The geologic history of seawater oxygen isotopes from marine iron oxides.

The oxygen isotope composition (δ18O) of marine sedimentary rocks has increased by 10 to 15 per mil since Archean time. Interpretation of this trend is hindered by the dual control of temperature and fluid δ18O on the rocks' isotopic composition. A new δ18O record in marine iron oxides covering the past ~2000 million years shows a similar secular rise. Iron oxide precipitation experiments reveal a weakly temperature-dependent iron oxide-water oxygen isotope fractionation, suggesting that increasing seawater δ18O over time was the primary cause of the long-term rise in δ18O values of marine precipitates. The 18O enrichment may have been driven by an increase in terrestrial sediment cover, a change in the proportion of high- and low-temperature crustal alteration, or a combination of these and other factors.

Se Isotopes as Groundwater Redox Indicators: Detecting Natural Attenuation of Se at an in Situ Recovery U Mine.

One of the major ecological concerns associated with the in situ recovery (ISR) of uranium (U) is the environmental release of soluble, toxic selenium (Se) oxyanions generated by mining. Post-mining natural attenuation by the residual reductants in the ore body and reduced down-gradient sediments should mitigate the risk of Se contamination in groundwater. In this work, we investigate the Se concentrations and Se isotope systematics of groundwater and of U ore bearing sediments from an ISR site at Rosita, TX, USA. Our results show that selenate (Se(VI)) is the dominant Se species in Rosita groundwater, and while several up-gradient wells have elevated Se(VI), the majority of the ore zone and down-gradient wells have little or no Se oxyanions. In addition, the δ82SeVI of Rosita groundwater is generally elevated relative to the U ore up to +6.14‰, with the most enriched values observed in the ore-zone wells. Increasing δ82Se with decreasing Se(VI) conforms to a Rayleigh type distillation model with an ε of -2.25‰ ± 0.61‰, suggesting natural Se(VI) reduction occurring along the hydraulic gradient at the Rosita ISR site. Furthermore, our results show that Se isotopes are excellent sensors for detecting and monitoring post-mining natural attenuation of Se oxyanions at ISR sites.

Isotopic and Geochemical Tracers for U(VI) Reduction and U Mobility at an in Situ Recovery U Mine.

In situ recovery (ISR) uranium (U) mining mobilizes U in its oxidized hexavalent form (U(VI)) by oxidative dissolution of U from the roll-front U deposits. Postmining natural attenuation of residual U(VI) at ISR mines is a potential remediation strategy. Detection and monitoring of naturally occurring reducing subsurface environments are important for successful implementation of this remediation scheme. We used the isotopic tracers (238)U/(235)U (δ(238)U), (234)U/(238)U activity ratio, and (34)S/(32)S (δ(34)S), and geochemical measurements of U ore and groundwater collected from 32 wells located within, upgradient, and downgradient of a roll-front U deposit to detect U(VI) reduction and U mobility at an ISR mining site at Rosita, TX, USA. The δ(238)U in Rosita groundwater varies from +0.61‰ to -2.49‰, with a trend toward lower δ(238)U in downgradient wells. The concurrent decrease in U(VI) concentration and δ(238)U with an ε of 0.48‰ ± 0.08‰ is indicative of naturally occurring reducing environments conducive to U(VI) reduction. Additionally, characteristic (234)U/(238)U activity ratio and δ(34)S values may also be used to trace the mobility of the ore zone groundwater after mining has ended. These results support the use of U isotope-based detection of natural attenuation of U(VI) at Rosita and other similar ISR mining sites.

Estimates of dietary overlap for six species of Amazonian manakin birds using stable isotopes.

We used stable isotope ratios to determine the metabolic routing fraction of carbon and nitrogen in feathers in addition to faecal analysis to estimate diet overlap of six sympatric species of manakins in the eastern lowland forest of Ecuador. Collectively, all species varied from-23.7 to-32.7 ‰ for δ(13)C, and from 6.0 to 9.9‰ for δ(15)N, with Machaeropterus regulus showing isotopic differences from the other species. We developed a mixing model that explicitly addresses the routing of carbon and nitrogen to feathers. Interestingly, these results suggest a higher proportion of nitrogen and carbon derived from insects than anticipated based on feeding observations and faecal analysis. A concentration-dependent mixing isotopic model was also used to look at dietary proportions. While larvae and arachnids had higher δ(15)N values, these two groups may also be preferred prey of manakins and may be more assimilated into tissues, leading to a potential overestimation of the contribution to diet. This study supports the finding that manakin species, previously thought be primarily frugivorous, contain a significant amount of arthropods in their diet.

Extended megadroughts in the southwestern United States during Pleistocene interglacials.

The potential for increased drought frequency and severity linked to anthropogenic climate change in the semi-arid regions of the southwestern United States (US) is a serious concern. Multi-year droughts during the instrumental period and decadal-length droughts of the past two millennia were shorter and climatically different from the future permanent, 'dust-bowl-like' megadrought conditions, lasting decades to a century, that are predicted as a consequence of warming. So far, it has been unclear whether or not such megadroughts occurred in the southwestern US, and, if so, with what regularity and intensity. Here we show that periods of aridity lasting centuries to millennia occurred in the southwestern US during mid-Pleistocene interglacials. Using molecular palaeotemperature proxies to reconstruct the mean annual temperature (MAT) in mid-Pleistocene lacustrine sediment from the Valles Caldera, New Mexico, we found that the driest conditions occurred during the warmest phases of interglacials, when the MAT was comparable to or higher than the modern MAT. A collapse of drought-tolerant C(4) plant communities during these warm, dry intervals indicates a significant reduction in summer precipitation, possibly in response to a poleward migration of the subtropical dry zone. Three MAT cycles ∼2 °C in amplitude occurred within Marine Isotope Stage (MIS) 11 and seem to correspond to the muted precessional cycles within this interglacial. In comparison with MIS 11, MIS 13 experienced higher precessional-cycle amplitudes, larger variations in MAT (4-6 °C) and a longer period of extended warmth, suggesting that local insolation variations were important to interglacial climatic variability in the southwestern US. Comparison of the early MIS 11 climate record with the Holocene record shows many similarities and implies that, in the absence of anthropogenic forcing, the region should be entering a cooler and wetter phase.

Chlorine-36 as a tracer of perchlorate origin.

Perchlorate (ClO4(-)) is ubiquitous in the environment. It is produced naturally by atmospheric photochemical reactions, and also is synthesized in large quantities for military, aerospace, and industrial applications. Nitrate-enriched salt deposits of the Atacama Desert (Chile) contain high concentrations of natural ClO4(-), and have been exported worldwide since the mid-1800s for use in agriculture. The widespread introduction of synthetic and agricultural ClO4(-) into the environment has contaminated numerous municipal water supplies. Stable isotope ratio measurements of Cl and O have been applied for discrimination of different ClO4(-) sources in the environment. This study explores the potential of 36Cl measurements for further improving the discrimination of ClO4(-) sources. Groundwater and desert soil samples from the southwestern United States (U.S.) contain ClO4(-) having high 36Cl abundances (36Cl/Cl = 3100 x 10(-15) to 28,800 x 10(-15)), compared with those from the Atacama Desert (36Cl/Cl = 0.9 x 10(-15) to 590 x 10(-15)) and synthetic ClO4(-) reagents and products (36Cl/Cl = 0.0 x 10(-15) to 40 x 10(-15)). In conjunction with stable Cl and O isotope ratios, 36Cl data provide a clear distinction among three principal ClO4(-) source types in the environment of the southwestern U.S.

Pretreatment technique for siderite removal for organic carbon isotope and C:N ratio analysis in geological samples.

A method for the removal of siderite from geological samples to determine organic carbon isotope compositions using elemental analysis isotope ratio mass spectrometry is presented which includes calculations for % organic carbon in samples that contain diagenetic carbonate. The proposed method employs in situ acidification of geological samples with 6 N HCl and silver capsule sample holders and was tested on modern peach leaf samples (NIST 1547) and ancient lacustrine samples from Valles Caldera, New Mexico. The in situ acidification technique eliminates potential errors associated with the removal of soluble organic material using standard acid decanting techniques and allows for removal of the less soluble siderite, which is not efficiently removed using vapor acidification techniques.

Coral microbial communities, zooxanthellae and mucus along gradients of seawater depth and coastal pollution.

The high incidence of coral disease in shallow coastal marine environments suggests seawater depth and coastal pollution have an impact on the microbial communities inhabiting healthy coral tissues. A study was undertaken to determine how bacterial communities inhabiting tissues of the coral Montastraea annularis change at 5 m, 10 m and 20 m water depth in varying proximity to the urban centre and seaport of Willemstad, Curaçao, Netherlands Antilles. Analyses of terminal restriction fragment length polymorphisms (TRFLP) of 16S rRNA gene sequences show significant differences in bacterial communities of polluted and control localities only at the shallowest seawater depth. Furthermore, distinct differences in bacterial communities were found with increasing water depth. Comparisons of TRFLP peaks with sequenced clone libraries indicate the black band disease cyanobacterium clone CD1C11 is common and most abundant on healthy corals in less than 10 m water depth. Similarly, sequences belonging to a previously unrecognized group of likely phototrophic bacteria, herein referred to as CAB-I, were also more common in shallow water. To assess the influence of environmental and physiologic factors on bacterial community structure, canonical correspondence analysis was performed using explanatory variables associated with: (i) light availability; (ii) seawater pollution; (iii) coral mucus composition; (iv) the community structure of symbiotic algae; and (v) the photosynthetic activity of symbiotic algae. Eleven per cent of the variation in bacterial communities was accounted for by covariation with these variables; the most important being photosynthetically active radiation (sunlight) and the coral uptake of sewage-derived compounds as recorded by the delta(15)N of coral tissue.

Stable isotope dynamics of nitrogen sewage effluent uptake in a semi-arid wetland.

Our objectives were to determine (1) how much N is transferred into the food web via plants from a wetland receiving not only inputs of treated sewage effluent, but also containing contaminants such as polychlorinated biphenyls (PCBs), (2) how birds, as consumers, utilize exogenous N and uptake PCBs in relation to the food web of the wetlands, (3) the feasibility of using isotopic analysis in estimating trophic levels in a semi-arid system. Our results demonstrate that there is very high spatial variability in the N isotopic composition of primary producers. Birds had lower variability in delta15N, despite feeding at multiple trophic levels. In very high spatial variability in delta15N of primary producers, it is difficult to use N isotope techniques to define trophic levels relevant to the bioaccumulation of organic pollutants, but it is possible to track the flow of exogenous N through the food web.

A benthic survey of Aliwal Shoal and assessment of the effects of a wood pulp effluent on the reef.

Aliwal Shoal lies south of Durban in South Africa and has been the subject of recent bathymetric, seafloor and benthic surveys. ANOVA of the biological data revealed that the biota were uniformly distributed on the reef with the exception of encrusting sponges and algae on rock. The variations in distribution of these biota were significant and, in the case of the encrusting sponges, appeared to be related to the discharge of a wood pulp effluent. Further evidence of this was suggested by stable isotope analyses of representative organisms. The encrusting sponges were recommended as good candidates for further monitoring of the effects of the wood pulp effluent on Aliwal Shoal as the effluent pipeline has been extended.