🔬 Phosphates / Total Phosphorus in Water

Physicochemistry PN-EN ISO 6878

In short

Spectrophotometric determination of orthophosphates and total phosphorus in water by ammonium molybdate and ascorbic acid method (molybdenum blue). The test is performed according to PN-EN ISO 6878:2006+Ap1:2010+Ap2:2010; Measurement range: 0.005–0.8 mg P/L (without dilution). The procedure comprises 8 steps (about 1 h 27 min–1 h 47 min in total); it is used for: Surface water eutrophication monitoring, Treated wastewater control (limit ≤1–2 mg P/L), Drinking water quality control.

At a glance

  • Standard: PN-EN ISO 6878:2006+Ap1:2010+Ap2:2010
  • Category: Physicochemistry
  • Procedure steps: 8
  • Total time of stages: 1 h 27 min–1 h 47 min
  • TWO Ap CORRIGENDA — TEXT READ 22 SEP 2026, AND THE FIRST CHANGES A FIGURE USED IN THE PROCEDURE: the designation of this article carries both elements ("+Ap1:2010+Ap2:2010"), yet until now it did not say what they change. Ap1 (March 2010, KT 121 for Water Quality — Chemical Testing — Inorganic Substances): "In 8.1.1, for 1.94 g/ml read 1.84 g/ml" — that is the DENSITY OF SULFURIC ACID, a figure entering directly into the preparation of the reaction mixture; without the corrigendum the standard gives a wrong value. Ap2 (June 2010): "In Annex B, Table B.3, in the column Relative Reproducibility, for mg/l read %" — a change of UNIT in the precision table, so the reproducibility figures are read as percentages, not as mg/l. The text of both corrigenda is FREE on the PKN site (links beside the "Additional elements" field on the card)
  • Measurement range: 0.005–0.8 mg P/L (without dilution)
  • Detection limit: 0.005 mg P/L (direct), 0.0005 mg P/L (after extraction)

Overview

Phosphorus is a key biogenic element responsible for eutrophication of surface waters — excessive algal growth, cyanobacterial blooms, oxygen deficiency, and aquatic ecosystem degradation. In natural waters phosphorus occurs as: orthophosphates (PO₄³⁻, reactive, directly assimilable by organisms), polyphosphates (hydrolyze to orthophosphates), and organic phosphorus (bound to organic matter).

Total phosphorus = orthophosphates + polyphosphates + organic phosphorus (after mineralization).

Standards: drinking water ≤0.4 mg PO₄³⁻/L, treated wastewater ≤2 mg P/L (>10 000 PE), surface waters class I ≤0.2 mg P/L. Urban Wastewater Directive requires phosphorus reduction in treatment plants above 10 000 PE.

ISO 6878 method (molybdenum blue with ascorbic acid) is reference method — highly sensitive, range 0.005–0.8 mg P/L.

ONE KEY, FOUR DIFFERENT DETERMINATIONS — WHAT THE TAB REALLY SHOWS HERE (23.09.2026). The key "PN-EN ISO 6878" is matched by the beginning of the value and covers 327 entries at 158 laboratories. BUT IN THE SCOPES THIS STANDARD IS BROKEN DOWN INTO CLAUSES, AND EACH CLAUSE IS A DIFFERENT DETERMINATION: the measurement (23.09, copy of the scopes) gives 67 laboratories with a record without a clause reference, 53 with "pkt 7" [clause 7], 50 with "pkt 4", 45 with "pkt 8" and one with "pkt 5", while 91 laboratories have ONLY a record referring to a specific clause and none without. SO THE LIST OF 158 LABORATORIES IS NOT A LIST OF LABORATORIES PERFORMING THE SAME TEST. Someone looking for the determination of orthophosphates and someone looking for total phosphorus after mineralization will get the same list — because the key distinguishes documents, while the laboratories distinguish clauses within a document. THIS IS A SEPARATE VARIETY OF OVER-INCLUSION: it is not a foreign standard pulled in by a common prefix, nor another part of the series, but a DIFFERENT PARAMETER DETERMINED ACCORDING TO THE SAME DOCUMENT. Across the whole set there are 4892 records with a reference to a clause of a standard, at 640 laboratories, so this is not a peculiarity of this one standard.

THE SECOND CORRECTION IS LESS VISIBLE THAN THE FIRST. After Ap2 the figures in Table B.3 stay the same; only their meaning changes — a reproducibility read as mg/l at a value of 5 means something different from 5 %. Anyone comparing a result with the table from before the correction will see no difference in the digits.

Method principle

Orthophosphate ions react with ammonium molybdate and antimony potassium tartrate in acidic environment (H₂SO₄), forming heteropolyacid phosphomolybdic complex (antimony-phosphomolybdate). Complex is reduced by ascorbic acid to intensely blue complex (molybdenum blue).

PO₄³⁻ + Mo(VI) + Sb³⁺ → (H⁺) → phosphomolybdate complex Complex + ascorbic acid → molybdenum blue (intensely blue)

Absorbance is measured at 880 nm (maximum sensitivity) or 700 nm (with lower sensitivity). Color develops in 10–30 minutes and is stable for 24 hours.

For total phosphorus: before analysis sample is mineralized (K₂S₂O₈ + H₂SO₄, 120°C/30 min) to convert all phosphorus forms to orthophosphates.

Applications

Key parameters

ParameterValue
TWO Ap CORRIGENDA — TEXT READ 22 SEP 2026, AND THE FIRST CHANGES A FIGURE USED IN THE PROCEDUREthe designation of this article carries both elements ("+Ap1:2010+Ap2:2010"), yet until now it did not say what they change. Ap1 (March 2010, KT 121 for Water Quality — Chemical Testing — Inorganic Substances): "In 8.1.1, for 1.94 g/ml read 1.84 g/ml" — that is the DENSITY OF SULFURIC ACID, a figure entering directly into the preparation of the reaction mixture; without the corrigendum the standard gives a wrong value. Ap2 (June 2010): "In Annex B, Table B.3, in the column Relative Reproducibility, for mg/l read %" — a change of UNIT in the precision table, so the reproducibility figures are read as percentages, not as mg/l. The text of both corrigenda is FREE on the PKN site (links beside the "Additional elements" field on the card)
Measurement range0.005–0.8 mg P/L (without dilution)
Detection limit0.005 mg P/L (direct), 0.0005 mg P/L (after extraction)
Wavelength880 nm (optimum) or 700 nm
Color development time10–30 minutes (stable 24 h)
Precision (CV)2–5%
Mineralization (total phosphorus)K₂S₂O₈ + H₂SO₄, 120°C, 30 min

Standard

Standard number
PN-EN ISO 6878:2006+Ap1:2010+Ap2:2010
Title (PL)
Jakość wody — Oznaczanie fosforu — Metoda spektrometryczna z molibdenianem amonu
Title (EN)
Water quality — Determination of phosphorus — Ammonium molybdate spectrometric method

Step-by-step procedure

  1. Mixed reagent preparation

    Mix in sequence: 50 mL H₂SO₄ 4.5M + 5 mL antimony potassium tartrate solution + 15 mL ammonium molybdate solution + 30 mL ascorbic acid solution. Prepare on day of use!

    ⏱ Time: 10 min

  2. Mineralization (total phosphorus only)

    To 40 mL sample add 5 mL K₂S₂O₈ solution and 1 mL H₂SO₄ 4.5M. Mineralize in autoclave 120°C/30 min or thermoreactor. Cool to room temperature.

    ⏱ Time: 60 min • 🌡 Temperature: 120°C

  3. Sample preparation (orthophosphates)

    Measure 40 mL sample into 50 mL volumetric flask. For turbid samples — filter through 0.45 μm filter. Sample must be at room temperature.

  4. Reagent addition

    Add 1 mL ascorbic acid, then 2 mL acidic molybdate solution (mixed reagent). Fill to 50 mL with water. Mix thoroughly.

    ⏱ Time: 2 min

  5. Color development

    Wait 10–30 minutes for full blue color development. Color stable up to 24 hours.

    ⏱ Time: 10–30 min

  6. Absorbance measurement

    Measure absorbance at 880 nm (or 700 nm) against blank. Read P concentration from calibration curve. Cuvette 10–40 mm (select for concentration).

    ⏱ Time: 5 min

  7. Calculations

    P concentration [mg/L] = curve reading × dilution factor. Conversion: PO₄³⁻ [mg/L] = P × 3.066.

  8. Quality control

    Control standard (e.g., 0.5 mg P/L) — deviation max ±10%. Blank — absorbance <0.01. Duplicates — RPD <10%.

Required equipment and apparatus

EquipmentExampleIndicative price
UV-VIS spectrophotometerHach DR6000, Shimadzu UV-1900, Analytik Jena Specord 250 Plus15 000–45 000 PLN
Optical cuvettes 10–50 mmGlass or quartz cuvettes, 10, 20, 40 mm50–300 PLN/pc
Autoclave or thermoreactorFor total phosphorus mineralization (120°C/30 min)4 000–30 000 PLN
Automatic pipettesEppendorf Research Plus 1–10 mL, 100–1000 μL800–2 000 PLN
Volumetric flasks 50 mLClass A, borosilicate glass30–80 PLN/pc

Reagents, media and consumables

ReagentCASDetails
Ammonium molybdate (NH₄)₆Mo₇O₂₄·4H₂O12054-85-2Acidic solution: 13 g molybdate in 100 mL H₂SO₄ 4.5 mol/L + 400 mL water. Solution I.
Ascorbic acid C₆H₈O₆50-81-7Reducer: 17.6 g/L in water. Prepare fresh (unstable — oxidizes). Valid max 1 week refrigerated.
Antimony potassium tartrate K(SbO)C₄H₄O₆·½H₂O28300-74-5Reaction catalyst: 0.34 g/L in water. Solution II. Shelf life: several months.
Sulfuric acid H₂SO₄7664-93-9Solution 4.5 mol/L (diluted 1+3). Acidic reaction medium.
Potassium persulfate K₂S₂O₈7727-21-1For total phosphorus mineralization: 5 g/100 mL. Strong oxidizer decomposing organic P forms.
PO₄³⁻ standard solution 1000 mg P/L7778-77-0KH₂PO₄ in water, certified CRM. For calibration curve.

Health and safety (OHS)

Frequently asked questions

Which standard describes this test?

The test is performed according to PN-EN ISO 6878:2006+Ap1:2010+Ap2:2010 — “Water quality — Determination of phosphorus — Ammonium molybdate spectrometric method”.

How does this method work?

Orthophosphate ions react with ammonium molybdate and antimony potassium tartrate in acidic environment (H₂SO₄), forming heteropolyacid phosphomolybdic complex (antimony-phosphomolybdate). Complex is reduced by ascorbic acid to intensely blue complex (molybdenum blue).

What is the measuring range and accuracy?

TWO Ap CORRIGENDA — TEXT READ 22 SEP 2026, AND THE FIRST CHANGES A FIGURE USED IN THE PROCEDURE: the designation of this article carries both elements ("+Ap1:2010+Ap2:2010"), yet until now it did not say what they change. Ap1 (March 2010, KT 121 for Water Quality — Chemical Testing — Inorganic Substances): "In 8.1.1, for 1.94 g/ml read 1.84 g/ml" — that is the DENSITY OF SULFURIC ACID, a figure entering directly into the preparation of the reaction mixture; without the corrigendum the standard gives a wrong value. Ap2 (June 2010): "In Annex B, Table B.3, in the column Relative Reproducibility, for mg/l read %" — a change of UNIT in the precision table, so the reproducibility figures are read as percentages, not as mg/l. The text of both corrigenda is FREE on the PKN site (links beside the "Additional elements" field on the card); Measurement range: 0.005–0.8 mg P/L (without dilution); Detection limit: 0.005 mg P/L (direct), 0.0005 mg P/L (after extraction); Wavelength: 880 nm (optimum) or 700 nm.

How long does the test take?

The times given for the individual stages add up to approximately 1 h 27 min–1 h 47 min. The procedure comprises 8 steps.

What equipment is required?

UV-VIS spectrophotometer, Optical cuvettes 10–50 mm, Autoclave or thermoreactor, Automatic pipettes, Volumetric flasks 50 mL. Indicative cost of the core instrument (UV-VIS spectrophotometer): 15 000–45 000 PLN.

Where is this test used?

Surface water eutrophication monitoring; Treated wastewater control (limit ≤1–2 mg P/L); Drinking water quality control; Chemical phosphorus removal process monitoring (coagulation); Enhanced biological phosphorus removal (EBPR) process control; Groundwater testing (agricultural impact).

What safety precautions apply?

Sulfuric acid — highly corrosive, causes severe burns. Use goggles and gloves.; Antimony potassium tartrate — contains antimony (Sb), toxic. Avoid inhalation and ingestion.; Potassium persulfate — strong oxidizer, irritating. Store away from combustibles.; Safety goggles, nitrile gloves, and coat mandatory.; Molybdenum and antimony-containing waste collect separately.

Which laboratory can perform this test?

The test is performed by laboratories accredited to ISO/IEC 17025. On LabCoda you can find them by the standard number PN-EN ISO 6878.

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