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In 2016, temperature recorders were recovered, temperatures were measured, and fluid samples were collected from Vent 1, a high temperature (338°C) hydrothermal discharge site on the southern Cleft Segment of the Juan de Fuca Ridge. Coupled with previous sampling efforts, this collection represents a 32-year record of discharge from a single chimney structure, the longest record to date. Remarkably, the fluid has remained brine-dominated for more than three decades. This brine formed during phase separation and segregation prior to initial observations in 1984. Although the chloride concentration of the discharging fluid has decreased with time, the fluid temperature has remained nearly constant for at least 3.3 years and probably for 15 or even 22 years. Compositions of the discharging fluids are consistent with inputs from a deep-sourced brine, which was last equilibrated at >400°C at a depth consistent with the base of the sheeted dikes and the brittle-ductile transition. This brine mixed (diffusion or dispersion) with a likely non-phase-separated, hydrothermal fluid prior to discharge. A survey of hydrothermal endmember fluids with chlorinities in excess of 700 mmol/kg shows, with the exception of Fe, a single trend between major ion concentrations and chlorinity even though data are from a range of crustal compositions, spreading rates, and water and magma depths. Calculated deep-sourced brines from hydrothermal fluid data are similar to data based on fluid inclusions and estimates of brine assimilation in magmas. A better understanding of brines is required given their potential duration of discharge and capacity for mobilizing metals.

The northernmost segment of the Gorda mid-ocean ridge is the site of a small-volume eruption in 1996 and the persistent off-axis Sea Cliff hydrothermal vent field. To better understand the geologic setting and formation of these features, 1-m resolution bathymetric mapping using autonomous underwater vehicles was completed in 2016. The mapped region covers 35 km2 and 15.6 km of the volcanic axis from south of the 1996 lava flows, and a cross section for ∼4.5 km perpendicular to the axis, that extends beyond the Sea Cliff hydrothermal vent field. A proposed 1996 flow ∼7 km south of previously mapped flows is an artifact from a poor pre-eruption survey. The 1996 flows consist of three discrete steep hummocky mounds of pillows and syneruptive talus. The Sea Cliff hydrothermal field is located a few km north of the narrowest, shallowest section of the ridge segment, 2.6 km east of the center of the neovolcanic zone, and ∼370 m above the average depth of the axial graben on the largest offset ridge-parallel fault. No evidence supports the prior hypothesis that the site is located where two fault systems intersect. The axial graben is asymmetrical with larger fault offsets on the east side. The ridge axis below the hydrothermal field and to the south toward the 1996 flows is constructed dominantly of hummocky flows of pillow basalt, many unusually steep-sided, with syneruptive talus at the base of their steep slopes. Three channelized flows ponded between steep hummocky flows, and then partially drained. Some low-eruption-rate hummocky flows and high-eruption-rate channelized flows have nearly identical compositions, supporting the idea that eruption rates on mid-ocean ridges vary because of different dike widths. Four volcanic structures with volumes between 0.18 and 0.25 km3 occur in the axial graben south of the 1996 flows. Two are flat-topped cones, another is a 1.5-km diameter inflated hummocky flow with 7 pit craters that demonstrate that the flow had a molten interior during growth. The fourth voluminous structure is a steep ridge with abundant syneruptive talus on its lower slopes. The North Gorda segment is an end-member, structurally and volcanically, compared with other Pacific intermediate-rate spreading ridges.

The aim of the Iceland Deep Drilling Project is to drill into supercritical geothermal systems and examine their economic potential. The exploratory well IDDP-2 was drilled in the Reykjanes geothermal field in SW Iceland, on the landward extension of the Mid-Atlantic Ridge. The Reykjanes geothermal field produces from a

Hydrothermal processes that lead to REE fractionation and redistribution are important for understanding water-rock interactions in geothermal energy resources and mineral deposits, and for determining how submarine hydrothermal activity affects the composition of oceanic crust. Much previous work on REE transport and deposition has focused on submarine hydrothermal vents. We report REE concentrations in boiled fluids sampled from five subaerial, basalt-hosted geothermal fields, and explore controls on aqueous REE concentrations by ligand complexation and mineral supersaturation. Samples that boiled at pressures between 0.8 and 2.83 MPa were obtained from the Reykjanes, Svartsengi, Hellisheidi, and Nesjavellir geothermal systems in Iceland, and the Puna geothermal system in Hawaii. For comparison, we also report REE concentrations in hydrothermal fluids from the sediment hosted submarine Middle Valley hydrothermal system, which boiled at >250 MPa. The pH(25°C) values of the sampled subaerial geothermal fluids range from 3.94 to 6.77, and Cl concentrations range from near seawater (502 mmol/kg) to dilute (1.9 mmol/kg). La, Ce and Eu are the only REE present at levels above 5 picomole/kg (pmol/kg) in the boiled geothermal fluids; and there are notable CI chondrite normalized La and Eu anomalies in the saline fluids. REE concentrations in Middle Valley hydrothermal fluids fall within the typical range reported for submarine hydrothermal fluids and have around two orders of magnitude higher REE than the boiled subaerial geothermal fluids. Bulk samples of precipitates in pipes from the Reykjanes geothermal system have detectable REE, confirming that downhole fluids have lost REE during boiling and production of fluids for geothermal energy. Isenthalpic boiling models show that the proportions of La and Eu chloride complexes increase relative to other aqueous species as boiling progresses, attenuating the incorporation of La and Eu into precipitated well scale solids. Fluorapatite is calculated to precipitate on boiling of low pH and saline fluids and calcite is calculated to precipitate from dilute and near-neutral pH fluids, and these minerals likely sequester REE in boiled subaerial fluids. Submarine hydrothermal fluids are constrained to boiling at higher temperatures than subaerial geothermal fluids owing to pressure from overlying cold seawater, therefore secondary minerals and solids that incorporate REE are not extensively precipitated and REE concentrations in the fluids are higher.

Hydrothermal vent fields located in the gap between known sites in Guaymas Basin and 21°N on the East Pacific Rise were discovered on the Alarcón Rise and in southern Pescadero Basin. The Alarcón Rise spreading segment was mapped at 1-m resolution by an autonomous underwater vehicle. Individual chimneys were identified using the bathymetric data. Vent fields were interpreted as active from temperature anomalies in water column data and observed and sampled during remotely operated vehicle dives. The Ja Sít, Pericú, and Meyibó active fields are near the eruptive fissure of an extensive young lava flow. Vent fluids up to 360 °C from Meyibó have compositions similar to northern East Pacific Rise vents. The Tzab-ek field is 850 m west of the volcanic axis, and active chimneys rise up to 33 m above a broad sulfide mound. The inactive field is 10 km north-northeast along the rift axis, and most sulfide chimneys are enriched in Zn and associated elements that are transported at lower temperature compared to the more Cu-rich active fields. In southern Pescadero Basin, the Auka field is on the margin of a sediment-filled graben at 3,670-m depth. Discharging fluids are clear, contain hydrocarbons, and have neutral pH, elevated salinity, and temperatures up to 291 °C. They have deposited massive mounds of calcite with minor sulfide. The fluids are compositionally similar to those in Guaymas Basin, produced by high-temperature basalt-seawater interaction followed by reaction with sediment. The paucity of sulfide minerals suggests subsurface deposition of metals.

Characterizing the geothermal system at Surprise Valley (SV), northeastern California, is important for determining the sustainability of the energy resource, and mitigating hazards associated with hydrothermal eruptions that last occurred in 1951. Previous geochemical studies of the area attempted to reconcile different hot spring compositions on the western and eastern sides of the valley using scenarios of dilution, equilibration at low temperatures, surface evaporation, and differences in rock type along flow paths. These models were primarily supported using classical geothermometry methods, and generally assumed that fluids in the Lake City mud volcano area on the western side of the valley best reflect the composition of a deep geothermal fluid. In this contribution, we address controls on hot spring compositions using a different suite of geochemical tools, including optimized multicomponent geochemistry (GeoT) models, hot spring fluid major and trace element measurements, mineralogical observations, and stable isotope measurements of hot spring fluids and precipitated carbonates. We synthesize the results into a conceptual geochemical model of the Surprise Valley geothermal system, and show that high-temperature (quartz, Na/K, Na/K/Ca) classical geothermometers fail to predict maximum subsurface temperatures because fluids re-equilibrated at progressively lower temperatures during outflow, including in the Lake City area. We propose a model where hot spring fluids originate as a mixture between a deep thermal brine and modern meteoric fluids, with a seasonally variable mixing ratio. The deep brine has deuterium values at least 3 to 4‰ lighter than any known groundwater or high-elevation snow previously measured in and adjacent to SV, suggesting it was recharged during the Pleistocene when meteoric fluids had lower deuterium values. The deuterium values and compositional characteristics of the deep brine have only been identified in thermal springs and groundwater samples collected in proximity to structures that transmit thermal fluids, suggesting the brine may be thermal in nature. On the western side of the valley at the Lake City mud volcano, the deep brine-meteoric water mixture subsequently boils in the shallow subsurface, precipitates calcite, and re-equilibrates at about 130 °C. On the eastern side of the valley, meteoric fluid mixes to a greater extent with the deep brine, cools conductively without boiling, and the composition is modified as dissolved elements are sequestered by secondary minerals that form along the cooling and outflow path at temperatures

Meter-scale AUV bathymetric mapping and ROV sampling of the entire 47 km-long Alarcon Rise between the Pescadero and Tamayo transforms show that the shallowest inflated portion of the segment hosts all four active hydrothermal vent fields and the youngest, hottest, and highest effusion rate lava flows. This shallowest inflated part is located ∼1/3 of the way between the Tamayo and Pescadero transforms and is paved by a 16 km2 channelized flow that erupted from 9 km of en echelon fissures and is larger than historic flows on the East Pacific Rise or on the Gorda and Juan de Fuca Ridges. Starting ∼5 km south of the Pescadero transform, 6.5 km of the Alarcon Rise is characterized by faulted ridges and domes of fractionated lavas ranging from basaltic andesite to rhyolite with up to 77.3 wt % SiO2. These are the first known rhyolites from the submarine global mid-ocean ridge system. Silicic lavas range from >11.7 ka, to as young as 1.1 ka. A basalt-to-basaltic andesite sequence and an andesite-to-dacite-to-rhyolite sequence are consistent with crystal fractionation but some intermediate basaltic andesite and andesite formed by mixing basalt with dacite or rhyolite. Magmatism occurred along the bounding Tamayo and Pescadero transforms as extensive channelized flows. The flows erupted from ring faults surrounding uplifted sediment hills inferred to overlie sills. The transforms are transtensional to accommodate magma migration from the adjacent Alarcon Rise.

The Iceland Deep Drilling Project research well RN-15/IDDP-2 at Reykjanes, Iceland, reached its target of supercritical conditions at a depth of 4.5 km in January 2017. After only 6 days of heating, the measured bottom hole temperature was 426 °C, and the fluid pressure was 34MPa. The southern tip of the Reykjanes peninsula is the landward extension of the Mid-Atlantic Ridge in Iceland. Reykjanes is unique among Icelandic geothermal systems in that it is recharged by seawater, which has a critical point of 406 °C at 29.8MPa. The geologic setting and fluid characteristics at Reykjanes provide a geochemical analog that allows us to investigate the roots of a mid-ocean ridge submarine black smoker hydrothermal system. Drilling began with deepening an existing 2.5 km deep vertical production well (RN-15) to 3 km depth, followed by inclined drilling directed towards the main upflow zone of the system, for a total slant depth of 4659m (~4.5 km vertical depth). Total circulation losses of drilling fluid were encountered below 2.5 km, which could not be cured using lost circulation blocking materials or multiple cement jobs. Accordingly, drilling continued to the total depth without return of drill cuttings. Thirteen spot coring attempts were made below 3 km depth. Rocks in the cores are basalts and dolerites with alteration ranging from upper greenschist facies to amphibolite facies, suggesting that formation temperatures at depth exceed 450 °C. High-permeability circulation-fluid loss zones (feed points or feed zones) were detected at multiple depth levels below 3 km depth to bottom. The largest circulation losses (most permeable zones) occurred between the bottom of the casing and 3.4 km depth. Permeable zones encountered below 3.4 km accepted less than 5% of the injected water. Currently, the project is attempting soft stimulation to increase deep permeability. While it is too early to speculate on the energy potential of this well and its economics, the IDDP-2 is a milestone in the development of geothermal resources and the study of hydrothermal systems. It is the first well that successfully encountered supercritical hydrothermal conditions, with potential high-power output, and in which on-going hydrothermal metamorphism at amphibolite facies conditions can be observed. The next step will be to carry out flow testing and fluid sampling to determine the chemical and thermodynamic properties of the formation fluids.

The region surrounding the Modoc Plateau, encompassing parts of northeastern California, southern Oregon, and northwestern Nevada, lies at an intersection between two tectonic provinces; the Basin and Range province and the Cascade volcanic arc. Both of these provinces have substantial geothermal resource base and resource potential. Geothermal systems with evidence of magmatic heat, associated with Cascade arc magmatism, typify the western side of the region. Systems on the eastern side of the region appear to be fault controlled with heat derived from high crustal heat flow, both of which are typical of the Basin and Range. As it has the potential to host Cascade arc-type geothermal resources, Basin and Range-type geothermal resources, and/or resources with characteristics of both provinces, and because there is relatively little current development, the Modoc Plateau region represents an intriguing potential for undiscovered geothermal resources. It remains unclear however, what specific set(s) of characteristics are diagnostic of Modoc-type geothermal systems and how or if those characteristics are distinct from Basin and Range-type or Cascade arc-type geothermal systems. In order to evaluate the potential for undiscovered geothermal resources in the Modoc area, we integrate a wide variety of existing data in order to evaluate geothermal resource potential and exploration risk utilizing ‘play-fairway’ analysis. We consider that the requisite parameters for hydrothermal circulation are: 1) heat that is sufficient to drive circulation, and 2) permeability that is sufficient to allow for fluid circulation in the subsurface. We synthesize data that indicate the extent and distribution of these parameters throughout the Modoc region. ‘Fuzzy logic’ is used to incorporate expert opinion into the utility of each dataset as an indicator of either heat or permeability, and thus geothermal favorability. The results identify several geothermal prospects, areas that are highly favorable for the occurrence of both heat and permeability. These are also areas where there is sufficient data coverage, quality, and consistency that the exploration risk is relatively low. These unknown, undeveloped, and under-developed prospects are well-suited for continued exploration efforts. The results also indicate to what degree the two ‘play-types,’ i.e. Cascade arc-type or Basin and Range-type, apply to each of the geothermal prospects, a useful guide in exploration efforts.

Geothermal resource exploration is generally limited to areas with surface expressions of thermal activity (fumaroles and hot springs), or relies on expensive geophysical exploration techniques. In this study, the hidden subsurface distribution of geothermal fluids has been identified using a free and publicly available water quality dataset from agricultural and domestic water wells in Surprise Valley, northeastern California. Thermally evolved waters in Surprise Valley have element ratios that vary in response to Ca carbonate and Mg silicate mineral precipitation, and have elevated total dissolved solids (TDS). The arid climate in Surprise Valley leads to surface water evaporation in a closed basin, producing high TDS Na-Cl-CO3-SO4 brines in three ephemeral alkali lakes and in shallow groundwater under elevated soil CO2 conditions. Evaporated fluids in Surprise Valley follow a chemical divide that leads to Ca carbonate and Mg silicate mineral precipitation. Plots of dissolved element ratios can be used to distinguish groundwater affected by evaporation from water affected by thermal water-rock interaction, however it is challenging to select components for plotting that best illustrate different fluid evolution mechanisms. Here, we use a principal component analysis of centered log-ratio transformed data, coupled with geochemical models of fluid evaporation and thermal mixing pathways, to identify components to plot that distinguish between groundwater samples influenced by evaporation from those influenced by thermal processes. We find that groundwater samples with a thermal signature come from wells that define a coherent, linear geographical distribution that closely matches the location of known and inferred faults. Modification of the general approach employed here provides promise for identifying blind geothermal resources in other locations, by applying low-cost geochemical modeling and statistical techniques to areas where large groundwater quality geochemical datasets are available.

Hydrothermal activity results in element exchanges between seawater and oceanic crust that contribute to many aspects of ocean chemistry; therefore, improving knowledge of the associated chemical processes is of global significance. Hydrothermally altered basaltic drill core samples from the seawater-recharged Reykjanes geothermal system in Iceland record elemental gains and losses similar to those observed in samples of hydrothermally altered oceanic crust. At Reykjanes, rocks originally emplaced on the seafloor were buried by continued volcanism and subsided to the current depths (>2250 m below surface). These rocks integrate temperature-dependent elemental gains and losses from multiple stages of hydrothermal alteration that correspond to chemical exchanges observed in rocks from different crustal levels of submarine hydrothermal systems. Specifically, these lithologies have gained U, Mg, Zn, and Pb and have lost K, Rb, Ba, Cu, and light rare earth elements (La through Eu). Alteration and elemental gains and losses in lithologies emplaced on the seafloor can only be explained by a complex multistage hydrothermal alteration history. Reykjanes dolerite intrusions record alteration similar to that reported for the sheeted dike section of several examples of oceanic crust. Specifically, Reykjanes dolerites have lost K, Rb, Ba, and Pb, and gained Cu. The Reykjanes drill core samples provide a unique analog for seawater-oceanic crust reactions actively occurring at high temperatures (275–345°C) beneath a seafloor hydrothermal system.

The wholerock major and trace element composition of drill cutting samples are compared to drill core samples from adjacent depths in the seawater recharged Reykjanes geothermal system in Iceland. The first appearance of alteration minerals and lithologies in drill cutting samples is a useful tool for interpreting broad subsurface characteristics. However, use of drill cutting samples for determining igneous affinity and elemental exchanges during hydrothermal alteration is problematic. Samples recovered from immediately above and below the cored intervals in wells RN-17B and RN-30 demonstrate that drill-cutting samples are biased towards preservation of least altered primary igneous minerals and more resistant alteration minerals, including albite, quartz, and epidote, with preferential loss of finer-grained and less resistant minerals including chlorite and actinolite. This selective recovery obscures elemental exchanges resulting from hydrothermal alteration processes. For some elements, compositional variations (enrichments and depletions) measured from 9.5 m of core exceeds that observed in ~3000 m of cutting analyses. Concentration ratios of hydrothermally immobile elements including Zr, Nb, V, Y, HREE, Hf, Ta and Th in deep (>2245 m) spot drill core samples record bimodal, trace element-enriched and trace element-depleted precursor compositions similar to subaerial Reykjanes Peninsula basalts. The same elements in nearly 3000 m of drill cutting samples from well RN-17 overwhelmingly reflect the more common trace element-enriched igneous precursor, demonstrating that mixing of drill cutting samples obscures details of their igneous affinity. A new and different drill rig was used to deepen well RN-17 below 2266 m in a sidetrack hole (RN-17ST), which resulted in a change in drilling conditions, accompanied with an increased well deviation angle from ~0° to ~4°. Wholerock geochemical results for drill cutting samples from RN-17ST are homogenous for virtually every element; suggesting the change in drilling conditions resulted in extreme mixing of the drill cuttings. Anomalously high concentrations of Cu, Ni, Cr and Ta in some drill cutting samples likely reflects contamination of drill cutting samples by metal alloys used in drill bits and drill collars or more resistant spinel and sulfide phases.

The Iceland Deep Drilling Program well RN-17 was drilled 3km into a section of hydrothermally altered basaltic crust in the Reykjanes geothermal system in Iceland. The system is located on the landward extension of the Mid-Atlantic Ridge, and the circulating hydrothermal fluid is modified seawater, making Reykjanes a useful analog for mid-oceanic ridge hydrothermal systems. We have determined whole-rock Sr and O isotope compositions, and Sr isotope compositions of epidote grains from the RN-17 cuttings and RN-17B core. Whole rock oxygen isotope ratios range from -0.13 to 3.61‰ V-SMOW, and are isotopically lighter than fresh MORB (5.8±0.2‰). The concentrations of Sr in the altered basalt range from well below to well above concentrations in fresh rock, and appear to be strongly correlated with the dominant alteration mineralogy. Whole rock Sr isotope ratios ranged from 0.70329 in the least altered crystalline basalt, to 0.70609 in the most altered hyaloclastite samples; there is no correlation with depth. Sr isotope ratios in epidote grains measured by laser ablation MC-ICP-MS ranged from 0.70360 to 0.70731. Three depth intervals, at 1000m, 1350m, and 1650m depth, have distinctive isotopic signatures, where 87Sr/86Sr ratios are elevated (mean value>0.7050) relative to background levels (mean altered basalt value ~0.7042). These areas are proximal to geothermal feed zones, and the 1350m interval directly overlies the transition from dominantly extrusive to dominantly intrusive lithologies. Oxygen isotope measurements yield integrated water/rock ratios of 0.4 to 4.3, and suggest that hydrothermal fluids must have formerly had a component of meteoric water. Strontium isotopic measurements provide a more sensitive indication of seawater interaction and require significant exchange with seawater strontium. Both isotopic systems indicate that the greenschist-altered basalts were in equilibrium with hydrothermal fluids at a relatively high mean water/rock (Wt.) ratio ranging from about 0.5 to 4. These ratios are higher than estimates from ODP Hole 504B and IODP Hole 1256D, but are consistent with values inferred from vent fluids from 21° and 13°N on the East Pacific Rise (Albarède et al., 1981; Michard et al., 1984; Alt et al., 1996; Harris et al., 2015).

We describe the lithology and present spatially resolved geochemical analyses of samples from the hydrothermally altered Iceland Deep Drilling Project (IDDP) drill core RN-17B. The 9.3m long RN-17B core was collected from the seawater-dominated Reykjanes geothermal system, located on the Reykjanes Peninsula, Iceland. The nature of fluids and the location of the Reykjanes geothermal system make it a useful analog for seafloor hydrothermal processes, although there are important differences. The recovery of drill core from the Reykjanes geothermal system, as opposed to drill cuttings, has provided the opportunity to investigate evolving geothermal conditions by utilizing in-situ geochemical techniques in the context of observed paragenetic and spatial relationships of alteration minerals. The RN-17B core was returned from a vertical depth of ~2560m and an in-situ temperature of ~345°C. The primary lithologies are basaltic in composition and include hyaloclastite breccia, fine-grained volcanic sandstone, lithic breccia, and crystalline basalt. Primary igneous phases have been entirely pseudomorphed by calcic plagioclase+magnesium hornblende+chlorite+titanite+albitized plagioclase+vein epidote and sulfides. Despite the extensive hydrothermal metasomatism, original textures including hyaloclastite glass shards, lithic clasts, chilled margins, and shell-fragment molds are superbly preserved. Multi-collector LA-ICP-MS strontium isotope ratio (87Sr/86Sr) measurements of vein epidote from the core are consistent with seawater as the dominant recharge fluid. Epidote-hosted fluid inclusion homogenization temperature and freezing point depression measurements suggest that the RN-17B core records cooling through the two-phase boundary for seawater over time to current in-situ measured temperatures. Electron microprobe analyses of hydrothermal hornblende and hydrothermal plagioclase confirm that while alteration is of amphibolite-grade, it is in disequilibrium and the extent of alteration is dependent upon protolith type and water/rock ratio. Alteration in the RN-17B core bares many similarities to that of Type II basalts observed in Mid-Atlantic Ridge samples.

Boron has been shown to be a useful trace element in clay-mineralization reactions, raising the possibility that B studies may provide a means to investigate environmental controls on palagonitization. The objective of the present study was to address calibration, matrix effects, and B exchangeability issues such that meaningful secondary ion mass spectrometry (SIMS) microanalysis of B in thin sections of palagonite will be feasible. Silver Hill illite (IMt-1) was found to be a suitable calibration reference material, based on compositional similarity, relatively high B content, and ease of mounting on thin-section samples for SIMS microanalysis. Matrix effects of borated sideromelane and illite were compared and found to be similar, confirming previous studies which showed no matrix effects for B among minerals. Boron substitutes for Si in tetrahedral sites and also can be adsorbed in exchangeable sites of 2:1 clay minerals. Similarly, B can be found in tetrahedral and exchangeable sites within palagonite, which consists of both layered and amorphous volumes. In order to measure tetrahedral B content and isotopic ratio in the palagonite, exchangeable B was removed by soaking sample thin sections in a 1 M NH4Cl solution until exchangeable cation concentrations were constant. Treated samples showed decreases in B content and isotopic ratio with exchange. Extraction of exchangeable B permits the direct measurement of tetrahedral B content and isotopic ratio. The exchange technique devised and tested here should have broad applicability to thin-section microanalysis of B in clay and clay-like materials where cation exchange can be used for surface-analytical techniques. The present study represents an initial attempt to address sample-preparation, calibration, and potential matrix-effects problems for analyses by SIMS. Further refinements may improve the accuracy of the measurements, but the results presented here indicate that meaningful measurements are possible.

A rhyolite magma body within the Krafla geothermal system that was encountered at a depth of 2.1km during drilling of the IDDP-1 borehole is producing high temperature metamorphism within a conductive boundary layer (CBL) in adjacent host rocks. Cuttings recovered during drilling within a few meters of the intrusive contact in IDDP-1 are mainly comprised of granoblastic hornfelses, the rock type which confirms the presence of the CBL at the base of the IDDP-1 bore hole. The two pyroxenes in these hornfelses record temperatures that are in the range of 800-950°C. The minimum heat flow across the CBL is 23Wm-2. Country rocks at distances beyond 30m of the intrusive contact are essentially unaltered, implying that they have been emplaced very recently and/or as yet unaffected by hydrothermal fluid flow. © 2012 Elsevier Ltd.

Sulfate-reducing bacteria (SRB) play a major role in the coupled biogeochemical cycling of sulfur and chalcophilic metal(loid)s. By implication, they can exert a strong influence on the speciation and mobility of multiple metal(loid) contaminants. In this study, we combined DsrAB gene sequencing and sulfur isotopic profiling to identify the phylogeny and distribution of SRB and to assess their metabolic activity in salt marsh sediments exposed to acid mine drainage (AMD) for over 100 years. Recovered dsrAB sequences from three sites sampled along an AMD flow path indicated the dominance of a single Desulfovibrio species. Other major sequence clades were related most closely to Desulfosarcina, Desulfococcus, Desulfobulbus, and Desulfosporosinus species. The presence of metal sulfides with low delta(34)S values relative to delta(34)S values of pore water sulfate showed that sediment SRB populations were actively reducing sulfate under ambient conditions (pH of approximately 2), although possibly within less acidic microenvironments. Interestingly, delta(34)S values for pore water sulfate were lower than those for sulfate delivered during tidal inundation of marsh sediments. 16S rRNA gene sequence data from sediments and sulfur isotope data confirmed that sulfur-oxidizing bacteria drove the reoxidation of biogenic sulfide coupled to oxygen or nitrate reduction over a timescale of hours. Collectively, these findings imply a highly dynamic microbially mediated cycling of sulfate and sulfide, and thus the speciation and mobility of chalcophilic contaminant metal(loid)s, in AMD-impacted marsh sediments.

Pore fluids from Clear Lake sediments collected near the abandoned Sulphur Bank Mercury Mine have low pH (locally <4) and elevated sulfate (> or =197 mmol/L), aluminum (> or =52 mmol/L), and iron (> or =28 mmol/L) contents derived from oxidation of sulfide minerals at the mine site. Acid mine drainage (AMD) is entering Clear Lake by advective subsurface flow nearest the mine and by diffusion at greater distances. Oxygen and hydrogen isotope ratios, combined with pore fluid compositions, constrain the sources and pathways of contaminated fluids. Sediment cores taken nearest the mine have the highest concentrations of dissolved sulfate, aluminum, and iron, which are contributed by direct subsurface flow of AMD from sulfide-bearing waste rock. Sediment cores as far as 100 m west of the Clear Lake shoreline show the presence of AMD that originated in the acidic lake that occupies the abandoned Herman Pit at the mine site. High sulfate content in the AMD has the potential to promote the activity of sulfate-reducing bacteria in the organic-rich lake sediments, which leads to methylation of Hg+2, making it both more toxic and bioavailable. Quantitative depletion of pore water sulfate at depth and sulfur isotope values of diagenetic pyrite near 0 per thousand indicate that sulfate availability limits the extent of sulfate reduction in the lake sediments away from the mine. Profiles of pore water sulfate in the sediments near the mine show that excess sulfate is available to support the activity of sulfate-reducing bacteria near the mine site. Enriched isotope values of dissolved sulfate (as high as 17.1 per thousand) and highly depleted isotope values for diagenetic pyrite (as low as -22.6 per thousand) indicate active bacterial sulfate reduction in the AMD-contaminated sediments. Sulfate- and iron-rich acid mine drainage entering Clear Lake by shallow subsurface flow likely needs to be controlled in order to lower the environmental impacts of Hg in the Clear Lake ecosystem.

We analyzed the sedimentological characteristics and magnetic properties of cores from the three basins of Clear Lake, California, USA, to assess the depositional response to a series of land use changes that occurred in the watershed over the 20th century. Results indicate that distinct and abrupt shifts in particle size, magnetic concentration/mineralogy, and redox conditions occur concurrently with a variety of ecological and chemical changes in lake bed sediments. This coincidence of events occurred around 1927, a datum determined by an abrupt increase in total mercury (Hg) in Clear Lake cores and the known initiation of open-pit Hg mining at the Sulphur Bank Mercury Mine, confirmed by 210Pb dating. Ages below the 1927 horizon were determined by accelerator mass spectrometry on 14C of coarse organic debris. Calculated sedimentation rates below the 1927 datum are approximately 1 mm/yr, whereas rates from 1927 to 2000 are up to an order of magnitude higher, with averages of approximately 3.5-19 mm/yr. In both the Oaks and Upper Arms, the post-1927 co-occurrence of abrupt shifts in magnetic signatures with color differences indicative of changing redox conditions is interpreted to reflect a more oxygenated diagenetic regime and rapid burial of sediment below the depth of sulfate diffusion. Post-1927 in the Oaks Arm, grain size exhibits a gradual coarsening-upward pattern that we attribute to the input of mechanically deposited waste rock related to open-pit mining activities at the mine. In contrast, grain size in the Upper Arm exhibits a gradational fining-upward after 1927 that we interpret as human-induced erosion of fine-grained soils and chemically weathered rocks of the Franciscan Assemblage by heavy earthmoving equipment associated with a road- and home-building boom, exacerbated by stream channel mining and wetlands destruction. The flux of fine-grained sediment into the Upper Arm increased the nutrient load to the lake, and that in turn catalyzed profuse cyanobacterial blooms through the 20th century. The resulting organic biomass, in combination with the increased inorganic sediment supply, contributed to the abrupt increase in sedimentation rate after 1927.

Clear Lake is the site of an abandoned mercury (Hg) mine (active intermittently from 1873 to 1957), now a U.S. Environmental Protection Agency Superfund Site. Mining activities, including bulldozing waste rock and tailings into the lake, resulted in approximately 100 Mg of Hg entering the lake's ecosystem. This series of papers represents the culmination of approximately 15 years of Hg-related studies on this ecosystem, following Hg from the ore body to the highest trophic levels. A series of physical, chemical, biological, and limnological studies elucidate how ongoing Hg loading to the lake is influenced by acid mine drainage and how wind-driven currents and baroclinic circulation patterns redistribute Hg throughout the lake. Methylmercury (MeHg) production in this system is controlled by both sulfate-reducing bacteria as well as newly identified iron-reducing bacteria. Sediment cores (dated with dichlorodiphenyldichlorethane [DDD], 210pb, and 14C) to approximately 250 cm depth (representing up to approximately 3000 years before present) elucidate a record of total Hg (TotHg) loading to the lake from natural sources and mining and demonstrate how MeHg remains stable at depth within the sediment column for decades to millenia. Core data also identify other stresses that have influenced the Clear Lake Basin especially over the past 150 years. Although Clear Lake is one of the most Hg-contaminated lakes in the world, biota do not exhibit MeHg concentrations as high as would be predicted based on the gross level of Hg loading. We compare Clear Lake's TotHg and MeHg concentrations with other sites worldwide and suggest several hypotheses to explain why this discrepancy exists. Based on our data, together with state and federal water and sediment quality criteria, we predict potential resulting environmental and human health effects and provide data that can assist remediation efforts.

Clear Lake, California, USA, is the site of the Sulphur Bank Mercury Mine, now a U.S. Environmental Protection Agency Superfund Site. Intermittent mining from 1873 to 1957 resulted in approximately 100 Mg of mercury (Hg) being deposited into the lake's ecosystem. Sediment cores to approximately 2.5 m depth (dated using 210Pb and 14C) represent approximately 3000 years of sedimentation. Clear Lake sediments have experienced Hg deposition from anthropogenic sources (mining) during historic times (to the mid-1900s) and geologic sources during prehistoric times (prior to the mid-1800s). This provides a unique opportunity to evaluate hypotheses relating to (1) the influence of the mine on Hg loading to the lake and (2) the potential upward mobilization of Hg by diagenetic processes proposed by some as an alternative explanation for increased Hg concentrations at the surface of the sediment column believed to be caused by increased global atmospheric deposition. Although Hg mining began in 1873, no significant evidence of anthropogenic Hg loading was detected in cores prior to open-pit mining ca. 1927, which also involved bulldozing mine waste rock and tailings into the lake. Exponential increases in total Hg (TotHg) and methylmercury (MeHg) were observed above the 1927 horizon, where estimated sedimentation rates were 2.2-20.4 mm/yr and peaks of both forms of Hg maintained vertical stability within the sediment column. Below the 1927 horizon, a slow increase in both TotHg and MeHg with depth was observed from approximately 1000 to 3000 years before present, where sedimentation rates ranged from approximately 0.6 to 2.0 mm/yr and elevated Hg profiles appear stable. Vertical stability of Hg in the shallow and deep sediment column suggests that both TotHg and MeHg do not undergo diagenetic upward mobilization within the sediment column under rapid or slow sedimentation rates. Because (1) these data were collected at a site with known anthropogenic and geologic sources and (2) regions of elevated Hg concentrations from both sources remain stable within the sediment column under very different sedimentation regimes, these results also support the hypothesis that elevated Hg at the surface of cores in other worldwide locations likely represents global atmospheric deposition rather than upward diagenetic mobilization.

Sediment cores were collected to investigate multiple stresses on Clear Lake, California, USA, through the period of European occupation to the present day. Earlier workers suggested the hypothesis that the use of mechanized earthmoving equipment, starting in the 1920s and 1930s, was responsible for erosion, mercury (Hg) contamination, and habitat loss stresses. Cores (approximately 2.5 m in depth) were collected in 1996 and 2000 from each of the three arms of the lake. Carbon-14 dating suggests that these cores represent as much as 3000 years of the lake's history, beginning long before European settlement. Total mercury (TotHg) and methylmercury (MeHg), dry matter, water, carbon, nitrogen, phosphorus, sulfur, and the stable isotopes 13C and 15N were measured at 5-cm intervals. Nearly all parameters show major changes at depths of 58-135 cm, beginning at ca. 1927 (dated with 210Pb). Accepting this date for concomitant major changes in seven cores yields an estimated 8.6 mm/yr average sedimentation rate after 1927. Pre-1927 sedimentation rates were approximately 1 mm/yr. Total mercury and MeHg, dry matter, phosphorus, and 15N increase significantly, whereas nitrogen, sulfur, carbon, and water content decrease significantly above the 1927 horizon. Both TotHg and MeHg show extremely large increases (roughly 10-fold) above the 1927 horizon. A peak in inorganic deposition rate and minimum values for percentage of water is present at depths corresponding to ca. 1970. Interestingly, the first 75 years of European settlement in the Clear Lake basin (including the most productive years of the Sulphur Bank Mercury Mine) appeared to have had undetectable effects on lake cores. Changes since 1927 were dramatic. The large increase in Hg beginning about 1927 corresponds to the use of heavy equipment to exploit the ore deposit at the mine using open-pit methods. Increases in sediment deposition from increased earthmoving in the basin and sulfate loading from the mine are the most likely explanations for the dramatic changes seen in the post-1927 sections of the cores.

Bottled and packaged waters are an increasingly significant component of the human diet. These products are regulated at the regional, national, and international levels, and determining the authenticity of marketing and labeling claims represents a challenge to regulatory agencies. Here, we present a dataset of stable isotope ratios for bottled waters sampled worldwide, and consider potential applications of such data for regulatory, forensic and geochemical standardization applications. The hydrogen and oxygen isotope ratios of 234 samples of bottled water range from -147 per thousand to +15 per thousand and from -19.1 per thousand to +3.0 per thousand, respectively. These values fall within and span most of the normal range for meteoric waters, indicating that these commercially available products represent a source of waters for use as laboratory working standards in applications requiring standardization over a large range of isotope ratios. The measured values of bottled water samples cluster along the global meteoric water line, suggesting that bottled water isotope ratios preserve information about the water sources from which they were derived. Using the dataset, we demonstrate how bottled water isotope ratios provide evidence for substantial evaporative enrichment of water sources prior to bottling and for the marketing of waters derived from mountain and lowland sources under the same name. Comparison of bottled water isotope ratios with natural environmental water isotope ratios demonstrates that on average the isotopic composition of bottled water tends to be similar to the composition of naturally available local water sources, suggesting that in many cases bottled water need not be considered as an isotopically distinct component of the human diet. Our findings suggest that stable isotope ratios of bottled water have the power to distinguish ultimate (e.g., recharge) and proximal (e.g., reservoir) sources of bottled water and constitute a potential tool for use in the regulatory monitoring of water products.