Precious metals and rare earth elements in municipal solid waste – Sources and fate in a Swiss incineration plant

In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2 mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are essential for the improvement of resource recovery in the Thermo-Re® process.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

PCDDs and PCDFs in sewage sludge, river and lake sediments from south west Germany

Sewage sludges and sediments of rivers and lakes are sinks for “persistent” organic compounds entering the environment. These matrices are therefore useful in the assessment of local and global pollution with certain compounds or classes of compounds. In recent years we have analyzed sediments of the rivers Neckar, Rhine, and Danube, from Lake Constance, and samples of sewage sludge from municipal waste water treatment plants of south-west Germany for PAH, phthalates, organochlorine pesticides, and PCBs. ¹ We have now analyzed a number of these samples for PCDDs and PCDFs. Isomer-specific analyses for 2,3,7,8-subsituted PCDDs/PCDFs were carried out in all cases.

In all samples PCDDs could be detected, and in most cases PCDFs as well. 2,3,7,8-TCDD was never detected at a detection limit of 0.01 ppb. In sediments (14 samples) the total PCDDs ranged from 0.1 to 2.9 ppb and PCDFs from “not detectable” to 1.2 ppb. The highest concentration for a 2,3,7,8-substituted PCDD^* was found for 1,2,3,6,7,8-hexaCDD with 0.06 ppb. In sewage sludges (15 samples) the total PCDDs ranged from 4 to 65 ppb and PCDFs from 1 to 7 ppb. The highest concentration for a 2,3,7,8-substituted PCDD^* was found for 1,2,3,6,7,8-hexaCDD with 0.57 ppb.

Comparison of PCDD/PCDF patterns of congeners and isomers for the sewage sludge and river sediment samples with those of stack gas emissions of waste incinerators and of pentachlorophenol allows the conclusion that the main source of PCDDs and PCDFs found in these samples is pentachlorophenol. Results of the Lake Constance sediment core indicate that here the atmospheric immission from waste incineration might be predominant.     

Dissolved Oxygen and Nutrient Fluxes Across the Sediment–Water Interface of the Neckar River,Germany: In Situ Measurements and Simulations

A benthic in situ flume and a 1D biogeochemical sediment model to evaluate solute fluxes across the sediment–water interface have been developed. The flume was successfully used to determine oxygen and nutrient fluxes at various locations of the Neckar River in Germany. The experimental results were linked with vertical pore water concentration profiles and independently verified with the model. By combining experimental and model results we assessed the influence of dissolved oxygen concentrations in the water column and the availability of degradable organic matter on sediment oxygen demand. The results and the derived relations can be used to parameterize the sediment module of large scale water quality models, allowing one to assess the influence of sediment–water interactions on various aspects of river water quality. Moreover, the biogeochemical sediment model can help to improve the general understanding of the processes governing solute concentrations and fluxes in sediments and across their interfaces.     

Untersuchungen zum ?kotoxikologischen Sch?digungspotenzial und Erosionsrisiko von kontaminierten Sedimenten in staugeregelten Flüssen

Schwebstoffgebundene Schadstoffe werden durch Sedimentation der Wasserphase und damit der Verfügbarkeit für viele aquatischen Organismen entzogen. W?hrend bei durchschnittlichen hydrologischen. Verh?ltnissen die Freisetzung von Schadstoffen aus stabil gelagerten Sedimenten meist weitgehend unterbunden wird, besteht bei Hochwassereignissen die Gefahr einer Remobilisierung von kontaminierten Ablagerungen. In diesem Beitrag wird ein kombiniertes ?kotoxikologisches und hydraulisches Untersuchungssystem zur Untersuchung der ?kotoxikologischen Belastung und des Erosionsrisikos von Sedimenten vorgestellt. Der integrierte Ansatz wurde am staugeregelten Neckar angewendet, um das Sch?digungspotenzial und die Gefahr einer Remobilisierung an Sedimentbohrkernen der Stauhaltung Lauffen sowie an Schwebstoffen zweier extremer Hochwasser zu überprüfen. Für die Bohrkernsegmente unterhalb einer Erosionsdiskordanz konnte eine sprunghafte Zunahme der ?kotoxikologischen Belastung ermittelt werden. Bei Hochwasserereignissen mit einer 5-j?hrlichen Wiederkehrwahrscheinlichkeit (=HQ₅) k?nnen prinzipiell alle Sedimente, auch die st?rker kontaminierten und erosionsresistenteren Altsedimente, remobilisiert werden. W?hrend der Hochwasserereignisse (HQ₁₅ bis HQ₂₀) kam es zu einer deutlichen Erh?hung des cytotoxischen und mutagenen Sch?digungspotenzials der Schwebstoffe im Vergleich zu einem mittleren Hochwasser im Jahre 1995/96 (HQ₁) Dies schien zumindest teilweise auf die Remobilisierung hochkontaminierter Altsedimente zurückzuführen zu sein.