1 Fingerprinting and Forensic Techniques for Landfill Gas Geochemical Assessment LEA/CIWMB Partnership Conference Monterey, CA - August 2, 2006 CIWMB Abel

11

Fingerprinting and Forensic Techniques for Fingerprinting and Forensic Techniques for Landfill Gas Geochemical AssessmentLandfill Gas Geochemical Assessment

LEA/CIWMB Partnership ConferenceLEA/CIWMB Partnership ConferenceMonterey, CA - August 2, 2006Monterey, CA - August 2, 2006

CIWMBCIWMBAbel M. CentenoAbel M. Centeno

Chemical EngineerChemical Engineer

1001 I Street MS #201001 I Street MS #20

Sacramento, CA 95814Sacramento, CA 95814

(916) 341-6724(916) 341-6724

Orange County LEAOrange County LEASam Abu-ShabanSam Abu-Shaban

Senior Civil EngineerSenior Civil Engineer

1241 E. Dyer Road, Suite 1201241 E. Dyer Road, Suite 120

Santa Ana, CA 92705Santa Ana, CA 92705

(714) 433-6271(714) 433-6271

22

Session AgendaSession Agenda

Theory of Gas GeochemistryI. Introduction – Stating the ProblemII. Identification of Methane SourcesIII. Analytical Procedures/MethodsIV. Data Interpretation Techniques

Case Studies in Orange CountyCase I (Newport Terrace Landfill – Newport Beach, CA) Case II (Cannery Street Landfill – Huntington Beach, CA)

V. Background/Description of Case StudiesVI. Workplan Implementation and Procedures VII. Results and InterpretationVIII. Conclusions

Questions

33

IIIntroductionIntroduction

Stating the ProblemStating the Problem

METHANE

Source 1 Source 2

Source… n Source 3

44

Problem SettingProblem Setting

Methane as greenhouse & explosive gas

CH4 Migration/Accumulation = Hazards

LEA/CIWMB task = Gas Monitoring and Control (27 CCR, Section 20919)

Fugitive methane from OTHER SOURCESOTHER SOURCES

55

Problem Setting (contd.)Problem Setting (contd.)

Identification and correlation of methane releases to their source

Why?Why?

Scenarios/Scenarios/Sources?Sources?

METHANE

Source 1 Source 2

Source… n Source 3

66

27 CCR20919

27 CCR20919

Why?Why?

To determine Responsible Parties

To determine LEA involvement

Adequate remediation design and implementation

“define the problem before the solution”

77

IIIIIdentification of Identification of Methane SourcesMethane Sources

What types of scenarios would the LEA encounter?

+Common(Most Likely)

Rare(Not Likely)LANDFILL

88

Most Common SourcesMost Common Sources

Sources that generate CHSources that generate CH44 in high enough volumes in high enough volumes and pressures to generate a migrating plume and pressures to generate a migrating plume

through soilsthrough soils

{FUGITIVE METHANE}

(Gas that you would see in your probes)

99

Natural Gas LeaksNatural Gas Leaks(Pipeline Gas)(Pipeline Gas)

Transportation Lines

Residential/CommercialSupply Lines

1010

Naturally Occurring MethaneNaturally Occurring Methane(Thermogenic/Petrogenic Gas)(Thermogenic/Petrogenic Gas)

Active/Abandoned Well Leaks

Natural Seepage(Underground Sources/Reservoirs)

1111

Other BiogasOther Biogas(Swamp/Marsh Gas)(Swamp/Marsh Gas)

Decay of Organic Matter(CH4 Formation)

&Seepage

Through Soil

1212

Other SourcesOther Sources(Less Common/Not Likely)(Less Common/Not Likely)

Low Potential – Underground Migrating PlumesLow Potential – Underground Migrating Plumes Not Enough Documented Data (CHNot Enough Documented Data (CH44 Migrating-Problems) Migrating-Problems)

(Gas that you wouldn’t likely see in your probes)

Sewer Lines/Systems Sewer Lines/Systems (accumulation @ enclosed spaces)

Coal MinesCoal Mines Rice FieldsRice Fields TermitesTermites OceansOceans LivestockLivestock

1313

Factoid LivestockFactoid Livestock

Got Gas?

A cow can belch up to

½ lb of CH4/Day

A cow can belch up to

½ lb of CH4/Day

+Sheep

Goats

Buffalo

Camels

Can Do It Too

1414

Factoid LivestockFactoid Livestock

Got Gas?

97.1 Million Cattle in the US

DO THE MATH!

48.5 Million lb CH4/Day

An untapped source of energy

1515

Not For Every Landfill in CANot For Every Landfill in CA

Common Scenario for the LEA

LANDFILLvs

THERMOGENIC SOURCE

DESPITEDESPITE CA ranked 4CA ranked 4thth oil producing state oil producing state

in the USin the US 100’s of oil/gas seeps found in 100’s of oil/gas seeps found in

28 counties in CA (Humboldt 28 counties in CA (Humboldt San DiegoSan Diego

Be InformedDo your Homework

There are tools available!

1616

Oil & Gas Fields in CAOil & Gas Fields in CA

Are there any oil fields located near Are there any oil fields located near the landfill?the landfill?(Maps for 6 Districts)(Maps for 6 Districts)

Are there any active/abandoned oil Are there any active/abandoned oil wells near the landfill? wells near the landfill? (Database -195,000 well locations)(Database -195,000 well locations)

Resources:Resources:http://www.consrv.ca.gov/

1717

Oil Production in CAOil Production in CA3 Major Regions3 Major Regions

• Kern County Region(69%)

• Los Angeles Basin Region(Central LA – Long Beach)(~10%)

• Outer Continental Shelf(Offshore 10.2%)

Kern

SL Obispo

Los Angeles

Ventura

Monterey

Orange

1818

IIIIIIAnalytical Procedures/MethodsAnalytical Procedures/Methods

ForensicsForensicsCorrelating CHCorrelating CH44 Releases Releases

to their Sourceto their Source

1919

Analytical Procedures/Methods

Fingerprinting Gas ReleasesFingerprinting Gas Releases(Gas Geochemistry)(Gas Geochemistry)

Groups:Groups:1.1. Looking at the Various ConstituentsLooking at the Various Constituents

− BTEXBTEX− HH22SS− CC22++− Fixed GasesFixed Gases− Chlorinated Hydrocarbons/VOCsChlorinated Hydrocarbons/VOCs− MercaptansMercaptans

2020

2.2. Stable Isotope CompositionStable Isotope Composition– Hydrogen Isotopic Ratio (Hydrogen Isotopic Ratio (22H/H/11H)H)– Carbon Isotopic Ratio (Carbon Isotopic Ratio (1313C/C/1212C)C)

3.3. Radio Isotope CompositionRadio Isotope Composition– 1414C Concentration (Carbon Dating)C Concentration (Carbon Dating)– 33H ConcentrationH Concentration

4.4. Measuring the Caloric ValuesMeasuring the Caloric Values– CHCH44 BTU value BTU value

Not an Easy Task!

2121

Screening ProcessScreening Process

Source x LandfillGas Probe

2222

Screening Process (contd.)Screening Process (contd.)

LFG

Swamp/Marsh Gas

Naturally Occurring

Pipeline Gas

Formation Process

BiogenicShallow depths/low tempsAnaerobic bacterial decompNew Gas (0-100 years)

ThermogenicHigh temps/depth/pressureThermal crack org. matterOld Gas (Millions of years)

2323

Elements for the ID of SourcesElements for the ID of Sources

LFGLFG

COCO22 + CH + CH44 almost equal proportions almost equal proportions VOCs/BTEX (trace)VOCs/BTEX (trace) Low OxygenLow Oxygen HH22S (0-100 ppm)S (0-100 ppm) Note: 3-5% (US EPA)Note: 3-5% (US EPA)

CC22-C-C55 (trace) (trace) Unique Isotopic Fingerprinting (Unique Isotopic Fingerprinting (1313C/C/1212C and C and 22H/H/11H)H) 1414C Detected (Modern/New Gas)C Detected (Modern/New Gas)

2424

Elements for the ID of SourcesElements for the ID of Sources(contd.)(contd.)

SWAMP/MARSH GASSWAMP/MARSH GAS

Easily mistaken with LFGEasily mistaken with LFG Same formation process (biogenic/anaerobic)Same formation process (biogenic/anaerobic) No VOCs/BTEXNo VOCs/BTEX No HNo H22S S Unique Isotopic Fingerprinting (Unique Isotopic Fingerprinting (1313C/C/1212C and C and 22H/H/11H)H)

2525


NATURALLY OCCURRING GASNATURALLY OCCURRING GAS

BTEX (trace)BTEX (trace) No VOCsNo VOCs HH22S Low–High (0.1 – 2.5%)/(0-98%)S Low–High (0.1 – 2.5%)/(0-98%)

CC22-C-C55 (up to 20%) (up to 20%) Unique Isotopic Fingerprinting (Unique Isotopic Fingerprinting (1313C/C/1212C and C and 22H/H/11H)H) 1414C (Not Detected/Old Gas)C (Not Detected/Old Gas)

2626


PIPELINE GASPIPELINE GAS

Almost Pure CHAlmost Pure CH4 4 (80-90%)(80-90%)

Some CSome C22-C-C55 (%) (%) Unique ID Element: Tracers (25-100 ppm)Unique ID Element: Tracers (25-100 ppm)

Mercaptans/Thiophene other OdorantsMercaptans/Thiophene other Odorants

2727

IVIVData Interpretation TechniquesData Interpretation Techniques

ForensicsForensicsCorrelating CHCorrelating CH44 Releases Releases

to their Sourceto their Source

2828

Data Interpretation

Tier Evaluation Process

Source’s Unique

IDELEMENTS

2929

Unique ID ElementsUnique ID Elements

Fixed Gases in SamplesSmelly Skunk Landfill

0

20

40

60

80

100

P-21B (B

)

W-5

6 (B

)

W-5

0 (B

)

P-32R (B

)

P-32R D

up (B

)

CP-7B (B

)

P-8A (B

)

Backg

roun

d (B)

Sample ID

Co

nce

ntr

atio

n (

% v

/v)

CH4 CO2 O2

3030

Unique ID Elements (contd.)Unique ID Elements (contd.)

VOCs in SamplesSmelly Skunk Landfill

0 0 0

4

0 0 0 0

2 2

3

0

1

2

3

4

5

Benze

ne

Ethyl

benze

ne

Toluen

e

Vinyl

Chlo

ride

Met

hylen

e Chlo

ride

Trichlo

roet

hyle

ne

cis-

1,2-

Dichlo

roet

hene

Tetra

chlo

roth

ene

1,4-

Dichlo

robe

nzen

e

Carbon D

isulfi

de

Dichlo

rodi

fluoro

met

hane

Occ

urr

ence

s

3131


Hydrogen Sulfide in SamplesSmelly Skunk Landfill

1

10

100

1000

10000

P-21B

(B)

W-5

6 (B

)

W-5

0 (B

)

P-32R

(B)

P-32R

Dup

(B)

CP-7B (B

)

P-8A (B

)

Backg

round

(B)

Sample ID

H2S

Co

nce

ntr

atio

n (

pp

mv)

(Lo

g S

cale

)

3232


Pipeline Gas Tracers in SamplesSmelly Skunk

0

5

10

t-But

yl M

ercap

tan

Tatra

hydro

thiop

hene

Compound

Oc

cu

rre

nc

es

Not Detected

3333


Hydrocarbons/Alkanes (C2-C5) & MethaneSmelly Skunk Landfill

0

1

10

100

1,000

10,000

100,000

1,000,000

10,000,000

P-2

1B (

B)

W-5

6 (B

)

W-5

0 (B

)

P-3

2R (

B)

P-3

2R D

UP

(B)

CP

-7B

(B

)

P-8

A (

B)

Bac

kgro

un

d(B

)

Co

nce

ntr

atio

ns

(pp

m)

(Lo

g S

cale

)

Concenrations (ppm) CH4 Concenrations (ppm) C2H6 Concenrations (ppm) C3H8

Concenrations (ppm) C4H10 Concenrations (ppm) C5H12

Trace Conc.in LFG

3434

Hydrocarbon Ratios (C1/C2-C5)Smelly Skunk Landfill

1

10

100

1,000

10,000

100,000

1,000,000

10,000,000

- - - - - -

Ra

tio

(Lo

g S

ca

le)

C1/C2 C1/C3 C1/C4 C1/C5

900

350

1,500

4,500


Biogas Indicator

Thermogenic Gas Indicator (after Jones et al. 1999)

3535

Sophisticated GeochemistrySophisticated Geochemistryto ID Sourcesto ID Sources

Stable Isotope CompositionStable Isotope Composition(Isotope Chemistry 101)(Isotope Chemistry 101)

Naturally Occurring Isotopes:Naturally Occurring Isotopes:

12C 98.89%13C 1.11%

1H ~99.98%2H 0.0184%

Same Element Different Atomic Weight

Same Element Different Atomic Weight

3636

The Principle of Employing IsotopesThe Principle of Employing Isotopes

Distribution of IsotopesDistribution of Isotopes

CHCH44

Biogenic Methane FormationBiogenic Methane Formation

CHCH33 -- |-- CO -- |-- CO22- + H a - + H a CHCH44 + CO + CO22

COCO22 + 8H + 8H CHCH44 + 2H + 2H22OO

1313C/C/1212C Ratio: Unique to the source C Ratio: Unique to the source 22H/H/11H Ratio: Unique to the sourceH Ratio: Unique to the source

12C13C

Bacterial DecompositionLight Isotopes 12C & 1HPreferentially Selected

3737

The Principle of Employing IsotopesThe Principle of Employing Isotopes

3838

The Principle of Employing IsotopesThe Principle of Employing IsotopesIsotope Fingerprint (Methane)

Smelly Skunk Landfill

-360

-320

-280

-240

-200

-160

-120

-80

-100 -90 -80 -70 -60 -50 -40 -30 -20

d 13 C of CH4 (0/00)

d D o

f C

H4 (

0/ 0

0)

Biogenic Fermentation

Mixed Gases

Thermogenic GasBiogenic CO2 Reduction

3939

Radioisotope CompositionRadioisotope Composition1414C Concentration – Carbon DatingC Concentration – Carbon Dating

Naturally Occurring Isotopes:Naturally Occurring Isotopes:

12C 98.89%13C 1.11%14C 0.0000000001% (Radioactive)

14C Decays = Half-life 5730 yrs

How much 14C is

remaining in the CH4?

4040

1414C Concentration – Carbon DatingC Concentration – Carbon Dating

Anything older than 60,000 years should have no detectable 14C (thermogenic gas)

If we detect 14C, it is good evidence that gas was generated less than 60,000 years (landfill gas)

1.LFG should contain 14C2.Thermogenic gas should not contain 14C

4141

How isHow is 14 14C MeasuredC Measured

Counting atoms/Accelerator MSCounting atoms/Accelerator MS AMS sophisticated - UCI & Livermore)AMS sophisticated - UCI & Livermore)

Measurement14C/12C

Equations for Correction

StatisticalNormalization

% Modern CAge (BP)

4242

How isHow is 14 14C MeasuredC Measured

1950 is year 0 BP

Atmospheric 14C/12C

14C/12CDecaying Matter

0-100 pMC 100-120 pMC

4343

ReportingReporting 14 14C ResultsC Results

14C Content (pMC)Smelly Skunk Landfill

102.60 98.30

116.70109.80 110.10

103.90 98.90

0.00

020406080

100120140

P-21B

W-5

6W

-50

P-32R

P-32R

DUP

CP-7B

P-8A

Backg

round

(B)

Probe

14C

Act

ivit

y (p

MC

)

4444

4545

VVCase BackgroundCase Background

&&DescriptionDescription

Case Studies in Orange CountyCase Studies in Orange County Case I

(Newport Terrace Landfill)Newport Beach, CA

4646

BackgroundBackground Originally a gravel mining pitOriginally a gravel mining pit

Owned and operated as a disposal site by Owned and operated as a disposal site by City of Newport Beach between 1953 – City of Newport Beach between 1953 – 19671967

Located near wetlands and encompasses Located near wetlands and encompasses 41 acres including 17 acres of Refuse Fill 41 acres including 17 acres of Refuse Fill and Rubble Fill areas and Rubble Fill areas

Accepted C&D, plastic, paper, cardboard, Accepted C&D, plastic, paper, cardboard, metals, glass and yard wastes metals, glass and yard wastes

4747

Site Fill AreasSite Fill Areas

REFUSE FILL

RUBBLE FILL

NATIVE SOIL

NATIVE SOIL

N

4848

Sold to a developer who, in 1974, built Sold to a developer who, in 1974, built condominiums on-sitecondominiums on-site

1974-1975 LFG control system was installed (archaic 1974-1975 LFG control system was installed (archaic by today’s standards)by today’s standards)

The LEA notified HOA on numerous occasions of the The LEA notified HOA on numerous occasions of the Site’s violation of SMS for LFGSite’s violation of SMS for LFG

1998 HOA’s consultant concluded that repairs to LFG 1998 HOA’s consultant concluded that repairs to LFG control system were impractical and uneconomicalcontrol system were impractical and uneconomical

Background (contd.)Background (contd.)

4949

2001, CIWMB detected CH2001, CIWMB detected CH44>5% in Rubble Fill >5% in Rubble Fill and Refuse Fill’s eastern and southern and Refuse Fill’s eastern and southern boundaries (Hboundaries (H22S > 1,000 ppm in Rubble Fill)S > 1,000 ppm in Rubble Fill)

In 2002, the LEA issued N&O to control LFGIn 2002, the LEA issued N&O to control LFG

Based on high HBased on high H22S levels, City argued the S levels, City argued the source of CHsource of CH44 in Rubble Fill is not buried waste in Rubble Fill is not buried waste

Background (contd.)Background (contd.)

5050

Site ProbesSite Probes

P-21

W-56

W-50

CP-7

P-8

P32

Refuse Fill Area

Rubble Fill Area

5151

VIVIWorkplan ImplementationWorkplan Implementation

&&ProceduresProcedures

5252

Investigation WorkplanInvestigation Workplan Focused on Rubble Fill area, southern and Focused on Rubble Fill area, southern and

eastern boundaries of Refuse Fill areaeastern boundaries of Refuse Fill area

Screening of sampling locations for COScreening of sampling locations for CO22, , OO22, N, N22, CH, CH44 and H and H22S S

If CHIf CH44>1% collect samples for lab analysis>1% collect samples for lab analysis

Background and duplicate samples Background and duplicate samples (QA/QC)(QA/QC)

5353

Investigation Workplan (contd.)Investigation Workplan (contd.)

Lab analysis:Lab analysis:- - COCO22, O, O22 and Balance (mostly N and Balance (mostly N22))- Hydrocarbons C- Hydrocarbons C11 – C – C55 - Pipeline gas tracers- Pipeline gas tracers- VOCs (including BTEX)- VOCs (including BTEX)- (- (1313C/C/1212C) + (C) + (22H/H/11H)H)- - 1414CC- H- H22SS

5454

Workplan ImplementationWorkplan Implementation June 2005June 2005

Sample locations were 1Sample locations were 1stst purged and purged and screened for CHscreened for CH44,, fixed gases, Hfixed gases, H22SS

Field measurements loggingField measurements logging

Lab samples were collected from:Lab samples were collected from:- Rubble Fill (P-21, W-50 and W-56)- Rubble Fill (P-21, W-50 and W-56)- Refuse Fill (P-32, CP-7 and P-8)- Refuse Fill (P-32, CP-7 and P-8)- Background- Background

5555

Location: Newport Beach Instrument: GEM-2000

Date:

Project: Newport Terrace Landfill Field Staff: AMC + DO

Weather Condition:

Bar. Pressure: 29.8" Hg Comments:

P21-B 8:08 n/a 70 10 1.6 84.5 0

P21-R 8:17 n/a 70 0 4.4 86.8 n/a

W-56 8:25 n/a 70 64.7 0.7 31.5 above scale

W-50 8:40 n/a 70 12.5 6.9 71.7 n/a

P-32 R 9:00 n/a 74 31 3.2 34.2 11

P-32 B 9:04 n/a 74 28.5 2 37.1 18

CP-7B 9:25 n/a 74 45.1 1.4 35.4 3

CP-7A 9:31 n/a 74 0 14.4 77.3 n/a

CP-7C 9:34 n/a 74 11.9 9.8 70.1 n/a

P-8B 9:39 n/a 74 0 13.3 78.7 n/a

P-8A 9:42 n/a 74 7.7 1.9 69.8 n/a

Background 9:58 - 74 - - - -

32.5

n/a Reading Stable

6/22/2005

Sunny and Clear

n/a Reading Stable

Shallow Reading Stable

17.7

8.3

7.9

8

22.1

-- -

n/a Reading Stable

n/a Reading Stable

Reading Stable

n/a Reading Stable

Deep Reading Stable

n/a


n/a Reading Stable

Samples Taken: None

Samples Taken: 2 Summa Canisters + 1 Tedlar Bag

CO2

(%)

3.9

Field Observations

Samples Taken: None

Samples Taken: 2 Summa Canister + 1 Tedlar Bag (H2S reading using GMI-442 above the instrument's scale/1000 ppm)2.9

9.2

31.2



Samples Taken: None

Samples Taken: None

Monitoring Data

CH4 (%)

O2

(%)H2S

(ppm)

Sample Taken: 2 Summa Canisters + 1 Tedlar Bag

Samples Taken: 2 Summa Canisters + 1 Tedlar Bag Duplicates Taken: 2 Summa Canisters + 1 Tedlar Bag

Samples Taken: 2 Summa Canisters + 1 Tedlar Bag H2S reading using GMI-442.

9

Samples Taken: None

ID TimeStatic

Pressure

Probe Depth (feet)

Purge Time (sec)

Samples taken for lab analysis.

Temperature

(oF)

Deep

Balance (%)

Reading Stable

California Integrated Waste Management Board1001 I Street - Sacramento, CA 95814

Permitting & Enforcement(Closed Illegal & Abandoned Site Investigation Unit)

Landfil Gas Monitoring Log

Field LogbookField Logbook

5656

P21-B 8:08 n/a 70 10 1.6 84.5 0

P21-R 8:17 n/a 70 0 4.4 86.8 n/a

W-56 8:25 n/a 70 64.7 0.7 31.5 above scale

W-50 8:40 n/a 70 12.5 6.9 71.7 n/a

P-32 R 9:00 n/a 74 31 3.2 34.2 11

P-32 B 9:04 n/a 74 28.5 2 37.1 1832.5Shallow Reading Stable

n/a Reading Stable

Deep Reading Stable


n/a Reading Stable

CO2

(%)

3.9

2.9

9.2

31.2

Monitoring Data

CH4 (%)

O2

(%)H2S

(ppm)

9

ID TimeStatic

Pressure

Probe Depth (feet)

Purge Time (sec)

Temperature

(oF)

Deep

Balance (%)

Reading Stable

Field LogbookField Logbook

5757

Field SamplingField Sampling

5858


5959

Workplan Implementation (contd.)Workplan Implementation (contd.)

Samples for HSamples for H22S and pipeline gas S and pipeline gas tracers lab analysis were collected tracers lab analysis were collected lastlast

Lab samples labeling, logging in Lab samples labeling, logging in COCs, packing and shippingCOCs, packing and shipping

3 different analytical labs3 different analytical labs

6060

VIIVIIResults and InterpretationResults and Interpretation

6161

Results and InterpretationResults and Interpretation

Since no tracers were detected in any Since no tracers were detected in any collected sample, leaking gas pipeline was collected sample, leaking gas pipeline was ruled out as a sourceruled out as a source

Consistent Hydrocarbons CConsistent Hydrocarbons C11 – C – C55 concentrations in all lab samplesconcentrations in all lab samples

Only one sample from Rubble Fill had very Only one sample from Rubble Fill had very high Hhigh H22S level – outside the typical range S level – outside the typical range for LFGfor LFG

6262

Hydrogen Sulfide in SamplesNewport Terrace Landfill

1

10

100

1000

10000

P-21B

(B)

W-5

6 (B

)

W-5

0 (B

)

P-32R

(B)

P-32R

Dup

(B)

CP-7B (B

)

P-8A (B

)

Backg

round

(B)

Sample ID

H2S

Co

nce

ntr

atio

n (

pp

mv)

(Lo

g S

cale

)

6363

Hydrocarbons/Alkanes (C2-C5) & MethaneNewport Terrace Landfill

01

10100

1,00010,000

100,0001,000,000

10,000,000

P-2

1B (

B)

W-5

6 (B

)

W-5

0 (B

)

P-3

2R (

B)

P-3

2R D

UP

(B)

CP

-7B

(B

)

P-8

A (

B)

Bac

kgro

un

d(B

)

Co

nce

ntr

atio

ns

(pp

m)

(Lo

g S

cale

)

Concenrations (ppm) CH4 Concenrations (ppm) C2H6 Concenrations (ppm) C3H8

Concenrations (ppm) C4H10 Concenrations (ppm) C5H12

6464

Results and Interpretation (contd.)Results and Interpretation (contd.)

Hydrocarbon ratios (CHydrocarbon ratios (C11/C/C22-C-C55) were outside ) were outside the thermogenic rangethe thermogenic range

((1313C/C/1212C) values were consistent and within C) values were consistent and within range of biogenic gasrange of biogenic gas

((1414C) content was consistent and very C) content was consistent and very close to the biogenic gas rangeclose to the biogenic gas range

6565

Hydrocarbon Ratios (C1/C2-C5)Newport Terrace Landfill

1

10

100

1,000

10,000

100,000

1,000,000

10,000,000

- - - - - -

Ra

tio

(Lo

g S

ca

le)

C1/C2 C1/C3 C1/C4 C1/C5

900

350

1,500

4,500

NTC Analytical Results

Ratios of hydrocarbons in the thermogenic range(after Jones et al. 1999)

6666

P-21BW-56W-50P-32RP-32R DUPCP-7BP-8ABackground (B)

NM Not able to measure

Genetic Classification after Waseda et al. 2003

Isotope Fingerprint (Methane)Plot of d13 C of CH4 vs C1/(C2+C3)

Newport Terrace Landfill

1

10

100

1000

10000

100000

1000000

-100 -90 -80 -70 -60 -50 -40d13 C of Methane (0/00)

C1

/(C

2+

C3

)

Biogenic Gas

Thermogenic Gas

Mixed Gases

P-21BW-50

CP-7B

P-32R DUPP-32R

6767

P-21BW-56W-50P-32RP-32R DUPCP-7BP-8ABackground (B)

NM Not able to measure

Genetic Classification after Bogner et al. 1996

Isotope Fingerprint (Methane)Plot of d13C of CH4 vs dD of CH4

Newport Terrace Landfill

-360

-320

-280

-240

-200

-160

-120

-80

-100 -90 -80 -70 -60 -50 -40 -30 -20

d13 C of CH4 (0/00)

d D o

f C

H4

(0 / 00)


Mixed Gases

Thermogenic GasBiogenic CO2 Reduction

P-21B

W-50

CP-7B

P-32R DUPP-32R

W-56

P-8A

6868

14C Content of the Methane (pMC)Newport Terrace Landfill

102.6098.30

116.70109.80 110.10

103.9098.90

0.00

0

20

40

60

80

100

120

140

P-21B

W-5

6W

-50

P-32R

P-32R D

UP

CP-7B

P-8A

Backg

roun

d (B)

Probe

14C

Act

ivit

y (p

MC

)

6969

VIIIVIIIConclusionsConclusions

7070

ConclusionsConclusions

CHCH44 detected in the Rubble Fill area is of a detected in the Rubble Fill area is of a biogenic source.biogenic source.

Since Rubble Fill gas samples had similar Since Rubble Fill gas samples had similar levels of Clevels of C11 – C – C55 to that of Refuse Fill to that of Refuse Fill (reference samples), CH(reference samples), CH44 detected in detected in Rubble Fill is more likely to be from Rubble Fill is more likely to be from biodegradation of buried waste.biodegradation of buried waste.

7171

Conclusions (contd.)Conclusions (contd.)

High levels of HHigh levels of H22S in some Rubble Fill S in some Rubble Fill samples are possibly due to:samples are possibly due to:

1.1. Reduction of gypsum (CASOReduction of gypsum (CASO44.2H.2H22O) in O) in discarded dry wall (C&D waste)discarded dry wall (C&D waste)

2.2. Drill cuttings from oil well explorations Drill cuttings from oil well explorations disposed of in Rubble Fill areadisposed of in Rubble Fill area

3.3. Others (sewage sludge, local soil type, Others (sewage sludge, local soil type, etc.)etc.)

7272

VVCase BackgroundCase Background

&&DescriptionDescription

Case Studies in Orange CountyCase Studies in Orange County Case II

(Cannery Street Landfill)Huntington Beach, CA

7373

BackgroundBackground Located in City of Huntington Beach Located in City of Huntington Beach

(approx. 1 mile from the ocean)(approx. 1 mile from the ocean)

Originally owned by SCEOriginally owned by SCE

1957 purchased by the County of Orange1957 purchased by the County of Orange

1957–1969 County-operated disposal site1957–1969 County-operated disposal site

7474

Background (contd.)Background (contd.) Total 27.7 acres (20.5 acres waste-fill)Total 27.7 acres (20.5 acres waste-fill)

Accepted mainly inert waste (C&D, logs, Accepted mainly inert waste (C&D, logs, stumps, timber, etc.)stumps, timber, etc.)

1970 County deeded Site to City for use as 1970 County deeded Site to City for use as a public parka public park

1971 City deeded NW 5 acres to School 1971 City deeded NW 5 acres to School District for elementary school playgroundDistrict for elementary school playground

7575

Site Site LayoutLayout

7676

Background (contd.)Background (contd.) 1996-2000 Several Site Assessments 1996-2000 Several Site Assessments

confirmed CHconfirmed CH44>5% along northern and >5% along northern and western boundaries western boundaries

2000 The LEA issued N&O to the City and 2000 The LEA issued N&O to the City and School DistrictSchool District

2001 City installed 5 vertical passive vents 2001 City installed 5 vertical passive vents (ineffective)(ineffective)

7777

C-GP-4A

C-GP-8A

C-GP-7A

C-GP-3A

7878

Background (contd.)Background (contd.) 2002 LEA issued a new N&O (Compliance 2002 LEA issued a new N&O (Compliance

Order)Order)

2003 Soil gas survey by School District 2003 Soil gas survey by School District (w/o LEA’s knowledge) in asphalted (w/o LEA’s knowledge) in asphalted playgrounds showed CHplaygrounds showed CH44 = 13% adjacent = 13% adjacent to School’s east wingto School’s east wing

2004 Additional soil gas surveys confirmed 2004 Additional soil gas surveys confirmed elevated levels of CHelevated levels of CH44

7979

Soil GasSoil GasSurveySurvey

Exhibit 1Exhibit 1

8080


Exhibit 2Exhibit 2

8181


Exhibit 3Exhibit 3

8282

Background (contd.)Background (contd.) School District’s consultant explained that School District’s consultant explained that

high CHhigh CH4 4 levels detected:levels detected:

1.1. Around the east wing Around the east wing “probably are “probably are related to gas migration from a source related to gas migration from a source area at the east wing” area at the east wing”

2.2. Along the south end of the asphalted Along the south end of the asphalted playgrounds playgrounds “probably are related to gas “probably are related to gas migration from former Cannery Street migration from former Cannery Street Landfill area”Landfill area”

8383

Background (contd.)Background (contd.) School District tried to keep field School District tried to keep field

results a secret, but…………………..results a secret, but…………………..

The genie was out of the bottle The genie was out of the bottle

8484

Background (contd.)Background (contd.) After field results were leaked out, the After field results were leaked out, the

School District:School District:

1.1. Promptly installed CHPromptly installed CH44 sensor/alarm in sensor/alarm in every class roomevery class room

2.2. Maintained that the disposal site was the Maintained that the disposal site was the source of source of allall CH CH44 detected throughout the detected throughout the elementary schoolelementary school

The LEA wanted to confirm that migrating The LEA wanted to confirm that migrating LFG plume has reached the school’s east LFG plume has reached the school’s east wingwing

8585

VIVIWorkplan ImplementationWorkplan Implementation

&&ProceduresProcedures

8686

Investigation WorkplanInvestigation Workplan To determine if the disposal site is (or To determine if the disposal site is (or

isn’t) the source of CHisn’t) the source of CH44 detected at all detected at all locations of the school facilitylocations of the school facility

Installation of 3 dual completion probes Installation of 3 dual completion probes along the potential migration pathway (1 along the potential migration pathway (1 in refuse and 2 in asphalt)in refuse and 2 in asphalt)

Sampling probe locations:Sampling probe locations:- 5 exist. near east wing (MDP series)- 5 exist. near east wing (MDP series)- 3 newly-installed (LFG series) - 3 newly-installed (LFG series) - 2 exist. along N side of Cannery St.- 2 exist. along N side of Cannery St.

(C-GP series)(C-GP series)

8787

LFG-1

LFG-2

LFG-3

MDP-1

MDP-2

MDP-5

MDP-4

MDP-3

C-GP-8A

C-GP-7A

8888

Investigation WorkplanInvestigation Workplan Screen sampling locations for COScreen sampling locations for CO22, O, O22, N, N22, ,

CHCH44 and H and H22S S

If CHIf CH44>1% collect samples for lab analysis>1% collect samples for lab analysis

Background and duplicate samples Background and duplicate samples (QA/QC)(QA/QC)

8989

Investigation Workplan (contd.)Investigation Workplan (contd.)

Lab analysis:Lab analysis:- - COCO22, O, O22 and Balance (mostly N and Balance (mostly N22))- Hydrocarbons C- Hydrocarbons C11 – C – C55 - Pipeline gas tracers- Pipeline gas tracers- VOCs (including BTEX)- VOCs (including BTEX)- (- (1313C/C/1212C) C) - - 1414CC- H- H22SS

9090

Workplan ImplementationWorkplan Implementation

June 2005June 2005

3 Proposed probes (LFG-1, -2 and -3) were 3 Proposed probes (LFG-1, -2 and -3) were installed installed

Sample locations were 1Sample locations were 1stst purged and purged and screened for CHscreened for CH44, fixed gases, H, fixed gases, H22SS

Field measurements loggingField measurements logging

9191


Collected samples if CHCollected samples if CH44>0.1%>0.1%

Added hydrogen isotope ratio (Added hydrogen isotope ratio (22H/H/11H) of H) of CHCH44 to the lab analysis to the lab analysis

Collected samples from probes:Collected samples from probes:- 3 exist. near east wing (MDP-2, -3, & -4)- 3 exist. near east wing (MDP-2, -3, & -4)- 3 newly-installed (LFG-1, -2 & -3) - 3 newly-installed (LFG-1, -2 & -3) - 1 exist. probe along N side of Cannery- 1 exist. probe along N side of Cannery

St. Landfill (C-GP-7)St. Landfill (C-GP-7)

9292


Samples for HSamples for H22S and pipeline gas S and pipeline gas tracers lab analysis were collected tracers lab analysis were collected lastlast

Lab samples labeling, logging in Lab samples labeling, logging in COCs, packing and shippingCOCs, packing and shipping

3 Different analytical labs3 Different analytical labs

9393


9494

VIIVIIResults and InterpretationResults and Interpretation

9595

Results and InterpretationResults and Interpretation

Since no tracers were detected in any Since no tracers were detected in any collected sample, leaking gas pipeline was collected sample, leaking gas pipeline was ruled out as a sourceruled out as a source

Except for LFG-1, (Except for LFG-1, (1313C/C/1212C) for CHC) for CH44 fell fell within range of biogenic gaseswithin range of biogenic gases

Except for MDP-4, (Except for MDP-4, (1414C) content was C) content was consistent and very close to biogenic gas consistent and very close to biogenic gas rangerange

9696

LFG-3 D (A)LFG-3 D (Dup 1)C-GP-7 (A)LFG-2 S (A)LFG-1 S (A)MDP-2 DBackground (A)

Note:

* Ratios in blue denote a non-detected C2-C5 and for the purposes of having

a graphical representation (ratio) a lower number was used. In these

case a value lower than the Reporting Limit was assigned = 0.1 ppm.

Hydrocarbon Ratios (C1/C2-C5)Kettler Elementary School & Cannery St. Landfill

1

10

100

1,000

10,000

100,000

1,000,000

10,000,000

- - - - - -

Rat

io(L

og

Sca

le)

C1/C2 C1/C3 C1/C4 C1/C5

900350

1,5004,500

9797

14C Content of the Methane (pMC)Kettler Elementary School & Cannery St. Landfill

101.10100.4099.50106.70

89.4097.90

65.50

0

20

40

60

80

100

120

140

LF

G-3

D

LF

G-3

D(D

up

lica

te)

C-G

P-7

LF

G-2

S

LF

G-1

S

MD

P-2

Int

MD

P-4

D

Probe

14C

Act

ivit

y (p

MC

)

9898

Results and Interpretation (contd.)Results and Interpretation (contd.)

C-GP-7, LFG-2 and LFG-3 had (C-GP-7, LFG-2 and LFG-3 had (1414C) C) and (and (22H/H/11H) values within the ranges H) values within the ranges of LFGof LFG

MDP-4 had (MDP-4 had (1414C) and (C) and (22H/H/11H) values H) values that clearly suggest commingling of that clearly suggest commingling of both landfill gas and thermogenic both landfill gas and thermogenic (older gas source)(older gas source)

9999

LFG-3 D LFG-3 D (Duplicate)C-GP-7 LFG-2 SLFG-1 S MDP-2 IntMDP-4 DBackground (B)

Formation of Detected MethanePlot of d13 C of CH4 vs dD of CH4 (

0/00)Kettler Elementary School & Cannery St. Landfill

-360

-320

-280

-240

-200

-160

-120

-80

-100 -90 -80 -70 -60 -50 -40 -30 -20d13 C of CH4 (

0/00)

d D o

f C

H4 (

0/ 0

0)


Mixed Gases

Termogenic GasBiogenic

CO2 Reduction

C-GP-7

MDP-4D

LFG-1S

LFG-2S

MDP-2 Int

LFG-3D

LFG-3D (Duplicate)

100100

VIIIVIIIConclusionsConclusions

101101

ConclusionsConclusions

LFG plume has migrated off-site under the LFG plume has migrated off-site under the school’s asphalted playgrounds.school’s asphalted playgrounds.

Cannery St. Landfill is one source of CHCannery St. Landfill is one source of CH44 detected around the school’s east wing, detected around the school’s east wing, there is-are other older source (s) for CHthere is-are other older source (s) for CH44 detecteddetected

Questions?Questions?

Documents

1 Fingerprinting and Forensic Techniques for Landfill Gas Geochemical Assessment LEA/CIWMB Partnership Conference Monterey, CA - August 2, 2006 CIWMB Abel