Methane cycling in the carbonate critical zone.

The carbonate critical zone (CZ) is characterized by extensive groundwater-surface water exchange that leads to highly variable redox states of groundwater. Changes in redox condition may cause either production or consumption of methane (CH4), thereby providing an atmospheric source or sink of this important greenhouse gas. To assess how groundwater-surface water exchange affects redox state and CH4 cycling in the carbonate CZ, we measured CH4 concentrations and 13C isotopes in water from streams, spring systems, and wells in north-central Florida. Sampled groundwater has subsurface residence times ranging from hours at a stream sink-rise system, to months following a flood recharge event into a spring vent, to decades at springs with limited point recharge. Concentrations of CH4 ranged from 0.002 to 89 µM, with an inverse relationship in springs between subsurface residence time and CH4 concentration. Where residence time is short, low CH4 concentrations result from methanotrophy linked to elevated dissolved oxygen (DO) concentrations. Following flooding, methanotrophy occurs soon after recharge and is followed by methanogenesis as groundwater becomes increasingly reducing. Groundwater extracted from wells had CH4 concentrations greater than spring water indicating CH4 is lost during flow to spring vents. CH4 concentrations covary with δ13C-CH4 values, which supports both methanogenesis and methanotrophy with changing residence times. Mean fluxes of CH4 ranged from -0.05 to 1.0 mg m-2 d-1 at spring vents, with negative values caused by CH4 uptake in water undersaturated with respect to atmospheric concentration. Most springs are dominated by methanotrophy, limiting atmospheric evasion of CH4 produced in the carbonate CZ. We estimate CH4 emissions to be 12.6 × 10-6 Tg a-1 across all Florida springs or about two orders of magnitude less than emissions from Floridan aquifer groundwater abstraction (3041 × 10-6 Tg a-1). Although CH4 is produced in the carbonate CZ, natural attenuation limits its effects on the global carbon cycle.

Statistical evidence of recharge and supply controlling nitrate variability at springs discharging from the upper Floridan Aquifer.

Over the last several decades, rising nitrate concentrations in springs discharging from north Florida's karstic Upper Floridan Aquifer have coincided with proliferation of algae in Florida spring runs and subsequent ecosystem degradation. As agriculture and development are primary contributors to groundwater nitrate and are predicted to continue expanding, understanding unique contributions and transmission pathways of nitrate pollution is vital to restoring impaired spring ecosystems. In this study, we use statistics and signal processing to analyze continuous nitrate timeseries data collected over five years at four north Florida springs. We quantified a significant, low-frequency annual signal in nitrate concentrations superimposed on increasing nitrate trends. We show nitrate concentrations at springs increase during the rainy season, potentially in response to recharge and seasonal fertilizer application. Thus, we suggest seasonal fluctuations observed in nitrate concentrations are caused by increased recharge of nutrient-rich soil waters through fractures that deliver water on relatively short timescales to conduits during the rainy season. We further speculate the steady, monotonically increasing concentration is maintained by accumulation of Nitrogen as slow flow through matrix porosity through the remainder of the year. Seasonal nitrate concentrations resulting from flow through karst aquifers may thus be poorly simulated using equivalent porous media models that are increasingly being used for nutrient management, because they do not capture heterogenous flow and transport dynamics.

Highly Tactic Cyclic Polynorbornene: Stereoselective Ring Expansion Metathesis Polymerization of Norbornene Catalyzed by a New Tethered Tungsten-Alkylidene Catalyst.

The tungsten alkylidyne [(t)BuOCO]W≡C((t)Bu) (THF)2 (1) reacts with CO2, leading to complete cleavage of one C═O bond, followed by migratory insertion to generate the tungsten-oxo alkylidene 2. Complex 2 is the first catalyst to polymerize norbornene via ring expansion metathesis polymerization to yield highly cis-syndiotactic cyclic polynorbornene.

Multicomponent assembly of 4-aza-podophyllotoxins: A fast entry to highly selective and potent anti-leukemic agents.

The aim of this study was the synthesis and lead structure selection of a best anti-leukemic agent from a library of aza-podophyllotoxin analogues (APTs). To this end, we report a scalable, modified multicomponent reaction using a "sacrificial" aniline partner as a more general route to rapidly construct the pivotal library of 50 APT analogues. Our preliminary structure activity relationship studies for anti-leukemic activity also address the innate toxicity of these compounds against non-malignant cells. As a result, we identified 2 novel compounds 2ca' and 2jc' more potent than etoposide 1 (25-60 fold) having high selectivity against the human THP-1 leukemia cell line and a minimal toxicity (IC50 of 9.3 ± 0.8 and 19.6 ± 1.4 nM respectively) which represent the best candidates for further pharmacological optimization.