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.     

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.     

Molecular distribution and 13C isotope composition of volatile organic compounds in the Murchison and Sutter's Mill carbonaceous chondrites

Volatile organic compounds (VOCs) are carbon-containing chemicals that may evaporate rapidly at room temperature and standard pressure. Such organic compounds can be preserved inside carbonaceous chondrite matrices. However, unlike meteoritic soluble organic matter (SOM) and insoluble organic matter (IOM), VOCs are typically lost (at least in part) during sample processing (meteorite crushing) and exposure to terrestrial atmosphere and/or solvents. Like SOM and IOM, VOCs can provide valuable insights into the chemical inventory of the meteorite parent body and even the presolar cloud from which our solar system formed, as well as the composition and processes that occurred during the early formation of our solar system and the asteroidal stage. Thus, in this work, we designed and built an instrument that allowed us to access the VOCs present in samples of the carbonaceous chondrites Murchison and Sutter's Mill after mineral disaggregation by means of freeze–thaw cycling. We simultaneously evaluated the abundances and compound-specific ¹³C-distributions of the volatiles evolving after meteorite powdering at ~20, 60, and 100°C. Carbon monoxide (CO) and methane (CH₄) were released from these meteorites as the most abundant VOCs. They were combusted together for analysis and showed positive δ¹³C values, indicative of their extraterrestrial origins. Carbon dioxide (CO₂) was also an abundant VOC in both meteorites, and its isotopic values suggest that it was mainly formed from dissolved carbonates in the samples. We also detected aldehydes, ketones, and aromatic compounds in low amounts. Contrary to Murchison, which mostly yielded VOCs with positive δ¹³C values, Sutter's Mill yielded VOCs with negative δ¹³C values. The less enriched ¹³C isotope composition of the VOCs detected in Sutter's Mill suggest that they are either terrestrial contaminants, such as VOCs in compressed gas dusters and common laboratory solvents, or compounds disconnected from interstellar sources and/or formed through parent body processing. Understanding the relative abundances and determining the molecular distributions and isotopic compositions of free meteoritic VOCs are key in assessing their extraterrestrial origins and those of chondritic SOM and IOM. Our newly developed technique will be valuable in the study of the samples brought to the Earth from carbonaceous asteroid Bennu by NASA's OSIRIS-REx mission.