Analysis and occurrence of bromate in raw water and drinking water

A method for the trace-level determination of bromate in raw and drinking water is reported. The procedure combines the quantitation of bromate by ion chromatography with a concentration step which in the main is composed of an unselective enrichment of all water constituents by means of a rotatory evaporator and a selective removal of the chloride ions. With this method, the reliable determination of bromate in raw and drinking waters is possible down to concentrations of at least 1 μg/L. The method is used for systematic examinations in several German waterworks which use ozone for the preparation of drinking water. The resulting data clearly prove that during the ozonation of bromide-containing waters, bromate is produced, whereby the concentration of bromate in the ozonated raw water can exceed 10 μg/L. Some correlations between the amount of bromate and the respective conditions of ozonation are pointed out.     

高纬电离层中非麦克斯韦分布等离子体的非相干散射谱的模拟

使用一个修正的双麦克斯韦分布函数，通过最小均方适应技术使它与高纬电离层Ｆ区中离子的非麦克斯韦速度分布函数相适配．结果表明，使用这样的分布函数可以简化非相干散射谱的计算，并有助于简化高纬地区电离层非相干散射谱的反演．     

Ion probe dating of a migmatite in SW Sweden: the fate of zircon in crustal processes

A migmatitic orthogneiss in the Western Segment in the Sveconorwegian Province of the Baltic Shield was dated using the ion-probe U–Pb method on zircon grains, which were also analysed for rare earth elements. Mesosome zircons have 1.605±0.010 Ga magmatic cores, which places the gneiss protolith in the same 1.61–1.59 Ga time bracket as continental arc-related gneisses, abundant in this part of the Sveconorwegian Province. These cores show REE profiles with strong HREE enrichment, positive Ce- and negative Eu-anomalies, typical of magmatic zircon. Migmatite leucosomes are folded and parallel with or slightly discordant to the fabric. They contain a small population of zircon with cores and metamorphic rims, which are interpreted as xenocrysts incorporated in the leucosome during melting of the mesosome. CL-bright metamorphic embayments and rims on xenocrysts reflect 1.01±0.05 Ga Sveconorwegian metamorphic reworking. Ce-anomalies are nearly absent and Eu-anomalies are reduced relative to igneous spots. This is probably a feature of fluid controlled environments where Ce and Eu oxidation states are buffered by the metamorphic fluid. From this and discordant rims from the mesosome we also conclude that the rims formed by reworking of the older zircon where the Pb-loss was also fluid induced. In the leucosome veins, magmatic acicular zircon gives 0.92±0.01 Ga, ascribed to the crystallisation of the veins. They originated by local melting, probably augmented by magma that formed at a deeper level. Widespread granitic and noritic late-Sveconorwegian magmatism close to 0.92 Ga in other parts of the Western Segment has equivalents in the Norwegian sectors of the Sveconorwegian Province. Leucosome formation was therefore part of a regional event related to exhumation of the Sveconorwegian Eastern Segment. We also provide the first unequivocal evidence for ductile deformation related to late-Sveconorwegian magmatism.     

Electrokinetic remediation of an electroplating site: design and scale-up for an in-situ application in the unsaturated zone

In-situ electrokinetic remediation of contaminated soils requires integrated approaches and adequately engineered setups to control relevant mass fluxes. Based on laboratory findings, this study presents the design of a pilot-scale remediation at an operating electroplating site. The fine-textured soil developed from Jurassic limestone exhibits a chromium, copper, nickel, and zinc contamination down to depths of more than 4 m. The feasibility of an electrokinetic remediation in the unsaturated zone was tested in a lab-scale experiment with subsoil material sampled at the site. The electrodes were placed in water-impermeable, ion-selective membrane wells. This construction allows the necessary watering of the electrodes, maintains unsaturated conditions in the soil compartment, and enables the transfer of contaminant ions into the wells. In addition, the soil is protected from pH changes caused by water electrolysis at the electrodes. The setup includes a watering and drainage system to compensate the electroosmotic water flux and impede desiccation of the anodic region. With a direct current of 70 V and an electric field strength of 2.2 V cm⁻¹, contaminant removal rates amounted up to 27% and 66% (w/w) of the initial zinc/copper and chromium/nickel concentrations. Copper, nickel, and zinc accumulated in the cathode well, while chromate species were enriched in the anode well. Given the successful lab-scale remediation, the pilot plant was designed for the in-situ treatment of a soil volume of 12 m³ below a production hall. A power of 500 V DC at a maximum current of 30 A is supplied by a transformer rectifier. This yields an electric field strength comparable to the lab-scale experiment and thereby similar contaminant transport velocities. A vacuum distillation unit is employed for process water reuse and to control electrolyte conductivity. To cope with chlorine gas generation at the anodes a gas absorber unit is employed. According to the lab-scale results, about 2, 9, 9, and 15 kg zinc, chromium, copper, and nickel, respectively, are expected to be removed from the field plot during an operation time of 10 months.     

SIMS analyses of oxygen isotopes: Matrix effects in Fe-Mg-Ca garnets

Large instrumental mass fractionation (IMF) may occur during measurements of oxygen isotope ratios by SIMS. Part of this fractionation depends on crystal structure and mineral composition. In order to improve the accuracy of SIMS measurements, we gathered 6 commonly used garnet standards and prepared 6 others to adequately cover the composition range Alm_0-73, Prp_0-99, Grs_0-20. Electron microprobe analyses were performed at UBP-Clermont to check the chemical homogeneity of these standards. Oxygen isotope compositions were determined by laser fluorination and mass spectrometry at UW-Madison. Ten SIMS sessions and 336 δ¹⁸O measurements at CRPG-Nancy, on a Cameca IMS1270 instrument, demonstrate that the standards are homogeneous with external reproducibility of 0.3‰ (1σ). In terms of δ¹⁸O, SIMS measurements indicate that, during a single session, IMF can vary up to 6.3‰ from one garnet standard to another. In most of the sessions, IMF can be correlated with the grossular content. However, for a satisfactory correction scheme, we suggest the combination of the 3 main components (Ca, Fe, Mg). This is done using a simple least square calculation routine. The correction coefficients determined for each session can be used to calculate the IMF and correct the measured isotopic ratio of a garnet of known chemical composition. This way, we were able to reproduce the δ¹⁸O values of most of the Fe-Mg-Ca garnet standards within ± 0.6‰. Interestingly, the use of only 3 end-member standards (AlmCMG, PrpMM, GrsSE) plus a standard of intermediate composition (e.g. UWG-2) is sufficient to reproduce δ¹⁸O within the same precision. Thus, linear interpolation among end-member standards is satisfactory in the case of the garnet solid-solutions. Two studies carried out on zoned garnets from the Alps and the Pyrenees indicate that matrix effects become significant when variations in grossular contents are important (> 10%). In order to obtain reliable isotope ratio measurements on Fe-Mg-Ca garnets using a SIMS, we suggest a correction scheme using at least 3 reliable end-member standards plus a standard of intermediate composition (a garnet standard closest to the average composition of the analysed garnet). This allows cross-checking and incorporates a correction based on the variations in composition of zoned crystals.     

Quick clay—A case study of chemical perspective in Southwest Sweden

Quick clay, a soil that changes from normal firm ground to a liquid mass when it is disturbed, has been involved in most of the large and serious clay slides in Sweden, Norway and Canada. The location, time of occurrence and size of quick clay slides are difficult to predict and large slides may cause great devastation. Some geochemical studies of Swedish quick clay were done in the 1960s and early 1970s, but no systematic studies of the interrelationships of pore water chemistry, mineralogy, geotechnical properties and other parameters on quick clays in Sweden have been published. Such studies are of national and general interest because of the many combinations of rock flour source areas and sedimentation conditions that occurred across central Sweden and into the Baltic Sea area during deglaciation. In this study, geotechnical properties related to the in situ chemistry at one quick clay site were extensively studied, and spot sampling was conducted at two other locations in Southwest Sweden. In this area the clay minerals mainly are non-expanding phyllosilicate minerals (illite) and primary minerals (quartz, feldspar), which is consistent with previous studies of quick clay mineralogy. Extensive leaching has occurred at all three locations. At the extensively studied site, Surte, the lowest salinity was found at the greatest depth, inferring that the leaching by fresh water was accomplished by water movement upward and laterally through the sediment from the underlying bedrock. This is consistent with the local setting where bedrock hills rise sharply to over 100 m above the marine sediment surface. An artesian pressure would also be anticipated at this location. There is a correlation (negative) between sensitivity and salinity but there is an indication that the maximum salinity or electrical conductivity consistent with the quick clay behaviour is higher than reported elsewhere. However, for high sensitivities the salinity is about the same as reported elsewhere. In the deepest part of the borehole, there is a higher content of Fe and Al in the pore water, indicating reduced state. Further work is needed to confirm the difference in salinity and to investigate the possible interplay of salinity and potential dispersing agents such as the role of anoxic conditions, in this region. Further work is especially needed in the locations where the sediment accumulation occurred under lower salinity conditions. At all three locations, high remoulded shear strength and low sensitivity have been seen near the surface together with a decrease in pore water cation concentrations.     

Trace element fractionation during high-grade metamorphism and crustal melting—constraints from ion microprobe data of metapelitic, migmatitic and igneous garnets and implications for Sm–Nd garnet chronology

Rare earth element (REE) and other trace element (Y, Sr, Ti, Cr, V, Na) abundances in garnet from a garnet-bearing metapelite, a pelitic migmatite, a syn-tectonic granite and a post-tectonic leucogranite were measured by secondary ion mass spectrometry (SIMS) in order to identify the effective variables on the trace element distribution between garnet and the host rock. Garnet from the garnet-bearing metapelite, the pelitic migmatite and the syn-tectonic granite is zoned with respect to REE. The cores are enriched by a factor of 2–3 relative to the rims. For the garnets from the garnet-bearing metapelite equilibrium distribution following a simple Rayleigh fractionation is responsible for the decreasing concentrations in REE from core to rim. Garnet from the pelitic migmatite shows a more complex trace element pattern following distinct enrichment and depletion patterns for Ti, V, Cr and REE from core to rim. These features suggest disequilibrium between garnet and the associated melt in which the enrichment of trace elements probably correspond to a period of open-system behaviour in these rocks at a time when the garnet, originally nucleated in the metamorphic environment was incorporated into the melt. The garnet from the syn-tectonic granite shows stepwise decreasing concentrations in REE from core to rim: a REE-rich core can be distinguished from a broad REE-depleted rim. Notably, from core to rim an inflection of the Yb / Er and Yb / Dy ratios is visible. Whereas the decrease of HREE abundance in the core region of the garnet from the syn-tectonic granite may arise from equilibrium partitioning during garnet growth, the inflection can be interpreted as a result of partial melting. Garnet cores with high Yb / Er and Yb / Dy >  1 nucleated in the metamorphic environment without the presence of a melt whereas the rims with lower Yb / Er and Yb / Dy <  1 crystallized in the presence of a melt. Garnet from the leucogranite has lower REE abundances and is considered to be of igneous origin. In contrast to garnet from the other samples, its core has low trace element abundances, whereas its rim is significantly enriched in REE but depleted in Ti. These features suggest that only the outermost rim was in equilibrium with the melt. For this garnet, liquid diffusion controlled partitioning is more likely to explain the extreme trace element variation. An evaluation of Sm and Nd concentrations in garnet and a comparison of Sm–Nd and U–Pb garnet ages and U–Pb monazite ages form the terrane indicate that the observed LREE systematics in the different garnet species are a primary feature and are not homogenized by volume diffusion during high grade amphibolite facies conditions.     

Solar activity effects in the ionospheric D region

Variations in the D-region electron concentration within the solar activity cycle are considered. It is demonstrated that conclusions of various authors, who have analyzed various sets of experimental data on [e], differ significantly. The most reliable seem to be the conclusions based on analysis of the [e] measurements carried out by the Faraday rotation method and on the theoretical concepts on the D-region photochemistry. Possible QBO effects in the relation of [e] to solar activity are considered and an assumption is made that such effects may be the reason for the aforementioned disagreement in conclusions on the [e] relation to solar indices.Paper Presented at the Second IAGA/ICMA (IAMAS) Workshop on Solar Activity Forcing of the Middle Atmosphere, Prague, August 1997     

Arsenic — a Review. Part II: Oxidation of Arsenic and its Removal in Water Treatment

In natural waters arsenic normally occurs in the oxidation states +III (arsenite) and +V (arsenate). The removal of As(III) is more difficult than the removal of As(V). Therefore, As(III) has to be oxidized to As(V) prior to its removal. The oxidation in the presence of air or pure oxygen is slow. The oxidation rate can be increased by ozone, chlorine, hypochlorite, chlorine dioxide, or H₂O₂. The oxidation of As(III) is also possible in the presence of manganese oxide coated sands or by advanced oxidation processes. Arsenic can be removed from waters by coprecipitation with Fe(OH)₃, MnO₂ or during water softening. Fixed‐bed filters have successfully been applied for the removal of arsenic.The effectiveness of arsenic removal was tested in the presence of adsorbents such as FeOOH, activated alumina, ferruginous manganese ore, granular activated carbon, or natural zeolites. Other removal technologies are anion exchange, electrocoagulation, and membrane filtration by ultrafiltration, nanofiltration or reverse osmosis.     

Characterisation of sphalerite and pyrite flotation samples by XPS and ToF-SIMS

The surface analytical techniques of X-ray Photoelectron Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS) have provided information on the type and concentration of species on the surface of sphalerite and pyrite particles in flotation concentrate and tail samples, but also on their distribution on each particle and across particles of different sizes. From this surface analytical study, a more accurate interpretation of the flotation results of sphalerite and pyrite minerals in a mixed mineral system could be made as a function of the concentrations of copper sulphate activator and xanthate collector, and particle size. In particular, it was found that sphalerite particles reporting to the concentrate are larger in size and contain less iron hydroxide on their surface than particles reporting to the tail. As for the pyrite particles, their lower recovery than the sphalerite particles is the result of a larger proportion of iron hydroxide on their surface inhibiting copper and collector adsorption.