File No: STD/1015 September 2002 NATIONAL INDUSTRIAL CHEMICALS NOTIFICATION AND ASSESSMENT SCHEME (NICNAS) FULL PUBLIC REPORT Component of Proban STi This Assessment has been compiled in accordance with the provisions of the Industrial Chemicals (Notification and Assessment) Act 1989 (Cwlth) (the Act) and Regulations. This legislation is an Act of the Commonwealth of Australia. The National Industrial Chemicals Notification and Assessment Scheme (NICNAS) is administered by the Department of Health and Ageing, and conducts the risk assessment for public health and occupational health and safety. The assessment of environmental risk is conducted by the Department of the Environment and Heritage. For the purposes of subsection 78(1) of the Act, this Full Public Report may be inspected at: Library National Occupational Health and Safety Commission 25 Constitution Avenue CANBERRA ACT 2600 AUSTRALIA To arrange an appointment contact the Librarian on TEL + 61 2 6279 1161 or + 61 2 6279 1163. This Full Public Report is available for viewing and downloading from the NICNAS website or available on request, free of charge, by contacting NICNAS. For requests and enquiries please contact the NICNAS Administration Coordinator at: Street Address: 334 - 336 Illawarra Road MARRICKVILLE NSW 2204, AUSTRALIA. Postal Address: GPO Box 58, SYDNEY NSW 2001, AUSTRALIA. TEL: + 61 2 8577 8800 FAX + 61 2 8577 8888. Website: www.nicnas.gov.au
Transcript
File No: STD/1015
September 2002
NATIONAL INDUSTRIAL CHEMICALS NOTIFICATION AND ASSESSMENT SCHEME (NICNAS)
FULL PUBLIC REPORT
Component of Proban STi
This Assessment has been compiled in accordance with the provisions of the Industrial Chemicals (Notification and Assessment) Act 1989 (Cwlth) (the Act) and Regulations. This legislation is an Act of the Commonwealth of Australia. The National Industrial Chemicals Notification and Assessment Scheme (NICNAS) is administered by the Department of Health and Ageing, and conducts the risk assessment for public health and occupational health and safety. The assessment of environmental risk is conducted by the Department of the Environment and Heritage.
For the purposes of subsection 78(1) of the Act, this Full Public Report may be inspected at:
LibraryNational Occupational Health and Safety Commission25 Constitution AvenueCANBERRA ACT 2600AUSTRALIA
To arrange an appointment contact the Librarian on TEL + 61 2 6279 1161 or + 61 2 6279 1163.
This Full Public Report is available for viewing and downloading from the NICNAS website or available on request, free of charge, by contacting NICNAS. For requests and enquiries please contact the NICNAS Administration Coordinator at:
FULL PUBLIC REPORT........................................................................................................................................41. APPLICANT AND NOTIFICATION DETAILS.....................................................................................42. IDENTITY OF CHEMICAL.....................................................................................................................43. COMPOSITION........................................................................................................................................44. INTRODUCTION AND USE INFORMATION......................................................................................55. PROCESS AND RELEASE INFORMATION.........................................................................................56. PHYSICAL AND CHEMICAL PROPERTIES........................................................................................67. TOXICOLOGICAL INVESTIGATIONS...............................................................................................108. ENVIRONMENT....................................................................................................................................189. RISK ASSESSMENT..............................................................................................................................2710. CONCLUSIONS – ASSESSMENT LEVEL OF CONCERN FOR THE ENVIRONMENT AND HUMANS...............................................................................................................................................2911. MATERIAL SAFETY DATA SHEET...................................................................................................3012. RECOMMENDATIONS........................................................................................................................3013. BIBLIOGRAPHY...................................................................................................................................32
File No: STD/1015
September 2002
NATIONAL INDUSTRIAL CHEMICALS NOTIFICATION AND ASSESSMENT SCHEME (NICNAS)
FULL PUBLIC REPORT
Component of Proban STi
This Assessment has been compiled in accordance with the provisions of the Industrial Chemicals (Notification and Assessment) Act 1989 (Cwlth) (the Act) and Regulations. This legislation is an Act of the Commonwealth of Australia. The National Industrial Chemicals Notification and Assessment Scheme (NICNAS) is administered by the National Occupational Health and Safety Commission which also conducts the occupational health and safety assessment. The assessment of environmental hazard is conducted by the Department of the Environment and Heritage and the assessment of public health is conducted by the Department of Health and Aged Care.
For the purposes of subsection 78(1) of the Act, this Full Public Report may be inspected at:
LibraryNational Occupational Health and Safety Commission25 Constitution AvenueCANBERRA ACT 2600AUSTRALIA
To arrange an appointment contact the Librarian on TEL + 61 2 6279 1161 or + 61 2 6279 1163.
This Full Public Report is available for viewing and downloading from the NICNAS website or available on request, free of charge, by contacting NICNAS. For requests and enquiries please contact the NICNAS Administration Coordinator at:
APPLICANT(S)Rhodia Australia Pty Ltd (ABN 24 050 029 000), 313 Middleborough Rd Box Hill VIC 3128.
NOTIFICATION CATEGORYStandard: Chemical other than polymer (more than 1 tonne per year).
EXEMPT INFORMATION (SECTION 75 OF THE ACT)Chemical name, CAS No., molecular weight, molecular and structural formulae, spectral data, exact import volume, impurities and identity of sites of end use.
VARIATION OF DATA REQUIREMENTS (SECTION 24 OF THE ACT)Variation to the schedule of data requirements is claimed as follows:
Substitution of data on ITC 826 Concentrate as follows: Schedule Part B, paragraphs 9(a) – 9(q); Schedule Part C, paragraphs (a) – (n), (q) and (r).
PREVIOUS NOTIFICATION IN AUSTRALIA BY APPLICANT(S)None.
NOTIFICATION IN OTHER COUNTRIESU.K. EU Notification number 01-06-1493-00.
2. IDENTITY OF CHEMICAL
OTHER NAME(S)Proban STi (contains the notified chemical at 55 – 65%.)
MARKETING NAME(S)Only the commercial product Proban STi has a marketing name.
SPECTRAL DATA Ultraviolet/Visible, infrared and nuclear magnetic resonance spectra for the analogue ITC 826 concentrate were provided as part of a report to the EC.
METHODS OF DETECTION AND DETERMINATIONUV/vis, IR and NMR spectroscopy.
3. COMPOSITION
DEGREE OF PURITY> 60%.
HAZARDOUS IMPURITIES/RESIDUAL MONOMERS Two hazardous impurities at a concentration of less than 1% may contribute to the notified chemical’s skin sensitisation potential.
ADDITIVES/ADJUVANTSNone.
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4. INTRODUCTION AND USE INFORMATION
MODE OF INTRODUCTION OF NOTIFIED CHEMICAL (100%) OVER NEXT 5 YEARSImport.
MAXIMUM INTRODUCTION VOLUME OF NOTIFIED CHEMICAL (100%) OVER NEXT 5 YEARS
Year 1 2 3 4 5Tonnes < 50 < 50 < 50 < 50 < 50
USEThe notified chemical will be used as a flame retardant treatment for finishing textiles used for industrial and domestic purposes. The notifier indicates that the product will only be sold to customers who enter into an agreement with the notifier.
5. PROCESS AND RELEASE INFORMATION
5.1. Distribution, Transport and Storage
PORT OF ENTRYUnknown.
TRANSPORTATION AND PACKAGINGProban Sti will be imported in 250 L plastic drums. Import in 1000 L IBCs may be undertaken in the future. No repackaging will be required.
5.2. Operation DescriptionThe fabric to be dyed is held in a 2000 m roll (for woven fabric) on an A frame or as a 1000 m plait (for knitted fabric) in a barrow. In either case the fabric is attached to a “leader” from the last batch by an industrial sewing machine. The fabric runs through the plant on stainless steel rollers, passing through the pad bath, the nip of a mangle and drying unit before being collected on an A frame or in a barrow. The notified chemical is pumped to a mixing vessel along with water or washings of the unit from a previous batch and diluted 35 – 60% before being introduced to the pad bath by gravity feed. After drying the fabric is transferred to the ammonia curing unit where it is again sewn onto a leader fabric then passes on steel rollers through rubber seals to a chamber where it is treated with anhydrous ammonia gas. The fabric then exits in the same way and is collected on an A frame or in a barrow.
After ammonia curing, the fabric is treated with 10% (w/w) hydrogen peroxide solution, neutralised with a cold dilute solution of 1% (w/w) sodium hydroxide/2% (w/w) sodium carbonate, boiled in alkaline detergent, washed and dried.
5.3. Occupational exposureNumber and Category of Workers
Category of Worker Number Exposure Duration Exposure FrequencyProcess operator (preparation of pad
batch liquor)2 2 hours/day 200 days/year
Pad bath, ammonia curing, oxidation 8 “ “Wash down 2 “ “
Exposure DetailsThere is potential for exposure when pumping the notified chemical to the mixing vessel, when transferring the liquor to the pad bath and during washing of the impregnation unit. Potential exposure is possible from drips and spills and residues on couplings and in lines. Exposure is also possible from washing the mixing vessel with water prior to transfer to the pad bath and collecting the pad bath
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liquor in drums to save for subsequent campaigns. The notifier states that workers will wear gloves, goggles and a boiler suit as personal protective equipment. The material safety data sheet for the notified chemical specifies PVC gloves. After the impregnation step the potential for worker exposure is limited.
5.4. Release
RELEASE OF CHEMICAL AT SITEThe notifier has indicated that a “zero discharge” licensing arrangement will apply to all users of the notified chemical in Australia. The customer must sign an agreement to follow the notifier’s code of practice and to comply with operational instructions regarding processing and effluent release. An important part of the code is the zero loss recycling procedure, which involves recycling and reuse of all washings, containing the notified chemical, used in the treatment process. Equipment, in the form of a refractometer is supplied to customers to allow the bath strength to be accurately measured. This allows the licensee to adjust the bath strength using recycled washings.
RELEASE OF CHEMICAL FROM USENo release of the notified chemical is expected once the polymer is cross-linked with the fibres in the fabric.
5.5. DisposalThe notifier recommends that accidental spills, which cannot be reused in the process bath, should be adsorbed onto an inert substance and disposed of by off-site methods, preferably by incineration. It is expected that container residues will be recycled. Some of the empty import containers will be used to store recycled product between production campaigns. Any contaminated bath water not able to be reused should also be incinerated.
5.6. Public exposureExposure of the general public as a result of transport, reformulation and disposal of products containing the notified chemical is assessed as being negligible. Neither the notified chemical nor products containing it will be sold directly to the general public. Public exposure to a reacted form of the notified chemical may occur as a result of dermal contact with textiles treated with the notified chemical. However the amounts to which people may be exposed is considered to be small since the notified chemical forms an insoluble polymer after processing that is trapped with the fibre matrix of the treated textile and is not bioavailable.
6. PHYSICAL AND CHEMICAL PROPERTIES
Unless otherwise stated, all physico-chemical tests were performed on a structurally related compound to the notified chemical, Proban ST (ITC 826 Concentrate). The latter substance differs from the notified chemical only in the relative percentages of its constituent phosphonium species.
Appearance at 20oC and 101.3 kPa
Off-white mobile gel.
Melting Point/Freezing Point -48 - -26oC
METHOD EC Directive 92/69/EEC A.1 Melting/Freezing Temperature.Remarks A small broad exotherm was observed with an onset temperature of ~ --48oC and a
peak maximum of ~ -26 - 27oC.TEST FACILITY ASG (1996).
Boiling Point Partial decomposition before boiling at 300oC at 101.3 kPa
METHOD EC Directive 92/69/EEC A.2 Boiling Temperature.Remarks Endotherm at 100 - 120 oC corresponding to volatilisation of water and exotherms
METHOD EC Directive 92/69/EEC Annex V, A4 Vapour Pressure. Static Method.Remarks The vapour pressure of ITC 826 was determined in a glass isoteniscope fitted with
a U-tube containing mercury as the means of pressure measurement. The initial test resulted in the test substance foaming and contaminating the mercury. A second test was performed with the isoteniscope immersed in an ice-water bath with the interconnecting tap open so that the pressure above the sample and in the mercury column remained at atmospheric. The sample was then isolated and heated to 25oC. The approximate vapour pressure was then determined. A test was also performed using the normal technique and with the addition of an antifoaming agent. The latter measurement is regarded as more reliable and was given more weight when calculating the mean value. The test results indicate the notified chemical is highly volatile, with a volatility value close to water, which most likely reflects the water component in the mixture.
TEST FACILITY ZENECA (1996a).
Water Solubility 2-3 g/L at 20oC.
METHOD OECD TG 105 Water Solubility.Remarks A preliminary test was conducted on ITC 836 Concentrate where varying
proportions of the test substance were weighed into vials and treated ultrasonically and shaken for approximately 30 minutes to mix. At high concentrations (10% w/w), the test material formed a thick mobile gel in water, at intermediate concentrations (1-5% w/w), the test material formed a cloudy solution, while at lower concentrations (0.25% w/w), the substance formed a clear solution. Attempts were made to separate the test substance by centrifuging and filtering but no separation was obtained. Water solubility was assessed visually. The test substance is miscible in water in all proportions. Further tests were carried out using lower concentrations. These tests showed the water solubility is between 0.2 and 0.3% w/w, indicating the substance is readily water soluble.
TEST FACILITY ASG (1996).
Hydrolysis as a Function of pH
METHOD EC Directive 92/69/EEC C.7 Degradation: Abiotic Degradation: Hydrolysis as a Function of pH.
pH T (C) t½ <hours or days>4 25 12.355 25 21.06
Remarks The hydrolysis test was performed on ITC 836 Concentrate at pH 4 and 5. It was not possible to perform the test at higher pH conditions due to the high acidity and insolubility of the test substance at pH 7 and 9. At higher pH conditions the test material precipitated to form hydroxides. Solutions of the test material were prepared in distilled water, adjusted to pH 4 and 5 with sodium hydroxide solution and stored in an oven at 50C and results extrapolated to 25C. The concentrations of the main components of the test substance were determined by titration to monitor release of hydrochloric acid. The expected hydrolysis reaction is:
Cl-P+(CH2OH)4 P(CH2OH)3 + HCHO + HClHydrolyses of the test substance is expected to be slower in higher pH conditions.
TEST FACILITY ASG (1996).
Partition Coefficient (n- log Pow at 25oC = -1.7.
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octanol/water)
METHOD EC Directive 92/69/EEC A.8 Partition Coefficient. Shake Flask MethodRemarks Solutions of the test substance were prepared in n-octanol saturated water. The
water phase was diluted with deionised water and the n-octanol phases were wet oxidised before determining the phosphorus content by inductively coupled plasma atomic emission spectrometry (ICP-AES). The test results indicate the notified chemical has a poor affinity to lipids.
TEST FACILITY ASG (1996).
Adsorption– screening test
METHOD In house method: Sorption and Desorption of substances to soil and sediment: Standard Operating Procedure P22.
Remarks A simple soil sorption-screening test was performed on ITC 826 using 4 g of sandy loam soil with pH 8.2. Of the initial nominal concentration of 34 mg/L of test substance added, 52% was adsorbed (or precipitated) onto soil. During the test, the test substance did not adsorb to the glass or PTFE containers. The concentration adsorbed to soils was determined by analysis of P content, which was regarded as too crude a method to obtain meaningful results.
TEST FACILITY BEL (1996).
Surface Tension 39.9 mN/m at 1000 mg/L and 25oC
METHOD OECD TG 115 Surface Tension of Aqueous Solutions.Remarks The surface tension of the test substance was measured in Milli Q distilled water
using a Kruss Processor Tensiometer fitted with a Wilhelrig plate. A small change in the surface tension over the test period indicates an ageing effect. The test substance can be classified as a surfactant.
TEST FACILITY ASG (1996).
Dissociation Constant Not done.
Particle Size Not done.
Flash Point No flash detected below 96oC.
METHOD EC Directive 92/69/EEC A.9 Flash Point.Remarks Chemical frothed out of test cup at approximately 96oC.TEST FACILITY Zeneca (1996a).
Flammability Limits Not flammable.
Autoignition Temperature 310oC
METHOD 92/69/EEC A.15 Auto-Ignition Temperature (Liquids and Gases).TEST FACILITY Zeneca (1996a).
Toxicological investigations were conducted with the analogue ITC 826 Concentrate. It is judged to be an acceptable analogue as one of the reaction components differs only by a short carbon chain length. The studies were conducted to GLP standards with the exception of eye irritation (section 7.5).
Endpoint and Result Assessment ConclusionRat, acute oral LD50 > 50 mg/kg bw* harmfulRat, acute dermal LD50 > 2000 mg/kg bw low toxicityRabbit, skin irritation corrosiveRabbit, isolated eyes, eye irritation severely irritatingGuinea pig, skin sensitisation - adjuvant test/non-adjuvant test. sensitisingRat, oral gavage repeat dose toxicity - 28 days. NOEL = 5 mg/kg/day bwGenotoxicity - bacterial reverse mutation mutagenic (- S9)Genotoxicity – in vitro mutagenesis in mouse lymphoma L5178Y cells mutagenic (+/- S9)Genotoxicity – in vivo mouse bone marrow micronucleus non genotoxic* discriminating dosage: no mortality
Toxicological investigations with extracts (20 g of fabric in 80 mL of water for 24 hours at 37°C) of fabric treated with the notified chemical or in the case of the skin irritation test, human insult patch test and Buehler test, with the fabric itself.
Endpoint and Result Assessment ConclusionRat, acute oral LD50 > 10 mL/kg bw low toxicityRabbit, skin irritation not irritatingHuman, repeat insult patch test not irritating, non-sensitiserGuinea pig, skin sensitisation - Buehler test. non-sensitiser
7.1. Acute toxicity – oral
7.1.1 ITC 826 Concentrae
TEST SUBSTANCE ITC 826 Concentrate.
METHOD Not stated but similar to OECD TG 420 Acute Oral Toxicity – Fixed Dose Method.
CONCLUSION The extract is of low toxicity via the oral route.
TEST FACILITY Safepharm (1997).
7.2. Acute toxicity - dermal
TEST SUBSTANCE ITC 826 Concentrate.
METHOD Not stated but similar to OECD TG 402 Acute Dermal Toxicity – Limit Test.
Species/Strain Rat/WistarVehicle Water.Type of dressing Occlusive.
RESULTS
Group Number and Sexof Animals
Dosemg/kg bw
Mortality
1 5/sex 2000 None.
LD50 > 2000 mg/kg bwSigns of Toxicity - Local Moderate irritation was observed in all animals including erythema,
oedema, desquamation, thickening and scabbing. Signs indicative of necrosis and blanching of the skin were observed in 2 males and one female.
Signs of Toxicity - Systemic None.Effects in Organs None.Remarks - Results
CONCLUSION The notified chemical is of low toxicity via the dermal route.
TEST FACILITY Zeneca (1996c)
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7.3. Acute toxicity - inhalationNo data provided.
7.4. Irritation – skin
7.4.1 ITC 826 Concentrate
TEST SUBSTANCE ITC 826 Concentrate.
METHOD Not stated.Species/Strain Rabbit/New Zealand WhiteNumber of Animals 1Vehicle None.Observation Period 3 days.Type of Dressing Occlusive.Remarks - Method Treatments were for 3 minutes and 1 hour on different sites on the same
animal.
RESULTS No irritation was seen at the 3 minute application site. For the 1 hour treatment, slight erythema was observed up to day 2 (Draize score 1) and moderate to severe erythema on day 3 (Draize score 3). Slight oedema was observed at 1 hour post-treatment (Draize score 2); moderate oedema developed to day 2 (Draize score 3) followed by severe oedema on day 3 (Draize score 4). Necrosis was observed from 4 hours to day 3. Histopathology indicated diffuse severe inflammatory cell infiltration (predominantly epidermal), diffuse slight oedema, diffuse severe necrosis and slight hair follicle loss at day 3.
CONCLUSION The notified chemical is corrosive to skin.
TEST FACILITY Zeneca (1996d)
7.4.2 Extract of ITC 826 Concentrate Treated Fabric
TEST SUBSTANCE Extract of fabric treated with ITC 826 Concentrate.
METHOD OECD TG 404 Acute Dermal Irritation/Corrosion.Species/Strain Rabbit/New Zealand WhiteNumber of Animals 3Vehicle None (the test substance was moistened with 0.5 mL distilled water).Observation Period 3 days.Type of Dressing Semi-occlusive.
RESULTS Neither erythema nor oedema was observed in any animal at any observation point during the study.
CONCLUSION The extract of fabric treated with ITC 826 Concentrate is not irritating to skin.
TEST FACILITY Safepharm (1995a).
7.5. Irritation - eye
TEST SUBSTANCE ITC 826 Concentrate.
METHOD Burton et al. (1981).Species/Strain Isolated rabbit eyes (strain unknown) were used.Observation Period 5 hours.Remarks - Method Isolated eyes were left to equilibrate under a saline drip for 45 – 60
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minutes and were rejected for study if more than 4% corneal swelling occurred. Two eyes were treated in petri dishes containing saline and either 0.1 mL or 25 mg of test substance (a white mobile gel) was applied to the cornea for 10 seconds followed by saline rinsing.
RESULTS Corneal swelling appeared to be linear with time up to 5 hours (approximately 4.4% per hour) to a maximum of 29.4%. Minimal opacity was seen in both eyes from 2 – 5 hrs post dosing.
Remarks - Results Materials causing the eyes to swell more than 15% are considered to have the potential to be severe eye irritants in vivo.
CONCLUSION The notified chemical is considered likely to be severely irritating to the eye.
TEST FACILITY Zeneca (1996e)
7.6. Skin sensitisation
7.6.1 ITC 826 Concentrate
TEST SUBSTANCE ITC 826 Concentrate.
METHOD Maximisation test (Magnusson and Kligman, 1970).Species/Strain Guinea pig/Crl:(HA)BR.PRELIMINARY STUDY Maximum Non-irritating Concentration:
intradermal: slight erythema and slight thickening was observed at 0.03%topical: 30% w/v.
MAIN STUDYNumber of Animals Test Group: 20 Control Group: 10
High dose males exhibited a reduction in bodyweight gain from day 4 to a maximum of 11% (compared to control animals) by day 29 correlated with a reduction in food consumption from week 2. Mid dose males exhibited a less marked reduction
Clinical Chemistry: Significant findings were elevated gamma-glutamyl transferase in high dose animals and elevated alanine and aspartate aminotransferases in high dose males. Mid and high dose males exhibited reduced triglyceride levels.
Haematology: No significant findings.
Effects in Organs
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High dose females exhibited an increase in liver weight.
Speckled livers were seen in 2 high dose males and accentuated lobular pattern/paleness was seen in livers from 2 high dose females. All high dose animals exhibited moderate to minimal periportal hepatocellular vacuolar degeneration. Two mid-dose males exhibited this effect to a minimal extent.
Remarks – Results
The clinical chemistry parameters and microscopic examinations indicated that the liver was the target organ. Minimal liver effects were seen in two mid-dose males and there was some reduction in triglyceride levels.
CONCLUSIONThe No Observed Effect Level (NOEL) was established as 5 mg/kg bw/day in this study, based on liver effects in males.
E. coli: WP2 uvrA (pKM101), WP2 (pKM101).Metabolic Activation System S9 fraction from livers of Phenobarbital/-naphthoflavone induced rats.Concentration Range inMain Test
a) With metabolic activation: 10 - 5000 µg/plate.b) Without metabolic activation: 10 - 5000 µg/plate.
Vehicle Sterile water.Remarks - Method As a result of toxicity in the first set of experiments two repeats were
conducted at a maximum concentration of 500 µg/plate. A background lawn was absent at above 1000 µg/plate and sparse at 500 µg/plate.
RESULTS
Metabolic Activation
Test Substance Concentration (µg/plate) Resulting in:Cytotoxicity in
Remarks - Results Genotoxicity was only observed in the absence of S9 fraction and in strain TA 1537. The maximum mutagenic potency was approximately 0.1 mutants per microgram.
CONCLUSION The notified chemical was mutagenic to bacteria under the conditions of the test.
1 5/sex 0 24 and 48 hours2 5 males 200 24 and 48 hours3 5 females 320 24 and 48 hours4 5/sex CP, 65 24 hours
CP = cyclophosphamide.
RESULTSDoses Producing Toxicity 320 mg/kg bw (males), 500 mg/kg/bw (females).Genotoxic Effects A statistically significant increase in micronucleus frequency at the 24
hour time point for females was apparently due to a low control value as confirmed by a further analysis of female vehicle controls.
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CONCLUSION The notified chemical was not clastogenic in this in vivo mouse bone marrow micronucleus test under the conditions of the test.
TEST FACILITY Zeneca (1996i).
ADDITIONAL INVESTIGATIONS
7.11. Skin sensitisation – human repeat insult patch test
TEST SUBSTANCE Proban ST treated fabric.
METHOD According to Kligman (1966).Study Design A single main study was conducted.Study Group Thirty volunteers aged 18 to 65 years were selected and 27 completed full
induction and challenge phases of the test. Three volunteers dropped out for reasons unrelated to the test.
Vehicle Not applicable.Induction Procedure The upper arm of each volunteer was exposed to a 23-hour occlusive
patch of 0.1% w/v sodium lauryl sulphate (SLS) in water, to produce a mild irritation at 2 test sites before application of the fabrics. This pre-treatment was carried out in the 24 hours prior to application of the fabric. During induction both Proban ST-treated and untreated fabric were applied to SLS-treated and non-SLS-treated sites. During challenge the fabrics were only tested on SLS pre-treated skin on the original arm and on non SLS pre-treated skin on the alternate arm.
Each subject received 5 induction patches, each of 48 hours duration, applied over a three week period. After the induction stage there was a 2 week rest period prior to challenge.
Rest Period 2 weeks.Challenge Procedure At challenge, the Proban ST-treated and non treated fabrics were applied
to both the original arm and alternative arm. The skin sites previously exposed on the original arm were again pre-irritated with SLS for 1 hour and the test fabrics applied. Similar patches were applied to the non pre-irritated alternate arm. Patches were removed at 47 hours and sites scored at 48 and 96 hours.
RESULTS Three volunteers produced strong erythematous reactions with either papules or oedema to untreated fabric on SLS pre-irritated skin. At challenge there was no evidence of delayed contact hypersensitivity to either fabric.
CONCLUSION A human repeat insult patch test was conducted using fabric treated with Proban ST under occlusive dressing. The test fabric was non-irritating and non-sensitising under the conditions of the test.
TEST FACILITY Inveresk (1998).
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8. ENVIRONMENT
8.1. Environmental fate
Environmental fate and ecotoxicity test studies were performed on either the notified chemical or a related compound to the notified chemical, Proban ST (ITC 826 Concentrate). The latter substance differs from the notified chemical only in the relative percentages of the constituents. All data are considered suitable to read-across from ITC 826 Concentrate.
8.1.1. Ready biodegradability
TEST SUBSTANCE ITC 826 Concentrate.
METHOD EEC/92/L383A, Part C.4-D, Biodegradation: Determination of Ready biodegradability - Manometric Respirometry Test.
Inoculum Activated sewage sludge.Exposure Period 28 days.Auxiliary Solvent None.Analytical Monitoring COD; BOD; dissolved non-purgeable organic carbon (DNPOC).Remarks - Method Nutrient solutions containing either 0 (control) or 25 mg/L of test
substance were seeded with activated sludge and incubated for 28 days. A reference substance, sodium acetate, seeded with the inoculum, was incubated for the same period to test the viability of the micro-organisms and the test system. The percentage degradation of test material was calculated as (BOD28/COD) X 100%. Chemical oxygen demand (COD) was determined by refluxing a known amount of test material with excess acidified potassium dichromate in the presence of silver sulphate and a chromium (III) salt, then titrating the excess dichromate with ferrous ammonium sulphate. Biological oxygen demand (BOD) was determined in a Hach manometric biochemical oxygen demand apparatus. At the end of the test, centrifuged samples of test media were analysed for DNPOC.
RESULTS
Test substance Sodium AcetateDay % degradation Day % degradation
5 0 5 7128 0 28 75
Remarks - Results The BOD of the test substance after 5 days and 28 days was zero. The average COD for the test substance was 0.67 g O2 g-1 while the COD for the reference substance was 0.68 g O2 g-1 demonstrating the validity of the analytical technique. The BOD:COD ratio of sodium acetate was in excess of 60% indicating the inoculum was viable. The results of DNPOC analysis indicated a loss of 25% test material. However, the removal of DNPOC may represent losses through adsorption onto solids, volatilisation or primary biodegradation.
CONCLUSION The test substance is not readily biodegradable.
TEST FACILITY BEL (1995a).
8.1.2. BioaccumulationNo bioaccumulation test was performed. The notified chemical is highly water soluble, has a low log Pow, and hence is expected to have a poor affinity to lipids, which together with its high molecular weight, indicate the substance should not bioaccumulate.
8.2. Ecotoxicological investigations
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8.2.1. Acute toxicity to fish
TEST SUBSTANCE ITC 826 Concentrate
METHOD EC Directive 92/69/EEC C.1 Acute Toxicity for Fish – static conditions.Species Rainbow trout (Oncorhynchus mykiss)Exposure Period 96 hoursAuxiliary Solvent NoneWater Hardness 55.3 mg CaCO3/LAnalytical Monitoring Test concentrations by ICP spectrometer.Remarks – Method Test solutions were prepared by directly adding the required amounts of
test substance into dilution water (dechlorinated tap water). The water was first filtered and sterilised with an ultraviolet steriliser. The test solutions were clear and colourless. Records of mortalities and abnormal behaviour were made at 24, 48, 72 and 96 hours after the start of the test. The concentrations of test material in the test solution were determined from the phosphorus content and measured at 0 and 96 hours. There was no measured loss of test material over the test period.
RESULTS
Concentration mg/L Number of Fish MortalityNominal Measured 24 h 48 h 72 h 96 h
LC50 3.8 mg/L at 96 hours.NOEC 1.0 mg/L at 96 hours.Remarks – Results No symptoms of toxicity were observed at ≤1.0 mg/L. Abnormal
behaviours were not described in the report, nor were the methods of calculation of endpoints. Results are expressed as nominal concentrations of active ingredient (a.i.: test material excluding water).
CONCLUSION The test substance is moderately acutely toxic to Rainbow trout (Mensink et al. 1995).
TEST FACILITY BEL (1995b).
8.2.2. Fish, Juvenile Growth Test
TEST SUBSTANCE ITC 826 Concentrate
METHOD Draft OECD TG Fish, Juvenile Growth Test – 28 days (September 1997) – dynamic conditions.
Species Rainbow trout (Oncorhynchus mykiss)Exposure Period 28 daysAuxiliary Solvent NoneWater Hardness 107 to 109 mg CaCO3/LAnalytical Monitoring Test concentrations.Remarks – Method Following a preliminary range-finding study, a definitive test was
performed under flow-through conditions to determine the effects of the test substance on the growth rate of juvenile fish. Fish were exposed in groups of 16 to aqueous dispersions of the test material over the concentration range of 0 (control), 1.6, 2.5, 4.0, 6.3 and 10 mg/L.
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Adverse reactions and mortalities were recorded daily throughout the exposure period. Fish weights and lengths were measured on day 0 and day 28. Prior to the start of the test, the fish were anaesthetised by immersion in anaesthetic, and removed from the tank when movement had stopped. The fish were then weighed and measured, and placed in fresh water to recover prior to being placed in test vessels. The concentrations and stability of the test material in solution were verified by chemical analysis on days 0, 1, 5, 7, 12, 14, 19, 21, 26 and 28. These concentrations ranged from 122 to 136% of nominal.
RESULTS
Concentration mg/L Number of Fish MortalityNominal 1 d 7 d 14 d 21 d 28 d
LC50 3.9 mg/L at 28 day (CI = 3.4-4.3 mg/L).NOEC (or LOEC) 2.5 mg/L at 28 days.Remarks – Results There was no significant inhibition of the tank-average specific growth
rate at the test concentration of 1.6 and 2.5 mg/L over the test period of 0-28 days when compared to the control group. Sub-lethal effects were observed at test concentrations of 4.0 mg/L and above. These effects were swimming at the bottom of the tank, loss of equilibrium, and the presence of moribund fish. The percentage inhibition of the tank-average specific growth rate could not be calculated for the 4.0, 6.3 and 10 mg/L test groups because the effects of the exposure to the test material resulted in 56%, 100% and 100% mortalities respectively by day 28. The NOEC is based on zero mortalities, insignificant differences in tank-average specific growth rates, or length and weight compared to the control, and the absence of any behavioural abnormalities. The LC50 values and associated confidence limits were calculated by the moving averages method. Results are expressed as nominal concentrations of active ingredient (a.i.: test material excluding water).
CONCLUSION The test substance had no effect on the growth of juvenile rainbow trout, but had a prolonged toxic effect on the fish, which resulted in mortalities at concentrations of 4.0 mg/L and above. These results indicate the test substance is very slightly chronically toxic to fish (Mensink et al. 1995). The acute/chronic ratio is very low.
TEST FACILITY Safepharm (1999).
8.2.3. Acute toxicity to aquatic invertebrates
TEST SUBSTANCE ITC 826 Concentrate
METHOD EEC/92/L383A Part C.2, Acute toxicity (immobilisation) for Daphnia – static conditions.
Species Daphnia magnaExposure Period 48 hoursAuxiliary Solvent NoneWater Hardness 224 mg CaCO3/LRemarks - Method Daphnids (4 X 5 replicates) were exposed to test media prepared by
adding appropriate volumes of stock solution in reconstituted water, aerated for 2 hours before use. Dissolved oxygen concentrations ranged
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from 8.8-9.0 mg/L and pH values ranged from 7.4 to 8.1. A visual assessment of response was made 24 and 48 hours after the start of the test. Test concentrations were verified by ICP spectrometry at the start and end of the test, and these ranged from 100-117% of nominal concentrations.
RESULTS
Concentration mg/L Number of D. magna Number ImmobilisedNominal Actual 24 h 48 h
NOEC 2.4 mg/L at 48 hoursRemarks - Results Methods of calculation of endpoints and confidence intervals, or sub-
lethal toxicity observations were not stated in the report. Environment Australia performed a Probit analysis on the above data to verify the results and found a 48 h LC50 of 6.3 mg/L (95% CI = 5.3-7.5 mg/l), an NOEC of 2.4 mg/L and an LOEC of 4.1 mg/L. Results are expressed as nominal concentrations of active ingredient (a.i.: test material excluding water).
CONCLUSION The test substance is moderately acutely toxic to Daphnia magna (Mensink et al. 1995).
TEST FACILITY BEL (1995c).
8.2.4. Chronic toxicity to aquatic invertebrates
TEST SUBSTANCE ITC 826 Concentrate
METHOD OECD TG 202 Daphnia sp. Acute Immobilisation Test and Reproduction Test – Reproduction test/semi-static.
Species Daphnia magnaExposure Period 21 daysAuxiliary Solvent NoneWater Hardness 250 mg CaCO3/LAnalytical Monitoring Temperature was recorded daily. Dissolved oxygen and pH were
recorded before each test media renewal.Remarks - Method Four replicates of 10 daphnids per groups were exposed to aqueous
solutions of the test substance in the concentration range of 0 (control), 0.064, 0.20, 0.64, 2.0 and 6.4 mg/L for a period of 21 days. Test solutions were renewed 3 times per week. The number of live and dead Daphnia was determined daily. The number of young Daphnia (live and dead) was determined at each test media renewal, as was the general condition of the parental and young daphnids, and unhatched eggs compared to the control. The concentrations of the test solutions were verified by HPLC analysis on days 0, 2, 4, 7, 9, 14, 16, 18 and 21. Measured test concentrations ranged from less than the limit of quantitation to 186% of nominal. However, the measured values given for the test groups, equal to and above the NOEC, were all greater than the required 80% of nominal with 3 exceptions, which were attributed to analytical variations.
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RESULTSLC50 1.8 mg/L at 14 days (immobilisation) (CI = 1.5-2.2)
1.12 mg/L at 21 days (immobilisation) (CI = 1.08-1.15)1.12 mg/L at 14 days (reproduction) (CI = 1.1-1.14)1.1 mg/L at 21 days (reproduction) (CI = 0.64-2.0)
NOEC (or LOEC) 0.64 mg/L at 21 days (immobilisation and reproduction)Remarks - Results Immobilisation end points are based on time-weighted mean measured
concentrations calculated by the moving average method of Thompson. Results show 100% immobilisation occurred at 6.4 mg/L by Day 7. Significant immobilisation also occurred throughout the study in the 2.0 mg/L test group resulting in 100% mortality by Day 16, indicating a prolonged toxic effect from exposure to the test substance. There was a significant effect on the colour of the daphnids as a result of exposure, with 100% of surviving daphnids exposed to concentrations of 2.0 mg/L being markedly paler than the controls.
Reproduction LC50s are based on nominal test concentrations, and were calculated from statistical comparisons between the controls and test solutions of the number of young produced per adult and the number of mortalities in the parental generations. There was no statistically significant difference in the number of young produced per adult in the control and the 0.064, 0.2, 0.64 mg/L test groups at days 14 and 21. The remaining live adults (40%) exposed to 2.0 mg/L produced no young after day 14. Daphnids exposed to the 6.4 mg/L were all dead prior to maturation and production of offspring. Filial daphnids produced by all test groups were in the same general condition as the young produced by the control. However, all young were removed soon after liberation from the brood pouch. Numbers of unhatched eggs and dead young were low in all control and treatment groups surviving to maturation. Results are expressed as nominal concentrations of active ingredient (a.i.: test material excluding water).
CONCLUSION The test substance results in significant prolonged mortality effects in adult daphnids, and biologically significant impairment of reproduction. The EC50 values indicate the test substance is slightly chronically toxic to Daphnia (Mensink et al. 1995).
TEST FACILITY Safepharm (1998a).
The notifier provided six test reports for algal toxicity. These are presented in chronological order below. An initial study using Proban ST (ITC 826) performed to GLP standards indicated the test material was highly toxic to Selenastrum (Test 1). Consequently, it was decided to investigate the potential for reducing toxicity by oxidation of the test substance, Proban ST. Hence a number of studies were performed using oxidised test material (Test 2-4). In one study (Test 3) it was found that formaldehyde, which is toxic to algae, was produced during the oxidation step. Therefore the test was repeated using steam distilled Proban ST to remove formaldehyde (Test 4). Two further tests were performed using the notified substance Proban Sti. Test 5 is non-GLP compliant, while Test 6 was performed using GLP standards.
8.2.5. Algal growth inhibition test (Test 1)
TEST SUBSTANCE ITC 826 Concentrate
METHOD EC Directive 92/69/EEC C.3 Algal Inhibition Test (GLP compliant).Species Selenastrum capricornutumExposure Period 72 hoursConcentration RangeNominal
0.018, 0.037, 0.074, 0.15, 0.30, 0.59, 1.2 and 2.4 mg/L of technical material excluding water.
Concentration RangeMeasured
Test concentrations were determined for the stock solution from the concentration of phosphorus. The measured concentration of the test material in the stock solution was 113% of nominal value.
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Auxiliary Solvent NoneWater Hardness Standard Test MediumAnalytical Monitoring pH, temperature, light intensity, test concentrations.Remarks - Method Six replicates of the control and three per each test concentration were
incubated at 24C, under continuous cool-white illumination, with orbital shaking at 160 rpm. After 24, 48 and 72 hours, samples were removed from each test and blank vessel. Algal cell densities of the inoculum and test cultures were determined using a Coulter counter. Cell densities were obtained by subtracting the test culture counts from the blank particle counts.
RESULTSRemarks - Results The 72-hour ErC50 is 0.15 mg/L and the NOEC growth is 0.037 mg/L
(95% CI = 0.085-0.25 mg/L). The 72-hour EbC50 is 0.073 mg/L and the NOEC biomass was 0.018 mg/L (95% CI = 0.03-0.13 mg/L). These results are based on nominal concentrations of the technical material excluding water and were calculated by statistical analysis of the area under the growth curve (expressed as percentage of control) for each replicate. To estimate the 95% confidence interval, the percentage areas were transformed to probability scales and analysed by linear regression against log concentrations.
CONCLUSION The test substance is highly toxic to algae (Mensink et al. 1995).
TEST FACILITY BEL (1995d).
8.2.6. Algal growth inhibition test (Test 2)
TEST SUBSTANCE Oxidised Proban ST
METHOD OECD TG 201 Alga, Growth Inhibition Test (Non-GLP compliant)Species Scenedesmus subspicatusExposure Period 72 hoursConcentration RangeNominal
6.25, 12.5, 25, 50 and 100 mg/L active ingredient.
Concentration RangeActual
Concentrations not verified.
Auxiliary Solvent NoneWater Hardness Standard culture mediumAnalytical Monitoring Cell densities determined using Coulter Counter at 0, 24, 48 and 72
hours. The pH was measured at 0 and 72 hours.Remarks - Method To oxidise the test substance, it was heated to 50C prior to weighing (no
other details were provided). The oxidised test material was dispersed directly into the culture medium. The concentrations employed a correction factor to account for the percentage active ingredient (15.3% w/w). Algal growth was determined using the area under the curve method and statistical analysis.
RESULTSBoth algal growth and biomass were affected by the presence of the test substance. The 72-hour EbC50 was 11 mg ai/L. The 0-72 hour ErC50 was 18 mg ai/L. The NOEC is 6.25 mg ai/L. No abnormalities were detected microscopically in the algae cells in the control of test cultures.
CONCLUSION The oxidised test substance is slightly toxic to algae (Mensink et al. 1995).
TEST FACILITY Safepharm (1998b).
8.2.7. Algal growth inhibition test (Test 3)
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TEST SUBSTANCE Oxidised Proban ST
METHOD OECD TG 201 Alga, Growth Inhibition Test (GLP compliant)Species Scenedesmus subspicatusExposure Period 72 hoursConcentration RangeNominal
6.25, 12.5, 25, 50 and 100 mg/L
Concentration RangeActual
Measured test concentrations at 0 hours were near nominal. Measured test concentrations at 72 hours showed a marked decline to between 13 and 85% of nominal.
Auxiliary Solvent NoneWater Hardness Standard culture medium. Composition provided.Analytical Monitoring Test concentrations, cell densities, pH.Remarks - Method The test substance was chemically oxidised at pH 9 using hydrogen
peroxide prior to testing. The stock solution was prepared by adding the required amount of test substance directly to the culture medium and then diluting to the required concentrations. The pH and test concentrations were measured at the start of the test and after 72 hours. Samples of algal populations were removed daily and cell concentrations determined with a Coulter Particle Counter. The pH deviation in the control cultures was in excess of Test Guidelines. This was thought to be due to the large number of cells in the log phase of growth respiring oxygen and producing carbonates and bicarbonates. The deviation was considered not to affect the integrity of the test. End points were calculated by statistical analysis of differences in the area under the growth curve of replicates compared to the controls.
RESULTSRemarks - Results The 72-hour EbC50 based on nominal test concentrations was 8.0 mg
ai/L, the 0-72 hour ErC50 was 8.8 mg/L, and the NOEC was 6.25 mg ai/L. However, because the test concentrations declined over the test period, the EC50 values were adjusted using the time-weighted mean measured test concentrations. The time-weighted 72-hour EbC50 was 4.8 mg ai/L, the 0-72 hour ErC50 was 6.4 mg ai/L, and the NOEC was 2.6 mg ai/L. No abnormalities were observed microscopically in test cultures at 6.25 mg ai/L. At test concentrations of 12.5 and 25 mg ai/L, cell debris was present, and at test concentrations of 50 and 100 mg ai/L no intact cells were visible.
CONCLUSION The oxidised test substance is moderately toxic to algae (Mensink et al. 1995). The notifier indicated that during the oxidation step, formaldehyde was produced, which could have increased the toxicity.
TEST FACILITY Safepharm (1998c).
8.2.8. Algal growth inhibition test (Test 4)
TEST SUBSTANCE Oxidised Proban ST (Steam distilled to remove formaldehyde)
METHOD OECD TG 201 Alga, Growth Inhibition Test (GLP compliant).Species Scenedesmus subspicatusExposure Period 72 hoursConcentration RangeNominal
Remarks - Method The test material was oxidised by the Sponsor prior to testing (methods not stated). The stock solution was prepared by adding the required amount of test substance directly to the culture medium and then diluting to the required concentrations. The pH and test concentrations were measured at the start of the test and after 72 hours. Cell concentrations were determined daily and after 72 hours with a Coulter Particle Counter. The pH deviation in the test cultures was in excess of Test Guidelines and followed a concentration dependent pattern with the lower test concentrations showing the greatest increase in pH. The deviation was thought to be due a greater number of viable cells in the lower test concentrations resulting in greater utilisation of carbonates and bicarbonates. The deviation was considered not to affect the integrity of the test.
RESULTSRemarks - Results The 72-hour EbC50 was 12 mg ai/L and the 0-72 hour ErC50 was 32 mg
ai/L. The NOEC was 6.25 mg/L.
CONCLUSION The oxidised test substance is slightly toxic to algae (Mensink et al. 1995).
TEST FACILITY Safepharm (2000a).
8.2.9. Algal growth inhibition test (Test 5)
TEST SUBSTANCE Proban STi
METHOD OECD TG 201 Alga, Growth Inhibition Test (Non-GLP compliant).Species Scenedesmus subspicatusExposure Period 72 hoursConcentration RangeNominal
0.1, 0.20, 0.40, 0.80, and 1.6 mg/L active ingredient.
Concentration RangeActual
Not reported
Auxiliary Solvent NoneWater Hardness Standard culture mediumAnalytical Monitoring Cell densities, pHRemarks - Method A non-GLP compliant test was performed using the notified chemical to
determine its effects on algal growth. Tests were performed in continuously illuminated (7000 lux) conical flasks incubated and shaken on an orbital shaker (100 rpm). Cell densities were measured with a Coulter Multisizer Particle Counter at 0, 24, 48 and 72 hours. The pH was determined and 0 and 72 hours. Test concentrations were not verified. Algal growth was determined using the area under the curve method and statistical analysis.
RESULTSBoth algal growth and biomass were affected by the presence of the test substance. The 72-hour EbC50 was 0.65 mg ai/L (CI = 0.55-0.77 mg/L). The 0-72 hour ErC50 was 1.7 mg ai/L. The NOEC is 0.40 mg ai/L. No abnormalities were detected microscopically in the algae cells in the control of test cultures.
CONCLUSION The notified chemical is highly toxic to algae (Mensink et al. 1995).
TEST FACILITY Safepharm (2000b).
8.2.10. Algal growth inhibition test (Test 6)
TEST SUBSTANCE Proban Sti
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METHOD OECD TG 201 Alga, Growth Inhibition Test (GLP compliant).Species Pseudokirchneriella subcapitata (= Selenastrum capricornutum)Exposure Period 72 hoursConcentration RangeNominal
0.10, 0.20, 0.40, 0.80 and 1.6 mg/L active ingredient.
Concentration RangeActual
Test concentrations were near nominal at the start of the test, but showed a marked decline after 72 hours from less than the limit of quantification to 33% nominal.
Auxiliary Solvent None.Water Hardness Standard Test MediaAnalytical Monitoring Temperature, pH, cell densities, test concentrations.Remarks - Method Following a preliminary range-finding test, algae were exposed to
aqueous solutions of the test material using three replicates per each concentration, held under constant illumination and shaking at a temperature of 24C. Samples of the algae populations were removed daily and cell concentrations determined using a Coulter Particle Counter. Test concentrations were verified using a chromatographic profile, which consisted of a number of peaks representing the various components in the mixture. One peak was chosen as a marker to monitor test concentrations. End points were calculated by statistical analysis of differences in the area under the growth curve of replicates compared to the controls.
RESULTSExposure of the algae to the test substance gave a 72-hour EbC50 of 0.60 mg ai/L (CI = 0.52-0.69 mg/L). The ErC50 was 1.2 mg ai/L (CI = 1.1-1.4 mg/L) and the NOEC was 0.20 mg ai/L. The toxicity could not be attributed to any one or more of the components in the test substance. There were no abnormalities observed in any of the test cultures below 0.40 mg ai/L. However, at the test concentration of 0.80 mg ai/L some enlarged cells were present, and at concentrations of 1.6 mg ai/L few intact cells were observed.
CONCLUSION The test substance is highly toxic to the algae Pseudokirchneriella subcapitata (Mensink et al. 1995).
TEST FACILITY Safepharm (2001).
8.2.11. Inhibition of microbial activity
TEST SUBSTANCE ITC 826 Concentrate (26.1% w/w water)
Remarks – Method The respiration rates of activated sludge micro-organisms were compared between organisms exposed to the test substance and non-exposed organisms. The rates of oxygen uptake were measured in a confined Perspex cell by a polarographic oxygen electrode, connected to a meter, whose output was recorded on a potentiometric chart recorder. The reference substance caused substantial inhibition of the respiration rates, giving a 3-hour IC50 of 5 mg/L, indicating the test system was viable.
RESULTSIC50 10-100 mg/LNOEC 10 mg/LRemarks – Results Results are based on nominal concentrations of the test substance
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technical material excluding water.
CONCLUSION The test substance is moderately toxic to sewage micro-organisms.
TEST FACILITY BEL (1995e).
9. RISK ASSESSMENT
9.1. Environment
9.1.1. Environment – exposure assessmentDuring treatment of the textiles, the notified chemical is polymerised to become cross-linked, and incorporated within the fibres in the fabric. Hence no environmental exposure of the notified chemical is expected from use of the treated fabric. According to tests carried out by the notifier, the polymer is stabilised in the fabric for 50 washes without degradation. At the end of their useful lives, the textiles are expected to be disposed of through domestic waste, and will most likely end up in landfill.
No aquatic exposure is expected as a result of the treatment process, which takes place in an isolated bath system with closed transfer systems. During fabric treatment, the notifier has indicated that a “zero discharge” licensing arrangement will apply to all users of the notified chemical in Australia. All bath water containing the notified chemical will be placed in storage containers for reuse in subsequent treatment batches. Equipment, in the form of a refractometer, is supplied to customers to allow the bath strength to be accurately measured, allowing licensees to adjust the bath strength using recycled washings. Because all wastes including drum residues are to be recycled, no wastes are expected, except in the case of accidental spills. Wastes resulting from accidental spills will be disposed of off-site by incineration.
9.1.2. Environment – effects assessmentThe aquatic toxicity tests indicate the notified chemical is moderately acutely toxic to fish and Daphnia magna, slightly toxic to sewage micro-organisms, and is highly acutely toxic to algal species, with the lowest 72 hour EbC50 being 0.073 mg/L. When the notified chemical is oxidised prior to toxicity testing, however, the toxicity of the chemical toward algae is reduced to being slightly to moderately toxic.
In chronic studies against fish and Daphnia magna, no effects were observed on the growth and reproduction of fish, whereas significant prolonged mortality effects and biologically significant impairment of reproduction was observed in adult daphnids. According to the Mensink et al (1995) scale, the test substance is slightly chronically toxic to Daphnia and very slightly chronically toxic to fish.
The Predicted No Effects Concentrations (PNEC), using a safety factor of 100, and the lowest acute 72 hour EbC50 for algae is 0.73 g/L.
9.1.3. Environment – risk characterisationNo PEC was calculated because no emissions are expected during polymerisation of the notified chemical. However, if the notified chemical were unintentionally released into the aquatic environment through accidental spills or leaks before it is polymerised within the fabric, it would be expected to enter trade waste treatment facilities at the two customer sites, one located in Sydney, and the other in Melbourne. Trade-waste effluent from these facilities would eventually enter the Metropolitan sewer after treatment.
If we assume that 1% of the chemical is released each year as a result of spills or leaks, the resulting daily PEC in the sewer would be 0.79 g/L, assuming the import volume is used evenly between 2 customers, and water usage is by a population of 3 million using 150 L of water each day. This figure also assumes no removal or degradation in trade-waste treatment facilities. The PNEC calculated using the acute toxicity for algae was 0.73 g/L, giving a PEC/PNEC ratio just over 1, indicating a potential concern if even 1% were released. However, the ecotoxicity tests indicate ITC826 concentrate results in the highest toxicity, while Proban STi is less toxic to algae. Consequently, if we use an average of the two lowest endpoints to
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predict the no effects concentration, the PEC/PNEC ratio is 0.2, indicating no immediate concern to the environment. Sewage effluent from Sydney is released into the marine environment after only primary treatment, which would dilute the calculated PEC significantly, while effluent from Melbourne undergoes a higher level of treatment before being eventually released into the ocean.
The notified chemical is readily soluble in water, and has a low partition coefficient, indicating a poor affinity to lipids. In addition, it is not readily biodegradable and is slightly toxic to sewage micro-organisms. Hence in the sewer, the notified chemical is not expected to undergo microbial degradation, but rather would partition into the water compartment from where it may be released into the natural aquatic environment and potentially persist for some time.
Test results suggest that, in trade waste and municipal sewage treatment plants, some of the notified chemical may partition into sludge and sediments thereby reducing aquatic exposure concentrations. The substance is hydrolysed at low pH (<5), while at pH 7 and 9, the test material was found to precipitate to form insoluble hydroxides. In addition, about half of the test material was adsorbed to a soil with pH of 8.2, possibly due to it becoming insoluble at this pH.
In any case, the notified chemical is not expected to be of concern to the environment provided that a “zero discharge” licensing arrangement is in place at all user sites, and provided all bath water containing the notified chemical is recycled, and spills are collected for reuse.
9.2. Human health
9.2.1. Occupational health and safety – exposure assessmentExposure of workers involved in handling imported drums or IBCs containing the notified chemical is unlikely except in the event of container rupture as a result of an accident during transport or in the storage facility.
Exposure to the notified chemical is possible when transferring the solution containing it from the containers in which it is imported to a mixing vessel where it is diluted with water. Intermittent drips and spills during transfer will occur and workers will wear impervious gloves, goggles and a boiler suit to prevent skin and eye contact. Because the liquor so produced is stable for several months, it is drummed off at the end of a campaign together with washings from import containers, lines and the pad bath. Exposure to drips and spills can be expected while drumming off is conducted although should be reduced by dilution with wash water. Again workers will wear gloves, goggles and a boiler suit as personal protective equipment.
After fabric has been impregnated with the notified chemical worker exposure should be minimal.
9.2.2. Public health – exposure assessmentThe notified chemical is to be used solely in an industrial setting. Therefore, public exposure will most likely be confined to accidental spillage where the public may be present such as in the event of a transport accident. The probability of this occurring is expected to be low.
9.2.3. Human health - effects assessmentAn analogue of the notified chemical (ITC 826 Concentrate) was harmful via the oral route (LD50 > 50 mg/kg bw : no mortality was observed at this dose) and of low toxicity via the dermal route (LD50 > 2000 mg/kg bw) in rats. It was corrosive to the skin and a severe eye irritant in rabbits and was a skin sensitiser in guinea pigs. It was mutagenic in bacteria and in mouse lymphoma cells but was non-genotoxic in a mouse in vivo erythrocyte micronucleus test. In a 28-day oral repeat dose study in rats, ITC 826 Concentrate exhibited toxic effects on the liver and a NOEL was established as 5 mg/kg/day bw.
From the results of toxicological studies with the analogue ITC 826 Concentrate, the notified chemical is a hazardous substance in accordance with the NOHSC Approved Criteria for Classifying Hazardous Substances (NOHSC, 1999b) and is assigned the risk phrases: R22: Harmful if swallowed; R34: Causes burns; R43: May cause sensitisation by skin contact;
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R48/22: Harmful: danger of serious damage to health by prolonged exposure if swallowed.
The notified chemical is a Class 8 Dangerous Good (corrosive liquid).
9.2.4. Occupational health and safety – risk characterisationThe main acute hazards to any worker coming into contact with the notified chemical as imported is burns to the skin and eyes. The workers most at risk are those involved in dilution of the notified chemical, introduction of the resultant liquour into the pad bath, washing the containers, drums and lines and drumming off the liquor for use in further campaigns. The amount and frequency of drips and spills is unknown. However, it is clear that chemical burns could occur (more or less frequently) unless gloves, goggles and suitable overalls were worn.
Skin sensitisation could be expected to occur over a longer period of time under the same circumstances as could systemic effects although it is not possible to quantify the risk.
Workers less at risk than those mentioned above would be those involved in transport and storage of the notified chemical.
9.2.5. Public health – risk characterisationThe risk to public health would most likely be burns to skin and eyes in the event of a major transport accident and this would be expected to occur infrequently.
10. CONCLUSIONS – ASSESSMENT LEVEL OF CONCERN FOR THE ENVIRONMENT AND HUMANS
10.1. Hazard classificationBased on the available data the notified chemical is classified as hazardous under the NOHSC Approved Criteria for Classifying Hazardous Substances. The classification and labelling details are:
R22: Harmful if swallowed; R34: Causes burns; R43: May cause sensitisation by skin contact; R48/22: Harmful: danger of serious damage to health by prolonged exposure if swallowed.
10.2. Environmental risk assessmentThe notified chemical is not expected to be of concern to the environment provided that a “zero discharge” licensing arrangement is in place and is complied with. The agreement states that all bath water containing the notified chemical is recycled, and all spills are collected for reuse.
10.3. Human health risk assessment
10.3.1. Occupational health and safetyThere is High Concern to occupational health and safety under the conditions of the occupational settings described.
10.3.2. Public healthThere is Negligible Concern Concern to public health when used in the manner described.
11. MATERIAL SAFETY DATA SHEET
11.1. Material Safety Data SheetThe MSDS of the imported product containing the notified chemical provided by the notifier was in accordance with the NOHSC National Code of Practice for the Preparation of Material Safety Data Sheets (NOHSC, 1994a). It is published here as a matter of public record. The accuracy of the information on the MSDS remains the responsibility of the applicant.
11.2. Label
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The label for the imported product containing the notified chemical provided by the notifier was in accordance with the NOHSC National Code of Practice for the Labelling of Workplace Substances (NOHSC, 1994b). The accuracy of the information on the label remains the responsibility of the applicant.
12. RECOMMENDATIONS
REGULATORY CONTROLSHazard Classification and Labelling
The NOHSC Chemicals Standards Sub-committee should consider the following health hazard classification for the notified chemical:
R22: Harmful if swallowed; R34: Causes burns; R43: May cause sensitisation by skin contact;
R48/22: Harmful: danger of serious damage to health by prolonged exposure if swallowed.
Use the following risk phrases for products/mixtures containing the notified chemical: [concentration cut-off]: risk phrases
1%: All 5%, < 10%: R36, 38 (Irritating to eyes and skin) 10%: R34, R48 25%: R22
The notified chemical should be classified as follows under the ADG Code: Dangerous goods class 8, Packaging group III
Suppliers should label the notified chemical as a Class 8 dangerous good with the signal word Corrosive liquid N.O.S and the risk and safety phrases listed above.
CONTROL MEASURESOccupational Health and Safety
Employers should implement the following safe work practices to minimise occupational exposure during handling of the notified chemical as introduced and as diluted for use: Spills should be cleaned up immediately and placed into correctly labelled
containers for disposal by a licensed contractor in accordance with Federal, State and/or Local government regulations
Employers should ensure that the following personal protective equipment is used by workers to minimise occupational exposure to the notified chemical as introduced and as diluted for use: Elbow length PVC gloves, chemical goggles or face mask, overalls.
Guidance in selection of personal protective equipment can be obtained from Australian, Australian/New Zealand or other approved standards.
A copy of the MSDS should be easily accessible to employees.
If products and mixtures containing the notified chemical are classified as hazardous to
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health in accordance with the NOHSC Approved Criteria for Classifying Hazardous Substances, workplace practices and control procedures consistent with provisions of State and Territory hazardous substances legislation must be in operation.
Environment
The following control measures should be implemented by all users to minimise environmental exposure during (manufacture, formulation, use) of the notified chemical: comply with the “zero discharge” licensing arrangement put in place by the
supplier by recycling all washings containing the notified chemical; follow the supplier’s code of practice to comply with operational instructions
regarding processing and effluent release; use equipment, in the form of a refractometer, which is supplied to customers by
the supplier, to accurately measure bath strength, so that the strength of washings and bath water can be adjusted for recycling.
Disposal
The notified chemical should be recovered and reused where possible, if disposal is necessary it should be disposed of incineration or in landfill in accordance with local, State or National legislation.
Emergency procedures
Spills/release of the notified chemical, which cannot be recovered and reused, should be contained with an absorbent material, collected and placed in properly labelled and sealable containers for disposal through a licensed waste contractor, preferably be incineration. Similarly, contaminated bath water containing the notified chemical should be incinerated.
12.1. Secondary notificationThe Director of Chemicals Notification and Assessment must be notified in writing within 28 days by the notifier, other importer or manufacturer:
(1) Under Section 64(1) of the Act; if use is proposed where significant release to the aquatic environment occurs
compared with the proposed no release policy.or
(2) Under Section 64(2) of the Act: if any of the circumstances listed in the subsection arise.
The Director will then decide whether secondary notification is required.
13. BIBLIOGRAPHY
ASG (1996). Substance ITC 826 Concentrate, data for new product notification in the EC (7 th Amendment to the Dangerous Substances Directive 92/32/EC). Project 503767. Report Reference: RD012175B. Analytical Sciences Group (AGS). Manchester, UK. (unpublished report provided by the notifier).
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