The fungal–mineral interface: challenges and considerations of micro-analytical developments

Over recent years, the role of fungi, especially mycorrhizal fungi, in the weathering of rock-forming minerals has been increasingly recognised. Much of our understanding of the effects of fungi on mineral weathering is based on macroscopic studies. However, the ability of fungi to translocate materials, including organic acids and siderophores, to specific areas of a mineral surface leads to significant spatial heterogeneity in the weathering process. Thus, geomycologists are confronted with unique challenges of how to comprehend and quantify such a high degree of diversity and complicated arrays of interactions. Recent advances in experimental and analytical techniques have increased our ability to probe the fungal–mineral interface at the resolution necessary to decouple significant biogeochemical processes. Modern microscopy, spectroscopy, mass spectrometry, wet chemistry, and scattering techniques allow for the selective extraction of physical, chemical, and structural data at the micro- to nano-scale. These techniques offer exciting possibilities to study fungal–mineral interactions at the scale of individual hyphae. In this review, we give an overview of some of these techniques with their characteristics, advantages and limitations, and how they can be used to further our understanding of biotic mineral weathering.     

Microbes: Mini Iron Factories

Microbes have flourished in extreme habitats since beginning of the Earth and have played an important role in geological processes like weathering, mineralization, diagenesis, mineral formation and destruction. Biotic mineralization is one of the most fascinating examples of how microbes have been influencing geological processes. Iron oxidizing and reducing bacteria are capable of precipitating wide varieties of iron oxides (magnetite), carbonates (siderite) and sulphides (greigite) via controlled or induced mineralization processes. Microbes have also been considered to play an important role in the history of evolution of sedimentary rocks on Earth from the formation of banded iron formations during the Archean to modern biotic bog iron and ochre deposits. Here, we discuss the role that microbes have been playing in precipitation of iron and the role and importance of interdisciplinary studies in the field of geology and biology in solving some of the major geological mysteries.     

Investigating Devonian trees as geo‐engineers of past climates: linking palaeosols to palaeobotany and experimental geobiology

We present the rationale for a cross‐disciplinary investigation addressing the ‘Devonian plant hypothesis’ which proposes that the evolutionary appearance of trees with deep, complex rooting systems represents one of the major biotic feedbacks on geochemical carbon cycling during the Phanerozoic. According to this hypothesis, trees have dramatically enhanced mineral weathering driving an increased flux of Ca²⁺ to the oceans and, ultimately, a 90% decline in atmospheric CO₂ levels through the Palaeozoic. Furthermore, experimental studies indicate a key role for arbuscular mycorrhizal fungi in soil–plant processes and especially in unlocking the limiting nutrient phosphorus in soil via Ca‐phosphate dissolution mineral weathering. This suggests co‐evolution of roots and symbiotic fungi since the Early Devonian could well have triggered positive feedbacks on weathering rates whereby root–fungal P release supports higher biomass forested ecosystems. Long‐standing areas of uncertainty in this paradigm include the following: (1) limited fossil record documenting the origin and timeline of the evolution of tree‐sized plants through the Devonian; and (2) the effects of the evolutionary advance of trees and their in situ rooting structures on palaeosol geochemistry. We are addressing these issues by integrating palaeobotanical studies with geochemical and mineralogical analyses of palaeosol sequences at selected sites across eastern North America with a particular focus on drill cores from Middle Devonian forests in Greene County, New York State.     

Rapid soil formation after glacial retreat shaped by spatial patterns of organic matter accrual in microaggregates

Global change contributes to the retreat of glaciers at unprecedented rates. The deglaciation facilitates biogeochemical processes on glacial deposits with initiating soil formation as an important driver of evolving ecosystems. The underlying mechanisms of soil formation and the association of soil organic matter (SOM) with mineral particles remain unclear, although further insights are critical to understand carbon sequestration in soils. We investigated the microspatial arrangement of SOM coatings at intact soil microaggregate structures during various stages of ecosystem development from 15 to >700 years after deglaciation in the proglacial environment of the Damma glacier (Switzerland). The functionally important clay‐sized fraction (<2 μm) was separated into two density fractions with different amounts of organo‐mineral associations: light (1.6–2.2 g/cm³) and heavy (>2.2 g/cm³). To quantify how SOM extends across the surface of mineral particles (coverage) and whether SOM coatings are distributed in fragmented or connected patterns (connectivity), we developed an image analysis protocol based on nanoscale secondary ion mass spectrometry (NanoSIMS). We classified SOM and mineral areas depending on the ¹⁶O^?, ¹²C^?, and ¹²C¹⁴N^? distributions. With increasing time after glacial retreat, the microspatial coverage and connectivity of SOM increased rapidly. The rapid soil formation led to a succession of patchy distributed to more connected SOM coatings on soil microaggregates. The maximum coverage of 55% at >700 years suggests direct evidence for SOM sequestration being decoupled from the mineral surface, as it was not completely masked by SOM and retained its functionality as an ion exchange site. The chemical composition of SOM coatings showed a rapid change toward a higher CN:C ratio already at 75 years after glacial retreat, which was associated with microbial succession patterns reflecting high N assimilation. Our results demonstrate that rapid SOM sequestration drives the microspatial succession of SOM coatings in soils, a process that can stabilize SOM for the long term.     

Geochemistry and palaeogeography of upper Ordovician glaciogenic sedimentary rocks in the Table Mountain Group, South Africa

Evidence for a late Ordovician glaciation is best known from northern Africa and locally in South Africa, and western South America. The South African glacial deposits (Pakhuis Formation of the Table Mountain Group) are present in the western part of the Cape Fold Belt. Two thin diamictites are succeeded by a coarsening upward shale-siltstone unit known as the Cedarberg Formation. These glaciogenic rocks are associated with one of the world's greatest accumulations of mature sandstones. The diamictites are under- and overlain by shales and sandstones that have undergone extensive alteration, presumably as a result of chemical weathering. Some diamictite samples have low values for a Chemical Index of Alteration (CIA), in keeping with their inferred glacial origin. Immediately above the glaciogenic diamictites, black shales, comprising the basal Soom Member of the Cedarberg Formation preserve an unusual soft bodied fauna and are enriched in Mo, U and other trace elements. The unusual chemical composition of these shales is attributed to starved basin conditions and a reducing environment during a rapid sea level rise that accompanied demise of the late Ordovician glaciers. The late Ordovician glacial deposits of western South Africa are widely regarded as the distal deposits of a large continental ice sheet centred on North Africa but they may have been partly derived from piedmont glaciers that descended from highlands formed as a result of late Ordovician orogeny.     

Thawing glacial and permafrost features contribute to nitrogen export from Green Lakes Valley,Colorado Front Range,USA

Alpine ecosystems are particularly susceptible to disturbance due to their short growing seasons, sparse vegetation and thin soils. Increased nitrogen deposition in wetfall and changes in climate currently affect Green Lakes Valley within the Colorado Front Range. Research conducted within the alpine links chronic nitrogen inputs to a suite of ecological impacts, resulting in increased nitrate export. The atmospheric nitrogen flux decreased by 0.56 kg ha^?1 year^?1 between 2000 and 2009, due to decreased precipitation; however alpine nitrate yields increased by 40 % relative to the previous decade (1990–1999). Long term trends indicate that weathering products such as sulfate, calcium, and silica have also increased over the same period. The geochemical composition of thawing permafrost, as indicated by rock glacial and blockfield meltwater, suggests it is the source of these weathering products. Furthermore, mass balance models indicate the high ammonium loads within glacial meltwater are rapidly nitrified, contributing ~0.5–1.4 kg N ha^?1 to the growing season nitrate flux from the alpine watershed. The sustained export of these solutes during dry, summer months is likely facilitated by thawing cryosphere providing hydraulic connectivity late into the growing season. This mechanism is further supported by the lack of upward weathering or nitrogen solute trends in a neighboring catchment which lacks permafrost and glacial features. These findings suggest that reductions of atmospheric nitrogen deposition alone may not improve water quality, as cryospheric thaw exposes soils to biological and geochemical processes that may affect alpine nitrate concentrations as much as atmospheric deposition trends.     

The Effect of Phosphorus Availability on Decomposition Dynamics in a Seasonal Lowland Amazonian Forest

Once the weathering of parent material ceases to supply significant inputs of phosphorus (P), vegetation depends largely on the decomposition of litter and soil organic matter and the associated mineralization of organic P forms to provide an adequate supply of this essential nutrient. At the same time, the decomposition of litter is often characterized by the immobilization of nutrients, suggesting that nutrient availability is a limiting factor for this process. Immobilization temporally decouples nutrient mineralization from decomposition and may play an important role in nutrient retention in low-nutrient ecosystems. In this study, we used a common substrate to study the effects of native soil P availability as well as artificially elevated P availability on litter decomposition rates in a lowland Amazonian rain forest on highly weathered soils. Although both available and total soil P pools varied almost three fold across treatments, there was no significant difference in decomposition rates among treatments. Decomposition was rapid in all treatments, with approximately 50% of the mass lost over the 11-month study period. Carbon (C) and nitrogen (N) remaining and C:N ratios were the most effective predictors of amount of mass remaining at each time point in all treatments. Fertilized treatments showed significant amounts of P immobilization (P < 0.001). By the final collection point, the remaining litter contained a quantity equivalent to two-thirds of the initial P and N, even though only half of the original mass remained. In these soils, immobilization of nutrients in the microbial biomass, late in the decomposition process, effectively prevents the loss of essential nutrients through leaching or occlusion in the mineral soil.     

Sedimentary response to sea level and climate changes in the inner sea of Maldives carbonate platform over the past 30 kyr

We applied AMS ¹⁴C dates, Mg/Ca estimated sea surface temperature (SST), planktonic foraminiferal abundance, coarse component and X-ray diffraction mineral composition analyses for an International Ocean Discovery Program (IODP) sediment Hole U1467C in the Maldives inner sea, to reveal factors that affected the depositional process in the Maldives inner sea over the past 30 kyr. We found that the linear sedimentation rate (LSR) in Holocene (6.8 cm/kyr) was obviously higher than that in glacial period (3.45 cm/kyr); the average SST during the Holocene was 2–3°C higher than that in glacial stage. High abundance of planktonic foraminifera occurred during the glacial period, which was consistent with the variation of pelagic biogenic component. Reef-sourced material showed apparent high percentage during the Holocene (43.5%), in contrast to the low values during the glacial stage (20.7%). Terrigenous matter, only accounting for a small percentage in carbonate platform, was relatively high during the glacial period than that in the Holocene. We therefore conclude that reef-sourced material, dominated in the glacial-interglacial sediment sources, was mainly affected by sea level and climate changes. During glacial stage, sea level low-stand and weakened weathering in Maldives limited the input of the eroded material into the inner sea, resulting in low LSR; while the Holocene high sea level accompanied with rapid growth of the reef atoll and enhanced weathering, brought more reef-sourced material to the inner sea, leading to increased LSR and lowered abundance of planktonic foraminifera. The sea level and climate-controlled reef-sourced material changes are the key to understand the sedimentary process of the Maldives inner sea. Our study will shed some light on the evolution of glacial-interglacial sedimentary process of carbonate platform.     

Clay minerals in Cenozoic sediments off Cape Roberts (McMurdo Sound, Antarctica) reveal palaeoclimatic history

The clay mineral assemblages of the ca. 1600 m thick Cenozoic sedimentary succession recovered at the CRP-1, CRP-2/2A and CRP-3 drill sites off Cape Roberts on the McMurdo Sound shelf, Antarctica, were analysed in order to reconstruct the palaeoclimate and the glacial history of this part of Antarctica. The sequence can be subdivided into seven clay mineral units that reflect the transition from humid to subpolar and polar conditions. Unit I (35-33.6 Ma) is characterised by an almost monomineralic assemblage consisting of well crystalline, authigenic smectite, and therefore does not allow a palaeoclimatic reconstruction. Unit II (33.6-33.1 Ma) has also a monomineralic clay mineral composition. However, the assemblage consists of variably crystallized smectite that, at least in part, is of detrital origin and indicates chemical weathering under a humid climate. The main source area for the clays was in the Transantarctic Mountains. Minor amounts of illite and chlorite appear for the first time in Unit III (33.1-31 Ma) and suggest subordinate physical weathering. The sediments of Unit IV (31-30.5 Ma) have strongly variable smectite and illite concentrations indicating an alternation of chemical weathering periods and physical weathering periods. Unit V (30.5-24.2 Ma) shows a further shift towards physical weathering. Unit VI (24.2-18.5 Ma) indicates strong physical weathering under a cold climate with persistent and intense illite formation. Unit VII (18.5 Ma to present) documents an additional input of smectite derived from the McMurdo Volcanic Group in the south.     

Microbial Precipitation of Arsenic Sulfides in Andean Salt Flats

An abiotic origin has traditionally been assumed for the arsenic minerals realgar and orpiment associated with thermal springs. Microbial precipitation of arsenic, however, has been studied in pure cultures and the isotopic composition of arsenic sulfides associated with some borate deposits suggests a biotic origin for those minerals. The aim of the present study is to demonstrate the role of bacterial arsenic precipitation in the biogeochemical cycle of arsenic in such borate deposits. For this purpose both enrichment and pure cultures were obtained from the natural arsenic minerals and the composition and isotopic signatures of the arsenic sulfide minerals precipitated by the cultures and those associated with boron deposits from an Andean salt flat in northern Chile were compared. Based on the microbiological and chemical evidence gathered, it is concluded that bacteria contributed to the formation of the arsenic minerals. This interpretation is based on the consistent association of a variety of features that strongly indicate microbial involvement in the precipitation process. These include: (1) enrichment and isolation of cultures with arsenic precipitation capacity from arsenic mineral samples, (2) high numbers of arsenic-precipitating bacteria in the Andean minerals and brines, (3) chemical and mineralogical properties of precipitates experimentally formed under biotic and abiotic conditions, (4) similarities in stoichiometry between natural and laboratory obtained minerals, and (5) the consistent depletion in δ³⁴S values for natural versus laboratory obtained sulfides. Thus, microbial precipitation of arsenic sulfides is a geochemically relevant metabolism.     

Occupation of the Antarctic continent by petrels during the past 35 000 years: Inferences from a 14C study of stomach oil deposits

Summary The dated material was taken from organic deposits occurring in snow petrel colonies of the Untersee Oasis, central Queen Maud Land, East Antarctica. These deposits have been formed by accumulation and solidification of stomach oil regurgitated by petrels over a long time period. Within the deposits the ¹⁴C ages tend to increase with depth. Local mixing and irregular ¹⁴C profiles are of minor importance. This confirms the suitability of such material for ¹⁴C dating. According to the ¹⁴C chronology the colonies near Lake Untersee have been continuously occupied at least during the past 8 kyr. Surprisingly old ages for three samples, namely 13.8, 18.4 and 33.9 kyr BP, suggest that breeding colonies must have been in the study area during the last glacial maximum. Information about the minimum age of moraines and the timing of local ice retreat can be obtained from a correlation between the oldest ¹⁴C age of the organic material accumulated on moraines and the altitude of the sample site.     

Winter climate change implications for decomposition in northeastern forests: comparisons of sugar maple litter with herbivore fecal inputs

Forests in northeastern North America are influenced by varying climatic and biotic factors; however, there is concern that rapid changes in these factors may lead to important changes in ecosystem processes such as decomposition. Climate change (especially warming) is predicted to increase rates of decomposition in northern latitudes. Warming in winter may result in complex effects including decreased levels of snow cover and an increased incidence of soil freezing that will effect decomposition. Along with these changes in climate, moose densities have also been increasing in this region, likely affecting nutrient dynamics. We measured decomposition and N release from ¹⁵N‐labeled sugar maple leaf litter and moose feces over 20 months in reference and snow removal treatment (to induce soil freezing) plots in two separate experiments at the Hubbard Brook Experimental Forest in New Hampshire, USA. Snow removal/soil freezing decreased decomposition of maple litter, but stimulated N transfer to soil and microbial biomass. Feces decomposed more rapidly than maple litter, and feces N moved into the mineral soil more than N derived from litter, likely due to the lower C : N ratio of feces. Feces decomposition was not affected by the snow removal treatment. Total microbial biomass (measured as microbial N and C) was not significantly affected by the treatments in either the litter or feces plots. These results suggest that increases in soil freezing and/or large herbivore populations, increase the transfer rate of N from plant detritus or digested plants into the mineral soil. Such changes suggest that altering the spatial and temporal patterns of soil freezing and moose density have important implications for ecosystem N cycling.     

Decomposition of duckweed (Lemna gibba) under axenic and microbial [-2pt] conditions: flux of nutrients between litter water and sediment, the impact of leaching and microbial degradation

The decomposition of axenic Lemna gibba has been studied over a 200 day period under laboratory conditions in the presence and absence of wastewater micro-organisms. The residual mass of plant litter in the decomposition vessels decreased three times more rapidly under biotic than abiotic conditions. The organic matter in the duckweed litter lost about half its weight within 67.9 days in the presence of micro-organisms while more than 200 days were required in axenic vessels. In the former case, AFDW loss followed an exponential pattern of decay. The rate constant was 0.0102 day ^–1 and the decay was virtually complete after 200 days. The C and K concentration of the remaining duckweed litter decreased; the N, Ca, Fe and B concentration increased in both treatments. The concentration of total N, P, K, Mg, and Mo increased in the receiving water in both treatments but was much higher under biotic than abiotic conditions. Mass balances of nutrients in the vessels and flux of these nutrients between compartments in the vessels (duckweed litter, water and sediment) have been determined. Under axenic conditions the release of elements was very slow. Only notably potassium leaching had occurred. Leaching of potassium, magnesium and organic carbon took place mainly during the first term of incubation and then slowed down. Under biotic decomposition the elemental content of the litter decreased by more than 50% over 43 days for K, 53 days for Mo, 64 days for C, 81 days for Mg, 101 days for S, 104 days for P, 108 days for Na, 111 days for N, 140 days for B. Calcium and iron immobilised in the litter. Most of the released N, S, P, K, Mg and Mo remained in the water, but B and Mn settled into the sediment. The result of the investigation demonstrated that the nutrient flux from decomposing duckweed litter is mainly a microbially mediated process.     

Carbon dioxide consumption during soil development

Carbon is sequestered in soils by accumulation of recalcitrant organic matter and by bicarbonate weathering of silicate minerals. Carbon fixation by ecosystems helps drive weathering processes in soils and that in turn diverts carbon from annual photosynthesis-soil respiration cycling into the long-term geological carbon cycle. To quantify rates of carbon transfer during soil development in moist temperate grassland and desert scrubland ecosystems, we measured organic and inorganic residues derived from the interaction of soil biota and silicate mineral weathering for twenty-two soil profiles in arkosic sediments of differing ages. In moist temperate grasslands, net annual removal of carbon from the atmosphere by organic carbon accumulation and silicate weathering ranges from about 8.5 g m^–2 yr^–1 for young soils to 0.7 g M^–2 yr^–1 for old soils. In desert scrublands, net annual carbon removal is about 0.2 g m^–2 yr^–1 for young soils and 0.01 g m^–2 yr^–1 for old soils. In soils of both ecosystems, organic carbon accumulation exceeds CO₂ removal by weathering, however, as soils age, rates of CO₂ consumption by weathering accounts for greater amounts of carbon sequestration, increasing from 2% to 8% in the grassland soils and from 2% to 40% in the scrubland soils. In soils of desert scrublands, carbonate accumulation far outstrips organic carbon accumulation, but about 90% of this mass is derived from aerosolic sources that do not contribute to long-term sequestration of atmospheric carbon dioxide.     

Soil–litter mixing and microbial activity mediate decomposition and soil aggregate formation in a sandy shrub-invaded Chihuahuan Desert grassland

Drylands account globally for 30% of terrestrial net primary production and 20% of soil organic carbon. Present ecosystem models under predict litter decay in drylands, limiting assessments of biogeochemical cycling at multiple scales. Overlooked decomposition drivers, such as soil–litter mixing (SLM), may account for part of this model-measurement disconnect. We documented SLM and decomposition in relation to the formation of soil-microbial films and microbial extracellular enzyme activity (EEA) in the North American Chihuahuan Desert by placing mesh bags containing shrub (Prosopis glandulosa) foliar litter on the soil surface within contrasting vegetation microsites. Mass loss (in terms of k, the decay constant) was best described by the degree of SLM and soil-microbial film cover. EEA was greatest during periods of rapid litter decomposition and associated SLM. Soil-microbial film cover on litter surfaces increased over time and was greater in bare ground microsites (50% litter surface area covered) compared to shrub and grass microsites (37 and 33% covered, respectively). Soil aggregates that formed in association with decomposing leaf material had organic C and N concentrations 1.5–2× that of local surface soils. Micrographs of soil aggregates revealed a strong biotic component in their structure, suggesting that microbial decomposition facilitates aggregate formation and their C and N content. Decomposition drivers in arid lands fall into two major categories, abiotic and biotic, and it is challenging to ascertain their relative importance. The temporal synchrony between surface litter mass loss, EEA, biotic film development, and aggregate formation observed in this study supports the hypothesis that SLM enhances decomposition on detached litter by promoting conditions favorable for microbial processes. Inclusion of interactions between SLM and biological drivers will improve the ability of ecosystem models to predict decomposition rates and dynamics in drylands.     

The role of fungi in biogenic weathering in boreal forest soils

In this article we discuss the possible significance of biological processes, and of fungi in particular, in weathering of minerals. We consider biological activity to be a significant driver of mineral weathering in forest ecosystems. In these environments fungi play key roles in organic matter decomposition, uptake, transfer and cycling of organic and inorganic nutrients, biogenic mineral formation, as well as transformation and accumulation of metals. The ability of lichens, mutualistic symbioses between fungi and photobionts such as algae or cyanobacteria, to weather minerals is well documented. The role of mycorrhizal fungi forming symbioses with forest trees is less well understood, but the mineral horizons of boreal forests are intensively colonised by mycorrhizal mycelia which transfer protons and organic metabolites derived from plant photosynthates to mineral surfaces, resulting in mineral dissolution and mobilisation and redistribution of anionic nutrients and metal cations. The mycorrhizal mycelia, in turn provide efficient systems for the uptake and direct transport of mobilised essential nutrients to their host plants which are large sinks. Since almost all (99.99 %) non-suberised lateral plant roots involved in nutrient uptake are covered by ectomycorrhizal fungi, most of this exchange of metabolites must take place through the plant–fungus interface. This idea is still consistent with a linear relationship between soil mineral surface area and weathering rate since the mycelia that emanate from the tree roots will have a larger area of contact with minerals if the mineral surface area is higher. Although empirical models based on bulk soil solution chemistry may fit field data, we argue that biological processes make an important contribution to mineral weathering and that a more detailed mechanistic understanding of these must be developed in order to predict responses to environmental changes and anthropogenic impact.     

Facies and diagenetic evaluation of the Permian–Triassic boundary interval and basal Triassic carbonates: shallow and deep ramp sections,Hungary

The Permian–Triassic boundary and basal Triassic shallow-marine successions were studied and correlated in sections of two structural units in Hungary (Transdanubian Range and Bükk units). Core sections in the Transdanubian Range unit recovered inner ramp deposits whereas outcrops in the Bükk unit expose deposits of the deeper ramp area of the western Tethys. The inner ramp section (studied ca. 10 m in thickness) is characterized by a succession of dolomites overlain by bioclastic limestones, peloidal grainstones (which recorded the biotic decline) and oolites with finely crystalline limestone interlayers. The deeper ramp section (studied ca. 15 m in thickness) is characterized by a succession of bioclastic limestones and marlstones, mudstone beds (recording the first biotic decline), the ‘boundary shales’ (recording the second biotic decline and the stable carbon isotope marker), mudstones with wackestone laminae, and stromatolite boundstones. Accordingly, oolite formation and microbial micrite precipitation represent carbonate sedimentary responses of end-Permian mass extinction on the carbonate shelf. In both successions, mudstones predominate the upsection, suggesting a relative sea-level rise. The succession of the deep ramp area exhibits a continuous sediment accumulation and the diagenesis here was influenced by marine and marine-derived pore water. The δ¹³C curve shows a continuous change towards more negative values, starting in bioclastic limestones, followed by a sharp symmetric negative peak at the second biotic decline that is a chemostratigraphic marker of the boundary event. Facies and microfacies trend of the inner ramp carbonates in the Transdanubian Range unit exhibits close similarities to that found in many South Alpine sections. Relict peloidal deposits, formed cemented submarine hardground substrate, indicate the extinction level. Sedimentary and diagenetic features of the overlying oolite bedset revealed slightly different depositional environments in the two studied Transdanubian Range unit sections. Petrography of the oolites highlighted shallow burial diagenetic alterations which includes marine cementation, marine-burial replacement and dolomitization. A lack of the specific negative peak in the δ¹³C values is most likely due to the multiple redeposition events of the sedimentary grains. This led to the conclusion that the deeper ramp deposits (e.g., in Bükk unit) have greater potential for recognizing trends in processes, affecting the marine environments and related to the end-Permian mass extinction, at the western Tethys.     

Montmorillonite-catalysed formation of RNA oligomers: the possible role of catalysis in the origins of life

Large deposits of montmorillonite are present on the Earth today and it is believed to have been present at the time of the origin of life and has recently been detected on Mars. It is formed by aqueous weathering of volcanic ash. It catalyses the formation of oligomers of RNA that contain monomer units from 2 to 30-50. Oligomers of this length are formed because this catalyst controls the structure of the oligomers formed and does not generate all possible isomers. Evidence of sequence-, regio- and homochiral selectivity in these oligomers has been obtained. Postulates on the role of selective versus specific catalysts on the origins of life are discussed. An introduction to the origin of life is given with an emphasis on reaction conditions based on the recent data obtained from zircons 4.0-4.5Ga.     

Biogeochemical controls on aluminum chemistry in the O horizon of a red spruce (Picea rubens Sarg.) stand in central Maine,USA

This study examined the biotic and abiotic processes controlling solution chemistry and cycling of aluminum (Al) in the organic horizons of a northern coniferous forest ecosystem. A mass balance budget indicated that aboveground inputs of Al to the O horizon averaged 0.9 kg ha^–1 1 yr^–1, with major inputs accounted for by litterfall (69%), followed by precipitation (21%), and net canopy throughfall plus stemflow (10%). Estimated leaching losses of Al from the O horizon averaged 2.1 kg Al ha^-1 yr1. We hypothesize that the difference between measured Al inputs and outputs can be accounted for by Al release from weathering of soil minerals admixed into the O horizon. Variations in O horizon solution Al chemistry were influenced by a number of factors, including pH, Al equilibria with different solid-phase organic exchange sites, and Al complexation with humic ligands in soil solution.     

The relationship between surface water chemistry and geology in the North Branch of the Moose River

The chemistry of lakes and streams within the North Branch of the Moose River is strongly correlated with the nature and distrubution of geologic materials in the watershed. The dominance of thin glacial till and granitic gneiss bedrock in the region north and east of Big Moose Lake results in a geologically sensitive terrain that is characterized by surface water with low alkalinity and chemical compositions only slightly modified from ambient precipitation. In contrast, extensive deposits of thick glacial till and stratified drift in the lower part of the system (e.g. Moss-Cascade valley) allow for much infiltration of precipitation to the groundwater system where weathering reactions increase alkalinity and significantly alter water chemistry.The hypothesis that surficial geology controls the chemistry of surface waters in the Adirondacks holds true for 70 percent of the Moose River watershed. Exceptions include the Windfall Pond subcatchment which is predominantly covered by thin till, yet has a high surface water alkalinity due to the presence of carbonate-bearing bedrock. The rapid reaction rates of carbonate minerals allow for complete acid neutralization to occur despite the short residence time of water moving through the system. Another important source of alkalinity in at least one of the subcatchments is sulfate reduction. This process appears to be most important in systems containing extensive peat deposits.An analysis of only those subcatchments controlled by the thickness of surficial sediments indicates that under current atmospheric loadings watersheds containing less than 3 percent thick surficial sediments will be acidic while those with up to 12 percent will be extremely sensitive to acidification and only those with over 50 percent will have a low sensitivity.