Priority Existing Chemical
f.3Biological monitoring methods
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- Table 2. Summary of the AVSR additive use scenarios
f.3Biological monitoring methodsA gas chromatography protocol has been developed to determine MMT in biological tissues or fluids. MMT present in small biological samples or fluids is extracted into hexane containing biphenyl as an internal standard followed by gas chromatography utilising a flame ionisation detector. As little as 1-2 ppm MMT can be quantified using this method (Hanzlik et al., 1979). More recently, Walton et al., (1991) have described a method that combines high-performance liquid chromatography with laser-excited atomic fluorescence for the detection of MMT in urine. The limit of detection was 1.6 ng/mL. This method was also able to distinguish MMT from several MMT-derived metabolites. A number of techniques have been described for the determination of inorganic Mn in biological fluids and tissues. These include flame atomic absorption analysis, furnace atomic absorption analysis, neutron activation analysis, spectrophotometry, mass spectrometry, and x-ray fluorimetry (ATSDR 2000).
f.4Water monitoring methodsA gas chromatography protocol has been developed to determine trace amounts of MMT in water. This protocol is applicable to MMT concentrations in water of 0.05-10 ppm (the solubility limit of MMT). All samples and standards must be protected from light because solutions of water (and other solvents) are photolytic. A water sample is mixed with carbon disulfide, the carbon disulfide layer is then removed, and the MMT quantified by gas chromatography (Ethyl Corporation 1989). A number of techniques have been described for the determination of inorganic Mn in water samples. These include inductivity coupled plasma atomic emission analysis, atomic absorption spectrophotometry, catalytic kinetic analysis and colourmetric analysis (ATSDR 2000). f.5Petrol monitoring methodsA number of procedures have been described for the determination of MMT in petrol. All utilise gas chromatography, with either an electron capture detector (Giand et al., 1992), argon plasma emission detector (Uden et al., 1978; Ombana and Barry 1994), flame photometric detector (Aue et al., 1990), or atmospheric pressure helium microwave detector (Quimby et al., 1978). A gas chromatography atomic emission spectroscopy protocol has been developed to determine organic Mn in petrol. This protocol requires minimal sample preparation and is able to quantify and speciate trace organic Mn levels (Swan 1999). f.6Soil monitoring methodsAn atomic absorption spectrophotometic protocol has been developed to determine MMT in soil at concentrations above 2 ppm. A soil sample is extracted with isooctane and bromine is added to decompose the MMT. Manganese is then extracted using a dilute hydrochloric acid solution and quantified by atomic absorption spectrophotometry (Albemarle Corporation 1976). Methods have been described for the determination of inorganic Mn in soil, sediments, and sludge. In general these procedures require acid extraction/digestion prior to analysis by atomic absorption spectrophotometry or inductivity coupled plasma atomic emission spectrophotometry (ATSDR 2000). g)Importation and Use of MMTg.1ImportationMMT is imported only. The manufacture of MMT does not occur in Australia. Three companies import AVSR products containing MMT into Australia. The products are imported in bulk as a 62% MMT petroleum distillate solution in 10 000 L isotanks (HiTEC 3062) and as similar 60 and 62% MMT solutions (Wynn’s Octane Booster Concentrate and TK-660 respectively) in 205L steel drums. Solutions are less commonly imported in 450 L steel cylinders. Drummed concentrates are blended into aftermarket fuel additives in 300, 350 or 500 mL plastic bottles. MMT is also imported in pre-packaged aftermarket fuel additive products in 350 mL plastic bottles. A total of less than 180 tonnes/year of MMT are imported into Australia with less than 10 tonnes/year imported pre-packaged or for formulation into aftermarket fuel additives.
g.2UsesMMT is a multifunctional fuel additive and is commonly added to internal combustion engine fuels as a smoke abatement agent, an octane enhancer and inhibitor of valve seat recession. MMT is also reported to reduce particulate smoke emissions from household, commercial, industrial, and marine burners. This report only considers the use of MMT as an AVSR in Australia. MMT is currently not sold in Australia solely as an octane enhancer. In LRP, MMT is recommended for use at treat rates of 72.6 mg MMT (18 mg Mn)/L (< 0.01% MMT/L fuel). Aftermarket fuel additives contain MMT at < 10% w/w and at recommended treat rates, treated fuel will contain MMT at < 150 mg MMT (38 mg Mn)/L (< 0.02% MMT/L fuel). g.2.1Demand for anti-valve seat recession additivesAnti-valve seat recession fuel additives are available for both oil refinery/terminal and consumer use. AVSR fuel additives may be delivered either by pre-blending to unleaded petrol at the oil refinery or terminal (LRP) or purchased separately and added to unleaded petrol by the vehicle owner. The total Australian AVSR additive market will be referred to as the “LRP market” in this report. Following the declaration of AVSR fuel additives as a Priority Existing Chemical, importers and manufacturers of various AVSR fuel additives provided information on the import/manufacturing quantities and uses of their chemicals for 2000 and 2001. This information was used to estimate a total LRP market for 2001 of approximately 2500 ML, calculated using AVSR additive treatment doses for LRP and AVSR import/manufacturing volumes as recommended by AVSR additive manufacturers. The calculated figure of 2500 ML is slightly higher than the bulk LRP sales volumes for July 2000 to June 2001 of 1848 ML (Department of Industry, Science and Research, 2001). The market share of individual AVSR fuel additives in Australia has not been disclosed in this report due to commercial-in-confidence considerations. An analysis of the import and manufacturing data demonstrated that the aftermarket application of AVSR additives in Australia was less than 10 % of the total LRP market in 2001. In Australia, vehicles requiring leaded petrol are the major consumers of LRP. These vehicles requiring leaded petrol include passenger vehicles, light commercial trucks, rigid trucks, articulated trucks, non-freight carrying trucks, buses and motorcycles (Australian Bureau of Statistics (ABS), 2001). It is likely there are also other VSR sensitive vehicles requiring AVSR additives, e.g., tractors and some plant and equipment engines, not included on the Australian Motor Vehicle Census. However, these vehicles and engines are not expected to represent a significant component of the AVSR market. There is a declining Australian market for LRP sales (Australian Institute of Petroleum, 1999) and hence AVSR additives. This is due to attrition from the Australian motor fleet of vehicles designed to run on leaded petrol (Figure 2). By 2004, bulk sales of LRP are expected to decline to less than 5 % of total petrol sales (Australian Petroleum Gazette, 1999). This may render the general provision and sale of bulk LRP by the oil refineries and terminals uneconomical. Phase-out by the oil refineries and terminals of the provision of bulk LRP is yet to be announced by the Australian petroleum industry. Aftermarket addition of AVSR fuel additives rather than bulk treatment by the oil refineries and terminals is likely to eventually become, therefore, the only option for motorists with vehicles designed to run on leaded petrol. This may occur as early as 2004 as the supply of LRP from the oil refineries and terminal diminishes significantly. Implementation of any partial or total changeover from bulk to aftermarket supply of LRP would, no doubt, require a broad consensus among stakeholders, entailing consideration of technical and practical needs of the program and understanding and acceptance by the public.
g.2.2 Use scenariosTwo use (exposure and emission) scenarios have been assessed in this report – the present state of the market, and that likely to occur at 2004. Both scenarios are considered because of anticipated changes in occupational health and safety, public health or environmental exposure as a result of a decreasing supply of bulk LRP and the consequent increasing use of aftermarket AVSR products and also the attrition from the Australia motor vehicle population of VSR sensitive vehicles. Details of the AVSR additive use-scenarios are presented in Table 2. Table 2. Summary of the AVSR additive use scenarios
The Present Use scenario was based upon import and manufacturing data provided by industry for the calendar year 2001. The calculation of 2,500,000 vehicles is based upon 2001 calendar year total AVSR additive import and manufacturing data and a petrol fill-up rate of 19.4 L/week/leaded vehicle (Appendix 1). The calculated figure of 2 500 000 vehicles for the Present Use scenario (Table 2) is slightly lower than the ABS Motor Vehicle Census 31 March 2001 of 2 904 342 vehicles. This is attributed to the inclusion in the ABS data of all leaded vehicles irrespective of the requirement for or use of an AVSR additive. For example, not all vehicles requiring leaded petrol are VSR susceptible and require an AVSR additive. In 2000, more than 30 % of cars built before 1986 were estimated to run efficiently on normal unleaded petrol, with the remaining 70 % requiring an AVSR additive (Hill 2000). The forecast 1 000 000 vehicles for the 2004 Scenario were derived from Australian Bureau of Statistics motor vehicle census data (Australian Bureau of Statistics, 1998, 2001). One million VSR susceptible vehicles equates to a demand for LRP of approximately 1 000 ML in 2004. A description of the calculation for LRP demand in 2004 is also given in Appendix 1. The calculated LRP demand of 1 000 ML in 2004 is slightly higher than the Australian Institute of Petroleum AIP sales forecast made in 1999 of nil to 800 ML (Australian Petroleum Gazette, 1999). In 2010, a remaining niche market of VSR-sensitive older vehicles and engines requiring leaded petrol is expected (National Heritage Trust, 2000). For the purposes of commercial-in-confidence and changes in market share, it has been assumed that only one AVSR additive has 100 % market share in each use scenario. Across the assessments of all AVSR additives, the same bulk to aftermarket share is assumed for each AVSR additive.
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