Water quality and risk assessment of dug wells: a case study for a poor community in the city of São Paulo, Brazil

Sparsely populated areas, or peripheral communities commonly lack access to a public water supply and sewerage systems. The inhabitants of these areas must make use of excavated wells to provide their water needs, and cesspits for domestic wastewater disposal. These on-site sanitation systems can release pathogens and nutrients into shallow groundwater. These poor communities urgently require cheap and efficient techniques for the detection of sanitary conditions, in order to prevent contamination of the water resources supplied by dug wells. The sanitary risk assessment methodology, applied in an irregular settlement south of the city of São Paulo, was based on a questionnaire with yes/no questions (risk factors), which allowed the identification of problems related to the well construction and operation, and the presence of potential contamination sources in its vicinity. These risk factors were compared against nitrate and bacterial analysis using the clustering statistical method, to verify the relationship between contamination and certain aspects surveyed in the questionnaire. Questions that were more related to contaminated wells were those concerning the presence of cover and its integrity; gaps between mouth and cover; the surrounding pavement and presence of ground irregularities; infiltration in the well casing; water-suspended materials; and proximity to contamination sources. Contamination models based on variograms allowed to observe that bacterial contamination presented a strong localized component, which was associated frequently with the way residents handled the wells, whereas nitrate contamination was related more to a regional (spatial) component; that is, the distance between wells and cesspits.     

A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ?25 but ?100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ∼1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO₂ gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO₂ gas, and a more mature (oxidized) kerogen with a lower H/C which in turn melts incongruently with further burial to produce more crude oil, CO₂ gas, and a kerogen with a lower H/C and so forth.The petroleum generated in the process progresses from heavy naphthenic crude oils at low temperatures to mature petroleum at ∼150 °C. For example, the results of Computer Experiment 27 (see below) indicate that the overall incongruent melting reaction in the water-absent region of the system C-H-O at 150 °C and a depth of ∼4.3 km of an immature type-II/III kerogen with a bulk composition represented by C₂₉₂H₂₈₈O_12(c) to produce a mature (oxidized) kerogen represented by C₁₂₈H₆₈O_7(c), together with a typical crude oil with an average metastable equilibrium composition corresponding to C_8.8H_16.9 (C_8.8H_16.9(l)) and CO₂ gas (CO_2(g)) can be described by writing

(A)     

Amphibole as an archivist of magmatic crystallization conditions: problems,potential, and implications for inferring magma storage prior to the paroxysmal 2010 eruption of Mount Merapi,Indonesia

Amphibole is widely employed to calculate crystallization temperature and pressure, although its potential as a geobarometer has always been debated. Recently, Ridolfi et al. (Contrib Mineral Petrol 160:45–66, 2010) and Ridolfi and Renzulli (Contrib Mineral Petrol 163:877–895, 2012) have presented calibrations for calculating temperature, pressure, fO₂, melt H₂O, and melt major and minor oxide composition from amphibole with a large compositional range. Using their calibrations, we have (i) calculated crystallization conditions for amphibole from eleven published experimental studies to examine the problems and the potential of the new calibrations; and (ii) calculated crystallization conditions for amphibole from basaltic–andesitic pyroclasts erupted during the paroxysmal 2010 eruption of Mount Merapi in Java, Indonesia, to infer pre-eruptive conditions. Our comparison of experimental and calculated values shows that calculated crystallization temperatures are reasonable estimates. Calculated fO₂ and melt SiO₂ content yields potentially useful estimates at moderately reduced to moderately oxidized conditions and intermediate to felsic melt compositions. However, calculated crystallization pressure and melt H₂O content are untenable estimates that largely reflect compositional variation in the crystallizing magmas and crystallization temperature and not the calculated parameters. Amphibole from Merapi’s pyroclasts yields calculated conditions of ~200–800 MPa, ~900–1,050 °C, ~NNO + 0.3–NNO + 1.1, ~3.7–7.2 wt% melt H₂O, and ~58–71 wt% melt SiO₂. We interpret the variations in calculated temperature, fO₂, and melt SiO₂ content as reasonable estimates, but conclude that the large calculated pressure variation for amphibole from Merapi and many other arc volcanoes is evidence for thorough mixing of mafic to felsic magmas and not necessarily evidence for crystallization over a large depth range. In contrast, bimodal pressure estimates obtained for other arc magmas reflect amphibole crystallization from mafic and more evolved magmas, respectively, and should not necessarily be taken as evidence for crystallization in two reservoirs at variable depth.     

Assessing Decomposition Rates of Rhizophora mangle and Laguncularia racemosa Leaves in a Tropical Mangrove

Studies exploring leaf decomposition in mangroves in the Brazilian northeast are scarce. Therefore, in a mangrove of the Cachoeira River estuary at Ilhéus, Bahia, the decomposition of senescent leaves of Rhizophora mangle L. and Laguncularia racemosa Gaertn was studied. The litter-bag method and the Olson exponential model were applied to estimate the decomposition rates. The decay pattern of leaf material of both species was similar to those reported in the literature, with rapid initial weight loss, followed by a deceleration and period of slow weight loss. L. racemosa had the highest decay constants at all the study sites which suggest that their leaves are more easily degraded than those of R. mangle. The constantly submerged site presented the highest decay constants of 0.022 g g^?1 day^?1 for R. mangle and 0.031 g g^?1 day^?1 for L. racemosa. Most (95 %) of the leaf material of the two species was lost in 135 and 98 days, respectively. Benthic macrofauna organisms were recorded in the litter bags from the fifth day after the start of the experiment. Such organisms play a key role in the first phase of decomposition in this mangrove system. The decay constants of the leaf litter were generally higher than those reported in other tropical and subtropical regions. This suggests that differences in the process of decomposition are in response to environmental conditions at each location.     

Calorimetry of silicate melts at 1773 K: measurement of enthalpies of fusion and of mixing in the systems diopside-anorthite-albite and anorthite-forsterite

Transposed-temperature-drop calorimetry, using a Setaram HT 1500 calorimeter, was used to study directly the melting at 1773 K of mixtures of crystalline albite, anorthite, and diopside and of anorthite and forsterite. The enthalpy of albite at 1000–1773 K, starting with both crystalline and glassy samples, was also measured. The results confirm previously measured enthalpies of fusion of albite, diopside and anorthite (Stebbins et al. 1982, 1983; Richet and Bottinga 1984,1986). The new results use thermochemical cycles which completely avoid the glassy state by transforming crystals directly to melts. The enthalpy of fusion of forsterite is estimated to be 89±12 kJ/mol at 1773 K and 114±20 kJ/mol at its melting point of 2163 K. The data allow semiquantitative evaluation of heats of mixing in the molten silicates. Along the Ab-An join, enthalpies of mixing in the liquid at 773 K are the same or somewhat more negative than those in the glass at 986 K, whereas along Ab-Di and An-Di, enthalpies of mixing in the liquid are distinctly more positive than in the glass. These differences correlate with excess heat capacities in the liquids suggested by Stebbins et al. (1984).     

Case study on the strategy and application of enhancement solutions to improve remediation of soils contaminated with Cu, Pb and Zn by means of electrodialysis

Numerous studies have been conducted with electrochemical removal of heavy metals from spiked kaolinite. Meanwhile, when moving from kaolinite to real soils, new factors must be taken into account—factors influencing, e.g., the buffering capacity of the soil against acidification and the adsorption/desorption processes of the heavy metals. The present study gives some examples where it is necessary to use an enhancement solution to aid desorption of Cu, Zn and Pb during electrodialytic treatment. Dependent on the composition of the pollution, different choices can be made. In the case of a Cu-polluted calcareous soil, ammonia may be used as enhancement solution, due to the formation of charged complexes between ammonia and Cu. Thus, Cu is mobile at high pH when ammonia is added and Cu can be removed without dissolving the calcareous parts. Zn is also mobilized by ammonia, but to a lesser extent than Cu. In the case of Cu, Zn and Pb at the same time, alkaline ammonium citrate may be a solution. It was shown that this enhancement solution could mobilize these three pollutants, but optimization of concentration and pH of the ammonium citrate is still needed. When choosing a remediation scheme for electrochemical treatment of an actual industrially polluted soil, this scheme must be chosen on basis of characterization of soil and pollution combination.     

U-Th dating of Lake Lisan (late Pleistocene dead sea) aragonite and implications for glacial east Mediterranean climate change

U-series dating can be an effective means to obtain accurate and precise ages on Quaternary carbonates. However, most samples require a correction for U and Th in admixed detritus. This complication is often addressed through generation of U-Th isochrons, requiring analyses of several coeval samples. In addition, presence of water-derived (hydrogenous) Th in the carbonate can cause inaccuracies in isochron ages.This study reports a high-resolution U-series chronology of sediments deposited by Lake Lisan, the last glacial precursor of the Dead Sea. The strategy employed combines multiple measurements from a few stratigraphic heights and fewer analyses from many heights in a single described and measured section. The resulting chronology is based on ages at 22 heights in a ∼40-m-thick section covering the interval of ∼70-14 calendar ka BP. The effects of admixed detritus are evaluated using trace elements. Nearly pure aragonite samples, indicated by very low abundances of insoluble elements such as Nb and Zr, were found to contain hydrogenous Th, which causes the uncorrected U-²³⁰Th age of a modern sample to be ∼2.5 ka. Nevertheless, accurate ages have been obtained by correcting for the detrital and aqueous interferences. The resulting ages are in stratigraphic order, and their accuracy is evidenced by consistency of Lisan Formation U-series and ¹⁴C ages with the coral-based calendar-radiocarbon age calibration.The U-Th ages provide a context to unravel the limnological history of Lake Lisan. Boundaries between the Lower, Middle, and Upper stratigraphic units correspond to the MIS 4/3 and 3/2 transitions, respectively. During MIS 2 and 4 the lake generally showed a stable two-layer configuration and a positive fresh-water balance, reflected by deposition of laminated aragonite-detritus. Dry intervals during MIS 2 and 4 are indicated by thick gypsum layers and an inferred depositional hiatus, which are temporally associated with Heinrich events H1 at ∼17 ka and H6 at ∼65 ka, respectively. During MIS 3 the lake level was unstable with intermittent dry periods indicated by abundant clastic layers and a significant hiatus between ∼43-49 ka. Clastic layers are associated with Dansgaard-Oeschger events during MIS 3, and indicate lake level declines during abrupt Northern Hemisphere warmings. Overall, the climate of the Eastern Mediterranean region shows a strong linkage to the Northern Hemisphere climate, with increasing lake size and stability during cold periods, and fluctuations and dessication during warmings and Heinrich events.     

Delineation of groundwater protection zones by the backward particle tracking method: theoretical background and GIS-based stochastic analysis

The backward particle tracking method, an effective and powerful tool that can be used to delineate groundwater protection zones, is presented. The theoretical background and insights on the applicability of this method are provided. Moreover, the present work enriches the backward particle tracking method with an uncertainty analysis concerning the porosity values, applying a Monte Carlo (MC) approach, coupled with the use of geographical information systems (GIS). As an application example, a wellfield in the Komotini area, Greece, is investigated. The present study may serve as a potential guideline for wellfield delineation, particularly in areas like Greece where lack of data related to the hydrogeological system is often a problem.     

Euro-Cordex Regional Projection Models: What Kind of Agreement for Europe?

Mathematical Geosciences - EURO-CORDEX is an international initiative which provides regional climate projections based on multiple dynamical and empirical–statistical downscaling models. The...