Composite surface soil samples were collected at 0, 25, and 50 cm from the base of 12 utility poles on the Kenai National Wildlife Refuge in Alaska, to assess the extent to which pentachlorophenol, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo furans may have leached from pentachlorophenol-treated poles. Six pairs of utility poles were included, consisting of an “old” pole manufactured in 1959 or 1963, a “new” pole manufactured within the past 20 years, and a suitable background soil sample from the same vicinity. Old poles had greater concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQs) near the pole base and at 25 cm than “new” poles did. For all 12 poles combined, the mean pentachlorophenol levels in soil were 1810, 157, and 17.8 ppm dry weight (d.w.) near the pole bases, at 25 and 50 cm from the poles, respectively, while the mean total TEQ levels in soil were 15,200, 5170, and 1510 parts per trillion d.w. at those distances. Surface soil levels of pentachlorophenol and TCDD-TEQs exceeded both human health and ecological risk-based screening levels. The design and results of this study were similar to another project in Montreal, Quebec in Canada. Together the results are cause for concern, indicating that millions of similarly treated utility poles in North America may be point sources of pentachlorophenol and dioxins/ furans to soil. . . . . . Keywords Pentachlorophenol Polychlorinated dibenzo-p-dioxins Polychlorinated dibenzo furans Utility pole Alaska Soil Introduction pentachlorophenol-treated utility poles in service in the USA (Malecki 1992). Commercial pentachlorophenol mixtures used In North America, pentachlorophenol has been used as a wood to treat wood are known to contain polychlorinated dibenzo-p- preservative since 1936. While pentachlorophenol is a general dioxins and polychlorinated dibenzo furans (PCDDs and biocide that has been used for a variety of purposes in the past, PCDFs); the concentration of these contaminants has decreased its only remaining use in the USA is as a heavy-duty wood since pentachlorophenol became more strictly regulated by the preservative, particularly for wood utility poles and cross arms US Environmental Protection Agency (USEPA) in 1987. In (USEPA 2008). In 1992, there were estimated to be 36 million 1987, the USEPA established that commercial pentachlorophe- nol products in the USA could not contain more than 4 ppm of hexachloro-dibenzo-p-dioxins (HxCDD) or exceed 2 ppm Responsible editor: Zhihong Xu HxCDD as a monthly average (Eduljee 1999). Pentachlorophenol-treated utility poles can contain substantial * Lori A. Verbrugge quantities of dioxins and furans and are an important reservoir email@example.com source of these toxic chemicals with the potential to contami- nate the environment (Lorber et al. 2002). U.S. Fish and Wildlife Service, Alaska Regional Office, 1011 E. PCDDs and PCDFs are a class of structurally similar com- Tudor Rd, Anchorage, AK, USA pounds that are toxic to a wide variety of organisms. U.S. Fish and Wildlife Service, Kenai National Wildlife Refuge, P.O. Laboratory animals experimentally exposed to PCDDs and Box 2139, Soldotna, AK, USA PCDFs have exhibited dermal, immunological, and hepatic toxicity; teratogenic, carcinogenic, and neurobehavioral 19188 Environ Sci Pollut Res (2018) 25:19187–19195 effects; endocrine disruption; and biochemical changes in- (EPRI 1995), PCDDs, and PCDFs (Gurprasad et al. 1995; cluding induction of several drug-metabolizing enzymes Bulle et al. 2010) migrate from treated poles into nearby soils. (Ahlborg et al. 1992). They share a common mechanism of Wood treated with pentachlorophenol may release the com- toxicity, and the relative toxicity of each congener is based on pound through volatilization or leaching. Leaching can occur its structural ability to bind with the Ah receptor, which me- as pentachlorophenol moves down the outside of the pole diates toxicity (Safe 1990). Toxic equivalency factors (TEFs) along with rainwater or pentachlorophenol can move with its have been developed for each congener, which express each carrier solvent with the downward force of gravity, either at congener’s toxicity relative to 2,3,7,8-tetrachlorodibenzo-p- the surface or within the pole (USEPA 2008). In water sys- dioxin (TCDD), the most potent PCDD (Van den Berg et al. tems, pentachlorophenol does not undergo hydrolysis in water 1998, 2006). The overall toxicity of a complex mixture of at pH 4to9(USEPA 2008), but it does rapidly photo- PCDDs and PCDFs can be calculated from measured conge- degrade in the presence of direct sunlight (Choudhury et ner concentrations and expressed as TCDD-equivalents or al. 1986). PCDDs and PCDFs are environmentally persis- TCDD-TEQs. PCDDs and PCDDs are environmentally per- tent, with estimated soil half-lives ranging from 17 to over sistent and lipophilic and biomagnify in aquatic food chains 100 years depending on the congener and estimated water (Ahlborg et al. 1992). half-lives ranging from 166 days to 21 years (Sinkkonen Pentachlorophenol uncouples oxidative phosphorylation, and Paasivirta 2000). which interferes with cell respiration and results in a marked The 800,000-ha Kenai National Wildlife Refuge (KENWR) increase in metabolism (Holmberg et al. 1972; Eisler 1989). is located on the Kenai Peninsula in southcentral Alaska, USA Oxygen radicals play a central role in the generation of lipid (60° N, 150° W). Mountains and glaciers characterize the east- peroxidation; in rats the primary metabolite of pentachloro- ern and southeastern portions of the Refuge. The Kenai phenol (tetrachlorohydroquinone) is more toxic than the par- Lowlands, on the western portion of the Refuge, are primarily ent compound (Wang et al. 2001). Pentachlorophenol was permafrost-free beneath a cap by silt loam derived from post- classified by the US EPA as “likely to be carcinogenic to glacial windblown loess (USFWS 2010). The Lowlands consist humans” during its last status review in 2010 (USEPA of wetlands and mixed boreal forest dominatedbyblackspruce 2010). Pentachlorophenol exhibits endocrine-disrupting ef- (Picea mariana), white spruce (Picea glauca), white birch fects at environmentally relevant concentrations, including (Betula neoalaskana), and quaking aspen (Populus anti-estrogenic and anti-androgenic activities at low exposure tremuloides). The climate is boreal with a maritime influence. concentrations in vitro and decreased ovulation in vivo (Orton Temperatures are rarely greater than 26 °C in summer or less et al. 2009). Human exposure to pentachlorophenol decreased than − 18 °C in winter. The frost-free growing season varies significantly in North America following regulatory restric- from 71 to 129 days depending on location, with about 480 mm tions. Pentachlorophenol levels in blood from North of total precipitation per year (USFWS 2010). Abundant wild- Americans had a geometric mean of 123.26 μg/L in the life occur in the Refuge, including moose, bears, mountain 1980s which fell to a geometric mean of 1.36 μg/L after goats, Dall sheep, wolves and other furbearers, salmonids and 1995 (Zheng et al. 2011). other fish, and other migratory and non-migratory birds. Pentachlorophenol accumulates rapidly in exposed fish, The Kenai Lowlands are bisected by the Sterling with uptake primarily from water rather than from the diet Highway that was constructed during 1947–1951. Along (Niimi and Cho 1983). Environmental exposures to high most of the highway segment that runs east to west through levels of pentachlorophenol have resulted in fish kills, bird KENWR lies the utility corridor that provides electricity to deaths, and poisoning of livestock (Eisler 1989). At lower communities on the western peninsula. A local member- concentrations more typically found in the environment, owned utility company has operated electric utility corri- pentachlorophenol may have adverse effects on the repro- dors within the KENWR under US Fish and Wildlife ductive and inter-renal systems of exposed fish. Fish ex- Service-issued Right-of-Way (ROW) Permits for many de- posed to environmentally relevant concentrations of penta- cades. Much of the ROW within the Refuge occurs in wet- chlorophenol for 28 days showed changes in steroid hor- lands that serve many ecological functions, including mone levels in plasma, inhibition of spermatogenesis in spawning and rearing habitat for juvenile salmonids. Most male fish, and degeneration of ovaries in female fish of the utility poles in the Refuge ROW were treated with (Yang et al. 2017). Species sensitivity distributions provide pentachlorophenol prior to being placed into service. helpful information about the relative toxicity of pentachlo- We undertook this study to determine whether pentachlo- rophenol to various aquatic species (Jin et al. 2012). rophenol, PCDDs and PCDFs have leached from the poles Given the toxicity of commercial pentachlorophenol mix- into adjacent soils on the KENWR, and if so to what extent. tures, the environmental fate of pentachlorophenol, PCDDs Refuge managers need this information to make decisions and PCDFs from in-service utility poles is of interest. about poles that are being decommissioned, replacement poles Several studies have documented that pentachlorophenol being installed, and potential risks to humans and wildlife Environ Sci Pollut Res (2018) 25:19187–19195 19189 from contaminated soils on KENWR. We aimed to address two research questions: (1) How far have pentachlorophenol, PCDDs, and PCDFs migrated from poles at the soil surface and at what concentrations are they found? (2) Is there a dif- ference in surface soil contaminant concentrations next to poles installed in the 1950s, relative to poles installed within the past 20 years? Methods Surface soil sampling was conducted in the KENWR ROW. Our experimental design consisted of six sets of poles, of two poles each. For each set, we identified a location where a pentachlorophenol-treated pole manufactured in 1959 or Fig. 1 Surface soil sample points located around pentachlorophenol- treated utility poles. The three samples collected at each distance (at 0°, 1963 was in close proximity to a pentachlorophenol-treated 120°, and 240°) were composited; hence, there was one composite pole installed less than 20 years ago. We collected a back- sample collected at 0 cm, at 25 cm and 50 cm from each pole ground soil sample for each set of poles, located between the two poles and with qualitatively similar moisture content, veg- rinsing in tap water, rinsing in purified water (Barnstead etative cover, and soil type. In order to qualify for study inclu- Nanopure Infinity), rinsing with acetone (Burdick & Jackson sion, poles had to be within the KENWR boundary and could ‘Purified Plus’ certified ACS Grade), rinsing with high-purity not be submerged under water, and the preservative treatment hexane (Burdick & Jackson GC ), and allowing to air-dry type and year had to be confirmed by reading the manufactur- completely. Aluminum foil was likewise acetone and hexane er “button” embedded in the pole. Since the utility corridor rinsed and allowed to air dry completely. Each piece of crosses vast seasonal wetland areas, the requirement to have cleaned sampling equipment was then wrapped in a piece of dry sampling locations was a slight challenge. We attempted cleaned aluminum foil, with all sampling surfaces touching to identify promising pole candidates using the utility’s re- the dull side of the aluminum foil, prior to transport to the cords, but on-the-ground surveillance was essential to the se- field. Sample jars were purchased as precleaned and quality lection of poles meeting the study criteria. All samples were assured by the manufacturer for use with semi-volatile organic collected the week of 15 June 2015. analytes (straight-sided wide mouth jars, 120 mL Amber glass Our sampling design was similar to that of Bulle et al. with Teflon®-lined solid caps, C&G Scientific Containers, (2010), except we only sampled at the soil surface and not at VWR). Samples were frozen at − 20 °C, shipped overnight depth. Soil samples were collected around each pole following on gel ice packs to two separate analytical laboratories, and three axes: 0° (magnetic north), 120°, and 240°, at three dis- then stored at − 20 °C until analysis. tances from thepole: next tothepole(at adistancebetween0 Pentachlorophenol, select polycyclic aromatic hydrocar- and5 cm)at25cmand 50 cm (Fig. 1). At each distance from bons, and total organic carbon (TOC) were analyzed by the pole, the samples from the three compass points were mixed ALS Global—Environmental laboratory in Kelso, WA together to form a composite sample. Extra soil was collected at (USA). EPA Method 3541 was used to extract pentachloro- the 25-cm distance from two of the poles and submitted to each phenol and polycyclic aromatic hydrocarbons from soil into of the two laboratories as blind duplicates using unique sample 1:1 (v/v) acetone/hexane using a Soxhlet apparatus. The ex- identification numbers. Following careful removal of pebbles, tracted samples were then analyzed using EPA Method vegetation, and roots and thoroughmixingin astainlesssteel 8270D. Briefly, samples were injected onto a narrow-bore bowl, an aliquot of each sample (approximately 100 g) was fused-silica capillary column that was temperature pro- placed in each of two chemically clean amber glass bottles. grammed to separate the analytes and detected by a mass Samples were placed in a chilled cooler during the field-work spectrometer. Identification of target analytes was accom- day,andthentransferredtoa − 20 °C freezer for storage. plished by comparing their mass spectra with the electron All sampling equipment (stainless steel bowls, spoons, impact spectra of authentic standards and quantified by com- heavy-duty spoons, and small trowels) was precleaned in an paring the response of a major quantitation ion relative to an analytical laboratory and was not used for more than one internal standard using a 5-point calibration curve. TOC was composite sample. This obviated the need for cleaning sam- measured using EPA Method 9060. Samples were combusted pling equipment while in the field and eliminated the potential in an oxygen atmosphere to convert all organic and inorganic for cross-sample contamination. Equipment was prepared by washing in a phosphate-free soap solution (Liquinox®), forms of carbon to carbon monoxide (CO). The combustion 19190 Environ Sci Pollut Res (2018) 25:19187–19195 product gases are swept through a barium chromate catalyst/ or the interaction between age and distance (P = 0.811) but did scrubber to ensure that all of the carbon is oxidized to CO, and decrease with distance from the pole (P < 0.001). Mean pen- other potentially interfering product gases such as SO , tachlorophenol concentrations were 1810, 157, and 17.8 ppm HX, and NO were removed from the gas stream in a dry weight (d.w.) near the pole bases, at 25 cm and 50 cm from series of chemical scrubbers. CO was determined using the poles, respectively (Table 2). Pentachlorophenol was only an infrared detector. detectable in one out of six background samples, at a concen- PCDD/F congeners were analyzed by AXYS Analytical tration of 0.150 ppm. Sample-specific detection limits for pen- Services in Sidney, British Columbia (Canada) using EPA tachlorophenol in the other five background samples ranged Method 1613B. Each sample was spiked with an aliquot of from 0.066 to 0.580 ppm.. cleanup surrogate solution containing C4-2,3,7,8-TCDD The ANOVA (F =8.77, df =7,40, P <0.001) revealed that and extracted in a Soxhlet apparatus using 80:20 toluene/ace- TCDD-TEQs within the surface soil samples varied by the age tone. The resulting extract was cleaned up on a series of lay- of the poles (P = 0.043) and distance from those poles (P < ered chromatographic columns consisting of silver nitrate/ac- 0.001) but not their interaction (P = 0.285) (Fig. 2). Mean id/base silica and alumina/carbon/Celite®. The final extract surface soil TCDD-TEQ levels adjacent to “old” (> was spiked with an aliquot of recovery standard solution con- 50 years) poles were nearly twice as high (mean = 7180 ppt, taining C12-TCDDs prior to instrumental analysis. Sample SD = 10,100) as levels adjacent to “new” (< 25 years) poles extracts were analyzed using high resolution gas (mean = 3780 ppt, SD = 5730). TCDD-TEQs decreased with chromatography/high resolution mass spectrometry detection. distance from the pole, averaging 15,200 ppt (SD = 8790) at Two masses from the molecular ion cluster were used to mon- the pole base, 5170 ppt (SD = 7610) at 25 cm from poles, and itor each of the target analytes and C12-labeled surrogate 1510 ppt (SD = 2080) at 50 cm from poles. The mean TCDD- standards. Five additional ions were monitored to check for TEQ level in background samples was 9.3 ppt (SD = 15). interference from chlorinated diphenyl ethers. A second gas Surface soil levels of pentachlorophenol and TCDD-TEQs chromatograph column was used for confirmation of 2,3,7,8- were above Alaska Department of Environmental TCDF identification. A 5-point calibration was used. The in- Conservation (ADEC) Method Two soil clean-up levels for ternal standard method was used for quantification; final ana- protection of human health at all distances sampled (Table 2). lyte concentrations were recovery-corrected based on the sur- Mean surface soil levels of TCDD-TEQs exceeded USEPA rogate standard recovery within each sample. ecological screening levels at all distances sampled (Table 2). Concentrations of individual PCDD and PCDF congeners Total organic carbon in soil samples ranged from 0.98 to were multiplied by their TEFs for human health (Van den Berg 54.4% (Table 1). The characteristics of the Kenai soils, as et al. 2006) to calculate TCDD-TEQs; the total 2,3,7,8- noted in field observations and total organic carbon content, led us to classify the predominant soil type as organic rather TCDD-like potency of each sample was calculated by sum- ming the TCDD-TEQs for each sample. Limits of detection than sand or clay. for individual PCDDs and PCDFs were mostly at the single Laboratory performance was acceptable for the blind du- part-per-trillion (ppt) level and were sample specific. Less plicate soil samples. The relative percent difference for the than 7% of the 714 data points for individual PCDD and two pentachlorophenol blind duplicate pairs was 39 and PCDF congeners were below the sample-specific detection 15%. The relative percent difference for the two TCDD- limit; non-detect values were substituted with a zero for sta- TEQ blind duplicate pairs was 14 and 10%. tistical analysis. We used a two-way analysis of variance (ANOVA) with interaction term (Proc GLM, SAS 9.4) to ex- amine TCDD-TEQ variance attributable to two class vari- Discussion ables: Age (Old, New) and Distance (0, 25, and 50 cm from pole and background values). Relative percent differences Prior to undertaking this project, we had two competing and were calculated for the pentachlorophenol and TCDD-TEQ opposing hypotheses regarding whether soil surrounding results for the two blind duplicate soil sample pairs. pentachlorophenol-treated poles installed in the 1950s would be more or less contaminated than soil surrounding poles installed less than 20 years ago. We hypothesized that soil Results might be more contaminated with dioxins and furans in soils surrounding the poles from the 1950s, because pentachloro- Dioxin and furan congeners and pentachlorophenol were phenol mixtures manufactured prior to 1987 were known to quantified in surface soil surrounding all 12 study poles contain higher concentrations of dioxins and furans than (Table 1). The ANOVA (F =3.12, df =7,40, P =0.010) sug- newer products do. Alternatively, we hypothesized that soils gested that pentachlorophenol concentrations within the sur- surrounding the poles from the 1950s might be less contami- face soil samples neither varied by age of the poles (P =0.722) nated than soils surrounding newer poles, because Environ Sci Pollut Res (2018) 25:19187–19195 19191 Table 1 Chemical analysis results for surface soil samples located near the twelve selected poles (dry wt) Pole 1 (new—2006) Pole 2 (old—1963) BG for poles 1 and 2 Pole 3 (new—1998) Pole 4 (old—1959) Distance(cm) 02550 025 50 02550 0 TOC (%) 4.80 4.60 3.60 9.10 14.6 12.7 8.23 9.43 4.06 3.66 29.8 1,2,3,4,6,7,8-HpCDD (pg/g) 2.45E+05 2.56E+04 2.25E+04 5.25E+03 2.42E+04 1.06E+04 2.32E+01 9.77E+05 4.53E+05 1.87E+05 1.17E+06 1,2,3,4,6,7,8-HpCDF (pg/g) 1.07E+05 1.24E+04 1.08E+04 1.76E+03 7.80E+03 3.38E+03 6.93E+00 9.91E+04 7.58E+04 3.18E+04 1.57E+05 1,2,3,4,7,8,9-HpCDF (pg/g) 1.11E+04 1.07E+03 9.20E+02 1.18E+02 5.84E+02 2.47E+02 5.17E−01 2.31E+04 1.01E+04 2.92E+03 1.38E+04 1,2,3,4,7,8-HxCDD (pg/g) 5.49E+02 2.84E+02 2.61E+02 1.14E+02 3.08E+02 2.19E+02 3.03E−1 3.20E+03 7.15E+03 3.29E+03 2.01E+04 1,2,3,4,7,8-HxCDF (pg/g) 3.26E+03 1.22E+03 7.65E+02 5.21E+02 2.43E+03 1.06E+03 1.16E+00 1.62E+03 3.18E+03 1.17E+03 8.57E+03 1,2,3,6,7,8-HxCDD (pg/g) 8.11E+03 1.32E+03 1.28E+03 2.62E+02 1.09E+03 6.43E+02 1.00E+00 8.43E+03 1.46E+04 5.79E+03 2.41E+04 1,2,3,6,7,8-HxCDF (pg/g) 6.47E+02 3.56E+02 2.84E+02 1.42E+02 5.20E+02 2.32E+02 3.04E−1 5.49E+02 2.11E+03 1.03E+03 3.35E+03 1,2,3,7,8,9-HxCDD (pg/g) 1.79E+03 6.37E+02 6.13E+02 2.50E+02 7.08E+02 5.58E+02 8.20E−01 1.23E+04 1.41E+04 7.31E+03 8.95E+04 1,2,3,7,8,9-HxCDF (pg/g) 3.24E+01 1.32E+01 2.00E+01 2.10E+01 2.45E+01 9.15E+00 < .0491 6.63E+01 4.94E+01 2.21E+01 3.78E+02 1,2,3,7,8-PeCDD (pg/g) 1.49E+02 8.37E+01 7.01E+01 4.59E+01 1.46E+02 8.63E+01 1.43E−01 2.33E+02 2.09E+03 1.03E+03 1.81E+03 1,2,3,7,8-PeCDF (pg/g) 4.26E+01 7.24E+01 3.08E+01 3.49E+01 2.60E+02 1.07E+02 1.04E−01 < 20.8 1.31E+02 7.65E+01 3.79E+02 2,3,4,6,7,8-HxCDF (pg/g) 3.73E+02 2.25E+02 1.80E+02 7.18E+01 2.35E+02 1.16E+02 2.04E−01 4.74E+02 1.75E+03 9.12E+02 2.49E+03 2,3,4,7,8-PeCDF (pg/g) 7.43E+01 2.22E+02 8.36E+01 1.22E+02 9.43E+02 3.86E+02 3.25E−01 < 20.8 2.02E+02 1.09E+02 2.85E+02 2,3,7,8-TCDD (pg/g) 1.83E+00 1.70E+00 1.47E+00 2.00E+00 6.35E+00 3.73E+00 < .0491 < 15.2 8.63E+01 5.96E+01 7.73E+01 2,3,7,8-TCDF (pg/g) 6.19E+00 1.79E+01 6.16E+00 7.18E+00 6.50E+01 2.76E+01 < .0968 < 75.3 2.28E+01 1.32E+01 5.33E+02 OCDD (pg/g) 1.13E+06 1.51E+05 1.30E+05 2.51E+04 1.57E+05 NQ 1.45E+02 2.39E+06 1.29E+06 1.05E+06 1.09E+06 OCDF (pg/g) 1.02E+06 7.70E+04 7.08E+04 2.55E+03 1.54E+04 6.48E+03 1.90E+01 1.16E+06 3.88E+05 1.07E+05 3.71E+05 TCDD-TEQ (pg/g)* 5.93E+03 1.02E+03 8.41E+02 3.04E+02 1.36E+03 6.40E+02 9.78E−01 1.50E+04 1.24E+04 5.64E+03 3.07E+04 Pentachlorophenol (mg/kg) 1.90E+03 3.50E+01 3.40E+01 2.30E+00 8.60E+00 3.80E+00 1.50E−01 8.10E+03 3.20E+02 3.50E+01 3.10E+02 Pole 4 (old—1959) BG for poles 3 and 4 Pole 5 (new—2009) Pole 6 (old—1959) BG for poles 5 and 6 Pole 7 (new—2011) Distance (cm) 25 50 0 25 50 0 25 50 0 TOC (%) 17.6 21.2 54.4 26.3 20.4 20.8 10.3 12.3 5.27 16.9 6.12 1,2,3,4,6,7,8-HpCDD (pg/g) 2.99E+05 2.09E+05 1.27E+03 3.70E+05 6.96E+03 2.10E+03 7.55E+05 2.70E+05 2.38E+04 5.86E+01 8.69E+04 1,2,3,4,6,7,8-HpCDF (pg/g) 1.03E+05 7.12E+04 2.37E+02 5.70E+05 1.04E+04 2.81E+03 3.11E+05 9.90E+04 8.48E+03 1.58E+01 1.35E+05 1,2,3,4,7,8,9-HpCDF (pg/g) 5.08E+03 3.86E+03 1.89E+01 1.92E+04 1.99E+02 9.47E+01 2.04E+04 5.61E+03 4.80E+02 7.76E−01 7.56E+03 1,2,3,4,7,8-HxCDD (pg/g) 2.81E+03 1.94E+03 2.17E+01 1.41E+03 5.67E+01 1.26E+01 4.55E+03 2.70E+03 2.87E+02 9.48E−01 3.08E+02 1,2,3,4,7,8-HxCDF (pg/g) 6.20E+03 4.21E+03 9.50E+00 1.48E+04 3.29E+02 6.45E+01 1.47E+04 6.78E+03 6.34E+02 1.11E+00 2.53E+03 1,2,3,6,7,8-HxCDD (pg/g) 9.71E+03 7.22E+03 4.20E+01 1.12E+04 2.24E+02 6.10E+01 2.32E+04 9.76E+03 7.60E+02 2.24E+00 1.72E+03 1,2,3,6,7,8-HxCDF (pg/g) 2.05E+03 1.39E+03 8.44E+00 1.76E+04 5.10E+02 7.68E+01 4.70E+03 2.39E+03 2.23E+02 5.12E−01 2.82E+03 1,2,3,7,8,9-HxCDD (pg/g) 6.62E+03 4.58E+03 5.35E+01 4.42E+03 1.58E+02 3.79E+01 1.24E+04 5.84E+03 5.95E+02 2.64E+00 7.51E+02 1,2,3,7,8,9-HxCDF (pg/g) 1.71E+02 1.41E+02 4.17E−01 1.47E+02 < 2.17 < 1.74 8.89E+02 1.48E+02 < 37 < 0.0481 < 69.7 1,2,3,7,8-PeCDD (pg/g) 6.99E+02 5.29E+02 8.47E+00 3.24E+02 1.35E+01 4.08E+00 4.44E+02 7.30E+02 1.27E+02 5.34E−01 6.80E+01 1,2,3,7,8-PeCDF (pg/g) 4.31E+02 3.57E+02 7.47E−01 9.95E+02 3.39E+01 4.92E+00 6.08E+02 4.95E+02 < 28.9 1.78E−01 8.36E+01 2,3,4,6,7,8-HxCDF (pg/g) 1.51E+03 1.13E+03 7.19E+00 8.37E+03 3.35E+02 4.47E+01 2.92E+03 1.71E+03 1.57E+02 3.51E−01 1.55E+03 2,3,4,7,8-PeCDF (pg/g) 4.51E+02 3.72E+02 9.35E−01 7.34E+02 3.04E+01 4.51E+00 3.12E+02 6.76E+02 8.45E+01 1.89E−01 1.08E+02 2,3,7,8-TCDD (pg/g) 2.33E+01 1.69E+01 5.72E−01 2.65E+00 < .556 1.54E−01 < 19.7 4.59E+01 < 10 7.04E−02 < 20.5 2,3,7,8-TCDF (pg/g) < 85.5 5.540E+01 2.400E−01 9.02E+01 5.43E+00 4.42E−01 < 14.9 8.06E+01 < 16.7 7.60E−02 < 19.4 OCDD (pg/g) 1.510E+06 1.010E+06 8.690E+03 1.52E+06 4.12E+04 1.36E+04 1.88E+06 1.57E+06 1.84E+05 3.92E+02 8.06E+05 OCDF (pg/g) 3.110E+05 2.210E+05 5.700E+02 1.07E+06 7.49E+03 7.29E+03 7.62E+05 2.87E+05 2.48E+04 3.18E+01 5.26E+05 TCDD-TEQ (pg/g)* 8.395E+03 5.945E+03 4.168E+01 1.67E+04 3.76E+02 9.18E+01 1.85E+04 8.24E+03 8.08E+02 2.33E+00 3.77E+03 Pentachlorophenol (mg/kg) 5.000E+01 4.700E+01 < 0.580 5.80E+02 4.70E+00 1.90E+00 2.40E+03 1.70E+02 6.30E+00 < 0.240 2.90E+02 Pole 7 (new—2011) Pole 8 (old—1959) BG for poles 7 and 8 Pole 9 (new—2011) Pole 10 (old—1959) 19192 Environ Sci Pollut Res (2018) 25:19187–19195 Table 1 (continued) Pole 7 (new—2011) Pole 8 (old—1959) BG for poles 7 and 8 Pole 9 (new—2011) Pole 10 (old—1959) Distance (cm) 25 50 0 25 50 0 25 50 0 25 TOC (%) 4.63 5.94 41.8 3.27 2.3 31.5 7.39 0.98 2.12 12.4 23.3 1,2,3,4,6,7,8-HpCDD (pg/g) 6.02E+02 4.83E+02 6.32E+05 3.81E+04 9.41E+03 1.53E+02 2.93E+05 4.80E+04 1.52E+04 9.20E+05 7.60E+05 1,2,3,4,6,7,8-HpCDF (pg/g) 8.25E+02 3.06E+02 2.71E+05 1.48E+04 3.62E+03 4.33E+01 4.26E+05 7.18E+03 1.22E+04 3.62E+05 3.37E+05 1,2,3,4,7,8,9-HpCDF (pg/g) 5.36E+01 1.17E+01 1.36E+04 6.89E+02 2.39E+02 2.86E+00 1.73E+04 4.28E+02 2.87E+02 2.37E+04 1.84E+04 1,2,3,4,7,8-HxCDD (pg/g) 4.56E+00 8.15E+00 6.60E+03 3.56E+02 9.80E+01 2.28E+00 9.05E+02 4.97E+02 1.05E+02 4.52E+03 1.03E+04 1,2,3,4,7,8-HxCDF (pg/g) 2.73E+01 1.53E+01 1.77E+04 8.88E+02 2.62E+02 3.47E+00 9.86E+03 1.22E+03 4.91E+02 1.20E+04 2.30E+04 1,2,3,6,7,8-HxCDD (pg/g) 1.64E+01 1.97E+01 2.41E+04 1.12E+03 3.67E+02 5.96E+00 7.82E+03 2.06E+03 4.86E+02 2.15E+04 3.51E+04 1,2,3,6,7,8-HxCDF (pg/g) 3.36E+01 1.77E+01 6.46E+03 3.28E+02 8.84E+01 1.75E+00 1.03E+04 4.87E+02 4.10E+02 4.22E+03 9.53E+03 1,2,3,7,8,9-HxCDD (pg/g) 1.28E+01 2.41E+01 1.62E+04 7.77E+02 2.25E+02 7.51E+00 3.18E+03 1.27E+03 2.85E+02 1.73E+04 2.18E+04 1,2,3,7,8,9-HxCDF (pg/g) < 0.355 2.82E−01 5.00E+02 < 43.2 < 34.2 5.16E−01 1.42E+02 7.60E+01 < 41.6 9.44E+02 6.79E+02 1,2,3,7,8-PeCDD (pg/g) 1.59E+00 3.88E+00 1.30E+03 8.28E+01 2.51E+01 1.36E+00 1.53E+02 2.67E+02 < 26.2 3.43E+02 2.41E+03 1,2,3,7,8-PeCDF (pg/g) 2.22E+00 1.92E+00 1.29E+03 5.79E+01 3.02E+01 4.21E−01 5.72E+02 2.21E+02 4.57E+01 3.72E+02 2.01E+03 2,3,4,6,7,8-HxCDF (pg/g) 2.21E+01 1.40E+01 4.17E+03 2.70E+02 5.13E+01 1.48E+00 5.18E+03 3.37E+02 2.86E+02 2.97E+03 5.85E+03 2,3,4,7,8-PeCDF (pg/g) 2.58E+00 2.40E+00 1.19E+03 1.01E+02 3.77E+01 4.69E−01 3.69E+02 2.19E+02 5.33E+01 2.39E+02 1.88E+03 2,3,7,8-TCDD (pg/g) < 0.118 3.18E−01 4.23E+01 < 12.6 < 13.3 2.02E−01 < 19.5 1.93E+01 < 9.53 < 10.6 6.68E+01 2,3,7,8-TCDF (pg/g) < 0.405 3.20E−01 2.36E+02 9.77E+00 < 7.67 1.85E−01 4.04E+01 6.04E+01 < 9.39 < 12.3 8.60E+01 OCDD (pg/g) 4.99E+03 2.90E+03 1.84E+06 2.59E+05 6.51E+04 1.04E+03 1.31E+06 3.50E+05 1.10E+05 1.78E+06 1.74E+06 OCDF (pg/g) 2.11E+03 2.68E+02 6.18E+05 3.93E+04 9.29E+03 9.07E+01 1.44E+06 4.53E+03 1.41E+04 9.18E+05 6.15E+05 TCDD-TEQ (pg/g)* 3.10E+01 2.39E+01 1.92E+04 1.12E+03 3.01E+02 6.36E+00 1.22E+04 1.62E+03 5.38E+02 2.06E+04 2.56E+04 Pentachlorophenol (mg/kg) 4.30E−01 1.90E−01 8.20E+02 1.60E+01 3.60E+00 < 0.360 1.50E+03 3.50E+01 4.30E+00 2.40E+03 1.20E+03 Pole 10 (old—1959) BG for poles 9 and 10 Pole 11 (new—2009) Pole 12 (old—1959) BG for poles 11 and 12 Distance (cm) 50 0 25 50 0 25 50 TOC (%) 6.66 14.3 23.4 11.7 12.8 14.6 1.91 10.8 1.59 1,2,3,4,6,7,8-HpCDD (pg/g) 4.27E+04 9.75E+01 2.42E+05 2.44E+03 1.85E+02 8.67E+05 5.88E+04 6.69E+04 1.74E+01 1,2,3,4,6,7,8-HpCDF (pg/g) 1.59E+04 2.35E+01 4.45E+05 8.72E+02 9.12E+01 4.11E+05 2.37E+04 2.61E+04 3.38E+00 1,2,3,4,7,8,9-HpCDF (pg/g) 1.03E+03 1.21E+00 1.03E+04 6.16E+01 2.85E+00 2.27E+04 1.29E+03 1.18E+03 1.70E−01 1,2,3,4,7,8-HxCDD (pg/g) 4.93E+02 1.57E+00 1.38E+03 2.59E+01 2.94E+00 8.59E+03 5.07E+02 6.59E+02 2.94E−01 1,2,3,4,7,8-HxCDF (pg/g) 9.83E+02 1.77E+00 1.41E+04 3.02E+01 3.75E+00 2.49E+04 1.37E+03 1.66E+03 3.04E−01 1,2,3,6,7,8-HxCDD (pg/g) 1.63E+03 3.90E+00 7.49E+03 6.64E+01 6.59E+00 3.40E+04 1.75E+03 2.13E+03 7.12E−01 1,2,3,6,7,8-HxCDF (pg/g) 3.83E+02 7.52E−01 2.15E+04 2.55E+01 4.77E+00 8.63E+03 5.81E+02 5.95E+02 1.34E−01 1,2,3,7,8,9-HxCDD (pg/g) 1.06E+03 6.07E+00 4.01E+03 7.16E+01 7.76E+00 1.85E+04 1.36E+03 1.40E+03 8.94E−01 1,2,3,7,8,9-HxCDF (pg/g) 7.89E+01 2.61E−01 1.46E+02 < 1.18 8.62E−02 7.27E+02 5.70E+01 4.52E+01 < 0.0514 1,2,3,7,8-PeCDD (pg/g) 8.83E+01 6.91E−01 3.19E+02 7.10E+00 1.34E+00 1.08E+03 1.72E+02 1.73E+02 1.74E−01 1,2,3,7,8-PeCDF (pg/g) 6.72E+01 1.92E−01 1.49E+03 2.65E+00 6.01E−01 1.18E+03 1.21E+02 1.35E+02 < 0.0514 2,3,4,6,7,8-HxCDF (pg/g) 2.51E+02 6.55E−01 1.26E+04 1.84E+01 3.77E+00 5.62E+03 4.15E+02 4.28E+02 9.63E−02 2,3,4,7,8-PeCDF (pg/g) 1.27E+02 2.04E−01 1.08E+03 2.15E+00 5.80E−01 8.73E+02 1.43E+02 1.79E+02 8.11E−02 2,3,7,8-TCDD (pg/g) < 34.9 < 0.0522 < 24.9 < 0.431 8.96E−02 2.25E+01 < 15.6 < 15.6 5.65E−02 2,3,7,8-TCDF (pg/g) < 22.5 6.90E−02 2.11E+02 4.23E−01 < 0.125 < 12.8 < 9.42 2.69E+01 < 0.0514 OCDD (pg/g) 2.96E+05 7.53E+02 1.23E+06 1.80E+04 1.26E+03 1.64E+06 4.10E+05 4.55E+05 1.22E+02 OCDF (pg/g) 4.18E+04 4.66E+01 4.48E+05 4.00E+03 1.17E+02 8.02E+05 6.37E+04 6.98E+04 5.79E+00 TCDD-TEQ (pg/g)* 1.31E+03 3.72E+00 1.43E+04 7.20E+01 7.79E+00 2.52E+04 1.80E+03 2.02E+03 7.46E−01 Pentachlorophenol (mg/kg) 2.70E+01 < 0.460 4.90E+02 5.00E−01 < 0.180 2.90E+03 4.90E+01 5.10E+01 < 0.0660 *TCDD-TEQs are based on human health using Toxic Equivalency Factors from van den Berg et al. (2006) Environ Sci Pollut Res (2018) 25:19187–19195 19193 contaminants from the older poles have had so much longer to potential contamination with PCDDs or PCDFs. weather and degrade in the environment. Our results showed Nevertheless, their work documented that drinking water that despite the passage of over 50 years since pole installa- contamination can occur from pentachlorophenol-treated tion, TCDD-TEQs were still present in surface soils near old utility poles, at levels that may pose a risk to human poles, at levels greater than those found near newer poles. This health. finding points both to the remarkable environmental persis- In May 2015, at the seventh meeting of the Conference of tence of PCDDs and PCDFs in Kenai soils and to the relative the Parties to the Stockholm Convention on Persistent Organic severity of dioxin/furan contamination of pentachlorophenol Pollutants (POPs) in Geneva, Switzerland, a final decision mixtures in wood treatment products from the late 1950s/early (UNEP/POPS/COP.7-SC-7/13) was made to list pentachloro- 1960s. phenol and its salts and esters in Annex A, with specific ex- Although pentachlorophenol and TCDD-TEQ levels in emptions for the production and use of pentachlorophenol for surface soils decreased significantly with distance from the utility poles and cross arms. The Stockholm Convention calls poles in this project, levels of both contaminants exceeded for international action to eliminate or restrict the production State of Alaska clean-up levels for all poles even at the farthest or use of specific listed POPs, and decisions are binding on the distance sampled (50 cm). The nature and extent of soil con- 179 signatory countries. An Annex A listing is the most re- tamination was not fully characterized during this project, be- strictive category of the Convention, calling for the elimina- cause soils were not sampled at depth or at a great enough tion of the production and use of listed POPs. The United distance to delineate the complete lateral extent of contamina- States has not ratified the Convention, and is not bound by tion. Thus, additional sampling is warranted, both at depth and the Convention’s decisions. The U.S. Environmental at greater distances from the pole, to characterize the full scope Protection Agency (EPA) currently allows the use of of soil contamination around the poles. pentachlorophenol-treated wood for utility poles; the re- It is unknown whether the poles we sampled are represen- registration of pentachlorophenol as a pesticide for this use tative of pentachlorophenol-treated utility poles located else- is reviewed periodically. The U.S. EPA last renewed the reg- where. The pentachlorophenol and TCDD-TEQ levels we de- istration of pentachlorophenol for wooden poles and cross tected in surface soil near new utility poles on KENWR were arms under the Federal Insecticide, Fungicide and similar to, but lower than, levels found in surface organic soils Rodenticide Act in 2008 (USEPA 2008). in the Montreal Quebec area near poles less than 20 years old While pentachlorophenol-treated utility poles pose a de- (Bulle et al. 2010). Montreal’s latitude is 15° further south gree of risk to human health and the environment, they also than KENWR. Pentachlorophenol, dioxins, and furans might provide effective infrastructure for the delivery of electricity be more persistent in the cold soils of the Kenai Peninsula throughout North America. The decision to continue to install pentachlorophenol-treated poles requires an analysis of alter- relative to the warmer soils found in many parts of the USA. However, our study and that of Bulle et al. (2010)provide natives, relative risks, and cost. Other wood preservation cause for concern, because they demonstrate the possibility chemicals are available for use, but often pose their own health that many of the millions of utility poles in North America and environmental risks. For example, copper, arsenic, and may each be point sources of pentachlorophenol and dioxin/ other inorganic chemicals are common ingredients in wood furan soil contamination. This may cause a problem both in preservation products such as copper naphthenate, ammonia- terms of potentially unacceptable risk, and from the perspec- cal copper zinc arsenate, ammoniacal copper arsenate, tive that dioxin-contaminated soil is costly to remediate. chromated copper arsenate, and ammoniacal copper quaterna- In 2009, the Vermont Department of Health responded ry (Hutton and Samis 2000). Copper-containing utility poles to two separate incidents of private drinking water con- may be unacceptable for use in wetland environments that tamination with pentachlorophenol from treated utility sustain early life stages of fish, such as in the Kenai NWR poles (Karlsson et al. 2013). In both cases, utility poles ROW, because copper is toxic to fish at very low concentra- upgradient from the drinking water source had been re- tions. There are also alternatives to the use of treated wood for cently replaced, and an odor in their water alerted resi- utility poles, such as non-treated cedar poles, cement, fiber- dents to the presence of a contaminant. In one residence glass, spun concrete, metal, or buried wires. with a shallow well, the water had a level of 2.06 mg/L of Site-specific environmental characteristics must be fac- pentachlorophenol, which was about 2000 times greater tored in to select the most appropriate material for a particular than the EPA maximum contaminant level of 0.001 mg/ project. Life-cycle assessment can be a useful tool to compare L. In the second household in a different area, which the environmental impacts of various pole alternatives from obtained its drinking water from a private spring, a pen- “cradle to grave,” including the growth or manufacture of the tachlorophenol level of 0.007 mg/L was documented from pole, transportation, time in use, and disposal following the tap. The Vermont Department of Health did not ana- decommissioning. Many factors can be considered, including lyze the drinking water from either household for greenhouse gas emissions, fossil fuel use, acidification, water 19194 Environ Sci Pollut Res (2018) 25:19187–19195 Fig. 2 Distribution of TCDD- TEQ levels in surface soils (ppt d.w.) at three lateral distances (0, 25, 50 cm) from old (> 50 years) and new (< 25 years) pentachlorophenol-treated utility poles with accompanying soil background levels (SAS GLM output). Upper and lower bounds of the shaded box represent the sample 75th and 25th percentiles; line within box is the sample median, and diamond is the sample mean. Whiskers outside box represent range of data within 1.5 inter-quartiles; data outside this range are represented by circles, with adjacent number indicating data ID use, eutrophication, ecological toxicity, etc. A recent life-cycle toxicity impacts would be a valuable addition to future assessment compared pentachlorophenol-treated wooden util- life-cycle assessments examining the environmental im- ity poles with steel and concrete utility poles (Bolin and Smith pacts of utility poles. 2011). While it found that pentachlorophenol-treated poles compared favorably in several respects, it unfor- tunately did not include consideration of dioxin and Conclusions and recommendations furan impurities, their potential impacts on the environ- ment, or the potential cost of contaminant remediation. Utility poles are present in many environments with po- Similarly, another life-cycle assessment that compared tential human receptors, including parks, schools, play- steel and concrete utility poles with Veneer-based com- grounds, and backyards. Vulnerable human receptors in posite (VBC) poles did not consider the potential envi- these environments may be being exposed to unacceptable ronmental toxicity associated with the preservative used levels of pentachlorophenol and dioxin/furans, from in the VBC poles (alkaline copper quaternary) (Lu and touching contaminated poles, exposure to contaminated El Hanandeh 2017). Consideration of environmental soils, or from consumption of contaminated drinking Table 2 Arithmetic mean a b EPA Eco ADEC HH ADEC Mig GW (standard deviation) concentration of Pentachlorophenol (ppm dry wt) pentachlorophenol and 2,3,7,8- tetrachlorodibenzo-p-dioxin At pole 1810 (2210) 2.1 (USEPA 2007)13 0.0043 equivalents in surface soil of 25 cm 157 (341) Kenai National Wildlife Refuge 50 cm 17.8 (19.5) and various regulatory values for TCDD-eqs-HH (ppt dry wt) comparison At pole 15,200 (8790) 3.15 (USEPA 2018)60 3.9 25 cm 5170 (7610) 50 cm 1510 (2080) Background 9.31 (16.0) Alaska Department of Environmental Conservation Statute 18 AAC 75.340: Method Two clean-up levels for soil based on human health (direct contact) Alaska Department of Environmental Conservation Statute 18 AAC 75.340: Method Three clean-up levels for soil based on human health—migration to groundwater 2,3,7,8-TCDD equivalents based on human health risk, using WHO toxic equivalence factors (van den Berg et al. 2006) Environ Sci Pollut Res (2018) 25:19187–19195 19195 Hutton KE, Samis SC (2000) Guidelines to protect fish and fish habitat water. Additional research is needed to characterize soil from treated wood used in aquatic environments in the Pacific re- contamination surrounding utility poles in other habitat gion. Fisheries and Oceans Canada, Vancouver types throughout the USA and determine whether soils Jin X, Zha J, Xu Y, Giesy JP, Wang Z (2012) Toxicity of pentachlorophe- in the continental USA are similarly contaminated. nol to native aquatic species in the Yangtze River. Environ Sci Pollut Res 19:609–618 Further characterization of the risks posed to human Karlsson L, Cragin L, Center G, Giguere C, Comstock J, Boccuzzo L, health and the environment should also be undertaken. Sumner A (2013) Pentachlorophenol contamination of private drinking water from treated utility poles. Am J Public Health Acknowledgements The authors appreciate the field work assistance 103(2):276–277 provided by Mallory Okuly and Mariah Stephens. 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Environmental Science and Pollution Research – Springer Journals
Published: Jun 1, 2018
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