Sulfur Chemistry May Have Paved the Way for Evolution of Antioxidants.

The first organisms on the young Earth, just 1-1.5 billion years old, were likely chemolithoautotrophic anaerobes, thriving in an anoxic world rich in water, CO2, and N2. It is generally assumed that, until the accumulation of O2 in the atmosphere, life was exempted from the oxidative stress that reactive oxygen species (ROS) impose on hydrocarbon-based life. Therefore, it is perplexing to note that life on the early Earth already carried antioxidants such as superoxide dismutase enzymes, catalase, and peroxiredoxins, the function of which is to counteract all forms of ROS, including H2O2. Phylogenetic investigations suggest that the presence of these enzymes in the last universal common ancestor, far predating the great oxygenation event (GOE) sometime between 2.3 and 2.7 billion years ago, is thought to be due to the appearance of oxygen-producing microorganisms and the subsequent need to respond to the appearance of ROS. Since the metabolic enzymes that counteract ROS have been found in all domains of life, they are considered of primitive origin. Two questions arise: (1) Could there be a nonbiological source of ROS that predates the oxygenic microbial activity? (2) Could sulfur, the homologue of oxygen, have played that role? Reactive sulfur species (RSS) may have triggered the evolution of antioxidants such that the ROS antioxidants started out as "antisulfur" enzymes developed to cope with, and take advantage of, various forms of RSS that were abundantly present on the early Earth.

The potential for impact of man-made super low and extremely low frequency electromagnetic fields on sleep.

An ever-growing number of electromagnetic (EM) emission sources elicits health concerns, particularly stemming from the ubiquitous low to extremely low frequency fields from power lines and appliances, and the radiofrequency fields emitted from telecommunication devices. In this article we review the state of knowledge regarding possible impacts of electromagnetic fields on melatonin secretion and on sleep structure and the electroencephalogram of humans. Most of the studies on the effects of melatonin on humans have been conducted in the presence of EM fields, focusing on the effects of occupational or residential exposures. While some of the earlier studies indicated that EM fields may have a suppressive effect on melatonin, the results cannot be generalized because of the large variability in exposure conditions and other factors that may influence melatonin. For instance, exposure to radiofrequency EM fields on sleep architecture show little or no effect. However, a number of studies show that pulsating radiofrequency electromagnetic fields, such as those emitted from cellular phones, can alter brain physiology, increasing the electroencephalogram power in selective bands when administered immediately prior to or during sleep. Additional research is necessary that would include older populations and evaluate the interactions of EM fields in different frequency ranges to examine their effects on sleep in humans.

A Quasi-Elastic Neutron Scattering Study of the Dynamics of Electrically Constrained Water.

We have measured the quasi-elastic neutron scattering (QENS) of an electrohydrodynamic liquid bridge formed between two beakers of pure water when a high voltage is applied, a setup allowing to investigate water under high-voltage without high currents. From this experiment two proton populations were distinguished: one consisting of protons strongly bound to oxygen atoms (immobile population, elastic component) and a second one of quasi-free protons (mobile population, inelastic component) both detected by QENS. The diffusion coefficient of the quasi-free protons was found to be D = (26 ± 10) × 10(-5) cm(2) s(-1) with a jump length lav ∼ 3 Å and an average residence time of τ0 = 0.55 ± 0.08 ps. The associated proton mobility in the proton channel of the bridge is ∼9.34 × 10(-7) m(2) V(-1) s(-1), twice as fast as diffusion-based proton mobility in bulk water. It also matches the so-called electrohydrodynamic or "apparent" charge mobility, an experimental quantity which so far has lacked molecular interpretation. These results further corroborate the proton channel model for liquid water under high voltage and give new insights into the molecular mechanisms behind electrohydrodynamic charge transport phenomena and delocalization of protons in liquid water.

Cows Come Down from the Mountains before the (Mw = 6.1) Earthquake Colfiorito in September 1997; A Single Case Study.

The September-October 1997 seismic sequence in the Umbria-Marche regions of Central Italy has been one of the stronger seismic events to occur in Italy over the last thirty years, with a maximum magnitude of Mw = 6.1. Over the last three years, a collection of evidence was carried out regarding non-seismic phenomena, by interviewing local residents using a questionnaire. One particular observation of anomalous animal behaviour, confirmed by many witnesses, concerned a herd of cows, which descended from a mountain close to the streets of a village near the epicentre, a few days before the main shock. Testimonies were collected using a specific questionnaire including data on earthquake lights, spring variations, human diseases, and irregular animal behaviour. The questionnaire was compiled after the L'Aquila earthquake in 2009, and was based upon past historical earthquake observations. A possible explanation for the cows' behavior-local air ionization caused by stress-activated positive holes-is discussed.

Nature of Pre-Earthquake Phenomena and their Effects on Living Organisms.

Earthquakes occur when tectonic stresses build up deep in the Earth before catastrophic rupture. During the build-up of stress, processes that occur in the crustal rocks lead to the activation of highly mobile electronic charge carriers. These charge carriers are able to flow out of the stressed rock volume into surrounding rocks. Such outflow constitutes an electric current, which generates electromagnetic (EM) signals. If the outflow occurs in bursts, it will lead to short EM pulses. If the outflow is continuous, the currents may fluctuate, generating EM emissions over a wide frequency range. Only ultralow and extremely low frequency (ULF/ELF) waves travel through rock and can reach the Earth surface. The outflowing charge carriers are (i) positively charged and (ii) highly oxidizing. When they arrive at the Earth surface from below, they build up microscopic electric fields, strong enough to field-ionize air molecules. As a result, the air above the epicentral region of an impending major earthquake often becomes laden with positive airborne ions. Medical research has long shown that positive airborne ions cause changes in stress hormone levels in animals and humans. In addition to the ULF/ELF emissions, positive airborne ions can cause unusual reactions among animals. When the charge carriers flow into water, they oxidize water to hydrogen peroxide. This, plus oxidation of organic compounds, can cause behavioral changes among aquatic animals.

Ground water chemistry changes before major earthquakes and possible effects on animals.

Prior to major earthquakes many changes in the environment have been documented. Though often subtle and fleeting, these changes are noticeable at the land surface, in water, in the air, and in the ionosphere. Key to understanding these diverse pre-earthquake phenomena has been the discovery that, when tectonic stresses build up in the Earth's crust, highly mobile electronic charge carriers are activated. These charge carriers are defect electrons on the oxygen anion sublattice of silicate minerals, known as positive holes, chemically equivalent to O- in a matrix of O2-. They are remarkable inasmuch as they can flow out of the stressed rock volume and spread into the surrounding unstressed rocks. Travelling fast and far the positive holes cause a range of follow-on reactions when they arrive at the Earth's surface, where they cause air ionization, injecting massive amounts of primarily positive air ions into the lower atmosphere. When they arrive at the rock-water interface, they act as •O radicals, oxidizing water to hydrogen peroxide. Other reactions at the rock-water interface include the oxidation or partial oxidation of dissolved organic compounds, leading to changes of their fluorescence spectra. Some compounds thus formed may be irritants or toxins to certain species of animals. Common toads, Bufo bufo, were observed to exhibit a highly unusual behavior prior to a M6.3 earthquake that hit L'Aquila, Italy, on April 06, 2009: a few days before the seismic event the toads suddenly disappeared from their breeding site in a small lake about 75 km from the epicenter and did not return until after the aftershock series. In this paper we discuss potential changes in groundwater chemistry prior to seismic events and their possible effects on animals.

Hydrogen in rocks: an energy source for deep microbial communities.

To survive in deep subsurface environments, lithotrophic microbial communities require a sustainable energy source such as hydrogen. Though H2 can be produced when water reacts with fresh mineral surfaces and oxidizes ferrous iron, this reaction is unreliable since it depends upon the exposure of fresh rock surfaces via the episodic opening of cracks and fissures. A more reliable and potentially more voluminous H2 source exists in nominally anhydrous minerals of igneous and metamorphic rocks. Our experimental results indicate that H2 molecules can be derived from small amounts of H2O dissolved in minerals in the form of hydroxyl, OH- or O3Si-OH, whenever such minerals crystallized in an H2O-laden environment. Two types of experiments were conducted. Single crystal fracture experiments indicated that hydroxyl pairs undergo an in situ redox conversion to H2 molecules plus peroxy links, O3Si/OO\SiO3. While the peroxy links become part of the mineral structure, the H2 molecules diffused out of the freshly fractured mineral surfaces. If such a mechanism occurred in natural settings, the entire rock column would become a volume source of H2. Crushing experiments to facilitate the outdiffusion of H2 were conducted with common crustal igneous rocks such as granite, andesite, and labradorite. At least 70 nmol of H2/g diffused out of coarsely crushed andesite, equivalent at standard pressure and temperature to 5,000 cm3 of H2/m3 of rock. In the water-saturated, biologically relevant upper portion of the rock column, the diffusion of H2 out of the minerals will be buffered by H2 saturation of the intergranular water film.