1. Bernine Khan University of Miami Arsenic Speciation of New & Weathered CCA-Treated Wood

2. Purpose Basic Arsenic Chemistry Solvent-Extraction Leaching Expts Arsenic Analysis of GW at Florida C&D Landfills Arsenic Leaching from Lysimeter Study Arsenic Leaching from CCA-Treated Deck Arsenic Study Outline

3. Purpose Basic Arsenic Chemistry Solvent-Extraction Leaching Expts Arsenic Analysis of GW at Florida C&D Landfills Arsenic Leaching from Lysimeter Study Arsenic Leaching from CCA-Treated Deck

4. Arsenic Study Outline Purpose Basic Arsenic Chemistry Solvent-Extraction Leaching Expts Arsenic Analysis of GW at Florida C&D Landfills Arsenic Leaching from Lysimeter Study Arsenic Leaching from CCA-Treated Deck

5. Arsenic Study Outline Purpose Basic Arsenic Chemistry Solvent-Extraction Leaching Expts Arsenic Analysis of GW at Florida C&D Landfills Arsenic Leaching from Lysimeter Study Arsenic Leaching from CCA-Treated Deck

6. Arsenic Study Outline Purpose Basic Arsenic Chemistry Solvent-Extraction Leaching Expts Arsenic Analysis of GW at Florida C&D Landfills As Leaching - Lysimeter Study (Jenna - UF) Arsenic Leaching from CCA-Treated Deck

7. Arsenic Study Outline Purpose Basic Arsenic Chemistry Solvent-Extraction Leaching Expts Arsenic Analysis of GW at Florida C&D Landfills Arsenic Leaching from Lysimeter Study Arsenic Leaching from a constructed CCA-Treated Deck

8. Identify & quantify arsenic species leaching from CCA-treated wood Arsenic toxicity varies with each species To study the migration of arsenic species [As(III) & As(V)] in soils Estimate the impact of arsenic leaching from in-service & disposed CCA-treated wood on groundwater Purpose of Study

9. Identify & quantify arsenic species leaching from CCA-treated wood Arsenic toxicity varies with each species To study the migration of arsenic species [As(III) & As(V)] in soils Estimate the impact of arsenic leaching from in-service & disposed CCA-treated wood on groundwater Purpose of Study

10. Identify & quantify arsenic species leaching from CCA-treated wood Arsenic toxicity varies with each species To study the migration of arsenic species [As(III) & As(V)] in soils Estimate the impact of arsenic leaching from in-service & disposed CCA-treated wood on groundwater Purpose of Study

11. Identify & quantify arsenic species leaching from CCA-treated wood Arsenic toxicity varies with each species To study the migration of arsenic species [As(III) & As(V)] in soils Estimate the impact of arsenic leaching from in-service & disposed CCA-treated wood on groundwater Purpose of Study

12. The individual parts that make up the whole: What is Speciation?  Element valence  Particle size  Molecular weight size  Inorganic & organic form

13. The individual parts that make up the whole: What is Speciation?  Element valence  Particle size  Molecular weight size  Inorganic & organic form

14. The individual parts that make up the whole: What is Speciation?  Element valence  Particle size  Molecular weight size  Inorganic & organic form

15. The individual parts that make up the whole: What is Speciation?  Element valence  Particle size  Molecular weight size (Sheena - FIU)  Inorganic & organic form

16. The individual parts that make up the whole: What is Speciation?  Element valence  Particle size  Molecular weight size  Inorganic & organic form

17. Speciation Arsenic As(III) As(V)MMAADMAA Various forms of an element that make up the total concentration of that element Inorganic Organic -30+1+3+5 Valence Inorganic Arsine (g)

18. Arsenic As(III) As(V)MMAADMAA Various forms of an element that make up the total concentration of that element Inorganic Organic -30+1+3+5 Valence Inorganic Arsine (g) Speciation

19. Arsenic As(III) As(V)MMAADMAA Various forms of an element that make up the total concentration of that element Inorganic Organic -30+1+3+5 Valence Inorganic Arsine (g) Speciation

20. In nature – arsenites (As(III)) & arsenates (As(V)) Soluble arsenic compounds As(III) - more soluble in water & body fluids Toxicity Interest in Speciation

21. In nature – arsenites (As(III)) & arsenates (As(V)) Soluble arsenic compounds (As(III)) are more toxic to humans than insoluble As(III) - more soluble in water & body fluids Toxicity Interest in Speciation

22. In nature – arsenites (As(III)) & arsenates (As(V)) Soluble arsenic compounds are more toxic to humans than insoluble As(III) compounds are generally more soluble in water & body fluids – not excreted readily – accumulates in body – toxic at low concentrations Toxicity Interest in Speciation

23. In nature – arsenites (As(III)) & arsenates (As(V)) Soluble arsenic more toxic to humans As(III) - more soluble in water & body fluids Toxicity is dependent upon: - arsenic compound - magnitude of exposure (conc. accumulated over time) - species Interest in Speciation

24. Toxicity of Arsenic Species Dependent on chemical form AsH 3 - arsine (gas) – most toxic (formed under reduced conditions) As(III) - arsenite As(V) - arsenate MMAA - monomethylarsonic acid DMAA - dimethylarsinic acid TMAO - trimethylarsine oxide AsB - arsenobetaine (marine) * AsC - arsenocholine (marine) *

25. Toxicity of Arsenic Species Dependent on chemical form AsH 3 - arsine (gas) As(III) - arsenite – inorganic (more toxic) As(V) - arsenate – inorganic - CCA MMAA - monomethylarsonic acid DMAA - dimethylarsinic acid TMAO - trimethylarsine oxide AsB - arsenobetaine (marine) * AsC - arsenocholine (marine) *

26. Toxicity of Arsenic Species Dependent on chemical form AsH 3 - arsine (gas) As(III) - arsenite – inorganic As(V) - arsenate – inorganic MMAA - monomethylarsonic acid DMAA - dimethylarsinic acid TMAO - trimethylarsine oxide AsB - arsenobetaine (marine) * AsC - arsenocholine (marine) * bacteria

27. Toxicity of Arsenic Species Dependent on chemical form AsH 3 - arsine (gas) As(III) - arsenite – inorganic As(V) - arsenate – inorganic MMAA - monomethylarsonic acid DMAA - dimethylarsinic acid TMAO - trimethylarsine oxide AsB - arsenobetaine (marine) * AsC - arsenocholine (marine) *

28. Arsenic Leaching From CCA-Treated Wood Solvent-Extraction Tests Toxicity Characteristic Leaching Procedure (TCLP) – EPA’s standardized leaching test to determine if treated wood waste is hazardous. CCA-treated wood carries an exemption. SPLP – EPA’s leaching test Other Solvents pH Stat – Leaching of As species under different pH conditions (similar to TCLP)

29. Arsenic Leaching From CCA-Treated Wood Solvent-Extraction Tests TCLP – EPA’s leaching test Synthetic Precipitation Leaching Procedure (SPLP) – EPA’s standardized leaching test to (simulate rainfall) determine if treated wood waste should be land applied Other Solvents pH Stat – Leaching of As species under different pH conditions (similar to TCLP)

30. Arsenic Leaching From CCA-Treated Wood Solvent-Extraction Tests TCLP – EPA’s leaching test SPLP – EPA’s leaching test Other Solvents – Deionized Water, Rainwater, & Seawater pH Stat – Leaching of As species under different pH conditions (similar to TCLP)

31. Arsenic Leaching From CCA-Treated Wood Solvent-Extraction Tests TCLP – EPA’s leaching test SPLP – EPA’s leaching test Other Solvents – Deionized Water, Rainwater, & Seawater pH Stat – Leaching of As species under different pH conditions (similar to TCLP)

32. CCA-treated wood subjected to leaching solvent, rotated for 18  2 hrs & filtered. Filtrate analyzed for arsenic species New CCA-treated wood TCLP SPLP DI Water Rainwater Untreated 0.25 pcf 0.6 pcf 2.5 pcf Weathered CCA-treated wood Playground Utility pole Fence C&D waste Solvent-Extraction of CCA-Treated Wood

33. CCA-treated wood subjected to leaching solvent, rotated for 18  2 hrs & filtered. Filtrate analyzed for arsenic species New CCA-treated wood TCLP SPLP DI Water Rainwater Untreated 0.25 pcf 0.6 pcf 2.5 pcf Weathered CCA-treated wood Solvent-Extraction of CCA-Treated Wood Playground Utility pole Fence C&D waste

34. TCLP Results New & Weathered Wood Is treated wood waste hazardous? (Acetic Acid) As(III) As(V) Total As TCLP 5 mg/L New Weathered T V

35. SPLP Results New & Weathered Wood Should treated wood waste be land applied? (Sulphuric Acid/Nitric Acid) SPLP 0.05 mg/L As(III) As(V) Total As New Weathered T V

36. Deionized Water New & Weathered Wood As(III) As(V) Total As TCLP 5 mg/L New Weathered TU

37. Rainwater Results New & Weathered Wood TCLP 5 mg/L As(III) As(V) Total As New Weathered T U

38. Results of TCLP & SPLP New & Weathered Wood Ash TCLP 5 mg/L As(III) As(V) As(III) As(V) TCLP SPLP New Weathered TV

39. pH Stat CCA-treated wood subjected to leaching solvent (HNO 3 or NaOH – to obtain desired pH) New (0.4 pcf) CCA-treated wood measured at 0.214 pcf pH 1 2 3 4 5 6 7 8 9 10 11 12 Weathered CCA-treated wood measured at 0.386 pcf

40. Results of pH Stat New Wood As(V) was the only specie detected Highest concentration at extreme pH Environmental pH range – As(V) ~ 5mg/L TCLP 5 mg/L Environmental pH

41. Results of pH Stat Weathered Wood Both As(III) & As(V) detected As(III) up to pH 8.5 Environmental pH range – Total As increase Total As > 5 mg/L TCLP 5 mg/L As(III) As(V) Total Environmental pH

42. Results of pH Stat Total Arsenic Total arsenic conc. (mg/L) New (0.214 pcf) Weathered (0.386 pcf) – 14 yrs TCLP 5 mg/L Environmental pH

43. Summary As(III) present in all wood – new & weathered. If CCA-treated wood did not carry the exemption – it would fail TCLP and be categorized as hazardous waste All new & weathered CCA-treated wood failed the SPLP Slightly more As leaching from rainwater than the SPLP (simulate rainwater)

44. Summary As(III) present in all wood – both new & weathered If CCA-treated wood did not carry the exemption – it would fail TCLP and be categorized as hazardous waste All new & weathered CCA-treated wood failed the SPLP Slightly more As leaching from rainwater than the SPLP (simulate rainwater)

45. Summary As(III) present in all wood – both new & weathered If CCA-treated wood did not carry the exemption – it would fail TCLP and be categorized as hazardous waste All new & weathered CCA-treated wood failed the SPLP Slightly more As leaching from rainwater than the SPLP (simulate rainwater)

46. Summary As(III) present in all wood – both new & weathered If CCA-treated wood did not carry the exemption – it would fail TCLP and be categorized as hazardous waste All new & weathered CCA-treated wood failed the SPLP Slightly more As leaching from rainwater than the SPLP (simulate rainwater)

47. CCA-treated wood should not be incinerated and dispose to MSW and C&D landfills or land applied As leaching is pH dependent As species leaching pH dependent At environmental pH range (6-10) – As ~ 5mg/L More As leaching from weathered wood than new Summary

48. CCA-treated wood should not be incinerated and dispose to landfills or land applied Total As leaching is pH dependent As species leaching pH dependent At environmental pH range (6-10) – As ~ 5mg/L More As leaching from weathered wood than new Summary

49. CCA-treated wood should not be incinerated and dispose to landfills or land applied As leaching is pH dependent As species leaching pH dependent At environmental pH range (6-10) – As ~ 5mg/L More As leaching from weathered wood than new Summary

50. CCA-treated wood should not be incinerated and dispose to landfills or land applied As leaching is pH dependent As species leaching pH dependent At environmental pH range (6-10) – As ~ 5mg/L More As leaching from weathered wood than new Summary

51. CCA-treated wood should not be incinerated and dispose to landfills or land applied As leaching is pH dependent As species leaching pH dependent At environmental pH range (6-10) – As ~ 5mg/L Overall, more As leaching from weathered wood than new Summary

52. ? ? Questions ?

53. Lysimeter Study Lysimeter 1 – Untreated Wood As(III) As(V) DMAA MMAA

54. Lysimeter Study Lysimeter 2 – CCA-Treated Wood (50% New & 50% Used As(III) As(V) DMAA MMAA Predominantly As(III) & As(V) Low organoarsenic species concentrations

55. Lysimeter Study Lysimeter 3 – Typical C&D Mix As(III) As(V) DMAA MMAA All species detected