Applied Geochemistry (v.65, #C)

Linking groundwater quality to residence times and regional geology in the St. Lawrence Lowlands, southern Quebec, Canada by Marion Saby; Marie Larocque; Daniele L. Pinti; Florent Barbecot; Yuji Sano; Maria Clara Castro (1-13).
The assessment of groundwater quality in shallow aquifers is of high societal relevance given that large populations depend directly on these water resources. The purpose of this study was to establish links between groundwater quality, groundwater residence times, and regional geology in the St. Lawrence Lowlands fractured bedrock aquifer. The study focuses on a 4500 km2 watershed located in the St. Lawrence Lowlands of the province of Quebec in eastern Canada. A total of 150 wells were sampled for major, minor, and trace ions. Tritium (3H) and its daughter element, 3He, as well as radiocarbon activity (A14C) were measured in a subset of wells to estimate groundwater residence times. Results show that groundwater evolves from a Ca–HCO3 water type in recharge zones (i.e., the Appalachian piedmont) to a Na–HCO3 water type downgradient, toward the St. Lawrence River. Locally, barium (Ba), fluoride (F), iron (Fe), and manganese (Mn) concentrations reach 90, 2, 18, and 5.9 mg/L respectively, all exceeding their respective Canadian drinking water limits of 1, 1.5, 0.3, and 0.05 mg/L. Release of these elements into groundwater is mainly controlled by the groundwater redox state and pH conditions, as well as by the geology and the duration of rock–water interactions. This evolution is accompanied by increasing 3H/3He ages, from 4.78 ± 0.44 years upgradient to more than 60 years downgradient. Discrepancies between calculated 3H/3He and 14C water ages (the latter ranging from 280 ± 56 to 17,050 ± 3410 years) suggest mixing between modern water and paleo-groundwater infiltrated through subglacial recharge when the Laurentide Ice Sheet covered the study area, and during the following deglaciation period. A linear relationship between 3H activity and corrected 14C versus Mg/Ca and Ba support a direct link between water residence time and the chemical evolution of these waters. The Ba, F, Fe, and Mn concentrations in groundwater originate from Paleozoic rocks from both the St. Lawrence Platform and the Appalachian Mountains. These elements have been brought to the surface by rising hydrothermal fluids along regional faults, and trapped in sediment during their deposition and diagenesis due to reactions with highly sulfurous and organic matter-rich water. Large-scale flow of meltwater during subglacial recharge and during the subsequent retreat of the Laurentide Ice Sheet might have contributed to the leaching of these deposits and their enrichment in the present aquifers. This study brings a new and original understanding of the St. Lawrence Lowlands groundwater system within the context of its geological evolution.
Keywords: Groundwater quality; Groundwater residence times; Regional geology; St. Lawrence Lowlands; Quebec (Canada);

Iodine-129 chronological study of brines from an Ordovician paleokarst reservoir in the Lunnan oilfield, Tarim Basin by Jian Chen; Dayong Liu; Ping'an Peng; Chen Ning; Hou Xiaolin; Zhang Baoshou; Xiao Zhongyao (14-21).
Previous studies have shown that brines in an Ordovician paleokarst reservoir of the Lunnan oilfield in the Tarim Basin, China, are the product of mixing of paleo-evaporated seawater in the east with paleometeoric waters in the west. In order to put time constraints on the brine and related hydrocarbons in this field, 10 brine samples were collected, for which the iodine concentrations and 129I/I ratios were measured and discussed. The iodine concentration (3.70–31.2 mg/L) and the 129I/I ratio (189–897 × 10−15) show that the iodine in the paleoseawater and meteoric water (MW) had different origins and 129I characteristics. The paleoseawater has a high iodine content (∼31 mg/L), indicating that iodine was introduced into the reservoir along with thermally generated hydrocarbons, possibly in the Cretaceous, from the Caohu Sag in the eastern area. Based on consideration of all possible origins of iodine and 129I in the brines, it is suggested that the meteoric water maintained its initial iodine content (0.01 mg/L) and 129I/I ratio (1500 × 10−15), whereas the iodine-enriched paloseawater (IPSW) exhibited a secular 129I equilibrium (Nsq = 39 atom/μL) as a result of fissiogenic 129I input in the reservoir over a long period of time. The model of brine evolution developed on that basis confirmed that meteoric water entered the reservoir in the Miocene at about 10 Ma, and partially mixed with the iodine-enriched paleoseawater. The movement of meteoric water was facilitated by faults created during the Himalayan orogeny, then became more dense after dissolving Paleogene halite and infiltrated into the reservoir at high pressure. The iodine and 129I concentration in the brine contains information about the path and history of the fluid in the reservoir. This may be useful in oil exploration, since the movement of water was, to some extent, related to hydrocarbon migration.
Keywords: Iodine; Iodine 129; Oilfield water; Tarim basin;

Geochemistry of organic-rich river waters in Amazonia: Insights on weathering processes of intertropical cratonic terrain by Adriana Maria Coimbra Horbe; Anderson da Silva Lages; Jean-Sébastien Moquet; Roberto Ventura Santos; Patrick Seyler; Gerard Cochonneau (22-35).
In this study, eight organic-rich rivers that flow through the Brazilian craton in the southwestern Amazon rainforest are investigated. This investigation is the first of its type in this area and focuses on the effects of lithology, long-term weathering, thick soils, forest cover and hydrological period on the dissolved load compositions in rivers draining cratonic terrain. The major dissolved ion concentrations, alkalinity (TAlk), SiO2, trace element concentrations, and Sr isotope contents in the water were determined between April 2009 and January 2010. In addition, the isotopic values of oxygen and hydrogen were determined between 2011 and 2013. Overall, the river water is highly dilute and dominated by the major dissolved elements TAlk, SiO2 and K+ and the major dissolved trace elements Al, Fe, Ba, Mn, P, Zn and Sr, which exhibit large temporal and spatial variability and are closely correlated with the silicatic bedrock and hydrology. Additionally, rainwater and recycled water vapor and the size of the basin contribute to the geochemistry of the waters. The total weathering flux estimated from our results is 2–4 t km−2.yr−1, which is one of the lowest fluxes in the world. The CO2 consumption rate is approximately 21–61 103 mol km−2 yr−1, which is higher than expected given the stability of the felsic to basic igneous and metamorphic to siliciclastic basement rocks and the thick tropical soil cover. Thus, weathering of the cratonic terrain under intertropical humid conditions is still an important consumer of CO2.
Keywords: Trace elements; Sr isotopes; O and D isotopes; Weathering rates; CO2 consumption rate;

Major and trace elements, noble gases, and stable (δD, δ18O) and cosmogenic (3H, 14C) isotopes were measured from geothermal fluids in two adjacent geothermal areas in NW-Mexico, Las Tres Vírgenes (LTV) and Cerro Prieto (CP). The goal is to trace the origin of reservoir fluids and to place paleoclimate and structural-volcanic constraints in the region. Measured 3He/4He (R) ratios normalized to the atmospheric value (Ra = 1.386 × 10−6) vary between 2.73 and 4.77 and are compatible with mixing between a mantle component varying between 42 and 77% of mantle helium and a crustal, radiogenic He component with contributions varying between 23% and 58%. Apparent U–Th/4He ages for CP fluids (0.7–7 Ma) suggest the presence of a sustained 4He flux from a granitic basement or from mixing with connate brines, deposited during the Colorado River delta formation (1.5–3 Ma). Radiogenic in situ 4He production age modeling at LTV, combined with the presence of radiogenic carbon (1.89 ± 0.11 pmC – 35.61 ± 0.28 pmC) and the absence of tritium strongly suggest the Quaternary infiltration of meteoric water into the LTV geothermal reservoir, ranging between 4 and 31 ka BP. The present geochemical heterogeneity of LTV fluids can be reconstructed by mixing Late Pleistocene – Early Holocene meteoric water (58–75%) with a fossil seawater component (25–42%), as evidenced by Br/Cl and stable isotope trends. CP geothermal water is composed of infiltrated Colorado River water with a minor impact by halite dissolution, whereas a vapor-dominated sample is composed of Colorado River water and vapor from deeper levels. δD values for the LTV meteoric end-member, which are 20‰–44‰ depleted with respect to present-day precipitation, as well as calculated annual paleotemperatures 6.9–13.6 °C lower than present average temperatures in Baja California point to the presence of humid and cooler climatic conditions in the Baja California peninsula during the final stage of the Last Glacial Pluvial period. Quaternary recharge of the LTV geothermal reservoir is related to elevated precipitation rates during cooler-humid climate intervals in the Late Pleistocene and Early Holocene. The probable replacement of connate water or pore fluids by infiltrating surface water might have been triggered by enhanced fracture and fault permeability through contemporaneous tectonic–volcanic activity in the Las Tres Vírgenes region. Fast hydrothermal alteration processes caused a secondary, positive δ18O-shift from 4‰ to 6‰ for LTV and from 2‰ to 4‰ for CP geothermal fluids since the Late Glacial infiltration.
Keywords: Las Tres Vírgenes; Cerro Prieto; Geothermal reservoir; Fluid provenance; Residence time; Noble gases; Environmental isotopes; Paleotemperature; Co-genetic volcanic activity;

Two experimental waste-rock piles (test piles), each 15 m in height × 60 m × 50 m, were constructed at the Diavik diamond mine in Northern Canada to study the behavior of low-sulfide content waste rock, with a similarly low acid-neutralization potential, in a continuous permafrost region. One test pile with an average of 0.035 wt.% S (<50 mm fraction; referred to as Type I) and a second test pile with an average of 0.053 wt.% S (<50 mm fraction; referred to as Type III) were constructed in 2006. The average carbon content in the <50 mm fraction of waste rock in the Type I test pile was 0.031 wt.% as C and in the Type III test pile was 0.030 wt.% as C. The NP:AP ratio, based on the arithmetic mean of particle-size weighted NP and AP values, for the Type I test pile was 12.2, suggesting this test pile was non-acid generating and for the Type III test pile was 2.2, suggesting an uncertain acid-generating potential. The Type I test pile maintained near-neutral pH for the 4-year duration of the study. Sulfate and dissolved metal concentrations were low, with the exception of Ni, Zn, Cd, and Co in the fourth year following construction. The pore water in the Type III test pile contained higher concentrations of SO4 2− and dissolved metals, with a decrease in pH to <4.7 and an annual depletion of alkalinity. Maximum concentrations of dissolved metals (20 mg L−1 Ni, 2.3 mg L−1 Cu, 3.7 mg L−1 Zn, 35 μg L 1 Cd, and 3.8 mg L−1 Co) corresponded to decreases in flow rate, which were observed at the end of each field season when the contribution of the total outflow from the central portion of the test pile was greatest. Bacteria were present each year in spite of annual freeze/thaw cycles. The microbial community within the Type I test pile included a population of neutrophilic S-oxidizing bacteria. Each year, changes in the water quality of the Type III test-pile effluent were accompanied by changes in the microbial populations. Populations of acidophilic S-oxidizing bacteria and Fe-oxidizing bacteria became more abundant as the pH decreased and internal test pile temperatures increased. Irrespective of the cold-climate conditions and low S content of the waste rock, the geochemical and microbiological results of this study are consistent with other acid mine drainage studies; indicating that a series of mineral dissolution–precipitation reactions controls pH and metal mobility, and transport is controlled by matrix-dominated flow and internal temperatures.
Keywords: Mine drainage; Arctic; Waste rock; Low-sulfide content;

Reductive weathering of black shale and release of barium during hydraulic fracturing by Devon Renock; Joshua D. Landis; Mukul Sharma (73-86).
Hydraulic fracturing is an important technological advance in the extraction of natural gas and petroleum from black shales, but water injected into shale formations in the fracturing process returns with extraordinarily high total-dissolved-solids (TDS) and high concentrations of barium, Ba. It is generally assumed that high TDS comes from the mixing of surface water (injected fluid) with Na–Ca–Cl formation brines containing elevated Ba, but the mechanisms by which such mixing might occur are disputed. Here we show that Ba in water co-produced with gas could originate from water-rock reactions, with Ba levels observed in produced waters reached on a time scale relevant to hydraulic fracturing operations. We examined samples from three drill cores from the Marcellus Shale in Pennsylvania and New York to determine the possible water-rock reactions that release barium during hydraulic fracturing. Two samples, one containing microcrystalline barite (BaSO4) and one without barite, contain elevated concentrations of Ba relative to the crustal average for shale rocks. A third sample is slightly depleted in Ba relative to the crustal average. Micro-XRF measurements and SEM/EDS analysis combined with chemical sequential extraction methods reveal that a majority of the Ba in all samples (55–77 wt.%) is present in clays and can only be leached from the rock by dissolution in hydrofluoric acid. Thus, a majority of barium in our samples is relatively inaccessible to leaching under hydraulic fracturing conditions. However, the balance of Ba in the rocks is contained in phases that are potentially leachable during hydraulic fracturing (e.g., soluble salts, exchangeable sites on clays, carbonates, barite, organics).We next studied how shale reacts with water at elevated temperatures (80 °C), low Eh (−100 to −200 mV), and a range of ionic strengths (IS = 0.85–6.4) that emulate conditions prevalent at depth during hydraulic fracturing. Our experimental results indicate that the amount of Ba released from the bulk rock has a positive correlation with the ionic strength of the reacting fluid. Between 5 and 25% of the total Ba in the rock can be leached from shale under ionic strength conditions and leachate compositions typical of produced waters over a contact time of just 7 days. We suggest that reductive weathering of black shale occurs during hydraulic fracturing due to: 1) Ba2+ in clays exchanging with Na+ and Ca2+ ions that are present in high concentrations in produced water, and 2) increased solubility and dissolution kinetics of barite under high ionic strength conditions. At the low Eh conditions prevalent during hydraulic fracturing the sulfate deficient water allows Ba to be dissolved into the produced water. Based on Ba yields determined from laboratory leaching experiments of Marcellus Shale and a reasonable estimate of the water/rock mass ratio during hydraulic fracturing, we suggest that all of the Ba in produced water can be reconciled with leaching directly from the fractured rock.
Keywords: Barium; Barite; Hydraulic fracturing; Marcellus Shale;

Occurrence and mobility of major and trace elements in groundwater from pristine volcanic aquifers in Jeju Island, Korea by Dong-Chan Koh; Gi-Tak Chae; Jong-Sik Ryu; Seung-Gu Lee; Kyung-Seok Ko (87-102).
Major and trace elements in groundwater from basaltic aquifers in pristine conditions were investigated in a volcanic island to evaluate sources, sinks, and mobility of elements over a wide range of mineralization conditions with total dissolved solids from 50 mg/L to 3400 mg/L. Groundwater was highly undersaturated with respect to primary silicate minerals, indicating that dissolution of basaltic rocks may continue under conditions with precipitation of calcite and secondary silicates. Evolution of B/Cl ratio in groundwater from marine aerosols to basaltic rocks showed that the ratio could be used as a conservative tracer for interactions between water and basaltic rocks. Relative mobility (RM) of elements calculated using the concentrations of elements in the local basaltic rocks and those in groundwater showed that mobility decreased in the order of B > Rb > Na > K > Mg > Ca > Mo > V > Si > Sr > Sc > P > U > Zn > Pb > Cr > Cu > Ba > Ni > Ti > (Mn, Al, Fe, Co, Th) indicating that oxyanion-forming elements and alkali metals had the highest mobility. Compared to average RM, V had decreased mobility, and Fe and Mn had increased mobility in anoxic groundwater while V, Mo, and U had higher mobility in oxic-alkaline water. The sources of V, Cr, Cu, and Zn in rocks were estimated using the partition coefficients between minerals and basaltic melt, and the disparity between sources and mobility indicated that sinks are more important for controlling the concentrations of these elements in groundwater than the contents in the rocks. Principal component analysis (PCA) of hydrogeochemical parameters in groundwater produced three principal components (PC) which represent dissolution of basaltic rocks without significant attenuation of released solutes, higher degree of water–rock interactions resulting in oxic-alkaline conditions, and attenuation of Zn and Cu in higher pH, respectively. Spatial distribution of PCs revealed that groundwater with elevated concentrations of mobile elements was concentrated in the southwestern area and that concentrations of V and Cr were more scattered, which is likely to be controlled by pH and redox states of groundwater as well as degree of water–rock interactions.
Keywords: Weathering; Hydrogeochemical evolution; Redox condition; Multivariate statistical analysis; Oxyanion-forming trace elements;