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13C NMR spectral characterization of epimeric rotenone and some related tetrahydrobenzopyranofurobenzopyranones

The 13 C nuclear magnetic resonance (nmr) spectra of epimers of rotenone and four 12a-hydroxy-analogues were examined to determine the stereochemical effect of the B/C ring fusion involving the 6a- and 12a-carbon centers. Chemical shift differences between the epimeric carbon resonances of cis- and trans-6a,12a-compounds were notably larger than those of diastereoisomers derived from the same B/C ring junction stereochemistry. Results of the spectral analysis have been useful for the quantification of mixtures of epimers and for the measurement of rates of epimerization and oxygenation.

Journal of Heterocyclic Chemistry

Geospace environment modeling 2008--2009 challenge: D st index

This paper reports the metrics-based results of the D st index part of the 2008–2009 GEM Metrics Challenge. The 2008–2009 GEM Metrics Challenge asked modelers to submit results for four geomagnetic storm events and five different types of observations that can be modeled by statistical, climatological or physics-based models of the magnetosphere-ionosphere system. We present the results of 30 model settings that were run at the Community Coordinated Modeling Center and at the institutions of various modelers for these events. To measure the performance of each of the models against the observations, we use comparisons of 1 hour averaged model data with the D st index issued by the World Data Center for Geomagnetism, Kyoto, Japan, and direct comparison of 1 minute model data with the 1 minute D st index calculated by the United States Geological Survey. The latter index can be used to calculate spectral variability of model outputs in comparison to the index. We find that model rankings vary widely by skill score used. None of the models consistently perform best for all events. We find that empirical models perform well in general. Magnetohydrodynamics-based models of the global magnetosphere with inner magnetosphere physics (ring current model) included and stand-alone ring current models with properly defined boundary conditions perform well and are able to match or surpass results from empirical models. Unlike in similar studies, the statistical models used in this study found their challenge in the weakest events rather than the strongest events.

Space Weather

Water depth tolerances of dominant tree island species: What do we know?

Common woody species growing on tree islands in the Water Conservation Areas of South Florida include redbay, sweetbay, coastal-plain willow, wax myrtle, dahoon holly, cocoplum, pond-apple, red maple, cypress, gumbo-limbo, strangler fig and buttonbush. Very little is known about the flooding tolerance of most of these species. In this paper, we review flooding impact studies, describe the most common species and discuss two methods that might be used to examine woody plant growth response to water level fluctuations. Although tree coring has been used effectively in many areas, the general lack of discernible rings and poor quality rings observed in these species makes this method of questionable use. Dendrometer bands, however, work well in any environment with any species and are recommended for further studies on tree islands.

Book chapter

Geologic setting of Boulder 1, Station 2, Apollo 17 landing site

Boulder 1 at Station 2 is one of three boulders sampled by Apollo 17 at the base of the South Massif, which rises 2.3 km above the floor of a linear valley interpreted as a graben formed by deformation related to the southern Serenitatis impact. The boulders probably rolled from the upper part of the massif after emplacement of the light mantle. Orbital gravity data and photogeologic reinterpretation suggest that the Apollo 17 area is located approximately on the third ring of the southern Serenitatis basin, approximately 1.25 times larger than the analogous but fresher Orientale basin structure. The massif exposures are interpreted to represent the upper part of thick ejecta deposited by the southern Serenitatis impact near the rim of the transient cavity. Basin ring structure and the radial grabens that give the massifs definition were imposed on this ejecta at a slightly later stage in the basin-forming process. There is no clear-cut compositional, textural, or photogeologic evidence that Imbrium ejecta was collected at the Apollo 17 site.

The Moon

Dendrogeomorphic evidence of debris flow frequency and magnitude at Mount Shasta, California

Debris-flow deposits and woody vegetation adjacent to and growing within the channels of Whitney, Bolam, Mud, Ash, and Panthe creeks provide a 300-year record of debris-flow frequency at Mount Shasta Dendrochronologic (tree-ring) dating methods for the debris flows proved consistent with available documented records of debris flows Nine debris flows not reported in the historic record were documented and dated dendrochronologically. The oldest tree-ring date for a mudflow was about 1670 Combined geomorphic and botanical evidence shows that debris flows are a common occurrence at Mount Shasta Debris flows traveling at least 2 km have occurred at the rate of about 8 3 per century Smaller debris flows occur substantially more frequently and usually do not proceed as far downslope as larger debris flows. Cyclic scouring and filling by debris flows, in and adjacent to the stream channels, is suggested by dendrogeomorphic evidence and appears to be related to their magnitude and frequency Debris flows, small and large, may be the major surficial geomorphic agent in the vicinity of mount Shasta, sculpturing the channels and developing large alluvial fans ?? 1984 Springer-Verlag New York Inc.

California

Integument coloration signals reproductive success, heterozygosity, and antioxidant levels in chick-rearing black-legged kittiwakes

Carotenoid pigments are important for immunity and as antioxidants, and carotenoid-based colors are believed to provide honest signals of individual quality. Other colorless but more efficient antioxidants such as vitamins A and E may protect carotenoids from bleaching. Carotenoid-based colors have thus recently been suggested to reflect the concentration of such colorless antioxidants, but this has rarely been tested. Furthermore, although evidence is accruing for multiple genetic criteria for mate choice, carotenoid-based colors have rarely been shown to reflect both phenotypic and genetic quality. In this study, we investigated whether gape, tongue, eye-ring, and bill coloration of chick-rearing black-legged kittiwakes Rissa tridactyla reflected circulating levels of carotenoids and vitamins A and E. We further investigated whether integument coloration reflected phenotypic (body condition and fledging success) and genetic quality (heterozygosity). We found that the coloration of fleshy integuments was correlated with carotenoid and vitamin A levels and fledging success but only in males. Furthermore, the coloration of tongue and eye-ring was correlated with heterozygosity in both males and females. Integument colors might therefore be reliable signals of individual quality used by birds to adjust their parental care during the chick-rearing period.

Alaska

Diet composition and body condition of polar bears (Ursus maritimus) in relation to sea ice habitat in the Canadian High Arctic

Polar bears ( Ursus maritimus ) rely on sea ice for hunting marine mammal prey. Declining sea ice conditions associated with climate warming have negatively affected polar bears, especially in the southern portion of their range. At higher latitudes, the transition from multi-year ice to thinner annual ice has been hypothesized to increase biological productivity and potentially improve polar bear foraging conditions. To investigate this possibility, we used quantitative fatty acid signature analysis to characterize the diet composition of 148 polar bears in two high-latitude subpopulations from 2012 to 2014: (1) Viscount Melville Sound, where little is known about marine mammal ecology, and (2) Northern Beaufort Sea, a subpopulation considered stable with comparatively more ecological data. We used adipose tissue lipid content as an index of body condition. To characterize long-term habitat conditions, we examined trends in sea ice metrics from 1979 to 2014 in both regions. Although the diets of bears in both subpopulations were dominated by ringed seal ( Pusa hispida, mean biomass consumption = 45%), bears in Viscount Melville Sound showed higher proportional consumption of beluga whale ( Delphinapterus leucas ; mean biomass consumption = 37%) than any other polar bear subpopulation studied to date. Although the three-year duration of our study precludes long-term insights, relatively lighter sea ice conditions in Viscount Melville Sound were associated with reduced consumption of preferred prey (i.e., ringed seal), especially among female polar bears. Further, polar bears in Viscount Melville sound were in poorer body condition than those in the Northern Beaufort Sea. Our results do not indicate that declining sea ice has had any positive effect on polar bear foraging at high-latitudes.

Canadian High Arctic

Recent summer precipitation trends in the Greater Horn of Africa and the emerging role of Indian Ocean sea surface temperature

We utilize a variety of climate datasets to examine impacts of two mechanisms on precipitation in the Greater Horn of Africa (GHA) during northern-hemisphere summer. First, surface-pressure gradients draw moist air toward the GHA from the tropical Atlantic Ocean and Congo Basin. Variability of the strength of these gradients strongly influences GHA precipitation totals and accounts for important phenomena such as the 1960s–1980s rainfall decline and devastating 1984 drought. Following the 1980s, precipitation variability became increasingly influenced by the southern tropical Indian Ocean (STIO) region. Within this region, increases in sea-surface temperature, evaporation, and precipitation are linked with increased exports of dry mid-tropospheric air from the STIO region toward the GHA. Convergence of dry air above the GHA reduces local convection and precipitation. It also produces a clockwise circulation response near the ground that reduces moisture transports from the Congo Basin. Because precipitation originating in the Congo Basin has a unique isotopic signature, records of moisture transports from the Congo Basin may be preserved in the isotopic composition of annual tree rings in the Ethiopian Highlands. A negative trend in tree-ring oxygen-18 during the past half century suggests a decline in the proportion of precipitation originating from the Congo Basin. This trend may not be part of a natural cycle that will soon rebound because climate models characterize Indian Ocean warming as a principal signature of greenhouse-gas induced climate change. We therefore expect surface warming in the STIO region to continue to negatively impact GHA precipitation during northern-hemisphere summer.

Greater Horn of Africa

Drivers and consequences of apex predator diet composition in the Canadian Beaufort Sea

Polar bears ( Ursus maritimus ) rely on annual sea ice as their primary habitat for hunting marine mammal prey. Given their long lifespan, wide geographic distribution, and position at the top of the Arctic marine food web, the diet composition of polar bears can provide insights into temporal and spatial ecosystem dynamics related to climate-mediated sea ice loss. Polar bears with the greatest ecological constraints on diet composition may be most vulnerable to climate-related changes in ice conditions and prey availability. We used quantitative fatty acid signature analysis (QFASA) to estimate the diets of polar bears ( n = 419) in two western Canadian Arctic subpopulations (Northern Beaufort Sea and Southern Beaufort Sea) from 1999 to 2015. Polar bear diets were dominated by ringed seal ( Pusa hispida ), with interannual, seasonal, age- and sex-specific variation. Foraging area and sea ice conditions also affected polar bear diet composition. Most variation in bear diet was explained by longitude, reflecting spatial variation in prey availability. Sea ice conditions (extent, thickness, and seasonal duration) declined throughout the study period, and date of sea ice break-up in the preceding spring was positively correlated with female body condition and consumption of beluga whale ( Delphinapterus leucas ), suggesting that bears foraged on beluga whales during entrapment events. Female body condition was positively correlated with ringed seal consumption, and negatively correlated with bearded seal consumption. This study provides insights into the complex relationships between declining sea ice habitat and the diet composition and foraging success of a wide-ranging apex predator.

Northwest Territories, Yukon

Changes in structure and physiological functioning due to experimentally enhanced precipitation seasonality in a widespread shrub species

Semi-arid shrub steppe occupies a vast geographic range that is characterized in part by distinct seasonal patterns in precipitation. Few studies have evaluated how variability in both the amount and timing of precipitation affect the structure and physiology of shrubs in these systems. We quantified changes in foliar crown parameters, xylem anatomy, gas exchange, and hydraulic transport capacity in deep-rooted Artemisia tridentata shrubs following 20 years of experimental manipulations in amount and seasonal timing of precipitation. We hypothesized that shrub growth (total leaf area per shrub and cover of shrub community), hydraulic transport efficiency, and gas exchange would increase in shrubs in irrigated plots compared to non-irrigated control plots, especially for irrigation applied in winter rather than summer. We also predicted similar changes in xylem anatomy (ring width, vessel size and frequency). Most treatment responses entailed changes in plant structure, and were generally consistent with our hypotheses: total-shrub leaf area, shrub basal area, canopy cover, and maximum sapwood-specific branch hydraulic conductivity were more than 2× greater in shrubs in winter-irrigated compared to control plots, while summer irrigation had few effects on these variables. Irrigation in either season did not affect xylem vessel size, but did increase xylem ring width by ~ 2 × and decreased xylem vessel frequency by about half. Anatomical, morphological, and stand-level abundance of A. tridentata appeared much more responsive to irrigation than state changes in gas exchange, particularly when the extra water is received during winter. Thus, it appears for sagebrush that seasonal timing is at least as important as the amount of precipitation, and that responses to changes in precipitation timing occur through changes in carbon allocation more so than changes in leaf-level carbon gain.

Plant Ecology

Craters on Earth, Moon, and Mars: Multivariate classification and mode of origin

Testing extraterrestrial craters and candidate terrestrial analogs for morphologic similitude is treated as a problem in numerical taxonomy. According to a principal-components solution and a cluster analysis, 402 representative craters on the Earth, the Moon, and Mars divide into two major classes of contrasting shapes and modes of origin. Craters of net accumulation of material (cratered lunar domes, Martian “calderas,” and all terrestrial volcanoes except maars and tuff rings) group apart from craters of excavation (terrestrial meteorite impact and experimental explosion craters, typical Martian craters, and all other lunar craters). Maars and tuff rings belong to neither group but are transitional. The classification criteria are four independent attributes of topographic geometry derived from seven descriptive variables by the principal-components transformation. Morphometric differences between crater bowl and raised rim constitute the strongest of the four components. Although single topographic variables cannot confidently predict the genesis of individual extraterrestrial craters, multivariate statistical models constructed from several variables can distinguish consistently between large impact craters and volcanoes.

Earth and Planetary Science Letters

Responsiveness of 6 to 14 generations of birds to dietary dieldrin toxicity

The lethal dietary toxicity of dieldrin was estimated repeatedly during 8 years of testing young bobwhites (Colinus virginianus), Japanese quail (Coturnix c. japonica), ring-necked pheasants (Phasianus colchicus), and mallards (Anas platyrhynchos). Toxicities, quantified as 8-day LC50 values (5 days on toxic diet, followed by 3 days of untreated feed), were estimated at least 18 times per species. Average dietary LC50 values (ppm) and their 95% confidence limits for 14-day-old quail and 10-day-old pheasants and mallards were: bobwhite, 38 (34?42); Japanese quail, 61 (58?64); ring-necked pheasant, 56 (53?59); and mallard, 179 (163?195). No time-related changes were detected in LC50 values for any of the species.

Toxicology and Applied Pharmacology

Studies of a peatified angiosperm log cross section from Indonesia by nuclear magnetic resonance spectroscopy and analytical pyrolysis

Samples from a 10 cm cross-sectional radius of a peatified angiosperm log from Sumatra, Indonesia, were examined by 13 C nuclear magnetic resonance and pyrolysis-gas chromatography in order to understand chemical changes due to the peatification process. NMR results show degradation by selective loss of carbohydrates in all parts of the log section compared with fresh wood; however, the degree of degradation is less near the center of the log section. The degree of ring substitution of aromatic lignin monomeric units, as measured by dipolar dephasing NMR methods, appears to be less at the center of the log section than at the periphery. The methoxyl carbon content of lignin in the log is lower than in unaltered angiospermous lignin but does not appear to change as a function of either radial position or the degree of aromatic ring substitution. Pyrolysis-gas chromatography indicates higher yields of catechols in the outer areas relative to the heartwood. Other than the variations in catechol contents and in the yields of carbohydrate-derived pyrolysis products (e.g. levoglucosan, angelicalactones), the pyrolysis results do not show significant changes related to radial position, indicating that the lignin is not significantly altered across the log section.

Organic Geochemistry

Quantitative solid-state 13C nuclear magnetic resonance spectrometric analyses of wood xylen: Effect of increasing carbohydrate content

Isolated lignin with a low carbohydrate content was spiked with increasing amounts of alpha-cellulose, and then analysed by solid-state 13 C nuclear magnetic resonance (NMR) using cross-polarization with magic angle spinning (CPMAS) and dipolar dephasing methods in order to assess the quantitative reliability of CPMAS measurement of carbohydrate content and to determine how increasingly intense resonances for carbohydrate carbons affect calculations of the degree of lignin's aromatic ring substitution and methoxyl carbon content. Comparisons were made of the carbohydrate content calculated by NMR with carbohydrate concentrations obtained by phenol-sulfuric acid assay and by the calculation from the known amounts of cellulose added. The NMR methods used in this study yield overestimates for carbohydrate carbons due to resonance area overlap from the aliphatic side chain carbons of lignin. When corrections are made for these overlapping resonance areas, the NMR results agree very well with results obtained by other methods. Neither the calculated methoxyl carbon content nor the degree of aromatic ring substitution in lignin, both calculated from dipolar dephasing spectra, change with cellulose content. Likewise, lignin methoxyl content does not correlate with cellulose abundance when measured by integration of CPMAS spectra.

Organic Geochemistry

Organic geochemistry applied to environmental assessments of Prince William Sound, Alaska, after the Exxon Valdez oil spill—a review

Organic geochemistry played a major role in the environmental assessments conducted following the Exxon Valdez oil spill, which occurred on March 24, 1989, and released about 258,000 bbls (41 million liters) of Alaska North Slope crude oil into Prince William Sound. Geochemical analyses of more than 15,000 sediment, tar, and biological samples and about 5000 water samples provide the largest database yet collected on oil-spill chemistry, and we review the results here. The marine environment of the Sound has a complex background of petrogenic, pyrogenic, and biogenic hydrocarbons from natural and anthropogenic sources. Geochemical evaluation of the fate and effects of the spilled oil required that this oil and its residues be distinguished from the background. A variety of molecular and isotopic techniques were employed to identify various hydrocarbon sources and to distinguish quantitatively among mixed sources in the samples. Although the specific criteria used to distinguish multiple sources in the region affected by the Exxon Valdez spill are not necessarily applicable to all spill situations, the principles that governed their selection are. Distributions of polycyclic aromatic hydrocarbons (PAH) and dibenzothiophenes distinguish Exxon Valdez oil and its weathered residues from background hydrocarbons in benthic sediments. Ratios of C 2 -dibenzothiophene C 2 -phenanthrene "> C 2 -dibenzothiopheneC 2 -phenanthrene and C 3 -dibenzothiophene C 3 -phenanthrene "> C 3 -dibenzothiopheneC 3 -phenanthrene were particularly useful. Carbon isotopes and terpane distributions distinguished Exxon Valdez residues found on shorelines from tars from other sources. Diesel and diesel soot were identified by the absence of alkylated chrysenes and a narrow distribution of n -alkanes, whereas pyrogenic products were distinguished by the dominance of 4- to 6-ring PAH over 2- to 3-ring PAH and by the dominance of non-alkylated over alkylated homologues of each PAH series. The presence of 18α(H)-oleanane in benthic sediments, coupled with its absence in Exxon Valdez oil and its residues, confirm another petrogenic source. Results of geochemical studies suggest that the petrogenic component in the background of benthic sediments is derived from oil seeps in the eastern Gulf of Alaska. In 1990 and 1991, Exxon Valdez residues, generally forming a small increment to the pre-spill background, were found to be only sporadically distributed in some shallow, near shore sediments adjacent to shorelines that had been heavily oiled in 1989. In 1994, occurrences of Exxon Valdez tars on shoreline surfaces were rare, although residues could be found buried in shoreline sediments at some isolated locations along the spill path where they were protected from wave action. Spilled oil residues collected 16 months after the spill were degraded, on average, by nearly 50%. Shoreline residues from sources other than the spill were also identified and are widespread throughout the Sound. These residues include (1) geochemically distinct tars and oils imported from California oil fields to Alaska for fuel and construction purposes prior to the discovery of the Cook Inlet and North Slope oil fields, (2) diesel and diesel soot, and (3) more highly refined products. Of the more than 2700 chemical analyses of biological samples of higher life forms (fish, birds, and mammals) about 150 (6%) indicate recognizable residues of Exxon Valdez oil, which were identified by their distribution of polycyclic aromatic hydrocarbons (PAH). Most of these samples (138) were collected in 1989 and most were associated with external surfaces or the gastrointestinal tract. Rarely do internal tissues or fluids contain recognizable fingerprints of spilled oil. This observation includes samples from marine mammals that were visibly oiled externally. Other hydrocarbon sources, including diesel and a non-petroleum artifact that occurs when concentrations of individual PAH are at or near their method detection limit, are also identified in biological samples.

Alaska

Studies of angiospermous woods in Australian brown coal by nuclear magnetic resonance and analytical pyrolysis: new insight into early coalification

Many Tertiary coals contain abundant fossilized remains of angiosperms, which commonly dominated the ancient peat-swamp environments; modern analogs of such swamps can be found in tropical and subtropical regions of the world. Comparisons of angiospermous wood from Australian brown coal with similar wood buried in modern peat swamps of Indonesia have provided some new insights into coalification reactions. These comparisons were made by using solid-state 13 C nuclear magnetic resonance (NMR) techniques and pyrolsis-gas chromatography-mass spectrometry (py-gc-ms). These two modern techniques are especially suited for detailed structural evaluation of the complex macromolecules in coal. The earliest transformation (peatification) of organic matter in angiospermous wood is the degradation and removal of cellulosic components and the concomitant selective preservation of lignin-derived components. The angiospermous lignin that becomes enriched in wood as a result of cellulose degradation also is modified by coalification reactions; this modification, however, does not involve degradation and removal of the lignin. Rather, the early coalification process transforms the lignin phenols (guiacyl and syringyl) to eventually yield the aromatic structures typically found in brown coal. One such transformation, which is determined from NMR data, involves the cleavage of aryl-ether bonds that link guaiacyl and syringyl units in lignin, and this transformation leads to the formation of free lignin phenols. Another transformation, which is also determined from the NMR data, involves the loss of methoxyl groups, probably via demethylation, to produce catechol-like structures. Coincident with ether-cleavage and demethylation, the aromatic rings derived from lignin phenols become more carbon-substituted and cross linked, as determined by dipolar-dephasing NMR studies. This cross linking is probably responsible for preventing the lignin phenols, which are freed from the lignin macromolecule by ether cleavage, from being removed from the coal by dissolution. Pyrolysis data suggest that the syringyl units are altered more readily than are guaiacyl units, and this difference in resistance leads to an enrichment of the guaiacyl units in fossil angiospermous woods. Many of the coalification reactions noted above occur to some degree in all angiospermous fossil wood examined; however, some significant differences are observed in the degree of coalification of the fossil wood samples from the same burial depth in the brown coal. These differences indicate that the depth and duration of burial are probably not entirely responsible for the variations in degree of coalification. Different rates of degradation in peat may have contributed to the variations in the apparent degree of coalification; some woods may have been altered more rapidly at the peat stage than others. Although preliminary, this systematic study of botanically related wood in peat and coal results in a more detailed differentiation of coalification reactions than have previous investigations. The combined use of solid-state 13 C NMR and py-gc-ms has facilitated this detailed insight into the coalification of angiospermous wood.

International Journal of Coal Geology

Water movement through an experimental soil liner

A field-scale soil liner was constructed to test whether compacted soil barriers in cover and liner systems could be built to meet the U.S. EPA saturated hydraulic conductivity requirement (⩽ 1 × 10 −7 cm s −1 ). The 8 × 15 × 0.9 m liner was constructed in 15 cm compacted lifts using a 20,037 kg pad-foot compactor and standard engineering practices. Water infiltration into the liner has been monitored for one year. Monitoring will continue until water break through at the base of the liner occurs. Estimated saturated hydraulic conductivities were 2.5 × 10 −9 , 4.0 × 10 −8 , and 5.0 × 10 −8 cm s −1 based on measurements of water infiltration into the liner by large- and small-ring infiltrometers and a water balance analysis, respectively. Also investigated in this research was the variability of the liner's hydraulic properties and estimates of the transit times for water and tracers. Small variances exhibited by small-ring flux data suggested that the liner was homogeneous with respect to infiltration fluxes. The predictions of water and tracer breakthrough at the base of the liner ranged from 2.4–12.6 y, depending on the method of calculation and assumptions made. The liner appeared to be saturated to a depth between 18 and 33 cm at the end of the first year of monitoring. Transit time calculations cannot be verified yet, since breakthrough has not occurred. The work conducted so far indicates that compacted soil barriers can be constructed to meet the saturated hydraulic conductivity requirement established by the U.S. EPA.

Waste Management and Research

Paleoproterozoic high-sulfidation mineralization in the Tapajós gold province, Amazonian Craton, Brazil: geology, mineralogy, alunite argon age, and stable-isotope constraints

The Brazilian Tapajós gold province contains the first evidence of high-sulfidation gold mineralization in the Amazonian Craton. The mineralization appears to be in large nested calderas. The Tapajós–Parima (or Ventuari–Tapajós) geological province consists of a metamorphic, igneous, and sedimentary sequence formed during a 2.10 to 1.87 Ga ocean−continent orogeny. The high-sulfidation mineralization with magmatic-hydrothermal alunite is related to hydrothermal breccias hosted in a rhyolitic volcanic ring complex that contains granitic stocks ranging in age from 1.89 to 1.87 Ga. Cone-shaped hydrothermal breccias, which flare upward, contain vuggy silica and have an overlying brecciated cap of massive silica; the deposits are located in the uppermost part of a ring-structure volcanic cone. Drill cores of one of the hydrothermal breccias contain alunite, natroalunite, pyrophyllite, andalusite, quartz, rutile, diaspore, woodhouseite–svanbergite, kaolinite, and pyrite along with inclusions of enargite–luzonite, chalcopyrite, bornite, and covellite. The siliceous core of this alteration center is surrounded by advanced argillic and argillic alteration zones that grade outward into large areas of propylitically altered rocks with sericitic alteration assemblages at depth. Several occurrences and generations of alunite are observed. Alunite is disseminated in the advanced argillic haloes that envelop massive and vuggy silica or that underlie the brecciated silica cap. Coarse-grained alunite also occurs in branching veins and locally is partly replaced by a later generation of fine-grained alunite. Silicified hydrothermal breccias associated with the alunite contain an estimated reserve of 30 tonnes of gold in rock that grades up to 4.5 g t −1 Au. Seven alunite samples gave 40 Ar/ 39 Ar ages of 1.869 to 1.846 Ga, with various degrees of apparent minor Ar loss. Stable isotopic data require a magmatic-hydrothermal origin for the alunite, typical for high-sulfidation mineralization. The δ 34 S values of most samples of alunite range from 14.0‰ to 36.9‰. Sulfur isotopic alunite–pyrite and oxygen isotopic alunite SO 4 −OH temperatures range from 130 to 420 °C. The δD H 2 O and δ 18 O H 2 O values for alunite-forming hydrothermal fluids suggest a predominance of magmatic water, with a small meteoric contribution. A rare sample of supergene alunite has a δ 34 S value of 4.1‰ and an 40 Ar/ 39 Ar age of 51.3±0.1 Ma. Other than local foliation in the volcanic rocks and recrystallization of alunite near faults, the mineralization and associated alteration appears to have been remarkably undisturbed by later metamorphism and by supergene alteration. The Au mineralization was preserved because of burial by sediments and tuffs in taphrogenic basins that probably developed shortly after mineralization and were probably first exhumed at about 60 Ma. Because high-sulfidation mineralization forms at relatively shallow crustal levels, the discoveries in Tapajós province provide new perspectives for mineral exploration for the Amazonian and perhaps for other Precambrian cratons.

Chemical Geology