Atmospheric deposition and isotope biogeochemistry of zinc in ombrotrophic peat

Zinc isotope ratios were measured in the top sections of dated ombrotrophic peat cores in Finland to investigate their potential as proxies for atmospheric sources and to constrain post depositional processes affecting the geochemical record. The peat deposits were located in Hietajärvi, a background site well away from any point pollution source and representing ‘background’ conditions, in Outokumpu, next to a mining site, and in Harjavalta, next to a smelter. Measured total concentrations, calculated excess concentrations and mass balance considerations suggest that zinc is subjected to important biogeochemical cycling within the peat. Significant isotopic variability was found in all three peat bogs, with heavier zinc in the deeper and lighter zinc in the upper sections. Isotope ratios and concentrations correlated in the two peats located next to dominant point sources, i.e. the smelting and mining site, suggesting that zinc isotopes trace pollution sources. Concentration and isotope peaks were offset from the period of mining and smelting activity, supporting migration of zinc down the profile. The δ⁶⁶Zn_JMC (where δ⁶⁶Zn = [(⁶⁶Zn/⁶⁴Zn)_sample/(⁶⁶Zn/⁶⁴Zn)_JMC-standard − 1] × 10³) of the top section sample at the remote Hietajärvi site was 0.9‰ and we suggest this represents the regional background isotope signature of atmospheric zinc. The deeper sections of the peat cores show isotopically heavier zinc than any potential atmospheric source, indicating that post depositional processes affected the isotopic records. The large variations encountered (up to 1.05‰ for δ⁶⁶Zn) and Rayleigh modelling imply that multiple fractionation of zinc during diagenetic alterations occurs and nutrient recycling alone cannot explain the fractionation pattern.We propose that zinc isotopes are amenable to identify different atmospheric zinc sources, including zinc derived from anthropogenic activities such as mining and smelting, but multiple biogeochemical processes seriously affect the record and they need to be evaluated and assessed carefully if zinc isotopes are used in terrestrial paleorecords.     

Sporormiella as a proxy for non-mammalian herbivores in island ecosystems

Spores of the dung-fungi Sporormiella are routinely used as a proxy for past megaherbivore biomass and to pinpoint the timing of extinctions. Further ecological insight can also be gained into the impacts that followed initial human arrival in a region through correlation of spore abundance with other proxies (e.g. pollen, charcoal). Currently, the use of Sporormiella as a palaeoecological proxy has been restricted to landmasses where large-herbivore guilds are dominated by mammals. Here, we use New Zealand as a case study to show that the method can also be applied effectively to islands dominated by large avian herbivores. We examine 44 dung samples from 7 localities to show that Sporormiella spores were widely distributed in the dung of endemic avian herbivores (South Island takahe (Porphyrio hochstetteri), kakapo (Strigops habroptilus), and several species of extinct moa, identified by ancient DNA analysis). In addition, we show that Sporormiella spores in a forest soil core from the Murchison Mountains, South Island, accurately trace the post-settlement decline of native avian herbivores, and combined with high-resolution radiocarbon dating reveal severely reduced local herbivore populations by the late 17th Century AD. The spores also trace the subsequent spread of Red deer (Cervus elaphus) introduced to the area in the early 20th Century AD. Our results suggest Sporormiella spores may provide a useful new tool for examining extinctions on numerous islands where terrestrial herbivore guilds were dominated by birds or reptiles. Our findings also highlight the need to consider entire herbivore communities (including birds and reptiles) when examining Late Pleistocene continental Sporormiella records, where the focus has often been tracing the decline of populations of large mammals.     

Carbonate spots: understanding the relationship to gold mineralization in Central Victoria,southeastern Australia

Historically, carbonate spots have been identified as an indicator of gold mineralization throughout central Victoria, Australia. However, the exact timing relationships between the growth of carbonates, development of deformation fabrics, and the introduction of gold has only been determined in more recent times through isolated studies on individual gold deposits. Detailed examination of the evolution of hydrothermal alteration associated with the Magdala gold deposit at Stawell recognized the fact that there were at least two generations of carbonate growth, an early rounded ankerite phase that predated gold mineralization and a later euhedral siderite phase coincident with gold mineralization. This pattern of carbonate growth is repeated in the majority of significant gold deposits, including Bendigo and Ballarat, throughout central Victoria. Timing relationships within the carbonates suggest that a fluid was introduced along bedding planes and early deformation fabrics prior to the main upright folding events that significantly modified the original sedimentary basin. It is suggested that the early rounded carbonates may have formed as a result of anaerobic oxidation of methane, derived from the sediments and advected along normal growth faults within the sedimentary basin, through interaction with downward diffusing seawater sulfate. Although the growth of the early carbonates is not related to gold mineralization, the change in the speciation of the carbonate during the later carbonate event is critical and can be tracked using a simple geochemical index that can be used not only in areas of outcrop but also in conjunction with exploration undercover.     

Which catchment characteristics control the temporal dependence structure of daily river flows?

Hydrological classification systems seek to provide information about the dominant processes in the catchment to enable information to be transferred between catchments. Currently, there is no widely agreed‐upon system for classifying river catchments. This paper develops a novel approach to classifying catchments based on the temporal dependence structure of daily mean river flow time series, applied to 116 near‐natural ‘benchmark’ catchments in the UK. The classification system is validated using 49 independent catchments. Temporal dependence in river flow data is driven by the flow pathways, connectivity and storage within the catchment and can thus be used to assess the influence catchment characteristics have on moderating the precipitation‐to‐flow relationship. Semi‐variograms were computed for the 116 benchmark catchments to provide a robust and efficient way of characterising temporal dependence. Cluster analysis was performed on the semi‐variograms, resulting in four distinct clusters. The influence of a wide range of catchment characteristics on the semi‐variogram shape was investigated, including: elevation, land cover, physiographic characteristics, soil type and geology. Geology, depth to gleyed layer in soils, slope of the catchment and the percentage of arable land were significantly different between the clusters. These characteristics drive the temporal dependence structure by influencing the rate at which water moves through the catchment and/or the storage in the catchment. Quadratic discriminant analysis was used to show that a model with five catchment characteristics is able to predict the temporal dependence structure for un‐gauged catchments. This method could form the basis for future regionalisation strategies, as a way of transferring information on the precipitation‐to‐flow relationship between gauged and un‐gauged catchments. © 2014 The Authors. Hydrological Processes by published by John Wiley & Sons, Ltd.     

A new method of snowmelt sampling for water stable isotopes

We modified a passive capillary sampler (PCS) to collect snowmelt water for isotopic analysis. Past applications of PCSs have been to sample soil water, but the novel aspect of this study was the placement of the PCSs at the ground‐snowpack interface to collect snowmelt. We deployed arrays of PCSs at 11 sites in ten partner countries on five continents representing a range of climate and snow cover worldwide. The PCS reliably collected snowmelt at all sites and caused negligible evaporative fractionation effects in the samples. PCS is low‐cost, easy to install, and collects a representative integrated snowmelt sample throughout the melt season or at the melt event scale. Unlike snow cores, the PCS collects the water that would actually infiltrate the soil; thus, its isotopic composition is appropriate to use for tracing snowmelt water through the hydrologic cycle. The purpose of this Briefing is to show the potential advantages of PCSs and recommend guidelines for constructing and installing them based on our preliminary results from two snowmelt seasons. Copyright © 2014 John Wiley & Sons, Ltd.     

Natural turbidity variability and weather forecasts in risk management of anthropogenic sediment discharge near sensitive environments

Coastal development activities can cause local increases in turbidity and sedimentation. This study characterises the spatial and temporal variability of turbidity near an inshore fringing coral reef in the central Great Barrier Reef, under a wide range of natural conditions. Based on the observed natural variability, we outline a risk management scheme to minimise the impact of construction-related turbidity increases. Comparison of control and impact sites proved unusable for real-time management of turbidity risks. Instead, we suggest using one standard deviation from ambient conditions as a possible conservative upper limit of an acceptable projected increase in turbidity. In addition, the use of regional weather forecast as a proxy for natural turbidity is assessed. This approach is simple and cheap but also has limitations in very rough conditions, when an anthropogenic turbidity increase could prove fatal to corals that are already stressed under natural conditions.     

Extracts of impact breccia samples from Sudbury, Gardnos, and Ries impact craters and the effects of aggregation on C60 detection

Fullerenes have been detected in carbonaceous chondrite meteorites and in breccia samples from meteorite impact craters, but questions have been raised about contradictory results from similar samples and the sensitivities and accuracies of different analytical methods. We analyzed samples from three impact craters and detected C₆₀ in samples from several locations; we also observed differences in the detection capabilities of various analytical techniques used in the search for fullerenes. The presence of C₆₀ in rocks from the Onaping Formation of the Sudbury impact crater was confirmed. Low levels of C₆₀ were also detected for the first time in samples from the Gardnos (Norway) and Ries (Germany) impact structures.We detected C₆₀ in these samples using surface-enhanced laser desorption/ ionization (SELDI), but the related technique of microprobe laser-desorption, laser-ionization mass spectrometry (μL²MS) did not observe C₆₀ above detection limits. We attribute the absence of μL²MS signal to aggregate formation caused by phthalic acid esters, which appear to easily contaminate samples either during storage or demineralization in plastic containers. The μL²MS technique is incapable of detecting aggregated C₆₀, but aggregation does not suppress detection in SELDI. Phthalate-induced aggregation did, however, enhance SELDI detection of C₆₀ in some cases, and we suggest that this enhancement may help explain previously reported differences in C₆₀ detection from natural samples between laser desorption mass spectrometry (LDMS, a technique analogous to SELDI that has detected fullerenes in meteorite and impact breccia samples) and high-pressure liquid chromatography (HPLC). This work highlights the effects of phthalates and other indigenous compounds or contaminants on certain mass spectrometric techniques and lends support to the idea that several complementary analytical methods should be employed to investigate complex natural samples.