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Archives of Environmental Health: An International Journal Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/vzeh20
Volatile Halogenated Hydrocarbons in Urban Atmosphere and in Human Blood a
a
Giorgio Gilli Ph.D. , Roberto Bono Ph.D. & Enzo Scursatone Ph.D.
a
a
Department of Hygiene and Community Medicine , University of Turin , Turino, Italy Published online: 03 Aug 2010.
To cite this article: Giorgio Gilli Ph.D. , Roberto Bono Ph.D. & Enzo Scursatone Ph.D. (1990) Volatile Halogenated Hydrocarbons in Urban Atmosphere and in Human Blood, Archives of Environmental Health: An International Journal, 45:2, 101-106, DOI: 10.1080/00039896.1990.9935933 To link to this article: http://dx.doi.org/10.1080/00039896.1990.9935933
PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content. This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http:// www.tandfonline.com/page/terms-and-conditions
Volatile Halogenated Hydrocarbons in Urban Atmosphere
Downloaded by [New York University] at 15:02 04 May 2015
and in Human Blood
GlORGlO GILLI, Ph.D. ROBERTO BONO, Ph.D. ENZO SCURSATONE, Ph.D. Department of Hygiene and Community Medicine University of Turin Turino, Italy
ABSTRACT. Atmospheric concentrations of volatile, halogenated hydrocarbons (VHH) can be correlated with intensity of industrial or commercial activities and with demographic density. Measurements of VHHs were performed in Turin, Italy. The VHH indoor/outdoor contamination ratio was calculated, and VHH blood concentrations were measured during 1 yr in Turin, Italy. The results showed a typical primary pollutant trend: 18.1 Clglm3 during winter and 12.02 &m3 during summer. During the winter, the VHH indoodoutdoor contamination ratio showed a greater indoor presence @ = 3006)and a higher VHH blood concentration (0.71 vs. 0.22 pg/l). The indoor and outdoor atmospheric VHH concentrations provide the major sources of human daily intake, especially during winter.
SOME volatile halogenated hydrocarbons (VHHs) are ubiquitous in the environment. Typically, they are primary pollutants related to industrial and civil activities. In fact, chloroform, l,l,l-trichloroethane, carbon tetrachloride, 1,1,2-trichloroethylene, and tetrachloroethylene, in different concentrations, have been found in rural, urban, and industrial atmospheres; indoor air; drinking water; and food (rarely).'-s In the United States, the concentrations of VHHs in drinking water average more than 30-40 pgll,' whereas in Piedmont (northwest Italy), no more than 5-10 pgll have been found.4 Thus, evaporation from drinking water is an unlikely source of high indoor air concentrations of some VHH? in our region. Atmospheric VHH concentrations could be related to either the intensity of industrial or other commercial activities and demographic density. The higher urban VHH concentrations (Table 1) may originate in part from automobile exhausts.' In Turin (northwest Italy), the atmospheric VHH concentrations are the major source of human exposure. March/April 1990 [Vol. 45 (No. 2 ) ]
Considering the different rates of absorption and metabolism, human exposure to VHHs could be monitored by exploiting some biological markers. The concentration of VHHs in blood* and exhaled breathg can assess long-term environmental exposure. Therefore, this study considers the following: (a) measurements during 1 yr of atmospheric VHH pollution in Turin relative to some meteorological parameters, (b) assessment of the relationship between indoor and outdoor VHH concentrations, and (c) measurement of the VHH concentrations in blood as a specific biological marker.
Materials and methods Air. Atmospheric sampling was conducted from October 1987 to September 1988 in an "urban canyon" in the center of Turin city. A total of 120 samples were taken during 10 consecutive d (24 h each) each month. Air was sampled at heights of 1.5 m and 2 m from the 101
I
I
Table 1.-Atmospheric
Concentrations of V H H @/m3) in Some Urban and Rural Sites Urban
VHH
1
Chloroform 1,l.l-Trichloroethane 1,1,2-trichloroethylene Tetrachloroethylene
0.68* 11 3.8 11.5
Rural
2
3
4
5
6
7
8
9
10
0.06t 1.4 0.35 4.6
N.M. 6.2 8.4 12.9
0.18* 5.85 N.M. 2.4
N.M. 14.2 6.4 12.2
0.05t 0.05 0.08 0.69
0.15* 1.13 0.09 0.11
N.M. 0.86 N.M. N.M.
0.06* 0.72 N.M. N.M.
N.M.' 1.2 0.32 1.0
-
Downloaded by [New York University] at 15:02 04 May 2015
Notes: 1 F r a n k f ~ r t , '2~ = New Jersey (U.S.A.),9 3 = Milan,I4 4 = California,' 5 = Torino," 6 = Devils Lake, North Dakota , ~ 10 = Susa (Turin)." N.M. = not measured. Each VHH con(U.S.A.),' 7 = Azorre, Portugal,' 8 = South P01e.l~9 = B e r m ~ d aand centration reported resulted from 4-6 h of sampling (n = 10-50). *Data are expressed as arithmetic means. tData are expressed as arithmetic mean of day and night median.
curb. Sampling and analytical techniques employed and quality control procedures have been described in a previous paper.' Meteorological parameters. A private company measured meteorological variables at the same rneteorological station used for measurements of atmospheric pollutants. Meteorological measurements were conducted during the same times as were the atmosphere pollutants. Meteorological variables included relative humidity (RH), temperature on ground (TG), solar irradiation (SI), and wind speed (WS). The mean value for nitrogen monoxide (NO) (24-h data) for each day (10 dlmo) was calculated. Indoor/outdoor measures. The relationship between indoor and outdoor concentrations of VHHs has been studied by sampling indoor (e .g., bedroom, bathroom, kitchen, etc.) and outdoor (i.e., outside the same flat) air at eight private apartment buildings located in the center of Turin. In these apartments, an average of 1 person lives in an area of 25-35 m2 (e.g., 3-4 persons in 80-120 m2). A measurement was made for 6 h (during the night, morning, and afternoon) for both indoor and outdoor air; a total of 31 measurements were made during the winter (1987/1988), and 28 were completed during the summer (1988). Blood. Blood samples were collected in 10-ml Vacutainer tubes (Becton-Dickinson, Ref. no. 606480; sterile, sodium heparin) from 15 males and 15 females during each of the 12 mo. These individuals were chosen randomly from blood donors who resided in Turin. Whole-blood samples were analyzed within 2-3 h after blood was collected (our storage test shows that VHH concentrations are stable up to 24 h). The blood analyses for VHHs were conducted by gas chromatography (head space technique) using an EC detector.' Values were determined by comparison to a curve obtained by standard addition techniques employing chloroform, l,l,l-trichloroethane, carbon tetrachloride, 1, I ,2-trichloroethylene, and tetrachloroethylene (concentrations added: 0.25-4 pdl) in pooled blood. Quality control of all materials used to collect and analyze blood was achieved by rinsing same with hexane and subsequent GC analysis. Identification of 102
chemicals was determined by assessing retention times with different columns: DB1, DB208, DB210 megabore columns (0.53-mm internal diameter [ID]), and with DB624 and DB5 capillary columns (0.25-mm ID) (J&W Scientific, Folson, CAI. The length of columns were 30 m and the thickness of the film was 1 pn. Quality control was maintained by analyzing a standard sample 20 times. The averages, standard deviations, and coefficients of variation are shown in Table 2.
ResuIts The total concentrations of VHHs in the atmosphere are shown in Figure 1. Each bar represents the mean of ten 24-h determinations measured each month for the five chemicals considered. During October 1987 through March 1988, the median was 18.1 pg/m3 (41-43 = 11.9-30.3 pg/m3), whereas during April through September 1988, the corresponding values were 12.02 pg/m3 (Q1-Q3 = 8.21-17.19 pg/rn3),. Concentrations of each VHH are shown in Figure 2. 1,l,l-Trichloroethane was found in the highest concentration, followed by tetrachloroethylene and 1,1,2-trichIoroethylene. Chloroform and carbon tetrachloride were present in much lower concentrations. The averages and ranges of atmospheric VHH concentrations during the 6 cold mo and 6 warm mo are reported in Table 3. The average concentration of VHHs observed during a "typical" week are shown for the cold and warm seasons. An obvious decrease occurred in the concentration of VHHs on Saturday and Sunday (Fig. 3).
Table 2.-Variation
Coefficients in Control Blood Samples' Mean (pg/l) SD
VHH Chlorforrn 1,1,1 Trichloroethane Carbon tetrachloride 1,1.2-Trichloroethylene Tetrachloroethylene
I
*Peak height; n
=
20.
9.05 17.08 28.53 9.03 10.08
1.68 4.19 4.04 1.99 2.67
cv
(010)
19 24 14 22 25
I Archives of Environmental Health
OCT
I)ov
DEC
JAN
FEE
)#R
APR
I#Y
JUL
JUN
AUC
SEP
Downloaded by [New York University] at 15:02 04 May 2015
Fig. 1. Total atmospheric concentrations of VHHs (Turin, Italy; 1987/1988).
m CHLOROFORM 0 1,I, 1,-1RI CHLOROETHANE
16 r
14
--
12
--
18
--
8
--
2
E
CnRBDN TETRllCHLORIDE
0
1,1,2.-IRICHLOROEIHYLENE
0 IEIMCHLOROETHY LENE
~
:j j::j::
:j j:
::
OC1
W
DEC
Fig. 2. Atmospheric concentrations of specific VHHs in Turin, Italy (1987/1988).
Table 3.-Atmospheric Concentrations of VHHs During October 1987-March 1988 (Cold Months) and April-September 1988 (Warm Months) @g/m3) Cold months
Chloroform 1,l,l-Trichloroethane Carbon tetrachloride 1,1,2-Trichlorcethylene Tetrachloroethylene
March/April 1990 [Vol. 45 (No.211
Warm months
Mean @cg/rn’)
Range
Mean @cg/m’)
Range
0.83 9.60 0.49 5.74 8.70
0-1.98 4.51-14.7 0.22-0.82 2.28-9.6 3.56-1 2.16
0.14 4.1 0.47 3.14 4.75
0-0.49 2.61-6.4 0.25-0.92 1.61-4.23 2.65-7.77
103
48
E COLD SECISON
0 ClCIRM SEASON
38
28
Downloaded by [New York University] at 15:02 04 May 2015
la
a Fig.
HON
TUE
i
UED
THU
FRI
SCIT
SUN
“Typical week” patterns of V H H concentrations in air (Turin, Italy).
Spearman’s correlation coefficients (rs) are reported in Table 4 for VHH concentrations vs. meteorological parameters and NO during the cold and warm seasons. Aside from the positive correlation between NO and the single VHH or the corresponding sum, no other parameter is correlated with VHH concentrations during either period of the year. The relationship (i.e., correlation coefficients) between VHHs and NO concentrations that were determined for each month (i.e., 10 d) from October 1987 to September 1988 i s provided in Table 5. Table 6 provides medians and ranges of indoorloutdoor atmospheric contamination ratios for total VHHs,
1 ,l,l-trichloroethane and tetrachloroethylene. The indoor/outdoor air contamination ratio was higher in winter than in summer. Ratios were not calculated for chloroform and carbon tetrachloride because some measurements were below the detection limit or were absent. The results of the analyses of blood for VHHs are shown in Table 7. No samples were collected during October 1987 and August 1988. The sum of VHHs shows a highly statistical difference between the two seasons. During the winter, chloroform, 1,1,1-trichloroethane, and often 1,1,2-trichloroethylene and tetrachloroethylene were present; during the summer, however, only l,l,l-trichloroethane was found.
Table 4.4pearman’s Correlation Coefficients (rs) between Atmospheric V H H Concentrations and Nitrogen Monoxide and Meteorological Parameters
Meteorological parameters
Total VHHz Cold Warm season season
NO
+ 0.40
+ 0.64
R.H.
-0.18 + 0.08 + 0.37 -0.11
- 0.02
T.G. S.I. W.S.
-0.25 -0.iS -0.28
1,1,1 -Trichloroethane
Cold season
Warm season
10.38 -0.21 + 0.05 +0.36 -0.13
+0.41
-0.10 - 0.03 - 0.04 - 0.36
1,1,2-TrichIoroethylene Cold Warm season season
+ 0.34 -0.15 + 0.05 +0.37 - 0.09
+ 0.62 - 0.07 - 0.32
-0.17 -0.28
Tetrachloroethylene Cold Warm season season
+ 0.47 -0.14 +0.15 +0.34 -0.12
+0.57 + 0.04 -0.20 -0.17 - 0.23
nitrogen monoxide, R.H. = relative humidity, T.G. = temperature on ground, 5.1. = solar irradiation, and W.S. = wind speed. Measurements during cold season occurred in 1987-1988 ( n = 60); during the warm season, measurements were taken 60). in 1988 (n
-
104
Archives of EnvironmentalHealth
tinuousness of the data measured are considered, and in view of the fact that there are no analogies with other studies. This envi ronmental observation becomes important when considering the next possible impact of the new E.E.C. guidelines that ban leaded gasoline (E.E.C. N.L. 96/25, 201311985). When Italy accepts and enforces this E.E.C. directive in 1991, this should result in a subsequent reduction of VHHs in the atmosphere.’ During the winter, the VHH indoorloutdoor atmospheric contamination ratio (Table 6) shows a greater role of indoor air in human intake, probably as a consequence of the limited air exchange from indoor to outdoor and vice versa. Therefore, the indoor human environment might represent another source of VHHs (or at least some .of them) in the air, especially during the winter. Indoor air exposure, especially during the winter, i s another important factor in total human intake of VHHs, because it has been calculated that humans spend about 80% of their time indoor^.^ Furthermore, the blood concentration of VHHs confirms that there is a higher human intake of VHHs during the winter (Table 7). Overall, blood concentrations of VHHs-particularly in summer-were low, and a more detailed epidemiological analysis could not be performed. Neverthelss, the VHH blood concentrations measured may be intepreted as a specific biological marker of human exposure to the complex environmental pollution with these chemicals. The parallels between VHH concentrations in air and blood relative to cold and warm seasons have not been observed previously. Other studies on VHHs were focused on experimental exposures or on the relationship between these biological markers and industrial exposures. Moreover, the study of these specific biological markers is of importance for public health because (a) several of these chemicals appear to have
Table 5.-Spearman‘s Correlation Cdicients (rs) between VHHs and Nitrogen Monoxide from October 1987-September 1988. Month October November December January February March
Month
+ 0.68 + 0.83 + 0.83 + 0.66
+ 0.67 + 0.43
April May June July August September
+0.59 + 0.44 + 0.39 + 0.52 + 0.35 + 0.85
I
‘Samples were taken 10 dlmo.
Downloaded by [New York University] at 15:02 04 May 2015
Discussion Apart from the January data, Figure 1 shows that a “primary pollutant pattern’’ existed during the winter. In summer, the trend was more irregular, and concentrations varied considerably around a mean value that was lower than during the winter. Concentrations decreased on the weekend in the cold season (Fig. 31, which may confirm the primary source of VHHs: there are few cars in the area on Saturdays and Sundays (with a consequent decrease of automotive exhaust emission) and a higher ”mixing ratio” during the warm season. A lack of correlation between meteorological parameters and atmospheric VHH concentrations was observed (Table 4). A good correlation was found during the entire year between VHHs and NO, which suggests a similar origin and environmental behavior (Table 5). Monitoring of the atmosphere for VHHs during 1 yr appears important when the completeness and con-
Table 6.-Correlation (Mann-Whitney Test) between Medians of Indoor/Outdoor Atmospheric Concentration Ratios ocg/m3) in Winter and Summer Winter (n
-
31)
Median
Range
VHHs
2.69
l,l,l-Trichloroethane
2.62
Tetrachloroethylene
2.15
1.85-29.45 p 1 .00-7.52 p 0.59-30.91 p
Table 7.-Blood
Summer (n
Range
1.33
0.79-2.75
- .m
-
- 28)
Median
1.105 ,0024 1.38 ,0281
0.68-2.27 1.03-4.22
Concentrations of VHHs among Residents in Turin City @@I) n
Mean
SD
Range
Median
Winter
133
1.33
1.66
0.02-9.56
0.71
Summer
131
0.46
0.87
0.00-6.82
0.22
p (Mann-Whitney)
Archives of Environmental Health: An International Journal Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/vzeh20
Volatile Halogenated Hydrocarbons in Urban Atmosphere and in Human Blood a
a
Giorgio Gilli Ph.D. , Roberto Bono Ph.D. & Enzo Scursatone Ph.D.
a
a
Department of Hygiene and Community Medicine , University of Turin , Turino, Italy Published online: 03 Aug 2010.
To cite this article: Giorgio Gilli Ph.D. , Roberto Bono Ph.D. & Enzo Scursatone Ph.D. (1990) Volatile Halogenated Hydrocarbons in Urban Atmosphere and in Human Blood, Archives of Environmental Health: An International Journal, 45:2, 101-106, DOI: 10.1080/00039896.1990.9935933 To link to this article: http://dx.doi.org/10.1080/00039896.1990.9935933
PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content. This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http:// www.tandfonline.com/page/terms-and-conditions
Volatile Halogenated Hydrocarbons in Urban Atmosphere
Downloaded by [New York University] at 15:02 04 May 2015
and in Human Blood
GlORGlO GILLI, Ph.D. ROBERTO BONO, Ph.D. ENZO SCURSATONE, Ph.D. Department of Hygiene and Community Medicine University of Turin Turino, Italy
ABSTRACT. Atmospheric concentrations of volatile, halogenated hydrocarbons (VHH) can be correlated with intensity of industrial or commercial activities and with demographic density. Measurements of VHHs were performed in Turin, Italy. The VHH indoor/outdoor contamination ratio was calculated, and VHH blood concentrations were measured during 1 yr in Turin, Italy. The results showed a typical primary pollutant trend: 18.1 Clglm3 during winter and 12.02 &m3 during summer. During the winter, the VHH indoodoutdoor contamination ratio showed a greater indoor presence @ = 3006)and a higher VHH blood concentration (0.71 vs. 0.22 pg/l). The indoor and outdoor atmospheric VHH concentrations provide the major sources of human daily intake, especially during winter.
SOME volatile halogenated hydrocarbons (VHHs) are ubiquitous in the environment. Typically, they are primary pollutants related to industrial and civil activities. In fact, chloroform, l,l,l-trichloroethane, carbon tetrachloride, 1,1,2-trichloroethylene, and tetrachloroethylene, in different concentrations, have been found in rural, urban, and industrial atmospheres; indoor air; drinking water; and food (rarely).'-s In the United States, the concentrations of VHHs in drinking water average more than 30-40 pgll,' whereas in Piedmont (northwest Italy), no more than 5-10 pgll have been found.4 Thus, evaporation from drinking water is an unlikely source of high indoor air concentrations of some VHH? in our region. Atmospheric VHH concentrations could be related to either the intensity of industrial or other commercial activities and demographic density. The higher urban VHH concentrations (Table 1) may originate in part from automobile exhausts.' In Turin (northwest Italy), the atmospheric VHH concentrations are the major source of human exposure. March/April 1990 [Vol. 45 (No. 2 ) ]
Considering the different rates of absorption and metabolism, human exposure to VHHs could be monitored by exploiting some biological markers. The concentration of VHHs in blood* and exhaled breathg can assess long-term environmental exposure. Therefore, this study considers the following: (a) measurements during 1 yr of atmospheric VHH pollution in Turin relative to some meteorological parameters, (b) assessment of the relationship between indoor and outdoor VHH concentrations, and (c) measurement of the VHH concentrations in blood as a specific biological marker.
Materials and methods Air. Atmospheric sampling was conducted from October 1987 to September 1988 in an "urban canyon" in the center of Turin city. A total of 120 samples were taken during 10 consecutive d (24 h each) each month. Air was sampled at heights of 1.5 m and 2 m from the 101
I
I
Table 1.-Atmospheric
Concentrations of V H H @/m3) in Some Urban and Rural Sites Urban
VHH
1
Chloroform 1,l.l-Trichloroethane 1,1,2-trichloroethylene Tetrachloroethylene
0.68* 11 3.8 11.5
Rural
2
3
4
5
6
7
8
9
10
0.06t 1.4 0.35 4.6
N.M. 6.2 8.4 12.9
0.18* 5.85 N.M. 2.4
N.M. 14.2 6.4 12.2
0.05t 0.05 0.08 0.69
0.15* 1.13 0.09 0.11
N.M. 0.86 N.M. N.M.
0.06* 0.72 N.M. N.M.
N.M.' 1.2 0.32 1.0
-
Downloaded by [New York University] at 15:02 04 May 2015
Notes: 1 F r a n k f ~ r t , '2~ = New Jersey (U.S.A.),9 3 = Milan,I4 4 = California,' 5 = Torino," 6 = Devils Lake, North Dakota , ~ 10 = Susa (Turin)." N.M. = not measured. Each VHH con(U.S.A.),' 7 = Azorre, Portugal,' 8 = South P01e.l~9 = B e r m ~ d aand centration reported resulted from 4-6 h of sampling (n = 10-50). *Data are expressed as arithmetic means. tData are expressed as arithmetic mean of day and night median.
curb. Sampling and analytical techniques employed and quality control procedures have been described in a previous paper.' Meteorological parameters. A private company measured meteorological variables at the same rneteorological station used for measurements of atmospheric pollutants. Meteorological measurements were conducted during the same times as were the atmosphere pollutants. Meteorological variables included relative humidity (RH), temperature on ground (TG), solar irradiation (SI), and wind speed (WS). The mean value for nitrogen monoxide (NO) (24-h data) for each day (10 dlmo) was calculated. Indoor/outdoor measures. The relationship between indoor and outdoor concentrations of VHHs has been studied by sampling indoor (e .g., bedroom, bathroom, kitchen, etc.) and outdoor (i.e., outside the same flat) air at eight private apartment buildings located in the center of Turin. In these apartments, an average of 1 person lives in an area of 25-35 m2 (e.g., 3-4 persons in 80-120 m2). A measurement was made for 6 h (during the night, morning, and afternoon) for both indoor and outdoor air; a total of 31 measurements were made during the winter (1987/1988), and 28 were completed during the summer (1988). Blood. Blood samples were collected in 10-ml Vacutainer tubes (Becton-Dickinson, Ref. no. 606480; sterile, sodium heparin) from 15 males and 15 females during each of the 12 mo. These individuals were chosen randomly from blood donors who resided in Turin. Whole-blood samples were analyzed within 2-3 h after blood was collected (our storage test shows that VHH concentrations are stable up to 24 h). The blood analyses for VHHs were conducted by gas chromatography (head space technique) using an EC detector.' Values were determined by comparison to a curve obtained by standard addition techniques employing chloroform, l,l,l-trichloroethane, carbon tetrachloride, 1, I ,2-trichloroethylene, and tetrachloroethylene (concentrations added: 0.25-4 pdl) in pooled blood. Quality control of all materials used to collect and analyze blood was achieved by rinsing same with hexane and subsequent GC analysis. Identification of 102
chemicals was determined by assessing retention times with different columns: DB1, DB208, DB210 megabore columns (0.53-mm internal diameter [ID]), and with DB624 and DB5 capillary columns (0.25-mm ID) (J&W Scientific, Folson, CAI. The length of columns were 30 m and the thickness of the film was 1 pn. Quality control was maintained by analyzing a standard sample 20 times. The averages, standard deviations, and coefficients of variation are shown in Table 2.
ResuIts The total concentrations of VHHs in the atmosphere are shown in Figure 1. Each bar represents the mean of ten 24-h determinations measured each month for the five chemicals considered. During October 1987 through March 1988, the median was 18.1 pg/m3 (41-43 = 11.9-30.3 pg/m3), whereas during April through September 1988, the corresponding values were 12.02 pg/m3 (Q1-Q3 = 8.21-17.19 pg/rn3),. Concentrations of each VHH are shown in Figure 2. 1,l,l-Trichloroethane was found in the highest concentration, followed by tetrachloroethylene and 1,1,2-trichIoroethylene. Chloroform and carbon tetrachloride were present in much lower concentrations. The averages and ranges of atmospheric VHH concentrations during the 6 cold mo and 6 warm mo are reported in Table 3. The average concentration of VHHs observed during a "typical" week are shown for the cold and warm seasons. An obvious decrease occurred in the concentration of VHHs on Saturday and Sunday (Fig. 3).
Table 2.-Variation
Coefficients in Control Blood Samples' Mean (pg/l) SD
VHH Chlorforrn 1,1,1 Trichloroethane Carbon tetrachloride 1,1.2-Trichloroethylene Tetrachloroethylene
I
*Peak height; n
=
20.
9.05 17.08 28.53 9.03 10.08
1.68 4.19 4.04 1.99 2.67
cv
(010)
19 24 14 22 25
I Archives of Environmental Health
OCT
I)ov
DEC
JAN
FEE
)#R
APR
I#Y
JUL
JUN
AUC
SEP
Downloaded by [New York University] at 15:02 04 May 2015
Fig. 1. Total atmospheric concentrations of VHHs (Turin, Italy; 1987/1988).
m CHLOROFORM 0 1,I, 1,-1RI CHLOROETHANE
16 r
14
--
12
--
18
--
8
--
2
E
CnRBDN TETRllCHLORIDE
0
1,1,2.-IRICHLOROEIHYLENE
0 IEIMCHLOROETHY LENE
~
:j j::j::
:j j:
::
OC1
W
DEC
Fig. 2. Atmospheric concentrations of specific VHHs in Turin, Italy (1987/1988).
Table 3.-Atmospheric Concentrations of VHHs During October 1987-March 1988 (Cold Months) and April-September 1988 (Warm Months) @g/m3) Cold months
Chloroform 1,l,l-Trichloroethane Carbon tetrachloride 1,1,2-Trichlorcethylene Tetrachloroethylene
March/April 1990 [Vol. 45 (No.211
Warm months
Mean @cg/rn’)
Range
Mean @cg/m’)
Range
0.83 9.60 0.49 5.74 8.70
0-1.98 4.51-14.7 0.22-0.82 2.28-9.6 3.56-1 2.16
0.14 4.1 0.47 3.14 4.75
0-0.49 2.61-6.4 0.25-0.92 1.61-4.23 2.65-7.77
103
48
E COLD SECISON
0 ClCIRM SEASON
38
28
Downloaded by [New York University] at 15:02 04 May 2015
la
a Fig.
HON
TUE
i
UED
THU
FRI
SCIT
SUN
“Typical week” patterns of V H H concentrations in air (Turin, Italy).
Spearman’s correlation coefficients (rs) are reported in Table 4 for VHH concentrations vs. meteorological parameters and NO during the cold and warm seasons. Aside from the positive correlation between NO and the single VHH or the corresponding sum, no other parameter is correlated with VHH concentrations during either period of the year. The relationship (i.e., correlation coefficients) between VHHs and NO concentrations that were determined for each month (i.e., 10 d) from October 1987 to September 1988 i s provided in Table 5. Table 6 provides medians and ranges of indoorloutdoor atmospheric contamination ratios for total VHHs,
1 ,l,l-trichloroethane and tetrachloroethylene. The indoor/outdoor air contamination ratio was higher in winter than in summer. Ratios were not calculated for chloroform and carbon tetrachloride because some measurements were below the detection limit or were absent. The results of the analyses of blood for VHHs are shown in Table 7. No samples were collected during October 1987 and August 1988. The sum of VHHs shows a highly statistical difference between the two seasons. During the winter, chloroform, 1,1,1-trichloroethane, and often 1,1,2-trichloroethylene and tetrachloroethylene were present; during the summer, however, only l,l,l-trichloroethane was found.
Table 4.4pearman’s Correlation Coefficients (rs) between Atmospheric V H H Concentrations and Nitrogen Monoxide and Meteorological Parameters
Meteorological parameters
Total VHHz Cold Warm season season
NO
+ 0.40
+ 0.64
R.H.
-0.18 + 0.08 + 0.37 -0.11
- 0.02
T.G. S.I. W.S.
-0.25 -0.iS -0.28
1,1,1 -Trichloroethane
Cold season
Warm season
10.38 -0.21 + 0.05 +0.36 -0.13
+0.41
-0.10 - 0.03 - 0.04 - 0.36
1,1,2-TrichIoroethylene Cold Warm season season
+ 0.34 -0.15 + 0.05 +0.37 - 0.09
+ 0.62 - 0.07 - 0.32
-0.17 -0.28
Tetrachloroethylene Cold Warm season season
+ 0.47 -0.14 +0.15 +0.34 -0.12
+0.57 + 0.04 -0.20 -0.17 - 0.23
nitrogen monoxide, R.H. = relative humidity, T.G. = temperature on ground, 5.1. = solar irradiation, and W.S. = wind speed. Measurements during cold season occurred in 1987-1988 ( n = 60); during the warm season, measurements were taken 60). in 1988 (n
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Archives of EnvironmentalHealth
tinuousness of the data measured are considered, and in view of the fact that there are no analogies with other studies. This envi ronmental observation becomes important when considering the next possible impact of the new E.E.C. guidelines that ban leaded gasoline (E.E.C. N.L. 96/25, 201311985). When Italy accepts and enforces this E.E.C. directive in 1991, this should result in a subsequent reduction of VHHs in the atmosphere.’ During the winter, the VHH indoorloutdoor atmospheric contamination ratio (Table 6) shows a greater role of indoor air in human intake, probably as a consequence of the limited air exchange from indoor to outdoor and vice versa. Therefore, the indoor human environment might represent another source of VHHs (or at least some .of them) in the air, especially during the winter. Indoor air exposure, especially during the winter, i s another important factor in total human intake of VHHs, because it has been calculated that humans spend about 80% of their time indoor^.^ Furthermore, the blood concentration of VHHs confirms that there is a higher human intake of VHHs during the winter (Table 7). Overall, blood concentrations of VHHs-particularly in summer-were low, and a more detailed epidemiological analysis could not be performed. Neverthelss, the VHH blood concentrations measured may be intepreted as a specific biological marker of human exposure to the complex environmental pollution with these chemicals. The parallels between VHH concentrations in air and blood relative to cold and warm seasons have not been observed previously. Other studies on VHHs were focused on experimental exposures or on the relationship between these biological markers and industrial exposures. Moreover, the study of these specific biological markers is of importance for public health because (a) several of these chemicals appear to have
Table 5.-Spearman‘s Correlation Cdicients (rs) between VHHs and Nitrogen Monoxide from October 1987-September 1988. Month October November December January February March
Month
+ 0.68 + 0.83 + 0.83 + 0.66
+ 0.67 + 0.43
April May June July August September
+0.59 + 0.44 + 0.39 + 0.52 + 0.35 + 0.85
I
‘Samples were taken 10 dlmo.
Downloaded by [New York University] at 15:02 04 May 2015
Discussion Apart from the January data, Figure 1 shows that a “primary pollutant pattern’’ existed during the winter. In summer, the trend was more irregular, and concentrations varied considerably around a mean value that was lower than during the winter. Concentrations decreased on the weekend in the cold season (Fig. 31, which may confirm the primary source of VHHs: there are few cars in the area on Saturdays and Sundays (with a consequent decrease of automotive exhaust emission) and a higher ”mixing ratio” during the warm season. A lack of correlation between meteorological parameters and atmospheric VHH concentrations was observed (Table 4). A good correlation was found during the entire year between VHHs and NO, which suggests a similar origin and environmental behavior (Table 5). Monitoring of the atmosphere for VHHs during 1 yr appears important when the completeness and con-
Table 6.-Correlation (Mann-Whitney Test) between Medians of Indoor/Outdoor Atmospheric Concentration Ratios ocg/m3) in Winter and Summer Winter (n
-
31)
Median
Range
VHHs
2.69
l,l,l-Trichloroethane
2.62
Tetrachloroethylene
2.15
1.85-29.45 p 1 .00-7.52 p 0.59-30.91 p
Table 7.-Blood
Summer (n
Range
1.33
0.79-2.75
- .m
-
- 28)
Median
1.105 ,0024 1.38 ,0281
0.68-2.27 1.03-4.22
Concentrations of VHHs among Residents in Turin City @@I) n
Mean
SD
Range
Median
Winter
133
1.33
1.66
0.02-9.56
0.71
Summer
131
0.46
0.87
0.00-6.82
0.22
p (Mann-Whitney)
