Environ. Scl. TeChnOl. 1983, 17, 13-19
either blue-green algae or heterotrophic bacteria (9,lO). Thus, Jones (11) found that unialgal cultures of Nostoc continued to reduce acetylene for several hours after being placed in darkness. Using a ratio of 3:l for the ratio of acetylene reduced to nitrogen reduced, it is possible to estimate that the amount of nitrogen fixed in these forest soils ranged from as low as 0.06 g/ (ha h) in the dark to as high as 0.62 g/ (ha h) in the light. In contrast, Loftis and Kurtz (12)report that up to 1.3 g of nitrogen/(ha h) may be added to the soils by blue-green algae. Although these amounts of nitrogen are small, they still may be important in a forest receiving little nitrogen from other sources. In nonforest soils, however, in which algae sometimes flourish and fix appreciable amounts of nitrogen (13), acid rain may have a significant impact on them, especially because the position of the algae at the soil surface places them at the site where they do not have the protection from atmospheric stresses afforded by soil constituents to the subterranean microorganisms. Growth at the soil surface is true of the eukaryotic as well as the prokaryotic algae, and hence COz fixation, organic matter formation, and other beneficial actions of the algal community may be significantly influenced by the prolonged exposure to acid precipitation. Therefore, additional study is required to determine whether such possible effects do indeed take place in nature. The simulated rain was applied at greater rates than are normal in the field in order to evaluete in short periods of time what occurs in nature during a long period of exposure. Using higher than natural levels of a potential toxicant in laboratory studies to predict long-term effects at natural concentrations is a common practice in developing toxicological models to predict epidemiological consequences. Although the validity of such an approach
has often been studied in toxicology, comparable field validations at low rainfall intensities have not yet been attempted in studies of acid rain.
Acknowledgments We thank Richard Lynn for technical assistance. Registry No. COz, 124-38-9.
Literature Cited Granhall, U. In “Nitrogen Fixation by Free-Living Microorganisms”; Stewart, W. D. P., Ed.; Cambridge University Press: Cambridge, 1975; p 189. Brock, T. D. Science (Wasington, D.C.) 1973, 179, 480. Wilson, J. T.; Alexander, M. Soil Sci. SOC.Am. J. 1979,43, 936. Watanabe, A. Soil Biol. Biochem. 1973, 5, 161. Evans, L. S.; Raynor, G. S. “Acid Rain Research Program Annual Progress Report. September 1975 through June 1976”;Brookhaven National Laboratory, Upton, NY, 1976. Cogbill, C. V.; Likens, G. E. Water Resour. Res. 1974,10, 1133. Zwarun, A. A.; Thomas, G. W. Soil Sci. SOC.Am. Proc. 1973, 37, 386. Wolin, M. J. Appl. Microbiol. 1969, 17, 83. Jones, K. New Phytol. 1977, 78, 437. Henriksson, L. E.; Enckell, P. H.; Henriksson, E. Oikos 1972, 23, 420. Jones, K. New Phytol. 1977, 78, 421. Loftis, S. G.; Kurtz, E. B. Soil Sci. 1980, 129, 150. Shtina, E. A.; Pankratova, E. M.; Perminova, G. No; Tretjakova, A. N.; Yung, L. A. Trans. 9th Zntl. Congr. Soil Sci. 1968, 2, 151. Received for review April 27,1982. Accepted August 20, 1982. This study was supported by Electric Power Research Institute as part of their Integrated Lake Acidification Study (RP-1109-5).
Distribution of Atmospheric Nitrogenous Pollutants at a Los Angeles Area Smog Receptor Site Danlel Grosjean
Environmental Research & Technology, Inc., Westlake Village, California 9 1361 An intensive field study of atmospheric nitrogenous pollutants was conducted at a Los Angeles area smog receptor site, during selected 1980 air pollution episodes. Highest 4-h averaged concentrations were 47 pg m-3 for particulate nitrate (NO3-) and 36 pg m-3 for nitric acid (HONOJ. HONOz and NO3- exhibited opposite diurnal variations. The highest peroxyacetyl nitrate (PAN) concentration recorded was 47 ppb. Methyl nitrate was consistently observed a t trace levels (4.1 10.2 22.0 14.5 11.7 21.1 6.3 >1.9 >1.7 6.1 5.1 >3.7 >3.3 >11.9 13.7 9.9 7.5 30.9 46.9 32.5 17.9 15.4 20.3 14.9 14.0 16.1 30.9 32.1 22.5 13.7 7.5 18.1 11.9 4.5 13.3 13.1 28.5 26.7 19.6 37.3 23.1 9.5 46.9 26.7 30.7 39.3 27.5 17.3 42.0 17.3 25.9 33.9 21.7 26.0 21.8 5.9 6.1 14.6 24.0 10.6 8.5 12.9 > 8.7
Teflon nvlon Teflon/ filter filter nylon (front) (backup) ratio NDa 7.1 5.9 2.7 3.7 7.5 2.1 1.9 1.7 3.9 3.3 3.7 3.3 11.9 3.5 5.9 6.1 29.3 44.3 11.5 1.9 3.3 2.9 2.5 9.8 11.9 26.3 5.5 1.3 0.7 2.1 13.3 8.3 0.9 1.3 1.9 20.3 19.5 6.1 1.3 0.7 1.1 33.1 17.3 14.3 5.1 2.1 2.5 28.3 8.3 10.1 3.9 1.9 1.1 0.5 0.5 3.1 11.9 21.7 8.8 6.5 11.3
ND
4.1 3.1 16.1 11.8 8.0 13.6 4.2
2.3 0.37 0.23 0.46 0.55 0.50
ND ND 2.2 1.8
1.8 1.8
ND ND ND 10.2 4.0 1.4 1.6 2.6 21.0 16.0 12.1 17.4 12.4 4.2 4.2 4.6 26.6 21.2 13.0 5.4 4.8 3.6 '3.6 12.0 11.2 8.2 6.2 13.4 36.0 22.4 8.4 13.8 9.4 16.4 34.2 25.4 14.8 14.0 9.0 15.8 30.0 19.8 24.9 21.3 5.4 3.0 2.7 2.3 1.8 2.0 1.6 8.7
0.34 1.5 4.3 18.3 17.0 0.55 0.12 0.27 0.17 0.20 2.3 2.8 5.7 0.21 0.06 0.05 0.39 2.8 2.3 0.25 0.11 ' 0.17 2.5 3.1 0.45 0.04 0.03 0.13 2.4 1.8 0.9 0.15 0.08 0.17 2.0 0.9 0.6 0.13 0.10 0.04 0.02 0.1 1.0 4.4 9.4 4.9 3.2 7.1
Not determined.
of photochemical origin at a smog receptor site, with late afternoon maxima on smog episode days. Thus, PAN and ozone exhibited essentially identical diurnal varihtions (Figure 2) but, as noted before (36), PAN-to-ozone concentration ratios were consistently higher during nighttime. Persistence of 10-20 ppb of PAN overnight may accelerate 16
Environ. Sci. Technol., Vol. 17, No. 1, 1983
---Sept.
25-
S e p t . 26---
Sept. 2 7 4
TIME, PDT
Figure 2. Diurnal variations of major nitrogenous pollutants and other selected parameters, Claremont, CA, Sept 25-27, 1980.
smog formation on the following day(s) of a multiday episode (38, 39). The gas chromatographic conditions employed for PAN measurements during this study are also suitable for the determination of several gaseous alkyl nitrates including methyl nitrate, CH30N02. A second peak with a retention time identical with that of an authentic sample of CH30NO2 was virtually always observed during smog episodes, with diurnal variations following closely those of PAN (formation mechanisms for CH30N02in the atmosphere include the decomposition of PAN as a major pathway (38). Up to -5 ppb of methyl nitrate were observed in Claremont during photochemical smog episodes assuming that the instrument response to CH30N02is approximately the same as that for PAN in our conditions. Nitrate Concentrations and Diurnal Variations. Total nitrate, Teflon filter collected nitrate, and nylon filter collected nitrate concentrations are listed in Table 11. Four-hour averaged concentrations ranged from 5 to 47 pg m-3 for total nitrate, 1 to 44 pg m-3 for Teflon filter nitrate, and 1to 36 pg m-3 for nylon filter nitrate. Two-, three-, and eight-hour averaged values were also within that range. The abundance of particulate nitrate in Los Angeles air, sometimes questioned by other investigators in the past on the basis of positive filter artifact considerations, is clearly demonstrated here since even our maximum measured concentration of 44 pg rnv3may be a lower limit if negative artifact is significant. Our maximum value for nylon filter nitrate, 36 pg m-3, is equivalent to -14 ppb nitric acid. Over the entire period studied as defined by the sampling schedule given in Table 11, the average total inorganic nitrate concentration in Claremont air was -20 pg m-3. Slightly less nitrate was collected as particulate nitrate on Teflon filters (average 8 pg m-3 or -42% of the total nitrate) than was collected as gaseous nitrate on nylon filters (average 11pg m-3, or 58% of the total nitrate).
~
Table 111. PAN and HONO, Interference in NO, Measurements by Chemiluminescence, Claremont, CA, Sept-Oct 1980 overestimate of PAN + untime, corrected HONO,, corrected corrected date PDT NO,,ppb ppb NO,, P P ~ NO,, % 9/19
17-20 20-23 9/20 8-1 1 9/22 16-20 20-24 9/23 0-4 4-8 8-12 12-16 9/25 8-12 12-16 16-20 20-24 9/26 0-4 4-8 9-13 13-17 17-21 9/26-27 21-1 9/27 1-5 5-9 10/1-2 10-14 14-18 18-22 22-2 2-6 6-10 10-14 1017-8 10-14 14-18 18-22 22-2 2-6 6-10 10-14
63 74 66 68 82 53 53 100 89 119 98 117 121 60 65 145 109 108 119 69 62 41 79 101 86 48 94 97 134 117 130 74 35 81 139
3 1 4 10 3 5 4 13 20 8 20 23 11 12 10 16 27 21 10 13 10 5 27 22 21 12 9 35 25 46 48 24 11 11 24
60 73 62 58 79 48 49 87 69 111 78 94 110 48 55 129 82 87 109 56 52 36 52 79 65 36 85 62 109 71 82 50 24 70 115
6 2 7 18 4 10 8 15 29 7 25 24 10 24 18 13 33 24 9 22 19 14 52 28 32 33 11 56 23 65 58 48 46 16 21
Gaseous and particulate nitrate exhibited nearly opposite diurnal variations, with concentration ratios ranging from 0.02 to 18.3 (Table 11). As is shown in Figure 2 for a selected multiday smog episode, Sept 25-27, gaseous nitrate exhibited daytime maxima with diurnal profiles similar to those of ozone and PAN, in agreement with the photochemical origin of these three species. Particulate nitrate consistently exhibited nighttime and early morning maxima, with low daytime values of a few pg m-3. As is discussed in detail elsewhere (40),these low daytime values for particulate nitrate can to a large extent be explained on the basis of thermodynamics (equilibrium) considerations for ammonium nitrate, the major component of nitrate aerosol in Los Angeles air (11). Total inorganic nitrate concentrations exhibited composite diurnal profiles, with both daytime and nighttime maxima. During daytime, most of the nitrate is present as nitric acid. The major daytime nitric acid production pathway is that involving reaction of nitrogen dioxide with the hydroxyl radical (5). For a range of NO2 and OH concentration of 0.05-0.25 and (1-3) X lo-' ppm, respectively, and with use of literature kinetic data (41),nitric acid is produced at a rate of -5-75 ppb/h. These estimated production rates are more than sufficient to account for our daytime nitric acid observations. The nighttime situation is more complex and probably involves several competing nitrate formation mechanisms. The decomposition of PAN in the presence of NO provides a source of OH radicals (381,which in turn react with NO2 to
Table IV. Distribution of Major Atmospheric Nitrogenous Pollutants, Claremont, CA, Sept-Oct 1980 ratios, % concn, Mg N m-' time, NO + inorg PAN + nitrate/ date PDT NO,a PAN nitrateb nitrate total NC 9/19 9/20 9/22-23
9/25-27
10/1-2
1017-8
17-20 20-23 8-11 16-20 20-24 0-4 4-8 8-12 12-16 8-12 12-16 16-20 20-24 0-4 4-8 9-13 13-17 17-21 21-1 1-5 6-9 10-14 14-18 18-22 22-2 2-6 6-10 10-14 10-14 14-18 18-22 22-2 2-6 6-10 10-14
37 73 45 35 55 31 47 60 42 93 46 55 81 31 39 87 49 54 106 40 32 21 31 46 38 21 66 37 69 43 50 30 15 63 65
1.5 0.4 0.2 5.0 1.5 2.3 1.8 2.9 7.9 1.7 7.4 10.2 5.4 5.8 4.6 3.3 10.8 9.3 4.6 6.2 4.8 2.2 12.4 10.1 10.2 5.9 2.4 12.3 7.0 20.9 24.2 11.1 4.3 2.6 9.7
1.4 1.1 3.1 2.2 1.7 7.0 10.6 7.3 4.0 3.5 4.6 3.4 3.2 3.6 7.0 7.2 5.1 3.1 1.7 4.1 2.7 1.0 3.0 3.0 6.4 5.8 4.4 8.4 8.9 6.2 3.9 9.5 3.9 5.8 4.2
52 27 6 69 47 25 15 28 66 33 62 75 63 62 40 31 68 75 73 60 64 69 80 77 61 50 35 59 44 77 86 54 52 31 70
7 2 7 17 6 23 21 14 22 5 21 20 10 23 23 11 25 18 6 20 19 13 33 22 30 36 9 36 19 39 36 40 35 12 18
NO, corrected for PAN and HONO, interference. Inorganic nitrate = Teflon filter nitrate + nylon filter nitrate. Total nitrogen = NO + NO, + PAN + inorganic nitrate, all in pg N m-3. a
produce nitric acid. On the basis of the nighttime PAN and NO, levels we measured during multiday episodes, this pathway may contribute to the still significant levels of nitric acid we observed at night (up to 15 pg m-3). The heterogeneous hydrolysis of N205 (formed by the sequence O3 + NO2 NO3 02,NO3 + NO2 = N205) probably contributes to nitric acid production in the early evening, when high levels of O3 and NO2, as well as lower sunlight intensity (the nitrate radical NO3 photolyzes rapidly) are conductive to higher levels of NO3 (42). Nitrate production via heterogeneous pathways involving incorporation of NO2 and HON02 into aqueous aerosols is higher at nighttime and at lower temperatures (7,8). These heterogeneous processes are also expected to contribute to the nighttime nitrate measured in Claremont air. Positive Interference from PAN and HON02 in NO2 Measurements. As discussed earlier, chemiluminescent NO, analyzers respond quantitatively to PAN and to nitric acid in the NO2 mode of the instrument (14,16). Since both PAN and HON02 are formed in chemical reactions consuming NO2,the possibility for significant interference is greatest during severe photochemical episodes. This is evident from data in Table 111, where PAN, HON02, and uncorrected and corrected NO2 levels are listed for all sampling periods for which these parameters were measured simultaneously. On relatively clear days, the combined interferences from PAN and HON02is small
-
+
Environ. Sci. Technol., Vol. 17, No. 1, 1983
17
~~_~
~~
~~~
9/25
Time. POT
~~~~~
'
~~
9/26
,
-..
.
'
9/27
+
e3. Ambient NO, ieveis. Ckremont. CA, Sept 25-27, 1980. wim
and without correction for interference from PAN and HONO,.
(e.g., see Sept 19 and 20 in Table IV, interference = 2-7%) and is probably not significant when compared to the combined uncertainties inherent to the measurement methods. On smoggy days, however, NO, can be seriously overestimated if the response of chemiluminescent instruments to PAN and HONO, is not taken into account. For example, measurements conducted around the clock during the Sept 25-27 smog episode show that NO, was overestimated by 19% over that 48-h period. Maximum NO, overestimates were 33%, 5670,and 65% (4-h averages) during the Sept 25-27, Oct 1-3, and Oct 7-9 smog episodes, respectively. As is shown in Figure 3, the interference is greatest in the mid and late afternoon when both PAN and HONO, are present at high levels (and when the contribution of particulate nitrate negative artifact, if any, to the measured nitric acid levels is minimum). This significant PAN and HONO, interference may have implications for monitoring, modeling, regulatory, and other issues pertaining to NOz measurements. Relative Importance of NO, PAN a n d NO, Nitrate Atmospheric Reaction Pathways. From the simultaneous measurements of NO, NO,, PAN, and nitrate conducted during this study, additional quantitative information can be gained concerning the transformations of atmospheric NO, during photochemical episodes. Listed in Table IV are concentrations and concentration ratios of the nitrogenous pollutants of interest, i.e., NO + NOz (with NO, corrected for.PAN and HONOz interference), PAN, and total inorganic nitrate, all expressed in the same mass concentration units as nitrogen (pg of N mil). Minor atmospheric products of NO, oxidation such as methyl nitrate, other gaseous alkyl nitrates, and particulate organic nitrates are not included. Two important observations can be derived from the data in Table IV. First, polluted air masses reaching Claremont (-4-5 h downwind from downtown Los Angeles (see Figure 1)) contain significant amounts of NO, oxidation products, with PAN and nitrate accounting for np to 40% of the "total nitrogen" (NO + NO2 + PAN + HON02+ NO,, all expressed in pg of N m") during smog episodes, as compared to only 2 9 % on relatively 'clean" days (e.g., Sept 19 and 20). The 24-h averaged products/total nitrogen ratios during multiday smog episodes were 17% on Sept 22 and 23 and Sept 25 and 27,2490 on Oct 1 and 2, and 30% on Oct 7 and 8. Second, PAN constitutes a major sink for atmospheric NO,, accounting typically for 30-80% of the NO, oxidation products. On a nitrogen basis, PAN was more abundant than inorganic nitrate in Claremont air on smoggy days, accounting for
-
18 Envkon. Sci. Technol.. Voi. 17,No. 1, 1983
-60% of the NO, oxidation products during multiday photochemical episodes: 59% on Sept 25 and 27,57% on Oct 7 and 8, and 62% on Oct 1and 2, during which the highest ozone levels for 1980 were recorded. Comparison with Other Studies. As mentioned earlier in this article, only a limited number of field studies conducted in the Los Angeles area have included simultaneous measurements of the nitrogenous pollutants of interest. Grosjean and Friedlander (11) reported PAN/ NO< ratios of 1.4-4 (pg of N basis) in Pasadena, CA, during the July 25, 1973, smog episode. Nitric acid was not included. Spicer (10) conducted measurements of PAN, HONO,, NO,, and particulate nitrate in West Covina, CA, in Aug-Sept 1973. One-hour averaged maxima were 90-270 ppb for ozone, 3-46 ppb for PAN, and 0-40 ppb for nitric acid. One-hour averaged PAN HONO,/NO + NO2 + PAN + HONO, ratios ranged up to 54% (ppb basis). Particulate nitrate data were not included in these calculations since only 24-h averaged values were obtained. Tuazon et al. (35) reported PAN/HON02 ratios of 0.34.8 (ppb basis) in Claremont, CA, during 1978 smog episodes. Particulate nitrate was not measured. More recently, Hanst et al. (43) reported 3-12 ppb nitric acid and 3-16 ppb PAN in Los Angeles, on June 26-27,1980, with PAN/HONO, ratios of 0.6-2.2 (ppb basis). Particulate nitrate was not measured. Thus, the results of this study are consistent with those of previous investigations with respect to PAN and HONO, concentrations, PANJHONO, ratios, and products/gasphase nitrogen ratios. Time-resolved products/total nitrogen ratios have not been presented prior to this work.
-
Acknowledgments We thank Gregory Kok and Joyce Nutall, Department of Chemistry, Harvey Mudd College, Claremont, CA, for their hospitality during the field phase of this project, and Kochy Fung of ERT for PAN calibrations and technical advice. Technical assistance provided by ERT staff including Daniel Womack, Beatriz Nuesca, Edith Oriola, Delores Youtz, Mark Stapel, Robert Swanson, John Collins, and Barbara Wright is gratefully acknowledged. Registry No. PAN, 227822-0; CH30N02,598-58-3;HON02, 7697-37-2; NO,10102-43-9;NO2. 10102-44-0; NO,, 11104-93-1: O,,
10028-15-6. Literature Cited (1) Niki, H.; Maker, P. D.; Savage, C. M.; Breitenhach, L. P.
In 'Nitrogenous Air Pollutants: Chemical and Biological Implications": Grosjean, D., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 1-16. (2) Uselman, W. M., Levine, S. Z.; Chan, W.H.; Calvert, J. G. In 'Nitrogenous Air Pollutants. Chemical and Biologid Imolications": Grosiean. D.. Ed.:' Ann Arbor Science: Ann Arior, MI, 1979; & 17-54: (3) Spicer, C. W.; Miller, D. F. J. Air Pollut. Control Assoc. 1976, 26,46.
Demerjian, K. L.: Kerr, J. A,: Calvert, J. G. Adu. Enuiron. Sci. Technol. 1974, 4, 1. (5) Graedel, T.E.; Farrow, L. A.; Weber, T. A. Atmos. Enuiron. 1976,10,1095-1116. (6) Orel, A. E.; Seinfeld,J. H. Enuiron. Sci. Technol. 1977,Il. (4)
1000.
(7) Peterson, T. W.: Seinfeld, J. H.In "Nitrogenous Air Pollutants: Chemical and Biological Implications"; Grosjean D., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 259-268. (8) Middleton, P.; Kiang, C. S. In 'Nitrogenous Air Pollutants: Chemical and Biological Implications"; Grosjean, D., Ed.;
Ann Arbor Science: Ann Arbor, MI, 1979;pp 269-288. (9) Grosjean, D., Ed. “Nitrogenous Air Pollutants: Chemical and Biological Implications”; Ann Arbor Science: Ann Arbor, MI, 1979. (10) Spicer, C. W. Adv. Environ. Sci. Technol. 1977, 7, 163. (11) Grosjean, D.; Friedlander, S. K. J. Air Pollut. Control Assoc. 1975,25,1038. (12) Chang, T. Y.;Norbeck, J. M.; Weinstock, B. Environ. Sci. Technol. 1979,13,1535. (13) Grosjean, D. Critical Evaluation and Comparison of Measurement Methods for Nitrogenous Compounds in the Atmosphere, Final Report A706-05to the Coordinating Research Council, Environmental Research and Technology, Westlake Village, CA, 1981. (14) Winer, A. M.; Peters, J. W.; Smith, J. P.; Pitts, J. N., Jr. Environ. Sci. Technol. 1974,8,1118. (15) Stevens, R. K., Ed.; Current Methods to Measure Atmospheric Nitric Acid and Nitrate Artifacts, U.S. Environmental Protection Agency Report No. EPA-600/2-79-051, Research Triangle Park, NC, 1979. (16) Stedman, D. H.; West, D. H.; Skelter, R. E. Measurements Related to Atmospheric Oxides of Nitrogen, Final Report to the Coordinating Research Council, University of Michigan, Ann Arbor, MI, Oct. 1981. (17) Martinez, R. I. Znt. J. Chem. Kinetics, 1980,12,771. (18) Grosjean, D.; Fung, K., submitted for publication in Anal. Chem. (19) Gay, B. W., Jr.; Noonan, R. C.; Bufalini, J. J.; Hanst, P. L. Environ. Sci. Technol. 1976,10,82-85. (20) Grosjean, D.; Fung, K.; Mueller, P.; Heisler, S.; Hidy, G. AZChE Symp. Ser. 1980,76,96-107. (21) Okita, T.; Morimoto, S.; Izawa, M.; Konno, S. Atmos. Environ. 1976,10,1085-1089. (22) Spicer, C. W.; Schumacher, P. Atmos. Environ. 1977,11, 873-876. (23) Appel, B. R.; Tokiwa, Y.; Haik, M. Atmos. Environ. 1981, 15,283-289. (24) Lazrus,A. L.;Gandrud, B. W., Greenberg, J. P. indophenol ammonia test in measurement of HNOBand NOa, U.S. EPA 1979,pp 45-50. Report No. EPA-600/2-79-051, (25) Durham, J. L.;Spiller, L. L. Measurements of gaseous, volatile and nonvolatile inorganic nitrate in the atmosphere, preprint, U.S.EPA, Research Triangle Park, NC, 1980. (26) Joseph, D. W.; Spicer, C. W. Anal. Chem. 1978,50,1400.
(27) Cox, R. A,; Roffey, M. J. Environ. Sci. Technol. 1977,11, 901. (28) Stelson, A. W.; Seinfeld, J. H. Atmos. Enuiron. 1982,16, 983. (29) Forrest, J.; Tanner, R. L.; Spandau, D.; D’Ottavio, T.; Newman, L. Atmos. Environ. 1980,14,137-144. (30) Appel, B. R.; Wall, S. M.; Tokiwa, Y.; Haik, M. Atmos. Environ. 1980,14,549-554. (31) Harker, A. B.,; Richards, L. W.; Clark, W. E. Atmos. Environ. 1977,11, 87-91. (32) Appel, B. R.; Tokiwa, Y. Atmos. Enuiron. 1981, 15, 1087-1089. (33) Grosjean, D.Anal. Lett., in press. (34) Hanst, P. L.;Wilson, W. E.; Patterson, R. K.; Gay, B. W., Jr.; Chaney, L. W.; Burton, C. S. Environmental Protection Agency Report No. 65014-76-06, 1975. (35) Tuazon, E. C.; Winer, A. M.; Pitts, J. N., Jr. Environ. Sci. Technol. 1981,15,1232-1237. (36) Pitts, J. N., Jr.; Grosjean, D. Detailed characterization of gaseous and size-resolved particulate pollutants at a South Coast Air Basin Smog Receptor Site, National Technical Information Service Report No. PB-301-294/5WP, Springfield, VA, 1979. (37) Tuazon, E. C.;Graham, R. A.; Winer, A. M.; Easton, R. R.; Pitts, J. N., Jr.; Hanst, P. L. Atmos. Environ. 1978,12,865. (38) Hendry, D. G.; Kenley, R. A. In “NitrogenousAir Pollutants Chemical and Biological Implications”; Grosjean, D., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979;pp 137-148. (39) Carter, W. P. L.; Winer, A. M.; Pitts, J. N., Jr. Environ. Sci. Technol. 1981,15,831. (40) Grosjean, D. Sci. Total. Environ., in press. (41) Hampson, R. F., Jr.; Garvin, D. NBS Spec. Publ. (V. S.) 1978,No. 513. (42) Platt, U.; Perner, D.; Winer, A. M.; Harris, G. W.; Pitts, J. N., Jr. Geophys. Res. Lett. 1980,7,89-92. (43) Hanst, P. L.;Wong, N:-W.; Bragin, J. Atmos. Environ. 1980, 16,969.
Received for review March 22,1982.Accepted August 19,1982. This work was supported by the Coordinating Research Council (CRC). We thank the members of the CRC-CAPA-1980Project Group for their support and for technical input during the course of this project.
Envlron. Sci. Technol., Vol. 17, No. 1, 1983 19
