Transcript DIOXIN 2003 BOSTON SESSION SUMMARY REPORT Rapid …

DIOXIN 2003 BOSTON
SESSION SUMMARY REPORT
Takeshi Nakano
DIOXIN 2003 Rapporteur Reports
＜Analytical＞
■FASTER ANALYSIS
AUTOMATED CLEANUP SYSTEMS
・Pressurized Fluid Extraction(ASE) with silica
cleanup in cell
・Semi-Automated Comprehensive Extraction
・Multiple Fractionation(SACEMF)
・Fluid Management System
・SFE-GC/MS & Bioassay
・Miniature and disposable cleanup procedures
■FASTER ANALYSIS
SAMPLE ANALYSIS
Bioassays – Excellent agreement with
GC/HRMS, Biased High, Biased Low
– Minimal Cleanup, Full Cleanup
・GC-TOF with Fast GC
・Combined analysis of analyte groups
・Parallel Columns Analysis
・GC Racer
■ MORE SELECTIVE ANALYSIS
Multidimensional Gas Chromatography
-GC/GC-TOF for PCBs and PBDEs
-GC/GC-ECD for PCDDs and PCBs
Stopped Flow Chromatography
Analyte Specific Columns
Congener methods for source identification
GC/MS/MS－QIT and TQMS(PCDDs, PCBs)
Additional Labeled Standards
13C12BDE 209, 13C-HBCD,PFOS
■ MORE SENSITIVE ANALYSIS
REQUIRED FOR FOOD ANALYSIS
Bioassays – Low fg/g TEQ DLs
Chromatographic Modulation
Larger sample sizes or large volume
injections
Requires more rigorous cleanup
■ NEW TECHNIQUES FOR ANALYSIS
・LC/MS－HBCD, TBBPA, PFOS, PFOA
Passive Sampling for Air
-Window sampling of Biofilms for
Halogenated Compounds
-Mosses for sampling
Passive sampling of water samples
-Semi permeable membranes
SPME for polar and non-polar compounds
Gas Monitors for Combustion Systems
■ ENHANCED QUALITY
Performance Based Methods with well
defined quality standards
－Ensure labs are measuring the same thing
the same way
Ensure Quality is part of lab’s culture
Accreditation, ISO 17025
Participation in interlaboratory and
Performance Evaluation Studies
Use of Certified Reference Materials and
Standards
■ ADDITIONAL QUALITY
Obtain Consensus and Direction on Low
Level Reporting
-Control Lab Contamination, e.g BFR material
in labs－reduces dust in lab, Teflon in LC/MS
values and tubing for PFOS
-Blank Subtraction－no common protocol
・Promote R&D and continual improvement
＜Brominated Flame Retardants＞
＜Brominated Flame Retardants＞
Background
From late 1980’s to 1997
1988 (15 papers)- 2002(30 papers)
2003
・Plenary Lecture by Jacob de Boer
・Over 110 presentations included BFRs
・4 special sessions over two days
・Roundtable discussion
・Two day workshop prior to Dioxin 2003
Highlights of the BFR Workshop
Plenary presentation by Åke Bergman
・Focused on other BFRs that we are not
currently investigating
・Reactivity of various Flame Retardants
Keynote Presentations by Linda Birnbaum
and Mehran Alaee
Similar presentations to Dioxin 2003,
however in smaller setting
BFR Sessions:
Brominated Flame Retardants & Related
Compunds,
・Åke Bergman, and Rob Letcher
・Levels in human tissue
Brominated Flame Retardants and Related
Compounds
・Mehran Alaee and Janice Huwe
・Metabolism and environmental occurrence
PBDEs Analysis and Environmental Levels
・Derek Muir and Shin-ichi Sakai
PBDEs Human Exposure and Biological Effects
・Linda Birnbaum and Andreas Sjödin
Levels in Human Tissue
・New data of levels and trends in human tissue
from US.
・Retrospective time trend study of PBDEs and
PBB in human serum from US
・PBDEs in maternal and fetal blood samples
・Congener specific measurement of PBDEs in
individual milk samples from nursing
mothers in US
・BDE-209 was detected in breast milk
Other studies from UK, Northern Quebec, and
Sweden
Metabolism
Debromination of PBDEs particularly BDE-209
PBDE metabolites, chromatographic
characterization and environmental occurrence
Possibility of naturally occurring hydroxy &
methoxy BDEs and tribromo-p-dibenzodioxin
were discussed
Environmental Occurrence
Information on levels of BFRs at this
symposium was overwhelming
・HBCDs are widespread in the environment
・In some instances the levels of HBCD was
similar to PBDEs in biota
・Levels of HBCD is on the rise in Europe
・Isomer specific determination of HBCD
demonstrated isomer specific bio-magnification
・Use of skipjack tuna as a global bio-indicator
for PBDEs was discussed
・Decabromodiphenyl ethane was detected in
the environment
Analysis
BFRs are not just another PCB
・Synthesis of isotope labeled HBCD, hydroxyBDEs and nona-BDEs
・GC conditions such as injection technique
plays an important role in the determination of
BDE-209
・Comprehensive GC/GC method showed some
promising data
・Some information of chromatographic behavior
of PBDD and PBDF was presented, however
there was lack of discussion on mixed
bromochloro dioxins
Human Exposure and Biological Effects
Co-exposure of BDE-99 and CB-52 enhanced
developmental neurotoxic effects
PBDEs have low dioxin-like activities
Estrogenic activity of PBDEs and other BFRs
were evaluated both in-vivo BDE-99 and invitro (TBBPA, HBCDD, TBP, HO-BDE)
Exprosure to 6-HO-BDE 47, resulted in
significant reduction in aromatase enzyme
activity
＜Formation and Remediation＞
■Formation
Introduction of X-ray absorption fine structure
spectroscopy (XAFS) provides new aspects to
de novo synthesis.
Identification of chemical state of copper in fly
ash
Cu, Cu2O, CuCl, CuCl2, CuO, Cu(OH)2, CuS,
CuCO3/Cu(OH)2/H2O
Strong correlation between copper oxides and
CBs/PCBs
Further application produces more information
Thermal Destruction
In Situ Thermal Desorption
Vacuum Heating Process
Indirect Heating
Super Critical Water Oxidation
High destruction rate of dioxins in soil/fly ash
Further investigation for the best available and
cost effective technology is necessary.
■Interest to Non-Stationary Combustion
(Reduction of Soot Formation)
Optimization of Cold Start-up Conditions
＊Optimization of burner
＊Reduction of air supply
＊Prevention of air leakage
＊Strictly control of the CO level
＊Activated carbon injection
Improvement of Shut-down
＊Stop of waste feed until back-up burner is
fired
＊Burner operation till burn out
Bioremediation
1.Bacteria Bacillus, Sphingomonas, mixed
culture
2.Fungi Pseudallescheria
It will be a low cost technology.
Destruction of highly chlorinated dioxins?
Establishment of application method in
large scale treatment is needed.
＜Toxicology＞
＜Toxicology＞
Topics in Toxicology
BFRs
Ah Receptors
Pharmacokinetics/Modeling
Endocrine Disruptors
TEFs
Developmental and reproductive Toxicoogy
Rats and mice vs Ecotoxicology
Why do we differentiate these two groups?
All species we examine have
－Endocrine systems
－Reproductive systems
－Immune systems
－Ah receptors
Suggestion:
－Have sessions on toxicology topics
(reproductive, endocrine, etc.)
It would make the rapporteur job easier
Ah Receptor
Non-halogenated Ligands
What is the role of the Ah receptor?
Biosensor for light, environmental
chemicals (natural products and POPs)
Ah receptor in C. Elegans to humans
Fish have multiple Ah receptors
Mammals have one Ah receptor
AhR Response Elements may have ligand
specific effects
TEFs
Expanding the methodology to other
chemicals
Why the broad range in REPs for a single
chemical
－Different systems (MCF-7 vs MCF-10A
cells)
－Different methods of estimating REPs
－Chemical impurities
－Pharmacokinetics/study design
・Frameworks for evaluating data used to
derive TEFs or RPFs.
EDCs
EDCs more complicated that we thought
－Chemicals act on more than ER, AR and TR
・Alter synthesis and catabolism of hormones
－Chemicals act on more than one system
・TCDD and DDE influence/disrupt both
estrogen and androgen pathways
－Interactions between Endocrine, Immune and
Nervous system
・Impossible to effect one of these systems and
not the others
・Call for more holistic approach to
understanding the effects of environmental
chemicals
Toxicology
Pharmacokinetics Animal and Human data
matching up
－Influence of disease states (animal and
human concurrence)
－Dose dependant elimination rates.
Mixtures of POPs
－Particular focus in wildlife studies
＜Level＞
Food levels
Food still can be a matter of concern for human
uptake of chlorinated components as reported:
Schecter et al. Presented new findings for
TCDD contamination of food, recently collected
at a HOT SPOT north of Saigon/Vietnam,
close to a former air base. For individuals
consuming this food regularly elevated blood
levels were reported even 30 years after the
Vietnam war.
First dioxin and PCB data in food were reported
for Greece by Papadopulus: The levels were
found to be quite similar as reported for other
southern European countries.
■Food, cont.
Human exposure to PCDD/Fs and PCBs
for Japanese infants and adults were given
in 2 papers:
The intake for infants was found to be
25times higher than the WHO-TDI, even
after theⅡ. delivery as reported by Uehara
et al.
For adults the estimated intake was
reported by Suzuki et al., at 1.5 pg TEQ/kg
BW/day. 97 % resulted from the diet.
■Food, cont.
Of specific help may be a paper of Focant et
al. from University Liege. They analyzed
Fast Food samples from 8 locations
worldwide for PCDD/Fs and PCBs.
Resulting from this we can expect the same
“dose” of about 2 pgTEQ/g fat in Sidney,
Atlanta, Zurich or other places when
consuming a Hamburger or Pizza.
■ Human Levels
Additional results of the WHO-coordinated
exposure study on the levels of PCBs, PCDDs
and PCDFs in human milk were reported by
Malisch and v. Leeuwen. Lowest values were
found for countries from the southern
hemisphere: e.g. Brazil, New Zealand, Australia,
Fiji. The 2 samples from US (east/west coast)
were found to be below the “world median value”
of 28 samples.
3 papers gave information on special
consumption habits on the Faroe Island:
■ Human Levels, cont.
D. Barr et al. reported on the successful
application of new analytical methodology on
PCBs and OC pesticides for 900 serum samples
from children from the F. Isld. Correlations
between selected PCBs and blubber
consumption and nursing could be demonstrated.
Weihe et al. reported on the sustained high
concentration of Faroese pregnant woman
despite dietary intervention while Heilmann et al.
gave information on decreased childhood vaccine
response in children exposed to PCBs from
maternal seafood diet at the F. Isld.
■ Levels other than Dioxins and PCBs
Fluorochemicals are used in a wide
variety of industrial and consumer
products. Increasing interest in these
components is reflected by 7 oral
presentations.
end products of these
components in the human body. This
and similar end products were reported
for background
exposed population in USA, Italy and
India. The values found were up to 10
times higher than
corresponding PCBs.
ng/ml.
Triclosan is a persistent and lipophilic
component that is acutely toxic to biota.
Mehran Alaee
et al. presented the first evidence for
Triclosan in fish plasma from 13 different
species of fish
collected in the Great Lakes area
(Detroit River).
■ Soil Levels
First background levels of PCDD/Fs in 42 soil
samples of Beijing area, China were reported
by Chen et al. at a mean of 0.8 pg TEQ/g.
Data are comparable to West- European
soils.
For site of a former PCP producing plant in
Taiwan, Chung et al. referred on highly
contaminated soil and sediment samples of
up to 2000 ng TEQ/g. The former industrial
field will be used as urban residential area.
First successes in cleaning activities could be
reported at.
■ Sediment Levels
The occurrence of elevated POP levels in
sediments can often be seen in association with
adverse biological effects.
Vosolo et al. provide first data for PCDD/Fs and
PCBs in sediments from South Africa. In general
the values are relatively low. Levels were highest
in urban and industrial areas and occur at lower
values in pristine areas.
Knoth et al. reported on the potential effect of a
historical flood of the river Elbe in 2002 on dioxin
concentration of sediments of the river.
■ Sediment Levels, cont.
Contaminated landfills and chemical factories
could have leaked out. Leaking of a highly
dioxin contaminated plant area in Czechia
could not be proved.
Historical and projected surficial sediment
concentration if dioxins and PCBs in Lower
Passaic River, New Jersey were given by Su
and Finley. Rates of 50 % decline were
calculated from the historical trend for most of
30 congeners at about 20 years.
■ Levels Ⅱ
Olaf Paepke and Susan Shaw
・Total number of papers 139 (18 %) Session
－POPs in Arctic SS
－POPs in Marine mammals SS
－POPs in Sediments and Aquatic Environments
・Wildlife SS
・Fish SS
■ POPs in the Arctic
AMAP Update: Muir et al. presented new data on
POP levels and trends. POPs in wildlife are
highest in the European Arctic and lowest in the
North American Arctic (except for HCHs).
“Legacy” POPs in biota declined until ～1990, then
began to stabilize. PBDEs are increasing
exponentially in beluga and ringed seals.
Novel Compounds: New chemicals detected in the
Arctic environment are: PBDEs, PCNs,
short-chain chlorinated paraffins (SCCPs) and
planar PCBs (Bidleman et al.). Planar PCBs and
PCDD/Fs were detected in Canadian birds (Braune
and Simon). TEQs were highest in reindeer on the
Kola Peninsula (Amirova et al.).
Levels in Humans (AMAP and New
Russian Study)
Indigenous human populations who
consume marine mammals have high
levels of POPs. Data on the Russians at
Chukotka (Sandanger et al.), the Inuit,
and the Faroe Islanders (Hansen et al.)
indicate the Inuit of east Greenland have
highest levels due to their polar bear diet.
Subtle POP-related effects are reported in
some of these groups and there is a need
to reduce exposure.
■ POPs in Marine Mammals
Levels and Trends
High levels of POPs in marine mammals inhabiting
industrialized areas are linked with
adverse effects and mass mortalities and are a
continuing focus of research.
Law et al. reported levels of OCs and PBDEs in
marine mammals stranded or bycaught in the
UK. The data will feed into on-going risk
assessments on flame retardants within the EU.
Novel flame retardants hexabromocyclododecane
(HBCD) and tetrabromobisphenol-A
(TBBP-A) were recently detected in blubber of
harbour porpoises.
■ POPs in Marine Mammals, cont.
Kajiwara et al. reported temporal trends for PBDE
residue levels as well as changes in
congener profiles of PBDEs in blubber of
northern fur seals collected between 1972 and
1997 from Asian waters.
Lebeuf et al. used patterns of PBDEs and PCBs
in blubber of harbor seals to distinguish
colonies in Atlantic Canada. This study
concluded that seals collected from three
sampling sites were adequately classified into
distinct colonies on the basis of their patterns of
POPs.
expression of the AhR and CYP
subfamilies was examined in Baikal seals
(Iwata et al.) and in
belugas from the St. Lawrence estuary
and Arctic Canada (Letcher, et al.).
An unusual field study in Sarasota Bay,
Florida (Wells et al.) is integratinf data on
history,
health and reproductive success to
examine effects of POPs on a local
population of
free-ranging bottlenose dolphins.
■ POPs in Marine mammals, cont.
A new approach (Shaw et al.) applied reporter
gene technology (CALUX) to assess
relationships between the induction potency
(TEQ) of planar PCBs and PCDD/Fs and
immune function in free-ranging harbor seals
along the US Atlantic coast. A positive
correlation between lymphocyte mitogenesis
and CALUX-TEQs was found, suggesting an
immunomodulatory effect of dioxin-like
compounds.
■ POPs in Sediments & Aquatic Environments
Reports on POPs in fish from the Baltic Sea
suggest that the occurrence of dioxins and other
persistent chemicals continues to be of concern
in the Nordic countries.
Isosaari et al. concluded from monitoring studies
in Finland that the levels in pelagic fish
younger than 3-5 years old are below maximum
permissible limits (4 pg WHO TEQ/g fw).
Bjerselius et al. reported similar findings in fish
from the Baltic Sea and along the Swedish
coast.
■ POPs in Sediments & Aquatic Environments,
Monitoring studies of fish conducted over the past
few years suggest that PCDD/Fs and other
POPs are approaching levels of concern, and
more data is needed.
Abalos et al. reported on dioxins and PCBs
monitored in fish and shellfish consumed in
Spain.
Munschy et al. provide one of the few reports on
PCDD/F levels in bottom fish from French
coastal waters along the East English Channel.
Vojinovic-Miloradov et al. present the only paper
on PCB and OC pesticide levels in amphibians.
Levels in the liver of frogs in Montenegro suggest
＜Transport and Fate＞
■ OVERVIEW
In total, over 40 papers presented, from all corners
of the world
Appropriate that several studies examined the
regional & global fate and cycling of PCDD/Fs and
PCBs
In the Eastern Mediterranean, ca 4 t ΣPCB/yr
eliminated as a result of the major removal
mechanism - OH radical attack
Extrapolated to a global scale, and OH radical
attack remains the predominant mechanism for
lower MW PCBs. For higher MW congeners like
153 & 180, the dominant removal process is burial
in continental shelf sediments.
■ OVERVIEW
Mean residence times in the global environment
for such higher MW congeners are ca 50-100
years, confirming the longevity of the PCB
legacy
For PCDD/Fs, the oceans and the atmosphere
(principally via OH radical reaction) shown to be
equally important global sinks for ΣT4-O8CDD/Fs. Steady state assumption estimates
total global emissions to equal ca 20 t/yr
et al.)
-Doubling of endometriosis but not
significant dose response
-Longer menstrual cycle but only in
women exposed pre-menarche
-No increase in spontaneous abortion or
birth defects (numbers too small)
weight/SGA
-Increasede breast cancer incidence
Could be an underestimate of effects due
to potentially high background
Longer menstrual cycle length showed
also in Yucheng women by Leon Guo et
al.
both in the Yucheng
cohort (Leon Guo et al.) And in Swedish
fisherman (Hagman et al.)
-No casual relationship between paternal
TCDD exposure and lowered birthweight
(Lawson
et al.)
Increase of:
Overall cancer, Prostate cancer,
Melanoma, Diabetes, Probable peripheral
neuropathy
Decrease of:
Logical memory score
(Michalek et al.)
papers (time!!!)
Much important new information was
presented
We have still a lot of work to do
Thank to all, Best wishes SEE YOU IN
BERLIN!!
presentation)
－Perfluorinated Compounds
Not all POPs are created equal
－Perfluorinated compounds have new
properties that need to be considered
”Re-Emerging POPs”
－PBFRs, PBDEs, some OC pesticides
－Polar (PFOS)
－Non-polar (sulfonamides)
Extraction techniques
GC/MS methods LC MS methods
Different methods work for different
compounds
many labs using different commercial
materials as ‘standards’
Need stable isotope standards － some
groups are now having these specially
synthesized so we can expect some
advance on this front in the near future.
membranes.
Physical properties also suggest effects
on membranes.
As well as short term affects on
membranes also long term alterations on
gene expression.
Human Exposure
Detected in human serum and milk
Still determining the range of specific
compounds that should be monitored PFOS,
PFOSA Net-FOS-OH, PFOA
Compounds measured in Fast Food Survey in
Canada
Concentrations of sulfonates seem to have
declined in the last few years
(US production ceased in 2000)
compounds accumulate in blood and liver.
Our standard BMF model may need to be
modified for these compounds as they do
not accumulate in lipids.
Concentrate in some marine mammals
(whales) but not others (walrus)
－Contamination in lab equipment
(plastics)
－Contamination in instruments (Teflon)
Measured in open ocean waters at pg/L
PFOA > PFOS
Showed greater concentrations nearer to
the surface than at depth
－Still detectable in deep waters
compartments
Better understanding of toxicological
effects
PFCs are “POPs of a different color”