**SW-846 Update V 9015 - 1 Revision 1**

**October 2012 METHOD 9015** 

**METAL CYANIDE COMPLEXES IN WATERS AND WASTE EXTRACT S USING** 

**ANION EXCHANGE CHROMATOGRAPHY AND UV DETECTION**

**SW-846 is not intended to be an analytical trainin g manual. Therefore, method**  **procedures are written based on the assumption that they will be performed by analysts who are**  **formally trained in at least the basic principles o f chemical analysis and in the use of the subject**  **technology.**

**In addition, SW-846 methods, with the exception of required method use for the analysis**  **of method-defined parameters, are intended to be gu idance methods which contain general**  **information on how to perform an analytical procedu re or technique which a laboratory can use**  **as a basic starting point for generating its own de tailed standard operating procedure (SOP),**  **either for its own general use or for a specific pr oject application. The performance data**  **included in this method are for guidance purposes o nly, and are not intended to be and must not**  **be used as absolute QC acceptance criteria for purp oses of laboratory accreditation.** 

**1.0 SCOPE AND APPLICATION**

**1.1 This method covers the determination of metal cyanide complexes in waters**  **and extracts of solid wastes using anion exchange c hromatography and UV detection (Refs. 1,**  **2). The following analytes have been determined by this method:** 

**Analyte Common Name**

**[Ag(CN) 2**  **] -**  **Dicyanoargentate(I)**

**[Au(CN) 2**  **] -**  **Dicyanoaurate(I)**

**[Co(CN) 6**  **] 3-**  **Hexacyanocolbaltate(III)**

**[Cu(CN) 3**  **] 2-**  **Tricyanocuprate(I)**

**[Fe(CN) 6**  **] 3-**  **Hexacyanoferrate(III) a** 

**[Fe(CN) 6**  **] 4-**  **Hexacyanoferrate(II) b** 

**[Ni(CN) 4**  **] 2-**  **Tetracyanonickelate(II)**

**a Also referred to as ferricyanide** 

**b Also referred to as ferrocyanide** 

**1.2 The use of alkaline sample preservation condit ions for aqueous samples**  **ensures that all metal cyanide species are solubili zed and recovered in the analysis (Refs. 3-6).** 

**1.3 Prior to the analysis of solid waste samples, the Method 9013 alkaline**  **extraction procedure is necessary (Ref. 7). For th e extract solutions to be analyzed by this**  **method, the procedure in Sec. 11.2 needs to be perf ormed after the Method 9013 extraction** 

**process.**

**1.4 This method may be applied to water and Method 9013 extract samples**  **containing metal cyanide complexes with concentrati ons ranging from 0.2-200 mg/L (measured**  **as [M(CN) b**  **] x-**  **, where M is the metal cation, b is the number of c yanide ions, and x is the overall** **SW-846 Update V 9015 - 2 Revision 1**

**October 2012 charge of the metal cyanide complex anion). This r**  **ange will differ depending on the specific metal cyanide analyte, with some exhibiting greater**  **or lesser detection sensitivity than others. Approximate calibration ranges are provided in Tabl**  **e 1. Concentrations greater than the specific analyte range may be determined after appr**  **opriate dilution.**

**1.5 Metal cyanide concentrations less than 0.2 mg/ L may be determined through**  **the use of on-line sample preconcentration coupled with anion exchange chromatography.**  **Specific instructions for performing anion exchange chromatography analysis using sample**  **preconcentration are given in Sec. 11.4. The conce ntration range for detection will vary**  **depending on the specific metal cyanide analyte, wi th some exhibiting greater or lesser**  **detection sensitivity than others. Approximate cal ibration ranges are provided in Table 2. The**  **preconcentration method is not applicable for silve r and copper cyanide complexes in matrices**  **with total dissolved solids (TDS) greater than 1000 mg/L.** 

**1.6 This test method is capable of resolving the m etal cyanide complexes of iron,**  **cobalt, silver, gold, copper, and nickel. The test method may also be applied to the**  **determination of additional metal cyanide complexes , such as those of palladium and platinum.**  **However, it is the responsibility of the user of th is method to establish the validity of the test**  **method for the determination of cyanide complexes o f other metals.** 

**1.7 This method cannot determine some weak metal c yanide complexes, such as**  **zinc- and cadmium-cyanide complexes. These complex es elute very quickly and therefore**  **cannot be differentiated from the solvent peak in t he chromatogram.** 

**1.8 This test method is not applicable for matrice s with high ionic strength**  **(conductivity greater than 70,000** μ **mhos/cm) or high TDS (greater than 30,000 mg/L).**

**1.9 The reactive cyanide content of a waste is not determined by this method and**  **this method is not required by the RCRA regulations for the determination of the hazardous**  **waste characteristic of reactivity. See 40 CFR 261 .23 for information on the characteristic of**  **reactivity.**

**1.10 This method is useful for the direct determin ation of metal cyanide complexes.**  **The method is important from an environmental persp ective in that it can differentiate between**  **the cyanide species of limited toxicity and the hig hly toxic free cyanide (HCN and CN** 
**- ) that**  **together make up total cyanide (Ref. 3). The toxic ity of metal cyanide complexes is generally**  **related to their ability to dissociate in the envir onment and release free cyanide (Ref. 8).**  **Table 3 presents the log K stability constants for selected metal complex cyanides which may**  **be used to provide an estimate of their relative en vironmental toxicity. Previous determinations**  **of metal cyanide complexes have been made based on the assumption that the concentration is**  **equivalent to the difference between total cyanide and free cyanide. This approach is subject to** 

**error because different methods used to determine f ree cyanide, such as the cyanides**  **amenable to chlorination method (Ref. 9-11) or the weak-acid dissociable cyanide method**  **(Refs. 10, 11) often provide widely varying results , thus impacting the metal cyanide complex**  **concentration that is determined by difference. Di rect analysis using anion exchange**  **chromatography avoids these method biases and provi des a more accurate and precise**  **determination of metal cyanide complexes.**

**1.11 Prior to employing this method, analysts shou ld consult the disclaimer** 

**statement at the front of the manual and the inform ation in Chapter Two for guidance on the**  **intended flexibility in the choice of methods, appa ratus, materials, reagents, and supplies, and** **SW-846 Update V 9015 - 3 Revision 1**

**October 2012 on the responsibilities of the analyst for demonstr**  **ating that the techniques employed are appropriate for the analytes of interest, in the ma**  **trix of interest, and at the levels of concern.**

**In addition, analysts and data users are advised t hat, except where explicitly required in**  **a regulation, the use of SW-846 methods is** not **mandatory in response to Federal testing requirements. The information contained in this me**  **thod is provided by EPA as guidance to be used by the analyst and the regulated community in**  **making judgments necessary to generate results that meet the data quality objectives for t**  **he intended application.**

**1.12 This method is restricted to use by, or under supervision of, properly**  **experienced and trained personnel knowledgeable of anion exchange chromatography and UV**  **detection. Each analyst must demonstrate the abili ty to generate acceptable results with this** 

**method.**

**2.0 SUMMARY OF METHOD**

**2.1 For aqueous samples containing 0.2 - 200 mg/L metal cyanide complexes,**  **dissolved metal cyanide complexes are separated and quantified using anion exchange**  **chromatography coupled with UV detection. For soli d waste samples, the alkaline extraction**  **procedure described in Method 9013 is necessary pri or to chromatographic analysis of the**  **resulting extract. A sample volume is injected int o the chromatograph and onto an anion**  **exchange column where the metal cyanide analytes ar e separated from the sample matrix by**  **temporary retention on the column. The metal cyani de complexes are eluted from the column**  **by the eluent gradient and detected as signal peaks using UV absorbance at 215 nm. Their**  **concentrations in the sample are determined by comp arison of the analyte peak area with a**  **standard calibration plot. The concentration range will differ depending on the specific metal**  **cyanide complex, with some complexes exhibiting gre ater or lesser detection sensitivity than**  **others based on their molar absorptivity. Under th e alkaline conditions of the analysis,**  **ferricyanide ([Fe(CN) 6**  **] 3-**  **) is reduced to ferrocyanide ([Fe(CN) 6**  **] 4-**  **) co-eluting as a single analyte peak, with any unreduced ferricyanide exhibited as**  **tailing on the ferrocyanide peak.**

**2.2 For aqueous samples containing 0.5 - 200 μg/L metal cyanide complexes,**  **dissolved metal cyanide complexes are determined us ing anion exchange chromatography**  **coupled with on-line sample preconcentration (Ref. 12). For solid waste samples, the alkaline**  **extraction procedure described in Method 9013 is ne cessary prior to chromatographic analysis**  **of the resulting extract. A sample volume is passe d through an anion exchange concentrator**  **column. As the sample passes through the column, t he metal cyanide complexes are retained** 

**and concentrated on the column while the remainder of the sample matrix is directed to waste.**  **Following concentration, the metal cyanide analytes are eluted from the concentrator column**  **through gradient elution onto an anion exchange col umn where the remainder of the analysis is**  **completed as described in Sec. 2.1. The calibratio n range using sample preconcentration is**  **nominally 0.5-200** μ **g/L metal cyanide complexes. This range will diffe r depending on the**  **specific metal cyanide analyte, with some species e xhibiting greater or lesser detection**  **sensitivity than others based on their molar absorp tivity.** 

**2.3 Samples containing 200** μ **g/L - 0.5 mg/L metal cyanide complexes may either be analyzed using the preconcentration chromatograp**  **hy method after appropriate dilution or as described in Sec. 2.1, using a larger injection vol**  **ume. SW-846 Update V 9015 - 4 Revision 1** 

**October 2012 3.0 DEFINITIONS** 

**Refer to Chapter One, Chapter Three, and the manuf acturer’s instructions for definitions**  **that may be relevant to this procedure.**

**4.0 INTERFERENCES**

**4.1 Solvents, reagents, glassware, and other sampl e processing hardware may**  **yield artifacts and/or interferences to sample anal ysis. Although common anions will not**  **interfere with the analysis, all materials that com e into contact with samples must be** 

**demonstrated to be free from contaminants under the conditions of the analysis by analyzing**  **method blanks. Specific selection of reagents and purification of solvents by distillation in all**  **glass systems may be necessary. Refer to each meth od to be used for specific guidance on**  **quality control procedures and to Chapter Three for general guidance on the cleaning of**  **glassware.**

**4.2 Photodecomposition of some metal cyanide compl exes such as those of iron**  **can reduce their concentration (Refs. 13, 14). Col lect samples so as to prevent exposure to**  **light (see Sec. 8.1.). Store samples in amber, pla stic/glass bottles before analysis and protect**  **the samples from light whenever possible.**

**4.3 Carbonate is not a method interferent, but it can accumulate by adherence to**  **the anion exchange resin of the analytical column. This may eventually lead to unstable**  **baselines and a reduction in column capacity and an alyte retention. Take care to avoid**  **carbonate contamination when preparing and using so dium hydroxide eluents.** 

**CAUTION : Carbonate is formed in sodium hydroxide solution**  **s by reaction with atmospheric carbon dioxide. Prepare all eluents using reagent**  **water degassed with helium to prevent carbonate contamination as well as eluent outgassin**  **g during the analysis. Guidelines are provided in this test method for preparing low-carb**  **onate sodium hydroxide eluent and reagent**

**solutions.**

**4.4 Commercial grade sodium cyanide used in the pr eparation of Eluent 1 (Sec.**  **7.4) often contains complexed-metal cyanide impurit ies. These impurities can cause noisy,**  **unstable baselines during the gradient elution prof ile. The installation of an anion trap column**  **between Eluent 1 and the gradient pump removes the impurities from the eluent stream and**  **results in improved chromatographic baselines. Gui delines for installing the anion trap column**  **are provided in Sec. 11.6.**

**4.5 The Dionex IonPac**  **AG5, AG11, AS5, and AS11 chromatography columns referenced in this test method (Secs. 6.1.7, 6.1.8,**  **and 6.2.4) are polymeric and accordingly will concentrate neutral organics and polyvalent organic**  **anions at the head of the column. Organic species containing a carbonate functional group wil**  **l absorb at 215 nm. These species can potentially cause "ghost" peaks when eluted during**  **the analysis. This effect is a function of the quality of the water used in the preparation of the**  **eluent solutions and of the column equilibration time. Sample preconcentration will e**  **nhance this effect. High purity reagent water free of organic contaminants should be used in the**  **preparation of reagents. SW-846 Update V 9015 - 5 Revision 1** 

**October 2012 4.6 Free-metal cations present in either the sampl**  **e matrix or as impurities in the combined eluent stream can combine with the free cy**  **anide present in Eluent 1 (Sec. 7.4) to form extraneous metal cyanide complexes. Metal-fre**  **e trap columns should be installed to prevent positive interference by extraneous metal c**  **yanide complexes when performing sample preconcentration (Sec. 6.2.5).** 

**4.7 The method calibration for iron cyanide is bas ed on its reduced form,**  **ferrocyanide. Although the alkaline conditions of the analysis favor the reduction of ferricyanide**  **to ferrocyanide, any unreduced species could potent ially contribute to a bias in the analytical** 

**results.**

**4.8 Matrices with relatively high ionic strength ( conductivity greater than 70,000** 

μ **mhos/cm) or total dissolved solids (TDS greater tha n 30,000 mg/L) will affect the performance**  **of the analytical columns, resulting in poor separa tion and recovery of the metal cyanide**  **complexes. Such samples, if encountered, cannot be analyzed by this method. However, this**  **does not apply to most environmental samples, where the ionic strength and TDS are generally** 

**well below these levels.**

**4.9 When performing anion exchange chromatography coupled with on-line sample**  **preconcentration, the silver and copper cyanide com plexes exhibit reduced precision and**  **increased bias, especially in high ionic strength m atrices. For the silver cyanide complex, large**  **front-end tailing in samples containing high total dissolved solids affects peak resolution. For**  **the copper and silver cyanide complexes, possible d issociation during the analysis might also**  **affect quantitation in samples containing high tota l dissolved solids. Any matrix with high ionic**  **strength and total dissolved solids (e.g., TDS grea ter than 1000 mg/L) could affect the**  **performance of the analytical columns when performi ng sample preconcentration, which may**  **result in poor separation and recovery of metal cya nide complexes. Typically, only industrial**  **process wastewaters have TDS levels exceeding 1000 mg/L. For such matrices, sample**  **dilution using pH 12 reagent water (Sec. 7.8) can b e used to lower the TDS level provided that**  **the concentrations of the metal cyanide complexes o f interest are not diluted below the lower** 

**limits of detection.**

**5.0 SAFETY**

**5.1 This method does not address all safety issues associated with its use. The**  **laboratory is responsible for maintaining a safe wo rk environment and a current awareness file**  **of OSHA regulations regarding the safe handling of the chemicals listed in this method. A**  **reference file of material safety data sheets (MSDS s) should be available to all personnel**  **involved in these analyses.**

**WARNING : KCN and NaCN are highly toxic. Avoid skin and e**  **ye contact and inhalation.**

**5.2 Because of the toxicity of cyanide, exercise g reat care in its handling.**  **Acidification of cyanide solutions produces lethal, toxic hydrogen cyanide (HCN) gas. Prepare**  **all cyanide-containing solutions within a ventilati on hood. Wear hand and eye protection at all**  **times when working with cyanide.**

**5.3 Some of the reagents and solutions used in thi s method contain cyanide.**  **Dispose of these materials properly. The effluent from the chromatograph will contain cyanide.**  **After analysis, collect the effluent and immediatel y adjust it to a pH of 12 or greater. Dispose of**  **the effluent in an appropriate manner. SW-846 Update V 9015 - 6 Revision 1** 

**October 2012 5.4 The toxicity or carcinogenicity of each reagen**  **t used in this method has not been fully established. Each chemical should be re**  **garded as a potential health hazard and exposure should be as low as reasonably achievable.**  **Warnings are included for known extremely hazardous materials or procedures.** 

**6.0 EQUIPMENT AND SUPPLIES**

**The mention of trade names or commercial products in this manual is for illustrative**  **purposes only, and does not constitute an EPA endor sement or exclusive recommendation for**  **use. The products and instrument settings cited in SW-846 methods represent those products**  **and settings used during method development or subs equently evaluated by the Agency.**  **Glassware, reagents, supplies, equipment, and setti ngs other than those listed in this manual**  **may be employed provided that method performance ap propriate for the intended application** 

**has been demonstrated and documented.**

**This section does not list all common laboratory g lassware (e.g., beakers and flasks)**  **that might be used.**

**6.1 Anion exchange chromatography apparatus equipm ent** 

**6.1.1 Pressurized eluent reservoir - Accessories m ust include a gas**  **regulator capable of maintaining a 2-10 psi head pr essure on the eluent solutions using**  **helium gas.**

**6.1.2 Pressurizable eluent bottles - Bottles must be capable of withstanding**  **an internal pressure of 7-10 psi. The bottles must be made of a chemically inert plastic**  **such as polypropylene, suitable for use with sodium hydroxide-based eluents.** 

**6.1.3 Tubing - To be used with the eluent reservoi r and made of a material**  **that is compatible with the eluent solutions.**

**6.1.4 Gradient pump - High performance liquid chro matography (HPLC) or**  **ion chromatography (IC) pump capable of delivering a constant flow in the range of 1-5**  **mL/min at a pressure of 200-2000 psi.**

**6.1.5 Chromatography tubing - The tubing must be p ressure resistant**  **(approximately 3000 psi) and made of a material tha t is compatible with the eluent**  **solutions. Examples of suitable materials are PEEK and 316 stainless steel.** 

**6.1.6 Anion trap column (ATC) - The ATC is a low p ressure column that is**  **placed between the Eluent 1 reservoir and the gradi ent pump inlet to trap and remove**  **metal cyanide impurities. The column is packed wit h a high-capacity anion exchange**  **resin. An example of a suitable column is the Dion ex IonPac**   **ATC-3 4-mm (9 x 24 mm) (Ref. 15) or equivalent. The column must be co**  **mposed of a material appropriate for use with sodium hydroxide eluents.** 

**6.1.7 Analytical column - Low-capacity anion excha nge chromatography**  **column. The selected column must provide for adequ ate selectivity of high valent metal**  **cyanide complexes. Examples include the Dionex Ion Pac**   **AS5 (4-mm) (Ref. 16) and**

**the Dionex IonPac**  **AS11 (4-mm or 2-mm) (Ref. 17) columns, or equivale nt. These** **SW-846 Update V 9015 - 7 Revision 1**

**October 2012 columns differ somewhat in selectivity. The AS5 co**  **lumn provides greater selectivity for the early eluting silver, copper and gold cyanide c**  **omplexes while the AS11 column provides greater selectivity for the iron cyanide c**  **omplex. The 2-mm column requires 1⁄4 the sample volume and operates at 1⁄4 the flow rate o**  **f a 4-mm column. Due to the decreased flow rate, the 2-mm column consumes only**  **1⁄4 the eluent required by a 4-mm**

**column.**

**6.1.8 Guard column - Optional low-capacity anion e xchange**  **chromatography guard column. This column may be us ed before the analytical column**  **to remove sample impurities and prevent them from p assing onto the analytical column.**  **The selected column must provide for adequate selec tivity of highly valent metal cyanide**  **species. Examples include the Dionex IonPac**  **AG5 (Ref. 16) and AG11 (Ref. 17) columns or equivalent.** 

**6.1.9 Ultraviolet/Visible Spectroscopic (UV/Vis) d etector - Liquid**  **chromatography UV/Vis detector, capable of low wave length detection at 215 nm.** 

**6.1.10 Instrument control and data collection syst em - Standard equipment**  **such as electronic control devices and computer and software and/or integrators for**  **providing automatic control of the chromatography s ystem, instrument calibration and**  **data analysis**

**6.2 On-line sample preconcentration accessories - Additional electrical contact**  **closures are required for establishing automatic co ntrol of the preconcentration hardware** 

**accessories.**

**6.2.1 Injection valve - 2-way switching valve capa ble of injecting volumes**  **ranging from 0.1 μL-1 mL.**

**6.2.2 Autosampler - Capable of handling 40-mL samp le vials for use in**  **performing sample preconcentration.**

**6.2.3 Large sample vials - 40-mL amber glass vials . The use of self-sealing**  **vials is recommended to prohibit exposure of the sa mple to light during and after sample**  **injection so as to prevent photodecomposition of so me metal cyanide complexes.** 

**6.2.4 Concentrator column - Low-capacity anion exc hange chromatography**  **concentrator column. The selected column must prov ide for adequate selectivity of**  **highly valent transition metal cyanide species. Ex amples are the Dionex IonPac**   **AG5 (Ref. 16) and AG11 (Ref. 17) columns or equivalent.** 

**6.2.5 Metal free trap column (MFC) - Specially des igned column for the on**  **line cleanup of eluent ionic transition metal impur ities. Two such columns should be**  **installed; one between the gradient pump outlet and the injection valve and the other**  **between the sample concentrator pump outlet and the injection valve (See Sec. 11.4.2.).**  **An example is the Dionex IonPac**  **MFC-1 (Ref. 18) or equivalent. Refer to the manufacturer’s instructions for column preparation**  **and clean-up.**

**6.2.6 Sample concentrator pump - Liquid chromatogr aphy or otherwise**  **equivalent pump capable of interfacing with the ins trument control and data collection**  **system. The selected sample pump must deliver a co nstant flow in the range of 1-5**  **mL/min at a pressure of 200 - 2000 psi. SW-846 Update V 9015 - 8 Revision 1** 

**October 2012 6.3 Amber reagent bottles - 100 mL and 1000 mL** 

**6.4 Membrane syringe filters - 25 mm diameter, 0.2 - 0.45 mm pore size, having** 

**low background extractables, used to filter and rem ove sample particulates** 

**6.5 Plastic syringes - 5 and 10 mL volumes**

**6.6 pH electrode, meter and calibration buffers or pH papers or test strips** 

**7.0 REAGENTS AND STANDARDS**

**7.1 Reagent-grade chemicals must be used in all te sts. Whenever available, HPLC**  **grade must be used in place of reagent grade. Unle ss otherwise indicated, it is intended that all**  **reagents conform to the specifications of the Commi ttee on Analytical Reagents of the American**  **Chemical Society, where such specifications are ava ilable. Other grades may be used,**  **provided it is first ascertained that the reagent i s of sufficiently high purity to permit its use**  **without lessening the accuracy of the determination . Reagents should be stored in glass to**  **prevent the leaching of contaminants from plastic c ontainers. Note, however, that sodium**  **hydroxide solutions of relatively moderate strength (i.e., 4.1 g/L and greater), should be stored**  **in HDPE plastic containers whenever possible.**

**7.2 Reagent water - ASTM Type I or deionized water , free of the analyte of interest.**  **The reagent water should contain particles no large r than 0.20 μm. It is recommended that**  **special precautions such as routine contaminant mon itoring and/or frequent replacement of**  **polishing cartridges be taken to ensure that the to tal organic carbon content of the water is**  #
**100** μ **g/L. This practice will limit the elution of organ ic species and subsequent appearance of**  **"ghost" peaks in the chromatograms. Figures 1 and 2 provide examples of method blank**  **chromatograms. All references to water in this met hod refer to reagent water as defined in**  **Chapter One unless otherwise specified.**

**7.3 Degassed reagent water - Sparge reagent water with helium gas for**  **approximately 20 min to remove dissolved gases such as carbon dioxide.** 

**7.4 Eluent 1 (20 mM NaOH, 150 mM NaCN) - Place 1.6 g of sodium hydroxide**  **solution (50% w/w) and 7.35 g of sodium cyanide int o a 1-L volumetric flask. Add approximately**  **300 mL of degassed reagent water and swirl to disso lve. Dilute to volume with degassed**  **reagent water and mix thoroughly. The sodium cyani de is used to maintain the integrity of the**  **metal cyanide complex throughout the analysis.**

**WARNING : NaCN is extremely toxic. Avoid inhalation and s**  **kin and eye contact (See Sec. 5.0.).** 

**7.5 Eluent 2 (20 mM NaOH, 300 mM NaClO 4**  **•H 2**  **O) - Place 1.6 g of sodium hydroxide solution (50% w/w) and 42.1 g of sodium p**  **erchlorate monohydrate into a 1-L volumetric flask. Add approximately 300 mL of dega**  **ssed reagent water and swirl to dissolve. Dilute to volume with degassed reagent water and mi**  **x thoroughly. The sodium perchlorate is used to elute the metal cyanide complexes from the**  **analytical column during the gradient**

**elution. SW-846 Update V 9015 - 9 Revision 1** 

**October 2012 7.6 Eluent 3 (20 mM NaOH) - Place 1.6 g of sodium**  **hydroxide solution (50% w/w)**

**into a 1-L volumetric flask. Dilute to volume with degassed reagent water and mix thoroughly.** 

**7.7 Sodium Hydroxide Solution I (50% w/w, 19.3 M) - It is recommended that the**  **solution be purchased from a vendor so as to have t he lowest possible carbonate**  **contamination. Attempts to prepare the solution ma nually within the laboratory may result in** 

**carbonate contamination. This solution is used for the preparation of the eluents (Secs. 7.4**  **through 7.6) and Sodium Hydroxide Solution II (Sec. 7.8).** 

**7.8 Sodium Hydroxide Solution II (10 mM, pH = 12) - Place 0.8 g of Sodium**  **Hydroxide Solution I into a 1-L volumetric flask. Dilute to volume with degassed reagent water**  **and mix thoroughly. Check to ensure that the pH is equal to 12 or greater using a pH paper/test**  **strip or a calibrated pH electrode. Add additional Sodium Hydroxide Solution I, if needed, to**  **bring the pH to 12.**

**NOTE : This solution is used in the preparation of all**  **standards in order to match the matrix of the standards to that of the alkaline preserved sam**  **ples or solid waste extracts. In addition, the high pH acts as a safety measure to prevent formati**  **on of gaseous HCN in the event of decomposition of the metal cyanide complex standard**  **s.**

**7.9 Method blank - Use Sodium Hydroxide Solution I I (Sec. 7.8).** 

**7.10 Cobalt Cyanide Stock Solution (1000 mg/L [Co( CN)**  **6 ]**  **3- ) - Dissolve exactly**  **0.1182 g of potassium cobalt cyanide, K 3**  **[Co(CN) 6**  **], with approximately 50 mL of Sodium Hydroxide Solution II in a 100-mL volumetric flask.**  **Dilute to volume with Sodium Hydroxide Solution II and store at ≤6 oC in an amber reagent**  **bottle. The solution is relatively stable and may be stored for up to one month. Bring to room t**  **emperature prior to use.**

**7.11 Cobalt Cyanide Standard Solution I (100 mg/L [Co(CN)**  **6 ]**  **3- ) - Dilute exactly 10**  **mL of [Co(CN) 6**  **] 3-**  **Stock Solution (Sec. 7.10) to 100 mL with Sodium H ydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.12 Cobalt Cyanide Standard Solution II (10 mg/L [Co(CN)**  **6 ]**  **3- ) - Dilute exactly 10**  **mL of [Co(CN) 6**  **] 3-**  **Standard Solution I (Sec 7.11) to 100 mL with Sodi um Hydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.13 Cobalt Cyanide Standard Solution III (100 μg/ L [Co(CN)**  **6 ]**  **3- ) - Dilute exactly 1**  **mL of [Co(CN) 6**  **] 3-**  **Standard Solution II (Sec 7.12) to 100 mL with Sod ium Hydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.14 Copper Cyanide Stock Solution (1000 mg/L [Cu( CN)**  **3 ]**  **2- ) - Combine exactly**  **0.0632 g of copper cyanide, CuCN, with approximatel y 90 mL of Sodium Hydroxide Solution II**  **in a 100-mL volumetric flask. Add exactly 0.0692 g of sodium cyanide, NaCN, and stir to**  **dissolve both the copper cyanide and sodium cyanide . Dilute to volume with Sodium Hydroxide**  **Solution II and store at ≤6 oC in an amber reagent bottle. The solution may be stored for up to**  **two weeks. Bring to room temperature prior to use.**

**NOTE : The copper cyanide will dissolve upon addition o**  **f sodium cyanide to form the tricyanocuprate(I) complex, [Cu(CN)**  **3 ]**  **2- that is the analyte of interest.** 

**WARNING : NaCN is extremely toxic. Avoid inhalation and s**  **kin and eye contact (See Sec. 5.0.).** **SW-846 Update V 9015 - 10 Revision 1**

**October 2012 7.15 Copper Cyanide Standard Solution I (100 mg/L**  **[Cu(CN) 3**  **] 2-**  **) - Dilute exactly 10 mL of [Cu(CN)**  **3 ]**  **2- Stock Solution (Sec. 7.14) to 100 mL with Sodium H**  **ydroxide Solution II. Store the solution in an amber reagent bottle. Pre**  **pare daily with analysis.**

**7.16 Copper Cyanide Standard Solution II (10 mg/L [Cu(CN)**  **3 ]**  **2- ) - Dilute exactly 10**  **mL of [Cu(CN) 3**  **] 2-**  **Standard Solution I (Sec. 7.15) to 100 mL with Sod ium Hydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.17 Copper Cyanide Standard Solution III (100 μg/ L [Cu(CN)**  **3 ]**  **2- ) - Dilute exactly 1**  **mL of [Cu(CN) 3**  **] 2-**  **Standard Solution II (Sec. 7.16) to 100 mL with So dium Hydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.18 Gold Cyanide Solution Stock Solution (1000 mg /L [Au(CN)**  **2 ]**  **- ) - Dissolve exactly**  **0.1157 g of potassium gold cyanide, K[Au(CN) 2**  **], with approximately 50 mL of Sodium Hydroxide Solution II in a 100-mL volumetric flask.**  **Dilute to volume with Sodium Hydroxide Solution II and store at ≤6 oC in an amber reagent**  **bottle. The solution is relatively stable and may be stored for up to one month. Bring to room t**  **emperature prior to use.**

**7.19 Gold Cyanide Standard Solution I (100 mg/L [A u(CN)**  **2 ]**  **- ) - Dilute exactly 10 mL**  **of [Au(CN) 2**  **] -**  **Stock Solution (Sec. 7.18) to 100 mL with Sodium H ydroxide Solution II. Store the**  **solution in an amber reagent bottle. Prepare daily with analysis.** 

**7.20 Gold Cyanide Standard Solution II (10 mg/L [A u(CN)**  **2 ]**  **- ) - Dilute exactly 10 mL**  **of [Au(CN) 2**  **] -**  **Standard Solution I (Sec. 7.19) to 100 mL with Sod ium Hydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.21 Gold Cyanide Standard Solution III (100 μg/L [Au(CN)**  **2 ]**  **- ) - Dilute exactly 1 mL**  **of [Au(CN) 2**  **] -**  **Standard Solution II (Sec. 7.20) to 100 mL with So dium Hydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.22 Iron Cyanide Solution Stock Solution (1000 mg /L [Fe(CN)**  **6 ]**  **4- ) - Dissolve exactly**  **0.1993 g of potassium ferrocyanide trihydrate, K 4**  **[Fe(CN) 6**  **]•3H 2**  **O, with approximately 50 mL of Sodium Hydroxide Solution II in a 100-mL volumetric**  **flask. Dilute to volume with Sodium Hydroxide Solution II and store at ≤6 oC in an ambe**  **r reagent bottle. The solution is relatively stable and may be stored for up to one month. Brin**  **g to room temperature prior to use.**

**7.23 Iron Cyanide Standard Solution I (100 mg/L [F e(CN)**  **6 ]**  **4- ) - Dilute exactly 10 mL**  **of Fe(CN) 6**  **4- Stock Solution (Sec. 7.22) to 100 mL with Sodium H**  **ydroxide Solution II. Store the solution in an amber reagent bottle. Prepare daily**  **with analysis.**

**7.24 Iron Cyanide Standard Solution II (10 mg/L [F e(CN)**  **6 ]**  **4- ) - Dilute exactly 10 mL of**  **Fe(CN) 6**  **4- Standard Solution I (Sec. 7.23) to 100 mL with Sod**  **ium Hydroxide Solution II. Store the solution in an amber reagent bottle. Prepare d**  **aily with analysis.**

**7.25 Iron Cyanide Standard Solution III (100 μg/L [Fe(CN)**  **6 ]**  **4- ) - Dilute exactly 1 mL of**  **Fe(CN) 6**  **4- Standard Solution II (Sec. 7.24) to 100 mL with So**  **dium Hydroxide Solution II. Store the solution in an amber reagent bottle. Prepare d**  **aily with analysis.**

**7.26 Nickel Cyanide Stock Solution (1000 mg/L [Ni( CN)**  **4 ]**  **2- ) - Dissolve exactly 0.1481**  **+ (0.0111 x** n **) g of potassium nickel cyanide mono- or polyhydrat e, K**  **2 [Ni(CN)**  **4 ]•**  n **H 2**  **O (where** n **= number of water molecules of hydration), with app roximately 50 mL of Sodium Hydroxide** **SW-846 Update V 9015 - 11 Revision 1**

**October 2012 Solution II in a 100-mL volumetric flask. Dilute t**  **o volume with Sodium Hydroxide Solution II and store at ≤6 oC in an amber reagent bottle. The sol**  **ution may be stored for up to two weeks. Bring to room temperature prior to use.** 

**7.27 Nickel Cyanide Standard Solution I (100 mg/L [Ni(CN)**  **4 ]**  **2- ) - Dilute exactly 10 mL**  **of [Ni(CN) 4**  **] 2-**  **Stock Solution (Sec. 7.26) to 100 mL with Sodium H ydroxide Solution II. Store the**  **solution in an amber reagent bottle. Prepare daily with analysis.** 

**7.28 Nickel Cyanide Standard Solution II (10 mg/L [Ni(CN)**  **4 ]**  **2- ) - Dilute exactly 10 mL**  **of [Ni(CN) 4**  **] 2-**  **Standard Solution I (Sec. 7.27) to 100 mL with Sod ium Hydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.29 Nickel Cyanide Standard Solution III (100 μg/ L [Ni(CN)**  **4 ]**  **2- ) - Dilute exactly 1 mL**  **of [Ni(CN) 4**  **] 2-**  **Standard Solution II (Sec. 7.28) to 100 mL with So dium Hydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.30 Silver Cyanide Stock Solution(1000 mg/L [Ag(C N)**  **2 ]**  **- ) - Dissolve exactly 0.1244**  **g of potassium silver cyanide, K[Ag(CN) 2**  **], with approximately 50 mL of Sodium Hydroxide**

**Solution II in a 100-mL volumetric flask. Dilute t o volume with Sodium Hydroxide Solution II and**  **store at ≤6 oC in an amber reagent bottle. The sol ution may be stored for up to two weeks.**  **Bring to room temperature prior to use.**

**7.31 Silver Cyanide Standard Solution I (100 mg/L [Ag(CN)**  **2 ]**  **- ) - Dilute exactly 10 mL**  **of [Ag(CN) 2**  **] -**  **Stock Solution (Sec. 7.30) to 100 mL with Sodium H ydroxide Solution II. Store the**  **solution in an amber reagent bottle. Prepare daily with analysis.** 

**7.32 Silver Cyanide Standard Solution II (10 mg/L [Ag(CN)**  **2 ]**  **- ) - Dilute exactly 10 mL**  **of [Ag(CN) 2**  **] -**  **Standard Solution I (Sec. 7.31) to 100 mL with Sod ium Hydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.33 Silver Cyanide Standard Solution III (100 μg/ L [Ag(CN)**  **2 ]**  **- ) - Dilute exactly 1 mL**  **of [Ag(CN) 2**  **] -**  **Standard Solution II (Sec. 7.32) to 100 mL with So dium Hydroxide Solution II.**  **Store the solution in an amber reagent bottle. Pre pare daily with analysis.** 

**7.34 Calibration blank - Use Sodium Hydroxide Solu tion II (Sec. 7.8).** 

**7.35 Iron(III) hexacyanoferrate(II), Fe 4**  **[Fe(CN) 6**  **] 3**  **- Certified ACS grade or equivalent**

**7.36 Helium gas - Ultra high purity**

**8.0 SAMPLE COLLECTION, PRESERVATION AND STORAGE**

**Sample collection, preservation and storage requir ements may vary by EPA program**  **and may be specified in a regulation or project pla nning document that requires compliance**  **monitoring for a given contaminant. Where such req uirements are specified in the regulation,**  **follow those requirements. In the absence of speci fic regulatory requirements, use the following**  **information as guidance in determining the sample c ollection, preservation and storage**  **requirements. SW-846 Update V 9015 - 12 Revision 1** 

**October 2012 8.1 Samples should be collected in polyethylene co**  **ntainers covered in aluminum foil or otherwise equivalent containers such as tho**  **se composed of amber plastic so as to filter UV light ≤ 300 nm in order to prevent photodecompos**  **ition of metal cyanide complexes.**

**8.2 Aqueous samples for complexed-metal cyanide an alysis should be preserved**  **under alkaline conditions by adjusting the pH to 12 or greater using sodium hydroxide. Solid**  **waste samples should be stored at ≤6 oC after colle ction and prior to extraction.** 

**8.3 Store all sample matrices at ≤6 oC for no long er than 14 days. Solid phase**  **samples must be extracted within 14 days of sample collection. Bring the samples to room**  **temperature prior to analysis. Analysis of aqueous samples and solid phase extract solutions**  **must be performed within 14 days of sample collecti on or extract generation.** 

**9.0 QUALITY CONTROL**

**9.1 Refer to Chapter One for guidance on quality a ssurance (QA) and quality**  **control (QC) protocols. When inconsistencies exist between QC guidelines, method-specific**  **QC criteria take precedence over both technique-spe cific criteria and those criteria given in**  **Chapter One, and technique-specific QC criteria tak e precedence over the criteria in Chapter**  **One. Any effort involving the collection of analyt ical data should include development of a**  **structured and systematic planning document, such a s a Quality Assurance Project Plan**  **(QAPP) or a Sampling and Analysis Plan (SAP), which translates project objectives and**  **specifications into directions for those that will implement the project and assess the results.**  **Each laboratory should maintain a formal quality as surance program. The laboratory should**  **also maintain records to document the quality of th e data generated. All data sheets and quality** 

**control data should be maintained for reference or inspection.** 

**9.2 Initial demonstration of proficiency Prior to the analysis of samples an initial**  **demonstration of method proficiency is accomplished through the successful calibration of**  **method-specific instruments according to project re quirements and criteria set forth in the**  **applicable analytical methodology. This initial de monstration should be performed prior to**  **independently running an analytical method, and sho uld be repeated if other changes occur**  **(e.g., instrument repair, significant change in pro cedure). Documentation of IDP should be**  **maintained by the Quality Assurance Manager.**

**An analytical instrument is said to be calibrated when an instrumental response can be**  **related to the concentration of an analyte. This r elationship may be depicted graphically, and** 

**referred to as a “calibration curve.” Initial cali bration curves must be established based upon**  **the requisite number of standards identified within the method for each target analyte (and**  **surrogate for organic compounds). All reported con centrations for target analytes should be**  **within the high and low initial calibration standar ds. Data generated above the high standard**  **should be diluted into the calibration range and re analyzed. The frequency requirements for the**  **initial calibration vary among the individual metho ds.** 

**Most analytical methods require multipoint (three or more) calibration that may include**  **calibration blanks and higher levels so that unknow ns fall within the calibration range and are**  **bracketed by calibration points. The number of cal ibration points, the calibration range, and the**  **frequency requirements should be specified in the Q APP.** 

**If an autosampler is used to perform sample diluti ons, before using the autosampler to**  **dilute samples, the laboratory should satisfy itsel f that those dilutions are of equivalent or better** **SW-846 Update V 9015 - 13 Revision 1**

**October 2012 accuracy than is achieved by an experienced analyst**  **performing manual dilutions. The laboratory must also repeat the demonstration of pr**  **oficiency whenever new staff members are trained or significant changes in instrumentation a**  **re made. See Method 8000D, Section 9.3 for information on how to accomplish a demonstration of**  **proficiency.**

**9.3 Initially, before processing any samples, the analyst should demonstrate that all**  **parts of the equipment in contact with the sample a nd reagents are free from contaminants and**  **interferences. This is accomplished through the an alysis of a method blank (See Sec. 7.9 and**  **9.4.1). As a continuing check, each time samples a re extracted, cleaned up, and analyzed, and**  **when there is a change in reagents, a method blank should be prepared and analyzed for the**  **compounds of interest as a safeguard against chroni c laboratory contamination. If a peak is**  **observed within the retention time window of any an alyte that would prevent the determination**  **of that analyte, determine the source of the contam ination or interference and eliminate it, if**  **possible, before processing the samples. The metho d blanks should be carried through all**  **stages of sample preparation and analysis.**

**The laboratory should not subtract the results of t he method blank from those of any**  **associated samples. Such "blank subtraction" may l ead to negative sample results. If the**  **method blank results do not meet the project-specif ic acceptance criteria and reanalysis is not**  **practical, then the data user should be provided wi th the sample results, the method blank**  **results, and a discussion of the corrective actions undertaken by the laboratory.** 

**9.4 Sample quality control for preparation and ana lysis** 

**The laboratory must also have procedures for docum enting the effect of the matrix on**  **method performance (precision, accuracy, method sen sitivity). At a minimum, this should**  **include the analysis of QC samples including a meth od blank, a matrix spike, a duplicate, and a**  **laboratory control sample in each analytical batch. Any method blanks, matrix spike samples,**  **and replicate samples must be subjected to the same analytical procedures (Sec. 11.0) as**  **those used on actual samples.**

**The following should be included within each analy tical batch:** 

**9.4.1 Method blank - For each batch of solid phase samples extracted using**  **Method 9013 (maximum 20), at least one extraction m ethod blank should also be carried**  **through the entire sample extraction, preparation a nd analytical process. An extraction**  **method blank is prepared by using a specified volum e or weight of the Method 9013**  **extraction solution and then carrying it through th e appropriate steps of the extraction**  **and analytical process. These steps may include, b ut are not limited to, prefiltering,**  **extraction, dilution, filtering, and analysis. If the method blank does not contain target**  **analytes at a level that exceeds the project-specif ic criteria requirements, then the**  **method blank would be considered acceptable. In th e absence of project-specific**  **criteria, if the blank is less than the lower limit of detection, less than 10% of the**  **regulatory limit, or less than 10% of the lowest sa mple concentration, whichever is**  **greater, then the method blank is considered accept able. If the method blank cannot be**  **considered acceptable, the method blank should be r e-run once, and if still**  **unacceptable, then all samples after the last accep table method blank must be prepared**  **again and reanalyzed along with the other appropria te batch QC samples. These blanks**  **will be useful in determining if samples are being contaminated. If the method blank**  **exceeds the criteria, but the samples are all eithe r below the reporting level or below the**  **applicable action level or other criteria, then the data should not be rejected based on**  **this analysis. SW-846 Update V 9015 - 14 Revision 1** 

**October 2012 9.4.2 MS/MSD - For each batch of waters processed**  **(maximum 20), at least one analytical MS/MSD sample must be carried throug**  **h the entire sample preparation and analytical process. MS/MSDs are intra-laborato**  **ry split samples spiked with identical concentrations of each analyte of interest. An MS/**  **MSD is used to document the bias and precision of a method in a given sample matrix.**  **MS/MSD samples should be spiked at the same level, with the same spiking material,**  **as that used to prepare the calibration standards and at the project-specific action level**  **or, when lacking project-specific action levels, between the low- and mid-level standards.**  **Acceptance criteria should be set at a laboratory-derived limit developed through the use**  **of historical analyses per matrix type analyzed. In the absence of historical data this l**  **imit should be set at ±25% of the spiked concentration for accuracy and 25 relative percent**  **difference (RPD) for precision. After the generation of historical data, 25% must still b**  **e the limit of maximum deviation for RPD to express precision and ±25% of the spiked con**  **centration for accuracy. A separate spiked sample and a separate duplicate uns**  **piked sample may be analyzed in lieu of MS/MSD analyses. If the bias and precision**  **indicators are outside the laboratory control limits, or if the percent recovery is less**  **than 75% or greater than 125%, or if the relative percent difference is greater than 25%, th**  **e interference test as discussed in**

**Method 8000 should be conducted.**

**9.4.3 MS/MSD - For each batch of solid phase sampl es extracted using**  **Method 9013 (maximum 20), at least one extraction M S/MSD sample should be carried**  **through the entire sample extraction, preparation a nd analytical process. Spiking is**  **performed directly on the solid sample matrix prior to extraction in order to assess the**  **efficiency of the extraction procedure. The spikin g source material should consist of a**  **solid phase metal cyanide compound that sufficientl y challenges the extraction**  **procedure. An example of such a compound is iron(I II) hexacyanoferrate(II),** 

**Fe 4**  **[Fe(CN) 6**  **] 3**  **(also known as Prussian Blue). Although insoluble under neutral and low**  **pH conditions, Fe 4**  **[Fe(CN) 6**  **] 3**  **will dissolve under the alkaline extraction condit ions of**  **Method 9013 and quantitatively yield [Fe(CN) 6**  **] 4-**  **in the extraction solution, which can subsequently be analyzed in order to verify extract**  **ion efficiency. Other metal cyanide compounds may be used for spiking the solid sample**  **matrix, depending on which aqueous metal cyanide complexes are of greatest int**  **erest in the analysis. Refer to the guidance given Sec. 9.5.3 for accuracy and precisio**  **n acceptance criteria for the**

**extraction MS/MSD.**

**9.4.5 LCS - For each batch of samples processed (m aximum 20), at least**  **one LCS must be carried through the entire sample p reparation and analytical process,**  **as described in Chapter One. The LCS is a reagent water solution fortified with method**  **analytes at known concentrations, prepared from a d ifferent source than that used to**  **prepare the calibration standards. The LCS should be spiked with each analyte of**  **interest at the project-specific action level or wh en lacking project-specific action levels,**  **between the low- and mid-level standards. Acceptan ce criteria should be set at a**  **laboratory-derived limit developed through the use of historical analyses. In the absence** 

**of historical data this limit should be set at** ± **20% of the spiked concentration. After the generation of historical data,**  ± **20% must still be the acceptable limit of maximum deviation. If the LCS recovery is not acceptable,**  **the LCS should be re-run once and, if still unacceptable, all samples after the last acce**  **ptable LCS must be prepared again and reanalyzed. Concurrent analyses of standard refere**  **nce materials (SRMs) containing known values of analytes in the media of interest a**  **re recommended and may be used as**

**an LCS. SW-846 Update V 9015 - 15 Revision 1** 

**October 2012 9.4.6 Also see Method 8000 for the details on carr**  **ying out sample quality control procedures for preparation and analysis. I**  **n-house method performance criteria for evaluating method performance should be develop**  **ed using the guidance found in**

**Method 8000.**

**9.5 Initial Calibration Verification (ICV)** 

**Immediately after the calibration standards have b een analyzed, the accuracy of the**  **calibration must be verified by the analysis of an ICV standard. The ICV is prepared in the** 

**same manner as a calibration standard at a concentr ation level within the calibration range of**  **the method and using a second source standard (prep ared using standards different from the**  **calibration standards) spiked into Sodium Hydroxide Solution II (see Sec. 7.8). The control limit** 

**for the ICV is ±15% of the true value. When the IC V exceeds the control limits, the analysis**  **should be terminated, the problem corrected, the in strument recalibrated, and the calibration re** 

**verified.**

**9.6 Continuing Calibration Verification (CCV)**

**Once the calibration curve has been established, t he continuing accuracy must be**  **verified by analysis of a CCV after every tenth fie ld sample, and at the end of the analysis**  **sequence. The CCV is equivalent to or prepared in the same manner as a calibration standard** 

**at a concentration level within the calibration ran ge of the method and using the same source**  **standard (prepared using the same source standards as those used to prepare the calibration**  **standards) spiked into Sodium Hydroxide Solution II (see Sec. 7.8). CCV concentrations**  **alternating between the low- and mid-range calibrat ion standard concentrations are**  **recommended. The control limit for the low-range C CV is ± 50% and for the mid-range CCV is** 

**± 15% of the true value. When the CCV exceeds the control limits, the analysis should be**  **terminated, the problem corrected, the instrument r ecalibrated, and the calibration re-verified**  **using an ICV analysis. Samples that are not bracke ted by acceptable CCV runs must be**  **reanalyzed.**

**9.7 Lower Limit of Quantitation (LLOQ) check stand ard** 

**The laboratory should establish the LLOQ as the lo west point of quantitation which, in**  **most cases, is the lowest concentration in the cali bration curve. The LLOQ verification is**  **recommended for each project application to validat e quantitation capability at low analyte**  **concentration levels. This verification may be acc omplished either with clean control material**  **(e.g., reagent water, method blank, Ottawa sand, di atomaceous earth, etc.) or a representative**  **sample matrix (free of target compounds). Optimall y, the LLOQ should be less than or equal to**  **the desired regulatory action levels based on the s tated project-specific requirements. The**  **LLOQ should be verified by the analysis of at least 7 replicate samples, spiked at the LLOQ and**  **processed through all preparation and analysis step s of the method. The mean recovery and**  **relative standard deviation of these samples provid e an initial statement of precision and**  **accuracy at the LLOQ. In most cases the mean recove ry should be +/- 35% of the true value**  **and RSD should be < 20%. In-house limits may be cal culated when sufficient data points exist.** 

**9.7.1 The determination of LLOQs using spiked cle an control material**  **represents a best-case scenario, and does not evalu ate the potential matrix effects of real**  **world samples. For the application of LLOQs on a p roject-specific basis, with established**  **DQOs, a representative matrix-specific LLOQ verific ation may provide a more reliable**  **estimate of the lower quantitation limit capabiliti es.** **SW-846 Update V 9015 - 16 Revision 1**

**October 2012 9.7.1.1 A matrix-free LLOQ check standard is**  **prepared by spiking a clean control material with the analyte(s) of inter**  **est at the predicted LLOQ concentration level(s). This LLOQ check is carried**  **through the same preparation procedures as the environmental samples and other Q**  **C. Recovery should be ±50% (or other such project-required acceptance lim**  **its for accuracy and precision) of the true value to verify the data reporting limi**  **ts(s). The low-range CCV standard (Sec. 9.6), if prepared at the appropriate concentr**  **ation, may also serve as the LLOQ verification for confirming method sensitivity** 

**.**

**9.7.1.2 Alternatively, a representative sample matrix may be spiked** 

**with the analytes of interest at the predicted LLOQ concentration levels. This**  **LLOQ check is carried through the same preparation procedures as the**  **environmental samples and other QC. Individual LLO Qs are verified when each**  **respective analyte is recovered at ±50% of the pred icted LLOQ concentration or**  **established DQO criteria. This check may also be a pplied towards establishing the**  **individual analyte reporting limit(s).**

**9.7.2 In-house limits may be calculated when suff icient data points exist.** 

**10.0 CALIBRATION AND STANDARDIZATION**

**10.1 Calibration standards - Prepare calibration s tandards so as to bracket the**  **ranges of each metal cyanide complex of interest by adding measured volumes of metal**  **cyanide standards (Sec. 7.0) to volumetric flasks a nd diluting to volume. Approximate**  **calibration ranges for each metal cyanide complex a re provided in Tables 1 and 2. Dilute the**  **standards to their respective final volumes using S odium Hydroxide Solution II (Sec. 7.8).**  **Prepare at least three standards or as otherwise re quired for data reporting. Store the** 

**standards in amber bottles.**

**10.2 To establish the calibration curve, analyze t he calibration blank (Sec. 7.34) and**  **calibration standards in accordance with the proced ure in Sec. 11.0. Plot calibration curves of**  **peak area response verses analyte concentration for each metal cyanide using the method**  **blank peak area integration for the zero point. Pe rform linear regressions of the plots. A**  **second order regression plot may be used if needed. The correlation coefficient of each**  **regression should be 0.995 or greater for accurate results. Once the calibration curve has been**  **established, verification must be performed on each analysis day, whenever fresh eluent is**  **prepared, and once per analysis batch as outlined i n Sec. 9.0.** 

**NOTE : Since all iron cyanide species are detected as f**  **errocyanide, that form of iron cyanide is used in the preparation of the calibration standard**  **s. The calibration and subsequent analysis results for iron cyanide should be presented as eit**  **her [Fe(CN) 6**  **] x-**  **or [Fe(CN)**  **6 ]**  **3-/4- so as to represent the total sum of ferrocyanide a**  **nd ferricyanide.**

**11.0 PROCEDURE**

**11.1 For aqueous samples, proceed to Sec. 11.3 or 11.4.** 

**11.2 For solid waste extract solutions to be analy zed by this method, the following**  **steps need to be performed after the Method 9013 ex traction process:** **SW-846 Update V 9015 - 17 Revision 1**

**October 2012 11.2.1 Following the 16 hour extraction, check the**  **pH of the extraction solution. Adjust the pH between 11 and 12, using 5**  **0% H 2**  **SO 4**  **. Recap the extraction flask and mix the solution. Repeat the procedure u**  **ntil the pH is in the desired range.**

**11.2.2 Prepare a Buchner funnel apparatus with a 0 .45-**  μ **m membrane filter.**

**11.2.3 Decant the extract to the Buchner funnel. Full recovery of the extract**  **is not necessary.**

**11.2.4 If not analyzed immediately, transfer the e xtract into a dark**  **plastic/glass bottle with no headspace and store it at ≤6 oC. Analyze the extract within**  **14 days.**

**11.3 Anion exchange chromatography analysis - Anal yze samples containing 0.2-**  **200 mg/L metal cyanide complexes by direct injectio n of sample or extract. Higher sample**  **concentrations may be analyzed after an appropriate dilution.** 

**Set up the chromatography hardware in an appropria te manner for analysis. An**  **example of a suitable hardware configuration using this method is displayed in Figure 3.** 

**11.4 Anion exchange chromatography analysis using on-line sample**  **preconcentration - Analyze samples containing 0.5**

- **200 μg/L metal cyanide complexes using on-line sample preconcentration prior to anion exch**  **ange chromatography analysis.**

**11.4.1 Set up the chromatography hardware for perf orming analysis with**  **initial on-line sample preconcentration. An exampl e of a suitable hardware configuration**  **using the method is displayed in Figures 4 and 5.**

**11.4.2 Condition the MFCs according to the manufac turer’s instructions and**  **install as shown in Figure 4.**

**11.4.3 Set the sample concentrator pump to achieve a flow rate of 2 mL/min.** 

**11.4.4 Prime the sample concentrator pump to remov e trapped air.**  **Disconnect the tubing from the pump head and withdr aw eluent using a plastic syringe** 

**until no air bubbles are observed. Reconnect the t ubing when finished.** 

**WARNING : The effluent from the chromatograph will contain**  **cyanide and should be handled and disposed in a safe manner (see Sec. 5.0**  **.).**

**11.5 Set up the method by programming the instrume nt control and data collection**  **system or the gradient pump directly to perform gra dient elution anion chromatography analysis**  **of metal cyanide complexes as specified in Tables 4 and 5. Portions of the analysis program**  **may be modified as appropriate provided the analyti cal results fall within the precision and bias**  **established for the method (see Sec. 13.0.).**

**11.6 Install the ATC.**

**11.6.1 Condition the ATC according to the manufac turer’s instructions.** 

**11.6.2 Set the gradient pump to 100% Eluent 1 and prime the gradient pump**  **line to remove trapped air. SW-846 Update V 9015 - 18 Revision 1** 

**October 2012 11.6.3 After priming, connect the conditioned ATC**  **directly to the outlet of the gradient pump and plumb the ATC outlet line to an a**  **ppropriate waste container. Pump Eluent 1 through the column at 1 mL/min for 60 min**  **to convert the resin from the hydroxide to the cyanide form. At the end of the t**  **ime period, stop the gradient pump and disconnect the ATC from the outlet of the gradient**  **pump. Dispose of the contents of the**

**waste container as hazardous waste.**

**11.6.4 Place the prepared ATC between the Eluent 1 reservoir and the**  **gradient pump inlet as shown in Figures 3 and 4 and reconnect the gradient pump outlet**  **line to the injection valve.**

**NOTE : The ATC is capable of treating only a limited am**  **ount of Eluent 1. For optimum performance, the column must be replaced or recondi**  **tioned following treatment of each**

**2-3 L of Eluent 1.**

**11.7 Prime the gradient pump lines for Eluents 1, 2 and 3 separately to remove**  **trapped air within each line. To do this, select o ne eluent, set to 100%, and begin priming.**  **Repeat this step for the remaining eluents.**

**11.8 Prime the gradient pump once more using the i nitial method settings.** 

**11.9 Connect the guard and analytical columns in b etween the injection valve and** 

**the inlet of the UV/Vis detector. Ensure that the columns are oriented in the appropriate** 

**direction for eluent flow.**

**11.10 Allow the instrument to equilibrate prior to the analysis by pumping eluent**  **through the concentrator column (if present), guard and analytical columns at a flow rate of 1**  **mL/min using the initial eluent settings.**

**11.11 Set the UV/Vis detector to 215 nm and offset the absorbance to zero.** 

**NOTE : Eluent is pumped through the concentrator column**  **by placing the injection valve in the "Inject" mode (See Figure 5.).** 

**11.12 Check the sample pH and adjust, if needed, t o pH 11-12 using 50% H**  **2 SO**  **4**

**.**

**11.13 Filter an appropriate volume of aqueous samp le using a plastic syringe fitted** 

**with a 0.45-** μ **m syringe filter. Alternatively, use a portion of filtered extract obtained from the**  **alkaline extraction procedure (e.g., Method 9013).**

**11.14 Transfer the filtered sample to an amber sam ple vial. Repeat this procedure for**  **the remaining samples.**

**11.15 Transfer the method blank, calibration blank , calibration standards and QA/QC**  **samples (see Sec. 9.0.) and standards to amber samp le vials.** 

**11.16 Place all of the vials in the autosampler.**

**11.17 Start the autosampler, and instrument contro l and data collection system, and**  **begin analyzing the samples. A water blank should be analyzed first to equilibrate the columns**  **followed by the method blank, calibration standards (Sec. 10.1) and samples, including QC** **SW-846 Update V 9015 - 19 Revision 1**

**October 2012 samples (Sec. 9.0). Use an injection volume of app**  **roximately 0.1 mL for samples containing 0.2 - 200 mg/L metal cyanide complexes and an injec**  **tion volume of approximately 5 - 20 mL when using sample preconcentration for samples cont**  **aining 0.5-200** μ **g/L metal cyanide complexes. Periodically and after the analysis of**  **no more than 20 samples, analyze a continuing calibration verification standard to ass**  **ess instrument drift throughout the run (See Sec. 9.6). Examples of method chromatograms are pr**  **ovided in Figures 6 through 11.**

**11.18 Confirmation**

**Tentative identification of the analyte occurs whe n a peak from the sample falls within**  **the retention time window established by the calibr ation standards. Confirmation is**  **recommended when the sample composition is not well characterized. Confirmatory techniques**  **such as anion exchange chromatography with a dissim ilar column or anion exchange**  **chromatography with a dissimilar detection method s uch as inductively coupled plasma-mass**  **spectrometry (ICP-MS) can be used.**

**When analyte identification is successfully confir med using two dissimilar columns or two**  **dissimilar detectors, the disparity between the qua ntitative results should be formally evaluated**  **by determining the RPD. The RPD acceptance criteri a and data reporting requirements should**  **be established based on the intended application of the data. See Method 8000, Sec. 11 (Ref.**  **19) for additional guidance.**

**12.0 DATA ANALYSIS AND CALCULATIONS**

**12.1 Derive the concentration of each respective m etal cyanide analyte in either**  **mg/L or μg/L in the samples using the regression pl ot as described in Sec. 10.2. Results must**  **be reported in units commensurate with their intend ed use and all dilutions must be taken into**  **account when computing final results.**

**12.2 Use the following calculation to convert samp le concentrations expressed as**  **mg/L to mg/kg for a solid waste matrix:**



## ( ) 

## [ ] ( )



## [ ] **kg g**  **1000**

**sample g**  **volume extraction**  **L CN**  **M L**  **mg CN**  **M kg**  **mg x**  **b x**  **b** 

### ×

× = − −

**12.3 Convert the metal cyanide results to cyanide when reporting the results "as**  **cyanide" based on the following calculation:**



## ( ) 

# [ ] ( )



# [ ] ( ) ( ) 

# [ ]

− −

− 

### × × μ

= μ

**x**

**b x** 

**b x** 
**b** 

### CN **M of** 

**. Wt**  **Formula CN** 

**of**

**. Wt**  **Formula b**  **CN M**  **L mg**  **or g**  **CN as**  **CN M**  **L mg**  **or g** 

**The formula weights for cyanide as well as those fo r each of the metal cyanide complexes are**  **provided in Table 6. SW-846 Update V 9015 - 20 Revision 1** 

**October 2012 13.0 METHOD PERFORMANCE** 

**13.1 Performance data and related information are provided in SW-846 methods**  **only as examples and guidance. The data do not rep resent required performance goals for**  **users of the methods. Instead, performance goals s hould be developed on a project-specific**  **basis, and the laboratory should establish in-house QC performance criteria for the application**  **of this method. These performance data are not int ended to be and must not be used as**  **absolute QC acceptance criteria for purposes of lab oratory accreditation.** 

**13.2 Tables 7 through 12 present precision and bia s data from multiple laboratories**  **for a spiked reagent water, groundwater and soil ex tract using anion exchange chromatography.**  **These data are provided for guidance purposes only.**

**13.3 Tables 13 through 18 present precision and bi as data from multiple laboratories**  **for a spiked reagent water, groundwater and soil ex tract using anion exchange chromatography**  **equipped with on-line sample preconcentration. The se data are provided for guidance purposes**  **only.**

**13.4 Table 19 presents total cyanide extraction re coveries for spiked solid waste**  **samples prepared using Method 9013. These data are provided for guidance purposes only.** 

**13.5 A lack of significant analytical bias has bee n confirmed by comparing the**  **results of the test method to those obtained using anion exchange chromatography coupled with**  **ICP-MS detection for a variety of environmental mat rices. (See Ref. 1.)** 

**14.0 POLLUTION PREVENTION**

**14.1 Pollution prevention encompasses any techniqu e that reduces or eliminates the**  **quantity and/or toxicity of waste at the point of g eneration. Numerous opportunities for pollution**  **prevention exist in laboratory operation. The EPA has established a preferred hierarchy of**  **environmental management techniques that places pol lution prevention as the management**  **option of first choice. Whenever feasible, laborat ory personnel should use pollution prevention**  **techniques to address their waste generation. When wastes cannot be feasibly reduced at the**  **source, the Agency recommends recycling as the next best option.** 

**14.2 For information about pollution prevention th at may be applicable to**  **laboratories and research institutions, consult** Less is Better: Laboratory Chemical Management for Waste Reduction, **a free publication available from the American Che mical Society (ACS),**  **Committee on Chemical Safety. http://portal.acs.org/portal/fileFetch/C/WPCP_01229**  **0/pdf/WPCP_012290.pdf**

**15.0 WASTE MANAGEMENT**

**15.1 The Environmental Protection Agency requires that laboratory waste**  **management practices be conducted consistent with a ll applicable rules and regulations. The**  **Agency urges laboratories to protect the air, water , and land by minimizing and controlling all**  **releases from hoods and bench operations, complying with the letter and spirit of any sewer**  **discharge permits and regulations, and by complying with all solid and hazardous waste**  **regulations, particularly the hazardous waste ident ification rules and land disposal restrictions.**  **For further information on waste management, consul t the ACS publication listed in Sec. 14.2.** **SW-846 Update V 9015 - 21 Revision 1**

**October 2012 15.2 Some of the reagents and solutions used in th**  **is method as well as the effluent from the chromatograph contain cyanide and should b**  **e handled and disposed of in an approved**

**manner.**

**16.0 REFERENCES**

**1. American Society for Testing and Materials, "Sta ndard Test Method for Determination of**  **Metal Cyanide Complexes in Wastewater, Surface Wate r, Groundwater and Drinking**  **Water using Anion Exchange Chromatography with UV D etection," D 6994, ASTM**  **International, 2004. This reference can be purchas ed on line at ASTM’s web site:**  **http://www.astm.org**

**2. Dionex Corporation, "Determination of Metal Cyan ides," Dionex Application Note No. 55,**  **November, 1989.**

**3. American Society for Testing and Materials, "Sta ndard Guide for Understanding Cyanide**  **Species," D 6696, ASTM International, 2004. This r eference can be purchased on line**  **at ASTM’s web site: http://www.astm.org**

**4. R. S. Ghosh, D. A. Dzombak, R. G. Luthy, "Equili brium Precipitation and Dissolution of**  **Iron Cyanide Solids in Water,"** Environ. Eng. Sci. **, Vol. 16, 293-313, 1999.**

**5. J. C. L. Meeussen, W. H. Keizer, F. A. M. de Haa n, "Chemical Stability and**  **Decomposition Rate of Iron Cyanide Complexes in Soi l Solutions,"**  Environ. Sci.

Technol. **, Vol. 26, 511-516, 1992.**

**6. J. C. L. Meeussen, M. G. Keizer, W. H. van Riems dijk, F. A. M. de Haan "Dissolution**  **Behavior of Iron Cyanide (Prussian Blue) in Contami nated Soils,"**  Environ. Sci. Technol.

**, Vol. 26, 1832-1838, 1992.** 

**7. U.S. Environmental Protection Agency, "Cyanide E xtraction Procedure for Solids and**  **Oils, Method 9013" U.S. EPA Office of Solid Waste S W-846 Manual.** 

**8. P. Doudoroff, "Toxicity to Fish of Cyanides and Related Compounds: A Review," EPA**  **Report No. 600/3-76-038, 1976.**

**9. U.S. Environmental Protection Agency, "Total and Amenable Cyanide: Distillation,** 

**Method 9010" U.S. EPA Office of Solid Waste SW-846 Manual.** 

**10. American Society for Testing and Materials, "St andard Test Methods for Cyanides in**  **Water," D 2036, ASTM International, 2004. This ref erence can be purchased on line at**  **ASTM’s web site: http://www.astm.org**

**11. American Public Health Association, "Standard M ethods for the Examination of Water**  **and Wastewater," 20 th**  **Edition, 1998.**

**12. R. A. Wetzel, C. L. Anderson, H. Schleicher, G. D. Crook, "Determination of Trace Level**  **Ions by Ion Chromatography with Concentrator Column s,"**  Analytical Chemistry **, Vol. 15, No. 9, 1532-1535, 1979.** **SW-846 Update V 9015 - 22 Revision 1**

**October 2012 13. W. S. Rader, L. Solujic, E. B. Milosavljevic, J**  **. L. Hendrix, "Sunlight-Induced Photochemistry of Aqueous Solutions of Hexacyanofer**  **rate(II) and –(III) Ions,"** Environ.

Sci. Technol. **, Volume 27, 1875-1879, 1993.**

**14. L. Moggi, F. Bolletta, V. Balzani, F. Scandola, "Photochemistry of Co-ordination**  **Compounds_XV,"** J. inorg. Nucl. Chem. **, Vol. 28, 2589-2597, 1966.**

**15. Dionex Corporation, "Product Manual IonPac**  **ATC-3 2-mm Anion Trap Column IonPac ATC-3 4-mm Anion Trap Column IonPac ATC-HC Anion Tr**  **ap Column," Document No. 032697, Revision 08, July 12, 2002.** 

**16. Dionex Corporation, "Product Manual IonPac**  **AG2 Guard Column IonPac**  **AG3**

**Guard Column IonPac**  **AG4 Guard Column IonPac**  **AG5 Guard Column IonPac** 

**CG2 Guard Column IonPac**  **AS2 Analytical Column IonPac**  **AS3 Analytical Column**

**IonPac**  **AS4 Analytical Column IonPac**  **AS5 Analytical Column IonPac**  **CS2 Analytical Column," Document No. 032226, Revision 1**  **4, May 12, 2002.**

**17. Dionex Corporation, "Product Manual IonPac**  **AG11 Guard Column IonPac**  **AS11 Analytical Column," Document No. 034791, Revision 0**  **8, May 14, 2003.**

**18. Dionex Corporation, "Dionex Installation and Tr oubleshooting Guide for the IonPac**   **MFC-1 Metal-Free Trap Column," Document No. 034990, Revision 02, June 26, 1998.** 

**19. U.S. Environmental Protection Agency, "Determin ative Chromatographic Separations,** 

**Method 8000" U.S. EPA Office of Solid Waste SW-846 Manual.** 

**20. R. M. Smith, A. E. Martell, "NIST Critically Se lected Stability Constants of Metal**  **Complexes Database, Version 5.0 Database Software" NIST Standard Reference**  **Database 46, U.S. Department of Commerce, Gaithersb urg, Maryland, 1998.** 

**21. D. D. Wagman, W. H. Evans, V. B. Parker, R. H. Shumm, I. Halow, S. M. Bailey, K. L.**  **Churney, R. L. Nuttal, "The NBS Tables of Chemical Thermodynamic Properties,**  **Selected Values for Inorganic and C 1**  **and C 2**  **Organic Substances in SI Units,"** Journal of Physical and Chemical Reference Data **, Vol. 11, Supplement 2, 1-392, 1982.**

**22. The RETEC Group, Inc., "Metal Cyanide Complexes by**  **Anion Exchange Chromatography and UV Detection Method Validation S**  **ummary Report," March, 2004.**

**23. U.S. Environmental Protection Agency, "Total an d Amenable Cyanide (Automated**  **Colorimetric, with Off-Line Distillation), Method 9 012" U.S. EPA Office of Solid Waste** 

**SW-846 Manual.**

**17.0 TABLES, DIAGRAMS, FLOW CHARTS, AND VALIDATION DATA** 

**The pages to follow contain the tables and figures referenced by this method.** **SW-846 Update V 9015 - 23 Revision 1**

**October 2012 TABLE 1** 

**APPROXIMATE CALIBRATION RANGES FOR METAL CYANIDE CO MPLEXES** 

**DETERMINED BY ANION EXCHANGE CHROMATOGRAPHY**

**Cyanide Species Calibration Range (mg/L)**

**[Ag(CN) 2**  **] -**  **0.5-100 [Au(CN)**  **2 ]**  **- 0.2-50**  **[Co(CN) 6**  **] 3** 

**- 0.5-100**  **[Cu(CN) 3**  **] 2** 

**- 0.2-20**  **[Fe(CN) 6**  **] 4** 

**- 0.10-20**  **[Ni(CN) 4**  **] 2** 

**- 1.0-200** 

**Data taken from Reference 1. SW-846 Update V 9015 - 24 Revision 1** 

**October 2012 TABLE 2** 

**APPROXIMATE CALIBRATION RANGES FOR METAL CYANIDE**

**COMPLEXES DETERMINED BY ANION EXCHANGE CHROMATOGRA PHY** 

**USING ON-LINE SAMPLE PRECONCENTRATION**

**Cyanide Species Calibration Range (μg/L)**

**[Ag(CN) 2**  **] -**  **10-120**

**[Au(CN) 2**  **] -**  **5.0-100**

**[Co(CN) 6**  **] 3-**  **1.0-200**

**[Cu(CN) 3**  **] 2-**  **1.0–5.0**

**[Fe(CN) 6**  **] 4-**  **0.5-20**

**[Ni(CN) 4**  **] 2-**  **50-100**

**Data taken from Reference 1. SW-846 Update V 9015 - 25 Revision 1** 

**October 2012 TABLE 3** 

**STABILITY CONSTANTS OF METAL CYANIDE COMPLEXES**

**Metal Cyanide Complex Stability Constant**  **(log K at 25oC, I a**  **= 0.0)**

**[Ag(CN) 2**  **] -**  **20.5**

**[Co(CN) 6**  **] 3-**  **64.0 b** 

**[Ni(CN) 4**  **] 2-**  **30.2**

**[Cu(CN) 4**  **] 3-**  **30.3**

**[Fe(CN) 6**  **] 4-**  **35.4**

**[Au(CN) 2**  **] -**  **126 c** 

**a I = Ionic Strength** 

**b The stability constant is considered to be an estim**  **ate**

**c For the reaction: [AuO**  **3 ]**  **3- + 2CN**  **- + 6H**  **+ +2e**  **-** → **[Au(CN) 2**  **] -**  **+ 3H 2**  **O**

**Data taken from References 20 and 21. SW-846 Update V 9015 - 26 Revision 1** 

**October 2012 TABLE 4** 

**METHOD SETTINGS FOR THE ANALYSIS OF METAL CYANIDE C OMPLEXES** 

**USING GRADIENT ELUTION**

Gradient Pump Absorbance Detector Comments

and

Function Time Flow Rate Eluent

1 Eluent

2 Eluent

3 Wavelength Data Collection

(min) (mL/min) (%) (%) (%) (nm) (Absorbance Units)

Init. 1.00 10 10 80 215 Initial Conditions

0.0 1.00 10 10 80 215 Offset baseline Analysis gradient 18.0 1.00 10 45 45 215 Begin

22.0 1.00 10 45 45 215 End

25.0 a 1.00 10 10 80 215 Equilibration

35.0 1.00 10 10 80 215

**a The eluents are reset to their initial concentratio**  **ns and allowed to pump for 10 min at the end of th e analysis run to**  **equilibrate the columns prior to the next sample in jection.** **SW-846 Update V 9015 - 27 Revision 1**

**October 2012 TABLE 5** 

**METHOD SETTINGS FOR THE ANALYSIS OF METAL CYANIDE C OMPLEXES** 

**USING GRADIENT ELUTION AND ON-LINE SAMPLE PRECONCEN TRATION** 

Two-way Switching

Valve Gradient Pump Absorbance

Detector Sample

Concentrator Pump Comments

and

Function

Position Flow Eluent Eluent Pump Data

Time Rate 1 2 3 Wavelength Collection
(min) (mL/min) (%) (%) (%) (nm) (Absorbance Units) (2 mL/min)

Init. Load 1.00 10 10 80 215 Initi al Conditions

0.0 Load 1.00 10 10 80 215

1.0 a Load 1.00 10 10 80 215 On Equilibration

11.0 Inject 1.00 10 10 80 215 Off Sample Injection

11.1 Inject 1.00 10 10 80 215 Offset baseline Analysis

Gradient 11.2 Inject 1.00 10 10 80 215 Begin

29.2 Inject 1.00 10 45 45 215

33.2 Load 1.00 10 45 45 215 End

**a The eluents are pumped through the guard and analyt**  **ical columns at their initial concentrations for 10 min at the**  **beginning of the analysis run to equilibrate the co lumns between sample injections. During this time,**  **the sample concentrator pump is turned on and 20 mL of sample**  **is pumped to the concentrator column. SW-846 Update V 9015 - 28 Revision 1** 

**October 2012 TABLE 6** 

**CYANIDE SPECIES FORMULA WEIGHTS**

**Cyanide Species Formula Weight**  **(mg/mmol)**

**CN -**  **26.0177**

**[Ag(CN) 2**  **] -**  **159.903**

**[Au(CN) 2**  **] -**  **249.002**

**[Co(CN) 6**  **] 3-**  **215.039**

**[Cu(CN) 3**  **] 2-**  **141.599**

**[Fe(CN) 6**  **] 4-**  **211.953**

**[Ni(CN) 4**  **] 2-**  **162.771 SW-846 Update V 9015 - 29 Revision 1** 

**October 2012 TABLE 7** 

**EXAMPLE [Fe(CN) 6**  **] 4-**  **ANALYSIS PRECISION AND BIAS**

**USING ANION EXCHANGE CHROMATOGRAPHY**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (mg/L) (mg/L) Samples Youden Pairs (mg/L) (m g/L) Bias** 

**Reagent Water 1.0 1.08 7 0.06 8.4%**

**1.2 1.30 6 6 0.03 0.03 8.2%**

**9.0 9.48 6 0.10 5.3%**

**10.0 10.49 7 6 0.14 0.31 4.9%**

**17.5 18.45 6 0.28 5.4%**

**18.5 19.30 7 6 0.24 0.57 4.3%**

**Groundwater 1.0 1.05 7 0.02 4.7%**

**1.2 1.28 7 7 0.02 0.04 6.4%**

**9.0 9.42 6 0.09 4.6%**

**10.0 10.51 7 6 0.07 0.24 5.1%**

**17.5 18.29 7 0.42 4.5%**

**18.5 19.28 7 7 0.07 0.36 4.2%**

**Soil Extract 1.0 1.09 3 0.08 8.7%**

**1.2 1.25 3 3 0.03 0.04 4.3%**

**9.0 9.36 3 0.14 4.0%**

**10.0 10.32 3 3 0.05 0.08 3.2%**

**17.5 18.06 3 0.16 3.2%**

**18.5 19.22 3 3 0.10 0.13 3.9%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories** 

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 30 Revision 1** 

**October 2012 TABLE 8** 

**EXAMPLE [Cu(CN) 3**  **] 2-**  **ANALYSIS PRECISION AND BIAS**

**USING ANION EXCHANGE CHROMATOGRAPHY**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (mg/L) (mg/L) Samples Youden Pairs (mg/L) (m g/L) Bias** 

**Reagent**

**Water 0.20 0.22 7 0.02 10.0%** 

**0.24 0.30 6 6 0.01 0.01 23.9%**

**0.90 0.97 6 0.06 7.3%**

**1.0 1.08 7 6 0.03 0.12 8.2%**

**1.6 1.81 7 0.15 13.0%**

**1.7 1.94 6 6 0.03 0.11 14.2%**

**Groundwater 0.20 0.22 7 0.01 7.9%**

**0.24 0.30 7 7 0.01 0.02 22.7%**

**0.90 0.96 6 0.04 6.9%**

**1.0 1.04 7 6 0.02 0.04 4.4%**

**1.6 1.74 7 0.11 8.7%**

**1.7 1.83 7 7 0.01 0.13 7.6%**

**Soil Extract 0.20 0.23 3 0.02 16.2%**

**0.24 0.26 3 3 0.01 0.01 7.2%**

**0.85 0.94 3 0.04 10.9%**

**0.95 1.00 3 3 0.01 0.03 5.1%**

**1.6 1.70 3 0.07 6.3%**

**1.7 1.80 3 3 0.01 0.09 6.1%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories** 

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 31 Revision 1** 

**October 2012 TABLE 9** 

**EXAMPLE [Ag(CN) 2**  **] -**  **ANALYSIS PRECISION AND BIAS**

**USING ANION EXCHANGE CHROMATOGRAPHY**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (mg/L) (mg/L) Samples Youden Pairs (mg/L) (m g/L) Bias** 

**Reagent Water 21.0 22.94 7 1.22 9.2%**

**23.0 25.31 7 7 0.59 1.09 10.1%**

**46.0 50.13 6 1.80 9.0%**

**51.0 55.46 7 6 0.49 1.56 8.7%**

**85.0 88.36 7 1.61 3.9%**

**90.0 94.00 7 7 1.42 1.82 4.4%**

**Groundwater 21.0 23.68 7 0.54 12.8%**

**23.0 25.90 7 7 0.84 0.92 12.6%**

**46.0 50.86 7 1.47 10.6%**

**51.0 55.86 7 7 0.47 1.11 9.5%**

**85.0 90.37 7 2.20 6.3%**

**90.0 94.77 7 7 0.45 2.08 5.3%**

**Soil Extract 21.0 22.47 3 0.37 7.0%**

**23.0 24.17 3 3 0.17 0.34 5.1%**

**46.0 48.45 3 0.77 5.3%**

**51.0 53.06 3 3 0.22 0.50 4.0%**

**85.0 88.58 3 0.46 4.2%**

**90.0 92.38 3 3 1.58 1.85 2.6%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories** 

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 32 Revision 1** 

**October 2012 TABLE 10** 

**EXAMPLE [Au(CN) 2**  **] -**  **ANALYSIS PRECISION AND BIAS**

**USING ANION EXCHANGE CHROMATOGRAPHY**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (mg/L) (mg/L) Samples Youden Pairs (mg/L) (m g/L) Bias** 

**Reagent Water 10.0 10.98 7 0.64 9.8%**

**12.0 12.59 6 6 0.40 0.26 4.9%**

**20.0 22.00 7 1.97 10.0%**

**22.0 23.09 6 6 1.34 0.58 5.0%**

**40.0 41.57 6 0.86 3.9%**

**42.0 43.29 6 6 0.47 0.93 3.1%**

**Groundwater 10.0 10.53 6 0.41 5.3%**

**12.0 12.38 7 6 0.43 0.69 3.1%**

**20.0 21.56 7 1.13 7.8%**

**22.0 22.73 7 7 1.43 1.26 3.3%**

**40.0 42.27 6 0.83 5.7%**

**42.0 44.00 6 6 0.55 0.81 4.8%**

**Soil Extract 10.0 10.35 3 0.37 3.5%**

**12.0 11.75 3 3 0.61 1.04 -2.1%**

**20.0 20.44 3 0.68 2.2%**

**22.0 22.62 3 3 0.16 0.65 2.8%**

**40.0 41.82 3 0.61 4.6%**

**42.0 44.12 3 3 0.60 1.12 5.1%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories** 

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 33 Revision 1** 

**October 2012 TABLE 11** 

**EXAMPLE [Co(CN) 6**  **] 3-**  **ANALYSIS PRECISION AND BIAS**

**USING ANION EXCHANGE CHROMATOGRAPHY**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (mg/L) (mg/L) Samples Youden Pairs (mg/L) (m g/L) Bias** 

**Reagent Water 15.0 15.63 7 0.39 15.0**

**18.0 18.67 7 7 0.23 0.40 18.0**

**46.0 47.78 6 0.40 46.0**

**50.0 51.42 6 6 0.25 0.14 50.0**

**85.0 86.17 7 0.66 85.0**

**90.0 91.01 7 7 0.68 1.52 90.0**

**Groundwater 15.0 15.71 7 0.48 4.7%**

**18.0 18.83 7 7 0.18 0.32 4.6%**

**46.0 47.87 7 0.91 4.1%**

**50.0 51.31 7 7 0.27 1.12 2.6%**

**85.0 86.48 7 1.75 1.7%**

**90.0 91.35 7 7 0.21 1.93 1.5%**

**Soil Extract 15.0 15.64 3 0.43 4.2%**

**18.0 18.53 3 3 0.07 0.51 3.0%**

**46.0 47.43 3 1.24 3.1%**

**50.0 50.96 3 3 0.34 1.08 1.9%**

**85.0 86.16 3 2.41 1.4%**

**90.0 91.55 3 3 0.25 2.18 1.7%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories** 

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 34 Revision 1** 

**October 2012 TABLE 12** 

**EXAMPLE [Ni(CN) 4**  **] 2-**  **ANALYSIS PRECISION AND BIAS**

**USING ANION EXCHANGE CHROMATOGRAPHY**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (mg/L) (mg/L) Samples Youden Pairs (mg/L) (m g/L) Bias** 

**Reagent Water 20.0 21.93 7 0.98 9.6%**

**24.0 25.91 7 7 0.48 1.18 7.9%**

**85.0 91.15 7 2.10 7.2%**

**95.0 101.6 7 7 0.72 2.40 6.9%**

**175 185.9 7 9.64 6.2%**

**185 193.5 7 7 2.33 8.65 4.6%**

**Groundwater 20.0 21.62 7 1.67 8.1%**

**24.0 25.47 7 7 0.43 1.74 6.1%**

**85.0 90.49 6 1.05 6.5%**

**95.0 99.72 7 6 0.75 3.32 5.0%**

**175 181.53 7 4.22 3.7%**

**185 190.73 7 7 1.58 2.99 3.1%**

**Soil Extract 20.0 21.29 3 0.27 8.4%**

**24.0 26.00 3 3 0.07 2.27 4.7%**

**85.0 89.02 3 1.97 5.6%**

**95.0 100.35 3 3 0.53 5.10 2.6%**

**175 179.47 3 6.31 3.1%**

**185 190.82 3 3 1.54 0.00 0.0%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories** 

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 35 Revision 1** 

**October 2012 TABLE 13** 

**EXAMPLE [Fe(CN) 6**  **] 4-**  **ANALYSIS PRECISION AND BIAS USING ANION EXCHANGE**

**CHROMATOGRAPHY AND ON-LINE SAMPLE PRECONCENTRATION**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (μg/L) (μg/L) Samples Youden Pairs (μg/L) (μ g/L) Bias** 

**Reagent Water 1.6 1.68 6 0.08 5.1%**

**1.8 1.87 5 5 0.06 0.02 3.9%**

**9.5 9.08 6 0.86 -4.4%**

**11.0 10.90 6 6 0.38 0.41 -1.0%**

**17.0 16.53 6 1.16 -2.8%**

**18.0 17.49 6 6 1.06 0.88 -2.9%**

**Groundwater 1.6 2.17 6 0.49 35.4%**

**1.8 2.22 5 5 0.28 0.16 23.5%**

**9.5 9.72 6 1.60 2.3%**

**11.0 10.94 5 5 0.30 0.50 -0.5%**

**17.0 17.53 5 0.98 3.1%**

**18.0 18.08 5 5 0.92 0.46 0.4%**

**Soil Extract 1.6 1.75 1 9.5%**

**1.8 1.98 1 1 NA NA 10.1%**

**9.5 9.72 1 2.3%**

**11.0 11.21 1 1 NA NA 2.0%**

**17.0 17.66 1 3.9%**

**18.0 18.57 1 1 NA NA 3.2%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories**  **NA = Not Applicable, single laboratory study**

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 36 Revision 1** 

**October 2012 TABLE 14** 

**EXAMPLE [Cu(CN) 3**  **] 2-**  **ANALYSIS PRECISION AND BIAS USING ANION EXCHANGE**

**CHROMATOGRAPHY AND ON-LINE SAMPLE PRECONCENTRATION**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (μg/L) (μg/L) Samples Youden Pairs (μg/L) (μ g/L) Bias** 

**Reagent Water 1.1 1.47 6 0.62 34.0%**

**1.3 1.05 5 5 0.45 0.30 -19.5%**

**2.3 2.25 6 0.20 -2.0%**

**2.5 3.22 6 6 0.25 0.35 28.8%**

**4.4 4.38 6 0.32 -0.5%**

**4.6 4.81 6 6 0.26 0.35 4.6%**

**Groundwater 1.1 0.89 4 0.74 -19.1%**

**1.3 0.73 5 4 0.25 0.92 -44.2%**

**2.3 0.87 5 0.62 -62.0%**

**2.5 0.89 5 5 0.09 0.71 -64.3%**

**4.4 1.30 5 0.77 -70.3%**

**4.6 1.27 5 5 0.21 0.99 -72.4%**

**Soil Extract 1.1 0.32 1 -71.0%**

**1.3 0.32 1 1 NA NA -75.5%**

**2.3 0.51 1 -78.0%**

**2.5 0.84 1 1 NA NA -66.3%**

**4.4 1.00 1 -77.3%**

**4.6 1.06 1 1 NA NA -76.9%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories**  **NA = Not Applicable, single laboratory study**

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 37 Revision 1** 

**October 2012 TABLE 15** 

**EXAMPLE [Ag(CN) 2**  **] -**  **ANALYSIS PRECISION AND BIAS USING ANION EXCHANGE**

**CHROMATOGRAPHY AND ON-LINE SAMPLE PRECONCENTRATION**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (μg/L) (μg/L) Samples Youden Pairs (μg/L) (μ g/L) Bias** 

**Reagent Water 20.0 25.05 6 8.62 25.2%**

**24.0 28.64 6 6 1.57 8.12 19.3%**

**50.0 49.57 6 10.15 -0.9%**

**54.0 60.33 6 6 6.69 15.66 11.7%**

**110 97.02 6 15.20 -11.8%**

**115 103.13 6 6 3.57 18.88 -10.3%**

**Groundwater 20.0 10.19 5 1.77 -49.1%**

**24.0 15.45 6 5 1.12 4.38 -35.6%**

**50.0 29.11 6 5.94 -41.8%**

**54.0 31.26 6 6 1.61 5.22 -42.1%**

**110 62.93 6 9.50 -42.8%**

**115 65.63 6 6 1.70 10.35 -42.9%**

**Soil Extract 20.0 15.27 1 -23.6%**

**24.0 18.11 1 1 NA NA -24.6%**

**50.0 52.56 1 5.1%**

**54.0 57.99 1 1 NA NA 7.4%**

**110.0 117.32 1 6.7%**

**115.0 122.13 1 1 NA NA 6.2%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories**  **NA = Not Applicable, single laboratory study**

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 38 Revision 1** 

**October 2012 TABLE 16** 

**EXAMPLE [Au(CN) 2**  **] -**  **ANALYSIS PRECISION AND BIAS USING ANION EXCHANGE**

**CHROMATOGRAPHY AND ON-LINE SAMPLE PRECONCENTRATION**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (μg/L) (μg/L) Samples Youden Pairs (μg/L) (μ g/L) Bias** 

**Reagent Water 15.0 16.47 6 1.14 9.8%**

**18.0 18.46 6 6 0.98 1.37 2.5%**

**57.0 58.49 6 3.91 2.6%**

**60.0 64.07 6 6 3.00 4.11 6.8%**

**85.0 87.04 5 0.63 2.4%**

**90.0 90.10 6 5 1.58 4.81 0.1%**

**Groundwater 15.0 14.25 6 1.49 -5.0%**

**18.0 17.14 5 5 0.77 2.28 -4.8%**

**57.0 53.66 6 5.58 -5.9%**

**60.0 56.16 6 6 4.12 6.63 -6.4%**

**85.0 82.05 6 4.72 -3.5%**

**90.0 84.58 6 6 2.75 8.31 -6.0%**

**Soil Extract 15.0 15.95 1 6.3%**

**18.0 18.10 1 1 NA NA 0.5%**

**57.0 60.63 1 6.4%**

**60.0 62.64 1 1 NA NA 4.4%**

**85.0 87.57 1 3.0%**

**90.0 95.84 1 1 NA NA 6.5%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories**  **NA = Not Applicable, single laboratory study**

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 39 Revision 1** 

**October 2012 TABLE 17** 

**EXAMPLE [Co(CN) 6**  **] 3-**  **ANALYSIS PRECISION AND BIAS USING ANION EXCHANGE**

**CHROMATOGRAPHY AND ON-LINE SAMPLE PRECONCENTRATION**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (μg/L) (μg/L) Samples Youden Pairs (μg/L) (μ g/L) Bias** 

**Reagent Water 12.0 12.46 7 0.88 3.9%**

**14.0 14.05 7 7 0.45 1.44 0.3%**

**95.0 90.48 7 7.06 -4.8%**

**105 102.92 7 7 3.74 3.47 -2.0%**

**180 173.95 7 12.40 -3.4%**

**190 182.39 7 7 9.87 7.99 -4.0%**

**Groundwater 12.0 12.96 6 1.49 8.0%**

**14.0 14.67 5 5 0.34 1.61 4.8%**

**95.0 93.61 6 5.42 -1.5%**

**105 104.31 6 6 1.81 3.30 -0.7%**

**180 176.25 6 7.52 -2.1%**

**190 189.16 6 6 2.70 4.52 -0.4%**

**Soil Extract 12.0 11.38 1 -5.1%**

**14.0 13.47 1 1 NA NA -3.8%**

**95.0 100.30 1 5.6%**

**105.0 109.09 1 1 NA NA 3.9%**

**180.0 188.41 1 4.7%**

**190.0 198.35 1 1 NA NA 4.4%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories**  **NA = Not Applicable, single laboratory study**

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 40 Revision 1** 

**October 2012 TABLE 18** 

**EXAMPLE [Ni(CN) 4**  **] 2-**  **ANALYSIS PRECISION AND BIAS USING ANION EXCHANGE**

**CHROMATOGRAPHY AND ON-LINE SAMPLE PRECONCENTRATION**

**Amount**

**Added Amount** 

**Found Number** 

**of**

**Retained Number of** 

**Retained S O**  **S T**  **Matrix (μg/L) (μg/L) Samples Youden Pairs (μg/L) (μ g/L) Bias** 

**Reagent Water 55.0 53.52 5 1.21 -2.7%**

**60.0 59.31 6 5 2.53 3.98 -1.1%**

**75.0 73.54 6 5.56 -2.0%**

**80.0 78.47 5 5 3.25 1.32 -1.9%**

**90.0 90.75 6 5.79 0.8%**

**95.0 95.72 6 6 5.50 6.86 0.8%**

**Groundwater 55.0 43.32 6 9.97 -21.2%**

**60.0 39.20 6 6 15.25 19.34 -34.7%**

**75.0 55.89 6 8.81 -25.5%**

**80.0 59.92 6 6 2.93 6.57 -25.1%**

**90.0 71.95 6 10.24 -20.1%**

**95.0 79.89 6 6 9.42 12.41 -15.9%**

**Soil Extract 55.0 50.58 1 -8.0%**

**60.0 55.17 1 1 NA NA -8.1%**

**75.0 72.77 1 -3.0%**

**80.0 76.02 1 1 NA NA -5.0%**

**90.0 87.76 1 -2.5%**

**95.0 91.23 1 1 NA NA -4.0%**

**S T**  **= Overall standard deviation across multiple labor atories** 

**S O**  **= Single operator standard deviation across multipl e laboratories**  **NA = Not Applicable, single laboratory study**

**These data are provided for guidance purposes only.**

**Data taken from References 1 and 22. SW-846 Update V 9015 - 41 Revision 1** 

**October 2012 TABLE 19** 

**TOTAL CYANIDE RECOVERIES IN SPIKED SOILS PREPARED U SING** 

**METHOD 9013 EXTRACTION**

**Sample Background Total** 

**Cyanide**

**Concentration a**  **(μg/g Cyanide) Spiking** 

**Concentration b** 
**(μg/g Cyanide) Average Total**  **Cyanide Recovery**  **b Standard** 

**Deviation c** 

**Soil 1 0.44 500 95% 1.8% (n = 2)**

**Soil 2 0.17 500 78% 0.1% (n = 2)**

**Soil 3 ND 500 86% 6.4% (n = 4)**

a **Total cyanide was determined in the soil extracti on solutions using EPA SW-846 Methods 9010 and 9012**  **(Ref. 23).**

b **Soils were spiked using solid Fe 4**  **[Fe(CN) 6**  **] 3**  **prior to extraction.**

c **n = Number of replicate analyses**

**These data are provided for guidance purposes only.**

**Data taken from Reference 22. SW-846 Update V 9015 - 42 Revision 1** 

**October 2012 FIGURE 1** 

**EXAMPLE BLANK REAGENT WATER CHROMATOGRAM**

**These data are provided for guidance purposes only.**

**Figure taken from Reference 1.** -0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### Column: IonPac ® 

### AS11 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 100 μL

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Reagent Water

-0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### Column: IonPac ® 

### AS11 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 100 μL

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Reagent Water**SW-846 Update V 9015 - 43 Revision 1**

**October 2012 FIGURE 2** 

**EXAMPLE BLANK REAGENT CHROMATOGRAM WATER USING**

**ON-LINE SAMPLE PRECONCENTRATION**

**These data are provided for guidance purposes only.**

**Figure taken from Reference 1.** -0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### Column: IonPac ® 

### AS11 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 100 μL

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Reagent Water

-0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### Column: IonPac ® 

### AS11 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 100 μL

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Reagent Water**SW-846 Update V 9015 - 44 Revision 1**

**October 2012 FIGURE 3** 

**CHROMATOGRAPH CONFIGURATION FOR THE ANALYSIS OF**

**METAL CYANIDE COMPLEXES**

**Figure taken from Reference 1. Anion trap** 

**column Gradient** 

**pump**

**Autosampler**

**Data analysis UV-Vis detector**  **Guard**

**column**

**Separator**

**column Eluents** 

**Anion trap**

**column Gradient** 

**pump**

**Autosampler**

**Data analysis UV-Vis detector**  **Guard**

**column**

**Separator**

**column Eluents** **SW-846 Update V 9015 - 45 Revision 1**

**October 2012 FIGURE 4** 

**CHROMATOGRAPH CONFIGURATION FOR THE ANALYSIS OF MET AL CYANIDE** 

**COMPLEXES USING SAMPLE PRECONCENTRATION**

**Figure taken from Reference 1.**

Metal free trap columns

**Data analysis UV-Vis detector**  **Guard**

**column**

**Separator**

**column Large volume**  **autosampler**

**To**

**waste Sample** 

**concentrator**

**pump**

**Concentrator**

**column Gradient** 

**pump Anion trap** 

**column**

**Eluents** Metal free trap columns

**Data analysis UV-Vis detector**  **Guard**

**column**

**Separator**

**column Large volume**  **autosampler**

**To**

**waste Sample** 

**concentrator**

**pump**

**Concentrator**

**column Gradient** 

**pump Anion trap** 

**column**

**Eluents SW-846 Update V 9015 - 46 Revision 1** 

**October 2012 FIGURE 5** 

**INJECTION VALVE CONFIGURATION FOR SAMPLE PRECONCENT RATION** 

**Figure taken from Reference 1. Guard and separator** 

**columns**

**To**

**waste Concentrator** 

**column Gradient Pump** 

**Sample**

**concentrator**

**pump**

**Load Inject**  **Guard and separator**

**columns**

**To**

**waste Concentrator** 

**column Gradient Pump** 

**Sample**

**concentrator**

**pump**

**Load Inject** **SW-846 Update V 9015 - 47 Revision 1**

**October 2012 FIGURE 6** 

**EXAMPLE SPIKED REAGENT WATER CHROMATOGRAM**

**These data are provided for guidance purposes only.**

**Figure taken from Reference 22.** -0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### 1

2

3 4
5 6 Column: IonPac ® 

### AS5 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 100 μL

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Spiked Reagent Water Peaks: 1. [Ag(CN) 2 

### ]

- 

### 22 mg/L

2. [Au(CN) 2 

### ]

- 

### 11 3. [Cu(CN) 3 

### ] 2- 

### 0.25 4. [Ni(CN) 4 

### ] 2- 

### 22 5. [Fe(CN) 6 

### ] 4- 

### 1.1 6. [Co(CN) 6 

### ] 3- 

### 17

-0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### 1

2

3 4
5 6 Column: IonPac ® 

### AS5 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 100 μL

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Spiked Reagent Water Peaks: 1. [Ag(CN) 2 

### ]

- 

### 22 mg/L

2. [Au(CN) 2 

### ]

- 

### 11 3. [Cu(CN) 3 

### ] 2- 

### 0.25 4. [Ni(CN) 4 

### ] 2- 

### 22 5. [Fe(CN) 6 

### ] 4- 

### 1.1 6. [Co(CN) 6 

### ] 3- 

### 17**SW-846 Update V 9015 - 48 Revision 1**

**October 2012 FIGURE 7** 

**EXAMPLE SPIKED GROUNDWATER CHROMATOGRAM**

**These data are provided for guidance purposes only.**

**Figure taken from Reference 1.** -0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### 1

2

3 4 5 6 Column: IonPac ® 

### AS5 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 100 μL

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Spiked Groundwater Peaks: 1. [Ag(CN) 2 

### ]

- 

### 22 mg/L

2. [Au(CN) 2 

### ]

- 

### 11 3. [Cu(CN) 3 

### ] 2- 

### 0.25 4. [Ni(CN) 4 

### ] 2- 

### 22 5. [Fe(CN) 6 

### ] 4- 

### 1.1 6. [Co(CN) 6 

### ] 3- 

### 17

-0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### 1

2

3 4 5 6 Column: IonPac ® 

### AS5 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 100 μL

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Spiked Groundwater Peaks: 1. [Ag(CN) 2 

### ]

- 

### 22 mg/L

2. [Au(CN) 2 

### ]

- 

### 11 3. [Cu(CN) 3 

### ] 2- 

### 0.25 4. [Ni(CN) 4 

### ] 2- 

### 22 5. [Fe(CN) 6 

### ] 4- 

### 1.1 6. [Co(CN) 6 

### ] 3- 

### 17**SW-846 Update V 9015 - 49 Revision 1**

**October 2012 FIGURE 8** 

**EXAMPLE SPIKED SOIL EXTRACT CHROMATOGRAM**

**These data are provided for guidance purposes only.**

**Figure taken from Reference 22.**



### Column: IonPac ® 

### AS11 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 100 μL

Detection: Absorbance at 215 nm Temperature: 35 °C

Sample: Spiked Soil Extract Peaks: 1. [Ag(CN) 2 

### ]

- 

### 75 mg/L

2. [Cu(CN) 3 

### ] 2- 

### 0.5 3. [Au(CN) 2 

### ]

- 

### 25 4. [Ni(CN) 4 

### ] 2- 

### 150 5. [Fe(CN) 6 

### ] 4- 

### 15 6. [Co(CN) 6 

### ] 3- 

### 75

-0.1 0.9Absorbance [AU]

Retention Time [min] 

### 1

2 3 4 5

6

0 10 20 

### Column: IonPac ® 

### AS11 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 100 μL

Detection: Absorbance at 215 nm Temperature: 35 °C

Sample: Spiked Soil Extract Peaks: 1. [Ag(CN) 2 

### ]

- 

### 75 mg/L

2. [Cu(CN) 3 

### ] 2- 

### 0.5 3. [Au(CN) 2 

### ]

- 

### 25 4. [Ni(CN) 4 

### ] 2- 

### 150 5. [Fe(CN) 6 

### ] 4- 

### 15 6. [Co(CN) 6 

### ] 3- 

### 75

-0.1 0.9Absorbance [AU]

Retention Time [min] 

### 1

2 3 4 5

6

0 10 20**SW-846 Update V 9015 - 50 Revision 1**

**October 2012 FIGURE 9** 

**EXAMPLE SPIKED REAGENT WATER CHROMATOGRAM USING**

**SAMPLE PRECONCENTRATION**

**These data are provided for guidance purposes only.**

**Figure taken from Reference 22.** -0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### 1
2

3 4 5 6 Column: IonPac ® 

### AS5 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 20 mL concentrated on AG5

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Spiked Reagent Water Peaks: 1. [Ag(CN) 2 

### ]

- 

### 100 μg/L

2. [Au(CN) 2 

### ]

- 

### 75 3. [Cu(CN) 3 

### ] 2- 

### 4 4. [Ni(CN) 4 

### ] 2- 

### 75 5. [Fe(CN) 6 

### ] 4- 

### 10 6. [Co(CN) 6 

### ] 3- 

### 100

-0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### 1
2

3 4 5 6 Column: IonPac ® 

### AS5 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 20 mL concentrated on AG5

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Spiked Reagent Water Peaks: 1. [Ag(CN) 2 

### ]

- 

### 100 μg/L

2. [Au(CN) 2 

### ]

- 

### 75 3. [Cu(CN) 3 

### ] 2- 

### 4 4. [Ni(CN) 4 

### ] 2- 

### 75 5. [Fe(CN) 6 

### ] 4- 

### 10 6. [Co(CN) 6 

### ] 3- 

### 100**SW-846 Update V 9015 - 51 Revision 1**

**October 2012 FIGURE 10** 

**EXAMPLE SPIKED GROUNDWATER CHROMATOGRAM USING**

**SAMPLE PRECONCENTRATION**

**These data are provided for guidance purposes only.**

**Figure taken from Reference 22.** -0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### 1

2

3 4 5 6 Column: IonPac ® 

### AS5 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 20 mL concentrated on AG5

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Spiked Groundwater Peaks: 1. [Ag(CN) 2 

### ]

- 

### 100 μg/L

2. [Au(CN) 2 

### ]

- 

### 75 3. [Cu(CN) 3 

### ] 2- 

### 4 4. [Ni(CN) 4 

### ] 2- 

### 75 5. [Fe(CN) 6 

### ] 4- 

### 10 6. [Co(CN) 6 

### ] 3- 

### 100

-0.1 0.9Absorbance [AU]

Retention Time [min] 0 10 20 

### 1

2

3 4 5 6 Column: IonPac ® 

### AS5 (4-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 1 mL/min Inj. Volume: 20 mL concentrated on AG5

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Spiked Groundwater Peaks: 1. [Ag(CN) 2 

### ]

- 

### 100 μg/L

2. [Au(CN) 2 

### ]

- 

### 75 3. [Cu(CN) 3 

### ] 2- 

### 4 4. [Ni(CN) 4 

### ] 2- 

### 75 5. [Fe(CN) 6 

### ] 4- 

### 10 6. [Co(CN) 6 

### ] 3- 

### 100**SW-846 Update V 9015 - 52 Revision 1**

**October 2012 FIGURE 11** 

**EXAMPLE SPIKED SOIL EXTRACT CHROMATOGRAM USING**

**SAMPLE PRECONCENTRATION**

**These data are provided for guidance purposes only.**

**Figure taken from Reference 22.** 

### Column: IonPac ® 

### AS11 (2-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 0.25 mL/min Inj. Volume: 5 mL concentrated on AG11

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Spiked Soil Extract Peaks: 1. [Ag(CN) 2 

### ]

- 

### 100 μg/L

2. [Cu(CN) 3 

### ] 2- 

### 4 3. [Au(CN) 2 

### ]

- 

### 75 4. [Ni(CN) 4 

### ] 2- 

### 75 5. [Fe(CN) 6 

### ] 4- 

### 10 6. [Co(CN) 6 

### ] 3- 

### 100

-0.1 0.9Absorbance [AU]

Retention Time [min]



### 1

2 3 4 5 6

0 10 20 

### Column: IonPac ® 

### AS11 (2-mm)

Eluent: NaClO 4 

### gradient in

20 mM NaOH/15 mM NaCN

Flow Rate: 0.25 mL/min Inj. Volume: 5 mL concentrated on AG11

Detection: Absorbance at 215 nm Temperature: ambient

Sample: Spiked Soil Extract Peaks: 1. [Ag(CN) 2 

### ]

- 

### 100 μg/L

2. [Cu(CN) 3 

### ] 2- 

### 4 3. [Au(CN) 2 

### ]

- 

### 75 4. [Ni(CN) 4 

### ] 2- 

### 75 5. [Fe(CN) 6 

### ] 4- 

### 10 6. [Co(CN) 6 

### ] 3- 

### 100

-0.1 0.9Absorbance [AU]

Retention Time [min]



### 1

2 3 4 5 6

0 10 20**SW-846 Update V 9015 - 53 Revision 1**

**October 2012 Appendix A**  **Summary of Revisions to Method 9015 (from Revision 1, November 2004)** 

**1. The entire document was formatted in Microsoft W ord 2007 .docx format from the**  **original .WPD and .PDF files. 2. Minor editorial and grammatical changes were mad**  **e throughout the document as**

**needed. 3. Text regarding the IDP (Sec. 9.2) and LLOQ (9.7)**  **consistent with SW-846 Chapter One**

**was added. 4. Graphics in the Figures Section were modified fr**  **om Corel Drawing Objects V.10 to .jpg graphical images where needed to remove artifacts f**  **rom the conversion process. The text titles of each figure was centered and formatt**  **ed. 5. This Appendix was added to document changes made**  **during the editorial process. 6. Updated and expanded the “QUALITY CONTROL” secti**  **on for better adherence to current SW-846 method guidelines and for improved a**  **lignment with current universal practices for published analytical methods.**