Solubility enhancement of seven metal contaminants using carboxymethyl-beta-cyclodextrin (CMCD).

Carboxymethyl-beta-cyclodextrin (CMCD) has been suggested as a complexing agent for remediation of sites co-contaminated with metals and organic pollutants. As part of an attempt to construct a geochemical complexation model for metal-CMCD interactions, conditional formation constants for the complexes between CMCD and 7 metal ions (Ba, Ca, Cd, Ni, Pb, Sr, and Zn) are estimated from experimental data. Stable metal concentrations were reached after approximately 1 day and estimated logarithmic conditional formation constants range from -3.2 to -5.1 with confidence intervals within +/-0.08 log units. Experiments performed at 10 degrees C and 25 degrees C show that temperature affects the solubility of the metal salts but the strength of CMCD-metal complexes are not affected by this temperature variation. The conditional stability constants and complexation model presented in this work can be used to screen CMCD as a potential remediation agent for clean-up of contaminated soil and groundwater.

Enhanced solubilization of a metal-organic contaminant mixture (Pb, Sr, Zn, and perchloroethylene) by cyclodextrin.

Prior work has suggested that (carboxymethyl)-beta-cyclodextrin (CMCD) is capable of simultaneously enhancing the solubility of organics and metals, but sparse experimental data and no theoretical models have been published on this process. Preciously, a geochemical model for metal complexation by CMCD was formulated using PHREEQC on the basis of conditional stability constants measured in experiments using single-metal salts. In this study, the model is expanded to simultaneous metal and organic (perchloroethylene, PCE) complexation by CMCD. Experiments to verify the application of the formulation to mixed-waste systems were performed using solutions containing multiple metal ions (Pb, Sr, and Zn) and in a separate experiment introducing PCE with multiple metal ions. These experimental results show simultaneous solubility enhancement of metals and PCE. For solutions up to about 50 g/L CMCD, the model accurately predicted the simultaneous solubility enhancement for PCE, Pb, and Zn, while the difference between the measured and predicted Sr concentrations was accurate to within 15%. At CMCD concentrations greater than 50 g/L, the observed metal solubilities were greater than predicted (10% for Pb and Zn), probably due to the difficulty in accurately representing the activity and the effect on the ionic strength of functional groups on large organic molecules at higher concentrations.

Using PHREEQC to simulate solute transport in fractured bedrock.

The geochemical computer model PHREEQC can simulate solute transport in fractured bedrock aquifers that can be conceptualized as dual-porosity flow systems subject to one-dimensional advective-dispersive transport in the bedrock fractures and diffusive transport in the bedrock matrix. This article demonstrates how the physical characteristics of such flow systems can be parameterized for use in PHREEQC, it provides a method for minimizing numerical dispersion in PHREEQC simulations, and it compares PHREEQC simulations with results of an analytical solution. The simulations assumed a dual-porosity conceptual model involving advective-reactive-dispersive transport in the mobile zone (bedrock fracture) and diffusive-reactive transport in the immobile zone (bedrock matrix). The results from the PHREEQC dual-porosity transport model that uses a finite-difference approach showed excellent agreement compared with an analytical solution.

Using UCODE_2005 and PHREEQC to determine thermodynamic constants from experimental data.

This article presents a method for estimating chemical thermodynamic constants from experimental data using the two computer programs UCODE_2005 and PHREEQC. As an example, the conditional stability constant for lead (Pb) complexation by a remediation agent (carboxymethyl-beta-cyclodextrin) is estimated, but the method can be applied to estimate other thermodynamic parameters such as sorption constants and degradation rate constants. Advantages of this technique include estimation of uncertainties associated with estimated parameters, evaluation of information content of observations, statistical evaluation of the appropriateness of the conceptual model, and statistical-based comparison of different models.

Determining conditional stability constants for Pb complexation by carboxymethyl-beta-cyclodextrin (CMCD).

Carboxymethyl-beta-cyclodextrin (CMCD) has been proposed for remediation of metal-contaminated sediments. This research presents stability constants for CMCD-lead complexes, and demonstrates a rigorous methodology for estimating stability constants for metal-complexing agents. The conditional stability constant for the lead-CMCD aqueous complex was determined to be 10(5.18) with the 95% confidence interval ranging from 10(5.14) to 10(5.22). The best fit for experimental data was made by assuming a reaction between divalent CMCD(2-) and Pb(2+) and using the WATEQ activity coefficient formulation. The optimized value was derived from experimental data with the geochemical model PHREEQC coupled to UCODE_2005, a parameter optimization program. Like FITEQL, UCODE has a built-in option to optimize parameter values by minimizing the weighted sum of squared residuals (WSSR). However, our approach not only allows rapid, automatic optimization of the stability constant, but also allows determination of uncertainties in estimated parameter values and statistical analysis to assess the appropriateness of the conceptual model. The automation of the process allows testing of multiple conceptual models and the final values produced are internally consistent with the PHREEQC database. In this case five different conceptual models to describe the metal complexation and protonation reactions of CMCD were considered.

Model parameters for simulating fate and transport of on-site wastewater nutrients.

This paper presents a critical review of model-input parameters for transport of on-site wastewater treatment system (OWS) pollutants. Approximately 25% of the U.S. population relies on soil-based OWS for effective treatment and protection of public health and environmental quality. Mathematical models are useful tools for understanding and predicting the transport and fate of wastewater pollutants and for addressing water-budget issues related to wastewater reclamation from site to watershed scales. However, input parameters for models that simulate fate and transport of OWS pollutants are not readily obtained. The purpose of this analysis is to illustrate an objective, statistically supported method for choosing model-input parameters related to nitrogen (N) and phosphorus (P). Data were gathered from existing studies reported in the literature. Cumulative frequency distributions (CFDs) are provided for OWS effluent concentrations of N and P, nitrification and denitrification rates, and linear sorption isotherm constants for P. When CFDs are not presented, ranges and median values are provided. Median values for model-input parameters are as follows: total N concentration (44 mg/L), nitrate-N (0.2 mg/L), ammonium (60 mg/L), phosphate-P (9 mg/L), organic N (14 mg/L), zero-order nitrification rate (264 mg/L/d), first-order nitrification (2.9/d), first-order dentrification (0.025/d), maximum soil capacity for P uptake (237 mg/kg), linear sorption isotherm constant for P (15.1 L/kg), and OWS effluent flow rates (260 L/person/d).