Synthesis of [13C]- and [14C]-labeled phenolic humus and lignin monomers

Natural phenolic monomers are ubiquitous in the environment and are involved in the stabilization of atmospheric carbon and the transformation of xenobiotics. Investigations on the stabilization of phenolic carbons and their environmental fate are hampered by the unavailability of commercial [13C]- and [14C]-labeled phenols. Here we report the complete chemical synthesis of the lignin and humus structural monomers p-coumaric, ferulic, and caffeic acids, p-hydroxybenzaldehyde, protocatechualdehyde, vanillin, catechol, and guaiacol, uniformly [13C]- or [14C]-labeled in the aromatic ring, starting from commercially available [U-ring-13C]- or [U-ring-14C]-labeled phenol. The synthesis of these compounds involved selective ortho-hydroxylation of the aromatic ring, Friedel-Crafts alkylation, and Knoevenagel condensation. [U-ring-13C]- or [U-ring-14C]-p-coumaric acid was synthesized via p-hydroxybenzaldehyde with a 75% yield with respect to phenol. Synthesis of [U-ring-13C]- or [U-ring-14C]-ferulic acid, consisting of six single steps via guaiacol and vanillin, had an overall yield of up to 45%. Uniformly ring-labeled caffeic acid was synthesized either via catechol and protocatechualdehyde in five single steps, yielding [U-ring-14C]-caffeic acid with a 37% yield, or via guaiacol, vanillin, and ferulic acid in seven steps, yielding [U-ring-13C]-caffeic acid with an 18% yield. Ferulic acid, [14C]-labeled at beta-C of the propenoic side chain, was synthesized from [2-14C]-malonic acid under Knoevenagel conditions with a 67% yield with respect to malonic acid. Demethylation of the [beta-14C]-ferulic acid with BBr3 in CH3CN resulted in [beta-14C]-caffeic acid with a 62% yield. All [U-ring-13C]-labeled phenolic products were analyzed by 13C nuclear magnetic resonance (13C-NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS).     

Desorption of arsenic from clay and humic acid-coated clay by dissolved phosphate and silicate

Arsenic (As) contaminated aquifers contain iron minerals and clays that strongly bind As at their surfaces. It was suggested that As mobilization is driven by natural organic matter (including fulvic acids (FA) and humic acids (HA)) present in the aquifers either via providing reducing equivalents for reductive dissolution of Fe(III) (hydr)oxides or via competitive desorption of As from the mineral surfaces. In the present study we quantified sorption of As(III) and As(V) to Ca(2+)-homoionized illite (IL) and to kaolinite (Kao) as well as to HA-coated clays, i.e., illite-HA (IL-HA) and kaolinite-HA (Kao-HA) at neutral pH. Clay-HA complexes sorbed 28-50% more As than clay-only systems upon addition of 100μM As(III)/As(V) to 0.5g of clay or HA-clay with Ca(2+) probably playing an important role for HA binding to the clay surface and As binding to the HA. When comparing sorption of As(V) and As(III) to clay and HA-clay complexes, As(V) sorption was generally higher by 15-32% than sorption of As(III) to the same complexes. IL and IL-HA sorbed 11-28% and 6-11% more As compared to Kao and Kao-HA, respectively. In a second step, we then followed desorption of As from Kao, Kao-HA, IL and IL-HA by 100 and 500μM phosphate or silicate both at high (0.41-0.77μmol As/g clay), and low (0.04 to 0.05μmol As/g clay) As loadings. Phosphate desorbed As to a larger extent than silicate regardless of the amount of As loaded to clay minerals, both in the presence and absence of HA, and both for illite and kaolinite. At high loadings of As, the desorption of both redox species of As from clay-HA complexes by phosphate/silicate ranged from 32 to 72% compared to 2-54% in clay only systems meaning that As was desorbed to a larger extent from HA-coated clays compared to clay only systems. When comparing As(III) desorption by phosphate/silicate to As(V) desorption in high As-loading systems, there was no clear trend for which As species is desorbed to a higher extent in the four clay systems meaning that both As species behave similarly regarding desorption from clay surfaces by phosphate/silicate. Similarly, no significant differences were found in high As-loading systems in the amount of As desorbed by phosphate/silicate when comparing Kao vs. IL and Kao-HA vs IL-HA systems meaning that both clay types behave similarly regarding desorption of As by phosphate/silicate. At low As loadings, up to 80% of As was desorbed by phosphate and silicate with no noticeable differences being observed between different As species, different types of clay, clay vs clay-HA or the type of desorbant (phosphate and silicate). The results of this study showed that HA sorption to Ca(2+)-homoionized clay minerals can increase As binding to the clay although the As sorbed to the clay-HA is also released to a greater extent by competing ions such as phosphate and silicate. Desorption of As depended on the initial loadings of As onto the clay/clay-HA. Based on our results, the effect of humic substances on sorption of As and on desorption of As by phosphate and silicate has to be considered in order to fully understand and evaluate the environmental behavior of As in natural environments.     

Thiourea leaching of gold from processed municipal solid waste incineration residues

Incineration is one of the key technologies in disposal of municipal waste, which produces municipal solid waste incineration (MSWI) residues with high valuable metal contents. The recycling strategy for the MSWI residues is typically focused on the recovery of scrap metals yielding processed municipal solid waste incineration residues (PIR) as the main byproduct. However, the PIR still contains valuable metals, particularly gold, which cannot be extracted by conventional methods. Here, we evaluated the feasibility of using the 0.5–2.0 mm grain size fraction of PIR containing 28.82 ± 1.62 mg/kg of gold as raw material for a two-stage extraction process. In the first stage the alkalic fine-grained PIR was acidified with a solution of 20% (v/v) of HCl-containing flue gas cleaning liquid that is obtained by the municipal waste incineration plant itself as a waste product. In the second stage we leached the acidified fine-grained PIR by thiourea with Fe³⁺ as an oxidant. Application of the thiourea-Fe³⁺ leaching system resulted in recovery of 16.4 ± 1.56 mg/kg of gold from the fine-grained PIR within 6 h of incubation. Due to high gold market prices, upscaling of the suggested technology can represent a suitable strategy for gold recovery from PIR and other MSWI residues.