Water Analysis Quality control of water 02 Metrohm... • is the global market leader in titration • offers a complete portfolio for NIR and Raman analysis, in addition to all of the methods of • ion analyses – 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 • anion chromatography • provides you with unparalleled application expertise • offers you more than 1800 applications free of charge • supports you with expert service through local representatives and regional support centers • is not listed on the stock exchange, but is owned by a foundation • gives the interest of customers and employees priority over maximizing profit Metrohm – customized water analysis Harmful substances in water You can count on our support 03 Water is the source and basis of all life. It is essential for As a leading manufacturer of instruments for chemical metabolism and is our most important foodstuff. As a analysis, we are aware of these challenges. For this rea-solvent and transporting agent it carries not only the vital son, Metrohm offers you not only the most advanced minerals and nutrients, but also, increasingly, harmful instruments, but complete solutions for very specific pollutants, which bioaccumulate in aquatic or terrestrial analytical issues. Your Metrohm contacts are competent organisms. Within the context of quality control and risk specialists, who develop customized applications for you assessment there is a need in the water laboratory for and provide you with professional support in all matters cost-effective and fast instruments and methods that can concerning water analysis. deal with the ever more complex spectrum of harmful substances, the increasing throughput of samples and Discover on the following pages what analytical solutions the decreasing detection limits. Metrohm is able to offer the water analysis sector in general and you in particular, to ensure the quality and reliability of your work. Challenge us! There is more than we’d like in water ... Thales of Miletus (ca. 625–545 BC), one of the first Greek 04 associated health risks, the World Health Orga ni zation natural philosophers and one of the «Seven Wise Men», (WHO) has issued guideline values for about 200 sub-considered water as the source of all things, to which stances found in water. These guideline values, together everything returns. This perception takes on a complete-with the hydrogeological conditions of the various coun-ly new meaning in view of the 1700 substances, mainly tries, form the basis for the setting of country-specific of anthropogenic origin, that can today be detected in limits. That is why water is the subject of a host of laws, water. As a source of food and energy, during use in regulations, and standards in most countries. irrigation, as a solvent, cleaning agent, or coolant, and also as a means of transportation and discharge system For many of these standards and regulations, Metrohm for effluents, water becomes contaminated with fertiliz-offers robust, reliable, and very precise analyzers and ers, pesticides, drugs, hormones, heavy-metal com-ana lytical methods. pounds, bodycare and synthetic products. Because of the Selected standards relating to water analysis The standards listed below describe the measurement of describe simultaneous determination of several analytes 05 conductivity and pH value as well as the determination of (e.g., EPA 300.1), one and the same analyte (e.g., chlo-anions and cations in various types of water. Metrohm ride) can also be determined using different analytical analyzers meet all the minimum requirements and limits techniques, depending on the prescribed limit and the set in the respective standards. Whilst some standards sample matrix. Parameter Standard Matrix Method Page DIN 38404-5 All types of water pH measurement Acid rain Drinking water pH value EPA 150.1 pH measurement 6 Seawater Wastewater USP<791> Pharmaceutical water pH measurement Conductivity DIN EN 27888 Drinking water measurement Acid rain Drinking water Conductivity Conductivity EPA 120.1 7 Seawater measurement Wastewater Conductivity USP<645> Pharmaceutical water measurement Drinking water EPA 130.2 Wastewater Total hardness Drinking water EN ISO 9963 Titration Ca, Mg Wastewater 8 Drinking water DIN 38406-3 Wastewater Acid and base capacity DIN 38409-7 All types of water Titration Drinking water Alkalinity as CaCO EPA 310.1 Seawater Titration 8 3 Wastewater Drinking water Cl– DIN 38405-1 Titration 8 Wastewater Permanganate index DIN EN ISO 8467 Drinking water Titration 9 DIN 38409-44 Sea water Chemical oxygen demand (COD) Titration 10 ASTM D1252 Wastewater Anions, e.g., F–, Cl–, Br–, NO –, Drinking water 2 NO –, SO 2–, etc. EPA 300.1, Part A Ion chromatography 12 3 4 Wastewater Drinking water EPA 300.1, Part B Wastewater EPA 317.0 Drinking water Oxohalides Ion chromatography 12 EPA 326.0 Drinking water DIN EN ISO 11206 ASTM D6581 Drinking water Drinking water ASTM D6919 Cations, e.g., Li+, Na+, K+, Ultrapure water NH +, Mg2+, Ca2+, etc. Ion chromatography 14 4 Ultrapure water ISO 14911 Wastewater Drinking water Zn, Cd, Pb, Cu, Tl, Ni, Co DIN 38406-16 Voltammetry Wastewater Groundwater 17 Uranium DIN 38406-17 Raw water Voltammetry Drinking water Sample preparation acc. Wastewater CN– Voltammetry to DIN 38405-13 Drinking water Cd, Pb, Cu, FeII/FeIII, CrVI – Seawater Voltammetry 18 Boiler feed water Cu, Fe, Zn, Co – Voltammetry 19 Cooling water pH value (Titration and Ion Conductivity Various All types of water Chromatography, TitrIC; 20 Anions Voltammetry and Ion Cations Chromatography, VoltIC) pH value, conductivity, TOC, and Wastewater various parameters that can be Process-dependent Cooling water Process analysis 24 determined by titration, IC, voltam- specifications Process water metry, or spectroscopy Drinking water pH and conductivity measurement The pH value is probably the most frequently measured 06 pH value, chloride, fluoride, and ammonium with parameter of aqueous solutions – ranging from mobile 780 pH Meter or 781 pH/Ion Meter measurement in drinking water, surface water, ground-The 780 pH Meter is the first choice if you wish to obtain water, and wastewater through to precise measurement highly precise results: nine-point calibration, stirrer of the pH value of water for pharmaceutical use. Wher-control, electrode test for pH glass electrodes, method ever pH values are determined, Metrohm offers the ideal me mo ry, and RS232 interface. solution for every application. In addition to pH measurement, the 781 pH/Ion Meter Drinking water allows the determination of specific ions (e.g., Cl–, F–, «Two-in-one» – for indoors and outdoors NH +) either by direct measurement or by fully automatic 4 The new Metrohm meters are «two in one»: precision standard addition with a Dosimat. instruments for measurements in the laboratory and robust companions for mobile use in the field and at the process. Optional battery operation makes the new meters independent of a power grid. They can even be recharged on the road with the use of a cigarette lighter car adapter. Results can be saved with the press of a button and can be uploaded onto the PC at the office. The 914 pH/Conductometer measures pH and conductiv- ity in parallel; the 913 pH Meter can simultaneously determine two pH values. 856 Conductivity Module and 867 pH Module 07 Thanks to the five-ring measuring cells the new 856 Conductivity Module is ideal for measurements in drink - ing water according to DIN EN 27888 and EPA 120.1. The large range of linearity allows various types of water to be measured without recalibration. By combining the 856 Conductivity Module with the 867 pH Module it is even possible to measure the conductivity and pH value simultaneously in the same vessel. Five-ring conductivity measuring cells The main feature of the new five-ring measuring cells is their large range of linearity (0.005–100 mS/cm). This means it is possible to measure anything from drinking water to seawater without any calibration in between. Water for pharmaceutical use (water for injection) Conductivity Particularly strict rules apply to the measurement of the conductivity of water for pharmaceutical use (water for injection) according to USP<645>. Apart from the highest level of precision, all the requirements of the U.S. FDA’s 21 CFR Part 11 must be satisfied. The 856 Conductivity Module, together with the 900 Touch Control, PC Control, or tiamo (full or multi) guarantees this. Conductivity measuring cell (stainless steel) with Pt 1000 This measuring cell was developed specifically for water samples with very low conductivity. The robust and easy to clean stainless-steel device is ideal for conductivity values <300 µS/cm and thus for measuring water for pharmaceutical use. pH value The 867 pH Module provides all that is needed for measuring the pH value according to USP<791>. With 900 Touch Control, PC Control, or tiamo (full or multi), intelligent sensors and five-point calibration it meets the requirements of FDA 21 CFR Part 11. In conjunction with PC Control or 840 Touch Control it is possible to carry out an electrode test. Con ductivity and pH value can be measured in the same vessel if the 856 Conductivity Module is combined with the 867 pH Module. Titration 08 Carbonate hardness (temporary hardness, Chloride alkalinity, or acid binding capacity) Chloride ions are determined by potentiometric titration Temporary hardness is determined by endpoint titration with AgNO as titrant and a combined Ag-ring electrode, 3 with 0.1 mol/L HCl. The combined pH glass electrode the Ag-Titrode, following prior pH adjustment with nitric Aqua trode plus was developed specifically for use in acid. The maintenance-free Ag-Titrode uses a pH glass aqueous solutions. The rapidly responding membrane membrane as reference electrode, which means that no glass and the fixed ground-joint diaphragm ensure pre-refilling of electrolyte is required. cise, low-noise measurements, and titration results with waters ranging from ultrapure to water with a high salt Fluoride according to ASTM D3868 and sulfide content. according to ASTM D4658 Fluoride and sulfide ions are determined by ion-selective Acid and base capacity according to DIN 38409-7 electrodes. Acid and base capacity are parameters that describe the buffering capacity of water with respect to acids and For fluoride determination, a buffer substance is added bases. These are important sum parameters in water to the sample. This buffer substance both maintains the analysis, which characterize the pH stability of the sam-ionic strength, regulates the pH value and complexes in - ple. Both parameters are determined by titration to the ter fering aluminum and iron(III) ions. pH values of 4.3 and 8.2. The former covers all alkaline parts by titration with hydrochloric acid, the latter all To measure sulfide, a buffer is added. This both regulates acidic parts by titration with caustic soda. Unlike stan-the pH value, and prevents the oxidation of sulfide by dard pH electrodes, the Aquatrode plus has a special at mos pheric oxygen. glass membrane that guarantees rapid, correct, and highly precise pH measurements and pH titrations in solutions that have a low ionic strength or are weakly buffered. Calcium and magnesium according to DIN 38406-3 and EPA 130.2 With regard to the determination of water hardness, a distinction is made between temporary hardness (carbonate hardness) and permanent hardness (sulfate hardness). Another important parameter includes the total hardness that represents the sum of the dissolved alkaline earth metals, but that is approximated as the sum of the calcium and magnesium hardness. Temporary hardness is determined by end point titration with hydrochloric acid, total hardness by complexometric titration with Na EDTA 2 as titrant, and a Ca2+-selective electrode. The tiamo titration software allows third-party devices to be incorporated, for example, for turbidity measurements according to DIN EN ISO 7027, or for determining color according to DIN EN ISO 7887. 907 Titrando with 900 Touch Control Titration – Sum parameters Sum parameters usually characterize similar chemical, Permanganate index according to DIN EN ISO 8467 09 physical, physicochemical or biological features of differ-The permanganate index determines the easily oxidizable ent components. Their advantage is in the fast determi-fraction of the organic constituents in water and is used, nation and informative value, which allow the sample to in a broader sense, to evaluate the or ga nic chemical con-be evaluated quickly. As an example, electrical conductiv-tamination in waters with minimal or low contamination, ity provides valuable information on the salt content of a such as drinking water samples. For determination, the water sample. Another important sum parameter is the water sample is heated for ten minutes with sulfuric acid chemical oxidizability of water components, which pro-and an excess of permanganate solution of known con-vides indications of the type and quantity of organic centration in a boiling water bath. After that, the per-material present in the sample. manganate consumption is determined by adding an excess of sodium oxalate solution and back-titrating the According to the oxidizing power of the oxidizing agents consumed oxalate with permanganate solution. The per-used, a distinction is made between the permanganate manganate index is expressed as the quantity of oxygen index and the chemical oxygen demand (COD). While the in mg/L that would be needed for oxidation. permanganate index is the more informative parameter for samples with minimal or low contamination, COD is suitable for severely contaminated samples. The MATi 13 (Metrohm Automated Titration) system for the fully automatic determination of the permanganate index 10 The MATi 12 system for fully automatic COD determination Chemical oxygen demand according to DIN 38409-44 and ASTM D1252 The chemical oxygen demand (COD) is a measured value dichromate. The remaining quantity of potassium dichro-for the sum of the substances in a certain volume of mate is then back-titrated with ammonium iron(II) sul-water that can be oxidized by chromate. Chromate is a fate. much stronger oxidizing agent than permanganate, which is why it also oxidizes most organic compounds The water constituents are oxidized either in a special practically completely into CO . In sewage treatment COD heating device with reflux condensing or in a closed 2 plants, COD is regarded as a valuable indicator for evalu-reaction vessel with an external heat source. Titration ating treatment performance. takes place directly in the reaction vessels without the need to transfer the content to other vessels. This pre-For volumetric determination of the COD, the sample of vents any sample losses and saves valuable time, especi-water is heated over a defined period with potassium ally when there is a high sample throughput. Fully automated water analyzing system Comprehensive water analysis includes the determina-The fully automated water analyzing system not only 11 tion of different sum parameters (e.g., conductivity, pH saves time, but also increases sample throughput as well value, alkalinity, hardness) and several individual sub-as precision and repeatability of your results. stances (e.g., ions). Frequently, these parameters – even in case of a high sample throughput – are sequentially All the devices are fully controlled and monitored determined on different instruments. This is very time by the powerful titration software tiamo. Results consuming and requires repetitive sample preparations are centrally recorded and administered in a well-and expensive laboratory space. Why not save time and arranged database. benefit from synergy effects by combining Metrohm devices in a single system that carries out all the men-tioned analyses and sample preparations in a single run? MATi 01 is just the answer to this question. The system is a customizable combination of the 815 Robotic USB Sample Processor XL, 905 Titrando, and 856 Conductivity Module. Apart from the determination of the aforemen-tioned parameters, the system automatically performs the necessary sample preparation steps. This includes the metering of the sample as well as further liquid handling steps such as the accurate addition of titrant and auxiliary reagents. Up to 59 samples can be placed on the sample rack. Aquatrode plus with Pt 1000 Fully automated water analysis with MATi 01 Ion chromatography 12 Modern ion chromatography (IC) allows efficient separa-formed by oxidation of the halides when drinking water tion and determination of inorganic and low-molecular and mineral water are disinfected. Their concentration weight organic anions and cations. Various separation needs to be monitored on account of their suspected car-mechanisms and types of detection as well as the possi-cin ogenic properties. bility of automation and sample preparation make IC a proven routine method in water and environmental Prior to injection, the samples pass through the ultrafiltra-analysis. tion cell mounted directly on the 858 Professional IC Sample Pro cessor. Sample preparation and analysis are fully Drinking water and mineral water automatic. The equipment is controlled, the data collected Oxyhalides and standard anions according to EPA and managed, and the system monitored by the intelligent method 300.1 MagIC Net chromatography software. The clear symbols, Chlorate, chlorite, and bromate are by-products that are well laid-out presentation, and intuitive operation make analysis remarkably easy. Drinking water sample, spiked with 10 µg/L of each ClO –, BrO –, ClO –, 40 µg/L of each NO –, 2 3 3 2 Br–, 100 µg/L PO 3–, 500 µg/L dichloroacetate; column: Metrosep A Supp 7 - 250/4.0; elu-4 ent: 3.6 mmol/L Na CO , 0.8 mL/min; column temperature: 45 °C; sample volume: 20 µL; 2 3 conductivity detection after sequential suppression 930 Compact IC Flex and 858 Professional Sample Processor, optionally equipped with Inline Ultrafiltration 13 Bromate in drinking water Because of the potentially carcinogenic properties of the suppression allows the determination of bromate in the bromate that can form during the ozonization of drink-lower µg/L range. In the ng/L range bromate can be ing water, this determination is very important. Depending detected by means of IC/MS coupling or post-column on the required detection limit, different detection meth-derivatization with potassium iodide and subsequent UV ods can be used. Conductivity detection with sequential detection. Bromate analysis: overview test methods and detection limits (acc. to DIN 32645) Detection limit EPA method Injection Ultrapure Drinking volume water water* [µL] [µg/L] Conductivity detection with 300.1 100 0.130 0.390 sequential suppression IC/MS coupling; MS detection – 100 0.006 0.007 Post-column derivatization with 317.0 100 0.210 0.640 o-dianisidine; VIS detection Post-column derivatization with 326.0 1000 0.032 0.066 Kl; UV detection *Drinking water matrix: 100 mg/L of each chloride, sulfate, and carbonate 14 Ultrapure water Anions and cations Ultrapure water is used, for example, in the production the water is therefore of crucial importance. Anions and of pharmaceuticals and semiconductors and as a central cations are im portant corrosion indicators and can be medium in thermal power plants. In the latter situation, determined reliably down to trace concentrations (ng/L) it serves as the coolant, drives the turbines, and moder-after inline preconcentration, one of the applications of ates nuclear fission. Determination of the substances in Metrohm Inline Sample Preparation (MISP). Cation detection limits of the 940 Professional IC for direct injection and after preconcentration Detection limit Lithium Sodium Ammonium Potassium Magnesium Calcium [ng/L] Direct injection; 100 µL* 200 250 370 2700 2500 3800 Sample preconc. from 10 mL* 2 3 2 6 5 4 *Column: Metrosep C 3 - 250/4.0; eluent: 2.5 mmol/L HNO , 1 mL/min; column temperature: 40 °C; conductivity detection 3 without suppression Anion detection limits of the 940 Professional IC for direct injection and after preconcentration Detection limit Fluoride Chloride Nitrite Bromide Nitrate Phosphate Sulfate [ng/L] Direct injection; 20 µL1 370 330 410 900 990 890 830 Sample preconc. from 10 mL2 0.7 1.2 0.8 2.3 2.5 2.6 2.3 1Column: Metrosep A Supp 5 - 100/4.0; eluent: 3.2 mmol/L Na CO , 1.0 mmol/L NaHCO , 0.7 mL/min; column temperature: 25 °C; con-2 3 3 ductivity detection after sequential suppression 2Column: Metrosep A Supp 7 - 250/4.0; eluent: 3.6 mmol/L Na CO , 0.8 mL/min; column temperature: 45 °C; conductivity detection after 2 3 sequential suppression The determination of cations in the secondary circuit of nuclear power plants is shown as an example. To prevent corrosion in the cooling circuit, the pH value is raised by adding Lewis bases such as, for example, ethanolamine and morpholine. Ion chromatographic determination of cations allows simultaneous, reliable determination of the amines, which means that IC can also be used to control the addition of amines. 940 Professional IC Vario with 800 Dosino (2×) and 815 Robotic USB Sample Processor XL 15 Spiked sample from the secondary circuit of a nuclear power plant; column: Metrosep C 4 - 250; Metrosep C PCC 1 HC for sample preconcentration; eluent: 2.5 mmol/L HNO , 3 1.0 mL/min; column temperature: 45 °C; sample volume: 2.5 mL; conductivity detection without suppression Voltammetry 16 Voltammetric trace and ultratrace analysis of drinking ronmental monitoring, limnology, hydrography, ocean-water, groundwater, surface water, seawater, and waste-ography, marine biology, and soil science. water is used to determine electrochemically active inorganic ions. It is frequently employed to complement and 884 Professional VA validate spectroscopic methods. Its features are: compact The 884 Professional VA is a flexible measuring instru-equipment, relatively low investment and running costs, ment for accurate and sensitive voltammetric analyses. simple sample preparation, short analysis times, and high The accompanying viva software enables individual opti-accuracy and sensitivity. In addition, unlike the spectro-mization of methods. scopic methods, voltammetry is able to distinguish between different oxidation states of metal ions (specia-909 UV Digester tion) as well as between free and bound metal ions. This With the 909 UV Digester, unwanted organics in surface provides important information regarding the bioavaila-water and wastewater samples can be digested quickly bility and toxicity of heavy metals. Voltammetry is espe-and safely, with no contamination. UV digestion is the cially suitable for laboratories in which only a few param-ideal sample preparation for the voltammetric determina-eters have to be monitored with a moderate sample tion of heavy metals. throughput. Important fields of application include envi- Drinking water and groundwater 17 Many toxic transition metals and a few anions can be determined easily and economically down to the ng/L determined voltammetrically, with a high degree of sen-range. By contrast, the spectroscopic analytical tech-sitivity and without prior sample preparation, in drinking niques are complicated and expensive. water and groundwater. Here are a few relevant examples: Arsenic and mercury with the scTRACE Gold Zinc, cadmium, lead, copper, thallium, nickel, Due to the toxicity of arsenic and mercury, the World and cobalt Health Organization recommends a maximum content These metal ions must be determined regularly in water in the drinking water of 6 or 10 µg/L, respectively. samples. DIN 38406 Part 16 describes the determination Anodic stripping voltammetry using the scTRACE Gold of these ions in different types of water. offers a simple, low-cost alternative to spectroscopic determination for both elements. The scTRACE Gold combines all three of the electrodes needed for the measurement. Selection of the measuring parameter makes it possible to distinguish between As(III) and As(V). Moreover, inorganic mercury can also be determined with the scTRACE Gold. The detection limit in this case is 0.1 µg/L. Voltammetric determination of zinc, cadmium, lead, and copper according to DIN 38406-16 Detection Limits Uranium Element [ng/L] For adults, the World Health Organization (WHO) recom-Antimony SbIII/SbV 200 mends a drinking water limit of 30 µg/L for uranium, Arsenic AsIII/AsV 100 which is radioactive and highly toxic. In Germany, the Bismuth Bi 500 Drinking Water Directive only stipulates a limit of Lead Pb 50 10 µg/L. Cadmium Cd 50 With the 884 Professional VA dissolved uranium can be Chromium CrIII/CrVI 25 Cobalt Co 50 -50 U Iron FeII/FeIII 50 Copper Cu 50 -40 Molybdenum Mo 50 -30 Nickel Ni 50 I [nA] Platinum Pt 0.1 -20 Mercury Hg 100 Rhodium Rh 0.1 -10 Selenium SeIV/SeVI 300 0 Thallium Tl 50 0 -0.03 -0.05 -0.08 Uranium U 25 U [V] Tungsten W 200 Voltammogram of a uranium(VI) determination in a drinking wa-Zinc Zn 50 ter sample 18 Seawater Whereas the seawater salt matrix interferes with the Important applications in seawater analysis include the determination of heavy metals in atomic spectrometric determination of a series of transition metals, some of analysis, voltammetry allows direct determination with-them toxic, as illustrated by the following examples: out any sample preparation. Only the presence of or - ganic compounds can affect voltammetric detection. By Determination of different chromium species using the 909 UV Digester it is possible to remove the Chromium species differ considerably in their ecotoxicity: organic matrix quantitatively by UV photolysis within 60 whereas Cr(III) is an important trace element for marine minutes. With regard to use on research ships, the com-organisms, the strongly oxidizing chromium(VI) com- pactness and robustness of the 884 Professional VA are pounds are highly toxic. decisive advantages. Apart from its use to determine total metal concentration, voltammetry makes it possible Cadmium, lead, copper, and iron to distinguish between the different oxidation states and Other important analytes are the elements cadmium, also between free and bound metal ions. lead, and copper, which are usually determined on a mercury film electrode. Iron may be present in oxidation states II and III and is determined at the hanging mercury drop electrode (HMDE). Wastewater 19 Voltammetric determination of many heavy metals is also possible in municipal or industrial wastewater. On account of the usually high organic load the sample is usually mineralized by means of UV digestion. Cooling water and boiler feed water All thermal power plants use water as the central medium for cooling and for generating steam. Only top-quality boiler water and cool ing water can ensure efficient and trouble-free operation of the plant. Voltammetry allows the easy and rapid checking of important monitoring parameters such as copper, iron, zinc, co balt, and manganese content. Multiparameter analysis – titration, ion chromatography, and voltammetry 20 Fully automatic drinking water analyses results are saved in the integral database and can be TitrIC and VoltIC combine the advantages of direct meas-processed to produce a combined report. urement of pH value and conductivity, titration, ion chromatography, and voltammetry in single systems that Intelligent control and thoroughly tested technology provide fully automatic drinking water analyses. TitrIC guarantee reliable analyses regardless of the time of day stands for the combination of direct measurement, titra-or night. Up to one hundred samples can be analyzed tion, and ion chromatography – VoltIC for that of vol-fully automatically. This reduces the time required and tammetry and ion chromatography. All ionic components in creases the precision of the measurements. are determined reliably, quickly, and reproducibly. The Minimal space requirements Particular attention has been given to keeping space requirements to a minimum. The synergies between titration, direct measurement, ion chromatography, and voltammetry are also evident here. All methods use the same liquid handling units and a common sample changer. This helps to save both costs and space; a rapid return on investment is guaranteed. 815 Robotic USB Sample Processor XL 28...100 samples, 75...200 mL TitrIC is flexible Conductivity 21 TitrIC can be adapted to suit the particular analytical task. Anions Cations Temperature The application determines which parameters are of F–, CI–, NO –, Br–, NO –, Li+, Na+, NH +, K+, 2 3 4 HPO 2–, SO 2– Mg2+, Ca2+ 4 4 pH value interest. Accordingly, different methods and procedures Titration K 8.2 (p value) A can be combined freely. Titration K 4.3 (m value) A MagIC Net Database, Report TitrIC Vario pro II – Flowchart TitrIC determines the following parameters: Direct measurements with TitrIC • pH value • Temperature • Conductivity Titrations with TitrIC • pH value (titration to pH = 8.2) • m value (titration to pH = 4.3) • Calcium • Magnesium Anion IC with TitrIC • Fluoride • Chloride • Bromide • Nitrite • Nitrate • Phosphate • Sulfate • ... Cation IC with TitrIC • Lithium • Sodium • Ammonium • Potassium • Calcium • Magnesium • ... Report of a TitrIC Vario pro system Calculations with TitrIC • Molar concentration of all cations • Molar concentration of all anions • Ionic balance • Total water hardness • ... 22 TitrIC Vario pro I – the basic system Fully automatic system for direct measurement of temperature, conductivity, and pH value; the titrimetric determination of p value, m value, calcium and magnesium, and the determination of anions by ion chromatography. 815 Robotic USB Sample Processor XL 28...100 samples, 75...250 mL Conductivity Titration K 8.2 (p value) A Anions Temperature Titration K 4.3 (m value) A F–, CI–, NO –, Br–, NO –, 2 3 HPO 2–, SO 2– Titration Ca2+ 4 4 pH value Titration Mg2+ MagIC Net Database, Report TitrIC Vario pro I: The system consists of the 856 Conductivity Module, four 800 Dosinos, 802 Stirrer (rod stirrer), 905 Titrando, 815 Robotic USB Sample Processor XL and 930 Compact IC Flex with sequential suppression. TitrIC Vario pro II – for the complete determination of anions and cations mination of p and m values, the determination of cations Fully automatic system for direct measurement of tempe-including calcium and magnesium, as well as anions by rature, conductivity, and pH value, the titrimetric deter-ion chromatography. 815 Robotic USB Sample Processor XL 28...100 samples, 75...200 mL Conductivity Anions Cations Temperature F–, CI–, NO –, Br–, NO –, Li+, Na+, NH +, K+, 2 3 4 HPO 2–, SO 2– Mg2+, Ca2+ 4 4 pH value Titration K 8.2 (p value) A Titration K 4.3 (m value) A MagIC Net Database, Report TitrIC Vario pro II: The system consists of the 856 Conductivity Module, two 800 Dosinos, one 802 Stirrer, 905 Titrando, 815 Robotic USB Sample Processor XL, and two 930 Compact IC Flex. TitrIC Vario pro III – The professional solution with 17 23 closed sample vessels Fully automatic system for direct measurement of temanions by ion chromatography. The sample changer is perature, conductivity, and pH value, the titrimetric equipped with the DisCover function for automatic sam-determination of p and m values, the determination of ple vessel cover removal. cations including calcium and magnesium, as well as 815 Robotic USB Sample Processor XL 28...1000 samples, 75...200 mL DisCover Conductivity Anions Cations Temperature F–, CI–, NO –, Br–, NO –, Li+, Na+, NH +, K+, 2 3 4 HPO 2–, SO 2– Mg2+, Ca2+ 4 4 pH value Titration K 8.2 (p value) A Titration Titration K 4.3 (m value) 4 3 (m al e) A MagIC Net Database, Report TitrIC Vario pro III: The system consists of the 856 Conductivity Module, two 800 Dosinos, 802 Stirrer (rod stirrer), 905 Titrando, 815 Robotic USB Sample Processor XL, and one 940 Professional IC for anions and cations. VoltIC Vario pro I – The hyphenated IC and voltammetry system for parallel determination of anions, cations, and heavy metals VoltIC Vario I is the perfect combination of IC and vol-ments, starts voltammetric determination, and summa-tammetry for simultaneous determination of anions, rizes the results from IC and voltammetry. cations, and heavy metals. MagIC Net controls IC instru-VoltIC Vario pro I: 940 Professional IC Vario for anion and cation analysis in combination with the 858 Professional Sample Processor and the 797 VA Computrace including Dosinos and Pump Station. Atline process analysis Frequently, water samples have to be analyzed rapidly to 24 into the process communication system through inputs pick up changing process conditions. However, skilled and outputs (typically 4–20 mA). Just a few minutes after laboratory staff is not always available around the clock a sample has been taken, the relevant process informa-and long distances to the laboratory often prevent fast tion is available to a LIMS or the control room. The pro-sample analysis. cess con ditions can be modified quickly and efficiently, if ne cessary. ProcessLab is therefore ideal for fast and If, in such cases, the water sample can be analyzed independent process monitoring in the plant en vi - directly on-site within the process, this is a decisive ronment. advantage. Metrohm ProcessLab, a robust and easy-to-use analysis system that is installed directly within the A ProcessLab analysis system consists of a TFT operating pro cess, makes this possible. The sample is brought to panel and an analysis module. For even easier and more the ProcessLab and the analysis is started with just one comfortable operation, the operating panel is also avail-press of a button. ProcessLab is based on proven able with touch function. With its splashproof housings, Metrohm components for titration and voltammetry. Its ProcessLab is ideally suited for use in harsh production design is entirely modular; it is configured according to environments. the analytical requirements and can be integrated ideally ProcessLab analysis system with touch monitor and analysis module Drinking water treatment 25 pH value, alkalinity, and active chlorine These parameters are important variables in drinking All three analytical parameters can be determined with water treatment. Processes such as deacidification, iron ProcessLab and the results saved in a database. The removal, flocculation, or disinfection are dependent on measure ments can be carried out quickly on-site, either the pH value. Alkalinity is determined by the basic com-centrally in the water treatment plant, or locally on the ponents present in the water, for example, carbonates storage or high-level tank. Because of the simple integra-and hydrogen carbonates. It defines the acid binding tion of the system into the process, the analytical data capacity or buffering capacity. Chlorine, by contrast, is and reports of off-limit conditions can be made available used in water treatment plants as a disinfecting agent. If internally on the Intranet or in the control room, or exter-the concentration of chlorine is too low, the disinfecting nally on the Internet. effect is inadequate; if the concentration is too high, unwanted disinfection by-products form. Cooling water and boiler feed water pH value, conductivity, chloride, and total hardness Cooling water and boiler feed water are used in thermal power plants, incinerators, and numerous industrial processes, including processes in the chemical industry. Once the pH value, conductivity, chloride concentration, and total hardness (Ca and Mg) have been determined, the key characteristics are known. In particular, cooling water and feed water with pH values below 7.0 or high chloride concentrations cause corrosion in the steel tanks and pipes. High total hardness leads to scale formation. All the parameters must remain below certain limits and can be determined reliably with ProcessLab. Wastewater Sample preparation – filtering of wastewater samples Water samples often have to undergo sample prepara- tion before analytical determination of their constituents. Sample preparation usually involves filtration or the addition of reagents. ProcessLab is able to perform many of these frequently repeated tasks automatically and can thereby considerably cut the time spent on routine analysis both in the production plant and in the laboratory. Online process analysis 26 Customized online process control Straightforward network integration Monitoring and control of water quality is of paramount Analysis alone is of no use for water quality control, and importance. We use surface or groundwater for drinking that is why the analyzers are all equipped with possibili-water or for industrial purposes such as boiler feed, cool-ties for digital as well as analog outputs. Results, for ing water, or make-up water. Furthermore, strict controls example, can be transferred via 4–20 mA outputs, on pollution require close control of surface and waste where as alarms can be transmitted via the digital out-water derived from power plants or the chemical indus-puts. Digital inputs, in turn, can be used for remote start-try. Whatever the source of the water or whatever type stop purposes. of water is involved, Metrohm Process Analytics has the analyzer to monitor water quality and determine concen-Single-Parameter online Analyzers trations of relevant species in water. The ICON Analyzers and Alert Ion Analyzers are based on colorimetric and ion-selective electrode (ISE) methods, Online analyzers from Metrohm Process Analytics run respectively. The ISE methods are generally used for continuously 24 hours a day, 7 days a week without any measurements in the ppm and percent range, whereas operator intervention. Whether a single parameter in a the colorimetric techniques are used for the ppb to ppm single sample stream is involved or several different range. Some typical applications: parameters in complex and multiple sample streams, Metrohm Process Analytics provides the right analyzer. Sodium and silica in power plants Both sodium and silica play a major role in corrosion Proven wet chemistry methods processes that occur in cooling water systems. For power All analyzers are based on wet chemical analysis tech-plants, it is essential to monitor the concentrations of niques such as titration, colorimetry, or ion-selective elec-these species. With the Alert Ion Analyzer equipped with t rode measurements. Most of the well-established labo-the Metrohm Na+ ISE, it is possible to measure sodium ratory methods for water analysis can be easily trans-concentrations down to 1 ppb. If lower detection limits ferred to the analyzers. In online analysis, sampling and are required, the Alert Ion Analyzer can be replaced by sample preparation are at least as important as the ana-the more accurate ICON Analyzer. Silica in cooling water lyzer itself. Metrohm Process Analytics has a lot of exper-or high-purity water can be determined with the ICON tise in this area and configures custom-made sampling Colorimeter at concentrations as low as 1 ppb. systems, for example, for filtration, sample taking from pressur ized containers, or degassing. ICON Analyzer for silicate analysis in high-purity water 27 The ADI 2035 Process Analyzer comes in 3 basic configurations for potentiometric, photometric, and thermometric measurements. Ammonia in drinking, waste or cooling water Chemical oxygen demand (COD) As stated in a WHO report on drinking water: «The pres-The COD sum parameter is commonly used to indirectly ence of elevated ammonia levels in raw water may inter-determine the amount of organic compounds in water. fere with the operation of manganese-removal filters because too much oxygen is consumed by nitrification, The COD is measured in mg/L using a colorimetric resulting in mouldy and earthy-tasting water. The pres-method in which dichromate is added and the sample is ence of ammonia in raw water can lead to nitrate-rich digested. Depending on the concentration range an drinking water due to catalytic oxidation or accidental ADI 2019 or an ADI 2040 Process Analyzer is employed. colonization of filters by ammonia-oxidizing bacteria.» Total organic carbon content (TOC) The analysis of ammonia can be done either colorimetri-The total organic carbon content (TOC) is a highly impor-cally with an ICON Analyzer or with ion-selective elec-tant sum parameter that indicates all of the organic car-trodes using an Alert Ion Analyzer, depending on the bon in the sample examined. This value represents the required concentration range and detection limit. level of organic contamination. As an online parameter, Manganese and nitrite can also be determined by both it can be readily automated and provides attractively high analyzers. precision and accuracy. Another advantage: the determination requires no toxic chemicals. More demanding applications For more complex determinations, multiple parameters The ADI 7010 TOC Analyzer is perfect for continuous or complex matrices such as surface water with high monitoring of the TOC value in all types of water. The organic contents, Metrohm Process Analytics offers the oxidation of organic carbon is accomplished using per-ADI 201Y and ADI 204Y and the 2035 family of Process sulfate in the presence of UV light, and complies with Analyzers. Typical applications for these analyzers are: EPA, ASTM, NAMUR and ISO regulations. Hardness in drinking, industrial waste and surface water This parameter is obtained by determining the calcium and magnesium concentration by complexometric titration with EDTA using a Cu2+ ISE. Depending on the desired concentration range and detection limit a Titrolyzer ADI 2016, a 2035 Process Analyzer configured for titration, or an ADI 2045TI Process Analyzer can be used. 28 Metrohm Quality Service – Service you can rely on Reliable results for the lifetime of your analytical Metrohm Compliance Service instruments Benefit from the Metrohm Compliance Service when it Water analysis is a key component of analytical che-comes to the professional initial qualification of your mistry and covers the analysis of all water types, from ana lytical instruments. Installation Qualification/ ultrapure water and drinking water to wastewater. Operational Qualification carried out by our experts Whoever is responsible in the laboratory for the accuracy saves you time and money, as your analytical system is of the results must not make compromises. Fortunately, configured ac cord ing to your needs and put into opera-systems installed and maintained by professionals on a tion fast and reliably. regular basis all but eliminate the threats of instrument failure and lost profits. Initial instructions and user trainings ensure error-free ope ration of your new instruments by your staff. The Relying on the Metrohm Quality Service gives you peace Metrohm Compliance Service includes comprehensive of mind from the very start. From the profes-do cumentation and guarantees compliance sional installation of your instruments with the stand ards of quality manage- to regular maintenance care and ment systems such as GLP/GMP – should a failure ever occur – and ISO. instant quality repairs, we do everything to make sure that you can rely 100 per cent on results produced during the entire lifetime of your Metrohm instruments. Metrohm Quality Service 29 Metrohm’s global Quality Service, and regularly sched-particular need. With a Total Care Contract, for example, uled preventive maintenance in particular, extends your you can rely on the optimum performance of your instrument’s lifetime and ensures trouble-free operation. Metrohm instruments at all times, incurring no additional Maintenance work is carried out by qualified and certi-costs whatsoever and benefit from complete and com- fied service engineers. You have the option of selecting pliant documentation. different types of service contracts depending on your Metrohm Quality Service Customer benefits • Minimizes downtime through preventive maintenance • Cost control and savings through free or discounted replacement materials and Metrohm Care Contracts consumables • Guaranteed reaction times and rapid on-site repair • Documented instrument certification as an ideal preparation for audits • High data security and maximum system performance through regular, professi-Metrohm Software Care onal software maintenance • Customized services and documentation for analytical instrument qualification (AIQ) Metrohm Compliance Service • Professional start-up (IQ/OQ or Certified Installation) and requalification or recertification by specifically trained employees Metrohm Remote Support • Quick resolution of software and application issues directly at the workplace • Calibration of burettes (e.g., dosing and exchange units) with certification Metrohm Dosing Test • Accurate measurement results • Verification documentation for compliance with regulations and efficient audits • Rapid availability of repaired instruments thanks to decentralized repair workshops around the world and a central workshop at the manufacturer site Metrohm Repair Service • Highly qualified service technicians ensure sustainable repair success • Rapid resolution of problems and minimized downtimes through on-site emer-gency services and express repairs • Original spare parts, made in Switzerland and available worldwide • Short delivery times through warehousing from local distributors Metrohm Spare Parts • Investment security through ten-year spare parts guarantee after discontinuation • Free access to the Metrohm Application Finder (www.metrohm.com/en/ applications/) with more than 1800 applications (Application Bulletins, Application Notes, monographs, technical posters, and technical articles) Metrohm Application Support • Rapid and professional resolution of any application issues through personal consultations with our specialists by e-mail, telephone, or remote support • Support for the solution of complex analytical problems, as well as method optimization on-site or at our application laboratories • Basic and advanced training with local representatives, at the Metrohm Academy or directly on-site Metrohm Training Programs • Efficient and proper use of all analytical methods, as well as results reliability through competently trained users • Training documentation and certificates for trouble-free audits Ordering information 30 A water analysis overview is provided in the Metrohm monograph: «The determination of water constituents with Metrohm instruments», which can be downloaded and obtained free of charge from your local Metrohm supplier. pH measurement, conductivity measurement, and titration pH measurement 2.913.0110 913 pH Meter with Primatrode and accessories case 2.913.0210 913 pH Meter, laboratory version 2.780.0010 780 pH Meter including Unitrode 2.781.0010 781 pH/Ion Meter including Unitrode 2.867.0110 867 pH Module with Touch Control including iUnitrode 2.867.0210 867 pH Module with tiamo light and iUnitrode Conductivity measurement 2.856.0110 856 Conductivity Module with Touch Control and five-ring conductivity measuring cell 2.856.0210 856 Conductivity Module with tiamo light and five-ring conductivity measuring cell 2.912.0210 912 Conductometer, laboratory version 2.912.0110 912 Conductometer with conductivity sensor and accessories case 2.914.0120 914 pH/Conductometer with Primatrode and accessories case 2.914.0220 914 pH/Conductometer, laboratory version 6.0915.100 Five-ring conductivity measuring cell c = 0.7 cm–1 with integrated Pt 1000 for 856 Conductivity Module 6.0915.130 Five-ring conductivity measuring cell c = 1.0 cm–1 with integrated Pt 1000 for 856 Conductivity Module 6.0916.040 Conductivity measuring cell (stainless steel) c = 0.1 cm–1 with Pt 1000 for 856 Conductivity Module 6.0917.080 Conductivity measuring cell, c = 0.5 cm–1 with Pt 1000 for 912/914 6.0918.040 Conductivity measuring cell made of stainless steel, c = 0.1 cm–1 with Pt 1000 for 912/914 6.0919.140 Conductivity measuring cell, c = 1.6 cm–1 with Pt 1000 for 912/914 Titration 2.905.0010 905 Titrando MATi 01 Fully automated water analysis MATi 12 Automated COD determination MATi 13 Fully automated determination of the permanganate index in accordance with DIN EN ISO 8467 6.0253.100 Aquatrode plus 6.0257.600 LL-Aquatrode plus with Pt 1000 6.0277.300 iAquatrode plus with Pt 1000 6.0510.100 Combined Ca2+-selective polymer membrane electrode 6.0502.150 F–-selective crystal membrane electrode 6.0430.100S Ag Titrode with Ag S coating 2 6.0750.100 LL ISE Reference Ion chromatography Oxohalides plus standard anions 2.930.2560 930 Compact IC Flex Oven/SeS/PP/Deg 2.850.9010 IC Conductivity Detector 2.858.0020 858 Professional Sample Processor – Pump 6.2041.440 Sample rack 148 × 11 mL 6.5330.110 IC equipment: Inline ultrafiltration 6.1006.630 Metrosep A Supp 7 - 250/4.0 6.6059.311 MagIC Net 3.1 Compact Anions and Cations in ultrapure water 31 2.940.2500 940 Professional IC Vario TWO/SeS/PP 2.850.9010 IC Conductivity Detector (2 ×) 2.815.0130 815 Robotic USB Sample Processor XL (2T/0P) 2.800.0010 800 Dosino (2 ×) 6.5330.140 IC equipment: MiPCT (2 x) 6.9920.191 Sample rack 35 × 50 mL + 3 × 300 mL 6.1006.510 Metrosep A Supp 5 - 100/4.0 6.1050.430 Metrosep C 4 - 250/4.0 6.1006.310 Metrosep A PCC 1 HC/4.0 6.1010.310 Metrosep C PCC 1 HC/4.0 6.6059.312 MagIC Net 3.1 Professional Suppressor rotors 6.2832.000 MSM Rotor A 6.2842.000 MSM-HC Rotor A 6.2844.000 MSM-LC Rotor A 6.2842.200 MSM-HC Rotor C 6.2842.020 Adapter sleeve for suppressor Vario to MSM and MSM-LC Voltammetry 2.884.0110 884 Professional VA (MME) 2.884.1110 884 Professional VA semiautomated MME consisting of 884 Professional VA, measuring head for MME, and two 800 Dosinos. MVA-22 Fully automated Professional VA system consisting of 884 Professional VA, measuring head for the MME, 919 IC Autosampler plus for VA, and two 800 Dosinos for automatic addition of auxiliary solutions. Allows the automatic processing of up to 28 samples. This system is the optimum solution for automatic analysis of small sample series. Required accessories 6.5339.030 VA Electrode Kit 884 MME 6.6065.202 viva 2.0 Full TitrIC and VoltIC systems TitrIC Vario pro I The basic hyphenated system combining titration and IC TitrIC Vario pro II The advanced hyphenated system combining titration and IC for complete ion analysis TitrIC Vario pro III The high-end version combining titration and IC with closed sample vessels VoltIC Vario pro I The hyphenated IC and voltammetry system for parallel determination of ions and heavy metals Process analysis We offer online and atline Analyzers that meet any requirement in the process industry, from single-parameter to the most advanced multiparameter analyzers. Every analyzer is custom-tailored to the specific task at hand. ADI 2045PL ProcessLab system for atline determination of various parameters using titration, colorimetry, and ISE ADI 201Y Series Single method Process Analyzers, available with titration, colorimetry, or ISE ADI 204Y Series Multifunctional Process Analyzers, available with titration, ISE, colorimetry, and voltammetry 2035 Series Analyzer family designed in 3 configurations: potentiometric, photometric, and thermometric titration 7010 TOC Analyzer for determination of the total organic carbon content (TOC) in liquid samples Furthermore, we offer the Plug and Analyze Series – ICON and Alert for single method, single component water analysis. Please contact your Metrohm supplier for further information. Please also consult www.metrohm.com water.metrohm.com G, CH-9101 Herisau ohm A witzerland by Metr , printed in S SW Subject to change Layout by Ecknauer+Schoch A 8.000.5141EN – 2015-09