Optical Reagent-Free Measurement of COD, Nitrate, Nitrite with photolab 7600 The Online Measurement transferred to the lab 2015 WTW GmbH, [June 2015]
Juni 2015 Susanne Gollor From Online transferred to Lab: OptRF Optical Reagent-Free Measurement COD, NITRATE AND NITRITE WITH photolab 7600 UV-VIS
One for All All in One photolab 7600 UV-VIS: Routine Analysis: Programs with method data for standard parameters Application support e.g. chlorophyll determination in water enzymatic test kit support, color for wine quality Color Measurement Spectral analysis of standard parameters - OptRF Optical Reagent-Free Measurement (UV range) 3
Online-Measurement in Sewage Plants Online-monitoring+process control: with spectral probes for COD, NO3 and NO2: CarboVis, NitraVis, NiCaVis Allowing wide measurement range In Inlet, aeration and outlet Polychromator optics: Turbidity not being a disturbing factor 4
Pioneering Online procedures transferred to Lab! Optical Reagent-Free Measurement OptRF for outlets of municipal waste water treatment plants (WWTP) COD, NO 3, NO 2 - Just measure! 5
OptRF The principle Direct absorbance from NO 3, NO 2 in UV range COD = sum parameter with absorbance behaviour depending on sample matrix Pipette sample in 10 mm quartz cuvette (UV!) Spectral reading from 200-390 nm Instant value output on display based on reference spectra by matrices from many sewage plant real samples Actual methods are matching sewage plant outlets! Not suitable for most of industrial waste water since not all carbon sources (sugar/alcohol ) absorb in UV-range! Turbidity of Inlet is disturbing in lab methods: time of scan with, settling behaviour 6
OptRF based on spectral measurement From spectral measurement to instant data output: Absorbance 2,5 2,0 1,5 1,0 Spectral measurement of sample Spectra evaluation with complex algorithms Review: comparing with stored reference Direct value output 0,5 0,0 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 λ (nm) 7
OptRF with menu guidance No water is alike = varying matrix! Background evaluation and qualitative review of spectra Extinktion 3,5 3,0 2,5 2,0 1,5 Spectrum OK Absorbance to high -> Dilution Unmatching matrix: shape differs strongly from reference User calibration recommended 1,0 0,5 0,0 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 λ (nm) 8
OptRF User Calibration Optimization for the individual sewage plant: Adjustmend of characteristics via raw & veference value pairs User calibration Directly measured sample (OptRF) Negative raw values must be entered negatively! Concentration determination with test kits or standard methods 9
OptRF User Calibration Adjustment of characteristics via reference measurements: 1-point calibration changing second pair at the end of measurement range: Slope correction 2-point calibration changing both pairs of variates: slope correction 2-point calibration, change of both pairs of variates: Offset-correction Periodical reference measurements recommended for dynamic processes: e.g. seasonal variations of NO 3 => seasonal optimisation 10
OptRF Optimization with User Calibration Best procedure to implement OptRF routine: Optimization increases accuracy Start a comparison list with references, here a sample of COD total Sampling Date Time OptRF raw value [#] COD total (mg/l) Reference value (Test kits) COD total (mg/l) 03.04.2015 07:30 23,5 26 03.04.2015 09:15 28 32 05.04.2015 16:30 13,5 15 06.04.2015 14:20 19 23 Important: correct assignment of #raw + reference value for value pairs 1 point calibration to start with (upper pair) 2 point calibration for better calibration over a period of time Many pairs for linear regression (WTW xls template available) 11
OptRF User Calibration Linear Regression For best optimization especially for high dynamics Enter the value pairs into a WTW-XLS template => automatic calculation of slope and even calculated ideal value pairs 12
Comparison of OptRF, WTW probes and test kits OUTLET, WWTP Austria Comparison: Spectral probe, OptRF & Lab reference before User calibration for OptRF: => corresponding values of all measurement procedures after 13
OptRF - Procedures Measurement ranges (based on standards) COD NO 2 -N NO 3 -N 0.0 75.0 mg/l 0.00-4.00 mg/l 0.00-3.00 mg/l Dilution To measure all parameters in a sample, it might be necessary to dilute with different dilution factors/parameter, e.g due to seasonal varying NO 3 concentrations. Reason: the absorbance behaviour of the parameters are different and thus require a parameter-specific algorithm with consequence on dilution needs. OptRF in Surface water et. al. Depending on environment and sample matrix, preliminary testing is required. Surface water works frequently: Water bodies with big dynamics and events (heavy rain..) must be surveyed for over a longer period of time. For other waters than surface water, CODs (dissolved) is the better matching method. 14
OptRF - Applications Fast + cost free Add-on control to (official) self control Fast check of abnormal events Investigate quickly the optimal range of a test kit Cost-free test of retainer samples Onsite testing Connecting WTW-Online via IQ LabLink-procedure for quick online reference like VARiON planned
Pioneering! Optical Reagent-Free measurement OptRF Benefits: Faster than any digestion (COD: 2.5 hrs min.) Cost free w/o need of chemicals Reduction of over-all costs Ecofriendly w/o potassium Dichromate, Hg Non-hazardous, non carcinogenic 16
Well-proven Routine Analysis with Test Kits Barcode for round and rectangular cells Benefitial: reagent test kits with AutoSelector Highest convenience for method/program selection Highest quality offering lot certificates at the price of powder pillows. Automatic cell recognition no adapters Round and rectangular cell identification (10, 20, 50 mm) => automatic switch to correct measurement range corresponding to cell size Dilution function => automatic calculation of real sample: Use dilution function, to secure correct raw/reference value pair for OptRF user calibration 17
Routine Analysis Standard parameters with test kits COD, NO 3, NO 2, NH 4, (already benefitial due to small reagent volumes) Faults and standard deviations: Sampling Sample Preparation and operation Pipetting, vials, best measurement ranges. Limitation of the chemical procedure (accuracy COD approx. ±10-15%, e.g. 0.1 ml volume for COD up to 50.000 mg/l) GLP compliant handling: Double, better triple determination required control standards => AQS => Tolerances are a factor for any measurement procedure! 18
To Go OptRF and more. Customer-Service and Analytics to Go Low weight, just 4.5 kg Power Supply via standard car battery Standard cable for car batteries Onsite : weather protected location or at customer lab Optional field case for transportation Ideal for service and ministry of several plants and sites!
Spectral Analysis and Complex Routine Tasks 20
Qualitative Analysis + QC Spektra + Kinetics OptRF Storage of user profiles Color definition Editing of spectra (Comparison, Addition, Transfer into LIMS) Spectra New data acquisition => Faster scan speed Scan steps adjustable 1, 2, 5, 10 nm steps 21
More Application Support Industrial / Environmental Multi-wavelength + Special Procedures Measurement with multi-wavelength Chlorophyll, QC in Wine,. Multistep procedures e.g. entry of extraction volumes, several Abs measurements at different wavelengths => caluclation of readings Complex Programings and user defined definitions menu guided entry of variables, operations, factors NEW: color measurement CIE, Gardner, Yellowness 22
Enzymatic testing 23
Measurement with Enzymatic Test Kits Source: from www.r-biopharm.com tests: can be programmed for easier use, Glucose, Acetaldeyde, Malate programmed
340 nm: Hub of Enzymatic Analysis NAD + /NADH + and NADP/NADPH + are a hub in many metabolistic processes with enzymes and can be measured at 340 nm when being reduced: The second peak at 340 nm gives a typical peak and thus is used for determination of substances 25
Enzymatic test kits: e.g. Sac, Glu, Fru Determination Saccharose D-Glucose Hexokinase + ATP G-6-P Enzymatic Inversion ( cracking of Suc into Glu and Fru) Content Glu and Fru can be measured: 3 individual methods to determine Fru, Glu, Suc D-Fructose Hexokinase + ATP F-6-P Enzyme PGI G-6-P Dehydrogenase + NADP+ -> NADPH NADP+ -> NADPH + Dehydrogenase D-Gluconate 6-P D-Gluconate 6-P 26 1 NADP is equivalent to 1 D-Glu / 1 D-Fru
even more options 27
NEW: Extended PC Software + photolab Data spectral NEW: Color measurement from CIE to Gardner available: September 2015 Data management offering link to LIMS List price 290.-- Application: mostly Quality control Markets: Food&Beverage: Juice, Sugar, Oil Resin, varnish
New Features PC control Triggering measurements from PC will be extended: First step: photolab color via PC New Interface: Ethernet Universal PC connection in networks possible => simplifying the data transfer into LIMS Using standard cables, no special cable required RS232 virtually via USB
photolab 7000 Series Technical Data photolab 7100 (VIS) Wavelength Range 320-1100 nm 190-1100 nm photolab 7600 (UV/VIS) Optics Monochromator with Grating and step motor / reference beam Lamp Wolfram-Halogen Xenon Flashlamp Display Bandwidth Measurement Scan speed Wavelength accuracy/reproduceability Photometric accuracy/reproduceability Barcode Cuvette Data storage Methods and Profiles Interface / Update IP Class Power Supply Temperature Range Weight / Dimensions Accessories Farbdisplay 7" backlit 4 nm Concentration, Absorbance, % Transmission, Kinetics and Spectra in Abs or %Transmission, Multiwavelengths and multistep readings 700-2000 nm/min, Scans in 1, 2, 5, 10 nm steps of wavelength range ± 1 nm / < 0,5 nm - 0,003 E for E < 0,600; 0,5% of values for 0,600 < E < 2,000 Automatic method recognition including measurement range for all cuvette 16 mm round, rectangular 10 mm, 20 mm, 50 mm with automatic detection w/o adapter 5000 meausrement values, spectra and kinetics approx. 40 MB => 500 spectra (300-900 nm) and 400 kinetics with 150 measurement values, > 250 pre-programmed methods, 1000 user-defined methods, 20 profiles for kinetics and spectra, comprehensive programming options 1 USB-A, 1 USB-B, 1 Ethernet / Update via Internet and USB-Stick IP 30 including drainage in optical compartment Universal power supply, optional supply via standard adaptor cable for car batteries Operation: +10 C bis +35 C, Storage: -25 C bis +65 C approx. 4,5 kg / 404 x 197 x 314 (BxHxT) PC software photolab Data spectral+photolab color, field case, checking tools for AQA
photolab 7000 Serie photolab 7100 VIS Spectrophotometer from 320-1100 nm 3.500.-- photolab 7600 UV-VIS Spectrophotometer from 190-1100 nm 5.900.-- available for order and sale Promotion: Ugrade New for old:any instrument from any model & make Until December 31th 2015 4999,-- List Price instead of 5900.--
Tips & Tricks for Photometry Here you find monthly episodes with webcast, answers and material for: Basics of photometry AQA, Handling of test kits, sample preparation and test kit handling, ph and much more information. Application notes in water analysis, environmental monitoring, industries.. www.photometrycompendium.com
Thank you for your attention! Customer Care Center: TechInfo.WTW@xyleminc.com 33