Naproxen Adsorption-Desorption in a Sandy Aquifer Matrix: Characterisation of Hysteretic Behavior at Two Different Temperature Values

Adsorption/desorption processes (sorption isotherms) of Naproxen in a sandy aquifer matrix sediment were investigated using batch tests to compare Naproxen sorption behavior at 15°C and 25°C. Both temperatures are representative of the aquifer media and environmental conditions. Adsorption was well described by linear isotherms with low sorption affinity to aquifer material (K_d of 0.4 μg kg^?1) at both temperatures (15°C and 25°C). Desorption isotherm coefficients at 15°C and 25°C were 5.0 and 4.9, respectively. Naproxen hysteresis indices were between 9.98 and 10.8, indicating that a Naproxen fraction may be irreversibly fixed in the aquifer media, being higher at 25°C (10.88) compared to 15°C, showing a decreasing trend with increasing compound concentration at 15°C. The low sorption of Naproxen leads to potential leaching to groundwater if present in irrigation water, and its prevalence in an aquifer media when directly injected in wells for groundwater recharge.     

Methanotrophic Bacteria and Facilitated Transport of Pollutants in Aquifer Material

In situ stimulation of methanotrophic bacteria has been considered as a methodology for aquifer remediation. Chlorinated aliphatic hydrocarbons such as trichloroethylene are fortuitously oxidized by the methane monooxygenase produced by methanotrophic bacteria. Experimental results are presented that indicate that both colloidal suspensions containing methanotrophic cells and the soluble extracellular polymers produced by methanotrophic cells have the potential to enhance the transport and removal of other environmental contaminants such as polynuclear aromatic hydrocarbons and transition metals in aquifer material. Three well-characterized methanotrophic bacteria were used in the experiments: Methylomonas albus BG8 (a type I methanotroph), Methylosinus trichosporium OB3b (a type II methanotroph), and Methylocystis parvus OBBP (a type II methanotroph). Isotherms were obtained for sorption of two radiolabeled pollutants, [¹⁴C] phenanthrene and ¹⁰⁹Cd, onto an aquifer sand in the presence and absence of washed cells and their extracellular polymer. Column transport experiments were performed with the washed methanotrophic cells and phenanthrene. The distribution coefficients for Cd with extracellular polymers were of the same order as that obtained with the aquifer sand, indicating that polymers from the methanotrophic bacteria could act to increase the transport of Cd in a porous medium. Polymer from BG8 significantly reduced the apparent distribution coefficient for Cd with an aquifer sand. [¹⁴C] phenanthrene also sorbed to extracellular polymer and to washed, suspended methanotrophic cells. The exopolymer of BG8 and OBBP significantly reduced the apparent distribution coefficient (K_d) for phenanthrene with aquifer sand. The distribution coefficients for phenanthrene with the methanotrophic cells were an order of magnitude greater than those previously reported for other heterotrophic bacteria. Cells of the methanotrophs also significantly reduced the apparent K_d for phenanthrene with an aquifer sand. The three strains of methanotrophs tested displayed mobility in a column of packed sand, and strain OBBP reduced the retardation coefficient of phenanthrene with an aquifer sand by 27%. These data indicate that both extracellular polymer and mobile cells of methanotrophic bacteria display a capacity to facilitate the mobility of pollutant metals and polynuclear aromatic hydrocarbons in aquifer material.     

Dispersal dynamics of groundwater bacteria

Dispersal of bacteria in saturated, porous soils can be characterized by the partitioning of cells between the aqueous and solid phases, as a result of the physical and chemical nature of the soil and water and cell surface modifications. The purpose of this work is to understand variations in partitioning as a consequence of the nutrient conditions and to use this information in mathematical models to predict the dispersal rate of bacteria in aquifer material. Two different models were used to describe dispersal: an advective-dispersive-sorptive model with a first order kinetic sink term to account for irreversible cell reactions, such as death and sorption; and a two-site reaction model, in which the retardation was assumed to be determined by two types of sites, one characterized by instantaneous equilibrium sorption reactions and the other by kinetic nonequilibrium reactions. Water-saturated sand columns were used as continuous-flow groundwater microcosms to test the models under different nutrient regimes. Two strains of indigenous groundwater bacteria were isolated from aquifer material and labelled with³H-alanine,¹⁴C-pyruvic acid,³H-glucose, and³H-adenosine for different measurements of sorption and dispersal, which were estimated from breakthrough curves. Both experimental data and model variables showed that dispersal of bacteria was a dynamic nonequilibrium process, possibly shaped by two subpopulations, one strongly, even irreversibly, adsorbing to the solid particles, and one with very slow adsorption kinetics. The cell surfaces were modified in response to the growth conditions, which was demonstrated by hydrophobic and electrostatic interaction chromatography. Cell surface hydrophobicity was about eight times higher in groundwater than in eutrophic lake water. The partition coefficient varied between 12.6 in the groundwater and 6.4 in the lake water, indicating the prime importance of hydrophobic binding for attachment in low nutrient conditions. The partitioning was also sensitive to the hydrodynamics of the system and the oxygen supply, as demonstrated by comparison of sorption in agitated test tubes, gently shaken vials, and air-flushed bottles. Sorption kinetics were demonstrated in a continuous flow cell. About 45% of a population was associated with sand particles with a continuous flow of pure groundwater and as little as 20% in lake water. However, more than 50% of the bacteria in the aqueous phase were associated with suspended material of less than 60 μm in diameter. This association may enhance dispersal for example, by size exclusion of the colloidal material in the interstitial pores.     

Biodegradation of atrazine in surface soils and subsurface sediments collected from an agricultural research farm

The purpose of the present study was to assess atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) mineralization by indigenous microbial communities and to investigate constraints associated with atrazine biodegradation in environmental samples collected from surface soil and subsurface zones at an agricultural site in Ohio. Atrazine mineralization in soil and sediment samples was monitored as ¹⁴CO₂ evolution in biometers which were amended with ¹⁴C-labeled atrazine. Variables of interest were the position of the label ([U-¹⁴C-ring]-atrazine and [2-¹⁴C-ethyl]-atrazine), incubation temperature (25°C and 10°C), inoculation with a previously characterized atrazine-mineralizing bacterial isolate (M91-3), and the effect of sterilization prior to inoculation. In uninoculated biometers, mineralization rate constants declined with increasing sample depth. First-order mineralization rate constants were somewhat lower for [2-¹⁴C-ethyl]-atrazine when compared to those of [U-¹⁴C-ring]-atrazine. Moreover, the total amount of ¹⁴CO₂ released was less with [2-¹⁴C-ethyl]-atrazine. Mineralization at 10°C was slow and linear. In inoculated biometers, less ¹⁴CO₂ was released in [2-¹⁴C-ethyl]-atrazine experiments as compared with [U-¹⁴C-ring]-atrazine probably as a result of assimilatory incorporation of ¹⁴C into biomass. The mineralization rate constants (k) and overall extents of mineralization (P _max ) were higher in biometers that were not sterilized prior to inoculation, suggesting that the native microbial populations in the sediments were contributing to the overall release of ¹⁴CO₂ from [U-¹⁴C-ring]-atrazine and [2-¹⁴C-ethyl]-atrazine. A positive correlation between k and aqueous phase atrazine concentrations (C _eq ) in the biometers was observed at 25°C, suggesting that sorption of atrazine influenced mineralization rates. The sorption effect on atrazine mineralization was greatly diminished at 10°C. It was concluded that sorption can limit biodegradation rates of weakly-sorbing solutes at high solid-to-solution ratios and at ambient surface temperatures if an active degrading population is present. Under vadose zone and subsurface aquifer conditions, however, low temperatures and the lack of degrading organisms are likely to be primary factors limiting the biodegradation of atrazine.Abbreviations C _eq solution phase atrazine concentration at equilibrium - C _s amount of atrazine sorbed - CLA [2-¹⁴C-ethyl]-atrazine - k first-order mineralization rate constant - K _d sorption coefficient - m slope - P _max maximum amount of CO₂ released - RLA [U-¹⁴C-ring]-atrazine     

Biodegradation of atrazine in surface soils and subsurface sediments collected from an agricultural research farm

The purpose of the present study was to assess atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) mineralization by indigenous microbial communities and to investigate constraints associated with atrazine biodegradation in environmental samples collected from surface soil and subsurface zones at an agricultural site in Ohio. Atrazine mineralization in soil and sediment samples was monitored as ¹⁴CO₂ evolution in biometers which were amended with ¹⁴C-labeled atrazine. Variables of interest were the position of the label ([U-¹⁴C-ring]-atrazine and [2-¹⁴C-ethyl]-atrazine), incubation temperature (25°C and 10°C), inoculation with a previously characterized atrazine-mineralizing bacterial isolate (M91-3), and the effect of sterilization prior to inoculation. In uninoculated biometers, mineralization rate constants declined with increasing sample depth. First-order mineralization rate constants were somewhat lower for [2-¹⁴C-ethyl]-atrazine when compared to those of [U-¹⁴C-ring]-atrazine. Moreover, the total amount of ¹⁴CO₂ released was less with [2-¹⁴C-ethyl]-atrazine. Mineralization at 10°C was slow and linear. In inoculated biometers, less ¹⁴CO₂ was released in [2-¹⁴C-ethyl]-atrazine experiments as compared with [U-¹⁴C-ring]-atrazine probably as a result of assimilatory incorporation of ¹⁴C into biomass. The mineralization rate constants (k) and overall extents of mineralization (P _max ) were higher in biometers that were not sterilized prior to inoculation, suggesting that the native microbial populations in the sediments were contributing to the overall release of ¹⁴CO₂ from [U-¹⁴C-ring]-atrazine and [2-¹⁴C-ethyl]-atrazine. A positive correlation between k and aqueous phase atrazine concentrations (C _eq ) in the biometers was observed at 25°C, suggesting that sorption of atrazine influenced mineralization rates. The sorption effect on atrazine mineralization was greatly diminished at 10°C. It was concluded that sorption can limit biodegradation rates of weakly-sorbing solutes at high solid-to-solution ratios and at ambient surface temperatures if an active degrading population is present. Under vadose zone and subsurface aquifer conditions, however, low temperatures and the lack of degrading organisms are likely to be primary factors limiting the biodegradation of atrazine.     

Modelling the production and transport of dissolved organic carbon in forest soils

DyDOC describes soil carbon dynamics, with a focus on dissolved organic carbon (DOC). The model treats the soil as a three-horizon profile, and simulates metabolic carbon transformations, sorption reactions and water transport. Humic substances are partitioned into three fractions, one of which is immobile, while the other two (hydrophilic and hydrophobic) can pass into solution as DOC. DyDOC requires site-specific soil characteristics, and is driven by inputs of litter and water, and air and soil temperatures. The model operates on hourly and daily time steps, and can simulate carbon cycling over both long (hundreds-to-thousands of years) and short (daily) time scales. An important feature of DyDOC is the tracking of ¹⁴C, from its entry in litter to its loss as DO¹⁴C in drainage water, enabling information about C dynamics to be obtained from both long-term radioactive decay, and the characteristic ¹⁴C pulse caused by thermonuclear weapon testing during the 1960s ("bomb carbon"). Parameterisation is performed by assuming a current steady state. Values of a range of variables, including C pools, annual DOC fluxes, and ¹⁴C signals, are combined into objective functions for least-squares minimisation. DyDOC has been applied successfully to spruce forest sites at Birkenes (Norway) and Waldstein (Germany), and most of the parameters have similar values at the two sites. The results indicate that the supply of DOC from the surface soil horizon to percolating water depends upon the continual metabolic production of easily leached humic material. In contrast, concentrations and fluxes of DOC in the deeper soil horizons are controlled by sorption processes, involving comparatively large pools of leachable organic matter. Times to reach steady state are calculated to be several hundred years in the organic layer, and hundreds-to-thousands of years in the deeper mineral layers. It is estimated that DOC supplies 89% of the mineral soil carbon at Birkenes, and 73% at Waldstein. The model, parameterised with "steady state" data, simulates short-term variations in DOC concentrations and fluxes, and in DO¹⁴C, which are in approximate agreement with observations.     

Superior Performance of Microporous Aluminophosphate with LTA Topology in Solar‐Energy Storage and Heat Reallocation

Hydrophilic porous materials are recognized as very promising materials for water‐sorption‐based energy storage and transformation. In this study, a porous, zeolite‐like aluminophosphate with LTA (Linde Type A) topology is inspected as an energy‐storage material. The study is motivated by the material's high predicted pore volume. According to sorption and calorimetric tests, the aluminophosphate outperforms all other zeolite‐like and metal‐organic porous materials tested so far. It adsorbs water in an extremely narrow relative‐pressure interval (0.10 < p /p ₀ < 0.15) and exhibits superior water uptake (0.42 g g^?1) and energy‐storage capacity (527 kW h m^?3). It also shows remarkable cycling stability; after 40 cycles of adsorption/desorption its capacity drops by less than 2%. Desorption temperature for this material, which is one of crucial parameters in applications, is lower from desorption temperatures of other tested materials by 10–15 °C. Furthermore, its heat‐pump performance is very high, allowing efficient cooling in demanding conditions (with cooling power up to 350 kW h m^?3 even at 30 °C temperature difference between evaporator and environment). On the microscopic scale, sorption mechanism in AlPO₄‐LTA is elucidated by X‐ray diffraction, nuclear magnetic resonance measurements, and first‐principles calculations. In this aluminophosphate, energy is stored predominately in hydrogen‐bonded network of water molecules within the pores.     

Evaluating Biodegradation as a Primary and Secondary Treatment for Removing RDX (Hexahydro-1,3,5-trinitro-1,3,5-triazine) from a Perched Aquifer

Ground water beneath the U.S. Department of Energy (USDOE) Pantex Plant is contaminated with the high explosive RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine). The authors evaluated biodegradation as a remedial option by measuring RDX mineralization in Pantex aquifer microcosms spiked with ¹⁴C-labeled RDX (75 g soil, 15 ml of 5 mg RDX/L). Under anaerobic conditions and constant temperature (16°C), cumulative ¹⁴CO₂ production ranged between 52% and 70% after 49 days, with nutrient-amended (C, N, P) microcosms yielding the greatest mineralization (70%). The authors also evaluated biodegradation as a secondary treatment for removing RDX degradates following oxidation by permanganate (KMnO₄) or reduction by dithionite-reduced aquifer solids (i.e., redox barriers). Under this coupled abiotic/biotic scenario, we found that although unconsumed permanganate initially inhibited biodegradation, > 48% of the initial ¹⁴C-RDX was recovered as ¹⁴CO₂ within 77 days. Following exposure to dithionite-reduced solids, RDX transformation products were also readily mineralized (> 47% in 98 days). When we seeded Pantex aquifer material into Ottawa Sand that had no prior exposure to RDX, mineralization increased 100%, indicating that the Pantex aquifer may have an adapted microbial community that could be exploited for remediation purposes. These results indicate that biodegradation effectively transformed and mineralized RDX in Pantex aquifer microcosms. Additionally, biodegradation may be an excellent secondary treatment for RDX degradates produced from in situ treatment with permanganate or redox barriers.     

Evidence for iron‐mediated anaerobic methane oxidation in a crude oil‐contaminated aquifer

In a methanogenic crude oil contaminated aquifer near Bemidji, Minnesota, the decrease in dissolved CH₄ concentrations along the groundwater flow path, along with the positive shift in δ¹³C_CH4 and negative shift in δ¹³C_DIC, is indicative of microbially mediated CH₄ oxidation. Calculations of electron acceptor transport across the water table, through diffusion, recharge, and the entrapment and release of gas bubbles, suggest that these processes can account for at most 15% of the observed total reduced carbon oxidation, including CH₄. In the anaerobic plume, the characteristic Fe(III)‐reducing genus Geobacter was the most abundant of the microbial groups tested, and depletion of labile sediment iron is observed over time, confirming that reduced carbon oxidation coupled to iron reduction is an important process. Electron mass balance calculations suggest that organic carbon sources in the aquifer, BTEX and non‐volatile dissolved organic carbon, are insufficient to account for the loss in sediment Fe(III), implying that CH₄ oxidation may also be related to Fe(III) reduction. The results support a hypothesis of Fe(III)‐mediated CH₄ oxidation in the contaminated aquifer.     

Biogeochemical processes in the groundwater discharge zone of urban streams

The influence of biogeochemical processes on nitrogen and organic matter transformation and transport was investigated for two urban streams receiving groundwater discharge during the dry summer baseflow period. A multiple lines of evidence approach involving catchment-, and stream reach-scale investigations were undertaken to describe the factors that influence pore water biogeochemical processes. At the catchment-scale gaining stream reaches were identified from water table mapping and groundwater discharge estimated to be between 0.1 and 0.8 m³ m^?2 d^?1 from baseflow analysis. Sediment temperature profiles also suggested that the high groundwater discharge limited stream water infiltration into the sediments. At the stream reach-scale, dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) concentrations were higher in stream water than in groundwater. However, DOC and DON concentrations were greatest in sediment pore water. This suggests that biodegradation of sediment organic matter contributes dissolved organic matter (DOM) to the streams along with that delivered with groundwater flow. Pore water ammonium (NH₄ ⁺) was closely associated with areas of high pore water DOM concentrations and evidence of sulfate (SO₄ ^2?) reduction (low concentration and SO₄:Cl ratio). This indicates that anoxic DOM mineralization was occurring associated with SO₄ ^2? reduction. However the distribution of anoxic mineralization was limited to the center of the streambed, and was not constrained by the distribution of sediment organic matter which was higher along the banks. Lower sediment temperatures measured along the banks compared to the center suggests, at least qualitatively, that groundwater discharge is higher along the banks. Based on this evidence anoxic mineralization is influenced by groundwater residence time, and is only measurable along the center of the stream where groundwater flux rates are lower. This study therefore shows that the distribution of biogeochemical processes in stream sediments, such as anoxic mineralization, is strongly influenced by both the biogeochemical conditions and pore water residence time.     

Impacts of Soil Organic Matter and Temperature on Sorption of Acetazolamide on Four Soils

Batch sorptions of acetazolamide (AZ) were conducted using four soils from China. Sorption of AZ was found to be impacted by OC, clay content, and soil pH, with higher k_d values for soils with higher clay content. The k_d values of SOM-removed soils are much lower than those of bulk soils. Sorption data were well fitted with a Freundlich model (r² > 0.99). Chelating with the metal ions on the surfaces of soil particles was probably involved. With pH increase, the electrostatic attraction between anionic AZ and positively charged soil surface may increase. The sorption capacity decreased when the temperature increased from 20 to 40°C, and the calculated thermodynamics parameters of ΔG₀, ΔH₀, and ΔS₀ indicated that the sorption was a non-spontaneous, physisorption, and exothermic process. Sorption coefficients (k_d) for the compound in soil were low (ranging from 0.42 to 1.19 L·kg^?1) and indicated that low level sorption of AZ with appreciable risk of ground water contamination.     

Carbon and Electron Flow in Mud and Sandflat Intertidal Sediments at Delaware Inlet, Nelson, New Zealand

An investigation of carbon and electron flow in mud and sandflat intertidal sediments showed that the terminal electron acceptor was principally sulfate and that the carbon flow was mainly to CO₂. Studies with thin layers of sediment exposed to H₂ showed that methane production accounted for virtually none of the H₂ utilized, whereas sulfate reduction accounted for a major proportion of the gas uptake. At all sampling sites except one (site B7), rates of methanogenesis were low but sulfate concentrations in the interstitial water were high (>18 mM). At site B7, the sulfate concentrations declined with depth from 32 mM at 2 cm to <1 mM at 10 cm or below, and active methanogenesis occurred in the low-sulfate zone. Sulfate-reducing activity at this site initially decreased and then increased with depth so that elevated rates occurred in both the active and nonactive methanogenic zones. The respiratory index (RI) [RI = ¹⁴CO₂/(¹⁴CO₂ + ¹⁴CH₄)] for [2-¹⁴C]acetate catabolism at site B7 ranged from 0.98 to 0.2 in the depth range of 2 to 14 cm. Addition of sulfate to sediment from the low-sulfate zone resulted in an increase in RI and a decrease in methanogenesis. At all other sites examined, RI ranged from 0.97 to 0.99 and was constant with depth. The results suggested that although methanogenesis was inhibited by sulfate (presumably through the activity of sulfate-reducing bacteria), it was not always limited by sulfate reduction.     

Migration of Naphthalene through Low Organic Content Sandy Soil Columns: Comparison of Unsaturated and Saturated Conditions

The transient transport of naphthalene through low organic matter content soil columns was investigated in different water-saturation and flow conditions. Some parameters were tested as flow rate, column height, and water saturation conditions. The soil was a clayed sandy soil from the Algerian coast near Boumerdes. The organic carbon content was 0.13% and the main mineral components were quartz (88%), clays minerals (7%) and calcite (3%). The height of the packing of the soil column (5.1 cm in diameter) varied from 15 to 40 cm. Simultaneous step injections of inert tracer (calcium chloride) and naphthalene at 10 mg L^?1 were performed. Tracer and naphthalene breakthrough curves (BTCs) were measured continuously by conductimetry and UV – 220 nm, respectively. The BTCs were simulated using the classical mixing cells in series with exchange model (MCE). In unsaturated conditions the comparison of the mean residence time of tracer BTCs with the geometrical pore volume gave us access to average water saturation along the column as a function of height. The higher the soil bed was, the higher the mean water saturation. The comparison of naphthalene distribution coefficients (K_d) in different flow conditions with the theoretical value from the Karickhoff law showed that in saturated conditions the obtained value was close to the theoretical one. In unsaturated conditions, the measured naphthalene K_d's were much lower than the theoretical value and correlated to the water saturation.     

Hymenolepis diminuta: membrane transport of glucose and beta-methylglucoside

Absorption kinetics of [¹⁴C]glucose and [β-methyl-¹⁴C]glucoside in Hymenolepis diminuta are reported. β-Methylglucoside (βMG) is a pure competitive inhibitor of [¹⁴C]glucose transport and has kinetic parameters, V_max and K_t, for transport similar to those reported for glucose. While absorbed ¹⁴C-βMG is not metabolized, transport of this glucose analog retains the general characteristics which have been established for glucose transport including: (1) Na⁺ dependence, (2) inhibition by K⁺, (3) sensitivity to phlorizin and various hexoses, (4) transport against an apparent concentration gradient, and (5) increase in worm water during accumulation. It is concluded that glucose and βMG are transported by the same system. The value of using βMG to study the mechanism of hexose transport and accumulation in H. diminuta is suggested.     

Impact of Bacterial Biomass on Contaminant Sorption and Transport in a Subsurface Soil

The objective of this study was to investigate the impact of bacterial biomass on the sorption and transport of three solutes (quinoline, naphthalene, and ⁴⁵Ca) in a subsurface soil. Miscible displacement techniques were employed to measure sorption and transport of the above compounds during steady, saturated water flow in sterile and/or bacterium-inoculated soil columns. The soil was inoculated with either a quinoline-degrading bacterium, Pseudomonas sp. 3N3A isolate, or its mutant isolate, B53, which does not degrade quinoline. In soil columns inoculated with the B53 and 3N3A isolates, quinoline sorption was reduced by about 60 and 20%, respectively. In contrast, ⁴⁵Ca sorption was minimally reduced, which indicated that biomass did not significantly alter the cation-exchange capacity of the soil. Biomass impacts on sorption were solute specific, even when the sorption mechanism for both quinoline and ⁴⁵Ca was similar. Thus, the differential response is attributed to biomass-induced changes in quinoline speciation; an increase in pH at the sorbent-water interface would result in a larger proportion of the neutral species and a decrease in sorption. Sorption of naphthalene was reduced by about 30%, which was attributed to accessibility of hydrophobic regions. Minimal biosorption of all solutes indicated negligible biofacilitated transport. Alteration of the soil surfaces upon addition of bacterial biomass reduced sorption of quinoline and naphthalene, thereby enhancing transport.     

Nitrous oxide and methane fluxes of a pristine slope mire in the German National Park Harz Mountains

Pristine peatlands covered by Histosols (bogs and fens) with high water table and a restricted oxygen (O₂) availability are known to have low emissions of nitrous oxide (N₂O) but may be a significant source for atmospheric methane (CH₄) which are both important greenhouse gases. For the first time N₂O and CH₄ fluxes of a pristine slope mire in the German Harz Mountains have been monitored. Previously reported peatlands are characterised by anaerobic conditions due to high water table levels. Slope mires monitored here receive O₂ through slope water inflow. Gas fluxes have been monitored deploying closed chamber method on a central non-forested area and a forested area at the periphery of the slope mire. By means of groundwater piezometers water table levels, ammonium and nitrate contents as well as hydro-chemical variables like oxygen content and redox potential of the mire pore water have been concurrently measured with trace gas fluxes at both monitoring sites of the slope mire. The slope mire took up small amounts of atmospheric methane at a rate of −0.02 ± 0.01 kg C ha⁻¹ year⁻¹ revealing no significant difference between the forested and non-forested site. Higher uptake rates were observed during low water table level. In contrast to pristine peatlands influx of oxygen containing pore water into slope mire does limit reduction processes and resultant CH₄ emission. N₂O fluxes of the forested and non-forested sites of the slope mire did not differ and amounted to 0.25 ± 0.44 kg N ha⁻¹ year⁻¹. Higher emissions were observed at low water table levels and during thawing periods. In spite of favourable conditions N₂O fluxes of the slope mire have been comparable to those of pristine peatlands.     

Thermodynamic analysis of nonelectrolyte sorption in plant cuticles: The effects of concentration and temperature on sorption of 4-nitrophenol

The sorption of 4-nitrophenol (4-NP) in enzymatically isolated cuticles ofLycopersicon esculentum fruits andFicus elastica leaves was studied as a function of temperature and solute concentration. Plots of the concentrations of 4-NP sorbed in the cuticle versus the equilibrium concentrations in the aqueous phase gave linear isotherms at low concentrations that tended to approach plateaus at higher sorbate concentrations ( 10 mmol·kg^-1). At low concentrations of sorbed 4-NP, cuticles have sorptive properties similar to those of organic solvents which are able to form intermolecular hydrogen bonds, while at higher concentrations their solid nature becomes apparent. During sorption of 4-NP the cutin matrix swells and new sorption sites are successively formed. The partition coefficients of 4-NP in the system cuticle/buffer are functions of temperature and concentration. At high sorbate concentrations (approx. 1 mol·kg^-1) they approach a value of 1. Different sorptive properties were observed for the cutin regions normally encrusted with soluble cuticular lipids (SCL) and those without SCL. Increasing temperature augmented the number of sorption sites in the cutin ofLycopersicon while no effect was observed withFicus. The changes of partial molar free energy (G ^o _tr), enthalpy (H ^o _tr), and entropy (S ^o _tr) for the phase transfer of 4-NP also depended on sorbate concentration: H ^o _tr and S ^o _tr were negative and steeply decreased at high sorbate concentrations. This is due to solute-solute interactions replacing solute-cutin interactions at high concentrations resulting in solid precipitates of solute within the cutin matrix. This formation of ordered solid domaines starting from a small number of nonelectrolyte molecules interacting with the cutin is proposed as a model for the intracuticular deposition of SCL.Abbreviations CM cuticular membrane - MX polymer matrix membrane - 4-NP 4-nitrophenol - SCL soluble cuticular lipids     

Functional convergence in water use of trees from different geographical regions: a meta-analysis

Functional convergence in water use of trees across species from diverse geographic locations was examined using data on tree water use parameters, with the intention of gaining an understanding on the capacity for water transport for trees with varying structural and functional traits. Wood density (ρ_w), which is reported to have a negative exponential relation with sap flow density (SFD), showed a bell-shaped curve when the daily SFD data from 101 tree species belonging to 35 angiosperm and gymnosperm families were plotted. The species came from 23 different geographical locations representing all continents. Trees were most efficient in water transport when the ρ_w was between 0.51 and 0.65 g cm^?3. When the ρ_w increased or decreased from this range, there was a gradual fall in their water transport rate as indicated by lower daily SFD. The unexpected reduction in SFD with decreasing ρ_w is explained in terms of reduced conductance in the transport pathway, which is a precaution taken by the tree for avoiding cavitation or implosion in larger conducting tubes, which is characteristic of low density wood. The development of severe leaf water potential variations, which is frequently reported in such trees, supports this notion. The SFD versus ρ_w relation has a potentially wide applicability in predicting water use by forest stands with varying ρ_w. In addition, the occurrence of a high number of tree species with ρ_w values in the range of 0.51–0.65 g cm^?3 across all continents examined points towards the importance of ρ_w in the evolutionary process as related to efficient functioning of the water transport mechanism.     

Effect of Irrigation Water Quality on the Leaching and Desorption of Phosphorous from Soil

Knowledge of the rate of decrease of nutrients from soils resulting from poor water quality application is essential for long-term planning of crop production while minimizing the impact on groundwater quality. In this study, we examined the effect of Ca²⁺ concentration of irrigation water on phosphorus (P) leaching and kinetic release in columns of sandy soil. Phosphorous sorption in the presence of CaCl₂ solutions with Ca²⁺ concentrations of 3, 5, 10, and 15 mM CaCl₂ was determined to understand the transport and leaching of P in the sandy soil. The geochemical Visual MINTEQ was used to calculate saturation indices. A considerable number of leachate samples contained P at concentrations that could cause eutrophication. Total P leached from soil due to application of different CaCl₂ solutions ranged from 1.7 to 1.8 kg ha^?1 after 20 pore volumes had passed through the soil. Comparison of the leaching experiments results with the kinetic desorption data indicated that leaching removed on average 50 times less P than cumulative P desorbed by successive extractions with different CaCl₂ solutions. Leaching in presence of different CaCl₂ solutions was controlled by rate-limited dissolution of calcium hydroxyappatite and ß-tricalcium phosphate.     

Processes regulating temporal and longitudinal variations in the chemistry of a low-order woodland stream in the Adirondack region of New York

Watershed processes influence the acid neutralizing capacity of surface waters by mediating changes in concentration of ionic solutes. Acidification of surface waters by atmospheric deposition of mineral acids and the extent to which ecosystem transformations neutralize this acidity are of particular concern. Seasonal variations in flow paths of water through soil and biological processes result in short-term changes in chemistry that may be critical to surface water ecology. In this study, we assessed longitudinal and temporal variations in the chemistry of a low-order stream, Pancake-Hall Creek, located in the west-central Adirondack region of New York. By quantifying changes in ionic solute concentration (e.g. Ca²⁺, Al^a+, SO ₄ ^2– , NO ₃ ^– ) we were able to evaluate processes responsible for short-term fluctuations in acid/base chemistry.In the headwater sites, stream water was acidic; changes in pH, acid neutralizing capacity (ANC) and Al were primarily due to seasonal variations in basic cation and NO ₃ ^– concentrations. At the downstream sites, water migrated through a large beaver impoundment and thick till resulting in higher pH, acid neutralizing capacity and basic cation concentrations, and lower concentrations of Al. Neutralization of acidity was particularly evident during the low flow summer period and coincided with retention of SO ₄ ^2– in the beaver impoundment. During the high flow non-summer (October to June) period, depressed pH and ANC, and elevated Al concentrations were observed in the downstream sites. Acidic conditions during the non-summer period were not due to the oxidation of reduced sulfur deposits (e.g. SO ₄ ^2– events) but rather the resumption of conservative SO ₄ ^2– transport through the beaver impoundment (e.g. minimal SO ₄ ^2– retention) coupled with increases in NO ₃ ^– .