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U.S. Department of the Interior
U.S. Geological Survey
Techniques and Methods 9-A6.2
Supersedes USGS Techniques of Water-Resources Investigations,Book 9, Chapter A6.2, Version 3.0
Dissolved Oxygen
Section A, National Field Manual for the Collection of Water-Quality Data Book 9, Handbooks for Water-Resources Investigations Cover: Accurate measurement of dissolved oxygen is essential in studies of aqua tic ecosystems. Photograph by Gerolamo C. Casile, U.S. Geological Survey.Dissolved Oxygen
By U.S. Geological Survey
Supersedes USGS Techniques of Water-Resources Investigations,Book 9, Chapter A6.2, Version 3.0
U.S. Department of the Interior
U.S. Geological Survey
Chapter 6.2 of
Section A, National Field Manual for the Collection of Water-Quality Data Book 9, Handbooks for Water-Resources InvestigationsU.S. Department of the Interior
DAVID BERNHARDT, Secretary
U.S. Geological Survey
James F. Reilly II, Director
U.S. Geological Survey, Reston, Virginia
First Release: April 1998, as Techniques of Water-Resources Investigations (TWRI), book 9, chapter A6.2, version 1.0 Revised: May 2006, online as TWRI 9-A6.2, version 2.0 Revised: June 2006, online as TWRI 9-A6.2, version 2.1 Revised: September 2013, online as TWRI 9-A6.2, version 3.0 Revised: October 2020, online as Techniques and Methods, book 9, chapter A6.2 resources, natural hazards, and the environment - visit https://www.usgs.gov or call 1-888-ASK-USGS. For an overview of USGS information products, including maps, imagery, and publications, visit https://store.usgs.gov. Any use of trade, firm, or product names is for descriptive purposes onl y and does not imply endorsement by theU.S. Government.
Although this information product, for the most part, is in the public d omain, it also may contain copyrighted materials as noted in the text. Permission to reproduce copyrighted items must be secured from the copyright owner.Suggested citation:
U.S. Geological Survey, 2020, Dissolved oxygen: U.S. Geological Survey Techniques and Methods, book 9, chap. A6.2,
33 p., https://doi.org/10.3133/tm9A6.2. [Supersedes USGS Techniques of Water-Resources Investigations, book 9,
chap. A6.2, version 3.0.]ISSN 2328-7055 (online)
iiiContents
Abstract ........................................................................ ...........1 1.0 Introduction ........................................................................ 1.1Overview of Dissolved Oxygen ........................................................................
............................2 2.0Optical (Luminescence) Sensor Method ........................................................................
....................3 2.1Equipment and Field Preparations ........................................................................
......................3 2.1.1Equipment Description and Maintenance .....................................................................3
2.1.2 Field-Trip Preparations ........................................................................ .............................5 2.2Calibration of Optical Sensors ........................................................................
.............................5 2.2.1Correction for Atmospheric Pressure and Salinity ......................................................6
2.2.2Selection of Calibration Method ........................................................................
.............7 2.2.3 Optical (Luminescence) DO Sensors - Calibration Procedures ...............................7Procedure 1 - Calibration in Air ........................................................................
...............8 Variation of Procedure 1 - Air Calibration with a Wet Towel ......................................8Procedure 2 - Calibration with Air-Saturated Water ..................................................9
2.3 Measurement ........................................................................ 2.3.1 Surface Water ........................................................................ 2.3.2 3.0Spectrophotometric (Rhodazine D and Indigo Carmine) Methods ..............................................13
3.1 Equipment and Supplies ........................................................................ .....................................14 3.2Calibration and Interferences ........................................................................
...........................14 3.3 Measurement ........................................................................ 4.0 Reporting ........................................................................ 17 5.0Correction Factors for Oxygen Solubility and Salinity ....................................................................17
Acknowledgments ........................................................................ References Cited........................................................................Appendix 1.
Example comparison between spectrophotometric and optical dissolved-oxyg en meter data........................................................................Tables
6.2-1. Equipment and supplies for the optical sensor method of determining
dissolved-oxygen concentration ........................................................................
........................46.2-2. Solubility of oxygen in freshwater at various temperatures and pressures
....................206.2-3. Equipment and supplies for the spectrophotometric method of determining
dissolved-oxygen concentration using Rhodazine D and Indigo Carmine reag ents ......146.2-4. Salinity correction factors for dissolved oxygen in water ..................................................26
1-1. Data for comparison between spectrophotometric and optical dissolved-oxy
gen meter methods ........................................................................1-1. Calibration data for readings in table 1-1A ........................................................................
...33 ivConversion Factors
International System of Units to U.S. customary unitsMultiplyByTo obtain
Length
centimeter (cm)0.3937inch (in.) millimeter (mm)0.03937inch (in.) meter (m)3.281foot (ft) Mass gram (g)0.03527ounce, avoirdupois (oz) kilogram (kg)2.205pound avoirdupois (lb)Volume
liter (L)0.2642gallon (gal) milliliter (mL)0.03381 cubic centimeter (cm 3 )0.06102cubic inch (in 3 T emperature in degrees Celsius (°C) may be converted to degrees Fahr enheit (°F) as follows:°F=(1.8×°C)+32
Specific conductance is reported in microsiemens per centimeter at 25 de grees Celsius (µS/cm at 25 °C). Siemens per centimeter are the equivalent of mhos per cen timeter. Molality of a solution is the number of moles (m) of a constituent per kilogram (kg) of solution. Units of molality are reported in moles per kilogram (m/kg).Abbreviations and Symbols
DIW deionized water with resistance greater than or equal to 18 megaohms (M ), and that has been quality assuredDO dissolved oxygen
EDI equal-discharge increment, isokinetic sampling method EWI equal-width increment, isokinetic sampling methodLED light emitting diode
LDO luminescent dissolved oxygen
µg/L micrograms per liter
mg/L milligrams per literM molar
NFM National Field Manual for the Collection of Water Quality Data" (USGS) NIST National Institute of Standards and Technology nm nanometer vNWIS National Water Information System (USGS)
NWS National Weather Service
RDO rugged dissolved oxygen
USGS U.S. Geological Survey
WMA Water Mission Area (USGS)
WSC Water Science Center (USGS)
YSI Yellow Springs Incorporated
> greater than < less thanChemical Formulas
H 2O water
H 2S hydrogen sulfide
Hg mercury
viRequirements and Recommendations
As used in the U.S. Geological Survey (USGS) "National Field Manual for the Collection of Water-Quality Data" (NFM), the terms "required" and "recommended" have the USGS- • The terms "require," "required," and "requirements" in reference to USGS protocols indicate that USGS Water Mission Area (WMA) policy has been established on the quality specialists and other professionals having the appropriate exper tise. Technical Technical Memorandum 2002.13 - U.S. Geological Survey, 2002). The terms "recommend," "recommended," and "recommendation" indicate that, on the basis of research or consensus, there are several acceptable alterna tives to a given procedure or equipment selection in the NFM. Relevant technical memorand ums and publications pertinent to such recommendations are cited in the NFM to t he extent procedures. Selection from among the recommended alternatives should be based on Memorandum 2002.13 - U.S. Geological Survey, 2002).Chapter 6.2. Dissolved Oxygen
By U.S. Geological Survey
Abstract
The "National Field Manual for the Collection of Water- Quality Data" (NFM) provides guidelines and procedures for guidance and protocols for the measurement of dissolved selection and maintenance of equipment, calibration, trouble- shooting, and procedures for measurement and reporting. It updates and supersedes USGS Techniques of Water-Resources A, Rounds, Franceska D. Wilde, and George F. Ritz. Dissolved lected, is often continually measured at USGS streamgages, and is a parameter regularly measured during laboratory solved oxygen described in this chapter is applicable to most in the USGS Techniques of Water-Resources Investigations being released in the USGS Techniques and Methods series; the NFM. More information is in the general introduction to the NFM (USGS Techniques and Methods, book 9, chapterA0 - U.S. Geological Survey, 2018) at
tm9A0 . The authoritative current versions of NFM chap- ters are available in the USGS Publications Warehouse at . Comments, questions, and sugges- tions related to the NFM can be addressed to nfm@usgs.gov.1.0 Introduction
The "National Field Manual for the Collection of Water- (WMA) of the U.S. Geological Survey (USGS). The NFM updates and supersedes USGS Techniques of Water-Resources Investigations, book 9, chapter A6.2, version 3.0, by Rounds and others (2013). Science Centers (WSCs), and including those conducting are mandated to use protocols provided in the NFM2002.13
- U.S. Geological Survey, 2002). Formal training, as provided in the USGS class "Field Water-Quality Methods for supplement the information provided in the NFM and are needed to collect unbiased, high-quality data.The USGS National Field Manual provides detailed,
comprehensive, and citable procedures for monitoring the quality of surface water and groundwater. Formal train- provided in the NFM. Chapter A6.2 of the NFM provides guidance and proto- samples are collected, is often measured continually at USGS streamgages, and is regularly measured during laboratory and protocols, and applications. in the USGS Techniques of Water-Resources Investigations are being released in the USGS Techniques and Methods format of the NFM. More information is in the general introduction to the NFM (USGS Techniques and Methods,2 Chapter A6.2. Dissolved Oxygen
measurement methods described are used by the USGS onsite for routine determination of DO concentrations in fresh to DO is the use of luminescence-based (optical) sensors. Opti- over previously used amperometric sensors because optical Optical sensor methods (section 2.0) are applicable to nearly all aqueous environmental conditions. Optical sensor technology is available in single-parameter DO meters or in multiparameter sondes and can be either handheld for discrete measurements or deployed for longer term, unattended con- tinuous and real-time measurements. Spectrophotometric (colorimetric) instrumental methods example, in certain aquifers and deep-lake horizons) and can that are available for visually determining DO concentrations conditions and an accuracy check of DO-sensor performance. Noninstrumental colorimetric methods that are available for visually determining DO concentrations should not be used to report DO concentrations.The iodometric (Winkler) method is regarded as an
accurate and precise method for the calibration of DO sensors performed under controlled laboratory conditions. Before to perform Winkler titrations onsite. Standard USGS practice no longer sanctions onsite Winkler titrations or the transport method. Step-by-step instructions for conducting a Win NFM chapter have been removed and are not included in this chapter.• Some procedures for equipment operation recom-mended in this guidance document may not apply to your equipment because of technological advances or other changes.
the standard USGS procedures given in this
book 9, chapter A0 - U.S. Geological Survey, 2018) at . The authoritative current ver- sions of NFM chapters are available in the USGS PublicationsWarehouse at . Comments, questions,
and suggestions related to the NFM can be addressed to nfm@usgs.gov.1.1 Overview of Dissolved Oxygen
factors, including ambient temperature, atmospheric pressure, dissolved-oxygen data are essential for understanding and result from natural phenomena and human activities. Sources include respiration, aerobic decomposition processes, ammo- The presence of DO in aquatic systems is necessary for the an indicator of the health and geochemical quality of surfaceDISSOLVED OXYGEN: Molecular oxygen (oxygen gas)
dissolved in water.Standard procedures used by the USGS to determine
the use of luminescence-based optical sensors, or spectro- phoometric methods of analysis. Before the advent in the 2000s of optical sensors for DO measurement, the amperometric the amperometric type of sensor. The amperometric sensor is an acceptable method for use in the measurement of DO; iodometric (Winkler) method is no longer used by the USGS acceptable method for verifying the results of DO measure-2.0 Optical (Luminescence) Sensor Method 3
2.0 Optical (Luminescence) Sensor
Method
The optical sensor method can yield accurate results for tions encountered in routine USGS data-collection activities. discrete (single) or continuous (unattended) DO measurements introduced by advances in applying luminescence technol- ogy to DO measurement, optical sensors are favored for mostOptical sensors -
The technology used in optical DO
sensors involves the measurement of light-emission charac- interface (see Technical Note 1). Some characteristics of the optical DO method are - Oxygen is not consumed by the sensor at the sensor- • consequently, no stirring mechanism is required at sites• Optical sensors are relatively stable. They are able to maintain calibration over long-term deployment and kept clean.
luminescence method in natural aquatic systems. - 2• Cleaning and maintenance are relatively simple. The optical sensor contains no anode or cathode to service, and uses no electrolyte solution, membranes, or O-rings.
Optical-sensor maintenance is dictated by manufac- • Manufacturers generally recommend annual to bian- nual replacement of the luminophore-containing module (also called lumiphore"). Some sensors may the sensor becomes inoperative. The modules are easily replaced. Sensors should be calibrated or undergo a calibration check after module replacement.