Effectiveness of Commercial Heavy Metal Chelators with New Insights for the Future in Chelate Design

Matthew M. Matlock, Kevin R. Henke, and David A. Atwood Department of Chemistry, University of Kentucky, halides@aol.com.

Abstract. Toxic heavy metals in air, soil, and water are global problems that are a growing threat to the environment. There are hundreds of sources of heavy metal pollution, including the coal, natural gas, paper, and chlor-alkali industries (1,2). To meet the federal and state guidelines for heavy metal discharge, companies often use chemical precipitation or chelating agents. In order to be competitive economically, many of these chelating ligands are simple, easy to obtain, and, generally offer weak bonding for heavy metals. Poor and indiscriminant metal binding often lead to unstable metal ligand complexes. Laboratory testing of three commercial reagents, TMT (Trimercaptotriazine), Thio-Red (potassium/sodium thiocarbonate), and HMP-2000 (sodium dimethyldithiocarbamate), has shown that the investigated compounds were unable to reduce independent solutions of 50.00 ppm (parts per million) cadmium, copper, ferrous, lead, or mercury to meet EPA standards (CFR, 1994). Additionally, the tested compounds displayed high leaching rates and in some cases decomposed to produce toxic substances. For this reason, a novel multidentate ligand has been developed for the safe and effective removal of heavy metals.

Introduction

Toxic heavy metals in air, soil, and water are global problems that are a growing threat to humanity. There are hundreds of sources of heavy metal pollution, including the coal, natural gas, paper, and chlor-alkali industries (1,2). In response to the growing problems, federal and state governments have instituted environmental regulations to protect the quality of surface and ground water from heavy metal pollutants, such as Cd, Cu, Pb, Hg, Cr, and Fe (3). To meet the federal and state guidelines for heavy metal discharge, companies often use chemical precipitation or chelating agents. For acid mine drainage (AMD) and wastewater treatment plants, the typical means of removing heavy metals is usually accomplished through pH neutralization and precipitation with lime, peroxide addition, reverse osmosis, and ion exchange (4). Extensive research and financial resources have been spent on each of these treatment processes with the overwhelmingly preferred method, based upon cost and effectiveness, being precipitation through neutralization (4). A major disadvantage of the liming process, however, is the need for large doses of alkaline materials to increase and maintain pH values of 4.0 to above 6.5 for optimal metal removal (2). Additionally, pH neutralization typically requires that the materials be appreciably fine-grained to provide the necessary reactive surface area (5). Furthermore, liming produces secondary wastes, such as metal hydroxide sludges, that necessitate highly regulated and costly disposal (6). As an alternative to the liming process many companies have developed chelating ligands to precipitate heavy metals from aqueous systems. In order to be competitive economically, many of these chelating ligands are simple, easy to obtain, and, in general, offer minimal bonding for heavy metals. Poor and indiscriminant metal binding criteria often lead to unstable metal ligand complexes. These tend to decompose over time

releasing the heavy metals back into the environment over varying, but usually short, periods of time (9). Many of the current remediation ligands on the market require high ligand to metal dosages to lower metal concentrations to EPA (Environmental Protection Agency) limits. In addition to high dosage ratios, many of the ligands decompose or are themselves hazardous materials (9). The purpose of this article is to examine the effectiveness of three major chelating ligands that are used commercially, and to introduce new research which promises to not only produce low-cost, highly selective ligands for heavy metal remediation, but also, products which can be used at low dosages. The remediation and wastewater treatment reagents discussed in this article are TMT (trimercaptotriazine), STC (potassium/sodium thiocarbonate), and SDTC (sodium dimethyldithiocarbamate) (Figures 1A-C). TMT, or 2,4,6-trimercaptotiazine, trisodium salt nonahydrate, Na3C3N3S39H2O (Figure 1A), is a chemical reagent commonly utilized for the precipitation of divalent and univalent heavy metals from water. TMT is manufactured and distributed by Degussa Corporation USA of Allendale and Ridgefield Park, New Jersey (7). Despite the widespread use of TMT, only limited information is available on how the product reacts with heavy metals in aqueous solutions and the chemistry and stability of the resulting heavy metal-TMT precipitates. A second chemical reagent for precipitating divalent heavy metals from contaminated waters is STC. STC is a sodium (with or without potassium) thiocarbonate ([Na, K]2CS3nH2O, where n 0), which has a trade name of Thio-Red and is distributed by ETUS Inc. (9; Figure 1B). Previous laboratory studies have demonstrated that Thio-Red ultimately removes copper, mercury, lead, and cadmium from aqueous

solutions through the formation of metal sulfides (that is, CuS, HgS, PbS, and ZnS) rather than metal thiocarbonates (that is, CuCS3, HgCS3, PbCS3, and ZnCS3) as claimed by ETUS Inc., 1994 (8,9). A byproduct of the metal sulfide precipitation with STC is carbon disulfide, which is volatile and toxic liquid. Another type of commercial remediation agent is SDTC. SDTC is a sodium thiocarbamate, which has the trade name of HMP-2000 (Figure 1C). Recently, an accidental release of over 1.5 million gallons of toxic wastewater laced with SDTC occurred when a local auto parts manufacturing plant in Anderson, Indiana, discharged large volumes of contaminated water to the city's wastewater (10). The SDTC reportably decomposed into toxic compounds, tetramethylthiuram and thiram, where it crippled the Anderson, Indiana, wastewater plant and was later discharged into local state waters (10). The Indiana Department of Environmental Management reported the deaths of 117 tons of fish over a 50-mile stretch from Anderson to Indianapolis, Indiana (10). Analytical Methods Lead, cadmium, iron (II), and copper analyses were performed with a 1999 Jarrell Ash Duo HR Iris Advanced Inductive Coupled Plasma (ICP-OES) Spectrometer. Mercury results were obtained using cold vapor atomic fluorescence spectroscopy (CVAF) on a Varsal Atomic Fluorescence Spectrometer, model number VI2000, using EPA techniques for mercury analyses (11). For powder XRD analyses, the samples were mounted on glass slides with ethanol and analyzed with a Rigaku unit at 40kV and 20 mA using Cu Ka1 (=1.540598 ) radiation. Infrared spectroscopy (IR) data on the TMT and STDC commercial reagents were obtained from the Aldrich IR library (12). For the metal-ligand complexes, the IR spectra were collected as potassium bromide pellets using

spectroscopy grade potassium bromide (KBr) using a Nicolet-Avatar 320 FT-IR series spectrometer. Elemental Analyses were determined on a Vario Elementar III. All masses were obtained with a Sartorius BP2100S or a Mettler AE 240 balance. Analytical Procedures for ICP Analyses Cadmium, Copper, Lead, and Iron (II) ICP Analyses A series of 100 ml 50.00 parts per million (ppm) Cd+2, Cu+2, Pb+2, Fe+2, and Hg+2 samples were prepared separately as water solutions. Based on one to one molar ratio, each of the reagents was added to the metal solutions. Aliquots (10 ml) were collected and filtered at 0.2 m at times 1 hour, 6 hours, and 20 hours following reagent addition (Tables 1-3). RESULTS AND DISCUSSION Characterization of Precipitates. For reactions between the metal-TMT and the metal-STC complexes, extensive research has been preformed by Henke and coworkers that describes resulting complexes (9,13,14). For the STC reactions, it has been proven that the resulting complexes are metal sulfide and carbon disulfide (9). Research on the STDC-metal complexes has also been conducted which shows a bidentate metal chelation through the terminal thio groups of the STDC (13,15). Each of the TMT, STC, and STDC metal complexes was confirmed to the corresponding literature using elemental analyses, IR, NMR, and XRD spectroscopy (12,15,16). Results of Pb+2, Cd+2, Cu+2, and Fe+2 Stoichiometry and Removal as Determined from the ICP.

It was found that at stoichiometric doses STC, STDC, or TMT was unable to remediate the cadmium, lead, copper, or iron from a 50.00 ppm (part-per-million) to meet the EPA discharge limits (3) (Tables 1-3). Even with a 10.00% molar excess dose, no additional significant removal was observed (Tables 1-3). The SDTC also displayed a higher affinity for cadmium, lead, copper, and iron than the STC but still EPA discharge limits were not achieved. TMT displays similar results as compared with the SDTC with the highest removal seen for lead and copper. Once again, it is seen that even at a 10% molar increase in dosage TMT was unable to reduce lead or cadmium concentrations to meet EPA standards (3). For the metal concentrations that increased over time for each ligand, it is believed that this is either contributed to the formation of more soluble metalligand complexes or a possible high leaching rate of the metal out of the ligand complexes. Results of Hg+2 Stoichiometry and Removal as Determined from the CVAF. For the mercury analyses, it was found that at stoichiometric and an 10% molar dose increase the STC, SDTC, and TMT were all unable to remove the concentration of mercury from the a 50.00 ppm solution the EPA limits (3) (Tables 1-3). Maximum results, for mercury removal with STC, were seen at 20 hours at a 10% molar dose increase with an average value of 3.97 ppm. At one hour the results of the SDTC, at a 10% molar dose increase, indicate a reasonably high removal of mercury with a final concentration of 0.690 ppm. Within 20 hours at stoichiometric doses, TMT was able to reduce the 50.00 ppm mercury concentrations to an average final concentration of 9.82 ppm. Insights for the Development of New Metal Chelators.

There is a definite need for new and more effective reagents to meet the growing environmental problem. Many reagents on the market today either lack the necessary binding criteria or pose too many environmental risks to be effectively utilized. For this reason, ligands utilizing multiple binding sites for heavy metals and mimicking biological systems for metal binding look to be a possible answer to heavy metal remediation and wastewater treatment. In order to create more effective and economical ligands, researchers at the University of Kentucky have developed a serious of new synthetic ligands, which utilize biological heavy metal binding motifs. These synthetic ligands provide multiple binding sites for heavy metals to secure the metals. Early results with the ligands have shown that heavy metal concentrations from aqueous solutions can be reduced well below EPA discharge limits, and the resulting precipitates have shown no solubility in organic solvents or aqueous systems over a pH range of 0.0 to 14.0 (17,18). For example, the synthetic ligands have been able to reduce mercury concentrations from a 50.00 ppm to 0.094 ppm and lead concentrations of a 50.00 ppm to 0.050 ppm (18). The newly developed ligands have also been effective in immobilizing mercury from contaminated soils. In recent tests with soils contaminated with 10270 ppm of elemental mercury, the multidentate ligand was capable of immobilizing 99.6% of the mercury. The resulting mercury-ligand compounds were shown to maintain stability even when subjected to the EPA digestion technique for mercury in solid or semisolid waste (19,20). Heavy metal pollution is a growing environmental problem, which requires immediate attention. With current commercial remediation reagents failing to provide the needed requirements as safe and effective metal chelators, the need for new technology is critical.

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Alloway, B.J. ed. (1995) Heavy Metals in Soils 2nd ed. Chapters 6,8,9,and 11. Chapman and Hall, Glasgow, UK. McDonald, D.G.; Grandt, A.F. (1981) Limestone- Lime Treatment of Acid Mine Drainage-Full Scale. EPA Project Summary (1981). EPA-600/S7-81-033. Code of Federal Regulations (CFR), 40, 141, 261, 268.40, U.S. Government Printing Office, Superintendent of Documents, Washington, DC. Wilmoth, R.C.; Kennedy, J.L. (1979) Industrial Environmental Research Laboratory, "Removal of Trace Elements from Acid mine Drainage." Drever, J.I., 1997, The Geochemistry of Natural Waters: Surface and Groundwater Environments, Prentice Hall, Upper Saddle River, NJ. Wang,W.; Zhenghe, X.; Finck, J. (1996) "Fundamental Study of an Ambient Temperature Ferrite Process in the Treatment of Acid Mine Drainage." Env. Sci. and Tech., 30, (8), 2604-2608. Degussa Corporation (1993) Data Sheets on TMT-15 and TMT, Ridgefield Park, New Jersey. ETUS, Inc. (1994) Product Information on Thio-Red, Sanford, Florida Henke, K.R. (1998) "Chemistry of Heavy Metal Precipitates Resulting from Reactions with Thio-Red". Wat. Env. Res., 70, (6), 1178-1185. State of Indiana's Data Fact's Sheet, http://www.state.in.us/idem/macs/factsheets/whiteriver/185. US Environmental Protection Agency (EPA), 1986, "Mercury in liquid waste (manual cold-vapor technique): Volume 1A: Laboratory Manual: Physical/Chemical Methods," SW-846, 3rd ed., Office of Solid Waste and Emergency Response, Washington DC.

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Figure 1. A. TMT (2,4,6-trimercaptotiazine, trisodium salt nonahydrate). B. STC (potassium/sodium thiocarbonate). C. SDTC (sodium dimethyldithiocarbamate).

A.
SN
-

N N S-

3Na+

B.

S-S S

+ 2 Na +

C.

SN S

+ Na +

10

Table 1. ICP and CVAF results of SDTC at stoichiometric doses and at 10% molar dosage increases.
Chelating Agent SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC SDTC Time (hours) 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 Initial metal Solution concentration (ppm) pH 3.5 3.5 3.5 4.0 4.0 4.0 3.5 3.5 3.5 4.0 4.0 4.0 3.0 3.0 3.0 4.0 4.0 4.0 4.0 4.0 4.0 4.5 4.5 4.5 4.0 4.0 4.0 4.0 4.0 4.0 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 Final metal concentration (ppm) 21.9 21.9 23.8 15.5 16.2 16.3 12.6 12.6 12.5 7.08 7.10 7.19 11.5 11.5 12.1 10.5 10.5 11.0 25.2 23.1 23.9 24.3 23.2 23.9 1.01 1.50 2.78 0.69 1.24 1.63 1.0 1.0 1.0 1.0 1.0 1.0 2.0 2.0 2.0 2.0 2.0 2.0 0.2 0.2 0.2 0.2 0.2 0.2 EPA Discharge Limit (ppm) (3) 5.0 5.0 5.0 5.0 5.0 5.0

Metal Pb Pb Pb Pb Pb Pb Cu Cu Cu Cu Cu Cu Cd Cd Cd Cd Cd Cd Fe (II) Fe (II) Fe (II) Fe(II) Fe(II) Fe(II) Hg Hg Hg Hg Hg Hg

Dose stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase

Table 2. ICP and CVAF results of STC at stoichiometric doses and at 10% molar dosage increases.
Final metal concentration (ppm) 38.2 44.8 48.2 33.7 41.6 48.0 27.8 29.0 28.9 27.1 25.8 26.8 34.4 39.5 47.1 27.1 34.9 41.5 35.2 34.4 33.0 34.8 34.6 33.6 8.59 8.07 6.85 6.72 5.20 3.97 1.0 1.0 1.0 1.0 1.0 1.0 2.0 2.0 2.0 2.0 2.0 2.0 0.2 0.2 0.2 0.2 0.2 0.2

Chelating Agent STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC STC

Metal Pb Pb Pb Pb Pb Pb Cu Cu Cu Cu Cu Cu Cd Cd Cd Cd Cd Cd Fe (II) Fe (II) Fe (II) Fe(II) Fe(II) Fe(II) Hg Hg Hg Hg Hg Hg

Dose stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase

Time (hours) 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20

Solution pH 6.0 6.0 6.0 5.5 5.5 5.5 5.0 5.0 5.0 4.5 4.5 4.5 5.5 5.5 5.5 5.0 5.0 5.0 6.0 6.0 6.0 5.0 5.0 5.0 6.0 6.0 6.0 6.0 6.0 6.0

Initial metal concentration (ppm) 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00

EPA Discharge Limit (ppm) (3) 5.0 5.0 5.0 5.0 5.0 5.0

Table 3. ICP and CVAF results of TMT at stoichiometric doses and at 10% molar dosage increases.
Chelating Agent TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT TMT Time (hours) 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 1 6 20 Solution Initial metal Final metal concentration pH concentration (ppm) (ppm) 5.0 5.0 5.0 5.5 5.5 5.5 5.0 5.0 5.0 5.5 5.5 5.5 5.0 5.0 5.0 5.5 5.5 5.5 5.0 5.0 5.0 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 18.2 18.5 21.1 16.1 16.6 17.3 16.2 13.3 10.1 16.2 14.2 12.6 37.1 36.1 38.2 21.0 21.0 21.6 25.0 25.5 25.3 23.6 22.4 21.8 18.1 13.4 9.82 15.2 16.9 10.5 1.0 1.0 1.0 1.0 1.0 1.0 2.0 2.0 2.0 2.0 2.0 2.0 0.2 0.2 0.2 0.2 0.2 0.2 EPA Discharge Limit (ppm) (3) 5.0 5.0 5.0 5.0 5.0 5.0

Metal Pb Pb Pb Pb Pb Pb Cu Cu Cu Cu Cu Cu Cd Cd Cd Cd Cd Cd Fe (II) Fe (II) Fe (II) Fe(II) Fe(II) Fe(II) Hg Hg Hg Hg Hg Hg

Dose stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase stoichiometric stoichiometric stoichiometric 10% dose increase 10% dose increase 10% dose increase