Polychlorinated Biphenyls in Tree Bark near Former Manufacturing

May 16, 2016 - We collected 27 tree bark samples near Sauget, IL, where 373 000 mt of polychlorinated biphenyls (PCB) was produced between 1936 and 19...
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Polychlorinated Biphenyls in Tree Bark near Former Manufacturing and Incineration Facilities in Sauget, Illinois, United States Mark H. Hermanson,*,†,‡ Richard Hann,‡ and Glenn W. Johnson§ †

Hermanson & Associates LLC, 2000 West 53rd Street, Minneapolis, Minnesota 55419 United States Department of Arctic Technology, University Center on Svalbard, NO-9171 Longyearbyen, Svalbard, Norway § Energy & Geosciences Institute, University of Utah, Salt Lake City, Utah 84108, United States ‡

S Supporting Information *

ABSTRACT: We collected 27 tree bark samples near Sauget, IL, where 373 000 mt of polychlorinated biphenyls (PCB) was produced between 1936 and 1977 and 10 245 mt was incinerated from 1971 to 1977. Our goal was observe PCB distribution and apparent movement to residential sites, where 24 of 27 samples were collected. Only one of several waste sites was accessible for sampling. We analyzed for 209 PCB congeners, and 85 peaks are reported (other congeners either coeluted or were near or less than the detection limit). Concentrations of ∑PCB ranged from 190 952 to 2 383 988 pg g lipid−1; 24 of 27 samples had less than 50% of the maximum concentration. Two samples with the highest ∑PCB concentrations were downwind from the plant site in residential areas, but both were among the farthest away from the production facility. One high-concentration sample was near the waste site. The three highest concentrations were in trees that were less than 20 years old, showing recent atmospheric PCB mobility. The percentage of ∑PCB distributions showed a consistent but variable pattern of diCB to nonaCB congeners. DecaCB was inconsistent, because PCB-209, which was manufactured at the site in Aroclor 1270 and 1271, was the most abundant congener in 10 of the samples but lower in others.

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INTRODUCTION Tree bark is a long-term passive sampler of atmospheric contaminants that is useful while the tree is alive and the bark remains on the tree. It has been used to identify the magnitude and distribution of persistent organic contaminants around manufacturing and disposal areas and at remote sites around the world.1−3 Bark is considered to be useful for locating sources of contaminants because tree exposure will be comparatively high near a source.4 In general, tree bark contaminants represent an average exposure over the life of the tree. The movement of organic contaminants to tree bark is related to the octanol/air partition coefficient (log Koa), which predicts the movement of a compound to octanol (a surrogate for bark lipid) or air at equilibrium. The log Koa of individual compounds has a linear relationship with a bark/air partition coefficient up to log Koa ∼ 10.5 At higher log Koa, it is assumed that contaminants are particle-associated and will be captured by the physical roughness of the bark surface. Polychlorinated biphenyls (PCBs) have been found in tree bark near sites where PCBs were made6 or discarded after use2,7−9 and in remote areas with no apparent local source.7 The accumulation of PCBs in bark results from extremely long environmental lifetimes for PCBs, especially for tetraCB and higher chlorinated homologues10 for which log Koa values range from 8.05 (PCB-40) to 12.29 (PCB-209).11 This suggests that © XXXX American Chemical Society

tetraCB through decaCB congeners will be found in bark but that heptaCB and higher congeners (all with log Koa > 10) and a few pentaCB and hexaCB compounds will have the same bark/air proportion and will be transported on particles, while other congeners will move to bark in the gas phase. Here we report the quantitative and qualitative characteristics of PCBs in tree bark in areas near one of two production sites in the United States, which was also the site of incineration of waste PCBs and production residue for the final ∼6 years of production. Our emphasis is on quantification of PCBs in trees growing in residential areas nearby. With 209 PCB-congener analysis, we have comprehensive coverage of all commercial PCB products made on site that may have been released to the environment. Study Site. Our study site is Sauget and surrounding communities, including East St. Louis and Cahokia [Figure S1, Supporting Information (SI)], all in St. Clair County, IL. The largest of two chemical manufacturing sites in the area, known as the W. G. Krummrich (WGK) plant, was the site of PCB production and incineration and is at the center of an industrial Received: March 2, 2016 Revised: May 7, 2016 Accepted: May 16, 2016

A

DOI: 10.1021/acs.est.6b01053 Environ. Sci. Technol. XXXX, XXX, XXX−XXX

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Environmental Science & Technology complex surrounded by another chemical plant, two metal production sites, and smaller manufacturing to north and south. WGK has a long history of chemical production (from ∼1917) and its contaminant emissions along with other plants in the area represent the largest single source of air pollution risk in the St. Louis Metropolitan Statistical Area (MSA).12 A further description of the site appears in the work by Hermanson and Johnson1 and United States Environmental Protection Agency.13 PCB Production at WGK. PCBs were manufactured at two sites in the United States, the original plant in Anniston, AL, beginning in the late 1920s and the second at WGK, beginning in 1936. The types of PCB products (Aroclors) produced at the two were different at various times, and the quality was higher at Anniston because of sulfur contamination in the chlorine produced at WGK.14 By 1967, annual PCB production capacity at WGK was 13 409 mt, with a plan to increase that to 31 591 mt assuming that the plant would continue production into the 1980s.15 A projection made in 1970 anticipated 32% production growth by 1973,16 but in fact, production peaked at WGK in 1970 at 22 540 mt and ended in 1977.17 It has been estimated that total PCB production at WGK was nearly 373 000 mt,17 which was ∼48% of total US production using earlier production estimates for Anniston.6 The different types of PCB production at Sauget included Aroclor 1270 and Aroclor 1271 beginning in 1938 and 1945,18 respectively, and MCS 1016 (later called Aroclor 1016) beginning in 1971.19 The latter was intended to replace Aroclor 1242 with a more biodegradable product. The distillation residue from MCS 1016 was used to make “late-production” Aroclor 1254 and Aroclor 1260, which had different congener distributions from earlier formulations.19,20 The MCS 1016 process reduced a long-standing PCB-production waste problem at WGK associated with Aroclor 1242.21 Waste products from PCB and other chemical production at WGK were deposited at what are now known as Sauget Area 2 (SA2) Sites P, Q, and R, with Site R being by far the largest (Figure S2, SI).16 Some wastes were incinerated beginning in 1973 (see below). Atmospheric PCB Emissions at WGK. In 1970, atmospheric emissions from PCB production were estimated to be 3.2 kg d−1.22 Considering that production peaked at 22 540 mt in 1970, this loss represents a production-related loss factor of 5.18 × 10−5. Using the total PCB production figure from WGK of 373 000 mt,17 19.2 mt of PCB would have been lost to the atmosphere between 1936 and 1977 from production, slightly less than the 20.5 mt estimated for Anniston6 and consistent with production amounts. This estimate does not consider that new equipment was installed in 1975 at WGK to reduce PCB production losses to the atmosphere.21 In 1976, an estimated proportion of atmospheric emission from outdoor storage tanks alone during PCB production years was nearly 1.0 × 10−4 (0.01% of production), nearly a factor of 2 greater than estimated from production loss in 1970. Total loss from 1936 to 1977 from this source alone would have been 37.3 mt, again assuming 373 000 mt total production.17 During that same year, air sampling outside the PCB production area at the heated PCB storage tanks (100 °C) showed an average daily loss of 1.6 kg to the atmosphere,23 although this amount was not related to production levels. This rate is about 50% of the other estimated loss from storage tanks.17

Air inside the PCB production area had variable amounts of PCBs. In October 1975, the amounts ranged from 6 to 338 × 103 ng m−3, which was apparently vented outside (see below).24 A report in 1976 showed that the work area concentrations in the PCB manufacturing area varied from 70 to 320 × 103 ng m−3, with the latter value being observed at a PCB drumming station and a peak value of 370 × 103 ng m−3 being recorded by a personal sampler worn by a plant worker.25 Again, these concentrations were clearly being vented to the atmosphere. Emissions before 1970 were well-known because of production losses inside the plant that were intended to be vented outside. For example, the procedure for drawing off final distillation residues, called Montars (which became a waste product), at the end of PCB production required exhaust of “toxic fumes” (>300 °C), presumably containing PCBs.26 The first investigation of PCBs in air inside a production facility were in Anniston in 1953, when concentrations were found to range between 0.35 to 5 mg m−3.27 Observations continued in 1954 when the amounts were found to be 2.1 mg m−3 near a distillation apparatus.28 Similar amounts would have been found at WGK, where production processes were similar.17 Both of these suggest that plant air often exceeded 1.0 mg m−3 ∑PCB, which was identified as a workplace maximum after toxicological studies by Drinker et al.,29 and the 0.5 mg m−3 maximum permissible in workplace air standard established in 1939 based on further toxicity studies.30 These workplace air limits from the 1930s assumed adequate ventilation inside the plant. There are no statements in available documents indicating the type or quality of ventilation used at WGK. But this air would eventually have left the production area and moved outside, where it is assumed to have affected the local environment.17 It was not until 1970 that an inventory of PCB production area vents was ordered to estimate plant PCB losses.31 PCB Incineration at WGK. When restrictions on PCB uses began in 1970, plans were developed to build an incinerator on the WGK site to burn PCBs that were returned by customers whose applications were no longer permitted.32 The incinerator was also intended to burn PCBs that were captured from production and transfer processes at WGK.33 The incinerator began operation in May 1971 and continued through October 1977,34 about the time that PCB production ended.17 Beginning in July 1973, the incinerator was also used to burn plant process wastes, including PCB distillation residues (Montars), which continued until production ended in 1977.35 The most detailed report available about the operation of the PCB incinerator appeared in 1975.36 The intended design of the system was to burn 570 kg of PCBs per hour.32 In reality, the average rate of feed in 1975, one of the more successful years, was 236 kg h−1. We have assumed earlier that a total of 10 455 mt of PCBs was burned in the incinerator over ∼6 years, with an average burn of ∼170 kg h−1 assuming continuous operation. However, there were many times when the incinerator was out of service,32 so the 1975 rate of 236 kg h−1 may be closer to an actual operational value. ∑PCB emissions from the incinerator from 46 measurements in 1971 (from May 27 to December 10) ranged from 0.08 to 43 g d−1, suggesting widely varying operating conditions.23,37 Emissions were less variable in 1973, when the range was from 0.47 to 2.7 g d−1. During 1975, the emissions were more consistent at ∼2 g d−1.37 This contrasts with the overestimated emission of 12 g d−1 during the incinerator lifetime assumed by Weeks.17 The average measureB

DOI: 10.1021/acs.est.6b01053 Environ. Sci. Technol. XXXX, XXX, XXX−XXX

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Figure 1. Distribution of ∑PCB in tree bark around the WGK plant in Sauget, IL. Sites ECS-11 and ECS-12 do not resolve at this map scale; both are in the same color category. Base map image copyright 2015 Microsoft Corp. and HERE.

ment from 1971 to 1975 = 2.1 g d−1 or ∼5 kg during the ∼6 year operation of the incinerator, suggesting a very high efficiency of PCB destruction, saving nearly all of 10 455 mt of incinerated PCBs from going into landfills or the atmosphere.24,37 It is assumed that PCB congeners measured were the same for all samples from 1971 to 1975, although the congeners analyzed are not identified. Materials and Methods. To investigate the residual atmospheric effects of decades of PCB production and emission at Sauget, a field team collected 27 tree bark samples at sites around the Sauget industrial complex (Figure 1), up to a distance of 4.2 km from WGK, in February 2009, largely in East St. Louis and Cahokia with a few samples collected in Sauget. Samples are designated “ECS”. Collection data (tree location, type, age, lipid content) appear in Table S1 (SI). Most of the samples were collected in residential areas downwind to the east and north from WGK, largely in East St. Louis and Cahokia (a wind rose appears in Figure S3, SI). Some samples were collected upwind: Three samples were collected to the west of WGK, two from trees growing on SA2 Site P (samples ECS-8, ECS-9), a WGK waste disposal site operating from 1973 to 1984 (see Figure S2, SI). Another westward site was located near the Mississippi River in St. Louis (sample ECS21). These were the only samples collected from industrial sites. We were not able to gain access to any other waste site in Sauget, particularly Sites Q and R (Figure S2, SI), which were used to discard WGK production wastes for decades until the late 1970s.38 Six samples were collected upwind (to the south) near Dead Creek (samples ECS-7, ECS-15−19), which drains the industrial complex located to the north. Sampling sites were selected largely based on the availability of trees and the permission of property owners where they were located.

We collected about 50−60 g of bark at breast height from each tree. Bark was cleaned if necessary by removing lichen, moss, or other nonbark material. Bark was removed with a chisel (rinsed with dichloromethane between samples) and allowed to fall into a precleaned 500 mL jar. After sampling, the jars were closed with Teflon-lined covers. At the time of bark sampling, a bore was taken from each tree with an increment borer to measure the tree’s age. In the laboratory, an aliquot of bark (100, except that of PCB-105 (4.25) and PCB-118 (15.6). The signal/detection ratios are all greater than 25, except for that of PCB-105 (7.23), PCB-109 (16), and PCB-137 (25). The average detection levels for all 27 samples are shown in Table S7a,b (SI).

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RESULTS AND DISCUSSION Total PCB Concentrations. Total PCB concentrations ranged from 190 945 to 2 383 988 pg g−1 lipid (Figure 1). Within this range, 24 of 27 samples had concentrations 30 for six of the congeners in the “all samples” category. The result taken from this is that there is a fairly common background type of PCB congener distribution in all samples, including those dominated by PCB-209. However, with PCB-209 there is a clear indication, again, that its source is generally unrelated to other PCB congeners, which is consistent with Aroclor 1270 or 1271 as sources because, in E

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was found to be more than 1% in five samples (ECS-3, -19, -22, -24, -27) which have no particular geographic relationship to one another (Figure 1). There does not appear to be a systematic pattern to PCB-11 in the samples from Sauget, suggesting that there is no major thermal or dye-related source common to the entire area. PCB-29 coelutes with PCB-26, which we report, and together they represent less than 0.5% of ∑PCB. PCB-121 was removed from the data set because of extremely low or less than detected concentrations. Dioxin-like (DL) PCBs. Among the 12 DL PCBs, we report six, including PCB-77, -105, -118, -167, and -156+157. Combined these make up 6.3% of ∑PCB in the average sample (see Figure 2), more than half of that being contributed by PCB-118 (3.2%). The total toxic equivalency (TEQ) for these congeners in the most concentrated tree (ECS-25), based on 2005 TEF values,48 was 6.4 pg g−1 lipid, in comparison to 410 pg g−1 lipid in this sample for ∑PCDD+PCDF TEQ.1 Clearly the contribution of DL-PCBs to TEQ at Sauget is small. In the tree bark PCB study in China by Wen et al.,9 the mean PCB-based TEQ using 2005 TEF values48 for DL PCBs was 460 pg g−1 lipid, 89% being contributed by PCB-126, which we did not report from Sauget. The mean Luqiao PCB TEQ without PCB-126 would be 50 pg g−1 lipid, nearly 8 times greater than our maximum Sauget sample. PCB-209. The dominance of PCB-209 in 10 tree bark samples (and second most in two others) indicates that PCB209 has an important history in Sauget. The high amounts of PCB-209 that we observe in many samples could be production residues of Aroclors 1270 and 1271. Another source may have been pentachlorophenol (PCP), which, when reacting with NaOH, releases sodium pentachlorophenolate (PCP-Na), which produces and releases PCB-209 when heated.49 Both PCP and NaOH were made at WGK into the 1970s.50 Between 1938 and 1949, Aroclor 1270 was manufactured at WGK.18 Aroclor 1271 production began in 1945 and also ended in 1949; it was considered to be 100% PCB-209.18 Hartmann et al.45 suggest that PCB-206 content in Aroclor 1270 was ∼5.9% and in Aroclor 1271 it was 1.7%. Both products were solids, unlike other Aroclors, and required a flaking process after chlorination. This flaking process was known to result in emission of “fumes” that had to be vented and may be how PCB-209 was distributed to soils and tree bark downwind from the plant.41,42,51 Fume production had special hazards because the “fumes” would solidify in the air which, on contact with skin, were known to result in cases of dermatitis among plant workers. The cure was assumed to be simple and effective,51 but lingering effects were suspected, resulting in legal settlements with some workers years later.52 Production of Aroclors with chlorine content greater than 68% required a two-step chlorination process, the second step requiring heating for 24 h at a temperature greater than 300 °C,18 which is why production of Aroclors 1270 and 1271 was likely considered to be uneconomical and ended in 1949. The special production equipment used for these formulations was dismantled in 1952 at WGK.18 Total production of these two Aroclors between 1938 and 1949 was ∼582 mt for Aroclor 1270 and ∼42 mt for Aroclor 1271,53 both low amounts in comparison to the ∑PCB production of 50 325 mt at that time (1.2% of total WGK production from 1938 to 1949).17 However, Aroclors 1270 and 1271 are not mixtures but are predominantly composed of one congener, so comparing production amounts directly to other PCB congener mixtures is not particularly meaningful.

effect, there were no other PCB congeners in the products beyond small amounts of PCB-206.45 Figure 4 also suggests that Aroclor mixtures dominated by PCB-199 (Aroclor 1262) or PCB-206 (Aroclor 1268) are not large contributors to the average Sauget tree bark sample. An exception is ECS-27 (Figure S31, SI), in which congeners from heptaCB to nonaCB homologues show a strong and significant correlation to Aroclor 1262 (r = 0.72, ρ ≪ 0.01) using data from Frame et al.40 In our tree bark PCB analysis in Anniston, PCB-70+74 dominated 10 of 44 trees sampled, about the same proportion of dominance at Sauget (7 of 27). However, PCB-70+74 was most or second-most concentrated in 14 Sauget samples (and in the top 3 of 18 samples; see Table S9, SI), suggesting a high level of persistence and a concentrated source. We have found that PCB-70+74 are among the more persistent abiotic environmental congeners in a completely different environment, for example, being among the most abundant five PCB congeners in glacier ice from Svalbard, Norway46 affected only by long-range atmospheric transport. The indication is a high level of persistence and transportability of PCB-70+74 in variable environments. The other common dominant congeners in Sauget, PCB-138 and PCB-209, were not dominant in any Anniston trees. The other most frequent dominant congeners in Anniston were PCB-28 and PCB-66 (seven samples each) and PCB-44 and PCB-180 (five samples each). The comparable PCB homologue abundance of the average Sauget sample is shown in Figure S4 (SI), a condensed version of Figure 3. Here the tetraCB, pentaCB, and hexaCB homologues are dominant, combined making up ∼57% of the average sample. This shows that the dominant parent products were likely to have been Aroclors 1242, 1248, and 1254, and what remains in Sauget tree bark is the persistent congeners. In the tree bark PCB study in China by Wen et al.,9 the dominant homologues (79.3% of ∑PCB) were triCB, tetraCB, and pentaCB, a significant contrast to our average result [Figures 3, S4 (SI)]. However, Wen et al. note that PCBs produced in China were dominated by triCB congeners. The 20 most concentrated PCB peaks in Sauget tree bark, and their log Koa values, are shown in Table S9a−e (SI). The data show many of the same congeners appearing among this group. The log Koa values of these range from 7.13 to 12.29. PCB-28 was found in 26 samples (not in ECS-10) and was the lowest log Koa for all but one (ECS-17). PCB-209 was found among the top 20 in 23 of 27 samples and, of course, had the highest log Koa for all of those samples. The average sample log Koa among the top 20 peaks in 27 samples was 9.58 ± 0.28, so the range is small (9.12−10.16), with only one sample with log Koa greater than 10 (ECS-27). This result supports the relationship between log Koa and bark/air partitioning proposed by Zaho et al.,5 although we have no air data for full verification. We assume that dominant congeners are also influenced by the magnitude of the source and not just log Koa, considering the presence of PCB-209 (log Koa = 12.29) at the highest concentration in 10 of the samples. Non-Aroclor PCB. It is necessary to investigate the appearance of what would be considered “non-Aroclor” PCBs in our Sauget samples, including those of interest to the dye industry, which would include PCB-11, PCB-29 and PCB121.47 Among these, PCB-11 was found in every sample; its average percent of ∑PCB was less than 1% in 22 samples. It F

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Figure 5. Distribution of PCB-209 in tree bark around the WGK plant in Sauget, IL, where PCB-209 was produced from 1938 to 1949. Sites ECS-11 and ECS-12 do not resolve at this map scale; both are in the same color category. Base map image copyright 2015 Microsoft Corp. and HERE.

Even though production of these Aroclors ended in 1949,58 Aroclor 1270 was listed as a product in company advertising into the 1960s.59 In addition, there was mention of the possibility of producing Aroclor 1272 as late as January 1971,52 perhaps because it was finding additional use by casting operations in the early 1970s.42 As late as 1973, there was mention of production of decachlorobiphenyl for specific customers.60 However, actual production of PCB-209 in the 1970s at WGK cannot be verified with available documents. In the 1976 soil PCB survey, all samples contained PCB-209: the percentage of ∑PCB ranged from 5.3−93% and averaged 36%. The samples 700 m away averaged 46.9%, suggesting that PCB-209 was traveling farther from the plant than congeners found in Aroclor 1242 and Aroclor 1260.42 In the 2009 soil survey,41 PCB-209 was found in 10 of 11 samples with detected PCBs in the north and was 100% of observed ∑PCBs in 7 of those samples. PCB-209 was found in all 17 samples where PCBs were detected in the south and was 100% of the observed ∑PCB in 5 of them. In other samples, PCB-209 ranged from 16 to 77% of ∑PCB. Other congener data are not available. In both soil surveys, the PCB-209 was a higher proportion of ∑PCB than we observed in tree bark, but it is not possible to assess the importance of this without knowing what congeners made up the “∑PCB” in soils.

The distribution of PCB-209 in samples from the Sauget site is shown in Figure 5. All eight of the highest-concentration samples are downwind from WGK, mostly to the north (ECS5, ECS-6, ECS-14, ECS-20, ECS-25), but two are downwind to the east (ECS-11, ECS-12) and one is near SA2 Site P (ECS-8), a WGK waste site. The indication is that PCB-209 moving off site was influenced by dominant wind. Of these eight trees, the age ranges from 8 to 55 years (Table S1, SI), suggesting that PCB-209 has been in the environment almost back to the time of Aroclor 1270 and 1271 production (ending in 1949) but also that it is still moving through the atmosphere, as shown by the two higher-concentration 8-year-old samples (ECS-8, ECS-12). The concentrations of PCB-209 among samples in comparison to highest-to-lowest ∑PCB are shown in Figure 2. There is no pattern consistency with ∑PCB, showing again that PCB-209 concentration distribution has little association with ∑PCB. In fact, the distributions are weakly correlated (r = 0.4576, ρ = 0.016). Uses of Aroclors 1270 and 1271 are not well documented, but it is known that Aroclor 1270 was useful as a hightemperature insulator in electrical cable.54 It was also found to be useful as an additive to polystyrene to increase dielectric properties and to increase resistance to physical failure at high temperatures (greater than100 °C).55 Aroclor 1270 was proposed as a flame retardant in rubber products during the 1940s.56 PCB-209 (or decachlorobiphenyl) was also used in the investment casting industry,41,42,54 and after 1949 was purchased by the industry from Italian manufacturers.57 There is no indication that investment casting was performed by any industry in the Sauget area, but areas with historic investment casting could be contaminated with PCB-209, considering its apparent persistence observed at Sauget.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.6b01053. An analytical method narrative, sample identification table, 7 QC data tables, an eigenvalue table, a table of 20 G

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(16) Krull, W. A.; McCutcheon, R. M.; Humphries, R. N.; Fabian, R. O. Manufacturing Improvement Plan for Aroclor. Department 246; Monsanto Chemical Co.: St. Louis, 1970; Bates No. MONS035010− MONS035032. (17) Weeks, D. A. Air Modeling Analysis of Potential Historical Releases at W. G. Krummrich Plant, Sauget, IL; Technical Report; Risk Management & Engineering, Ltd.: Garland, TX, January 2011. (18) Mather, E. Process for the Production of Aroclors, Pyranols, etc. at the Anniston and at the Wm. G. Krummrich Plant. Monsanto Chemical Co.: St. Louis, MO, April 1955; Bates No. MONS045979− MONS046486. (19) Silver, J. E. Tentative Process on MCS 1016; Organic Chemicals Division Research Report P-1579; Monsanto Co., October 7, 1970; Bates No. MONS034954−MONS034997. (20) Johnson, G. W.; Hansen, L. G.; Hamilton, M. C.; Fowler, B.; Hermanson, M. H. PCB, PCDD and PCDF congener profiles in two types of Aroclor 1254. Environ. Toxicol. Pharmacol. 2008, 25, 156−163. (21) Johnson, G. L. Standard Manufacturing Process for Aroclor 1016. Department 246; Monsanto Chemical Co.: St. Louis, MO, March 1976; Bates No. MONS061791−MONS061903. (22) Krull, W. A. Aroclor Pollution, Air Pollution Reduction Program; Progress Report, Technical Services Program; W. G. Krummrich Plant, Monsanto Chemical Co.: Sauget, IL, Dec 4, 1970; Bates No. MONS056604−MONS056605. (23) Zylstra, R. E. Calculation of PCB air Emission from Storage and Dispensing Operations at the Krummrich Plant of Monsanto; U.S. Environmental Protection Agency, March 5, 1976; Bates No. MONS054043−MONS054048. (24) PCB Concentrations in Atmosphere; Monsanto Chemical Co.; Sauget, IL, 1975; Bates No. MONS077966−MONS077967. (25) Air Sampling Data, Department 246, Aroclor 1016 Production Area; W. G. Krummrich Plant, Monsanto Chemical Co., Sauget, IL, 1976; Bates No. MONS076117−MONS076121. (26) Process Function Outline, Aroclor Department; Monsanto Chemical Co., 1965; Bates No. DSW001758−DSW001788. (27) Richards, H. B., Jr. Interim Report on Aroclor in Gases; Report No. 2892; Phosphate Division, Monsanto Chemical Co.: Anniston, AL, 1953; Bates No. MONS058945−MONS058957. (28) Richards, H. B., Jr. Final Report on Aroclor in Gases; Report No. 2970; Phosphate Division, Monsanto Chemical Co.: Anniston, AL, 1954; Bates No. DSW147758−DSW147773. (29) Drinker, C. K.; Warren, M. F.; Bennet, G. A. The problem of possible systemic effects from certain chlorinated hydrocarbons. J. Ind. Hyg. Toxicol. 1937, 19, 283−299. (30) Drinker, C. K. Further observations on the possible systematic toxicity of certain of the chlorinated hydrocarbons with suggestions for permissible concentrations in the air of workrooms. J. Ind. Hyg. Toxicol. 1939, 21, 155−159. (31) Wright, E. G., et al. Sampling of Atmosphere and Water for Aroclor Losses; Memo to G. W. Miller, et al.; Monsanto Chemical Co.: Anniston, AL, July 20, 1970; Bates No. DSW015029−DSW015030. (32) Pier, A. F. Incineration of Polychlorinated Biphenyls; Corporate Engineering Division, Monsanto Chemical Co.: St. Louis, MO, August 1972; Bates No. MONS044175−MONS044183. (33) Rasmussen, A. L. Waste PCB Transferring; Memo to various department heads; Monsanto Chemical Co., September 15, 1970; Bates No. MONS098958. (34) Questions & Answers Regarding the Monsanto PCB Incinerator; Monsanto Chemical Co., Oct 31, 1977. Bates No. MONS000476− MONS000478. (35) Boucher, K. E. Manufacturing Improvement Plan for Aroclor, Pyranol, and Aroclor Incineration, Departments 246, 259, 831; W. G. Krummrich Plant, Monsanto Chemical Co.: Sauget, IL, 1974; Bates No. MONS038305−MONS038317. (36) Department 790, Aroclor Incineration; Operations Report; Monsanto Chemical Co., 1975; Bates No. MONS045856− MONS045860. (37) PCB Waste Handling at Sauget and Anniston; Monsanto Chemical Co., 1976; Bates No. MONS049349−MONS049351.

most-concentrated peaks in each sample, and Figures S1−S31 (PDF)

AUTHOR INFORMATION

Corresponding Author

*Telephone: 267 207 7895 (US), +47 46230186 (Norway); email: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are grateful to private property owners who allowed their trees to be sampled. J. R. Brozowski dated the tree bores and keyed the trees. Michelle Donnelly-Kelleher analyzed lipids. Georgina Brooks from AXYS Analytical offered helpful interpretations of the data.

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REFERENCES

(1) Hermanson, M. H.; Johnson, G. W. Chlorinated dibenzo-p-dioxin and dibenzofuran congener and homologue distributions in tree bark from Sauget, Illinois, US. Environ. Sci. Technol. 2015, 49, 855−862. (2) Salamova, A.; Hites, R. A. Evaluation of tree bark as a passive atmospheric sampler for flame retardants, PCBs, and organochlorine pesticides. Environ. Sci. Technol. 2010, 44, 6196−6201. (3) Simonich, S. L.; Hites, R. A. Global distribution of persistent organochlorine compounds. Science 1995, 269, 1851−1854. (4) Peverly, A. A.; Salamova, A.; Hites, R. A. Air is still contaminated 40 years after the Michigan Chemical Plant disaster in St. Louis, Michigan. Environ. Sci. Technol. 2014, 48, 11154−11160. (5) Zhao, Y.; Yang, L.; Wang, Q. Modeling persistent organic pollutant (POP) partitioning between tree bark and air and its application to spatial monitoring of atmospheric POPs in mainland China. Environ. Sci. Technol. 2008, 42, 6046−6051. (6) Hermanson, M. H.; Johnson, G. W. Polychlorinated biphenyls in tree bark from a former manufacturing area in Anniston, Alabama. Chemosphere 2007, 68, 191−198. (7) Hermanson, M. H.; Hites, R. A. Polychlorinated biphenyls in tree bark. Environ. Sci. Technol. 1990, 24, 666−671. (8) Meredith, M. L.; Hites, R. A. Polychlorinated biphenyl accumulation in tree bark and wood growth rings. Environ. Sci. Technol. 1987, 21, 709−712. (9) Wen, S.; Yang, F.; Li, J. G.; Gong, Y.; Zhang, X.; Hui, Y.; Wu, Y. N.; Zhao, Y. F.; Xu, Y. Polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs) monitored by tree bark in an E-waste recycling area. Chemosphere 2009, 74, 981−987. (10) Paasivirta, J.; Sinkkonen, S. I. Environmentally relevant properties of all 209 PCB congeners for modeling their fate in different natural climactic conditions. J. Chem. Eng. Data 2009, 54, 1189−1213. (11) Chen, J.; Xue, X.; Schramm, K.-W.; Quan, X.; Yang, F.; Kettrup, A. Quantitative structure-property relationships for octanol-air partition coefficients of polychlorinated biphenyls. Chemosphere 2002, 48, 535−544. (12) Abel, T. D. Skewed riskscapes and environmental injustice: A Case Study of Metropolitan St. Louis. Environ. Manage. 2008, 42, 232−248. (13) Statement of Basis for Solutia Inc., Sauget, IL; U.S. EPA I.D. No. ILD 000 802 702; U.S. Environmental Protection Agency: Chicago, 2007; 31 pp. (14) Yates, R. S. Changes to Anniston and Krummrich Aroclor Production; Monsanto Chemical Co., July 9, 1965; Bates No. MONS036162−MONS036173. (15) Yates, R. S. AroclorsIncrease Aroclor CapacityOrganic Division; Monsanto Chemical Co., August 28, 1967; Bates No. MONS036255. H

DOI: 10.1021/acs.est.6b01053 Environ. Sci. Technol. XXXX, XXX, XXX−XXX

Article

Environmental Science & Technology (38) Public Health Assessment Sauget Area 2, Landfill Sites P, Q, R, Sauget, St. Clair County, Illinois, EPA Facility ID# ILD000672329; Illinois Department of Public Health, 2004. (39) Odabasi, M.; Ozgunerge Falay, E.; Tuna, G.; Altiok, H.; Kara; Dumanoglu, Y.; Bayram, A.; Tolunay, D.; Elbir, T. Biomonitoring of spatial and historical vatiations of persistent organic pollutants (POPs) in an industrial region. Environ. Sci. Technol. 2015, 49, 2105−2114. (40) Frame, G. M.; Cochran, J. W.; Bøwadt, S. S. Complete PCB congener distributions for 17 Aroclor mixtures determined by 3 HRGC systems optimized for comprehensive, quantitative, congenerspecific analysis. J. High Resolut. Chromatogr. 1996, 19, 657−668. (41) Gonzalez, J.; Feng, L.; Sutherland, A.; Waller, C.; Sok, H.; Hesse, P. G. R.; Rosenfeld, P. PCBs and dioxins/furans in attic dust collected near former PCB production and secondary copper facilities in Sauget, IL. Procedia Environ. Sci. 2011, 4, 113−125. (42) Stratton, C. L.; Sosebee, J. B., Jr. PCB and PCT contamination of the environment near sites of manufacture and use. Environ. Sci. Technol. 1976, 10, 1229−1233. (43) Final Decision and Response to Comments for Solutia Inc., Sauget, IL; EPA I. D. No. ILD 000 802 702; U.S. Environmental Protection Agency: Chicago, 2008; 12 pp. (44) Zhou, L.; Dong, L.; Huang, Y.-R.; Shi, S.-X.; Zhang, L.-F.; Zhang, X.-L.; Yang, W.-L. Tree bark as a biomonitor for the determination of polychlorinated biphenyls and polybronminated diphenyl ethers from Southern Jiangsu, China: levels, distribution and possible sources. Environ. Monit. Assess. 2015, 187, 603. (45) Hartmann, P. C.; Quinn, J. G.; Cairns, R. W.; King, J. W. Polychlorinated biphenyls in Narragansett Bay surface sediments. Chemosphere 2004, 57, 9−20. (46) Garmash, O.; Hermanson, M. H.; Isaksson, E.; Schwikowski, M.; Divine, D.; Teixeira, C.; Muir, D. C. G. Deposition history of polychlorinated biphenyls to the Lomonosovfonna glacier, Svalbard: A 209 congener analysis. Environ. Sci. Technol. 2013, 47, 12064−12072. (47) Alarie, Y.; Iwasaki, M.; Stock, M. F.; Pearson, R. C.; Shane, B. S.; Lisk, D. J. Effects of inhaled municipal refuse incinerator fly ash in the gunea pig. J. Toxicol. Environ. Health 1989, 28, 13−25. (48) Van den Berg, M.; Birnbaum, L. S.; Denison, M.; De Vito, M.; Farland, W.; Feeley, M.; Fiedler, H.; Hakansson, H.; Hanberg, A.; Haws, L.; Rose, M.; Safe, S.; Schrenk, D.; Tohyama, C.; Tritscher, A.; Tuomisto, J.; Tysklind, M.; Walker, N.; Peterson, R. E. The 2005 World Health Organization reevaluation of human and mammalian toxic equivalency factors for dioxins and dioxin-like compounds. Toxicol. Sci. 2006, 93, 223−241. (49) Hagenmaier, H.; Berchtold, A. Analysis of waste from production of Na-pentachlorophenolate for polychlorinated dibenzodioxins (PCDD) and dibenzofurans (PCDF). Chemosphere 1986, 15, 1991−1994. (50) Esposito, M. P.; Tiernan, T. O.; Dryden, F. E. Dioxins; EPA600/2-80-197; U.S. Environmental Protection Agency: Cincinnati, OH, 1980. (51) Mather, E. Aroclors: Toxicity; Memo to P. J. C. Haywood; Monsanto Chemical Co.: St. Louis, MO, December 11, 1951; Bates No. DSW001106−DSW001107. (52) Williams, M. Memo to B. O. Severson; Monsanto Chemical Co.: St. Louis, MO January 20, 1971; Bates No. MONS099489− MONS099490. (53) Department 246 Production Figures; Monsanto Chemical Co., October 7, 1947; Bates No. MONS046348. (54) Rosch, S. J. Heat resistant electric insulation comprising rubber and chlorinated diphenyls. U.S. Patent Application 2,416,955, May 29, 1942. (55) Berberich, L. J.; Swiss, J. Plastic composition. U.S. Patent Application 2,333,513, May 3, 1941. (56) The Aroclors: Physical Properties and Suggested Applications; Application Data Bulletin No. P-115; Monsanto Chemical Co.: St. Louis, MO, 1945; Bates No. FUN001991−FUN002011. (57) Development of a Study Plan for Definition of PCBs Usage, Wastes and Potential Substitution in the Investment Casting Industry. Task III; EPA 560/6-76-007; U.S. EPA, 1976.

(58) AroclorSynopsis of the Process; Monsanto Chemical Co.: St. Louis, MO, 1955; Bates No. MONS045984. (59) The Aroclors: Physical Properties and Suggested Applications; Application Data Bulletin No. O-P-115; Monsanto Chemical Co.: St. Louis, MO, 1960; Bates No. FUN001922−FUN001954. (60) Paton, C. OECD/PCBs; Memo to T. L. Gossage; Monsanto Chemical Co., July 3, 1973; Bates No. MONS029393−MONS029395.

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DOI: 10.1021/acs.est.6b01053 Environ. Sci. Technol. XXXX, XXX, XXX−XXX