Influence of sea ice on Arctic precipitation.

Global climate is influenced by the Arctic hydrologic cycle, which is, in part, regulated by sea ice through its control on evaporation and precipitation. However, the quantitative link between precipitation and sea ice extent is poorly constrained. Here we present observational evidence for the response of precipitation to sea ice reduction and assess the sensitivity of the response. Changes in the proportion of moisture sourced from the Arctic with sea ice change in the Canadian Arctic and Greenland Sea regions over the past two decades are inferred from annually averaged deuterium excess (d-excess) measurements from six sites. Other influences on the Arctic hydrologic cycle, such as the strength of meridional transport, are assessed using the North Atlantic Oscillation index. We find that the independent, direct effect of sea ice on the increase of the percentage of Arctic sourced moisture (or Arctic moisture proportion, AMP) is 18.2 ± 4.6% and 10.8 ± 3.6%/100,000 km(2) sea ice lost for each region, respectively, corresponding to increases of 10.9 ± 2.8% and 2.7 ± 1.1%/1 °C of warming in the vapor source regions. The moisture source changes likely result in increases of precipitation and changes in energy balance, creating significant uncertainty for climate predictions.

Influence of sample preparation on estuarine macrofauna stable isotope signatures in the context of contaminant bioaccumulation studies.

The ratios of stable isotopes of carbon and nitrogen provide important information on food sources of aquatic organisms and trophic structure of aquatic food webs. For many studies, trophic position and food source are linked to bioaccumulation and trophic transfer of contaminants from prey to predators. In these cases, it is useful to use measurements on whole organisms to make direct comparisons of contaminant bioaccumulation and food web attributes. There is a great deal of variation in methods used for stable isotope analysis, particularly in the selection of tissue type and sample preparation prior to stable isotope analysis. While there have been aquatic studies that examined methodological differences, few have focused on estuarine organisms. In this study, the effects of depuration and tissue dissection on the stable isotope enrichment of common estuarine invertebrates and fish were examined. Homogenized tissues of non-depurated whole organisms were compared to dissected muscle tissue or depurated whole organisms. A 24 h depuration did not change the mean δ15N and δ13C values for most species examined. Additionally, as expected, significant differences in carbon and nitrogen signatures were found when muscle tissues were compared to whole organisms. However, differences were small enough that food source as inferred by δ13C or trophic level as inferred from δ15N would not be inaccurately represented (differences of <1.9‰ for δ13C and <1.2‰ for δ15N). The results of this study suggest that for these common estuarine fish and macroinvertebrates, stable isotopes ratios of samples can be analyzed without depuration in the same way as samples for contaminant analysis, but differences in tissue types must be taken into account when combining data from different sources.

Response of plants' water use efficiency to increasing atmospheric CO2 concentration.

This study assesses plants' adaptation to the elevated atmospheric CO(2) concentrations (c(a)) using 83 tree-ring δ(13)C series from the mid- to high-latitudes of the northern hemisphere. We found that the variation of Δ with the atmospheric CO(2) concentration is nonlinear and that the range of Δ change is relatively small. After 1950, the mean increase in Δ is 0.43‰, corresponding to the average coefficient of Δ-c(a) relationship to be about 0.006‰/ ppmv CO(2). In contrast to the changes in Δ, intercellular CO(2) concentration (c(i)) and intrinsic water-use efficiency (W(i)) both increase linearly with c(a). For the past two and a half centuries, changes in the intercellular CO(2) concentration (c(i)) and intrinsic water-use efficiency (W(i)) are, on average, both about 30%, while the mean change of the c(i)/c(a) ratio is 3%. Most changes have occurred after 1950. W(i) responds to c(a) linearly with sensitivities ranging from 0.06 to 0.6 µmol CO(2)/mmol H(2)O ppmv(-1), and an average 0.33 µmol CO(2)/mmol H(2)O ppmv(-1) during the past 50 years. Statistical analysis shows that the increase in c(a) accounts for 98% of the W(i) variation. The remaining small variance is explained by altitude and temperature. Trees at higher elevations show slightly higher increase in W(i), and they are also more sensitive to the CO(2) increase than trees at lower altitudes. Trees growing at low temperature environments are slightly more sensitive to CO(2) increase than those at higher temperature sites. No significant relationship between precipitation and plants' W(i) response to the atmospheric CO(2) increase is found with these data. Although the temperature and altitude both impact the W(i) response to elevated CO(2), the size of the impact is physically small and can be omitted from ecological models.

Radium in hydraulic fracturing wastewater: distribution in suspended solids and implications to its treatment by sulfate co-precipitation.

High concentrations of barium (Ba), strontium (Sr) and radium (Ra) are present in both the liquid and suspended solid portions of wastewater produced from hydraulic fracturing. These high concentrations often require special treatment in which the solid and liquid portions are separated and then independently treated prior to disposal. The solids are typically disposed in landfills while the liquids are further treated, recycled for future hydraulic fracturing, or disposed via injection wells. Finding optimal treatment methods of both the solid and the liquid fractions requires a thorough understanding of potential Ra mobility from both the raw suspended solids and mineral precipitates formed during treatment. Using a sequential extraction procedure, we found that, without treatment, more than 50% of Ra-226 in the suspended solids was associated with soluble salts and readily exchangeable fractions. When the liquid portion of the wastewater was treated by mixing with acid mine drainage (AMD), which contained high sulfate concentrations, approximately 80-97% of the total Ra-226 in the mixture solution is found in the insoluble sulfate fraction of the precipitate. The activity of Ra-226 sequestered in the precipitated solid sulfate fractions is positively correlated with the Sr/Ba ratio of the wastewater-AMD solution. We discuss implications of these findings for effective long-term management of elevated radium in both solid and liquid wastes.

Impact of land disturbance on the fate of arsenical pesticides.

Increasing development of historic farmlands raises questions regarding the fate of pesticides applied when these land were in cultivation. We quantified As and Pb budgets in field soils in two orchards where arsenical pesticides were applied in the early 20th century and a third uncontaminated control field. Sequential extractions and X-ray analyses also were used to determine mineral phases. In addition, we measured metal loads in drainages adjacent to the fields and in two common macroinvertebrate taxa within the wetland at the outlet of the drainages. We find that the applied As and Pb have undergone little vertical redistribution; concentrations of As and Pb in the top 25 cm of contaminated orchard soils are higher than in the uncontaminated control field. However, none of the applied lead arsenate (PbHAsO4) remains in its original mineral phase. Instead, the metals are now primarily adsorbed onto fine silt and clay-sized amorphous oxides and organic matter. Further, physical erosion associated with tilling and replanting appears to have mobilized the fine-particulate-bound As and Pb in one orchard. The remobilized metals are found in sediments in the stream channel draining the tilled orchard. It is unclear if the As and Pb transported sediments are biologically active; average macroinvertebrate metal burdens in the wetland are not elevated above those observed elsewhere in the region. However, little of the mobilized metals may have reached the wetland. These results demonstrate that land use change can significantly impact the retention of arsenical pesticides.

Long-term c i /c a response of trees in western North America to atmospheric CO2 concentration derived from carbon isotope chronologies.

To evaluate how the land carbon reservoir has been responding to the rising CO2 concentration of the atmosphere, it is important to study how plants in natural forests adjust physiologically to the changing atmospheric conditions. Many experimental studies have addressed this issue, but it has been difficult to scale short-term experimental observations to long-term ecosystem-level responses. This paper derives carbon-isotope-related variables for the past 100-200 years from measurements on trees from natural forests. Calculations show that the c i/c a ratios [c i/c a is the ratio of the CO2 concentration (µmol mol-1) in the intercellular space of leaves to that in the atmosphere] of the trees were constant or increased slightly before the 20th century, but changed more rapidly in the 20th century; some increased, some decreased, and some stayed constant. In contrast, the CO2 concentration inside plant leaves increased monotonically for all trees.

The use of isotope tracers for identifying populations of migratory birds.

To determine whether stable isotopes can be used for identifying the geographic origins of migratory bird populations, we examined the isotopic composition of hydrogen (deuterium, δD), carbon (δ13C), and strontium (δ87Sr) in tissues of a migratory passerine, the black-throated blue warbler (Dendroica caerulescens), throughout its breeding range in eastern North America. δD and δ13C values in feathers, which are grown in the breeding area, varied systematically along a latitudinal gradient, being highest in samples from the southern end of the species' breeding range in Georgia and lowest in southern Canada. In addition, δD decreased from east to west across the northern part of the breeding range, from New Brunswick to Michigan. δ87Sr ratios were highest in the Appalachian Mountains, and decreased towards the west. These patterns are consistent with geographical variation in the isotopic composition of the natural environment, i.e., with that of precipitation, plants, and soils for δD, δ13C, and δ87Sr, respectively. Preliminary analyses of the δD and δ13C composition of feathers collected from warblers in their Caribbean winter grounds indicate that these individuals were mostly from northern breeding populations. Furthermore, variances in isotope ratios in samples from local areas in winter tended to be larger than those in summer, suggesting that individuals from different breeding localities may mix in winter habitats. These isotope markers, therefore, have the potential for locating the breeding origins of migratory species on their winter areas, for quantifying the degree of mixing of breeding populations on migratory and wintering sites, and for documenting other aspects of the population structure migratory animals - information needed for studies of year-round ecology of these species as well as for their conservation. Combining information from several stable isotopes will help to increase the resolution for determining the geographic origins of individuals in such highly vagile populations.

Analyzing trophic transfer of metals in stream food webs using nitrogen isotopes.

This study examines detrimental effects of acid mine drainage (AMD) on stream invertebrate communities and tests for a direct relationship between trophic position and accumulation of three metals (Fe, Cu, Zn) by stream invertebrates in situ. On two dates in each of seven stream sites, we measured food chain length, mean trophic level, taxa richness, and trophic position of stream macroinvertebrates comprising the food webs using stable nitrogen isotope ratios. Metals in tissue of representatives of 35 taxa were measured by ICP-OES. Our results are the first direct comparison of uptake of these metals in stream invertebrate taxa according to trophic position as identified by delta15N. As predicted, metal concentrations were generally greater in water and insects from sites adjacent to mining activity and invertebrate taxa richness was significantly lower. Taxa richness increased with distance away from contaminated headwaters. Despite reductions in diversity at sites nearest AMD, food chain length and mean trophic level did not differ between streams. The relationship between trophic position and metal accumulation differed considerably among metals. Specifically, Fe declined (biodilution) and Zn increased (biomagnification) with trophic level, but trophic position had no effect on Cu levels in these insects. Our results highlight fundamental differences in trophic transfer of specific metals through aquatic food webs and identify ecologically important impacts of AMD on stream invertebrates.

Landfill-stimulated iron reduction and arsenic release at the Coakley Superfund Site (NH).

Arsenic is a contaminant at more than one-third of all Superfund Sites in the United States. Frequently this contamination appearsto resultfrom geochemical processes rather than the presence of a well-defined arsenic source. Here we examine the geochemical processes that regulate arsenic levels at the Coakley Landfill Superfund Site (NH), a site contaminated with As, Cr, Pb, Ni, Zn, and aromatic hydrocarbons. Long-term field observations indicate that the concentrations of most of these contaminants have diminished as a result of treatment by monitored natural attenuation begun in 1998; however, dissolved arsenic levels increased modestly over the same interval. We attribute this increase to the reductive release of arsenic associated with poorly crystalline iron hydroxides within a glaciomarine clay layer within the overburden underlying the former landfill. Anaerobic batch incubations that stimulated iron reduction in the glaciomarine clay released appreciable dissolved arsenic and iron. Field observations also suggest that iron reduction associated with biodegradation of organic waste are partly responsible for arsenic release; over the five-year study period since a cap was emplaced to prevent water flow through the site, decreases in groundwater dissolved benzene concentrations at the landfill are correlated with increases in dissolved arsenic concentrations, consistent with the microbial decomposition of both benzene and other organics, and reduction of arsenic-bearing iron oxides. Treatment of contaminated groundwater increasingly is based on stimulating natural biogeochemical processes to degrade the contaminants. These results indicate that reducing environments created within organic contaminant plumes may release arsenic. In fact, the strong correlation (>80%) between elevated arsenic levels and organic contamination in groundwater systems at Superfund Sites across the United States suggests that arsenic contamination caused by natural degradation of organic contaminants may be widespread.