High-resolution historical records from Pettaquamscutt River basin sediments: 1. Pb and varve chronologies validate record of Cs released by the Chernobyl accident

Cesium-137 derived from the explosion of the Chernobyl reactor in 1986 was preserved in anoxic sediments from a coastal environment in southern Rhode Island. Although the radioactive plume was detected in surface air samples at several locations in the United States, this is the first known record of a Chernobyl ¹³⁷Cs peak in sediments from North America. The inventory of Chernobyl ¹³⁷Cs that was preserved in the Pettaquamscutt River is small compared to European counterparts and should only be detectable for the next 15-20 yr. However, the presence of two ¹³⁷Cs peaks (1963 and 1987) identifies a well-dated segment of the sediment column that could be exploited in understanding the decomposition and preservation of terrestrial and aquatic organic matter. Different methods for calculating the ²¹⁰Pb chronology were also evaluated in this study and checked against independent varve counting. The end result is a detailed chronology of a site well suited for reconstruction of historical records of environmental change.     

Ab initio molecular orbital calculations for boron isotope fractionations on boric acids and borates

Ab initio quantum chemistry calculations have been performed on the isotopic exchange reaction between B(OH)₃ and B(OH)₄⁻. Several calculation methods have been carefully compared and evaluated. The “water-droplet” method is chosen to investigate this isotope exchange reaction using cluster models with up to 34 water molecules surrounding the solute. HF/6-31G* level calculations coupled with a 0.920 scaling factor are used for the frequency calculations. A larger K value (1.027) is obtained from this study compared to the commonly used 1.0194 (Kakihana et al., 1977).The fractionations for several boric acid polymers and boron minerals are also studied. Our results suggest that assuming the BO₄ bonding in B(OH)₄⁻ is identical to that in borosilicates is wrong. Tetrahedral boron in silicates has a significantly smaller reduced isotopic partition function ratio (RPFR) and hence will be much isotopically lighter than in B(OH)₄⁻.The new theoretical curve of pH vs. δ¹¹B composition of B(OH)₄⁻ using our calculated 1.027 can be used to predict pH values for equilibrium cases such as incorporation into inorganic calcite. We also find that the shape of this curve is very sensitive to both K and pK_a value, giving the possibility of also predicting salinity from the different shapes of the curve.     

Thallium diagenesis in lacustrine sediments

Dated sediment cores and porewaters from two Canadian Shield lakes, located 40 km from Québec City (L. Tantaré) and 25 km downwind from an important smelter in northwestern Québec (L. Vose), were analyzed for thallium and other geochemical variables. Atmospheric deposition is the only source of anthropogenic Tl to these lakes. The porewater Tl concentration profiles in L. Tantaré display a peak below the sediment-water interface that suggests post-depositional Tl remobilization and transport to the overlying water and deeper sediments; such a dissolved Tl peak occurs just above the sediment-water interface in L. Vose. Modeling the porewater Tl profiles with a diagenetic reaction-transport equation reveals a zone of dissolved Tl production lying above a zone of Tl consumption in L. Tantaré sediments. In contrast, in L. Vose, Tl diffuses across the sediment-water interface from the anoxic hypolimnion and is fixed to the surficial sediments. The localization of the consumption zones, the shape of the dissolved Tl, sulfide and iron profiles, as well as calculations of saturation states are all consistent with the removal of Tl from porewater by co-precipitation with and/or adsorption to Fe sulfides. The concentrations of Tl removed from or added to sediments after their deposition (i.e., diagenetic Tl) amount to up to 36% of measured sediment Tl concentrations. Comparison of the reconstructed historical Tl records with those of polycyclic aromatic hydrocarbons (PAHs) and of Pb originating from coal burning or from smelting activities indicate that coal combustion is the major source of atmospheric Tl to L. Tantaré and that an additional important Tl source to L. Vose is the nearby smelter.     

Including spatial distribution in a data‐driven rainfall‐runoff model to improve reservoir inflow forecasting in Taiwan

Multi‐step ahead inflow forecasting has a critical role to play in reservoir operation and management in Taiwan during typhoons as statutory legislation requires a minimum of 3‐h warning to be issued before any reservoir releases are made. However, the complex spatial and temporal heterogeneity of typhoon rainfall, coupled with a remote and mountainous physiographic context, makes the development of real‐time rainfall‐runoff models that can accurately predict reservoir inflow several hours ahead of time challenging. Consequently, there is an urgent, operational requirement for models that can enhance reservoir inflow prediction at forecast horizons of more than 3 h. In this paper, we develop a novel semi‐distributed, data‐driven, rainfall‐runoff model for the Shihmen catchment, north Taiwan. A suite of Adaptive Network‐based Fuzzy Inference System solutions is created using various combinations of autoregressive, spatially lumped radar and point‐based rain gauge predictors. Different levels of spatially aggregated radar‐derived rainfall data are used to generate 4, 8 and 12 sub‐catchment input drivers. In general, the semi‐distributed radar rainfall models outperform their less complex counterparts in predictions of reservoir inflow at lead times greater than 3 h. Performance is found to be optimal when spatial aggregation is restricted to four sub‐catchments, with up to 30% improvements in the performance over lumped and point‐based models being evident at 5‐h lead times. The potential benefits of applying semi‐distributed, data‐driven models in reservoir inflow modelling specifically, and hydrological modelling more generally, are thus demonstrated. Copyright © 2012 John Wiley & Sons, Ltd.     

Mid‐Miocene initiation of E‐W extension and recoupling of the Himalaya

The Tibetan plateau is host to numerous ~N‐S striking graben that have accommodated E‐W directed extension. The development of these structures has been interpreted to reflect a variety of different geological processes including plateau collapse, oroclinal bending or mid‐to‐lower crustal flow. New ⁴⁰Ar/³⁹Ar thermochronology and quartz c‐axis data from the Thakkhola graben of west‐central Nepal show that E‐W extension was ongoing at least locally by the early Miocene (ca. 17 Ma). Our new, and previously published chronologic information on the initiation of graben across the orogen shows that they typically developed immediately after cessation of the South Tibetan detachment system, a structural network that facilitated differential southward movement of the upper and middle crust. We interpret this fundamental switch in orogen kinematics to reflect recoupling of the middle and upper Himalayan crust such that the subsequent widespread flow of the mid‐to‐lower crust out of the system to the east forced brittle accommodation in the upper crust.     

Late Holocene environmental conditions in Coronation Gulf,southwestern Canadian Arctic Archipelago: evidence from dinoflagellate cysts,other non‐pollen palynomorphs,and pollen

Boxcore 99LSSL‐001 (68.095° N, 114.186° W; 211 m water depth) from Coronation Gulf represents the first decadal‐scale marine palynology and late Holocene sediment record for the southwestern part of the Northwest Passage. The record was studied for organic‐walled microfossils (dinoflagellate cysts, non‐pollen palynomorphs), pollen, terrestrial spores, and sediment characteristics. ²¹⁰Pb, ¹³⁷Cs, and three accelerator mass spectrometry ¹⁴C dates constrain the chronology. Three prominent palaeoenvironmental zones were identified. During the interval AD 1470–1680 (Zone I), the climate was warmer and wetter than at present, and environmental conditions were more favourable to biological activity and northward boreal forest migration, with reduced sea‐ice and a longer open‐water (growing) season. The interval AD 1680–1940 (Zone II) records sea‐ice increase, and generally cool, polar conditions during the Little Ice Age. During AD 1940–2000 (Zone III), organic microfossils indicate an extended open‐water season and decreased sea‐ice, with suggested amelioration surpassing that of Zone I. Although more marine studies are needed to place this record into an appropriate context, the succession from ameliorated (Zone I) to cooler, sea‐ice influenced conditions (Zone II) and finally to 20th‐century warming (Zone III) corresponds well with several terrestrial climatic records from the neighbouring mainland and Victoria Island, and with lower‐resolution marine records to the west. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of soil‐hydraulic properties and infiltration timescales in wildfire‐affected soils

We collected soil‐hydraulic property data from the literature for wildfire‐affected soils, ash, and unburned soils. These data were used to calculate metrics and timescales of hydrologic response related to infiltration and surface runoff generation. Sorptivity (S) and wetting front potential (Ψ_f) were significantly different (lower) in burned soils compared with unburned soils, whereas field‐saturated hydraulic conductivity (K_fs) was not significantly different. The magnitude and duration of the influence of capillarity during infiltration was greatly reduced in burned soils, causing faster ponding times in response to rainfall. Ash had large values of S and K_fs but moderate values of Ψ_f, compared with unburned and burned soils, indicating ash has long ponding times in response to rainfall. The ratio of S²/K_fs was nearly constant (~100 mm) for unburned soils but more variable in burned soils, suggesting that unburned soils have a balance between gravity and capillarity contributions to infiltration that may depend on soil organic matter, whereas in burned soils the gravity contribution to infiltration is greater. Changes in S and K_fs in burned soils act synergistically to reduce infiltration and accelerate and amplify surface runoff generation. Synthesis of these findings identifies three key areas for future research. First, short timescales of capillary influences on infiltration indicate the need for better measurements of infiltration at times less than 1 min to accurately characterize S in burned soils. Second, using parameter values, such as Ψ_f, from unburned areas could produce substantial errors in hydrologic modeling when used without adjustment for wildfire effects, causing parameter compensation and resulting underestimation of K_fs. Third, more thorough measurement campaigns that capture soil‐structural changes, organic matter impacts, quantitative water repellency trends, and soil‐water content along with soil‐hydraulic properties could drive the development of better techniques for numerically simulating infiltration in burned areas.     

Watershed structural influences on the distributions of stream network water and solute travel times under baseflow conditions

Watershed structure influences the timing, magnitude, and spatial location of water and solute entry to stream networks. In turn, stream reach transport velocities and stream network geometry (travel distances) further influence the timing of export from watersheds. Here, we examine how watershed and stream network organization can affect travel times of water from delivery to the stream network to arrival at the watershed outlet. We analysed watershed structure and network geometry and quantified the relationship between stream discharge and solute velocity across six study watersheds (11.4 to 62.8 km²) located in the Sawtooth Mountains of central Idaho, USA. Based on these analyses, we developed stream network travel time functions for each watershed. We found that watershed structure, stream network geometry, and the variable magnitude of inputs across the network can have a pronounced affect on water travel distances and velocities within a stream network. Accordingly, a sample taken at the watershed outlet is composed of water and solutes sourced from across the watershed that experienced a range of travel times in the stream network. We suggest that understanding and quantifying stream network travel time distributions are valuable for deconvolving signals observed at watershed outlets into their spatial and temporal sources, and separating terrestrial and in‐channel hydrological, biogeochemical, and ecological influences on in‐stream observations. Copyright © 2016 John Wiley & Sons, Ltd.