Green inhibitors reduce unwanted calcium carbonate precipitation: Implications for technical settings.

Mineral scale deposits in water drainage and supply systems are a common and challenging issue, especially by clogging the water flow. The removal of such unwanted deposits is cost intensive arguing for case-specific and sustainable prevention strategies. In the present study, a novel on-site approach to prevent calcium carbonate (CaCO3) scale formation was assessed in two road tunnel drainages: Application of the eco-friendly green inhibitor polyaspartate (PASP) caused (i) a significant inhibition of CaCO3 precipitation, (ii) a more porous or even unconsolidated consistence of the deposits, and (iii) a shift from calcite to the metastable aragonite and vaterite polymorphs. Even relatively low PASP concentrations (1-33 mg/l) can significantly decrease CaCO3 scale deposition, removing up to ∼7 t CaCO3/year at an efficiency up to 84%. Application of PASP for water conditioning should also consider case-specific microbial activity effects, where consumption of PASP, e.g. by Leptothrix ochracea, can limit inhibition effects.

Scale deposits in tunnel drainage systems - A study on fabrics and formation mechanisms.

Rapid deposition of chemical sediments, particularly calcium carbonate, is a widespread phenomenon in tunnel constructions, which can significantly disturb water draining. The removal of the scale deposits in the drainage setting is labor and cost intensive. Prediction or prevention of these unwanted scale deposits are challenging and require detailed knowledge on their site-specific source, formation mechanisms and environmental dependencies. This case study combines a mineralogical, (micro)structural, isotopic, microbiological, and hydrochemical approach to understand the formation of scale deposits in an Austrian motorway tunnel. Chemical and isotopic results revealed that all investigated solutions originate from a distinct local aquifer. High pH (11), indicative high alkaline element concentrations (Na 26 mg/l; K 67 mg/l), originated from concrete leaching, and a strong supersaturation in respect to calcite (SI > 1) are representative for the environmental setting of scaling type 1. This type is characterized by the formation of calcite, aragonite, and rarely documented dypingite (Mg5(CO3)4(OH)2*5H2O), and yields in a highly porous material showing minor indications of microbial presence. In contrast, scale deposits of type 2 are strongly microbially influenced, yielding dense and layered mineral deposits, typically consisting of calcite. The corresponding aqueous solution revealed elevated Mg concentration (38 mg/l) and a high molar Mg/Ca ratio (0.8). Scale deposits containing distinct aragonite precipitates next to calcite, mostly growing in pore spaces of the scale fabric, are accounted as type 3. Therein, dypingite is always growing on top of aragonite needles, indicative for prior CaCO3 precipitation. The composition of corresponding solutions shows the highest Mg/Ca ratio (1.1). Scale type 4 is characterized as a compact deposit consisting entirely of calcite. Its corresponding solution exhibits a molar Mg/Ca ratio of 0.6. From the obtained data sets a conceptual model was developed describing the distinct operative and (micro)environmental conditions responsible for the distinct diversity of scale deposits.

The Combyn™ ECG: Adding haemodynamic and fluid leads for the ECG. Part II: Prediction of total body water (TBW), extracellular fluid (ECF), ECF overload, fat mass (FM) and "dry" appendicular muscle mass (AppMM).

Simultaneous with a 12 channel ECG, body composition was analysed by segmental multi-frequency impedance analysis in 101 healthy subjects and in 118 patients with chronic heart failure (CHF, n= 40), chronic renal failure with haemodialysis (HD, n= 20), and miscellaneous internal diseases (n= 58). Whole body DXA and sodium bromide dilution were used as reference methods for total body water (TBW), extracellular fluid (ECF), appendicular muscle mass (AppMM) and fat mass (FM). Empirical prediction equations were developed in a randomized evaluation sample and then evaluated in unknowns. TBW, ECF, AppMM and FM could be predicted with regression coefficients of 0.96, 0.90, 0.95 and 0.93, respectively, all with p< 0.001. Only segmental impedances and height, but not age, sex, weight and BMI contributed to the prediction of water compartments. About half the patients with CHF and half of those on HD showed increased ECF/ICF ratio in relation to % FM at the legs but not at the thorax. The predicted AppMM was additionally corrected for increased ECF to determine "dry AppMM", which is markedly lower than the misleading reference DXA. This methodology shows promise as a combination of routine ECG with measurement of body composition, assessment of sarcopenia and detection of overhydration.

Temporal and spatial variability of chemical and isotopic composition of soil solutions from cambisols - field study and experiments.

The chemical and isotopic composition of soil solutions is highly relevant for environmental and forensic tasks. We investigated interstitial solutions from soil horizons of three cambisols in Styria (Austria). The soils consisted mainly of quartz, feldspar and clay minerals with a vertical variability. Two soil solution fractions from meso-, macro- and micropores (m) and micropores only (µ) were extracted at two subsequent hydraulic pressure steps corresponding to matrix potentials of up to pF 5.43 and from 5.43 to 5.73, respectively. While solute concentrations indicated diverse distribution in soil solution fractions m and µ, heavy stable hydrogen and oxygen isotopes of H2O (-92.5‰<δ2H<-34.4‰; -11.9‰<δ18O<-4.0‰, VSMOW) are clearly enriched in the µ versus m fractions. Principal component analysis on the hydrochemical data set indicates that the intensity of the overall silicate weathering is higher in autumn versus spring, whereas the anthropogenic impact on weathering behaves inversely. The anthropogenic impact is related to seasonal variability of nitrification of N-fertilizers. In consequence of evaluated signals for overall silicate weathering about three-fourths of the soil solutions sampled in autumn indicated elevated total dissolved solid concentration vs. those in spring accompanied with washing out solutes from the soil cover following precipitation events in autumn before sampling. Isotopic shift of soil solutions from the local meteoric water line in spring obviously followed an evaporation trend because of less precipitation and high evaporation before sampling. Experimentally simulated evaporation of soil samples confirmed the observed isotopic evaporation trend. Wetting experiments indicated the infiltration of water within minutes into the micropores of the soils. Exchange of water molecules between micro-, meso- and macropores is an almost instantaneous process and soil solutions in micropores are not as isolated from the soil water system as it was formerly suggested, e.g. for plant uptake. Highly dynamic and complex mechanisms in the gas-water-solid system of soils have to be considered for the application of elemental and isotope proxies related to environmental, forensic and agricultural tasks.

Tracing formation and durability of calcite in a Punic-Roman cistern mortar (Pantelleria Island, Italy).

Ancient hydraulic lime mortar preserves chemical and isotopic signatures that provide important information about historical processing and its durability. The distribution and isotopic composition of calcite in a mortar of a well-preserved Punic-Roman cistern at Pantelleria Island (Italy) was used to trace the formation conditions, durability, and individual processing periods of the cistern mortar. The analyses of stable carbon and oxygen isotopes of calcite revealed four individual horizons, D, E, B-1 and B-2, of mortar from the top to the bottom of the cistern floor. Volcanic and ceramic aggregates were used for the production of the mortar of horizons E/D and B-1/B-2, respectively. All horizons comprise hydraulic lime mortar characterized by a mean cementation index of 1.5 ± 1, and a constant binder to aggregate ratio of 0.31 ± 0.01. This suggests standardized and highly effective processing of the cistern. The high durability of calcite formed during carbonation of slaked lime within the matrix of the ancient mortar, and thus the excellent resistance of the hydraulic lime mortar against water, was documented by (i) a distinct positive correlation of δ(18)Ocalcite and δ(13)Ccalcite; typical for carbonation through a mortar horizon, (ii) a characteristic evolution of δ(18)Ocalcite and δ(13)Ccalcite through each of the four mortar horizons; lighter follow heavier isotopic values from upper to lower part of the cistern floor, and (iii) δ(18)Ocalcite varying from -10 to -5 ‰ Vienna Pee Dee belemnite (VPDB). The range of δ(18)Ocalcite values rule out recrystallization and/or neoformation of calcite through chemical attack of water stored in cistern. The combined studies of the chemical composition of the binder and the isotopic composition of the calcite in an ancient mortar provide powerful tools for elucidating the ancient techniques and processing periods. This approach helps to evaluate the durability of primary calcite and demonstrates the importance of calcite as a proxy for chemical attack and quality of the ancient inorganic binder.

A critical analysis of whole body bioimpedance spectroscopy (BIS) for the estimation of body compartments in health and disease.

Aim of the study was to assess the accuracy and precision of a BIS device and the relative contribution of BIS beyond the anthropometric parameters. The output of the Impedimed device (SFB7) and the relative contribution of height, weight, age, sex and resistance values at zero and infinite frequency (Rzero and Rinf respectively) to the prediction of total body water (TBWd, deuterium space), of extracellular fluid (ECFbr, sodium bromide space) and of fat mass (FMDXA) were assessed in 116 subjects (32 healthy subjects and 84 patients with disorders of body composition). Using a repeated randomization procedure, new equations for TBW, ECF and FM were derived. The SFB7 gave measures of determination similar to those obtained with equations that included only anthropometric data. The SFB7, but not the newly derived regression equations, underestimated TBW and ECF by 3.82±3.37 (mean±SD) and by 0.93±2.62l and overestimated FM by 6.55±3.86kg. Nine of 16 patients with ECF overload as detected by ECFbr were also detected by BIS. BIS measurements contribute marginally but not significantly beyond anthropometric data to the prediction of TBW, ECF and FM, either in healthy subjects or in patients with disturbed body composition.

Concrete under sulphate attack: an isotope study on sulphur sources.

The formation of secondary sulphate minerals such as thaumasite, ettringite and gypsum is a process causing severe damage to concrete constructions. A major key to understand the complex reactions, involving concrete deterioration is to decipher the cause of its appearance, including the sources of the involved elements. In the present study, sulphate attack on the concrete of two Austrian tunnels is investigated. The distribution of stable sulphur isotopes is successfully applied to decipher the source(s) of sulphur in the deteriorating sulphate-bearing minerals. Interestingly, δ(34)S values of sulphate in local groundwater and in the deteriorating minerals are mostly in the range from+14 to+27 ‰. These δ(34)S values match the isotope patterns of regional Permian and Triassic marine evaporites. Soot relicts from steam- and diesel-driven trains found in one of the tunnels show δ(34)S values from-3 to+5 ‰, and are therefore assumed to be of minor importance for sulphate attack on the concretes. In areas of pyrite-containing sedimentary rocks, the δ(34)S values of sulphate from damaged concrete range between-1 and+11 ‰. The latter range reflects the impact of sulphide oxidation on local groundwater sulphate.

Comparison of monthly and daily isotopic composition of precipitation in the coastal area of Slovenia.

The stable isotopic composition (delta(2)H and delta(18)O) of short-term (daily) precipitation collected from October 2002 to September 2003 at two stations in a coastal, karstic area in south-western Slovenia was investigated. In addition, monthly composite samples were collected and analysed for comparison with amount-weighted monthly means. The delta(2)H and delta(18)O values obtained show a wide range and reflect seasonal climatic variations. Deuterium excess and local meteoric water lines (LMWLs) were determined and cumulative frequency analysis and coincidence tests were performed. The statistical coincidence test showed that the LMWLs calculated from monthly data for Portoroz and Kozina are coincident, but the LMWLs calculated from daily precipitation events are not. This difference could be explained by the greater variance of the isotopic composition of daily precipitation in comparison to monthly composite samples and also to the influence of evaporation during events below<1 mm at Portoroz during the extremely dry and warm spring-summer season of 2003. Finally, synoptic maps and backward trajectories of a selected precipitation event showed that changes of isotopic composition are related to mixing of air masses originating from the continent and Mediterranean cyclogenesis.