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USGS2010

Effects of groundwater-flow paths on nitrate concentrations across two riparian forest corridors

Groundwater levels, apparent age, and chemistry from field sites and groundwater-flow modeling of hypothetical aquifers collectively indicate that groundwater-flow paths contribute to differences in nitrate concentrations across riparian corridors. At sites in Virginia (one coastal and one Piedmont), lowland forested wetlands separate upland fields from nearby surface waters (an estuary and a stream). At the coastal site, nitrate concentrations near the water table decreased from more than 10 mg/L beneath fields to 2 mg/L beneath a riparian forest buffer because recharge through the buffer forced water with concentrations greater than 5 mg/L to flow deeper beneath the buffer. Diurnal changes in groundwater levels up to 0.25 meters at the coastal site reflect flow from the water table into unsaturated soil where roots remove water and nitrate dissolved in it. Decreases in aquifer thickness caused by declines in the water table and decreases in horizontal hydraulic gradients from the uplands to the wetlands indicate that more than 95% of the groundwater discharged to the wetlands. Such discharge through organic soil can reduce nitrate concentrations by denitrification. Model simulations are consistent with field results, showing downward flow approaching toe slopes and surface waters to which groundwater discharges. These effects show the importance of buffer placement over use of fixed-width, streamside buffers to control nitrate concentrations.

Virginia↗

USGS2010

Biologic origin of iron nodules in a marine terrace chronosequence, Santa Cruz, California

The distribution, chemistry, and morphology of Fe nodules were studied in a marine terrace soil chronosequence northwest of Santa Cruz, California. The Fe nodules are found at depths <1 m on all terraces. The nodules consisted of soil mineral grains cemented by Fe oxides. The nodules varied in size from 0.5 to 25 mm in diameter. Nodules did not occur in the underlying regolith. The Fe-oxide mineralogy of the nodules was typically goethite; however, a subset of nodules consisted of maghemite. There was a slight transformation to hematite with time. The abundance of soil Fe nodules increased with terrace age on the five terraces studied (aged 65,000-226,000 yr). Scanning electron microscopy (SEM) revealed Fe-oxide-containing fungal hyphae throughout the nodules, including organic structures incorporating fine-grained Fe oxides. The fine-grained nature of the Fe oxides was substantiated by M??ssbauer spectroscopy. Our microscopic observations led to the hypothesis that the nodules in the Santa Cruz terrace soils are precipitated by fungi, perhaps as a strategy to sequester primary mineral grains for nutrient extraction. The fungal structures are fixed by the seasonal wetting and dry cycles and rounded through bioturbation. The organic structures are compacted by the degradation of fungal C with time. ?? Soil Science Society of America. All rights reserved.

Soil Science Society of America Journal↗

USGS2014

Reconnaissance of pharmaceuticals and wastewater indicators in streambed sediments of the lower Columbia River basin, Oregon and Washington

One by-product of advances in modern chemistry is the accumulation of synthetic chemicals in the natural environment. These compounds include contaminants of emerging concern (CECs), some of which are endocrine disrupting compounds (EDCs) that can have detrimental reproductive effects. The role of sediments in accumulating these types of chemicals and acting as a source of exposure for aquatic organisms is not well understood. Here we present a small-scale reconnaissance of CECs in bed sediments of the lower Columbia River and several tributaries and urban streams. Surficial bed sediment samples were collected from the Columbia River, the Willamette River, the Tualatin River, and several small urban creeks in Oregon. Thirty-nine compounds were detected at concentrations ranging from <1 to >1,000 ng [g sediment] -1 dry weight basis. Columbia River mainstem, suggesting a higher risk of exposure to aquatic life in lower order streams. Ten known or suspected EDCs were detected during the study. At least one EDC was detected at 21 of 23 sites sampled; several EDCs were detected in sediment from most sites. This study is the first to document the occurrence of a large suite of CECs in the sediments of the Columbia River basin. A better understanding of the role of sediment in the fate and effects of emerging contaminants is needed.

Oregon;Washington↗

USGS2021

The structure and volume of large geysers in Yellowstone National Park, USA and the mineralogy and chemistry of their silica sinter deposits

Siliceous sinter is formed by biogenic and abiogenic opal deposition around hot springs and geysers. Using Structure-from-Motion photogrammetry we generated three-dimensional models of Giant and Castle Geysers from the Upper Geyser Basin of Yellowstone National Park. We use these models to calculate an approximate mass of sinter for each (~2 and ~ 5 kton, respectively) and estimate a range of plausible long-term deposition rates for Castle Geyser (470 to 940 kg·yr −1 ). We estimate ~2% of the silica discharged from Castle Geyser is deposited as sinter in the cone and proximal terraces. We collected 15 sinter samples following the stratigraphy of each geyser from an older terrace to a younger cone and examined them using a variety of analytical methods. We find that young opaline sinter with a water content of <12 wt% (from loss on ignition) contains higher concentrations of major and trace elements, notably As, Sb, Rb, Ga and Cs, relative to older dehydrated sinter. Rare earth element (REE) concentrations in sinter are 2–3 orders of magnitude higher than in the thermal water from which they are deposited. Sinter deposits are enriched in light REE, Gd and Yb when normalized to concentrations in thermal water and enriched in Eu, Tm, and Yb when normalized to the underlying rhyolite. Sinter samples with the highest REE concentrations are also enriched in organic material, implying either microbial uptake of REE, or that organic molecules are efficient ligands that form metal complexes.

Wyoming↗

USGS2006

Use of field-applied quality control samples to monitor performance of a Goulden large-sample extractor/GC-MS method for pesticides in water

Since 1985, the Goulden large-sample extractor (GLSE) has been used to isolate a broad array of trace-organic contaminants from large volumes of water. In this study, field-applied quality control measures, including matrix and surrogate spikes and blanks, were used to monitor method performance from GLSE extraction through GC-MS analysis. The method was applied to the determination of multiple classes of pesticides isolated from 4- to 112-L filtered surface-water samples. Average recoveries of six surrogate compounds ranged from 84 ?? 18% for [2H10]diazinon to 15 ?? 13% for 4,4'-[2H8]DDT, the low recoveries for which were largely a result of unmonitored breakdown of this surrogate by the GC injection system. Field-matrix-spike samples were prepared by fortifying 10-L, 35-L, and 110-L filtered surface-water samples with 68 pesticides to amended concentrations of 11- to 50-ng/L each. Recoveries ranged from not detected to greater than 100%. Variability in pesticide recoveries from triplicate 10-L water samples collected at one site averaged 5.7% relative standard deviation and did not exceed 19%.Since 1985, the Goulden large-sample extractor (GLSE) has been used to isolate a broad array of trace-organic contaminants from large volumes of water. In this study, field-applied quality control measures, including matrix and surrogate spikes and blanks, were used to monitor method performance from GLSE extraction through GC-MS analysis. The method was applied to the determination of multiple classes of pesticides isolated from 4- to 112-L filtered surface-water samples. Average recoveries of six surrogate compounds ranged from 84 ?? 18% for [2H10]diazinon to 15 ?? 13% for 4,4???-[2H8]DDT, the low recoveries for which were largely a result of unmonitored breakdown of this surrogate by the GC injection system. Field-matrix-spike samples were prepared by fortifying 10-L, 35-L, and 110-L filtered surface-water samples with 68 pesticides to amended concentrations of 11- to 50-ng/L each. Recoveries ranged from not detected to greater than 100%. Variability in pesticide recoveries from triplicate 10-L water samples collected at one site averaged 5.7% relative standard deviation and did not exceed 19%.

International Journal of Environmental Analytical ↗

USGS2011

Limnogeology in Brazil's "forgotten wilderness": A synthesis from the large floodplain lakes of the Pantanal

Sediment records from floodplain lakes have a large and commonly untapped potential for inferring wetland response to global change. The Brazilian Pantanal is a vast, seasonally inundated savanna floodplain system controlled by the flood pulse of the Upper Paraguay River. Little is known, however, about how floodplain lakes within the Pantanal act as sedimentary basins, or what influence hydroclimatic variables exert on limnogeological processes. This knowledge gap was addressed through an actualistic analysis of three large, shallow (<5 m) floodplain lakes in the western Pantanal: Lagoa Gaíva, Lagoa Mandioré and Baia Vermelha. The lakes are dilute (CO3 2- > Si 4+ > Ca 2+ ), mildly alkaline, freshwater systems, the chemistries and morphometrics of which evolve with seasonal flooding. Lake sills are bathymetric shoals marked by siliciclastic fans and marsh vegetation. Flows at the sills likely undergo seasonal reversals with the changing stage of the Upper Paraguay River. Deposition in deeper waters, typically encountered in proximity to margin-coincident topography, is dominated by reduced silty-clays with abundant siliceous microfossils and organic matter. Stable isotopes of carbon and nitrogen, plus hydrogen index measured on bulk organic matter, suggest that contributions from algae (including cyanobacteria) and other C3-vegetation dominate in these environments. The presence of lotic sponge spicules, together with patterns of terrigenous sand deposition and geochemical indicators of productivity, points to the importance of the flood pulse for sediment and nutrient delivery to the lakes. Flood-pulse plumes, waves and bioturbation likewise affect the continuity of sedimentation. Short-lived radioisotopes indicate rates of 0.11-0.24 cm year -1 at sites of uninterrupted deposition. A conceptual facies model, developed from insights gained from modern seasonal processes, can be used to predict limnogeological change when the lakes become isolated on the floodplain or during intervals associated with a strengthened flood pulse. Amplification of the seasonal cycle over longer time scales suggests carbonate, sandy lowstand fan and terrestrial organic matter deposition during arid periods, whereas deposition of lotic sponges, mixed aquatic organic matter, and highstand deltas characterizes wet intervals. The results hold substantial value for interpreting paleolimnological records from floodplain lakes linked to large tropical rivers with annual flooding cycles.

Bahia Vermelha, Brazilian Pantanal, Lagoa Gaiva, L↗

USGS1998

Influence of an igneous intrusion on the inorganic geochemistry of a bituminous coal from Pitkin County, Colorado

Although the effects of igneous dikes on the organic matter in coal have been observed at many localities there is virtually no information on the effects of the intrusions of the inorganic constituents in the coal. Such a study may help to elucidate the behavior of trace elements during in situ gasification of coal and may provide insights into the resources potential for coal and coke affected by the intrusion. To determine the effects of an igneous intrusion on the inorganic chemistry of a coal we used a series of 11 samples of coal and natural coke that had been collected at intervals from 3 to 106 cm from a dike that intruded the bituminous Dutch Creek coal in Pitkin, CO. The samples were chemically analyzed for 66 elements. SEM-EDX and X-ray diffraction analysis were performed on selected samples. Volatile elements such as F, Cl, Hg, and Se are not depleted in the samples (coke and coal) nearest the dike that were exposed to the highest temperatures. Their presence in these samples is likely due to secondary enrichment following volatilization of the elements inherent in the coal. Equilibration with ground water may account for the uniform distribution of Na, B, and Cl. High concentrations of Ca, Mg, Fe, Mn, Sr, and CO2 in the coke region are attributed to the reaction of CO and CO2 generated during the coking of the coal with fluids from the intrusion, resulting in the precipitation of carbonates. Similarly, precipitation of sulfide minerals in the coke zone may account for the relatively high concentrations of Ag, Hg, Cu, Zn, and Fe. Most elements are concentrated at the juncture of the fluidized coke and the thermally metamorphosed coal. Many of the elements enriched in this region (for example, Ga, Ge, Mo, Rb, U, La, Ce, Al, K, and Si) may have been adsorbed on either the clays or the organic matter or on both.Although the effects of igneous dikes on the organic matter in coal have been observed at many localities there is virtually no information on the effects of the intrusions on the inorganic constituents in the coal. Such a study may help to elucidate the behavior of trace elements during in situ gasification of coal and may provide insights into the resource potential of coal and coke affected by the intrusion. To determine the effects of an igneous intrusion on the inorganic chemistry of a coal we used a series of 11 samples of coal and natural coke that had been collected at intervals from 3 to 106 cm from a dike that intruded the bituminous Dutch Creek coal in Pitkin, CO. The samples were chemically analyzed for 66 elements. SEM-EDX and X-ray diffraction analysis were performed on selected samples. Volatile elements such as F, Cl, Hg, and Se are not depleted in the samples (coke and coal) nearest the dike that were exposed to the highest temperatures. Their presence in these samples is likely due to secondary enrichment following volatilization of the elements inherent in the coal. Equilibration with ground water may account for the uniform distribution of Na, B, and Cl. High concentrations of Ca, Mg, Fe, Mn, Sr, and CO2 in the coke region are attributed to the reaction of CO and CO2 generated during the coking of the coal with fluids from the intrusion, resulting in the precipitation of carbonates. Similarly, precipitation of sulfide minerals in the coke zone may account for the relatively high concentrations of Ag, Hg, Cu, Zn, and Fe. Most elements are concentrated at the juncture of the fluidized coke and the thermally metamorphosed coal. Many of the elements enriched in this region (for example, Ga, Ge, Mo, Rb, U, La, Ce, Al, K, and Si) may have been adsorbed on either the clays or the organic matter or on both.

International Journal of Coal Geology↗

USGS2006

Metallogeny of the Great Basin: Crustal evolution, fluid flow, and ore deposits

The Great Basin physiographic province in the Western United States contains a diverse assortment of world-class ore deposits. It currently (2006) is the world’s second leading producer of gold, contains large silver and base metal (Cu, Zn, Pb, Mo, W) deposits, a variety of other important metallic (Fe, Ni, Be, REE’s, Hg, PGE) and industrial mineral (diatomite, barite, perlite, kaolinite, gallium) resources, as well as petroleum and geothermal energy resources. Ore deposits are most numerous and largest in size in linear mineral belts with complex geology. U.S. Geological Survey (USGS) scientists are in the final year of a research project initiated in the fall of 2001 to increase understanding of relations between crustal evolution, fluid flow, and ore deposits in the Great Basin. Because of its substantial past and current mineral production, this region has been the focus of numerous investigations over the past century and is the site of ongoing research by industry, academia, and state agencies. A variety of geoinformatic tools was used to organize, reinterpret, and display, in space and time, the large amounts of geologic, geophysical, geochemical, and hydrologic information deemed pertinent to this problem. This information, in combination with concentrated research on (1) critical aspects of the geologic history, (2) an area in northern Nevada that encompasses the major mineral belts, and (3) important mining districts and deposits, is producing new insights about the interplay between key tectonic events, hydrothermal fluid flow, and ore genesis in mineral belts. The results suggest that the Archean to Holocene history of the Great Basin was punctuated by several tectonic events that caused fluids of different origins (sea water, basinal brine, meteoric water, metamorphic water, magmatic water) to move through the crust. Basement faults reactivated during these events localized deformation, sedimentation, magmatism, and hydrothermal fluid flow in overlying rocks to form mineral belts that contain ore deposits of different types and ages that are locally superimposed (demonstrating inheritance). Fluid flow in these systems also was influenced by the distribution of permeable lithologies and paleotopographic highs and lows. Hydrothermal fluids evolved from their initial chemistries towards compositions that reflect the ƒ O 2 and ƒ S 2 buffering capacity of, and the ligands and metals present in, the rocks (±older mineralization) through which they moved. In northern Nevada, where gold deposits are relatively common, carbonaceous, pyritic strata buffered fluids of diverse origins to H 2 S-rich compositions so they could transport gold repeatedly over Paleozoic-Cenozoic time (convergent evolution). Ore formed where metal-laden fluids encountered effective physicochemical traps. Maps of Neogene basin fill and erosion surfaces identify areas where preexisting ore deposits have been progressively exposed or concealed. Comparisons with analogous terrains and deposit types in other parts of the world provide global context. The initial findings and some of the databases, geologic maps, sections, reconstructions, hydrogeologic models, topical syntheses, regional overviews, short courses, field guides, and deposit comparisons produced by project staff and associated managers, contractors, and collaborators have been presented in numerous abstracts, symposia, USGS publications, and professional journals over the last 5 years (see the extensive bibliography). Notable among these was the 2005 Geological Society of Nevada symposium in Reno, Nevada, and the 2005 Geological Society of America annual meeting in Salt Lake City, Utah, where project results were presented to audiences from around the nation and world. The final results of the project will be submitted for publication in 2007 to appropriate USGS and professional journals. A special issue of GEOSPHERE, scheduled for publication in 2007, will be devoted to the results of this project and related work. This special issue will reach an international audience and be available worldwide on the internet. Much of the research for this project has concentrated on areas that will receive the focused attention of the mining industry in the future. As such, the data and interpretations generated by this project have direct use for land-use managers in Federal, State, and local agencies. Improved hydrogeologic models developed by this project will considerably enhance ongoing and future water resource investigations in the region. The increased understanding of when, where, and how hydrothermal systems produce significant economic deposits has direct uses for mineral exploration and for future USGS mineral resource assessments in the Great Basin and other parts of the world.

Great Basin↗

USGS1998

Recovery and validation of historical sediment quality data from coastal and estuarine areas: An integrated approach

A comprehensive database of sediment chemistry and environmental parameters has been compiled for Boston Harbor and Massachusetts Bay. This work illustrates methodologies for rescuing and validating sediment data from heterogeneous historical sources. It greatly expands spatial and temporal data coverage of estuarine and coastal sediments. The database contains about 3500 samples containing inorganic chemical, organic, texture and other environmental data dating from 1955 to 1994. Cooperation with local and federal agencies as well as universities was essential in locating and screening documents for the database. More than 80% of references utilized came from sources with limited distribution (gray literature). Task sharing was facilitated by a comprehensive and clearly defined data dictionary for sediments. It also served as a data entry template and flat file format for data processing and as a basis for interpretation and graphical illustration. Standard QA/QC protocols are usually inapplicable to historical sediment data. In this work outliers and data quality problems were identified by batch screening techniques that also provide visualizations of data relationships and geochemical affinities. No data were excluded, but qualifying comments warn users of problem data. For Boston Harbor, the proportion of irreparable or seriously questioned data was remarkably small (<5%), although concentration values for metals and organic contaminants spanned 3 orders of magnitude for many elements or compounds. Data from the historical database provide alternatives to dated cores for measuring changes in surficial sediment contamination level with time. The data indicate that spatial inhomogeneity in harbor environments can be large with respect to sediment-hosted contaminants. Boston Inner Harbor surficial sediments showed decreases in concentrations of Cu, Hg, and Zn of 40 to 60% over a 17-year period.A comprehensive database of sediment chemistry and environmental parameters has been compiled for Boston Harbor and Massachusetts Bay. This work illustrates methodologies for rescuing and validating sediment data from heterogeneous historical sources. It greatly expands spatial and temporal data coverage of estuarine and coastal sediments. The database contains about 3500 samples containing inorganic chemical, organic, texture and other environmental data dating from 1995 to 1994. Cooperation with local and federal agencies as well as universities was essential in locating and screening documents for the database. More than 80% of references utilized came from sources with limited distribution (gray Task sharing was facilitated by a comprehensive and clearly defined data dictionary for sediments. It also served as a data entry template and flat file format for data processing and as a basis for interpretation and graphical illustration. Standard QA/QC protocols are usually inapplicable to historical sediment data. In this work outliers and data quality problems were identified by batch screening techniques that also provide visualizations of data relationships and geochemical affinities. No data were excluded, but qualifying comments warn users of problem data. For Boston Harbor, the proportion of irreparable or seriously questioned data was remarkably small (<5%), although concentration values for metals and organic contaminants spanned 3 orders of magnitude for many elements or compounds. Data from the historical database provide alternatives to dated cores for measuring changes in surficial sediment contamination level with time. The data indicate that spatial inhomogeneity in harbor environments can be large with respect to sediment-hosted contaminants. Boston Inner Harbor surficial sediments showed decreases in concentrations Cu, Hg, and Zn of 40 to 60% over a 17-year period.

Massachusetts↗

USGS2000

Nitrite fixation by humic substances: Nitrogen-15 nuclear magnetic resonance evidence for potential intermediates in chemodenitrification

Studies have suggested that NO − 2 , produced during nitrification and denitrification, can become incorporated into soil organic matter and, in one of the processes associated with chemodenitrification, react with organic matter to form trace N gases, including N 2 O. To gain an understanding of the nitrosation chemistry on a molecular level, soil and aquatic humic substances were reacted with 15 N-labeled NaNO 2 , and analyzed by liquid phase 15 N and 13 C nuclear magnetic resonance (NMR). The International Humic Substances Society (IHSS) Pahokee peat and peat humic acid were also reacted with Na 15 NO 2 and analyzed by solid-state 15 N NMR. In Suwannee River, Armadale, and Laurentian fulvic acids, phenolic rings and activated methylene groups underwent nitrosation to form nitrosophenols (quinone monoximes) and ketoximes, respectively. The oximes underwent Beckmann rearrangements to 2° amides, and Beckmann fragmentations to nitriles. The nitriles in turn underwent hydrolysis to 1° amides. Peaks tentatively identified as imine, indophenol, or azoxybenzene nitrogens were clearly present in spectra of samples nitrosated at pH 6 but diminished at pH 3. The 15 N NMR spectrum of the peat humic acid exhibited peaks corresponding with N-nitroso groups in addition to nitrosophenols, ketoximes, and secondary Beckmann reaction products. Formation of N-nitroso groups was more significant in the whole peat compared with the peat humic acid. Carbon-13 NMR analyses also indicated the occurrence of nitrosative demethoxylation in peat and soil humic acids. Reaction of 15 N-NH 3 fixated fulvic acid with unlabeled NO − 2 resulted in nitrosative deamination of aminohydroquinone N, suggesting a previously unrecognized pathway for production of N 2 gas in soils fertilized with NH 3

Soil Science Society of America Journal↗

USGS2008

Tile drainage as karst: Conduit flow and diffuse flow in a tile-drained watershed

The similarity of tiled-drained watersheds to karst drainage basins can be used to improve understanding of watershed-scale nutrient losses from subsurface tile drainage networks. In this study, short-term variations in discharge and chemistry were examined from a tile outlet collecting subsurface tile flow from a 963 ha agricultural watershed. Study objectives were to apply analytical techniques from karst springs to tile discharge to evaluate water sources and estimate the loads of agricultural pollutants discharged from the tile with conduit, intermediate and diffuse flow regimes. A two-member mixing model using nitrate, chloride and specific conductance was used to distinguish rainwater versus groundwater inputs. Results indicated that groundwater comprised 75% of the discharge for a three-day storm period and rainwater was primarily concentrated during the hydrograph peak. A contrasting pattern of solute concentrations and export loads was observed in tile flow. During base flow periods, tile flow consisted of diffuse flow from groundwater sources and contained elevated levels of nitrate, chloride and specific conductance. During storm events, suspended solids and pollutants adhered to soil surfaces (phosphorus, ammonium and organic nitrogen) were concentrated and discharged during the rapid, conduit flow portion of the hydrograph. During a three-day period, conduit flow occurred for 5.6% of the time but accounted for 16.5% of the total flow. Nitrate and chloride were delivered primarily with diffuse flow (more than 70%), whereas 80-94% of total suspended sediment, phosphorus and ammonium were exported with conduit and intermediate flow regimes. Understanding the water sources contributing to tile drainage and the manner by which pollutant discharge occurs from these systems (conduit, intermediate or diffuse flow) may be useful for designing, implementing and evaluating non-point source reduction strategies in tile-drained landscapes. ?? 2007 Elsevier B.V. All rights reserved.

Journal of Hydrology↗

USGS2014

Relationships between water and gas chemistry in mature coalbed methane reservoirs of the Black Warrior Basin

Water and gas chemistry in coalbed methane reservoirs of the Black Warrior Basin reflects a complex interplay among burial processes, basin hydrodynamics, thermogenesis, and late-stage microbial methanogenesis. These factors are all important considerations for developing production and water management strategies. Produced water ranges from nearly potable sodium-bicarbonate water to hypersaline sodium-chloride brine. The hydrodynamic framework of the basin is dominated by structurally controlled fresh-water plumes that formed by meteoric recharge along the southeastern margin of the basin. The produced water contains significant quantities of hydrocarbons and nitrogen compounds, and the produced gas appears to be of mixed thermogenic-biogenic origin. Late-stage microbial methanogenesis began following unroofing of the basin, and stable isotopes in the produced gas and in mineral cements indicate that late-stage methanogenesis occurred along a CO 2 -reduction metabolic pathway. Hydrocarbons, as well as small amounts of nitrate in the formation water, probably helped nourish the microbial consortia, which were apparently active in fresh to hypersaline water. The produced water contains NH 4 + and NH 3 , which correlate strongly with brine concentration and are interpreted to be derived from silicate minerals. Denitrification reactions may have generated some N 2 , which is the only major impurity in the coalbed gas. Carbon dioxide is a minor component of the produced gas, but significant quantities are dissolved in the formation water. Degradation of organic compounds, augmented by deionization of NH 4 + , may have been the principal sources of hydrogen facilitating late-stage CO 2 reduction.

Alabama↗

USGS2008

Environmental presence and persistence of pharmaceuticals: An overview

Emerging contaminants (ECs) in the environment – that is, chemicals with domestic, municipal, industrial, or agricultural sources that are not commonly monitored but may have the potential for adverse environmental effects – is a rapidly growing field of research. The use of “emerging” is not intended to infer that the presence of these compounds in the environment is new. These chemicals have been released into the environment as long as they have been in production or, in the case of hormones and other endogenous compounds, since the rise of animal life. What is emerging is the interest by the scientific and lay communities in the presence of these chemicals in the environment, the analytical capabilities required for detection, and the subtle effects that very small concentrations of these chemicals appear to have on aquatic biota. In December 2006, Environmental Science & Technology devoted an entire special issue (volume 40, number 23) to the topic of ECs, illustrating the increased interest in the subject. Within the EGs, one particular class that has seen a substantial increase in research over the past 10 years is pharmaceuticals and personal-care products (PPCPs). This increased research interest can be demonstrated by several means, including requests for proposals from funding agencies, but the clearest indication of a focused effort to understand the introduction, transformation, and potential health and environmental effects of PPCPs and ECs, in general, is the number of published reports. This increase can be shown by examining six environmental journals that regularly publish PPCP-related papers – Chemosphere , Environmental Science & Technology , Environmental Toxicology and Chemistry , Science of the Total Environment , Water Research , and Water Science and Technology . In 1998 there were 22 papers published on pharmaceuticals, antibiotics, or drugs in these 6 journals; by 2006, this number increased sixfold to 132 papers (Figure 1.1). This growth can be attributed to a number of factors. The presence of pharmaceuticals in surface-water samples from Europe and the United States was documented in several sentinel papers. These ground-breaking works encouraged other scientists to examine the rivers, streams, lakes, and reservoirs in their regions for such chemicals. In addition, the intense public attention paid to news reports on the environmental detections of these chemicals and possible effects of aquatic life has made this issue visible to the wastewater-treatment, drinking-water treatment, and regulatory communities. This has driven the funding bodies associated with these communities to fund studies or request proposals that address the presence, fate, and effects of PPCPs in aquatic systems. The release of the first comprehensive reconnaissance of pharmaceuticals and other wastewater contaminants in the United States provides an example of the intense media interest in this topic. Within 6 days on online publication of this study, 72 newspapers across the United States had published articles describing the results, either locally written or based on international media syndicate reports. There also was substantial concurrent coverage by local and national radio and television outlets, including the Cable News Network, ABC World News Tonight , and National Public Radio. A substantial fraction of these news stories may be attributable to press releases and media briefings prior to publication. However, the interest by television and print journalists in reporting the results of a peer-reviewed journal article to the general public was motivated by the recognition that describing the presence of PPCPs in water supplies would be of interest to the public. To better convey the results of the study published by Koplin et al. to the public, a separate general-interest fact sheet was published to summarize the important points of the study. Because PPCPs are commonly and widely used by individuals, there is likely a preexisting, personal identification with these compounds that does not occur for the wide range of other organic and inorganic contaminants whose presence in the environment has previously been described. This greater public “name recognition” makes itself known through the media to the regulatory and technical community and has prompted interest in sponsoring research that defines the composition and concentrations of PPCPs in potential sources and their fate and effects following relase into the environment. Independent of the drivers that potentially fuel the interest in studies of PPCPs, it is clear that PPCP research has grown beyond surface-water studies to examine issues such as: • Presence in other matrices, such as groundwater, landfill leachates, sediments, and biosolids. • Environmental transport and fate in surface water, groundwater, and soils amended with reclaimed water or biosolids. • PPCP source elucidation, such as wastewater treatment plant (WWTP) effluents, confined animal feeding operations (CAFOs), and aquaculture. • Removal during wastewater and drinking-water treatment. • Effects on aquatic ecosystems, terrestrial ecosystems, and human health. The chapters in this book provide an extensive examination of current environmental pharmaceutical research and are divided into three sections: “Occurrence and Analysis of Pharmaceuticals in the Environment,” “Environment Fate and Transformations of Veterinary Pharmaceuticals,” and “treatment of Pharmaceuticals in Drinking Water and Wastewater.” The purpose of this introductory overview chapter is to outline current (2004-2006) knowledge about the presence and concentration of PPCPs as described in the published literature. Previous reviews should be consulted for discussions on pre-2004 publications. Those reviews will provide the reader with a comprehensive introduction to the topic of PPCPs in the environment. This chapter describes the sources of PPCPs and other organic contaminants often associated with human wastewater into the environment, the range of concentrations present in various environmental compartments, and the potential routes of removal/sequestration. An overview of the sources and fate of veterinary pharmaceuticals will be discussed in Chapter 5, “Fate and Transport of Veterinary Medicines in the Soil Environment.”

Book chapter↗

USGS1989

Chemistry and origin of minor and trace elements in vitrinite concentrates from a rank series from the eastern United States, England, and Australia

A rank series consisting of twelve vitrinite concentrates and companion whole-coal samples from mined coal beds in the eastern United States, England, and Australia were analyzed for C, H, N, O, ash, and 47 trace and minor elements by standard elemental, instrumental neutron activation analysis (INAA), and direct-current-arc spectrographic (DCAS) techniques. The reflectance of vitrinite, atomic H:C and O:C, and ash-free carbon data were used to determine ranks that range from high-volatile C bituminous coal to meta-anthracite. A van Krevelen (atomic H:C vs. O:C) diagram of the vitrinite concentrates shows a smooth curve having its lowest point at H:C = 0.18 and O:C = 0.01. This improves the van Krevelen diagram by the addition of our vitrinite concentrate from meta-anthracite from the Narragansett basin of New England. Boron content (400–450 ppm) in two Illinois basin vitrinite concentrates was about an order of magnitude higher than B contents in other concentrates analyzed. We attribute this to marine origin or hydrothermal activity. The alkaline-earth elements Ca, Mg and Ba (DCAS) have higher concentrations in our vitrinite concentrates from bituminous coals of the Appalachian basin, than they do in vitrinite concentrates from the marine-roofed bituminous coals of the Illinois basin; therefore, a nonmarine origin for these alkaline-earth elements is postulated for the Appalachian basin coals. An ion-exchange mechanism due to high concentrations of these elements as ions in diagenetic water, but probably not recent ground water, may be responsible for the relatively high values of these elements in Appalachian concentrates. Higher concentrations of Ni and Cr in one of the English vitrinite concentrates and of Zr in the Australian concentrate probably indicate organic association and detrital influence, respectively.

International Journal of Coal Geology↗

USGS2013

Emissions of carbon dioxide and methane from a headwater stream network of interior Alaska

Boreal ecosystems store significant quantities of organic carbon (C) that may be vulnerable to degradation as a result of a warming climate. Despite their limited coverage on the landscape, streams play a significant role in the processing, gaseous emission, and downstream export of C, and small streams are thought to be particularly important because of their close connection with the surrounding landscape. However, ecosystem carbon studies do not commonly incorporate the role of the aquatic conduit. We measured carbon dioxide (CO 2 ) and methane (CH 4 ) concentrations and emissions in a headwater stream network of interior Alaska underlain by permafrost to assess the potential role of stream gas emissions in the regional carbon balance. First-order streams exhibited the greatest variability in fluxes of CO 2 and CH 4, and the greatest mean p CO 2 . High-resolution time series of stream p CO 2 and discharge at two locations on one first-order stream showed opposing p CO 2 responses to storm events, indicating the importance of hydrologic flowpaths connecting CO 2 -rich soils with surface waters. Repeated longitudinal surveys on the stream showed consistent areas of elevated p CO 2 and p CH 4 , indicative of discrete hydrologic flowpaths delivering soil water and groundwater having varying chemistry. Up-scaled basin estimates of stream gas emissions suggest that streams may contribute significantly to catchment-wide CH 4 emissions. Overall, our results indicate that while stream-specific gas emission rates are disproportionately high relative to the terrestrial landscape, both stream surface area and catchment normalized emission rates were lower than those documented for the Yukon River Basin as a whole. This may be due to limitations of C sources and/or C transport to surface waters.

Journal of Geophysical Research G: Biogeosciences↗

USGS2010

Identification of a novel arsenite oxidase gene, arxA, in the haloalkaliphilic, arsenite-oxidizing bacterium alkalilimnicola ehrlichii strain MLHE-1

Although arsenic is highly toxic to most organisms, certain prokaryotes are known to grow on and respire toxic metalloids of arsenic (i.e., arsenate and arsenite). Two enzymes are known to be required for this arsenic-based metabolism: (i) the arsenate respiratory reductase (ArrA) and (ii) arsenite oxidase (AoxB). Both catalytic enzymes contain molybdopterin cofactors and form distinct phylogenetic clades (ArrA and AoxB) within the dimethyl sulfoxide (DMSO) reductase family of enzymes. Here we report on the genetic identification of a “new” type of arsenite oxidase that fills a phylogenetic gap between the ArrA and AoxB clades of arsenic metabolic enzymes. This “new” arsenite oxidase is referred to as ArxA and was identified in the genome sequence of the Mono Lake isolate Alkalilimnicola ehrlichii MLHE-1, a chemolithoautotroph that can couple arsenite oxidation to nitrate reduction. A genetic system was developed for MLHE-1 and used to show that arxA (gene locus ID mlg _ 0216 ) was required for chemoautotrophic arsenite oxidation. Transcription analysis also showed that mlg _ 0216 was only expressed under anaerobic conditions in the presence of arsenite. The mlg _ 0216 gene is referred to as arxA because of its greater homology to arrA relative to aoxB and previous reports that implicated Mlg_0216 (ArxA) of MLHE-1 in reversible arsenite oxidation and arsenate reduction in vitro . Our results and past observations support the position that ArxA is a distinct clade within the DMSO reductase family of proteins. These results raise further questions about the evolutionary relationships between arsenite oxidases (AoxB) and arsenate respiratory reductases (ArrA). Arsenic is toxic to most organisms and is known to cause cancer in humans. However, bacteria have adapted several biotransformation pathways that function to either couple the reduction or oxidation of arsenicals to energy conservation and growth (1). The enzymologies of these two pathways have several features in common. The arsenate respiratory reductase (ArrAB) and arsenite oxidase (AoxAB) enzymes are usually composed of at least two subunits, a small iron-sulfur cluster-containing subunit (ArrB and AoxA) and a larger molybdopterin-containing catalytic subunit (ArrA and AoxB). Although they catalyze arsenic redox chemistry, ArrA and AoxB form distinct phylogenetic clades within the dimethyl sulfoxide (DMSO) reductase family of molybdenum-containing enzymes (16, 24). Culture-dependent approaches have resulted in the isolation of a variety of diverse bacteria that metabolize arsenic (reviewed in reference 26). Many of these isolates have had their genomes sequenced, which has been insightful for understanding the composition and diversity of arr and aox gene clusters. In the arsenite-oxidizing nitrate reducer Alkalilimnicola ehrlichii strain MLHE-1 (a haloalkaliphile isolated from Mono Lake [CA]) (10, 15), bioinformatic analysis of its genome revealed the absence of genes homologous to the arsenite oxidase genes of the aoxB type. Instead, two genes ( mlg _ 0216 and mlg _ 2426 ) were identified that better resembled the catalytic subunit of the arsenate respiratory reductase (20); however, MLHE-1 has not been shown to respire (or reduce) arsenate (15). Recent work by Richey et al. (20) showed that the Mlg_0216 protein (and not Mlg_2426) was expressed under chemolithoautotrophic (10 mM arsenite and 10 mM nitrate) growth conditions. Moreover, it was shown that Mlg_0216 exhibits both arsenate reductase and arsenite oxidase activities in vitro . These observations raised the question, is the mlg _ 0216 gene required for arsenite oxidation in vivo ? In this report, we addressed this question by developing a genetic system in MLHE-1, generating strains with mutations in mlg _ 0216 and mlg _ 2426 , and physiologically characterizing the resulting strains. Our results implicate mlg _ 0216 in chemolithoautotrophic arsenite oxidation coupled to nitrate respiration.

Journal of Bacteriology↗

USGS1988

Ferromanganese deposits from the Gulf of Alaska Seamount Province: Mineralogy, chemistry, and origin

Ferromanganese-oxide deposits dredged from four seamounts (Welker, Miller, Murray, and Patton) in the Gulf of Alaska Seamount Province include poorly crystallized microlaminated crusts on basalt substrate, well-crystallized Mn-oxide veins in epiclastic sedimentary rocks, and crystalline Mn-oxide layers and micronodules in phosphorite. The principal rock types dredged are alkali-basalt pillow fragments and tuffaceous conglomerate and sandstone. The glassy rims of pillow fragments, the glassy goundmass of large volcanic clasts, and the tuffaceous component of the sediment are altered to palagonite. Other low-temperature alteration products include phillipsite, smectite, and carbonate-apatite.Thick (10–50 mm) Fe–Mn crusts consist mainly of δ-MnO 2 ; straight and cuspate growth laminae indicate variable growth rates and periods of nondeposition. A larger number of detrital particles toward the top of thick crusts record the increasing influence of active volcanoes of the Aleutian arc during northwestward movement of the Pacific plate. Thick crusts on basalt substrate have higher Mn/Fe ratios and lower Co content than Fe–Mn crusts from low-latitude seamounts of the central Pacific region. Thin (< 10 mm) crusts on volcaniclastic substrate contain todorokite and birnessite and have higher Mn/Fe ratios, Ni, and Cu and lower Fe and Co than thick Gulf of Alaska crusts.Veins of todorokite and cryptomelane with complex internal structure occur in altered tuffaceous sandstone and conglomerate from Miller Seamount. Fibrous todorokite has a composition similar to those of other marine examples but may contain up to 7% Mn 2+ in M2 sites. Microprobe analysis of the marine cryptomelane indicates a composition that is approximately (K,Ba) 1–2 (Mn 4+ ,Co) 7–8 O 16 ∙ x (H 2 O).A third type of Fe–Mn deposit in phosphorite is an intimate mixture of todorokite (and minor δ-MnO 2 )-bearing layers and micronodules, carbonate-apatite, and phillipsite that encloses grains of altered volcanic glass and lithic fragments.The microlaminated structure, mineralogy (predominantly δ-MnO 2 ), and composition (Mn/Fe ratio and transition metal, rare earth element, U, and Th contents) of the thick crusts are characteristic of hydrogenetic Fe–Mn crusts elsewhere in the Pacific. Conversely, the crystallinity and chemical composition of the Mn-oxide veins and thin crusts indicate formation during diagenesis of the volcanogenic sediment substrate. Mn and other transition metals are mobilized during low-temperature oxidative alteration (palagonitization) of basaltic volcanic glass; the oxidation of Fe 2+ to Fe 3+ during palagonitization and the dissolution of the dilute biogenic fraction of the sediment combine to lower the Eh of ambient pore fluid and enhance the mobility of Mn 2+ . Diagenesis in the phosphatic sandstone from Patton Seamount involves organic-rich sediment and pore waters elevated in phosphorus owing to upwelling above a large volcanic edifice.

Alaska↗

USGS1989

The geology, botany and chemistry of selected peat-forming environments from temperate and tropical latitudes

Peat has been studied in several geologic settings: (1) glaciated terrain in cold temperate Maine and Minnesota, U.S.A.; (2) an island in the Atlantic Ocean off the coast of Maine, where sea level is rising; (3) the warm temperate U.S. Atlantic and Gulf Coastal Plains, where sea level has changed often; and (4) the tropical coast of Sarawak, Malaysia, and the tropical delta of the Batang Hari River, Sumatra, Indonesia. Most of these deposits are domed (ombrotrophic or partly ombrotrophic) bogs in which peat accumulation continued above the surface of the surrounding soil. However, the bogs of the U.S. Atlantic and Gulf Coastal Plains are comparatively not as domed, and many have almost level surfaces. In some bogs, aquatic or semi-aquatic plant materials accumulated, replaced water in the depressions, and formed a surface on which marsh or swamp vegetation could subsequently live, die, and accumulate. In others, the plant materials accumulated initially on level silt or sand surfaces supporting marshes or swamps. As the peat dome formed, plants growing on it changed from luxuriant ones near the base of the dome, where nutrients were brought into the bog by surface and ground water, to stunted ones at the top of the dome, where the raised bogs are fed by nutrient-poor precipitation. The physical and chemical changes that take place in the sequence of environments from the pond stage of deposit development, through the grassy marsh stage, through the forested swamp stage, and finally through the heath dome stage can be measured in terms of acidity and ash, volatile matter, carbon, hydrogen, nitrogen, sulfur and oxygen contents, as well as in the kind and distribution of trace elements. The organic and inorganic contents of the deposits relate to geomorphology, and geomorphology relates to their settings. As models of coal formation, some domed peat deposits may help in solving problems of distribution and character of ancient coal beds. But clearly not all peat deposits are precursors of coal. Most Holocene peat deposits are subject to destruction by erosion, fire and decomposition through microbial and chemical oxidation before burial. The best environments for coal precursors have biomass accumulation, a continuously rising water table within the mass, and minimum influx of clay and silt until preservation by burial. The most suitable settings for future economic coal deposits are domed bogs that accumulate thick, widespread peat having low ash and low sulfur contents. The ombrotrophic peat deposits of tropical Sarawak and Sumatra are thick and extensive, contain low-ash and low-sulfur peat, and have high heating values. They are considered to be the best tropical coal analogs because of their extent and chances of preservation; the base of the peat is below adjacent river levels, and chemical and structural conditions are favorable for accumulation.

International Journal of Coal Geology↗