Predicting Biogeochemical Calcium Precipitation in Landfill Leachate Collection Systems

Clogging of leachate collection systems within municipal solid waste landfills can result in greater potential for contaminants to breach the landfill barrier system. The primary cause of clogging is calcium carbonate (CaCO_3(s)) precipitation from leachate and its accumulation within the pore space of the drainage medium. CaCO_3(s) precipitation is caused by the anaerobic fermentation of volatile fatty acids (VFAs), which adds carbonate to and raises the pH of the leachate. An important relationship in modeling clogging in leachate collections systems is a yield coefficient that relates microbial fermentation of VFAs to precipitation of calcium carbonate. This paper develops a new, mechanistically based yield coefficient, called the carbonic acid yield coefficient (Y_H), which relates the carbonic acid (H₂CO₃) produced from microbial fermentation of acetate, propionate, and butyrate to calcium precipitation. The empirical values of Y_H were computed from the changes in acetate, propionate, butyrate, and calcium concentrations in leachate as it permeated through gravel-size material. The theoretical and empirical results show that the primary driver of CaCO_3(s) precipitation is acetate fermentation. Additionally, other non-calcium cations (e.g., iron and magnesium) precipitated with carbonate (CO_2-) when present in the leachate. A common yield between total cations bound to CO₃ ^2- and H₂CO₃ produced, called the calcium carbonate yield coefficient (Y_c), can reconcile the empirical yield coefficient for synthetic and actual leachates.     

Peat characteristics and groundwater geochemistry of calcareous fens in the Minnesota River Basin, U.S.A.

Calcareous fens in Minnesota are spring-seepage peatlands with adistinctive flora of rare calciphilic species. Peat characteristics andgroundwater geochemistry were determined for six calcareous fens in theMinnesota River Basin to better understand the physical structure andchemical processes associated with stands of rare vegetation. Onset of peataccumulation in three of the fens ranged from about 4,700 to 11,000 ¹⁴C yrs BP and probably resulted from acombination of climate change and local hydrogeologic conditions. Most peatcores had a carbonate-bearing surface zone with greater than 10%carbonates (average 27%, dry wt basis), an underlyingcarbonate-depleted zone with 10% or less carbonates (average4%), and a carbonate-bearing lower zone again with greater than10% carbonates (average 42%). This carbonate zonation washypothesized to result from the effect of water-table level on carbonateequilibria: carbonate precipitation occurs when the water table is above acritical level, and carbonate dissolution occurs when the water table islower. Other processes that changed the major ion concentrations inupwelling groundwater include dilution by rain water, sulfate reduction orsulfide oxidation, and ion adsorption or exchange. Geochemical modelingindicated that average shallow water in the calcareous fens during the studyperiod was groundwater mixed with about 6 to 13% rain water.Carbonate precipitation in the surface zone of calcareous fens could bedecreased by a number of human activities, especially those that lower thewater table. Such changes in shallow water geochemistry could alter thegrowing conditions that apparently sustain rare fen vegetation.     

Changes in osmotic and ionic concentrations in the hemolymph of Macrobrachium rosenbergii exposed to varying salinities and correlation to ionic and crystalline composition of the cuticle

Osmotic and ionic regulatory ability were examined in the giant freshwater prawn, Macrobrachium rosenbergii in response to varying salinities. In freshwater, and under conditions of low salinity, hemolymph osmolality was maintained around 450 mOsm. Under high salinity, osmolality values increased in a time-wise manner until reaching levels of the surrounding rearing water. Changes in sodium concentration generally paralleled osmotic change, and potassium and magnesium concentrations increased upon exposure to extremely high salinity. In contrast, total calcium concentration was maintained at high levels regardless of salinity treatment. Examination of crystalline structure and ionic composition of the cuticle revealed that it was comprised principally of an α-chitin-like material, and calcite (calcium carbonate). Calcite accounted for 25% of total bulk weight in freshwater, while sodium, potassium and magnesium constituents combined comprised less than 2.5% of this total. Although sodium, potassium and magnesium contents increased nearly 2-fold in response to changing salinity, calcium levels remained relatively constant.     

Modified future diurnal variability of the global surface ocean CO2 system

Our understanding of how increasing atmospheric CO₂ and climate change influences the marine CO₂ system and in turn ecosystems has increasingly focused on perturbations to carbonate chemistry variability. This variability can affect ocean-climate feedbacks and has been shown to influence marine ecosystems. The seasonal variability of the ocean CO₂ system has already changed, with enhanced seasonal variations in the surface ocean pCO₂ over recent decades and further amplification projected by models over the 21st century. Mesocosm studies and CO₂ vent sites indicate that diurnal variability of the CO₂ system, the amplitude of which in extreme events can exceed that of mean seasonal variability, is also likely to be altered by climate change. Here, we modified a global ocean biogeochemical model to resolve physically and biologically driven diurnal variability of the ocean CO₂ system. Forcing the model with 3-h atmospheric outputs derived from an Earth system model, we explore how surface ocean diurnal variability responds to historical changes and project how it changes under two contrasting 21st-century emission scenarios. Compared to preindustrial values, the global mean diurnal amplitude of pCO₂ increases by 4.8 μatm (+226%) in the high-emission scenario but only 1.2 μatm (+55%) in the high-mitigation scenario. The probability of extreme diurnal amplitudes of pCO₂ and [H⁺] is also affected, with 30- to 60-fold increases relative to the preindustrial under high 21st-century emissions. The main driver of heightened pCO₂ diurnal variability is the enhanced sensitivity of pCO₂ to changes in temperature as the ocean absorbs atmospheric CO₂. Our projections suggest that organisms in the future ocean will be exposed to enhanced diurnal variability in pCO₂ and [H⁺], with likely increases in the associated metabolic cost that such variability imposes.     

Stable isotope ratios of soil carbonate and soil organic matter as indicators of forest invasion of prairie near Ames,Iowa

Stable isotope ratios of pedogenic carbonate and organic matter were measured in a prairie-transition-forest soil biosequence near Ames, Iowa to determine the vegetation succession. The modern vegetation is dominated by non-native C₃ plants which have been introduced by agricultural practices. The ¹³C values of soil organic matter from the prairie and forest endmembers indicate C₄ and C₃ dominated ecosystems, respectively, during the accumulation of soil organic matter. Pedogenic carbonate from all soils, including rare pedogenic carbonate from the forested soil, has an average ¹³C of-2.0, indicating that the carbonate formed under a C₄ vegetation. These results indicate that the ecosystem was a C₄-dominated prairie and therefore suggest a recent arrival of forests and other C₃ plants in the area. This study also implies that the primary features of the transitional Lester soil series, which has soil properties intermediate between Alfisols and Molisolls, formed under prairie conditions and were overprinted by an invading forest.     

Paleoecologic,temporal, and spatial analysis of early Silurian Reefs of the Chicotte Formation,Anticosti Island,Quebec, Canada

Summary Reefs of the Lower Silurian Chicotte Formation are the largest and most faunally diverse known on Anticosti Island, Quebec. They reach up to 25 m in thickness and 250 m in diameter and are present predominantly at two intervals, forming a lower and upper reef cluster. Remnants of bioherms are represented on the present-day wave-cut terrace as 60 to 100 m diameter, subcircular erosional depressions known as Philip structures or as outcrop. The bioherms were relatively low structures, with approximately 3 to 5 m maximum synoptic relief, some of which developed on hardgrounds and possible paleokarst surfaces of crinoidal wackestone and packstone. Dominant skeletal framework builders and sediment producers within all of the reefs are laminar to low domical stromatoporoids, colonial cerioid and fasciculate rugose corals, colonial tabulate corals, and cryptostome bryozoans. Vertical zonation of reef biota is evident within well-exposed reefs of the lower reef cluster. Three to four stages are recognizable:1) a low-diversity tabulate coral-dominatedpioneering community including large tabulate coral colonies (halysitids and favositids), and few stromatoporoids (clathrodictyids, ecclimadictyids), fasciculate rugosans, large generally monotypic stalked crinoids, and shelly benthos (brachiopods, few ostracodes and trilobites);2) an intermediate- to high-diversity, mixed tabulate coral-stromatoporoid-dominatedreef-core community;3) a slightly lower diversity stromatoporoid-tabulate coral-dominatedclimax community with laminar coenitids and alveolitids; and,4) in a few localities, a capping, low-diversity tabulatecoral-dominated (alveolitid and coenitid), and stromatoporoid-bearing community comprising laminar forms. Amelioration of Early Silurian climates, following Late Ordovician glaciation, allowed gradual reestablishment of extensive shallow-water reef growth, by mainly new and increasingly diverse genera and species of metazoans. Reef development within the Chicotte Formation coincided with global, widespread development of latest Llandovery and earliest Wenlock reefs in subtropical to tropical areas. Chicotte reefs have broad characteristics, in terms of overall biotic composition, vertical successions recognized, and paleogeographic setting, similar to those of equivalent and slightly younger age from intracratonic settings in Baltica (Gotland, Sweden and Estonia) and central and northern Laurentia (Midcontinent, U.S.A.; Hudson Bay, Canada; and North Greenland, Denmark).     

Microwaves Applied to Silver Impregnations with Ammoniacal Silver Carbonate

Techniques for impregnation with ammoniacal silver carbonate provide valuable information on all types of tissue; however, the time investment required to impregnate a few sections has limited their application. We have shortened the impregnation times by using microwaves in techniques for reticular fibers, astrocytes, nerve fibers and chromaffin cells. The results were satisfactory with markedly reduced impregnation time and elimination of nonspecific silver deposits.     

Orchestin, a calcium-binding phosphoprotein, is a matrix component of two successive transitory calcified biomineralizations cyclically elaborated by a terrestrial crustacean

Orchestia cavimana is a crustacean that cyclically replaces its calcified cuticle during molting cycles in order to grow. Its terrestrial way of life requires storage of calcium during each premolt period, as calcareous concretions, in tubular diverticula of the midgut. During the postmolt period the stored calcium is reabsorbed and is translocated through the storage organ epithelium as calcified small spherules. In a previous study, we sequenced and characterized a remarkable component of the organic matrix of the premolt storage structures, Orchestin, which is a calcium-binding phosphoprotein. In this paper, we analyzed the spatiotemporal expression of the orchestin gene by Northern blotting and in situ hybridization, and its translated product by immunocytochemistry. We found evidence that the gene and the protein are expressed specifically during premolt in the storage organs. More interestingly, we demonstrated that the protein is synthesized also during the postmolt period, as a component of the organic matrix of the calcium resorption spherules. Thus, Orchestin is a matrix component that is synthesized by the same cells to contribute alternately to the elaboration of two different calcifications. These results, in addition to the physical and chemical features of the protein, suggest that Orchestin is probably a key molecule in the calcium carbonate precipitation process leading to the cyclic elaboration of two transitory calcified mineralizations by the crustacean Orchestia.     

Microbial Geochemical Calcium Cycle

The participation of microorganisms in the geochemical calcium cycle is the most important factor maintaining neutral conditions on the Earth. This cycle has profound influence on the fate of inorganic carbon, and, thereby, on the removal of CO₂ from the primitive atmosphere. Most calcium deposits were formed in the Precambrian, when the prokaryotic biosphere predominated. After that, calcium recycling based on biogenic deposition by skeletal organisms became the main process. Among prokaryotes, only a few representatives, e.g. cyanobacteria, exhibit a special calcium function. The geochemical calcium cycle is made possible by the universal features of bacteria involved in biologically mediated reactions and is determined by the activities of microbial communities. In the prokaryotic system, the calcium cycle begins with the leaching of igneous rocks, predominantly through the action of the community of organotrophic organisms. The release of carbon dioxide to the soil air by organotrophic aerobes leads to leaching with carbonic acid and soda salinization. Under anoxic conditions, of major importance is the organic acid production by primary anaerobes (fermentative microorganisms). Calcium carbonate is precipitated by secondary anaerobes (sulfate reducers) and to a smaller degree by methanogens. The role of the cyanobacterial community in carbonate deposition is recorded by stromatolites, which are the most common organo–sedimentary Precambrian structures. Deposition of carbonates in cyanobacterial mats as a consequence of photoassimilation of CO₂ does not appear to be a significant process. It is argued that carbonates were deposited at the boundary between the soda continent, which emerged as a result of subaerial leaching with carbonic acid, and the ocean containing Ca²⁺. Such ecotones provided favorable conditions for the development of the benthic cyanobacterial communities, which were the precursors of stromatolites.     

On the nature and causes of luminescent lines and bands in coral skeletons

Holes pushed into the surface of laboratory grade CaCO₃ powder reproduced visible and measurable luminescence similar to that seen and measured in coral skeletons. Heating such powder to 450 °C for 2 h did not destroy the luminescence although it did destroy luminescence in powdered coral skeleton. The effect in coral skeletal powder was probably due to carbonisation of contained organics because addition of small and increasing amounts of powdered charcoal to laboratory grade CaCO₃ increasingly attenuated luminescence. Luminescent lines and bands in coral skeletons have previously been ascribed to incorporation of humic substances. However, coating laboratory grade powder with humic acid attenuates rather than enhances luminescence. Ultra-violet lamps used to display coral luminescent lines and bands emit significant amounts of violet and blue visible light. Reflection of these visible wavelengths from the surface of laboratory grade CaCO₃ powder obscured luminescence of the powder. Multiple reflections within a hole in the powder resulted in absorption of the short wavelengths of visible light, including violet and blue light that would otherwise mask luminescence, and their re-emission at longer wavelengths. Luminescent bands in offshore corals were associated with the low-density regions of the annual density banding pattern. Luminescent lines in skeletons of inshore corals were in narrow regions of low-density skeleton, probably resulting from altered growth during periods of lowered salinity. Accepted: 20 April 2000