Persistent organic pollutants
- sample analysis
Jana Klánová
klanova@recetox.muni.cz
1. Environmental analytical chemistry
Specific features, general scheme
2. Sampling
Sampling plan, strategy, sampling protocol, sample size and quality, transport, storage
3. Sample preparation
Extraction of solid (Soxhlet, automatic extraction, MAE, ASE, SFE) and liquid (L-L, SPE,
SPME, head-space) samples, fractionation and clean-up (column chromatography,
gel permeation)
4. Analytical techniques
Chromatographic techniques, principals, instrumentation, HPLC, GC, GC-MS
5. Persistent organic pollutants
Priority pollutants (PCBs, PCDDs/Fs, PAHs, pesticides), emerging pollutants
(SCCPs/MCCPs, antibiotics, degradation products)
6. QA/QC
Calibration, limit of detection and quantification, internal and recovery standards, blanks,
certified reference materials, interlaboratory calibration tests, method validation and
verification, GLP
Environmental science brings together scientists from many fields to perform
complex studies of various environmental compartments, processes, and
interactions.
They may include:
- water and food quality monitoring
- level of contamination of environmental compartments
- ozone depletition as a result of the presence of certain chemicals in the atmosphere
- regional contamination studies
- evaluation of the impact of local sources of pollution
- toxicity of chemical compounds as a function of their chemical structure
- impact of chemical substances on living organisms
- bioavailability
- bioaccumulation
- biotic and abiotic transformations
- transport of pollutants in the environment
- global fate of pollutants
- international directives and their impact on the global contamination
- remediation actions and their quality control
- sustainable development
Most of them involve the chemical analysis as one of necessary steps.
Environmental analytical chemistry chalenges:
- international conventions focus attention on the new groups of pollutants
- old contamination brings the problem of residue analyses
- lowering limits as well as environmental levels require low detection limits
- large-scale monitoring is crutial for the studies of the long-range transport
- development of new sampling techniques is encouraged
- increasing number of samples stresses the need for automatization
- fate studies require understanding of distribution processes and equilibria
- photochemical reaction complicate the sampling and data interpretation
- consideration of both, analytical and toxicological data is important
for successful risk assessment
- methods of biochemistry and molecular-biology are often implemented in
toxicological studies
- international studies require standardization of all procedures
There are several steps necessary for
environmental contamination control:
- problem definition
- screening of the situation, data interpretation
- evaluation of the extent of the problem
- selection of the best procedure to monitor the situation
- evaluation of the present state and future development
- exposure evaluation and risk assessment
- suggestion of correcting measures or remediation activities
- new directives to control the situation
- monitoring designed to evaluate effectiveness of measures
Košetice
alfa-HCH
beta-HCH
gama-HCH
delta-HCH
Košetice
16.2.-15.3.2004
15.3.-13.4.2004
13.4.-11.5.2004
11.5.-8.6.2004
8.6.-7.7.2004
Specific problems of environmental analysis
- low homogenity of samples (soil)
- low stability of samples (biota)
- various matrices (methods for extraction of analytes from matrices)
- wide range of analytes (method development)
- wide range of concentration (robust methods)
- monitoring on the levels close to the detection limits (high deviations)
- risk of secondary contamination
- price of ultra-trace analysis (instrumentation, chemicals, standards)
General scheme of environmental analysis
- Sampling - homogenization
- conservation
- transport
- storage
- Sample preparation - extraction
- clean-up
- selective elution
- concentration
- derivatization
- Sample analysis
- Data interpretation
Sampling – documentation required
- sampling plan (a goal, selection of sampling sites, analytes, sampling method,
number of samples, sampling period and frequency, safety procedures),
seeks the balance between the value of data and its price
- standard operational procedure for sampling various matrices (sampling devices,
steps involved in collecting of representative sample -homogenous, of reasonable
size and stability, quality of transport and storage)
-sampling protocols (name and number of the sample, sampling site, matrix,
date of sampling, local conditions and measurements, methods, sample size,
responsible person)
GPS:
49°29’48’’
17°57’14’’
245 m
Local conditions:
Sampling site 1. DEZA
Polyurethane Foam Filter PUF
Air Pump
Sampling Techniques
High-Volume sampler
Particulate Phase
Gas Phase
Glass Fiber Filter GFF
Particles
Gas
Passive sampling
Can environmental concentrations of pollutants be calculated
from the analyte levels accumulated in an integrative
passive sampler?
- Calibration conditions should approximate field conditions
- Performance Reference Compounds
Calibration of a passive sampler in a flow-through system
Peristaltic pump
30 ml/min
Peristaltic pump
100 l/min Exposure tank
Water
waste
water
Stirrer
Chemicals
in MeOH
Water
reservoir
overheadstirrer
Samplers
Analytes
In MeOH
B. Vrana, R. Greenwood, G. Mills
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
AcenaphtheneFluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benz[a]anthraceneC
hrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Indeno[1,2,3-cd]pyrene
D
ibenz[a.h]anthracene
Benzo[g,h,i]perylene
70 rpm
40 rpm
no sampler stirring
Rs[L/d]
Sampling rates of PAHs
B. Vrana, R. Greenwood, G. Mills
PRCs are non-interfering compounds added to the sampler prior to exposure.
They are used for in situ calibration approach, where the rate
of PRC loss during an exposure is related to the target compound uptake.
This is accomplished by measuring PRC loss rates during calibration studies and
field exposures.
Performance reference compounds
0
0.2
0.4
0.6
0.8
1
1.2
0 50 100 150 200 250 300 350
no stirring
40 rpm
70 rpm
Time (h)
c(t)/c(0)
PRC = D10-Biphenyl
Temperature = 11°C
Use of performance reference compounds
B. Vrana, R. Greenwood, G. Mills
Preparation of the sample before extraction
Soil samples
- lyofilization or air-drying
- sieving (< 2mm) and homogenization
- appropriate storage (protected from sunlight, heat and humidity)
Sediment samples
- stone and water removal, lyofilization or air-drying
- grating and sieving (<63um), homogenization
- powder copper treatment for sulphur removal
Plant samples
- lyofilization or air-drying
- grating, homogenization
Animal samples
- lyofilization or
- homogenization of a wet sample with sodium sulphate
Extraction and clean-up
The goal: transfer of analytes to the chemical phase suitable for analysis,
removal of interferences and pre-concentration of the sample.
Extraction techniques:
- solvent extraction (Soxhlet, automatic Soxtec, MAE, ASE, SFE)
- liquid-liquid extraction
- solid phase extraction and microextraction (SPE, SPME)
- semipermeable membrane separation
- head space analysis
Clean-up techniques
- sulphuric acid treatment
- column liquid chromatography (silica gel, alumina, florisil)
- gel permeation chromatography
Solid sample extraction
Liquid sample extraction
Air samples
- filters from high volume samplers or passive samplers are extracted as solid samples
(Soxhlet, MAE, ASE, SFE)
Water samples
- direct analysis of the samples with high concentration of pollutants
- head space, SPE, L-L
Soil and sediment samples
- Soxhlet, MAE, ASE, SFE
- powder copper treatment for the sulphur removal in sediment samples
Biotic samples
- high molecular compounds removal by gel permeation chromatography and column
chromatography
Presence Availability Activity
Total mass Fraction of
total mass
Measure that
drives diffusion
and partitioning
How much
is there?
How much is
available for ... ?
How high is the
diffusive pressure
into other media?
Exhaustive
Extraction
Depletive
Extraction/
Sampling
Equilibrium
Sampling
Devices
P. Mayer, F. Reichenberg
Supercritical Fluid Extraction (SFE)
High pressure CO2 (100 to 400 bar, 40 to 150 oC) is pumped through a sample,
and extracted analytes are collected in a suitable solvent for GC analysis.
Why to use supercritical carbon dioxide?
- CO2 is a lipophilic solvent much like biological lipids in polarity
- PAH solubilities in CO2 are proportional to those in water, but ca. 104 higher
- pressure and temperature gradients enable the extraction of both, non-polar and
polar compounds
- mild SFE can be used to predict bioavailability of compounds
Earthworm Mortality Depends on Available PAHs
(measured by SFE), not on Total PAH Concentrations
Soil Total PAH Available Available Total Mortality
(ug/g soil) Fraction (SFE) PAH (ug/g C) %
Mortality
CG15 1020 0.25 1040 0
OG14 168 0.46 2720 0
CG11 15600 0.06 3280 0
CG12 3790 0.16 7880 0
OG17 17200 0.27 9720 0
OG5 1870 0.41 11100 0
OG10 42100 0.33 16300 0
CG3 4100 0.83 45700 100
OG18 17300 0.74 50100 100
S. B. Hawthorne, C. B. Grabanski, D. J. Miller
Sam
pling
train
Rinsing of
sampling
device
Extraction
Concentration
Silica
Silica
+
H2SO4
Silica
Silica
+
NaOH
Silica
Silica
+
AgNO3
Sampling
standards
Extraction
standards
Basic
Alumina
Super I
column
Active
carbon
column
Concentration
GC/MS
Syringe
standards
Flow chart of a clean-up procedure for stack emission samples
A. Kočan, Slovak Medical University
Priority pollutants
- polychlorinated biphenyls
- polychlorinated dibenzo-p-dioxins and furans
- organochlorinated pesticides and their metabolites
- polyaromatic hydrocarbons
- aromatics and nitro-aromatics
- chlorinated benzenes
- fenol and chlorinated fenols
- halogenated alkans
Polychlorinated biphenyls
ClyClx
- sulphuric acid treatment
- silica gel column chromatography
- activated carbon for non-ortho PCBs
- GC-ECD, GC-MS, GC- HRMS
Organochlorinated pesticides
HCH
p,p’-DDT p,p’-DDD p,p’-DDE
(DDT, HCH, hexachlorobenzene, toxaphene, aldrin, dieldrin, endrin, endosulfane, chlordane)
- analytical procedures similar to PCBs for toxaphene,
- sulphuric acid has to be omitted for aldrin or endosulfane
- GC-MS, NCI-MS, HRMS
- for HCHs and DDTs analytical procedures similar
to PCBs
- GC-ECD, GC-MS, NCI-MS, HRMS
Polychlorinated dibenzodioxins and dibenzofurans
- combined modified silica gel clean-up
- fractionation on alumina/florisil column
- non-ortho PCBs separation on activated carbon column
- HRGC-HRMS
- kapilary columns 50-60m (DB-5, DB-17, DB-DIOXIN)
- EI, NCI
- SIM
- MS-MS
Polyaromatic hydrocarbons
- silica gel column chromatography
- GC-MS, FLD-HPLC
Sample analysis
Chromatographic separation (GC, HPLC) is the most common technique for
the analysis of environmental samples.
It is a physical method based on the distribution of compounds between two
phases (stationary and mobile). Process of continuous sorption and desorption
of compounds in contact with the stationary phase is responsible for different
migration times and for separation of analytes.
Two dimensional (GC-GC) and two modal (HPLC-GC) chromatography provide
even more sofisticated tools for environmental analysis
GC-MS, HPLC-MS and HRMS enable the trace and ultra-trace analysis
GC separation:
 Non-polar stationary phase (e.g. DB-5) – used for the
samples of animal origin and higher chlorinated congeners
 Polar phase (e.g. SP-2330) – used for environmental samples
(good separation but shorter lifetime)
 Splitless, on-column or
large-volume injection
 Direct connection of
the column to the ion
source
out of
splitless
injector
to mass
spectrometer
A. Kočan, Slovak Medical University
Chromatogram
Ion
Source
Mass
Analyzer
Ion
Detector
Vacuum
Pumps
Inlet
Sample
Introduction
Data
System
Data
Output
Mass Spectrometer
• All the MS systems compose of the following parts:
Ionization, separation of ions
and their detection
take place in vacuum
(~ 10-4 – 10-6 Pa)
•Electron multiplier
•Photomultiplier
•Microchannel plate
•Magnetic-sector
•Quadrupole
•Ion trap
•Time-of-flight
•Ion-cyclotron resonance
•Electron impact (EI)
•Chemical ionization (CI)
•Electrospray (ESI)
•Fast-atom bombardment (FAB)
•Laser ionization (LIMS)
•Resonance ionization (RIMS)
•ˇThermal ionization (TIMS)
•Plasma-desorption ionization (PD)
•Matrix-assisted laser desorption ionization (MALDI)
•GC
•LC
•Direct inlet
A. Kočan, Slovak Medical University
Electron Impact Ionization Source
~70 Volts
+
_
+
_
e- e-e++
+++
+
_
Electron Collector (Trap)
Repeller
Extraction
Plate
Filament
to
Analyzer
Inlet
Electrons
Neutral
Molecules
Positive
Ions
10 to 20 eV out of those 70 eV are
transferred to the molecules during the
ionization process;
Since ~ 10 eV are
enough to ionize
most organic
molecules the
excess energy leads
to extensive
fragmentation;
Hence EI is
classified as a
„hard“ ionization
technique
The fragmentation
gives structural
information
A. Kočan, Slovak Medical University
Detector
Ion
Source
+
_
_
DC and AC
Voltages
resonant ion
non-resonant ion
+
Quadrupole Mass Filter
• Consists of 4 parallel metal rods.
• Two opposite rods have an
applied potential combined from
DC and AC voltages.
• A mass spectrum is obtained by
monitoring the ions passing
through the quadrupole filter as
the voltages or frequency on the
• For given dc and ac voltages, only
ions of a certain mass-to-charge
ratio pass through the filter and
all other ions are thrown out of
their original path.
• The voltages affect the trajectory
of ions traveling down the flight
path centered between the rods.
Ion Trap Mass Spectrometry
• The advantages of the ion-trap mass
spectrometer include compact size, and
the ability to trap and accumulate ions to
increase the signal-to-noise ratio of a
measurement.
Wolfgang Paul
1989 Nobel Price
for Physics „for
the development
of the ion trap
technique“
• This technique can be used easily in the
MS/MS (MSn
) mode
• The ion-trap analyzer consists of 3
electrodes with hyperbolic surfaces to
trap ions in a small volume – the central
ring electrode and 2 adjacent endcap
electrodes. A mass spectrum is obtained
by changing the electrode voltages to
eject the ions from the trap.
A. Kočan, Slovak Medical University
Time-Of-Flight Mass Spectrometry (TOFMS)
• It uses differences in transit time through a drift region to separate ions of different
masses
• It operates in a pulsed mode so ions must be produced or extracted in pulses
• An electric field accelerates all ions into a field-free drift region with the same initial
kinetic energy for all the ions produced
• Since the ion kinetic energy is 0.5mv2, lighter ions have a higher velocity than heavier ions
and reach the detector sooner (e.g., ions of m/z 500 arrive in ~ 15 s and m/z 50 in ~ 4.6 s
• By TOF-MS, up to 50000 full spectra can
be measured in a second
• Since full spectra are available, peak
deconvolution software enabling to
differentiate non-separated GC peaks may
be applied
• The TOF ultra-fast scanning is suitable for
fast GC where peak widths can be much
less then a second
A. Kočan, Slovak Medical University
ion trajectory
not in register
(too heavy)
Ion
Source
Detector
ion trajectory
not in register
(too light)
ion trajectory
in register
S
N
Electromagnet
Magnetic Sector Mass Analyzer
Mass spectra
What is the SCAN Mode in Mass Spectrometry ?
• The scanning mode provides mass spectra. They are recorded (scanned) at
regular intervals (typically 0.5 – 1 /s; much faster if TOFMS is used) during the
GC separation and stored in the instrument data system for subsequent
qualitative or quantitative evaluation.
• From mass spectra, it is often possible to deduce structural features (mass
spectral interpretation) but this requires experience and can be very timeconsuming,
particularly as a complex mixture might contain hundreds of
components.
• The spectra can also be
compared with those
stored in mass spectral
libraries. Although
library searching is a
very useful and
timesaving technique, it
is important to
remember that such
searches do not identify
compounds – analysts
do!
A. Kočan, Slovak Medical University
What is the SIM (or MID) Mode in Mass Spectrometry ?
• SIM (Selected Ion Monitoring) or MID (Multiple Ion
Detection) is much more sensitive technique
suitable for trace quantitative analysis. Here,
instead of scanning a whole spectrum, only a few
ions (generally, the most abundant but
characteristic selected from the mass spectrum)
are detected during the GC run.
• This can result in as much as a 500-fold increase
in sensitivity, at the expense of selectivity.
Depending on the analyte, low picogram to even
low femtogram amounts can be measured using
this powerful technique.
• Stable isotope-labeled
internal standards can be
employed.
HRMS/LRMS-SIM
chromatogram from the
analysis of 2378-TCDD in a
soil extract by the isotope
dilution method
2,3,7,8-TCDD 13
C12-2,3,7,8-TCDD
M+.
A=1392 (82%)
m/z 319.9
m/z 321.9
m/z 323.9
[M+2]+.
A=1688 (100 %)
[M+4]+.
A=829 (49%)
M+.
A=1936 (80%)
m/z 331.9
m/z 333.9
m/z 335.9
[M+2]+.
A=2415 (100%)
[M+4]+.
A=1198 (50%)
A. Kočan, Slovak Medical University
• In general, more ions have the
same nominal mass
• To distinguish between them
certain MS resolution is
needed
• For example, to separate these 2
ions we need a resolution of 5124
R = 122 / (122.060585 – 122.036776) = 5 124
A. Kočan, Slovak Medical University
• This conversion is based on the assumption that all
the 2,3,7,8-substituted PCDDs and PCDFs (17 cong.),
as well as the dioxin-like PCBs (12 cong.), bind to the
same receptor, the Ah receptor, and show comparable
qualitative (toxic) effects, but with different potencies
TEQ = (PCDDi × TEFi) + (PCDFi × TEFi ) + (PCBi × TEFi )
Conversion of Analytical Results
into the Toxic Equivalent (TEQ)
• These differences in
toxicity are
expressed in the
toxic equivalency
factors (TEFs)
• TEF of the most toxic
2378-TCDD = 1
Congener I-TEF WHO-TEF Congener I-TEF
WHO-
TEF
2378-TCDD 1 1 2378-TCDF 0.1 0.1
12378-PeCDD 0.5 1 23478-PeCDF 0.5 0.5
123478-HxCDD 0.1 0.1 12378-PeCDF 0.05 0.05
123678-HxCDD 0.1 0.1 123478-HxCDF 0.1 0.1
123789-HxCDD 0.1 0.1 123789-HxCDF 0.1 0.1
1234678-HpCDD 0.01 0.01 123678-HxCDF 0.1 0.1
OCDD 0.001 0.0001 234678-HxCDF 0.1 0.1
1234678-HpCDF 0.01 0.01
1234789-HpCDF 0.01 0.01
OCDF 0.001 0.0001
A. Kočan, Slovak Medical University
Quality assurance/quality control (QA/QC)
Quality assurance
Preventive measures (quality of facilities, personnel and education,
equipment and service, calibration, internal and recovery standards)
Quality control
Control measures (internal – blank and reference material analyses,
external – interlaboratory comparison, audit)
Reasons
- repeatibility of measurements
- comparison of results between laboratories
- political and economical importance of results
Terminology
Calibration
Limit of detection and quantification
Sensitivity and specificity
Accuracy, trueness, precision
Method validation and verification
Internal standards
Recovery and surrogate recovery standards
Certified reference materials
interlaboratory calibration tests,
GLP
Standard operational procedure
- General information (terminology, principles, range of use, limitations,
safety
procedures, toxicology, waste treatment)
- Directives
- Consumables and chemicals (glass, standards, solvents, reference materials)
- Equipment (sampling and analytical equipment, service)
- Calibration (standards, procedures)
- Analytical scheme (method validation and verification)
- Quality control (internal - blank, reference material, external –
intercalibration)
- Data interpretation
- Annexes
Mokrá - půdy 2002 - 4 vyhodnoceno: 25.4.2003
Koncentrace ng/g
Číslo vzorku toluen 02-753 02-752 02-740 02-741 02-742 02-743 02-744 02-745 02-746 02-747 02-748 02-749 02-750 02-751
Lokalita GC blank Lab. blank RM 454
Hosten
Čihálky 332
Vodojem
Velká
Bata1
Velká
Bata2
Prostřed
kopec
420Vel
Bata
Chlumek
1
Chlumek
2
Horák
mysl.
Nové pole jižní CVM LOQ
Číslo zadavatele 303S 304S 305S 306S 307S 308S 309S 310S 311S 312S 313S 314S
Datum odbě ru 14.11.02 14.11.02 14.11.02 14.11.02 14.11.02 14.11.02 14.11.02 14.11.02 14.11.02 14.11.02 14.11.02 14.11.02 KALIB30
Naváž ka (g) 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0
Ředění 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Naftalen 0,10 1,86 26,74 12,5 6,6 7,5 5,2 5,5 11,8 13,5 7,1 6,6 8,6 5,9 8,5 0,10
Acenaftylen - 0,02 0,58 0,8 0,3 0,7 0,4 0,5 2,2 1,8 0,6 0,5 1,2 2,4 0,8 0,10
Acenaften - 0,04 1,22 1,4 0,3 1,4 1,6 0,6 5,3 3,4 2,5 0,8 2,0 5,4 1,2 0,10
Fluoren - 0,04 2,26 1,7 0,6 1,4 1,3 0,7 4,9 3,8 2,0 1,0 2,2 4,7 1,5 0,10
Fenantren - 0,12 23,96 24,9 6,4 20,5 18,8 8,4 69,1 59,4 14,2 13,6 29,5 109,3 16,8 0,10
Antracen - - 1,12 2,0 0,4 1,9 3,4 1,1 6,1 5,2 2,1 1,4 2,9 16,9 1,8 0,10
Fluoranten - - 27,78 68,2 13,7 58,0 42,0 24,2 213,0 162,5 40,7 37,6 82,5 450,2 42,9 0,10
Pyren - - 19,38 50,5 9,7 45,6 35,4 20,2 159,3 123,6 32,0 28,6 63,8 377,2 33,0 0,10
Benz(a)antracen - - 4,60 17,9 2,9 14,4 14,7 9,1 61,5 49,3 18,3 13,1 26,3 206,3 13,6 0,10
Chrysen - - 11,50 32,4 7,3 25,6 18,4 12,2 102,6 75,9 22,3 16,8 41,2 204,2 20,0 0,10
Benzo(b)fluoranten- - 18,30 61,0 11,7 32,2 23,6 20,4 169,5 128,2 28,0 29,4 67,7 261,1 31,2 0,10
Benzo(k)fluoranten- - 6,04 18,1 3,8 14,4 11,0 7,9 56,4 41,9 13,0 11,2 22,4 134,8 11,6 0,10
Benzo(a)pyren - - 8,34 27,6 3,5 23,6 20,3 13,3 92,8 71,6 24,2 18,4 38,4 285,9 21,3 0,10
Indeno(123cd)pyren- - 8,22 33,1 6,4 21,4 14,8 11,1 98,7 72,0 22,6 19,6 41,0 216,1 20,7 0,10
Dibenz(ah)antracen- - 0,82 2,7 0,6 2,4 1,6 0,9 7,1 8,3 1,8 2,3 4,1 25,8 1,8 0,10
Benzo(ghi)perylen- - 11,26 29,7 5,3 20,6 14,8 11,4 83,9 61,4 19,4 16,3 36,0 181,8 18,5 0,10
Suma PAHs 0,10 2,08 172,12 384,5 79,5 291,6 227,3 147,5 1144,2 881,8 250,8 217,2 469,8 2488,0 245,2 1,60
100% D-PAHs (ng)2 000 2 000 2 000 2 000 2 000 2 000 2 000 2 000 2 000 2 000 2 000 2 000 2 000 2 000 2 000
ředění 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
D8-naftalen 0% 0% 88% 72% 79% 66% 65% 80% 62% 66% 21% 61% 75% 81% 81%
D10-fenantren 0% 0% 90% 77% 91% 68% 72% 86% 77% 79% 88% 79% 85% 94% 92%
D12-perylen 0% 0% 86% 74% 34% 67% 73% 86% 83% 83% 89% 82% 93% 101% 96%
GC blank ..... slepý vzorek přístroje GC-MS - nástřik čistého rozpouštědla do plynového chromatografu CRM ..... analýza certifikovaného referenčního materiálu
Lab. blank ..... laboratorní slepý vzorek - analyzovaný celým analytickým postupem s čistými rozpouštědly a všemi použitými materiály RM ..... analýza laboratorního referenčního materiálu
GPC blank ..... slepý vzorek GPC chromatografu NQ ..... nekvantifikováno - analyt byl překryt interferentem
PUF blank, GF blank ..... terénní slepé vzorky - pasivní odběr na polyuretanovou pěnu a skleněné vlákno LOQ ..... meze stanovitelnosti
PAHs in Ambient Air - Košetice 1996-2004
Weekly Sampling - Gas Phase
0
20
40
60
80
100
120
3.1.1996
3.7.1996
1.1.1997
2.7.1997
31.12.1997
1.7.1998
30.12.1998
30.6.1999
29.12.1999
28.6.2000
27.12.2000
27.6.2001
26.12.2001
26.6.02
25.12.02
25.6.03
24.12.03
23.6.04
22.12.04
Sampling Date
PAHs[ng.m-3]
Benzo[ghi]perylene
Dibenzo[ah]anthracene
Indeno[123cd]pyrene
Benzo[a]pyrene
Benzo[k]fluoranthene
Benzo[b]fluoranthene
Chrysene
Benzo[a]anthracene
Pyrene
Fluoranthene
Anthracene
Phenanthrene
Fluorene
Acenaphthene
Acenaphthylene
Naphthalene