PHYTOTOXICOLOGY BACKGROUND SAMPLING IN THE CITY OF WINDSOR: 1972- 1986 MARCH 1990 Environment Environnement OntSriO Jim BrdcHtiy, Minislef/minislre ISBN 0-7729-5350-3 PHYTOTOXICOLOGY BACKGROUND SAMPLING IN THE CITY OF WINDSOR: 1972-1986 Report prepared by: R. G. Pearson Phytotoxicology Section Air Resources Branch ARB-120-87-Phyto MARCH 1990 Q Copyright: Queen's Printer for Ontario, 1990 This publication may be reproduced for non-commercial purposes with appropriate attribution. Phytotoxicology Background Sampling in the City of Windsor: 1972-1986 Phytotoxicology Section Air Resotirces Branch In an effort to ascertain background concentrations of inorganics in soils and vegetation throughout the Windsor urban complex and to examine the data for any directional and spatial trends, a full examination of all Phytotoxicology investigations conducted during the period from 1972 - 1986 has been undertaken. These data will serve as a background for site selection and trend analysis in future assessment studies in Ontario that are planned to commence in 1989, following the start-up of the Detroit Incinerator. This compilation was accomplished by reviewing all historical Phytotoxicology Section investigation files for external requests (complaints from property owners) and assessment surveys (collections around stationary sources and city-wide sampling surveys) in the Windsor area. In total, 32 separate investigation files were utilized consisting of sampling in all except two (1974, 1982) of the 15-year time interval. The data totals are as follows: Sample No. Different Total Analyses Medium Elements Analyzed Utilized Soil 18 2375 Vegetation 18 3197 TOTAL 18 5572 - 2 - Because of the confidential nature of external request investigations (public complaints), all files were given an identification number and all sampling data pertaining to the various private and/or municipal property sampling sites were assigned a N-S and E-W grid co-ordinate (see attached Fig. 1) . The separated data sets for soil and vegetation are presented in Appendices 1 and 2, respectively. Data for the two sampling media also were examined for the number of individual exceedances of the respective Upper Limits of Normal (ULN) guidelines as established by the Phytotoxicology Section. The totals are shown on the last page of each of the two appendices. The complete listing of the ULN guidelines for soil and vegetation as well as their rationale are presented separately as Appendix 3. In an effort to identify directional trends in the analytical results, the data in Appendices 1 and 2 were positioned into N-S and E-W gradients to permit an assessment of overall directional trends. The results of this partitioning are shown in the following summary tcibles : Table 1 Soil N-S Trends Table 2 Soil E-W Trends Table 3 Vegetation N-S Trends Table 4 Vegetation E-W Trends As a final step, the data in Appendices 1 and 2 were further partitioned into individual elemental grid means (Appendices 5 and 6) to enable a full spatial analysis of the data set. Discussion A. No. of Samples Exceeding the Respective ULN The number of exceedances of the ULN for both soils and vegetation are summarized in attached Table 5. It is apparent from this comparison that in the case of both soil and vegetation, almost one-half of the elements which have been analyzed have yielded one or more analytical results in excess of the respective Upper Limits of Normal guidelines for an urban area. In the case of those elements displaying exceedances, the percentage of the total data for each element which was comprised of values in excess of the respective ULN ranged from 0.7% - 19.8% for soil and from 0.6% - 33.9% for vegetation (Table 5). Although most of the exceedances were related to contamination by known sources, the -soil Mo values remain an anomaly. This will be examined in greater detail in future surveys. B. Directional Trend Analysis An examination of Tables 1-4 for evidence of a clearly defined N-S or E-W gradient in the soils and vegetation data has revealed that this type of pattern does not exist. There were a limited number of cases where a significant difference was detected in one or more of the N-S or E-W averages based on standard deviation values; however, these differences are, in all likelihood, due to differences in species analyzed or proximity to local contamination sources. In a further attempt to display the data in a spatial context a more rigorous evaluation of the data on a grid by grid basis was performed. In order to eliminate some of the variability in the vegetation data the analyses result* included in this evaluation were limited to maple species. A complete summary of - 4 - the soil and maple grid means (with standard deviation and number of samples) is shown in Appendices 5 and b, respectively. To assist in visually assessing the grid means, the data for all elements in which a mean for at least 10 grids was available have been shown in the following grid maps: Soil grid means: Figures 2-13 Maple grid means: Figures 14-27 This type of city-wide data analysis to identify spatial trends also was performed in one of the specific assessment surveys which was included in the 1972-1986 data set. The findings of that assessment survey (Appendix 4) revealed that three general sources of contamination had influenced concentrations of fluoride, chloride, sulphur and certain heavy metals (iron, lead, cadmium and zinc) in soils and/or vegetation foliage in the west Windsor area. 1. The industrialized areas of south Detroit, particularly surrounding Zug Island, Michigan. 2. The industrialized areas of west amd central Windsor. 3. Vehicular activity in the general area. Contours of contamination for the various elements also were presented and are shown in Appendix 4. In order to compare the findings of the more encompassing data set for 1972-1986 with the trends identified earlier in the more limited assessment - 5 - survey of 1975-79 (Appendix 4) a summary table was prepared and is attached (Table 6). An evaluation of this trend analysis summary for the 1972-1986 grid means can be further summarized as follows : 1. Although not necessarily all statistically significant, evidence of spatial trends similar to those reported in Appendix 4 were apparent for 10 soil and 8 maple elemental grid means. 2. A more limited N-S or E-W trend also was apparent for 1 additional soil and 2 additional maple elemental grid meams . 3. In comparing the elemental grid means with corresponding single sample Upper Limits of Normal guidelines for elements with at least 10 available grid means it was found that 2 (As, Mo) of the soil and 3 (Cu, F, Pb) of the maple elemental grid means were in excess of the corresponding U.L.N. guidelines . C. Comparison of MOE Data with other Published Results While no directly comparaible findings for the Phytotoxicology data base have been located, there is one report which presents the analysis of soils and vegetation in the Windsor area for lead and cadmium (1). In that report, the authors found significantly higher levels of both lead and cadmium in soil and vegetation collected in the Windsor area than in corresponding Essex County (rural) samples. With the exception of root lead concentrations, the elevated urban levels were significantly correlated with traffic volume. Unfortunately, the soils data are not - 6 - directly comparable with those reported by the Phytotoxicology Section due to differences in analytical technique. A direct comparison of the vegetation data also is not possible as only root tissue results were reported for the Windsor sites. Summary A complete Phytotoxicology Section data listing for all samples collected during soils and vegetation complaint and assessment survey investigations in the City of Windsor during the 15-year period 1972 - 1986 is presented. The data have been compared with current 'Upper Limits of Normal' guidelines established by the Phytotoxicology Section and also have been keyed into a grid system for examination of N-S and E-W trends as well as individual grid mean spatial trends. The results of these comparisons confirm that soils and vegetation in the Windsor area are for the most part, fairly representative of a large urban complex. However, a noticeably large number of individual samples and area grid means were found to have exceeded the established Upper Limits of Normal for an urban area. From a spatial aspect, the large degree of variability in the data base caused by the collection of samples over a 15-year period amd without any commonality in species selection precluded any definitive conclusions being made as to N-S or E-W directional trends. However, when the data were further reduced to individual grid means for maple and soil only, spatial trends similar to those reported in the 1975-79 West Windsor assessment survey were apparent for the majority of the elemental grid means. These findings confirm the influence of three general contamination sources on soils and vegetation in the Windsor area: - 7 - 1. The industrialized areas of South and Central Detrcil particularly those in the vicinity of Zug Island, Michigan. 2. The industrialized areas of West and Central Windsor 3. Vehicular activity in the general urban complex. Reference Cited 1. Great Lakes Institute, University of Windsor. 1986. A Case Study of Selected Toxic Contaminants in the Essex Region. Vol. I, Physical Sciences, Part Two. Task Group Vlllb - Terrestrial Biology, pp.41. RE876 ,? !s a si" si" s a ac o^ SB ac *J O (M ^ o § .1 ^ 9 ^ s := 9 :: 9 ^ 9 :: 9 s 9 :: 9 ^4* CI a> a at *-n 3K 3C o o 9 04* A •» t-TlA* fTtt* tT^ *t tJHH *Z ».^« »^« .^!w B l.f I5 1^ IJ^ i.5 ii^ iJ^ 15 ii^ (I t^t an »4k^ t^jt^ »^t.i ti».t •^(.j k4*4 *4»4 O a>*Jo a*»->o 4**'0 tw«^o «>*«o •w»'o <***>o «**'0 <«•««> -~' a:o)HK a:t^Mi a:*-'!** s:t>-iBi »:o>mi BZi/iM* kwihi kuimi k^. !■> a s I E-.-J- — - " -. ^ ^ . » Table 5: Sumnary of ULN Exceedences for Soil and Vegetation Collected in Windsor: 1972-1986 MediuB No. of Elements Elements No. X of Analyses Analyzed Exceeding ULN Guideline Ezceed^nces Exceeding ULN Soil 18 As 4 4.2 Cd 4 1.3 Cr 1 0.7 Fe 7 2.4 Mn 1 4.8 Mo 22 19.8 Pb 7 2.4 Vegetation 18 Cr • 1 0,6 Cu 6 3.9 F 47 19.0 Fe 10 3.0 Mo 3 2.2 Na 20 33.9 Pb 3 0.9 S 4 1.4 V 2 1.2 4J Elements in 1972-86 Grid Mean Data Set Which Display a Limited N-S or E-W Spacial Pattern o 3 o t. 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"-- ^ < ■ u o •• Ik a I APPENDICIES 1-6 »— >- 5S — • cs C3t!3t3C3c:iOQQC*c»*r5c»C»c»ca*r>irs<::»fc-»."».^ c_^ t_j c_^ cz» ca Q Cl a Q C^ C5 C_> t_J C_> oQ CO OQ OQ CO en C_J t_> f_» m rr» r~» (=1 Q c^ CJ t_J t_i t_i i»j c^ *-* 1^ *-■* t_*t^e_jc_j<^c_jCiQ C_J C_> t_J crj C5 CJ f*» (^ CI ir» c-» t_» l_J *_» (Ti t*> c»jbJC!3C3c=t(=)cnc:ic_j <_) (_J C_J C3 (T» r-» d cj (_j i_j <_» t_j c_) d <=» iT* *~> *r> »^ «^ t^i i_i ci:)c::30O£=i(=3c=)£=> C->t_*t->C_><^CJt_>t_>^_>OQCO(»t^t_Jt_> Q £^ (=> C^ Q Q C=i « e s a O c>J bJ ou (_> CJtDCDCJCJCDtDCJtacJtD •—••<:•«: -c "—• ou -c .«c •< m: — ) a: a: •< 3e: ac a: a: a: 3c aaocic_)t_^c:i c_jc^t3tD en £=> £=) <=! C=3 sssssssssisiissssssssssssssssiiillss t/iuiuii/itiicotni/ic/iLOi/i(/) i>ii/iLn(/i«.ouii/ii/ii.o<>ii/it/i <=> o a c!) U t_i O in ir:i oo<=>Qc» C_J t-> C_> Q Q Q Q Q Ci Q ddSSSSS£S3S3g333SiSS33SS$ss3sllls$$$i||$ CO cyi CO CO <=»<=» O C=> c:^ ££££££ -<■*: -^ -<-<:■*: •*: ^^^'<-<:-<:.<:'-<'<:^ cac:iQQc:iQt_jt_jcjaic_j(_j iiiiiiiiiiiiiiiii iii^immmmm (_*»-> c_> f-i cr» m <=i »^ (-^ .r^ »-* »-> SSSSSS££S3ESS -<-<-<-< ££££^^£^£££ a: a! a: t/J oi CO to to Q Q Q <_) t_J t_> tj (_^ c_j Q ca cn r^r>r~»t_i(_»t_>»«oo»«t_>(_ji^t_iuuCaCiCiQCiOCaQQ fa» te. Ck^ l_> t_> i'<'*:-<'<:-<-<'*: ac: 3C 3C 3E:3cz:a:3C7:ae:x:z:x:z: oo <_> t_^ tj (L-><-JC_JC_>t_>ciacDt_><_j QCicacaCiQCscicri WE stry the ronment Mmistere de TEnvironnement APPENDIX 3 Ontano AIR RESOURCES BRANCH Phytotoxicology Section 880 Bay Street, Suite 347 Toronto, Ontario MSS 1Z8 135 Si Clair Avenue West Suite too Toronto. Ontario M4V 1P5 13S ouest. avenue St Clan Bureau 100 Toronto (Ontario) M4V IPS DERIVATION AND SIGNIFICANCE OF MOE "UPPER LIMITS OF NORMAL" CONTAMINANT GUIDELINES The MOE "upper limits of normal" contaminant guidelines shown in the attached table essentially represent the expected maximum concentrations of contaminants in surface soil (non-agricultural), foliage (deciduous and current year coniferous trees and shrubs), grass, moss bags and/or snow from areas of Ontario not subject to the influence of point sources of emissions. "Urban" guidelines are based upon samples collected from centres of minimum 10,000 population. "Rural" guidelines are based upon samples collected from non-bailt-up areas. Samples were collected by MOE personnel using standard sampling techniques (ref: Ministry of the Environment, 1983. Field Investigation Manual. Phytotoxicology Section - Air Resources Branch; Technical Support Sections - NE and NW Regions). Chemical analyses were performed by the MOE Laboratory Services Branch. The guidelines were calculated by taking the arithmetic mean of available analytical data and adding three standard deviations of the mean. For those distributions that are "normal", 99% of all contaminant concentration results for samples from "background" locations (Le. not affected by point sources nor agricultural activities) vill lie below these upper limits of normal. For those distributions that are "non-normal", the calculated upper limits of normal will not actually equal the 99th percentile, but nevertheless they lie within the otxserved upper range of MOE results for Ontario samples. Geometric means were not employed in calculating the guidelines because: 1) tests of two representatiw non- normal distributions showed that normality was not significantly improved by using log-transformed data, and 2) the guideline concentrations calculated using the geometric mean were considerably higher than the maximum otwerved concentra- tions. vca -2 Due to the large variability in element concentrations which may be present across Ontario, even in background data, control samples should always be collected. This is particularly important for soils, which may show large regional variations in element composition due to differences in parent material Species of vegetation which naturally accumulate high levels of an element also may be encountered. It is stressed that these guidelines do not represent maximum desirable or allowable levels of contaminants. Rather, they serve as levels which, if exceeded, would prompt further investigation on a case by case basis to determine the significance, if any, of above-normal concentration(s). Concentrations which exceed the guidelines are not necessarily toxic to plants, animals or maru Concentrations which are below the guidelines would not normally be considered toxic. A brief review of world literature has shown that the guideline con- centrations are generally within the ranges of results reported by other investigators. The table of guidelines will be expanded and revised as more data become available. (August, 1986) PH74/12 Containinanc Guidelines Representing -pp«r Liauts of Noraal Concentrations (ppm, dry weight) of Parameters _in_S oili_Folia3e^_^j3as_^_Mo3s_&3S_and_Snow_in_0ntario_JCrtan_and_aur^^ The guidelines are approximately equal to the mean of the data plus three standard deviations. Para.Tieter Sou (0-J cm) Urban Rural Foliage (unwashed) Urban Rural Grass (unwashed! Rural Moss Bag Urban 1** Rural Snow*** Rural Aluminum a a 300*»« 500 a a 1700 0.6 Antimony S !•• 0.5«« 0.3«« a a Arsenic 20 10 2 0.3, 2* c, J* :.o* Boron 15 10 •• 175 75 20 a Cadmium » 3, ♦• 3* 1* 0.3, 2* 0.003 Calcium b 6 a 3% a 2 Chloride a a b 0.13% 1% 0.03% < Chromoim 30 50 S i 3 a Cobalt 25"« 23 2*** 2 2, »• c Copper 100 &0 20 20 7, 20* 60 0.36 Fluoride a a 33 13 12 »5 a Iron 3.5%**' 3.5% 1000 300 300 3000 1700 0.7 Lead 300 130 60 30 20 20c 33 0.07 Magnesium a 1% 0.71 0.7% a o.« Manganese 700 700.1Q00 b 6 30, a* » Mercury 0.3 0.15 0.3 0.1 a 0.2 O.OOOI** Molybdenum 3 2 — 1.5 1.3 6 a Nickel 60*** 60 7 3, 30* 3, 23» 13 0.0* Nitrogen a a b b b 1 (as nitrate) Phosphonjs a a a a a 0.0« Potajjium a d a a a 1 Selenium 2 2 0.7 0.3 0.3 0.6 a SUver c a a a a a Sodium a a 330 30 a 2 Sulphur a 0.1% 0.«r« two values are shown, the first is based mainly on Southern Ontario data xhile t.he seccr. la based on NE Region data. Also, there are indications chat sorae of the <7uidalines. at least for foliage, may be somewhat liberal for the NW Region. THESE ^UICCIINB ARC nTA-VT ?C SUPPLTMENT, RATHER THAN REPLACE, SPECIFIC CONTROL DATA. Provisional guideluw estimated trom range at results, pending additional data. Rural reiult} higher than urban results • urban guideline basei] on rural results. Data for species considered to be accumulators (Populus spp., ftetuU »pp.. Salu ipp.) escluded. Moss bag guidelines based on )0 day exposure. No data from NC Region. Snow guidelines 4re mgyl ol meliwaier, except conAjctiviry which ,sA>mno»/cm. BaseO -naini> on s« a^o Nf Reg,on .sata. Sample sue miutlicieni (4 )0) to establish guideline. Concentration nlgnly varlaole - gyUellne not esteblished. 10% or rno€m ot results less than ileteciion iimii • guideline rwi estabusned Discrepancy between Ontario data and literature values • guideline not estaausned. nor sDO 1 1 : sole . r*s« *00. T<»o« APPENDIX 4 Ontario Ministry of the Environment 1 35 St. Clair Avenue West Suite 100 Toronio. Ontario M4V1P5 MEMORANDUM June 16, 1981 TO: Dr. G. Van Volkenburgh Director Air Resources Branch FROM: S.N. Linzon, Supervisor Phytotoxicology Section Air Resources Branch SUBJECT! Phytotoxicology Surveys West-Windsor 1975-1979 Please find attached a report of phytotoxi- cology surveys conducted in the west end of Windsor during the years 1975 through 1979. Thirty sampling stations were established in a grid fashion and soil and vegetation were sampled annually for chemical analysis. Excessive levels of fluoride amd iron were found at westerly stations influenced by emissions from the Zug Island area industries in Michigan. ^^.--'-'^^/V .z^-^^c^ C^K^ S.N. LINZON, Ph.D. SNL/hm Attach. c.c. F.N. Durham C. Schenk Ontario Ministry 1 35 St.Clair Avenue west Suite 100 of the Toronto. Ontario Environment mavips An Examination of Fluoride, Chloride, Metals and Sulphur Contamination of Vegetation and Soils in West Windsor, 1975 to 1979 Phytotoxicology Section Air Resources Branch PURPOSE OF THE STUDY In 1975 Phytotoxicology Section activities in the west half of the City of Windsor were expeinded to determine the existence and extent of airborne contamination of vegetation and soils. The new expanded survey was designed not to supplant air quality data but to augment it by assessing the fate of several airborne contaminants and their possible effect on vegetation. Furthermore the survey was not designed to monitor particular industries and may, by virtue of the rather large grid pattern utilized, have missed detecting small, localized point sources of one or more of the contaminants. SURVEY DESIGN During the second week of August in 1975, 1976 and 1977 triplicate samples each of vegetation (silver or Manitoba maple) foliage and of soils (0-5 cm depths) were collected at Z'f (1975 and 1976) or 30 (1977) locations in west Windsor. In 1979 a similar sampling program was carried out at a smaller number (seven) of locations grouped awound the Morton terminal area. The western sector of Windsor was chosen because it has been the area considered most contaminated by various pollutants emitted from industries both in Canada (the 3. Clark Keith power station, the salt mines, and a number o( smaller industries) and in the United States (power generating stations, steel manufacturers, automobile manufacturers, etc.). Earlier Phytotoxicology Section surveys (2) had shown abnormally high fluoride levels in maple foliage in the area. Continuing air quality monitoring (1) has revealed fluoridation levels in the area frequently above the Provincial monthly criteria. Air Quality monitoring has also shown levels of chromium, cadmium, copper, iron, lead and sulphur dioxide to be consistently higher in West Windsor than in the surrounding areas. Sampling sites were chosen with several criteria in mind. First, the sites should not have been disturbed recently (within at least 5 years) by grading or soil addition. The ages of trees growing in the immediate vicinity of the soil sampling sites were used as a normally reliable indicator of lack of such activity. Unused lauids (open undeveloped areas common in Windsor by virtue of the fragmented nature of the urban development) were selected often. Secondly, sites were chosen wherever possible, well away ( 100 m if possible) from major thoroughfares in order to minimize the influence of vehicular activity. Finally, the pattern of sampling sites was generally that of a grid with intersects approximately 1.5 km apart, modified where necessary by the above considerations and by the availability of mature silver or Manitoba maple trees. Maples were chosen for their ubiquity, their size (not as easily shaded or protected by buildings and other trees as would less statuesque vegetation) and because this Section has over several years developed a substantial data base for these species. All samples were transported to the Phytotoxicology Section processing laboratory in Toronto, dried, ground and submitted to the Vegetation and Soils Unit, Inorganic Trace Contaminamts Section, Laboratory Services Branch for chemical analysis. Soil samples were passed through a 'fO mesh sieve prior to submission for analysis. Soils were not analysed for either halide due to either the normally large background concentrations (fluorides) which easily mask small airborne additions or the high solubility (chlorides) which result in rapid leaching from soil. The Phytotoxicology Section established in the early 1970's and has since updated, excessive concentration levels for various elements in vegetation -3- foliage and/or soil, that serve as a guide to when an area or site can be considered significantly contaminated by man's activities. Concentrations which are considered excessive for the elements under study in these surveys are shown circled in each table of results. RESULTS (a) Fluoride Results of the analyses of maple foliage samples collected 1975-1977, unwashed samples, are displayed in figures 1 through 3. The fluoride contamination observed in West Windsor probably originated from two areas: Michigan, primarily in the vicinity of Zug Island, and the Morton Terminal. Previous Phytotoxicology Section Reports (3) have documented fluoride contamination near this Terminal. A comparison similar to that made in the 1970-1973 Phytotoxicology studies (2) is shown in Table 'f. Fluoride levels at Mic Mac Park, after declining each year between 1970 and 1972, remained relatively constant in the following 5 years. At station 2 (Broadway and Sandwich) fluoride levels have remained relatively constant since 1970 with the possible exception of 1972. Some anomalies exist in the data for the more inland locations, specifically the abnormally high concentrations at stations 13 and 2^* in 1975 and the somewhat lower than would be expected fluoride concentrations in foliage samples from site 7 in 1975. The inconsistency of these results suggests that the degree of exposure of the sampled trees (not always the same trees were sampled each year) rather than local fluoride sources was the major influencing factor. (b) Chloride Chloride concentrations in maple foliage were low (generally less than 0.35% dry weight) throughout the survey area with the exception of those concentrations found at site 1 in 1976 and 1977, and that found at site 2'» in 1976. All elevated results are probably the re^sult -n of road deicing salt applications. A Phytotoxicology report W has documented a salt blow-off problem related to the Canadian Rock Salt Co. Ltd., however, this blow-off would be most likely detected at sites 2,3, or 'f. Chlorides were not significantly higher at these sites than in the surrounding area. (c) Sulphur The area around sampling site 1 has been used for the disposal of sludge-like material with an apparently higher than normal organic content*. This has resulted in substantially higher than normal sulphur and iron concentrations in the soil. If these site 1 results are ignored however, no coherent pattern of sulphur contamination of soil remains in west Windsor. Vegetation foliage results for sulphur did show a vague trend with stations 1 and 2 in 1975, station 1 in 1977 and station 12 in all years somewhat higher than the apparently normal range of 0.15 to 0.25 percent of dry weight. Sulphur dioxide levels in air (1) do not appear to support a conclusion that these elevated sulphur concentrations are the result of foliar absorption from aur. Ambient air quality, with resjject to sulphur, improved through the period 1975-1977. ♦ This observation is based on both field observations and total carbon/organic carbon analyses (not shown) performed on the 1976 collection soils. This material did not however contain appreciably higher than normal concentrations of the other heavy metals. (d) Iron When, as above, site 1 soil results have been disregarded and the results of all year's collections for each site are averaged and presented in map form (Figure <*), it is apparent that iron concentrations in soil have been influenced by two general factors. Firstly, as a result of industrial and/or vehicular activity, iron concentrations in soils from mid-Windsor were higher than in soils from more southerly, less densely populated areas surveyed. Secondly, some iron contamination has originated in Michigan as evidenced by higher concentrations in soils from site 2. Vegetation foliage collections/analyses support these observations, in particular the second observation related to Michigan sources. Iron concentrations in vegetation were generally higher in 1976 with 4 results exceeding that level considered excessive by the Phytotoxicology Section. (e) Lead The lead concentrations in vegetation and soils are tabulated in tables 2 and 3 and shown graphically in figures 6 and 7. Lead concentrations in foliage were generally low and fell only roughly into 2 patterns: very slightly elevated levels along to the river's edge probably related to transboundary movement and somewhat elevated levels related to Hwy. 3 (Huron Church Road). From table 2 it is apparent that the markedly higher mean value from station 12 is due to the anamolous result from 1976 which probably should be disregcirded. Soil contamination fell into patterns more easily related to industrial and/or automobile activity. Transboundary movement of industry related contamination and automobile activity in downtown Windsor are strongly implicated. (f) Cadmium Cadmium concentrations in vegetation and soils are tabulated in Tables 2 and 3 and shown graphically in figures 8 and 9. Both vegetation and soils results show general trends of decreasing concentrations with increasing distance from the south Detroit industrial area. Downtown Windsor appears to have been the least contaminated area surveyed. (g) Zinc Zinc concentrations in vegetation and soils are tabulated in Tables 2 and 3 and shown graphically in Figures 10 and 11. Zinc levels in vegetation fall rather poorly into coherent patterns. Neither industrial or downtown Windsor nor industrial south Detroit appear to have contributed significantly. Soil zinc concentrations however did -6 relate to both transboundary contamination and to downtown Windsor. In 1977 samples of both tree foliage and soils were analysed for an additional seven elements: copper, chromium, molybdenum, nickel, vanadium, arsenic and selenium. These elements are occasionally associated with industrial activity. Vanadium and arsenic concentrations in soil were barely measurable in tree foliage collected at sites near the river but were at or below the analytical detection limit elsewhere. No coherent patterns of the other elements materialized. DISCUSSION Three general sources of contamination have influenced concentrations of fluoride, chloride, sulphur and heavy metals in soils and/or vegetation foliage in the West Windsor area: The industrialized areas of south Detroit particularly surrounding Zug Island, Michigan; the industrialized areas of west and central Windsor and vehicular activity in the general area. The influence of the Zug Island area industries is evidenced by fluoride concentrations in vegetation foliage, iron in vegetation and soils and lead, cadmium and zinc in soils. In each year since 1970, fluoride concentrations in maple foliage from the Broadway and Sandwich area were found to exceed the Phytotoxicology Section excessive levels. Injury due to exposure to airborne fluorides has been observed each year since 1969 on wild grape foliage and occasionally on silver maple foliage growing in the Broadway/Sandwich Streets area. Although measureable, the elevation of metals concentrations was not great enough to visibly impair the health of vegetation. The impact of Windsor industry is less easily distinguised. As noted above from earlier reports, emissions from the Canadian Rock Salt Company have influenced chloride levels In the vicinity of the company. An earlier Phytotoxicology report (it) described blow-off of sodium chloride from storage piles which caused injury to nearby vegetation. Later reports on the Morton Terminal area have indicated also some very localized salt contamination problems near the Rock Salt Company. In these same reports, the Morton Terminal fluorspar transhipment operation was shown to have had a measureable impact on fluoride concentrations in grass foliage from the vicinity of the Terminal buildings; but, as these reports also indicate, this problem is very localized and was not responsible for the generalized fluoride problem in west Windsor. The impact of vehicular activity in central Windsor and possibly industrial activity in this area have resulted in elevated lead, iron and zinc levels in soils. Although significantly above background levels such concentrations have not visibly injured vegetation. For the most part the levels of metals contamination were below those which we have found in Toronto. Table (5) is taken from Table 2.5-1 of the Working Group on Lead report 5 (197^*) on Toronto lead levels in vegetation and soil. Virtually all Windsor results (only the anomolous site 12 excepted) for lead in vegetation fell well within that range referred to as "Suburban, remote from traffic and industry". All Windsor lead in soil results fell into "Suburban and /or downtown, remote from traffic and industry". SUMMARY Airborne contamination, the result of industrial and vehicular activity in the Windsor/Detroit area has resulted in elevated levels of several elements in soils and/or vegetation foliage in the west Windsor area. These contaminants include iron, lead, cadmium, zinc, fluoride and chloride. Only fluoride levels, detected in the docks area, were high enough to cause visible impairment to the health of sensitive vegetation. D. S.VHjf per. Head Controlled Environinent Unit Phytotoxicology Section REFERENCES Grosse, G. A., (1978), Ambient Air Quality in Windsor ,1972 to 1977, A Technical Support Section Report, Southwestern Region, Ministry of the Environment. Harper, D. S., (197'f), Vegetation surveillance investigations in Metropolitan Windsor, 1970 - 1973, A Phytotoxicology Section Report, Air Resources Branch, Ministry of the Environment. Harper, D. S. (1980), Vegetation Sampling near MortonTerminal, Windsor, September 26, 1979, A Phytotoxicology Section Report, Air Resources Branch, Ministry of the Environment. Temple, P. J. (1972), Investigation of salt injury complaints to vegetation in the vicinity of the Ojibway Salt Mine, Canadian Rock Salt Co. Ltd., LaSalle, Ontario, July, 1972. A Phytotoxicology Section Report, Air Resources Branch, Ministry of the Environment. Working Group on Lead (197t), Studies of the Relationship of Environmental Lead Levels and Human Lead Intake. Report to the Ontario Minister of the Environment. TABLE 1 Fluoride, Chloride and Sulphur Concentrations in Maple Foliage Collected 1975 to 1979 in Windsor Sampling Maple Chemical Analyses Result s by Element Site No. Species Code and year of collection (MM » (Unwashed Samples) Sulphur Fluoride Chlori de Manitoba (Z, dry wt . ) (ppm, dry rft.) (Z, dry wt. ) maple, SiM = silver maple) 1975 1976 1977 1975 1976 1977 1979 1975 1976 1977 1979 1 MM 0.33 0.27 0.32 B. M ® _ 0.22 0.83 0,39 _ 2 SiM 0.35 0.16 0.12 0463 UO^ Q2D do9^ 0.09 0.11 0.14 0.16 3 SiM (red oak in 1975 and 1976) 0.21 0.21 0.24 9 15 ® w 0.04 0.03 0.08 0.21 4 SiM 0.15 0.20 0.15 (S) ® ® <^2^ 0.15 0.29 0.31 0.21 5 SiM 0.15 0.18 0.19 25 Qg3 0.15 0.18 0.17 0.18 6 SiM 0.21 0.27 0.21 16 16 8 - 0.11 0.10 0.05 - 7 SiM 0.22 0.22 0.21 12 21 30 - 0.13 0.12 0.08 - 8 MM 0.15 0.26 0.26 29 34 17 (2) 0.10 0.19 0.15 0.09 9 SiM 0.28 0.26 0.21 31 33 <2) 31 0.22 0.24 0.14 0.27 10 SiM 0.18 0.19 0.22 34 (^ 34 ® 0.09 0.14 0.13 0.33 11 SiM 0.23 0.22 0.22 15 26 22 0.04 0.29 0.20 - 12 MM 0.33 0.30 0.36 27 23 14 - 0.07 0.07 0.05 - 13 SiM 0,22 0.22 0.22 di) Q) 23 - 0.15 0.15 0.16 - 14 SiM 0.26 0.19 0.19 17 Q§) 24 - 0.15 0.10 0.13 - 15 SiM 0.20 0.26 0.20 13 - 0.07 0.11 0.11 - 16 SiM 0.18 0.25 0.18 14 17 19 - 0.04 0.23 0.10 - 17 SiM 0.21 0.25 0.18 14 32 12 - 0.13 0.16 0.13 - 18 SiM 0.26 0.19 0.24 16 28 12 - 0.14 0.11 0.14 - 19 SiM 0.27 0.26 0.21 17 25 13 - 0.23 0.16 0,13 - 20 SiM 0.17 0.04 0.21 15 29 16 - 0.35 0.29 0.26 - 21 SiM 0.25 0.20 0.20 17 23 15 - 0.16 0.22 0.25 - 22 SiM 0.20 0.15 0.19 24 28 18 - 0.16 0.14 0.16 - 23 SiM 0.20 0.19 0.25 14 22 9 - 0.05 0.03 0.06 - 24 SiM 0.18 0.22 0.17 18 @ 15 - 0.25 0.45 0.19 - 25 SiM - - 0.19 9 - - - 0.04 - 26 SiM - - 0.24 - 12 - - - 0.11 - 27 SiM - - 0.16 - 11 - - - 0.19 - 28 SiM - - 0.19 - 9 - - - 0.18 - 29 SiM - - 0.21 - 19 - - - 0.27 - 30 SiM - - 0. 16 - 24 - - - 0.19 - Phytotoxi cology Excessi ve 35 35 35 35 levels Coacentrations of Cadmium, Iron, Lead and Zinc in Tree Foliage Samples Collected in Windsor 1975 through 1977 TABLE 2 (Unwashed Sample) Element Concentration by year of collection . (ppm,. dry weight) Station 4 Cadmium Iron Lead Zinc 1975 1976 1977 1975 1976 1977 1975 1976 1977 1975 1976 1977 1 0.5 0.7 0.7 697 J39^ 663 11 25 23 19 42 28 2 0.2 0.6 0.9 623 (5^ 640 11 i8 20 50 86 54 3 0.4 0.3 0.7 183 262 493 20 18 18 38 41 59 4 0.5 0.8 1.0 440 (^50^ 563 17 41 23 36 177 63 5 0.4 0.5 0.5 457 793 400 15 22 17 33 113 35 6 1.1 0.4 0.5 243 260 227 14 13 5 43 50 46 7 0.7 0.5 0.7 220 286 437 11 16 13 31 47 64 8 1.0 0.5 0.8 423 587 417 15 27 14 22 41 29 9 1.2 0.5 0.6 437 490 613 15 16 23 44 61 44 10 1.1 0.6 0.7 537 687 727 17 26 27 26 56 49 11 0.3 0.6 1.1 176 360 543 10 17 28 38 69 47 12 0.3 0.5 0.4 426 493 448 20 92 21 27 39 27 13 0.3 0.4 0.6 459 517 400 18 30 25 30 46 38 14 0.5 0.9 0.5 603 453 343 17 39 17 41 71 66 15 0.3 0.5 0.2 242 438 247 15 46 19 78 71 51 16 0.3 0.5 0.4 227 214 240 10 16 9 32 33 29 17 0.3 0.5 0.5 255 487 243 13 32 16 36 71 35 18 0.5 0.8 0.6 283 500 307 10 25 13 55 89 67 19 0.4 0.5 0.3 239 427 303 21 42 24 42 65 42 20 0.2 0.4 0.4 230 390 457 11 12 22 21 45 26 21 0.2 0.4 0.3 215 387 293 10 13 17 33 48 25 22 0.2 0.2 0.2 318 537 607 13 16 19 33 61 36 23 0.3 0.3 0.2 170 227 265 14 19 16 41 55 47 24 0.4 0.4 0.3 312 (827) 767 12 45 23 28 95 26 25 - - 0.3 - - 221 - 9 - - 27 26 - - 0.5 - - 307 - 14 - - 35 27 - - 0.8 - - 470 - 15 - - 41 28 - - 0.5 - - 320 - 14 - - 24 29 - - 0.6 - - 433 - 20 - - 22 30 ~ - 0.8 - - 567 - 27 - - 60 Phyto- 5 5 5 800 800 800 100 100 100 250 250 250 toxicology level s TABLE 3 Average Concentrations of Sulphur and Pour Metals in Soils Collected in West Windsor 1975 to 1977 [Concentration o f element, dry weight analysis Station Sulphur Iron Lead Cadmium Zinc pH No. (Z) (Z) (ppm) (ppm) (ppm) (1976) 1 0.43 3.1 225 3.1 258 7.2 2 0.11 2.7 154 3.4 315 6.7 3 0.09 1.4 89 2.2 209 6.2 4 0.08 1.3 105 2.4 197 7.3 5 0.07 0.82 47 1.7 97 6.7 6 0.05 0.97 45 1.9 77 6.7 7 0.09 1.1 54 . 2.2 114 6.6 8 0.05 1.0 40 2.1 81 7.5 9 0.08 1.6 69 1.4 127 6.0 10 0.08 1.3 108 1.7 190 7.7 11 0.08 1.4 225 1.9 194 7.0 12 0.07 1.6 69 1.4 127 6.0 13 0.07 0.83 75 1.0 76 6.6 14 0.05 0.96 41 1.0 76 6.6 15 0.07 0.87 223 1.0 171 7.0 16 0.06 0.88 44 0.9 82 5.8 17 0.06 1.5 51 1.4 108 7.3 18 0.08 1.5 156 1.3 181 6.6 19 0.07 1.4 158 1.3 176 6.9 20 0.06 1.4 297 1.2 262 6.7 21 0.06 1.4 116 1.1 147 6.7 22 0.07 1.7 163 1.2 180 6.5 23 0.07 1.7 131 1.4 138 7.6 24 0.08 1.6 126 1.4 180 7.6 25 0.08 1.2 80 2.2 88 - 26 0.07 1.0 56 1.9 85 - 27 0.08 1.0 50 2.0 90 - 28 0.08 1.0 128 2.4 112 - 29 0.06 1.0 50 1.8 79 - 30 0.11 1.1 248 2.1 150 Phy to- - - 600 8 400 - toxicology Excessive levels TABLE 4 Fluoride Content of Maple foliage at tvo Locations in Heat Windsor, 1970 - 1979 Sampling Location Sample Preparation* Fluoride Content of Silver Mapl« (ppm, dry weight) ; Foliage Aug. 31 1970 Sept. 23 1971 Sept. 5 1972 Aug. 22 1973 Aug. 7 1975 Aug. 10, 11 1976 Aug. 9, 10 1977 Sept. 26 1979 Mic Mac Park (1970- (Sta. 9 1975-77) NW -73) W ® 28 25 35 22 31 33 20 30 31 Broadway & Sandwich NW o <® © © © ® <©) (^9) Streets (Sta. 2) W ® ® ® © - ® ® - Phyto- toxicology NW 35 35 35 35 35 35 35 35 Excessive Levels W - - - - - - - * NW: unwashed preparation W: washed preparation - one 30 second wash in 0.05Z Alconox detergent, 0.05X EDTA followed by three 10 second rinses in distilled water. 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