The Chemistry of Acid Rain - American Chemical Society

The Chemistry of Acid Rain - American Chemical Societyhttps://pubs.acs.org/doi/pdf/10.1021/bk-1987-0349.ch022cultural and livestock feeding activités...
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Chapter 22

Pollutant Deposition in Radiation Fog 1

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Jed M. Waldman , Daniel J. Jacob , J. William Munger, and Michael R. Hoffmann

Downloaded by CORNELL UNIV on September 5, 2016 | http://pubs.acs.org Publication Date: September 3, 1987 | doi: 10.1021/bk-1987-0349.ch022

Department of Environmental Engineering Science, California Institute of Technology (138-78), Pasadena, CA 91125

A. study of atmospheric pollutant behavior was conducted in the southern San Joaquin Valley of California during periods of stagnation, both with and without dense fog. Measurements were made of gas-phase and aerosol pollutant concentrations, fogwater composition, and deposition of solutes to surrogate surfaces. Deposition rates for major species were 5 to 20 times greater during fogs compared to nonfoggy periods. Sulfate-ion deposition velocities measured during fog were 0.5 to 2 cm s . Rates measured for nitrate ion were generally 50% below those for sulfate, except for acidic fog (pH3 d) for valley air. -1

D e p o s i t i o n d u r i n g fog e p i s o d e s can make a s i g n i f i c a n t c o n t r i b u t i o n to the o v e r a l l f l u x o f p o l l u t a n t s i n c e r t a i n e c o s y s t e m s . Further­ more, when a t m o s p h e r i c s t a g n a t i o n p r e v e n t s normal v e n t i l a t i o n i n a r e g i o n , f o g d e p o s i t i o n may become t h e m a i n r o u t e o f p o l l u t a n t removal. Fogs c a n c o n s e q u e n t l y e x e r t dominant c o n t r o l over p o l l u t a n t l e v e l s i n c e r t a i n environments. The s o u t h e r n San J o a q u i n V a l l e y ( S J V ) o f C a l i f o r n i a i s a

'Current address: Department of Environmental & Community Medicine, UMDNJ-Robert Wood Johnson Medical School, Piscataway, NJ 08854 Current address: Center for Earth & Planetary Physics, Harvard University, Cambridge, MA 02138

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0097-6156/87/0349~0250$06.00/0 © 1987 American Chemical Society

Johnson et al.; The Chemistry of Acid Rain ACS Symposium Series; American Chemical Society: Washington, DC, 1987.

22.

WALDMAN ET AL.

Pollutant

Deposition

in Radiation

251

Fog

r e g i o n prone t o w i n t e r t i m e e p i s o d e s o f atmospheric s t a g n a t i o n . These l e a d t o e l e v a t e d p o l l u t a n t c o n c e n t r a t i o n s and/or dense, widespread f o g s . Major o i l - r e c o v e r y o p e r a t i o n s p l u s widespread a g r i c u l t u r a l and l i v e s t o c k f e e d i n g activités a r e i m p o r t a n t sources o f S 0 , Ν€χ, and NH . i n t h e v a l l e y . A m u l t i - f a c e t e d program o f f i e l d m o n i t o r i n g was conducted i n t h e SJV d u r i n g t h e w i n t e r 1984-85, f o c u s i n g on a s p e c t s o f p o l l u t a n t scavenging and removal i n t h e f o g ladden atmosphere. C o n c e n t r a t i o n s o f major s p e c i e s were measured i n gas, d r y a e r o s o l , and fogwater phases. In a d d i t i o n , d e p o s i t i o n a l f l u x e s were m o n i t o r e d by s u r r o g a t e - s u r f a c e methods. These measure­ ments were employed t o d i r e c t l y assess t h e magnitude o f enhanced removal r a t e s caused by f o g . Downloaded by CORNELL UNIV on September 5, 2016 | http://pubs.acs.org Publication Date: September 3, 1987 | doi: 10.1021/bk-1987-0349.ch022

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METHODS F i e l d m o n i t o r i n g was conducted a t two SJV s i t e s , B a k e r s f i e l d A i r p o r t and B u t t o n w i l l o w . Fogwater was sampled by event u s i n g r o t a t i n g - a r m c o l l e c t o r s (RAC) w i t h sampling i n t e r v a l s o f 1 t o 2 h . L i q u i d water c o n t e n t (LWC) v a l u e s were a v e r a g e d o v e r t h e f o g w a t e r s a m p l i n g i n t e r v a l s , c a l c u l a t e d from t h e r a t e o f RAC c o l l e c t i o n . Atmospheric c o n c e n t r a t i o n s o f a e r o s o l , n i t r i c a c i d and ammonia were monitored u s i n g d u a l - f i l t e r methods. T o t a l a e r o s o l samples were c o l l e c t e d on open-faced T e f l o n f i l t e r s operated s i d e - b y - s i d e . N y l o n f i l t e r s and g l a s s - f i b e r f i l t e r s impregnated w i t h o x a l i c a c i d c o l l e c t e d HN0 (g) and N H ( g ) , r e s p e c t i v e l y . Samplers were r u n t w i c e d a i l y (0000 t o 0400 and 1200 t o 1600 P S T ) , except d u r i n g f o g e p i s o d e s , when they were r u n c o n t i n u o u s l y f o r 2 t o 4-h i n t e r v a l s . Further d e t a i l s of sampling methods and s i t e s a r e g i v e n elsewhere ( 1 , 2 ) . 3

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P o l y s t y r e n e p e t r i d i s h e s (154 cm ) w i t h t h e i r l i p (1.2 cm) upwards were deployed t o c o n t i n u o u s l y m o n i t o r f o g and d r y p a r t i c l e deposition. These were changed t w i c e p e r day (0800 and 1600 PST) d u r i n g nonfoggy p e r i o d s o r , more f r e q u e n t l y d u r i n g f o g , c o n c u r r e n t to f i l t e r sampling i n t e r v a l s . P e t r i d i s h e s (PD) were e x t r a c t e d w i t h 10 mL o f d i s t i l l e d , d e - i o n i z e d water immediately f o l l o w i n g t h e end of ambient e x p o s u r e . Subsequent e x t r a c t i o n s i n d i c a t e d t h a t complete r e c o v e r y (i.e.,>90%) was a c h i e v e d . S i d e - b y - s i d e sample comparisons were i n good agreement· The use o f s u r r o g a t e s u r f a c e s t o measure d e p o s i t i o n r a t e s remains c o n t r o v e r s i a l due t o t h e u n c e r t a i n t y i n e x t r a p o l a t i n g these r e s u l t s t o n a t u r a l surfaces, e s p e c i a l l y regarding deposition of gases o r submicron a e r o s o l ( 3 ) . The c o n d i t i o n s i n t h e SJV d u r i n g the f o g / a e r o s o l study a l l o w e d us t o a p p l y s i m p l i f y i n g assumptions regarding t h e dominant d e p o s i t i o n p r o c e s s e s . The v a l l e y i s u n i f o r m l y f l a t , and over 85% o f t h e s u r f a c e cover i s open c r o p l a n d or rangeland. There i s m i n i m a l canopy s t r u c t u r e , e s p e c i a l l y d u r i n g wintertime. On a r e g i o n a l s c a l e , t h e t e r r a i n i s r e l a t i v e l y sparse and r a t h e r i n e f f i c i e n t f o r i m p a c t i o n . Furthermore, winds i n the_SJV u n d e r s t a g n a n t c o n d i t i o n s a r e u s u a l l y q u i t e l i g h t (