Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

Considerations for conducting incubations to study the mechanisms of As release in reducing groundwater aquifers

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.     

Deep-seated gravitational slope deformations and their influence on consequent mass movements (case studies from the highest part of the Czech Carpathians)

Gravitational spreading of mountain ridges displays primary disequilibrium of flysch mountain areas of the Czech Carpathians. The progression of various types of mass movements is a product of long-term ridge disintegration and is predisposed by the geological structure of the area and the upper Tertiary-Quaternary morphogenesis of the mountain area. Deep-seated slope deformations are spatially interconnected by the occurrence of some other types of slope deformations (e.g. debris flows, debris slides, slumps, rock avalanches, etc.), which pose a considerable risk for the existence of human society. An important causative factor in these dynamically developing hazardous processes is, among other factors, the way in which land has been used in the last three centuries. Therefore, the occurrence of various types of slope deformations is studied in terms of their relation to deep-seated gravitational deformations and in terms of other limiting factors (structural geological, morphological and climatic factors, manmade impacts, etc.). The paper presents several case studies of slope deformations (Velká Čantoryje Mt, Lysá hora Mt, Ropice Mt and Smrk Mt) in the area of the Outer Carpathians within the territory of the Czech Republic and also adverts to some consequences in terms of the socioeconomic structure of the landscape.     

The effect of naturally acidified irrigation water on agricultural volcanic soils. The case of Asembagus, Java, Indonesia

Acid water from the Banyuputih river (pH  3.5) is used for the irrigation of agricultural land in the Asembagus coastal area (East Java, Indonesia), with harmful consequences for rice yields. The river water has an unusual composition which is caused by seepage from the acidic Kawah Ijen crater lake into the river. This unique irrigation setting allows the study of soil acidification in situ. This paper assesses the effects of volcanogenically contaminated irrigation water on the chemical properties of the agricultural soils.The changes in soil properties were evaluated by comparing samples taken from the topsoil and sub-soil (1–3 m depth) from areas irrigated with acid water and areas irrigated with neutral water. The field survey thus resulted in four soil categories. Bulk soil composition, organic matter content, moisture content and particle size distribution were determined. Reactive phases were quantified with the selective extractions 1 M KCl, 0.1 M Na-pyrophosphate and 0.2 M acid ammonium oxalate (AAO).By comparing the four soil categories it is shown that the use of the naturally polluted irrigation water has had a large influence on the chemical composition of the topsoil. The composition of the soil solution has changed over the entire investigated soil profile. Furthermore the acid irrigation water has strongly modified the composition of the reactive phases, extracted as KCl, pyrophosphate, and AAO extractable elements, and also the bulk soil composition has been significantly modified. Overall this has resulted in the net dissolution of some elements and the net precipitation of others. The changes in the reactive phases and bulk soil composition are only apparent in the topsoil (0–20 cm) but not in the deeper soil.     

Identification of chlorite and chlorite-related minerals in sediments

A scheme is presented for the identification and classification of chlorite and related minerals in sediments which is mainly based on X-ray characteristics of the orginal sample and the sample heated at 350°C and treated with K⁺ and with glycerol. Examples are given. It is emphasized that additional data about clay mineral genesis, electron microscopy, infrared spectroscopy and chemical analyses are needed for the ordening of a certain mineral in the proposed scheme. Many names of minerals so far found to occur in the clay separate of sediments proved to be synonymous (52 of a total of 88) and thus should be abandoned. They only give confusion and needlessly increase the many difficulties which already exist in the identification, classification and quantitative determination of this complicated group of minerals of about 36 well defined specimens which may be found in sediments.     

Fate and effects of a heavy fuel oil spill on a Georgia salt marsh

Addition of a heavy oil to a Spartina salt marsh in the autumn resulted in high concentrations of polycyclic aromatic hydrocarbons in sediment and benthic animals. The highest concentrations of phenanthrene, chrysene and fluoranthene in the sediment were 112, 105 and 75 ng/g sediment, respectively. These concentrations rapidly decreased during the 20 week period following the spill. The times for these hydrocarbons to decrease to 50% of their highest values, i.e. half-life, were approximately 100, 70 and 30 days in sediment, mussels and oysters, respectively. Benthic macrofauna species showed three responses to oil addition which included no change, an increase, or a decrease in the population. No changes were noted in populations of fiddler crabs (Uca pugnax), oysters (Crassostrea virginica), and mussels (Modiolus demissus). Mud snails (Nassarius obsoleta) increased in density after the spill due to immigration of adult snails from untreated areas to scavenge on animals killed by the oil. Many of the adult periwinkles (Littorina irrorata) were killed by the oil. In the spring, juvenile periwinkles recolonised to oiled areas as a result of larvae settling.     

An alkaline unwinding assay for the detection of DNA damage in aquatic organisms

This paper reports a rapid and facile procedure for obtaining of DNA from small, whole aquatic organisms (fathead minnow, Pimephales promelas) as well as from the liver of another species (bluegill sunfish, Lepomis macrochirus) and the subsequent estimation of its double strandedness. DNA was isolated from various tissues by homogenization in a basic pH solution containing detergent followed by differential extraction using organic solvents. Additional purification was accomplished by molecular sieve chromatography. Under defined alkaline unwinding conditions, the amount of double-stranded and single-stranded DNA was determined using the bisbenzimidazole dye Hoechst 33258. The technique was used to detect the occurrence of strand breaks in DNA of fathead minnows chemically exposed to benzo[a]pyrene.     

Internal generation of waves: Delta source function method and source term addition method

In this study, we investigate two internal wave generation methods in numerical modeling of time-dependent equations for water wave propagation, i.e., delta source function method and source term addition method, the latter of which has been called the line source method in literatures. We derive delta source functions for the Boussinesq-type equations and extended mild-slope equations. By applying the fractional step splitting method, we show that the delta source function method is equivalent to the source term addition method employing the energy velocity. This suggests that the energy velocity should be used rather than the phase velocity for the transport of incident wave energy in the source term addition method. Finally, the performance of the delta source function method is verified by accurately generating nonlinear cnoidal waves as well as linear waves for horizontally one-dimensional cases.     

Generation of random waves in time-dependent extended mild-slope equations using a source function method

We develop techniques of numerical wave generation in the time-dependent extended mild-slope equations of Suh et al. [1997. Time-dependent equations for wave propagation on rapidly varying topography. Coastal Engineering 32, 91–117] and Lee et al. [2003. Extended mild-slope equation for random waves. Coastal Engineering 48, 277–287] for random waves using a source function method. Numerical results for both regular and irregular waves in one and two horizontal dimensions show that the wave heights and the frequency spectra are properly reproduced. The waves that pass through the wave generation region do not cause any numerical disturbances, showing usefulness of the source function method in avoiding re-reflection problems at the offshore boundary.     

An optimized method for automated analysis of algal pigments by HPLC

A recent development in algal pigment analysis by high-performance liquid chromatography (HPLC) is the application of automation. An optimization of a complete sampling and analysis protocol applied specifically in automation has not yet been performed. In this paper we show that automation can only be successful if the various methodological aspects of the sampling and analysis protocol are considered in coherence. We introduce an optimized protocol that involves freeze-drying of the sample, subsequent extraction in 90% acetone and the application of water-packing during analysis. The method was evaluated on both natural plankton populations and a broad spectrum of microalgal cultures: Thalassiosira weisflogii (Bacillariophyceae), Emiliania huxleyi (Prymnesiophyceae), Phaeocystis globosa and Phaeocystis antarctica (Prymnesiophyceae) and Pyramimonas sp. (Prasinophyceae). Whereas pigment extracts were unstable in methanol, with recorded chlorophyll a losses from 10% to 60% per day, pigment degradation rates in acetone were generally less than 1% over 18 h storage in the autosampler (4 °C). In addition, it was found that the extraction efficiency of acetone significantly increased upon freeze-drying prior to extraction. Increases as high as 50–60% were measured in P. antarctica. The application of water-packing of the sample during injection resulted in improved peak shape and peak separation, without diluting the pigment concentrations. Automation is especially beneficial for application in the field, when mixed algal assemblages and low biomass put a high demand on the sensitivity as well as reproducibility of the method.