A record of pre-Variscan Barrovian regional metamorphism in the eastern part of the Slavonian Mountains (NE Croatia)

Summary Petrological investigations and monazite dating are carried out on medium-grade metamorphic rocks (micaschist, gneiss and amphibolite) from the Kutjevačka Rijeka transect in the Slavonian Mts., Tisia Unit (NE Croatia). Field, mesoscopic and microstructural observations, as well as the preserved mineral chemistry, point to a single metamorphic event during peak assemblage growth reaching amphibolite facies conditions of ca. 600–650 °C and 8–11 kbar. Th, U and Pb contents of yttrium-rich accessory monazites indicate a pre-Variscan, i.e. Ordovician-Silurian age (444 ± 19 and 428 ± 25 Ma) for the medium-grade metamorphism of garnet-bearing micaschist.     

Arsenic fixation on iron-hydroxide-rich and plant litter-containing sediments in natural environments

Iron-hydroxide-rich and plant litter-containing sediments from natural sites contaminated with uranium mine tailing leachates were examined for their ability to adsorb arsenic. The samples with high contents of iron hydroxides (Fe_total concentration, >300 g kg⁻¹) exhibited remarkable fixation of arsenic (up to 40 g As kg⁻¹). This value corresponded approximately to the supersaturation point for natural iron hydroxides under the present conditions, and it was significantly lower than the value found for synthetic iron hydroxides. There was a strong correlation (R=0.8999) between the concentration of iron and that of arsenic at low arsenic contents, indicating adsorption on strong binding sites. Although all the samples had noticeable contents of organic carbon (plant litter), calcium, and manganese, no obvious effect of these elements on arsenic fixation could be detected. The amount of iron hydroxides was found the only fixation-controlling parameter immediately below a leaching water source.     

Predicting catchment sediment yield in Mediterranean environments: the importance of sediment sources and connectivity in Italian drainage basins

Predicting sediment yield at the catchment scale is one of the main challenges in geomorphologic research. The application of both physics‐based models and regression models has until now not provided very satisfying results for prediction of sediment yield for medium to large sized catchments (c. >50 km²). The explanation for this lies in a combination of the large data requirements of most models and a lack of knowledge to describe all processes and process interactions at the catchment scale. In particular, point sources of sediment (e.g. gullies, mass movements), connectivity and sediment transport remain difficult to describe in most models. From reservoir sedimentation data of 44 Italian catchments, it appeared that there was a (non‐significant) positive relation between catchment area and sediment yield. This is in contrast to what is generally expected from the theory of decreasing sediment delivery rates with increasing catchment area. Furthermore, this positive relation suggests that processes other than upland erosion are responsible for catchment sediment yield. Here we explore the potential of the Factorial Scoring Model (FSM) and the Pacific Southwest Interagency Committee (PSIAC) model to predict sediment yield, and indicate the most important sediment sources. In these models different factors are used to characterize a drainage basin in terms of sensitivity to erosion and connectivity. In both models an index is calculated that is related to sediment yield. The FSM explained between 36 and 61 per cent of the variation in sediment yield, and the PSIAC model between 57 and 62 per cent, depending on the factors used to characterize the catchments. The FSM model performed best based on a factor to describe gullies, lithology, landslides, catchment shape and vegetation. Topography and catchment area did not explain additional variance. In particular, the addition of the landslide factor resulted in a significantly increased model performance. The FSM and PSIAC model both performed better than a spatially distributed model describing water erosion and sediment transport, which was applied to the same catchments but explained only between 20 and 51 per cent of the variation in sediment yield. Model results confirmed the hypothesis that processes other than upland erosion are probably responsible for sediment yield in the Italian catchments. A promising future development of the models is by the use of detailed spatially distributed data to determine the scores, decrease model subjectivity and provide spatially distributed output. Copyright © 2006 John Wiley & Sons, Ltd.     

The influence of urbanization of sinkhole development in central Pennsylvania

The karsted limestone valleys of central Pennsylvania contain two populations of sinkholes. Solution sinkholes occur in the Champlainian limestone units along the margins of the valleys. Solution sinkholes are permanent parts of the landscape and, although a nuisance to construction, do not present other problems. The second population is the suffosional or soil-piping sinkholes These occur on all carbonate rock units including the Beekmantown and Gatesburg dolomites that comprise the two principal carbonate aquifers in the valley. Suffosional sinkholes are the principal land-use hazard. Suffosional sinkholes are transient phonomena. They occur naturally but are exacerbated by runoff modifications that accompany urbanization Suffosional sinkholes are typically 1.5–2.5 m in diameter depending on soil thickness and soil type. The vertical transport of soil to form the void space and soil arch that are the precursors to sinkhole collapse is through solutionally widened fractures and cross-joints and less often through large vertical openings in the bedrock. The limited solution development on the dolomite bedrock combined with soil thickness, seldom greater than 2 m, limits the size of the sinkholes. All aspects of suffosional sinkhole development are shallow processes: transport, piping, void and arch formation, and subsequent collapse take place usually less than 10 m below the land surface Factors exacerbating sinkhole development include pavement, street, and roof runoff which accelerates soil transport Such seemingly minor activities as replacing high grass and brush with mowed grass is observed to accelerate sinkhole development. Dewatering of the aquifer is not a major factor in this region     

Molecular mimicry of the bond length-bond strength variations in oxide crystals

Minimum energy theoretical bond lengths R _t obtained with robust split-basis molecular orbital calculations for 27 hydroxyacid molecules containing first- and second-row cations X ⁿ⁺ reproduce XO bond lengths in crystals. Plots of ln(R _t ) vs. ln(s), where s is the Pauling bond strength, define two different but essentially parallel trends (for first- and second-row cations, respectively) as observed for crystals. A new bond strength parameter p=s/r is defined where r=1 for first- and r=2 for second-row main-group cations. When a ln(R _t ) vs. ln(p) plot is prepared with these theoretical bond lengths, a single trend is obtained. A regression analysis of this data set shows that more than 99 percent of the variation of ln(R _t can be explained in terms of a linear dependence on ln(p), yielding R=1.39 p ^?0.22 as an estimator of the bond lengths. A comparison of 153 mean XO bond lengths compiled by Shannon (1976) for main-group closed-shell X-cations from all 6 rows of the periodic table with those estimated with this formula for r=1, 2, ..., 6, respectively, shows that these bond lengths are estimated within 0.05 Å on average with nearly 85 percent estimated within 0.10 Å of the observed value. More than 97 percent of the variation of these observed bond lengths can be ranked in terms of a linear dependence on the estimated bond lengths. The success of these calculations is further evidence that the forces that govern bond length variations in oxide crystals behave as if they are short-ranged.     

Saharan Dust Transport and High-Latitude Glacial Climatic Variability: The Alboran Sea Record

Millennial to submillennial marine oscillations that are linked with the North Atlantic's Heinrich events and Dansgaard–Oeschger cycles have been reported recently from the Alboran Sea, revealing a close ocean-atmosphere coupling in the Mediterranean region. We present a high-resolution record of lithogenic fraction variability along IMAGES Core MD 95-2043 from the Alboran Sea that we use to infer fluctuations of fluvial and eolian inputs to the core site during periods of rapid climate change, between 28,000 and 48,000 cal yr B.P. Comparison with geochemical and pollen records from the same core enables end-member compositions to be determined and to document fluctuations of fluvial and eolian inputs on millennial and faster timescales. Our data document increases in northward Saharan dust transports during periods of strengthened atmospheric circulation in high northern latitudes. From this we derive two atmospheric scenarios which are linked with the intensity of meridional atmospheric pressure gradients in the North Atlantic region.     

Holocene seasonal sea‐surface temperature variations in the southern Adriatic Sea inferred from a multiproxy approach

Holocene cooling events have been reconstructed for the southern Adriatic Sea (central Mediterranean) by means of analyses of organic walled dinoflagellate cysts, planktonic foraminifera, oxygen isotopes, calcareous nanoplankton, alkenones and pollen from a sediment core. Two cooling events have been detected, during which sea‐surface temperatures (SSTs) were ca. 2°C lower. Unravelling the SST signal into dominant seasonal components suggests maximum winter cooling of 2°C at around 6.0 ka, whereas the cooling at ca. 3.0 ka might be the result of a spring temperature cooling of 2–3°C. The events, lasting several hundred years, are apparently synchronous with those in the Aegean Sea, where they have been related to known cooling events from the Greenland ice‐core record. A distinct interruption in Adriatic Sea sapropel S1 is not clearly accompanied by a local drop in winter temperatures, but seems to be forced by ventilation, which probably occurred earlier in the Aegean Sea and was subsequently transmitted to the Adriatic Sea. Copyright © 2003 John Wiley & Sons, Ltd.     

Temporal trends of dissolved weathering products released from a high Arctic coal mine waste rock pile in Svalbard (78°N)

It is well known that oxidation of sulphide-containing coal mine waste has considerable environmental impacts due to generation of acid mine drainage (AMD) containing high dissolved metal concentrations. This study is the first to evaluate seasonal trends in the release of AMD from high arctic coal mine waste rock. Runoff from an abandoned coal mine waste pile in Svalbard (78°N) was studied during the entire 3–4 month period with running water in 2005. Temporal variation in concentrations and fluxes of dissolved elements were quantified based on daily water sampling and used to evaluate weathering processes and estimate element budgets on a daily, seasonal and annual basis. Apart from alkali- and alkaline earth metals; Fe, Al, Mn, Zn and Ni were found to be the most abundant metals in the runoff. Element concentrations were highly correlated and suggest that the processes of sulphide oxidation, ion exchange and silicate weathering occurring within the waste pile were linked throughout the measuring period. Observed pH values varied from 2.8 to 5.2 and SO₄ concentrations from 21 to 1463 mg L⁻¹. Manganese and Al concentrations were observed above phytotoxic levels (up to 4 and 23 mg L⁻¹, respectively) and were considered the most critical elements in terms of environmental impact. Throughout the summer a total dissolved quantity of 58 kg Mn, 238 kg Al and 13,700 kg SO₄ was released from the pile containing approximately 200,000 m³ of pyritic waste material (<1% FeS₂). The highest concentrations of metals, lowest pH values and a very high daily release of H₂SO₄ (up to twice as high as the following month) were observed during the first week of thaw. This is considered a result of an accumulation of weathering products, generated within the waste pile during winter and released as a pollution-flush during early spring. Similar accumulation/flush sequences were observed later in the summer where rain events following relatively long dry periods caused high daily metal fluxes and on some occasions also elevated dissolved metal concentrations. Despite highly variable weather/climate conditions during the rest of the summer the investigated waste rock pile acted like a relative constant pollution-source during this period. Future investigations regarding the environmental impact of mine waste in the region should include measurements of bioavailable metals in order to provide further details on the seasonal trends in environmental impact.     

Separation of He and CH4 signals on the Mid-Atlantic Ridge at 5°N and 51°N

Abiogenic methane may be produced in submarine hydrothermal systems by degassing of basalts or serpentinization of ultramafic outcrops. The latter process presumably releases little primordial helium and is therefore implicated by high CH₄/³He ratios in vent fluids from the ultramafic-hosted Rainbow field and in methane plumes near ultramafic outcrops. In two segments of the Mid-Atlantic Ridge, at 5.4°N and 51°N, we have observed depth-separated CH₄ and ³He plumes. In both cases, the helium plume was deeper, near the valley floor. It may be that the plumes issue from separate vents, where the helium is discharged near the volcanic axis and the methane is generated by serpentinization on the valley wall. However, at the present time the locations of the vents that produce these plumes are not known. Using a one-pass model, we investigated whether separate venting could arise from heat conduction from a primary, helium-carrying, hydrothermal circulation to a second, shallower fracture loop intersecting ultramafic rock. The model results indicate that the flow rate through the secondary loop would have to be relatively low in order for it to stay warm enough for serpentinization to proceed. In this case, some of the exothermic heat production is lost by conduction, and the temperature increase in the circulating fluid is only a fraction of that expected from a water/rock ratio of 1:1.