I 'i
'1!;
II !'!,
H
I *«illl'HI! > fl
ill
1",
°OOR70008
1
n
-------
ir
-------
REPORT TO
THE TECHNICAL COMMITTEE
OF THE CALUMET AREA-LAKE MICHIGAN
ENFORCEMENT CONFERENCE
A STUDY OF PRECISION AMD ACCURACY OF
LABORATORIES AND METHODS OF ANALYSIS
OF PHOSPHATE IK LAKE MICHIGAN WATERS
BY
THE LABORATORY DIRECTORS OF THE
CALUMET AREA-LAKE MICHIGAN
ENFORCEMENT CONFERENCE
UNITED STATES DEPARTMENT OF THE INTERIOR
FEDERAL WA'i'T? QUALITY .'ri-aiTIS^PATIO:;
GREAT LAKES REGION
LAKE MICHIGAN BASIN OFFICE
CHICAGO, ILLINOIS
MAY 1970
-------
TABLE OF CCi:i_~"
Page
ACKNOWLEDGEMENTS i i i
LIST OF PARTICIPATING LABORATORIES iv
o
LIST OF TABLES v
LIST OF FIGURES vi
I. INTRODUCTION 1
II. PROCEDURES. CHROKOLOGICAL DV.1" 2
III.FINDINGS AND DISCU3SIOII 13
IV. CONCLUSIONS AIID RECC^'ZUDAIJ,;. " 20
BIBLIOGRAPHY 30
APPENDIX 31
Procedural Details 32
Literature Review 35
-------
AOKKOWLEDGE4EHTS
The time and energy that has been given so graciously in the
inter-laboratory comparison of phosphate determinations, initiated
*
by the Technical Committee of the Calumet Area-Lake Michigan
o
Enforcement Conference, is gratefully acknowledged.
The Laboratory Directors of the Calumet Area-Lake Michigan
Enforcement Conference vishes to extend their thanks and appreciation
to each analyst who participated in the study and to each supervisor
and director who made facilities and services available for these
studies.
iii
-------
The laboratories and directors participating in the total
phosphate round robin study were:
1. American Oil Company - Robert J. Austin and Robert Babcock
2. Cities Service Oil Company - George Jackson
3. City of Chicago Bureau of Water, Dept. of Water and Sewers -
Carlton Duke
h. Gary-Hobart Water Corporation - Herbert L. Plowman, Jr.
5. Lake Michigan Basin Office - LeRoy E. Scarce
6. Indiana State Board of Health - Stephen R. Kin
7- Inland Steel Company - Thomas Voges
8. Lake Huron Basin Office - Ralph G. Christensen
9. Lake Ontario Basin Office - Herbert F. Mcore
10. Metropolitan Sanitary District of Greater Chicago - Alfred W. Tenny
11. Robert A. Taft Sanitary Engineering Center - Dwight G. Ballinger
12. Milwaukee Sewage Commission - Larry H. Docta
13. East Chicago Sewage Disposal Plant - Bail Poppa
iv
-------
LIST OF TABLES
No. Title Page
1 Comparison of Precision and Accuracy of Phosphate kO
Determinations
2a, 2b Phosphate Determinations by Stannous Chloride Without 4i
Potassium Persulfate, Average Results (mg/l)
3a, 3b Phosphate Determinations by Stannous Chloride and 43
Potassium Persulfate, Average Results (mg/l)
h Phosphate Determinations by Stannous Chloride, 45
Potassium Persulfate and Extraction, Average Results(mg/l)
5a, 5b Phosphate Determinations by Potassium Antimony! Tartrate 4g
and Potassium Persulfate, Average Results (mg/l)
6a, 6b Phosphate Determinations by Stannous Chloride and }^Q
Potassium Persulfate, Average Recoveries (mg/l)
Ja, 7b Phosphate Determinations by Stannous Chloride 50
Without Potassium Persulfate, Average Recoveries (mg/l)
8 Phosphate Determinations by Stanncus Chloride, Potassium 52
Persulfate and Extraction, Average Recoveries (mg/l)
9a, 9"b Pnosphate Recoveries by Potassium Antimony! Tartrate 53
and Potassium Persulfate, Average Recoveries (mg/l)
lOa, lOb, Phosphate Determinations by Stannous Chloride Without 55
lOc, lOd, Potassium Persulfate, Original Data (mg/l)
and lOe (lOe - Individual Laboratory Recoveries)
lla, lib, Pnosphate Determinations by Stannous Chloride and 60
lie, and Potassium Persulfate, Original Data (mg/l)
lid (lid - Individual Laboratory Recoveries)
12a, 12b Phosphate Determinations by Stannous Chloride, 64
Potassium Persulfate and Extraction, Original Data (mg/l)
Vl2b - Individual Laboratory Recoveries)
13s/ 13t>> Phosphate Determinations by Potassium Antimony! Tartrate 66
13c, 13d, and Potassium Persulfate, Original Data (mg/l)
13e, 13f, (l3h, 13i, and 13j-Individual Laboratory Recoveries)
13i, and
13 j
-------
LIST 07 FIGURES
Mo. Title Page
1 Percent Distribution of All Total Phosphate Deter- 22
minations by Stannous Chloride Without Potassium
Persulfate; 0.05 mg/l> and 0.05 mg/1 / 2.5 rag/I
Iron and 0.25 mg/1 Chromium
Percent Distribution of All Total Phosphate Deter- 23
minations by Stannous Chloride and Potassium
Persulfate, 0.03 mg/1 and 0.06 mg/1
3 Percent Distribution of All Total Phosphate Deter- 24
minations by Stannous Chloride, Potassium Persulfate
and Extraction, 0.03 mg/1; and Potassium Antimony!
Tartrate and Potassium Persulfate, 0.00 mg/1 and 0.03 fflg/1
k Total Phosphate Recoveries from Spiked Lake and River 25
Samples by Stannous Chloride Without Potassium
Persulfate, 0.02, 0.06 and 1.0 ng/1
5 Total Fnosphate Recoveries from Spiked Lake and 26
River Samples by Stannous Chloride and Potassium
Persulfate, 0.05, 0.06, 0.90 and 1.0 ng/1
6 Total Phosphate Recoveries from Spiked Lake and River 2J
Samples by Stannous Chloride, Potassium Persulfate
and Extraction, 0.05 mg/1 and 0.90 mg/1
7 Total Phosphate Recoveries from Spike Lake Samples 28
by Potassium Antimonyl Tartrate and Potassium
Persulfate, 0.02, 0.05 and 0.50 mg/1
8 Total Fnosphate Recoveries from Spiked River Samples 29
by Potassium Antimonyl Tartrate and Potassium
Persulfate, 0.80, 0.90, 1.0 and 1.1 mg/1
9 Probability Curve. Total Phosphate Determination by 76
Stannous Chloride Without Potassium Persulfate -
0.05 mg/1 Standard Sample, ?j?,rch 8, 1967
10 Probability Curve. Total Fnosphate Determination by 77
Stannous Chloride With Potassium Persulfate -
0.03 mg/1 Standard Sample, September 19, 1966
11 Probability Curve. Total Phosphate Determination by 78
Stannous Chloride With Potassium Persulfate and
Extraction- 0.03 mg/1 Standard Sample, October 27, 1966
VI
-------
LIST OF FIGURES
No. Title Page
12. Probability Curve. Total Phosphate Determination 79
by Potassium Antimonyl Tartrate With Potassium
Persulfate - 0.03 mg/1 Standard Sample, December 1, 1966
13 Probability Curve. Recovery of Total Fnosphate, 80
Determination by Stannous Chloride Without Potassium
Persulfate - 0.06 mg/1 Lake Sample, March 8, 1967
ih Probability Curve. Recovery of Total Fnosphate, 8l
Determination by Stannous Chloride With Potassium
Persulfate - 0.05 Eg/1 Lake Sample, October 27, 1966
15 Probability Curve. Recovery of Total Phosphate, 82
Determination by Potassium Antimcnyl Tartrate With
Potassium Persulfate - O.JO mg/1 Lake Sample,
December 30, 1966
16 Probability Curve. Recovery of Total Fnosphate, 83
Determination by Stanncus Chloride With Potassium
Persulfate - 0.90 mg/1 River Sample, October 27, 1966
17 Probability Curve. Recovery of Total Fnosphate, 84
Determination by Stannous Chloride With Potassium
Persulfate and Extraction - 0.90 mg/1 River Sample,
October 27, 1966
18 Probability Curve. Recovery of Total Phosphate, 85
Determination by Potassium Antimonyl Tartrate With
Potassium Persulfate - 1.1 mg/1 River Sample,
- December 1, 1966
Vll
-------
A STUDY OF PRECISION AND ACCURACY OF LABORATORIES AND
METHODS OF ANALYSIS OF PHOSPHATE IN LAKE MICHIGAN WATERS
A Report to the Technical Committee of the Calumet Area-
Lake Michigan Enforcement Conference
The Laboratory Directors of the Calumet Area-Lake Michigan
Enforcement Conference
I. INTRODUCTION
This is a report of comparison studies performed by cooperating
laboratories concerned with analysis of Lake Michigan waters and stream
waters in the Calumet Area of Indiana and Illinois.
A series of comparison studies is to be made for determination
of ammonia nitrogen, phosphate, phenol, cyanide, and threshold odor.
Part I presents the findings from a series of eight comparison studies
on phosphate completed between July 13, 19&6 and April 11, 1967-
i-
The objectives of the comparison studies are:
1. To determine the reliability (precision and accuracy)
of the analytical procedures as normally used in the
desired concentration range.
2. To determine if there is a change in the accuracy of these
procedures arising from departures from prescribed
analytical routine.
3. To determine the degree of variation between the
participating laboratories.
4. To determine the sensitivity of the methods as used.
5. To recommend necessary changes in procedures.
-------
II. PROCEDURES. CHRONOLOGICAL DEVELOPMENT
This section of our report presents a brief chronological commentary-
on the conditions, implied and explicit, which were obtained in the
various Test Series. It is intended to provide "background for assess-
ment of the results obtained in individual Series and also for comparison
of any or all Series. All results are summarized in Tables 1 to 13j in
the Appendix.
SERIES I. July 13, 1966
Number of samples analyzed: Two (synthetic)
Participating laboratories:
1. Lake Michigan Basin Office, FtfPCA
2. City of Chicago, Bureau of Water, Dept. of Water and Sewers
3. Metropolitan Sanitary District of Greater Chicago
k. American Oil Company
5. Inland Steel Company
6. Indiana State Board of Health
7. Lake Huron Basin Office, FWPCA
8. Lake Ontario Basin Office, F.fPCA
Conditions: The following conditions were stipulated by
advance notice to the participating laboratories.
Stannous Chloride Method: Standard Methods, 12th Ed., pp.236-237,
except for one modification (the addition of ammonium persulfate).
Samples should be run in triplicate. Emphasis was placed on the
cleanliness and pretreatment of glassware, and the importance of using
glassware for phosphate analysis only.
-------
SERIES II. September l6, 1966
Number of samples analyzed: Five (one synthetic, one lake,
one lake spiked, one river and. one river spiked)
Participating laboratories:
1. Lake Michigan Basin Office, WPCA
2. Gary-Ho"bart Water Corporation
3. Metropolitan Sanitary District of Greater Chicago
4. Inland Steel Company
5. Indiana State Board of Health
6. Cities Service Oil Company
7- American Oil Company
8. Lake Ontario Basin Office, FWTCA
9- East Chicago Sewage Disposal Plant
10. City of Chicago, Bureau of Water, Dept. of Water and Sewers
Conditions: The following conditions were stipulated "by advance
notice to the participating laboratories.
Stannous Chloride Method: Standard Methods, 12th Ed., pp.236-237,
except for one modification (the addition of ammonium persulfate).
Samples should be run in triplicate. Emphasis was placed on the same
items as listed in Series I.
September 29, 1966
Calumet Area Laboratory Directors met for the purpose of reviewing
the results obtained from the July 13 "and September 16 Test Series I and
II, respectively. The results from Series I and II were fairly good for
the synthetic, lake and spiked lake samples. The river sample and spiked
river samples showed a wide range of results and very poor recoveries.
-------
From a review of these
laboratories agreed upo:.
1. It was agreed t^r..
total phosphate.
2. It was agreed tr ,
analyzed in trip.":..'
depending upon 1
3. It was agreed t'.:-? ,
persulfate.
k. It was agreed tv. ',
of choice for f j:..
5. It was agreed th .-.
veek of October 17]
(one spiked with £\
6. It was agreed that
aspects of the prr
series of the phr .
Board of Health c/
work. All Labc"? -
Michigan Basin C."
Basin Office wv.:
test procedure.
with the next 5s:-'
and after considerable discussion,
llowing points:
terminations would include only
*
\aple in each test series would be
two or more consecutive days,
capability.
.-oratories would use potassium
.brane filter would be the method
;posed procedure (to be mailed the
be accompanied by two river samples
j and interfering substances).
/as need for research on various
procedure used in the first two
aparison test. Indiana State
lichigan Basin Office were to do this
Actors were to submit to the Lake
'r suggestions and the lake Michigan
'.sh the official phosphate comparison
done and the procedure was sent out
-------
SERIES III. October 17. 1966
Number of samples analyzed: Two (one river sample and one river
sample spiked with phosphate and interfering substances (Fe and Cr)
Participating laboratories:
1. Lake Michigan Basin Office, FrfPCA
2. Gary-Hobart Water Corporation
3. City of Chicago, Bureau of Water, Dept. of Water and Sewers
4. Inland Steel Company
5. Indiana State Board of Health
6. East Chicago Sewage Disposal Plant
. 7. Lake Huron Basin Office, FWPCA
Conditions: All laboratories were to follow the procedure
exactly as outlined. Each laboratory was to perform analyses in
triplicate each day for five consecutive days.
Potassium Antimony1 Tartra,te Method: Determination of Ortho
Phosphate in Fresh and Saline Waters, G.P.Edwards, A.H.Molcf, and
R. W. Schneernan. Journal American Water Works Association, Vol. 57,
July 1965? PP- 91T-925 (except for the addition of potassium persulfate).
October 27, 1966
A meeting of the Calumet Area Laboratory Directors, under the
chairmanship of Mr. LeRoy E. Scarce, was held to discuss phosphate
analytical procedures and the results of the phosphate comparison test
on samples distributed October 17, 1966.
-------
The results of the October 17 series were examined and discussed.
It was agreed that the results indicated fairly good precision within
each laboratory, but significant variation between laboratories. The
results were far better in Series III than those in Series II for the
river sample.
After a great deal of discussion, no consensus of opinion could
be reached regarding the most preferable method. It was agreed that
the next comparison series would be analyzed according to the four
methods listed below:
1. Standard Methods - stannous chloride with persulfate.
2. Standard Methods - stannous chloride, persulfate with
extraction.
3« Stannous chloride, perchloric acid, without extraction,
according to method provided by the Ontario Water Resources
Commission.
4. Potassium antimonyl tartrate with persulfate, using a
30-minute digestion and read at 15 minutes.
Sets of five samples were distributed to each Laboratory Director
present, to be analyzed as specified above.
SERIES IV. October 2J, 1966
JMumber of samples analyzed: Five (one synthetic, one lake, one
lake spiked, one river and one river spiked).
Participating laboratories:
1. Lake Michigan Basin Office, FWFCA
2. Gary-Hobart Water Corporation
-------
7
3. City of Chicago, Bureau of Water, Dept. of Water and Sewers
k. Inland Steel Company
5. Indiana State Board, of Health
6. Cities Service Oil Company
»
7- American Oil Company
8. Lake Huron Basin Office, FWPCA
9. Lake Ontario Basin Office, F/TPCA
Conditions: The synthetic sample, lake sample and spiked lake
sample vsre to be analyzed in duplicate for four days or in triplicate
for two days. The river and the spiked river samples were to be run
in triplicate for five days, if possible, or at least two days.
The following procedures were to be followed:
1. Standard Methods^ - stannous chloride with persulfate.
2. Standard Methods - stannous chloride, persulfate with
extraction.
3. Stannous chloride, perchloric acid, without extraction.
k. Potassium antimonyl tartrate with persulfate, using 30~Biinute
digestion and read at 15 minutes.
December 1, 1966
A meeting of the Calumet Area Laboratory Directors, under the
chairmanship of Mr. LeRoy Scarce, vas held to discuss phosphate
analytical procedures and the analytical results of the samples distributed
October 27, 1966.
-------
8
Several laboratories failed to provide any data at all, and some
of those returning results were not able to conduct a complete series
of comparisons for even one day. Therefore, this particular effort
in comparing the four methods was delimited through insufficient data.
Various laboratory difficulties encountered in making these analyses
were discussed. After much discussion pertaining to the choice of
method for further comparison series, it was decided that the next
series of samples would be analyzed according to the tartrate method.
It was agreed that the following modifications be made:
1. Ninety minute digestion of all samples.
2. Concentration of those samples in the range of 0.00-0.10 mg/1.
SERIES V. December 1. 1966
Number of samples analyzed: Five (one synthetic, one lake, one
lake spiked, one river and one river spiked).
<-
Participating laboratories:
1. Lake Michigan Basin Office, FWPCA
2. Gary-Eobart Water Corporation
3. Metropolitan Sanitary District of Greater Chicago
k. City of Chic230, Bureau of Water, Dept. of Water and Sewers
5. Inland Steel Company
6. Indiana State Board of Health
7. Lake Huron Program Office, FWPCA
8. Lake Ontario Program Office, F/rPCA
9. East Chicago Sewage Treatment Plant
-------
Conditions: Triplicate analyses wers per.?
employing the tartrate method. Samples vere d.'.
and the synthetic, lake and spiked lake s£-T.ple:-
evaporation.
SERIES VI. December 30, 1966
Nusiber of samples analyzed: Five (one syrr,
lake spiked, one river and one river spi!;
Participating laboratories:
1. Lake Michigan Basin Office, FWPCA
2. Gary-Hobart Water Corporation
3. Metropolitan Sanitary District of Gre:
4. City of Chicago, Bureau of Water, Dsp
5. Inland Steel Company
6. Indiana State Board of Health
7. American Oil Company
8. Lake Huron Basin Office, JVPCA
9. Lake Ontario Basin Office, FVIPCA
10. Milwaukee Sewage Commission
Conditions: The same as in Series V.
January 26, 1967
Calumet Area Laboratory Directors met fo;1
the results obtained from the December 1 Test ,
Test Series VI. The lake data in Test Series "
improper mixing in the preparation of samples.
showed a substantial improvement over the prev:
LI samples
90 minutes
:-n.trated by
lake, one
r and Sewers
e of reviewing
i the December 30
r.ed because of
es V and VI
eries.
-------
10
It was agreed that further analyses, comparing stannous chloride
and tartrate methods, was desirable in order to demonstrate relative
performance when applied to waters containing iron and chromium inter-
fering substances. It was agreed that the Lake Michigan Basin Office
and Indiana State Board of Health laboratories would analyze a lake
sample and a river sample spiked with interferences and twenty replicas
were run on each sample employing the following methods; stannous
chloride with persulfate, stannous chloride with persulfate,and extraction
and tartrate with persulfate. Both laboratories would investigate time
required for color development and the optimum acid strength to be used.
It was further agreed that one more round robin involving all laboratories
would be necessary.
SERIES VII. March 8, 196?
Number of samples analyzed: Six (one synthetic, one synthetic
spiked with 2.5 mg/1 of iron and 0.25 fflg/1 of chromium, one lake,
one lake spiked with phosphate, one river and one river spiked
with phosphate).
Participating laboratories:
1. Lake Michigan Basin Office, F//PCA
2. Gary-Hobart Water Corporation
3. Metropolitan Sanitary District of Greater Chicago
4. City of Chicago, Bureau of Water, Dept. of Water and Sewers
5. Inland Steel Company
6. Indiana State Board of Health
7« Cities Services Oil Company
8. .American Oil Company
9. Lake Huron Basin Office, FWPCA
-------
11
10. Lake Ontario Basin Office, FWPCA.
11. East Chicago Sewage Treatment Plant
12. Milwaukee Sewage Comroission
Conditions: Synthetic samples were to "be concentrated from 200 ml
o
down to 50 ml, lake samples from 100 nil down to 50 ral and river samples
were to be diluted from 25 ml to 100 ml. All samples were to be digested
90 minutes and ran in triplicate and,if possible,ten replicas.
Under the chairmanship of Mr. LeRoy Scarce, the Laboratory Directors
met March 30, 1967. It was agreed that one more round robin should be
run at extremely low levels as found in Lake Michigan waters.
SERIES VIII. April 11, 196?
Number of samples analyzed: Two (one lake and one lake spiked).
Participating laboratories:
1. Lake Michigan Basin Office, FWPCA
2. Metropolitan Sanitary District of Greater Chicago
3. City of Chicago, Bureau of Water, Dept. of Water and Sewers
k. Inland Steel Company
5. Indiana State Board of Health
6. Cities Service Oil Company
T- Lake Huron Basin Office, WPCA
8. Lake Ontario Basin Office, K-/PCA
9. Milwaukee Sewage Commission
-------
12
Conditions: Lake sample not spiked using the stannous chloride
method were run in triplicate and concentrated from 200 ml down to
50 ml. Ten replicas were run employing the tratrate method with
persulfate. Lake sample spiked was run .in the manner as above. All
samples were digested for 90 minutes.
April 27, 196?
Calumet Area Laboratory Directors met for the purpose of reviewing
the results obtained from the April 11, 1967 Test Series VIII. The
potassium antimonyl tartrate method showed greater accuracy and precision.
The stannous chloride method with persulfate and extraction and potassium
antimonyl tartrate with persulfate when applied to lake and river samples
gave equally good results. It was agreed that Mr. Docta would make a
statistical evaluation of the data end the results will determine if
further analytical work is required. It was further agreed that Mr. Kin
and Mr. Duke would make a study to determine the limit of detectability
of total phosphate
May 24, 1967
A meeting of the Calumet Area Laboratory Directors was held
May 24, 19^7 under the chairmanship of Mr. LeRoy Scarce to discuss the
results of the statistical analysis of the phosphate data and special
studies to determine the minimum detectable limits of total phosphate.
It was unanimously agreed that the phosphate comparison tests should be
terminated and the final report prepared as soon as possible.
-------
13
Series VIII showed that when all laboratories followed the same
procedure, most of the laboratories obtained a precision of ± 0.01 mg/1
on a lake sample containing O.Co mg/1. When the lake sample was spiked
with 0.02 mg/1, a.11 laboratories obtained, a precision and an accuracy
of ± 0.01 ing/1, employing both the stannous chloride method without
persulfate and tartrate with persulfate.
The subject of choice of method was again brought up and the
opinion was expressed that when analyzing lake water there was not
much choice. On the other hand, when analyzing grossly polluted water,
the tartrate and extraction methods were equally as good, but the
tartrate method was preferred because of ease of manipulation.
Clean glassware was imperative. Cleaning glassware with hot 1:1
hydrochloric acid, rinsing with distilled water and treating the glass-
ware with distilled water containing all reagents was found to be the
best method for cleaning.
This section on procedures indicate"', that with conformity of
procedure, reliable results can be obtained.
The results of the comparative series are discussed and summarized
in detail in the next section of this report.
III. FINDINGS AHD DISCUSSION
Stannous Chloride Method Without Potassium ,P_ersul£ate
As indicated in the preceding section, Series VIII showed nuch
better agreement of results from the individual laboratories than
Series VII when employing the stannous chloride method without potassium
-------
persulfate. In Series VIII the results were more consistent and
gave "better indications of the precision and accuracy that can "be
achieved when the recommended procedure is carefully followed.
Table 1 presents a comparison of precision and accuracy of phosphate
methods. Table 2 presents individual laboratory average results chrono-
logically and anonymously. When analyzing a lake sample in Series VII,
a precision of ± 0.03 mg/1 (one standard deviation) was obtained;
whereas in a repeat analysis in Series VIII, a precision of ± 0.01 mg/1
was realized. A precision and accuracy of ± 0.01 mg/1 was obtained
when analyzing a standard containing 0.05 mg/1 of phosphate.
Series VIII indicates that equally good precision and accuracy
can be obtained when analyzing lake samples containing 0.06 mg/1 of
phosphate.
Recoveries of known amounts of phosphate by the stannous chloride
method without potassium persulfate are shown in Table 7« The precision
and accuracy was ± 0.02 mg/1 and ± 0.01 mg/1 for recoveries of 0.0-5 and
0.02 mg/1,respectively, of phosphate from Lake Michigan water. The
precision and accuracy for recovery of 1.0 mg/1 of phosphate from river
water (collected from the Indiana Harbor Canal) was ± 0.26 and 0.33,
respectively.
Stannous Chloride Method with Potassium Persulf ate
Table 3 presents individual laboratory average results chrono-
logically and anonymously. The precisions obtained, using the stannous
chloride method with potassium persulfate, in Series I and IV when
-------
analyzing Lake Michigan water and Lake Michigan water spiked with
0.05 mg/1 were ± 0.01 mg/1. Series II showed a precision of
0.02 mg/1 for the lake sample spiked with 0.06 mg/1 of phosphate.
The river sample in Series II showed a precision of ± 0.32 mg/1
and the spiked river sample (l.O mg/1) ±O.Vf; whereas in a repeat
analysis in Series IV showed precisions of ± 0.17 end ± 0»33 ^g/1
for the river and river spiked (0.90 ing/l) samples, respectively.
A precision and accuracy of ± 0.01 mg/1 was obtained when analyzing
standards containing 0.03 and 0.06 mg/1 of phosphate.
Equally good results can be obtained when analyzing Lake Michigan
water, Lake Michigan water spiked and standards.
Recoveries of known amounts of phosphate by the stannous chloride
method with potassium persulfate are presented in Table 6. The precision
and accuracy was ± 0.01 and ± 0.02 mg/1 respectively for recoveries of
0.06 mg/1 of phosphates from Lake Michigan water in Series II, whereas
Series IV showed a precision and accuracy of ± 0.01 mg/1. The precision
and accuracy for recovery of 1.0 mg/1 of phosphate from river water was
± 0.25 and ±0.57 mg/1 respectively in Series II and ± 0.12 and ±0.30 mg/1
in Series IV.
Stannous Chloride Method With Potassium Persulfate Followed by Extraction
Table k presents individual laboratory average results chrono-
logically and anonymously. When using the stannous chloride method with
potassium persulfate followed by extraction, the precision and accuracy
was the same as the two preceding methods in case of the standard, Lake
-------
16
Michigan vater and Lake Michigan water spiked. The precision for
the river and the river spiked samples was considerably better than
the two preceding methods.
A standard of 0.03 nsg/1 showed a precision and accuracy of ± 0.01 mg/1.
Lake Michigan water and Lake Michigan water spiked with 0.05 mg/l showed
a precision of ± 0.01 and 0.00 mg/1 respectively. Precisions of ± 0.06
and ± 0.20 rog/1 were observed for river water and river water spiked
with 0.90 mg/1 of phosphate.
Recoveries of known amoiints of phdsphate by the stannous chloride
method with potassium persulfate followed by extraction are presented in
Table 8. A precision and accuracy of ± 0.01 mg/1 was obtained for a
Lake Michigan water sample spiked with 0.05 mg/1 of phosphate. A river
sample spiked with 0.90 mg/1 of phosphate showed a precision of ± 0.11 mg/1
and an accuracy of ± 0.20 mg/1.
s-
Potassium Antimony1 Tartrate Method With Potassjura Persulfate
Table 5 presents individual laboratory average results chrono-
logically and anonymously. When analyzing a river sanple containing
0.83 to 1.59 mg/1 of phosphate, precisions ranging from ± 0.09 to
± 0.29 mg/1 were obtained. River water spiked with phosphate ranging
from 0.80 to 1.1 mg/1 gave precisions in the range of ± 0.2^ to ± O.kO mg/1.
Lake Michigan water samples containing 0.0k to 0.70 rag/1 of phosphate gave
precisions ranging from ± 0.01 to ± 0.07 mg/1. Precisions in the range
of ± 0.02 to ± 0.0k mg/1 were obtained for Lake Michigan water spiked
with phosphate in the range of 0.02 to 0.50 mg/1. Precision and accuracy
for standards ranging from 0.00 to 0.03 mg/1 was ± 0.01 mg/1.
-------
17
Recoveries of known amounts of phosphate by the potassium anti-
monyl tartrate method with potassium persulfate are presented in Table 9
Precisions and accuracies of ± 0.01, 0.02 and 0.07 mg/1 were obtained
for Lake Michigan water samples that had been spiked with 0.02, 0.05
and 0.50 mg/1 of phosphate respectively. River samples spiked with
0.80, 0.90, 1.0, and 1.1 mg/1 of phosphate gave precisions of ± 0.27,
0.13, 0.23 and 0.13 mg/1 and accuracies of + 0.29, 0.14, 0.32 and
0.1^ mg/1 respectively.
Data Evaluation
Figures 1 and 2 summarizes the results from the stannous chloride
method without potassium persulfate in terms of deviation from the known
amounts of total phosphate. The range of deviation from known amount
and distribution of individual values are presented as percent of all
determinations occurring from all, participating laboratories. The
i-
reliability of the method as used in the various laboratories may, in
this manner, be estimated. Approximately 80 to 85$ of all the deter-
minations for standard samples containing 0.05 nig/1 are within ± 0.01 mg/1
(one standard deviation). Approximately 55 to 8l$ of all the deter-
minations for spiked lake sesiples ranging from 0.02 to 0.06 mg/1 are
within ± 0.01 mg/1 and for a spiked river sample at the 1.0 mg/1 level,
k$% era vithin ±0.10 mg/1.
Figures 3 and k summarize the results from the stannous chloride
method with potassium persulfate. Approximately 65 to 95$ of all the
determinations for standard samples ranging from 0.03 "to 0.06 mg/1
are within ± 0.01 mg/1. Approximately 52 to 95$ of all the determinations
-------
18
for spiked lake samples ranging from 0.05 to 0.06 mg/1 are within
±0.01 mg/1 and for spiked river water samples 4 to 12$ ranging from
0.90 to 1.0 mg/1 were within ± 0.01 rug/1.
Figure 5 summarises the results from the stannous chloride method
with potassium persulfate followed by extraction. Approximately $0 to
100$ of all the determinations for a standard containing 0.03 ff-gA
total phosphate values are all within 0.01 mg/1 of the known value.
The same is true for a lake sample spiked with 0.05 Jag/1 of total
phosphate. Zero to 31$ of the determinations for a river sample spiked
with 0.90 mg/1 of total phosphate are within ± 0.10 iag/1 of the known
value.
Figure 6 summarizes the results from the potassium antimonyl
tartrate (PAT) method with potassium persulfate. Forty to 100$ of
fl.li the determinations for standard samples ranging =from 0.00 to
0.03 mg/1 are within ± 0.01 mg/1. In Figure 7, 17 to 82$ of all the
determinations for spiked lake samples ranging from 0.02 to 0.50 mg/1
are within ± 0.01 mg/1. In Figure 8, 32 to 66$ of all the deter-
minations for spiked river samples ranging from 0.80 to 1.1 rag/1 are
within ±0.10 mg/1.
The findings are presented in further graphic detail in Figures 9
through 18, located in the Appendix in the form of probability curves
for selected samples used in the study.
-------
19
Laboratory Evaluation
Since the data are herein presented anonymously, a direct comparison
of laboratory performance in using the four methods is not possible.
However, all laboratories, of course, did not show equal performance.
As indicated in the Procedure Section, consistency of relative achieve-
ment was present at the beginning of these comparisons. Most of the
laboratories did demonstrate that, with enough effort and special pre-
cautions, the data so generated might be considered as interchangeable
if a standard deviation of ± 0.01 rag/1 for l?,ke samples in the range of
0.00-0.06 mg/1 and a standard deviation of ± 0.10 mg/1 for river samples
in the range of 0.80 to 1.1 mg/1 is allowable.
Mr. Lawrence H. Docta, Laboratory Supervisor, Milwaukee Sewage
Commission, Milwaukee, Wisconsin did a statistical analysis of LMBO February
data to compare methods, stannous chloride, stannous chloride with ammonium
persulfate and potassium antinonyl tartrate with ammonium persulfate,
and to determine which is the best method.
Mr. Docta's analysis shows that the PAT method with ammonium
persulfate is far superior to the stainous chloride method in Standard
Methods, Twelfth Edition (1965) and the modified standard methods
procedure employing ammonium persulfate. The coefficients of variation
are the lowest for the PAT method. The lower the coefficient of
variation, the better the method is. The ideal coefficient of variation
is 1$ and 5$ is considered to be undesirable.
-------
20
In order to ensure the "best possible results, only those
laboratories demonstrating ability to meet a precision level of
±0.01 mg/1 should be included in a nutrient monitoring operation.
In conclusion, this section on procedures shows that good
results can be obtained by the PAT method for phosphate, especially
at the low levels encountered in Lake Michigan water, provided that
at great amount of care in preparation and skill in technique are
exercised, and that there is strict adherence to the method outlined
in the Appendix of this report.
IV. CONCLUSIONS AMD REOTLMENDAIIONS
1. This study indicated that an accuracy of ± 0.01 mg/1 and
a precision of ± 0.01 rag/1, both expressed as one standard
deviation, can be achieved when analyzing Lake Michigan open
vater, inshore and harbor samples by the PAT method.
i-
2. The above results have been obtained by complying strictly
with the procedure as presented in the Appendix of this report.
3. The PAT method was de.: cnstrated to be superior (more accurate,
greater precision and freer of interferences,especially iron)
to the stannous chloride method.
4. Of the eleven participating laboratories, the majority was
able to achieve the above accuracy using the PAT method. These
results were not achieved on a routine basis, but under conditions
requiring extraordinary care and precautions.
-------
21
5- The limit of detectability using the PAT method, as presented
' herein for the detection of total phosphate in Lake Michigan
waters, appears to "be 0.01 iag/1.
6. Only those results from laboratories showing the continuing
capability to analyze at an accuracy of ± 0.01 mg/1, or better,
should "be accepted in a monitoring operation when analyzing
for total phosphate levels below 0.10 mg/1.
7. Historic data reporting total phosphate levels below 0.10 mg/1
should be evaluated with extreme caution. There appears to be
no practical way to develop a correction factor to apply to
the latter data which would provide acceptable correlations
in the lower concentration ranges.
-------
ij ! I | I I
! n ' ! !
22
H
o
tJ h
H O
k
O rH
IT\
CM
S J*
H <| >j O
\ CO rQ fX(
E R CQ H
H H
ti LTS
O O
SO..
<2 o
fe- -;J H
oJ> (j*N
d o
p-t »
*P, O
<(H 2 O
^^1 «^^
C M PH
LT\
O
-P PH c3
CJ K -P
H <^ ^O O
\> _ EH
C' EH
-------
23
--Hf-H-
±rhr
lirrr-n
TI i T i TTTi rr
-\TT-\rrr rfi~
W^TPWH+c
I [_'_'_ ~^i * L
ZTLI.I i,L P--
I M | I j I ->
; r i i"1 t~t~'
-------
b3
H
fr
$
g
<§
!?«
*8
r-l M
-P§
§£i
Q O
e§
5 M
r- ''
s2 6
H
I8
£S
C
O I
H jrH
rQ^--
«^
r-<
O VO
H O
+? *
o5 O
C!
H T(
i-* £Q
b
4^ O1
S^
O
-------
iL L.}_L_j a P.
i_L_.4_L4_i._; J_J.!_. o r cb 3
_I_J_I_L _i '"LL*T
-------
i : ! i I ; I
izrrnx
-------
VD
to
H
F-4
H
CO W
fa c ro
M O O
Pj Tl
C GO CD O
.,-1 H 43 o
K O
-P < R O
2 *=J 0 o
O O -P -I-3
d o GJ c3
"^i ^_ rC S-l
^ Jj P< rj
§ O O w
n t*-( l^i CD
t4 O PH
o '"* -P 3
£ H o -H
o i H -p
H -g
-------
'.i ;,!>. -, i I ! i !
ZTT-l-r-irr _.j"r-TTIZi:
LLTTZH.ILJ3T
_. .
M--T--'-V- S
. r . CO
C r-j ~, OJ
H « d O
4
o <-d a
H ' -H O
t-i-\rrrrr
! ! rTT I TTT
-------
29
r-rrntr
nirrnirr
fRfFFFF
gg#o
-------
BIBLIOGRAPHY
1. Standard Methods for the Examination of Water and Wastevater,
12th Edition, American Public Health Association, Inc.
New York, K.Y. 196p.
2. Edwards, Gail Pj Molof, Alan H.; and Schneeman, Richard W.
"Determination of Orthophosphate in Fresh and Saline Waters."
Journal American Water Works Association, July 1965.
-------
APPENDIX
-------
32
ANALYTICAL PROCEDURAL DETAILS FOR THE ANALYSIS OF TOTAL PHOSPHATE
1. General Discussion
1.1 'Principle: Ammonium nolybdate and. potassium antimony! tartrate p/nT
react in an acid medium with dilute solutions of ortho-
phosphate to form a heteropoly acid (phcsphonolytdic acid)
which is reduced to the intensely colored rcclybden-oxi "blue by
ascorbic acid.
1.2 Interferences: Arsenates react with the molybdate reagent to
produce a blue color sinilar to that formed with phosphate.
Concentrations as low as 0.10 mg/1 of arsenic interfere with
the phosphate determination. Hexavalent chromium and nitrite
interfere to give results about 3% lev; at concentrations of
1.0 mg/1 and 10-l5£ low at concentrations of 10 mg/1
chromium and nitrite. Sulfide (l^S) and silicate do not
interfere in concentrations of 1.0 and 10 ing/1.
1.3 Sampling and preservation: Samples should be preserved with
^ ml of chloroform per liter at the time of collection to
inhibit bacterial activity.
2. Apparatus
2.1 Acid-washed glassware: All glassware used in the determination
-'should be washed with not 1:1 KC1 and rinsed with distilled
water". The acid-washed glassware should be Tilled, with distil-
led water and treated with all the reagents -to remove the
last traces of phosphate that might be adsorbed on the glass-
ware. Preferably, this glassware should be -used only for the
determination of phosphate and after use it should, be washed
and kept covered up until needed again. If -this is dene, the
treatment with 1:1 HC1 and reagents is only required occasionally.
Commercial detergents jshould never be used .
2.2 Colorimetric equipment: A spectrophotometer with EH infrared
phototube for use at 880 r+n, providing a light path of 1" or .
longer, should be used.'.
3. Reagents
3.1 Sulfuric acid solution, 8N : Dilute 112 ml of cone. HgSO^ with
distilled water to 500 ml.
3.2 Potassium antimony! tartrate: Dissolve h.3538 g KC
H20 in 200 pi of distilled water. Store in a dark bottle at
-------
33-
]
3.3 Ammonium colybdat-e solution: Dissolve 20 g (i'Ki^MoyC^.li H20
in 5OO ml cf distilled water. Store in a plastic bottle at
h°c. .
3«h Ascorbic acid, 0.11-1: Dissolve- l.?6 g of ascorbic acid in
100 ml of distilled water. The solution is stable for about
a week if stored at li°C.
3«5> Combined reagent: Kbc the above reagents in the following
proportions for ICO ml of the combined reagent: $0 ml of
8H H^SO]^, 5> *& °£ potassium antimony! tartrate solution,
13> ml of arcrr.oniun ir.olybdate solution, and 30 ml of ascorbic
acid solution. Mix after addition of each reagent. All
reagents mist reach room temperature before they are mixed
and they should be mixed in the order given. If turbidity
forms in the combined reagent, shake and let it stand for a
few minutes until the turbidity disappears before proceeding.
The reagent- Is stable for one week if stored at li°C.
3.6 Alcohol, ethyl (£p percent) or isopropyl.
3.7 Stock phosphate solution: Dissolve in distilled water
0.716^ g of potessiun dihydrogen phosphate, KF^POi , which
has been dried in an oxren at 105°C. Dilute the solution to
1000 El. 1 ml equals O.£0 mg
phosphate solution: Dilute 20 ml of st-sck phosphate
solution to 10CO rol with distilled water. 1 ml ~ 0.01 mg
3«? Potassium persulTatc, reagent grade.
lt.0 Strong-acid solution: Slowly add 3CO ml cone. HpSO^ to 600 ml
distilled -Eater. VJhen cor-1, add U.O ml cone. H1IO_3 and dilute
to 1 liter,
It* Procedure
lj.1 Make a spot test en each sample to determine the approxir^ate
phosphate concentration. If the color is very dark, a proper
aliquot of sarrple should be used, diluted to 5>0 ml; if the
color Is very light, the sample should be concentrated by
evaporating 200 ml of sample containing strong-acid and
- persulfate, down to 50 ml.
___ . _ Placft appropriate aliquot of the
sample containing not mere than
0.6 mg of PO^ in suitable containers for digestion.
-------
3
1
]
]
]
3
3
3
3
Iu3 Add 1 drop of phenolphthalein indicator to both the filtered
and the unfiltered portions. If a red color develops, add
strong-acid solution dropwise to just discharge the color.
Then add 1 ml in excess.
li.ll Add 0,U g of potassium persulfate to each container.
I{.5> Boil gently for 90 minutes, adding distilled water if neces-
sary to keep the volume between 25 and $0 ml.
li.6 Cool, filter the unfiltered aliquot if necessary through a
membrane filter and transfer both portions to 50 rol nessler
tubes.
il.7 Neutralize to a faint pink color with IN NaOH and dilute to
50 ml with distilled water.
li.8 Add 2.5 nil of ethyl or isopropyl alcohol and mix thoroughly.
lt«9 Add 2.5 ml of combined reagent. Mix thoroughly and allow to
stand exactly 10 minutes for color development. Read at 8802-41.
Samples, standards, and blanks should be read against distilled
water set at zero op'tical density. If final volume is not 5>0 ml,
the volume of reagents used should be adjusted so that the same
ratio of reagents to sample is maintained.
ii.10 Standard curve and blanks: The standards and blanks should be
processed exactly as the samples. At least one standard should
be run either with each set of samples or once each day that
analyses are performed. If the standard does not fall very
close to the curve, then a new calibration curve should be
prepared.
5« Calculations
rng/1 PO^ = O.D. of sample x slope x cone, or dil. factor.
6. Bibliography
1. Standard Methods for the Examination of Water and Wastewater,
12th Ed., 1965.
2. Gail, E.P., Molaf, A.H., and Schnuman, R.Vf. Determination
of Orthophosphate in Fresh and Saline Waters. Journal AVJV7A
57:917 (July 1965).
-------
35
To: A. M. Tenny
From: G. R. Richardson
Re: PHOSPHATE LITERATURE REVIEW
In prior years, the primary complication involved in a suitable method for the
determination of phosphate has been the selection of an adequate reducing agent
coupled with the proper selection of pH.
Various methods are based upon the fact that a suitable reducing agent, when
added to an ammonium molybdate solution of proper acidity will produce a blue
* '
color if the solution contains phosphate. Parker and Fudge (1927) showed color
can be developed in five minutes and remain stable for one hour under their
experimental conditions. Truog and Meyer (1929) improved Denige's colormetric
methods for phosphate and arsenic. They prepared a stock solution of stannous
chloride by dissolving the pure salt in acidified water, doubled the amount of
ammonium molybdate and increased acidity. This eliminated the effect of even high
amounts of silica.
A method of extracting phosphomolybdic acid with isobutyl alcohol was described
by Berenblum and Chain (1938). This method was later modified by Pons and Guthrie
(1946) inorder to analyze samples with large, amounts of protein or colored and
turbid extracts. In (1949) Martin and Doty used equal volumes of an isobutyl
alcohol and benzene mixture to extract phosphate. This mixture only required a
single extraction step.
Young and Golledge (1950) found that tannins and their oxidations products give
a slight color even in the absence of phosphate. If large quantities of tannins
are present, they may be removed by absorbing and decolorizing with charcoal.
-------
-2-
36
They report very little absorption of phosphate though recent work in our laboratory
indicates phosphate is absorbed in charcoal.
Interferences from other ions in the colormetric determination of phosphate has
caused errors. Greenberg (1950) used sulfamic acid to control nitrite nitrogen.
Ferric iron above 10 ppm not only decreases the intensity of the color it also
produces troublesome greenish tints. Aluminum, manganese, calcium and magnesium
may be present in concentration equivalent to 1000 P.P.M without any influence on
the color.
The use of stannous chloride as a reducing agent in the molybdenum blue method for
the determination of phosphate in sea water was reviewed by Burton and Riley (1956).
This reagent has a number of disadvantages. The color fades quite rapidly and
different batches of molybdate reagent give different intensities with the same
amount of phosphorous. Burton and Riley found P-methylaminophenol sulfate (metol)
used at 100 C for a reducing agent offers a number of advantages over stannous
chloride.
The use of ascorbic acid for the reduction of phosphornobydic acid was first reported
by Ammon and Hinsberg (1936), but their method was modified by several investigators.
A single solution containing ammonium molybdate, ascorbic acid and sulfuric acid was
introduced by Burton and Riley (1958).
The single solution method was modified by Murphy and Riley in (1962), to include
potassium antimonyl tartrate. The color developed rapidly and the procedure still
maintained the advantages of the original method.
There was no interference by copper, iron, or silicate at concentration many times
greater than their normal concentration in fresh water.
Sletten and Bach (1961) overcame the weaknesses of the stannous chloride method
due to the instability of the stannous chloride reagent. They dissolved stannous
chloride in reagent grade glycerine, thus stabilizing the stannous chloride. Gales,
M. E., Julian, E. C. and Kroner, R. C. (1966) described a method of converting meta,
-------
-3-
37
pyro, and organic phosphorus into measurable phosphate in natural water. They used
persulphate for oxidation of the sample followed by reduction in an acid medium.
The colorimetric determination of total phosphate was with stannous chloride.
A rapid, accurate and sensitive automated method for the determination of orthophos-
phate in fresh water was developed by Molof (1965), patterned after the manaul
method using ascorbic acid.
-------
33
REFERENCES
AASGP Committee Report, Determination of orthophosphate, hydrolyzable phosphate,
in total phosphate in surface water. Jour. Am. Wat. Wk. Assoc. 50:1563, 1958.
Berenblura, I. and Chain, E. Biochem - Jour. 32:295 1938.
Burton, J. D. and Riley, J. P. "Determination of soluble phosphate and total
phosphate in sea water and total phosphorus in marine muds."
Micro Chim. Acta. 9:1350, 1956.
Edwards, G. P. Molof, A. H. and Schneeman, R. W., "Determination of orthophosp-
hates in fresh and saline water". Jour. Am. Wat. Wks.
Assoc. 57:917, 1965.
Fontaine, T. D. Spectrophotemetric determination of phosphorus. Ind. and Eng.
Chem., Anal. Ed. 14:77, 1942.
Gales, M. E. Jr., Julian, E. C. and Kroner, R. C., "Method for quantitative
determination of total phosphorus in water." Jour. Am, Wat. Wk.
Assoc. 58:1363, 1966.
Greenbert, A. E., Weinberger, S. W. and Sayer, C. N. "Control of nitrates inter-
ference in colorimetric determination of phosphorus".
Anal Chem. 22:499, 1950.
Martin, J. B. and Doty, D. M. "Determination Inorganic Phosphate". Modification
of Isobutyl Alcohol Procedure.
Anal Chem. 21:965 1949.
Molof, A. H., Gail, E. P. and Schneeman, R. W. "An automated analysis for
orthophosphate in fresh and saline waters". Automation in Analytical Chemistry.
Technician Symposia, 1965,
Murphy, J. and Riley, J. P. " A single solution method for the determination of
soluble phosphate in natural waters".
Jour. Marine Biol. Assoc. UK, 37:9, 1958.
Murphy, J. and Riley, J. P. "A modified single solution method for the determina-
tion of phosphate in natural waters".
Anal. Chem. Acta. 27:31, 1962.
-------
-2-
39
Parker and Fudge, Soil Science, 24:109, 1927
Ports, W. A. and Guthrie, J. D. "Determination of Inorganic Phosphorus in Plant
Materials". Ind. Eng. Chem. Anal Ed. 18:184, 1946
Sletten, 0. and Bach, C. M. "Modified stannous chloride reagent for orthophos-
phate determination. Jour. A. Wat. Wk. Assoc. 53:1031, 1961.
Young, R. S. and Golledge, A. "Determination of hexametaphosphate in water
after threshold treatment, Ind. Chemist 26:13, 1950.
-------
CO
0
OJ
CQ
~K
12
Pn
<
PH
H
O"H"
^^X
^5 3"
+i oo
H ^"^
O H
H 00
H
o'er
o'cvT
-H CO
i ( * *»
O O
O OJ
+1 OO
O C\
+1 oo
CM O
O ^~-
ro
O VD
+1 H
00
O H
O
+!
O
O H
OO
oo
O CO.
+1 H
o o
+1 ON
Hco
OJ-'
vo
o co
+1 H
m-"* co co
o o HV_^
. > . vo
o -=* o co
+1 ON +1 H
EH
o03
OJ
CO
o
en
o
&
oro
PH
OJ
rH
O
CO
PH
O
O« '
H
O *~^
O
41 ^
O 00
H ** ^
O oo
O'H'
H !^-
o o
o o
O'H'
41 IPk
H O
.'o> 'o'
H"-.
O ro
+1 OJ
O O O OJ O -d-
41 0? °l ^ 41^-
OH O IA
d^ d^
-H CO +1 CO
rH
+1 -d-
\C"~ > O -^^ H
0 O OJ O O'
>^-» s O
+1 H +1 H -H -4-
OJ *-^
O OJ
o ^vT
+1 -3-
CQ
-------
o
o
tr\
o
H
H
O
VO
H
CO
OJ
VO
o
w
EH
<2
§
tD
i
g
£3
H
CO
si
^ s
^W~
& [EX.
8^' K tp
S-S
c3 Sg &""'
OJ < 0 en
O -P
W H CO H
H ffi £> P
PQ O O w
SJ H g «
E-5 S § «
W EH O
S CO M
H ^
1 £Q
^>
<2*
&
o
-P
o
1
H
C)
d
H
"5
r3
^.^
ir\
O
*
0
IP\
0
d
ir\
O
d
3
0
tr\
O
*
O
d
ir\
O
o
tpv
o
»
o
OJ
o
0
^_
o
o
o
»
0
l/N
C3
d
CO
0
d
B
o
ir\
O
d
o
d
H
o
o
_^J-
o
»
o
OJ
o
VD
O
O
T*-f
H
*
O
OJ
o
CO
H
d
8
o
o
CO
H
d
i
H
d
t"~~
H
o
OJ
H
O
CO
H
d
^r
0?
O
o
OJ
o
t-
H
d
3
o
H OJ
0 H
CO I ITN
H H OJ
O H OJ
CO t*~ t^
i 1 oo r
O H H
O CO ro
04 O H
O H OJ
O^ r-J OJ
H H O
0 H OJ
H VD U\
OJ OA LP\
O O H
0
0
ir\
O
*
O
vo
o
d
vo
o
o
*
o
vo
o
o
ir\
0
o
vo
o
*
o
ir\
0
0
vo
o
*
o
3
0
b-
o
o
^*~
o
d
£
o
c9
*
o
o
o
vo
o
o
\Q
0
0
vo
o
o
CD
0
o
a
co
H
0)
"ft
a
co
H
CO
0)
CO
b-
vo
CO
0)
H O
lf\
OJ
LTN
o
o o
OJ
vo
o
0)
CO
o
H
g
ft
CO
OJ
M
H
0)
CO
H
H
OJ
o
H
ft
CO
-------
H
fxj
1 £
pti ^
B
M
Ps
o
cd
f-l
2
o
Q
O
O
+1
c
o
H
W
r-i
O
o
fn
o
- o
-H
H
CO
8
O till
+1 till
H CO -d- OJ t
O O O H OJ
« *
O O O O O
+1 +1 . +1 +1 +1
1 1
1 1
rH H
0 0
O O
+1 +1
O
CO
<1)
-P
H:
31
a
a;
K
41
£
o
OJ
H
ir\
H
LT\
CVJ
^.x
LT\
(M
CVJ
OJ
ir\
O
o
o
VD
H
rH
OJ
VD
O
t-
o
H
5
93
1
KI
s
PH
§
t
o
*
o
t£
K
o
8
o
-
H
p>
W
4>
w
o
r-l
^1
0) 41
CO H
f^
OJ
o
1TN 0
* Cy
O M
LTN t
(M 00
O H
-=f VO
rH ON
O 0
^^^
«
o
oi
4)
^4
H
ft
CO
0) G)
W *r-t
1-3 £H
LT\
OJ
*
OJ
IfN
ir\
H
^^*V
O
H
""CJ
-d
CJ
X
H
ft
CO
<0 4)
w ra
K-3 M
*
-p
o
4)
JH
w
^
3
ta
t.
ft.
o
t.
4)
c2
r-3
^
"*
^~^
V-X
-------
co
co
CO
w
ra
v.
M O
Lf\
O
0
vo
o
o
_^
o
o
o
o
ir\
O
O
VO
0
0
VO
o
o
o
o
H
H
03
0)
H
O
CO
1
VO
VO
vo vc
O .H
O ON
co
o
*
o
ro
O
o
3
o
^
o
o
VO
0
0
CO
o
o
CO
0
0
CO
o
o
o
o
ro
0
o
0
o
co
o
o
CM
o
o
LfN
o
9
o
LT\
o
o
lf\
o
*
o
CM
o
o
CM
o
o
ro
o
o
o
o
ro
o
*
0
VO
o
o
CO
o
o
V
2
t-
o
*
o
&
*
o
H
iH
o
8
o
VD
0
o
VO
o
o
s
o
0
0
ITS
o
o
8
o
^S"
o
*
o
nj
V
H
CO
tt)
l£*
A
co
o
OJ
rH ON
t CO
*
CM OJ
o t-
O CM
*
OJ CO
o o
CM CO
CM CM
t- 0
VO OJ
H OJ
t- t-
CO O
OJ OJ
ro ro
CM CO
CM OJ
-d- b-
-=f U~\
OJ CO
LTN CO
ON co
H OJ
oo ro
ON ^
H OJ
o" P^
H 0
v_x 0
H
Ci JH
O CJ
X CQ
iH 1
ft VD
CO VD
M in "t^
O O Cvl
iH «H O
K K H
OJ VD
0 0
o a
co oj o
o q H
odd
fH H t
000
O O O
oo co co
o o o
0
o o o
CM CM ^-
o o o
o o o
co co ON
o o o
O 0 O
»^-,
ITN
o
d
g
e^(
H
ft
CO
ro 0) 0)
C* J!*j ^*i
d 3 2
H
co
H
a
H
CO
H
<5
*
H
O
CO
r-i
ir\
oo
H
£_j
Q)
K
CO
H
VO
CM
OO
CO
H
H
VO
CVJ
o
o
CM
ON
H
R
d
n3
.M
H
ft
CO
J^
0)
s
-------
H
£
-___!
1
^
Cj
O
c
o
H
CQ
H
O
o;
£
g
CD
+1
H
O
0
4-1
g
d
4-1
H
O
*
O
4H
H
O
O
4-1
H
O
O
44
1 1 1 1
1 1 1 1
H OJ OJ t-
o o ro -3-
o o o o
4-1 4-1 41 4-1
g
O
+1
r~*4
0
o
4-1
1 1
1 1
H H
O O
O O
4-1 +1
1 1
1 1
t- ro
rH OO
o o
4-1 4-!
CQ H
H CQ
M CO
p. 3
K-l W O CO
PQ C_} «S2 Q^
3 ii CJ2 rr*
§ "-* 3
A EH 0)
M CQ t£
^ >4 fH
t3 R tt)
1 >
O
ro vo j* -=h ^ ir\ r
O O O O O rH t
O O O O O OJ OJ
****** <*"'» s~>* x*°-*fc *****
O OJ H H O
^^* ^-LJ-* ^fc^ ^W4^ *^«X
co ir\ _^h CN ro
H H H OJ no
O O O ro H
O O O H OJ
§
I
w
e
5
w
s!
K
CQ
S
PH
ro
0
0
t£ £VI
§ °
« o
&
*
o
1
f^j*
o
VD
O
*
o
1
OJ
0
o
vo
o
o
1
OJ
o
o
H
H
O
1
LTN
O
O
H
t-
OJ
1
VO
r4
^
ro
i
t-
o
OJ
ro
o
o
rH
O
d
ro
O
*
O
H
O
d
S
o
1
VD
O
O
vo
rH
OJ
OJ
H
LTN
VD
*
OJ
1
ro
CO
H
t
0
-
f-^ ^~
M
03
OJ
T!
4)
CQ
1
VO
VD
^"-^
ro vo vo.
O O r-i
O O O"N
VD
o
d
d
cu
r*t*t
H
P)
CQ
ro o a>
O X X
w S
O »^ >3
* N
©
H
Ig
pM
r~i
Pt
CQ
f-t JH
0) 4)
H -H
^>
H*)
CO
(1)
H
^1
O
CQ
1
VD
VO
"^^^
t-
**
O
H
^^
ir\
O
d
-d
^j
H
Pf
CQ
ro O QJ
d iS 2
O
O\
*
o
'S
ti*
H
P)
CQ
J^ J^j
O 0)
« S
H
W
J^
"o
?H
-------
8
g
*?*
CO
£5
o
CQ
H
§
8
%~-t
J^J" |
p3
rH
CQ
3~
E-5\
o to
nT| cf
v_x
*v
W w
O -P
Q Kl
P Q)
s «
0)
g §P
O fH
||
EH
CO
>H
«
CQ
a
s
E~i
^^
a
S
Cs3
S
Q
CQ
0
W
PM
i
v>
1-1
H
c\3
^
OJ
o
&
^3
s}
O
,Q
5
1
r^J
"d
-H
r*
H
CQ
Oi
H
CJ
CO
1
Q)
-P
03
P
H
8
o
^
H
o
CD
s
^_.i
Tl
K>
H
0)
&
rH
O
o
-H
CO
_|_3
^
03
0>
*
_
O
9.
0?
J_^
>
<^
CO
^>
o
CO
o
*
. 0
(11 1
fil no
d 0
CD I
Kl 0
co
0
*
o
co
O
o
>
H
CQ
0>
H
CU
1 j
p
^
cd
CO
0)
CO
1
VD
VQ
"**-*^,
t*~
OJ CO
^ o
o
1
1
H
O
0
+1
^^
o
CO
£}
C5
CO
O
0
1
CO
o
ft
0
CO
*
o
co
o
«
o
G)
r^f
jrt
t 1
1
1
O
CD
O
+1
^^
O
~i.
CO
O
*
o
CO
o
o
1
CO
o
o
CO
*
o
s
0
LPv
o
0
13
0)
^bd
H
O^
CO
0)
cl
h-5
1
1
vo
o
o
+1
o
i !
ir\
LT\
*
H
vo
^
1
o
LTN
H
0
tr\
H
u*\
ir\
H
H
vo
H
^
0)
*H
K
1
1
O
O
+1
o
^.x
t-
VD
CO
OJ
L^
vo
OJ
i
VO
o
OJ
V£>
O
CXI
LT\
OJ
ro
CXI
ON
o
1
H
CO
JH
O
>
H
K
c!
0)
+>
O
0)
ta
S
-------
k6
H
CO
s
O E-t'
CO H
03
EH 43
o
w
O
5 3
i W
W 01
eg s
<< o
H
i«!
^e
B
CO
§
to
to
K"
K
R
p
M
o
^
>
H
0
-p
cS
rH
o
s
__J
^
s
-d
t
r>
H
-a
M
w
0)
H
rH
0) 0)
CO rH
1 P-
to ?
-i-5 t6
cS co
n
ON t-
t- CM
O rH
t LTN
ON ON
O H
CO CO
t CM
O H
CO oo
VO J-
O rH
ON O
ON CO
O H
O t
CO VO
O rH
r"%
H
L_J C
K 0 rH
tQ H CD
<1) N ' (I)
H -H
rH -d rH
> \
O iH iH O
rH K K H
if\ CM
O O
0 0
OJ -3-
0 0
0 0
co -3-
0 0
o o
CO VO
0 0
o o
% £'
o o
CO -3-
o o
o o
-3- LTN
0 0
o o
co v
0 X
d 5
ON _^-
0 -3-
O H
VO CO
O O
O CM
ON ITN
O CM
O H
O *
H VO
0 H
CO CM
O VO
O rH
t LTN
0 -3-
O rH
rH VO
H u\
O H
lf\
O
0
g
X
H
ft
CO
r^
to ty
-^ >
ri -H
^ K
CO
eg
CM
t-
t-
CM
ON
CO
OJ
LT\
-d-
OJ
O
VO
OJ
o
ro
OJ
t
ro
OJ
^_^
0
°^ >
0
CO
i CU
TH CO
ft 1
w ^8
M ---.
(U H
> \
H CM
K H
-3-
O
d
CO J-
0 C-^
d d
LfN -4"
O ON
d d
CO rH
O CO
d d
oo ro
O ON
d d
co O
O ON
d d
00 CM
O CO
d d
ro ON
0 t^-
d d
j- t-
O ON
d d
-d- H
O ON
d d
h
ro a>
0 >
-H
O K
-*
ON
H
8
CM
CM
CM
H
OJ
LTN
O
OJ
s
H
H
OO
OJ
t-
OJ
oo
rH
CM
^-x
H
H
d
JS
H
ft
02
?-i
d)
>
H
«
rH
O
o
8
o
8
o
8
o
o
o
0
H
O
0
81
o
o
0
o
8
o
rH
O
O
s
a
0)
H
rH
CD
CO
1
VO
VO
o
rolo
\.O
CM
rH O
oo
t-
o
H
VO
O
VO
VO
o
<£
o
s
o
LTN
VO
o
CO
VO
o
H
VO
o
8<
o
oo
F-
o
o
X.
rS
ON ON
rH VO
H rH
H -3-
CM ON
rH rH
rH t-
OJ ir\
H H
VO O
OJ O
H rH
CO CO
H ITN
H H
3 £
H H
t- VO
H CM
rH H
CM CM
CM CO
rH rH
ON CO
OJ F-
H -. rH
t- O
OJ LT\
r-i rH
LT\
s^_- "
d
o
X
H
ft
CO
rH
0) to
X >
a -ri
.-3 «
H
CO
OJ
VO
rH
OJ
VO
OJ
OJ
OJ
LTN
H
H
ITN,
OJ
£
OJ
o
o
OJ
-3-
LTN
OJ
CO
CO
CM
ON
CM
CM
«"% H
O H
« £
**^-
o
v' 03
0)
d -H
0) rH
X H
H \
K -3-
^- CT\
0 £
«
0 o
o £
«
0 0
£
0 o
00 LTN
H H
0 o
8 8
*
0 o
£r <*
0 0
<
0 0
& 8
*
0 o
8 8
* *
0 o
& s
«
0 0
ON .-i
o a
* *
0 0
"CM"
o
O
d
(D
^ ^
5 a
-------
1!
a
B
pp
£3
CM
^
p
CO
!
1
CO EH
SW
cqS
^ tn^H
i@j
p^i -p
LT\ § E-l H
P3 H
i £ <§
<^
p^3 ^H
gjpq
CO
H O
5- 1 i
*"*i EH
U§
*>
1
B
P
PH
CO
O
w
t)'
03
3
o
o
H
O
0)
pS
CO
(y
H
.
VDt OCOOOO OH
LTNITN HCOOHCVI HCO
^t ^t OOOJOOLTNlrN IT\_H;
cot-- oo_*o\t^-tr\ _^-t
COlfN OOOlTN^t OCO
OH OOOHOJ OO
ONO ITNVOHOOb- VDt
ONCO OOHOt OON
OH OOOOJOJ OO
II (III! II
ro^ OJOJVOLTNCO co-4-
VOOJ OOOOJOJ Ot-
OH OOOHOJ OO
In
to
1 I g ^*-^
H > ^-N 0
H O H LP> ON
o >
M H la O
> ^x O ^! X > > ~~^-O >
O-Hi-IO* Cj3 dvH-HCU'-r-!
cHKl K HO t ] t 5 K cq HO K
H
O
I O I I 1 I
1 +| 1 1 l 1
O H t -=} ON VO
-4- O O O OJ OJ
0 OOOOO
+! +1 +1 -H +1 +1
O H CM O O 00
-d- -3- 00 VO .3- CO
LfN CO CO OO CO OO
CO O O H ON O
O O t OJ LTN H
OJ O O H H OJ
H H OJ ON -3- o"i
oo O ON OJ ON co
OJ O O H H OJ
1 1 1 1 1 1
CO O H -3- Q OJ
CO O VO H O ir\
H O O H H H
"->. H
^-x H OH
H > "^ CO H
O !>
H to u^ O
rH *^-^ O
T^ ^H T^ T-1
C) Q^ nil (DP
£* CO 1J 4^J O
HI 4tJ -H CO
ft VO TH ft 1
CO VO ft CO t-
^ CO VO
P O f-t P \
OOOO -\O^!^ > >H
H OJ <3 ri -H -H ~^~.
Kt iOtHnCnK-4
1 1
1 1
H OJ
O O
d d
+1 +1
-=* o
vo t-
OJ ON
s &
d d
CO I/N
H H
d d
1 1
0 O
d d
?
*
0
*^_^
f^j
0)
4^
H
ft
CO
OJ O
'"""t *5
1-^1 H
o
+>
o
m
0)
w
+J
H
-------
o
*
o
C*-
O
vo
o
a
to
V
H
H
£
H
R
K
s
5
CO H
H CO
M CO
£1 "^
<2 ^5
CO ft
o §^
HP
"
& « s
8§£
a 6 >
H
C!
C
M
«
o
V£> VD
O CO
* »
O O
-=f C\
O LPv
*
o o
OO O
o ^t
0 0
V0 t
. VO
CO Pi V^
o § vo
-P CO iH
Gj "^^^v
P ON
^-^ ^-^
MD O
O
H
O >
*^s
fa
D <1)
^J r"
Crf «r-{
i i K
I-H
W
0
H
0)
CO
1
VO
"^^^
t-
CVJ
o
H
'-^ 'S*
LT\ C7\
O
O
0 ^-
J_,
0 1>
pb^ r*
nj *H
i-5 P^
-------
H
b
EH
§
5
CQ
PM
>*?
H
!>3
O
03
JH
^
o
q
CM t
O u~\
O O
+1 +1
g
H
CQ
;H
o
Ti
K
H
m
4>
Tl
O
CO
t
\o
vo
"--^
t-
CM
H
s~^
LPv
o
o
0)
"S
s4
. ^
O
o
£H
CD
>
H
K
P
O
O
1-3
0)
03
P
H
-------
w
1
a
1
B
s
H
CO CO
g £3
E §
Is
CO
§1
CO S
K M
s IS r-H
p-j ~*-*^
^5 P1^ t-"
8|^
|||
H~f C^ ^
0 CO >
Sou
H|K
i3 co t;
i rJ
w w o
^ CO ^
£55
f^ O
l§
§ 1
£Lj
1
i
C^t
CQ
O
£
PL(
CO
H
CD
^>
O
O
0)
K
d)
5r
Cj
j^
QJ
r?
o
1
0
1
3
'd
5!
-H
"^
H
O
C>
vo
o
o
tr\
o
O
LTN
0
*
O
_-j.
o
o
VQ
o
0*
U"\
o
m
c?
o
C\J
o
o
oo
o
o
0
o
H
O
vo
*
o
vo
t
o
^
ON
0
-3-
o
o
d
CXI
o
iH
o
d
H
o
o
.H
0
o
o
*
o
H
o
o
o
o
0
H
o
o
CXI
o
o
<&
-p
o
d)
/>!
t
M
rn
H
'>
CQ
0
CQ
H
J_l
0) CD
CQ H
1 P-
cu e
-p ro
a3 CQ
Pi
H
t-f
0)
CQ
1
VD
00
m
s~^
vo
o
o
0)
r^H
cj
M
y^^^
0
H
^1
o
^
H
K
H
M
^1
^1
w
d)
*T~I
J-(
0)
CO
1
t-
vo
H
r-i
**^*^
-^~
*^~s,
CM
0
*
o
CD
c5
i-3
CQ
-------
51
o
ca
3
cj
r-! O
W 5 d
?
3
p~>
23
U
PH
§
CO CQ
ll ^
<3 ft
S S
O Q
H EH'M
P-4 HH "°^~-
< ?s fcC
§w3
80 m
05
W PQ <
^ CQ
B
EH o
pr"] t_J
g <;
^B
o y
5
ij
H
xj
Pi
H
CQ
O
e
O
H
CQ
H
O
0
}-*
CM
O
O
+1
CM
0
*
O
+1
CQ
to
o
ir\
O
*
O
H
O
0)
I
1
CM
O
O
H
1 1
P
CO
c^
to
ID
H
^i
GJ
CO tH
(U E
P TO
£CO
H * *
^ VD
o o
CO
1 O
t v -
vo
CO ^!
o"3 i-5
oo
°?
CJ
-H
MD
CM
O
+1
^_^
O
'o'
CM
LT\
t-
O
o
o
H
l
3
«
o
H
H
W
CJ
H
*^""* M
O CO
CO
H 1
^^ t~
\o
H
> H
s >
t-{
O
O
+1
r-l
O
O
+1
^~~.
0
In"
OO
H
o
o
0
o
1
o
o
o
**"%.
CM
O
*
o
0)
r^J
5
0)
-p
o
td
p
rH
^
ra
-------
53} H
%
O
73?
o 0
<3i
t
i
§
M
6
<
K
|
H
H
<
1
3 ^
dj g
§ S
<, PH
CO CO
co.
la <
O E-I-
CO P H
o? K>
<^l
fog-
^ f-H
O K O
CO Q -H
£j r-l rH
M 3 trt 4)
a 5 o >
pa H o
£ M CO O
H O £>
^S4
K CO
*~^ ^H
O
E^ M
H Ej
B§
^g
o S
w
It
P
H
g
S
CO
o
g
t> c
rH O
»-J
od
t-l
O
>
0 <
rH
O
0
+1
s~~^.
o
~^t
ir\
O
O
Lf\
o
0)1 ?
ta ur\
d| 0
col
(21 0
&
M
o
-p W
cd o
f , j
M *r\
O h
£> 0)
5 0
1 i O
C)
rH CO
vH !n
rd
H <
UN
O
O
Lf\
O
O
>
H
w
0)
H
ra
0)
H
^l
H
«
TJ
0)
-P
O
0)
<~3
O
fn
ra
-P
w
0>
rH
%
&
r9
-------
53
88
CQ
a
w H
M
§
c8 fe H
ON£3 Q JH
< S. O
W O H >
M M E~l O
p (D
w
CU
H
cu
^
o
o
CU
K
0>
co
OJ
<
o
-P
^
O
,0
1
t!
1
-^t*
O
«
o
ON ro
t- 0
* *
0 0
O U"\
CO O
o o
^
3- o
0* 0
CO U-N
ON O
0 0
O LfN
LTN O
O* O*
t- vo
CO O
d o
H
H >
H H
CQ CQ
CU CU
H H
CQ
CU
H
f-,
CU CU
03 H
1 P
CU g
-f3 CO
P W
0) --x CU --^
CQ O CO LT\
1 1 O
vo H vo
VO - VO O
£* £^j £ -
HI' CM 0
OH o "3
H PH H t-^
0^
CO
o
VD
t-
o
_^J-
H
H
H
CO
d
CO
ON
d
OJ
CO
d
CO
t
d
t>
CO
0>
O ^-i
ON O
CQ
O 1
% VO
vo
^4 "v*v^-
0) r^
r* '%'^^.
^ 9
o
OJ
H
-i.
"H
H
CO
H
H
on
OJ
*
H
O\
H
LTN
H
H
VO
q
H
CM
H
O
CM
H
OJ
OJ
H
^^
H
*
: !
*^s
?-{
0)
£>
^
vo
*
o
H
VO
CO
o
LTN
ON
d
LTN
O
H
VO
t
01
ON
O
CM
vo
H
K
on
o
8
OJ
o
OJ
o
o
H
O
OJ
o
H
1-1
n
cu
H
fc
0!
VO
H'
CM
*
O
^s
o
-------
ON
o"
oj
3
o
q
rH <,
1
g
CO
pi
PH
PH
§
CO
PH EH
M O
£^j ft
f~j
CQ &
<^J
IS **""s
O W rH
CO Ej^
o-j ^5 £
<| |j -sS-
P-j pi
p>| <3^ CO
8 EH
C5 O O
a a 0
H
C-> EH K
JS ^C O
EA-LAKE :
TASSIUM
Averap;
§8
PH >H
^ w
tJ3 jjrj
< M
o pg
pi^
O
8
«3
P^
P=q
CO
o
w
Pk
OJ OJ
CO O
d d
+i +i
?
O ill
H O
H
03
H
O
0)
ro oj
OJ O
d d
+i +i
Hi
w
-P
^j
to
K
^
x"*x <"~x
OJ O
"ON "o"
-* ro
o;
g
JH
H
g
(U
O
-^- LTN
^7 o.
d d
CO MD
ON O
, d d
gj i ^
H s o1
C3| « .
Kl O O
M
H >
H H
CQ CO
aj D
T! ^
CQ
O
H
fa
0) (D
CO i-t
1 P-
flj |
-p a
c3 co
P)
O ^~^ (U -*^*
CO O CO u-N
1 10
VO H VO
VO VO O
t- JH 7^
<-{ V OJ 0
O -H O ro
H K; H H^
^
H
d
+1
ro
H
o
+1
****N
OJ
^ON
^J-
CO
CO
d
__^J-
H
^
1
^O
o
^.^
o
ON
*
o
£H
o
r*
H
P^I
O
+1
ro
d
+i
LT\
O
OJ
OJ
LT\
I
VO
O
CO
0)
H
H
a;
CO
i
VO
VO
HI O
OJ, H
r~i C-C*
f-
o
d
-H
t
O
O
+1
LTN
ro
H
Lf\
vo
O
I
t-
ro
CQ
fl)
H
GO
VO
O
O
LTN
*
O
-.^
0)
ON
OJ
d
+i
t
OJ
*
o
+i
ro
OJ
OJ
o
o
CO
JH
O
H
O
d
-H
o
+1
o
OJ
ro
o
H
CQ
CD
I
vo
tH
H
OJ
O
m
-p
CJ
03
-P
H
3
ca
0)
I
-------
55
w
1
i
-,H . 5
W/ >-M "1
^ b ° £
1-1 M M
« o co
H
E-< S 0 c!
|1|
M CO fi
1 O
CO M
1 B
o g
-p 9
CJ CO
ft
t t t U^, LT\ L'N
O O O O O O
O 0 O O O 0
.* ^t ^f- j- m.^- CM oj oj
ooo ooo ooo
000 000 000
LT\ U*\ LP\ LT\ "j" LT\ VO lf\ LT\
ooo ooo ooo
ooo ooo ooo
Lr\ir\LT\ ir\ u\\j~\ tr\u-\ir\
OOO OOO OOO
ooo ooo ooo
ir\_rt- LT\ _y- + .-+ ir\ ir\ UA
OOO OOO OOO
ooo ooo ooo
-3-_3--^- LTN-rf-LTN _=*-ir\Lf\
ooo ooo ooo
ooo 0*00 dod
M
^
. w
o
H
JH
CO
1
t^~
*o
^^-^- r-p\
CO O
>fc*v-^- *
c^SJO
* ^
*^f" d" -^J" r-f C\ ^^O
ooo H o o
ooo ooo
ooo ooo
000 000
LT\ LT\ LT\ H H H
ooo ooo
ooo ooo
-4. S- .3. -- ^J- ^J.
ooo ooo
ooo ooo
ro ro ro -d- --t -*
ooo ooo
ooo ooo
Lf\ U~\ UT\ LT\ U~\ -+
ooo ooo
ooo ooo
0)
fa
H
bOU
E
rH
CJ S"
"^K LTN
CM
LT\
o o
O"^t-~
CM CM OJ
ooo
ooo
Lf\ LTN-^*
ooo
000
__j. ^, ln>
ooo
ooo
+ * ir\
boo
ooo
LT\.;+ ~r
ooo
ooo
-P
o
0)
03
I
-------
1
1
g
)N SAMPLES
)UT POTASS
CO K
p.. , J
oPt:
0 H E
O W -P
W H o ri
3 W P
E-« S O o
2 9 To
1 O
«J CO
gl
o H
s
K
CO
s
H
03
o
Moratory
rt
w
-&
H
H
1
CO CO CO VO C7\ l/N H OACO
HHrH HHrH CUHH
ooo ooo ooo
H-=J-cn CO H H OJOJH t LT\_^-
HHH OHH HHH HHH
OOO OOO OOO OOO
LT\ -3" LPv ON OA CO CO OJ OJ rH O UA
HHH HHH HHH OJOJH
OOO OOO OOO OOO
oj oj CM m oj cvj t en-* t~-co t~-
HHH HHH HHH HHH
odd ood dod odd
HHOJ OJcntrx HHH tOON
OOO OOO OOO OOO
t1 VD V3 VD VD VO VO t t*-- LT\^D iTv
HHH HHH HHH CMOJOJ
OOO OOO OOO OOO
o
CM
d
* *
^ CO O\
H O O
ooo
H tnco
OJ OJ H
OOO
t CO CO
HHH
OOO
t- t- o
H H OJ
OOO
OJ OJ OJ
ooo
C7\ H H
O OJ OJ
000
CO O-NCO
HHH
OOO
CO ON O\
HHH
OOO
VO t~-VD
HHH
OOO
OJ OJ OJ
ooo
a
o
H
5-f
O
CO
P C3
rt 02
O
H
(1)
CO
CO
H
CO
4)
P
ed
P,
-------
57
CO CO
w eg
i "| «£
g O
^ Pi
CO
p5 B
o o
CO K
H ei
-q £3 »"-
O j | J
^T pr} "^^Si
C5 (-^ t~r
C^ H r-
o c=;O
o « q
H < M r;
O K -P
SS^^
CQ O CO
< H ^ H
EH S 0 r;
^ < t:
S CO "S
I O
P^
±.
E
o
-p
c3
Jn
0
1
H
§
H
>
H
C
H
*
OJ -3" H CO CO H LT\ H C
H O -d- t/\ ro CN CT\ C O
HHH HHO O H H
*
t oo OJ VO _-i- en O O c ";
H V~O PO H 04 O H OJ r-
H H H HHH H H r ;
H VD VD O O C> O C,' C-
O O H O O H r i H -
HHH HHH H .-'
VO O
H OJ
_-t vo \o
LTN LT\ LT\
-I H
O CD
OJ OJ
CO ^
o\d
H CM 04
CQ
CO
0
H
O 0)
CO H
1 P-
p 3
ri co
ft
0>
^
OJ
CO
1
vo
CO
ro
-P
CJ
0>
o
-------
o
03
-p
r->.
3
w
o
K
&
o
p
5!
fn
o
§
1^
iH
rt
w
s
d
H
K*
H
r~"<
fi
-3-_=f -* 1A U-NVQ
O O 0 O O 0
odd odd
vovava t t ir\ t t co
ooo ooo ooo
ooo ooo ooo
*
LTN LT\ LT\ ON ON H VO VO VD
OOO O O H OOO
ooo ooo ooo
LO.VO VQ IT\ LT\ LT\ VO t VD
ooo ooo ooo
ooo ooo ooo
-d-VOVD VO U-\ t VOVOVQ
ooo ooo ooo
ooo ooo ooo
vovovo UA^VO rococo
ooo ooo ooo
ooo ooo ooo
CO O\cp
ooo
ooo
*
O\ H LrN
0 H H
ooo
t- t co
000
ooo
t- t- _
o o
o o
t t- r-~
000
ooo
ta
O
O 0)
-a
a
K
0)
3
0)
AJ
u
CO
-------
59
I
H
^
CO CO K
H CO CO
t] g -H
IS 2
CO O
EH o
f? £> CD
O O PH
!>-, &
n. , : O
W? £q ^^ [ »
o p t' O
o « o .9
H < H c: d
O X -p i^i
H H 0 ri
pa O co d
P--1 ^-^ t *rn
C t t OJ H LT\HLf\
HOO OOO O0\0\ ONOCX3
OOO OOO HOO OHO
H
H
!>
03
CD
H
'o' ^
. CO
H ^
~*~^ VO
t, ^^-^.
CU H
£> rH
H ~^-
CJ H-4- o~>
OOO O
*
OOO O
CJ O H H CJ OJ CM en
OOO OOO OO
OOO OOO OO
-
H H H H H CM H H
OOO OOO OO
OOO OOO OO
OJ CJ CM CJ O O H H
OOO OOO OO
OOO OOO OO
CJ
o
o
CO
|^J s
$
-------
10
3
(D
K
Si
0
-P
0
jqj
rH
03
§
H
H
W
O
H
O O
en rH
° ^
rt en
oo co co
o o o
o o o
CM OJ CM
000
o o o
OJ OJ CM
O O O
o o o
OO CO CO
0 O O
000
OJ H O
o o o
o o o
oo O
0 H
d d i
oo oo J-
000
o o o
OJ CM CO
o o o
o o o
H
05
4)
CO
1
VD
VD
ro co
ITN LTN LTN
o o o
o o o
VD LTNVD
o o o
o o o
'o'a o
o o o
IT\ LTN LTN
o o o
o o o
LTN LT\ LTN
o o o
o o o
*«
O O I
b'b o
o o o
t- 1- 1-
O 0 O
o o o
VD
o
*
0
OJ OJ -3-
o o o
* *
o o o
oo oo oo
o o o
* »
o o o
I
d i i
d d i
co ir\ ir\
O O O
*
o o o
I U"\ LTN
000
odd
OJ OOCM
O O O
odd
co co r o
o o o
odd
oo-d- oo
o o o
odd
LT\ LTN LTNVO
O O 0 O
o o o o
oo oo
o o
d d i
OJ CO OO
o o o
o o o
vo oo co
o o o
odd
|
d i i
o o
d d i
LT\ LTN LT\
O O O
odd
CM CM OJ
000
*
000
CM CM ^J
O O O
odd
OO CO CO
o o o
* *
000
O 0 O .
odd
OO CO OO CO
o o o o
o o o o
vo VD
o o
d d i
oo-d- oo
o o o
VO VO CO
O O 0
*
o o o
ON O. CO
0 0 O
*
000
0
CO
d i i
*
O O J
CM H H
O O O
* *
o o o
*
o o o
VD VO t
o o o
odd
VD VD VD
O O 0
*
000
0NO O
O H H
odd
VD vo VD VD
O O 0 O
o o o o
U"N ITS LPv
000
*>
o o o
3<8£
60
o o o
H
H
CQ
O
O
en
vo
vo
VO'
C\JO
000
000
vo
o
d
0)
en
a)
-P
o
0
^3
0)
03
3
-------
61
§00 H
.* l__I K,- /-?
n%
-p
3
W
O
PH
^
r^
Ck
-p
d
o
9
>5
^
rt
-5
H
C
H
ra
o
H
O a)
r^i 5
o^|«
ir\ H iH
CO ON OA
«
OJ CM CJ
CO O OJ
OJ OJ ro
ro ro ro
O
CO
OJ 1
-3- CT\ ON
CU O OJ
* «
OJ OJ C.<
OJ t UA
o o o
»
OJ OJ OJ
OJ 0 0
a\ o\ t
CM CM CM
O O O
VO LT\VO
ro ro ro
80 o O
O\CO CO
rooj oj OJ
* *
O 0
vo vo
H H 1
O O O
UAVQ CM
» *
OJ OJ CM
O
*
H
^*
s
*->H
H
CO
JH
Qj
"T-!
K
o
OA
OJ
H
m
H
0)
i
vo
vo
t-
OJ
o
H
OJ OJ CM
O O 0
O O 0
H
O
O f 1
-4-
"£>
O 1 I
S3
* *
O O t
ro ro
O q
O O i
rocj
0 0
* t
0 0 I
H OJ
O O
o d i
H r-l <-!
O O O
o o o
ro ro
O O
*
O O 1
ro
O
*
O
CM CM OJ
O O O
O O O
0
H
O 1 l
0
CM
d i i
OJ O
o o
*
O O 1
ro-3-
q q
o d i
-^-3-
o o
*
0 0 1
OJ
o
d i i
H OJ r-i
000
o o o
ro ro
O O
* *
O O 1
o
£*
ci
jjj
H
0 f
o
H
d i
t-vo
o o
*
o o
CO CO
o o
d d
CO CO
o o
o o
C-VO
o o
d d
CO £--
O O
o o
ON ON
O O
*
0 0
g
^\
H
ft
CO
V
1^
qj
f-5
r
i
t
i
i
t
vr>
o
o
1
8
-p
o
Q)
K
03
13
-------
O
H
CO
g
W
-P
w
K
O
o
H
s
-s
H
c
H
Date-Series
Sample
CM CM O\
CO CO CM
.H H rH
LT\
t
H 1 1
*
O 1 1
LT\ CO
CO CO
rH H 1
OJ VO CM
t LTN LO,
r-l H
O-T COCM
H H rH
CO CXI LTN
(~H r~i ri
H
CD
H
f .
10/27 /"66-Sei
River
ro co CM
C7N O*, O.
H H r-i
0
LT\
CM 1 1
O
CO
CM 1 1
ir\ o
CO CO
r-i H 1
CM CM VO
CJ\ IS- ir\
CM CM CM
V5 VQ CM
c; CM oj
0 O
°i °i
CM CM 1
o o o
O CM CO
CM CM H
ON O I-TN
ON CA N-
H i-l r-i
-3- -3- ON
ON O\co
H H H
H O CM
ON ON CN
r-i i--: r-i
H VO H
CO t CO
H H .H
VO O\ O
H O H
CM CM CM
H
Pi
CO
J-i
CJ
H
62
-------
1
1
CO P
3 CO
a S
00 S
feu
0 0
CO 3
H o
vo 1 " H
'c; 1 o ' N_X
i i a O O
-^ N ' * ^
^*^~1 *~ >
HM «
t-CJ LTN
-3" H f-
O CJ O
f-
* *
VO VD CO O -^- O
VO LTN t O CO C\l
OOO H O i-l
OOO _-j-_rj-_^- O\ O LTN
U-\VOO OOO COtTNC
OOO OOO OOO
* *
OOO ^t ~^T \f\ -4- IT\\O J- C\ t
OJ LT\V£) OOO OOO LOLTN'O
HHO OOO OOO OOO
OOO VQVOC UAl/NL^ COt LTN
rOL^LTN OOO OOO VOVOVO
OOO OOO OOO OOO
>
1-1
CQ
OJ
H
-------
Oj
a
o
H
EH
0
Q
W
1
CQ M
1-3 CO
S? W
<-4 P .
CO
O i-H
CO CO
III
K O p
O PH ft
H q
i-1-* K -i r~i
O W oj
S ° -H
DO t>:
W D -H
M O S-l
g g O
is
H ^
S o
-.
o
p
o
i i
-d
r§
TH
r-i
c
H
O O 0
L^ LTN LTN
H r-l H
C7N O
LTv LT\
H H 1
CXI -=? ^
V£) 'vD O
H H H
CTNMD CO
IT\ LT\ LT\
H r-l H
OJ -=} -* OJ co co r^; rovo
OO OO O<5 VOVOLT\
OOI OOI OOI H H r--l
OOPO ooro coco oororo
OO OO OO VD^OO
OOl OOI OOI H H H
O O u>
O H H
OJ OJ OJ
LTN LT\
LT\ t^
CM OJ 1
-=}- OJ O
-=f -3- -3~
OJ OJ CM
\O OJ t-
m ro ro
OJ OJ CM
^
VD O\ L^
OJ OJ OJ
CM OJ OJ
-d- -d- ij^s
OJ OJ OJ
E-f
PH
CO
s
PH
CQ
-------
H
Hi
o
la
H
^"^ OJCOVD OLT\O
00 cot t C7\ OJ LT\
OOO
O
OO
H rH CXI
CCCOCD
00 OOO
oovo OA
vo vo vo
* *
OOO
C- VD 0\
t- t~-t
*
OOO
K
H
05
0)
Ti
CQ
(U
H
h
O 0)
CO rH
I P-
v £5
+5 cd
^CO
fn
0
CO
VO
Vo
N
u?J
o
H
X~N
U^
o
o
Jrf
5
«
-p
o
4)
«
CJ
I
-------
1
PH
CO
<£
EH
£3 8
£ 8
CO "* '
w
JSi EH
O i ri
co fe; 4^
H K O o;
< ^ o
WOM
1-3 M E-I H
<; O <5 C
EH H £-:.
3 -H"
2 co o
i 1
1 ^
PQ
H co
S§
H L-'
°l
1
w
EH
P4
CO
0
-M
ffi
w
p
CO
K
fc
O
-P
03
^
0
^>
03
-!
H
c3
S
*i~i
rl
H«<
X)
C
H
to
O
H
fn
C! O
CO 1-1
1 P
-r^ W
C3 CO
0
-^OJH CVJ IT\ OJ UAOO
VOVOVO VQVOVO VOOrH
OOO OOO O.HH
VO-3-H H CO OJ t-COCO
OAOO OHO C\COCO
OHH HHH OOO
,
U"\ OJ CO t-- --t CO CO OJ CO
ON t~- 1- t~- t-vo t vj o
OOO OOO HrHOJ
O t L'N OJ CT\-i- CO H CO
CO C^ C CO t- t CO CO CO
OOO OOO OOO
H
M
H
w
-~~- >
O -H
H <&
ir\ u-\u~\ co Oj O vo
O CN ON co i-'N -d- -=i-
H 0 0 O HHH
CQVOCO COH-cf OJOfO
VO C t t-VOVD £~-OON
OOO OOO HOJH
^
OJ CM VO OOO -* CO CO
CN LT\ CO LT\ C\ H CO H H
HHH O O H HHH
ON H ro H oj oj r co t
f CO CO CO CO CO U~\ LT\ VO
OOO OOO HHH
H
"""-v^
to
g
O
H
TlS
-------
1
CM
H
CO
to
*3«
EH
M S
rd O
CO
£^ £"1
O -< cj
oo ^ pq -P
<£ *? p|
w o Pi
§ O §* p
EH H -H
'""' 5 -H
PH 1 I ?H
i^ CO O
j °3
i EH
IS
B P
S f3
Ss
O *H
r~n C^
-------
w
-p
rH
CQ
0
PH
h
o
-p
c3
O
c5
3
r-l
cc!
H
^>
H
rj~^
a
H
CO
H
O 0)
CO rH
n> S
P CO
Cw CO
Pi
ro co co
O O O
odd
H
O
O I 1
o
O » I
O CO -3- -=t
o o o o
« * * »
O O 1 O O 1
ro ro -d~ -=r
O 0 O 0
*
o o i o o e
co ro u~\ ir\
O O 0 O
* »
O O 1 O O 1
CM CM CM VO VO
O O O O O
O O O O O 1
ro ro ro ro
O O O O
O O O Oil
.=! -3- ro ro ro
O O O O O
O O 1 O O O
H
w
OJ-
H
. LTN
0 0
« *
O O 1
_d- co co
o o o
o o o
o "o o
o o o
LT\ LO.
O 0
O 0 1
0
^v^
c?
M
O\CO CN
o o o
o o o
VO ir\vo
q o o
d o d
vo o
q H
O rH 1
VO LTN
O O
* *
O O 1
co CO'
c3 o
O O 1
IT\ LTN O O
O O H H
* * *
O O 1 O O 1
-3- ITS CO CO CO
o o o o o
O O 1 O O O
LTN LT\ CT\ O O
O O O H H
oat o o o
ro t CT\ H H
O 0 O H H
O O O O O 1
^.
o
o
"
g
^
H
CO
a>
V)
c5
h-H
cr\ a\
o o
*
O O i
o o
H H
O O I
O rH
rH H
O O 1
83
O O 1
tt)
H->
O
03
*
-------
^
*
1
PH
§
CO
£Q
"^
E~f
$8
M
1 1
CO
^ EH
O
0)
rH
d)
00
i
vo
vo
^^
i>- rH
cj 5;
O H
rH (2
'OACO OJ
^- L,-\H
H rH OJ
-* CO O
H iH iH
cr\ ro ro
-^ ro j-
rH H rH
O CO VO
OJ OJ C\
OJ OJ rH
OJ LPv L-\
OJ lf\ t~
OJ H H
O O LT\
OJ r-f O
OJ OJ OJ
-d- ir\ O
ONO 0
rH OJ OJ
U~\ rH OO
-i- ro ro
H H H
O O t
_d- LPi-^-
OJ OJ OJ
O O CO
CO CO -=1-
CJ OJ OJ
CJ O OJ
U^ LTN LTv
CJ OJ OJ
O 0 O
OJ _3--3-
OJ OJ CJ
0 O O
o -^--=t-
OJ OJ OJ
rH CJ CO
ro ro oo
OJ OJ OJ
-=*- co OJ
ro ro-cf
CJ OJ OJ
CO VO OJ
ro ro-cj-
OJ OJ OJ
-3- -=f O
ro ro ro
OJ OJ OJ
^ s,
o
d
rC!
0>
rM
H
P^
CO
i-H
o
^>
s
OJ ON OJ
ro OJ oo
oj eg OJ
OJ O O
CJ CJ OJ
H rH O
ro ro iH
OJ OJ CJ
rooi ro
OJ 0 OJ
OJ OJ OJ
VO CO CO
0,00 CO
OJ CJ OJ
000
^ ir\\0
OJ OJ OJ
O O LT\
CO CO t
OJ OJ OJ
CO CO "3\
OJ OJ OJ
0
ro
OJ 1 1
£*
10
0)
H
a)
1
VO
VO
H
OJ.
oo oo ro
o q q
odd
oo oo oo
o o o
o o o
ro ro ro
O 0 0
O O 0
oo ro-3-
o o o
O O 0
-3- oo ro
o o o
o o o
OO-4- 00
000
o o o
ro ro ro
o o o
o o o
-3- -=f -^f
o o o
o o o
o "6 "6
O 0 O
oo
o
*
o
0 O O
o o o
ro oo oo
O O 0
0 O O
-3- oo oo
o o o
O O 0
L"\ ~^~ LT\
o "6 o
0 O O
_4- irx LT\
O 0 0
o o o
IT\ LT\ LT\
O O 0
o o o
vo vo vo
o o o
o o o
00 OJ 00
O O 0
o o o
o
o
o
o;
(X
0}
I
-------
70
r_~)
W
13
I
PH
2
H
CO
^
E3g
i-5 PH
§ S
CO «i
^ P3
0 EH
en <; « *
M K r-!
K EH^.
m
V
H
to
CU
T-l
?H
O O
CO H
1 P
d> £;
-P c3
05 LO
O
!.
d
CO
1
VO
xD
H
CM
I i
k
o
>
3
cf
o
Pi
CO
(U
Ti
0)
CO
I
VD
VO
a
o
-p
o
0)
K
(S
s
-------
71
pr"]
t!
1
£>
H
CO
CO
<£
EH
K S
1-3
Q. £^
§ y
w
^H *~H
O <
00 0-' - <
H EH H
t, cs\
i j
|rao
jjll
g S
" w
H to
^ o
c3
r^
H
W
0)
H
0) (Li
03 r-i
'. B
j..]i f-?
n o:!
t ro-^-
VO VO VO
o o o
VO VO VO
*
o o o
t CA O\
I>- t t-
O* O 0
(**~\ r*~*, r~O
x xf W
*
o o o
u^-4- 01
VO VO VO
«
O O 0
OJ O -3-
VO VO VO
o o o
OJ OJ O
VO VO VO
o o o
*
J* 0
O O I
SLOT'S.
t t L~-
o o o
ID
H
a
CO
I
VO
*-^o
~^^
o
0" (D
~^v^_ J|y^
CXJ c5
H J
J- -4- -t-
rH r-l r-l
r-i i i i {
a\ o LT\
r-i OJ OJ
* *
r-l rH H
ro 01 ro
OJ OJ OJ
rH H H
CO CO CO
1 It { 1 i
rH H r-i
VO VO t
rH rH H
H H H
t t-CO
r-i H H
*
H H H
OJ -3- ro ro r-i ro
t t t>- OJ OJ CXJ
O 0 O r-i H H
O O CA VD C\ H
VO VO u~\ OJ OJ OO
o o o rH r-: r-i
OJ O O CO u-\CO
VO VO VO OJ OJ CU
O O O rH r-' H
t3
o
^J
iH
U3
0
J^
i3
OJ rovo
LTNVO U~\
H H rH
ON O ON
OHO
roco ro
UA LT\VO
H H rH
OJ VO ^t
t- O- >-
H H H
CO C
H ro
H H I
ro^J-
OJ OJ
*
H H t
t-O C\ t- OJ t-
H OJ H CO tCO
H H H H r-i H
ro r-l rH OJ VO VO
OJ OJ OJ CO t t
r-i H rH H r-f H
O. t ro oj cr\ c\
H H OJ L^ ,^- _^-
H r-t H r-{ r! H
£_l
-------
w
1
1
p [
g
H
CO
^n
H rj
ro ^_ fe -p
SSpH
PQ JirJ ^3 c3
<| o <; c
^ ti .-. T1.
" S -H
W CO O
< CO
KH <3
<£ C^
2 £H
P5
EH
S t§
P O
t3 M
a|
s
w
E-i
CO
Q
txl
fit
w
+i
tfl
o
ir
o
""ri
SH
o
rQ
A
r-j
CJ
^)
ti
H
C
H
W
0
H
JH
0! C.I
OO r^
1 P.
0 g
4^ 3
ri oo
-3- co t
ro OJ H
OJ OJ CM
* * *
CO VO OJ
^t- LTN LT\
H H H
OJ VO VO
_J- LT\ LT\
OJ CM OJ
CO CO VO^
OJ OJ OJ
_"t CO VO
ooo
OJ OJ OJ
CO O
G"i CT\
H H 1
CO VO CO C7NVO CO
ITN^f- ITS OJ OJ rr-j
OJ OJ OJ OJ OJ CM
ro no 00 ro o O
CO CO CO H OJ OJ
OJ OJ OJ OJ OJ OJ
o co o CAVO O
ro OJ ro o H OJ
OJ OJ CM OJ OJ CJ
H
H H
to
o ta
H 0
H
CVJ" ,-! \
H K -d-
\O tcc: O C~> rri o^ c\
O C Ci .H O O O O
ooo ooooo
_^
ooo ooooo
ooo ooooo
*
OJ LP> lf\ \O OJ O\ CT\CQ
OOO 0 H O O O
ooo ooooo
*J. i-i
T- T-
ro ro ri -5- t ir\ co vo
H r-i <-l H H rH r- S H
OOO OOOOO
LT\VO VO t CO t^- CO CO
ooo ooooo
ooo ooooo
t ^vo c\ c~-\ c\ r-i o
O C O O O O H H
ooo ooooo
t t- VQ CO CO CO C\ t-
o c o ooooo
ooo ooooo
CD CO CO O. C\ O C\ O\
OOO OOHOO
ooo ooooo
t t~- co co cr> cr> c i co
OOO OOOC3O
ooo ooooo
C\ C\ CT\ r-! r~[ H H H
OOO r-i r-! r~I r-j i-I
ooo ooooo
t3
0
p^i
H
cL
LO
o p
C^ CJ
c\ ^ a o\
O
-------
73
w
1!
Pn
«_i
a
H
CO
EH
|S
^ P
<* t- LT\
OOO
CM rH t
C^ O\CO
OOO
t V? CM
!>- t ON
OOO
H
n
H
w
V
H
H
ra
O t3
H O
O * o
C3 ' *~v O
I ' '^. - *
s? ^* ^y"
~\>* -J"
t- " (S
CV O -p
'~^^, ^ C^
o 15 f3
-------
w
s
5
H
CO
CO.
EH
Kq PH
M
& i
CO
£5 £~f
co S -^>
1 1 P [
K S "^
<^i *^ E;T
H O W G}
CO ^_ H -P
1-1 § § .S
MOM
a g EH r-j
P T-
§ CO O
3
I EH
1 ^
FP
H &3
P O
0 <|
a
0
w
EH
02
0
PX,
ffi
CJ
H
f-I
>
o
o
-f:
^
^~
o
-P
c3
o
^
H
g
H
s
"CJ
C
03 1
0.'
H I
?H '
0) C *
CO rV
(U ^:-
-P sf
«J CO
R
CO CO OJ O ro H
O\CO C\ OACO t~-
o o o coo
ir\LT\MD O OJ J- C\ O O
O\cOt VOG>CC- VO&OO
OOO OOO OOH
* *
OJLT\O -^--d-O OOCO
-3-cocr\ cocSvo t t^-H
HOO OOO OOO
U"\CXIO VOO'vO VDt--tr\
COOACA ONOJH t t CO
OOO O H H OOO
HCMCO OOO OOO
CX) CO CO u^O\ON COOOD
OOO OOO OHO
OJ H H O-3-CO 'vO-^J-O
CT\ t E^- COt>-^ tCOcO
OOO OOO OOO
s>
H
'.J CO
r! «J
;-' i ' " n-t
O- J-(
: CA a
t fj
0 i
' "*' S VO
1 * ^
sD , i
> *-^
-- -H |OJ
~'f CH H
OAOJCO O-=fCO C7NOCXI
HHOJ OJOO H OJ OJ
HHH HHH HHH
00 OA Ovl OJ -* 1A VO O O
CO O r-i CO H OJ _j- OJ r-!
HHH HHH HHH
* *
Hco-d- cr\ojoj t vo ir\
O O 00 O\ H LT\ OOVO CO
HHO OHH HHO
LPv LTN O O LfN^t J- CO H
OHH OJHH OJHOJ
HHH HHH HHH
OJ -3- -3- OO H CJ OOO
HOOJ HOO OOO
HHH HHH H H H
* *i
HOJH OJo~iC>. UAVOoo
HHH HHO H H H
. ->»
H
H
^_S
^
(i)
j>
J
K
fj
o
-P
u
o
--3
o
-------
-4- CMH
o oo
O 00
75
o o o
* * *
o oo
1
1
r§
rH
CQ
EH
gs
P-I ft
CO _,
w
K EH
o ! Cl
CO « -P
-"§ £2 «
"-^ ,ci| f -
S H EH <"
5 S
C
CJ
c
^
o
-p
cC
c
iS
H
cC
r^
>d
r
C
Ln
c5
.r-j
v
oo O X) oj c.;
1 jA CO ""3
VO O 1 O
VO O > ' t K
~^~~. ' VO
O fn "^~~ Cj
< ' <3J 4J n' CJ -p
"^M ^ <^ -^ &
?- J K ^l^ v"
-------
?/:, / /
-------
-------
78
0
tr
=
o"
Cw
o
If)
o
' '
c.
1
^
(_:
c;
cr
'-
c-
!
3.:
-,
,!
t
i
i
£|
<*
| :
1
i
1
i
-
,
L__
- -
- "-
~-~ ' -^
t .-
-
--
r - ' ~ "
i
i
r ,
_ . -
"
r " r '
i
-
---
~ : -
_
!
i
!
1
- - t
. .- L
1
1
j
«:
j
' <~~\ '
}
l
1
1
|
;
i
__ j
' , "
-'-,--
' \
. -^
_ !- -
.-.-'. _..
_: .: - -
- r - -
- - - - V
- - ; - ;
:.:
-
- ----- i
i
1
; |
: |
. ,
t
- -
- _.
-
-- -
1
\
\
,
U _
-
-
" " "
-"'-,
'-"
-'- !
\
I
i
i
- -
- j
I
r
i
s
|
,
\
\ ',
-,
,,
,
L ' -
i \
" " " V
\
1
"
~
--'
.
-- - :
_ - _ -
- --
\
.' .
- - - - - -
..
i" ^c
- ^--
i
1
i
i
i
T ! -71 _ '
1
I
1
V" i : ~
S l
" A
\
- - _
_ -_ " i -
--;--- -
'-'.'-
- -~~~ -
- - - - - -
-T -' --
- - -
-- ;
~ ~~. ".".
-- .
. _ :. - -
1
-
- " "_"_" .- .._
- --
r
~
- .
i
;
-^*.
<
11 " "-
'
1
"-":
;\
- -
- -
. _ -
- - -
1 :
--«.
"
._.
-- -
Y
\ v.
--\
/-
<.
- -
- - -
_..
i
-
--
7 - -
:'-
\~
- - - -
i
-
...
: - '- '
-
-
\
:
\ -
- N
_
- ;
l_
r~
C
1 i i '
I
!
,- ._ .
i '
1
_. _ _ .-! _.
1
i ,
. __,
i
- - _
- _ _ ! __ - _
- - , -
- -
!
' 1
" ". J ! '. --"-"
-;:-.. r
\
S
\
\
-:^._-.--
V
' \
\
...--: -: : ;
_ .. - .
r r
-- - Vi
i rS,
|
- _ -
;
1 , .
\
\
C
c
H
r; r- ^ V
h ^ «J
__ 3 .H i
p-f ^ r
c
- ^oc
< -H C
E,d g
W £i ?.
- -s-: d -p
5 ? J
r; SP;^
-
1
.
"
--.
\ --; - .
.-: -\r .-_
_ \
C \
- _ , _ . .
1
i 1 ' ' '
^J
vc
rf G^
~ H
«J »N
^ CO
"j ~°
^' O
H 03
-i O
- 5s
, j
I
t ^
o
,
s
o
ci
-P
1-"
1
~
^
^
-
c
=
-
ri
Nb
-------
,A
\:^r:^n^}-:-
! -__
- -_L-
r
-K"
o L .
't-
79
V£)
O
H
;s (=> _j
Cj ^ ! I ^
C -H c->
rH w o ;-
& a w ^
< o -P
CO -P p
fj
t-:t:i--ri-
_r_
:i::
8 o j--> s~
M -p -r-i d
S « +i ?-!
O O c' cO
O ,£! M ~J
H, p~' i3 S
H o d
E-f -; c; - i
o
O
>
1
(- -
r: v -1.
* - \ I
l-
^L
4-Y--
..V
_" _' \
" : ' \-
"-"-- t
r
j O
-------
80
0
in
r-t
0
(N
O
If}
O
*~ '
_
r-
O
0
c:
c
^_
c
cc
"1
i
cc
o-f
cr-
1
ci
1 ' ' \
~~ " "f r" >^ [
j
- _ _ T - -
_ . , I - - - - - - -i
1 i
' ! !
I ' '
; 1
| :
.. .. . - . t - - . - - --
! - i
~ '
. t -
' 1 ' r
-i--- -- ' --
|
- - -i- '-
- -! - -
I:':: : ' "
L_ - - -1 - - i
." ~"
- 1
,
!- - - ' -
i
!
" __,..
-r - -
!
i
1
! i
i" 1
1 ! '
l
\
V 1
\ _,
:- YT- ------
- - - - \
\
1 \
" "l""\
-I -- .*
!
. . .. - -
- -
i.
._, - j .
' " '
.
.. -
"""' --
1 -
- - I
; - "I "
: 1
, I
i ' i
i
i
c '-.-:_
r ' ~ ~ .
-
j
i
r ;
... .. , - -
%-
\ ' ' . " '
-.'
'
< v
\
,
...
- _
'
- -" "
, . .
-._.'..
-- -
-
_
-- , ---
I
W
i
!
- -
. _. ,. .___
i j
i
,
- - . i - . -
_____
V
\
\
\
- s
\ \
.^
-_--.- _-
r - .
-
i
.--_
" *
1
XJ
!
i
'
,
i __
i_ - _
r
-- -
\ --
-
_ _ .
7
1 i '
~~~ '
) 1 - . -
. . ..
_ , ,
^
;
/;
"-
:.
- --
i
; '
__ _L :_
_
-----
. .
j
-- -
. ._
\
*c
|
-
-- -
-
"
\ 4
"
v
i
- - !
!
- T-.--
1
-.;._-.
L^
r r
__ -- :- -: _-
1
!
'
. i _.
7 -i
" " '
"-" " : ^-
.
}
; T"
S -
> . ~
-"\
\
' - -
{
X}
1
_ . _ -
i
oT
- p., a" -p 'S- '
- < ^ o B Ln
- CO P-l rC Cj
p
ZZ r-i -H 0
o a ^ x
ci -p rj
H O CJ i-J
- eg E^ ^
-^ .- j 1- ]
=.' 'o O '""i
- ° f?6vo
O O 2 O
fcl 9. y ,
"-H ^ J~, 1
O frl C
- i-i do
a p -f-"1
CO C.
C,J ^> |>w rH
3 ^ ^ r
i o c; s^ t
c" o t: o
?--; >~. >.-i P-i C i
C-. -P -P. ^J
<; -,-: cj &.
3 i-; O O c
o r-i Q A .-
7 -"-"-!
. " ' 7 '- ' '-
i
:.; _ ^-i -
: ; ' -r -. i
'
:
\ !
" \
- \ ;
- -
-
,
^
c
- 1
- : - - - j '-
i i
f ' :"i i
w>
Vi
-------
-------
-------
0
C-,
o
_<
o
es,
0
u-i
c
«-
r-
r-j
O
*""
r-.
C,
O
c.
'
?l
1 . i
i :
- ; --
_.-_
i '
IT -!~7"~
-~~ -
-^
'
t-
- - -^
-
" -.
;
:^;j
i ; i
^
-v
- -
X '
1
\
\
~
1
J
i
1
1
. i
. - . .
I - . .- -
\
" V "
.
1
~"
*"
_
-
/_._;
'.':
- _"- r
*
" '
-
.
_
'
-
. 1
j
i
- :. .-_! . -_..
1
i 1 :
1
\
" ;_1" _ ._
T
\
-'
- " -~d- :
"
"-.
,
;.-
- ;
-
~ "
,
. .
*
-
_
i
.
»
:; -1
: i
j . .
t
-
^
\.
i i
. _ j. . . . . j. . ,.
__ .. ( - .
- - ' : -.(-"---'
| '
|
1
'L I
\ ,
r ; ~ -
t , i ~
"
! . --,-_.
I:... -_-_:.-
^_ _ _ ~_ _ (
N
" ~i
, }
\
: \
' ' !
' i
- _'-._ _. i _
, i
! i
; j --
;-""
__ i
J/ 1%
1 i
i ":
i -
' *
\ \
; j
i ! ' ! ' i!
f"-""] "r^" ---
i " ' .
; - j - -r
1 . . r._ . . t " - - -
t .i1
i
I
1 ' J
i
U I
._ , . .
, . j .
- -- -: '-
\
i [
1 . i t.
r"£:~!::;" ; -. .
"
/- - " '- - '-
'^' i
'V /-
"/ r.i *;'"" -
\,
1 "
. _ _ : _ , _ .- .
;
-i "-' - i
* , - I "" "T
i ! _ . '. __ 1
1 i
; f f
.".:' r :-. ; ."::.
I
1 [ . : vS
. - .
_t " r " a H -^ °
" . " i~ :"" i : " ' o cJ & ^
. 1 ._._.( _. CO -I-' £>
i i ulj O (1^ : J
0 i ' 5r *H S
' " . " " " r " a! vi ^ 2
r i . . . ___ _ . ___ goo ',:
. j... . - . L C'O O
o o s «
- - i_i o o
^ l>^ -p ^
:--." "-:"- .".'"". "" R« P,
- - -- " " - IOC
--- ' ' 5^ . 0 «
p:. >s -r!
- - - , f^ 4^ .p o
~ "- i c,'1^ R /J
:^-- " - - - i; cj ^ VJ
- - - - - ^ cj O C"
' ' ' ~ i_3 O !> f-.
^T^ t, (< ) - ,
; , . -.- ; O^P^
i i - - . -- -
.'"""F:j:-Y!V: i,:-,;'"-:
1 | . J .
"_'_."_". i _ 1 \ " _J .
\c- " - ^ "- !---:"- - -
\
'\ r , j
\ '
' \ i ' <
\ .
-.-.:--: ' \ , '
"\ ; - - -
. _ _ j . \ i. .
1 \
i j \
...__ _ii_.:.t:;:;.ci:
--- "" " - ! - -"
...:..-;:.-. ::::j._.|:.-:_
\c
<*.
3>
CC
^>
'i
i.
a-
*
-
u-
-------
L.T
0
,_,
O
Cs.
O
in
o
'
r-
CO
c:
c>
Cf.
"
"
cc
C'
i
1
i
g
| j * '
1 | , '
" *~
.... ._.
, i
I
-:-_-_
I'M
.
:
:
- -
-" -:-
_
L
__ _
_* .
i
*~* ""
- - ~.
__
1 i
.
- -- -
-
_..
-
"
-
-
1- "--:
"
_
- -
- .. 1
. -_r
__.
-
"0
^v,
-
...
-
i ' J
f
^p
- i ' -
\ i
' \i
;\
. \
- .
I-- \
-- - _ _ i
i
"__ _ ;
- -
1 - -
" _
. - _.
- -
--; Jo
.
".' "~ . ~.
- - ' - r-
' ' , i ! '
~ -, i . ' i
. . _
I
f
-_-;-
t
i
IV"
! \
j
ris
i
i
f -
.1 . .:
,
1
"-- -
i
' -
I
i
i
, .
. . . i
;!! ,'
' - -
\
\v
\
; - "_ \
--
-
..
, -
_ _
.. .:
i
r
\
L
~
-
_ .
. i !
i
t
j
j
j
: - : t.
-- t
. _ i
!
- _._ L
" :'" i
^,w
."
_ i
j
i _
- -
i
-- 1
- --
_ ^.
, , ' t i
. n
| |
1
J, -
i i !
i
I -
j
H.r
'-.
'
I
--
--
i
-
-:
;;
_ __
_.
_-
-
1,
\
\
\
_
: :
i
j
T
I
--- 1
i
: : : i
t
i
---
-
c
"
"'
.
-
^
4
i "
I j
"]'!."'
' ' ^ Si'Q
E~-r^-.- -;- |
- - : r - " tl
" i . " r %
; i CO
i ' | a
. . j... p
H
:-rr: .:|.r_;^: ; - £j
:.- _L_::: :. rz: _-_ 8
i c
" K
: C
V
: ' _ ' . ~_ , '"T
- - r-
:..".:"-£?
-- - - - >
__ _ ;
" "- ^" J
. :
. . - - __ -
Kx V- _ - ., . '
\
\
\:
\
\
"^ <.
\ -
v
\
,
'H'"
- - -
r
',
. ' . '
^
£ !_' L~~"
^ P f i r-I
0> fl ^
p, -P (^
P-* rg XJ
3 - H
P "^~-
o QJ y
&~^ *v-J ^
»_l
Vi ^ 0
O O CA
H
>5fa o
CD 1
> w s
050
0) C -J
P; H c.'
o5 d
-p ^i
CQ ^3
1 ^r"o
>> -H -
; i-i C -p -:-,'
r-l P O
1 T-! ," -j ' -i M
J rb o p 'o
\£^>8
' I ~ '
[
-
-_ .
\
\
" - \ ' .
- - \
!
) -
! i
i
'[
' , ' I i '
«->
i-
cc
D
c-
-
-=r
'
'
^
_
~
C
<'\
-------
-------
-------
|