Wagerup Ambient Air Quality Monitoring Programme Intensive Ambient Air Quality Study Phase 2: August to October 2004 REPORT April 2005 Dr Bob van Emden Dr Greg Power Central Chemical Consulting PO Box 2546 Malaga Western Australia 6944 Greg Power & Associates PO Box 975 Canning Bridge Western Australia 6153 -1- Table of Contents List of Figures .............................................................................................................................................................2 Executive Summary ................................................................................................................................................3 1 Introduction ..........................................................................................................................................................4 2 Sampling and Analysis........................................................................................................................................5 3 Results .................................................................................................................................................................6 4 Discussion .........................................................................................................................................................16 5 Conclusions .......................................................................................................................................................26 6 Recommendations .............................................................................................................................................26 APPENDICES...........................................................................................................................................................28 List of Figures Figure 1 Mean and maximum concentrations of formaldehyde and acetaldehyde at 11 locations over the 6 weeks as determined by passive sampling.. ............................................................................................................ 7 Figure 2 Concentrations of aldehyde and ketone compounds at the Boundary Rd 2 sampling site over the 6 week programme around the Wagerup region....................................................................................................... 8 Figure 3 Concentrations of aldehyde and ketone compounds at Hoffman Road over the 6 week sampling programme around the Wagerup region. .................................................................................................... 9 Figure 4 Concentrations of aldehyde and ketone compounds at the Yarloop Lawn Bowls over the 6 week sampling programme around the Wagerup region.. ..................................................................................... 9 Figure 5 Concentrations of aldehyde and ketone compounds at Bremnar Road over the 6 week sampling programme around the Wagerup region..................................................................................................... 10 Figure 6 Concentrations of aldehyde and ketone compounds at the Hamel Training Centre over the 6 weeks sampling programme around the Wagerup region. .................................................................................... 10 Figure 7 Weekly average formaldehyde concentrations at the 5 key sampling points around Wagerup as determined by TO-11A active sampling. ................................................................................................. 11 Figure 8 Weekly average acetaldehyde concentrations at the 5 key sampling points around Wagerup as determined by TO-11A active sampling.. .................................................................................................. 12 Figure 9 Weekly average acetone concentrations at the 5 key sampling points around Wagerup as determined by TO-11A active sampling. . ........................................................................................................................ 13 Figure 10 Average and maximum concentrations of benzene and toluene at 11 locations over the 6 week programme as determined by passive sampling. ........................................................................................ 14 -2- Wagerup Ambient Air Quality Monitoring Programme Intensive Ambient Air Quality Study Phase 2: August to October 2004 Executive Summary This report summarises and analyses the results of the second phase of an extensive air quality monitoring campaign carried out in the winter and spring months of 2004. Phase 2 included more intensive sampling at selected locations over a six week period from 23 August to 1 October 2004 in the region surrounding the Wagerup alumina refinery. The work was conducted on behalf of Alcoa World Alumina Australia (Alcoa) and the local community by independent, NATA accredited sampling and analytical specialist laboratories using USEPA or other applicable standard techniques1. Air samples were analysed for a broad spectrum of organic and inorganic species, including Volatile Organic Compounds (VOCs), Semi-Volatile Organic Compounds (SVOCs), inorganic anions, acids, and metals. Products of combustion (CO2, CO, NOx, SOx) were not included in this study. A total of 274 volatile chemical compounds were analysed for. Of these, a total of 35 were identified at quantifiable levels, and a further 31 were indicated in some samples at levels too low to quantify. The overall air quality was found to be typical of rural environments in both the nature and the levels of chemical compounds detected, except for acetaldehyde which was at levels more typical of urban environments (refer to Table 5 in the text). All of the compounds detected were at levels well below applicable environmental and health standards. These most commonly detected compounds were formaldehyde, acetaldehyde and acetone, which were found at levels similar to those measured in the DoE study in 20032. Most samples also showed the presence of lower levels of other aldehydes and ketones, as well as benzene and toluene. The main chemical compounds detected are all known to be present in refinery emissions. The levels found in the ambient environment are generally many times greater than the calculated refinery influence for each compound. There was a lack of any clear spatial distribution that would indicate a refinery influence on the levels of the compounds detected. This is consistent with the proposition that the levels of chemicals in the ambient atmosphere are dominated by human and natural processes other than the refinery operation. The chemical compounds detected and their levels in the atmosphere showed little spatial variation and for the most part appeared to be randomly distributed, limiting the ability to attribute specific sources. Elevated levels of both carbonyls and VOCs were found at the Waroona and Yarloop township sites, consistent with the effects of human activities associated with the use of fossil fuels. Sampling sites closest to the refinery generally showed lower concentrations of the compounds detected, although indications of higher than average levels of carbonyls at the Boundary Rd and to a lesser extent the Hoffman Rd sites could warrant further investigation. The study provides quality assured information on the overall air quality on a daily and weekly average basis over the study period (late winter to early spring). No clear evidence was found of an influence of the refinery on overall air quality of the study region for averaging times of 8 hours to one week. Similar results were found in the earlier study (Phase 1), carried out over a fifteen week period from 1 All sampling was carried out by Environmental Consulting Services (ECS), Unit 4, 7 Day Road, Rockingham, WA 6168, and all analysis was carried out by Leeder Consulting, Unit 5, 18 Redland Drive, Mitcham, Victoria 3132. 2 “Results of Carbonyl Sampling at Wagerup”, WA Department of Environment, January 2004. -3- May to August 2004. This is consistent with the results of recent dispersion modelling, which indicates that the contribution of the refinery to the levels of the VOCs detected in the ambient air is in general far lower than the background concentrations present from other sources. It is therefore to be expected that refinery influence will be difficult if not impossible to detect by examining the regional distribution VOC concentrations. Recommendations are made regarding additional work to further clarify the contributions of the refinery and other sources of chemical emissions to air quality in the region. 1 Introduction An intensive sampling and analysis programme has been conducted to assess air quality in the region around the Wagerup alumina refinery. The programme was developed using information from previous studies, in particular the 15-week Phase 1 Study carried out from May to September 2004. The Phase 2 Study scope was developed by Alcoa with input from the community, DoE, the Chemistry Centre and CSIRO. The independent specialists contracted to perform the sampling and analysis were chosen through a formal, open competitive bidding process managed by Alcoa on behalf of the stakeholders and with direct input from community representatives. NATA accreditation of procedures was a condition of the selection process. USEPA methods were used wherever possible, otherwise applicable Australian Standard or International Standard methods were used. This report is an analysis of the data as presented, and while all due care was taken in relation to data integrity, the authors are not responsible for any errors in the original data. The methodology and data were not derived or directly audited by the authors. -4- 2 Sampling and Analysis 2.1 Sampling and analysis: an overview of methods The three main sampling techniques used were: • Passive sampling for aldehydes, ketones and VOCs using the Radiello3 sampling technique, in which samples were collected weekly at 11 locations, in duplicate; • Active sampling for aldehyde and ketones using the USEPA methods TO-11A & TO-5A, VOCs using USEPA method TO-17, SVOCs using USEPA method TO-13, inorganic acids using NIOSH 7903, and halogens using NIOSH 6011. Samples were collected at 5 locations in duplicate, 3 times per week for 8 hours starting about 8:00am; • Active sampling for metals associated with particulates. Method AS 2800-1985, which is for the determination of lead, was the sampling method used for all metals. The sample is collected using a High Volume Sampler. Samples were collected at four sites, each sample being taken over a period of one week. Between one and six samples were taken at each site. The lead component was determined as by Atomic Flame Mass Spectroscopy (AFMS), as per AS 28001985. The additional metals were analysed by the method most appropriate for each particular metal, using either AFMS or vapour generation and Inductively Coupled Plasma Spectroscopy (ICP). Radiello sampling is a proprietary method for the passive collection of VOCs from ambient air using cylindrical cartridges containing an inner adsorbent and outer radial diffusion layer1. It has the advantage of requiring no pumping or metering of air, and no power supply. Radiello sampling can be used to collect under ambient conditions over a long period of time, and so can be used where the concentration of VOCs is below the normal detection limits for active sampling over a shorter time. Any transient excursions in the concentrations of VOCs are captured by this sampling method and included in the overall average concentrations. The USEPA TO-11A methodology for monitoring air with low carbonyl content requires a calibrated pumping system to sample ambient air for a known time between 1 and 24 hours. The ambient air flow can be between 100 mL/minute and 2000 mL/minute, depending on the concentration of organics present. The ambient air is passed through a cartridge containing an adsorbent such as silica coated with 2,4-dinitrophenylhydrazine (DNPH) and a strong acid catalyst. The hydrazones resulting from reaction with airborne aldehydes and ketones are later analysed using high performance liquid chromatography. Before contacting the DNPH adsorbent, the ambient air is passed through granular potassium iodide to remove ozone, necessary to prevent loss of the DNPH product prior to analysis. Using TO-11A, low molecular weight carbonyl compounds including benzaldehyde are commonly measured to less than 0.5 ppb by volume. The USEPA TO-5A method is an older operating procedure in which air is passed through an impinger containing solutions of DNPH, so that the solutions capture the ambient aldehydes and ketones. As with TO-11A, the hydrazones formed are analysed using HPLC. The accuracy of the TO-5A method can allow measurements down to 1-2 ppb by volume. A USEPA TO-17 sampling protocol collects ambient VOCs by passing a known volume of air through suitable media, followed by thermal desorption, then gas chromatography and mass spectrometry for analysis. The method is considered capable of measuring VOC concentrations of 0.5 ppb to 25 ppb in ambient air. 3 For further details visit the web page at: http://www.radiello.it/english/ -5- The USEPA TO-13A technique utilises the collection of polyaromatic hydrocarbons (PAHs), typically onto polyurethane foam (PUF) or a similar adsorbent, followed later by desorption and analysis of the PAHs. Analysis is achieved by separation of components by gas chromatography followed by detection by mass spectrometry. A known volume of approximately 300,000 litres of air is typically drawn through the PUF adsorbent filters during rapid flow sampling (220 litres/minute). The TO-13A method is applicable to the measurement of easily condensed PAHs containing three or more aromatic rings. 2.2 Sampling sites Passive sampling was conducted at the following 11 locations throughout the 6 weeks of the comprehensive programme: Boundary Road, Hoffman Road; Bremnar Road, Hamel Training Centre, the Yarloop Lawn Bowls, Residue Area, Residue South, Hamel Neighbour, Yarloop Neighbour, the Waroona Lawn Bowls and the Willowdale Mine. Refer to Appendix 1 for the location of each sampling point on the aerial photograph. Active sampling was conducted at the following 5 locations throughout the 6 weeks of the comprehensive programme: Boundary Rd 2 (8), Hoffman Road (10), Bremnar Road (11), Hamel Training Centre (2), and the Yarloop Lawn Bowls (5). Refer to Appendix 1 for the location of each sampling point. 3 Results 3.1 Background aldehyde and ketones by passive sampling Over the 6 week period of passive sample collection at 11 locations, five compounds: formaldehyde, acetaldehyde, propanal, butanal and benzaldehyde, were measured at concentrations above their respective method detection limits (see Appendix 2A&B). Formaldehyde and acetaldehyde concentrations are frequently above their detectable limit and show measurable variation between the different sampling sites (see Appendix 3). Figure 1 shows the mean and maximum weekly (background) formaldehyde and acetaldehyde concentrations at the 11 different sites during the 6 week period from 23rd August to 1st October 2004 (source data is in Appendix 3). -6- 5.00 Formaldeyde Acetaldehyde Maximum Maximum Aldehyde Conc. (ug/m3) 4.00 3.00 2.00 1.00 0.00 Bremnar Road Residue Area Residue South Boundary Road 3 Boundary Road 2 Hoffman Road Clifton Road Yarloop Yarloop Lawn Bowls Willowdale Mine Waroona Lawn Bowls Hamel Training Centre Figure 1 Mean and maximum concentrations of formaldehyde and acetaldehyde at 11 locations over the 6 weeks as determined by passive sampling. Both compounds are well below applicable health limits (11 and 50ug/m3 respectively for chronic health effects) and their odour thresholds (60 to 1230 for formaldehyde and 380 for acetaldehyde) – see Table 4. The highest concentration of formaldehyde and acetaldehyde (8 to 10 times the Method Detection Limit (MDL – see Appendix 4 for definition) occurs at Waroona Lawn Bowls (Sample Point 1) some 10 km north of the refinery (see Figure 1 and Appendix 1). This is attributable to sources associated with various localized activities including emissions from vehicles and other combustion engine devices, domestic and other wood fires, tobacco smoke, domestic chemicals and building products (Table 6), which are expected to be more concentrated in the town than in the surrounding rural environment. Bremnar Road (Sample Point 11) and Hamel Neighbour (Sample Point 9) (labeled “Point 1 Boundary Road” on aerial photo) sample points had the lowest mean background concentration of these 2 compounds. At the latter sites the mean values are only 2 - 4 times the average MDL (indicated by the dashed line in Figure 1). The concentration of propanal, butanal and benzaldehyde was frequently measured at below the method detection limits. This makes averaging of duplicate results unreliable, in which case they are recorded as “D” (when detected but not quantified) or “nd” (not detected) in Appendix 2. 3.2 Concentrations of aldehydes and ketones at 5 key sites by active sampling A total of twelve different aldehyde and ketone (carbonyl) compounds: formaldehyde, acetone, acetaldehyde, benzaldehyde, hexanal, butanal/isobutyraldehyde, propanal, acrolein, methacrolein, pentanal, 2-pentanone/3-methyl-2-butanone and methyl ethyl ketone, were measured at concentrations above their respective detection limits (by USEPA TO-11A), though only the first three were present in the majority of samples. The formaldehyde and acetaldehyde concentrations are consistently above -7- their MDLs at each of the 5 sampling locations (see Figures 2–6 & Appendix 5). concentrations recorded were well below the applicable 24 hour health standards (Table 4). All the The concentrations of carbonyls at the 5 key sampling sites are also shown in Figures 2 to 6. Yarloop Lawn Bowls and Bremnar Road sites recorded several higher propanal concentrations, while the other six compounds generally lower than at the other four sites (see Figures 2 to 6). Propanal is associated with vegetative and fossil fuel burning, wood heaters, tobacco smoke, and burning plastics, and is emitted naturally from trees and shrubs (Table 6). The Hoffman Road site reports several mean duplicate benzaldehyde concentrations that are well above the MDL and higher than the other sites (see Figure 3). The other 5 compounds (not displayed in Figures 2 to 6) are detected infrequently at the 5 sampling points (see Appendix 6). There are no significant differences in the concentration levels of these compounds at the 5 different sites. Recent dispersion modelling (CSIRO, 2005) indicates that the observed concentrations of these compounds in the ambient air are not explained by their presence in refinery emissions, because the calculated contribution of the refinery is in every case many times less than the concentrations observed. This indicates that the measured levels are dominated by other natural and anthropomorphic processes (Table 6). 12.0 Boundary Rd 2 10.0 Week 1 Week 2 Week 3 Week 4 Week 5 Week 6 Ave MDL Concentration (ug/m3) 8.0 Site Mean 6.0 4.0 2.0 0.0 Formaldehyde Acetaldehyde Acetone Propanal Hexanal MEK Benzaldehyde Figure 2 Concentrations of aldehyde and ketone compounds at the Boundary Rd 2 sampling site over the 6 week programme around the Wagerup region. All concentrations are well below applicable health standard levels (Table 4). Each point represents the average of duplicates on a given day. -8- 12.0 Hoffman Road Week 1 Week 2 Week 3 Week 4 Week 5 Week 6 10.0 Ave MDL Site Mean Concentration (ug/m3) 8.0 6.0 4.0 2.0 0.0 Formaldehyde Acetaldehyde Acetone Propanal Hexanal MEK Benzaldehyde Figure 3 Concentrations of aldehyde and ketone compounds at Hoffman Road over the 6 week sampling programme around the Wagerup region. All concentrations are well below applicable health standard levels (Table 4). Each point represents the average of duplicates on a given day. 12.0 Yarloop Lawn Bowls 10.0 Week 1 Week 2 Week 3 Week 4 Week 5 Week 6 Ave MDL Site Mean Concentration (ug/m3) 8.0 6.0 4.0 2.0 0.0 Formaldehyde Acetaldehyde Acetone Propanal Hexanal MEK Benzaldehyde Figure 4 Concentrations of aldehyde and ketone compounds at the Yarloop Lawn Bowls over the 6 week sampling programme around the Wagerup region. All concentrations are well below applicable health standard levels (Table 4). Each point represents the average of duplicates on a given day. -9- 12.0 Bremnar Road Week 1 Week 2 Week 3 Week 4 Week 5 Week 6 10.0 Ave MDL Site Mean Concentration (ug/m3) 8.0 6.0 4.0 2.0 0.0 Formaldehyde Acetaldehyde Acetone Propanal Hexanal MEK Benzaldehyde Figure 5 Concentrations of aldehyde and ketone compounds at Bremnar Road over the 6 week sampling programme around the Wagerup region. All concentrations are well below applicable health standard levels (Table 4). Each point represents the average of duplicates on a given day. 12.0 Hamel Training Centre Week 1 Week 2 Week 3 Week 4 Week 5 Week 6 10.0 Ave MDL Site Mean Concentration (ug/m3) 8.0 6.0 4.0 2.0 0.0 Formaldehyde Acetaldehyde Acetone Propanal Hexanal MEK Benzaldehyde Figure 6 Concentrations of aldehyde and ketone compounds at the Hamel Training Centre over the 6 weeks sampling programme around the Wagerup region. All concentrations are well below applicable health standard levels (Table 4). Each point represents the average of duplicates on a given day. - 10 - The mean concentration of formaldehyde in week four (4.4 ug/m3), is higher than all other weeks at each of the 5 sample collection points. Reliable mean (duplicate) values are obtained during this week since they are frequently more than twice the average detection limit (MDL - see Figure 7 & Appendix 5). The concentration of formaldehyde at all 5 sites in week 3 is lower than for the other 5 weeks (see Figures 7 & 8). The concentrations of formaldehyde and acetaldehyde during this week were often less than 1.5 times their MDLs. The calculated mean concentrations are therefore less reliable (see Appendix 4 & 5). The highest weekly formaldehyde concentrations occurred at the Boundary Rd 2 and Hoffman Road sampling points, but the differences between these and the other sites are small and the weekly variation in mean formaldehyde concentration is greater than the differences between the 5 sampling points (see Figure 7). Week 1 Week 2 Week 3 Week 4 Week 5 Week 6 Maximum 10.0 Formaldehyde Conc. (ug/m3) 6 week mean Ave MDL 7.5 5.0 2.5 0.0 Boundary Rd 2 Hoffman Road Yarloop Lawn Bowls Bremnar Road Hamel Training Centre Figure 7 Weekly average formaldehyde concentrations at the 5 key sampling points around Wagerup as determined by TO-11A active sampling. The bars show weekly average values. The points show the highest value recorded each week, with the week identified by the colour of the symbol. All concentrations are well below applicable health standard levels (Table 4). - 11 - Week 1 Week 2 Week 3 Week 4 Week 5 Week 6 Maximum S i 4 10.0 Acetaldehyde Conc. (ug/m3) 6 week mean Ave MDL 7.5 5.0 2.5 0.0 Boundary Rd 2 Hoffman Road Yarloop Lawn Bowls Bremnar Road Hamel Training Centre Figure 8 Weekly average acetaldehyde concentrations at the 5 key sampling points around Wagerup as determined by TO-11A active sampling. The bars show weekly average values. The points show the highest value recorded each week, with the week identified by the colour of the symbol. All concentrations are well below applicable health standard levels (Table 4). The highest weekly mean concentration of acetaldehyde over all sites for the 6 week programme was 2.5 ug/m3 (Appendix 5), and this occurred in weeks 4 & 5. The highest individual weekly value of 4.9 ug/m3 was recorded in week 5 at Boundary Rd. (see Figure 8 & Appendix 5). Week 3 has the lowest mean concentration of acetaldehyde (1.5 ug/m3), although the difference with other weeks is smaller than for formaldehyde. The average differences between sites do not appear to be statistically significant because the weekly variation in mean acetaldehyde concentration (1.5 – 2.5 ug/m3) is similar to the differences between the 5 sampling points. The mean concentrations of acetone in weeks two and four (1.5 - 1.6 ug/m3) are higher than for the other weeks (0.5 – 1.3 ug/m3) (see Appendix 5). Week three has the lowest mean concentration, at approximately half the average method detection limit (see Appendix 4). The highest weekly acetone concentrations appear to be at the Boundary Rd 2 and Hoffman Road sampling points, although it is doubtful that this is statistically significant because they lie only slightly above the average six-week MDL. Hamel Training Centre records the lowest mean acetone concentrations, with no acetone detected in weeks one and three4. The weekly variation in mean acetone concentration is greater than the differences between the 5 sampling points (see Figure 9). While the variations between sites are too small in relation to overall variability to be definitive, the average values appear to be marginally higher at the Boundary Rd and Hoffman Rd sites, and these sites also show the majority of highest individual results for the carbonyl compounds. No comparative data are available for Waroona, which would be expected to be higher based on the Radiello results. 4 Only one duplicate run was performed at Hamel Training Centre during week one. - 12 - Week 1 Week 2 Week 3 Week 4 Week 5 Week 6 Maximum Weekly 10.0 6 Week Mean Acetone Conc. (ug/m3) Ave MDL 7.5 5.0 2.5 0.0 Boundary Rd 2 Hoffman Road Yarloop Lawn Bowls Bremnar Road Hamel Training Centre Figure 9 Weekly average acetone concentrations at the 5 key sampling points around Wagerup as determined by TO-11A active sampling. The bars show weekly average values. The points show the highest value recorded each week, with the week identified by the colour of the symbol. All concentrations are well below applicable health standard levels (Table 4). Ambient air samples were also collected by an alternative active sampling method, USEPA Method TO-5A, for aldehyde and ketone analysis. Formaldehyde, acetone, acetaldehyde, butanal/isobutyraldehyde, hexanal, and 2-pentanone/3-methyl-2-butanone were detected by this method. However the results are less useful than from TO-11A because of the lower sensitivity of TO5A, which meant that most results failed to satisfy reporting quality criteria (see Appendices 4 & 7). 3.3 VOCs collected by passive sampling at 11 different sites A total of eleven VOC compounds were detected by passive sampling at the 11 passive sampling points: benzene, toluene, xylenes, n-decane, n-hexane, n-heptane, isooctane, isobutanol, 2-methyl pentane, 3-methyl pentane and cylcohexane. All of these compounds were measured at low concentrations and often were not detected in individual samples (see Appendix 8). Benzene and toluene were the species most frequently detected at the 11 sampling points over the 6 week programme. The mean concentration of benzene and toluene is highest in ambient air sampled at the Waroona and Yarloop Lawn Bowls sampling locations (see Figure 10). These sample points are the only ones to have mean concentrations of any VOC above the average MDL (see Figure 10 & Appendix 8). It is therefore not possible to present a true average concentration for these compounds for each site, and the values shown below the MDL in Figure 10 are indicative only. A greater proportion of samples from Waroona and Yarloop Lawn Bowls record individual VOC concentrations above their MDLs (see Appendix 8). The higher concentrations of VOCs recorded at the township sites are consistent with the presence of general fuel burning activities (vehicles, wood fires, etc – see Table 6). All values recorded are well below applicable health standard levels (Table 4). - 13 - 3.00 Benzene Toluene maximum maximum 2.50 Ave MDL = 0.12 ug/m3 Concentration (ug/m3) 2.00 1.50 1.00 0.50 0.00 Bremnar Road Residue Area Residue South Boundary Road 3 Boundary Road 2 Hoffman Road Clifton Road Yarloop Willowdale Waroona Yarloop Lawn Bowls Mine Lawn Bowls Hamel Training Centre Figure 10 Average and maximum concentrations of benzene and toluene at 11 locations over the 6 week programme as determined by passive sampling. The influence of fuel burning activities in townships is evident. All concentrations are well below applicable health standard levels (Table 4). 3.4 Concentration of VOCs at the 5 key sampling sites Benzene, toluene, xylene and carbon tetrachloride were the only VOCs collected by active sampling with ambient concentrations above detection limits. However it is not possible to report a reliable mean concentration for these compounds since most values were below the MDLs (see Appendix 9A). There are no clear differences between VOC concentrations in a particular week or between sampling locations. The following VOCs were detected but not quantified by USEPA TO-17 during the 6 week period: n-hexane, n-pentane, iso-pentane, 2-methyl pentane, 3-methyl pentane and methyl cyclopentane. They were detected most frequently at the Yarloop Lawn Bowls site (see Appendix 9B). All concentrations are well below applicable health standard levels (Table 4). 3.6 Concentration of SVOCs the 5 key sampling sites The following SVOCs were detected and quantified using USEPA Method TO-13A during the 6 week sampling programme at the five key sampling sites: fluorene, naphthalene, phenanthrene, dibenzofuran, 1-methyl naphthalene, 2- methyl naphthalene, m&p-cresol, o-cresol, phenol, 2,4-dimethylphenol, 1,4 dichlorobenzene, fluoranthene, pyrene and benzyl alcohol (see Appendix 10A&B). These compounds were at the greatest concentration, and most frequently detected at Yarloop Lawn Bowls where three or more were detected on most sampling days (see Appendix 10B)5. All concentrations are well below applicable health standard levels (Table 4). 5 No samples were collected by TO-13A at Boundary Rd 2 or Waroona during the 6 weeks. - 14 - 3.7 Trace metal concentrations in suspended particulates Samples of ambient air were collected at the Hoffman Road, Hamel Training Centre, Bremnar Road and Boundary Rd 2 sites to determine the lead and other metals content on solid particulates. The results of the weekly samples show levels of lead, mercury and other heavy metals (see Appendix 11). All concentrations measured are at very low levels. Examples of comparisons with applicable health standard levels are shown in Table 4A. 3.8 Inorganic acid concentrations at the 5 key sites Samples of ambient air were collected at the 5 key sampling sites to determine the concentration of six different inorganic acids. The results of weekly 6 hour samples collected at each site showed the absence of all inorganic acids except for occasional traces of sulphuric acid at the Bremnar Road and Hamel Training Centre sites at different times (see Appendix 12). The highest value recorded was 130ug/m3, well below the NPI 8 hour TWA standard of 1000ug/m3. All other samples were below 110ug/m3. No source of the traces of sulphuric acid was identified. 3.9 Chlorine and bromine concentrations at the 5 key sites Samples of ambient air were collected at the Boundary Rd 2, Hoffman Road, Bremnar Road and Hamel Training Centre sites for determination of bromine and chlorine. The results of the weekly samples show traces of both bromine and chlorine at each site on occasions (Appendix 13). Two samples showed quantifiable levels of chlorine, at 170 and 150 ug/m3, and all other samples were below these levels. These results are well below the 8 hour TWA of 1500 ug/m3 according to NIOSH and OSHA. No specific source was identified for either element. . - 15 - 4 Discussion 4.1 Comparison between passive and active sampling results: Carbonyls The passive sampling apparatus adsorbs sample over an entire week which results in averaging of air concentration over this period. This type of sampling results in high sensitivity (low method detection limits) because a larger quantity of compound can be collected over the longer sampling periods made available by this method. Transient peaks occurring within the period are captured and included in the average concentration recorded. The aldehyde and ketone data acquired by this technique are different to the data from samples collected by active sampling over of 8 hour periods during daylight hours. A comparison of formaldehyde and acetaldehyde concentrations determined by passive (Radiello) and active sampling (TO-11A) is shown in Table 1. Both formaldehyde and acetaldehyde concentrations are recorded higher at all sites when sampled and analysed by TO-11A. The aldehyde and ketone contributions to ambient air from human activity (in particular vehicular traffic and other fuel burning activities) may be expected to be greatest during daylight hours, which may at least partly explain the observed difference. However no investigation of method biases was done, so artefacts due to the differences between the sampling techniques cannot be discounted. The weekly average concentrations measured by passive sampling showed that the average and individual highest values were greatest at the Waroona Lawn Bowls site. The lowest values were recorded at Residue South, the closest site to the refinery, and Bremnar Rd, which is farthest from both the refinery and the towns (Fig 1). This indicates that the influence of general human activities associated with the town (principally fuel burning) have a significant influence on the overall levels of carbonyls in the atmosphere, whereas a refinery influence could not be discerned. The results of the active sampling show indications of higher values at the Boundary Rd and Hoffman Rd sites than at the other key sites sampled. Whether this could be indicative of a refinery influence is unclear, and no comparison with Waroona can be drawn because it was not included in the group of key sites for active sampling. Table 1. Mean formaldehyde and acetaldehyde concentration at each of the 5 key sampling sites determined by TO-11A and Radiello Formaldehyde (ug/m3) Location Acetaldehyde (ug/m3) Active (8 hrs) Passive (1 week) Active (8 hrs) Passive (1 week) Boundary Rd 2 3.27 0.80 2.60 0.37 Hoffman Road 3.15 0.45 2.36 0.25 Yarloop Lawn Bowls 2.57 0.93 1.73 0.43 Bremnar Road 2.68 0.34 1.84 0.26 Hamel Training Centre 2.22 0.70 1.68 0.32 All sites 2.8 0.6 2.0 0.3 - 16 - 4.2 Comparison between passive and active sampling results: VOCs The results from passive and active sampling for VOCs show a similar pattern to the aldehydes and ketones discussed above. This is illustrated in Table 1a, which shows the maximum concentrations recorded for benzene and toluene at the same sites (maximum values are given because it was not possible to determine averages due to the large number of non-detects – see Appendices 7&8). The maximum concentrations of benzene and toluene (4.6 & 1.7 ug/m3) obtained by active sampling are higher than the weekly maximum VOC concentrations at the corresponding 5 sites determined by passive sampling (0.37 & 0.41 ug/m3). A larger number of different VOCs were detected by passive sampling due to the lower method detection limits (see Appendices 7&8). The results of passive sampling show the highest concentrations of benzene and toluene at the Waroona and Yarloop township sampling sites, with Waroona the greater. The Residue sites, which are the closest sampling sites to the refinery, show among the lowest concentrations. This again indicates that fuel burning activities in the towns are the most notable influence on the overall concentrations of the measured compounds in the atmosphere. The pattern is similar for active sampling, with the Yarloop site showing the highest levels of benzene and toluene, and also the largest number of individual VOCs detected. Comparison with Waroona could not be made because it was not included in the group of key sites. An exception is the single high benzene result recorded at Hoffman Rd. Table 1a. Maximum benzene and toluene concentration at each of the 5 key sampling sites determined by TO-17 and Radiello Benzene (ug/m3) Location Toluene (ug/m3) Active (8 hrs) Passive (1 week) Active (8 hrs) Passive (1 week) Boundary Rd 2 0.58 0.12 nd 0.14 Hoffman Road 4.6 nd nd nd Yarloop Lawn Bowls 0.62 0.37 1.7 0.41 Bremnar Road 0.62 0.12 nd 0.13 Hamel Training Centre 0.73 0.12 0.60 0.27 - 17 - 4.3 Summary of all compounds detected during ambient study A total of 66 different volatile compounds were detected (at least once) using both active and passive sampling techniques during the 6 week ambient programme. The compound types identified were: aldehyde and ketones (29 different compounds), aromatics (9), alkanes & cycloalkanes (14), alcohols, phenols & cresols (8), heterocycles (2), organohalides & halides (3) and others (1) (see Table 2). Table 2. Comprehensive list of all VOCs detected by active ambient sampling in this study of the region surrounding the Wagerup Refinery. Compound detected Aldehydes and Ketones Formaldehyde Acetaldehyde 2-Propenal (Acrolein) Acetone Propanal 2-methylPropenal (Methacrolein) Butenal Methyl Vinyl ketone 2-Butanone (MEK) Butanal* Methylglyoxal 3-Penten-2-one Pentanal 2-Pentanone** 3-Methyl-2-butanone** Cyclohexanone trans-2-Hexenal 3,3-Dimethyl-2-butanone Hexanal Benzaldehyde Heptanal Tolualdehyde 6-Methyl-5-hepten-2-one Octanal Ambient Concentration (ug/m3) Active Passive nd - 7.0 nd - 11.4 nd - 0.25 nd - 5.4 nd - 4.6 nd - 0.56 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 Radiello Radiello nd - 0.096 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 D, SQ nd - 0.56 nd - 0.52 D, SQ D, SQ nd - 0.95 nd - 0.89 D, SQ D, SQ D, SQ D, SQ nd - 0.54 nd - 3.6 D, SQ nd - 0.15 D, SQ D, SQ Nonanal Vanillin D, SQ D, SQ Decanal Undecanal Dodecanal D, SQ D, SQ D, SQ Alcohols, Phenols & Cresols isoButanol Phenol Benzyl Alcohol 2 methylPhenol (o-Cresol) 3&4 methylPhenol (m&p-Cresol) 2,4 Dimethyl Phenol 2-ethylHexanol Eucalyptol TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 Radiello Radiello Radiello TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5 TO-11A, TO-5, TO13A TO-11A TO-11A, TO-5, TO13A TO-11A, TO-5 TO-11A, TO-5 nd - 1.8 nd - 0.0099 nd - 0.068 nd - 0.0092 nd - 0.018 nd - 0.013 T, SQ TO-13A TO-13A TO-13A TO-13A TO-13A Radiello T, SQ TO-13A Radiello Molecular Weight 30.0 44.0 56.1 58.1 58.1 70.1 CAS 120.1 126.2 128.2 50-00-0 75-07-0 107-22-2 67-64-1 123-38-6 78-85-3 4170-303 78-94-4 78-93-3 123-72-8 78-98-8 96-22-0 110-62-3 107-87-9 563-80-4 108-94-1 6728-263 75-97-8 66-25-1 100-52-7 111-71-7 1334-787 110-93-0 124-13-0 142.1 152.1 124-19-6 121-33-5 156.1 170.1 184.1 112-31-2 112-44-7 112-54-9 74.1 94.1 108.1 108.2 108.2 122.2 130.3 75-65-12 108-95-2 100-51-6 95-48-7 106-44-5 105-67-9 104-76-7 470-82 to 6 70.1 70.1 72.1 72.1 72.1 86.1 86.1 86.1 86.2 98.1 98.1 100.1 100.2 106.1 114.2 154.1 - 18 - Table 2. (cont.) Compound detected Ambient Concentration (ug/m3) Active Alkanes and Cycloalkanes n-Pentane Isopentane methylCyclopentane 2-methyl-Pentane 3-methyl-Pentane n-Hexane n-Decane Undecane Dodecane Tridecane Tetradecane Hexadecane Heptadecane Octadecane T, SQ T, SQ T, SQ T, SQ T, SQ nd - >L, SQ T, SQ T, SQ T, SQ T, SQ T, SQ T, SQ T, SQ T, SQ TO-17 TO-17 TO-17 TO-17 TO-17 TO-17 TO-17 TO-13A Aromatics Benzene Toluene Xylenes Naphthalene 1-Methyl Naphthalene 2-Methyl Naphthalene Flourene Phenanthrene Fluoanthene nd - 4.6 nd - 1.7 nd - 1.1 nd - 0.030 nd - 0.0099 nd - 0.02 nd - 0.0033 nd - 0.0066 nd - 0.0011 Heterocycles Dibenzofuran Pyrene Organo Halides & Halides Chlorine 1,4 Dichlorobenzene Carbon tetrachloride Passive Molecular Weight CAS 72.2 72.2 84.2 86.2 86.2 86.2 142.3 156.3 170.3 184.4 198.4 226.5 240.2 109-66-0 78-78-4 96-37-7 107-83-5 96-14-0 1120-21-4 124-18-5 1120-21-4 112-40-3 629-50-5 629-59-4 544-76-3 TO-17 TO-17 TO-17 TO-13A TO-13A TO-13A TO-13A TO-13A TO-13A 78.1 92.1 106.2 128.2 142.2 142.2 166.2 178.2 202.3 71-13-2 108-88-3 108-38-3 91-20-3 90-12-0 91-57-6 86-73-7 85-01-8 206-44-0 nd - 0.0033 nd - 0.0032 TO-13A TO-13A 168.2 202.2 132 to 64-9 129-00-0 nd - 170 nd - 0.0099 nd - 0.73 NIOSH-6011 TO-13A TO-17 70.9 147.0 153.8 7782-50-5 106-46-7 56-23-5 nd - 360 NIOSH-7903 98.1 7664-38-2 Radiello Radiello Radiello Radiello Radiello TO-13A TO-13A TO-13A Others Sulphuric acid Notes: nd: not detected T, SQ: tentative assignment & semi –quantitative D, SQ: assigned but semi-quantitative only >L, SQ: exceeds calibration limit so semi-quantitative results. Shading indicates the compounds are not present in Wagerup Refinery emissions, according to the Wagerup Refinery Air Emissions Inventory Final Report, 2002. Source Alcoa TDG - 19 - Of the 66 species detected, just over half (35), have been determined quantitatively in this study (see Table 3 for more details). The remaining compounds were recorded with tentative assignments and semi-quantitative values only, due to low levels and/or lack of appropriate standards and accreditation for the analysis . Table 3 Summary of sampling methods and detection limits used to identify all compounds throughout the programme. Compound/ type Aldehydeyor ketone acetone propanal, hexanal etc Sampling method Passive or active Collection time Ave MDL ug/m3 # Species analysed for # Species quantified # Species detected only TO-11A TO-11A Active Active 8 hours 8 hours 1.2 0.12 29 14 15 TO-5A Active 12 hours 13 27 6 13 Radiello Passive 1 week 0.11 Radiello Radiello Passive Passive 1 week 1 week 0.25 0.87 9 5 0 TO-17 Active 2 hours 0.6 - 1.2 52 4 6 Radiello Passive 1 week 0.11 - 0.16 35 11 4 TO-13A Active 1-3 days 0.001 - 0.004 212 14 6 NIOSH-7903 NIOSH-7903 Active Active 6 hours 6 hours 90 - 130 45 - 64 6 1 0 AS-2800 Active 1 week 0.000001-0.0001 18 17 0 NIOSH-6011 Active 3 1/2 hours 130 - 170 2 1 0 y Aldehyde or ketone formaldehyde, acetaldehyde & acetone including propanal, hexanal etc Aldehydes formaldehyde, acetaldehyde & benzaldehyde propanal butanal VOC benzene, toluene & carbon tetrachloride etc VOC benzene, toluene, xylenes hexane etc & n- SVOC naphthalene, phenol cresol etc & o- Inorganics sulphuric acid, hydrochloric acid, hydrogen fluoride Metals lead, aluminium, arsenic, boron,barium, beryllium, cadmuim, cobalt, copper, gallium, mercury, lithium, molybdenum, nickel, selenium, thalium, vanadium Halogens chlorine & bromine - 20 - 4.4 Comparison of concentrations of species at the 5 key sampling sites with odour thresholds, ambient guidelines, and typical rural air quality The peak concentrations of the VOCs measured are well below ambient air guideline levels (Table 4). This is also true for odour thresholds, with the possible exception of benzaldehyde which was occasionally measured at the lower end of its range of reported odour threshold values and has a pleasant, fruity smell. Table 4: Ambient Air Quality Guidelines and Odour Thresholds Species Formaldehyde Acetaldehyde Acetone Propanal Benzaldehyde 2-Butanone (MEK) Hexanal Methacrolein Acrolein Butanal Butenal Pentanal Tolualdehyde 2-Pentanone Maximum Concentration Measured (ug/m3) 7.0 11.4 5.4 4.6 3.6 0.56 0.54 0.56 0.25 0.52 0.10 0.95 0.15 0.89 Acute Health Effects Value Averaging (ug/m3) Period Reference 54 24 h NEPC(AT) 2,000 24hr WHOa 66,000 24hr ATSDR 3 24hr OAQC 13,000 1hr OEHHA 4 0.2 1h 1h TCEQ OEHHA 0.4 0.06 Annual Annual 100 Odour TCEQ 10 Odour 530 1h TCEQ Carbon Tetrachloride 0.73 1900 130 7h 1h Benzene 4.6 174 1,300 150 600 12000 4,113 1,083 152 19,000 5,800 500 22,000 24hr 6h 8hr Dibenzofuran 1,4-Dichloro Benzene) 0.0033 0.0099 Toluene Xylenes iso-Butanol Phenol 2.3 1.1 1.8 0.0099 2,4-Dimethyl Phenol Benzyl Alcohol m&p-Cresol o-Cresol Cresol mixtures 0.0130 0.068 0.018 0.0092 Chronic Health Effects Value Averaging (ug/m3) Period Reference 11 Annual NEPC(AT) 50 Annual WHOa 33,000 Annual ATSDR 2 Annual TCEQ 2.2 Annual TCEQ 5,000 Annual IRIS 24hr 24hr 1h 8hr 1h 1h 8hr Carcinogenic Effects Probability (per ug/m3) Reference 1.30E-05 NEPC(AT) 9.00E-07 WHOa TCEQ OEHHA TCEQ TCEQ NOHSC OSHA (STL) NIOSH (REL) OEHHA TCEQ ATSDR OEHHA 6.00E-06 WHO 5300 Annual 705000 TWA 410000 TWA 250 TWA OEHHA 40 TCEQ 13 0.2 (0.03 ppm) ATSDR 60 Annual OEHHA 20 pg/m3 based on TGA TMI of 70 pg/kg/day for dioxin ACGIH TCEQ 60 TCEQ ATSDR 120 ATSDR NEPC(AT) 411 Annual NEPC(AT) NEPC(AT) 946 Annual NEPC(AT) TCEQ 1520 Annual TCEQ OSHA 150 Annual TCEQ OEHHA 200 OEHHA 73 US EPA PRG TCEQ 50 Annual TCEQ OSHA OEHHA 0.5 Annual TCEQ - The following should all be handled as PAH using TEF for chronic effects Pyrene 0.0032 1-Methyl Naphthalene 0.0099 2-Methyl Naphthalene 0.020 Naphthalene 0.03 Total Naphthalenes 0.06 Phenanthrene 0.0066 100 10hr NIOSH Fluorene 0.0033 Fluoranthene 0.0011 - 4 - Annual - ATSDR - - Odour Threshold ug/m3 60 -1,230 380 47,300 22 - 400 0.8 - 180 15,900 19 >300,000 - Odour Guideline - >8,000 150 - ug/m3 20 22 5 - 440 - - Reference TCEQ TCEQ TCEQ - Indicates values close to a known exposure standard References: NEPC(AT) WHOa OEHHA ATSDR OAQC NIOSH ACGIH National Environmental Protection (Air Toxics) Measure (NEPC, 2004) World Health Organisation Guidelines for Air Quality (2000a) California Office of Environmental Health Haxard Assessment (OEHHA) Toxicity Criteria Database U S Agency for Toxic Substances and Disease Registry (ATSDR) Minimal Risk Levels (MRLs) for Hazardous Substances Ontario Air Quality Criteria National Institute for Safety and health American Conference of Governmental Industrial Hygenists - 21 - Table 4A: Exposure Guidelines for Metals in Airborne Particulates1 Note that in this table short term values are compared with annual average guidelines, which is an extremely conservative comparison, ie the safety margin is very large. Metal Speciation Lead Mercury Chromium Chromium Arsenic Metal Metal V 0 & III Inorganic Guideline Value ug/m3 0.2 0.33 0.0011 0.11 0.0055 Averaging Period 3 months Annual Annual Annual Annual Max Found ug/m3 0.00080 <0.00001 -2 0.0023 0.00014 1 New Zealand Ambient Air Quality Guidelines, AQ Report No 32, NZ Ministry for the Environment, May 2002. 2 It is highly unlikely that the Cr(VI) is present, however even if all were in that form the highest spot sample recorded would still be below the annual average guideline value. The concentrations observed for the organic compounds quantified are comparable values for rural air elsewhere, and significantly lower than typically observed in urban and residential situations (see Table 5). An exception is acetaldehyde, which is in the range normally associated with urban environments. The highest average and peak concentrations of most carbonyls were found at the Boundary Rd and Hoffman Rd sites. While the differences involved are of the same order as the variability between sites, nevertheless this could be worthy of further investigation in that these carbonyls are components of the refinery emissions. The highest level of propanal was found at the Yarloop site, and was not associated with maxima in any of the other key compounds. Table 5 Comparison of Ambient Air Quality determined in this study to others. All concentrations in micrograms/cubic metre (ug/m3) Typical Concentrations of VOCs in Ambient Air Concentrations in this study Compound Rural Ambient Urban Ambient Indoor Residential 6 Week Mean Weekly Max Formaldehyde 1 – 6(1) 2 – 20(1) 30 – 100(1,2) 2.7 5.6 Acetaldehyde 0.0 – 1.4(3) 1.6 – 44(3) 30 – 100(3) 1.9 4.9 Acetone 0.5 – 5(4) 10 – 100(4) 5 – 27(3) 1.1 2.4 Propanal 0.1 – 0.2(6) 0.5 – 10(5,6) - 0.4 4.6 Hexanal 0.00 – 0.25(6) 0.06 – 1.55(6) - 0.17 0.54 MEK 0.2 – 2.3(6) 0.6 – 6.5(6) - 0.15 0.56 (6) - 0.19 3.65 Benzaldehyde (6) 0.00 – 0.15 0.1 – 0.7 References: 1. International Programme on Chemical Safety Bulletin EHC89, 1989 - 22 - 2. State of Knowledge report: Air Toxics and Indoor Air Quality in Australia, Environment Australia 2001 3. Acetaldehyde as a Toxic Air Contaminant, California EPA, November 1993 4. International Programme on Chemical Safety Bulletin EHC207, 1998 5. Characterisation and identification of Sources of Volatile Organic Compounds in an Industrial Area in Brisbane, O Hawas et al, ANSTO, 1991 6. Tilson Air Quality Study, Manitoba Environmental, August 2000 4.5 Sampling techniques and detection limits The various sampling methods used have differing collection times and hence also detection limits. Aldehydes, ketones and VOCs concentration determined by passive sampling generally have lower detection limits due to the considerably longer collection time (see Table 3). A low method detection limit allows compounds to be measured to a lower concentration and with greater reliability. The less concentrated aldehydes and ketones such as propanal and hexanal have lower method detection limits when determined by the active sampling method TO-11A, as indicated in Table 3. This appears to be due to species-specific difficulties in analysis of samples collected by the Radiello technique. - 23 - 4.6 Common origins and source of ambient species The likely sources for the species most frequently detected in ambient air in this programme are given in Table 6. Table 6 Common origins of VOCs detected in ambient air in the current programme. 1,2 Formaldehyde Acetaldehyde1,2 Vegetative fires & fossil fuel burning, wood heaters, tobacco smoke, combustion engines, natural decomposition processes including atmospheric oxidation of hydrocarbons, glues, detergents, cosmetics, building products. The most common aldehyde in the environment. Vegetative fires & fossil fuel burning, wood heaters, tobacco smoke, combustion engines, atmospheric conversion of other compounds, respiration of plants, ripening of fruit. Acetone3 Vegetative fires & fossil fuel burning, evaporation from living plants and trees, breakdown of body fats, solvents, tobacco smoke, landfill sites, vehicle exhaust. Propanal4 Vegetative & fossil fuel burning, wood heaters, tobacco smoke, combustion engines, burning plastics, natural emissions from trees and bushes. Benzaldehyde5 Natural emissions from plants and grasses, decomposition of leaf litter, common flavouring in foods, combustion processes, atmospheric photo-oxidation of toluene and other aromatic hydrocarbons. MEK1 Hexanal6,7 Benzene1 Toluene1 Acrolein (2 Propenal)1 Vegetative fires & fossil fuel burning, wood heaters, biological degradation processes, veneer & plywood manufacture, varnishes & lacquers, paints & primers, tobacco smoke, vehicle exhaust, cleaners, dyes, inks, insecticides, laundry starches, lubricants, nail polish & remover, shoe polish, furniture, particle board. Natural degradation of plant matter, storage and drying of wood, food flavouring. Vegetative fires & fossil fuel burning, oil and coal, landfills, service stations and all machinery using liquid fuel, burning crop residues and forest management burning, tobacco smoke. Vegetative fires & fossil fuel burning, service stations and all machinery using liquid fuel, burning crop residues and forest management burning, tobacco smoke, consumer products including adhesives, polishes, varnish removers & thinners, coatings, particle board, leather dressings, lubricating oils, pens and markers, furniture, vinyl products. Fuel and vegetative burning, tobacco smoke, livestock feeds, pesticides References: 1. State of Knowledge Report: Air Toxics and Indoor Air Quality in Australia, Environment Australia, 2001 2. WHO Air Quality Guidelines 2002 3. eco-usa.net, extract from Toxicological Profile of Acetone, Agency for Toxic Substances & Disease Registry, US Public Health Service, May 1994 - 24 - 4. Spectrum Chemical Fact Sheet for Propanal, www.speclab.com 5. Spectrum Chemical Fact Sheet for Benzaldehyde, www.speclab.com 6. Spectrum Chemical Fact Sheet for Hexanal, www.speclab.com 7. “Emission of Hexanal and CO from Storage of Wood Pallets”, U Svedberg et al, Ann Occup Hyg, Vol 48, pp339-349, 2004 4.7 Calculated Refinery Contributions to Ambient Concentrations of Key Compounds Table 7 outlines the levels of the most prevalent Volatile Organic Compounds detected at Boundary Road. All compounds were detected at concentrations typical of rural environments and well below levels of concern. The same compounds are present in refinery emissions and the Ground Level Concentrations GLCs) resulting from those emissions have been calculated by CSIRO using the TAPM model. It is therefore possible to estimate the contribution of the refinery emissions to the GLCs of each compound. In all cases it can be seen that the contribution from the refinery is small in comparison to the background concentrations from other sources, which are a combination of natural and anthropogenic sources. Table 7 Ambient VOC Concentrations at Boundary Rd Measured Ambient Levels ug/m3 ug/m3 Refinery Contribution ug/m3 % ug/m3 Max Average Average(1) Detected 24hr 95%(2) Formaldehyde 3.3 6.8 0.00340 0.1% 0.05 Acetaldehyde 2.6 11.4 0.01000 0.4% 0.10 Acetone 1.3 5.4 0.06100 4.7% 0.64 1.0 0.00272 (1) 0.9% <0.00003 (1) Propanal Hexanal 0.31 0.2 0.5 MEK 0.16 0.6 0.00660 4.1% Benzaldehyde 0.14 0.6 0.00080 0.7% - (3) 0.58 0.00085 0.02 Toluene - (3) - (4) 0.00580 0.05 Acrolein -(3) 0.25 0.0019(1) Benzene 0.06 (1) Numbers in italics are estimated as ratio to acetone on basis of emission rates (2) 95th percentile 24-hour maximum values (3) Insufficient data to calculate averages (4) Toluene was not detected at Boundary Rd above the average MDL (0.60 ug/m3) by the TO17 method. The maximum value detected over all sites was 1.7ug/m3 at the Yarloop Lawn Bowls site. - 25 - 5 Conclusions This study provides detailed knowledge of the ambient air quality in the region surrounding the Wagerup alumina refinery, including the townships of Waroona and Yarloop and the associated rural environment. The study was carried out over a six week period and built on data and information gathered in the previous fifteen week preliminary study. A variety of recognised sampling and analytical techniques were employed, including USEPA methods for determining volatile organic compounds (VOCs), carbonyls, metals and inorganic compounds. A total of 274 volatile chemical compounds were analysed for. Of these, 35 were detected and quantified, a further 31 were detected at levels too low to quantify, and the remainder were not detected. The main chemical compounds detected are all known to be present in refinery emissions. The levels found in the ambient environment are generally many times greater than the calculated refinery influence for each compound. There was a lack of any clear spatial distribution that would indicate a refinery influence on the levels of the compounds detected. This is consistent with the proposition that the levels of chemicals in the ambient atmosphere are dominated by human and natural processes other than the refinery operation. All chemical compounds detected were found to be at levels well below applicable limits set for the protection of human health, and were generally within the ranges expected for rural environments. An exception to the latter is acetaldehyde, which was found at levels more typical of urban environments. This could warrant further investigation to establish the source, but the distribution, levels and relativity to other compounds mean that the refinery is unlikely to be the cause. The chemical compounds detected and their levels in the atmosphere showed little spatial variation and for the most part appeared to be randomly distributed, limiting the ability to attribute specific sources. Elevated levels of both carbonyls and VOCs were found at the Waroona and Yarloop township sites, consistent with the effects of human activities associated with the use of fossil fuels. Sampling sites closest to the refinery were generally showed lower concentrations of the compounds measured, although indications of higher than average levels of carbonyls at the Boundary Rd and to a lesser extent the Hoffman Rd sites could warrant further investigation. The exclusion of sampling sites at Waroona and close to the refinery in the group of key sites for intensive monitoring is a weakness of the study, as comparisons between Waroona and close to the refinery could be expected to be informative on the basis of the Radiello passive sampling results. Significant differences were observed between the weekly results from Radiello passive sampling and the USEPA methods for VOCs and carbonyls. It is not clear to what extent this is due to differences in sampling technique or real differences in ambient concentrations between day and night, and between workdays and weekends. It would be useful to resolve this by parallel sampling and analysis. 6 Recommendations To resolve the issues raised by this study and further investigate the possibility of detecting influences of the refinery on ambient air quality, the following recommendations are made: 1. A comparative study of Radiello and USEPA sampling techniques over the same time periods should be carried out to investigate the apparent bias between the techniques and indicate possible reasons; 2. An investigation of the cause of the apparent elevated levels of carbonyls at Boundary Rd could be informative; 3. Investigation of techniques for monitoring short-term concentrations of compounds of interest should be progressed, preferably by continuous monitoring techniques such as the Opsis that is currently being trialed for formaldehyde and benzene. This should attempt to correlate variations in - 26 - concentrations with short term influences of refinery emissions on the ambient atmosphere indicated by marker compounds, in particular NOx. 4. Information from 3 should be used in combination with dispersion modeling and emission source measurements to improve knowledge of the influences of the refinery on ambient air quality. This provides a practical alternative to the approach of event monitoring with ultra-trace analysis, which is not recommended due to the difficulties involved in identifying and capturing events, the high dilution from dispersion, and the background levels of chemicals existing in the atmosphere from other natural and anthropogenic sources. 5. An investigation of the hexanes, pentanes and PAHs detected at the Yarloop site could be carried out to confirm their concentrations and identify likely sources. - 27 - APPENDICES - 28 - Appendix 1: Aerial Photo showing the location of the 11 sampling points used in the comprehensive Wagerup ambient air program. - 29 - Appendix 2: Aldehyde and ketones concentration at 11 sampling points around Wagerup as determined by passive sampling (Radiello). Formaldehyde ug/m3 1 2 3 4 5 6 Waroona Lawn Bowls run 1 run 2 1.0 1.2 1.5 3.3 0.87 0.97 0.93 1.1 1.1 1.3 0.59 0.59 Yarloop Lawn Bowls run 1 run 2 0.57 0.47 2.1 2.4 0.58 0.58 0.41 0.91 0.96 0.77 0.61 0.81 Clifton Rd Yarloop run 1 run 2 0.38 0.47 1.2 1.6 0.19 0.097 0.74 0.41 0.58 0.39 0.51 0.61 Residue South run 1 run 2 0.19 0.19 0.59 0.39 0.30 0.30 0.25 0.68 0.94 0.75 0.30 0.20 Hoffman Road run 1 run 2 0.20 0.20 0.90 1.0 0.29 0.29 0.33 0.58 0.48 0.77 0.31 0.10 Bremnar Road run 1 run 2 0.37 0.37 0.49 0.68 0.19 0.19 0.17 0.25 0.57 0.57 0.099 0.099 Mean Acetaldehyde 1 2 3 4 5 6 1.00 1.41 0.87 0.99 0.60 0.60 0.43 0.42 0.42 0.49 0.31 0.36 0.36 0.85 0.80 0.50 0.68 0.70 0.36 3.1 0.80 0.60 0.90 0.47 0.22 0.58 0.46 0.29 0.45 0.48 0.11 0.58 0.46 0.39 0.57 0.60 0.11 0.58 0.34 0.39 0.46 1.3 0.22 0.70 0.23 0.48 0.46 0.48 0.055 0.35 0.23 0.30 0.33 0.36 0.055 0.46 0.35 0.40 0.33 0.36 0.12 0.35 0.11 0.29 0.34 0.48 0 0.35 0.11 0.39 0.23 0.24 0.055 0.34 0.23 0.20 0.34 0.23 0.22 0.34 0.23 0.30 0.45 0.23 Mean Propanal 1 2 3 4 5 6 0.65 1.04 0.41 0.45 0.53 0.43 0.27 0.33 0.28 0.22 0.23 0.30 nd nd 0.25 0.21 0.24 0.5 nd 1.2 nd 0.21 0.49 0.5 nd nd nd nd 0.49 0.52 nd nd nd 0.21 0.24 0.26 nd nd nd 0.21 0.25 0.26 nd nd nd nd 0.25 0.26 nd nd nd nd 0.48 0.51 nd nd nd 0.21 0.24 0.51 nd nd nd nd 0.25 0.26 nd nd nd 0.21 0.25 nd nd nd nd nd 0.24 0.50 nd nd nd nd 0.24 0.50 Butanal 1 2 3 4 5 6 nd nd 0.87 nd nd nd nd nd 1.7 nd nd nd nd nd 0.87 nd nd nd nd nd 0.87 nd nd nd nd nd nd nd nd nd nd nd 0.88 nd nd nd nd nd nd nd nd nd nd nd 0.89 nd nd nd nd nd nd nd nd nd nd nd 0.87 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Benzaldehyde 1 2 3 4 5 6 nd nd nd nd nd nd nd 0.20 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd - 30 - Appendix 2 (cont.) Boundary Rd 3 run 1 run 2 0.38 0.38 0.60 0.50 0.48 0.39 0.41 0.25 0.48 0.48 0.31 0.20 Boundary Road 2 run 1 run 2 0.29 0.29 2.1 2.4 0.19 0.19 na na 0.58 0.58 0.82 0.51 Willowdale Mine run 1 run 2 0.67 0.48 1.2 1.7 0.29 0.29 0.86 1.2 0.47 0.65 1.2 0.20 Mean Acetaldehyde 1 2 3 4 5 6 0.44 0.37 0.80 0.79 0.78 0.75 0.80 0.55 0.67 0.70 0.11 0.47 0.23 0.29 0.34 0.48 0.055 0.47 0.34 0.29 0.34 0.36 0.11 0.35 0.57 na 0.45 0.36 0.22 0.35 0.34 na 0.45 0.48 0.11 0.23 0.35 0.20 0.33 0.35 0.11 0.34 0.23 0.40 0.33 0.35 0.12 0.32 0.34 0.40 0.34 0.47 0.12 0.43 0.34 na 0.34 0.23 0.23 0.35 0.35 0.30 0.44 0.51 0.055 0.46 0.23 0.30 0.33 0.51 Mean Propanal 1 2 3 4 5 6 0.32 0.31 0.37 0.37 0.26 0.29 0.33 0.29 0.36 0.31 nd nd nd 0.21 0.24 0.26 nd nd nd nd 0.24 0.52 nd nd 0.24 na 0.24 0.52 nd nd nd na nd 0.26 nd nd nd nd nd 0.51 0.24 nd nd 0.22 0.24 0.51 nd nd 0.25 nd 0.25 0.50 nd nd nd na nd 0.25 0.24 nd nd nd 0.24 0.51 nd nd nd 0.21 0.48 0.51 Butanal 1 2 3 4 5 6 nd nd nd nd nd nd nd nd nd nd nd nd nd nd 1.7 na nd nd nd nd 0.87 na nd nd nd nd 0.88 nd nd nd 1.7 nd nd nd nd nd nd nd 0.88 nd nd nd nd nd 0.88 na nd nd nd nd 0.89 nd nd nd nd nd 0.89 nd nd nd Benzaldehyde 1 2 3 4 5 6 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd na nd nd nd nd nd nd nd nd nd nd nd nd nd nd Formaldehyde ug/m3 1 2 3 4 5 6 Hamel Training Centre run 1 run 2 0.40 0.40 1.8 1.5 0.29 0.097 0.84 na 0.48 0.57 0.99 0.20 - 31 - Residue Area run 1 run 2 0.38 0.57 1.7 1.1 0.39 0.3 0.76 1.0 0.57 1.0 0.20 0.20 Appendix 3: Formaldehyde and acetaldehyde concentration at 11 sampling points around Wagerup as determined by passive sampling (Radiello). Formaldehyde Sampling Sites Boundary Road Willowdale Mine Hamel Training Centre Residue Area Waroona Lawn Bowls Yarloop Lawn Bowls Clifton Road Yarloop Residue South Hoffman Road Bremnar Road Boundary Road 3 Week 1 mean Std Error 0.29 0.00 0.58 0.27 0.40 0.00 0.48 0.27 1.10 0.14 0.52 0.14 0.43 0.13 0.19 0.00 0.20 0.00 0.37 0.00 0.38 0.00 Week 2 mean 2.25 1.45 1.65 1.40 2.40 2.25 1.40 0.49 0.95 0.59 0.55 ALL 11 sites 0.45 1.40 0.09 Std Error 0.42 0.71 0.42 0.85 0.42 0.42 0.57 0.28 0.14 0.27 0.14 0.42 Week 3 mean Std Error 0.19 0.00 0.29 0.00 0.19 0.27 0.35 0.13 0.92 0.00 0.58 0.00 0.14 0.13 0.30 0.00 0.29 0.00 0.19 0.00 0.44 0.13 Week 4 mean Std Error No samples 1.03 0.48 0.84 0.00 0.88 0.34 1.02 0.71 0.66 0.71 0.58 0.47 0.47 0.61 0.46 0.35 0.21 0.11 0.33 0.23 Week 5 mean Std Error 0.58 0.00 0.56 0.25 0.53 0.13 0.79 0.61 1.20 0.27 0.87 0.27 0.49 0.27 0.85 0.27 0.63 0.41 0.57 0.00 0.48 0.00 Week 6 mean Std Error 0.67 0.44 0.70 1.41 0.60 1.12 0.20 0.00 0.59 0.28 0.71 0.28 0.56 0.14 0.25 0.14 0.21 0.30 0.10 0.00 0.26 0.16 Combined 1 - 6 mean Std Error 0.80 0.17 0.77 0.52 0.70 0.39 0.68 0.37 1.20 0.30 0.93 0.30 0.60 0.28 0.42 0.22 0.45 0.20 0.34 0.06 0.41 0.11 0.35 0.65 0.68 0.44 0.66 0.06 0.40 0.22 0.39 0.27 Acetaldehyde Boundary Road Willowdale Mine Hamel Training Centre Residue Area Waroona Lawn Bowls Yarloop Lawn Bowls Clifton Road Yarloop Residue South Hoffman Road Bremnar Road Boundary Road 3 Week 1 mean Std Error 0.17 0.16 0.11 0.00 0.12 0.00 0.14 0.25 0.36 0.00 0.17 0.16 0.17 0.16 0.06 0.00 0.06 0.17 0.14 0.23 0.08 0.08 Week 2 mean 0.35 0.29 0.38 0.41 1.98 0.58 0.64 0.41 0.35 0.34 0.47 ALL 11 sites 0.14 0.56 Sampling Sites 0.11 Std Error 0.00 0.16 0.16 0.16 3.18 0.00 0.17 0.16 0.00 0.00 0.00 0.36 Week 3 mean Std Error 0.46 0.33 0.29 0.17 0.34 0.00 0.29 0.17 0.80 0.00 0.46 0.00 0.29 0.16 0.29 0.17 0.11 0.00 0.23 0.00 0.29 0.16 Week 4 mean Std Error No samples 0.30 0.28 0.40 0.00 0.30 0.00 0.55 0.14 0.34 0.14 0.44 0.13 0.35 0.14 0.34 0.14 0.25 0.14 0.29 0.00 Week 5 mean Std Error 0.45 0.00 0.33 0.00 0.34 0.00 0.39 0.16 0.79 0.31 0.51 0.17 0.46 0.00 0.33 0.00 0.29 0.16 0.40 0.16 0.34 0.00 Week 6 mean Std Error 0.42 0.17 0.35 0.00 0.35 0.34 0.51 0.00 0.59 0.33 0.54 0.17 0.89 1.16 0.36 0.00 0.36 0.34 0.23 0.00 0.42 0.17 Combined 1 - 6 mean Std Error 0.37 0.13 0.28 0.10 0.32 0.10 0.34 0.12 0.84 0.66 0.43 0.11 0.48 0.29 0.30 0.08 0.25 0.13 0.26 0.09 0.32 0.07 0.35 0.36 0.42 0.46 0.38 0.10 0.11 Summary Sampling Site Site No. 11 3 4 9 8 10 6 5 12 1 2 Bremnar Road Residue Area Residue South Boundary Road 3 Boundary Road Hoffman Road Clifton Road Yarloop Yarloop Lawn Bowls Willowdale Mine Waroona Lawn Bowls Hamel Training Centre ALL 11 sites mean 0.34 0.68 0.42 0.41 0.80 0.45 0.60 0.93 0.77 1.20 0.70 0.66 Formaldeyde Min Maximum mean 0.10 0.59 0.26 0.20 1.40 0.34 0.19 0.85 0.30 0.26 0.55 0.32 0.19 2.25 0.37 0.20 0.95 0.25 0.14 1.40 0.48 0.52 2.25 0.43 0.29 1.45 0.28 0.59 2.40 0.84 0.40 1.65 0.32 0.28 1.43 0.38 Acetaldehyde Min Maximum 0.14 0.40 0.14 0.51 0.06 0.41 0.08 0.47 0.17 0.46 0.06 0.36 0.17 0.89 0.17 0.58 0.11 0.35 0.36 1.98 0.12 0.40 0.14 - 32 - 0.62 0.09 0.24 0.17 Appendix 4: Method Detection Limit defined, and low concentration assignments, used in this study. The Method Detection Limit (MDL) refers to the lowest concentration a detected compound can be reliably reported. The value equates to 4 times the compound concentration of a method blank sample. “D” is assigned to a single value or mean duplicate (for recording purposes) if: ½ MDL < x1 < MDL. To obtain representative averages (at a sampling site or for a given week) the measurements were allocated a value equal to ½ MDL. “nd” is assigned to a single value or mean duplicate where x2 < ½ MDL. A value of zero (“0”) was chosen for these measurements when averaging. Duplicate values are considered “reportable” if both of the conditions below are met: (a) One value x1 > 2 MDL, and the other value x2 > MDL & (b) │x1 – x2│ < ¼ mean. - 33 - Appendix 5: Formaldehyde, acetaldehyde and acetone concentrations at 5 key sampling points around Wagerup determined by the active sampling USEPA method TO-11A. Formaldehyde Week number and commencement date 1 rd 23 Aug 2004 2 th 30 Aug 2004 3 th 6 Sept 2004 4 th 13 Sept 2004 5 6 th 20 Sept 2004 th 27 Sept 2004 Site Ave Boundary Rd 2 2.57 3.04 1.96 4.53 4.46 3.07 3.27 Hoffman Road 3.32 3.58 1.23 5.57 3.00 2.17 3.15 Yarloop Lawn Bowls 1.75 2.75 1.23 4.48 2.84 2.35 2.57 Bremnar Road 2.46 3.47 1.62 3.82 2.57 2.12 2.68 Hamel Training Centre 0.00 1.96 1.23 3.84 2.65 1.88 1.93 Weekly Ave 2.02 2.96 1.45 4.45 3.10 2.32 2.72 Acetaldehyde Site Week number 1 2 3 4 5 6 Ave Boundary Rd 2 1.87 2.39 1.99 2.75 4.87 1.75 2.60 Hoffman Road 2.38 1.82 1.51 2.98 2.23 2.52 2.24 Yarloop Lawn Bowls 1.79 1.87 1.23 2.29 1.89 1.28 1.73 Bremnar Road 1.08 2.11 1.55 2.37 1.64 1.65 1.73 Hamel Training Centre 0.00 1.49 1.32 2.28 1.82 1.41 1.39 Weekly Ave 1.42 1.94 1.52 2.54 2.49 1.72 1.94 Acetone Site Week 1 Week 2 Week 3 Week 4 Week 5 Week 6 Ave Boundary Rd 2 0.71 1.52 0.77 1.82 2.43 0.46 1.29 Hoffman Road 1.58 2.15 0.70 1.12 1.06 0.89 1.25 Yarloop Lawn Bowls 0.63 1.68 0.44 2.20 0.72 0.40 1.01 Bremnar Road 0.88 1.19 0.62 1.25 0.75 1.59 1.05 Hamel Training Centre 0.00 1.50 0.00 1.24 1.67 0.37 0.80 Weekly Ave 0.76 1.61 0.51 1.53 1.33 0.74 1.08 - 34 - Appendix 6: Aldehyde and ketones concentration at the 5 key sampling points around Wagerup as determined by USEPA TO-11A. Boundary Rd 2 (Weeks) Acetone Propanal Butanal/ Isobutyraldehyde Day # 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 Acrolein Methacrolein Methyl Ethyl Ketone Pentanal Hexanal 2-Pentanone/ 3-Methyl-2-butanone Benzaldehyde 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 nd (1.9) D (2.7) 2 2.0 (1.8) 1.3 (0.95) 2.4 (1.1) 3 1.1 (0.18) 0.34 (0.094) D (0.11) D (0.18) D (0.092) 0.72 (0.093) D (0.14) nd (0.19) D (0.27) 0.20 (0.18) 0.11 (0.094) D (0.11) 0.19 (0.18) D (0.090) 0.13 (0.093) D (0.14) nd (0.19) nd (0.14) nd (0.094) nd (0.094) nd (0.11) nd (0.095) nd (0.090) nd (0.091) nd (0.13) nd (0.19) D (0.27) D (0.18) 0.15 (0.095) 0.13 (0.11) nd (0.095) nd (0.090) 0.11 (0.093) nd (0.13) nd (0.19) D (0.27) 0.24 (0.18) 0.17 (0.095) 0.28 (0.11) D (0.18) D (0.092) D (0.091) D (0.14) nd (0.19) nd (0.14) nd (0.094) nd (0.094) nd (0.11) nd (0.095) nd (0.090) 0.093(0.093) nd (0.13) 0.54 (0.19) 0.31 (0.18) 0.14 (0.14) 0.095(0.095) 0.42 (0.18) nd (0.11) 0.090(0.090) 0.22 (0.092) 0.23 (0.13) nd (0.19) 0.37 (0.18) 0.26 (0.095) 0.35 (0.18) 0.35 (0.27) 0.24 (0.11) D (0.092) 0.091(0.091) 0.22 (0.14) 0.63 (0.19) 0.24 (0.18) 0.19 (0.14) 0.095(0.095) 0.19 (0.11) 5 6.8 (0.97) 6 1.3 (0.92) * 1.8 (1.0) 1.4 (1.0) 0.98 (0.98) 1.4 (1.0) nd (1.0) 1.0 (1.0) 1.5 (0.19) 0.81 (0.097) D (0.092) 0.20 (0.10) D (0.10) D (0.099) 0.62 (0.10) 1.2 (0.20) 0.58 (0.10) 0.13 (0.096) 0.37 (0.097) 0.099(0.092) * 0.15 (0.10) nd (0.099) nd (0.098) 0.17 (0.10) 0.10 (0.10) nd (0.10) nd (0.096) nd (0.097) nd (0.092) * nd (0.10) nd (0.095) 0.12 (0.098) 0.25 (0.10) nd (0.10) nd (0.10) 0.12 (0.096) 0.15 (0.097) nd (0.092) * 0.38 (0.10) 0.12 (0.10) 0.12 (0.098) 0.24 (0.10) nd (0.10) nd (0.10) 0.41 (0.15) 0.64 (0.097) 0.18 (0.092) * 0.21 (0.10) 0.18 (0.10) 0.098(0.098) 0.20 (0.10) 0.30 (0.20) 0.16 (0.10) 0.12 (0.096) nd (0.097) nd (0.092) * 0.12 (0.10) nd (0.099) 0.30 (0.15) nd (0.098) 0.16 (0.10) 0.37 (0.097) nd (0.10) nd (0.10) 0.24 (0.092)* 0.32 (0.10) 0.20 (0.10) 0.47 (0.15) 0.20 (0.098) 0.24 (0.10) 0.44 (0.097) 0.22 (0.10) 0.12 (0.10) 0.20 (0.092) 0.30 (0.10) 0.18 (0.10) 0.15 (0.098) 0.34 (0.10) 0.10 (0.10) 0.18 (0.10) 0.19 (0.096) 0.31 (0.097) 0.15 (0.092) * 0.12 (0.10) nd (0.099) nd (0.098) 0.14 (0.10) nd (0.10) nd (0.10) D (1.8) 1.3 (0.92) 1.5 (0.93) 1.6 (1.4) D (0.19) 0.64 (0.27) 4 2.7 (0.96) D (0.18) nd (0.090) 0.091(0.091) 0.16 (0.14) * Value is for run 2 only. Shaded cells show days when no samples were collected. Bold typeface indicates measured value is "reportable" as > 2 times MDL. - 35 - Appendix 6 (cont.) Hoffman Road (Weeks) Acetone Day # 1 2 3 4 1 3.8 (1.9) None 2.4 (1.3) 1 2 3 4 D (0.13) 1 Acrolein Methacrolein Methyl Ethyl Ketone 2 3 4 5 Hexanal 2-Pentanone/ 3-Methyl2-butanone Benzaldehyde nd (0.93) D (0.19) D (0.18) D (0.13) D (0.099) D (0.099) D (0.095) D (0.19) 0.13 (0.096) 6 1.4 (1.0) 1.2 (0.97) 0.98 (0.98) 3.4 (0.96) 1.4 (1.0) 0.94 (0.94) 1.7 (0.95) 1.1 (0.95) nd (1.0) 0.47 (0.20) 0.26(0.097) 1.2 (0.20) 0.32 (0.10) 0.45 (0.094) 0.26(0.095) 0.17 (0.095) 0.46 (0.10) 0.53 (0.20) 0.12 (0.10) nd (0.098) nd (0.096) 0.11 (0.095) 0.12 (0.095) nd (0.096) nd (0.092) nd (0.094) nd (0.10) nd (0.10) nd (0.098) nd (0.096) nd (0.092) nd (0.096) nd (0.094) nd (0.10) 0.14 (0.10) D (0.20) 0.16 (0.097) 0.27 (0.095) nd (0.096) 0.095(0.095) nd (0.096) nd (0.094) nd (0.10) D (0.20) 0.12 (0.10) 0.11 (0.095) 0.84 (0.096) 0.11 (0.094) 0.12 (0.10) 1 2 3 4 5 nd (0.16) * None nd (0.13) D (0.16) * None D (0.13) 5 Pentanal 1.4 (0.99) 5 None D (0.13) nd (0.16) * None nd (0.13) 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1.8 (0.99) 4 D (0.16) * 1 2 3 4 5 1 2 3 4 2.5 (1.3) D (0.16) * None 5 Butanal/ Isobutyraldehyde 3 D (1.8) D (1.6) * 5 Propanal 2 nd (0.16) * None 0.13 (0.13) 0.16 (0.16) * None 0.52 (0.13) D (0.16) * None 0.89 (0.13) 0.16 (0.16) * None 2.3 (0.13) 0.15 (0.13) D (0.099) D (0.099) nd (0.093) nd (0.094) nd (0.096) nd (0.13) nd (0.094) nd (0.098) nd (0.093) 0.21 (0.094) nd (0.096) nd (0.13) nd (0.094) 0.12 (0.098) nd (0.093) D (0.19) D (0.18) nd (0.095) nd (0.093) 0.16 (0.10) 0.25 (0.13) D (0.099) 0.099 (0.099) 0.11 (0.095) D (0.19) 0.096 (0.096) nd (0.13) nd (0.094) nd (0.098) nd (0.093) 0.40 (0.19) 0.40 (0.18) 0.28 (0.13) 0.14 (0.098) 0.26 (0.099) 0.093 (0.093) D (0.19) 0.096 (0.096) 0.16 (0.097) 0.21 (0.095) nd (0.10) nd (0.098) nd (0.095) nd (0.093) nd (0.096) nd (0.092) 0.13 (0.096) nd (0.094) nd (0.10) 0.24 (0.10) 0.12 (0.098) 0.18 (0.10) 0.16 (0.092) 0.25 (0.096)) 0.17 (0.096) 0.14 (0.10) 0.10 (0.098) 0.10 (0.096) 0.16 (0.095) 0.41 (0.096) 0.16 (0.094) 0.14 (0.10) nd (0.098) 0.10 (0.096) nd (0.092) 0.78 (0.096) nd (0.094) nd (0.10) 0.25 (0.095) 0.30 (0.095) D (0.21) 0.18 (0.13) 0.18 (0.099) 0.14 (0.099) D (0.095) 0.13 (0.094) 0.17 (0.096) D (0.097) 0.19 (0.095) 0.12 (0.10) 3.65 (0.13) 2.4 (0.098) nd (0.094) nd (0.093) 0.12 (0.097) 0.11 (0.095) Shaded cells show days when no samples were collected. Bold typeface indicates measured value is "reportable" as > 2 times MDL. - 36 - Appendix 6 (cont.) Yarloop Lawn Bowls (Weeks) Acetone Propanal Day # 1 2 3 4 5 1 2 nd (1.4) 3 4 5 6 D (1.9) 4.0 (1.0) 2.8 (1.9) 1.4 (0.99) 3.8 (2.4) 1.1 (0.94) 1.2 (0.99) 1.2 (0.99) nd (0.94) nd (0.98) nd (1.7) 1.4 (0.99) nd (0.97) 1.3 (0.95) nd (0.95) nd (1.0) 0.32 (0.099) 3.2 (0.99) 1 D (0.15) 4.6 (0.15) 1.4 (0.20) 0.78 (0.15) 2 3 4 5 3.5 (0.24) D (0.19) 0.26 (0.099) 0.20 (0.098) 0.59 (0.094) D (0.099) D (0.20) D (0.099) D (0.097) D (0.10) D (0.096) 0.52 (0.10) D (0.10) 1 nd (0.14) D (0.19) 0.29 (0.20) nd (0.093) nd (0.099) Butanal/ Isobutyraldehyde 2 3 4 5 0.33 (0.24) D (0.19) 0.14 (0.099) 0.12 (0.098) 0.11 (0.094) nd (0.098) nd (0.20) D (0.099) 0.16 (0.099) D (0.099) 0.14 (0.095) nd (0.095) nd (0.10) 1 nd (0.14) nd (0.093) nd (0.099) nd (0.093) 0.18 (0.099) Acrolein 2 3 4 5 1 nd (0.11) nd (0.094) nd (0.093) nd (0.098) nd (0.094) nd (0.098) nd (0.17) nd (0.099) nd (0.097) 0.11 (0.095) nd (0.095) nd (0.10) 2 3 4 5 1 2 3 4 5 1 2 3 4 5 0.31 (0.24) 1 D (0.15) 2 3 4 5 1 D (0.24) Methacrolein Methyl Ethyl Ketone Pentanal Hexanal 2-Pentanone/ 3-Methyl2-butanone Benzaldehyde 2 3 4 5 1 2 3 4 5 nd (0.099) nd (0.14) nd (0.17) nd (0.093) 0.20 (0.20) nd (0.093) nd (0.099) nd (0.094) nd (0.093) nd (0.098) nd (0.094) nd (0.098) nd (0.099) nd (0.097) nd (0.095) nd (0.095) nd (0.10) nd (0.099) nd (0.14) 0.29 (0.24) 0.20 (0.20) D (0.19) 0.30 (0.099) D (0.19) 0.57 (0.20) 0.26 (0.19) 0.24 (0.20) D (0.099) D (0.099) 0.20 (0.099) 0.12 (0.10) 0.11 (0.094) 0.13 (0.095) 0.18 (0.099) 0.16 (0.10) 0.32 (0.10) nd (0.14) D (0.19) 0.25 (0.20) 0.13 (0.093) 0.099(0.099) nd (0.11) nd (0.094) nd (0.093) 0.14 (0.098) 0.11 (0.096) nd (0.098) nd (0.17) nd (0.099) nd (0.097) nd (0.095) nd (0.095) nd (0.10) nd (0.099) 0.17 (0.17) D (0.093) 0.51 (0.20) 0.40 (0.15) 0.18 (0.099) 0.15 (0.094) 0.20 (0.099) 0.24 (0.098) 0.11 (0.096) 0.20 (0.098) 0.12 (0.099) 0.16 (0.099) 0.19 (0.095) 0.17 (0.096) 0.16 (0.10) D (0.19) D (0.099) D (0.099) 0.76 (0.20) 0.13 (0.099) 0.18 (0.095) 0.39 (0.19) 0.15 (0.096) 0.14 (0.096) 0.20 (0.20) 0.11 (0.099) D (0.10) D (0.19) nd (0.093) nd (0.097) 0.31 (0.20) nd (0.098) nd (0.095) 0.13 (0.093) nd (0.094) nd (0.095) nd (0.099) nd (0.098) nd (0.10) 0.22 (0.099) D (0.15) 0.71 (0.24) 0.23 (0.17) D (0.15) 0.14 (0.11) 0.20 (0.17) 0.094(0.094) 0.14 (0.099) 0.33 (0.10) nd (0.094) 0.20 (0.099) 0.20 (0.099) Shaded cells show days when no samples were collected. Bold typeface indicates measured value is "reportable" as > 2 times MDL. - 37 - Appendix 6 (cont.) Bremnar Road (Weeks) Acetone Propanal Butanal/ Isobutyraldehyde Acrolein Methacrolein MEK Pentanal Hexanal 2-Pentanone/ 3-Methyl2-butanone Benzaldehyde Day # 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 6 None 1.7 (0.93) 1.5 (1.0) 2.0 (1.3) 1.2 (0.96) 2.2 (2.0) nd (0.94) 1.0 (1.0) nd (0.99) 1.2 (0.99) 1.6 (0.94) 1.1 (0.91) 1.2 (0.99) nd (1.5) 2.0 (0.90) 3.5 (1.7) D (0.13) None 2.5 (0.19) 2.5 (0.20) 1.9 (0.97) D (0.24) 0.98 (0.20) D (0.20) 1.4 (0.092) D (0.096) 0.32 (0.10) 0.48 (0.099) 0.40 (0.10) D (0.091) 0.30 (0.089) 0.22 (0.15) 1.7 (0.17) None D (0.013) 0.15 (0.10) 0.15 (0.13) nd (0.096) nd (0.098) 0.20 (0.09) nd (0.094) nd (0.098) nd (0.099) nd (0.096) nd (0.090) nd (0.15) 0.38 (0.17) None nd (0.15) nd (0.17) None 0.15 (0.15) nd (0.17) None 0.15 (0.15) 0.19 (0.19) None nd (0.15) 0.21 (0.17) None 0.22 (0.15) 0.38 (0.17) None D (0.15) D (0.19) None nd (0.15) nd (0.17) 0.28 (0.09) 0.12 (0.097) 360 D (0.013) nd (0.093) nd (0.092) nd (0.013) 0.11 (0.093) 0.15 (0.094) nd (0.013) 0.32 (0.19) 0.21 (0.094) 0.075 (0.013) D (0.19) 0.13 (0.094) nd (0.013) 0.28 (0.093) 0.26 (0.094) D (0.013) 0.19 (0.19) 0.30 (0.09) D (0.013) 0.30 (0.19) 0.13 (0.094) nd (0.013) nd (0.10) nd (0.094) nd (0.090) nd (0.10) nd (0.094) nd (0.090) 0.10 (0.10) 0.11 (0.096) 0.11 (0.090) 0.10 (0.10) nd (0.094) nd (0.090) 0.27 (0.10) 0.096(0.096) 0.18 (0.090) 0.46 (0.10) 0.38 (0.096) 0.23 (0.090) 0.27 (0.10) 0.21 (0.096) nd (0.090) 0.12 (0.099) 0.11 (0.097) nd (0.13) nd (0.098) nd (0.097) 0.13 (0.13) nd (0.098) 0.21 (0.097) 0.38 (0.24) 0.15 (0.10) 0.20 (0.10) 0.13 (0.13) nd (0.098) 0.12 (0.097) 0.26 (0.13) 0.12 (0.098) 0.38 (0.10) 0.26 (0.13) 0.17 (0.098) 0.21 (0.097) 0.59 (0.24) 0.12 (0.10) 0.12 (0.097) nd (0.096) nd (0.099) nd (0.089) nd (0.096) nd (0.099) 0.16 (0.099) 0.21 (0.096) nd (0.099) 0.16 (0.099) nd (0.096) nd (0.099) nd (0.089) 0.19 (0.096) 0.14 (0.099) 0.20 (0.099) 0.31 (0.20) 0.13 (0.099) 0.18 (0.089) 1.6 (0.20) nd (0.099) nd (0.089) 0.092 (0.092) 0.12 (0.098) nd (0.096) nd (0.089) 0.35 (0.20) D (0.099) nd (0.089) 0.33 (0.20) 0.17 (0.096) 0.11 (0.089) nd (0.098) nd (0.096) nd (0.089) 0.41 (0.20) 0.16 (0.099) 0.17 (0.092) 0.31 (0.20) 0.24 (0.10) 0.18 (0.092) 1.0 (0.20) nd (0.096) nd (0.089) Shaded cells show days when no samples were collected. Bold typeface indicates measured value is "reportable" as > 2 times MDL. - 38 - Appendix 6 (cont.) Hamel Training Centre (Weeks) Acetone Propanal Butanal/ Isobutyraldehyde Acrolein Methacrolein Methyl Ethyl Ketone Pentanal Hexanal 2-Pentanone/ 3-Methyl-2-butanone Benzaldehyde Day # 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 6 1.0 (1.0) None 1.5 (1.9) nd (0.94) D (2.0) 1.4 (0.99) None 1.6 (0.91) nd (0.92) 1.8 (0.98) 1.2 (1.0) nd (1.0) nd (1.3) 1.5 (0.95) nd (0.96) 1.4 (1.0) 2.6 (1.0) 1.2 (0.98) None 0.73 (0.094) 0.80 (0.19) 0.28 (0.20) 0.34 (0.15) 0.45 (0.21) None D (0.093) D (0.097) D (0.098) 0.34 (0.10) 0.25 (0.10) 1.5 (0.25) D (0.095) D (0.096) D (0.10) 0.76 (0.10) 0.28 (0.10) None 0.17 (0.094) nd (0.094) D (0.20) nd (0.099) nd (0.10) None 0.15 (0.13) D (0.093) D (0.095) D (0.097) D (0.096) nd (0.097) nd (0.10) 0.12 (0.097) 0.32 (0.10) nd (0.10) nd (0.098) None nd (0.094) nd (0.094) nd (0.099) nd (0.099) nd (0.10) None nd (0.091) nd (0.092) nd (0.097) nd (0.097) nd (0.10) nd (1.3) nd (0.090) nd (0.096) nd (0.10) 0.20 (0.10) nd (0.098) None nd (0.094) nd (0.094) D (0.20) nd (0.099) nd (0.10) None nd (0.091) nd (0.092) 0.22 (0.098) 0.14 (0.097) nd (0.10) nd (0.13) nd (0.090) nd (0.096) 0.16 (0.10) 0.29 (0.10) nd (0.098) None None 0.19 (0.094) 0.11 (0.091) D (0.19) D (0.097) 0.22 (0.20) 0.16 (0.097) 0.18 (0.099) 0.14 (0.097) 0.30 (0.21) 0.18 (0.10) nd (0.13) D (0.090) 0.12 (0.098) 0.10 (0.10) 0.43 (0.10) 0.20 (0.098) None nd (0.094) nd (0.094) nd (0.099) nd (0.099) nd (0.10) None nd (0.091) nd (0.092) nd (0.097) nd (0.097) nd (0.10) nd (0.13) nd (0.090) nd (0.096) nd (0.10) 0.14 (0.10) nd (0.098) None nd (0.094) 0.094(0.094) D (0.20) nd (0.099) nd (0.10) None D (0.093) nd (0.092) 0.14 (0.097) 0.26 (0.10) 0.14 (0.10) 0.25 (0.25) D (0.090) nd (0.096) 0.14 (0.10) 0.48 (0.10) 0.18 (0.098) None None 0.33 (0.25) 0.25 (0.19) D (0.093) D (0.095) 0.11 (0.094) D (0.097) 0.12 (0.098) D (0.20) 0.15 (0.098) 0.10 (0.10) 0.16 (0.099) 0.30 (0.10) 1.0 (0.10) 0.34 (0.21) 0.14 (0.10) 0.27 (0.098) None None 0.25 (0.25) 0.11 (0.094) 0.091(0.091) 0.095(0.095) 0.63 (0.19) 0.14 (0.097) 0.13 (0.096) 0.78 (0.20) 0.12 (0.098) 0.12 (0.10) nd (0.099) 0.12 (0.10) 0.16 (0.10) nd (0.10) nd (0.10) nd (0.098) Shaded cells show days when no samples were collected. Bold typeface indicates measured value is "reportable" as > 2 times MDL. - 39 - Appendix 7: Aldehyde and ketones concentration at the 5 key sampling points around Wagerup as determined by USEPA TO-5A. Formaldehyde Acetaldehyde Acetone Butanal/ Isobutyraldehyde Hexanal 2-Pentanone/ 3-methyl-2-butanone Boundary Rd 2 (Days) Hoffman Road (Days) Bremnar Road (Days) Hamel Training Centre (Days) 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 Week # 1 None None None None None None None None None 2 25 (12) 14 (14) 13 (13) nd (12) 13 (13) None 3 Invalid None None None None 4 None nd (15) 13 (13) nd (10) nd (11) nd (14) 5 nd (13) nd (13) nd (14) nd (14) None nd (12) 6 None 13 (13) nd (11) None nd (14) nd (13) 1 None None None None None None None None None 2 D (14) 13 (13) D (12) D (12) D (13) None 3 Invalid None None None None 4 None D (15) D (13) D (10) D (11) 28 (14) 5 13 (13) D (13) 14 (14) 14 (14) None D (12) 6 None nd (13) nd (11) None D (14) D (13) 1 None None None None None None None None None 2 D (14) 13 (13) D (12) D (12) D (13) None 3 Invalid None None None None 4 280 (10) None D (15) 25 (13) D (11) D (14) 5 D (13) D (13) D (14) D (14) None D (12) 6 None D (13) D (11) None D (14) D (13) 1 None None None None None None None None None 2 D (14) 22 (13) D (12) D (12) D (13) None 3 Invalid None None None None 4 51 (13) 25 (10) None D (15) nd (11) nd (14) 5 nd (13) D (13) nd (14) nd (14) None nd (12) 6 None 14 (13) nd (11) None 20 (14) nd (13) 1 None None None None None None None None None 2 nd (14) nd (13) nd (12) nd (12) nd (13) None 3 Invalid None None None None 4 None nd (15) 13 (13) nd (10) nd (11) nd (14) 5 nd (13) D (13) nd (14) nd (14) None nd (12) 6 None 14 (13) nd (11) None nd (14) nd (13) 1 None None None None None None None None None 2 34 (12) D (14) 39 (13) D (12) D (13) None 3 Invalid None None None None 4 59 (13) 34 (10) None D (15) D (11) D (14) 5 18 (13) D (13) D (14) D (14) None D (12) 6 None D (13) D (11) None D (14) D (13) Only run 2 analysed. Collection flow rate at end many times higher than at start. No sample collected. Bold typeface indicates measured value is "reportable" as > 2 times MDL. - 40 - Yarloop Lawn Bowls (Days) 1 2 3 4 5 None None nd (14) None nd (13) None None D (14) None nd (13) None None D (14) None D (13) None None nd (14) None nd (13) None None nd (14) None nd (13) None None D (14) None nd (13) None None nd (14) 14 (14) nd (13) nd (14) None None 14 (14) 14 (14) D (13) nd (14) None None D (14) D (14) D (13) D (14) None None nd (14) nd (14) nd (13) nd (14) None None nd (14) nd (14) nd (13) nd (14) None None D (14) D (14) D (13) nd (14) None None None None None None None None None None None None Appendix 8: VOCs concentration at 11 sampling points around Wagerup as determined by passive sampling (Radiello). n-Hexane n-decane n-Heptane Isooctane nd (0.16) nd (0.14) nd (0.21) 0.16 (0.16) nd nd nd nd nd 0.15 (0.15) nd nd 0.14 (0.14) nd nd 0.89 (0.22) nd nd nd nd nd nd nd nd nd (0.16) nd (0.14) nd (0.22) nd nd nd nd nd nd (0.16) nd nd nd nd nd nd (0.15) nd nd nd nd nd 0.59 (0.15) nd nd nd nd 0.29 (0.14) 0.15 (0.15) nd nd nd nd 0.57 (0.14) 0.15 (0.15) nd nd nd nd nd D (0.23) nd nd nd nd (0.22) nd D (0.23) nd nd nd 0.22 (0.22) 0.23 (0.23) D (0.22) nd nd nd Benzene Toluene Xylenes 1 nd (0.11) nd (0.12) 2 3 4 5 6 0.12 (0.12) 0.12 (0.12) nd nd nd nd 0.12 (0.12) nd 0.13 (0.13) nd 1 nd (0.12) nd (0.13) 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 nd nd nd nd nd nd (0.12) 0.12 (0.12) nd nd nd nd 0.12 (0.12) nd 0.12 (0.12) nd nd nd nd nd 0.11 (0.11) nd 0.13 (0.13) nd (0.13) nd nd nd nd 0.13 (0.13) 0.13 (0.13) 0.27 (0.13) 0.12 (0.12) nd nd nd Cyclohexane Others nd (0.17) nd (0.17) nd nd nd nd 0.17 (0.17) nd 0.36 (0.18) nd nd nd nd nd nd nd nd nd nd (0.16) nd (0.17) nd (0.19) nd nd nd nd nd nd 0.16 (0.16) nd nd nd nd nd 0.65 (0.16) 0.51 (0.17) nd 0.56 (0.14) 0.26 (0.13) 0.35 (0.17) nd nd nd nd nd nd (0.17) nd nd nd nd nd nd (0.17) nd nd nd nd nd nd nd nd nd nd 0.18 (0.18) nd nd nd nd nd 0.52 (0.17) nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Week # Bremnar Road (11) Residue Area (3) Residue South (4) Boundary Road 3 (7) 1 nd (0.12) nd (0.13) nd (0.15) 4.1 (0.14) nd (0.22) 0.16 (0.16) 0.17 (0.17) nd (0.19) nd Boundary Road 2 (8) 2 3 4 5 6 nd 0.12 (0.12) nd 0.12 (0.12) nd nd 0.13 (0.13) 0.14 (0.14) 0.13 (0.13) 0.14 (0.14) nd nd nd nd nd nd nd nd nd nd nd D (0.22) nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 0.20 (0.20) nd nd nd nd Y1 nd nd 1 nd (0.12) nd (0.13) nd (0.16) 12 (0.15) nd (0.23) 0.33 (0.17) 0.53 (0.18) nd (0.18) nd Hoffman Road (10) 2 3 4 5 6 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd D (0.22) nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Note : Y 1 : Isobutanol 1.8 (0.14) - 41 - Appendix 8 (cont.) Clifton Road (6) Yarloop Lawn Bowls (5) Willowdale Mine (12) Week # 1 2 3 4 5 Benzene Toluene Xylenes n-Hexane n-decane n-Heptane Isooctane Cyclohexane Others 0.23 (0.12) nd 0.12 (0.12) nd nd nd (0.13) nd 0.13 (0.13) 0.11 (0.11) nd nd (0.15) nd nd nd nd nd (0.14) nd nd nd nd nd (0.22) nd D (0.22) nd nd nd (0.16) nd nd nd nd nd (0.17) nd nd nd nd 0.17 (0.17) nd nd nd nd nd nd nd nd nd 6 nd 0.27 (0.14) nd nd nd nd nd nd nd 1 2 3 0.12 (0.12) 0.37 (0.12) 0.25 (0.13) nd (0.15) nd (0.14) nd (0.22) D (0.16) nd (0.17) nd (0.17) nd 0.24 (0.12) nd 0.26 (0.13) nd nd nd nd nd D (0.22) nd nd nd nd nd nd nd nd 4 0.20 (0.10) 0.22 (0.11) nd 0.12 (0.12) nd 0.14 (0.14) nd 0.30 (0.15) nd 5 0.12 (0.12) 0.26 (0.13) nd nd nd nd nd nd nd 6 0.25 (0.13) 0.41 (0.14) 0.16 (0.16) nd nd nd nd nd nd 1 2 3 4 nd (0.12) nd nd nd nd (0.13) nd nd nd nd (0.15) nd nd nd 0.43 (0.14) nd nd nd nd (0.22) nd D (0.23) nd nd (0.16) nd nd nd nd (0.17) nd nd nd nd (0.19) nd nd nd nd nd nd nd 5 nd nd nd nd nd nd nd nd nd 6 nd nd nd nd nd nd nd nd nd 1 0.63 (0.13) 0.41 (0.12) 0.16 (0.16) 0.30 (0.15) nd (0.23) 0.17 (0.17) nd (0.18) nd (0.19) nd Waroona 2 0.22 (0.11) 0.36 (0.12) 0.29 (0.15) 0.68 (0.14) nd nd nd nd nd Lawn Bowls (1) 3 0.48 (0.12) 0.39 (0.13) nd nd D (0.22) nd nd nd nd 4 0.42 (0.10) 0.68 (0.11) 0.27 (0.14) 0.25 (0.13) nd 0.14 (0.14) nd 0.31 (0.15) nd 5 0.36 (0.12) 0.38 (0.13) nd nd nd nd nd nd nd 6 0.49 (0.12) 0.72 (0.13) 0.32 (0.16) nd nd nd nd nd nd 1 2 3 4 5 6 nd (0.12) nd 0.12 (0.12) nd nd nd nd (0.14) nd nd nd 0.13 (0.13) nd nd (0.15) nd nd 2.2 (0.16) nd nd nd (0.15) nd nd nd 0.43 (0.14) nd nd (0.23) 0.42 (0.21) D (0.22) nd nd nd nd (0.17) nd nd nd nd nd nd (0.18) nd nd 0.57 (0.19) 0.17 (0.17) nd nd (0.19) nd nd 0.39 (0.19) nd nd nd nd nd Y2 nd nd Hamel Training Centre (2) Note : Y 2 : 2-Methylpentane: 0.74 (0.15) & 3-Methylpentane: 0.74 (0.15) - 42 - Appendix 9A: VOCs concentration at the 5 key sampling points around Wagerup as determined by active sampling method USEPA TO-17. Carbon tetrachloride (Days) 2 3 4 Week # 1 1 nd nd Boundary 2 nd nd nd Rd 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 nd nd nd 0.62 (0.62) nd nd 1 nd 2 3 4 5 6 1 2 3 4 5 6 nd 0.62 (0.62) nd nd 1 Lost Hoffman Road Yarloop Lawn Bowls Bremnar Road Hamel Training Centre nd nd nd 1 Lost nd nd nd 2 Lost nd nd nd nd D nd nd nd nd nd nd nd 1 Lost nd nd nd nd nd 1 nd 0.58 (0.58) nd D (1.2); D (0.59) D (1.2); D (0.60) nd nd nd nd nd nd nd 0.62 (0.62) nd nd nd nd nd nd nd nd 1 Lost nd nd nd nd nd nd nd 0.62 (0.62) nd nd nd nd nd 0.73 (0.61) nd nd nd nd nd nd nd nd 1.6 (1.6); 0.85 (0.85) Y Toluene 2.3 ug/m3 and Xylene 1.1 on Run 1/AM (MDLs 0.60 ug/m3) * S-B-benzene: 360.0 ug/m3 on Run 1/AM (MDL 1.2 ug/m3) nd nd nd 2 Lost nd D (1.2); D (0.60) nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd Benzene (Days) 2 3 5 * nd nd nd 1 Lost nd nd nd nd nd nd nd nd nd nd nd nd 1 Lost nd nd nd nd nd 4 nd nd nd nd nd nd 1 2 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 4.6 (1.2) nd 0.86 (0.62) nd nd nd nd nd nd 1 Lost nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 1.7 (1.2) nd nd nd 0.95 (0.59) 0.73 (0.61) nd Y nd nd nd nd * nd nd nd nd 1 Lost nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 5 nd nd nd nd nd 0.74 (0.62) nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd D (0.62) nd nd 0.60 (0.60) nd nd nd nd Shaded cells show days when no samples were collected Italic typeface indicates one run has measured value more than 2 times the MDL. - 43 - 4 nd nd nd nd 1.3 (1.3) 0.79 (0.57)* nd nd nd nd Toluene (Days) 3 5 Appendix 9B: Additional VOCs at the 5 key sampling points as determined by USEPA TO-17. Additional Compounds (Days) Boundary Rd 2 Hoffman Road Yarloop Lawn Bowls Bremnar Road Hamel Training Centre Week # 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 nd MCP, Hexane 2 nd nd nd 3 nd nd nd nd nd 1 Lost nd Hexane nd 2 Lost 2-MP, Pentane Iso-Pentane nd D nd Hexane D nd nd 1 Lost nd nd nd nd nd 2-MP nd 1 Lost nd D 2-MP, Pentane 2-MP, Pentane nd nd nd nd nd nd 4 nd nd nd Hexane Hexane Hexane nd nd nd nd nd nd nd D Hexane D nd nd 2-MP, Pentane nd nd nd nd nd nd nd nd nd 5 nd nd Hexane nd nd nd nd nd nd 2-MP, Pentane nd Hexane nd nd 2-MP, Pentane nd Hexane nd nd D More than 3 additional compounds found - semi-quantative analysis only MCP: methyl cyclopentane 2-MP: 2-methylpentane - 44 - Appendix 10 A: VOCs concentration at 4 key sampling points as determined by USEPA TO-13A. (Days) Week # Boundary 1 1-6 2 3 4 5 No samples collected over 6 week period. Rd 2 1 2 Hoffman Road None Naphthalene 0.0034 1-Mnaph 0.0033 2-Mnaph 0.0033 nd nd nd 3 Benzyl Alcohol 0.068 Benzyl Alcohol 0.0063 nd nd Naphthalene 0.0061 1-Mnaph 0.0041 2-Mnaph 0.0081 m&p Cresol 0.0051 o-Cresol 0.0010 4 Naphthalene 0.0033 Benzyl Alcohol 0.0033 nd Addnl Addnls Addnls 5 nd nd Addnls Addnl 2-Mnaph 0.0010 Addnl 6 nd m&p Cresol 0.0032 Pyrene 0.0032 m&p Cresol 0.016 nd 2-Mnaph 0.00078 m&p Cresol 0.0016 Addnls None 10 11 7 6 3 Naphthalene 0.0036 Addnl 5 plus 7 plus Addnl Addnls Addnl m&p Cresol 0.00098 Phenol 0.00098 Addnl 1 2 Yarloop Lawn Bowls ** 3 4 5 6 plus 6 plus Addnls Addnls Naphthalene 0.0034 nd 3 plus Addnls Naphthalene 0.016 5 plus Addnls 6 plus Addnls 6 Addnl nd Addnl Phenol 0.0025 Addnl 4 plus 1 nd nd None nd nd nd None nd nd nd nd (Addnl) nd (Addnl) nd (Addnl) nd nd (Addnls) nd m&p Cresol 0.0051 nd (Addnls) Bremnar 2 nd nd Road 3 None nd Hamel Training 4 5 6 1 2 3 Centre 4 None nd 5 Naph 0.0031 6 m&p Cresol 0.015 Addnls 2-MNaph 0.0053 Mnaph 0.0026 nd 1- m&p Cresol 0.0050 Addnls ** See Appendix 2B for more detailed information at this locality. Shading indicates no samples were collected. - 45 - Appendix 10 B: PAHs concentration at Yarloop Lawn Bowls as determined by active sampling method USEPA TO-13A. Week # 1 2 2 3 4 5 Fluorene 0.0033 Naphthalene 0.030 Phenanthrene 0.0066 Dibenzofuran 0.0033 1-Mnaph 0.0099 2-Mnaph 0.020 m&p Cresol 0.0039 o-Cresol 0.0020 Phenol 0.0099 2,4-Dimethylphenol 0.013 1,4-Dichlorobenzene 0.0099 Naphthalene 0.0032 1-MNaph 0.0099 2-MNaph 0.020 m&p Cresol 0.0050 o-Cresol 0.0050 Phenol 0.0011 1,4-Dichlorobenzene 0.0011 Naphthalene 0.0098 1-MNaph 0.0033 2-Mnaph 0.0033 m&p Cresol 0.016 o-Cresol 0.0033 1,4-Dichlorobenzene 0.0033 Naphthalene 0.0090 2-Mnaph 0.0030 1,4-Dichlorobenzene 0.0030 Fluoranthene 0.0011 Fluorene 0.0022 Naphthalene 0.018 Phenanthrene 0.0056 Pyrene 0.0011 1-MNaph 0.0056 2-MNaph 0.010 m&p Cresol 0.0011 1,4-Dichlorobenzene 0.0022 Addnls nd Naphthalene 0.0036 Addnl Naphthalene 0.016 1-Mnaph 0.0040 2-Mnaph 0.0080 m&p Cresol 0.0080 o-Cresol 0.0040 Addnl Naphthalene 0.0061 Phenanthrene 0.0020 1-MNaph 0.0020 2-MNaph 0.0031 m&p Cresol 0.0080 o-Cresol 0.0040 1,4-Dichlorobenzene 0.0022 Addnls Naphthalene 0.016 Naphthalene 0.0095 1-Mnaph 0.0040 2-Mnaph 0.0032 m&p Cresol 0.0032 1,4-Dichlorobenzene 0.0032 Addnls Addnl m&p Cresol 0.00098 Phenol 0.00098 Addnl Addnl Phenol 0.0025 Addnl 1-Mnaph 0.0040 2-Mnaph 0.0032 m&p Cresol 0.014 o-Cresol 0.0016 Addnls Lost 1-Mnaph 0.0033 2-Mnaph 0.0033 m&p Cresol 0.0065 o-Cresol 0.0033 2,4-Dimethylphenol 0.0033 1,4-Dichlorobenzene 0.0033 Addnls 4 Naphthalene 0.0034 5 Naphthalene 0.0032 m&p Cresol 0.0096 o-Cresol 0.0064 Addnls 6 3 DAYS No samples Collected. 1 Addnl 1-Mnaph 0.0037 2-Mnaph 0.0074 m&p Cresol 0.011 o-Cresol 0.0037 2,4-Dimethylphenol 0.0037 Benzyl Alcohol 0.015 1,4-Dichlorobenzene 0.0037 Addnls nd Naphthalene 0.025 Phenanthrene 0.0031 Dibenzofuran 0.0031 1-MNaph 0.0062 2-MNaph 0.012 m&p Cresol 0.018 o-Cresol 0.0092 Phenol 0.0062 2,4-Dimethylphenol 0.0092 1,4-Dichlorobenzene 0.0031 - 46 - Appendix 11: Metals concentrations at the 5 key sampling points around Wagerup as determined by AS-2800. Hoffman Road (Weeks) (ug/m3) Ave MDL TSP Bremnar Road (Weeks) 1 2 3 4 5 6 9 12 12 16 13 16 1 2 3 8.0 9.4 9.6 Lead 0.0000042 0.00017 0.00031 0.000051 0.00017 0.00025 0.00066 0.00018 0.00080 nd Aluminium 0.0000167 nd 0.26 nd 0.67 0.53 0.78 Arsenic Boron Barium Beryllium Cadmium Cobalt Chromium Copper Galium Mercury Lithium Molybdenum Nickel Selenium Thallium Vanadium Zinc 0.0000042 0.0000836 0.0000084 0.0000004 0.0000004 0.0000167 0.0000084 0.0000167 0.0000004 0.0000143 0.0000167 0.0000836 0.0000418 0.0000418 0.0000004 0.0000167 0.0000167 0.000019 nd nd nd 0.000015 nd nd 0.00010 nd nd nd nd nd 0.00017 0.000019 nd 0.00038 0.000051 nd nd 0.000010 0.0000038 nd 0.00077 0.00067 nd nd nd nd 0.00028 0.000077 0.0000036 0.00077 nd nd nd nd nd nd nd nd 0.000051 nd nd nd 0.000034 0.00014 0.000068 0.0000038 nd nd nd 0.017 nd nd nd 0.000051 0.0010 0.00037 0.00034 nd 0.00017 nd 0.00049 0.000098 0.0000051 0.0015 0.0017 0.0000071 nd nd nd nd nd 0.00071 0.00014 nd nd 0.00018 nd 0.00025 0.000053 nd 0.0012 nd 0.000075 0.11 nd 0.0000063 nd 0.000016 0.0013 0.00036 nd nd 0.00063 nd 0.00094 0.000094 0.0000047 0.0016 nd nd 0.000040 nd nd 0.000012 0.000006 nd 0.0018 0.00018 nd nd nd nd 0.00060 nd 0.0000074 0.00020 nd 2.1 0.00014 0.44 0.012 0.000026 0.0000047 0.00016 0.0023 0.0011 0.00094 nd 0.0016 0.00012 0.00068 0.00012 0.0000044 0.0023 0.0094 nd nd nd nd nd nd nd nd 0.00049 nd nd nd nd nd nd nd nd nd - 47 - 4 5 6 NO samples collected Hamel Training Centre (Weeks) Ave MDL TSP Lead 0.0000041 Aluminium Arsenic Boron Barium Beryllium Cadmium Cobalt Chromium Copper Galium Mercury Lithium Molybdenum Nickel Selenium Thallium Vanadium Zinc 0.0000165 0.0000041 0.0000823 0.0000082 0.0000004 0.0000004 0.0000165 0.0000082 0.0000165 0.0000004 0.0000150 0.0000165 0.0000823 0.0000411 0.0000411 0.0000004 0.0000165 0.0000165 1 2 Boundary Rd 2 (Weeks) 3 4 5 6 1 12 17 16 19 10 0.00039 nd nd nd nd nd nd nd N0 samples collected nd 0.00086 nd nd nd nd nd nd 0.0000043 nd nd 0.00028 0.35 0.000035 nd nd nd nd 0.000053 0.0021 0.00049 nd nd nd nd 0.0010 0.000071 0.0000053 0.00088 nd 0.00045 1.3 0.000050 0.25 nd nd nd 0.00010 0.0025 0.00065 nd 0.00000050 0.0012 0.00012 0.00094 0.000050 nd 0.0022 nd 0.00064 0.60 0.000072 0.10 nd 0.0000045 0.0000075 0.000045 0.0034 0.00075 0.000030 nd 0.00045 0.00010 0.0017 0.000090 0.0000030 0.00075 nd nd nd nd nd nd nd nd 0.000056 0.0014 nd nd nd nd nd 0.00056 nd 0.0000061 0.00028 nd ** No samples were collected for TSP and metals analysis at Yarloop Lawn Bowals. - 48 - 2 3 4 NO samples collected 5 6 Appendix 12: Inorganic acids concentration at the 5 key sampling points around Wagerup as determined by NIOSH 7903. Sulphuric Acid Nitric Acid Phosphoric Acid Hydrogen Bromide Hydrogen Chloride Hydrogen Fluoride Week # 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 Boundary Rd 2 (Days) 2 3 4 5 nd (95) nd (93) 1 Hoffman Road (Days) 2 3 4 nd (110) Invalid D (110) None nd (100) nd (110) nd (110) 5 1 Yarloop Lawn Bowls (Days) 2 3 4 nd (90) nd (110) 130 (110) Invalid nd (100) D (100) nd (90) nd (95) nd (93) None nd (100) nd (110) nd (110) nd (110) Invalid nd (110) nd (110) nd (110) Invalid nd (100) nd (100) nd (90) nd (90) nd (110) Invalid nd (110) nd (110) nd (110) Invalid nd (100) nd (100) nd (90) nd (110) Invalid nd (110) nd (110) nd (110) Invalid nd (100) nd (100) nd (90) nd (110) Invalid nd (110) nd (110) nd (110) Invalid nd (100) nd (100) nd (90) nd (57) Invalid nd (54) nd (56) nd (57) Invalid nd (51) nd (50) nd (45) nd (95) nd (93) None nd (100) nd (110) nd (110) nd (90) nd (95) nd (93) None nd (100) nd (110) nd (110) nd (90) nd (95) nd (93) None nd (100) nd (110) nd (110) nd (90) nd (47) nd (46) None nd (51) nd (56) nd (57) nd (45) No sample collected. Bold typeface indicates measured value is "reportable" as > 2 times MDL. - 49 - 5 Appendix 12 (cont.) Sulphuric Acid Nitric Acid Phosphoric Acid Hydrogen Bromide Hydrogen Chloride Hydrogen Fluoride Week # 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 1 Bremnar Road (Days) 2 3 4 5 nd (90) 360 (91) D (97) D (100) nd (110) nd (130) 1 Hamel Training Centre (Days) 2 3 4 D (93) Invalid nd (120) nd (110) 260 (110) nd (90) nd (91) nd (97) nd (100) nd (110) nd (130) nd (93) nd (93) Invalid nd (120) nd (110) nd (110) nd (90) nd (91) nd (97) nd (100) nd (110) nd (130) nd (93) nd (93) Invalid nd (120) nd (110) nd (110) nd (90) nd (91) nd (97) nd (100) nd (110) nd (130) nd (93) nd (93) Invalid nd (120) nd (110) nd (110) nd (90) nd (91) nd (97) nd (100) nd (110) nd (130) nd (93) nd (93) Invalid nd (120) nd (110) nd (110) nd (45) nd (45) nd (48) nd (53) nd (56) nd (64) 5 D (93) nd (47) nd (46) Invalid nd (61) nd (54) nd (56) No sample collected. Bold typeface indicates measured value is "reportable" as > 2 times MDL. - 50 - Appendix 13: Bromine and chlorine concentrations at the 5 key sampling points around Wagerup as determined by NIOSH 6011. Week # 1 Boundary Rd 2 2 Property 3 4 5 6 1 2 3 4 5 6 1 2 3 4 5 6 Hoffman Road Yarloop Lawn Bowls 1 2 Bromine (Days) 3 4 5 1 2 Chlorine (Days) 3 nd (140) nd (140) 4 5 nd (140) nd (140) nd (140) nd (140) nd (140) nd (140) nd (140) nd (140) nd (150) 150 (150) nd (140) nd (140) 170 (140) nd (140) 1 Bremnar Road Hamel Training Centre 2 3 4 5 6 1 2 3 4 5 6 nd (130) nd (130) nd (140) nd (140) nd (140) nd (170) nd (140) nd (170) nd (140) nd (170) nd (160) nd (140) nd (140) nd (170) nd (160) nd (140) Shaded cells show days when no samples were collected - 51 -