Municipal waste incineration fly ashes: from a multi-element approach to market potential evaluation.

BACKGROUND: Fly ashes from municipal solid waste incineration contain significant amounts of (technology critical) elements. Processes to recover Cu or Zn are already in practice, but it still remains difficult to evaluate the full secondary resource potential of the ashes. One reason is the absence of a worldwide comparable analytical basis for detailed market analyses. To encounter this, (i) an advice on how to analyse 65 elements after microwave-assisted digestion by ICP-OES and ICP-MS is delivered, (ii) the heterogeneity (hours to annual cycle) is evaluated for a incineration plant, (iii) leaching efficiency with three different eluents and (iv) the market potential of the elements as commodities are evaluated. RESULTS AND CONCLUSIONS: Aqua regia digestion was found to be sufficient to evaluated the recovery potential; except for the mass constituents Al, Si, Sn, Ti and the trace components Cr, Hf, Nb, U and W, for which HF-containing digestions delivered better recoveries. On different time scales, ashes were very homogenous and HCl- as well as H2SO4-supported leaching delivered, satisfying results within an hour (exceptions are, e.g., Bi and Sb). By applying characterisation factors of the life cycle assessment impact category "Resource depletion-minerals and metals" supplemented by the list of critical raw materials of the EU: Ag, Bi, Cd, Ga, In and Sb are most interesting elements to be recovered in future activities.

Sediment water (interface) mobility of metal(loid)s and nutrients under undisturbed conditions and during resuspension.

The contribution of the release from sediments to the overall river Trave budget was evaluated with respect to 16 metal(loid)s, three non-metals and the ions PO43- and NH4+. To consider undisturbed conditions and sediment resuspension in-situ dialyses-based and ex-situ suction-based pore water sampling was complemented by sequential extraction and suspension reactor experiments. In the investigated sediments, representative for the study area, metal(loid) partitioning between the different geochemical fractions was very similar despite some higher contaminated spots. Pore water investigations emphasis that profiling and peeper based analyses are comparable and deliver an indication that sediment dwelling organisms are exposed to elevated metal(loid) concentrations. However, higher toxicity of the contaminated sediments compared to the sediment treated as background reference was not revealed. During resuspension only few metal(loid)s exceeded specified guideline values. The maximum amounts released, were only between 10-5 and 10-1% of the average daily load of the river Trave per ton of suspended sediment. Overall the "most pristine sediments" and not the potentially hazardous materials in the study area are found to be from highest concern. The results support requests to better include fractionation and speciation demands in legal assessments of sediments.

Impact of mechanical disturbance and acidification on the metal(loid) and C, P, S mobility at the sediment water interface examined using a fractionation meso profiling ICP-QQQ-MS approach.

The impact of mechanical disturbance and oxygen induced acidification on the concentration and size fractionation of the 12 metal(loid)s As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sb, Tl, V and the polyatomic nonmetals C, P and S in the pore water was studied. Using the meso profiling and sampling system (messy) 12 pore water depth profiles were sampled from two incubation experiments undertaken in parallel, which were both mechanically disturbed in the lab and subsequently exposed to a different air supply. In parallel to the low invasive, automated sampling process the redox potential, the pH value and the O2 concentration were detected. Simultaneous quantification of all analytes by inductively coupled plasma-triple quad-mass spectrometry in the two different size classes dissolved (<0.45 µm) and colloidal (0.45-16 µm) showed: i) the predominant influence of the pH on the mobility of metals; ii) the mobility of metalloids was strongly impacted by the mechanical disturbance; and iii) the colloidal release is less important except for Fe, P, and Ni.

Metal(loid) speciation and size fractionation in sediment pore water depth profiles examined with a new meso profiling system.

In an exemplary incubation study with an anaerobic sediment sampled at an oxbow of the river Lahn in Germany (50°18'56.87″N; 7°37'41.25″E) and contaminated by former mining activity, a novel meso profiling and sampling system (messy) is presented. Messy enables a low invasive, automated sampling of pore water profiles across the sediment water interface (SWI), down to ∼20 cm depth with a spacial resolution of 1 cm. In parallel to the pore water sampling it measures physicochemical sediment parameters such as redox potential and pH value. In an incubation experiment of 151 days the ability of the setup was proven to address several different aspects relevant for fresh water and marine sediment studies: (i) The influence of mechanical disturbance and oxygen induced acidification on the mobility of 13 metals and metalloids (Cd, Co, Cu, Fe, Mn, Mo, Ni, Sb, U, V, Zn) was quantified based on 11 profiles. The analytes were quantified by inductively coupled plasma-mass spectrometry. Three groups of elements were identified with respect to the release into the pore water and the overlying water under different experimental conditions. (ii) The capability to investigate the impacts of changing physicochemical sediment properties on arsenic and antimony (III/V) speciation is shown. (iii) An approach to obtain information on size fractionation effects and to address the colloidal pore water fractions (0.45 µm-16 µm) was successfully conducted for the elements Ag, As, Cu, Fe and Mn.

A Framework to Evaluate the Impact of Armourstones on the Chemical Quality of Surface Water.

Today, basic requirements for construction works include the protection of human health and of the environment. In the tension area between economic demands, circular flow economy and environmental safety, a link between the results from standardized leaching tests and the respective environmental quality standards must be created. To derive maximum release limits of metals and metalloids for armourstones in hydraulic engineering, this link is accomplished via a simple model approach. By treating natural materials and industrial by-products the same way, the article delivers an overview on the recent regulative situation in Europe as well as describes and discusses an innovative approach to derive maximum release limits for monolithic construction products in hydraulic engineering on a conceptual level. On a practical level, a list of test parameters is derived by connecting an extensive dataset (seven armourstone materials with five repetitions and 31 elements tested with the worldwide applied dynamic surface leaching test) with surface water quality standards and predicted no effect concentrations. Finally, the leaching tests results are compared with the envisaged maximum release limits, offering a direct comparison between natural materials and industrial by-products.

Metal and Metalloid Size-Fractionation Strategies in Spatial High-Resolution Sediment Pore Water Profiles.

Sediment water interfaces (SWIs) are often characterized by steep biogeochemical gradients determining the fate of inorganic and organic substances. Important transport processes at the SWI are sedimentation and resuspension of particulate matter and fluxes of dissolved materials. A microprofiling and micro sampling system (missy), enabling high resolution measurements of sediment parameters in parallel to a direct sampling of sediment pore waters (SPWs), was combined with two fractionation approaches (ultrafiltration (UF) and cloud point extraction (CPE)) to differentiate between colloidal and dissolved fractions at a millimeter scale. An inductively coupled plasma-quadrupole mass spectrometry method established for volumes of 300 µL enabled the combination of the high resolution fractionation with multi-element analyzes. UF and CPE comparably indicated that manganese is predominantly present in dissolved fractions of SPW profiles. Differences found for cobalt and iron showed that the results obtained by size-dependent UF and micelle-mediated CPE do not necessarily coincide, probably due to different fractionation mechanisms. Both methods were identified as suitable for investigating fraction-related element concentrations in SPW along sediment depth profiles at a millimeter scale. The two approaches are discussed with regard to their advantages, limitations, potential sources of errors, further improvements, and potential future applications.

Can cloud point-based enrichment, preservation, and detection methods help to bridge gaps in aquatic nanometrology?

Coacervate-based techniques are intensively used in environmental analytical chemistry to enrich and extract different kinds of analytes. Most methods focus on the total content or the speciation of inorganic and organic substances. Size fractionation is less commonly addressed. Within coacervate-based techniques, cloud point extraction (CPE) is characterized by a phase separation of non-ionic surfactants dispersed in an aqueous solution when the respective cloud point temperature is exceeded. In this context, the feature article raises the following question: May CPE in future studies serve as a key tool (i) to enrich and extract nanoparticles (NPs) from complex environmental matrices prior to analyses and (ii) to preserve the colloidal status of unstable environmental samples? With respect to engineered NPs, a significant gap between environmental concentrations and size- and element-specific analytical capabilities is still visible. CPE may support efforts to overcome this "concentration gap" via the analyte enrichment. In addition, most environmental colloidal systems are known to be unstable, dynamic, and sensitive to changes of the environmental conditions during sampling and sample preparation. This delivers a so far unsolved "sample preparation dilemma" in the analytical process. The authors are of the opinion that CPE-based methods have the potential to preserve the colloidal status of these instable samples. Focusing on NPs, this feature article aims to support the discussion on the creation of a convention called the "CPE extractable fraction" by connecting current knowledge on CPE mechanisms and on available applications, via the uncertainties visible and modeling approaches available, with potential future benefits from CPE protocols.

New microprofiling and micro sampling system for water saturated environmental boundary layers.

The spatial high resolution of a microprofiling system was combined with the multi element capability of ICP-MS to enable a better understanding of element distributions and related processes across environmental boundary layers. A combination of a microprofiling system with a new micro filtration probe head connected to a pump and a fraction collector (microprofiling and micro sampling system, missy) is presented. This enables for the first time a direct, dynamic, and high resolution automatic sampling of small water volumes (<500 µL) from depth profiles of water saturated matrices (e.g., sediments, soils, biofilms). Different membrane cut-offs are available, and resolutions of a few (matrices with a high physical resistance) to a submillimeter scale (matrices with low physical resistance) can be achieved. In this Article, (i) the modular setups of two missys are presented; (ii) it is demonstrated how the micro probe heads are manufactured; (iii) background concentrations and recoveries of the system as well as (iv) exemplary results of a sediment water interface are delivered. On the basis of this, potentials, possible sources of errors, and future applications of the new missy are discussed.

ICP-MS-based characterization of inorganic nanoparticles--sample preparation and off-line fractionation strategies.

Validated and easily applicable analytical tools are required to develop and implement regulatory frameworks and an appropriate risk assessment for engineered nanoparticles (ENPs). Concerning metal-based ENPs, two main aspects are the quantification of the absolute mass concentration and of the "dissolved" fraction in, e.g., (eco)toxicity and environmental studies. To provide information on preparative aspects and on potential uncertainties, preferably simple off-line methods were compared to determine (1) the total concentration of suspensions of five metal-based ENP materials (Ag, TiO2, CeO2, ZnO, and Au; two sizes), and (2) six methods to quantify the "dissolved" fraction of an Ag ENP suspension. Focusing on inductively coupled plasma-mass spectrometry, the total concentration of the ENP suspensions was determined by direct measurement, after acidification and after microwave-assisted digestion. Except for Au 10 nm, the total concentrations determined by direct measurements were clearly lower than those measured after digestion (between 61.1 % for Au 200 nm and 93.7 % for ZnO). In general, acidified suspensions delivered better recoveries from 89.3 % (ZnO) to 99.3 % (Ag). For the quantification of dissolved fractions two filtration methods (ultrafiltration and tangential flow filtration), centrifugation and ion selective electrode were mainly appropriate with certain limitations, while dialysis and cloud point extraction cannot be recommended. With respect to precision, time consumption, applicability, as well as to economic demands, ultrafiltration in combination with microwave digestion was identified as best practice.