Carbon Isotope Analysis to Evaluate Nanoscale Fe(O) Treatment at a Chlorohydrocarbon Contaminated Site

Remediation of groundwater contaminated by chlorinated hydrocarbons via in situ technologies such as direct injection of nanoscale zero valent iron (ZVI, Fe(O)) particles is increasingly common. However, assessing target compound degradation by abiotic processes is difficult because (1) the injection may displace the contaminant plume so that concentration measurements alone are often inconclusive and (2) biodegradation may also occur, making it challenging to identify and evaluate the abiotic degradation component. In this study, trichloroethylene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA) were treated in a highly heterogeneous hydrogeologic setting. The purpose of this study was to evaluate the potential for compound-specific stable isotope analysis (CSIA) to monitor the effectiveness of ZVI injection by assessing TCE and 1,1,1-TCA degradation. Prior to ZVI injection, carbon isotope measurements demonstrated biodegradation of TCE by native microorganisms. This in situ biodegradation was quantified by measuring the enrichment of ¹³C in TCE samples downstream of the suspected source. When ZVI was injected through only two injection wells, no changes in TCE and 1,1,1-TCA isotope signatures were detected compared to preinjection values. In contrast, when ZVI was injected through 11 wells covering a greater portion of the contaminated area, 5 out of 10 monitoring wells showed further enrichment of ¹³C in either TCE or 1,1,1-TCA, indicating additional target compound transformation. The abiotic nature of this TCE transformation was confirmed through temporal trends in carbon isotope values of the putative transformation products cis-dichloroethylene (cis-DCE), ethene and ethane. This demonstrates the usefulness of CSIA in distinguishing abiotic vs. biotic transformation in the field.     

Temporal correlations and clustering of landslides

This paper examines temporal correlations and temporal clustering of a proxy historical landslide time series, 2255 reported landslides 1951–2002, for an area in the Emilia‐Romagna Region, Italy. Landslide intensity is measured by the number of reported landslides in a day (D_L) and in an ‘event’ (S_event) of consecutive days with landsliding. The non‐zero values in both time series D_L and S_event are unequally spaced in time, and have heavy‐tailed frequency‐size distributions. To examine temporal correlations, we use power‐spectral analysis (Lomb periodogram) and surrogate data analysis, confronting our original D_L and S_event time series with 1000 shuffled (uncorrelated) versions. We conclude that the landslide intensity series D_L has strong temporal correlations and S_event has likely temporal correlations. To examine temporal clustering in D_L and S_event, we consider extremes over different landslide intensity thresholds. We first examine the statistical distribution of interextreme occurrence times, τ, and find Weibull distributions with parameter γ << 1·0 [D_L] and γ < 1·0 [S_event]; thus D_L and S_event each have temporal correlations, but S_event to a lesser degree. We next examine correlations between successive interextreme occurrence times, τ. Using autocorrelation analysis applied to τ, combined with surrogate data analysis, we find for D_L linear correlations in τ, but for S_event inconclusive results. However, using Kendall's rank correlation analysis we find for both D_L and S_event the series of τ are strongly correlated. Finally, we apply Fano Factor analysis, finding for both D_L and S_event the timings of extremes over a given threshold exhibit a fractal structure and are clustered in time. In this paper, we provide a framework for examining time series where the non‐zero values are strongly unequally spaced and heavy‐tailed, particularly important in the Earth Sciences due to their common occurrence, and find that landslide intensity time series exhibit temporal correlations and clustering. Many landslide models currently are designed under the assumption that landslides are uncorrelated in time, which we show is false. Copyright © 2010 John Wiley & Sons, Ltd.     

Carbon dioxide concentration in temperate climate caves and parent soils over an altitudinal gradient and its influence on speleothem growth and fabrics

Carbon dioxide (CO₂) concentrations in caves and parent soils in the Italian Alps have been studied along a 2100 m altitudinal range – corresponding to a mean annual temperature (MAT) range of 12°C – in order to investigate the relationship between MAT, soil pCO₂ and cave air pCO₂, and to test the influence of soil pCO₂ on speleothem growth and fabric to ultimately gain insight into their palaeoclimatic significance in temperate climate settings. Our findings indicate that soil CO₂ is linearly correlated to MAT and its mean annual concentration is described by the equation: soil CO₂ (ppmv) = 1112 + 460 MAT. Soil pCO₂ can also be exponentially correlated to actual evapotranspiration. The pCO₂ in the aquifer is linearly correlated to MAT at the infiltration site and is more influenced by summer soil pCO₂. Cave air CO₂ in the innermost part of the caves exhibits a similar seasonal pattern, and commonly reaches concentrations of about 15% to 35%, with respect to the corresponding soil values, and is exponentially correlated to the MAT at the infiltration site. The combination of these parameters (soil pCO₂, dripwater pCO₂ and cave air pCO₂) results in speleothem growth and controls their fabrics which are typical of four MAT/elevation belts broadly corresponding to the present‐day vegetation zones. In the lower montane zone [100–800 m above sea level (a.s.l.)] speleothems mostly consist of columnar fabric, in the upper montane zone (800–1600 m a.s.l.) both columnar and dendritic fabrics are common, the Subalpine zone (1600–2200 m a.s.l.) is characterized mostly by moonmilk deposits, whereas in the Alpine zone (above 2200 m a.s.l.) no speleothems are forming today. Therefore, fabric changes in fossil speleothem can potentially be used to reconstruct MAT changes in temperate climate karst areas. Copyright © 2015 John Wiley & Sons, Ltd.     

地磁数据分析的一些思考

通过若干实例,本文讨论了地磁数据分析中的一些方法.这些方法包括时间序列的多项式拟合,相关性分析,频谱分析和小波分析等.在Matlab和AutoSignal软件下实现了以上方法,并基于这些方法研究了地磁场形态和地磁现象的频谱特征.我们分析了Surlari观测台（余纬45.3°,经度26.3°）的地磁时间序列,并与Ottawa（余纬44.6°,〖JP2〗经度284.5°）,Canberra（余纬125.3°,经度149.3°）, Kakioka（余纬53.8°,经度140.2°）,Vernadsky〖JP〗（余纬155.3°,经度295.7°）等台站的结果进行了对比分析,讨论了Fourier变换时间窗和小波基函数选取的影响,有限长时间序列引起的边缘效应,以及小波尺度和Fourier频率的关系等问题.我们采用谱分析和小波分析处理了2007年两个台站的地磁数据,研究了地磁场形态和地磁现象的频谱特征,并讨论了Fourier变换和小波变换的优缺点.     

A high-resolution Holocene record on the Southern Brazilian shelf: Paleoenvironmental implications

A high-resolution, multi-proxy record has been used to determine the environmental changes during the Holocene on the southern Brazilian shelf. Present oceanographic conditions reveal wind and freshwater input as the determinants of short-term productivity changes in the study area. Magnetic susceptibility and grain-size variations, together with proxies of productivity (organic carbon, carbon accumulation rate, Ba, Sr, and Ca content, Ba/Al, Ba/Ti, and Al/Ti ratios) were analyzed and compared with proxies of redox condition (V/Ti ratio), terrigenous input (Fe/Ca and Ti/Ca ratios), as well as other Element/Ti ratios, to evaluate the paleoceanographic and paleoclimatic changes over the period.The core covers a time interval of about 7650 years, with sedimentation rates varying from 0.025 to 0.250 cm a⁻¹, which represent time intervals of between 8 and 80 a per sample. There is a clear change in the sedimentation rate at about 2800 B.P.All grain-size and elemental results indicate the occurrence of conspicuous changes between 5200 and 5000 cal. B.P., as well as between 3000 and 2800 cal. B.P. A comparison of the results with the palynological information available from the adjacent continental areas suggests that the sedimentary changes in this last interval may be correlated with the onset of modern climatic conditions in South America, and especially, with the onset of the Plata Plume Water, a water mass that carries cold, less saline waters towards the north. However, minor changes are observed at ca. 1500 B.P. and are correlated with an increase in the atmospheric humidity. Furthermore, a time-series analysis undertaken using several proxies indicated the occurrence of Sub-Milankovitch cycles, which may be compared with those reported worldwide.     

Seasonal and inter-annual zooplankton dynamics in temporary pools with different hydroperiods

The results of a research carried out in 2001 on nine temporary mountain pools (Northern Apennines, Italy) underlined a major role of hydroperiod in shaping zooplankton communities of temporary habitats. In 2002, the same pools were studied to assess inter-annual differences in zooplankton seasonal patterns. Data on precipitations (both snow and rainfalls) were collected to evaluate the influence of precipitation regimes on hydroperiod and concurrently on hydrochemical features and zooplankton dynamics.Mean annual snow and rainfall abundances were highly similar in both years but precipitation patterns were different. Moreover, different air temperatures were measured in the 2 years of study. These factors influenced water persistence and dry and wet cycles in the pools: in 2001, three pools dried out in summer and remained dry until autumn rainfalls (type A pools), in five pools (type B pools) the summer dry period was interrupted by re-filling due to storms in July and only in one pool water did remain for the entire research period (C1). In 2002, type A and B pools underwent only one dry phase (June–July) while C1 showed a hydroperiod similar to the one that occurred in the previous year. Overall, type A and B pools can be classified as ‘seasonal’ and C1 as ‘near-permanent or permanent’.Principal component analysis and paired t-tests did not show significant differences between years in the hydrochemical features of the pools. However, the seasonal pools showed a wide range of variation in their hydrochemical parameters while water features of the permanent pool presented less variability.Within the pools, divergences in the number and in the type of zooplankton taxa between the 2 years were limited. Rotifer and copepod density of the seasonal pools were comparable over years and only cladocerans exhibited distinct density dynamics. Cladoceran appeared to be associated with ionic content and influenced by the occurrence of ice-melting and by the wet phase length of the pools.On the contrary, the permanent pool showed diverse zooplankton seasonal patterns in 2001 compared to 2002. Over years, different pH values were measured; pH and conductivity varied with changing water volume, which in turn explained a significant amount of the observed variation in zooplankton densities in 2002.     

Seasonal and event-controlled export of organic matter from the shelf towards the Gulf of Lions continental slope

To investigate the role of coastal canyons in the transfer of organic matter from the shelf to the slope and basin, we deployed sediment trap/current meter pairs at the head of five canyons in the Gulf of Lions (GoL) between November 2003 and May 2004. Analysis of organic carbon, biogenic silica, Corg isotopic composition, Corg/total nitrogen, chloropigments, and amino acids clearly shows the seasonal influence and effect of extreme meteorological events on the composition of collected particles. The sampling period was divided into three “scenarios”. The first corresponded to a large easterly storm and flood of the Rhone river during stratified water column conditions; the composition of material collected during this event was influenced by increased transfer of riverine and coastal particulate matter, with a lower Corg content. During the second “fall-winter” scenario, northern and northwestern winds blowing over the shelf caused cooling and homogenization of the shelf water column; particles collected at this time reflected the homogeneous source of particulate matter transported through canyons; particles sitting in the vicinity of canyon heads are most likely swept downslope by the general south-westward circulation. Organic tracers indicate a degraded origin for organic matter transported during this period. A third “spring” scenario corresponded to northern winds alternating with eastward windstorms that triggered and/or enhanced the cascading of dense waters accumulated on the bottom of the shelf due to previous cooling. These conditions occurred in conjunction with increased phytoplankton productivity in shelf surface waters. Organic matter advected mainly by dense shelf water cascading was fresher due to the transport of newly produced particles and a variable terrestrial fraction; this fraction depended on the proportion of resuspended material accumulated during previous high discharge periods that was involved in each transport pulse. The tight link shown between meteorological conditions and organic matter transport is important for continental margin geochemical studies as future changes in climatic conditions may lead to dramatic changes in carbon sequestration capability and in the ecosystems of deep margin environments.     

Sonoran Desert productivity and the effect of trap size on litterfall estimates in dryland vegetation

We describe the temporal and spatial litterfall and test the accuracy of different litter collection devices in a Sonoran Desert community. Two low-lying PVC litter trap designs were tested and compared against a standard IBP trap. The test traps collected significantly more plant litter than the IBP traps, which failed to capture most of the litter of ephemerals and low shrubs. The largest differences between the traps appeared after the pulses of growth of ephemeral plants. Data collection for a period of almost 2 years showed an annual total litterfall of 3·43 Mg ha⁻¹for the test traps and 2·77 Mg ha⁻¹for the IBP traps. These values are well above the average for deserts and fit better into the lower range of tropical dry forests. The test PVC traps are inexpensive, economical in collecting and sorting effort, and less prone to vandalism. Also, they can be laid in higher numbers than IBP traps, thus providing a better representation of the highly heterogeneous desert environment.     

A GIS-based approach for gully erosion susceptibility modelling: a test in Sicily, Italy

The aim of this study is to analyze the susceptibility conditions to gully erosion phenomena in the Magazzolo River basin and to test a method that allows for driving the factors selection. The study area is one of the largest (225 km²) watershed of southern Sicily and it is mostly characterized by gentle slopes carved into clayey and evaporitic sediments, except for the northern sector where carbonatic rocks give rise to steep slopes. In order to obtain a quantitative evaluation of gully erosion susceptibility, statistical relationships between the spatial distributions of gullies affecting the area and a set of twelve environmental variables were analyzed. Stereoscopic analysis of aerial photographs dated 2000, and field surveys carried out in 2006, allowed us to map about a thousand landforms produced by linear water erosion processes, classifiable as ephemeral and permanent gullies. The linear density of the gullies, computed on each of the factors classes, was assumed as the function expressing the susceptibility level of the latter. A 40-m digital elevation model (DEM) prepared from 1:10,000-scale topographic maps was used to compute the values of nine topographic attributes (primary: slope, aspect, plan curvature, profile curvature, general curvature, tangential curvature; secondary: stream power index; topographic wetness index; LS-USLE factor); from available thematic maps and field checks three other physical attributes (lithology, soil texture, land use) were derived. For each of these variables, a 40-m grid layer was generated, reclassifying the topographic variables according to their standard deviation values. In order to evaluate the controlling role of the selected predictive variables, one-variable susceptibility models, based on the spatial relationships between each single factor and gullies, were produced and submitted to a validation procedure. The latter was carried out by evaluating the predictive performance of models trained on one half of the landform archive and tested on the other. Large differences of accuracy were verified by computing geometric indexes of the validation curves (prediction and success rate curves; ROC curves) drawn for each one-variable model; in particular, soil texture, general curvature and aspect demonstrated a weak or a null influence on the spatial distribution of gullies within the studied area, while, on the contrary, tangential curvature, stream power index and plan curvature showed high predictive skills. Hence, predictive models were produced on a multi-variable basis, by variously combining the one-variable models. The validation of the multi-variables models, which generally indicated quite satisfactory results, were used as a sensitivity analysis tool to evaluate differences in the prediction results produced by changing the set of combined physical attributes. The sensitivity analysis pointed out that by increasing the number of combined environmental variables, an improvement of the susceptibility assessment is produced; this is true with the exception of adding to the multi-variables models a variable, as slope aspect, not correlated to the target variable. The addition of this attribute produces effects on the validation curves that are not distinguishable from noise and, as a consequence, the slope aspect was excluded from the final multi-variables model used to draw the gully erosion susceptibility map of the Magazzolo River basin. In conclusion, the research showed that the validation of one-variable models can be used as a tool for selecting factors to be combined to prepare the best performing multi-variables gully erosion susceptibility model.     

A contribution to the reconstruction of Miocene seepage from authigenic carbonates of the northern Apennines (Italy)

Authigenic carbonates from outcrops of the northern Apennines consist of small and irregular lenses and exhibit numerous features indicative of cold-seep settings. Detailed petrographic, mineralogical and geochemical studies from two Miocene deposits are presented. The first carbonate outcrop, named Fosso Riconi, is located in the foredeep basin of the Apenninic chain, whereas the second deposit represents a satellite basin called Sarsetta. The stable isotope data from specific carbonate minerals show a wide range of values well known from other palaeoseeps of the Apennine Mountains. The majority of seep carbonates are formed by low-Mg calcite and ankerite. Those minerals have δ¹³C values between ?7 and ?23‰ V-PDB, suggesting variable amounts of carbonate derived from oxidized methane, seawater (dissolved inorganic carbon) and sedimentary organic matter. Dolomite samples have the lowest δ¹³C values (?30.8 to ?39.0‰ V-PDB), indicating methane as the main carbon source. The findings suggest an evolutionary formation of the seeps and development of authigenic carbonates influenced by the activity of chemosynthetic organisms, of which large lucinid clams are preserved. Bioirrigation by the clams controlled the sediment–water exchange, and is here considered as an explanation for the anomalous Mg content of the calcite. We hypothesize that the seep carbonates were formed during periods of active methane-rich seepage, whereas during periods of slow seepage carbonate formation was reduced. Despite different geological settings, the two examined deposits of Sarsetta and Fosso Riconi show similar features, suggesting that a common pattern of fluid circulation played a major role in carbonate formation at both seep sites.