Merenja u hidrotehnici

Dusan Prodanovi\'c

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Contents

10  (10) Merenje parametara kvaliteta
    10.1  Parametri kvaliteta vode
        10.1.1  Ammonium
            10.1.1.1  What is ammonium?
            10.1.1.2  How is ammonium measured?
            10.1.1.3  How is ammonium measurement useful in water quality monitoring applications?
            10.1.1.4  How is ammonium measurement implemented in Hydrolab instruments?
            10.1.1.5  Should I consider Hydrolab ammonium measurement?
        10.1.2  Nitrate
            10.1.2.1  What is nitrate?
            10.1.2.2  How is nitrate measured?
            10.1.2.3  How is nitrate measurement useful in water quality monitoring applications?
            10.1.2.4  How is nitrate measurement implemented in Hydrolab instruments?
            10.1.2.5  Should I consider Hydrolab nitrate measurement?
        10.1.3  Chloride
            10.1.3.1  What is chloride?
            10.1.3.2  How is chloride measured?
            10.1.3.3  How is chloride measurement useful in water quality monitoring applications?
            10.1.3.4  How is chloride measurement implemented in Hydrolab instruments?
            10.1.3.5  Should I consider Hydrolab chloride measurement?
        10.1.4  Chlorophyll
        10.1.5  Transmissivity
            10.1.5.1  What is transmissivity?
            10.1.5.2  How is transmissivity measured?
            10.1.5.3  How is transmissivity useful in water quality monitoring applications?
            10.1.5.4  How is transmissivity measurement implemented in Hydrolab instruments?
            10.1.5.5  Should I consider Hydrolab transmissivity measurement?

List of Figures

    10.1  Transmissivity is measured with a transmissometer
    10.2  Turbidity measurement with a nephelometer
Uvod je sa stranom broj 1

Chapter 10
Merenje parametara kvaliteta vode

10.1  Parametri kvaliteta vode

Temperatira, Hlor, pH, Provodnost, mutno\'ca (f(l svetlosti), automatski sampleri (i poluautomatski - tocak iz Nisa!). Koncentracija druge faze.

10.1.1  Ammonium

Hydrolab Technical Note 210 - 2/98

10.1.1.1  What is ammonium?

Ammonium, NH 4+, is an ionized form of nitrogen. There are many naturally-occurring forms of nitrogen, including the nitrogen gas that comprises nearly 80% of the atmosphere. Nitrogen compounds dissolved in water are usually classified as organic or inorganic. Soluble inorganic nitrogen compounds include ammonia, nitrite, and nitrate. Nitrate is related to ammonia in that nitrifying bacteria convert ammonia to nitrate, which is less toxic to animal life.
Ammonia has two forms - the ammonium ion, and unionized, dissolved ammonia gas (NH 3). The form depends on pH, with ammonium predominating when the pH is below 8.75, and ammonia predominating above pH 9.75. The forms are freely interconverted during a change in pH. Total ammonia is the sum of ammonium and ammonia concentrations.

10.1.1.2  How is ammonium measured?

Ammonium ion concentration is measured with a number of wet-chemistry or instrumental methods. Ammonium ion concentration is also measured with an ammonium ion-selective electrode (ISE). Inside the ammonium ISE is a reference electrode immersed in a solution of fixed ammonium ion concentration. This solution is separated from the sample by a polymer membrane containing a chemical compound that reacts, selectively, with ammonium ions. Am-monium ions on each side of the membrane equilibrate with the reactive compound at the inner and outer membrane surfaces. A result of the partitioning into the membrane surface of the ammonium ions from the internal solution and the ammonium ions from the sample is a measurable electrical potential that varies with the concentration of ammonium ions in the sample. This potential is measured with an external reference electrode (which is not the same reference electrode immersed in the sealed solution), and then scaled to ammonium ion concentration (provided the ISE has been calibrated with ammonium ion calibration solutions).
Because the relationship between ammonium ion concentration and dissolved ammonia gas concentration is controlled by pH, total ammonia can be calculated if the ammonium ion concentration and the pH of the water are known. However, if the pH of the sample is above 10, most of the total ammonia is in the form of dissolved ammonia gas (which is not measured by the ammonium sensor). Accurate measurements become difficult as the ammonium ion form becomes very small compared to total ammonia.
Notice that ISEs are sensitive only to the ionized form of the chemical in question. Un-ionized forms of the chemical (for instance, insoluble salts or organic compounds), will not be detected by the ISE.

10.1.1.3  How is ammonium measurement useful in water quality monitoring applications?

Nitrogen is an essential nutrient for all forms of life, including all levels of aquatic organisms. Biologically-available nitrogen is found in both suspended solids and dissolved compounds in natural waters. Many natural waters are nitrogen-limited, meaning that nitrogen compounds are the limiting nutrients. Thus even small changes in biologically-available nitrogen levels can dramatically effect the levels of microbiological, plant, and eventually, animal life. High levels of accessible nitrogen, of which total ammonia is one form, can lead to an over abundance of microorganisms, a situation which often results in mortality to higher organisms (such as fish and shrimp) because of depleted dissolved oxygen.
Excessive total ammonia can also result in mortality to the higher organisms, especially when high pH levels favor dissolved ammonia gas, which is more toxic than the ammonium form.
Applications of ammonium ion measurement include tracing the movement of point- or non-point source pollutants (for instance, runoff from agricultural operations), monitoring aquaculture projects for excessive waste concentrations, and surveying nutrient levels in natural water bodies.

10.1.1.4  How is ammonium measurement implemented in Hydrolab instruments?

Hydrolab uses the ammonium ISE, and the same external reference electrode used for pH measurement, for ammonium measurement. Because the electrical response of the ammonium ISE changes with temperature, ammonium readings are corrected automatically for temperature effects. However, the temperature response can vary between ammonium sensors -so calibration at a second temperature is needed if the temperature of the sample will be different from that of the calibration standards. Three- or four-point calibrations are recommended: two different standards at room temperature, and at least one standard at a temperature close to that expected of the samples.
The ammonium ISE response also changes with the ionic strength of the sample, since the ammonium ion appears less "active" when surrounded by other ions. Hydrolab corrects for ionic strength by measuring the conductivity of the sample water, calculating the approximate ionic strength of the water (assuming "typical" river water ionic composition) and then adjusting the ammonium reading for any difference between the ionic strengths of the calibration standards and the sample.
For example, suppose you calibrate your ammonium ISE with a solution whose ammonium concentration is 5 mg/l-N, and whose conductivity (an approximation of ionic strength) is 100 µmhos. Suppose then that you made a measurement in a sample whose ammonium concentration as also 5 mg/l-N, but whose conductivity was 1000 µmhos. The higher ionic strength of the sample would cause the ammonium ion to appear less active, meaning the ammonium ISE reading would be approximately 0.4 mg/l-N lower than the calibration standard – even though the true concentrations are both 5 mg/l-N. The Hydrolab system largely prevents this error by measuring conductivity, calculating an approximate ionic strength, and then correcting the ISE reading.
As a result of Hydrolab's ionic strength correction, the ammonium activity, rather than the ammonium concentration, of the standard is used forcalibration. Hydrolab supplies calibration standards labeled with ammonium activity, rather than concentration. For instance, a de-ionized water solution that is: 
    0.00357 ± 0.00001 molar in ammonium chloride,
    0.000477 ± 0.000004 molar in magnesium acetate,
    0.000954 ± 0.000004 molar in acetic acid, with
    0.055% glutaraldehyde preservative added,
has an ammonium concentration of 50 mg/l-N, but an ammonium activity of just 46.2 mg/l-N. For a lower ammonium concentration, Hydrolab supplies a solution that is: 
    0.000357 ± 0.000001 molar in ammonium chloride,
    0.001548 ± 0.00001 molar in magnesium acetate,
    0.003095 ± 0.00001 molar in acetic acid, with 0.055%
    glutaraldehyde preservative added,
resulting in a 5 mg/l-N ammonium concentration, and a 4.62 mg/l-N activity.
The ammonium sensor has a measurement range of 0-100 mg/l-N (mg/l-N means mg/l of nitrogen, present, in this case, in the ammonium form), with a 90% response in less than one minute, at depths to 15 meters.
Leaching of chemicals from the membrane, coating of the membrane with surfactants or biological growth, or damage to the membrane can leads to a decreased sensitivity of the sensor. Eventually, the sensor will no longer calibrate or operate properly. The lifetime of the sensor depends greatly on deployment conditions. The ammonium sensor will last longer in clean waters than in severely contaminated waters.
All ammonium ISEs suffer interferences from other ions, especially sodium and potassium. Even though the sensor is most selective to ammonium, other ions, when found in high concentrations, can dominate the sensor response. For example, concentrations of 23 mg/l of potassium ion, 821 mg/l of sodium ion, or 4,340 mg/l of magnesium ion all "look like" about 1 mg/l-N of ammonium ion to an ammonium ISE. Significant interferences are not likely to be encountered in water with conductivity below 1,000 µS, but in sea water, which contains over 10,000 mg/l of sodium ion, an ammonium sensor would read over 12 mg/l-N for ammonium concentration, even in the absence of ammonium, because of the sodium interference. Because of the sodium ion interference, the ammonium sensor performs poorly in salt water.

10.1.1.5  Should I consider Hydrolab ammonium measurement?

Hydrolab ammonium measurement provides these benefits:

10.1.2  Nitrate

Hydrolab Technical Note 211 - 2/98

10.1.2.1  What is nitrate?

Nitrate, NO3-, is an ionized form of nitrogen. There are many naturally-occurring forms of nitrogen, including the nitrogen gas that comprises nearly 80% of the atmosphere. Nitrogen compounds dissolved in water are usually classified as organic or inorganic. Soluble inorganic nitrogen compounds include ammonia, nitrite, and nitrate. Nitrate is related to ammonia in that nitrifying bacteria convert ammonia to nitrate, which is less toxic to animal life.

10.1.2.2  How is nitrate measured?

Nitrate ion concentration is measured with a number of wet-chemistry or instrumental methods. Nitrate ion concentration is also measured with an nitrate ion-selective electrode (ISE). Inside the nitrate ISE is a reference electrode immersed in a solution of fixed nitrate ion concentration. This solution is separated from the sample by a polymer membrane containing a chemical compound that reacts, selectively, with nitrate ions. Nitrate ions on each side of the membrane equilibrate with the reactive compound at the inner and outer membrane surfaces. A result of the partitioning into the membrane surface of the nitrate ions from the internal solution and the nitrate ions from the sample is a measurable electrical potential that varies with the concen-tration of nitrate ions in the sample. This potential is measured with an external reference electrode (which is not the same reference electrode immersed in the sealed solution), and then scaled to nitrate ion concentration (provided the ISE has been calibrated with nitrate ion calibration solutions).
Notice that ISEs are sensitive only to the ionized form of the chemical in question. Un-ionized forms of the chemical (for instance, insoluble salts or organic compounds), will not be detected by the ISE.

10.1.2.3  How is nitrate measurement useful in water quality monitoring applications?

Nitrogen is an essential nutrient for all forms of life, including all levels of aquatic organisms. Biologically-available nitrogen is found in both suspended solids and dissolved compounds in natural waters. Many natural waters are nitrogen-limited, meaning that nitrogen compounds are the limiting nutrients. Thus even small changes in biologically-available nitrogen levels can dramatically effect the levels of microbiological, plant, and eventually, animal life. High levels of accessible nitrogen, of which nitrate is one form, can lead to an over abundance of microorganisms, a situation which often results in mortality to higher organisms (such as fish and shrimp) because of depleted dissolved oxygen.
Applications of nitrate ion measurement include tracing the movement of point or non-point source pollutants (for instance, runoff from agricultural operations), monitoring aquaculture projects for excessive waste concen-trations, and surveying nutrient levels in a natural water bodies.

10.1.2.4  How is nitrate measurement implemented in Hydrolab instruments?

Hydrolab uses the nitrate ISE, and the same external reference electrode used for pH measurement, for nitrate measurement. Because the electrical response of the nitrate ISE changes with temperature, nitrate readings are corrected automatically for temperature effects. However, the temperature response can vary between nitrate sensors - so calibration at a second temperature is needed if the temperature of the sample will be different from that of the calibration standards. Three or fourpoint calibrations are recommended: two different standards at room temperature, and at least one standard at a temperature close to that expected of the samples.
The nitrate ISE response also changes with the ionic strength of the sample, since the nitrate ion appears less "active" when surrounded by other ions. Hydrolab corrects for ionic strength by measuring the conductivity of the sample water, calculating the approximate ionic strength of the water (assuming "typical" river water ionic composition), and then adjusting the nitrate reading for any difference between the ionic strengths of the calibration standards and the sample.
For example, suppose you calibrate your nitrate ISE with a solution whose nitrate concentration is 5 mg/l-N, and whose conductivity (an approximation of ionic strength) is 100 µmhos. Suppose then that you made a measurement in a sample whose nitrate concentration was also 5 mg/l-N, but whose conductivity was 1000 µmhos. The higher ionic strength of the sample would cause the nitrate ion to appear less active, meaning the nitrate ISE reading would be approximately 0.4 mg/l-N lower than the calibration standard – even though the true concentrations are both 5 mg/l-N. The Hydrolab system largely prevents this error by measuring conductivity, calculating an approximate ionic strength, and then correcting the ISE reading.
As a result of Hydrolab's ionic strength correction, the nitrate activity, rather than the nitrate concentration, of the standard is used for calibration. Hydrolab supplies calibration standards labeled with nitrate activity, rather than concentration. For instance, a de-ionized water solution that is: 
    0.00357 ± 0.00001 molar in potassium nitrate,
    0.000477 ± 0.000004 molar in potassium sulfate, with
    0.055% glutaraldehyde preservative added,
has a nitrate concentration of 50 mg/l-N, but an nitrate activity of just 46.2 mg/l-N. For a lower nitrate concentration, Hydrolab supplies a solution that is: 
    0.000357 ± 0.000001 molar in potassium nitrate, 
    0.001548 ± 0.00001 molar in potassium sulfate, with
    0.055% glutaraldehyde preservative added,
resulting in a 5 mg/l-N nitrate concentration, and a 4.62 mg/l-N activity.
The nitrate sensor has a measurement range of 0 - 100 mg/l-N (mg/l-N means mg/l of nitrogen, present, in this case, in the nitrate form), with a 90% response in less than one minute.
Leaching of chemicals from the membrane, coating of the membrane with surfactants or biological growth, or damage to the membrane can leads to a decreased sensitivity of the sensor. Eventually, the sensor will no longer calibrate or operate properly. The lifetime of the sensor depends greatly on deployment conditions. The nitrate sensor will last longer in clean waters than in severely contaminated waters.
All nitrate ISEs suffer interferences from other ions, especially chloride, bromide, bicarbonate, perchlorate, and chlorate. Even though the sensor is most selective to nitrate, other ions, when found in high concentrations, can dominate the sensor response. For example, concentrations of 250 mg/l of chloride ion, 115 mg/l of bromide ion, 40 mg/l of bicarbonate, or 0.3-0.4 mg/l of chlorate or perchorate ion all "look like" about 1 mg/l-N of nitrate ion to an nitrate ISE. Significant interferences are not likely to be encountered in water with conductivity below 1,000 µS, but in sea water, which contains over 18,000 mg/l of chloride ion, a nitrate sensor would read over 70 mg/l-N for nitrate concentration, even in the absence of nitrate, because of the sodium interference.
Because of the chloride ion interference, the nitrate sensor performs poorly in salt water.

10.1.2.5  Should I consider Hydrolab nitrate measurement?

Hydrolab nitrate measurement provides these benefits:

10.1.3  Chloride

Hydrolab Technical Note 212 - 2/98

10.1.3.1  What is chloride?

Chloride, Cl - , is an ionized form of chlorine. Because most chloride salts are ubiquitous and highly soluble, chloride is one of the most common ions found in natural waters, and is the prevalent ion in sea water. Though not considered a nutrient, chloride is abundant in all living cells.

10.1.3.2  How is chloride measured?

Chloride ion concentration is measured with a number of traditional, wet-chemistry methods (titrations), instrumentally (colorimeters), or by correlation with electrical conductivity measurements.
Chloride ion concentration is also measured with a chloride ion-selective electrode (ISE). The chloride ISE is a pellet of silver chloride in direct contact with the sample water. Because silver chloride has extremely low solubility in water, the silver chloride pellet never reaches chemical equilibrium with the sample water. Instead, a small amount of chloride ion dissolves into the sample. The resulting relative surplus of silver ions at the surface of the pellet creates a measurable electrical potential that varies with the concentration of chloride ions in the sample. This potential is measured with an external reference electrode, and then scaled to chloride ion concentration (provided the ISE has been calibrated with chloride ion calibration solutions).
Notice that ISEs are sensitive only to the ionized form of the chemical in question. Un-ionized forms of the chemical (for instance, insoluble salts or organic compounds), will not be detected by the ISE.

10.1.3.3  How is chloride measurement useful in water quality monitoring applications?

The chloride ion does not react with, or adsorb to, most components of rocks and soils, and so is easily transported through water columns. Thus chloride is an effective tracer for pollution from chemicals moving from man-made sources into natural water bodies, or for salt water intrusion.
Applications of chloride ion measurement include monitoring landfills for leaks, tracing the movement of point-or non-point source pollutants (for instance, storm water runoff) within a natural water body, monitoring estua-rine waters for changes in salinity, and detection of salt water intrusion into drinking water supplies (ground or surface waters).

10.1.3.4  How is chloride measurement implemented in Hydrolab instruments?

Hydrolab uses the chloride ISE, and the same external reference electrode used for pH measurement, for chloride measurement. Because the electrical response of the chloride ISE changes with temperature, chloride readings are corrected automatically for temperature effects. However, the temperature response can vary between chloride sensors - so calibration at a second temperature is needed if the temperature of the sample will be different from that of the calibration standards. Three- or four-point calibrations are recommended: two different standards at room temperature, and at least one standard at a temperature close to that expected of the samples.
The chloride ISE response also changes with the ionic strength of the sample, since the chloride ion appears less "active" when surrounded by other ions. Hydrolab corrects for ionic strength by measuring the conductivity of the sample water, calculating the approximate ionic strength of the water (assuming "typical" river water ionic composition at low conductivities, or sea water ionic composition at high conductivities), and then adjusting the chloride reading for any difference between the ionic strengths of the calibration standards and the sample.
For example, suppose you calibrate your chloride ISE with a solution whose chloride concentration is 46 mg/l, and whose conductivity (an approximation of ionic strength) is 500 µmhos. Suppose then that you made a measurement in a sample whose chloride concentration was also 46 mg/l, but whose conductivity was 5,000 µmhos (due to presence of other ions). The higher ionic strength of the sample would cause the chloride ion to appear less active, meaning the chloride ISE reading would be below 40 mg/l - even though the true concentration is 46 mg/l. The Hydrolab system largely prevents this error by measuring conductivity, calculating an approximate ionic strength, and then correcting the ISE reading.
As a result of Hydrolab's ionic strength correction, the chloride activity, rather than the chloride concentration, of the standard is used for calibration. Hydrolab supplies calibration standards labeled with chloride activity, rather than concentration. For instance, a de-ionized water solution that is: 
    0.001410 ± 0.000003 molar in potassium chloride,
    0.00359 ± 0.00003 molar in potassium nitrate, with
    0.055% Glutaraldehyde preservative added,
has a chloride concentration of 50 mg/l, but a chloride activity of just 46.2 mg/l. For a higher chloride concentration, Hydrolab supplies a solution that is: 
    0.0100 ± 0.00005 molar in potassium chloride,
resulting in a 354.5 mg/l chloride concentration, and a 319.3 mg/l activity. (This solution, 0.1 molar potassium chloride, is also used as a 1.413 mS conductivity calibration standard.)
The chloride sensor has a measurement range of 0.5-18,000 mg/l, with a 90% response in less than one minute, at depths to 15 meters. All chloride sensors suffer interferences from other ions, working best when the concentrations of bromide, iodide, cyanide, silver, and sulfide ions are much lower than the chloride ion concentration.

10.1.3.5  Should I consider Hydrolab chloride measurement?

Hydrolab chloride measurement provides these benefits:

10.1.4  Chlorophyll

Pogledaj SCUFA-Technotes.pdf file!

10.1.5  Transmissivity

Hydrolab Technical Note 206 - 4/97

10.1.5.1  What is transmissivity?

Pure water naturally reduces the intensity of light as the light travels farther through the water, with higher attenuation at the longer light wavelengths. That's why scuba divers seem to be immersed in bluish light - the lower-energy, reddish light has suffered greater natural attenuation. Dissolved, colloidal, and suspended particles in water cause further attenuation by absorbing and scattering the incident light beam.
Transmissivity is the ability of water to transmit light along a straight path. Any incident light attenuated, scattered, or absorbed decreases the transmissivity of the water - thus the "dirtier" the water, the lower the transmissivity.

10.1.5.2  How is transmissivity measured?

Transmissivity is measured with a transmissometer, a device that sends an incident light beam in a single direction, and measures the light transmitted in that same direction. If the water contains a lot of foreign materials (solutes or turbidity particles), very little of the incident beam will reach the receiver because most of the light will be scattered away or absorbed by the foreign materials. If, however, the water is very clean, most of the light will reach the receiver.
Figure 10.1: Transmissivity is measured with a transmissometer
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A transmissometer reports units of percent transmission: a reading of 80% transmission means that only 20% of the incident light was attenuated by the water, and 80% of the incident light made it to the receiver. Another way of reporting transmissivity measurement is the beam attenuation coefficient, which is related to perent transmission as:
percent transmission = (100%) e-cz ,
where c is the beam attenuation coefficient in units of meter -1 , and z is the length of the light path in meters.
Another method for quantifying water "cloudiness" is turbidity measurement, made in field situations most commonly with a nephelometer. This device sends an incident light beam in a single direction, and senses light scattered at a right angle (instead of transmitted) to the incident beam.
Figure 10.2: Turbidity measurement with a nephelometer
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Turbidity particles in water scatter the light: the more particles, the more scattered light, and so the higher the turbidity reading. Very clean water scatters very little light, and so has a low turbidity reading.Hydrolab's turbidity sensor is a nephelometer, for which the unit of measurement is the nephelometric turbidity unit (NTU). Notice that a transmissometer's sensitivity is the opposite of a nephelometer's. Field practitioners concerned with relatively clean waters might prefer a transmissometer (high signal in clean waters) to a nephelometer (low signal in clean waters). The reverse also applies: the cloudier the water, the less sensitive a transmissometer.
Because the optical measurement methods are different, the readings of a transmissometer and a nephelometer cannot be directly related - there's no table that converts NTUs to percent transmission for all waters. For purposes of rough estimation, though, percent transmission can be related to NTUs as defined by formazin dilutions. For a transmissometer with a path length of 10 cm, the span of 20% to 80% transmission corresponds roughly to a turbidity span of 230 to 20 NTUs. For a 25-cm path length, the turbidity span is 60 to 10 NTUs.
Practitioners can relate NTUs and percent transmission for their particular waters only by comparing nephelometer readings with transmissometer readings for a number of samples, and generating a custom conversion table or algorithm.

10.1.5.3  How is transmissivity useful in water quality monitoring applications?

There are many applications for measurement of water "clarity", including sediment transport prediction, primary productivity analysis, drinking-water reservoir management, regulatory monitoring, scientific research, etc. The value and implementation of transmissivity measurement is different for each of these applications.
Again, transmissivity measurements are most useful in relatively clean waters.

10.1.5.4  How is transmissivity measurement implemented in Hydrolab instruments?

Transmissometers have variable path lengths - generally the longer the path length, the greater the sensitivity in clean waters. Because the minimum path length is usually 10 centimeters, a transmissometer will not fit into Hydrolab's standard sensor guard or storage cup. Thus, Hydrolab mounts its transmissometer alongside the DataSonde ® 4 Water Quality Multiprobe. The transmissometer can be removed easily for storage, calibration, or when transmissivity measurements are not needed.
The transmissometer is powered and controlled by the DataSonde 4 Multiprobe, and the readings are integrated with the standard multiprobe data stream or logging records.
Hydrolab transmissometers are configured to measure with red light.
Calibration is made with a water standard for which the transmissivity is known.
Because transmissometer lenses are exposed to the water being measured, sedimentary or biological deposits can impair calibration.

10.1.5.5  Should I consider Hydrolab transmissivity measurement?

Hydrolab transmissivity measurement provides these benefits:

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