Respirable Crystalline Silica (RCS) Understanding the Regulations, Science & Results. Marc Hugus Manager, Business Development

Transcription

1 Respirable Crystalline Silica (RCS) Understanding the Regulations, Science & Results Marc Hugus Manager, Business Development

2 Marc Hugus Manager, Business Development Over 30 years consultative technical business development, sales and marketing experience in Oil and Gas, Engineering, Environmental Consulting and Automated Mapping and GIS Bachelors and Masters degrees in Geography Over 6 years experience in environmental and industrial hygiene laboratory sales and customer service Knowledgeable in OSHA and EPA regulations for air, water, soil and industrial hygiene sampling and analysis Involved with IPO s for 4 companies, including MapQuest.com MTA-PALMS RCS Understanding the Regulations, Science & Results 2

3 What is Silica? Family of materials consisting of silicon dioxide (SiO 2 ) Crystalline mineral and amorphous material Concern is Crystalline Form a solid 3D structure of SiO 2 atoms having fixed distances, preferred orientation(s) and arrangement Quartz is the most ubiquitous compound on earth (~43% by weight) Regulated Crystalline Silica Polymorphs (Respirable) Quartz Cristobalite Tridymite MTA-PALMS RCS Understanding the Regulations, Science & Results 3

4 What is a Respirable Particle? < 10 microns (aerodynamic mass diameter) Inhaled particles can reach deep regions of lung (Alveoli) ACGIH TLVs and BEIs Appendix C Fraction Collected (%) Aerodynamic Diameter (microns) MTA-PALMS RCS Understanding the Regulations, Science & Results 4

5 Exposure to Crystalline Silica Source material Nature.rocks Igneous granite, other felsic igneous rocks Sedimentary sandstone, shale, carbonates Metamorphic schist, gneiss, quartzite, etc. How is it released? Pulverized, crushed, fractured, etc. Potential risk for delayed health effects: Silicosis Lung cancer Chronic obstructive pulmonary disease (COPD) Kidney disease MTA-PALMS RCS Understanding the Regulations, Science & Results 5

6 Work Activities of Concern Stone Cutting, Grinding and Polishing Foundry Operations Sand Blasting Manufacturing (e.g. Glass and Ceramics) Building Demolition/Renovation Concrete, Masonry and other Construction Materials Mining/Quarrying (various) Materials Handling/Packaging Bulk shipping/transportation Agriculture Etc. MTA-PALMS RCS Understanding the Regulations, Science & Results 6

7 Assess, Recognize, Evaluate, Control & Confirm Review possible risks and exposures - Risk = Exposure (amount and duration) X Potential Toxicity Implement OEHS program(s) Evaluate containment capabilities - Conduct containment assessment Enhance containment systems - Work practices - Engineering controls Re-evaluate and confirm controls - Conduct exposure assessment MTA-PALMS RCS Understanding the Regulations, Science & Results 7

8 New OSHA Rules Summary Permissible Exposure Limit (PEL) reduced to 50 mg/m 3 for 8 hour TWA Action Level (AL) reduced to 25 mg/m 3 for 8 hour TWA Key Dates - Construction September 23, General Industry/Maritime June 23, Hydraulic Fracturing* June 23, 2018 *Engineering Controls June 23, 2021 On-going evaluation If above AL but below PEL Reevaluate exposure within 6 months If above PEL Reevaluate exposure within 3 months - If below AL Repeat monitoring within six months (2 samples at least 7 days apart) to confirm controls Changes in the production, process, control equipment, personnel, or work practices MTA-PALMS RCS Understanding the Regulations, Science & Results 8

9 OSHA Record Keeping Exposure Monitoring Air Sampling Sample dates and tasks Sampling and analytical method used Number, duration and results for samples Laboratory identity PPE utilized during sampling Social Security Numbers for employees covered Objective Data Materials in question Comparable industry/task data sources Testing protocols/results Descriptions of processes and tasks Other relevant data MTA-PALMS RCS Understanding the Regulations, Science & Results 9

10 Various Sampling and Lab Methods (Crystalline Silica on Filters) MSHA P7 (FTIR) coal mines MSHA P2 method (XRD) metal/non metal mines NIOSH 7500 (XRD) NIOSH 7602 (IR-KBr pellet) NIOSH 7603 (IR-redeposition) OSHA ID 142 (XRD) similar to NIOSH 7500 MTA-PALMS RCS Understanding the Regulations, Science & Results 10

11 NIOSH 7500 Method Summary OSHA approved for analysis of silica in airborne dust Filter redisposition - Polyvinyl Chloride (PVC) Analysis by X-Ray Diffraction (XRD) MTA-PALMS RCS Understanding the Regulations, Science & Results 11

12 Polyvinyl Chloride (PVC) Filters Suitable for multiple NIOSH/OSHA/ASTM air sampling methods Silica Metals Dust (silica-free, low ash) Hydrophobic - low tare weight and moisture pickup for gravimetric stability Non-oxidizing surface Standard pore size 5mm for silica Secondary electron image of a PVC filter MTA-PALMS RCS Understanding the Regulations, Science & Results 12

13 Sample Collection Chain of Custody XYZ Company Sample Collection Record Sample Date Sample No. Sample Description Media Pump No. Pre-Flow Rate (L/min) Start Time Post-Flow Rate (L/min) Stop Time Avg. Flow Rate Total Time (min) Volume (L) Analysis Personal - Total Dust PVC (5.0) NIOSH 0500 Personal - Resp / Silica PVC (5.0) NIOSH 0600/7500 Area 1 - Total Dust PVC (5.0) NIOSH 0500 Area 1 - Resp / Silica PVC (5.0) NIOSH 0600/7500 Area 2 - Total Dust PVC (5.0) NIOSH 0500 Area 2 - Resp / Silica PVC (5.0) NIOSH 0600/7500 PDR - Resp / Silica PVC (5.0) NIOSH 0600/7500 Field Blank PVC (5.0) NIOSH 0500 Field Blank PVC (5.0) NIOSH 0600/7500 Relinquished by: Date/Time Method of Shipment: Hand delivered Received by: Date/Time Sample Condition Upon Receipt: Acceptable Other (explain on reverse) Request for Laboratory Analytical Services - Chain of Custody Page of ATTENTION TO: Lab Use Project No.: Client No.: Purchase Order Number: Client Job Number: Only Date Logged In: Logged In By: Name: Name: Company: Send Company: Fax: Address: Invoice Address: Report City, State, Zip: To City, State, Zip: Results Phone: Fax: Phone: To Call with verbal results: Rush Charges Yes Date Results Standard TA assumed if left blank; results to: Authorized? Requested please do not use vague terms like ASAP (circle one) Fax results to: No Accreditations required to be followed: yes no Analysis Requested Special Instructions or Comments Quality System ISO (Please specify): Requirements Circle which ones cgmp: (if applicable) to follow: Other (Please specify): Client Sample ID Sample Description Sample Location Sample Date Chain of Relinquished By (Signature): Date: Time: Chain of Received By (Signature): Date: Time: Custody Relinquished By (Print Name): Relinquished To: Custody Received By (Print Name): Relinquished To: Company Name: Method of Shipment: Company Name: Method of Shipment: Chain of Relinquished By (Signature): Date: Time: Chain of Received By (Signature): Date: Time: Custody Relinquished By (Print Name): Relinquished To: Custody Received By (Print Name): Relinquished To: Company Name: Method of Shipment: Company Name: Method of Shipment: MTA-PALMS RCS Understanding the Regulations, Science & Results 13

14 Size Selective Sampling Cyclones Cyclone 10-mm nylon cyclone Higgins-Dewell (HD) cyclone SKC Aluminum cyclone BGI GK 2.69 cyclone Flow Rate 1.7 L/min 2.2 L/min 2.5 L/min 4.2 L/min Ensure the cassette is loaded into the cyclone properly Do not invert sampler assembly while using the cyclone Air Inlet Respirable Coarse Grit pot MTA-PALMS RCS Understanding the Regulations, Science & Results 14

15 Sampler Calibration Calibrate flow rate to primary standard Include entire sampling train Direct flow check (rotameter) or Bell Jar ( old school ) Check flow rate before and after sampling MTA-PALMS RCS Understanding the Regulations, Science & Results 15

16 SKC PPI Sampler Parallel Particle Impactor (PPI) from SKC, Inc. Alternative sampler - Eliminates need for cyclone (no inversion issues) - Compatible with multiple sampling pumps - Available in 2L, 4L and 8L - Increases worker comfort OSHA approved MTA-PALMS RCS Understanding the Regulations, Science & Results 16

17 Exposure Monitoring Tips Inspect and Test Equipment Cassettes for cracks/leaks Integrity of tubing O-rings and seals Clean cyclone and grit pot Orientation of Sample Inlet and Cyclone Maximize Sampling Air Volume Know Where your Sampler has Been Augment with Direct-reading Instruments Avoid Sampler Contact with Settled Dust Moderate Potential Interferences MTA-PALMS RCS Understanding the Regulations, Science & Results 17

18 NIOSH 7500 Laboratory Analysis Follow a Sample through the Laboratory MTA-PALMS RCS Understanding the Regulations, Science & Results 18

19 X-Ray Diffraction (XRD) Used to Evaluate Crystalline Materials NIOSH 7500, Crystalline Silica by XRD Three regulated crystalline silica minerals - Quartz, cristobalite, and tridymite - Other methods may not differentiate the 3 polymorphs MTA-PALMS RCS Understanding the Regulations, Science & Results 19

20 Cassette Assembly Filters Used (typical) 5 µm pore size 37 mm diameter Polyvinyl chloride (PVC) Pre-weights Weighed in sets of 10 Every 10 th weight is reweighed to ensure that the balance did not drift during weighing of the set MTA-PALMS RCS Understanding the Regulations, Science & Results 20

21 Cassette Assembly (continued) Assemble Cassette 2 or 3 piece depending on cyclone SKC PPIs Tracking Number Unique ID for each cassette Identifies pre-weight of filter and time/date of assembly MTA-PALMS RCS Understanding the Regulations, Science & Results 21

22 Sample Preparation (1) Samples received Dried in a desiccator Cassettes carefully opened to remove filters Filters post-weighed Total respirable dust mass calculated Gravimetric Analysis NIOSH 0500 NIOSH 0600 MTA-PALMS RCS Understanding the Regulations, Science & Results 22

23 Sample Preparation (2) NIOSH 7500 Options Low temperature plasma ashing (beaker) 1 ~ 150 C Muffle furnace ashing (crucible) C Filter dissolution Tetrahydrofuran (THF) MTA-PALMS RCS Understanding the Regulations, Science & Results 23

24 Sample Preparation (3) 15 ml of 2-Proponal is added to each beaker Cover and sonicate Obtain a silver membrane filter 25 mm 0.45 µm Attach funnel MTA-PALMS RCS Understanding the Regulations, Science & Results 24

25 Sample Preparation (4) Pour suspension into the funnel Rinse walls of beaker Apply vacuum Remove the silver filter with the sample deposited on it MTA-PALMS RCS Understanding the Regulations, Science & Results 25

26 Sample Preparation (5) Mount into XRD holder Place in orderly fashion Ready for analysis MTA-PALMS RCS Understanding the Regulations, Science & Results 26

27 X-Ray Diffractometer X-ray Source Detector Sample Goniometer PANalytical Cubix 3 Diffractometer MTA-PALMS RCS Understanding the Regulations, Science & Results 27

28 XRD Basics λ = 1.54 Å, CuKa Incident X-ray beam λ Diffracted beam Atomic Planes q q d nλ=2dsinθ Bombardment of X-rays results in scattering of the X-rays off of atomic planes X-Ray diffraction produces patterns that are indicative of the atomic planes in a material, which serve as a fingerprint for individual minerals MTA-PALMS RCS Understanding the Regulations, Science & Results 28

29 XRD Data Counts Position [ 2Theta] (Copper (Cu)) MTA-PALMS RCS Understanding the Regulations, Science & Results 29

30 XRD Data Counts Quartz Silver Silver Chloride Primary Silver Peak Primary Quartz Peak Secondary Quartz Peak Position [ 2Theta] (Copper (Cu)) MTA-PALMS RCS Understanding the Regulations, Science & Results 30

31 NIOSH External Standard Method Create standards from a pure mineral Construct a calibration curve Compare unknown samples to known standard results to determine silica quantification MTA-PALMS RCS Understanding the Regulations, Science & Results 31

32 Calibration Standard Data 2.5 µg Qtz 5 µg Qtz 10 µg Qtz 25 µg Qtz µg µg Qtz Qtz 250 µg Qtz Blank Quartz Detection Limit MTA-PALMS RCS Understanding the Regulations, Science & Results 32

33 XRD Method Potential Interferences Mica* Potash Feldspars* Zircon Graphite Aluminosilicates Best way to determine interferences: collect a bulk settled dust sample or send the bulk material in question for XRD analysis for phase identification. MTA-PALMS RCS Understanding the Regulations, Science & Results 33

34 Lower LOQ Analysis Detection limit reduced by 50% mg vs 5.0 mg Accomplished through advanced instrumentation and software upgrades Requires additional sample prep and analysis AIHA LAP Approved Uniquely available from RJ Lee Group MTA-PALMS RCS Understanding the Regulations, Science & Results 34

35 Standard vs. Enhanced Spectral Analysis Standard analysis 5.0 mg/filter Enhanced analysis 2.5 mg/filter MTA-PALMS RCS Understanding the Regulations, Science & Results 35

36 Advantages of Lower LOQ Low sample volume on filter - Short duration sample event - Clean working environment Requirement for numerical reporting below industry standard Environmental (ambient/fence line) monitoring MTA-PALMS RCS Understanding the Regulations, Science & Results 36

37 Standard Report Overview RJ Lee Group, Inc. 350 Hochberg Road, Monroeville, PA Tel: (724) Fax: (724) LABORATORY REPORT ABC Company 1 Industrial Way Pittsburgh, PA REPORT DATE June 4, 2014 ATTENTION: Crystal N. Silica SAMPLES RECEIVED May 30, 2014 TELEPHONE: 724-XXX-XXX RJ LEE GROUP JOB NO. PA CLIENT JOB NO. N/A ANALYSIS: Respirable Dust and Crystalline Free Silica Dust on 5 µm PVC Air Filters PURCHASE ORDER NO: N/A METHODS: Gravimetry, NIOSH 0600 and X-Ray Diffraction, NIOSH 7500 LOD: mg Quartz, Cristobalite, and Tridymite mg Respirable Dust Air* Respirable Masses of Free Weight Percentages of Airborne Dust Sample Identification Volume Dust Mass Silica Minerals (mg/filter) Crystalline Silica Minerals Concentrations (mg/m 3 ) Client I.D. RJ Lee Group (liters) (mg/filter) Quartz Cristobalite Tridymite Quartz Cristobalite Tridymite Respirable Quartz Cristobalite Tridymite Sample A < < < 1.0 < < < Sample B < < < 1.0 < < < Sample C < < < 1.0 < < < Sample D < < < 1.0 < < < Sample E < < < 1.0 < < < Blank 006 N/A < < < N/A N/A N/A N/A N/A N/A N/A * Supplied by the client. N/A Not Applicable Air volume during a worker s shift Mass of material on filter from micro-balance Mass ofmineral Mass of total dust 100 Mass Air Volume 1000 MTA-PALMS RCS Understanding the Regulations, Science & Results 37

38 Balance Calibration daily Gravimetric test samples Calibration Curve Reanalyze and re-measure standards (every 3 mos.) CCV Continuing Calibration Verification Set of standards run after every 10 th sample To ensure the calibration curves remain accurate RL Reporting limit Set of standards run daily To ensure that tube intensity is strong enough to see the RL (0.5µg) Sample Preparation Blanks every day To check for cross contamination between samples during preparation Analysis 10% of unknown samples are re-measured by a second analyst 10% of CCVs and RLs are re-measured by a second analyst Audits AIHA audit every 2 years Internal audits annually Quality Assurance MTA-PALMS RCS Understanding the Regulations, Science & Results 38

39 Lab Considerations Laboratory Selection Sample preparation per method considerations Capability to address interferences Quality assurance and accreditation Detection limits Sampling guidance and support Technology Advancement Sample concentration and sampling methods Advances in instrumental analysis / optimization MTA-PALMS RCS Understanding the Regulations, Science & Results 39

40 RJ Lee Group Using the power of science to prove your products safe and environmentally friendly Marc Hugus: MTA-PALMS RCS Understanding the Regulations, Science & Results 40