A pan-European art trade in the late middle ages: Isotopic evidence on the master of Rimini enigma.

The identity of artists and localisation of workshops are rarely known with certainty before the mid-15th century. We investigated the material used by one of the most prolific and enigmatic medieval sculptors, the Master of the Rimini Altarpiece or Master of Rimini, active around 1420-40. The isotope fingerprints (Sr, S and O) of a representative corpus of masterpieces but also minor artworks, attributed to the Master of Rimini and his workshop, are virtually identical, demonstrating the unity of the corpus and a material evidence behind the stylistic and iconographic ascriptions. The material used is exclusively Franconian (N-Bavarian) alabaster, 600 km distant from the supposed zone of activity of the Master of Rimini workshop according to recent literature. The same material was later used by the prominent Late Medieval German carver Tilman Riemenschneider, active in Würzburg after 1483, whose small corpus of alabaster sculptures we have been able to characterize almost entirely. Based on these findings, we propose here an alternative to the prevailing hypothesis of a Flemish or N-French workshop being founded on similarities of the Rimini sculpture with motives in Flemish and French painting. Our scenario, returning to the initial proposal of a German localisation of the Master of Rimini workshop, assumes the migration of an artist, perhaps trained in the Low Countries or strongly inspired by the Flemish art, to Southern Germany where he founded a highly productive export workshop, well situated on the crossroads of medieval trade, with a pan-European radiance. This study sheds a spotlight on the on the trade networks of luxury goods, the raw material used for their production, and the high-end art market in Europe as well as on international migration of artists and styles, at the eve of the Renaissance.

Natural gas of radiolytic origin: An overlooked component of shale gas.

Natural gas is an important fossil energy source that has historically been produced from conventional hydrocarbon reservoirs. It has been interpreted to be of microbial, thermogenic, or, in specific contexts, abiotic origin. Since the beginning of the 21st century, natural gas has been increasingly produced from unconventional hydrocarbon reservoirs including organic-rich shales. Here, we show, based on a careful interpretation of natural gas samples from numerous unconventional hydrocarbon reservoirs and results from recent irradiation experiments, that there is a previously overlooked source of natural gas that is generated by radiolysis of organic matter in shales. We demonstrate that radiolytic gas containing methane, ethane, and propane constitutes a significant end-member that can account for >25% of natural gas mixtures in major shale gas plays worldwide that have high organic matter and uranium contents. The consideration of radiolytic gas in natural gas mixtures provides alternative explanations for so-called carbon isotope reversals and suggests revised interpretations of some natural gas origins. We submit that considering natural gas of radiolytic origin as an additional component in uranium-bearing shale gas formations will lead to a more accurate determination of the origins of natural gas.

Potential Impacts of Shale Gas Development on Inorganic Groundwater Chemistry: Implications for Environmental Baseline Assessment in Shallow Aquifers.

The potential contamination of shallow groundwater with inorganic constituents is a major environmental concern associated with shale gas extraction through hydraulic fracturing. However, the impact of shale gas development on groundwater quality is a highly controversial issue. The only way to reliably assess whether groundwater quality has been impacted by shale gas development is to collect pre-development baseline data against which subsequent changes in groundwater quality can be compared. The objective of this paper is to provide a conceptual and methodological framework for establishing a baseline of inorganic groundwater quality in shale gas areas, which is becoming standard practice as a prerequisite for evaluating shale gas development impacts on shallow aquifers. For this purpose, this paper first reviews the potential sources of inorganic contaminants in shallow groundwater from shale gas areas. Then, it reviews the previous baseline studies of groundwater geochemistry in shale gas areas, showing that a comprehensive baseline assessment includes documenting the natural sources of salinity, potential geogenic contamination, and potential anthropogenic influences from legacy contamination and surface land use activities that are not related to shale gas development. Based on this knowledge, best practices are identified in terms of baseline sampling, selection of inorganic baseline parameters, and definition of threshold levels.

A Probabilistic Approach for Predicting Methane Occurrence in Groundwater.

Aqueous geochemistry datasets from regional groundwater monitoring programs can be a major asset for environmental baseline assessment (EBA) in regions with development of natural gases from unconventional hydrocarbon resources. However, they usually do not include crucial parameters for EBA in areas of shale gas development such as methane concentrations. A logistic regression (LR) model was developed to predict the probability of methane occurrence in aquifers in Alberta (Canada). The model was calibrated and tested using geochemistry data including methane concentrations from two groundwater monitoring programs. The LR model correctly predicts methane occurrence in 89.8% (n = 234 samples) and 88.1% (n = 532 samples) of groundwater samples from each monitoring program. Methane concentrations strongly depend on the occurrence of electron donors such as sulfate and to a lesser extent on well depth and the total dissolved solids of groundwater. The model was then applied to a province-wide public health groundwater monitoring program (n = 52,849 samples) providing aqueous geochemistry data but no methane concentrations. This approach allowed the prediction of methane occurrence in regions where no groundwater gas data are available, thereby increasing the resolution of EBA in areas of shale gas development by using basic hydrochemical parameters measured in high-density groundwater monitoring programs.

A geochemical and multi-isotope modeling approach to determine sources and fate of methane in shallow groundwater above unconventional hydrocarbon reservoirs.

Due to increasing concerns over the potential impact of shale gas and coalbed methane (CBM) development on groundwater resources, it has become necessary to develop reliable tools to detect any potential pollution associated with hydrocarbon exploitation from unconventional reservoirs. One of the key concepts for such monitoring approaches is the establishment of a geochemical baseline of the considered groundwater systems. However, the detection of methane is not enough to assess potential impact from CBM and shale gas exploitation since methane in low concentrations has been found to be naturally ubiquitous in many groundwater systems. The objective of this study was to determine the methane sources, the extent of potential methane oxidation, and gas-water-rock-interactions in shallow aquifers by integrating chemical and isotopic monitoring data of dissolved gases and aqueous species into a geochemical PHREEQC model. Using data from a regional groundwater observation network in Alberta (Canada), the model was designed to describe the evolution of the concentrations of methane, sulfate and dissolved inorganic carbon (DIC) as well as their isotopic compositions (δ34SSO4, δ13CCH4 and δ13CDIC) in groundwater subjected to different scenarios of migration, oxidation and in situ generation of methane. Model results show that methane migration and subsequent methane oxidation in anaerobic environments can strongly affect its concentration and isotopic fingerprint and potentially compromise the accurate identification of the methane source. For example elevated δ13CCH4 values can be the result of oxidation of microbial methane and may be misinterpreted as methane of thermogenic origin. Hence, quantification of the extent of methane oxidation is essential for determining the origin of methane in groundwater. The application of this model to aquifers in Alberta shows that some cases of elevated δ13CCH4 values were due to methane oxidation resulting in pseudo-thermogenic isotopic fingerprints of methane. The model indicated no contamination of shallow aquifers by deep thermogenic methane from conventional and unconventional hydrocarbon reservoirs under baseline conditions. The developed geochemical and multi-isotopic model describing the sources and fate of methane in groundwater is a promising tool for groundwater assessment purposes in areas with shale gas and coalbed methane development.

Origins and processes of groundwater salinization in the urban coastal aquifers of Recife (Pernambuco, Brazil): A multi-isotope approach.

In the coastal multilayer aquifer system of a highly urbanized southern city (Recife, Brazil), where groundwaters are affected by salinization, a multi-isotope approach (Sr, B, O, H) was used to investigate the sources and processes of salinization. The high diversity of the geological bodies, built since the Atlantic opening during the Cretaceous, highly constrains the heterogeneity of the groundwater chemistry, e.g. Sr isotope ratios, and needs to be integrated to explain the salinization processes and groundwater pathways. A paleoseawater intrusion, most probably the 120 kyB.P. Pleistocene marine transgression, and cationic exchange are clearly evidenced in the most salinized parts of the Cabo and Beberibe aquifers. All (87)Sr/(86)Sr values are above the past and present-day seawater signatures, meaning that the Sr isotopic signature is altered due to additional Sr inputs from dilution with different freshwaters, and water-rock interactions. Only the Cabo aquifer presents a well-delimitated area of Na-HCO3 water typical of a freshening process. The two deep aquifers also display a broad range of B concentrations and B isotope ratios with values among the highest known to date (63-68.5‰). This suggests multiple sources and processes affecting B behavior, among which mixing with saline water, B sorption on clays and mixing with wastewater. The highly fractionated B isotopic values were explained by infiltration of relatively salty water with B interacting with clays, pointing out the major role played by (palaeo)-channels for the deep Beberibe aquifer recharge. Based on an increase of salinity at the end of the dry season, a present-day seawater intrusion is identified in the surficial Boa Viagem aquifer. Our conceptual model presents a comprehensive understanding of the major groundwater salinization pathways and processes, and should be of benefit for other southern Atlantic coastal aquifers to better address groundwater management issues.

Isotope and ion selectivity in reverse osmosis desalination: geochemical tracers for man-made freshwater.

A systematic measurement of ions and 2H/1H, 7Li/6Li, 11B/10B, 18O/ 16O, and 87Sr/86Sr isotopes in feed-waters, permeates, and brines from commercial reverse osmosis (RO) desalination plants in Israel (Ashkelon, Eilat, and Nitzana) and Cyprus (Larnaca) reveals distinctive geochemical and isotopic fingerprints of fresh water generated from desalination of seawater (SWRO) and brackish water (BWRO). The degree of isotope fractionation during the passage of water and solutes through the RO membranes depends on the medium (solvent-water vs. solutes), chemical speciation of the solutes, their charge, and their mass difference. O, H, and Sr isotopes are not fractionated during the RO process. 7Li is preferentially rejected in low pH RO, and B isotope fractionation depends on the pH conditions. Under low pH conditions, B isotopes are not significantly fractionated, whereas at high pH, RO permeates are enriched by 20 per thousand in 11B due to selective rejection of borate ion and preferential permeation of 11B-enriched boric acid through the membrane. The specific geochemical and isotopic fingerprints of SWRO provide a unique tool for tracing "man-made" fresh water as an emerging recharge component of natural water resources.

Health impact evaluation of boron in drinking water: a geographical risk assessment in Northern France.

OBJECTIVE: To evaluate health impact of boron in drinking water. METHODS: A regional scale geographical study in Northern France was conducted. Assessment of boron blood levels in a group of 180 healthy individuals and correlation with boron content in drinking water were followed by an assessment of health indicators such as birth rates, mortality rates, and sex ratios in zones of different boron content in drinking water. RESULTS: After necessary adjustments, men living in municipalities with more than 0.30 mg/L of boron in drinking water had elevated but not significant boron blood levels compared with those living in municipalities with boron water levels of less than 0.30 mg/L (159.1 versus 123.0 ng/g; p > 0.05). The standardized birth ratio adjusted for the reference geographic zone and calendar time period was 1.07 and 1.28 in the low and high (>0.3 mg/L) boron content municipalities, respectively. The birth rate in municipalities with high boron content in drinking water was higher than that of the reference geographic zone and of the French general population (p < 10(-4)). The standardized mortality ratio adjusted for the reference geographic zone and calendar time period was 0.94 and 0.92 in the low and high boron content municipalities, respectively. The mortality rate in municipalities with high boron content in drinking water was less than that of the reference geographic zone and of the French general population (p < 10(-3)). No statistical difference was noted in the male-female sex ratios between the different municipality zones (p = 0.45). CONCLUSIONS: The results of this study do not support the idea of a deleterious effect of boron on human health, at the boron water level contents found in this specific region. In fact, there is a tendency toward a beneficial effect with low-dose environmental exposure (less than 1 mg/L of boron) in drinking water.

Nitrate in groundwater: an isotopic multi-tracer approach.

In spite of increasing efforts to reduce nitrogen inputs into groundwater from intensive agriculture, nitrate (NO3) remains one of the major pollutants of drinking-water resources worldwide. Determining the source(s) of NO3 contamination in groundwater is an important first step for improving groundwater quality by emission control, and it is with this aim that we investigated the viability of an isotopic multi-tracer approach (delta15N, delta11B, 87Sr/86Sr), in addition to conventional hydrogeologic analysis, in two small catchments of the Arguenon watershed (Brittany, France). The main anthropogenic sources (fertilizer, sewage effluent, and hog, cattle and poultry manure) were first characterized by their specific B, N and Sr isotope signatures, and compared to those observed in the ground- and surface waters. Chemical and isotopic evidence shows that both denitrification and mixing within the watershed have the effect of buffering NO3 contamination in the groundwater. Coupled delta11B, delta15N and 87Sr/86Sr results indicate that a large part of the NO3 contamination in the Arguenon watershed originates from the spreading of animal manure, with hog manure being a major contributor. Point sources, such as sewage effluents, contribute to the NO3 budget of the two watersheds.

Environmental boron exposure and activity of delta-aminolevulinic acid dehydratase (ALA-D) in a newborn population.

Following boron intake, multiple effects have been observed in animal experiments. However, human data is lacking, and no data is available on the ability of boron to accumulate in fetal tissues. Positive responses in animal species suggest that developmental toxicity may be an area of concern in humans, following exposure to boron. Two hypotheses have seemed to account for the multiple effects described in scientific findings. One hypothesis is that boron is a negative regulator that influences a number of metabolic pathways by competitively inhibiting some key enzyme reactions. The other hypothesis is that boron has a role in ionic membrane transport regulations. To better understand boron potential toxicity, the present study examined the relationship between boron exposure and some key enzymes, well-known for their affinity for mineral elements, such as delta-aminolevulinic acid dehydratase (ALA-D), and two fundamental enzymes having a role in ionic membrane transport regulations (Ca-pump and Na(+)K(+)-ATPase). We investigated the potential effects of an environmental boron exposure on the activity of these enzymes in an urban population of 197 "normal" newborns. Environmental boron exposure was assessed in placental tissue. Because of the well-known inhibiting effect of lead on these enzymes, cord blood and placental lead were also analyzed. After adjustment for potential confounders, including lead, placental boron levels were negatively significantly correlated to ALA-D activity while Ca-pump and Na(+)K(+)-ATPase activities did not seem to be affected by the level of boron exposure. Given boron's ability, as a Lewis acid, to complex with hydroxyl groups, we suggest that such a mechanism would explain the inhibiting effect of boron on ALA-D.