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USGS2015

Effects of land use on greenhouse gas fluxes and soil properties of wetland catchments in the Prairie Pothole Region of North America

Wetland restoration has been suggested as policy goal with multiple environmental benefits including enhancement of atmospheric carbon sequestration. However, there are concerns that increased methane (CH 4 ) emissions associated with restoration may outweigh potential benefits. A comprehensive, 4-year study of 119 wetland catchments was conducted in the Prairie Pothole Region of the north-central U.S. to assess the effects of land use on greenhouse gas (GHG) fluxes and soil properties. Results showed that the effects of land use on GHG fluxes and abiotic soil properties differed with respect to catchment zone (upland, wetland), wetland classification, geographic location, and year. Mean CH 4 fluxes from the uplands were predictably low (< 0.02 g CH 4 m − 2 day − 1 ), while wetland zone CH 4 fluxes were much greater (< 0.001–3.9 g CH 4 m − 2 day − 1 ). Mean cumulative seasonal CH 4 fluxes ranged from roughly 0–650 g CH 4 m − 2 , with an overall mean of approximately 160 g CH 4 m − 2 . These maximum cumulative CH 4 fluxes were nearly 3 times as high as previously reported in North America. The overall magnitude and variability of N 2 O fluxes from this study (< 0.0001–0.0023 g N 2 O m − 2 day − 1 ) were comparable to previously reported values. Results suggest that soil organic carbon is lost when relatively undisturbed catchments are converted for agriculture, and that when non-drained cropland catchments are restored, CH 4 fluxes generally are not different than the pre-restoration baseline. Conversely, when drained cropland catchments are restored, CH 4 fluxes are noticeably higher. Consequently, it is important to consider the type of wetland restoration (drained, non-drained) when assessing restoration benefits. Results also suggest that elevated N 2 O fluxes from cropland catchments likely would be reduced through restoration. The overall variability demonstrated by this study was consistent with findings of other wetland investigations and underscores the difficulty in quantifying the GHG balance of wetland systems.

Iowa, Minnesota, North Dakota, South Dakota↗

USGS2016

Contrasting distributions of groundwater arsenic and uranium in the western Hetao basin, Inner Mongolia: Implication for origins and fate controls

Although As concentrations have been investigated in shallow groundwater from the Hetao basin, China, less is known about U and As distributions in deep groundwater, which would help to better understand their origins and fate controls. Two hundred and ninety-nine groundwater samples, 122 sediment samples, and 14 rock samples were taken from the northwest portion of the Hetao basin, and analyzed for geochemical parameters. Results showed contrasting distributions of groundwater U and As, with high U and low As concentrations in the alluvial fans along the basin margins, and low U and high As concentrations downgradient in the flat plain. The probable sources of both As and U in groundwater were ultimately traced to the bedrocks in the local mountains (the Langshan Mountains). Chemical weathering of U-bearing rocks (schist, phyllite, and carbonate veins) released and mobilized U as UO 2 (CO 3 ) 2 2 − and UO 2 (CO 3 ) 3 4 − species in the alluvial fans under oxic conditions and suboxic conditions where reductions of Mn and NO 3 − were favorable (OSO), resulting in high groundwater U concentrations. Conversely, the recent weathering of As-bearing rocks (schist, phyllite, and sulfides) led to the formation of As-bearing Fe(III) (hydr)oxides in sediments, resulting in low groundwater As concentrations. Arsenic mobilization and U immobilization occurred in suboxic conditions where reduction of Fe(III) oxides was favorable and reducing conditions (SOR). Reduction of As-bearing Fe(III) (hydr)oxides, which were formed during palaeo-weathering and transported and deposited as Quaternary aquifer sediments, was believed to release As into groundwater. Reduction of U(VI) to U(IV) would lead to the formation of uraninite, and therefore remove U from groundwater. We conclude that the contrasting distributions of groundwater As and U present a challenge to ensuring safe drinking water in analogous areas, especially with high background values of U and As.

Hetao Basin, Inner Mongolia↗

USGS2016

Surface-air mercury fluxes across Western North America: A synthesis of spatial trends and controlling variables

Mercury (Hg) emission and deposition can occur to and from soils, and are an important component of the global atmospheric Hg budget. This paper focuses on synthesizing existing surface-air Hg flux data collected throughout the Western North American region and is part of a series of geographically focused Hg synthesis projects. A database of existing Hg flux data collected using the dynamic flux chamber (DFC) approach from almost a thousand locations was created for the Western North America region. Statistical analysis was performed on the data to identify the important variables controlling Hg fluxes and to allow spatiotemporal scaling. The results indicated that most of the variability in soil-air Hg fluxes could be explained by variations in soil-Hg concentrations, solar radiation, and soil moisture. This analysis also identified that variations in DFC methodological approaches were detectable among the field studies, with the chamber material and sampling flushing flow rate influencing the magnitude of calculated emissions. The spatiotemporal scaling of soil-air Hg fluxes identified that the largest emissions occurred from irrigated agricultural landscapes in California. Vegetation was shown to have a large impact on surface-air Hg fluxes due to both a reduction in solar radiation reaching the soil as well as from direct uptake of Hg in foliage. Despite high soil Hg emissions from some forested and other heavily vegetated regions, the net ecosystem flux (soil flux + vegetation uptake) was low. Conversely, sparsely vegetated regions showed larger net ecosystem emissions, which were similar in magnitude to atmospheric Hg deposition (except for the Mediterranean California region where soil emissions were higher). The net ecosystem flux results highlight the important role of landscape characteristics in effecting the balance between Hg sequestration and (re-)emission to the atmosphere.

Science of the Total Environment↗

USGS2017

A hybrid machine learning model to predict and visualize nitrate concentration throughout the Central Valley aquifer, California, USA

Intense demand for water in the Central Valley of California and related increases in groundwater nitrate concentration threaten the sustainability of the groundwater resource. To assess contamination risk in the region, we developed a hybrid, non-linear, machine learning model within a statistical learning framework to predict nitrate contamination of groundwater to depths of approximately 500 m below ground surface. A database of 145 predictor variables representing well characteristics, historical and current field and landscape-scale nitrogen mass balances, historical and current land use, oxidation/reduction conditions, groundwater flow, climate, soil characteristics, depth to groundwater, and groundwater age were assigned to over 6000 private supply and public supply wells measured previously for nitrate and located throughout the study area. The boosted regression tree (BRT) method was used to screen and rank variables to predict nitrate concentration at the depths of domestic and public well supplies. The novel approach included as predictor variables outputs from existing physically based models of the Central Valley. The top five most important predictor variables included two oxidation/reduction variables (probability of manganese concentration to exceed 50 ppb and probability of dissolved oxygen concentration to be below 0.5 ppm), field-scale adjusted unsaturated zone nitrogen input for the 1975 time period, average difference between precipitation and evapotranspiration during the years 1971–2000, and 1992 total landscape nitrogen input. Twenty-five variables were selected for the final model for log-transformed nitrate. In general, increasing probability of anoxic conditions and increasing precipitation relative to potential evapotranspiration had a corresponding decrease in nitrate concentration predictions. Conversely, increasing 1975 unsaturated zone nitrogen leaching flux and 1992 total landscape nitrogen input had an increasing relative impact on nitrate predictions. Three-dimensional visualization indicates that nitrate predictions depend on the probability of anoxic conditions and other factors, and that nitrate predictions generally decreased with increasing groundwater age.

California↗

USGS2018

Oil and gas development footprint in the Piceance Basin, western Colorado

Understanding long-term implications of energy development on ecosystem functionrequires establishing regional datasets to quantify past development and determine relationships to predict future development. The Piceance Basin in western Colorado has a history of energy production and development is expected to continue into the foreseeable future due to abundant natural gas resources. To facilitate analyses of regional energy development we digitized all well pads in the Colorado portion of the basin, determined the previous land cover of areas converted to well pads over three time periods (2002–2006, 2007–2011, and 2012–2016), and explored the relationship between number of wells per pad and pad area to model future development. We also calculated the area of pads constructed prior to 2002. Over 21 million m 2 has been converted to well pads with approximately 13 million m 2 converted since 2002. The largest land conversion since 2002 occurred in shrub/scrub (7.9 million m 2 ), evergreen (2.1 million m 2 ), and deciduous (1.3 million m 2 ) forest environments based on National Land Cover Database classifications. Operational practices have transitioned from single well pads to multi-well pads, increasing the average number of wells per pad from 2.5 prior to 2002, to 9.1 between 2012 and 2016. During the same time period the pad area per well has increased from 2030 m 2 to 3504 m 2 . Kernel density estimation was used to model the relationship between the number of wells per pad and pad area, with these curves exhibiting a lognormal distribution. Therefore, either kernel density estimation or lognormal probability distributions may potentially be used to model land use requirements for future development. Digitized well pad locations in the Piceance Basin contribute to a growing body of spatial data on energy infrastructure and, coupled with study results, will facilitate future regional and national studies assessing the spatial and temporal effects of energy development on ecosystem function.

Colorado↗

USGS2019

Drinking water quality in the glacial aquifer system, northern USA

Groundwater supplies 50% of drinking water worldwide, but compromised water quality from anthropogenic and geogenic contaminants can limit usage of groundwater as a drinking water source. Groundwater quality in the glacial aquifer system, USA (GLAC), is presented in the context of a hydrogeologic framework that divides the study area into 17 hydrogeologic terranes. Results are reported at aquifer-system scale and regional (terrane) scale. This paper presents a quantitative assessment of groundwater quality in the GLAC using data from numerous sources for samples collected 2005–2013, compared to health-based and aesthetic (non-health) benchmarks, and evaluated with areal and population metrics. Concentrations above a benchmark are considered high. Trace elements are widespread across the study area, with an estimated 5.7 million people relying on groundwater with high concentrations of one or more trace elements; manganese and arsenic are most often at high concentration. Nitrate is found at high concentration in 4.0% of the study area, serving about 740 thousand people. Organic compounds including pesticides and volatile organic compounds are high in 2.0% of the assessed study area, with about 870 thousand people relying on groundwater with high concentrations of an organic compound. High arsenic and manganese concentrations occur primarily in the terranes with thick, stratigraphically complex, fine-grained glacial sediment, coincident with groundwater under reducing conditions (indicated by iron concentrations >100 μg/L); high nitrate is uncommon in those same terranes. When nitrate is high in thick, fine-grained, complex terranes, though, it is much more commonly associated with groundwater under more oxidizing conditions. Common geogenic trace elements occur at high concentration due to characteristic geologic and geochemical conditions. Conversely, anthropogenic nitrate and organic compounds are introduced at or near the land surface. High concentrations of nitrate or organic compounds are generally limited to areas in proximity where people live and use the chemicals.

Science of Total Environment↗

USGS2020

Spatial variability of phytoplankton in a shallow tidal freshwater system reveals complex controls on abundance and community structure

Estuaries worldwide are undergoing changes to patterns of aquatic productivity because of human activities that alter flow, impact sediment delivery and thus the light field, and contribute nutrients and contaminants like pesticides and metals. These changes can influence phytoplankton communities, which in turn can alter estuarine food webs. We used multiple approaches-including high-resolution water quality mapping, synoptic sampling, productivity and nitrogen uptake rates, Lagrangian parcel tracking, enclosure experiments and bottle incubations-over a short time period to take a “spatial snapshot” of conditions in the northern region of the San Francisco Estuary (California, USA) to examine how environmental drivers like light availability, nutrients, water residence time, and contaminants affect phytoplankton abundance and community attributes like size distribution, taxonomic structure, and nutrient uptake rates. Zones characterized by longer residence time (15–60 days) had higher chlorophyll-a concentrations (9 ± 4 µg L −1 ) and were comprised primarily of small phytoplankton cells (<5 µm, 74 ± 8%), lower ammonium concentrations (1 ± 0.8 µM), higher nitrate uptake rates, and higher rates of potential carbon productivity. Conversely, zones characterized by shorter residence time (1–14 days) had higher ammonium concentration (13 ± 5 µM) and lower chlorophyll-a concentration (5 ± 1 µg L −1 ) with diatoms making up a larger percent contribution. Longer residence time, however, did not result in the accumulation of large (>5 µm) cells considered important to pelagic food webs. Rather, longer residence time zones had a phytoplankton community comprised primarily of small cells, particularly picocyanobacteria that made up 38 ± 17% of the chlorophyll-a – nearly double the concentration seen in shorter residence time zones (22 ± 7% picocyanobacterial of chlorophyll-a). Our results suggest that water residence time in estuaries may have an effect as large or larger than that experimentally demonstrated for light, contaminants, or nutrients.

California↗

USGS2020

Estuarine submerged aquatic vegetation habitat provides organic carbon storage across a shifting landscape

Submerged aquatic vegetation (SAV) thrives across the estuarine salinity gradient providing valuable ecosystem services. Within the saline portion of estuaries, seagrass areas are frequently cited as hotspots for their role in capturing and retaining organic carbon (C org ). Non-seagrass SAV, located in the fresh to brackish estuarine areas, may also retain significant soil C org , yet their role remains unquantified. Given rapidly occurring landscape and salinity changes due to human and natural disturbances, landscape level carbon pool estimates from estuarine SAV habitat blue carbon estimates are needed. We assessed C org stocks in SAV habitat soils from estuarine freshwater to saline habitats (interior deltaic) to saline barrier islands (Chandeleur Island) within the Mississippi River Delta Plain (MRDP), Louisiana, USA. SAV habitats contain C org stocks equivalent to those reported for other estuarine vegetation types (seagrass, salt marsh, mangrove). Interior deltaic SAV C org stocks (231.6 ± 19.5 Mg C org ha −1 ) were similar across the salinity gradient, and significantly higher than at barrier island sites (56.6 ± 10.4 Mg C org ha −1 ). Within the MRDP, shallow water SAV habitat covers up to an estimated 28,000 ha, indicating that soil C org storage is potentially 6.4 ± 0.1 Tg representing an unaccounted C org pool. Extrapolated across Louisiana, and the Gulf of Mexico, this represents a major unaccounted pool of soil C org . As marshes continue to erode, the ability of coastal SAV habitat to offset some of the lost carbon sequestration may be valuable. Our estimates of C org sequestration rates indicated that conversion of eroding marsh to potential SAV habitat may help to offset the reduction of C org sequestration rates. Across Louisiana, we estimated SAV to offset this loss by as much as 79,000 Mg C yr −1 between the 1960s and 2000s.

Louisiana↗

USGS2020

Biological nitrogen fixation across major biomes in Latin America: Patterns and global change effects

Biological nitrogen fixation (BNF) supports terrestrial primary productivity and plays key roles in mediating human-induced changes in global nitrogen (N) and carbon cycling. However, there are still critical uncertainties in our understanding of the amount of BNF occurring across terrestrial ecosystems, and of how terrestrial BNF will respond to global change. We synthesized BNF data from Latin America, a region reported to sustain some of the highest BNF rates on Earth, but that is underrepresented in previous data syntheses. We used meta-analysis and modeling approaches to estimate BNF rates across Latin America's major biomes and to evaluate the potential effects of increased N deposition and land-use change on these rates. Unmanaged tropical and subtropical moist forests sustained observed and predicted total BNF rates of 10 ± 1 and 14 ± 1 kg N ha −1 y −1 , respectively, supporting the hypothesis that these forests sustain lower BNF rates than previously thought. Free-living BNF accounted for two-thirds of the total BNF in these forests. Despite an average 30% reduction of free-living BNF in response to experimental N-addition, our results suggest free-living BNF rate responses to current and projected N deposition across tropical and subtropical moist forests are small. In contrast, the conversion of unmanaged ecosystems to crop and pasture lands increased BNF rates across all terrestrial biomes, mostly in savannas, grasslands, and dry forests, increasing BNF rates 2-fold. The information obtained here provides a more comprehensive understanding of BNF patterns for Latin America.

Science of the Total Environment↗

USGS2022

Stable isotopes provide insight into sources and cycling of N compounds in the Sacramento-San Joaquin Delta, California, USA

River deltas and their diverse array of aquatic environments are increasingly impacted by anthropogenic inputs of nitrogen (N). These inputs can alter the N biogeochemistry of these systems and promote undesirable phenomena including harmful algae blooms and invasive aquatic macrophytes. To examine N sources and biogeochemical processes in the Sacramento-San Joaquin Delta, a river delta located in central California, USA, that is fed primarily by the Sacramento River, we utilized a multi-tracer approach that measured N species concentrations and stable isotope values monthly from April 2011 to November 2012 in samples collected from the channelized mainstem of the Sacramento River, two channelized distributaries of the Sacramento River, and the Cache Slough Complex, a network of Sacramento River tributaries and shallow water wetland habitat. We found that the Sacramento River and its channelized distributaries received N primarily in the form of NH 4 + from treated wastewater effluent and that NH 4 + was lost rapidly while NO 3 − was gained more slowly during subsequent downstream transit, driven by an array of biogeochemical processes whose identities could be constrained via examination of stable isotope values. The Cache Slough Complex, which was characterized by lower net flows and higher water residence times than the Sacramento River and its distributaries, received variable inputs of low conductivity water elevated in NH 4 + from the Sacramento River and higher conductivity water elevated in NO 3 − from landward tributaries. Deviations from expected conservative mixing of these sources were spatially variable but broadly indicative of local inputs of treated wastewater effluent NO 3 − , conversion of Sacramento River NH 4 + to NO 3 − via nitrification, uptake of NH 4 + and NO 3 − by phytoplankton, and remineralization of organic N. These findings highlight both the diversity in N dynamics in anthropogenically impacted river delta environments and the utility of a multi-tracer approach in constraining these processes in such complex systems.

California↗

USGS2024

The interplay of future solar energy, land cover change, and their projected impacts on natural lands and croplands in the US

Projections for deep decarbonization require large amounts of solar energy, which may compete with other land uses such as agriculture, urbanization, and conservation of natural lands. Existing capacity expansion models do not integrate land use land cover change (LULC) dynamics into projections. We explored the interaction between projected LULC, solar photovoltaic (PV) deployment, and solar impacts on natural lands and croplands by integrating projections of LULC with a model that can project future deployment of solar PV with high spatial resolution for the conterminous United States. We used scenarios of LULC projections from the Intergovernmental Panel on Climate Change Special Report on Emission Scenarios from 2010 to 2050 and two electricity grid scenarios to model future PV deployment and compared those results against a baseline that held 2010 land cover constant through 2050. Though solar PV's overall technical potential was minimally impacted by LULC scenarios, deployed PV varied by −16.5 to 11.6 % in 2050 from the baseline scenario. Total land requirements for projected PV were similar to other studies, but measures of PV impacts on natural systems depended on the underlying land change dynamics occurring in a scenario. The solar PV deployed through 2050 resulted in 1.1 %–2.4 % of croplands and 0.3 %–0.7 % of natural lands being converted to PV. However, the deepest understanding of PV impacts and interactions with land cover emerged when the complete net gains and losses from all land cover change dynamics, including PV, were integrated. For example, one of the four LULC projections allows for high solar development and a net gain in natural lands, even though PV drives a larger percentage of natural land conversion. This paper shows that integrating land cover change dynamics with energy expansion models generates new insights into trade offs between decarbonization, impacts of renewables, and ongoing land cover change.

conterminous United States↗

USGS2024

Seasonally varying contributions of contemporaneous and lagged sources of instream total nitrogen and phosphorus load across the Illinois River basin

Quantifying nutrient sources in streams, their temporal and spatial variability, and drivers of that variability can support effective water resources management. Yet a lack of data and modeling capabilities has previously prevented comprehensive quantification across both space and time. Here a dynamic SPARROW (Spatially Referenced Regressions on Watershed attributes) model that accounts for a lagged delivery of nutrients to streams was developed and applied to simulate seasonal and source-specific total nitrogen (TN) and total phosphorus (TP) loads in streams across the Illinois River basin (IRB). Dynamic load predictions from 2000 through 2020 revealed that a third of the TN and a quarter of the TP instream load originated from non-point sources that were lagged in their delivery from land-application to streams by more than a season. This lagged mass was the largest overall TN source—which was estimated as a lagged expression of previous seasonal non-point sources including fertilizer, manure, atmospheric deposition and fixation, and urban land use. Treated wastewater effluent was the largest TP source exported from the basin, contributing 39 % of the TP load and 15 % of the TN load, and dominated the load in the upper Illinois River near Chicago. Loads in the lower river during this period, conversely, were attributed primarily to a mix of agricultural sources and their lagged fractions from headwater tributaries. Instream processes removed 10 % of the TN load while only 4 % of the TP load was removed during instream transport. With appropriate datasets, the models could be extended to other basins or time periods and used to forecast future seasonal nutrient loads.

Illinois↗

USGS2020

Probabilistic regional-scale liquefaction triggering modeling using 3D Gaussian processes

Liquefaction is a major cause of coseismic damages, occurring irregularly over hundreds or thousands of square kilometers in large earthquakes. Large variations in the extent and location of liquefaction have been observed in recent earthquakes, motivating the need for prediction methods that consider the spatial heterogeneity of geologic deposits at a regional scale. Contemporary regional-scale liquefaction hazard analyses are typically performed using only surficial data, which does not address the complicated subsurface mechanics and spatial variability associated with artificial fill and natural soil deposits. In this study, we develop a probabilistic, regional-scale, subsurface model using data from hundreds of borings to better understand subsurface conditions that could influence liquefaction. We then use this subsurface sample database to train Gaussian process models, yielding 3D independent random fields of groundwater depth, soil plasticity, and penetration resistance for each geologic unit. We incorporate the Gaussian process models into probabilistic liquefaction triggering procedures, producing 3D estimates of the probability of liquefaction for an example study area in Portland, Oregon. Near sampling locations, the variance of the Gaussian process models approaches the variance of site-specific liquefaction triggering procedures. Conversely, when no sample data are nearby to condition a Gaussian process, the variance approaches the marginal variance of the entire recorded dataset. Thus, the procedure described in this study unifies probabilistic site-specific and regional-scale liquefaction triggering procedures and provides an important step towards quantitative liquefaction hazard assessments for regionally distributed infrastructures, such as levees, pipelines, roadways, and electrical transmission facilities.

Oregon↗

USGS2013

Regulation of gonadal sex ratios and pubertal development by the thyroid endocrine system in zebrafish ( Danio rerio )

We examined associations between thyroid condition, gonadal sex and pubertal development in zebrafish. Seventy-two-hour postfertilization larvae were reared in untreated medium or in the presence of goitrogens (sodium perchlorate, 0.82 mM; methimazole, 0.15 and 0.3 mM) or thyroxine (1 and 10 nM) for 30 days. Thyrocyte height, gonadal sex and gonadal development were histologically determined at 45 and 60 days postfertilization (dpf). Thyrocyte hypertrophy, an index of hypothyroidism, was observed at 45 and 60 dpf in perchlorate-treated but only at 45 dpf in methimazole-treated fish. Similarly, gonadal sex ratios were biased toward ovaries relative to control animals at 45 and 60 dpf in perchlorate-treated fish but only at 45 dpf in methimazole-treated fish. Gonadal sex ratios were biased toward testes at 45 and 60 dpf in thyroxine-treated fish. Spermatogenesis was delayed in testes from goitrogen-treated fish at 60 dpf relative to control values, but was unaffected in testes from thyroxine-treated individuals. Oogenesis seemed to be nonspecifically delayed in all treatments relative to control at 60 dpf. This study confirmed the previously reported association between hypothyroid condition and ovarian-skewed ratios, and hyperthyroid condition and testicular-skewed ratios, and also showed that male pubertal development is specifically delayed by experimental hypothyroidism. The simultaneous recovery from the hypothyroid and ovary-inducing effects of methimazole by 60 dpf (27 days post-treatment) suggests that the ovary-skewing effect of goitrogens is reversible when thyroid conditions return to basal levels before developmental commitment of gonadal sex. Conversely, the masculinizing effect of hyperthyroidism seems to be stable and perhaps permanent.

General and Comparative Endocrinology↗

USGS2017

Development of the mixed conifer forest in northern New Mexico and its relationship to Holocene environmental change

Chihuahueños Bog (2925 m) in the Jemez Mountains of northern New Mexico contains one of the few records of late-glacial and postglacial development of the mixed conifer forest in southwestern North America. The Chihuahueños Bog record extends to over 15,000 cal yr BP. An Artemisia steppe, then an open Picea woodland grew around a small pond until ca. 11,700 cal yr BP when Pinus ponderosa became established. C/N ratios, δ 13 C and δ 15 N values indicate both terrestrial and aquatic organic matter was incorporated into the sediment. Higher percentages of aquatic algae and elevated C/N ratios indicate higher lake levels at the opening of the Holocene, but a wetland developed subsequently as climate warmed. From ca. 8500 to 6400 cal yr BP the pond desiccated in what must have been the driest period of the Holocene there. C/N ratios declined to their lowest Holocene levels, indicating intense decomposition in the sediment. Wetter conditions returned after 6400 cal yr BP, with conversion of the site to a sedge bog as groundwater levels rose. Higher charcoal influx rates after 6400 cal yr BP probably result from greater biomass production rates. Only minor shifts in the overstory species occurred during the Holocene, suggesting that mixed conifer forest dominated throughout the record.

Quaternary Research↗

USGS1972

Microcoulometric measurement of water in minerals

A DuPont Moisture Analyzer is used in a microcoulometric method for determining water in minerals. Certain modifications, which include the heating of the sample outside the instrument, protect the system from acid gases and insure the conversion of all hydrogen to water vapor. Moisture analyzer data are compared to concurrent data obtained by a modified Penfield method. In general, there is a positive bias of from 0.1 to 0.2% in the moisture analyzer results and a similarity of bias in minerals of the same kind. Inhomogeneity, sample size, and moisture pick-up are invoked to explain deviations. The method is particularly applicable to small samples.

Analytica Chimica Acta↗

USGS1985

Retention behavior of long chain quaternary ammonium homologues and related nitroso-alkymethylamines

Several chromatographic methods have been utilized to study the retentionbehavior of a homologous series of n -alkylbenzyldimethylammonium chlorides (ABDAC) and the corresponding nitroso- n -alkylmethylamines (NAMA). Linear correlation of the logarithmic capacity factor ( k ') with the number of carbons in the alkyl chain provides useful information on both gas chromatographic (GC) and high-performance liquid chromatographich (HPLC) retention parameters of unknown components. Under all conditions empolyed, GC methodology has proved effective in achieving complete resolution of the homologous mixture of NMA despite its obvious inadequacy in the separation of E-Z configurational isomers. Conversely, normal-phase HPLC on silica demonstrates that the selectivity (a) value for an E-Z pair is much higher than that for an adjacent homologous pair. In the reversed-phase HPLC study, three different silica-based column systems were examined under various mobile phase conditions. The extent of variation in k ' was found to be a function of the organic modifier, counter-ion concentration, eluent pH, nature of counter-ion, and the polarity and type of stationary phase. The k '—[NaClO 4 ] profiles showed similar trends between the ABDAC and the NAMA series, supporting the dipolar electronic structures of the latter compounds. Mobile phase and stationary phase effects on component separation are described. The methodology presented establishes the utility of HPLC separation techniques as versatile analytical tools for practical application.

Journal of Chromatography↗

USGS1987

Chiral-phase high-performance liquid chromatography of rotenoid racemates

The high-performance liquid chromatograhic (HPLC) behavior of parent rotenoids (type I) and the hydroxyl-analogues (type II) on three different chiral stationary phases (CSPs) was studied. Separations of optical isomers were achieved in various degrees depending largely upon the rotenoidal structures and the CSP types employed. Enantiomers of all but elliptone compounds were separable on β-cyclodextrin-bonded silica (CDS). Without exception, the 12a-hydroxyrotenoid antipodes were resolved on Pirkle's phenylglycine-bonded silica (PGS) despite unsuccessful attenmpts to resolve the type I rotenoidal racemates. Conversely, optical resolution of the latter rotenoids was accomplished by using a helical polytriphenylmethylacrylate-coated silica (TPS) column and the observed separation factors (α values) ranged from 1.14 to 1.90. The results from HPLC of type II rotenoids on TPS (α = 1.00–1.63) suggested that variations in E-ring structures had profound influence on the resolution outcome. Conjugated double bonds on the E-ring and the desisopropylation of the five-membered E-ring ot type II rotenoids appeared to be important structural features for chiral recognition involving the TPS substrate. In both reversed-phase (CDS) and normal-pahse (PGS and TPS) HPLC modes, the less polar enantiomers were the 6aβ,12aβ-rotenoids as observed in most cases, though this relationship was reversed in the cases of deguelin and hydroxyelliptone probably due to conformational effects of rotenoidal ring systems.

Journal of Chromatography↗