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Atmospheric mercury deposition during the last 270 years: A glacial ice core record of natural and anthropogenic sources

Mercury (Hg) contamination of aquatic ecosystems and subsequent methylmercury bioaccumulation are significant environmental problems of global extent. At regional to global scales, the primary mechanism of Hg contamination is atmospheric Hg transport. Thus, a better understanding of the long-term history of atmospheric Hg cycling and quantification of the sources is critical for assessing the regional and global impact of anthropogenic Hg emissions. Ice cores collected from the Upper Fremont Glacier (UFG), Wyoming, contain a high-resolution record of total atmospheric Hg deposition (ca. 1720−1993). Total Hg in 97 ice-core samples was determined with trace-metal clean handling methods and low-level analytical procedures to reconstruct the first and most comprehensive atmospheric Hg deposition record of its kind yet available from North America. The record indicates major atmospheric releases of both natural and anthropogenic Hg from regional and global sources. Integrated over the past 270-year ice-core history, anthropogenic inputs contributed 52%, volcanic events 6%, and background sources 42%. More significantly, during the last 100 years, anthropogenic sources contributed 70% of the total Hg input. Unlike the 2−7-fold increase observed from preindustrial times (before 1840) to the mid-1980s in sediment-core records, the UFG record indicates a 20-fold increase for the same period. The sediment-core records, however, are in agreement with the last 10 years of this ice-core record, indicating declines in atmospheric Hg deposition.

Environmental Science & Technology↗

Use of ICP/MS with ultrasonic nebulizer for routine determination of uranium activity ratios in natural water

A method is described that allows precise determination of 234 U/ 238 U activity ratios (UAR) in most natural waters using commonly available inductively coupled plasma/mass spectrometry (ICP/MS) instrumentation and accessories. The precision achieved by this technique (±0.5% RSD, 1 sigma) is intermediate between thermal ionization mass spectrometry (±0.25% RSD, 1 sigma) and alpha particle spectrometry (±5% RSD, 1 sigma). It is precise and rapid enough to allow analysis of a large number of samples in a short period of time at low cost using standard, commercially available quadrupole instrumentation with ultrasonic nebulizer and desolvator accessories. UARs have been analyzed successfully in fresh to moderately saline waters with U concentrations of from less than 1 μg/L to nearly 100 μg/L. An example of the uses of these data is shown for a study of surface-water mixing in the North Platte River in western Nebraska. This rapid and easy technique should encourage the wider use of uranium isotopes in surface-water and groundwater investigations, both for qualitative (e.g. identifying sources of water) and quantitative (e.g. determining end-member mixing ratios purposes.

Environmental Science & Technology↗

Evaluation of current techniques for isolation of chars as natural adsorbents

Chars in soils or sediments may potentially influence the soil/sediment sorption behavior. Current techniques for the isolation of black carbon including chars rely often on acid demineralization, base extraction, and chemical oxidation to remove salts and minerals, humic acid, and refractory kerogen, respectively. Little is known about the potential effects of these chemical processes on the char surface and adsorptive properties. This study examined the effects of acid demineralization, base extraction, and acidic Cr2O72- oxidation on the surface areas, surface acidity, and benzene adsorption characteristics of laboratory-produced pinewood and wheat-residue chars, pure or mixed with soils, and a commercial activated carbon. Demineralization resulted in a small reduction in the char surface area, whereas base extraction showed no obvious effect. Neither demineralization nor base extraction caused an appreciable variation in benzene adsorption and presumably the char surface properties. By contrast, the Cr2O 72- oxidation caused a >31% reduction in char surface area. The Boehm titration, supplemented by FTIR spectra, indicated that the surface acidity of oxidized chars increased by a factor between 2.3 and 12 compared to nonoxidized chars. Benzene adsorption with the oxidized chars was lower than that with the non-oxidized chars by a factor of >8.9; both the decrease in char surface area and the increase in char surface acidity contributed to the reduction in char adsorptive power. Although the Cr 2O72- oxidation effectively removes resistant kerogen, it is not well suited for the isolation of chars as contaminant adsorbents because of its destructive nature. Alternative nondestructive techniques that preserve the char surface properties and effectively remove kerogen must be sought.

Environmental Science & Technology↗

Long-term natural attenuation of carbon and nitrogen within a groundwater plume after removal of the treated wastewater source

Disposal of treated wastewater for more than 60 years onto infiltration beds on Cape Cod, Massachusetts produced a groundwater contaminant plume greater than 6 km long in a surficial sand and gravel aquifer. In December 1995 the wastewater disposal ceased. A long-term, continuous study was conducted to characterize the post-cessation attenuation of the plume from the source to 0.6 km downgradient. Concentrations and total pools of mobile constituents, such as boron and nitrate, steadily decreased within 1-4 years along the transect. Dissolved organic carbon loads also decreased, but to a lesser extent, particularly downgradient of the infiltration beds. After 4 years, concentrations and pools of carbon and nitrogen in groundwater were relatively constant with time and distance, but substantially elevated above background. The contaminant plume core remained anoxic for the entire 10-year study period; temporal patterns of integrated oxygen deficit decreased slowly at all sites. In 2004, substantial amounts of total dissolved carbon (7 mol C m-2) and fixed (dissolved plus sorbed) inorganic nitrogen (0.5 mol N m-2) were still present in a 28-m vertical interval at the disposal site. Sorbed constituents have contributed substantially to the dissolved carbon and nitrogen pools and are responsible for the long-term persistence of the contaminant plume. Natural aquifer restoration at the discharge location will take at least several decades, even though groundwater flow rates and the potential for contaminant flushing are relatively high.

Environmental Science & Technology↗

Using chromate to investigate the impact of natural organics on the surface reactivity of nanoparticulate magnetite

Chromate was used as a chemical probe to investigate the size-dependent influence of organics on nanoparticle surface reactivity. Magnetite–chromate sorption experiments were conducted with ∼90 and ∼6 nm magnetite nanoparticles in the presence and absence of fulvic acid (FA), natural organic matter (NOM), and isolated landfill leachate (LL). Results indicated that low concentrations (1 mg/L) of organics had no noticeable impact on chromate sorption, whereas concentrations of 50 mg/L or more resulted in decreased amounts of chromate sorption. The adsorption of organics onto the magnetite surfaces interfered equally with the ability of the 6 and 90 nm particles to sorb chromate from solution, despite the greater surface area of the smaller particles. Results indicate the presence of organics did not impact the redox chemistry of the magnetite–chromate system over the duration of the experiments (8 h), nor did the organics interact with the chromate in solution. Brunauer–Emmett–Teller (BET) and scanning electron microscopy (SEM) results indicate that the organics blocked the surface reactivity by occupying surface sites on the particles. The similarity of results with FA and NOM suggests that coverage of the reactive mineral surface is the main factor behind the inhibition of surface reactivity in the presence of organics.

Environmental Science & Technology↗

Geochemistry of inorganic nitrogen in waters released from coal-bed natural gas production wells in the Powder River Basin, Wyoming

Water originating from coal-bed natural gas (CBNG) production wells typically contains ammonium and is often disposed via discharge to ephemeral channels. A study conducted in the Powder River Basin, Wyoming, documented downstream changes in CBNG water composition, emphasizing nitrogen-cycling processes and the fate of ammonium. Dissolved ammonium concentrations from 19 CBNG discharge points ranged from 95 to 527 μM. Within specific channels, ammonium concentrations decreased with transport distance, with subsequent increases in nitrite and nitrate concentrations. Removal efficiency, or uptake, of total dissolved inorganic nitrogen (DIN) varied between channel types. DIN uptake was greater in the gentle-sloped, vegetated channel as compared to the incised, steep, and sparsely vegetated channel and was highly correlated with diel patterns of incident light and dissolved oxygen concentration. In a larger main channel with multiple discharge inputs ( n = 13), DIN concentrations were >300 μM, with pH > 8.5, after 5 km of transport. Ammonium represented 25−30% of the large-channel DIN, and ammonium concentrations remained relatively constant with time, with only a weak diel pattern evident. In July 2003, the average daily large-channel DIN load was 23 kg N day −1 entering the Powder River, an amount which substantially increased the total Powder River DIN load after the channel confluence. These results suggest that CBNG discharge may be an important source of DIN to western watersheds, at least at certain times of the year, and that net oxidation and/or removal is dependent upon the extent of contact with sediment and biomass, type of drainage channel, and time of day.

Wyoming↗

Quantification of natural vapor fluxes of trichloroethene in the unsaturated zone at Picatinny Arsenal, New Jersey

The upward flux of trichloroethene (TCE) vapor through the unsaturated zone above a contaminated, water-table aquifer at Picatinny Arsenal, New Jersey, has been studied under natural conditions over a 12-month period. Vertical gas-phase diffusion fluxes were estimated indirectly by measuring the TCE vapor concentration gradient in the unsaturated zone and using Fick's law to calculate the flux. The total gas-phase flux (e.g., the sum of diffusion and advection fluxes) was measured directly with a vertical flux chamber (VFC). In many cases, the upward TCE vapor flux was several orders of magnitude greater than the upward TCE diffusion flux, suggesting that mechanisms other than steady-state vapor diffusion are contributing to the vertical transport of TCE vapors through the unsaturated zone. The measured total flux of TCE vapor from the subsurface to the atmosphere is approximately 50 kg/yr and is comparable in magnitude to the removal rate of TCE from the aquifer by an existing pump-and-treat system and by discharge into a nearby stream. The net upward flux of TCE is reduced significantly during a storm event, presumably due to the mass transfer of TCE from the soil gas to the infiltrating rainwater and its subsequent downward advection. Several potential problems associated with the measurement of total gas-phase fluxes are discussed.

Environmental Science & Technology↗

Comparison of denitrification activity measurements in groundwater using cores and natural-gradient tracer tests

The transport of many solutes in groundwater is dependent upon the relative rates of physical flow and microbial metabolism. Quantifying rates of microbial processes under subsurface conditions is difficult and is most commonly approximated using laboratory studies with aquifer materials. In this study, we measured in situ rates of denitrification in a nitrate-contaminated aquifer using small-scale, natural-gradient tracer tests and compared the results with rates obtained from laboratory incubations with aquifer core material. Activity was measured using the acetylene block technique. For the tracer tests, co-injection of acetylene and bromide into the aquifer produced a 30 μM increase in nitrous oxide after 10 m of transport (23−30 days). An advection−dispersion transport model was modified to include an acetylene-dependent nitrous oxide production term and used to simulate the tracer breakthrough curves. The model required a 4-day lag period and a relatively low sensitivity to acetylene to match the narrow nitrous oxide breakthrough curves. Estimates of in situ denitrification rates were 0.60 and 1.51 nmol of N 2 O produced cm - 3 aquifer day - 1 for two successive tests. Aquifer core material collected from the tracer test site and incubated as mixed slurries in flasks and as intact cores yielded rates that were 1.2−26 times higher than the tracer test rate estimates. Results with the coring-dependent techniques were variable and subject to the small-scale heterogeneity within the aquifer, while the tracer tests integrated the heterogeneity along a flow path, giving a rate estimate that is more applicable to transport at the scale of the aquifer.

Environmental Science & Technology↗

The interaction of natural organic matter with iron in a wetland (Tennessee Park, Colorado) receiving acid mine drainage

Pore water from a wetland receiving acid mine drainage was studied for its iron and natural organic matter (NOM) geochemistry on three different sampling dates during summer 1994. Samples were obtained using a new sampling technique that is based on screened pipes of varying length (several centimeters), into which dialysis vessels can be placed and that can be screwed together to allow for vertical pore-water sampling. The iron concentration increased with time (through the summer) and had distinct peaks in the subsurface. Iron was mainly in the ferrous form; however, close to the surface, significant amounts of ferric iron (up to 40% of 2 mmol L-1 total iron concentration) were observed. In all samples studied, iron was strongly associated with NOM. Results from laboratory experiments indicate that the NOM stabilizes the ferric iron as small iron oxide colloids (able to pass a 0.45μm dialysis membrane). We hypothesize that, in the pore water of the wetland, the high NOM concentrations (>100 mg C L-1) allow formation of such colloids at the redoxcline close to the surface and at the contact zone to the adjacent oxic aquifer. Therefore, particle transport along flow paths and resultant export of ferric iron from the wetland into ground water might be possible.

Aquatic Geochemistry↗

Attention turns to naturally occurring methane seepage

Methane is the most abundant organic compound in the Earth's atmosphere. As a powerful greenhouse gas, it has implications for global climate change. Sources of methane to the atmosphere are varied. Depending on the source, methane can contain either modern or ancient carbon. Methane exiting from swamps and wetlands contains modern carbon, whereas methane leaking from petroleum reservoirs contains ancient carbon. The total annual source of methane to the atmosphere has been constrained to about 540 teragrams (Tg) per year “ Cicerone and Oremland , 1988”. Notably absent from any identified sources is the contribution of geologically sourced methane from naturally occurring seepage.

Eos, Earth and Space Science News↗

Comparison of constitutive flow resistance equations based on the Manning and Chezy equations applied to natural rivers

A set of conceptually derived in‐bank river discharge–estimating equations (models), based on the Manning and Chezy equations, are calibrated and validated using a database of 1037 discharge measurements in 103 rivers in the United States and New Zealand. The models are compared to a multiple regression model derived from the same data. The comparison demonstrates that in natural rivers, using an exponent on the slope variable of 0.33 rather than the traditional value of 0.5 reduces the variance associated with estimating flow resistance. Mean model uncertainty, assuming a constant value for the conductance coefficient, is less than 5% for a large number of estimates, and 67% of the estimates would be accurate within 50%. The models have potential application where site‐specific flow resistance information is not available and can be the basis for (1) a general approach to estimating discharge from remotely sensed hydraulic data, (2) comparison to slope‐area discharge estimates, and (3) large‐scale river modeling.

Water Resources Research↗

Long-term evolution of sand transport through a river network: Relative influences of a dam versus natural changes in grain size from sand waves

Temporal and spatial nonuniformity in supplies of water and sand in a river network leads to sand transport that is in local disequilibrium with the upstream sand supply. In such river networks, sand is transported downstream as elongating waves in which coupled changes in grain size and transport occur. Depending on the magnitude of each sand‐supplying event and the interval between such events, changes in bed‐sand grain size associated with sand‐wave passage may more strongly regulate sand transport than do changes in water discharge. When sand transport is controlled more by episodic resupply of sand than by discharge, upstream dam construction may exacerbate or mitigate sand‐transport disequilibria, thus leading to complicated and difficult‐to‐predict patterns of deposition and erosion. We analyzed all historical sediment‐transport data and embarked on a 4‐year program of continuous sediment‐transport measurements to describe disequilibrium sand transport in a river network. Results indicate that sand transport in long river segments can evolve over ≥50‐year timescales following rare large sand‐supplying events. These natural changes in sand transport in distal downstream river segments can be larger than those caused by an upstream dam. Because there is no way to know a priori whether sand transport in a river has changed in response to changes in the upstream sand supply, contemporary continuous measurements of sand transport are required for accurate sand loads and budgeting. Analysis of only historical sediment‐transport measurements, as is common in the literature, may lead to incorrect conclusions with respect to current or future sediment‐transport conditions.

Journal of Geophysical Research: Earth Surface↗

The finicky nature of earthquake shaking-triggered submarine sediment slope failures and sediment gravity flows

Since 2011, seafloor temperatures, pressures, and seismic ground motions have been measured by the seafloor cabled Dense Oceanfloor Network system for Earthquakes and Tsunamis (DONET) on the Nankai margin. These measurements, high-resolution bathymetry, and abundant contextual information make the DONET region seem ideally suited to provide constraints on seismic shaking-triggered sediment slope failures and gravity flows, particularly since numerous published studies have linked paleo- to modern earthquakes to failures and flows within the DONET. The occurrences of the local 2016 M6.0 Mie-ken and regional M7.0 Kumamoto earthquakes within and at regional distances, respectively, from the DONET data set provided an opportunity to explore this potential. We used DONET seismic recordings of the posited triggering shaking and to search for submarine slide signals and continuous temperature and pressure data to detect pulses of warm and densified water indicative of passing flows. We developed and applied a variety of analytical methods to eliminate signals generated by water column processes, while leaving slope failures and sediment gravity flow anomalies as residuals. Our explorations yielded no evidence that earthquake shaking initiated either phenomenon, which we suggest reflects the finicky nature both of the detection of and the physical processes that contribute to slope failures and flows (i.e., both require satisfying precise suites of conditions). Nonetheless, this negative result, our analyses, and the estimates of physical properties we derived for them, provide useful lessons and inputs for future studies.

Journal of Geophysical Research↗

Vegetation-generated turbulence does not impact the erosion of natural cohesive sediment

Previous studies have demonstrated that vegetation-generated turbulence can enhance erosion rate and reduce the velocity threshold for erosion of non-cohesive sediment. This study considered whether vegetation-generated turbulence had a similar influence on natural cohesive sediment. Cores were collected from a black mangrove forest with aboveground biomass and exposed to stepwise increases in velocity. Erosion was recorded through suspended sediment concentration. For the same velocity, cores with pneumatophores had elevated turbulent kinetic energy compared to bare cores without pneumatophores. However, the vegetation-generated turbulence did not increase bed stress or the rate of resuspension, relative to bare cores. It was hypothesized that the short time-scale fluctuations associated with vegetation-generated turbulence were not of sufficient duration to break cohesion between grains, explaining why elevated levels of turbulence associated with the pneumatophores had no impact on the erosion threshold or rate.

Louisiana↗

Light absorbing particles deposited to snow cover across the Upper Colorado River Basin, Colorado Rocky Mountains, 2013-16: Interannual variations from multiple natural and anthropogenic sources

Atmospheric particulate matter (PM) as light-absorbing particles (LAPs) deposited to snow cover can result in early onset and rapid snow melting, challenging management of downstream water resources. We identified LAPs in 38 snow samples (water years 2013–2016) from the mountainous Upper Colorado River basin by comparing among laboratory-measured spectral reflectance, chemical, physical, and magnetic properties. Dust sample reflectance, averaged over the wavelength range of 0.35–2.50 μm, varied by a factor of 1.9 (range, 0.2300–0.4444) and was suppressed mainly by three components: (a) carbonaceous matter measured as total organic carbon (1.6–22.5 wt. %) including inferred black carbon, natural organic matter, and carbon-based synthetic, black road-tire-wear particles, (b) dark rock and mineral particles, indicated by amounts of magnetite (0.11–0.37 wt. %) as their proxy, and (c) ferric oxide minerals identified by reflectance spectroscopy and magnetic properties. Fundamental compositional differences were associated with different iron oxide groups defined by dominant hematite, goethite, or magnetite. These differences in iron oxide mineralogy are attributed to temporally varying source-area contributions implying strong interannual changes in regional source behavior, dust-storm frequency, and (or) transport tracks. Observations of dust-storm activity in the western U.S. and particle-size averages for all samples (median, 25 μm) indicated that regional dust from deserts dominated mineral-dust masses. Fugitive contaminants, nevertheless, contributed important amounts of LAPs from many types of anthropogenic sources.

Colorado↗

A method to implement natural flow regimes for regulated rivers

Rivers throughout the world have been dammed for flood control, irrigation, hydropower, and water storage for centuries. Dams service the economic and development needs of societies, but degrade the ecology of rivers. To conserve diminishing aquatic species and their habitats, methods are needed to help managers implement flow releases with timescales and patterns that are relevant to aquatic species and physical processes. We present a method to synchronize flow releases from dams with local hydrology, while ensuring constraints of flood control and water allocations are met. We demonstrate an optimization technique that scales flows of a proximal unregulated river and results in discharges that are synchronized with natural hydrologic patterns. Importantly, our method preserves operational and regulatory requirements such as water allocation volumes and flood control thresholds. This technique can be used at various timescales, and can incorporate many system-specific constraints. We selected the Trinity River, California as an example, and scale flows according to a proximal gage on the Salmon River in California. We evaluate our technique using an array of flow regime metrics from the literature, and our method produced hydrographs with greater flow variation throughout a larger portion of the water year than current management strategies. These hydrographs yielded flow metrics more similar to those from unimpaired flow patterns, including those measuring within and among year flow variability. The Real Time Management framework is a new tool that can be implemented to improve the health of rivers and the aquatic species that depend upon them.

California↗

Natural source zone depletion of crude oil in the subsurface: Processes controlling mass losses of individual compounds

At many petroleum hydrocarbon spill sites, residual spilled product forms a long-term source of groundwater contamination. The phrase source zone natural depletion is used to refer to the mass loss rates. Overall mass lost under environmental conditions was analyzed using conservative biomarker concentrations for a 1979 oil spill in northern Minnesota, USA. After 40–41 years, an average of 50% of the mass was lost with values ranging from 22% to 57% depending on location. It is also important to understand the composition changes in the source. To understand controls on the losses of individual compounds, concentrations of volatile hydrocarbons in oil samples were compared with aqueous solubilities, and pore-space oil saturations. The results of the comparison show that losses of the oil compounds were controlled by pore-space oil saturations, solubility, and susceptibility to degradation under methanogenic conditions. Compounds that degrade under methanogenic conditions, including toluene, o -xylene, and n -alkanes are more depleted compared to benzene, ethylbenzene, and m - and p -xylene for which losses are dominated by dissolution. These rates and compound-specific behaviors form a foundation for improved modeling approaches and risk analyses.

Minnesota↗

Large-scale natural gradient tracer test in sand and gravel, Cape Cod, Massachusetts: 1. Experimental design and observed tracer movement

A large-scale natural gradient tracer experiment was conducted on Cape Cod, Massachusetts, to examine the transport and dispersion of solutes in a sand and gravel aquifer. The nonreactive tracer, bromide, and the reactive tracers, lithium and molybdate, were injected as a pulse in July 1985 and monitored in three dimensions as they moved as far as 280 m down-gradient through an array of multilevel samplers. The bromide cloud moved horizontally at a rate of 0.42 m per day. It also moved downward about 4 m because of density-induced sinking early in the test and accretion of areal recharge from precipitation. After 200 m of transport, the bromide cloud had spread more than 80 m in the direction of flow, but was only 14 m wide and 4–6 m thick. The lithium and molybdate clouds followed the same path as the bromide cloud, but their rates of movement were retarded about 50% relative to bromide movement because of sorption onto the sediments.

Massachusetts↗