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Pentachlorophenol Aquatic Fate and Effects David Kent Keller and Heckman  LLP 1001 G St. NW, Suite 500 West Washington, DC 20001 [email_address] www.khlaw.com Washington, D.C.  ●  Brussels  ●  San Francisco  ●  Shanghai May 18, 2007 Diana Graham Keller and Heckman  LLP 50 California Street, Suite 1500 San Francisco, CA 94111 [email_address]
Background ,[object Object],[object Object],[object Object]
Physical Properties Readily dissolves in most solvents Organic solvent solubility 10 mg/L at pH 6 20 mg/L at pH 8 Water solubility 5.1 (pH 4) 3.3 (pH 7) 1.9 (pH 8) Log K ow 1.6x10 -14 Dissociation Constant K a 0.00415 Pa (1.1x10 -4  Torr at 25°C) Vapor pressure 1.98 g/cm 3  at 22°C Density 310°C (decomposes) Boiling point 191°C Melting point 266.34 Mol wt C 6 Cl 5 OH Formula Structure
Speciation and Partitioning Influence of pH on solubility and log K ow pH dependent speciation
Photodegradation ,[object Object],[object Object],[object Object]
Biodegradation ,[object Object],[object Object],[object Object],[object Object]
Biodegradation/Photodegradation Mixed bacterial cultures  ~1.5  Yu and Ward (1994)  pH 7.3 (natural sun-light)  2.0  Wong and Crosby (1981)  Anaerobic in laboratory, dark   190.0  Liu  et al.  (1981)  Aerobic in the laboratory  0.36  Liu  et al.  (1981)  Outdoor mesocosms  2.0 to 4.7  Crossland and Wolff (1985)  Anaerobic in the laboratory (dark – biodegradation only) 79.8  Boyle  et al.  (1980)  Aerobic in the laboratory  18.6  Boyle  et al.  (1980)  Conditions Half-life, days Author
Effect of pH on Photodegradation Rate ,[object Object],1  UV portion of sunlight,  λ max  = 320 nm 10  7.3 Wong and Crosby (1981) simulated sunlight  72 7.3 Wong and Crosby (1981) natural sunlight 100 3.3 Wong and Crosby (1981) simulated sunlight 1  Half-Life, hours pH Author
Effect of pH on Biodegradation Rate ,[object Object],36 6.3 – 8.0 Wolski et al. (2006) 90 5.5 Wolski et al. (2006) Half-life, hours pH Author
Effect of Temperature on Degradation Rate ,[object Object],<12 20 Topp  et al.  (1988) No degradation 0 Trevors (1982) >80 4 Topp  et al.  (1988) Half-life (days) Temperature (°C) Author
Monitoring Data – Washington State 1  note that reported values below the MDL of 0.007 ug/L are estimates  ND ND 0 2005 0.0051 1 0.0041 1 6 2004 0.0014 1 0.0014 1 5 2003 Spring Creek ND ND 0 2005 0.0054 1 0.0054 1 3 2004 0.0078 0.0063 1 10 2003 Sulfur Creek Wasteway ND ND 0 2005 ND ND 0 2004 0.01 0.01 5 2003 Marion Drain 0.03 0.0081 21 2005 0.078 0.016 42 2004 0.083 0.015 78 2003 Thornton Creek Max, µg/L Median µg/L Frequency %
Monitoring Data - Illinois
Fate in Sediment ,[object Object],[object Object],[object Object],[object Object],[object Object]
Conclusions on Fate ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Acute Toxicity ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Acute Toxicity – Rainbow Trout Change in formulation has reduced toxicity 2003 160 Dwyer et. al. (2005)  1980 - 1987 34 to 121 Eisler (2000) 1980 and 2001 15 and 75 USEPA (2005) Study Year LC 50  (µg penta/L)  Author
Chronic Toxicity ,[object Object],[object Object],[object Object],[object Object]
Chronic Toxicity 1.0 10 100 1000 0 0.8 2.2 3.9 5 10 99% Level of Concern   95% Level of Concern   90% Level of Concern   duckweed daphnia daphnia daphnia plant flagfish FHM FHM FHM FHM snail Cerio diatom RBT G algae BG algae FHM RBT sockeye 99 95 50 Pentachlorophenol Concentration, ppb Chronic NOECs FHM – fathead minnow RBT – rainbow trout G algae – green algae BG algae – blue-green algae Cerio - ceriodaphnia Rank order of data (% species tested)
Effects of pH and temperature on toxicity ,[object Object],[object Object],[object Object],[object Object]
Biotransformation ,[object Object],[object Object],[object Object],Glickman  et al.  (1977) 6.2 hrs (blood); 23.7 hrs (fat) Rainbow Trout Nuutinen, et. al (2003) 3.6 hrs Hyalella azteca Lydy  et al.  (1994) 15 hours Midge Kukkonen and Oikari (1988) 24 hrs Daphnia magna Reference Half-life Species
Bioaccumulation/Bioconcentration ,[object Object],[object Object],[object Object],[object Object],[object Object]
Bioconcentration no significant bioaccumulation Sub-adult African clawed frogs Oral - PCP  in meal worms 424 Blackworm Lumbriculus variegatus Sediment 229 – water 7.3 sediment Midge larvae Water & sediment 458 midge  Chironomus riparius Water & sediment 79 and 62 Duckweed  Lemna polyrhiza Water 25.2 – 38.7, 37.7 and 103.4 – 188.5 for eggshell, yolk sac and embryo Salmon eggs Water 132 Scud  Hyalella azteca Water 73 Depressed River Mussel Pseudanodonta complanata Water 100 freshwater mussels  Anadonta anatina Water 145 to 342 freshwater mussels  Anadonta anatina Water BCF Test Species Route of Exposure
EPA Aquatic Criteria ,[object Object],[object Object],7.9  13  15  19  chronic (µg/L) acute (µg/L) chronic (µg/L) acute (µg/L) Saltwater Freshwater
Conclusions on Effects ,[object Object],[object Object],[object Object],[object Object],[object Object]
Exposure – Rainwater Runoff ,[object Object],[object Object],[object Object],[object Object]
Dilution in Receiving Water ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Concentration in Receiving Water ,[object Object],[object Object],[object Object],[object Object],[object Object]
Estimated Water Concentrations – Skull Canyon Example ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Sediment Concentrations ,[object Object],[object Object]
Sediment Monitoring: Cougar Smith Bridge - Washington ,[object Object],[object Object],[object Object],[object Object],[object Object]
Sediment Monitoring: Upper Dairy Creek Bridge - Oregon No adverse affects were noted when a bioassay was conducted on  sediments collected from under the bridge
Sediment Benchmarks ,[object Object],[object Object],[object Object]
Conclusions on Fate, Effects and Exposure ,[object Object],[object Object],[object Object],[object Object]
Thank you! www.khlaw.com Washington, D.C.  ●  Brussels  ●  San Francisco  ●  Shanghai Diana Graham Keller and Heckman  LLP 50 California Street, Suite 1500 San Francisco, CA 94111 [email_address] David Kent Keller and Heckman  LLP 1001 G St. NW, Suite 500 West Washington, DC 20001 [email_address]

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Penta aquaticf ate and effects

  • 1. Pentachlorophenol Aquatic Fate and Effects David Kent Keller and Heckman LLP 1001 G St. NW, Suite 500 West Washington, DC 20001 [email_address] www.khlaw.com Washington, D.C. ● Brussels ● San Francisco ● Shanghai May 18, 2007 Diana Graham Keller and Heckman LLP 50 California Street, Suite 1500 San Francisco, CA 94111 [email_address]
  • 2.
  • 3. Physical Properties Readily dissolves in most solvents Organic solvent solubility 10 mg/L at pH 6 20 mg/L at pH 8 Water solubility 5.1 (pH 4) 3.3 (pH 7) 1.9 (pH 8) Log K ow 1.6x10 -14 Dissociation Constant K a 0.00415 Pa (1.1x10 -4 Torr at 25°C) Vapor pressure 1.98 g/cm 3 at 22°C Density 310°C (decomposes) Boiling point 191°C Melting point 266.34 Mol wt C 6 Cl 5 OH Formula Structure
  • 4. Speciation and Partitioning Influence of pH on solubility and log K ow pH dependent speciation
  • 5.
  • 6.
  • 7. Biodegradation/Photodegradation Mixed bacterial cultures ~1.5 Yu and Ward (1994) pH 7.3 (natural sun-light) 2.0 Wong and Crosby (1981) Anaerobic in laboratory, dark  190.0 Liu et al. (1981) Aerobic in the laboratory 0.36 Liu et al. (1981) Outdoor mesocosms 2.0 to 4.7 Crossland and Wolff (1985) Anaerobic in the laboratory (dark – biodegradation only) 79.8 Boyle et al. (1980) Aerobic in the laboratory 18.6 Boyle et al. (1980) Conditions Half-life, days Author
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  • 11. Monitoring Data – Washington State 1 note that reported values below the MDL of 0.007 ug/L are estimates ND ND 0 2005 0.0051 1 0.0041 1 6 2004 0.0014 1 0.0014 1 5 2003 Spring Creek ND ND 0 2005 0.0054 1 0.0054 1 3 2004 0.0078 0.0063 1 10 2003 Sulfur Creek Wasteway ND ND 0 2005 ND ND 0 2004 0.01 0.01 5 2003 Marion Drain 0.03 0.0081 21 2005 0.078 0.016 42 2004 0.083 0.015 78 2003 Thornton Creek Max, µg/L Median µg/L Frequency %
  • 12. Monitoring Data - Illinois
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  • 16. Acute Toxicity – Rainbow Trout Change in formulation has reduced toxicity 2003 160 Dwyer et. al. (2005) 1980 - 1987 34 to 121 Eisler (2000) 1980 and 2001 15 and 75 USEPA (2005) Study Year LC 50 (µg penta/L) Author
  • 17.
  • 18. Chronic Toxicity 1.0 10 100 1000 0 0.8 2.2 3.9 5 10 99% Level of Concern 95% Level of Concern 90% Level of Concern duckweed daphnia daphnia daphnia plant flagfish FHM FHM FHM FHM snail Cerio diatom RBT G algae BG algae FHM RBT sockeye 99 95 50 Pentachlorophenol Concentration, ppb Chronic NOECs FHM – fathead minnow RBT – rainbow trout G algae – green algae BG algae – blue-green algae Cerio - ceriodaphnia Rank order of data (% species tested)
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  • 22. Bioconcentration no significant bioaccumulation Sub-adult African clawed frogs Oral - PCP in meal worms 424 Blackworm Lumbriculus variegatus Sediment 229 – water 7.3 sediment Midge larvae Water & sediment 458 midge Chironomus riparius Water & sediment 79 and 62 Duckweed Lemna polyrhiza Water 25.2 – 38.7, 37.7 and 103.4 – 188.5 for eggshell, yolk sac and embryo Salmon eggs Water 132 Scud Hyalella azteca Water 73 Depressed River Mussel Pseudanodonta complanata Water 100 freshwater mussels Anadonta anatina Water 145 to 342 freshwater mussels Anadonta anatina Water BCF Test Species Route of Exposure
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  • 31. Sediment Monitoring: Upper Dairy Creek Bridge - Oregon No adverse affects were noted when a bioassay was conducted on sediments collected from under the bridge
  • 32.
  • 33.
  • 34. Thank you! www.khlaw.com Washington, D.C. ● Brussels ● San Francisco ● Shanghai Diana Graham Keller and Heckman LLP 50 California Street, Suite 1500 San Francisco, CA 94111 [email_address] David Kent Keller and Heckman LLP 1001 G St. NW, Suite 500 West Washington, DC 20001 [email_address]

Notas do Editor

  1. Penta is somewhat soluble in water. The log K ow from 1.9 to 5.1 depending on pH. It is not particularly volatile. The physico-chemico properties are very dependent on pH.
  2. pKa is 4.7. It is not dissociated at pH less than 5. Above 5, dissociation to pentachlorophosphenate increases with increasing pH. As pH increases, water solubility increases. As pH increases, log Kow decreases. At environmentally relevant pHs mostly present as the more water soluble anion This effects the ultimate fate of penta.
  3. For the guideline study, the temperature range did not change the photodegradation rate.
  4. McAllister e. al. 1996; degradation/dissipation for all pathways
  5. See section starting at line 177 in fate paper
  6. The results of monitoring studies show that concentrations of penta in the environment have declined since agricultural uses stopped. Concentrations in urban streams are well below the EPA aquatic criteria
  7. Concentrations in rural areas are also below the criteria
  8. (Wong and Crosby, 1981).
  9. (Apache trout, Lahontan cutthroat trout, greenback cutthroat trout, bonytail chub, Colorado pike minnow, razorback sucker, Leon Springs pupfish, and desert pupfish)
  10. At pH 4 it is fully protonated and therefore highly lipophilic resulting in higher bioconcentration potential At pH 9.0 it is completely ionized with lower bioconcentration potential and significantly reduced toxicity For algae, snails and fish at pH 4 BCF = 117.2 to 681.9 but at environmentally realistic pH values of 6.0 and 8.0 ranged from 3.8 (algae at pH = 8.0) to 271.1 (fish at pH = 6.0). Similar levels were found in blood plasma benthic-feeding fish species (0.06 to 3.43 mg/kg) and in pelagic and piscivorious fish species (0.21 to 1.62 mg/kg) from the Detroit River
  11. Morrell and Simonsen investigated the rate of loss of penta from treated boards. The average loss rate was 0.015 ug/ml-cm 2
  12. Environmental Impact of Treated Wood in Service Stan Lebow, Kenneth Brooks, and John Simonsen From “Enhancing the Durability of Lumber and Engineered Wood Products”, Forest Products Society 2801 Marshall Court Madison, WI 53 705-2295
  13. Assessment of the Environmental Effects Associated With Wooden Bridges Preserved With Creosote, Pentachlorophenol, or Chromated Copper Arsenate Kenneth M. Brooks