Bestimmung eines Gruppenparameters für organische Halogenverbindungen in Wasserproben mit hohen Salzgehalten unter Verwendung von XAD-4-Harz

Determination of a Group Parameter for Organic Halogen Compounds in High Salt-laden Water Samples Using XAD-4 Resin Concerning the often discussed ‘chloride error’ in AOX determination, a method is described with allows the determination of the group parameter organic halogen compounds (OX) for chloride concentrations more than 1 g/L. In opposite to the standard method DIN 38409 part 14, no chloride influence up to a concentration of 10 g/L in real water samples occurs. The basis of the method is the adsorption of the organic compounds from the water sample on XAD-4 resin, a nonpolar copolymer of styrene and divinylbenzene. The organic compounds are concentrated on the XAD-4 resin conditioned with methanol. After the enrichment step, the adsorption columns are treated with sodium nitrate solution. Model experiments with p-chlorophenol and chloride concentrations of 50 g/L showed the effectiveness of this method. The loaded and washed adsorption columns are first eluated with acetone and then with ethyl acetate. Quantification of the OX compounds in the eluates is carried out by microcoulometric detection after combustion in a furnace equipped with a special injector for eluates. For optimal work, the instrument was modified and improved. The presented method was developed on model samples and tested on different real samples.     

氯离子守恒法确定土壤生态蓄水量

通过实验测得降水及土壤水的氯离子浓度,依据化学守恒原理,即降水与包气带土壤水中氯离子的质量守恒关系,计算出长春市丘陵、台地、阶地3类不同地貌区土壤一年内所得水量,该水量为土壤生态蓄水量。将土壤生态蓄水量与土壤的田间持水量、作物的生态需水量进行对比分析,评述了三者之间的关系。阐明土壤生态蓄水量不仅能客观反映土壤中的水分含量情况,也能对植被生态需水量的满足情况给予客观评价。     

Fate of Benzalkonium Chloride in a Sewage Sludge Low Temperature Conversion Process Investigated by LC‐LC/ESI‐MS/MS

Thermocatalytic low temperature conversion (LTC) is a new method for the disposal of sewage sludge. Using this method, sludge is converted into a residual solid (coal) along with reaction water, oil, and non‐condensable gases. The oil can be used as an energy source and the coal as a substitute for charcoal. To this end, it is important to determine whether there are any easily available contaminants present in the coal generated by the process. Contaminants that can be strongly sorbed by sewage sludge solids are, e. g., pharmaceuticals and disinfectants. As an example the fate of the persistent and strong adsorbing disinfectant benzalkonium chloride (BAC) has been investigated within the LTC process. The sewage sludge was spiked with BAC and then subjected to the LTC process. The resulting coal was extracted and analyzed using LC‐LC/ESI‐MS/MS (ion trap). BAC could not be detected in the LTC coal, although it could be extracted from the spiked sludge before the LTC treatment. It can thus be concluded that the investigated compound is not easily available in the coal, and hence that its use does not present a risk.     

应力腐蚀开裂的一种概率竞争机制

１９９８年１月,采用极化曲线,慢应变速率及扫描电镜等试验技术,研究了奥氏体不锈钢的应力腐蚀开裂。结果表明,奥氏体不锈钢在酸性氯离子溶液中处于活性阳极溶解状态,但去发生应力腐蚀开裂,其断口形貌具有解理特征。这种ＳＣＣ无法用钝化膜破裂一再钝化理论和氢脆理论解释。本文以阳极溶解和表变的相互作用,激光散斑干涉术对裂纹尖端应变行为的测量,断口形貌观察等实验结果为基础,结合韧性和脆性断裂概率竞争的观点,提出了     

Mass transport modelling for assessement of groundwater contamination around Mathura oil refinery, Mathura, Uttar Pradesh, India

Mathura oil refinery was commissioned during 1977 and effluent storage ponds were constructed at the same time. These storage ponds receive wastewater from the refinery at a rate of 10000 m³/day. After treatment, waste water is discharged through a 3-km pipeline to a stream leading to the Yamuna river. The groundwater-monitoring as well as water-quality monitoring was carried at 24 observation wells in the refinery site during 1997. The water quality measurements indicated total dissolved chloride and sulphate concentration of native groundwater as 400 mg/l, whereas elevated levels up to 600 mg/l were found at the wells close to polishing ponds. Thus combined transport of chloride and sulphate was simulated in the mass transport model. A three-dimensional flow, pathlines and mass transport model of the aquifer system were constructed to analyze the impact of seepage from polishing ponds contaminating the groundwater regime. The permeability of aquifer varies between 1.5–2.5 m/day. The porosity of formation was assumed as 0.2. The constant head and constant concentration boundaries were assigned to the nodes representing effluent storage ponds. Longitudinal dispersivity of 100 m, horizontal transverse dispersivity of 10 m and vertical transverse dispersivity of 0.01 m were assumed. The mass transport model was calibrated for 20 years by comparing total dissolved chloride and sulphate concentrations from 1997. The model predictions indicate further migration of contaminants on the east of effluent ponds in future. Received: 4 January 1999 · Accepted: 12 July 1999     

Genetic link between saline and carbonatitic mantle fluids: The system NaCl-CaCO3-MgCO3 ± H2O ± Fe0 at 6 GPa

Melt inclusions in kimberlitic minerals and diamonds indicate that chlorides are important constituents of mantle carbonatite melts. Besides, alkaline chlorides are important constituents of saline high-density fluids (HDFs) found in diamonds from kimberlites and placers around the world. Continuous compositional variations suggest that saline and carbonatitic HDFs could be genetically linked. However, the essence of this link remains unclear owing to the lack of data on phase relations in the chloride-carbonate systems under pressure. Here we studied subsolidus and melting phase relations in the system NaCl–CaCO₃–MgCO₃ at 6 GPa and 1000–1600 °C using a Kawai-type multianvil press. We found that at 1000 °C, subsolidus assemblage consists of halite, magnesite, and aragonite. At higher temperatures, the stabilization of dolomite splits the subsolidus area into two partial ternary fields: halite + magnesite + dolomite and halite + dolomite + aragonite. The minimum on the liquidus surface corresponds to the halite-dolomite-aragonite ternary eutectic, situated at 1100 °C. The eutectic melt has Ca# 89 and contains 30 wt.% NaCl (26 mol% 2NaCl). The system has two ternary peritectics: halite + dolomite = magnesite + liquid located near the ternary eutectic and magnesite + dolomite = Mg-dolomite + liquid situated between 1300 and 1400 °C. Although under dry conditions incipient melting yields carbonate-dominated melt, the addition of water facilitates the fusion of NaCl and expands the liquid field to NaCl-rich compositions with up to 70 wt.% NaCl. The obtained results favor the idea that hydrous saline melts/fluids (brines) found as inclusions in diamonds could be a lower temperature derivative of mantle carbonatite melts and disagree with the hypothesis on chloride melt generation owing to the chloride-carbonate liquid immiscibility since no such immiscibility was established. We also studied the interaction of the NaCl–CaCO₃–MgCO₃ system with iron metal and found that carbonate reduction produces C-bearing species (Fe⁰, Fe-C melt, Fe₃C, Fe₇C₃, C⁰) and wüstite containing Na₂O, CaO, and MgO. Besides, a carbonate chloride compound, Ca₂Cl₂CO₃, was established among the reaction products. The interaction between NaCl-bearing carbonate melt shifts its composition toward Mg-poor and NaCl-rich. Given the above, an alternative hypothesis can be proposed, according to which the interaction of alkaline chloride-bearing carbonate melts formed in the subduction zones with the reduced mantle should be accompanied by diamond crystallization and shift the composition of the melt from carbonatitic to alkali-rich saline.     

Influence of mineral weathering reactions on the chemical composition of soil water,Springs, and ground water,Catoctin Mountains,Maryland

During 1983 and 1984, wet precipitation was primarily a solution of dilute sulphuric acid, whereas calcium and bicarbonate were the major ions in springs and ground water in two small watersheds with a deciduous forest cover in central Maryland. Dominant ions in soil water were calcium, magnesium, and sulphate. The relative importance of mineral weathering reactions on the chemical composition of these subsurface waters was compared to the contribution from wet precipitation, biological processes, and road deicing salts. Mineral reaction models, developed from geochemical mass-balance relationships, involved reactions of primary and secondary minerals in metabasalt and metarhyolite with hydrogen ion. Geochemical weathering reactions account for the majority of total ion equivalents in soil water (46 per cent), springs (51 per cent), and ground water (68 to 77 per cent). The net contribution of total ion equivalents from biological processes was 20 and 16 per cent for soil water and springs, respectively, but less than 10 per cent for ground water. The contribution of total ion equivalents from deicing salts (10 to 20 per cent) was related to proximity to roads. Strong acids in precipitation contributed 44 per cent of the total amount of hydrogen ions involved in mineral-weathering reactions for ground water in contact with metarhyolite compared to 25 per cent for ground water in contact with metabasalt, a less resistant rock type to weathering.     

Coupled study of water-stable isotopes and anions in porewater for characterizing aqueous transport through the Mesozoic sedimentary series in the eastern Paris Basin

This study presents data on chloride and bromide concentrations in porewater, water and anion diffusion coefficients, and their accessible porosities based on radial diffusion experiments on rock samples collected from a 2000 m-deep borehole (EST433) drilled by Andra in the eastern Paris Basin. The distributions of water stable isotope and chloride concentrations in porewater along this column reveal transient flows of water and solutes between the aquitard layers and the surrounding aquifers. These distributions confirm the occurrence of two separate aquitard/aquifer systems: “Oxfordian/Callovo–Oxfordian/Dogger” and “Dogger/Liassic/Rhaetian”. This separation is confirmed by Cl⁻/Br⁻ ratios, which are low in Liassic and Dogger porewater, suggesting the influence of primary brines, and which are close to the marine ratio in the Dogger groundwater. Based on these results, transport simulations in the two systems were carried out according to different scenarios. The simulation results confirm that transport properties obtained in the laboratory at sample scale may be extrapolated to the formation scale. It is highly probable that diffusion is the main transport process in the Callovo–Oxfordian formation. This may also be the case in the Dogger/Liassic layer, although a limited contribution from advection cannot be totally excluded. By testing different scenarios of boundary conditions in diffusive models, it is proposed that the Dogger aquifer was first activated in the Early Miocene.     

Precipitation induced stream flow: An event based chemical and isotopic study of a small stream in the Great Plains region of the USA

A small stream in the Great Plains of USA was sampled to understand the streamflow components following intense precipitation and the influence of water storage structures in the drainage basin. Precipitation, stream, ponds, ground-water and soil moisture were sampled for determination of isotopic (D, ¹⁸O) and chemical (Cl, SO₄) composition before and after two intense rain events. Following the first storm event, flow at the downstream locations was generated primarily through shallow subsurface flow and runoff whereas in the headwaters region – where a pond is located in the stream channel – shallow ground-water and pond outflow contributed to the flow. The distinct isotopic signatures of precipitation and the evaporated pond water allowed separation of the event water from the other sources that contributed to the flow. Similarly, variations in the Cl and SO₄ concentrations helped identify the relative contributions of ground-water and soil moisture to the streamflow. The relationship between deuterium excess and Cl or SO₄ content reveals that the early contributions from a rain event to streamflow depend upon the antecedent climatic conditions and the position along the stream channel within the watershed. The design of this study, in which data from several locations within a watershed were collected, shows that in small streams changes in relative contributions from ground water and soil moisture complicate hydrograph separation, with surface-water bodies providing additional complexity. It also demonstrates the usefulness of combined chemical and isotopic methods in hydrologic investigations, especially the utility of the deuterium excess parameter in quantifying the relative contributions of various source components to the stream flow.