Complexation of iron(ll) by catechol and thiol ligands leads to the formation of aqueous species that are capable of reducing substituted nitroaromatic compounds (NACs) to the corresponding anilines. No reactions of NACs are observed in FelI-only or ligand-only solutions. In solutions containing FeII and tiron, a model catechol, rates of NAC reduction are heavily dependent on pH, ligand concentration, and ionic strength. Observed pseudo-first-order rate constants (k(obs)) for 4-chloronitrobenzene reduction vary by more than 6 orders of magnitude, and the variability is well described by the expression k(obs) = k(FeL2)(6-) [FeL2(6-)], where [FeL2(6-)] is the concentration of the 1:2 FeII-tiron complex and kFeL2(6-) is the bimolecular rate constant for 4-chloronitrobenzene reaction with this species. The high reactivity of this FeII species is attributed to the low standard one-electron reduction potential of the corresponding FeIII/FeII redox couple (EH0 = -0.509 V vs NHE). The relative reactivity of different NACs can be described by a linear free-energy relationship (LFER) with the one-electron reduction potentials of the NACs, EH1'(ArNO2). The experimentally derived slope of the LFER indicates that electron transfer is rate determining. These findings suggest that FeII-organic complexes may play an important, previously unrecognized, role in the reductive transformation of persistent organic contaminants.

Complexation of Fe(II) by dissolved and surface-bound ligands can significantly modify the metal's redox reactivity, and recent work reveals that Fe(II) complexes with selected classes of organic ligands are potent reductants that may contribute to the natural attenuation of subsurface contaminants. In the present study, we investigated the reactivity of Fe(II)-organothiol ligand complexes with nitroaromatic contaminants (NACs; ArNO(2)). Experimental results show that NACs are unreactive in Fe(2+)-only and ligand-only solutions but are reduced to the corresponding aniline compounds (ArNH(2)) in solutions containing both Fe(II) and a number of organothiol ligands. Observed reaction rates are highly dependent on the structure of the Fe(II)-complexing ligand, solution composition, Fe(II) speciation, and NAC structure. For two model ligands, cysteine and thioglycolic acid, observed pseudo-first order rate constants for 4-chloronitrobenzene reduction (k(obs); 1/s) are linearly correlated with the concentration of the respective 1:2 Fe(II)- organothiol complexes (FeL(2)(2-)), and k(obs) measurements are accurately predicted by k(obs) = k(FeL(2-)(2))[FeL(2-)(2)], where k(FeL(2-)(2)) = 1.70 (+/-0.59) 1/M/s and 26.0 (+/-4.8) 1/M/s for cysteine and thioglycolic acid, respectively. The high reactivity of these Fe(II) complexes is attributed to a lowering of the standard one-electron reduction potential of the Fe(III)/Fe(II) redox couple on complexation by organothiol ligands. The relative reactivity of a series of substituted NACs with individual Fe(II) complexes can be described by linear free-energy relationships with the apparent one-electron reduction potentials of the NACs. Tests also show that organothiol ligands can further promote NAC reduction indirectly by re-reducing the Fe(III) that forms when Fe(II) complexes are oxidized by reactions with the NACs.

Sponge carrier media provide a large surface area for biofilm support; however, little information is known about how to model their dual nature as a moving bed and as porous media. To investigate the interaction of mass transfer and detachment with bio-clogging, a novel biofilm model framework was built based on individual-based modelling, and hydrodynamics were modelled using the lattice Boltzmann method. The combined model structure enabled the simulation of oxygen and biomass distribution inside the porous network as well as inside the biofilm. In order to apply the model to moving bed biofilm reactors (MBBR), biofilm detachment due to abrasion (carrier collisions) was modelled to be dependent on intracarrier distance. In the initial growth stage, biofilm grew homogeneously on the internal skeleton after which a more discontinuous growth developed which significantly increased permeability. Low detachment rates caused clogging in the outer pores which limited growth of biofilm to the surface region of the sponge. High detachment rates on the surface enabled deeper oxygen penetration with higher internal biomass activity. The degree of clogging was also sensitive to the presence of extracellular polymeric substances because of its large spatial occupancy.

Activated Sludge Models (ASMs) are widely used for biological wastewater treatment plant design, optimisation and operation. In commonly used ASMs, the nitrification process is modelled as a one-step process. However, in some process configurations, it is desirable to model the concentration of nitrite nitrogen through a two-step nitrification process. In this study, the benchmark datasets published by the Water Environment Research Foundation (WERF) were used to develop a two-step nitrification model considering the kinetics of Ammonium Oxidising Bacteria (AOB) and Nitrite Oxidising Bacteria (NOB). The WERF datasets were collected from a chemostat reactor fed about 1,000 mg-NH3-N/L synthetic influent with at different sludge retention times of 20, 10 and 5-d, whereas the pH in the reactor varied in the range of 5.8 and 8.8. Supplemental laboratory batch experiments were conducted to assess the toxicity of nitrite-N on nitrifying bacteria. These tests suggested that 500 mg-N/L of nitrite at pH 7.3 was toxic to NOB and resulted in continuous decrease in bulk oxygen uptake rate. To model this phenomenon, a poisoning model was used instead of the traditional Haldane-type inhibition model. The poisoning model for NOB and AOB with different threshold poisonings for unionised NO2-N and NH3-N concentrations could successfully reproduce the three WERF datasets.

A computation model for inorganic composition of anaerobically digested sludge (ADS) was developed using 9 datasets taken from digesters at 9 different wastewater treatment plants. The model employed assumptions and calibration parameters based on stoichiometry and kinetics, combined with thermodynamic equilibrium computation. Through the model development process, the primarily precipitating solid species for Ca, Mg and Fe were determined to be CaHPO4, Mg(NH4)PO4·6H2O and FeCO3, respectively. Then, assuming that phosphorous (P), Ca and Mg contents in sludge biomass to be 1% of digested sludge volatile solid, respectively, that Al(OH)3 adsorb P with 0.05 mol-P/mol-Al(OH)3, and that CaHPO4 and FeCO3 to experience slow solid-to-solid reaction to CaCO3 and Fe3(PO4)2·8H2O with first-order reaction rates of 0.05 day-1 and 0.01 day-1 , respectively, the developed model successfully reproduced aqueous P, Ca and Mg concentrations of the datasets. The model predicted the average inorganic composition of the tested ADS inside the digester of P (as 52% aqueous and 20% inorganic solid), Ca (as 5% aqueous and 65% inorganic solid) and Mg (as 52% aqueous and 6% inorganic solid).