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Metrohm ...
is the global market leader in titration offers a complete portfolio for NIR analysis, in addition to all of the methods of ion analysis titration, voltammetry, and ion chromatography is a Swiss company and manufactures exclusively in Switzerland grants a 3-year instrument warranty and a 10-year warranty on chemical suppressors for ion chromatography supports you with unparalleled application expertise offers you more than 1400 applications free of charge supports you with dependable on-site service worldwide is not listed on the stock exchange, but is owned by a foundation takes a sustainable approach to corporate management, putting the interests of customers and employees ahead of maximizing profit
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Metrohm instruments comply with numerous official directives, including the FDA regulation Title 21 CFR, Part 11.
refer to the specific application. Metrohm also offers suitable analytic methods for evaluating cleaning and disinfection steps in beverage manufacturing plants and quality control for coatings in beverage packaging.
Standard
AOAC 950.15 ISO 15212-1
Method
Page*
pH value measurement 68 Titration 9, 3233 Density measurement with oscillating U-tube 3233 Pressure and temperature measurement Process analysis, colorimetry or titration 35 Titration 9 Titration Ion chromatography 20 Ion chromatography 23 Ion chromatography 24 Voltammetry 27 pH value measurement Titration Process analysis, colorimetry, or titration Titration Titration (Thermometric) titration Ion chromatography 9 35 9 15
ISO 10523 ASTM D 1293 EPA 150.1 EPA 130.2 ISO 9963 DIN EN ISO 8467 DIN EN ISO 10304-1 ASTM D 4327 EPA 300.1, Part A
ISO 11206 DIN EN ISO 10304-4 Oxyhalides: bromate, chlorite, chlorate ASTM D 6581 EPA 300.1, Part B Cations Phenols CN
Ion chromatography
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Ion chromatography
U(VI) Zn, Cd, Pb, Cu, Tl, Ni, Co Mn, Al Vitamin C (ascorbic acid) Caffeine Soft drinks Vitamin C (ascorbic acid) Vitamin C (ascorbic acid) Titratable acidity Formol number Ash alkalinity Potassium Fruit and vegetable (Organic) acids juices Phenylalanine, aspartame, caffeine Glucuronlactone Vitamin C (ascorbic acid) Fumaric acid Saccharin Pb pH value of cocoa products Titratable acidity of roasted coffee Kjeldahl nitrogen Water content in cocoa products Infusion beverages Water content in instant coffee (Coffee, tea, cocoa, etc.) Water content in roasted coffee Free and total carbohydrate content in instant coffee Direct reducing sugars Caffeine
Ion chromatography Sample preparation Voltammetry acc. to DIN 38405-13 DIN 38406-17 Voltammetry DIN 38406-16 Voltammetry Process analysis, colorimetry Titration Ion chromatography Voltammetry AOAC 967.21 Titration Titration Titration Titration Titration Ion chromatography Ion chromatography Ion chromatography Voltammetry AOAC 968.16 Voltammetry SLB 41-2.5 Voltammetry AOAC 979.17 Voltammetry AOAC 970.21 pH value measurement AOAC 920.92 Titration Titration via Kjeldahl distillation AOAC 977.10 Karl Fischer titration ISO 20938 Karl Fischer titration ISO 11817 Karl Fischer titration ISO 11292 Ion chromatography Ion chromatography Ion chromatography
27 35 9 27 9
24
27
27 9
1617 23 23
Alcoholic beverages
Parameters
Titratable acidity Sugar concentration in Brix Carbon dioxide content Chloride Sulfate Anions and cations Carbohydrates, sugar alcohols pH value Alpha acids in hops Alkalinity of brewing water pH value Sulfurous acid Carbon dioxide content Titratable acidity Wine Ash alkalinity Vitamin C (ascorbic acid) (Organic) acids Biogenic amines Zn, Cd, Pb, Cu, Ni, Co, Cr, Fe Titratable acidity in distilled alcoholic beverages
Standard
AOAC 940.15 ISO 15212-1
Method
Titration Density measurement via oscillating U-tube Pressure and temperature measurement Titration Titration Ion chromatography Ion chromatography pH value measurement Titration Process analysis, titration pH value measurement Titration Titration Titration Titration Titration Ion chromatography Ion chromatography Voltammetry
Page*
9, 3233 3233 9 20, 24 23 7 1213 35 7 9
05
AOAC 945.10
Beer
EBC 7.4
AOAC 960.19 AOAC 940.20 AOAC 988.07 AOAC 962.12 AOAC 950.07
24 27 9
Distilled spirits
AOAC 945.08
Titration
Liquid food
Parameters
pH value Iodine and peroxide value Titratable acidity Anions and cations (Organic) acids Carbohydrates, sugar alcohols Zn, Cd, Pb, Cu, Ni, Co, Cr, Fe Chloride in dairy products Sodium in dairy products Vitamin C (ascorbic acid) Calcium Kjeldahl nitrogen Choline Melamine Lactose in lactose-free products Carbohydrates, sugar alcohols Pb AOAC 974.13 AOAC 979.17
Standard
Method
pH value measurement Titration Titration Ion chromatography Ion chromatography Ion chromatography Voltammetry Titration Thermometric titration Titration Titration Titration via Kjeldahl distillation Ion chromatography Ion chromatography Ion chromatography Ion chromatography Voltammetry
Page*
67 9 22 24 23 27 9 15 9 22 23 27
Monitoring of cleaning and disinfection processes in beverage manufacturing plants and quality controls of coatings in beverage packaging
Parameters
Cleaning progress Beverage packaging pH value and conductivity Peracetic acid in filling systems Coating quality
Standard
Method
pH value and conductivity measurement Process analysis, colorimetry Electrochemical impedance spectroscopy
Page
67 35 28
*Areas that contain no page reference stand for Metrohm applications that are not described in this brochure. For more information, please contact your local Metrohm representative.
pH measurement 06
The pH value is an important parameter for the quality control of beverages. It has a significant effect on the digestibility, flavor, and stability of the beverage. The pH value controls enzyme activity during alcoholic fermentation, which is why it must be checked regularly. The requirements of the pH electrode used to perform measurements are as diverse as the range of beverages to be analyzed. The selection of a diaphragm suitable for the beverage sample is particularly important, since otherwise the sample can quickly block the electrolyte bridge, leading to inaccurate results. The following table lists examples of the Metrohm electrodes suitable for pH determination in various beverages.
Sample
Properties Precise results and very rapid response times even in ion-deficient, poorly buffered solutions Fixed ground-joint diaphragm, insensitive to contamination Maintenance-free reference electrolyte, variable bridge electrolyte for special applications Optimized length for sample changer applications Universal use Rapid response to temperature changes Fixed ground-joint diaphragm, insensitive to contamination Especially for highly contaminated, protein-containing, or viscous samples Low maintenance capillary diaphragm
Drinking water
Beverages in general, e.g., wine and spirits, fruit and vegetable juices Beverages containing protein, e.g., milk
Unitrode (6.0258.600)
Porotrode (6.0235.200)
pH determination in alcoholic beverages The pH value is of great importance in biological systems. It influences microorganism growth, color/hue, flavor, redox potential, the ratio of free to bound SO2, the formation or prevention of iron phosphate turbidity, etc. There is no direct correlation between pH value and titratable acidity; there is however an empirical relationship between the pH value and the ratio of potassium hydrogen tartrate to tartaric acid. For wine, beer, and spirits, it is advisable to use a Unitrode as a universal pH electrode. The Unitrode has a fixed ground-joint diaphragm which protects against contamination. Selected examples pH value in beer pH value in wine AOAC 945.10 AOAC 960.19
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pH value in beverages with the 826 pH mobile Easy operation, thanks to a clearly structured multiline display Automatic buffer recognition Wide range of accessories from a single source
Buffer sachets pH 4, 7, and 9 buffer solutions in sachets ensure precise calibration of the pH electrode.
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Robust, dependable, and easy to use: Metrohm pH meters pH value determination with the 826 pH mobile and 827 pH lab meters Whether for routine pH value measurements in the laboratory or for use in the field, you will never have to go without GLP: 3-point calibration, automatic buffer recognition, temperature compensation, sample identification, GLP-compliant printout, and a large data memory. 780 pH Meter and 781 pH/Ion Meter When you need absolute precision, reach for the 780 pH Meter: 9-point calibration, stirrer control, electrode test for pH glass electrodes, method memory, and RS 232 interface. Besides measuring pH, the 781 pH/Ion Meter can also determine the concentration of individual ions (e.g., Cl , + F , NH4 ) by either direct measurement or fully automatic standard addition.
Titration
Benefit from our application experience We offer you a comprehensive selection of potentiometric applications for the beverage industry, many of which are based on the following publications: German standard methods for the examination of water, waste water and sludge Official Methods of Analysis of the Association of Official Analytical Chemists (AOAC, U.S.A.) Schweizerisches Lebensmittelbuch (SLMB; Swiss Manual on Food Safety) U.S. Environmental Protection Agency (EPA) Example: sulfite stabilization Sulfites have antimicrobial and antioxidant properties and they extend the shelf life of wine, but some consumers have adverse reactions to them. Increasingly, modern wine-making technologies are making it possible to create sulfite-free wines (less than 10 mg/l of sulfite). An overview of selected applications Sulfurous acid in wine Titratable acidity in distilled spirits Total hardness of drinking water Titratable acidity in nonalcoholic beverages Titratable acidity of roasted coffee Oxalic acid in fruit and canned fruit Ascorbic acid (vitamin C) in juices AOAC 940.20 AOAC 945.08 EPA 130.2 AOAC 950.15 AOAC 920.92 AOAC 974.24 AOAC 967.21
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It is impossible to make high-quality sweet wines that are sulfur-free because the high sugar content provides an ideal breeding ground for a broad range of microorganisms. Limit values for residual SO2 content vary by region and wine.
Electrodes for titration The right electrode for every application Choosing the right electrode is crucial for successful titration. For combined electrodes, the correct diaphragm must be chosen to avoid blockage. The response behavior of the electrode is also of critical importance, in particular if the titration is to be carried out to a defined
endpoint. If the electrode reacts too slowly, the solution will be over-titrated and incorrect results are obtained. The following table lists Metrohm electrodes suitable for various applications.
Field of application General Titratable acidity of alcoholic beverages Determination of Ca , Mg Permanganate index Titratable acidity in dairy products Calcium content in dairy products Kjeldahl nitrogen in milk Vitamin C in fruit juice Formol number Iodine and peroxide values General chloride, table salt content in beverages Additional examples and practical tips on using Metrohm electrodes are provided in the leaflets "Electrodes for
2+ 2+
Metrohm electrode Ecotrode Plus Unitrode Ca2+ ISE Pt Titrode Porotrode Cu ISE Ecotrode Gel Double Pt-sheet electrode Unitrode Pt Titrode Ag Titrode
2+
6.0262.100 6.0258.600 6.0257.600 6.0510.100 6.0431.100 6.0235.200 6.0502.140 6.0221.100 6.0309.100 6.0259.100 6.0431.100 6.0430.100
Carbonate hardness, acid capacity of water, p and m values Aquatrode Plus (complexometric)
Titration" and "Electrodes for pH Measurement". These can be downloaded free of charge at www.metrohm.com.
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Titration with Metrohm: solutions for every budget and requirement With the Food Titrino plus, the Food Ti-Touch, and the Food Titrando, Metrohm offers you three complete titration packages. No matter which package you choose, ease of use and reliability is guaranteed: Intelligent exchange or dosing units ensure the use of the correct titration solution and also enable its monitoring. All important titration parameters are stored with the methods, enabling any user to obtain reliable results quickly. GLP-compliant data output, either in printed or digital form.
Food Ti-Touch the economically priced titrator for routine analysis in the food laboratory. This all-inclusive package also includes a USB stick with 100 stored methods for the most important applications in food analysis.
814 USB Sample Processor Depending on the application, different sample racks can be used on the 814 USB Sample Processor, i.e., 22 vessels 120 mL. Measurement of the prescribed beverage volume is also fully automated, as is the option enabling complete decarbonization of wine samples. Automation improves reproducibility of results and saves time. The cost of automation amortizes quickly. Control of the system and all data handling is managed by the tiamoTM software. tiamoTM is the leading control and database software for titrators and dosing devices, as well as total laboratory automation, to include client/server systems, which is why the name tiamoTM stands for titration and more tiamoTM can do more than just titration, and it does it in numerous languages.
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815 Robotic USB Sample Processor the automated system for wine analysis. Up to 100 samples can be placed on the sample rack and titrated directly, depending on the application. Optionally, the system can automatically measure the sample into an external titration vessel or perform decarbonization. The high degree of automation ensures that every sample is titrated under identical conditions, thus guaranteeing traceable and reproducible results.
862 Food Beverage Compact Titrosampler the compact automatic titration station for medium sample throughput. The titrosampler excels in minimal space requirements; titrator and sample changer are combined in a single instrument.
Food Titrando the high-end titrator for the most sophisticated requirements. Complete traceability of measuring results, central data management through client/server option, method templates, frequently used methods started at the press of a button, individual method development, possibility of complete automation, and much more.
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Alpha acids in hops according to EBC 7.4 Hops play an important role in the brewing process, as they have a critical effect on the flavor, bitterness and shelf life of beer. The alpha acids contained in hops are crucial for the bitterness of the beer. Bitterness is expressed in IBU (International Bittering Units), for which one IBU corresponds to 1 milligram of dissolved alpha acids. In order to achieve the required bitterness at the end of the brewing process, the quantity of hops added
must be dosed precisely. Depending on the type of beer, different varieties of hops are used, each with a different alpha acids content. According to the European Brewery Convention (EBC 7.4), the content of alpha acids is determined by conductometric titration with lead acetate solution. This method can be used for all hop products, e.g., hop umbels, pellets, or extracts.
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Easy, quick, and cost-effective With the 856 Conductivity Module and tiamoTM titration software, Metrohm offers an easy, quick, and cost-effective system for determining alpha acids in hops in accordance with EBC 7.4. The hop products are first extracted with toluene. The user simply places an aliquot of the toluene in the titration vessel; the addition of methanol
and the subsequent titration are performed automatically at the push of a button. At the end of the determination, the result can be calculated in whatever format is required, and a freely configurable report can either be saved as a PDF file or printed out directly. All of the determination data are stored in the tiamoTM database.
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Selected examples Sulfate in drinking water Sulfate is precipitated in an acidic solution through the addition of a barium chromate solution. Excess barium chromate is also precipitated through the additional dosing of ammonia. The remaining, soluble chromate fraction corresponds to the quantity of sulfate and can be determined by titration using thermometric endpoint detection with an iron(II) solution.
Sodium in dairy products The sodium content of beverages is usually determined indirectly through a precipitation reaction with silver nitrate. The assumption behind this approach is that the chloride ions are present in a molar ratio of 1:1 with the sodium ions. However, this is not true if other chemical substances such as sodium benzoate, monosodium glutamate, or salts such as potassium chloride are present in the matrix, as is often the case in beverages containing sodium. Established methods for the direct determination of sodium such as AAS or ICP/MS have the disadvantage of requiring instruments that are very expensive. Thermometric titration is a cost-effective and easy alternative. In this method, proteins in the milk sample are first precipitated with trichloroacetic acid and then separated through filtration or centrifugation. An aliquot is titrated in the presence of NH4F at a pH value of 3 with an aluminum nitrate solution with an excess of potassium ions. The exothermic reaction produces insoluble NaK2AlF6 .
Thermometric determination of sulfate content in a drinking water sample. The titration software determines the endpoint with the help of a second derivative (red) of the titration curve (blue).
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Examples The following overview contains various sample matrices from the beverage industry with water contents that can be determined by Karl Fischer titration. Detailed informaSample matrix Nonalcoholic beverages Dairy products Raw materials for juice and juice drink production Luxury foods (alcohol, coffee, tea, cocoa) Raw materials for beer production Samples
tion and titration regulations can be found in the free Metrohm monograph "Water Determination by Karl Fischer Titration". Type of titration Volumetric Volumetric Volumetric
Fruit juice, vegetable juice, syrup, sodas Milk Various fruit and vegetables Cognac, gin, spirits, liqueur, whiskey, wine, cocoa beans, cocoa powder (AOAC 977.10), instant coffee (ISO 20938), roasted coffee, raw coffee (ISO 11817), cappuccino powder Barley, hops
Volumetric
Volumetric
901 Titrando with 900 Touch Control and Polytron PT 1300 D: samples are pulverized directly in the titration cell. This prevents the absorption of additional moisture during sample preparation, thus assuring accurate results.
Laboratory automation 18
The complete range of automatic sample preparation from a single supplier Normally, accurate pipetting and dilution of the sample is sufficient for determining pH value, titratable acidity, or chloride content in beverages and liquid foods. Metrohm offers you a wide range of products for the fully automated, precise, and time-saving preparation of liquid samples. Automation time savings and greater accuracy In beverage analysis, it is primarily chromatographic methods, such as IC, HPLC, and GC that are employed in addition to direct titration. These measuring techniques require that the sample be available as a filtered liquid before it can be injected into the column. When carried out manually, as is often the case, sample preparation steps such as decarbonization of carbonated beverages pulverization and/or homogenization filtration pipetting and/or dilution are tedious and time-consuming. Furthermore, manual sample preparation involves the risk of inaccurate results. Specifically, it is scarcely possible to ensure reproducible sample preparation quality when a large number of samples is involved and several different people are processing the samples.
Fully automated titration of an homogenized sample: The 815 Robotic Titration Soliprep performs sample preparation and titration in a single procedure without the need for filling out multiple copies of sample tables or shifting beakers around. This prevents mix-ups and shortens the standing times prior to the analysis.
Robotic Soliprep automatic sample preparation tailored to your needs With the instruments of the Robotic-Soliprep family, neither deviation in results nor time-consuming manual routines are an issue any longer. The solid substance is simply weighed out and placed in the sample rack everything else is completely automated. Depending on the model selected, different steps can be combined including the direct connection to a chromatograph or the performance of the titration in the homogenized sample.
Robotic Titration Soliprep Homogenization + + + + + Robotic Filtration Soliprep + Robotic Flexible Soliprep + Robotic Soliprep for LC +
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Fully automated filtration: The 815 Robotic Filtration Soliprep filters away remaining solid matter from the homogenized sample. What remains is a clear filtrate that can be either directly injected into an analytical instrument or further diluted.
Ion chromatography 20
Ion chromatography (IC) is a standard method for beverage analysis. Numerous main ingredients, components with effects on taste and health and traces of contaminants can be reliably and precisely determined with the help of IC. Multicomponent determinations in a single analysis In addition to anions and cations, also carbohydrates, organic acids, and polar substances can be quantified in a variety of beverages. The advantage of ion chromatography is that parallel determinations of chemically similar substances can be carried out in a single analysis. Furthermore, the concentration of the analytes can vary from the ng/L up to the percentage range. Of course, all Metrohm IC instruments and the MagIC Net chromatography software are in compliance with FDA standards. Save time and costs through automatic sample preparation As in titration, sample preparation has an important role to play in ion chromatography. Unique inline methods (some patented by Metrohm) permit the integration and complete automation of sample preparation into the analytical process. This increases security, reduces the number of manually performed steps, improves reproducibility, and guarantees the traceability of the entire analysis (including sample preparation).
Metrohm Inline sample preparation methods for beverage analysis Inline Ultrafiltration Inline Dialysis Inline Dilution Inline Extraction Inline Matrix Elimination Inline Preconcentration Inline Degassing Intelligent Partial Loop Injection
Inline Ultrafiltration reliably removes unwanted particles from the sample solution and thus protects the separation column from contamination.
Analysis of mineral waters The anionic and cationic substances in table and mineral waters are analyzed by IC. Numerous ISO, ASTM, and EPA standards specify ion chromatography testing methods and binding limit values for ions hazardous to health such as bromate. The German drinking water ordinance originally stipulated a limit of 25 g/L for bromate, but lowered it to 10 g/L in 2008. The limit for mineral water is 3 g/L. The EU and the U.S. Environmental Protection Agency (EPA) have set the same maximum bromate concentrations for their drinking water guidelines. Other ions such as iodide influence flavor, which is why their concentration in mineral water is monitored.
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Intensity [mAU]
Time [min]
Analysis of a mineral water sample enriched with 0.5 g/L of bromate with post-column derivatization and UV/VIS detection; column: Metrosep A Supp 16 - 100/4.0; eluent: 100 mmol/L H2SO4, 19.3 mol/L ammonium heptamolybdate, 0.8 mL/min; column temperature: 45 C; post-column reagent: 0.27 mol/LKI, 0.2 mL/min, wavelength 352 nm; sample volume: 1 mL
940 Professional IC Vario with 944 Professional UV/VIS Detector Vario and 943 Professional Reactor Vario: the ideal system for your bromate analysis.
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22 20 18
16 14 12 10 8 6 4 2 0 0 1 2 3 4
10
11
12
13
14
15
Time [min]
Anion analysis of an ultraheat-treated milk, IC with conductivity detection; column: Metrosep A Supp 5 - 100/4.0; eluent: 3.2mmol/L Na2CO3, 1.0 mmol/L NaHCO3, 0.7 mL/min; column temperature: 30 C; injection volume: 20 L
Analysis of dairy products For dairy products be it baby food, yogurt, milk, or lactose-free foods ion analysis is essential to quality control. Inline Dialysis is the efficient sample preparation technique for fully automated separation of proteincontaining matrices, thus replacing the time-intensive, manual protein precipitation step with Carrez reagent. Ion chromatography enables not only the determination of anions (e.g., iodide, chloride, phosphate, sulfate, nitrate, nitrite, thiocyanate, cyanurate, and perchlorate) and cations (e.g., sodium, ammonium, potassium, calcium, magnesium, and melamine), but also that of carbohydrates (e.g., galactose and lactose).
Conductivity [S/cm]
Inline Dialysis the ideal inline sample preparation for the removal of proteins, oils, and particles before ion chromatographic analysis.
Carbohydrate and sweetener analysis How sweet is sweet? This is not an easy question to answer for some beverages. To get the right answer, you first have to know the carbohydrate composition. In addition, the level of sugar alcohols and sweeteners, such as steviol glycosides, has to be determined. The fol-
lowing table lists a wide array of components that can be reliably analyzed in various beverage matrices using ion chromatography and pulsed amperometric detection (PAD). The table also shows the method of sample preparation.
Steviol glycoside (stevia)
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Sample preparation
Propylene glycol
Maltopentaose
Maltotriose
Matrix
Cola Diet cola Apple juice Orange juice Tomato juice Maple syrup Corn syrup Red beet extract Instant coffee Instant tea Beer Beer wort Vodka Dairy beverages
D D F, D F, D F, D D D D E, F, D F, D U, D + F, D D Dialysis
+ +
+ +
+ +
+ +
+ + + + + + + + + + + + +
+ + + + + + + + + + + + + + + + + + +
+ + + + + + + + + + + + + + + +
Polyols, sugar alcohols, monosaccharides, disaccharides, oligosaccharides, steviol glycosides E: extraction, F: filtration, U: ultrasonic treatment, D: dilution
940 Professional IC Vario with 858 Professional Sample Processor for ion analysis with Inline Dialysis.
Maltoheptaose
Maltohexaose
Maltotetraose
Cellobiose
Arabinose
Galactose
Lactulose
Raffinose
Mannose
Mannitol
Fructose
Glycerol
Maltose
Glucose
Sorbitol
Sucrose
Lactose
Inositol
Ribose
Xylose
Xylitol
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Acids and anions in wine Acids are a key component of wine. They preserve the wine and lend it expression and character. Wines contain a number of different types of acids. Tartaric, malic, and lactic acids are particularly important, as is carbon dioxide with champagne and sparkling wines. The method is also suitable for analyzing many other beverages.
Biogenic amines in wine In addition to the individual acids, ion chromatography can determine the presence of biogenic amines produced during malolactic fermentation, such as histamine, tyramine, putrescine, and phenylethylamine.
18 16 14
Conductivity [S/cm]
Tartrate
12 10 8 6 4 2 0 0 1 2 3 4 5 6 7 8 Chloride Succinate
Analysis of ions and organic acids in wine; column: Metrosep A Supp 10 - 100/4.0; eluent: 5.0 mmol/L Na2CO3 and 5.0 mmol/L NaHCO3, 1.0 mL/min; sample volume: 20 L; Inline Dilution: 1:10
Malate
9 10 11 12 13 14 15 16 17 18 19 20
Time [min]
Sulfite
Free choice of eluents For every application, there is an optimal eluent characterized by an ideal composition, whether it be a certain combination of dissolved salts or the addition of organic solvents. Metrohm offers you a fully automated solution for every chromatographic separation: the 941Eluent Production Module is a very flexible system component that can be used with every inline eluent preparation imaginable.
Sulfate
Analysis at its most effective Flexibility enables a wide range of applications Ion chromatography is practically predestined for beverage analysis. Anions, cations, organic acids, amines, carbohydrates they can all be detected with a single system. Manual operations can easily be integrated in automated processes to save time and increase reproducibility and accuracy.
MagIC Net MagIC Net is a high-performance ion chromatography software that ensures an efficient workflow. Key advantages of MagIC Net Easy and intuitive operation Freely configurable user interface High flexibility Modern data management Powerful report generator Comprehensive monitoring and control functions Complete traceability of all data Client/server software Meets all FDA and GLP requirements Available in numerous languages
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Analysis of a wine standard with Li+, Na+, NH4+, K+, Mg2+, Ca2+, putrescine, cadaverine and histamine with the 940 Professional IC Vario; column: Metrosep C 1 - 125/4.6; eluent: 2.5mmol/L HNO3 with 10% acetone; Inline Dilution 1:10; sample volume: 10 L
Save time with Metrohm Inline Ultrafiltration Metrohm Inline Dilution Inline eluent preparation
Save money with Low operating costs 10-year suppressor guarantee 3-year guarantee on all instruments Guaranteed availability of replacement parts for 10years after production discontinuation date of the instrument
Voltammetry 26
High detection sensitivity at low cost Voltammetry is an electrochemical analytical method that provides information on the type and amount of substances contained in a dissolved sample on the basis of a current-voltage curve. The importance of voltammetry lies in its high accuracy and sensitivity, the possibility of performing a speciation analysis, and its competitive price. Heavy metal ions present as contaminants in beverages can be determined with high detection sensitivity through the use of voltammetry. Because the organic beverage matrix complexates the heavy metals to a certain extent,
the samples must first be digested. Some organic substances in beverages, such as vitamin C, vitamins of the Bgroup, or quinine, can also be determined by voltammetry. 797 VA Computrace The 797 VA Computrace is a modern, PC-controlled voltammetric analysis system. The potentiostat/galvanostat built into the instrument guarantees highest precision with low noise. The PC software supplied controls the determination and calculates and archives the results.
The 909 UV Digester: for rapid removal of interfering organic sample components via UV digestion
The 797 VA Computrace: for sensitive determination of trace metals and certain vitamins in beverages
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Selected examples Uranium in mineral water in accordance with DIN38406, Part 17 For the highly toxic and radioactive metal uranium, the World Health Organization (WHO) recommends a limit value in drinking water of 30 g/L for adults. Unlike the complicated and very expensive spectroscopic analysis procedures, the 797 VA Computrace can determine levels of dissolved uranium simply and cost-effectively in the ng/L range. The analytic procedure is described in Application Note V-045, Uranium in drinking water.
Cadmium, lead, and copper in wine (also zinc, nickel, cobalt, chrome, iron, etc.) The analysis of heavy metals in wine provides information on the type and concentration of contaminants. In view of the significance of these elements, their exact determination with high-performance methods is essential. Following a UV digestion in the 909 UV Digester, the 797 VA Computrace enables the determination of heavy metals in wine (Application Notes V-092 to V-094 and V-201). This method also yields outstanding results for other beverage matrices.
Cu 150
I [nA]
100
50 Cd 0
Pb
Zinc, cadmium, lead, copper, thallium, nickel and cobalt in water in accordance with DIN 38406, Part 16 Drinking water has to be tested regularly to determine levels of these metal ions. DIN 38406, Part 16 describes the method for determining levels of these ions in different types of water. Heavy metal determination in drinking water is described in the following notes: AN-V-086 Cadmium, lead, and copper in drinking water AN-V-087 Nickel and cobalt in drinking water AN-V-091 Iron in drinking water
-0.60
-0.40
-0.20
0.00
U [V]
Voltammetric determination of cadmium (concentration < detection limit), lead (17.7 g/L) and copper (192.8 g/L) in red wine following UV digestion
Vitamin C in fruit, vegetables, and juices Commercially available fruit and vegetable juices can bedirectly and easily analyzed as sample liquids. Freshsqueezed fruit juices are also suitable (V-073), carbonated beverages should be degassed before analysis (V-095).
The Metrohm database offers more than 1400 other applications which can be downloaded for free at: http://www.metrohm.com/com/Applications
For sensitive electrochemical impedance measurements: the Autolab PGSTAT204 with the FRA32M module
www.metrohm-autolab.com
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Offline laboratory analysis Manual sample collection during operation Transport of the sample to the laboratory Registration and analysis in the laboratory
Atline analysis Manual sample collection during operation Automatic analysis directly in the production process Determination of one or more parameters Numerous measuring points Low to medium frequency of analyses Rapid onsite analytical results
Online analysis Sample collection via bypass line Automated sample preparation Fully automated analysis Fastest response time and high frequency of analyses Results as controller input
ProcessLab ADI 2045PL analysis system: each system is configured with the relevant modules according to user preferences.
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Examples Nitrites in drinking water Nitrites are toxic to humans. They react with the iron in hemoglobin, thus interfering with oxygen uptake. In addition, nitrites, in the presence of secondary amines, can lead to the formation of carcinogenic n-nitrosamines in the body. Strict limit values on nitrite content are in place worldwide. The World Health Organization prescribes a maximum nitrite content in drinking water of 500 g/L. Drinking water leaving public water works is held to the more stringent limit value of 100 g/L. In Germany, baby food may not be prepared with table or mineral waters that have nitrite concentrations of 20g/L or more. Nitrite levels are colorimetrically determined: in an acidic solution, nitrites react with primary amines to produce diazonium salt, which bonds with aromatics to form an azo dye detectible down to the low g/L range. ProcessLab ensures convenient atline determination of nitrite levels at waterworks around the clock seven days a week if necessary. Consumers can thus be assured that they are being supplied at all times with healthy and impeccable water.
Iron in drinking water In groundwater aquifers, water comes into contact with various types of iron-containing stone, thus introducing iron ions into the ground water. Although this is not harmful to health, brown iron precipitates can develop which can form deposits, resulting in unpleasant aromas and flavors, particularly when stored in bottles. The World Health Organization prescribes a limit value of 200 g/L for iron in drinking water. Water works employ a number of aeration and filtration systems to comply with the guideline. The ProcessLab atline analysis system performs colorimetric determination of iron levels, thus enabling monitoring of the iron removal processes. Operators regularly collect samples in barcode-labeled containers from individual water batches. The containers are then placed on a sample changer and the sample series is started at the ProcessLab manager. The rest of the process is fully automated: from sampling the containers to sample preparation, analysis and documentation of the results.
Fully automated beverage analysis with Anton Paar and the Metrohm ProcessLab system 32
Simultaneous analysis directly from the container Once the samples are arranged on the sample changer, the tiamoTM controller and database software handles sample identification and measurement method coding using a USB barcode reader. The Anton Paar PBA-S takes the beverage sample directly out of the container to determine density in order to calculate sugar concentration in degrees Brix (Bx), as well as CO2 content. Metrohms ProcessLab system determines the titratable acidity. First, the sample is degassed in a separate titration vessel. Then an aliquot is transfered into the measuring cell where it is titrated with 0.1 molar caustic soda. The individual determination results are displayed in the tiamoTM database. The results of entire sample series can be graphically displayed and checked on user-defined control charts. The modern user interface of tiamoTM can generate user-specific or method-specific views. It is also capable of simultaneously combining several analytical methods, such as density determination and titration, significantly reducing measuring time.
Automatic sample degassing (left) and determination of titratable acidity (right). tiamoTM-controlled beverage analysis is exceptionally robust and can be extended at any time with additional analytic parameters.
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The Multiparameter Measuring System at a glance Simultaneous and fully automated determination of degrees Brix (Bx), CO2 content, and titratable acidity Direct sampling from containers with Anton Paar PBA-S Complete control with tiamoTM software Lower time and personnel requirements through higher degree of automation Very high reproducibility Straightforward operation Safe, easy, and robust procedure Additional parameters can be integrated Measuring time < 6 minutes
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The ADI 201Y process analyzer in stainless steel for the beverage industry
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Examples Peracetic acid in beverage industry filling systems Peracetic acid is used in the beverage industry to sterilize bottles before filling. Too much peracetic acid compromises the taste of the beverage, requires more rinsing and causes unnecessary costs. On the other hand, if too little peracetic acid is used, mold can start growing in the bottles. Peracetic acid is determined by its reaction with iodide through which elemental iodine is formed. The iodine, in turn, can be determined colorimetrically. The entire analysis, including sample preparation, can be automated with an ADI 2019 analyzer. Alkalinity of brewing water The alkalinity of water is the decisive factor for determining whether it is suitable for use as brewing water for the production of beer. Whereas water with a high degree of hardness is suitable only for the production of bock beer, the brewing of lager beer requires soft water. Beer producers must therefore constantly monitor the hardness of the brewing water. The alkalinity of water is determined by acid titration; the hardness of water is measured in mg of CaCO3 per liter. The ADI 2045 TI analyzer is ideally suited to the fully automated performance of this important analysis.
Determination of water hardness The hardness of water used for beverage production has a significant influence on the flavor of the end product. Furthermore, excessive water hardness can result in troublesome deposits on the metal surfaces of processing equipment. Water hardness can be determined either colorimetrically using hydroxynaphthol blue as an indicator or by complexometric titration with EDTA and an ionselective electrode. Determination can be performed conveniently using an Alert analyzer either the Alert ADI 2003 for ISE determination or the Alert ADI 2004 for colorimetric measurement. Higher degrees of hardness can be determined conveniently with ADI analyzers. Manganese and aluminum Concentrations of manganese and aluminum in water can also affect the flavor of drinks. Aluminum is determined colorimetrically. Depending on the concentration range required, determination can be performed using Eriochrome cyanine R, pyrocatechol violet, or a combination of Chromazurol S and cetylpyridinium chloride, in ascending order of detection sensitivity. Manganese is first oxidized with periodate, and then converted with leucomalachite green to form a blue complex. The ADI 2019 or the ADI 2045 can be used as an online analyzer.
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Metrohm Quality Service Global Metrohm Quality Service, particularly preventive maintenance carried out on a regular basis, extends the service life of your analysis systems while ensuring trouble-free operation. Maintenance work is carried out by qualified service experts who have received certified
training. You can choose between different types of service contracts. A full-service contract, for example, offers you optimum security for worry-free work with full cost control and completely compliant verification documentation.
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Depending on the type, Metrohm maintenance contracts (Care Contracts) include maintenance, instrument Cost security and savings, rapid reaction times and quick troubleshooting. Low downtime and ideal prepacertification, on-site repairs, free or reduced-price ration for audits replacement parts and consumables, and guaranteed reaction times. Application support in the form of Application Bulletins, Application Notes, monographs, validation brochures, technical posters and specialist articles Personal support from our specialists by e-mail or telephone Training courses Certified calibrations, e.g., of dosing and exchange units Remote maintenance Back-up support Emergency services, e.g., express on-site repairs Worldwide availability of spare parts, made by Metrohm in Switzerland with ten-year replacement parts guarantee after last production date Decentralized repair workshops located around the world and a central workshop in Switzerland Quick and professional solutions to any application questions and complex analytical problems Competent users contribute substantially to reliable results Precise results Verification documentation for compliance with regulations and efficient audits Quick solutions to software questions High data security Short response times for rapid problem resolution Minimization of downtime Sustainably successful repair; short delivery times Minimization of downtime Rapid availability of repaired instruments
Applications 38
This brochure illustrates a small selection of applications (AB: Application Bulletin, AN: Application Note) from Metrohm's comprehensive beverage analysis product range. The following list contains additional applications. If you do not see your application on the list, please contact your local Metrohm representative. You can download the applications at: www.metrohm.com/com/Applications Beverages General AN-S-141 Chloride, nitrate, phosphate, sulfate, and citrate in beverages AN-T-042 Citric and oxalic acid in mixtures
Nonalcoholic beverages Mineral, spring, table and medicinal waters The number of applications is too great to list here. Please visit the website listed above and navigate to Industries > General application literature database > Environment > Water > Drinking and tap water. Soft drinks AN-N-052 Caffeine in cola soft drinks AN-P-003 Glucose, fructose, and sucrose in a cola drink AN-P-004 Mannitol, glucose, and xylose in a diet cola drink AN-S-185 Phosphoric acid in soft drinks AN-S-307 Phosphate in cola drink AN-U-026 Phenylalanine, aspartame, caffeine, and benzoate in soft drinks AN-V-095 Quinine in bitter lemon 8.792.5011 Monograph: Practical Ion Chromatography, experiment 11: Phosphoric acid in cola drinks Fruit juices AB-180 Automatic determination of the formalin number in fruit and vegetable juices AB-085 Analysis of jams, fruit and vegetable juices, and their concentrates AB-070 Polarographic determination of nitrate in water samples, soil and plant extracts, vegetable juices, meat and sausages, fertilizers, liquid manure, etc. AN-C-067 Cations in grapefruit soft drink using inline dialysis AN-C-102 Standard cations in orange juice AN-O-032 Malate and ascorbate in fruit juice AN-P-006 Inositol, glucose, fructose, and sucrose in orange juice AN-P-033 Cellobiose in apple juice AN-S-112 Five organic acids in fruit juice using chemical suppression after ion-exclusion separation AN-S-164 Five anions in orange juice AN-S-189 Citrate and isocitrate in fruit juices AN-T-030 Ascorbic acid (vitamin C) in fruit juices AN-V-073 Ascorbic acid in orange juice AN-C-068 AN-O-003 AN-O-025 AN-O-037 AN-P-036 Functional drinks Cations in functional fruit juice using inline dialysis Citrate and acetate in isotonic solutions Sorbate and benzoate in functional drinks Infusion beverages Organic acids in roasted coffee Determination of free and total sugar in instant coffee (according to ISO 11292)
AN-C-048
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Alcoholic beverages Beer AN-P-017 Propylene glycol in a bitter (dark) beer AN-P-023 Fermentable sugars in beer wort AN-P-034 Sugars and sugar alcohols in beer AN-S-124 Chlorite, chloride, sulfite, and oxalate in beer AN-S-193 Four anions in beer wort AN-S-225 Sulfite in the presence of standard anions in beer on the column Metrosep A Supp 10 - 100/4.0 Wine AB-112 Quantitative determination of metals that can be precipitated by potassium hexacyanoferrate(II) in wine ("dcassage" of wine) AB-139 Simple wine analysis AB-225 Simple wine analysis with the Titrino AN-C-070 Cations and biogenic amines in wine AN-C-105 Copper, zinc, iron(II), and manganese in wine by ion chromatography with post-column reaction and UV/VIS detection AN-O-006 Organic acids and phosphate in wine AN-S-281 Anions in wine AN-T-072 Reducing sugars in wine and candies AN-V-092 Nickel in white wine after UV digestion AN-V-093 Zinc, cadmium, lead, and copper in red wine after UV digestion AN-V-094 Rhodium and platinum in red wine after UV digestion AN-V-201 Nickel and cobalt in red wine after UV digestion 8.792.5011 Monograph: Practical Ion Chromatography, experiment 12: Organic acids in wine AN-P-021 AN-V-031 AN-V-039 AN-V-040 8.792.5011 Distilled spirits Glucose, fructose, and sucrose in vodka Coumarin and tartrazine in vodka Zinc, cadmium, lead, and copper in whiskey after UV digestion Aluminum and chromium in whiskey after UV digestion Monograph: Practical Ion Chromatography, experiment 9: Anions in ethanol and spirits (liquor)
Liquid food AB-342 Automated calcium and magnesium determination in milk using 859 Titrotherm and 814 USB Sample Processor AN-H-103 Determination of calcium and magnesium in milk AN-K-007 Water in yogurt powder AN-P-005 Seven carbohydrates in milk after sample preparation by Inline Dialysis AN-P-046 Lactose in lactose-free dairy products applying pulsed amperometric detection after Inline Dialysis AN-S-297 Iodide, thiocyanate, and perchlorate in milk applying Inline Dialysis AN-C-030 Four cations in a soybean drink (chocolate flavor) using dialysis for sample preparation AN-H-125 Determination of sodium in soy milk AN-P-046 Lactose in lactose-free dairy products applying pulsed amperometric detection after Inline Dialysis
Ordering Information 40
2.826.0110 2.827.021x 2.780.0010 2.781.0010 2.867.0110 2.867.0210 pH measurement 826 pH mobile with carrying case and Primatrode 827 pH lab IrDA with Unitrode 780 pH meter with Unitrode 781 pH/Ion meter with Unitrode 867 pH Module with Touch Control including iUnitrode 867 pH module with tiamoTM light including iUnitrode
Conductivity measurement/titration of alpha acids 856 Conductivity Module with Touch Control 856 Conductivity module with tiamoTM light Conductometric titrator
Titration 2.848.1010 Food/beverage Titrino plus 2.859.1010 859 Titrotherm 2.848.1020 Food/beverage Titrino plus with printer 2.848.2010 Salt Titrino plus 2.848.1020 Salt Titrino plus with printer 2.905.4010 Food Titrando with tiamoTM light 2.916.2010 Salt Ti-Touch 2.916.4010 Food Ti-Touch
Water determination according to Karl Fischer Volumetric KF Titration 915 KF Ti-Touch including accessories 890 Titrando with 900 Touch Control 890 Titrando with tiamoTM light 870 KF Titrino plus complete 901 Titrando including titrator vessel and indicator electrode KF sample preparation Polytron PT 1300 D
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Automation MATi07 Automated titration system for up to 28 samples MATi08 Automated pipetting and titration system for up to 100 samples 2.862.1010 Food/Beverage Compact Titrosampler 2.862.1110 Food/Beverage Compact Titrosampler with printer 2.862.2010 Salt Compact Titrosampler 2.862.2110 Salt Compact Titrosampler with printer 2.815.1110 2.815.2110 2.815.3110 2.815.4110 815 Robotic Titration Soliprep 815 Robotic Flexible Soliprep 815 Robotic Filtration Soliprep 815 Robotic Soliprep for LC
Ion chromatography 940 Professional IC Vario TWO/SeS/PP for anion and cation determination 930 Compact IC Flex Oven/SeS/PP/Deg for the analysis of anions IC Conductivity Detector for anion and cation determination IC Amperometry Detector for carbohydrate determination 944 Professional UV/VIS Detector Vario for bromate determination in water 943 Professional Reactor Vario for post-column derivatization
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2.858.0020 2.800.0010 2.941.0010 6.3032.210 6.5330.090 6.5330.100 6.5330.110 6.5330.120 6.5330.170 6.5330.180 6.5337.010 6.6059.301 6.6059.302 6.6059.303 6.1031.410 6.1006.510 6.1013.010
858 Professional Sample Processor for automated determinations 800 Dosino for the fully automated Liquid Handling of samples 941 Eluent Production Module Dosing unit 10 mL IC Equipment: Additional Eluent on the Eluent Production Module IC Equipment: Inline Dialysis IC Equipment: Inline Ultrafiltration IC Equipment: Inline Dilution IC Equipment: MiPuT IC Equipment: MiPT IC Equipment Wall-Jet cell: carbohydrate determination MagIC Net 3.0 Compact MagIC Net 3.0 Professional MagIC Net 3.0 Multi Metrosep A Supp 16 - 100/4.0 for bromate determination Metrosep A Supp 5 - 100/4.0 for anion determination Metrosep Carb 1 - 150/4.0 for carbohydrate determination
Voltammetry 2.797.0010 797 VA Computrace for trace analysis (manual operation) MVA-2 797 VA Computrace system for trace analysis with automatic standard addition (comprised of 797VA Computrace with two 800 Dosinos for the automatic addition of auxiliary solutions) MVA-3 Fully automated 797 VA Computrace system for trace analysis (comprised of 797 VA Computrace with 863 Compact VA Autosampler and two 800 Dosinos for automatic addition of auxiliary solutions; automatic processing of up to 18 samples)
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Subject to modifications Layout by Ecknauer+Schoch ASW, printed in Switzerland at Metrohm AG, CH-9100 Herisau 8.000.5093EN 2013-08
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