No abstract

Mud volcanoes represent the largest expression of natural methane release into the atmosphere; however, the gas flux has never been investigated in detail. Methane output from vents and diffuse soil degassing is herewith reported for the first time. Measurements were carried out at 5 mud volcano fields around Sicily (Italy). Each mud volcano is characterized by tens of vents and bubbling pools. In the quiescent phase, methane emission from single vents ranges between 0.01 and 6.8 kg/day. Diffuse soil leakage around the vents is in the order of 102–104 mg m−2 d−1. An exceptional flux of 106 mg m−2 d−1 was recorded close to an everlasting fire. Soil CH4 flux is positive even at large distances from the mud volcano fields suggesting a diffuse microseepage over wider areas. A total of at least 400 tons CH4 per year can be estimated over the area investigated alone (∼1.5 km2).

International audienceThe geochemistry of groundwaters from the Pannonian Basin (Hungary and Romania) were analysed to elucidate the general geochemistry and processes controlling elevated levels of arsenic. Using cluster analysis 4 main groups were identified. Group 4, influenced by geothermal and saline inputs (Na-HCO3 to Na-Cl type, high Li, Si, NH4 and B, low δ7Li values) with low As levels (mean 33.1 μg/L, range <0.5 to 240 μg/L). Group 3 waters, sampling only dug wells with geochemistry influenced by rain water and surface contamination (Ca-Mg-HCO3 type, elevated K, NO3, S(tot) and Cl) and also with low As (mean 1 μg/L, range <0.5 to 2.1 μg/L). Groups 1 and 2 represented general reducing groundwaters of the area (Mg/Ca-HCO3 to Na-HCO3). Despite such similarities, both groups had different redox characteristics, (i) group 1 indicative of waters dominated by methanogenesis (high CH4, low to absent S(tot)), (ii) group 2 indicative of waters dominated by SO4-reduction (low CH4, moderate S(tot)), and (iii) both group 1 and 2 having similar ranges of Fe concentrations indicating that Fe-reduction is occurring equally in both groups. Arsenic levels in group 1 (methanogenesis) were high, ranging from 23.4 to 208 μg/L (mean 123 μg/L) and predominantly as As(III). Levels in group 2 (SO4-reducing) were much lower, ranging from <0.5 to 58 μg/L (mean 11.5 μg/L), again predominantly as As(III). Typically low levels of As in group 4 waters (geothermal), combined with positive correlations between δ7Li and As(tot) indicate that elevated As is not from an external input, but is released due to an in-aquifer process. Geochemical reasoning implies As mobilisation is controlled by redox-processes, most likely reductive dissolution of As bearing Fe-oxides, known to occur in sediments from the area. More important however is an overlying retention mechanism determined by the presence or absence of SO4.. Ongoing SO4-reduction will release S2-, removing As from solution either by the formation of Assulphides, or from sorption onto Fe-sulphide phases (group 2). In the group dominated by methanogenesis (group 1), any As released by reductive dissolution is not removed from solution and can rise to the high levels observed. Levels of organic carbon are thought to be the ultimate control on the redox conditions in these 2 groups. High levels of organic carbon (as found in group 1) would quickly exhaust any SO4 present in the waters, driving the system to methanogenesis and subsequent high levels of As. Group 2 has much lower concentrations and so SO4 is not exhausted. Therefore, As levels in waters of the Pannonian Basin are controlled not by release but by retention mechanisms, ultimately controlled by levels of TOC and SO4 in the waters

Information about heavy metal concentrations in food products and their dietary intake are essential for assessing the health risk of local inhabitants. The main purposes of the present study were (1) to investigate the concentrations of Zn, Cu, Pb, and Cd in several vegetables and fruits cultivated in Baia Mare mining area (Romania); (2) to assess the human health risk associated with the ingestion of contaminated vegetables and fruits by calculating the daily intake rate (DIR) and the target hazard quotient (THQ); and (3) to establish some recommendations on human diet in order to assure an improvement in food safety. The concentration order of heavy metals in the analyzed vegetable and fruit samples was Zn > Cu > Pb > Cd. The results showed the heavy metals are more likely to accumulate in vegetables (10.8-630.6 mg/kg dw for Zn, 1.4-196.6 mg/kg dw for Cu, 0.2-155.7 mg/kg dw for Pb, and 0.03-6.61 mg/kg dw for Cd) than in fruits (4.9-55.9 mg/kg dw for Zn, 1.9-24.7 mg/kg dw for Cu, 0.04-8.82 mg/kg dw for Pb, and 0.01-0.81 mg/kg dw for Cd). Parsley, kohlrabi, and lettuce proved to be high heavy metal accumulators. By calculating DIR and THQ, the data indicated that consumption of parsley, kohlrabi, and lettuce from the area on a regular basis may pose high potential health risks to local inhabitants, especially in the area located close to non-ferrous metallurgical plants (Romplumb SA and Cuprom SA) and close to Tăuții de Sus tailings ponds. The DIR for Zn (85.3-231.6 μg/day kg body weight) and Cu (25.0-44.6 μg/day kg body weight) were higher in rural areas, while for Pb (0.6-3.1 μg/day kg body weight) and Cd (0.22-0.82 μg/day kg body weight), the DIR were higher in urban areas, close to the non-ferrous metallurgical plants SC Romplumb SA and SC Cuprom SA. The THQ for Zn, Cu, Pb, and Cd was higher than 5 for <1, <1, 12, and 6% of samples which indicates that those consumers may experience major health risks.

Gas flux measurements have for the first time been taken from vents and soil of eastern Romania mud volcanoes, the largest geological structures in Europe releasing methane into the atmosphere. In the quiescent phase, the methane emission from single vents is up to 28 t yr−1. Diffuse soil microseepage is of the order of 102−105 mg m−2 day−1. A total output of at least 1200 tonnes of CH4 per year can be conservatively estimated over the area investigated alone (∼ 2.3 km2). Helium fluxes are up to five orders of magnitude higher than the average flux in a stable continental area, pointing to a close link between mud volcanoes and crustal degassing through faults crossing the deep hydrocarbon reservoirs. These data represent a key contribution towards refining global CH4‐emission estimates, which indicate mud volcanoes as a significant and unavoidable source of greenhouse gases for the atmosphere.