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USGS2022

Level and pattern of overstory retention shape the abundance and long-term dynamics of natural and created snags

Standing dead trees, or snags, serve myriad functions in natural forests, but are often scarce in forests managed for timber production. Variable retention (VR), the retention of live and dead trees through harvest, has been adopted globally as a less intensive form of regeneration harvest. In this study, we explore how two key elements of VR systems — level (amount) and spatial pattern of live-tree retention — affect the carryover and post-harvest dynamics of natural and artificially created snags. We present nearly two decades of data from the DEMO Study, a regional-scale experiment in VR harvests of Douglas-fir-dominated forests in the Pacific Northwest. Snag losses to harvest were greater at 15 than at 40% retention (67 vs. 47% declines in density) and greater in dispersed than in aggregated treatments (64 vs. 50% declines). Densities of hard and tall (≥5 m) snags were particularly sensitive to low-level dispersed retention, declining by 76 and 81%, respectively. Despite these losses, post-harvest densities correlated with pre-harvest densities for most snag size and decay classes. In contrast to initial harvest effects, snag densities changed minimally over the post-harvest period (years 1 to 18 or 19), with low rates of recruitment offsetting low rates of loss. Post-harvest survival of snags was greater at 15 than at 40% retention (79 vs. 69%), as were rates of decay (68 vs. 52% of hard snags transitioned to soft). However, pattern had no effect on either process. Snag recruitment did not vary with retention level or pattern at the scale of the 13-ha harvest unit, but was several-fold greater in the 1-ha aggregates (14.3–27.8 snags ha −1 ) than in the corresponding dispersed treatments (4.2–5.3 snags ha −1 ). Snag size (diameter) distributions showed greater change in dispersed than in aggregated treatments, reflecting greater loss of smaller snags and recruitment biased toward larger snags. Created snags showed uniformly high survival (97%), irrespective of treatment, but rates of decay were greater at lower retention. If a goal of VR is to sustain snag abundance and diversity through harvest, emphasis should be placed on minimizing initial losses, either by reducing the intensity of felling in areas of dispersed retention or locating forest aggregates in areas of greater initial snag density, diversity, or incipient decay.

Forest Ecology and Management↗

USGS2011

Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ 13 C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.

Geochimica et Cosmochimica Acta↗

USGS2014

Re-Os geochronology and Os isotope fingerprinting of petroleum sourced from a Type I lacustrine kerogen: insights from the natural Green River petroleum system in the Uinta Basin and hydrous pyrolysis experiments

Rhenium–osmium (Re–Os) geochronology of marine petroleum systems has allowed the determination of the depositional age of source rocks as well as the timing of petroleum generation. In addition, Os isotopes have been applied as a fingerprinting tool to correlate oil to its source unit. To date, only classic marine petroleum systems have been studied. Here we present Re–Os geochronology and Os isotope fingerprinting of different petroleum phases (oils, tar sands and gilsonite) derived from the lacustrine Green River petroleum system in the Uinta Basin, USA. In addition we use an experimental approach, hydrous pyrolysis experiments, to compare to the Re–Os data of naturally generated petroleum in order to further understand the mechanisms of Re and Os transfer to petroleum. The Re–Os geochronology of petroleum from the lacustrine Green River petroleum system (19 ± 14 Ma – all petroleum phases) broadly agrees with previous petroleum generation basin models (∼25 Ma) suggesting that Re–Os geochronology of variable petroleum phases derived from lacustrine Type I kerogen has similar systematics to Type II kerogen (e.g., Selby and Creaser, 2005a, Selby and Creaser, 2005b and Finlay et al., 2010). However, the large uncertainties (over 100% in some cases) produced for the petroleum Re–Os geochronology are a result of multiple generation events occurring through a ∼3000-m thick source unit that creates a mixture of initial Os isotope compositions in the produced petroleum phases. The 187Os/188Os values for the petroleum and source rocks at the time of oil generation vary from 1.4 to 1.9, with the mode at ∼1.6. Oil-to-source correlation using Os isotopes is consistent with previous correlation studies in the Green River petroleum system, and illustrates the potential utility of Os isotopes to characterize the spatial variations within a petroleum system. Hydrous pyrolysis experiments on the Green River Formation source rocks show that Re and Os transfer are mimicking the natural system. This transfer from source to bitumen to oil does not affect source rock Re–Os systematics or Os isotopic compositions. This confirms that Os isotope compositions are transferred intact from source to petroleum during petroleum generation and can be used as a powerful correlation tool. These experiments further confirm that Re–Os systematics in source rocks are not adversely affected by petroleum maturation. Overall this study illustrates that the Re–Os petroleum geochronometer and Os isotope fingerprinting tools can be used on a wide range of petroleum types sourced from variable kerogen types.

Utah↗

USGS2018

Position-specific 13C distributions within propane from experiments and natural gas samples

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, ‘bulk’ isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13 C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13 C/ 12 C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ 13 C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ 13 C and then increasing in both center and terminal position δ 13 C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems.

Geochimica et Cosmochimica Acta↗

USGS2020

Position-specific distribution of hydrogen isotopes in natural propane: Effects of thermal cracking, equilibration and biodegradation

Intramolecular isotope distributions, including isotope clumping and position specific fractionation, can provide proxies for the formation temperature and formation and destruction pathways of molecules. In this study, we explore the position-specific hydrogen isotope distribution in propane. We analyzed propane samples from 10 different petroleum systems with high-resolution molecular mass spectrometry. Our results show that the hydrogen isotope fractionation between central and terminal positions of natural propanes ranges from −102‰ to +205‰, a much larger range than that expected for thermodynamic equilibrium at their source and reservoir temperatures (36–63‰). Based on these findings, we propose that the hydrogen isotope structure of catagenic propane is largely controlled by irreversible processes, expressing kinetic isotope effects (KIEs). Kinetic control on hydrogen isotope composition of the products of thermal cracking is supported by a hydrous pyrolysis experiment using the Woodford Shale as substrate, in which we observed isotopic disequilibrium in the early stage of pyrolysis. We make a more general prediction of KIE signatures associated with kerogen cracking by simulating this chemistry in a kinetic Monte Carlo model for different types of kerogens. In contrast, unconventional shale fluids or hot conventional reservoirs contain propane with an isotopic structure close to equilibrium, presumably reflecting internal and/or heterogeneous exchange during high temperature storage (ca. 100–150 °C). In relatively cold (<100 °C) conventional gas accumulations, propane can discharge from its source to a colder reservoir, rapidly enough to preserve disequilibrium signatures even if the source rock thermal maturity is high. These findings imply that long times at elevated temperatures are required to equilibrate the hydrogen isotopic structure of propane in natural gas host rocks and reservoirs. We further defined the kinetics of propane equilibration through hydrogen isotope exchange experiments under hydrous conditions; these experiments show that hydrogen in propane is exchangeable over laboratory timescales when exposed to clay minerals such as kaolinite. This implies rather rapid transfer of propane from sources to cold reservoirs in some of the conventional petroleum systems. Propane is also susceptible to microbial degradation in both oxic and anoxic environments. Biodegradation of propane in the Hadrian and Diana Hoover oil fields (Gulf of Mexico) results in strong increases in central-terminal hydrogen isotope fractionation. This reflects preferential attack on the central position, consistent with previous studies.

Geochimica et Cosmochimica Acta↗

USGS2026

Distinguishing natural from mining-related metal sources by including streambank groundwater data in a stream mass loading study

Distinguishing stream metal loading caused by mine features from that caused by natural background sources remains challenging, yet this distinction is essential for making effective remedial decisions at many legacy mine sites. We combine a stream tracer injection and synoptic sampling study with data from shallow near-stream groundwater wells to estimate left-bank versus right-bank metal loading contributions at the 100-m spatial scale. The study was performed in the East Mancos River, a mountain headwater stream in Colorado, USA. The dominant source of elevated stream metal concentrations could be either groundwater infiltration through right-bank Doyle Mine waste piles or natural acid rock drainage from hydrothermally altered bedrock located mainly on the left bank. For the five metals of concern (Cu, Al, Zn, Cd, and Mn), we find that 15 % of the load contributed by diffuse groundwater inputs in the section potentially influenced by Doyle mine waste originates from the right bank. This right-bank potential mine contribution equates to only 3 % of the total watershed instream load for these metals. Furthermore, apparent 3 H/ 3 He groundwater ages in segments contributing most of the right-bank metal loading are sufficiently old (9–12 yr) to suggest that infiltration through the waste piles, located only 140–180 m from the stream, is unlikely. Estimated potential Doyle mine loading contributions can therefore be considered maximum values. Study results thus indicate that Doyle mine waste piles are a minor source of metal loading under low-flow conditions, and streambank groundwater data can provide valuable additional information in stream mass loading studies.

Colorado↗

USGS2005

Multi-stage sampling for large scale natural resources surveys: A case study of rice and waterfowl

Large-scale sample surveys to estimate abundance and distribution of organisms and their habitats are increasingly important in ecological studies. Multi-stage sampling (MSS) is especially suited to large-scale surveys because of the natural clustering of resources. To illustrate an application, we: (1) designed a stratified MSS to estimate late autumn abundance (kg/ha) of rice seeds in harvested fields as food for waterfowl wintering in the Mississippi Alluvial Valley (MAV); (2) investigated options for improving the MSS design; and (3) compared statistical and cost efficiency of MSS to simulated simple random sampling (SRS). During 2000–2002, we sampled 25–35 landowners per year, 1 or 2 fields per landowner per year, and measured seed mass in 10 soil cores collected within each field. Analysis of variance components and costs for each stage of the survey design indicated that collecting 10 soil cores per field was near the optimum of 11–15, whereas sampling >1 field per landowner provided few benefits because data from fields within landowners were highly correlated. Coefficients of variation (CV) of annual estimates of rice abundance ranged from 0.23 to 0.31 and were limited by variation among landowners and the number of landowners sampled. Design effects representing the statistical efficiency of MSS relative to SRS ranged from 3.2 to 9.0, and simulations indicated SRS would cost, on average, 1.4 times more than MSS because clustering of sample units in MSS decreased travel costs. We recommend MSS as a potential sampling strategy for large-scale natural resource surveys and specifically for future surveys of the availability of rice as food for waterfowl in the MAV and similar areas.

Arkansas, Kentucky, Louisiana, Mississippi, Missou↗

USGS2021

Perspectives from natural resource professionals: Attitudes on lead ammunition risks and use of nonlead ammunition

Hunting is a popular activity but continued use of lead ammunition poses risks to wildlife and human health. To inform adoption of the voluntary use of nonlead ammunition, natural resource professionals were surveyed to understand their attitudes about threats to bald eagles, lead poisoning in bald eagles, human health risks from lead bullet fragments in venison, use of nonlead hunting ammunition, and socio-economic nonlead ammunition factors. Differences were examined by hunter status, ammunition type used, and intentions to use nonlead ammunition. Of participants surveyed, 61.0% were hunters and 39.0% nonhunters, with 59.5% of hunters using lead ammunition and 40.5% using nonlead. Concurrently, 68.5% of hunters reported likely intentions to continue using nonlead or convert to nonlead in the future, while 31.5% reported nonlead use was unlikely. Also, some hunters currently using nonlead ammunition indicated they would unlikely continue using nonlead (17.8%). Nonhunters agreed more strongly than hunters regarding general mortality threats to bald eagles. Additionally, nonhunters, hunters using nonlead, and likely nonlead users more strongly agreed about threats of lead exposure to eagles than their counterparts. Nonhunters and likely nonlead users also more strongly agreed than hunters and unlikely nonlead users about the human health risks of lead ammunition and about shooting characteristics of nonlead. Finally, nonhunters and nonlead users agreed more strongly than their counterparts about the socio-economic factors of using nonlead ammunition. Understanding natural resource professional hunters’ attitudes may help with audience segmentation when designing future nonlead outreach messages.

Journal of Outdoor Recreation and Tourism↗

USGS2020

An international code comparison study on coupled thermal, hydrologic and geomechanical processes of natural gas hydrate-bearing sediments

Geologic reservoirs containing gas hydrate occur beneath permafrost environments and within marine continental slope sediments, representing a potentially vast natural gas source. Numerical simulators provide scientists and engineers with tools for understanding how production efficiency depends on the numerous, interdependent (coupled) processes associated with potential production strategies for these gas hydrate reservoirs. Confidence in the modeling and forecasting abilities of these gas hydrate reservoir simulators (GHRSs) grows with successful comparisons against laboratory and field test results, but such results are rare, particularly in natural settings. The hydrate community recognized another approach to building confidence in the GHRS: comparing simulation results between independently developed and executed computer codes on structured problems specifically tailored to the interdependent processes relevant for gas hydrate-bearing systems. The United States Department of Energy, National Energy Technology Laboratory (DOE/NETL), sponsored the first international gas hydrate code comparison study, IGHCCS1, in the early 2000s. IGHCCS1 focused on coupled thermal and hydrologic processes associated with producing gas hydrates from geologic reservoirs via depressurization and thermal stimulation. Subsequently, GHRSs have advanced to model more complex production technologies and incorporate geomechanical processes into the existing framework of coupled thermal and hydrologic modeling. This paper contributes to the validation of these recent GHRS developments by providing results from a second GHRS code comparison study, IGHCCS2, also sponsored by DOE/NETL. IGHCCS2 includes participants from an international collection of universities, research institutes, industry, national laboratories, and national geologic surveys. Study participants developed a series of five benchmark problems principally involving gas hydrate processes with geomechanical components. The five problems range from simple geometries with analytical solutions to a representation of the world’s first offshore production test of methane hydrates, which was conducted with the depressurization method off the coast of Japan. To identify strengths and limitations in the various GHRSs, study participants submitted solutions for the benchmark problems and discussed differing results via teleconferences. The GHRSs evolved over the course of IGHCCS2 as researchers modified their simulators to reflect new insights, lessons learned, and suggested performance enhancements. The five benchmark problems, final sample solutions, and lessons learned that are presented here document the study outcomes and serve as a reference guide for developing and testing gas hydrate reservoir simulators.

Journal of Marine and Petroleum Geology↗

USGS2024

Protocol for monitoring and analyzing pheromone-mediated behavioral response of sea lamprey in a natural system

Olfactory-mediated behaviors in fish are often examined in artificial microcosms that enable well-controlled treatments but fail to replicate environmental and social contexts. However, observing these behaviors in nature poses challenges. Here, we describe a protocol for recording sea lamprey (Petromyzon marinus) behaviors in a natural system. We describe steps for administering and verifying accurate odorant concentrations, surveying sea lamprey abundance, and tracking sea lamprey movements. We also detail procedures to analyze treatment effects on pheromone-mediated spawning in a high-density population.

STAR Protocols↗

USGS2011

The hypothalamus–pituitary–thyroid axis in teleosts and amphibians: Endocrine disruption and its consequences to natural populations

Teleosts and pond-breeding amphibians may be exposed to a wide variety of anthropogenic, waterborne contaminants that affect the hypothalamus-pituitary-thyroid (HPT) axis. Because thyroid hormone is required for their normal development and reproduction, the potential impact of HPT-disrupting contaminants on natural teleost and amphibian populations raises special concern. There is laboratory evidence indicating that persistent organic pollutants, heavy metals, pharmaceutical and personal care products, agricultural chemicals, and aerospace products may alter HPT activity, development, and reproduction in teleosts and amphibians. However, at present there is no evidence to clearly link contaminant-induced HPT alterations to impairments in teleost or amphibian population health in the field. Also, with the exception of perchlorate for which laboratory studies have shown a direct link between HPT disruption and adverse impacts on development and reproductive physiology, little is known about if or how other HPT-disrupting contaminants affect organismal performance. Future field studies should focus on establishing temporal associations between the presence of HPT-disrupting chemicals, the occurrence of HPT alterations, and adverse effects on development and reproduction in natural populations; as well as determining how complex mixtures of HPT contaminants affect organismal and population health.

General and Comparative Endocrinology↗

USGS2003

Stable isotope fractionation of selenium by natural microbial consortia

The mobility and bioavailability of Se depend on its redox state, and reduction of Se oxyanions to less mobile, reduced species controls transport of this potentially toxic element in the environment. Stable isotope fractionation of Se is currently being developed as an indicator of Se immobilization through reduction. In this study, Se isotope fractionation resulting from reduction of Se(VI) and Se(IV) oxyanions by natural microbial consortia was measured in sediment slurry experiments under nearly natural conditions, with no substrate added. Experiments were conducted with a wide range of initial Se concentrations and with sediment and water from three locations with contrasting environmental settings. The products of Se(VI) and Se(IV) reduction were enriched in the lighter isotopes relative to the reactants. Shifts of -2.6 0 / 00 to -3.1 0 / 00 and -5.5 0 / 00 to -5.7 0 / 00 , respectively, were observed in the 80 Se/ 76 Se ratio. These isotopic fractionations did not depend significantly on initial Se concentrations, which were varied from 22 μg/l to 8 mg/l, or on geochemical differences among the sediments. These results provide estimates of Se isotope fractionation in organic-rich wetland environments but may not be appropriate for substrate-poor aquifers and marine sediments.

Chemical Geology↗

USGS1998

Fluid-deposited graphitic inclusions in quartz: Comparison between KTB (German Continental Deep-Drilling) core samples and artificially reequilibrated natural inclusions

We used Raman microsampling spectroscopy (RMS) to determine the degree of crystallinity of minute (2–15 μm) graphite inclusions in quartz in two sets of samples: experimentally reequilibrated fluid inclusions in a natural quartz grain and biotite-bearing paragneisses from the KTB deep drillhole in SE Germany. Our sequential reequilibration experiments at 725°C on initially pure CO 2 inclusions in a quartz wafer and the J. Krautheim 1993 experiments at 900–1100°C on organic compounds heated in gold or platinum capsules suggest that, at a given temperature, (1) fluid-deposited graphite will have a lower crystallinity than metamorphosed organic matter and (2) that the crystallinity of fluid-deposited graphite is affected by the composition of the fluid from which it was deposited. We determined that the precipitation of more-crystalline graphite is favored by lower f H 2 (higher f O 2 ), and that the crystallinity of graphite is established by the conditions (including gas fugacities) that pertain as the fluid first reaches graphite saturation. Graphite inclusions within quartz grains in the KTB rocks show a wide range in crystallinity index, reflecting three episodes of carbon entrapment under different metamorphic conditions. Isolated graphite inclusions have the spectral properties of totally ordered, completely crystalline graphite. Such crystallinity suggests that the graphite was incorporated from the surrounding metasedimentary rocks, which underwent metamorphism at upper amphibolite-facies conditions. Much of the fluid-deposited graphite in fluid inclusions, however, shows some spectral disorder. The properties of that graphite resemble those of experimental precipitates at temperatures in excess of 700°C and at elevated pressures, suggesting that the inclusions represent precipitates from C-O-H fluids trapped under conditions near those of peak metamorphism at the KTB site. In contrast, graphite that is intimately associated with chlorite and other (presumably low-temperature) silicates in inclusions is highly disordered and spectrally resembles kerogens. This graphite probably was deposited during later greenschist-facies retrograde metamorphism at about 400–500°C. The degree of crystallinity of fluid-deposited graphite is shown to be a much more complex function of temperature than is the crystallinity of metamorphic graphite. To some extent, experiments can provide temperature-calibration of the crystallinity index. However, the difference in time scales between experimental runs and geologic processes makes it difficult to infer specific temperatures for naturally precipitated graphite.

Bohemian Massif↗

USGS1999

The effect of temperature on experimental and natural chemical weathering rates of granitoid rocks

The effects of climatic temperature variations (5-35??C) on chemical weathering are investigated both experimentally using flow-through columns containing fresh and weathered granitoid rocks and for natural granitoid weathering in watersheds based on annual solute discharge. Although experimental Na and Si effluent concentrations are significantly higher in the fresh relative to the weathered granitoids, the proportional increases in concentration with increasing temperature are similar. Si and Na exhibit comparable average apparent activation energies (E(a)) of 56 and 61 kJ/mol, respectively, which are similar to those reported for experimental feldspar dissolution measured over larger temperature ranges. A coupled temperature-precipitation model, using an expanded database for solute discharge fluxes from a global distribution of 86 granitoid watersheds, produces an apparent activation energy for Si (51 kJ/mol), which is also comparable to those derived from the experimental study. This correlation reinforces evidence that temperature does significantly impact natural silicate weathering rates. Effluent K concentrations in the column study are elevated with respect to other cations compared to watershed discharge due to the rapid oxidation/dissolution of biotite. K concentrations are less sensitive to temperature, resulting in a lower average E(a) value (27 kJ/mol) indicative of K loss from lower energy interlayer sites in biotite. At lower temperatures, initial cation release from biotite is significantly faster than cation release from plagioclase. This agrees with reported higher K/Na ratios in cold glacial watersheds relative to warmer temperate environments. Increased release of less radiogenic Sr from plagioclase relative to biotite at increasing temperature produces corresponding decreases in 87Sr/86Sr ratios in the column effluents. A simple mixing calculation using effluent K/Na ratios, Sr concentrations and 87Sr/86Sr ratios for biotite and plagioclase approximates stoichiometric cation ratios from biotite/plagioclase dissolution at warmer temperatures (35??C), but progressively overestimates the relative proportion of biotite with decreasing temperature. Ca, Mg, and Sr concentrations closely correlate, exhibit no consistent trends with temperature, and are controlled by trace amounts of calcite or exchange within weathered biotite. The inability of the watershed model to differentiate a climate signal for such species correlates with the lower temperature dependence observed in the experimental studies.

Geochimica et Cosmochimica Acta↗

USGS1999

Relationships between the structure of natural organic matter and its reactivity towards molecular ozone and hydroxyl radicals

Oxidation reaction rate parameters for molecular ozone (O3) and hydroxyl (HO) radicals with a variety of hydrophobic organic acids (HOAs) isolated from different geographic locations were determined from batch ozonation studies. Rate parameter values, obtained under equivalent dissolved organic carbon concentrations in both the presence and absence of non-NOM HO radical scavengers, varied as a function of NOM structure. First-order rate constants for O3 consumption (k(O3)) averaged 8.8 x 10-3 s-1, ranging from 3.9 x 10-3 s-1 for a groundwater HOA to > 16 x 10-3 s-1 for river HOAs with large terrestrial carbon inputs. The average second-order rate constant (k(HO,DOC) between HO radicals and NOM was 3.6 x 108 l (mol C)-1 s-1; a mass of 12 g C per mole C was used in all calculations. Specific ultraviolet absorbance (SUVA) at 254 or 280 nm of the HOAs correlated well (r > 0.9) with O3 consumption rate parameters, implying that organic ??-electrons strongly and selectively influence oxidative reactivity. HO radical reactions with NOM were less selective, although correlation between k(HO,DOC) and SUVA existed. Other physical-chemical properties of NOM, such as aromatic and aliphatic carbon content from 13C-NMR spectroscopy, proved less sensitive for predicting oxidation reactivity than SUVA. The implication of this study is that the structural nature of NOM varies temporally and spatially in a water source, and both the nature and amount of NOM will influence oxidation rates.

Water Research↗

USGS2001

Chemotaxonomy for naturally macerated tree-fern cuticles (Medullosales and Marattiales), Carboniferous Sydney and Mabou Sub-Basins, Nova Scotia, Canada

Naturally macerated cuticles (NMC) and one synangium, representing medullosalean and marattialean tree-fern species, from two Carboniferous coalfields in Nova Scotia, Canada, are investigated. The samples were analyzed by infrared spectroscopy (FTIR), and by pyrolysis-gas chromatograph/mass spectrometry (py-Gc/Ms) techniques in search for chemical signatures that would help in developing a chemotaxonomic classification of Carboniferous fern species, assuming genetically dependent make-up of cuticles. FTIR-derived CH2/CH3 ratios, in conjunction with contributions from carboxyl groups, demonstrated a better potential for discriminating between medullosalean genera and species than molecular signatures obtained by py-Gc/Ms. However, the latter provided better data for differentiating medullosalean from marattialean tree ferns as a group. Changes in the chemical make-up of naturally macerated cuticles due to sample preparation are discussed. ?? 2001 Elsevier Science B.V. All rights reserved.

International Journal of Coal Geology↗

USGS1998

The role of natural history collections in documenting species declines

Efforts to document the decline of extant populations require a historical record of previous occurrences. Natural history museums contain such information for most regions of the world, at least at a coarse spatial scale. Museum collections have been successfully used to analyse declines in a wide range of plants and animals, at spatial scales ranging from single localities to large biotic and political regions. Natural history museum collections, when properly analysed, can be an invaluable tool in documenting changes in biodiversity during the past century.

Trends in Ecology and Evolution↗

USGS2000

Selective trace enrichment of chlorotriazine pesticides from natural waters and sediment samples using terbuthylazine molecularly imprinted polymers

Two molecularly imprinted polymers were synthesized using either dichloromethane or toluene as the porogen and terbuthylazine as the template and were used as solid-phase extraction cartridges for the enrichment of six chlorotriazines (deisopropylatrazine, deethylatrazine, simazine, atrazine, propazine, and terbuthylazine) in natural water and sediment samples. The extracted samples were analyzed by liquid chromatography/diode array detection (LC/DAD). Several washing solvents, as well as different volumes, were tested for their ability to remove the matrix components nonspecifically adsorbed on the sorbents. This cleanup step was shown to be of prime importance to the successful extraction of the pesticides from the aqueous samples. The optimal analytical conditions were obtained when the MIP imprinted using dichloromethane was the sorbent, 2 mL of dichloromethane was used in the washing step, and the preconcentrated analytes were eluted with 8 mL of methanol. The recoveries were higher than 80% for all the chlorotriazines except for propazine (53%) when 50- or 100-mL groundwater samples, spiked at 1 ??g/L level, were analyzed. The limits of detection varied from 0.05 to 0.2 ??g/L when preconcentrating a 100-mL groundwater sample. Natural sediment samples from the Ebre Delta area (Tarragona, Spain) containing atrazine and deethylatrazine were Soxhlet extracted and analyzed by the methodology developed in this work. No significant interferences from the sample matrix were noticed, thus indicating good selectivity of the MIP sorbents used.

Analytical Chemistry↗