Significance,mechanisms and environmental implications of microbial biomineralization

Microorganisms can mediate the formation of minerals by a process called biomineralization. This process offers an efficient way to sequester inorganic pollutants within relatively stable solid phases. Here we review some of the main mechanisms involved in the mediation of mineral precipitation by microorganisms. This includes supersaturation caused by metabolic activity, the triggering of nucleation by production of more or less specific organic molecules, and the impact of mineral growth. While these processes have been widely studied in the laboratory, assessment of their importance in the environment is more difficult. We illustrate this difficulty using a case study on an As-contaminated acid mine drainage located in the South of France (Carnoulès, Gard). In particular, we explore the potential relationships that might exist between microbial diversity and mineral precipitation. The present review, far from being exhaustive, highlights some recent advances in the field of biomineralogy and provides non-specialists an introduction to some of the main approaches and some questions that remain unanswered.     

Trace elements in tissues of cetacean species rarely stranded along the Israeli Mediterranean coast

In this paper we present the concentrations of Hg, Cd, Se, Pb, Cu, Mn, Zn and Fe in organs of 6 non-common specimens of cetaceans that were stranded along the Israeli Mediterranean coast (IMC), during 2002–2010: two fin whales, one minke whale, one Cuvier’s beaked whale, one rough-toothed dolphin, and one Risso’s dolphin. Most of the specimens were calves stranded by accident. Concentrations of Hg and Cd were low in tissues of the baleen whales and higher in the toothed whales, with maximum concentrations of 1067 mg kg⁻¹ Hg in the liver of the Risso’s dolphin and 29 mg kg⁻¹ Cd in the kidney of the Cuvier’s beaked whale. As far as we are aware, this is the first report of trace elements in baleen whales in the Eastern Mediterranean, and the first report of trace elements in minke whale and rough-toothed dolphin in the Mediterranean.     

Rainfall, spring discharge and past human occupancy in the Eastern Mediterranean

In ancient times human activities were tightly related and sensitive to rainfall amounts and seasonal distribution. East Mediterranean settlements were concentrated around numerous small to large springs, such as the Judean Mountains area. The goals of this study were to determine (a) the sensitivity of total discharge, recession curve, and response time of such springs to annual precipitation patterns, and (b) how spring hydrology responds to series of drought or wet years and to transitions from drought to normal and/or wet episodes (and vice versa). These goals were achieved by setting a finite-element hydro-geological flow model for selected perched springs that characterize the numerous springs throughout the carbonate karst terrain in the Judean Mountains. In addition, we estimated the effect of proposed regional past climate changes on the springs; in so doing, we transfer climate change to community size, livelihood and economic strength that were highly dependent on agricultural productivity. The results of the hydro-geological model revealed that these mountainous communities had the potential to prosper during historically wetter episodes and were probably adapted to short-term variability in annual rainfall. However, moderate to extreme droughts lasting only a few years could have led to a partial or even total abandonment of the springs as focal sites of intensive agricultural production. Spring drying eliminated the primary cause for the location of settlement. This occurred simultaneously in numerous settlements around the mountains of the southern Levant and therefore, must have caused dramatic economic and societal changes in the entire region, perhaps even resonating afar.     

Remobilization of arsenic from buried wastes at an industrial site: mineralogical and geochemical control

An industrial area contaminated by As was studied to determine the source of this element and its speciation in As-bearing solids and in run-off waters. Mineral precipitates and water samples were collected and analyzed to assess processes controlling As mobility at this site. The integrated study of a contaminated industrial area allowed identification of the source of the As and of the nature of secondary As-bearing phases. The results obtained both on solid and water samples were used to model As behavior during waste leaching on carbonate rocks. At the upper end of a topographic transect across the site, run-off waters (pH=7.9) interact with surficial waste piles (containing arsenolite, arsenopyrite and pyrite), becoming acidic (pH=2.2) and concentrated in dissolved arsenate species (As⁵⁺) (ΣAs ranging from 0.961 to 3.149·10⁻³ mol/l). Those acidic waters interact with the limestone substratum, providing dissolved Ca which reacts with As to precipitate 1:1 Ca arsenates (weilite CaHAsO₄, haidingerite CaHAsO₄.H₂O and pharmacolite CaHAsO₄.2H₂O) and, in minor amounts, Ca–Mg arsenates (picropharmacolite (Ca,Mg)₃(AsO₄)₂ 6H₂O). The 1:1 Ca arsenates identified are known to precipitate at low pH (3–6) and seem to be stable in media with high dissolved CO₂, in comparison with other types of Ca arsenates. However, due to their high solubilities, they are not strictly relevant candidates to immobilize As in contaminated surficial environments. Although reported solubilities decrease to values close to the French and US drinking standards in Ca-rich solutions, a thorough examination of the precipitation/dissolution kinetics of Ca arsenates should be undertaken to assess their long-term stability and their efficiency in rapidly immobilizing As in contaminated surficial environments.     

Spatio-temporal evolution of the Choisille River (southern Parisian Basin,France) during the Weichselian and the Holocene as a record of climate trend and human activity in north-western Europe

The morpho-sedimentary evolution of the Choisille floodplain (lowland river, catchment: 288 km²), a tributary of the River Loire in the south-western Parisian Basin, was studied through 61 core drillings along eight transects and a geophysical survey located in four stretches of the river: stretches A and B correspond to two sub-catchments, and stretches C and D are in the main valley. Sixty ¹⁴C and four OSL datings were obtained, and sediments were analysed on seven reference cores. Eight phases of evolution differing markedly from the evolution of more northern areas in the Parisian Basin and north-western Europe were identified from spatio-temporal distribution of nine lithological facies. The deepest incision phase (1) occurred during the first part of the Weichselian, followed by the deposition of a gravelly-sandy unit (phase 2) during the Middle Pleniglacial, which was deeply incised (phase 3), probably during the Bölling. From the Allerød up to the last third of the Boreal (phase 4), sedimentation was continuously dominated by peaty deposits, with no evidence of either increased hydraulic energy during the Younger Dryas, or of incision during the LateGlacial–Holocene transition. This trend seems to reflect the specificity of the south-western Parisian Basin climate from the Late Weichselian up to the end of the Boreal, due to the influence of the Atlantic Ocean, compared to more northern areas where the climate was more continental. The downstream incision trend during the last third of the Boreal up to the Subatlantic (phases 5 and 6) indicates a sharp increase in precipitation and vegetation cover; the lack of peaty sediments, widespread in north-western Europe, and also of precipitated carbonates frequent in the Parisian Basin, seems to be due to local physiographic characteristics. The main part of the sediment filling, which is principally silty and retrograde, began during the Subatlantic (phase 7 and 8) as a result of deforestation of the plateaux for crop farming. High human-induced sediment yield and storage concealed the possible impacts of climate change on fluvial dynamics: lithological facies change from phase 7 to 8 can only indicate the autogenic morphological evolution of the floodplain in accretion. The non-univocal upstream–downstream variation in the start of phase 7 shows that sediment yield varied in space and time in the catchment, particularly in relation to the agricultural potential of the different areas; this observation could be used to testify human-induced sedimentation in other catchments.     

Reactivity at (nano)particle-water interfaces,redox processes,and arsenic transport in the environment

Massive deleterious impacts to human health are resulting from the use of arsenic-bearing groundwaters in South-East Asia deltas and elsewhere in the world for drinking, cooking and/or irrigation. In Bangladesh alone, a fifth of all deaths are linked to arsenicosis. In the natural and engineered subsurface environment, the fate of arsenic is, to a large extent, controlled by redox potential, pH, as well as total iron, sulfur and carbonate content, via sorption and coprecipitation on a variety of natural and engineered (nano)particles. In the present article, we address: (1) new insights in the sorption mechanisms of As on Fe(II) and Fe(III) nanophases recognized to play an important role in the microbial cycling of As and Fe; (2) artifacts often encountered in field and laboratory studies of As speciation due to the extreme redox sensitivity of the Fe-As-O-H phases; and (3) as a conclusion, the implications for water treatment. Indeed the specific reactivity of nanoparticles accounts not only for the As bioavailability within soils and aquifers, but also opens new avenues in water treatment.     

Line-broadening effects in the powder infrared spectrum of apatite

The crystallinity of natural and synthetic apatite samples is often determined from the broadening of ν ₄ PO₄ infrared absorption bands. However, various physical mechanisms contribute to the observed linewidth. In the present study, the factors determining the linewidth in the powder spectrum of synthetic fluorapatite and hydroxyapatite samples are investigated. The temperature dependence of the infrared spectrum (10–270 K) is used to assess the respective contributions of homogeneous broadening, related to the decay of phonons through anharmonic coupling, and heterogeneous broadening related to elastic strain and macroscopic electrostatic effects. This latter contribution is dominant in the investigated samples and depends on the shape of powder particles. It is discussed under the light of the theoretical modeling of the low-frequency dielectric properties of apatite based on first-principles density functional theory calculations. The linewidth of the weak ν ₁ PO₄ absorption band provides a reliable information on microscopic sources of broadening, i.e., apatite crystallinity. In comparison, the other more intense PO₄ bands are more sensitive to long-range electrostatic effects.