Comportement thermique des géopolymères obtenus à partir d'une argile kaolinite

The aim of this work is to study the thermal behavior of geopolymers derived from kaolinite (clay). The geopolymers were characterized by various technics: Thermal analysis (DTA, TGA and dilatometer), X-ray diffractography (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Certain physical properties of the products were equally determined: linear shrinkage of curing, percentage of water absorption and compressive strength. The results obtained after drying and thermal treatment showed that the products preserved their initial forms, but showed variable colours based on the temperatures they were treated at. The products obtained at 90, 300 and 500 °C contained hydroxysodalite. The synthesis of geopolymers is not complete at 300 °C (presence of kaolinite in the material) but the products obtained are quite consolidated. The geopolymers obtained have weak values of linear shrinkage of curing (less than 0.6 %) and the compressive strength increases from room temperature (4.9 Mpa) up to 400 °C (8.9 MPa) then becomes constant between 400 and 500 °C. The combination of results demonstrates the efficiency of the temperature parameter during the synthesis of geopolymers based on kaolinite. // L’objet de ce travail est l’étude du comportement thermique des géopolymères à base d’une argile kaolinite. Les produits obtenus ont été caractérisés au moyen de plusieurs techniques : analyses thermiques (ATD, ATG et dilatométrie), microscopie électronique à balayage (MEB), analyse par diffraction de rayons X (DRX), analyse infrarouge par transformée de Fourier (IRTF). Certaines propriétés physiques des produits obtenus ont également été déterminées : retrait linéaire de cuisson, pourcentage d’absorption d’eau et résistance à la compression. Les résultats obtenus montrent qu’après le séchage et à la fin du traitement thermique, les éprouvettes des produits conservent leur forme initiale mais présentent une variation de couleur en fonction de la température de traitement. Les produits obtenus à 90, 300 et 500 °C contiennent de l’hydroxysodalite. La réaction de synthèse géopolymère n’est pas encore terminée au moins à 300 °C (présence de kaolinite dans le matériau) mais les produits obtenus sont assez consolidés. Les géopolymères obtenus présentent de faibles valeurs de retrait linéaire de cuisson (inférieure à 0,6 %) et une résistance à la compression qui augmente de la température ambiante (4,9 MPa) jusqu’à 400 °C (8,9 MPa) puis devient constante entre 400 et 500 °C. L’ensemble de ces résultats permet de mettre en exergue l’efficacité du paramètre « température » au cours de la synthèse des géopolymères à base de kaolinite.

Faulted Structures in Li Ion Exchanged NaMO2 (M=Ni(0.25)Mn(0.75))

A family of LiMO2 materials (M=Ni0.25Mn0.75) was prepared from Na1.2-xLixMO∂ precursors (0≤x≤0.6) via ion exchange. The resulting IE products were examined via XRD and compared to simulated XRD patterns produced using DIFFax to determine the defect structures resulting from the IE process. For the 0.1≤x≤0.6 materials, it is observed that there are 3 LiMO2 sub-phases with different Li contents present. As the amount of Li in the precursor increases, the amount of each phase changes resulting in a net shift to higher 2-theta; corresponding to an overall decrease in lattice parameter, approaching the theoretical values for LiMO2. Additionally, as x increases, the probability of O3-type shifting increases, most likely due to an increase in the amount O3-Li2MO3 minority phase which acts to weaken bonds in the TM layer, allowing the O3 shift to occur more easily. For the x=0 IE product, it was seen that the product had an ~O2-type structure, but with lattice parameters closer to those expected for a NaMO2 material.

Response of a First-Order Stream in Maine to Short-Term In-Stream Acidification

An experimental short-term acidification with HCl at a first-order stream in central Maine, USA was used to study processes controlling the changes in stream chemistry and to assess the ability of stream substrate to buffer pH. The streambed exerted a strong buffering capacity against pH change by ion exchange during the 6-hour acidification. Streambed substrates had substantial cation and anion exchange capacity in the pH range of 4.1 to 6.5. The ion exchange for cations and SO42- were rapid and reversible. The speed of release of cations from stream substrates was Na1+ > Ca2+ > Mg2+ > Aln+ > Be2+, perhaps relating to charge density of these cations. Ca2+ desorption dominated neutralisation of excess H+ for the first 2 hr. As the reservoir of exchangeable Ca diminished, desorption land possibly dissolution) of Al3+ became the dominant neutralising mechanism. The exchangeable land possibly soluble) reservoir of Al was not depleted during the 6-hour acidification. Sulphate adsorption during the acidification reduced the concentration of SO42- in stream water by as much as 20 mu eq L-1 (from 70 mu eq L-1). Desorption of SO42- and adsorption of base cat ions after the artificial acidification resulted in a prolongation of the pH depression. The streambed had the capacity to buffer stream water chemistry significantly during an acidifying event affecting the entire upstream catchment.

Relationships between soil nitrate desorbed from anion-exchange membranes, canopy reflectance and nitrate leaching losses from cool-season lawn turf.

Nutrient leaching studies are expensive and require expertise in water collection and analyses. Less expensive or easier methods that estimate leaching losses would be desirable. The objective of this study was to determine if anion-exchange membranes (AEMs) and reflectance meters could predict nitrate (NO3-N) leaching losses from a cool-season lawn turf. A two-year field study used an established 90% Kentucky bluegrass (Poa pratensis L.)-10% creeping red fescue (Festuca rubra L.) turf that received 0 to 98 kg N ha-1 month-1, from May through November. Soil monolith lysimeters collected leachate that was analyzed for NO3-N concentration. Soil NO3-N was estimated with AEMs. Spectral reflectance measurements of the turf were obtained with chlorophyll and chroma meters. No significant (p > 0.05) increase in percolate flow-weighted NO3-N concentration (FWC) or mass loss occurred when AEM desorbed soil NO3-N was below 0.84 µg cm-2 d-1. A linear increase in FWC and mass loss (p < 0.0001) occurred, however, when AEM soil NO3-N was above this value. The maximum contaminant level (MCL) for drinking water (10 mg L-1 NO3-N) was reached with an AEM soil NO3-N value of 1.6 µg cm-2 d-1. Maximum meter readings were obtained when AEM soil NO3 N reached or exceeded 2.3 µg cm-2 d-1. As chlorophyll index and hue angle (greenness) increased, there was an increased probability of exceeding the NO3-N MCL. These data suggest that AEMs and reflectance meters can serve as tools to predict NO3-N leaching losses from cool-season lawn turf, and to provide objective guides for N fertilization.

Chlorine stable isotopic composition of basement fluids from ODP Leg 168 sites

This paper presents chlorine stable isotope compositions (delta37Cl) of sediment pore waters collected by squeezing sediment cores from the sediment-basement interface along an East-West transect through the eastern flank of the Juan de Fuca Ridge (ODP Leg 168). These "near basement fluids" (NBF) are generally thought to be representative of low-temperature fluids circulating in the off-axis basaltic crust. The delta37Cl value of the fluid directly sampled from a flow at the base of Site 1026 (WSTP1026) is also reported. NBF display delta37Cl values between -2.09? and -0.12? relative to the Standard Mean Ocean Chloride (SMOC defined as 0?) and small variations in chlorinity (~4%). These data contrast with the homogeneity of delta37Cl values associated with highly variable chlorinities observed in high-temperature on-axis fluids [Bonifacie et al., 2005, doi:10.1016/j.chemgeo.2005.06.008]. The NBF delta37Cl values show a general decreasing trend with distance from the ridge-axis except for two fluids. When plotted against delta18O values, the delta37Cl of the NBF show two different trends. This paper discusses the possible contributions on NBF delta37Cl values of fluid-mixing, water-rock interactions and transport processes (diffusion, ion membrane filtration) that can occur in the igneous basement. However, as none of these processes can fully explain the observed delta37Cl variations, the potential effect of the sediment cover is also investigated. At site 1026, the interstitial pore fluid displays a delta37Cl signature significantly lower than that of the fluid discharge sample (-1.90? and -0.28?, respectively). This difference, demonstrated here cannot be an artifact of the sampling method, rather indicates the influence of the sediment cover on NBF delta37Cl values. The potential contributions of physical processes associated with transport/compaction (e.g., diffusion, ion membrane filtration, adsorption, ion exchange) on NBF delta37Cl values are qualitatively discussed here but require additional studies for further insights. However, this study indicates that "near basement fluids" (NBF) are not, at least for Cl isotopic compositions, necessarily as representative of fluids circulating in the basaltic crust as initially thought. These results add new constraints on Cl geodynamics and show that Cl-isotopes fractionate during low-temperature circulation of fluids in off-axis and off-margin flow contexts, but not to the extent observed for active margins. Fluids circulating at low-temperature in the magmatic and/or the sedimentary part of the oceanic crust might have played a major role on the delta37Cl evolution of seawater over geologic time.

Exchange capacity and chemical composition of Fe-Mn nodules from the Central Pacific

Constants of calcium, magnesium, zinc, cobalt, copper, and nickel exchange for sodium in iron-manganese nodules taken from different parts of the Pacific Ocean were determined under static conditions at constant ionic strength (?=0.05). These determinations revealed high capacity of nodules for sorbing the referred ions (their exchange constants range from 1.93 to 20.85). Obtained data demonstrate the major role of MnO and Fe2O3 in sorption processes in iron-manganese nodules.

Lithium and strontium isotopic compositions of sediments and pore waters at ODP Sites 152-918 and 152-919

The distribution of Li isotopes in pore waters to a depth of 1157 m below seafloor is presented for ODP Sites 918 and 919 in the Irminger Basin, offshore Greenland. Lithium isotope data are accompanied by strontium isotope ratios to decipher diagenetic reactions in the sediments which are characterized by the pervasive presence of volcanic material, as well as by very high accumulation rates in the upper section. The lowering of the 87Sr/86Sr ratio below contemporaneous seawater values indicates several zones of volcanic material alteration. The Li isotope profiles are complex suggesting a variety of exchange reactions with the solid phases. These include cation exchange with NH4+ and mobilization from sediments at depth, in addition to the alteration of volcanic matter. Lithium isotopes are, therefore, a sensitive indicator of sediment-water interaction. d6Li values of pore waters at these two sites vary between -42 and -25?. At shallow depths (<100 mbsf), rapid decreases in the Li concentration, accompanied by a shift to heavier isotopic compositions, indicate uptake of Li into alteration products. A positive anomaly of d6Li observed at both sites is coincident with the NH4+ maximum produced by organic matter decomposition and may be related to ion exchange of Li from the sediments by NH4+. In the lower sediment column at Site 918, dissolved Li increases with depth and is characterized by enrichment of 6Li. The Li isotopic compositions of both the waters and the solid phase suggest that the enrichment of Li in deep interstitial waters is a result of release from pelagic sediments. The significance of sediment diagenesis and adsorption as sinks of oceanic Li is evaluated. The maximum diffusive flux into the sediment due to volcanic matter alteration can be no more than 5% of the combined inputs from rivers and submarine hydrothermal solutions. Adsorption on to sediments can only account for 5-10% of the total inputs from rivers and submarine hot springs.

Interstitial water and sediment chemistry at DSDP Sites 87-582 and 87-584

Two trenches off Japan were explored during DSDP Leg 87. One is the Nankai Trough and the other is the Japan Trench; Site 582 is located on the floor of the former and Site 584 is situated on the deep-sea terrace of the latter. Cores from Site 582 and 584 consist mainly of hemipelagic sediments and diatomaceous silts and mudstone, respectively. In this report we analyze the chemistry of the interstitial water and sediments, as well as the sediment mineralogy. Sulfate reduction is accompanied by the production of secondary pyrite, which is rich in the sediment at both sites. Dissolved Ca concentration is relatively low and changes only slightly at both sites, probably because of the formation of carbonate with high alkalinity. Concentrations of dissolved Mg decrease with depth at Site 584. The dissolved Mg depletion probably results from the formation of Mg-rich carbonate and/or ion exchange and reaction between interstitial water and clay minerals. Higher Si/Al values are due to biogenic opal in the sediments and roughly correlate with higher values of interstitial water SiO2. Increases in dissolved Li concentrations may be related to its release from clay minerals, to advection that results from dewatering, and/or to fluid transport.

Lead 210 and silicate profiles from sediments of the equatorial Pacific and South Atlantic

Particle mixing rates have been determined for 5 South Atlantic/Antarctic and 3 equatorial Pacific deep-sea cores using excess 210Pb and 32Si measurements. Radionuclide profiles from these siliceous, calcareous, and clay-rich sediments have been evaluated using a steady state vertical advection diffusion model. In Antarctic siliceous sediments210Pb mixing coefficients (0.04-0.16 cm**2/y) are in reasonable agreement with the 32Si mixing coefficient (0.2 or 0.4 cm**2/y, depending on 32Si half-life). In an equatorial Pacific sediment core, however, the 210Pb mixing coefficient (0.22 cm**2/y) is 3-7 times greater than the 32Si mixing coefficient (0.03 or 0.07 cm**2/y). The difference in 210Pb and 32Si mixing rates in the Pacific sediments results from: (1) non-steady state mixing and differences in characteristic time and depth scales of the two radionuclides, (2) preferential mixing of fine-grained clay particles containing most of the 210Pb activity relative to coarser particles (large radiolaria) containing the 32Si activity, or (3) the supply of 222Rn from the bottom of manganese nodules which increases the measured excess 210Pb activity (relative to 226Ra) at depth and artificially increases the 210Pb mixing coefficient. Based on 32Si data and pore water silica profiles, dissolution of biogenic silica in the sediment column appears to have a minor effect on the 32Si profile in the mixed layer. Deep-sea particle mixing rates reported in this study and the literature do not correlate with sediment type, sediment accumulation rate, or surface productivity. Based on differences in mixing rate among three Antarctic cores collected within 50 km of each other, local variability in the intensity of deep-sea mixing appears to be as important as regional differences in sediment properties.

Organic compounds at DSDP Hole 90-593

Corg and Norg contents in the acid insoluble mineral fraction were studied in sediments of Site 593. Both decrease systematically from Recent to early Miocene over 425 m of carbonate facies. C/N ratios (7-11) are typically marine and indicate that residual organic matter, bound to clay minerals, was originally scavenged from the marine habitat rather than being of terrigenous origin. Variations of Corg and Norg are almost entirely controlled by rates of sedimentation, which gradually increase from Recent to early Miocene. Preliminary results of carbohydrate distribution indicate that epigenetic and diagenetic processes alter both the concentrations and the ratios of individual monomers with depth. Total carbohydrate concentrations in the samples diminish from 91 µg/g sediment at 18 m sub-bottom depth to 49 µg/g at 335 m. In contrast, sugars in the acid insoluble residue increase with depth, suggesting release of structural polysaccharides and their subsequent association with clay minerals. Ratios of arabinose to fucose, which are about 6:1 in Recent carbonaceous sediments intercepted by sediment traps, vary from 1:1 in the youngest sample to 1:2.5 in the oldest.

Interstitial water chemistry at DSDP Leg 67 Holes

Interstitial water chemistry has proved to be a sensitive indicator for early diagenetic reactions, particularly those related to organic matter oxidation. Downhole chemical variations in the pore waters from Deep Sea Drilling Project Holes 496 and 497 on the Middle America Trench slope off Guatemala are anomalous because both salinity and chlorinity show strong decreases to half the values of seawater, and d18O values become positive (maximum of about +2.5% at the bottom of the holes). These observations are explained in terms of dilution of pore waters after retrieval as a result of decomposition of the gas hydrates before removal of pore waters by shipboard squeezing techniques. In all holes, except Hole 495 (drilled in pelagic sediments), decomposition of organic matter leads to rapid sulfate depletion and subsequent methane generation. Associated with methane generation are large increases in alkalinity and dissolved ammonia. The latter component causes ion exchange reactions with clay minerals, which results in maxima in magnesium and perhaps potassium. At greater depths, as yet unidentified reactions cause the removal of magnesium. Especially in the deeper Trench Sites 499 and 500, rapid variations in calcium, magnesium, and alkalinity occur in turbidite sequences.

Strontium isotope ratios of fish teeth from ODP sites in the central North Pacific

Strontium isotopic compositions of ichthyoliths (microscopic fish remains) in deep-sea clays recovered from the North Pacific Ocean (ODP holes 885A, 886B, and 886C) are used to provide stratigraphic age control within these otherwise undatable sediments. Age control within the deep-sea clays is crucial for determining changes in sedimentation rates, and for calculating fluxes of chemical and mineral components to the sediments. The Sr isotopic ages are in excellent agreement with independent age datums from above (diatom ooze), below (basalt basement) and within (Cretaceous-Tertiary boundary) the clay deposit. The 87Sr/86Sr ratios of fish teeth from the top of the pelagic clay unit (0.7089891), indicate an Late Miocene age (5.8 Ma), as do radiolarian and diatom biostratigraphic ages in the overlying diatom ooze. The 87Sr/86Sr ratio (0.707887) is consistent with a Cretaceous-Tertiary boundary age, as identified by anomalously high iridium, shocked quartz, and sperules in Hole 886C. The 87Sr/86Sr ratios of pretreated fish teeth from the base of the clay unit are similar to Late Cretaceous seawater (0.707779-0.7075191), consistent with radiometric ages from the underlying basalt of 81 Ma. Calculation of sedimentation rates based on Sr isotopic ages from Hole 886C indicate an average sedimentation rate of 17.7 m/Myr in Unit II (diatom ooze), 0.55 m/Myr in Unit IIIa (pelagic clay), and 0.68 m/Myr in Unit IIIb (distal hydrothermal precipitates). The Sr isotopic ages indicate a period of greatly reduced sedimentation (or possible hiatus) between about 35 and 65 Ma (Eocene-Paleocene), with a linear sedimentation rate of only 0.04 m/Myr The calculated sedimentation rates are generally inversely proportional to cobalt accumulation rates and ichthyolith abundances. However, discrepancies between Sr isotope ages and cobalt accumulation ages of l0-15 Myr are evident, particularly in the middle of the clay unit IIIa (Oligocene-Paleocene).

Geochemical analysis of sediments and interstitial water in sediment cores from the North-West African continental margin and from the Central Pacific

A. Continental slope sediments off Spanish-Sahara and Senegal contain up to 4% organic carbon and up to 0.4% total nitrogen. The highest concentrations were found in sediments from water depths between 1000 and 2000 m. The regional and vertical distribution of organic matter differs significantly. Off Spanish-Sahara the organic matter content of sediment deposited during glacial times (Wuerm, Late Riss) is high whereas sediments deposited during interglacial times (Recent, Eem) are low in organic matter. Opposite distribution was found in sediments off Senegal. The sediments contain 30 to 130 ppm of fixed nitrogen. In most sediments this corresponds to 2-8 % of the total nitrogen. Only in sediments deposited during interglacial times off Spanish-Sahara up to 20 % of the total nitrogen is contained as inorganically bound nitrogen. Positive correlations of the fixed nitrogen concentrations to the amounts of clay, alumina, and potassium suggest that it is primarily fixed to illites. The amino acid nitrogen and hexosamine nitrogen account for 17 to 26 % and 1.3 to 2.4 %, respectively of the total nitrogen content of the sediments. The concentrations vary between 200 and 850 ppm amino acid nitrogen and 20 to 70 ppm hexosamine nitrogen, both parallel the fluctiations of organic matter in the sediment. Fulvic acids, humic acids, and the total organic matter of the sediments may be clearly differentiated from one another and their amino acid and hexosamine contents and their amino acid composition: a) Fulvic acids contain only half as much amino acids as humic acids b) The molar amino acid/hexosamine ratios of the fulvic acids are half those of the humic acids and the total organic matter of the sediment c) The amino acid spectra of fulvic acids are characterized by an enrichment of aspartic acid, alanine, and methionine sulfoxide and a depletion of glycine, valine, isoleucine, leucine, tyrosine, phenylalanine, lysine, and arginine compared to the spectra of the humic acids and those of the total organic matter fraction of the sediment. d) The amino acid spectra of the humic acids and those of the total organic matter fraction of the sediments are about the same with the exception that arginine is clearly enriched in the total organic matter. In general, as indicated by the amino compounds humic acids resemble closer the total organic matter composition than the low molecular fulvic acids do. This supports the general idea that during the course of diagenesis in reducing sediments organic matter stabilizes from a fulvic-like structure to humic-like structure and finally to kerogen. The decomposition rates of single aminio acids differ significantly from one another. Generally amino acids which are preferentially contained in humic acids and the total organic matter fraction show a smaller loss with time than those preferably well documented in case of the basic amino acids lysine and arginine which- although thermally unstable- are the most stable amino acids in the sediments. A favoured incorporation of these compounds into high molecular substances as well as into clay minerals may explain their relatively high "stability" in the sediment. The nitrogen loss from the sediments due to the activity of sulphate-reducing bacteria amounts to 20-40 % of the total organic nitrogen now present. At least 40 % of the organic nitrogen which is liberated by sulphate-reducing bacteria can be explained ny decomposition of amino acids alone. B. Deep-sea sediments from the Central Pacific The deep-seas sediments contain 1 to 2 orders of magnitude less organic matter than the continental slope sediments off NW Africa, i.e. 0.04 to 0.3 % organic carbon. The fixed nitrogen content of the deep-sea sediments ranges from 60 to 270 ppm or from 20 to 45 % of the total nitrogen content. While ammonia is the prevailing inorganic nitrogen compound in anoxic pore waters, nitrate predominates in the oxic environment of the deep-sea sediments. Near the sediment/water interface interstital nitrate concentrations of around 30 µg-at. N/l were recorded. These generally increase with sediment depth by 10 to 15 µg-at. NO3- N/l. This suggests the presence of free oxygen and the activity of nitrifying bacteria in the interstitial waters. The ammonia content of the interstitial water of the oxic deep-sea sediments ranges from 2 to 60 µg-at. N/l and thus is several orders of magnitude less than in anoxic sediments. In contrast to recorded nitrate gradients towards the sediments/water interface, there are no ammonia concentration gradients. However, ammonia concentrations appear to be characteristic for certain regional areas. It is suggested that this regional differentiation is caused by ion exchange reactions involving potassium and ammonium ions rather than by different decomposition rates of organic matter. C. C/N ratios All estimated C/N ratios of surface sediments vary between 3 and 9 in the deep-sea and the continental margin, respectively. Whereas the C/N ratios generally increase with depth in the sediment cores off NW Africa they decrease in the deep-sea cores. The lowest values of around 1.3 were found in the deeper sections of the deep-sea cores, the highest of around 10 in the sediments off NW Africa. The wide range of the C/N ratios as well as their opposite behaviour with increasing sediment depth in both the deep-sea and continental margin sediment cores, can be attributed mainly to the combination of the following three factors: 1. Inorganic and organic substances bound within the latticed of clay minerals tend to decrease the C/N ratios. 2. Organic matter not protected by absorption on the clay minerals tends to increase C/N ratios 3. Diagenetic alteration of organic matter by micro-organisms tends to increase C/N ratios through preferential loss of nitrogen The diagenetic changes of the microbially decomposable organic matter results in both oxic and anoxic environments in a preferential loss of nitrogen and hence in higher C/N ratios of the organic fraction. This holds true for most of the continental margin sediments off NW Africa which contain relatively high amounts of organic matter so that factors 2 and 3 predominate there. The relative low C/N ratios of the sediments deposited during interglacial times off Spanish-Sahara, which are low in organic carbon, show the increasing influence of factor 1 - the nitrogen-rich organic substances bound to clay minerals. In the deep-sea sediments from the Central Pacific this factor completely predominates so that the C/N rations of the sediments approach that of the substance absorbed to clay minerals with decreasing organic matter content. In the deeper core sections the unprotected organic matter has been completely destroyed so that the C/N ratios of the total sediments eventually fall into the same range as those of the pure clay mineral fraction.

Ion concentrations and extracelluar pH of Calanus glacialis in Billefjorden, Svalbard

Arctic shelf zooplankton communities are dominated by the copepod Calanus glacialis. This species feeds in surface waters during spring and summer and accumulates large amounts of lipids. Autumn and winter are spent in dormancy in deeper waters. Lipids are believed to play a major role in regulating buoyancy, however, they cannot explain fine-tuning of the depth distribution. To investigate whether ion exchange processes and acid-base regulation support ontogenetic migration as suggested for Antarctic copepods, we sampled C. glacialis in monthly intervals for 1 yr in a high-Arctic fjord and determined cation concentrations and the extracellular pH (pHe) in its hemolymph. During the winter/spring transition, prior to the upward migration of the copepods, Li+ ions were exchanged with cations (Na+, Mg2+, and Ca2+) leading to Li+ concentrations of 197 mmol/L. This likely decreased the density and promoted upward migration in C. glacialis. Our data thus suggest that Li+ has a biological function in this species. Ion and pHe regulation in the hemolymph were not directly correlated, but the pHe revealed a seasonal pattern and was low (5.5) in winter and high (7.9) in summer. Low pHe during overwintering might be related to metabolic depression and thus, support diapause.