Comparative study of sampling methods and in situ and laboratory analysis for shallow-water submarine hydrothermal systems

A primary aim for sampling of submarine hydrothermal vents is to minimize inclusion of ambient seawater. Here, we compare the results of three different sampling methods (air displacement, two-valve bottle, and syringes) for shallow submarine systems. Mixing of hydrothermal fluid with seawater is unavoidable; however, calculations based on linear mixing models allow estimation of the hydrothermal fluid end-member composition. The results show that sampling with a two-valve bottle and syringes are the best options because they allow collection of samples with a large proportion of hydrothermal fluid. Additionally, we compare the results of in situ and laboratory analyses of the fluid samples, and demonstrate that determination of chemical composition in situ is the best option for some components, as re-equilibration affects some component concentrations (i.e. bicarbonate). Conversely, silica determination in situ usually underestimates the concentration in the fluid, as it does not account for polymeric silica. Other components can be measured either in the field or in the laboratory.     

Variations of Pb in a mine-impacted tropical river,Taxco, Mexico: Use of geochemical,isotopic and statistical tools

The potential environmental threat from Pb in Mexican rivers impacted by historic mining activities was studied using geochemical, isotopic and statistical methods. Lead geochemical fractionation and factor analysis of fractionated and total Pb indicate that anthropogenic sources have contributed significantly to Pb concentrations, while natural sources have contributed only small amounts. The analyses also indicate that two main processes are controlling the total Pb variation throughout the year in both rivers: erosion with discharge processes, and proportional dilution related to differences in grain-size distribution processes. Bio-available Pb in riverbed sediments was greater than 50% in 80% of the sampling stations indicating a high potential environmental risk, according to the risk assessment criteria (RAC). Nevertheless, based on the environmental chemistry of Pb and on multivariate statistical analysis, these criteria did not apply in this particular case. Significant differences (p < 0.05) in total Pb concentrations (from 50 to 5820 mg kg⁻¹) and in the geochemical fractionation were observed as a function of seasonality and location along the river flow path. In the Cacalotenango and Taxco rivers, the highest concentrations of total Pb were found at stations close to tailings during the rainy and post-rainy seasons. The geochemistry of Pb was mainly controlled, during the dry and post-rainy seasons by the organic matter and carbonate content, and in the rainy season by hydrological conditions (e.g., the increase in river flux), hydrological basin erosion, and the suspended solids concentration. Isotopic analyses of the ²¹⁰Pb/²¹⁴Pb ratio showed three processes in the Cacalotenango and Taxco rivers. First, the accumulation of atmospheric excess ²¹⁰Pb, favoured during calmer hydrodynamic conditions in the river basin commonly during dry periods, is recorded by a ²¹⁰Pb/²¹⁴Pb ratio of >1. In the case of the Cacalotenango river, ²¹⁰Pb did show preferential accumulation in sediments. Second, a ²¹⁰Pb/²¹⁴Pb ratio of <1 in some samples might be indicating (a) the presence of eroded material from weathered tailings with similar ²¹⁰Pb depletion (probably by secular disequilibrium caused by weathering or mining processes, which was observed in both rivers), or (b) preferential transport of Pb and sediments during high energy events (e.g., flow increase, as is the case of Taxco river). Third, no significant changes in the ²¹⁰Pb/²¹⁴Pb ratio might be reflecting a situation where mining material is not entering the system, or where hydrodynamic changes throughout the year of equal magnitude allow the system to reach a new equilibrium for the ²¹⁰Pb/²¹⁴Pb ratio. Finally, based on these results it is recommended that inhabitants of the studied area avoid using water from the Cacalotenango river in the rainy and post-rainy seasons, and to take precautions for its use in the dry season, such as allowing suspended material to settle before use, and that they should avoid use of Taxco river water at all times.     

Chemical characteristics of the crater lakes of Popocatetetl, El Chichon, and Nevado de Toluca volcanoes, Mexico

Three crater lakes from Mexican volcanoes were sampled and analyzed at various dates to determine their chemical characteristics. Strong differences were observed in the chemistry among the three lakes: Nevado de Toluca, considered as dormant, El Chichón at a post-eruptive stage, and Popocatépetl at a pre-eruptive stage. Not surprisingly, no influence of volcanic activity was found at the Nevado de Toluca volcano, while the other volcanoes showed a correlation between the changing level of activity and the evolution of chemical trends. Low pHs (<3.0) were measured in the water from the active volcanoes, while a pH of 5.6 was measured at the Nevado de Toluca Sun lake. Changes with time were observed at Popocatépetl and El Chichón. Concentrations of volcanic-gas derived species like Cl⁻, SO₄²⁻ and F⁻ decreased irregularly at El Chichón from 1983 until 1997. Major cations concentrations also diminished at El Chichón. A 100% increase in the SO₄²⁻ content was measured at Popocatépetl between 1985 and 1994. An increase in the Mg/Cl ratio between 1992 (Mg/Cl=0.085) and 1994 (Mg/Cl=0.177) was observed at Popocatépetl, before the disappearance of the crater lake in 1994. It is concluded that chemical analysis of crater lakes may provide a useful additional tool for active-volcano monitoring.     

Origin of arsenic in the groundwater of the Rioverde basin, Mexico

Groundwater in the semiarid Rioverde basin in the northern part of Mexico was investigated with respect to major and minor elements including arsenic, as well as As(III) and As(V). The total arsenic concentrations varied from less than 5 to 50 g/L. The in situ arsenic determination method produced reliable results with deviations from -5.6 to 2.2 g/L compared to laboratory HGAAS. Since arsenic and barium were found to be inversely correlated, it was suspected that precipitation of barium arsenate controlled arsenic solubility. Thermodynamically modeling by means of PHREEQC indicated that BaHAsO₄·H₂O (not BaAsO₄) might be a limiting phase, however only at higher concentrations than those determined in this study. Increased arsenic groundwater concentrations were found with lacustrine sediments and decreased concentrations with fluvial Quaternary sediments. Increased total arsenic concentrations correlate with increased As(III) concentrations in the groundwater of the lacustrine sediments.     

Geochemistry of the volcano-hydrothermal system of El Chichón Volcano, Chiapas, Mexico

 The 1982 eruption of El Chichón volcano ejected more than 1 km³ of anhydrite-bearing trachyandesite pyroclastic material to form a new 1-km-wide and 300-m-deep crater and uncovered the upper 500 m of an active volcano-hydrothermal system. Instead of the weak boiling-point temperature fumaroles of the former lava dome, a vigorously boiling crater spring now discharges  / 20 kg/s of Cl-rich (∼15 000 mg/kg) and sulphur-poor ( / 200 mg/kg of SO₄), almost neutral (pH up to 6.7) water with an isotopic composition close to that of subduction-type magmatic water (δD=–15‰, δ¹⁸O=+6.5‰). This spring, as well as numerous Cl-free boiling springs discharging a mixture of meteoric water with fumarolic condensates, feed the crater lake, which, compared with values in 1983, is now much more diluted (∼3000 mg/kg of Cl vs 24 030 mg/kg), less acidic (pH=2.6 vs 0.56) and contains much lower amounts of S ( / 200 mg/kg of SO₄, vs 3550 mg/kg) with δ³⁴S=0.5–4.2‰ (+17‰ in 1983). Agua Caliente thermal waters, on the southeast slope of the volcano, have an outflow rate of approximately 100 kg/s of 71  °C Na–Ca–Cl water and are five times more concentrated than before the eruption (B. R. Molina, unpublished data). Relative N₂, Ar and He gas concentrations suggest extensional tectonics for the El Chichón volcanic centre. The ³He/⁴He and ⁴He/²⁰Ne ratios in gases from the crater fumaroles (7.3R_a, 2560) and Agua Caliente hot springs (5.3R_a, 44) indicate a strong magmatic contribution. However, relative concentrations of reactive species are typical of equilibrium in a two-phase boiling aquifer. Sulphur and C isotopic data indicate highly reducing conditions within the system, probably associated with the presence of buried vegetation resulting from the 1982 eruption. All Cl-rich waters at El Chichón have a common source. This water has the appearence of a "partially matured" magmatic fluid: condensed magmatic vapour neutralized by interaction with fresh volcaniclastic deposits and depleted in S due to anhydrite precipitation. Shallow ground waters emerging around the volcano from the thick cover of fresh pumice deposits (Red waters) are Ca–SO₄–rich and have a negative oxygen isotopic shift, probably due to ongoing formation of clay at low temperatures. Received: 21 July 1997 / Accepted: 4 December 1997     

Determination of the Concentration of Carbonic Species in Natural Waters: Results from a World‐Wide Proficiency Test

The results of an international interlaboratory proficiency test for the determination of carbonic species are presented. Eight laboratories analysed twelve water samples (four synthetic waters, one lake water, four geothermal waters, one seawater and two petroleum waters) by two methods: (a) individual laboratory analytical procedure and (b) acid–base titration curves in tabular form following a standardised protocol. In case (b), the concentrations of carbonic species were calculated by the organiser using the (1) Hydrologists' method, (2) Geochemists' method and/or (3) initial pH and total alkalinity method. For synthetic waters, the averaged % trueness and precision of measurement of the two methods were (trueness = 7.6, precision = 9.4) and (9.0, 3.4) for total alkalinity, and (6.6, 31.0) and (7.8, 6.1) for carbonic alkalinity, respectively. This indicates that the total alkalinity calculation procedure is in general correct in the individual laboratory method, but the carbonic alkalinity calculation procedure has serious problems. The measurements of total alkalinity for lake and seawaters were in agreement in both the methods; however, the individual laboratory measurement method for geothermal and petroleum waters was conceptually incorrect. Thus, the analytical procedures for the determination of carbonic species were reviewed. To apply the Hydrologists' and/or Geochemists' methods, the location of NaHCO₃EP and H₂CO₃EP is necessary, even for samples with pH lower than that of NaHCO₃EP, and a backward titration curve after complete removal of CO₂ must be performed. The initial pH and total alkalinity method is appropriate where a complete analysis of species that contribute to the alkalinity is known.     

Geochemical processes and mobilization of toxic metals and metalloids in an As-rich base metal waste pile in Zimapán,Central Mexico

The geochemistry and mineralogy of samples collected along depth profiles from an As-rich tailing deposit with abundant calcite was studied to determine the processes that influence the mobility of Fe, Zn, Cu, Ni, Cd, As, Sb, Cr and Tl. In spite of their near neutral pH, almost all of them are acid potential generators. Total concentrations decreased as: Fe > As > Zn > Pb > Cu > Sb > Cd > Cr > Ni > Tl. Soluble contents were lower and followed a slightly different order. Mobility decreased as: Tl > Cd, Zn, Cu, Sb, Ni, As > Fe, Pb > Cr. Higher soluble concentrations of Fe, Cu, Zn, As, Pb, and Ni were found in low-pH samples and of Sb and Tl in near-neutral samples. Sulfide oxidation processes are developing in the tailing’s dam. These processes do not have a trend with depth but occur mainly in acid layers. Near neutral layers formed by primary sulfides and calcite probably correspond to wastes produced from the processing of ore coming mainly from pods within the skarn, and acid layers with abundant secondary minerals from material mined from chimneys and mantos. The presence of calcite influences speciation, neutralizes acid mine drainage (AMD), and decreases the mobility of most toxic metals and metalloids (TMMs). However, a hard-pan layer was not observed in the studied profiles. Retention of TMM within tailings probably occurs through the formation of low solubility metal carbonates and from elevation of pH that promotes Fe hydroxides precipitation that may retain As, Sb and metals. Calcite occurrence promotes As, Cd, Cu, Fe, Zn, Pb, Cd and Cr retention, does not play a role on Tl and Ni mobilization, and increases Sb release.     

The origin of groundwater arsenic and fluorine in a volcanic sedimentary basin in central Mexico: a hydrochemistry hypothesis

A groundwater sampling campaign was carried out in the summer of 2013 in a low-temperature geothermal system located in Juventino Rosas (JR) municipality, Guanajuato State, Mexico. This groundwater presents high concentrations of As and F^? and high Rn counts, mainly in wells with relatively higher temperature. The chemistry of major elements was interpreted with different methods, like Piper and D’Amore diagrams. These diagrams allowed for classification of four groundwater types located in three hydrogeological environments. The aquifers are hosted mainly in alluvial-lacustrine sediments and volcanic rocks in interaction with fault and fracture systems. The subsidence, faults and fractures observed in the study area can act as preferential channels for recharge and also for the transport of deep fluids to the surface, especially in the basin plain. The formation of a piezometric dome and the observed hydrochemical behavior of groundwater suggest a possible origin of the As and F^?. Geochemical processes occurring during water–rock interaction are related to high concentrations of As and F^?. High temperatures and alteration processes (like rock weathering) induce dissolution of As and F^?-bearing minerals, increasing the content of these elements in groundwater.