Persistent organic pollutants and stable isotopes in biopsy samples (2004/2006) from Southern Resident killer whales

“Southern Resident” killer whales include three “pods” (J, K and L) that reside primarily in Puget Sound/Georgia Basin during the spring, summer and fall. This population was listed as “endangered” in the US and Canada following a 20% decline between 1996 and 2001. The current study, using blubber/epidermis biopsy samples, contributes contemporary information about potential factors (i.e., levels of pollutants or changes in diet) that could adversely affect Southern Residents. Carbon and nitrogen stable isotopes indicated J- and L-pod consumed prey from similar trophic levels in 2004/2006 and also showed no evidence for a large shift in the trophic level of prey consumed by L-pod between 1996 and 2004/2006. ∑PCBs decreased for Southern Residents biopsied in 2004/2006 compared to 1993–1995. Surprisingly, however, a three-year-old male whale (J39) had the highest concentrations of ∑PBDEs, ∑HCHs and HCB. POP ratio differences between J- and L-pod suggested that they occupy different ranges in winter.     

Responses of benthic macroinvertebrates to thin-layer disposal of dredged material in Mississippi Sound, USA

Benthic community responses to thin-layer disposal of dredged material were assessed at three sites in Mississippi Sound, USA. Community composition differed between disposal and reference sites (ANOSIM) for each disposal event. Oweniid sand worms, Amphinomid fire worms, and brittle stars (Ophiuriodea) contributed the most to community distinctions between disposal and reference sites (SIMPER), with higher abundances at the disposal sites. Total infaunal abundance was similar to pre-disposal and reference conditions within 3-10 months of thin-layer disposal. Distinctions in community composition between disposal and reference sites (nMDS) persisted throughout the 16-month study period, but were less pronounced at the site where sediment composition was unchanged by disposal. Size distributions of some taxa (e.g., gastropod and hemichordate) suggest adults recolonized the newly deposited sediments either through vertical migration or lateral immigration from adjacent areas. Thin-layer disposal offers a viable alternative to conventional open-water disposal practices and warrants further exploration for other areas with deeper bathymetries and different hydrodynamic regimes.     

Stable sulfur isotopes in the water column of the Cariaco Basin

Previous geochemical and microbiological studies in the Cariaco Basin indicate intense elemental cycling and a dynamic microbial loop near the oxic-anoxic interface. We obtained detailed distributions of sulfur isotopes of total dissolved sulfide and sulfate as part of the on-going CARIACO time series project to explore the critical pathways at the level of individual sulfur species. Isotopic patterns of sulfate (δ³⁴S_SO4) and sulfide (δ³⁴S_H2S) were similar to trends observed in the Black Sea water column: δ³⁴S_H2S and δ³⁴S_SO4 were constant in the deep anoxic water (varying within 0.6‰ for sulfide and 0.3‰ for sulfate), with sulfide roughly 54‰ depleted in ³⁴S relative to sulfate. Near the oxic-anoxic interface, however, the δ³⁴S_H2S value was ∼3‰ heavier than that in the deep water, which may reflect sulfide oxidation and/or a change in fractionation during in situ sulfide production through sulfate reduction (SR). δ³⁴S_H2S and Δ³³S_H2S data near the oxic-anoxic interface did not provide unequivocal evidence to support the important role of sulfur-intermediate disproportionation suggested by previous studies. Repeated observation of minimum δ³⁴S_SO4 values near the interface suggests ‘readdition’ of ³⁴S-depleted sulfate during sulfide oxidation. A slight increase in δ³⁴S_SO4 values with depth extended over the water column may indicate a reservoir effect associated with removal of ³⁴S-depleted sulfur during sulfide production through SR. Our δ³⁴S_H2S and Δ³³S_H2S data also do not show a clear role for sulfur-intermediate disproportionation in the deep anoxic water column. We interpret the large difference in δ³⁴S between sulfate and sulfide as reflecting fractionations during SR in the Cariaco deep waters that are larger than those generally observed in culturing studies.     

Paleofire reconstruction for high-elevation forests in the Sierra Nevada, California, with implications for wildfire synchrony and climate variability in the late Holocene

Here, we present two high-resolution records of macroscopic charcoal from high-elevation lake sites in the Sierra Nevada, California, and evaluate the synchroneity of fire response for east- and west-side subalpine forests during the past 9200 yr. Charcoal influx was low between 11,200 and 8000 cal yr BP when vegetation consisted of sparse Pinus-dominated forest and montane chaparral shrubs. High charcoal influx after ∼ 8000 cal yr BP marks the arrival of Tsuga mertensiana and Abies magnifica, and a higher-than-present treeline that persisted into the mid-Holocene. Coeval decreases in fire episode frequency coincide with neoglacial advances and lower treeline in the Sierra Nevada after 3800 cal yr BP. Independent fire response occurs between 9200 and 5000 cal yr BP, and significant synchrony at 100- to 1000-yr timescales emerges between 5000 cal yr BP and the present, especially during the last 2500 yr. Indistinguishable fire-return interval distributions and synchronous fires show that climatic control of fire became increasingly important during the late Holocene. Fires after 1200 cal yr BP are often synchronous and corroborate with inferred droughts. Holocene fire activity in the high Sierra Nevada is driven by changes in climate linked to insolation and appears to be sensitive to the dynamics of the El Niño-Southern Oscillation.     

A digitized global flood inventory (1998–2008): compilation and preliminary results

Floods have profound impacts on populations worldwide in terms of both loss of life and property. A global inventory of floods is an important tool for quantifying the spatial and temporal distribution of floods and for evaluating global flood prediction models. Several global hazard inventories currently exist; however, their utility for spatiotemporal analysis of global floods is limited. The existing flood catalogs either fail to record the geospatial area over which the flood impacted or restrict the types of flood events included in the database according to a set of criteria, limiting the scope of the inventory. To improve upon existing databases, and make it more comprehensive, we have compiled a digitized Global Flood Inventory (GFI) for the period 1998–2008 which also geo-references each flood event by latitude and longitude. This technical report presents the methodology used to compile the GFI and preliminary findings on the spatial and temporal distributions of the flooding events that are contained in the inventory.     

Geochemical and mineralogical evidence for Sahara and Sahel dust additions to Quaternary soils on Lanzarote,eastern Canary Islands,Spain

Africa is the most important source of dust in the world today, and dust storms are frequent on the nearby Canary Islands. Previous workers have inferred that the Sahara is the most important source of dust to Canary Islands soils, with little contribution from the Sahel region. Soils overlying a late Quaternary basalt flow on Lanzarote, Canary Islands, contain, in addition to volcanic minerals, quartz and mica, exotic to the island’s bedrock. Kaolinite in the soils also likely has an exotic origin. Trace‐element geochemistry shows that the soils are derived from varying proportions of locally derived basalt and African dust. Major‐element geochemistry, clay mineralogy and interpretation of satellite imagery suggest that dust additions to the Canary Islands come not only from the Sahara Desert, but also from the Sahel region.     

The Role of One- and Two-Electron Transfer Reactions in Forming Thermodynamically Unstable Intermediates as Barriers in Multi-Electron Redox Reactions

In the aquatic geochemical literature, a redox half-reaction is normally written for a multi-electron process (n > 2); e.g., sulfide oxidation to sulfate. When coupling two multi-electron half-reactions, thermodynamic calculations indicate possible reactivity, and the coupled half-reactions are considered favorable even when there is a known barrier to reactivity. Thermodynamic calculations should be done for one or two-electron transfer steps and then compared with known reactivity to determine the rate controlling step in a reaction pathway. Here, thermodynamic calculations are presented for selected reactions for compounds of C, O, N, S, Fe, Mn and Cu. Calculations predict reactivity barriers and agree with one previous analysis showing the first step in reducing O₂ to O₂ ^? with Fe²⁺ and Mn²⁺ is rate limiting. Similar problems occur for the first electron transfer step in these metals reducing NO₃ ^?, but if reactive oxygen species form or if two-electron transfer steps with O atom transfer occur, reactivity becomes favorable. H₂S and NH₄ ⁺ oxidation in a one-electron transfer step by O₂ is also not favorable unless activation of oxygen can occur. H₂S oxidation by Cu²⁺, Fe(III) and Mn(III, IV) phases in two-electron transfer steps is favorable but not in one-electron steps indicating that (nano)particles with bands of orbitals are needed to accept two electrons from H₂S. NH₄ ⁺ oxidation by Fe(III) and Mn(III, IV) phases is generally not favorable for both one- and two-electron transfer steps, but their reaction with hydroxylamine and hydrazine to form N₂O and N₂, respectively, is favorable. The anammox reaction using hydroxylamine via nitrite reduction is the most favorable for NH₄ ⁺ oxidation. Other chemical processes including photosynthesis and chemosynthesis are considered for these element–element transformations.     

Biogeochemical Zones Within a Macrotidal,Dry-Tropical Fluvial-Marine Transition Area: A Dry-Season Perspective

The Fitzroy River delivers large amounts of nutrients and fine sediments to Keppel Bay (contiguous with the Great Barrier Reef Lagoon) during intermittent flow events. This study explores sources, forms and transformations of nutrients in Keppel Bay, and develops a functional process zonation that integrates seabed geochemistry and water column nutrient characteristics which are controlled by suspended sediment. The water column and seabed properties were investigated over two dry seasons, with supplementary core incubations taken to measure carbon decomposition rates and nutrient fluxes. Keppel Bay can be divided into three zones, the: zone of maximum resuspension (ZMR); coastal transitional zone (CTZ); and blue water zone (BWZ). Mineralisation of predominantly terrestrial organic matter occurs in the ZMR where nutrient uptake by phytoplankton is light limited. The CTZ and BWZ had higher light penetration and phytoplankton growth was likely limited by N and P, respectively. The identified zones conform to the bathymetry and hydrodynamic characteristics of the bay, allowing for the development of an integrated conceptual model accounting for the benthic and pelagic biogeochemical processes. Recognition of these different zones shows that considerable variation in benthic and water column properties is possible within a small system with the bathymetric and hydrodynamic characteristics of the fluidized bed reactor.