chemistry of oil in water

Transcription

1 Factors affecting the chemistry of oil in water

2 Factors affecting the chemistry of oil in water Mark G. Carls, Larry Holland, Marie Larsen NOAA, NMFS, Auke Bay Laboratory

3 Factors affecting the chemistry of oil in water (water-accommodated fractions) Mark G. Carls, Larry Holland, Marie Larsen NOAA, NMFS, Auke Bay Laboratory

4 3 Parts: 1. Methods determine PAH composition 2. PAH composition influences toxicity 3. Match assay methods to toxicant

5 Part I: Methods determine PAH composition

6 Example: low energy mixing nt of total aroma atics Perce W S F M o n o - D i-a ro m a tic (Carls 1987)

7 PAH in crude oil: (Fresh Exxon Valdez oil in PWS sediment) substitution: Molecular size Naph Flu Dib Phen Chry

8 PAH in crude oil:

9 PAH in crude oil:

10 PAH in crude oil:

11 PAH in crude oil:

12 PAH in crude oil:

13 PAH in crude oil:

14 PAH in crude oil:

15 PAH in crude oil:

16 PAH in crude oil:

17 PAH in crude oil:

18 PAH in crude oil:

19 PAH in crude oil:

20 PAH in crude oil:

21 PAH in crude oil:

22 PAH in crude oil:

23 PAH in crude oil:

24 PAH in crude oil:

25 PAH in crude oil:

26 PAH in crude oil:

27 PAH in crude oil: Molecular size Environmental persistence Solubility

28 The point: Know what you wish to emulate

29 Methods Oiled rock columns Water-accommodated fractions of oil

30 (High Energy mix)

31 Results:

32 Oil Only Energy polynuclear aroma atic hydrocarbons Percent of total % % 84.9% 79.7% 5.6% 1.% 18.4% Weathered Alaska North Slope crude oil 1.6% Low energy mix,.5 h 6.4 ug/l aq. TPAH.1 joules 2.4% 1.4% 1.4%.3% 1, c Medium energy mix, Oil only,.5 h12 h 31.1 ug/l aq. Dispersed TPAH oil, 12 h TP PAH conc. in wate er (ug/l) 1.6 joules 1 Dispersed oil,.5 h 4.4% 3.8% 6.2%.4% High energy mix,.5 h 47ug/Laq 47. aq. TPAH 12 Energy: 6 4.7% 4.7% 7.5%.5% weathering NPH C1NPH C2NPH C3NPH C4NPH BPH ACY ACE FLU C1FLU C2FLU C3FLU DBT C1DBT C2DBT C3DBT PHN C1PHN C2PHN C3PHN C4PHN ANT Oil only,.5 h joules Mixing energy (joules) FLA PYR Low C1FLA BAA CHR C1CHR C2CHR C3CHR C4CHR Medium High Open system

33 Oil High energy mix,.5 h ug/l aq. TPAH % 12 rocarbons Only % 4.7% 4.7% 7.5%.5% Mid-energy mix 16.3 ug/l aq. TPAH 2.3% High-energy mix High energy mix, 6 h 9.9% 14.% % 6 r aromatic hydr Time % 5 2.2% 2% 5 34.% High energy mix, 12 h 12.9 ug/l aq. TPAH Percent of total polynuclea r (ug/l) r (ug/l) % % 9.9% 13.7% 2 25.% 4 3 Dispersed oil 3.6% 14.8 ug/l aq. TPAH High energy mix, 18 h TPAH conc. in water TPAH conc. in water Time: weathering i % 5.4% 1 1 NPH C1NPH C2NPH C3NPH C4NPH BPH ACY ACE FLU C1FLU C2FLU C3FLU DBT C1DBT C2DBT C3DBT PHN C1PHN C2PHN C3PHN C4PHN ANT FLA PYR C1FLA BAA CHR C1CHR C2CHR C3CHR C4CHR Mixing time (hours) Oil only Mixing time (hours) Open system, high energy

34 Oil Only 1 2.4% % 21.% 3 ul oil Yield: ug/l aq. TPAH 37.9% 3.7% % 3 ul oil Yield: 87 ug/l aq. TPAH 15 1 Percent of total polynuclear aromatic hydrocarbons Volume % 9.5% 1, 16.1% a 1.5% 2 ul oil Yield: 286 ug/l aq. TPAH g/l) % 1 Dispersed oil 5 43% 4.3% 46% 4.6% 73% 7.3% 6%.6% 1 Oil only conc. in water (u Volume: NPH C1NPH C2NPH C3NPH C4NPH BPH ACY ACE FLU C1FLU C2FLU C3FLU DBT C1DBT C2DBT C3DBT PHN C1PHN C2PHN C3PHN C4PHN ANT FLA PYR C1FLA BAA CHR C1CHR C2CHR C3CHR C4CHR TPAH weathering , 1, Oil quantity (ul) Open system, high energy

35 In the short term (.5 h), dispersant increased weathering 3 24 Oil only High energy mix,.5 h 47. ug/l aq. TPAH % 6 47% 4.7% 47% 4.7% 75% 7.5%.5% N N1 N2 N3 N4 BPH ACY ACE F F1 F2 F3 D D1 D2 D3 P P1 P2 P3 P4 ANT FLA PYR FP1 BAA C C1 C2 C3 C % Oil + Dispersant 61.5 ug/l aq. TPAH High energy mix,.5 h 1 4.7% 7.3% 12.3%.9% 2 N N1 N2 N3 N4 BPH ACY ACE F F1 F2 F3 D D1 D2 D3 P P1 P2 P3 P4 ANT FLA PYR FP1 BAA C C1 C2 C3 C4 Open system

36 The image cannot be displayed. Your computer may not have enough memory to open the image, or the image may have been corrupted. Restart your computer, and then open the file again. If the red x still appears, you may have to delete the image and then insert it again. The image cannot be displayed. Your computer may not have enough memory to open the image, or the image may have been corrupted. Restart your computer, and then open the file again. If the red x still appears, you may have to delete the image and then insert it again. In the longer term, dispersant decreased weathering % TPAH % 13.7% Oil only 25.% High energy mix, 18 h 14.8 ug/l aq. TPAH 43.9% 5.4% N N1 N2 N3 N4 BPH ACY ACE F F1 F2 F3 D D1 D2 D3 P P1 P2 P3 P4 ANT FLA PYR FP1 BAA A C C1 C2 C3 C4 Oil + Dispersant % TPAH % 2.1% 27.1% 4.4% High energy mix, 18 h 2.9 ug/l aq. TPAH 1.2% N N1 N2 N3 N4 BPH ACY ACE F F1 F2 F3 D D1 D2 D3 P P1 P2 P3 P4 ANT FLA PYR FP1 BAA C C1 C2 C3 C4 Composition changes Open system

37 Open system Closed system

38 Oil Only Open/closed Closed: Open System (o+d) 27.1% 4.4% Open system 3 ug/l aq. TPAH 2.1% 9.7% 1.2% Closed System (o+d) Closed system 69.6% ug/l aq. TPAH 5.7% 7.7% 13.2% 1.2% NPH C1NPH C2NPH C3NPH C4NPH BPH ACY ACE FLU C1FLU C2FLU C3FLU DBT C1DBT C2DBT C3DBT PHN C1PHN C2PHN C3PHN C4PHN ANT FLA PYR C1FLA BAA CHR C1CHR C2CHR C3CHR C4CHR BbF BkF BEP BAP PER IDP DBA BZP No weathering

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40 Conclusion (Part I) Methods are important! Weathering can be controlled by: Energy Time Volume Dispersants Other system/environmental attributes

41 Part II: PAH composition influences toxicity 2 examples

42 More weathered Less weathered PAH influences toxicity t = t = 33 d Percent of f total PAH NPH C1NPH C2NPH C3NPH C4NPH BPH ACY ACE FLU C1FLU C2FLU C3FLU DBT C1DBT C2DBT C3DBT PHN C1PHN C2PHN C3PHN C4PHN ANT FLA PYR C1FLA BAA CHR C1CHR C2CHR C3CHR C4CHR BbF BkF BEP BAP PER IDP DBA BZP Carls et al Pacific herring Oil only

43 PAH influences toxicity % Total dea ad + moribun nd1 Control light Larvae, oil-only Larvae, oil+dispersant 1 1 1, 1, tpah conc. in tissue (ng/g) (Barron et al. 23)

44 1 Sun PAH influences toxicity % % 9.5% 16.1% Larval oil-only exposure: 87 ug/l tpah 1.5%.1% Larval oil+dispersant exposure: 44 ug/l tpah 36.% 4.3% 19.% 35.3% % Total dead + moribund NPH C1NPH C2NPH C3NPH C4NPH BPH ACY YE ACE FLU C1FLU C2FLU C3FLU DBT TT C1DBT C2DBT C3DBT PHN C1PHN C2PHN C3PHN C4PHN ANT TA FLA PYR C1FLA AA BAA CHR C1CHR C2CHR C3CHR C4CHR BbF FF BkF BEP BAP PER IDP PA DBA BZP Percent of total tpah Percent of total tpah nd1 Control light Larvae, oil-only Larvae, oil+dispersant 1.4%.2% Dispersant (alone) was not toxic % Total dead + moribun moribund + dead 1 1 1, 1, tpah conc. in tissue (ng/g) d 8 d Percent Dispersant concentration (ul/l)

45 Part III: Match assay methods to toxicant Short assays for rapid toxins Long assays for slow toxins & longer observation times

46 Short assays for rapid toxins (or high conc.) tics t of total aromat W S F 2. Percent 1 M o n o - D i-a ro m a tic EC5 or LC C5 (ppm) Time (days) Feeding rate (herring larvae) (Carls 1987)

47 Short assays for rapid toxins (or high conc.) tics t of total aromat W S F 2. Percent 1 M o n o - D i-a ro m a tic EC5 or LC C5 (ppm) Time (days) Swimming inhibition

48 Short assays for rapid toxins (or high conc.) tics t of total aromat W S F 2. Percent 1 M o n o - D i-a ro m a tic EC5 or LC C5 (ppm) Time (days) Death

49 Long-term consequences: Pink salmon: Marine survival decreased with dose LOEC = 5.2 µg/l aq. TPAH

50 Conclusions: 1. Methods determine PAH composition 2. PAH composition influences toxicity 3. Match assay methods to toxicant

51 Thank you!