Determination of Halogens (F, Cl, Br, I), Sulfur and Water in Seventeen Geological Reference Materials

Fluorine, chlorine, bromine, iodine and sulfur were determined in seventeen geological reference materials after extraction by pyrohydrolysis. Fluorine, Cl and S (as sulfate ions) were determined in the extraction solution by ion chromatography with detection limits of around 0.2 mg l⁻¹. Bromine and I were measured by ICP-MS with detection limits of 1 μg l⁻¹ for Br and 0.1 μg l⁻¹ for I. For rock samples, using normal extraction conditions (500 mg of sample and 100 ml of final solution) detection limits were 40 mg kg⁻¹ for F and Cl, 15 mg kg⁻¹ for S, 0.2 mg kg⁻¹ for Br and 0.02 mg kg⁻¹ for I. These detection limits may be improved by increasing the amount of sample and hence the concentration of the final solution. Water was also determined using an extraction technique based on H₂O degassing, reduction on zinc at 1000 °C and H₂ manometry. Our results for fluorine, chlorine, sulfur and water are in good agreement with literature data. Very few reference materials have recommended values for bromine and especially for iodine. Among the analysed samples, three are new reference materials: BHVO-2, BCR-2 and AGV-2.     

Trends in the frequency of synoptic types in central-southern Chile in the period 1961–2012 using the Jenkinson and Collison synoptic classification

Atmospheric circulation patterns in southern Chile (42° 30′ S) were studied in order to determine and analyse the most characteristic synoptic types and their recent trends, as well as to gain an understanding of how they are associated with low-frequency variability patterns. According to the Jenkinson and Collison (J&C) classification method, a 16-point grid of sea-level pressure data was employed. The findings reveal that some synoptic types show statistically significant trends with a 95% confidence level, positively for anticyclonic westerly hybrids (AW) and advective types for third and fourth quadrant wind flows (W, NW, and N) and negatively for SW and cyclonic hybrids (CS and CSW). A model has been constructed of the linear regression of some weather types with teleconnections that most affect Chile: the undetermined types (U), AW were associated with El Niño or the warm phase of the Pacific Decadal Oscillation (PDO), whereas the cyclonic northerly and cyclonic northeasterly types (CN and CNE) were associated with La Niña or cool phase of the PDO. The weather types associated with Antarctic Oscillation (AAO) in its positive phase are anticyclonic northerly and northeasterly and northerly advection types, while in its negative phase are cyclonic southwesterly and advection types.     

Iron(II) oxide determination in rocks and minerals

The determination of FeO of geologic materials by modern instrumental methods (such as atomic absorption spectroscopy (AAS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray fluorescence (XRF), etc.) cannot distinguish between different oxidation states of elements. In many cases, the oxidation state of Fe has to be known in order to perform several chemical calculations (norms, etc.) and discuss the reactions that occur during weathering, hydrothermal alteration and other processes. A modified Wilson method is proposed, giving reproducible results in a much shorter time than the classical method. Back-titration with potassium dichromate and an Fe(II) and ammonia sulphate solution is used, after dissolution of the sample powder in a heated HF/H₃PO₄ mixture and an ammonium vanadate solution. This modified method, tested with several international reference materials, gives reliable results, equivalent to the ones cited in the literature for the reference materials.     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

Regional retrograde alteration of sub-greenschist facies chlorite to smectite

Dioctahedral smectite is present as a retrograde alteration product of chlorite in Permian-Triassic red slates of the Malaguide Complex in Sierra de Espuña (Betic Cordillera). Mineral assemblages and textures, illite crystallinity indices, and fluid inclusion data indicate sub-greenschist facies conditions that reached at least 180°C in the higher-grade tectonic unit of the Malaguide Complex, preceding formation of smectite. Smectite, having K as the dominant interlayer cation, occurs ubiquitously intercalated with trioctahedral chlorite as thin packets of layers and as individual layers that commonly change to chlorite along layers. Although some chlorite is typically homogeneous and trioctahedral, much chlorite shows signs of alteration and has compositions corresponding to different degrees of smectite contaimination. The incompatibility of metamorphic grade with the occurrence of smectite, the general association of chlorite and smectite, and the textural relations collectively show that dioctahedral smectite is derived through replacement of trioctahedral chlorite. Such replacement occurs on a regional basis and demonstrates that caution must be used in interpreting the occurrence of smectite in pelites as being due to prograde processes. Alteration of trioctahedral chlorite under oxidizing conditions due to introduction of phreatic water after uplift of the Betic Cordillera is proposed as the cause of formation of smectite.     

Risk assessment of groundwater pollution using sensitivity analysis and a worst-case scenario analysis

This paper illustrates how sensitivity analysis and a worst-case scenario analysis can be useful tools in risk assessment of groundwater pollution. The approach is applied to a study area in Hungary with several known groundwater pollution sources and nearby drinking water production wells. The main concern is whether the contamination sources threaten the drinking water wells of the area. A groundwater flow and transport model is set up to answer this question. Due to limited data availability, the results of this model are associated with large uncertainty. Sensitivity analysis and a worst-case scenario analysis are applied to estimate this uncertainty and build confidence in the model results.     

Evaluation of methods of spatial interpolation for monthly rainfall data over the state of Rio de Janeiro,Brazil

Five deterministic methods of spatial interpolation of monthly rainfall were compared over the state of Rio de Janeiro, southeast Brazil. The methods were the inverse distance weight (IDW), nearest neighbor (NRN), triangulation with linear interpolation (TLI), natural neighbor (NN), and spline tension (SPT). A set of 110 weather stations was used to test the methods. The selection of stations had two criteria: time series longer than 20 years and period of data from 1960 to 2009. The methods were evaluated using cross-validation, linear regression between values observed and interpolated, root mean square error (RMSE), coefficient of determination (r ²), coefficient of variation (CV, %), and the Willmott index of agreement (d). The results from different methods are influenced by the meteorological systems and their seasonality, as well as by the interaction with the topography. The methods presented higher precision (r ²) and accuracy (d, RMSE) during the summer and transition to autumn, in comparison with the winter or spring months. The SPT had the highest precision and accuracy in relation to other methods, in addition to having a good representation of the spatial patterns expected for rainfall over the complex terrain of the state and its high spatial variability.     

Impact of single-point GPS integrated water vapor estimates on short-range WRF model forecasts over southern India

Specifying physically consistent and accurate initial conditions is one of the major challenges of numerical weather prediction (NWP) models. In this study, ground-based global positioning system (GPS) integrated water vapor (IWV) measurements available from the International Global Navigation Satellite Systems (GNSS) Service (IGS) station in Bangalore, India, are used to assess the impact of GPS data on NWP model forecasts over southern India. Two experiments are performed with and without assimilation of GPS-retrieved IWV observations during the Indian winter monsoon period (November–December, 2012) using a four-dimensional variational (4D-Var) data assimilation method. Assimilation of GPS data improved the model IWV analysis as well as the subsequent forecasts. There is a positive impact of ～10 % over Bangalore and nearby regions. The Weather Research and Forecasting (WRF) model-predicted 24-h surface temperature forecasts have also improved when compared with observations. Small but significant improvements were found in the rainfall forecasts compared to control experiments.     

Evaluation of global climate model on performances of precipitation simulation and prediction in the Huaihe River basin

Using climate models with high performance to predict the future climate changes can increase the reliability of results. In this paper, six kinds of global climate models that selected from the Coupled Model Intercomparison Project Phase 5 (CMIP5) under Representative Concentration Path (RCP) 4.5 scenarios were compared to the measured data during baseline period (1960–2000) and evaluate the simulation performance on precipitation. Since the results of single climate models are often biased and highly uncertain, we examine the back propagation (BP) neural network and arithmetic mean method in assembling the precipitation of multi models. The delta method was used to calibrate the result of single model and multimodel ensembles by arithmetic mean method (MME-AM) during the validation period (2001–2010) and the predicting period (2011–2100). We then use the single models and multimodel ensembles to predict the future precipitation process and spatial distribution. The result shows that BNU-ESM model has the highest simulation effect among all the single models. The multimodel assembled by BP neural network (MME-BP) has a good simulation performance on the annual average precipitation process and the deterministic coefficient during the validation period is 0.814. The simulation capability on spatial distribution of precipitation is: calibrated MME-AM > MME-BP > calibrated BNU-ESM. The future precipitation predicted by all models tends to increase as the time period increases. The order of average increase amplitude of each season is: winter > spring > summer > autumn. These findings can provide useful information for decision makers to make climate-related disaster mitigation plans.     

Ecological quality assessment of small estuaries from the Portuguese coast based on benthic macroinvertebrate assemblages indices

Benthic macroinvertebrates communities are the most consistently emphasized biotic component of aquatic ecosystems and are one of the biological indicators required for assessment by the European Water Framework Directive. In this context, several indices based on these communities have been developed in order to assess ecological quality of estuarine systems. In the present work we used AMBI, M-AMBI, BENTIX and BAT to distinguish ecological status of five small estuarine systems of the Portuguese south and southwest coasts. Although indices outputs did not differ between systems and sampling seasons, results indicated that the metrics in which these indices are based could differentiate community structures as a result of two main gradients that force these communities: the natural variability, and the anthropogenic impact.