Air Pollution Correlation of the macro- and micrometeorological characteristics of the pine blight area with the concentrations of acid gases found in the atmosphere explains the shape of the area of visible damage. The cross-sectional concentrationp atterns obtained by analysis of rain-water samples collected a t 82 locations during the months of September and October 1950 show that the major source of fluorides in the north Spokane area coincides with the center of the observed ponderosa pine damage; that significant quantities of fluorides do not originate outside the area t o be transported into the area by the winds (the one area of high fluoride outside the blighted area may be explained by the proximity of a portland cement operation and the resultant leaching of fluoride from the cement dust deposited in the rain collector); that the sulfur dispersion pattern does not coincide with the fluoride patterns; that sulfur found in the rain water resulted from industrial operations, a burning trash dump, domestic heating, and internal combustion engines; and that fluorine found in the rain water resulted primarily from industrial operations. ACKNOWLEDGMENT
Many individuals and organizations have given assistance, suggestions, and cooperation during the investigation of the role of atmospheric pollution in the ponderosa pine blight. A complete listing of all groups and individuals would he voluminous; however, special mention Fhould be made of the following: The City of Spokane, Spokane County, and the Washington State Department of Agriculture through the Inland Empire Pine Damage Committee for the financial aid which helped make the investigation possible. Technical personnel of the Division of Industrial Research shops.
Citizens of Spokane County who generously allowed various pieces of sampling equipment t o be located on their roperty. Wind direction and speed data from Kaiser Aruminum and Chemical Corp., Spokane, Wash. Pacific Northwest Alloys, Inc., Spokane, Wash. Phillips Petroleum Co., Spokane, Wash. Bud’s Welding and Auto Repair, Spokane, Wash. Damage pattern map by C. G. Shaw. Robert McComb, officer in charge, U. S. Weather Bureau, Spokane Airport. LITERATURE CITED
(1) Assoc. Offic. Agr. Chemists, “Official and Tentative Methods of
Analysis,” 6 t h ed., pp. 477 ff., 1945. (2) De Ong, E. R., PhytopathoEogy, 36, 469-71 (1946). (3) “International Critical Tables,” Val. 111, p. 2 8 , New York.
McGraw-Hill Book Co., 1926. (4) Katz, Morris, IND. ENG.CHEM.,41, 2450-65 (1949). (5) La Fleur, W., Monthly BuEl. Ohio Florists’ Assoc., No. 232, (January 1949). (6) Laurie, A,, Hasek, R. F.. and La Fleur, W., Proc. Am. SOC.Hort. Sci., 53, 466-72 (1949). (7) MacIntire, W. H., et al., IND. ENG.CHEM.,4 1 , 2 4 6 6 - 7 5 (1949). ( 8 ) Miller, V. L., Johnson, Folke, and Allmendinger, D. F.. Phytopathology, 38, 30-7 (1948). (9) Ibid., 4 0 , 2 3 9 - 4 6 (1950). (10) “Scott’s Standard Methods of Chemical Analysis,” 6th ed., N. H. Furman, ed., Vol. 1, p. 925, New York, D. Van Nostrand Co., 1939. (11) Shaw, C. G., Abbitt, W. H., and Adams, M. F., personal com-
munication. (12) Thomas, M. D., and Hill, G. R., Plant Physiot., 10, 241-307 (1935).
(13) Willett, H. C., “Lectures Presented a t Inservice Training
Course in Air Pollution,” p. 26, Ann Arbor, Mich., University of Michigan, 1950. RECEIVED for review June 5, 1951. ACCEPTEDMarch 31, 1952. Presented before the Division of Industrial and Engineering Chemistry at the 119th Meeting of the AMERICANCHEMICAL SOCIETY, Cleveland, Ohio.
Measurement of Atlnospheric Fluorine 1
ANALYSES OF RAIN WATERS AND SPANISH MOSS EXPOSURES W. H. MACINTIRE, L. J. HARDIN, AND WINNIFRED HESTER The University of Tennessee Agricultural Experiment Station, Knoxville, Tenn.
Rainfall collections at six points were analyzed to measure the periodic washdowns of fluorine from the atmosphere in relation to the locations of operations that emit fluoric effluents, and charges of Spanish moss were exposed to measure progressive intake of fluorine from the atmosphere. Longer intervals between rainfall caused higher concentrations of fluorine at the several locations. Proximities of samplings to sources of emissions were reflected by higher concentrations of fluorine in rain waters. Exposures of Spanish moss acquired substantial progressive enhancements in fluorine uptake at points near those where fluoric emissions occurred. The findings demonstrate that these two feasible and economical procedures can be implemented in parallel to establish whether a particular locale is subject to atmospheric pollution and the degree of pollution. Through integration with meteorological records, the determined occurrences of fluorine in the rain waters might indicate the origins of the contaminative effluents.
June 1952
I
N 1943, according to Sappington ( 5 ) , flouric effluents were
being emitted to the atmosphere by 29 industrial operations in the United States. Such emissions occur a t certain locales of two Tennessee counties, in which are located experiment station farms of The University of Tennessee. The farm in Blount County is about 6 miles distant from the aluminum production operations at Alcoa and is located on a soil formation that has a meager content of fluorine; but the farm in Maury County is within a 10-mile radius of several manufacturing operations for production of phosphorus and phosphates and is located on the Maury soils that are characterized by their unusual contents of phosphorus and fluorine. (Use of the word “fluorine” in this text connotes the occurrence of that element as a component of some fluoric combination.) Because of the many contentions that fluoric emissions have caused injurious effects upon plant and animal life in certain locales of those two counties and because of the direct concern of the university, an over-all study of the effluent problem was inau-
INDUSTRIAL AND ENGINEERING CHEMISTRY
1365
Air Pollution gurated as a joint responsibility of the departments of chemistry and animal husbandry of the Tennessee Agricultural Experiment Station. One phase of the chemical approach w-as t,o deterniine occurrences of fluorine in the atmosphere, rain, stream and pond waters, soils, and vegetation and animal bones in the specified east Tennessee and middle Tennessee locales. ATMOSPHERIC OCCURRENCES OF FLUORIZl E
I n an initial approach to the occurrence of fluorine in the atmosphere, determinations Tvere made on 60-cubic foot samples of air that were drawn through cellulose filters by means of a gas-driven pump, which was mounted on a truck. CROS?.VILLE STATION CUMBERL4ND PLATEAU -UNIVERSITY
O F T E N N . FARM
SPRINGFIELD STATION
MAURY COUNTY AREA F THE U.T RADIUSINOBOMlLE UPERIMENT STAnON
L
UNIVERSITYOOF TENN. FARM BLOUNT COUNTY
Figure 1. Locations in Tennessee Where Rain Waters Were Collected and Where Charges of Spanish Rloss Were Exposed
-J
I :31
m 2m C A N NCCO
600
I
?
I
= A M(DN
e 3,1
0
From the analyses of several series of filtered and unfilt,ered samples of atmosphere that were drawn at different points in the locales under study, it became evident, that to obtain significant and conclusive data, this approach xould require the operation of several truck-mounted units for long ,successionsof daily analyses of large volumes of air in the field arid that increases in chcmistry personnel would he necessaq-. -4ftw it appeared iniprohahle that t,he analytical result's would justify the expense, the periodic analyses of field samples of the at,mosphere were discontinued. Similar approaches x-ere made and corresponding decisions were arrived a t , separately and independently, b>- corporations interested in t,heoccurrence of fluorine in the atmosphere in t x o localities that Twre purported to be affected adversely because of fluoric effluents. AKALYSES OF RAlK WATERS
hCCh
97"
NMC?
w
h m
1366
I n 1937, a single collection of rainfall a t Knoxville was fount1 t o have brought doxn 0.15 pound of fluorine per acre. Because of this finding and because of ohservations in a 10-year study of the washdown of sulfur gases and solid aerosols at ten points in Tennessee ( d ) , it seemed probable that much could be learned as to atmospheric occurrences of fluorine through the determina.tion of the fluoride content of everj- rainfall over extended periods. Therefore, in 1948, the fluorine contents of the rainfall collections from six points in Tennessee were determined and result'ant washdowns per acre were computed, as recorded in Table I. The per acre washdovms of fluorine a t Crossville on the Cumberland Plateau and a t Springfield, which is near the Kentucky border (Figure 1), vere decidedly smaller than corresponding m-ashdowns a t Knoxville and on the Blount County farm some 6 miles from an aluminum production operation. The a-ashdowns a t Crossville and Springfield were also decidedly smaller than the washdowns at two collection points on the Rliddle Tennessee Station farm, which is near several extensive phosphate operations in Maury County ( 1 ) . Because of the decisive indications from t'he determinations of 1948, the analyses of rain waters were continued, and the findings for 1949 and 1950 are reported in detail in Tables I1 and 111. The range of concentration of fluorine in the periodic collectioiis
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
Vol. 44, No. 6
Air Pollution
. . 0. 0
d a m mmN oi-
Nhh
000
000
mot-
2 h 0
i
!
Hi
m
h
0
41
i
C o? 0
C.
N 0-C b CN
399
ccc
and totals for the three annual washdown increments of fluorine are given as pounds per acre in Table 117. The values reported for fluorine brought down per acrr per annum by the rain waters in 1948, 1949, and 1950 were obtained by multiplying the p.p.m. of fluorine in the precipitation for each interval against the per acre weight of that precipitation and aggregating the several values so obtained. The findings embodied in Tables I to IV show a common order for the inwash of atmosphere-derived fluorine a t the several locations where the collections of the rainfalls were made periodically in east Tennessee and in middle Tennessee. Each year the highest concentrations of fluorine in the rain waters and the largest washdowns were at the locations nearest the manufacturing operations that produce either aluminum or phosphatic materials and the lowest concentrations and smallest washdowns were at the distant points, Crossville and Springfield. The quantities of fluorine washed down a t the Knoxville lysimeters and a t the Blount County farm in 1948 and 1950 were comparable. In 1949, however, the washdown at the Knoxville location was considerably less than the washdown a t the Blount County farm, which is equidistant between the Alcoa plant and the Knoxville lysimeters. The relatively high occurrence of fluorine in the collections of rain waters a t Knoxville are deemed attributable to aerosols resultant from the extensive use of bituminous coal, the fluorine content of which has been placed a t 100 p.p.m. ( 3 ) . With one exception, the quantities of fluorine in the washdowns per acre per annum a t the several locations were less in 1949 and showed further decrease in 1950. Those decreases may reflect the engineering provisions that have been made to diminish the quantity of the fluoric emissions in the aluminum manufacturing operations in Blount County and in certain of the phosphorus operations in Maury County. Because of the similarities in annual precipitations, variations between the washdowns of fluorine. per annum cannot be attributed to difference in rainfall. The drier and longer the interval between the collections of rain waters, the larger will be the quantities of aerosols and solids in the atmosphere, and these are washed down almost entirely in the early inch-fractions of normal precipitations. This conclusion is based upon related findings that the air was virtually cleansed of occurrences of calcium sulfate after the first half inch of rain (9)and assumption that a like air-wash of fluoiic materials would occur. The data embodied in Table I are corrective replacements for data given in Table I of a previous presentation ( 1 ) . The data there recorded were .obtained by multiplying the weight of the rainfall per acre per month against the mean of the concentrations of fluorine in the several rain water collections for the month. But, when the p.p.m. of fluorine in each periodic collection of rain waters is multiplied against the per acre weight of the rainfall for the same period and the separate quantities so computed are aggregated per month, the results are less than those obtained when the weight of each month's precipitation per acre is multiplied against the mean of the several p.p.m. of fluorine in the month's collections. The presently reported values for 1948 in Table I and those for 1949 and 1950 in Tables I1 and 111,respectively, and summarized in Table IV, therefore, register the successive quarterly and annual aggregates of those quantities of fluorine t h a t were washed from the atmosphere by the periodic rainfalls. SPANISH IMOSS EXPOSURES
Because of different factors, chemical solids had not proved entirely satisfactory as exposures t o register, cumulatively, the fixations of fluoric compounds from the atmosphere, and use of reagent materials was discontinued. After a Florida visitor revealed that Spanish moss, an epiphyte, had been used as a medium for the sorbtion of fluoric volatiles from the atmosphere a t one point in June 1952
INDUSTRIAL AND E
Z I N E E R I N G CHEMISTRY
1367
Air Pollution TABLE 111. FLUORIKE WASHDOWN AND CONCENTRATION RANGE19RAINWATERSOF 1950 Knoxville Rainfall, Fluorinea, inches lb./aore
1950
January 9.79 February 6.44 March 5.95 Subtotals 22.18 April 1.69 May 7.37 June 4.94 Subtotals 14.00 July 5.99 4.38 August September 2.08 Subtotala 12.45 October 1.19 November 2.83 December 3.55 Subtotals 7.57 Annual totals 56.20
0.184 0.088 0.116
Blount C o u n t y Rainfall, FluorineQ, inches Ib./acre
- 0.044
-
- 0.086
- 7.43
- 0.066
-
-
-
0.065 0,083
0.081 0.045 0.168 0.450
0.388
0.192
0.212
0.684 1.476
0.191 0.075 0.118
9.39 5.72 5.17 1.06 5.24 3.10
- 0.173 9.40
4.37 1.75
1.55 2.48 3.07
0.053 0.207 0.088
13.55 __ 7.10 50.33
TABLE I\i.
0 348
0.131 0.054
0 358
1.96 7.04 4.90 5.22 7.74 3.40
~
0.061 0.099 0.045
Range of fluorine content of individual samples, 1950, p.p.m. Knoxville 0.01-0.56 Blount C o u n t y 0.02-0.62 Crossvil!e 0.01-0.12 Columbia office 0.11-1.03 Columbia plot 0.08-0.36 b Office collector. C Plot collector.
a
14.79 6.78 6.32
0.384
20.28
__.
Crossville Rainfall, FluorineQ, inches 1b.iacre
~
0,205 1.295
0.93 5,31 3.29
d
d d
27.89 -
...
e
0.093f 9
0.093 13.90 0,074 O.017h I
16.36 0.009
0,091 -
9.53 67.68
rn
0.023 0.015k
0.047
Rainfall, inches 16.42 8.23 5.21 2.06 5.87 4.12
Columbia Fluorinea, Lb./Acre l b 2c d d d
d d
29.86 -
3.07 6.23 1.96 0.60 6.66 2.45
d
...
0.160 0.173
12.06 0.305
-
-
0.679
0.333
0.374i d
11.26
...
I 0.182 0.164
0.346
0.152 0.117i d
0.268 d
d d d
d d
9.71 62.88
1.012
~
0.615
d S o samples collected during this quarter. e No collections in April. i Six d a y s of rainfall totaling 1.79 inches, n o t sampled. 0 KO collections a t Plateau Experiment Station in June. h Nine d a y s of rainfall totaling 5.53 inches, n o t sampled. i Eight days of rainfall totaling 3.18 inches, not sampled. i No collections in September. k Kine d a y s of rainfall totaling 0.65 inch, not sampled.
SCMMARIZ.4TION O F \JTASHDOWNO F FLUORINE A S D COiYCESTRATION RANGES I N RAINWATERS OF 1948, 1949, AND 1950
Florida moss also were exposed, sheltered and unsheltered, at foul points either on Collections or near the Middle Tennessee ExneriKnoxville 1.986 1.741 1.476 0.02-1.23 0.010-0.790 0.010-0.560 ment Station in hlaury County, between Blount Co. farm 2,130 2,530 1,295 0.05-0.72 0.013-0.780 0.020-0,620 Crossville 0.624 0.311 0.:31 0.00-0.26 0,014-0.069 0.010-0.120 November 16, 1950, and February 15, Springfield 0.163” 0.085b 0.03-0.14 0,061-0.152b 1951. Each of these charges showed a Columbia, office 2.681 2.284 1.012d 0.10-1.23 0.058-0 910 0,1iOii:030d Columbia, plot 2.491 1.950 0.615d 0.06-1.40 0.053-0.950 0.080-0 36d substantial intake of fluorine, and one final content \vas six times tjhe initial cona Second a n d third uarters only. c N o t collected. h Second quarter on?y. d L a s t three quarters. tent of 26 p.p.m. The differences between fluorine intakes by the charges exposed under shelter and without shelter were TABLEv. FLUORINE CONTENT O F SPANISH MOSS A-FTER 3 MOSTH’SEXPOSURE AT Two EXPERIMENT STATIONLOCATIOXS, not so large as those found for the exposures made in Knoxville KNOXVILLE and vicinity, and the respective comparisons recorded in Table Fluorinea, Sample VI were not so consistent as those given in Table V. P. P. 1’1. NO. Point of Exposure The duration of the exposures a t Knoxville and in Maury 26 Initial sample of moss6 County included periods in which weather conditions were unusu2222 Under eaves of barn, Blount County farm0 117 2224 I n tree near same b a r n Blount County f a r m e 74 ally severe and, apparently, the moss was killed by the intense cold 2303 I n tree a t U. T. lysimeier installation Knoxvilled 109 79 2304 Under eaves of lysimeter bldg., K n o x h l e d in one of those periods. In case the intake of fluorine by the moss is primarily through respiration, the killing of the moss a Air-dry basis. b Obtained from near Gainesville Fla. resulted in a cessation in the biological intake of fluorine. Further September 20, 1950, t o Decernder 20, 1950. work may determine whether the intake of fluorine by the moss is d October 22, 1950, to J a n u a r y 23, 1951. t,hrough respiration or is effected through fixation, either chemical or physical. The two foregoing trial-exposure experiments were elaborated that state, quantities of the moss were obtained through the courthrough subsequent series of 4-month exposures of a second lot tesy of the Black Laboratories of Gainesville, Fla., and were used, of Florida moss a t eight “inside” and “outside” locations in the as shown in Table V, for the exposures a t the University’s Blount Blount County and Knoxville vicinities (Table 1711) and through County farm, September 20 to December 20, 1950, and a t Knoxcorresponding exposures on the nine farms identified on the conville from October 22, 1950, to January 23, ti^^
of
Pounds Precipitated per Acre 1948 1949 1950
acquired by the companion charge of sheltered moss. Corresponding charges of the initial lot of
1368
P.P.3I. Range in Rainwater 1948 1949 1950
D
Figure 2.
Illustrations of Spanish Moss Used for Exposures A
-
bulk X 2
B = follicles X 2
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 44, No. 6
Air Pollution TABLEVI. FLUORINE CONTENTOF SPANISHMoss AFTER 3 MONTHS’ EXPOSURE AT FOUR LOCATIONSNEAR MIDDLE TENNESSEE EXPERIMENT STATION^ (November 16, 1950, to February 15, 1951) Point of Fluorineb, Exposure P.P.M. Near operation A 80 In tiee 3371A 96 Under shelter 3372 Operation MTES 54 Outside 3373 48 Under shelter 3374 Near operation M 51 Outside 3375 62 Under shelter 3376 Near operation V 163 Outside 3377 139 Under shelter 3378 Fluorine oontent of moss before exposure was 26 p.p.m. Air-dry basis. Sample NO.
a b
centric circle diagram and legend and in Figure 3. The designation “inside” connotes exposure under either a shed or the eaves of a barn for protection against rain, but without restriction as t o atmospheric circulation, whereas “outside” connotes exposure without cover and usually in a tree. As shown in Table VII, substantial intakes of fluorine from the atmosphere were registered by all the charges that were exposed at heights of 10 to 15 feet on the three farms in Blount County and a t the other specified locations. In general, fluorine intake progressed with the duration of an exposure. However, the dissolvant action by the 2.89-inch rainfall during the last 25 days is reflected through the lessening of the maximal fluorine concentration of 2418 p.p.m. in the collection of August 24, near the pot room, t o the final concentration of 1760 p.p.m. in the collection of September 18, and a decrease from 210 to 67 p.p.m. in the moss exposure in the tree near the pumping station. The minor variances in the relationships between the occurrences of fluorine in the inside and outside charges are probably attributable to differences in the local precipitations. The Spanish moss used in the 4-month exposures on the farms in Maury County (Table VIII) was obtained from near Wilmington, N. C., and contained 22 p.p.m. of fluorine, air-dry basis. The locations of the exposures are registered by letters in Figure 3, where they appear spaced within 10-mile radius from the office of the old Middle Tennessee Experiment Station. Enhancements in fluorine contents were progressive in all charges of moss t h a t were exposed inside. Again, however, not every final part per
TABLE VII.
Map Location 90-5
S Figure 3. Locations of Maury County Farms Where MOSS Was Exposed within 10-Mile Radius of Old Experiment Statihn and Where Several Processing Operat i o n s That E m i t Fluorine Are Located G Old M.T. S t a t i o n H = Baker, B . I = New M.T. Station
million was maximal in the charges t h a t had been subjected to rainfall. The final part per million of fluorine in the outside exposures on the Hitch and Magill farms were greater than the occurrences in the companion inside exposures. The opposite relationship obtained, however, in the comparisons for the University of Tennessee Stations in Blount and Knoxville. The data of Table VI11 afford two comparisons that were not developed by the data of Table VII. The intakes of fluorine by the exposured charges of moss were a t inside and outside locations on nine Maury County farms, one of which is the former Middle Tennessee Station. The intakes of fluorine by the inside and outside placements of moss on t h a t farm were considerably greater than the intakes by t h e charges correspondingly exposed on the farm recently acquired by the university as a new experiment sta-
FLUORINE CONTENT OF SPANISH Moss AFTER EXPOSURES IN BLOUNT AND KNOXCOUNTIES (Fluorine content of Florida moss, 27 p.p.m. on air-dry basis) First Collection Second Collection Third Colleotion Rainfall, Fluorineb, Rainfall, Fluorineb, Rainfall, Fluorineb, Inches P.P.M. Inches P.P.M. Inches P.P.M. --6-15-51~7-12-51-------. --8-24-51-
-.
Exposurea Hitch farm (5-2-51) Inside .. 8.91 25 Outside 5,:41“ 50 3.50 75 180-3 Magill farm (5-4-51) Inside 4.97 38 3.50 34 Outside 4.97 53 3.50 107 Kidd farm (5-4-51) 270-3 4.97 91 Inside 3.50 80 4.97 64 Outside 3.50 105 45-3.5 Pumping station (5-14-51) In shed 4.19 52 3.50 91 4.19 99 In tree 3.50 107 --7-5-51-0-0 ~--7-30-51Near pot room (5-26-51) 7.78 1240 Outside 1.86 1300 315-1 Operation A (5-26-51) Outside 7.78 50 1.86 127 0-5 U.T. farm (Blount), (5-26-51) Inside 7.78 38 1.86 99 7.78 29 Outside 1.86 44 0-9 U.T. lysimeters (5-26-51) .. Inside 2.12 31 Outside 6:3ld 61 2.12 51 a Inside = protection from rain but subject to atmospheric circulation; outside, generally in a tree. b Air-dry basis. C Rainfall a t locations other than 0-9 measured a t U. S. Weather Bureau, Knoxville airport. d Rainfall a t 0-9 locations measured a t U. S. Weather Bureau, U.T. lysimeter.
-
June 1952
-
D = Cecil, P. E = Hargrove F = Garrett
A = Dungye B = Baker, J. C = Mafisey
Fourth Collection Rainfall, Fluorineb. Inches P.P.M. ,-9-18-51-
3.50 3.50
32 76
2.89 2.89
54 92
3.50 3.50
70 101
2.89 2.89
130 146
3.50 3.50
168 63
2.89
..
192
3.50 3 50
268 210
2.89 2.89
534 67 1760
..
1.42
2418
2.89
1.42
126
2.89
133
1.42 1.42
79 58
2.89 2.89
103 48
1.57 1.57
29 60
4.83 4.83
27 70
INDUSTRIAL A N D ENGI‘NEERING CHEMISTRY
1369
A
i
r Pollution ~~
~
-
~~
TABLE T7111. FLUORISE C O S T E N T O F SPANISH
>lap Location 315-6 3 15-4 225-12 225-6 90-8 180-8
0-0
45-4 45-10
‘1
h
Exposure“ Dungye (5-1-51) Inside Outside Baker, J. R . (5-1-51) Inside Outside Massey (5-1-51) Inside Outside Cecil (5-1-51) Inside Outside Harprove (5-2-51) Inside Outside Garret,t (5.2-51) Inside Outside Charge enc. in paper
h1OSS AFTER EXPOSCRES O S FARhlS I N J 1 4 U R Y C O U S T Y
(Fluorine content of North Carolina moss, 22 p.p.m. o n air-dry basis) __ Second Collection Third Collection First Collection Rainfall, Fluorineb, Rainfall, Fluorineb, Rainfall, Fluorineb: Inches P.P.M. Inches P.P.M. Inches P.P.hI. ~6-1-51-----. ,-7-1-51--8-1-51-
Old M T E S (.5-7-51) Inside Outside Charge enc. in paper bag Baker, R . (5-8-61) Inside Outside New MTES (5-8.51) Inside Outside Charge enc. in paper bag
-
7
1.01 1.01
1.!* a3
F o u r t h Collection Rainfall, Fluorineb, Inches P. P. M. 9-1-51-
-
7 69 7.69
243 271
2.6% 2.68
214
1 16
1.16
256 290
340
1.01 1.01
53 52
7.69 7.69
Id7 196
2.68 2 68
141 264
1.16 1.16
184 200
1.01 1.01
31
7.69 7.69
56
46
112
2 68 2.68
51 131
1,16 1.16
56 192
1.01 1.01
34 41
7.69 7.69
51 111
2.68 2.68
38 146
i:i6
164
1.01 1.01
28 53
7 69 7.69
63 86
2.68 2.68
31 109
1.16 1.16
112
37 38
7.69 7 69
42 86
2.68 2.68
46 169
1.16 1.16
1.01 1.01
..
..
1.71 1.74
43 48
-4-7-51-
..
..
8.36 8.36
63 92
. ---7-7-51-
1.74 1.74
51 103
8.36
8.36
158 233
1.74 1.74
20 34
8.36 8 36
30
..
..
-
17
..
..
--8-741-
..
1.25 1.25
..
62
___
..
9.7-51-
246
1.25
226
1 72 1.72
1 25
82 64
1.72 1.72
, .
..
--
113 2?!
204
..
48
137 52
1.72 1.72
..
1.25
40
33
..
624
.
21
67
4 .i
Inside = protection from rain but subject t o atmospheric circulation; outside, generally in a tree. Air-dry basis.
tion in Maury County. Uniformly, the four monthly analyses of outside charges of moss showed intakes of fluorine substantially greater than the intakes effected by the inside charges. The fluorine analyses for the Garrett farm, location 180-8, and those for the old and new experiment station farms, locations 0-0 and 45-10, serve to establish a second distinction. At each of those locations charges of moss were enclosed in paper bags and then placed adjacent to unbagged charges that were exposed a t outside locations, as specified in Table T’III. After 4 months, simultaneous analyses of the several charges of moss showed some increases in the fluorine content of the bagged charges, but those increases were decidedly less than the increases in fluorine content shown for t,he companion charges that were not bagged. Ahnoted, it is not known whether the intake of fluorine by the moss is a function of respiration or one of chemical activity by the fluoric compounds or one of sorbtion. It is expected that this aspect will bedeveloped through findings obtained as to differential intake by the moss, after charges of it are subjected t o various extractions and then exposed in fluorine-contaminated atmospheres.
tions. Higher concentrations of fluorine in the rain miters and larger washdowns occurred after longer and drier intervals betvieen rains. I n 1950, charges of Spanish moss >?ereexposed 3 months, with and without protection against rainfall, a t several points i n Blount and Knox Counties in east Tennessee and in hlaury County in middle Tennessee, and, in 1951, similar exposures of 3 months’ duration were made a t four points near phosphatic operations in Maury County. Four pairs of charges of moss were made inside and outside, for successive sampling a t each of eight points in Knox and Blount Counties and on nine I l a u r y County farms, locations of which were specified in relation to the hliddle Tennessee Experiment Station. A11 the exposures acquired significant enhancements in fluorine contents that were cumulative and indicative of proximity to fluoric emissions. In general, the enhancements in fluorine content acquiied by the moss in outside exposures exceeded the contents acquired by the inside exposures, rain waters being causal for the exceptions. Only slight increases in fluorine content mere registered b>- the charges of moss that were enclosed in paper bags placed adjacent to outside evposures that showed high intakes a t three points in l l a u r y County ACKNOW LEDGMERT
SUMMARY
.Itmospheric fluorine was one aspect of a comprehensive chemistry-animal husbandry study of the possible effects of fluoric effluents upon plant and animal life in two widely separated counties in Tennessee. Following several series of periodic analyses of large volumes of field air, filtered and unfiltered, that approach was deemed unfeasible and mas discontinued in favor of t,he procedures nox- reported. I n 1948 t o 1950, p.p.m. of fluorine in all precipitations and resultant washdowns per acre were determined and aggregated per annum for six Tennessee locales in relation t o proximities t o operat,ions that emit fluoric effluents. This procedure is deemed more exact than the one in which the monthly means of parts per million are applied t o the respective monthly weights of rain waters per acre. The fluorine concentrations and the washdowns per acre were significantly greater with nearness t o the operations that process either alumina or rock phosphate, but the 1950 findings indicate that corrective inst,allations served t o diminish fluoric emissions. The 3-year washdown of fluorine a t the university farm in Knoxville \vas 87% of the washdown at the Blount County Farm some 5 t,o 6 miles from the Alcoa opera-
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hclrnowledgment is made to G. E. Hunt of the Department of Botany, College of Liberal Arts, The Cnivwsity of Tennessee, for t h r pictwes of the moss. REFERENCES
(1) hIacIntire, W. H., and Associates, ISD. ENG.CHEM.,41, 2468 (1949).
( 2 ) MacIntire, W. H., and Young,
J. B.. Soil Science, 15, 205-27
(1923). (3) Robinson, ’177. O., and Edington, G., Ibid., 61, 341-53 (1946). (4) Yanchis, J. M., ISD.EA-G.CHEDI., 26, 134-5 (1934). ( 5 ) Sappington, C. O., “Essentials of Industrial Health,” pp, 227 -8, Philadelphia, J. B. Lippincott Co., 1943. (6) Viillard, H. H., and TTinter, 0. B., ISD. EKG.CHEM.,25, 7- LO (1933). RECEIVED for re\-iew Noirember 8, 1951. ACCEPTED >larch 6, 1952, Paper presented a t Southwide Meeting of Wilson Dam Section of t h e AMERICASCHEYICALSOCIETYa n d Southern Association of Science and Industry, Inc., Wilson Dam, Bla., October 18-20, 1951. T h e findings were obtained in t h e operation of a research a n d marketing project, approved b y t h e U. S. Office of Experiment Stations.
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 44, No. 6
