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USGS2023

Ammonia and aquatic ecosystems – A review of global sources, biogeochemical cycling, and effects on fish

The purpose of this review is to better understand the full life cycle and influence of ammonia from an aquatic biology perspective. While ammonia has toxic properties in water and air, it also plays a central role in the biogeochemical nitrogen (N) cycle and regulates mechanisms of normal and abnormal fish physiology. Additionally, as the second most synthesized chemical on Earth, ammonia contributes economic value to many sectors, particularly fertilizers, energy storage, explosives, refrigerants, and plastics. But, with so many uses, industrial N 2 -fixation effectively doubles natural reactive N concentrations in the environment. The consequence is global, with excess fixed nitrogen driving degradation of soils, water, and air; intensifying eutrophication, biodiversity loss, and climate change; and creating health risks for humans, wildlife, and fisheries. Thus, the need for ammonia research in aquatic systems is growing. In response, we prepared this review to better understand the complexities and connectedness of environmental ammonia. Even the term “ammonia” has multiple meanings. So, we have clarified the nomenclature, identified units of measurement, and summarized methods to measure ammonia in water. We then discuss ammonia in the context of the N-cycle, review its role in fish physiology and mechanisms of toxicity, and integrate the effects of human N-fixation, which continuously expands ammonia's sources and uses. Ammonia is being developed as a carbon-free energy carrier with potential to increase reactive nitrogen in the environment. With this in mind, we review the global impacts of excess reactive nitrogen and consider the current monitoring and regulatory frameworks for ammonia. The presented synthesis illustrates the complex and interactive dynamics of ammonia as a plant nutrient, energy molecule, feedstock, waste product, contaminant, N-cycle participant, regulator of animal physiology, toxicant, and agent of environmental change. Few molecules are as influential as ammonia in the management and resilience of Earth's resources.

Science of the Total Environment↗
USGS1997

Experiments on the role of water in petroleum formation

Pyrolysis experiments were conducted on immature petroleum source rocks under various conditions to evaluate the role of water in petroleum formation. At temperatures less than 330°C for 72 h, the thermal decomposition of kerogen to bitumen was not significantly affected by the presence or absence of liquid water in contact with heated gravel-sized source rock. However, at 330 and 350°C for 72 h, the thermal decomposition of generated bitumen was significantly affected by the presence or absence of liquid water. Carbon-carbon bond cross linking resulting in the formation of an insoluble bitumen (i.e., pyrobitumen) is the dominant reaction pathway in the absence of liquid water. Conversely, thermal cracking of carbon-carbon bonds resulting in the generation of saturate-enriched oil, which is similar to natural crude oils, is the dominant reaction pathway in the presence of liquid water. This difference in reaction pathways is explained by the availability of an exogenous source of hydrogen, which reduces the rate of thermal decomposition, promotes thermal cracking, and inhibits carbon-carbon bond cross linking. The distribution of generated n -alkanes is characteristic of a free radical mechanism, with a broad carbon-number distribution (i.e., C 5 to C 35 ) and only minor branched alkanes from known biological precursors (i.e., pristane and phytane). The generation of excess oxygen in the form of CO 2 in hydrous experiments and the high degree of hydrocarbon deuteration in a D 2 O experiment indicate that water dissolved in the bitumen is an exogenous source of hydrogen. The lack of an effect on product composition and yield with an increase in H + activity by five orders of magnitude in a hydrous experiment indicates that an ionic mechanism for water interactions with thermally decomposing bitumen is not likely. Several mechanistically simple and thermodynamically favorable reactions that are consistent with the available experimental data are envisaged for the generation of exogenous hydrogen and excess oxygen as CO 2 . One reaction series involves water oxidizing existing carbonyl groups to form hydrogen and carbonyl groups, with the latter forming CO 2 by decarbonylation with increasing thermal stress. Another reaction series involves either hydrogen or oxygen in dissolved water molecules directly interacting with unpaired electrons to form a hydrogen-terminated free-radical site or an oxygenated functional group, respectively. The latter is expected to be susceptible to oxidation by other dissolved water molecules to generate additional hydrogen and CO 2 . In addition to water acting as an exogenous source of hydrogen, it is also essential to the generation of an expelled saturate-enriched oil that is similar to natural crude oil. This role of water is demonstrated by the lack of an expelled oil in an experiment where a liquid Ga In alloy is substituted for liquid water. Experiments conducted with high salinity water and high water/rock ratios indicate that selective aqueous solubility of hydrocarbons is not responsible for the expelled oil generated in hydrous pyrolysis experiments. Similarly, a hydrous pyrolysis experiment conducted with isolated kerogen indicates that expelled oil in hydrous pyrolysis is not the result of preferential sorption of polar organic components by the mineral matrix of a source rock. It is envisaged that dissolved water in the bitumen network of a source rock causes an immiscible saturate-enriched oil to become immiscible with the thermally decomposing polar-enriched bitumen. The overall geochemical implication of these results is that it is essential to consider the role of water in experimental studies designed to understand natural rates of petroleum generation, expulsion mechanisms of primary migration, thermal stability of crude oil, reaction kinetics of biomarker transformations, and thermal maturity indicators in sedimentary basins.

Geochimica et Cosmochimica Acta↗
USGS2005

Inhibition of calcite precipitation by natural organic material: Kinetics, mechanism, and thermodynamics

The inhibition of calcite precipitation by natural organic material (NOM) in solutions seeded with calcite was investigated using a pH-stat system. Experiments were carried out using three NOMs with different physical/chemical properties. For each of the materials, inhibition was found to be more effective at lower carbonate/calcium ratios and lower pH values. The reduction in the precipitation rate could be explained by a Langmuir adsorption model using a conditional equilibrium constant. By identification of the type of site on the NOM molecules that is involved in the adsorption reaction, the "conditional" equilibrium constants obtained at different solution compositions converged to a single "nonconditional" value. The thermodynamic data determined at 25??C and 1 atm suggest that the interaction between NOM molecules and the calcite surface is chemisorptive in nature and that adsorption is an endothermic reaction driven by the entropy change. The greatest degree of inhibition was observed for the NOM with the highest molecular weight and aromatic carbon content. For a given type of NOM, the degree of inhibition of calcite precipitation was dictated by the balance between the enthalpy change and the entropy change of the adsorption reaction. ?? 2005 American Chemical Society.

Environmental Science & Technology↗
USGS1998

Models of metal binding structures in fulvic acid from the Suwannee River, Georgia

Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The 'metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-1R spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short- chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The `metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-IR spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short-chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.

Georiga↗
USGS1999

Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter

Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently first-order in pyrene to one that was apparently second-order in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.

Environmental Science & Technology↗
USGS2009

Reflectance spectroscopy of organic compounds: 1. Alkanes

Reflectance spectra of the organic compounds comprising the alkane series are presented from the ultraviolet to midinfrared, 0.35 to 15.5 /??m. Alkanes are hydrocarbon molecules containing only single carbon-carbon bonds, and are found naturally on the Earth and in the atmospheres of the giant planets and Saturn's moon, Titan. This paper presents the spectral properties of the alkanes as the first in a series of papers to build a spectral database of organic compounds for use in remote sensing studies. Applications range from mapping the environment on the Earth, to the search for organic molecules and life in the solar system and throughout the. universe. We show that the spectral reflectance properties of organic compounds are rich, with major diagnostic spectral features throughout the spectral range studied. Little to no spectral change was observed as a function of temperature and only small shifts and changes in the width of absorption bands were observed between liquids and solids, making remote detection of spectral properties throughout the solar system simpler. Some high molecular weight organic compounds contain single-bonded carbon chains and have spectra similar to alkanes even ' when they fall into other families. Small spectral differences are often present allowing discrimination among some compounds, further illustrating the need to catalog spectral properties for accurate remote sensing identification with spectroscopy.

Journal of Geophysical Research E: Planets↗
USGS2011

Sources and physical processes responsible for OH/H2O in the lunarsoil as revealed by the Moon Mineralogy Mapper (M3)

Analysis of two absorption features near 3 μ m in the lunar reflectance spectrum, observed by the orbiting M 3 spectrometer and interpreted as being due to OH and H 2 O, is presented, and the results are used to discuss the processes producing these molecules. This analysis focuses on the dependence of the absorptions on lunar physical properties, including composition, illumination, latitude, and temperature. Solar wind proton-induced hydroxylation is proposed as the creation process, and its products could be a source for other reported types of hydrogen-rich material and water. The irregular and damaged fine-grained lunar soil seems especially adapted for trapping solar wind protons and forming OH owing to abundant dangling oxygen bonds. The M 3 data reveal that the strengths of the two absorptions are correlated and widespread, and both are correlated with lunar composition but in different ways. Feldspathic material seems richer in OH. These results seem to rule out water from the lunar interior and cometary infall as major sources. There appear to be correlations of apparent band strengths with time of day and lighting conditions. However, thermal emission from the Moon reduces the apparent strengths of the M 3 absorptions, and its removal is not yet completely successful. Further, many of the lunar physical properties are themselves intercorrelated, and so separating these dependencies on the absorptions is difficult, due to the incomplete M 3 data set. This process should also operate on other airless silicate surfaces, such as Mercury and Vesta, which will be visited by the Dawn spacecraft in mid-2011.

Journal of Geophysical Research E: Planets↗
USGS2012

Linkages between denitrification and dissolved organicmatter quality, Boulder Creek watershed, Colorado

Dissolved organic matter (DOM) fuels the majority of in-stream microbial processes, including the removal of nitrate via denitrification. However, little is known about how the chemical composition of DOM influences denitrification rates. Water and sediment samples were collected across an ecosystem gradient, spanning the alpine to plains, in central Colorado to determine whether the chemical composition of DOM was related to denitrification rates. Laboratory bioassays measured denitrification potentials using the acetylene block technique and carbon mineralization via aerobic bioassays, while organic matter characteristics were evaluated using spectroscopic and fractionation methods. Denitrification potentials under ambient and elevated nitrate concentrations were strongly correlated with aerobic respiration rates and the percent mineralized carbon, suggesting that information about the aerobic metabolism of a system can provide valuable insight regarding the ability of the system to additionally reduce nitrate. Multiple linear regressions (MLR) revealed that under elevated nitrate concentrations denitrification potentials were positively related to the presence of protein-like fluorophores and negatively related to more aromatic and oxidized fractions of the DOM pool. Using MLR, the chemical composition of DOM, carbon, and nitrate concentrations explained 70% and 78% of the observed variability in denitrification potential under elevated and ambient nitrate conditions, respectively. Thus, it seems likely that DOM optical properties could help to improve predictions of nitrate removal in the environment. Finally, fluorescence measurements revealed that bacteria used both protein and humic-like organic molecules during denitrification providing further evidence that larger, more aromatic molecules are not necessarily recalcitrant in the environment.

Colorado↗
USGS2022

Sedimentary organics in Glen Torridon, Gale Crater, Mars: Results from the SAM instrument suite and supporting laboratory analyses

The Sample Analysis at Mars (SAM) suite instrument on board NASA's Curiosity rover has characterized the inorganic and organic chemical composition of seven samples from the Glen Torridon (GT) clay-bearing unit. A variety of organic molecules were detected with SAM using pyrolysis (up to ∼850°C) and wet chemistry experiments coupled with evolved gas analysis (EGA) and gas chromatography-mass spectrometry. SAM EGA and GCMS analyses revealed a greater diversity and abundance of sulfur-bearing aliphatic and aromatic organic compounds in the sediments of this Gale crater unit than earlier in the mission. We also report the detection of nitrogen-containing, oxygen-containing, and chlorine-containing molecules, as well as polycyclic aromatic hydrocarbons found in GT, although the sources of some of these organics may be related to the presence of chemical reagents in the SAM instrument background. However, sulfur-bearing organics released at high temperature (≥600°C) are likely derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources and consistent with the presence of recalcitrant organic materials in the sample. The SAM measurements of the GT clay-bearing unit expand the inventory of organic matter present in Gale crater and is also consistent with the hypothesis that clay minerals played an important role in the preservation of ancient refractory organic matter on Mars. These findings deepen our understanding of the past habitability and biological potential of Gale crater.

JGR Planets↗
USGS1998

Non-water-ice constituents in the surface material of the icy Galilean satellites from the Galileo near-infrared mapping spectrometer investigation

We present evidence for several non‐ice constituents in the surface material of the icy Galilean satellites, using the reflectance spectra returned by the Galileo near infrared mapping spectrometer (NIMS) experiment. Five new absorption features are described at 3.4, 3.88, 4.05, 4.25, and 4.57 μm for Callisto and Ganymede, and some seem to exist for Europa as well. The four absorption bands strong enough to be mapped on Callisto and Ganymede are each spatially distributed in different ways, indicating different materials are responsible for each absorption. The spatial distributions are correlated at the local level in complex ways with surface features and in some cases show global patterns. Suggested candidate spectrally active groups, perhaps within larger molecules, producing the five absorptions include C‐H, S‐H, SO 2 , CO 2 , and C≡N. Organic material like tholins are candidates for the 4.57‐ and 3.4‐μm features. We suggest, based on spectroscopic evidence, that CO 2 is present as a form which does not allow rotational modes and that SO 2 is present neither as a frost nor a free gas. The CO 2 , SO 2 , and perhaps cyanogen (4.57 μm) may be present as very small collections of molecules within the crystal structure, perhaps following models for radiation damage and/or for comet and interstellar grain formation at low temperatures. Some of the dark material on these surfaces may be created by radiation damage of the CO 2 and other carbon‐bearing species and the formation of graphite. These spectra suggest a complex chemistry within the surface materials and an important role for non‐ice materials in the evolution of the satellite surfaces.

Journal of Geophysical Research E: Planets↗
USGS1890

The molecular stability of metals, particularly of iron and steel

(1) ALLOW me to add some words relative to the very timely lecture on the hardening and tempering of steel, recently published by Prof. Roberts-Austen (NATURE, xli. pp. 11, 42). I desire, in the first place, to point out the bearing of the singular minimum of the viscosity of hot iron ( loc. cit ., p. 34) on the interpretation given of Maxwell's theory of viscosity ( Phil. Mag . (5), xxvi. pp. 183, 397, 1888; xxvii. p. 155, 1889). When iron passes through Barrett's temperature of recalescence, its molecular condition is for an instant almost chaotic. This has now been abundantly proved (cf. John Hopkinson, Phil. Trans., London, clxxx. p. 443, 1889, where the literature may be found; cf. Osmond, below). The number of unstable configurations, or, more clearly, the number of configurations made unstable because they are built up of disintegrating molecules, is therefore at a maximum. It follows that the viscosity of the metal must pass through a minimum. Physically considered, the case is entirely analogous to that of a glass-hard steel rod suddenly exposed to 300°. If all the molecules passed from Osmond's β state to his a state together, the iron or steel would necessarily be liquid. This extreme possibility is, however, at variance with the well-known principles of chemical kinetics. The ratio of stable to unstable configurations cannot at any instant be zero. Hence the minimum viscosity in question, however relatively low, may yet be large in value as compared with the liquid state.

Nature↗
USGS1996

Crystal structures of [NEt3H]5[XCoIIW11O39]·3H2O (X = P or As)

The orthorhombic crystal structures of [NEt3H]5[XCoIIW11O39]·3H2O for X = P and As have been determined with data collected at room temperature, and for X = P at –100 °C, using Mo-Kα radiation. For the latter the space group is Pna21, a= 21.670(11), b= 14.805(4), c= 20.393(5)Å and Z= 4. The structure consists of chains of α-Keggin-type molecules joined by W–O–links aligned in the a-axis direction. The Co/W occupancy at the link is disordered, with 61% Co on one side and 39% on the other. Further probable disorder, by lamellar merohedral twinning on (001) and by misorientation of the triethylammonium ions, has obscured the ethyl groups and the water molecules. In polarized light the crystals are deep wine-red normal to the chains (in the b direction), but nearly colourless in the a and c directions. The structure of the arsenate is similar to that of the phosphate.

Journal of the Chemical Society, Dalton Transactio↗
USGS2022

Great diversity of KSα sequences from bat-associated microbiota suggests novel sources of uncharacterized natural products

Polyketide synthases (PKSs) are multidomain enzymes in microorganisms that synthesize complex, bioactive molecules. PKS II systems are iterative, containing only a single representative of each domain: ketosynthase alpha (KS &#x03B1; "> α � ⁠ ), ketosynthase beta and the acyl carrier protein. Any gene encoding for one of these domains is representative of an entire PKS II biosynthetic gene cluster (BGC). Bat skin surfaces represent an extreme environment prolific in Actinobacteria that may constitute a source for bioactive molecule discovery. KS &#x03B1; "> α � sequences were obtained from culturable bacteria from bats in the southwestern United States. From 467 bat bacterial isolates, we detected 215 (46%) had KS &#x03B1; "> α � sequences. Sequencing yielded 210 operational taxonomic units, and phylogenetic placement found 45 (21%) shared <85% homology to characterized metabolites. Additionally, 16 Actinobacteria genomes from the bat microbiome were analyzed for biosynthetic capacity. A range of 69–93% of the BGCs were novel suggesting the bat microbiome may contain valuable uncharacterized natural products. Documenting and characterizing these are important in understanding the susceptibility of bats to emerging infectious diseases, such as white-nose syndrome. Also noteworthy was the relationship between KS &#x03B1; "> α � homology and total BGC novelty within each fully sequenced strain. We propose amplification and detection of KS &#x03B1; "> α � could predict a strain's global biosynthetic capacity.

FEMS Microbiology Ecology↗
USGS2006

The importance of physiological ecology in conservation biology

Many of the threats to the persistence of populations of sensitive species have physiological or pathological mechanisms, and those mechanisms are best understood through the inherently integrative discipline of physiological ecology. The desert tortoise was listed under the Endangered Species Act largely due to a newly recognized upper respiratory disease thought to cause mortality in individuals and severe declines in populations. Numerous hypotheses about the threats to the persistence of desert tortoise populations involve acquisition of nutrients, and its connection to stress and disease. The nutritional wisdom hypothesis posits that animals should forage not for particular food items, but instead, for particular nutrients such as calcium and phosphorus used in building bones. The optimal foraging hypothesis suggests that, in circumstances of resource abundance, tortoises should forage as dietary specialists as a means of maximizing intake of resources. The optimal digestion hypothesis suggests that tortoises should process ingesta in ways that regulate assimilation rate. Finally, the cost-of-switching hypothesis suggests that herbivores, like the desert tortoise, should avoid switching food types to avoid negatively affecting the microbe community responsible for fermenting plants into energy and nutrients. Combining hypotheses into a resource acquisition theory leads to novel predictions that are generally supported by data presented here. Testing hypotheses, and synthesizing test results into a theory, provides a robust scientific alternative to the popular use of untested hypotheses and unanalyzed data to assert the needs of species. The scientific approach should focus on hypotheses concerning anthropogenic modifications of the environment that impact physiological processes ultimately important to population phenomena. We show how measurements of such impacts as nutrient starvation, can cause physiological stress, and that the endocrine mechanisms involved with stress can result in disease. Finally, our new syntheses evince a new hypothesis. Free molecules of the stress hormone corticosterone can inhibit immunity, and the abundance of "free corticosterone" in the blood (thought to be the active form of the hormone) is regulated when the corticosterone molecules combine with binding globulins. The sex hormone, testosterone, combines with the same binding globulin. High levels of testosterone, naturally occurring in the breeding season, may be further enhanced in populations at high densities, and the resulting excess testosterone may compete with binding globulins, thereby releasing corticosterone and reducing immunity to disease. This sequence could result in physiological and pathological phenomena leading to population cycles with a period that would be essentially impossible to observe in desert tortoise. Such cycles could obscure population fluctuations of anthropogenic origin. ?? 2006 The Author(s).

Conference Paper↗
USGSDate not supplied

Garnet types from the Cazadero area, California

This is the third in a series of papers on glaucophane schists from the Franciscan Formation near Cazadero, California. Previous papers describe three distinct types of glaucophane-bearing Franciscan metamorphic rocks near Cazadero. The purpose of this study is to investigate the garnets present in metamorphic types III (bedrock schists) and IV (tectonic blocks) as defined by Coleman & Lee (1963). Twenty-four garnet analyses are presented. Sixteen of these are from (aragonite-bearing) type III glaucophane schists, and eight are from type IV glaucophane schists. Type IV rocks include California eclogites. Type III rocks include metabasalt, metachert, metashale, meta-ironstone, and metacarbonate that were formed under high pressure and relatively low temperature. These rocks contain garnets that display a wide range of composition, but the dominant molecules represented are consistently almandine, spessartine, and grossular. Type IV rocks are mainly metabasalts that were probably formed under higher temperatures and pressures than type III rocks. There is a distinct difference between garnets from type III rocks and those from type IV (including eclogites); the lattercontain less spessartine and more pyrope, and the dominant molecules are almandine and grossular. The four analyses of garnets from California eclogites have an average pyrope content of about ten molecular per cent, and they extend the range of composition reported for eclogite garnets. Quantitative spectrographic determinations of minor elements are listed for each of the garnets described. The values determined for some of the minor elements have a wide range and a capricious distribution over a few feet of outcrop area. As a group, both the garnets from type III rocks and those from type IV are pyralspites with large contents (as much as 35 molecular per cent) of ugrandite. This unusual admixture of the pyralspite and ugrandite garnet series may have resulted in part from the conditions (high pressures and relatively low temperatures) under which the enclosing rocks were recrystallized.

California↗
USGS2006

The role of free and bound water in irradiation preservation: Free radical damage as a function of the physical state of water

English sole fillets previously equilibrated with aqueous 0.1% cysteine were dehydrated by three methods to moisture levels ranging from 2 to 72%. Model systems using cellulose to replace the fish tissue were also used. The samples were irradiated at 1 Mrad in an air, nitrogen, or oxygen atmosphere. The destruction of −SH groups was measured and related to the amount and physical state of the tissue water. As free water was removed, destruction steadily increased, reaching a maximum at about 20% moisture. Destruction decreased markedly at moisture levels below 10%, and calorimetric measurements confirmed that 10% moisture was about the level of bound water in this species. These data suggest that dehydration favors the reaction of solute molecules with free radicals formed in the free water of muscle cells. At moisture levels greater than about 20%, simple free radical recombination is more likely than reaction with solute molecules, while below 20% moisture the reverse is true. The calculated α values support this conclusion, as do the results from model systems using cellulose.

Journal of Food Science↗
USGS1963

Boron-oxygen polyanion in the crystal structure of tunellite

The crystal structure of tunellite, SrO·3B 2 O 3 ·4H 2 O, with infinite sheets of composition n[B 6 O 9 (OH) 2 ] 2- , has cations and water molecules in the spaces within the sheets. Adjacent sheets are held together by hydrogen bonding through the water molecules. The boron-oxygen polyanions provide the first example in hydrated borate crystals of one oxygen linked to three borons.

Science↗
USGS2011

Biogeochemistry of microbial coal-bed methane

Microbial methane accumulations have been discovered in multiple coal-bearing basins over the past two decades. Such discoveries were originally based on unique biogenic signatures in the stable isotopic composition of methane and carbon dioxide. Basins with microbial methane contain either low-maturity coals with predominantly microbial methane gas or uplifted coals containing older, thermogenic gas mixed with more recently produced microbial methane. Recent advances in genomics have allowed further evaluation of the source of microbial methane, through the use of high-throughput phylogenetic sequencing and fluorescent in situ hybridization, to describe the diversity and abundance of bacteria and methanogenic archaea in these subsurface formations. However, the anaerobic metabolism of the bacteria breaking coal down to methanogenic substrates, the likely rate-limiting step in biogenic gas production, is not fully understood. Coal molecules are more recalcitrant to biodegradation with increasing thermal maturity, and progress has been made in identifying some of the enzymes involved in the anaerobic degradation of these recalcitrant organic molecules using metagenomic studies and culture enrichments. In recent years, researchers have attempted lab and subsurface stimulation of the naturally slow process of methanogenic degradation of coal.

Annual Review of Earth and Planetary Sciences↗