Atmospherically Deposited Metal and Metalloid Contaminated Dust in Inner Townsville, Queensland Headland Park, The Strand, Townsville, Queensland (Source: Paris Spellson) December 5th 2014 Prepared by Professor Mark P. Taylor with Ali Maadh, Audrey Quicke, Emilia Rupsys, Paris Spellson Discipline of Environmental Science Department of Environment and Geography Faculty of Science and Engineering Macquarie University ~ Sydney North Ryde, NSW 2109 Email contact: [email protected] Telephone: 0422 940 916; 02 9850 4221(w) Report finalised and uploaded to NQCC website, Dec 5th 2014 SUMMARY This study presents the results of metal and metalloids (arsenic, cadmium, lead and nickel) in surface wipes and in pre- and post-play hand wipes following 10 minutes of child-simulated play activity at playgrounds across the inner city of Townsville. The study was undertaken over a 6-day period from September 26th to October 1st 2014. The purpose of the study was to determine the extent of contamination from all elements tested in wipes in places used frequently by children. Data from the study reveal a level of contamination that needs to be addressed. All playgrounds tested showed that, on at least one day, lead dust on surfaces exceeded 400 µg/m2, the goal applied by the Government of Western Australia (2011) for surfaces accessible by children. The mean increase in lead on post-play hand wipes was more than 10 times pre-play loadings. The maximum post-play loading on hands was 3012 µg/m2 (more than seven times the goal of 400 µg/m2 used by the Government of Western Australia, 2011). Repeat sampling of surfaces over the 5-day study period showed that surfaces were re-contaminated daily by the deposition of metal-rich atmospheric dusts. Lead isotopic composition analysis of dust wipes showed that the lead is similar to Mount Isa type ores, which are exported through the Port of Townsville. In the short-term we recommend that thorough daily cleaning of the playgrounds be implemented, along with signage recommending that hands are washed after play. To facilitate this it is suggested that the necessary facilities for cleaning of hands (water or wipes, for example) are made available at playgrounds. For the long-term, however, it is recommended that the source(s) of contamination associated with ore transport into and out of the Port of Townsville be identified and eliminated. Without taking this action, the data suggest that frequent and cumulative metal contamination will perpetuate exposure risks associated with deposited metal-rich dusts across the city 2 1. INTRODUCTION This report evaluates the extent and significance of dust metal deposition in the city of Townsville, Queensland and the potential risk of harm to children. The study focuses on playgrounds because these are readily accessible public places where children interact with the outside environment. Previous work in Port Pirie, South Australia, and Broken Hill, NSW, has demonstrated the potential risk of exposure in playgrounds (Taylor et al., 2013; 2014b). Children are at higher risk of heavy metal poisoning because of their small body size, developmental stage, and because of their tendency to engage in hand-to-mouth behaviour (Jarup, 2003; National Toxicology Program (NTP), 2012; Needleman, 2004). The effects of metal exposure in children, particularly in the case of lead, include irreversible damage to neurological functioning (National Toxicology Program (NTP), 2012; Needleman, 2004; Taylor et al., 2012a,b). For this reason, identifying childhood exposure pathways is critical in order to break the cycle of adverse health effects associated with environmental metals. Lead is a specific focus for this report because of its well-known adverse effects on human health. The report responds to long-standing complaints from sectors of the local community who have raised concerns in regards to dust deposits and their composition coming from loading and unloading operations at the Port of Townsville (Wolanski and Ducrotoy, 2013). Mineral transport operations at the Port of Townsville include the importation of nickel ore and zinc concentrate and the export of copper, lead and zinc concentrate from a range of sources (Port of Townsville Limited, 2012). Ores are moved via rail, with nickel ore being moved in open wagons, and processed concentrates moved in covered wagons. With respect to the metal ores being transported, lead in particular, has a well-known toxicological profile, while the human health effects of nickel are relatively less well understood (ATSDR, 2011). Nevertheless, nickel has known adverse outcomes on respiratory health, can increase dermatitis, is considered to be a human carcinogen and can affect neonatal development (ATSDR, 2011). A Queensland Government study (Queensland Government, 2010) reported on a range of aerosol contaminants in the Townsville environment, including total suspended particles (TSP), and concentrations (µg/m3) of arsenic, cadmium, lead, manganese, mercury, nickel, vanadium and mercury. Total insoluble dust (µg/m2/day) and the lead concentrations in those deposited dusts (lead µg/m2/day) were also reported. The Queensland Government report issued the followed relevant conclusions (Queensland Government, 2010, page iii): 3 “The monitoring program was unable to find any evidence that dust emissions from the Townsville Port contributed significantly to ambient levels of nickel, manganese and vanadium, or to dust deposition, at any monitoring site. While compliance with EPP (Air) objectives was maintained at all times, the monitoring program identified that dust emissions from Townsville Port activities did contribute to ambient levels of TSP, lead, copper, zinc, arsenic and cadmium, and to lead deposition, at the closest monitoring site, Coast Guard. Measurable contributions of these pollutants from Townsville Port activities at monitoring sites located further from the Port were only observed for lead. Queensland Health has concluded that the total exposure to lead from inhalation and ingestion of dust in the residential community areas near the Townsville Port is highly unlikely to be associated with any known adverse health effects.” This report presents the results from surface dust and post-play hand wipe dust samples collected from six locations across Townsville. The study focuses on atmospheric lead deposition but also reports on the post-play hand wipe loadings (µg/m2) of arsenic, cadmium and nickel (cf. Taylor et al., 2013; 2014b). These elements formed part of the Queensland Government’s (2010) air quality study (measured primarily as metals in µg/m3) and are included as part of regular air quality monitoring programs in the city (Queensland Government, 2014). However, only lead in dust was, and continues to be, measured in dust deposition. This study asks 3 main questions: 1. What is the spatial and temporal distribution of heavy metal contamination in playgrounds around inner Townville and how, if at all, do they relate to the operations at the Port? 2. What are the risks to public health? 3. What action is required to reduce the risk of exposure? 2. METHODS The methods and approach undertaken in this study of surface dusts are similar to those conducted recently by the lead author in Port Pirie and Broken Hill (Taylor et al. 2013; 2014b). A brief description of the field methods undertaken for this study is provided below. 2.1 Field Sampling Six flat surfaces across Townsville city were sampled daily for arsenic, cadmium, lead and nickel loadings from 26th September to 1st October 2014. The six sample surfaces were wiped before the start of the daily playground sampling program. The purpose of this ‘pre-wipe’ (conducted 26th 4 September), was to establish a historical measure of longer-term deposition as compared to the daily 24-hour values that were collected subsequently via the surface wipes. It should be noted that the length of time these ‘pre-wiped’ surfaces had been exposed to atmospheric loading without prior wiping or any cleaning or washing from precipitation is unknown. Subsequent surface wipes (n = 30) provided a measure of the 24-hour metal and metalloid (hereafter referred to as metals) loading over the remaining study period 27th September to 1st October, 2014. Sample sites were determined partly by access to suitable playgrounds, paint-free surfaces, locations proximal and downwind from the Port and existing environmental data for Townsville (Queensland Government, 2010; 2014). The surfaces selected for sampling were exposed to the atmosphere and were considered unlikely to be disturbed by users of the playgrounds. The surfaces at Sister Kenny Park, Headland Park, Soroptimist Park, Queens Park Oval and Anzac Memorial Park were stainless steel surfaces of council rubbish bins or other utility boxes. At Reid Park similarly constructed surfaces were not available so a flat surface on top of the playground equipment was marked out and sampled for surface dust metal loading. Surface areas were demarked using masking tape and the dimensions measured. Wiped surface areas were 30 cm x 30 cm, except where suitably sized surfaces were unavailable: Reid Park - 60 cm x 13 cm; Queens Park Oval - 40 cm x 24 cm; Anzac Memorial Park - 30 x 29 cm. Metals measured in the wipe samples (µg/wipe) were subsequently standardised to µg/m2, to allow comparison with a range of relevant surface dust standards. Dust wipes were collected using the method described in ASTM E 1728-03 (American Society for Testing and Materials, 2003), which is standard protocol for surface dust lead measurement. The dust wipes used were the Lead WipeTM, which is designed specifically for lead dust sampling. A minimum of two soil samples was taken from each of the six locations (Figure 1) where surface and playground wipes were collected (n = 15). Samples were taken from a depth of 0-2 cm in line with AS 4874-2000 (Standards Australia, 2000). Bulk soil samples were collected in labelled, sealed plastic bags and oven dried for 48 hours or until dry, to remove moisture. 5 Soroptimist Park Headland Park North Ward – Qld Govt site Sister Kenny Park Queens Park Oval Port of Townsville Coast Guard– Qld Govt site Anzac Memorial Park Reid Park Figure 1. Map of Townsville showing locations of soil, playground and surface wipe sample sites (marked with red circles). Sample sites collecting both playground and surface wipes: Sister Kenny Park; Headland Park; Soroptimist Park; Reid Park. Sites sampled only for surface dusts were: Queens Park Oval and Anzac Memorial Park. Queensland Government dust lead monitoring sites (marked in blue) North Ward and Coast Guard are also shown. Dust wipes were collected at approximately the same time in the morning of each sample day in the same sequence: Sister Kenny Park, Headland Park, Soroptimist Park and Reid Park. Nitrile gloves were worn at all times to prevent accidental contamination and sampled wipes were stored in labelled, sealed lead-free zip lock plastic bags prior to analysis at the Australian Government’s National Measurement Institute, Sydney. In addition, four playgrounds were sampled daily for five days: 27th September to 1st October 2014 (Figure 1) using a combination of pre-play and post-play hand wipes, which were taken after 10 minutes of child-simulated play on the playgrounds. The playground sampling protocol utilised ‘simulated play’ to measure metal loadings that children might be exposed to during interaction with the playgrounds (see methods in Taylor et al. 2013; 2014b). Each day, the same researcher ‘played’ on the play equipment at the allocated site for 10 minutes, mimicking the exploratory behaviour of a child. The researcher’s hands were wiped thoroughly with dust wipes prior to play and following play using the method employed by Taylor et al. (2013; 2014b). Samples from both hands were combined into a single sample, resulting in 40-paired samples. Pre- and post-play wipes were analysed separately for metals (arsenic, cadmium, lead and nickel) and compared 6 subsequently to measure the effect of contact with the play equipment. The frontal hand surface area was calculated for each play participant using DuBois and DuBois (1916) and then converted to µg/m2 to allow comparison between each of the playgrounds over the 5 day sample period. 2.2 Laboratory Analysis Dust wipes were analysed by the National Measurement Institute, Sydney, for arsenic, cadmium, lead and nickel. Dust wipes were digested in a 3:1 ratio of aqua regia and measured for their metal concentrations using a Varian 730-ES ICP-OES and Perkin Elmer Elan DRC II ICP-MS. Blanks, duplicates, matrix spike and reference samples were also analysed to verify sample data quality. After drying, soil samples were sieved to < 2 mm prior to hand held XRF analysis using an Olympus Delta 40kV instrument. This approach was taken to screen soils to ascertain if higher precision, wet chemistry analysis was warranted. 2.3 Laboratory Quality Assurance / Quality Control Field dust blanks returned < 0.1 µg/wipe for arsenic, < 0.05 µg/wipe for cadmium, 0.074 µg/wipe for lead and 0.275 µg/wipe for nickel, respectively, suggesting there may have been some detectable ambient lead and nickel during sampling. Laboratory blanks were below the limits of reporting – < 0.1 µg/wipe for arsenic, and < 0.05 µg/wipe for cadmium, lead and nickel. Recovery rates for the in-house laboratory control sample (AGAL-10) were as follows: arsenic 100 %; cadmium 98 %; lead 106 % and nickel 110%. Matrix spike recoveries were within laboratory reporting procedures for all elements, ranging from a minimum of 88 % (lead) to 107 % (arsenic). Lead isotopic compositions of selected samples (n = 10) were determined using a Perkin Elmer Elan DRC II ICP-MS after optimizing sample concentrations. Analyses were conducted with concentration-matched measurements of NIST SRM 981 bracketing each sample, which were used to correct for isotopic mass fractionation. Analytical precision (RSD) for lead isotopic compositions was 1.606%, 0.684% and 2.007% for 206Pb/207Pb, 208Pb/207Pb and 206Pb/204Pb, respectively. 2.4 Statistical Analysis Wilcoxon signed-rank tests for hand wipe data were performed using the web-based statistical application developed by Stangroom (2014). Regression analysis was also used to assess the relationship between surface metal loadings and compared with those recovered on post-play hand wipes. 7 3. RESULTS 3.1 Surface Dust In order to understand the loading metal values recovered from the surface wipes, a range of relevant benchmark values need to be considered. These include the arsenic (4 µg/m2/day), cadmium (2 µg/m2/day), and lead (100 µg/m2/day), dust deposition limits and trigger values listed under schedule B, Table 4 of the Mount Isa Mines Environmental Authority (available in the supplementary data of Taylor et al., 2014a). These trigger values are calculated as an annual average per calendar year. The German Federal Immission Control Act 2002 (TA Luft 2002) also contains on the same dust deposition standards as those in the Mount Isa Mines Environmental Authority, and lists a maximum value for nickel at 15 µg/m2/day, averaged over a year. Other relevant values include the surface lead dust standard provided by the Government of Western Australia (2011) of 400 µg/m2 for surfaces accessible to children. This value was applied to the lead carbonate spill clean-up program in Esperance (Government of Western Australia (2011). There is also the more general Australian Standard for outdoor dust of 8000 µg/m2, which was devised for lead paint management (Standards Australia, 1998). In this study of surface dust metal deposition, we rely on the values promulgated by the Queensland Government in the Mount Isa Mines Environmental Authority for arsenic, cadmium and lead and on the German Federal Immission Control Act 2002 (TA Luft 2002), for nickel. In addition, for dust lead, particularly with respect to playground activity, we rely primarily on the Government of Western Australia (2011) lead dust standard of 400 µg/m2 because it refers specifically to children and the potential hazard lead dust may pose to them. The data returned from the dust pre-wipes collected on 26th September 2014 show that deposition of lead-rich particles in the inner city is accumulating to levels that exceed acceptable standards (Table 1, Figure 2). The wipes collected on the first day of the study (i.e. 26th September 2014) are referred to as ‘pre-wipes’ and reflect the longer-term metal loading because, to the best of our knowledge, they had not been subject to recent cleaning (Figures 2, 3). 8 Table 1. Dust loadings measured on September 26th 2014 (pre-wipe samples). Because surfaces were not pre-cleaned, the values can be taken to indicate ‘typical’ loading on surfaces not cleaned regularly. Bold and underlined values exceed the Government of WA (2011) lead carbonate clean-up value of 400 µg/m2 of lead on surfaces accessible to children. No equivalent values exist for the other elements. Where values were below the limits of reporting they were assigned zero for statistical purposes. Long-term surface dust lead and nickel loadings 10000 Dust loading values (µg/m2) Lead Nickel WA Govt lead clean-up value for surfaces accessible to children (400 µg/m2) 1000 100 10 1 Sister Kenny Park Headland Park Soroptimist Park Reid Park Queen's Park Oval Anzac Memorial Park Figure 2. Lead and nickel dust loadings on horizontal surfaces collected on 26th September 2014. Surface lead loadings are compared with the Government of WA (2011) lead carbonate clean-up value of 400 µg/m2 of lead on surfaces accessible to children. No similar value exists for nickel. Note the y-axis is scaled logarithmically. See Table 1 for raw data. 9 Long-term surface dust arsenic and cadmium loadings 20 Arsenic Cadmium 18 Dust loading values (µg/m2) 16 14 12 10 8 6 4 2 0 Sister Kenny Park Headland Park Soroptimist Park Reid Park Queen's Park Oval Anzac Memorial Park Figure 3. Arsenic and cadmium dust loadings on horizontal surfaces collected on 26th September 2014. There are no Australian loading values for arsenic or cadmium. See Table 1 for raw data. In terms of the surface dust metal loading measures collected on a daily basis from the six sites across inner Townsville, the data shows that lead and nickel are the elements that most commonly exceed relevant standards (Table 2). It is worth noting that on September 29th and 30th the surfaces at Sister Kenny Park, Headland Park and Soroptomist Park (September 30th only) appeared to have been cleaned by Council workers, which may have had the effect of lowering the loading values in the analysed wipes. 10 Mean St Devn Min Max Mean Headland St Devn Park Min Max Mean Soroptimist St Devn Park Min Max Mean St Devn Reid Park Min Max Mean Queen's St Devn Park Oval Min Max Mean Anzac St Devn Memorial Min Park Max Sister Kenny Park Arsenic µg/m 2 1.60 0.99 0.00 2.44 2.53 1.55 1.22 5.22 0.82 1.16 0.00 2.44 5.00 0.87 3.97 6.28 3.46 0.71 2.40 4.27 0.97 1.38 0.00 2.99 Cadmium µg/m 2 0.51 0.49 0.00 1.11 0.93 0.58 0.00 1.56 0.22 0.50 0.00 1.11 1.91 0.48 1.22 2.56 2.38 0.90 1.15 3.44 0.85 0.52 0.00 1.38 Lead µg/m 2 107.56 86.09 40.00 222.22 127.56 90.22 32.22 255.56 54.89 37.75 34.44 122.22 243.59 55.14 166.67 294.87 412.50 131.06 250.00 562.50 110.81 97.39 29.89 264.37 Nickel µg/m 2 46.42 37.71 4.33 88.89 67.33 47.54 6.67 133.33 65.67 54.72 10.56 155.56 38.41 15.60 12.56 51.28 88.54 21.10 61.46 114.58 7.96 1.59 6.21 10.00 Table 2. Summary of daily (24-hour) dust metal and metalloid loadings across all six sites sampled in Townsville city, Queensland, 27th September to 1st October, 2014. Bold and underlined values exceed the trigger values (averaged over a year) set by the Queensland Government for the environmental monitoring of Mount Isa Mines (arsenic - 4 µg/m2/day; cadmium - 2 µg/m2/day; and lead - 100 µg/m2/day) and that for nickel (15 µg/m2/day) in the German air quality control document, TA Luft (2002). 3.2 Pre- and Post-play Hand Wipe Metal Values Figures 4 and 5 and Supplementary Tables S2-S5 show that metal loadings on hands increased postplay, indicating the availability of contaminated dust to children using play equipment. The mean level of increase in lead on post-play hand wipes (965 µg/m2/day) across all sites was more than 10 times mean pre-play loadings (95 µg/m2/day). The maximum post-play lead loading (Reid Park, day 5) measured was 3012 µg/m2 (more than 30 times the trigger value for surface lead loading of 100 µg/m2/day and more than 7 times Government of Western Australia (2011) of 400 µg/m2 for surfaces accessible to children). Maximum daily nickel post-play hand loadings (404 µg/m2, Sister Kenny Park, day 2) were more than 26 times above the German benchmark of 15 µg/m2/day. Maximum arsenic and cadmium post-play hand wipe values (Reid Park, day 2) were also elevated at 43 µg/m2 and 68 µg/m2, respectively. Compared with the trigger values applied in Environmental 11 Authority for Mount Isa Mines, these elements were more than 10 and 34 times over the respective annual average trigger values of 4 µg/m2/day (arsenic) and 2 µg/m2/day (cadmium). A Wilcoxon signed-rank test showed that the increase in metal loading on hands for arsenic, cadmium, nickel and lead post-play compared with pre-play (all sites combined) was significant (95 % confidence). Summary statistical results are provided in Table 3. Element in hand wipe Mean loading (µg/m2 ) Arsenic Pre-play 3.63 Arsenic Post-play 20.25 Cadmium Pre-play 4.54 Cadmium Post-play 25.19 Nickel Pre-play 51.24 Nickel Post-play 174.69 Lead Pre-play 95.03 Lead Post-play 964.91 Standard Deviation 3.07 10.86 3.23 18.63 20.29 99.34 54.89 870.26 n 19 19 20 20 20 20 20 20 z p (1 tail) -3.823 <0.0001 -3.7146 0.0001 -3.8826 <0.0001 -3.9199 <0.0001 Table 3. Summary statistics for post-play increases in metal loadings on hands. Analysis using the Wilcoxon signedrank test shows that post-play arsenic, cadmium, nickel and lead mean loadings are significantly different (p < 0.05) compared with pre-play wipe metal loadings. Note that values below instrument detection limit were treated as zero for statistical analyses. 3.3 Soils Mean concentrations of all metals in the < 2 mm fraction with the exception of a single sample were below the National Environmental Protection (Assessment of Site Contamination) Measure 1999 (NEPM, 2013) guidelines for soils in recreational areas. Only one sample taken from Anzac Memorial Park (1294 mg/kg) exceeded the lead guideline of 600 mg/kg provided by NEPM guidelines for soils in recreational areas (NEPM, 2013). The results are provided in Supplementary Table S1. 12 Sister Kenny Park Soroptimist Park WA Govt lead clean-up value (400 µg/m2) Pre-play 500 Hand lead dust loading (µg/m2) Hand lead dust loading (µg/m2) 2500 Post-play 2000 1500 1000 500 0 Post-play WA Govt lead clean-up value (400 µg/m2) Pre-play Day 1 Day 2 Day 5 400 300 200 100 0 Day 1 Day 2 Day 3 Day 4 Day 5 Headland Park Post-play Day 4 Reid Park WA Govt lead clean-up value (400 µg/m2) Pre-play 3200 Hand lead dust loading (µg/m2) Hand lead dust loading (µg/m2) 1200 Day 3 900 600 300 Post-play WA Govt lead clean-up value (400 µg/m2) Pre-play 2800 2400 2000 1600 1200 800 400 0 0 Day 1 Day 2 Day 3 Day 4 Day 5 Day 1 Day 2 Day 3 Day 4 Day 5 Figure 4. Lead loadings on hands pre- and post-play for each of the four playgrounds sampled (see Figure 1). Post-play hand wipes had significantly higher loadings than pre-play for all metals (see Table 3 for data). The dashed line represents the Government of Western Australia’s (2011) value of 400 µg/m2 for surfaces accessible to children. 13 Sister Kenny Park 400 Headland Park 300 Post-play Hand nickel dust loading (!g/m2) Hand nickel dust loading (!g/m2) 500 Pre-play 300 200 100 0 Day 1 Day 2 Day 3 Day 4 Post-play Pre-play 200 100 0 Day 5 Day 1 Day 2 Soroptimist Park 400 Pre-play 100 50 0 Day 1 Day 2 Day 3 Day 4 Day 5 Day 4 Day 5 Reid Park Post-play Hand nickel dust loading (!g/m2) Hand nickel dust loading (!g/m2) 150 Day 3 Day 4 Day 5 Post-play Pre-play 300 200 100 0 Day 1 Day 2 Day 3 Figure 5. Nickel loadings on hands pre- and post-play for each of the four playgrounds sampled (see Figure 1). Post-play hand wipes had significantly higher loadings than pre-play for all metals (see Table 3 for data). 14 3.4 Lead Isotopic Composition of Dust Wipe Samples Two surface wipes collected from Headland Park and Reid Park on 26th September 2014 were analysed for their lead isotopic composition. The four post-play dust wipes collected from day 1 and day 5 of the playground sampling (n = 8) were also analysed for their lead isotopic composition (Figure 6). The data show that the majority of samples are clustered towards the isotopic composition of Mount Isa type ores (Figure 6). The hand wipes collected on day 5 show the greatest similarity to the probable source materials, Mount Isa type ores, which are transported through the Port in concentrate form. 1.22 Surface dust 1.20 1.18 Post-play hand wipe Day 5 1.16 Mount Isa type ores 1.14 206Pb/207Pb Post-play handwipe Day 1 Townsville aerosols (1998) Present-day crustal average 1.12 1.10 1.08 1.06 1.04 1.02 2.30 2.32 2.34 2.36 2.38 2.40 208Pb/207Pb 2.42 2.44 2.46 2.48 Figure 6. Lead isotopic composition of selected surface dust wipes and post-play hand wipes from this Townsville dust study. Other relevant values for Townsville are also included: Mount Isa type ore lead isotopic compositions (which include Cannington Mine ore, David Huston, Geoscience Australia, pers. com.; Mount Isa Mine ore, Gulson, 1985); Townsville aerosols from 1998 (Bollhöfer and Rosman, 2000) and the present-day crustal average (Stacey and Kramers, 1975). 4. DISCUSSION 4.1. Atmospherically Sourced and Deposited Dust Metals Metal contamination found in the dust in Townsville playgrounds, particularly with respect to lead, demonstrates a potential risk to the health of children living in the city. Minus the single sample at Anzac Memorial Park, which had a substantive grass cover, soil metal loadings were below Australian levels of concern (NEPM, 2013). The data show that, with the exception of the Anzac Memorial Park site, the longer-term accumulation of surface lead dust exceeded the Government of Western Australia’s (2011) benchmark for lead on surfaces accessible to children of 400 µg/m2. The daily (24-hour) sampling carried out over 5-days between September 27th and October 1st 2014 15 showed the short-term elevated measures were largely limited to lead and nickel (Table 2), when benchmarked against trigger values used elsewhere in Queensland (Taylor et al., 2014a) or international standards (TA Luft, 2002). The most dust metal-contaminated playground sites were those close to the Port but not sheltered from the prevailing wind (as is Soroptimist Park) during the study period (Bureau of Meteorology, 2014a). The Bureau of Meteorology (2014b) average annual wind rose data show the 9 am wind direction is from the south-east, with the prevailing wind at 3 pm coming from the north-east across the Port and then the city. These winds, which are dominated by air speeds of 20-30 kmph, would have the capacity to entrain and transport dusts generated at the Port during unloading and loading activities. Data from the pre- and post-play hand wipes provide a direct measure of the dust metal exposure risk available to children during the use of the play facilities. All playgrounds were found to have lead dust on surfaces in excess of the Government of Western Australia’s (2011) goal of 400 µg/m2 for surfaces accessible to children on at least one day of the 5-day sample period. Reid Park had the highest average post-play hand wipe lead loadings, with an average of 1981 µg/m2 over the study period, but did not have the highest long-term loadings on surface wipes. Overall, Soroptimist Park returned the lowest values in post-play wipes across the week compared with the other playgrounds. Soroptimist Park is partly sheltered by the headland at the end of The Strand, which may account for its lower values. Reviewing the data as whole, it is clear that the values returned for the dust metals analysed are elevated by comparison with Queensland State dust deposition limits and trigger values and international standards. The values returned in this study, albeit with its limitations due to the short time period of sampling, are a cause for concern with respect to young children who frequent the playground facilities and for whom susceptibility to metal toxicity is greatest (Jarup, 2003; Needleman, 2004). The research literature is replete with studies of arsenic, cadmium and lead human toxicity effects (e.g. Calderón et al. 2001; Rosado et al. 2007; von Ehrenstein, 2007; Roy et al. 2011; Ciesielski et al. 2012; NTP, 2012). Nickel is less well studied by comparison but the highly respected USA Agency for Toxic Substances and Disease Registry, for example, has established clearly that nickel exposures are potentially damaging to human health in terms of respiratory health and function, are associated with an increased occurrence of contact dermatitis and are also considered to be a possible human carcinogen (ATSDR, 2011). Certainly, exposures to nickel dust cannot be considered neutral and, in the absence of sufficient causal relationships, it would not be unreasonable to apply the precautionary principle, particularly where vulnerable members of the community (young children and pregnant women) are at risk of exposure. Young 16 children are more susceptible to metal exposure and toxicity due to their persistent hand-to-mouth behaviours, developing skeletal and neurological systems and the fact that they are closer to the ground where dust is generated. In addition, because children are small, they have a high surface area to volume ratio compared with adults, which increases their potential for dermal loading and exposure. In this regard, Queensland Health (Queensland Government, 2010) noted that with respect to lead “it is a basic principle that lead exposure be maintained as low as possible” and by deduction, the same would apply to exposures to other potentially toxic metals deposited in dust across residential environments. The elevated total metal loading values returned in the surface and hand wipes, the prevailing wind and the known operations at the Port of Townsville point strongly to the source of the dust. Indeed, there are no other alternative sources in the city of Townsville and the daily lead loading values returned in this study are not inconsistent with some of the Queensland Government values reported at the Townsville Coast Guard site (Queensland Government 2014). In this Queensland Government report, values from October 2013 show a maximum daily lead dust deposition rate of 714 µg/m2/day at the Coast Guard site, equalling a total lead dust deposition loading of 22,134 µg/m2 over that month. The annual average lead dust deposition rate reported in the Queensland Government (2014) air quality bulletin for the Coast Guard site is 180 µg/m2/day or 5,400 µg/m2 month, meaning that the Australian Standard for outdoor lead dust of 8000 µg/m2 (Standards Australia, 1998) would be exceeded, on average, every 44.4 days. Our study shows that the deposition of lead and other metals is not limited to the Coast Guard site, but depositions blanket large parts of the inner city, including the most important tourist area, known as The Strand, along Townsville city’s waterfront. While this study does not examine aerosol metal concentrations (expressed as µg/m3), it is noted that these are well described and detailed in recent reports (Queensland Government, 2010; 2014). Specific understanding of the concentrations of aerosol metals in particulate matter less than 10 microns (PM10) in the Queensland Government (2010) report was not possible because the field sample method used only allowed for analysis of metals in total suspended particulates (TSP). The field sample method and sensitivity of the laboratory analytical technique was most problematic with respect to nickel aerosol concentrations because, unlike the other metals analysed, the 12month average TSP values at the Coast Guard and North Ward (Figure 1) monitoring sites were greater than Queensland’s Environmental Protection (Air) Policy 2008 (EPP (Air)) PM10 objective for nickel of 20 ng/m3 (Queensland Government, 2010). 17 With respect to lead dust deposition rates, the Queensland Government (2010) study showed that the monitoring sites of Coast Guard and North Ward in the months of September to December returned the four highest values over the study period (maximum of 839 µg/m2/day at Coast Guard, October 2009 and a maximum at North Ward of 233 µg/m2/day (October 2008) at the North Ward site, see Figure 1 for site locations). The Coast Guard lead dust deposition values for 2008-2009 are not dissimilar to those reported in the most recent North Queensland Air Bulletin (Queensland Government, 2014). However, it is worth noting that for the North Ward site, the data show that between July 2013 and June 2014 values were below the limit of reporting obtainable from the sampling equipment and laboratory method used by Queensland Government (2014). The data reported in the Queensland Government (2010, their Figure 34; Table 18) study show quite clearly that lead dust deposition increases at the Coast Guard and North Ward sites when the predominant wind direction is from north-east or east, the general direction of the Port. The same relationship between prevailing wind direction from the Port and a range of metal aerosol concentrations (µg/m3) is also evident, in particular with respect to this study: arsenic, cadmium and lead, but not nickel (see below for discussion). These factors point to a common source of dust metals measured in previous studies and also in this study. The relationship between surface dust metal loadings and those recovered from post-play hand wipes was also undertaken. Our data returned positive and significant relationships (Pearson Correlation Coefficient, p = <0.05) for arsenic, cadmium and lead, but not for nickel (p = 0.7185), indicating the importance of atmospheric dust deposition for contaminating playgrounds. These findings corresponded to those reported in the Townville Dust Monitoring program (2008-2009), (Queensland Government, 2010), which focused largely on aerosols as opposed to dust metal deposition, with the exception of lead. It is likely that similar dust deposition loadings will also be impacting neighbouring residential and commercial environments. The absence of a relationship between surface nickel dust deposition and that in post-play hand wipe values is not readily explained, though it is worth noting that the Townville Dust Monitoring program (Queensland Government, 2010) showed that there was no relationship between the proportion of winds coming from the Port and TSP nickel air values recorded across Townsville. This suggests that nickel deposition is more complicated than the other dust metals and may be influenced by different processes and sources, possibly including the fact that ore is moved out of Townsville to the Yabulu smelter in open rail wagons. Although nickel is enriched in regional soils (e.g. Greenvale Nickel Mine), soil samples collected in this study returned low concentrations with 18 a mean of 31 mg/kg nickel (Supplementary Table S1). The loss of metalliferous minerals from rail wagons is not well established in the peer-reviewed literature but two Australian studies show that significant amounts of lead and zinc concentrate were lost from uncovered rail wagons moving ore from Broken Hill to Port Pirie (Body, 1996; Kristensen et al., in review). In 1996, after a series of complaints, the New South Wales Environment Protection Authority ordered that the rail ore wagons were to be covered to prevent ore dust from being blown into the surrounding environment. In 1997, fiberglass covers were introduced for ore wagons carrying lead and zinc ores to eliminate product loss and reduce the environmental risk of ore wagon dust emissions (Kristensen et al., in review). 4.2 Lead Isotopic Fingerprinting of Dust Wipe Samples The lead isotopic composition analysis conducted as part of this study provides strong evidence that the dust lead is derived predominantly from operations at the Port (Figure 6). The dust collected in the Day 5 post-play wipes (Figure 6) are most similar in composition to the various Mount Isa type ores that are shipped out as concentrate from the Port. Of the four wipes collected on the final day of play, the sample most different from the Mount Isa type ores is that from Soroptimist Park, which returned 208 Pb/207Pb and 206 Pb/207Pb ratios of 2.3567 and 1.0776. This suggests Soroptimist Park is less impacted by lead sourced from the Port operations, a fact that is mirrored by the total post-play hand lead loading values, which are the lowest in the study (Supplementary Tables S2S5). 4.3 Blood Lead and Exposure Risks from Metal-Contaminated Dust Deposition Queensland Health (Queensland Government, 2010) undertook blood lead modelling estimates arising from dust lead loading values recorded in Townsville during the period March 2008 to December 2009. The returned estimates of blood lead levels ranged between 1 and 3 µg/100 mL (commonly expressed as µg/dL [decilitre] i.e. 1 and 3 µg/dL), which was well below the then National Health and Medical Research Council (NHMRC, 2009) blood lead goal for all Australians of 10 µg/dL. Since that time, the NHMRC has been recommended that the blood lead level for intervention and investigation level should be lowered to 5 µg/dL (NHMRC, 2014). Queensland Health (2014) responded to the NHMRC (2014) review of blood lead levels by recommending in July 2014 that the blood lead notification level for Queensland be lowered to 5 µg/dL. The Queensland Health (Queensland Government, 2010) modelling relied on the former World Health Organization Provisional Tolerable Weekly Intake (PTWI) for lead of 25 µg/kg body weight/week. This value has now been withdrawn because “it was not possible to establish a new PTWI that would be health protective” (WHO, 2010). Similarly, the PTWI for cadmium was also effectively 19 adjusted downward from a PTWI of 7 µg/kg body weight/week to a Provisional Tolerable Monthly Intake value of 25 µg/kg body weight/month. This equates to an 18 % reduction in acceptable exposure levels for cadmium. In light of the shift to a new, lower intervention level for blood lead along with the Townsville dust metal data reported herein and elsewhere, it would be prudent for the relevant stakeholders to revisit dust control protocols associated with the import and export of minerals from the Port of Townsville. Given the potential risk of exposure to children’s health identified in the present study, coupled to the near universal acceptance that there is no safe exposure limit for lead, it would be prudent to consider strategies to mitigate any risks. Treating the source of the emissions would represent the best outcome (primary prevention). In the interim, additional and improved frequency of playground cleaning along with covering play equipment where this is not already the case (e.g. Reid Park) should be instigated until measures to lower dust metal deposition rates to acceptable levels are achieved. Signs encouraging hand-washing after play, along with regular cleaning of contaminated playgrounds, occurs at Port Pirie in order to reduce exposure hazards (Port Pirie Regional Council, 2013). However, Taylor and co-workers have demonstrated in unpublished data, that significant re-contamination of playground surfaces occurs within 24 hours of washing. This indicates that limiting source emissions is crucial to reducing permanently dust metal hazards. Washing should not be considered a long-term solution to the problem of daily dust contamination because the dust found at the playgrounds will also be affecting neighbouring residences, schools and kindergartens and commercial properties. Therefore, a more sustainable mitigation strategy in the longer-term would need to review and address directly the source(s) of contamination from the Port and losses associated with the movement and transport of nickel ore in uncovered rail wagons. 5. CONCLUSIONS The environmental evidence presented in this report indicates that: 1. Elevated loadings of arsenic, cadmium, nickel and lead is found in surface dusts and on hands after using public playgrounds in Townsville’s inner city area. 2. The similarity of the lead isotope composition of dust wipes to those of Mount Isa type ores confirms that the Port is the most likely source of surface dust contamination. There are two likely primary sources of nickel – the open air unloading of ore and its transport in uncovered rail wagons to Queensland Nickel at Yabulu, 25 km north-west of Townsville city. Regional soil contributions to dust metals also need to be evaluated to exclude this as a possible other source. 20 3. Deposition of atmospheric metal-rich dust containing arsenic, cadmium, lead and nickel is ongoing and re-contamination to unacceptable levels occurs daily. 4. The amount of metal-contaminated dust identified on surfaces close to children’s play areas and also on hands after play on four Townsville playgrounds sampled in this study frequently exceeds State trigger values and international benchmarks for metal dust loadings. 5. At all playgrounds, at least once during the study, hand lead loading values exceeded the Government Western Australia’s (2011) clean-up value for lead (400 µg/m2) on surfaces accessible to children. 6. Although playgrounds were used to measure environmental dust-metal exposures, similar dust metal hazards are likely to be occurring concurrently in neighbouring properties. Consequently, clean-up of the dust in playgrounds will not protect all children because contaminated dust deposition will be impacting areas beyond the study sites examined in this study. In the interests of public health, it is recommended that action should be taken as soon as possible to mitigate against the immediate risk. Subsequent efforts need to focus on identifying point and diffuse sources of re-contamination in order to eliminate or reduce significantly metal-rich dust emissions and subsequent depositions. 6. RECOMMENDATIONS 1. The cause contamination at the Port must be identified, significantly reduced and preferably eliminated. 2. Effective treatments are likely to also involve covering the trains transporting ore to Queensland Nickel, fully enclosing loading and unloading operations and/or checking the effectiveness of existing dust cover and mitigation programs. 3. In the interim, daily washing of playgrounds may help reduce metal loading and the risk of exposure from playground use. The provision of hand-washing facilities (including soap) along with appropriate signage would also be advantageous in encouraging adults and children to wash hands after playground use. 4. All playgrounds should be washed on a more regular basis to reduce the immediate risk to children’s health. The focus should be on playgrounds that are closest to and most exposed to wind blowing from the direction of the Port. 5. The effectiveness of any remedial treatments should be evaluated for the efficacy. 21 6. The community should be kept informed of mitigation measures taken and subsequent contamination measures. 7. ACKNOWLEDGEMENTS M.P. Taylor would like to thank the North Queensland Conservation Council for funding the dust wipe analysis costs and for travel to present the findings of the study to stakeholders on the 4th December 2014. M.P. Taylor also acknowledges funding support from the Department of Environment and Geography, Macquarie University, for fieldwork travel costs in September 2014. Macquarie University’s PACE (Professional and Community Engagement) program is thanked for travel support to Ali Maadh, Audrey Quicke, Emilia Rupsys and Paris Spellson, who undertook the majority of the field sampling. 8. REFERENCES Agency for Toxic Substances and Disease Registry (ATSDR). 2011. Toxic Disease Portal. Nickel. http://www.atsdr.cdc.gov/substances/toxsubstance.asp?toxid=44 (accessed 3rd December, 2014). American Society for Testing and Materials, 2003. ASTM E 1728-10 Standard Practice for Collection of Settled Dust Samples Using Wipe Sampling Methods for Subsequent Lead Determination. 4, http://www.astm.org/Standards/E1728.htm (accessed 3rd December, 2014). Body, P. E. 1986. Port Pirie Lead Project Railway Lane Survey: Port Pirie to Broken Hill. South Australia Department of Environment and Planning Report No. 80. 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Joint FAO/WHO Expert Committee on Food Additives, Geneva, Switzerland. http://www.who.int/foodsafety/publications/chem/summary73.pdf (accessed 3rd December, 2014). 25 Supplementary Tables S1-S5 Sample name TVD_14_S_D2_S1 TVD_14_S_D2_S1_C TVD_14_S_D2_S1_D TVD_14_S_D2_S2_C TVD_14_S_D2_S2_D TVD_14_S_D2_S3 TVD_14_S_D2_S3_C TVD_14_S_D2_S3_D TVD_14_S_D2_S4 TVD_14_S_D2_S4_C TVD_14_S_D2_S4_D TVD_14_S_D3_S5_C TVD_14_S_D2_S5_D TVD_14_S_D2_S6_C TVD_14_S_D2_S6_D Location Zn (mg/kg) ± Pb (mg/kg) 15.6 2 12.9 Sister Kenny Park (3 Soil Samples) 97 3 60 75 3 35.9 89 3 43.3 124 3 36.9 Headland Park (2 Soil Samples) 14.4 2 5.1 137 4 45 136 4 48.8 Soroptimist Park (3 Soil Samples) 13 2 9.2 152 4 31.5 101 3 32.7 Reid Park (3 Soil Samples) 148 4 42.6 273 5 98 Queens Park Oval (2 Soil Samples) 456 6 126 3459 20 1294 Anzacc Memorial Park (2 Soil Samples) ± Ni (mg/kg) 1.4 32 2 32 1.7 20 1.8 29 1.7 1.1 1.9 26 2 15 1.2 34 1.6 1.7 24 1.8 16 2 19 3 9 95 ± 4 4 4 4 4 4 4 4 4 4 5 Cu (mg/kg) ± 16 21 18 25 7 11 20 2 3 2 3 2 2 3 28 24 12 41 76 440 3 3 2 3 3 7 Cr (mg/kg) 16 ± 4 As (mg/kg) ± 25.8 34.5 9.2 37.4 Cd (mg/kg) ± 2 2 1 2 Location Sister Kenny Park (3 Soil Samples) Headland Park (2 Soil Samples) Soroptimist Park (3 Soil Samples) 27 4 Reid Park (3 Soil Samples) Queens Park Oval (2 Soil Samples) 59 4 6.3 43 2 6 19 5 Anzacc Memorial Park (2 Soil Samples) Table S1. Soil analysis results from playground and surface wipe sample sites. The value in bold and underlined indicates value about Australian guideline for open space, 600 mg/kg (NEPM, 2013). Where samples have the notation (gravel), this indicates that the sample consisted predominantly of fine gravel with little organic matter present. 26 Sister Kenny Park Day 1 Day 2 Day 3 Day 4 Day 5 Mean Std Devn n Day 1 Day 2 Day 3 Day 4 Day 5 Mean Std Devn n Day 1 Day 2 Day 3 Day 4 Day 5 Pre-play hand wipe metal loadings Arsenic Cadmium Lead µg/m 2 µg/m 2 µg/m 2 0.00 0.00 0.00 0.00 0.00 31.06 0.00 2.11 34.16 0.00 0.00 49.69 0.00 0.00 37.27 0.00 0.42 30.43 0.00 0.84 16.48 5 5 5 Post-play hand wipes 0.00 3.11 40.37 34.16 29.81 2204.97 15.84 16.77 869.57 17.08 17.70 652.17 18.63 18.63 1055.90 17.14 17.20 964.60 12.12 9.49 791.78 5 5 5 2 Post-play increase (µg/m ) 0.00 3.11 40.37 34.16 29.81 2173.91 15.84 14.66 835.40 17.08 17.70 602.48 18.63 18.63 1018.63 Nickel µg/m 2 0.00 37.27 34.16 43.48 55.90 34.16 18.63 5 86.96 403.73 208.07 170.81 341.61 242.24 128.78 5 86.96 366.46 173.91 127.33 285.71 Table S2. Data showing pre- and post-play hand metal loadings for Sister Kenny Park. 27 Headland Park Day 1 Day 2 Day 3 Day 4 Day 5 Mean Std Devn n Day 1 Day 2 Day 3 Day 4 Day 5 Mean Std Devn n Day 1 Day 2 Day 3 Day 4 Day 5 Pre-play hand wipe metal loadings Arsenic Cadmium Lead µg/m 2 µg/m 2 µg/m 2 5.59 10.56 152.17 8.07 9.01 229.81 4.97 3.73 74.53 4.04 4.04 68.32 3.42 4.04 108.70 5.22 6.27 126.71 1.61 2.91 59.56 5 5 5 Post-play hand wipes 10.56 16.15 304.35 14.91 24.22 559.01 26.71 26.71 1149.07 18.01 29.19 496.89 9.32 30.75 714.29 15.90 25.40 644.72 6.97 5.74 317.91 5 5 5 2 Post-play increase (µg/m ) 4.97 5.59 152.17 6.83 15.22 329.19 21.74 22.98 1074.53 13.98 25.16 428.57 5.90 26.71 605.59 Nickel µg/m 2 105.59 74.53 37.27 52.80 65.22 67.08 22.96 5 93.17 167.70 236.02 133.54 99.38 145.96 58.51 5 -12.42 93.17 198.76 80.75 34.16 Table S3. Data showing pre- and post-play hand metal loadings for Headland Park. 28 Soroptimist Park Day 1 Day 2 Day 3 Day 4 Day 5 Mean Std Devn n Day 1 Day 2 Day 3 Day 4 Day 5 Mean Std Devn n Day 1 Day 2 Day 3 Day 4 Day 5 Pre-play hand wipe metal loadings Arsenic Cadmium Lead µg/m 2 µg/m 2 µg/m 2 3.42 7.45 99.38 5.28 8.07 130.43 4.35 5.28 167.70 4.04 4.97 80.75 0.00 9.01 136.65 3.42 6.96 122.98 1.81 1.58 30.28 5 5 5 Post-play hand wipes 25.47 9.32 403.73 13.98 7.45 248.45 11.80 5.90 251.55 13.35 6.21 236.02 8.70 7.45 204.97 14.66 7.27 268.94 6.38 1.35 77.57 5 5 5 2 Post-play increase (µg/m ) 22.05 1.86 304.35 8.70 -0.62 118.01 7.45 0.62 83.85 9.32 1.24 155.28 8.70 -1.55 68.32 Nickel µg/m 2 68.32 55.90 52.80 40.37 49.69 53.42 9.09 5 121.12 77.64 74.53 80.75 77.64 86.34 19.57 5 52.80 21.74 21.74 40.37 27.95 Table S4. Data showing pre- and post-play hand metal loadings for Soroptimist Park. 29 Reid Park Day 1 Day 2 Day 3 Day 4 Day 5 Mean Std Devn n Day 1 Day 2 Day 3 Day 4 Day 5 Mean Std Devn n Day 1 Day 2 Day 3 Day 4 Day 5 Pre-play hand wipe metal loadings Arsenic Cadmium Lead µg/m 2 µg/m 2 µg/m 2 3.42 3.73 93.17 5.28 6.83 121.12 4.04 3.73 130.43 4.97 2.70 52.80 11.80 5.59 102.48 5.90 4.52 100.00 3.02 1.49 27.03 5 5 5 Post-play hand wipes 29.19 46.58 869.57 43.48 68.32 2795.03 30.75 30.75 1366.46 34.16 46.58 1863.35 28.88 62.11 3012.42 33.29 50.87 1981.37 6.07 14.77 915.60 5 5 5 2 Post-play increase (µg/m ) 25.78 42.86 776.40 38.20 61.49 2673.91 26.71 27.02 1236.02 29.19 43.88 1810.56 17.08 56.52 2909.94 Nickel µg/m 2 46.58 55.90 59.01 37.27 52.80 50.31 7.71 5 121.12 208.07 341.61 263.98 186.34 224.22 83.20 5 74.53 152.17 282.61 226.71 133.54 Table S5. Data showing pre- and post-play hand metal loadings for Reid Park. 30
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