1. Perturbaciones antropogénicas de la quimiosfera orgánica: Implicaciones a escala global.
Jordi Dachs
Departamento de Química Ambiental,
Instituto de Investigaciones Químicas y Ambientales de Barcelona
Consejo Superior de Investigaciones Científicas (CSIC)

2. Objetivos Perturbaciones antropogénicas de la quimiosfera
¿Es posible cuantificar y caracterizar las perturbaciones químicas por compuestos sintéticos?
Transporte y sumideros de contaminantes orgánicos a escala global.
Evaluación de riesgo de las familias de compuestos químicos antropogénicos.
Cambio climático y la quimiosfera tóxica

3. Anthropogenic perturbations of the chemosphere
Emissions from fossil fuels (CO2, CO, NO, hydrocarbons….).
Emissions from combustion processes (Dioxins and Furans, PAHs, …)
Sinthetic chemicals used in industry and consumer products.
Emission of anthropogenic aerosols.
Changes in atmospheric chemistry and composition produced by all the above perturbations.

4. Emissions from Gasoline Combustion
Schauer et al. Environ. Sci. Technol. 40, , 2002.

5. H’=CGas / CWater FAbs=k CGas / H’
Semivolatile Compounds Dominate Air to Water Fluxes of OC
H’=CGas / CWater
Gas absorption
Emissions
FAbs=k CGas / H’
(Schauer et al. ES&T 2002)
More than 95% of anthropogenic emissions of OC are as gas phase compounds

6. Emissions from Gasoline Combustion
Shauer et al. Environ. Sci. Technol. 40, , 2002.

7. Semi-Volatile Aliphatic Hydrocarbons in Petroleum (Quantified by GC-MS)
UCM
Cn = CnH2n+2
CPI = Odd Cn/Even Cn = 1
The UCM has a toxic effect in marine organisms (Rowland et al. ES&T 2001, Donkin et al. 2003…)

8. Aliphatic Hydrocarbons in the NE Atlantic atmosphere
Gas Phase nmol m-3
CPI =1.2
UCM
Aerosol Phase nmol m-3
(6% of total AOC)
CPI =1.9
UCM

10. The anthropogenic chemosphere
(from non-combustion sources)
There are more than 8 millions substances available…
There are over substances registered and in use, most of them in low volume production (less than 1 ton/year).
The world production of synthetic chemicals is of tons y-1 (1993).

11. The anthropogenic chemosphere
(except from combustion sources)
New chemicals are produced every year

12. The anthropogenic chemosphere
(not including combustion sources)
About chemicals are commercially available and have a production higher than 1 ton/year.
10000 chemicals have a production higher than 4.5 tons y-1.
4000 chemicals have a production higher than 1000 tons y-1.
Muir & Howard. Environ. Sci. Technol. 40, , 2006.

13. The anthropogenic chemosphere, last 30 years
(not including combustion sources)
Muir & Howard. Environ. Sci. Technol. 40, , 2006.

14. Risk criteria to identify priority chemicals (PBT chemicals)
Production volume
Use profile
Physical-chemical characteristics:
Persistent
Bioaccumulative
Toxicity
Potential for long range transport.

15. ¿Qué contaminantes orgánicos estudiar?
(Hermens, J.L.M. En Toxicology, Niesink R.J.M. (Editor) CRC Press, New York, 1996)
log KOW

16. Persistent Organic Pollutants (POPs)
Polychlorinated Dibenzo Dioxins and Furans (PCDD/Fs)
Polychlorinated Biphenyls (PCBs)
Cln
Clm O
Cln
Clm
Cln
Clm O
Used in capacitors and transformers. Other uses in paints, plasticizers, etc.
- Carcinogens. Neurological, reproductive and immune effects.
By-product of combustion (plastics..)
Carcinogens.

17. Other POPs …. Nonylphenols Polycyclic Aromatics Hydrocarbons (PAH)
Degradation product of alkylphenol polyethoxylates (industrial surfactants).
Endocrine disrupter.
Polycyclic Aromatics Hydrocarbons (PAH)
Produced during the incomplete combustion of organic matter (fossil fuels, vegetation ….).
Some are carcinogens.

18. Global Distribution of POPs in the atmosphere
PCBs
PBDEs
Pozo et al. Environ. Sci. Technol

19. Gas-Particle Partitioning Atmospheric Transport
Environmental fate of organic pollutants CG CW CP CA
Air-Water
Exchange
Water-Particle Partitioning
Gas-Particle Partitioning
Dry Deposition
Wet Deposition
Vertical Fluxes
Advection
Bioaccumulation
Continental Inputs
Atmospheric Transport
Degradation
Major Permanent sinks:
- Ocean interior (sediments, deep waters)
- Atmospheric OH degradation

20. Persistent Organic Pollutants (POPs)
Multimedia Partitioning of POPs
air
water
octanol H=

21. Western Mediterranean Sea
Off-shore Banyuls sur Mer
Off-shore Barcelona
SW Mediterranean
Sampling Locations
Western Mediterranean Sea

22. Air-Water Exchange and Dry Aerosol Deposition of Nonylphenols to the Western Mediterranean Sea

23. Atmospheric Occurrence of Nonylphenols Driven by Air-Water Exchange
1/Temp (K -1 )
0.0033
0.0034
0.0035
0.0036 1 2
Sandy Hook - E
NPs
Jun
Jul
Aug
Sep
Oct
Nov
Dec
Jan 10 20 30 40
Gas Phase
Aerosol Phase
Concentration (ng m-3)
Log CG ( ng m-3)
( Dachs, J., D.A. Van Ry, S.J. Eisenreich. Environ. Sci. Technol., 1999 and )

24. Atmospheric occurrence of Persistent Organic Pollutants (POPs)
PCBs
Nonylphenols
Log Cg = -9135/T
R2 = 0.88

25. Global distillation of semivolatile organic compounds
(Wania, F. and Mackay, D. , Environ. Sci. Technol. 30, 390A-396A, 1996)

26. Selective Sequestration of Atmospheric POPs in Sediments from High Mountain Lakes
Inventories in sediments vs. Temperature
(Grimalt et al. Environ. Sci. Technol. 2001)

27. (Lake Redo, Pyrenees Mountains)
Controls on the Sequestration of atmospheric POPs in Sediments from High Mountain Lakes
(Lake Redo, Pyrenees Mountains)
k’W-Sed/k’W-Air = 0.5
k’W-Sed/k’W-Air = 2.5
Fluxes in mg y-1
(Meijer, S. et al. J. Geophys. Res.. On revision 2007)

28. Evidence for Gas-Phase Driven Phytoplankton accumulation of PCBs
NW Atlantic Ocean
Correlated:
R2 = 0.90
un-correlated
R2 = 0.96
R2 = 0.70
(Yan, et al. Environ. Pollut. 2007)

29. To which extend atmospheric inputs control water concentrations of POPs?

30. Influence of turbulence on water column concentrations and variability (Example: Adriatic Sea)
PCB 28
(Jurado et al. 2007, Mar. Pollut. Bull 54, )

31. Acumulación de contaminantes orgánicos
en la vegetación
PCBs
PCDDs
PCDFs
(Böhme et al. Environ. Sci. Technol. 33, , 1999)

32. La vegetación como filtro de contaminantes
(Mclachlan M.S. y M. Horstmann, Environ. Sci. Technol. 32, , 1998)
Flujo de deposición en la vegetación
Flujo de deposición en el suelo
________________________________ F=

33. Global distribution of PCBs in Soils
Meijer et al. Environ. Sci. Technol

34. Potential Environmental Reservoirs of POPs
Inventory in soil or ocean mixed layer / Inventory in atm boundary layer
PCB 101
Soil Conc (pg g-1)
PCB usage (tn)
(Dalla valle, M., Dachs, J., Sweetman, A.J., Jones, K.C. Global Biogeochem. Cycles 2004.
Dalla valle, M., Jurado, E., Dachs, J., Sweetman, A.J., Jones, K.C. Environ. Pollut )

35. Potential Drivers of Oceanic Sink of POPs

36. Cl5DD atmospheric concentration
>> cruise data
GAS: Cg
[fg m-3]
AEROSOL: Cp
(Lohmann et al. EST 2001, Jaward et al. EST 2004)
Cl5DD atmospheric concentration
RRS Bransfield Oct-Dec 1998,
Rainer Lohmann PCDD/Fs
RV PELAGIA Jan-Feb 2001
Foday Jaward PCBs

37. Climatological and Remote Sensing Data
Mixed Layer Depth
Chlorophyll
90N
60N
30N
30S
60S
90S
90N
60N
30N
30S
60S
90S
180W W E E
180W W E E
MLD (m)
Chlorophyll ( mg m-3)
Water-Phytoplankton Fluxes

38. Comparison of Measured and Predicted PCB Sinking Fluxes
North Atlantic Ocean
Mediterranean Sea
(Gustafsson et al 1997)
(Dachs et al 1996)
PCB 180
Arabian Sea
(Dachs et al 1999)
(Dachs et al. Environ Sci. Technol, 2002)

39. Atmospheric Depositional Processes of POPs
AEROSOLS
contaminants associated with particles
WATER DROPLETS
gaseous contaminants
VOLATILIZATION
Air-water exchange dominates Wet and Dry deposition of POPs except in rainy regions and close to urban areas, and for chemicals that have a strong affinity to aerosols such as PAHs (Mackay 2001, Dachs et al. 1999, Eitzer and Hites 1989)
Controversy between dry and wet deposition fluxes of particles; it seems that they are comparable, with the former being more important for species associated with larger particles and where surface waters lie in close proximity to large anthropogenic sources (Zufall et al. 1994).
DRY DEPOSITION
OF PARTICLES
WASHOUT OF PARTICLES
WASHOUT OF GASES
ABSORPTION OF GASES

40. Comparison of Atmospheric Depositional Processes for PCBs and PCDD/Fs
(Atlantic Ocean)
(Jurado et al. Environ. Sci. Technol. 2005)

41. Comparison of Predictions and Measurements of Wet Deposition of POPs

42. Global Sinks for atmospheric PCDD/Fs
(Lohmann R., Jurado E. Dachs J., Lohmann U. Jones K.C 2006.
J. Geophys. Res. DOI /2005JD006923)

43. PCB Cycling Over the Open Atlantic Ocean
Occurrence of Gas Phase PCBs
(Jaward, F. et al. Evidence for dynamic air-water coupling and cycling of POPs over the Atlantic ocean Environ. Sci. Technol. 2004)

44. POP air-water coupling and cycling in the Open Atlantic Ocean
Diurnal Cycling of Gas Phase PCBs
Air-water exchange controls the diurnal cycle
Air-water mass transfer coefficient
Are Atmospheric Diurnal Cycles of PCBs Driven by the Marine Organic Carbon Cycle?

45. Persistent Organic Pollutants (POPs)

46. Sampling Cruise in the NE Atlantic (Off-shore Sahara, May-June 2003)

47. PAHs Along Two East-West Transects
(NE Atlantic)
Phenanthrene
Pyrene
(Del Vento & Dachs ES&T, 2007)

48. Atmospheric Residence times of PAHs
The observed atmospheric residence times are 3.5 and 3.7 days for gas and aerosol phase PAHs

49. Atmospheric residence time over the ocean
(atm. dep + reaction with OH radical)
Air-deep water mass transfer coefficient (kADW)
kADW = kAT kSink / (kAT + kSink)
kAT= kAW + k’DD+ k’WD
Then
FAtm-Ocean = kADW CG/H’
Atmospheric Residence Time of POPs
τ = inventory/net output = 1 / (rdeg + rADW)

50. Atmospheric Residence times
PCB 180 as example
Role of the Biological Pump and Temp.
(air-deep water mass transfer coef.)
Role of precipitation intensity
(Jurado 2006)

51. How pollutants reach the Arctic and Antarctica?
Wania & Mackay 1996

52. How pollutants reach the Arctic and Antarctica?
Atmospheric Concentrations of PCBs
(june-july 2005)
(Gioia et al. 2008)

53. How pollutants reach the Arctic and Antarctica?
Air-water gradient of PCB fugacity
(Gioia et al. 2008)

54. Is the Formation of Deep Oceanic Water a Sink of POPs

55. Formation of Deep Oceanic Water as a Sink of POPs
Lohmann R., Jurado E. Pilson M. , Dachs, J
Geophys. Res. Lett. DOI /2006GL

56. Clobal Change and POPs in the Arctic
(MacDonald et al. Sci. Total Environ. 2005)

57. Case Study: POPs in the Arctic
MacDonald and coworkers have published the first comprehensive study on the implications of climate change on POP cycling and impact. This will modify:
Atmospheric inputs of POPs/pesticides
Atmosphere-ocean gas exchange and delivery of ice-cover content of POPs
Riverine inputs
Chemical partitioning and degradation of POPs.
These changes are also linked to:
Altered food web structure
Food deprivation or shifts in diet
Altered migration pathways and invading species
The literature suggests that there is a dynamic link between organochlorine compounds and disease and epidemics in wildlife arctic populations.

58. The anthropogenic chemosphere, last 30 years
(except from combustion sources)
Muir & Howard. Environ. Sci. Technol. 40, , 2006.

59. Persistent Organic Pollutants

60. Production and occurrence of Legacy POPs
Lohmann, R., Breivik, K., Dachs, J., Muir, D , Environ. Pollut. In press.

61. Production and Occurrence of Emerging POPs

62. Potential POPs
Muir & Howard. Environ. Sci. Technol. 40, , 2006.

63. The anthropogenic chemosphere, last 30 years
(except from combustion sources)
Muir & Howard. Environ. Sci. Technol. 40, , 2006.

64. Bioaccumulative and Persistent
Potential POPs
Bioaccumulative and Persistent
Muir & Howard. Environ. Sci. Technol. 40, , 2006.

65. Potential POPs: Bioaccumulative and Persistent and with long-range transport potential
Muir & Howard. Environ. Sci. Technol. 40, , 2006.

66. POPs in the global environment
The potential for sintetic compounds to become global pollutants is a function of their physical chemical properties and toxicity.
Carbon cycle and temperature are important variables controlling global distribution of POPs
Atmospheric transport is important for legacy POPs while oceanic transport is important for many emerging POPs.
Only the environmental fate and impact of few pollutants is know. Difficult to get the key information from other chemicals.
The organic fraction of the chemosphere is largely uncharacterized.
Since the different vectors of global change (climatic, biodiversity, hydrologic cycle…) will modify the ecosystem functioning, the fate and impact fo POPs will also be modified under a global change scenario…