A multi-compartment modeling system for estimating emissions and transport of persistent organic pollutants

The case of benzo(a)pyrene

Presented at the 13 th Annual CMAS conference 11/27/14 • Chapel Hill, NC by Christos Efstathiou, Jana Matejovicova, Martin Tomas, Tom Rebok, Gerhard Lammel Research Center for Toxic Compounds in the Environment Centrum pro výzkum toxických látek v prostředí Kamenice 753/5, pavilon A29, 625 00 Brno, Czech Republic

• • • • •

Introduction Setting up the models Adaptations to treat POPs Model results Summary and future aims

Outline 13 th Annual CMAS conference, Chapel Hill, North Carolina RECETOX Modeling Group - 2

Rationale: POPs & Environment

• POPs have been an active topic of environmental chemistry and toxicology since the 1960s • Several POPs including PCBs and agrochemicals banned – still observed!

• Different intrinsic physical-chemical properties dictate environmental fate

Single-hoppers, Multi-hoppers, swimmers, flyers - Persistent in various environmental compartments (e.g. soil, vegetation) – LRT a concern

• Significant adverse effects at low doses • Highly bioaccumulative Object of the Stockholm Convention and the Aarhus Protocol (UNECE, 98) BaP target values for air concentrations – national policymaking EU: 1 ng/m 3 (annual average) - UK: 0.25 ng/m 3 Benzo(a)pyrene has received attention as a representative toxic substance for PAHs with substantial experimental and modeling efforts

13 th Annual CMAS conference, Chapel Hill, North Carolina RECETOX Modeling Group - 3

Research Objectives

Enhance CMAQ to account for emission and transport of POPs between environmental compartments Which POPs ? •BaP (PAH) •PCBs (representative congeners) •DDT (insecticide) Study specifics •Seasonal and inter-annual variation of the concentration and depositions •Implement and evaluate relevant Gas – Particle Partitioning (GPP) and heterogeneous chemistry schemes •Include soil-atmosphere exchange scheme – additional soil compartment

13 th Annual CMAS conference, Chapel Hill, North Carolina RECETOX Modeling Group - 4

Research Objectives 13 th Annual CMAS conference, Chapel Hill, North Carolina RECETOX Modeling Group - 5

Model Setup physical schemes and parameterisations Weather Research Forecast (WRF) Model version 3.2.1

• GFS inputs (spatial resolution 0.5

° x 0.5

° ) • Long wave radiation scheme `RRTM` • Short wave radiation scheme `Dudhia` • Near-surface `Monin-Obukhov` scheme • `WSM` 3-class simple ice scheme • Land-surface scheme `Noah` with 4 soil layers

Community Multiscale Air Quality (CMAQ) Model version 4.7.1

• Carbon Bond 5 (CB-5) chemistry scheme incl. aqueous chemistry • 4th Generation aerosol module (AERO4) • Emissions from SMOKE-EU model (Biogenic + Anthropogenic + BaP) Bieser, J., Aulinger, A., Matthias, V., Quante, M., & Builtjes, P. (2011). SMOKE for Europe – adaptation, modification and evaluation of a comprehensive emission model for Europe. Geosci Model Dev , 4 (1), 47–68. doi:10.5194/gmd-4-47-2011

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B(a)P Emissions – major sources

PAHs are formed by any incomplete combustion of organic matter

• • • • • • • • Incineration of household and medical waste Iron and steel production Electricity generation Residential heating Road transport Ship engines Oil platforms Wildfires Emission Inventories for legacy POPs and agro chemicals are limited (Breivik et al., 2002)

13 th Annual CMAS conference, Chapel Hill, North Carolina RECETOX Modeling Group - 7

CMAQ modifications for POPs

Emissions mapping to different aerosol modes (99% into accumulation) IC & BC were obtained from global model (Stemmler & Lammel, ‘12) Gas-phase chemistry •Reaction with ozone for BaP •Reaction with OH for PCBs General considerations and implicit assumptions for GPP schemes: •Instantaneous relaxation to phase equilibrium •Compound does not irreversibly reacting in particulate phase •Sorption processes do not interact

13 th Annual CMAS conference, Chapel Hill, North Carolina RECETOX Modeling Group - 8

Gas-Particle Partitioning schemes

• J-P adsorption model (Junge ‘77 – Pankow ‘87) • Dissolution to aerosol water (Aulinger et al., ‘07, Cooter & Hutzell ‘02) • Absorption to organic matter (OM – Harner & Bidleman ’98) • Absorption to elemental carbon (EC – Dachs & Eisenreich ‘00) Developed CMAQ Fortran modules • Set the partitioning scheme(s) configuration • Calculate the physico-chemical parameters of POPs • Solve the system of equations for the selected GPP(s) Heterogeneous chemistry • Reaction with O 3 (Langmuir-Hinshelwood mech., Kwamena et al., ‘04)

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Soil-atmosphere exchange module

Soil-Atmosphere exchange module according to Jury

F vol

= 0

C soil e

m

t D E

p

t

æ 1 -

L

2

e

4

Dgt

æ æ Linked to : •Initial soil burden from global model output (Stemmler & Lammel, ‘12) •WRF output (driver variables soil Temperature, moisture) •European Soil Database (key soil parameters, including OC fraction) + Harmonized World Soil Database (gap filling) •Depositions from CMAQ output

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Annual means and spatial distribution of the effect of GPP schemes

J-P annual mean J-P / J-P_W (=+ Water dissol.) J-P_W / J-P_W_K OA

13 th Annual CMAS conference, Chapel Hill, North Carolina

J-P_W_K OA / J-P_W_K OA _EC (= + Dual Model K OA +EC)

RECETOX Modeling Group - 11

Comparison against measurements: GENASIS database 13 th Annual CMAS conference, Chapel Hill, North Carolina RECETOX Modeling Group - 12

Comparison against Active and passive samples: Kosetice 13 th Annual CMAS conference, Chapel Hill, North Carolina RECETOX Modeling Group - 13

Comparison against GENASIS database

1119 observation – modeled pairs Median Mean Std. dev R 2

Measurement J-P only

0.022130

0.004420

0.085950

0.343190

0.005175

0.003519

0.980519

JP_W

0.004398

0.005513

0.004130

0.979035

JP_W_KOA

0.007350

0.009197

0.006825

0.928591

JP_W_DL

0.007527

0.009389

0.006935

0.925308

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Size distribution

Brno, 2006 Kosetice, 2006

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CMAQ model output – wet deposition

Wet deposition Jan 17-18 g/ha/h Concentrations of BaP Jan 17 -18 0,45 0,4 0,35 0,3 0,25 0,2 0,15 0,1 0,05 0 17 .1

0 :0 17 0 .1

2 :0 17 0 .1

4 :0 17 0 .1

6 :0 17 0 .1

8 :0 17 0 .1

1 0: 17 00 .1

1 2: 17 00 .1

1 4: 17 00 .1

1 6: 17 00 .1

1 8: 17 00 .1

2 0: 17 00 .1

2 2: 00 18 .1

0 :0 18 0 .1

2 :0 18 0 .1

4 :0 18 0 .1

6 :0 18 0 .1

8 :0 18 0 .1

1 0: 18 00 .1

1 2: 18 00 .1

1 4: 00 18 .1

1 6: 18 00 .1

1 8: 18 00 .1

2 0: 18 00 .1

2 2: 00 Aspvreten Kosetice Rucava Zoseni

13 th Annual CMAS conference, Chapel Hill, North Carolina RECETOX Modeling Group - 16

Summary

• Simulations showed good correlations to measurements, improving with more complex GPP schemes • Simulations underestimate measurements – further analysis needed to evaluate usefulness of PUF samplers • Emissions seem to be missing a background winter component – possibly domestic heating? • Evaluate the new compartment with more volatile POPs (PCBs) – include soil degradation, effects of vegetation • Develop data assimilation methods to incorporate information of initial soil burdens • Evaluate different heterogeneous reactions (Perraudin et al., ‘07) • Evaluate the effect of different meteorological inputs and land surface models (LSM) on the soil-atmosphere exchange module

13 th Annual CMAS conference, Chapel Hill, North Carolina RECETOX Modeling Group - 17

Thank you!

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