Comparison of selected volatile organic compounds during the summer and winter at urban sites in New Jersey

The Science o f the Total Environment, 38 (1984) 259--274 Elsevier Science Publishers B.V., Amsterdam -- Printed in The Netherlands

259

COMPARISON OF SELECTED VOLATILE ORGANIC COMPOUNDS DURING THE SUMMER AND WINTER AT URBAN SITES IN NEW JERSEY

RONALD

HARKOV

Office of Science and Research, N e w Jersey Department of Environmental Protection, C N 402 Trenton, N J 08625 (U.S.A.) BARBARA

KEBBEKUS

and J O S E P H W. B O Z Z E L L I

Department of Chemical Engineering and Chemistry, N e w Jersey Institute of Technology, Newark, N J (U.S.A.) P A U L J. L I O Y and J O A N D A I S E Y

Institute of Environmental Medicine, N e w York University Medical Center, N e w York, N Y (U.S.A.)

(Received October 4th, 1983; accepted February 14th, 1984) ABSTRACT This paper presents a comparison of summer and winter levels of twenty-five selected volatile organic compounds (VOC) measured as part of the New Jersey project on Airborne Toxic Elements and Organic Substances (ATEOS). Most of the selected VOC were found in the range of 0.01--1.00 ppbv, with the exception of toluene (1--5 ppbv) and benzene (1--3 ppbv). However, peak levels of many compounds increased more than 100 fold during specific pollutant episodes. Generally, VOC levels were higher in the winter than the summer. Day to day variations of measured aromatic VOC showed significant correlations at each site suggesting an area source (motor vehicles), while there was little relationship between chlorinated species. During summer oxidant episodes, selected VOC increased from 2--10 times at Newark and Elizabeth, but not at Camden. In the winter, nocturnal temperature inversions caused levels of selected VOC to increase from 2--3 times seasonal average at all sites.

INTRODUCTION T h e c h a r a c t e r i z a t i o n o f organic c o m p o u n d s in t h e a t m o s p h e r e is an i m p o r t a n t r e q u i r e m e n t in t h e s t u d y o f the r e l a t i o n s h i p b e t w e e n h u m a n h e a l t h a n d air p o l l u t i o n . Organic air p o l l u t a n t s are i m p o r t a n t because t h e y t e n d to have a high level o f biological activity [ 1 - - 3 ] a n d because t h e f o r m a t i o n o f p h o t o c h e m i c a l s m o g is d e p e n d e n t o n a n d p r o d u c e s a large 0048-9697/84/$03.00

© 1984 Elsevier Science Publishers B.V.

260 number of organic atmospheric contaminants [4]. Volatile organic compounds (VOC) include a large number of pollutants which are animal/human carcinogens and which are photochemically reactive [3, 4]. As discussed here VOC include those organic compounds with a vapor pressure greater than or equal to 0.02 psi (1.0 mm). The study of selected VOC has been initiated in a number of recent research programs [ 5--11 ]. While these efforts have added much information to the air pollution literature about VOC concentrations in ambient air, few data have been gathered to examine the daily and seasonal variations of the pollutants and their relationship to other contaminants. Selected VOC were measured at three urban sites in New Jersey during the summer (1981) and winter (1982) seasons to: (1) characterize the atmospheric concentrations and variability of these contaminants (2) study the interrelationships between VOC and other non-criteria pollutants (3) establish VOC source relationships and (4) develop a monitoring strategy for VOC that is compatible with the health risks associated with the pollutant(s). The VOC selected for measurement as part of the New Jersey Program on Airborne Toxic Elements and Organic Substances (ATEOS) were evaluated for known animal/human carcinogenicity, use patterns in New Jersey, current or proposed regulation, future air quality trends and available monitoring and analytical technology [11, 24]. Of all compounds selected for the VOC portion of the ATEOS project, only nitrobenzene and p-dichlorobenzene do n o t have vapor pressures greater than or equal to 0.02 psi.

METHODS

Sampling Although the sampling protocols and VOC sampler have been described in detail [11--13], a brief description will be given. In the ATEOS program VOC samples were collected on a continuous 24-h basis, seven days per week for six weeks during the summer and winter at three urban sites (Newark, Elizabeth and Camden). The summer 1981 campaign included the time period from 7/6--8/14 while the winter 1982 effort was from 1/18--2/26. The VOC were collected using a sampier developed by the New Jersey Institute of Technology--Air Pollution Research Laboratory (NJIT--APRL). These samplers included a low-volume diaphragm p u m p (Gillian-10020), equipped with needle valves and a pressure regulator to maintain constant pressure across the needle valves. The flow rates were measured by a calibrated rotometer. A sodium thiosulfate treated glass-fiber pre-filter was used to reduce any ozone reactions on the adsorbent and was placed in f r o n t o f two side-by-side stainless-steel adsorbent cartridges containing Tenax-GC and Spherocarb respectively. Ambient air was p u m p e d through the cartridges at 1 0 - - 1 5 m l / m i n for 2 4 h . A series of test runs ( N - - 120) revealed that the average deviation in flow rates was less than 9%.

261

Site description The selection process for monitoring locales used in the ATEOS program was discussed in a previous report [12]. The VOC portion of the ATEOS project did not include a background location because of our previous experience of sampling in rural areas in NJ [10] and because of cost considerations. The Newark site is at the interface of a highly industrialized area and a residential c o m m u n i t y ; petrochemical, inorganic and organic chemical, leather tanning, truck and auto painting, and precious metal facilities are located within 1 km of the site. Refineries, petrochemical and commercial areas are adjacent to the c o m m u n i t y surrounding the Elizabeth site while the Camden locale is influenced b y a variety of industries located along the Delaware River and the Philadelphia airshed [12, 25]. For additional information on identified local VOC sources at the three urban sites, reference should be made to previous publications from the ATEOS project [12, 14, 16, 2 5 ] . Analysis Samples were thermally desorbed from the Tenax-GC (at 250°C) and Spherocarb (at 350°C) traps into an evacuated 10 ml stainless steel cylinder fitted with a stainless steel bellows valve. For the Tenax samples analysis was done on a Varian 3700 gas chromatograph equipped with a fused silica SP2100 column. A gas sampling valve introduced a 2 ml sample which is focused at the head of the column at - - 9 0 ° C ; column temperature is then raised to 140°C in 45 min. The effluent was split sending 90% to the FID for quantification and 10% to ECD for qualitative confirmation of the halogenated hydrocarbons. The detector signals were integrated and the sample concentrations were calculated using a Spectra-Physics Model 4000 multichannel integrator. All recorder o u t p u t s were manually compared with the Spectra-Physics calculations to assure proper qualitative identification. Spherocarb samples were analyzed only for vinyl chloride on a Tracor gas chromatograph using a temperature program which starts at 40°C and rises to 300°C using a 1/18in. × 39in. length carbosieve-B/60/80 mesh column. The effluent was m o n i t o r e d with FID. Selected samples were analyzed on a Varian MAT 44 quadrupole mass spectrometer equipped with a fused silica SP2100 GC column and a liquid nitrogen cryofocusing trap. A more complete discussion of the analytical m e t h o d can be f o u n d in Bozzelli and Kebbekus [13]. Data assurance All sampling and analysis in the ATEOS program has been subjected to a rigorous quality assurance/quality control (qa/qc) plan [ 1 4 ] . The field qa/qc plan for the VOC included calibration of the samplers, training personnel to use the samplers, checking daily flow rates and flow stability studies. The laboratory plan included analysis of spiked samples, sample trap blanks, use of quantitative and qualitative standards, trap cleaning, recovery and

262 break-through studies. Approximately 30 side-by-side duplicate samples were analyzed for the 18 most frequently detected VOC. The overall precision of the entire sampling and analytical m e t h o d was + 48% for an average VOC concentration of 0.67 ppb. During the summer of 1981, mass spectrometric analyses were conducted on more than 15% of the Tenax-GC cartridges and on approximately 10% of the Spherocarb (vinyl chloride only) cartridges. In the winter of 1982 campaign, mass spectrometric analyses were conducted on 25% of the Tenax-GC cartridges and 12% of the Spherocarb cartridges.

RESULTS

The geometric concentrations for 25 selected VOC in NJ during the summer and winter are shown in Table 1 and Table 2, respectively. The lower limit of detection for all compounds was 0.005 ppbv, while the quantitation limits w e r e 0 . 0 5 ppbv for aromatics and 0.10 ppbv for the chlorinated VOC. Five to six compounds were generally f o u n d in unquantifiable amounts during the two monitoring campaigns, while 2--5 pollutants were quantified in 20--75% of the samples and 15--17 substances were quantified in 75% of the samples. The mass spectrometric analysis verified the presence of the selected pollutants detected by GC in virtually 100% of the samples. Carbon tetrachloride and ethylene dibromide proved to be particularly troublesome during this study. Laboratory recovery studies indicated that these compounds had a recovery of only about 40% from Tenax-GC cartridges, as opposed to 80--110% for the remaining compounds. It is also known t h a t Tenax-GC is n o t the ideal adsorbant for lightweight halogenated hydrocarbons [28, 29]. Thus the levels reported here for carbon tetrachloride and ethylene dibromide are likely to be underestimates of the actual concentrations in NJ. Generally, VOC levels were highest in Newark followed by Elizabeth and Camden. However, each site was influenced by particular VOC as evidenced by the relatively high concentrations recorded in these locales. Newark had the highest levels of toluene and trichloroethylene, Camden of m e t h y l e n e chloride and vinylidene chloride and Elizabeth of b e n z e n e . The aromatic VOC (benzene, toluene, o, p, m-xylenes, ethylbenzene and styrene) were generally f o u n d to have the .highest concentrations and frequency of occurrence. Of the chlorinated VOC measured in the ATEOS program vinylidene chloride, methylene chloride, trichloroethylene, perchloroethylene and chlorobenzene were f o u n d to have the highest concentrations. During the winter season chloroform could be included in the group of chlorinated organics f o u n d in high concentrations. For illustrative purpose, the day-to-day variations of benzene for all sites during both seasons are shown in Figs. 1 and 2. Generally, the aromatic compounds had similar day-to-day trends within a site. This pattern of covariation among the selected aromatic VOC occurred during both seasons and at all sites. Spearman-rank correlation matrices (Table 3) show that these pollutants were highly correlated at each site during both seasons. Additional

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similarities were n o t e d for day-to-day trends in aromatic VOC between the three urban areas. These observations cont rast with the chlorinated VOC which were p o o r l y correlated among themselves, Spearman-rank correlation coefficients were ~ 0.40 at all sites during b o t h seasons.

267 TABLE 3 SPEARMAN-RANK CORRELATION MATRICES FOR SELECTED AROMATIC VOC (Summer 1981 and Winter 1982) Benzene

Toluene

mdg-Xylene

Ethylbenzene

1.0 1.0

0.83 0.50 a 1.0 1.0

0.72 0.66 0.90 0.71 1.0 1.0

0.73 0.57 0.86 0.69 0.95 0.93 1.0 1.0

S'81 W'82 S'81 W'82 S'81 W'82 S'81 W'82

1.0 1.0

0.89 0.50 a 1.0 1.0

0.79 0.57 0.88 0.71 1.0 1.0

0.79 0.55 0.88 0.71 0.99 0.99 1.0 1.0

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1.0 1.0

0.78 0.62 1.0 1.0

0.66 0.65 0.79 0.61 1.0 1.0

0.66 0.62 0.81

Camden

Benzene Toluene m~o-Xylene

Ethylbenzene

S'81 W'82 8'81 W'82 S'81

W'82 S'81

W'82

Elizabeth

Benzene Toluene m~o-Xylene Ethylbenzene Newark

Benzene Toluene muo-Xylene Ethylbenzene

0.66

0.99 0.92 1.0 1.0

ap ~> 0.001, N = 30 -- 38. During the summer, the meteorological conditions associated with peak c o n c e n t r a t i o n s o f V O C also c o r r e s p o n d t o high levels o f 0 3 , SO4 2- a n d e x t r a c t a b l e p a r t i c u l a t e organic m a t t e r . F o r t h e p e r i o d s o f s t a g n a t i o n ( 7 / 1 9 - - 2 1 , 8 / 1 0 - - 1 3 ) a n d w i t h t h e p r e s e n c e o f a B e r m u d a high p r e s s u r e s y s t e m ( 8 / 3 - - 5 ) [ 1 5 ] p e a k V O C w e r e as m u c h as 2 - - 1 0 t i m e s the seasonal averages. I n a d d i t i o n , t h e average c o n c e n t r a t i o n s o f 6 s e l e c t e d V O C a t N e w a r k a n d E l i z a b e t h sites i n c r e a s e d b y as m u c h as 155% d u r i n g t h e s e e p i s o d e s ( T a b l e 4). T h e C a m d e n site did n o t s h o w a general increase in V O C levels d u r i n g t h e t h r e e episodes. P o l l u t i o n e p i s o d e s d u r i n g t h e w i n t e r season o c c u r r e d m o r e f r e q u e n t l y ( 1 / 1 9 , 1 / 2 8 - - 2 9 , 2/5, 2 / 1 1 , 2 / 1 5 ) b u t w e r e o f s h o r t e r d u r a t i o n t h a n t h e p r e v i o u s s u m m e r . N o c t u r n a l t e m p e r a t u r e inversions c o u p l e d w i t h l o w v e l o c i t y SW w i n d s c a n a c c o u n t f o r t h e general b u i l d u p o f p o l l u t a n t s d u r i n g t h e w i n t e r in N e w J e r s e y [ 2 7 ] . I n a d d i t i o n , fossil fuel c o m b u s t i o n is

268 TABLE 4 LOCALLY ACCUMULATED EPISODES (in ppbv)

VOC

DURING

Newark

Methylene chloride Trichloroethylene Perchloroethylene Benzene Toluene m~v-Xylene

SUMMER

REGIONAL

Elizabeth

OXIDANT

Camden

EP a

SWG b

EP

SWG

EP

SWG

0.56 0.69 0.56 1.57 11.89 1.86

0.35 0.50 0.45 1.03 4.65 0.99

0.27 0.70 0.70 1.84 6.47 1.51

0.23 0.27 0.31 1.05 2.89 0.75

0.48 0.23 0.26 2.82 1.80 0.43

0.72 0.21 0.24 1.11 1.82 0.49

aEp: episode periods associated with regional oxidant (7/10--21, 8/3--5,8/10--13), geometric mean (N ----10). SWG: six week geometric mean (N ----22--28).

at a peak during the winter season, and has a substantial influence on the l e v e l s o f m a n y p o l l u t a n t s in N J . W h i l e p e a k V O C l e v e l s i n c r e a s e d b y as m u c h as f i v e t i m e s , t h e m e a n e p i s o d i c l e v e l s o f s e l e c t e d V O C i n c r e a s e d f r o m 4 / 3 t o 4 t i m e s t h e g e o m e t r i c m e a n w i n t e r l e v e l s ( T a b l e 5). T h e s e l e c t e d V O C a c c u m u l a t e d in t h e a t m o s p h e r e a t all t h r e e s i t e s d u r i n g t h e w i n t e r as o p p o s e d t o i n c r e a s e s o b s e r v e d o n l y a t N e w a r k a n d E l i z a b e t h in t h e s u m m e r . T h e l a r g e s t w i n t e r e p i s o d i c i n c r e a s e in s e l e c t e d V O C o c c u r r e d a t t h e N e w a r k s i t e .

TABLE 5 LOCALLY ACCUMULATED VOC DURING WINTER POLLUTION EPISODES (in ppbv) Newark

Methylene chloride Trichloroethylene Perchloroethylene Benzene Toluene m,p-Xylene

Elizabeth

Camden

EP a

SWG b

EP

SWG

EP

SWG

2.7 0.85 0.87 3.65 14.04 3.17

0.68 0.59 0.46 2.61 4.93 1.79

1.18 0.82 0.77 5.23 7.40 2.71

0.87 0.46 0.44 3.11 4.09 1.10

2.0 0.59 0.47 4.83 4.51 1.89

1.19 0.32 0.29 2.82 3.38 0.90

aEp: episodic periods during nocturnal temperature inversions (1/19, 1/28--29, 2/5, 2/11, 2/15), geometric mean (N = 6). bSWG: six-week geometric mean (N = 15--28).

269

DISCUSSION A r o m a t i c VOC The levels of aromatic VOC reported here are consistent with those reported in the recent air pollution literature for urban air (Table 6). Motor vehicles and gasoline loading and unloading are the major source of hydrocarbon emissions in urban areas and aromatic hydrocarbons represent a significant fraction of the tailpipe and evaporative emissions from these sources (Table 7). Comparison of the proportions of toluene: benzene: p-xylene: ethylbenzene, indicates t h a t m o t o r vehicle exhaust and evaporative emissions are making a major contribution to ambient levels of these pollutants at the Newark and Elizabeth sites during the 1981 summer. At the Camden site, it was hypothesized that urban plume transport from the Philadelphia airshed coupled with photochemical reactions were the most important determinants of the atmospheric concentrations of the selected aromatic VOC [16]. The evidence to support this hypothesis is (1) on 78% of the days during the summer of 1981 campaign prevailing winds were from the westerly direction for at least 12 h / d a y at the Camden site, (2) published atmospheric reaction rate estimates suggest that these aromatic compounds are preferentially degraded in the following order m ~ - x y l e n e ~ ethylbenzene ~ toluene ~ benzene, although actual atmospheric half-lives are uncertain [6, 19, 26], (3) a survey of industries in the Camden area did not identify any major benzene users or manufacturers within a 4 km radius from the monitoring site. Thus the greater proportion of benzene at this site does n o t appear to be related to localized point sources. It should be n o t e d that a number of oil refineries are located southwest of the Camden site; however, the closest facility is more than 15 km away. Also, the Elizabeth site is within 3 km of the largest refinery in NJ, y e t the results from this locale do n o t appear to reveal the influence of this source category on the relative proportions of these aromatic VOC during the summer season. A comparison of the ratio of selected aromatic VOC in automobile exhaust, combined exhaust and evaporative emissions and tunnel atmospheres indicates that additional source contributions influence the levels of these pollutants at the three sites during the winter (Table 7). The most pronounced shift is the increased proportion of benzene f o u n d during this season. An initial hypothesis developed from this data assessment is that residential No. 2 oil combustion, which is a major f u e l u s e d in NJ during the heating season, is contributing to the shift in the ratio of the various aromatic VOC species. Additional evidence exists in support of this hypothesis in that oil combustion in stationary boilers produced a 2:1 ratio of benzene to toluene in the flue gases [20]. As shown in Table 8, toluene, benzene, p-xylene and ethylbenzene are significantly correlated with both Pb and Ni, tracers for m o t o r vehicle and residential oil combustion respectively. The poorest relationship occurs at the Camden site and m a y be a function of an aged-pollution plume from the Philadelphia airshed impacting this site. The prevailing winds at the Camden site were from the westerly direction for

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271 TABLE 7 COMPARISON OF RATIOS OF SELECTED AROMATIC VOC FROM AUTOMOTIVE EXHAUST, EXHAUST AND EVAPORATION AND TUNNEL ATMOSPHERE WITH THOSE REPORTED FOR THREE URBAN NJ LOCATIONS Site

Toluene : Benzene : mJ~-Xylene : Ethylbenzene

Automotive exhaust Automotive exhaust and evaporation Tunnel Summer 1981 Newark Elizabeth Camden Winter 1982 Newark Elizabeth Camden

Reference

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TABLE 8 SPEARMAN-RANK CORRELATION MATRICES FOR SELECTED AROMATIC A N D T W O T R A C E E L E M E N T S F O R W I N T E R 1982 C A M P A I G N

Sites Newark Pb Ni Elizabeth Pb Ni Camden Pb Ni

VOC

Toluene

Benzene

m~p-Xylene

Ethylbenzene

0.65 0.65

0.63 0.68

0.68 0.60

0.81 0.67

0.56 0.48 a

0.69 0.51

0.71 0.53

0.72 0.54

0.67 0.47 a

0.42 a 0.59

0.52 0.39 a

0.43 a 0.26 a

ap > 0.001. 67% of the d a y s for at least 1 2 h / d a y d u r i n g the w i n t e r of 1982. T h e C a m d e n site is also t h e f u r t h e s t f r o m m a j o r r o a d w a y s , t h u s t h e p o o r P b c o r r e l a t i o n m a y be a f u n c t i o n of this aspect of this locale. T h e i m p a c t of P h i l a d e l p h i a u r b a n p l u m e o n t h e p o l l u t i o n levels r e c o r d e d a t t h e C a m d e n site, will b e t h e s u b j e c t o f f u t u r e a n a l y s e s f r o m t h e A T E O S d a t a set. Chlorinated VOC T h e c h l o r i n a t e d V O C a p p e a r t o b e m i n o r c o m p o n e n t s o f t h e air q u a l i t y a t t h e u r b a n s i t e s i n c l u d e d i n t h e A T E O S p r o g r a m . T h i s o b s e r v a t i o n is c o n s i s t e n t w i t h t h e r e s u l t s o f S i n g h e t al. [ 7 ] a n d P e l l i z z a r i [ 8 ] . W h i l e e a c h o f

272 the monitoring sites was influenced by chlorinated VOC, the daily variation of these pollutants was poorly coupled with the other contaminants measured in this study, indicating the likelihood t h a t localized point sources are the primary contributors to the ambient levels of these pollutants. In addition, these chlorinated compounds are poorly correlated with each other at a given site (rsp ~< 0.40). This result is n o t entirely unexpected since chlorinated VOC are used widely in a variety of industrial/commercial processes. Only those compounds which are used extensively by a large number of industrial/commercial enterprises were f o u n d in relatively high frequencies and concentrations. These compounds are vinylidene chloride, methylene chloride, trichloroethylene and perchloroethylene. Vinylidene chloride is primarily used in production of various co-polymers c o m m o n l y known as "Sarans" [21]. Methylene chloride is used as a solvent in paint remover, aerosol sprays, metal degreasing and plastics production [22]. Of the trichloroethylene 90% is used for degreasing and cleaning metals, while most of the perchloroethylene is used in textile cleaning [ 21]. The vinylidene chloride results from this study are somewhat of a surprise. Singh et al. [6, 7, 24] have identified vinylidene chloride in a number of urban areas t h r o u g h o u t the U.S. in the 1--50 ppt range, which is lower than reported here. In the present study, mass spectrometry positively identified vinylidene chloride in all samples in which gas chromatography detection was also noted. A statewide survey of industries in NJ has only been successful in locating three small to intermediate users of vinylidene chloride in the state. Thus we have no satisfactory explanation for the presence, in relatively high concentrations, of vinylidene chloride in the NJ urban atmosphere. Vinylidene chloride is formed commercially from the dehydrochlorination of 1,1,1-trichloroethane or 1,1,2-trichloroethane. Both of these substances are high use c o m p o u n d s in NJ, with 1,1,1-trichloroethane occurring in the 1--5 ppb range, in ambient air [30]. There thus remains the possibility that vinylidene chloride is formed either in the atmosphere or on Tenax-GC, as an artifact, from 1,1,1-trichloroethane dehydrochlorination. However, 1,1,1trichloroethane is t h o u g h t to be recalcitrant in the atmosphere [6], thus leaving the vinylidene chloride issue uncertain. Obviously, additional studies are needed to resolve this problem. TABLE 9 PEAK LEVELS OF SELECTED CHLORINATED VOC FOUND AT THREE URBAN NJ SITES DURING THE WINTER (1982) SEASON (ppbv) Pollutant

Newark

Elizabeth

Camden

Ethylene dichloride Chloroform 1,1,2-trichloroethane

1.7 36.0 12.0 0.7

1.9 10.1 18.1 1.4

5.3 77.4 16.0 2.8

Chlorobenzene aDate of peak value.

(1/19) a (1/29) (2/14) (2/3)

(1/18) (1/30) (2]28) (1/28)

(1/26) (2/2) (2/2) (2/16)

273 While the r e m a i n i n g c h l o r i n a t e d c o m p o u n d s are generally m i n o r c o m p o n e n t s o f u r b a n air q u a l i t y o f the three A T E O S sites, t h e y o c c a s i o n a l l y b e c o m e a m a j o r f r a c t i o n o f the selected V O C m e a s u r e m e n t s . S o m e e x a m p l e s o f p e a k w i n t e r c o n c e n t r a t i o n s o f selected c h l o r i n a t e d VOC are s h o w n in Table 9. These peak c o n c e n t r a t i o n s were generally p o o r l y c o r r e l a t e d (rsp~0.40) with the m e t e o r o l o g i c a l variables a n d o t h e r air p o l l u t a n t s m e a s u r e d d u r i n g t h e A T E O S project. In t o t o , these o b s e r v a t i o n s suggest t h a t w h e n o n e is i n t e r e s t e d in s t u d y i n g the h e a l t h risks associated with c h l o r i n a t e d VOC, m e a s u r e m e n t s s h o u l d be t a k e n near s u s p e c t e d local p o i n t sources as o p p o s e d to c o l l e c t i o n in c o n j u n c t i o n with o t h e r a m b i e n t air q u a l i t y parameters.

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