Deconvolving the δO seawater component from subseasonal coral δO and Sr/Ca at Rarotonga in the southwestern subtropical Pacific for the period 1726 to 1997

To reconstruct oceanographic variations in the subtropical South Pacific, 271-year long subseasonal time series of Sr/Ca and δ¹⁸O were generated from a coral growing at Rarotonga (21.5°S, 159.5°W). In this case, coral Sr/Ca appears to be an excellent proxy for sea surface temperature (SST) and coral δ¹⁸O is a function of both SST and seawater δ¹⁸O composition (δ¹⁸O_sw). Here, we focus on extracting the δ¹⁸O_sw signal from these proxy records. A method is presented assuming that coral Sr/Ca is solely a function of SST and that coral δ¹⁸O is a function of both SST and δ¹⁸O_sw. This method separates the effects of δ¹⁸O_sw from SST by breaking the instantaneous changes of coral δ¹⁸O into separate contributions by instantaneous SST and δ¹⁸O_sw changes, respectively. The results show that on average δ¹⁸O_sw at Rarotonga explains ∼39% of the variance in δ¹⁸O and that variations in SST explains the remaining ∼61% of δ¹⁸O variance. Reconstructed δ¹⁸O_sw shows systematic increases in summer months (December-February) consistent with the regional pattern of variations in precipitation and evaporation. The δ¹⁸O_sw also shows a positive linear correlation with satellite-derived estimated salinity for the period 1980 to 1997 (r = 0.72). This linear correlation between reconstructed δ¹⁸O_sw and salinity makes it possible to use the reconstructed δ¹⁸O_sw to estimate the past interannual and decadal salinity changes in this region. Comparisons of coral δ¹⁸O and δ¹⁸O_sw at Rarotonga with the Pacific decadal oscillation index suggest that the decadal and interdecadal salinity and SST variability at Rarotonga appears to be related to basin-scale decadal variability in the Pacific.     

In situ sampling reveals rapid uptake and depuration of polycyclic aromatic hydrocarbons by surf clams (Paphies subtriangulata) affected by the Rena oil spill

ABSTRACT

To investigate the uptake and depuration of polycyclic aromatic hydrocarbons associated with the Rena oil spill we sampled the surf clam Paphies subtriangulata at two open coast locations (6?km apart) just prior to oil coming ashore (7 October 2011), then at 1–3 week intervals for the next 4 months. Total polycyclic aromatic hydrocarbons (tPAH) increased at both sites from 1 to 96–124?µg?kg^?1 (wet weight) by 18 October before declining to low levels (<4?µg?kg^?1) by February 2012. Ongoing sampling throughout 2012–2014 included three additional sites to the north east (up to 30?km away) and a site 5?km to the south east revealing tPAH levels generally <10?µg?kg^?1 except in October 2013 where levels ranged between 39–45?µg?kg^?1 at all sites. A comparison of PAH component profiles with oil-contaminated beach sediment indicated that the high levels observed in surf clams between October–December 2011 were clearly associated with the Rena spill. However, the October 2013 peak had a PAH profile inconsistent with weathered Rena oil, suggesting an alternative source of contamination. Our results highlight the potential for P. subtriangulata as a PAH monitoring tool but recognise more study is needed to better quantify baseline levels and uptake and depuration dynamics.     

Kinetic oxygen isotope effects during dissimilatory sulfate reduction: A combined theoretical and experimental approach

Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ³⁴S_SO4 and δ¹⁸O_SO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ¹⁸O_H2O and initial δ¹⁸O_SO4, all strains show ³⁴S enrichment, whereas only six strains show significant ¹⁸O enrichment. The remaining six show no (or minimal) change in δ¹⁸O_SO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO₃²⁻), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.     

Clumped isotope thermometry of carbonatites as an indicator of diagenetic alteration

We measure the clumped isotopic signature of carbonatites to assess the integrity of the clumped isotope paleothermometer over long timescales (10⁷-10⁹ years) and the susceptibility of the proxy to closed system re-equilibration of isotopes during burial diagenesis. We find pristine carbonatites that have primary oxygen isotope signatures, along with a Carrara marble standard, do not record clumped isotope signatures lighter than 0.31‰ suggesting atoms of carbon and oxygen freely exchange within the carbonate lattice at temperatures above 250-300 °C. There is no systematic trend in the clumped isotope signature of pristine carbonatites with age, although partial re-equilibration to lower temperatures can occur if a carbonatite has been exposed to burial temperatures for long periods of time. We conclude that the solid-state re-ordering of carbon and oxygen atoms is sufficiently slow to enable the use of clumped isotope paleothermometry on timescales of 10⁸ years, but that diagenetic resetting can still occur, even without bulk recrystallization. In addition to the carbonatite data, an inorganic calibration of the clumped isotope paleothermometer for low temperature carbonates (7.5-77 °C) is presented and highlights the need for further inter-lab standardization.     

The danger of overvaluing methane’s influence on future climate change

Minimizing the future impacts of climate change requires reducing the greenhouse gas (GHG) load in the atmosphere. Anthropogenic emissions include many types of GHG’s as well as particulates such as black carbon and sulfate aerosols, each of which has a different effect on the atmosphere, and a different atmospheric lifetime. Several recent studies have advocated for the importance of short timescales when comparing the climate impact of different climate pollutants, placing a high relative value on short-lived pollutants, such as methane (CH₄) and black carbon (BC) versus carbon dioxide (CO₂). These studies have generated confusion over how to value changes in temperature that occur over short versus long timescales. We show the temperature changes that result from exchanging CO₂ for CH₄ using a variety of commonly suggested metrics to illustrate the trade-offs involved in potential carbon trading mechanisms that place a high value on CH₄ emissions. Reducing CH₄ emissions today would lead to a climate cooling of approximately ~0.5 °C, but this value will not change greatly if we delay reducing CH₄ emissions by years or decades. This is not true for CO₂, for which the climate is influenced by cumulative emissions. Any delay in reducing CO₂ emissions is likely to lead to higher cumulative emissions, and more warming. The exact warming resulting from this delay depends on the trajectory of future CO₂ emissions but using one business-as usual-projection we estimate an increase of 3/4 °C for every 15-year delay in CO₂ mitigation. Overvaluing the influence of CH₄ emissions on climate could easily result in our “locking” the earth into a warmer temperature trajectory, one that is temporarily masked by the short-term cooling effects of the CH₄ reductions, but then persists for many generations.     

Hydrological conditions over the western Mediterranean basin during the deposition of the cold Sapropel 6 (ca. 175 kyr BP)

A new oxygen isotope record is reported from a stalagmite collected in the Argentarola Cave located on the Tyrrhenian coast of Italy. As shown from observations and numerical modeling of δ¹⁸O in modern precipitation, the recorded δ¹⁸O variability for this zone is dominated by the amount of precipitation (so-called ‘amount effect’). The δ¹⁸O profile measured in the stalagmite is characterized by a prominent negative excursion (ca. 2-3‰) between 180 and 170 kyr BP. This paleoclimatic feature is interpreted as being due to a relatively wet period which occurred during the penultimate glacial period, more precisely, during Marine Isotope Stage 6.5. This pluvial phase is shown to correspond chronologically to the deposition of the sapropel event 6 (S6). Although this particular sapropel event occurred during a cold phase, the δ¹⁸O excursion is similar to those corresponding to other sapropels (S4, S3 and S2). The evidence for humid conditions during S6 in the western Mediterranean basin agrees with previous studies based on deep-sea sediment cores. Taken collectively, the data suggest that during sapropel events dilution of ocean surface waters was not restricted to the output of the river Nile but was rather widespread over the entire Mediterranean Sea due to increased rainfall.     

Defining an absolute reference frame for ‘clumped’ isotope studies of CO2

We present a revised approach for standardizing and reporting analyses of multiply substituted isotopologues of CO₂ (i.e., ‘clumped’ isotopic species, especially the mass-47 isotopologues). Our approach standardizes such data to an absolute reference frame based on theoretical predictions of the abundances of multiply-substituted isotopologues in gaseous CO₂ at thermodynamic equilibrium. This reference frame is preferred over an inter-laboratory calibration of carbonates because it enables all laboratories measuring mass 47 CO₂ to use a common scale that is tied directly to theoretical predictions of clumping in CO₂, regardless of the laboratory’s primary research field (carbonate thermometry or CO₂ biogeochemistry); it explicitly accounts for mass spectrometric artifacts rather than convolving (and potentially confusing) them with chemical fractionations associated with sample preparation; and it is based on a thermodynamic equilibrium that can be experimentally established in any suitably equipped laboratory using commonly available materials.By analyzing CO₂ gases that have been subjected to established laboratory procedures known to promote isotopic equilibrium (i.e., heated gases and water-equilibrated CO₂), and by reference to thermodynamic predictions of equilibrium isotopic distributions, it is possible to construct an empirical transfer function that is applicable to data with unknown clumped isotope signatures. This transfer function empirically accounts for the fragmentation and recombination reactions that occur in electron impact ionization sources and other mass spectrometric artifacts. We describe the protocol necessary to construct such a reference frame, the method for converting gases with unknown clumped isotope compositions to this reference frame, and suggest a protocol for ensuring that all reported isotopic compositions (e.g., Δ₄₇ values; [Eiler and Schauble, 2004] and [Eiler, 2007]) can be compared among different laboratories and instruments, independent of laboratory-specific analytical or methodological differences. We then discuss the use of intra-laboratory secondary reference frames (e.g., based on carbonate standards) that can be more easily used to track the evolution of each laboratory’s empirical transfer function. Finally, we show inter-laboratory reproducibility on the order of ±0.010 (1σ) for four carbonate standards, and present revised paleotemperature scales that should be used to convert carbonate clumped isotope signatures to temperature when using the absolute reference frame described here. Even when using the reference frame, small discrepancies remain between two previously published synthetic carbonate calibrations. We discuss possible reasons for these discrepancies, and highlight the need for additional low temperature (<15 °C) synthetic carbonate experiments.     

Climate-change impacts on sagebrush habitat and West Nile virus transmission risk and conservation implications for greater sage-grouse

Greater sage-grouse (Centrocercus urophasianus) are threatened by loss of sagebrush habitat and the spread of West Nile virus throughout much of their range in North America; yet, future impacts of climate change on these potential stressors have not been addressed. Here, we aim to quantify the potential impacts of climate change on the distribution of climatically suitable habitat for sagebrush and on transmission risk for West Nile virus in the eastern portion of the species’ range. We used Maxent to model the current and future climatically suitable habitat for two dominant sagebrush species in the study area, and we used a degree-day model to predict future West Nile virus transmission risk under likely climate-change scenarios. Our models suggest that areas with the highest future suitability for sagebrush habitat will be found in southwestern Wyoming and north-central Montana. The degree-day model suggests that greater sage-grouse in western portions of the study area, which are generally higher in elevation than where West Nile virus currently occurs, will see increasing risk of transmission in the future. We developed a spatially explicit map of suggested management actions based on our predictions that will aid in conservation of the species into the coming decades.     

Patterns and trends in seabird bycatch in the pelagic longline fishery off South Africa

Both foreign and domestic pelagic longline fishing vessels operate in South Africa’s Exclusive Economic Zone and adjacent international waters where they kill hundreds of seabirds each year as bycatch. To update assessments of the impact of the pelagic longline fishery on seabirds off South Africa, information on necropsied seabirds and national fisheries observer bycatch records were summarised for 2006–2013. Foreign-flagged (Asian) vessels had 100% observer coverage throughout the study period, whereas only 6% of the fishing effort by South African-flagged vessels was observed (with no coverage in 2011–2013). Vessels with observers caught seabirds at a rate of 0.132 birds per 1 000 hooks, resulting in an estimated mortality of 2 851 individuals (356 per year) comprising 14 species. Extrapolation of the observed fishing sets to the unobserved fishing sets by the South African domestic longline fleet suggested that approximately 750 additional birds were likely killed during the study period, therefore a combined 450 birds were killed per year. White-chinned petrel Procellaria aequinoctialis was the most frequently killed species (66%), followed by ‘shy-type’ albatrosses Thalassarche cauta/steadi (21%), black-browed albatross T. melanophris (7%), Indian yellow-nosed albatross T. carteri (3%), and Cape gannet Morus capensis (2%). The seabird bycatch rates were lower than in 1998–2005. Nationality of the vessel, time of line-setting, moon phase, year, season, fishing area, and seabird bycatch mitigation measures all influenced seabird mortality. Concurrent with 100% observer coverage, significant reductions in the seabird bycatch rate occurred in the Asian fleet in the latter years of the study, and these rates now approximate the national target (0.05 birds per 1 000 hooks). However, seabird bycatch rates remained high in the South African fleet, where no observers were deployed during 2011–2013, highlighting the need for independent observer programmes in fisheries—a matter of global interest. Suggestions are made as to how seabird bycatch by pelagic longline fisheries off South Africa may be further reduced.     

Remediation of a major acid mine drainage point source discharge restores headwater connectivity for a diadromous native fish

Rivers receiving acid mine drainage (AMD) are frequently depauperate in fish and impacts may extend long distances downstream. AMD inputs may form chemical barriers for migratory species and isolate fish in unimpacted headwaters. We investigated the response of a diadromous fish, kōaro (Galaxias brevipinnis), to remediation of an AMD tributary in a 5th order river in New Zealand. A 2005 survey indicated limited recruitment of kōaro in the river likely due to the chemical barrier of AMD. By 2010, water treatment in the contaminated tributary had raised pH from a median value of 4.3 to 6 and reduced metals in the lower river, notably aluminium from a median of 2.48 to 0.41?mg/L. In 2012, kōaro density had increased by an order of magnitude relative to 2005. Furthermore, a greater proportion of juvenile fish were present. These results indicate that large-scale remediation of discharges can reverse the impacts of AMD on fish migration.