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Department of Toxic Substances Control Cal/EPA
Bruce La Belle, Ph.D.Laboratory Chief
December 9, 2016Berkeley, CA
Environmental Chemistry Laboratory
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Speakers• Overview
• Dr. Bruce La Belle
• Analytical Chemistry Support • Dr. Robert Ramage
• Scientific Leadership, Biomonitoring, and Emerging Chemical Issues• Dr. Myrto Petreas
• External Perspectives
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Mission
The Environmental Chemistry Laboratory provides scientific leadership
for DTSC in analytical and environmental chemistry to protect
public health and the environment from adverse effects of chemicals
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Vision
Nationally recognized scientific leadership in the analytical and
environmental chemistry of toxic chemicals for a healthy, sustainable, and
prosperous California
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Executive Decision-Making
Safer Products & Workplaces
Brownfields & Environmental Restoration
Analytical Testing
ConsumerProducts Testing
Environmental Chemistry &
Biomonitoring
ECL
Emerging Scientific Issues
Conceptual ModelDecember 9, 2016
HWMPEnforcement
OCIPermitting
Policy
Foundation for DTSC Decision-Making
& Scientific Expert Support
PresenterPresentation NotesI suggest to rework on animation. By looking at it, it doesn’t capture my eyes at first time.
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We Test a Wide Variety of Materials
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Scientific Expert Technical Support
• Analytical methods selection• Project plans/sampling plan review• Split sample testing• Data quality review/interpretation/validation• Training• Reference Lab
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Values Scientific Excellence Integrity Impartiality Independence Defensibility Consistency Traceability
Transparency Customer Service
Workplace Diversity Courtesy Respect
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ECL as an Organization
Analytical ChemistryDr. John Quinn
Quality Manager & Technical
Support
BiomonitoringDr. June-Soo Park
Environmental Chemistry
Dr. Myrto Petreas
ECL Lab Chief
Director
Chief Deputy Director
CleanupHWMPSafer Products & Workplaces
Environmental Justice
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ECL as Centers of Excellence:The People
• ECL-Berkeley : 37 Staff• ECL Pasadena : 12 Staff
• Visiting Scholars: ~10• Postdoctoral researchers, visiting professors
• Graduate students, undergraduates• Highly Experienced Scientists
PresenterPresentation NotesWe do not have visiting professor
MS17% is not really lined up
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Centers of Excellence:Laboratory Infrastructure
• ECL-Berkeley – Specialized facilities including Clean Room laboratories
• ECL-Pasadena – New, state-of-the-art laboratory replaces 1950’s facility
• Ability to serve major areas of State• Inter-laboratory method validations• Continuity of operations in event of earthquake
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Centers of ExcellenceState-of-the-Art Analytical Equipment
A
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• GC-MS/MS• GC-HRMS• LC/MS/MS• LC-QTOF-MS• LC-ICP-MS• ICP-OES• GC-MS• GC-ECD• HPLC• XRF
~$12 Million in instruments and other equipment
PresenterPresentation NotesI changed a bit to be consistent: e.g., GC/MS/MS GC-MS/MS
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• Quality Control• Instrument calibration and monitoring• Quality Control samples with every batch
• Quality Assurance• Standard Operating Procedures• Review of data package by second chemist
• Quality Management• Manager review of each analytical report• Performance Evaluation Samples
• Demonstration of competency
Ensuring the Quality of Our Work
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• ECL has over 100 SOPs and Worksheets:• Sample Receiving & Log-in• Sample Preparation• Sample Analysis• Report Formats• Glassware cleaning
• EPA Standard Methods (SW-846)• 8260B-Volatile Organics by GC/MS• 8270C-Semivolatie organics by GC/MS• 6010B-Total metals by ICP
Standard Operating Procedures
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Foundation for Decision-Making
• Current Core Program activities
• Emerging issues that will affect DTSC in 1-5 years• New chemicals• New technologies• New matrices• New laws and regulations
PresenterPresentation NotesNew regulations?
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Thank You
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Department of Toxic Substances Control Cal/EPA
Analytical Support – Berkeley
Robert Ramage, Ph. D.Supervisor
December 9, 2016Environmental Chemistry Laboratory
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Introduction / Outline
• What we do• How we do it • Types of special projects• Uses of lab results
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What We Do: Test Using EPA Methods
• Organics: chemicals and compounds• Inorganics: metals and elements• Other tests: pH, flash point• Develop new methods
PresenterPresentation NotesStress our own methods….
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Samples to TestDTSC
• Enforcement• Office of Criminal Investigation• Cleanup• Safer Consumer Products
Other agencies
• Dept. of Consumer Affairs
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Types of Samples
• Soil, water, waste• Consumer products• Glass, plastic, metal
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Steps in Sample Analysis
Sample receiving
Sample log-in and management
Homogenization and pre-prep
Sample preparation
Instrumental analysis
Results and data interpretation
Report preparation
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Sample Pre-Prep – Grinding
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Sample Pre-Prep – Sieving
To particle sizes:9.5 mm, 2.0 mm, 1.0 mm
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Sample Preparation – Organic Extraction
• Liquid-liquid extraction• Reflux extraction of solids• Solid phase extraction
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Extraction Tests for Hazardous Waste Classification
• Determine whether a waste is toxic• Simulate what happens in a landfill • Prep the sample and analyze • Determine whether the samples are toxic by comparing to threshold values
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Hazardous Waste Classification
US EPA TCLP• Toxic Characteristic Leaching Procedure• 20-fold dilution, acetic acid, 18 hours shaking• test for 7 metals
CA WET• Waste Extraction Test • 10-fold dilution, citric acid, 48 hours tumbling• test for 17 metals
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Sample Preparation – Inorganic Acid Digestion
PresenterPresentation Notesspecialized
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Sample Analysis Instruments
• Gas Chromatography
• Liquid Chromatography
• Inductively Coupled Plasma
• X-Ray Fluorescence
• Spectrophotometry
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GC Chromatogram
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Gas Chromatography -Detector
• MS, Mass Spectroscopy
• FID, Flame Ionization Detector
• ECD, Electron Capture Detector
• PID, Photo-Ionization Detector
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MTBE
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Gas Chromatography –Mass Spectrometry (GC-MS)
Volatile Organic Compounds (VOCs)
EPA Method 8260
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Quality Control Samples
Duplicate
Matrix Spike
Lab Control Sample
MethodBlank
Matrix Spike
Duplicate
Sample Batch
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Quantitation
Calibration Curve
y = 102509x + 18101R2 = 0.9975
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Calibration Curve
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Instrument Response
Calibration Curve
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Anticipate Needs
• Expand the capabilities of the lab, new chemicals and new matrices
• Establish new methods through development and validation
• Respond to DTSC mandates
PresenterPresentation NotesAnticipating needs?Beyond std methods?
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Metals in Glass
• Toxics in Packaging Prevention Act• California laws to limit cadmium, lead,
mercury, and hexavalent chromium in product packaging
• Glass Beads
• Metal-Containing Jewelry
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Establish and Validate a Method
• Research methods• Adapt and optimize to the lab• Determine calibration range• Run Quality Control materials
Method blank, duplicate, matrix spike,laboratory control sample, certified reference material
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Special Projects: Waste Stream Studies
• Metal Shredder Waste• eWaste• Alkaline and dry cell batteries • Treated wood waste• LED lamps• Cathode ray tubes
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mixture of metal, plastic, glass, wire, resin, rubber, fabric, foam, fiber, fluff, etc.
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Our Lab Results Support
Enforcement• Citations, fines, penalties• Prosecution• Settlements
• AT&T $52 million• Comcast $26 million
Foundation for new regulations
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SummaryECL Analytical Chemistry
• Sample analysis• Develop new methods• Special projects
• Consultation and support
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Department of Toxic Substances Control Cal/EPA
Scientific Leadership:Chemicals of Emerging Concern
Myrto Petreas, Ph.D., MPHChief, Environmental Chemistry Branch
December 9, 2016Environmental Chemistry Laboratory, Berkeley
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• Dr. June-Soo Park, Biomonitoring Branch Chief
• All ECL staff
Acknowledgement
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Our history with emerging chemicalsExamples of our workFlame RetardantsFluorinated Chemicals (PFAS)
BiomonitoringUnknown ChemicalsHow our work benefits other DTSC activities
Outline
PresenterPresentation NotesDHS1991
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In the late 1970s, the Hazardous Materials Laboratory (HML) was formed within the Department of Health Services to support enforcement and clean up of hazardous waste sites.
How it all started
PresenterPresentation NotesDHS1991
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Mid-70s HML at DHS
Toxics Program at DHS
2006
HML=>ECL
1991 HML moves to
DTSC
Administrative Changes
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Emerging Concern: Dioxins
PresenterPresentation NotesEmerging issue
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Fire at Koppers Wood Treatment Plant
Pentachlorophenol Dioxins
Extensive sampling of soil, vegetation, grazing animals and residents
Explosion in Oroville (1987)
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Staff, trained at CDC, were able to analyze Dioxins in soil, chicken eggs and tissues
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In Oroville's Aftermath
• First grant (USEPA) to study Dioxin uptake in grazing animals with chickens as a model
• Chicken feeding study (bioaccumulation and depuration in eggs, liver, muscle)
Publications used extensively during Belgian egg crisis
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Supported Department’s studies of Dioxin-like Chemicals in 1990s
• Transformer explosion (Dept. of Education building in Sacramento)
• Metal recovery site cleanups (Mobile Smelting)
• Superfund sites (McCormick-Baxter)
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New class of chemicals with Dioxin-like structure
Ready for Our Next Challenge
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Polybrominated Diphenylethers (PBDEs)
• Flame retardants• Added to products to meet CA Flammability Standard (TB117)
• Dubious efficacy
PresenterPresentation NotesEmerging issue
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• Persistent, Bioaccumulative, Toxic
• Endocrine disruption (Thyroid)• Developmental effects
• Reduced fertility• Lower IQ of offspring
PBDEs: Health Concerns
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Californians Have the Highest PBDEsPetreas et al, 2001
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Exponential Increase of PBDEs in SF Bay Harbor Seals
She et al, 2002
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Record PBDE Levels in CA Wastes, Wildlife and Humans
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Our Data Help Californians
• Legislature restricts PBDE use (2003)• Flammability standard revised (TB117-2013)• SB1019 Labelling Law (2015)
PBDE levels dropping in blood and breast milk
PresenterPresentation NotesNamed in billSupport enforcement
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PBDE Levels Are Dropping in CaliforniaGuo et al. 2016
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Press Event on Dropping PBDE Levels
“This study shows that regulatory and public health interventions work. The new findings underscore the importance of biomonitoring studies, and highlight the concrete benefits of product reformulation.”
- DTSC Director Barbara Lee, Feb 24, 2016
http://www.sacbee.com/news/local/article62345647.html
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http://www.sacbee.com/news/local/article62345647.html#storylink=cpy
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Shifts to other flame retardants –regrettable substitutes
Stapleton et al. 2012
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Children’s Foam-padded Sleeping Products containing Tris (TDCPP and TCEP) selected as Initial Priority Products
ECL developed methods to measure Tris and other flame retardants in products, dust and urine
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Measuring chemicals in biological material such as blood, milk or urine
Over 30 years of experience at ECL
HUMAN BIOMONITORING
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• Established by state legislation in 2006 (SB 1379)
• Tri-departmental structure
• Public involvement
• Scientific Guidance Panel
• Public participation
• Public website: www.biomonitoring.ca.gov
http://www.biomonitoring.ca.gov/
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Mandates:
• Determine chemical levels in Californians using:Statewide surveysCommunity studies (vulnerable groups)
• Return and communicate results to participants
• Examine trends in chemical levels
• Help assess the effectiveness of: Environmental regulations Regulatory interventions
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Some Significant Findings:
• Babies are born with chemical contaminantsProvided information on reducing exposures
• Firefighters have higher PBDE levels than the general populationUse of protective gear reduces exposures
• Declining trends in PBDEs
PresenterPresentation NotesLeg reporet
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• Consultation and measurements of Persistent Chemicals (PCBs, Pesticides, Flame Retardants, PFASs)
• Identification of new chemicals of emerging concern• Method development• Link to Safer Consumer Products
• ECL continues its own biomonitoring studies outside of Biomonitoring California
ECL’s Roles:
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Fluorinated Chemicals (PFASs)
Our Next Emerging Issue
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• Persistent, Bioaccumulative, Toxic
• Endocrine disruption • Developmental effects• Immune system effects• Cancer
PFASs: Health Concerns
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PFASs: In Every-day Products
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Product-chemical combination:
PFASs in carpets, rugs, upholstered furniture and their care and treatment products
1st Informational Workshop in Sacramento: January 31, 2017
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PFASs: Water Contaminants
Aqueous Fire Fighting Foams (AFFF)• Ground water, surface water• Wastewater• Drinking water
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• Analyzed treated effluent from major treatment plants that discharge in SF Bay
• All had PFASs• Highest PFASs (>10x) in treatment plants
serving airports (SFO and Suisun/Travis AFB)• Markers of AFFF
PFASs in Wastewater EffluentHoutz et al, 2016
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USEPA Report on Chemicals in Public Drinking Water Systems
• Unregulated Chemicals Monitoring Report (UCMR)
• Latest round (UCMR3, 2013-15) included some PFAS
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Our CA Teachers Study
oCase-control breast cancer studyoOver 3,000 female teachers (median age=67)oBlood analyzed for contaminants, including PFASsoEpidemiology not yet completed
Women were matched by residential zip codes to drinking water systems tested for these chemicals
PresenterPresentation Notesleveraging
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Higher Blood PFASs Linked to PFASs in Drinking Water
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PFAS in blood linked to drinking waterHurley et al 2016
PresenterPresentation NotesPaper selected to make the journal coverCredit Linnah Marlow, graphic designer (DTSC)
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Unknown Chemicals
Our Newest Emerging Issue
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Data from: U.S. Federal Reserve Board, Division of Research and Statistics
Many Regrettable Substitutions
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Are Labs Only Looking Under the Street Light?
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Labs can only measure a very small fraction
~1300 Potential Chemicals
One Sample, Many Chemicals
PresenterPresentation Notes
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Short of a Tricorder…
Untargeted Suspect Screening
• Check key characteristics of chemicals
• Check against databases for potential matches
• Tentative identification
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Untargeted Suspect Screening Using Newer Instrumentation (LC-QTOF MS)
• ECL among very small number of labs
• Participating in USEPA’s cross-testing of labs
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Newly Identified Chemicals:
• Several replacement flame retardants in products
• Several additional PFASs in blood and water
• Markers of AFFF in wastewater
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• Expands our capabilities
• Serves as an Early Warning System
• Helps Safer Consumer Products Program
Benefits of Untargeted Screening
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• Grants from USEPA, NIH, CDC, CBCRP, EU• Projects within DTSC’s mandate• Collaborations with Universities, other agencies• Funds used for equipment, operating expenses,
visiting scholars
Leveraging Resources
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• Post docs, graduate students, professors• Work alongside our staff for the duration
of the grant cross-training
• Many transition to State jobs great recruiting tool
Visiting Scholars Add Value to ECL
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Over 230 Scientific Peer-reviewed Publications
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Recipe for Scientific Leadership
• Management’s vision and support• Synergy through collaborations, cross-training• Extramural grants to augment resources• State-of-the-art methodologies• QUALITY!
Our Work Supports DTSC Decision Making
Slide Number 1SpeakersMissionVisionSlide Number 5We Test a Wide Variety of MaterialsScientific Expert Technical SupportValuesECL as an OrganizationECL as Centers of Excellence:�The PeopleCenters of Excellence:�Laboratory InfrastructureCenters of Excellence�State-of-the-Art Analytical EquipmentEnsuring the Quality of Our WorkStandard Operating ProceduresFoundation for Decision-Making Thank YouAnalytical Support – BerkeleyIntroduction / OutlineWhat We Do: �Test Using EPA MethodsSamples to TestTypes of Samples Slide Number 22Steps in Sample AnalysisSample Pre-Prep – GrindingSample Pre-Prep – SievingSample Preparation – Organic �ExtractionExtraction Tests for �Hazardous Waste ClassificationHazardous Waste ClassificationSample Preparation – Inorganic �Acid DigestionSample Analysis InstrumentsGC ChromatogramGas Chromatography - DetectorMTBEGas Chromatography – �Mass Spectrometry (GC-MS)Quality Control Samples�QuantitationAnticipate NeedsMetals in GlassEstablish and Validate a MethodSpecial Projects: �Waste Stream StudiesSlide Number 41Slide Number 42Slide Number 43Our Lab Results SupportSummary�ECL Analytical Chemistry��Scientific Leadership:�Chemicals of Emerging Concern��Myrto Petreas, Ph.D., MPH�Chief, Environmental Chemistry Branch����AcknowledgementOutlineHow it all startedAdministrative ChangesEmerging Concern: DioxinsExplosion in Oroville (1987) �Slide Number 53In Oroville's AftermathSupported Department’s studies of Dioxin-like Chemicals in 1990sReady for Our Next Challenge�Polybrominated Diphenylethers (PBDEs)�PBDEs: Health Concerns Californians Have the Highest PBDEs�Petreas et al, 2001�Exponential Increase of PBDEs in SF Bay Harbor Seals�She et al, 2002�Record PBDE Levels in CA Wastes, Wildlife and Humans�Our Data Help CaliforniansPBDE Levels Are Dropping in California�Guo et al. 2016�Press Event on Dropping PBDE Levels Slide Number 65Shifts to other flame retardants – regrettable substitutesSlide Number 67HUMAN BIOMONITORINGSlide Number 69Mandates:Some Significant Findings:ECL’s Roles:Slide Number 73PFASs: Health Concerns PFASs: In Every-day ProductsSlide Number 76PFASs: Water ContaminantsPFASs in Wastewater Effluent�Houtz et al, 2016USEPA Report on Chemicals in Public Drinking Water SystemsOur CA Teachers StudySlide Number 81Slide Number 82Our Newest Emerging Issue Slide Number 84Slide Number 85Slide Number 86Short of a Tricorder…Untargeted Suspect Screening Using Newer Instrumentation (LC-QTOF MS)Newly Identified Chemicals: �Benefits of Untargeted ScreeningLeveraging ResourcesVisiting Scholars Add Value to ECLOver 230 Scientific Peer-reviewed PublicationsRecipe for Scientific Leadership