-32494-014035] - 2015-11-06 - 15:04:43
EC number: 232-089-9
Manganese sulphate
CAS number: 7785-87-7
Consumer exposure No consumer exposure will result from the manufacture of manganese sulphate.
Indirect exposure of humans via the environment (oral) No significant exposure of humans via the environment is anticipated since manganese sulphate is not predicted to accumulate or be transferred to animal tissues and nor is it expected to reach significant levels in groundwater.
Environmental exposure An exposure assessment for the manufacturing life stage of Manganese sulphate has been conducted in accordance with the “Guidance on Information Requirements and Chemical Safety Assessment' (IRCSA), published by ECHA (in particular, Chapter R.16 – Environmental exposure estimation). Up to 11,000 tonnes of Manganese sulphate will be produced per year in the EU. ECETOC TRA (ECETOC/CEM 2009) has been used to estimate tier 1 exposures and EUSES 2.1 was subsequently used to refine these values. The Environmental Release category (ERCs) chosen for the scenario in ECETOC TRA and the underlying assumptions are given below. Scenario ES1
Life cycle stage manufacture
Tonnage 11,000
Fraction of tonnage for region 1*
ERC used 1
STP YES
(Manufacture) *
Assumes default of a single manufacturing facility within Europe, as a worst case
In reality, the assumptions of ERC1 are overly conservative in respect of emission fractions etc and hence EUSES 2.1 was parameterised in a refined approach taking into account the following specific data that were available. Number of emission days was assumed to be 365. Manganese sulphate is manufactured at a single facility where the wet waste from the manufacturing processes is collected in a very large collecting pond on site. This is double plastic lined and has a capacity of 100,000 tonnes. The loss of managanese sulphate to waster water can therefore be excluded for this location. Refined value
Justification
Refined release to air
0.0
EUSES default value for IC8 (metal refining and processing with main category production1b (Intermediate stored on site/continuous production). Also Technical Guidance Document default for substances of vapour pressure 4 h
0.7
0.252
1.371
0.274
0.099
0.006
2
Outdoors
-
Yes (90)
Yes (80)
>4 h
0.07
0.025
1.371
0.274
0.099
0.001
3
Indoors
no
no
Yes (80)
>4 h
1
0.36
0.343
0.069
0.025
0.008
3
Indoors
Yes (90)
no
Yes (80)
>4 h
0.1
0.036
0.343
0.069
0.025
0.001
3
Outdoors
-
no
Yes (80)
>4 h
0.7
0.252
0.343
0.069
0.025
0.005
3
Outdoors
-
Yes (90)
Yes (80)
>4 h
0.07
0.025
0.343
0.069
0.025
0.001
4
Indoors
no
no
Yes (90)
>4 h
25
9
6.86
0.686
0.247
0.188
4
Indoors
Yes (90)
Yes (95)
Yes (90)
>4 h
0.125
0.045
6.86
0.686
0.247
0.003
4
Outdoors
-
no
Yes (90)
>4 h
17.5
6.3
6.86
0.686
0.247
0.132
4
Outdoors
-
Yes (95)
Yes (90)
>4 h
0.875
0.315
6.857
0.686
0.247
0.008
5
Indoors
no
no
Yes (95)
>4 h
25
9
13.7
0.685
0.247
0.188
5
Indoors
Yes (90)
Yes (95)
Yes (95)
>4 h
0.125
0.045
13.7
0.685
0.247
0.003
5
Outdoors
-
no
Yes (95)
>4 h
17.5
6.3
13.7
0.685
0.247
0.132
5
Outdoors
-
Yes (95)
Yes (95)
>4 h
0.875
0.315
13.7
0.685
0.247
0.008
Indoors/ outdoors**
Dermal exposure to MnSO4 * (mg/kg/day) calculated by TRA
Yes (80)
Derived inhalation exposure to 3 Mn (mg/m )
no
Inhalation exposure to MnSO4 3 (mg/m ) calculated by TRA
duration
no
Respiratory protection (efficacy in %)
Indoors
LEV (efficacy in %)
1
PROC
Dermal protection (efficacy in %)
Table 57 – ES 2: Exposure to manganese sulphate monohydrate during formulation of fungicides
* No reduction of dermal exposure by LEV is taken into account. ** TRA takes into account a 30% reduction of concentrations for outdoor uses due to natural ventilation.
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EC number: 232-089-9
Manganese sulphate
CAS number: 7785-87-7
Respiratory protection (90 % efficacy)
Inhalation exposure to MnSO4 3 (mg/m ) calculated by TRA
Derived inhalation exposure to 3 Mn (mg/m )
Dermal exposure to MnSO4 * (mg/kg/day) calculated by TRA
Indoors
no
no
Yes (80)
>4 h
4 h
4 h
4 h
4 h
4 h
4 h
4 h
4 h
4 h
4 h
0.007
0.003
0.343
0.069
0.025
0.0002
2
Indoors
no
no
Yes (80)
>4 h
1
0.36
1.371
0.274
0.099
0.008
2
Indoors
Yes (90)
no
Yes (80)
>4 h
0.1
0.036
1.371
0.274
0.099
0.002
2
Outdoors
-
no
Yes (80)
>4 h
0.7
0.252
1.371
0.274
0.099
0.006
2
Outdoors
-
Yes (90)
Yes (80)
>4 h
0.07
0.025
1.371
0.274
0.099
0.001
3
Indoors
no
no
Yes (80)
>4 h
1
0.36
0.343
0.069
0.025
0.008
3
Indoors
Yes (90)
no
Yes (80)
>4 h
0.1
0.036
0.343
0.069
0.025
0.001
3
Outdoors
-
no
Yes (80)
>4 h
0.7
0.252
0.343
0.069
0.025
0.005
3
Outdoors
-
Yes (90)
Yes (80)
>4 h
0.07
0.025
0.343
0.069
0.025
0.001
4
Indoors
no
no
Yes (90)
>4 h
25
9
6.86
0.686
0.247
0.188
4
Indoors
Yes (90)
Yes (95)
Yes (90)
>4 h
0.125
0.045
6.86
0.686
0.247
0.003
4
Outdoors
-
no
Yes (90)
>4 h
17.5
6.3
6.86
0.686
0.247
0.132
4
Outdoors
-
Yes (95)
Yes (90)
>4 h
0.875
0.315
6.857
0.686
0.247
0.008
5
Indoors
no
no
Yes (95)
>4 h
25
9
13.7
0.685
0.247
0.188
5
Indoors
Yes (90)
Yes (95)
Yes (95)
>4 h
0.125
0.045
13.7
0.685
0.247
0.003
5
Outdoors
-
no
Yes (95)
>4 h
17.5
6.3
13.7
0.685
0.247
0.132
5
Outdoors
-
Yes (95)
Yes (95)
>4 h
0.875
0.315
13.7
0.685
0.247
0.008
Indoors/ outdoors**
Dermal protection (efficacy in %)
no
Respiratory protection (efficacy in %)
Indoors
LEV (efficacy in %)
1
PROC
duration
Table 73 – ES 4: Exposure to manganese sulphate monohydrate during formulation of preparations used for leather tanning
* No reduction of dermal exposure by LEV is taken into account. ** TRA takes into account a 30% reduction of concentrations for outdoor uses due to natural ventilation.
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EC number: 232-089-9
Manganese sulphate
CAS number: 7785-87-7
Leather tanning The workers may experience inhalation exposure to dusts during the use of manganese sulphate monohydrate in leather tanning. No measured long-term occupational exposure concentrations are available. The long-term occupational exposure concentrations are calculated with the ECETOC TRA tool (ECETOC 2010), taking into account a high dustiness of the substance. PROC 4 (process with opportunity for exposure) and PROC 5 (mixing and blending) are used to model the processes covered in this scenario (Table 74). The maximum 8-hour TWA concentration is 25 mg/m 3 when no LEV and respiratory protection is used. This corresponds to a manganese concentration of 9 mg/m3. During the handling of aqueous manganese sulphate solutions, no inhalation exposure is expected because the vapour pressure of manganese sulphate is very low which makes evaporation of the substance very unlikely. Further, no aerosols or mists will be formed during the processes. In such cases, where the vapour pressure is very low (4 h
0.875
0.315
6.857
0.686
0.247
0.008
5
Indoors
no
no
Yes (95)
>4 h
25
9
13.7
0.685
0.247
0.188
5
Indoors
Yes (90)
Yes (95)
Yes (95)
>4 h
0.125
0.045
13.7
0.685
0.247
0.003
5
Outdoors
-
no
Yes (95)
>4 h
17.5
6.3
13.7
0.685
0.247
0.132
5
Outdoors
-
Yes (95)
Yes (95)
>4 h
0.875
0.315
13.7
0.685
0.247
0.008
Indoors/ outdoors**
4
PROC
Dermal protection (efficacy in %)
Respiratory protection (efficacy in %)
LEV (efficacy in %)
Table 74 – ES 4: Exposure to manganese sulphate monohydrate powder
* No reduction of dermal exposure by LEV is taken into account. ** TRA takes into account a 30% reduction of concentrations for outdoor uses due to natural ventilation.
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EC number: 232-089-9
Manganese sulphate
CAS number: 7785-87-7
LEV (efficacy in %)
Respiratory protection (efficacy in %)
Dermal protection (efficacy in %)
duration
Inhalation exposure to 3 MnSO4 (mg/m ) calculated by TRA
Derived inhalation 3 exposure to Mn (mg/m )
Dermal exposure to MnSO4 * (mg/kg/day) calculated by TRA
Dermal exposure to MnSO4 , with gloves (mg/kg/day)
Derived dermal exposure to Mn, with gloves (mg/kg/day)
Total systemic exposure according to Equation 1 (page 102) (mg/kg/day)
4
Indoors
no
no
Yes (80)
>4 h
4 h
4 h
4 h
4 h
17.5
6.3
6.86
0.686
0.247
0.132
8b
Outdoors
-
Yes (95)
Yes (90)
>4 h
0.875
0.315
6.86
0.686
0.247
0.008
9
Indoors
no
no
Yes (90)
>4 h
20
7.2
6.86
0.686
0.247
0.151
9
Indoors
Yes (90)
Yes (95)
Yes (90)
>4 h
0.1
0.036
6.86
0.686
0.247
0.003
9
Outdoors
-
no
Yes (90)
>4 h
14
5.0
6.86
0.686
0.247
0.106
9
Outdoors
-
Yes (95)
Yes (90)
>4 h
0.7
0.252
6.86
0.686
0.247
0.007
Total systemic exposure according to Equation 1 (page 102) (mg/kg/day)
Inhalation exposure to MnSO4 (mg/m3) calculated by TRA
no
Derived dermal exposure to Mn, with gloves (mg/kg/day)
duration
Dermal exposure to MnSO4 , with gloves (mg/kg/day)
Dermal protection (efficacy in %)
Indoors
Respiratory protection (efficacy in %)
Indoors/ outdoors**
8a
LEV (efficacy in %)
PROC
Dermal exposure to MnSO4 * (mg/kg/day) calculated by TRA
Table 91 – ES 6: Exposure to manganese sulphate monohydrate powders
* No reduction of dermal exposure by LEV is taken into account. ** TRA takes into account a 30% reduction of concentrations for outdoor uses due to natural ventilation.
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Manganese sulphate
CAS number: 7785-87-7
Indoors/ outdoors**
LEV (efficacy in %)
Dermal protection (efficacy in %)
duration
Inhalation exposure to 3 MnSO4 (mg/m ) calculated by TRA
Derived inhalation 3 exposure to Mn (mg/m )
Dermal exposure to MnSO4 * (mg/kg/day) calculated by TRA
Dermal exposure to MnSO4 , with gloves (mg/kg/day) Derived dermal exposure to Mn, with gloves (mg/kg/day)
Total systemic exposure according to Equation 1 (page 102) (mg/kg/day)
8a
Indoors
no
no
Yes (90)
>4 h
4 h
4 h
4 h
4 h
4 h
4 h
0.007
0.003
0.343
0.069
0.025
0.0002
2
Indoors
no
no
Yes (80)
>4 h
1
0.36
1.371
0.274
0.099
0.008
2
Indoors
Yes (90)
no
Yes (80)
>4 h
0.1
0.036
1.371
0.274
0.099
0.002
2
Outdoors
-
no
Yes (80)
>4 h
0.7
0.252
1.371
0.274
0.099
0.006
2
Outdoors
-
Yes (90)
Yes (80)
>4 h
0.07
0.025
1.371
0.274
0.099
0.001
3
Indoors
no
no
Yes (80)
>4 h
1
0.36
0.343
0.069
0.025
0.008
3
Indoors
Yes (90)
no
Yes (80)
>4 h
0.1
0.036
0.343
0.069
0.025
0.001
3
Outdoors
-
no
Yes (80)
>4 h
0.7
0.252
0.343
0.069
0.025
0.005
3
Outdoors
-
Yes (90)
Yes (80)
>4 h
0.07
0.025
0.343
0.069
0.025
0.001
4
Indoors
no
no
Yes (90)
>4 h
25
9
6.86
0.686
0.247
0.188
4
Indoors
Yes (90)
Yes (95)
Yes (90)
>4 h
0.125
0.045
6.86
0.686
0.247
0.003
4
Outdoors
-
no
Yes (90)
>4 h
17.5
6.3
6.86
0.686
0.247
0.132
4
Outdoors
-
Yes (95)
Yes (90)
>4 h
0.875
0.315
6.857
0.686
0.247
0.008
5
Indoors
no
no
Yes (95)
>4 h
25
9
13.7
0.685
0.247
0.188
5
Indoors
Yes (90)
Yes (95)
Yes (95)
>4 h
0.125
0.045
13.7
0.685
0.247
0.003
5
Outdoors
-
no
Yes (95)
>4 h
17.5
6.3
13.7
0.685
0.247
0.132
5
Outdoors
-
Yes (95)
Yes (95)
>4 h
0.875
0.315
13.7
0.685
0.247
0.008
Indoors/ outdoors**
Dermal protection (efficacy in %)
no
Respiratory protection (efficacy in %)
Indoors
LEV (efficacy in %)
1
PROC
duration
Table 111 – ES 9: Exposure to manganese sulphate monohydrate during formulation of fertilizers
* No reduction of dermal exposure by LEV is taken into account. ** TRA takes into account a 30% reduction of concentrations for outdoor uses due to natural ventilation.
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Manganese sulphate
CAS number: 7785-87-7
Application of fertilizers The worker exposure to manganese sulphate during the application of the fertilizer is calculated with the PSD's interpretation of the German model (BBA, 1992). Concentrated manganese sulphate powder is mixed with water and is applied to the field by a tractor-mounted or trailed broadcast air assisted sprayer. 7 kg manganese sulphate are applied per ha, corresponding to around 2.5 kg manganese. The workers are expected to fertilize up to 8 ha per day. The predicted inhalation and the dermal exposure are given in mg/day in the PSD spreadsheet. These values are converted to mg/m3 and mg/kg body weight/day, respectively, by taking into account a respiratory volume of 10 m3 per worker per work day and a body weight of 70 kg. The inhalation exposure during mixing and loading is predicted to be 3.92 mg MnSO4/day (0.392 mg MnSO4/m3) and the dermal exposure is 3.36 mg MnSO4/day (0.048 mg MnSO4/kg body weight/day) if the workers wear gloves .The predicted inhalation exposure during the application is 1.01 mg MnSO4/day (0.10 mg MnSO4/m3) and the dermal exposure 30.632 mg MnSO4/day (0.438 mg MnSO4/kg body weight/day).
gloves
4.8
Gloves, coverall, application 0.101 0.0363 9.2 sturdy footwear, face shield * An efficacy of 99% if taken into account for gloves (PSD default value).
Total systemic exposure according to Equation 1 (page 102) (mg/kg/day)
Derived dermal exposure to Mn, with RMMs * (mg/kg/day)
0.1411
Dermal exposure to MnSO4 , with RMMs * (mg/kg/day)
0.392
Dermal exposure to MnSO4 * (mg/kg/day) calculated by PSD without RMMs
Derived inhalation exposure to Mn 3 (mg/m )
Mixing/loading
Inhalation exposure to 3 MnSO4 (mg/m ) calculated by PSD
RMMs
Activity
Table 112 – ES 9: Exposure concentrations
0.048
0.0173
0.0031
0.092
0.0331
0.0010
Consumer exposure There will be no consumer exposure from the uses described in this scenario.
Indirect exposure of humans via the environment (oral) No significant exposure of humans via the environment is anticipated since manganese sulphate is not predicted to accumulate or be transferred to animal tissues and nor is it expected to reach significant levels in groundwater.
Environmental exposure An exposure assessment for formulation/use of Manganese sulphate as a liquid fertilizer has been conducted in accordance with the “Guidance on Information Requirements and Chemical Safety Assessment' (IRCSA), published by ECHA (in particular, Chapter R.16 – Environmental exposure estimation). Up to 5000 tonnes of Manganese sulphate will be used per year in the EU. ECETOC TRA (ECETOC/CEM 2009) has been used to estimate tier 1 exposures. The Environmental Release category (ERCs) chosen for the scenario in ECETOC TRA and the underlying assumptions are given below. Scenario
Life cycle stage ES9
(Fertilizer - liquid)
Tonnage 5000
Fraction of tonnage for region 0.1
ERC used 2, 8d
STP YES
Formulation/end use
ERC8d is used as a worst-case (100% release to water compared with 2% release for ERC2). The formulation stage is covered separately in ES10.
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CAS number: 7785-87-7
The following substance specific parameters were entered into the ECETOC TRA model. Molecular weight:
151 g/mol
Vapour pressure:
1x 10-6 Pa at 20°C (default for metals and therefore considered reasonable for a solid substance containing various metallic compounds)
Water solubility:
450 g/L at 20°C (measured value Manganese sulphate)
Log Kow:
Not available, or required
Biodegradability:
No degradation (default for metals therefore considered reasonable for a solid substance containing various inorganic metallic compounds)
Kd (soil, sediment ,suspended solids): 1355 ml/g (median value from experimental study over 100 days with Manganese chloride, another soluble form of Manganese)
Environmental releases Table 113: Summary of the releases to the environment Assessment
Release from point source (kg/d) (local exposure estimation)
Compartment
Tier 1
Total release for regional exposure estimation (kg/d)
Justification
Aquatic (without STP)
2.74
1100
Release prior to STP based on tonnage of 5000 and ERC8d Default release of 100%.
Aquatic (after STP)
-
271
Regional loss to freshwater
Air (direct + STP)
-
1370
based on tonnage of 5000 and ERC8d Default release of 100%.
Soil (direct releases only – to industrial soil)
-
30.1
based on tonnage of 5000 and ERC8d Default release of 20%. (regional only)
Exposure concentration in sewage treatment plants (STP) Table 114: Predicted Exposure Concentrations (PEC) in sewage
Tier 1
Value
Justification
Concentration in sewage (PECstp)(in mg/l)
1.3
ECETOC-TRA calculation
Concentration in sewage sludge (in mg/kg d.w.)
Not relevant
Not simulated in ECETOC-TRA
By definition, manganese sulphate is applied to agricultural fields or pots of soil where there is a manganese deficiency and therefore the application of the manganese sulphate will not result in levels significantly about the natural range of manganese levels in soil. Since the compound is specifically targeted to soil application there can be expected to be no
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significant loss to STP. Overall it is therefore concluded that there is no adverse environmental impact from the formulation/use of manganese sulphate as a liquid fertilizer and that the tier 1 PEC values in STP have no relevance in this context.
Exposure concentration in aquatic pelagic compartment Table 115: Predicted Exposure Concentrations (PEC) in aquatic compartment
Tier 1
Compartments
PEC aquatic (local)
Justification
Freshwater (in mg/l)
0.696
ECETOC-TRA Calculation
Marine water (in mg/l)
0.0709
ECETOC-TRA Calculation
By definition, manganese sulphate is applied to agricultural fields or pots of soil where there is a manganese deficiency and therefore the application of the manganese sulphate will not result in levels significantly about the natural range of manganese levels in soil. Since the compound is specifically targeted to soil application there can be expected to be no significant loss to surface water. Overall it is therefore concluded that there is no adverse environmental impact from the formulation/use of manganese sulphate as a liquid fertilizer and that the tier 1 PEC values in surface waters have no relevance in this context. Exposure concentration in sediments Table 116: Predicted Exposure Concentrations (PEC) in sediments
Tier 1
Compartments
PEC sediment (local)
Justification
Freshwater sediments (in mg/kg d.w)
946
ECETOC-TRA
Marine water sediments (in mg/kg d.w.)
96.4
ECETOC-TRA
By definition, manganese sulphate is applied to agricultural fields or pots of soil where there is a manganese deficiency and therefore the application of the manganese sulphate will not result in levels significantly about the natural range of manganese levels in soil. Since the compound is specifically targeted to soil application there can be expected to be no significant loss to sediment. Overall it is therefore concluded that there is no adverse environmental impact from the formulation/use of manganese sulphate as a liquid fertilizer and that the tier 1 PEC values in sediment have no relevance in this context.
Exposure concentrations in soil and groundwater Table 117: Predicted Exposure Concentrations (PEC) in soil and groundwater
Tier 1
PEC soil/groundwater (local)
Justification
Soil (mg/kg d.w)
955
ECETOC-TRA
Groundwater(mg/l)
-
Not reported in ECETOC-TRA
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CAS number: 7785-87-7
By definition, manganese sulphate is applied to agricultural fields or pots of soil where there is a manganese deficiency and therefore the application of the manganese sulphate will not result in levels significantly about the natural range of manganese levels in soil. Overall it is therefore concluded that there is no adverse environmental impact from the formulation/use of manganese sulphate as a liquid fertilizer and that the tier 1 PEC values in soil have no relevance in this context. Atmospheric compartment Table 118: Predicted Exposure Concentration (PEC) in air PEC air (local) Tier 1
Annual average (μg/m3)
-
Justification Not reported in ECETOC-TRA
9.10. Formulation of granulate fertilizers and professional and private use of fertiliser granulates containing MnSO4 (SU no code; PROC 1, 2, 3, 4, 5, 8a, 14,19; PC 12; AC not applicable) – IU 9 9.10.1. ES 10: Professional and private use of fertiliser granulates containing MnSO4 The scenario is meant to cover the formulation of granulate fertilizers, the preparation of solutions by dissolving granular fertilisers in water (emptying of transport bags into vessel, mixing with water, filling of watering can or irrigation system) and the irrigation of plants. Further, it covers the use of fertilizer in form of a small rod that can be placed in flowerpots and is meant to release the nutrients over a longer period.
Description of activities and processes covered in the exposure scenario The formulation of fertilizers containing manganese sulphate takes place in a range of processes, such as closed, contained processes with almost no possibility of direct contact to semi-closed or open multistage processes providing the opportunity for significant exposure at any stage. Fertilisers containing manganese sulphate are available to professional and private users. These preparations normally are in the form of granulates, which can be dissolved in irrigation water or in the form of a small rod that can be placed in flowerpots and is meant to release the nutrients over a longer period. Gardeners may use such fertilisers regularly, e.g. on 100 to 150 days per year, whereas private users will use the fertilisers infrequently, e.g. 4 times a year.
Operational conditions Formulation of fertilizers with manganese sulphate monohydrate powder may occur on approximately 200 to 300 days per year up to 24 hours a day. The exposure duration during the application of the fertilizer is expected to be considerably less than 8 hours per day.
Risk management measures It is recommended that the workers wear appropriate gloves during formulation of fertilizer if there is a potential for dermal exposure. If manganese sulphate monohydrate is formulated in closed formulation processes with no likelihood for exposure, no additional RMMs are needed. If manganese sulphate monohydrate is formulated in closed continuous formulation processes with occasional controlled exposure (e.g. sampling), LEV with ≥90% efficacy should be present if the process equipment is places inside a building. If the process equipment is placed outside, the workers have to wear respiratory protection with ≥90% efficacy. If manganese sulphate monohydrate is formulated in open processes running inside a building, LEV with ≥90% efficacy should be installed and the workers have to wear respiratory protection with ≥95% efficacy. If such open processes are run outside, no safe conditions could be shown and it should therefore be avoided to run open processes outside if manganese sulphate monohydrate is used in formulation. No RMMs are necessary if fertilizer in granulate form is dissolved in water and subsequently poured on plants or if rods are placed in flowerpots.
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Manganese sulphate
CAS number: 7785-87-7
Waste related measures No specific measures required for the environment
9.10.2. Exposure estimation Worker’s exposure estimation Formulation The workers may experience inhalation exposure to dusts when using manganese sulphate monohydrate in the formulation of fertilizers. The long-term occupational exposure concentrations are calculated with the ECETOC TRA tool (ECETOC 2010), taking into account a high dustiness of the substance. PROC 1 (closed process), PROC 2 (closed continuous process with occasional exposure), PROC 3 (closed batch process), PROC 4 (process with opportunity for exposure), PROC 5 (mixing and blending) and PROC 14 (tabletting, compression) are used to model the formulation processes covered in this scenario. The maximum 8-hour TWA concentration of dusts is 25 mg/m3 for open and mixing processes when no LEV and respiratory protection is used. This corresponds to a manganese concentration of 9 mg/m 3. The modelled dermal exposure to manganese sulphate monohydrate is 0.34 mg/kg body weight/day for PROC 1, 1.37 mg/kg body weight/day for PROC 2, 0.34 mg/kg body weight/day for PROC 3, 6.86 mg/kg body weight/day for PROC 4, 13.7 mg/kg body weight/day for PROC 5 and 3.43 mg/kg body weight/day for PROC 14 in the absence of gloves and other protective clothes. Table 119 – ES 10: Exposure to manganese sulphate monohydrate
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Dermal exposure to MnSO4 * (mg/kg/day) calculated by TRA
Dermal exposure to MnSO4 , with gloves (mg/kg/day)
Derived dermal exposure to Mn, with gloves (mg/kg/day)
Total systemic exposure according to Equation 1 (page 102) (mg/kg/day)
no
Yes (80)
>4 h
0.01
0.004
0.343
0.069
0.025
0.0003
1
Outdoors
-
no
Yes (80)
>4 h
0.007
0.003
0.343
0.069
0.025
0.0002
2
Indoors
no
no
Yes (80)
>4 h
1
0.36
1.371
0.274
0.099
0.008
2
Indoors
Yes (90)
no
Yes (80)
>4 h
0.1
0.036
1.371
0.274
0.099
0.002
2
Outdoors
-
no
Yes (80)
>4 h
0.7
0.252
1.371
0.274
0.099
0.006
2
Outdoors
-
Yes (90)
Yes (80)
>4 h
0.07
0.025
1.371
0.274
0.099
0.001
3
Indoors
no
no
Yes (80)
>4 h
1
0.36
0.343
0.069
0.025
0.008
3
Indoors
Yes (90)
no
Yes (80)
>4 h
0.1
0.036
0.343
0.069
0.025
0.001
3
Outdoors
-
no
Yes (80)
>4 h
0.7
0.252
0.343
0.069
0.025
0.005
3
Outdoors
-
Yes (90)
Yes (80)
>4 h
0.07
0.025
0.343
0.069
0.025
0.001
4
Indoors
no
no
Yes (90)
>4 h
25
9
6.86
0.686
0.247
0.188
4
Indoors
Yes (90)
Yes (95)
Yes (90)
>4 h
0.125
0.045
6.86
0.686
0.247
0.003
4
Outdoors
-
no
Yes (90)
>4 h
17.5
6.3
6.86
0.686
0.247
0.132
4
Outdoors
-
Yes (95)
Yes (90)
>4 h
0.875
0.315
6.857
0.686
0.247
0.008
5
Indoors
no
no
Yes (95)
>4 h
25
9
13.7
0.685
0.247
0.188
5
Indoors
Yes (90)
Yes (95)
Yes (95)
>4 h
0.125
0.045
13.7
0.685
0.247
0.003
5
Outdoors
-
no
Yes (95)
>4 h
17.5
6.3
13.7
0.685
0.247
0.132
5
Outdoors
-
Yes (95)
Yes (95)
>4 h
0.875
0.315
13.7
0.685
0.247
0.008
14
Indoors
no
No
80%
>4 h
10
3.6
3.43
0.686
0.247
0.077
14
Indoors
Yes (90)
Yes (90)
80%
>4 h
0.1
0.036
3.43
0.686
0.247
0.003
Indoors/ outdoors**
Dermal protection (efficacy in %)
no
Respiratory protection (efficacy in %)
Indoors
LEV (efficacy in %)
1
PROC
Derived inhalation exposure to 3 Mn (mg/m )
CAS number: 7785-87-7
Inhalation exposure to MnSO4 3 (mg/m ) calculated by TRA
Manganese sulphate
duration
EC number: 232-089-9
* No reduction of dermal exposure by LEV is taken into account. ** TRA takes into account a 30% reduction of concentrations for outdoor uses due to natural ventilation. Application of fertilizer The professionals may be exposed to manganese sulphate when transferring the granulates from commercial bags to a vessel (PROC 8a), when dissolving the granulates in water (PROC 19) and when pouring the solution over the plants (PROC 8a). It is not expected that aerosols are formed during the pouring of the solution. The exposure concentrations are calculated with PSD's interpretation of the German model (BBA, 1992). For the mixing of wettable granulates with water, the tool predicts an inhalation exposure of 0.02 mg/kg active substance. It is expected that professional gardeners mix up to 1 kg manganese sulphate contained in wettable fertilizer granulates with water during a working day and therefore the exposure to MnSO 4 is 0.02 mg/day. This value is converted to mg/m3 by taking into account a respiratory volume of 10 m3 per worker per work day, resulting in an exposure concentrations of 0.002 mg/m3. The dermal exposure is predicted to be 21 mg/day. This value is converted to mg/kg body weight/day by taking into account a body weight of 70 kg, resulting in 0.3 mg/kg body weight/day. No specific model for the pouring of fertilizers is available, but as no aerosols are built during the pouring and because the vapour pressure of manganese sulphate is very low, it is expected that the exposure during the mixing represents a worst case and is therefore covering the application of the fertilizer as well. During the use of small rods that can be placed in flowerpots, no inhalation exposure is expected. The dermal exposure is expected to be comparable to the one calculated with the PSD’s interpretation of the German model for mixing and loading. 2010-07-15 CSR-PI-5.2.1
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CAS number: 7785-87-7
-
0.3
0.108
Total systemic exposure according to Equation 1 (page 102) (mg/kg/day)
0.00072
Derived dermal exposure to Mn, (mg/kg/day)
0.002
Dermal exposure to MnSO4 (mg/kg/day) calculated by PSD
Derived inhalation exposure to Mn 3 (mg/m )
Mixing/loading
Inhalation exposure to 3 MnSO4 (mg/m ) calculated by PSD
RMMs
Activity
Table 120 – ES 10: Exposure to manganese sulphate during application of fertilizer
0.00089
Consumer exposure Consumers may experience the same acute exposure to manganese sulphate as the professionals when using fertilizer, i.e. an inhalation exposure of 0.002 mg/m3 and a dermal exposure of 0.3 mg/kg body weight/day. However, it is expected that they use fertilizers infrequently and for short durations only.
Indirect exposure of humans via the environment (oral) No significant exposure of humans via the environment is anticipated since manganese sulphate is not predicted to accumulate or be transferred to animal tissues and nor is it expected to reach significant levels in groundwater.
Environmental exposure An exposure assessment for formulation/use of Manganese sulphate as a granulate fertilizer has been conducted in accordance with the “Guidance on Information Requirements and Chemical Safety Assessment' (IRCSA), published by ECHA (in particular, Chapter R.16 – Environmental exposure estimation). Up to 3000 tonnes of Manganese sulphate will be used per year in the EU. ECETOC TRA (ECETOC/CEM 2009) has been used to estimate tier 1 exposures and EUSES 2.1 was subsequently used to refine these values. The Environmental Release category (ERCs) chosen for the scenario in ECETOC TRA and the underlying assumptions are given below. Scenario
Life cycle stage
ES10 (Fertilizer - granulate)
Tonnage 3000
Fraction of tonnage for region 0.1
ERC used 2, 11b
STP YES
Formulation/end use
ERC11b is used as a worst-case (100% release to water compared with 2% release for ERC2). The following substance specific parameters were entered into the ECETOC TRA model. Molecular weight:
151 g/mol
Vapour pressure:
1x 10-6 Pa at 20°C (default for metals and therefore considered reasonable for a solid substance containing various metallic compounds)
Water solubility:
450 g/L at 20°C (measured value Manganese sulphate)
Log Kow:
Not available, or required
Biodegradability:
No degradation (default for metals therefore considered reasonable for a solid substance containing various inorganic metallic compounds)
Kd (soil, sediment ,suspended solids): 1355 ml/g (median value from experimental study over 100 days with Manganese chloride, another soluble form of Manganese) Environmental releases
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CAS number: 7785-87-7
Table 121: Summary of the releases to the environment Assessment
Release from point source (kg/d) (local exposure estimation)
Compartment
Tier 1
Total release for regional exposure estimation (kg/d)
Justification
Aquatic (without STP)
1.64
658
Release prior to STP based on tonnage of 3000 and ERC11b Default release of 100%.
Aquatic (after STP)
-
163
Regional loss to freshwater
Air (direct + STP)
-
822
based on tonnage of 3000 and ERC11b Default release of 100%.
Soil (direct releases only – to industrial soil)
-
-
based on tonnage of 35000 and ERC11b Default release of 0%. (regional only)
Exposure concentration in sewage treatment plants (STP) Table 122: Predicted Exposure Concentrations (PEC) in sewage
Tier 1
Value
Justification
Concentration in sewage (PECstp)(in mg/l)
0.779
ECETOC-TRA calculation
Concentration in sewage sludge (in mg/kg d.w.)
Not relevant
Not simulated in ECETOC-TRA
By definition, manganese sulphate is applied to agricultural fields or pots of soil where there is a manganese deficiency and therefore the application of the manganese sulphate will not result in levels significantly about the natural range of manganese levels in soil. Since the compound is specifically targeted to soil application there can be expected to be no significant loss to STP. Overall it is therefore concluded that there is no adverse environmental impact from the formulation/use of manganese sulphate as a granulate fertilizer (including slow release rod) and that the tier 1 PEC values in STP have no relevance in this context.
Exposure concentration in aquatic pelagic compartment Table 123: Predicted Exposure Concentrations (PEC) in aquatic compartment
Tier 1
Compartments
PEC aquatic (local)
Justification
Freshwater (in mg/l)
0.649
ECETOC-TRA Calculation
Marine water (in mg/l)
0.0658
ECETOC-TRA Calculation
By definition, manganese sulphate is applied to agricultural fields or pots of soil where there is a manganese deficiency and therefore the application of the manganese sulphate will not result in levels significantly about the natural range of manganese levels in soil. Since the compound is specifically targeted to soil application there can be expected to be no
2010-07-15 CSR-PI-5.2.1
CHEMICAL SAFETY REPORT
Quick-FDS [17477-54283-32494-014035] - 2015-11-06 - 15:04:43
86/87
EC number: 232-089-9
Manganese sulphate
CAS number: 7785-87-7
significant loss to surface water. Overall it is therefore concluded that there is no adverse environmental impact from the formulation/use of manganese sulphate as a granulate fertilizer (including slow release rod) and that the tier 1 PEC values in surface waters have no relevance in this context. Exposure concentration in sediments Table 124: Predicted Exposure Concentrations (PEC) in sediments
Tier 1
Compartments
PEC sediment (local)
Justification
Freshwater sediments (in mg/kg d.w)
876
ECETOC-TRA
Marine water sediments (in mg/kg d.w.)
89.4
ECETOC-TRA
By definition, manganese sulphate is applied to agricultural fields or pots of soil where there is a manganese deficiency and therefore the application of the manganese sulphate will not result in levels significantly about the natural range of manganese levels in soil. Since the compound is specifically targeted to soil application there can be expected to be no significant loss to sediment. Overall it is therefore concluded that there is no adverse environmental impact from the formulation/use of manganese sulphate as a granulate fertilizer (including slow release rod) and that the tier 1 PEC values in sediment have no relevance in this context.
Exposure concentrations in soil and groundwater Table 125: Predicted Exposure Concentrations (PEC) in soil and groundwater
Tier 1
PEC soil/groundwater (local)
Justification
Soil (mg/kg d.w)
954
ECETOC-TRA
Groundwater(mg/l)
-
Not reported in ECETOC-TRA
By definition, manganese sulphate is applied to agricultural fields or pots of soil where there is a manganese deficiency and therefore the application of the manganese sulphate will not result in levels significantly about the natural range of manganese levels in soil. Overall it is therefore concluded that there is no adverse environmental impact from the formulation/use of manganese sulphate as a granulate fertilizer (including slow release rod) and that the tier 1 PEC values in soil have no relevance in this context. Atmospheric compartment Table 126: Predicted Exposure Concentration (PEC) in air PEC air (local) Tier 1
Annual average (μg/m3)
2010-07-15 CSR-PI-5.2.1
-
CHEMICAL SAFETY REPORT
Quick-FDS [17477-54283-32494-014035] - 2015-11-06 - 15:04:43
Justification Not reported in ECETOC-TRA
87/87
