PHYTOTOJX,IC; CD ('34Y 43` INTHE VICINITY VVEL.1_AND SARNIA ON AI GLYWIDIF -2 3f l l' 89 FEBRUARY' V60019-1 NI r o n rri rv ,( A. wr e ritt ri ef in n,,in _, rr ru r91 pool Ontario Copyright Provisions and Restrictions on Copying: This Ontario Ministry of the Environment work is protected by Crown copyright (unless otherwise indicated), which is held by the Queen's Printer for Ontario. It may be reproduced for non-commercial purposes if credit is given and Crown copyright is acknowledged. It may not be reproduced, in all or in part, for any commercial purpose except under a licence from the Queen's Printer for Ontario. For information on reproducing Government of Ontario works, please contact ServiceOntario Publications at copyright aontario.ca ISBN 0-7729-7892-1 PHYTOTOXICOLOGY SECTION INVESTIGATION IN THE VICINITY OF WELLAND CHEMICAL, SARNIA ON AUGUST 23, 1989 Report prepared by: Phytotoxicology Section Air Resources Branch Ontario Ministry of the Environment FEBRUARY 1991 0 RECYCLMU Cette publication technique nest disponible qu'en anglais Copyright: Queen's Printer for Ontario, 1991 This publication may be reproduced for non-commercial purposes with appropriate attribution 90-2231-015 PISS 1434 ar /?s / P5-'s qt' 1 Background 1 Welland Chemical, Scott Road, Sarnia is a manufacturer of anhydrous aluminum chloride. The product is manufactured by passing gaseous chlorine through molten aluminum and precipitating out the resulting product. During the removal of the product from the precipitators and in the subsequent handling and packaging there are fugitive emissions of the product. The 0 product reacts with the moisture in the air to produce hydrochloric acid and aluminum oxide. Complaints of damage to vegetation in the immediate vicinity of the company have been observed since 1970. The Phytotoxicology Section, Ministry of Environment has carried out assessment surveys around Welland Chemical Ltd. since 1970 (1). Annual surveys were carried out continuously from 1978 to 1987 (2,3,4,5,6,7,8). In all of the investigations to date there has been documented injury to vegetation in the vicinity of Welland Chemical. This injury has been attributed to emissions from the company. The injury, which usually develops in late July, is typical of chloride injury. Chemical analysis has revealed significantly elevated levels of aluminum and chlorine in the vegetation around Welland Chemical. On August 23, 1989 Mr. R.D. Jones of the Phytotoxicology Section conducted a Phytotoxicology investigation in the vicinity of Welland Chemical. This is a report of the results of that investigation. 2 Methods Duplicate bur oak (Quercus macrocarpa) foliage samples were collected at eleven stations within 750 meters of Welland Chemical. The sampling stations were the same as those that have been sampled annually since 1978 (see Figure 1). The samples were collected using standard Phytotoxicology sampling techniques (3). All samples were delivered to the Phytotoxicology Section sample processing laboratory in Toronto where they were dried and ground before being submitted to the Inorganic Trace Contaminants Section, Laboratory Services Branch for chemical analysis. The samples were analysed for aluminum, cadmium, chlorine, chromium, cobalt, copper, iron, lead, manganese, molybdenum, nickel, sodium, strontium, vanadium and zinc. At each collection site, in addition to sampling for chemical analysis, numerous indigenous plant species were examined for air pollution injury. These species included: bur oak, basswood, hawthorn, elm and white ash. 1 ARB-015-90-PHYTO Figure 1: Map of the Vicinity of Welland Chemical Limited Showing the Location of 11 Vegetation Collection and Observation Sites, August 23, 1989. Churchill Rood i i i B I i 5 IN. i j Ontario Hydra Welland I Chemical i j Limited 2 i 1 r 9 8 = a 10 r+ c Approilmst Semite (materel 1 0 100 700 300 400 121 3 Results Trace to moderate injury was observed on basswood, oak, hawthorn, sumac and elm at station one. This injury was greatest at the edge of the road and dropped off rapidly east of the road. There was trace injury on oak at station four and trace to light injury on oak and basswood at station seven. All of the observed injury was typical chloride-type injury. There was no injury at any of the other sampling stations. The injury was similar to that observed in 1987. The results for chloride analysis for 1982 to 1987 and 1989 are given in Table 1. The results for aluminum, cadmium, chromium, cobalt, copper, iron, lead, manganese, molybdenum, nickel, sodium, strontium, vanadium and zinc analysis for 1989 are given in Tables 2 and 3. The results are expressed as either % or µg/g dry weight and are the mean of the duplicate samples collected at each site. All results were spatially evaluated using a mapping program called Surfer ver. 3.00 (Golden Software, Inc.) to determine if there was any pattern of declining levels with distance from the company. The distribution patterns for chloride, aluminum, sodium and molybdenum are given in Figures 2,3,4 and 5. Table 1: Results of Analysis for Chlorine in Bur Oak Foliage Collected in the Vicinity of Welland Chemical, Sarnia (% dry weight). Sampling 1982 1983 1984 1985 1986 1987 1989 r Site 1 1.18 033 038 031 0.61 036 039 2 0.11 0.08 0.08 0.10 0.13 0.07 0.06 4 OA2 039 0.23 037 034 0.53 0.22 5 036 032 0.18 0.23 0.24 0.28 0.18 6 0.09 0.10 0.11 0.12 0.15 0.17 0.04 7 0.82 0.49 0.23 034 0.25 0.52 032 8 0.06 0.05 0.07 0.04 0.06 0.08 0.05 9 0.07 0.02 0.05 0.05 0.05 0.04 0.01 10 0.60 0.27 0.27 OA3 0.73 030 0.19 11 031 0.19 0.20 0.26 0.19 0.14 0.18 12 0.24 0.13 0.13 0.09 0.12 0.11 0.17. Mean of Sites 1.4,7&10 0.76 037 0.28 036 036 0.43 0.28 Rural 0.15 0.15 0.15 0.15 0.15 0.15 0.15 ULN Table 2: Results of Analysis for Aluminum, Cadmium, Chromium, Cobalt, Copper, Iron and Lead in Bur Oak Foliage Collected in the Vicinity of Welland Chemical, Sarnia 1989 (expressed as µglg dry weight). Smnpling Site Aluminum Cadmium Chromium Cobalt Copper Iron Lead 1 120 <0.1 0.7 03 5.2 114 1.1 2 37 <0.1 0.5 0.4 4.6 80 <03 4 65 <0.1 0.6 <0.2 6.2 110 0.9 5 58 <0.1 0.5 <0.2 5.7 98 1.0 6 25 <0.1 <03 <02 5.6 76 0.7 7 99 <0.1 0.8 03 6.2 195 0.8 8 31 <0.1 0.5 <0.2 63 120 0.6 9 30 <0.1 0.6 03 5.8 99 <0.5 10 170 <0.1 0.7 <0.2 5.0 101 0.8 11 105 <0.1 0.8 <0.2 52 110 13 12 54 <0.1 0.8 01 4.9 90 0.5 Rural 500 1 8 2 20 500 30 ULN 3- An-015-WP1iM Table 3: Results of Analysis for Manganese, Molybdenum, Nickel, Sodium, Strontium, Vanadium and Zinc in Bur Oak Foliage Collected in the Vicinity of Welland Chemical, Samia 1989 (µg/g dry weight). Sampling Site Manganese Molybdenum Nickel Sodium Strontium Vanadium Zinc 1 51 1.7 09 112 12 0.9 22 11 2 77 1.3 0.8 18 10 <0.5 14 4 46 1.0 0.9 49 21 <0.50 21 5 36 1.1 0.8 39 10 0.7 37 6 27 0.9 <0.6 13 2.7 <0.5 19 7 58 13 0.8 79 15 0.8 23 8 67 1.0 <0.6 29 13 <0.5 18 9 86 0.6 <0.6 44 11 <0.5 18 10 73 2.2 <0.6 66 9 0.5 27 11 23 1.1 <0.6 280 13 0.7 18 12 45 0.9 <0.6 115 15 0.6 16 Rural 1.5 5 50 5 250 ULN Figure 2: Distribution of Chloride in Bur Oak. 1989 Figure 3: Distribution of Aluminum in Bur Oak, 1989 4- ARB-015.90-PHYTO Figure 4: Distribution of Sodium in Bur Oak, 1989 Figure 5: Distribudon of Molybdenum in Bur Oak. 1989 t 4 Discussion Typical chloride injury has been observed on foliage of sensitive plant species near the company in all years in which this survey has been conducted. Until 1982 extensive chloride injury was observed on foliage in an area up to 250 meters from the company. Since 1982, significantly less injury has been observed on sensitive plant species with injury being limited to Sites 1,4,7 and 10 (within 100 meters of the company's perimeter). Significant regeneration of less sensitive plant species, typically weed species, has been observed at Site 1. There was no injury at Site 10 in 1989. This was considered due in part, however, to the death of chloride sensitive bur oaks in the immediate vicinity of that site in 1986. The death of these trees also necessitated a change in the oak tree sampled for chemical analysis. As noted in the 1986 and 1987 reports (7,8), significant declines in both leaf injury and foliar chloride concentrations were observed between the 1982 and 1983 growing seasons. With the exception of a small increase in chloride concentration at Sites 1,4,7 and 10 in 1987 there has been relatively little change in both parameters since that time. While the levels of chloride in bur oak are low with respect to pre-1983 levels, there were exceedances of the Rural Upper Limit of Normal for chloride at six sites around the company in 1989. 5- ARB-015-90-PHYT0 Aluminum levels in bur oak have followed the pattern for chloride. Levels dropped significantly after 1982, remained constant from 1983 to 1986, rose in 1987 and were back to 1983 levels in 1989. Although there was a pattern of declining aluminum concentration with distance from the company, all values in 1989 were well below the Rural Upper Limit of Normal for aluminum in tree foliage. Sodium results for the 1989 vegetation collection were in the same range as the results from h 1982 to 1987. Although uptake of sodium as sodium chloride from the roadside ditch continues to result in obvious contamination of foliage at Site 11, the amount taken up was not high enough to influence the interpretation of the chloride results at this site, vis-a-vis Welland Chemical. This uptake from the ditch can be readily seen in the distribution of sodium in bur oak foliage as shown in Figure 4. Twelve of the other thirteen elements analysed for were well below the Rural Upper Limit of Normal for each element. For these twelve (cadmium, chromium, cobalt, copper, iron, lead, manganese, nickel, sodium, strontium, vanadium and zinc) there was no pattern of declining concentration with distance from the company. There was a weak pattern of declining concentration with distance from the company for molybdenum (see Figure 5). While the levels of molybdenum were very low (09 to 2.2 ppm), the Upper Limit of Normal was exceeded at sampling sites and 1 10. 6- AR.B-015-WPHYTO