34th Annual Conference & Exhibition Environmental Information Association Orlando, FL - March 2017
Erionite: The New Asbestos? Co-presenters: Rob DeMalo Ed Cahill EMSL Analytical, Inc.
1 Zeolites : Erionite
Erionite is a natural occurring mineral; member of the Zeolites Occurs when volcanic ash reacts with ground water and forms fibrous masses inside hollow spaces of rock Hydrated aluminum silicates of the alkaline and alkaline-earth metals. Have large pores and can absorb large quantities Several hundred occurrences of zeolite deposits worldwide Synthetic Zeolites are manufactured
Erionite: Exposure Pathways Past occupational exposures during mining and production operations
No longer mined or marketed for commercial purposes since the late 1980’s
Road construction and maintenance workers exposed to Erionite containing gravel used in road surfacing
Erionite can be found in some other commercial zeolite products, therefore workers and public can be exposed from manufacture and use of these products: Commercial uses of natural zeolites: pet litter, soil conditioners, animal feed, wastewater treatment and gas absorbents
4 Zeolite Use/ Production
Three US Companies account for 85% of total domestic production.
~71,100 tons of natural zeolites were consumed in the US in 2015.
~ 80 % of usage is animal feed, odor control, water purification, pet litter, and wastewater treatment . Industry & Erionite Today 5
1970’s used as a catalyst in a hydrocarbon-cracking process for the oil and gas industry ; replaced synthetics Today it’s mostly found as environmental contaminate and as incidental mineral in zeolite mining. 2004, a congressional hearing took place in Las Vegas, NV for workers who were exposed to Erionite and Silica while drilling in the Yucca Mountain site in Nevada. Yucca Mtn. Nevada (US DOE)
Erionite: Reducing Exposures Some of the mineral’s properties are similar to those of amphibole asbestos; for example, the fibers pose a hazard only if they are disturbed and become airborne.
There are no regulatory or consensus standards or occupational exposure limits for airborne erionite fibers
The U.S. Occupational Safety and Health Administration’s guidance for working with asbestos could serve as a model for limiting the generation and inhalation of dust known or thought to be contaminated with erionite.
Erionite in Turkey & Mexico • Villages in Turkey & Mexico where malignant mesothelioma is a frequent cause of death – • Adobe homes built with Erionite bearing material – Cappadocia Region of Turkey
(2013) Health Implications of Erionite Exposure Near San Miguel de Allende, Mexico: Preliminary Findings - Ortega, A.; Carrasco, G. Erionite in the US 8
Image credits: Map by U.S. Geological Survey, R. Sheppard, Open File Report 96-018 and Electron Micrographs by EMSL Analytical, Inc. Map of occurrences of Erionite in sedimentary rock -1996 9 US Zeolite deposits
(U.S. Geological Survey, Mineral Commodity Summaries, January 2016)
~120 Million tons is present in near-surface deposits
Resources may approach 10 trillion tons for zeolite-rich deposits.
New Mexico was estimated to be the leading natural zeolite- producing State, followed by Idaho, Texas, California, Oregon, and Arizona. 10 US Zeolite deposits
Geologic formations have been found throughout western US(Carbone et al., 2011;Van Gosen et al., 2013).
Gravel pits are contaminated with Erionite excavated in western North Dakota(Dunn County Erionite Workgroup, 2010).
Sine the 1980’s, this gravel has been used to construct more than 300 miles of local rods, parking lots, baseball fields playgrounds and other areas(Carbone et al., 2011).
11 US Zeolite deposits
Erionite Bulk Sampling Guidelines for ND – October 2007 Sampling equipment and strategies – ASTM references
Trained personnel; i.e., asbestos exp., PPE, etc.
Laboratory personnel; at least 2 years experience
Sampling plan; sample size - 1quart
Number of samples, composite bulk sample from:
Every acre containing pit exploration test borings, proposed excavations or excavation – min 3 random samples
Every 1,000 tons of aggregate stores in piles –min 3 samples Randomly chosen over surface of pile, due to sloughing; size segregation, finer material at top of pile
Lab analysis; bulk samples a combination of SEM and XRD
12 US Zeolite deposits – USGS Study 2010
13 US Zeolite deposits – USGS Study 2010
April 2008, USGS and US EPA Region 8 scientists collected samples in Cappadocian region of Turkey North Dakota samples collected by North Dakota Geological Survey Rome, OR samples collected by US EPA Region 10 SEM/EDS & EPMA analysis
14 US Zeolite deposits – USGS Study 2010
Findings: General morphology of Erionite from studied localities similar Erionite composed of single fibers, bundles of fibers and radiating bundles of fibers
15 US Zeolite deposits – USGS Study 2010
Findings: Fiber sizes ranged from less than 0.2 µm to 10 µm in diameter and lengths that range from 2 µm to over 200 µm
16 US Zeolite deposits – USGS Study 2010
Findings: Erionite fibers from the Turkey air samples tend to have a greater AR than North Dakota air samples ABS and Perimeter air samples
17 US Zeolite deposits – USGS Study 2010
Findings: Elemental composition varies by locality
18 US Zeolite deposits
Not new;
Published Erionite paper 1959, citation from Harvard professor Eakle from 1898 Reported unusual zeolite from Durkee, OR
ERIONITE: NEVADA Boulder City Bypass
Erionite is believed to be present in NV and is being investigated with NOA in the areas around the proposed BCBP site.
19 N. Dakota Erionite
Erionite is present in Killdeer Mountain
Pits are primary source of gravel
90 Day Notice must be provided to EPA before putting Erionite to use
More Info can be found on ND DOH website
Photos courtesy of Mark Dihle, ND DOH Erionite: Deadly Danger
Health Studies Classified as an Not have shown an Class I regulated increased risk of carcinogen by and no developing the WHO and established malignant mesothelioma in IARC. exposure Turkey where the limits Erionite-rich rock was used to build houses.
Image from Wikimedia
Erionite Induced Auto Immune Disease
Studies have shown that Erionite and amphibole asbestos induce auto immune responses in mice.
Mouse model data suggests that erionite may encourage the production of autoantibodies commonly seen in people with systemic autoimmune diseases.
Zebedeo, C.N., et al., Erionite induces production of autoantibodies and IL-17 in C57BL/6mice, Toxicol. Appl. Pharmacol. (2014), http://dx.doi.org/10.1016/j.taap.2014.01.018 Erionite – Health Effects
Numerous published studies show evidence of environmental exposures to Erionite and the onset of adverse health effects, including malignant mesothelioma
Ferruginous bodies (FBs) and fibers found in bronchoalveolar lavage fluid (BALF) from inhabitants of villages in Cappadocia, Turkey
Erionite exposure
In 2015, NIOSH and the CDC released a report: Evaluation of Erionite and Silica Exposure During Forestry Activities.
Collected air, rock and soil samples for erionite mineral fibers during forestry activities collected in the vicinity of the employees.
All employees were exposed to erionite mineral fiber. PHOTO BY NIOSH. NIOSH [2015]. Health hazard evaluation report: evaluation of erionite and silica exposure during forestry activities. By Beaucham C, Harper M, King B, Dozier A. Cincinnati, OH: U.S. Department of Health and Human Services, Centers for Disease Control and Prevention, National Institute for Occupational Safety and Health, NIOSH HHE Report No. 2013-0061-3244. Erionite exposure
Activity Based Sampling (ABS) demonstrated exposures in Dunn County 0.175 fibers/cm3
Higher or similar levels to those found in Turkish villages (0.0421-0.221 fibers/cm3 which are experiencing mesothelioma rates as high as 1 in 1,000
Karain, Turkey over 50% of all deaths (1990-2006) are due to mesothelioma
Latency period in this town was 53.8 years (Metintas et al., 2010).
US rates of mesothelioma are 1-15 per 106 (Carbone et al., 2011).
Therefore too early to tell in ND, however Dunn County study did report evidence of fibrotic pleural disease consistent with Erionite exposures (workers did not history of asbestos exposure) Reducing Exposure
Proper Hazard disposal Training
Avoid Erionite Wet Gravel Controls use
Limit Bystanders PPE
Know Establish location Decon of Erionite Protocols
27 Erionite Analysis
ASBESTOS TECHNIQUES ZEOLITE ISSUES
28
Identifying Erionite - XRD one of the first “go to” analyses for characterizing bulk materials for Zeolites - Sensitivity is only around <1% - Can’t tell fibrous from non-fibrous - Not usable for air samples on filters - Erionite and Offretite can occur together and have very similar XRD patterns By TEM Individual Fibers Can Look Like Asbestos
31 • Some have very small diameters like Chrysotile • Typically we are seeing bundles or aggregates of fibers • More ribbon like bundles rather than rod like TEM Identifying Erionite
2009 NVLAP TEM PT - Erionite • All 76 labs reported it correctly as “other” • 9 of the 76 labs attempted to ID it further • Only 3 correctly ID as Erionite.
In 2013 the same sample was given again • 46/76 Labs correctly identified it as Erionite 34 Distinguishing from Asbestos is Easy
Aluminum Silicate with varying amounts of K, Ca, and Na
Al:Si ratio 1:3 or 1:4 Lots of compositional variation
These overlapping spectra are all from fibers from the same sample with North Dakota Erionite
35 But Individual Zeolites Can Have Varying Chemistry
Erionite-Ca Erionite-Na Erionite-K
36 Different Zeolites Can Have Similar Chemistry
Offretite Erionite Mordenite
37 >80 Natural Zeolites >150 Synthetic Zeolites
• Arizona is one of the nations largest producers (mostly chabazite and mordenite) for industrial applications such as fuel drying, odor absorbing, catalysts, filtration, etc. • Fortunately only 6 or 7 truly fibrous Zeolites • A dozen elongate Erionite Arizona
Macro Inside vesicle (vug) 39 Additional Zeolites
Offretite & Chabazite Mordenite & Heulandite
40 Offretite & Chabazite Lake Arno - Alta Val Saviore – Mt. Adamello - Brescia prov. - Lombardy - Italy
Offretite Chabazite
41 42 Mordenite Ugas Quarry Sardinia Italy Erionite Chemistry (Passaglia et al, 1998) (Dogan et.al. 2006) The Crystal chemistry of the zeolites erionite and Offretite
(USGS: Lowers, Adams, Meeker, Nutt)
Range of Tsi 0.68-0.79 Ca is most dominant extra framework Cation K is always present in considerable amounts (1.6-3.4) Mg cannot really be higher than 0.82 apfu in Erionite Chemistry is reliable if Charge Balance Error aka Balance Error aka E Balance aka E% is <10%
*TSi the proportion of tetrahedron sites occupied by Si atoms as reported in published results of acceptable 43 analyses . For many zeolites this value varies widely, and the values reported may not indicate the full range possible. Especially in rare zeolites. Identifying Erionite-Quant Chemistry
Most research to date has focused on bulk sample chemistry techniques – EMPA, ICP-MS or Electron Backscatter & calculating charge balance (E Balance %) In a 2011 paper, Erionite from Turkey was characterized using TEM EDS from an Air cassette. Applying the criteria: E < 10% and the Mg Content <0.8 Out of 60 analyses: 11 passed E% test (18.3%), 33 passed Mg-content test (55.0%) 3 passed both E% and Mg-content tests (5.0%).
Identifying Erionite-Quant Chemistry
Out of 60 analyses: 11 passed E% test (18.3%), 33 passed Mg-content test (55.0%) 3 passed both E% and Mg-content tests (5.0%) Demonstrates the difficulty of quantitatively characterizing erionite by EDS alone
In 2010 USGS Paper (EPMA data) Lowers,Adams, Meeker set an acceptable E% of 20% due to fibrous nature, small widths and volatile losses
TEM Erionite TEM Beam Damage
Prior to focused beam interaction After focused beam interaction
47 Erionite Beam Sensitivity
~ 3 um damaged area from 15 kv electron beam Within 15 seconds the K Ka intensity reduced by ~ 1/3 TEM is operating at 80-100 Kv for routine asbestos analysis.
Electron Beam damage Erionite
Michele Carbone, et. Al Erionite exposure in North Dakota and Turkish villages with Mesothelioma PNAS 2011 108 (33) 13618-13623; published ahead of print July 25, 2011,doi:10.1073/pnas.1105887108 48 Dehydration Changes Inter-row Spacing
Thermal behavior of Erionite – Na and Erionite – K are just being understood. In a study in 2015, Erionite –Na and Erionite- K had contrasting thermal behaviors. Shows that the importance of thermal stability of chemistry. Erionite –Na has shown high compressibility of the C- Ballirano, P. and Pacella, A. Erionite-Na upon heating: dehydration parameter contracting from dynamics and exchangeable cations mobility. Sci. Rep. 6, 22786; doi: 15.14 A to 14.87A 10.1038/srep22786 (2016).
Beam Degradation = No Diffraction Pattern
Diffraction Pattern Typically < 10 seconds Not enough time for ID These beam interactions effect re-analysis, because once the fiber is degraded this diagnostic information is gone
50 Beam Sensitivity also the Reason for Poor EDS Chemistry !!
Potassium and Sodium volatility
So no diffraction or good chemistry??
What to do? Give up? 51
Cryo Holder
-321 degrees Fahrenheit -196 degrees Centigrade
52 Gatan Cryo Holder
Double walled insulated dewar Packed with an insulation material that doubles as a moisture absorber.
List price $67,000 Erionite Diffraction Pattern
Erionite Fibers Standard Holder LN Cold Stage Rome, Oregon Lasts <15 seconds Lasts more than 5 minutes
54 Crystal Spacing for Select Zeolites
Zeolite C TSi* Comment
Erionite-Na 15.048 0.74-0.79 Fibrous Erionite-K 15.075 0.74-0.79 Fibrous Erionite-Ca 15.091 0.68-0.79 Fibrous Offretite 7.592 0.69-0.74 Fibrous Levyne-Ca 23.014 0.62-0.70 Levyne-Na 22.684 0.65-0.68 Mordenite 7.501-7.537 0.80-0.86 Fibrous Chabazite-Ca 15.040 0.58-0.80 Cubic Chabazite-Na 15.165 0.62-0.79 Cubic Chabazite-K 15.165 0.60-0.74 Cubic Mazzite 7.646 0.72 Fibrous Mesolite 6.544 0.59-0.62 Fibrous Natrolite 6.593 0.59-0.62 Fibrous Perlialite 7.510 0.65-0.67 Fibrous *TSi the proportion of tetrahedron sites occupied by Si atoms as reported in published results of acceptable analyses . For many zeolites this value varies widely, and the values reported may not indicate the full range possible. Especially in rare zeolites. SAED Success Rate
SAED SAED >15 s % >15s Achieved Source Holder out of 10
Rome (OR) cold holder 9 9 100%
Rome (OR) warm holder 8 4 47%
Custer (SD) cold holder 10 8 80%
Custer (SD) warm holder 8 1 13%
JEOL 1200 EX II STEM Operating at 100 keV aperature < 250 nm. CRYO Holder and EDS 57
Specimen Holder Potassium Counts Source % Decline @ 30s
Rome, Standard 52.4 Oregon
Rome, Cryo Holder 29.2 Oregon
Custer Cryo Holder 17.6
Custer Standard 31.0 Quantitative Chemistry Improved
Si:Al ratio Oxygen wt% Ca wt% K wt% Na wt% EMPA TEM Cryo TEM EMPA TEM Cryo TEM EMPA TEM Cryo TEM EMPA TEM Cryo TEM EMPA TEM Cryo TEM 3.9 4 3.97 48 51 49.1 4.5 3.2 3.36 4.4 1.9 3.38 0.4 0 0.11 Rome (microprobe17/ Old TEM10) Rome 4 45 3.4 4.3 0
New TEM (30)
CGNF (microprobe19/ 3.9 4 3.97 49 52 49.5 1.8 1.3 1.7 3.1 1.7 3.54 0.9 0.4 0.7
Old TEM10)
CGNF 3.9 47 1.5 3.8 0.9
New TEM (24)
Karain (microprobe19/ 3.8 3.4 3.59 49 43 49.6 1.4 1.1 1.19 3.6 4.7 3.64 1.8 1.9 1.55
Old TEM11)
58 Morphology Diffraction EDXA 15.00 Ang
59 Erionite Sample vs. Reference
Reference Criteria Value 1 2 3 4 5 6 7 8 9 10 Si+Al 36 36.03 36.30 35.77 36.04 35.91 36.06 36.17 36.11 36.43 35.87 Tsi ( Si/Si+Al) 0.68-0.79 0.77 0.77 0.76 0.78 0.77 0.77 0.77 0.77 0.77 0.78 Mg / (Ca+Na) <0.15 0.01 0.03 0.17 0.05 0.02 0.01 0.02 0.02 0.01 0.02 Mg (Based 72O) <0.8 0.03 0.09 0.36 0.16 0.06 0.03 0.05 0.06 0.03 0.06 Si/Al^ 2.85-3.6 3.34 3.31 3.25 3.48 3.38 3.43 3.39 3.34 3.36 3.48 K+Na > Ca+Mg^ TRUE TRUE TRUE TRUE TRUE TRUE TRUE TRUE TRUE TRUE TRUE Abundant Cation Ca, Na, K K K K K K K K K K K E%* < 20% 2.56 19.30 28.59 9.56 2.92 13.17 11.07 14.55 26.76 8.73 Inter-Row 15.07 15.10 15.20 15.50 15.30 15.20 15.40 15.30 14.90 15.40 15.40
60 Morphology Diffraction EDXA 7.62 Ang
61 Offretite Sample vs. Reference
Reference Criteria Value 1 2 3 4 5 6 7 8 9 10 Si+Al (72 O) 36 36.48 36.20 36.26 35.96 36.06 36.18 36.36 35.94 35.82 36.49 Tsi ( Si/Si+Al) 0.69-0.74 0.71 0.71 0.71 0.71 0.70 0.71 0.70 0.70 0.70 0.71 Mg / (Ca+Na) 0.7-1.1 0.44 0.37 0.41 0.26 0.37 0.39 0.61 0.45 0.29 0.44 Mg (Based 72O) 1.4-2.0 0.85 0.93 0.88 0.57 0.77 0.89 1.08 1.01 0.73 0.85 Si/Al^ 1.99-2.8 2.42 2.44 2.48 2.49 2.35 2.45 2.36 2.37 2.35 2.42 K+Na < Ca+Mg^ TRUE FALSE TRUE FALSE FALSE FALSE FALSE FALSE FALSE FALSE FALSE Inter-Row 7.592 7.74 7.60 7.69 7.62 7.53 7.51 7.64 7.57 7.57 7.52 E%* < 20% 26.36 10.97 13.56 13.21 5.54 11.23 31.90 -0.63 -3.32 26.47 Morphology Diffraction EDXA 7.58 Angstrom
63 Mordenite Sample vs. Reference
Reference Criteria Value 1 2 3 4 5 6 7 8 9 10 Tsi ( Si/Si+Al) 0.80-0.86 0.81 0.82 0.82 0.80 0.81 0.82 0.83 0.81 0.81 0.82 Na/ (Na+Ca) 0.50-0.81 0.40 0.60 0.51 0.53 0.39 0.47 0.48 0.45 0.17 0.44 Inter-Row 7.501-7.537 7.35 7.50 7.56 7.58 7.55 7.52 7.59 7.27 7.63 7.50 E%* < 20% 31.39 -5.33 10.25 0.12 24.45 20.77 7.51 17.19 29.07 24.80 Conclusions • Erionite vs Asbestos is Easy • Erionite vs other zeolites not always easy • Need Good Quantitative Chemistry and Diffraction • Both are non starters due to beam sensitivity • Cryo holder to the rescue • Now, Chemistry gets us in the ballpark • SAED nails it down References • Robyn Ray, EMSL Analytical, Inc. • https://www.cancer.gov/about-cancer/causes-prevention/risk/substances/erionite • National Toxicology Program. Erionite, Report on Carcinogens, Thirteenth Edition. Triangle Park, NC: National Institute of Environmental Health and Safety, 2014. • Weissman D and Kiefer M Erionite: An Emerging North American Hazard. NIOSH Science Blog, November 22, 2011 • (U.S. Geological Survey, Mineral Commodity Summaries, January 2016) Zebedeo, C.N., et al., Erionite induces production of autoantibodies and IL-17 in C57BL/6mice, Toxicol. Appl. Pharmacol.(2014), http://dx.doi.org/10.1016/j.taap.2014.01.018 • Passaglia E., The Crystal Chemistry of Chabazites, The American Mineralogist, 1970 • Arizona Zeolites, Mineral Report No.-01, State of Arizona department of Mineral Resources • Cametti, Pacella, et.al.,New morphological, chemical, and structural data of wooly erionite- Na from Durkee, Oregon, U.S.A., American mineralogist, 2013 • Dogen A., Dogan M., Re-Evaluation and re-classification of erionite series minerals, Environ Geochem Health, 2008 • Tschernich Rudy, Zeolites of the World, Geoscience Press, Inc., 1992 • https://www.ndhealth.gov/EHS/Erionite/Contractors/Erionite_Bulk_Sampling_Guidelines.pdf • Lowers, H.A., Adams, D.T., Meeker, G.P., and Nutt, C.J., 2010, Chemical and morphological comparison of erionite from Oregon, North Dakota, and Turkey: U.S. Geological Survey Open- File Report 2010–1286, 13 p.
Questions?
• Robert DeMalo, M.Sc. Senior Vice President, Laboratory Services & Business Development • Edward Cahill, Vice President, Asbestos • EMSL Analytical, Inc. • 200 Route 130 N • Cinnaminson, NJ 08077 • 800-220-3675 • [email protected] • [email protected] • www.emsl.com
• Thank you for your attention and thank you EIA!