Isotopic and geochemical characterization of salinization in the shallow aquifers of a reclaimed subsiding zone: The southern Venice Lagoon coastland

The coastal plain bordering the southern Venice Lagoon is a reclaimed lowland characterized by high subsidence rate, and ground level and water-table depth below sea level. In this agricultural region, where the surface hydrologic network is entirely artificially controlled by irrigation/drainage canals, salinization problems have long been encountered in soils and groundwaters. Here we use isotopic and geochemical tracers to improve our understanding of the origin of salinization and mineralization of the semi-confined aquifer (0–40 m), and the freshwater inputs to this hydrological system. Water samples have been collected at different seasons in the coastal Adriatic Sea, lagoon, rivers and irrigation canals, as well as in the semi-confined aquifer at depths between 12 and 35 m (14 boreholes), and in the first confined aquifer (three boreholes drilled between 40 and 80 m depth). Stable isotopes (δ¹⁸O and δD) and conductivity profiles show that direct saline intrusion from the sea or the lagoon is observed only in a restricted coastal strip, while brackish groundwaters are found over the entire topographic and piezometric depression in the centre of the study area. Fresh groundwaters are found only in the most western zone. The sharp isotopic contrast between the western and central regions suggests disconnected hydrological circulations between these two parts of the shallow aquifer. The border between these two regions also corresponds to the limits of the most strongly subsiding zone.Our results can be interpreted in terms of a four end-member mixing scheme, involving (1) marine water from the lagoon or the open sea, (2) alpine and pre-alpine regional recharge waters carried either by the main rivers Adige, Bacchiglione and Brenta (irrigation waters) or by the regional groundwater circulation, (3) local precipitation, and (4) evaporated waters infiltrated from the surface. Infiltration from the surface is also revealed by the stratification of the electrical conductivity profiles, showing that the brackish groundwaters are overlain by a shallow layer of less saline water all over the central depression. In the first confined aquifer, the groundwaters have isotopic compositions similar to the deep groundwaters of the Venetian confined aquifers (40–400 m depth). The isotopic data and the Br/Cl ratio show that the origin of the salinization of the phreatic aquifer can be ascribed to seawater intrusion alone, with no indication of the involvement of deep brines (identified at 450 m depth) in the process.The chemical composition of the saline and brackish groundwaters is characterized by an excess of sodium and a deficit of calcium compared to conservative mixing between fresh groundwaters and seawater. This suggests that the phreatic aquifer is progressively freshening, as a consequence of the beneficial influence of the extensive irrigation/drainage network, including raised canals acting as a hydraulic barrier along the coast. This freshening tendency may have been lasting since the reclamation in the mid-twentieth century, and has probably been accelerated by the ban on groundwater abstraction since the 1970s.     

Assessment of long term change in sediment condition after organic enrichment: defining recovery

Sediment condition at an Atlantic salmon (Salmo salar) culture site in S.E. Tasmania, Australia was evaluated to determine the rate and extent of recovery after removal of farmed fish. By local standards the cage sediment at the start of this survey was markedly degraded but comparison with results from impact studies in Scotland, Canada and Norway suggests that the sediments were considerably less impacted than in northern temperate areas. The impact at the cages diminished rapidly with both time and distance; after only 2 months conditions were markedly improved. The macrobenthos indicated a slower recovery than chemical measures, after 36 months the benthic faunal community structure under the cages still differed from reference conditions even though other sediment measures had recovered. This study highlighted two other key issues in relation to monitoring and management of sediment recovery. First, techniques used to determine impact may not be appropriate for evaluation of recovery. Second, establishment of local baseline standards is extremely important to ensure appropriate evaluation of both impact and recovery.     

MTBE in Drinking Water Production – Occurrence and Efficiency of Treatment Technologies

In Germany, the gasoline additive methyl tert‐butyl ether (MTBE) is almost constantly detected in measurable concentrations in surface waters and is not significantly removed during riverbank filtration. The removal of MTBE from water has been the focus of many studies that mostly were performed at high concentration levels and centred in understanding the mechanisms of elimination. In order to assess the performance of conventional and advanced water treatment technologies for MTBE removal in the low concentration range further studies were undertaken. Laboratory experiments included aeration, granulated activated carbon (GAC) adsorption, ozonation and advanced oxidation processes (AOP). The results show that the removal of MTBE by conventional technologies is not easily achieved. MTBE is only removed by aeration at high expense. Ozonation at neutral pH values did not prove to be effective in eliminating MTBE at all. The use of ozone/H₂O₂ (AOP) may lead to a partly elimination of MTBE. However, the ozone/H₂O₂ concentrations required for a complete removal of MTBE from natural waters is much higher than the ozone levels applied nowadays in waterworks. MTBE is only poorly adsorbed on activated carbon, thus GAC filtration is not efficient in eliminating MTBE. A comparison with real‐life data from German waterworks reveals that if MTBE is detected in the raw water it is most often found in the corresponding drinking water as well due to the poor removal efficiency of conventional treatment steps.     

Relations between metamorphism and orogeny in a typical section of the Indian Himalayas

Summary A comprehensive geological and petrological investigation has been undertaken in an area of about 10 000 km² in the Indian Himalaya (S-Lahul, Himachal Pradesh). The development of mineral assemblages in metamorphic rocks of medium grade is considered to be a dominant Alpine event, although almost exclusively Paleozoic and Precambrian rocks have been involved. The Barrowian type of this metamorphism, ranging from the anchi- to the sillimanite zone, took place under the elavated T-gradient of about 4°C/100 m. It is suggested that normal geothermal conditions prevailed only in the outermost zone of this orogenic belt. In the Late Tertiary this metamorphic series has been moved as a huge nappe upon the Lower Himalaya. During this process a unique feature of reverse metamorphism has been formed. It can be shown that this feature was caused by a combination of metamorphism and very rapid tectonic movements.

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Beziehungen zwischen Metamorphose und Orogenese in einem typischen Querschnitt des Indischen Himalaya

Zusammenfassung Ein etwa 10 000 km² großes Gebiet des Indischen Himalaya (S-Lahul, Himachal Pradesh) wurde einer umfassenden geologischen und petrographischen Bearbeitung unterzogen. Die Ausbildung der in den mittelgradig metamorphen Gesteinen vorliegenden Mineralparagenesen wird als ein dominant alpines Ereignis betrachtet, obwohl fast nur paläozoische und präkambrische Gesteine einbezogen wurden. Die Metamorphose selbst ist von Barrow-Typus und reicht von der Anchi- bis zur Sillimanitzone. Sie fand unter einem erhöhten Temperaturgradienten von etwa 4°C/100 m statt. Nur in der äußersten Zone des Orogens entsprach der Gradient etwa normalen geothermischen Verhältnissen. Im Spättertiär wurde diese alpin-metamorphe Serie in Form einer mächtigen Kristallindecke dem Niedrigen Himalaya aufgeschoben. Dabei wurde eine einzigartige Zone inverser Metamorphose ausgebildet. Es konnte gezeigt werden, daß diese inverse Metamorphose durch das Zusammenwirken von Metamorphose und sehr rasch ablaufender Tektonik entstand.

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With 13 Figures

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Dedicated to Prof. Dr. Dr. h. c.B. Sander on the occasion of his 90th birthday.     

Specific effects of background electrolytes on the kinetics of step propagation during calcite growth

The mechanisms by which background electrolytes modify the kinetics of non-equivalent step propagation during calcite growth were investigated using Atomic Force Microscopy (AFM), at constant driving force and solution stoichiometry. Our results suggest that the acute step spreading rate is controlled by kink-site nucleation and, ultimately, by the dehydration of surface sites, while the velocity of obtuse step advancement is mainly determined by hydration of calcium ions in solution. According to our results, kink nucleation at acute steps could be promoted by carbonate-assisted calcium attachment. The different sensitivity of obtuse and acute step propagation kinetics to cation and surface hydration could be the origin of the reversed geometries of calcite growth hillocks (i.e., rate of obtuse step spreading < rate of acute step spreading) observed in concentrated (ionic strength, IS = 0.1) KCl and CsCl solutions. At low IS (0.02), ion-specific effects seem to be mainly associated with changes in the solvation environment of calcium ions in solution. With increasing electrolyte concentration, the stabilization of surface water by weakly paired salts appears to become increasingly important in determining step spreading rate. At high ionic strength (IS = 0.1), overall calcite growth rates increased with increasing hydration of calcium in solution (i.e., decreasing ion pairing of background electrolytes for sodium-bearing salts) and with decreasing hydration of the carbonate surface site (i.e., increasing ion pairing for chloride-bearing salts). Changes in growth hillock morphology were observed in the presence of Li⁺, F⁻ and , and can be interpreted as the result of the stabilization of polar surfaces due to increased ion hydration. These results increase our ability to predict crystal reactivity in natural fluids which contain significant amounts of solutes.     

The role of baseflow in dissolved solids delivery to streams in the Upper Colorado River Basin

Salinity has a major effect on water users in the Colorado River Basin, estimated to cause almost $300 million per year in economic damages. The Colorado River Basin Salinity Control Program implements and manages projects to reduce salinity loads, investing millions of dollars per year in irrigation upgrades, canal projects, and other mitigation strategies. To inform and improve mitigation efforts, there is a need to better understand sources of salinity to streams and how salinity has changed over time. This study explores salinity in the baseflow fraction of streamflow, assessing whether groundwater is a significant contributor of dissolved solids to streams in the Upper Colorado River Basin (UCRB). Chemical hydrograph separation was used to estimate baseflow discharge and baseflow dissolved solids loads at stream gages (n = 69) across the UCRB. On average, it is estimated that 89% of dissolved solids loads originate from the baseflow fraction of streamflow, indicating that subsurface transport processes play a dominant role in delivering dissolved solids to streams in the UCRB. A statistical trend analysis using weighted regressions on time, discharge, and season was used to evaluate changes in baseflow dissolved solids loads in streams (n = 27) from 1986 to 2011. Decreasing trends in baseflow dissolved solids loads were observed at 63% of streams. At the three most downstream sites, Green River at Green River, UT, Colorado River at Cisco, UT, and the San Juan River near Bluff, UT, baseflow dissolved solids loads decreased by a combined 823,000 metric tons (mT), which is approximately 69% of projected basin‐scale decreases in total dissolved solids loads as a result of salinity control efforts. Decreasing trends in baseflow dissolved solids loads suggest that salinity mitigation projects, landscape changes, and/or climate are reducing dissolved solids transported to streams through the subsurface. Notably, the pace and extent of decreases in baseflow dissolved solids loads declined during the most recent decade; average decreasing loads during the 2000s (28,200 mT) were only 54% of average decreasing loads in the 1990s (51,700 mT).     

Evolution of the winonaite parent body: Clues from silicate mineral trace element distributions

Abstract— We have measured the trace element compositions of individual plagioclase, pyroxene, and olivine grains in 6 different winonaites that span the range of textures and mineralogies observed in these meteorites. Textural evidence in these meteorites, including the presence of a plagioclase/clinopyroxene‐rich lithology and coarse‐grained olivine lithologies, suggests that they may have experienced some silicate partial melting. However, trace element distributions in these lithologies do not show any clear signatures for such an event. Pyroxene trace element compositions do exhibit systematic trends, with abundances generally lowest in Pontlyfni and highest in Winona. The fact that the same trends are present for both incompatible and compatible trace elements suggests, however, that the systematics are more likely the result of equilibration of minerals with initially heterogeneous and distinct compositions, rather than partial melting of a compositionally homogeneous precursor. The winonaites have experienced brecciation and mixing of lithologies, followed by varying degrees of thermal metamorphism on their parent body. These factors probably account for the variable bulk rare earth element (REE) patterns noted for these meteorites and may have led to re‐equilibration of trace elements in different lithologies.     

Comparison of ladderane phospholipid and core lipids as indicators for anaerobic ammonium oxidation (anammox) in marine sediments

We investigated anaerobic ammonium oxidation (anammox) in continental shelf and slope sediments of the Irish and Celtic Seas by using anammox specific ladderane biomarker lipids. We used the presence of an intact ladderane phospholipid as a direct indicator for living anammox bacteria, and compared it with the abundance of ladderane core lipids derived from both living and dead bacterial biomass. All investigated sediments contained ladderane core lipids as well as the intact ladderane phospholipid, in agreement with ¹⁵N-labeling experiments, which revealed anammox activity at all sites. Ladderane core lipid and intact ladderane phospholipid concentrations were significantly correlated (R² = 0.957 and 0.464, respectively) with anammox activity over the transect of the continental shelf and slope sediments. In the Irish Sea (50-100 m water depth) highest abundances of the intact ladderane phospholipid were found in the upper 2 cm of the sediment, indicating a zone of active anammox. A sharp decline further down-core suggested a strong decrease in anammox biomass and rapid degradation of the intact lipids. In comparison, ladderane core lipids were 1-2 orders of magnitude higher in concentration than the intact ladderane phospholipid and accumulated as dead cell remnants with depth. In the slope sediments of the Celtic Sea both ladderane core lipids and the intact ladderane phospholipid were found in sediments at water depths ranging from 500 to 2000 m. Here, anammox seemed to be active at greater depths of the sediment (>2 cm). Mean abundances of both intact and core ladderane lipids in whole sediment cores increased downslope, indicating an increasing importance of anammox in deeper slope sediments.     

The presolar grain inventory of fine‐grained chondrule rims in the Mighei‐type (CM) chondrites

We investigated the inventory of presolar silicate, oxide, and silicon carbide (SiC) grains of fine‐grained chondrule rims in six Mighei‐type (CM) carbonaceous chondrites (Banten, Jbilet Winselwan, Maribo, Murchison, Murray and Yamato 791198), and the CM‐related carbonaceous chondrite Sutter's Mill. Sixteen O‐anomalous grains (nine silicates, six oxides) were detected, corresponding to a combined matrix‐normalized abundance of ~18 ppm, together with 21 presolar SiC grains (~42 ppm). Twelve of the O‐rich grains are enriched in ¹⁷O, and could originate from low‐mass asymptotic giant branch stars. One grain is enriched in ¹⁷O and significantly depleted in ¹⁸O, indicative of additional cool bottom processing or hot bottom burning in its stellar parent, and three grains are of likely core‐collapse supernova origin showing enhanced ¹⁸O/¹⁶O ratios relative to the solar system ratio. We find a presolar silicate/oxide ratio of 1.5, significantly lower than the ratios typically observed for chondritic meteorites. This may indicate a higher degree of aqueous alteration in the studied meteorites, or hint at a heterogeneous distribution of presolar silicates and oxides in the solar nebula. Nevertheless, the low O‐anomalous grain abundance is consistent with aqueous alteration occurring in the protosolar nebula and/or on the respective parent bodies. Six O‐rich presolar grains were studied by Auger Electron Spectroscopy, revealing two Fe‐rich silicates, one forsterite‐like Mg‐rich silicate, two Al‐oxides with spinel‐like compositions, and one Fe‐(Mg‐)oxide. Scanning electron and transmission electron microscopic investigation of a relatively large silicate grain (490 nm × 735 nm) revealed that it was crystalline åkermanite (Ca₂Mg[Si₂O₇]) or a an åkermanite‐diopside (MgCaSi₂O₆) intergrowth.