Documente Academic
Documente Profesional
Documente Cultură
0 (5/2006)
DO 1
DISSOLVED OXYGEN 6.2
Revised by Michael E. Lewis
Page
Dissolved oxygen .................................................................... DO3
6.2.1 Amperometric and luminescent-sensor methods ............5
6.2.1.A Equipment and supplies ....................................... 6
6.2.1.B Calibration .........................................................10
One-point and two-point calibrations ........................ 10
Correction for atmospheric pressure and salinity..... 11
Calibration procedures................................................ 13
1. Air-calibration chamber in air........................... 13
2. Calibration with air-saturated water................. 15
3. Air-calibration chamber in water ...................... 17
6.2.1.C Measurement......................................................19
Surface Water .............................................................19
Ground Water.............................................................22
6.2.1.D Troubleshooting
(amperometric instruments) ...........................24
6.2.2 Spectrophotometric method..........................................25
6.2.2.A Equipment and supplies ................................... 25
6.2.2.B Calibration and interferences ...........................26
6.2.2.C Measurement ....................................................... 27
Dissolved Oxygen, Version 2.0 (5/2006) U.S. Geological Survey TWRI Book 9
2 DO
6.2.3 Iodometric (Winkler) method ...................................... 29
6.2.3.A Equipment and supplies.................................... 30
6.2.3.B Measurement ..................................................... 31
6.2.4 Reporting ....................................................................... 33
6.2.5 Correction factors for oxygen solubility
and salinity .................................................................. 33
Selected references............................................................................46
Acknowledgments ......................................................................... 48
Illustrations
6.21. Graph showing factors used to correct atmospheric
pressures adjusted to sea level .......................................... 12
Tables
6.21 Equipment and supplies for the amperometric and
luminescent-sensor methods of dissolved-oxygen
determenation ......................................................................7
6.22 Factors used to correct atmospheric pressures adjusted
to sea level..............................................................................12
6.23 Troubleshooting guide for amperometric instruments .....24
6.24 Equipment and supplies for the spectrophotometric
method of dissolved-oxygen determination........................26
6.25 Equipment and supplies for the iodometric (Winkler)
method of dissolved-oxygen determination........................30
6.26 Solubility of oxygen in water at various temperatures
and pressures.........................................................................35
6.27 Salinity correction factors for dissolved oxygen in water
(based on conductivity) ..................................................... 41
Chapter A6. Field Measurements Dissolved Oxygen, Version 2.0 (5/2006)
DO 3
DISSOLVED OXYGEN 6.2
The concentration of dissolved oxygen in water is affected by many
factors including ambient temperature, atmospheric pressure, and ion
activity. Accurate data on the concentration of dissolved oxygen (DO)
in environmental water resources are essential for documenting
changes that result from natural phenomena and human activities.
Sources of DO in water include atmospheric aeration and photosyn-
thetic activities of aquatic plants. Many chemical and biological reac-
tions in ground water and surface water depend directly or indirectly
on the amount of available oxygen. Dissolved oxygen is necessary in
aquatic systems for the survival and growth of many aquatic organisms
and is used as an indicator of the health of surface-water bodies.
DISSOLVED OXYGEN:
molecular oxygen
(oxygen gas)
dissolved in water.
Standard field methods used by the U.S. Geological Survey (USGS) for
determining concentrations of DO in surface and ground waters include
the use of amperometric and luminescent-based-sensor instruments and
spectrophotometric analysis. Selection of a measurement method
should take into consideration environmental conditions, the specific
data-quality objectives of the data-collection program, and the inherent
benefits of a given technology. Except where noted, these methods are
used routinely to determine the concentration of dissolved oxygen in
fresh to saline unfiltered surface and ground waters.
Dissolved Oxygen, Version 2.0 (5/2006) U.S. Geological Survey TWRI Book 9
4 DO
The amperometric method (section 6.2.1) has been the standard
USGS procedure for the past 10 to 15 years for determining
aquatic DO concentrations that exceed 1 milligram per liter
(mg/L).
The luminescent-based sensor method (section 6.2.1) uses
relatively new technology, and applies to the same
environmental conditions as the amperometric method.
The spectrophotometric method (section 6.2.2 - for example, the
Rhodazine-D
1
technique) is recommended for determining
concentrations of DO less than 2.0 mg/L.
The iodometric (Winkler) method (section 6.2.3) is regarded as
an accurate and precise method for the determination of
dissolved oxygen in water; however, it is not a standard USGS
method for field determinations of DO because the accuracy and
reproducibility achieved depend largely on knowledge of the
presence of possible sources of interference (nitrite, ferrous or
ferric iron, and organic matter, for example) and on the
experience and technique of the data collector. In a laboratory
environment, the method is excellent for calibrating DO
instrument systems.
Some procedures for equipment operation recommended in
this guidance document may not apply to your equipment as
a result of recent technological advances. Document any
changes made to standard USGS procedures.
1
Rhodazine-D
TM
, a colorless, reduced phenzone dye, is a proprietary product of
CHEMetrics, Incorporated, and constitutes approximately 0.01 volume percent of
solution in the ampoule. Remaining constituents in the ampoule are water, diethylene
glycol, hydroxymethyl aminomethane, and potassium hydroxide.
Chapter A6. Field Measurements Dissolved Oxygen, Version 2.0 (5/2006)
DO5
AMPEROMETRIC AND 6.2.1
LUMINESCENT-SENSOR
METHODS
The amperometric and luminescent-sensor methods are appropriate for
routine measurement of DO concentrations under most of the field
conditions encountered by USGS data-collection personnel. Calibra-
tion procedures are similar for these methods.
The amperometric method has been the most commonly used
field method for measuring DO in water for USGS data-
collection efforts. The DO concentration is determined using a
temperature-compensating meter connected to a polarographic-
membrane type of sensor.
The method is relatively simple to use and is well-suited to
making discrete or continuous in situ measurements of DO
concentration in surface water or ground water.
Method performance can be negatively affected by calibration
drift; by loose, wrinkled, or damaged membranes; or by sen-
sor contact with hydrogen sulfide. Unfortunately, poor perfor-
mance can occur without any indications from the instrument
readings.
The luminescent-sensor technology that has been developed
for environmental monitoring of DO in water is considered an
appropriate alternative to the amperometric method. The
luminescent-sensor method involves the measurement of light-
emission characteristics of a luminescent-based reaction at the
sensor-water interface (see TECHNICAL NOTE). While the relative
benefits of the technology are apparent, it should be recognized
that its application at typical USGS sampling sites is relatively
new; therefore, it does not benefit from the experience derived
from years of use, as is the case with the amperometric method.
There are no consumables such as membranes or filling solu-
tions with the new method, unlike the amperometric method.
The technology does not consume oxygen at the sensor-water
interface; therefore, no stirring is required in slow or stagnant
water.
There are no known sources of interference to the method in
natural aquatic systems.
Dissolved Oxygen, Version 2.0 (5/2006) U.S. Geological Survey TWRI Book 9
6DO
TECHNICAL NOTE: The luminescent sensor employs a light-
emitting diode (LED) to provide incident light, which excites the
oxygen- sensi t i ve l umi nescent - dye mol ecul e subst r at e
(luminophore) of the sensor. After dissipation of the excitation
energy, longer-wavelength light is emitted (luminescence). The
magnitude of steady-state luminescence (intensity)that is, the
average luminescent lifetime (the phase difference between the
excitation light and the returned light)is measured by the
sensor and is inversely proportional to the DO concentration in
the water.
6.2.1.A EQUIPMENT AND SUPPLIES
DO instruments (meters and sensors) are available from a number of
commercial vendors. Because the instructions for use, calibration, and
maintenance often differ for each manufacturer, the user is cautioned
to read and carefully follow the instructional manual for the instrument
system to be used. DO instruments, and expecially the sensors, are
sophisticated electronic equipment and require care in handling and
operation. The equipment and supplies required for the amperometric
and luminescent-sensor methods of measuring the DO concentration
in a water body are listed in table 6.2-1.
Amperometric instrument systems consist of the entire sensor
assembly, including the electrolyte solutions, membranes, and
thermistor thermometers.
Protect sensors and other supplies from being jostled during
transportation, from sudden impacts, sudden temperature
changes, and extremes of heat and cold.
Follow the manufacturers recommendations for short-term
(field) and long-term (office) storage of sensors and for
performance checks.
Chapter A6. Field Measurements Dissolved Oxygen, Version 2.0 (5/2006)
DO7
Table 6.21. Equipment and supplies for the amperometric and luminescent-
sensor methods of dissolved-oxygen determination
1
[DO, dissolved oxygen; mg/L, milligrams per liter; NFM, National Field Manual
for the Collection of Water-Quality Data; , minus; +, plus; C, degrees Celsius;
and , plus or minus]
Spare batteries
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4
Dissolved Oxygen, Version 2.0 (5/2006) U.S. Geological Survey TWRI Book 9
36DO
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0
Chapter A6. Field Measurements Dissolved Oxygen, Version 2.0 (5/2006)
DO37
T
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9
Dissolved Oxygen, Version 2.0 (5/2006) U.S. Geological Survey TWRI Book 9
38DO
T
a
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6
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2
6
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S
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0
Chapter A6. Field Measurements Dissolved Oxygen, Version 2.0 (5/2006)
DO39
T
a
b
l
e
6
.
2
6
.
S
o
l
u
b
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s
C
o
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e
d
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
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9
Dissolved Oxygen, Version 2.0 (5/2006) U.S. Geological Survey TWRI Book 9
40DO
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0
Chapter A6. Field Measurements Dissolved Oxygen, Version 2.0 (5/2006)
DO41
T
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42DO
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2
Chapter A6. Field Measurements Dissolved Oxygen, Version 2.0 (5/2006)
DO43
T
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6
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Dissolved Oxygen, Version 2.0 (5/2006) U.S. Geological Survey TWRI Book 9
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4
Chapter A6. Field Measurements Dissolved Oxygen, Version 2.0 (5/2006)
DO45
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Dissolved Oxygen, Version 2.0 (5/2006) U.S. Geological Survey TWRI Book 9
46DO
SELECTED REFERENCES
American Public Health Association, 2005, Standard methods for the
examination of water and wastewater (21st ed.): Washington, D.C., American
Public Health Association, American Water Works Association, and Water
Environment Federation, p. 4-136 to 4-137, http://www.standardmethods.org/.
ASTM International, 2006, D888-05 standard test methods for dissolved oxygen
in water: accessed May 17, 2006, at
http://www.astm.org/cgi-bin/SoftCart.exe/DATABASE.CART/REDLINE_PA
GES/D888.htm?L+mystore+zmtx1699.
ASTM International, 2005, D5543-94 (2005) standard test methods for low-level
dissolved oxygen in water: accessed May 15, 2006, at
http://www.astm.org/cgi-bin/SoftCart.exe/DATABASE.CART/REDLINE_PA
GES/D5543.htm?L+mystore+aaam0310.
Brown, Eugene, Skougstad, M.W., and Fishman, M.J., 1970, Methods for
collection and analysis of water samples for dissolved minerals and gases:
U.S. Geological Survey Techniques of Water-Resources Investigations,
book 5, chap. A1, p. 126-129.
CHEMetrics, Inc., 2006, Oxygen, dissolved: accessed May 15, 2006, from
http://www.chemetrics.com/catalogpdfs.html.
Gilbert, T.W., Behymer, T.D., Castaneda, H.B., March 1982, Determination of
dissolved oxygen in natural and wastewaters: American Laboratory,
p. 119-134.
Hach Company, Hach LDO technologyreal-world FAQ: accessed September
27, 2005 at
http://www.hach.com/hc/view.document.only.invoker/View=HTML_LDO_R
EALWORLD_FAQ/NewLinkLabel=Hach+LDO+Technology:+Real-
World+FAQ/PREVIOUS_BREADCRUMB_ID=HC_SEARCH_KEYWORD
/SESSIONID|ATBwTU1URXlOemMwTmpVek9UazJNeVpuZFdWemRFVl
dXQT09QQ==|.
Hem, J.D., 1985, Study and interpretation of the chemical characteristics of
natural water (3d ed.): U.S. Geological Survey Water-Supply Paper 2254,
p. 155-156.
In-Situ Inc., Multi-parameter water quality Troll