Diel oxygen dynamics and anoxic events in an eutrophic estuary of Waquoit Bay,Massachusetts

As a result of nutrient loading from septic systems, a thick canopy of macroalgae covers the bottom of Waquoit Bay, an embayment on Cape Cod, Massachusetts. Using automated conductivity-temperature-oxygen recorders and manual profiles, we measured diel water column O₂ changes during summer in the Childs River, the estuary of the bay with the highest housing density. At dawn in midsummer, bottom waters in the Childs River are chronically hypoxic due to high rates of benthic respiration. On sunny days benthic photosynthesis drives bottom water O₂ to 10–15 mg l^?1 by afternoon. The extent of the daily O₂ excursion is directly proportional to daily irradiance. Large diel O₂ excursions in bottom water are due to limited mixing of surface and bottom water. Density stratification exceeded two sigma-t units 85% of the time during midsummer in the Childs River. Because of stratification, hypoxia and even anoxia occur in this estuary. The first of several anoxic events was observed in Waquoit Bay in 1988, and we have attempted to evaluate factors that trigger anoxia. High rates of benthic respiration result in anoxia when replenishment of O₂ during the day is limited by insufficient light. Our analysis of meteorological records during two recent anoxic events shows that anoxia develops overnight in midsummer during periods of peak summertime temperatures after several days of cloudy, moderately calm weather. Similarly critical conditions existed most summers since 1975, yet anoxic events in the bay have not been reported historically. If climatic warming occurs, anoxic events in the bay may occur more frequently even if algal stocks remain unchanged. Eutrophication of Waquoit Bay is similar to many other embayments in populated coastal areas, and anoxic events may indicate a chronic growing problem in these important ecosystems. However, in shallow, stratified embayments, anoxia may be transient and easily missed without frequent monitoring.     

Manganese minerals and associated fine particulates in the streambed of Pinal Creek,Arizona, U.S.A.: a mining-related acid drainage problem

The Pinal creek drainage basin in Arizona is a good example of the principal non-coal source of mining-related acid drainage in the U.S.A., namely copper mining. Infiltration of drainage waters from mining and ore refining has created an acid groundwater plume that has reacted with calcite during passage through the alluvium, thereby becoming less acid. Where O₂ is present and the water is partially neutralized, iron oxides have precipitated and, farther downstream where the pH of the stream water is near neutral, high-Mn crusts have developed.Trace metal composition of several phases in the Pinal Creek drainage basin illustrates the changes caused by mining activities and the significant control Mn-crusts and iron oxide deposits exert on the distribution and concentration of trace metals. The phases and locales considered are the dissolved phase of Webster Lake, a former acid waste disposal pond; selected sections of cores drilled in the alluvium within the intermittent reach of Pinal Creek; and the dissolved phase, suspended sediments, and streambed deposits at specified locales along the perennial reach of Pinal creek.In the perennial reach of Pinal Creek, manganese oxides precipitate from the streamflow as non-cemented particulates and coatings of streambed material and as cemented black crusts. Chemical and X-ray diffraction analyses indicate that the non-cemented manganese oxides precipitate in the reaction sequence observed in previous laboratory experiments using simpler solution composition, Mn₃O₄ to MnOOH to an oxide of higher oxidation number usually <4.0, i.e. Na-birnessite, and that the black cemented crusts contain (Ca,Mn,Mg)CO₃ and a 7-Åphyllomanganate mixture of rancieite ((Ca,Mn)Mn₄O₉ · (3H₂O)) and takanelite ((Mn,Ca)Mn₄O₉ · (3H₂O)). In the laboratory, aerating and increasing the pH of Pinal Creek water to 9.00 precipitated (Ca,Mn,Mg)CO₃ from an anoxic groundwater that contained CO₂ HCO₃, and precipitated Mn₃O₄ and subsequently MnOOH from an oxic surface water from which most of the dissolved CO₂ had been removed.It is suggested that the black cemented crusts form by precipitation of Fe on the Mn-enriched carbonates, creating a site for the MnFe oxidation cycle and thus encouraging the conversion of the carbonates to 7-Åphysllomanganates. The non-magnetic <63-μm size-fractions of the black cemented crusts consisted mostly of the manganese-calcium oxides but also contained about 20% (Ca,Mn,Mg)CO₃, 5% Fe (calculated as FeOOH), 2–4% exchangeable cations, and trace amounts of several silicates.     

Vesicles,water, and sulfur in Reykjanes Ridge basalts

Dredge hauls of fresh submarine basalt collected from the axis of the Reykjanes Ridge (Mid-Atlantic Ridge) south of Iceland were taken aboard R/ V TRIDENT in 1967 and 1971. The samples show systematic changes as the water depth of collection (and eruption) decreases: radially elongate vesicles and concentric zones of vesicles appear at about 700 m depth and are conspicuous to shallow water; the smoothed volume percent of vesicles increases from 5% at 1000 m, 10% at 700 m, to 16% at 500 m, and the scatter in degree of vesicularity increases in shallower water; specific gravity decreases from 2.7±0.1 at 1000 m to 2.3±0.3 at 100 m. Bulk sulfur content for the outer 2 cm averages 843 ppm up to a depth of 200 m, then drops off rapidly in shallower water owing to degassing. Sulfur content below 200 m is independent of depth (or geographic position), and the melt is apparently saturated with sulfur, but the excess cannot escape the lava unless another vehicle carries it out. Only shallower than 200 m, where intense vesiculation of other gases occurs can excess sulfur be lost from the lava erupting on the sea floor. H₂O^+110° averages about 0.35 percent and H₂O^+150° about 0.25 percent, and both apparently decrease in water shallower than 200 m as a result of degassing. H₂O⁺ (below 200 m) decreases with distance from Iceland or increasing depth, presumably as a result of either adsorption of water on the surface of shallower, more vesicular rocks; or more likely due to the presence of the Iceland hot mantle plume supplying undifferentiated primordial material, relative to lavas of the Reykjanes Ridge supplied from the low velocity layer already depleted in volatiles and large lithophile elements. The H₂O^+110°/S ratio of lava erupting below 200 m water depth ranges from 3 to 5 which is comparable to reliable gas analyses from oceanic basaltic volcanoes. Publication authorized by the Director, U.S. Geological Survey.     

Particulate sulfur species in the water column of the Cariaco Basin

The biogeochemistry of iron sulfide minerals in the water column of the Cariaco Basin was investigated in November 2007 (non-upwelling season) and May 2008 (upwelling season) as part of the on-going CARIACO (CArbon Retention In A Colored Ocean) time series project. The concentrations of particulate sulfur species, specifically acid volatile sulfur (AVS), greigite, pyrite, and particulate elemental sulfur, were determined at high resolution near the O₂/H₂S interface. In November 2007, AVS was low throughout the water column, with the highest concentration at the depth where sulfide was first detected (260 m) and with a second peak at 500 m. Greigite, pyrite, and particulate elemental sulfur showed distinct concentration maxima near the interface. In May 2008, AVS was not detected in the water column. Maxima for greigite, pyrite, and particulate elemental sulfur were again observed near the interface. We also studied the iron sulfide flux using sediment trap materials collected at the Cariaco station. Pyrite comprised 0.2-0.4% of the total particulate flux in the anoxic water column, with a flux of 0.5-1.6 mg S m⁻² d⁻¹.Consistent with the water column concentration profiles for iron sulfide minerals, the sulfur isotope composition of particulate sulfur found in deep anoxic traps was similar to that of dissolved sulfide near the O₂/H₂S interface. We conclude that pyrite is formed mainly within the redoxcline where sulfur cycling imparts a distinct isotopic signature compared to dissolved sulfide in the deep anoxic water. This conclusion is consistent with our previous study of sulfur species and chemoautotrophic production, which suggests that reaction of sulfide with reactive iron is an important pathway for sulfide oxidation and sulfur intermediate formation near the interface. Pyrite and elemental sulfur distributions favor a pathway of pyrite formation via the reaction of FeS with polysulfides or particulate elemental sulfur near the interface. A comparison of thermodynamic predictions with actual concentration profiles for iron sulfides leads us to argue that microbes may mediate this precipitation.     

The geochemistry of primary and weathered oil shale and coquina across the Julia Creek vanadium deposit (Queensland, Australia)

A significant resource of vanadium and molybdenum exists near Julia Creek, Australia, where the middle Cretaceous organic-rich Toolebuc Formation lies between 0 and 25 m of the surface. We present and discuss a comprehensive geochemical study of the Toolebuc Formation and its enclosing stratigraphy near Julia Creek to understand this ore deposit. V and Mo contents in fresh facies are strongly associated with total organic carbon (TOC) contents, but not with Al or CaCO₃; this suggests that V and Mo were originally concentrated in the organic fraction. However, chemical extractions using H₂O₂ indicate that Mo was originally concentrated in pyrite. The data also suggest that V was mobilised from organic matter during early diagenesis and became associated with clays as little V was extracted by H₂O₂ in the fresh samples. TOC contents in the Toolebuc Formation were removed during weathering, residually enriching trace metals including V and Mo, and as a result, the TOC relationship with V and Mo disintegrates. With weathering, both V and Mo predominantly became associated with iron oxide/hydroxide phases (and possibly other unidentified phases) as these elements in the weathered facies were highly soluble in the sodium citrate–sodium dithionite digestion. Large shale-hosted V and Mo deposits such as Julia Creek offer a potentially viable alternative to the currently mined magnetite-hosted deposits. A thorough understanding of the formation and host mineral phases for V and Mo of these shale deposits, however, is critical to ensure that these valuable metals can be feasibly extracted.     

Phosphorus cycling in a managed lake ecosystem: Seasonal and longer-term trends

Irondequoit Bay, adjacent to Rochester, New York, is one of the larger embayments along the southern coast of Lake Ontario. Since the 1980s, management activities have been focused on improving water quality and the trophic status of the bay, including a program of hypolimnetic oxygenation. During the summers of 2003, 2004 and 2009, a program of basic water quality parameter profiles and sediment sampling completed. Results of these surveys show an increase in hypolimnetic P throughout each summer season. The increase in P is concordant with decreasing dissolved O₂ concentrations. Although the dissolved O₂ levels are persistent in the suboxic range for most of the summer season, the oxygenation program prevents anoxic conditions, limiting the release of P to that associated with Mn oxyhydroxides. Longer-term trends show an upward linear trend in metalimnetic P which is associated with the trophic status of the bay. This upward trend may be linked to cycling and enrichment of the near surface sediment in P.     

Biogeochemistry of Major Redox Elements and Mercury in a Tropical Reservoir Lake (Petit Saut,French Guiana)

The hydroelectric reservoir of Petit Saut, French Guiana, was created in 1994–1995 by flooding 350 km² of tropical forest. When sampled in 1999, the lake exhibited a permanent stratification separating the 3–5 m thick, oxygenated epilimnion from the anoxic hypolimnion. The rate of anaerobic organic carbon mineralization below the oxycline was on the order of 1 μmol C m⁻² s⁻¹ and did not show a pronounced difference between wet and dry seasons. Methanogenesis accounted for 76–83% of anaerobic carbon mineralization, with lesser contributions of sulfate reduction and dissimilatory iron reduction. Upward mixing of reduced inorganic solutes explained 90% of the water column O ₂ demand during the dry season, while most O ₂ consumption during the wet season was coupled to aerobic respiration of organic matter synthesized in the surface waters. Inorganic mercury species represented 10–40% of total dissolved mercury in the epilimnion, but were of relatively minor importance (≤10%) in the anoxic portion of the water column. Net production of soluble organic mercury compounds in the flooded soils and anoxic water column did not vary significantly between wet and dry seasons. Methylmercury accounted for about 15% of total dissolved mercury below the oxycline. Its estimated net production rate, 0.04 mg m⁻² yr⁻¹, is of the same order of magnitude as values reported for contaminated lakes and flooded terrestrial ecosystems.     

Response of resource excavations in Mobile Bay, Alabama, to extreme forcing

Fossil reef deposits of the American oyster,Crassostrea virginica, are a common component of the near surface sediments in the middle and upper reaches of Mobile Bay, northern Gulf of Mexico. Mining of these deposits occurred from 1946 through 1982 in open areas of undisturbed bay bottom, outside of the shipping channel corridors, in water depths of 3–5 m. The mining process resulted in the formation of pit to furrow-shaped depressions with elevated rims at some sites and troughs and ridges in other areas. Studies carried out in the early 1970s predicted normal physical processes would restore the bottom to pre-shell mining conditions within 1 yr, thus minimizing any long-term effects on the Mobile Bay estuary. However, over the period 1974–1976 unfilled excavations, some with raised rims and ridges, were observed where mining had occurred 3–5 yr earlier. In addition, the depressions tended to be sites of relatively high salinity, hypoxic to anoxic water. In 1992–1993, close grid bathymetric surveys produced no indication of either depressions or raised features at any of the old mining sites. Evidence suggests this leveling of the bay’s bathymetry was the result of two major hurricanes, Frederic in 1979 and Elena in 1985, which mobilized and redistributed significant quantities of sediments within Mobile Bay. These findings indicate currents and waves associated with Mobile Bay’s normal tidal activity and annual recurrent storms were acting very slowly to refill depressions and flatten elevated features. In contrast, the direct impact of major hurricanes appears to have served as an effetive agent to return Mobile Bay’s bathymetry to a state similar to pre-shell mining conditions.     

Reduced sulfur and iron species in anoxic water column of meromictic crater Lake Pavin (Massif Central, France)

The vertical distribution of reduced sulfur species (RSS including H₂S/HS⁻, S⁰, electroactive FeS) and dissolved Fe(II) was studied in the anoxic water column of meromictic Lake Pavin. Sulfide concentrations were determined by two different analytical techniques, i.e. spectophotometry (methylene blue technique) and voltammetry (HMDE electrode). Total sulfide concentrations determined with methylene blue method (∑H₂S_MBRS) were in the range from 0.6 µM to 16.7 µM and were substantially higher than total reduced sulfur species (RSS_V) concentrations determined by voltammetry, which ranged from 0.1 to 5.6 μM. The observed difference in the sulfide concentrations between the two methods can be assigned to the presence of FeS colloidal species.Dissolved Fe was high (> 1000 µM), whereas dissolved Mn was only 25 µM, in the anoxic water column. This indicates that Fe is the dominant metal involved in sulfur redox cycling and precipitation. Consequently, in the anoxic deep layer of Lake Pavin, “free” sulfide, H₂S/HS⁻, was low; and about 80% of total sulfide detected was in the electroactive FeS colloidal form. IAP calculations showed that the Lake Pavin water column is saturated with respect to FeS_am phase. The upper part of monimolimnion layer is characterized by higher concentrations of S(0) (up to 3.4 µM) in comparison to the bottom of the lake. This behavior is probably influenced by sulfide oxidation with Fe(III) oxyhydroxide species.     

Application of in-situ and on-line measurements to environmental studies in Lake Müritz,northern Germany

A new system, MINIBAT, for in-situ measurements and continuous collection of water samples was used in Lake Müritz (Mecklenburg-Vorpommern) to make detailed and simultaneous measurements of temperature, conductivity, pressure, particle density, H₂S, O₂, pH, nutrients and heavy metals. The underwater measuring unit consists of a multisensor unit, a micro-processor and an underwater pump (pumping rate up to 0.8 l/min) carried in a small, towed frame. The onboard unit (IBM compatible computer) is able to record sensor and location data transmitted from a GPS system and echosounder. Onboard, the water samples are split for introduction into a H₂S flow-through sensor and for aliquots which are filtered through standard membrane filters and preserved either for trace metal determination or nutrient analysis. All data are stored in a data bank which can be used as a base for mapping the different parameters within the water body. This compact and portable system represents a breakthrough for hydrochemical investigations of lakes and rivers and was used to map the hydrochemical parameters and anthropogenic influences in Lake Müritz. In-situ measurements made during the summer stagnation showed that a 10 m-thick layer enriched in H₂S built up in the bottom water. This anoxic hypolimnion was characterized by a steadily increasing H₂S content approaching the sediment surface and with an associated increase in the contents of the nutrients NH₄⁺ and PO₄³⁻ and a decrease in the heavy metal contents.     

Quantification of water content and speciation in natural silicic glasses (phonolite, dacite, rhyolite) by confocal microRaman spectrometry

The determination of total water content (H₂O_T: 0.1-10 wt%) and water speciation (H₂O_molecular/OH) in volcanic products by confocal microRaman spectrometry are discussed for alkaline (phonolite) and calcalkaline (dacite and rhyolite) silicic glasses. Shape and spectral distribution of the total water band (H₂O_T) at ∼3550 cm⁻¹ show systematic evolution with glass H₂O_T, water speciation and NBO/T. In the studied set of silicic samples, calibrations based on internal normalization of the H₂O_T band to a band related to vibration of aluminosilicate network (TOT) at ∼490 cm⁻¹ vary with glass peraluminosity. An external calibration procedure using well-characterized glass standards is less composition-dependent and provides excellent linear correlation between total dissolved water content and height or area of the H₂O_T Raman band. Accuracy of deconvolution procedure of the H₂O_T band to quantify water speciation in water-rich and depolymerized glasses depends on the strength of OH hydrogen bonding. System confocal performance, scattering from embedding medium and glass microcrystallinity have a crucial influence on accuracy of Raman analyses of water content in glass-bearing rocks and melt inclusions in crystals.     

Time dependence of organic matter decay and mixing processes in Framvaren, a permanently anoxic fjord in South Norway

Three different layers have been identified in Framvaren, which has a maximum water depth of 184 m. One oxic layer above the redoxcline at 18–20 m. One anoxic layer from 20 to 100 m which is occasionally ventilated by a flow over the sill (which has a depth of 2.5 m), and finally a stagnant layer below 100 m. Using the release rate of silica from the bottom and measurements of the concentration of HTO it is possible to make some calculations on the annual volume of interleaving in the layers 25–50 m, 50–75 m, and 75–100 m together with the advective flows. Reliable values of the sulfide concentration were obtained by precipitating and weighing HgS together with careful protection of all anoxic water samples with argon. The light yellow color of the precipitate in the depth range 25 to 80 m indicates that the occasional ventilation will cause such reactions as 0.50₂ + H₂S S(colloidal) + H₂O. The elemental sulfur, being stabilized with HS^–, is set free upon the precipitation of HgS. The new data for the concentration of sulfide give an acceptable stoichiometry for the decay reaction of organic matter. This is not the case with the data of Yao and Millero. The mean values for the concentrations of ammonium and phosphate agree with the new data of Yao and Millero. The mol/mol C/N ratio of 10.1 found in trapped material by Naess and coworkers (1988) agrees with the stoichiometry of the dissolved constituents, i.e. C/N = 9.92 ± 0.45. A denitrification reaction is suggested to explain the high values of C/N. The vertical diffusion coefficient at 100 m calculated from the depth profile of silica was 0.92 × 10^–6 m² s^–1 which lies in the range of values given by Fröyland. Finally, the ¹⁴C age of the total dissolved inorganic carbon (Ct) in the water below 90 m was about 1600 years indicating a bioproduction in the period 8000 years B.P. to A.D. 1853 when a channel was opened between the fjord outside (Helvikfjord) and Framvaren.     

Stenols and stanols in the oxic and anoxic waters of the Black Sea

Water samples collected from a slope station and two deep stations in the western basin of the Black Sea were analyzed for stenols and stanols by glass capillary gas chromatography. These results were used in conjuction with hydrographic, particulate organic carbon, and chlorophyll a data to better understand sterol sources and their transport and transformation mechanisms in anoxic basins.The total free sterol concentrations found in the surface waters were 450–500 ng/l dropping rapidly to values well below 100 ng/l at depths below the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. In the upper 200 m of the water column a strong association of sterols with particulate matter is suggested. Structural elucidation by a gas chromatograph-mass spectrometer-computer system revealed the presence of at least sixteen different stenols and stanols in the surface waters of the Black Sea. Cholesterol, 24-methylenecholesterol and 24-methylcholesta-5,22-dien-3β-ol were the major sterols in the surface waters. Cholesterol and 24-ethylcholesterol both exhibited a subsurface maximum at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. In the anoxic deep waters (200–2000 m) only cholesterol and 24-ethylcholesterol were found. Two stenols were found that have not been reported in seawater: a C₂₆ stenol with a saturated C₇H₁₅ side chain (presumably 24-norcholesterol) and 24-ketocholesterol. At least six 5α-stanols could be identified in the surface samples, each of them comprising about 10–20% of the concentration of the corresponding Δ5-stenol. From these comparatively high surface values the stanol concentrations drop rapidly to values near zero at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. Except for very low concentrations of 5α-cholestanol (< 4ng/l) no other stanols could be detected in the anoxic zone.From this data it appears that no detectable stenol → stanol conversion is occurring at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface or in the deep anoxic waters of the Black Sea.     

Long-Term and Seasonal Changes in Nutrients,Phytoplankton Biomass,and Dissolved Oxygen in Deep Bay,Hong Kong

Deep Bay is a semienclosed bay that receives sewage from Shenzhen, a fast-growing city in China. NH₄ is the main N component of the sewage (>50% of total N) in the inner bay, and a twofold increase in NH₄ and PO₄ concentrations is attributed to increased sewage loading over the 21-year period (1986–2006). During this time series, the maximum annual average NH₄ and PO₄ concentrations exceeded 500 and 39 μM, respectively. The inner bay (Stns DM1 and DM2) has a long residence time and very high nutrient loads and yet much lower phytoplankton biomass (chlorophyll (Chl) <10 μg L⁻¹ except for Jan, July, and Aug) and few severe long-term hypoxic events (dissolved oxygen (DO) generally >2 mg L⁻¹) than expected. Because it is shallow (~2 m), phytoplankton growth is likely limited by light due to mixing and suspended sediments, as well as by ammonium toxicity, and biomass accumulation is reduced by grazing, which may reduce the occurrence of hypoxia. Since nutrients were not limiting in the inner bay, the significant long-term increase in Chl a (0.52–0.57 μg L⁻¹ year⁻¹) was attributed to climatic effects in which the significant increase in rainfall (11 mm year⁻¹) decreased salinity, increased stratification, and improved water stability. The outer bay (DM3 to DM5) has a high flushing rate (0.2 day⁻¹), is deeper (3 to 5 m), and has summer stratification, yet there are few large algal blooms and hypoxic events since dilution by the Pearl River discharge in summer, and the invasion of coastal water in winter is likely greater than the phytoplankton growth rate. A significant long-term increase in NO₃ (0.45–0.94 μM year⁻¹) occurred in the outer bay, but no increasing trend was observed for SiO₄ or PO₄, and these long-term trends in NO₃, PO₄, and SiO₄ in the outer bay agreed with those long-term trends in the Pearl River discharge. Dissolved inorganic nitrogen (DIN) has approximately doubled from 35–62 to 68–107 μM in the outer bay during the last two decades, and consequently DIN to PO₄ molar ratios have also increased over twofold since there was no change in PO₄. The rapid increase in salinity and DO and the decrease in nutrients and suspended solids from the inner to the outer bay suggest that the sewage effluent from the inner bay is rapidly diluted and appears to have a limited effect on the phytoplankton of the adjacent waters beyond Deep Bay. Therefore, physical processes play a key role in reducing the risk of algal blooms and hypoxic events in Deep Bay.     

Hydrogen sulfide and organic carbon at the sediment–water interface in coastal brackish Lake Nakaumi, SW Japan

The relationship among H₂S, total organic carbon (TOC), total sulfur (TS) and total nitrogen contents of surface sediments (0–1 cm) was examined to quantify the relationship between H₂S concentrations and TOC content at the sediment water interface in a coastal brackish lake, Nakaumi, southwest Japan. In this lake, bottom water becomes anoxic during summer due to a strong halocline. Lake water has ample dissolved SO₄ ^2? and the surface sediments are rich in planktic organic matter (C/N 7–9), which is highly reactive in terms of sulfate reduction. In this setting the amount of TOC should be a critical factor regulating the activity of sulfate reduction and H₂S production. In portions of the lake where sediment TOC content is less than 3.5 %, H₂S was very low or absent in both bottom and pore waters. However, in areas with TOC >3.5 %, H₂S was correlated with TOC content (pore water H₂S (ppm) = 13.9 × TOC (%) ? 52.1, correlation coefficient: 0.72). H₂S was also present in areas with sediment TS above 1.2 % (present as iron sulfide), which suggests that iron sulfide formation is tied to the amount of TOC. Based on this relationship, H₂S production has progressively increased after the initiation of land reclamation projects in Lake Nakaumi, as the area of sapropel sediments has significantly increased. This TOC–H₂S relationship at sediment–water interface might be used to infer H₂S production in brackish–lagoonal systems similar to Lake Nakaumi, with readily available SO₄ ^2? and reactive organic matter.     

The nature of water in chalcedony and opal-C from brazilian agate geodes

The water species (H₂O_(SiOH) and H₂O_(mol)) of length-fast chalcedony and opal-C in Brazilian agates were studied with thermoanalytical, chemical and infrared absorption methods. Specific surfaces were measured with the BET nitrogen adsorption method and the specific densities were determined. Chalcedony and opal-C have fully hydrated crystal surfaces at the open porosity. They contain additional water at inner surfaces, which are closed micropores in the case of opal-C and regions of accumulated defects (e.g. twinlamellae boundaries) in chalcedony. All surfaces are covered with silanole groups, hydrogen-bonded to molecular water. Additional hydroxyl groups, weakly hydrogen bonded to the structural framework within the crystallites, are located at structural point defects. Wall-lining chalcedony ranges from translucent gray to milky white bands corresponding with decreasing total water content, the H₂O_(SiOH)/H₂O_(mol)-ratio, BET-surfaces and increasing density. The H₂O_(SiOH)/H₂O_(mol)-ratio is sensitive to subsequent hydrothermal treatment and indicates a low temperature formation of chalcedony.     

Experiments on liquid immiscibility in silicate melts with H2O, P, S, F and Cl: implications for natural magmas

Isobaric (200 MPa) experiments have been performed to investigate the effects of H₂O alone or in combination with P, S, F or Cl on liquid-phase separation in melts in the systems Fe₂SiO₄–Fe₃O₄–KAlSi₂O₆–SiO₂, Fe₃O₄–KAlSi₂O₆–SiO₂ and Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ with or without plagioclase (An₅₀). Experiments were heated in a rapid-quench internally heated pressure vessel at 1,075, 1,150 or 1,200 °C for 2 h. Experimental fO₂ was maintained at QFM, NNO or MH oxygen buffers. H₂O alone or in combination with P, S or F increases the temperature and composition range of two-liquid fields at fO₂ = NNO and MH buffers. P, S, F and Cl partition preferentially into the Fe-rich immiscible liquid. Two-liquid partition coefficients for Fe, Si, P and S correlate well with the degree of polymerization of the SiO₂-rich liquid and plot on similar but distinct power-law curves compared with equivalent anhydrous or basaltic melts. The addition of 2 wt% S to the system Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ stabilizes three immiscible melts with Fe-, FeS- and Si-rich compositions. H₂O-induced suppression of liquidus temperatures in the experimental systems, considered with the effects of pressure on the temperature and composition ranges of two-liquid fields in silicate melts, suggests that liquid-phase separation may be stable in some H₂O-rich silicate magmas at pressures in excess of 200 MPa.     

The application of lithogeochemistry in the search for unconformity-type uranium deposits, Northern Saskatchewan, Canada

Lithogeochemical-mineralogical haloes around unconformity-type uranium deposits in northern Saskatchewan can expand the size of drill targets up to fifteen times. The deposits are located at or near the unconformity between Aphebian metamorphosed basement rocks in close proximity to Archean granitoids and overlying unmetamorphosed sandstones of the Helikian Athabasca Group. Deposits studied include Key Lake (Deilmann), Midwest Lake and Eagle Point.Unconformity-type deposits are associated with broad alteration haloes in the overlying sandstones and more restricted haloes in the basement rocks. The haloes in the sandstone are localized around steeply dipping fault structures and are characterized by zones of intense leaching of specular hematite and detrital heavy mineral layers and by changes in chemistry related to clay mineral alteration and tourmalinization.Clay mineral alteration haloes are common in the sandstone and basement host rocks. Interstitial clays consist mainly of kaolinite and illite with lesser amounts of chlorite. The ratio K₂O/AI₂O₃ proved useful in delineating illite-kaolinite patterns in the sandstone and in the uppermost portions of the paleoweathering profile in basement rocks. The Midwest deposit is characterized by a broad bell-shaped zone (500 m across strike) of high K₂O/AI₂O₃ ratios (>0.18) in which illite is the dominant clay mineral. The sandstone above the Deilmann deposit, on the other hand, is characterized by silicification and kaolinitization with low K₂O/AI₂O₃ ratios (<0.04). This kaolinite cap overprints a preexisting illite zone.Anomalously high boron values are characteristic of the three deposits considered in this study. Boron anomalies are similar in extent to the anomalous clay mineral alteration haloes. Altered sandstones commonly contain aggregates of radiating magnesium-rich dravite needles within the clay matrix. The interpretation of boron patterns is problema tical however, mainly because of the detrital tourmaline component in sandstones and metamorphic tourmalines present in the Aphebian metasediments.Trace elements such as U, Ni, As and Co are generally of limited use in expanding targets in sandstone because their haloes are restricted to a few tens of metres horizon-anomalies along the steeply dipping zones of mineralization related to fault structures. Uranium (>3 ppm) does form an anomaly more than 200 metres laterally across the Midwest deposit. At the Deilmano deposit anomalous uranium dispersion is restricted to within a few metres of high grade ore.In the basement rocks, the various layers of the paleoweathering profile are geochemically overprinted up to 250 m from mineralization. Bleaching related to illitization and chloritization is associated with enrichment in K₂O, MgO, B, S, U, As, Ni and P₂O₃. The ratio Fe₂O₃/MgO is useful in delineating chloritization in the upper portion of the paleo weathering profile.Deposits with large root extensions in the Aphebian metasediments such as Eagle Point, have intense dravite-chlorite-illite alteration zones which are restricted to within a few metres of mineralization across strike. ‘Quartzite” units are alteration related. The complexity of the basement lithology inhibits the use of individual elements as alteration guides other than in the intensely altered zone. The application of multivariant techniques, element ratios and clay mineralogical work prove useful in identifying the mineralogical changes at Eagle Point.     

Application of the stable isotope composition of S04 to tracing anomalous TDS in Nose Creek,southern Alberta,Canada

Nose Creek, a tributary of the Bow River, has a TDS load that is significantly higher than the Bow River or its other tributaries. Chemical and stable isotope analyses were used to elucidate the sources of TDS in Nose Creek. Oxygen and H isotopes indicate that water is added to Nose Creek by leaky municipal pipes, via groundwater infiltration, as the creek flows through the cities of Airdrie and Calgary. Upstream of Airdrie, the high δ³⁴S of dissolved S0₄ (+ 17‰), is consistent with derivation from the local sour gas industry. The S0₄ concentration of Nose Creek doubles as the creek flows through agricultural land between Airdrie and Calgary, while the δ³⁴S composition remains a consistent 5‰. This is indicative of S derived from local soils. Within Calgary, S0₄ is derived from oxidation of reduced forms of S in the till, related to the influx of municipal groundwater.     

Low temperature abiotic formation of mesopyrophaeophorbide a from pyrophaeophorbide a under conditions simulating anoxic natural environments

Reduction of the C-3 vinyl group to an ethyl substituent is a key, yet poorly understood, event in the diagenetic pathway linking chlorophyll a to sedimentary alkyl porphyrins. Laboratory simulation experiments employing conditions that mimic those of natural anoxic environments (aqueous media, low temperature, presence of H₂S and limitation of oxygen) lead to partial conversion of the chlorophyll a derivative methyl pyrophaeophorbide a to mesopyrophaeophorbide a via reduction of the C-3 vinyl substituent mediated by H₂S. The mild conditions employed, and the apparent susceptibility of methyl pyrophaeophorbide a to reductive transformation, implies that reduction mediated by H₂S could be a widespread process occurring in anoxic depositional environments. Our findings have implications for the geological preservation of chlorins and other biological markers and provide clear evidence that reactions involving H₂S are important in the geochemical reduction of sedimenting organic matter and can occur at temperatures within the range for natural environments.