trends in analytical chemistry, vol. 16, 90.7, 1997 Data related to standard calibration (SC) Intercept Slope Concentration value used to predict the corre- sponding analytical signal Each concentration of the different calibration sets ‘Average concentration of each calibration set Solution analyte concentration Confidence interval on predicted analytical signal Number of replicates for each concentration value Number of total measurements for each calibration set FR Measured analytical signal Fm Arithmetic mean ofthe signal values obtained fromm _ replicates FR _ Average analytical signal of calibration measure- ment set Ry Each analytical signal value of the measurement set, Fy Predicted analytical signal by linear regression model Fx Test solution analytical signal RSD Relative standard deviation Standard deviation Concentration standard deviation ofthe biank signal Sa Standard deviation of the predicted analytical signal R gon 2 3QpoI9 2 Seo Standard deviation of the analytical signal corre- ‘sponding to a zero concentration value Residual standard deviation of AC Residual standard deviation of SC Regression standard deviation of YC Pooled standard deviation of sxc and Sse HLeEe 385 References [11 L. Cuadros Rodriguez, A.M. Garefa Campaiia, C. Jiménez Linares, M. Romén Ceba, Anal. Lett, 26 (1993) 1243, [2] AM. Garefa Campaiia, L. Cuadros Rodriguez, C. Jiménez. Linares, F. Alés Barrero, M. Romén Ceba, Anal, Lett. 28 (1995) 369. [3] AL. Wilson, Talanta 12 (1965) 701 [4] AL. Wilson, Talanta 21 (1974) 1109. [5] L. Cuadros Rodriguez, A.M. Garcia Campaiia, F. Alés Barrero, C. Jiménez Linares, M. Romén Ceba, J. Assoc. Off. Anal. Chem. 78 (1995) 795. [6] MJ. Cardone, J. Assoc. Off. Anal. Chem. 66 (1983) 1283, [7] Turbo Pascal version 6.0 User's Guide, Borland Intemational Inc., 1992. [8]L. Cuadros Rodriguez, A.M. Garcfa Campafa, JM, Bosque Sendra, Anal. Lett. 29 (1996) 1231 [9] AM. Garefa Campaiia, Ph.D. Thesis, University of Granada, 1995, [10] AM. Garcia Campaita, F. Alés Barrero, M. Roman Ceba, Anal. Sci. 12 (1996) 647. cadre The analytical problem Miguel Vaicarcel*, Angel Rios Department of Analytical Chemistry, Univer- sity of Cordoba, E-14004 Cordoba, Spain Chemical analysis allows one to obtain the basic information for solving - partially or totally - a variety of social problems and needs. However, this information will be use- ful only if itis representative of the system or population under study. The appropriate definition of the analytical problem, which depends on the interaction between the ana- lytical chemist and the client, isa key factor to * Corresponding author. (0165-9936197/S17.00 PISO165-9936(97)00045-9 achieve such representativeness. This article deals with the main aspects and ele- ments involved in the characterisation of the analytical problem, the steps to be con- sidered and the relationship between the definition of the analytical problem and the quality of the results delivered. © 1997 Elsevier Science B.V. 1. Introduction Analytical chemistry aims at obtaining analytical information that is latent in one or more objects or systems in order to assist in the making of founded, © 1997 Elsevier Scince B.V. All ight reserved386 ECONOMIC SOCIAL PROBLEM 7) anaurncar PROCESS ANALYTICAL PROBLEM anayrtica // ‘ANALYTICAL QUALTY EXTERNAL| ‘QUALITY of | [anion dese Fig. 1. The analytical problem as an interface between the client's problem and the different analytical aspects. effective, timely decisions. The ultimate goal of this discipline is to minimise uncertainty in the qualitative, quantitative and structural information on matter in space and time. However, if the information derived is not fitted to the purpose [ 1], it will hardly be quality infor- mation, however excellent it may be in other respects (e.g. highly accurate and subject to little uncertainty). In practical terms, ensuring quality is essential for satisfying the ‘client’. If the client's demands regarding the analytical information required (e.g. expeditiousness, cost-effectiveness) are not met or are unrealistic, then the analytical chemist in charge of the laboratory that delivers it will obviously have failed in the analysis or in com- municating with the client to adequately define the problem. This intrinsic aspect of analytical chemistry is often not considered or dealt with in a systematic manner. Ultimately, an active two-way interface between the client and the analytical chemist must trond in analytical chemistry, vol. 16, no. 7, 1997 be established. The interface relates different aspects of the two connected parties and ensures consistency between requirements and their fulfil- ment (see Fig. 1), The underlying social-economic problem (e.g. toxic species in foods) entails meet- ing the requirements imposed by legislation or the client(e.g. the maximum concentration allowed ) in order to ensure quality from the body or organisa- tion delivering the products (e.g. foods) or serv- ices, which is external quality because it lies out- ide the laboratory proper. The analytical problem an be viewed as the link between these three spects and the analytical process, analytical prop- erties (capital, basic and accessory) [2] and ana- lytical quality [3], respectively. ‘The analytical problem has superseded the sim- ple concept of samples and analytes of classical analytical chemistry in today’s discipline. Many current definitions of analytical chemistry already include the problem as a substantial part. This article discusses and systematises the ana- lytical problem concept. To this end, the ‘problem’ is placed in the analytical chemical context, and the steps involved in its resolution are analysed. The degree of consistency between the information pro- duced and that required is also examined, and the way the problem is situated in the context of ana- lytical quality is explained. ANALYTICAL PROBLEM APPLIED. Basic APPROACH APPROACH suPLy ror | — BaD CHEMICAL ANALYTICAL INFORMATION | mmm | CHEMISTRY ‘weagvewen || ncorronarion sGiewnre Teena. tanto more PmoRtens oemcrnea. |] on Tecuaca l ‘ones tens Fig. 2. Basic and applied sides of the analytical prob- tem in relation to the three general types of stimuli (1— 3) that ‘arouse’ them.trends in analytical chemistry, vol. 18, no. 7, 1997 387 —i id TO ANALYZE TO CHARACTERISE — TOOETECT EXTERNAL CuALITY OF GUATTY OF FE Quali TRERECUTS ——_AMMLTIOAL PROCESS i [_croretres cies __ SEAR J neronts resus sawown | ANALYSER WNSTRUMENT.—seoanuTUE come Process yecnucue erica sass ANALYSIS DETERMINATION MEASUREMENT Fig. 3. Relationships of the analytical problem to other aspects of analytical chemistry. Links to various significance and scope ranks are also shown. 2. The problem in the analytical chemical context Analytical chemistry, as a scientific discipline, relies on special, characteristic basic and applied developments that distinguish it from other scien- tific and technical areas of knowledge. The most salient of these relate two of its essential compo- nents (in addition to education), namely (a) research and development, and (b) analytical tech- niques and methods as a whole. In this context, the word ‘problem’ can have the two meanings illus- trated in Fig. 2. Thus, it can be regarded as a demand of chemical information posed by a social-economic or scientific-technical problem (applied); also, it can be viewed as an innovative approach related to the intrinsic foundation of ana- lytical chemistry and the incorporation (adapta- tion) of developments from other scientific and technical areas (basic). This paper is essen- tially concemed with the first aspect, as depicted in Fig. 1. The analytical problem has changed the tradi- tional role of the analytical chemist. This has entailed a switch from a typically passive attitude to an active one that involves a symbiotic, two-way relationship with both economic and social bodies, and other scientific and technical areas. In addition, analytical chemistry is playing an increasingly prominent role outside the laboratory, for exam- ple in sampling and on-site delivery of analytical information. As recently pointed out by Thorpe and Ullman [4] in relation to industry profes- sionals, this new approach should be taken into account in training new generations of analytical chemists. A hierarchical approach to analytical chemistry [5] reveals relations between the different signifi- ‘cant parts and the scope of analytical chemistry. As shown below, the analytical problem arising froma388 ECONOMIC, SOCIAL, SCIENTIFIC OR TECHNICAL PROBLEM. ty th tt (eM //7/ OBJECT SAMPLE(S) MEASURAND(S) YZ ANALYTES) yy) wvTE( Sos TANGIBLE SIDE tends in analytical chemisty, vol. 16, no. 7,1997 ooars ‘ANALYTICAL CHEMISTRY CLASSICAL ANALYTICAL CHEMISTRY L Fig. 4, Tangible and intangible elements of the analytical problem. social-economic or scientific-technical problem is at the top of a hierarchy that is connected to the top positions of other orderings as shown in Fig. 3 Thus, the problem is related to the action of analy- sing; this involves characterising and interpreting, both of which are subsequent to detecting and sens- ing. Therefore, solving the problem entails issuing reports rather than simply delivering results or raw data, Also, the analytical problem is directly related to the external quality as set by the social or eco- nomic body that demands the information. Fig. 3 also relates other analytical aspects of the hierarchy at levels below that of the problem. 3. Elements of the analytical problem An analytical problem consists of four basic ele- ‘ments that can be ranked in terms of significance and scope as shown in Fig. 4. The object is the entity to be described in chem- ical terms via the analytical results and their inter- pretation, Typical examples of objects include sea water, ariver, a mineral shipment, the gas that flows by a given point over a preset period, etc. As arule, three spatial coordinates and one temporal coordi- nate are needed to fully describe an object — some require additional coordinates such as pressure, temperature, etc. The object must be a faithful reflection of the social-economic or scientific-tech- nical problem addressed. In statistical terms, it could be defined as a population consisting of an infinite number of samples. The representativeness of the results produced is a capital property —akin to accuracy in importance — that encompasses the con- sistency between the results and the aliquots assayed (the object), the analytical problem and the social-economic problem (6 The sample can be defined in broad terms as a part of the object, coinciding with its statistical definition. However, the analytical chemical defini- tion distinguishes various types of samples, includ- ing bulk samples, composite samples, gross sam- ples, batches, strata, sub-samples, increments, test portions, specimens, etc., depending on size and on their relationship to the object and to one another (71. The measurand is the quantity to be measured. In chemical analysis, this usually coincides with the amount or concentration of an analyte but can also encompass other quantities such as pH, colour, etc. Fig. 4 also shows that classical analytical chem- istry must be expanded beyond its traditional fron- tiers. The above elements make up the tangible part of the analytical problem related to the matter to be analysed in order to derive the information required, The analytical problem also includes other major components such as planning the ana- lytical strategy, designing the analytical proc-trends in analytical chemistry, vol. 16, no. 7, 1997 TSENTIRCATION AND CONF AUATION took ene [J2Kec>e| HSE copnecrve ferione | Fig. 5. Steps involved in planning and resolving an analytical problem, ess(es) required, checking the quality of the results, etc., which are discussed in the following section, 4. Steps of the analytical problem-solving process Integrating the tangible and intangible aspects of an analytical problem with its relationship to the original social-economic problem (Fig. 4) allows one to envisage the steps required for its correct approach and resolution (i.e. for delivering analyt- ical information of use in resolving the social-eco- nomic problem addressed ). Such steps are depicted in Fig. 2 and commented on below. 4.1. Identifying and confirming the analytical information required The analytical problem cannot be approached effectively from a single side; in fact, both parties 389 (the client and the analytical chemist) should take an active role in its planning and resolution, partic- ularly in the first step [8], where the interface shown in Fig. | is crucial. The analytical chemist should co-operate with the client in identifying the information needed for the making of informed, effective, and timely decisions on the particular problem addressed. This requires that the analytical chemist know the characteristics of the social, eco- nomic, scientific or technical problem concerned and have proper answers to such questions as what, why, how, when and where. Both parties should communicate fluently both at the beginning and at the end of the cycle implicit in Fig. 5. To what extent the analytical chemist needs to be involved in this step will depend on the profile of the other party’s representative, who can range from an ana- lytical chemistry expert to a professional with no technical qualifications. No doubt, this step is crit- ical; without correct planning, tackling the analyt- ical problem makes no sense. The analytical chem- ist, whether by imposition or tradition, has been scarcely involved in this step. Obviously, modern analytical chemistry would be meaningless if the analytical chemist were only assigned his former roles. 4.2. Pinpointing the analytical information required This second step should be implemented by the analytical chemist, who must convert the chemical information defined in the first step into the analyt- ical information actually needed to help resolve the social-economic problem addressed, By the end of this step, some specific characteristics should have been determined (see Fig. 6). First, the object and the sampling plan should be unequivocally estab- lished. Second, the measurands (analytes) whose presence or concentration is to be determined should be identified. Third, the types of analysis to be performed (qualitative, quantitative, struc- tural; static, temporal, spatial; global —total content = or individual) should be decided upon. Finally, the quality level demanded from the analytical information to be delivered in terms of the three types of analytical properties (capital, basic and accessory) and their mutual relationships should also be identified [2]. This last requirement is cru- cial because an overall quality compromise must usually be made between accuracy and representa- tiveness — which rely on precision, sensitivity, selectivity and correct sampling ~ in relation to390 tends in analytical chemistry, vol. 16, 0. 7, 1997 WEASURAND|S), ‘ANALYTE(S) ‘SPECIFIC DETAILS OF THE REQUIRED ANALYTICAL INFORMATION | Teporat, stanc| 'ANDIOR SPATIAL ‘QUALITATIVE, QUANTITATIVE ‘STRUCTURAL GLoBAL DISCRIINATED| LEVELS OF ANALYTICAL PROPERTIES Fig. 6, Analytical characteristics of the information required: second step in the analytical problem-solving process. productivity (expeditiousness, cos and personal safety and comfort ). The compromisi should be consistent with the definition of the an: lytical problem, which was defined above as the interface between the two parties. The performance to be achieved in terms of the properties that deter- mine quality and those that describe productivity in order to provide an effective solution to the analyt- ical problem should be established. 4.3, Planning the analytical strategy ‘The immediate consequence of the laboratory’s role in resolving the problem is the need to design one or more analytical processes suited to the objectives. In so doing, one should consider the following four factors: (a) the characteristics of the information required; () those of the object and/or sample; (c) the material, instrumental and human resources available; and (d) the price the client is willing to pay for the analytical informa- tion to be delivered. The analytical process to be implemented should encompass every step and sub-step between the uncollected, unmeasured, untreated sample and the results, delivered as required. The need for specific classical analytical and instrumental systems, hyphenated techniques, automatic systems, screening devices, process ana- lysers, etc., will be dictated by these factors, which should therefore be examined in a systematic man- ner. The analytical strategy may lead to the need to develop specific or global innovations in order to meet the information demands. The analytical work to be carried out inside and outside the laboratory should inevitably include the implementation of quality control and monitoring systems in the framework of quality assurance programmes. These provide solid support in meeting objectives consistent with the analytical problem. 4.4. Monitoring the results produced This step involves two distinct actions, both of which are related to validation and to the first two steps of the analytical problem-solving process. First, one must assess internal quality, which entails validating the results in terms of the analytical prop- erties and compromises made in setting their expected levels in the second step ~ a task assigned tothe analytical chemist. Second, the results must be validated in relation to the information requested by the client by assessing their external quality, which again entails establishing the interface implicit in the first step. In this way, the circle that constitutes the analytical problem is closed. 4.5. Implementing corrective actions When the results obtained do not meet the ©~ Fig. 7. Comparison between the amount of analytical information produced and the client's actual needs.tends in analytical chemistry, vol. 16, no. 7, 1997 BASIC APPROACH 0 SET OF PROPERTIES: TO MEET THE 391 APPLIED APPROACH 0 "ANALYTICAL PROPERTIES ANALYTICAL QUALITY. "ANALYTICAL PROBLEM RESOLUTION ——" Fig. 8. Basic and applied sides of analytical quality in relation to the generic definition of quality. client's requirements or fail to reach the preset lev- els for the analytical properties, one must recon- sider the analytical strategy used after careful anal- ysis of the data produced by the quality systems employed, which are of great assistance in diagnos- ing the source of deviations. This may lead to changes affecting specific conditions (standards, instrumental settings) or measuring elements (cal- ibration system, type of instrument), or even the whole system (methodology )employed in the ana- lytical process(es) used. The results produced by the adjusted analytical strategy should be subjected to double validation. Frequently, these corrective actions are improvised rather than carefully planned and inevitably result in a waste of time and work, 5. Consistency between the information required and delivered Frequently, the information expected from the laboratory is divorced from that which it actually delivers, as a result of the analytical strategy being incorrectly planned and resolved. Fig. 7 compares these two types of information in the various respects that are briefly discussed below. Ideally (Fig. 7a), the two types of information coincide in both qualitative (measurands, types of analyses ) and quantitative terms (global or discrete determinations, uncertainty levels). The informa- tion produced can depart from that demanded in two ways. Thus, the two may not coincide fully (Fig. 7b) as the main result of a serious misunder- standing (e.g. the laboratory provides the hydro- carbon concentration rather than that of metal traces requested by the client). Also (Fig. 7c), the information delivered by the laboratory may be inadequate to fulfil the information needs of the client (e.g. the client demands a speciation analysis and the laboratory provides the overall concentra- tion or the former requires quantitative composition and is supplied with qualitative composition only). Finally (Fig. 7d), the information delivered may be partly excessive and superfluous (e.g. only global contamination values are required and an endless ist of species with their concentrations and uncer- tainty is provided, or estimated concentrations are more than fit for the purpose but the laboratory delivers data with low uncertainty that can only have been obtained by working under excellence conditions); the result is a waste of material and human resources. This latter situation is far from uncommon: only a small portion of the analytical information supplied is used in making social-eco- nomic decisions. If the analytical problem is cor- rectly defined, then the information produced will be consistent with that required. Itis often the case that the client is unaware of the laboratory's capacity to provide special information that could help re-approach the social-economic problem and increase external quality. Also, the client occasion- ally requests information with some connotations (e.g. low cost, expeditiousness) that are technically unfeasible. These situations can be avoided by using the analytical problem as a functional inter- face392 6. Analytical problem and quality The ISO definition of quality includes the basic (properties, characteristics) and applied approaches (meeting the explicit or implicit requirements), as well as their relationships, which are echoed in the analytical chemical domain: analytical properties/ metrological char- acteristics (traceability, uncertainty) and resolu- tion of the analytical problem (see Fig. 8). The relationships between the basic and applied sides of analytical chemistry are also self-obvious and are reflected in steps b, ¢ and d of the analytical process, One essential component of analytical quality is thus resolving the analytical problem in order to meet external quality requirements (client satisfac- tion), as shown in Fig. 1. Itis interesting to note that analytical quality is currently associated almost exclusively with internal quality (the metrological quality of the results, laboratory quality control); by contrast, representativeness of the results and resolving the analytical problem have only recently started to be considered essential to laboratory quality. As a result, analytical chemistry has long. been confined to a very low technical rank; unless it gradually expands its traditional frontiers, it will hardly be able to effectively fulfil its objectives. Dealing seriously with analytical quality entails systematically considering all these issues. ‘A brief review of the previous definitions of quality supports this integral approach. Thus, it has been stated that “no quality is to be expected unless the objectives are properly defined”; in fact, the analytical problem prompts such objectives to the analytical chemist. “Quality is the concern of all of us rather than a few” — quite an adept assertion because analytical quality is only meaningful within the framework of global quality, which is outside the laboratory. 7. Concluding remarks In the preceding sections we have presented and discussed an aspect of analytical chemistry that has frequently been mentioned in its recent definitions but has scarcely been dealt with in a systematic manner. The analytical problem has superseded samples and analytes, which used to be the key objectives in the past, thereby leading to a more general, creative and innovative approach to ana- lytical chemistry. ‘rand in analytical chemistry, vol. 16, no. 7, 1997 The proposed scheme for defining and resolving the analytical problem is flexible and adjustable to any situation. Obviously, routine control laborato- ries should replan the above-described steps every time a new client requests their services or poses a new information need. After the problemis planned and resolved, the analytical chemist should monitor both the results and the client’s objectives, which may change with time and call for adjustments in the analytical strategy and hence in the analytical process. Existing laboratories can also benefit from this approach; if more analytical chemists were to implement steps A and B in Fig. 5, the analytical strategies they are currently using would most likely be changed. Systematically addressing the analytical prob- Jem should become a key pedagogical message in the training of future analytical chemists. The mes- sage should be transmitted not at the end of the taining cycle, by which time students should have acquired a broad view of analytical chemistry, but from the very beginning, via meaningful exam- ples. This is a Subliminal mechanism for placing analytical chemist in its right place. 8. Glossary of terms Analytical problem. An interface between the information that society and industry require from the analytical laboratory and the information the laboratory returns. Social-economic problem. A problem that arises, from the objectives of a public or private body in seeking to maintain, improve or guarantee the qual- ity of their products and /or services. External quality. Features of the products and/or systems of the public or private body to which the laboratory is answerable [3]. It is ‘external’ from the analytical standpoint. Analytical quality. Features of the chemical measurement process and the analytical results that are reflected in analytical properties [3]. This is ‘internal’ quality in analytical terms. Acknowledgements Financial support provided by the DGICyT (PB95-0977) is gratefully acknowledged.tronds in analytical chemistry, vol. 16, no. 7, 1997 References [1] M. Thompson, T. Fearn, Analyst 21 (1995) 275, [2] M. Valeareel, A. Rios, Anal. Chem. 65 (1993) BIA [3] M. Valedrcel, A. Rios, Trends Anal. Chem. 13 (1994) 17, [4] TM. Thorpe, A.H. Ullman, Anal. Chem. 68 (1996) 4774. 393 [5] M. Valedrcel, M.D. Luque de Castro, Trends Anal, Chem. 14 (1995) 242. [6]B. Kratochvil, D. Wallace, J.K. Taylor, Anal. Chem. 56 (1984) 114R. [7] A. Rios, M. Valedrcel, Analyst 119 (1994) 109. [8] K. Roberts, Chem. Br., January (1996) 11. hiends Advances in stationary phase development in suppressed ion chromatography Peter E. Jackson’, Christopher A. Pohl R&D, Dionex Corporation, 1228 Titan Way, Sunnyvale, CA 94088-3606, USA Selectivity variations in suppressed ion chro- matography (IC) are most commonly intro duced through the use of different stationary phases. In recent years, considerable advan- ces have been made in developing new sta- tionary phases for IC. Advances include the development of solvent compatible p. mers, methacrylate-based latex materials for the analysis of oxyhalide species, high capacity, weak acid cation exchangers for the simultaneous determination of ammo- nium and alkali/alkaline earth cations, and hydroxide selective anion exchange resins for improved isocratic and gradient hydrox- ide separations. These advances continue to broaden the applicability of ion chromatogra- phy, and it appears likely that future develop- ments in stationary phase technology will continue to enhance the utility of this tech- nique. © 1997 Elsevier Science B.V. 1. Introduction Ton chromatography (IC ), which was first intro- duced over two decades ago [ 1], has become a well established, regulatory approved methodology for the determination of ionic species [2]. While IC *Corresponding author. 0165-9936/97/S17.00 PUSO165-9936(97)00050-2 was initially seen as a tool for the analysis of inor- ganic anions and cations, particularly in environ- mental samples [3,4], the use of different separa- tion and detection methods has greatly expanded the range of solutes and applications to which the technique can be applied. Nevertheless, the simul- taneous analysis of common anions (fluoride, chloride, nitrite, bromide, nitrate, phosphate and sulfate) remains the most important routine appli- cation of IC, followed by determination of ammo- nium and the alkali/alkaline earth cations [ 5-7]. These solutes are typically determined using an ion exchange separation with suppressed conductivity detection, consequently the manipulation of ion exchange selectivity remains the important means of moderating separations in ion chromatography. In the case of traditional high performance liquid chromatography (HPLC), stationary phase devel- ‘opment has largely been directed toward improving column efficiency and eliminating any non-ideal behavior, ie. interaction with residual surface sila- nol groups [8 J. Changes in selectivity are primarily achieved through varying the nature of the mobile phase rather than the stationary phase [8,9 ]. Alter- natively, selectivity variations in suppressed IC have typically been achieved through the use of different stationary phases. Historically, the major- ity of the stationary phases used in suppressed IC have been agglomerated ion exchange resins [5— 7). These agglomerated (or peliicular) materials consist of a monolayer of charged latex particles which are electrostatically attached to a surface functionalized, PS-DVB core particle. This inner particle is totally covered by the fully functional- © 1997 Elsevier Science B.V, AI rights reserved.