Phytotoxicology Investigation in the Vicinity of Algoma Steel Inc. Sault Ste. Marie - 2005 Report No.: Phyto-S5020-2005 April 2006 Prepared by: Ontario Ministry of the Environment Environmental Monitoring and Reporting Branch Last Revision Date: May 2013 Cette publication hautement spécialisée n’est disponible qu’en anglais en vertu du règlement 671/92, qui en exempte l’application de la Loi sur les services en français. Pour obtenir de l’aide en français, veuillez communiquer avec le ministère de l’Environnement au 705-564-3237. For more information: Ministry of the Environment Public Information Centre Telephone: 416-325-4000 Toll free: 1-800-565-4923 Email:[email protected] www.ontario.ca/environment © Queen’s Printer for Ontario, 2013 PIBS 9481e Phytotoxicology Investigation in the Vicinity of Algoma Steel Inc. Sault Ste. Marie - 2005 Background Algoma Steel Incorporated is an integrated primary iron and steel producer located on the St. Mary's River in Sault Ste. Marie, Ontario. Integrated mills produce steel in blast furnaces where iron ore is mixed with coke and the coke is burned under controlled conditions so that carbon monoxide is produced. This carbon monoxide chemically reduces the ore, consisting primarily of iron oxides, to metallic iron. Limestone added to the furnace provides an additional source of carbon monoxide as well as acting as a flux to fuse with silicates in the ore. The resulting calcium silicate floats to the top of the molten iron and is drawn off as slag. A critical material in steel making is the coke. Coke is produced by heating coal to high temperatures and distilling off the volatile components of the coal. The remaining material consists primarily of carbon and is known as coke. Coke provides the high heating value to smelt the iron ore and is also the source of carbon in steel. Integrated mills produce their own coke in coke ovens. The ovens consist of narrow vertical chambers known as 'batteries'. The heat to distill the coal is generated by burning gases in spaces between adjoining chambers. Volatile compounds released as the coal is distilled are condensed to produce coal tar, while the non-condensed gases are recovered and burned to distill fresh charges of coal. Polycyclic Aromatic Hydrocarbons During coke production there are inevitable emissions of volatilized coal tar or of coal gas to the atmosphere. Major constituents of coke oven emissions are a class of organic compounds known as polycyclic aromatic hydrocarbons (PAHs). PAHs consist of three or more fused aromatic rings. Some consist only of carbon and hydrogen atoms, while some PAHs have other atoms substituting for carbon in the benzene ring, or functional groups substituting for hydrogen atoms. Consequently, it is possible to have a great diversity of PAHs. It should be noted that PAHs are not necessarily constituents of coal but can be formed during the coal distillation process. The boiling points of PAHs are usually high enough so that they will not persist in the atmosphere in vapour form, but will condense onto particulates acting as condensation nuclei. Consequently, the dispersion and deposition characteristics of PAHs are dependant on the behaviour of the particulate nuclei. Small particles will be transported greater distances than larger particles and can theoretically contain a higher mass to volume ratio of adsorbed PAHs. However, since the greater the dispersion distance, the greater the dilution, ambient air concentrations of PAHs, either in vapour or particulate form, are invariably higher near a point source. The primary concern about PAHs is that some are considered probable human carcinogens. One of these, benzo(a)pyrene, has been the subject of considerable toxicological research and is the only PAH compound for which Ontario has an ambient air standard. The benzo(a)pyrene ambient air standard of 1.1 nanograms per cubic metre of outdoor ambient air per 24 hours is regularly exceeded at a MOE monitoring station located near a residential neighbourhood near and to the northwest of the Algoma Steel complex. Page 1 of 12 Report No.: Phyto-S5020-2005 Phytotoxicology Investigation in the Vicinity of Algoma Steel Inc. Sault Ste. Marie - 2005 Investigation Design The investigation which is the subject of this report follows previous investigations conducted in 1998 and 2003. These investigations were reported in MOE Phytotoxicology reports SDB-075-3511-1999 and Phyto-S5020-2003. The 1998 investigation concluded that Algoma Steel was a source of airborne PAHs, but that the soil sampling site distribution was too wide and that there were an inadequate number of sites in the adjacent residential neighbourhood to adequately assess the effect of PAH emissions from Algoma Steel on the soil of that neighbourhood. There were three soil sampling sites in the neighbourhood adjacent to the northwest of Algoma Steel and 17 more between one and four kilometres from the coke ovens. The 2002 investigation focussed only on the neighbourhood adjacent to the northwest of Algoma Steel. Twenty new sampling sites were established, primarily on lawns of residential properties. Soil from the near surface (0 to 2.5 centimetres) was collected at these sites. This investigation determined that soil PAH concentrations were indeed elevated and that Algoma Steel was the source. However, the soil PAH concentrations but did not exceed health-based criteria. For 2005 the MOE Sault Ste. Marie District Office requested that the Phytotoxicology Investigations Unit (PIU) expand the investigation to more definitively determine whether the PAH emissions and resultant air concentrations were resulting in soil contamination that could be a concern to the health of residents in this neighbourhood. The investigation was conducted on August 9 and 10, 2005. The locations sampled in 2002 were re-sampled in the same manner. Ten additional locations were added, concentrating in the part of the neighbourhood that was closest to the coke oven batteries of Algoma Steel. After the surface sampling at the 30 locations was completed, three were re-visited to determine whether the soil in this neighbourhood exhibited a PAH concentration gradient with depth. To accomplish this, soil samples were collected at four depth increments of five centimetres each to a depth of 20 centimetres. A fourth location was also sampled in five centimetre increments to a depth of 20 centimetres. This location was not in the subject neighbourhood. It was a location sampled in 1998 when the wider geographic area was addressed. This location was distinguished with much higher PAH concentrations than all other 1998 locations. In addition to sampling soil, three Norway maple trees were selected for foliage sampling. This was one more attempt to use tree foliage as an indicator of the relative magnitude of PAHs in the air in the vicinity of the coke ovens. The foliage samples were collected in the mid- afternoon on August 9, 2005, immediately before a major thunderstorm. This provided an opportunity to sample again the following day in an attempt to establish how significant rain can be in washing accumulated particulates from foliage surfaces. Figure 1 consists of an orthorectified image of the investigation area captured during an air photography survey in 2004. Sampling locations for the soil and tree foliage samples have been added to this image. Page 2 of 12 Report No.: Phyto-S5020-2005 Phytotoxicology Investigation in the Vicinity of Algoma Steel Inc. Sault Ste. Marie - 2005 Figure 1: Soil Sampling Locations - Algoma Steel Inc., Sault Ste. Marie - 2005 Sampling Procedures Prior to sampling, all sampling equipment that would be in contact with the soil sample was washed with a high-phosphate detergent, rinsed with de-mineralized water, and then successively rinsed with acetone and hexane. The sample containers were amber glass jars with TeflonTM lids. These containers were previously washed with a detergent solution followed by several de-ionized water rinses and were provided by the MOE Laboratory Services Branch. A sampling location for the surface soil samples consisted of the whole of the sodded portion of the yard, or an area about 10 metres by 10 metres if the yard was particularly large. Page 3 of 12 Report No.: Phyto-S5020-2005 Phytotoxicology Investigation in the Vicinity of Algoma Steel Inc. Sault Ste. Marie - 2005 Ten cores of soil to a depth of 2.5 centimetres were removed over a grid pattern with a soil coring device consisting of a hollow, two centimetre diameter, stainless steel tube fitted with a cutting tip. The individual cores were placed into a stainless steel bowl, homogenized and transferred to a labelled glass sample jar. The soil profile sampling used the same equipment but the corer was inserted to depth of at least 20 centimetres. The extracted soil core was sectioned into the four increments of five centimetres each and placed into the jars. Five cores were collected and each increment class was placed into a common jar. The jars were shaken vigorously to homogenize the samples. Tree foliage samples were collected by cutting a branch from a portion of the canopy that was well exposed to the Algoma Steel coke ovens. The leaves from the branch were removed by hand while wearing neoprene gloves and placed into an amber glass jar. All samples were forwarded to the MOE Laboratory Services Branch for determination of PAH concentrations by gas chromatography - mass spectrometry (GC-MS). The analytical method applied to the 2005 soil samples differed from previous methods. The analysis included spiking of the samples with deuterium-labelled PAH compounds and determining the proportion of the spikes recovered during the concentration determination. This recovery value was used to correct the apparent concentrations of the target PAH compounds. This methodology is more precise and expands the list of PAHs that are quantified by two for a total of 18 PAH compounds. The analysis of the foliage samples followed older methodology, using labelled spikes of only three PAHs as a quality control to ensure that recoveries were within acceptable limits. Corrections for recovery were not applied and 16 PAH compounds are reported. Results Table 1 contains the concentrations of the 18 PAH compounds in the surface soil from the 30 locations collected during this investigation. The data are reported in nanograms per gram (ng/g), also known as parts per billion, on a dry weight basis. The last two columns in this table contain the concentrations from Table 1 (Full Depth Background Site Condition Standards) and Table 3 (Full Depth Generic Site Condition Standards in a Non-Potable Ground Water Condition) as contained in O. Reg. 153/04, the Soil, Ground Water and Sediment Standards for Use Under Part XV.1 of the Environmental Protection Act. The Appendix contains information on the legislation governing standards for soil contaminants. Table 2 contains PAH data from the three locations in the subject neighbourhood where soil was sampled to a depth of 20 centimetres, as well as the fourth location where anomalously high PAH concentrations were detected in 1998. Table 3 reports the PAH concentrations for the foliage samples, in nanograms per gram, on a fresh weight basis. Data for samples collected before and after the rain storm are listed, as are the % differences. Reductions in PAH concentrations in tree foliage after the rain event are indicated by data in brackets. It must be recognized that before and after samples are not the same samples. However, the post rain samples came from branches that were next to those cut before the rain. Page 4 of 12 Report No.: Phyto-S5020-2005 Phytotoxicology Investigation in the Vicinity of Algoma Steel Inc. Sault Ste. Marie - 2005 Table 1: PAHs (ng/g dw) in Surface Soil (0-2.5 cm) near Algoma Steel, SSM - 2005 Site 21 22 23 24 25 26 27 28 29 30 Naphthalene 460 280 230 180 300 240 140 200 120 170 Acenaphthylene 53 39 45 26 62 83 41 52 24 85 Acenaphthene 13 12 13 8 33 19 12 14 5 10 Fluorene 62 40 40 29 61 41 29 35 21 30 Phenanthrene 490 340 410 240 670 480 270 360 170 340 Anthracene 62 45 53 31 98 74 53 49 22 48 Fluoranthene 620 460 630 310 1,100 980 680 570 240 670 Pyrene 510 360 500 250 930 830 580 470 190 550 Benzo(a)anthracene 270 190 240 130 500 430 310 250 97 290 Chrysene 520 340 450 250 840 710 440 460 210 500 Benzo(b)fluoranthene 510 360 480 260 960 760 490 490 240 570 Benzo(k)fluoranthene 210 150 210 110 430 340 230 210 96 250 Benzo(e)pyrene 350 230 330 170 600 480 320 330 140 390 Benzo(a)pyrene 310 220 300 170 650 520 350 300 130 370 Perylene 84 59 95 51 190 160 120 88 42 120 Indeno(1,2,3-c,d)pyrene 350 250 330 280 910 690 470 450 220 560 Dibenz(a,h)anthracene 58 44 52 31 130 82 59 58 27 66 Benzo(g,h,i)perylene 280 200 260 160 570 470 260 270 130 320 Table 1(cont.): PAHs (ng/g dw) in Surface Soil (0-2.5 cm) near Algoma Steel, SSM - 2005 Site 31 32 33 34 35 36 37 38 39 40 Naphthalene 210 320 280 160 250 190 170 170 110 210 Acenaphthylene 92 65 39 25 74 69 66 59 19 31 Acenaphthene 14 22 10 4 15 12 15 7 7 10 Fluorene 40 56 32 21 40 34 33 21 16 24 Phenanthrene 490 530 330 200 410 390 410 260 160 250 Anthracene 80 74 40 30 63 57 56 39 19 33 Fluoranthene 1,000 740 440 350 650 640 890 540 230 320 Pyrene 810 580 340 270 510 520 720 440 180 250 Benzo(a)anthracene 410 300 170 140 260 280 340 230 87 130 Chrysene 730 580 360 250 550 560 590 410 170 280 Benzo(b)fluoranthene 760 580 350 270 540 550 680 490 190 300 Benzo(k)fluoranthene 340 250 150 110 230 240 310 210 82 130 Benzo(e)pyrene 460 360 230 170 350 330 380 300 120 210 Benzo(a)pyrene 470 370 220 170 330 330 440 310 120 180 Perylene 150 110 57 48 100 91 120 100 35 68 Indeno(1,2,3-c,d)pyrene 690 520 370 260 520 510 670 510 200 340 Dibenzo(a,h)anthracene 96 68 45 32 62 64 89 58 22 38 Benzo(g,h,i)perylene 400 310 210 140 300 290 360 270 110 200 Page 5 of 12 Report No.: Phyto-S5020-2005 Phytotoxicology Investigation in the Vicinity of Algoma Steel Inc. Sault Ste. Marie - 2005 Table 1(cont.): PAHs (ng/g dw) in Surface Soil (0-2.5 cm) near Algoma Steel, SSM - 2005 Site 41 42 43 44 45 46 47 48 49 50 Naphthalene 450 420 250 260 480 230 210 170 180 200 Acenaphthylene 48 110 64 42 57 110 47 42 20 41 Acenaphthene 13 14 10 14 14 16 55 11 8 10 Fluorene 48 51 36 32 44 45 86 31 26 34 Phenanthrene 500 680 370 340 480 580 1,200 290 240 370 Anthracene 48 85 52 40 46 80 150 39 29 59 Fluoranthene 610 1,400 680 510 610 1,300 2,800 470 280 540 Pyrene 500 1,400 550 420 480 1,000 2,300 400 210 410 Benzo(a)anthracene 240 700 310 200 260 520 1,100 210 110 210 Chrysene 540 1,100 510 430 590 910 1,800 410 280 390 Benzo(b)fluoranthene 500 1,200 540 430 570 1,000 2,100 410 250 370 Benzo(k)fluoranthene 240 550 250 220 250 480 1,000 200 100 160 Benzo(e)pyrene 290 660 300 260 330 580 1,200 240 150 220 Benzo(a)pyrene 300 780 330 280 350 640 1,400 260 130 230 Perylene 77 200 88 75 89 180 420 66 29 55 Indeno(1,2,3-c,d)pyrene 420 950 450 370 560 880 1,700 400 200 330 Dibenzo(a,h)anthracene 61 150 71 54 69 120 220 45 32 43 Benzo(g,h,i)perylene 300 640 270 250 350 540 1,100 220 140 220 Table 1(cont.): PAHs (ng/g dw) in Surface Soil (0-2.5 cm) near Algoma Steel, SSM - 2005 Soil Standards* Table 1 Table 3 Naphthalene 90 40,000 Acenaphthylene 80 100,000 Acenaphthene 70 1,000,000 Fluorene 120 350,000 Phenanthrene 690 40,000 Anthracene 160 28,000 Fluoranthene 1,100 40,000 Pyrene 1,000 250,000 Benzo(a)anthracene 740 40,000 Chrysene 690 12,000 Benzo(b)fluoranthene 470 19,000 Benzo(k)fluoranthene 480 19,000 Benzo(e)pyrene - - Benzo(a)pyrene 490 1,200 Perylene - - Indeno(1,2,3-c,d)pyrene 380 12,000 Dibenzo(a,h)anthracene 160 1,200 Benzo(g,h,i)perylene 680 40,000 *O. Reg. 153/04 - see Appendix Page 6 of 12 Report No.: Phyto-S5020-2005 Phytotoxicology Investigation in the Vicinity of Algoma Steel Inc. Sault Ste. Marie - 2005 Table 2: PAHs (ng/g dw) in Soil Depth Increments near Algoma Steel, SSM - 2005 Site Site 21 Site 25 Table 1* Depth Increment (cm) 0-5 5-10 10-15 15-20 0-5 5-10 10-15 15-20 Naphthalene 450 410 200 170 300 380 180 110 90 Acenaphthylene 58 51 35 41 71 110 48 22 80 Acenaphthene 12 11 6.2 4.5 37 62 36 16 70 Fluorene 55 40 22 19 48 61 33 17 120 Phenanthrene 480 400 230 220 600 890 500 270 690 Anthracene 62 54 33 34 74 120 67 37 160 Fluoranthene 620 560 400 480 980 1600 920 520 1,100 Pyrene 530 500 360 430 840 1400 800 440 1,000 Benzo(a)anthracene 270 250 180 220 380 640 390 210 740 Chrysene 550 500 330 360 740 1200 700 370 690 Benzo(b)fluoranthene 510 470 320 360 730 1200 700 380 470 Benzo(k)fluoranthene 240 220 160 180 360 560 340 180 480 Benzo(e)pyrene 340 290 200 210 490 720 440 240 - Benzo(a)pyrene 330 300 220 260 500 830 510 260 490 Perylene 99 93 69 72 140 250 130 67 - Indeno(1,2,3-c,d)pyrene 510 380 260 320 590 1000 680 440 380 Dibenzo(a,h)anthracene 56 52 37 43 96 160 100 48 160 Benzo(g,h,i)perylene 290 270 170 190 450 700 450 230 680 *O. Reg. 153/04 - see Appendix Table 2: PAHs (ng/g dw) in Soil Depth Increments near Algoma Steel, SSM - 2005 Site Site 32 Site 20 1998 Table 3 Depth Increment (cm) 0-5 5-10 10-15 15-20 0-5 5-10 10-15 15-20 Naphthalene 300 260 210 230 160 130 120 200 40,000 Acenaphthylene 59 63 55 68 180 170 170 200 100,000 Acenaphthene 37 15 15 13 260 130 130 670 1,000,000 Fluorene 48 35 26 30 240 130 130 650 350,000 Phenanthrene 570 440 420 420 2800 1900 1800 5900 40,000 Anthracene 86 57 60 60 290 180 160 800 28,000 Fluoranthene 920 680 670 730 4200 3300 3200 8000 40,000 Pyrene 750 550 550 610 3500 2800 2600 6400 250,000 Benzo(a)anthracene 430 280 280 310 1300 1100 1000 2900 40,000 Chrysene 790 570 540 570 2400 2100 1900 4900 12,000 Benzo(b)fluoranthene 780 530 530 570 2200 1900 1900 4200 19,000 Benzo(k)fluoranthene 380 260 260 280 1100 990 950 2100 19,000 Benzo(e)pyrene 470 340 340 370 1400 1200 1200 2400 - Benzo(a)pyrene 550 350 360 390 1600 1400 1400 3100 1,200 Perylene 170 110 100 97 450 380 370 840 - Indeno(1,2,3-c,d)pyrene 890 590 610 660 2100 1900 2000 3400 12,000 Dibenzo(a,h)anthracene 100 67 81 83 270 240 240 510 1,200 Benzo(g,h,i)perylene 450 290 290 330 1200 1000 990 2100 40,000 *O. Reg. 153/04 - see Appendix Page 7 of 12 Report No.: Phyto-S5020-2005 Phytotoxicology Investigation in the Vicinity of Algoma Steel Inc. Sault Ste. Marie - 2005 Table 3: PAHs (ng/g fw) in Norway Maple Foliage near Algoma Steel Before and After Rain Storm - SSM - 2005, values in brackets are % less PAHs after the rain event. Site 1 Site 1 Site 1 % Site 2 Site 2 Site 2 % Site 3 Site 3 Site 3 % before after difference before after difference before after difference Naphthalene 1 20 20 0 20 20 0 20 20 0 Acenaphthylene 1 20 20 0 20 20 0 20 20 0 Acenaphthene 1 20 20 0 20 20 0 20 20 0 Fluorene 1 20 20 0 20 20 0 20 20 0 Phenanthrene 1 88 59 (33) 120 35 (71) 110 55 (50) Anthracene 1 20 20 0 27 20 (26) 20 20 0 Fluoranthene 1 93 74 (20) 250 83 (67) 130 140 7 Pyrene 1 60 51 (15) 160 64 (60) 90 85 (6) Benzo(a)anthracene 1 51 44 (14) 120 54 (55) 85 61 (28) Chrysene 1 85 87 2 230 56 (76) 170 80 (53) Benzo(b)fluoranthene 1 47 45 (4) 110 86 (22) 67 110 39 Benzo(k)fluoranthene 1 20 20 0 33 25 (24) 23 30 23 Benzo(a)pyrene 2 40 40 0 40 40 0 40 40 0 Indeno(1,2,3-c,d)pyrene 2 40 40 0 40 40 0 40 40 0 Dibenzo(a,h)anthracene 2 40 40 0 40 40 0 40 40 0 Benzo(g,h,i)perylene 2 40 40 0 40 40 0 40 40 0 1: Concentrations listed as ‘20' were flagged with “no measurable response”. Concentrations listed as less than 100 were flagged with “a measurable trace amount”. 2: Concentrations listed as ‘40' were flagged with “no measurable response”. In Tables 1 and 2, data are highlighted in bold text if a concentration exceeded the O. Reg. 153/04 Table 1 background-based concentration. If concentrations exceeded the O. Reg. 153/04 Table 3 health-based criteria the data are bolded and underlined. Discussion Confirmation that there are PAHs in the air is drawn from the Norway maple foliage data. There are no legislated criteria for these compounds in vegetation, nor are there published background data other than in MOE Phytotoxicology reports that address other PAH sources. These limited reports indicate that background concentrations of PAHs in vegetation are at or below the MOE LSB method detection limit. Consequently, it can be said that detection of PAHs in vegetation samples is evidence that a nearby source exists. Table 3 reveals detectable concentrations at all three foliage sampling locations. The PAHs that were detected appear to be primarily the mid-molecular weight PAHs. The sequence in which the PAH compounds are listed in the preceding data tables is from the low molecular weight, two-ring naphthalene, to the five-ring higher molecular weight compounds. It also appears that foliage at Site 2 is exposed to higher air concentrations of these compounds, Page 8 of 12 Report No.: Phyto-S5020-2005