(2) Niki, H.; Maker, P. D.; Savage, C. M.; Breitenbach, L. P. Chem.
Phys. Lett. 1978,55,289. (3) Graham, R. A.; Winer, A. M.; Pitts, J. N. Jr. Chem. Phys. i e t t .
1977.51.215.
(4) Uselman, W. M.; Levine, S. Z.; Chan, W. H.; Calvert,J. G.; Shaw, J. H. “Nitrogeneous Air Pollutants”; Grosjean, D., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; Chapter 2. ( 5 ) Cox, R. A.; Roffey, M. J. Enuiron. Sci. Technol. 1977,11,900. (6) Spence, J. W.; Edney, E. 0.;Hanst, P. L. Chem. Phys. Lett. 1978,
56,478. (7) Sander, S.P.; Watson, R. T. J . Phys. Chem. 1980,84,1664. ( 8 ) Niki, H.; Maker, P. D.; Savage, C. M.; Breitenbach,C. P. Chem. Phys. Lett 1979,61,100. (9) Morel, 0.; Simonaitis, R.; Heicklen, J. Chem. Phys. Lett. 1980, 73, 38.
(10) Ohta, T.; Su, F.; Calvert, J. G.; Shaw, H. J., presented in the
Proceedings of the 14th InternationalSymposium on Free Radicals, Japan, 1979. (11) Heuss, T. M.; Glasson, W. A. Enuiron. Sci. Technol. 1968,2, 1109. (12) Cox, R. A. NBS Spec. Publ. ( U S . )1979, No. 557, Section IV; p 69. (13) Hager, R. N. Jr. Anal. Chem. 1973,45,1131A. (14) Gay, B. W. Jr.; Noonan, R. C.; Bufalini, J. J.; Hanst, P. L. Enuiron. Sci. Technol. 1976,10, 82. (15) Niki, H.; Maker, P. D.; Savage, C. M.; Breitenbach,L. P. “Nitrogeneous Air Pollutants”;Grosjean, D., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; Chapter 1;p 1. Received for reuiew January 2,1981. Reuised manuscript received June 3,1981. Accepted June 19,1981.
Trace Pollutant Concentrations in a Multiday Smog Episode in the California South Coast Air Basin by Long Path Length Fourier Transform Infrared Spectroscopy Ernest0 C. Tuazon, Arthur M. Winer, and James N. Pitts, Jr.” Statewide Air Pollution Research Center, University of California, Riverside. California 92521
A kilometer path length FT-IR study of trace atmospheric pollutants was conducted during the 1978 photochemical smog season in Claremont, CA, a receptor site -30 mi east (and during this study generally downwind) of central Los Angeles. Detailed time-concentration data for 03,PAN, “03, HCOOH, and HCHO, as well as for “3, are reported for October 9-13,1978. This week was characterized by photochemical air pollution episodes of progressively increasing intensities; the maximum O3 concentration increased from 0.16 ppm on Monday, October 9, to 0.45 ppm on Friday, October 13. FT-IR measurements were performed daily for 10-12 h during the October 9-11 period, and data were collected for a continuous 38-h period for the more severe smog episodes of October 1 2 and 13. Maximum concentrations measured on October 13 were as follows: 0 3 , 454 ppb; PAN, 37 ppb; HNO3,49 ppb; HCOOH, 19 ppb; and HCHO, 71 ppb. Ratios of the total concentrations of the gaseous trace pollutants to the corresponding ozone concentration are presented for various averaging periods during this multiday smog episode.
provides in situ, -2-6-ppb detection sensitivities and unambiguous spectroscopic identification for several important oxygenated and nitrogenous pollutants. Our initial studies in 1976 and 1977 (19-22)were conducted in Riverside, CA, a location 60 mi east and generally 6-12 h downwind of the primary emission sources in the CSCAB. These results included the first spectroscopic identification and measurements of HCHO and ” 0 3 in the troposphere, The as well as measurements of HCOOH, PAN, and “3. kilometer path length FT-IR spectrometer was then moved 30 mi upwind, toward Los Angeles, with a view to examining the ambient concentrations of trace pollutants closer to the current epicenter for peak ozone levels during severe smog episodes. We report here measurements a t the Claremont, CA, site (see Figure l),made during the week of October 9-13,1978, a period characterized by photochemical smog episodes of progressively increasing intensity. The measurements included a 38-h continuous monitoring period in which we observed the highest ambient concentrations of 0 3 , PAN, HCOOH, HCHO‘, and H N 0 3 measured to date with our long path length FT-IR system.
Introduction The role of “trace” pollutants such as formaldehyde, formic acid, peroxyacetyl nitrate (PAN), and nitric acid in the chemistry of photochemical air pollution, as well as their potential impacts on humans and vegetation, has been discussed for some two decades (2-9). However, only a limited number of experimental measurements of the ambient concentrations of these species had been made through 1975. These included wet-chemical measurements of formaldehyde and formic acid in the 1950s and 1960s by Altshuller and others (10-12) and spectroscopic measurements of HCOOH and PAN in the early 1970s by Hanst and co-workers (13);Coulometric measurements of “ 0 3 were made in the mid-1970s by Spicer ( 1 4 , 15). The lack of detailed and reliable data on the ambient concentrations of such “noncriteria” pollutants has been a serious deficiency in the inputs to airshed models (26, 27) and has hampered assessments of the health impacts of these components of photochemical air pollution. Therefore, in 1976, we undertook an EPA-sponsored ambient air measurement program in California’s South Coast Air Basin (CSCAB) employing a kilometer path length FT-IR spectrometer originally designed and assembled by Hanst (18).This system 1232
Environmental Science & Technology
Experimental Section During the summer of 1978, the kilometer path length FT-IR facility was installed on the roof of the Jacobs Science Center of Harvey Mudd College in Claremont, CA. Details of its design and operation have been described previously (19-22), and only a brief description will be given here. The system consists of a Digilab Model 296 interferometer (0.5cm-l maximum resolution) interfaced to an eight-mirror, long-path cell with a 22.5-m base path and capable of achieving kilometer path lengths. The cell optics are gold coated for maximum reflectivity in the infrared. Liyuid-nitrogen-cooled detectors equipped with appropriate optical filters were employed: HgCdTe for the 700-2000-~m-~region and InSb for the 2000-3900-~m-~ region. Ambient air was sampled by drawing the air through the cell a t a rate of 330 L s-l for a minimum of 4 min before the start of the measurement. This corresponded to a displacement of the previous cell contents by a minimum of five volumes of fresh sample. Thus, the sample averaging period for these measurements was less than 5 min. A total path length of 900 m and a resolution of 0.5 cm-l were routinely employed. Data collection of 30 co-added interferograms resulting in a 0013-936X/81/0915-1232$01.25/0
@ 1981 American Chemical Society
Table 1. Detection Sensitivities a approx.
compd
measurement t.e,q"e.?cy. cm-3
PAN NHJ
"03
HCHO
Flgure 1. Distribution of lh ozone maxima (ppm) in the California south Coast Air Basin. October 13. 1980 (genwated from Ih averaged ozone maxima reponed by the CaliforniaSoUm Coast Air Ouality Management
District (48)). 0.5-cm-' spectrum took no more than 6 min. I t was established (21,ZZ) that no significant change in the concentrations of the above pollutants took place in the FT-IR cell during this short measurement period. Concentrations were determined from the ratio of the polluted air spectra to clean-air reference spectra (21,ZZ). The absorption frequencies employed for analysis along with typical detection sensitivities are given in Table I. The measurement uncertainties are within the following values: PAN, f 2 ppb; "3, *2 ppb; HCOOH, f 2 pph; HCHO, f4 ppb; f4 ppb. "03,
Results Extended periods of air monitoring were carried out during the week of October 9-13,1978, a period characterized by a
(RTP).
HCOOH
resol~tlOn.
om-' aim-1
9.7
1055 1162 931 967.5 993 896 2779 2781.5 1105
03
...
absorptlvIIIes
-
9
I800
PPb
16d
0.5 0.5
10 3 4 3 4 6 6
70"
0.5
2
27 35 21 124
*See ref 27 and 22for details. aCalcdated in base e. -23 ' C . 760 torr. Measured from the intensity of the 0 branch only.
continuous rise in the daily peak Os readings from 0.16 ppm on Monday, October 9, to 0.45 ppm on Friday, Octoher 13. This pattern typifies, in a more pronounced manner, trends found io a study by the California Air Resources Board (23) of weekend vs. weekday 0 3 levels during the period 19661977: a progressive increase occurs in the average daily maximum 1-h 0 3 concentrations for Sunday to WednesdayThursday-Friday periods, followed hy a decrease on Saturday. Moreover, the severe pollution episodes of October 12 and 13, 1978, appear to constitute an example of stagnant-air events involving pollutant "carryover". The concentrations of 0 3 ,PAN, NHs, HCOOH, and HCHO as a function of time are presented in Tables 11-VI (see paragraph a t the end of the text regarding supplementary material). Measurements during the episodes of October 12 and 13 made for the continuous 38-h period are plotted in Figure 2. Supplemental data on NO, concentrations were also OCTOBER 13, 1978
PACIFIC DAYLIGHT TIME 1400
--1
1-2 2-4 0.5 0.5 0.5
32
OCTOBER 12, 1978c -
801000
2200
0200
0600
1000
1400
1800
1
2200
g
4o
a
60
30 2
40
20
a a
0 I
detection limit at 900-m p d h length.
10
I
z
5
1-
20
10
I
0
-
0
500
50
400
40
B
30
W
g
-z
a
a
300
200
20
IO0
IO
N
8
0
0
z 0
I800
2200
0200
0600
1000
PACIFIC DAYLIGHT TIME loLd:::BER
12, 1978c -
Flgure 2. Time-concentration profiles of
1400
2200
=
0
1
OCTOBER 13. 1978
ozone and other gaseous pollutants present in photochemical smog at Claremont. CA. October 12 and
13,1978.
Volume 15,Number IO. October 1981 1233
Table VII. Daily Average Claremont, CA
a
and Daily Maximum Pollutant Concentrations (ppb) for the 1000-1800-h period in PAN
03
date
HNO3
HCOOH
100[TP]1031 av max
HCHO
av
max
av
max
av
max
av
max
i V
10/9/80 10/10/80
66 79
163 227
2 3
6 14
13
16
23
51
32
30
47
34
124
280
5
13
19
3
5 5 7
18
10/11/80
18 28 30
2
14
23
31
40
29
1O/ 12/80
176
360
22
21
29
5
17
31
52
36
33
10/13/80
227
454
7 17
37
32
49
11
19
49
71
48
39
2
max
a For time blocks with concentrations below detection limits, the figure reported is the average between two values, one with the indeterminate concentrations assumed to be zero, and the other with such concentrations set equal to the established detection limit (Table I) [TP] = [PAN] ["OB] [HCOOH] -t
+
1 HCHO]
obtained on October 13 (Table VI) with a TECO chemiluminescence analyzer. For the particular instrument employed, the NO2 concentrations (Table VI) have been corrected for quantitative interferences (24,25)due t o PAN and "03.
Discussion The results obtained in the present study are consistent with our earlier measurements in Riverside, CA (20-22), suggesting that these data may be generalized with some confidence to other locations in the CSCAB and possibly t o other urban airsheds as well. Principal findings are that the sum of the trace pollutants is significant when compared to ozone and that the ambient concentrations of individual and HCHO can be quite high (550 ppb) species such as "03 in severe episodes. The implications of these findings are discussed in some detail below, after a discussion of the concentrations and time-dependent behavior of the individual pollutants studied. Formaldehyde. I t is now well established through smogchamber and modeling studies that HCHO is a key initiator of photochemical smog (4-6,17,26).Formaldehyde absorbs solar radiation in the near-UV region and, as a major reaction channel, photodissociates into H atoms and HCO radicals. These react with 0 2 to produce hydroperoxyl radicals, HOz, which in turn react with NO to give OH radicals and NOz; NO2 photolysis leads to ozone formation. Experimental verification of the effect of HCHO in accelerating the formation of 0 3 and other photochemical oxidants in environmental chamber studies has been reported (26). Our FT-IR measurements showed that morning HCHO concentrations in Claremont were in the range of 20-40 ppb. A slight decrease in these concentrations occurred around noon before the peak O3 readings. During the moderate episodes on Monday to Wednesday (October 9-11), the HCHO levels did not significantly rise above the morning HCHO concentrations. However, well-defined HCHO peaks corresponding to O3 maxima were observed (Figure 2, Tables V and VI) during the more severe episodes of Thursday and Friday (October 12 and 13) with HCHO reaching a peak concentration of 71 ppb on October 13. Figure 2 also shows the persistence of -20 ppb of HCHO during the night. The HCHO concentrations observed in this study, particularly on October 12 and 13, fall in the range of those reported by Altshuller and McPherson (12) for several days of measurements in September-November, 1961, in downtown Los Angeles. They reported peak concentrations as high as 160 ppb with an average level of 40 ppb. While obviously a direct comparison of the present results with the former measurements may not be wholly justified, the present values are also consistent with more recent wet-chemical measurements made at locations in the U S . and Japan. Measurements of formaldehyde concentrations by the New Jersey Department of Environmental Protection in the at1234
Environmental Science & Technology
+
mospheres of four New Jersey cities have been reported by Cleveland et ai. (27). They reported hourly average peak formaldehyde concentrations a t the four sites in the range 14-20 ppb and also provided diurnal concentration data for two of the sites. Aldehyde measurements by a liquid-chromatographic technique (28)showed that formaldehyde and acetaldehyde were virtually the only aldehyde components in the urban air of Osaka, Japan, with daytime concentrations of formaldehyde and acetaldehyde during summer 1978 being in the range 20-35 and 2-8 ppb, respectively. The values of HCHO observed spectroscopically in the present study are somewhat higher than the data from New Jersey and Osaka, presumably because of the greater severity of photochemical smog at Claremont, although some of these differences could be due to the influence of vehicular traffic. Formic Acid. The HCOOH levels observed during the moderate episodes of October 9-11 (Tables 11-IV) were low, typically less than 10 ppb, and their time dependence generally did not follow those of 0 3 formation. This is in agreement with the majority of our measurements in 1977 in Riverside (21). For the more intense episodes of October 12 and 13 in Claremont, however, HCOOH concentrations built up to well-defined maxima (Figure 2, Tables V and VI) with the highest HCOOH concentration of 19 ppb recorded on October 13. A peak HCOOH concentration of 72 ppb was reported by Hanst e t al. (13)in their FT-IR study of the intense episode which occurred in Pasadena on July 23,1973. However, their HCOOH data must be divided by 3.8 to be compatible with our recent absorptivity measurement (21,22)of the 1105 cm-l Q branch. This gives a corrected peak concentration for HCOOH of 19 ppb. The HCOOH concentration peaks on October 12 and 13 occurred -1 h after the HCHO maxima (Figure 2), possibly because of chemical processes which further oxidize HCHO to HCOOH. Peroxyacetyl Nitrate. PAN is formed from the reaction of NO2 with peroxyacetyl radicals formed in hydrocarbonNO, photooxidations: 0
0
/I CH,C-OO.
I/
CH,C-OONO, On the basis of model calculations, Hendry and Kenley (29) have predicted that PAN, which is initially present, will significantly enhance the rate of photochemical smog formation due to radicals formed from its thermal decomposition. + NO,
0
/I CH,C-OONO,
--+
-
I/
CH,C-OO.
+ NO,
0
0
/I CH,C-OO.
0
+ NO
--+
I1
CH,C-O.
+ NO,
Nz05
0
/I CH,C-O. CH,+O, CH,OO, + NO C H 3 0 , + 0,
--
.CH, + CO,
CH,O.
+
NO,
HOO. + HCHO
This has been verified by recent smog-chamber experiments (30).Thus, if PAN formed on a previous day persists through the night, it would be expected to have an impact on photochemical smog formation on the following day. PAN was measured a t 1162 cm-l with a detection limit of 3 ppb. On October 9 and 10, its concentration was above this level only during the afternoon, but PAN was observed throughout most of the monitoring periods on October 11-13 a t progressively higher concentrations. The PAN concentration declined throughout the evening of October 12 and early morning hours of October 13 but did not disappear completely until -0530 h, when increasing NO emissions from traffic presumably began. A peak value of 37 ppb was observed a t 1618 h on October 13 a t which time the ozone concentration was observed to be 454 ppb. This peak level is consistent with the data of Hanst and co-workers (13) for the severe episodes in Pasadena during the summer of 1973, e.g., 47 ppb PAN a t 590 ppb 0 3 and 51 ppb PAN a t 680 ppb 0 3 . Our 1977 data for Riverside (21,22) yielded a daily ayerage PAN/03 ratio of 0.04 during periods of photochemical activity. This ratio was also observed during the comparably moderate episodes of October 10-12, 1978, in Claremont. However, during the severe episodes of the 1973 Pasadena study (13), an average PAN/03 ratio of 0.1 was found; we observed the same average ratio for the severe episode of October 13,1978, in Claremont during the 0800-1800-h period of intense photochemical activity. Additional aspects of our PAN data are discussed below. Nitric Acid. Although we had accumulated substantial H N 0 3 data during the 1977 study in Riverside (21), H N 0 3 concentrations were below the detection limit during many periods; thus a detailed characterization of its concentration as a function of photochemical activity was not possible. Riverside is downwind from a significant source of ammonia (see below) which has been suggested as a cause of gaseous H N 0 3 depletion and NH4N03 aerosol formation (20). The Claremont site is upwind from this major source of ammonia, allowing measurements of ambient levels of H N 0 3 to be made a t the prevailing low NH8 concentrations which are more typical of the western and middle portions of the South Coast Air Basin. Figure 2 shows that the rise in H N 0 3 concentration is strongly coincident with the increase in oxidant levels (e.g., O3 and PAN). This behavior is also characteristic of the more moderate episodes on October 9-11 (Tables 11-IV). The highest H N 0 3 concentration measured was 49 ppb on October 13, which coincided with an O3 concentration of 454 ppb. This can be compared with H N 0 3 concentrations measured by Spicer (15) in 1973 a t West Covina: 1-h maxima of 34 ppb H N 0 3 with 213 ppb 03,and 40 ppb H N 0 3 with 271 ppb 03. These measurements (15) were made with a modified aciddetecting MAST Coulometric analyzer (continuous) and supplemented by a modified chromotropic acid procedure (integrated). Possible reactions for H N 0 3 formation in the atmosphere are the heterogeneous process
-+
2HN03
and the homogeneous reaction OH
CH,OO
+ H20
+ NO2 + M
+
"03
+M
Although the first reaction may be a possible pathway for "03 formation ( 4 ) ,the second reaction probably accounts for most of the "0.7 formed early in the day, since NzO5 is formed from reactions initiated by 03.Using the well-accepted rate constant of 1.6 X lo4 ppm-l min-l a t 298 K and 760 torr of air (31,32)for the second reaction, OH radical concentra~ ) and NO2 contions of ppm (2.4 X lo6 ~ m - (33-35), centrations of 0.1 ppm, calculations indicate that, in the absence of a rapid removal process, 16 ppb of H N 0 3 could be generated by this reaction pathway over a period of 100 min. Indeed, midmorning (e.g., 1000 h) concentrations of H N 0 3 in Claremont were in the range of 10-15 ppb on October 9-12 (Tables 11-V); midmorning levels of H N 0 3 up to 20 ppb on October 13 were consistent with the prevailing high concentrations (20.15 ppm) of NO2 (Table VI). Of particular interest is the concentration of "03 relative to that of PAN. Spicer ( 1 5 , 3 6 )reported that the PAN/HN03 ratio varied between 1and 3 during their field study in West Covina, CA, in August-September 1973; the ratio was usually in the range 1-2 on smoggy afternoons. However, Spicer's measurements ( 1 5 ) a few weeks earlier in St. Louis, MO, indicated H N 0 3 concentrations which were generally higher than those of PAN. The present FT-IR data for the week October 9-13,1978, in Claremont showed PAN/HN03 ratios in the range 0.3-0.8 a t about the peak of the smog, with lower values observed earlier in the daily episodes. PAN/HN03 ratios could not be deduced from the data of our 1977 study in Riverside (21,22) because of the effective removal of "03 from the gas phase by prevailing high concentrations of NH3 (20). The generally higher levels of H N 0 3 compared to PAN found in our present study, relative to Spicer's West Covina measurements, are more consistent with recent kinetic computer modeling studies of photochemical smog formation (see, for example, ref 37 and 38) in which H N 0 3 is predicted to be the dominant nitrogenous product. Ammonia. As discussed above, NH3 has been assigned a prominent role in the formation and neutralization of sulfate and nitrate aerosols. Particulate sulfates and nitrates in the inland areas of the South Coast Air Basin have been shown (39-42) to exist mainly in the form of ammonium salts, and their spatial distribution has been strongly correlated with prevailing local NH3 concentrations. The average NH3 concentration measured in Claremont during the week of October 9-13 was -8 ppb. During the months of July and August 1978, NH3 levels a t this site were generally less than 10 ppb. Recent measurements by a filter collection method employing oxalic acid-coated filters (43) found average NH3 concentrations of 1-10 ppb in other locations in the South Coast Air Basin outside of the Riverside-San Bernardino area. The NH3 concentrations measured by FT-IR spectroscopy in Claremont were approximately 5 times lower than those found in Riverside during our 1976 and 1977 studies. Incorporation of high NH3 levels into the polluted air mass from primary sources (Le., feedlots) in the Chino and Ontario area was evident in the Riverside data (21,22). Claremont is -7 mi northwest of the Chino-Ontario area, and, although air mass transport from there is mainly eastward toward the Riverside-San Bernardino area, occasional increases in NH3 concentrations up to -25 ppb (see Figure 2) observed a t Claremont may be attributed to transport from this primary source. Volume 15, Number 10, October 1981
1235
Air Quality Considerations The results presented here, which confirm and extend previous studies in the California South Coast Air Basin, impact on a number of air quality issues. In addition to providing a better basis for the validation of computer kinetic models of photochemical smog formation, these new data are relevant to the effects of photochemical oxidant on human health and vegetation and to the role of HNO:3 in acid-rain formation. The latter subject is, however, too broad to be discussed here. Clearly the health impact of photochemical air pollution can result not just from ozone alone but from the entire spectrum of gas-phase and particulate pollutants which In light of the coexist along with it in ambient smog (44,451. recent revision of the Federal air quality standard from oxidant to ozone, it is interesting to examine what the total levels of gaseous trace pollutants are relative to ozone concentrations in photochemical smog. The data accumulated in this study appear to encompass a wide enough range of concentrations to provide a basis for a t least an initial assessment. The ratios presented below are based on our FT-IR data for HN03, PAN, HCHO, and HCOOH. Although the choice of this group of gaseous trace pollutants may seem arbitrary, these products are those (along with 0 3 and NO,) for which data are consistently sought in the characterization of secondary pollutants in chamber experiments, modeling studies, and specialized air monitoring programs. Over a period of several hours encompassing the peak ozone concentrations, the sum of the concentrations of PAN, HN03, HCOOH, and HCHO is typically -30% of the O3 concentration (Tables 11-VI, Figure 3). However, the percentage of “trace” pollutants is even higher when the sums of their concentrations are averaged over an 8-h period of photochemical activity (1000-1800 h). Thus, for the block averaged data for the 1000-1800-h period (Table VII) of October 9-13, the ratio of the trace pollutant-to-ozone concentrations ranges between 35% and 50%,with an overall average of -44%. The ratio averages for the periods from 1000 h to peak-of-smog times fall in a similar range; those from the 1000-2000-h period yield a slightly higher average trace pollutant-to-ozone ratio mainly due to the fast depletion of 0 3 during the early evening hours. Whether or not the ratios, [trace species]/[03], observed in the present study will be generally applicable to other cities suffering from photochemical smog remains to be tested. Certainly if primary emissions of H&O are large (e.g., from industrial plants, incomplete combustion of methanol, etc.), this ratio will increase accordingly.
5001
-
-3rd
i
STAGE
400
P
-
D
+
300
2 2
Finally, the present calculated ratios do not include other known copollutants of ozone such as hydrogen peroxide, acrolein, acetaldehyde, nitrous acid, etc. For example, levels of nitrous acid (HONO) reaching 2-4 ppb in Riverside and Claremont (46) and 6-8 ppb near central Los Angeles ( 4 7 ) were recently observed by using a long path differential UV-visible absorption spectrometer. Acknowledgment We thank Dr. Richard A. Graham for his assistance during one of the monitoring periods; we thank him and Dr. Roger Atkinson for helpful discussions. The cooperation of Professor Gregory Kok and Dr. Kenneth Baker, President of Harvey Mudd College, in siting the FT-IR facility on the Harvey Mudd campus is appreciated. Literature Cited (1) Leighton, P. A. “Photochemistry of Air Pollution”; Academic Press: New York, 1961. (2) Altshuller, A. P.; Bufalini, J. J. Photochem. Photobiol. 1965,4, 97. (3) Altshuller, A. P.; Bufalini, J. J. Enuiron. Sci. Technol. 1971,5, 39. (4) Demerjian, K. L.; Kerr, J. A,; Calvert, J. G. Adu. Enuiron. Sei. Technol. 1974,4,1. (5) Finlavson. B. J.: Pitts. J. N.. Jr. Science 1976.192.111. (6) Finlaison-Pitts,B. J.; Pitts, J. N., Jr. Adu. Enutron. Sci. Technol. 1977, 7, 75. (7) “Ozone and Other Photochemical Oxidants”; National Academy of Sciences: Washington, DC, 1977. (8)“Air Quality Criteria for Ozone and Other Photochemical Oxidants”; U.S. Environmental Protection Agency, Office of Research and Development: Washington, DC, 1.979;Vol. 1. (9) Carter, W. P. L.; Lloyd, A. C.; Sprung, J. L.; Pitts, J. N., Jr. Int. J. Chem. Kinet. 1979,11,45. (10) ‘Mader, P. P.; Cann, G.; Palmer, L. Plant Physiol. 1955, 30, 318. (11) Renzetti, N. A.; Bryan, R. J. J . Air Pollut. Control Assoc. 1961, 1,421. (12) Altshuller, A. P.; McPherson, S. P. J. Air Pollut. Control Assoc. 1963,13,109. (13) Hanst, P. L.; Wilson, W. E.; Patterson, R. K.; Gay, B. W., Jr.; Chaney, L. W.; Burton, C. S.Research Triangle Park, NC, 1975, EPA Publication No. 650/4-75-06. (14) Miller, D. F.; Spicer, C. W. J . Air Pollut. Control Assoc. 1975, 25,940. (15) Spicer, C. W. Adu. Enuiron. Sci. Technol. 1977, 7, 163. (16) Calvert, J. G.; McQuigg, R. D. Int. J . Chem. Kinet. Symp. 1975, 1,113. (17) Lloyd, A. C. NBS Spec. Publ. (U.S.)1979, No. 557. (18) Hanst, P. L. Adu. Enuiron. Sei. Technol. 1971,2, 91. (19) Tuazon, E. C.; Graham, R. A.; Winer, A. M.; Easton, R. R.; Pitts, J. N., Jr.; Hanst, P. L. Atmos. Enuiron. 1978,12,865. (20) Doyle, G. J.; Tuazon, E. C.; Graham, R. A.; Mischke, T. M.; Winer, A. M.; Pitts, J. N., Jr. Enuiron. Sci. Technol. 1979, 13, 1416. (21) Tuazon, E. C.; Winer, A. M.; Graham, R. A.; Pitts, J. N., Jr. Adu. Enuiron. Sei. Technol. 1980,10, 259. (22) Tuazon, E. C.; Winer, A. M.; Graham, R. A.; Pitts, J . N., Jr. “Atmospheric Measurements of Trace Pollutants by Long Path FT-IR Spectroscopy”; Final Report to U S . Environmental Protection Agency (Grant No. R-804546): Research Triangle Park, NC, 1981. (23) California Air Resources Board, Air Quality Data, Jan-March 1978. (24) Winer. A. M.: Peters. J. W.: Smith., J. P.:, Pitts. J. N.. Jr. Enuiron. Sei. Technol. 1974,8,118. (25) Miller, D. F.; Spicer, C. W. 67th Annual Meeting of the Air Pollution Control Association. Denver. CO.IPaDer . No. 74-247. June 9-13,1974. (26) Pitts, J. N.; Winer, A. M.; Darnall, K. R.; Doyle, G. J.; McAfee, J. M. “Chemical Consequences of Air Quality Standards and of Control Implementation Programs: Roles of Hydrocarbons, Oxides of Nitrogen and Aged Smog in the Production of Photochemical Oxidant”; Final Report, University of California, Riverside-California Air Resources Board Contract No. 4-214, May 1976. (27) Cleveland, W. S.; Graedel, T. E.; Kleiner, I3. Atmos. Enuiron. 1977,11,357. (28) Kuwata, K.; Uebari, M.; Yamasaki, Y. J . Chromatogr. Sci. 1979, 17, 264. I
i
IO0
0
OZMYE
FORMbLEHYE
NITRIC KID
P4N
F(RMIC
KID
TOT& m l 4 T E D GesECUS F U L U T ~ MEISUREO IN T H I S STUDY
Figure 3. Maximum concentrations of trace pollutants and their percent of maximum ozone observed at Claremont, CA, on October 13, 1978, by kilometer path length FT-IR spectroscopy; California air quality standard (CAQS) for ozone and episode levels are indicated. 1236
Environmental Science & Technology
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(29) Hendry, D. G.; Kenley, R. A. In “Nitrogenous Air Pollutants”; Grosjean, D., Ed.; Ann Arbor Press: Ann Arbor, MI, 1979. (30) Carter, W. P. L.; Winer, A. M.; Pitts, J. N., Jr., submitted for publication in Enuiron. Sci. Technol. (31) Hampson, R. F., Jr.; Garvin, D. NBS Spec. Publ. (U.S.) 1978, No. 513. (32) “Chemical Kinetic and Photochemical Data for Use in Stratospheric Modeling”; J e t Propulsion Laboratory Publication 79-27, April 15, 1979. (33) Calvert, J . G. Enuiron. Sci. Technol. 1976,10, 256. (34) Campbell, M. J.; Sheppard, J. C.;Au, B. F. Geophys. Res. Lett. 1979,6,175. (35) Davis, D. D.; Heaps, W.; Philen, D.; McGee, T . Atmos. Enuiron. 1979,13,1197. (36) Spicer, C. W. Atmos. Enuiron. 1977,11,1089. (37) Whitten, G. Z.; Killus, J. P.; Hogo, H. “Modeling of Simulated Photochemical Smog with Kinetic Mechanism”; Final Report, EPA-6003-80-028a,Feb 1980; Vol. 1. (38) Isaksen, I. S. A.; Hov, 0.;Hesstvedt, E. Enuiron. Sci. Technol. 1978,12,1279. (39) Hidy, G. M. J . Air Pollut. Control Assoc. 1975,25, 1106. (40) Grosjean, D.; Friedlander, S. K. J . Air Pollut. Control Assoc. 1975,25,1038. (41) Grosjean, D.; Smith, J. P.; Mischke, T. M.; Pitts, J. N., Jr. In “Atmospheric Pollution”; Benarie, M. M., Ed.; Elsevier: Amsterdam, 1976; p 549-63. (42) Appel, B. R.; Kothny, E. L.; Hoffer, E. M.; Hidy, G. M.; Wesolowski, J. J. Environ. Sci. Technol. 1978,12,418. (43) Richards, L. W., Rockwell International, Air Monitoring Center, private communication, 1979. (44) Pitts, J. N., Jr.; Winer, A. M. Written testimony to U.S. Environmental Protection Agency hearing on proposed revision of the primary air quality standard for ozone, Los Angeles, CA, Aug. 24, 1978.
(45) Pitts, J . N., J r . Testimony presented to the Subcommittee on Natural Resources and the Environment of the Committee on Science and Technology of the US.House of Representatives, Feb 15, 1979; in “1980 Authorization for the Office of Research and Development, Environmental Protection Agency”, Committee on Science and Technology Publication No. 96-5. (46) Platt, U.; Perner, D.; Harris, G. W.; Winer, A. M.; Pitts, J. N., Jr. Nature (London) 1980,285,312. (47) Carter, W. P. L.; Harris, G. W.; Winer, A. M.; Pitts, J. N., Jr.; Perner, D. Statewide Air Pollution Research Center, University of California, Riverside, CA, unpublished data. (48) Table IX, Air Quality and Meteorology Report, Oct 1978, California South Coast Air Quality Management District, El Monte, CA.
Received for review January22,1981. Accepted June 15,1981. We gratefully acknowledge the support of this work by the U.S. Enuironmental Protection Agency (Grant No. R-804546) and by Dr. Philip L. Hanst, the project monitor and developer of the kilometer path length FT-IR facility. Supplementary Material Available: Tables 11-VI containing pollutant concentrations measured in this study on October 9-13,1978, a t Claremont, CA (6 pages), will appear following these pages in the microfilm edition of this volume of the journal. Photocopies of the supplementary material from this paper or microfiche (105 X 148 mm, 24X reduction, negatives) may be obtained from Business Operations, Books and Journals Division, American Chemical Society, 1155 16th St., N.W., Washington, DC 20036. Full bibliographic citation (journal, title of article, author) and prepayment, check or money order for $6.00 for photocqpy ($7.50 foreign) or $4.00 for microfiche ($5.00 foreign), are required.
Organic Compounds Found Near Dump Sites in Niagara Falls, New York Vincent A. Elder, Bertha L. Proctor, and Ronald A. Hites” School of Public Environmental Affairs and Department of Chemistry, Indiana University, Bloomington, Indiana 47405 Water and sediment samples were taken from sites adjacent to hazardous waste disposal areas in Niagara Falls, NY. The samples were analyzed by gas-chromatographic mass spectrometry. The following compounds were identified: chlorobenzenes, chlorotoluenes, polycyclic aromatic hydrocarbon derivatives, PCBs, trichlorophenol and other phenols, benzotrifluorides, mirex, and phenothiazine. A large number of benzyl derivatives and a few unusual fluorinated compounds were also found; they were probably waste byproducts of the industrial chemical production of benzyl chloride and itrifluoromethyl)chlorobenzene, respectively. The hazardous waste disposal sites were the major sources for most of the compounds which were found.
Introduction Love Canal is a 6-hta, rectangular site located in the southeast corner of the city of Niagara Falls. Chemicals buried within the boundaries of this unfinished canal 30 yr ago have infiltrated several homes, and some known or presumed carcinogens have been found in their basements ( I ) . Unfortunately, Love Canal is only one of the waste disposal sites in western New York. An interagency task force (state and federal agencies) has identified 152 hazardous waste disposal sites in Erie and Niagara Counties, NY ( I ) . Because leachate from many of these disposal sites could contaminate the Niagara River and because the Niagara River is an important drinking-water source for several United States and Canadian cities and the major source of water for Lake Ontario ( 2 ) ,identifying 0013-936X/81/0915-1237$01.25/0
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the waste industrial organic compounds in the Niagara River-Lake Ontario system is imperative. This paper reports on the identification of anthropogenic organic compounds at three sites in and near the Niagara River.
Experimental Section The three sampling sites were in the city of Niagara Falls (see Figure 1).The 102nd Street dump site forms a bay 0.8 km long and 0.4 km wide which is actually part of the Niagara River. Four different dump sites make up the shoreline of the 102nd Street bay; it also receives runoff from the Love Canal area through a storm sewer. Bloody Run Creek is 200 m long and is little more than a drainage ditch for the Hyde Park landfill. The third sampling site was Gill Creek, which runs through an industrialized complex; the companies in the complex have several dump sites located on their property (1). All three sampling sites drain directly into the Niagara River. With the cooperation of the New York State Department of Environmental Conservation, a series of water and sediment samples were collected from these sites during June and November 1979. Gill Creek was sampled midstream at -100 m upstream from the Niagara River. Bloody Run Creek was sampled at -30 and 150 m downstream from the boundary of the Hyde Park landfill. The 102nd Street bay was sampled at four places along the bay and -30 m from the shore. Water samples were collected in 3.8-L, amber glass bottles with Teflon-lined caps. Sediment samples were collected at each site with a shovel or Eckman dredge and were stored in Volume 15, Number 10, October 1981 1237
