Environmental analysis

Quality control of water, soil, and air

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Metrohm ...
is the global market leader in titration is the only company to offer a complete range of ion analysis equipment 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 provides you with unparalleled application expertise offers you more than 1300 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 environmental analysis for water, soil, and air samples
The importance of environmental analysis The rapid growth in the world population has led to sharp increases in the consumption of energy and resources mi cals. and in the production of consumer goods and che It is estimated that there are a total of 17 million chemical compounds on the market, including as many as 100,000 that are produced on a large industrial scale. The effects of human activities on the environment are complex and call for sensitive analytical methods and powerful analytical instruments. As a leading manufacturer of instruments for chemical ana lysis we know about these challenges. We offer you state-of-the-art instruments and systems, with which you can monitor the composition of your water, soil, and air samples. You can count on our know-how Metrohm offers you complete solutions for very specific analytical issues. Your Metrohm contacts are professionals, who develop customized applications for you and pro vide you with professional support in all matters concerning environmental analysis. Discover on the following pages the solutions Metrohm offers for analysis in the environmental compartments water, soil, and air.

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Selected methods from the field of environmental analysis 04

Substances introduced into the environment are distributed among the environmental compartments water (hy drosphere), soil (pedosphere), rock (lithosphere), and air (atmosphere), as well as among the organisms living on them (biosphere). Only if we know the type and quantity of these contaminants can we protect the environment and its inhabitants. This requires internationally accepted standards, in which limits and test methods are defined. Metrohm instruments comply with numerous environmental standards. The following list contains a selec tion broken down according to environmental compartments. I. Water As its physical state changes, water passes through all spheres. It is the most frequently analyzed environmental compartment and is also the easiest, because unlike air or soil it already exists in the liquid phase. If drinking water samples are to be analyzed, sample preparation is usually not necessary; however, it is usually unavoidable in the case of wastewater samples.

Parameter Standard Matrix Method Page ISO 8467 Drinking water Permanganate index Titration 6 DIN 38409-5 Surface water ISO 6060 Drinking water, Chemical oxygen demand ISO 15705 Seawater, Titration 7 (COD) ASTM D 1252 Wastewater DIN 38409-44 DIN 38406-3 Ca, Mg Drinking water Titration 8 EPA 130.2 Sulfide ASTM D 4658 All types of water Titration ASTM D 3868 Drinking water Titration 9 Fluoride EPA 340.2 Wastewater Titration, Ion-selective Electrode (ISE) Free chlorine EPA 330.1 All types of water Titration DIN EN ISO 10304-1 All types of water Anions, e.g., F , Cl , Br , EPA 300.0, Part A Drinking and wastewater Ion chromatography 10 NO2, NO3, SO42, etc. EPA 300.1, Part A Drinking water EPA 9056 Drinking and wastewater Chromium(VI), anions DIN EN ISO 10304-3 All types of water Ion chromatography ASTM D 5257 All types of water Chromium(VI) Ion chromatography EPA 218.7 Wastewater ISO 11206 Drinking water ASTM D 6581 Drinking water DIN EN ISO 10304-4 All types of water DIN EN ISO 15061 Drinking and mineral water Ion chromatography Oxyhalides 11 EPA 300.0, Part B Drinking and wastewater EPA 300.1, Part B Drinking water EPA 317.0 Drinking water EPA 326.0 Drinking water Cations, e.g., Li+, Na+, K+, NH4+, ISO 14911 Surface and drinking water Ion chromatography 2+ 2+ Mg , Ca , etc. ASTM D 6919 Wastewater Amines (MMA, guanidine) Wastewater Ion chromatography 12 Bromate EPA 321.8 Drinking water Ion chromatography (IC-ICP/MS) Bromate, halogenated acetic acids EPA 557 Drinking water Ion chromatography (IC-MS/MS) EPA 314.0 Perchlorate Drinking water Ion chromatography 13 EPA 332.0 Hg, As, Cr EPA 6800 Hydrosphere, Ion chromatography (IC-ICP/MS) Biosphere Zn, Cd, Pb, Cu, Tl, Ni, Co DIN 38406-16 Drinking and wastewater Voltammetry II III VI Cd, Pb, Cu, Fe /Fe , Cr Seawater Voltammetry 15 Sample preparation acc. CN Drinking and wastewater Voltammetry to DIN 38405-13 Groundwater, raw water, U DIN 38406-17 Voltammetry drinking water EDTA, NTA DIN 38413-5 Wastewater, sludge Voltammetry Anions, cations, VoltIC (Voltammetry and Various All types of water 16 heavy metals ion chromatography) pH value, conductivity, TitrIC (Titration and Various All types of water 17 anions, cations ion chromatography) Drinking water, pH value, conductivity, Boiler feed water, and parameters that can Process-dependent Online and atline Cooling water, 19 be determined by titration specifications process analysis Process water, or voltammetry Wastewater Further standard-compliant methods for water analysis can be found in the brochure water analysis (8.000.5027EN).

II. Soil The soil is a multiphase system in which the hydrosphere, atmosphere, lithosphere, and biosphere exist side by side. It serves as a source of water and nutrients for plants, is a habitat for a large number of organisms, and is an im portant carbon sink. Harmful soil pollutants can easily

enter the human body through plants and animals. The constituents of soil are very difficult to access and difficult to mobilize. Sample preparation usually involves extraction and digestion procedures.

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Parameter Standard Matrix Method Page pH value ISO 10390 Soil pH measurement 22 Conductivity ISO 11265 Soil Conductivity measurement 23 Total organic carbon Soil Titration 24 (TOC) Cyanide ISO 11262 Soil Continuous flow analysis 25 Anions, e.g., F, Cl Soil Titration Anions EPA Method 9056 Solid waste Ion chromatography Perchlorate EPA Method 6860 Soil Ion chromatography Solid waste ISO 15192 DIN EN 15192 Soil Ion chromatography 26 Chromium(VI) EPA 3060A EPA 7199 Anions and cations Soil Ion chromatography 27 ISO 11466 Soil Voltammetry Trace elements ISO 19730 28 Organophosporus pesticide AOAC 970.53 Soil Voltammetry residues

III. Air The atmosphere is an important thermal buffer against space, and protects the earth from cosmic radiation. It is the place where clouds are formed and water is present there in all its physical states. Thus it is a hete ro geneous mixture of finely dispersed, solid or liquid par ticles in a gas (air). Its constituents are characterized by extreme

bility, enter our organism easily through breathing, mo and influence the climate and weather. Filter methods, and aerosol and gas collectors bring the constituents of air into the aqueous phase, which is preferable for che mical analysis.

Parameter Standard Matrix Saccharidic tracers Particulate matter ISO 16740 Workplace air Chromium(VI) ASTM D 6832 Pb, Cd, Zn, Cu Particulate matter Anions and cations Particulate matter Pb, Cd, Zn, Cu Particulate matter Anions and cations Particulate matter Pb, Cd, Zn, Cu Hydrogen chloride DIN EN 14791 Emissions, Chimneys Sulfur dioxide DIN EN 14791 Emissions, Chimneys Nitrogen dioxide DIN EN 16339 Ambient air

Method Ion chromatography, filter Ion chromatography, filter Voltammetry, filter Ion chromatography, PILS* Voltammetry, PILS* Ion chromatography and voltammetry, PILS* Ion chromatography, MARGA* Ion chromatography, MARGA* Ion chromatography, MARGA*

Page 31 32 33 35 36 38

* PILS is a semicontinuous aerosol sampler that is coupled to one or two analyzers (e.g., IC and/or VA); MARGA is the combination of aerosol and gas sampler including ion chromatographs.

I. Water 06 Titration
Sum parameters usually characterize similar chemical, physical, physicochemical or biological features of different components. Their advantage is in the fast determination and informative value, which allow the sample to be evaluated quickly. Thus, for example, electrical conductivity provides valuable information on the salt content of a water sample. Another important sum parameter is the chemical oxidizability of water components, which provides indications of the type and quantity of organic material present in the sample. According to the oxidizing power of the oxidizing agents used, a distinction is made between the permanganate index and the chemical oxygen demand (COD). While the permanganate index is the more informative parameter for samples with minimal or low contamination, COD is suitable for severely contaminated samples. Permanganate index according to DIN EN ISO 8467 The permanganate index determines the easily oxidizable fraction of the organic constituents in water and is used, in a broader sense to evaluate the or ga nic chemical contamination in waters with minimal or low contamination, such as drinking water samples. For determination, the water sample is heated for ten minutes with sulfuric acid and an excess of permanganate solution of known concentration in a boiling water bath. After that, the permanganate consumption is determined by adding an excess of sodium oxalate solution and back-titrating the consumed oxalate with permanganate solution. The per manganate index is expressed as the quantity of oxygen in mg/L that would be needed for oxidation.

The MATi13 system for fully automatic determination of the permanganate index

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The Mati12 system for fully automatic COD determination

Chemical oxygen demand according to DIN 38409-44 and ASTM D 1252 The chemical oxygen demand (COD) is a measured value for the sum of the substances in a certain volume of water that can be oxidized by chromate. Chromate is a much stronger oxidizing agent than permanganate, which is why it also oxidizes most organic compounds practically completely into CO2. In sewage treatment plants, COD is regarded as a valuable indicator for evaluating treatment performance. For volumetric determination of the COD, the sample of water is heated over a defined period with potassium dichromate. The remaining quantity of potassium dichromate is then back-titrated with ammonium iron(II) sulfate. The water constituents are oxidized either in a special COD heating device with reflux condensing or in a closed reaction vessel with an external heat source. Titration takes place directly in the reaction vessels without the need to transfer the content to other vessels. This prevents any sample losses and saves valuable time, especi ally when there is a high sample throughput.

Automation solutions from Metrohm Manual determination of the permanganate index and COD involves a great deal of work and, because the in dividual manual steps are difficult to reproduce, usually means inaccurate results. Metrohm solves this problem with a fully au tomated system in which tiamoTM titration software controls all the individual steps from sample preparation and the addition of the various solutions right through to the recording and archiving of data. Identical sequences guarantee unique reproducibility. New applications can be added to the freely configurable systems at any time, no matter whether they are for the determination of the pH value, conductivity, acid capacity, or for coupling with an ion chromatograph. Thus, it is possible to adapt any standard system individually to the particular task in the laboratory.

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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 (carbo nate hardness) and permanent hardness (sulfate hardness). Another important parameter includes the total hardness that represents the sum of the dissolved alcaline 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 Na2EDTA as titrant and a Ca2+-selective electrode.

Combined polymer membrane electrode for calcium determination

Chloride Chloride ions are determined by potentiometric titration with AgNO3 as titrant and a combined Ag-ring electrode, the Ag Titrode, following prior pH adjustment with nitric acid. The maintenance-free Ag-Titrode uses a pH glass membrane as reference electrode, which means that no refilling of electrolyte is required.

The Ag-Titrode for chloride determination

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Fluoride (ASTM D 3868) and sulfide (ASTM D 4658) Sulfide and fluoride ions are determined by ion-selective electrodes. For fluoride determination, a buffer substance is added to the sample. This buffer substance both maintains the ionic strength, regulates the pH value and complexes in ter fering aluminum and iron(III) ions. To measure sulfide, a buffer is added. This both regulates the pH value and prevents the oxidation of sulfide by at mospheric oxygen.

Automation greater efficiency and reproducibility With Metrohms titrators and automation solutions, it is possible, upon request, to offer any fully automated titration system, no matter whether the requirement is for de termination of a single parameter or several parameters in one sample run (e.g., pH value, conductivity, alkalinity, and total hardness). But that is not all: the tiamoTM titration software also allows numerous thirdparty devices to be incorporated for example, for de ter mining turbidity according to DIN EN ISO 7027 or for determining color according to DIN EN ISO 7887.

Ion chromatography 10
Modern ion chromatography (IC) allows efficient separation and determination of inorganic and low-molecular organic anions and cations. Various separation mechanisms and types of detection as well as the possibility of automated sample preparation make IC a proven routine method in water and environmental analysis. Oxyhalides and standard anions in drinking water (EPA 300.1) Chlorate, chlorite, and bromate are by-products that are formed by oxidation of the halides when drinking water and mineral water are disinfected. Their concentration needs to be monitored on account of their suspected car cin o genic properties. Before injection, the samples pass through the ultrafiltration cell mounted directly on the 858 Professional IC cessor. Sample preparation and analysis are fully Sample Pro automatic. The equipment is controlled, the data collected and managed, and the system monitored by the intelligent MagIC NetTM chromatography software. The clear symbols, well laid-out presentation, and intuitive operation make analysis remarkably easy.

chloride; 11 mg/L

nitrate; 12 mg/L

2.4 2.2

Conductivity [S/cm]

2.0 1.8 1.6 1.4 1.2 1.0 0 2 4 6

fluoride; 95 g/L

bromide; 47 g/L chlorate; 18 g/L dichloroacetate; 500 g/L

chlorite; 10 g/L bromate; 11 g/L

10

12

14

16

18

20

22

24

phosphate 100 g/L

nitrite; 40 g/L

26

28

sulfate; 8 mg/L

30

Time [min]
Drinking water sample, spiked with 10 g/L of each ClO2, BrO3, ClO3, 40 g/L of each NO2, Br, 100 g/L PO43, 500 g/L dichloroacetate; column: Metrosep A Supp 7 - 250/4.0 (6.1006.630); eluent: 3.6 mmol/L Na2CO3, 0.8 mL/min; column temperature: 45 C; sample volume: 20 L

Bromate in drinking water (EPA 326.0) Bromate forms during the ozonization of drink ing water. Several international standards stipulate detection limits and test methods. Depending on the required detection limit, different detection methods can be used. Conduc ti vity detection with chemical suppression allows the

de termination of bromate in the lower g/L range. In the ng/L range bromate can be detected by means of IC/MS coupling or post-column derivatization with potassium iodide and subsequent UV detection.

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3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 0

tap water sample spiked with 1 g/L bromate unspiked tap water sample
bromate

Intensity [mAU]

Time [min]
Spiked and unspiked drinking water sample; column: Metrosep A Supp 16 - 100/4.0 (6.1031.410); eluent: 100 mmol/L H2SO4, 19.3 mol/L ammonium molybdate tetrahydrate, 0.8 mL/min; post-column reagent: 0.27 mol/L KI, flow rate: 0.2 mL/min; column temperature: 45 C, wavelength: 352 nm; sample volume: 1000 L

Bromate determination: overview of test methods and detection limits (acc. to DIN 32645) EPA method Injection volume Detection limit Ultrapure water Drinking water* [L] [g/L] Conductivity detection with 300.1 100 0.130 0.390 chemical 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 KI; 326.0 1000 0.032 0.066 UV detection
*Drinking water matrix: 100 mg/L of each chloride, sulfate, and carbonate

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Aliphatic amines in wastewater Aliphatic amines are important starting materials and in termediate products in the chemical and pharmaceutical industries. They are used to produce solvents, crop protection agents, polymers, detergents, dyes, explosives, lubricants, and pharmaceuticals. Their use on a large in dustrial scale has led to significant discharges into aqua tic systems. Secondary amines, especially, are re gar ded as hazardous to waters, as they react even at trace concentrations with nitrite to form carcinogenic nitrosamines.

Short-chain aliphatic amines in industrial wastewaters can be determined easily on a cation-exchange column with subsequent conductivity detection. Not only important amines (methylamine, dimethylamine, trimethylamine, ethanolamines, guanidine, etc.), but also alkali metals and alkaline earth metals can be detected in a single de termination. There is no need for complicated deriva ti zation procedures, such as those in gas chromatography. Interfering particles, colloids, algae, or bacteria pre sent in many (waste)water samples are removed fully automatically by inline ultrafiltration before analysis.

-560
sodium; 20 mg/L ammonium; 10 mg/L

-565

Conductivity [S/cm]

-570

methylamine; 10 mg/L

-575

-580

-585

-590 0 1 2 3 4 5 6 7 8 9 10 11 12

Time [min]
Water sample spiked with wastewater-typical amines; column: Metrosep C 4 - 100/4.0 (6.1050.410); eluent: 1.7 mmol/L HNO3, 0.7 mmol/L dipicolinic acid, 5% acetone, 0.9 mL/min; sample volume: 10 L

aminoguanidine; 5 mg/L

guanidine; 5 mg/L

Modern detection methods in IC Coupling IC with mass spectrometry (MS) and inductively coupled plasma mass spectrometry (ICP/MS) brings detection limits down to ultratrace levels. Whereas the great advantage of structure-specific IC/MS is that it is possible to identify compounds not only by way of their retention time but also on the basis of their MS spectrum (organic acids), IC-ICP/MS enables a distinction to be

made between the different oxidation states of one and the same element. This element species analysis is important for elements such as arsenic, chromium, mercury, selenium, and gadolinium, which occur as simple elemental and molecular ions or as polar and ionic coordination compounds, and display different toxicities, depending on their bonding.

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Separation and detection of arsenite, monomethylarsenate, dimethylarsenate and arsenate by IC-ICP/MS; column: Metrosep A Supp 15 - 150/4.0 (6.1030.420); eluent: 8 mmol/L ammonium nitrate, pH = 8.3, 0.7 mL/min; sample volume: 10 L; ICP/MS: without reaction and collision mode, m/z: 75

Further applications Analyte Bromate Perchlorate Anions and organic acids Amines Organic acids Acetate Propionate Butyrate Chromium(VI) Arsenic Selenium Mercury Gadoliniumcontaining MRI contrast agents Coupling IC/MS IC-MS/MS IC-ICP/MS IC/MS IC/MS IC/MS IC/MS EPA method EPA 557 EPA 321.8 EPA 332.0 EPA 6860 Remark along with other oxyhalides along with haloacetic acids and dalapon after removal of haloacetic acids in water and soil samples parallel determination in various matrices very sensitive determination in water samples occur in process water along with a high salt matrix

IC-ICP/MS IC-ICP/MS IC-ICP/MS IC-ICP/MS IC-ICP/MS

EPA 6800 EPA 6800 EPA 6800

speciation analysis speciation analysis speciation analysis isotope dilution mass spectrometry analysis of gadolinium chelates (Gadovist, Magnevist, etc.) and free gadolinium ions

Voltammetry 14
Voltammetric trace and ultratrace analysis of drinking water, groundwater, surface water, seawater and waste water is used to determine electrochemically active inor ganic ions. It is frequently employed to complement and validate spectroscopic methods. Its features are: compact equipment, relatively low investment and running costs, simple sample preparation, short analysis times, and high accuracy and sensitivity. Speciation analysis Another advantage of voltammetry is the possibility to distinguish bet ween different oxidation states of metal ions (speciation) as well as between free and bound metal ions. This pro vides important information regarding the bioavailability and toxicity of heavy metals. Determination of the complexation capacity Natural waters often contain dissolved organic compounds that complex heavy metals and thus change bio availability and toxicity of the latter. The parameter used to quantify the organic ligands in a sample is the complexation capacity; it indicates the amount of heavy metal ions which is barely complexed. Determination is achieved by voltammetric titration. After each addition of me tal tit rant, a voltammogram is registered. Plotting the currents of the respective peak heights versus the metal concentration provides a titration curve from which the complexation capacity is deduced. Versatile application areas Voltammetry is especially suitable for laboratories in which only a few parameters have to be monitored with a moderate sample throughput. Important fields of application include environmental monitoring, limnology, hy dro gra phy, oceanography, marine biology, and soil science. 797 VA Computrace The 797 VA Computrace is a modern, user-friendly allround measuring stand that enables accurate and sensitive determination of metal and nonmetal traces with the help of voltammetric and polarographic methods.

Detection limits Element Detection limit [ng/L] Antimony SbIII/SbV 200 Arsenic AsIII/AsV 100 Bismuth Bi 500 Cadmium Cd 50 Chromium CrIII/CrVI 25 Cobalt Co 50 Copper Cu 50 II III Iron Fe /Fe 50 50 Lead Pb Mercury Hg 100 Molybdenum MoIV/MoVI 50 50 Nickel Ni Platinum Pt 0.1 Rhodium Rh 0.1 Selenium SeIV/SeVI 300 50 Thallium Tl Tungsten W 200 Uranium U 25 Zinc Zn 50

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Many toxic transition metals and a few anions can be de termined voltammetrically, with a high degree of sensitivity and without prior sample preparation, in drinking water and groundwater. Here are a few relevant examples: Nickel and cobalt These metal ions must be determined regularly in water samples. DIN 38406 Part 16 describes the determination of these ions in different types of water.

Cyanide Apart from heavy metals, voltammetry can also be used for trace analysis of a few anions. For example, free cyanide in a concentration range of 0.01...10 mg/L can be determined easily and reliably even in sulfide-containing solutions with a large excess of phosphate, nitrate, sulfate, and chloride.

-150 Ni -125

-100

I [nA]

-70

-50 Co -25

0 -0.80

-0.90

-1.00

-1.10

-1.20

-1.30

U [V]
Voltammetric determination of nickel and cobalt in sea water according to DIN 38406-16

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The fully automatic VoltIC pro consists of several 800 Dosinos, a 797 VA Computrace, an 858 Professional Sample Processor, and an 850 Professional IC AnCat (from right to left).

VoltIC pro Voltammetry and ion chromatography

VoltIC pro combines voltammetry (VA) and ion chromatography (IC) in a single system and permits the fully automatic analysis of anions, cations, and heavy metals. The necessary sample preparation steps are performed by sharing the same liquid handling system and sample changer, which directs the samples to the VA analyzer and the ion chromatographs. VoltIC pro can be controlled with just one software. All the results are filed in a single database and can be converted into an easily readable report by pressing a button. VoltIC pro is very flexible and can be easily adapted to a wide variety of requirements in the analytical laboratory. Available Metrohm instruments (IC and VA) can be easily extended to a VoltIC pro system.

The VoltIC Report: All the results at a glance

TitrIC pro Titration and ion chromatography

TitrIC pro stands for a unique combination of direct mea surement, titration, and ion chromatography and permits the fully automatic determination of temperature, conductivity, pH as well as p and m value, alkalinity, total hardness and numerous ion concentrations. Just as in the VoltIC pro system, the analysers use the same liquid hand ling instruments, a common sample changer, and the same database. The system is controlled by the master software MagIC NetTM, while the titration software tiamoTM runs in the background. TitrIC pro has impressively short analysis times, uses little space and gives high precision results. TitrIC pro comes in three versions the basic, ad van ced and high end systems. All three systems determine temperature and conductivity, pH as well as p and m value, and analyse anions by ion chromatography. In the basic system, TitrIC pro I, the content of Ca and Mg is measured by titrimetry. In TitrIC pro II and TitrIC pro III, cations are determined by ion chromatography. In addition, TitrIC pro III has a sample changer with the DisCover function for the automatic removal of the lid of the sample vessel. If required, additional determinations can be integrated into the TitrIC pro systems.

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The High-End-System TitrIC pro III consists of 856 Conductivity Module, two 800 Dosinos, an 802 Stirrer, a 905 Titrando, and 815 Robotic USB Sample Processor XL and the 850 Professional IC for anions and cations.

Potentiostats and galvanostats 18

Energy from wastewater: the microbial fuel cell Like all living beings, microorganisms meet their energy requirements by breaking down energy-rich substances. Humans make use of this in sewage treatment plants, where bacteria mineralize the organic pollutant load to a large extent. The microorganisms release electrons, which they transfer to electron acceptors such as oxygen, nitrate, and sulfate. If this transfer of electrons is from a mediator i.e., an electron bridge to a solid elec tron receptor such as an anode, an electric current will flow, provided there is also a cathode and a power consumer. This way, bacterial energy is directly converted to electrical energy. It is essential that the bacteria are in di rect contact with the electrode in the form of a biofilm.

Initial results show that the degradation of pollutants in wastewater can be used to recover energy. The target is energy-neutral wastewater purification. For this, however, the electron transfer processes still need to be optimized, e.g., by increasing the size of the electrode surface. At present, work is being done with electrodes made up of countless conducting carbon fibers on which the bacteria sit. The electrochemical impedance spectroscopy ca pabilities of the Autolab PGSTAT128N with FRA32M module allow the electron transfer kinetics and interfacial properties to be monitored.

www.metrohm-autolab.com

Online and atline analysis systems from Metrohm Applikon

Online and atline Process Analyzers from Metrohm Applikon are the preferred solution for process monitoring in a wide range of industries. Using the complete range of modern ion analysis (pH value, conductivity, and redox potential titration, KF titration, photometry, ISE measurecess ments, and voltammetry) Metrohm Applikon Pro Ana lyzers pro vide high precision results for any wet-che mical parame ters you need right at your production line. Metrohm Applikon has specialized in online and atline process analysis for over 35 years. With this vast experience, we offer a wide range of analyzer products and integrated systems for diverse applications and industries to meet the challenging requirements and demands of your process. Metrohm Applikon is part of the Metrohm Group and represented in over 35 countries. Our regional and local presence offers knowledgeable support in sales, applications, project engineering and start-up. We intend to be your pro cess monitoring partner for years to come.

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Offline lab analysis Manual sampling Sample transport to the lab Sample registration and analysis in the lab

Atline analysis Manual sampling Continuous manpower needed Automated lab analysis close to sampling point inside plant Ideal where mutiple samples have to be taken at several sampling points along the process

Online analysis In-process measurement & response Automated sampling & registration Automated sample preconditioning Automated lab analysis Fast feedback of results Very limited manpower needed Close loop control

Process analysis 20
Customized online and atline process control Because of the outstanding dissolving properties of wa ter a large number of organic and inorganic compounds accumulate in it. This requires powerful analysis that mo ni tors the composition of the water continuously. With the process analyzers from Metrohm Applikon this is possible 24 hours a day, 7 days a week. The analyzers are used directly on-site, as close as possible to the process, and run without any operator intervention. More over, it makes no difference whether a single parameter is to be determined in a single sample stream or several different parameters are to be determined simultaneously in complex, multiple sample streams whatever your requirement, Metrohm Applikon can offer you an appropriate online or atline analyzer. Proven wet-chemistry methods All analyzers are based on wet-chemical analysis techniques such as titration, colorimetry, or ion-selective elec t rode measurements. Most of the well-established laboratory methods for water analysis can be easily transferred to the analyzers. In online analysis, sampling and sample preparation are at least as important as the analyzer itself. Metrohm Applikon has a lot of expertise in this area and configures custom-made sampling systems, for example, for filtration, sample taking from pressur ized containers or degassing. Straightforward network integration The analyzers are all equipped with possibilities for digital as well as analog outputs. Results, for example, can be as alarms can be transferred via 4...20 mA outputs, where transmitted via the digital outputs. Digital inputs, in turn, can be used for remote start-stop purposes. Alert range of analyzers The Alert analyzers are either based on colorimetric or ion-selective electrode (ISE) methods. The ISE methods are generally used for measurements in the ppm and percent range, whereas the colorimetric techniques are used for the ppb to ppm range. Some typical applications for the Alert analyzers are: Sodium and silica in power plants Both sodium and silica play a major role in corrosion processes that occur in cooling water systems. For power plants, it is essential to monitor the concentrations of these species. With the Alert Ion Analyzer equipped with the Metrohm Na+ ISE, it is possible to measure sodium concentrations down to 1 ppb. If lower detection limits are required, the Alert analyzer can be replaced by the more accurate ADI 2018 analyzer. Silica in cooling water or high-purity water can be determined with the Alert Colorimeter at concentrations as low as 1 ppb.

www.metrohm-applikon.com
ADI 2045TI the flexible analyzer for online applications

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Chemical oxygen demand The chemical oxygen demand (COD) is one of the most important sum parameters for assessing wastewater pollution. Metrohm Applikon offers both titrimetric determination, described already on page 7, and also colorimetric determination: depending on the required detection limit, continuous COD determination can be performed by either the ADI 2045TI or the ADI 2019 online analyzer. Heavy metals, phosphates, nitrates, and COD in wastewater Numerous parameters need to be continuously monitored in industrial and municipal wastewaters. These in clude, for example, the heavy metals cadmium, lead, zinc, and cobalt, and also the anions nitrate, ammonium, phosphate, and sulfate. Metrohm Applikon has a wide range of analyzers available: while the ADI 2045VA is designed specifically for determining heavy metals, the ALERT analyzers ADI 201Y and ADI 2045TI perform the

lyses. In addition, Metrohm Applikon offers a other ana ber of sample preparation systems that can be large num combined with any application, no matter how unusual that application might be. Iron in drinking water The taste of drinking water depends to a large extent on its origin and treatment. Water contains different amounts of magnesium, iron, sulfate, and carbonate, de pending on whether it has passed through stone, clay or gravel sand. Low concentrations of iron below 2 mg/L, especially, have a significant effect on taste. Many water suppliers use sand filters to remove the iron. ALERT analyzers, developed specifically for water analysis, ensure continuous monitoring of the filter performance. Iron can be detected colorimetrically in the presence of a color indicator and this can be done every six minutes.

II. Soil 22 Determination of pH value and conductivity

The pedosphere is the name given to a highly complex boundary area where the lithosphere, hydrosphere, at mosphere and biosphere coexist. As a multiphase system, the pedosphere consists predominantly of soil mineral matter, approximately equal proportions of soil air and soil water, and a small amount of organic matter. The pedosphere forms the key basis of life for plants, animals, and humans. Harmful substances contained in it come mainly from weathering, cultivation, or the air. Soil pH value soil reaction according to ISO 10390 The pH value of a soil sample is the most frequently de termined parameter in soil analysis. It is the characteristic value of what is known as soil reaction and allows soils to be classified according to their acidity and alkalinity. Determination of the pH value provides information about the acid or base action of the soil solution. This in turn is enormously important for the nutrient supply and microbial activity of the soil. For example, many metals (trace elements) are considerably more mobile in acidic soils. If the soil pH values are very low, toxic levels can soon be reached and these can damage the roots of plants. On the other hand, excessively high pH values quickly lead to a shortage of trace elements because of immobilization. A simple method for determining the pH value is de s cri bed in ISO 10390. It describes the slurrying of an airdried and sieved (max. 2 mm sieve) soil sample with distilled water and subsequent measurement. Alter na ti vely, ex trac tion can be performed using 0.01 molar CaCl2 or 1 molar KCl. The cations in these solutions displace the protons that are absorbed on the ion exchangers of the soil as quantitatively as possible.

The flat membrane electrode is ideal for pH measurements in sediment-containing sample solutions.

The 827 ph lab for the laboratory

23

Determination of electrical conductivity in soil samples according to ISO 11265 The determination of conductivity provides qualitative formation about the amount of dissolved salts in the in soil. It allows conclusions about the ability of the soil water to mobilize mineral substances in the soil. To determine electrical conductivity, a weighed-out quan tity of a dried soil sample is shaken up with a de fined volume of distilled water and then measured directly.

Titration 24
Total organic carbon (TOC value) Dead soil organic matter is known collectively as humus. Humus does not form a homogeneous soil fraction, but exists in a variety of forms, depending on the degree of decomposition. It provides plants with nutrients and forms an important habitat for many soil-dwelling organisms. The most important component of humus is the total organic carbon (TOC), which is also used generally as a measure of the humus content. The determination of the TOC value of a soil sample is based on the Walkley-Black method. For this, an air-dried soil sample is treated (after determination of the water content) with a potassium dichromate solution to which sulfuric acid has been added. As a result, all the organic carbon constituents in the soil sample are oxidized. The unconsumed dichromate is then back-titrated with an iron sulfate solution.

Stand-alone Titrator 916 Ti-Touch for routine analysis

25

Important soil parameters overview Method Sample preparation Detection type pH value (ISO 10390) Slurrying Direct measurement pH value for the determina- Continuous pH control to Direct measurement tion of the leaching behavior determine the influence (with continuous eluate of inorganic components from of pH value on leaching analysis) behavior waste Conductivity (ISO 11265) Slurrying Direct measurement Total organic carbon Visually with barium (TOC), Walkley-Black K2Cr2O7/H2SO4 digestion diphenylamine sulfonate method Aluminium Extraction Visually, phenolphthalein Soil sample is shaken with Carbonate content, a) Photometrically with 0.2 mol/L HCl and allowed Piper method phenolphthalein to settle; 10 mL of the (also known as rapid titration b) phenolphthalein, supernatant solution is or acid neutralization method) SET titration to pH 7.8 back-titrated with NaOH a) Photometrically with Ion exchange with phenolphthalein Acidity Exchangeable acidity (H + Al) 1 mol/L KCl b) Potentiometrically, SET titration to pH 7.6 Total cyanide and easily a) Photometrically with Distillation phenolphthalein released cyanide (ISO 11262) b) Potentiometrically Soluble anions Extraction with CO2-free SET titration to carbonate/bicarbonate dist. Water pH 8.4 and 4.4 (alkalinity) Titrant

1 mol/L FeSO4 (acidic) 0.02 mol/L NaOH

0.1 mol/L NaOH

0.025 mol/L NaOH

0.005 mol/L AgNO3

0.1 mol/L HCl

Ion chromatography 26
Chromate(VI) in soil samples Chromium occurs primarily in the stable oxidation states Cr(III) and Cr(VI). The oxidation state determines the biological and toxicological properties, which could hardly be any more different: Cr(III) is one of the essential trace elements and plays an important role especially in the metabolism of fats and glucose, whereas hexavalent chromium is very toxic and carcinogenic. Chromium is present in different concentrations in all types of soil and rock. It usually occurs in the cationic and less bioavailable trivalent form; it can, however, also oc cur as toxic and very mobile chromium(VI) anion usually as a result of anthropogenic input. Because of the differences in toxicity, the total concentration of chromium is of less interest than the concentration of chromate.

Ion chromatography can detect chromate in the soil down to g/L levels. Here, the relatively large, doubly charged chromate anion is separated from the other anions on an anion-exchange column and then converted by post-column reaction with 1,5-diphenylcarbazide solution to form a reddish-violet complex that is analyzed at 540 nm with a UV/VIS detector. The sample preparation of soil samples is a demanding task. It is essential to ensure that the extraction solution releases the chromate from the samples without there being any change in the oxidation state of the chromate. For most soil samples, alkaline digestion according to EPA 3060A or ISO EN 15192 is recommended. Before ion chro matographic determination, filtering with 0.45 m filters is required. This can also be automated conveniently with the use of an inline ultrafiltration cell.

12

10

Intensity [mAU]

8 Chromium(VI); 6.9 mg/kg 6

10

11

12

13

Time [min]
Worked-up soil sample (2.5 g soil in 100 mL 0.25 mol/L NaOH/0.14 mol/L Na2CO3, then dilute with ultra pure water 1:10); column: Metrosep A Supp 5 - 250/4.0 (6.1006.530); eluent: 15 mmol/L Na2CO3, 10 mmol/L NaOH, 0.7 mL/min; sample volume: 100 L; post-column derivatization with 0.5 g/L 1,5-diphenylcarbazide, 10% methanol, 0.5 mol/L H2SO4, flow rate post-column reagent: 0.5 mL/min; UV/ VIS detection at 540 nm

27

Anions and cations in soil samples The nutrient content in soil samples determines plant growth and is of great importance especially with regard to agricultural use. Of prime interest here are the concentrations of the main nutrient elements (macronutrient elements) nitrogen, phosphorus, potassium, calcium, mag nesium, and sulfur.
chloride; 262.9 mg/kg

Ion chromatography with conductivity detection enables rapid determination of the nitrogen components nitrate, nitrite, and ammonium, and also of the ions sulfate, phosphate, calcium, magnesium, and potassium. Sample preparation includes aqueous extraction of the soil samples.

3.8 3.4 3.0

Conductivity [S/cm]

2.6 2.2 1.8 1.4 1.0 0.6 0.2 0 2 4 6 8

nitrate; 406.4 mg/kg

phosphate; 104.2 mg/kg

nitrite; 30.2 mg/kg

sulfate; 183.6 mg/kg

10

12

14

16

18

20

22

24

26

28

30

Time [min]
Anion determination in a worked-up soil sample, 10 g seed compost in 100 g water, then extract for 10 minutes in the ultrasonic bath, dilute with ultrapure water 1:10 (v/v) and then filter with 0.45 m filters and RP cartridges; column: Metrosep A Supp 5 - 250/4.0 (6.1006.530); eluent: 3.2 mmol/L Na2CO3,1.0 mmol/L NaHCO3, 5% acetone, 0.7 mL/min; column temperature: 30 C; sample volume: 20 L

Voltammetry 28
Trace elements and harmful pollutants in the soil The determination of the nutrient content in the soil re quires not only ion chromatographic analysis of the main nutrient elements, but also determination of the essential trace elements iron, manganese, zinc, and copper. This can be achieved very accurately and sensitively by voltammetry. Moreover, voltammetry is suitable for analyzing harmful heavy metals such as lead, cadmium, chromium, mercury, uranium, and zinc in the soil. In contrast to water analyses, ion analysis in soils is usually preceded by extraction or digestion to transfer the ions into the aqueous solution. Various sample prepara-

tion methods are described in standards (e.g., ISO 12914). The extracts obtained can usually be determined directly by voltammetry. Another application of voltammetry is the determination of organophosphorus pesticide residues, such as, for example, diazinon, malathion, parathion-methyl, and pa ra thion, according to AOAC 970.53. Through extraction with organic solvents the electrochemically active substances are separated from the soil matrix and then enriched by adsorption on the HMDE and determined by reduction.

Potentiostats and galvanostats

Analysis for the electroremediation of contaminated soils Soils contaminated with heavy metals and organic compounds represent a serious risk to the environment, which is why cost-effective and environmentally compatible re mediation of contaminated sites is becoming in creas in gly urgent. In situ methods where contaminated soils are treated without being excavated are the state of the art. A very promising method is electroremediation (also known as electrochemical remediation), where se ries of anodes and cathodes installed in the soil body and connected to a direct-current source induce an electrical field, under the influence of which electrokinetic transport and redox processes take place. As a result, heavy metals are reduced on the cathode and harmful organic

29
substances, such as phenols, aromatic amines, or haloge nated hydrocarbons, are oxidized on the anode. Elec tro remediation is ideal for fine-grained clay, loam, or silt soils with a high water-retention capacity, where other in situ remediation techniques usually fail. The first Autolab potentiostats/galvanostats were developed exactly two decades ago for this type of application. By combining a PGSTAT128N potentiostat/galvanostat (cyclic voltammetry and galvanostatic analysis) and a booster it is possible to track the redox reactions the oxidation of organic compounds and the reduction of heavy metals taking place in the soil body.

Autolab PGSTAT128N with BSTR10A 10A Current Booster

www.metrohm-autolab.com

30

III. Air
On average about 300,000 m3 air pass through a persons respiratory system in the course of a lifetime. In this way, impurities in the atmosphere directly enter the lungs. Especially dangerous are the aerosols that contain particles with diameters of less than 10 m also know as particulate matter. These are airborne heterogeneous mixtures of substances made up of minute particles, some of which are solid and some liquid. The smaller these particles are, the deeper they go into the lungs. Once they reach the place where the gas exchange occurs, the pulmonary alveoli, there is just one micron of tissue between them and the blood stream. Aerosols come both from natural sources (volcanic eruptions, sea spray, desert dust, fire, biogenic input) and from anthropogenic sources (burning of fossil fuels, industrial production). By reflecting sunlight and acting as condensation seeds for cloud formation, they influence our climate and weather. The chemical composition of aerosols is highly complex and not yet fully understood. To estimate the effects of aerosols on health and climate, it is essential to know their chemical composition. Sampling is done using two different types of aerosol collector. The first type are filter collectors that are based on the deposition of suspended particles on surfaces; they usually require a pump, are operated in offline mode, and supply data over prolon ged ac cumulated periods. The second type are powerful aerosol collectors such as PILS or MARGA that work primarily in online mode and provide semicontinuous data.

Filter methods
The particulate matter contained in the air is collected on filters with a certain air flow over a defined period of time. Sampling is usually in accordance with DIN EN 12341. The composite air samples of particulate matter are extracted and the extract is then analyzed using ion chromatography (IC) or voltammetry (VA). Saccharidic tracers in particulate matter by IC The anhydrosugars levoglucosan, mannosan, and galactosan are produced when cellulose and hemicellulose are burnt and act as tracers for the combustion of biomass. By contrast, the sugar alcohols arabitol and mannitol are tracer substances for biological processes: when fungi fling spores into the air, the concentration of mannitol in the aerosol increases. Studies in the Amazon rain forest showed that the biogenic fraction consisted of fungal spores and formed up to 50% of the ambient aerosol. Thus, concentration profiles of these saccharidic tracers make it possible to obtain indications of sources of aerosols. For example, analysis of the saccharide composition in summer filters shows a significantly higher proportion of sugar alcohols. In winter filters, by contrast, there is a predominance of anhydrosugars, especially levoglucosan. Following direct water extraction by the aerosol filters, the saccharidic tracers are separated by ion chromatography and determined reliably down to lower ng/m3 levels by way of pulsed amperometric detection (PAD). The IC-PAD method requires no derivatization, can be automated easily and is suitable for routine use with large sample series.

31

Determination of saccharidic tracers in filter extracts from a) a winter filter and b) a summer filter; ultrasound-assisted extraction with ultrapure water; columns: Metrosep A Supp 15 - 150/4.0 (6.1030.420) coupled to Metrosep Carb 1 - 150/4.0 (6.1013.010); eluent: 70 mmol/L sodium hydroxide, 0.65 mL/min; column temperature: 32 C; sample volume: 100 L; PAD measuring mode (gold working electrode), measuring time: 100 ms

32

Chromium(VI) in the particulate matter of indoor air IC method according to ASTM D 6832 When breathed in, water-soluble chromium(VI) particles in the PM2.5 fraction pass all the way through to the pulmonary alveoli. There they penetrate the extremely thin tissue and enter the liver and kidney cells by way of the blood plasma. Starting out from the red cells, Cr(VI) thus interacts with the cellular protein molecules of the DNA. Like other carcinogenic compounds, chromium(VI) is subject not to an occupational exposure limit, but to the ALARA principle of minimization (as low as reasonably achievable). It requires the emissions of carcinogenic substances to be reduced to the minimum. This calls not only for speciation analysis, but also for detection limits in the low g/L range.

The method described in ASTM D 6832 for chromium(VI) determination in the particulate matter of indoor spaces describes an ion chromatographic separation of the chromium(VI) species with post-column derivatization and spectrophotometric detection. The sampling and sample preparation techniques chosen are such that no transformation occurs between trivalent and hexavalent chromium compounds. Furthermore, a distinction can be made between soluble and insoluble chromium(VI) compounds by choosing the appropriate extracting agent.

26 24 22 20 chromium(VI); 390 g/L

Intensity [mAU]

18 16 14 12 10 8 6 4 2 0 0 1 2 3 4 5 6 7

10

11

12

Time [min]
Determination of the insoluble chromium(VI) content in filter extracts of an air sample; ultrasound-assisted extraction with 3% Na2CO3 and 2% NaOH with a subsequent 1:1 (v/v) dilution of the extract; column: Metrosep A Supp 10 - 250/4.0 (6.1020.030); eluent: 0.25 mol/L (NH4)2SO4, 0.05 mol/L NH4OH, 0.6 mL/min; column temperature: 25 C; sample volume: 1000 L; post-column derivatization with 2 mmol/L 1,5diphenylcarbazide, 10% methanol, 0.5 mol/L H2SO4; flow rate post-column reagent: 0.2 mL/min; UV/VIS detection at 540 nm

33

Heavy metals in the particulate matter by voltammetry The heavy metals (e.g., lead, cadmium, and zinc) contained in particulate matter and dust deposits not only act directly on the respiratory system through inhaled air, but can also accumulate in soil and water as a result of wet and dry deposition from the air and thus enter the food cycle, and from there make their way into the or ga nism. Apart from having a carcinogenic effect, heavy me tals damage especially the kidneys, liver, nervous system, and cardiovascular system. Although the ambient air concentrations of heavy metals have decreased considerably since the ban on leaded gasoline, particulate matter samples from sites exposed to traffic and industry still show noticeable amounts of lead, arsenic, and cadmium. Directive 2008/50/EC of the European Parliament and of the Council on ambient air quality and cleaner air sets limits and targets for various concentrations of harmful substances in the air. With the help of voltammetry, heavy metals in the air can be determined right down to trace levels.

Semicontinuous methods 34
PILS Particle Into Liquid Sampler Compared with the filter methods, the Particle Into Liquid Sampler (PILS) allows a much higher time resolution. Semi continuous measurements are possible approximately every 15 minutes. This high time resolution allows changes in the aerosol composition to be correlated with meteorological and other data. Furthermore, there is no need for complicated and error-prone manual sample preparation, and no hassle of storing samples. The way PILS works is simple. At the intake a size-selective cyclone limits the particle size of the aerosols to a maximum of 1, 2.5 or 10 m (PM1, PM2.5, PM10), as requi red. The aerosols then enter a condensation chamber, where they meet a supersaturated water vapor phase. Within a very short time they grow into droplets, are se parated out, and transported to the ion chromatograph or the voltammetric measuring cell by a carrier fluid.

PILS can be connected directly to a wide range of analyzers. Apart from coupling to ion chromatographs and vol tammetric measuring stands, which is described in this brochure, coupling to TOC or ICP analyzers is also widespread. Whereas the former determines the total organic carbon in the aerosol, ICP is used for multi-element ana lysis. Offline sampling with an autosampler is also possible. Semicontinuous determination of anions and cations by PILS-IC Coupling with ion chromatography allows climate-related water-soluble anions and cations in the aerosol to be determined. This enables important conclusions to be drawn about the precursors and thus about the question of whether particles are emitted directly as in the case of the primary sea salt aerosols (NaCl) or whether the materials are secondary aerosols that are not formed until a chemical reaction has taken place (e.g., sulfate aerosols).

2.8 2.6 2.4

bromide; 920.0 g/L

765.5 766.0

Conductivity [S/cm]

Conductivity [S/cm]

lithium; 80.0 g/L sodium; 6.2 g/L ammonium; 91.1 g/L

2.0 chloride; 11.0 g/L 1.8 1.6 1.4 1.2 1.0 0 1 2 3 4 5 6

nitrate; 295.2 g/L

2.2

766.5 767.0 767.5 768.0 768.5

potassium; 11.4 g/L

sulfate; 31.5 g/L

10

11

12

13

14

15

10

calcium; 7.0 g/L 11

nitrite; 2.5 g/L

12

13

14

15

Time [min]

Time [min]

Anions in an aerosol sample (PM2.5) from outside air; the internal standard is LiBr; column: Metrosep 5 - 100/4.0 (6.1006.510); eluent: 3.2 mmol/L Na2CO3, 1.0 mmol/L NaHCO3, 0.7 mL/min; sample volume: 250 L

Cations in an aerosol sample (PM2.5) from outside air; the internal standard is LiBr; column: Metrosep C 4 - 100/4.0 (6.1050.410); eluent: 1.7 mmol/L HNO3, 0.7 mmol/L dipicolinic acid, 0.9 mL/min; sample volume: 250 L

Anions and cations by PILS-IC Semicontinuous determination of anions and cations in atmospheric aerosols allows high time resolution, which enables the concentration to be recorded over a prolon ged period. Sudden changes in aerosol composition can

be detected immediately. The falling nit rate and ammonium concentrations between 12.00 a.m. and 1.00 p.m. are a consequence of the lower volume of traffic during the lunch break.

35

Semicontinuous ion chromatographic determination of anion and cation concentrations in air samples from Herisau (Switzerland) by a PILS sampling system

Heavy metals by means of PILS-VA The combination of the PILS aerosol collector with the 797 VA Computrace allows semicontinuous determination of various heavy metals (Cd, Pb, Zn, Cu, Ni, Co, etc.) in particulate matter. The high time resolution picks up even the smallest changes in the chemical composition

of the aerosols: the concentrations of copper and cadmium in the air increase steadily over several days until it starts to rain and a large proportion of the copper and cadmium are washed out of the air (wet deposition).

Semicontinuous voltammetric determination of heavy metal concentrations (Cd, Pb, and Cu) in air samples from Herisau (Switzerland) by a PILS sampling system

36

Standard ions and heavy metals by PILS-IC-VA Simultaneous coupling with several analyzers is also possible: in PILS-IC-VA the particles brought into solution are conveyed in three streams to a two-channel ion chroma-

tograph for anion and cation determination and to a voltammetric measuring stand for determination of the heavy metal ions.

Semicontinuous ion chromatographic determination of the anion and cation concentrations and voltammetric determination of the heavy metal concentrations in air samples from Herisau (Switzerland). To simulate contamination events, sparklers that had been previously immersed in heavy metal salt solutions were burnt.

MARGA Monitor for AeRosols and GAses While the PILS aerosol collector enables semicontinuous determination of water-soluble ions in aerosol particles, MARGA (Monitor for AeRosols & Gases in Ambient Air) offers the option of also analyzing the composition of the water-soluble gas phase. As in the PILS system, air is sucked into the analyzer through a size-selective particle separator. Together, gases and aerosols enter a rotating gas-phase diffusion separator (denuder), where the former are absorbed in a thin layer of water (NH4+, SOx, NOx, HCl), and sent to the ion chromatograph for determination of the anions and cations. From the denuder, the aerosols go to the Steam-Jet Aerosol Collector (SJAC),

where they meet a supersaturated steam phase, absorb an increasing amount of water as condensation seeds, grow as a result of this, and are finally separated out me chanically in a glass spiral (cyclone). The resulting solution is collected, and its anion and cation content is de ter mined hourly by the integral ion chromatograph. A MARGA system provides exact results every hour. Be cause the system can work for days on end without the addition of new solutions, MARGA is ideal for field use in remote regions.

37

The MARGA system at a glance. At the top is the box with the air inlet, diffusion separator, Steam-Jet Aerosol Collector (SJAC), eluent container and some pumps; in the middle are the sample delivery and the two ion chromatographs for determination of anions and cations. The bottom shelf accommodates various storage containers, an uninterruptable power supply, and a vacuum pump.

www.epa.gov/etv
Disclaimer: The EPA Environmental Technology Verification Program (ETV) Name and/or Logo does not imply approval or certification of this product, nor does it make any explicit or implied warrantees or guarantees as to product performance. Information on the performance characteristics of Metrohm Applikon ADI 2080 MARGA can be found at www.epa.gov/etv, or call Metrohm Applikon at +31 10 29 83 555 to obtain a copy of the ETV verification report.

MARGA simultaneous monitoring of gases and aerosols MARGA is a combination of sample preparation system and online ion chromatographs, it is able to determine,

simultaneously, the gas and aerosol composition of the ambient air fully automatically every hour.

38

Changes over time in the concentration of some gases in the ambient air in Schiedam (Nether lands), April 2012. The concentration curve of the gases was determined by semicontinuous IC analyses of the aqueous phases from the rotating gas diffusion separator.

Changes over time in the ionic aerosol constituents in the ambient air in Schiedam (Netherlands), April 2012. The aqueous samples for ion analysis come from the Steam-Jet Aerosol Collector (SJAC).

www.metrohm-applikon.com

Potentiostats and galvanostats

From greenhouse gas to a source of carbon electrochemical reduction of CO2 Atmospheric carbon dioxide is a climate-related gas that is produced as a product of oxidation when organic ma terial is burnt. Reducing the concentration of CO2 in the atmosphere is a worldwide target. One promising app roach is using the CO2 in the atmosphere as a raw material source, e.g., to synthesize raw materials for fuels or chemicals. The principle is a formal reversal of combustion according to the photosynthesis model. In the process, CO2 is reduced by electrical direct current in the presence of various catalysts to produce reactive carbon monoxide or methanol. By varying the catalysts on the electrodes it is possible to synthesize a large number of organic products, such as formic acid, formaldehyde, and higher alco hols, as energy sources.

39
The PGSTAT 302N potentiostat/galvanostat makes it possible to track the reactions taking place on the catalyst surfaces and thereby provides an indispensable tool for optimizing the catalysts.

www.metrohm-autolab.com

40

Service you can rely on Metrohm Quality Service

Reliable results for the lifetime of your analytical instruments Environmental analysis is a key component of analytical chemistry and covers the analysis of water, soil, and air samples. Whoever is responsible in the laboratory for the accuracy of the results must not make compromises. Fortunately, systems installed and maintained by professionals on a regular basis all but eliminate the threats of instrument failure and lost profits. Relying on the Metrohm Quality Service gives you peace of mind from the very start. From the professional installation of your instruments to regular maintenance care and should a failure ever occur 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 Compliance Service Benefit from the Metrohm Compliance Service when it comes to the professional initial qualification of your ana lytical instruments. Installation Qualification/Operational Qualification carried out by our experts saves you time and money, as your analytical system is configured ac cord ing to your needs and put into operation fast and reliably. Initial instructions and user trainings ensure error-free ope ration of your new instruments by your staff. The Metrohm Compliance Service includes comprehensive do cumentation and guarantees compliance with the stand ards of quality management systems such as GLP/ GMP and ISO.

Metrohm Quality Service ven Metrohm Quality Service is available worldwide. Pre tive maintenance carried out on a regular basis extends your instruments lifetime while providing for troublefree operation. All maintenance work done under the label Metrohm Quality Service is carried out by our own certified service engineers. You can choose the service contract that suits you best. An overview of Metrohm Quality Service Our Services Metrohm Care Contracts that, depending on contract type, include preventive maintenance, instrument certification, on-site repair, free or discount on spare sparts and consumables as well as guaranteed response times. Application support by our vast selection of Application Bulletins, Applications Notes, monographs, validation brochures, technical posters, and articles Personal consultation by our specialists per telephone or e-mail Training courses Certified calibrations, for example, of dosing and exchange units Remote maintenance Back-up support Emergency service, for example, express on-site repairs Original spare parts, made in Switzerland and available world wide Guaranteed spare parts available for at least 10 years beyond instrument discontinuation date Decentralized repair workshops located around the world and a central workshop in Switzerland

With a full service contract, for example, you can rely on the optimum performance of your Metrohm instruments, incur no additional costs and benefit from complete and compliant verification documents. Thanks to our service you are perfectly prepared for audits.

41

Benefit for the Customer Cost certainty and cost savings, coverage of repair risk, quick response times and rapid problem solving, minimal downtimes, and ideal preparation for audits

Quick and professional solution to all arising application questions and complex analytical challenges

Competent users contribute substantially to reliable results Accurate measurements Verification documentation for compliance with regulations and for efficient audits Expeditious resolution of software questions High data security Short response times and thus, rapid problem resolution Minimization of downtime Lasting, successful repair; short delivery times Minimization of downtime Protection of your investment through long-term availability of spare parts and accessories Quality repairs done quickly, so your instruments are ready for use again

Ordering information 42
pH/Ion measuring 2.826.0110 826 pH mobile with case and Primatrode 2.827.011X 827 pH lab with Primatrode or Unitrode 2.780.0010 780 pH Meter including Unitrode 2.781.0010 781 pH/Ion Meter including Unitrode 2.140.0200 Printer Custom DP40-S4N for 780 pH Meter and 781 pH/Ion Meter 2.867.0110 867 pH Module for pH and ion measuring with Touch Control including iUnitrode 2.801.0010 801 Stirrer for 780 pH Meter, 781 pH/Ion Meter and 867 pH Module 6.0502.150 Ion-selective electrode F 6.0502.180 Ion-selective electrode Ag/S 6.0750.100 ISE Reference electrode 6.2104.020 Plug-in head G plug F, 1 m 6.2106.020 Plug-in head B plug B, 1 m

Conductivity 2.856.0110 6.0915.100 6.0915.130 6.0916.040

measurement 856 Conductivity Module with Touch Control and five-ring conductivity measuring cell c = 0.7 cm1 Five-ring conductivity measuring cell c = 0.7 cm1 with Pt 1000 Five-ring conductivity measuring cell c = 1.0 cm1 with Pt 1000 Conductivity measuring cell (stainless steel) c = 0.1 cm1 with Pt 1000

Titration (Alcalinity, COD, chloride, Ca/Mg hardness, TOC value) 2.905.0010 905 Titrando 2.800.0010 800 Dosino 2.801.0040 801 Stirrer 6.0253.100 Aquatrode plus 6.0257.600 Aquatrode plus with Pt 1000 6.0277.300 iAquatrode plus with Pt 1000, plug-in head U, without cable 6.0470.300 iAg-Titrode 6.0471.300 iPt-Titrode 6.0510.100 Combined ion-selective electrode Ca2+ 6.0750.100 ISE Reference electrode 6.2104.020 Plug-in head G plug F, 1 m 6.2106.020 Plug-in head B plug B, 1 m 6.2104.600 Plug-in head U plug F + 2 B (2 mm), 1 m SET Titration 2.877.0010 2.801.0010 2.141.0100 6.0221.600 6.2104.600 6.3026.220 soil analysis (Carbonate/bicarbonate/exchangeable Acidity) 877 Titrino plus 801 Stirrer USB Thermal printer Neos Ecotrode Gel with temperature sensor, plug-in head U Plug-in head U plug F + 2 B (2 mm), 1 m Exchange unit 20 mL

Ion chromatography Oxyhalides and standard ions in mineral water 2.881.0030 881 Compact IC pro Anion MCS 2.850.9010 IC Conductivity Detector 2.858.0020 858 Professional Sample Processor Pump 6.2041.440 Sample Rack 148 11 mL 6.1006.630 Metrosep A Supp 7 - 250/4.0 6.1011.030 Metrosep RP 2 Guard/3.5 6.6059.241 MagIC NetTM 2.4 Compact 6.5330.010 IC Equipment for Inline-Ultrafiltration Bromate in drinking water 2.850.1220 850 Professional IC Cation Gradient 2.886.0110 886 Professional Reactor 2.887.0010 887 Professional UV/VIS Detector 2.858.0020 858 Professional Sample Processor Pump 6.2041.440 Sample Rack 148 11 mL 6.1031.410 Metrosep A Supp 16 - 100/4.0 6.1031.500 Metrosep A Supp 16 Guard/4.0 6.6059.242 MagIC NetTM 2.4 Professional Aliphatic amines in wastewater 2.881.0010 881 Compact IC pro Cation 2.850.9010 IC Conductivity Detector 2.858.0020 858 Professional Sample Processor Pump 6.2041.440 Sample Rack 148 11 mL 6.1050.410 Metrosep C 4 - 100/4.0 6.1050.500 Metrosep C 4 Guard/4.0 6.6059.241 MagIC NetTM 2.4 Compact Chromium(VI) in soil and air samples 2.850.1220 850 Professional IC Cation Gradient 2.886.0110 886 Professional Reactor 2.887.0010 887 Professional UV/VIS Detector 2.858.0020 858 Professional Sample Processor Pump 6.2041.440 Sample Rack 148 11 mL 6.1006.530 Metrosep A Supp 5 - 250/4.0 6.1006.500 Metrosep A Supp 4/5 Guard/4.0 6.6059.242 MagIC NetTM 2.4 Professional 6.1020.030 Metrosep A Supp 10 - 250/4.0 6.1020.500 Metrosep A Supp 10 Guard/4.0 Anions and cations in soil samples 2.850.3030 850 Professional IC AnCat MCS 2.850.9010 IC Conductivity Detector (2 ) 2.858.0020 858 Professional Sample Processor Pump 6.2041.440 Sample Rack 148 11 mL 6.1006.530 Metrosep A Supp 5 - 250/4.0 6.1006.500 Metrosep A Supp 4/5 Guard/4.0 6.1050.430 Metrosep C 4 - 250/4.0 6.1050.500 Metrosep C 4 Guard/4.0 6.6059.242 MagIC NetTM 2.4 Professional

43

44

Saccharidic tracers in aerosols by IC 2.881.0010 881 Compact IC pro Cation 2.850.9110 IC Amperometric Detector 2.858.0020 858 Professional Sample Processor Pump 6.2041.440 Sample Rack 148 11 mL 6.5337.010 IC Equipment Wall-Jet cell for Carbohydrate Analysis 6.1013.010 Metrosep Carb 1 - 150/4.0 6.1013.020 Metrosep Carb 1 Guard/4.0 6.1030.420 Metrosep A Supp 15 - 150/4.0 6.6059.241 MagIC Net 2.4 Compact Anions and cations in aerosols (PILS-IC) 2.850.3030 850 Professional IC AnCat MCS 2.850.9010 IC Conductivity Detector (2 ) 2.136.0400 PILS, Particle into Liquid Sampler 2.136.0500 Peristaltic Pump, 8 channels with 6 rollers 6.5335.000 IC Equipment for Liquid Handling Set for PILS 6.1006.510 Metrosep A Supp 5 - 100/4.0 6.1825.290 PEEK sample loop 250 L 6.1006.500 Metrosep A Supp 4/5 Guard/4.0 6.1050.410 Metrosep C 4 - 100/4.0 6.1050.500 Metrosep C 4 Guard/4.0 6.6059.242 MagIC NetTM 2.4 Professional

Further application-specific equipment For sample delivery, it is possible to use a vacuum pump with a drying system made by KNF (vacuum pump N840.3ft.40p). The gas phase is separated with denuder systems (e.g., Multi Channel Annular Denuders made by URG, model no. URG2000-30x242-4CSS). Intake systems such as the cyclones made by URG (e.g., PM 2.5 URG, model no. URG-2000-30EH) allow aerosols to be differentiated by particle size.

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Voltammetry 2.797.0010 MVA-2 MVA-3

797 VA Computrace for manual operation VA Computrace system with automatic standard addition consisting of 797 VA Computrace and two 800 Dosinos Fully automated VA Computrace system consisting of 797 VA Computrace with 863 Compact VA Autosampler and two 800 Dosinos for automatic addition of auxiliary solutions. Allows the automatic processing of up to 18 samples. This system is the optimum solution for automatic analysis of small sample series.

VoltIC pro VoltIC pro I TitrIC pro TitrIC pro I TitrIC pro II TitrIC pro III

Heavy metals are determined by voltammetric measuring stand, anions and cations by ion chromatography.

The basic system: pH value, conductivity, and temperature are determined by direct measurement, anion concentrations by ion chromatography, and m value as well as p value plus Ca and Mg by titration. The advanced system: pH value, conductivity, and temperature are determined by direct measurement, anion and cation concentrations by ion chromatography, and m and p value by titration. The high-end system: pH value, conductivity, and temperature are determined by direct measurement, anion and cation concentrations by ion chromatography, and m and p value by titration. Additionally, this system is equipped with a DisCover function for the automatic removal of the sample caps.

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Metrohm support is always available to talk or answer my questions, be it someone from their field staff or someone from their central application support.
Dieter Bossmann, SGS Institut Fresenius

State-of-the-art environmental analysis in China

The Institute of Tropical and Marine Meteorology is lo ca ted in Guangzhou in Southern China. One of the insti tutes missions is to extend the monitoring stations ob servation capabilities to aerosols and gases to study their influence on the climate and air quality in the Pearl River Delta. To this end, they have acquired a MARGA system from Metrohm Applikon.

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