wEPA
United States
Environmental Protection
Agency
Office of Water
{WH-S56F!
EPA 842^8-92-007
June 1992
Final Data Report for
Analysis of Water Quality
Samples Taken During a
New York Bight Survey
in July 1988
106 Mile
Dump Site
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FINAL DATA REPORT
ANALYSIS OF WATER QUALITY
SAMPLES TAKEN DURING A
NEW YORK BIGHT SURVEY IN JULY 1988
December 8, 1988
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office, of Marine and Estuarine Protection
Washington, DC
and
Region II
New York, NY
Prepared Under Contract No. 68-03-3319
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TABLE OF CONTENTS
Page
1. 0 INTRODUCTION 1
1.1 Objectives 1
1.2 Survey Area , 1
2.0 SAMPLING AND ANALYTICAL METHODS 3
2.1 Methods for Collection and Analysis of
Trace Metal Samples 3
2.2 Methods for Collection and Analysis of
Nutrient Samples 5
3.0 RESULTS 7
3.1 Trace Metal Results 7
3.2 Nutrients 7
4 . 0 REFERENCES 11
LIST OF APPENDICES
Appendix A. Automated Analysis of Nutrients
in Seavater: A Manual of Techniques
Provided by Dr. Theodore C. Loder of the
University of New Hampshire A-l
Appendix B. Summary of the Hg Results for Samples
Collected During the July 1988 New York
Bight Survey B-l
Appendix C. Summary of Trace Metals Data (Excluding Hg)
for Samples Collected During the July 1988
New York Bight Survey C-l
Appendix D. Summary of the Nutrient Results
for Samples Collected During the July 1988
New York Bight Survey D-l
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LIST OF TABLES
Paqe
Table 1. Summary of the Samples Collected During the New
York Bight Water Quality Survey.
Table 2, Summary of the Data Requirements for Seawater
Samples Collected in the New York Bight,
Table 3. Method Detection Limits (//g/L) for Analysis of
Metals From the New York Bight July 1988 ,
Table 4
Procedural Blanks (//g/L) Determined for the
Analysis of Water Samples Collected From the
New York Bight in July 1988
4
6
8
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LIST OF FIGURES
Page
Figure 1. Station Locations for Samples Collected
During the New York Bight Survey in
July 1988 2
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1.0 INTRODUCTION
In support of the New York Bight Restoration Plan/ Region II
of the U.S. Environmental Protection Agency (IPA) conducted a
survey from 3tily 5-8, 1988, in the New York Bight to collect water
quality samples. The following report presents the results of
these analyses. Section 1.0 discusses the objectives and study
area of the survey. Section 2.0 describes the collection,
processing, and analytical methods. Section 3.0 presents the
analytical results and quality control (QC) data.
1.1 OBJECTIVES
Two objectives were accomplished during the survey. The
first objective was to collect samples for water quality measure-
ments from selected stations within the Bight. The second
objective was to analyze those samples for the following trace
metals and nutrients:
1. Total Dissolvable Trace Metalscadmium (Cd), copper
(Cu), nickel (Ni), lead (Pb), zinc (Zn), iron (Fe),
and mercury (Hg).
2. Nutrientstotal phosphorus (Tot P) total nitrogen
(Tot N)i total and dissolved orthophosphorus (PO.)j
ammonia nitrogen (NH.), nitrate (NO.,), nitrite (N0~);
JS * i » if** ^% % * ' " **
and silica (Sio,).
1.2 STUDY AREA
The study area consisted of three transects (A, B, and C)
located in or near the boundaries of the New York Bight. Figure 1
shows the study area and the locations of each transect and
associated stations.
Transect A15 stations circumscribing the entire
Bight area from Long Island to Cape May.
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75 '00'
74 °00'
41'00'-
40'00' -
FIGURE 1. STATION LOCATIONS FOR SAMPLES COLLECTED DURING THE NEW YORK BIGHT
SURVEY IN JULY 1988.
2
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Transect B12 stations circumscribing the Apex of the
Bight.
Transect C15 stations extending from Governors
Island, New York, through the mouth of the
Hudson-Raritan Bay and into the Apex of
the Bight.
2.0 SAMPLING AND ANALYTICAL METHODS
Trace metal and nutrient samples were collected at selected
stations during the survey. Table 1 summarizes the samples
collected for all analytes.
2.1 METHODS FOR COLLECTION AND ANALYSIS OF TRACE METAL SAMPLES
During the survey, 65 samples for analysis of acid-soluble
total Cd, Cu, Fe, Hi, Pb, and Zn were collected from 26 selected
stations along the three designated transects (A, B, and C).
Acid-soluble total metal is defined for these metals as the
dissolved and the particulate fraction obtained following
acidification of unfiltered samples to a pH of 2, Samples were
collected from the surface and pyconocline at 8 stations along
Transect A, 6 stations along Transect B, and 12 stations along
Transect C (a total of 52 samples). In addition, samples were
collected in duplicate from each depth at 5 stations {a total of
12 duplicate samples). One field blank was also collected during
the survey.
Samples for acid-soluble total Hg determinations were
collected at the same 26 stations sampled for the other trace
metals. The Hg samples were composite samples obtained by
combining approximately 500 mL from surface seawater and 500 mL
from pycnocline seawater into 1-L containers (a total of 26
samples), in addition, one field blank and one duplicate were
collected. Acid-soluble total dissolvable Hg is defined here as
the dissolved metal and the particulate fraction obtained
following acidification of the unfiltered sample to a pH of 1.
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TABLE 1. SUMMARY OF THE SAMPLES COLLECTED DURING THE HEW YORK BISHT HATER
QUALITY SURVEY
Analyte
Trace Metals
Mercury^
Nutrients
Surface
26
26
39
Samples
Subpycnocl i ne Bl anks
26 1
1
3
Other
QC
12
1
0
Total
65
28
78
aSurface and pycnocline samples composited Into a single sample.
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Samples for total trace metals (Cd, Ni, Cu, Pb, Zn, Fe, and
Hg) were collected and processed according to EPA standard
operating procedures (SOPs 5-01 and 6-01) prepared by Battelle for
EPA under the 106-Mile Site monitoring program { EPA , 1987a).
Stations were sampled using GO-FLO bottles. Aliquots were then
transferred to Teflon containers for subsequent Hg determinations,
and to polyethylene containers for the remaining trace metals.
Each 1-L Hg sample was acidified with 5 mL high-purity nitric
acid. The samples collected for the other metals were acidified
with 1 mL nitric acid per liter of sample.
Hg samples were analyzed in accordance with SOP 4-55
( EPA , 1987b). The other trace metal samples were analyzed in
accordance with SOP 4-53 ( EPA , 1987b). The analytical
requirements for all targeted analytes are presented in Table 2.
To verify precision and accuracy of analytical measurements, a
number of quality control samples were analyzed. Precision
(expressed as relative percent difference) was estimated from the
variation in the results of duplicate samples. Analytical
accuracy was determined from standard reference materials (when
available), from a matrix spiking exercise, or both and expressed
as percent recovery in each case,
2.2 METHODS FOR COLLECTION AND ANALYSIS OF NUTRIENT SAMPLES
Seventy-eight dissolved and total nutrient samples were
collected at 39 stations along the three transects: 16 stations
along Transect A, 11 stations along Transect B, and 12 stations
long Transect C, At each station samples were collected from two
depths, the surface and the pycnocline. Three 20-mL subsamples
were collected from each sample; two .were filtered for analysis of
dissolved nutrients, and the unfiltered sample was analyzed for
total nitrogen and phosphorus.
Samples for dissolved (PO^, NH,, NO,, NO2, and SiO*) and
total nutrients were collected in accordance with SOP 6-01
{ EPA , 1987a). For the dissolved fraction, two 20-mL
subsamples were filtered into polyethylene bottles and stored
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TABLE 2. SUMMARY OF THE DATA REQUIREMENTS FOR SEAWATER SAMPLES COLLECTED IH THE HEW YORK BIGHT
Parameter
Seawater Metals
Hg
Cd, Zn, Cu, Pb
Fe, Ni
Nutrients*
Total Phosphorus
Total Nitrogen
NH4-Nb
H03-Hb
N020-Nb
P04-PC
Si02-Sid
Units
W/L
/»g/L
«/L
pmo]/L
/*g/L
imol/L
MJ/L
imol/L
M/L
janol/L
H9/L
/dnol/L
«/L
/imol/L
M/L
/tmol/L
^g/L
Detection
Limit
0.0002
O.OOi
0.050
0.08
2.5
2.5
6.0
0.08
1.1
0.04
0.5
0.02
0.3
0.02
0.6
0.08
2.2
Accuracy
50
50
50
30
30
30
30
30
30
30
Precision
30
30
30
10
10
10
10
10
10
10
Method
Gold amalgamation, Hg analyzer
Chel at ion -extract ion, GFAA
Chel at ion -extract ion, GFAA
3-channel Technicon auto
analyzer
3-channel Technicon auto
analyzer
3-channel Technicon auto
analyzer
3-channel Technicon auto
analyzer
3-channel Technicon auto
analyzer
3-channel Technicon auto
analyzer
3-channel Technicon auto
analyzer
^Detection limits for nutrients = 2x standard deviation for triplicate analysis of standards.
^Detection limits for nitrogen containing NO2, NO3, NH4 reported as ^g/L of Nk
CDetection limits for phospates containing P04 reported as /*g/L of P.
^Detection limits for silica contining SiOg reported as /*g/L of Si.
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frozen until analysis. For the total fraction, one 20-mL
unfiltered subsample was stored frozen in polyethylene bottles
until analysis.
These samples were subsequently processed and analyzed
according to the protocol entitled "Automated Analysis of
Nutrients in Seawater: A Manual of Techniques" (Appendix A).
Analytical requirements for the targeted nutrients are presented
in Table 2.
3.0 1ESULTS
The analytical results for all samples collected during the
New York Bight Survey (July 1988) are presented in Appendices B, C
and D.
3.1 T1ACE METALS
3.1.1 Analytical Results
All Hg data are presented in Table B-l of Appendix B. Only
general conclusions can be drawn from these Hg data, because
surface and pycnocline aliquots were combined to form a single Hg
sample.
The concentrations of Cd, Cu, Fe, Ni, Pb and Zn determined
from New York Bight samples are tabulated in Appendix C (Table
C-l). In general, the consistency the data set for metals
indicates a contamination-free sampling effort.
3.1.2 QUALITY CONTROL ANALYSIS
Tables 3 and 4 list the method detection limits and
contribution of metals to the analytical results from the
procedural blanks. All field samples contained metal
concentrations that were well above the method detection limits
for all metals determined. The metal data have been corrected for
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TABLE 3. METHOD DETECTION LIMITS («/L) FOR ANALYSIS OF METALS IN SAMPLES
COLLECTED FROM THE NEW YORK BI6HT IN JULY 1988
Cd Cu Fe Ni Pb Zn Hg
0.002 0.03 0.10 0.02 0.004 0.01 0.00015
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TABLE 4. ANAYTE COKTENT (fQ/l) IN THE PROCEDURAL BLANKS ASSOICATED WITH THE
SAMPLES COLLECTED FROM THE NEW YORK BIGHT IN JULY 1988
Sample
ID
GI52-PB
GI53-PB
GI56-PB
6I57-PB
GI48-PB
GI49-PB
GH66-AB
GH67-AB
GH72-AB
GH73-AB
6H88-AB
GH89-AB
GH94-AB
G101-AB
GI02-AB
Cd* Cua Fea
0.016 0.09 2.37
0.016 0.18 1.90
0.005 <.02 0.13
0.005 <.02 0.13
0.005 <.01 <.10
0.005 <.01 <.10
- _ _
-
-
_ _ _
-
-
- -
.
Nia
7.89
8.06
0.06
0.04
<.02
<.02
_
_
_
_
-
-
-
_
"
Pba
0.013
0.013
<.003
<.003
0.004
<.004
_
_
-
.
-
-
-
-
Zna
0.09
0.09
0.02
0.02
0.01
0.07
-
-
-
.
-
.
-
-
Hgb
0.000790
0.000694
0.000238
0.000266
0.000362
0.000322
0.000092
0.000022
0.000002
aCa1culated using an extract volume of 2 mL and a sample volume of 200 ml.
^Calculated using a sample volume of 500 ml.
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blanks where the analyte blank concentrations were consistent
within a processing batch. All of the metal data generated met the
precision and accuracy criteria outlined in Table 2, with the
exception of the duplicate Hg analyses (Tables B-2 and 3,; C-2,3,
and 4). The Hg precision results were determined to be 31 and 36
(RPD), falling outside of the specified limit of 30 percent. Two
of ten blank samples spiked with a known amount of Hg fell outside
of the 50 percent recovery criterion. The two field samples
spiked with Hg resulted in recoveries of 53 and 73 percent.
3.2 NUTRIENTS
Results for all nutrient samples collected during the survey
are presented in Table D-l of Appendix D. Concentrations of NH4,
NO,, and PO. from unfiltered samples were not required. However,
because the analyses were performed and the data are available,
the values are reported. All nutrient values are reported in
micromoles per liter (>uM).
The nitrate data from filtered samples for Transects A and B
indicate that many of the filtered samples may have been contami-
nated during filtration. The values for NO, are considerably
higher (in some cases an order of magnitude or greater) than those
for Total N analyzed froin the unfiltered samples. High NO,
concentrations may have been caused by cross contamination from
nitric acid used in processing the trace metal samples. Dissolved
nitrate values can be estimated for the contaminated samples by
using the NO, results from the unfiltered fraction if it is
understood that some of the NO^ may be contributed by the
particulate fraction.
The ammonia data from Transects A and B indicate that some of
the samples (filtered and unfiltered) may have been contaminated
or that some of the ammonia may have volatilized from the samples
during processing and analysis. Although filtered samples
collected along Transects A and B appear to be contaminated with
NO, and NH, , those collected along Transect C show no evidence of
contamination. In addition, contamination from the other
10
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dissolved and total nutrient parameters is not evident in any of the samples
collected along Transects A, B, and C. This data set, with the exception of
N03 and NH^, falls within the quality conto guidelines described in the
protocol in Appendix A.
4.0 REFERENCES
EPA. 1987a. Quality Assurance/Quality Control (QA/QC) Document for the
106-Mile Deepwater Dumpsite Monitoring Program. Environmental
Protection Agency Oceans and Coastal Protection Division (formerly
QMEP), Washington, DC.
EPA. 1987b. Sampling and Analytical Procedures for the Ocean
Incineration Research Burn Program (RBSA Plans) Volumes I and II.
Environmental Protection Agency Oceans and Coastal Protection
Division (formerly OMEP), Washington, DC.
11
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APPENDIX A
AUTOMATED ANALYSIS OF NUTRIENTS IN SEAWATERi
A MANUAL OF TECHNIQUES
Provided by Dr. Theodore C. Loder
of the University of New Hampshire
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WHOI-77-47
AUTOMATED ANALYSIS OF NUTRIENTS IN SEAWATER:
A KAN UAL OF TECHNIQUES
Patricia M. Gilbert
and
Theodore C. Loder
WOODS HOLE OCEANOSRAPHIC INSTITUTION
Woods Hole, Massachusetts 02543
June 1977
TECHNICAL REPORT
Supported by the Ocecr. Industry Program of the
Woods Hole Oceanographic Institution.
Reproduction in whole or in part is permitted
for any purpose of the United States Government,
In citing this manuscript in a. bibliography,
the reference should be followed by the phrase:
UNPUBLISHED MANUSCRIPT.
Approved for Distribution;
Derek W. Spencer, Chairman
Department of Chemistry
-------
Table of Contents
I. Introduction 1
II. Nutrient Methods
1. Phosphate 2
2. Silicate 4
3, Nitrate + Nitrite 6
4. Nitrite 9
5. Ammonia 11
6. Urea 14
7. Total Nitrogen 16
8. Total Phosphorus 1?
9. Dissolved Organic Carbon 18
III. Operational Procedures
1, Set-Up 19
2. Standards and Calibration; Samples 20
3, Blank and Salinity Corrections 23
4. Shut-Down 27
5. Data Calculations 28
IV. Sensitivity and Reproducibility of Automated Analyses 33
V. General Maintenance and Troubleshooting
1, Maintenance 35
2. Troubleshooting 37
VI. Operating an AutoAnalyzer at Sea
1. Packing and Shipping an AutoAnalyzer 38
2. Setting Up and AutoAnalyzer on Board 39
3. Operating the AucoAnalyzer on Board 40
VII, References 41
Appendix I: Manufacturers and Suppliers of AutoAnalyzer Equipment 44
and Supplies
Appendix II: Recommended Sample Collection and Storage Procedures 45
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I. INTRODUCTION
This manusl is written for the person who has some familiarity with
the principles of automated chemistry. A few of the principles will be
repeated here, but for a more complete treatment of the topic the reader
is referred to the following articles: Technicon Industrial Systems,
Manual TNO-0210-00 (1970) and Snyder et al. (1976).
The fundamental feature of continuous flow automated chemistry is
the segmentation of the flow stream of samples and reagents with small
bubbles of air. The bubbles serve three primary purposes. First, the
bubbles in the fluid stream cause friction with the tubing, creating
turbulent rather than laminar flow; this keeps the liquids well mixed.
Second, the bubbles keep each sample separated from the next. Finally,
the bubbles continually scrub the walls of the tubing, thus removing any
traces of material adhering to the walls.
A second feature of continuous flow automated chemistry is that all
operational conditions are systematically maintained the same. Thus,
each sample is subjected to exactly the same quantity of reagents, the
same temperature, and the same mixing time as every other sample and
standard. This, therefore, eliminates the necessity to have reactions
go to completion, although many reactions do. This approach will not
decrease reliability or substantially affect the sensitivity, as each-
recorded result represents the sura of the measurements of a large number
of analyses performed on each sample. Thus, although a steady-state
completed reaction may not be achieved, each sample is repeatedly measured
at some constant percentage of steady-state.
This manual is intended to document the methods in use by the Univer-
sity of New Hampshire and Woods Hole Oceanographic Institution at the
time of this writing. It describes what the authors feel are the most
sensitive and reliable methods for the commonly determined nutrients in
seawater, and the problems associated with, each method.
The authors thank Gordon Smith (University of New Hampshire) for his
assistance in the preparation of this manual, and Roger Shepherd (Duke
Marine Laboratory) for teaching us the problems of operating an Auto-
Analyzer at sea.
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II. NUTRIENT METHODS
1, PHOSPHATE
The basic method is Technicon Industrial Method No. 155-71W (1973) ,
which -is a modification of the Murphy and Riley (1962) single solution
method. The method depends on the formation of a phosphomolybdate blue
complex, the color of which is read at a wavelength of 880 run.
Below are described the reagents used in the phosphate system. All
reagents should be ACS grade; all water should be distilled and deionized
(DDW) . DDW is also used as Sampler IV wash water and in setting Auto-
Analyzer baseline. We find a reagent blank absorbanee ranging from 0.01
to 0.02 using DDW as a sample (see Section III - 3).
4.9H H^SOz,: Add 136 ml cone H2S04 to 600 ml "DDW; after
dilute to one liter.
Diluent Water; Add 1.0 ml Wetting Agent A (Technicon Mo. TQ1-Q214)
to one liter DDW just before use. We recommend you do not use Levor IV
as a wetting agent even though it is recommended by Technicon,
Ammonium Molybdate; Dissolve 40g ammonium molybdate in one liter
DDW. Stable for several weeks.
Antimony Potassium Tartrate; Dissolve 0.75g antimony potassium
tartrate in 250 ml DDW. Stable for several months.
, Mixed Reagent: Dissolve 0.648 g ascorbic acid in 36 ml DDW; add 60 ml
4.9N H2S04, 18 ml ammonium molybdate solution and 6 ml antimony potassium
tartrate solution. Keep in amber bottle and use within 8 hrs. Makes
120 ml reagent, which is adequate for 8 hrs at & consumption rate of 13.8 ml/
hr.
The flow diagram for the system is shown in Figure 1.
_. Some operational notes for this method are summarized below.
a. A 40/hr 1:1 cam gives good, reproducible results
b. The colorimeter phototubes must be S-l (Technicon No. 199-BQ21-04)
c. The colorimeter must he in the Damp 1 mode
d. For routine analysis a STD CAL of 8.00 is used, giving a full
scale value of approximately 5.00 pg at/£
e. For a discussion of calibration and blank problems refer to
Sections III 2-3
£. 0.1 N NaOH should be used for 5 min at the beginning of set-up
to clean out system
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PHOSPHATE
l ST-T5 9^3-
HEATING BATH
LOftSTE
cat..
je. /
^H
Cift-N/^EW
1>0-OIO3 IT-O-O103
\ OflQQ 0000 -BUK/BL.K l^iLugMT
TH
>l*~°^OM ^^
D^M/U>^T I^Eftqf.NT
r^
COLORIMETER RECORDER
I.S"
SAMPLER IV
/HA..
I- 1
4-ubi
tvj
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II.
2. SILICATE
The method is basically Technicon Industrial Method No, 186-72W
(1973). The method Involves the formation of a silicomolybdate blue
complex, which is analyzed colorimetrically at a wavelength of 660 run.
Below are described the reagents used in the silicate system. All
reagents should be ACS grade; all water should be distilled and deionized
(DDW). DDW is also used as Sampler IV wash water and in setting Auto-
Analyzer baseline. We find a reagent blank absorbance ranging from 0.01
to 0.02 using DDW as a sample.
Ammonium Holybdate; Dissolve lOg ammonium tnolybdate in one liter
0.1 N H2S04 (prepare by diluting 2,8 ml cone H2S04 to one liter with DDW).
Stable for several weeks if stored in amber plastic. Should be discarded
if any precipitate forms in the solution.
Oxalic Acid; Dissolve 50g oxalic acid and dilute to one liter with
DDW. Stable for many months.
Ascorbic Acid; Dissolve 17.6 g ascorbic acid in BDW containing 50 ml
acetone; dilute .to one liter with DDW. Add 0.5 ml Lever IV Wetting Agent
{Technicon No. T21-0332). Stable for several weeks if refrigerated.
The flow diagram for the system is shown in Figure 2.
Some operational notes for this method are summarized below.
a. All volumetrics used for standards should be made of linear
polyethylene, to avoid contamination by leaching from the glass.
b. When analyzing only silicate or silicate in combination with
nitrite a 50/hr 6:1 cam should be used; when analyzing in combination with
any other nutrient a 40/hr 1:1 cam is recommended.
c. The colorimeter phototubes must be S-l (Technicon No. 199-B021-04).
d. The colorimeter must be in the Damp 1 mode.
e. For routine analysis a STB CAL of 5.00 is used, giving a full
scale value of approximately 50 ug at/&.
f. For a discussion of calibration and blank problems refer to
Sections III 2-3.
g. This is one reaction that does not go to completion; the degree of
completion is temperature sensitive^ Thus, care should be taken to ensure
that a given set of samples are analyzed under similar laboratory temperatures
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SILICATE
STT>
ftflM6£, 0 -
X
COLORIMETER
I i *v
towO r> rf\
SO mm P/C
RECORDER
QQQQ
OQQQ
SAMPLER IV
,
P/C
erve
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II.
3, NITRATE & NITRITE
The basic method for this analysis is Technieon Industrial Method
No. 158-71W/Tentative (1972), which utilizes copper-cadmium reduction
of nitrate to nitrite with NH^Cl as a buffer. For a discussion of the
problems associated with EDTA as the buffer choice (Brewer & Riley, 1965)
refer to Gilbert & Mlodzinska (1977).
Below are described the reagents in use in the nitrate system. All
reagents should be ACS grade; all water should be distilled and deionized
(DBW). DDW is also used as Sampler IV wash water and in setting Auto-
Analyzer baseline. We find a reagent blank absorbance ranging from 0.02
to 0.04 using DDW as a sample with the column In line.
Ammonium Chloride: Dissolve lOg NlfyCl and 3-4 pellets NaOH in one
liter of DDW. Stable for several months if refrigerated.
Color Reagent; Dissolve lOg sulfanilatnide and O.Sg N-1-napthylethylene
diamine dihydrochloride to one liter with 10% phosphoric acid. Add 0.5 ml
Brij35 (Technicon No. T21-0110). Stable for one month if refrigerated.
Cadmium Powder: Clean with concentrated BC1, rinse well (10-20 times)
with DDW. Treat cadmium with 2% w/v copper sulfate; swirl the mixture
until no blue color remains. Wash thoroughly with DDW (10-20 times).
Transfer the treated cadmium to a glass column using an eye-dropper or
Pasteur pipette. Insert a glass wool plug at each end of the column.
The flow diagram for the nitrate and nitrite system is shown in
Figure 3.
Some operational notes for this method are summarized below:
a) A A-way valve (Hamilton Syringe Co. No. 4mnmm4 (ML3300) inserted
just before the cadmium column greatly facilitates setup and
helps eliminate air bubbles in the column.
b) A 40/hr 1:1 cam gives best results.
c) The colorimeter phototubes must be S-10 (Technicon No. 199-BQ21-01).
d) The operational STD CAL will depend on the age and efficiency of
the column. For a new column a STD CAL of 3.00 gives a full scale
value of approximately 20 ug at/i.
e) For a discussion of calibration and blank problems refer to
Sections III 2-3.
f) When analyzing pore water samples, or samples with either a high
sulfide or high organic content, the following procedure is
recommended, A short column (3 cm or longer) of activated charcoal
-------
II.
3. NITRATE & NITRITE (Continued)
or of Atnberlite ion-exchange resin XAD-4 is inserted just before
the cadmium column in the cartridge. This will eliminate the
organics without affecting the nitrate concentration. The char-
coal or resin may be fitted into a piece of purple-white pump
tubing, which may be cut to the desired length. The type of
samples will determine what length column will be necessary,
and whether the charcoal or resin will work better. Slight
smearing of the peaks may be expected with this procedure. When
analyzing samples with this method it is best to run standards
after every 3-A samples, and to run at least duplicates on each
sample.
-------
NITRATE s NITRITE
a^ - 01
Oft I- 3.OO
, o-
Cu^Cd
25cm
TO P/C 4
flsre c
/B
L.MT
ftlfi.
, WHT/WHT
SAMPLER IY
P/C
irv«
-------
II.
4. NITRITE
The basic method for this analysis is Technicon Industrial Method
No. 161-71W, which is a modification of APHA (1977).
The only reagent utilised in the nitrite system is the color rea_gent>
which is prepared exactly as described under the discussion of the nitrate
+ nitrite method. DDH is used in the preparation of this reagent, as SampI
IV wash water, and in setting AutoAnalyzer baseline. We find a reagent bl<
absorbanee ranging from 0.02 to 0,04 using DDW as a sample.
The flow diagram for the nitrite system is shown in Figure 4.
Some operational notes for this method are summarized below:
a) A phase separator (Technicon No. 021-G001-01) helps"reduce noise
by eliminating the inter-sample bubble which may tend to bs 2
problem.
b) A 40/hr 4:1 or 50/hr 6:1 cam gives good, reproducible results.
c) The colorimeter phototubes must be S-10 (Technicon Mo. 199-B021-0:
d) For routine analysis a STD CAL of 8.00 will give a full scale
value of approximately 2 yg at/£.
e) For a discussion of calibration and blank problems refer to
Sections III 2-3.
f) He have, in the past, had noise in this system due to "bubble-dip"
in front of the flow cell when the pump phased just right with the
bubble position. This problem was solved by replacing the white/
white pull-through pump tube with an orange/orange, thereby reduc
ing the rate of pull through.
-------
NITRITE
o-
12 x
V4
o
TO
TUBE
COLORIMETER RECORDER
Ficure 4. Flow diacram for automnt
-------
II.
5, AMMONIA
The method described here is that of O'Connor and Miloski (1974),
with a few modifications, The basic method, however, was described by
Grasshoff and Johannsen (1972),
Below are described the reagents used in the ammonia system. All
reagents should be ACS grade; all water should be distilled and deionized
(DDW). DDW is also used as Sampler IV wash water and in setting Auto-
Analyzer baseline. We find a reagent blank absorbance ranging from.0,02
to 0,05 using DDW as a. sample.
Buffer: Dissolve each of the following separately, then mix and
dilute to 250 ml: 2.25 g boric acid, 30.0 g sodium citrate, and 0.5 g
sodium hydroxide. Stable for a few weeks if refrigerated.
Reagent A; Dissolve 8,75 g phenol and 0.1 g sodium nitroprusside and
make to 250 ml with DDW. Stable for a few weeks if refrigerated.
Reagent B; Dissolve 5 g sodium hydroxide and 0.5 g sodium dichloro-
s-triazine-trione (sodium dichloro-isocyanurate) and make to 250 ml with
DDW. Prepare fresh daily. This volume may be reduced depending on the
amount needed for a set of samples. Consumption rate is 6 ml/hr.
Some operational notes for this method are sutnmariEed below:
a) A phase separator (Technicon No. 021-G001-01) helps reduce noise
by eliminating the inter-sample bubble which may tend to be a
problem.
b) A 40/hr 1:1 will give good, reproducible results.
c) The colorimeter phototubes must be S-10 (Technicon No. 199-B021-01)
d) For routine analysis a STD CAL of 8.00 will yield a full scale
value of approximately 5 yg at/fc.
e) For a discussion of calibration and blank problems refer to
Sections III 2-3.
f) Smoking in the laboratory, and the use of ammonia-containing
cleaning agents should be avoided to "help reduce atmospheric
contamination of ammonia.
g) Segmented air supply should be scrubbed through concentrated
to further avoid atmospheric contamination.
11
-------
II.
5. AMMONIA (Continued)
h) Plastic sample cups should be well rinsed (3-4 times) with the
sample before use. They need not be acid washed.
i) The sodium dichloro-s-triazine-trione may be purchased from the
following supplier:
K & K Laboratories, Inc.
Plainview, New York
catalog no.: 17779
12
-------
AMMONIA
-o \
rt>
S.OO
o-
/ JL
A »?^ /§ R
ll-o-
COLORIMETER RECORDER
ne.
a
-------
III. OPERATIONAL PROCEDURES
1. SET-UP
The following procedures should be followed every day the Auto-
Analyzer is set up:
1. Colorimeters, heating baths and recorders should be turned on
at least one hour before instrument calibration.
2. Pump DDW through all lines for 10-15 min. Use a separate water
bottle for each chemistry and do not mix under any circumstances.
3, Wash for 5 min with IN HC1 or NaOH if necessary to establish a
smooth bubble pattern. This will be particularly important for phosphate.
4. Rinse with DDW again for 5-10 minutes.
5. Set STD CAL on colorimeters to 1.00. Check zero and full scale.
Establish a baseline with DDW in all lines (Sampler IV and reagents).
6. Begin pumping reagents with DDW from the Sampler IV,
7. Record the height of the reagent baseline. This should remain
constant for fresh reagents; if not, it is a good indication that one of
the reagents should be repla-ced.
8. Reset baseline. Turn STD CAL to approximate operating value.
9. Proceed with standards and calibration.
19
-------
III.
2. STANDARDS AND CALIBRATION; SAMPLES
For routine operation one standard of approximately mid-scale value
will be sufficient. The procedure for this will be discussed in detail
below.
However, it is of utmost importance to check the system with several
standards over a range of concentrations under the following circumstances:
1, each time the colorimeter has been aligned or "peaked".
2. whenever analyzing samples that are at the limit of the range of
the method.
3. if the system has not bean used for several months.
4. if the system has undergone a relocation. This is important
when a system is moved from laboratory to shipboard and vice versa,
This type of check is important to establish the following information:
1. linearity of the system. This is frequently overlooked by many
analysts, and consequently samples are analyzed above the Beer's
Law range of the system, leading to erroneous values.
2. sample carry-over. Although it is recommended that all samples
of a similar concentration be analyzed together, this is not
always possible. Thus, it is extremely important to know whether
low values will be contaminated by higher ones. If this effect
is large, a different cam nay solve the problem. The following
series is recommended to determine linearity and sample carry-over.
The numbers represent chart paper values, which correspond to an
appropriate concentration of a standard.
Sample cup $_ Chart paper value
1 60 set calibration with
2 60 the.se standards
3 60 using STD CAL
4 20
5 20
6 40
7 40
8 60
9 60
10 80
11 80
12 100
13 100
14 20
15 20
20
-------
III.
2. STANDARDS AND CALIBRATION; SAMPLES (Continued)
Samples number 2-13 will establish whether or not the system is
responding linearly through that range of standards; samples number 13-15
will establish whether or not there is inter-sample contamination.
"For routine operation samples should be analyzed in 40-sample batches
(the capacity of a Sampler tray}. Three standards of one concentration
for each nutrient are placed at the beginning of the tray. The values for
these standards should approximate the values of the samples. This
standard is then adjusted to mid-scale using the STD CAL, This STD CAL
value is recorded on the chart paper along with identification of the
nutrient being analyzed, the date and the run number.
When running many trays in sequence allow 3-4 minutes of DDW baseline
between trays to determine drift and reset the baseline if necessary.- If
you allow longer time between trays we recommend using 4 standards of each
type at the start of a tray since the system must "coat up" and come to
equilibrium with the nutrient being analyzed. Important to note: When
setting up a sequence of samples on the tray, always run duplicates of the
first sample after standards since a change in ionic strength (addition
of seawater) always makes the first seawater sample 10-30% higher than it
should be due to desorption probleffis. Use data from the second sample.
A typical data sheet is shown in Figure 7. On it there are appro-
priate spaces for identifying the sample (station number and depth),
recording the peak height value from the chart paper, and recording inter-
mediate and final concentration, values. There is also a place to record
baseline drift from that run. Calculations are discussed
ir. nore detail in section III - 5.
-------
III.
3. BLANK AND SALINITY CORRECTIONS
The absorbance peak obtained by an automated system for a given
nutrient in a seawater sample (when compared to a deionized distilled
water baseline) represents the sum of absorbances from at least four
sources (Fig.8 ): 1) the light loss due to the differences in the index
of refraction of the seawater and the deionized distilled water baseline;
2) reaction products (i.e. precipitates) of appropriate wetting agents
and the seawater; 3) the absorbance of colored substances in the sample,
either particulate or dissolved; and 4) reaction products of the nutrient
in the sample and the color reagents. These reaction products may be
variable due to a "salt error" caused by a shift in the position of
equilibrium as a function of a change in the ionic strength of the solu-
tion (Brewer and Riley, 1965).
Loder and Gilbert (1977) provide a full explanation of the rationale
of applying such corrections to each nutrient; here we will just summarize
the magnitude of such corrections, and methods for determining them.
The corrections for refractive index for each chemistry are given
in Table I ; the percent salt error relative to distilled deionized water
standards for each chemistry is shown in Figure 9. These corrections
are intended only as a guide to show the extent and type of correction
necessary. It is important that individual analysts determine the appro-
priate corrections for their own system and methodology.
On a routine basis, Loder and Gilbert (1977) suggest the following
methods for determining the refraction and salt errors. In both methods
DDW is used to set the baseline and as a wash between samples.
Method 1: Open ocean or narrow salinity range samples. Prepare
standards with low nutrient naturalseawater (NSW). Prepare standards in
volumetric flasks using precision small volume auto-pipets; this way
the standard addition does not significantly alter the salinity. Silicate
standards must be prepared in polypropylene volumetrics to avoid leaching
of silica from glass.
Analyze standards using normal reagents and run a blank on the
water used to make the standards. Subtract the blank from the standards,
and then determine the full scale value for that analysis.
Determine the refractive index correction for the samples by analyzing
representative samples with only deionized water in the diluent lines and
a reagent from which one of the color formers has been eliminated in the
reagent lines. The concentration of the nutrient in the samples is then
determined: corrected concentration = C(peak height of sample)(full
scale value) * lOOD - Crefractive index corr. in cc:\c. units].
23
-------
Color products of specific reaction,
f(method, temp., S°/oo, pH, etc).
Wetting agent, f(amount and S°/oo).
Refraction, f(A Ref. Index between
wash and sample).
Turbidity, f(sample type, handling).
Figure 8. Sources of absorbance for a seawater nutrient sample.
-------
Table I, Summary of Refractive Index (RI) corrections for
methods discussed in text.
Method and
Reference
Phosphate
Silicate
Nitrite
Nitrate
Ammonia
(4)
(2)
(24)
(26)
(33)
STD CAL
8.
8.
7.
3.
8.
00
00
70
CO
00
Full Scale Value RI correction
(ug.at/A) f(S°/00)**
5 0.
23 0.
2 0.
7.6 0.
5 0.
(vg-
006
012
0019
0045
0057
at/i)
(S0/oo)*
(So/oo)
(So/oo)
(SO/oo)
(So/oo)
*Includes effect of Levor IV at 0.5 ml /$, concentration in the diluent
**These values can be approximated at different STD CAL settings if the
dilution ratios remain the same. Multiply f by the ratio:full scale
absorbance at STD CAL given above * full scale absorbance at new
SIB CAL.
25
-------
III.
3. BLANK AND SALINITY CORRECTIONS (Continued)
Method 2! Estuarine br variable salinity samples. For samples with
a wide range of salinities we suggest that routine standards be prepared
in DDW and that a separately determined salt error factor be applied to
the observed concentration to obtain the correct value.
We suggest the following procedure to determine the salt error correc-
tion value: Dilute low nutrient NSW with DDW to make a range of salinities.
Prepare standard additions as described in Method 1 above, as well as
DDW standards, using a precision small volume auto-pipet. Analyze the
DDW standards and each dilution as well as the dilutions with the standard
additions.
Determine the difference in concentrations between the seawater
dilutions and those with the standard additions. Calculate the change in
apparent nutrient concentration relative to the DDW standards as a func-
tion of salinity. Finally, to obtain the corrected concentration, subtract
the appropriate refractive index correction, as described in Method 1, fro^i
the observed apparent concentration and multiply by the salt error factor.
26
-------
III.
4. SHUT-DOWN
At the end of an operation day, the following procedures should be
carried out:
1. Place all reagent lines in the DDW bottles specific for that
analysis.
2. Return the sampler probe to the Sampler IV.
3. Pump DDW through the system for 10-15 minutes.
4. If system will not be set up the following day, then remove all
reagent lines from DDW bottles and remove the sampler probe from sampler
wash, and pump air through the system until all lines are dry.
5. Unplug heating baths.
6. Remove recorder pins, cap the tips, and turn recorder to off
position,
7, Turn off colorimeters.
8. Remove pump platen and loosen pump tubes.
27
-------
III.
5. DATA CALCULATIONS
Aspects of data calculations have been discussed in Sections III-2 and
III-3; here the procedure will be summarized.
1. Peak heights for standards and samples are read and recorded
on the data sheets as shown in Figure 7.
2. Baseline drift for the analysis set is read and also recorded
on the same data sheet.
3. Full scale value for the data set is determined as follows:
full scale value = (cone of std - cone of blk)
(pk ht of std - pk ht of blk)
4. The concentration of each sample is then determined by using
one of the following calculator programs which corrects each peak for
the appropriate baseline drift and then determines the sample concen-
tration based on the full scale value determined above. Program 1 is
algebraic. It was written for a Texas Instruments 56, but could easily
be adapted to any algebraic calculator. Program 2 was written in reverse
Polish notation for a Hewlett-Packard 55. The algebraic program has an
option to subtract a refractive index correction and multiply by a salt
correction factor. It is important that the analyst be aware of which
corrections must be applied to which chemistries and the magnitude of
such corrections.
28
-------
IV. SENSITIVITY AND REPRODUCIBILITY OF AUTOMATED ANALYSES
Hager et al. (1972) summarize, what quality data from an automated
system depends on;
"As the literature indicates, the quality of the results is usually
more dependent on the operator than the method - a point well ap-
preciated by seagoing scientists"
Instrumental variability and replicate sampling variability were
determined for very low level analyses at the University of New Hampshire
laboratory (Glibert and Loder, in prep.). In order to determine instru-
mental variability, four 500 ml samples were analyzed approximately 9 to
10 times throughout a day. The standard deviations and percent variations
were calculated for each nutrient (Table 10. Nitrite proved to have the
highest variability (2.6%).
Replicate sampling variability was determined by collecting six sets
of quintuplicate samples. These samples were then analyzed during the
same time period (to minimize machine drift), and the average standard
deviation and percent variation were calculated (TableII). Only in the
case of silicate was the replicate sampling variability higher than the
analytical variability. There is evidence that this high silicate sampling
variability may have been due to planktonic or sedimentological contamina-
tion, but this is uncertain.
33
-------
Table II. Analytical and replicate sampling variability for nutrient samples.
parameter salinity NO--N N03-N P04-p Si02~S
(units) ( °/oo) (ug it/I) (ug at/O (ug at/fc) (ug at/fc)
range of
method 0-40 0-2 0-5 0-5
range of
sample cone. 28-30 0.1-0.4 0.1-1.0 1.0-2.0 4.0-7.0
analytical
variability3 - 0.009 0.05 0.02 0.08
(2.6%) (1.2%) (1.7%) (1.4%)
replicate
sampling
variability13 0.003 0.002 0.04 0.01 0.43
(0.01%) (0.7%) (0.8%) (1-0%) (6.4%)
a Based on the average standard deviations of 9-10 replicate runs of the same
samples.
k Based on the average standard deviations of numerous sets of replicate
samples run at the same time.
-------
VII. REFERENCES
APHA, AWWA, and WPCF. 1976. Standard methods for the examination of
water and wastewater (14th ed).
Brewer, P.G. and J.P. Riley. 1965. The automatic determination of
nitrate in seawater. Deep-Sea Res. 12 : 765.
and . 1966. The automatic determination of
silicate - silicon in natural waters with special reference to
seawater. Anal. Chim. Acta _35_ : 514.
Collins, K..J. and P.J. LeB. Williams. 1977. An automated photochemical
method for the determination of dissolved organic carbon in sea and
estuarine waters. Mar. Chen. _5_ : 123-141.
D'Elia, C.F, » P.A. Steudler and N. Corwin. 1977. Determination of
total nitrogen in aqueous samples using persulfate digestion.
Limnol. Oceanogr. (in press).
DeManche, J.M., H. Curl, Jr. and D.D. Coughenower. 1973. An automated
analysis for urea in seawater. Limnol. Oceanogr. _1_8 : 686-689.
Ehrhardt, M. 1969. A new method for the automatic determination of
dissolved organic carbon in seawater. Deep-Sea Res. 16 r 393-397,
Gilbert, P.M., C.F. D'Elia and Z. Mlodzinska. 1977. A semiautomated
persulfate oxidation technique for simultaneous total nitrogen
and total phosphorus determination in natural water samples.
Envir. Scl. Tech. (submitted).
and T.C. Loder. 1977. Distributions of chemical parameters
in an estuarine system. I. Analytical and short-term variability
(in preparation).
and Z. Mlodzinska. 1977. A comparison of two buffer systems
used in the standard method for the determination of nitrate in
seawater. Limnol. Oceanogr.(submitted).
Gfasshoff, K. and J. Johannsen. 1972. A new sensitive and direct
method for the automatic determination of ammonia in seawater.
J. Cons. int. Explor. Her _34_ : 516.
Eager, S.M., E.L. Atlas, L.I. Gordon, A.W. Mantyla and P.K. Park. 1972.
A comparison at sea of manual and AutoAnalyzer analyses of phosphate,
nitrate and silicate. Limnol, Oceanogr. 17 : 931-137.
41
-------
Koroleff, F. 1969. Determination of total nitrogen in natural waters
by means of persulfate oxidation. International Council for the
Exploration of the Sea (ICES) Paper C.M. 1969/C:8, Revised Version,
1970 (In Swedish).
Loder, T.C. and P.M. Gilbert. 1977. Blank and salinity corrections for
automated nutrient analysis of estuarine and sea waters. Advances
in Automated Analysis, in press.
Mantaura, R.F.C. 1977. Personal communication. Institute for Marine
Environmental Research, 67/69 Citadel Road, Plymouth, Pll 3DH,
Devon, England.
Murphy, J. and J.P. Riley, 1962. A modified single solution method for
the determination of phosphate in natural waters. Anal. Chim. Acta
22 : 31-
Newell, B.S., B. Morgan and J. Cundy. 1967. The determination of urea
in seawater, J. Mar. Res. 25_ : 201-202.
O'Connor, B. and W. Miloski. 1974. Ammonia analysis of seawater using
a Technicon AutoAnalyzer II. Suffolk County Department of Environ-
mental Control. Unpublished manuscript.
Snyder, L., J. Levine, R, Stoy and A. Conetta. 1976. Automated chemical
analysis : update on continuous-flow approach. Anal. Chem. 48 :
942A-956A.
Technicon Industrial Systems. 1970. The Industrial AutoAnalyzer. Manual
No, TNO-0210-00.
_^_^^_ 1970. Operation manual for the Technicon
proportioning pump, models II, III, and H. Manual No. TAO-0159-10.
1971. Operation manual for the Technicon
AutoAnalyzer II single-channel colorimeter. Manual No. TA1-0257-10.
1971. Operation manual for the Technicon
AutoAnalyzer Sampler IV. Manual No, TAO-0219-20.
1972. Nitrate and nitrite in water and
seawater. Industrial Method No. 158-71W.
1973. Nitrite in water and seawater.
Industrial Method No. 161-71W.
1973. Orthophosphate in water and sea-
water. Industrial Method No. 155-71W.
42
-------
1973. Silicates in water and seawater.
Industrial Method No. 186-72W.
Wood, E.D., F.A.J. Armstrong and F.A. Richards. 1967. Determination of
nitrate in seawater by cadmium - copper reduction to nitrite. J.
Mar, Biol. Assoc. U.K. 4_7 : 23.
-------
APPENDIX II: RECOMMENDED SAMPLE COLLECTION AND STORAGE
PROCEDURES
It is well known that variability or error can be introduced to a
sample from: the type of storage container, chemical preservation,
filtering, the temperature of storage, and the length of time samples
have been stored* No single storage method will be suitable for all
water types» or for all seasons. As a guideline, the following is
suggested;
1. type of bottle. High density linear polyethylene or polycarbonate
is superior to soft polyethylene,
2. Pretreatment of bottle. Rinse a c.'ean bottle with acid (10% HC£),
then distilled deionized water, then several times with the sample.
3. Chemical preservation. No preservative is necessary for open
ocean samples if immediately frozen. A preservative should be
used if samples have a high organic content. HgCl2 (of final
concentration in sample of vlOO ppm) is recommended for nitrate,
nitrite, phosphate and silicate. We use 0.5 ml of a 2% w/v
solution added to a 100 ml sample. HgCl2 should be avoided in
preserving ammonia; instead a phenol-alcohol mixture is recommended.
(Dissolve lOg phenol in 100 ml of 95% v/v ethyl alcohol USP. Add
2 ml phenol solution to 50 ml sample.)
4. Means of storage. Samples should be immediately frozen if possible,
Allow plenty of air space at top of bottle (at least 1.5 cm) for
expansion. Caps should be very tight. Keep samples upright until
fully frozen, to avoid leakage through cap. Tighten caps again
after samples are frozen.
5. Filtration. Depends on samples, Millipore filters may contami-
nate ammonia and phosphate; glass fiber filters may contaminate
silicate.
6. Length of storage time. Samples should be analyzed as soon after
collection as possible. Significant changes will occur in
ammonia, even if a preservative is used.
The above is meant merely as a guideline. For more exhaustive treatments
of the subject, the reader is referred to the articles listed on the next
page.
45
-------
REFERENCE LIST FOR APPENDIX II
Gilmartin, M. 1967. Changes in inorganic phosphate concentration
occurring during seawater sample storage, Limnol, Oceanogr.
12_ : 325-328.
Gilbert, P.M. and T.C. Loder. 1977. Distributions of chemical
parameters in an estuarine system. I. Analytical and short-
term variability (in preparation).
Harvey, H.W. 1941. On changes taking place in seawater during
storage. J. Mar. Biol. Assoc. U.K. 2_5 : 225-233.
Hassenteufel, W,, R. Jagitsch, and F.F. Koczy. 1963. Impregnation
of glass surface against sorption of phosphate traces. Limnol.
Oceanogr. B : 152-156.
Marvin, K.T. and R.R. Proctor, Jr. 1965. Stabilizing the aranonia-
nitrogen content 01 estuarine and coastal waters by freezing.
Limnol. Oceanogr. 10 : 288-290.
, and R.A. Neal. 1972. Some effects of. filtra-
tion on the determination of nutrients in fresh and salt water.
Limnol, Oceanogr. 17 : 777-785.
Murphy, J. and J.P. Riley. 1956. The storage of seawater samples for
the determination of dissolved inorganic phosphate. Anal. Chim.
Acta _14_ : 318-319.
Riley, J.P. 1975. Analytical chemistry of seawater. p. 193-514.
In: Riley, J.P. and G. Skirrow (eds.), Chemical Oceanography,
2nd ed., v. 3. Academic.
Thayer, G.W. 1970. Comparison of two storage methods for the
analysis of ritrogen and phosphorus fractions in estuarine
water. Ches. Sci. _11 : 155-158.
United States Environmental Protection Agency. 1974. Methods for
chemical analysis of water and wastes. Methods Development and
Quality Assurance Research Laboratory, National Environmental
Research Center, Cincinnati, Ohio.
Zobell, C.E. and B.F. Brown. 1944. Studies on the chemical preserva-
tion of water samples. J. Mar. Res. _5 : 178-184.
46
-------
APPENDIX B
SUMMARY OF THE Hg RESULTS FOR SAMPLES
COLLECTED DURING THE JULY 1988
NEW YORK BIGHT SURVEY
-------
TABLE B-l. CORRECTED Hg RESULTS FOR SAMPLES COLLECTED DURING THE
NEW YORK BIGHT SURVEY (JULY 1988).
Station
A2
A4
A6
AS
AlO^
All
A13
A15
B2
B4
B5
86
, 88
BIO
Cl
C2
C3^
C3d
C4
C5
C6
C7
C8
CIO
Cll
C13
C15
Field Blank
Depth ia
11.4
7.6
13.3
9.5
9.5
13.3
7.6
7.6
5.7
9.5
9.5
9.5
7.6
3.8
5.7
5.7
5.7
5.7
5.0
5.7
3.8
3.0
3.0
3.0
5.0
5.0
5.0
Depth 2b
17.1
34.3
66.6
95.2
104.7
104.7
55.2
38.1
15.2
40.0
32.4
28.6
24.7
17.1
15.2
13.3
20.9
20.9
15.2
15.2
13.0
7.6
15.0
10.0
15.0
35.0
20.0
Batch
1
1
1
2
l,4Be
1
1
1
2
2
2
2
2
2
3
3
4Ae
4A6
4B«
3
3
3
3
3
A D fi
^1 Pfi
2
1
Hgc
(9/1}
1.515
4.616
0.248
2.768
3.536
1.648
3.295
1.264
1.441
3.245
0.826
0.982
0.539
2.110
11.376
13.250
6.220
6.644
49.759
9.782
10.061
6.329
7.392
4.978
6.316
2.484
1.089
f
^Surface depth.
bpycnocline depth.
cSamples were pooled from surface and pycnocline depths; 1/2 from each depth
dMean value.
eBatch 4 samples analyzed on 2 days designated A and 8.
f?he field blank was determined to contain less mercury than the procedural
blank
-------
TABLE B-2. QUALITY CONTROL DATA FOR Hg SAMPLESi
REPLICATES
Measured
Concentration
Sample No. (ng Hg/L)
GG89-HG-1-1
SG89-H6-1-2
Mean
Percent RPD
GS89-HG-2-1
GG89-HG-2-2
Mean
Percent RPD
5.088
7.351
6.220
36
5.608
7.680
6.644
31
-------
TABLE B-3. QUALITY CONTROL DATA FOR Hg SAMPLES:
BUNK SPIKING EXERCISE
Batch No.
Batch 1
Batch 2
Batch 3
Batch 4A
Batch 4B
*
Sample No.
GH68-BS
GH69-BS
GH74-BS
GH75-BS
GH90-BS
GH91-BS
GI03-BS
GI04-BS
SI05-BS
GI06-BS
Measured
(in ng)
2.549
3.413
1.718
2.323
2.575
2.810
1.871
2.292
2.166
4.322
Kg
Added
(in ng)
4.08
-
4.08
-
4.08
-
-
-
4.08
-
Percent
Recovery
62
84
42
57
63
69
46
56
53
106
-------
TABLE B-4. QUALITY CONTROL DATA FOR Hg SAMPLES: MATRIX SPIKING EXERCISE,
Expected
Measured Concentration Hg
Concentration of Hg Added Percent
Sample No. (ng Hg/L) (n§ Hg/L) (ng) Recovery
GS89-HG-1 16.275 22.22 4.08 73
6G89-HG-2 12.248 22.964 - 53
-------
APPENDIX C
SUMMARY OF TRACE HETALS DATA
(EXCLUDING Hq) FOR SAMPLES
COLLECTED DURING THE JULY 1968
NEW YORK BIGHT SURVEY
-------
TABLE C-l. SUMMARY OF ACID SOLUBLE TOTAL TRACE METAL CONCENTRATIONS FOR
SAMPLES COLLECTED DURING THE JULY 1988 NEW YORK BIGHT SURVEY.
RESULTS ARE IN /*g OF METAL/L OF SEAWATER. FIELD REPLICATES ARE
DESIGNATED WITH PARENTHESES.
Station
A2(l)
A2(2)
A2(l)
A2(2)
A43
A4
A6
A6
A8
A8
A10
A10
All
All
A13(l)
A13(2)
A13(l)
A13(2)
A15
A15
810(1)
B10(2)
B10(l)
B10(2)
B8
B8
B6a
B6
B5
B5
B4(l
B4(2
B4(l
B4(l
B2
82
C15
C15
C13C1)
C13(2)
C13(l)
C13(2)
Cll
Cll
Depth
11.4
11.4
17.1
17.1
7.6
34.3
13.3
66.6
9.5
95.2
9.5
104.7
13.3
104.7
7.6
7.6
55.2
55.2
7.6
38.1
3.8
3.8
17.1
17.1
7.6
2i.8
9.5
28.6
9.5
32.5
9.5
9.5
40.0
40.0
5.7
15.2
5.0
20.0
5.0
5.0
35.0
35.0
5.0
15.0
Cd
0.026
0.028
0.023
0.024
0.025
0.024
0.010
0.018
0.017
0.015
0.020
0.017
0.017
0.019
0.022
0.021
0.020
0.022
0.024
0.027
0.033
0.038
0.034
0.033
0,030
0.032
0.029
0.031
0.030
0.029
0.031
0.033
0.044
0.043
0.044
0.049
0.040
0.034
0.055
0.051
0.048
0.051
0.065
0.038
Cu
0.32
0.32
0.28
0.26
0.48
0.19
0.14
0.12
0.19
0.07
0.21
0.09
0.13
0.09
0.20
0.19
0.13
0.15
0.24
0.18
0.56
0.63
0.59
0.58
0.43
0.47
0.45
0.32
0.48
0.34
0.50
0.52
0.56
0.53
0.76
0.75
0.64
0.39
0.91
1.04
0.74
0.80
1.29
1,03
Fe
4.05
3.73
2.73
2.57
5.69
2.85
0.55
1.02
0.34
0.30
0.42
1.49
0.40
3.41
0.46
0.40
2.10
2.24
1.86
7.53
3.19
3.79
47.9
46.7
4.75
4.70
0.65
3.11
0.95
5.65
1.44
1.49
30.6
33.0
7.4
34.7
4.0
5.5
17.0
22.7
49.7
58.1
57.4
46,2
Ni
0.36
0.39
0.33
0.32
0.48
0.28
0.21
0.23
0.26
0.29
0.29
0.20
0.25
0.23
0.32
0.31
0.28
0.35
0.32
0.29
0.48
0.55
0.44
0.43
0.38
0.37
0.38
0.30
0.42
0.33
0.44
0.42
0.39
0.38
0.64
0.48
0.54
0.35
0.81
0.88
0.42
0.43
0.99
0.45
Pb
0.033
0.024
0.021
0.021
0.061
0.022
0.054
0.017
0.020
0.015
0.029
0.017
0.018
0.027
0.028
0.022
0.067
0.019
0.020
0.021
0.044
0.052
0.200
0.200
0.041
0.041
0.022
0.026
0.023
0.033
0.027
0.028
0.238
0.239
0.086
0.289
0.045
0.040
0.179
0.212
0.437
0.485
0.466
0.345
Zn
0.55
0.60
0.43
0.36
1.42
0.30
0.39
0.14
0.18
4.44
0.15
0.23
0.07
0.09
0.20
0.28
0.11
0.17
0.22
0.24
1.12
1.30
1.31
1.30
0.71
1.11
0.53
0.61
0.58
0.77
0.75
0.81
1.64
1.63
1.93
3.11
1.70
1.20
3.12
2.87
2.82
2.37
4.22
2.60
-------
TABLE C-l. (Continued)
Station
CIO
CIO
C8
C8
C7
C7
C6
C6
C5
C5
C4
C4
C3(l)
C3(2
C3{1)
C3(2)
C2
C2«
Cl
Cl
Bottle
Blank
Depth
3.0
10.0
3.0
15.0
3.0
7.6
3.8
13.0
5.7
15.2
5.0
15.2
5,7
5.7
20.9
20.9
5.7
13.3
5.7
15.2
Cd
0.070
0.066
0.067
0.047
0.087
0.077
0.063
0.055
0.082
0.064
0.104
Q.Q68
0.090
0.088
0.075
0.074
0.109
0.121
0.104
0.093
NO
Cu
1.83
1.43
1.78
1.36
2.33
2.33
1.79
1.49
2.42
2.05
3.30
2.27
2.70
2.81
2.46
2.46
4.44
3.77
3.36
2.96
0.012
Fe
100.0
95.2
81.5
70.1
95.2
97.9
84.5
78.2
147.9
135.5
228.1
194.8
180.8
187.8
184.0
187.2
207.6
345.0
268.4
223.0
oai
Hi
1.44
0.87
1.46
0.91
1.90
1.84
1.51
1.21
2.02
1.47
2.46
1.46
2.24
2.33
1.87
1.76
2.60
2,40
2.58
2.37
<0.02
Pb
0.863
0.704
0.825
O.S49
0.867
0.855
0.801
0.656
1.39
1.11
1.96
1.35
1.57
1.70
1.40
1.46
1.86
2.96
2.01
1.72
O.QQ3
Zn
9.28
5.31
6.86
5.21
8.42
8.18
6.52
4.70
7.23
5,76
9.42
4.83
9.63
10.08
6.21
6.51
9.25
18.77
9.38
9.13
0.03
NO = Not detectable.
aMean of duplicates.
-------
TABLE C-2. RESULTS OF ANALYSIS OF DUPLICATE SAMPLE EXTRACTIONS. RESULTS ARE
IN jg OF HETAL/L OF SEAHATER. MEAN AND RELATIVE PERCENT
DIFFERENCE (PERCENT RPD) REPORTED FOR EACH SET OF DUPLICATE
ANALYSES.
Sample
A4(l)
A4(2)
Mean
Percent
B6(I)
B6(2)
Mean
Percent
C2(l)
C2(2)
Mean
Percent
Depth
7
7
RPD
9
9
RPD
13
13
RPD
.6
.6
.5
.5
.3
.3
0
0
0
24
0
0
0
3
0
0
0
2
Cd
.022
.028
.025
.030
.029
.029
.120
.122
.121
0
0
0
32
0
0
0
7
3
3
3
1
Cu
.40
.55
.48
.46
.43
.45
.75
.80
.77
Fe
5.69
5.68
5.69
0
0.71
0.59
0.65
18
347.3
342.7
345.0
1
0
0
0
42
0
0
0
5
2
2
2
0
Hi
.38
.58
.48
.39
.37
.38
.40
.41
.40
Pb
0.56
0.67
0.61
18
0.024
0.020
0.022
18
2.87
2.92
2.90
2
Zn
1.37
1.46
1.42
6
0.55
0.50
0.53
10
18.71
18.82
18.77
1
-------
TABLE C-3. SUMMARY OF THE RECOVERY OF METALS FROM CANADIAN STANDARD
REFERENCE SEAWATER CASS-1 PROCESSED AND ANALYIED WITH SAMPLES.
CONCENTRATIONS ARE IN *g/l AND RECOVERY IN PERCENT (% R).
Sample
Expected
1
2
3
4
5
6
Mean
Expected
1
2
3« *
4
5
6
Mean
Cd
0.026
0.026
0.022
0.020
0.023
0.019
0.022
0.022
N1
0.290
0.39
0.37
0.29
0.30
0.30
0.32
0.33
%R
100
85
77
88
73
85
85
%R
134
128
100
103
103
110
113
Cu
0.291
0.34
0.29
0.31
0.33
0.31
0.33
0.32
Pb
0.251
0.209
0.231
0.222
0.233
0.215
0.235
0.224
*R
117
100
107
113
10?
113
109
%R
83
92
88
93
86
94
89
Fe
0.873
1.03
0.87
0.74
0.72
0.70
0.82
0.81
Zn
0.980
1.14
1.05
1.58
1.09
0.95
1.06
1.15
%R
118
100
85
82
80
94
93
m
116
107
161
111
97
108
117
-------
TABLE C-4. SUMMARY OF THE SPIKING MATERIALS RECOVERY OF METAL ADDED TO
SAMPLES DURING PROCESSING OF WATER SAMPLES. THE AMOUNT OF
METAL FOUND, THE EXPECTED AMOUNT. AND THE PERCENT RECOVERY
(*R) OF THE KNOWN ADDITION ARE SHOWN.
Sample
A4 7.6 m
B6 9.5 m
C2 13.3 m
A4 7.6 m
B6 9.5 m
C2 13.3 m
A4 7.6 m
B6 9.5 m
C2 13.3 m
Found
(ng)
17.0
28.6
44.6
1292
253
74360
32.3
27.2
622
Expected
(ng)
Cd
25.4
26.0
44.9
Fe
1262
228
70267
Pb
36.6
28.4
614
*R
67
no
99
102
111
106
88
96
101
Found
(ng)
101.8
116.0
804
136
128
554
323
181
3939
Expected
(ng)
Cu
120.3
110.3
789
Ni
148
124
538
Zn
357
171
3885
*R
85
105
102
92
103
103
90
106
101
-------
APPENDIX D
SUMMARY OF THE NUTRIENT RESULTS
FOR SAMPLES COLLECTED DURING THE JULY 1988
NEW YORK BIGHT SURVEY
-------
TABLE D-l. SUHKARY OF TOTAL AND DISSOLVED NUTRIENT DATA (IN
fiH OF NUTRIENT/L OF SEAffATER) FOR SAMPLES
COLLECTED DURJNG THE NEW YORK BIGHT SURVEY
(JULY 1988).
Station Repa
A-l
A- 2
A- 3
A- 4
A- 6
1
2C
3
1
2C
3
1
3
1
3
1
3
1
3
1
3
1
3
1
2C
3
1
2C
3
1
3
1
3
Depth
3.8
-
11.4
-
11.4
-
17,1
-
9,5
34.2
-
7.6
34.3
-
7.6
-
41.9
-
13.3
_
66.6
»H4b
2.15
0.24
0.02
3.78
0.45
3.24
0.10
1.38
0.71
9.73
0.10
ND
1.34
NA
23. 6d
4.50
A
5.21d
4.85
104d
0.16
1.13
17.3
0.70
ND
9.96d
ND
0.72
0.37
N03b
2.35
7.05
0.27
358d
36ld
0.45
21. 2d
0.28
52.7
0.28
7.92
0.31
19.1
NA
350b .
36. 5d
A
60. 6a
31.8
69. 5d
24. 6d
4.52
399d
137
67.5
H2d
0.2
65. 4d
7.28
0
0
-
0
0
-
0
-
0
0
0
-
0
0
-
0
0
-
0
0
-
0
-
0
-
N^^«%
.04
.03
.18
.18
.03
.07
.05
.07
.04
.10
.06
.03
.15
.12
.04
.15
<
0.23
0.26
0.35
0.31
0.30
0.29
0.28
0.27
0.31
0.31
0.18
0.12
0.35
NA
0.14
0.10
0.40
0.36
0.43
0.48
0,45
0.56
0.56
0.07
0,12
0,07
0.73
0.58
sio4
3.00
3.48
-
3.46
3.50
-
3.98
-
3.72
1.71
4.20
-
1.21
3.95
-
2.73
2.33
-
2.54
2.02
-
1.52
-
S.31
TOT
14.
_
14.
*
17.
»
69.
_
65.
_
1802
14.
36.
_
11.
171
_
8.
w*.
17.
N
6
3
9
8
3
1
4
3
97
8
TOT P
0.79
0.73
0.70
_
0.72
_
0.43
_
0.97
0.20
-
0.83
0.76
-
0.71
_
0.36
0.88
-------
TABLE D-l. (CONTINUED).
STATION REPA DEPTH
A-7 1
3
1
3
A-8 1
3
1
3
A-9 1
3
1
3
A-10 1
2
3
1
2C
3
A-ll 1
3
1
3
A-12 1
3
1
3
A-13 1
3
1
3
3
-
62
9
-
95
9
-
81
_
9
-
-
104
-
13
_
104
_
15
60
7
-
55
-
.8
.8
.5
.2
.5
.9
.5
.7
.3
.7
.2
.9
.6
.2
NH4B
0.04
ND
1.69
0.39
0.21
NA
0.79
ND
0.06
ND
7.26
ND
0.1|
43.9°
0.24
0.30
0.29
ND
0.14
2.39
21.9 1
NA
0.08
0.58
0.02
ND
0.04
0.04
6.55
NA >
NO/
1.3
0.14
18. 6d
7.18
10.7
83.1
115d
14.9
5.95
0.5
13.7
8.22
67 ld
51
1.12
17.3d
15.0
13.2
0.57
0.19
136d
11.9
31. ld
4.18
14.8
7.36
0.86
0.81
260d
118
NO
2
ND
-
0.
_
0.
-
0.
-
0.
-
0.
-
0.
0.
-
0.
0.
-
0.
-
0.
-
0.
-
0.
-
0.
-
0.
-
38
08
17
07
09
11
22
14
12
15
16
14
10
11
61
P.1 SIO..
4 4
0.09
0.09
0.69
0.75
0.21
NA
0.79
0.88
0.19
0.32
0.57
1.13
0.21
0.23
0.14
0.70
0.72
0.58
0.24
0.11
0.69
NA
0.23
0.15
0.55
0.46
0.22
0.15
0.68
NA
1.
-
5.
1.
-
5.
2.
_
4.
-
2.
2.
-
6.
5.
-
2.
-
7.
2.
-
5.
-
2.
-
5.
TOT N TOT
47 -
10.3
31 -
15.6
64 -
669
80 -
22.4
16 -
9.12
38 -
16.1
29 -
66 -
8.98
02 -
94 -
16.9
17 -
8.59
66 -
662
04 -
11.8
36 -
15.0
22 -
15.2
57 -
163
_
0
1
-
0
*_<
1
_
0
_
0
_
0
_
0
0
0
_
0
_
0
«_
0
0
p
.49
.16
.43
.27
.48
.78
.49
.82
.36
.85
.47
.78
.50
.87
-------
TABLE D-l. (Continued).
Station
A-14
A-15
A-16
B-2
B-3
B-4
B-5
Repa
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
2
3
1
2C
3
Depth
9,
-
51.
-
7.
-
38.
-
7.
22.
-
5.
-
15.
-
2
_
28.
-
9.
-
40
-
9.
9.
-
32.
32.
5
4
6
1
6
8
7
2
.5
6
5
5
5
.5
,5
NH/
0.10
ND
2.84
5.94
3.12
ND
4.26
NA
0.65
6.65
1.58
ND
0.84
0.35
6.17
-
2.36
0.08
1.24
2.01
0.21
1.75
1.86
13.9
73. 7d
0.34
0.32
3.75
1.10
2.07
N03b
0.18
0.09
9.27
12.8
24. 9d
0.04
2.15
85.6
0.93
19.0
21.1
0.2
10.8
0.4
15.8
75.4
16.3
0.43
0.69
1.62
0.23
3.04
2.08
>15.1
348d
13.5
4.54
34.3d
1.06
2.77
N02
0.10
-
0.69
-
0.09
_
0.15
-
0,07
-
0.13
-
0.06
-
0.20
PO., SiO,, Tot N
4 4
0.17
0.13
1.92
0.74
0.39
0.15
0.95
NA
0.68
0.42
0.50
0.38
0.59
0.48
1.22
3
_
9
-
3
-
14
.17
.13
.67
.5
11.1
_
24.1
«
11.8
949
10
9
-
2
-
11
.0
.62
.89
.8
mm
25.5
_
29.3
_.
19.0
_
- 324
0.07
0.12
_
0.06
0.18
-
0.17
0.07
-
0.13
0.11
-
0.54
0.18
0.88
0.68
0.15
0.09
0.87
0.77
0.26
0.43
ND
0.52
0.52
0.28
2
9
-
1
9
-
1
0
-
5
4
-
.90
.18
.62
.88
.74
.95
.50
.67
_
17.4
_
16.0
_-.
25.2
«.
54.4
_
_
17.1
_
13.9
Tot P
0.55
_
1.07
***
0.59
HH*
1.14
_
1.16
__
0.92
_
1.37
_
1.60
_
1.00
1.33
*»
0.69
1.24
_
_
0.60
_
0.80
-------
TABLE D-l. (Continued).
Station
B~6
B-7
B-8
B-9
B-10 %
B-ll
B-12
Repa
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
i-
3
:2<
3
Depth
9.5
28.6
7.6
24.7
7.6
24.7
7.6
22.8
3.8
17.1
3.8
15.2
1.9
7.6
NHEN KO-, NO* PO,. SiO. Tot
4 3244
0.04
20.6
0.57
2.07
0.53
ND
0.67
0.95
0.57
0.07
0.04
0,75
2.48
0.04
0.56
0.04
0.05
ND
0.22
0.31
0.47
ND
1.30
0.55
0.15
0.15
0.22
0.33
0.22
2.39
0
>24
0
<4
0
0
0
0
0
0
0
1
7
0
10
0
0
0
1
0
0
0
1
0
0
0
0
0
0
0
.07
.3
.89
.88
.09
.29
.51
.92
.32
.39
.16
.23
.15
.24
.9
.72
.3
.49
.92
.12
.33
.09
.07
.72
.22
.08
.36
.25
,08
.89
0.06
0.10
0.07
0.16
0.13
0.07
0.07
0.08
0.10
0.07
0.07
0.17
0.06
0.06
0.05
0.06
0.21
0.02
0.38
0.20
0.15
0.02
0.62
0.42
0.34
0.15
0.30
0.13
1.06
0.07
0.56
0.22
0.32
0.10
1.50
0.75
0.53
0.21
1.70
0.79
0,48
0.30
0.28
0.73
0.67
0.49
1.01
4.43
1.05
6.11
2.96
3.45
2.06
5.14
0.90
8.34
3.23
9.48
5.13
4.28
8.05
8.18
362
78.
10.
17.
13.
16*
13,
13.
14.
16.
14.
15.
14.
42.
N
8
6
4
5
0
9
8
9
9
9
5
9
7
TOt P
0.51
0.96
0.52
0.9
0.73
0.73
0.66
0.89
0,86
1.44
1.07
1.44
1.16
1.63
-------
TABLE D-l. (Continued)
Station Rep Depth
C-l 1
3
1
3
C-2 1
3
1
3
C-3 1
3
1
3
C-4 1
3
1
3
C-5 1
3
1
3
C-6 1
3
1
3
C-7 1
3
1
3
5.7
15.2
5.7
13.3
5.7
20.9
-
5
-
15.2
-
5.7
_
15.2
-
3.8
-
13
-
3
-
7.6
_
NE4b
26
>20
25
>24
29
>20
24
>22
23
>20
14
13
28
>20
10
<9
17
19
11
10
13
11
6
6
11
7
8
8
.5
.6
.3
.0
.0
.0
.1
.0
.7
.0
.9
.7
.6
.6
.6
.58
.4
.7
.1
.6
.9
.7
.75
.02
.1
.70
.48
.23
b b
3 24
16
15
15
14
16
15
12
11
12
14
8
8
14
12
6
<8
11
13
7
6
10
6
4
4
34
5
5
5
.7
.6
.2
.4
.1
.14
.5
.9
.71
.24
.5
.3
.38
.03
.2
.7
.89
.63
.4
.8
.55
.1
.23
.75
.28
2
2
2
0
2
-
1
-
2
-
1
_
1
-
1
-
1
-
0
-
0
0
.74
.40
.69
.09
.14
.40
.50
.02
.89
.06
.02
.71
.89
.84
3.01
2.91
3.14
2.78
3.45
2.82
3.54
3.57
2.79
3.64
2.31
2.03
3.00
2.22
1.67
1.47
2.42
3.23
1.95
1.68
1.83
1.88
1.44
1.17
2.00
2.14
2.08
2.05
13.
13.
13.
13.
12.
-
9.
-
12.
-
8.
-
10.
8.
-
7.
-
7.
-
11.
-
12.
'4 Tot
0
71
7
61
7
66
^ _
57
5
86
96 -
43
9
55
97 -
35
7
53
66 -
36
07 -
43
78 -
31
6
40
0
41
N
.3
.9
.8
.4
.4
.7
.2
.5
.3
.5
.6
.1
.8
.9
Tot P
4.53
4.05
4.12
4.40
4.12
«.
3.18
_
3.38
_
2.82
_
3.49
2.76
_
3.16
2.34
3.79
,
3.75
-------
TABLE D-l. (Continued).
Station
C-8
c-io
C-ll
C-13
C-15
Rep*
1
2C
3
1
2C
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
1
3
Depth
3
_
-
15'
3
10
5
15
-
5
35
-
5
-
20
*"*"
HH4b
10.1
10.1
18.6
5.03
4.29
4.37
5.00
7.62
2.13
1.89
1.76
2.03
0.11
0.08
0.74
ND
1.54
1.46
2.69
20.7
0.05
3.74
NO
7.
7.
>24.
3.
3.
6.
4.
5.
3.
1.
1.
1.
0.
0.
2.
0.
1.
1.
3.
>24.
0.
17.
b
3
72
15
3
15
49
84
18
44
08
32
49
23
4
35
22
2
48
03
83
3
2
6
N
1
1
-
0
0
-
0
-
0
-
0
-
0
-
0
-
0
_
0
-
0
°2
.24
.21
.45
.37
.65
.21
.23
.07
.16
.14
.07
.12
*°4b
1.83
2.66
1.75
0.96
1.34
0.89
1.85
1.55
1.01
0.86
1.13
1.05
0.94
1.03
0.53
0.41
0.84
0.53
0.22
0.10
0.60
0.36
sio4
8.93
8.70
-
5.47
6.63
-
8.87
-
7.71
-
7.45
-
7.68
-
3.59
-
8.76
-
2.52
-
Tot N
99.7
_
25.9
*_
36.3
_
22.0
23.0
15.0
*w
17.5
w.
14.1
>
493
Tot P
-
2.94
.
_
2.02
«_
2.81
_
1.92
_.
2.18
,,,
1.44
1.53
_
1.24
«
0.60
5.77 -
mm.
20.2
1.22
NA * Not analyzed; ND » Not detected.
> - Greater than; < « Less than.
aReplicates 1 and 2 at each station are filtered and represent
dissolved nutrient data. Replicate 3 at each station is not
filtered and represents total nutrient data.
Analysis of unfiltered samples (Rep 3) for NH4, NO,, and PO.
was not originally planned, but because contamination was
evident in the NO, data, these parameters were analyzed.
'Replicate 2 was collec
for selected stations.
Replicate 2 was collected at all stations, but only analyzed
Contamination suspected.
------- |