This EnviroMail highlights important practices for the collection of water samples for analysis of trace metals and mercury which can greatly improve the quality of test results, preventing false positives and false negatives, while also improving the efficiency of field sampling events.<h3>Ultra-Clean Sample Bottles for Trace Metals</h3>One of the most crucial aspects of trace metals analysis is the quality of the sample container. All plastics will leach trace amounts of common metals when exposed to nitric acid preservative, and for many metallic elements, the quality of the sample container is the most limiting factor where trace-level detection limits (DLs) are needed.ALS recently conducted a global study of sample containers to identify the best and cleanest bottles used by any of our trace metals labs around the world, evaluating over forty sample containers sourced from seven countries. We conducted ultra-trace metals testing down to 1/10th of the ALS Canada trace metals DLs, with testing done at two ALS labs that offer some of the lowest commercially available metals DLs in the world – in Vancouver and Lulea, Sweden. Testing protocols included short and long-term leaching studies with acidified samples as well as suitability testing for use with pre-charged concentrated nitric acid, which is a common practice for metals testing in some regions. Our studies confirmed that pre-charging any plastic containers with concentrated nitric acid tends to liberate higher concentrations of many common elements from the container walls (e.g., chromium), which can limit the levels to which reliable DLs can be provided.By using sample containers selected specifically for their suitability and cleanliness for trace metals, in conjunction with rigorous bottle proofing protocols, ALS can offer lower DLs with confidence that false positives will not occur due to contamination from sample bottles.Our container selection and proofing protocols are designed to ensure that prerinsing with sample is never required or even recommended for any tests we offer.<h3>Preservation of Metals with Nitric Acid</h3>Sample preservation is used with many tests to ensure test analytes are stabilized, so measured sample concentrations represent the sample condition at time of collection. For trace metals, preservation with nitric acid reduces sample pH to &lt; 2 to ensure solubility of metals prior to analysis, preventing sorption to container walls or precipitation as metal oxides or hydroxides.Traditionally, preservation for metals has been conducted in the field, but recently there has been recognition that lab preservation of metals samples is preferable for numerous reasons. In fact, the US EPA has recommended lab preservation as the best practice for sampling of metals in water for at least 35 years (Method 200.2, 1989). Among other benefits, lab preservation avoids restrictions with Transportation of Dangerous Goods (TDG), and avoids contamination risks and hazards that can occur when handling concentrated acids in the field.<h3>Lab Preservation – Best Practice for Trace</h3>Lab preservation is recommended as the best practice for trace metals analysis of waters to maximize data quality and to improve sampling logistics. Requirements for lab preservation of metals are that samples must be preserved with nitric acid in their original sampling container, with no sub-sampling or analysis permitted until completion of a 16-hour equilibration period, to ensure full solubilization of metals prior to analysis. Because of the 16-hour equilibration requirement, lab preservation is unsuitable for same-day analysis requirements. Hold times are the same as for field preservation (6 months from time of sampling), as long as preservation occurs within 14 days of sampling.Lab preservation is suitable for total metals and for fieldfiltered dissolved metals. In all cases, field filtration is required to provide defensible test results for dissolved metals (refer to section on field filtration for more details).&nbsp;Lab preservation offers data quality improvements over other preservation options for several reasons:<ul><li>Lower and more reliable detection limits can be offered - especially for chromium - versus containers pre-charged with nitric acid, due to leaching of metals over time from plastics by concentrated acid. Low-level chromium DLs are useful to screen for aquatic life risks due to hexavalent chromium.</li><li>Contamination risks are minimized by reducing physical handling in the field, and by collecting samples quickly with minimal exposure to dust (e.g., at windy mine sites).</li><li>Eliminates potential cross-contamination of nutrient samples with nitrate from nitric acid.</li><li>Addition of acid preservatives in the lab utilizes highgrade nitric acid, tested daily before use for purity control, and added to samples in a clean, controlled, dustfree environment.</li></ul>Where the absolute lowest possible DLs are required, ALS recommends lab preservation with specially prepared acidcleaned bottles (ACBs), which we provide for specific specialty test codes for ultra-trace level metals.<h3>Field Preservation for Metals: Applications and Precautions</h3>ALS also offers two field preservation options for metals in special circumstances.The use of pre-charged sample containers for metals in water is an effective and easy-to-use approach, although the DLs of some metals (chronium) are limited.Field preservation can also be achieved using small vials of 18% wt/wt nitric acid which are added to samples in the field. This is a good option where same-day analysis is required (to avoid the 16-hour equilibration time for lab preservation), but requires additional precautions to reduce contamination risks for metals or nitrate during sampling.<h3>Mercury Sampling with Pre-Charged Glass Vials</h3>Best practice for collection of water samples for testing of mercury is quite different from other metals. Because dissolved mercury can readily sorb to plastics (especially at low or trace levels). Unlike other metals, dissolved mercury is stabilized much more effectively with hydrochloric acid than with nitric acid, because mercury tends to form the stable anion [HgCl4]2- in the presence of HCl, which helps to prevent sorption to container walls.Lab preservation is also possible for mercury, but the equilibration period at the lab after preservation is longer than for other metals, at 24 hours versus 16 hours, which often adds an additional day to turnaround times. Water samples for routine-level mercury testing are normally sampled in 40 mL glass vials with tightly-sealed leakproof PTFE-lined septa caps, which virtually eliminates leaks. ALS recommends pre-charged mercury vials for routine-level testing because this practice expedites turnaround times with no significant disadvantages.

EnviroMail™23/Europe: Global Best Practices for High Quality Analysis of Waters for Trace Metals & Mercury

Each SPE mechanism/phase has a general set of solvent conditions under which SPE may be performed. Use the solvents/pH conditions listed below, volumes as determined in <a target="_blank" rel="noopener noreferrer" href="https://discover.phenomenex.com/0623-spe-technical-tip-part2-en?elqTrackId=E9D53E5725E641C0655E0409B9A065B7&amp;elq=00000000000000000000000000000000&amp;elqaid=4878&amp;elqat=2&amp;elqCampaignId=&amp;elqak=8AF59AC35AC6CFF8178E68A8DF72C3B8D482CF7C906A90E1BF5C55FDC1EA7D8B80B0">Method and Sorbent Volume Selection</a>.<h4>Reversed Phase SPE Method</h4><h5>Sorbent - SDB-L, C18, C8, PH, CN, X, XL</h5><ul><li>Analyte Properties: Low to moderate polarity (or nonpolar) Hydrophobic Neutralized/uncharged – Pharmaceuticals, Pesticides, Herbicides</li><li>Sample/Matrix: Aqueous, diluted with buffer – Biological fluids, Water</li><li>Conditioning Step<ul><li>Solvation – polar organic solvents – Methanol</li><li>Equilibration – aqueous, buffers – Water or buffer</li></ul></li><li>Wash Step: Aqueous buffers with 5 to 50 % polar organic solvent – Methanol:Water (5:95)</li><li>Elution Step: Polar or non-polar organic solvent(s) with or without water, buffer and/or strong acid or base – Methanol:Acetonitrile (50:50)</li></ul><h4>Normal Phase SPE Method</h4><h5>Sorbent - Silica, Florisil®, NH2, CN</h5><ul><li>Analyte Properties: Moderate to high polarity compounds (neutralized/uncharged) – Pesticides</li><li>Sample/Matrix: Non-polar organic solvents or moderately polar organic solvents – Hexane, chloroform, petroleum ether, toluene or methylene chloride</li><li>Conditioning Step<ul><li>Solvation – polar organic solvents (optional) – Methanol (optional)</li><li>Equilibration – sample/matrix solvent – Hexane or chloroform</li></ul></li><li>Wash Step: Non-polar organic solvents with a low concentration (1 to 5 %) of moderate to low polarity organic solvents – Hexane with 1 % THF, ethyl acetate, acetone, acetonitrile or IPA</li><li>Elution Step: Non-polar organic solvents containing higher concentrations (5 to 50 %) of moderate to high polarity organic solvents – Hexane with 10 % THF, ethyl acetate, acetone, acetonitrile or IPA</li></ul><h4>Strong Ion-Exchange SPE Method</h4><h5>Sorbet:&nbsp;Anion exchange: Screen-A, SAX, X-A, X-AW, XL-A, XL-AW Cation exchange: Screen-C, SCX, X-C, X-CW, XL-C, XL-CW</h5><ul><li>Analyte Properties: Ionized/charged compounds – Anion exchange: Acidic analytes Cation exchange: Basic drugs</li><li>Sample/Matrix: Aqueous; Low ionic strength buffers (&gt;30 mM), pH adjusted – Biological fluids plus buffer</li><li>Conditioning Step<ul><li>Conditioning – polar organic solvents – Methanol</li><li>Equilibration – low ionic strength buffers, pH adjusted – 25 mM Tris-OAc, pH 7</li></ul></li><li>Wash Step: Aqueous buffers of low salt concentrations with or without organic solvent<ul><li>Anion exchange: Buffer pH 7: Methanol (50:50)</li><li>Cation exchange:<ul><li>Buffer pH 6</li><li>1 M acetic acid</li><li>3. Methanol</li></ul></li></ul></li><li>Elution Step:<ul><li>Neutralize the charge on the weak anion or cation</li><li>Increase the ionic strength and counter ion concentration</li><li>Add a strong counter ion displacer<ul><li>Anion exchange: Hexane:ethyl acetate (75:25) + 1 % glacial acetic acid</li><li>Cation exchange: Methanol + 5 % NH₃</li></ul></li></ul></li></ul><blockquote>NOTE: These are general starting conditions. Please <a target="_blank" rel="noopener noreferrer" href="https://discover.phenomenex.com/customersupportEU?elqTrackId=9FD41A83311DD308567C001F2CC9485A&amp;elq=00000000000000000000000000000000&amp;elqaid=4878&amp;elqat=2&amp;elqCampaignId=&amp;elqak=8AF530A7A08EE95226A9F3C49828A74B76F7CF7C906A90E1BF5C55FDC1EA7D8B80B0">contact </a>your Phenomenex technical consultant for more assistance.</blockquote>

Generic SPE Method by Retention Mechanism

Normal phase SPE uses polar interactions as retention mechanism. These interactions include hydrogen bonding, dipole-dipole, induced dipole, π-π, etc. The interactions are between polar functional groups of analytes and polar sorbent chemistries.Reversed phase uses nonpolar, hydrophobic interactions as retention mechanism. These interactions include Van-der-Waals, London dispersion, π-π, etc. These interactions are between carbon rich, hydrophobic parts of both analytes and sorbent.When dealing with sample matrices that are only soluble in organic solvents, one would use a normal phase method. Examples of such matrices are oil, grease, or butter.Ideally, the sample is diluted with a nonpolar solvent (i.e. hexane) prior to sample loading. The sample can then be washed with hexane or 5% methylene chloride in hexane (analogous to washing with 5% MeOH in water in RP SPE methods to remove matrix interferences). Elution will be done with a polar solvent that can interrupt polar interactions between analytes and sorbent.Fractionation can be done by applying solvents in the order of increasing polarity or mixtures of solvents with different polarities.Below is a quick reference of solvents in ascending polarity, for Normal Phase SPE methods.<h4>Solvents in Polarity Order</h4><h5>From high to low</h5><ul><li>Hexane</li><li>Isooctane</li><li>Carbon tetrachloride</li><li>Toluene</li><li>Benzene</li><li>t-butyl methyl ether</li><li>Chloroform</li><li>Dichloromethane</li><li>Diethyl ether</li><li>Ethyl acetate</li><li>Tetrahydrofuran (THF)</li><li>Acetone</li><li>Acetonitrile</li><li>40% MeOH in acetonitrile</li><li>20% MeOH in diethyl ether</li><li>20% MeOH in dichloromethane</li><li>Isopropanol</li><li>Methanol</li><li>Water</li><li>Acetic acid</li></ul><h5>Positive Pressure Manifold for Streamlined Sample Prep</h5><ul><li><a target="_blank" rel="noopener noreferrer" href="https://www.phenomenex.com/products/presston-positive-pressure-manifold#how%20it%20works">Presston 1000</a></li></ul><img src="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/Phenomenex_Positive_Pressure_Manifold_for_Streamlined_Sample_Prep_aea498cf21.jpg" alt="Phenomenex: Positive Pressure Manifold for Streamlined Sample Prep" srcset="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/thumbnail_Phenomenex_Positive_Pressure_Manifold_for_Streamlined_Sample_Prep_aea498cf21.jpg 245w," sizes="100vw" width="960" height="350">

How is Normal Phase (NP) SPE Different from Reversed-Phase (RP) SPE?

Validation of analytical methods (i.e. procedures) usually excludes the primary sampling, but this is now widely recognised as the first step in the measurement procedure [1] (Fig.1). Validation of the whole measurement procedure therefore requires consideration of a performance characteristic that reflects the quality of all of the steps (including sampling and physical sample preparation). The uncertainty of the final measurement value is that key characteristic that unifies this whole measurement procedure and enables its validation, particularly when supported by performance characteristics that have an established role in the validation of an analytical procedure as a standalone activity [2]. This leaflet summarises the new Eurachem/CITAC guidance on the Validation of Measurement Procedures that Include Sampling (VaMPIS) [3]. It can be applied to the whole measurement process either simultaneously, where the sampling and analytical procedures are validated as a unified measurement procedure, or sequentially when the analytical procedure has previously been validated in isolation.<h4>In situ and ex situ measurement</h4>There are now many in situ measurement techniques (e.g. portable XRF in Fig. 1c), where the measurement is taken directly from the sampling target, without the need to extract a physical sample. This new mode of measurement highlights the need for an integrated approach to the definition of the measurement process so that it includes sampling. This approach is also equally applicable to the traditional mode of ex situ measurement (Fig. 1b) of a physical sample extracted from a sampling target (Fig. 1a). Both modes require the primary sampling to be included within the measurement procedure, its validation, and in the estimation of measurement uncertainty.<img src="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/Eurachem_Figure_1_Representation_of_the_whole_measurement_process_7e63297705.jpg" alt="Eurachem: Figure 1. Representation of the whole measurement process that requires validation. In the ex situ mode this includes the two steps of (a) primary sampling (in this case of a bay of lettuce heads) followed by (b) chemical analysis. In in situ mode this usually requires just one step (c) both sampling and analysis within the same measurement process (in this case in situ pXRF on an area of soil)." srcset="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/thumbnail_Eurachem_Figure_1_Representation_of_the_whole_measurement_process_7e63297705.jpg 172w," sizes="100vw" width="857" height="778"><h4>How to apply VaMPIS</h4>The only parameter of a measurement procedure that can effectively integrate the effects on data quality from all of the steps in the procedure (including sampling) is the measurement uncertainty. This uncertainty is stated within the final measurement result. It allows the user of that result to assess the effects of both random and systematic effects arising at every stage of the measurement procedure on decisions that are to be made using that result (e.g. compliance of a batch of material with a regulatory threshold). The VaMPIS approach therefore uses the uncertainty of the measurement value to judge the fitness for purpose (and hence validity) of the whole measurement procedure by comparing it with a ‘target’ uncertainty. It is essential that the target uncertainty should also include the contribution from sampling, and it can either be set by an external body (e.g. a regulator) or, if that is not available, by the user, using a technique such as the Optimum Uncertainty method ([3] Appendix B). Worked examples of validation are given where the whole measurement procedure is applied, either ex situ (Appendix A1: Nitrate in extracted composite samples of lettuce, Fig. 1a) or in situ (A2: Pb in soil by pXRF without removal of physical samples, Fig. 1c). There are eleven broad steps for the application of VaMPIS (Fig. 2). Measurement uncertainty is generally estimated using the Duplicate Method in which duplicate primary samples are taken from at least eight sampling targets by an independent reinterpretation of the sampling procedure. Both duplicate samples are then analysed in duplicate. The measurement uncertainty, and its main components from sampling and analysis (as repeatability), are estimated by applying ANOVA to the resultant measurement values, and also including analytical bias and sampling bias where possible [1]. The fitness for purpose of the procedure is judged by comparing the estimated measurement uncertainty against a value of target uncertainty set for that particular purpose [3].<img src="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/Eurachem_Figure_2_Flow_chart_for_Va_MPIS_application_0371d52580.jpg" alt="Eurachem: Figure 2. Flow chart for VaMPIS application" srcset="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/thumbnail_Eurachem_Figure_2_Flow_chart_for_Va_MPIS_application_0371d52580.jpg 127w," sizes="100vw" width="735" height="898">There are planning steps followed by implementation steps. The measurement uncertainty (MU) and its component arising from sampling (UfS) are usually estimated using the Duplicate Method followed by Analysis of Variance (ANOVA) [1]. The decision on whether the measurement procedure (MP) is fit for purpose (FFP) is based upon comparing the actual MU against the target MU. If not FFP, the decision on whether to improve the sampling procedure (SP) or the analytical procedure (AP) depends on their respective contributions to both the MU and the measurement cost. In the sequential approach to VaMPIS, the FFP of the AP, that has been previously validated in isolation, is checked to see if it is still FFP within this whole MP. If the MU from the analytical procedure needs to be improved, the most appropriate of the traditional performance characteristics [2] need to be modified to that end. (AQC is Analytical Quality Control.)The VaMPIS guide [3] also includes a discussion of the role of ongoing quality control of the whole measurement procedure (integrated measurement quality control, IMQC) to ensure ongoing quality compliance after the initial validation. One major challenge for implementation that is also discussed, is to ensure effective communication and cooperation between the laboratory staff and the oftendifferent organisation that takes the samples.<blockquote>Produced by the Joint Technical Group on VaMPIS with representatives from the Eurachem and AMC Sampling Uncertainty and Eurachem Method Validation Working Groups, as well as from CITAC &amp; Nordtest. First English edition, [April 2025], <a href="www.eurachem.org">www.eurachem.org</a></blockquote>

VaMPIS - Validation of Measurement Procedures that Include Sampling

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