Focused groundwater discharge of phosphorus to a eutrophic seepage lake (Lake Væng, Denmark): implications for lake ecological state and restoration

A study on Lake Væng in Denmark demonstrates a high potential for loading of phosphorous via groundwater to seepage lakes. Groundwater discharges are displayed as an important source of phosphorous to a lake due to: (1) high concentrations in the aquifer just below the lake, and (2) the main flow paths through the aquifer–lakebed interface either being overland flow through a seepage face, or focused in zones with very high discharge rates. In-lake springs have measured discharge of up to 7.45 m³ per m² of lakebed per day. These findings were based on seepage meter measurements at 18 locations, stable isotope (δ¹⁸O) analyses, temperature profiles and mapping of ice cover distribution. Groundwater–lake interaction was modelled with a 2D conceptual flow model (MODFLOW) with hydrogeology interpreted from catchment multi electrode profiling, on-lake ground-penetrating radar, well logging and borehole data. Discharge was found to be much focused and opposite to expected increase away from the shoreline. The average total phosphorus concentration in discharging groundwater sampled just beneath the lakebed was 0.162 mg TP/l and thereby well over freshwater ecological thresholds (0.043–0.612, median = 0.117 mg TP/l). The study illustrates a direct link between groundwater and lake chemistry.     

Trace metals mass balances for a lake and its catchment

In this study, the size of the metal pools and the fluxes between the pools of eight trace metals (Cu, Ni, Zn, Pb, Cd, Al, Mn, Fe) were measured in a small, oligotrophic, dilute lake located in south-central Ontario, Canada. The lake (Plastic Lake) and it…     

Geochemical Behavior of Manganese in Weathering Environments and Its Significance in Exploration

Under and climate conditions the chemical weathering of manganese ores is govermed by the fugacities of O2,CO2 and S2 in the atmosphere and soils.Manganese minerals exhibit solid phase transformations without migration of Fe and Mn.Under tropical and subtropical humid climate condi-tions low-valent Mn is instable and apt to be oxidized into high valency state.High-valent Mn miner-als are stable and easy to form secondary high-grade Mn ores.Secondary concentration is possible for Mn ores in carbonate formations,while those in clastic rocks tend to migrate and may be washed away.Such differences are the main obstacles in prospecting Mn ore deposits.     

Special phase transformation and crystal growth pathways observed in nanoparticles†

Phase transformation and crystal growth in nanoparticles may happen via mechanisms distinct from those in bulk materials. We combine experimental studies of as-synthesized and hydrothermally coarsened titania (TiO₂) and zinc sulfide (ZnS) with thermodynamic analysis, kinetic modeling and molecular dynamics (MD) simulations. The samples were characterized by transmission electron microscopy, X-ray diffraction, synchrotron X-ray absorption and scattering, and UV-vis spectroscopy. At low temperatures, phase transformation in titania nanoparticles occurs predominantly via interface nucleation at particle–particle contacts. Coarsening and crystal growth of titania nanoparticles can be described using the Smoluchowski equation. Oriented attachment-based crystal growth was common in both hydrothermal solutions and under dry conditions. MD simulations predict large structural perturbations within very fine particles, and are consistent with experimental results showing that ligand binding and change in aggregation state can cause phase transformation without particle coarsening. Such phenomena affect surface reactivity, thus may have important roles in geochemical cycling.     

Is iron redox cycling in a high altitude watershed photochemically or thermally driven?

Many studies have shown that the concentration of aqueous Fe²⁺ increases in surface waters during exposure to sunlight and attribute this phenomenon either to photoreductive dissolution of ferric minerals/colloids or to ligand-to-metal charge transfer within organic complexes of Fe³⁺. In a multi-summer study of iron redox cycling in a relatively high pH stream (Middle Crow Creek, MCC) that drains a mostly-granitic watershed at an altitude of 2400 m, aqueous Fe³⁺ (not Fe²⁺) concentrations were correlated with both sunlight and temperature. A steady state model fails to explain the [Fe²⁺] and [Fe³⁺] data from this stream. However, Fe²⁺ concentrations can be explained using a simple kinetic model in which rate constants for oxidation and reduction were obtained by fitting data from in situ oxidation experiments, including first-order thermal (nonphotochemical) reduction of Fe³⁺. Rate constants obtained from experiments in the dark result in too much Fe²⁺ to match the data from illuminated experiments, requiring a net photooxidation process to explain [Fe³⁺] measured in MCC. The organic content of MCC results in high concentrations of Fe–DOM complexes that not only act as a reservoir contributing to daily changes in [Fe_tot] as measured by our methods, but whose photochemistry may contribute highly oxidizing reactive oxygen species to the stream. In situ studies suggest that photochemical reduction of organically bound Fe³⁺ occurs, followed by thermal release of Fe²⁺ to the water column and subsequent rapid re-oxidation.     

Effects of aridity and vegetation on plant-wax δD in modern lake sediments

We analyzed the deuterium composition of individual plant-waxes in lake sediments from 28 watersheds that span a range of precipitation D/H, vegetation types and climates. The apparent isotopic fractionation (ε_a) between plant-wax n-alkanes and precipitation differs with watershed ecosystem type and structure, and decreases with increasing regional aridity as measured by enrichment of ²H and ¹⁸O associated with evaporation of lake waters. The most negative ε_a values represent signatures least affected by aridity; these values were −125 ± 5‰ for tropical evergreen and dry forests, −130‰ for a temperate broadleaf forest, −120 ± 9‰ for the high-altitude tropical páramo (herbs, shrubs and grasses), and −98 ± 6‰ for North American montane gymnosperm forests. Minimum ε_a values reflect ecosystem-dependent differences in leaf water enrichment and soil evaporation. Slopes of lipid/lake water isotopic enrichments differ slightly with ecosystem structure (i.e. open shrublands versus forests) and overall are quite small (slopes = 0-2), indicating low sensitivity of lipid δD variations to aridity compared with coexisting lake waters. This finding provides an approach for reconstructing ancient precipitation signatures based on plant-wax δD measurements and independent proxies for lake water changes with regional aridity. To illustrate this approach, we employ paired plant-wax δD and carbonate-δ¹⁸O measurements on lake sediments to estimate the isotopic composition of Miocene precipitation on the Tibetan plateau.     

Early diagenesis in anaerobic lake sediments—II. Thermodynamic and kinetic factors controlling the formation of iron phosphate

The ion activity product of Fe and phosphate in interstitial waters from four sediment cores taken from Greifensee, Switzerland indicate the presence of vivianite [Fe₃(PO₄)₂ · 8 H₂O] in the solid phase. Analysis of the sediment using an electron microprobe and by electron microscopy revealed P-rich grains to be also enriched in Fe. The combined methods provide strong evidence that vivianite is forming authigenically in the sediments. Thermodynamic stability calculations demonstrate that the most stable Fe and phosphate minerals (pyrite, siderite and apatite) are not the ones controlling the pore water chemistry. The results emphasize the importance of rate processes of mineral formation in early diagenesis.Calculations based on the sediment phosphate concentration, and the degree of supersaturation of Fe and phosphate in the upper portion (0–15 cm) of the pore waters, indicate that the rate of vivianite mineral growth is controlled by a surface reaction rather than a diffusion mechanism. The response time of dissolved phosphate in the sediment pore waters with respect to mineral precipitation is on the order of 1–20 days. Less than 15% of the phosphate released by organic matter degradation at the sediment-water interface and below is retained in the sediments.     

Lake Müggelsee —the use of lake water and its consequences

Lake Müggelsee (Groer Müggelsee) — the largest lake in the area of Berlin — is the main drinking water reservoir for Berlin (East), but also a center of numerous recreational activities and fishing. The use of the lake and its catchment area has continuously increase during the past decase and has caused a substantail deterioration of the lake water quality. Mass development of algae has become a limiting factor to all future utilizations of the lake. Since the beginning of this century up to the seventies the lake water has shown signs of a permanently growing eutrophication, e.g. the content of particulate matter in the lake water has nearly doubled. During and after World War II the lake quality (Secchi depth and seston content) improved remarkably due to a reduced input of nutrients.According to time series analyses of buoyant seston and meterologica elements the development of blue-green algae seems to depend more on weather conditions than on the nutrient content of the lake water.Therefore, a certain probability of blue-green algae blooms will remain, also in the case of reduced nutrient input. Phosphorous is the main cause for eutrophication. It was responsible for distinctly higher mass developments of algae during spring and autumn in the past two decades. As a consequence, comprehensive measures are to be taken to reduce phosphorus inputs into the Spree river and lake Müggelsee, e.g. by the substitution of P in detergents, construction of tertiary sewage treatment plants and a substantially reduced application of fertilizers in agriculture.     

Pesticides and other micro-organic contaminants in freshwater sedimentary environments—a review

A wide range of issues relating to the presence and fate of pesticides and other micro-organic contaminants (MOCs) in surface freshwater sedimentary environments is reviewed. These issues include the sources, transport and occurrence of MOCs in freshwater environments; their ecological effects; their interaction with sedimentary material; and a range of processes related to their fate, including degradation, diffusion in bed sediments, bioturbation and slow contaminant release. An emphasis is placed on those processes—chemical, physical or biological—in which sediments play a role in determining the fate of micro-organics in freshwater environments. The issues of occurrence, source and transport, and the ecological effects of micro-organics are introduced more briefly, the focus where these aspects are concerned being largely on pesticides. In the concluding section, key points and issues relating to the study of micro-organics in freshwater environments are summarised and areas where initial or further research would be welcome are highlighted. It is hoped that this paper will both form a useful reference for workers in the field of micro-organic contaminants, and also stimulate new work in the freshwater environment and beyond.     

14C in bicarbonate and dissolved organics—a useful tracer?

The tunnel excavation at the Äspö Hard Rock Laboratory opened several fracture zones at various depths in the crystalline bedrock. One of these zones is the `Redox zone', a vertical fracture zone penetrated at 70 m depth. Except for the tunnel intersection, several boreholes were drilled to intersect the zone at various depths (ranging from 5 to 70 m) and distances from the tunnel. The response in groundwater chemistry to the opening of the zone has been monitored in these boreholes during 3 a, starting in 1991 and for the boreholes at 70 m depth the monitoring is still ongoing. The water chemistry during this monitoring can be largely explained by mixing between fresh water and native saline groundwater (4900 ppm Cl⁻). An increase in HCO⁻₃ was recorded, which was interpreted as due to anaerobic respiration. This was supported by ¹⁴C-contents in dissolved organic Carbon and HCO⁻₃, indicating that recent organic C is transported into the zone and oxidised to CO₂. This study exemplifies the use of ¹⁴C-analyses of HCO⁻₃ in order to trace different C sources contributing to the HCO⁻₃ in the groundwater. Three sources were identified: (1) dissolved CO₂, dominantly soil-CO₂ possibly with some contribution of atmospheric CO₂; (2) dissolution of calcite, with low ¹⁴C content, which dominantly occurs in the near-surface recharge area; and (3) oxidation of organic material through anaerobic respiration. Corrections for ¹⁴C and HCO⁻₃ in the native saline water made it possible to determine 2 different fresh water components corresponding to different flow paths. The C isotope data are in accordance with the results from the tracer test and the groundwater flow model, and support that the extensive build up of HCO₃⁻ does not mainly takes place locally within the zone but is transported into the zone by dominantly lateral flow. The results from the monitoring showed that new hydrochemical stability is established, which also comprises the interaction between the organic and inorganic C cycles.     

Rock avalanching into a landslide-dammed lake causing multiple dam failure in Las Conchas valley (NW Argentina) — evidence from surface exposure dating and stratigraphic analyses

Generally landslide dams which exist for several hundreds to thousands of years are considered as stable. We show with an example from the Argentine Andes that such dams can exist for several thousands of years but still may fail catastrophically. Multiple rock avalanches impounded two lakes with surface areas of ~8 km² and ~600 km², respectively, in Las Conchas valley, NW Argentina. Surface exposure dating (SED) by ¹⁰Be of the rock-avalanche deposits or landslide scars indicates that these landslides occurred at 15,300±2,000 yr and 13,550±900 yr. The dams were stable during a strong earthquake, as suggested by seismites within related lake sediments and by multiple coeval landslides in this region, which occurred at ~7.5 kyr. However, when a further rock-avalanche fell into the lower, smaller lake at 4,800±500 yr the dam downriver was destroyed, presumably by the resulting tsunami wave. The resulting flood also destroyed an additional rock-fall dam which had formed at ~5,630 yr ¹⁴C cal BP 30 km downriver. The new dam formed by the second rock avalanche was eroded prior to 3,630 yr ¹⁴C cal BP. This dam erosion coincides with an important climatic shift towards more humid conditions in the Central Andes. Our results show that instead of direct effects of strong seismicity on landslide dams, (1) landsliding into a landslide-dammed lake, (2) abrupt hydrological changes, and (3) climate change towards conditions related to enhanced run-off are processes which can produce failures of quasi-stable natural dams.     

Measurement of the total nitrogen in lake sediments： Comparison and its environmental significance

Nitrogen cycle is an important bio-geochemical process in the environment. Measurement of the total nitrogen （TN） is a routine experiment in agriculture, biology and environmental sciences. The Kjeldahl method （KM） and elemental analyzer method （EA） are both commonly used to determine TN. Total nitrogen by EA is the sum of nitrate （NO3）, nitrite （NO2）, organic nitrogen and ammonia. Total nitrogen by KM （TKN） is made up of both organic nitrogen and ammonia. A comparative study focused on the two methods is conducted by analysis of TN in 97 samples from the sediment sequence of Gouchi, a salt lake in North China. KM presents a higher degree of accuracy than EA with a standard deviation of 0.007 vs. 0.024. With the presence of nitrate and/or nitrite nitrogen, however, measurement by KM is considerably lower than that by EA. Therefore, for samples from lake sediment sequences or soils in North China, KM is inapplicable to determining TN because of usually high contents of nitrous salt. Despite the inconsistency, use of both methods to the same samples makes sense in reconstructions of climatic and environmental changes from lake sediments. In Lake Gouchi, the contents of nitrate and nitrite nitrogen vary from 1.40% in the lower part of the sequence to 14.77% in the uppermost part, suggesting a gradual evolution process from a fresh water lake to the present-day salt lake.     

Detection of the historical Askja ad 1875 and modern Icelandic cryptotephras in varved lake sediments – results from a first systematic search in northern Poland

Volcanic ash can disperse thousands of kilometres from the source volcano and provide valuable chronostratigraphic markers for palaeoclimate studies. We present new cryptotephra findings of historical and modern Icelandic eruptions in annually laminated lacustrine sediment records from several sites within a 570 km SW–NE transect across northern Poland. Sediments from the two lakes Wąsoskie and Szurpiły contain glass shards originating from the Plinian Askja ad 1875 eruption and showing bimodal, rhyolitic and dacitic affinities. A further cryptotephra finding in Lake Lubińskie suggests a potential origin from the Hekla ad 1845 eruption. These new findings extend the tephra dispersal map towards the south-east and provide valuable isochrons for the synchronisation of palaeoclimate proxy data at the termination of the Little Ice Age in central eastern Europe. Very low glass concentrations of modern cryptotephra in Lake Wąsoskie were potentially correlated with the Eyjafjallajökull ad 2010 eruption. Further findings in the uppermost sediments of lakes Szurpiły and Żabińskie in north-eastern Poland tentatively suggest other sources from either the Hekla and/or Kamchatkan volcanoes.     

Oxidation of As^Ⅲ by Several Manganese Oxide Minerals in Absence and Presence of Goethite

Oxidation of As^Ⅲ by three types of manganese oxide minerals affected by goethite was investigated by chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Three synthesized Mn oxide minerals of different types, birnessite, todorokite, and hausmannite, could actively oxidize As^Ⅲ to Asv, and greatly varied in their oxidation ability. Layer structured birnessite exhibited the highest capacity of As^Ⅲ oxidation, followed by the tunnel structured todorokite. Lower oxide hansmannite possessed much low capacity of As^Ⅲ oxidation, and released more Mn^2＋ than birnessite and todorokite during the oxidation. The maximum amount of Asv produced during the oxidation of As^Ⅲ by Mn oxide minerals was in the order： birnessite （480.4 mmol/kg） 〉 todorokite （279.6 mmol/kg） 〉 hansmannite （117.9 mmol/kg）. The oxidation capacity of the Mn oxide minerals was found to be relative to the composition, crystallinity, and surface properties. In the presence of goethite oxidation of As^Ⅲ by Mn oxide minerals increased, with maximum amounts of Asv being 651.0 mmol/kg for birnessite, 332.3 mmol/kg for todorokite and 159.4 mmol/kg for hansmannite. Goethite promoted As^Ⅲ oxidation on the surface of Mn oxide minerals through adsorption of the Asv produced, incurring the decrease of Asv concentration in solutions. Thus, the combined effects of the oxidation （by Mn oxide minerals）-adsorption （by goethite） lead to rapid oxidation and immobilization of As in soils and sediments and alleviation of the As^Ⅲ toxicity in the environments.     

Awheel in Edwardian Bedfordshire: A 1905 Geologists’ Association cycling excursion revisited and contextualised

Most of the excursions organised by the Geologists’ Association in the late 19th C. and early 20th C. were essentially pedestrian in nature. However, around the turn of the 20th C. and up to the Great War (1914–1918), the Association experimented with either specific cycling-based excursions or those that accommodated the needs of cyclist excursionists. At the time, the Association, with its London base, was ideally placed to employ the railway network as the basis for its excursions. Railways were then the principal mode of transport for middle- and long- distance journeys and were increasingly promoting suburban expansion, creating potential new field excursion areas. The railways catered for those pedestrian excursionists and cyclists who wished to venture further afield from London than was previously possible on a day- or half- day trip. The notices and reports of excursions published by the Association are examined and critiqued. The cycling excursions are examined and contextualised within a combined technological and socio-historical framework; parallels are drawn with today. A re-examination of the excursions also provides a benchmark, useful for geoconservation purposes, of the availability and accessibility of historical geosites. It can underpin new self-guided geotrails suitable for use by a wider audience than traditional geological excursionists. These various themes are explored through the consideration of a specific 1905 excursion to Bedfordshire from which general conclusions are drawn.     

Crude oil in a shallow sand and gravel aquifer—I. Hydrogeology and inorganic geochemistry

Changes in the distribution of inorganic solutes in a shallow ground water contaminated by crude oil document a series of geochemical reactions initiated by biodegradation of the oil. Upgradient of an oil body floating on the water table, oxidation of oil to carbonic acid dissolves carbonate minerals in the aquifer matrix. In this oxidized zone pH is depressed ∼1 pH unit, and the concentrations of Ca, Mg and HCO₃⁻ increase to more than twice that of the native ground water. In the anoxic zone beneath the oil body concentrations of dissolved SiO₂, Sr, K, Fe and Mn increase significantly. Here, Fe is mobilized by microbial reduction, pH is buffered by the carbonate system, and silicates weather via hydrolysis and organic-acid-enhanced dissolution. Farther down-gradient the ground water is reoxygenated and Fe precipitates from solution, possibly as iron hydroxide or iron carbonates, while SiO₂ precipitates as amorphous silica. Other solutes, such as Mg, are transported more conservatively down-gradient where contaminated and native ground water mix.The observed changes in inorganic aqueous chemistry document changes in water-mineral interactions caused by the presence of an organic contaminant. These organic-initiated interactions are likely present in many contaminated aquifers and may be analogous to interactions occurring in other organic-rich natural waters.     

Purines,pyrimidines and organic carbon in lake sediments — A comparison of sediments from lakes of varying degrees of eutrophication

Sediment cores from the Great Lakes of North America and the Bodensee (Lake Constance) were analysed for purine and pyrimidine contents and total organic carbon. Lakes subject to recent cultural eutrophication showed steep increases in both organic carbon and purine and pyrimidine concentrations in the recently deposited sediments. Analytical results for Lake Huron (oligotrophic) and for a highly eutrophic area of the Bodensee (Gnadensee) appeared remarkably similar, in that only gradual, linear increases were observed in the total organic carbon curves. The curves for total purines and pyrimidines were also less steep for these cores as compared to the others studied. A possible explanation is that both areas represent lakes with no serious, recent changes in productivity. Uracil was found to decrease in concentration faster than any other purine or pyrimidine in the first few centimeters of all cores, supporting previous suggestions of more rapid turnover of this pyrimidine in sediments.