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USGS2005

Development of a solenoid pumped in situ zinc analyzer for environmental monitoring

A battery powered submersible chemical analyzer, the Zn-DigiScan (Zn Digital Submersible Chemical Analyzer), has been developed for near real-time, in situ monitoring of zinc in aquatic systems. Microprocessor controlled solenoid pumps propel sample and carrier through an anion exchange column to separate zinc from interferences, add colorimetric reagents, and propel the reaction complex through a simple photometric detector. The Zn-DigiScan is capable of self-calibration with periodic injections of standards and blanks. The detection limit with this approach was 30 μg L −1 . Precision was 5–10% relative standard deviation (R.S.D.) below 100 μg L −1 , improving to 1% R.S.D. at 1000 μg L −1 . The linear range extended from 30 to 3000 μg L −1 . In situ field results were in agreement with samples analyzed by inductively coupled plasma mass spectrometry (ICPMS). This pump technology is quite versatile and colorimetric methods with complex online manipulations such as column reduction, preconcentration, and dilution can be performed with the DigiScan. However, long-term field deployments in shallow high altitude streams were hampered by air bubble formation in the photometric detector.

Analytica Chimica Acta↗

USGS2009

Assessing the impact of land use change on hydrology by ensemble modelling (LUCHEM) II: Ensemble combinations and predictions

This paper reports on a project to compare predictions from a range of catchment models applied to a mesoscale river basin in central Germany and to assess various ensemble predictions of catchment streamflow. The models encompass a large range in inherent complexity and input requirements. In approximate order of decreasing complexity, they are DHSVM, MIKE-SHE, TOPLATS, WASIM-ETH, SWAT, PRMS, SLURP, HBV, LASCAM and IHACRES. The models are calibrated twice using different sets of input data. The two predictions from each model are then combined by simple averaging to produce a single-model ensemble. The 10 resulting single-model ensembles are combined in various ways to produce multi-model ensemble predictions. Both the single-model ensembles and the multi-model ensembles are shown to give predictions that are generally superior to those of their respective constituent models, both during a 7-year calibration period and a 9-year validation period. This occurs despite a considerable disparity in performance of the individual models. Even the weakest of models is shown to contribute useful information to the ensembles they are part of. The best model combination methods are a trimmed mean (constructed using the central four or six predictions each day) and a weighted mean ensemble (with weights calculated from calibration performance) that places relatively large weights on the better performing models. Conditional ensembles, in which separate model weights are used in different system states (e.g. summer and winter, high and low flows) generally yield little improvement over the weighted mean ensemble. However a conditional ensemble that discriminates between rising and receding flows shows moderate improvement. An analysis of ensemble predictions shows that the best ensembles are not necessarily those containing the best individual models. Conversely, it appears that some models that predict well individually do not necessarily combine well with other models in multi-model ensembles. The reasons behind these observations may relate to the effects of the weighting schemes, non-stationarity of the climate series and possible cross-correlations between models. Crown Copyright ?? 2008.

Advances in Water Resources↗

USGS2006

A review of isotopic composition as an indicator of the natural and anthropogenic behavior of mercury

There are seven stable isotopes of Hg that can be fractionated as a result of inorganic and organic interactions. Important inorganic reactions involve speciation changes resulting from variations in environmental redox conditions, and phase changes resulting from variations in temperature and/or atmospheric pressure. Important organic reactions include methylation and demethylation, reactions that are bacterially mediated, and complexing with organic anions in soils. The measurement of Hg isotopes by multi-collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) is now sufficiently precise and sensitive that it is potentially possible to develop the systematics of Hg isotopic fractionation. This provides an opportunity to evaluate the utility of Hg isotopes in identifying source processes, transport mechanisms, and sinks. New values are provided for, 201Hg/198Hg, 200Hg/198Hg, 199Hg/198Hg for three standard materials (IRMM-AE639, SRM 1641c, SRM 3133) that can be used to make inter-laboratory data comparisons, and these values are tabulated with published isotopic information. Overall, the isotopic data for these standards agree to approximately 0.2???. The paper reviews Hg isotope studies that deal with hydrothermal ore deposits, sediments, coal and organic complexing. ?? 2006 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2008

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d'Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models.

Idaho↗

USGS2015

The fate of cyanide in leach wastes at gold mines: an environmental perspective

This paper reviews the basic chemistry of cyanide, methods by which cyanide can be analyzed, and aspects of cyanide behavior that are most relevant to environmental considerations at mineral processing operations associated with gold mines. The emphasis is on research results reported since 1999 and on data gathered for a series of U.S. Geological Survey studies that began in the late 1990s. Cyanide is added to process solutions as the CN − anion, but ore leaching produces numerous other cyanide-containing and cyanide-related species in addition to the desired cyanocomplex of gold. These can include hydrogen cyanide (HCN); cyanometallic complexes of iron, copper, zinc, nickel, and many other metals; cyanate (CNO − ); and thiocyanate (SCN − ). The fate of these species in solid wastes and residual process solutions that remain once gold recovery activities are terminated and in any water that moves beyond the ore processing facility dictates the degree to which cyanide poses a risk to aquatic organisms and aquatic-dependent organisms in the local environment. Cyanide-containing and cyanide-related species are subject to attenuation mechanisms that lead to dispersal to the atmosphere, chemical transformation to other carbon and nitrogen species, or sequestration as cyanometallic precipitates or adsorbed species on mineral surfaces. Dispersal to the atmosphere and chemical transformation amount to permanent elimination of cyanide, whereas sequestration amounts to storage of cyanide in locations from which it can potentially be remobilized by infiltrating waters if conditions change. From an environmental perspective, the most significant cyanide releases from gold leach operations involve catastrophic spills of process solutions or leakage of effluent to the unsaturated or saturated zones. These release pathways are unfavorable for two important cyanide attenuation mechanisms that tend to occur naturally: dispersal of free cyanide to the atmosphere and sunlight-catalyzed dissociation of strong cyanometallic complexes, which produces free cyanide that can then disperse to the atmosphere. The widest margins of environmental safety will be achieved where mineral processing operations are designed so that time for offgassing, aeration, and sunlight exposure are maximized in the event that cyanide-bearing solutions are released inadvertently.

Applied Geochemistry↗

USGS2014

Assessing the solubility controls on vanadium in groundwater, northeastern San Joaquin Valley, CA

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from <3 μg/L to 70 μg/L with a median of 21 μg/L. Concentrations of V were highest in samples collected from oxic groundwater (49% > 25 μg/L) and lowest in samples collected from anoxic groundwater (70% < 0.8 μg/L). In oxic groundwater, speciation modeling (SM) using PHREEQC predicted that V exists primarily as the oxyanion H 2 VO 4 − . Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V 5+ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4–8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH) 3 + ]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH) 3 molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V 3+ - or mixed V 3+ /Fe 3+ -oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions. Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO 3 ) extract (37–71%), followed by the oxalate-ascorbic acid extract (19–60%) and the oxalate extract (3–14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO 3 extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system.

California↗

USGS2018

The sensitivity of ecosystem service models to choices of input data and spatial resolution

Although ecosystem service (ES) modeling has progressed rapidly in the last 10–15 years, comparative studies on data and model selection effects have become more common only recently. Such studies have drawn mixed conclusions about whether different data and model choices yield divergent results. In this study, we compared the results of different models to address these questions at national, provincial, and subwatershed scales in Rwanda. We compared results for carbon, water, and sediment as modeled using InVEST and WaSSI using (1) land cover data at 30 and 300 m resolution and (2) three different input land cover datasets. WaSSI and simpler InVEST models (carbon storage and annual water yield) were relatively insensitive to the choice of spatial resolution, but more complex InVEST models (seasonal water yield and sediment regulation) produced large differences when applied at differing resolution. Six out of nine ES metrics (InVEST annual and seasonal water yield and WaSSI) gave similar predictions for at least two different input land cover datasets. Despite differences in mean values when using different data sources and resolution, we found significant and highly correlated results when using Spearman's rank correlation, indicating consistent spatial patterns of high and low values. Our results confirm and extend conclusions of past studies, showing that in certain cases (e.g., simpler models and national-scale analyses), results can be robust to data and modeling choices. For more complex models, those with different output metrics, and subnational to site-based analyses in heterogeneous environments, data and model choices may strongly influence study findings.

Applied Geography↗

USGS2005

Contaminants as viral cofactors: assessing indirect population effects

Current toxicological methods often miss contaminant effects, particularly when immune suppression is involved. The failure to recognize and evaluate indirect and sublethal effects severely limits the applicability of those methods at the population level. In this study, the Vitality model is used to evaluate the population level effects of a contaminant exerting only indirect, sublethal effects at the individual level. Juvenile rainbow trout ( Oncorhynchus mykiss ) were injected with 2.5 or 10.0 mg/kg doses of the model CYP1A inducer, β-naphthoflavone (BNF) as a pre-stressor, then exposed to a challenge dose of 10 2 or 10 4 pfu/fish of infectious hematopoietic necrosis virus (IHNV), an important viral pathogen of salmonids in North America. At the end of the 28-d challenge, the mortality data were processed according to the Vitality model which indicated that the correlation between the average rate of vitality loss and the pre-stressor dose was strong: R 2 = 0.9944. Average time to death and cumulative mortality were dependent on the BNF dose, while no significant difference between the two viral dosages was shown, implying that the history of the organism at the time of stressor exposure is an important factor in determining the virulence or toxicity of the stressor. The conceptual framework of this model permits a smoother transfer of results to a more complex stratum, namely the population level, which allows the immunosuppressive results generated by doses of a CYP1A inducer that more accurately represent the effects elicited by environmentally-relevant contaminant concentrations to be extrapolated to target populations. The indirect effects of other environmental contaminants with similar biotransformation pathways, such as polycyclic aromatic hydrocarbons (PAH), could be assessed and quantified with this model and the results applied to a more complex biological hierarchy.

Aquatic Toxicology↗

USGS2010

Ecological hierarchies and self-organisation - Pattern analysis, modelling and process integration across scales

A continuing discussion in applied and theoretical ecology focuses on the relationship of different organisational levels and on how ecological systems interact across scales. We address principal approaches to cope with complex across-level issues in ecology by applying elements of hierarchy theory and the theory of complex adaptive systems. A top-down approach, often characterised by the use of statistical techniques, can be applied to analyse large-scale dynamics and identify constraints exerted on lower levels. Current developments are illustrated with examples from the analysis of within-community spatial patterns and large-scale vegetation patterns. A bottom-up approach allows one to elucidate how interactions of individuals shape dynamics at higher levels in a self-organisation process; e.g., population development and community composition. This may be facilitated by various modelling tools, which provide the distinction between focal levels and resulting properties. For instance, resilience in grassland communities has been analysed with a cellular automaton approach, and the driving forces in rodent population oscillations have been identified with an agent-based model. Both modelling tools illustrate the principles of analysing higher level processes by representing the interactions of basic components.The focus of most ecological investigations on either top-down or bottom-up approaches may not be appropriate, if strong cross-scale relationships predominate. Here, we propose an 'across-scale-approach', closely interweaving the inherent potentials of both approaches. This combination of analytical and synthesising approaches will enable ecologists to establish a more coherent access to cross-level interactions in ecological systems. ?? 2010 Gesellschaft f??r ??kologie.

Basic and Applied Ecology↗

USGS2020

Turtle biogeography: Global regionalization and conservation priorities

Defaunation in the Anthropocene has created a need to focus limited conservation resources on geographically-explicit areas with high conservation significance. Priority conservation areas are often defined as those with high biodiversity – hotspots. While these conservation areas are critical to securing global biodiversity, prevailing approaches for their delineation are often qualitative. Here, we demonstrate the benefits of a clade-specific approach that improves conservation. We use the distinct, imperiled clade of turtles (tortoises and freshwater turtles) to delineate biogeographical regions and characterize their comparative levels of biodiversity and conservation values. We produce a quantitative, revisable map of 63 global turtle regions and identify several turtle regions, mostly in the Indomalayan turtle realm, that are high-priority conservation regions. While our high-priority turtle regions include those previously reported in the literature as turtle hotspots, we also describe a new priority conservation region in Southeast Asia (Yangtze-Huang He-Xi Yiang) which has both high species and endemism richness. Although not considered a high or intermediate conservation priority, our analyses delineated another previously unidentified turtle hotspot – the Kalahari Basin-Rift Valley. Additionally, we identify several turtle regions, largely in Central America, with intermediate conservation priority. Our results reveal that many turtle hotspots represent complex biogeographical areas with high inter-regional β -diversity, and several of these turtle-hotspots occur in transition zones with high biogeographical complexity. In these cases, inter-regional conservation efforts will be necessary to ensure turtle biodiversity conservation.

Biological Conservation↗

USGS2020

Moving from decision to action in conservation science

Biodiversity loss is a major threat to the integrity of ecosystems and is projected to worsen, yet the path to successful conservation remains elusive. Decision support frameworks (DSFs) are increasingly applied by resource managers to navigate the complexity, uncertainty, and differing socio-ecological objectives inherent to conservation problems. Most published conservation research that uses DSFs focuses on analytical stages (e.g., identifying an optimal decision), making it difficult to assess and learn from previous examples in a conservation practice context. Here, we (1) evaluate the relationship between the application of decision science and the resulting conservation outcomes, and (2) identify and address existing barriers to the application of DSFs to conservation practice. To do this, we develop a framework for evaluating conservation initiatives using decision science that emphasizes setting attainable goals, building momentum, and obtaining partner buy-in. We apply this framework to a systematic review of amphibian conservation decision support projects, including a follow-up survey of the pertinent conservation practitioners, stakeholders, and scientists. We found that all projects identified optimal solutions to reach stated objectives, but positive conservation outcomes were limited when implementation challenges arose. Further, we identified multiple barriers (e.g., dynamic and hierarchical leadership, scale complexity, limited resource availability) that can inhibit the progression from decision identification to action implementation (i.e., ‘decision-implementation gap’), and to successful conservation outcomes. Based on these results, we provide potential actionable steps and avenues for future development of DSFs to facilitate the transition from decision to action and the realization of conservation successes.

Biological Conservation↗

USGS2023

Positive but un-sustained wildlife community responses to reserve expansion and mammal reintroductions in South Africa

The creation and expansion of protected areas, coupled with wildlife reintroductions, are increasingly used as conservation measures to combat wildlife declines worldwide. Although these types of restoration efforts are expected be beneficial to wildlife populations, variable species management and interactions among species within complex food webs have the potential to lead to unintended species-specific responses to reserve expansion which can counteract the anticipated positive effects. We used a multi-season camera trap study to investigate community-wide responses of wildlife to a reserve expansion and associated wildlife releases in South Africa. We analyzed the camera trap data using community occupancy and N-mixture models to assess how the occupancy and intensity of use of individual species changed in the four seasons following reserve expansion. We found species-specific responses to reserve expansion, although responses were generally positive in occupancy and intensity of use but un-sustained. The apex predator, the lion ( Panthera leo ) and the majority of managed herbivores exhibited sustained or delayed positive responses, whereas most subordinate predators and unmanaged herbivores had short-lived, fluctuating, or neutral responses. Interactive effects of top-down suppression, competitive pressure, and increased space and food resources likely resulted in the temporally-variable responses of most species. Although no species responded negatively to reserve expansion and mammal reintroductions, the lack of sustained positive responses for most species indicates the complexities of implementing conservation actions to benefit multiple wildlife species. Our results highlight the importance of monitoring the entire wildlife community following management actions such as reserve expansion or wildlife reintroductions.

Biological Conservation↗

USGS2006

Sorption processes affecting arsenic solubility in oxidized surface sediments from Tulare Lake Bed, California

Elevated concentrations of arsenic (As) in shallow groundwater in Tulare Basin pose an environmental risk because of the carcinogenic properties of As and the potential for its migration to deep aquifers that could serve as a future drinking water source. Adsorption and desorption are hypothesized to be the major processes controlling As solubility in oxidized surface sediments where arsenate [As(V)] is dominant. This study examined the relationship between sorption processes and arsenic solubility in shallow sediments from the dry Tulare Lake bed by determining sorption isotherms, pH effect on solubility, and desorption-readsorption behavior (hysteresis), and by using a surface complexation model to describe sorption. The sediments showed a high capacity to adsorb As(V). Estimates of the maximum adsorption capacity were 92 mg As kg- 1 at pH 7.5 and 70 mg As kg- 1 at pH 8.5 obtained using the Langmuir adsorption isotherm. Soluble arsenic [> 97% As(V)] did not increase dramatically until above pH 10. In the native pH range (7.5-8.5), soluble As concentrations were close to the lowest, indicating that As was strongly retained on the sediment. A surface complexation model, the constant capacitance model, was able to provide a simultaneous fit to both adsorption isotherms (pH 7.5 and 8.5) and the adsorption envelope (pH effect on soluble As), although the data ranges are one order of magnitude different. A hysteresis phenomenon between As adsorbed on the sediment and As in solution phase was observed in the desorption-readsorption processes and differs from conventional hysteresis observed in adsorption-desorption processes. The cause is most likely due to modification of adsorbent surfaces in sediment samples upon extensive extractions (or desorption). The significance of the hysteresis phenomenon in affecting As solubility and mobility may be better understood by further microscopic studies of As interaction mechanisms with sediments subjected to extensive leaching in natural environments. ?? 2006 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2009

Changing sources of strontium to soils and ecosystems across the Hawaiian Islands

Strontium isotope ratios assist ecosystem scientists in constraining the sources of alkaline earth elements, but their interpretation can be difficult because of complexities in mineral weathering and in the geographical and environmental controls on elemental additions and losses. Hawaii is a "natural laboratory" where a number of important biogeochemical variables have either limited ranges or vary in systematic ways, providing a unique opportunity to understand the impact of time, climate, and atmospheric inputs on the evolution of base cation sources to ecosystems. There are three major sources of strontium (Sr) to these ecosystems, each with distinct isotopic compositions: basalt lava, Asian dust, and rainfall. We present Sr isotope and concentration data on both bulk soil digests and NH 4 Ac extracts from soil profiles covering a wide range of environments and substrate ages. Bulk soil material from dry climates and/or young substrate ages with > 80????g g - 1 Sr retain basalt-like Sr isotopic signatures, whereas those with Sr concentrations < 80????g g - 1 can have isotope signatures that range from basalt-like values to the more radiogenic values associated with continental dust. Although both dust accumulation and lava weathering are time- and rainfall-dependent, the overall concentration of Sr drops with increasing leaching even as quartz and mica derived from continental dust sources increase to > 40% by mass. At elevated dust levels, lava-derived Sr is low and dust-derived Sr is the dominant control of 87 Sr/ 86 Sr in bulk soils; however, 87 Sr/ 86 Sr of NH 4 Ac-extractable Sr largely reflects atmospheric deposition of marine aerosol in these situations. Overall, whole-soil Sr isotope values are controlled by complex interactions between Sr provided by lava weathering but partially lost by leaching, and Sr provided by dust but held in more resistant minerals. The isotopic composition of NH 4 Ac-extractable Sr and of the biota is controlled by lava weathering and rainfall contribution of Sr with only minor contributions from radiogenic dust sources. ?? 2009 Elsevier B.V.

Chemical Geology↗

USGS2014

Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and Mössbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe 2 O 3 /FeO): szomolnokite, rozenite, siderotil, halotrichite, römerite, voltaite, copiapite, monoclinic Fe 2 (SO 4 ) 3 , Fe 2 (SO 4 ) 3 ·5H 2 O, kornelite, coquimbite, Fe(SO 4 )(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750–4000 cm −1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe 3+ octahedra and sulfate tetrahedra. Mössbauer spectra of selected samples were obtained at room temperature and 80 K for ferric minerals jarosite and rhomboclase and mixed ferric–ferrous minerals römerite, voltaite, and copiapite. Values of Fe 2+ /[Fe 2+ + Fe 3+ ] determined by Mössbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases.

California↗

USGS2012

The effect of diagenesis and fluid migration on rare earth element distribution in pore fluids of the northern Cascadia accretionary margin

Analytical challenges in obtaining high quality measurements of rare earth elements (REEs) from small pore fluid volumes have limited the application of REEs as deep fluid geochemical tracers. Using a recently developed analytical technique, we analyzed REEs from pore fluids collected from Sites U1325 and U1329, drilled on the northern Cascadia margin during the Integrated Ocean Drilling Program (IODP) Expedition 311, to investigate the REE behavior during diagenesis and their utility as tracers of deep fluid migration. These sites were selected because they represent contrasting settings on an accretionary margin: a ponded basin at the toe of the margin, and the landward Tofino Basin near the shelf's edge. REE concentrations of pore fluid in the methanogenic zone at Sites U1325 and U1329 correlate positively with concentrations of dissolved organic carbon (DOC) and alkalinity. Fractionations across the REE series are driven by preferential complexation of the heavy REEs. Simultaneous enrichment of diagenetic indicators (DOC and alkalinity) and of REEs (in particular the heavy elements Ho to Lu), suggests that the heavy REEs are released during particulate organic carbon (POC) degradation and are subsequently chelated by DOC. REE concentrations are greater at Site U1325, a site where shorter residence times of POC in sulfate-bearing redox zones may enhance REE burial efficiency within sulfidic and methanogenic sediment zones where REE release ensues. Cross-plots of La concentrations versus Cl, Li and Sr delineate a distinct field for the deep fluids (z > 75 mbsf) at Site U1329, and indicate the presence of a fluid not observed at the other sites drilled on the Cascadia margin. Changes in REE patterns, the presence of a positive Eu anomaly, and other available geochemical data for this site suggest a complex hydrology and possible interaction with the igneous Crescent Terrane, located east of the drilled transect.

Vancouver↗

USGS2025

Characterizing sedimentary organic carbon in a hydrothermal spreading center, the Escanaba Trough

Sediments in critical marine mineral environments are of wide importance due to their preservation of both marine minerals and organic carbon (OC) stocks. However, OC storage and cycling is often overlooked in mineral system studies. This work characterizes sedimentary OC within the Escanaba Trough, a hydrothermal sulfide system off the coast of northern California. By utilizing ROV-based push coring, we collected sediments near and far from high temperature, low temperature, and inactive vents. We applied a multipronged organic geochemical approach, measuring bulk sediment, OC fractions of varying labilities, and biomarkers to tease apart the storage, source, and cycling of OC within this complex system. In contrast to past work indicating a primarily terrestrial source to deeper, Pleistocene sediments, our results suggest a primarily marine source in surface sediments at least 50 m away from active venting. Near active venting, we see evidence of locally produced chemosynthetic OC in addition to the background marine source. This chemosynthetic OC appears to be rapidly remineralized and supports more complex deep-sea food webs compared to hemipelagic sites. Still, the greatest contribution of labile OC was observed at inactive vent sites, which we suggest is due to hydrothermal fluid alteration of more labile OC at actively venting sites. Depending on fluid temperature, hydrothermally altered OC is either preserved in the sediments as petroleum or migrated with fluid flow. Considering inactive sites are those most likely to be targeted by potential mining, we suggest additional studies could verify if these results apply at other sedimented seafloor massive sulfide systems.

California↗

USGS2026

Trace element heterogeneity and crystallization history of the Plesovice zircon: Implications for its use as a U–Pb LA-ICP-MS reference material

Zircon crystals from Plešovice hyperpotassic granulite (HPG) have been widely used as a reference material for LA-ICP-MS dating. Detailed cathodoluminescence (CL) imaging and trace element analysis reveal a complex internal structure of Plešovice zircon linked to extreme chemical heterogeneity, which allows us to distinguish different zircon domains formed during its crystallization: (i) rare low-CL cores enriched in U, Nb, HREE and Y; (ii) dominant sector-zoned to oscillatory-zoned domains, and (iii) CL-bright rims poor in trace elements. Relic fine oscillatory zoned areas are chemically homogeneous, whereas coarsened and blurred areas, and CL-dark replacement domains, are heterogeneous. Based on these data we suggest a complex and protracted zircon evolution: (i) crystallization of metamorphic zircon in anatectic calc-alkaline granulite; (ii) magmatic zircon crystallization at high temperature and pressure in a dry ultrapotassic melt at presence of peritectic garnet; (iii) coupled zircon dissolution-precipitation processes triggered by percolating hydrous residual melt; and (iv) coarsening and replacement of the pre-existing zircon due to prolonged exposure to a reactive fluid/hydrous melt. New CA-ID-TIMS U Pb dates between 337.167 ± 0.080 and 337.840 ± 0.080 Ma confirm crystallization age for HPG zircon at around 337.4 Ma and suggest that previously published dates of 336.37 Ma were biased by non-mitigated lead loss. We thus confirm the U/Pb homogeneity of Plešovice reference zircon despite its chemical heterogeneity. We further discuss the implications of using the chemically extremely heterogeneous Plešovice reference zircon as primary or secondary standard for in-situ LA-ICP-MS geochronology, in particular for quantification of the chemical matrix-dependence of the relative sensitivity factor ( β ) of laser ablation.

Plešovice quarry↗