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Dennis D. Eberl

Publications and source records attributed to Dennis D. Eberl.

At least 19 recordsLinked to original sources
USGS2024

Effects of exchanged cation on the microporosity of montmorillonite

The micropore volumes of 2 montmorillonites (SAz-1 and SWy-1), each exchanged with Ca, Na, K, Cs and tetramethylammonium (TMA) ions, were calculated from the measured vapor adsorption data of N 2 and neo -hexane by use of t - and α s -plots. The corresponding surface areas of the exchanged clays were determined from Brunauer-Emmett-Teller (BET) plots of N 2 adsorption data. Micropore volumes and surface areas of the samples increased with the size of exchanged cation: TMA > Cs > K > Ca > Na. The SAz-1 exchanged clays showed generally greater micropore volumes and surface areas than the corresponding SWy-1 clays. The vapor adsorption data and d (001) measurements for dry clay samples were used together to evaluate the likely locations and accessibility of clay micropores, especially the relative accessibility of their interlayer spacing. For both source clays exchanged with Na, Ca and K ions, the interlayer spacing appeared to be too small to admit nonpolar gases and the accessible micropores appeared to have dimensions greater than 5.0 Å, the limiting molecular dimension of neo -hexane. In these systems, there was a good consistency of micropore volumes detected by N 2 and neo -hexane. When the clays were intercalated with relatively large cations (TMA and possibly Cs), the large layer expansion created additional microporosity, which was more readily accessible to small N 2 than to relatively large neo -hexane. Hence, the micropore volume as detected by N 2 was greater than that detected by neo -hexane. The micropore volumes with pore dimensions greater than 5 Å determined for clays exchanged with Na, Ca and K likely resulted from the pores on particle edges and void created by overlap regions of layers. The increase in micropore volumes with pore dimensions less than 5 Å determined for clays exchanged with TMA and possibly Cs could be caused by opening of the interlayer region by the intercalation of these large cations.

Clays and Clay Minerals↗
USGS2024

XRD measurement of mean thickness, thickness distribution and strain for illite and illite-smectite crystallites by the Bertaut-Warren-Averbach technique

A modified version of the Bertaut-Warren-Averbach (BWA) technique (Bertaut 1949, 1950; Warren and Averbach 1950) has been developed to measure coherent scattering domain (CSD) sizes and strains in minerals by analysis of X-ray diffraction (XRD) data. This method is used to measure CSD thickness distributions for calculated and experimental XRD patterns of illites and illite-smectites (I-S). The method almost exactly recovers CSD thickness distributions for calculated illite XRD patterns. Natural I-S samples contain swelling layers that lead to nonperiodic structures in the c * direction and to XRD peaks that are broadened and made asymmetric by mixed layering. Therefore, these peaks cannot be analyzed by the BWA method. These difficulties are overcome by K-saturation and heating prior to X-ray analysis in order to form 10-Å periodic structures. BWA analysis yields the thickness distribution of mixed-layer crystals (coherently diffracting stacks of fundamental illite particles). For most I-S samples, CSD thickness distributions can be approximated by lognormal functions. Mixed-layer crystal mean thickness and expandability then can be used to calculate fundamental illite particle mean thickness. Analyses of the dehydrated, K-saturated samples indicate that basal XRD reflections are broadened by symmetrical strain that may be related to local variations in smectite interlayers caused by dehydration, and that the standard deviation of the strain increases regularly with expandability. The 001 and 002 reflections are affected only slightly by this strain and therefore are suited for CSD thickness analysis. Mean mixed-layer crystal thicknesses for dehydrated I-S measured by the BWA method are very close to those measured by an integral peak width method.

Clays and Clay Minerals↗
USGS2024

Measurement of illite particle thickness using a direct Fourier transform of small-angle X-ray scattering data

It has been suggested that interstratified illite-smectite (I-S) minerals are composed of aggregates of fundamental particles. Many attempts have been made to measure the thickness of such fundamental particles, but each of the methods used suffers from its own limitations and uncertainties. Small-angle X-ray scattering (SAXS) can be used to measure the thickness of particles that scatter X-rays coherently. We used SAXS to study suspensions of Na-rectorite and other illites with varying proportions of smectite. The scattering intensity ( I ) was recorded as a function of the scattering vector, q = (4 /) sin(/2), where  is the X-ray wavelength and  is the scattering angle. The experimental data were treated with a direct Fourier transform to obtain the pair distance distribution function (PDDF) that was then used to determine the thickness of illite particles. The Guinier and Porod extrapolations were used to obtain the scattering intensity beyond the experimental q , and the effects of such extrapolations on the PDDF were examined. The thickness of independent rectorite particles (used as a reference mineral) is 18.3 Å. The SAXS results are compared with those obtained by X-ray diffraction peak broadening methods. It was found that the power-law exponent (α) obtained by fitting the data in the region of q = 0.1-0.6 nm -1 to the power law ( I = I 0 q -α ) is a linear function of illite particle thickness. Therefore, illite particle thickness could be predicted by the linear relationship as long as the thickness is within the limit where α <4.0.

Clays and Clay Minerals↗
USGS2024

Chemical and mineralogical characteristics of French green clays used for healing

The worldwide emergence of infectious diseases, together with the increasing incidence of antibiotic-resistant bacteria, elevate the need to properly detect, prevent, and effectively treat these infections. The overuse and misuse of common antibiotics in recent decades stimulates the need to identify new inhibitory agents. Therefore, natural products like clays, that display antibacterial properties, are of particular interest. The absorptive properties of clay minerals are well documented for healing skin and gastrointestinal ailments. However, the antibacterial properties of clays have received less scientific attention. French green clays have recently been shown to heal Buruli ulcer, a necrotic or ‘flesh-eating’ infection caused by Mycobacterium ulcerans . Assessing the antibacterial properties of these clays could provide an inexpensive treatment for Buruli ulcer and other skin infections. Antimicrobial testing of the two clays on a broad-spectrum of bacterial pathogens showed that one clay promotes bacterial growth (possibly provoking a response from the natural immune system), while another kills bacteria or significantly inhibits bacterial growth. This paper compares the mineralogy and chemical composition of the two French green clays used in the treatment of Buruli ulcer. Mineralogically, the two clays are dominated by 1 Md illite and Fe-smectite. Comparing the chemistry of the clay minerals and exchangeable ions, we conclude that the chemistry of the clay, and the surface properties that affect pH and oxidation state, control the chemistry of the water used to moisten the clay poultices and contribute the critical antibacterial agent(s) that ultimately debilitate the bacteria.

Clays and Clay Minerals↗
USGS2024

The role of clay minerals in the preservation of organic matter in sediments of Qinghai Lake, NW China

The role of saline lake sediments in preserving organic matter has long been recognized. In order to further understand the preservation mechanisms, the role of clay minerals was studied. Three sediment cores, 25, 57, and 500 cm long, were collected from Qinghai Lake, NW China, and dissected into multiple subsamples. Multiple techniques were employed, including density fractionation, X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM), total organic carbon (TOC) and carbon compound analyses, and surface area determination. The sediments were oxic near the water-sediment interface, but became anoxic at depth. The clay mineral content was as much as 36.8%, consisting mostly of illite, chlorite, and halloysite. The TEM observations revealed that organic matter occurred primarily as organic matter-clay mineral aggregates. The TOC and clay mineral abundances are greatest in the mid-density fraction, with a positive correlation between the TOC and mineral surface area. The TOC of the bulk sediments ranges from 1 to 3% with the non-hydrocarbon fraction being predominant, followed by bitumen, saturated hydrocarbon, aromatic hydrocarbons, and chloroform-soluble bitumen. The bimodal distribution of carbon compounds of the saturated hydrocarbon fraction suggests that organic matter in the sediments was derived from two sources: terrestrial plants and microorganisms/algae. Depthrelated systematic changes in the distribution patterns of the carbon compounds suggest that the oxidizing conditions and microbial abundance near the water-sediment interface promote degradation of labile organic matter, probably in adsorbed form. The reducing conditions and small microbial biomass deeper in the sediments favor preservation of organic matter, because of the less labile nature of organic matter, probably occurring within clay mineral-organic matter aggregates that are inaccessible to microorganisms. These results have important implications for our understanding of mechanisms of organic matter preservation in saline lake sediments.

Qinghai Lake↗
USGS2024

The formation of illite from nontronite by mesophilic and thermophilic bacterial reaction

The formation of illite through the smectite-to-illite (S-I) reaction is considered to be one of the most important mineral reactions occurring during diagenesis. In biologically catalyzed systems, however, this transformation has been suggested to be rapid and to bypass the high temperature and long time requirements. To understand the factors that promote the S-I reaction, the present study focused on the effects of pH, temperature, solution chemistry, and aging on the S-I reaction in microbially mediated systems. Fe(III)-reduction experiments were performed in both growth and non-growth media with two types of bacteria: mesophilic ( Shewanella putrefaciens CN32) and thermophilic ( Thermus scotoductus SA-01). Reductive dissolution of NAu-2 was observed and the formation of illite in treatment with thermophilic SA-01 was indicated by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). A basic pH (8.4) and high temperature (65°C) were the most favorable conditions for the formation of illite. A long incubation time was also found to enhance the formation of illite. K-nontronite (non-permanent fixation of K) was also detected and differentiated from the discrete illite in the XRD profiles. These results collectively suggested that the formation of illite associated with the biologically catalyzed smectite-to-illite reaction pathway may bypass the prolonged time and high temperature required for the S-I reaction in the absence of microbial activity.

Clays and Clay Minerals↗
USGS2024

The influence of oxalate-promoted growth of saponite and talc crystals

The intercalating growth of new silicate layers or metal hydroxide layers in the interlayer space of other clay minerals is known from various mixed-layer clay minerals such as illite-smectite (I-S), chlorite-vermiculite, and mica-vermiculite. In a recent study, the present authors proposed that smectite-group minerals can be synthesized from solution as new 2:1 silicate layers within the low-charge interlayers of rectorite. That study showed how oxalate catalyzes the crystallization of saponite from a silicate gel at low temperatures (60ºC) and ambient pressure. As an extension of this work the aim of the present study was to test the claim that new 2:1 silicate layers can be synthesized as new intercalating layers in the low-charge interlayers of rectorite and whether oxalate could promote such an intercalation synthesis. Two experiments were conducted at 60ºC and atmospheric pressure. First, disodium oxalate solution was added to a suspension of rectorite in order to investigate the effects that oxalate anions have on the structure of rectorite. In a second experiment, silicate gel of saponitic composition (calculated interlayer charge −0.33 eq/O 10 (OH) 2 ) was mixed with a suspension of rectorite and incubated in disodium oxalate solution. The synthesis products were extracted after 3 months and analyzed by X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). The treatment of ultrathin sections with octadecylammonium (n C = 18) cations revealed the presence of 2:1 layer silicates with different interlayer charges that grew from the silicate gel. The oxalate-promoted nucleation of saponite and talc crystallites on the rectorite led to the alteration and ultimately to the destruction of the rectorite structure. The change was documented in HRTEM lattice-fringe images. The crystallization of new 2:1 layer silicates also occurred within the expandable interlayers of rectorite but not as new 2:1 silicate layers parallel to the previous 2:1 silicate layers. Instead, they grew independently of any orientation predetermined by the rectorite crystal substrate and their crystallization was responsible for the destruction of the rectorite structure.

Clays and Clay Minerals↗
USGS2024

Thickness distributions and evolution of growth mechanisms of NH4-illite from the fossil hydrothermal system of Harghita Bai, Eastern Carpathians, Romania

The crystal growth of NH 4 -illite (NH 4 -I) from the hydrothermal system of Harghita Bãi (Eastern Carpathians) was deduced from the shapes of crystal thickness distributions (CTDs). The 4-illite-smectite (I-S) interstratified structures (R1, R2, and R3-type ordering) with a variable smectite-layer content. The NH 4 -I-S (40–5% S) structures were identified underground in a hydrothermal breccia structure, whereas the K-I/NH 4 -I mixtures were found at the deepest level sampled (−110 m). The percentage of smectite interlayers generally decreases with increasing depth in the deposit. This decrease in smectite content is related to the increase in degree of fracturing in the breccia structure and corresponds to a general increase in mean illite crystal thickness. In order to determine the thickness distributions of NH 4 -I crystals (fundamental illite particles) which make up the NH 4 -I-S interstratified structures and the NH 4, -I/K-I mixtures, 27 samples were saturated with Li + and aqueous solutions of PVP-10 to remove swelling and then were analyzed by X-ray diffraction. The profiles for the mean crystallite thickness (T mean ) and crystallite thickness distribution (CTD) of NH 4 -I crystallites were determined by the Bertaut-Warren-Averbach method using the MudMaster computer code. The T mean of NH 4 -I from NH 4 -I-S samples ranges from 3.4 to 7.8 nm. The T mean measured for the NH 4 -I/K-I mixture phase ranges from 7.8 nm to 11.7 nm (NH 4 -I) and from 12.1 to 24.7 nm (K-I). The CTD shapes of NH 4 -I fundamental particles are asymptotic and lognormal, whereas illites from NH 4 -I/K-I mixtures have bimodal shapes related to the presence of two lognormal-like CTDs corresponding to NH 4 -I and K-I. The crystal-growth mechanism for NH 4 -I samples was simulated using the Galoper code. Reaction pathways for NH 4 -I crystal nucleation and growth could be determined for each sample by plotting their CTD parameters on an α–β 2 diagram constructed using Galoper . This analysis shows that NH 4 -I crystals underwent simultaneous nucleation and growth, followed by surface-controlled growth without simultaneous nucleation.

Harghita Bai↗
USGS2019

Soil mineralogy and geochemistry along a north-south transect in Alaska and the relation to source-rock terrane

Soils collected along a predominately north-south transect in Alaska were used to evaluate regional differences in the soil mineralogy and geochemistry in the context of a geotectonic framework for Alaska. The approximately 1,395-kilometer-long transect followed the Dalton, Elliott, and Richardson Highways from near Prudhoe Bay to Valdez. Sites were selected with a site spacing of approximately 10 road-kilometers; soil was sampled by soil horizon at 175 sites. Terrane boundaries were estimated from digitized versions of the lithotectonic terrane map of Alaska (Silberling and others, 1994). Terrane assignments for each site were based on the site’s distance along the transect. We also present data for 15 minerals or mineral groups and 58 elements, as well as total, inorganic, and organic carbon. Quantitative mineralogy of the mineral-soil horizons was characterized by X-ray diffraction. Elemental contents were determined by a combination of inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) analysis following a multi-acid or sodium-sinter decomposition of the samples. Total carbon and carbonate carbon contents were determined using an automated carbon analyzer and coulometric titration, respectively; organic carbon content was obtained by calculating the difference between total and carbonate carbon. Mercury and selenium were analyzed using cold-vapor atomic absorption (CV-AA), and hydride-generation atomic absorption spectrometry (HG-AAS), respectively. The mineralogical and geochemical patterns from these soils are used to assess the relation between soil characteristics and the geology of surrounding terranes.

Alaska↗
USGS2015

Biogeochemical environments of streambed-sediment pore waters with and without arsenic enrichment in a sedimentary rock terrain, New Jersey Piedmont, USA

Release of arsenic (As) from sedimentary rocks has resulted in contamination of groundwater in aquifers of the New Jersey Piedmont Physiographic Province, USA; the contamination also may affect the quality of the region's streamwater to which groundwater discharges. Biogeochemical mechanisms involved in the release process were investigated in the streambeds of Six Mile Run and Pike Run, tributaries to the Millstone River in the Piedmont. At Six Mile Run, streambed pore water and shallow groundwater were low or depleted in oxygen, and contained As at concentrations greater than 20 μg/L. At Pike Run, oxidizing conditions were present in the streambed, and the As concentration in pore water was 2.1 μg/L. The 16S rRNA gene and the As(V) respiratory reductase gene, arrA , were amplified from DNA extracted from streambed pore water at both sites and analyzed, revealing that distinct bacterial communities that corresponded to the redox conditions were present at each site. Anaerobic enrichment cultures were inoculated with pore water from gaining reaches of the streams with acetate and As(V). As(V) was reduced by microbes to As(III) in enrichments with Six Mile Run pore water and groundwater, whereas no reduction occurred in enrichments with Pike Run pore water. Cloning and sequencing of the arrA gene indicated 8 unique operational taxonomic units (OTUs) at Six Mile Run and 11 unique OTUs at Pike Run, which may be representative of the arsenite oxidase gene arxA . Low-oxygen conditions at Six Mile Run have favored microbial As reduction and release, whereas release was inhibited by oxidizing conditions at Pike Run.

New Jersey↗
USGS2013

K-Ar dating and delta O-18-delta D characterization of nanometric illite from Ordovician K-bentonites of the Appalachians: illitization and the Acadian-Alleghenian tectonic activity

Nanometric (<0.02, 0.02–0.05, 0.05–0.1, 0.1–0.2 μm) illite fractions were separated from K-bentonite samples from northwestern Georgia, and studied by X-ray diffraction, oxygen and hydrogen isotope geochemistry, and K-Ar dated to more tightly constrain the tectono-thermal history of the Appalachian orogeny. Their XRD patterns are very similar for a given sample with respect to the peak shapes and positions. They are ordered illite-smectite mixed layers with only small variations in the relative proportions of illite and smectite interlayers. The illite crystal thickness distributions also are very homogeneous across the various size fractions of the same sample, but crystallite thickness varies from sample to sample. It can be concluded from the α-β 2 diagram that illitization occurred in all fractions by simultaneous nucleation and crystal growth, except for one sample. In that sample, a period of growth without nucleation was detected on top of the nucleation and growth episode. The K-Ar ages organize into two isochrons, the first at 319.9 ± 2.0 Ma with an initial 40 Ar/ 36 Ar ratio of 271 ± 66 Ma, and the second at 284.9 ± 1.2 Ma with an initial 40 Ar/ 36 Ar ratio of 310 ± 44. One data point above the older isochron and three between the two isochrons suggest a detrital contamination for the former separate and a possible further generation of nanoparticles for the three others. The samples with the older crystallization age consist of illite and illite-rich mixed-layers, and those with the younger age contain smectite-rich mixed-layers without illite, or illite-enriched illite-smectite mixed-layers. The K-Ar ages fit the age trends published previously for similar K-bentonites with regional age patterns between 240 and 270 Ma in the southwestern region, between 270 and 300 Ma in the central zone and the southern Appalachians, and between 315 and 370 Ma in the northernmost. Each of the two generations of illite crystals yields very consistent δ 18 O (V-SMOW) values at 17 ± 1‰ for the older and at 21 ± 1‰ for the younger. If crystallization temperatures of the nanometric illite were between 100 and 200 °C, as suggested by microthermometric determinations, the hydrothermal fluids had δ 18 O values of 4 ± 1‰ in the Dalton district and of 8 ± 1‰ in the Lafayette, Trenton, and Dirtseller districts at 100 °C, and of 11 ± 1 and 15 ± 1‰ in the same locations at 200 °C, probably because the water-rock isotope exchanges at elevated temperature occurred in rock-dominated systems. The δ 18 O of the fluids remained unchanged during local crystal growth, but varied depending on the geographic location of the samples and timing of illitization. The δD (V-SMOW) values of the different size fractions do not provide consistent information; they range from −70 to −45‰ for most nanometric and micrometric fractions (V-SMOW), but with no apparent coherent pattern. Nanometric illite-rich crystals from K-bentonite that underwent tectono-thermal alteration yield constant ages, constant clay mineralogy, constant crystallite size distributions for all of the nucleating and growing illite-type crystals of each sample, as well as constant δ 18 O values implying constant fluid chemistry, all pointing to geologically sudden crystallization.

Georgia↗
USGS2013

A quantitative X-ray diffraction inventory of the tephra and volcanic glass inputs into the Holocene marine sediment archives off Iceland: A contribution to V.A.S.T.

This paper re-evaluates how well quantitative x-ray diffraction (qXRD) can be used as an exploratory method of the weight percentage (wt%) of volcaniclastic sediment, and to identify tephra events in marine cores. In the widely used RockJock v6 software programme, qXRD tephra and glass standards include the rhyodacite White River tephra (Alaska), a rhyolitic tephra (Hekla-4) and the basaltic Saksunarvatn tephra. Experiments of adding known wt% of tephra to felsic bedrock samples indicated that additions ≥10 wt% are accurately detected, but reliable estimates of lesser amounts are masked by amorphous material produced by milling. Volcaniclastic inputs range between 20 and 50 wt%. Primary tephra events are identified as peaks in residual qXRD glass wt% from fourth-order polynomial fits. In cores where tephras have been identified by shard counts in the > 150 µm fraction, there is a positive correlation (validation) with peaks in the wt% glass estimated by qXRD. Geochemistry of tephra shards confirms the presence of several Hekla-sourced tephras in cores B997-317PC1 and -319PC2 on the northern Iceland shelf. In core B997-338 (north-west Iceland), there are two rhyolitic tephras separated by ca. 100 cm with uncorrected radiocarbon dates on articulated shells of around 13 000 yr B.P. These tephras may be correlatives of the Borrobol and Penifiler tephras found in Scotland. The number of Holocene tephra events per 1000 yr was estimated from qXRD on 16 cores and showed a bimodal distribution with an increased number of events in both the late and early Holocene.

Polar Research↗
USGS2013

Arsenic in New Jersey Coastal Plain streams, sediments, and shallow groundwater: effects from different geologic sources and anthropogenic inputs on biogeochemical and physical mobilization processes

Arsenic (As) concentrations in New Jersey Coastal Plain streams generally exceed the State Surface Water Quality Standard (0.017 micrograms per liter (&micro;g/L)), but concentrations seldom exceed 1 &micro;g/L in filtered stream-water samples, regardless of geologic contributions or anthropogenic inputs. Nevertheless, As concentrations in unfiltered stream water indicate substantial variation because of particle inputs from soils and sediments with differing As contents, and because of discharges from groundwater of widely varying chemistry. In the Inner Coastal Plain, streams draining to lower reaches of the Delaware River traverse As-rich glauconitic sediments of marine origin in which As contents typically are about 20 milligrams per kilogram (mg/kg) or greater. In some of these sedimentary units, As concentrations exceed the New Jersey drinking-water maximum contaminant level (5 &micro;g/L) in shallow groundwater that discharges to streams. Microbes, fueled by organic carbon beneath the streambed, reduce iron (Fe) and As, releasing As and Fe into solution in the shallow groundwater from geologic materials that likely include (in addition to glauconite) other phyllosilicates, apatite, and siderite. When the groundwater discharges to the stream, the dissolved Fe and As are oxidized, the Fe precipitates as a hydroxide, and the As sorbs or co-precipitates with the Fe. Because of the oxidation/precipitation process, dissolved As concentrations measured in filtered stream waters of the Inner Coastal Plain are about 1 &micro;g/L, but the total As concentrations (and loads) are greater, substantially amplified by As-bearing suspended sediment in stormflows. In the Outer Coastal Plain, streams draining to the Atlantic Ocean traverse quartz-rich sediments of mainly deltaic origin where the As content generally is low (<8 mg/kg). In unfiltered and filtered water samples, As concentrations typically are less than 1 &micro;g/L in the acidic stream water and groundwater of the Outer Coastal Plain, but are greater in waters from urban areas. Despite the generally small geologic contributions to Outer Coastal Plain groundwater, where wastewater inputs were indicated, concentrations of As in unfiltered shallow groundwater discharging to small urban streams exceeded the maximum contaminant level. With a history of agriculture in the New Jersey Coastal Plain, anthropogenic inputs of As, such as residues from former pesticide applications in soils, can amplify any geogenic As in runoff. Such inputs contribute to an increased total As load to a stream at high stages of flow. As a result of yet another anthropogenic influence, microbes that reduce and mobilize As beneath the streambeds are stimulated by inputs of dissolved organic carbon (DOC). Although DOC is naturally occurring, anthropogenic contributions from wastewater inputs may deliver increased levels of DOC to subsurface soils and ultimately groundwater. Arsenic concentrations may increase with the increases in pH of groundwater and stream water in developed areas receiving wastewater inputs, as As mobilization caused by pH-controlled sorption and desorption reactions are likely to occur in waters of neutral or alkaline pH (for example, Nimick and others, 1998; Barringer and others, 2007b). Because of the difference in As content of the geologic materials in the two sub-provinces of the Coastal Plain, the amount of As that is mobile in groundwater and stream water is, potentially, substantially greater in the Inner Coastal Plain than in the Outer Coastal Plain. In turn, streams within the Inner and Outer Coastal Plain can receive substantially more As in groundwater discharge from developed areas than from environments where DOC appears to be of natural origin.

New Jersey↗
USGS2012

Formation of replicating saponite from a gel in the presence of oxalate: implications for the formation of clay minerals in carbonaceous chondrites and the origin of life

The potential role of clay minerals in the abiotic origin of life has been the subject of ongoing debate for the past several decades. At issue are the clay minerals found in a class of meteorites known as carbonaceous chondrites. These clay minerals are the product of aqueous alteration of anhydrous mineral phases, such as olivine and orthopyroxene, that are often present in the chondrules. Moreover, there is a strong correlation in the occurrence of clay minerals and the presence of polar organic molecules. It has been shown in laboratory experiments at low temperature and ambient pressure that polar organic molecules, such as the oxalate found in meteorites, can catalyze the crystallization of clay minerals. In this study, we show that oxalate is a robust catalyst in the crystallization of saponite, an Al- and Mg-rich, trioctahedral 2:1 layer silicate, from a silicate gel at 60°C and ambient pressure. High-resolution transmission electron microscopy analysis of the saponite treated with octadecylammonium (n(C)=18) cations revealed the presence of 2:1 layer structures that have variable interlayer charge. The crystallization of these differently charged 2:1 layer silicates most likely occurred independently. The fact that 2:1 layer silicates with variable charge formed in the same gel has implications for our understanding of the origin of life, as these 2:1 clay minerals most likely replicate by a mechanism of template-catalyzed polymerization and transmit the charge distribution from layer to layer. If polar organic molecules like oxalate can catalyze the formation of clay-mineral crystals, which in turn promote clay microenvironments and provide abundant adsorption sites for other organic molecules present in solution, the interaction among these adsorbed molecules could lead to the polymerization of more complex organic molecules like RNA from nucleotides on early Earth.

Astrobiology↗
USGS2011

What makes a natural clay antibacterial?

Natural clays have been used in ancient and modern medicine, but the mechanism(s) that make certain clays lethal against bacterial pathogens has not been identified. We have compared the depositional environments, mineralogies, and chemistries of clays that exhibit antibacterial effects on a broad spectrum of human pathogens including antibiotic resistant strains. Natural antibacterial clays contain nanoscale (<200 nm), illite-smectite and reduced iron phases. The role of clay minerals in the bactericidal process is to buffer the aqueous pH and oxidation state to conditions that promote Fe 2+ solubility. Chemical analyses of E. coli killed by aqueous leachates of an antibacterial clay show that intracellular concentrations of Fe and P are elevated relative to controls. Phosphorus uptake by the cells supports a regulatory role of polyphosphate or phospholipids in controlling Fe 2+ . Fenton reaction products can degrade critical cell components, but we deduce that extracellular processes do not cause cell death. Rather, Fe 2+ overwhelms outer membrane regulatory proteins and is oxidized when it enters the cell, precipitating Fe 3+ and producing lethal hydroxyl radicals.

Environmental Science & Technology↗
USGS2011

The effects of sediment and mercury mobilization in the South Yuba River and Humbug Creek confluence area, Nevada County, California: Concentrations, speciation, and environmental fate – Part 1: Field characterization

Millions of pounds of mercury (Hg) were deposited in the river and stream channels of the Sierra Nevada from placer and hard-rock mining operations in the late 1800s and early 1900s. The resulting contaminated sediments are relatively harmless when buried and isolated from the overlying aquatic environment. The entrained Hg in the sediment constitutes a potential risk to human and ecosystem health should it be reintroduced to the actively cycling portion of the aquatic system, where it can become methylated and subsequently bioaccumulated in the food web. Each year, sediment is mobilized within these fluvial systems during high stormflows, transporting hundreds of tons of Hg-laden sediment downstream. The State of California and resource-management agencies, including the Bureau of Land Management (BLM) and the U.S. Forest Service, are concerned about additional disturbances, such as from suction gold dredging activities, which have the potential to mobilize Hg associated with buried sediment layers elevated in Hg that are otherwise likely to remain buried under normal storm conditions. The BLM initiated a study looking at the feasibility of removing Hg-contaminated sediment at the confluence of the South Yuba River and Humbug Creek in the northern Sierra Nevada of California by using standard suction-dredge technology. Additionally, the California State Water Resources Control Board (SWRCB) supported a comprehensive characterization of the intended dredge site. Together, the BLM and SWRCB supported a comprehensive characterization of Hg contamination at the site and the potential effects of sediment disturbance at locations with historical hydraulic mining debris on downstream environments. The comprehensive study consisted of two primary components: field studies and laboratory experiments. The field component, described in this report, had several study elements: 1) a preliminary, smallscale, in-stream dredge test; 2) comprehensive characterization of grain size distribution, Hg speciation, and mineralogy of bed and suspended sediment; 3) a determination of the past and current sources of sediment in the study area; 4) an assessment of Hg bioaccumulation in the local invertebrate population; and 5) a comparison of potential Hg transport caused by natural storm disturbances with potential Hg mobilization caused by suction dredging as a method of Hg removal at the study site. The laboratory component of the study assessed the potential influence of the disturbance of Hg-contaminated sediment through experiments designed to simulate in-stream transport, deposition, and potential methylation of Hg, described in a companion report (see Marvin-DiPasquale and others, 2011). Results of the field studies indicate that the fine-grained fraction (silt-clay, less than 0.063 millimeters) contains the greatest concentration of Hg in contaminated sediment. Because the fine-grained fraction is the most susceptible to longrange fluvial transport, disturbance of Hg-contaminated sediment is likely to increase the concentration and load of Hg in downstream waters. The preliminary, small-scale dredge test showed an increase in the concentration of fine particles and Hg in the water column caused by the dredge activity, despite relatively low concentrations of fine particles and Hg (about 300 nanograms per gram) at the dredge site. Characterization of sediment from two test pits and other sites in the vicinity of the confluence of the South Yuba River and Humbug Creek revealed a highly variable distribution of fine- and coarse-grained sediment. The highest levels of Hg contamination (up to 11,100 ng/g) were associated with the fine-grained fraction of sediment from the bedrock contact zone of Pit 2, a horizon which also yielded grains of gold and gold-Hg amalgam. A closed-circuit tank experiment with a venturi dredge at the base of Pit 1, in a gravel bar within the South Yuba River, resulted in fine-grained suspended sediment remaining in suspension more than 40 hours following the disturbance simulation. Although the volumetric concentration of Hg declined over time as particles settled out, the concentration of Hg on the suspended particles increased over time as the suspended material became finer grained, because Hg is preferentially adsorbed on to clay-sized particles. Mineralogical and chemical analyses indicated that the buried fine-grained material with the greatest Hg contamination was derived from hydraulic mining debris, which consist primarily of Eocene gravels mined in the Malakoff Diggins, North Bloomfield, and Lake City areas within the South Yuba River watershed. Coarse material and more recently deposited sediment were derived primarily from upstream sources on the South Yuba River. The biota assessment indicated that invertebrate taxa collected from all sites on the South Yuba River in 2007, including lower Humbug Creek, had elevated concentrations of total mercury (THg) and methylmercury (MeHg) compared to a reference site on the Bear River, upstream of mining effects. Differences with the reference site were less pronounced in 2008 when a significant reduction in MeHg concentrations was observed in biota across all taxa from concentrations in 2007. It is possible that the inter-annual variation was related to the fact that suction dredging was active in the South Yuba River in 2007 but not in 2008 when a local moratorium was imposed by the BLM. There were significant variations among taxa for both THg and MeHg concentrations, with the water striders (Gerridae) having the highest concentrations of both THg and MeHg; variation among sites was not as strong as between years or among taxa. These results suggest that additional monitoring would be helpful to investigate the possible linkage between variations in MeHg bioaccumulation and levels of suction dredge activity in areas of historical gold mining. Results from the field studies indicate that disturbance of the finegrained Hg-contaminated sediment would likely lead to enhanced mobilization of Hg to downstream environments; therefore, the use of suction dredging to remove Hg at the South Yuba River and Humbug Creek confluence area would likely result in enhanced Hg transport downstream relative to natural conditions.

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USGS2010

Holocene variations in mineral and grain-size composition along the East Greenland glaciated margin (ca 67°–70°N): local versus long-distance sediment transport

Quantitative X-Ray Diffraction (qXRD) analysis of the <2 mm sediment fraction from surface (sea floor) samples, and marine sediment cores that span the last 10-12 cal ka BP, are used to describe spatial and temporal variations in non-clay mineral compositions for an area between Kangerlussuaq Trough and Scoresby Sund (???67??-70??N), East Greenland. Bedrock consists primarily of an early Tertiary alkaline complex with high weight% of pyroxene and plagioclase. Farther inland and to the north, the bedrock is dominantly felsic with a high fraction of quartz and potassium feldspars. Principal Component (PC) analysis of the non-clay sediment compositions indicates the importance of quartz and pyroxene as compositional end members, with an abrupt shift from quartz and k-feldspar dominated sediments north of Scoresby Sund to sediments rich in pyroxene and plagioclase feldspars offshore from the early Tertiary basaltic outcrop. Coarse (<2 mm or <1 mm) ice-rafted sediments are largely absent from the trough sediments between ???8 and 5 cal ka BP, but then increase in the last 4 cal ka BP. Compositional unmixing of the sediments in Grivel Basin and Kangerlussuaq Trough indicate the dominance of local over long distance sediment sources, with pulses of sediment from tidewater glaciers in Kangerlussuaq and Nansen fjords reaching the inner shelf during the Neoglaciation. The change in IRD is more dramatic in the sediment grain-size proxies than in the quartz wt%. Forty to seventy percent of the variance in the quartz records from either side of Denmark Strait is explained by low frequency trends, but the data from the Grivel Basin, East Greenland, are distinctly different, with an approximate 2500 yr periodicity. ?? 2010 Elsevier Ltd.

Quaternary Science Reviews↗