EC number: dibutyl phthalate CAS number: 201-5574 84-74-2 9.1. Exposure scenario 1: Use as an absorption solvent in a closed system in the manufacture of Maleic Anhydride (MA) PC 2: Adsorbents Sector of use: SU 8, Manufacture of bulk, large scale chemicals (including petroleum products) |Environment contributing scenario(s): Use as an absorption solvent in a closed system in the manufacture of MA ERC4 Use as an absorption solvent in a closed system in the manufacture of MA ERC7 Worker contributing scenario(s): |Closed system (minimal contact during routine operations) PROC | Material transfer PROC 8b Laboratory use PROC 15 Description of the activities and technical processes covered in the exposure scenario: This scenario covers all the industrial activities associated with use of dibutyl phthalate as a solvent in closed system in manufacture of MA. Explanation on the approach taken for the ES Two environmental contributing scenarios are reported for formulation. Operational conditions and release factors for ERC 4 and ERC 7 are based on specific data from maleic anhydride production site of Sasol- Huntsman GmbH & Co KG in Germany, Dibutyl phthalate (DBP) is used as processing aid (absorbent) in the production process of maleic anhydride and is not detectable in the final product. The DBP solvent is recovered and recycled for reuse within the plant. DBP losses are due to decomposition of DBP and to vapour phase losses from distillation tower overheads — each such stream is incinerated. Dibutyl phthalate is used in closed, continuous process with occasional controlled exposure and is controlled and operated via a central control room, Standard operational procedures are in place were the required personal protective equipment requirements are strictly mandatory. Potential exposure to dibutyl phthalate can occur during the sampling (one sample per day in average, in duration of two minutes). Exposure assessment for PROC 8b the RISKOFDERM (version 2.1) modelling tool was used to derive dermal ‘exposure estimate, since Tier I model (ECETOC TRA) did not indicate safe use. As a relevant activity in RISKOFDERM for these assessments was chosen the process refers to filling, mixing and loading. Regarding PROC 8b and the unloading of dibutyl phthalate (DBP) this site specific information was considered: ‘The Moers plant needs 2-3 trucks per month of DBP. These trucks are unloaded within one hour by one worker. The DBP is at ambient temperature, The amount of DBP is about 20 tons per one unloading. The truck container is connected to a capsuled unloading pump by a flexible stainless steel hose. The work is done within two minutes, where the worker closes the quick connection to the truck. This is the time of a possible exposure, The valves at the truck and at the pumps are opened. The pump is started and the DBP is filled via hard piped system into a storage tank. The tank is connected to a vent gas system. The truck replaced the unloaded DBP by sucking in air, The system to the pump is also a suction system which avoids leaks to atmosphere. Once the truck is empty also the rest of DBP in the flexible hose is sucked in, No leakages occur during disconnecting the hose 2013-07-17 CHEMICAL SAFETY REPORT aEC number; dibutyl phthalate CAS number: 201-5574 84-742 9.1.1. Environmental contributing scenario 1: Use as an absorption solvent in a closed system in the manufacture of MA—ERC 4 [Amount used, frequency and duration of use (or from service life) = Daily use at site: <= 1.7 tonnes/day + Annual use at a site 500 tonnes/year + Percentage of tonnage used at regional scale: = 100 % [Technical and organisational conditions and measures + Exhaust air treatment: Onsite incineration [Effectiveness Air: 99%] [Conditions and measures related to sewage treatment plant = Municipal STP: Yes [Effectiver = Discharge rate of STP: >= 263 m3/d + Application of the STP sludge on agricultural soil: No [Conditions and measures related to treatment of waste (including article waste) + Particular considerations on the waste treatment operations: Closed system required to prevent any release to lhe environment, |Other conditions affecting environmental exposure + Receiving surface water flow rate: >= 1.8E4 mid + On site treatment of wastewater: pH adjustment and subsequent filration/sedimentation - metal salts other lthan Ni [Effectiveness Water: 99%] 9, 2. Releases ‘The local releases to the environment are reported in the following table. ‘Table 5. Local releases to the environment [Release [Release factor estimation Explanation / Justification lmethod Water [Measured release [Final release factor: 0% Local release rate: 0 ky/day (site specific) Explanation / Justification: Biological waste water treatment plant (on site). Sludge is eliminated in external incineration Air [Measured release Final release factor: 0% [Local release rate: 0 kg/day (Site specific) Explanation / Justification: The process off gas stream and all lother waste streams are thermally treated by an incinerator to |completely climinate hydrocarbon emissions to the environment lby thermal degradation. The incinerator is equipped with an lonline analyzer to measure and record the effectiveness of the |combustion. The effectiveness of the treatment related to the [contained hydrocarbons and specifically for the relevant substance [DBP is 100% Soil [Release factor Final release factor: 0% [Explanation / Justification: No direct release to soil (closed system) Releases to waste Release factor to waste from the process: 6.75% Dibutyl phthalate is used as processing aid in the production process of maleic anhydride and is not detectable in CHEMICAL SAFETY REPORT 3EC number; dibutyl phthalate CAS number: 201-5574 84-74-2 the final product. Waste waters are treated by biological waste water treatment plant and concentration of dibutyl phthalate in treats waste water is 0.00 mg/L.. The maleic anhydride production plant was built and ‘operated in strict compliance with the German water and soil protection regulations (VAWS). The process off gas stream and all other waste streams are thermally treated by an incinerator to completely eliminate hydrocarbon emissions to the environment by thermal degradation. Based on available data from the clients the highest volume of substance used in identified use as solvent in maleic anhydride production is 53.14 t/a and 10.86954 kg/d waste is produced. 3.66 t/a of waste containing dibutyl phthalate entering to hazardous waste incineration ic, 6.75% (Fwaste_HW_incineration = 0.0675), Release factor to waste from on site treatment: 0% ‘Waste containing substance is incinerated on site, No waste containing DBP is expected to be generated from incineration process 9. 3. Exposure and risks for the environment and man via the environment ‘The exposure concentrations and risk characterisation ratios (RCR) are reported in the following table, ‘Table 6. Exposure concentrations and risks for the environment Protection target Exposure concentration Risk characterisation Freshwater [Local PEC: 1.531E-6 mg/l. RCR <0.01 [Sediment (Freshwater) [Local PEC: 1.826E-4 mgikg dw RCR<001 [Marine water [Local PEC: 1-342E-7 mg/L RCR<0.01 [Sediment (marine water) GO1E-5 mgike w RCR<0.01 Predator (freshwater) ‘TS5E-6 mgike ww ROR <0.01 Predator (marine water) AISE-T meike ww RCR <0.01 Top predator (marine water) [Local PEC: 2.415E-7 mg/kg ww RCR<0.01 [Sewage treatment plant [Local PEC: 0 mg/L RCR<0.01 [Agricultural soil [Local PEC: 2.294E-7 meike dw ROR =0.01 Predator (terrestrial) [Local PEC: 5.855E-8 mg/kg ww ROR <0.01 Man via Environment - [Local PEC: 5.441E-9 mg/m” ROR = 0.01 Huhalation [Man via Environment - Oral _ [Exposure via food consumption: 4.767E- [RCR <0.01 [7 mg/kg bwiday [Man via environment - ROR <0.01 |combined routes ‘Table 7. Contribution to oral intake for man via the environment from local contribution [Type of food Kstimated daily dose |Concentration in food [Drinking water __[2.187E-8 mg/kg bw/day 7.65367 mg/L [Fish 4.526E-9 mgikg bwiday 2.755E-6 melke ww [Leaf crops 4.284E-7 mg/kg bwiday [2.499E-5 melke ww Root crops 1.338E-8 mg/kg bwiday 2440-6 make ww Meat 5.395E-9 mgikg bwiday 1.2558-6 mylke ww Milk 3.18E-9 melke bwiday 5.968E-7 mgike ww CHEMICAL SAFETY REPORT 6EC number; dibutyl phthalate CAS number: 201-5574 84-74-2 9.1.2. Environmental contributing scenario 2: Use as an absorption solvent in a closed system in the manufacture of MA~ ERC 7 [Amount used, frequency and duration of use (or from service life) = Daily use at site: <= 1.7 tonnes/day + Annual use ata site 500 tonnes/year + Percentage of tonnage used at regional scale: = 100 % [Technical and organisational conditions and measures + Exhaust air treatment: Onsite incineration [Effectiveness Air: 99%] [Conditions and measures related to sewage treatment plant + Municipal STP: Yes [Effectiveness Water: 100%] = Discharge rate of STP: >= 2E3 mid + Application of the STP sludge on agricultural soil: No [Conditions and measures related to treatment of waste (including article waste) = Particular considerations on the waste treatment operations: Closed system required to prevent any release to lhe environment, |Other conditions affecting environmental exposure + Receiving surface water flow rate: >= 1.8E4 m3/d + On site treatment of wastewater: pH adjustment and subsequent filration/sedimentation - metal salts other than Ni [Effectiveness Water: 99%] 9, 2. Releases ‘The local releases to the environment are reported in the following table. ‘Table 8, Local releases to the environment [Release [Release factor estimation Explanation / Justification lmethod Water [Measured release [Final release factor: 0% Local release rate: 0 ky/day (site specific) Explanation / Justification: Biological waste water treatment plant (on site). Sludge is eliminated in external incineration Air [Measured release Final release factor: 0% [Local release rate: 0 kg/day (Site specific) Explanation / Justification: The process off gas stream and all lother waste streams are thermally treated by an incinerator to |completely climinate hydrocarbon emissions to the environment, lby thermal degradation. The incinerator is equipped with an Jonline analyzer to measure and record the effectiveness of the |combustion. The effectiveness of the treatment related to the |contained hydrocarbons and specifically for the relevant substance [DBP is 100% Soll [Release factor Final release factor: 0% [Explanation / Justification: No direct release to soil (closed system) Releases to waste Release factor to waste from the process: 6.75% Dibutyl phthalate is used as processing aid in the production process of maleic anhydride and is not detectable in CHEMICAL SAFETY REPORT 7EC number; dibutyl phthalate CAS number: 201-5574 84-74-2 the final product, Waste waters are treated by biological waste water treatment plant and concentration of dibutyl phthalate in treated waste water is 0.00 mg/L. The maleic anhydride production plant was built and ‘operated in strict compliance with the German water and soil protection regulations (VAWS). The process off gas stream and all other waste streams are thermally treated by an incinerator to completely eliminate hydrocarbon emissions to the environment by thermal degradation. Based on available data from the clients the highest volume of substance used in identified use as solvent in maleic anhydride production is 53.14 va and 10,86954 kg/d waste is produced. 3.66 tia of waste containing Dibutyl phthalate entering to hazardous waste incineration i.e, 6.75% (Fwaste_HW_incineration = 0.0675) Release factor to waste from on site treatment: 0% ‘Waste containing substance is incinerated on site, No waste containing DBP is expected to be generated from incineration process 9.1.2.3. Exposure and risks for the environment and man via the environment ‘The exposure concentrations and risk characterisation ratios (RCR) are reported in the following table. ‘Table 9. Exposure concentrations and risks for the environment Protection target [Exposure concentration [Risk characterisation [Freshwater [Local PEC: 1.531E-6 meiL. RCR=0.01 [Sediment (Freshwater) 3265-4 melke Ow ROR =0.01 3428-7 mel. RCR <0.01 GOTE-5 mgikg dw ROR <0.01 : 2.735E-6 mgikg ww RCR=0.01 AISE-T mgikg ww RCR<0.01 Marine water [Sediment (marine water) Predator (Freshwater) Predator (marine water) [Top predator (marine water) 41SE-T mgike ww RCR<0.01 [Sewage treatment plant mell RER <0.01 Agricultural soil 2948-7 mgikg dw RCR=0.01 Predator (terrestrial) [Local PEC: 5.855E-8 mg/kg ww RCR = 0.01 [Man via Environment - [Local PEC: 5.441E-9 mgim* RCR<0.01 Hnhalation [Man via Environment - Oral [Exposure via food consumption: 4.767E- [RCR <0.01 7 marke bwiday [Man via environment - RCR<0.01 lcombined routes ‘Table 10. Contribution to oral intake for man the environment from local contribution [type of food [Estimated daily dose [Concentration in food Drinking water [2.187E-8 mu/kg bwiday [7.653E-7 mg/l Fish 4.52619 mg/kg bwiday 2.7558-6 meke ww Leaf crops 4.2846-7 mg/kg bwiday [24998-5 mglke ww Root crops 1.33RE-8 mgike bwiday [2448-6 melke ww [Meat 5.395E-9 mgikg bwiday 1255E-6 mplke ww [Mak 3.18E-9 mekkg bwiday 3.968E-7 melke ww CHEMICAL SAFETY REPORT 3EC number; dibutyl phthalate CAS number: 201-5574 84-742 9.1.3. Worker contributing scenario 1: Closed system (minimal contaet during routine operations) (PROC 1) 9.1.3.1. Conditions of use [Method [Product (article) characteristics + Concentration of substance in mixture: Substance as such TRA Worker v3 [Amount used (or contained in articles), frequency and duration of use/exposure + Duration of activity: <4 hours TRA Worker v3 |Technical and organisational conditions and measures + Containment: Closed system (minimal contact during routine operations) [TRA Worker v3 + Occupational Health and Safety Management System: Advanced TRA Worker v3 [Conditions and measures related to personal protection, hygiene and health evaluation = Dermal Protection: Yes (chemically resistant gloves conforming to EN374 with [TRA Worker v3 specific activity training) (Effectiveness Dermal: 95%] + Respiratory Protection: Yes (Respirator with APF of 20) [Effectiveness Inhal: [TRA Worker v3 195%) [Other conditions affecting workers exposure + Place of use: Outdoor [TRA Worker v3 + Process temperature (for liquid) [TRA Worker v3 + Skin surface potentially exposed: One hand face only (240 em2) [TRA Worker v3 9.1.3.2. Exposure and risks for workers ‘The exposure concentrations and risk characterisation ratios (RCR) are reported in the following table. Table 11. Exposure concentrations and risks for workers [Route of exposure and type of |Exposure concentration [Risk characterisation effects Ishatation, systemic, long-term [0,002 mg/m? (TRA Worker v3) RCR=0.019 Inhalation, systemic, acute [0.004 mg/m? (TRA Worker v3) RCR <0.01 Dermal, systemic, long-ierm [0.002 mg/kg bw/day (TRA Worker v3) _[RCR=0.01 [Combined routes, systemic, RCR=0.028 long-term [Combined routes, systemic, ROR = 0.01 lacute Conelusion on risk characterisation ‘The exposure by inhalation and dermal is below the DNELs. This indicates that the likelihood of adverse effects due to adverse systemic effects arising via long-term and acute inhalation and dermal exposure is low. 9.1.4, Worker contributing scenario 2: Material transfer (PROC 8b) 9.1.4.1. Conditions of use Method Product (article) characteristics + Concentration of substance in mixture: Substance as such [TRA Worker v3 CHEMICAL SAFETY REPORT 9EC number; dibutyl phthalate CAS number: 201-5574 84.14-2 [Method [Amount used (or contained in articles), frequency and duration of use/exposure + Duration of activity: < 15 minutes TRA Worker v3 Duration of activity: 2 minutes External Tool (Riskofdlerm 2.0) [Technical and organisational conditions and measures = Containment: Semi-closed process with occasional controlled exposure __ [TRA Worker v3 + Oceupetional Health and Safety Management System: Advanced [TRA Worker v3 [Conditions and measures related to personal protection, hygiene and health evaluation = Respiratory Protection: Yes (Respirator with APF of 20) (Effectiveness [TRA Worker v3 Inhal: 95% = Dermal Protection: Yes (chemically resistant gloves conforming to EN374__ [External Tool (Riskofderm 2.0) lwith specific activity training) [Effectiveness Dermal: 95%] [Other conditions affecting workers exposure + Place of use: Outdoor TRA Worker v3 + Process temperature (for liquid): <= 40 °C [TRA Worker v3 + Quality of the ventilation: normal or good ventilation [External Tool (Riskofderm 2.1) - Frequency of skin contact with the contamination: rare contact External Tool (Riskofderm 2.1) = Kind of skin contact: light contact External Tool (Riskofderm 2.1) ‘evel of automation of the task; aulomated or semi-automated task External Tool (Riskofderm 2.1) = Use rate: 333 kg/min [External Tool (Riskofderm 2.1) + Skin surface potentially exposed: hands (820 em2) [External Tool (Riskofderm 2.1) 9. 2. Exposure and risks for workers ‘The exposure concentrations and risk characterisation ratios (RCR) are reported in the following table Table 12, Exposure concentrations and risks for workers [Route of exposure and type of Exposure concentration [Risk characterisation effects Inhalation, systemic, long-term [0.004 mg/m’ (TRA Worker v3) ROR = 0.031 Ishalation, systemic, acute [0.041 mg/m (TRA Worker v3) ROR = 0.014 Dermal, systemic, long-ierm [0.013 mg/kg bw/day (External Tool RCR= 0.071 (Riskofderm 2.0) Additional data not used for RCR: 0.686 mg/kg bw/day (TRA Worker v3) [Combined routes, systemic, RCR=0.102, long-term [Combined routes, systemic, RCR=0.014 lacute Remarks on exposure dat External Tool (Riskofderm 2.0) + Hand loading was 18.9 mg (75th percentile), © Body weight of 70 kg - default value set in the Guidance on information requirements and chemical safety assessment, Chapter R.8: Characterisation of dose [concentration] -response for Jhuman health) v2.1, 2012 = was used (Conclusion on risk characterisation ‘The exposure by inhalation and dermal is below the DNELs. This indicates that the likelihood of adverse effects CHEMICAL SAFETY REPORT 10EC number; dibutyl phthalate CAS number: 201-5574 84-742 due to adverse systemic effets arising via long-term and acute inhalation and dermal exposure is low. 9.1.5. Worker contributing scenario 3: Laboratory use (PROC 15) 9.1.8.1. Conditions of use Method Product (article) characteristics + Concentration of substance in mixture: Substance as such [TRA Worker v3 |Amount used (or contained in articles), frequency and duration of use/exposure + Duration of activity: <4 hours [TRA Worker v3 [Technical and organisational conditions and measures = General ventilation: Good general ventilation (3-5 air changes per hour) TRA Worker v3 = Containment: No [TRA Worker v3 + Local exhaust ventilation: yes [Effectiveness Inhal: 90%] [TRA Worker v3 + Local exhaust ventilation (for dermal): yes [Effectiveness Dermal: 90%] [TRA Worker v3 ement System: Advanced + Occupational Health and Safety Mana [TRA Worker v3 [Conditions and measures related to personal protection, hygiene and health evaluation + Dermal Protection: Yes (chemically resistant gloves conforming to EN374 with specific activity training) (Effectiveness Dermal: 95° TRA Worker v3 + Respiratory Protection: Yes (Respirator with APF of 20) [Elfectivens lose s Tahal: [TRA Worker v3 [Other conditions affecting workers exposure + Place of use: Indoor [TRA Worker v3 + Process temperature (for liquid): <= at TRA Worker v3 + Skin surface potentially exposed: One hand face only (240 em2) [TRA Worker v3 9. 2. Exposure and risks for workers The exposure concentrations and risk characterisation ratios (RCR) ate reported in th ‘Table 13. Exposure concentrations and risks for workers 1 following table. [Route of exposure and type of |Exposure concentration [Risk characterisation effects Inhlation, systemic, long-term [0.002 mg/m (TRA Worker v3) RCR= 0.019 Inhalation, systemic, acute [0.004 mg/m (TRA Worker v3) RCR<0.01 Dermal, systemic, long-term [0.002 mg/kg bw/day (TRA Worker v3)__[RCR<0.01 mbined routes, systemic, RCR= 0.028 long-term [Combined routes, systemic, RCR=0.01 lacute ynclusion on risk The exposure by inhalation and dermal is below the DNELs. This indicates due to adverse systemic effects arising via long-term and acute inhalation and dermal exposure is low. thatthe likelihood of adverse effects CHEMICAL SAFETY REPORTEC number: dibutyl phthalate CAS number: 201-5574 84-74-2 9.1.6 Supporting data In 2011 Sasol Solvents, in cooperation with the Institut fiir Privention und Arbeitsmedizin der Deutchen Geseizlichen Unfallversicherung (IPA, undertook @ dibutyl phthalate (DBP) exposure biomonitoring study of Moers site maleic anhydride (MA) plant workers. Urine samples were collected from plant workers and were analyzed for monobutyl phthalate (MBP), which is the primary metabolite and a reliable indicator marker for DBP exposure. The study found no evidence of exposures exceeding established threshold values. However, patterns were observed within the data suggesting opportunities to further minimize the potential for ‘worker exposure. A team was formed to review the findings and compare plant practices against Huntsman's MA plants in Pensacola, Florida and Geismar, Louisiana. The German Berufsgenossenschaft was also invited to inspect the plant and offer advice from an independent perspective. As a result of these activities, numerous small procedural changes were identified and implemented, reducing the potential for worker exposure across a variety of tasks including sample acquisition and handling, personal protective equipment replacement, cleaning, and maintenance, Sasol-Huntsman also made significant capital investment to upgrade sampling systems and other small equipment changes to provide the highest level of protection for workers and the ‘environment according to the identified best practices. In order to verify that the procedural and equipment changes had indeed improved (reduced) actual worker ‘exposure, a second, more comprehensive biomonitoring study was commissioned in 2012, again in cooperation with the IPA. The follow-up study clearly demonstrated that median and 9S" percentile worker exposures were reduced by more than 50% relative to the 2011 study. ‘The following box-and-whisker chart is extracted from IPA’s report on the two studies, Creatinine correction \was not performed in the pilot study so all values shown are uncorrected, ieee ey sect os Sc ——talaw Up 7 sins eee oe es zm: — = I 4 2 os 5 e L fr + g o 2 wo if a | n=82 0 on=15, n=122 n=47 {pre and (pre and post shift) post shit) 2013-07-17 CHEMICAL SAFETY REPORT 2EC number: dibutyl phthalate CAS number: 201-5574 84-74-2 As demonstrated by the two leftmost columns, the study also found no evidence of occupational exposure to DBP amongst Sasol-Huntsman and Sasol Solvents workers not engaged in the operation or maintenance of the MA plant as compared to other German factory workers without the potential for DBP exposure. Amongst plant workers with the potential for DBP exposure, the 2012 study found the following on a creatinine corrected basis: 2012 Results hielliter MBP, creatinine corrected Median 44 95" Percentile | 404 Maximum —_| 1672 According to the Chemical Safety Report (CSR), the highest predicted worker exposure is 0.0135 mg DBP per kg body weight per day according to PROC 8b, Reasonable assumptions for rate of metabolism to MBP, body weight, and urinary output can be applied to show that daily DBP exposure at the CSR PROC 8b concentration would lead to a MBP concentration of $75 jg/liter, demonstrating that actual median exposure is more than an ‘order of magnitude lower than what is modelled by Riskofderm 2.0 in the CSR. Likewise, DBP exposure at the DNEL limit of 0.19 mg/kg/day would be expected to produce a finding of approximately 8000 ygyliter. Thus the biomonitoring results plainly show that even the highest observed values in the 2011 study are well below the DNEL for DBP and that median occupational exposures are less than 1% of the DNEL. In conclusion, the biomonitoring studies clearly prove that workplace exposure to DBP in the course of facturing MA according to the Huntsman process and in compliance with Sasol Solvents safety practices is very well controlled and does not pose a significant risk to the health of plant workers. Nevertheless, Sasol~ Huntsman is committed to ongoing improvement of workplace safety practices and will conduct additional biomonitoring studies to assure the effectiveness of measures employed to assure worker safety. 2013-07-17 CHEMICAL SAFETY REPORT is