LDEPARTMENT Ir) ATMOSPHERIC SCIENCES · r ldepartment of ir) atmospheric sciences university of...
Transcript of LDEPARTMENT Ir) ATMOSPHERIC SCIENCES · r ldepartment of ir) atmospheric sciences university of...
r
LDEPARTMENT OF
Ir) ATMOSPHERIC SCIENCESUNIVERSITY OF WASHINGTON
0
SCIENTIFIC REPORT
OFFICE OF NAVAL RESEARCH
Contract N00014-67-A-0103-0007NR 307-252
AN ANALYSIS OF CARBON DIOXIDE IN THE APRTICATMOSPHERE NEAR BARROW, ALASKA
2 1961 TO 1967
by
JOHN J. KELLEY, JR.
69
. -- PRIL 1969
1 2 :--:...-\d
[ . j.A
AN ANALYSIS OF CARBON DIOXIDE
IN THE ARCTIC ATMOSPHERE
NEAR BARROW, ALASKA
1961 TO 1967
Final Report
by
John J. Kelley, Jr.
University of Washington
REPRODUCTION IN WHOLE OR IN PART IS -PERMITTED FOR ANY PURPOSE OF THE
UNITED STATES GOVERNMENT
The North Meadow Lake Research Field
Station near Barrow, Alaska. August 1965.
ABSTRACT
The results of the measurements of carbon dioxide in
air at Barrow, Alaska, are presented. Reference gas com-
parison data are tabulated, and methods of calculations
are discussed. The average daily concentrations of
atmospheric carbon dioxide are tabulated for the period
10 July 1961 to 15 September 1967. The diurnal variations
of carbon dioxide during this period are also presented.
TABLE OF CONTEIMS
Page
List of Figures........................................................ i
List of Tables ..................................................... iii
Preface..............................................................
I Introductlon.................................................. 2
II Reference Gas Comparisons...................................... 2
III Recorder Scale Factors ......................................... 5
A. Definition.............................................. 5
B. Standard Computation for ThreeMuitually Compared Tanks.................................5
C. Determination of Index Differences........................6
D. Weighted Average Recorder ScaleFactors................................................ 7
IV Summ~ary of Recorder Scale Factors..............................7
V Index Values of Reference Gases................................8
VI Combined Scripps and Barrow Index
Values of Working Reference Gases........................8
VII Corapailfoot of Sczippa and BarrowIndex Values of Working ReferenceGases................................................ 9
VIII Index Valuea of Air.......................................... 10
A. Computation of Index Values.............................10
B. Manometric Concentration Scale..........................1U
Page
IX Monthly Average Index of CarbonDioxide ................................................ 12
X Monthly Average Index of CarbonDioxide, Manometric ConcentrationScale .................................................. 12
XI Twelve Month Running Mean Concentraticnof Carbon Dioxide ....................................... 12
XII Values c'i Table 9 and 9a Referredto a Constant Datum ..................................... 13
XIII The Diurnal Variation of CO2 .. ... .. . .. .. .. .. .. .. .. .. .. .. .. . .. . .14
Tables ............................................................. 15
References........................................................ 163
Appendix 1........................................................ 164
Appendix 2........................................................ 166
r
LIST OF FIGUPES
Figure 1 Map of Point Barrow vicinity showing the atmos-
pheric chemistry site near the ocean beach and the
North Meadow Lake field station.
Figure 2 Mutual Camparison Method for Tank Standardization.
Figure 3 Recorder Scale Factors (RSF'a) Adjusted to Standard
Barometric Pressure Versus Calendar Dates, Period
1-11, Arctic Ocean Beach Site.
Figure 4 Recorder Scale Factors (RSF's) Adjusted to Standard
Barometric Pressure Versus Calendar Dates, Period
13-14, Arctic Ocean Beach Site.
Figure 5 Recorder Scale Factors (RSF's) Adjusted to Standard
Barometric Pressure Versus Calendar Dates, Period 15,
Arctic Ocean Beaca Site.
Figure 6 Recorder Scale Factors (RSF's) Adjusted to Standard
Barometric Pressure Versus Calendar Dates, Period
1-4, North Meadow Lake.
Figure 7 Recorder Scale Factors (RSF's) Adjusted to Standard
Barometric Pressure Versus Calendar lates, Period
4-10, North Meadow Lake.
Figure 8 Pecorder Scale Factors (PSF's) Adjusted to
Standard Barometric Pressure Versus Calendar
Pates. Period 10-17, North Mendow 'Lake.
Figure 9 Differences Between Index Values (ppm) Obtained
from Measurements at Barrow and Scripps, 1961-1963.
Figure 10 Differences Between Index Values (nnm) Obtained
from Measurements at North Meadow Lake and Scripps,
1965-1967.
Figure 11. Daily Average Concentration of CO, ]q61-1963.
Figure 12 Daily Average Concentration of Cn, 19f65-1067.
firure 13 T.elve-Month Punninp Mean of the Concentration of
Atmospheric CO 2 Near Barrow, A]aska.
Figure 14 "onthiv Average Concentration of CO 2 Near Barrow,
Alaska Peferred to a Constant Datun (.lanunrv ])~f).
rigure 15 Averape Diurnal Variation of cno, " ear Barrow, Alaslk,
1961-1Q67.
- tt -
IT ST OF TABLES
Table 1 Refer,nce (as Comparisons - Barrov
Table In Rcf._rence Gas Comparisons - nlvcrsJtv of Vanshinpton
Table 2 Recorder Scale Factors - Barrow, Alaska
Table 2a Recorder Scale Factors - niver.,itv of W4aqhinrton
Table 3 Surunarv of Recorder Scale Factors, 1961-1063
Table 3a Summary of Recorder Scale Factors - ,Iutunl
Comparison Miethod, 1962-1963
Table 3b Summary of Pecorder S cale Factors - Mxuttal
Comrarison "ethod. 1965-1n67
Table 3c .ummarv of Recorder Scale Factors - Slldinp.
Pecorder Scale ractor ;, Barrow Alask' Carboti
Dioxide rroject
Table 4 Index Values of Vorkinp Reference Cases
Table 5 Combined Scripns and Barrow Index Values of
,orkinp. Peference Cases
Table 6 Comparison of Scrinis and Barrow Index Values
of Working Reference e
Table 7 Indices of Air With Continuous A nalvzer, 1961-163
Table 7a Indices of Air With Continuous Analvzer, 1965-1067
Table 8 onthlv Index of Carbon Dioxide (ann) at Barrow,
Alaska, 1961-1963
- iii -
Table 8a Monthly hiaex of Carbon Dioxide (pm) at Barrow,
Alaska, 1965-1967
Table 9 m .thlv Index of Carbon Dioxide (rpm) at Barrow,
Alaska - M3nometric Concentration Scale, 1961-1963
Table 9a Monthly Index of Carbon Dioxide (rpm) at Barrow,
Alamkq - Mfanometric Concentration Scale, 1q65-1967
Table 10 Twelve Month Running Mean Concentration of
Atmospheric Carbon Dioxide at Barrow, Alaqka
Tahle 11 Values of Tables 9, 9a Peferred to a Constant Datum
(January 1960)
Table 12 Dliurnal Variation of Carbon Dioxide, Barro-, Alaqkp
1961-1963
Ta le 12c Diurnal Variation of Carbon Dioxide, ,larrow, Aaq.a,
1965-1967
Table 12b Averace Diurnal Variation of CaTrbon Dioxide,
1961-1967
- iv -
PREFACE
This eport presents a summary of measurements of the concentration
of carbon dioxide near Barrow, Alaska, and at the North Meadow Lake field
station of the Arctic Research Laboratory, Barrow, Alaska.
This work was supported under a contract from the Office of Naval
Research (ONR 477(24)) with the Department of Atmospheric Sciences,
UTniversity of Washington. The analytical program was conducted cooperatively
with Dr. C. D. Keeling's (The Scripps Instzution of Oceanography, La
Jolla, Califarnla) atmospheric csrba--, diox-Th pogra. at Mauna Loa,
Hawaii, and the South Pole Sv' on, Ant, .
The carbon dioxide t rogi -. ,t ,-' j nitiated and maintained
from July 1961 to -ugust j J, . J. Pelilcy, .r. Operation of the carbon
dioxide i yzer was ;.ti:e . J. Unpt:r frDt September 1962 to March
I -i, ., rp . v-£1. lc: " 9t:. , t. Strzoschein.
T .- ca-- Q .-n dioxie prt:,.x.c at the N.-t, 14eadow Lake field station
, .* t..&.: , f, -iVer 1, Ja *.', !'o5 to September 1965, by
~2~> Ja.'.Y >r. : , pte!W- ik!: ". r 5 i,:" i.C0.U. , , and by W. wald from
c~r~ ~rI tob the U i of it ' o'.v 'Septe--ie 1967.
~?of ! ,:i - At4C Pe'ieaf-C. i ro Dr. M. C. Brewer
. -J.js .alf h.je ;'c-id, i u:u e :';.m.e to the project.
I
I. INTRODUCTION
This report presents the final results of a program to measure the con-
centration of carbon dioxide in the atmosphere at Barrow, Alaska from
July 1961 to October 1963, and at the North Meadow lAke field station
of t>':e Arctic Research Laboratory, Barrow, Alaska from January 1965
to September 1967. The location of each site is shown in Figure 1.
Daily average values of the concentration of CO2 in the surface air
are computed from da.a derived from original strip chart records of a
continucus recording infrared gas analyzer installed at the station.
All relevant data and computations for the years ln6l through 1967
are contained in this report. The experimental method is described
in a Technical Report by Kellev (1964). Interpretation of the data
will be published in a scientific journal.
All data in this retort are final values. The procedure for
computation follows that used at the Scripps Institution of Oceanogranhv,
La Jolla, California as described in Research Rerorts I throuph VIII*.
II. REFERENCE ZA5 COITARISONS - TABLE 1, Ia
This table lists, in chronological order, both the observed scale
differences which were used to calibrate the gas analyzer, and their
conversion into index values proportional to CO2 concentration. The
*Coples of these reports may he obtained from Dr. Charles D. Keelinp,
S.T.O., La Jolla, California.
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calibrations of the analyzer consisted of repeastd comparisons of pairs
of specially prepared gas mixtures of CO2 in nitrogen obtained from the
Scripps Institution of Oceanography. These reference gas mixtures were
stored in stainless steel cylinders called "tanks."
Under normal operating conditions ten comparisons were obtained by
alternately passing one gar of the pair, and then the other, through
the infrared analyzer for five minutes at the same flow rate employed
in the air measurements (normally 0.5 liters per minute), As soon as
one series of trn comparisons was run, one or both tanks were replaced
and another pair of tanks compared. This process was repeated, as a
rule, three times during the life of a "working reference" tank: at
the beginning of use, when the gas pressure was half depleted, and at
400 p.s.i., before return of the cylinder to Scripps for final calibration.
The scale difference between two successive traces, in recorder chart
ordinates, was read with a straightedge scale (30 divisions to the inch)
by drawing parallel straight lines through each of the traces belonging
to the reference gases. The successior of individual scale differences
for each tank pair was entered on data sheets. The calibrations described
served to establish the recorder sensitivity of the infrared gas analyzer.
They were also used to determine the index values of reference gases
known as "working references," used in connection with air m e-Irementa.
The general method used by the Scripps Institution for tank standardization
(Figure 2) was modified somewhat a& Barrow during the period covered
by the report. Initially, two reference gases were compared with air
every 30 minutes. Fro= 1962 to the end of the program in 1967, three
reference gases were employed. Two of the reference gases were used
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as comparison standards. The third reference gas was ranked as a
"working reference" and compared with air every 30 minutes. The "working
reference" was compared directly to the comparison standards, primary
and span (high or low), in the absence of a suitable secondary reference
at Barrow.
In Table 1, tanks related to each calibration run are identified by
tank numbers. They are listed in columns 1 and 2. Column 1 lists the
number of the standard tank; column 2 lists the number of the tank with
which it is compared. The average observed scale difference for each
tank pair is listed in column 3. A positive number indicates that the
compared tank, for that particular comparison, has a higher scale reading,
and consequently a higher C02 concentration than the standard; a negative
number indicates the reverse. The number of comparisons (not always
10) which entered into each average scale difference is listed in column 4.
The recorder sensitivity, determined by comparisons of the primary
and secondary standards, is expressed by a "recorder scale factor" listed
in column 5. The computed index differences, each with the same sign
as the corresponding scale difference, and the index value of the compared
tank, in terms of a prescribed, or "assigned" value of the standard tank,
are listed in columns 6 and 7.
Weighted average recorder scale factors, column 5, are copied from
column 7 of table 2. Index differences, column 6, were computed bv -
formula given in Section III-D.
- 4-
The computed index values, column 7, are the algebraic sums of the
index values of the standard tanks listed in column 1 and the index
differences of column 6. The index values of the standard tanks are those
listed in column 7 of Table 6. In the case of the primary tanks designated
as I and Ihs or ILS in Figure 2, they depend solely on the measurements
made at Scripps.
The data listed in Table 1 are for the period 2 January 1965 to
18 September 1967 at the North Meadow Lake field station. The data in
Table la are for the period 1 April 1964 to 14 June 1967 at the University
of Washington. The data for reference gas comparisons at the Arctic
Ocean beach site from 6 January 1962 to 21 August 1963 are given in
Report 2 (Kelley, 1966).
The scale differences entered in column 3 of Table 1 and la are
copied from original entries on the reference gas data sheets.
III.RECORDER SCALE FACTORS - TABLE 2, 2a
A. Definition
The Recorder Scale Factor, RSF, is defined as the index difference
between two reference gases divided by the number of scale divisions
(30 div. to the inch) between the recorder chart traces for each reference
gas recorded in units. Ten divisions on the scale were equal to one unit.
The index of a reference gas tank is defined as a provisional CO2
concentration, or mixing ratio, in ppm based on the initial analysis of the
tank.
B. Standard Computation for Three Mutually Compared Tanks
Columns I through 4, except values with asterisks explained below, and
the last entry in column 4 for each calibration day, list selected data
- 5-
copied directly from the corresponding columns of Table 1. These data are
employed, as shown below, to obtain daily RSF's.
The following format has been adapted from the Scripps (SIO Reports
1-8) scheme for tank standardizations, where the standard tank index
values have been assigned the symbols A and B , and the compared tank,
without such assignment, the symbol X:
Standard Compared Observed Scale No. ofTank No. Tank No. Difference Comparisons
A X IXI- (A] aB X [X)- (BI bA B [YI* (a or b)*
[i I (IxI - (A]) - (IX) - (B)) ((B] - A])
The asterisk on [Ylindicates the calculated value, and the brackets
indicate index values. The number of comparisons assigned to tY] is "a"
or "b", whichever is smaller. The observed scale differences were taken
from the averages of the individual chart scale differences (Table 1).
The observed comparisons and calculated values of any group of three
tanks, A, B, and X are set off in the table by boxes.
C. Determination of Index Differences
Index differences shown in Tables 2 and 2a, column 5, were obtained
from index values of the standard tanks as follows:
Tank Numbers Index Values Difference
11589 vs 18206 314.59 - 310.70 3.8911589 vs 18207 314.59 - 312.7d 1.8118206 vs 18208 314.59 - 312.40 2.1911589 vs 10071 -314.59 + 339.00 24.41
-6-
L _______
The index values of separate tanks are obtained from Table 4.
D. Weighted Average Recorder Scale Factors
Column 6 presents RSF's computed according to the definition given
in section III-A. Column 7 presents the weighted average values of the
recorder scale factors for each calibration day. The index differences
in column 6 of Table 1 are computed by the formula:
Computed Index - (Observed Scale Difference)(Weighted Average RSF)Difference
IV. SU44ARY OF RECORDER SCALE FACTORS - TABLES 3. 3a. 3b. 3c
Values of RSF's are assembled in chronological order in column
5 of Table 3 for Periods I through 11, 10 July 1961 to 16 December 1961.
A graph for the data from Period I through Period 11 is shown in Figure 3.
During these periods, breaks in continuity were extreme due to the
development of a method for determining a standard operating method for
infrared analysis at the Arctic Ocean beach site. Each break is charac-
terized by a change in the span control on the infrared analyzer. There-
fore, discrete periods of relatively constant recorder scale factors are
created between span changes.
During periods 12 to 15, from 6 January 1962 to 21 August 1963,
(Table 3a) a constant recorder span setting was used and a mutual comparisrr
method of tank standardization was set up. These data are 9rhown In
Figures 4 and 5.
Table 3b presents a sumnary of recorder scale factors for the period
2 January 1965 to 18 September 1967 at the North Meadow Lake field station.
-7-
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BARROW, ALASKA
w- PR -ia- I
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U','
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LLJ--
PERIOD 9. *PERIODOD
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Figure 3 Recorder Scale Factors (RSF's) Adjusted to StandardBarometric Pressure Versus Calendar Dates, Period
1-11, Arctic Ocean Beach Site.
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The data are derived by means of the mutual comparison method. Discon-
tinuities in the recorder scale factors occurred at vArious times during the
period of analysis at North Meadow Lake. Table 3c provides daily
recorder scale factors for the periods where discontinuities occur.
The data in Table 3c were produced by drawing a line between the end
point of the average RSF curve for one period to the starting point of
the average RSF curve of the next period. Daily RSF's were recorded and
defined as sliding recorder scale factors. The recorder scale factors
adjusted for pressure barometric for the period 2 January 1965 to 18
September 1967 are shown in Figures 6, 7, and 8.
All recorder scale factors were adjusted to a standard barometric
pressure of 30.00 inches of mercury (1015.9 mb). The following formula
was used:
Adjusted Recorder (Weighted Average RSF)(Observed Barometric Pressure)Scale Factor 30.00 inches of mercury
V. INDEX VALUES OF REFERENCE GASES - TABLE 4
This table presents the index values of all reference gases usedU
in the Arctic field program and at the University of Washington. All
of the analyses were performed at the Scripps Institution of Oceanography.
VI. COMBINED SCRIPPI AND BARJ'.OW INDEX VALUESOF WORKING REFERUNCE GASES - TABLE 5
This table sunnarizes the index values of all working reference
gases used at the North Meadow Lake field station from 1965 to 1967.
The data for working reference gases for 1961 to 1963 are given in Report
2, Table 7 (Kellev, 1966).
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Entries in columns 2 and 3 are the numbers of comrarlsons and wel%'hted
averepe index values based on measurements at Scripps prior to and after
Use. These data are taken from Table 4.
Tntries in columns 4 and 5 are the numbers of comparisons and weirhted
average index values based on measurements at the North Meadov. Lake
fieldl sr.-ton near Barrow, Alask-a.
flntries in columns 6 and 7 list the total number cf conarIF~on- and
veighted averape Index values based on all measuremients at S crinrs and
ait Parro-.
".T1. C(,'TARTrON OF SCRTPPS A'-D Bj~PR' P!TW\'V.ALtrr. OF "ORVINr RVFTrTrN'CTr CAsy-S -- TAV.Lr F.
This tahie rrvsents the results of all analvsis of Pnrrol-' reference
tais uqed In the di.'conarison i0, Air durinp lnf.5 to l167. 7 t is
Cir--Criqon forZ the years 1On'1 to 1"63l is Plven In 'ePnnrt 2, rTable P
0. ellev, 196A). The tablle cornares the results of the analysqes rade
ait the Fcrinps Tnstittlon of Oceanorranmhv iwith those r-ade at Tarrow.
Fhie total numher of indices and comnarisons sqhoi.'n in columnsq 2 and 3 arc
tal~en fret' the coluns headed cumulative runs Pand cumuantive Index< of
Table 4. The numb+er of cornarisons -ind reference tank indices In colur-r-
4 and 5 are conierl fror. columrns 4 and 5 of Table 5. E'ntrie-s in column
0 ire the di fferences bietwyeen index values in nartsz nor mill1ion I'v volume-l
C()2 obtAined froT- meastiremerits at PBarrov- and 5Qcrinns, aind represent
tho Indey. denarturo fror- qcrinns values. Thoev da.tA arp neotted in rl-uuro 0
for tiie nerio(I 1061 -19~63, and rifure 10 for thei Period 1I %5-l%(7.
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VIII. INDEX VALUES OF AIR - TABLE 71 7a
A. Computation of Index Values
These tables contain all daily CO2 values at the Arctic Ocean
beach site and the North Meadow Lake field station for the period
1961-1967. Column 1 lists the calendar date of the analysis. Column 2
shows the observed daily average scale difference between the air trace
and the working reference gas trace. Column 3 lists the total number
of comparisons for the day. A full day consists of forty-eight half-
hour comparisons. Column 4 records the average barometric pressure for
the day. These values are obtained from the original carbon dioxide
daily data sheets. All of the data for the years 1961 to 1963, Table 7,
were processed manually. All of the data from 1965 to the termination
of the program in 1967 were precessed with the aid of an IBM 7094
computer. The Fortran 4 format is given in Appendix 2.
The observed scale difference in column 2 was adjusted to a standard
barometric pressure of 30.00 inches of mercury (1015.9 mb) by the
formula:
Adjusted Scale , Observed Scale x 30.00 inches of HgDifference Difference Average pressure for the day
and this adjusted scale difference is recorded in column 5.
Column 6 lists the RSF's to be used in converting scale uifferences
to index units. These are based on values listed in Tables 3, 3a, 3b,
and 3c which have been adjusted to standard atmospheric pressure.
The computed index difference in column 7 is obtained by:
Computed Index Difference = RSF X Adjusted Scale Difference
- 10-
The working reference tank used in the comparison with air is listed
in column 8, its index in column 9. These data are taken from Table 5.
The daily average index values in column 10 are the algebraic sme of the
entries in columns 7 and 9.
In several instances reference tank changes were made during the
day. In these cases the daily index was computed by first computing
an air index for all of the observations with one tank in use, and doing
the same for the data taken with the replacement tank. These data are
reported separately in column 10. The daily index is taken as the average
of the two separate index values.
B. Manometric Concentration Scale
Throughout this report, the CO2 data have been reported in terms of
an index scale. It was established provisionally at Scripps in 1959
that the true concentration in parts per million by volume is related to
the ,.[dex scale by:
Manometric Concentration - (C - 311.51) 1.2186 + 311.51
wh.ere C 1 r the 1 'nucx value.
This equation is based on the absolute calibration of primary and
span reference gases by means of a mercury manometer. It is possible
that future manometric calibrations may result in further adjustment of
the index scale. The intercept value (311.51) is believed to be correct
within 1 ppm; the slope value (1.2186) within 0.03.
- 11 -
U
This equation has been used to report atmospheric CO2 concentrations
in the reports and journal contributions listed in Appendix 1.
Column 11 lists the manometric concentration of the index values
reported in column 10 in ppm CO2 by volume dry air. The data are shown
graphically in Figure 11 for the period 1961-1963, and Figure 12 for
the period 1965-1967.
IX. MONTHLY AVERAGE INDEX OFCARBON DIOXIDE - TABLE 8. Ba
This table presents the monthly average index of atmospheric CO2
at Barrow, Alaska for the years 1961-1963 (Table 8), and 1965-1967
(Table 8a). Columns 2, 5, and 8 list the number of days for which air
index values are quoted in Tables 7 and 7a. Columns 3, 6, and 9 list
the monthly carbon dioxide index values.
X. MONTHLY AVERAGE INDEX OF CARBON DIOXIDE,MANOMETRIC CONCENTRATION SCALE - TABLE 9. 9a
The data in Tables 9 and 9a are the manometric indices in ppm
CO2 for index values quoted in Tables 8 and 8a.
The averages of the monthly values for each year are given in
columns 3, 6. and 9.
XI. TWELVE MONTH RUNNING MEAN CONCENTRATION
OF CARBON DIOXIDE - TABLE 10
A twelve-month running mean concentration of CO2 was calculated to
smooth out the seasonal variation in CO2. Concentrations for CO2
are presented for the period 1962 to 1967. Means are plotted in Figure
13 versus the sixth month of the appropriate 12-month interval. Least
squares regression lines were fitted to the data for the periods 1962-
1963 and 1965-1967. Equations for each regression line were determined as
- 12 -
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1961
315 ""320 L
305
3o0 L L J L_. _ _ J 1 _ _
JAN FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DEC325-
F 315'°z I
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L 300J4N FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DEC
32.0 , ,____ _ q
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JAN FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DEC
Fu 1 i C o C 1 -
320 ':
315 "
310 " .. " >'
305K
300 - LJAN FEB MAR APR MAY JUN JUL AuG SEP OCT NOV DEC;
F'igure 11 Daily Average Concentration of CO2 1961-1963.
S1965
315 " -I .*. o
- i
310 I
305 -
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JAN FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DECE 325 . .-.,,
Q ,-: r . 1966
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r -- -'"-." ".' - - • - I 1967
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315
305 - --
300 _l. - L I i IJAN FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DEC
Figure 12 Daly Average Concentration of CO2 1965-1967.
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nix-brr of m % . ln &ayue.- frc:T- t' Ie f i:tlt a m X 0.
s';,- tr i ht line for trt puio i9 2-1Th3 tr at.. a rat,- of
icc,., cf CC, in tht hrt.-:tc atupher( oi 0.02f. pur. per Manth. The
&:ra.'-.t line for the per'o, 19£4-i96 in.-liatea a rist c0 lncrease of
ct2 3f 'V. r,5t, ppm pe" tzont . 7 veig,;t@, Avf-¢n.st .--f th two rites
t Irre-,Ae JE CC... in th~e Arctic striosneve If ~CSp. mcr 'th
X1, VAi'S OF TAbLt 9 P Nl. 9a TO.....F . . '1" TA L-?! A 11
ThI.F. table .ises t .I? avs->t& 'trlLione ?tc i':,ea 9 and
~ai~ 'L . A -4!jMr C 1--st c~8Ll rtch ct~c: . h! concen-
0.!. 0%: f. 't r,. O'e t . h,2 e e - t~c rrtc' nrea increased --At
,,- cf C. ppT. p.ez , 'h (;.Ob ppm per month rate of increase
it, ba;ed o.r, the ohserva~cin *t Ha.na Ly- by Pales and Keeling (1965)
.nt Aint; ct by brcwt, _rid Keelina (1965), and by the rate given in
02 - for t;,e Arctic.
Co,4 wuste averages appear in column 5. Column 6 lists the departure
cl these averages frcm the annual meat, value of 314.69. The monthly
average concentration of CO 2 near Barrow, Alaska referred to a constant
datum (1960) is shown in Figure 14.
-13-
0
cc
:3 *
C-
co
4j
Icc
-u c
W 00zn n -o
Ludd)~- N8(GN3)OO?':
rI
XIII. T1;'£ DIURNAL VARIATION OF CO2 - TAI'TYr 12, 12a, 13c
The diurnal variation of C0 2 was calculntpd from the half-hourly
ob.ervations recorded on the oripinal carbon dioxide data sheets.
The ieturnal variations are based on hourly air indices by findinp, the
average index for each hour of the day for each month.
rPiure 15 and Table 12c show the averape diurnal variation of
CO, for each month based on the data for CO 2 from 1961 to 1967.
- 14 -
321 -Tm-
~J
320- JANUARY
319
322
FEBRUARY
322
321 MARCH
322 --
321 APRIL
324 'E 323 -------.
MAYMI
z 321 -
3W0 K JUNE" 315 -
Z 314 -LJULY
33 -z0 311
310
, AUGUST /312
SEPTEMBER310 --
316 , L
31 5- OCTOBER
318
i NOVEMBER
DECEMBER
318__._____•____,_,__'_______ i i i i . i j
C 2 4 6 8 10 12 14 16 18 20 22 24
TIME (hour of day)Figure 15 Average Diurnal Variation of CO2 Near Barrow, Alaska,
1961-1967.
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0' O~~ 0% 0% OC000O 0% 0% 0% 0 0% 0% C%0 0:0% 0% 0% N0% 0 00 C 0 ON 0% 0% 0% 0 0% m% Ch 0 ON 0 0 0% *%-- 4 -4~ N N N N (4 CN r4 .-4 .4-4 .4 N .-4 .-4 -4 N .4 .-4 N .-4 -4
4f ca
t-
-4 1.4 -4 .4..4 -4 Pb4 . -4 4 ~N N eq
-a
-159-
-4 M 0v- 0 0%- 0 -4 r4 4-4 C40 4% .- 4 -4-4 -
; (*4 C 4 C i N4 C4 N N N4 C4 N N 4 N4 C4 e4 C N N NC4N C4 NCN4 N N1 . . N . . . . . N N N N N . . . .
r4 "l C4 (4 (%1 C C4 04 "l t4 .l . . N C14 C4 "l C4 C-4 ( CN C4 C4
fn . " N Cq(nC' -4 4 -40 N - NN-Cl.4r- C4 N I N q M N T
N, N4 N 4 N N1 N4 N N- N N4 N NI N4 N N4 N NI C4 N% N' N N(Nnecn M (1)V) en mcn M m en m m m r) m m m cn m l% en
0 - 4Q 14a 7%(0O 0000 A N 1 z -
PN N4 N N4 N N4 N4 N4 N4 N4 N C N4 N: N4 N N NNN 40' 4 C4 C-4 C4 r4 C14 " "C " C4 'C 4 (C C-C4 04 V4 C C4
N , N N N 4 N N N r,~ -N ~ ~ ~ ~ ~ c N, N N NNNNN9N l C! N!
N C N N 6 C; C; C; :; C; N ; N ; N N C; 8N S N N ; ; NNC4 C4~ Clr ClrVe Cq C4 C4~ C C "ClA C C4 " C4 C%4 N "N C4~
en It~ tm Cl i l co cs 0 1.N-1 C14 m -. U 'D C-- 0' 0'C 0~ .4 C -4 m 4
14 ~ ~ 00 0 00 00 00 0 0 01 -- -0 -0 0 00 0 -4 4C I 1
'U160
9-4,
C4 ~ ~ 9 61% C4 14 4% NO N4 Nr %n -4 1 1 NN N% - N1 %a V
O . -4 -4 44- -- 4 4 - -4 - - - - - ---m nmc )e n ne nc - nine n( ne
0r-
M MMMM M MM M MMMM M MM M M
0 '0 QM 0 0. 0 0 0 '0 P-1 -. 0 r4 '0 i' C4 c-4 c-4 C40 M
al 0 .1 Co .1 M . (4NNNNNNC
II0 161
0' 00 cy O0 % 0, I 000 , O C'. 0% CA 0% 00 00 CI 0'0 CN47 0 0
en fn1( en fl ml ml en 4-* fn1 Cl en An en ml ml ml en mI m l el el
11: 1" r OC ) I'- %0 1 11 0 ' C-. P 0% 9 -. ! C 0 0' O% 0: 01 0'
r- I'C l IC l .r1 P, r- r- r- r, r- Cl r- r- r- r. r- (I
Z l- ~- ~- ~C -4 pl -4 -4 -N -4 -1 t - 4 -4 -4. -l 4 0 -t 4
ClC C l lil~ C l lC Cl el Cl (1' Cl C lCC Cl n l C (1
4 .) -4- - 4 --4 r4.44 -10C00 700 0% ONON 01 4 -4C4
W- 1(2 -- , 4 -4 -4-4 ;- 4 4-4 -.4 .4 4 .-4 .-4 -4 -4 -4 .-4 '4 '4.-4 -4
CC 0% (N, ClJ M4 40 C. U%.l' 7 (1n ('21( en4 M (M- CIA M%0 C-. e r-
06
0
'0 c 0- '.t r- C3 -. c0 ' C 0- 0- 0 c3 CA 0 '.0 . G4 .7 - C)
;m oe ooolo co o o o c o-4-Z4- 4 4- 1- -4 0 0 CY, N'01 NJN(N(DiC 0% a(CJ((-
P,- c44r 4 44 ;4 3r 44rC- ,C4C4C4C4 ..- - - - - -4C- 1 - I Q CAA
rn e c i -
v.-4 .4 r4 .4 r.4 '.4 v-4 -4 4i - 4 - 4 r-4 ~4 .4 .4 A. '.4 '.4 r4 ,. 4 .-4 ,C*4 ~C4 " , ' C,4A Alt1 ( C i4 C "1( r4 .C C C4 C4 cA "I C,4 c,4 c,4
<1 W 1 C, 00 CO . ON CO f CID(' C, Cl (I cl Cl (1 ( a l a l Cl Cl a
TZ -4 1' 41 -' l- ( t 4 4 4 - 40 -4 4~( C.4 -4 _4 -4 -j -4 .-
C.) 11 .- 4-m.-4. An--4-4.4.In47-4 4.. -4.4-4 A AN CI -'-'C.4
M3 C.) 'C en r-) M C- Ml n' C-'(2 C,) M 0 C. en . j,~ t '0 M. M. el' C-.C
~~~~L 00'C CQ.00 C0 0 0'C 0
QI. 3 '~ - ( C, C.4 " -4 -. -LI -.0 C-. -220 0. r C4 C4 -zt
-IG
REMMENCES
1. Brown, C.W., and C.D. Keeling, The concentr tion of atmosphe,:ic
carbon dioxide in Antarctica, .. Gftovhys. Res., 70, 6077-6086,
1965.
2. Kelley, J.J., Jr., Analysis of carbon dioxide in the Arctit. ti-osphere,
at Point Barrow, Alaska, Tecchnical Repor.t, Office o aval
Research Contract 477(24), University of Washington, 1964.
3. Kelley, J.J., Jr., Analysis of carbon dioxide in the Arctic
atmosphere at Barrow, Alaska during 1961-1962-1963, Technical
Report No._2, Office of Naval Research, Contract 477(24),
University of Waehington, 1966.
4. Pales, J.C. and C.D. Keeling, The concentration of atmospheric
carbon dioxide in the Hawaiian Islands, .J. Geophys. Res., 70
6053-6076, 1965.
- 163
APPENDIX 1
The following is a list of publications and reports based on the
atmspheric carbon dioxide program in the Arctic and at the University
of Washington.
1. Kelley, J.J., Jr., An Analysis of Carbon Dioxide in the Arctic
Atmosphere at Barrow, Alaska, 'mechnical RePort, University of
Washington, Department of Atmospheric Sciences, ONR 477(24),
1964.
2. Felley, J.J., Jr. and D.F. Weaver, Carbon Dioxide and Ozone in
the Arctic Atmosphere, Proceedings of the 16th Alaskan Scienice
Conference, AAAS, 1965.
3. Kelley, J.J., Jr. and E. LaChapelle, Atmospheric CarL-on Dioxide
Variations on Mt. Olympus, J. Geophys. Res, Vol. 71, No. 8,
1966.
4. Kelley, J.J., Jr., An Analysis of Carbon Dioxide in the Arctic.
Atmosrhere, Report 2, Technical Report, ONR 477(24), Department
of Atmospheric Sciences, University of Washington, Seattle
Washington.
5. Kelley, J.J., Jr., Carbon Dioxide in the Surface Waters of Puget
Sound, FinalRetport, prepared under Contract Nonr 477(24),
Department of Atmoepheric Sciences, University of Washington,
Seattle, 1966.
- 164-
i
6. Kelley, J.J., Jr. and S.M. Podge, Measurements of the Chemlcal
Constitution of the Atmosphere at the Blue Glacier Field Station,
Mount O1)wpus, Washington, Summer, 1966, Scientific Report,
Department of Atmoshperic Sciences, University of Washington,
Seattle, 1967.
7. Kelley, J.J., Ji., Carbon Dioxide and Ozone Studies in the Arctic
Atmosphere, Proc. of the ONR-AINA Arctic Drifting Stations
SyMposium, 1967.
8. KeIley, J.J., jr., D. Weaver, and B. Smith, The Variation of Carbon
Dioxide under the Snow in the Arctic, ECOLOGY, 49(2),
pp 358-361, 1968.
9. Kelley, J.J., Jr., Carbon Dioxide in the Sea Water under the Arctic
Ice, NATURE, Vol 218, No 5144, pp 862-864, June, 196S.
10. Kelley, J.J., Jr., Atmospheric Trace Gases and Suspended Particulate
Matter on Mt. Olympus, Olympic National Park, Washington,
J. Geophys. Res. (in press), 1968.
11. Kelley, J.J., Jr., Observations of Carbon Dioxide In the Atmosphere
over the Western Urited States, J. Geophys. Res. (in press),
1968.
12. Kelley, J.J., Jr., Equilibrium Partial Pressure of CO2 in the
Kara, Barnts, and Norwegian Seas, Progrfss Report, AINA-ONR,
ConLract 401, Department of Atmospheric Sciences, Universitv of
Waehington, Seattle, 1968.
- 165 -
APPENDIX 2
FORTRAN 4 COMPUTER PROGRAM
This program is designed for use on the IBM 7094 computer. Data
for CO2 from five sources of air are entered into the program for each
half hour interval. The CO2 index for each half hour interval is
computed. Wind direction, wind speed, barometric pressure, and ambient
air tempe'ature are logged in the data output. A summary of the dat.
is given for each day as follows:
Number of half hourly observaticns
Recorder Scale Factor
Mean Index 1
Mean Index 2
Mean Index 3
Mean Index 4
Mean Index 5
Mean Index all levels
Mean barometric pressure
Mean temperature, OC
Location of levels I through 5
INSTRUCTIONS FOR KEYPUNCHING DATA
1. The first data card has the form: three blank spaces, then
the data of the day's run, e.g.:
17 March 1965
Other data may also be placed on this card and will be reproduced in the
166 -
heading of the output just as printed on the card.
2. The second card contains the chart nual'er (3 spaces), reference
tank nwu.ner (6 spaces), and the index (8 spaces)
For example, if chart number 12, reference tank, 11633, and the
tank 1.,dex, 310.68, are the data, then the card reads as follows:
0120116330310.680
3. Data Cards: There must be a total of forty-eight cards;
i.e., one for each half hour of data even if data are missing for part
of the time. The pressure, temperature, wind direction, and wind
speed data mist start on the first card. All data must start on the half-
hour and alternate from there. For example:
Wind WindTime Ll L2 L3 L4 L5 Press. TeDir. Ied
0030 2.93 7.82 10.63 15.72 2.93 130 13 1.029 00100 2.83 7.89 11.01 15.47 2.83 - - -
Cards read:
002.93007.82010.63015.72002.9310.29032.1300 .002.83007.89011.01015.47002.8399.99
4. Missing Data:
a) If more than one of the index values are missing, punch 99.99
in the first five columns. Then skip to column 31 and punch in the wind,
temperature and pressure data on the half hour.
b) If only one of the index values is missing, substitute an average
value for the missing index value.
- 167 -
c) if the pressure, temperature, and wind observations are missing
for a particular half hour, punch 99.99 in columns 31-35.
S. Program For'mat;
The Fortian-4 program and a specimen of the arrangement of the
data for one day are given.
168 -
$JOB 3,5,6000 2002650$FORMS OUI PROGRAM,141326$MxCUTE IBJOB$IBJOB GO,MAPsmrrTC co'rwiC CARBON DIOXIDE INDEX PROGRAM-SUMMER 5 LEVEL VERSION(REVISED)
DIMENSION S (5,4B),AI(5,48) ,Kr(48),SDA(48),T(24),P(24),IWD(24) tIws1(24)
1 FORMAT(13,16,F8.3)2 FORMAT(SF6.2,F5.2,T4.0,213)10 FORMAT(1H1,4OX,38H DAILY C/.RBON DIOXIDE AIR INDEX VALLES/53X,15H B
1ARROW, ALASKA/48X,26H NORTH MEADOW LAKE STATION/I11 FORMAT(83H
12 FORNAT(19X,15H CHAPT N'UMBER =13,15%.,18H REFERENCE GAS W c16,8X,S8HlINDEX zF9.3/)
13 FORMAT(6H AST,10X,2L&H HALF HOURLY SCALE DIFF..,19X,23H HALF HOU1Y INrE:X, AIR,13X,35H WIND DIR SPEED PRESSURE TEMlP/IOX,3Hl 1.,24X,3H 2.14X,3H 3.,4X,3H 4.,4X,3H !.,SX,3H 1.,7X,3H 2.,7X,3H 3.,7X,33H 4 .,,7X,SH 5.,4X,33H DEGREES 101. BARS C.)
14 FORMAT(2X,14,1X,F7.2,F7.2,F7.2,F7.2,F7.2,4XF8.3,2X,re.3,2X,r8.3,21X,FS.3,2X,F8.3,SX,13,6X,13X.X,F7.4,3X,F5.0)
15 FORHAT(2H I*,16H DATA MISSING)16 FORMATUf/3H0 NUMBER OF HALF HOURLY OBSERVATIONS:FL4.0/26HO RECORDE
1R SCALE FACTOR vF?.3/1640 MEAN INDEX 1 v FB.3/16H0 MEAN INDEX 2 =F82.3/1640 MEAN INDEX 3 a F8.3/16H0 MEANi INDEX 4 a F8.3/16H0 MEAN INDEX3 5 = F8.3/28HO MEAN INDEX AT ALL LEVELS z F8.3/17H0 MEAN PRESSURE zF47.1,10H MILLIBARS/20H0 MEAN TEMPERATURE :F5.0,19H DEGREES CENTIGRA5DE/16H0 L1=16.0 METERS/ISHO L2*1.O METERS/iSHO L3*0.5 ML7ERS/16H06L420.25 KETERS/17H0 L5=0.125 METERS)
17 FORMAT(2H 14,16H DATA NISSING,77X,13,6X,13,4X,F7.4,3X,r5.0)18 FORNAT(1H,114X,7H PAGE 2)
RSF=1 .7201(1:0DO 50 J=1,48MJ~JiF(moD(mj,2))51,52,51
51 1(1:1(+30KT(J )::KK1=KI,+70GO TO 50
52 KT(J):K.50 CONTINUE200 ITR=0
READ(5,11)READ(5,1) ICNIRT,WRGDO 75 J=1,48
J 1=JIF(MOD(J,2 ) )76 ,77,76
76 X2=K1-ITR
IYTR:ITR+ 1GO TO 75
-169-
77 IED52 S(,)I15
75 CONTINUEDO 99 J-1,48SDA(J)a-O.ODO 99 1:1,5
99 AM(,3)ZO.OAVvO .0AV2=.0OAV 3=0.0AV4O0.0AV=MDINCO.0DO 100 J=1,48A=SD(1,J)iF(A-99. 99)101,100,101
101 DIN:DIN+1.OAV1&AVl+SD(l,J)AV2.AV2+SD(24,J)AV3=AV3+SD(3 ,J)AVL=AYA4+SD( is,J)AV5=AV5+SD(5 ,J)
100 CONTINUEAVI=AV1/DINAV2=AV2/DINAV3=AV3IDINAV4=AVI4/DINAVS=AVS/DINAV =0.0DO 102 J=1,48A=SD(,J)IF(A-99.99)103 ,102,103
103 S:0.0DO 104 I=1,5AI(I,3)=WRG+(SD(I,J)*RSF)
104 S=StSD(I,J)
AV=AV+SDA(J')102 CONTINUE
AV=AV/DINAV1:WRG+(AV1*RSF)AV2=WRG+(AV2*RSF)AV3=WRG+(AV3*Rsr)AVis:WRG+(AV4*Rsr)AV5=WRG+(AV5*RSF)Av=WdRG+(CAV*RSF)DO 105 I=1,24T(I)=0.556*(T(I)-32.0)IF(P(I-15.00316.316,317
316 P(I)=P(I)/10.J)GO TO 105
317 F(I)=(33.864*P(I))/1000.O105 CONTINUE
PA0 .0TA=0.0DIT=0.0DO 125 1=1.24
-170-
AzP(I)IF(A-99. 99).'26 ,125,126
126 IYITtDIT+1. 0PANPA4P( I)TAmTA+T(I)
125 CONTINUEPAx(PA*1000. )IDITTARtTA/DTWRITE(6 ,10)WRITE(6 ,11)WRTTE(6,12) 1CNIRTWRGWRITE(6,13)KlzODO 150 Tnl,49AnSD(1,J)IF(A-99 .99)151,152,151
152 JimJIF(MOD(J1,2))155 ,156,155
155 K12X1+1BzP(K1)ir(B-g9. 99)157,156,157
157 WRITE(6,17) KT(J),IWD(K1),TWS(KI),P(K1),T(Kl)GO TO 150
155 WRITE(6,15) Kr(J)GO TO 150
151 J1 aJIF(MOD(J1,2) )153,1S4,153
153 Kl=1I1+l
1AI(2,J),AI(3,J),AI(4,J),AI(5,J),IWD(K1),IWS(K1),P(K1),T(K1)GO TO 150
154 WRITE(6 ,14) KT(J),SD(1,J),SD(2,J) ,SD(3,J),SD(4,J),SD(5,J),AI(1,J),
150 CONTINUEWRITE(6,18)WRIM6,11)WRITE(6,16) DIN,RSF,AV1,AV2,AV3,AV4,AV5,AV,PA,TAGO TO 200EN])
SENTRY COTM$ DATA
I PAY 19671.280100670311.71C002.9300"1.82010.6301S.72002.9310.29032.1300130 2.83007.89011.01015.47002.8399.99002 .96007 .75011. 26015. 30002. 9610. 2qo32 140011002.93007.50011.05015.18002.9399.99003 .08007 .61009 .02015 .72003 .0810. 29032. 140011002. 90007 .75010 .96016 .17002-.9099 .99002. B9008 .09010 .75016 .78002. t~91O. 2903] .1500100 2.89008.20010.87017.39002.8999.99002 .83008. 57008. 57017. 88002.89310 .28031. 140011002.93008.87011. 23017.93002.9399.99002.94008.91011. 35018.29002.9410.28031.14U009002.88009.21011. 13018. 54002.8899.99002.90008.66011. 21019.23002.9010.28032.140008
-171-
DOCUMENT CONTROL DATA - R & 0
UN I VLPS ITV OF WASH1,M UNC SSI OIL
AN A:AALYSIS OF CAFO,' DIOXIDE 1A~ ME ARCTIC ,1OSPiIEE A4EA'1 BAPPIt' j"LASKA1961 TO 1967
* OISCO-P 1-9 VC? TES Ip 01 o'*Po-t -d -l. diiie)
SCIE1NTIFIC REPOPT*~~ ~ ~ AwTo48(- " ,odl ntil at..
JOHN' J. KELLEY, JR.
0 11PORT OArIF IS. TO'AL NO 00 IIIIACO S
APRIL 1969 172 4B.CON YAC* oft rM.N1 NO 0. oGNATOWS RE(PORT NVVS~~l
rJOO04-67-A0103-J007 SCIENTIFIC REPORT #3L. "FlOjOc T .40
th.. *p.,r)
01S UPPLEMCNI4A'* NOTIgS 12 SPONSORING -LITARY ACTVITYfOFFICE nr UI\'iAL rESEP"CI, C)DE 4~15ARCTIC PPOflA11'-!A"SHIJ(TON, D, C. 2 22 5
The results of the measurements of carbon dioxide in air At Barrow, AM~are presented. Reference gas comparison data are tabulated, and methods 0.-calculations are discussed. The average daily concentrAtions of atfnosnohericcarbon dioxide Are tabulated for the period 1r) July 1961 to 15 September 1-9(7The diurnal variations of carbon dioxide durinn this neriod Are also nresc-nt .
- 4 0!01-I , I S.- brt R.,~,I, I,,