White Paper 70682 Automated Ion Chromatography Titration System for Water Analysis

Bernard Sheldon and Monika Verma Thermo Fisher Scientific, Sunnyvale, CA, USA

Executive Summary The U.S. EPA lists a set of secondary water quality standards in addition to the National Primary Drinking Water Regulations. These secondary standards recommend maximum levels of certain analytes in water. These analytes can cause a variety of issues for the water consumer, ranging from poor taste and appearance to detrimental health effects. Some parameters, such as water hardness, can cause system problems related to scale formation. As a result, drinking water consumers and industries that utilize water may need to understand the secondary qualities of the water they source. Fortunately, Titration Ion Chromatography systems are fully automated to quickly and easily provide the levels of many of the secondary analytes suggested by the U.S. EPA.

Keywords Water Quality Standards Titration, Ion Chromatography, In addition to the well-known and highly regulated National Primary Drinking Water Regulations METTLER TOLEDO, Conductivity, (NPDWRs or primary standards), the U.S. EPA lists a set of secondary water quality standards pH, Alkalinity called the National Secondary Drinking Water Regulations, detailed in Table 1. These regulations recommend non-mandatory limits for 15 water quality contaminants. While the EPA does not mandate these levels, the recommendations are designed to control deleterious effects in water. For example, too much fluoride in drinking water can cause pitting in consumers’ tooth enamel. High “permanent” or calcium hardness will cause scale formation in pipes or boilers, and spotting on cleaned products. Due to such issues as these, water consumers, including industries that use water directly or treat the water before use (to eliminate a problem resulting from contaminants), are concerned with the quality of water they source. 2 Table 1. Water Quality- EPA secondary standards.

Contaminant Secondary MCL Noticeable Effects above the Secondary MCL Aluminum 0.05 to 0.2 mg/L colored water Chloride 250 mg/L salty taste Color 15 color units visible tint Copper 1.0 mg/L metallic taste; blue-green staining Corrosivity Non-corrosive metallic taste; corroded pipes/ fixtures staining Fluoride 2.0 mg/L tooth discoloration Foaming agents 0.5 mg/L frothy, cloudy; bitter taste; odor Iron 0.3 mg/L rusty color; sediment; metallic taste; reddish or orange staining Manganese 0.05 mg/L black to brown color; black staining; bitter metallic taste Odor 3 TON (threshold odor #) “rotten-egg”, musty or chemical smell low pH: bitter metallic taste; corrosion pH 6.5 - 8.5 high pH: slippery feel; soda taste; deposits Silver 0.1 mg/L skin discoloration; graying of the white part of the eye Sulfate 250 mg/L salty taste Total Dissolved Solids (TDS) 500 mg/L hardness; deposits; colored water; staining; salty taste Zinc 5 mg/L metallic taste

SMCL: Secondary Maximum Contaminant Level. The EPA Secondary Drinking Water Regulations are “non-enforceable guidelines”- U.S. EPA Recommended. These standards impact the quality of the water, but not necessarily its safety. According to the U.S. EPA, qualities influenced can be: • Aesthetic effects — undesirable tastes or odors; cloudiness • Cosmetic effects — effects which do not damage the body but are still undesirable • Technical effects — damage to water equipment or reduced effectiveness of treatment for other contaminants. Some parameters, especially hardness and total ion content, have impacts on industrial processes, as well. Scale formation, for example, in pipes. Spotting after a washing process can occur. If the water has to be treated to alleviate these problems the levels before treatment need to be known to control the treatment process and qualify it.

Manual vs Automated Approaches Drinking water utilities (i.e. municipalities) and industrial water consumers often test and report on a number of secondary water quality parameters, because of their importance to their customers. These values can be obtained using a number of different analytical techniques, as basic as manual titration to determine pH and alkalinity. Table 2 contrasts manual and automated approaches to a selection of analyses, demonstrating the benefit of automated approaches.

Table 2. Water quality analysis: methods.

Parameter Manual Method Automation Titration or IC pH Direct Measurement Automated Conductivity Direct Measurement Automated Temperature Direct Measurement Automated Alkalinity Titration Automated Titration Total Hardness Ion-Selective Electrode (ISE), Titration Ion Chromatography Ca2+ ISE, Complexometric Titration Ion Chromatography Mg2+ ISE, Complexometric Titration Ion Chromatography Cl- ISE, Colorimetry Ion Chromatography

2- SO4 Turbidimetry Ion Chromatography Automating even a single analysis like titration provides significant reductions in the amount of 3 manual labor required in addition to cutting costs. As an example, Table 3 shows an estimation of the labor time saved for 10 samples for a single titration analysis.

Table 3. Water quality analysis: Manual vs. Automation.

Labor Time- Automated Labor Time- Manual Operation Time Saved 10 samples Operation 10 Samples Measure 50 mL sample 4 minutes Fill sample beakers 1 minute 3 minutes Add indicator 5 minutes Automatic None 5 minutes Enter sample ID, Situate beaker 3 minutes Load autosampler 3 minutes None Titrate 20 minutes Titrate None 20 minutes Remove samples Rinse and change sample 5 minutes 1 minute 4 minutes from autosampler Total labor time, Total labor time, manual 37 minutes 5 minutes 32 minutes automate

Combining Titration and Ion Chromatography for Water Analysis Titration and ion chromatography can, as separate systems, provide the results of several different types of analyses automatically. Automated titration can be implemented to provide values such as conductivity, pH, alkalinity and carbonate hardness. Ion chromatography provides automated analysis of the individual anion and cation concentrations. Operation of these systems separately involves loading at least two autosamplers and operating at least two instrument control/data acquisition software packages. Additionally there is the issue of data compilation. Utilizing separate IC and Titration systems requires data from the ion chromatographs and the titrator to be combined by manual entry into a spreadsheet to calculate ion balance and permanent (or calcium) hardness. Unfortunately, this process of manual data entry increases required labor time and introduces the possibility of transcription errors and loss of fidelity and accuracy of results. What Automated Methods exist on the market? The METTLER TOLEDO™ titration system and liquid handler combined with two Thermo Scientific™ Dionex™ ion chromatography systems creates a fully automated water analysis system. This fully automated system measures sample conductivity and determines the best sample injection volume for ion chromatography analysis. The system can automatically dilute ion standards, removing the need for manual standards dilutions. The system provides automated multilevel calibration enabling analysis of a large number of drinking surface and ground water samples. The parameters determined by this water analysis system include:

- - - - - 3- 2- • Anions (F , Cl , NO2 , Br , NO3 , PO4 , SO4 ) • Cations (Na+, NH4+, K+, Mg2+, Ca2+) • Conductivity, temperature and pH measurement • Titration of acid capacity • Total hardness (calculated from measured Mg2+ and Ca2+ amounts) • Ion balance automatically calculated for each sample The Ion Chromatography part of the solution comprises either two Thermo Scientific Dionex ICS-1100 systems or two Dionex ICS-1600 systems; or one each for anion and cation analysis. Anions are analyzed on a Thermo Scientific™ Dionex™ IonPac™ AS22-Fast (4 mm) column; cations are separated on a Dionex IonPac CS12A-5μm (3 mm) column. IC analysis is performed simultaneously with titration for a completed analytical procedure in approximately 20 minutes. A system with a single IC is also available for laboratories requiring only anion results. Additional features that enhance the productivity and accuracy of the system include automated dilution of ion chromatography concentration standards, pH electrode calibration and verification.

For ion analysis by IC, automatic selection of the correct sample loop size based on a conductivity White Paper 70682 value is also enabled. This eliminates time-consuming and costly rework of samples.

Thermo Scientific™ Dionex™ Chromeleon™ Chromatography Data System Software integrates all results into a single convenient report ensuring automatic data analysis and reporting. The combined Titration IC system provides traceable ion analysis of water samples using the audit trail feature of Chromeleon software.

Figure 4. METTLER TOLEDO titration system and liquid handler combined with two Dionex IC Systems.

Works Cited • (n.d.). http://www.dionex.com/en-us/webdocs/86525-Bro-Water-Analysis-03May2010-LPN2527.pdf • IC Titration Product Support Package • Automated Ion Chromatography Titration System for Water Analysis, Pittcon 2013, (2360-4) • http://www.dionex.com/en-us/products/ion-chromatography/ic-rfic-systems/ic-titrator/ lp-113695.html

www.thermofisher.com/dionex ©2016 Thermo Fisher Scientific Inc. All rights reserved. METTLER TOLEDO is registered trademark of Mettler-Toledo International Inc. All other trademarks are the property of Thermo Fisher Scientific Inc. and its subsidiaries. This information is presented as an example of the capabilities of Thermo Fisher Scientific Inc. products. It is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others. Specifications, terms and pricing are subject to change. Not all products are available in all countries. Please consult your local sales representative for details.

Australia +61 3 9757 4486 Denmark +45 70 23 62 60 Japan +81 6 6885 1213 Switzerland +41 62 205 9966 Austria +43 1 333 50 34 0 France +33 1 60 92 48 00 Korea +82 2 3420 8600 Taiwan +886 2 8751 6655 Belgium +32 53 73 42 41 Germany +49 6126 991 0 Netherlands +31 76 579 55 55 UK/Ireland +44 1442 233555 Brazil +55 11 3731 5140 India +91 22 6742 9494 Singapore +65 6289 1190 USA and Canada +847 295 7500 China +852 2428 3282 Italy +39 02 51 62 1267 Sweden +46 8 473 3380

WP70688_E 09/16S