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Assessment of PDMS-water partition coefficients: implications for passive environmental sampling of hydrophobic organic compounds

Solid-phase microextraction (SPME) has shown potential as an in situ passive-sampling technique in aquatic environments. The reliability of this method depends upon accurate determination of the partition coefficient between the fiber coating and water (K f ). For some hydrophobic organic compounds (HOCs), K f values spanning 4 orders of magnitude have been reported for polydimethylsiloxane (PDMS) and water. However, 24% of the published data examined in this review did not pass the criterion for negligible depletion, resulting in questionable K f values. The range in reported K f is reduced to just over 2 orders of magnitude for some polychlorinated biphenyls (PCBs) when these questionable values are removed. Other factors that could account for the range in reported K f , such as fiber-coating thickness and fiber manufacturer, were evaluated and found to be insignificant. In addition to accurate measurement of K f , an understanding of the impact of environmental variables, such as temperature and ionic strength, on partitioning is essential for application of laboratory-measured K f values to field samples. To date, few studies have measured K f for HOCs at conditions other than at 20 degrees or 25 degrees C in distilled water. The available data indicate measurable variations in K f at different temperatures and different ionic strengths. Therefore, if the appropriate environmental variables are not taken into account, significant error will be introduced into calculated aqueous concentrations using this passive sampling technique. A multiparameter linear solvation energy relationship (LSER) was developed to estimate log K f in distilled water at 25 degrees C based on published physicochemical parameters. This method provided a good correlation (R2 = 0.94) between measured and predicted log K f values for several compound classes. Thus, an LSER approach may offer a reliable means of predicting log K f for HOCs whose experimental log K f values are presently unavailable. Future research should focus on understanding the impact of environmental variables on K f . Obtaining the data needed for an LSER approach to estimate K f for all environmentally relevant HOCs would be beneficial to the application of SPME as a passive-sampling technique.

Environmental Science & Technology↗

Sampling bird communities in bottomland hardwood forests of the Mississippi Alluvial Valley: Number of points visited versus number of visits to a point

Within each of 4 forest stands on Delta Experimental Forest (DEF), 25 points were visited 5 to 7 times from 8 May to 21 May 1991, and 6 times from 30 May to 12 June 1992. During each visit to a point, all birds detected, visuallyor aurally, at any distance were recorded during a 4-minute interval. Using these data, our objectives were to recommend the number of point counts and the number of visits to a point which provide the greatest efficiency for estimating the cumulative number of species in bottomland hardwood forest stands within the Mississippi Alluvial Valley, and to ascertain if increasing the number of visits to points is equivalent to adding more points. Because the total number of species detected in DEF were different between years, 39 species in 1991 and 55 species in 1992, we considered each year independently. Within each stand, we obtained bootstrap estimates of the mean cumulative number of species obtained from all possible combinations of six points and six visits (i.e., 36 means/stand). These bootstrap estimates were subjected to ANOVA; we modelled cumulative number of species as a function of the number of points visited, the number of visits to each point, and their interaction. As part of the same ANOVA we made an a priori, simultaneous comparison of the 15 possible reciprocal treatments (i.e., 1 point-2 visits vs. 2 points-1 visit, etc.). Results of analyses for each year were similar. Although no interaction was detected between the number of points and the number of visits, when reciprocals were compared, more points visited yielded significantly greater cumulative number of species than more visits to each point. Significant differences were detected among both the number of points visited and among the number of visits to a point. Scheffe's test of differences among means indicated that the cumulative number of species increased significantly with each added point, through five points, but six points did not differ from five points in 1991. Similarly, the cumulative number of species increased significantlywith each revisit, up to four visits, but four visits did not differ significantly from five visits. Starting with one point, which yielded about 33 percent of the total species pool when averaged among one through six points, each subsequent point resulted in an increase of about 9 percent, 5 percent, 3 percent, and 3 percent, respectively. Each sequential increase in the number of visits, however, only resulted in increases of 7 percent, 4 percent, 2 percent, and 2 percent of the total species pool.

Book chapter↗

The occurrence and significance of polychlorinated biphenyls in the environment

SUMMARY: Polychlorinated biphenyls constitute a group of chlorine-bearing compounds of industrial origin that have permeated the natural environment throughout the world. Their chemical structure resembles that of some of the organochlorine pesticides. They are troublesome interferences in gas chromatographic analysis of these pesticides. Although methods have been developed to overcome analytical problems, measurements of quantity still are only approximate. Special studies in the United States, Netherlands, and Great Britain have traced PCB's to industrial effluent, but other possible sources have not been followed. Their use in paints, cartons, and insulating fluids suggests that environmental pollution may be from many different sources. PCB's are present in fish and wildlife in many countries of the world. Quantities are higher in animals living near industrial areas. PCB's build up in biological food chains with increases of tens to thousands of times from lower to higher organisms. Experimental studies have shown that PCB's have a toxicity to mallards, pheasants, bobwhite quail, coturnix quail, red-winged blackbirds, starlings, cowbirds, and grackles that is of the same order as the toxicity of DDE to these species. Overt signs of poisoning also are similar to those caused by compounds of the DDT group. Toxic effects of DDE and Aroclor 1254 to coturnix chicks were additive, but not synergistic. PCB's containing higher percentages of chlorine are more toxic to birds than those containing lower percentages. PCB's of foreign manufacture contained contaminants to an extent that greatly increased their toxicity Aroclor 1242. Statistical evaluations of the role that different chemicals may play in thinning of eggshells of brown pelicans show that DDE residues correlate better with shell thinning than do residues of dieldrin or PCB's. Studies of the effects of PCB's in the environment are as yet insufficient for well-rounded conclusions. The evidence available indicates that they must be viewed as potential problems until fuller data can be assembled. Toxicity to insects of PCB's of different degrees of chlorination is the reverse of the pattern in birds: the lower chlorinations are more toxic to insects. PCB's enhanced the toxicity of dieldrin and DDT to insects. Shrimp are very sensitive to PCB's and most will die as a result of 20-day exposure to a concentration of 5 ppb. PCB's also inhibit shell growth of oysters. Fish and crabs are less sensitive; all accumulate residues to many times the concentrations in the water, and a test with crabs showed that they lost the residues very slowly. Residues of PCB's in the brains of birds killed by these compounds measure in the hundreds of parts per million. PCB's may have contributed to mortality of some birds in the field. PCB's induce microsomal enzyme activity in birds and mammals and the lower chlorinated mixtures have estrogenic activity in rats. Exposure to PCB's increased the susceptibility of mallard ducklings to duck hepatitis virus. Offspring of pheasants whose parents received high dosages of PCB's made poor choices in visual cliff tests. Egg production and hatching after pipping also were affected. Long-term studies of the reproductive effects of Aroclor 1254 on mallards and bobwhite quail and of Aroclor 1254 plus DDE on quail showed no significant differences from controls. In studies of chickens, however, egg production, hatchability, and shell thickness were impaired by high doses of Aroclor 1254 and by low doses of Aroclor 1242. Statistical evaluations of the role that different chemicals may play in thinning of eggshells of brown pelicans show that DDE residues correlate better with shell thinning than do residues of dieldrin or PCB's. Studies of the effects of PCB's in the environment are as yet insufficient for well-rounded conclusions. The evidence available indicates that they must be

Transactions of the North American Wildlife and Na↗

Inorganic N and P dynamics of Antarctic glacial meltwater streams as controlled by hyporheic exchange and benthic autotrophic communities

The McMurdo Dry Valleys of South Victoria Land, Antarctica, contain numerous glacial meltwater streams that drain into lakes on the valley floors. Many of the streams have abundant perennial mats of filamentous cyanobacteria. The algal mats grow during streamflow in the austral summer and are in a dormant freeze-dried state during the rest of the year. NO 3 and soluble reactive P (SRP) concentrations were lower in streams with abundant algal mats than in streams with sparse algal mats. NO 3 and SRP concentrations were higher in the hyporheic zone of a stream with abundant algal mats than in the stream itself. An experimental injection of LiCl, NaNO 3 , and K 3 PO 4 was conducted in Green Creek, which has abundant algal mats. Substantial hyporheic exchange occurred. The NO 3 and PO 4 concentrations at 50 m below the injection were 55 μM and 18 μM, respectively, during the experiment. NO 3 and PO 4 concentrations were below the detection limit of 1 to 2 μM at a site 497 m below the injection during the Cl tracer arrival, indicating a high capacity for nutrient uptake by algal communities. NO 2 and NH 4 were present at sites 226 and 327 m below the injection, indicating that, in addition to denitrification and algal uptake, dissimilatory NO 3 reduction to NO 2 and NH 4 may be a NO 3 sink during transport. Transport modelling with nutrient uptake represented as a 1 st -order process yielded reach-scale parameters of 4.3 × 10 −5 to 3.9 × 10 −4 /s and 1.4 × 10 −4 to 3.8 × 10 −4 /s for uptake of NO 3 and PO 4 , respectively. The best match with the observed data was a model in which PO 4 uptake occurred only in the main channel and NO 3 uptake occurred in the main channel and in the hyporheic zone. Hyporheic NO 3 uptake was 7 to 16% of the total uptake for the different stream reaches. These results demonstrate that nutrient flux to the lakes is controlled by hyporheic exchange and nutrient uptake by algal mats in dry valley streams. Streams without algal mats contribute more nutrients to the lakes than streams with algal mats.

Journal of the North American Benthological Societ↗

Osmotic potential and projected drought tolerance of four phreatophytic shrub species in Owens Valley, California

A large part of the water used by plant communities growing on the floor of Owens Valley, California, is derived from a shallow unconfined aquifer. Fluctuations in the water table caused by groundwater withdrawal may result in periods when this water supply is not accessible to plants. The capacity of the plants to adapt to these periods of water loss depend on the availability of water stored in the soil and on physiological characteristics related to the ability of the plants to resist dehydration and wilting. Osmotic adjustment occurred in four phreatophytic shrub species at sites near bishop, California, where the water table had been lowered by a system of pump-equipped wells installed in the vicinity of vegetation transects. The pressure-volume techniques was used to determine osmotic potential and cell-wall elasticity between March 1985 and September 1986 for Atriplex torreyi, Chrysothamnus nauseosus , Sarcobatus vermiculatus, and Artemisia tridentata. Although not usually classified as a phreatophyte, Artemisia tridentata, where it grows on the valley floor, is apparently dependent on the depth to the water table. During late summer, osmotic potentials were 0.37 to 0.41 megapascal lower in plants growing on the site where the water table had been lowered compared to an adjacent site where the water table remained at its natural levels. Measurements of soil matric potential at the two sites indicated that osmotic adjustment occurred in response to stress caused by lowering the water table. A theoretical lower limit of osmotic adjustment was determined by comparing initial cell osmotic potentials with initial xylem water potentials. These experimentally derived limits indicated that A. torreyi and S. vermiculatus may maintain leaf cell turgor at significantly lower cell water potentials (about -4.5 megapascals) than C. nauseosus or A. tridentata (about -2.5 megapascals) and allows them to function in dryer soil environments. (Author 's abstract)

California↗

Final integrated trip report: site visits to Area 50, Andersen Air Force Base, Guam National Wildlife Refuge, War in the Pacific National Historical Park, Guam, Rota and Saipan, CNMI, 2004-2005

Limestone forests are the most diverse natural plant communities of Guam. Like other natural vegetation types, these forests have a long history of anthropogenic disturbances, being altered and shaped by humans for more than 4,000 years. Although this occupation represents a relatively long human influence in comparison to other Pacific islands, animals associated with humans, such as commensal rodents, arrived in these islands beginning only 1,000 years ago, and larger mammals, such as pigs (Sus scrofa), may not have arrived until European contact. Limestone forests, which also occur on several other Mariana Islands, developed in the presence of frequent tropical storms and are therefore well adapted to this type of natural disturbance regime. However, recent human activities including large scale clearing and conversion combined with the presence of high levels of alien herbivores and seed predators, and the loss of ecological services provided by the former native avifauna may be causing the decline of Guam's forests. Limestone forests on northern Guam, much like those of other Mariana Islands, were heavily cleared for the construction of military installations during World War II. The accidental introduction of the Brown Tree Snake (Boiga irregularis; BTS) around this same period subsequently accelerated the disappearance of Guam's native avifauna and other endemic terrestrial vertebrates, and with them, seed dispersal, pollination, and the predatory regulation of herbivorous insects. Guam and the Mariana Islands contained a high proportion (32 pecent) of endemic bird species, with 4 forms endemic to Guam alone: the now extinct Guam Flycatcher (Myiagra freycineti), and Guam Bridled White-eye (Zosterops conspicillatpicillata), one of three island endemic subspecies from the Marianas; Guam rail (Rallus owstonii); and Guam Kingfisher (Todiramphus cinnamominus cinnamominus), an island endemic subspecies of the regionally endemic Micronesian Kingfisher. Guam once supported the Mariana Gallinule (Gallinula chloropus guami), the Mariana Mallard (Anas platyrhynchos oustaleti), Mariana Fruit-Dove (Ptilinopus roseicapilla), White-throated Ground Dove (Gallicolumba xanthonura xanthonura), Mariana Crow (Corvus kubaryi), and the Nightingale Reed-warbler (Acrocephalus luscinia), all endemic to the Mariana Islands. Other regionally endemic endangered species include the Micronesian Megapode (Megapodius laperouse), and the Mariana Swiftlet (Aerodramus bartschi), now reduced to a small population on Guam. Likewise, the flora of Guam is unique, with 21percent of its native vascular plants endemic to the Mariana Islands. In limestone forests of Northern Guam, a number of tall forest tree species such as joga, Elaeocarpus joga (Elaeocarpaceae); pengua or Macaranga thompsonii (Euphorbiaceae); ifit or Intsia bijuga (Fabaceae); seeded breadfruit or Artocarpus marianensis (Moraceae); and umumu or Pisonia grandis (Nyctaginaceae) may be in decline as a result of herbivory by mammals. All show reduced regeneration and age distributions highly skewed towards older individuals. These species provided important habitat for some of Guam's endangered forest birds that remain in captivity such as the Mariana Crow, Guam Kingfisher, and Guam Rail. The recent high frequency of intense tropical storms and herbivory caused by large populations of feral pigs and Philippine sambar deer (Cervus mariannus), as well as invasive alien vines that may suppress tree regeneration, could be permanently altering the structure of regenerating forests and composition of important canopy species on secondary limestone substrates that were cleared and compacted during airfield construction from 1944 through the 1970s. Guam National Wildlife Refuge (GNWR) was established at Ritidian Point, after it was determined to be excess property by the U.S. Navy. Most of the refuge, about 9,087 hectares, is an 'overlay refuge' on lands administered by the U.S. Air Force and U.S. Navy. Although the military mission comes first on these lands, the U.S. Fish and Wildlife Service assists in protecting native species and habitats. The recovery of limestone forest on Guam for forest bird habitat may require intensive management, including reduction of feral herbivores, propagation, out-planting, weed control, and periodic suppression of herbivorous insects. Research to support these techniques may be best accomplished in small areas where potential limiting factors can easily be experimentally manipulated. Area 50, a 24 ha enclosure, contains a relictual patch of relatively undisturbed limestone forest surrounded by tarmac allowing easy access and management opportunities to control alien mammals and snakes. These species have been periodically managed in the past, but recent typhoons have damaged snake-proofing on the enclosure fence. A new concrete barrier is planned to provide more permanent control opportunities within this enclosed area or another similar area, thereby allowing experimental research for various management regimes. Eradication and control of alien vertebrate and plant pests will provide habitat where native communities can be restored in a small, intensively managed area. The stated aim of this project is to "affect ecosystem restoration through the removal and exclusion of introduced species and the reestablishment and propagation of native species, with focus on the reintroduction of native forest bird species." This will be achieved by constructing a multispecies barrier surrounding the area, coordinated eradication of selected alien species within the area, and possible reintroduction of Mariana Crow, Guam Kingfisher, and Guam Rail. This barrier also allows experimental research questions to be addressed within the small enclosure around Area 50 that may be applied to manage and restore the larger areas of limestone forest on northern Guam and also similar forests on other islands of the Marianas.

Open-File Report↗

Osmotic potential and projected drought tolerance of four phreatophytic shrub species in Owens Valley, California

A substantial quantity of the water used by plant communities growing on the floor of Owens Valley, California, is derived from a shallow unconfined aquifer. Fluctuations in the water table caused by ground-water withdrawal may result in periods when this water supply is not accessible to plants. The capacity of the plants to adapt to these periods of water loss depends on the availability of water stored in the soil and on physiological characteristics related to the ability of the plants to resist dehydration and wilting. Osmotic adjustment occurred in four phreatophytic shrub species at sites near Bishop, California, where the water table had been lowered by a system of pump-equipped wells installed in the vicinity of vegetation transects. The pressure-volume technique was used to determine osmotic potential and cell-wall elasticity between March 1985 and September 1986 for Atriplex torreyi, Chrysothamnus nauseosus , Sarcobatus verm iculatus , and Artemisia tridentata. Although not usually classified as a phreatophyte, Artemisia tridentata, where it grows on the valley floor, is apparently dependent on the depth to the water table. During late summer, osmotic potentials were 0.37 to 0.41 MPa (megapascal) lower in plants growing on the site where the water table had been lowered compared to an adjacent site where the water table remained at its natural levels. Measurements of soil matric potential at the two sites indicated that osmotic adjustment occurred in response to stress caused by lowering the water table. A theoretical lower limit of osmotic adjustment was determined by comparing initial cell osmotic potentials with initial xylem water potentials. These experimentally derived limits indicated that Atriplex torreyi and S. vermiculatus may maintain leaf cell turgor at significantly lower cell water potentials (about -4.5 MPa) than C. nauseosus or Artemisia tridentata (about -2.5 MPa), which allows them to function in drier soil environments.

Water Supply Paper↗

An introduced predator alters Aleutian Island plant communities by thwarting nutrient subsidies

The ramifying effects of top predators on food webs traditionally have been studied within the framework of trophic cascades. Trophic cascades are compelling because they embody powerful indirect effects of predators on primary production. Although less studied, indirect effects of predators may occur via routes that are not exclusively trophic. We quantified how the introduction of foxes onto the Aleutian Islands transformed plant communities by reducing abundant seabird populations, thereby disrupting nutrient subsidies vectored by seabirds from sea to land. We compared soil and plant fertility, plant biomass and community composition, and stable isotopes of nitrogen in soil, plants, and other organisms on nine fox-infested and nine historically fox-free islands across the Aleutians. Additionally, we experimentally augmented nutrients on a fox-infested island to test whether differences in plant productivity and composition between fox-infested and fox-free islands could have arisen from differences in nutrient inputs between island types. Islands with historical fox infestations had soils low in phosphorus and nitrogen and plants low in tissue nitrogen. Soils, plants, slugs, flies, spiders, and bird droppings on these islands had low d15N values indicating that these organisms obtained nitrogen from internally derived sources. In contrast, soils, plants, and higher trophic level organisms on fox-free islands had elevated d15N signatures indicating that they utilized nutrients derived from the marine environment. Furthermore, soil phosphorus (but not nitrogen) and plant tissue nitrogen were higher on fox-free than fox-infested islands. Nutrient subsidized fox-free islands supported lush, high biomass plant communities dominated by graminoids. Fox-infested islands were less graminoid dominated and had higher cover and biomass of low-lying forbs and dwarf shrubs. While d15N profiles of soils and plants and graminoid biomass varied with island size and distance from shore, after accounting for these effects differences between fox-infested and fox-free islands still existed. Fertilization over four years caused a 24-fold increase in graminoid biomass and a shift toward a more graminoid dominated plant community typical of fox-free islands. These results indicate that apex predators can influence plant productivity and composition through complex interaction web pathways involving both top-down forcing and bottom-up nutrient exchanges across systems. ?? 2006 by the Ecological Society of America.

Ecological Monographs↗

Experimental stocking of sport fish in the regulated Tallapoosa River to determine critical periods for recruitment

The stocking of fish in riverine systems to re-establish stocks for conservation and management appears limited to a few species and often occurs in reaches impacted by impoundments. Stocking of sport fish species such as centrarchids and ictalurids is often restricted to lentic environments, although stocking in lotic environments is feasible with variable success. R. L. Harris Dam on the Tallapoosa River, Alabama is the newest and uppermost dam facility on the river (operating since 1983); flows from the dam have been managed adaptively for multiple stakeholder objectives since 2005. One of the stakeholders’ primary objectives is to provide quality sport fisheries in the Tallapoosa River in the managed area below the dam. Historically, ictalurids and cyprinids dominated the river above Lake Martin. However, investigations after Harris Dam closed have detected a shift in community structure to domination by centrarchids. Flow management (termed the Green Plan) has been occurring since March 2005; however, sport fish populations as measured by recruitment of age-1 sport fishes below the dam has not responded adequately to flow management. The objectives of this research were to: (1) determine if stocking Channel Catfish Ictalurus punctatus and Redbreast Sunfish Lepomis auritus influences year-class strength; (2) estimate vital rates (i.e. growth, mortality, and recruitment) for Channel Catfish populations for use in an age-based population model; and (3) identify age-specific survivorship and fecundity rates contributing to Channel Catfish population stability. No marked Redbreast Sunfish were recaptured due to poor marking efficacy and therefore no further analysis was conducted with this species. Stocked Channel Catfish, similarly, were not recaptured, leaving reasons for non-recapture unknown. Matrix models exploring vital rates illustrated survival to age-1 for Channel Catfish to be less than 0.03% and that survival through ages 2 – 4 had equal contribution to overall population growth, indicating recruitment limitation may impact population size and stability. Results from this study indicate stock enhancement of sport fish populations below Harris Dam may not be an effective management technique at this time.

Alabama↗

Lethal impacts of selenium counterbalance the potential reduction in mercury bioaccumulation for freshwater organisms☆

Mercury (Hg), a potent neurotoxic element, can biomagnify through food webs once converted into methylmercury (MeHg). Some studies have found that selenium (Se) exposure may reduce MeHg bioaccumulation and toxicity, though this pattern is not universal. Se itself can also be toxic at elevated levels. We experimentally manipulated the relative concentrations of dietary MeHg and Se (as selenomethionine [SeMet]) for an aquatic grazer (the mayfly, Neocloeon triangulifer) and its food source (diatoms). Under low MeHg treatment (0.2 ng/L), diatoms exhibited a quadratic pattern, with decreasing diatom MeHg concentration up to 2.0 μg Se/L and increasing MeHg accumulation at higher SeMet concentrations. Under high MeHg treatment (2 ng/L), SeMet concentrations had no effect on diatom MeHg concentrations. Mayfly MeHg concentrations and biomagnification factors (concentration of MeHg in mayflies: concentration of MeHg in diatoms) declined with SeMet addition only in the high MeHg treatment. Mayfly MeHg biomagnification factors decreased from 5.3 to 3.3 in the high MeHg treatment, while the biomagnification factor was constant with an average of 4.9 in the low MeHg treatment. The benefit of reduced MeHg biomagnification was offset by non-lethal effects and high mortality associated with ‘protective’ levels of SeMet exposure. Mayfly larvae escape behavior (i.e., startle response) was greatly reduced at early exposure days. Larvae took nearly twice as long to metamorphose to adults at high Se concentrations. The minimum number of days to mayfly emergence did not differ by SeMet exposure, with an average of 13 days. We measured an LC50SeMet for mayflies of 3.9 μg Se/L, with complete mortality at concentrations ≥6.0 μg Se/L. High reproductive mortality occurred at elevated SeMet exposures, with only 0–18% emergence at ≥4.12 μg Se/L. Collectively, our results suggest that while there is some evidence that Se can reduce MeHg accumulation at the base of the food web at specific exposure levels of SeMet and MeHg, Se is also toxic to mayflies and could lead to negative effects that extend across ecosystem boundaries.

Environmental Pollution↗

Greenhouse gas fluxes from salt marshes exposed to chronic nutrient enrichment

We assessed the impact of nutrient additions on greenhouse gas fluxes using dark static chambers in a microtidal and a macrotidal marsh along the coast of New Brunswick, Canada approximately monthly over a year. Both were experimentally fertilized for six years with varying levels of N and P. For unfertilized, N and NPK treatments, average yearly CO 2 emissions (which represent only respiration) at the microtidal marsh (13, 19, and 28 mmoles CO 2 m -2 hr -1 , respectively) were higher than at the macrotidal marsh (12, 15, and 19 mmoles m -2 hr -1 , respectively, with a flux under the additional high N/low P treatment of 21 mmoles m -2 hr -1 ). Response of CH 4 to fertilization was more variable. At the macrotidal marsh average yearly fluxes were 1.29, 1.26, and 0.77 μmol CH 4 m -2 hr -1 with control, N, and NPK treatments, respectively and 1.21 μmol m -2 hr -1 under high N/low P treatment. At the microtidal marsh CH 4 fluxes were 0.23, 0.16, and -0.24 μmol CH 4 m -2 hr -1 in control, N, and NPK and treatments, respectively. Fertilization changed soils from sinks to sources of N 2 O. Average yearly N 2 O fluxes at the macrotidal marsh were -0.07, 0.08, and 1.70, μmol N 2 O m -2 hr -1 in control, N, NPK and treatments, respectively and 0.35 μmol m -2 hr -1 under high N/low P treatment. For the control, N, and NPK treatments at the microtidal marsh N 2 O fluxes were -0.05, 0.30, and 0.52 μmol N 2 O m -2 hr -1 , respectively. Our results indicate that N 2 O fluxes are likely to vary with the source of pollutant nutrients but emissions will be lower if N is not accompanied by an adequate supply of P (e.g., atmospheric deposition vs sewage or agricultural runoff). With chronic fertilization the global warming potential of the increased N 2 O emissions may be enough to offset the global cooling potential of the C sequestered by salt marshes.

New Brunswick↗

Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining

Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles. Average δ 66 Zn and δ 65 Cu values for streams varied from +0.02‰ to +0.46‰ and −0.7‰ to +1.4‰, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ∼0.3‰ ( 66/64 Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales.

Geochimica et Cosmochimica Acta↗

Paired air-water annual temperature patterns reveal hydrogeological controls on stream thermal regimes at watershed to continental scales

Despite decades of research into air and stream temperature dynamics, paired air-water annual temperature signals have been underutilized to characterize watershed processes. Annual stream temperature dynamics are useful in classifying fundamental thermal regimes and can enhance process-based interpretation of stream temperature controls, including deep and shallow groundwater discharge, when paired with air signals. In this study, we investigated multi-scale variability in annual paired air-water temperature patterns using sine-wave linear regressions of multi-year daily temperature data from streams of various sizes. A total of 311 sites from two spatially intensive regional datasets (Shenandoah National Park and Olympic Experimental State Forest) and a spatially extensive national dataset spanning the contiguous United States (U.S. Geological Survey gages) were evaluated. We calculated three annual air-water thermal metrics (mean ratio, phase lag, and amplitude ratio) to deduce the influence of groundwater and other watershed processes on stream thermal regimes at multiple spatial scales. Site-specific values of the three annual air-water thermal metrics ranged from 0.69 to 5.29 (mean ratio), −9 to 40 days (phase lag), and 0.29 to 1.12 (amplitude ratio). Regional patterns in the annual thermal metrics revealed persistent yet spatially variable influences of shallow groundwater discharge and high levels of thermal variability within watersheds, indicating the importance of local hydrogeological controls on stream temperature. Furthermore, annual thermal metric patterns from the regional datasets were generally concordant with the national dataset suggesting the utility of these annual thermal metrics for analysis at multiple scales. Analysis of the national dataset showed that previously defined thermal regimes based on water temperature alone could be further refined using air-water metrics and these metrics were related to physiographic watershed characteristics such as contributing area, elevation, and slope. This research demonstrates the importance of spatial scale and heterogeneity for inferring hydrological process in streams and provides guidance for the interpretation of annual air-water temperature metrics that can be efficiently applied to the growing database of multi-year temperature records. Results from this research can aid in the prediction of future thermal habitat suitability for coldwater-adapted species at ecologically and management-relevant spatial scales with readily available data.

Continental United States↗

Predicting landslide vegetation in patches on landscape gradients in Puerto Rico

We explored the predictive value of common landscape characteristics for landslide vegetative stages in the Luquillo Experimental Forest of Puerto Rico using four different analyses. Maximum likelihood logistic regression showed that aspect, age, and substrate type could be used to predict vegetative structural stage. In addition it showed that the structural complexity of the vegetation was greater in landslides (1) facing the southeast (away from the dominant wind direction of recent hurricanes), (2) that were older, and (3) that had volcaniclastic rather than dioritic substrate. Multiple regression indicated that both elevation and age could be used to predict the current vegetation, and that vegetation complexity was greater both at lower elevation and in older landslides. Pearson product-moment correlation coefficients showed that (1) the presence of volcaniclastic substrate in landslides was negatively correlated with aspect, age, and elevation, (2) that road association and age were positively correlated, and (3) that slope was negatively correlated with area. Finally, principal components analysis showed that landslides were differentiated on axes defined primarily by age, aspect class, and elevation in the positive direction, and by volcaniclastic substrate in the negative direction. Because several statistical techniques indicated that age, aspect, elevation, and substrate were important in determining vegetation complexity on landslides, we conclude that landslide succession is influenced by variation in these landscape traits. In particular, we would expect to find more successional development on landslides which are older, face away from hurricane winds, are at lower elevation, and are on volcaniclastic substrate. Finally, our results lead into a hierarchical conceptual model of succession on landscapes where the biota respond first to either gradients or disturbance depending on their relative severity, and then to more local biotic mechanisms such as dispersal, predation and competition.

Landscape Ecology↗

Experimental infection of nontarget species of rodents and birds with Brucella abortus strain RB51 vaccine

The Brucella abortus vaccine strain RB51 (SRB51) is being considered for use in the management of brucellosis in wild bison ( Bison bison ) and elk ( Cervus elaphus ) populations in the Greater Yellowstone Area (USA). Evaluation of the vaccine's safety in non-target species was considered necessary prior to field use. Between June 1998 and December 1999, ground squirrels ( Spermophilus richardsonii , n = 21), deer mice ( Peromyscus maniculatus , n = 14), prairie voles ( Microtus ochrogaster , n = 21), and ravens ( Corvus corax , n = 13) were orally inoculated with SRB51 or physiologic saline. Oral and rectal swabs and blood samples were collected for bacteriologic evaluation. Rodents were necropsied at 8 to 10 wk and 12 to 21 wk post inoculation (PI), and ravens at 7 and 11 wk PI. Spleen, liver and reproductive tissues were collected for bacteriologic and histopathologic evaluation. No differences in clinical signs, appetite, weight loss or gain, or activity were observed between saline- and SRB51-inoculated animals in all four species. Oral and rectal swabs from all species were negative throughout the study. In tissues obtained from SRB51-inoculated animals, the organism was isolated from six of seven (86%) ground squirrels, one of six (17%) deer mice, none of seven voles, and one of five (20%) ravens necropsied at 8, 8, 10, and 7 wk PI, respectively. Tissues from four of seven (57%) SRB51-inoculated ground squirrels were culture positive for the organism 12 wk PI; SRB51 was not recovered from deer mice, voles, or ravens necropsied 12, 21, or 11 wk, respectively, PI. SRB51 was not recovered from saline-inoculated ground squirrels, deer mice, or voles at any time but was recovered from one saline-inoculated raven at necropsy, 7 wk PI, likely attributable to contact with SRB51-inoculated ravens in an adjacent aviary room. Spleen was the primary tissue site of colonization in ground squirrels, followed by the liver and reproductive organs. The results indicate oral exposure to SRB51 does not produce morbibity or mortality in ravens, ground squirrels, deer mice, or prairie voles.

Colorado, Montana, Wyoming↗

Extending the turbidity record: making additional use of continuous data from turbidity, acoustic-Doppler, and laser diffraction instruments and suspended-sediment samples in the Colorado River in Grand Canyon

Turbidity is a measure of the scattering and absorption of light in water, which in rivers is primarily caused by particles, usually sediment, suspended in the water. Turbidity varies significantly with differences in the design of the instrument measuring turbidity, a point that is illustrated in this study by side-by-side comparisons of two different models of instruments. Turbidity also varies with changes in the physical parameters of the particles in the water, such as concentration, grain size, grain shape, and color. A turbidity instrument that is commonly used for continuous monitoring of rivers has a light source in the near-infrared range (860±30 nanometers) and a detector oriented 90 degrees from the incident light path. This type of optical turbidity instrument has a limited measurement range (depending on pathlength) that is unable to capture the high turbidity levels of rivers that carry high suspended-sediment loads. The Colorado River in Grand Canyon is one such river, in which approximately 60 percent of the range in suspended-sediment concentration during the study period had unmeasurable turbidity using this type of optical instrument. Although some optical turbidimeters using backscatter or other techniques can measure higher concentrations of suspended sediment than the models used in this study, the maximum turbidity measurable using these other turbidimeters may still be exceeded in conditions of especially high concentrations of suspended silt and clay. In Grand Canyon, the existing optical turbidity instruments remain in use in part to provide consistency over time as new techniques are investigated. As a result, during these periods of high suspended-sediment concentration, turbidity values that could not be measured with the optical turbidity instruments were instead estimated from concurrent acoustic attenuation data collected using side-looking acoustic-Doppler profiler (ADP) instruments. Extending the turbidity record to the full range of sediment concentrations in the study area using data from the ADP instruments is particularly useful for biological studies. In Grand Canyon, turbidity has been correlated with food availability for aquatic organisms (gross primary production) as well as with fish behavior specific to predator-prey interactions. On the basis of the complete “extended” turbidity record and the relation between suspended-sediment concentration and turbidity, levels were higher before the construction of Glen Canyon Dam by a factor of approximately 2,000 at the Lees Ferry monitoring station (15 miles downstream from the dam) and by a factor of approximately 20 at the monitoring station 87 miles downstream from Lees Ferry (102 miles downstream from the dam). A comparison of turbidity data with data from Laser In-Situ Scattering and Transmissometry (LISST) laser-diffraction instruments, suspended-sediment concentration data, and ADP data shows the influence of the physical properties of suspended sediment. Apparent outliers in relations between turbidity, ADP, and suspended-sediment data during two events within the study period, a 2007 tributary flood from a watershed altered by a recent wildfire and a 2008 experimental controlled-flood release from Glen Canyon Dam, are explained in part by atypical grain sizes, shapes, densities, colors, and (or) clay mineral assemblages of suspended sediment occurring in the Colorado River during these two events. These analyses demonstrate the value of using multiple data-collection strategies for turbidity and sediment-transport studies and of continuous monitoring for capturing the full range and duration of turbidity and sediment-transport conditions, identifying the provenance of the sediment causing turbidity, and detecting physical and chemical processes that may be important for management of critical physical and biological resources.

Arizona↗

A laboratory investigation of the suspension, transport, and settling of silver carp eggs using synthetic surrogates

Asian carp eggs are semi-buoyant and must remain suspended in the water to survive, supported by the turbulence of the flow, until they hatch and develop the ability to swim. Analysis of the transport and dispersal patterns of Asian carp eggs will facilitate the development and implementation of control strategies to target the early life stages. Experimenting with Asian carp eggs is complicated due to practical issues of obtaining eggs in close proximity to experimental facilities and extensive handling of eggs tends to damage them. Herein, we describe laboratory experiments using styrene beads (4.85 mm diameter) as synthetic surrogate eggs to mimic the physical properties of water-hardened silver carp eggs. The first set of experiments was completed in a rectangular vertical column filled with salt water. The salinity of the water was adjusted in an iterative fashion to obtain a close approximation of the fall velocity of the styrene beads to the mean fall velocity of silver carp water-hardened eggs. The terminal fall velocity of synthetic eggs was measured using an image processing method. The second set of experiments was performed in a temperature-controlled recirculatory flume with a sediment bed. The flume was filled with salt water, and synthetic eggs were allowed to drift under different flow conditions. Drifting behavior, suspension conditions, and settling characteristics of synthetic eggs were observed. At high velocities, eggs were suspended and distributed through the water column. Eggs that touched the sediment bed were re-entrained by the flow. Eggs saltated when they touched the bed, especially at moderate velocities and with a relatively flat bed. At lower velocities, some settling of the eggs was observed. With lower velocities and a flat bed, eggs were trapped near the walls of the flume. When bedforms were present, eggs were trapped in the lee of the bedforms in addition to being trapped near the flume walls. Results of this research study provide insights about transport, suspension, and dispersion of silver carp eggs. The knowledge gained from this study is useful to characterize the critical hydrodynamic conditions of the flow at which surrogates for silver carp water-hardened eggs settle out of suspension, and provides insight into how eggs may interact with riverbed sediments and morphology.

PLoS ONE↗

Depth calibration and validation of the Experimental Advanced Airborne Research Lidar, EAARL-B

The original National Aeronautics and Space Administration (NASA) Experimental Advanced Airborne Research Lidar (EAARL), was extensively modified to increase the spatial sampling density and improve performance in water ranging from 3–44 m. The new (EAARL-B) sensor features a 300% increase in spatial density, which was achieved by optically splitting each laser pulse into 3 pulses spatially separated by 1.6 m along the flight track and 2.0 m across-track on the water surface when flown at a nominal altitude of 300 m. Improved depth capability was achieved by increasing the total peak laser power by a factor of 10, and incorporating a new “deep-water” receiver, optimized to exclusively receive refracted and scattered light from deeper water (15–44 m). Two clear-water missions were conducted to determine the EAARL-B depth calibration coefficients. The calibration mission was conducted over the U.S. Navy’s South Florida Testing Facility (SFTF), an established lidar calibration range located in the coastal waters southeast of Fort Lauderdale, Florida. A second mission was conducted over Lang Bank, St. Croix, U.S. Virgin Islands. The EAARL-B survey was spatially and temporally coincident with multibeam sonar surveys conducted by the National Oceanic and Atmospheric Administration (NOAA) ship Nancy Foster. The NOAA depth data range from 10–100 m, whereas the EAARL-B captured data from 0–41 m. Coefficients derived from the SFTF calibration mission were used to correct the EAARL-B data from both missions. The resulting calibrated EAARL-B data were then compared with the original reference dataset, a jet-ski-based single beam sonar dataset from the SFTF site, and the deeper NOAA data from St. Croix. Additionally, EAARL-B depth accuracy was evaluated by comparing the depth results to International Hydrographic Organization (IHO) standards. Results show good agreement between the calibrated EAARL-B data and all three reference datasets, with 95% confidence levels well within the maximum allowable total vertical uncertainty for IHO Order 1 surveys.

Journal of Coastal Research↗