Effects of permafrost degradation on thermokarst lake hydrochemistry in the Qinghai-Tibet Plateau,China

Thermokarst lakes play a key role in the hydrological and biogeochemical cycles of permafrost regions. Current knowledge regarding the changes caused by permafrost degradation to the hydrochemistry of lakes in the Qinghai-Tibet Plateau (QTP) is limited. To address this gap, a systematic investigation of thermokarst lake water, suprapermafrost water, ground ice, and precipitation was conducted in the hinterland of the QTP. The thermokarst lake water in the QTP was identified to be of the Na-HCO₃-Cl type. The mean concentrations of HCO₃⁻ and Na⁺ were 281.8 mg L⁻¹ (146.0–546.2 mg L⁻¹) and 73.3 mg L⁻¹ (9.2–345.8 mg L⁻¹), respectively. The concentrations of Li⁺, NH₄⁺, K⁺, F⁻, NO₂⁻, and NO₃⁻ were relatively low. Freeze-out fractionation concentrated the dissolved solids within the lake water during winter, which was deeply deepened on lake depth and lake ice thickness. Owing to solute enrichment, the ground ice was characterized by high salinity. Conversely, repeated replenishment via precipitation led to lower solute concentrations in the ground ice near the permafrost table compared to that within the permafrost. Although lower solute concentration existed in precipitation, the soil leaching and saline ground ice melting processes enhanced the solute load in suprapermafrost water, which is considered an important water and solute resource in thermokarst lakes. The influencing mechanism of permafrost degradation on thermokarst lake hydrochemistry is presumably linked to: (1) the liberation of soluble materials sequestered in ground ice; (2) the increase of solutes in suprapermafrost water and soil pore water; and (3) the changes in lake morphometry. These results have major implications on the understanding of the effects of ground ice melting on ecosystem functions, biogeochemical processes, and energy balance in a rapidly changing climate.     

Water quality and hydrogeochemical characteristics of the River Buyukmelen,Duzce, Turkey

The River Buyukmelen is located in the province of Duzce in northwest Turkey and its water basin is approximately 470 km². The Aksu, Kucukmelen and Ugursuyu streams flow into the River Buyukmelen. It flows into the Black Sea with an output of 44 m³ s⁻¹. The geological succession in the basin comprises limestone and dolomitic limestone of the Yılanlı formation, sandstone, clayey limestone and marls of the Akveren formation, clastics and volcano‐clastics of the Caycuma formation, and cover units comprised of river alluvium, lacutrine sediments and beach sands. The River Buyukmelen is expected to be a water source that can supply the drinking water needs of Istanbul until 2040; therefore, it is imperative that its water quality be preserved. The samples of rock, soil, stream water, suspended, bed and stream sediments and beach sand were collected from the Buyukmelen river basin. They were examined using mineralogical and geochemical methods. The chemical constituents most commonly found in the stream waters are Na⁺, Mg²⁺, SO²⁻₄, Cl⁻ and HCO₃⁻ in the Guz stream water, Ca²⁺ in the Abaza stream water, and K⁺ in the Kuplu stream water. The concentrations of Na⁺, K⁺, Ca²⁺, Mg²⁺, SO²⁻₄, HCO⁻₃, Cl⁻, As, Pb, Ni, Mn, Cr, Zn, Fe and U in the Kuplu and Guz stream waters were much higher than the world average values. The Dilaver, Gubi, Tepekoy, Maden, Celik and Abaza streams interact with sedimentary rocks, and the Kuplu and Guz streams interact with volcanic rocks. The amount of suspended sediment in the River Buyukmelen in December 2002 was 120 mg l⁻¹. The suspended and bed sediments in the muddy stream waters are formed of quartz, calcite, plagioclase, clay (kaolinite, illite and smectite), muscovite and amphibole minerals. As, Co, Cd, Cr, Pb, Ni, Zn and U have all accumulated in the Buyukmelen river‐bed sediments. The muddy feature of the waters is related to the petrographic features of the rocks in the basin and their mineralogical compositions, as most of the sandstones and volcanic rocks (basalt, tuffite and agglomerate) are decomposed to a clay‐rich composition at the surface. Thus, the suspended sediment in stream waters increases by physical weathering of the rocks and water–rock interaction. Owing to the growing population and industrialization, water demand is increasing. The plan is to bring water from the River Buyukmelen to Istanbul's drinking‐water reservoirs. According to the Water Pollution Regulations, the River Buyukmelen belongs to quality class 1 based on Hg, Cd, Pb, As, Cu, Cr, Zn, Mn, Se, Ba, Na⁺, Cl⁻, and SO²⁻₄; and to quality class 3 based on Fe concentration. The concentration of Fe in the River Buyukmelen exceeds the limit values permitted by the World Health Organization and the Turkish Standard. Because water from the River Buyukmelen will be used as drinking water, it will have an adverse effect on water quality and humans if not treated in advance. In addition, the inclusion of Mn and Zn in the Elmali drinking‐water reservoir of Istanbul and Fe in the River Buyukmelen water indicates natural inorganic contamination. Mn, Zn and Fe contents in the waters are related to geological origin. Moreover, the River Buyukmelen flow is very muddy in the rainy seasons and it is inevitable that this will pose problems during the purification process. Copyright © 2005 John Wiley & Sons, Ltd.     

Effect of iron salt counter ion in dose–response curves for inactivation of Fusarium solani in water through solar driven Fenton-like processes

The inactivation of Fusarium solani in water was assessed by solar driven Fenton-like processes using three different iron salts: ferric acetylacetonate (Fe(acac)₃), ferric chloride (FeCl₃) and ferrous sulfate (FeSO₄). The experimental conditions tested were [Fe] ≈ 5 mg L⁻¹, [H₂O₂] ≈ 10 mg L⁻¹ and [Fe] ≈ 10 mg L⁻¹; [H₂O₂] ≈ 20 mg L⁻¹ mild and high, respectively, and pH 3.0 and 5.0, under solar radiation. The highest inactivation rates were observed at high reaction conditions for the three iron salts tested at pH 5.0 with less than 3.0 kJ L⁻¹ of accumulate energy (Q_UV) to achieve over 99.9% of F. solani inactivation. Fe(acac)₃ was the best iron salt to accomplishing F. solani inactivation. The modified Fermi equation was used to fix the experimental inactivation, data showed it was helpful for modeling the process, adequately describing dose–response curves. Inactivation process using FeSO₄ at pH 3.0 was modeled fairly with r² = 0.98 and 0.99 (mild and high concentration, respectively). Fe(acac)₃, FeCl₃ and FeSO₄ at high concentration (i.e. [Fe] ≈ 10 mg L⁻¹; [H₂O₂] ≈ 20 mg L⁻¹) and pH 5.0 showed the highest fitting values (r² = 0.99). Iron salt type showed a remarkable influence on the Fenton-like inactivation process.     

Effects of Fenton Pre‐Treatment on Waste Activated Sludge Properties

Fenton process was investigated for the purpose of biological sludge disintegration. The Box–Wilson experimental design was employed to evaluate the effects of major process variables (Fe(II) and H₂O₂ concentrations) on both disintegration and dewatering performance of sludge. Results showed that 4 g Fe(II)/kg total solids (TSs) and 60 g H₂O₂/kg TS are efficient for floc disintegration. Fenton pre‐treatment enhanced the biodegradability of sludge. For 4 g Fe(II)/kg TS and 60 g H₂O₂/kg TS, 19.4% higher methane production was achieved compared to raw sludge in biochemical methane potential assay. Fenton pre‐treatment resulted in the release of organic sludge components into the liquid phase. For 4 g Fe(II)/kg TS and 60 g H₂O₂/kg TS, dissolved organic carbon and total nitrogen in sludge's supernatant increased by 75.74 and 60.60%, respectively. Fenton pre‐treatment enhanced the filterability of sludge and it can be applied for conditioning purpose before mechanical dewatering units.     

Zur indirekten Ermittlung von Selektivitätskoeffizienten für Ionenaustauschreaktionen

A relation is derived for the calculation of unknown selectivity coefficients from unknown values of tertiary reactions and its validity is proved by experimental investigations of the systems H⁺/Na⁺/Ca²⁺, H⁺/Na⁺/Co²⁺ and H⁺/Na⁺/Al³⁺ at the strongly acid cation exchanger Wofatit KPS.     

Photochemistry of Ions at D-region Altitudes of the Ionosphere: A Review

The current state of knowledge of the D-region ion photochemistry is reviewed. Equations determining production rates of electrons and positive ions by photoionization of atmospheric neutral species are presented and briefly discussed. Considerable attention is given to the progress in the chemistry of O⁺(⁴S), O⁺(²D), O⁺(²P), N⁺, N₂ ⁺, O₂ ⁺, NO⁺, N₄ ⁺, O₄ ⁺, NO⁺(N₂), NO⁺(CO₂), NO⁺(CO₂)₂, NO⁺(H₂O) _n for n = 1–3, NO⁺(H₂O)(N₂), NO⁺(H₂O)₂(N₂), NO⁺(H₂O)(CO₂), NO⁺(H₂O)₂(CO₂), O₂ ⁺(H₂O), H₃O⁺(OH), H⁺(H₂O) _n for n = 1–8, O^?, O₂ ^?, O₃ ^?, O₄ ^?, OH^?, CO₃ ^?, CO₄ ^?, NO₂ ^?, NO₃ ^?, ONOO^?, Cl^?, Cl^?(H₂O), Cl^?(CO₂), HCO₃ ^?, CO₃ ^?(H₂O), CO₃ ^?(H₂O)₂, NO₃ ^?(H₂O), NO₃ ^?(H₂O)₂, OH^?(H₂O), and OH^?(H₂O)₂ ions. The analysis of the D-region rocket ion mass spectrometer measurements shows that, among these ions, O₂ ⁺, NO⁺, NO⁺(H₂O), and H⁺(H₂O) _n for n = 1–7 can make the main contribution to the total positive ion number density, and O^?, O₂ ^?, Cl^?, OH^?(H₂O), CO₃ ^?, HCO₃ ^?, NO₃ ^?, ONOO^?, CO₄ ^?, NO₃ ^?(H₂O), NO₃ ^?(H₂O)₂, and ³⁵Cl^?(CO₂) ions can be responsible for the main contribution to the total negative ion number density. Photodetachment of electrons from O^?, Cl^?, O₂ ^?, O₃ ^?, OH^?, NO₂ ^?, and NO₃ ^?, dissociative electron photodetachment of O₄ ^? and OH^?(H₂O), and photodissociation of O₃ ^?, O₄ ^?, CO₃ ^?, CO₄ ^?, ONOO^?, HCO₃ ^?, CO₃ ^?(H₂O), NO₃ ^?(H₂O), O₂ ⁺(H₂O), O₄ ⁺, N₄ ⁺, NO⁺(H₂O), NO⁺(H₂O)₂, H⁺(H₂O) _n for n = 2–4, NO⁺(N₂), and NO⁺(CO₂) are studied, and the photodetachment and photodissociation rate coefficients are calculated using the current state of knowledge on the cross sections of these processes and fluxes of solar radiation.     

Water and nutrient fluxes in a cool temperate rainforest at the Cordillera de la Costa in southern Chile

Water and nutrient fluxes were studied during a 12-month period in an alerce (Fitzroya cupressoides) forest, located in a remote site at the Cordillera de la Costa (40°05′S) in southern Chile. Measurements of precipitation, throughfall, stemflow, effective precipitation, soil infiltration and stream flow were carried out in an experimental, small watershed. Simultaneously, monthly water samples were collected to determine the concentrations and transport of organic-N, NO₃-N, total-P, K⁺, Ca²⁺, Na⁺ and Mg²⁺ in all levels of forest. Concentration of organic-N, NO₃-N, total-P and K⁺ showed a clear pattern of enrichment in the throughfall, stemflow, effective precipitation and soil infiltration. For Ca²⁺ and Mg²⁺, enrichment was observed in the effective precipitation, soil infiltration and stream flow. Annual transport of K⁺, Na⁺, Ca²⁺ and Mg²⁺ showed that the amounts exported from the forest via stream flow (K⁺=0·95, Na⁺=32·44, Ca²⁺=8·76 and Mg²⁺=7·16 kg ha⁻¹ yr⁻¹) are less than the inputs via precipitation (K⁺=6·39, Na⁺=40·99, Ca²⁺=15·13 and Mg²⁺=7·61 kg ha⁻¹ yr⁻¹). The amounts of organic-N and NO₃-N exported via stream flow (organic-N=1·04 and No₃-N=3·06 kg ha⁻¹ yr⁻¹) were relatively small; however, they represented greater amounts than the inputs via precipitation (organic-N=0·74 and NO₃-N=0·97 kg ha⁻¹ yr⁻¹), because of the great contribution of this element in the superficial soil horizon, where the processes of decomposition of organic material, mineralization and immobilization of the nutrients occurs. © 1998 John Wiley & Sons, Ltd.     

The effect of beech stemflow on spatial patterns of soil solution chemistry and seepage fluxes in a mixed beech/oak stand

Stemflow of beech (Fagus sylvatica L.) represents a significant input of water and elements to the soil and might influence the spatial patterns and the rate of seepage fluxes at the stand scale. We investigated the soil solution chemistry at different depths and distances from the stem and the element fluxes with stemflow, throughfall and seepage in proximal and distal stem areas of a 130‐year‐old beech/oak forest in Steigerwald (northern Bavaria, Germany). The proximal stem area (in total 286 m² ha⁻¹) was defined as a 1 m², 60 cm deep cylinder around the beech stem. Seepage fluxes were calculated by a soil hydrological model for 1996 using measured soil matrix potentials and tree xylem flow data for calibration. Stemflow represented 6·6% of the annual soil water input. With the exception of H⁺ fluxes, less than 10% of the total element fluxes with throughfall and stemflow reached the soil via stemflow. The volume‐weighted concentrations of H⁺, K⁺ and SO₄²⁻ in stemflow were higher than those in throughfall, while other elements had similar concentrations. Soil solution K⁺ concentrations decreased with stem distance, but the Na⁺, Mg²⁺, Cl⁻ and SO₄²⁻ concentrations increased. Gradients for other elements were not statistically significant. Stemflow had a strong influence on the spatial patterns of element fluxes with seepage. The water fluxes through the soil of the proximal stem areas at a depth of 60 cm contributed 13·5% to the total seepage at the stand scale. Proximal to the stems about 20% of total seepage for K⁺, Mn²⁺, Alⁿ⁺, dissolved organic N and dissolved organic C were concentrated, but only 8–10% for Na⁺, Mg²⁺ and Ca²⁺. The loss of acid‐neutralizing capacity calculated from the flux balance was about four times higher proximal to the stems compared with distal areas, indicating high rates of soil acidification proximal to the stems. Our results confirm the concept of a microsite around beech stems, characterized by high element and water fluxes in comparison with distal stem areas. Calculations of seepage fluxes and element budgets in beech stands have to consider the spatial heterogeneity of fluxes induced by stemflow. Copyright © 2000 John Wiley & Sons, Ltd.     

Influence of Atmospheric Solar Radiation Absorption on Photodestruction of Ions at D-Region Altitudes of the Ionosphere

The influence of atmospheric solar radiation absorption on the photodetachment, dissociative photodetachment, and photodissociation rate coefficients (photodestruction rate coefficients) of O^?, Cl^?, O₂ ^?, O₃ ^?, OH^?, NO₂ ^?, NO₃ ^?, O₄ ^?, OH^?(H₂O), CO₃ ^?, CO₄ ^?, ONOO^?, HCO₃ ^?, CO₃ ^?(H₂O), NO₃ ^?(H₂O), O₂ ⁺(H₂O), O₄ ⁺, N₄ ⁺, NO⁺(H₂O), NO⁺(H₂O)₂, H⁺(H₂O) _n for n = 2–4, NO⁺(N₂), and NO⁺(CO₂) at D-region altitudes of the ionosphere is studied. A numerical one-dimensional time-dependent neutral atmospheric composition model has been developed to estimate this influence. The model simulations are carried out for the geomagnetically quiet time period of 15 October 1998 at moderate solar activity over the Boulder ozonesonde. If the solar zenith angle is not more than 90° then the strongest influence of atmospheric solar radiation absorption on photodestruction of ions is found for photodissociation of CO₄ ^? ions when CO₃ ^? ions are formed. It follows from the calculations that decreases in the photodestruction rate coefficients of ions under consideration caused by this influence are less than 2 % at 70 km altitude and above this altitude if the solar zenith angle does not exceed 90°.     

Lithological and hydrological controls on water composition: evaporite dissolution and glacial weathering in the south central Andes of Argentina (33°–34°S)

Lithological and hydrological influence on fluvial physical and chemical erosion was studied in a glacierized sedimentary basin with high evaporite presence. Suspended particulate matter (SPM), total dissolved solids (TDS) and major ion concentrations were analysed for 2 years of different hydrologic condition: (i) 2009–2010, Q = 100% average; and (ii) 2010–2011, Q = 60% average. Annual hydrograph was simple regime‐type with one peak in summer related to snow melting. The intra‐annual SPM and TDS variations were directly and inversely associated to Q, respectively. Snow chemistry showed continental influence (Na⁺/Ca²⁺ = 0.17), and atmospheric input of TDS was <1% of the total exported flux. River water was highly concentrated in Ca²⁺ and SO₄²⁻ (~4 mmol l⁻¹) and in Na⁺ and Cl⁻ (~3 mmol l⁻¹). Ca²⁺/SO₄²⁻ and Na⁺/Cl⁻ molar ratios were ~1 and related to Q, directly and inversely, respectively. Major ion relationships suggest that river chemistry is controlled by evaporite (gypsum and halite) dissolution having a summer input from sulfide oxidation and carbonate dissolution, and a winter input from subsurface flow loaded with silicate weathering products. This variation pattern resulted in nearly chemostatic behaviour for Ca⁺, Mg²⁺ and SO₄²⁻, whereas Na⁺, Cl⁻ and SiO₂ concentrations showed to be controlled by dilution/concentration processes. During the 2009–2010 hydrological year, the fluxes of water, SPM and TDS registered in the snow melting–high Q season were, respectively, 71%, 92% and 67% of the annual total, whereas for equal period in 2010–2011, 56% of water, 86% of SPM and 54% of TDS annual fluxes were registered. The SPM fluxes for 2009–2010 and 2010–2011 were 1.19 × 10⁶ and 0.79 × 10⁶ t year⁻¹, whereas TDS fluxes were 0.68 × 10⁶ and 0.55 × 10⁶ t year⁻¹, respectively. Export rates for 2009–2010 were 484 t km² year⁻¹ for SPM and 275 t km² year⁻¹ for TDS. These rates are higher than those observed in glacierized granite basins and in non‐glacierized evaporite basins, suggesting a synergistic effect of lithology and glaciers on physical and chemical erosion. Copyright © 2014 John Wiley & Sons, Ltd.     

Spatial patterns of soil nitrate in Japanese forested watersheds: importance of the near-stream zone as a source of nitrate in stream water

Spatial patterns of N dynamics in soil were evaluated within two small forested watersheds in Japan. These two watersheds were characterized by steep slopes (>30°) and high stream NO⁻₃ drainage rates (8·4 to 25·1 kg N ha⁻¹ yr⁻¹) that were greater than bulk precipitation N input rates (7·5 to 13·5 kg N ha⁻¹ yr⁻¹). Higher rates of nitrification potential at near-stream zones were reflected in greater NO⁻₃ contents for soil at the near-stream zones compared with ridge zones. Both stream discharge rates and NO⁻₃ concentrations in deep unsaturated soil at the near-stream zones were positively correlated to NO⁻₃ concentrations in stream water. These relationships, together with high soil NO⁻₃ contents at the near-stream zones, suggest that the near-stream zone was an important source of NO⁻₃ to stream water. Nitrate flux from these near-stream zones was also related to the drainage of cations (K⁺, Ca²⁺ and Mg²⁺). The steep slope of the watersheds resulted in small saturated areas that contributed to the high NO⁻₃ production (high nitrification rates) in the near-stream zone. © 1998 John Wiley & Sons, Ltd.     

Degradation of Bezafibrate with UV/H2O2 in Surface Water and Wastewater Treatment Plant Effluent

Bezafibrate (BZF), a widely used lipid regulator, is a potential threat to ecosystems and human health in water, and the recent research showed that advanced oxidation processes (AOPs) are much more effective for BZF degradation. In this study, we investigated the photochemical decomposition of BZF in surface water and effluent from waste water treatment plants (WWTP) by UV/H₂O₂ process. The results showed that the UV/H₂O₂ process was a promising method to remove BZF at low concentration, generally at µg L^?1 level. When initial concentrations reach 100 µg L^?1 in the deionized water, >99.8% of BZF could be removed in 16 min under UV intensity of 61.4 µm cm^?2, at the H₂O₂ concentration of 0.1 mg L^?1, and neutral pH condition. Moreover, BZF degradation was inhibited in this process when humic acid (HA) and inorganic solution anions were added to the deionized water solutions, including chloride, nitrate, bicarbonate, and sulfate, significantly. In the surface water and effluent of WWTP, however, the removal efficiency of BZF was lower than that in the deionized water because of the interference of complex constituents in the surface water and effluent. Some main intermediates at the m/z range of 100–400 were observed by high performance LC‐MS (HPLC/MS) and a simple pathway of BZF degradation by UV/H₂O₂ was proposed.     

Seasonal mixing from intermittent flow drives concentration-discharge behaviour in a stream affected by coal mine drainage

Abandoned mining operations continue to severely degrade many ecosystems worldwide by releasing acidic water and/or heavy metals into surface and groundwater. Contaminant concentrations in affected streams vary with discharge in patterns that reflect both geochemical reactions and variable mixing of contaminated and non-contaminated waters. However, controls on concentration-discharge (C-Q) patterns remain unclear, particularly for constituents that experience changing solubility across redox and pH gradients. Understanding the C-Q behaviour of contaminants aids in predicting both downstream transport and effects on aquatic life under variable flow. Here, we examined the C-Q behaviours of non-reactive (Na, K, Ca, Mg, Cl⁻) and reactive (Fe, Mn, Al, H⁺, SO₄²⁻) solutes in a stream contaminated with acid mine drainage in northeastern Ohio, USA. Concentration-discharge patterns at the watershed outlet primarily reflected mixing of contaminated baseflow with intermittent inputs of high pH water draining from a passive limestone treatment system into the stream. The treatment system acted as an ephemeral tributary that mitigated contamination in the stream by diluting solutes, raising pH, and driving metal precipitation, but only when flow was present during wet seasons. Consequently, AMD-derived reactive solutes (H⁺, Fe, Mn, Al) decreased with increasing stream discharge while relatively conservative solutes (e.g., Ca, Mg, K, Na) decreased only slightly or were chemostatic. This study highlights both the unique C-Q patterns of reactive solutes when compared to those of non-reactive solutes and the potential for intermittent streams to control C-Q behaviour in headwater catchments.     

The chemistry of aqueous iron

Zusammenfassung Bei der Berechnung der L?slichkeiten des zwei-und des dreiwertigen Eisens müssen neben den Fe⁺² und Fe⁺³ Ionen auch die Eisen(II)- und Eisen(III)-Hydroxokomplexe ([Fe(OH)]⁺, [Fe(OH)]²⁺, [Fe(OH)₂]⁺, [Fe(OH)₃] (d), und [Fe(OH)₄]⁻) berücksichtigt werden. Die L?slichkeit des zweiwertigen Eisens in natürlichen (Bikarbonat enthaltenden) W?ssern ist in der Regel durch die L?slichkeitsgleichgewichte des Eisenkarbonats beschr?nkt, w?hrend die L?slichkeit des dreiwertigen Eisens durch die L?slichkeitsgleichgewichte des Eisen(III)-Hydroxyds bestimmt wird (Abbildungen 2 und 4). Die L?slichkeitsverh?ltnisse k?nnen durch Komplexbildung, vor allem mit organischen Basen, ver?ndert werden. Dreiwertiges Eisen hat eine viel st?rkere Tendenz, Hydroxokomplexe zu bilden, as zweiwertiges Eisen. Dementsprechend ist das hydratisierte Eisen-(III)-Ion eine so?rkere S?ure (im SinneBr?nsteds) als das Eisen-(II)-Ion. Die Oxydation von Eisen-(II) zu Eisen-(III) ist deshalb von einer Erniedrigung des pH-Wertes begleitet. Die Hydroxoeisen-(III)-Komplexe haben eine starke Tendenz, Polymerisationsreaktionen einzugehen, wobei im schwach sauren oder neutralen Bereich positiv geladene im alkalischen Bereich hingegen negative geladene Kolloidpartikel entstehen k?nnen. Die allf?llige Koagulation dieser Kolloide zu Eisenoxydhydrat ist vom Elektrolytgehalt abh?ngig und kann durch hydrophile organische Schutzkolloide verhindert werden. Zweiwertiges Eisen ist in Gegenwart von gel?stem Sauerstoff unbest?ndig und wird zu dreiwertigem Eisen oxydiert. Die Oxydationsgeschwindigkeit nimmt mit zunehmendem pH stark zu. Kupfer-, Platinsalze und Aktivkohle als Katalysatoren sowie Komplexbildner, welche mit dreiwertigem Eisen Komplexe bilden,beschleunigen die Autoxidation. Elektrodenpotential-pH-Diagramme (Abbildung 5) erm?glichen einen zusammenfassenden überblick über den Einfluss von Potential und pH auf die L?slichkeitsverh?ltnisse. Im Eisenkreislauf der Seen (Abbildung 7) kommt das Wechselspiel von Oxydation und Reduktion sowie von F?llung und L?sung eindrücklich zur Geltung.      

Hydrogeochemical balance of forest umbrisol profiles (‘Sierra de Gata’, central western Spain)

Three techniques for obtaining soil water solutions (gravitational and matrical waters extracted using both in situ tension lysimeters and in vitro pressure chambers) and their later chemical analysis were performed in order to know the evolution of the soil‐solution composition when water moves down through the soil, from the Ah soil horizon to the BwC‐ or C‐horizons of forest soils located in western Spain. Additionally, ion concentrations and water volumes of input waters to soil (canopy washout) and exported waters (drainage solutions from C‐horizons) were determined to establish the net balance of solutes in order to determine the rates of leaching or retention of ions. A generalized process of sorption or retention of most components (even Cl^?) was observed, from the soil surface to the C‐horizon, in both gravitational and matrical waters, with H₄SiO₄, Mn²⁺, Na⁺, and SO₄^2? being the net exported components from the soil through the groundwater. These results enhance the role of the recycling effect in these forest soils. The net percentages of elements retained in these forest soils, considering the inputs and the outputs balance, were 68% K⁺, 85% Ca²⁺, 58% Mg²⁺, 7% Al³⁺, 5% Fe³⁺, 34% Zn²⁺, 57% Cl^?, and 20% NO₃^?, and about 75% of dissolved organic carbon was mineralized. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of ultrafiltration on salt migration and isotopic composition of pore water in groundwater depression area in Hengshui,NCP

Clay aquitards are semipermeable membranes that allow groundwater flow while retarding solute migration has been researched extensively but also subjected to much debate. At present, there is no evidence of whether the physical and chemical properties of clay soil and the isotopic composition of pore water affect the semipermeable membrane effect. In this study, we collected clay samples from drilling cores (30–90 m) in the Hengshui area located in the North China Plain (NCP), then extracted pore water using a high-pressure squeezing device. Vertical hydrochemical and isotopic profile variation trends for the pore water were revealed using hydrochemical (Cl⁻, Na⁺, Ca²⁺, K⁺, Mg²⁺, and SO₄²⁻) and stable isotopic measurements of H, O and Cl. The results showed that the hydrochemical clay interlayer pore water of the saline aquifer is Cl/SO₄-Na/Mg type and the average total dissolved solids (TDS) are 10.17 g/L. However, the hydrochemical clay aquitard pore water is of the Cl/SO₄-Na/Ca type with an average TDS of 1.90 g/L. The hydrochemical clay interlayer pore water of aquifer II is of Cl-Na/Ca type with an average TDS of 1.10 g/L. Our results showed that the water quality of the aquifer II is not affected by the upper part of the saline aquifer, thus the clay aquitard acts as a significant barrier to salt movement. A polarization layer concentrated in ions was formed between the upper part of the saline aquifer and the clay aquitard. The concentration polarization layer increases the salt-inhibition effect. H, O and Cl isotopic composition results showed significant fractionation. The pore water of aquifer II lacked heavy isotopes (²H, ¹⁸O, ³⁷Cl), but had significant heavy isotope enrichment in the concentrated polarized layer (the δ²H value was −76‰, the δ¹⁸O value was −8.4‰, and the δ³⁷Cl value was 1.59‰). Hyperfiltration thus played a significant role in isotope fractionation.     

Rainfall intensity affects runoff responses in a semi-arid catchment

The source and hydrochemical makeup of a stream reflects the connectivity between rainfall, groundwater, the stream, and is reflected to water quantity and quality of the catchment. However, in a semi-arid, thick, loess covered catchment, temporal variation of stream source and event associated behaviours are lesser known. Thus, the isotopic and chemical hydrographs in a widely distributed, deep loess, semi-arid catchment of the northern Chinese Loess Plateau were characterized to determine the source and hydrochemical behaviours of the stream during intra-rainfall events. Rainfall and streamflow were sampled during six hydrologic events coupled with measurements of stream baseflow and groundwater. The deuterium isotope (²H), major ions (Cl⁻, SO₄²⁻, NO₃⁻, Ca²⁺, K⁺, Mg²⁺, and Na⁺) were evaluated in water samples obtained during rainfall events. Temporal variation of ²H and Cl⁻ measured in the groundwater and stream baseflow prior to rainfall was similar; however, the isotope compositions of the streamflow fluctuated significantly and responded quickly to rainfall events, likely due to an infiltration excess, overland dominated surface runoff during torrential rainfall events. Time source separation using ²H demonstrated greater than 72% on average, the stream composition was event water during torrential rainfall events, with the proportion increasing with rainfall intensity. Solutes concentrations in the stream had loglinear relationships with stream discharge, with an outling anomaly with an example of an intra-rainfall event on Oct. 24, 2015. Stream Cl⁻ behaved nonconservative during rainfall events, temporal variation of Cl⁻ indicated a flush and washout at the onset of small rainfall events, a dilution but still high concentration pattern in high discharge and old water dominated in regression flow period. This study indicates rainfall intensity affects runoff responses in a semi-arid catchment, and the stored water in the thick, loess covered areas was less connected with stream runoff. Solute transport may threaten water quality in the area, requiring further analysis of the performance of the eco-restoration project.     

The solubility mechanisms of volatiles in silicate melts and their relations to crystal-andesite liquid equilibria

The anionic structure of magmatic liquids has been estimated at 1 atm and at pressures corresponding to those of the upper mantle. These estimates are based predominantly on spectroscopic data on binary metal oxide-silica and ternary metal oxide-silica-alumina melts. Structural information on melt compositions in aluminate-silica joins has been used to provide detailed information on the role of Al³⁺ in natural magma at atmospheric and high pressure.Regardless of pressure, andesitic melts may be described as combinations of chain, sheet, and three-dimensional network units. Nearly all Al³⁺ in the magmatic liquid resides in the three-dimensional network units. This Al³⁺ is locally charge-balanced with Na⁺, K⁺, Ca²⁺, and Mg²⁺. In the latter two cases, Al³⁺ and Si⁴⁺ are ordered, whereas for Na⁺ and K⁺, Si⁴⁺ and Al³⁺ are randomly mixed. Solution of water in natural magma results in the formation of new nonbridging oxygens in addition to OH groups attached to Si⁴⁺ and metal cations.On the basis of determined solution mechanisms of CO₂ and H₂O in silicate melts, thermodynamic properties of HO+CO₂, fluids and hydrous silicate melts and melting phase relations in peridotite-H₂O-CO₂, systems, it is found that natural andesitic magma in equilibrium with spinel Iherzolite in the upper mantle (10–20 kbar) must contain at least 5–7 wt.% H₂O. Andesitic magma with 5–7 wt.% H₂O in solution may be described as a mixture of Al-free three-dimensional units, sheets, and chains with a small proportion (less than 10%) of monomers.     

Sampling strategy to describe the temporal hydrochemical characteristics of an alpine proglacial stream

A hierarchical sampling programme (including continuous monitoring, twice-daily sampling and sampling at hourly intervals over selected 24 hour periods) was devised to support hydrochemical and hydrological research programmes on an alpine proglacial stream. The rationale for the research and for the sampling programme are explained and the hydrochemical time series generated over an ablation season are analysed to assess the degree to which they support the study aims. It appears that there is no satisfactory substitute for the chemical analysis of at least two water samples taken at approximately maximum and minimum discharge every day, if seasonal variations in meltwater chemistry are to be effectively characterized. Such time series data can be used to estimate Box-Jenkins transfer function-noise models between particular solutes (SO²⁻₄, Ca²⁺, Mg²⁺, Na⁺ and possibly K⁺) and either discharge or electrical conductivity, which can then be used to fill any short gaps in the data. This approach is not satisfactory even for filling short gaps in the twice-daily determinations of pH, HCO⁻₃ and NO⁻₃. At the diurnal time-scale (based on hourly determinations over 24 hour periods) electrical conductivity seems to provide a good surrogate for most of the solutes studied. HCO⁻₃, SO²⁻₄, Ca²⁺ and Mg²⁺ were found to be particularly strongly related to electrical conductivity and there was little if any significant serial autocorrelation in the residuals from all of the simple linear regression relationships that were estimated between individual species and conductivity. It is concluded that the hierarchical sampling design was suitable for the purposes of the study, and that the continuous monitoring of electrical conductivity provides excellent supporting information to the chemical analysis of water samples if it is used carefully as a means of short term calibration and interpolation of the solute record.