Application Bulletin - Ortho P in WW

®
ChemScan
PROCESS ANALYZERS
©2002, Applied Spectrometry Associates, Inc. www.chemscan.com
Rev. 9/02
ChemScan® Method Summary

#40
Ortho-Phosphorous in Water or Wastewater
Phosphorus Analysis Classifications
Phosphorous analysis can be classified by the type of preprocessing performed on a

sample. Phosphorous may be found in several forms in water or wastewater, including
dissolved form (orthophosphate), inorganic form (reactive plus condensed or acid
hydrolyzable phosphate) and organically bound forms. Total Phosphorous is the sum of
reactive, condensed and organic phosphate.
Total Phosphorous (TP) is the form of analysis typically cited as an effluent parameter for
municipal and industrial wastewater treatment plants. Total Phosphorous in effluent is a
measure of the remaining dissolved phosphate plus any insoluble phosphate carried over
into the effluent in the form of precipitates or within microbes. Following digestion, all
phosphorous is converted into dissolved phosphate for analysis. This is not, however, the
form of analysis that is the most useful for process monitoring or control purposes
because the Total Phosphorous analysis does not identify the original source of the
effluent phosphorous. The most basic form of analysis for process control is reactive
phosphorous (orthophosphate), which can indicate the amount of phosphorous that is
available to participate in chemical reactions or biological activity. This concentration can
be measured before and after chemical precipitation or biological assimilation and settling.
Measurement of dissolved reactive phosphorous requires filtration of the sample at 0.45
micron prior to analysis.
ChemScan Analytical Method
The standard ChemScan method for orthophosphate analysis is based on the

Vanadomolybdo- phosphoric Acid Method (Standard Method 4500-PC.). Ammonium
molybdate reacts under acid conditions with orthophosphate to produce
molybdophosphoric acid. Further reaction with vanadium produces
Vanadomolybdophosphoric acid, which has strong absorbance spectra in the ultraviolet
and visible wavelength range. Dissolved orthophosphate analysis is performed on a
filtered sample. If the sample is not filtered (0.45 micron or less) prior to analysis, any
acid hydrolyzable phosphate precipitates or particulates in the sample may be redissolved
and detected.
On-line orthophosphate analysis using ChemScan can also be performed based on the
precipitation of orthophosphate with a known concentration of iron salt followed by
measurement of the residual dissolved iron. Liquid ferrous chloride is the reagent of
choice, particularly in wastewater with pH of 7 to 8. Lower pH samples may use liquid
ferric chloride. Higher pH samples may require buffering with acid in the iron salt solution.
The reaction between ferrous chloride and phosphate can be approximated by the
following:
3FeCl2 + 2PO43- ---> Fe3(PO4)2 + 6Cl
The ChemScan Process Analyzer must be set up to characterize any background iron
concentration in the sample prior to introduction of the ferrous reagent. The analyzer
must also be calibrated to compensate for the effects of variable sample turbidity and
possible interference from nitrate, sulfate, chloride, bromide, organic matter and other
metals. The ChemScan multiple wavelength detection and pattern recognition software is
fully capable of this analysis and the necessary background correction.
Monitoring System Requirements
Sample extraction points are a function of the phosphate removal process (chemical,
biological or combined). (See ChemScan Application Summaries #91, Chemical
Phosphorous Removal and #92, Biological Phosphorous Removal.) Chemical
precipitation processes typically use aluminum or iron salts, applied upstream of the
primary clarifier, in the aeration basin or immediately after the aeration basin. Some
designs have multiple addition points. Another option is the use of separate tertiary
chemical precipitation tank as a polishing step following the chemical or biological
treatment.
The ChemScan Process Analyzer can accommodate samples with up to 150 mg/l of total
suspended solids and turbidity of up to 60 NTU. Samples extracted from points in the
treatment process ahead of secondary clarification will typically exceed these solids or
turbidity specifications. These samples will require filtration or settling prior to analysis to
produce a sample meeting ChemScan solids and turbidity requirements. ChemScan has
cross flow membrane filters and porous plastic cyclic filters available for use with on-line
analyzer systems. Sample points should be selected to assure that fat, oil and grease
(FOG) will be low enough not to interfere with the sample filtration method selected for the
analyzer system. Raw wastewater samples (especially prior to screens, grit removal,
FOG removal and primary clarification) are difficult to analyze and are of questionable
value. Much of the Total Phosphorous load on the process is the sum of the soluble
phosphate contributed by the incoming wastewater plus the phosphorous from the organic
fraction contributed by the Return Activated Sludge plus the phosphorous of any
recirculation flow back from the later stages of the treatment process. The ideal initial
sample point is after RAS and recirculation addition to the primary effluent.

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ChemScan® Method Summary

Phosphorus Analysis Classifications

Phosphorous analysis can be classified by the type of preprocessing performed on a

ChemScan Analytical Method

The standard ChemScan method for orthophosphate analysis is based on the

3FeCl2 + 2PO43- ---> Fe3(PO4)2 + 6Cl

Monitoring System Requirements

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