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July 2014 

METHOD 9013A 

CYANIDE EXTRACTION PROCEDURE FOR SOLIDS AND OILS

 SW-846 is not intended to be an analytical training manual. Therefore, method 

procedures are written based on the assumption that they will be followed by analysts who are 

formally trained in at least the basic principles of 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 guidance methods which contain general 

information on how to perform an analytical procedure or technique which a laboratory can use 

as a basic starting point for generating its own detailed standard operating procedure (SOP), 

either for its own general use or for a specific project application. The performance data 

included in this method are for guidance purposes only, and are not intended to be and must not 

be used as absolute QC acceptance criteria for purposes of laboratory accreditation.

1.0 SCOPE AND APPLICATION 

 1.1 The extraction procedure described in this method is designed for the extraction 

of soluble and insoluble cyanides from solid, oil, and multi-phase wastes. The resulting 

extraction solutions may be analyzed for total cyanide and/or cyanides amenable to chlorination 

(e.g., Methods 9010, 9012 and 9014) as well as analyzed for metal cyanide complexes (e.g., 

Method 9015). 

 1.2 Prior to employing this method, analysts should consult the disclaimer 

statement at the front of the manual and the information in Chapter Two for guidance on the 

intended flexibility in the choice of methods, apparatus, materials, reagents, and supplies, and 

on the responsibilities of the analyst for demonstrating that the techniques employed are 

appropriate for the analytes of interest, in the matrix of interest, and at the levels of concern. 

 In addition, analysts and data users are advised that, 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 method 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 the intended application. 

 1.3 This method is restricted to use by, or under supervision of, properly 

experienced and trained personnel. Each analyst must demonstrate the ability to generate 

acceptable results with this method. 

2.0 SUMMARY OF METHOD 

 The waste sample is extracted with water at pH 10 or greater, and the extract distilled 

and analyzed (e.g., by Methods 9010, 9012 and 9014). Samples that contain free water are 

filtered and separated into an aqueous component and a combined oil and solid component. 

The nonaqueous component is then extracted, and an aliquot of the extract combined with an 

aliquot of the filtrate in proportion to the composition of the sample. Alternatively, the 

components may be analyzed separately, and cyanide levels reported for each component. . 
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In the presence of free iron and high levels of suspended solids, some cyanide may combine 

with iron to form iron cyanide precipitates or possibly adsorb to suspended solids under the very 

low pH conditions encountered during the total cyanide distillation step (e.g., Methods 9010 and 

9012) (Refs. 1-6). When this occurs, some cyanide may remain in the distillation flask and not 

be distilled over into the absorber solution, resulting in incomplete recovery of cyanide. 

Therefore, alkaline extraction followed by distillation and analysis of the extract is the preferred 

method for determining total and amenable cyanide in solid samples. 

NOTE: This method has not been validated for recovery of free cyanide. Studies indicate that 

free cyanide may not be fully recovered for certain waste types. If recovery of free cyanide is 

important to meet project objectives, spiking studies should be performed for the specific 

matrices being tested. 

3.0 DEFINITIONS 

 Refer to Chapter One, Chapter Three, and the manufacturer's instructions for definitions 

that may be relevant to this procedure.

4.0 INTERFERENCES 

 4.1 Solvents, reagents, glassware, and other sample processing hardware may 

yield artifacts and/or interferences to sample analysis. All of these materials must be 

demonstrated to be free from interferences under the conditions of the analysis by analyzing 

method blanks. Specific selection of reagents and purification of solvents by distillation in allglass systems may be necessary. Refer to each method to be used for specific guidance on 

quality control procedures and to Chapter Three for general guidance on the cleaning of 

glassware. 

 4.2 Chlorine and sulfide are potential interferences in this method. Interferences 

are eliminated or reduced by using the distillation procedure. Distillation of samples for cyanide 

can result in both positive and negative bias depending upon the matrix of the sample. All 

interferences should be evaluated prior to the distillation of unknown samples. Negative bias is 

detected by incomplete spike recoveries. Positive bias cannot be detected using matrix spikes. 

Thiosulfate, sulfite, and other Sulfur (IV) oxides react with cyanide during distillation resulting in

a negative bias. Levels of the compounds below 20 mg/L do not generally interfere. 

 4.3 Oxidizing agents (such as chlorine) decompose most cyanide in solution. 

Chlorine interferences can be removed by adding an excess of sodium arsenite to the waste 

prior to preservation and storage of the sample. This reduces the chlorine to chloride which 

does not interfere. 

 4.4 Sulfide interference can be removed by adding an excess of bismuth nitrate to 

the waste (to precipitate the sulfide) before distillation. Samples that contain hydrogen sulfide, 

metal sulfides, or other compounds that may produce hydrogen sulfide during the distillation 

should be treated by the addition of bismuth nitrate. 

NOTE: ASTM studies have indicated that [Fe(CN)6]

-3 recoveries may be low when distilling 

samples containing bismuth nitrate. 
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 4.5 High results may be obtained for samples that contain nitrate and/or nitrite. 

During the distillation, nitrate and nitrite will form nitrous acid, which will react with some organic 

compounds to form oximes. These compounds, once formed, will decompose under test 

conditions to generate HCN. The possibility of interference of nitrate and nitrite is minimized by 

pretreatment with sulfamic acid just before distillation. Nitrate and nitrite are interferences when 

present at levels higher than 10 mg/L and in conjunction with certain organic compounds and 

thiocyanate. 

 4.6 Thiocyanate is reported to be an interferent when present at very high levels. 

Levels greater than 10 mg/L can interfere by decreasing the cyanide concentration. Nitrate and 

thiocyanate combined is a positive interference. 

 4.7 Fatty acids, detergents, surfactants, and other compounds may cause foaming 

during the distillation when they are present in high concentrations and may make the endpoint 

for the titrimetric determination difficult to detect. They may be extracted at pH 6-7 to eliminate 

this interference. 

 

 

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 work environment and a current awareness file 

of OSHA regulations regarding the safe handling of the chemicals specified in this method. A 

reference file of material safety data sheets (MSDSs) should be available to all personnel 

involved in these analyses. 

WARNING: KCN and NaCN are highly toxic. Avoid skin and eye contact and inhalation. 

 5.2 Because of the toxicity of cyanide, exercise great care in its handling. 

Acidification of cyanide solutions produces toxic, gaseous hydrogen cyanide (HCN). Perform all 

manipulations in the hood so that any HCN gas that is formed is safely vented. Wear hand and 

eye protection at all times when working with cyanide. 

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 endorsement 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 subsequently evaluated by the Agency. 

Glassware, reagents, supplies, equipment, and settings other than those listed in this manual 

may be employed provided that method performance appropriate for the intended application 

has been demonstrated and documented.

 This section does not list all common laboratory glassware (e.g., beakers and flasks) 

that might be used.

 6.1 Extractor - Any suitable device that sufficiently agitates a sealed container of 

one liter volume or greater. For the purpose of this analysis, agitation is sufficient when (1) all 

sample surfaces are continuously brought into contact with extraction fluid, and (2) the agitation 

prevents stratification of the sample and fluid. 
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 6.2 Buchner funnel apparatus 

 6.2.1 Buchner funnel - 500-mL capacity, with 1-L vacuum filtration flask 

 6.2.2 Glass wool - Suitable for filtering, 0.8-μm diameter such as Corning 

Pyrex 3950 

 6.2.3 Millipore 0.45-μm membrane filters - Suitable for filtering into a 

vacuum filtration flask 

 6.2.4 Vacuum source - Vacuum pump or a water driven aspirator. A 

valve or stopcock to release vacuum is required. 

 6.3 Top-loading balance - Capable of weighing 0.1 g 

 6.4 Separatory funnels - 500-mL 

 6.5 pH papers or test strips 

7.0 REAGENTS AND STANDARDS 

 7.1 Reagent grade chemicals must be used in all tests. Unless otherwise 

indicated, it is intended that all reagents conform to the specifications of the Committee on 

Analytical Reagents of the American Chemical Society, where such specifications are available. 

Other grades may be used, provided it is first ascertained that the reagent is 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 containers. 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 - Reagent water must be interference free. All references to 

water in this method refer to reagent water, as defined in Chapter One, unless otherwise 

specified. 

 7.3 Sodium hydroxide (50% w/v), NaOH - Commercially available 

 7.4 Sulfuric acid (50%v/v), H2SO4 - Commercially available 

 7.5 n-Hexane, C6H14

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 

 Sample collection, preservation and storage requirements may vary by EPA program 

and may be specified in a regulation or project planning document that requires compliance 

monitoring for a given contaminant. Where such requirements are specified in the regulation, 

follow those requirements. In the absence of specific regulatory requirements, use the following 

information as guidance in determining the sample collection, preservation and storage 

requirements. 

 8.1 See the introductory material to Chapter Three, “Inorganic Analytes.” 
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 8.2 Samples should be collected in plastic or glass (preferably plastic) containers 

that are either amber or covered with aluminum foil so as to filter light at 400 nm and below and 

prevent photodecomposition of metal cyanide complexes. All containers must be thoroughly 

cleaned and rinsed prior to use. All sample containers must be prewashed with acids, water, 

and metal-free detergents, if necessary, depending on the use history of the container. For 

further information, see Chapter Three.

 8.3 Store solid samples at ≤6 oC after collection and prior to extraction. Bring 

samples to room temperature just prior to extraction. 

 8.4 Store solid samples at ≤6 oC for no longer than 14 days. Solid phase samples 

must be extracted within 14 days of sample collection. 

 8.5 After generation, store solid phase extract solutions at ≤6 oC prior to analysis by 

the determinative method. Bring the extract solutions to room temperature just prior to analysis. 

 8.6 Store solid phase extract solutions at ≤6 oC for no longer than 14 days. 

Analysis of solid phase extracts must be performed within 14 days of extract generation. 

 8.7 If fatty acids, detergents, and surfactants are a problem, they may be extracted 

using the following procedure. Acidify the sample with acetic acid (1.6 M) to pH 6.0 to 7.0. 

CAUTION: This procedure can produce lethal HCN gas. 

Extract with isooctane, hexane, or chloroform (preference in order named) with solvent volume 

equal to 20% of the sample volume. One extraction is usually adequate to reduce the 

compounds below the interference level. Avoid multiple extractions or a long contact time at low 

pH in order to keep the loss of HCN at a minimum. When the extraction is completed, 

immediately raise the pH of the sample to 12 with a 50% NaOH solution. 

 8.7 Also see the applicable distillation and determinative method for additional 

guidance. 

9.0 QUALITY CONTROL 

 9.1 Refer to Chapter One for guidance on quality assurance (QA) and quality 

control (QC) protocols. When inconsistencies exist between QC guidelines, method-specific 

QC criteria take precedence over both technique-specific criteria and those criteria given in 

Chapter One, and technique specific QC criteria take precedence over the criteria in Chapter 

One. Any effort involving the collection of analytical data should include development of a 

structured and systematic planning document, such as 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 assurance program. The laboratory should 

also maintain records to document the quality of the data generated. All data sheets and quality 

control data should be maintained for reference or inspection. 

 9.2 Initial demonstration of proficiency 

 Each laboratory must demonstrate initial proficiency with each sample preparation and 

determinative method combination it utilizes by generating data of acceptable accuracy and 

precision for target analytes in a clean matrix. The laboratory must also repeat the 
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demonstration of proficiency whenever new staff members are trained or significant changes in 

instrumentation are made. 

 9.3 Initially, before processing any samples, the analyst should demonstrate that all 

parts of the equipment in contact with the sample and reagents are interference free. This is 

accomplished through the analysis of a method blank. As a continuing check, each time 

samples are extracted 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 chronic 

laboratory contamination. If a measurable absorbance is observed at or in close proximity to 

the measurement wavelength of the target analyte that would prevent the accurate 

determination of that analyte, determine the source and eliminate it, if possible, before 

processing the samples. The blanks should be carried through all stages of sample preparation 

and analysis. When new reagents or chemicals are received, the laboratory should monitor the 

preparation and/or analysis blanks associated with samples for any signs of contamination. It is 

not necessary to test every new batch of reagents or chemicals prior to sample preparation if 

the source shows no prior problems. However, if reagents are changed during a preparation 

batch, separate blanks need to be prepared for each set of reagents. 

 The laboratory should not subtract the results of the method blank from those of any 

associated samples. Such "blank subtraction" may lead to negative sample results. If the 

method blank results do not meet the project specific acceptance criteria and reanalysis is not 

practical, then the data user should be provided with 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 analysis 

 The laboratory must also have procedures for documenting the effect of the matrix on 

method performance (precision, accuracy, method sensitivity). At a minimum, this should 

include the analysis of QC samples including a method 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. 

 9.4.1 Method blank - For each batch of solid phase samples extracted using 

this method, at least one method blank should also be carried through the entire sample 

extraction, preparation and analytical process. A method blank is prepared by using a 

specified volume or weight of the extraction solution and then carrying it through the 

appropriate steps of the extraction and analytical process. These steps may include, but 

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 specific criteria 

requirements, then the method blank would be considered acceptable. In the 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 sample concentration, 

whichever is greater, then the method blank is considered acceptable. If the method 

blank cannot be considered acceptable, the method blank should be re-run once, and if 

still unacceptable, then all samples after the last acceptable method blank must be 

prepared again and reanalyzed along with the other appropriate 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 either below the reporting 

level or below the applicable action level or other criteria, then the data should not be 

rejected based on this analysis. 

 

 9.4.2 Matrix spike (MS)/ Duplicate - For each batch of solid phase samples 

extracted using this method, at least one matrix spike (MS) and one duplicate unspiked 
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sample or one matrix spike/matrix spike duplicate (MS/MSD) pair should be carried 

through the entire sample extraction, preparation and 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 decision on whether to prepare and analyze 

duplicate samples or a MS/MSD must be based on a knowledge of the samples in the 

sample batch. If samples are expected to contain the target analyte, laboratories may 

use a matrix spike (MS) and a duplicate analysis of an unspiked field sample. If samples 

are not expected to contain the target analyte, the laboratories should use a MS/MSD 

pair. A separate spiked sample and a separate duplicate unspiked sample may be 

analyzed in lieu of MS/MSD analyses. 

 9.4.3 LCS - For each batch of samples processed, at least one LCS must 

be carried through the entire sample preparation 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 different 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 when lacking project specific action levels, between the 

low- and mid-level standards. Concurrent analyses of standard reference materials 

(SRMs) containing known values of analytes in the media of interest are recommended 

and may be used as an LCS. 

NOTE: If insoluble or complexed cyanides (such as Prussian blue) are of interest, the 

recovery of cyanide should be evaluated from a similar species as that which is 

expected to be present in the samples. 

9.4.4 In order to verify the extraction process at the Lower Level of 

Quantitation (LLOQ), a matrix-free LLOQ check standard is prepared by spiking a clean 

control material with the analyte(s) of interest at the predicted LLOQ concentration 

level(s). This LLOQ check is carried through the same preparation procedures as the 

environmental samples and other QC. Recovery should be within established limits, or 

other such project required acceptance limits, for precision and bias to verify the data 

reporting limits. Until the laboratory has sufficient data to determine acceptance limits 

statistically, a limit of 20% +/- the LCS Criteria may be used for the LLOQ acceptance 

criteria. The frequency of this LLOQ verification is not mandated, but should be 

determined by the laboratory’s quality plan. Additional information on LLOQ can be 

found in 8000D, Section 9.7. 

 9.5 Standard quality assurance practices should be used with this method as 

included in appropriate systematic planning documents and laboratory SOPs. 

 9.6 Also refer to the applicable distillation and determinative method for appropriate 

quality control guidelines. 

10.0 CALIBRATION AND STANDARDIZATION 

 There are no calibration or standardization steps directly associated with this procedure. 
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11.0 PROCEDURE 

 11.1 If the waste does not contain any free aqueous phase, go to Sec. 11.6. If the 

sample is a homogeneous fluid or slurry that does not separate or settle in the distillation flask 

when using a polytetrafluorethylene (PTFE) coated magnetic stirring bar (but mixes so that the 

solids are entirely suspended); the sample may be analyzed by Method 9010 without an 

extraction step. 

 11.2 Assemble Buchner funnel apparatus. Unroll glass filtering fiber and fold the 

fiber over itself several times to make a pad about 1 cm thick when lightly compressed. Cut the 

pad to fit the Buchner funnel. Weigh the pad, and then place it in the funnel. Turn the aspirator 

on and wet the pad with a known amount of water. 

 11.3 Transfer the sample to the Buchner funnel in small aliquots, first decanting the 

fluid. Rinse the sample container with known amounts of water and add the rinses to the 

Buchner funnel. Record the total volume of rinses used. When no free water remains in the 

funnel, slowly open the stopcock to allow air to enter the vacuum flask. A small amount of 

sediment may have passed through the glass fiber pad. This will not interfere with the analysis. 

 11.4 Transfer the solid and the glass fiber pad to a tared weighing dish. Since most 

greases and oils will not pass through the fiber pad, solids, oils, and greases will be extracted 

together. If the filtrate includes an oil phase, transfer the filtrate to a separatory funnel. Collect 

and measure the volume of the aqueous phase. Transfer the oil phase to the weighing dish 

with the solid. 

 11.5 Weigh the dish containing solid, oil (if any), and filter pad. Subtract the weight 

of the dry filter pad. Calculate the net volume of water present in the original sample by 

subtracting the total volume of rinses used from the measured volume of the filtrate. 

 11.6 Place the following in a 1-L, wide-mouthed bottle: 

 500 mL water, 

 5 mL 50% w/v NaOH, and 

 50 mL n-hexane (if a heavy grease is present). 

If the weight of the solids (Sec. 11.5) is greater than 25 g, weigh out a representative aliquot of 

25 g and add it to the bottle; otherwise add all of the solids. Cap the bottle. 

 11.7 The extract must be maintained above pH 10 throughout the extraction step 

and subsequent filtration. Since some samples may release acid, the pH must be monitored as 

follows. Shake the extraction bottle and after one minute, check the pH. If the pH is below 12, 

add 50% NaOH in 5 mL increments until it is at least 12. Recap the bottle, and repeat the 

procedure until the pH does not drop. 

 11.8 Place the bottle or bottles in the tumbler, making sure there is enough foam 

insulation to cushion the bottle. Turn the tumbler on and allow the extraction to run for about 16 

hours. 

 11.9 For extract solutions to be subsequently distilled for total cyanide or cyanides 

amenable to chlorination (e.g., Method 9010 or 9012): 
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 11.9.1 Prepare a Buchner funnel apparatus as in Sec. 11.2 with a glass 

fiber pad filter. 

 11.9.2 Decant the extract to the Buchner funnel. Full recovery of the 

extract is not necessary. 

 11.10 For extract solutions to be subsequently analyzed for metal cyanide complexes 

(Method 9015): 

 11.10.1 Check the pH of the extraction solution. Adjust the pH to between 

11 and 12, using 50% H2SO4. Recap the bottle and mix the solution. Repeat the 

procedure until the pH is in the proper range. 

 11.10.2 Prepare a Buchner funnel apparatus with a 0.45-μm membrane 

filter. 

 11.10.3 Decant the extract to the Buchner funnel. Full recovery of the 

extract is not necessary. 

 11.11 If the extract contains an oil phase, separate the aqueous phase using a 

separatory funnel. Neither the separation nor the filtration are critical, but are necessary to be 

able to measure the volume of the aliquot of the aqueous extract analyzed. Small amounts of 

suspended solids and oil emulsions will not interfere. 

 11.12 At this point, an aliquot of the filtrate of the original sample may be combined 

with an aliquot of the extract in a proportion representative of the sample. Alternatively, they 

may be distilled and analyzed separately and concentrations given for each phase. This is 

described by the following equation: 

( )

( )

( )

( )

( )

( )d

c

b

a

Total Extraction Fluid mL

Total Sample Filtrate mL

Total Solid g

Solid Extracted g

Extract Aliquot mL

Liquid Sample Aliquot mL

= ×

a From Sec. 11.6. Weight of solid sample used for extraction. 

b From Sec. 11.5. Weight of solids and oil phase with the dry weight of filter and tared dish 

subtracted. 

c Includes volume of all rinses added to the filtrate (Secs. 11.2 and 11.3). 

d 500 mL of water plus total volume of NaOH solution. Does not include hexane, which is 

subsequently removed (Sec. 11.11). 

Alternatively, the aliquots may be distilled and analyzed separately, concentrations for each 

phase reported separately, and the amounts of each phase present in the sample reported 

separately. 

 11.13 Determination of percent dry weight 

 In certain cases, the reporting of sample results is desired based on a dry weight basis. 

When such data are desired, a separate portion of sample for this determination should be 

weighed out at the same time as the portion used for analytical determination. 
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CAUTION: The drying oven should be contained in a hood or vented. Significant laboratory 

contamination may result from a heavily contaminated waste material. 

 11.13.1 Immediately after weighing the sample aliquot to be extracted, 

weigh an additional 5-10 g aliquot of the sample into a tared crucible. Dry this aliquot 

overnight at 105 °C. Allow to cool in a desiccator before weighing. 

 11.13.2. Calculate the % dry weight as follows: 

100

g of sample

g of dry sample % Dry Weight = ×

NOTE: This oven-dried aliquot is not used for the extraction and should be appropriately 

disposed of once the dry weight is determined.

12.0 DATA ANALYSIS AND CALCULATIONS 

 12.1 There are no determinative data analysis and calculation steps directly 

associated with this procedure. Follow the directions given in the determinative method. 

 12.2 Results must be reported in units commensurate with their intended use and all 

dilutions must be taken into account when computing final results. 

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 represent required performance goals for 

users of the methods. Instead, performance goals should 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 intended to be and must not be used as 

absolute QC acceptance criteria for purposes of laboratory accreditation.

 13.2 In a single laboratory study, recoveries of 78-95% were reported for soils spiked 

with Fe4[Fe(CN)6]3, an insoluble iron cyanide compound (see Table 1.). These data are 

provided for guidance purposes only. 

14.0 POLLUTION PREVENTION 

 14.1 Pollution prevention encompasses any technique that reduces or eliminates the 

quantity and/or toxicity of waste at the point of generation. Numerous opportunities for pollution 

prevention exist in laboratory operation. The EPA has established a preferred hierarchy of 

environmental management techniques that places pollution prevention as the management 

option of first choice. Whenever feasible, laboratory 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 that 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 Chemical Society (ACS), 

Committee on Chemical Safety, 

http://portal.acs.org/portal/fileFetch/C/WPCP_012290/pdf/WPCP_012290.pdf. 
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15.0 WASTE MANAGEMENT 

 The Environmental Protection Agency requires that laboratory waste management 

practices be conducted consistent with all 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 identification rules and land disposal restrictions. For further information 

on waste management, consult the ACS publication listed in Sec. 14.2. 

16.0 REFERENCES 

1. American Society for Testing and Materials, "Understanding Cyanide Species," D 6696, 

ASTM International, 2004. This reference can be purchased on line at ASTM’s web site: 

www.astm.org. 

2. R. S. Ghosh, D. A. Dzombak, R. G. Luthy, "Equilibrium Precipitation and Dissolution of 

Iron Cyanide Solids in Water," Environ. Eng. Sci., Vol. 16, 293-313, 1999. 

3. J. C. L. Meeussen, M. G. Keizer, W. H. van Riemsdijk, F. A. M. de Haan, "Dissolution 

Behavior of Iron Cyanide (Prussian Blue) in Contaminated Soils," Environ. Sci. Technol., 

Vol. 26, 1832-1838, 1992. 

4. J. C. L Meeussen, W. H. Keizer, F. A. M. de Haan, "Chemical Stability and 

Decomposition Rate of Iron Cyanide Complexes in Soil Solutions," Environ. Sci.

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

5. J. T. Bushey, D. A. Dzombak, "Ferrocyanide Adsorption on Aluminum Oxides," J. Coll. 

Int. Sci., Vol. 272, 46-51, 2004. 

6. T. L. Theis, M. L West, "Effects of Cyanide Complexation on the Adsorption of Trace 

Metals at the Surface of Goethite," Environ. Technol. Letters, Vol. 7, 309-318, 1986. 

7. The RETEC Group, Inc., "Metal Cyanide Complexes by Anion Exchange 

Chromatography and UV Detection Method Validation Summary Report," March, 2004. 

17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA 

 The following page contains the table referenced by this method.
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TABLE 1 

EXAMPLE TOTAL CYANIDE RECOVERIES IN SPIKED SOILS PREPARED 

USING METHOD 9013 EXTRACTION 

Sample 

Background Total 

Cyanide 

Concentrationa

(μg/g Cyanide) 

Spiking 

Concentrationb 

(μg/g Cyanide) 

Average Total 

Cyanide 

Recoveryb

Standard 

Deviationc

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) 

aTotal cyanide was determined in the soil extraction solutions using Methods 9010 and 9012. 

 bSoils were spiked using solid Fe4[Fe(CN)6]3 prior to extraction. 

cn = Number of replicate analyses 

These data are provided for guidance purposes only.

Data taken from Reference 7. 
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Appendix A 

Summary of Revisions to Method 9013 (From Revision 1, November 2004) 

1. Improved overall method formatting for consistency with new SW-846 methods style 

guidance. The version number was changed to two and the date published was updated to 

July 2014. 

2. Significantly updated and expanded “QUALITY CONTROL” section (Sec. 9.0) for better 

adherence to current SW-846 method guidelines and for improved alignment with current 

universal practices for published analytical methods. 

3. Updated “INTERFERENCES” in section 4 to add additional information on the effects of 

certain interferences and deleted reference to method 9010. 

4. The method performance information was updated in Section 13.2 and Table 1. 

5. Minor editorial and technical revisions were made throughout to improve method clarity. 

6. Inserted new section (Sec. 9.4.4) describing the preparation and use of an LLOQ standard.