Environ. Sci. Technol. 1987, 27, 556-561
Measurement of Polycyclic Aromatic Hydrocarbons in the Air along the Niagara River Raymond M. Hoff” and Kar-Wah Chant Atmospheric Environment Service, Downsview, Ontario, M3H 5T4 Canada
Two week-long studies in 1982-1983 have measured ambient concentrations of polycyclic aromatic hydrocarbons (PAH) and phthalate esters in air in both the particulate and gas phase along the U.S.-Canadian border and the Niagara River. Concentrations of the PAH species monitored varied from 3 pg m-3 to 40 ng m-3. PAH’s with three rings or less were found in significant proportions in the gas phase while larger molecules are almost solely in the particulate phase. Particulate components of the PAH loadings appear to originate locally with Buffalo, NY, Niagara Falls, NY,and Niagara Falls, Ontario, as probable sources. Gas-phase PAH components have a more regional character indicating regional or long-range transport. Levels of benzo[a]pyrene are consistent with previous particulate measurements made along the river since 1981.
Introduction The introduction and movement of toxic chemicals into the Niagara River and subsequently into Lake Ontario is one of the more serious current environmental issues. There is, however, little published data on the concentration of toxic species in the air along the river. Such data are useful not only to ascertain whether the river may be a source of such chemicals in the air (or vice versa) but also to assess the fluxes of such chemicals to and from the lower Great Lakes. This assessment is beyond the scope of the work discussed in this paper, but the data presented here should be of interest to those attempting toxic chemical mass balances in the Great Lakes watershed. In order to address some concerns about the atmospheric concentrations of toxics along the river, a series of sampling studies was undertaken between 1982 and 1984 by the Atmospheric Environment Service. In this paper, results of the air samples from two sampling periods during 1982-1983 will be interpreted in terms of the levels of polycyclic aromatic hydrocarbons and phthalate esters seen in the air along the river. In addition, qualitatively identified species in the air will be reported. Figure 1shows the Niagara River from Buffalo, NY, and Fort Erie, Ontario, on the south to Niagara-on-the-Lake, Ontario, on the north. The river flows from Lake Erie northward to Lake Ontario with a 100-m drop at Niagara Falls. The eastern Tonawanda Channel and the upper river on the U.S. side are heavily industrialized. The Canadian side in comparison is only lightly industrialized, predominantly in the areas near Fort Erie and Chippewa. Niagara Falls, NY, is the suspected source of numerous outfalls from old waste dumps, such as the Love Canal, the Hyde Park landfill, and the “S” area of Occidental Petroleum (previously known as Hooker Chemical) (I,2). These sources are of serious concern to both American and Canadian government agencies with regard to the water quality of the river. It is reasonable to assume that this industrialized section of the river would present a possible source of airborne contaminants from direct emission from industry, from urban emissions, and from volatilization +Present address: Research and Development, Dow Chemical, Fort Saskatchewan, Alberta, T8L 2P4 Canada. 556
Environ. Sci. Technol., Vol. 21, No. 6, 1987
from the river itself. To our knowledge, this report comprises the first Canadian measurement of mid molecular weight organic compounds in both the gas and particulate phases in the air in this area. For a number of years, the Ontario Ministry of the Environment has been monitoring PAH’s by glass fiber filters at several sites within 20 km of the river, and these results will also be reviewed.
Sampling Methodology A General Metal Works sampler with a particulate 2-pm upper cutoff uncoated impactor plate on the inlet was modified to allow insertion of two polyurethane foam (PUF) plugs below the filter, similar to the technique used by Keller and Bidleman (4). The inlet impactor was used not for size speciation but rather to eliminate nonrespirable aerosols (fly ash, etc.) from entering the system. The flow through the filter and PUF was regulated with a Sierra Instruments mass flow regulator inserted between the filter and the foam plugs. The flow was lowered from the standard high-volume flow rate to about 0.35 m3 min-l, giving a daily volume of about 500 m3. The PUF plugs were 3 cm in diameter by 7.5 cm. As was done in previous work (4),the foam plugs were cut into two equal lengths to provide a front sampling plug and a backup plug. The plugs were precleaned by Soxhlet extraction for 24 h in benzene and stored in individual glass jars with Teflon liners. The use of two plugs allows determination in a qualitative sense of the efficiency of the gas-phase sampling. Since the PUF acts as a chromatographic column, the shape of the frontal elution profile allows determination of the sampling efficiency as a function of sampling volume (at a given temperature) (5). Burdick and Bidleman show, for example, that 84% of trichlorobiphenyl is retained by 3 cm of foam for up to 400 m3 of sample volume. Given the range of compounds studied here and the varying temperatures over the sampling period, it is difficult to quantitatively correct for sampling inefficiencies if a breakthrough does occur. During this project, if the ratio of mass on the first plug to that on the second plug was 4:l [;.e., FP/(FP + BP) > 0.81, it was assumed from the general shape of chromatographic elution profiles that efficiency was over 90% when the total mass of the two plugs was added. If more was found on the back trap, a significant breakthrough is indicated, and the results should be regarded as minima for the gas-phase concentrations. Each 24-h sample was changed near noon of the study day. Gelman AE glass fiber filters were folded, placed in manila envelopes, and placed in a refrigerated cooler. The PUF plugs were placed in glass jars with Teflon-lined polypropylene lids. The longest period between sampling and extraction was 2 weeks with most of the samples extracted within 2 days of sampling. All samples were held between 0 and 5 “C after removal from the sampler. Field blanks for particulate filters and foam plugs were put through the complete handling procedure with the exception that the sampler was not turned on. Samplers were placed at three sites: Fort Erie (FE), Niagara Falls (NF), and Niagara-on-the-Lake (NOL). The published 1987 by the American Chemical Society
Table 1. Specter ldentlfied In the Air benzsne heptanoic acid hexatriacontane octanoic acid biphenyl 1,2-dibromododecane undecanoic acid diethyl phthalate phoephoric acid tributyl eater phosphoric acid diethyl pentyl ester butyl 2-methylpropyl phthalate nonanedioic acid dibutyl ester diirrooctyl phthalate dibutyl phthalate benzecenaphthalene anthracene benzou] fluoranthene benzo[e]pyrene benzolalpyrene phenanthrene
-
Flgw 1. Mapoflhestudy mhomLaka Erk on the south ‘9Lake ontark on ule north. fhethrse srrmprno slte8 are w e d with drdss.
Fort Erie hi-vol was placed to the north of the old fort itself in an open grassy field (669S5OE,4751OOON;UTM Zone 17). A residential road p d mme 60 m to the west of the sampler, and the river was 160 m to the east. The Niagara Falls sampler w a placed ~ on the Ontario Hydro Causeway to Coal lelaod and W%B abut 100 m off the river shoreline (65SOOOE, 4770200N). The sampler was about 4 m above the river surface. The third eampler was placed on Parks Canada property to the east of Fort George in Niagara-on-the-Lake (657600E, 4790300N). A small residential road W M 20 m to the east, and the river was some 150 m to the eaet. sampline at the N ~ - o n - & L a k e aite was conducted during both Study ~ r i o d a :Sept. 14-21,1982,and Jan. 26-31,1983.The other two sitae were in operation during the January study only. Samples were Sorhlet-extracted in benzene for 24 h. The extract was reduced in volume from 100 to 0.6 mL by rotary evaporation and high purity nitrogen purging. Aliquota (1pL) were injected onto a Gmbtype splitter at moc. prognunrmng * of the O.%mm DE6 eilica capillary in a Finnigan 4023 gas chmatagraph-mamspedrometer (GC-Ms) was 83-280 OC at 2 deg/min. Analyeis of PAH, phthalate eaters, and csrtain long-chainhydrocarbons was done by s e l d v e ion modtoring With the ion temperature at 260 OC and the electron multiplier at 1300 eV. Both laboratory and field blnnka were analyzed. Blank levels varied by compound from being undetectable to an equivalent air concentration blank level of lese than 5 pg m-8.
Rerults from the September 14-21, IM2, Period The September experiment WM the firet field trial of the mnplen, and mme problemr with emuring ample
&octadecenoic acid 1-tetradecanol phenol naphthnlenc 2-ethylhexanoic acid nonanoic acid hexadecanoic acid octedecanoI dodecylcyclohexanol 3,4,S-trimethyl-l-hexene benzo[k]fluoranthene chrysene benz[o]anthracene pyrene ’ benzo[k]fluoranthene benzo[ghi]perylene CI4-Ca chain hydrocarborn tetradecanoic acid 5-octadecenal 2-octadecenal
integrity, misfitting PUF plugs, and losses during extraction procedures were encountered. Since the first phase of the project was to be a screening for a full range of compounds, reconstructed ion chromatograms (RIC’e)with large mass ranges (40-550 amu) were examined. Table I gives a list of some of the identified organic species. Consistent with other studies of urban and rural environments (6),the majority of the organics detected coneisted of alkanes, aliphatic acids, aryl hydrocarbons, carboxylic acids, and phthalate esters. A surprising amount of fatty acids was seen in the September samples, leading to worries about local contamination from vegetative burning or meat rendering. No obvious local eource was found however. Later work on extracts of river foam (which is produced in copious amounts from Niegara Falls) has shown that the foam has a high concentration of them acids and points to the river as a possible eource. These acids have also been noted in urban samples from Detroit and New York (7). As would be expected from an atmospheric transport perspective, compounds found on the particulate fraction either have well-known anthropogenicpyrolytic murces, such aa the PAH’s, or have ideal physicochemical properties for becoming aerwls. Dioctyl phthalate, for example, makes such an excellent submicronmeter aeroeol that it is used to calibrate lightscattering particle countera Not surprisingly, it is also a ubiquitous compound in the atmoepheric particulate samples. The 8ource of the phthalates has been attributed to municipal incineration (6). Unfortunately, ch!winated species were not seen in this full-range screening of compounds. Subsequent studiee designed to look for PCBs, for example, have shown that selective ion monitoring of only two or three m m m ir required to get enough eeneitivity on the GC-MS to see chlorinated isomers and that significant cleanup of the sample is required. Chlorinated species are more easily analyzed by GC-electron capture detection (ECD) w i t h GC-MS confirmation on selected samples. In order to simplify the problem to one which m d d giw some useful information on the questions of spatial m d temporal variations of the samples, it was decided to focus on t h e e compounds that appeared in nearly rll the rrmplee. Phthalate estere (which were the d3rnin-t pgah on the RIC’e) and PAN’S were chosen for study. Table I1 gives the mean air and particulate concentmtionr of naphthalene, biphenyl, phenanthrene, pyrene, diethyl phthalate (DEP),dibutyl phthalate (DBP), end d i w phthalate (DOP) for the September atudy. Ab0 ahown t EW~IW. m.TWW..
val. p i , M.e, IMT
u v
Table 11. September Air Sampling Results
compound naphthalene biphenyl phenanthrene pyrene diethyl phthalate dibutyl phthalate diisooctyl phthalate
n
particulate concn, pgm"
air concn, Pg m-3
Table 111. J a n u a r y Air Sampling Results
FP/(FP
+ RP)
5 1000 f 671 5 490 f 500 5 180 f 140 3 65 f 53 5 2800 i2300
2400 f 1600 690 f 310 4800 f 1100 300 i 350 3700 i 900
0.62 f 0.07 0.53 f 0.19 0.79 i 0.12 -1 0.59 f 0.14
5 4000 f 2200
1900 f 1300
0.95 f 0.03
340 f 300
0.73 f 0.22
3 4700 f 4500 5
the mean ratio of the front foam plug to total foam plug concentrations [FP/(FP BP)]. The temporal variability in the data accounts for most of the uncertainty in the concentrations. While individual samples and time series are discussed below, data from the individual samples are available in the supplementary material (see paragraph at end of paper regarding supplementary material).
+
Results from the January 25-February 1, 1983, Sampling Period During the midwinter study, volatilization from the river was not likely to occur since the water temperature during the period was 0.4-1.1 "C. The study period was more likely to discern the differences between local scale input of toxics into the air and longer range transport. Consistent with previous work in this area by the Ontario Ministry of the Environment (OME) (8),concentrations of atmospheric particulate PAHs were larger during winter months. This study found much higher levels (3-10 times) of phenanthrene and pyrene in both the gas and particulate phases in winter over late summer. This indicates that source input is the controlling factor for the summer/ winter difference rather than volatilization from particles. Air temperatures during the study varied from -9 to 4 "C with a warm, wet air mass arriving on January 30. Winds were favorable for determining the air mass influence with most points of the compass seen during the period. Thirteen species were measured in both the gas and particulate phases at the three sites. The daily results for Niagara-on-the-Lake, Niagara Falls, and Fort Erie are available in the supplementary material. Mean air concentration data for the three sites have been synthesized in Table I11 as for the previous period. The maximum concentration of lighter weight PAH's is about 30 ng m-3, and the minimum concentration detected was 3 pg m-3. As in the September study, much of the standard deviation of the results is due to temporal variation, but there is also a spatial component to the variability in concentration from these three sites (see below). An additional group of PAHs was seen only on the glass fiber filters and thus can be inferred to have little or no gas-phase component below 4 "C. These were benzouland benzo[k]fluoranthene, benzo[e]- and benzo[a]pyrene, perylene, and benzo[ghi] perylene.
Discussion The two studies showed that a significant gas-phase component exists for PAHs of molecular weight less than 252. It is clear that at even low temperature naphthalene, biphenyl, diethyl phthalate, and dibutyl phthalate are not efficiently trapped with glass fiber filters and PUF. PAHs 558
Environ. Sci. Technol.. Vol. 21, No. 6, 1987
compound naphthalene biphenyl phenanthrene anthracene fluoranthene benzacenaphthalene pyrene benz[a]anthracene chryeene n-C16
n-czz n-Cz4 n-czs diethyl phthalate dibutyl phthalate diisooctyl phthalate benzoulbenzo[k]fluoranthene benzo[e]pyrene benzo[a]pyrene perylene benzo[ghi]perylene CzzH1z
+
n
particulate concn, pg m-3
n
air concn, pg m-3
FP/(FP + RP)
19 160f 170 16 3200 i 1200 19 9600 f 3000 16 22000 f 4100 19 830 f 1000 16 13000 f 5900 19 45 f 57 9 990 960 19 1400 f 1900 9 3700 f 2200 19 1 5 0 f 330 1 770
*
0.63 f 0.15 0.63 f 0.13 0.97 f 0.04 0.96 f 0.03 0.97 f 0.03 0.97
19 1200f 1800 19 2800 f 5600
8
3000 i 2100 bdl"
0.97 f 0.04
3900 f 5500 770 f 360 16 3700 f 3400 9 2800 f 2300 5 680 f 910 2700 f 2600 16
bdi 4200 f 3200 970 f 310 160 f 140 bdl 3800 i 2800
19 6200 f 2600 15
4500 f 3500
0.47 f 0.21
670 i 1100 =
0.69 f 0.21
19 19 19 19 18 19
19 2300
* 1600
15
18 1100 f 1500
bdl
18
420 f 620
bdl
17
230 f 440
bdl
11 23 f 52 12 530 f 1500
bdl bdl
11 390 f 1000
bdl
0.69 f 0.17 0.83 f 0.13 0.50 f 0.12 0.83 f 0.11
bdl = below detection level.
of M, 178 and above can be quantitatively monitored by using this system, which is in agreement with Keller and Bidleman ( 4 ) . Some care may have to be used in interpreting the low molecular weight end of this range when ambient temperatures rise above 30 "C. These results draw into question previously reported particulate concentrations of phenanthrene, anthracene, fluoranthene, benzacenaphthalene, pyrene, and benz[a]anthracene since these have a gas-phase component. Results in the literature from sampling with only filters should be considered to be underestimates of the ambient concentrations of those PAH's in air. Results from the winter sampling period have shown that there is a strong local influence of heavier weight particulate PAH's. In general, the air concentrations of PAH's are highest at Fort Erie, lower at Niagara Falls, and lowest at Niagara-on-the-Lake, which is clearly indicative of the general industrial and automotive inputs of these chemicals into the region. The highest air concentrations for benz[a]anthracene, chrysene, n-C2zand n-CZ4hydrocarbons, and the particulate PAWS were seen at Fort Erie during the January 27-28 period, when there were southeasterly winds (from Buffalo). In order to show the directional influence of the particulate PAH levels seen, the concentrations of the above compounds were normalized to the highest value seen during the week at each site. Average normalized concentration roses for the particulate PAH's are plotted in Figure 2. The lengths of the vectors are site-specific and are intended to show the localinfluence at each site rather than intersite variability. Clearly, the large urban areas of Buffalo, Niagara Falls, NY, and Niagara Falls, Ontario, are the main sources of these PAH's. Also visible is an increase at Niagara-on-the-Lake during NNW flow and is possibly an indication of PAH
PHENANTHRENE (GAS PHASE)
PARTICULATE PAH LAKE
ONTARIO
LAKE
Figure 2. Pollution roses of normaiized average particulate PAH concentration at the three sites. Note that the vectors point into the daily averaged wind and have lengths that are maximized independently at each site.
transport from the Toronto-Hamilton urban corridor. The results for a gas-phase component, phenanthrene, are not so clear-cut (Figure 3). Higher relative concentration levels are seen from sectors that are generally free of major local sources. For lighter components (naphthalene and biphenyl) the roses look even more isotropic. This indicates that longer range transport is involved with the gas-phase components. Another indication of this is the time scale of the behavior of the concentration of these components. Figure 4 shows the time series of the concentrations of phenanthrene (gas phase) and benzo[a]pyrene (particulate phase) at Niagara Falls. Clearly, the short-term (local) episodes seen in the benzo[a]pyrene concentrations are not seen in the phenanthrene levels, and the slow variation of the concentration is more indicative of a regional or mesoscale influence. It should be noted that the general flow into the area was southerly during the middle of the week with the air coming from the eastern seaboard of the U.S. Since this period was also one of relatively warmer air, a possible reason for the rise in phenanthrene levels might be due solely to vapor pressure effects. Yamasaki et al. (3)showed that the ratio of particulate to gas-phase concentrations should be related through a Langmuir relation: log [A][TSP]/[F] = A - B / T where [A] and [F] are the adsorbent and filter concentrations (here in pg m-3) and [TSP] is the suspended particulate concentration in ng m-3. Unfortunately, during this study, filter mass (TSP)was not measured, and direct “YamasakY-type plots cannot be constructed. However, if one takes one component of the sample that is known
ERIE
Flgure 3. Pollution roses of normalized gas-phase phenanthrene concentration at the three sites. 5
I 0.5
0
’
,
P1
v.e
v.8
30
Iinusn 1983
Figure 4. Comparison of gas-phase phenanthrene and particulate+) and Niagara Falls ( 0 , A), phase benzo[a]pyrene at Fort Erie (0, respectively; data for the January study period.
to obey a Langmuir isotherm relationship, such as phenanthrene, as a reference, then
where AA and AB are the differences from the reference compound coefficients. For phenanthrene plus anthracene, Yamasaki et al. obtained 4117 and 21.45 for A and B (3). Figure 5 shows Yamasaki plots of the referenced gas/filter concentration ratios for 10 compounds. Since the air temperature varied significantly during the sampling period of most samples (typical temperature variations are indicated on three of the plots), a large degree of the uncertainty in the slopes is probably due to temperature variation. The coefficients of the slopes of the regressions are given in Table IV. In general, the accuracy of the Environ. Sci. Technol., Vol. 21, No. 6, 1987
559
..
10,001
1
BENZO (a) PYRENE -2
i
-3
tI
I
-4'
I
1
1
,
,
NAPHTHALENE
FLUORANTHENE
,
1
1,00(
-
c
0
1
-2
1
3
,
4
BIPHENYL
,
1
,
I
,
,
/I
e ,
,
ANTHRACENE
,
I
,
2
F
IO(
E 2
e
0
' -1 1
,
,
,
,
,
,
PYRENE
I!
1
,
,
,
,
, 10
.....
.:t
DIBUTYLPHTHALATE 34
U
T I - - - - -
'------
-4 I
4
L
--A
35
L- L _ I - - L
38
i_
2
-2
3 8 351
37
D11SOOCTYLPHTWL4TE
I LA---._ 3 82 37 3 78
1
CHIPPAWA PRESENT STUDY NIAGARA FALLS
. L A 73
74
75
76
77
78 79 YEAR
80
81
82
83
Flgure 6. Time series of Ontario Ministry of the Environment sampling since 1973 at ChippewaINiagara Falls for benzo[a]pyrene in the particulate phase. The particulate-phase results from Niagara Falls from this study are included against those from 1983. The geometric mean concentration plus or minus one geometric standard deviation is plotted.
lOOO/Tl'K)
Flgure 5. Yamasaki plots of the relative gas to particulate ratio vs. inverse temperature. Plots are referenced to phenanthrene, which has coefficients of 4117 and 21.45 for A and B . Temperatures are mean daily temperature, and typical temperature variations over a day are shown for naphthalene, dibutyl phthalate, and n-CIB. Estimated errors in the ratio are taken from the standard deviations in the last column of Tables I1 and 111.
--___
Table IV. Parameters for Plots of AF-'/A rF;* compound naphthalene biphenyl anthracene fluoranthene pyrene n-C16
n-Cz2 n-C24
diethyl phthalate dibutyl phthalate dijsooctyl phthalate _"
B
A
r2
3700 f 1500 480 f 750 -400 f 2300 -3100 f 1300 89 f 960 5000 f 2600 -1400 f 1400 -2200 f 3100 -480 f 1400 1600 f 820 1600 f 2900
-13.5 f 0.6 -2.8 f 0.3 1.4 f 0.5 10.6 f 0.3 -1.3 f 0.3 -19.2 f 0.5 3.3 f 0.3 5.3 f 0.6 0.5 f 0.5 -7.5 f 0.3 -7.9 f 0.6
0.26 0.02 0.002 0.30 0.0005 0.22 0.07 0.04 0.007 0.18 0.02
_ I I -
regression was not as good as in Yamasaki et al. or in Keller and Bidleman ( 4 ) . However, the correlation coefficient is also a less accurate measure of the fit when the slope approaches zero (as it does in these differential plots). Correcting for the phenanthrene reference values, this study has anthracene at 22.713700, fluoranthene at 22.511000, and pyrene at 20.2/4000 for AIB. This agrees well with Yamasaki's values of 21.4514117 for anthracene and 20.5514183 for pyrene, but there is a significant difference for fluoranthene's coefficients. In a limited data set such as this, a single outlier can affect the slope significantly. 560
Environ. Sci. Technol., Vol. 21, No. 6, 1987
As indicated in a previous section, particulate phase sampling of PAH's has been conducted in this area before. The Ontario Ministry of the Environment (OME) sampling program from 1973 to 1982 operated a sampler at a site approximately 2 km to the south of the Niagara Falls site used in this study. In addition, during the years 1974-1976, a sampler was located at the site used in this study. Figure 6 shows a time series of annual averaged geometric mean concentrations of benzo[a]pyrene (8). The results from this study are consistent with the trend obtained by OME to lower benzo[a]pyrene concentrations in Niagara Falls. Finally, the data obtained for the phthalates is intriguing. The concentrations of diisooctyl phthalate show a highly irregular particulatelgas ratio, which does not correlate well with either temperature, air mass origin, or precipitation. The possibility exists that there is a local source of phthalates that is uncorrelated with the processes that are producing the PAH's or that there is an unknown source of contamination of the samples. Given that phthalates were not seen in the field blanks, the former is more likely true. Although sampling efficiency for the diethyl phthalate is not good, the relative particulate concentrations at Fort Erie and Niagara Falls would indicate a source to the southwest of Niagara Falls and to the west and northwest or Fort Erie. Conclusions Sampling for gas- and particulate-phase polycyclic aromatic hydrocarbons in the Niagara River area has indicated that, as in previous studies, concentrations of PAH in the air are greatest when the air mass is under the influence of urban and industrial sources. Along the Ni-
agara frontier, this indicates that there will generally be a south to north gradient in the concentration due to the larger population on the U S . side at the Lake Erie end of the river, The study has shown, however, that there is a gas-phase component of the PAH concentration that is more regional in nature and indicates regional and mesoscale transport. The identification of the gas-phase PAH signature highlights the need to monitor both phases in the air, especially when sampling at moderate climatic temperatures. A significant fraction of the PAH’s of molecular weight less than 252 could be lost by solely using filter sampling. For the most toxic PAH’s, those with carcinogenic and teratogenic potential, previous results should be more consistent since little gas-phase component is seen for these species at the temperature monitored here. These results may have impact on sampling techniques to be used for the nitro-PAH’s and oxy-PAH’s. Nitropyrene, for example, may be expected to have a considerable gas-phase component, extrapolating from these results. This indicates that gas-phase sampling should not be neglected in searching for these compounds.
Acknowledgments We thank P. Fellin for his encouragement in starting this project. The cooperation of Ontario Hydro and Parks Canada at the sampling sites was greatly appreciated. The sampling itself was conducted by F. Froude, who made the project successful. Data from the OME network were provided by K. Heidorn of OME, and sampling was under the supervision of K. Trent, OME/West Central Region. A critical reading of the manuscript by D. Lane and S. Jenkins was appreciated.
Supplementary Material Available Five tables showing the air concentration of seven compounds in Niagara-on-the-Lake, the daily air concentrations of 16 compounds in Niagara-on-the-Lake,Niagara Falls, and Fort Erie, and the PAH particulate concentrations (5 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 Microforms Office, American Chemical Society, 1155 16th St., N.W., Washington, DC 20036. Full bibliographic citation (journal, title ofarticle, authors’ names, inclusive pagination, volume number, and issue number) and prepayment, check or money order for $13.00 for photocopy ($15.00 foreign) or $10.00 for microfiche ($11.00 foreign), are required. Registry No. n-CI6,544-76-3; n-Czz,629-97-0; n-Cz4,646-31-1; n-Czs,630-02-4; naphthalene, 91-20-3; biphenyl, 92-52-4;phenanthrene, 85-01-8;anthracene, 120-12-7;fluoranthene, 206-44-0; benzacenaphthalene, 76774-50-0; pyrene, 129-00-0; benz[alanthracene, 56-55-3; chrysene, 218-01-9; diethyl phthalate, 84-66-2; dibutyl phthalate, 84-74-2;benzo[e]pyrene, 192-97-2;benzo[a]pyrene, 50-32-8; perylene, 198-55-0;benzo[ghi]perylene, 191-24-2; diisooctyl phthalate, 27554-26-3;benzene, 71-43-2;heptanoic acid, 111-1444; hexatriacontane, 630-06-8; octanoic acid, 124-07-2; l,Qdibromododecane, 55334-42-4; undecanoic acid, 112-37-8; tributyl ester phosphoric acid, 126-73-8;diethyl pentyl phosphoric acid, 20195-08-8; butyl 2-methylpropyl phthalate, 17851-53-5; dibutyl ester nonanedioic acid, 2917-73-9; benzolj]fluoranthene, 205-82-3; 9-octadecenoicacid, 2027-47-6; 1-tetradecanol, 112-72-1; phenol, 108-95-2;2-ethylhexanoic acid, 149-57-5;nonanoic acid, 112-05-0; hexadecanoic acid, 57-10-3; octadecanol, 26762-44-7; dodecylcyclohexanol, 55000-30-1; 3,4,5-trimethyl-l-hexene, 56728-10-0; benzo[k]fluoranthene, 207-08-9;tetradecanoic acid, 544-63-8; 5-octadecenal, 56554-88-2;2-octadecenal, 56554-96-2.
Literature Cited (1) New York Interagency Task Force on Hazardous Waste. Preliminary Report; New York Interagency Task Force on Hazardous Waste: Albany, NY, March 1979. (2) Smith, R. M.; O’Keefe, P. W.; Aldous, K. M.; Hilker, D. R.; O’Brien, J. E. Environ. Sei. Technol. 1983, 17,6. (3) Yamasaki, H.; Kuwata, K.; Miyamoto, H. Environ. Sci. Technol. 1982,16, 189. (4) Keller, C. D.; Bidleman, T. F. Atmos. Environ. 1984, 18, 837. ( 5 ) Burdick, N. F.; Bidleman, T. F. Anal. Chem. 1981,53,1926. (6) Cautreels, W.; Van Cauwenberghe, E.Atmos. Enuiron. 1976, 10, 447. (7) Hoffman, D.; Wynder, E. L. Air Pollution; Academic: New York, 1978; Vol. 2, p 192. (8) Heidorn, K., Ontario Ministry of the Environment, private communication, 1985.
Received for review June 4,1986. Revised manuscript received December 31, 1986. Accepted February 16, 1987.
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