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MAGCORP / US MAGNESIUMDIOXIN TESTING

September - November 1998

Source: UDEQ Div. of Air Quality Transmittal DAQB-004-98, Nov. 9, 1998 Dr. Steve Packham to Howard Gross, Citizens Against Chlorine Contamination

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STUDY PARTICIPANTS

• MagCorp - Tom Tripp, Environmental Mgr.

• Department of Environmental Quality– Steve Packham, Ph.D.

• Region VIII EPA - William Yellowtail, Reg. VIII Director

• Citizens Against Chlorine Contamination– Howard Gross

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PROBLEM

• With limited resources (~$20k), assess degree of probability that dioxins are being formed in MagCorp processes

• Identify likely media for sampling and analysis (air, soils, natural waters, process water, etc.)

• Produce scientifically credible data

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Sampling Plan Designed by CACC, Approved by UDEQ, EPA VIII

• Stack sampling was likely to be inaccurate due to high concentrations of chlorine gas, concentrated hydrochloric acid and extreme temperatures in exhaust gases

• Reaction of chlorine gas with metal catalyst and multi-ringed hydrocarbons (petroleum) is ideal for creating dioxins– See M. Oehme, Formation

of Polychlorinated Dibenzofurans and Dibenzo-p-dioxins by Production Processes for Magnesium and Refined Nickel,

• Atmosphere, Vol. 18, Nos. 7-8, pp1379-1389, 1989

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Sampling Plan Designed by CACC, Approved by UDEQ, EPA VIII

• Limited funding from DEQ precluded any comprehensive sampling and analysis plan, especially stack sampling analyses– “grab” samples chosen as

sampling method• 4 Liquids

• 3 Solids

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SAMPLING PLAN: LIQUIDS

LIQUIDS:

• Well Water– Process water (control)

• Great Salt Lake

• Waste Pond

• Waste Ditch

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SAMPLING PLAN: SOLIDS

SOLIDS:

• Great Salt Lake Sediments

• Waste Pond

• Waste Ditch

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SAMPLING PLAN: unit conversions

Liquids• mg/L or ug/mL = ppm• ug/L or ng/mL = ppb• ng/L or pg/mL = ppt• pg/L or fg/mL = ppq

Solids• mg/kg or ug/g = ppm• ug/kg or ng/g = ppb• ng/kg or pg/g = ppt• pg/L or fg/g = ppq

mg = milligramsug = micrograms ng = nanograms

pg = picograms

ppm = parts per millionppb = parts per billionppt = parts per trillionppq = parts per quadrillion

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RESULTS: LIQUIDS

All values are parts per quadrillion (ppq)

Well water Great Salt Lake Waste Pond Waste Ditch* Waste Ditchliquid (pg/L) liquid (pg/L) liquid (pg/L) liquid (pg/L) liquid (pg/L)

2,3,7,8-TCDD 4.821,2,3,7,8-PeCDD 50.141,2,3,4,7,8-HxCDD 147.871,2,3,6,7,8-HxCDD 176.991,2,3,7,8,9-HxCDD 230.231,2,3,4,6,7,8-HpCDD 1.71 24.18 1,241.33 1,553.81OCDD 6.02 145.62 9,784.91 9,833.21

2,3,7,8-TCDF 179.04 816.98 772.041,2,3,7,8-PeCDF 98.66 985.98 1,032.962,3,4,7,8-PeCDF 44.47 665.16 687.631,2,3,4,7,8-HxCDF 308.91 6,687.10 6,493.301,2,3,6,7,8-HxCDF 199.51 2,998.89 2,886.881,2,3,7,8,9-HxCDF 70.38 776.60 1,106.622,3,4,6,7,8-HxCDF 94.33 954.06 1,661.131,2,3,4,6,7,8-HpCDF 2.65 1,435.19 38,866.67 26,910.461,2,3,4,7,8,9-HpCDF 313.71 13,808.61 7,985.08OCDF 19.68 44,609.14 1,834,715.55 204,331.57

Sum 0.0 30.1 47,523 1,912,302 265,865

*re-extracted samplesSource: Utah State Dept. of Environmental Quality Analytical Results, November 1998

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All values are parts per trillion (ppt)

Great Salt Lake Waste Pond* Waste Pond Waste Ditch* Waste Ditchsolids (ng/Kg) solids (ng/Kg) solids (ng/Kg) solids (ng/Kg) solids (ng/Kg)

2,3,7,8-TCDD 62.101,2,3,7,8-PeCDD 585.75 492.441,2,3,4,7,8-HxCDD 850.44 941.531,2,3,6,7,8-HxCDD 3.47 1,786.40 1,672.611,2,3,7,8,9-HxCDD 1,923.88 1,997.821,2,3,4,6,7,8-HpCDD 12.87 14.70 7,873.90 6,106.78OCDD 2.99 44.77 50.16 19,318.74 20,698.07

2,3,7,8-TCDF 88.44 102.26 10,678.80 11,268.811,2,3,7,8-PeCDF 98.15 110.75 36,693.73 38,222.332,3,4,7,8-PeCDF 37.95 52.57 14,248.54 14,631.371,2,3,4,7,8-HxCDF 245.94 242.78 96,193.43 100,219.521,2,3,6,7,8-HxCDF 185.86 226.71 55,881.00 57,246.611,2,3,7,8,9-HxCDF 30.63 21.49 15,617.01 23,166.202,3,4,6,7,8-HxCDF 85.22 73.17 9,013.41 9,371.891,2,3,4,6,7,8-HpCDF 1,409.09 1,431.59 122,358.28 321,920.761,2,3,4,7,8,9-HpCDF 112.31 130.75 95,306.08 99,176.03OCDF 6,255.36 8,649.13 536,350.51 4,506,532.12

Sum 2.99 8,607 11,110 1,024,742 5,213,665

*re-extracted samples

RESULTS: SOLIDS

Source: Utah State Dept. of Environmental Quality Analytical Results, November 1998

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DIOXIN CHLORINE SATURATIONPattern in Great Salt Lake mirrors ‘peaks’ pattern in

MagCorp waste ditch and waste pond

• Dioxins and furans are extremely hydrophobic

• Tend to adsorb to particles, settle out

• Graph’s pattern of highly Cl-saturated congeners found in the Lake purple trace points clearly to the source, mirroring MagCorp samples (well water ‘control’shows none of characteristic dioxins)

Well water Great Salt Lake

Waste Pond Waste Ditch

dioxin and furan distribution in MagCorp waters11/98

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Consequences• Dioxin is a

generational toxin that causes harm at incomprehensibly low concentrations– Concentrations of

parts per million ARE HIGHLY SIGNIFICANT

– TEQs of parts per trillion and per quadrillion ARE HIGHLY SIGNIFICANT

• Transient nature of waterfowl make testing difficult

• Symptoms are hard to diagnose causally in both animals and humans– immuno-suppression,

“failure to thrive”

– developmental defects

– reproductive toxicity

– cancer, endometriosis

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Consequences• Great Salt Lake is a critical

stopover for >10 million migratory shorebirds & waterfowl / year from throughout the Western Hemisphere

• Migratory birds are protected by international treaty - Migratory Bird Treaty/Act of 1918

• $25,000 fine applies per each ‘take’ of a migratory bird covered under the MBT

• Much of the biomass generated for these species is in brine shrimp and brine flies

• These are a product of the water column and are likely to transfer these contaminants to the higher predators/consumers

• Includes humans who eat seafood raised on brine shrimp from the Great Salt Lake, a primary feed for shrimp and prawns in aquaculture, worldwide

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MAGCORP TOTAL DIOXINSUDEQ Sampling Sept.-Nov. 1998

• Solids:– Great Salt Lake 2.99 ppt

– Waste Pond 8,607 ppt (re-extracted)

– Waste Pond 11,110 ppt

– Waste Ditch 1,024,742 ppt (re-extracted)

– Waste Ditch 5,213,666 ppt

• Liquids:– Well Water 0.000 ppt

– Great Salt Lake 0.031 ppt

– Waste Pond 47.5 ppt

– Waste Ditch 1,912 ppt (re-extracted)

– Waste Ditch 265 ppt

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TEQ vs. TOTAL DIOXINS

• TEQ = ‘Toxic Equivalency Quotient’

• Based on 2,3,7,8-TCDD as most toxic form of dioxin = 1.0 TEF (Toxic Equivalency Factor)

• Other dioxins assigned factors (TEF) less than 1.0 , based on fractional toxicity compared to 2,3,7,8-TCDD

• Multiply total level of particular dioxin / furan by TEF to get TEQ

• Dioxin science still relatively new; human health and ecological effects, especially, not fully known

• Recent discussion in Our Stolen Future by T. Colborn, D. Dumanoski and J.P. Myers raises extensive catalog of urgent issues and concerns warranting investigation

• Great Salt Lake ecosystems and wildlife exposures probable

• Human health exposures through food and air possible, especially through shrimp and prawns, fed Great Salt Lake brine shrimpeggs in fish farms around the world

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RESULTS: SOLIDSWell water

TEF liq. (pg/L) liq. (pg/L) sol. (ng/Kg) liq. (pg/L) sol. (ng/Kg) liq. (pg/L) sol. (ng/Kg)2,3,7,8-TCDD 1 0.000 0.000 0.000 0.00 0.00 4.82 62.11,2,3,7,8-PeCDD 0.5 0.000 0.000 0.000 0.00 0.00 25.1 2931,2,3,4,7,8-HxCDD 0.1 0.000 0.000 0.000 0.00 0.00 14.8 85.01,2,3,6,7,8-HxCDD 0.1 0.000 0.000 0.000 0.00 0.00 17.7 1791,2,3,7,8,9-HxCDD 0.1 0.000 0.000 0.000 0.00 0.00 23.0 1921,2,3,4,6,7,8-HpCDD 0.01 0.000 0.017 0.000 0.24 0.13 15.5 78.7OCDD 0.001 0.000 0.006 0.003 0.15 0.04 9.83 19.3

2,3,7,8-TCDF 0.1 0.000 0.000 0.000 17.9 8.84 77.2 10681,2,3,7,8-PeCDF 0.05 0.000 0.000 0.000 4.93 4.91 51.6 18352,3,4,7,8-PeCDF 0.5 0.000 0.000 0.000 22.2 19.0 344 71241,2,3,4,7,8-HxCDF 0.1 0.000 0.000 0.000 30.9 24.6 649 96191,2,3,6,7,8-HxCDF 0.1 0.000 0.000 0.000 20.0 18.6 289 55881,2,3,7,8,9-HxCDF 0.1 0.000 0.000 0.000 7.04 3.06 111 15622,3,4,6,7,8-HxCDF 0.1 0.000 0.000 0.000 9.43 8.52 166 9011,2,3,4,6,7,8-HpCDF 0.01 0.000 0.027 0.000 14.4 14.1 269 12241,2,3,4,7,8,9-HpCDF 0.01 0.000 0.000 0.000 3.14 1.12 79.9 953OCDF 0.001 0.000 0.020 0.000 44.6 6.26 204 536

TEQ (ppt) 0.0000 0.0001 0.0030 0.175 109 2.35 31319

* re-extracted

Great Salt Lake* Waste Pond* Waste Ditch*

*re-extracted samples

RESULTS: TEQ

METHODOLOGY: USEPA/625/3-89/016, March 1989 ‘Interim Procedures for Estimating RisksAssociated with Exposures to Mixtures of Chlorinated Dibenzo-p-Dioxin and -Dibenzofurans (CDDs and CDFs)’ and 1989 Update

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COMPARATIVE TOXICOLOGICAL SIGNIFICANCE MAGCORP / US MAGNESIUM DIOXINS vs.

OTHER US OCCURRENCES Units: 2,3,7,8-TCDD (ng/g)

= parts per billion (ppb)

• Times Beach, MOSource: US Public Health Service ATSDR “Toxicological

Profile for 2,3,7,8 - Tetrachloro Dibenzo-p-Dioxin, Table 7.1 (ATSDR/TP-88/23, June 1989)

• Love Canal, NYSource: Love Canal: A Special Report to the Governor &

Legislature, A Special Report to the Governor and Legislature, April 1981 (http://www.health.state.ny.us/nysdoh/lcanal/lcreport.htm#toxicological)

• MagCorp /US Magnesium, UTSource: UDEQ analytical report transmittal, Nov. 1998NOTE: MagCorp/US Mag. Produces extended catalog of dioxin

and furan compounds on-site, whereas other well-known sites were dumping grounds for 2,3,7,8-TCDD only

4.4 - 317 2,3,7,8-TCDD only

0.001 - 0.312,3,7,8-TCDD only

0.11 - 38 ‘TEQ’

Total Dioxins more than 100 x TEQ