Tier II Results forMultimedia Risk Assessment of Biodiesel ... · Tier II Results forMultimedia...
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Tier II Results forMultimediaRisk Assessment of Biodiesel:
Relative Mobility,Biodegradation, and Aquatic
Toxicity8 December 2010 MMRA
Workshop
TR Ginn1, ML Johnson2, KM Scow3, J Miller4, L Rastegarzadeh1, T Hatch1, AEpple1, V Nino1, T Schetrit1, T Barkouki1, D Rice5, T McKone6
1 UC Davis Civil & Environmental Engineering2 UC Davis Aquatic Ecosystems Analysis Laboratory
3 UC Davis Department of Land, Air, and Water Resources4 Aquascience Inc., Davis CA
5 Consultant to UC6 UC Berkeley, Environmental Health Sciences
Conceivemodel
Tier 1PreliminaryReview
Tier 2 MultimediaRisk AssessmentDesign Review
Tier 3Final MultimediaRisk Review
- Define framework and approach- Identify information needs and gaps- Peer review
- Experimental designdeveloped and submitted
- Design peer reviewed,feedback provided for Tier 3
- Final report is used as the basis forrecommendations submitted to theEnvironmental Policy Council
- Final report is peer reviewed
Multimedia Risk AssessmentTier 1Tier IITier III
Multimedia Risk Assessment1
Tier 1Tier II2
Tier IIITier 1PreliminaryReview
Tier 2 MultimediaRisk AssessmentDesign Review
Tier 3Final MultimediaRisk Review
- Define framework and approach- Identify information needs and gaps- Peer review
- Experimental designdeveloped and submitted
- Design peer reviewed,feedback provided for Tier 3
- Final report is used as the basis forrecommendations submitted to theEnvironmental Policy Council
- Final report is peer reviewed
1 http://www.arb.ca.gov/fuels/multimedia/multimedia.htm2 http://www.arb.ca.gov/fuels/diesel/altdiesel/biodiesel.htm
• Mobility- Side-by-side infiltration in 2D “ant farm” flow cells
• Biodegradation Tests- Microcosm respirometry in soil slurry, 29 day
• Aquatic Toxicity- Suite of freshwater/estuarine toxicity tests
Multimedia Risk Assessment1
Tier II2
Experiments Performed
1 http://www.arb.ca.gov/fuels/multimedia/multimedia.htm2 http://www.arb.ca.gov/fuels/diesel/altdiesel/biodiesel.htm
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Mobility
Fuel Blends
• Image analysis of biodiesel vertical infiltration in Sandbox• 30x20x2cm, #20 (coarse) sand, water table• Soy- and Animalfat-based 100% and 20% blends, 1 additive
Mobility
• Sandbox preparation - Wet-pluviated sand - Drain to water table - simultaneous 50mL ULSD#2 and biodiesel side-by-side, both dyed
• Data collected - infiltration rate in vadose zone - redistribution - lens form & surface area, on water table
Mobility
• Soy B20 least different
Sample Results Final Lenses
Soy B20a CARB ULSD#2
Mobility
• Animalfat B100 strongest effect - similar traveltimes - Less lateral dispersion - thicker, deeper lens - more residual, less sfc area
Sample Results Final Lenses
AF B100a CARB ULSD#2
Mobility
• Minor differences in traveltimes• AF B100a only shows
Moderate differences - thicker lens formation - more residual
Summary
Mobility
• Minor differences in traveltimes• AF B100a only shows
Moderate differences - thicker lens formation - more residual• Interfacial Tensions1 (mN/m):
ULSD: 7.4Soy (B20/B100): 8.5/12.0AF (B20/B100): 15.0/19.5
• Viscosity1
Summary
Soy
Animal Fat
1.Yang et al., ULSD/Biodiesel blend and its effect on fuel/ water separation, Amer.Filtration & Separation Soc. Annual Conf., May 19-22 (2008), Valley Forge, PA
• 29-day Respirometry using soil slurry inoculum - Soy- and Animalfat-based 100% and 20% blends, 2 additives• Microcosm preparation - 250 mL flask that consists of 200 ml mineral medium - 2 g soil (Yolo silt loam) as bacterial inoculums - 5uL of test substrate• For each fuel type:
- triplicate batch- one sterilize control (1% sodium azide) - showed no CO2.
Biodegradation Tests
Fuel Blends
Biodegradation Tests
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Results
Biodegradation Tests
ULSDSoy B-20Soy B-20AAF B-20A
ULSDSoy B-20AAAF B-20AASoy B-100AA
ULSDSoy B-100AF B-20AF B-100
Biodegradation Tests
29Day Cumulative degradation percentages
ULS
D
AF B
-20
Soy B
-20 A
ULS
D
ULS
D
AF B
-100
AF B
-20 AA
AF B
-20 A
Soy B
-20
Soy B
-20 AA
Soy B
-100
Soy B
-100 AA
• All fuel blends more readilydegrable than ref. fuel
• Soy-based blends somewhatmore degrable than Animalfat-based blends
• 20% biodiesel blendssomewhat more degrable than100% biodiesel
• Additives effect are minor
Biodegradation Tests
Summary
• 6 fuel blends• 3 freshwater and 3 estuarine organisms• 6 dilutions plus a control per species/fuel• Using published USEPA chronic toxicity
testing protocols• “100% solutions” produced using the
“slow stir” method, defining equilibriumsolubility conditions
• All tests met protocol QA/QCrequirements
Aquatic Chronic Toxicity Tests
Aquatic Chronic Toxicity Tests
6 Blends in addition to reference fuel (ULSD) - Animalfat biodiesel (100% 20%, 20% w/additive) - Soy biodiesel (100% 20% 20% w/additive)
100% solubility solution by slow stir method - solutions 100%, 50%, 25%, 10%, 5%, and 1%, w/stock # 2 samples/test archived frozen for later analysis # Replicates for particular combinations.
Interpolate among dilutions to determine EC25 - “Toxicity” as TU = 100/EC25 # TU<1 no effects # TU = 1 effects seen only at 100% solution # TU = 100 effects seen at 1% solution
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Fuel Blends
Aquatic Chronic Toxicity Tests
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• ULSD - low but detectable toxicity on mysid growth (1.0 TU) andCeriodaphnia reproduction (1.8 TUc) only.
• No unadditized Animalfat or Soy Biodiesel blends produceddetectable toxicity to the mysid, topsmelt or fathead minnow.
• Animal Fat and Soy B-100 and B-20 mixtures caused toxicity toalgae cell growth, abalone shell development, and Ceriodaphniasurvival and/or growth.
• Except for algae, the additized Biodiesel B-20 test materials weresubstantially more toxic than the corresponding unadditizedmaterial.
Aquatic Chronic Toxicity Tests
Results
Aquatic Chronic Toxicity Tests
Examples
Red Abalone (Haliotis Rufecens) shell development
Aquatic Chronic Toxicity Tests
Examples
Water flea (Ceriodaphnia dubia) survival and reproduction
Aquatic Chronic Toxicity Tests
Summary Toxicity with additive
Toxicity apparent in all 6 species per growth endpoint
Aquatic Chronic Toxicity Tests
Summary
• Biodiesel blends are significantly more toxic than CARB ULSD#2 - algae cell growth - abalone shell development - Ceriodaphnia survival and growth
• Biodiesel 20% blends with antioxidant additive were substantiallymore toxic than the corresponding unadditized blend
- abalone shell development - Ceriodaphnia survival and growth
Tier II for Biodiesel Blends Tested
Summary• Mobility
- AFB100a shows thicker lens, more residual - due to higher viscosity, IFT
• Biodegradation - All biodiesel blends more readily degrable than ULSD
- Soy-based blends, or 20%s, somewhat more degrable - Additives effect are minor
• Aquatic Toxicity- Biodiesel blends are more toxic than ULSD#2
- Biodiesel 20% blends with antioxidant additive are moretoxic than the corresponding unadditized blend
Tier II for Biodiesel Blends Tested
Summary• Mobility
- AFB100a only shows smaller lens, more residual
• Biodegradation - All biodiesel blends more readily degrable than ULSD
- Soy-based blends, or 20%s, somewhat more degrable - Additives effect are minor
• Aquatic Toxicity- Biodiesel blends are more toxic than ULSD#2
- Biodiesel 20% blends with antioxidant additive are moretoxic than the corresponding unadditized blend