Department of Toxic Substances Control Cal/EPA

Bruce La Belle, Ph.D.Laboratory Chief

December 9, 2016Berkeley, CA

Environmental Chemistry Laboratory

Speakers Overview

Dr. Bruce La Belle

Analytical Chemistry Support Dr. Robert Ramage

Scientific Leadership, Biomonitoring, and Emerging Chemical Issues Dr. Myrto Petreas

External Perspectives

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 doesnt capture my eyes at first time.

We Test a Wide Variety of Materials

Scientific Expert Technical Support

Analytical methods selection Project plans/sampling plan review Split sample testing Data quality review/interpretation/validation Training Reference Lab

Values Scientific Excellence Integrity Impartiality Independence Defensibility Consistency Traceability

Transparency Customer Service

Workplace Diversity Courtesy Respect

PresenterPresentation NotesI rearranged text and font and changed the color of checkmark to be more visible

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

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

Centers of Excellence:Laboratory Infrastructure

ECL-Berkeley Specialized facilities including Clean Room laboratories

ECL-Pasadena New, state-of-the-art laboratory replaces 1950s facility

Ability to serve major areas of State Inter-laboratory method validations Continuity of operations in event of earthquake

Centers of ExcellenceState-of-the-Art Analytical Equipment

A

aa

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

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

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

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?

Thank You

Department of Toxic Substances Control Cal/EPA

Analytical Support Berkeley

Robert Ramage, Ph. D.Supervisor

December 9, 2016Environmental Chemistry Laboratory

Introduction / Outline

What we do How we do it Types of special projects Uses of lab results

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.

Samples to TestDTSC

Enforcement Office of Criminal Investigation Cleanup Safer Consumer Products

Other agencies

Dept. of Consumer Affairs

Types of Samples

Soil, water, waste Consumer products Glass, plastic, metal

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

Sample Pre-Prep Grinding

Sample Pre-Prep Sieving

To particle sizes:9.5 mm, 2.0 mm, 1.0 mm

Sample Preparation Organic Extraction

Liquid-liquid extraction Reflux extraction of solids Solid phase extraction

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

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

Sample Preparation Inorganic Acid Digestion

PresenterPresentation Notesspecialized

Sample Analysis Instruments

Gas Chromatography

Liquid Chromatography

Inductively Coupled Plasma

X-Ray Fluorescence

Spectrophotometry

GC Chromatogram

Gas Chromatography -Detector

MS, Mass Spectroscopy

FID, Flame Ionization Detector

ECD, Electron Capture Detector

PID, Photo-Ionization Detector

MTBE

Gas Chromatography Mass Spectrometry (GC-MS)

Volatile Organic Compounds (VOCs)

EPA Method 8260

Quality Control Samples

Duplicate

Matrix Spike

Lab Control Sample

MethodBlank

Matrix Spike

Duplicate

Sample Batch

Quantitation

Calibration Curve

y = 102509x + 18101R2 = 0.9975

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Concentration (ppb)

Inst

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Chart1

99555

500101

1100201

2120500

2523201

Concentration (ppb)

Instrument Response

Calibration Curve

Sheet1

ConcentrationResponse

199,555

5500,101

101,100,201

202,120,500

252,523,201

Sheet1

Concentration (ppb)

Instrument Response

Calibration Curve

Sheet2

Sheet3

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?

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

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

Special Projects: Waste Stream Studies

Metal Shredder Waste eWaste Alkaline and dry cell batteries Treated wood waste LED lamps Cathode ray tubes

mixture of metal, plastic, glass, wire, resin, rubber, fabric, foam, fiber, fluff, etc.

Our Lab Results Support

Enforcement Citations, fines, penalties Prosecution Settlements

AT&T $52 million Comcast $26 million

Foundation for new regulations

SummaryECL Analytical Chemistry

Sample analysis Develop new methods Special projects

Consultation and support

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

Dr. June-Soo Park, Biomonitoring Branch Chief

All ECL staff

Acknowledgement

Our history with emerging chemicalsExamples of our workFlame RetardantsFluorinated Chemicals (PFAS)

BiomonitoringUnknown ChemicalsHow our work benefits other DTSC activities

Outline

PresenterPresentation NotesDHS1991

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

Mid-70s HML at DHS

Toxics Program at DHS

2006

HML=>ECL

1991 HML moves to

DTSC

Administrative Changes

Emerging Concern: Dioxins

PresenterPresentation NotesEmerging issue

Fire at Koppers Wood Treatment Plant

Pentachlorophenol Dioxins

Extensive sampling of soil, vegetation, grazing animals and residents

Explosion in Oroville (1987)

Staff, trained at CDC, were able to analyze Dioxins in soil, chicken eggs and tissues

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

Supported Departments 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)

New class of chemicals with Dioxin-like structure

Ready for Our Next Challenge

Polybrominated Diphenylethers (PBDEs)

Flame retardants Added to products to meet CA Flammability Standard (TB117)

Dubious efficacy

PresenterPresentation NotesEmerging issue

Persistent, Bioaccumulative, Toxic

Endocrine disruption (Thyroid) Developmental effects

Reduced fertility Lower IQ of offspring

PBDEs: Health Concerns

Californians Have the Highest PBDEsPetreas et al, 2001

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

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

PBDE Levels Are Dropping in CaliforniaGuo et al. 2016

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

65

Shifts to other flame retardants regrettable substitutes

Stapleton et al. 2012

Childrens 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

Measuring chemicals in biological material such as blood, milk or urine

Over 30 years of experience at ECL

HUMAN BIOMONITORING

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/

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

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

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

ECLs Roles:

Fluorinated Chemicals (PFASs)

Our Next Emerging Issue

Persistent, Bioaccumulative, Toxic

Endocrine disruption Developmental effects Immune system effects Cancer

PFASs: Health Concerns

PFASs: In Every-day Products

Product-chemical combination:

PFASs in carpets, rugs, upholstered furniture and their care and treatment products

1st Informational Workshop in Sacramento: January 31, 2017

PFASs: Water Contaminants

Aqueous Fire Fighting Foams (AFFF) Ground water, surface water Wastewater Drinking water

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

USEPA Report on Chemicals in Public Drinking Water Systems

Unregulated Chemicals Monitoring Report (UCMR)

Latest round (UCMR3, 2013-15) included some PFAS

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

Higher Blood PFASs Linked to PFASs in Drinking Water

PFAS in blood linked to drinking waterHurley et al 2016

PresenterPresentation NotesPaper selected to make the journal coverCredit Linnah Marlow, graphic designer (DTSC)

Unknown Chemicals

Our Newest Emerging Issue

Data from: U.S. Federal Reserve Board, Division of Research and Statistics

Many Regrettable Substitutions

Are Labs Only Looking Under the Street Light?

Labs can only measure a very small fraction

~1300 Potential Chemicals

One Sample, Many Chemicals

PresenterPresentation Notes

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 USEPAs cross-testing of labs

Newly Identified Chemicals:

Several replacement flame retardants in products

Several additional PFASs in blood and water

Markers of AFFF in wastewater

Expands our capabilities

Serves as an Early Warning System

Helps Safer Consumer Products Program

Benefits of Untargeted Screening

Grants from USEPA, NIH, CDC, CBCRP, EU Projects within DTSCs mandate Collaborations with Universities, other agencies Funds used for equipment, operating expenses,

visiting scholars

Leveraging Resources

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

Over 230 Scientific Peer-reviewed Publications

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Recipe for Scientific Leadership

Managements 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 ExcellenceState-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 SamplesQuantitationAnticipate NeedsMetals in GlassEstablish and Validate a MethodSpecial Projects: Waste Stream StudiesSlide Number 41Slide Number 42Slide Number 43Our Lab Results SupportSummaryECL Analytical ChemistryScientific Leadership:Chemicals of Emerging ConcernMyrto Petreas, Ph.D., MPHChief, Environmental Chemistry BranchAcknowledgementOutlineHow it all startedAdministrative ChangesEmerging Concern: DioxinsExplosion in Oroville (1987) Slide Number 53In Oroville's AftermathSupported Departments studies of Dioxin-like Chemicals in 1990sReady for Our Next ChallengePolybrominated Diphenylethers (PBDEs)PBDEs: Health Concerns Californians Have the Highest PBDEsPetreas et al, 2001Exponential Increase of PBDEs in SF Bay Harbor SealsShe et al, 2002Record PBDE Levels in CA Wastes, Wildlife and HumansOur Data Help CaliforniansPBDE Levels Are Dropping in CaliforniaGuo et al. 2016Press Event on Dropping PBDE Levels Slide Number 65Shifts to other flame retardants regrettable substitutesSlide Number 67HUMAN BIOMONITORINGSlide Number 69Mandates:Some Significant Findings:ECLs Roles:Slide Number 73PFASs: Health Concerns PFASs: In Every-day ProductsSlide Number 76PFASs: Water ContaminantsPFASs in Wastewater EffluentHoutz 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 TricorderUntargeted 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