Determination of Total Nitrogen in Wastewater by Steam Distillation
Determination of Total Nitrogen in Wastewater by Steam Distillation
Determination of Total Nitrogen in Wastewater by Steam Distillation
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<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong><strong>by</strong> <strong>Steam</strong> <strong>Distillation</strong><strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Bill IckesProduct Manager Kjeldahl and ExtractionBuchi CorporationBrad MillerRegional Sales ManagerBuchi Corporation<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Who is Buchi Corporation?<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Buchi HeadquartersFlawilSwitzerland<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Buchi Corporation• Rotavapor®• Parallel Evaporation• Industrial Evaporation• Kjeldahl Solutions• Extraction Solutions (Soxhlet, Hot, Pressurized)• Spray Dry<strong>in</strong>g• Melt<strong>in</strong>g Po<strong>in</strong>t <strong>Determ<strong>in</strong>ation</strong>• Flash and Preparative Chromatography• Near Infrared Spectroscopy• Vacuum Pumps• Chillers<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Buchi Corporation USA• Direct Affiliate• New Castle, DE• 37 Employees Represent<strong>in</strong>g Sales, Market<strong>in</strong>g, TechnicalSupport, Service, and Warehouse Activities<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Content• Introduction to <strong>Total</strong> <strong>Nitrogen</strong> Analysis• Introduction to the Kjeldahl Method• Step I: Digestion• Step II: <strong>Distillation</strong>• Step III: Titration• Calculation <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong>• Other <strong>Steam</strong> <strong>Distillation</strong> Analysis• Summary<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Introduction to Analysis <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong><strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
What is <strong>Total</strong> <strong>Nitrogen</strong>?• Ammonia (Volatile Gas)• Ammonium Salts (Ex. Ammonium Sulfate)• Organic <strong>Nitrogen</strong> (Derived from Prote<strong>in</strong>, Urea, NucleicAcids, etc.)• Nitrates• Nitrites<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Why Analyze for <strong>Total</strong> <strong>Nitrogen</strong>?• Good Indicator <strong>of</strong> Water Quality• Clues to <strong>Nitrogen</strong> Source• Comparison Between Influent and Effluent Waste Water• Determ<strong>in</strong>es Waste Water Treatment Efficiency<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Differences <strong>in</strong> Analysis• Ammonia – Direct steam distillation <strong>of</strong> sample with noaddition <strong>of</strong> NaOH• Ammonium Salts – Direct steam distillation <strong>of</strong> samplewith addition <strong>of</strong> NaOH• Organic <strong>Nitrogen</strong> – Digestion, <strong>Distillation</strong>, and Titration <strong>by</strong>Kjeldahl Method• Nitrates/Nitrites – Digestion, <strong>Distillation</strong>, and Titration <strong>by</strong>Kjeldahl Method with the addition <strong>of</strong> Devarda’s Alloy priorto distillation<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Introduction to the Kjeldahl Method<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Who was Kjeldahl?Johan Kjeldahl 1849 – 19001849 born <strong>in</strong> Denmark1867 graduation from university1876 Scientist at Carlsberg Breweries Fermentation studies Development <strong>of</strong> a method for exact determnation<strong>of</strong> nitrogen <strong>in</strong> animal and vegetablematerial Research on carbohydrates <strong>in</strong> barley and malt1883 Publication <strong>of</strong> the Kjeldahl method<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Pr<strong>in</strong>ciple Kjeldahl Method1.DigestionConversion <strong>of</strong>Prote<strong>in</strong>-<strong>Nitrogen</strong> toNH 4+2.3.<strong>Distillation</strong> TitrationSeparation <strong>of</strong> Measure <strong>of</strong>NH the Amount <strong>of</strong>3Acid that wasneutralised <strong>by</strong>NH 3<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Step 1: Digestion<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
DigestionTarget <strong>of</strong> digestion: Breakage <strong>of</strong> organic bonds Conversion <strong>of</strong> <strong>Nitrogen</strong> to AmmoniumOrganic N NH 4+H 2 SO 4 conc.Digestion Mixture<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Digestion Mixture Digestion mixture is a mixture <strong>of</strong>- a salt (i.g. potassium or sodium sulphate)- and a catalyst (Hg, Se, Cu or Ti) Reason for addition <strong>of</strong> digestion mixtureIncreas<strong>in</strong>g <strong>of</strong> the digestion temperature→ faster and more efficient digestionImportant for reproducible results:Ratio <strong>of</strong> sulphuric acid and digestion mixtureIdeal proportion: 20ml/10g<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
RatioSulphuric Acid – Digestion MixtureThe ratio sulphuric acid – digestion mixture def<strong>in</strong>esthe boil<strong>in</strong>g po<strong>in</strong>t <strong>of</strong> the sulphuric acidIdeal digestion temperature: 370°CQuantityH 2 SO 4QuantityK 2 SO 4Boill<strong>in</strong>gpo<strong>in</strong>tRemarks20 ml -- 330 °C pure H 2 SO 420 ml 5 g 350 °C20 ml 10 g 370 °C20 ml 15 g 390 °Coptimaldigestion temp.already firstnitrogen loss<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Summary Digestion (I)Sample Homogenisation, Weigh<strong>in</strong>gand Addition <strong>of</strong> ReagentsSample2 tabs <strong>of</strong>CatalystSulphuric acidDigestion1.072BlankWeigh sample• 1 g <strong>of</strong> dry organic material(homogeneous)Add reagents• 10 g or 2 tabs <strong>of</strong> Kjeldahlcatalyst mixture• 20 ml <strong>of</strong> H 2 SO 4Sample Blank• add everyth<strong>in</strong>g exceptsample<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Summary Digestion (II)Digestionvapours toScrubberDigestion• digest at 370 °C for 90 m<strong>in</strong>or until the mixture is clear(green / blue color) + 30 m<strong>in</strong>Digestion<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Step 2: <strong>Distillation</strong>Step 3: Titration<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Pre-<strong>Distillation</strong> Steps1) Cool<strong>in</strong>gDigested sample is cooled down to RT2) DilutionDigested sample is diluted with deionised water3) Preparation <strong>of</strong> receiv<strong>in</strong>g vesselReceiv<strong>in</strong>g solution necessary to capture volatileammonia<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Preparation <strong>of</strong> Receiv<strong>in</strong>g Vessel (I) Reason for receiv<strong>in</strong>g vessel:Ammonia is volatile -> has to be captured <strong>in</strong>receiv<strong>in</strong>g solution Possibilities for receiv<strong>in</strong>g solutions:Boric acid solution (2% or 4%)M<strong>in</strong>eral acid standard solution (HCl or H 2 SO 4 )<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Preparation <strong>of</strong> Receiv<strong>in</strong>g Vessel (II)Recommendation for Kjeldahl determ<strong>in</strong>ation:Boric Acid 4% Easier handl<strong>in</strong>g No risk <strong>of</strong> too low capacity to capture all NH 3 Method <strong>of</strong> most <strong>of</strong>ficial methods<strong>Steam</strong> <strong>Distillation</strong>NH 3Receiv<strong>in</strong>g AcidNH 4 [B(OH) 4 ](Boric Acid)<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
<strong>Distillation</strong>: Addition <strong>of</strong> NaOHTarget <strong>of</strong> addition <strong>of</strong> NaOH:Release <strong>of</strong> ammonia <strong>in</strong> the form <strong>of</strong> NH 3NaOH(NH 4 ) 2 SO 4 NH 3<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Titration Possibilities <strong>of</strong> titration methods- potentiometric titration (pH)- visual titration (colour)- colorimetric titration (absorbance)Recommendation for Kjeldahl determ<strong>in</strong>ation:Potentiometric titration Advantages potentiometric titration:- more precise than visual and colorimetric titration- more robust than colorimetric titration(colorimetric titration is very susceptible)<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Potentiometric TitrationPo<strong>in</strong>ts to consider: Initial pH <strong>of</strong> the boric acid should be 4.65 Endpo<strong>in</strong>t <strong>of</strong> the titration should be pH 4.65Reason: pH 4.65 is turn<strong>in</strong>g po<strong>in</strong>t <strong>of</strong> the titration curvemLEnd po<strong>in</strong>t pH 4.65Warn<strong>in</strong>g po<strong>in</strong>tpH3.0 4.0 5.0 6.0 7.0 8.0<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Summary <strong>Distillation</strong> / Titration (I)DilutionmanuallyorautomatedDilution• dilute the cooled digestionsolution with 50 ml deionisedwater<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Summary <strong>Distillation</strong> / Titration (II)Preparation <strong>of</strong> ReceiverBoric acid titration• add 60 ml <strong>of</strong> Boric acid 4%• add 2 to 3 drops <strong>of</strong> <strong>in</strong>dicatoraccord<strong>in</strong>g to Sher<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Summary <strong>Distillation</strong> / Titration (III)Neutralisation and <strong>Distillation</strong>Sodium hydroxide• add 90 ml <strong>of</strong> NaOH 32% tothe diluted digestion solution<strong>Distillation</strong>• distill for 4 m<strong>in</strong>.<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Summary <strong>Distillation</strong> / Titration (IV)Titration7.15Boric acid titration• titrate the condensate withsulphuric acid standard solution(0.5 N or equivalent) to the endpo<strong>in</strong>t <strong>of</strong> pH 4.65<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Calculation<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Calculation% N =% P =(Consumption-Blank) x 1.4007 x n x 100Sample Size(Consumption-Blank) x 1.4007 x n x PF x 100Sample Size1.4007: 1 ml 0.1 N Volumetric Solution = 1.4007 mg Nn: Normality AcidPF:Prote<strong>in</strong> factor N Prote<strong>in</strong>(e.g. 6.25; Milk Sample 6.38; Nuts 5.4)<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Other Methods <strong>of</strong> Analysis w/ <strong>Steam</strong> <strong>Distillation</strong><strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Analysis Us<strong>in</strong>g <strong>Steam</strong> <strong>Distillation</strong>• Cyanides• Phenols• Volatile Acids<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Cyanide <strong>Determ<strong>in</strong>ation</strong><strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Method Reference: EPA Method 9010 C/335.2<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> Free Cyanide and Weak AcidDissociable Cyanide In Waste Water<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Why Analyze For Cyanide?• One <strong>of</strong> Natures Toxic Substances<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Sources <strong>of</strong> Cyanide?• Metal F<strong>in</strong>ish<strong>in</strong>g• Photographic Bleach<strong>in</strong>g• Galvanic Industry Waste Water<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
How is Cyanide Analyzed?• <strong>Steam</strong> distillation with strong acid• Collected <strong>in</strong> a receiv<strong>in</strong>g solution <strong>of</strong> NaOH• Cyanide concentration determ<strong>in</strong>ed colorimetrically at578nm<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Phenol <strong>Determ<strong>in</strong>ation</strong><strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Method Reference: EPA Method 9065<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> Phenolic Material <strong>by</strong>Spectrophotometric 4-am<strong>in</strong>oantipyr<strong>in</strong>e Method<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Why Analyze for Phenols?• Phenolic compounds are commonly found <strong>in</strong> sludge• Phenolic compounds can be traced to differentcontam<strong>in</strong>ation sources<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Sources <strong>of</strong> Phenols?• Plant Material• Chemical Industry Processes• Wood Process<strong>in</strong>g• Plastic Process<strong>in</strong>g<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
How are Phenols Analyzed?• <strong>Steam</strong> distillation <strong>in</strong> the presence <strong>of</strong> acid• Collected <strong>in</strong> water <strong>in</strong> the receiv<strong>in</strong>g solution• Photometric measurement <strong>of</strong> the receiv<strong>in</strong>g solution<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Volatile Acids <strong>Determ<strong>in</strong>ation</strong><strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Method Reference: Buchi Application Note K-355.004 Version A<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> Volatile Acids <strong>in</strong> Sludge<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Why Analyze for Volatile Acids?• Ratio <strong>of</strong> volatile acids -> total alkal<strong>in</strong>ity content <strong>in</strong> sludgesubmitted to anaerobic conditions is a good <strong>in</strong>dex <strong>of</strong>process performance <strong>in</strong>hibition<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Source <strong>of</strong> Volatile Acids?• Acetic Acid<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
How are Volatile Acids Analyzed?• <strong>Steam</strong> <strong>Distillation</strong>• Titration<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes
Questions?<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>Total</strong> <strong>Nitrogen</strong> <strong>in</strong> <strong>Wastewater</strong> 10/19/10 William H. Ickes