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At least 991 records · Page 55Linked to original sources

USGS2005

Identifying calcium sources at an acid deposition-impacted spruce forest: A strontium isotope, alkaline earth element multi-tracer approach

Depletion of calcium from forest soils has important implications for forest productivity and health. Ca is available to fine feeder roots from a number of soil organic and mineral sources, but identifying the primary source or changes of sources in response to environmental change is problematic. We used strontium isotope and alkaline earth element concentration ratios of trees and soils to discern the record of Ca sources for red spruce at a base-poor, acid deposition-impacted watershed. We measured 87 Sr/ 86 Sr and chemical compositions of cross-sectional stemwood cores of red spruce, other spruce tissues and sequential extracts of co-located soil samples. 87 Sr/ 86 Sr and Sr/Ba ratios together provide a tracer of alkaline earth element sources that distinguishes the plant-available fraction of the shallow organic soils from those of deeper organic and mineral soils. Ca/Sr ratios proved less diagnostic, due to within-tree processes that fractionate these elements from each other. Over the growth period from 1870 to 1960, 87 Sr/ 86 Sr and Sr/Ba ratios of stemwood samples became progressively more variable and on average trended toward values that considered together are characteristic of the uppermost forest floor. In detail the stemwood chemistry revealed an episode of simultaneous enhanced uptake of all alkaline earth elements during the growth period from 1930 to 1960, coincident with reported local and regional increases in atmospheric inputs of inorganic acidity. We attribute the temporal trends in stemwood chemistry to progressive shallowing of the effective depth of alkaline earth element uptake by fine roots over this growth period, due to preferential concentration of fine roots in the upper forest floor coupled with reduced nutrient uptake by roots in the lower organic and upper mineral soils in response to acid-induced aluminum toxicity. Although both increased atmospheric deposition and selective weathering of Ca-rich minerals such as apatite provide possible alternative explanations of aspects of the observed trends, the chemical buffering capacity of the forest floor-biomass pool limits their effectiveness as causal mechanisms.

Biogeochemistry↗

USGS2007

Decomposition of soil organic matter from boreal black spruce forest: Environmental and chemical controls

Black spruce forests are a dominant covertype in the boreal forest region, and they inhabit landscapes that span a wide range of hydrologic and thermal conditions. These forests often have large stores of soil organic carbon. Recent increases in temperature at northern latitudes may be stimulating decomposition rates of this soil carbon. It is unclear, however, how changes in environmental conditions influence decomposition in these systems, and if substrate controls of decomposition vary with hydrologic and thermal regime. We addressed these issues by investigating the effects of temperature, moisture, and organic matter chemical characteristics on decomposition of fibric soil horizons from three black spruce forest sites. The sites varied in drainage and permafrost, and included a “Well Drained” site where permafrost was absent, and “Moderately well Drained” and “Poorly Drained” sites where permafrost was present at about 0.5 m depth. Samples collected from each site were incubated at five different moisture contents (2, 25, 50, 75, and 100% saturation) and two different temperatures (10°C and 20°C) in a full factorial design for two months. Organic matter chemistry was analyzed using pyrolysis gas chromatography-mass spectrometry prior to incubation, and after incubation on soils held at 20°C, 50% saturation. Mean cumulative mineralization, normalized to initial carbon content, ranged from 0.2% to 4.7%, and was dependent on temperature, moisture, and site. The effect of temperature on mineralization was significantly influenced by moisture content, as mineralization was greatest at 20°C and 50–75% saturation. While the relative effects of temperature and moisture were similar for all soils, mineralization rates were significantly greater for samples from the “Well Drained” site compared to the other sites. Variations in the relative abundances of polysaccharide-derivatives and compounds of undetermined source (such as toluene, phenol, 4-methyl phenol, and several unidentifiable compounds) could account for approximately 44% of the variation in mineralization across all sites under ideal temperature and moisture conditions. Based on our results, changes in temperature and moisture likely have similar, additive effects on in situ soil organic matter (SOM) decomposition across a wide range of black spruce forest systems, while variations in SOM chemistry can lead to significant differences in decomposition rates within and among forest sites.

Biogeochemistry↗

USGS2025

Seasonal synchronicity and multi-decadal stability of headwater biogeochemistry in the northern temperate zone

Temporal patterns in chemistry of headwater streams reflect responses of water and elemental cycles to perturbations occurring at local to global scales. We evaluated multi-scale temporal patterns in up to 32 y of monthly observations of stream chemistry (ammonium, calcium, dissolved organic carbon, nitrate, total dissolved phosphorus, and sulfate) in 22 reference catchments within the northern temperate zone of North America. Multivariate autoregressive state-space (MARSS) models were applied to quantify patterns at multi-decadal, seasonal, and shorter intervals during a period that encompassed warming climate, seasonal changes in precipitation, and regional declines in atmospheric deposition. Significant long-term trends in solute concentrations within a subset of the catchments were consistent with recovery from atmospheric deposition (e.g., calcium, nitrate, sulfate) and increased precipitation (e.g., dissolved organic carbon). Lack of evidence for multi-decadal trends in most catchments suggests resilience of northern temperate ecosystems or that subtle net effects of simultaneous changes in climate and disturbance regimes do not result in directional trends. Synchronous seasonal oscillations of solute concentrations occurred across many catchments, reflecting shared climate and biotic drivers of seasonality within the northern temperate zone. Despite shared patterns among catchments at a seasonal scale, multi-scale temporal patterns were statistically distinct among even adjacent headwater catchments, implying that local attributes of headwater catchments modify the signals imparted by atmospheric phenomena and regional disturbances. To effectively characterize hydrologic and biogeochemical responses to changing climate and disturbance regimes, catchment monitoring programs could include multiple streams with contributing areas that encompass regional heterogeneity in vegetation, topography, and elevation. Overall, detection of long-term patterns and trends requires monitoring multiple catchments at a frequency that captures periodic variation (e.g., seasonality) and a duration encompassing the perturbations of interest.

Biogeochemistry↗

USGS2006

Using diatom assemblages to assess urban stream conditions

We characterized changes in diatom assemblages along an urban-to-rural gradient to assess impacts of urbanization on stream conditions. Diatoms, water chemistry, and physical variables of riffles at 19 urban and 28 rural stream sites were sampled and assessed during the summer base flow period. Near stream land use was characterized using GIS. In addition, one urban and one rural site were sampled monthly throughout a year to assess temporal variation of diatom assemblages between the urban and rural stream sites. Canonical correspondence analysis (CCA) showed that the 1st ordination axis distinctly separated rural and urban sites. This axis was correlated with conductivity (r = 0.75) and % near-stream commercial/industrial land use (r = 0.55). TWINSPAN classified all sites into four groups based on diatom assemblages. These diatom-based site groups were significantly different in water chemistry (e.g., conductivity, dissolved nutrients), physical habitat (e.g., % stream substrate as fines), and near-stream land use. CCA on the temporal diatom data set showed that diatom assemblages had high seasonal variation along the 2nd axis in both urban and rural sites, however, rural and urban sites were well separated along the 1st ordination axis. Our results suggest that changes in diatom assemblages respond to urban impacts on stream conditions. ?? Springer 2006.

Hydrobiologia↗

USGS2019

Subsurface water piping prevents meromixis in a deep volcanic crater lake (Dominica, West Indies)

Boeri Lake—a small (3.6 ha) but deep (39.6 m) crater lake on Morne Micotrin in Dominica, West Indies—presents a limnological enigma; it exhibits strong morphometric and circumstantial evidence for meromixis, yet it is not stratified. We tested the hypothesis that water seepage from Boeri Lake overcomes morphometric drivers of stratification and prevents the onset of meromixis. We compared water chemistry and plankton community composition in Boeri Lake to perennial streams on Morne Micotrin to assess if water discharging from these springs originates in Boeri Lake. Lacustrine phytoplankton and zooplankton taxa were detected in nearby streams, which also had similar water chemistry to Boeri Lake. In contrast, two other streams that drain Morne Micotrin and one neighboring reference stream had little in common with waters from Boeri Lake. This suggests that Boeri Lake’s anomalous limnology is explained by hydrologic connectivity to nearby flanking streams, and supports our hypothesis that subsurface water piping, combined with high annual rainfall, stymies the onset of meromixis. We provide an explanation for how holomictic lakes can persist and transport organisms through the ground in tropical mountain ecosystems and discuss implications of consistent water piping for plankton community assembly on island lakes.

Hydrobiologia↗

USGS2011

A Holocene record of endogenic iron and manganese precipitation and vegetation history in a lake-fen complex in northwestern Minnesota

Little Shingobee Lake and Fen are part of the extensive network of lakes and wetlands in the Shingobee River headwaters of northwestern Minnesota, designed to study the interactions between surface and ground waters. Prior to about 11.2 cal. ka, most of these lakes and wetlands were interconnected to form glacial Lake Willobee, which apparently formed when a debris flow dammed the Shingobee River. Between 11.2 and 8.5 cal. ka, the level of Lake Willobee fell as a result of breaching of the dam, transforming the deep lake into the existing lakes and wetlands. Analyses of a 9-m core from Little Shingobee Lake (LSL-B), and lacustrine sediments under 3.3 m of peat in a 17-m core from Little Shingobee Fen (LSF-10), show that the dominant components are allogenic clastic material, and endogenic CaCO 3 and organic matter. In both cores almost all of the iron (Fe) and manganese (Mn) are incorporated in endogenic minerals, presumed to be X-ray amorphous oxyhydroxide minerals, that occur in significant quantities throughout the cores; almost no Fe and Mn are contributed from detrital aluminosilicate minerals. This suggests that, for most of the Holocene, the allogenic watershed contributions to lake chemistry were minor compared to the dissolved mineral load. In addition, prior to 3.5 cal. ka, pollen zone boundaries coincide with large changes in lake-sediment mineralogy, indicating that both landscape and climate processes were linked to early- and mid-Holocene lake chemistry. The pollen time series, with sequential domination by spruce, pine, sagebrush-oak, birch-oak and, finally, white pine is typical of the region and reflects the changing location of the prairie-forest transition zone over time. These changes in vegetation had some profound effects on the geochemistry of the lake waters.

Minnesota↗

USGS2021

Machine learning can assign geologic basin to produced water samples using major ion geochemistry

Understanding the geochemistry of waters produced during petroleum extraction is essential to informing the best treatment and reuse options, which can potentially be optimized for a given geologic basin. Here, we used the US Geological Survey’s National Produced Waters Geochemical Database (PWGD) to determine if major ion chemistry could be used to classify accurately a produced water sample to a given geologic basin based on similarities to a given training dataset. Two datasets were derived from the PWGD: one with seven features but more samples (PWGD7), and another with nine features but fewer samples (PWGD9). The seven-feature dataset, prior to randomly generating a training and testing (i.e., validation) dataset, had 58,541 samples, 20 basins, and was classified based on total dissolved solids (TDS), bicarbonate (HCO 3 ), Ca, Na, Cl, Mg, and sulfate (SO 4 ). The nine-feature dataset, prior to randomly splitting into a training and testing (i.e., validation) dataset, contained 33,271 samples, 19 basins, and was classified based on TDS, HCO 3 , Ca, Na, Cl, Mg, SO 4 , pH, and specific gravity. Three supervised machine learning algorithms—Random Forest, k-Nearest Neighbors, and Naïve Bayes—were used to develop multi-class classification models to predict a basin of origin for produced waters using major ion chemistry. After training, the models were tested on three different datasets: Validation7, Validation9, and one based on data absent from the PWGD. Prediction accuracies across the models ranged from 23.5 to 73.5% when tested on the two PWGD-based datasets. A model using the Random Forest algorithm predicted most accurately compared to all other models tested. The models generally predicted basin of origin more accurately on the PWGD7-based dataset than on the PWGD9-based dataset. An additional dataset, which contained data not in the PWGD, was used to test the most accurate model; results suggest that some basins may lack geochemical diversity or may not be well described, while others may be geochemically diverse or are well described. A compelling result of this work is that a produced water basin of origin can be determined using major ions alone and, therefore, deep basinal fluid compositions may not be as variable within a given basin as previously thought. Applications include predicting the geochemistry of produced fluid prior to drilling at different intervals and assigning historical produced water data to a producing basin.

Natural Resources Research↗

USGS2006

The viability of a nonenzymatic reductive citric acid cycle - Kinetics and thermochemistry

The likelihood of a functioning nonenzymatic reductive citric acid cycle, recently proposed as the precursor to biosynthesis on early Earth, is examined on the basis of the kinetics and thermochemistry of the acetate → pyruvate → oxaloacetate → malate sequence. Using data derived from studies of the Pd-catalyzed phosphinate reduction of carbonyl functions it is shown that the rate of conversion of pyruvate to malate with that system would have been much too slow to have played a role in the early chemistry of life, while naturally occurring reduction systems such as the fayalite–magnetite–quartz and pyrrhotite–pyrite–magnetite mineral assemblages would have provided even slower conversions. It is also shown that the production of pyruvate from acetate is too highly endoergic to be driven by a naturally occurring energy source such as pyrophosphate. It is thus highly doubtful that the cycle can operate at suitable rates without enzymes, and most unlikely that it could have participated in the chemistry leading to life.

Origins of Life and Evolution of the Biosphere↗

USGS2010

Soil and periphyton indicators of anthropogenic water-quality changes in a rainfall-driven wetland

Surface soils and periphyton communities were sampled across an oligotrophic, soft-water wetland to document changes associated with pulsed inputs of nutrient- and mineral-rich canal drainage waters. A gradient of canal-water influence was indicated by the surface-water specific conductance, which ranged between 743 and 963 μS cm −1 in the canals to as low as 60 μS cm −1 in the rainfall-driven wetland interior. Changes in soil chemistry and periphyton taxonomic composition across this gradient were described using piecewise regressions models. The greatest increase in soil phosphorus (P) concentration occurred at sites closest to the canal while soil mineral (sulfur, calcium) concentrations increased most rapidly at the lower end of the gradient. Multiple periphyton shifts occurred at the lower end of the gradient and included; (1) a decline in desmids and non-desmid filamentous chlorophytes, and their replacement by a diatom-dominated community; (2) the loss of soft-water diatom indicator species and their replacement by hard-water species. Increased dominance by cyanobacteria and eutrophic diatom indicators occurred closer to the canals. Soil and periphyton changes indicated four zones of increasing canal influence across the wetland: (1) a zone of increasing mineral concentrations where soft-water taxa remained dominant; (2) a transition towards hard-water, oligotrophic diatoms as mineral concentrations increased further; (3) a zone of dominance by these hard-water species; (4) a zone of rapidly increasing P concentrations and dominance by eutrophic taxa. In contrast to conclusions drawn from routine water-chemistry monitoring, measures of chemical and biological change presented here indicate that most of this rainfall-driven peatland receives some influence from canal discharges. These changes are multifaceted and induced by shifts in multiple chemical constituents.

Florida↗

USGS2009

Conceptual hierarchical modeling to describe wetland plant community organization

Using multivariate analysis, we created a hierarchical modeling process that describes how differently-scaled environmental factors interact to affect wetland-scale plant community organization in a system of small, isolated wetlands on Mount Desert Island, Maine. We followed the procedure: 1) delineate wetland groups using cluster analysis, 2) identify differently scaled environmental gradients using non-metric multidimensional scaling, 3) order gradient hierarchical levels according to spatiotem-poral scale of fluctuation, and 4) assemble hierarchical model using group relationships with ordination axes and post-hoc tests of environmental differences. Using this process, we determined 1) large wetland size and poor surface water chemistry led to the development of shrub fen wetland vegetation, 2) Sphagnum and water chemistry differences affected fen vs. marsh / sedge meadows status within small wetlands, and 3) small-scale hydrologic differences explained transitions between forested vs. non-forested and marsh vs. sedge meadow vegetation. This hierarchical modeling process can help explain how upper level contextual processes constrain biotic community response to lower-level environmental changes. It creates models with more nuanced spatiotemporal complexity than classification and regression tree procedures. Using this process, wetland scientists will be able to generate more generalizable theories of plant community organization, and useful management models. ?? Society of Wetland Scientists 2009.

Wetlands↗

USGS2025

Observing northern high-latitude river systems to understand changes in a warming Arctic

Purpose of Review Streams and rivers are undergoing rapid change as the Arctic warms and thaws. We review recent observations in Arctic stream systems to identify ubiquitous changes and the most useful tools for observing change and exploring the underlying processes. Recent Findings Recent literature indicates increasingly significant trends in river hydrology and chemistry due to persistent warming in the Arctic and longer observational records for analysis. However, regional differences in the magnitude and direction of these trends persist. We also observe thresholds in ground thaw and surface–groundwater interactions that can impact river hydrology and chemistry. Summary Warming and thaw are occurring rapidly at high latitudes, resulting in increasing, yet variable responses in stream systems across regions and scales. These differences highlight the need for long-term records and an interdisciplinary approach to explain trends and predict future states. Stream systems respond to multiple landscape changes related to hydrology (changing precipitation and subsurface flow), geology (ground thaw dynamics), and ecology (vegetation change).

Current Climate Change Reports↗

USGS1985

Element mobility studies of two drill-cores from the Götemar Granite (Kråkemåla test site), southeast Sweden

A pilot study was carried out on two relatively deep drill-cores (&sim; 600 m) from the Götemar Granite massif in S.E. Sweden. This granite is typical of the 1400-Ma anorogenic granites of the northern hemisphere. Samples from representative, unfractured parts of the cores, together with four samples taken along a profile tangential to a fracture plane at &sim; 280-m depth, were investigated chemically, mineralogically and isotopically. The results show that after crystallisation, subtle and pervasive open-system modifications of the trace-element chemistry of the granite took place. Whereas the major-element chemistry and minera-logical data emphasised the relative homogeneity of the Götemar Granite samples investigated, trace elements such as U, Rb, and Pb revealed irregular distributions which are probably the result of large-scale hydrothermal alteration processes. This conclusion is supported by isotopic studies which indicate that whole-rock samples were open to a gain or loss of Pb and possibly U at &sim; 420 ± 171 Ma ago. In addition, isotopic data for U-Pb and U-Ra are consistent with a recent minor loss of U. The pervasive alteration and the more recent mobilisation of U are evident to a depth of at least 600 m. The effects are most prevalent along major fracture zones and within the upper 250–300 m of one drill-hole where a high frequency of crush zones has been noted. Higher Fe oxidation ratios, higher Rb contents, lower U contents and correspondingly higher Th/U ratios, all characterise this zone.

Chemical Geology↗

USGS1987

The geochemistry of water near a surficial organic-rich uranium deposit, northeastern Washington State, U.S.A.

The chemistry of three stream, three spring and six near-surface waters in the vicinity of a Holocene organic-rich uranium deposit is described, with particular emphasis on the chemistry of U. Results characterize the solution behavior of uranium as U-bearing water interacts with relatively undecomposed, surficial organic matter. Of the measured major and trace chemical species, only U is consistently highly enriched (17-318 ppb) relative to reported values for regional waters, or to literature values for waters in largely granitic terrains. R-mode factor analysis of the chemical data suggests that most U is present in a soluble form, but that some U is also associated with fine suspended particulates of clay, organic matter, or hydrous oxides. Calculations that apply thermodynamic data to predict U speciation in solution indicate the relative importance of uranyl carbonate and uranyl phosphate complexes. Analysis of more finely filtered samples (0.05 ??m vs. 0.45 ??m), and direct radiographic observations using fission-track detectors suspended in the waters indicate the presence of some uraniferous particulate matter. Application of existing thermodynamic data for uranous- and uranyl-bearing minerals indicates that all waters are undersaturated with U minerals as long as ambient Eh ??? +0.1 v. If coexisting surface and near-surface waters are sufficiently oxidizing, initial fixation of U in the deposit should be by a mechanism of adsorption. Alternatively, more reducing conditions may prevail in deeper pore waters of the organic-rich host sediments, perhaps leading to direct precipitation or diagenetic formation of U4+ minerals. A 234U 238U alpha activity ratio of 1.08 ?? 0.02 in a spring issuing from a hillslope above the deposit suggests a relatively soluble source of U. In contrast, higher activity ratios of 234U 238U (??? 1.3) in waters in contact with the uraniferous valley-fill sediments suggest differences in the nature of interaction between groundwater and the local, U-rich source rocks. ?? 1987.

Chemical Geology↗

USGS1992

Mechanisms of iron photoreduction in a metal-rich, acidic stream (St. Kevin Gulch, Colorado, U.S.A.)

Iron photoreduction in metal-rich, acidic streams affected by mine drainage accounts for some of the variability in metal chemistry of such streams, producing diel variations in Fe(II). Differentiation of the mechanisms of the Fe photoreduction reaction by a series of in-stream experiments at St. Kevin Gulch, Colorado, indicates that a homogeneous, solution-phase reaction can occur in the absence of suspended particulate Fe and bacteria, and the rate of reaction is increased by the presence of Fe colloids in the stream water. In-stream Fe photoreduction is limited during the diel cycle by the available Fe(III) in the water column and streambed. The quantum yield of Fe(II) was reproducible in diel measurements: the quantum yield, in mol E-1 (from 300 to 400 nm) was 1.4 ?? 10-3 in 1986, 0.8 ?? 10-3 in 1988 and 1.2 ?? 10-3 in 1989, at the same location and under similar streamflow and stream-chemistry conditions. In a photolysis control experiment, there was no detectable production of Fe(II) above background concentrations in stream-water samples that were experimentally excluded from sunlight. ?? 1992.

Chemical Geology↗

USGS1961

Aqua de Ney, California, a spring of unique chemical character

The chemistry of water of Aqua de Ney, a cold spring of unusual character located in Siskiyou County, Calif., has been re-examined as part of a study of the relation of water chemistry to rock environment. The water has a pH of 11·6 and a silica content of 4000 parts per million (p.p.m.), the highest values known to occur in natural ground waters. The rocks exposed nearby consist of two volcanic sequences, one predominantly basaltic in composition, the other highly siliceous. Neither these rocks nor the sedimentary and igneous rocks presumed to underlie the area at depth seem to offer explanation of the unusual mineralization which includes 240 p.p.m. of boron, 1000 p.p.m. of sulphide (as H 2 S), and 148 p.p.m. of ammonia nitrogen (as NH 4 ) in a water that is predominantly sodium chloride and sodium carbonate in character. By analogy, it is assumed that water from Aqua de Ney is the product of an initial mixture of connate sea water with a calcium magnesium sulphate water. It is postulated that ion exchange has increased the content of sodium and reduced that of calcium and magnesium, and that sulphate reduction has brought about the high alkalinity, high pH, and high content of sulphide. The large silica value is explained as the result of solution of silica by water having the high pH observed.

California↗

USGS1981

Experimental seawater-basalt interaction at 300°C, 500 bars, chemical exchange, secondary mineral formation and implications for the transport of heavy metals

Seawater and NaCl solutions were reacted with basalt (basalt glass and diabase) for several months at 300°C, 500 bars and a water/rock ratio of 10. During reaction, seawater was significantly modified, increasing in Ca, H 2 S, CO 2 . SiO 2 , K. Fe, Mn. Ba, Al and H + , and decreasing in Mg and SO 4 . Basalt glass was completely replaced by smectite, wairakite, anhydrite and hematite, and diabase was partially replaced by mixed layered smectite-chlorite, anhydrite and magnetite (?). Diabase was altered more slowly than basalt glass and the corresponding changes in seawater chemistry were less pronounced. Basalt glass reacted with a 0.45 m NaCl solution resulted in the formation of smectite, albite. truscottite and wairakite. Solutions from this experiment were characterized by a relatively high pH and dominated by Ca for Na exchange reactions. At no point in this experiment were heavy metals solubilized, in contrast to the seawater experiments. This behavior illustrates the fundamental importance of seawater chemistry to heavy-metal solubility; that is, the removal of Mg from seawater generates acidity which maintains heavy metals in solution. Apparently seawater chlorinity is not capable of enhancing heavy-metal solubility by chloride complexing. Seafloor heavy-metal deposits can result from the following: Seawater-basalt interaction at moderate temperature (&sim;-300°C and high effective water/rock ratios; or at relatively high temperatures (&sim;-400°C) and low (e.g.< 10) water/rock ratios.

Geochimica et Cosmochimica Acta↗

USGS1984

Pegmatite/wallrock interactions, Black Hills, South Dakota: Progressive boron metasomatism adjacent to the Tip Top pegmatite

Interaction between country rock and fluids derived from the Tip Top pegmatite has resulted in a series of boron enriched assemblages. Between unaltered quartz-mica schist to the pegmatite contact is a succession of four mineral assemblages: 1. (1) Quartz-Biotite-Potassium Feldspar assemblage (Q-B-K), which consists essentially of the original metamorphic silicate assemblage plus anomalously high amounts of modal tourmaline 2. (2) Quartz-Biotite-Tourmaline assemblage (Q-B-T) 3. (3) Tourmaline-Quartz-Muscovite assemblage (T-Q-M) 4. (4) Tourmaline-Quartz assemblage (T-Q). Alkali elements (Cs, Rb, K, Li), SiO 2 , and Ba show a decrease from the Q-B-K assemblage to the T-Q assemblage. A1 2 O 3 , Ga, B, total Fe and Zn increase moderately from the Q-B-K assemblage to the T-Q assemblage. The mineral chemistries also change considerably. The Mg/(Mg + Fe 2+ ) ratios in biotites range from 0.54 to 0.50 in samples from the Q-B-K assemblage to 0.39 in the (Q-B-T) assemblage. The range in tourmaline end-member components from the Q-B-K assemblage to the T-Q assemblage is as follows: Q-B-K: Dravite .63 Schorl .23 Elbaite .05 Buergerite .09 T-Q: Dravite .23 Schorl .37 Elbaite .17 Buergerite .23 . Observed variations in mineral assemblage and whole rock chemistry within the alteration zone appear to a first approximation to be a function of μB 2 O 3 (boron metasomatism) and μK 2 O (alkali leaching). The breakdown of feldspar and biotite may be approximated by reactions: 2HCl + 2(K, Na)AlSi 3 O 8 /ai 2(K, Na)Cl + Al 2 SiO 5 + 5SiO 2 + H 2 O and 2 Annite + SiO 2 + 5Al 2 SiO 5 + 2NaCl + 6H 3 BO 3 /ai 2 Tourmaline + 2KCl + 7H 2 O. The alteration zone may represent either a single episode (B-, Cs-, Li-, Rb-enriched fluid) or multiple episodes (B, Zn, Mn fluid and Cs, Li, Rb fluid) of pegmatite fluid-schist interactions. In both situations, B in the aqueous fluid from the pegmatite reacts with the schist breaking down sheet silicate “traps” for Cs, Rb, Li, and K and forming tourmaline-rich assemblages.

Geochimica et Cosmochimica Acta↗

USGS1991

Rare earth elements in Japan Sea sediments and diagenetic behavior of Ce/Ce∗: results from ODP Leg 127

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (ΣREE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO 2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. ΣREE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlated slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and L (l n /Yb n suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

Geochimica et Cosmochimica Acta↗