Environmental analysis Quality control of water, soil, and air 02 Metrohm ... • is the global market leader in titration • offers a complete portfolio for NIR and Raman analysis, in addition to all of the methods of • ion analysis – titration, voltammetry, and ion chromatography • is a Swiss company and manufactures exclusively in Switzerland • grants a 3-year instrument warranty and a 10-year warranty on chemical suppressors for anion chromatography • provides you with unparalleled application expertise • offers you more than 1800 applications free of charge • supports you with dependable on-site service worldwide • is not listed on the stock exchange, but is owned by a foundation • takes a sustainable approach to corporate management, putting the interests of customers • and employees ahead of maximizing profit Metrohm – customized environmental analysis for water, soil, and air samples The importance of environmental analysis You can count on our know-how 03 The rapid growth in the world population has led to sharp Metrohm offers you complete solutions for very specific increases in the consumption of energy and resources analytical issues. Your Metrohm contacts are profession-and in the production of consumer goods and che mi cals. als, who develop customized applications for you and It is estimated that there are a total of 17 million chemi-pro vide you with professional support in all matters concal compounds on the market, including as many as cerning environmental analysis. 100,000 that are produced on a large industrial scale. Discover on the following pages the solutions Metrohm The effects of human activities on the environment are offers for analysis in the environmental compartments complex and call for sensitive analytical methods and water, soil, and air. 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. Selected methods from the field of environmental analysis 04 Substances introduced into the environment are distrib- I. Water uted among the environmental compartments water (hy - As its physical state changes, water passes through all drosphere), soil (pedosphere), rock (lithosphere), and air spheres. It is the most frequently analyzed environmental (atmosphere), as well as among the organisms living on compartment and is also the easiest, because – unlike air them (biosphere). Only if we know the type and quantity or soil – it already exists in the liquid phase. If drinking of these contaminants can we protect the environment water samples are to be analyzed, sample preparation is and its inhabitants. This requires internationally accepted usually not necessary; however, it is usually unavoidable in standards, in which limits and test methods are defined. the case of wastewater samples. Metrohm instruments comply with numerous environ- mental standards. The following list contains a selec tion broken down according to environmental compartments. Parameter Standard Matrix Method Seite Drinking water, Permanganate index DIN EN ISO 8467 Titration 6 surface water ISO 6060 Drinking water, ISO 15705 Chemical oxygen demand (COD) seawater, Titration 7 ASTM D1252 wastewater DIN 38409-44 ASTM D1126-12 EPA 130.2 Ca, Mg Drinking water Titration DIN 38406-3 DIN 38409-6 8 Acid and base capacity DIN 38409-7 All types of water Titration Sulfide ASTM D4658 All types of water Titration ASTM D3868 Drinking water Titration Fluoride EPA 340.2 Wastewater Titration, Ion-selective electrode (ISE) ASTM D1253-12 Free chlorine All types of water Titration EPA 330.1 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 NO –, NO –, SO 2– etc. EPA 300.1, Part A Drinking water 2 3 4 EPA 9056A Drinking water, wastewater Chromium(VI), Anions DIN EN ISO 10304-3 All types of water Ion chromatography ASTM D5257 All types of water Chromium(VI) Ion chromatography EPA 218.7 Wastewater DIN EN ISO 11206 Drinking water ASTM D6581 Drinking water DIN EN ISO 10304-4 All types of water Oxyhalides DIN EN ISO 15061 Drinking and mineral water Ion chromatography 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+, NH +, ISO 14911 Surface and drinking water 4 Ion chromatography Mg2+, Ca2+ etc. ASTM D6919 Wastewater Amines (MMA, guanidine) – Wastewater Ion chromatography 12 Bromate EPA 321.8 Drinking water Ion chromatography (IC-ICP/MS) Bromate, halogenated acetic EPA 557 Drinking water Ion chromatography (IC-MS/MS) acids EPA 314.0 13 Perchlorate Drinking water Ion chromatography EPA 332.0 Hydrosphere, Hg, As, Cr EPA 6800 Ion chromatography (IC-ICP/MS) biosphere Zn, Cd, Pb, Cu, Tl, Ni, Co DIN 38406-16 Drinking water, wastewater Voltammetry Cd, Pb, Cu, FeII/FeIII, CrVI – Sea water Voltammetry 15 CN– Sample preparation Drinking water, Voltammetry acc.to DIN 38405-13 wastewater Groundwater, raw water U DIN 38406-17 Voltammetry drinking water 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) pH value, conductivity, TOC, Drinking water, and parameters that can Process-dependent boiler feed water, Online and atline 19 be determined by titration specifications cooling water, process analysis or voltammetry wastewater Further standard-compliant methods for water analysis can be found in the brochure water analysis (8.000.5141EN). II. Soil The soil is a multiphase system in which the hydrosphere, enter the human body through ingestion of animal and atmosphere, lithosphere, and biosphere exist side by side. plant matter. The constituents of soil are very difficult to It serves as a source of water and nutrients for plants, is access and difficult to mobilize. Sample preparation usua habitat for a large number of organisms, and is an im - ally involves extraction and digestion procedures. portant carbon sink. Harmful soil pollutants can easily 05 Parameter Standard Matrix Method Seite pH value ISO 10390 Soil pH measurement 22 Conductivity ISO 11265 Soil Conductivity measurement 23 Total organic carbon (TOC) – Soil Titration 24 Cyanide ISO 11262 Soil Continuous flow analysis 25 Anions, e.g., F–, Cl– – Soil Titration Anions EPA Method 9056 Solid waste Ion chromatography Soil Perchlorate EPA Method 6860 Ion chromatography Solid waste ISO 15192 DIN EN 15192 Chromium(VI) Soil Ion chromatography 26 EPA 3060A EPA 7199 Anions and cations – Soil Ion chromatography 27 DIN ISO 11466 Trace elements Soil Voltammetry DIN ISO 19730 28 Organophosporus pesticide AOAC 970.53 Soil Voltammetry residues III. Air The atmosphere is an important thermal buffer against mo bility, enter our bodies easily through breathing, and space, and protects the earth from cosmic radiation. It is influence the climate and weather. Filter methods, and the place where clouds are formed and water is present aerosol and gas collectors bring the constituents of air there in all its physical states. Thus it is a hete ro geneous into the aqueous phase, which is preferable for che mi cal mixture of finely dispersed, solid or liquid par ticles in a analysis. gas (air). Its constituents are characterized by extreme Parameter Standard Matrix Method Seite Saccharidic tracers – Particulate matter Ion chromatography, filter 31 ISO 16740 Chromium(VI) ASTM D6832 Workplace air Ion chromatography, filter 32 ASTM D7614-12 Pb, Cd, Zn, Cu – Particulate matter Voltammetry, filter 33 Anions and cations – Particulate matter Ion chromatography, PILS* 35 Pb, Cd, Zn, Cu – Particulate matter Voltammetry, PILS* Anions, cations, Ion chromatography and – Particulate matter 36 Pb, Cd, Zn, Cu voltammetry, PILS* Hydrogen chloride DIN EN 14791 Emissions, chimneys Ion chromatography, MARGA* Sulfur dioxide DIN EN 14791 Emissions, chimneys Ion chromatography, MARGA* 38 Nitrogen dioxide DIN EN 16339 Ambient air Ion chromatography, MARGA* * 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, Permanganate index according to DIN EN ISO 8467 physical, physicochemical or biological features of differ-The permanganate index determines the easily oxidizable ent components. Their advantage is in the fast determi-fraction of the organic constituents in water and is used, nation and informative value, which allow the sample to in a broader sense to evaluate the or ga nic chemical con-be evaluated quickly. Thus, for example, electrical contamination in waters with minimal or low contamination, ductivity provides valuable information on the salt con-such as drinking water samples. For determination, the tent of a water sample. Another important sum param- water sample is heated for ten minutes with sulfuric acid eter is the chemical oxidizability of water components, and an excess of permanganate solution of known con-which provides indications of the type and quantity of centration in a boiling water bath. After that, the per-organic material present in the sample. manganate consumption is determined by adding an excess of sodium oxalate solution and back-titrating the According to the oxidizing power of the oxidizing agents consumed oxalate with permanganate solution. The per-used, a distinction is made between the permanganate manganate index is expressed as the quantity of oxygen index and the chemical oxygen demand (COD). While the in mg/L that would be needed for oxidation. permanganate index is the more informative parameter for samples with minimal or low contamination, COD is suitable for severely contaminated samples. The MATi 13 system for fully automatic determination of the permanganate index 07 The MATi 12 system for fully automatic COD determination Chemical oxygen demand according to Automation solutions from Metrohm DIN 38409-44 and ASTM D1252 Manual determination of the permanganate index and The chemical oxygen demand (COD) is a measured value COD involves a great deal of work and, because the in - for the sum of the substances in a certain volume of dividual manual steps are difficult to reproduce, usually water that can be oxidized by chromate. Chromate is a means inaccurate results. much stronger oxidizing agent than permanganate, which is why it also oxidizes most organic compounds Metrohm solves this problem with a fully au tomated practically completely into CO . In sewage treatment system in which tiamo titration software controls all the 2 plants, COD is regarded as a valuable indicator for evalu-individual steps − from sample preparation and the addiating treatment performance. tion of the various solutions right through to the recording and archiving of data. Identical sequences guarantee For volumetric determination of the COD, the sample of unique reproducibility. New applications can be added to water is heated over a defined period with potassium the freely configurable systems at any time, no matter dichromate. The remaining quantity of potassium dichro-whether they are for the determination of the pH value, mate is then back-titrated with ammonium iron(II) sul-conductivity, acid capacity, or for coupling with an ion fate. chromatograph. Thus, it is possible to adapt any standard system individually to the particular task in the laboratory. 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, especially when there is a high sample throughput. 08 Acid and base capacity according to DIN 38409-7 Chloride Acid and base capacity are parameters that describe the Chloride ions are determined by potentiometric titration buffering capacity of water with respect to acids and with AgNO as titrant and a combined Ag-ring elec-3 bases. These are important sum parameters in water trode, the Ag-Titrode, following prior pH adjustment analysis, which characterize the pH stability of the sam-with nitric acid. The maintenance-free Ag-Titrode uses a ple. Both parameters are determined by titration to the pH glass membrane as reference electrode, which pH values of 4.3 and 8.2. The former covers all alkaline means that no refilling of electrolyte is required. parts by titration with hydrochloric acid, the latter all acidic parts by titration with caustic soda. Unlike standard pH electrodes, the Aquatrode Plus has a special glass Fluoride according to ASTM D3868 and sulfide membrane that guarantees rapid, correct, and highly according to ASTM D4658 precise pH measurements and pH titrations in solutions Fluoride and sulfide ions are determined by ion-selective that have a low ionic strength or are weakly buffered. electrodes. Calcium and magnesium according to For fluoride determination, a buffer substance is added DIN 38406-3 and EPA 130.2 to the sample. This buffer substance both maintains the With regard to the determination of water hardness, a ionic strength, regulates the pH value and complexes in - distinction is made between temporary hardness (carbo- ter fering aluminum and iron(III) ions. nate hardness) and permanent hardness (sulfate hard- ness). Another important parameter includes the total To measure sulfide, a buffer is added. This both regulates hardness that represents the sum of the dissolved alkaline the pH value and prevents the oxidation of sulfide by at - earth metals, but that is approximated as the sum of the mos pheric oxygen. calcium and magnesium hardness. Temporary hardness is determined by endpoint titration with hydrochloric acid, and total hardness by complexometric titration with Na EDTA as titrant and a Ca2+-selective electrode. 2 Combined polymer membrane electrode Ag-Titrode for chloride determination Ion-selective electrode, F for calcium and magnesium determination 09 Automation – efficient and more reproducible The MATi 01 is an excellent example of how our system to the time savings, more reproducible results can be solutions simplify your everyday laboratory work, whether achieved through automation, especially when many sam-it be sample preparation, conductivity and pH measure- ples are involved, and particularly in shift operations. But ments, or the fully automatic determination of alkalinity that is not all: the tiamo titration software also allows and water hardness in a single run from a prepared sample numerous third-party devices to be incorporated − for beaker. Gone are the days when a different instrument was example, for de ter mining turbidity according to required for each parameter, after which the data had to DIN EN ISO 7027 or for determining color according to be transferred tediously by hand into the LIMS. In addition DIN EN ISO 7887. The MATi 01 system for fully automatic water analysis, including sample measurement Ion chromatography 10 Modern ion chromatography (IC) allows efficient separa- to be monitored on account of their suspected car cin o-tion and determination of inorganic and low-molecular genic properties. organic anions and cations. Various separation mecha- nisms and types of detection as well as the possibility of Before injection, the samples pass through the ultrafiltra-automated sample preparation make IC a proven routine tion cell mounted directly on the 858 Professional Sample method in water and environmental analysis. Pro cessor. Sample preparation and analysis are fully automatic. The equipment is controlled, the data collected and Oxyhalides and standard anions in drinking managed, and the system monitored by the intelligent water (EPA 300.1) MagIC Net chromatography software. The clear symbols, Chlorate, chlorite, and bromate are by-products that are well laid-out presentation, and intuitive operation make formed by oxidation of the halides when drinking water analysis remarkably easy. and mineral water are disinfected. Their concentrations need 2.4 2.2 2.0 chloride; 11 mg/L nitrate; 12 mg/L sulfate; 8 mg/L 1.8 1.6 Conductivity [µS/cm] 1.4 1.2 fluoride; 95 µg/L dichloroacetate; 500 µg/L phosphate; 100 µg/L 1.0 chlorite; 10 µg/L bromate; 11 µg/L nitrite; 40 µg/L bromide; 47 µg/L chlorate; 18 µg/L 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time [min] Drinking water sample, spiked with 10 µg/L of each ClO –, BrO –, ClO –, 40 µg/L of each NO –, Br–, 2 3 3 2 100 µg/L PO 3–, 500 µg/L dichloroacetate; column: Metrosep A Supp 7 - 250/4.0; eluent: 4 3.6 mmol/L Na CO , 0.8 mL/min; column temperature: 45 °C; sample volume: 20 µL; conductivity detec-2 3 tion after sequential suppression. 940 Professional IC Vario with 941 Eluent Production Module and 858 Professional Sample Processor for the fully automated anion and cation analysis in drinking water. Bromate in drinking water (EPA 326.0) 11 Bromate forms during the ozonization of drink ing water. de termination of bromate in the lower µg/L range. In the Several international standards stipulate detection limits ng/L range bromate can be detected by means of IC/MS and test methods. Depending on the required detection coupling or post-column derivatization with potassium limit, different detection methods can be used. Conduc-iodide and subsequent UV detection. ti vity detection with sequential suppression allows the tap water sample spiked with 1 µg/L bromate 3.0 unspiked tap water sample 2.5 bromate 2.0 U] 1.5 1.0 Intensity [mA 0.5 0.0 -0.5 0 1 2 3 4 5 6 7 Time [min] Spiked and unspiked drinking water sample; column: Metrosep A Supp 16 - 100/4.0; eluent: 100 mmol/L H SO , 19.3 µmol/L ammonium molybdate tetrahydrate, 0.8 mL/min; post-column reagent: 0.27 mol/L KI, 2 4 flow rate: 0.2 mL/min; column temperature: 45 °C; UV detection, wavelength: 352 nm; sample volume: 1000 µL Bromate analysis: overview of test methods and detection limits (acc. to DIN 32645) Injection Detection limit Ultrapure Drinking EPA method volume water water* [µL] [µg/L] Conductivity detection with 300.1 100 0.130 0.390 sequential suppression IC/MS coupling; MS detection – 100 0.006 0.007 Post-column derivatization with 317.0 100 0.210 0.640 o-dianisidine; VIS detection Post-column derivatization with 326.0 1000 0.032 0.066 Kl; UV detection *Drinking water matrix: 100 mg/L of each chloride, sulfate, and carbonate Aliphatic amines in wastewater Aliphatic amines are important starting materials and in - Short-chain aliphatic amines in industrial wastewaters termediate products in the chemical and pharmaceutical can be determined easily on a cation-exchange column industries. They are used to produce solvents, crop pro-with subsequent conductivity detection. Not only impor- 12 tection agents, polymers, detergents, dyes, explosives, tant amines (methylamine, dimethylamine, trimethylamine, 12 lubricants, and pharmaceuticals. Their use on a large in - ethanolamines, guanidine, etc.), but also alkali metals dustrial scale has led to significant discharges into aqua-and alkaline earth metals can be detected in a single de - tic systems. Secondary amines, especially, are re gar ded as termination. There is no need for complicated deriva ti-hazardous to waters, as they react even at trace concen-zation procedures, such as those in gas chromatography. trations with nitrite to form carcinogenic nitrosamines. Interfering particles, colloids, algae, or bacteria pre sent in many (waste)water samples are removed fully automatically by Inline Ultrafiltration before analysis. -560 -565 ] -570 sodium; 20 mg/L -575 ammonium; 10 mg/L -580 Conductivity [µS/cm methylamine; 10 mg/L -585 guanidine; 5 mg/L aminoguanidine; 5 mg/L -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; eluent: 1.7 mmol/L HNO , 0.7 mmol/L dipicolinic acid, 5% acetone, 0.9 mL/min; sample volume: 10 µL; non-suppressed con-3 ductivity detection Cation analysis after Inline Ultrafiltration using 930 Compact IC Flex with 919 IC Autosampler plus Modern detection methods in IC Coupling IC with mass spectrometry (MS) and inductively made between the different oxidation states of one and coupled plasma mass spectrometry (ICP/MS) brings the same element. This element species analysis is impor-detection limits down to ultratrace levels. Whereas the tant for elements such as arsenic, chromium, mercury, great advantage of structure-specific IC/MS is that it is selenium, and gadolinium, which occur as simple elemen-possible to identify compounds not only by way of their tal and molecular ions or as polar and ionic coordination 13 retention time but also on the basis of their MS spectrum compounds, and display different toxicities, depending (organic acids), IC-ICP/MS enables a distinction to be on their bonding. Separation and detection of arsenite, monomethylarsenate, dimethylarsenate, and arsenate by IC-ICP/MS; column: Metrosep A Supp 15 - 150/4.0; eluent: 8 mmol/L ammonium nitrate, pH = 8.3, 0.7 mL/min; sample volume: 10 µL; ICP/MS: without reaction and collision mode, m/z: 75 Further applications Analyte Coupling EPA method Remark IC/MS – along with other oxyhalides Bromate IC-MS/MS EPA 557 along with haloacetic acids and dalapon IC-ICP/MS EPA 321.8 after removal of haloacetic acids EPA 332.0 Perchlorate IC/MS in water and soil samples EPA 6860 Anions and IC/MS – parallel determination in various matrices organic acids Cations IC/MS – alkali and alkaline earth metals as well as transition metals Amines IC/MS – very sensitive determination in water and food samples Organic acids IC/MS – in process water along with a high salt matrix for peak confirmation after quantitative analysis using Carbohydrates IC/MS – pulsed amperometric detection Chromium IC-ICP/MS EPA 6800 speciation analysis Arsenic IC-ICP/MS – speciation analysis Selenium IC-ICP/MS EPA 6800 speciation analysis Mercury IC-ICP/MS EPA 6800 isotope dilution mass spectrometry Gadolinium-contain- analysis of gadolinium chelates (Gadovist, Magnevist, ing MRI contrast IC-ICP/MS – etc.) and free gadolinium ions agents Voltammetry 14 Voltammetric trace and ultratrace analysis of drinking me tal tit rant, a voltammogram is registered. Plotting the water, groundwater, surface water, seawater, and waste-currents of the respective peak heights versus the metal water is used to determine electrochemically active inor-concentration provides a titration curve from which the ganic ions. It is frequently employed to complement and complexation capacity is deduced. validate spectroscopic methods. Its features are: compact equipment, relatively low investment and running costs, Versatile application areas simple sample preparation, short analysis times, and high Voltammetry is especially suitable for laboratories in which accuracy and sensitivity. only a few parameters have to be monitored with a mod- erate sample throughput. Important fields of application Speciation analysis include environmental monitoring, limnology, hy dro - Another advantage of voltammetry is the possibility to gra phy, oceanography, marine biology, and soil science. distinguish bet ween different oxidation states of metal ions (speciation) as well as between free and bound 884 Professional VA metal ions. This pro vides important information regard-The 884 Professional VA is a flexible measuring instru- ing the bioavailability and toxicity of heavy metals. ment for accurate and sensitive voltammetric analyses. The accompanying viva software enables individual opti- Determination of the complexation capacity mization of methods. Natural waters often contain dissolved organic com- pounds that complex heavy metals and thus change bio - 909 UV Digester availability and toxicity of the latter. The parameter used With the 909 UV Digester, unwanted organics in surface to quantify the organic ligands in a sample is the compl-water and wastewater samples can be digested quickly exation capacity; it indicates the amount of heavy metal and safely, with no contamination. UV digestion is the ions which are barely complexed. Determination is per-ideal sample preparation for the voltammetric determina-formed by voltammetric titration. After each addition of tion of heavy metals. 15 Many toxic transition metals and a few anions can be tion for both elements. de termined voltammetrically, with a high degree of sensitivity and without prior sample preparation, in drinking The scTRACE Gold combines all three of the electrodes water and groundwater. Here are a few relevant examples: needed for the measurement. Selection of the measuring parameter makes it possible to distinguish between Nickel and cobalt As(III) and As(V). These metal ions must be determined regularly in water samples. DIN 38406 Part 16 describes the determination Moreover, inorganic mercury can also be determined of these ions in different types of water. with the scTRACE Gold. The detection limit in this case is 0.1 µg/L. -150 Ni Detection limits -125 Detection limit Element -100 [ng/L] Antimony SbIII/SbV 200 -70 I [nA] Arsenic AsIII/AsV 100 Bismuth Bi 500 -50 Cadmium Cd 50 Co -25 Chromium CrIII/CrVI 25 Cobalt Co 50 0 Copper Cu 50 -0.80 -0.90 -1.00 -1.10 -1.20 -1.30 U [V] Iron FeII/FeIII 50 Lead Pb 50 Mercury Hg 100 Voltammetric determination of nickel and cobalt in seawater according to DIN 38406-16 Molybdenum Mo 50 Nickel Ni 50 Platinum Pt 0.1 Arsenic and mercury with the scTRACE Gold Rhodium Rh 0.1 Due to the toxicity of arsenic and mercury, the World Selenium SeIV/SeVI 300 Health Organization recommends a maximum content in Thallium Tl 50 the drinking water of 6 or 10 µg/L, respectively. Anodic Tungsten W 200 stripping voltammetry using the scTRACE Gold offers a Uranium U 25 simple, low-cost alternative to spectroscopic determina-Zinc Zn 50 16 The fully automatic VoltIC Vario pro consists of several 800 Dosinos, a 797 VA Computrace, an 858 Professional Sample Processor, and a 940 Professional IC Vario (from right to left). VoltIC Vario pro – Voltammetry and Ion Chromatogra- phy VoltIC Vario pro combines voltammetry (VA) and ion chromatography (IC) in a single system and permits the fully au tomatic 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 Vario 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 Vario 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 Vario pro» system. The VoltIC Vario pro Report: All the results at a glance TitrIC Vario pro – Titration and Ion Chromatography TitrIC Vario pro stands for a unique combination of direct TitrIC Vario pro comes in three versions. All three systems 17 mea surement, titration, and ion chromatography and determine temperature and conductivity, pH as well as p permits the fully automatic determination of tempera-and m value, and analyze anions by ion chromatography. ture, conductivity, pH as well as p and m value, alkalinity, total hardness, and numerous ion concentrations. Just as In the basic system, TitrIC Vario pro I, the content of Ca in the VoltIC Vario pro system, the analysers use the same and Mg is measured by titrimetry. In TitrIC Vario pro II liquid hand ling instruments, a common sample changer, and TitrIC Vario pro III, cations are determined by ion and the same database. The system is controlled by the chromatography. In addition, TitrIC Vario pro III has a master software MagIC Net, while the titration software sample changer with the DisCover function for the auto- tiamo runs in the background. TitrIC Vario pro has matic removal of the lid of the sample vessel. If required, impressively short analysis times, uses little space, and additional determinations can be integrated into the gives high precision results. «TitrIC Vario pro» systems. The TitrIC Vario pro III consists of an 856 Conductivity Module, two 800 Dosinos, an 802 Stirrer, a 905 Titrando, an 815 Robotic USB Sample Processor XL, and the 940 Professional IC Vario for anions and cations. Potentiostats and galvanostats 18 Energy from wastewater: the microbial fuel cell Like all living beings, microorganisms meet their energy Initial results show that the degradation of pollutants in requirements by breaking down energy-rich substances. wastewater can be used to recover energy. The target is Humans make use of this in sewage treatment plants, energy-neutral wastewater purification. For this, how-where bacteria mineralize the organic pollutant load to a ever, the electron transfer processes still need to be opti-large extent. The microorganisms release electrons, which mized, e.g., by increasing the size of the electrode surface. they transfer to electron acceptors such as oxygen, At present, work is being done with electrodes made nitrate, and sulfate. If this transfer of electrons is from a up of countless conducting carbon fibers on which the mediator – i.e., an electron bridge – to a solid elec tron bacteria sit. The electrochemical impedance spectroscopy receptor such as an anode, an electric current will flow, ca pabilities of the Autolab PGSTAT128N with FRA32M provided there is also a cathode and a power consumer. module allow the electron transfer kinetics and interfacial This way, bacterial energy is directly converted to electri-properties to be monitored. cal energy. It is essential that the bacteria are in di rect contact with the electrode in the form of a biofilm. www.metrohm-autolab.com Online and atline analysis systems from Metrohm Process Analytics Online and atline Process Analyzers from Metrohm experience, we offer a wide range of analyzer products 19 Process Analytics are the preferred solution for process and integrated systems for diverse applications and monitoring in a wide range of industries. Using the com-industries to meet the challenging requirements and plete range of modern ion analysis (pH value, conductiv-demands of your process. ity, and redox potential titration, KF titration, photometry, ISE measurements, and voltammetry) Metrohm Process Metrohm Applikon, with Process Analyzers sold under Analytics pro vides high precision results for any wet-che-the brand name Metrohm Process Analytics, is part of the mical parame ters you need right at your production line. Metrohm Group and represented in over 45 countries. Our regional and local presence offers knowledgeable Metrohm Process Analytics has specialized in online and support in sales, applications, project engineering, and atline process analysis for over 40 years. With this vast start-up. We intend to be your pro cess monitoring part-ner for years to come. Process analysis 20 Customized online and atline process control Single-Parameter online Analyzer Because of the outstanding dissolving properties of wa - The ICON Analyzers and Alert Ion Analyzers are based on ter a large number of organic and inorganic compounds colorimetric and ion-selective electrode (ISE) methods, accumulate in it. This requires powerful analysis that mo - respectively. The ISE methods are generally used for ni tors the composition of the water continuously. With measurements in the ppm and percent range, whereas the Process Analyzers from Metrohm Process Analytics the colorimetric techniques are used for the ppb to ppm this is possible 24 hours a day, 7 days a week. The analyz-range. Some typical applications: ers are used directly on-site, as close as possible to the process, and run without any operator intervention. Sodium and silica in power plants More over, it makes no difference whether a single Both sodium and silica play a major role in corrosion parameter is to be determined in a single sample stream processes that occur in cooling water systems. For power or several different parameters are to be determined plants, it is essential to monitor the concentrations of simultaneously in complex, multiple sample streams – these species. With the Alert Ion Analyzer equipped with whatever your requirement, Metrohm Applikon can offer the Metrohm Na+ ISE, it is possible to measure sodium you an appropriate online or atline Process Analyzer. concentrations down to 1 µg/L. If lower detection limits are required, the Alert Ion Analyzer can be replaced by Proven wet-chemistry methods the more accurate ICON Analyzer. Silica in cooling water Most analyzers are based on wet-chemical analysis tech-or high-purity water can be determined with the ICON niques such as titration, colorimetry, or ion-selective elec-Analyzer at concentrations as low as 1 µg/L. t rode measurements. Most of the well-established labo- ratory methods for water analysis can be easily trans- ferred 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 pressurized 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 transferred via 4–20 mA outputs, where as alarms can be transmitted via the digital outputs. Digital inputs, in turn, can be used for remote start-stop purposes. ADI 2045TI Process Analyzer – the flexible analyzer for online applications 21 Total organic carbon content (TOC) Heavy metals, phosphates, nitrates, and COD The total organic carbon content (TOC) is a highly impor-Numerous parameters need to be continuously moni- tant sum parameter that indicates all of the organic car-tored in industrial and municipal wastewaters. These in - bon in the sample examined. This value represents the clude, for example, the heavy metals cadmium, lead, level of organic contamination. As an online parameter, zinc, and cobalt as well as the anions nitrate, ammoni-it can be readily automated and provides attractively high um, phosphate, and sulfate. Metrohm Process Analytics precision and accuracy. Another advantage: the determi-has a wide range of analyzers available: while the nation requires no toxic chemicals. ADI 2045VA Process Analyzer is designed specifically for determining heavy metals, the ADI 201Y and ADI 2045TI The 7010 TOC Analyzer is perfect for continuous moni- Process Analyzers perform the other ana lyses. In addi- toring of the TOC value in all types of water. The oxidation, Metrohm Process Analytics offers a large num ber of tion of organic carbon is accomplished using persulfate sample preparation systems that can be combined with in the presence of UV light, and complies with EPA, any application, no matter how unusual that application ASTM, NAMUR and ISO regulations. might be. Chemical oxygen demand Iron in drinking water The chemical oxygen demand (COD) is one of the most The taste of drinking water depends to a large extent important sum parameters for assessing wastewater pol-on its origin and treatment. Water contains different lution. Metrohm Process Analytics offers both titrimetric amounts of magnesium, iron, sulfate, and carbonate, determination, described already on page 7, and also de pending on whether it has passed through stone, clay colorimetric determination: depending on the required or gravel sand. Iron concentrations above 2 mg/L have a detection limit, continuous COD determination can be significant effect on taste. Many water suppliers use sand performed by either the ADI 2045TI Process Analyzer or filters to remove the iron. Alert Ion Analyzers, developed the Process Colorimeter ADI 2019. 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 A simple method for determining the pH value is de s cri-boundary area where the lithosphere, hydrosphere, at - bed in ISO 10390. It describes the slurrying of an mosphere and biosphere coexist. As a multiphase system, air-dried and sieved (max. 2 mm sieve) soil sample with the pedosphere consists predominantly of soil mineral distilled water and subsequent measurement. Alter na ti-matter, approximately equal proportions of soil air and vely, ex trac tion can be performed using 0.01 molar CaCl 2 soil water, and a small amount of organic matter. The or 1 molar KCl. The cations in these solutions displace the pedosphere forms the key basis of life for plants, animals, protons that are absorbed on the ion exchangers of the and humans. Harmful substances contained in it come soil as quantitatively as possible. 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. The flat membrane electrode is ideal for pH measurements in sediment-containing sample solutions. 914 pH/Conductometer: ideal for routine use in the lab and as robust companion in the field 23 Determination of electrical conductivity in soil samples according to ISO 11265 The determination of conductivity provides qualitative in formation about the amount of dissolved salts in the 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 Titrant 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 of (with continous eluate – of inorganic components from pH value on leaching behav- analysis) waste (DIN CEN/TS 14997) ior Conductivity (ISO 11265) Slurrying Direct measurement – Total organic carbon Visually with barium (TOC), Walkley-Black K Cr O /H SO digestion 1 mol/L FeSO (acidic) 2 2 7 2 4 diphenylamine sulfonate 4 method Aluminium Extraction Visually, phenolphthalein 0.02 mol/L NaOH Soil sample is shaken with Carbonate content, Piper a) Photometrically with 0.2 mol/L HCl and allowed method a) phenolphthalein to settle; 10 mL of the 0.1 mol/L NaOH (also known as rapid titration supernatant solution is back- b) Potentiometrically, or acid neutralization method) titrated with NaOH b) SET titration to pH 7.8 a) Photometrically with Acidity Ion exchange with a) phenolphthalein 0.025 mol/L NaOH «Exchangeable acidity» (H + Al) 1 mol/L KCl b) Potentiometrically, b) SET titration to pH 7.6 Total cyanide and easily a) Photometrically with released cyanide Distillation a) phenolphthalein 0.005 mol/L AgNO3 (ISO 11262) b) Potentiometrically Soluble anions carbonate/ Extraction with CO -free SET titration to 2 0.1 mol/L HCl bicarbonate (alkalinity) distilled Water pH 8.4 and 4.4 Ion chromatography 26 Chromate in soil samples Chromium occurs primarily in the stable oxidation states Ion chromatography can detect chromate in the soil Cr(III) and Cr(VI). The oxidation state determines the bio-down to µg/L levels. Here, the relatively large, doubly logical and toxicological properties, which could hardly charged chromate anion is separated from the other be any more different: Cr(III) is one of the essential trace anions on an anion-exchange column and then convert-elements and plays an important role especially in the ed by post-column reaction with 1,5-diphenylcarbazide metabolism of fats and glucose, whereas hexavalent solution to form a reddish-violet complex that is analyzed chromium is very toxic and carcinogenic. at 540 nm with a UV/VIS detector. Chromium is present in different concentrations in all The sample preparation of soil samples is a demanding types of soil and rock. It usually occurs in the cationic and task. It is essential to ensure that the extraction solution less bioavailable trivalent form; it can, however, also releases the chromate from the samples without there oc cur as toxic and very mobile chromium(VI) anion – usu-being any change in the oxidation state of the chromate. ally as a result of anthropogenic input. Because of the For most soil samples, alkaline digestion according to differences in toxicity, the total concentration of chromi-EPA 3060A or ISO EN 15192 is recommended. Before ion um is of less interest than the concentration of chromate. chro matographic determination, filtering with 0.45 µm filters is required. This can also be automated conveniently with the use of an Inline Ultrafiltration cell. 12 10 U] 8 Chromium(VI); 6.9 mg/kg 6 Intensity [mA 4 2 0 1 2 3 4 5 6 7 8 9 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 Na CO , then di-2 3 lute with ultra pure water 1:10); column: Metrosep A Supp 5 - 250/4.0; eluent: 15 mmol/L Na CO , 2 3 10 mmol/L NaOH, 0.7 mL/min; sample volume: 100 µL; post-column derivatization with 0.5 g/L 1,5-diphenylcarbazide, 10% methanol, 0.5 mol/L H SO ; flow rate post-column reagent: 0.5 mL/min; 2 4 UV/VIS detection at 540 nm Anions and cations in soil samples 27 The nutrient content in soil samples determines plant Ion chromatography with conductivity detection enables growth and is of great importance especially with regard rapid determination of the nitrogen components nitrate, to agricultural use. Of prime interest here are the concen-nitrite, and ammonium, and also of the ions sulfate, trations of the main nutrient elements (macronutrient phosphate, calcium, magnesium, and potassium. Sample elements) nitrogen, phosphorus, potassium, calcium, mag-preparation includes aqueous extraction of the soil samples. nesium, and sulfur. 3.8 3.4 3.0 ] 2.6 chloride; 262.9 mg/kg 2.2 1.8 nitrate; 406.4 mg/kg 1.4 Conductivity [µS/cm 1.0 sulfate; 183.6 mg/kg 0.6 nitrite; 30.2 mg/kg phosphate; 104.2 mg/kg 0.2 0 2 4 6 8 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 extracted for 10 minutes in an ultrasonic bath, diluted with ultrapure water 1:10 (v/v), and finally filtered with 0.45 μm filters and RP cartridges; column: Metrosep A Supp 5 - 250/4.0 eluent: 3.2 mmol/L Na CO ,1.0 mmol/L 2 3 NaHCO , 5% acetone, 0.7 mL/min; column temperature: 30 °C; sample volume: 20 µL; conductivity detec-3 tion after sequential suppression 940 Professional IC Vario with 944 Professional UV/VIS Detector Vario and 943 Professional Reactor Vario: the ideal system for chromate analysis Voltammetry 28 Trace elements and harmful pollutants in the soil The determination of the nutrient content in the soil re - tion methods are described in standards (e.g., ISO 12914). quires not only ion chromatographic analysis of the main The extracts obtained can usually be determined directly nutrient elements, but also determination of the essential by voltammetry. trace elements: iron, manganese, zinc, and copper. This can be achieved very accurately and sensitively by vol-Another application of voltammetry is the determination tammetry. Moreover, voltammetry is suitable for analyz-of organophosphorus pesticide residues, such as, for ing harmful heavy metals such as lead, cadmium, chro- example, diazinon, malathion, parathion-methyl, and pa - mium, mercury, uranium, and zinc in the soil. ra thion, according to AOAC 970.53. Through extraction with organic solvents the electrochemically active sub- In contrast to water analyses, ion analysis in soils is usu-stances are separated from the soil matrix and then ally preceded by extraction or digestion to transfer the enriched by adsorption on the HMDE and determined by ions into the aqueous solution. Various sample prepara-reduction. Potentiostats and galvanostats Analysis for the electroremediation of 29 contaminated soils Soils contaminated with heavy metals and organic com- substances, such as phenols, aromatic amines, or haloge-pounds represent a serious risk to the environment, which nated hydrocarbons, are oxidized on the anode. Elec tro - is why cost-effective and environmentally compatible re - remediation is ideal for fine-grained clay, loam, or silt mediation of contaminated sites is becoming in creas in gly soils with a high water-retention capacity, where other in urgent. In situ methods where contaminated soils are situ remediation techniques usually fail. treated without being excavated are the state of the art. A very promising method is electroremediation (also The first Autolab potentiostats/galvanostats were devel-known as electrochemical remediation), where a se ries of oped exactly two decades ago for this type of applica-anodes and cathodes installed in the soil body and con- tion. By combining a PGSTAT128N potentiostat/galva- nected to a direct-current source induce an electrical nostat (cyclic voltammetry and galvanostatic analysis) field, under the influence of which electrokinetic trans-and a booster it is possible to track the redox reactions port and redox processes take place. As a result, heavy – the oxidation of organic compounds and the reduction metals are reduced on the cathode and harmful organic 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 per- production). By reflecting sunlight and acting as conden-son’s respiratory system in the course of a lifetime. In this sation seeds for cloud formation, they influence our cli-way, impurities in the atmosphere directly enter the mate and weather. lungs. Especially dangerous are the aerosols that contain particles with diameters of less than 10 µm – also know The chemical composition of aerosols is highly complex as particulate matter. These are airborne heterogeneous and not yet fully understood. To estimate the effects of mixtures of substances made up of minute particles, aerosols on health and climate, it is essential to know some of which are solid and some liquid. The smaller their chemical composition. Sampling is done using two these particles are, the deeper they go into the lungs. different types of aerosol collector. The first type are filter Once they reach the place where the gas exchange collectors that are based on the deposition of suspended occurs, the pulmonary alveoli, there is just one micron of particles on surfaces; they usually require a pump, are tissue between them and the blood stream. operated in offline mode, and supply data over prolon- ged ac cumulated periods. The second type are powerful Aerosols come both from natural sources (volcanic erup- aerosol collectors such as PILS or MARGA that work pri- tions, sea spray, desert dust, fire, biogenic input) and from marily in online mode and provide semicontinuous data. anthropogenic sources (burning of fossil fuels, industrial Filter methods The particulate matter contained in the air is collected on Thus, concentration profiles of these saccharidic tracers 31 filters with a certain air flow over a defined period of time. make it possible to obtain indications of sources of aero-Sampling is usually in accordance with DIN EN 12341. sols. For example, analysis of the saccharide composition The composite air samples of particulate matter are ex - in summer filters shows a significantly higher proportion tracted and the extract is then analyzed using ion chro-of sugar alcohols. In winter filters, by contrast, there is a ma tography (IC) or voltammetry (VA). predominance of anhydrosugars, especially levogluco san. Saccharidic tracers in particulate matter by IC Following direct water extraction by the aerosol filters, The anhydrosugars levoglucosan, mannosan, and galac-the saccharidic tracers are separated by ion chromatog- tosan are produced when cellulose and hemicellulose are raphy and determined reliably down to lower ng/m3 lev-burnt and act as tracers for the combustion of biomass. els by way of pulsed amperometric detection (PAD). The By contrast, the sugar alcohols arabitol and mannitol are IC-PAD method requires no derivatization, can be auto-tracer substances for biological processes: when fungi mated easily and is suitable for routine use with large fling spores into the air, the concentration of mannitol in sample series. 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. 800 750 700 650 inositol 600 galactosan 550 mannosan galactose 500 xylitol fucose 450 sorbitol glucose mannitol levoglucosan 400 mannose Current [nA] 350 lactitol sucrose sorbose lactose 300 250 fructose 200 150 100 50 0 4 8 12 16 20 24 28 32 36 40 44 Time [min] Determination of saccharidic tracers; columns: Metrosep Carb 2 - 150/4.0; eluent: 5 mmol/L sodium hy-droxide, 2 mmol/L sodium acetate 0.6 mL/min; column temperature: 40 °C; sample volume: 20 µL; PAD measuring mode (gold working electrode) 32 Chromium(VI) in the particulate matter of indoor air – IC method according to ASTM D6832 When breathed in, water-soluble chromium(VI) particles The method described in ASTM D6832 for chromium(VI) in the PM2.5 fraction pass all the way through to the determination in the particulate matter of indoor spaces pulmonary alveoli. There, they penetrate the extremely describes an ion chromatographic separation of the thin tissue and enter the liver and kidney cells by way of chro mium(VI) species with post-column derivatization the blood plasma. Starting out from the red cells, Cr(VI) and spectrophotometric detection. The sampling and thus interacts with the cellular protein molecules of the sample preparation techniques chosen are such that no DNA. transformation occurs between trivalent and hexavalent chromium compounds. Furthermore, a distinction can be Like other carcinogenic compounds, chromium(VI) is made between soluble and insoluble chromium(VI) com-subject not to an occupational exposure limit, but to the pounds by choosing the appropriate extracting agent. 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 µg/L range. 26 24 22 20 chromium(VI); 390 µg/L 18 U] 16 14 12 10 Intensity [mA 8 6 4 2 0 0 1 2 3 4 5 6 7 8 9 10 11 12 Time [min] Determination of the insoluble chromium(VI) content in filter extracts of an air sample; ultrasound-assisted extraction with 3% Na CO and 2% NaOH with a subsequent 1:1 (v/v) dilution of the extract; column: 2 3 Metrosep A Supp 10 - 250/4.0; eluent: 0.25 mol/L (NH ) SO , 0.05 mol/L NH OH, 0.6 mL/min; col-4 2 4 4 umn temperature: 25 °C; sample volume: 1000 µL; post-column derivatization with 2 mmol/L 1,5-diphenylcarbazide, 10% methanol, 0.5 mol/L H SO ; flow rate post-column reagent: 0.2 mL/min; UV/VIS 2 4 detection at 540 nm 33 Heavy metals in the particulate matter by voltammetry The heavy metals (e.g., lead, cadmium, and zinc) con- tained 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 ganism. Apart from having a carcinogenic effect, heavy me tals especially damage 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 PILS – Particle Into Liquid Sampler Semicontinuous determination of anions and 34 Compared with the filter methods, the Particle Into Liquid cations by PILS-IC Sampler (PILS) allows a much higher time resolution. Semi-Coupling with ion chromatography allows climate-relat- continuous measurements are possible approximately every ed water-soluble anions and cations in the aerosol to be 15 minutes. This high time resolution allows changes in determined. This enables important conclusions to be the aerosol composition to be correlated with meteoro-drawn about the precursors and thus about the question logical and other data. Furthermore, there is no need for of whether particles are emitted directly – as in the case complicated and error-prone manual sample preparation, of the primary sea salt aerosols (NaCl) – or whether the and no hassle of storing samples. materials are secondary aerosols that are not formed until a chemical reaction has taken place (e.g., sulfate The way PILS works is simple. At the intake, a size-aero sols). selective glass spiral (cyclone) limits the particle size of the aerosols to a maximum of 1, 2.5 or 10 µm (PM , 1 PM , PM ), as re qui red. The aerosols then enter a con-2.5 10 densation 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 wide-spread. Whereas the former determines the total organic carbon in the aerosol, ICP is used for multi-element analysis. Offline sampling with an autosampler is also possible. The Particle Into Liquid Sampler. PILS coupled with IC and VA can be used to measure the ionic substances of the aerosols. 2.8 765.5 2.6 766.0 2.4 lithium; 80.0 µg/L ] 2.2 bromide; 920.0 µg/L 766.5 2.0 767.0 1.8 L 1.6 767.5 nitrate; 295.2 µg/L ammonium; 91.1 µg/L Conductivity [µS/cm] Conductivity [µS/cm 1.4 768.0 1.2 chloride; 11.0 µg/L nitrite; 2.5 µg/L sodium; 6.2 µg/ sulfate; 31.5 µg/L 768.5 potassium; 11.4 µg/L calcium; 7.0 µg/L 1.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Time [min] Time [min] Anions in an aerosol sample (PM ) from outside air; the in - Cations in an aerosol sample (PM ) from outside air; the internal 2.5 2.5 ternal standard is LiBr; column: Metrosep A Supp 5 - 100/4.0; standard is LiBr; column: Metrosep C 4 - 100/4.0; eluent: 1.7 eluent: 3.2 mmol/L Na CO , 1.0 mmol/L NaHCO , 0.7 mL/min; mmol/L HNO , 0.7 mmol/L dipicolinic acid, 0.9 mL/min; sample 2 3 3 3 sample volume: 250 µL; conductivity detection after sequential volume: 250 µL; Conductivity detection without sequential sup-suppression pression Anions and cations by PILS-IC 35 Semicontinuous determination of anions and cations in be detected immediately. The falling nit rate and ammo-atmospheric aerosols allows high time resolution, which nium concentrations between 12:00 and 1.00 p.m. are a enables the concentration to be recorded over a prolon-consequence of the lower volume of traffic during the ged period. Sudden changes in aerosol composition can lunch break. 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 of the aerosols: the concentrations of copper and cad-797 VA Computrace allows semicontinuous determina- mium in the air increase steadily over several days until it tion of various heavy metals (Cd, Pb, Zn, Cu, Ni, Co, etc.) starts to rain and a large proportion of the copper and in particulate matter. The high time resolution picks up cadmium are washed out of the air (wet deposition). even the smallest changes in the chemical composition 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 pos-tograph for anion and cation determination and to a sible: in PILS-IC-VA the particles brought into solution are voltammetric measuring stand for determination of the conveyed in three streams to a two-channel ion chroma-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 37 While the PILS aerosol collector enables semicontinuous where they meet a supersaturated steam phase, absorb determination of water-soluble ions in aerosol particles, an increasing amount of water as condensation seeds, MARGA (Monitor for AeRosols & Gases in Ambient air) grow as a result of this, and are finally separated out me - offers the option of also analyzing the composition of chanically in a glass spiral (cyclone). The resulting solution the water-soluble gas phase. As in the PILS system, air is is collected, and its anion and cation content is de ter - sucked into the analyzer through a size-selective particle mined hourly by the integral ion chromatograph. separator. Together, gases and aerosols enter a rotating gas-phase diffusion separator (denuder), where the for-A MARGA system provides exact results every hour. Be - mer are absorbed in a thin layer of water (NH +, SO , NO , cause the system can work for days on end without the 4 x x HCl), and sent to the ion chromatograph for determina- addition of new solutions, MARGA is ideal for field use in tion of the anions and cations. From the denuder, the remote regions. aerosols go to the Steam-Jet Aerosol Collector (SJAC), 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, along with an integrated computer. The bottom shelf accommodates various storage containers, an uninterruptible 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 Process Analytics 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 simultaneously, the gas and aerosol composition of the and online ion chromatographs, it is able to determine, 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). Potentiostats and galvanostats From greenhouse gas to a source of carbon – 39 electrochemical reduction of CO2 Atmospheric carbon dioxide is a climate-related gas that The PGSTAT 302N potentiostat/galvanostat makes it is produced as a product of oxidation when organic ma - possible to track the reactions taking place on the cata-terial is burnt. Reducing the concentration of CO in the lyst surfaces and thereby provides an indispensable tool 2 atmosphere is a worldwide target. One promising app- for optimizing the catalysts. roach is using the CO in the atmosphere as a raw mate- 2 rial 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, CO is 2 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 alcohols, as energy sources. www.metrohm-autolab.com 40 Metrohm Quality Service – Service you can rely on Reliable results for the lifetime of your analytical Metrohm Compliance Service instruments Benefit from the Metrohm Compliance Service when it Environmental analysis is a key component of analytical comes to the professional initial qualification of your chemistry and covers the analysis of water, soil, and air ana lytical instruments. Installation Qualification/ samples. Whoever is responsible in the laboratory for Operational Qualification carried out by our experts the accuracy of the results must not make compromises. saves you time and money, as your analytical system is Fortunately, systems installed and maintained by profes-configured ac cord ing to your needs and put into opera-sionals on a regular basis all but eliminate the threats of tion fast and reliably. instrument failure and lost profits. Initial instructions and user trainings ensure error-free Relying on the Metrohm Quality Service gives you peace ope ration of your new instruments by your staff. The of mind from the very start. From the professional instal-Metrohm Compliance Service includes comprehensive lation of your instruments to regular mainte- do cumentation and guarantees compliance nance care and – should a failure ever with the stand ards of quality manage- occur – instant quality repairs, we ment systems such as GLP/GMP do everything to make sure and ISO. that you can rely 100 per cent on results produced during the entire lifetime of your Metrohm instruments. Metrohm Quality Service Metrohm Quality Service is available worldwide. Pre ven-With a full service contract, for example, you can rely on tive maintenance carried out on a regular basis extends the optimum performance of your Metrohm instruments, your instrument’s lifetime while providing for trouble-incur no additional costs and benefit from complete and free operation. All maintenance work done under the compliant verification documents. Thanks to our service label Metrohm Quality Service is carried out by our own you are perfectly prepared for audits. 41 certified service engineers. You can choose the service contract that suits you best. Metrohm Quality Service Customer benefits • Minimizes downtime through preventive maintenance • Cost control and savings through free or discounted replacement materials Metrohm Care Contracts and consumables • Guaranteed reaction times and rapid on-site repair • Documented instrument certification as an ideal preparation for audits • High data security and maximum system performance through regular, Metrohm Software Care professional software maintenance • Customized services and documentation for analytical instrument qualification (AIQ) Metrohm Compliance Service • Professional start-up (IQ/OQ or Certified Installation) and requalification or recertification by specifically trained employees Metrohm Remote Support • Quick resolution of software and application issues directly at the workplace • Calibration of burettes (e.g., dosing and exchange units) with certification Metrohm Dosing Test • Accurate measurement results • Verification documentation for compliance with regulations 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remote support • Support for the solution of complex analytical problems, as well as method optimization on-site or at our application laboratories • Basic and advanced training with local representatives, at the Metrohm Academy or directly on-site Metrohm Training Programs • Efficient and proper use of all analytical methods, as well as results reliability through competently trained users • Training documentation and certificates for trouble-free audits Ordering information 42 pH/Ion measuring 2.913.0110 913 pH Meter with Primatrode and accessories case 2.913.0210 913 pH Meter, laboratory version 2.780.0010 780 pH Meter including Unitrode 2.781.0010 781 pH/Ion Meter including Unitrode 2.867.0110 867 pH Module for pH and ion measuring with Touch Control including iUnitrode 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 measurement 2.856.0110 856 Conductivity Module with Touch Control and five-ring conductivity measuring cell c = 0.7 cm–1 2.912.0210 912 Conductometer Lab, laboratory version 2.912.0110 912 Conductometer with conductivity sensor and accessories case 2.914.0120 914 pH/Conductometer with Primatrode and accessories case 2.914.0220 914 pH/Conductometer, laboratory version 6.0915.100 Five-ring conductivity measuring cell, c = 0.7 cm–1 with Pt 1000 for 856 Conductivity Module 6.0915.130 Five-ring conductivity measuring cell, c = 1.0 cm–1 with Pt 1000 for 856 Conductivity Module 6.0916.040 Conductivity measuring cell (stainless steel), c = 0.1 cm–1 with Pt 1000 for 856 Conductivity Module 6.0917.080 Conductivity measuring cell, c = 0.5 cm–1 with Pt 1000 for 912/914 6.0918.040 Conductivity measuring cell made of stainless steel, c = 0.1 cm–1 with Pt 1000 for 912/914 6.0919.140 Conductivity measuring cell, c = 1.6 cm–1 with Pt 1000 for 912/914 Titration (Alkalinity, COD, chloride, Ca/Mg hardness, TOC) 2.905.0010 905 Titrando 2.800.0010 800 Dosino 2.801.0040 801 Stirrer MATi 01 Fully automated water analysis MATi 12 Automated COD determination MATi 13 Fully automated determination of the permanganate index in accordance with DIN EN ISO 8467 6.0253.100 Aquatrode plus 6.0257.600 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 soil analysis (Carbonate/bicarbonate/exchangeable Acidity) 2.877.0010 877 Titrino plus 2.801.0010 801 Stirrer 2.141.0100 USB Thermal printer Neo’s 6.0221.600 Ecotrode Gel with temperature sensor, plug-in head U 6.2104.600 Plug-in head U – plug F + 2 × B (2 mm), 1 m 6.3026.220 Exchange unit 20 mL Ion chromatography Oxyhalides and standard ions in mineral water 2.940.2500 940 Professional IC Vario TWO/SeS/PP 2.850.9010 IC Conductivity Detector (2 x) 2.858.0020 858 Professional Sample Processor – Pump 43 2.941.0010 941 Eluent Production Module 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 6.2842.000 MSM-HC Rotor A 6.6059.312 MagIC Net 3.1 Professional 6.5330.110 IC Equipment for Inline Ultrafiltration Bromate in drinking water 2.930.2160 930 Compact IC Flex Oven/Deg 2.943.0110 943 Professional Reactor Vario 2.944.0010 944 Professional UV/VIS Detector Vario 2.858.0020 858 Professional Sample Processor – Pump 2.800.0010 800 Dosino 6.3032.150 Dosing Unit 5 mL 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 6.6059.311 MagIC Net 3.1 Compact Aliphatic amines in wastewater 2.930.1160 930 Compact IC Flex Deg 2.850.9010 IC Conductivity Detector 2.919.0020 919 IC Autosampler plus 6.1050.410 Metrosep C 4 - 100/4.0 6.1050.500 Metrosep C 4 Guard/4.0 6.6059.311 MagIC Net 3.1 Compact 6.5330.110 IC Equipment for Inline Ultrafiltration Chromate in soil and air samples 2.940.1100 940 Professional IC Vario ONE 2.943.0110 943 Professional Reactor Vario 2.944.0010 944 Professional UV/VIS Detector Vario 2.858.0020 858 Professional Sample Processor – Pump 2.800.0010 800 Dosino 6.3032.150 Dosing Unit 5 mL 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 6.6059.312 MagIC Net 3.1 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 2.940.2500 940 Professional IC Vario TWO/SeS/PP 2.850.9010 IC Conductivity Detector (2 ×) 2.858.0020 858 Professional Sample Processor – Pump 2.941.0010 941 Eluent Production Module 44 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 6.2842.000 MSM-HC Rotor A 6.6059.312 MagIC Net 3.1 Professional Saccharidic tracers in aerosols by IC 2.930.2160 930 Compact IC Flex Oven/Deg 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 6.1090.420 Metrosep Carb 2 - 150/4.0 6.1090.500 Metrosep Carb 2 Guard/4.0 6.6059.311 MagIC Net 3.1 Compact Anions and cations in aerosols (PILS-IC) 2.940.2500 940 Professional IC Vario TWO/SeS/PP 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 6.1825.290 PEEK sample loop 250 µL 6.1006.510 Metrosep A Supp 5 - 100/4.0 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 6.2842.000 MSM-HC Rotor A 6.6059.312 MagIC Net 3.1 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. URG-2000-30x242-4CSS). 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. Voltammetry 2.884.0110 884 Professional VA manual for Multi-Mode Electrode (MME) 2.884.1110 884 Professional VA semiautomated for MME consisting of 884 Professional VA, measuring head for MME and two 800 Dosinos. MVA-22 Fully automated Professional VA system consisting of 884 Professional VA, measuring head for MME, 919 IC Autosampler plus for VA and two 800 Dosinos for automatic addition of auxiliary solutions. Allows the automatic processing of up to 28 samples. This system is the optimum solution for automatic analysis of small sample series. Required Accessories 6.5339.030 VA-Elektrodenkit with Multi-Mode Electrode 6.6065.202 viva 2.0 Full 45 VoltIC Vario pro VoltIC Vario pro I Heavy metals are determined by voltammetric measuring stand, anions and cations by ion chromatography. TitrIC Vario pro TitrIC Vario pro I 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. TitrIC Vario pro II 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. TitrIC Vario pro III 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. Process analysis We offer online and atline Analyzers that meet any requirement in the process industry, from single-parameter to the most advanced multiparameter analyzers. Every analyzer is custom-tailored to the specific task at hand. ADI 2045PL ProcessLab system for atline determination of various parameters using titration, colorimetry, and ISE ADI 201Y Series Single method Process Analyzers, available with titration, colorimetry, or ISE ADI 204Y Series Multifunctional Process Analyzers, available with titration, ISE, colorimetry, and voltammetry MARGA Online Analyzer for continuous monitoring of aerosols and gases in ambient air 7010 TOC Analyzer for determination of the total organic carbon content (TOC) in liquid samples Furthermore, we offer the Plug and Analyze Series – ICON Analyzer and Alert Ion Analyzer for single method, single component water analysis. Please contact your Metrohm supplier for further information. Please also consult www.metrohm.com 46 You want to be sure The new handheld Metrohm Instant Raman Analyzer (Mira) for chemical and pharmaceutical analysis. With 9000 spectra in its library, Mira gives you unparalleled power to identify what you are looking for – at the push of a button, anywhere! metrohm-nirs.com Ins_Mira_A4_EN State-of-the-art environmental analysis in China The Institute of Tropical and Marine Meteorology is lo ca-47 ted in Guangzhou in Southern China. One of the insti- tute’s missions is to extend the monitoring station’s 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 Process Analytics. You want to be sure Fei Li, researcher at the Institute of Tropical and Marine Meteorology, Guangzhou, China The new handheld Metrohm Instant Raman Analyzer (Mira) for chemical and pharmaceutical analysis. With 9000 spectra in its library, Mira gives you unparalleled power to identify what you are looking for – at the push of a button, anywhere! metrohm-nirs.com Ins_Mira_A4_EN environment.metrohm.com Herisau CH-9100 G, A ohm Metr by Switzerland in printed , SWA modifications Ecknauer+Schoch to by Subject Layout 8.000.5107EN – 2015-09