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Ecotoxicology of wild mammals

An international group of 32 scientists has critically reviewed the scientific literature on exposure and effects of environmental contaminants in wild mammals. Although the absolute number of toxicological studies in domesticated and wild mammals eclipses that for birds, a detailed examination of scientific publications and databases reveal that information for 'wild' birds is actually greater than that for 'wild' mammals. Of the various taxa of mammals, ecotoxicological data is most noticeably lacking for marsupials and monotremes. In contrast, rodents (comprising 43% of all mammal species) have been studied extensively, despite evidence of their tolerance to some organochlorine compounds, rodenticides, and even radionuclides. Mammalian species at greatest risk of exposure include those that consume a high percentage of their body weight on a daily basis (e.g., shrews, moles and bats). Aquatic mammals tend to bioaccumulate tremendous burdens of lipophilic contaminants, although storage in their fat depots may actually limit toxicity. Carnivores appear to be more sensitive to adverse effects of environmental contaminants than herbivores. Remarkably few of the thousands of compounds manufactured worldwide have been toxicologically evaluated in wild mammals, and concentrations of even fewer have been monitored in tissues. Overarching research needs include: development of new exposure/effects models and better methods for estimation of species sensitivities; generation of comparative data on contaminant bioavailability, sublethal responses and detoxication mechanisms; enhanced understanding of pesticide, industrial contaminant and metal interactions; identification of endocrine disruptive contaminants and their overall ecological significance; and finally, estimating the relative contribution of environmental contamination as a factor affecting wild mammal populations.

Society of Environmental Toxicology and Chemistry,

Spatial dependence of reduced sulfur in Everglades dissolved organic matter controlled by sulfate enrichment

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

Florida

Preliminary Surficial Geology of the Dove Spring Off-Highway Vehicle Open Area, Mojave Desert, California

Introduction As part of a U.S. Geological Survey (USGS) monitoring plan to evaluate the environmental impact of off-highway vehicle (OHV) use on Bureau of Land Management (BLM) land in California, this report presents results of geologic studies in the Dove Spring OHV Open Area. This study produced baseline data, which when combined with historic and current patterns of land use, forms the basis for vegetation and wildlife monitoring designed to address the following questions: 1. Is the density and length of OHV routes increasing? 2. Are there cumulative effects of past and current OHV use associated with changes in the environmental integrity of soils, plants, and wildlife? 3. Is the spread of invasive species associated with levels of OHV use? 4. Is there a threshold of OHV impact that might be translated to management action by the BLM? The monitoring studies will be used to collect baseline environmental information to determine levels of environmental impact of OHV use. This approach will use a low-impact area as a proxy for pre-impact conditions (substituting space for time) to determine thresholds of OHV impacts beyond which environmental integrity is affected. Indicators of environmental integrity will emphasize factors that are fundamental to ecosystem structure and function and likely to be sensitive to OHV impacts. Surficial geology is studied because material properties such as texture and chemistry strongly control soil moisture and nutrient availability and therefore affect plant growth and distribution. An understanding of surficial geology can be used to predict and extrapolate soil properties and improve understanding of vegetation assemblages and their distribution. In the present study, vegetation associations may be examined as a function of surficial geology as well as other environmental variables such as slope, aspect, NRCS (National Resources Conservation Service) soil classification, elevation, and land-use history. Ground measurements of vegetation, biological soil crusts, compaction, and other information may be correlated with land use to identify possible ecological thresholds in OHV use that require monitoring. Surficial geology is relevant for several other studies of OHV impact, such as soil compaction, dust emissions, and acceleration of erosion. Compaction, reduced infiltration, and accelerated erosion have been documented in Dove Spring Canyon because of OHV use (Snyder and others, 1976) and elsewhere in the Mojave Desert (e.g., Webb, 1983; Langdon, 2000). A surficial geologic map enables the use of geomorphic process models, which when combined with measured soil properties, such as texture, nutrient chemistry, and bulk density, allows spatial extrapolation of the properties. Maps can be produced that predict compaction susceptibility, moisture conditions, dust emissions, flood hazards, and erodibility, among other applications.

Open-File Report

Endocrine active contaminants in aquatic systems and intersex in common sport fishes

Male fish are susceptible to developing intersex, a condition characterized by the presence of testicular oocytes. In the present study, the relationship between intersex and exposure to estrogenic endocrine active contaminants (EACs) was assessed for 2 genera of sport fish, Micropterus and Lepomis , at 20 riverine sites. Seasonal trends and relationships between EACs and intersex (prevalence and severity) were examined at varying putative sources of EACs throughout North Carolina, identified as point sources, nonpoint sources, and reference sites. Intersex was identified in both genera, which was documented for the first time in wild-caught Lepomis . Intersex was more prevalent (59.8%) and more severe (1.6 mean rank) in Micropterus , which was highly correlation to EACs in sediment. In contrast, intersex was less common (9.9%) and less severe (0.2 mean rank) in Lepomis and was highly correlated to EACs in the water column. The authors found that concentrations of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, industrial EACs, and estrogens were highest at point source sites; however, no source type variation was identified in the prevalence or severity of intersex, nor were there seasonal trends in intersex or EAC concentrations. The authors’ results associate genus-specific prevalence of intersex with specific EAC classes in common sport fishes having biological, ecological, and conservation implications.

Environmental Toxicology and Chemistry

Fate and effects to the benthic community of a copper treatment to eradicate invasive mussels in a large western river, USA

Copper-based chemical treatments are commonly used to eradicate invasive mussels in small ponds and lakes, but their use in large rivers has been limited. In 2023, in response to a detection of invasive quagga mussels, a 10-km reach of the Snake River (Idaho, USA), was treated with an unprecedented 19,300 kg of chelated copper molluscicide to a target concentration of 1,000 µg/L for 10 days. We assessed the transport and fate of the copper and its exposure and effects on the nontarget benthic community downstream. Water samples were collected at seven locations throughout the treatment period, and sediment, periphyton, and benthic macroinvertebrates were collected pre- and posttreatment. Nearly half of the original mass of copper was removed from the water column via sedimentation, sorption to algae, or biological uptake within the 10-km treatment reach and the first 15 km downstream. Even so, dissolved copper concentrations exceeded the acute toxicity threshold at least as far as 28 km downstream for more than 2 weeks. Sediment copper increased by up to 8.3-fold, exceeding the consensus-based sediment quality threshold effect concentration at several sites. Effects on benthic macroinvertebrates varied by taxa. From 0–28 km downstream, invertebrate abundances decreased 52%–94%, with gastropods among the most affected. Of the unique taxa present at these sites pretreatment, 52%–64% were not found posttreatment but were replaced by other taxa, indicating a reorganization of the base of the food web. Additionally, from 0–15 km downstream, the percentage of individuals from tolerant taxa increased two to15-fold. Findings from this study can help watershed managers plan future invasive mussel responses while protecting culturally, economically, and ecologically important nontarget species in large rivers.

Idaho

Temporal changes in aquatic-invertebrate and fish assemblages in streams of the north-central and northeastern U.S.

Many management agencies seek to evaluate temporal changes in aquatic assemblages at monitoring sites, but few have sites with ecological time series that are long enough for this purpose. Trends in aquatic-invertebrate and fish assemblage composition were assessed at 27 long-term monitoring sites in the north-central and northeastern United States. Temporal changes were identified using serial trend analysis. Sites with significant serial trends were further evaluated by relating explanatory environmental variables (e.g., streamflow, habitat, and water chemistry) to changes in assemblage composition. Significant trends were found at 19 of 27 study sites; however, differences in the sensitivity of the aquatic fauna to environmental stressors were identified. For example, significant trends in fish assemblages were found at more sites (15 of 27) than for aquatic-invertebrate assemblages (10 of 27 sites). In addition, trends in the invertebrate assemblage were most often explained by changes in streamflow processes (e.g., duration and magnitude of low- and high-flows, streamflow variability, and annual rates of change), whereas trends in the fish assemblage were more related to changes in water chemistry. Results illustrate the value of long-term monitoring for the purpose of assessing temporal trends in aquatic assemblages. The ability to detect trends in assemblage composition and to attribute these changes to environmental factors is necessary to understand mechanistic pathways and to further our understanding of how incremental anthropogenic alterations modify aquatic assemblages over time. Finally, this study's approach to trends analysis can be used to better inform the design of monitoring programs as well as support the ongoing management needs of stakeholders, water-resource agencies, and policy makers.

Connecticut, Illinois, Indiana, Iowa, Massachusett

Choosing indicators of natural resource condition: A case study in Arches National Park, Utah, USA

Heavy visitor use in many areas of the world have necessitated development of ways to assess visitation impacts. Arches National Park recently completed a Visitor Experience and Resource Protection (VERP) plan. Integral to this plan was developing a method to identify biological indicators that would both measure visitor impacts and response to management actions. The process used in Arches for indicator selection is outlined here as a model applicable to many areas facing similar challenges. The steps were: (1) Vegetation types most used by visitors were identified. Impacted and unimpacted areas in these types were sampled, comparing vegetation and soil factors. (2) Variables found to differ significantly between compared sites were used as potential indicators. (3) Site-specific criteria for indicators were developed, and potential indicators evaluated using these criteria. (4) Chosen indicators were further researched for ecological relevancy. (5) Final indicators were chosen, field tested, and monitoring sites designated. In Arches, indicators were chosen for monitoring annually (soil crust index, soil compaction, number of used social trails and soil aggregate stability) and every five years (vegetation cover and frequency; ground cover; soil chemistry; and plant tissue chemistry).

Environmental Management

Growth and defense characteristics of whitebark pine (Pinus albicaulis) and lodgepole pine (Pinus contorta var latifolia) in a high-elevation, disturbance-prone mixed-conifer forest in northwestern Montana, USA

Recent, widespread tree mortality in the western U.S. resulting from changes in climate, pathogens, insect activity, and forest management practices has led to concerns for many ecologically and culturally important species. Within conifers, resin-based defenses have long been recognized as a primary defense mechanism against a variety of insects and pathogens. Oleoresin produced by trees contain complex mixtures of terpenoids that have numerous insecticidal and fungicidal properties. Research has also identified links between resin duct characteristics and increased probability of survival during bark beetle outbreaks. Whitebark pine ( Pinus albicaulis ) is a culturally significant high elevation species that provides numerous ecological services within subalpine and alpine ecosystems. Whitebark pine has co-evolved with a suite of biotic and abiotic disturbances. Individual trees allocate resources towards growth and resin-based defenses, making it a good candidate species to evaluate growth and defense relationships and tradeoffs. In this study we compared constitutive resin chemistry, tree growth and resin duct anatomy between similarly aged whitebark and lodgepole pine ( P. contorta var latifolia ) growing in proximity within a disturbance-prone, mixed-conifer forest in northwestern Montana. These two host species have varying degrees of historical exposure to mountain pine beetle. Our research yields four important findings. First, we did not find evidence of a tradeoff between tree growth and tree defenses (resin duct morphology and resin chemistry). This suggests that trees growing under favorable field conditions can experience high growth rates and still allocate ample resources towards defense. Second, we found that resin ducts and constitutive mono- and sesqui- terpenes were not correlated in lodgepole pine while duct production and area were positively related to constitutive monoterpenes, and duct size and area were positively related to constitutive sesquiterpenes, in whitebark pine. The lack of distinct, consistent relationships between these defensive features suggests that both whitebark and lodgepole pine trees present beetles with numerous, complex combinations of resin-based defenses. Third, based on constitutive terpene profiles, bark beetles are more likely to enter lodgepole pine but more likely to successfully elicit mass attacks in whitebark pine, which agrees with beetle attack and success patterns observed in the field. Fourth, overstory competition, particularly by Engelmann spruce ( Picea engelmannii ), can influence tree defenses, specifically by reducing constitutive terpene concentrations in lodgepole and whitebark pine. Competitive tree interactions could lead to altered bark beetle-conifer interactions as host and nonhost species migrate in response to changing climate. Our results suggest that strategies designed to support whitebark pine populations can benefit from better understanding interactions among growth, competition and physical and chemical defenses in response to multiple disturbance.

Montana

Chemical ecology of red mangroves, Rhizophora mangle, in the Hawaiian Islands

The coastal red mangrove, Rhizophora mangle L., was introduced to the Hawaiian Islands from Florida 100 yr ago and has spread to cover many shallow intertidal shorelines that once were unvegetated mudflats. We used a field survey approach to test whether mangroves at the land-ocean interface could indicate watershed inputs, especially whether measurements of leaf chemistry could identify coasts with high nutrient inputs and high mangrove productivities. During 2001-2002, we sampled mangroves on dry leeward coasts of southern Moloka'i and O'ahu for 14 leaf variables including stable carbon and nitrogen isotopes (delta 13 C, delta 15 N), macronutrients (C, N, P), trace elements (B, Mn, Fe, Cu, Zn), and cations (Na, Mg, K, Ca). A new modeling approach using leaf Na, N, P, and delta 13 C indicated two times higher productivity for mangroves in urban versus rural settings, with rural mangroves more limited by low N and P nutrients and high-nutrient urban mangroves more limited by freshwater inputs and salt stress. Leaf chemistry also helped identify other aspects of mangrove dynamics: especially leaf delta 15 N values helped identify groundwater N inputs, and a combination of strongly correlated variables (C, N, P, B, Cu, Mg, K, Ca) tracked the mangrove growth response to nutrient loading. Overall, the chemical marker approach is an efficient way to survey watershed forcing of mangrove forest dynamics.

Hawai'i

Quality assurance report for Loch Vale Watershed, 2010–19

The Loch Vale Watershed Research and Monitoring Program collects long-term datasets of ecological and biogeochemical parameters in Rocky Mountain National Park to support both (1) management of this protected area and (2) research into watershed-scale ecosystem processes as those processes respond to atmospheric deposition and climate variability. The program collects data on precipitation depth and atmospheric deposition chemistry—as well as surface water biogeochemistry—within the watershed and in other areas of the park. These data are used by resource managers, scientists, policy makers, and students, so it is important that all collected data meet high quality standards. This report presents an evaluation of data quality for precipitation, atmospheric ammonia, and surface water quality samples collected from 2010 to 2019. This report also presents changes made to the monitoring and laboratory equipment used during the study period and describes new data streams added to the project, including atmospheric ammonia, surface water chlorophyll-a, and dissolved oxygen in two lakes: The Loch and Sky Pond. Quality-assurance procedures looked at the accuracy and precision of measurements made over the study period and found that precipitation and surface water chemistry data were 99 percent accurate and precise. Records that failed to meet quality standards were removed from published databases. From 2010 to 2014, a colocated precipitation gauge and deposition collector were installed on site as quality checks. From 2014 to 2018, power loss at the site resulted in significant loss of precipitation data records during the snow seasons. Those problems were addressed by installing new solar-power equipment in 2019. Measurements of deposition chemistry, atmospheric ammonia deposition, and surface water biogeochemistry were all sufficiently complete and consistent to support project data needs.

Colorado

Integration of genotoxicity and population genetic analyses in kangaroo rats ( Dipodomys merriami ) exposed to radionuclide contamination at the Nevada Test Site, USA

We examined effects of radionuclide exposure at two atomic blast sites on kangaroo rats (Dipodomys merriami) at the Nevada Test Site, Nevada, USA, using genotoxicity and population genetic analyses. We assessed chromosome damage by micronucleus and flow cytometric assays and genetic variation by randomly amplified polymorphic DNA (RAPD) and mitochondrial DNA (mtDNA) analyses. The RAPD analysis showed no population structure, but mtDNA exhibited differentiation among and within populations. Genotoxicity effects were not observed when all individuals were analyzed. However, individuals with mtDNA haplotypes unique to the contaminated sites had greater chromosomal damage than contaminated-site individuals with haplotypes shared with reference sites. When interpopulation comparisons used individuals with unique haplotypes, one contaminated site had greater levels of chromosome damage than one or both of the reference sites. We hypothesize that shared-haplotype individuals are potential migrants and that unique-haplotype individuals are potential long-term residents. A parsimony approach was used to estimate the minimum number of migration events necessary to explain the haplotype distributions on a phylogenetic tree. The observed predominance of migration events into the contaminated sites supported our migration hypothesis. We conclude the atomic blast sites are ecological sinks and that immigration masks the genotoxic effects of radiation on the resident populations.

Nevada

Sampling dragonflies for mercury analysis in Grand Canyon National Park, 2018–2024: A contribution of the Dragonfly Mercury Project

The Dragonfly Mercury Project is a collaborative initiative that utilizes dragonfly larvae as biosentinels to monitor mercury concentrations across 180 national parks and other protected lands, including Grand Canyon National Park (GRCA). These indicators serve as surrogates for environmental risk and can indicate where fish consumption could pose health risks through exposure to mercury. From 2018–2024, citizen scientists and staff from the National Park Service and U.S. Geological Survey helped collect close to 400 larvae from 25 GRCA sites across nearly 300 river miles, revealing mercury concentrations ranging 3.0–1337 ng/g (parts per billion) dry weight. Results were available for 20 sites. Upon comparing mercury concentrations to an impairment index, most sites were classified as low or no risk for ecological impairment, though 10% (2 sites) exceeded moderate or severe risk benchmarks (Pete’s Pocket and Buck Farm Canyon, respectively). Sources of mercury to GRCA likely stem from a combination of atmospheric deposition, upstream discharge from Lake Powell, and other watershed contributions. In addition, food web dynamics, underlying water chemistry, and environmental disturbances (e.g., floods) contribute to mercury mobilization, production, and bioaccumulation. Report findings provide a baseline for connecting ongoing science in the Colorado River watershed, informing management actions, and enhancing public engagement through citizen science.

Arizona

Resilience in ecotoxicology: Toward a multiple equilibrium concept

The term resilience describes stress–response patterns across scientific disciplines. In ecology, advances have been made to clearly define resilience based on underlying mechanistic assumptions. Engineering resilience (rebound) is used to describe the ability of organisms to recover from adverse conditions (disturbances), which is termed the rate of recovery. By contrast, the ecological resilience definition considers a systemic change, that is, when ecosystems reorganize into a new regime following disturbance. Under this new regime, structural and functional aspects change considerably relative to the previous regime, without recovery. In this context, resilience is an emergent property of complex systems. In the present study, we argue that both definitions and uses are appropriate in ecotoxicology, and although the differences are subtle, the implications and uses are profoundly different. We discuss resilience concepts in ecotoxicology, where the prevailing view of resilience is engineering resilience from chemical stress. Ecological resilience may also be useful for describing systemic ecological changes because of chemical stress. We present quantitative methods that allow ecotoxicologists and risk managers to assess whether an ecosystem faces an impending regime shift or whether it has already undergone such a shift. We contend that engineering and ecological resilience help to distinguish ecotoxicological responses to chemical stressors mechanistically and thus have implications for theory, policy, and application.

Environmental Toxicology and Chemistry

Impacts of temporal revisit designs on the power to detect trend with a linear mixed model: An application to long-term monitoring of Sierra Nevada lakes

Long-term ecological monitoring programs often use linear mixed models to estimate trend in an ecological indicator sampled across large landscapes. A linear mixed model is versatile for estimating a linear trend in time as well as components of spatial and temporal variationin the case of unbalanced data structures , which are common in complex monitoring designs where limited sampling effort must be optimized over time and space. A power analysis was used to inform a lake chemistry monitoring design, including selecting the most appropriate temporal revisit design. Pilot data from surveys of lakes across large wilderness national parks (Sequoia, Kings Canyon, and Yosemite national parks) were used to obtain variance components for a Monte Carlo power simulation. Using a linear mixed model for a range of temporal revisit designs, sample sizes, and trend magnitudes, we evaluated the power to detect trend, the trend test size, and the relative bias of trend coefficient estimates for four continuous and normally distributed indicators. Contrary to prior research based on large-sample approximations that identified a single panel of sites visited annually as the revisit design generating the highest power, we found that the power to detect a 12-year trend based on the Wald t-test from a linear mixed model may be optimized by obtaining unbalanced data sets with limited to no annual replication. We emphasize the importance of examining variance composition, sample size, and the power and size of the trend test with Monte Carlo simulation when allocating sampling effort over time and space.

Ecological Indicators

Wildfire-resistant biological soil crusts and fire-induced loss of soil stability in Palouse prairies, USA

Frequent low-intensity fires are a natural component of the ecology of the Palouse prairies of northwestern North America. To study the effects of fire upon biological soil crusts (BSCs) occurring in these grasslands, we sampled three burned (in 2000) sites and three unburned sites in the Hell's Canyon area (OR, USA) ???1 year post-fire. We measured vascular plant and BSC cover, soil microbe pigmentation, texture and chemistry, and soil surface physical properties (stability and rugosity). Festuca idahoensis was two times more abundant in unburned plots (P=0.0006), and vascular plant and litter cover were generally higher in unburned plots. At the community scale, there was no difference in the lichen and moss species composition, suggesting much less drastic effects of fire on BSCs than reported in other systems. Soil surface stability (measured using slake value) was significantly lower in burned sites than unburned sites (median value=5 versus 6, P=0.008), a result which is likely due to the greater density of lichens and mosses encountered in the unburned plots. Soil microbe pigmentation was lower in burned plots (P=0.03), suggesting that the biomass of photosynthetic microbes had decreased; however, the presence of intra- and extracellular pigments in burned soils indicates that microorganisms were not eradicated. Pigments most strongly associated with cyanobacteria were more abundant in unburned sites, suggesting that cyanobacteria may have been more strongly impacted by the fire than other BSC components. Composition of nutrients and surface rugosity did not differ significantly between treatments. We hypothesize that Palouse prairie soil crusts are relatively resistant to wildfire because of low fire intensity and their occupation of space away from the vascular plant fuel load.

Applied Soil Ecology

Streamwater chemistry and nutrient budgets for forested watersheds in New England: Variability and management implications

Chemistry of precipitation and streamwater and resulting input-output budgets for nutrient ions were determined concurrently for three years on three upland, forested watersheds located within an 80 km radius in central New England. Chemistry of precipitation and inputs of nutrients via wet deposition were similar among the three watersheds and were generally typical of central New England. In contrast, chemistry and nutrient outputs in streamwater varied dramatically between watersheds, with chemistries ranging from acidic to alkaline. Comparisons with data reported for 159 other upland, forested watersheds in central New England show that our study watersheds span the regional range likely to be encountered in stream chemistry. The regional variability stems in part from past natural disturbances such as wildfire, and variations in source of soil parent material. An approach is presented for predicting the important influence of glacial till on stream chemistry, including acid-base relationships, aluminum content, and nutrient outputs. Knowledge of streamwater chemistry and controlling factors can serve as an index of how terrestrial and aquatic ecosystems will respond to forest management activities and atmospheric deposition.

Forest Ecology and Management

Patterns and controls of foliar nutrient stoichiometry and flexibility across United States forests

Plant element stoichiometry and stoichiometric flexibility strongly regulate ecosystem responses to global change. Here, we tested three potential mechanistic drivers (climate, soil nutrients, and plant taxonomy) of both using paired foliar and soil nutrient data from terrestrial forested National Ecological Observatory Network sites across the USA. We found that broad patterns of foliar nitrogen (N) and foliar phosphorus (P) are explained by different mechanisms. Plant taxonomy was an important control over all foliar nutrient stoichiometries and concentrations, especially foliar N, which was dominantly related to taxonomy and did not vary across climate or soil gradients. Despite a lack of site-level correlations between N and environment variables, foliar N exhibited intraspecific flexibility, with numerous species-specific correlations between foliar N and various environmental factors, demonstrating the variable spatial and temporal scales on which foliar chemistry and stoichiometric flexibility can manifest. In addition to plant taxonomy, foliar P and N:P ratios were also linked to soil nutrient status (extractable P) and climate, especially actual evapotranspiration rates. Our findings highlight the myriad factors that influence foliar chemistry and show that broad patterns cannot be explained by a single consistent mechanism. Furthermore, differing controls over foliar N versus P suggests that each may be sensitive to global change drivers on distinct spatial and temporal scales, potentially resulting in altered ecosystem N:P ratios that have implications for processes ranging from productivity to carbon sequestration.

Ecology

U/Th series radionuclides as coastal groundwater tracers

The study of coastal groundwater has recently surfaced as an active interdisciplinary area of research, driven foremost by its importance as a poorly quantified pathway for subsurface material transport into coastal ecosystems. Key issue in coastal groundwater research include a complete geochemical characterization of the groundwater(s); quantification of the kinetics of subsurface transport, including rock-water interactions; determination of groundwater ages; tracing of groundwater discharge into coastal waters using radiochemical fingerprints; and an assessment of the potential ecological impact of such subsurface flow to a reviving water body. For such applications, the isotopic systemics of select naturally occurring radionucludes in the U/Th series has proven to be particularly useful. These radionuclides (e.g., U, Th, Ram and Rn) are ubiquitous in all groundwaters ad are represented by several isotopes with widely different half-lives and chemistries (Figure 1). As a result, varied biogeochemical processes occurring over a broad range of time scales can be studied. In source rock, most U/Th series isotopes in secular equilibrium; that is, the rate of decay of a daughter isotope is equal to that of it radiogenic parent, and so will have equal activities (in this context, the specific activity is simply a measure of the amount of radioactivity per unit amount). In contrast, these nuclides exhibit strong fractionations within the surrounding groundwaters because of their respective physiochemical differences. Disequilibria in U/Th series radionuclides can thus be used to identify distinct water masses, quantify release rates from source rocks, assess groundwater migration rates, and assess groundwater discharge rates in coastal waters., Large isotopic variations also have the potential for providing precise fingerprints for groundwaters from specific aquifers and have been explored as a means for calculating groundwater ages and estuarine water mass transit times. The highly fractionated nature of U/Th series nuclides in groundwater is illustrated by the range in some measured activities. highest activities are typically observed for 222 Rn, reflecting the inert nature of this noble gas. Groundwater 222 Rn (t 1/2 =3.8) activities are thus controlled only by rapid in situ decay (Table 1) and production within host rocks, without the added complications of reversible removal via absorption or precipitation. Uranium, which is soluble as U(VI) in oxidizing waters, is present in intermediate activities in groundwaters that are moderated by redox-initiated removal onto aquifer rocks. The alkaline earth Ra and, to a greater extent, the less soluble actinide Th are readily removed from groundwater by water -- rock interactions and so are strongly depleted. Both of these elements have very short-lived as well as longer-lived isotopes, and so isotopes compositions reflect processes over a range of time scales. Many studies have evaluated and behavior of select radionuclides in groundwater and surface water systems. Recent advances in high-=precision mass spectrometry have opted new possibilities for more subtle interpretations in select long-lived U/Th series isotopes, such as U, Ra, Pa, and Th. However, these techniques have yet to be fully developed, ahns as a consequence, such data remain largely scarce and underutilized. Although many different approaches have been developed to study radionucluide behavior in groundwater, all are based on principles of radioactive production and decay and knowledge of source terms from weathering and recoil processes, as well as removal terms from the interaction with aquifer host rock surface by sorption and precipitation. This review is structured to present first a brief description of the background, driving forces, scales, and ecological significance of submarine groundwater discharge. Following this, a description of the geochemistry and behavior of select radionuclides in groundwater will be presented, and their application to tracing submarine groundwater discharge will be discussed.

Chemical Reviews