Beschreibung: The chemical and isotope compositions of slab dehydration fluids from convergent margins have been theorized by many authors who have adopted several approaches. A direct collection of natural water is possible only in an oceanic environment, despite several difficulties in estimating the deepest component due to the mixing with seawater or hydrothermal fluids from the ridge. Accordingly, the study of melt inclusions is a valuable alternative. However, the latter mainly represents high temperature/pressure conditions in deep magmatic or metamorphic settings. Here, we present new H, O, Li and B isotope along with a revision of previously published chemical data from a potential natural example of slab dehydration water, sampled in a forearc region and affected by low-temperature metamorphism and serpentinization processes (Aqua de Ney, Northern California). Its extreme composition challenges the understanding of its origin and deep temperature, but this work is a further step on a topic of increasing interest for several scientists from different academic disciplines.

Beschreibung: In this study, the experimental results from long-term solubility experiments up to 1146 days on micro-crystalline neodymium hydroxide, Nd(OH) 3 (micro-cr), in high ionic strength solutions at 298.15 K under well-constrained conditions, are presented. Hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH) 3 (micro-cr) without artificial adjustment with addition of either an acid or a base, preventing the possibility of phase change that could be induced especially by addition of a base. Such an experimental design also provides the information about the hydrogen ion concentrations buffered by the dissolution of Nd(OH) 3 , which is currently lacking. The solubility data produced in this work, applicable to geological repositories in high ionic strength environments, are compared with the solubilities of Am(OH) 3 (s) predicted by using the Waste Isolation Pilot Plant (WIPP) thermodynamic model. The predicted values for Am(OH) 3 (s) are in good agreement with the experimental values for Nd(OH) 3 (micro-cr) obtained in this work. Our experimental data indicate that the pH m (negative logarithm of hydrogen ion concentration on a molal scale) buffered by dissolution of Nd(OH) 3 (micro-cr) ranges from ~ 9.5 to ~ 9.9. As the equilibrium constant for amorphous neodymium hydroxide, Nd(OH) 3 (am), is useful for several fields, the equilibrium constant regarding the dissolution of Nd(OH) 3 (am) for the following reaction, $$ {\text{Nd}}\left( {\text{OH}} \right)_{3} \left( {\text{am}} \right) + 3{\text{H}}^{ + } = {\text{Nd}}^{3 + } + 3{\text{H}}_{2} {\text{O}}\left( {\text{l}} \right) $$ is also obtained by evaluating the experimental data in a wide range of ionic strengths from the literature by using the WIPP thermodynamic model. The \( \log_{10} K_{{{\text{s}}0}}^{0} \) at 298.15 K for the above reaction obtained in this work is 16.85 ± 0.20 (2 σ ), which is similar to, but slightly lower than, the values in the literature evaluated in the low ionic strength range. This value can be applied to amorphous americium hydroxide, Am(OH) 3 (am), using Nd(III) as an analog to Am(III).

Beschreibung: Polycyclic aromatic hydrocarbons (PAHs) released from diverse sources passing through water column carry information into the sediment where they can be used to assess the environmental status of an ecosystem over specified geologic time frame. The vertical distributions of PAHs in two recent sediment cores (RS and RC, 30 cm long) from Refome Lake, South–South Nigeria, were investigated using gas chromatography–mass spectrometry in order to evaluate their sources and historical trends of deposition over the last ca. century. The total PAHs (TPAHs—sum of parent and retene) concentrations ranged from 66.99 ng/g dry weight (dw) at the middle layer of RC core (RC3 10–15 cm) to 182.24 ng/g dw at the near-bottom layer of RS core (RS5 20–25 cm) with a mean of 102.21 ± 24.32 ng/g. The elevated TPAH level at the near-bottom layer of the RS core, corresponding to geologic time-frame ca. 1930–1947, coincided with the period of inhabitation of the European settlers along the lake’s catchments when utilization of coal and/or coal products for domestic/recreational activity was at its peak. A decline in TPAH levels up-cores thereafter reflected the periods of gradual evacuation of inhabitants of the lake area hinterland following the departure of the White after the Nigerian independence in 1960. Evaluation of PAH category according to ring size coupled with data from specific molecular ratios revealed inputs dominated by wood/coal combustion with a moderate contribution from petrochemical/liquid fossil fuel exhaust emissions and a minor diagenetic sources. Principal component analysis result not only distinctively separated RS from RC core samples but also revealed that the RS samples were more impacted by wood/coal combustion emissions than the RC, while liquid fossil fuel exhaust emission dominated the RC over the RS samples. Although short-range eolian transport did play a role in the delivery of PAHs to the lake, localization of source contamination was more important.

Beschreibung: In application at the Zlatna gold mining area (Apuseni Mountains, Romania), the correlation of water isotopes and geochemical data were successfully used to assess the genetic relationships between surface running water, groundwater and mine water, as well as to evaluate the mining effects on the surrounding environment after the cessation of mining operations. The majority of mine water sources display pH values between 4 and 5, i.e. acid mine water. The mine water characterized by slightly higher pH values (~6) interacts with ophiolitic rocks which have high pH buffering capacity. The neutral mine water (pH ~ 7) does not come into direct contact with reactive minerals, either because it is discharged from an exploration adit or because of the complete leaching of pyrite and other sulphides in old abandoned mining works. The later also shows low levels of heavy metals concentrations. Calcium is the dominant cation in mine water and in the majority of surface running water and groundwater sources, indicating the same mechanisms of mineralization. All mine water sources are \(\text{SO}_{4}^{2 - }\) type and show very high \(\text{SO}_{4}^{2 - }\) concentrations (6539 mg/l mean value). Surface and groundwater sources are classified either as \(\text{SO}_{4}^{2 - }\) or as \(\text{HCO}_{3}^{ - }\) type water. Linear correlation between δD and δ 18 O values indicates that all water sources belong to the meteoric cycle. Low δD and δ 18 O values of mine water (δD 〈 −70‰; δ 18 O 〈 −10‰) suggest snow melt and high-altitude precipitations as the main source of recharge. The mine water is less affected by the seasonal variation of temperature. In most cases, the variations in isotopic composition are within narrow limits (less than 1‰ for both δD and δ 18 O), and this result suggests well-mixed underground systems. Elevated concentration of sulphates, Zn and Fe in mine waters are the main issues of concern. For the study area, no relevant contamination of springs or phreatic water by mine water was revealed. On the contrary, surface running water is contaminated by mine water, and the negative effects of acid mine drainage occur mainly in the summer months when the flow of the surface running water decreases.

Beschreibung: Nitrogen inputs to Great Salt Lake (GSL), located in the western USA, were quantified relative to the resident nitrogen mass in order to better determine numeric nutrient criteria that may be considered at some point in the future. Total dissolved nitrogen inputs from four surface-water sources entering GSL were modeled during the 5-year study period (2010–2014) and ranged from 1.90 × 10 6 to 5.56 × 10 6  kg/year. The railroad causeway breach was a significant conduit for the export of dissolved nitrogen from Gilbert to Gunnison Bay, and in 2011 and 2012, net losses of total nitrogen mass from Gilbert Bay via the Causeway breach were 9.59 × 10 5 and 1.51 × 10 6  kg. Atmospheric deposition (wet + dry) was a significant source of nitrogen to Gilbert Bay, exceeding the dissolved nitrogen load contributed via the Farmington Bay causeway surface-water input by 〉100,000 kg during 2 years of the study. Closure of two railroad causeway culverts in 2012 and 2013 likely initiated a decreasing trend in the volume of the higher density Deep Brine Layer and associated declines in total dissolved nitrogen mass contained in this layer. The large dissolved nitrogen pool in Gilbert Bay relative to the amount of nitrogen contributed by surface-water inflow sources is consistent with the terminal nature of GSL and the predominance of internal nutrient cycling. The opening of the new railroad causeway breach in 2016 will likely facilitate more efficient bidirectional flow between Gilbert and Gunnison Bays, resulting in potentially substantial changes in nutrient pools within GSL.

Beschreibung: This work assessed both the fractionation and the seasonal mobility variations of Ga and In in systems impacted by acidic thermal waters. This was accomplished by performing thermodynamic calculations using the PHREEQC algorithm and by assessing the activity of acidophilic iron-oxidizing bacteria. The pH of the Kusatsu thermal waters in Gunma Prefecture, central Japan, is rapidly increased following the addition of a lime suspension. After an abrupt pH increase, under which conditions free ions of Ga and In and their complexes with Cl − and SO 4 2− exist only in negligible quantities, the majority of dissolved Ga and In is removed by sorption onto suspended hydrous ferric oxides (HFOs). These HFOs are then transported to an artificial lake without significant sedimentation along the river. Subsequently, the suspended HFOs settle out and are added to sediments without significant fractionation between Ga and In. The Tamagawa thermal waters in Akita Prefecture, northeast Japan, are also treated with lime. However, complete neutralization requires mixing with some tributary streams, leading to a gradual downstream increase in pH. Dissolved Ga is, in general, sorbed by HFOs in upstream areas, leading to wide dispersal of Ga across the entire watershed. In comparison, In is transported to the lake inlet predominantly as a Cl − complex species without significant removal along the river, with the majority being precipitated in an artificial lake, where Cl − concentrations are too low to form stable complex species with In, and thus, dissolved In is sorbed by HFOs. As a result, In is effectively concentrated within downstream lakebed sediments, whereas Ga is dispersed along the river. Seasonal variations in Ga mobility within the Tamagawa field between snowmelt and low-flow seasons are primarily controlled by pH, because hydrolysis reactions of these metals, which are related to sorption reactions, tend to occur in the upstream regions in the snowmelt season. However, under warmer conditions, HFO formation preferably occurs due to the activity of acidophilic iron-oxidizing bacteria. Thus, under similar pH variations, dissolved Ga is more effectively removed by HFOs during warmer seasons. On the contrary, because HFOs are abundantly formed in low-flow season, even under colder conditions, before In hydrolysis reaction starts to occur, In mobility is less affected by water temperature and then bacterial activity.

Beschreibung: In the boreal and subarctic zone, the moss and peat interactions with rainwater and snowmelt water in shallow surface ponds control the delivery of dissolved organic matter (DOM) and metal to the rivers and further to the Arctic Ocean. The transformation of peat and moss leachate by common aquatic microorganisms and the effect of temperature on DOM mineralization by heterotrophs remain poorly known that does not allow predicting the response of boreal aquatic system to ongoing climate change. We used experimental approach to quantify the impact of boreal aquatic bacteria P. reactans , and two culturable bacteria extracted from a thaw lake of the permafrost zone (Bolshezemelskaya tundra, NE Europe): Iodobacter sp. and cyanobacterial associate dominated by order Chroococcales ( Synechococcus sp). The interaction of these bacterial cultures with nutrient-free peat and moss leachate was performed in order to (1) quantify the impact of temperature (4, 25 and 45 °C) on peat leachate processing by heterotrophs; (2) compare the effect of heterotrophic bacteria and cyanobacterial associate on moss and peat leachate chemical composition, and (3) quantify the DOC and metal concentration change during cyanobacterial growth on leachate from frozen and thawed peat horizon and moss biomass. The efficiency of peat DOM processing by two heterotrophs was not modified by temperature rise from 4 to 45 °C. The DOC concentration decreased by a factor of 1.6 during 3 days of moss leachate reaction with Iodobacters sp. or cyanobacterial associate at 25 °C. The SUVA 245 increased twofold suggesting an uptake of non-aromatic DOM by both microorganisms. The growth of cyanobacteria was absent on peat leachate but highly pronounced on moss leachate. This growth produced tenfold decrease in P concentration, a factor of 1.5–2.0 decrease in DOC, a factor of 4 and 100 decrease in Fe and Mn concentration, respectively. Adsorption of organic and organo-mineral colloids on bacterial cell surface was more important factor of element removal from organic leachates compared to intracellular assimilation and/or Fe oxyhydroxide precipitation. Overall, we demonstrate highly conservative behavior of peat leachate compared to moss leachate in the presence of culturable aquatic bacteria, a lack of any impact of heterotrophs on peat leachate and their weak impact on moss leachate. A very weak temperature impact on DOM processing by heterotrophs and lack of difference in the biodegradability of DOM from thawed and frozen peat horizons contradict the current paradigm that the warming of frozen OM and its leaching to inland waters will greatly affect microbial production and C cycle. Strong decrease in concentration of P, Fe and Mn in the moss leachate in the presence of cyanobacterial associate has straightforward application for understanding the development of thermokarst lakes and suggests that, in addition to P, Fe and Mn may become limiting micronutrients for phytoplankton bloom in thermokarst lakes.

Beschreibung: With the continuous rise in CO 2 emissions, the pH of seawater may decrease extensively in the coming centuries. Deep-sea environments are more vulnerable to decreasing pH since sediments in deep oceans below the carbonate compensation depth (CCD) are often completely devoid of carbonate particles. In order to assess the potential risk of heavy metal release from deep-sea deposits, the mobility of elements from ferromanganese (Fe–Mn) nodules and pelagic clays was examined by means of leaching experiments using phosphate buffer solutions ranging in pH from 7.1 to 8.6 (NBS scale). With decreasing pH, the results showed an enhanced leaching of elements such as Li, B, Mg, Si, Sc, Sr, Ba, Tl, and U, but a reduced leaching of V, Cu, Mo, Cd, and W. Elements in leachates originate mainly from exchangeable fractions, and tend to be affected by sorption–desorption processes. Concentrations of most elements did not exceed widely used international water quality criteria, indicating that changes in pH caused by future ocean acidification may not increase the risk of heavy metal release during deep-sea nodule mining operations.

Beschreibung: Oil samples collected from the Pearl River Mouth Basin (PRMB) were analyzed using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC × GC-TOFMS). High abundances of compounds in the 2α-methylhopane series were observed and accurately quantified. Although the 2α-methylhopane series can be a prominent biomarker in the oil and source rock samples, it has generally been used less than non-methylated hopanes. In this study, the 2α-MHI [C 31 2α-methylhopane × 100/(C 31 2α-methylhopane + C 30 -αβ-hopane) (%)] ranges from 0.81 to 5.77% and 9.06 to 23.93% in Enping Formation- and Wenchang Formation-derived oils, respectively. The high abundance of the 2α-methylhopane series in Wenchang Formation-derived oils is attributed to anoxygenic phototrophs. The relevant 2α-methylhopane parameters showed correlations with C 30 -4-methyl steranes/∑C 29 steranes, Pr/Ph and bicadinane-T/C 30 -αβ-hopane. Furthermore, the 2α-methylhopane series are rich in middle-deep lacustrine environments as well as marine sedimentary environment. The results indicated that the 2α-methylhopane series could be used as effective biomarkers to distinguish oils derived from different source rocks, as well as to enlarge the PRMB biomarker assemblages, which is beneficial to the evaluation of petroleum resources.

Beschreibung: Dissolution kinetic experiments of actinolite in water were performed using a flow-through reactor at temperatures from 20 to 400 °C and 23.5±0.5 MPa. The results indicate that the steady-state release rates of the different elements of actinolite vary with temperature. Generally, Ca, Mg, Fe, and Al dissolve more quickly than Si at temperatures from 20 °C to near 300 °C, but slower from 300 to 400 °C. The Si release rate increases with temperatures from 20 to 300 °C and then decreases from 300 to 400 °C. Si release rate reaches the maximum at 300 °C. Amorphous Si-rich surface layers occur at temperature 〈300 °C. Hydrations of actinolite are relatively faster, and proton–metal exchange reactions are weakening across the critical point. M i -rich (Fe, Ca, Mg) and Si-deficient surface layers form at temperatures ≥300 °C. XPS, TEM, and SEM observations indicate that the hydrated silicate occurred at surface as temperature 〉300 °C. Water property variations within the critical region strongly affect the dissolution rates and the modification of surface.