Environmental Letters
ISSN: 0013-9300 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/lesa17
Determination of Nickel and Vanadium in the Atmosphere of Eastern Massachusetts Eugene F. Barry , Manuel T. Rei , H. H. Reynolds & Joseph O'brien To cite this article: Eugene F. Barry , Manuel T. Rei , H. H. Reynolds & Joseph O'brien (1975) Determination of Nickel and Vanadium in the Atmosphere of Eastern Massachusetts, Environmental Letters, 8:4, 381-385, DOI: 10.1080/00139307509437448 To link to this article: http://dx.doi.org/10.1080/00139307509437448
Published online: 02 Sep 2009.
Submit your article to this journal
Article views: 2
View related articles
Full Terms & Conditions of access and use can be found at http://www.tandfonline.com/action/journalInformation?journalCode=2esa20 Download by: [NUS National University of Singapore]
Date: 06 November 2015, At: 12:33
ENVIRONMENTAL LETTERS, 8(4), 381-385 (1975)
DETERXINATION OF NICKEL AND VANADIIJN I N THE ATMOSPHERE OF EASTERN MASSACHLEETTS
Downloaded by [NUS National University of Singapore] at 12:33 06 November 2015
KEY WOWS:
Atmospheric p a r t i c u l a t e s , n i c k e l , vanadium, atomic absorption spectroscopy
Eugene F. Barry, Department of Chemistry Manuel T. R e i and H.H. Reynolds, Department of Enviromental Studies L o w e l l Technological I n s t i t u t e L o w e l l , Massachusetts 01854 Joseph O'Brien Commonwealth o f Massachusetts Department of P u b l i c Health Lawrence Experiment S t a t i o n Lawrence, llassachusetts 01843 INTRODUCTION
For t h e p a s t t e n y e a r s t h e r e has been a growing concern about t h e presence of heavy metals i n urban and i n d u s t r i a l atmospheres.
Although l e a d has been
t h e s u b j e c t of many ~ t u d i e s , l - recent ~ research e f f o r t s have focused on t h e determination of o t h e r r n e t a l ~ . ~ Of , ~ p a r t i c u l a r i n t e r e s t i n t h e p r e s e n t inv e s t i g a t i o n were n i c k e l and vanadium s i n c e t h e i r main known source i n t h e atmosphere of t h e Northeastern United S t a t e s i s r e s i d u a l f u e l o i l combustion a s s o c i a t e d w i t h t h e generation of e l e c t r i c power and h e a t i n g requirements. Tabulations l i s t i n g t h e v a r i o u s trace components of crude o i l s by oil f i e l d l o c a t i o n are a v a i l a b l e which i n d i c a t e t h a t t h e r e a r e r e l a t i v e l y high l e v e l s of vanadium and n i c k e l a t very constant r a t i o s . 6
In f a c t , t h e s e n i c k e l /
vanadium r a t i o s a r e so c o n s i s t e n t t h a t i t i s a common p r a c t i c e of agencies d e a l i n g with o i l s p i l l s t o determine t h e source of s p i l l by f i r s t determining t h e N i / V r a t i o and then comparing i t w i t h t h e r a t i o of t h e of1 in a nearby
3 81 Copyright D 1975 by hlarcel Dekker, Inc. 1\11 Rights Reserved. Neither this work nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical. including photocopying, microfilming, and recording. or by any information storage and retrieval system, without permission in writing from the publisher.
BARRY ET AL.
ship.
It s e e m reasonable t h a t p a r t i c u l a t e s produced i n t h e combustion of a n
o i l should e x h i b i t a N i / V r a t i o c h a r a c t e r i s t i c of t h e f u e l burned. The S t a t e of Massachusetts A i r Quality Monitoring System had r o u t i n e l y gathered and provided us with atmospheric p a r t i c u l a t e samples c o l l e c t e d by means of high volume a i r samplers a t c a r e f u l l y s e l e c t e d s i t e s i n Boston (Kenmore Square), Lawrence, and Franingham, Nassachusetts, during 1972.
These
Downloaded by [NUS National University of Singapore] at 12:33 06 November 2015
l o c a t i o n s r e p r e s e n t decreasing degrees of u r b a n i z a t i o n and i n d u s t r i a l a c t i v i t y . The g o a l of t h i s study i s t h e determination of n i c k e l and vanadium f o r
a one year period i n anbient atmospheres i n Eaatern llassachusetts i n order t h a t s e a s o n a l f l u c t u a t i o n s of each element and t h e i r concentration t r e n d s a t sampling l o c a t i o n s of varying degrees of u r b a n i z a t i o n could be e l u c i d a t e d .
In a d d i t i o n , t h e c o r r e l a t i o n of t h e concentration of N i w i t h t h a t of V i s of special interest. EXPERDENTAL PROCEDURE Recently, a r a p i d , a c c u r a t e method has been developed f o r t h e e x t r a c t i o n of s e v e r a l heavy netals from g l a s s f i l t e r s a s s o c i a t e d with high volume a i r samplers.
This technique involved modification of a comonly used procedure.2
The a c i d i c e x t r a c t s were analyzed f o r n i c k e l and vanadium content on a PerkinE l m e r Node1 403 atomic absorption spectrophotometer; standard s o l u t i o n s were
prepared and t h e o p e r a t i n g conditions were e s t a b l i s h e d i n accordance w i t h t h e reconmendation of t h e manufacturer. RESULTS AND DISCUSSION
The average s e a s o n a l d i s t r i b u t i o n s of vanadium and n i c k e l during 1972 a r e presented i n Table 1. Both metals show s t r o n g s e a s o n a l f l u c t u a t i o n s t h a t are i n v e r s e l y p r o p o r t i o n a l t o t h e average seasonal, ambient temperature.
The winter months e x h i b i t
markedly higher concentrations a s s o c i a t e d w i t h increased f u e l consumption i n a d d i t i o n t o a decrease i n concentration w i t h decreasing degree of urbanization.
382
ATMOSPHERIC NICKEL
AM)
VANADIlM CONTENT
TABLE 1
SEASONAL DISTRIBUTIONOF NICKEL AND VANADIUM DURING 1972*
Vanadium
Downloaded by [NUS National University of Singapore] at 12:33 06 November 2015
Kenmore Square (37)
Lawrence (60)
Franinghan(57)
Winter
0.215(9)
0.184(9)
0.115(9)
Spring
0.088 (11)
0.133(20)
0.040(20)
Summer
0.057 (10)
0.091 (20)
0.048(20)
Fall
0.126 (7)
0.176 (11)
0.068 (8)
Nickel Winter
0.055
0.040
0.029
Spring
0.030
0.033
0.017
Summer
0.021
0.021
0.018
Fall
0.039
0.046
0.021
*Concentrations in u n i t s of pg /m3. Numbers i n parentheses r e p r e s e n t p a r t i c u l a t e samples c o l l e c t e d during a given season.
Nickel concentration i n p a r t i c u l a t e s a t each sampling s i t e e x h i b i t e d s u b s t a n t i a l c o r r e l a t i o n with vanadium concentration; t h e c o r r e l a t i o n d a t a f o r t h e elements i s sursnarized i n Table 2.
TABLE 2 NICKEL-VANADILPI CORRELATION DATA FOR 1972 Kenmore Square
Lawrence
Frdngham
Correlation Coefficient
0.911
0.976
0.842
Slope, B
0.230
0.223
0.275
Intercept, C
0.009
0.003
0.004
Nunber of Samples
60
37 N i Conc. = Bx(V conc.)
383
+C
57
BARRY ET AL.
The f a c t t h a t t h e i n t e r c e p t of t h e r e g r e s s i o n curves a s s o c i a t e d w i t h each l o c a t i o n approaches zero i n d i c a t e s t h a t atmospheric n i c k e l and vanadium have a common source. Since samples were a v a i l a b l e f o r t h e y e a r 1966 a t many Boston l o c a t i o n s , i t was decided t h a t a one-month period in t h e w i n t e r would b e analyzed f o r
comparison w i t h t h e corresponding t i m e span in 1972.
The Beacon H i l l s i t e
Downloaded by [NUS National University of Singapore] at 12:33 06 November 2015
was chosen from t h e a v a i l a b l e 1966 Boston sampling s i t e s , because i t was t h e c l o s e s t s i t e of t h e 1966 s i t e s t o t h e p r e s e n t Kenmore Square l o c a t i o n .
The
purpose of t h e intended comparison was t o determine t h e e f f e c t of r e g u l a t i o n s imposed during t h e i n t e r v e n i n g y e a r s t h a t s e v e r e l y l i m i t e d t h e combustion of r e s i d u a l f u e l oils i n favor of t h e cleaner burning d i s t i l l a t e f u e l s .
As
t h e concentration of metals i s higher i n t h e r e s i d u a l f u e l o i l and t h e p a r t i c u l a t e emissions a r e a l s o g r e a t e r due t o higher ash c o n t e n t s , i t w a s expected t h a t a r e s u l t of t h i s change would b e most n o t i c e a b l e i n t h e concentrat i o n s of both n i c k e l and vanadiun.
A s can be observed i n Table 3, n i c k e l and
vanadium concentrations were narkedly higher in Eastern Massachusetts during 1966 because of t h e increased use of r e s i d u a l f u e l o i l s during t h a t period. During t h e r e c e n t energy c r i s i s t h e r e has been considerable s p e c u l a t i o n a s t o t h e e f f e c t of burning r e s i d u a l o i l s of high s u l f u r content i n s t a t i o n a r y power p l a n t s and t h e impact which t h i s s i t u a t i o n n i g h t have on t o t a l contamfnat i o n of t h e atmosphere.
A p o t e n t i a l a p p l i c a t i b n of n i c k e l and vanadiun con-
c e n t r a t i o n d a t a would b e i n an area where f u e l o i l combustion is t h e only s i g n i f i -
TABLE 3 TRACE METAL CONCENTRATIONS I N THE BOSTON ATNOSPHERE DURING NOVENBER. 1966 and 1972* Kemore Square, 11/72 Ni
V
0.036 0.114
*Concentrations i n u n i t s of ~ d m 3 384
Beacon H i l l 11/66 0.160 1.07
ATMOSPHERIC NICKEL AND VANADIUM CONTEm cant source of s u l f u r dioxide.
I n such a n a r e a i t seems l i k e l y t h a t t h e r e nay
be a r e l a t i o n s h i p between s u l f u r dioxide and n i c k e l and/or vanadiun concentrations.
I f c o r r e l a t i o n does indeed e x i s t , then very s i g n i f i c a n t s u l f u r dioxide
concentration d a t a could be e x t r a p o l a t e d f r o n n i c k e l and/or vanadium concentration data. ACKNOWLEDCPIENT
Downloaded by [NUS National University of Singapore] at 12:33 06 November 2015
W e g r a t e f u l l y acknowledge t h e New England Consortium on Environnental P r o t e c t i o n f o r providing a Fellowship t o Manuel R e i .
We a l s o a p p r e c i a t e t h e
Lawrence Experiment S t a t i o n , Massachusetts Division of Environmental Health f o r providing us with t h e f i l t e r s used in t h i s study. REFERENCES
1. E. F. Barry, M. T. Rei. H. €1. Reynolds, J. O'Brien, Environnental Letters, i n press. 2.
J . L. Moyers, W. H. Z o l l e r , R. A. Duce and G. L. Hoffnan, Environ. S c i . Technol, 6 (11, 68 (1972).
3.
N. L. Morrow and R. S. B r i e f , Environ. Sci. Technol.
4.
E. S. Gladney, W. H. Z o l l e r , A. G. Jones, G. E. Gordon, Environ. Sci. Technol., 8 (6) 551 (1974).
5.
C.
6.
I n t e r n a t i o n a l P e t r o l e m Encyclopedia, The P e t r o l e u n Publishing Company, Tulsa, Okla., 1972.
7.
E. F. Barry, M. T. Rei. H. H. Reynolds, J. O'Brien, Environ. S c i . Technol., submitted f o r p u b l i c a t i o n .
5
(9) (1971).
S. Martens, J. J . Wesolowski, R. Kaifer, W. John, R. C. H a r r i s s , Environ. Sci. Techol. I (9) 817 (1973).
Received February 11, Accepted February 17,
385
1975 1975
ISSN: 0013-9300 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/lesa17
Determination of Nickel and Vanadium in the Atmosphere of Eastern Massachusetts Eugene F. Barry , Manuel T. Rei , H. H. Reynolds & Joseph O'brien To cite this article: Eugene F. Barry , Manuel T. Rei , H. H. Reynolds & Joseph O'brien (1975) Determination of Nickel and Vanadium in the Atmosphere of Eastern Massachusetts, Environmental Letters, 8:4, 381-385, DOI: 10.1080/00139307509437448 To link to this article: http://dx.doi.org/10.1080/00139307509437448
Published online: 02 Sep 2009.
Submit your article to this journal
Article views: 2
View related articles
Full Terms & Conditions of access and use can be found at http://www.tandfonline.com/action/journalInformation?journalCode=2esa20 Download by: [NUS National University of Singapore]
Date: 06 November 2015, At: 12:33
ENVIRONMENTAL LETTERS, 8(4), 381-385 (1975)
DETERXINATION OF NICKEL AND VANADIIJN I N THE ATMOSPHERE OF EASTERN MASSACHLEETTS
Downloaded by [NUS National University of Singapore] at 12:33 06 November 2015
KEY WOWS:
Atmospheric p a r t i c u l a t e s , n i c k e l , vanadium, atomic absorption spectroscopy
Eugene F. Barry, Department of Chemistry Manuel T. R e i and H.H. Reynolds, Department of Enviromental Studies L o w e l l Technological I n s t i t u t e L o w e l l , Massachusetts 01854 Joseph O'Brien Commonwealth o f Massachusetts Department of P u b l i c Health Lawrence Experiment S t a t i o n Lawrence, llassachusetts 01843 INTRODUCTION
For t h e p a s t t e n y e a r s t h e r e has been a growing concern about t h e presence of heavy metals i n urban and i n d u s t r i a l atmospheres.
Although l e a d has been
t h e s u b j e c t of many ~ t u d i e s , l - recent ~ research e f f o r t s have focused on t h e determination of o t h e r r n e t a l ~ . ~ Of , ~ p a r t i c u l a r i n t e r e s t i n t h e p r e s e n t inv e s t i g a t i o n were n i c k e l and vanadium s i n c e t h e i r main known source i n t h e atmosphere of t h e Northeastern United S t a t e s i s r e s i d u a l f u e l o i l combustion a s s o c i a t e d w i t h t h e generation of e l e c t r i c power and h e a t i n g requirements. Tabulations l i s t i n g t h e v a r i o u s trace components of crude o i l s by oil f i e l d l o c a t i o n are a v a i l a b l e which i n d i c a t e t h a t t h e r e a r e r e l a t i v e l y high l e v e l s of vanadium and n i c k e l a t very constant r a t i o s . 6
In f a c t , t h e s e n i c k e l /
vanadium r a t i o s a r e so c o n s i s t e n t t h a t i t i s a common p r a c t i c e of agencies d e a l i n g with o i l s p i l l s t o determine t h e source of s p i l l by f i r s t determining t h e N i / V r a t i o and then comparing i t w i t h t h e r a t i o of t h e of1 in a nearby
3 81 Copyright D 1975 by hlarcel Dekker, Inc. 1\11 Rights Reserved. Neither this work nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical. including photocopying, microfilming, and recording. or by any information storage and retrieval system, without permission in writing from the publisher.
BARRY ET AL.
ship.
It s e e m reasonable t h a t p a r t i c u l a t e s produced i n t h e combustion of a n
o i l should e x h i b i t a N i / V r a t i o c h a r a c t e r i s t i c of t h e f u e l burned. The S t a t e of Massachusetts A i r Quality Monitoring System had r o u t i n e l y gathered and provided us with atmospheric p a r t i c u l a t e samples c o l l e c t e d by means of high volume a i r samplers a t c a r e f u l l y s e l e c t e d s i t e s i n Boston (Kenmore Square), Lawrence, and Franingham, Nassachusetts, during 1972.
These
Downloaded by [NUS National University of Singapore] at 12:33 06 November 2015
l o c a t i o n s r e p r e s e n t decreasing degrees of u r b a n i z a t i o n and i n d u s t r i a l a c t i v i t y . The g o a l of t h i s study i s t h e determination of n i c k e l and vanadium f o r
a one year period i n anbient atmospheres i n Eaatern llassachusetts i n order t h a t s e a s o n a l f l u c t u a t i o n s of each element and t h e i r concentration t r e n d s a t sampling l o c a t i o n s of varying degrees of u r b a n i z a t i o n could be e l u c i d a t e d .
In a d d i t i o n , t h e c o r r e l a t i o n of t h e concentration of N i w i t h t h a t of V i s of special interest. EXPERDENTAL PROCEDURE Recently, a r a p i d , a c c u r a t e method has been developed f o r t h e e x t r a c t i o n of s e v e r a l heavy netals from g l a s s f i l t e r s a s s o c i a t e d with high volume a i r samplers.
This technique involved modification of a comonly used procedure.2
The a c i d i c e x t r a c t s were analyzed f o r n i c k e l and vanadium content on a PerkinE l m e r Node1 403 atomic absorption spectrophotometer; standard s o l u t i o n s were
prepared and t h e o p e r a t i n g conditions were e s t a b l i s h e d i n accordance w i t h t h e reconmendation of t h e manufacturer. RESULTS AND DISCUSSION
The average s e a s o n a l d i s t r i b u t i o n s of vanadium and n i c k e l during 1972 a r e presented i n Table 1. Both metals show s t r o n g s e a s o n a l f l u c t u a t i o n s t h a t are i n v e r s e l y p r o p o r t i o n a l t o t h e average seasonal, ambient temperature.
The winter months e x h i b i t
markedly higher concentrations a s s o c i a t e d w i t h increased f u e l consumption i n a d d i t i o n t o a decrease i n concentration w i t h decreasing degree of urbanization.
382
ATMOSPHERIC NICKEL
AM)
VANADIlM CONTENT
TABLE 1
SEASONAL DISTRIBUTIONOF NICKEL AND VANADIUM DURING 1972*
Vanadium
Downloaded by [NUS National University of Singapore] at 12:33 06 November 2015
Kenmore Square (37)
Lawrence (60)
Franinghan(57)
Winter
0.215(9)
0.184(9)
0.115(9)
Spring
0.088 (11)
0.133(20)
0.040(20)
Summer
0.057 (10)
0.091 (20)
0.048(20)
Fall
0.126 (7)
0.176 (11)
0.068 (8)
Nickel Winter
0.055
0.040
0.029
Spring
0.030
0.033
0.017
Summer
0.021
0.021
0.018
Fall
0.039
0.046
0.021
*Concentrations in u n i t s of pg /m3. Numbers i n parentheses r e p r e s e n t p a r t i c u l a t e samples c o l l e c t e d during a given season.
Nickel concentration i n p a r t i c u l a t e s a t each sampling s i t e e x h i b i t e d s u b s t a n t i a l c o r r e l a t i o n with vanadium concentration; t h e c o r r e l a t i o n d a t a f o r t h e elements i s sursnarized i n Table 2.
TABLE 2 NICKEL-VANADILPI CORRELATION DATA FOR 1972 Kenmore Square
Lawrence
Frdngham
Correlation Coefficient
0.911
0.976
0.842
Slope, B
0.230
0.223
0.275
Intercept, C
0.009
0.003
0.004
Nunber of Samples
60
37 N i Conc. = Bx(V conc.)
383
+C
57
BARRY ET AL.
The f a c t t h a t t h e i n t e r c e p t of t h e r e g r e s s i o n curves a s s o c i a t e d w i t h each l o c a t i o n approaches zero i n d i c a t e s t h a t atmospheric n i c k e l and vanadium have a common source. Since samples were a v a i l a b l e f o r t h e y e a r 1966 a t many Boston l o c a t i o n s , i t was decided t h a t a one-month period in t h e w i n t e r would b e analyzed f o r
comparison w i t h t h e corresponding t i m e span in 1972.
The Beacon H i l l s i t e
Downloaded by [NUS National University of Singapore] at 12:33 06 November 2015
was chosen from t h e a v a i l a b l e 1966 Boston sampling s i t e s , because i t was t h e c l o s e s t s i t e of t h e 1966 s i t e s t o t h e p r e s e n t Kenmore Square l o c a t i o n .
The
purpose of t h e intended comparison was t o determine t h e e f f e c t of r e g u l a t i o n s imposed during t h e i n t e r v e n i n g y e a r s t h a t s e v e r e l y l i m i t e d t h e combustion of r e s i d u a l f u e l oils i n favor of t h e cleaner burning d i s t i l l a t e f u e l s .
As
t h e concentration of metals i s higher i n t h e r e s i d u a l f u e l o i l and t h e p a r t i c u l a t e emissions a r e a l s o g r e a t e r due t o higher ash c o n t e n t s , i t w a s expected t h a t a r e s u l t of t h i s change would b e most n o t i c e a b l e i n t h e concentrat i o n s of both n i c k e l and vanadiun.
A s can be observed i n Table 3, n i c k e l and
vanadium concentrations were narkedly higher in Eastern Massachusetts during 1966 because of t h e increased use of r e s i d u a l f u e l o i l s during t h a t period. During t h e r e c e n t energy c r i s i s t h e r e has been considerable s p e c u l a t i o n a s t o t h e e f f e c t of burning r e s i d u a l o i l s of high s u l f u r content i n s t a t i o n a r y power p l a n t s and t h e impact which t h i s s i t u a t i o n n i g h t have on t o t a l contamfnat i o n of t h e atmosphere.
A p o t e n t i a l a p p l i c a t i b n of n i c k e l and vanadiun con-
c e n t r a t i o n d a t a would b e i n an area where f u e l o i l combustion is t h e only s i g n i f i -
TABLE 3 TRACE METAL CONCENTRATIONS I N THE BOSTON ATNOSPHERE DURING NOVENBER. 1966 and 1972* Kemore Square, 11/72 Ni
V
0.036 0.114
*Concentrations i n u n i t s of ~ d m 3 384
Beacon H i l l 11/66 0.160 1.07
ATMOSPHERIC NICKEL AND VANADIUM CONTEm cant source of s u l f u r dioxide.
I n such a n a r e a i t seems l i k e l y t h a t t h e r e nay
be a r e l a t i o n s h i p between s u l f u r dioxide and n i c k e l and/or vanadiun concentrations.
I f c o r r e l a t i o n does indeed e x i s t , then very s i g n i f i c a n t s u l f u r dioxide
concentration d a t a could be e x t r a p o l a t e d f r o n n i c k e l and/or vanadium concentration data. ACKNOWLEDCPIENT
Downloaded by [NUS National University of Singapore] at 12:33 06 November 2015
W e g r a t e f u l l y acknowledge t h e New England Consortium on Environnental P r o t e c t i o n f o r providing a Fellowship t o Manuel R e i .
We a l s o a p p r e c i a t e t h e
Lawrence Experiment S t a t i o n , Massachusetts Division of Environmental Health f o r providing us with t h e f i l t e r s used in t h i s study. REFERENCES
1. E. F. Barry, M. T. Rei. H. €1. Reynolds, J. O'Brien, Environnental Letters, i n press. 2.
J . L. Moyers, W. H. Z o l l e r , R. A. Duce and G. L. Hoffnan, Environ. S c i . Technol, 6 (11, 68 (1972).
3.
N. L. Morrow and R. S. B r i e f , Environ. Sci. Technol.
4.
E. S. Gladney, W. H. Z o l l e r , A. G. Jones, G. E. Gordon, Environ. Sci. Technol., 8 (6) 551 (1974).
5.
C.
6.
I n t e r n a t i o n a l P e t r o l e m Encyclopedia, The P e t r o l e u n Publishing Company, Tulsa, Okla., 1972.
7.
E. F. Barry, M. T. Rei. H. H. Reynolds, J. O'Brien, Environ. S c i . Technol., submitted f o r p u b l i c a t i o n .
5
(9) (1971).
S. Martens, J. J . Wesolowski, R. Kaifer, W. John, R. C. H a r r i s s , Environ. Sci. Techol. I (9) 817 (1973).
Received February 11, Accepted February 17,
385
1975 1975
