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.     

Deep-sea ostracods as indicators of palaeoceanographic changes: a case history from the middle–late Miocene of southern Italy (Central Mediterranean)

ABSTRACT The middle–late Miocene palaeoceanography of the Central Mediterranean was investigated using bio-chronostratigraphically constrained (estimated ages are based on plancktonic foraminifers) ostracod faunas from the Tremiti Islands and the Hyblean Plateau (southern Italy). Specifically, differences and similarities between the hydrographical evolution of the two study areas, inferred from the ostracod record, are herein used to provide new insights into the evolution of the Mediterranean deep-water circulation. Ostracod assemblage compositions suggest a simultaneous progressive trend from deep thermospheric towards psychrospheric conditions in both the areas during the Langhian. However, this trend seems to have developed fully only in the Hyblean Plateau. Notably, the first sign of an oceanic deep water-mass supply is shown by the almost synchronous entry of the upper psychrospheric genus Agrenocythere in the middle Langhian. The youngest reliable evidence of deep oceanic influences (common occurrence of Agrenocythere ) in the Central Mediterranean comes from the Tremiti Islands and dates back to the earliest Serravallian. Similarities between the two study areas suggest large-scale modifications in the Central Mediterranean deep basins. This hypothesis is discussed in the context of the global middle Miocene oceanographic scenario.     

Precipitation and evaporation budgets over the Baltic Proper: observations and modelling

Precipitation and evaporation budgets over the Baltic Sea were studied in a concerted project called PEP in BALTEX (Pilot study of Evaporation and Precipitation in the Baltic Sea), combining extensive field measurements and modelling efforts. Eddy-correlation-measurements of turbulent heat flux were made on a semi-continuous basis for a 12 month period at four well-exposed coastal sites in the Baltic Proper (the main basin of the Baltic Sea). Precipitation was measured at land-based sites with standard gauges and on four merchant ships travelling between Germany and Finland with the aid of specially designed ship rain gauges (SRGs). The evaporation and precipitation regime of the Baltic Sea was modelled for a 12 month period by applying a wide range of numerical models: the operational atmospheric High Resolution Limited Area Model (HIRLAM, Swedish and Finnish versions), the German atmospheric REgional-scale MOdel, REMO, the operational German Europe Model (only precipitation), the oceanographic model PROBE-Baltic, and two models that use interpolation of ground-based data, the Swedish MESAN model of SMHI and a German model of IFM-GEOMAR Kiel. Modelled precipitation was compared with SRG measurements on board the ships. A reasonable correlation was obtained, but the regional-scale models and MESAN gave some 20% higher precipitation over the sea than is measured. Bulk parameterisation schemes for evaporation were evaluated against measurements. A constant value of C_HN and C_EN with wind speed, underestimated large fluxes of both sensible and latent heat flux. The limited area models do not resolve the influence of the height of the marine boundary layer in coastal zones and the entrainment (on the surface fluxes), which may explain the observed low correlations between modelled and measured latent heat fluxes. Estimates of evaporation, E, and precipitation, P, for the entire Baltic Proper were made with several models for a 12 month period. While the annual variation was well represented by all predictions, there are still important differences in the annual means. Evaporation ranges from 509 to 625 mm year^-1 and precipitation between 624 and 805 mm year^-1 for this particular 12 month period. Taking the results of model verification from the present study into account, the best estimate of P-E is about 100 ± 50 mm for this particular 12 month period. But the annual mean of P-E varies considerably from year to year. This is reflected in simulations with the PROBE-Baltic model for an 18 year period, which gave 95 mm year^-1 for the 12 month period studied here and 32 mm year^-1 as an average for 18 years.     

Wave reflection in 3D conditions

Based on recent experiments carried out in wave basin on breakwaters with armour layer of rocks and cubes, this paper examines the dependence of the reflection coefficient on wave directional spreading and obliquity. Results suggest that long-crested and short-crested waves give similar reflection. The reflection coefficient is markedly dependent on the wave angle of incidence. The performance of formulae available in the literature is checked against the new dataset and a significant improvement is proposed by including the wave obliquity factor that appears in the traditional expression for the overtopping discharge.     

An Approach to Quantify the Heat Wave Strength and Price a Heat Derivative for Risk Hedging

Mitigating the heat stress via a derivative policy is a vital financial option for agricultural producers and other business sectors to strategically adapt to the climate change scenario. This study has provided an approach to identifying heat stress events and pricing the heat stress weather derivative due to persistent days of high surface air temperature (SAT). Cooling degree days (CDD) are used as the weather index for trade. In this study, a call-option model was used as an example for calculating the price of the index. Two heat stress indices were developed to describe the severity and physical impact of heat waves. The daily Global Historical Climatology Network (GHCN-D) SAT data from 1901 to 2007 from the southern California, USA, were used. A major California heat wave that occurred 20-25 October 1965 was studied. The derivative price was calculated based on the call-option model for both long-term station data and the interpolated grid point data at a regular 0.1 ×0.1 latitude-longitude grid. The resulting comparison indicates that (a) the interpolated data can be used as reliable proxy to price the CDD and (b) a normal distribution model cannot always be used to reliably calculate the CDD price. In conclusion, the data, models, and procedures described in this study have potential application in hedging agricultural and other risks.     

The oxidation state of manganese in marine sediments and ferromanganese nodules

Marine sediments and ferromanganese nodules from the Pacific Ocean have been analyzed for the $\text{O}\text{Mn}$ ratio of solid manganese. We tested six chemical methods and concluded that the iodometric and oxalate methods were equivalent and were the best choice in terms of accuracy and precision on natural samples. We choose the iodometric method for most of our analyses because the oxalate procedure is a method of differences.The ferromanganese nodules that we analyzed were all from MANOP site H and had $\text{Mn}\text{Fe}$ ratios that ranged from 5.6 to 70. These nodules were invariably highly oxidized with $\text{O}\text{Mn}$ values ranging from 1.90 to 2.00. Our most precise analyses suggest that less than 1% of the total manganese is present as Mn(II).We also analyzed red clay and hemipelagic sediments from the eastern tropical Pacific (Baja borderland and MANOP site H) and carbonate ooze samples from the equatorial Pacific. These sediments are also highly oxidized ($\text{O}\text{Mn}\text{= 1.90 to 2.00}$) except when Mn(II) appears in the interstitial water. As dissolved Mn(II) increases the value of the $\text{O}\text{Mn}$ ratio in the solid phase decreases. The $\text{O}\text{Mn}$ ratio decreases to values as low as 1.40. This decrease appears to be due to a decrease in oxidized manganese by reduction, however, an increase in reduced manganese in the solid sediments by adsorption or MnCO₃ formation can not be ruled out in all cases.     

The last interglacial ocean

The final effort of the CLIMAP project was a study of the last interglaciation, a time of minimum ice volume some 122,000 yr ago coincident with the Substage 5e oxygen isotopic minimum. Based on detailed oxygen isotope analyses and biotic census counts in 52 cores across the world ocean, last interglacial sea-surface temperatures (SST) were compared with those today. There are small SST departures in the mid-latitude North Atlantic (warmer) and the Gulf of Mexico (cooler). The eastern boundary currents of the South Atlantic and Pacific oceans are marked by large SST anomalies in individual cores, but their interpretations are precluded by no-analog problems and by discordancies among estimates from different biotic groups. In general, the last interglacial ocean was not significantly different from the modern ocean. The relative sequencing of ice decay versus oceanic warming on the Stage 6/5 oxygen isotopic transition and of ice growth versus oceanic cooling on the Stage 5e/5d transition was also studied. In most of the Southern Hemisphere, the oceanic response marked by the biotic census counts preceded (led) the global ice-volume response marked by the oxygen-isotope signal by several thousand years. The reverse pattern is evident in the North Atlantic Ocean and the Gulf of Mexico, where the oceanic response lagged that of global ice volume by several thousand years. As a result, the very warm temperatures associated with the last interglaciation were regionally diachronous by several thousand years. These regional lead-lag relationships agree with those observed on other transitions and in long-term phase relationships; they cannot be explained simply as artifacts of bioturbational translations of the original signals.     

Time constraints for Mesoproterozoic upper amphibolite facies metamorphism in NW Namibia: a multi-isotopic approach

This study presents the chronological evolution of the upper amphibolite facies Orue Unit in NW Namibia. Metasedimentary and meta-igneous rocks of the Orue Unit were investigated using the Pb–Pb stepwise leaching technique on garnet and rutile, U–Pb multi-grain analysis on rutile, Sm–Nd–Lu–Hf leaching technique on garnet, SHRIMP analysis on zircon and Ar–Ar dating on amphibole. Each of these techniques pertains to different processes that occurred before, during, or after the metamorphic peak. Our age data can be integrated with petrological constraints to provide a more complete understanding of the metamorphic cycle. Our pre-peak metamorphic zircon ages, peak metamorphic garnet ages and peak to late peak metamorphic amphibole ³⁹Ar–⁴⁰Ar ages bracket the upper amphibolite facies metamorphic event including hydration or dehydration processes into a time span of only ca. 20 Ma. The age data obtained by peak metamorphic mineral analyses cluster around 1340–1320 Ma. Based on age data and field observation, we interpret the upper amphibolite facies metamorphism as a large-scale regional mid-crustal event. Spot analyses of inherited zircon cores obtained by SHRIMP reflect the sedimentary origin of the respective rocks of the Orue Unit and derivation from Palaeoproterozoic protoliths. The metamorphic rocks south of the anorthositic Kunene Intrusive Complex (KIC) have previously been ascribed to the Palaeoproterozoic Epupa Complex at the SW margin of the Congo craton and were thus thought to be older than the Mesoproterozoic KIC. Our data show that the high-grade metamorphic overprint took place 30–50 Ma after emplacement of the KIC. Rutile growth ages of 1248 Ma in one sample reflect fluid activity which seems to be a local phenomenon since there is no other evidence of geological activity throughout the Orue Unit at that time. The rutile ages predate the emplacement of satellite intrusions in that area by 30 Ma and there is no causal relation between these two events.     

A multi-method approach for the identification and quantification of water balance components of two lentic small water bodies

The protection of the globally widespread lentic small water bodies (LSWB) must be based on detailed knowledge about their hydrological connectivity and water balance. The study aimed to identify and quantify water balance components as well as surface-groundwater interaction of two LSWB in a characteristic lowland region with a combination of different methods. This includes the collection of hydrological data and the use of bromide and water stable isotopes (δ²H and δ¹⁸O) as tracers. With their help, mixing models were established, and daily water balances were assessed. The results show a strong bidirectional interaction of both LSWB systems with shallow groundwater. Bromide and stable isotope tracers allowed for the identification of the most relevant in- and outflow sources and pathways. Thereby, isotope data revealed isotopic enrichment typical for open-water bodies and only minor precipitation inputs mainly relevant at the end of the dry season. Water balance calculations suggested accentuated seasonal dynamics that were strongly influenced by shallow groundwater, which represented large inputs into both LSWB. By that, different phases could be identified, with high inflow rates in winter and spring and decreasing fluxes in summer. In one LSWB, a drainage system was found to have a major impact next to the shallow groundwater interaction. The findings of this research provide detailed insights into the influence and importance of shallow groundwater for LSWB in lowland regions. This impacts the diffuse input of agricultural pollutants into these ecologically important landscape features.