Urs Eggenberger

Assessing the Cr(VI) reduction efficiency of a permeable reactive barrier using Cr isotope measurements and 2D reactive transport modeling

In Thun, Switzerland, a permeable reactive barrier (PRB) for Cr(VI) reduction by gray cast iron was installed in May 2008. The PRB is composed of a double array of vertical piles containing iron shavings and gravel. The aquifer in Thun is almost saturated with dissolved oxygen and the groundwater flow velocities are ca. 10-15m/day. Two years after PRB installation Cr(VI) concentrations still permanently exceed the Swiss threshold value for contaminated sites downstream of the barrier at selected localities. Groundwater δ(53/52)Cr(SRM979) measurements were used to track Cr(VI) reduction induced by the PRB. δ(53/52)Cr(SRM979) values of two samples downstream of the PRB showed a clear fractionation towards more positive values compared to four samples from the hotspot, which is clear evidence of Cr(VI) reduction induced by the PRB. Another downstream sample did not show a shift to more positive δ(53/52)Cr(SRM979) values. Because this latter location correlates with the highest downstream Cr(VI) concentration it is proposed that a part of the Cr(VI) plume is bypassing the barrier. Using a Rayleigh fractionation model a minimum present-day overall Cr(VI) reduction efficiency of ca. 15% was estimated. A series of 2D model simulations, including the fractionation of Cr isotopes, confirm that only a PRB bypass of parts of the Cr(VI) plume can lead to the observed values. Additionally, the simulations revealed that the proposed bypass occurs due to an insufficient permeability of the individual PRB piles. It is concluded that with this type of PRB a complete and long-lasting Cr(VI) reduction is extremely difficult to achieve for Cr(VI) contaminations located in nearly oxygen and calcium carbonate saturated aquifer in a regime of high groundwater velocities. Additional remediation action would limit the environmental impact and allow to reach target concentrations.

Mineralogy‐based quantitative precipitation and temperature reconstructions from annually laminated lake sediments (Swiss Alps) since AD 1580

[1] We present quantitative autumn, summer and annual precipitation and summer temperature reconstructions from proglacial annually laminated Lake Silvaplana, eastern Swiss Alps back to AD 1580. We used X-ray diffraction peak intensity ratios of minerals in the sediment layers (quartz qz, plagioclase pl, amphibole am, mica mi) that are diagnostic for different source areas and hydrometeorological transport processes in the catchment. XRD data were calibrated with meteorological data (AD 1800/ 1864–1950) and revealed significant correlations: mi/pl with SON precipitation (r = 0.56, p < 0.05) and MJJAS precipitation (r = 0.66, p < 0.01); qz/mi with MJJAS temperature (r = � 0.72, p < 0.01)and qz/am with annual precipitation (r = � 0.54, p < 0.05). Geological catchment settings and hydro-meteorological processes provide deterministic explanations for the correlations. Our summer temperature reconstruction reproduces the typical features of past climate variability known from independent data sets. The precipitation reconstructions show a LIA climate moister than today. Exceptionally wet periods in our reconstruction coincide with regional glacier advances. Citation: Trachsel, M., U. Eggenberger, M. Grosjean, A. Blass, and M. Sturm (2008), Mineralogy-based quantitative precipitation and temperature reconstructions from annually laminated lake sediments (Swiss Alps) since AD 1580, Geophys. Res. Lett., 35, L13707, doi:10.1029/2008GL034121.

The Molecular Environment of Phosphorus in Sewage Sludge Ash: Implications for Bioavailability

Producing a P fertilizer from sewage sludge ash (SSA) is a strategy to efficiently recycle P from a secondary raw material. The P speciation in four SSAs was characterized before and after the removal of heavy metals by a thermo-chemical treatment that involved CaCl addition. We chose complementary techniques to determine the direct P speciation, including X-ray powder diffraction, solid-state P direct-polarization magic-angle spinning nuclear magnetic resonance, and X-ray absorption near edge structure. Results from these techniques were compared with operational and functional speciation information obtained from a sequential P extraction and a plant biotest with Italian ryegrass grown on a soil-sand mixture with little available P. The speciation of P in untreated and thermo-chemically treated SSAs depended on their elemental composition. At a molar ratio of Ca:P ≤ 2, SSAs contained combinations of polymorphs of AlPO, β-tricalcium phosphate, and apatite-like P species. In SSAs with a molar ratio of Ca:P > 2, an apatite-like molecular environment was predominant. The thermo-chemical process induced an increase in crystalline phases and enhanced the crystallinity of the P species. The structural order of the bulk sample was the most decisive parameter in controlling the P availability of the studied SSAs to plants. We conclude that, to produce a high-quality fertilizer and despite of the successful heavy metal removal, the thermo-chemical process requires further development toward enhanced P bioavailability.

Chemical associations and mobilization of heavy metals in fly ash from municipal solid waste incineration

This study focusses on chemical and mineralogical characterization of fly ash and leached filter cake and on the determination of parameters influencing metal mobilization by leaching. Three different leaching processes of fly ash from municipal solid waste incineration (MSWI) plants in Switzerland comprise neutral, acidic and optimized acidic (+ oxidizing agent) fly ash leaching have been investigated. Fly ash is characterized by refractory particles (Al-foil, unburnt carbon, quartz, feldspar) and newly formed high-temperature phases (glass, gehlenite, wollastonite) surrounded by characteristic dust rims. Metals are carried along with the flue gas (Fe-oxides, brass) and are enriched in mineral aggregates (quartz, feldspar, wollastonite, glass) or vaporized and condensed as chlorides or sulphates. Parameters controlling the mobilization of neutral and acidic fly ash leaching are pH and redox conditions, liquid to solid ratio, extraction time and temperature. Almost no depletion for Zn, Pb, Cu and Cd is achieved by performing neutral leaching. Acidic fly ash leaching results in depletion factors of 40% for Zn, 53% for Cd, 8% for Pb and 6% for Cu. The extraction of Pb and Cu are mainly limited due to a cementation process and the formation of a PbCu0-alloy-phase and to a minor degree due to secondary precipitation (PbCl2). The addition of hydrogen peroxide during acidic fly ash leaching (optimized acidic leaching) prevents this reduction through oxidation of metallic components and thus significantly higher depletion factors for Pb (57%), Cu (30%) and Cd (92%) are achieved. The elevated metal depletion using acidic leaching in combination with hydrogen peroxide justifies the extra effort not only by reduced metal loads to the environment but also by reduced deposition costs.

Derivatization technique to increase the spectral selectivity of two-dimensional Fourier transform infrared focal plane array imaging: analysis of binder composition in aged oil and tempera paint.

The interpretation of standard Fourier transform infrared spectra (FT-IR) on oil-based paint samples often suffers from interfering bands of the different compounds, namely, binder, oxidative aging products, carboxylates formed during aging, and several pigments and fillers. The distinction of the aging products such as ketone and carboxylic acid functional groups pose the next problem, as these interfere with the triglyceride esters of the oil. A sample preparation and derivatization technique using gaseous sulfur tetrafluoride (SF4), was thus developed with the aim to discriminate overlapping signals and achieve a signal enhancement on superposed compounds. Of particular interest in this context is the signal elimination of the broad carboxylate bands of the typical reaction products developing during the aging processes in oil-based paints, as well as signal interference originating from several typical pigments in this spectral range. Furthermore, it is possible to distinguish the different carbonyl-containing functional groups upon selective alteration. The derivatization treatment can be applied to both microsamples and polished cross sections. It increases the selectivity of the infrared spectroscopy technique in a fundamental manner and permits the identification and two-dimensional (2D) localization of binder components in aged paint samples at the micrometer scale. The combination of SF4 derivatization with high-resolution 2D FT-IR focal plane array (FPA) imaging delivers considerable advances to the study of micro-morphological processes involving organic compounds.

A soil acidification study using the PROFILE model on two contrasting regions in Switzerland

Abstract The steady-state soil chemistry model PROFILE was used to calculate the chemical status of forest soils under present deposition loads for two areas with dissimilar ecosystem properties. Two regions in Switzerland, with contrasting bedrock geology were selected to be investigated in detail: 88 locations in the Jura Mountains, representative for carbonate bedrock and 91 locations in the Ticino Area dominated by metamorphic crystalline host rocks. Weathering rates calculated for the key regions cover the tremendous range between 0.013 and 25 keq ha −1 yr −1 . In the Ticino Area, the effect of increased abundance of relatively fast weathering silicates (epidote, hornblende and plagioclase) on the weathering rate is apparently masked by the total effects of the physical conditions applied and by the variation in the deposition load. In the Jura Mountains, generally high weathering rates occur with about 50% of the sites yielding rates above 1 keq ha −1 yr −1 . In many of the sites investigated, however, carbonates have already been dissolved completely in the soil horizons of interest resulting in very low weathering rates. The critical load of actual acidity was calculated according to: CL Acidity = R Weathering −ANC Leaching , where alkalinity leaching is estimated by keeping the base cation to aluminum molar ratio at the critical limit of 1 at steady-state. The minimum critical load calculated was 0.2 keq ha −1 yr −1 and the maximum was 6.2 keq ha −1 yr −1 . Comparing the cumulative frequency distributions of critical loads of actual acidity for forest soils in the individual areas it can be seen that the differences between the key regions are less substantial than with the weathering rates. Critical loads of acidity for the Ticino Area range from 1 to 3.9 keq ha −1 yr −1 . Sites yielding the lowest critical loads of acidity are observed in the Jura Mountains. Among these apparent sensitive soils are soils with intermediate or high weathering rates, although it has depleted topsoil layers. Within the context of this model application, it becomes apparent that the sensitivity of these soils with respect to acidification is also governed by the alkalinity leaching term and not only by the susceptibility of its minerals to weathering.

Influence of sample matrix on the alkaline extraction of Cr(VI) in soils and industrial materials

An accurate and efficient determination of the highly toxic Cr(VI) in solid materials is important to determine the total Cr(VI) inventory of contaminated sites and the Cr(VI) release potential from such sites into the environment. Most commonly, total Cr(VI) is extracted from solid materials following a hot alkaline extraction procedure (US EPA method 3060A) where a complete release of water-extractable and sparingly soluble Cr(VI) phase is achieved. This work presents an evaluation of matrix effects that may occur during the hot alkaline extraction and in the determination of the total Cr(VI) inventory of variably composed contaminated soils and industrial materials (cement, fly ash) and is compared to water-extractable Cr(VI) results. Method validation including multiple extractions and matrix spiking along with chemical and mineralogical characterization showed satisfying results for total Cr(VI) contents for most of the tested materials. However, unreliable results were obtained by applying method 3060A to anoxic soils due to the degradation of organic material and/or reactions with Fe2+-bearing mineral phases. In addition, in certain samples discrepant spike recoveries have to be also attributed to sample heterogeneity. Separation of possible extracted Cr(III) by applying cation-exchange cartridges prior to solution analysis further shows that under the hot alkaline extraction conditions only Cr(VI) is present in solution in measurable amounts, whereas Cr(III) gets precipitated as amorphous Cr(OH)3(am). It is concluded that prior to routine application of method 3060A to a new material type, spiking tests are recommended for the identification of matrix effects. In addition, the mass of extracted solid material should to be well adjusted to the heterogeneity of the Cr(VI) distribution in the material in question.

Early Viridian Pigment Composition CHARACTERIZATION OF A (HYDRATED) CHROMIUM OXIDE BORATE PIGMENT

Abstract Pigment analyses on more than 90 paintings dating from between 1885 and 1943 (A. Jawlensky, W. Kandinsky, F. Hodler and C. Amiet) have revealed that the majority of samples with chromium oxide hydrate green contain a spectroscopically conspicuous by-product. With the aim of tracking down the origin of this component, the so-called Guignet green, a variation of viridian produced by calcination, was systematically synthesized under varying conditions. The resulting products were characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, energy dispersive spectrometry, electron microprobe microanalysis with wavelength dispersive spectrometry, X-ray diffraction, thermogravimetric analysis, secondary electron and backscattered electron imaging by scanning electron microscopy, polarized light microscopy and colorimetry. The composition of pigment products varies with the calcination conditions. Higher temperatures and/or longer calcination times lead to an insoluble borate matrix incorporating chromium oxide particles. The result is an amorphous chromium oxide borate Cr2O3·(xH2O)–Cr3BO6 polymorph with low water content. Interpreting chromium oxide hydrate green samples within this context, it turns out that calcination conditions in the past were highly variable, leaving behind considerable amounts of borates in the final product. Current data covering more than 60 paintings by Jawlensky suggest that the use of a specific production batch can be resolved in time. Identification of borates in chromium oxide hydrate green samples from paintings may thus provide information about the origin of the paint product used.

Chemistry and mineralogy of municipal solid waste incinerator bottom ash

Abstract A petrographic study was conducted on a suite of bottom ash samples from 28 municipal solid waste incinerators in Switzerland. Chemical and mineralogical analyses of bottom ash from waste combustors with comparable technology show similar major oxide composition. A significant decrease of SiO2 was observed in comparison to the chemical composition of bottom ash from 10 years ago. In contrast to major oxide contents, heavy metal concentrations vary significantly in the bottom ash samples, but without any correlation to the type of input waste or plant operating conditions. Similar types and contents of crystalline phases were observed in all samples. The content of newly formed melilite increases with decreasing bulk Si/Ca ratio, indicating that the type of Ca-Mg-Al-silicates crystallizing during incineration and cooling follow petrogenetic rules. A considerable recycling potential for ferrous and non-ferrous metals was identified in the bottom ash. Optimized mechanical metal separation technologies could reduce the waste volume, heavy metal content, H2 production, and exothermic reactions of the bottom ash in landfills and might be economically viable.

Recrystallization of Amorphized α-TCP

Phase-pure α-TCP powder was milled using a high-energy planetary mill to obtain a partially X-ray amorphous material. Calcination at temperatures between 350 and 600 °C was employed to recrystallize the powder. The phase composition as a function of calcination time and temperature was determined in-situ using high-temperature XRD equipment. It was found that the amorphous fraction recrystallized mainly to α-TCP, with only small amounts of β-TCP formed. At low temperatures (≤ 450 °C), a stable composition with approximately 85 wt-% α-TCP was found once 100% crystallinity was reached. The time required to reach full crystallinity depended on the calcination temperature. For temperatures > 450 °C a slow transformation to β-TCP was observed. The transformation rate depended on the calcination temperature and on the milling intensity. A moderately milled powder recrystallized to α-TCP, followed by a slow transformation to β-TCP at 600 °C, whereas an intensely milled powder also recrystallized to α-TCP, followed by a fast transformation to β-TCP at the same temperature.