A STUDY OF NUTRIENT VARIATIONS IN THE SURFACE
AND MIXED LAYER OF MONTEREY BAY
USING AUTOMATIC ANALYSIS TECHNIQUES
Gaylord Oneil Paulson
Library
Naval Postgraduate School
Monterey, California 93940
Monterey, California
T
A
STUDY OF NUTRIENT
VARIATIONS IN
THE
SURFACE
AND
MIXED LAYER OF
MONTEREY
BAY
USING
AUTOMATIC
ANALYSIS TECHNIQUES
i
by
Gay lord
Dneil
Paulson
Thesis Advisor:
N. E
. J.
Boston
September 1972
T 1
Apph.o\j<id ^oK pubLlc. sizZnaA e; dii.tA^u£Lov/unLurU£e.d.
itudy of Nutrient Variations in the Surface
and Mixed Layer of Monterey Bay
Using Automatic Analysis Techniques
by
Gaylord Oneil Paulson
Lieutenant Commander, United States Navy
B.S., University of Utah, 1962
Submitted in partial fulfillment of the
requirements for the degree of
MASTER OF SCIFNCE IN OCEANOGRAPHY
from the
NAVAL POSTGRADUATE SCHOOL
September 1972
Library
Naval Postgraduate School
Monterey, California 93940
ABSTRACT
Concentrations of silicate, phosphate, nitrate, and
nitrite were determined in Monterey Bay, California. Data
were collected aboard ship during four cruises in April and
May 1972 using the Techmcon AutoAnalyzer^ II System in dual
channel operation. The sensitivity, reproducibility, and
accuracy of this system were investigated and the results
presented. Nutrient concentratiors were presented as surface
variations, depth variations, and vertical profiles. The
large variability of nutrient concentrations in the ocean
area studied was discussed. Upwelling areas were investigated
for nutrient concentrations, circulation patterns, and vari-
ations in nutrient ratios. Planktonic bloom areas have been
identified from the low nutrient levels, low nutrient ratio
values, and high chlorophyll correlations. Results indicate
that silicate was the limiting nutrient to biological activity
in the waters studied. Assimilation, ratios for biological
activity were found to be 16.33 for NO -.PO, and 21.14 for
2 3 4
SiO.tPO.. Nutrient plateau regions were analysed and sources
discussed. The major cause of nutrient concentration changes
in the area (except plankton blooms) as determined from
nutrient ratio studies was found to be circulation of the
water masses.
TABLE OF CONTENTS
I. INTRODUCTION 12
II. INSTRUMENTATION 14
A. SAMPLER 14
B. PUMP 14
C. ANALYTICAL CARTRIDGES 16
D. COLORIMETERS 17
E. RECORDER 18
III. ANALYSES 19
A. SILICATE ANALYSIS 19
1. Reagents 19
2. Standards 21
3. Baseline 22
4. Linearity 24
5. Salt Error 24
6. Blanks 28
7. Data Reduction < — « 28
8 . Interference • 32
9. Summary 32
B. ORTHO PHOSPHATE ANALYSIS 35
1. Reagents 35
2. Standards 37
3. Baseline 38
4. Linearity 40
5. Salt Error 40
6. Blanks 41
7. Data Reduction 41
8. Interference 41
9. Summary 43
C. NITRATE-NITRITE ANALYSIS 44
1. Reagents 44
2. Standards 47
3. Baseline ■ 48
4. Linearity 50
5. Salt Error 50
6. Blanks 50
7. Data Reduction 52
8. Interference 52
9. Summary 52
IV. SHIPBOARD OPERATION 55
A. EQUIPMENT PREPARATION 55
B. SAMPLING PROCEDURE 58
C. DIFFICULTIES AND PROBLEMS 59
D. FUTURE IMPROVEMENTS 61
V. CRUISE INFORMATION 63
A. CRUISE ONE 63
B. CRUISE TWO ; 63
C. CRUISE THREE 67
D. CRUISE FOUR 67
VI. RESULTS 75
A. SURFACE DATA 75
1. Cruise One 75
2. Cruise Two 77
3. Cruise Three 77
4. Cruise Four 77
a. Leg One 77
b. Leg Two 82
c. Leg Three 84
d. Leg Four 84
e. Leg Five 84
f. Leg Six 89
B. MIXED LAYER VARIATIONS 91
C. VERTICAL PROFILE VARIATIONS 99
VII. DISCUSSION OF RESULTS 113
A. VARIABILITY AND CONCENTRATION CORRELATIONS — 113
B. UPWELLING SIGNATURES 114
C. NUTRIENT PLATEAU - BLOOM SIGNATURES 115
D. BAY AREA VARIATIONS 117
E. RATIO ANALYSIS 119
1. Area Identification by Surface
Ratios 119
2. Seventy Meter Ratio Stability 122
3. Analysis of Nutrient Ratios of
Concentration Changes Due to
Biological Activity 123
F. TIME VARIATION STUDY 126
VIII. SUMMARY AND CONCLUSIONS 132
APPENDIX A: SAMPLE DATA WORK SHEET 134
APPENDIX B: NUTRIENT CONCENTRATION DATA 135
LIST OF REFERENCES 150
INITIAL DISTRIBUTION LIST 152
FORM DD 1473 154
LIST OF TABLES
I. Sources and Magnitudes of Errors (ygat Si/1)
in the Concentration Range of 0-50 ygat Si/1 34
II. Sources and Magnitude of Errors (ygat P/l)
±1 the Concentration Range of 0-4 ygat P/l 43
III. Sources and Magnitude of Errors (ygat N/1)
in the Concentration Range of 0-25 ygat N/1 53
IV. Cruise Data 1972 64
V. Maximum-Minimum Nutrient Concentrations
Found in the Photic Zone 114
VI. Surface Nutrient Ratios 120
VII. Seventy Meter Depth Nutrient Ratios 124
VIII. Ratios of Nutrient Changes from 70 Meters
Depth to the Surface (Cruise Four) 125
IX . Ratios of Nutrient Changes from 70 Meters
Depth to the Nutrient Minimum (Cruise Four) 127
LIST OF FIGURES
1. Basic AutoAnalyzer II System (Dual Channel) 15
2. Silicate Method Flow Diagram 20
3. Silicate Linearity Check 23
4. Silicate Salt Error (Distilled Water Wash) 26
5. Silicate Salt Error (Sea Water Wash) 27
6. Silicate Salt Error Correction Curve 29
7. Dual Channel Operation Recorder Output 31
8. Ortho Phosphate Method Flow Diagram 36
9. Phosphate Linearity Check 39
10. Phosphate Salt Error Test 42
11. Nitrate-Nitrite Method Flow Diagram 45
12. Nitrate Linearity Check 49
13. Nitrate Salt Error Test 51
14. Shipboard Arrangement of Components 56
15. Shipboard Dual Pen Recorder Operation 57
16. Exploratory Cruise Number One 65
17. Cruise No. 2 Track 28 April 1972 66
18. Cruise No. 3 Track 5 May 1972 68
19. Cruise No. 4 Track Leg One 18-19 May 1972 69
20. Cruise No. 4 Track Leg Two 19 May 1972 70
21. Cruise No. 4 Track Legs Three and Four
19 - 20 May 1972 71
22. Cruise No. 4 Track Legs 5A and 5B
20 - 21 May 1972 72
23. Cruise No. 4 Track Leg Six 21 May 1972 73
24. Nutrient Concentrations Versus Distance
- Cruise #1 76
25. Nutrient Concentrations Versus Distance
- Cruise #2 78
26. Nutrient Concentrations Versus Distance
- Cruise #3 Legs One and Two 79
27. Nutrient Concentrations Versus Distance
- Cruise #3 Legs Three and Four 80
28. Nutrient Concentrations Versus Distance
- Cruise #4 Leg One 81
29. Nutrient Concentrations Versus Distance
- Cruise #4 Leg Two 83
30. Nutrient Concentrations Versus Distance
- Cruise #4 Leg Three 85
31. Nutrient Concentrations Versus Distance
- Cruise #4 Leg Four 86
32. Nutrient Concentrations Versus Distance
- Cruise #4 Leg 5A 87
33. Nutrient Concentrations Versus Distance
- Cruise #4 Leg 5B 88
34. Nutrient Concentrations Versus Distance
- Cruise #4 Leg 6 90
35. Nutrient Concentrations Versus Distance
- Cruise #4 10 Meters Depth 92
36. Nutrient Concentrations Versus Distance
- Cruise #4 20. Meters Depth — 9 3
37. Nutrient Concentrations Versus Distance
- Cruise #4 30 Meters Depth 94
38. Nutrient Concentrations Versus Distance
- Cruise #4 40 Meters Depth 95
39. Nutrient Concentrations Versus Distance
- Cruise #4 50 Meters Depth 96
40. Nutrient Concentrations Versus Distance
- Cruise #4 60 Meters Depth 97
41. Nutrient Concentrations Versus Distance
- Cruise #4 70 Meters Depth : 98
42. Vertical Profile Leg One Station 3 100
43. Vertical Profile Leg Four Station 4 101
44. Vertical Profile Leg Four Station 5 102
45. Vertical Profile Leg Four Station 6 104
46. Vertical Profile Leg 5A Station D-30 105
47. Vertical Profile Leg 5A Station D-25 106
48. Vertical Profile Leg 5A Station D-20 • 107
49. Vertical Profile Leg 5B Station D-15 109
50. Vertical Profile Leg 5B Station D-12.5 110
51. Vertical Profile Leg 5B Station D-10 111
52. Vertical Profile Leg 5B Station D-7 112
53. Vertical Contour Plot of Silicate Isolines
in Upwelling Area Leg 5B 116
54. Bloom/Plateau Boundaries Found During Legs
Three and Four 118
55. Correlation Diagram of the Nitrate/Phosphate
Assimilation Relationship 128
56. Correlation Diagram of the Silicate/Phosphate
Assimilation Relationship 129
57. Surface Nutrient Time Variations 19 May 1972 130
ACKNOWLEDGEMENTS
I wish to thank my advisor, Professor Noel E. Boston,
of the Department of Oceanography, for his assistance and
advise during the preparation of this thesis. I also thank
Professor Eugene D. Traganza, of the Department of Oceano-
graphy, for his assistance and support during the many months
of initial project planning, procurement and preparation of
the necessary equipment. I am also indebted to Professor
Stevens P. Tucker for his very capable assistance before and
during the major effort of data collection on cruise four.
Without his help much of this data probably would not have
been obtained.
I would like to express my special appreciation for the
invaluable help given me by Professor Charles F. Rowell, of
the Department of Physics and Chemistry, during the data
evaluation and laboratory phases of this study. His careful
analysis, critical evaluation, and enthusiastic support was
much appreciated.
Finally, I must express my sincere thanks to my co-worker
LT Robert A. Killion, USN for his tireless assistance during
all the data collection phases. Without his assistance we
would not have been able to effectively collect the necessary
data on a twenty-four hour basis. His help in cruise prepar-
ation and laboratory assistance was greatly appreciated.
10
Technicon Industrial Corporation deserves special
mention. Mr. Robert M. Gasco was quite helpful and always
willing to discuss any equipment difficulties. He authorized
the use of Technicon procedures and drawings in this paper.
11
I. INTRODUCTION
The three major nutrients in sea water (nitrate, phos-
phate, and silicate) have been analysed and studied for many
years [Riley and Skirrow 1965]. Large volumes of data have
been collected of nutrient concentrations from all the
world oceans.
Until recently most observations were obtained from
manual chemical analyses performed in laboratories ashore.
This necessitated a significant sample storage time in tran-
sit during which most investigators attempted to prevent
nutrient changes by freezing the samples. Whether this
practice actually prevents all nutrient changes is still
questionable. Collection has normally been accomplished
using the traditional method of bottle sampling tens of
meters apart in depth and with casts spaced a few (or a few
hundred) miles apart.
Nutrient concentrations in the open oceans have been
found to be quite variable [Riley and Skirrow 1965] . This
variability is caused by both biological and physical
effects. There is a lack of significant data from coastal
regions, but in these waters the nutrient variability is
even greater than found in the open oceans due to complex
circulation patterns and the patchiness of biological
activity [Margalef 1970] . These complex influences tend to
complicate the nutrient variations such that when using
12
traditional sampling techniques correlations have been dif-
ficult to obtain. Sampling procedures were required which
would give better spacial resolution than previously obtained,
Furthermore, the rapidity of nutrient changes are such that
much shorter time lapses between sampling and analysis and
shorter time intervals between samples were desired in order
to produce statistically meaningful results. Hence, ship-
board operations were necessary in order to reduce storage
and handling effects and allow for near real-time determina-
tions to be obtained.
In an attempt to improve the quality and increase the
rapidity of nutrient concentration determinations during
shipboard analysis automatic analysis techniques have been
developed and tested [Brewer and Riley 1965, Grasshoff 1965,
Chan and Riley 1966, Molof et a_l. 1966]. Technicon Instru-
ments Corporation produced an automated analytical system
(called the AutoAnalyzer I (AA-I) system) whereby nutrient
concentrations were colorimetrically determined [Strickland
and Parsons 1968, Atlas et aJL. 1971]. Recently, a second
generation AutoAnalyzer II (AA-II) system has been developed,
This system is significantly different from the AA-I system
and uses improved components and modified procedures.
This study was performed to determine the capabilities of
the AA-II system, test and/or develop analytical procedures
and techniques for shipboard operation, and study the
nutrient variations in the photic zone of the ocean in the
area of Monterey, California.
13
II. INSTRUMENTATION
® ®
A Technicon AutoAnalyzer II system was used to measure
nutrient concentrations. The basic components of the Auto-
®
Analyzer system will be discussed following the physical
arrangement shown in Figure 1.
A. SAMPLER
This sampler has a 40 sample-cup tray capacity and two
wash receptacles. Cups are available in various sizes.
Five ml sample cups were used exclusively during this study.
A sample probe, installed in a movable arm, aspirates the
samples into the analytical system. Between each sample a
segment of wash solution aids in cleaning the system and in
segregating the samples. An interchangeable timing cam is
located in the sampler to control the time allotted for
sampling each cup and for aspirating wash solution between
samples. For dual operation of nutrient analysis, a sampling
rate of 40 samples/hour with a sample-to-w.ash ratio of 4:1
was found satisfactory for all four analysis procedures.
B . PUMP
This peristaltic proportioning pump was used to pump all
reagents, wash, samples, and air into the analytical stream.
It operates at a constant speed driving a roller system
which, when forced against pump tubes, produces a constant
flow through the tubes. The rate of flow is determined by
14
DIGITAL
RECORDER PRINTER COLORIMETERS
PROPORTIONING
PUMP III *
MANIFOLDS
SAMPLER IV *
Figure 1. Basic AutoAnalyzer II System (Dual Channel)
*Note: Type Numbers indicate supplier model designations
Digital
Printer
Recorder
Colorimeter Analytical
Pump
Sampler"
Cartridge
III
IV
Timepac
Reagents
15
the selection of the proper tube diameter. A set of pump
tubes was made up and attached to each analytical cartridge
so that when a cartridge change was desired the replaced
tubes were slipped off and the new set slipped in place.
This worked very well and saved the time necessary to attach
pump tubes to the cartridges for each change. An air bar
is installed on this model which reproducibly allows an air
bubble to enter the analytical stream every two seconds.
This performed satisfactorily during this study. A single-
speed pump was used. A two-speed model is available from
Technicon and would save considerable time during the wash-
ing phases between cartridge changes when operating contin-
uously for an extended period.
C. ANALYTICAL CARTRIDGES
®
The analytical cartridges produced by Technicon were
used for all nutrient analysis performed. Three cartridges
were purchased, one for ORTHO-PHOSPHATE in sea water, one
for REACTIVE SILICATE in sea water, and one for NITRATE-
NITRITE in sea water. In the cartridges the sample, air,
and reagents are properly mixed, the chemical reactions take
place and the reaction color develops. These cartridges were
compact units, highly portable and sufficiently rigid to
withstand transportation and shipboard use without damage.
They are, however, not versatile in that all components for
a particular procedure are permanently mounted in the car-
tridge and would be difficult to modify if a different
procedure was desired. Two cartridges were normally operated
16
at one time in dual channel operation. Silicate and nitrate
or phosphate and nitrite were normally determined together.
This allowed 80 analyses per hour to be performed when the
sampler was operating at 40 samples/hour. After about 80
samples were analysed (2 hours) , the cartridges were changed
and the samples again analysed for the remaining two nutri-
ents. This procedure proved quite satisfactory and an ex-
tended period of sampling sea water every 10 minutes could
be maintained with a minimum delay before sample analysis.
The optimum would obviously be to analyse for all four
nutrients at one time but additional equipment would then
be necessary.
D. COLORIMETERS
Two Technicon AutoAnalyzer II single-channel colori-
meters were used in these continuous flow analytical systems.
®
This model is somewhat different from the older AutoAnalyzer I
colorimeter and uses a longer flowcell (five cm vice 1.0 to
1.5 cm). The flow stream from the analytical cartridge enters
the colorimeter, is debubbled and then colorimetrically
detected at a specified wavelength for the nutrient caused
absorbance changes due to nutrient concentration variations.
This is accomplished by a dual optical system with two
detecting phototubes. This model colorimeter has a log
ratio circuit which converts the logarithmic output signal
to a linear signal proportional to the nutrient concentration.
The standard calibration control allowed the selection of
17
the desired full scale concentration range during the stan-
dardization procedure and was found quite convenient and
reproducible. In addition, the adjustment for zero, 100%
deflection and baseline (reference) were available and
satisfactory. The colorimeters were usually operated with-
out any damping or time averaging circuits used (Normal
Mode) . At low phosphate levels a two second time averaging
mode (Damp 1) was sometimes used if the noise interference
was significant. A voltage stabilizer was supplied with each
colorimeter. Although some difficulties have been attributed
P
to power fluctuations [Atlas et a_l. 1971] no problems
related to power fluctuations were experienced with this
equipment either at sea or in the laboratory.
E. RECORDER
A two-pen BRISTOL RECORDER specified and supplied by
® ®
Technicon Corporation for the AutoAnalyzer was used.
1?
III. ANALYSES
A. SILICATE ANALYSIS
The automated procedure supplied by Technicon , Prelim-
inary Industrial Method No. 186-72W AAII, was followed for
reactive silicate analysis with modifications for dual channel
operation and standardization procedures. This procedure
utilizes ascorbic acid in the reduction of silicomolybdate
in acidic solution to molybdenum blue. Oxalic acid is
introduced in the flow stream to prevent phosphate inter-
ference. The flow diagram for this procedure is shown in
Figure 2. As noted in this diagram, the total volume of
sample, reagents and air in the Autoanalyzer II (AA II)
system is much lower (about 1/3 or less) than in the older
system. This results in smaller components, smaller bore
tubing and ultimately better performance due to less noise
and better mixing conditions. A 5 cm flow cell and 660 nm
interference filters were used for this procedure. The
sampler was operated at 40 samples/hour with a 4:1 sample-
to-wash ratio.
1. Reagents :
AMMONIUM MOLYBDATE: 10 g of reagent-grade ammonium
molybdate were dissolved in 1000 ml. of 0 . IN sulfuric acid.
OXALIC ACID: 50 g of reagent grade oxalic acid were
dissolved in 1000 ml. of double distilled deionized water.
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ASCORBIC ACID: 17.6 g of reagent-grade ascorbic
acid were dissolved in 500 ml. of double distilled deionized
water (DDDW) containing 50 ml. of acetone. This was then
diluted to 1000 ml. and 10 drops of Wetting Agent A (avail-
®
able from Technicon ) were added. This reagent was kept
refrigerated except when in use and mixed fresh for each
cruise.
2 . Standards :
STOCK STANDARD A, 10,000 ygat Si/1: This method of
STRICKLAND and PARSONS [196 8] was doubled and followed, rather
®
than the referenced Technicon procedure, in order to mini-
mize the time required for the standard to be in a glass
volumetric flask during dissolution. 1.9 2 g of fine powder
sodium silicof luoride were dissolved in a plastic beaker,
transferred to a 1000 ml. volumetric flask, and diluted to
the mark with DDDW.
STOCK STANDARD B, 1000 ygat Si/1: 10 ml. of Stock
Standard A were diluted to 100 ml. in a volumetric flask and
stored in a polyethylene bottle.
WORKING STANDARDS:
ml. Stock B ygat Si/1
1.0 10
2.0 20
3.0 30
4.0 40
5.0 50
10.0 100
21
The required volume of Stock Standard B was pipetted into a
100 ml. volumetric flask and diluted to 100 ml. v/ith DDDW.
These standards were prepared fresh at most every 10 hours.
During at sea operations only the 30 ygat Si/1 standard
was used to set and check the equipment calibration as the
calibration curve proved to be linear (Figure 3) . All
reagents and standards were mixed in double distilled water
which was passed through an ion exchange column just prior
to use to minimize silica interference from glass storage
vessels. All reagents and standards were stored in poly-
ethylene bottles to prevent additional silica contamination.
All glassware, sample cups, and storage bottles were
thoroughly washed, rinsed, then rinsed with IN HCl and
finally rinsed three times with DDDW before use.
3 . Baseline
The reagent baseline was adjusted to 0% recorder
reading with all reagents being introduced into the flow
stream and DDDW introduced instead of the sea water sample.
This silicate baseline was normally very constant and showed
little drift after the system was on line for a short time
(about 15 min.). To check the baseline and adjust if
necessary, the sampler was stopped in the wash cycle about
every 15 minutes for 3 minutes. A baseline adjustment was
then made, if necessary, when the recorder reached a steady-
state baseline condition. This minimized the baseline cor-
rection necessary when correcting data.
22
10 20 30 40 50
Silicate Concentration (ygat Si/1)
Figure 3. Silicate Linearity Check.
23
4 . Linearity
The silicate procedure was checked twice for
linearity using DDDW standards mixed to 10, 20, 30, 40 and
50 ygat Si/1. In both runs the results were satisfactory
and reproducible. Figure 3 shows the results of one
linearity test where recorder percentage is plotted versus
standard concentration. Each datum point represents the
average value of two standard samples analysed. These tests
indicate the maximum deviation from linearity of =■ % in the
range of 0-50 ygat Si/1. This range was tested because all
sea water analysed during this study was below 50 ygat Si/1.
For more concentrated sea water further tests will be
necessary.
5. Salt Error
All automated procedures [Strickland and Parsons
®
1968, Atlas et al. 1971, and others] and the Technicon
silicate procedure specify that all standards be mixed with
low nutrient sea water or synthetic sea water because of
the salt effect on the equilibrium of the silicomolybdate
reduction reaction. This procedure was undesirable because
of apparent optical interference found when synthetic sea
water blanks were determined with respect to DDDW baseline
without reagents. This effect was also noted by Atlas et al.
[1971]. Furthermore, synthetic sea water was found to show
significant variation depending on quality of reagents and
age of solution. This was also true of sea water obtained
at different locations and stored for different periods of
24
time. Finally, the stability and reproducibility of stan-
dards prepared in DDDW was found to be excellent. In order
to calibrate with DDDW standards, tests were performed for all
analyses to determine the salt error correction necessary.
Silicate standards were prepared in concentrations
of 10, 20, 30, and 40 ygat Si/1 in sea water obtained from
the area of study (Monterey Bay) . A DDDW standard of 30 ygat
Si/1 was also prepared for use in calibrating the system
before analysing the sea water standards. Three samples of
each standard were used for each run performed. Two test
runs were performed using DDDW as wash water and baseline.
The three sea water standards for each concentration were
averaged, then the average recorder value of the silicate
concentration in sea water only was subtracted. The results
were compared to the DDDW standard calibration curve obtained
from the linearity tests. The resulting curves are plotted
in Figure 4. Two identical salt effect runs were also per-
formed using sea water only for the wash and baseline
[Strickland and Parsons 1968] . The results of the standards
were again averaged but no baseline subtraction was necessary.
The DDDW standard reference point for the comparison curve
was obtained by adding the average recorder percentage value
to the sea water silicate value obtained with DDDW baseline.
The result of one run is plotted in Figure 5. Both plots
gave nearly identical results, as expected, and a near
linear salt error of 10% for 100% of tested range is indi-
cated. The combined results were then converted to
25
100
90
80
70
DISTILLED J/*
WATER
/
//^SEA WATER
/ o STANDARDS
J_
I
J_
10 20 30 40 50
Silicate Concentration (ygat Si/L)
Figure 4. Silicate Salt Error (Distilled. Water Wash)
26
100
90
80 -
70
g.60
rd
•p
C
<D
u
5-1
(D
ft 50
0)
•a
o
dJ 40
ft
30
20
10 -
DISTILLED J^
WATER
SEA WATER
STANDARDS
10 20 30 40
Silicate Concentration (ygat Si/L)
Figure 5. Silicate Salt Frror (Sea Water Wash).
27
concentration values (multiplied by the factor; DDDW Standard
... - 100% Recorder Reading, m, ..,,
Concentration for — — 2-) . The differences
between the concentration values obtained in sea water stan-
dards from those obtained in DDDW was then plotted as a
concentration correction versus the DDDW standard concen-
trations in Figure 6. This linear correction curve obtained
was used to correct all silicate values obtained using DDDW
standards. The maximum error in this procedure should be
±.5% or ±0.25 ygat Si/1 and is considered acceptable when
the greater stability of it is considered.
For waters higher in silicate concentration, further
investigation should be performed to determine if the range
can be extended without significant nonlinear effects.
6 . Blanks
A blank determination should be performed daily by
sampling the analysed sea water with only DDDW in the reagent
lines. This absorbance in the flowcell is believed due to
the change in optical density of the higher salinity sea
water and is assumed to occur also during analysis with
reagents. Silicate blanks determined varied from 0.36 ygat
i
Si/1 to 0.46 ygat Si/1 with an average value of 0.40 ygat
Si/1 used in data correction.
7 . Data Reduction
Baseline drift was approximately linear [Strickland
and Parsons 1968, Atlas et al. 1971] and the resultant cor-
rection was added or subtracted from the sample recorder
percentage value assuming this linearity between baseline
28
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29
checks. When the baseline was checked every 15 minutes this
correction was normally very small.
The standardization factor was determined each hour
from the calibration standard and used to determine all
sample concentrations during the subsequent hour. Consecu-
tive standardization values were compared for significant
changes but no attempt was made to correct for variations
because of a number of reasons. Linearity could not be
assumed. The same change could not be assumed to hold over-
the entire range of concentrations tested, and the small
variation (±.5%) in standard percentage values was considered
to be within the precision of the technique.
Samples were identified on the recorder and the
percentage of full scale was logged using the highest value
of the peak nearest the trailing edge (closest to the end
of sample when steady state or near steady state was
obtained) . This is indicated in a representative plot
(Figure 7). Percentage values can be read to 0.1%. The
baseline correction was then applied, the blank correction
subtracted and the concentration with respect to DDDW stan-
dard was determined by multiplying by the concentration
conversion factor. Finally, the salt error correction
was applied as discussed above and the final corrected con-
centration obtained.
During this study all data reductions were performed
manually but for a larger volume of data a computer program
would be desirable [Atlas et al . 1971].
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8. Interference
No specific interference tests were conducted during
this study, however phosphate and nitrate standards analysed
in dual operation with this silicate procedure showed no
significant effect. This confirms the results of Atlas
et al. [1971] who used the AAI system. Atlas et al [1971]
also reported no noticeable arsenic interference (to 0.8 ygat
Ar/1) in their studies. The Technicon procedure indicates
tannin, large amounts of iron, color, turbidity and sulfide
may interfere with this procedure. All samples obtained in
this study were analysed directly without filtration and
gave good results with little or no noise attributed to
turbidity.
9 . Summary
Extreme care must be used to prevent silica contam-
ination from glass containers for this analysis. Careful
analysis during linearity tests indicated a silicate increase
of 2 - 5% (1.0 - 2.5 ygat Si/1) when standards remained in
glass volumetric flasks for only 10-30 minutes. Also,
synthetic sea water stored in a brown glass bottle indicated
a 25.0 ygat Si/1 increase during one month storage. During
cruise four analyses (see below) , approximately 10 samples
taken in nutrient deficient open sea water gave negative 2%
(-1.0 ygat Si/1) results. These results below baseline
indicate a 1.0 ygat Si/1 contamination level in the DDDW
wash and/or reagents used during this cruise. The absolute
silicate concentration values are therefore probably low by
32
1.0 ygat Si/1 for this cruise and are indicated as errors
below. The relative values of concentration variations are
believed to be much better. Strickland and Parsons [1968]
note that synthetic sea water used for standard preparation
should be below 1 or 2 ygat Si/1. This is the range of
contamination found to exist during cruise four. Additional
tests in the laboratory and a review of other cruise data
indicate the normal contamination level is significantly
lower if the above precautions are followed.
The silicate procedure was found quite stable with
little noise interference from bubble patterns or optical
density changes. The peak plateaus were very good at 40
samples/hour. Proper wash procedures must be followed and
sufficient time for baseline stabilization allowed prior to
commencing analysis (at least 15 min . ) in order to minimize
baseline drift during analysis. By checking the baseline
every 15 minutes during analysis, baseline corrections
normally can be reduced to below 1%. Hourly standardization
gave good results and corrected for significant temperature
changes or reagent deterioration experienced.
Table I gives a summary of errors determined for the
silicate procedure during both laboratory and shipboard opera-
tion for 0-50 ygat Si/1 range of calibration. Error data
from Atlas et al [1971] (AA-I procedure) is also presented
for comparison purposes. With additional experience using
this equipment and refinement of techniques these errors
probably can be reduced.
33
TABLE I
SOURCES AND MAGNITUDE OF ERRORS (ygat Si/1)
IN THE CONCENTRATION RANGE OF 0-50 ygat Si/1
AA-II (Note 2)
Atlas et al.
(AA-I) (Note 2)
Recorder Reading
Error
±0.05
±0.15
Precision (2a)
±0.049 (Note 1)
±0.06
Salt Effect
±0.250
*
Salt Error
*
-.045 ± .004/1%
increase in salinity
Non-linearity Error
±0.250
±0.25 (est.)
Minimum Detection
0.5 ygat Si/1
**
Limit
above baseline
Contamination Level
±1.0 ygat Si/1
**
Error
Maximum Total
±0.55 ygat Si/1
**
Relative Error
Est. Maximum
1.0 ± 0.55 ygat Si/1
**
Absolute Error
-
Note 1: Calculated from results of 32 triplicate standards,
Note 2: AA-I (AutoAnalyzer® I) ; AA-II (AutoAnalyzer® II ) .
*
AA-I procedure used standardization in artificial seawater
and defined salt error differently.
**
Not specified.
34
B. ORTHO PHOSPHATE ANALYSIS
®
Technicon Industrial Method No. 155-71W was followed
for phosphate analysis as modified for dual channel opera-
tion. In this automated procedure ortho phosphate is
colorimetrically determined as the phosphomolybdenum blue
complex at 880 nm [Murphy and Riley 1962], The flow diagram
for this procedure is shown in Figure 8. A single reagent
solution is used consisting of an acidified solution of
ammonium molybdate containing ascorbic acid and a small
amount of antimony. A heating bath of 37.5°C provides for
temperature stability and time regulation of the chemical
reaction. Silicon (SI) phototubes are used for improved
sensitivity while using 880 nm interference filters. The
sampling rate was modified to 40 samples/hour at a 4:1
sample- to-wash ratio for compatible dual channel operation.
All sea water analysed v/as within the specified range of
0-4 ygat P/l.
1. Reagents
SULFURIC ACID: 136 ml. of concentrated sulfuric
acid were added to 800 ml of DDDW while cooling. The cooled
solution was diluted to 1000 ml.
AMMONIUM MOLYBDATE: 40 g of reagent-grade ammonium
molybdate were dissolved in 800 ml of DDDW, then diluted to
1000 ml.
ASCORBIC ACID: 18 g of reagent-grade ascorbic acid
were dissolved in 800 ml of DDDW, then diluted to 1000 ml.
This reagent was refrigerated when not in use.
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ANTIMONY POTASSIUM TARTRATE: 3.0 g of reagent-grade
antimony potassium tartrate were dissolved in 800 ml of DDDW,
then diluted to 1000 ml.
COMBINED WORKING REAGENT: The combined color
reagent (Figure 8) was prepared by mixing the above reagents
in order; 50 ml sulfuric acid, 15 ml of ammonium molybdate,
30 ml of ascorbic acid, and 5 ml of antimony potassium
tartrate. This reagent was mixed well and used from a
brown reagent bottle to reduce deterioration. A new solu-
tion was mixed every 8 hours or when significant discolora-
tion developed.
WATER DILUENT: 10 drops of Wetting Agent A were
added to 1000 ml of DDDW. This solution assisted in pro-
ducing good bubble patterns. It must not be used for wash
water or rinse due to possible resulting contamination.
2. Standards
STOCK STANDARD A, 1000 ygat P/l: 0.136 g of anhy-
drous potassium dihydrogen phosphate was dissolved in 500 ml
of DDDW and diluted to 1000 ml in a volumetric flask. 1 ml
of chloroform was added as a preservative.
STOCK STANDARD B, 40 ygat P/l: 10 ml of Stock
Standard A were diluted to 100 ml with DDDW in a volumetric
flask. This standard was prepared fresh daily.
37
WORKING STANDARDS:
ml Stock B ygat P/l
0.20 0.08
2.0 0.8
4.0 1.6
6.0 2.4
8.0 3.2
10.0 4.0
The required volume of Stock Standard B was pipetted into
a 100 ml volumetric flask and diluted to 100 ml with DDDW.
These standards were prepared fresh daily. During at sea
operations only the 2.4 ygat P/l standard was used to set
and check the equipment calibration as the calibration
curve proved to be linear (Figure 9). All glassware, sample
cups, and storage bottles were thoroughly washed, rinsed,
then rinsed with IN HC1 and finally rinsed three times with
DDDW before use.
3. Baseline
The phosphate baseline adjustment was similar to the
silicate procedure. This pr6cedure, however, being of much
lower concentration range was more subject to baseline
fluctuations and noise. Contamination of wash water is
extremely easy and all foreign material, dust, etc. must
be guarded against. Contamination of wash or reagents is
indicated by an erratic baseline condition. Bubble noise
was sometimes a problem with this procedure and Damp 1
38
1.0 2.0 3.0 4.0
Phosphate Concentration (ygat P/l)
Figure 9. Phosphate Linearity Check
39
operation of the colorimeter (as specified by Technicon )
was sometimes necessary.
4 . Linearity
Four linearity test runs were performed using DDDW
standards of 0.8, 1.6, 2.4, 3.2, and 4.0 ugat P/l. All
results were satisfactory and reproducible. The linearity
was within ±0.7% (0.028 ygat P/l) over the range tested.
Figure 9 illustrates a typical result. Again, each datum
point represents the average value of two standard samples
analysed.
5. Salt Error
Although past authors [Strickland and Parsons 196 8,
Atlas et_ a_l. 1971] using similar procedures with the AA-I
system indicate there is a significant salt error involved
and specify standardization in artificial sea water or low
nutrient sea water, Technicon 's procedure indicates a salt
error of less than 1%. Two salt error test runs were per-
formed comparing DDDW standard results with standards
mixed in sea water. The results are shown in Figure 10 and
confirm the Technicon procedure showing a maximum salt
error of 1% at very low concentrations. A single test run
for salt error comparing DDDW standards with artificial sea
water standards indicated a possible salt effect of 10%
(0.4 ygat P/l). This may explain the reported errors but
further tests would be necessary to confirm these results.
40
6 . Planks
Blank determinations were performed similar to those
discussed for silicate. The results, however, were much
more significant and indicated an average of 4.4 8% (.18 ygat
P/l) optical density blank correction was necessary for the
phosphate determinations. Further tests in the laboratory
confirmed this value. The average artificial sea water
blank, determined for a check, was 4.35%, in good agreement
with the subject sea water results.
7. Data Reduction
Data reduction of the phosphate analysis was like
that of silicate except no salt error corrections were
necessary.
8. Interference
Although no specific tests were performed, no sig-
nificant interference was noted during dual operation by
either silicate or nitrate standards prepared in DDDW.
Artificial sea water standards gave varying interference
results from a low of 4% to a high of 21% I This was a major
concern when operating dual with nitrate-nitrite or silicate
standards prepared in artificial sea water and resulted in
the salt effect experimentation. As noted above, this
procedure is measuring a very low concentration and subject
to contamination and noise when in the lower end of the
range.
Arsenate interference [Johnson 1971, Atlas et. al.
1971} is expected if the phosphate is low level and arsenate
concentration abnormally high.
41
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1.0 2.0 3.0
Phosphate Concentration (ygat P/l)
4.0
Figure 10. Phosphate Salt Error Test.
42
9 . Summary
Although greater difficulties with blank corrections,
baseline stability, and contamination problems were found
with this procedure than the others used, the techniques
adopted and discussed above were reliable and very sensitive.
Here, as in the silicate technique, the baseline,
after proper washout, must be allowed to stabilize well
before analysis is attempted. Baseline and standardization
procedures as discussed for the silicate procedure are
considered necessary.
Table II gives a summary of errors determined for
the phosphate procedure for the range of 0-4 ygat P/l tested.
TABLE II
SOURCES AND MAGNITUDE OF ERRORS (ygat P/l) IN
THE CONCENTRATION RANGE OF 0-4 ygat P/l
Recorder Reading Error
Precision (2a)
Salt Effect
Non-linearity Error ,
Minimum Detection Limit
Calculated Maximum Absolute Error
* ®
Technicon procedure indicates 0.08 ygat P/l as minimum
detection limit. Results indicate better performance pro-
viding all errors indicated above are not maximum and
cumulative.
Note 1: Calculated from results of 33 duplicate standards
±0.004
±0.037
(Note 1)
±0.020
±0.028
±0.04*
±0.089
43
C. NITRATE-NITRITE ANALYSIS
Technicon Industrial Method No. 158-71W was followed
for the nitrate and nitrite analysis. This procedure was
modified to extend the concentration range to 25 ygat N/1
and change the standardization procedure.
The flow diagram for this procedure is given in Figure 11,
Determination of nitrate is accomplished by first reducing
the nitrate to nitrite in a 14 inch reductor tube filled
with copper-cadmium [Armstrong et a_l. 1967, Grasshoff 1969].
The nitrite ion then reacts with acidified sulfanilamide to
form a diazo compound. This compound couples with N-l-
napthylethylene-diamine dihydrochloride to form a purple
azo dye. The color produced is colorimetrically determined
at 550 nm. A sampling rate of 40 samples/hour and a 4:1
sample-to-wash ratio was used. When analysing using the
reduction column the resultant value represented total
nitrate plus nitrite concentrations. Nitrite alone was
determined by removing the reduction column. The nitrate
concentration value was then determined by difference. This
method was normally calibrated for the range of 0-25 ygat N/1
instead of the specified range of 0-5 ygat N/1.
1 . Reagents
AMMONIUM CHLORIDE: 10 g of reagent-grade ammonium
chloride were dissolved in DDDW (made basic to PH 8.5 with
ammonium hydroxide) and diluted to 1000 ml.
COLOR REAGENT: 200 ml of concentrated phosphoric
acid were added to 1500 ml of DDDW. 20 g of reagent-grade
44
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sulfanilamide were then added and dissolved (solution heated) .
One gram of reagent-grade N-1-naphthylethylene-diamine
dihydrochloride was added and dissolved. The solution was
diluted to two liters with DDDW and 20 drops of Brij-35 wet-
®
ting agent (available from Technicon ) added. This solution
was stored in polyethylene bottles and refrigerated when not
in use.
CADMIUM COLUMN: 10 g coarse cadmium powder (pur-
®
chased from Technicon ) was rinsed well with one Normal HC1
solution and then with DDDW to remove any grease and dirt.
The cadmium powder was then treated with 50 ml of two per-
cent copper sulfate (CuSO,«5 H„0) solution. The Cd powder
was stirred well in this solution until brownish semi-
colloidal copper particles formed in the liquid. The super-
natent liquid was decanted and the powder thoroughly washed
with DDDW until no copper particles remained in the clear
water (10 to 15 washings) . It is very important to remove
all colloidal materials which would restrict flow and carry-
over into the tubing and flowcell.
A glass U-tube (0.0 81 inch I.D.) was used for the
column. This tube performed satisfactorily but was difficult
to fill and empty. To fill the column the tube was submerged
under water and all air allowed to escape. The treated
cadmium powder, still in the final wash water, was sucked
into a long glass dropper, the tip of which had been cut so
the powder could pass. The dropper was then submerged above
the tube and the cadmium water mixture discharged into the
46
tube. Care was taken to prevent any bubbles from entering
the tube. During filling, the column was gently tapped to
insure proper packing. When the column was nearly filled
(about -t inch from the ends) glass wool was inserted to
prevent the cadmium from dropping out. After starting the
pump to remove air from the analytical stream, the column
was inserted as indicated in the flow diagram.
The reductor column was activated by sampling Stock
Standard B (see below) solution for five minutes, followed
by a -r- hour wash with DDDW. Columns prepared in this
manner with fresh cadmium performed well for over 500
samples .
2. Standards
STOCK STANDARD A, 1000 ygat N/1: 0.101 g of potas-
sium nitrate was dissolved in DDDW and diluted to 1000 ml.
One ml of chloroform was added as a preservative. This
standard was stored in a brown glass bottle.
STOCK STANDARD B, 50 ygat N/1: Five ml of Stock
Standard A were diluted to 100 ml in a volumetric flask.
This standard was prepared each time Working Standards were
required.
47
WORKING STANDARDS
ml Stock B pgat N/1
0.20 0.1
2.0 1.0
4.0 2.0
6.0 3.0
8.0 4.0
10.0 5.0
20.0 10.0
40.0 20.0
The required volume of Stock Standard B was pipetted into a
100 ml volumetric flask and diluted to 100 ml with DDDW.
These standards were prepared fresh daily. During at sea
operations usually either the 10.0 ygat N/1 or 20.0 ygat N/1,
depending on the range desired, standard was prepared to set
and check the equipment calibration as the calibration curve
proved to be linear (Figure 12) . All glassware, sample cups,
and storage bottles were thoroughly washed, rinsed, then
rinsed with one Normal HC1 and finally rinsed three times
with DDDW before use.
3. Baseline
The nitrate and nitrite baseline adjustment was
identical to the silicate procedure. This procedure proved
to be the most stable of those used and very little baseline
drift was noted after the system had stabilized. It was not
uncommon to have zero baseline correction during a two hour
run.
48
5 10 15 20 25
Nitrate Concentration (ygat N/1)
Figure 12. Nitrate Linearity Check.
49
4 . Linearity
Three linearity test runs were performed using DDDW
standards of 2.5, 5.0, 10.0, 15.0, 20.0, and 25.0 ygat N/1.
All results were satisfactory and reproducible and indicated
linearity of ±1.0% (0.25 ygat N/1) over the range tested.
Figure 12 illustrates a typical result. Each datum point
represents the average value of two standard samples analysed
5. Salt Error
Here again, published data is not consistent on the
®
degree of salt effect. Technicon's procedure indicated
slight salt effect and specified standards be prepared in
artificial sea water. Atlas et a_l. [1971] indicated negli-
gible salt effect in the range 0-40 ygat N/1 but still
specified standards prepared in artificial sea water.
Strickland and Parsons [1968] indicated salt effects and
recommended standards be prepared in low nitrate surface sea
water.
Four salt effect test runs were performed comparing
DDDW standard results with standards mixed in sea water.
One representative run is shown in Figure 13 and indicates
a maximum difference of 0.6% (0.15 ygat N/1). All results
were comparable and indicate an insignificant error in the
tested range.
6. Blanks
Blank determinations were performed similar to those
for silicate. Average values for blanks obtained were:
Nitrate 0.40% (0.1 ygat N/1), Nitrite 0.38% (0.095 ygat N/1).
50
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0 5 10 15 20
Nitrate Concentration (ygat N/1)
25
Figure 13. Nitrate Salt Error Test.
51
7 . Data Reduction
Data reduction for nitrate and nitrite analysis was
the same as for phosphate analysis.
8 . Interference
No significant interference was noted from phosphate
®
or silicate standards when operating dual. Technicon indi-
cates abnormally high concentrations of metal ions may
produce positive interference on this analysis.
9 . Summary
This procedure for nitrate-nitrite analysis was
very stable and reproducible. Very little recalibration or
baseline adjustment was necessary after proper stabilization
and initial adjustment. •
The Cadmium column proved to be the most troublesome
element [Atlas et al. 1971, Strickland and Parsons 1968].
One column, prepared from reactivated cadmium powder,
apparently not well cleaned, rapidly clogged causing up-
stream back pressure and leakage. Proper cleaning and copper
treatment should prevent this. Care in column preparation
and exclusion of air resulted in good performance and no
significant decrease in reduction efficiency for over 500
analyses .
Table III gives a summary of errors determined for
the nitrate-nitrite analysis for the range of 0-25 ygat N/1
tested.
52
TABLE III
SOURCES AND MAGNITUDE OF ERRORS (ygat N/1)
FOR CONCENTRATION RANGE OF 0-25 ygat N/1
Recorder Reading Error ±0.025
Precision (2a) ±0.107 (ave of 23 trip-
licate samples)
Salt Effect ±0.075
Non-Linearity Error ±0.250
Minimum Detection Limit 0.100
Calculated Maximum Absolute Error ±0.457
Although the precision determined from laboratory
tests of this procedure is quite good (less than 0.5%) com-
pared to earlier results [Atlas et a_l. 1971] of ±2%, the
maximum absolute error becomes significant when analysing
low nitrate-nitrite concentration waters. This problem was
partially corrected by recalibrating the system for a lower
concentration range when low nitrate waters were experienced,
The nitrite concentrations generally did not vary signifi-
cantly with changing nitrate lvalues and all nitrite concen-
trations obtained in this study were below 1.0 ygat N/1.
The nitrite analysis was not calibrated with nitrite stan-
dards but used the nitrate standards prior to removal of the
cadmium column and checked after the column was reinstalled
following a run (about 2 hours) . This appeared to be satis-
factory and no significant calibration change was noted
53
during this period. A serious deficiency in technique
resulted from not reducing full scale range down to
0-5 ygat N/1 or less when preparing for nitrite analysis
but continuing to operate at the previous nitrate range
(0-25 ygat N/1 or 0-10 ygat N/1). Consequently, the
values obtained for nitrite concentrations are subject to
rather large relative errors (approaching the values of the
determined concentrations) and must be considered only
approximate. In further study the equipment must be cali-
brated for the range of concentrations determined to mini-
mize the errors found in the higher ranges.
54
IV. SHIPBOARD OPERATION
To enable near real-time analysis and prevent the neces-
sity of freezing samples with the subsequent changes of
nutrient concentration resulting from storage, time,
®
hendling, etc., the AutoAnalyzer was operated at sea.
A. EQUIPMENT PREPARATION
The AA-II system was prepared for shipboard use by
installing the components in three heavy plywood cases
(Figure 14) . The first case contained the sampler and pump.
The second case contained the three reagent cartridges, two
colorimeters and associated voltage stabilizers. The third
case housed the recorder (Figure 15) . The components were
secured to the bottom of the case using nylon securing
straps. Foam rubber padding was under and around the sides
of all components to prevent shock damage. During transpor-
tation the components were further padded above with foam
rubber and the case covers securely attached. Reagent
bottles were held in circular wells cut into a false bottom
built IV above the actual bottom. This arrangement pre-
vented sliding motion of the bottles and components during
heavy seas even if the retaining straps were removed for
short periods. The cases were placed together as seen in
Figure 14 with the sampler located near a sink and firmly
secured to the bench. Half the hold down straps were
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positioned so as to remain in place and not affect operation
of the equipment.
The recorder was installed in case three. This compo-
nent is quite heavy so rather than pad, as with the lighter
components, the case was shock mounted on four heavy duty
shock mounts. This prevented any damage from transporta-
tion or shipboard motion.
B. SAMPLING PROCEDURE
The nature of this study required a large number of sur-
face or near surface samples. The simplest method of sample
collection available was desired to simplify operation and
minimize the time between samples. A 3/8 inch I.D. tygon
tube was installed to the ship's encrineroom and attached to
a salt water circulating pump casing vent. The selected
pump was one with a short piping run from the sea suction
located near the keel. This reduced chances of contamina-
tion from the piping system and was representative of the
water immediately below the ship, least effected by ship
motions and any ship discharge higher on the hull. The
selected pump was required to be a continuously operating
pump with a large flow rate which maximized water turnover
and minimized any sampling time delays. The flow rate
through the tubing was adjusted to about four liters/minute.
The time delay for sample passage from the sea chest to the
sampler was calculated as 13 seconds for this setup.
58
Samples were tested, for contamination by comparing with
Nansen bottle samples and deck pump samples taken from the
depth of the engineroom sea chest. Results indicated all
nutrient concentrations were the same within the precision
of the technique and contamination was insignificant.
The sampling tube discharged a continuous flow into the
sink. At the time desired, a sample cup was rinsed three
times, filled from the tube and placed in the sampler. The
time, depth and sample number was recorded on the data work
sheet (Appendix A) for later correlation with the ships
position.
Sampling through the mixed layer (to 100 meters) was
performed using a deck operated gear pump with a garden hose
attached to the hydro wire for varying depth of sampling.
This pump also discharged into the sink and samples v/ere
taken in the same manner as above.
C. DIFFICULTIES AND PROBLEMS
During cruise four (see below) a submersible pump was
obtained and used to collect samples through the mixed
layer. This pump was lowered over the fantail to the
desired depth and the water pumped to the surface. The
results were satisfactory although the pump and hose weight
became difficult to handle manually when 80-100 meters deep.
Only three stations were obtained before the hose became
entangled in the propulsion unit of the active rudder and
the pump was lost. Subsequent depth samples were obtained
using the deck pump as discussed above.
59
Some difficulties with bubble interference appeared
to be related to ship roll during heavy seas. The sample
stream must be debubbled prior to flowing through the cell
or bubble spikes result on the recorder output. During
heavy seas it seemed that the bubbles were not properly
removed when the ship rolled. This problem was later iden-
tified as being caused by the use of an incorrect I.D.
coupling used to join the reagent cartridge to the colori-
meter. After the correct coupling was made up, ship roll
did not affect the operation.
The time required to properly washout, exchange
cartridges, change filters (and phototubes for the phosphate
procedure) , stabilize baseline and restandardize using
fresh standards proved to be much longer than originally
expected. An hour was normally required from completing one
dual operation to commencing the next. This became a con-
trolling factor when samples were being taken at short
intervals (less than 10 minutes). When all required opera-
tions were included (washout, standardization, baseline
checks, etc.), the time required to perform all four nutrient
analyses on 80 samples was about 7 hours. This resulted in
an average of 45 analyses per hour or about 11 samples per
hour. If the sampling rate was greater than 11/hour for an
extended time, samples began stacking up and were tempor-
arily stored in the refrigerator.
All depth samples were taken while stopped. The suction
hose was manually tied to the hydro wire as it was lowered
60
to 80 meters depth. When coming up the hose was handled by
hand after being cut away from the wire. This procedure
required two men and a considerable amount of time. During
this period the ship drifted significantly in strong current
areas, making accurate determinations of the vertical profile
difficult.
D. FUTURE IMPROVEMENTS
To reduce the time required for cartridge changes and
improve sampling techniques a number of improvements are
under preliminary investigation:
1. An accurate study of standard deterioration is
necessary to determine if DDDW standards show the deteriora-
tion reported for sea water and artificial standards. Pre-
liminary results indicate no significant deterioration for
over 24 hours if properly stored.
2. A combined standard may be possible [Strickland and
Parsons 196 8] which would further reduce the time required
for shipboard operation.
3. A solenoid valve was obtained and an attempt to
install in the flow line to automatically fill the sample
cups looks promising and will reduce operator time. Diffi-
culties with back pressure on the line now prevent operation.
4. A system of pumps set for different depths, each
with a depressor attached, would allow depth samples to be
taken when underway at a constant speed and allow greater
selectivity of sample spacing and should produce results
61
less subject to ship drift from current effects. This
method would also save much handling time and effort result-
ing in greater data output per operator.
62
V. CRUISE INFORMATION
During this study four cruises were performed to collect
nutrient data. Table IV indicates the pertinent data asso-
ciated with each cruise.
A. CRUISE ONE
Figure 16 illustrates the ship track followed for cruise
one on 19 April 19 72. The purpose for this cruise was to
test the shipboard operation of the AA-II system and deter-
mine the variability of nutrient concentrations in the
surface waters. Data were obtained for surface waters
located eight feet below the surface (R/V ACANIA suction
depth) . The weather was extremely rough during this cruise
and made depth sampling difficult. Four casts were performed
to 40 meters and proved the feasibility of using a portable
deck pump for sampling.
B. CRUISE TWO
Figure 17 illustrates the ship track followed for cruise
two on 28 April 1972. During this season upwelling along
the Monterey area coast was developing and cruise two was
planned to obtain an early season upwelling signature. The
weather was again rough with winds to 35 knots and sea/swell
running 14-18 feet. This prevented all topside operations
including vertical depth sampling. The performance of the
internal sampling rig and AA-II system was satisfactory and
good surface data were obtained.
63
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Figure 16.
Exploratory Cruise Number One
19 April 1972.
65
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Figure 17. Cruise No. 2 Track 28 April 1972.
66
C. CRUISE THREE
Figure 18 illustrates the ship track for cruise three on
5 May 19 72. This cruise gathered both surface and subsur-
face data inside the Monterey Bay circulation patterns. The
weather was calm and the mixed layer stable. The data
obtained were used to correlate the four nutrients with
sampled areas and observe changes in nutrient concentrations
with time of day.
D. CRUISE FOUR
Cruise four was performed on the USNS BARTLETT from 18
to 21 May 1972. This cruise was divided into six legs, the
tracks were as illustrated in Figures 19-23. Track one was
a general survey of the Monterey Bay area and used to
correlate with data obtained during cruise three. Leg one
was interrupted after the loss of the submersible pump (see
Difficulties and Problems . above) and the ship was forced to
return to port for an underwater inspection. Leg two resumed
on 19 May following the inspection. The purpose of this leg
was to pass through and out of the shoreward upwelling area
to a point 50 miles to sea to, obtain open ocean nutrient
concentration levels. The open sea levels were then to be
used as a baseline to correlate with the higher concentra-
tion values near shore. In this manner upwelling strength
and biological activity were to be determined by nutrient
concentration changes. Data from legs three and four were
obtained in this open sea area. Leg five returned shoreward
67
-, -, k-^i , , 1 , , , 1 , 1 1 r 1 1 1 , , , , , . 1 , p
A^ I I I I I I I ~\l I I I i I Sr. t> I
Figure 18. Cruise No. 3 Track 5 May 1972
68
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Figure 19. Cruise No. 4 Track Leg One 18-19 May 1972
69
/f" I i i i i i ' ~ni ' i I i i !i
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Figure 20. Cruise No. 4 Track Leg Two 19 May 1972.
70
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t — i — n^ri — I — i — i — i — i — i — r — i — i — I — i — i — i — i — i — i — i — i — i — I — i — i — r
Figure 23. Cruise No. 4 Track Leg Six 21 May 1972
73
obtaining a nutrient signature of a different upwelling
area. Finally, leg six passed across Monterey Bay again
furnishing bay area variation data.
Operations during the cruise four period furnished the
bulk of the data for this study. All surface samples from
the installed tube system were taken at a depth of 13.5 feet
of water. Vertical temperature data were obtained with
Expendable Bathythermograph (XBT) equipment. Particle
density, light transmittance , and chlorophyll data were
obtained and are presented elsewhere [Killion 1972].
74
VI. RESULTS
A. SURFACE DATA
1. Cruise One
Cruise one results were rather disappointing due to
bad weather, equipment difficulties, and chemical problems.
Satisfactory results of only the silicate and total nitrate
analyses were obtained and are presented in Figure 24.
Phosphate values were not obtained due to chemical problems
with the color reagent which prevented satisfactory calibra-
tion and caused an unstable baseline. This problem was
believed caused by a bad ascorbic acid reagent. This
reagent was prepared fresh for each subsequent cruise.
Figure 24 indicates the silicate and total nitrate variation
in the surface waters of the two mile track between points
1A and 2A of Figure 16. The distance is plotted from the
initial point 1A. This track was selected perpendicular
to the wind direction outside the area of expected upwelling
Both the silicate variation (0.8 ygat Si/lj and the total
nitrate changes (0.20 ygat N/1) were found to be very small
and could be considered near constant within the accuracy of
the analysis techniques. These results indicate a very well
mixed water mass which was confirmed by isothermal BT traces
and a weather history of heavy seas for the previous five
days .
75
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2 . Cruise Two
Cruise two results were very interesting and are
illustrated in Figure 25. Here the distance is measured
along the track from station 10 toward Monterey Bay (Figure
17) . Station separation was one mile. An upwelling signa-
ture was obtained where all three major nutrient concentra-
tions (SiO. ,PO„ ,N0o) first increased shoreward, then remained
quite constant, finally rapidly decreasing across the 100
fathom curve and into the Monterey Bay area. The major
nutrient concentrations indicated an extremely close, although
expected, correlation.
3. Cruise Three
Cruise three surface data is illustrated in Figures
26 and 27. A significant variability in the three major
nutrient concentrations was found, over most of the track.
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along track), however, showed a constant nutrient plateau.
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although sampled 16 days later. The three major nutrients
tested varied almost identically as noted in cruise two.
The results of leg one show a close relationship to the last
half of kg four (distance 22 to 27 miles) where the tracks
nearly coincided but were analysed five hours apart.
4 . Cruise Four
a. Leg One
Surface data obtained during cruise four, leg
one (Figure 19) is illustrated in Figure 28. A significant
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change in the Bay nutrient signature was found from that
obtained 12 days earlier (cruise 3) . The level plateau
noted previously had developed in Monterey Bay and existed
across the submarine canyon to the 50 fathom curve (station
2). The nutrient signature for the harbor to 50 fathoms had
not changed significantly. This plateau pattern again
identifies the well mixed high nutrient surface layer
indicative of developed upwelling.
b. Leg Two
Surface data from cruise four, leg two (Figure
20) is illustrated in Figure 29. When compared to cruise
two data (Figure 25), these results indicate the changing
upwelling signature 21 days apart. The major nutrients
(SiO ,PO ,NO ) were still very well correlated but the
fr t —)
plateau values for phosphate had decreased 23% and for
silicate had decreased 27%. The average nitrate plateau
values remained, constant. The width of the upwelling
signature had grown from about seven miles (cruise two) to
13 miles for cruise four, leg two. An interesting phosphate
maximum was found on the seaward edge of both upwelling
areas and appears to correspond with high biological
activity. Chlorophyll data from cruise four indicated a
rapid increase in chlorophyll concentration at 18 miles
[Killion 1972]. This high chlorophyll level was maintained
for 28 miles along the track. Indications of plankton bloom
areas were found to clearly correlate with the minimum
nutrient concentrations in this area.
82
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c. Leg Three
Surface data from leg three (Figure 21) is
presented in Figure 30. A four mile continuation of the
nutrient low found on leg two is followed by a rapid increase
to another nutrient high over 14 miles wide. Inside this
area of high surface nutrient concentration the chlorophyll
values were found to be very low. Major nutrient concentra-
tions continued to provide outstanding correlations. Plateau
values had changed significantly from values found on the
leg two plateau only 12 miles away. The phosphate concen-
tration decreased 33% whereas silicate (47% decrease) and
nitrate (44% decrease) changes were nearly equal. At 45
miles another plankton bloom was found driving surface
nutrients to near zero values. This two mile bloom was
followed by another three mile wide plateau.
d. Leg Four
Figure 31 illustrates surface data obtained
from cruise four, leg four (Figure 21) . Again three plateaus
were obtained between which were strong planktonic blooms
which had driven the nutrient concentrations down.
e. Leg Five
Leg five (Figure 22) was divided into two sec-
tions 5A (72 to 90 miles) and 5B (90 to 110 miles) . Leg 5A
surface data is illustrated in Figure 32 and clearly indi-
cates a continuation of the bloom-plateau signatures found
in legs four and five. Leg 5B surface data is illustrated
in Figure 33 and is representative of another well developed
84
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upwelling signature 14 miles wide increasing in concentration
levels as the coastline is approached.. After completion of
station D-2 (two miles from the coastline) the track turned
and paralleled the coast. Nutrient concentrations dropped
significantly in this area (from 105 miles along track)
indicating a reduced upwelling intensity due to shallow
water. Station positions D-30, D-15, D-7, D-5, D-3, and D-2
show peak surface values for the major nutrients signifi-
cantly greater than surrounding waters. These spikes were
first believed caused by the differing sampling techniques.
The installed tube system showed reduced values and the
portable deck pump indicated higher concentrations during
the vertical determinations. The vertical profiles (see
Vertical Variations) later proved that the different equip-
ment was not at fault but the actual concentrations dra-
matically decreased from the surface to 13.5 feet. This
decrease in values correlated with the spike values noted.
This unexpected result does distort the surface signature
somewhat because all surface and 13.5 foot samples are
plotted together. The results are significant and real and
will be further discussed when presenting the vertical
profiles .
f. Leg Six
Leg six (Figure 23) surface data is illustrated
in Figure 34. This final leg of cruise four represents the
profile across the Monterey Bay submarine canyon. A rapid
increase in concentrations was noted at 109 miles as the
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track moved away from the coastal area. This was followed
by a slower increase to the plateau values reached at
station M2 directly over the deepest water (500 fathoms) .
The southern half (122 to 132 miles) again shows the con-
stant plateau area described in leg one with concentration
values much like those found three days previously. Nitrate
and nitrite data from 122 to 132 miles was not obtained
because of insufficient reagents on board.
B. MIXED LAYER VARIATIONS
Cruise four mixed layer nutrient concentrations are
illustrated in Figures 35 through 41. Each figure is a
horizontal plot of the three major nutrient (SiO, ,P04 ,NO_J
concentrations versus distance along the track. Each figure
presents data at one of seven depth sampled; 10, 20, 30, 40,
50, 60, and 70 meters. The first 50 miles was not signifi-
cant because of lack of data but does indicate the general
variation. From 50 to 130 miles the data were more complete
and the mixed layer variations were clearly seen. The
nutrient variations were found to be quite similar for all
depths to 50 meters. Close examination of the 50, 60, and
70 meter variations indicated a lesser correlation with the
near surface results and a more significant effect from
circulation patterns, especially the upwelling area from 85
to 105 miles along the track. The depth of the seasonal
thermocline was found to be from 25 to 45 meters near land
and near 50 meters at stations farther to sea.
91
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C. VERTICAL PROFILE VARIATIONS
Figures 42 to 52 illustrate representative results of
vertical nutrient profiles found during cruise four.
Figure 42 is the profile found in 100 fathoms of water during
leg one (Station 3) . This represents a "normal" profile
where the three major nutrients are well correlated, essen-
tially constant through the mixed layer (depth 40 meters)
then show a rapid increase through the thermocline. The
major nutrients show a gradual increase with depth below
the thermocline. Nitrite concentration indicates the
reverse effect, decreasing through the thermocline.
Figure 43 is a vertical profile of the nutrient con-
centrations representative of the profiles obtained in the
nutrient plateau areas of legs three and four (Stations 2,
3, 4). In these areas the nutrient concentrations were
found to be relatively high and constant from the surface
to the depth of the thermocline (40-50 meters) . Across the
thermocline the concentrations increased significantly.
Figure 44 illustrates the type profiles obtained in the
areas of plankton blooms along legs three and four (Stations
1 and 5) . This station was taken at 0140 in the morning
and indicates the significant decrease in all nutrient
concentrations in the upper 10 to 15 meters. The biological
population appears to be very shallow and has driven the
concentration levels down. The concentrations found below
the planktonic layer (greater than 20 meters) is much like
those found throughout the plateau region and indicates the
same water mass.
99
Figure 42. Vertical Profile Leg One Station 3
100
200029
6 0.80 miles
60
Figure 43. Vertical Profile Leg Four Station 4
101
Figure 44. Vertical Profile Leg Four Station 5
102
Figure 45 is the profile of station six (leg four)
located close to the edge of a nutrient plateau (Figure 31) .
This station was sampled at sunrise and indicates a combined
plateau-bloom activity. The surface concentrations were
again near constant to 20 meters but having concentration
values intermediate between those found for "pure" plateau
and bloom areas. Between 20 and 45 meters the concentrations
were again significantly depressed. This indicated the
downward movement of biological organisms as the light
intensified. Below 45 meters the profile values dramatically
increased to the maximum values found on legs three and four.
The temperature profile was near isothermal to 70 meters in
this area.
Figure 46 is the vertical profile of station D-30, leg
5A (Figure 22) . This profile was obtained three hours later
and seven miles shoreward of the last (Figure 45) . Two
changes are important. First, the concentrations were even
more depressed and extend from 10 to 40 meters. Second, the
surface nutrient values had increased indicating physical
effects (upwelling, currents) are mixing higher nutrient
waters in the upper 10 meters. This station was the first
where significant spikes were found in the surface values
caused by sampling at zero versus 13.5 foot depths. The
strong negative gradient observed in the upper 10 meters of
the vertical profile explain the differences observed.
Figures 47 and 48 illustrate profiles of stations D-25
and D-20 (leg 5A, Figure 22) . Station D-25 was located in
103
Figure 45. Vertical Profile Leg Four Station 6
104
Figure 46. Vertical Profile Leg 5A Station D-30
105
Figure 47. Vertical Profile Leg 5A Station D-25
106
2 0 .1 4 0 0
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0.2
0.3
87.10 miles
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Figure 48. Vertical Profile Leg 5A Station D-20
107
a nutrient plateau region. Station D-20 was located in a
surface bloom area and closely follows those found in leg
three and four blooms (Figure 44).
Figure 49 and 50 illustrate adjacent stations D-15 and
D-12.5 (2.5 miles apart) (Figure 22). These stations were
noticeably different, especially in the upper 30 meters.
Again a depressed region is found from 10 to 20 meters for
station D-15 but lacking in station D-12.5. The concentra-
tions at all depths increased notably over those found
farther to sea, indicating upwelling was more significant.
Figures 51 and 52 illustrate another pair of stations
located in the leg 5B upwelling area (Figure 33) . Station
D-10 showed a strong positive concentration gradient with
depth. Station D-7 indicated the common surface to 10 meter
negative concentration gradient below which was found a
strong increase in concentrations with depth.
The remaining vertical profiles had many of the same
characteristics discussed above relating to the different
areas sampled.
108
Figure 49. Vertical Profile Leg 5B Station D-15
109
Figure 50. Vertical Profile Leg 5B Station D-12.5
110
NO,
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20
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202100
97.50 miles
20. 0
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30
Figure 51. Vertical Profile Leg 5P Station D-10
111
Figure 52. Vertical Profile Leg 5B Station D-7
112
VI I . DISCUSSION OF RESULTS
Some discussion was included with the data presentation
of this study in an attempt to explain and clearly indicate
meaningful results obtained. Further discussion is believed
necessary to bring together the various areas and differing
methods used in the data presentation. Also, some develop-
ment is desirable to explain the major nutrient variations
found.
A. VARIABILITY AND CONCENTRATION CORRELATIONS
All data obtained during this study have been presented.
No attempt was made to discard any results because they
didn't fit a particular criterion or correlate with surround-
ing values. One sample point was thrown out, however, because
one nutrient value indicated contamination and drove the
recorder off scale (estimated 130%). The correlations of
the three major nutrients throughout this study indicated
extremely close effects from physical (mixing, upwelling,
etc.) and biological influences. This result was expected
for the phosphate and nitrate variations but was not expected
to be as close for the silicate variations influenced by
differing biological mechanisms. The nitrite variations did
not change directly with the other nutrients but did show
an indirect relationship with nitrate concentrations in areas
of high biological activity. This result was expected.
113
All major nutrients in the surface waters and the mixed
layer varied over a wide range of concentrations for the
area and times studied. Table V indicates the max-min
values obtained from this study. As the results presented
clearly indicate, not only do the concentrations vary
greatly, but change significantly in small horizontal dis-
tances and vertical depths. It is obvious that data
obtained from relatively widely spaced stations and taken
at intervals from weeks to years can not be used for mean-
ingful comparisons or as an accurate indication of water
type in the photic zone of the oceans.
TABLE V
MAXIMUM-MINIMUM NUTRIENT CONCENTRATIONS
FOUND IN THE PHOTIC ZONE (ygat /l)
SILICATE
MAX MIN
PHOSPHATE
MAX MIN
NITRATE
MAX MIN
Surface
Subsurface
32.63 0.0
34.21 0.0
1.72 0.14
2.34 0.19
24.18 0.0
26.21 0.36
B. UPWELLING SIGNATURES
Three upwelling area signatures have been obtained and
discussed (Figures 25, 29, and 33). The last (Figure 33)
was investigated more thoroughly than the others. A verti-
cal contour plot of isolines of equal silicate concentration
114
10
25
20 15 w
DISTANCE FROM LAND (MILES)
Figure 53.
Vertical Contour Plot of Silicate Isolines
in Upwelling Area Leg 5B.
116
along legs three and four (Figures 30 and 31) of cruise four,
The results as presented are difficult to understand, because
of a complicated ship track in that area. Figure 54 illus-
trates the limits of the bloom/plateau boundaries along the
track as discussed for legs three and four. The data
obtained represents only two plateau regions. The larger
region contains stations 2, 3, 4, and 6 while the smaller
region encloses no stations. Stations one and five are
close together outside the plateau in a bloom area. The
limits of the plateau regions parallel to the track are
estimated from the dimensions of the actual boundaries
obtained along the track. The axis of the plateaus closely
parallels- the submarine canyon valley and may be indicative
of vertical water motions from the canyon maintaining the
nutrient surface levels. Further data must be obtained in
this area.
D. BAY AREA VARIATIONS
Three Monterey Bay area signatures were obtained; cruise
three (Figures 26 and 27) , cruise four leg one (Figure 28)
and cruise four leg six (Figure 34) . These surface signa-
tures significantly differ from each other although they
were along much of the same track location. This indicates
the variation in data obtained when sampling at intervals of
a few days or weeks. Cruise three data, as discussed
earlier, were highly variable with a significant plateau
developing in the outer area. Cruise four data showed
a more constant distribution over the Monterey Canyon. This
117
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o
LD
o
o
ro
118
may have been caused by either intensification of circula-
tion above the canyon or a reduction in biological activity
in the surface waters. Data were insufficient to confirm
either condition.
E. RATIO ANALYSIS
Nutrient ratios for SilicaterPhosphate, Silicate:Nitrate,
Nitrate : Phosphate , and Total Nitrate: Phosphate were calcu-
lated for all data obtained.
1 . Area Identification by Surface Ratios
An evaluation of the calculated surface ratios was
attempted to determine if the surface ratio values would
identify the water masses found earlier from concentration
distribution patterns. All ratios associated with the
earlier upwelling plateau regions, open sea nutrient pla-
teaus, planktonic bloom areas, and Bay area plateaus were
separated, analysed, and averaged. The results are indi-
cated in Table VI. The differences between maximum and
minimum values for all ratios and all areas are quite
significant and do not show paricularly constant results
throughout a specific area. -The average values for the
determined ratios, however, do seem to be more representa-
tive of the water masses. The values for the specified
areas of interest do show some interesting results. The
highest surface nutrient concentrations were found in the
strongest upwelling areas and generally decreased seaward.
The nutrient ratios, however, for the upwelled areas were
119
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121
jantly different from the open sea plateau
lis forces the conclusion that the change in
eventration was from circulation and mixing
utrient ocean waters, resulting in a dilution
(L reduced the concentrations but maintained
i: proportions. The ratios determined from open
reas were drastically different from the others.
:;;ios (SiO.rPO. and SiO.rNO.) had been depressed
>:> but the N03:P04 and Total NO-rPO. ratios,
jailer than before, were still significant. This
j> that for these areas studied the silicate is
l;j nutrient for the biological population. This
Jh generally recognized [Riley and Skirrow 1965] .
ra plateau ratios appear to show significantly
las than those found in the other nutrient plateau
lis effect may be partially caused by a greater
otion due to river runoff into the Bay.
g5nty Meter Ratio Stability
orients have been used by some investigators
1 Chow and Mantyla 1965] as a quasiconservative
eabling them to identify intermediate and deep
Is. Apparant oxygen utilization and deep ocean
eventrations have been found to be related
:sand Kester 1966] . The assumption is made that
lof nutrients found just below the photic layer
he mixed layer consists of preformed nutrients
'( is zero). These values are believed to be quite
122
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125
the data are somewhat limited and do show some spread , the
results (Table IX) appear significant. The average values
obtained for ANC>3 : APO. and ATotal NO.. : APO. of 16.33
and 16.46, respectively, are in close agreement with the
16 : 1 ratio given by Fleming [1940] for average plankton.
This value was also confirmed by Grill and Richards [196 4]
in laboratory studies of decomposing phytoplankton . The
average value obtained for ASiO. : APO. was 21.14. This
is much different from the value of 16.00 suggested by
Richards [1958]. It does agree very well with the ASiO.:
A/PO. ratio of 23:1 obtained in laboratory decomposition
studies [Grill and Richards 1964]. Figures 55 and 56 are
correlation diagrams of Table IX data. The high value of
SiO./PO. assimilation ratio is again an indication of sili-
cate as the limiting nutrient. In no samples tested was
the SiO^/PCK ratio this high. The NO /PO. assimilation
ratio determined from Table IX is close to that found in
the 70 meter samples (Table VII) . Additional data and
further studies in this area are considered promising.
F. TIME VARIATION STUDY '
One additional result of this study must be included.
During the period at anchorage outside Monterey Harbor on
19 May 1972, surface samples were taken at 10 minute
intervals for four hours. The results of these time vari-
ations are indicated in Figure 57. Although the variations
were small, the nutrients do seem to correlate quite well
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Figure 57. Surface Nutrient Time Variations 19 May 1972
130
and indicate the sensitivity of the analytical techniques.
The tide record is shown for this time period.
Phosphate and nitrate concentration levels appear to
have a minimum at time 09 50. This was also the time of low
tide. Superimposed on the apparent nutrient tidal changes
are oscillations. Phosphate and nitrate show oscillations
with a 20 minute period over about 40% of the record. These
oscillations appear real and may be caused by langmuir cir-
culation [Langmuir 19 38] patterns in the surface waters as
the water mass moved by the ship in the tidal current. This
would explain why the oscillations stopped during the time
of low tide when outflow stopped and before significant
inflow had developed. Nitrite and silicate data also show
an oscillation tendency (silicate period of 40 minutes end
nitrite period of 20 minutes) . Insufficient data prevents
further evaluation but these suggest an area for further
study. Results indicate nutrient variations caused by
surface circulation and internal wave motions may be deter-
mined by sampling at closer time intervals (1-2 minutes) or
continuously without wash separation [Armstrong and LaFond
1966] .
131
VIII. SUMMARY AND CONCLUSIONS
This study has demonstrated the capabilities of the
Techmcon AutoA.nalyzer II System. The sensitivity, repro-
ducibility, and accuracy of this system for sea water
nutrient analysis have been found to be very satisfactory.
The system was capable of operating at sea, even under
adverse weather conditions, and accurate, meaningful data
were obtained.
Results obtained were examined in light of the many areas
of biological and physical oceanography which might be
studied "using these high resolution techniques. The high
nutrient variations in the sampling area have been presented
and explanations for them offered. Upwelling areas have
been investigated for nutrient concentrations, circulation
patterns, and variations in nutrient ratios. Planktonic
bloom areas have been identified from the low nutrient levels,
low nutrient ratio values and high chlorophyll correlations.
Results indicate that silicate was the biological limiting
nutrient in the waters studied. Vertical nutrient profiles
have been presented for the areas studied. The biological
and physical influences on these profiles have been discussed
and separated. Assimilation ratios for biological activity
of 16.33 for N03:PO. and 21.14 for SiO.tPO. were obtained
which agree well with laboratory decomposition values.
Nutrient plateau regions have been analysed and sources
132
discussed. The major cause of nutrient concentration
changes in the area (outside the blooms) studied appears
to be mixing caused by circulation patterns which reduce
the concentrations while maintaining nutrient ratios.
Areas of further investigation have been identified
throughout this paper. Additional evaluation and improve-
ments in sampling techniques, operating procedures, and
data processing have been identified. Additional investiga-
tion in promising areas of mixed layer circulation and
biological/physical relationships with nutrient variations
have been indicated.
Three major conclusions have resulted from this study:
1. ~ _S-atisf actory automated equipment exists which
permits high resolution real-time study of oceanic processes
which affect nutrient concentrations.
2. Among the environmental processes that may be
studied are biological processes, mixing internal waves,
tidal variations and circulation patterns such as Langmuir
cells .
3. The possibility of real-time measurements should
allow better field decisions when interesting phenomena
are encountered.
133
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LIST OF REFERENCES
nstrong, F. A. J. and LaFond, E. C, "Chemical Nutrient
Concentrations and Their Relationship to Internal
Waves and Turbidity Off Southern California,"
Limnology and Oceanography, v. 11, p. 538-547, 1966.
nstrong, F. A. J., Sterns, C. R. and Strickland, J.D.H.,
"The Measurement of Upwelling and Subsequent Bio-
logical Processes by Means of the Technicon Auto-
Analyzer and Associated Equipment," Deep-Sea Research,
v. 14 (3) , p. 381-389, 1967.
2gon State University Technical Report 215, A Practical
Manual for Use of the Technicomv AutoAn a lyz erffi"~in
Seawater Nutrient Analyses; Revised, by E . L. Atlas,
L. I. Gordon, S. W. Hager, and P. K. Park, p. 48,
September 1971.
*wer, P. G. and Riley, J. P., "The Automatic Determina-
tion of Nitrate in Sea Water," Deep-Sea Research,
v. 12, p. 765-772, 1965.
-
in, K. M. and Riley, J. P., "The Automatic Determina-
tion of Phosphate in Sea Water," Deep-Sea Research,
v. 13, p. 467-471, 1966.
w, T. J. and Mantyla, A. W. , "Inorganic Nutrient
Anions in Deep Ocean Waters," Nature , v. 206 n4982,
p. 383-385, 24 April 1965.
liming, R. H. , "The Composition of Plankton and Units
for Reporting Populations and Production," Proceed-
ings of the 6th Pacific Sci. Congress Pacific Sci.
Ass. Vancouver, v. 3, p. 535-540, 1940.
Usshof f , K. , A Simultaneous Multiple Channel System
for Nutrient Analysis in Seawater with Analog an d
Digital Data Record, paper presented at Technicon^
International Congress, Chicago, Illinois, 4-6 June
1969.
usshoff, K. , Automatic Determination of Fluoride,
Phosphate, and Silicate in Sea Water, paper presented
at Technicon1^ Fifth International Symposium, London,
England, 13 October 1965.
150
10. Grill, E. V. and Richards, F. A., "Nutrient Regenera-
tion from Phytoplankton Decomposing in Seawater,"
Journal of Marine Research, v. 22(1), p. 52-69, 1964.
11. Johnson, D. L. , "Simultaneous Determination of Arsenate
and Phosphate in Natural Waters , " Environmental
Science and Technology, v. 5(5), p. 411-414, May 1971.
12. Killion, R. A., A Multivariant Analysis of Physical and
Chemical Properties Observed in the Ocean, M.S. Thesis,
Naval Postgraduate School, Monterey, California,
September 1972.
13. Langmuir, I., "Surface Motion of Water Induced by Wind,"
Science, v. 87, p. 119-123, 11 February 1938.
14. Instituto de Investigaciones Pesqueras Technical Report
AD 70 246 8, Organization and Distribution of Phyto-
plankton Communities, by R. Margalef and others,,
p. 16, 30 January 1970.
15. Molof, A. H. , Edwards, G. P., and Schneeman , R. W. ,
An Automated Analysis for Orthophosphate in Fre s h
and Saline Waters , paper presented at Technicon®"
" — Symposium, New York, N. Y. , 8 September 1965.
16. Murphy, J. and Riley, J. P., "A Modified Single Solution
Method for the Determination of Phosphate in Natural
Waters," Anal. Chim. Acata, v. 27, p. 31-36, 1962.
17. Park, K., "Nurtient Regeneration and Preformed Nutrients
off Oregon," Limnology and Oceanography, v. 12(2),
p. 353-357, April 19 67.
18. Pytkowicz, R. M. and Kester, D. R.f "Oxygen and Phos-
phate as Indicators for the Deep Intermediate Waters
in the Northeast Pacific Ocean," Deep-Sea Research,
v. 13, p. 373-379, 1966.
19. Riley, J. P. and Skirrow, G., Chemical Oceanography, v. 1,
Academic Press, 1965.
20. Stavn, R. H. , "The Horizontal-Vertical Distribution
Hypothesis: Langmuir Circulation and Daphnia Distri-
butions," Limnology and Oceanography, v. 16(2),
p. 453-466, March"l971.
21. Strickland, J. D. H. , and Parsons, T. R. , A Practical
Handbook of Seawater Analysis, p. 119-138, Fisheries
Research Board of Canada, 1968.
151
INITIAL DISTRIBUTION LIST
No. Copies
1. Defense Documentation Center 2
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Naval Postgraduate School
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732 North Washington Street
Alexandria, Virginia 22314
4. Office of Naval Research, Code 4 80 1
Arlington, Virginia 22217
5. Naval Oceanographic Office (Tech Director) 1
Suitland, Maryland 20390
6. Department of Oceanography (Code 58) 3
Naval Postgraduate School
Monterey, California 93940
7. Assoc. Prof. Noel E. J. Boston (Code 58) 2
Department of Oceanography
Naval Postgraduate School
Monterey, California 93940
8. Assoc. Prof. Charles F. Rowell (Code 61) 2
Department of Physics/Chemistry
Naval Postgraduate School
Monterey, California 93940
9. Assoc. Prof. Eugene D. Traganza (Code 58) 2
Department of Oceanography
Naval Postgraduate School
Monterey, California 93940
10. Asst. Prof. Robert H. Bourke (Code 58) 1
Department of Oceanorgaphy
Naval Postgraduate School
Monterey, California 93940
11. Asst. Prof. Stevens P. Tucker (Code 58) 1
Department of Oceanography
Naval Postgraduate School
Monterey, California 93940
152
12. Mr. Robert M. Gasko, Manager
Technicon Industrial System
Tarry town, New York 10 591
13. Mr. Elliot L. Atlas
Department of Oceanography
School of Science
Oregon State University
Corvallis, Oregon 97331
14. Mr. Donald Seibert (C127)
National Marine Fisheries Service
Southwest Fisheries Center
LaJolla, California 92037
15. LCDR Gaylord O. Paulson, USN
358 San Miguel Drive
Chula Vista, California 92011
16. LT Robert A. Killion, USN
USS SAILFISH SS572
FPO San Francisco, California 96601
153
UNCLASSIFIED
Security Classification
— nan iimirfiiT i iiit — ~~ ~*
DOCUMENT CONTROL DATA -R&D
{Security das si licetion of title, body ot abstract and indexing annotation must be entered when the overall report Is clr ssltied)
41 G in A Ti NC ACTIVITY (Corporate author)
Naval Postgraduate School
Monterey, California 93940
2a. REPORT SECURITY CLASSIFICATION
Unclassified
2b. GROUP
A STUDY OF NUTRIENT VARIATIONS IN THE SURFACE AND MIXED LAYER OF
MONTEREY BAY USING AUTOMATIC ANALYSIS TECHNIQUES
EPOR T TITLE
ESCRIPTIVE NOTES (Type ol report and.lnclusive dates)
Master's Thesis; September 19 72
UTHORIS) (Firsl n«m», middle Initial, la tt name)
Gay lord O. Paulson; Lieutenant Commander, United States Navy
EPOR T D A TE
September 1972
7«. TOTAL NO. OF PAGES
155
7b. NO. OF REFS
21
CONTRACT OR GRANT NO.
PROJEC T NO.
Ba. ORIGINATOR'S REPORT NUMfcER(3)
8b. OTHER REPORT NOISI (Any ol/ief numboM that may be at clgnad
till.: report)
I DISTRIBUTION STATEMENT
Approved for public release; distribution unlimited
SUPPLEMENTARY NOTES
12. SPONSORING MILITARY ACTIVITY
Naval Postgraduate School
Monterey, California 93940
ABSTKAC T
Concentrations of silicate, phosphate, nitrate, and nitrite were
determined in Monterey Bay, California. Data were collected aboard
ship during four cruises in April and May 19 72 using the Technicon®
lAutoAnalyzer® n System in dual channel operation. The sensitivity,
-reproducibility, and accuracy of this system were investigated and
the results presented. Nutrient concentrations were presented as
I surface variations, depth variations, and vertical profiles. The
large variability of nutrient concentrations in the ocean area
studied was discussed. Upwelling areas were investigated for nutrient
concentrations, circulation patterns, and variations in nutrient
ratios. Planktonic bloom areas have been identified from the low
nutrient levels, low nutrient ratio values, and high chlorophyll
correlations. Results indicate that silicate was the limiting
nutrient to biological activity in the waters studied. Assimilation
ratios for biological activity were found to be 16.33 for N03:P04 and
21.14 for Si04:P04. Nutrient plateau regions were analysed and
sources discussed. The major cause of nutrient concentration changes
, in the area (except plankton blooms) as determined from nutrient
ratio studies was found to be circulation of the water masses.
FORM
lofi I NOV 86
N 010! -807-681 1
1473
(PAGE 1)
UNCLASSIFIED
154
kf-cority Classification
i-31408
UNCLASSIFIED
Security Cla?; ifirotion
KEY WO RDI
SEAWATER
NUTRIENTS
SILICATE
PHOSPHATE
NITRATE
NITRITE
ANALYSIS
AUTOMATED
CHEMICAL ANALYSIS
AUTOANALYZER
NUTRIENT RATIOS
CENTRAL CALIFORNIA COAST
NUTRIENT DISTRIBUTION
CIRCULATION
MONTEREY BAY, CALIFORNIA
NUTRIENT TIME VARIATIONS
NUTRIENT DEPTH VARIATIONS
SEAWATER CHEMISTRY
TECHNICON
NUTRIENT VARIATIONS
ORTHOPHOSPHATE
INORGANIC NITRATES
INORGANIC NITRITES
REACTIVE SILICATES
INORGANIC NITROGEN . COMPOUNDS
BIOLOGICAL POPULATION
ASSIMILATION RATIOS
BIOLOGICAL ASSIMILATION
PLANKTON
PLANKTON DISTRIBUTION
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iQ F0RM
t^ i no v e»
N 0101-807-6821
(BACK)
155
UNCLASSIFIED
Security Classification
A- 3 1 409
29 JAN79
596
Thesis
P274
c.l
141369
Paulson
A study of nutrient
variations in the sur-
face and mixed layer
of Monterey Bay using
automatic analysis
techniques.
29 JAM79
506
Thesis
P274
c.l
141369
Paulson
A study of nutrient
variations in the sur-
face and mixed layer
of Monterey Bay using
automatic analysis
techniques.
Astudy of nutrient variations in the su
3 2768 001 98091 5
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