Metrohm Inline Sample Preparation. Ion chromatography analyses could not be easier

Transcription

1 Metrohm Inline Sample Preparation Ion chromatography analyses could not be easier

2 Metrohm Inline Sample Preparation for precise and accurate analysis 02 Crystal clear, clinically pure, no bacteria and no particles: this would be an ideal sample for ion chromatography. Unfortunately things are often very different in real life. Apart from the ions to be determined, the samples still contain matrix components, which may be aggressive or lead to precipitation in the system. They can sometimes make analysis difficult, if not impossible. Samples with a high load can destroy the separating column or lead to blockages in the system. That is why suitable sample preparation is essential for reliable and accurate analysis. In the past, all sample preparation steps had to be carried out manually. This is history. With the unique Metrohm Inline Sample Preparation («MISP») techniques, some of which have been patented, it is now possible to automate these processes in full and make each individual step traceable. The high precision and accuracy of liquid handling are based on the outstanding properties of the patented 800 Dosino. The use of Dosino technology ensures that up to 0.2 μl liquid can be measured out and transferred exactly, quickly and precisely. The advantages are obvious: you save a significant amount of time and cost, while also increasing the reliability of your analyses. Methods of Metrohm Inline Sample Preparation: Inline Ultrafiltration Inline Dialysis Inline Dilution Intelligent Partial Loop Injection Inline Extraction Inline Matrix Elimination Inline Neutralization Inline Cation Removal Inline Preconcentration Inline Calibration Inline Spiking Metrohm Inline Sample Preparation (MISP): These techniques are the key to automate of your analyses. Samples are introduced by a Sample Processor. Subsequently, they are subjected to one of Metrohm s Inline Sample Preparation techniques. Finally, they are directly injected into an ion chromatograph. This fully automated sequence is the common principle of all MISP techniques.

3 Highlights Unique, fully automatic sample preparation (including patented items) Inline transfer of a solid, liquid or gaseous sample through to injection Improves precision and accuracy of the analysis results Minimizes the time needed Reduces manual steps Guarantees traceability for each sample preparation step Minimizes the risk of contamination Opens up new application areas Makes ultratrace analysis possible Self-optimizing analyses based on logical decisions of the system Professional liquid handling due to Dosino technology 03

4 Metrohm Inline Ultrafiltration 04 In modern ion chromatography, it is recommended to filter all samples before injection; otherwise, particles may become deposited in the injection valve, in capillaries or on the column. This leads to a higher pressure in the system, which in turn reduces the chromatographic performance and the lifetime of the columns. With Inline Ultrafiltration, Metrohm offers a fast and thus economical alternative to manual filtration. Inline Ultrafiltration combines sample delivery directly with filtration. Because of this unique functional feature, filters with a pore size of 0.2 μm can be used for 100 or more samples. This is ideal sample preparation for routine analysis. Inline Ultrafiltration at a glance: Fully automatic filtering (0.2 μm) of samples during sample delivery Lifetime of the column is increased Saving of a manual step and, as a result, reduced risk of contamination Low-maintenance requirement More than 100 samples with one filter, because carryover from sample to sample is negligibly small (<0.1%) Cost-saving solution for routine analysis Can be combined with Inline Dilution and Intelligent Partial Loop Injection technique Inline Ultrafiltration is possible by combining a dual-channel peristaltic pump with the ultrafi ltration cell. The sample can be delivered either manually or automatically by a sample changer.

5 Applications with Inline Ultrafiltration: Analysis of anions, cations as well as carbohydrates and other polar substances in the μg/l to g/l range Samples slightly or moderately contaminated with particles, algae or bacteria Drinking water and surface water Process water and waste water Extracts Digestion solutions Diluted fruit and vegetable juices 05 The two parts of the ultrafiltration cell are separated by a filter membrane. On one side the sample is carried through the cell. On the other side some of the sample is drawn off through the membrane and transported to the injection valve. The formation of fi lter cake is prevented by continuous movement of the sample stream at an appropriately high fl ow rate.

6 Metrohm Inline Dialysis 06 Inline Dialysis is the answer to complex sample matrices. This technique separates not only particles from their analytes, but also colloids, oil components and large mole cules. Protein-containing samples can be injected directly after inline dialysis. This saves time-consuming manual steps such as the precipitation of proteins with Carrez reagent. To separate the analytes from the matrix, a cellulose acetate or nylon membrane (pore size 0.2 μm) is used. Even if your samples are heavily contaminated with particles and filtration is not feasible because the filters would get blocked, inline dialysis is able to help. Inline Dialysis at a glance: Time- and cost-saving inline sample preparation for analysis of complex samples Metrohm s patented Stopped-Flow Dialysis Fully automatic dialysis of samples during sample delivery Increased column lifetime due to elimination of large molecules, oily sample components, proteins and particles No time-consuming manual working steps Low-maintenance requirement (replacement of dialysis membrane every samples) Minimal carryover (<0.2%) Almost complete dialysis rates Possibility of combination with Inline Dilution and Inline Extraction Setup for Inline Dialysis: In the traditional setup two dual-channel peristaltic pumps are combined with the dialysis cell. Inline Dialysis can also be carried out manually or with a sample changer.

7 Applications with Inline Dialysis: Analysis of anions, cations, carbohydrates and small polar substances in the μg/l to g/l range Samples heavily contaminated with particles, algae or bacteria Emulsions and dispersions Process water, washing water and waste water Oil-containing samples such as cutting oils and petroleum-containing samples Samples from fermentation processes Dairy products and other protein-containing samples, e.g., flour and honey Body fluids, e.g., blood, urine and sweat Organically contaminated samples such as tobacco and ink Concentrated fruit and vegetable juices 07 The principle of Stopped-Flow Dialysis: Sample is delivered continuously on the sample side. After a rinsing phase the acceptor stream is stopped. Because of the concentration gradient, the ions pass through the membrane until an equilibrium is achieved and thus the concentration in the acceptor solution matches the concentration of the original sample. The acceptor solution is directly injected into the IC.

8 Metrohm Logical Inline Dilution 08 One of the oldest sample preparation techniques is the dilution of samples. Nowadays, this step too can be carried out inline using an automated system. A further development is Logical Inline Dilution (Metrohm Inline Dilution Technique «MIDT»). For this, the sample just needs to be placed on the sample changer and the analysis started. The system automatically calculates the optimum dilution factor and analyzes the sample. Thus your results are always reliable, because they are within the calibration range. Of course, not only samples, but also standards can be diluted. Consequently, Metrohm offers you the possibility of automatic calibration, i.e., you only need to prepare a single multi-ion standard. The system dilutes this standard with different dilution factors and thus carries out multipoint calibration. Logical Inline Dilution at a glance: Time- and cost-saving inline sample preparation technique for routine analysis Unique dilution system based on logical decisions of the system Fully automatic sample dilution during sample delivery Accurate and reliable results, irrespective of the initial concentration of the sample Low-maintenance equipment Automatic calibration; preparation of a single multi-ion standard is enough High flexibility: one method for all dilution factors between 1 and 100 Sample concentrations in the range 1: can be analyzed reliably with automatic calibration Possibility of combination with Inline Ultrafiltration and Inline Dialysis Setup for Inline Dilution: Dilution takes place in an external dilution vessel, so all positions on the sample rack are available for samples. The concentrated sample, as well as the diluting agent, are measured exactly and added by means of an 800 Dosino. After homogenization, the diluted sample is transferred by a peristaltic pump to the injection valve of the ion chromatograph. Undiluted samples can also be analyzed with the same setup.

9 Applications with Logical Inline Dilution: Analysis of anions, cations, carbohydrates and other polar substances in the mg/l to g/l range Samples with high ion concentration Samples from all industry branches 09 Determination of the optimum dilution factor. Peak area [µs min/cm] calibration range logical dilution Concentration [mg/l] sample If the sample is outside the calibration range, it is diluted with the optimum dilution factor and analyzed. Thus your results are always within the calibration range.

10 Metrohm Intelligent Partial Loop Injection Technique 10 Unlike in Logical Inline Dilution, the dilution factor is not varied in the intelligent Partial Loop Injection Technique (Metrohm intelligent Partial Loop Technique «MiPT»). With the intelligent Partial Loop Technique, the injection volume of an undiluted sample is adjusted between 2 and 200 μl. The method is «intelligent» because it calculates the optimum injection volume. As a result, here too it is possible to cover a very wide range of sample concentrations. Furthermore, this technique is almost free of any carryover (<0.001%). Therefore, in practice it is possible to carry out analyses in the mg/l range and μg/l range one after the other with the same calibration and in the same sample sequence without any time-consuming rinsing procedures. This ensures flexibility in dayto-day laboratory work. «MiPT» is characterized by excellent linearity over the entire volume range. For this reason, this technique can also be used for automatic calibration with just a single multi-ion standard. So calibration can be done easily and quickly. Intelligent Partial Loop Injection Technique at a glance: Time- and cost-saving intelligent injection technique for routine applications and method development High-performance analysis system which, on the basis of logical decisions of the system, adjusts the injection volume to the concentration of the sample Exact and reliable results, because the results are always within the calibration range Faster and more precise (n=10: RSD <0.1%) than manual dilution Almost maintenance-free equipment Automatic calibration; preparation of just one single multi-ion standard Optimum flexibility one method for all injection volumes between 2 and 200 μl Smallest carryover from sample to sample of all sample preparation techniques: <0.001% Sample concentrations in the range 1: can be analyzed reliably with automatic calibration Possibility of combination with Inline Ultrafiltration Setup of the intelligent Partial Loop Injection Technique: Here too an 800 Dosino measures out the sample exactly. It can dose exactly 0.2 μl. The intelligent Partial Loop Injection Technique can be carried out both with and without a sample changer and is also suitable for combined anion-cation systems.

11 Applications with intelligent Partial Loop Injection Technique: Analysis of anions, cations, carbohydrates and polar substances in the μg/l to mg/l range Universal use for all types of samples in the typical IC concentration range: trace analysis through to wastewater analysis 11 Flowchart of an intelligent partial loop injection: (1) conditioning of the sample path and aspiration of the sample, (2) injection valve switches to «Inject», (3) exact dosing of the injection volume into the sample loop, (4) injection of the volume supplied.

12 Metrohm Inline Extraction 12 Extractions transfer ingredients into another medium. In ion chromatography water is used as the basis of the mobile phase. Therefore, inline extraction allows watersoluble components to be transferred from a nonpolar organic phase into an aqueous phase. The aqueous phase can then be injected directly after inline dialysis and analyzed. Thus whole sample series can be dealt with fully automatically. Inline Extraction at a glance: Time- and cost-saving inline sample preparation for the analysis of organic samples Unique inline technique for fully automatic extraction of samples during sample delivery Facilitates ion chromatographic analysis of the watersoluble components of nonpolar, organic samples No time-consuming manual steps Low-maintenance requirement Minimal carryover from sample to sample (<0.2%) Combination with Inline Dialysis possible Setup and operation of Inline Extraction: An exactly measured-out sample is transferred into an external vessel. There the extraction medium is added and stirred for a certain time. During a waiting time that follows, two phases form. The aqueous phase now contains all the extractable, water-soluble ingredients of the sample. In subsequent Inline Dialysis any remaining organic droplets are removed from this phase. Now the sample can be injected and analyzed.

13 Applications with Inline Extraction: Analysis of water-soluble anions, cations and carbohydrates in the μg/l to mg/l range Quality control of biodiesel Determination of impurities in edible oils 13

14 Metrohm Inline Matrix Elimination 14 The determination of anions or cations in polar organic solvents or other aggressive matrices is an analytical challenge. Such samples can damage the column or affect the chromatograms in such a way that evaluation is im - possible. This challenge can be met with Inline Matrix Elimination. Inline Matrix Elimination is a technique that is able to separate ionic analytes from the uncharged matrix without sample preparation cartridges (SPE cartridges). In addition, the counterions of the analytes and of the matrix are removed. In contrast to Inline Dialysis, small matrix molecules (e.g. isopropanol, hydrogen peroxide and undissociated boric acid) can also be eliminated with Inline Matrix Elimination. Inline Matrix Elimination at a glance: Universal sample preparation to remove an uncharged or oppositely charged matrix during sample delivery Increased column lifetime Opens up the possibility of applications that are impossible with direct injection Alternative to time-consuming and expensive manual sample preparation with SPE cartridges Ultratrace analysis in combination with inline calibration No risk of contamination due to blank-free liquid handling Low-maintenance requirement Can be combined with Inline Preconcentration and Inline Neutralization Setup of Inline Matrix Elimination, as used, e.g., to analyze fuel mixtures. The sample is measured by way of a sample loop, which is placed on an additional valve, and then washed by means of a transfer solution onto a preconcentration column. The transfer solution can be ultrapure water or a diluted solvent. It washes any uncharged and organic matrix components down from the preconcentration column. In addition, all counterions in the sample are removed.

15 15 Applications with Inline Matrix Elimination: Analysis of anions or cations in the ng/l to g/l range Trace analysis in polar solvents such as isopropanol, ethanol, THF Trace and ultratrace analysis in extracting agents Quality control in fuels, fuel mixtures and biofuels Analysis of the ionic components in hydrogen peroxide Quality assurance of ultrapure chemicals Ultratrace analysis in samples from nuclear power plants and conventional power plants Cation determination in alcohol-containing samples Anion determination with Inline Matrix Elimination in a fuel-ethanol mixture (E85: 85% ethanol, 15% gasoline); column: Metrosep A Supp 7-250/4.0; eluent: 3.6 mmol/l Na 2 CO % acetone, 0.8 ml/min; sample volume: 10 μl; transfer solution: 7.5% acetone.

16 Metrohm Inline Neutralization 16 When strongly acidic or alkaline samples are involved, Inline Neutralization is recommended. With the help of this technique, such samples can be prepared fully automatically during sample delivery and then analyzed directly. This technique is also suitable for determining ultratraces. After Inline Neutralization, even strongly alkaline samples can be preconcentrated, facilitates analyses in the ng/l concentration range. The Sample Prep Module «SPM» is used for Metrohm Inline Neutralization. The heart of the «SPM» is a rotor, filled with cation-exchange resin, that contains three cartridges. While one cartridge is used for sample preparation, a regeneration step takes place automatically on the second. The third cartridge is automatically rinsed during this time. Thus, a freshly regenerated cartridge is available for each sample. The choice of regenerant depends on the nature of the sample. For strongly acidic samples, sodium hydroxide is used. Thus, the protons of the sample are exchanged for Na + in the «SPM» and the sample is neutralized. If, however, strongly alkaline samples are analyzed, perchloric acid is used as regenerant. In this case the relevant cation is exchanged for a proton in the «SPM». Inline Neutralization at a glance: Fully automatic sample preparation for strongly alkaline or acidic samples during sample delivery Allows preconcentration even for strongly alkaline samples Neutralizes the ph-value of your sample to Replaces the time-consuming and cost-intensive manual sample preparation with SPE cartridges Ultratrace analysis in combination with inline calibration Eliminates the risk of contamination by avoiding manual sample preparation steps Almost maintenance-free and very robust Can be combined with Inline Preconcentration and Inline Matrix Elimination Applications with Inline Neutralization: Analysis of anions in the ng/l to g/l range Trace analysis in concentrated alkaline solutions and acids Samples from aluminum production, e.g., «Bayer Liquor» samples Starter substances from the electroplating industry Ultratrace analysis for nuclear power plants in matrices such as lithium hydroxide/boric acid or with high amine concentrations Inline Neutralization in the ultratrace range: Sample is drawn into a buffer volume by way of a valve; the valve is then switched and the sample passes the inline calibration valve, which is used for inline calibration of the system (see page 20). After that, the sample passes through the «SPM». Here neutralization takes place. The neutralized sample is transferred to the preconcentration column. Finally, the sample is injected and the chromatogram recorded.

17 Metrohm Inline Cation Removal The technique of Inline Cation Removal is used especially to remove transition metals from electroplating samples. Inline Cation Removal is similar to Inline Neutralization in its setup and the way it works. As in the case of Inline Neutralization of strongly acidic samples, sodium hydroxide or lithium hydroxide is used as regenerant. The metal ions are exchanged for Na + in the «SPM». Spe cifi cally for samples from the electroplating industry a simple exchange for protons is unsuitable, since this would render the sample too acidic. Inline Cation Removal prevents the precipitation of metal hydroxides in the system and enrichment in the chemical suppressor. Analysis with integrated Inline Cation Removal is fully automatic, robust and reliable. Inline Cation Removal at a glance: Fully automatic sample preparation to remove metals and transition metals during sample delivery Eliminates the risk of precipitation and deposits in the system Increases the lifetime of the column and chemical suppressor Replaces time-consuming manual sample preparation with SPE cartridges Almost maintenance-free system Cost-saving inline sample preparation, because no SPE cartridges are needed Can be combined with Inline Preconcentration and Inline Matrix Elimination Applications with Inline Cation Removal: Analysis of anions in the ng/l to g/l range Analysis of electroplating samples contaminated with different transition metals Analysis of impurities in electroplating baths, e.g., nickel or zinc baths Samples from aluminum production, e.g., «Bayer Liquor» samples 17 Inline Cation Removal for samples from the electroplating industry: The sample is measured in a sample loop on an additional valve. The sample is then washed with a transfer solution onto a preconcentration column by way of the «SPM». The trans fer solution usually consists of ultrapure water.

18 Metrohm Inline Preconcentration 18 For each analytical method, there are limits regarding the smallest detectable concentration. In ion chromatography, depending on the system used, these limits are between 0.1 μg/l and 100 μg/l. Inline Preconcentration in - creases measuring sensitivity considerably and opens up concentration ranges in the single-digit ng/l range. For Inline Preconcentration, a preconcentration column is used instead of a sample loop. This column has functional features very similar to those of separating columns, except that the material has a considerably higher capacity and consists of comparatively large particles, which ensure a much lower backpressure. If a defined volume of sample is passed over the preconcentration column, the relevant ions are retained. Through injection the accumulated ions are eluted with the eluent onto the separating column. The crucial step is exact measurement of the volume. Here you benefit from the outstanding accuracy of the 800 Dosino. On account of its performance capability, the preconcentration of variable volumes is possible. Inline Preconcentration is linear over a wide range. This means the method is enormously flexible and automatic calibration is possible. Consequently, you only need to prepare one single multi-ion standard; the system takes care of the preparation of a multipoint calibration. Inline Preconcentration for samples in the μg/l range: The sample is drawn through the injection valve (inject position) into a buffer volume. Then the valve is switched to the fi ll position and the exact volume fed onto the preconcentration column. After injection, the ions elute from the preconcentration column and are analyzed.

19 19 Inline Preconcentration at a glance: Very flexible sample preparation technique for determining traces and ultratraces Allows limits of detection (LOD) in ion chromatography in the single-digit ng/l range Variable preconcentration volume: based on logical decisions, the system optimizes the preconcentration volume Always reliable results, because they are always within the calibration range Very precise and exact analyses down to the ultratrace range Almost maintenance-free equipment Automatic calibration; the preparation of a single multi-ion standard is enough A single analytical method for variable preconcentration volumes between 0.5 and 20 ml Minimal risk of contamination due to blank-free liquid handling Combination with Inline Calibration possible, the ideal calibration method for the ng/l range High-capacity preconcentration columns allow this technique also to be used for samples with high ionic load Can be combined with Inline Matrix Elimination and Inline Neutralization Applications with Inline Preconcentration: Analysis of anions or cations in the ng/l to μg/l range Numerous applications from ultrapure water analysis through to drinking water analysis Quality control of cooling water in conventional power plants Analyses of various samples from nuclear power plants Process control and monitoring of rinsing solutions in the semiconductor industry

20 Metrohm Inline Calibration 20 Inline Calibration is a unique technique that allows calibration to be carried out reliably and precisely in the ng/l range. For this, a single multi-ion standard is prepared in the μg/l range. This is considerably more stable and easier to prepare than a ng/l standard. The standard is introduced into the system via an additional valve, which is fitted with a sample loop (e.g., 10 μl). A multipoint calibration emerges from multiple filling of the sample loop and preconcentration of the standard prior to injection. How is it possible to calibrate with a μg/l standard and measure samples in the ng/l range? The answer lies in the linearity of the method. If 10 μl of a 100 μg/l standard solution is transferred onto the preconcentration column, that corresponds exactly to the preconcentration of 10 ml of a solution of 100 ng/l. The great advantage of Inline Calibration is the elimination of the contamination risk during the preparation of various standards in the ng/l range and calibration. In this way you can calibrate reliably and precisely down to the single-digit ng/l range. Inline Preconcentration with Inline Calibration for samples in the ng/l range: The injection of 1, 2 or x sample loop volumes onto the preconcentration column produces the different calibration points. Peak area [µs/cm min] lithium ammonium sodium potassium R 2 = R 2 = R 2 = R 2 = Concentration [µg/l] Example calibration for cations recorded with Inline Calibration.

21 Metrohm Inline Spiking Inline Spiking is used to verify the results of calibration and also of sample analyses. For this technique, the same arrangement is used as for inline preconcentration with Inline Calibration. During the preconcentration of ultrapure water or sample, a sample loop volume of the standard solution is injected, i.e., defined quantities of substance from the standard solution are added to the traces of ions present in the sample without any contamination. Thus, Inline Preconcentration can be checked quickly and easily. Conductivity [µs/cm] lithium; 200 µg/l sodium; 6.68 µg/l ammonium; 5.07 µg/l zinc; 4.89 µg/l potassium; 5.18 µg/l Time [min] 10 Example of a boric acid/lithium hydroxide matrix in a nuclear power plant sample. A system with Inline Neutraliza tion and Inline Calibration was used for the Inline Spiking. Column: Metrosep C 4-250/4.0; eluent: 2.5 mmol/l oxalic acid, 1.0 ml/min; sample preconcentration volume: 1 ml; sample contained 2 g/l boric acid and 200 μg/l lithium (in black), this sample was spiked with 5 μg/l sodium, ammonium, zinc and potassium (in red).

22 Inline Sample Preparation by Professional Liquid Handling 22 The 850 Professional IC is a modern, compact ion chromatograph that is highly flexible regarding the configuration of its modular components. The instrument grows with your demands. Were your analytical requirements to change, you could adapt the equipment of the 850 Professional IC at any time. One option is the use of the 872 Extension Module. For Inline Sample Preparation, Metrohm offers the 872 Extension Module Sample Prep. It is used if a technique requires an additional injection valve or a peristaltic pump (e.g., Inline Preconcentration with Inline Calibration). The 872 Extension Module Liquid Handling was developed specifically for professional liquid handling. Apart from a peristaltic pump and an injection valve, it also contains a 10-port selector valve. This enables the direct linking of Inline Sample Preparation with sophisticated liquid handling. In addition, the system can accommodate a reaction vessel, a buffer volume and up to 6 auxiliary solutions. Short paths ensure very short rinsing times. The accuracy of the volumetric transfer is ensured in this instrument, once again, by an 800 Dosino. Thus, work can be carried out very precisely and reliably. A whole range of new possibilities open up for Inline Sample Preparation. The 872 Extension Module extend the confi guration of Professional IC systems. Here an 850 Professional IC AnCat MCS is combined with an 872 Extension Module Sample Prep and 858 Professional Sample Processor. Professional liquid handling is made possible by the 872 Extension Module Liquid Handling. Applications of the 872 Extension Module Liquid Handling Mixing of solutions Variations in the ph-value of samples Pre-column derivatizations, reactions of samples prior to analysis (e.g., complexing reactions) Sample preparation steps (e.g., dilution of samples) 10-port sampling valve

23 23 Contaminant-free liquid handling Contamination-free liquid handling is essential for analyses in the trace and ultratrace range. By combining the patented 800 Dosino with a buffer volume and a trap column, Metrohm offers you a system that meets this requirement perfectly. This well-devised setup ensures that there is neither any carryover from sample to sample nor any interference in the chromatogram due to impurities from the transfer solution. As a result, you can work fast and without a blank value. Professional liquid handling based on the accuracy and precision of the patented 800 Dosino. The transfer water is added by the trap column (red arrows). Thus, the transfer solution can be used without any contamination. Solutions are aspirated along the path marked with the blue arrow. Sample is only drawn along as far as the buffer volume. Because of the lower backpressure, this can be done very quickly.

24 Inline Sample Preparation for gaseous samples 24 The old cliché that ion chromatography can only be used to analyze liquid samples is no longer valid. Modern in - line sample preparation methods also allow gases and solids to be analyzed, so the way is open for new application areas. Air analysis, in particular, has become more important in recent years in recognition of the adverse effects of at - mospheric pollution on human health. No matter whether you want to analyze air or other gaseous samples Metrohm offers you two possibilities for determining the ionic components in your samples. The advantages of this coupling technique are obvious. The ionic profile of aerosols can be analyzed with a high time resolution of only 15 minutes. Moreover, problems in storing the samples are completely avoided. Inline coup ling with the ion chromatograph guarantees contamination-free analysis. Typical areas of application of such PILS-IC coupling are monitoring of pollutants inside build ings, emission control at the workplace, moni toring of ambient air, measurements of tunnel air, determination of stack emissions, analysis of fine dust or mobile use, e.g., on aircraft. Particle-Into-Liquid-Sampler «PILS» 1 «PILS» is a sample preparation module that samples aerosol particles from an airstream and transfers them to the aqueous phase. When it is combined with an ion chromatograph, it is possible to determine all water-soluble anions and cations in aerosols very easily at the same time. «PILS» puts aerosols into a supersaturated water steam phase, where they quickly grow into droplets. These droplets are separated out and transferred with a carrier solution into an ion chromatograph. The size of the aerosol particles to be determined can be limited by a preceding cyclone or impactor (e.g., PM 1, PM 2.5, PM 10 ). 1 «PILS» is a coproduction of Applikon Analytical B.V. and Metrohm AG

25 Monitor for Aerosols and Gases «MARGA» 2 MARGA is an online ion chromatograph that completely integrates sample preparation for gaseous samples. The system determines the entire water-soluble ionic load of aerosols and the gas phase. Anions and cations are measured in parallel. Compared with filter packs, the MARGA system is more economical to maintain and allows a better time resolution. A MARGA system provides exact hourly results, round the clock and seven days a week; and, if required, these can also be sent to any location via the Internet. The data can be used to establish trends, monitor pollution, examine movements of air masses and to study the day-night rhythm. The largest area of application is environmental research. Here, the MARGA system is used for online monitoring of environmentally relevant parameters such as SO x, NO x and NH 4 +. In this way it is possible to carry out extremely accurate analyses of climatic influences or of acid rain and also monitor local occurrences such as emissions from the burning of biomass. 25 The MARGA system simultaneously measures gases such as NH 3, HNO 2, HNO 3, HCl and SO 2 as well as the ionic load of aerosols such as NH 4 +, Na +, K +, Ca 2+, Mg 2+, Cl, NO 3, SO 4 2, SO 3 2, NO 2 and PO 4 3. The system operates autonomously. Solutions only need to be replenished once a week. 2 «MARGA» can be obtained through Metrohm s subsidiary Applikon Analytical B.V.

26 Inline Sample Preparation for Solids 26 Soliprep for LC Complete automation of all manual steps is a major aim in modern analysis. The goal is to achieve better precision and accuracy in the results and also ensure the tracea bility of each modification that the sample has been through. With the 815 Robotic Soliprep for Liquid Chro - ma tography, Metrohm offers you a modern solution for automation that achieves this aim. The 815 Robotic Soliprep is more than a sample changer. The instrument is able to homogenize, extract, dilute and filter your solid or liquid samples. The sample is then trans ferred directly to your IC or HPLC system. Depending on the requirements of the application, the 815 Robotic Soliprep offers enormous flexibility in the system configuration and integrates all manual sample preparation steps into a fully automated analysis system. The Soliprep IC system for inline sample preparation of solid samples.

27 27 Ion chromatography for solid samples With the 815 Robotic Soliprep, the scope of use of ion chromatography can also be extended to solid samples. Typical samples come from the pharmaceutical industry. But this system is also ideally suited to foods, feedstuffs and environmentally relevant samples such as sediments. Fully automated sample preparation saves time and costs while providing for more ease of use and better accuracy of results. Automated sample preparation: In the first step, solvent is added and the sample homogenized. After that, sample is drawn up with a metal-free needle, filtered and finally transferred directly to the IC system by way of a connection port.

28 Combustion IC «CIC» 28 Combustion IC is the modern combination of pyrolysis and ion chromatography. With this coupling, it is possible to analyze solids and highly viscous samples fully automatically. In contrast to previously employed methods (e.g., sample digestion with the oxygen bomb), no timeconsuming manual steps are needed in combustion IC. Even the supply of sample is automa tic. In addition, the method is characterized by excellent precision and a high sample throughput. The principle of combustion IC is as follows. In a fully au tomated process the samples are pyrolyzed in the com bustion unit under an argon-oxygen atmosphere. The resulting gaseous compounds are passed into an absorption solution, which is then transferred inline to a Metrohm IC system, where it is injected. Combustion IC is used for quality control of raw materials, intermediates and finished products of pharmaceuticals and electronic components as well as for a variety of samples from environmental research. Additionally, samples from the plastics industry, as well as fuels such as gasoline, biodiesel, crude oil, heating oil and coal can be analyzed with this technique.

29 Combustion IC at a glance: Fully automatic sample preparation for solids and liquids during sample delivery and subsequent ion chromatographic analysis Simultaneous determination of sulfur and halogens Differentiated determination of the concentrations of various halogens Material tests with regard to halogen-free products (RoHS) High sample throughput High precision and accuracy 29 Configuration of a Combustion IC system. The sample is pyrolyzed at a maximum temperature of 1200 C in the combustion unit. The resulting gaseous compounds are passed into an absorption solution, which is transferred inline to an ion chromatograph.

30 Ordering information 30 Depending on your application, we can offer you different ProfIC systems. These are completely automated Metrohm Inline Sample Preparation methods combined with an 850 Professional IC, an intelligent conductivity detector and an 858 Professional Sample Processor. In addition, the package includes all peripheral devices and accessories that are required for the particular technique. Professional IC system with Inline Ultrafiltration Professional IC system with Inline Dialysis Professional IC system with Inline Dilution (MIDT) Professional IC system with Inline Dilution with Inline Ultrafiltration Professional IC system with Inline Dilution with Inline Dialysis Professional IC system with intelligent Partial Loop Injection Professional IC system with Inline Extraction Professional IC system with Inline Matrix Elimination Professional IC system with Inline Matrix Elimination with Inline Calibration Professional IC system with Inline Matrix Elimination with Inline Spiking Professional IC system with Inline Neutralization Professional IC system with Inline Neutralization with Inline Calibration Professional IC system with Inline Neutralization with Inline Spiking Professional IC system with Inline Cation Removal Professional IC system with Inline Cation Removal with Inline Calibrationg Professional IC system with Inline Cation Removal with Inline Spiking Professional IC system with Inline Preconcentration (MiPCT) Professional IC system with Inline Preconcentration with Inline Calibration Professional IC system with Inline Preconcentration with Inline Spiking ProfIC 2 Anion ProfIC 2 Cation ProfIC 2 AnCat ProfIC 3 Anion ProfIC 3 Cation ProfIC 4 Anion ProfIC 4 Cation ProfIC 6 Anion ProfIC 6 Cation ProfIC 7 Anion ProfIC 7 Cation ProfIC 15 Anion ProfIC 15 Cation ProfIC 15 AnCat ProfIC 7 Anion ProfIC 7 Cation ProfIC 8 Anion ProfIC 8 Cation ProfIC 9 Anion ProfIC 9 Cation ProfIC 9 Anion ProfIC 9 Cation ProfIC 10 Anion ProfIC 11 Anion ProfIC 11 Anion ProfIC 10 Anion ProfIC 11 Anion ProfIC 11 Anion ProfIC 5 Anion ProfIC 5 Cation ProfIC 9 Anion ProfIC 9 Cation ProfIC 9 Anion ProfIC 9 Cation

31 Of course, you can also put your ion chromatography system together according to your own particular requirements: 31 Ion chromatograph 850 Professional IC 881 Compact IC pro 882 Compact IC plus For detection, an intelligent conductivity detector or an alternative detector can (for example, a UV/VIS or amperometric detector) are used. Automation Professional Sample Processor Professional Sample Processor Pump Professional Sample Processor Pump Valve IC Equipment for dialysis IC Equipment for ultrafiltration IC Equipment for dilution IC Equipment for Rinsing Station IC Equipment for Liquid Handling with Dosino Liquid Handling Extension Module Sample Prep Extension Module Liquid Handling Dosino Dosing Unit 2 ml Dosing Unit 5 ml Dosing Unit 10 ml Dosing Unit 20 ml Dosing Unit 50 ml Inline Sample Preparation for gaseous samples Particle-Into-Liquid Sampler ADI Peristaltic pump, 8 channels with 6 rollers Liquid Handling Set for PILS MARGA systems can be ordered via Applikon Analytical B.V. Inline Sample Preparation for solid samples Robotic Soliprep for LC Combustion digestion unit and its sample changers are available from PAC and Mitsubishi Chemical Corporation.

32 Subject to modifi cations Layout by Ecknauer+Schoch ASW, printed in Switzerland by Metrohm Ltd., Herisau EN