Dissolved Oxygen: Winkler Test

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Dissolved Oxygen

Introduction:
What is dissolved oxygen?
Dissolved oxygen (DO) refers to microscopic bubbles of gaseous oxygen (O
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) that are mixed in water and available to aquatic organisms for respirationa critical process for almost all organisms.

The is used to determine the level of dissolved oxygen in fresh water samples. What follows is a set of instructions on how to perform the test.

Winkler test

Materials
Stage 1

Manganese(II) sulfate 48% Potassium iodide 15% in potassium hydroxide 70% Sample of fresh water Latex gloves Safety glasses

Stage 2

Sulfuric acid 50% Sodium thiosulfate 0.31% Starch making up solutions|solution 0.1% Burette Burette stand 10 ml pipette and pipette filler 100 ml conical flasks Filter paper Latex gloves Safety glasses

Method
Stage 1
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Dissolved Oxygen
Collect and label water samples in 25 ml stoppered bottles. (Two samples per location are required for Biological Oxygen Demand testing.) Add 0.1 ml of manganese(II) sulfate solution, and mix carefully, without letting in air. Add 0.2 ml of alkaline potassium iodide, and again mix without letting in air. A pinky-brown precipitate should appear. At this point the sample may be stored for later analysis in the laboratory.

Stage 2
Add 0.3 ml sulfuric acid to each sample, and mix. Allow the sample to stand for two minutes. If the precipitate does not dissolve into iodine solution, add a further 0.1 ml acid. Fill the burette with thiosulfate solution and adjust to zero (or note the burette reading). Transfer 10 ml of the sample to a conical flask, and add a few drops of starch solution. The subsample should turn blue. Titrate the subsample with thiosulfate until it turns clear. (You may find the endpoint easier to see if the conical flask is stood on a sheet of filter paper.) Record and repeat the titration.

Notes
Each milliliter of thiosulfate titer is equivalent to 0.1 mg of oxygen in the 10 ml subsample. Thus 1 ml of thiosulfate is equivalent to 1 mg oxygen per 100 ml fresh water. To determine five-day Biological Oxygen Demand (BOD5), several dilutions of a sample are analyzed for dissolved oxygen before and after a five-day incubation at 20 degrees Celsius (68 degrees Fahrenheit) in the dark. In some cases the sample must be provided a source of oxygenusing bacteria, called "seed", in order to obtain results. The difference in DO and the dilution factor are used to calculated BOD5. The resulting number (usually reported in parts per million or milligrams per Liter) is useful in determining the relative organic strength of sewage or other polluted waters. The BOD5 test is an example of analysis that determines classes of materials in a sample. Instrumental methods for measurement of Dissolved Oxygen have widely supplanted the routine use of the Winkler test, although it is still widely used to check instrument calibration.

Advanced projects in chemistry


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Dissolved Oxygen
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Advanced Projects in Chemistry Author: Anjali Gharpure Advanced Projects in Chemistry Dissolved Oxygen levels in water bodies For students of theK-11 or K-12 grades with a background in biological sciences, the dissolved oxygen tests would be both a worthwhile and a learning effort. Measuring dissolved oxygen levels is important to determine the level of contamination of groundwater, an important water quality parameter. Dissolved oxygen levels are important as they indicate ground water pollution. Oxygen is vitally important for healthy aquatic life and low dissolved oxygen levels are indicative of polluted waters. The optimum value for dissolved oxygen determined should be between 4-6 mg/L. Tests commonly monitored for determining the oxygen content in water masses are-Biological oxygen demand (BOD), Chemical oxygen demand (COD) and Dissolved oxygen (DO) by Winklers method. Biochemical Oxygen Demand (BOD) is an empirical test determining the relative oxygen requirement of effluent and polluted waters. BOD tests consist of a 5 day period in which a sample is placed in an airtight bottle under controlled conditions temperature (20C 1C), under dark conditions to prevent photosynthesis. The dissolved oxygen (DO) in the sample is measured before and after the 5 day incubation period. In contrast, Chemical Oxygen Demand (COD) is often preferred for daily analysis. The COD analysis is reproducible and requires a shorter period of time for completion. It measures both the biologically oxidizable and biologically inert organic materials present in sewage. Waste water sample is refluxed with excess potassium dichromate in dilute sulfuric acid. In the presence of silver sulfate as catalyst and mercuric sulfate. The organic matter of the sample is oxidized to water, carbon dioxide and ammonia. The excess dichromate remaining unreacted in the solution is titrated against standard Ferrous ammonium sulfate. The Chemical Oxygen Demand (COD) test measures the oxygen equivalent consumed by organic matter in a sample during strong chemical oxidation. Potassium dichromate is used as the oxygen source with concentrated sulfuric acid added to yield a strong acidic oxidizing medium. Other reagents added, in the analysis serve to drive the oxidation reaction to completion. These include mercuric sulfate, silver sulfate and sulfamic acid. Mercuric sulfate is added to remove complex chloride ions present in chlorinated water samples. Without the mercuric sulfate the chloride ions would get oxidized form chlorine compounds in the strong acidic medium. These chlorine compounds would in turn oxidize the organic matter in the water sample. The resulting COD value determined would then be lower than the actual value. Silver sulfate is added as a catalyst for the oxidation of short, straight chain organic compounds and alcohols. In the absence of silver sulfate the COD of the sample would be lower than the actual value. Sulfamic acid prevents interference of the nitrite ions. In the absence of sulfamic acid, the COD reading of the sample determined would be higher than the actual value. However, the oxidation of the organic matter is not always 100% complete with the COD test. Volatile organics, ammonia and aromatic hydrocarbon are not oxidized completely by this method. Despite these observations, the COD test has a number of merits over the BOD test. COD results are available much sooner. COD tests require very little sample preparation. The COD test oxidizes a wider range of chemical compounds and can be standardized more easily. The major disadvantage of the COD test is that the results are not directly applicable to the 5-day BOD
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Dissolved Oxygen
results without correlation studies over a long period of time. The Winkler Method is a technique used to measure dissolved oxygen in freshwater systems. Dissolved oxygen is used as an indicator of the health of a water body, where higher dissolved oxygen concentrations are correlated with high productivity and little pollution. This test is performed on-site, as delays between sample collection and testing may result in an alteration in oxygen content. The Winkler Method also uses titration to determine dissolved oxygen in the water sample. The sample is filled completely with water in an airtight bottle. The dissolved oxygen in the sample is then "fixed" by adding a series of reagents- managnous sulfate, alkaline azide iodide till a floc forms. The floc is allowed to settle after which concH2SO4 is added to form an acid compound. It is titrated with a neutralizing compound that results in a color change. The point of color change, the "endpoint," coincides with the dissolved oxygen concentration in the sample. Dissolved oxygen analysis is best done in the field, as the sample is left unaltered by atmospheric equilibration. The liberated iodine is titrated against a standard solution of sodium thiosulfate, from which the amount of dissolved oxygen is calculated. Water pollutants include organic and inorganic effluents from industries, radioactive materials and thermal pollutants. A K-12 grade project that includes these experiments tests the students learning outcome and awareness in environmental chemistry. It gives the students the chance to determine and analyse for themselves the level of water contamination in their city or town.

Hydroculture/Aeration
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Dissolved Oxygen
Fine bubble aeration

Oxygenation is important to the sustainability of a hydroculture ecosystem. Plant roots, aerobic bacteria, hydrophytes, fish and or other aerobic organisms and tissue require oxygenation. Insufficient oxygen (environmental hypoxia) may occur in water or substrate, creating a hazardous environment for aerobic organisms and tissue. Deoxygenation increases the relative population of anaerobic organisms such as certain bacteria, resulting in root rot, fish kills and other adverse events. Increasing the concentration of aerobic conditions provides a a healthy hydroculture ecosystem. Water aeration is required in water bodies that suffer from anoxic conditions. Aeration can be achieved by using an air pump with a diffuser, or by surface agitation from a fountain or spraylike device to allow for oxygen exchange at the surface and the release of noxious gases such as carbon dioxide, methane or hydrogen sulfide. Dissolved oxygen (DO) is a major contributor to water quality. Not only do fish and other aquatic animals need it, but oxygen breathing aerobic bacteria decompose organic matter. When oxygen concentrations become low, anoxic conditions may develop which can decrease the ability of the water body to support life.

Hypoxia
Hypoxia, or oxygen depletion, is a phenomenon that occurs in aquatic environments as dissolved oxygen (DO; molecular oxygen dissolved in the water) becomes reduced in concentration to a point where it becomes detrimental to aquatic organisms living in the system. Dissolved oxygen is typically expressed as a percentage of the oxygen that would dissolve in the water at the prevailing temperature and salinity (both of which affect the solubility of oxygen in water; see oxygen saturation and underwater). An aquatic system lacking dissolved oxygen (0% saturation) is termed anaerobic, reducing, or anoxic; a system with low concentrationin the range between 1 and 30% saturationis called hypoxic or dysoxic. Most fish cannot live below 30% saturation. A "healthy" aquatic environment should seldom experience less than 80%. The exaerobic zone is found at the boundary of anoxic and hypoxic zones.

Aeration methods

Dissolved Oxygen

Here are ways of infusing air into the nutrient solution and aquaponic tank. Also, keeping the plant roots suspended above the nutrient solution is beneficial, since there is a limit to the amount of oxygen saturation that can be contained in water.

Fountains
Fountains aerate by pulling water from the surface of the water and propelling it into the air. This process utilizes air-water contact to transfer oxygen. As the water is propelled into the air, it breaks into small droplets. Collectively, these small droplets have a large surface area through which oxygen can be transferred. Upon return, these droplets mix with the rest of the water and thus transfer their oxygen back to the ecosystem. Fountains are a popular method of surface aerators because of the aesthetic appearance that they offer. However, most fountains are unable to produce a large area of oxygenated water.[1]

Fine bubble aeration

Dissolved Oxygen
Fine bubble aeration is an efficient way to transfer oxygen into water. Attached to the unit are a number of diffusers. These bubbles are known as fine bubbles. The EPA defines a fine bubble as anything smaller than 2mm in diameter.[2] Fine bubble diffused aeration is able to maximize the surface area of the bubbles and thus transfer more oxygen into water per bubble. Additionally, smaller bubbles take more time to reach the surface so not only is the surface area maximized but so are the number of seconds each bubble spends in the water, allowing it more time to transfer oxygen to the water. As a general rule, smaller bubbles and a deeper release point will generate a greater oxygen transfer rate.[3] However, almost all of the oxygen dissolved into the water from an air bubble occurs when the bubble is being formed. Only a negligible amount occurs during the bubbles transit to the surface of the water. This is why an aeration process that makes many small bubbles is better than one that makes fewer larger ones. The breaking up of larger bubbles into smaller ones also repeats this formation and transfer process. [4] One of the drawbacks to fine bubble aeration is that the membranes of ceramic diffusers can sometimes clog and must be cleaned in order to keep them working at their optimum efficiency. Also, they do not possess the ability to mix as well as other aeration techniques, such as coarse bubble aeration.[1]

Drain
In certain types of hydroculture, such as flood drain systems, water can be cycled to frequently drain away from the hydroculture system. Plant roots suspended in air provides them aeration that can not be accomplished by allowing plant roots to be saturated in water.

Measurement
Further information: w:Cubic feet per minute In aquatic environments, oxygen saturation is a relative measure of the amount of oxygen (O2) dissolved in the water. Supersaturation can sometimes be harmful for organisms and cause decompression sickness. Dissolved oxygen (DO) is measured in standard solution units such as millilitres O2 per liter (ml/L), millimoles O2 per liter (mmol/L), milligrams O2 per liter (mg/L) and moles O2 per cubic meter (mol/m3). For example, in freshwater under atmospheric pressure at 20C, O2 saturation is 9.1 mg/L.

Effects On Dissolved Oxygen:


The solubility of oxygen is affected by temperature and by the partial pressure of oxygen over the water.

Dissolved Oxygen
How does temperature affect dissolved oxygen levels? The solubility of oxygen is greater in colder water than in warm water. Oxygen slips into "pockets" that exist in the loose hydrogen-bonded network of water molecules without forcing them apart. The oxygen is then caged by water molecules, which weakly pin it in place. The dissolution is exothermic overall, so cooling shifts the equilibrium towards the dissolved form [1]. How does oxygen partial pressure affect dissolved oxygen levels? Oxygen in water obeys Henry's law rather well; the solubility is roughly proportional to the partial pressure of oxygen in the air: pO2 = KO2 xO2 where pO2 is the partial pressure of oxygen in Torr, xO2 is the mole fraction of oxygen in oxygen-saturated 7 water, and KO2 is the Henry's law constant for oxygen in water (about 3.30 10 K/Torr for at 298 K [2]). Higher air pressure means higher partial pressure of oxygen, so waters at sea level can contain dissolve slightly more oxygen than mountain streams at the same temperature. High humidity very slightly lowers the fraction of oxygen in the air, and so lowers saturated dissolved oxygen levels slightly. Many empirical equations are available to accurately estimate oxygen solubility as a function of temperature, pressure, and humidity. The more accuracy you require, the more complex the equations are. Here are some very simple empirical equations that give the saturated dissolved O 2 concentration (DO) in mg O2/L water. They apply to oxygen in distilled water at a barometric pressure of P (in torr), at a temperature of t (C), with a water vapor pressure of p (in torr) [3]:

0C < t < 30C

DO =

(P-p) 0.678 35 + t (P-p) 0.827 49 + t

30C < t < 50C

DO =

Here's a quick DO calculator based on these functions. Just enter the barometric pressure in torr, and the water temperature in C. Hit the Calculate button to see the saturated water vapor pressure and the predicted DO concentration.

Barometric Water Pressure Temperature (torr) (C)

Water Vapor Saturated DO Pressure Concentration (torr) (mg/L)

The saturated water vapor pressure is estimated by linear interpolation from a table of experimental values, and is reliable to 3-4 figures. The DO concentration is reliable to 2-3 figures.

Dissolved Oxygen
Importance Of Dissolved Oxygen:
Dissolved Oxygen
A good level of dissolved oxygen Is essential for aquatic life.

Dissolved Oxygen Testing Field Kit Information Back to Parameters List

Why Dissolved Oxygen is Important


Dissolved oxygen analysis measures the amount of gaseous oxygen (O2) dissolved in an aqueous solution. Oxygen gets into water by diffusion from the surrounding air, by aeration (rapid movement), and as a waste product of photosynthesis. When performing the dissolved oxygen test, only grab samples should be used, and the analysis should be performed immediately. Therefore, this is a field test that should be performed on site.
Environmental Impact:

Total dissolved gas concentrations in water should not exceed 110 percent. Concentrations above this level can be harmful to aquatic life. Fish in waters containing excessive dissolved gases may suffer from "gas bubble disease"; however, this is a very rare occurrence. The bubbles or emboli block the flow of blood through blood vessels causing death. External bubbles (emphysema) can also occur and be seen on fins, on skin and on other tissue. Aquatic invertebrates are also affected by gas bubble disease but at levels higher than those lethal to fish. Adequate dissolved oxygen is necessary for good water quality. Oxygen is a necessary element to all forms of life. Natural stream purification processes require adequate oxygen levels in order to provide for aerobic life forms. As dissolved oxygen levels in water drop below 5.0 mg/l, aquatic life is put under stress. The lower the concentration, the greater the stress. Oxygen levels that remain below 1-2 mg/l for a few hours can result in large fish kills.

Dissolved Oxygen
Dissolved oxygen (DO) is the amount of oxygen that is present in the water. It is measured in milligrams per liter (mg/L), or the number of milligrams of oxygen dissolved in a liter of water.

Why is dissolved oxygen important?


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Dissolved Oxygen
Just like humans, all of the Chesapeake Bay's living creatures from the fish and crabs that swim through its waters to the worms that bury themselves in its muddy bottom need oxygen to survive. Humans use their lungs to inhale oxygen from the air. But worms, fish, crabs and other underwater animals use gills to get oxygen from the water. As water moves across an animals gills, oxygen is removed and passed into the blood. Gills work better when there is more oxygen in the surrounding water. As dissolved oxygen levels decrease, it becomes harder for animals to get the oxygen they need to survive.

How much dissolved oxygen do animals need?


Scientists generally agree that the Bays creatures need dissolved oxygen concentrations of 5.0 mg/L or more to live and thrive. However, the amount of oxygen an animal needs varies depending on how large or complex the animal is and where it lives.

Worms and clams that live in the Bay's muddy bottom where oxygen levels are naturally low only need dissolved oxygen concentrations of at least 1 mg/L. Fish, crabs and oysters that live or feed along the bottom require dissolved oxygen concentrations of 3 mg/L or more. Spawning migratory fish and their eggs and larvae need up to 6 mg/L during these sensitive life stages.

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Dissolved Oxygen

Areas with less than 0.2 mg/L of dissolved oxygen are called anoxic. Most animals cannot live in these areas, which is why they are often called dead zones.

How does oxygen get into the water?


Oxygen gets into the water when:
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Dissolved Oxygen

Oxygen from the atmosphere dissolves and mixes into the waters surface Algae and bay grasses release oxygen during photosynthesis Water flows into the Bay from streams, rivers and the ocean. Ocean waters generally have more oxygen. River waters are fast-moving, which helps oxygen from the air mix in.

How do low-oxygen areas form?


Most areas in the Bay that have low dissolved oxygen levels are the result of a complex interaction of several natural and man-made factors. These include temperature, nutrient pollution, how water flows in the Bay, and the shape of the Bay's bottom.

High temperatures
Temperature limits the amount of oxygen that can dissolve in water. The Bays waters can hold more oxygen during winter than during the hot summer months. However, even at the warmest temperatures seen in the Bay (around 91 degrees Fahrenheit), water is capable of having dissolved oxygen concentrations of 6-7 mg/L. So although high temperatures can influence dissolved oxygen levels, temperature is not the only cause of lowoxygen areas found in the Bay each summer.

Nutrient pollution
Too many nutrients in the water (called eutrophication) can fuel the growth of algae blooms. Oysters, menhaden and other filter feeders eat a portion of the excess algae, but much of it does not end up being consumed. The leftover algae die and sink to the Bays bottom, where they are decomposed by bacteria. During this process, bacteria consume oxygen until there is little or none left in these bottom waters.

Flow of water
Another factor influencing dissolved oxygen levels is the division between water flowing in from the ocean and out of the Bays freshwater rivers and streams. Water flowing from the ocean is generally salty and cooler, while river water is fresh and warmer. Because of these differences, river water weighs less than ocean water and actually floats on top of it. (Wind and other strong mixing forces may change this pattern.) The boundary where the fresh water layer meets the saltier water layer below is called the pycnocline. The pycnocline acts as a physical barrier that prevents the two layers from mixing together. During the summer, when algae-consuming bacteria are most active, the pycnocline cuts off oxygen-deprived bottom waters from oxygen-rich surface waters. This can create large areas of low or no oxygen at the bottom of the Bay.
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Dissolved Oxygen
Shape of the Bay's bottom
The Bay's bottom is not flat; rather, it has varying shallow and deep areas. In certain bowlshaped areas of the Bay's bottom, the pycnocline can act like a lid that cuts off bottom waters from receiving any oxygen. This phenomenon often takes place each summer in:

The middle of the Bay's mainstem, from the Bay Bridge south to the mouth of the Potomac River The lower Chester, Potomac and Rappahannock rivers The lower part of Eastern Bay, near Kent Island

Oxygen saturation
From Wikipedia, the free encyclopedia Jump to: navigation, search

Oxygen saturation or dissolved oxygen (DO) is a relative measure of the amount of oxygen that is dissolved or carried in a given medium. It can be measured with a dissolved oxygen probe such as an oxygen sensor or an optode in liquid media, usually water. The standard unit is milligrams per litre (mg/l) or parts per million (ppm). Oxygen saturation can be measured regionally and non-invasively. Arterial oxygenation is commonly measured using pulse oximetry. Tissue saturation at peripheral scale can be measured using NIRS. This technique can be applied on both muscle and brain.

Oxygen in medicine
Main article: Oxygenation (medical)

In medicine, oxygen saturation refers to oxygenation, or when oxygen molecules (O2) enter the tissues of the body. In this case blood is oxygenated in the lungs, where oxygen molecules travel from the air and into the blood. Oxygen saturation, or (O2) stats measure the percentage of hemoglobin binding sites in the bloodstream occupied by oxygen. Fish, invertebrates, plants, and aerobic bacteria all require oxygen for respiration. Blood is also vital to the body system.

Environmental oxygen saturation


Main article: Oxygenation (environmental)

Oxygen saturation in the environment generally refers to the amount of oxygen dissolved in the soil or bodies of water. Environmental oxygenation can be important to the sustainability of a
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Dissolved Oxygen
particular ecosystem. A well-mixed body of water will be fully saturated, with approximately 10mg/L at 15 C (here is a table of dissolved oxygen versus temperature). The optimal levels in an estuary for Dissolved Oxygen (DO) is higher than 6 ppm.[citation needed] Insufficient oxygen (environmental hypoxia), often caused by the decomposition of organic matter, may occur in bodies of water such as ponds and rivers, tending to suppress the presence of aerobic organisms such as fish. Deoxygenation increases the relative population of anaerobic organisms such as plants and some bacteria, resulting in fish kills and other adverse events. The net effect is to alter the balance of nature by increasing the concentration of anaerobic over aerobic species

Dissolved Oxygen & Temperature Data Summary for Middle Rouge Subwatershed
3/12/00

Introduction
Beginning in 1993, the RPO and its grantees have measured dissolved oxygen (DO) and temperature at various sites throughout the Middle Rouge Subwatershed, including: Numerous river locations Four storm water outfalls The inlet and outlet of several nonpoint source evaluation projects. The effluent of the newly constructed Dearborn Heights CSO Basin. This packet addresses DO and temperature results from river monitoring only, and the data summarized are only from some of the river monitoring surveys performed. A complete list of DO and temperature river monitoring performed by the RPO is presented in Table 1. A map and table identifying all river monitoring locations in the Middle Rouge Subwatershed have been provided separately. Data results should be viewed in light of several significant changes which have occurred in the subwatershed in recent years. Approximately half of the Dearborn Heights CSO areas tributary in the Lower Rouge have been controlled by a CSO basin which became operational in the Fall of 1997. The treated
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Dissolved Oxygen
effluent enters the Middle Rouge River just east of Telegraph Road. All CSO areas in Plymouth Township, Livonia, Westland, and Garden City which are tributary to the Middle Rouge River were controlled by sewer separation projects. However, due to problems with some of these projects, untreated sanitary sewer overflows are still occurring during some precipitation events. The Newburgh Lake remediation project took place in 1997-98, which included completely emptying the lake.

Dry Weather Grab DO Observations (Figure 1 and Table 2)


Note: Grab sampling results dep end greatly on the time of day when sampling occurred. At both sites monitored, mean dry weather water temperature is highest in 1998 and lowest in 1997. At both sites monitored, mean dry weather DO is highest in 1997 and lowest in 1998.

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