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At least 307 records · Page 17Linked to original sources

USGS2014

Dendrochemical patterns of calcium, zinc, and potassium related to internal factors detected by energy dispersive X-ray fluorescence (EDXRF)

Energy dispersive X-ray fluorescence (EDXRF) provides highly sensitive and precise spatial resolution of cation content in individual annual growth rings in trees. The sensitivity and precision have prompted successful applications to forensic dendrochemistry and the timing of environmental releases of contaminants. These applications have highlighted the need to distinguish dendrochemical effects of internal processes from environmental contamination. Calcium, potassium, and zinc are three marker cations that illustrate the influence of these processes. We found changes in cation chemistry in tree rings potentially due to biomineralization, development of cracks or checks, heartwood/sapwood differentiation, intra-annual processes, and compartmentalization of infection. Distinguishing internal from external processes that affect dendrochemistry will enhance the value of EDXRF for both physiological and forensic investigations.

Chemosphere↗

USGS2012

Analogues of doxanthrine reveal differences between the dopamine D1 receptor binding properties of chromanoisoquinolines and hexahydrobenzo[a]phenanthridines

Efforts to develop selective agonists for dopamine D 1 -like receptors led to the discovery of dihydrexidine and doxanthrine, two bioisosteric β-phenyldopamine-type full agonist ligands that display selectivity and potency at D 1 -like receptors. We report herein an improved methodology for the synthesis of substituted chromanoisoquinolines (doxanthrine derivatives) and the evaluation of several new compounds for their ability to bind to D 1 - and D 2 -like receptors. Identical pendant phenyl ring substitutions on the dihydrexidine and doxanthrine templates surprisingly led to different effects on D 1 -like receptor binding, suggesting important differences between the interactions of these ligands with the D 1 receptor. We propose, based on the biological results and molecular modeling studies, that slight conformational differences between the tetralin and chroman-based compounds lead to a shift in the location of the pendant ring substituents within the receptor.

European Journal of Medicinal Chemistry↗

USGS2024

Variable climate-growth relationships of quaking aspen (Populus tremuloides) among Sky Island mountain ranges in the Great Basin, Nevada, USA

The Great Basin is an arid province located in the interior western United States. The region encompasses millions of hectares and quaking aspen ( Populus tremuloides Michx.) forests comprise a minor portion of the total area. However, montane aspen forests play a disproportionately large role in providing ecosystem services in the region, including water retention, biodiversity, wildlife habitat, livestock forage, and recreational uses. With warming temperatures, increasing evaporative demand, and heightened precipitation variability, the future of aspen has become a critical concern. Using dendroecological approaches, we assessed growth patterns of 20 aspen stands across three geographically isolated “sky island” mountain ranges spanning portions of the north-central Great Basin. We anticipated that the growth of Great Basin aspen would be strongly influenced by regional climatic patterns and largely in synchrony. Results revealed a more complex growth dynamic that varied among mountain ranges and across environmental gradients. In particular, aspen climate-growth relationships in the slightly dryer Ruby Mountains were strongly and positively correlated (r > 0.5) with previous fall to winter moisture availability. The Jarbidge Mountains had a positive but modest relationship with previous fall to winter moisture availability (r > 0.3). Climate-growth response in the Santa Rosa Mountains, the wettest range, showed no significant response to moisture availability during any time period examined but had greater tree-ring growth with warmer May temperatures. Although tree-ring centennial (1910 – 2010) growth trends were positive for all three mountain ranges, only the Santa Rosa Mountains maintained a positive recent growth trend (1970 – 2010). Moreover, distinct temporal shifts in tree growth-climate relationships in each mountain range suggest potentially unique aspen population adaptations to climate variability. For instance, in two of the mountain ranges, there was a shift from positive/neutral to negative growth relationships with temperature starting around the 1963 – 1987 time period, while tree growth also began simultaneously responding more positively to moisture availability. These growth shifts and observed enhanced sensitivities to monthly and seasonal climate variables over time may reflect dynamic tree growth responses caused by ongoing global climate change, but that may be tempered by local or regional factors, such as the relative availability and timing of soil moisture provided by spring snowmelt. A better understanding of biogeographic variation and causality in aspen growth could provide multiple management pathways governed by resilience characteristics in the face of future anthropogenic and climatic threats.

Nevada↗

USGS2024

Trees have similar growth responses to first-entry fires and reburns following long-term fire exclusion

Managing fire ignitions for resource benefit decreases fuel loads and reduces the risk of high-severity fire in fire-suppressed dry conifer forests. However, the reintroduction of low-severity wildfire can injure trees, which may decrease their growth after fire. Post-fire growth responses could change from first-entry fires to reburns, as first-entry fires reduce fuel loads and the vulnerability among trees to fire effects, which may result in trees sustaining less damage during reburns. To determine whether trees had growth responses that varied from first-entry fires to reburns, we cored 87 ponderosa pine trees in the Gila Wilderness, New Mexico, USA that experienced 3–5 fires between 1950 and 2012 following long-term fire-exclusion and 67 unburned control trees from the Gila and Apache-Sitgreaves National Forests. We assessed tree growth response to fire by comparing tree-ring growth among burned and unburned trees from two years before to two years after fires. We compared growth between burned and unburned trees using a bootstrapping procedure to calculate annual median tree-ring width index values with 95 % confidence intervals. We compared post-fire growth after first-entry fires and reburns following long-term fire-exclusion. Burned trees had similar growth responses following first-entry fires and reburns, with lower growth during the fire year through two years post-fire compared to unburned controls. Burned tree growth returned to expected rates following these immediate post-fire growth reductions. Interestingly, trees had lower growth during the year before and the year of reburns compared to the first-entry fire, reflecting greater aridity before reburns. Greater aridity may have contributed to larger-than-expected growth reductions following reburns, which could explain similar growth responses to first-entry fires and reburns. Our results indicate that trees had consistent short-term growth responses to low-severity fires following long-term fire-exclusion. As trees retained vigor after multiple fires, managing fires for resource benefit is an effective approach to reduce the likelihood of high-severity fire without long-term negative effects on tree growth.

Forest Ecology and Management↗

USGS2010

Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13 C NMR spectroscopy

We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R 0 from 0.29% to 1.27%). Specific functional groups such as CH 3 , CH 2 , alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as "oil prone" and "gas prone" carbons, have been quantified by 13 C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (???30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ???30 carbons, and of ???20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1 H- 13 C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters. ?? 2010 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗

USGS2005

The Zamama-Thor region of Io: Insights from a synthesis of mapping, topography, and Galileo spacecraft data

We have studied data from the Galileo spacecraft's three remote sensing instruments (Solid-State Imager (SSI), Near-Infrared Mapping Spectrometer (NIMS), and Photopolarimeter-Radiometer (PPR)) covering the Zamama–Thor region of Io's antijovian hemisphere, and produced a geomorphological map of this region. This is the third of three regional maps we are producing from the Galileo spacecraft data. Our goal is to assess the variety of volcanic and tectonic materials and their interrelationships on Io using planetary mapping techniques, supplemented with all available Galileo remote sensing data. Based on the Galileo data analysis and our mapping, we have determined that the most recent geologic activity in the Zamama–Thor region has been dominated by two sites of large-scale volcanic surface changes. The Zamama Eruptive Center is a site of both explosive and effusive eruptions, which emanate from two relatively steep edifices (Zamama Tholi A and B) that appear to be built by both silicate and sulfur volcanism. A ∼100-km long flow field formed sometime after the 1979 Voyager flybys, which appears to be a site of promethean-style compound flows, flow-front SO 2 plumes, and adjacent sulfur flows. Larger, possibly stealthy, plumes have on at least one occasion during the Galileo mission tapped a source that probably includes S and/or Cl to produce a red pyroclastic deposit from the same vent from which silicate lavas were erupted. The Thor Eruptive Center, which may have been active prior to Voyager , became active again during the Galileo mission between May and August 2001. A pillanian-style eruption at Thor included the tallest plume observed to date on Io (at least 500 km high) and new dark lava flows. The plume produced a central dark pyroclastic deposit (probably silicate-rich) and an outlying white diffuse ring that is SO 2 -rich. Mapping shows that several of the new dark lava flows around the plume vent have reoccupied sites of earlier flows. Unlike most of the other pillanian eruptions observed during the Galileo mission, the 2001 Thor eruption did not produce a large red ring deposit, indicating a relative lack of S and/or Cl gases interacting with the magma during that eruption. Between these two eruptive centers are two paterae, Thomagata and Reshef. Thomagata Patera is located on a large shield-like mesa and shows no signs of activity. In contrast, Reshef Patera is located on a large, irregular mesa that is apparently undergoing degradation through erosion (perhaps from SO 2 -sapping or chemical decomposition of sulfur-rich material) from multiple secondary volcanic centers.

Icarus↗

USGS2008

Compositional mapping of Saturn's satellite Dione with Cassini VIMS and implications of dark material in the Saturn system

Cassini VIMS has obtained spatially resolved imaging spectroscopy data on numerous satellites of Saturn. A very close fly-by of Dione provided key information for solving the riddle of the origin of the dark material in the Saturn system. The Dione VIMS data show a pattern of bombardment of fine, sub-0.5-??m diameter particles impacting the satellite from the trailing side direction. Multiple lines of evidence point to an external origin for the dark material on Dione, including the global spatial pattern of dark material, local patterns including crater and cliff walls shielding implantation on slopes facing away from the trailing side, exposing clean ice, and slopes facing the trailing direction which show higher abundances of dark material. Multiple spectral features of the dark material match those seen on Phoebe, Iapetus, Hyperion, Epimetheus and the F-ring, implying the material has a common composition throughout the Saturn system. However, the exact composition of the dark material remains a mystery, except that bound water and, tentatively, ammonia are detected, and there is evidence both for and against cyanide compounds. Exact identification of composition requires additional laboratory work. A blue scattering peak with a strong UV-visible absorption is observed in spectra of all satellites which contain dark material, and the cause is Rayleigh scattering, again pointing to a common origin. The Rayleigh scattering effect is confirmed with laboratory experiments using ice and 0.2-??m diameter carbon grains when the carbon abundance is less than about 2% by weight. Rayleigh scattering in solids is also confirmed in naturally occurring terrestrial rocks, and in previously published reflectance studies. The spatial pattern, Rayleigh scattering effect, and spectral properties argue that the dark material is only a thin coating on Dione's surface, and by extension is only a thin coating on Phoebe, Hyperion, and Iapetus, although the dark material abundance appears higher on Iapetus, and may be locally thick. As previously concluded for Phoebe, the dark material appears to be external to the Saturn system and may be cometary in origin. We also report a possible detection of material around Dione which may indicate Dione is active and contributes material to the E-ring, but this observation must be confirmed.

Icarus↗

USGS2023

Field and laboratory validation of new sampling gear to quantify coregonine egg deposition and larval emergence across spawning habitat gradients

The influence of habitat and environmental conditions on Great Lakes coregonine reproduction is not well described, in part, because we lack sampling gears for early life stages that are effective across habitats. We designed new egg and larval emergence traps to quantify coregonine reproductive success across variable depths and substrates and tested them in laboratory and field settings. In the laboratory, our new metal ring egg traps had greater egg retention (94–100%) and faster post-catch processing (5–7 min) relative to a commonly employed fiber mat trap (30–67% and 30–60 min). In Lake Ontario’s Chaumont Bay, egg densities for lake whitefish Coregonus clupeaformis (0–5,832 eggs m −2 ) and cisco Coregonus artedi (0–426,501 eggs m −2 ) measured with metal ring traps (n = 112) varied across habitats but were greatest between 2–5 m on rock and dreissenid mussel substrates. Emergence traps used an inverted cone, fine mesh, and a clear collection chamber to capture positively phototactic emerging larvae. In the laboratory, traps captured 69–80% of emerged larvae. In Chaumont Bay, emergence traps deployed for 21 days after ice out caught only cisco larvae. Emergence rates varied across habitats (0–118 larvae m −2 day −1 , n = 85) but were highest on dreissenid mussel reef substrate. Our samplers improved processing efficiency and facilitated large sample sizes to quantify variability in egg deposition densities and emergence rates across habitats. These methods can advance coregonine conservation by determining how anthropogenic changes to habitat and environmental conditions influence incubation success.

Journal of Great Lakes Research↗

USGS2004

Volcanological perspectives on Long Valley, Mammoth Mountain, and Mono Craters: Several contiguous but discrete systems

The volcanic history of the Long Valley region is examined within a framework of six successive (spatially discrete) foci of silicic magmatism, each driven by locally concentrated basaltic intrusion of the deep crust in response to extensional unloading and decompression melting of the upper mantle. A precaldera dacite field (3.5–2.5 Ma) northwest of the later site of Long Valley and the Glass Mountain locus of >60 high-silica rhyolite vents (2.2–0.79 Ma) northeast of it were spatially and temporally independent magmatic foci, both cold in postcaldera time. Shortly before the 760-ka caldera-forming eruption, the mantle-driven focus of crustal melting shifted ∼20 km westward, abandoning its long-stable position under Glass Mountain and energizing instead the central Long Valley system that released 600 km 3 of compositionally zoned rhyolitic Bishop Tuff (760 ka), followed by ∼100 km 3 of crystal-poor Early Rhyolite (760–650 ka) on the resurgent dome and later by three separate 5-unit clusters of varied Moat Rhyolites of small volume (527–101 ka). West of the caldera ring-fault zone, a fourth focus started up ∼160 ka, producing a 10×20-km array of at least 35 mafic vents that surround the trachydacite/alkalic rhyodacite Mammoth Mountain dome complex at its core. This young 70-vent system lies west of the structural caldera and (though it may have locally re-energized the western margin of the mushy moribund Long Valley reservoir) represents a thermally and compositionally independent focus. A fifth major discrete focus started up by ∼50 ka, 25–30 km north of Mammoth Mountain, beneath the center of what has become the Mono Craters chain. In the Holocene, this system advanced both north and south, producing ∼30 dike-fed domes of crystal-poor high-silica rhyolite, some as young as 650 years. The nearby chain of mid-to-late Holocene Inyo domes is a fault-influenced zone of mixing where magmas of at least four kinds are confluent. The sixth and youngest focus is at Mono Lake, where basalt, dacite, and low-silica rhyolite unrelated to the Mono Craters magma reservoir have erupted in the interval 14 to 0.25 ka. A compelling inference is that mantle-driven magmatic foci have moved repeatedly, allowing abandoned silicic reservoirs, including the formerly vigorous Long Valley magma chamber, to crystallize. A 100-fold decline of intracaldera eruption rate after 650 ka, lack of crystal-poor rhyolite since 300 ka, limited volumes of moat rhyolite (most of it crystal-rich), absence of postcaldera mafic volcanism inside the structural caldera (or north and south adjacent to it), low thermal gradients inside the caldera, and sourcing of hydrothermal underflow within the western array well outside the ring-fault zone all suggest that the Long Valley magma reservoir is moribund.

California↗

USGS2009

A preliminary study of older hot spring alteration in Sevenmile Hole, Grand Canyon of the Yellowstone River, Yellowstone Caldera, Wyoming

Erosion in the Grand Canyon of the Yellowstone River, Yellowstone Caldera (640 ka), Wyoming, has exposed a cross section of older hydrothermal alteration in the canyon walls. The altered outcrops of the post-collapse tuff of Sulphur Creek (480 ka) extend from the canyon rim to more than 300 m beneath it. The hydrothermal minerals are zoned, with an advanced argillic alteration consisting of an association of quartz (opal) + kaolinite ± alunite ± dickite, and an argillic or potassic alteration association with quartz + illite ± adularia. Disseminated fine-grained pyrite or marcasite is ubiquitous in both alteration types. These alteration associations are characteristic products of shallow volcanic epithermal environments. The contact between the two alteration types is about 100 m beneath the rim. By analogy to other active geothermal systems including active hydrothermal springs in the Yellowstone Caldera, the transition from kaolinite to illite occurred at temperatures in the range 150 to 170 °C. An 40 Ar/ 39 Ar age on alunite of 154,000 ± 16,000 years suggests that hydrothermal activity has been ongoing since at least that time. A northwest-trending linear array of extinct and active hot spring centers in the Sevenmile Hole area implies a deeper structural control for the upflowing hydrothermal fluids. We interpret this deeper structure to be the Yellowstone Caldera ring fault that is covered by the younger tuff of Sulphur Creek. The Sevenmile Hole altered area lies at the eastern end of a band of hydrothermal centers that may mark the buried extension of the Yellowstone Caldera ring fault across the northern part of the Caldera.

Wyoming↗

USGS2009

Mesoscale raised rim depressions (MRRDs) on Earth: A review of the characteristics, processes, and spatial distributions of analogs for Mars

Fields of mesoscale raised rim depressions (MRRDs) of various origins are found on Earth and Mars. Examples include rootless cones, mud volcanoes, collapsed pingos, rimmed kettle holes, and basaltic ring structures. Correct identification of MRRDs on Mars is valuable because different MRRD types have different geologic and/or climatic implications and are often associated with volcanism and/or water, which may provide locales for biotic or prebiotic activity. In order to facilitate correct identification of fields of MRRDs on Mars and their implications, this work provides a review of common terrestrial MRRD types that occur in fields. In this review, MRRDs by formation mechanism, including hydrovolcanic (phreatomagmatic cones, basaltic ring structures), sedimentological (mud volcanoes), and ice-related (pingos, volatile ice-block forms) mechanisms. For each broad mechanism, we present a comparative synopsis of (i) morphology and observations, (ii) physical formation processes, and (iii) published hypothesized locations on Mars. Because the morphology for MRRDs may be ambiguous, an additional tool is provided for distinguishing fields of MRRDs by origin on Mars, namely, spatial distribution analyses for MRRDs within fields on Earth. We find that MRRDs have both distinguishing and similar characteristics, and observation that applies both to their mesoscale morphology and to their spatial distribution statistics. Thus, this review provides tools for distinguishing between various MRRDs, while highlighting the utility of the multiple working hypotheses approach. ?? 2008 Elsevier Ltd.

Planetary and Space Science↗

USGS2001

Tannin diagenesis in mangrove leaves from a tropical estuary: A novel molecular approach

Molecular-level condensed tannin analyses were conducted on a series of mangrove (Rhizophora mangle) leaves at various stages of decomposition in a tropical estuary. Total molecular tannin yields ranged from 0.5% ash-free dry weight (AFDW) in the most highly degraded black leaves (6-7 weeks in the water) up to >7% AFDW in fresh leaves (<1 week in the water). Total tannin exhibits an intermediate lability in these leaves relative to other measured biochemicals. Leaching is an important mechanism in tannin removal from leaves as indicated by the 30% loss of measurable tannin during a leaching experiment. Condensed tannin was >80% procyanidin (PC) with the remainder being prodelphinidin (PD). PD tannin, with its higher degree of hydroxylation, proved to be more labile than PC tannin. Average chain length of condensed tannin (degree of polymerization) exhibited an initial increase in response to leaching, but later decreased in the subsequent shift toward abiotic or microbially mediated chemical reactions. Several trends point toward a possible condensation reaction in which tannin plays a role in nitrogen immobilization. These include an apparent inverse correlation between molecular tannin and nitrogen, a positive correlation between molecular tannin and percent basic amino acids, 13C-NMR data indicating transformation of tannin as opposed to remineralization, and 13C-NMR data showing loss of condensed tannin B-ring phenolic carbons coupled with preservation of A-ring phenolic carbon. In addition to condensed tannin, the molecular method used also yielded several triterpenoids. Triterpenoids accounted for up to 3.5% AFDW of the leaf material and exhibited a threefold increase between yellow senescent leaves entering the estuary and black leaves. This trend is likely due to the weakening of protective cuticular membranes during leaf decomposition, which leads to increased yields in the acidic conditions used for tannin analyses. Copyright ?? 2001 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗

USGS1986

Cambrian nepheline syenite complex at Jabal Sawda, Midyan region, Kingdom of Saudi Arabia

The only nepheline syenite complex presently known in the Arabian Shield is at Jabal Sawda, about 30 km S of Haql in the extreme NW of Saudi Arabia. It is a post-tectonic, composite intrusion with a crudely concentric structure. A core of leuco-nepheline syenite, a partial ring of mela-nepheline syenite, and an almost complete outer ring of alkali-feldspar syenite are the main rock units. Several mega-inclusions of porphyritic nepheline syenite, nepheline monzosyenite, malignite and ijolite are present in the leuco-nepheline syenite. The chemical composition is notable for very high values of Al 2 O 3 , Na 2 O, Ba, La, Nb, Sr and Zr. U Pb isotope dating indicates an emplacement age of 553 ± 4 Ma, one of an increasing number of reliable Cambrian isotope dates in the northern Red Sea region.

Journal of African Earth Sciences↗

USGS1986

Jabal Silsilah tin prospect, Najd region, Kingdom of Saudi Arabia

A significant Sn deposit at Jabal Silsilah (26°07′N, 42°41′E), a prominent ring complex in the NE Arabian Shield, is associated with greisen in flat-topped cupolas of a highly evolved, zinnwaldite- and topaz-bearing alkali-feldspar granite. This granite is peraluminous, enriched in incompatible trace elements and characterized by a chondrite-normalized REE profile showing a large negative Eu anomaly, but otherwise flat. It is overlain by a carapace of aplite and pegmatite, beneath which accumulated residual fluids caused greisenization and deposition of disseminated cassiterite. Quartz—wolframite veins cut both granite and carapace. The other components of the Silsilah complex, from oldest to youngest, are: alkaline dacite, peralkaline granite and hypabyssal rocks. Their occurrence in a single ring structure and geochemical affinities indicate that they comprise a differentiation series. Fractionation of sodic plagioclase, apatite and Fe and Ti oxides resulted in parental alkaline dacite magma becoming peralkaline and granitic. Subsequent fractionation of alkali feldspar, soda pyribole and zircon resulted in a peraluminous melt enriched in incompatible trace elements.

Journal of African Earth Sciences↗

USGS2002

Determination of selected azaarenes in water by bonded-phase extraction and liquid chromatography

A method for the rapid and simple quantitative determination of quinoline, isoquinoline, and five selected three-ring azaarenes in water has been developed. The azaarene fraction is separated from its carbon analogues on n-octadecyl packing material by edition with acidified water/acetonitrile. Concentration as great as 1000-fold is achieved readily. Instrumental analysis involves high-speed liquid chromatography on flexible-walled, wide-bore columns with fluorescence and ultraviolet detection at several wavelengths employing filter photometers in series. Method-validation data is provided as azaarene recovery efficiency from fortified samples. Distilled water, river water, contaminated ground water, and secondary-treatment effluent have been tested. Recoveries at part-per-billion levels are nearly quantitative for the three-ring compounds, but they decrease for quinoline and isoquinoline.

Analytical Chemistry↗

USGS2002

Dipolar-dephasing 13C NMR studies of decomposed wood and coalified xylem tissue: Evidence for chemical structural changes associated with defunctionalization of lignin structural units during coalification

A series of decomposed and coalified gymnosperm woods was examined by conventional solid-state 13C nuclear magnetic resonance (NMR) and by dipolar-dephasing NMR techniques. The results of these NMR studies for a histologically related series of samples provide clues as to the nature of codification reactions that lead to the defunctionalization of lignin-derived aromatic structures. These reactions sequentially involve the following: (1) loss of methoxyl carbons from guaiacyl structural units with replacement by hydroxyls and increased condensation; (2) loss of hydroxyls or aryl ethers with replacement by hydrogen as rank increases from lignin to high-volatile bituminous coal; (3) loss of alkyl groups with continued replacement by hydrogen. The dipolar-dephasing data show that the early stages of coalification in samples examined (lignin to lignite) involve a decreasing degree of protonation on aromatic rings and suggest that condensation is significant during coalification at this early stage. An increasing degree of protonation on aromatic rings is observed as the rank of the sample increases from lignite to anthracite.

Energy & Fuels↗

USGS2009

Biodegradation of 17β-estradiol, estrone and testosterone in stream sediments

Biodegradation of 17β-estradiol (E2), estrone (E1), and testosterone (T) was investigated in three wastewater treatment plant (WWTP) affected streams in the United States. Relative differences in the mineralization of [4- 14 C] substrates were assessed in oxic microcosms containing saturated sediment or water-only from locations upstream and downstream of the WWTP outfall in each system. Upstream sediment demonstrated significant mineralization of the “A” ring of E2, E1, and T, with biodegradation of T consistently greater than that of E2 and no systematic difference in E2 and E1 biodegradation. “A” ring mineralization also was observed in downstream sediment, with E1 and T mineralization being substantially depressed relative to upstream samples. In marked contrast, E2 mineralization in sediment immediately downstream from the WWTP outfalls was more than double that in upstream sediment. E2 mineralization was observed in water, albeit at insufficient rate to prevent substantial downstream transport. The results indicate that, in combination with sediment sorption processes which effectively scavenge hydrophobic contaminants from the water column and immobilize them in the vicinity of the WWTP outfall, aerobic biodegradation of reproductive hormones can be an environmentally important mechanism for nonconservative (destructive) attenuation of hormonal endocrine disruptors in effluent-affected streams.

Colorado, Iowa↗

USGS2004

Aqueous photolysis of niclosamide

The photodegradation of [ 14 C]niclosamide was studied in sterile, pH 5, 7, and 9 buffered aqueous solutions under artificial sunlight at 25.0 ± 1.0 °C. Photolysis in pH 5 buffer is 4.3 times faster than in pH 9 buffer and 1.5 times faster than in pH 7 buffer. In the dark controls, niclosamide degraded only in the pH 5 buffer. After 360 h of continuous irradiation in pH 9 buffer, the chromatographic pattern of the degradates was the same regardless of which ring contained the radiolabel. An HPLC method was developed that confirmed these degradates to be carbon dioxide and two- and four-carbon aliphatic acids formed by cleavage of both aromatic rings. Carbon dioxide was the major degradate, comprising ∼40% of the initial radioactivity in the 360 h samples from both labels. The other degradates formed were oxalic acid, maleic acid, glyoxylic acid, and glyoxal. In addition, in the chloronitroaniline-labeled irradiated test solution, 2-chloro-4-nitroaniline was observed and identified after 48 h of irradiation but was not detected thereafter. No other aromatic compounds were isolated or observed in either labeled test system.

Journal of Agricultural and Food Chemistry↗