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Full text of "PAH Exposure at the World Trade Center Site"

NDTHEWTC 
rfftpONSE 

Glenn Talaska, Ph.D., CIH 

Department of Environmental Health, 
University of Cincinnati College of 

Medicine 



Polycyclic aromatic 
Hydrocarbons (PAH) 

Benzene rings fused during burning with 
insufficient oxygen 

Well absorbed from lungs and skin 





benzo(a)pyrene 



dibenz(a,h)anthracene 





^^pn«pwi 





B 






*• 1 






/• ■ s 4' '*.• 






' SftiiVs 




m $$& Li l V §fe 'vS 






-JM l'..' 4*3K-_~ <£&*• 





Allfn 


i 




1 J 


***** 


1 **^nfl 


[ ^^^^^^^^^M 




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- -^ 





AH exposure associated with 




MM 



cane 



h Smokers 

h Coke Oven Workers 

h Aluminum Smelter Workers 

h Chimney sweeps 



PAH are absorbed by the body and metabolized to 
compounds that can bind to DNA and then cause 
mutations that can initiate carcinogenesis. 

It IS biologically plausible that PAH can cause 
cancer. . . .IF. . . .there is sufficient exposure. 




Exposures at WTC 



Sources: -90,000 1 of jet fuel, 500,000 1 
transformer oil, 380,0001 of diesel and heating 
oil and approximately the same amount of 
gasoline burned plus any and all burning items 

Area samples collected at the fence line 
beginning 9/16-23/01; no personal samples. 
(Pleil et al, 2004) 

Biomarker samples collected once on October 
1, 2001 (Edelman,2003) 

Window film samples Oct. 27 and 29, 2001 
(Butt et al, 2004) 



Pleil et al, 2004 data 




Ground Zero 



Broadway 

O 



Elapsed Time after Sept. 11 , 2001 (d) 



rate exposure estimates? 





All air measurements and estimates based on 
area samples collected at the fence line; area 
samples typically underestimate worker 
exposure. Difference can be 3-40 fold. . .or 
more; or less 

Included only PAH in the particulate phase; 
Burstyn et al.(2002) estimated that 10X more 
PAH was found in the vapor phase in asphalt 

workers but Quinlan et al (1995) saw about 

equal amts. for coal liquefaction workers 



Unmeasured effects 



What is the impact of being in a plume? 

What was the effect of exercise/ exertion? 

Data were collected to determine ground level 
environmental exposure; no attempt to capture 
peaks; or to assess exposed worker exposure; 
Authors state that exposure to workers at the 
site could be "much higher " 



Butt et aL, 2004 data 



Windows in buildings at var. distances 
sampled: 

Within 1 km (0.6 mi) average was 77,100 ng/m : 

Downwind sites had averaged 130,000 ng/m 2 

Upwind sites averaged 18,500 ng/m 2 

Upwind sites >2km averaged 6000 ng/m 2 

Can't be used for exposure estimates but 
indicate differences of proximity and in the 
plume 



Indr/icJ 



al Variation In Absorption Of 
■ Contaminants Can Be Assessed 



Pulmona: 
Rate 



•sorption Rate Varies with the Ventilation 



Phys 

Work 



icaj 



oad (W) 



50 (Light Work) 
100 (Moderate) 
150 (Heavy) 



Alveolar 
Ventilation 
(L Air/Min) 

5.0 

16.0 

27.0 

1 38.0 



Heart 
Rate 

(L/Min) 



13.0 
19.0 



increase 
Ventilatio 



(vs. Light) 



onitoring PAH exposure 

1HP 



Pyrene is an important component of PAH 

There IS a Biological Exposure Index for 1HP, 
the major metabolite of pyrene. ACGIH BEI 

Biomonitoring can account for differences in 
absorption, distribution, metabolism and 
elimination if it is done correctly. 

Can take into account both skin and inhalation 
exposures 

Exposures can be reconstructed 

But it is easily mis-used 



(D 



LU 



LU 

o 
cc 

LU 

a. 



200 



ELIMINATION OF A COMPOUND FROM THE BODY 

24 HOUR HALF-LIFE 




160 - 



120 - 



80 - 



40 -, 




M 16 24 T 16 24 W 16 24 T 16 24 F 16 24 S 16 24 S 16 24 M 

TIME (Hours) 



a (ug/l): Edelman et al, 
T 2004 



a All Exposed 

h Controls 

h Day 1 + FF@collapse 

a Day 1+2 NC 

a Spec Ops Command 

a ACGIHBEI 



0.092 
0.062 
0.110 
0.113 
0.159 
1.000* 



a *end of shift, end of workweek sample 
specified 



-e Edelman's data accurate 
-xposure estimates? 

Samples were collected 22-24 days after peak 
exposures; the half-lives of 1HP are 5.5h, 23h 
and 23 days. 

No variances reported (the outliers are what 
count in IH) 4% were said to be in the upper 
5% of CDCs NHANES values. . ..how many 
controls were in the upper 5 % ? 

May have sampled at lowest point prior to an 
exposure; Sampling time relative to last 
exposure not given. 



Edelman data:ll 



Sampling time relative to last exposure not 
given 

Firefighters seem to have lower 1HP levels 
than many workers to begin with. 

Absorption from lung complete? What about 
large particle masses? PAH on particles might 
not be rapidly absorbed (Gerde, et al data, 
below) 



Pre- and Post- 1HP Levels in Aluminum Plant 

Reduction Workers 




Days 



Preshift 



Postshift 



VanSchooten et al, 1995, Cancer Epi. Biomarkers and Prev., 4,69-77 



c 

o 

E 

CO 

CD 
> 

-I— ■ 

_CO 
CD 



175 



140 



105 - 



70 



35 




TWTFSsivrTwrFssivrTwrFssi\/rTwrFssi\^^ 

Days 
384 hr/ h 5.5 hr hal 23 hr half urinary le 



Timecourse of DNA adducts and 1HP levels in 
Psoriasis Patients treated with coal tar 



275 
240 
205 
170 
135 



VMWA 







PreTreatment 1 treatment 5 treatments 1 week after tr 



Events 



4.00 



3.20 



2.40 



1.60 



0.80 



0.00 



Skin Adds 



Lymph Add 



1-HP 



Godschalk et al. (1998) Cancer Epi. Biomarkers Prev., 7, 767-73. 



CERDE. MEDINSKY, AND BOND 




0.01 



1 MIM 1 HOUR 

TIME (ttcondl) 



1 DAY t MONTH 



Fig. 3. The simulated release rates of a pah iw.— ■ j 

« •*-. from pure crysu. a«^S„ (M^S ^TsSS^X^l " WU " a *« D ** ed «— *°~ 

sorting from (heir surfaces (Model C) The numr^?..^.. ?^ "*" d,m »»*«"** «•«* a PAH 

h PAHs from diBerem *« a£re££ i^ h '': 22^3' T^ PAHi BeC » U ~ "*^« 
hatotKW exposures, carrier i^icte win i^^rsr^2^' '" " me - " " Hke, y *•«• « low-dose 



£5S£l£""" ma,l °" " **— •««• «**. ,„ »„,„,, rwon , _ Ih> 



Mouth 



Secondary bronchi 



450 cm 3 Tidal air 



Percent retention 

1500 cm 3 Tidal air 



20 



1 ° 6 02 20 6 2 0.6 0.2 



Pharynx . 15 J 18 1 

Trachea m ° 10 1 

Pulmonary bronchi ,? 1 ° ° ° 19 3 a 








12 2 20 ? i ° 

-~ lQ 4 1 A 5 * 

Tertiary bronchi 17 o o ° 21 ( T2 N 2 " 

Quarternary bronchi 6 7 ? ° ° 9 ^° 5 

Terminal bronchioles * io * ' 1 10 3 1 








Respiratory bronchioles n i c 4 6 * 9 3 2 4 

Alveolar ducts a^ 34 ° 3 2 2 4 

Alveolar sacs a < * * U ° « 26 10 n 

T ^Is =? =| £ -2 J J 18 17 6 7 



93 83 41 16 



22 99 95 59 



21 29 



sorb on particles 



Soot and concrete particles attract PAH 
differently ; but both do 

Particles my accumulate in lung and slow 
absorption into the body 

Particles may be coughed up, expectorated or 
swallowed, but this seems a detoxification 
pathway 




racting exposures 



h Metabolic enhancers 

■ PCBsandTCDD 

■ Highest ambient level of TCDD ever measured 
anywhere in the world after 9/11 

h Silica: PAH enhance the carcinogenicity of 
silica exposures.... Additive plus! 

h Asbestos: PAH enhance the carcinogenicity of 
asbestos exposures; Multiplicative! 



Conclusions 



Exposure of workers to PAH within the Ground 
Zero site was almost certainly higher and maybe 
substantially so, than what is indicated by the 
major exposure studies. I 

A fuller report of the biological monitoring data is 
needed to predict what the exposures may have 
been during the early periods after 9/11 and who 
may have had highest exposures. 

If the effective half life is -24 hours, 1HP levels on 
9/12 could have been well above the BEI level 
assuming NO Exposure since 9/11/01 



Cell 
Replication 



Mutations? 



Mutations? 



Mutations 



Metastases 



Mutation 



Initiation 



Promotion 



Progression 



May have to Cell Growth Selection 
happen >1 Changes Pressure 



\ Aggressive 
Growth 



Point Mutations 
Gene Mutations 



Table 1. Adjusted geontetrii 


: mean chemical concentrations and ANCQVA results. 
















[»M, 






towal time 






Unit assignment 








Days H 


P-Value, 


Special 










■i -icepi 




hi at 


pent alter 


present at 


Operations 


Other 


p-Value, 






controls 


Control 


'ipse 


collapse 


collapse vs 


Command 


firefighters 


special 


Chemical 


Units 


1/1=3181 


|/t=47| 


(ii=148| 


(n=142| 


1-2 days 


|/i=95l 


|/i=195l 


vs other 


'•Hflfonypyrene 


■: ii-h 


331' 


62.5 


110' 


113' 


NS 


159' 


77.9 


>0.01 


1 -Hydrwyphenandmne 


1 urins 


188 


156 


197 


206 


NS 


2*8* 


164 


< 001 


Z-Hydro^yphangn^fene 


ng/l urine 


164 


119 


153 


w 


NS 


21V 


147 


401 


3-Hydroitvphenanifv8ne 


ng/L unne 


162 


127 


158 


185' 


NS 


214' 


145 


<0.01 


IZ3AW,8ICD8D 


iiw 


m 


19.2 


301* 


264* 


NS 


30.6* 


25.9* 


NS 


1 llicfibrt 


|m 


0.235 


0.165 


0274 


0289 


NS 


0.343' 


0,231 


<o.ot 


iwtfpwXvta 


pg/l liiooil 


0.066* 


0.051 


0066 


0.021 


NS 


0.081* 


0.05? 


m 


MeAiyl for/ butyl oilier 


Mg/L Wood 


0124 


0101 




0.138 


NS 


0.165' 


0107 


'0.01 


Lead 


iq/dL blood 


2.76' 


1.93 


303' 


298' 


NS 


377* 


143* 


<0.0I 




eJg/1 urine 


11/ 


101 


1,1' 


119 


NS 




0.96 


401 




jjg.'L urine 


0,203' 


0.165 


0271' 


0.238* 


<001 


0.381' 


8.109 


001 


Cadmium 


pg/l urine 


0.324 


0.377 


0.355 


0.299 


■001 


0.351 


0.303* 


401 


Uranium 


pg/L urine 


0.00611' 


1100752 


0.00643 


0.00576* 


NS 


OffilO' 


'■■•w 


NS 



Abbreviations; HCDBO, heptachlorotJibeniodrnxm; NS, not significant To be listed in this table, a chemical had to show a difference between any two oi tlie groups by Kruskal-Wallis 
testing lp < OIL All chemicals listed m tire table were sipiont by ANCQVA at p < 11.111, except 1 -hydnncy phenainhreite Ip ■- 0,02461 and uranium ij = 0,0273), for differences between 
any two of the m exposure pups adjusted lor coronates oi age, race, creatinine, and log cotmine 
'Significantly different Irani controls, p < 0.01 , 



Influence of selected variables on 1-HP post shift 
samples in 2 groups of needle coke plant workers 

with chronic exposure to PAH 



Workers Variable 



Maintenance 



|Pre-shift level 
|Dermal Exp. 
|Air Levels 



P-value 

p.0003 

P.028 

W581 



g^^lU£ 



0.521 



Operations 



|Pre-shift Levels 0.0008 
Dermal| ||p.318 

|Air Levels ||p.067 



IBI424 



Boogaard and van Sittert (1995) Sci. Tot. Environ. 163, 203-9 



c 

o 

E 

CO 

CD 
> 

-I— ■ 

_CO 
CD 



200 



160 



120 - 



80 - 



40 - 




MTWTFS IWIWTFS IWTWTFS IWIWTFS IWTWTFS IWTWTFS IWTWTFS IWTWTFS IWTWTFS U 

Days 

384 hr/ h 5.5 hr hal ■ -♦- 23 hr half ■ body bur 



PAH and other exposures 



h Asbestos and smoking: Multiplicative effect? 
h Silica and smoking: Additive effect 
h Arsenic and smoking: Multiplicative