➢Pollutants distributed across and within the
multiphase systems air, seawater, soil, biota
➢Bioaccumulative substances do cycle in
ecosystems even decades after emission bans
➢Tendency to accumulate in polar regions;
cycling is enhanced by the grasshopper effect
➢Many combustion byproducts are carcinogens
(or precursors thereof), many environmental
chemicals are endocrine disruptors.
(UNEP, 2003)
Large-scale cycling of bioaccumulative and/or health hazardous
substances → Exposure of the environment and humans
Motivation
Towards
• understanding pollutant distributions in abiotic environment on large
spatiotemporal scales
• characterisation of exposure of ecosystems and humans
Motivation:
• Understand the fate of persistent semivolatile substances
"Chemodynamika znečištění životního prostředí / Chemodynamics of environmental pollution" research group
Burden of
anthropogenic substance
(synthetic chemical)
Large-scale cycling, bioaccumulative, health hazardous substances
→ Exposure of the environment and humans
"Chemodynamika znečištění životního prostředí / Chemodynamics of environmental pollution - Air" research group
prof. Gerhard Lammel, Ludovic Mayer MSc, Dr. John K. Mwangi, Dr. Karla Pozo G. (office = D29-423)
Elements of research work
• Translate question or hypothesis into experimental design
• Sample air gas-phase, particulate phase on adsorbents and filter membranes; soil, water using polymeric sorption materials;
generate field blanks
• Extract the sampling medium, clean-up of the extract, chromatographic analysis
• Derive concentrations in air, soil, water, concentration gradients, ratios, time series, mass fluxes; discuss uncertainties
• Get supporting data from meteorological/oceanographic services and cooperating groups on site
• Predict concentrations gradients, ratios, time series, mass fluxes based on theory or hypothesis (‘modelling’), and compare with
measured (statistical tools), eventually limit values; draw conclusions
Studies
• Field campaigns in Czech Rep. 2016, ‘17, ‘18, ‘19, ‘21, ‘22, Greece and Turkey 2012, Hungary 2013, India 2014, Chile 2014, ‘21, ‘22, Svalbard
2022, open ocean 2010, ‘16, ‘17, ‘19, ’22, ‘23
• 20 studies published as articles in scientific journals 2011-20 with journal impact factor 3-6, cited by average 30 times/paper
• Contributed to 12 studies lead by others and published 2011-20, cited by average 20 times/paper
Cooperations - internal:
• doc. Branislav Vrana: water sampling techniques for ocean surface waters
• doc. Klára Hilscherová: bioassays to determine toxicity of atmospheric aerosols and gaseous samples
• prof. Jakub Hofman: sampling and characterization of soil samples
- external:
• Max Planck Institute for Chemistry (Mainz/DE): bioaccessibility, analysis
• Czech Acad. Sci.- Inst. Chemical Process Fundamentals, Praha, Natl. Observatory Košetice: sampling, supporting data
• Hellenic Centre for Marine Research; University Centre of Svalbard; USS Concepción/Chile; …
Motivation:
• Understand chemodynamics of persistent semivolatile substances (which are bioaccumulative
and toxic)
• which are re-volatilising from ground compartments (multi-hopping)
• → study the processes and understand large scale spatiotemporal trend
Air-sea N Sea 2009 episode Mai et al. ESPR 2016
E Mediterranean 2010 seasonal Mulder et al ACP 2014
E Mediterranean 2012 episode Lammel et al ESPR 2015, ACP 2016
ConcepciónBay Chile 2014 seasonal Pozo et al MPB 2022
S Atlantic 2016 episode Sobotka et al MPB 2021
Mediterranean, Red Sea,
Arabian Sea, Persian Gulf 2017 episode Wietzoreck et al ACP 2022
Eq Atlantic 2019, 2023 episodes unpublished
Air-soil W Balkans 2008 episode Lammel et al. J Env Mon 2011
Pannonian Plain 2013 episode Degrendele et al. EST 2016
India 2014 seasonal Lammel et al. ACP 2018
Finokalia observatory
Water sampling, 3 sites (3-31 July 2012)
1 = ca. 8 m each from 2 cliffs (no anker), d =
2.5 m
2 = ca. 30 m from cliffs, 50 m from pebble
beach, d = 4 m
3 = ca. 50 m from cliffs, d = 4 m
• Passive (silicon rubber strips) + TOC (grab
water sample); PSM-associated = total –
dissolved
Active air sampling (2-13 July 2012)
Selles (0.5 m a.s.l.)
•12hly vertical gradient low-vol sampling
gaseous fraction (PUF) +PM10 particulate
fraction (QFF)
•Passive (PUF disk)
•Supporting data: meteorology,
micrometeorology
Selles Beach
Crete coast (night and day sampling):
Gaseous halogenated semivolatile compounds‘ vertical gradients
cz1 =1.05m
Δcz = cz1 - cz2
0.0
0.5
1
c(ng/m³)
subsequent day and night samples 2.-13.7.12
PCB 101
PCB 52
PCB 28
γ-HCH
α-HCH
HCB
PeCB
• downward in 18 cases ranging Fc =
-0.56±0.80 µg m-2 d-1)
• upward in 7 cases, ranging Fc =
0.26±0.30 µg m-2 d-1; these were
0.11-0.26 for -HCH, 0.04 for both
PCB28 and DDE and 0.91 µg m-2 d-
1 for BDE47
• insignificant in 29 cases (│Fc│ ≲
0.15±0.39 µg m-2 d-1) (
Night-time maxima
2-box model for SOC cycling b [µg m-2], part. mass fractions 
dba/dt = Fem/ha + Fvolbw/ha – a bavdep/ha + kvolcw – (1-a) kOHcOHca
dbw/dt = w vexpbw/hw – (1- w) Fvolbw/hw + a bavdep/hw – kocbw
Aegean, 5 days of homogeneous advection
Observed and model predicted concentrations in air and diffusive
air-sea exchange mass flux of PAHs (pg m-2 d-1; downward
upward)
dMBL (m)
dMBL=variable
→ Volatilisation from the sea surface has significantly
contributed to the night-time maxima of (at least) HCB, HCH,
PCB28, PCB52 and PYR. in combination with variation of dMBL
↓ : FLT, PYR, PCB52, PBDEs
↕: PYR, PCB52
↑: HCB, PCB28
Canopy and soil at 3 soil sampling plots. Soil type: nitisol (GOI, 1985; FAO,
2014)
Tea garden Shrub Forest
TOC = 4.4% 10.7% 4.0 %
0
50
100
150
200
250
300
tea shrub forest
ng/g
PBDE (7/10)
DDT (6/6)
HCH (3/5)
PeCB+HCB*100
PCB (7/7)*100
PAH (16/25)
o,p'-DDE 1.84
p,p'-DDE 12.13
o,p'-DDD 0.49
p,p'-DDD 0.17
o,p'-DDT 11.34
p,p'DDT 1.90
opDDT/ppDDT:
≈ 1 most IND Chakraborty’15
Chakraborty‘10
>>1 some MEX Wong‘10
3/5 RO Ene‘12
Arrival of extremely clean air with the southwest
monsoon in southern India early June
2014:
Air-soil exchange in India before and during the onset of the southwest monsoon 2014
Change of air-soil fugacity ratio (2-film model; Harner et al., 2001),
fs/fa=cs H(T) ⁄ (0.411 OM KOW)/[ca Rg T], with the onset of monsoon
in tea plantation:
in forest:
0.1
1.0
10.0
100.0
1000.0
f_s/f_a
all
pre-monoon episode
monsoon episode
0.0
0.1
1.0
10.0
100.0
f_s/f_a
…and upon onset of SW monsoon:
↑ upward: PCB28 (forest), -HCH (tea, forest) and -HCH (all)
↓ predominantly downward: (g) PHE, FLT, PYR, - and -HCH, BDE47 and -99
Mass flux
from soil to air
from air to soil
Air-soil exchange India before and during onset of SW monsoon 2014
volatilisation triggered by the drop of air pollution levels ? → Modelling the chemodynamics
Response of the air-soil chemical sub-system to meteorological and chemical changes in
advection: regional simulation of the episode (WRF/Chem with soil compartment)
γ-HCH (pg m-3) p,p’-DDE (pg m-3)
cpre monsoon in air (ground level, mean of 1-3 June)
Δcobs/cobs
S India (%)
Δcpred/cpred
S / C / N India (%)
PHE -91 -89/-92/-100
CHR -83 -91/-96/-100
α-HCH -85 -78/-45/-39
γ-HCH -89 -83/-54/-53
p,p’-DDE -91 -86/-61/-67
hBL n.d. +0.2/-25/+70
→ In S India the change of pollutant
level reflects the drop in the advected,
clean air, while with propagation
northward the signal decreases for the
pesticides
Pollution drop: cpre monsoon - cmonsoon (means of 1-3 and 8-10
June, respectively)
Open ocean measurements
known history of air masses
2019
Jan + Aug
2015
2017
2019 Jan
2016
2019 Aug
2019
Emission and transport
Predictions
ECMWF-CAMS 2019
air air
soil water
Open ocean measurements
known history of air masses
and the trace substances transported
Pesticides cycling
14
Emissions
Gas
Particle
Degradation
·OH - ·NO3 - O3
Deposition
Dry Wet Volatilisation
Long-range atmospheric transport
Ludovic Mayer - Pesticides Behaviour in Soils, Water and Air 2022 - York
15
Results - Long-Range Atmospheric Transport
N
Equator
Latitude
Planetary boundary
layer (PBL)
Free troposphere
TROPOSPHERE
(0–10km)
Ludovic Mayer - Pesticides Behaviour in Soils, Water and Air 2022 - York
Pesticide long-range transport
over Europe
project(Ludovic Mayer)
̶ Air sampling campaign
̶ Active air samplers
̶ Spring 2020
̶ Simultaneously
̶ 29 sampling sites in 17 countries
̶ 25 partner institutions
1
6
Ludovic Mayer - Pesticides Behaviour in Soils, Water and Air 2022 - York
14 CUPs
11 in common with
polar sites
Found in PESPAT polar sites
17
Results – Long–Range Atmospheric Transport
Mountain sites
̶ 5 out of 10 samples in Free Troposphere
̶ From 3 sites (HAC, SBO & UFS)
CUPs found in Mountain free tropospheric sites
Atrazine Metazachlor
Boscalid Prochloraz
Chlorpyrifos S-metolachlor
Cyprodinil Spiroxamine
Fenpropidin Tebuconazole
Fenpropimorph Terbuthylazine
Iprovalicarb Thiacloprid
Ludovic Mayer - Pesticides Behaviour in Soils, Water and Air 2022 - York
Scientists (since 2012):
• John K. Mwangi (since 2020)
• Karla Pozo G. (since 2012)
• Céline Degrendele (2016-21; now U Aix-Marseille)
• Marie D. Mulder (2012-18, now Austrian Hydromet., Wien)
• Jana Matejovičová (part time, 2012-16, Slovak Hydromet., Bratislava)
• Christos Efstathiou (2011-15, now U North Carolina, Chapel Hill/US)
Doctoral students (since 2010):
• Ludovic Mayer: Fate of currently-used pesticides in the atmospheric environment (PhD ongoing)
• Barbora Nežiková: Investigation of semivolatile pollutants' partitioning in and wet scavenging from aerosols (PhD 2022)
• Marie D. Mulder: Semi-volatile organic pollutants in the Mediterranean: Long-range atmospheric transport, (photo)chemistry and air-sea
exchange (PhD 2019)
• Lenka Škrdliková: Scavenging by rain and aerosol size distributions of persistent organic pollutants in near-ground air (PhD 2014)
MSc, BSc, internships (since 2010):
• Baptiste Delaunay: Uptake of PAHs into plants (Erasmus internship, 2022)
• Hippolyte Leuridan: Spatial and temporal variation in air quality at Brno (Erasmus internship, 2020)
• Nils Paragot: Multi-year atmospheric concentrations of per- and polyfluoroalkyl substances (PFASs) at a background site (Erasmus
internship, 2019)
• Dušan Lago: model (data processing, scripting) (student assistant 2013-15)
• Michal Jaroš: model (thermodynamics) (student assistant 2010-11)
• Kateřina Benčaťová: PAHs in oxidant-rich air - sampling methodology and atmospheric chemistry (BSc. 2010)
"Chemodynamika znečištění životního prostředí / Chemodynamics of environmental pollution - Air" research group
Open
BSc (defense June 2023):
• Pesticides in air – sampling of particles and gas-phase (supervisor Gerhard Lammel/Ludovic Mayer)
• Evaluation of a novel passive air sampler and determination of organic pollutants
gerhard.lammel@recetox.muni.cz