Robert M. Kalin

Environmental Controls on the Petrology of a Late Holocene Speleothem from Botswana with Annual Layers of Aragonite and Calcite

ABSTRACT A carbonate stalagmite from Drotskys Cave in northwestern Botswana consists of alternating layers of calcite and aragonite. Layer counts and radiocarbon ages indicate that the calcite-aragonite pairs are annual layers representing about 1500 years of deposition. The annual layering probably resulted from highly seasonal rainfall. Comparison of the uppermost layers of the speleothem with meteorological records shows that precipitation of CaCO3 in Drotskys Cave was controlled by climate. Thickness of calcite layers correlates with rainfall, suggesting that calcite precipitation was largely dependent on the quantity of water supplied to the speleothem. By contrast, thickness of aragonite layers correlates with temperature, although variation in temperature cannot explain greater aragonite abundance on the sides of the speleothem compared to its center. Mg/Ca ratios in calcite layers increase upward to the bases of overlying aragonite layers, and analyses of cave waters suggest that fluid Mg/Ca ratios reach levels sufficient to cause aragonite precipitation. Increasing evaporation, which caused greater ionic strength and supersaturation, resultant increasing Mg/Ca ratios in the fluid, and perhaps increasing temperature probably combined to cause aragonite precipitation. Detailed petrographic analysis suggests that each annual cycle of CaCO3 precipitation began with relatively intense fluid flow, sometimes sufficient to dissolve some of the underlying aragonite before precipitation of calcite. Calcite precipitation under a thick fluid layer allowed euhedral crystals to form at first, but thinning of the fluid to a film allowed only flatly terminated calcite crystals by seasons end. As fluid flow diminished, increasing evaporation, increasing Mg/Ca ratios in the fluid, and perhaps increasing temperature combined to cause aragonite precipitation to begin, particularly on the sides of the speleothem. In some years, fluid flow diminished to the point that dust accumulated on aragonite surfaces before the onset of the next years precipitation. /P>

Ten Year Performance Evaluation of a Field-Scale Zero-Valent Iron Permeable Reactive Barrier Installed to Remediate Trichloroethene Contaminated Groundwater

The Monkstown zero-valent iron permeable reactive barrier (ZVI PRB), Europes oldest commercially-installed ZVI PRB, had been treating trichloroethene (TCE) contaminated groundwater for about 10 years on the Nortel Network site in Northern Ireland when cores from the reactive zone were collected in December, 2006. Groundwater data from 2001-2006 indicated that TCE is still being remediated to below detection limits as the contaminated groundwater flows through the PRB. Ca and Fe carbonates, crystalline and amorphous Fe sulfides, and Fe (hydr)oxides have precipitated in the granular ZVI material in the PRB. The greatest variety of minerals is associated with a approximately 1-2 cm thick, slightly cemented crust on top (up-gradient influent entrance) of the ZVI section of the PRB and also with the discontinuous cemented ZVI material ( approximately 23 cm thick) directly below it. The greatest presence of microbial communities also occurred in the up-gradient influent portion of the PRB compared to its down-gradient effluent section, with the latter possibly due to less favorable conditions (i.e., high pH, low oxygen) for microbial growth. The ZVI filings in the down-gradient effluent section of the PRB have a projected life span of >10 years compared with ZVI filings from the continuous to discontinuous cemented up-gradient ZVI section (upper approximately 25 cm) of the PRB, which may have a life span of only approximately 2-5 more years. Supporting Information from applied, multi-tracer testing indicated that restricted groundwater flow is occurring in the upper approximately 25 cm of the ZVI section and preferential pathways have also formed in this PRB over its 10 years of operation.

Influence of carbonates on the riverine carbon cycle in an anthropogenically dominated catchment basin: evidence from major elements and stable carbon isotopes in the Lagan River (N. Ireland)

Abstract Investigation of anthropogenic versus natural controls of the carbon cycle in the Lagan River revealed a strong influence of carbonates. This was evident by increasing pH values along the river as well as isotopic compositions of the riverine dissolved inorganic carbon (δ13CDIC) that approached expected values for carbonate dissolution. This predominant influence of carbonates existed despite their minor abundance of only ∼5% in this densely populated catchment basin and outlines their capacity of buffering anthropogenic influences and CO2 turnover. These effects should be even more pronounced in other rivers where carbonates occupy a larger proportion of the catchment basin geology. Other controls on the riverine carbon cycle were silicate weathering and respiratory turnover of organic material that originated mainly from anthropogenic inputs and increased the DIC pool by up to 26.6%. Predominant natural controls on the Lagan River carbon cycle changed to anthropogenic ones closer to the mouth. Before discharging into Belfast Lough, a recently installed weir caused stagnant seawater to make up between 53% and 92% of the water mass. Poor vertical mixing caused O2 decreases and anaerobic sedimentary activity that resulted in methane production. Recently installed aerators at the sediment surface did not prevent ongoing methanogenesis. This was documented by decreased pCO2 and more 13C-enriched DIC values at the sediment–water interface when compared to those of surface waters from the same sampling sites. Installations of such weirs in estuaries of other rivers may cause similar anoxic effects that influence their biogeochemistry.

Selection of organic substrates as potential reactive materials for use in a denitrification permeable reactive barrier (PRB)

The aim of the present study was to select a suitable natural organic substrate as a potential carbon source for use in a denitrification permeable reactive barrier (PRB). A number of seven organic substrates were first tested in batch tests. The materials attained varying degrees of success at promoting denitrification. Some of the organic substrates performed very well, achieving complete nitrate removal (>98%), while others were considered unsuitable for a variety of reasons, including: insufficient nitrate or nitrogen removal, excessive release of leachable nitrogen from the substrate or excessive reduction of nitrate to ammonium rather than removing it as gaseous N2. The top performing substrate in terms of denitrification extent (>98%) and rate (0.067 mgNO3(-)-N dm(-3)d(-1)g(sub)(-1)) was then selected for two bench-scale column experiments in an attempt to simulate the PRB. The inlet concentration was 50 mg dm(-3) NO3(-)-N and the columns operated at two different flow rates: 0.3 cm3 min(-1) (Column 1) and 1.1cm3 min(-1) (Column 2). The two columns showed different general patterns, making it clear that the flow rate was a key factor at the nitrate removal. Nitrate was completely removed (>96%) by the passage through Column 1, while only partially removed in Column 2 (66%). The results indicated that the selected organic substrate (Softwood) was applicable for further use as a filling material for a PRB.

Resolving genetic functions within microbial populations: in situ analyses using rRNA and mRNA stable isotope probing coupled with single-cell raman-fluorescence in situ hybridization

ABSTRACT Prokaryotes represent one-half of the living biomass on Earth, with the vast majority remaining elusive to culture and study within the laboratory. As a result, we lack a basic understanding of the functions that many species perform in the natural world. To address this issue, we developed complementary population and single-cell stable isotope (13C)-linked analyses to determine microbial identity and function in situ. We demonstrated that the use of rRNA/mRNA stable isotope probing (SIP) recovered the key phylogenetic and functional RNAs. This was followed by single-cell physiological analyses of these populations to determine and quantify in situ functions within an aerobic naphthalene-degrading groundwater microbial community. Using these culture-independent approaches, we identified three prokaryote species capable of naphthalene biodegradation within the groundwater system: two taxa were isolated in the laboratory (Pseudomonas fluorescens and Pseudomonas putida), whereas the third eluded culture (an Acidovorax sp.). Using parallel population and single-cell stable isotope technologies, we were able to identify an unculturable Acidovorax sp. which played the key role in naphthalene biodegradation in situ, rather than the culturable naphthalene-biodegrading Pseudomonas sp. isolated from the same groundwater. The Pseudomonas isolates actively degraded naphthalene only at naphthalene concentrations higher than 30 μM. This study demonstrated that unculturable microorganisms could play important roles in biodegradation in the ecosystem. It also showed that the combined RNA SIP-Raman-fluorescence in situ hybridization approach may be a significant tool in resolving ecology, functionality, and niche specialization within the unculturable fraction of organisms residing in the natural environment.

Radiocarbon Dating of Groundwater Systems

Groundwater is an increasingly important water resource in arid or semi-arid regions, as well as a conjunctive resource in humid environments. Because of the long residence time for groundwater in the hydrologic cycle, the last few decades have seen expanding study of groundwater systems. It is therefore important to continually refine our interpretation of hydrogeologic, geochemical and isotopic data to better understand the spatial and temporal movement of water in the subsurface. With our ever-increasing understanding of the magnitude of climate variations during the last 40 000 years and the impact of our industrialised society on groundwater quality and quantity, hydrogeologists will continue to require more information about the rate of groundwater movement on scales from the subannual to millenium. The 5730 year half-life of 14C and the ubiquity of carbon (as organic and inorganic forms) in groundwater, makes it a potentially ideal tracer on these timescales.

Isotopic evidence for temperature variation during the early Cretaceous (late Ryazanian–mid‐Hauterivian)

Oxygen and carbon isotopic compositions have been determined from the belemnite genera Acroteuthis and Hibolites sampled from the early Cretaceous (Ryazanian–Hauterivian) interval of the Speeton Clay Formation, Filey Bay, England. The Speeton Clay Formation consists of a series of claystones and calcareous mudrocks deposited in an epicontinental sea. δ18O values from belemnites, which met petrographic and chemical criteria for well preserved skeletal carbonate, indicate warm marine palaeotemperatures (c. 12–15°C) for much of the early Valanginian whilst cool temperatures (<9°C) are inferred for the earliest Hauterivian. During the remainder of the Hauterivian, temperatures fluctuated considerably and rose to a maximum of 15.5°C. Changes in kaolinite and smectite abundances, considered to reflect humid and arid phases of climate, correlate with warm and cool episodes. The palaeotemperature record, appears to contradict evidence from cephalopod faunas, which show a Tethyan influx during the inferred early Hauterivian cool period. However, this was a transgressive phase and thus the cephalopods could have been less sensitive to temperature than to water column stability and to land barriers. A positive shift in the carbon isotope profile obtained from the Speeton belemnites appears correlatable with carbon isotope profiles recorded from pelagic Tethyan successions, albeit with somewhat differing absolute values. The data support earlier models of carbon isotope variation, in that positive excursions are associated with an inferred global rise in sea level.

Late-surviving megafauna in Tasmania, Australia, implicate human involvement in their extinction

Establishing the cause of past extinctions is critical if we are to understand better what might trigger future occurrences and how to prevent them. The mechanisms of continental late Pleistocene megafaunal extinction, however, are still fiercely contested. Potential factors contributing to their demise include climatic change, human impact, or some combination. On the Australian mainland, 90% of the megafauna became extinct by ≈46 thousand years (ka) ago, soon after the first archaeological evidence for human colonization of the continent. Yet, on the neighboring island of Tasmania (which was connected to the mainland when sea levels were lower), megafaunal extinction appears to have taken place before the initial human arrival between 43 and 40 ka, which would seem to exonerate people as a contributing factor in the extirpation of the island megafauna. Age estimates for the last megafauna, however, are poorly constrained. Here, we show, by direct dating of fossil remains and their associated sediments, that some Tasmanian megafauna survived until at least 41 ka (i.e., after their extinction on the Australian mainland) and thus overlapped with humans. Furthermore, a vegetation record for Tasmania spanning the last 130 ka shows that no significant regional climatic or environmental change occurred between 43 and 37 ka, when a land bridge existed between Tasmania and the mainland. Our results are consistent with a model of human-induced extinction for the Tasmanian megafauna, most probably driven by hunting, and they reaffirm the value of islands adjacent to continental landmasses as tests of competing hypotheses for late Quaternary megafaunal extinctions.

Kinetics of the oxidation of methyl tert-butyl ether (MTBE) by potassium permanganate

The occurrence of the fuel oxygenate methyl tert-butyl ether (MTBE) in the environment has received considerable scientific attention. The pollutant is frequently found in the groundwater due to leaking of underground storage tanks or pipelines. Concentrations of more than several mg/L MTBE were detected in groundwater at several places in the US and Germany in the last few years. In situ chemical oxidation is a promising treatment method for MTBE-contaminated plumes. This research investigated the reaction kinetics for the oxidation of MTBE by permanganate. Batch tests demonstrated that the oxidation of MTBE by permanganate is second order overall and first order individually with respect to permanganate and MTBE. The second-order rate constant was 1.426 x 10(-6) L/mg/h. The influence of pH on the reaction rate was demonstrated to have no significant effect. However, the rate of MTBE oxidation by potassium permanganate is 2-3 orders of magnitude lower than of other advanced oxidation processes. The slower rates of MTBE oxidation by permanganate limit the applicability of this process for rapid MTBE cleanup strategies. However, permanganate oxidation of MTBE has potential for passive oxidation risk management strategies.

Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria

The largest biological fractionations of stable carbon isotopes observed in nature occur during production of methane by methanogenic archaea. These fractionations result in substantial (as much as ≈70‰) shifts in δ13C relative to the initial substrate. We now report that a stable carbon isotopic fractionation of comparable magnitude (up to 70‰) occurs during oxidation of methyl halides by methylotrophic bacteria. We have demonstrated biological fractionation with whole cells of three methylotrophs (strain IMB-1, strain CC495, and strain MB2) and, to a lesser extent, with the purified cobalamin-dependent methyltransferase enzyme obtained from strain CC495. Thus, the genetic similarities recently reported between methylotrophs, and methanogens with respect to their pathways for C1-unit metabolism are also reflected in the carbon isotopic fractionations achieved by these organisms. We found that only part of the observed fractionation of carbon isotopes could be accounted for by the activity of the corrinoid methyltransferase enzyme, suggesting fractionation by enzymes further along the degradation pathway. These observations are of potential biogeochemical significance in the application of stable carbon isotope ratios to constrain the tropospheric budgets for the ozone-depleting halocarbons, methyl bromide and methyl chloride.