Arsenic in volcanic geothermal fluids of Latin America.

Numerous volcanoes, hot springs, fumaroles, and geothermal wells occur in the Pacific region of Latin America. These systems are characterized by high As concentrations and other typical geothermal elements such as Li and B. This paper presents a review of the available data on As concentrations in geothermal systems and their surficial discharges and As data on volcanic gases of Latin America. Data for geothermal systems in Mexico, Guatemala, Honduras, El Salvador, Nicaragua, Costa Rica, Ecuador, Bolivia, and Chile are presented. Two sources of As can be recognized in the investigated sites: Arsenic partitioned into volcanic gases and emitted in plumes and fumaroles, and arsenic in rocks of volcanic edifices that are leached by groundwaters enriched in volcanic gases. Water containing the most elevated concentrations of As are mature Na-Cl fluids with relatively low sulfate content and As concentrations reaching up to 73.6 mg L⁻¹ (Los Humeros geothermal field in Mexico), but more commonly ranging from a few mg L⁻¹ to tens of mg L⁻¹. Fluids derived from Na-Cl enriched waters formed through evaporation and condensation at shallower depths have As levels of only a few µg L⁻¹. Mixing of Na-Cl waters with shallower meteoric waters results in low to intermediate As concentrations (up to a few mg L⁻¹). After the waters are discharged at the ground surface, As(III) oxidizes to As(V) and attenuation of As concentration can occur due to sorption and co-precipitation processes with iron minerals and organic matter present in sediments. Understanding the mechanisms of As enrichment in geothermal waters and their fate upon mixing with shallower groundwater and surface waters is important for the protection of water resources in Latin America.

Mechanisms of arsenic enrichment in geothermal and petroleum reservoirs fluids in Mexico.

The lack of chemical similarity between thermal fluids in geothermal and petroleum reservoirs in Mexico indicates a distinct origin for arsenic in both types of reservoirs. Deep fluids from geothermal reservoirs along the Transmexican Volcanic Belt (TMVB) are characterized by elevated arsenic concentrations, within a range between 1 and 100 mg L(-1) at a depth from 600 to 3000 m b.s.l. Based on hierarchical cluster analysis (HCA), arsenic is linked to typical geothermal species like lithium, silica, and boron. The lack of correlation between arsenic and salinity reflects the importance of secondary water-rock interaction processes. The predominance of arsenic compared to Fe- and Cu-concentrations, and the occurrence of secondary minerals (sulfides and clay minerals) in temperature-dependent hydrothermal zones, supports this hypothesis. Neither magmatic fluids input, nor As mineralization is a prerequisite for As enrichment in Mexican geothermal fluids. In contrast, petroleum reservoir waters from sedimentary basins in SE-Mexico show maximum As concentrations of 2 mg L(-1), at depths from 2900 to 6100 m b.s.l. The linear chloride-arsenic correlation indicates that evaporated seawater represents the major source for aqueous arsenic in oil reservoirs, and only minor arsenic proportions are derived from interaction with carbonate host rock. Speciation modeling suggests the lack of arsenic solubility control in both geothermal and petroleum reservoirs, but precipitation/co-precipitation of As with secondary sulfides could occur in petroleum reservoirs with high iron concentrations. Geothermal fluids from magmatic-type reservoirs (Los Azufres and Los Humeros at the TMVB and Las Tres Vírgenes with a granodioritic basement) show relative constant arsenic concentrations through varying temperature conditions, which indicates that temperatures above 230-250 °C provide optimal and stable conditions for arsenic mobility. In contrast, temperature conditions for sedimentary-type reservoirs are irrelevant for water-rock interaction processes, as suggested by low arsenic aqueous concentration for both Cerro Prieto geothermal fluids (high temperature - sedimentary type) and oil field formation water (low temperature - sedimentary type).

Legal aspects and technical alternatives for the treatment of reservoir brines at the Activo Luna oilfield, Mexico.

Deep formation water, extracted as an undesired byproduct from on-shore production wells at the Activo Luna oilfield and processed in adjacent oil fields, are highly enriched in salt minerals, especially in sodium chloride (NaCl) (262 000 mg/L), but also in metals and nonmetals, such as strontium (Sr) (2068 mg/L), bromine (Br) (2034 mg/L), boron (B) (396 mg/ L), iodine (I) (43.4 mg/L), selenium (Se) (3.74 mg/L), and arsenic (As) (0.55 mg/L). Direct reinjection of the brine underground is not possible because of elevated pressure conditions within the petroleum reservoir. The disposal into near shore areas of the Gulf of Mexico without treatment must be rejected because of a) elevated concentrations of some toxic elements, such as B, silver (Ag), thallium (Tl), Se and cadmium (Cd), which exceed permissible limits of environmental legislation for surface discharge (Official Mexican norms NOM-001-ECOL-1998 and CE-CCA-001/89), and b) differences in density that could cause the descent of hypersaline fluid to the ocean floor, potentially affecting the diversity and survival of the benthic ecosystem. Conventional treatment techniques, such as microfiltration or reverse osmosis, are not suitable for the Activo Luna brines because of their extreme mineralization, which will cause pressure conditions exceeding 200 bars across the membrane. As an alternative process, the evaporation of the entire brine volume of approximately 200 m3/day by solar ponds or industrial crystallization plants is suggested. The residual precipitated residuals are composed mainly of chlorine (Cl) (9460 tons/year), sodium (Na) (4230 tons/ year), calcium (Ca) (1028 tons/year), potassium (K) (207 tons/year), and magnesium (Mg) (65.8 tons/year). As an alternative to its disposal on a dumpsite, some special minerals (especially NaCl, Mg, Sr, and Br) could be recovered for its economic value.