BNL Citric Acid Technology: Pilot Scale Demonstration

The objective of this project is to remove toxic metals such as lead and cadmium from incinerator ash using the Citric Acid Process developed at Brookhaven National Laboratory. In this process toxic metals in bottom ash from the incineration of municipal solid waste were first extracted with citric acid followed by biodegradation of the citric acid-metal extract by the bacterium Pseudomonas fluorescens for metals recovery. The ash contained the following metals: Al, As, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Se, Sr, Ti, and Zn. Optimization of the Citric Acid Process parameters which included citric acid molarity, contact time, the impact of mixing aggressiveness during extraction and pretreatment showed lead and cadmium removal from incinerator ash of >90%. Seeding the treated ash with P. fluorescens resulted in the removal of residual citric acid and biostabilization of any leachable lead, thus allowing it to pass EPA?s Toxicity Characteristic Leaching Procedure. Biodegradation of the citric acid extract removed >99% of the lead from the extract as well as other metals such as Al, Ca, Cu, Fe, Mg, Mn, Ti, and Zn. Speciation of the bioprecipitated lead by Extended X-ray Absorption Fine Structure at the National Synchrotron Light Source showed that the lead is predominantly associated with the phosphate and carboxyl functional groups in a stable form. Citric acid was completely recovered (>99%) from the extract by sulfide precipitation technique and the extraction efficiency of recovered citric acid is similar to that of the fresh citric acid. Recycling of the citric acid should result in considerable savings in the overall treatment cost. We have shown the potential application of this technology to remove and recover the metal contaminants from incinerator ash as well as from other heavy metal bearing wastes (i.e., electric arc furnace dust from steel industry) or soils. Information developed from this project is being applied to demonstrate the remediation of lead paint contaminated soils on Long Island

BNL Citric Acid Technology: Pilot Scale Demonstration

The objective of this project is to remove toxic metals such as lead and cadmium from incinerator ash using the Citric Acid Process developed at Brookhaven National Laboratory. In this process toxic metals in bottom ash from the incineration of municipal solid waste were first extracted with citric acid followed by biodegradation of the citric acid-metal extract by the bacterium Pseudomonas fluorescens for metals recovery. The ash contained the following metals: Al, As, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Se, Sr, Ti, and Zn. Optimization of the Citric Acid Process parameters which included citric acid molarity, contact time, the impact of mixing aggressiveness during extraction and pretreatment showed lead and cadmium removal from incinerator ash of >90%. Seeding the treated ash with P. fluorescens resulted in the removal of residual citric acid and biostabilization of any leachable lead, thus allowing it to pass EPA?s Toxicity Characteristic Leaching Procedure. Biodegradation of the citric acid extract removed >99% of the lead from the extract as well as other metals such as Al, Ca, Cu, Fe, Mg, Mn, Ti, and Zn. Speciation of the bioprecipitated lead by Extended X-ray Absorption Fine Structure at the National Synchrotron Light Source showed that the lead is predominantly associated with the phosphate and carboxyl functional groups in a stable form. Citric acid was completely recovered (>99%) from the extract by sulfide precipitation technique and the extraction efficiency of recovered citric acid is similar to that of the fresh citric acid. Recycling of the citric acid should result in considerable savings in the overall treatment cost. We have shown the potential application of this technology to remove and recover the metal contaminants from incinerator ash as well as from other heavy metal bearing wastes (i.e., electric arc furnace dust from steel industry) or soils. Information developed from this project is being applied to demonstrate the remediation of lead paint contaminated soils on Long Island

Random Matrices in 2D, Laplacian Growth and Operator Theory

Since it was first applied to the study of nuclear interactions by Wigner and Dyson, almost 60 years ago, Random Matrix Theory (RMT) has developed into a field of its own within applied mathematics, and is now essential to many parts of theoretical physics, from condensed matter to high energy. The fundamental results obtained so far rely mostly on the theory of random matrices in one dimension (the dimensionality of the spectrum, or equilibrium probability density). In the last few years, this theory has been extended to the case where the spectrum is two-dimensional, or even fractal, with dimensions between 1 and 2. In this article, we review these recent developments and indicate some physical problems where the theory can be applied.Comment: 88 pages, 8 figure

Computation of currents at microelectrodes using hp-DGFEM

We describe how a discontinuous Galerkin finite element method with interior penalty can be used to compute the current flowing at a microdisc electrode for the steady-state E and EC′ reaction mechanisms and at a channel microband electrode for the steady-state E, ECE, EC2E, DISP1 and DISP2 reaction mechanisms. We then state an a posteriori error bound for the computed current and use this as the basis of an hp-adaptive discontinuous Galerkin finite element algorithm to deliver the current to within a prescribed error tolerance. For all problems we demonstrate excellent agreement with previous results using comparatively coarse meshes. © 2005 Elsevier B.V. All rights reserved

Finite element solution of a membrane covered electrode problem

Membrane covered oxygen sensors, or Clark electrodes, are used for monitoring the concentration of oxygen in blood. The operation of such sensors is governed by the diffusion equation with different diffusion coefficients in different sub-domains. The form of the boundary conditions and the material interface conditions means that the derivative of the solution has discontinuities which restrict the convergence of standard numerical methods on regular meshes. We describe and computationally compare adaptive finite element methods based on continuous and discontinuous basis functions to overcome this problem. © 2005 Elsevier B.V. All rights reserved

Adaptive finite element methods in electrochemistry.

In this article, we review some of our previous work that considers the general problem of numerical simulation of the currents at microelectrodes using an adaptive finite element approach. Microelectrodes typically consist of an electrode embedded (or recessed) in an insulating material. For all such electrodes, numerical simulation is made difficult by the presence of a boundary singularity at the electrode edge (where the electrode meets the insulator), manifested by the large increase in the current density at this point, often referred to as the edge effect. Our approach to overcoming this problem has involved the derivation of an a posteriori bound on the error in the numerical approximation for the current that can be used to drive an adaptive mesh-generation algorithm, allowing calculation of the quantity of interest (the current) to within a prescribed tolerance. We illustrate the generic applicability of the approach by considering a broad range of steady-state applications of the technique

Multiparameter estimation in voltammetry when an electron transfer process is coupled to a chemical reaction

Estimation of thermodynamic and kinetic parameters in electrochemical studies is usually undertaken via comparison of the experimental results with theory based on a model that mimics the experiment. The present study examines the credibility of transient d.c. and a.c. voltammetric theory-experiment comparisons for recovery of the parameters needed to model the ubiquitous mechanism when an electron transfer (E) reaction is followed by a chemical (C) step in the EC process ([Formula: see text]). The data analysis has been undertaken using optimization methods facilitated in some cases by grid computing. These techniques have been applied to the simulated (5% noise added) and experimental (reduction of trans-stilbene) voltammograms to assess the capabilities of parameter recovery of E(0) (reversible potential for the E step), k(0) (heterogeneous electron transfer rate constant at E(0)), α (charge transfer coefficient for the E step), and k(f) and k(b) (forward and backward rate constants for the C step) under different kinetic regimes. The advantages provided by the use of a.c. instead of d.c. voltammetry and data optimization methods over heuristic approaches to "experiment"-theory comparisons are discussed, as are the limitations in the efficient recovery of a unique set of parameters for the EC mechanism. In the particular experimental case examined herein, results for the protonation of the electrochemically generated stilbene dianion demonstrate that, notwithstanding significant advances in experiment and theory of voltammetric analysis, reliable recovery of the parameters for the EC mechanism with a fast chemical process remains a stiff problem

Role of Microbes as Biocolloids in the Transport of Actinides from a Deep Underground Radioactive Waste Repository

We investigated the interaction of dissolved actinides Th, U, Np Zgpu, and Am, with a pure and a mixed culture of halophilic bactezia isolated from the Waste Isolation H.Iot Plant repository under anaerobic conditions to evaluate their potentiaI transport as biocolloids from the waste site. The sizes of the bacterial cells studied ranged from ().54 x 0.48 pm to 7.7 x 0.67pm Using sequential mimofiltration, we determined the ~~ation of actinides with fi-ee-living (mobile) bacterial cells suspended in a fluid medium containing. NaCl or M=W12 brine, at various phaes of their growth cycIes. The number of suspended kcteria rangy-d born 106 to 109 cells ml-*. Tine amount of actinide associatd with the wspend~ cell fraction (cakzdated & mol cell-*) was very Iow: Th, 10-*2; U, 10-1s - 10-lS; - ~ Np, 1o-15- 10-19; Pu, 10-ls -10-21 ; and h, 10-1* - 10-*9 ; and it varied with the bacteihl - CUIture studied. l%e differe&es in the asswiation are amibuted to the extent of bioamxmdation and biosorption by the bacteria pH, the compo&on of the brine, and the speziation and bioavaiIability of the actinides