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Total Cyanide Analysis of NPDES Wastewater Samples by ASTM D 7511-09e2

Introduction
The Federal Water Pollution Control Act Amendments of 1972 directed the U.S. EPA to complete a list of toxic pollutants in water for which effluent standards were subsequently proposed.(1) Cyanide was included on the list of toxic pollutants. The first generation of U.S. EPA cyanide analysis methods from the 1970s employ an acid distillation sample pretreatment step to dissociate cyanide from metal-cyanide complexes and separate cyanide from the matrix. Acid distillation is known to cause either negative or positive analytical biases depending upon the composition of the sample matrix being tested. In fact, the U. S. EPA Solutions to Analytical Chemistry Problems with Clean Water and Methods(2) (Pumpkin Guide) notes; Next to oil and grease, cyanide is the pollutant for which the most matrix interferences have been reported. Table 1 provides a summary of cyanide analysis interferences associated with acid distillation of samples.

ASTM D 7511-09e2
ASTM D 7511-09 e2(3) defines a method for the determination of total cyanide in various types of water (such as ground, municipal waste, industrial effluent, leachate, and surface water). This automated method is applicable to a mass concentration range of 3500 g/L CN, however, higher concentrations can be determined by either performing dilutions or changing the operating conditions. ASTM D 7511-09e2 was validated according to the U.S. EPA ATP protocol for EPA Approval of New Methods for Organic and Inorganic Analytes in Wastewater and Drinking Water(4) and complies with ASTM D 2777-08e1 Standard Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water(5). ASTM D 7511-09e2 was specifically developed to mitigate interferences commonly encountered with other cyanide methods, especially those that utilize a high temperature acid distillation step.

ASTM D 7511-09e2 uses narrow-band, low- watt UV irradiation to decompose cyanide complexes in samples at ambient temperature in a continuously flowing acidic stream. Reducing and complexing reagents, combined with ambient temperature UV digestion minimizes the formation of matrix interferences. Elimination of the sample distillation step enables measurement of cyanide at lower concentrations with improved precision. Table 1: Summary of Known Cyanide Analysis Interferences from Acid Distillation of Samples Compound Oxidizers* (chlorine and hypochlorite) Sulfur/Sulfide* Description of Interference React with cyanide decreasing its concentration Distills into absorber solution and reacts with CN forming thiocyanate. Reacts with cyanide decreasing its concentration. Distills into absorber solution and reacts with cyanide decreasing its concentration. Decompose to form native sulfur and sulfur dioxide. React with cyanide decreasing its concentration. Sulfur dioxide distills into absorber solution and reacts with cyanide decreasing its concentration. Decomposes to sulfur dioxide and reacts with cyanide decreasing its concentration. Sulfur dioxide distills into absorber solution. Decompose to form cyanide Decompose to form cyanide Excessive foaming and possible violent release of carbon dioxide in distillation flask. Can reduce pH of absorber solution and cause incomplete cyanide recovery.

Sulfite* (or Sulfur Dioxide)

Thiosulfate* and other oxidized sulfur species (except sulfate)

Thiocyanate* Thiocyanate + Nitrate or Nitrite Misc. Organics + Nitrate or Nitrite Carbonate*

* These cyanide interferences are specifically cited in the U.S. EPA Pumpkin Guide.(2)

Regulatory Status of ASTM D 7511-09e2 within the U.S.


On August 6th, 2010, the U.S. EPA Administrator signed a Methods Update Rule (MUR) proposing approval of new analytical methods for testing of pollutants in wastewater under the Clean Water Act.(6) The proposed rule was published in the Federal Register(7) on September 23, 2010. Six ASTM methods (including ASTM D 7511-09e2) covering sampling, preservation, and analysis of free, available and total cyanide species were included in the MUR. Facilities with National Pollutant Discharge Elimination System (NPDES) permits can now use ASTM D 7511-09e2 to test wastewater samples for regulatory compliance reporting.

Total Cyanide Analysis of NPDES Wastewater Samples by ASTM D 7511-09e2


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Principle of Operation
A flow diagram for performing total cyanide analysis by ASTM D 7511-09e2 is shown in Figure 1. In operation a sample is injected into a carrier stream, segmented, and acidified. Under acidic conditions the weak acid dissociable cyanide complexes convert to HCN (1) and the strong metal-cyanide complexes are irradiated by ultraviolet light in the UV digestion module (2) where they break down and release HCN. The HCN gas from all cyanide species present in the sample diffuses across a hydrophobic membrane into a basic acceptor solution (3), where it converts back to CN- and is carried into a flow cell of an amperometric detector. Cyanide ions react with a silver electrode and generate current proportional to the cyanide ion concentration (4). The detector response is displayed as a peak. The resulting peak height is proportional to the cyanide concentration present in the sample.
Gas Diffusion Module

Pump Waste Carrier

Sample

2 1
UV Digestion Module

3
Waste

Valve

4
Membrane

Inj. Loop Acid Air Total Acid 2 Base

Detector

Waste

.................

Figure 1. Flow Diagram for Total Cyanide Analysis by ASTM Method D 7511-09e2

Instrumentation for Cyanide Analysis by ASTM D 7511-09e2


ASTM D 7511-09e2 defines design and performance characteristics a flow injection analysis (FIA) instrument should possess to perform the method. Among the design features needed for this in-line UV digestion, gasdiffusion amperometry method are a UV digestion module with a 312-nm lamp, a gas diffusion manifold with a hydrophobic membrane, an amperometric detector equipped with a silver working electrode, an AgCl reference electrode, and a Pt or stainless steel counter electrode. The CNSolution Cyanide Analyzer (Figure 2) is a compact, modular, laboratory instrument that meets the requirements stated in ASTM D 7511-09e2.

Total Cyanide Analysis of NPDES Wastewater Samples by ASTM D 7511-09e2


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Figure 2. OI Analytical CNSolution Cyanide Analyzer for ASTM D 7511-09e2

Advantages of ASTM D 7511-09e2 for Lab Operation


Laboratories gain a number of operational benefits by employing ASTM D 7511-09e2 for cyanide analysis beyond a reduction in matrix interferences and improved analytical performance(8). ASTM D 7511-09e2 does not require the preliminary acid distillation step specified in method 335.4. Eliminating the distillation step provides laboratories the following operational advantages. Higher sample throughput Lower labor costs Lower cost per analysis for reagents and consumables Eliminates analyst exposure to hazardous reagents (boiling, concentrated sulfuric acid and pyridine)

Sample Throughput Figure 3 illustrates the maximum capacity possible when performing manual distillation and analysis by 335.4 compared to in-line UV digestion and gas-diffusion amperometry per ASTM D 7511-09e2. The maximum capacity is based on the samples possible to distill in an 8 hour work day using a 10-position midi distillation block, a 21position MICRO DIST apparatus, or a CNSolution cyanide analyzer configured to run ASTM D 7511-09e2. Data for the midi and MICRO DIST distillations are from a supplier website and probably overstate potential capacity by not taking into account factors such as operator fatigue, coffee breaks, etc. Data for the CNSolution analyzer is based on the number of samples it can run in an 8 hour period at 1 minute per injection with simultaneous UV-digestion and analysis of samples by ASTM D 7511-09e2.

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250 225
Number of Samples

200 150 125 100 50 25 0 Midi-Dist MICRO DIST CNSolution

Figure 3. Sample throughput in an 8-hour shift for manual distillation and analysis by Method 335.4 versus in-line UV digestion and analysis by ASTM D7511-09e2 Labor Costs Figure 4 illustrates the estimated annual labor costs required for manual distillation and analysis of 40 samples per month by method 335.4 versus in-line UV digestion and analysis by ASTM D 7511-09e2. A cost of $15.00 per hour for technician time was used in these estimates.

$7,000.00 $6,000.00 $5,000.00 $4,000.00 $3,000.00 $2,000.00 $1,000.00 $0.00 Midi Dist MICRO DIST CNSolution

Figure 4. Estimated annual labor cost for distilling and analyzing 40 samples per month by Method 335.4 versus ASTM D 7511-09e2 The labor involved in performing midi distillations includes estimated time spent on glassware setup, disassembly and washing. Labor also includes hands-on labor associated with pipetting samples and reagents (MgCl2,

Total Cyanide Analysis of NPDES Wastewater Samples by ASTM D 7511-09e2


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NaOH, etc.). The MICRO DIST apparatus uses disposable polypropylene distillation tube, which eliminates some of the labor costs associated with re-usable Midi distillation glass tubes/flasks. ASTM D 7511-09e2 uses automated in-line UV digestion instead of a manual distillation step so there are no labor costs for sample distillation. Reagent and Consumables Cost Per Analysis Figure 5 presents the estimated cost per analysis of reagents and consumable items to perform cyanide analysis by method 335.4 versus ASTM D 7511-09e2. While the MICRO Dist apparatus uses reduced amounts of reagents, the potential savings is offset by the high cost of disposable polypropylene distillation tubes. The larger volume of reagents required to perform Midi distillations increases its cost per analysis. The cost per analysis for performing ASTM D 7511-09e2 on a CNSolution cyanide analyzer is less than $1.00 because no distillation reagents or consumables are required.

8 7 6 Dollars 5 4 3 2 1 0 Midi-Dist MICRO DIST CNSolution

Figure 5. Estimated reagent and consumable cost per analysis for cyanide analysis by Method 335.4 versus ASTM D 7511-09e2

Comparison of U.S. EPA 335.4 and ASTM D 7511-09e2


U.S. EPA 335.4
U.S. EPA Method 335.4(9) utilizes a manual reflux-distillation to release hydrocyanic acid (HCN) from cyanide complexes, which is absorbed in a sodium hydroxide scrubber solution and transferred to a continuous flow analyzer for colormetric measurement. In operation, the NaOH scrubber solution from the distillation step is injected into a carrier stream and reacted with chloramine-T, converting the cyanide ion to cyanogen chloride. A pyridine and barbituric acid reagent is then reacted with cyanogen chloride producing a red-colored complex that passes through a 37 C heater and into the flow cell of a photometric detector for measurement of 570 nm.

Total Cyanide Analysis of NPDES Wastewater Samples by ASTM D 7511-09e2


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Analytical Interferences Encountered with Method 335.4 The U.S. EPA identified a potential drawback of Method 335.4 in the Pumpkin Guide(2) stating; If sulfite and thiosulfate are present there is no way to accurately determine cyanide if heat is applied. In these situations a nondistillation method such as D 6888-04, or method OIA-1677 may be used. This guidance document also recommended use of a UV digestion or ligand exchange method (OIA-1677) instead of an acid distillation method if thiocyanate is known or suspected to be present. Section 4.0 of Method 335.4 identifies interferences related to both the acid distillation step and colorimetric determinative step. Samples containing nitrate and/or nitrite may yield high results attributable to acid distillation. An explanation in section 4.3 states; During the distillation nitrate and nitrite will form nitrous acid that will react with some organic compounds to form oximes. These oximes will decompose under test conditions to generate HCN.

ASTM D 7511-09e2
ASTM D 7511-09e2 is a non-distillation method that operates on a principle similar to ASTM D 6888-09(10) and U.S. EPA OIA-1677.(11) ASTM D 7511-09e2 was developed in conjunction with OIA-1677 as a non-distillation methods for analysis of total cyanide and free/available cyanide respectively. Mitigation of Analytical Interferences Encountered with Method 335.4 ASTM D 7511-09e2 mitigates sulfide interference at concentrations up to 50 mg/L. This concentration of sulfide approximates the concentration that is detected by commonly used lead acetate test strips. The ASTM also experimentally determined that concentrations greater than 50 mg/L S rapidly deplete cyanide concentrations from the time of sampling to the time of analysis. ASTM D7511-09e2 recommends testing for sulfide when sampling and only treating the sample if the lead acetate paper detects sulfide. ASTM D 7511-09e2 uses UV irradiation at 312 nm to dissociate cyanide as HCN from metal cyanide complexes. In environmental samples the complexes that comprise total cyanide are usually complexes of ferrous and ferric iron. ASTM D 7511-09e2 minimizes recovery of cyanide from thiocyanate to <0.1%. For instance, 20-ppm thiocyanate recovers 20 ppb or less cyanide. While still a positive interference, this recovery from thiocyanate is lower than any other total cyanide method. ASTM D 7511-09e2 separates the HCN generated by the UV irradiation by gas diffusion and then measures the cyanide by amperometry. Amperometry is a very sensitive electrochemical technique that directly and selectively measures only the cyanide ion. Salt concentrations greater than 10,000 mg/L do not interfere. Method Validation and Supporting Data ASTM evaluated over 20 potential interferences at two different concentrations in the absence of and in the presence of cyanide (also at two different concentrations). The results of these interference studies are summarized in the standard with the remainder available in the supporting research report for ASTM D 7511-09e2. ASTM evaluated the recovery of 15 metal cyanide complexes at two different concentrations, and also compared results to two different distillation cyanide methods (EPA335.4 and ASTM D 7284). Results were considered equivalent and the data is included in the standard and/or the research report.

Total Cyanide Analysis of NPDES Wastewater Samples by ASTM D 7511-09e2


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ASTM D 7511-09e2 evaluated nine very complex matrices known, and demonstrated, to be problematic for analysis by conventional cyanide methods. These nine matrices were first thoroughly tested in a single lab study, and then the same samples were distributed and evaluated in a multiple laboratory trial. This data is also available in the standard(3) and the supporting research report. A direct comparison of ASTM D 7511-09e2 and EPA 335.4 methods for total cyanide analysis is presented in Table 2. Table 2: Comparison of ASTM D 7511-09e2 and 335.4 Parameter NPDES/CWA compliance Measurement Range (g/L) UV irradiation >295nm Separation of HCN Measurement of CN Matrices evaluated ASTM D 7511-09e2 Yes 3500 Yes Gas diffusion Amperometry 9 Drum handling facility, municipal wastewater, petroleum refinery effluent, coke plant effluent, rolling mill effluent, metals forming plant effluent, die casting plant effluent, precious metals operation reclaim water, water treatment plant filter effluent Sulfide, nitrite, nitrate, nitrate plus thiocyanate, thiocyanate, thiosulfate, sulfite, formaldehyde, ammonium, chloride, bromide, iodide, sulfate, carbonate, cyanate, glycerol, glucose, ascorbic acid citric acid Cadmium, copper, zinc, silver, mercury, iron (II), iron (III), palladium, gold, cobalt, platinum, and ruthenium Iron (II), iron (III), nickel, and mercury >10 g/L <10 g/L 80107% 110153% 335.4 Yes 5500* N/A Distillation Colorimetry 1

Types of matrices tested

Reagent water

Interferences evaluated

No data

Metal cyanide species evaluated for recovery Metal cyanide species evaluated in multi-laboratory study Recovery Data (Total Cyanide) from multi-laboratory study

No data

No data >20 g/L 9198% <20 g/L No data

* Inter-laboratory study did not evaluate samples below 20ppb.

Total Cyanide Analysis of NPDES Wastewater Samples by ASTM D 7511-09e2


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Summary and Conclusions


ASTM D 7511-09e2 and 335.4 are test methods for total cyanide analysis in wastewater samples. ASTM D 751109e2 was included in the proposed Methods Update Rule (MUR) published in the Federal Register on September 23, 2010. This action allows facilities with NPDES permits to use ASTM D 7511-09e2 to test wastewater samples for Clean Water Act compliance reporting. The principal differences between these two U.S. EPA approved methods can be summarized as follows. U.S. EPA Method 335.4: 1. Requires a time-consuming manual acid distillation step that delays availability of the first test result for hours. Limits sample throughput to the number of positions available on the distillation apparatus. Typical sample throughput is 10-20 samples every 3-4 hours. Utilizes hazardous chemicals including boiling sulfuric acid and pyridine, and requires use of barbituric acid, which is a controlled substance in many states within the United States. Is subject to significant false positive and/or false negative results. If the composition of sample matrices is not well characterized for interferences the test results cannot be trusted.

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ASTM Method D 7511-09e2: 1. 2. Measures total cyanide without a preliminary 2-hour acid distillation step providing results in minutes. Employs automated in-line UV digestion to dissociate cyanide complexes, which supports a sample throughput of 30 samples per hour. Determined the recovery of cyanide from 15 metal cyanide complexes at two different concentrations, and compared the results to distillation methods. Evaluated over 20 different potential interferences at two different concentrations with and without cyanide present. Accurately determines cyanide in solutions containing up to 50 ppm Sulfide. Provides details on testing and treatment of samples containing higher sulfide concentrations. Does not suffer from sulfite interference. Was evaluated in nine very complex matrices known to be problematic with conventional cyanide methods. Recovers less cyanide when thiocyanate is present in samples than any other cyanide method, avoiding positive analytical interference and bias.

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References
1. U.S. EPA, Proposed Toxic Pollution Effluent Standards, 40 CFR Part 129, Federal Register, Vol. 38, 35388, 1973. Solutions to Analytical Chemistry Problems with Clean Water Act Methods, U. S. EPA Office of Science and Technology, March 2007. ASTM D 7511-09e2 Standard Test Method for Total Cyanide by Segmented Flow Injection Analysis, In-line Ultraviolet Digestion and Amperometric Detection, ASTM International. Protocol for EPA Approval of New Methods for Organic and Inorganic Analytes in Wastewater and Drinking Water, www.epa.gov/waterscience/methods/atp/EPA821B98003.pdf. ASTM D 2777-08e1 Standard Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water, ASTM International. U.S. EPA Clean Water Act Analytical Methods Recent Regulatory Changes; http://www.epa.gov/waterscience/methods/update. Federal Register, Vol. 75, No. 184, September 23, 2010, Guidelines Establishing Test Procedures for Analysis of Pollutants Under the Clean Water Act; Analysis and Sampling Procedures; Proposed Rule, http://edocket.access.gpo.gov/2010/pdf/2010-20018.pdf. OI Analytical Application Note #3515, Cyanide Analysis - Reducing Laboratory Operating Costs without Compromising Data Quality or Regulatory Compliance, 2010. USEPA Method 335.4: Determination of Total Cyanide by Semi-Automated Colorimetry, in Methods for the Chemical Analysis of Water and Wastes, EPA-60014-79-020, U.S. Environmental Protection Agency, National Exposure Research Laboratory, Cincinnati, Ohio, 1979. ASTM D 6888-09 Standard Test Method for Available Cyanide with Ligand Displacement and Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and Amperometric Detection, ASTM International. U.S. EPA Method OIA-1677 Available Cyanide by Flow Injection, Ligand Exchange, and Amperometry, EPA-821-R-99-013, August 1999.

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