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• pH

• Conductivity

• Temperature

• Dissolved oxygen

Each of these is described by standard method published by the EPA or ASTMhttp://www.standardmethods.org/

National Environmental Methods Indexhttps://www.nemi.gov/

Standard Operating Procedures: Continuous Water Quality Monitoring Network (TCEQ)http://www.tceq.texas.gov/waterquality/monitoring/cwqm_sops.html

Aquatic Sensor Workgrouphttp://www.watersensors.org/

Surface Water Quality Monitoringhttp://www.tceq.texas.gov/waterquality/monitoring/index.html

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• ORP – oxidation/reduction potential

• Turbidity – cloudiness or haziness. Measured with a nephelometer.

• Nitrate (NO3-)

• Ammonium (NH4+) / ammonia (NH3-)

• Chloride (Cl-)

• Rhodamine – for monitoring dyes

• Chlorophyll

• Reference: http://www.ysi.com/parameters.php

A measurement of the average kinetic energy of particles

in a substance.

Thermistor – a semiconductor material that has a change in

resistance in proportion to the change in temperature

Calibration standards are based on a constant room temperature

of 25ºC (77ºF)

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• In chemistry, a measurement of the acidity or alkalinity of a solution which is determined by the number of H+ or OH- ions in solution.

• First introduced by a Danish chemist in 1909 and revised to the modern version in 1924.

• Origins of ‘pH’: The subscript ‘h’ referenced in first papers. Could have been ‘power’ or ‘power of hydrogen’ (from German or French).

• Based on a logarithmic scale (10x) and is from the range of 0 to 14 where 7 is defined as neutral

• Streams, creeks, rivers, lakes, groundwater

• Affected by: bedrock and soil composition, organic growth in the water, dumping of chemicals, acid rain, drainage waste (from mine tailings for example)

• References: http://www.all-about-ph.com/ , http://en.wikipedia.org/wiki/PH

Always remember:

● Logarithmic

● 10x for pH

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The pH probe is made up of a few essential parts.

The glass bulb, KCL reference gel, Silver Chloride coated wire,

and the reference junction.

The glass bulb is filled with a stable pH solution, usually pH 7,

that experiences constant binding of Hydrogen ions.

The outside of the bulb is exposed to the water, where the

Hydrogen ions vary.

The difference in Hydrogen ions creates a potential that is read

versus the stable potential of the reference electrode.

This signal is sent via the Silver Chloride coated wire to the

instrument, where it is measured as a voltage and then

converted to pH units.

References: http://www.all-about-ph.com/ph-electrode.html

http://www.ysi.com/media/support/YSI-Making-Good-pH-Measurements-web.pdf

Based on the Nernst Equation which is Mathematical description of an ideal pH electrodeBehavior. Introduced by the German chemistHermann Nernst in 1889.

For a (3) point calibration, buffers 4, 7, 10 used.

One can do a 1, 2, or 3 point calibration.

The figure to right shows the effect on the electrode signal at various temperatures. The isothermal pointof a pH electrode is defined as the intersection point of different temperature lines, see the figure. The isopotential point, or the zero point, is then point where electrode output is 0.0 mV.

For an ideal pH electrode, this would represent anisothermal intersection at the zero point (0 mV at pH 7) for different temperatures.

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Do’s:• Be sure you always store your pH probe in a moist environment, at the least, to prevent it

from drying out.• Water-saturated air is the minimum you would need to store your probe in a short-term

situation. Short-term is three weeks or less.• The best way to store your probe when not in use is submerged in pH 4 buffer or pH storage

solution. This is also recommended for long-term storage, which is longer than three weeks. • Do develop a routine maintenance program that includes reconditioning the pH probe prior

to the field season.• Do maintain good calibration records to track your probes performance.

Don’ts:• Never store pH Probe submerged in DI water. It will dilute the internal electrolyte and

shorten the probe’s life. • Never allow your probe to sit in dry air for extended periods of time. If the probe has been

improperly stored or allowed to dry out, it is very likely the probe will need to be replaced.• Be sure to prevent probes from being subjected to below freezing temperatures or exposed to

excessive heat. • When cleaning, avoid using a brush or any other material that could scratch the surface of the

glass bulb. Scratches will affect your probe’s stability.

Reference: http://www.ysi.com/media/support/YSI-Making-Good-pH-Measurements-web.pdf

Conductivity is a measure of the ability of water to pass an electrical current.

Conductivity in water is affected by the presence of inorganic dissolved solids

such as chloride, nitrate, sulfate, and phosphate anions (ions that carry a

negative charge) or sodium, magnesium, calcium, iron, and aluminum cations

(ions that carry a positive charge).

Organic compounds like oil, phenol, alcohol, and sugar do not conduct electrical current very well and therefore have a low conductivity when in water.

Conductivity is also affected by temperature: the warmer the water, the higher the conductivity. For this reason, conductivity is reported as conductivity at 25 degrees Celsius (25 C).

● Units: milli-Siemens/cm, micro-Siemens/cm

Reference: http://water.epa.gov/type/rsl/monitoring/vms59.cfm

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Fig 2: Most conductivity meters have atwo-electrode cell (see illustration)available in either dip or flow-throughstyles. The electrode surface is usuallyplatinum, titanium, gold-plated nickel, orgraphite.

● Fig 1: The basic unit of conductance is thesiemen (S), formerly called the mho. Sincecell geometry affects conductivity values,standardized measurements areexpressed in specific conductivity units(S/cm) to compensate for variations inelectrode dimensions. Specificconductivity (C) is simply the product ofmeasured conductivity (G) and theelectrode cell constant (L/A), where L isthe length of the column of liquid betweenthe electrodes and A is the area of theelectrodes (see illustration). C = G x (L/A)Reference: http://www.coleparmer.com/TechLibraryArticle/78

Varies slightly from manufacturer, but typically a (1) point calibration. TCEQ uses 1413 uS.

The procedure is to rinse the probe in DI water, and shake and wipe excess water. Place the probe into the calibration solution and make sure to dunk the entire probe into the solution.

Once the reading is settled, set the calibration point (depends upon meter).

Conductivity solution maybe a potassium chloride, sodium chloride, or TDS 442 (mix of mixture of sodium sulfate (40%), sodium bicarbonate (40%) and sodium chloride (20%). The 442 mixture is designed to mimic the ions often present in natural fresh water systems.

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Each is a measure of salts dissolved in sample.

● Conductivity – how well the water conducts electrical current which is proportional to the dissolved ions in a sample

● Salinity - is a special measure of dissolved solids based upon concentration of ocean salts. Technically, the measurement of salinity requires comparing a sample's TDS (Total Dissolved Solids), conductivity, or other physio-chemical property with that of a standard sea water.

● Salinity is the usual measure of salts in sea water and in brackish water derived from mixing of fresh and sea water.

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The amount of oxygen (O2) dissolved in water.

Also referred to sometimes as oxygen saturation.

Cold water can hold higher levels than warm water.

Correction factors for solubility and salinity

Typical units: 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), 'percent saturation‘

Percent saturation - the amount of oxygen in a liter of water relative to the total amount of oxygen that the water can hold at that temperature

Dissolved Oxygen Values above 100% (Read)http://www.ysi.com/media/pdfs/T602-Environmental-Dissolved-Oxygen-Values-Above-100-percent-Air-Saturation.pdf

Reference: http://water.epa.gov/type/rsl/monitoring/vms52.cfm

Note: mg/L is ppm

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The electrochemical method of measuring DO requires a cathode, anode, electrolyte solution and a gas permeable membrane. The material of the membrane is specially selected to permit oxygen to pass through. Oxygen is consumed by the cathode which will create a partial pressure across the membrane. Oxygen will then diffuses into the electrolyte solution.

Thus, a DO meter actually measures the pressure of oxygen in water. It can be used to measure DO in any medium.

Polarographic or Clark Cell Method

Dr. Clark first discovered the cell to measure oxygen in 1956. This is basically an amperometric (polarographic) cell that is polarized around 800 mV. This cell, named after Dr. Clark, is built around the popular Ag/AgCl half-cell and a noble metal such as gold, platinum or palladium. Reduction of oxygen is achieved between 400 to 1200 mV, hence a need for a voltage of around 800 mV. This is provided externally by a battery source.

Galvanic Method using to dissimilar metals and an electrolyte, so it requires no warm up time or external voltage source

Reference: http://www.eutechinst.com/techtips/tech-tips15.htm

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Lifetime and intensity optical measurement methods detect dissolved oxygen

based on the well documented principle that dissolved oxygen quenches

both the lifetime and intensity of the luminescence associated with carefully chosen chemical dyes. When there is no oxygen present, the lifetime and

intensity of the signal are at their maximum. As oxygen is introduced

to the sensing element, both the lifetime and intensity of the luminescence

become shorter. Therefore, the lifetime and intensity of the luminescence

are inversely proportional to the amount of oxygen present. The relationship

between the oxygen pressure outside the sensor and the lifetime or intensity

of the luminescence in the dye layer of the sensing element can be generally

quantified by the Stern-Volmer equation (Io/I = 1 + kqt0 * O2). However, the Stern-

Volmer equation implies an inversely linear relationship which is not strictly

true especially at higher oxygen concentrations; therefore, YSI employs the

use of a 3rd order polynomial to correct for this non-linearity and to obtain

the desired range of dissolved oxygen readings.

Reference: The Dissolved Oxygen Handbook

According to YSI, the sensors should be calibrated in the following order:

Specific Conductance, pH mid-range (7.0), pH low (4.0) or high range (10), Dissolved Oxygen

http://www.tceq.texas.gov/assets/public/compliance/monops/water/wqm/forms/YSI_CaLogbook.pdf

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• pH

• Conductivity/TDS

• DO

• Temperature

Compare with values at FM 70 and past values.

http://www.tceq.texas.gov/waterquality/tmdl/nav/32-petronila/32-petronila-tds

“Petronila Creek, Segment 2204, is a 44-mile freshwater stream spanning Kleberg and Nueces counties. Located southwest of Corpus Christi, PetronilaCreek is part of the Baffin Bay watershed.

In 2000, water quality testing found elevated levels of chloride, sulfate, and TDS in the creek. High concentrations of these salts are indicators of general water quality that are not tied to a specific use, but may affect several uses.

“

Water temperature and conductivity collected in real time at the creek:

http://www.tceq.state.tx.us/cgi-bin/compliance/monops/water_site_photo.pl?cams=731

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