Soil Organic Matter and Phosphate Sorption on Natural and Synthetic Fe Oxides under in Situ Conditions.

Iron (Fe) oxides in soils are strong sorbents for environmentally important compounds like soil organic matter (SOM) or phosphate, while sorption under field conditions is still poorly understood. We installed polyvinyl chloride plastic bars which have been coated either with synthetic Fe or manganese (Mn) oxides for 30 days in a redoximorphic soil. A previous study revealed the formation of newly formed ("natural") Fe oxides along the Mn oxide coatings. This enables us to differentiate between sorption occurring onto the surfaces of synthetic versus natural Fe oxides. After removal of the bars, they were analyzed by nanoscale secondary ion mass spectrometry (NanoSIMS) to study the distribution of Fe (56Fe16O-), SOM (12C14N-), and phosphorus (31P16O2-) at the microscale. Image analysis of individual Fe oxide particles revealed a close association of Fe, SOM, and P resulting in coverage values up to 71%. Furthermore, ion ratios between sorbent (56Fe16O-) and sorbate (12C14N- and 31P16O2-) were smaller along the natural oxides when compared with those for synthetic Fe oxides. We conclude that both natural and synthetic Fe oxides rapidly sequester SOM and P (i.e., within 30 days) but that newly, natural formed Fe oxides sorbe more SOM and P than synthetic Fe oxides.

New Insights into the Formation and Properties of Wellbore Skin: Why We Have to Rethink the Concept.

The deposition of fine-grained material of low permeability on the borehole wall during drilling (wellbore skin) is a common problem affecting the operation and efficiency of water wells. Here, we present new data and novel insights from four excavated dewatering wells from a lignite surface mine. All wells have the same age, are of similar construction, and were sampled at two different depths each. The thickness of the skin layer increases with depth. Its composition and permeability is strongly influenced by the surrounding aquifer material. Nonuniform sediments of low permeability result in less permeable wellbore skin deposits. The presence of discontinuities in the skin layer may be a determining feature for the resulting flow to wells, especially with skin layers of low permeability. The presence of naturally occurring swelling clay (smectite) provides the skin layer with a significant self-sealing capacity.

Natural incorporation of mercury in bone.

Mercury (Hg) is a highly toxic element that causes bone defects and malformations. Structure and surface analyses using quantitative x-ray diffraction using the Rietveld method, High-Resolution Transmission Electron Microscopy and nanodiffraction analyses, and Fourier-Transformed Infrared spectroscopy showed that bone enriched naturally with Hg (≤ 2.3 %) contained Hg3PO4 [(Hg2)3(PO4)2] and HgO. Bone [mostly as apatite, verified as carboxyapatite Ca10(PO4)4(CO3)3(OH)2(s)] and cinnabar (HgS) dissolved releasing Hg+ (existing as dimer Hg22+) and PO43-, both of which became immobilized as (Hg2)3(PO4)2. Besides, released Hg2+ became oxidized to form HgO. The outcome of this work is novel, provided that only a handful of stable compounds of Hg22+ are found in nature.

Continuous-feed carbonation of waste incinerator bottom ash in a rotating drum reactor.

Carbonation is a key process in the aging of waste incinerator bottom ash (BA). The reaction with CO2 decreases the BA alkalinity and lowers the leachability of amphoteric trace metals. Passive ageing over several months is usually performed in intermittently mixed BA heaps. Here we aimed at accelerating the process in a rotating drum reactor continuously fed with the BA and the reactant gas (10 vol-% CO2, volumetric flow rate 60 L/min). In one test, the gas was heated and humidified. Since carbonation depends on the specific CO2-supply, experiments were conducted at varied BA residence time (60, 80, and 100 min). Residence time was calculated by mass balancing and confirmed by the breakthrough time of two tracers. Leachates and solid phase properties of the treated BA served to evaluate the carbonation performance. The residence time of BA could be adequately controlled by the reactor loading and feed rate. A residence time of 80 min was sufficient to reduce the BA leachability such as to comply with the German regulatory standards for non-hazardous waste, whereas the untreated BA was hazardous waste. Decreased alkalinity was indicated by lower leachate pH and Ca(OH)2 contents of the BA as compared to the input. Leachate concentrations of amphoteric trace metals (Pb, Zn, Cu) decreased by at least one order of magnitude while oxyanions became slightly more mobile upon carbonation. In view of relatively short residence times and stable process performance, the rotating drum reactor seems promising for a full-scale implementation of BA carbonation.

Antibacterial clay against gram-negative antibiotic resistant bacteria.

Antibiotic resistant bacteria persist throughout the world because they have evolved the ability to express various defense mechanisms to cope with antibiotics and the immune system; thus, low-cost strategies for the treatment of these bacteria are needed, such as the usage of environmental minerals. This paper reports the antimicrobial properties of a clay collected from Brunnenberg, Germany, that is composed of ferroan saponite with admixtures of quartz, feldspar and calcite as well as exposed or hidden (layered at inner regions) nano Fe(0). Based on the growth curves (log phase) of six antibiotic resistant bacteria (4 gram-negative and 2 gram-positive), we concluded that the clay acted as a bacteriostat; however, the clay was only active against the gram-negative bacteria (except for resilient Klebsiella pneumonia). The bacteriostatic mode of action was evidenced by the initial lack of Colony Forming Units on agar plates with growth registered afterward, certainly after 24h, and can be explained because interactions between membrane lipopolysaccharides and the siloxane surfaces of the clay. Labile or bioavailable Fe in the clay (extracted by EDTA or DFO-B) induced the quantitative production of HO as well as oxidative stress, which, nevertheless, did not account for by its bacteriostatic activity.

Role of bentonite clays on cell growth.

Bentonites, naturally occurring clays, are produced industrially because of their adsorbent capacity but little is known about their effects on human health. This manuscript reports on the effect of bentonites on cell growth behaviour. Bentonites collected from India (Bent-India), Hungary (Bent-Hungary), Argentina (Bent-Argentina), and Indonesia (Bent-Indonesia) were studied. All four bentonites were screened in-vitro against two human cancer cell lines [U251 (central nervous system, glioblastoma) and SKLU-1 (lung adenocarcinoma)] supplied by the National Cancer Institute (USA). Bentonites induced growth inhibition in the presence of U251 cells, and growth increment in the presence of SKLU-1 cells, showing that interactions between bentonite and cell surfaces were highly specific. The proliferation response for U251 cells was explained because clay surfaces controlled the levels of metabolic growth components, thereby inhibiting the development of high-grade gliomas, particularly primary glioblastomas. On the other hand, the proliferation response for SKLU-1 was explained by an exacerbated growth favoured by swelling, and concomitant accumulation of solutes, and their hydration and transformation via clay-surface mediated reactions.

Porosity and distribution of water in perlite from the island of Milos, Greece.

A perlite sample representative of an operating mine in Milos was investigated with respect to the type and spatial distribution of water. A set of different methods was used which finally provided a consistent view on the water at least in this perlite. Infrared spectroscopy showed the presence of different water species (molecular water and hydroxyl groups / strongly bound water). The presence of more than 0.5 mass% smectite, however, could be excluded considering the cation exchange capacity results. The dehydration measured by thermal analysis occurred over a wide range of temperatures hence confirming the infrared spectroscopical results. Both methods point to the existence of a continuous spectrum of water binding energies. The spatial distribution of water and/or pores was investigated using different methods (CT: computer tomography, FIB: scanning electron microscopy including focused ion beam technology, IRM: infrared microscopy). Computer tomography (CT) showed large macropores (20 - 100 µm) and additionally revealed a mottled microstructure of the silicate matrix with low density areas up to a few µm in diameter. Scanning electron microscopy (FIB) confirmed the presence of µm sized pores and IRM showed the filling of these pores with water. In summary, two types of pores were found. Airfilled 20 - 100 µm pores and µm-sized pores disseminated in the glass matrix containing at least some water. Porosity measurements indicate a total porosity of 26 Vol%, 11 Vol% corresponding to the µm-sized pores. It remains unsolved wether the water in the µm-sized pores entered after or throughout perlite formation. However, the pores are sealed and no indications of cracks were found which indicated a primary source of the water, i.e. water was probably entrapped by quenching of the lava. The water in these pores may be the main reason for the thermal expandability which results in the extraordinarily porous expanded perlite building materials.