TN295 f \'''^mS ^^^^ ^^^OIF*' .*^'"^^. '.■^I^-- ^♦'"^'J:. Hc^ 4 o X^^V\..rv*^^'> "°^^^*^%°' V"^'*y'' "-^^--^-So^ -% '...- ' • •''"^.. .c°'..^;r>o /,-^^,X. >°^.:^^'>o y^^i^A co^ •^.-0^ o ■ • , /■\ '■^.•y\ '^.- /% -.w-* **''^- '™- /% **'% yy >vl t^. o « ■" «,» • • " *y V » 1 * " |: '^-^' :»: '^--^^ -^M: \.^^ .^M^» \/ .■^" .. vS '^^^^^ - -^^0^ !^^i^': -ov^' IC 8953 Bureau of Mines Information Circular/1983 Methods for Characterizing Manganese Nodules and Processing Wastes By Benjamin W. Haynes, David C. Barron, Gary W. Kramer, and Stephen L. Law UNITED STATES DEPARTMENT OF THE INTERIOR Information Circular 8953 1 Methods for Characterizing Manganese Nodules and Processing Wastes By Benjamin W. Haynes, David C. Barron, Gary W. Kramer, and Stephen L. Law UNITED STATES DEPARTMENT OF THE INTERIOR James G. Watt, Secretary BUREAU OF MINES Robert C. Norton, Director Library of Congress Cataloging in Publication Data: ^> .p V^''■ Methods for characterizing manganese nodules and processing wastes. (Information circular / Bureau of Mines ; 8953) Bibliography: p. 10. Supt. of i:)ocs, no,: I 28.27:8953. 1. Manganese nodules— Analysis. 1. Haynes, Benjamin VC. 11. Se- ries: Information circular (United States. Bureau af Mines) ; 8953. -^WWOSOJi [QE390.2.IV135] 622s r553.4'629'0287] 83-600240 CONTENTS Page Abstract 1 Introduction 2 Physical methods 2 Compound identification methods 2 Chemical characteristics 4 Atomic absorption spectrophotometry 4 Inductively coupled plasma atomic emission spectroscopy 6 Neutron activation analysis 6 X-ray fluorescence spectrography 6 Ion chromatography 6 Wet chemical methods 7 Comparison of chemical analysis results 7 Leaching tests 8 EP toxicity test 8 ASTM shake extraction test 8 U.S. Army Corps of Engineers seawater elutriant test 9 Results of leaching tests 9 Conclusions 9 References 10 TABLES 1 . Suggested test procedures for determining physical properties of manganese nodule reject waste materials 3 2. Physical properties of pilot plant- and laboratory-generated Cuprion process tailings 3 3. Compo.und identification and elemental analysis methods for manganese nodule materials 3 4. Sources of interference in elemental determination by quantitative instrumental methods 5 5. Sample dissolution and elemental analysis procedures for manganese nodule materials 5 6. Ion chromatograph operating conditions for determining anions and NH4^ 7 7. Comparison of interlaboratory analyses of manganese nodule standards 7 8. Round-robin results for Cuprion process reject waste material, solid phase 8 9. Round-robin results for Cuprion process reject waste material, liquid phase 8 10. Element concentration in leachate from leaching tests on Cuprion process reject waste material 9 LIST OF UNIT OF MEASURE ABBREVIATIONS USED IN THIS REPORT cm/s centimeter per second mUmin milliliter per minute deg degree mm millimeter °C degree Celsius mm minute g gram nm nanometer h hour pet percent pg microgram pcf pound per cubic foot pg/mL microgram per milliliter psi pound per square inch pm micrometer wt pet weight percent mL milliliter METHODS FOR CHARACTERIZING MANGANESE NODULES AND PROCESSING WASTES By Benjamin W. Haynes,^ David C. Barron,^ Gary W. Kramer,^ and Stephen L. Law'* ABSTRACT Analytical procedures are described for the quantitative determination of 1 6 elements (As, Ba, Be, Cd, Co, Cr, Cu, Fe, Mn, Mo, Nl, Pb, Sb, Se, Tl, and Zn) and 7 ionic species (NH4*, COa^", cr, F", NO3", P04^", SO/'), identification of major and minor mineral components, and measurement of physical properties associated with manganese nodules and nodule pro- cessing reject waste materials. Compound identification methods discussed include X-ray diffraction, infrared spectroscopy, scanning and transmission electron microscopy, selective area electron diffraction, and optical and reflected light microscopy. Methods for elemental analysis Include atomic absorption spectrophotometry, inductively coupled plasma emission spectroscopy, neu- tron activation analysis, fluorescent X-ray spectrography, and ion chromatography. Thermal gravimetric analysis, ultraviolet-visible spectrophotometry, ion specific electrodes, and stan- dard wet chemical procedures are briefly discussed. Physical properties determined In manganese nodule materials include grain size distribution, specific gravity, triaxlal shear, permeability, maximum density, Atterberg limits, and slurry density. The results of a round-robin analysis of an ammonia process waste material and manga- nese nodule standards demonstrate the applicability of the discussed methods. Tests discussed for the evaluation of the waste materials for disposal options include the Environmental Protection Agency (EPA) EP toxicity test, the ASTM shake extraction test, and the U.S. Army Corps of Engineers EPA seawater elutriant test. 'Supervisory research chemist. ^Chemist. ^Research chemist. ■•Research supervisor. Avondale Research Center, Bureau of Mines, Avondale, MD. INTRODUCTION Deep seabed mining for manganese nodules, including the processing of nodules to recover value metals, raises a variety of environmental, social, and economic considerations. To address the waste management aspects of the recovery of value metals from nodules, the National Oceanic and Atmo- spheric Administration (NOAA) of the Department of Commerce, the Environmental Protection Agency (EPA), and the Depart- ment of the interior's Bureau of Mines and Fish and Wildlife Service, after consultation with industry, academia, and other concerned interests, entered a multiyear cooperative research program which has as its overall objective: "To provide information needed by Federal and State agencies in preparation for receipt of industry's commer- cial waste management plans." The NOAA-funded research conducted by the Bureau of Mines has the objective of obtaining a "first-order chemical and physical characterization of rejects from the types of manganese nodule processing techniques representative of those being developed by industry." Three reports have been published since commencement of this research that delin- eate mineralogical and elemental composition of Pacific man- ganese nodules (16),^ five potential process flowsheets for first-generation plants (17), and prediction of the compositions of the reject waste materials from the five potential processes (75) using information obtained in the first two reports. The five processes considered feasible for first-generation nodule pro- cessing are as follows (7,77): 1 . Gas reduction and ammoniacal leach. 2. Cuprion ammoniacal leach. 3. High-temperature and high-pressure sulfuric acid leach. 4. Reduction and hydrochloric acid leach. 5. Smelting and sulfuric acid leach. In order to assess any potential environmental impact of waste disposal from manganese nodule processing, accurate and precise analytical methods are essential. Because this industry is still in the developmental stage, actual waste materi- als are not available, and the direct applicability of commonly used analytical methods was uncertain. The combination of high manganese and high iron content is unique to these materials, and interferences will result in incorrect data unless precautions are taken. This report outlines methods that Bureau of Mines experi- ence has indicated are applicable to the characterization of nodule feed materials and the reject waste materials from all five potential processes. The report is divided into five sections: methods for determining physical properties, methods for com- pound identification, methods for determining chemical characteristics, interlaboratory comparisons of results, and leach tests for hazardous waste and ocean disposal assessment. The chemical characteristics section discusses the determi- nation of elements of potential economic and/or environmen- tal interest and anion or cation combining species. Elements of interest are As, Ba, Be, Cd, Cr, Co, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, Tl, and Zn (75). Silver and mercury are not specifically addressed in this report as their levels in nodules are too low to warrant environmental concern (75-76). Ions of interest include ammonium, carbonate, chloride, flouride, nitrate, phosphate, and sulfate. The various methodologies for testing physical properties incorporate standard ASTM and soil mechanics procedures. Analysis of liquid and solid phase components for chemical characteristics involve the use of atomic absorption spectro- photometry (AAS), inductively coupled plasma spectroscopy (ICP), ion chromatography (IC), X-ray fluorescence (XRF), X-ray diffraction (XRD), and/or wet chemical procedures. Parame- ters such as pH, reduction-oxidation potential, and chemical oxygen demand may also need to be determined. Modifica- tions of these basic methods and the use of other methods may be required for specific needs of different laboratories. The procedures and methods presented in this report are not to be considered as proposed standard methods or as the only methods suitable for characterization of these types of materials. Attention has been given to methods that are capa- ble of multielement analysis, thereby reducing the amount of sample and the time required for analyses. PHYSICAL METHODS Physical characteristics are determined by the application of ASTM methods outlined for soils and rock testing (3). The test procedures listed in table 1 have been successfully applied to coal refuse by the Bureau of Mines (6). The same test procedures were used to determine the physical characteris- tics of tailings generated in pilot-plant and laboratory operations, and the results are presented in table 2. The agreement between results of the two types of tailings in table 2 demonstrates the ability to simulate the pilot-plant physical characteristics on the laboratory scale. However, these results may not be typi- cal of tailings that may be produced in a full-scale plant because optimization of all processing parameters is not achievable on a pilot-plant or laboratory scale. COMPOUND IDENTIFICATION METHODS Identification of the various compounds present in nodule reject waste materials allows a preliminary evaluation of the wastes' environmental impact. An element present in one chemical form may be environmentally inert, whereas a more ^Italicized numbers in parentheses refer to Items in the list of references at the end of this report. chemically active form of the element may pose problems if disposed of improperly. However, this identification is inher- ently difficult because of the poorly crystalline, fine-grained, or amorphous nature of the minerals in manganese nodules and their tailings. Methods, such as XRD, optical microscopy, infrared spectroscopy, thermal analysis, and scanning and transmission electron microscopy, are available to identify Table 1. — Suggested test procedures for determining physical properties of manganese nodule reject waste materials Property Procedure' Grain size distributions: Plus 200 mesh ASTM D422-63. Minus 200 mesh Allen (1). Specific gravity ASTM D854-58. Triaxial shear ASTM D2850-70. Permeability ASTM 02434-68.= Maximum density ASTM D698-78. Minimum density ASTM D2049-69. Atterberg limits: Liquid ASTM D423-66. Plastic ASTM D424-59 Soil class ASTM D2487-69. Slurry density ASTM D2216-71. ASTM tests are found in reference 3. ■ Using Bureau of Reclamation Earth Manual Procedure E13. Table 2. — Physical properties of pilot plant- and laboratory- generated Cuprion process tailings Parameter Pilot plant Labora- tory Grain size distribution, \xm: 1 00 pet pass 74 6 1 '3.19 38 5 8.46 90.1 45 41.2 3 ML 41.8 600 50 pet pass 13 pet pass 1 Specific gravity 3 10 Triaxial shear: Friction angle deg . . Cohesion psi. . Permeability^ 1 0~^ cm/s . . Maximum density pcf . . Atterberg limits: Liquid pet. . Plastic pet. . Soil class ... 38.5 4 6.7 92.5 42.1 34.4 ^ML Slurry density pet solids. . 31 1 ' Dry solids. ■ At 95 pet maximum density. ' Lean silt. major and minor compounds. Table 3 includes a brief sketch of each of these methods along with the methods primarily used for elemental and anion determinations discussed in the next section. XRD is the conventional technique used to identify and sometimes quantify major and minor crystalline compounds. However, in the iron and manganese matrix of manganese nodules, compounds that are present at less than 5 wt pet and/or are extremely fine grained, generally cannot be identi- fied by this method. Many of the minerals present in nodules (76) are very poorly crystalline, and often amorphous, given only a diffuse XRD pattern. The reject waste materials from manganese nodule processing are also relatively fine grained but do show better crystallinity and thus better diffraction patterns than nodules. The major and minor components such as manganese carbonate, manganese oxides, silica, clays, and feldspars can be determined. Positive association of trace elements with specific compounds is virtually impossible by this method. Identification of compounds in single grains requires the use of the transmission electron microscope (TEM) using selec- tive area electron diffraction (SAED) (30). This technique uses very small samples and applies to single particles. Quantifica- tion on this scale is impractical because of the lack of appropri- ate standards for manganese nodule materials. Infrared spectroscopy (IR) is useful for the mineralogical analyses of manganese nodules, which cannot be performed by XRD {22-23). For example, it eliminates the ambiguity fre- quently caused in XRD by silicate components, such as the confusion of kaolinite and birnessite (23). Being sensitive to short-range order, IR provides mineralogical information on the disordered and fine-particulate phases that cannot be studied by XRD (22). However, because IR is not a primary structural technique like XRD, it is necessary to calibrate it Table 3. — Compound identification and elemental analysis methods for manganese nodule materials Atomic absorption spectroscopy: Application — Quantitative determination of a specific element, especially minor and trace concentrations. Principle — Absorption of atomic resonance line proportional to the con- centration of the specific element. Limitations — Usually not applicable to nonmetals. Metals are determined individually and not simultaneously. Atomic emission spectroscopy: Application — General qualitative and semiquantitative survey of all metallic elements. Principle — Light emission from excited electronic states of atoms propor- tional to concentration. Limitation — Poor for detecting volatile elements. Quantitative determina- tions are difficult. Chemical reaction methods (classical analysis): Application — Variety of specialized quantitative applications. Principle — Stoichiometry of chemical reactions. Limitations — Time consuming, interferences often a problem. Electron microscopy and microanalysis (SEM, TEM, and probe): Application — Morphological information and elemental composition of fine particles. Principle — A focused beam of electrons gives rise to secondary, bacl<- scattered, reflected, or transmitted electrons for morphological informa- tion, and X-rays for elemental information. Limitations — Sample must be small enough to fit in the sample chamber. Less than about 6-mm square maximum area is viewed by SEM, less than 1.5-mm square area for TEM, and about 50-mm square area for an electron probe. Inductively coupled plasma: Application — Minor, trace and ultratrace quantitative and semiquantitative element analysis including B, P, and S, wWn linearity often over 4 orders of magnitude. Principle — Characteristic emissions from elements excited by an inductively coupled argon plasma have intensities proportional to concentrations. Limitations — Some spectral and scattered light interferences may come from the high concentrations of Fe and Mn in nodules. Ion chromatography: Application— Rapid quantitative determination of anions. Rapid cation determination for alkali and alkaline earth metals, NH4"' and 1st row transition elements. Principle — Ions separated by ion exchange techniques followed by ion electrical conductance proportional to the concentration of the specific ion. Limitations — Usually not applicable to anions with pKa >7. Most 2d and 3d row cations are determined with difficulty. Infrared spectroscopy: Application — Identification of compounds, amorphous and crystalline. Principle — Excitation of molecular vibrations by light absorption. Limitations — Medium sensitivity down to 1 to 2 pet. Broad absorption bands of OH group may overlap other spectral features in application to nodules. Neutron activation: Application — Trace and ultratrace elemental analysis of most elements including N, O, and F. Principle — Counting of radioactive species produced by neutron reactions. Limitations — The multielement nature of nodules present problems in spectral overlaps, which require chemical separation for some elements. Table 3. — Compound identification and elemental analysis methods for manganese nodule materials — Continued Optical microscopy: Application — Mineral or phase identification. Principle — Properties sucli as color, cleavage, refractive index, and characteristic crystal shapes using plane and polarized, transmitted, and reflected light systems. Limitations — Resolution limit is about 0.2 |xm but identification of particles <5 (xm is not practical, limiting the use of this technique for fine-grained nodule materials. Thermal analysis (TGA and DTA): Application — Qualitative and quantitative studies of materials including phase transitions, dehydration, reduction decomposition, crystallization, oxidation, and other heat-related properties. Principle — Changes in weight are measured as a function of Increased temperature over time. Limitations — Information is often empirical, and complementary analytical methods are needed to properly interpret data. Ultraviolet-visible spectrophotometry: Application — Quantitative analysis usually for final determination in chemical analysis schemes. Principle — Excitation of loosely bonded electrons with absorption of characteristic wavelength being proportional to the concentration of the compound. Limitations — Low specificity requiring chemical separation procedures prior to final determination. X-ray diffraction: Application — Identification of crystalline substances. Principle — Diffraction of X-rays from crystal planes providing "fingerprint" identification of crystalline materials. Limitations — Many nodule minerals are too fine grained or amorphous, making X-ray diffraction inapplicable. Generally not useful in the atomic number matrix of nodules for concentrations <5 wt pet. X-ray fluorescence spectrography: Application — Quantitative analysis of elements and semiquantitative survey of all elements of atomic number 1 1 or greater. Principle — X-ray excitation of characteristic X-rays. Limitations — Nonsensitive to elements of atomic numbers <1 1 (Na). Best sensitivity for heavier atomic number elements. against well-crystallized materials where mineralogy has been previously determined by XRD. Similar to XRD, direct IR is limited to compounds present at 2 to 5 pet or more in the sample. Other methods of compound identification such as optical microscopy, visual inspection, reflectivity, and other chemical and physical methods have definite applications. A combination of procedures is usually important to obtain reli- able compound identification on the macrocrystalline and micro- crystalline scale. A detailed description of over 50 minerals identified in manganese nodules is given in reference 1 6. CHEMICAL CHARACTERISTICS Elemental determination in manganese nodule processing reject waste material is amenable to several standard analyti- cal methods. (See table 3.) Interferences for 16 elements of interest in manganese nodule materials are listed in table 4 for four major instrumental analysis methods. Because of their importance in the determination of element concentrations in nodule materials, a brief discussion of each instrumental method listed in table 4 is given, followed by a brief discussion of ion chromatography for the determination of ions. ATOMIC ABSORPTION SPECTROPHOTOMETRY Atomic absorption spectrophotometric (AAS) techniques are readily adaptable for analysis of both the solid and liquid phases (75). In the liquid phase, direct flame, electrothermal, and hydride methods of AAS are applicable depending on the element and the concentration levels. Most elements are readily determined by flame AAS, but may require the use of electro- thermal AAS if the levels are below flame AAS detection limits. For As, Sb, and Se, either hydride or electrothermal AAS should be used. Specific methods or the use of a standard addition method may be required for some elements (24). Instrumental parameters and conditions for determining these elements can be found in the EPA manual, "Methods for Chemical Analysis of Water and Wastes" (32). For solid phase analysis (nodules or tailings), several multielement dissolution procedures are available. This report will address only three simple, rapid dissolution procedures. One method is used for the determination of the seven major and minor elements (Mn, Fe, Cu, Ni, Co, Pb, and Zn) and several trace elements (Cr, Tl, Cd, and Ba) by flame AAS. The other two dissolution procedures are used for determining trace elements by either electrothermal or hydride AAS. The dissolution procedure for determining the major, minor, and some trace elements in nodules and in the solid phase of the reject waste material uses HCI-HF acids with the resultant solution evaporated to dryness. This dried residue is then dissolved in 6A/ HCI, diluted to volume, and analyzed by flame AAS. Determination of the trace elements As, Sb, and Se by electrothermal or hydride AAS requires a separate dissolution procedure (73) to avoid analyte loss of the volatile compounds formed during evaporation of the solution and during the drying and charring stages prior to electrothermal atomization. The sample is dissolved in a HNO3-HF mixture with the addition of Ni(N03)2 and Mg(N03)2 as matrix modifiers. Additional trace elements that can be determined by electrothermal AAS are Ba, Cd, Cr, and Pb. High iron levels cause a spectral interference at the primary selenium wavelength of 196.0 nm (27). This spectral overlap problem can be solved by adjusting the pH of the solution to 3 to 4 to precipitate the iron, with the selenium quantitatively carried on the Fe(0H)3 precipitate. This precipitate is sepa- rated and redissolved in 7N HCI and the solutions are ana- lyzed by hydride AAS to determine selenium. The selenium forms a hydride whereas iron does not react and therefore does not interfere. The use of polarized Zeeman- effect AAS on the original solution is a more direct way to eliminate the spectral interference caused by iron (79). This technique uses the magnetic portions of the selenium analyti- cal line, which facilitates the instrumental separation of iron and selenium spectral lines. A third dissolution procedure for the analysis of nodules and solid phase reject materials is a Parr^ bomb dissolution with aqua-regia-HF acid (28). All 16 elements are solubilized with- out loss and can be determined using flame AAS for the major and minor elements, and the remaining trace elements can be determined by flame, hydride, or electrothermal AAS. In deter- ^Reference to specific products does not Imply endorsement by the Bureau of Mines. Table 4. — Sources of interference in elemental determination by quantitative instrumental methods Arsenic: AAS High Fe, Mn, and ottier metals will depress the sensitivity in hydride generation. Flame method gives poor sensitivity. ICP 2d-order spectral overlap from Ar. NAA Interference from Se, Ge, and Br. XRF Pb spectral interference at more sensitive Ka peak. Kp peak lacks sensitivity for quantities below 0.02 pet. Barium; AAS Ionization controlled by adding KCI. CaOH bands interfere. ICP None reported. NAA Interference from Ce and La. XRF None reported for quantities above 0.05 pet. Beryllium: AAS High Al, Mg, and Si will depress sensitivity. ICP 2d-order spectral overlap from Ar and OH band interference. NAA Not recommended. XRF Atomic number too low for XRF. Cadmium: AAS High Si interferes. ICP None reported. NAA Interference from Sn and from shielding. XRF None reported for quantities above 0.02 pet. Cobalt: AAS Some heavy metals and transition metals depress signal. ICP 2d-order spectral overlap from Ar. NAA Ni, Cu, and Fe cause enhancements. XRF Fe spectral interference below 0.01 pet. Chromium: AAS Fe, Ni, and PO/" depress the signal. ICP OH band interference. NAA Interference from Fe. XRF Enhanced by high iron. Copper: AAS None reported. ICP 2d-order spectral overlap from Ar. NAA Interference from Ni and Zn. XRF None reported for quantities above 0.005 pet. Iron: AAS Co, Cu, Ni, Si, and organic acids depress signal. ICP None reported. NAA Poor detectability from Co, Cr, Mn, and Ni. XRF None reported for quantities above 0.005 pet. Manganese: AAS Si depresses signal. High concentration of Fe enhances signal. ICP 2d-order spectral overlap from Ar and OH band interference. NAA Interference from Fe, Co. and Cr. XRF None reported for quantities above 0.005 pet. Molybdenum: AAS Cu, Fe, Sr, and S04^" depress the signal. ICP OH band interference. NAA Interference from Ru. XRF None reported for quantities above 0.02 pet. Nickel: AAS High Fe or Cr will enhance signal. ICP 1st order spectral overlap from Si. NAA Interference from Cu and Zn for Ni-64. No apparent interference for Ni-58. XRF None reported for quantities above 0.005 pet. Lead: AAS High Fe or other metals will enhance the signal. ICP 2d-order spectral overlap from H. NAA Interference from Bi. XRF None reported for quantities above 0.01 pet. Antimony: AAS Spectral interference from Cu and Pb. Depressed signal in high acidity. ICP 1st order spectral overlap from Si and 2d-order overlap from Ar. NAA Interference from Te and from self-shielding. XRF None reported for quantities above 0.02 pet. Selenium: AAS Some metals will depress the hydride generation signal. Flame absorbs signal. ICP None reported. * NAA Interference from Ge and Br. XRF None reported for quantities above 0.01 pet. Thallium: AAS None reported. ICP 1st order spectral overlap from Ar. NAA Interference from Pb and Hg. XRF None reported for quantities above 0.02 pet. Zinc: AAS High Cu, Fe, and Ni depress signal. ICP None reported. NAA Interference from Cu and Ni. XRF None reported for quantities above 0.005 pet. AAS ICP Atomic adsorption spectrophotometry. Inductively coupled plasma. NAA XRF Neutron activation analysis. X-ray diffraction. mining As, Sb, and Se by electrothermal AAS, matrix modifi- ers must be added to prevent losses during the drying and charring stages prior to atomization (73). Table 5 identifies each of the major elements as a major, minor, or trace component in manganese nodules, and gives suggested dissolution procedures and applicable methods for determination. For flame AAS conditions, relative error is gen- erally 2 to 5 pet of the actual value. At the very low levels determined by hydride or electrothermal AAS, the relative error is within 5 to 7 pet of the actual value. Table 5. — Sample dissolution and elemental analysis procedures for manganese nodule materials Element Concentration Dissolution procedure' Method of analysis^ Element Concentration Dissolution procedure' Method of analysis^ HCI-HF Flame AAS. HCI-HF Do. HCI-HF Do. HCI-HF Do. HCI-HF; Flame or electro- HN03-Ni(N03)2. thermal AAS. HN03-Ni(N03)2 Hydride or electro- thermal AAS. HN03-Ni(N03)2 Do. HCI-HF Flame AAS. HCI-HF Do. As Trace HN03-Ni(N03)2. . . Ba Minor HCI-HF; HN03-Ni(N03)2. Be Trace HCI-HF; HN03-Ni(N03)2. Cd do HCI-HF; HN03-Ni(N03)2. Co Minor HCI-HF Cr Trace HCI-HF; HN03-Ni(N03)2. Cu Major HCI-HF Hydride or electro- thermal AAS. Flame or electro- thermal AAS. Do. Do. Flame AAS. Flame or electro- thermal AAS. Flame AAS. Fe Major . Mn do. Mo Minor . Ni Major . Pb Minor . Sb Trace . Se do. Tl do. Zn Minor . ' The Parr bomb dissolution procedure is suitable for all 16 elements. ^ Inductively coupled plasma atomic emission spectroscopy is suitable for all 16 elements. INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION SPECTROSCOPY The same sample preparation techniques used for atomic absorption are used for preparing solutions for the inductively coupled plasma (ICP) technique for multielement analysis by atomic emission spectroscopy. Atomic emission lends itself more readily to multielement analysis than does atomic absorption, and the interelement effects, self-absorption problems, and poor excitation of refractory elements, which create problems in conventional atomic emission spectroscopy, are greatly reduced in ICP. Spectral and interelement interfer- ences are a basic problem in any emission technique; however, interferences from background emission, flame gases, com- bustion products, and molecular species are greatly reduced in ICP. The few interferences that may cause problems in the analyses of manganese nodule materials are listed in table 4. The relative error in determining major, minor, and trace ele- ments in nodule materials by ICP is slightly higher compared with the 2 to 5 pet cited for AAS in the previous section. NEUTRON ACTIVATION ANALYSIS Neutron activation analysis (NAA) can provide concentra- tion values, especially on a trace level (< 0.001 pet), which might otherwise be impractical. However, a number of interfer- ences (18, 25) may create problems in measuring specific activities (see table 4). With materials such as manganese nodules, sensitivity and accuracy can be obtained in the measurement of the radioac- tive products from most of the elements only after chemical separation. The major types of counting interferences include the masking of trace element activities by the much greater activities of one or more other elements because of amounts, cross sections, or long half-lives, and the occurence of similar gamma-ray photopeaks or B" emissions that are not conve- niently resolved (for example, Fe-59 and Co-60). Postirradia- tion separations are preferred over preirradiation because no reagent blank is involved and the postirradiation separation need not be quantitative in many cases to obtain quantitative results. The chemical separations, whether performed before or after irradiation, follow conventional methods except for added precautions in working with the radioactive samples. A procedure using chemical separations for the determination of 42 elements in lunar material (5) would appear to require very little modification to provide good results for manganese nod- ule materials. X-RAY FLUORESCENCE SPECTROGRAPHY The application of X-ray fluorescence (XRF) spectrography to manganese nodule and reject waste materials involves conventional methods of XRF analysis with corrections for peak overlap and enhancement and depression effects. The wavelength- and energy-dispersive methods of XRF are appli- cable for Co, Cu, Fe, Mn, Ni, Zn, and Pb where these elements are major or minor constituents of the solid phase (nodules or tailings). The remaining elements of interest for this report are at levels not usually detectable by direct XRF methods. A good general reference on XRF analysis is Bertin (4). Sample preparation of nodules or tailings for XRF analysis requires drying to remove moisture, followed by one of two methods of sample preparation: pressed pellets or fused disks. To prepare pressed pellets, the dry weighed sample is mixed with a binder and pressed into a pellet at -1 5 tons per square inch pressure. These pellets are then analyzed and compared with standards of known composition for the elements of interest. The second sample preparation procedure, fused disks, requires a dry weighed sample to be mixed with a glass-forming low- atomic number material, followed by fusion at high tempera- ture (-' 800°-1 ,200° C). This method eliminates particle size problems and reduces matrix effects. However, sensitivity is decreased because of dilution of the sample by the glass- forming material. The dilution is usually about six parts flux to one part sample in fusions compared with pressed pellets where 85 pet of the final pellet is sample. This loss of sensitivity by using fused disks may pose a problem if concentrations of the element of interest are already low. Major and minor elements can be determined by XRF pro- vided that adequate primary and secondary standards can be obtained and/or made for the elements of interest in an appro- priate matrix. The precision of analysis will vary from ± 1 pet of the amount present for the major elements (>5 pet) such as manganese and iron, and ranges up to ± 20 pet of the concen- tration present for elements in the very low (<0.1 pet) range. This relative error is also very dependent on atomic number in the lower concentration range, with the greater problems occur- ring with the lower atomic number elements. Applications of XRF to nodule analysis has been reported (70, 12), giving X-ray values in good agreement with atomic absorption analy- ses of nodules (11). ION CHROMATOGRAPHY Conventional, standard wet chemical, and colorimetric meth- ods for chloride, fluoride, nitrate, ammonium, phosphate, and sulfate are available (32). In order to determine five anions of interest in the manganese nodule materials using the con- ventional methods, a separate sample would be required for each anion determination. Since the introduction of ion chro- matography (IC) (29), this multi-ion method has been used to determine many anions and cations in a variety of environmen- tal and geological matrices (14, 20, 26-27). In the liquid phases from processing nodules, NH4*, CI', S04^", and COa^" can be determined by sample dilution followed by injection into the IC. Table 6 summarizes the operating conditions for determining six anions and one cation of interest. The six anions, F, CI", NO3", P04^", S04^", and COa^" can be determined in less than 20 min on one sample using one set of conditions. The ammonium ion can be determined in a separ- ate sample of the liquid fraction using another set of IC con- ditions (20). For liquid samples, IC methods for determining carbonate (COa^) depend on concentration. At >500-pg/mL levels, the parameters outlined in table 6 are adequate. For <500-^g/mL levels, a separate method, called ion exclusion is required. In ion exclusion only a suppressor column is required and dis- tilled water is used as the eluent; this procedure is applicable down to the l-pg/mL level. Transition metal ions such as Fe^^ tie up active sites in the resins used in IC, effectively "poisoning" the resin. This prob- lem is resolved by inserting a small precolumn in the system. The transition ions remain in the precolumn without affecting the separator's column efficiency. The precolumn is periodi- cally replaced to prevent carryover to the separator column. Acid dissolution of solids is not practical because the acid or combination of acids used in the dissolution will prevent the determination of the acid anions in the original sample. By fusing the sample with Na2C03 and leaching with deionized water, the anions in the sample are converted to the water Table 6. — Ion chromatograph operating conditions for determining anions and NH4' Elution Detection time' Possible limits, Constituent min interferences M-g/mL Chloride (Cr) =4 HighCOa^- (>1,000ji.g/mL). 0.5 Fluoride (F') -1.5 None expected .2 Nitrate (NO3-) -9 High P04^- (>100tJLg/mL). 1.0 Phosphate =7 High NO3" 1.0 (P04^-). (>100 M-g/mL). Sulfate -15 None expected 1.0 (S04=-). Carbonate -3 Higher ^500.0 (CO32-). (>50 |i,g/mL). Ammonium -16 High Na 5.0 (NH4*). (>100|jLg/mL). ' All elution times are based on using a 0.003/W NaHCO3/0.0024W NajCOj eluent and a 3- by 500-mm anion separator column for all except ammonium (0.005/W HNO3 eluent and a 6- by 250-mm cation separator) at a flow rate of 2.5 mL/min. ^ A limit of ~1 |oLg/mL can be detected by use of ion exclusion using distilled H2O as an eluent and the suppressor column only. soluble Na^ form. This fusion technique has the additional advantage of forming transition metal carbonates that gener- ally remain insoluble, thereby eliminating the transition metal poisoning of the column. After the samples are fused and water leached, the liquid is injected into the IC for analysis. A Bureau of Mines developed fusion technique was applied successfully to the anion IC characterization of phosphate minerals (14) and cement kiln dust (20). The carbonate ion in the solid phase cannot be analyzed by IC using the fusion method because of the COa^' contribution from the flux. Thermal gravimetric analysis of the unfused solid allows the determination of COa^" concentration based on the thermal evolution of CO2 coupled with gas chromatograpy. The evolution of CO2 by acid with subsequent capture of CO2 could also be applicable. Detection limits for the various ions by IC are given in table 6. The IC method is generally within ±5 pet relative of the actual value depending on the concentration of the ions of interest. WET CHEMICAL METHODS Classical wet chemical methods of analysis are available for use in determining individual elements and ionic species of interest, but they are generally time consuming and require a separate sample for each determination. Various standard analytical methods are listed by EPA (32) including titrimetric, gravimetric, spectrophotometric, potentiometric, and specific ion electrode methods in addition to specific parameter meth- ods such as chemical oxygen demand (COD) and pH. The focus of this report is on the use of multielement techniques however, and no detailed discussion will be made of these single constituent analytical methods. COMPARISON OF CHEMICAL ANALYSIS RESULTS Several nodule materials were used for interlaboratory com- parisons of analytical methods. Seven manganese nodule standards were received, five were in-house standards from two industrial laboratories (A and B) and the other two were available from the U.S. Geological Survey (USGS) (7 1). Ana- lytical results from laboratories A and B and the two USGS standards are compared with results obtained by the Bureau's Avondale (MD) Research Center in table 7. Both industrial laboratories had obtained their data using AASforthe elemental determinations, although different disso- lution procedures were used. USGS published data are based on average results reported by various laboratories by several Table 7. — Comparison of interlaboratory analyses of manganese nodule standards Standard Micrograms per gram As Be Cd Cr Pb Sb Se Weight percent Ba Co Cu Fe Mn Mo Ni Zn A-1;' Lab A ... . BOM A-2:' Lab A ... . BOM A-3:' Lab A ... . BOM B-1:' Lab B ... . BOM B-2:' Lab B ... . BOM USGS A-1 :2 USGS.... BOM USGSP-1:2 USGS.... BOM ND ND ND ND ND ND ND 48 ND 73 298 306 39 45 ND ND ND <20 ND <20 2 3 2 2 6 ND 3 4 ND ND ND 21 ND 20 ND 14 ND 20 6.5 8.0 22 22 ND ND ND 30 ND 30 ND 60 ND 50 24 30 17.5 15 ND ND ND 490 ND 400 480 450 490 455 846 860 555 495 ND ND ND ND ND ND ND 41 ND 57 34 25 50 44 ND ND ND ND ND ND ND ND ND ND ND <0.26 ND <0.26 ND ND ND 220 ND 180 ND 190 ND 230 61 ND 154 150 ND ND ND 0.14 ND .15 .26 .26 .25 .25 .17 .19 .34 .31 0.24 .22 .25 .25 .24 .24 .22 .24 .26 .25 .31 .31 .22 .24 0.97 1.00 1.23 1.18 1.28 1.28 1.01 1.00 1.30 1.27 .11 .12 1.15 1,17 7.3 7.0 6.4 6.2 5.0 4.8 6.8 6.4 5.9 5.7 10.9 11.3 5.8 6.1 24.2 23.4 29.8 28.4 34.0 32.2 26.7 26.6 31.4 31.8 18.5 20.0 29.1 29.9 ND ND ND ND ND ND 0.05 .06 .06 .05 .04 ND .08 .07 1.19 1.15 1.46 1.40 1.26 1.24 1.36 1.33 1.55 1.51 .64 .69 1.34 1.36 0.10 .09 BOM Bureau of Mines. ND Not determined. USGS U.S. Geological Survey. ' Industrial laboratory in-house reference standard. ^ See reference 11 for information on the USGS reference sample. Table 8. — Round-robin results for Cuprlon process reject waste material, solid phase Element As . Be. Cd. Cr . Mo. Pb. Sb. Se. Tl.. Bureau of Mines SLCRC AIRC RRC AvRC Industrial LabB CONCENTRATION, ixg/g AIRC Albany (OR) Research Center. AvRC Avondale (MD) Research Center. ND Not determined. RRC Reno (NV) Research Center. SLCRC Salt Lake City (UT) Research Center. LabC CONCENTRATION, wt pet Ba 0.26 0.33 0.54 0.24 0.29 ND Co .17 .17 .19 .18 .17 0.18 Cu .14 .14 .13 .14 .15 .12 Fe 5.5 7.8 4.8 5.8 5.6 6.4 Mn 26.0 27.4 25.8 27.0 27.8 32.2 Ni .20 .21 .32 .22 .20 .28 Zn .11 .12 <.01 .13 ,11 .11 45 46 <40 49 ND ND ND 2 <3 ND 40 30 21 20 19 29 56 <500 30 21 50 ND 28 68 <100 590 650 540 500 600 <10 24 72 40 ND <1 <5 ND ND ND 150 <10 ND 83 ND 55 ND 49 ND 190 410 38 1 160 Table 9. — Round-robin results for Cuprion process reject waste material, liquid phase, micrograms per milliliter Elsmsnt Bureau of Mines Industrial SLCRC AIRC RRC AvRC labC As 0.015 0.01 <0.03 0.018 0.025 Ba .16 .11 .17 <.8 .27 Be ND ND .003 <.03 <.01 Cd <.01 <.05 <.004 <.03 <.05 Co <.01 <.1 <.2 <.3 .10 ■ Cr <.1 .3 <.04 <.2 <.1 Cu .15 <.01 <.1 <.10 <.20 <.1 <.50 <.20 <.03 <.11 <.50 <.7 < 05 Fe <.05 Mn <.02 Mo 14 ND 15 30 63 Ni <.01 <.10 <.03 <.10 <.20 Pb <.1 <.01 .02 <.5 <.01 <.02 <.06 <.02 .16 <.2 .007 .02 <.01 Sb <.018 Se <.03 Tl .4 <.1 ND <.2 .11 Zn <.1 <.1 3.3 <.03 <.04 AIRC Albany (OR) Research Center. AvRC Avondale (MD) Research Center. ND Not determined. RRC Reno (NV) Research Center. SLCRC Salt Lake City (UT) Research Center. methods (7 7). The Avondale results were obtained from the HCI-HF and the HNO3-HF dissolution procedures. Results obtained by AAS by Avondale personnel agree well with results reported by the industrial laboratories and the USGS. A reject waste slurry material from the Cuprion process was prepared, blended, and samples were sent to the Bureau's Salt Lake City (UT), Albany (OR), Reno (NV), and Avondale (MD) Research Centers and to two independent industrial laboratories (B and C). Analytical data were requested for the 1 6 elements of interest, as well as any other element or ionic species they could conveniently determine. Analyses of both the liquid and solid phases were performed by all laboratories except industrial laboratory B, which reported only the solid phase analysis. Table 8 gives the results obtained by the six laboratories for the solid phase. Good agreement was obtained for the major and minor elements; Co, Cu, Ni, and Zn, and the trace elements; As, Be, Cr, Pb, and Se. The elements Ba, Fe, Cd, Mn, Mo, Sb, and Tl had only moderate agreement. It should be noted that the Avondale laboratory and industrial laboratory B have more experience in analyzing nodules and nodule waste materials than the other four laboratories. However, agreement overall can be considered acceptable for this initial round robin. Table 9 gives the round-robin results for the liquid phase of the tested material. Again agreement for most of the elements provides confidence in the analytical methods used. The results for both phases of the tested material and the manganese nodule standards indicate that standard dissolu- tion procedures listed in this report for nodules as well as procedures used in laboratories accustomed to analyzing inor- ganic matrices are adequate for determining the elemental content of nodules and reject waste materials. LEACHING TESTS EP TOXICITY TEST According to EPA regulations under the Resource Conser- vation and Recovery Act (RCRA) (37), a solid waste must be listed as a hazardous waste if it exhibits any of the following characteristics as defined in RCRA: ignitability, corrosivity, reactivity, and/or extraction procedure (EP) toxicity (8-9). Reject waste materials from manganese nodule processing will not exhibit any properties of ignitability or reactivity. Corrosivity applies primarily to liquid wastes and should not be a problem if adequate waste management practices are used in the washing of the tailings. The only applicable hazardous waste criterion is the EP toxicity test. Briefly, the EP toxicity test consists of agitating, for 24 h, a minimum sample weight of 1 00 g of filtered material in 1 ,600 mL of distilled water (maintain a 16:1 water-to-solids ratio for larger sample weights) to which a maximum of 400 mL of 0.5N acetic acid (4 mL of acid per gram of material) may be added to maintain a pH of 5.0 ± 0.2. If all 400 mL of the acid is not required to achieve the desired pH, the remaining volume to make 2,000 mL (20:1 liquid-to-solid ratio) is added as dis- tilled water. The solution is filtered on a 0.45-pm pore size filter. The resulting extract (liquid portion) in the EP toxicity test is not to exceed 100 times the National Drinking Water Stan- dard for concentrations of eight metals: Ag, As, Ba, Cd, Cr, Hg, Pb, and Se. The EP toxicity limits, in micrograms per milliliter, are as follows: Ag, 5; As, 5; Ba, 1 00; Cd, 1 ; Cr, 5; Hg, 0.2; Pb, 5; and Se, 1 . ASTM SHAKE EXTRACTION TEST A second leaching test, the American Society for Testing Materials (ASTM) shake extraction test (2), has been pro- posed by ASTM as an alternate method for evaluating wastes, especially those of low organic content such as mining waste. This test consists of contacting a minimum of 350 g of dried material with distilled deionized water; the weight of water to be four times the sample weight. The slurry is agitated in a closed container for 48 h and the liquid portion filtered on 0.45-^im filter paper. The extract is then analyzed for the desired components including those outlined in the RCRA criteria. U.S. ARMY CORPS OF ENGINEERS SEAWATER ELUTRIANT TEST In the possible case of ocean disposal of nodule reject waste materials, either by ocean dumping or by ocean outfalls, a seawater leachate test may provide more appropriate data than the previous two leach tests. The Corps of Engineers dredge material elutriant test can be used to evaluate the extent of seawater-leachable metals in the waste materials {33). The procedure consists of mixing a weighed volume of material with four times the volume of seawater, agitating for 1 h, filtering and analyzing the seawater solution. Concentra- tions are compared with those in the seawater prior to leaching. Based on this analysis, concentrations of the elements at proposed mixing levels found in ocean outfalls or in ocean dumping can be extrapolated. Depending on final regulations in regard to ocean disposal, the degree of mixing required can be regulated by either dumping large amounts at once for minimal mixing rates or by trickling to provide for high mixing rates. NOAA has an ongoing study to establish requirements in this area. RESULTS OF LEACHING TESTS The EP toxicity test, the ASTM shake extraction test, and the Corps of Engineers seawater elutriant test were all applied to the Cuprion pilot plant tailings described in table 8. The results are listed in table 1 0. Comparison of the established Table 10. — Element concentration in leachate from leaching tests on Cuprion process reject waste material, micrograms per milliliter Element EP toxicity test ASTM shake ex- traction test Seawater elu- triant test Ag As Ba Be Cd Co Cr Cu Fe Hg Mn Mo Ni Pb Sb Se Tl Zn <0.07 .004 <2 <.06 .06 12 <.4 1.3 <.5 .019 1,690 <.6 9.9 <.7 .003 <.003 <2 2.5 <0.07 <.003 <2 <.06 <.05 <.3 <.4 <.2 <.5 ND <.06 3.8 <.1 <.7 <.003 <.003 <2 <.02 <0.07 <.003 <2 <.06 <.05 <.3 <.4 <.2 <.5 ND .28 <.6 <.10 <.7 <.003 <.003 <2 <.04 ND Not determined. NOTE. — EP toxicity test has the following maximum allowable concentration of contaminants for 8 elements, in micrograms per milliliter: Ag, 5; As, 5; Ba, 100; Cd, 1 ; Cr, 5; Hg, 0.2; Pb, 5; and Se, 1 . EP toxicity test limits listed in table 1 with the concentrations leached from the Cuprion pilot plant rejects show that leachate concentrations from this waste material are consistently one to three orders of magnitude lower than would be required to be classified as hazardous. Manganese, cobalt, and nickel were leached from the rejects to some extent by the EP toxicity test but none of these are considered in the hazardous waste criteria. CONCLUSIONS In general, the conventional physical and chemical analyti- cal procedures used by laboratories experienced in working with inorganic matrices are applicable to manganese nodules and their processing reject waste materials. The high iron and manganese content of nodule materials must be taken into account in chemical analyses, especially for possible interfer- ences in trace element determinations. The precautions are described or referenced in the text for each of the various methods discussed. The fine-grained or amorphous nature of manganese nod- ules and nodule tailings generally limit the identification of mineral compounds to the major and minor constituents such as manganese carbonate or oxide, quartz, feldspars, and clays. The use of referenced electron microscopic techniques is purported to identify minerals in concentrations less than about 5 wt pet. The iron compounds are often amorphous, requiring the use of referenced infrared spectroscopy or chemi- cal methods for identification. In comparisons of leachate tests on Cuprion pilot-plant tailings, the EP toxicity test seemed to show greater leaching ability for the eight regulated elements than the ASTM shake extraction test or the Corps of Engineers seawater elutriant test. However, these levels were one to three orders of magnitude lower than would be required for the wastes to be classified as hazardous. Three elements not listed in classifying a waste as hazardous, Mn, Co, and Ni, showed some leachability, but the leaching was minimal. The procedures described in this report are not being sug- gested as standard methods, but are simply a review of state- of-the-science analytical techniques as applied to manganese nodule materials. Any skilled inorganic analyst taking the pre- cautions described in this report for the interferences should be capable of providing reliable analyses of manganese nod- ules and nodule processing reject waste materials. 10 REFERENCES 1 . Allen, T. Particle Size Measurement. 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Methods for Chemical Analysis of Water and Wastes. Environmental Monitoring and Sup- port Laboratory, Cincinnati, OH, EPA-600/4- 79-020, March 1 979, 460 PP- 33. U.S. Environmental Protection Agency and U.S. Army Corps of Engineers. Ecological Evaluation of Proposed Discharge of Dredged Material Into Ocean Waters. Environmental Effects Laboratory, Water- ways Experiment Station, U.S. Army Corps of Engineers, Vicksburg, MS, July 1977, 103 pp. •CiU.S. GOVERNMENT PRINTING OFFICE: 1983-605-015/63 INT.-BU.OF MINES, PGH., PA. 27 144 f5 Q ^ v^^^ ■- *-^* :'^*: "-^' -'Jfe- %^** -M^-' \/ .*'^'- •>* %vf.^^->* \--^'\^*' \°-T/«?-/ \--^^--y'** --w^--/' 'bV V'^' ^^° y ^.- **'% •.^•' /%. l^.- **'% •.^•- /\ •..<»... * 4 o »"•- **..** ■ yM/i'. x.s**' .-ai&'v ' **^«* ' /^v;;.. 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