Isotopes and geochemistry in a managed aquifer recharge scheme: a case study of fresh water injection at the Damascus University Campus,Syria

A combination of stable isotopes (¹⁸O and ²H) and hydrochemistry has been applied to investigate storage processes in relation to aquifer storage and recovery (ASR) of the shallow alluvial Quaternary aquifer in Damascus basin. The stored water, entirely taken from the Figeh springs during flood periods, was injected in a single well having a brackish groundwater. Water samples were collected from four observation wells drilled in the Damascus University Campus (DUC) site during a 3‐year period (2006–2008). The injectant water, which deviates in its chemical and isotopic signatures from that of the ambient groundwater, shows that the stored water plume remains within close proximity to the injection well (IW) (<≈ 100 m). Thus, only two wells (W13 and W14) located at a distance less than 80 m from the injection point were affected by this injection. The observation wells located at longer distances from the IW (≈145 m and ≈ 600 m for wells W15 and WHz, respectively) were completely unaffected by the injection. Although most of the chemical and isotopic parameters usefully reflected the mixing process that occurs between the injectant water and ambient groundwater, the stable isotope (¹⁸O) and chloride (Cl⁻) were the most sensitive parameters that quickly reflect this signature. Using a simple mass balance, the calculated proportion of injectant water reaching the well W13 was in the range of 50–90%. This proportion was even lower (30–55%) in the case of well W14. Although the drought event prevailing during this study did not much help to inject further amounts of water, higher than the injected volume (0·2416 M m³) and also not favourable to better evaluate the fate and subsurface hydrological processes, these findings offer encouragement to continue the ASR activities, as an alternative way for better management of water resources in this basin facing intensive problems. Copyright © 2010 John Wiley & Sons, Ltd.     

Fluid generation, vein formation and the degree of fluid–rock interaction during decompression of high-pressure terranes: the Schistes Lustrés, Alpine Corsica, France

Centimetre‐ to decimetre‐wide quartz+calcite veins in schistes lustrés from Alpine Corsica were formed during exhumation at 30–40 Ma following blueschist facies metamorphism. The δ¹⁸O and δ¹³C values of the veins overlap those of the host schistes lustrés, and the δ¹⁸O values of the veins are much higher than those of other rocks on Corsica. These data suggest that the vein‐forming fluids were derived from the schistes lustrés. Fluids were probably generated by reactions that broke down carpholite, lawsonite, chlorite and white mica at 300–350 °C during decompression between c. 1400 and 800 MPa. However, the δ¹⁸O values of the veins are locally several per mil higher than expected given those of their host rocks. The magnitude of oxygen isotope disequilibrium between the veins and the host rock is inversely proportional to the δ¹⁸O value of the host rock. Additionally, calcite in some schists is in isotopic equilibrium with calcite in adjacent veins, but not with the silicate fraction of the schists. Locally, the schists are calcite bearing only within 1–20 cm of the veins. The vein‐forming fluids may have been preferentially derived from calcite‐bearing, high‐δ¹⁸O rocks that are common within the schistes lustrés and that locally contain abundant (>15%) veins. If the fluids were unable to completely isotopically equilibrate with the rocks, due to relatively rapid flow at moderate temperatures or being confined to fractures, they could form veins with higher δ¹⁸O values than those of the surrounding rocks. Alteration of the host rocks was probably inhibited by isolation of the fluid in ‘quartz‐armoured’ veins. Overall, the veins represent a metre‐ to hectometre‐scale fluid‐flow system confined to within the schistes lustrés unit, with little input from external sources. This fluid‐flow system is one of several that operated in the western Alps during exhumation following high‐pressure metamorphism.     

Evaluating sulfur dynamics during storm events for three watersheds in the northeastern USA: a combined hydrological,chemical and isotopic approach

Concerns related to climate change have resulted in an increasing interest in the importance of hydrological events such as droughts in affecting biogeochemical responses of watersheds. The effects of an unusually dry summer in 2002 had a marked impact on the biogeochemistry of three watersheds in the north‐eastern USA. Chemical, isotopic and hydrological responses with particular emphasis on S dynamics were evaluated for Archer Creek (New York), Sleepers River (Vermont) and Cone Pond (New Hampshire) watersheds. From 1 August to 14 September 2002, all three watersheds had very low precipitation (48 to 69 mm) resulting in either very low or no discharge (mean 0·015, 0·15 and 0·000 mm day^?1 for Archer Creek, Sleepers River and Cone Pond, respectively). From 15 September to 31 October 2002, there was a substantial increase in precipitation totals (212, 246 and 198 mm, respectively) with increased discharge. Archer Creek was characterized by a large range of SO₄^2? concentrations (152 to 389 µeq L^?1, mean = 273 µeq L^?1) and also exhibited the greatest range in δ³⁴S values of SO₄^2? (?1·4 to 8·8 ‰ ). Sleepers River's SO₄^2? concentrations ranged from 136 to 243 µeq L^?1 (mean = 167 µeq L^?1) and δ³⁴S values of SO₄^2? ranged from 4·0 to 9·0 ‰ . Cone Pond's SO₄^2? concentrations (126–187 µeq L^?1, mean = 154 µeq L^?1) and δ³⁴S values (2·4 to 4·3 ‰ ) had the smallest ranges of the three watersheds. The range and mean of δ¹⁸O‐SO₄^2? values for Archer Creek and Cone Pond were similar (3·0 to 8·9 ‰ , mean = 4·5 ‰ ; 3·9 to 6·3 ‰ , mean = 4·9 ‰ ; respectively) while δ¹⁸O‐SO₄^2? values for Sleepers River covered a larger range with a lower mean (1·2 to 10·0 ‰ , mean = 2·5). The difference in Sleepers River chemical and isotopic responses was attributed to weathering reactions contributing SO₄^2?. For Archer Creek wetland areas containing previously reduced S compounds that were reoxidized to SO₄^2? probably provided a substantial source of S. Cone Pond had limited internal S sources and less chemical or isotopic response to storms. Differences among the three watersheds in S biogeochemical responses during these storm events were attributed to differences in S mineral weathering contributions, hydrological pathways and landscape features. Further evaluations of differences and similarities in biogeochemical and hydrological responses among watersheds are needed to predict the impacts of climate change. Copyright © 2008 John Wiley & Sons, Ltd.     

Late glacial and Holocene environmental change in the Lake Baikal region documented by oxygen isotopes from diatom silica

We investigate late glacial and Holocene climate change recorded in Lake Baikal using the oxygen isotope composition of diatom silica (δ¹⁸O_DIAT). Evaporation from the lake is minor, and the temperature fractionations of δ¹⁸O are unable to explain variations in the δ¹⁸O_DIAT record alone. Isotopically, low meltwater input from glaciers may have some influence on δ¹⁸O_DIAT, but the assumed periods of climatic warming and wastage do not coincide with large shifts in δ¹⁸O_DIAT. There is a gradual oxygen isotope lowering from 27.0‰ to 20.6‰ over the late glacial, while, during the Holocene, δ¹⁸O_DIAT values return to relatively high values. Previous studies of the modern oxygen and hydrogen isotope composition of Lake Baikal's inputs reveal that fluvial input to the lake's North Basin are isotopically lower than fluvial input from South Basin rivers. This north–south gradient of river δ¹⁸O and δD is mainly due to the greater input from isotopically low winter precipitation in the north and isotopically higher summer precipitation in the south. As a result, the δ¹⁸O_DIAT record from Lake Baikal can at least in part be explained by varying input from these sources related to seasonal changes in precipitation. Changes in atmospheric conditions may have a role in altering seasonality and the distribution of precipitation over Lake Baikal's catchment. A feedback mechanism is well known linking higher Eurasian spring snow cover extent (ESSC) to the development of anticyclonic conditions and low precipitation the following summer in the areas south of Lake Baikal. A simultaneous increase in the importance of depleted water (snowmelt) input from the north and decreased enriched summer precipitation in the south is needed to explain depletions in δ¹⁸O of lake water and subsequently δ¹⁸O_DIAT during colder periods. The opposite of this situation is required to enrich lake water during warmer periods. The analysis of δ¹⁸O from diatom silica is a useful proxy for environmental change, especially in lakes, like Lake Baikal, where carbonates are absent or diluted. However, analysis must be based on near pure diatom samples as even trace amounts of silt can have a dominating effect on δ¹⁸O_DIAT values.     

Geochemical evidence (C,N and Pb isotopes) of recent anthropogenic impact in south‐central Chile from two environmentally distinct lake sediment records

In this paper, we compare the elemental and isotopic (C, N, Pb) geochemistry of lake sediments from two contrasted environments in south‐central Chile. The first lake, Laguna Chica de San Pedro (LCSP), is situated in the urbanised area of the Biobio Region (36°S). The second lake, Lago Puyehue (40° S), is located 400 km to the southeast of LCSP and within an Andean national park. Our aim is to identify environmental impacts associated with increasing industrial activities and land degradation during the last 150 a. In LCSP, shifts in C/N atomic ratios, δ¹³C and δ¹⁵N from 1915–1937 to the late 1980s are attributed to successive land degradation episodes in the lake watershed. Based on a Pb isotopic mixing model, we estimate that up to 20% of lead in LCSP sediments is supplied from urban atmospheric pollution. By contrast, human impact in the watershed of Lago Puyehue is very limited. We observe no change in organic geochemistry during the last 150 a and lead contamination remains lower than 5%, even during the last decades. Although contamination levels are much higher in LCSP than in Lago Puyehue, a peak in anthropogenic Pb is recorded during the same period (1974–1976) at both sites. This maximum contamination level is consistent with increased industrial activity in the vicinity of Concepción. Copyright © 2010 John Wiley & Sons, Ltd.     

Deepwater Ventilation and Stratification in the Neogene South China Sea

Combined data of physical property, benthic foraminifera, and stable isotopes from ODP Sites 1148, 1146, and 1143 are used to discuss deep water evolution in the South China Sea (SCS) since the Early Miocene. The results indicate that 3 lithostratigraphic units, respectively corresponding to 21-17 Ma, 15-10 Ma, and 10-5 Ma with positive red parameter (a*) marking the red brown sediment color represent 3 periods of deep water ventilation. The first 2 periods show a closer link to contemporary production of the Antarctic Bottom Water (AABW) and Northern Component Water (NCW), indicating a free connection of deep waters between the SCS and the open ocean before 10 Ma. After 10 Ma, red parameter dropped but stayed higher than the modern value (a*=0), the CaCO3 percentage difference between Site 1148 from a lower deepwater setting and Site 1146 from an upper deepwater setting enlarged significantly, and benthic species which prefer oxygen-rich bottom conditions dramatically decreased. Coupled with a major negative excursion of benthic δ13C at ~10 Ma, these parameters may denote a weakening in the control of the SCS deep water by the open ocean. Probably they mark the birth of a local deep water due to shallow waterways or rise of sill depths during the course of sea basin closing from south to east by the west-moving Philippine Arc after the end of SCS seafloor spreading at 16-15 Ma. However, it took another 5 Ma before the dissolved oxygen approached close to the modern level. Although the oxygen level continued to stabilize, several Pacific Bottom Water (PBW) and Pacific Deep Water (PDW) marker species rapidly increased since ~6 Ma, followed by a dramatic escalation in planktonic fragmentation which indicates high dissolution especially after ~5 Ma. The period of 5-3 Ma saw the strongest stratified deepwater in the then SCS, as indicated by up to 40% CaCO3 difference between Sites 1148 and 1146. Apart from a strengthening PDW as a result of global cooling and ice cap buildup on northern high latitudes, a deepening sea basin due to stronger subduction eastward may also have triggered the influx of more corrosive waters from the deep western Pacific. Since 3 Ma, the evolution of the SCS deep water entered a modern phase, as characterized by relative stable 10% CaCO3 difference between the two sites and increase in infaunal benthic species which prefer a low oxygenated environment. Thesubsequent reduction of PBW and PDW marker species at about 1.2 Ma and 0.9 Ma and another significant negative excursion of benthic δ13C to a Neogene minimum at ~0.9 Ma together convey a clear message that the PBW largely disappeared and the PDW considerably weakened in the Mid-Pleistocene SCS. Therefore, the true modern mode SCS deep water started to form only during the "Mid-Pleistocene climatic transition" probably due to the rise of sill depths under the Bashi Strait.     

A North-South Transect across the Central Mexican Volcanic Belt at ~100{degrees}W: Spatial Distribution, Petrological, Geochemical, and Isotopic Characteristics of Quaternary Volcanism

Within the Zitácuaro–Valle de Bravo (ZVB) regionof the central Mexican Volcanic Belt (MVB), three lava serieshave erupted during the Quaternary: (1) high-K₂O basaltic andesitesand andesites; (2) medium-K₂O basaltic andesites, andesitesand dacites; (3) high-TiO₂ basalts and basaltic andesites. Thedominant feature of the first two groups is the lack of plagioclaseaccompanying the various ferromagnesian phenocrysts (olivine,orthopyroxene, augite, and hornblende) in all but the dacites.This absence of plagioclase in the phenocryst assemblages ofthe high-K₂O and medium-K₂O intermediate lavas is significantbecause it indicates high water contents during the stage ofphenocryst equilibration. In contrast, the high-TiO₂ group ischaracterized by phenocrysts of plagioclase and olivine. Thespatial distribution of these three lava series is systematic.The southern section of the ZVB transect, 280–330 km fromthe Middle America Trench (MAT), is characterized by high-K₂Omelts that are relatively enriched in fluid-mobile elementsand have the highest ⁸⁷Sr/⁸⁶Sr ratios. Medium-K₂O basaltic andesiteand andesite lavas are present throughout the transect, butthose closest to the MAT are MgO-rich (3·5–9·4wt %) and have phenocryst assemblages indicative of high magmaticwater contents (3·5–6·5 wt % water) andrelatively low temperatures (950–1000°C). In markedcontrast, the northern section of the ZVB transect (380–480km from the MAT) has high-TiO₂, high field strength element(HFSE)-enriched magmas that have comparatively dry (< 1·5wt % magmatic water) and hot (1100–1200°C) phenocrystequilibration conditions. The central section of the ZVB transect(330–380 km from the MAT) is a transition zone and producesmoderately light rare earth element (LREE) and large ion lithophileelement (LILE)-enriched, medium-K₂O lavas with phenocryst assemblagesindicative of intermediate (1·5–3·5 wt %)water contents and temperatures. The high-K₂O series compositionsare the most enriched in LILE and LREE, with a narrow rangeof radiogenic ⁸⁷Sr/⁸⁶Sr from 0·704245 to 0·704507,¹⁴³Nd/¹⁴⁴Nd values ranging from 0·512857 to 0·512927(_Nd = 4·27–5·63), and ²⁰⁸Pb/²⁰⁴Pb valuesfrom 38·248 to 38·442, ²⁰⁷Pb/²⁰⁴Pb values from15·563 to 15·585, and ²⁰⁶Pb/²⁰⁴Pb values from18·598 to 18·688. The medium-K₂O series compositionsare only moderately enriched in the LILE and LREE, with a broaderrange of ⁸⁷Sr/⁸⁶Sr, but similar ¹⁴³Nd/¹⁴⁴Nd and ²⁰⁸Pb/²⁰⁴Pbvalues to those of the high-K₂O series. In contrast, the high-TiO₂series compositions have little enrichment in LILE or LREE andinstead are enriched in the HFSE and heavy rare earth elements(HREE). The high-TiO₂ lavas are isotopically distinct in theirlower and narrower range of ¹⁴³Nd/¹⁴⁴Nd. The isotopic variationsare believed to reflect the upper mantle magma source regionsas the low content of phenocrysts in most lavas precludes significantupper crustal assimilation or magma mixing, other than thatrepresented by the presence of quartz xenocrysts (< 2 vol.%) with rhyolitic glass inclusions, which are found in manyof these lavas. The systematic spatial variation in compositionof the three lava series is a reflection of the underlying subduction-modifiedmantle and its evolution. KEY WORDS: central Mexico; geochemistry; isotopes; Quaternary volcanism; hydrous lavas     

Intermediate Alkali-Alumino-silicate Aqueous Solutions Released by Deeply Subducted Continental Crust: Fluid Evolution in UHP OH-rich Topaz-Kyanite Quartzites from Donghai (Sulu, China)

Minerals, fluid inclusions and stable isotopes have been studiedin ultrahigh-pressure (UHP) OH-rich topaz–kyanite quartzitesfrom Hushan (west of Dongai), in southern Sulu (China). Thequartzites underwent a metamorphic evolution characterized bya peak stage (3·5 GPa and 730–820°C) with theanhydrous assemblage coesite + kyanite I, followed by an earlynear-isothermal decompression stage (2·9 GPa and 705–780°C)with growth of kyanite II, muscovite, and OH-rich topaz, andby decompression-cooling stages, represented by paragonite (1·9GPa and 700–780°C) and pyrophyllite (0·3 GPaand 400°C) on kyanite (I and II) and OH-rich topaz, respectively.These rocks may exhibit unusually low ¹⁸O and D values acquiredbefore undergoing UHP metamorphism. Five distinct fluid generationsare recognized. Type I: concentrated peak solutions rich inSi, Al, and alkalis, present within multiphase inclusions inkyanite I. Type II: CaCl₂-rich brines present during the growthof early retrograde OH-rich topaz. Type III, IV, and V: lateaqueous fluids of variable salinity, and rare CO₂ present duringamphibolite- and late greenschist-facies conditions. A numberof conclusions may be drawn from these relationships that havean effect on fluid evolution in deeply subducted continentalrocks. (1) At a pressure of about 3·5 GPa alkali–alumino-silicateaqueous solutions, with compositions intermediate between H₂Ofluid and melt (H₂O > 25 and 50 wt %) evolved from quartzites,probably generated by dehydration reactions. (2) During earlydecompression stages, at the transition from UHP to high-pressure(2·9 GPa) conditions, brines of external origin withhigher water contents (82 wt % H₂O) initiated the growth ofOH-rich topaz and muscovite. (3) The subsequent decompression,at P <2 GPa, was defined by a limited circulation of NaClaqueous fluids, and CO₂ infiltration. Overall, fluid inclusionsand stable isotopes highlight a metamorphic fluid–rockinteraction characterized by internally derived intermediateaqueous solutions at UHP, followed by infiltration of Cl-richbrines with higher water activities. KEY WORDS: ultrahigh-pressure metamorphism; OH-rich topaz; fluid inclusions; stable isotopes; supercritical liquids     

The Upper Crustal Evolution of a Large Silicic Magma Body: Evidence from Crystal-scale Rb Sr Isotopic Heterogeneities in the Fish Canyon Magmatic System, Colorado

Batholith-sized bodies of crystal-rich magmatic ‘mush’are widely inferred to represent the hidden sources of manylarge-volume high-silica rhyolite eruptive units. Occasionallythese mush bodies are ejected along with their trapped interstitialliquid, forming the distinctive crystal-rich ignimbrites knownas ‘monotonous intermediates’. These ignimbritesare notable for their combination of high crystal contents (35–55%),dacitic bulk compositions with interstitial high-silica rhyoliticglass, and general lack of compositional zonation. The 5000km³ Fish Canyon Tuff is an archetypal eruption deposit of thistype, and is the largest known silicic eruption on Earth. Ejectafrom the Fish Canyon magmatic system are notable for the limitedcompositional variation that they define on the basis of whole-rockchemistry, whereas 45 vol. % crystals in a matrix of high-silicarhyolite glass together span a large range of mineral-scaleisotopic variability (microns to millimetres). Rb/Sr isotopicanalyses of single crystals (sanidine, plagioclase, biotite,hornblende, apatite, titanite) and sampling by micromillingof selected zones within glass plus sanidine and plagioclasecrystals document widespread isotopic disequilibrium at manyscales. High and variable ⁸⁷Sr/⁸⁶Sr_i values for euhedral biotitegrains cannot be explained by any model involving closed-systemradiogenic ingrowth, and they are difficult to rationalize unlessmuch of this radiogenic Sr has been introduced at a late stagevia assimilation of local Proterozoic crust. Hornblende is theonly phase that approaches isotopic equilibrium with the surroundingmelt, but the melt (glass) was isotopically heterogeneous atthe millimetre scale, and was therefore apparently contaminatedwith radiogenic Sr shortly prior to eruption. The other mineralphases (plagioclase, sanidine, titanite, and apatite) have significantlylower ⁸⁷Sr/⁸⁶Sr_i values than whole-rock values (as much as –0·0005).Such isotopic disequilibrium implies that feldspars, titaniteand apatite are antecrysts that crystallized from less radiogenicmelt compositions at earlier stages of magma evolution, whereashighly radiogenic biotite xenocrysts and the development ofisotopic heterogeneity in matrix melt glass appear to coincidewith the final stage of the evolution of the Fish Canyon magmabody in the upper crust. Integrated petrographic and geochemicalevidence is consistent with pre-eruptive thermal rejuvenationof a near-solidus mineral assemblage from 720 to 760°C (i.e.partial dissolution of feldspars + quartz while hornblende +titanite + biotite were crystallizing). Assimilation and blendingof phenocrysts, antecrysts and xenocrysts reflects chamber-wide,low Reynolds number convection that occurred within the last10 000 years before eruption. KEY WORDS: Fish Canyon Tuff; Rb–Sr isotopes; microsampling; magmatic processes; crystal mush     

Evaluation of the Residual Mass Fractionation in High-Precision Cr Isotopic Analysis with TIMS

The Cr isotope ratios of terrestrial and extra-terrestrial materials are emerging as one of the most important tracers in geosciences. Previous studies on Cr isotopic measurements using TIMS have found that there is residual Cr isotopic fractionation between the mass-fractionation-corrected ⁵³Cr/⁵²Cr and ⁵⁴Cr/⁵²Cr ratios, which may cause an offset of obtained ratios from the reference values. The residual fractionation was thought to be caused by the evaporation of Cr-oxide species during thermal ionisation, but the mechanism by which this residual fractionation could be reduced remained unclear. Here we revisit the issue of residual fractionation and propose that this problem can be alleviated by utilising W filaments instead of conventionally used Re filaments for Cr ionisation. Using W filaments, the formation of CrO⁺ was suppressed during heating as the filament temperature was ~ 100 °C lower than when Re filaments were used. In repeated measurement of a carbonaceous chondrite, the intermediate precisions of ⁵³Cr/⁵²Cr and ⁵⁴Cr/⁵²Cr ratios in the W filament runs were two to three times better than those of the Re filament runs. Therefore, the new finding of this study will be of key importance for future studies of Cr isotopes for terrestrial and extra-terrestrial materials.