Simultaneous biological organic matter and nutrient removal in an anaerobic/anoxic/oxic (A<Superscript>2</Superscript>O) moving bed biofilm reactor (MBBR) integrated system

In the present study, the performance of three moving bed biofilm reactors (MBBRs) has been evaluated in series with anaerobic/anoxic/oxic (A²O) units for simultaneous removal of organic matter and nutrients (nitrogen and phosphorous) from a synthetic wastewater with characteristics similar to those of a typical municipal wastewater. Response surface methodology based on central composite design was used to investigate the effects of nitrate recycle ratio, hydraulic retention time (HRT), and influent chemical oxygen demand (COD) on the organic and nutrient removal and optimization process. The optimized values of influent COD, HRT, and R were 462 mg/L, 10 h, and 3.52, respectively. The predicted and observed values at optimized conditions were 92.8% and 93 ± 1.3%, 84.3% and 84 ± 1.3%, 71.7% and 68 ± 1.6% for COD, TN, and TP removals and 100 and 97 ± 1.2 mL/g for sludge volume index, respectively. After that, the influent COD, TN, and TP were increased to 550, 48, and 12 mg/L, respectively, to partly simulate the organics and nutrient variations of real wastewater treatment plants. The COD, TN, and TP removals were 91 ± 1.3, 82 ± 1.1, and 71 ± 0.8%, respectively. The influent COD, TN, and TP were increased again to 650, 56, and 14 mg/L, respectively. After this phase, the COD, TN, and TP removals were 90 ± 0.8, 80 ± 1.2, and 70 ± 1.0%, respectively. Obtained results indicated the good stability of the optimized system and the ability of MBBRs to remain stable at influent organics and nutrient variations. The ratio of attached volatile solids to mixed liquor volatile suspended solids was 1.90 ± 0.10, 2.07 ± 0.09, and 2.25 ± 0.14 in phases 1, 2, and 3, respectively. These high ratios indicate that the microorganisms had favored the attached growth to the suspended growth within the whole operation time.     

High-pressure synthesis,long-term stability of single crystals of diboron trioxide,B<Subscript>2</Subscript>O<Subscript>3</Subscript>, and an empirical electronic polarizability of <Superscript>[3]</Superscript>B<Superscript>3+</Superscript>

Single crystals of B₂O₃ are needed for the precise determination of the refractive indices used to calculate the electronic polarizability α of 3-coordinated boron. The α(B) values in turn are used to predict mean refractive indices of borate minerals. Since the contribution of boron to the total polarizability of a mineral is very low, the synthetic compound B₂O₃ represents an ideal model system because of its high molar content of boron. Millimeter-sized crystals were synthesized at 1 GPa in a piston-cylinder apparatus. The samples were heated above the liquidus (800 °C), subsequently cooled at 15 °C/h to 500 °C and finally quenched. The refractive indices were determined by the immersion method using a microrefractometer spindle stage. The refractive indices n _o = 1.653 (3) and n _e = 1.632 (3) correspond to a total polarizability for B₂O₃ of α = 4.877 Å³. These values were used to determine the electronic polarizability of boron of α(B) = 0.16 Å³. Although the surface of the B₂O₃ crystals was coated with a hydrous film immediately after being exposed to air, its bulk crystallinity is retained for a period of at least 2 months.     

Elimination of natural organic matter by electrocoagulation using bipolar and monopolar arrangements of iron and aluminum electrodes

The aim of this research was to evaluate the efficiency of electrocoagulation (EC) for the removal of natural organic matter (NOM) by using iron (Fe) and aluminum (Al) electrodes. The effects of several operational parameters such as initial pH (3–10), time of electrolysis (5–30 min), initial concentration of organic matter (10–50 mg NOM/L), current density (0.25–1.25 mA/cm²), type of electrode material (n = 4, 2 sides × 11 cm × 10 cm, wall thickness = 2 mm, distance between each electrode = 5 mm), and type of connection of electrodes (bipolar and monopolar configurations) were explored for the removal of NOM from synthetic humic acid solution in a 2 L laboratory-scale EC cells (A _s/V = 0.110 cm^?1). The optimum conditions for the process were identified as pH = 3 and 7, electrolysis time = 20 and 10 min for Fe and Al electrodes, respectively. Using both electrodes at current density = 0.25 mA/cm² and initial concentration of organic matter = 50 mg/L, a NOM removal efficiency of almost 100% could be achieved in the bipolar mode. Based on the optimum conditions, specific reactor electrical energy consumptions were 14.90 kWh/kg Al (or 0.092 kWh/m³) and 2.88 kWh/kg Fe (or 0.11 kWh/m³). Specific electrode consumptions were obtained to be 0.0062 and 0.0382 kg/m³, and operating costs of the EC system were preliminary estimated at 0.057 and 0.119 $/m³ for Al and Fe electrodes, respectively.     

Continuous process study on simultaneous nitrification–denitrification of high ammoniacal nitrogen load wastewater in aerobic–anoxic sequencing bioreactors

The study focused on the feasibility of high NH₄ ⁺–N (400–600 mg/L) and COD load at two different hydraulic retention times (HRTs = 36 and 24 h) in two identical aerobic–anoxic sequencing bioreactors which were constructed in series in a single system using a specifically designed single biomass containing autotrophic nitrifying and heterotrophic denitrifying bacteria. Internal recirculation of synthetic wastewater from one tank to other was not carried out like the conventional aerobic–anoxic processes. Cycles of 15 days under sequences of aerated and non-aerated periods of three hour each were repeated during each continuous flow experiment conducted. Sodium bicarbonate and sodium acetate were selected as the appropriate inorganic and organic carbon sources. The results showed that the HRT may not affect the simultaneous nitrification and denitrification processes. Average nitrification ratio was obtained to be above 20 mg/L NH₄ ⁺–N/h daily. Results of 90 days’ operation also showed high removal efficiencies of ammoniacal nitrogen of about 83% daily. The main advantage of this process includes efficient ammoniacal nitrogen removal without separated aerobic and anoxic tanks, decrease operating costs due to the lesser oxygen concentration requirement in the bioreactors.     

Principal component analysis on sewage sludge characteristics and its implication to dewatering performance with Fe<Superscript>2+</Superscript>/persulfate-skeleton builder conditioning

Sludge samples taken from different sources and times may have different characteristics that could affect dewatering performance. In this study, 20 sludge samples from five wastewater treatment plants and different seasons in 1 year were characterized. Pearson correlation analysis indicated that solid content (SC), total suspended solid (TSS), polysaccharides and proteins contents had positive correlations with the capillary suction time (CST), whereas volatile suspended–solid/total suspended solid (VSS/TSS) exhibited negative correlations with CST. Moreover, no correlations between CST and specific resistance to filtration were found among these different sludge samples. The principal component analysis confirmed that only two group variables could represent most of the sludge characteristic parameters. The first set of variables represents the particulate nature of the biotic factors (SC, VSS/TSS, SCOD, TSS, polysaccharides and proteins), and the second set is the pH. CST could not be a reasonable indicator of dewaterability in sludge deep dewatering by Fe²⁺/S₂O₈ ^2?-phosphogypsum composite conditioning. Furthermore, the results of diaphragm filter press dewatering showed that initial SC and VSS/TSS were the most dominant sludge characteristics affecting the solid content of dewatered cake (R _p = 0.610, p = 0.016; R _p = ?0.838, p = 0.000, respectively) with Fe²⁺/S₂O₈ ^2?-phosphogypsum composite conditioning. Results from this study suggest that dewatering performance is predictable by sludge characteristics parameters for Fe²⁺/S₂O₈ ^2?-phosphogypsum conditioning.     

Deducing the source and composition of rare earth mineralising fluids in carbonatites: insights from isotopic (C,O, <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) data from Kangankunde,Malawi

Carbonatites host some of the largest and highest grade rare earth element (REE) deposits but the composition and source of their REE-mineralising fluids remains enigmatic. Using C, O and ⁸⁷Sr/⁸⁶Sr isotope data together with major and trace element compositions for the REE-rich Kangankunde carbonatite (Malawi), we show that the commonly observed, dark brown, Fe-rich carbonatite that hosts REE minerals in many carbonatites is decoupled from the REE mineral assemblage. REE-rich ferroan dolomite carbonatites, containing 8–15 wt% REE₂O₃, comprise assemblages of monazite-(Ce), strontianite and baryte forming hexagonal pseudomorphs after probable burbankite. The ⁸⁷Sr/⁸⁶Sr values (0.70302–0.70307) affirm a carbonatitic origin for these pseudomorph-forming fluids. Carbon and oxygen isotope ratios of strontianite, representing the REE mineral assemblage, indicate equilibrium between these assemblages and a carbonatite-derived, deuteric fluid between 250 and 400 °C (δ¹⁸O + 3 to + 5‰_VSMOW and δ¹³C ? 3.5 to ? 3.2‰_VPDB). In contrast, dolomite in the same samples has similar δ¹³C values but much higher δ¹⁸O, corresponding to increasing degrees of exchange with low-temperature fluids (< 125 °C), causing exsolution of Fe oxides resulting in the dark colour of these rocks. REE-rich quartz rocks, which occur outside of the intrusion, have similar δ¹⁸O and ⁸⁷Sr/⁸⁶Sr to those of the main complex, indicating both are carbonatite-derived and, locally, REE mineralisation can extend up to 1.5 km away from the intrusion. Early, REE-poor apatite-bearing dolomite carbonatite (beforsite: δ¹⁸O + 7.7 to + 10.3‰ and δ¹³C ?5.2 to ?6.0‰; ⁸⁷Sr/⁸⁶Sr 0.70296–0.70298) is not directly linked with the REE mineralisation.     

A novel continuous magnetic nano-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/perlite fixed bed reactor for catalytic wet peroxide oxidation of dyes: reactor structure

In the present work, a continuous catalytic wet peroxide oxidation fixed bed reactor was employed to treat a simulated wastewater sample with malachite green dye, as a contaminant. Natural perlite particle-supported nano-Fe₃O₄ catalyst was used as a fixed bed inside a reactor, and it was immobilized by a persistent magnetic field. The range of (perlite) particle sizes was from 100 to 1000 nm. The effects of various operating parameters, including temperature of the reactor, pH, initial hydrogen peroxide concentration and initial dye concentration, were investigated on the percentage removal of malachite green dye. Load of catalyst of 2 g and volumetric flow rate of 1 L/h were selected for all the tests. Maximum malachite green degradation was 99.5 ± 0.3%. This removal percentage was attained at temperature of 80 °C, pH = 6, initial dye concentration of 6 mg/L and initial hydrogen peroxide concentration of 100 mg/L. The process was isotherm, and the catalyst showed high catalytic activity in the steady-state condition. The loss of catalyst was less than 0.3%.     

Degradation of polyvinyl alcohol in aqueous solutions using UV-365 nm/S2O8 2− process

This investigation evaluates the effectiveness of UV-365 nm/S₂O₈ ^2? process in degrading polyvinyl alcohol in aqueous solutions. The effects of pH, Na₂S₂O₈ dosage, and temperature on the degradation efficiency of polyvinyl alcohol were studied. Under acidic conditions, the degradation efficiency of polyvinyl alcohol exceeded that under alkaline conditions. Additionally, a higher Na₂S₂O₈ dosage and a higher temperature were associated with a higher degradation efficiency of polyvinyl alcohol. The degradation rates of polyvinyl alcohol followed a pseudo-first-order kinetic model. Moreover, the observed degradation rate coefficient increased from 0.0078 to 0.4081 min^?1 when the temperature was increased from 10 to 55 °C. Also, the activation energy estimated using the observed degradation rate coefficients and the Arrhenius equation was 64 kJ/mol. At UV-365 nm, pH 3, an Na₂S₂O₈ dosage of 0.06 g/L, a temperature of 55 °C, and an initial polyvinyl alcohol concentration of 20 mg/L, around 100 % of polyvinyl alcohol was degraded, indicating that UV-365 nm/S₂O₈ ^2? process has great potential in degrading polyvinyl alcohol in aqueous solutions.     

Fluoride contamination of groundwater in parts of eastern India and a preliminary experimental study of fluoride adsorption by natural haematite iron ore and synthetic magnetite

Incidence of high fluoride (F^?) in groundwater (>1.5 mg/L) in two tribal belts of eastern India, one around Chukru in the Palamau district of Jharkhand and the other around Karlakot in the Nuapada district of Odisha, has been studied. The maximum concentration of F^? in groundwater from dug wells and tube wells is 10.30 mg/L in Chukru and 4.62 mg/L in Karlakot. The groundwaters are mildly alkaline with pH ranges of 7.52–8.22 and 7.33–8.20 in Chukru and Karlakot, respectively. The F^? concentration is positively correlated with pH, electrical conductivity and SO₄ ^2? in both areas. The high F^? in groundwater resulted mainly from dissolution of biotite and fluorapatite in quartzofeldspathic gneiss. The ionic dominance pattern (in meq/L) is mostly in the order Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ among cations and HCO₃ ^? > SO₄ ^2? > < Cl^? > F^? among anions in the Karlakot groundwater. Preliminary adsorption experiments were conducted on natural haematite iron ore and synthetic magnetite to evaluate their potential for F^? removal from water. Effects of different parameters such as contact time, pH, adsorbent dose and initial F^? concentration on the adsorption capacity of these materials were investigated. Strong dependence of F^? removal on pH was observed for both the adsorbents. With natural haematite iron ore, the maximum F^? removal of 66 % occurred at an initial pH of 3.2 for a solution with F^? concentration of 3 mg/L, adsorbent dose of 7 g/L and overnight contact time. The haematite iron ore was observed to increase the pH of the F^? solution. Adsorption equilibrium was not achieved with this adsorbent even after a contact time of 45.2 h. In the case of synthetic magnetite, 84 % F^? removal was achieved after 2 min of contact time for a solution with F^? concentration of 6 mg/L, adsorbent dose of 10 g/L and initial pH of 7. The results indicate high potential of both natural haematite iron ore and synthetic magnetite as adsorbents of F^? in water.     

Single-crystal EPR and DFT studies of a [BO<Subscript>4</Subscript>]<Superscript>0</Superscript> center in datolite: electronic structure,formation mechanism and implications

A natural datolite CaBSiO₄(OH) (Bergen Hill, NJ, USA), before and after gamma-ray irradiation (up to ~70 kGy), has been investigated by single-crystal and powder electron paramagnetic resonance (EPR) spectroscopy from 10 to 295 K. EPR spectra of gamma-ray-irradiated datolite show the presence of a boron-associated oxygen hole center (BOHC) and an atomic hydrogen center (H⁰), both of which grow with increasing radiation dose. The principal g and A(¹¹B) values of the BOHC at 10 K are: g ₁ = 2.04817(3), g ₂ = 2.01179(2), g ₃ = 2.00310(2), A ₁ = −0.401(7) mT, A ₂ = −0.906(2) mT, A ₃ = −0.985(2) mT, with the orientations of the g ₁ and A ₁ axes approximately along the B–OH bond direction. These experimental results suggest that the BOHC represents hole trapping on the hydroxyl oxygen atom after the removal of the proton (i.e. a [BO₄]⁰ center): via a reaction O₃BOH → O₃BO^· + H⁰, where · denotes the unpaired electron. Density functional theory (DFT) calculations (CRYSTAL06, B3PW, all-electron basis sets, and 1 × 2 × 2 supercell) support the proposed structural model and yield the following ¹¹B hyperfine coupling constants: A ₁ = −0.429 mT, A ₂ = −0.901 mT, A ₃ = −0.954 mT, in excellent agreement with the experimental results. The [BO₄]⁰ center undergoes the onset of thermal decay at ~200°C and is completely annealed out at 375°C but can be restored readily by gamma-ray irradiation. Isothermal annealing experiments show that the [BO₄]⁰ center exhibits a second-order thermal decay with an activation energy of 0.96 eV. The confirmation of the [BO₄]⁰ center (and its formation from the O₃BOH precursor) in datolite has implications for not only understanding of BOHCs in alkali borosilicate glasses but also their applications to nuclear waste disposal.     

Dissolution sequestration mechanism of CO<Subscript>2</Subscript> at the Shiqianfeng saline aquifer in the Ordos Basin,northwestern China

This study focused on the target injection layers of deep saline aquifers in the Shiqianfeng Fm. in the Carbon Capture and Sequestration (CCS) Demonstration Projects in the Ordos Basin, northwestern China. The study employed a combination method of experiments and numerical simulation to investigate the dissolution mechanism and impact factors of CO₂ in these saline aquifers. The results showed (1) CO₂ solubility in different types of water chemistry were shown in ascending order: MgCl₂-type water < CaCl₂-type water < Na₂SO₄-type water < NaCl-type water < Na₂CO₃-type water < distilled water. These results were consistent with the calculated results undertaken by TOUGHREACT with about 5% margin of error. CO₂ solubility of Shiqianfeng Fm. saline was 1.05 mol/L; (2) compared with distilled water, the more complex the water’s chemical composition, the greater the increase in HCO₃ ^?concentration. While the water’s composition was relatively simple, the tested water’s HCO₃ ^?concentrations were in close accord with the calculated value undertaken by the TOUGHREACT code, and the more complex the water’s composition, the poorer the agreement was, probably due to the complex and unstable HCO₃ ^? complicating matters when in an aqueous solution system including both tested HCO₃ ^?concentration and calculated HCO₃ ^?concentration; (3) the CO₂ solubility in the saline at the temperature conditions of 55 °C and 70 °C were 1.17 and 1.02 mol/L. When compared with the calculated value of 1.20 and 1.05 mol/L, they were almost the same with only 1 and 3% margin of error; concentrations of HCO₃ ^? were 402.73 mg/L (0.007 mol/L) and 385.65 mg/L (0.006 mol/L), while the simulation results were 132.16 mg/L (0.002 mol/L) and 128.52 mg/L (0.002 mol/L). From the contrast between the tested data and the calculated data undertaken by the TOUGHREACT code, it was shown that TOUGHRACT code could better simulate the interaction between saline and CO₂ in the dissolution sequestration capacity. Therefore, TOUGHREACT code could be used for the inter-process prediction of CO₂ long-term geological storage of CO₂; (4) The Ca²⁺ concentration and SO₄ ^2?concentration in saline water had less effect on the solubility of CO₂ and HCO₃ ^?concentration. In addition, TDS and pH values of saline affected not only the solubility of CO₂, but also the conversion of CO₂ to HCO₃ ^? due to that they can affect the activity and acid-base balance. So in fact, we just need to consider that the TDS and pH values are main impact factors in the dissolution sequestration capacity of CO₂ geological sequestration in deep saline aquifers.     

A poly-ε-caprolactone based biofilm carrier for nitrate removal from water

Nitrate removal from water has been accomplished by heterotrophic biofilms using organic carbon as a source of reducing power. To overcome the natural limitation in organic carbon in water, a poly-ε-caprolactone based biofilm carrier that serves simultaneously as a biofilm carrier and as a source of organic carbon was developed and tested in the present work. The feasibility of the new biofilm carrier for nitrate removal from water was evaluated in a packed bed reactor. The combination of size and structure provided a carrier element having high surface area and void volume, 1,170 m²/m³ and 67 %, respectively. A maximum denitrification rate of 4.4 mg N–NO₃ ^?/(L.h) (9.2 mg N–NO₃ ^?/(m².h)) was achieved in the packed bed reactor at 20 °C and pH 7.0. Main advantages of the biofilm carrier developed in the present work are its mechanical stability in water even after biofilm formation and controlled release of organic carbon by enzymatic reactions. The proposed biotechnology to remove nitrate from groundwater is robust and easy to operate.     

Optimization of aqueous methylparathion biodegradation by Fusarium sp in batch scale process using response surface methodology

Biotreatment of methylparathion (O,O-dimethyl-O-4-nitrophenyl phosphorothioate) was studied in aqueous mineral salts medium containing fungal culture to demonstrate the potential of the pure culture (monoculture) of Fusarium sp in degrading high concentration of methylparathion. A statistical Box–Behnken design of experiments was performed to evaluate the effects of individual operating variables and their interactions on the methylparathion removal with initial concentration of 1,000 mg/L as fixed input parameter. A full factorial Box–Behnken design of experiments was used to construct response surfaces with the removal, the extent of methylparathion biodegradation, removal of chemical oxygen demand and total organic carbon, and the specific growth rate as responses. The temperature (X ₁), pH (X ₂), reaction time (X ₃) and agitation (X ₄) were used as design variables. The result was shown that experimental data fitted with the polynomial model. Analysis of variance showed a high coefficient of determination value of 0.99. The maximum biodegradation of methylparathion in terms of the methylparathion removal (Y ₁), chemical oxygen demand removal (Y ₂) and total organic carbon removal (Y ₃) were found to be 92, 79.2 and 57.2 % respectively. The maximum growth in terms of dry biomass (Y ₄) was 150 mg/L. The maximum biodegradation corresponds to the combination of following factors of middle level of temperature (X ₁ = 30 °C), pH (X ₂ = 6.5), agitation (X ₄ = 120 rpm) and the highest level of reaction time (X ₃ = 144 h). The removal efficiency of methylparathion biodegradation was achieved 92 %. It was observed that optimum biotreatment of methylparathion can be successfully predicted by response surface methodology.     

Influence of dissolved oxygen concentration and aeration time on nitrite accumulation in partial nitrification process

This study investigated the influence of dissolved oxygen concentration and aeration time on nitrification and nitrite accumulation in an attempt to optimize the recently developed biological-partial-nitritation process for the treatment of strong nitrogen wastewaters. Investigation of dissolved oxygen concentration on ammonium and nitrite oxidation was carried out in a batch reactor. The dissolved oxygen concentration of 0.5 mg O₂/L inhibited both ammonium as well as nitrite oxidation, while increase of dissolved oxygen concentration to ～1 mg O₂/L increased the ammonium oxidation rate and was comparable to that at higher dissolved oxygen concentrations. Experiments were carried out in a sequencing batch reactor for more than 100 days to investigate the influence of aeration time on nitrite accumulation. The dissolved oxygen concentration was controlled at ～1.0 mg O₂/L (in the range of 0.8–1.5 mg/L) during the aeration stage, and volatile suspended solid was maintained at 2.0 g/L while temperature and pH were 30±1°C and 8.3±0.1, respectively. In a typical cycle, complete nitrification occurred at aeration time longer than 6 h. When the aeration time was reduced to 4 h., ～80 % of partial nitritation was achieved. With a further reduction in aeration time to 3 h., nearly 1:1 nitrite/ammonium ratio was yielded. This result revealed that for the reactor design, aeration time determined by feasibility experiments must be considered based on the nitrogen strength in wastewater and biomass concentration in the reactor with dissolved oxygen concentration of ～1.0 mg O₂/L for satisfactory partial nitrification with subsequent processes such as anaerobic ammonium oxidation.     

Influence of hydraulic retention time on heterotrophic biomass in a wastewater moving bed membrane bioreactor treatment plant

Wastewater treatment using moving bed membrane bioreactor technology was tested with real urban wastewater at a pilot plant, combining moving bed treatment as a biological process with hybrid biomass (suspended and fixed) and the advantages of a membrane separation system. The evolution of the kinetic constants of the hybrid biomass and organic matter removal were studied in a pilot plant under different operational conditions, by varying hydraulic retention time (HRT), mixed liquor suspended solids (MLSS) and temperature, and considering the attached biomass of the carrier and the dispersed biomass of the flocs to reproduce real treatment conditions. The rates of organic matter removal were 97.73 ± 0.81 % of biochemical oxygen demand (BOD₅), 93.44 ± 2.13 % of chemical oxygen demand (COD), 94.41 ± 2.26 % of BOD₅ and 87.62 ± 2.47 % of COD using 24.00 ± 0.39 and 10.00 ± 0.07 h of HRT, respectively. The influence of the environmental variables and operational conditions on kinetic constants was studied; it was determined that the most influential variable for the decay coefficient for heterotrophic biomass was HRT (0.34 ± 0.14 and 0.31 ± 0.10 days^?1 with 10.00 ± 0.07 and 24.00 ± 0.39 h of HRT, respectively), while for heterotrophic biomass yield, this was temperature (0.61 ± 0.04 and 0.52 ± 0.06 with 10.00 ± 0.07 and 24.00 ± 0.39 h of HRT, respectively). The results show that introducing carriers in an MBR system provides similar results for organic matter removal, but with a lower concentration of MLSS.     

Spatial and Temporal Variability of Benthic Respiration in a Scottish Sea Loch Impacted by Fish Farming: A Combination of In Situ Techniques

The effects of fish farm activities on sediment biogeochemistry were investigated in Loch Creran (Western Scotland) from March to October 2006. Sediment oxygen uptake rates (SOU) were estimated along an organic matter gradient generated from an Atlantic salmon farm using a combination of in situ techniques: microelectrodes, planar optode and benthic chamber incubations. Sulphide (H₂S) and pH distributions in sediment porewater were also measured using in situ microelectrodes, and dissolved inorganic carbon (DIC) fluxes were measured in situ using benthic chambers. Relationships between benthic fluxes, vertical distribution of oxidants and reduced compounds in the sediment were examined as well as bacterial abundance and biomass. Seasonal variations in SOU were relatively low and mainly driven by seasonal temperature variations. The effect of the fish farm on sediment oxygen uptake rate was clearly identified by higher total and diffusive oxygen uptake rates (TOU and DOU, respectively) on impacted stations (TOU: 70 ± 25 mmol O₂ m^?2 day^?1; DOU: 70 ± 32 mmol O₂ m^?2 day^?1 recalculated at the summer temperature), compared with the reference station (TOU: 28.3 ± 5.5 mmol O₂ m^?2 day^?1; DOU: 21.5 ± 4.5 mmol O₂ m^?2 day^?1). At the impacted stations, planar optode images displayed high centimetre scale heterogeneity in oxygen distribution underlining the control of oxygen dynamics by small-scale processes. The organic carbon enrichment led to enhanced sulphate reduction as demonstrated by large vertical H₂S concentration gradients in the porewater (from 0 to 1,000 μM in the top 3 cm) at the most impacted site. The impact on ecosystem functions such as bioirrigation was evidenced by a decreasing TOU/DOU ratio, from 1.7 in the non-impacted sediments to 1 in the impacted zone. This trend was related to a shift in the macrofaunal assemblage and an increase in sediment bacterial population. The turnover time of the organic load of the sediment was estimated to be over 6 years.     

Effects of strong network modifiers on Fe<Superscript>3+</Superscript>/Fe<Superscript>2+</Superscript> in silicate melts: an experimental study

The effect of CaO, Na₂O, and K₂O on ferric/ferrous ratio in model multicomponent silicate melts was investigated in the temperature range 1450–1550?°C at 1-atm total pressure in air. It is demonstrated that the addition of these network modifier cations results in an increase of Fe³⁺/Fe²⁺ ratio. The influence of network modifier cations on the ferric/ferrous ratio increases in the order Ca?<?Na?<?K. Some old controversial conceptions concerning the effect of potassium on Fe³⁺/Fe²⁺ ratio in simple model liquids are critically evaluated. An empirical equation is proposed to predict the ferric/ferrous ratio in SiO₂–TiO₂–Al₂O₃–FeO–Fe₂O₃–MgO–CaO–Na₂O–K₂O–P₂O₅ melts at air conditions.     

Argon retention properties of silicate glasses and implications for <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar age and noble gas diffusion studies

Sized aggregates of glasses (47–84 wt% SiO₂) were fused from igneous-derived cohesive fault rock and igneous rock, and step-heated from ~400 to >1,200 °C to obtain their ³⁹Ar diffusion properties (average E=33,400 cal mol^?1; D _o=4.63×10^?3 cm² s^?1). At T<~1,000 °C, glasses containing <~69 wt% SiO₂ and abundant network-forming cations (Ca, Fe, Mg) reveal moderate to strong non-linear increases in D and E, reflecting structural modifications as the solid transitions to melt. Extrapolation of these Arrhenius properties down to typical geologic T-t conditions could result in a 1.5 log₁₀ unit underestimation in the diffusion rate of Ar in similar materials. Numerical simulations based upon the diffusion results caution that some common geologic glasses will likely yield ⁴⁰Ar/³⁹Ar cooling ages rather than formation ages. However, if cooling rates are sufficiently high, ambient temperatures are sufficiently low (e.g., <65–175 °C), and coarse particles (e.g., radius (r) >~1 mm) are analyzed, glasses with compositions similar to ours may preserve their formation ages.     

Using multiple chemical indicators to characterize and determine the age of groundwater from selected vents of the Silver Springs Group, central Florida, USA

The Silver Springs Group, Florida (USA), forms the headwaters of the Silver River and supports a diverse ecosystem. The 30 headwater springs divide into five subgroups based on chemistry. Five selected spring vents were sampled in 2007 to better understand the contaminant sources and groundwater flow system. Elevated nitrate-N concentrations (>0.8 mg/L) in the five spring vents likely originate from inorganic (fertilizers) and organic sources, based on nitrogen and oxygen isotope ratios of nitrate. Evidence for denitrification in the Lost River Boil spring includes enriched δ¹⁵N and δ¹⁸O, excess N₂ gas, and low dissolved O₂ concentrations (<0.5 mg/L). Multiple age-tracer data (SF₆, ³H, tritiogenic ³He) for the two uppermost springs (Mammoth East and Mammoth West) indicate a binary mixture dominated by recent recharge water (mean age 6–7 years, and 87–97% young water). Tracer data for the three downstream spring vents (Lost River Boil, Catfish Hotel-1, and Catfish Conventional Hall-1) indicate exponential mixtures with mean ages of 26–35 years. Contamination from non-atmospheric sources of CFCs and SF₅CF₃ precluded their use as age tracers here. Variations in chemistry were consistent with mean groundwater age, as nitrate-N and dissolved O₂ concentrations were higher in younger waters, and the Ca/Mg ratio decreased with increasing mean age.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ¹³C_CARB value of +2.2 ‰. The major groundwater geochemical composition is HCO₃ ^? > Ca²⁺ > Mg²⁺. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg²⁺/Ca²⁺ ratios and low Na⁺, K⁺ and Si values. Trace element and nutrient concentrations (SO₄ ^2?, NO₃ ^?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO₂ was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ¹⁸O_H2O), hydrogen (δD_H2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ¹⁸O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ¹³C_DIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.