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Sooke River Twelve Month Baseline Water Quality Study for Salmonids

by Judith R. Burke

Rose

Waterose Environmental Services

Vancouver Island, BC


Fish

3. Methods


3.1 Methods

The methods are based on a combination of factors, which include the desired objectives, technical experience, cost, and, time. The study involved over 150 sample days; therefore, affordable methods are an integral factor when selecting methods. The primary instruments include a colorimeter, digital titrator, and an electrochemical multi-meter. The study occurred from September 22, 1999 to September 21, 2000.


3.2 Quality Control and Quality Assurance

The high volume of sample days and frequency of tests limited the extent of a rigorous Quality Control and Quality Assurance program. This is one of the limitations of this study. Furthermore, because there were no previous test results for this area, the standard deviations were not available to pre-determine minimum sampling requirements. Therefore, it was determined that a minimum sample number of 12 were required for each test for each season for each site.

Ideally, one would implement a rigorous field program with field-split samples, duplicate samples, spiked samples, and an additional control site and external laboratory analysis; all of which would have rendered the project economically unfeasible. The compromise was to implement affordable methods, which were within the control of the project and still obtain quantified results. These include consistent methods, dedicated glassware and tools for each test, pretreated containers, triplicate rinsing with triple distilled de-ionized water and sample water, constant temperature control, laboratory water for reagent blanks, and extreme diligence and care.


3.3 Sample Collection

The water samples were collected clean glass or plastic containers, which were pretreated as required by the manufacturers specifications depending on the parameter tested. Different pre-treatments included acid rinse with hydrochloric acid, nitric acid, and/or industrial bleach solution. The samples were obtained in-stream in laminar flow below a point of mixing such as a waterfall or a stream riffle. The samples were tested immediately at streamside for half of the parameters. A second set of fresh samples were obtained and tested immediately off site for the balance of the parameters, which required more complex sample preparation for the test procedure. Every reasonable attempt was made to maintain the temporal spacing of sample collection.


3.4 Instrumentation

The selection of instruments was based on three factors: cost, operator knowledge, and instrument performance. The budget was limited to $5,000 for the purchase of instruments.

The primary objective was to obtain quantified test results. There are alternate instruments available to test water chemistry; however, the limiting factor is primarily the cost associated with using high performance laboratory analytical equipment. The primary instruments included a colorimeter, digital titrator, and, an electrochemical multi-meter.

3.4.1 Colorimeter

The colorimetric analysis was completed using a colorimeter. The basic principle of analysis is to mix a known quantity of chemical reagent with an unknown quantity of the species of interest. The product of the reaction changes colour and the colour intensity is proportional to the concentration of the species of interest. The colour intensity is measured by a light beam with a known frequency directed through the reaction chamber to a photovoltaic receptor cell. The amount of light that does not pass through the sample is measured as light absorbed. The absorbance reading is related to known absorbance for known quantities of the species of interest in different solution concentrations, which are precalibrated into the instrument. The relative absorbance is plotted against the known slope of known concentrations and the concentration of the sample is interpolated from the slope of the line. For some parameters, there is a direct mathematical relationship between a specific species and an alternate form of the same species. The readings are stored into the memory of the colorimeter and downloaded daily for statistical analysis at the conclusion of the season.

The ranges and estimated detection limits vary depending on the selected test. The specific colorimetric tests completed for this study are described in Table 13.

Table 13. Colorimetric Analysis Parameters, Ranges, and EDL's.

Parameter

Primary

Alternates

Range

EDL

Aluminum

Al

Al

Al2O3

0 to 0.80 mg/L Al

0.013 mg/L Al

Bromine

Br2

Br2

0 to 4.50 mg/L Br2

0.04 mg/L Br2

Chlorine, Total

Cl2

Cl2

0 to 2.00 mg/L Cl2

0.02 mg/L Cl2

Chromium, Hexavalent

Cr6+

Cr6+

CrO4

Cr2O7

0 to 0.60 mg/L Cr6+

0.01 mg/L Cr6+

Copper, Low Range

Cu

Cu

0-210 �g/L

5.4 �g/L Cu

Fluoride

F

F

0 to 2.00 mg/L F-

0.05 mg/L F-

Iron, Ferrous

Fe

Fe

0 to 3.00 mg/L Fe

0.03 mg/L Fe

Manganese

Mn

Mn

MnO4

KMnO4

0 to 0.700 mg/L Mn

0.007 mg/L Mn

Molybdenum Molybdate, Low Range

Mo6+

Mo6

MoO4

0 to 3.00 mg/L Mo6+

0.07 mg/L Mo6

Nickel

Ni

Ni

0 to 1.000 mg/L Ni

0.013 mg/L Ni

Nitrate, Low Range

NO3--N

NO3-N

NO3

0 to 0.50 mg/L

NO3-N

0.01 mg/L NO3--N

Nitrite, Low Range

NO2-

NO2-

NO2- - N

NaNO2-

0 to 0.350 mg/L NO2- N

0.005 mg/L NO2N

Nitrogen Ammonia

NH3-N

NH3-N

NH3

NH4

0 to 0.50 mg/L NH3-N

0.02 mg/L NH3-N

Phosphorus

PO43-

0-2.50 mg/L PO43-

0.05 mg/L PO43-

Silica, High Range

Si

SiO2

Si

0 to 75.00 mg/L SiO2

1.00 mg/L SiO2

Sulphate

SO4 -

SO4 -

0 to 70 mg/L SO4 -

4.9 mg/L SO4 -

Sulphide

S2-

S2-

0 to 0.70 mg/L S2-

0.01 mg/L S2-

Tannin & Lignin

Tannic

Tannic

0 to 9.0 mg/L tannic

0.1 mg/L tannin & lignin

Turbidity

0-1000 FAU

21 FAU

Zinc

Zn

Zn

0 to 3.00 mg/L Zn

0.02 mg/L Zn

3.4.2 Digital Titrator

The titration analysis was completed using a digital titrator. The basic principle of analysis is to add a known titrant to the water sample. The product of the reaction changes colour and the concentration is determined by relating the quantity of titrant relative to the volume of the water sample. The specific titrations completed for this study are described in Table 14.

Table 14. Description of Titration Analysis Parameters, Ranges, and, EDL's.

Parameter

Range

EDL

Carbon Dioxide CO2

20 to 100 mg/L

+/- 1%

Hardness, as Calcium Carbonate CaCO3

10 to 40

+/- 1%

3.4.3 Electrochemical Probe

The electrochemical analysis was completed using an electrochemical multi-meter with three probes to measure dissolved oxygen, conductivity, and pH. The EDL's of the probes are: dissolved oxygen +/- 1%, dissolved oxygen +/- 0.1 mg/L, conductivity +/- 1�s, total dissolved solids +/- 1 mg/L, and, pH +/- 0.01 pH units.

The probe was calibrated before each field trip in manufacturer calibration solutions. Duplicate meters with stable triplicate readings were used to obtain the data.


Next Section 4. Results


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For more information about the Sooke River Watershed:

Mail Email Judith Burke at Waterose Environmental Services

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