Groundwater chemistry of Al under Dutch sandy soils: Effects of land use and depth

Aluminium has received great attention in the second half of the 20th century, mainly in the context of the acid rain problem mostly in forest soils. In this research the effect of land use and depth of the groundwater on Al, pH and DOC concentration in groundwater under Dutch sandy soils has been studied. Both pH and DOC concentration play a major role in the speciation of Al in solution. Furthermore, the equilibrium with mineral phases like gibbsite, amorphous Al(OH)₃ and imogolite, has been considered. Agricultural and natural land use were expected to have different effects on the pH and DOC concentration, which in turn could influence the total Al concentration and the speciation of Al in groundwater at different depths (phreatic, shallow and deep). An extensive dataset (n = 2181) from the national and some provincial monitoring networks on soil and groundwater quality was used. Land use type and groundwater depth did influence the pH, and Al and DOC concentrations in groundwater samples. The Al concentration ranged from <0.4 μmol L⁻¹ at pH > 7 to 1941 μmol L⁻¹ at pH < 4; highest Al concentrations were found for natural-phreatic groundwater. The DOC concentration decreased and the median pH increased with depth of the groundwater. Natural-phreatic groundwater showed lower pH than the agricultural-phreatic groundwater. Highest DOC concentrations were found for the agricultural-phreatic groundwater, induced by the application of organic fertilizers. Besides inorganic complexation, the NICA-Donnan model was used to calculate Al³⁺ concentrations for complexation with DOC. Below pH 4.5 groundwater samples were mainly in disequilibrium with a mineral phase. This disequilibrium is considered to be the result of kinetic constraints or equilibrium with organic matter. Log K values were derived by linear regression and were close to theoretical values for Al(OH)₃ minerals (e.g. gibbsite or amorphous Al(OH)₃), except for natural-phreatic groundwater for which lower log K values were found. Complexation of Al with DOC is shown to be an important factor for the Al concentrations, especially at high DOC concentrations as was found for agricultural-phreatic groundwater.     

The Ecological Impact of Conquest and Colonization on a Medieval Frontier Landscape: Combined Palynological and Geochemical Analysis of Lake Sediments from Radzyń Chełminski,Northern Poland

Slavic and German colonization of the southern Baltic between the 8th and 15th centuries A.D. is well‐documented archaeologically and historically. Despite the large number of pollen profiles from Poland, few palaeoecological studies have examined the ecological impact of a process that was central to the expansion of European, Christian, societies. This study aims to redress this balance through multiproxy analysis of lake sediments from Radzyń Chełminski, Northern Poland, using pollen, element geochemistry (Inductively Coupled‐Optical Emission Spectroscopy [ICP‐OES]), organic content, and magnetic susceptibility. The close association between lake and medieval settlements presents the ideal opportunity to reconstruct past vegetation and land‐use dynamics within a well‐documented archaeological, historical, and cultural context. Three broad phases of increasing landscape impact are visible in the pollen and geochemical data dating from the 8th/9th, 10th/11th, and 13th centuries, reflecting successive phases of Slavic and German colonization. This involved the progressive clearance of oak‐hornbeam dominated woodland and the development of an increasingly open agricultural landscape. Although the castles and towns of the Teutonic Order remain the most visible signs of medieval colonization, the palynological and geochemical data demonstrate that the major phase of woodland impact occurred during the preceding phase of Slavic expansion; Germans colonists were entering a landscape already significantly altered.     

Experimental and theoretical study of the vibrational properties of diaspore (α-AlOOH)

Vibrational properties of diaspore, α-AlOOH, have been re-investigated using room-temperature single-crystal Raman spectroscopy and low-temperature powder infrared (IR) transmission spectroscopy. First-principles harmonic calculations based on density functional theory provide a convincing assignment of the major Raman peaks and infrared absorption bands. The large width of the Raman band related to OH stretching modes is ascribed to mode–mode anharmonic coupling due to medium-strength H-bonding. Additional broadening in the powder IR spectrum arises from depolarization effects in powder particles. The temperature dependence of the IR spectrum provides a further insight into the anharmonic properties of diaspore. Based on their frequency and temperature behavior, narrow absorption features at ~2,000 cm⁻¹ and anti-resonance at ~2,966 cm⁻¹ in the IR spectrum are interpreted as overtones of fundamental bending bands.     

Formation process of two massive dams following rainfall-induced deep-seated rapid landslide failures in the Kii Peninsula of Japan

Extreme heavy rainfall due to Typhoon Talas on September 2–4, 2011 in the Kii Peninsula, Japan, triggered numerous floods and landslides. This study investigates the mechanism and the entire process of rainfall-induced deep-seated landslides forming two massive dams in the Kuridaira and Akatani valleys, respectively. The mechanism of the rapid deep-seated landslides is examined through a series of laboratory experiments on samples from sliding surfaces by using undrained high-stress dynamic-loading ring-shear apparatus. The test results indicate that the failure of samples is triggered by excess pore water pressure generation under a shear displacement from 2 to 7 mm with a pore pressure ratio ranging from 0.33 to 0.37. The rapid movement of landslides is mainly attributed to high mobility due to the liquefaction behavior of both sandstone-rich and shale samples. Geomorphic settings and landslide mobility are major contributing factors to the dam formation. Additionally, shear displacement control tests show that a certain amount of shear displacement between 2 and 7 mm along the sliding surfaces of the gravitationally deformed slopes might have led to the failures. Importantly, computer simulation with LS-RAPID software using input parameters obtained from physical experiments is employed to interpret the entire formation process of the abovementioned two landslide dams. The simulation results are examined in accordance with the observed on-site geomorphic features and recorded data to explain the possibility of sliding processes. The results further point out that local failures are initiated from the lower middle part of the landslide bodies where the geological boundary exists. This condition most probably influences the landslide initiation in the two case studies. This research is therefore helpful for hazard assessment of slopes that are susceptible to deep-seated landslides and other sequential processes in areas with geology and geomorphology similar to that of the Kii Peninsula.     

Late glacial and postglacial pollen and plant macrofossils from Lake West Okoboji, Northwestern Iowa

Pollen and plant macrofossils preserved in lake sediment from Lake West Okoboji, Dickinson County, Iowa, indicate how the vegetation of that area changed during the late glacial and postglacial. A closed coniferous forest, dominated by spruce and larch trees, produced the Picea-Larix pollen assemblage zone. Fir trees were a minor constituent of this forest; pine trees were probably absent. Black ash trees increased in abundance at Lake West Okoboji and by 13,500 yr ago were an important constituent of the forest. The sediment accumulation rate and the pollen influx were low throughout this time. Birch and alder pollen peaked in abundance approximately 11,800 yr ago. Pollen influx increased rapidly as birch and alder replaced coniferous trees on the uplands. A deciduous forest, containing abundant oak and elm trees, replaced the birch-alder-coniferous forest. This forest inhabited northwestern Iowa from approximately 11,000 to 9000 yr B.P. Nonarboreal species became prevalent between approximately 9000 and 7700 yr B.P. as prairie began to replace deciduous forest on the uplands. Charred remains of Amorpha canescens and other upland species attest to the presence of prairie fires as an aid in establishing prairie and destroying the forest. The pollen influx declined. The warmest, driest part of the postglacial occurred in northwestern Iowa from approximately 7700 to 3200 yr ago. Lake level fell 9 to 10 m, and prairie extended to the edge of the lake. Wet-ground weeds inhabited areas near lake level which were alternately flooded, then dry. Pollen influx was approximately 100 grains/cm²/yr during the driest time in this dry interval.Deciduous trees, particularly oaks, returned after approximately 3200 yr B.P. Prairie continued to occupy the uplands but trees were more common in the lowlying wet areas. Settlement by Europeans in northwestern Iowa about 1865 is marked by an increase in weed pollen. Macrofossil deposition changed in 1910 in response to the stabilization of lake level.     

Variogram Fitting by Generalized Least Squares Using an Explicit Formula for the Covariance Structure

In the context of spatial statistics, the classical variogram estimator proposed by Matheron can be written as a quadratic form of the observations. If data are Gaussian with constant mean, then the correlation between the classical variogram estimator at two different lags is a function of the spatial design matrix and the variance matrix. When data are independent with unidimensional and regular support, an explicit formula for this correlation is available. The same is true for a multidimensional and regular support as can be shown by using Kronecker products of matrices. As variogram fitting is a crucial stage for correct spatial prediction, it is proposed to use a generalized least squares method with an explicit formula for the covariance structure (GLSE). A good approximation of the covariance structure is achieved by taking account of the explicit formula for the correlation in the independent situation. Simulations are carried out with several types of underlying variograms, as well as with outliers in the data. Results show that this technique (GLSE), combined with a robust estimator of the variogram, improves the fit significantly.     

Sources of very high heavy metal content in soils of volcanic island (La Réunion)

The objective of this study was to conduct an inventory of heavy metal concentrations (Cd, Cr, Cu, Hg, Ni, Pb and Zn) in the soils of La Réunion. 39 sampling sites were selected to cover the distribution of soils of the island. The results show that soils of La Réunion are rich in heavy metals: most of them exceed the French standard values beyond which sewage sludge spreading is not authorized. To identify the sources of heavy metals, we used: (i) the relationship between the heavy metal content in soils and the origin of the volcanic parent material; (ii) the comparison of heavy metal content between cultivated and uncultivated soils; and (iii) the heavy metal distribution in soil profiles. Cd and Pb evolution in soil profiles indicate an impact of human activities. High Hg concentrations in soils can be explained by the volcanic activity of the island. For Cr, Cu, Ni and Zn, we demonstrate that high concentrations in soils are mainly determined by the natural pedo-geochemical background.     

The global-average production rate ofBe

Precipitation collected in continuously open containers for about a year at seven sites around the United States was analyzed for¹⁰Be,⁹⁰Sr,²¹⁰Pb and²³⁸U. Based on these data and long-term precipitation,⁹⁰Sr and²¹⁰Pb delivery patterns, the stratospheric, tropospheric and recycled¹⁰Be components in the collections were estimated and the global¹⁰Be production rate was assessed. Single station production rate estimates range from 0.52 × 10⁶ atoms cm⁻² yr⁻¹ to 2.64 × 10⁶ atoms cm⁻² yr⁻¹. The mean value is 1.21 × 10⁶ atoms cm⁻² yr⁻¹ with a standard error of 0.26 × 10⁶ atoms cm⁻² yr⁻¹.