Copper removal by algae Gelidium, agar extraction algal waste and granulated algal waste: kinetics and equilibrium

Biosorption of copper ions by an industrial algal waste, from agar extraction industry has been studied in a batch system. This biosorbent was compared with the algae Gelidium itself, which is the raw material for agar extraction, and the industrial waste immobilized with polyacrylonitrile (composite material). The effects of contact time, pH, ionic strength (IS) and temperature on the biosorption process have been studied. Equilibrium data follow both Langmuir and Langmuir-Freundlich models. The parameters of Langmuir equilibrium model were: q(max)=33.0mgg(-1), K(L)=0.015mgl(-1); q(max)=16.7mgg(-1), K(L)=0.028mgl(-1) and q(max)=10.3mgg(-1), K(L)=0.160mgl(-1) respectively for Gelidium, algal waste and composite material at pH=5.3, T=20 degrees C and IS=0.001M. Increasing the pH, the number of deprotonated active sites increases and so the uptake capacity of copper ions. In the case of high ionic strengths, the contribution of the electrostatic component to the overall binding decreases, and so the uptake capacity. The temperature has little influence on the uptake capacity principally for low equilibrium copper concentrations. Changes in standard enthalpy, Gibbs energy and entropy during biosorption were determined. Kinetic data at different solution pH (3, 4 and 5.3) were fitted to pseudo-first-order and pseudo-second-order models. The adsorptive behaviour of biosorbent particles was modelled using a batch reactor mass transfer kinetic model, which successfully predicts Cu(II) concentration profiles.     

The kinetics of the cytochrome-c-azurin redox equilibrium

A preliminary analysis of the temperature-jump relaxation spectrum of the cytochrome-c-azurin redox system from $\text{Pseudomonas fluorescens}$ revealed two chemical relaxation times. These are explained in terms of two association steps and an electron transfer between the associated species.     

The kinetics of algal photoadaptation in the context of vertical mixing

The responses of phytoplankton to turbulent motions in the surfacemixed layer can be measured to estimate the rate of verticalmixing. If the time scale for the response (photoadaptation)is shorter than that for vertical mixing, phytoplankton willexhibit a vertical gradient associated with adaptation to ambientlight, whereas if mixing occurs with a time scale shorter thanthat of photoadaptation, the surface mixed layer will be uniformwith respect to the photoadaptive parameter. To examine thephysiological bases for a model of vertical mixing and photoadaptation,we grew the marine diatom Thalassiosira pseudonana (clone 3H)at three photon flux densities and subjected the cultures toreciprocal light shifts, measuring physiological and chemicalchanges over the following 10 h. Several parameters, easilymeasured in nature and attributable primarily to phytoplankton,responded to fluctuating light on different time scales. Aftercultures were exposed to relatively bright light, both the initialslope of the photosynthesis-irradiance curve and in vivo fluorescencewere depressed on a time scale of less than an hour. Photosyntheticcapacity was also reduced transiently, but recovered over manyhours to a high level characteristic of an adapted state. First-orderkinetics (the current model of choice for describing photoadaptation)reasonably described the rapid responses of phytoplankton tobright light, but other parameters (i.e. cellular chemical compositionand photosynthetic capacity) changed as a result of unbalancedgrowth and required much longer to adapt from low to high lightas compared to from high to low light. A logistic model of thisadaptation is presented. The model suggests that hysteresisof adaptation during vertical mixing may have important consequences.The vertical distributions of photoadaptive properties in mixedlayers not only reveal the rate of vertical mixing, but showhow phytoplankton integrate environmental fluctuations.     

Soil carbon dioxide partial pressure and dissolved inorganic carbonate chemistry under elevated carbon dioxide and ozone

Global emissions of atmospheric CO₂ and tropospheric O₃ are rising and expected to impact large areas of the Earths forests. While CO₂ stimulates net primary production, O₃ reduces photosynthesis, altering plant C allocation and reducing ecosystem C storage. The effects of multiple air pollutants can alter belowground C allocation, leading to changes in the partial pressure of CO₂ (pCO₂) in the soil , chemistry of dissolved inorganic carbonate (DIC) and the rate of mineral weathering. As this system represents a linkage between the long- and short-term C cycles and sequestration of atmospheric CO₂, changes in atmospheric chemistry that affect net primary production may alter the fate of C in these ecosystems. To date, little is known about the combined effects of elevated CO₂ and O₃ on the inorganic C cycle in forest systems. Free air CO₂ and O₃ enrichment (FACE) technology was used at the Aspen FACE project in Rhinelander, Wisconsin to understand how elevated atmospheric CO₂ and O₃ interact to alter pCO₂ and DIC concentrations in the soil. Ambient and elevated CO₂ levels were 360±16 and 542±81 l l^–1, respectively; ambient and elevated O₃ levels were 33±14 and 49±24 nl l^–1, respectively. Measured concentrations of soil CO₂ and calculated concentrations of DIC increased over the growing season by 14 and 22%, respectively, under elevated atmospheric CO₂ and were unaffected by elevated tropospheric O₃. The increased concentration of DIC altered inorganic carbonate chemistry by increasing system total alkalinity by 210%, likely due to enhanced chemical weathering. The study also demonstrated the close coupling between the seasonal ¹³C of soil pCO₂ and DIC, as a mixing model showed that new atmospheric CO₂ accounted for approximately 90% of the C leaving the system as DIC. This study illustrates the potential of using stable isotopic techniques and FACE technology to examine long- and short-term ecosystem C sequestration.     

The effect of land use on dissolved organic carbon and nitrogen uptake in streams

1. Agricultural and urban land use may increase dissolved inorganic nitrogen (DIN) concentrations in streams and saturate biotic nutrient demand, but less is known about their impacts on the cycling of organic nutrients. To assess these impacts we compared the uptake of DIN (as ammonium, NH₄⁺), dissolved organic carbon (DOC, as acetate), and dissolved organic nitrogen (DON, as glycine) in 18 low‐gradient headwater streams in southwest Michigan draining forested, agricultural, or urban land‐use types. Over 3 years, we quantified uptake in two streams in each of the three land‐use types during three seasons (spring, summer and autumn). 2. We found significantly higher NH₄⁺ demand (expressed as uptake velocity, V_f) in urban compared to forested streams and NH₄⁺V_f was greater in spring compared to summer and autumn. Acetate V_f was significantly higher than NH₄⁺ and glycine V_f, but neither acetate nor glycine V_f were influenced by land‐use type or season. 3. We examined the interaction between NH₄⁺ and acetate demand by comparing simultaneous short‐term releases of both solutes to releases of each solute individually. Acetate V_f did not change during the simultaneous release with NH₄⁺, but NH₄⁺V_f was significantly higher with increased acetate. Thus, labile DOC V_f was not limited by the availability of NH₄⁺, but NH₄⁺V_f was limited by the availability of labile DOC. In contrast, neither glycine nor NH₄⁺V_f changed when released simultaneously indicating either that overall N‐uptake was saturated or that glycine and NH₄⁺ uptake were controlled by different factors. 4. Our results suggest that labile DOC and DON uptake can be equivalent to, or even higher than NH₄⁺ uptake, a solute known to be highly bioreactive, but unlike NH₄⁺ uptake, may not differ among land‐use types and seasons. Moreover, downstream export of nitrogen may be exacerbated by limitation of NH₄⁺ uptake by the availability of labile DOC in headwater streams from the agricultural Midwestern United States. Further research is needed to identify the factors that influence cycling of DOC and DON in streams.     

The kinetics of calcium uptake by roots

Summary Barley leaves extracted 35 min after a 15-min pulse of 10^-6 M ¹⁴C-labelled cis,trans-(±)-abscisic acid (ABA) showed very little breakdown of the ABA. Leaves extracted 2 h after a 30-min pulse of 10^-5 M labelled ABA showed at least 34% degradation of the hormone. The pattern of degradation was very similar for leaves kept in either light or darkness following the labelling pulse, and the products formed resembled those described in tomato fruit and bean axes. No detectable isomerization to the physiologically inactive trans,trans-(±)-ABA isomer occurred in these leaves during the 2-h period. ABA-induced stomatal closure is partially reduced 30 min after the pulse. The reversal cannot be attributed to catabolism of the hormone and must be explained by removal of the hormone into storage sites where it cannot act on the stomata.     

The use of adjacency analysis for quantifying landscape changes

Abstract

The analysis of landscape changes in space and time plays an important role in landscape ecology. Analyzing landscape dynamics through time may be crucial for identifying historical and current processes that shape the actual landscapes and for developing predictive landscape models for ecosystem management and conservation. In this view, the propensity of land cover patches to change is at least partially related to the nature of their contact types. The interactions of a given patch with adjacent land cover types affect both land use exploitation by humans and vegetation dynamics. The aim of this paper is to use patch boundary dynamics for describing the landscape changes that occurred in the Lepini Mountains (central Italy) during 1954 – 2000. Results show an increase in landscape complexity in the Mediterranean land units and a corresponding decrease in landscape complexity in the Temperate land units. This differential trend is due to a complex, human-driven temporal dynamics of Mediterranean ecosystems that generates heterogeneity as opposed to a diffuse landscape abandonment in the Temperate region that leads to a more homogeneous boundary structure.     

Bacterial metabolism of algal extracellular carbon

Measurements of microbial utilization of extracellular organic carbon (EOC) released by phytoplankton commonly consider only EOC fractions subject to rapid uptake. Questions remain whether other EOC fractions are metabolized, what portion is labile, and with what assimilation efficiency this carbon substrate is utilized. ¹⁴C-EOC was prepared by incubation of the natural mixed planktonic community from an oligotrophic lake with H¹⁴CO₃ in the light. ¹⁴C-EOC which was not rapidly removed by heterotrophs remained in solution and was isolated by filtration. This residual EOC was inoculated with lake microheterotrophs in laboratory microcosms, and utilization kinetics were determined through long-term assays of cumulative ¹⁴CO₂ production. Time-courses for ¹⁴CO₂ production were consistent for all assays and were well described by a deterministic mixed-order degradation model. On twelve sampling occasions, from 29% to 76% of residual ¹⁴C-EOC was labile to further metabolism by lake heterotrophs. First-order rate constants for EOC utilization showed a mode of 0.05 to 0.15 per day. From 33% to 78% of gross ¹⁴C-EOC uptake was respired (mean 50%), indicating appreciable return of algal EOC to the pelagic food web as microbial biomass.Contribution No. 596, W. K. Kellogg Biological Station, Michigan State University.     

The kinetics of NH4 uptake by Ceratophyllum

The relationship between growth of aquatic plants and their nutrient supply is poorly understood, because of the lack of suitable models which could be tested in the field. The purpose of this research was to learn if the Michaelis-Menten expression describes the relationship between the uptake of NH₄ by Ceratophyllum and the concentration of NH₄ in solution.A hyperbola results when uptake of NH₄ by Ceratophyllum (v) is plotted against the concentration of NH₄ in solution (S). The relationship is not described well by the Michaelis-Menten expression. Linearily between v and S at concentrations less than 7 mg NH₄-N(1)-¹, suggests that a model for first order saturation kinetics might be appropriate. However, uptake is depressed by one half at low temperatures and some of the uptake is apparently related to processes which are not completely passive. The ecological usefulness of the Michaelis-Menten constants derived for Ceratophyllum is discussed.     

Comparison of different algal carbon estimates by use of the Droop-model for nutrient limited growth

Three different estimates of algal carbon were derived fromfield experiments in plastic enclosures and tested as measureof algal biomass in the growth model of Droop. Fresh weightderived carbon and total paniculate organic carbon correctedfor detritus were both found to behave as good estimates ofalgal biomass in the model, while total paniculate organic carbondid not. The study also provided results which suggested thatthe relation between growth rate and endogenous phosphorus differedfor two species involved. Growth was maintained at lower Q_p-ratiosin Staurastrum dominated communities compared with communitiesconsisting mainly of Anabaena flos-aquae.     

The use of optical spectroscopy in combinatorial chemistry

Infrared and Raman spectroscopy allow direct spectral analysis of the solid‐phase, thus avoiding the tedious cleavage of compounds from the solid support. With diagnostic bands in starting materials or products, infrared and Raman spectroscopy are efficient in monitoring each reaction step directly on the solid phase. Consequently, infrared and Raman spectroscopy have evolved as the premier analytical methodology for direct analysis on the solid support. While infrared transmission spectroscopy is a general analytical method for resin samples, internal reflection spectroscopy is especially suited for solid polymer substrates known as “pins” or “crowns.” Single bead analysis is done best by infrared microspectroscopy, whereas photoacoustic spectroscopy allows totally nondestructive analysis of resin samples. With an automated accessory, diffuse reflection spectroscopy provides a method for high throughput on‐bead monitoring of solid‐phase reactions. Providing identification based on molecular structure, HPLC‐FTIR is, therefore, complementary to LC‐MS. Additionally, Raman spectroscopy as a complement to infrared spectroscopy can be applied to resin samples and—using a Raman microscope—to single beads. Fluorometry as an extremely sensitive spectroscopic detection method allows rapid quantification of organic reactions directly on the resin. © 1999 John Wiley & Sons, Inc. Biotechnol Bioeng (Comb Chem) 61:179–187, 1998/1999.     

Inorganic carbon acquisition in potentially toxic and non-toxic diatoms: the effect of pH-induced changes in seawater carbonate chemistry

The effects of pH-induced changes in seawater carbonate chemistry on inorganic carbon (C(i)) acquisition and domoic acid (DA) production were studied in two potentially toxic diatom species, Pseudo-nitzschia multiseries and Nitzschia navis-varingica, and the non-toxic Stellarima stellaris. In vivo activities of carbonic anhydrase (CA), photosynthetic O(2) evolution and CO(2) and HCO(3)(-) uptake rates were measured by membrane inlet MS in cells acclimated to low (7.9) and high pH (8.4 or 8.9). Species-specific differences in the mode of carbon acquisition were found. While extracellular carbonic anhydrase (eCA) activities increased with pH in P. multiseries and S. stellaris, N. navis-varingica exhibited low eCA activities independent of pH. Half-saturation concentrations (K(1/2)) for photosynthetic O(2) evolution, which were highest in S. stellaris and lowest in P. multiseries, generally decreased with increasing pH. In terms of carbon source, all species took up both CO(2) and HCO(3)(-). K(1/2) values for inorganic carbon uptake decreased with increasing pH in two species, while in N. navis-varingica apparent affinities did not change. While the contribution of HCO(3)(-) to net fixation was more than 85% in S. stellaris, it was about 55% in P. multiseries and only approximately 30% in N. navis-varingica. The intracellular content of DA increased in P. multiseries and N. navis-varingica with increasing pH. Based on our data, we propose a novel role for eCA acting as C(i)-recycling mechanism. With regard to pH-dependence of growth, the 'HCO(3)(-) user' S. stellaris was as sensitive as the 'CO(2) user' N. navis-varingica. The suggested relationship between DA and carbon acquisition/C(i) limitation could not be confirmed.     

Inorganic carbon uptake kinetics of the stream macrophyte Callitriche cophocarpa Sendt.

Photosynthetic carbon uptake of Callitriche cophocarpa Sendt. was examined in plants collected from six Danish streams and in plants grown under variable inorganic carbon conditions in the laboratory. Both field and laboratory plants showed a low affinity for inorganic carbon (CO₂ compensation points ranging from 0.7 to 22 μM, and K_0.5(CO₂) from 51 to 121 μM), consistent with C-3 photosynthesis and use of CO₂ alone. Variation in inorganic carbon uptake characteristics was low in both groups of plants. Only in laboratory-grown plants was a coupling found between carbon uptake and the inorganic carbon regime of the medium. The carbon extraction capacity, expressed as a percentage of the initial amount of dissolved inorganic carbon (DIC) assimilated in PH-drift experiments, increased from −1.4 to 11.8% with declining external carbon availability, and the initial slope of the CO₂ response curve increased from 6.4 to 15.3 g⁻¹ h⁻¹ dm³. The plasticity of the inorganic carbon uptake system of C. cophocarpa was very low compared to the plasticity observed for submerged macrophytes with accessory carbon uptake systems (i.e. HCO₃⁻ use or C-4 photosynthesis), suggesting that the plasticity of the C-3 photosynthetic apparatus as such is restricted. The low carbon affinity of C. cophocarpa indicates that this species depends on CO₂ oversaturation for a sufficient supply of CO₂ for photosynthesis and growth.     

Cadmium uptake kinetics in human erythrocytes

Cross-membrane transport of cadmium in human erythrocytes was studied using 109Cd+(+) and liquid scintillation counting. Uptake rates were determined by depletion of radioactivity in the incubation medium and the amount of hemolyzate radioactivity taken up by the erythrocytes. Both saturable and nonsaturable components for cadmium transport were observed. The mean maximum uptake rate (Jmax) of the saturable component was 4.9 X 10(-6) mol/L/h. The transport constant (Kt) was estimated at 6.9 X 10(-5) mol/L. The diffusion constant (Kd) of the non-saturable component was 1.4 X 10(-2)/h. Both Jmax and Kt of cadmium generally decreased when Zn+(+) was present, with a biphasic response in the presence of Cu+(+). Kd of cadmium increased as Zn+(+) or Cu+(+) levels were increased. It is suggested that cadmium may penetrate human red cells via cation transport sites owing to its behavior as an analog of one or more nutrient species.     

The use of eddy covariance to infer the net carbon dioxide uptake of Brazilian rain forest

• 1 Eddy covariance measurements of CO₂ flux, based on four and six week campaigns in Rondôdnia, Brazil, have been used in conjunction with a model to scale up data to a whole year, and thus estimate the carbon balance of the tropical forest ecosystem, and the changes in carbon balance expected from small interannual variations in climatological conditions.
• 2 One possible source of error in this estimation arises from the difficulty in measuring fluxes under stably stratified meteorological conditions, such as occur frequently at night. Flux may be ‘lost’ because of low velocity advection, caused by nocturnal radiative cooling at sites on raised ground. Such effects may be detected by plotting the net ecosystem flux of CO₂, F_eco is a function of wind speed. If flux is ‘lost’ then F_eco is expected to decline with wind speed. In the present data set, this did not occur, and F_eco was similar to the nocturnal flux estimated independently from chamber measurements.
• 3 The model suggests that in 1992/3, the Gross Primary Productivity (GPP) was 203.3 mol C m^?2 y^?1 and ecosystem respiration was 194.8 mol C m^?2 y^?1, giving an ecosystem carbon balance of 8.5 mol C m^?2 y^?1, equivalent to a sink of 1.0 ton C ha^?1 y^?1. However, the sign and magnitude of this figure is very sensitive to temperature, because of the strong influence of temperature on respiration.
• 4 The model also suggests that the effect of temperature on the net carbon balance is strongly dependent on the partial pressure of CO₂.

     

The equilibrium between cytochrome oxidase and carbon monoxide

An evolution argument which attempted to trace the development of hemoglobins from such respiratory pigments as cytochrome oxidase presupposed that the latter possesses, in addition to its high affinity for oxygen, an approximately hyperbolic equilibrium function, and little if any Bohr effect (decline in affinity for oxygen with rise in acidity). Since cytochrome oxidase, unlike hemoglobin, is irreversibly oxidized by oxygen, the present experiments examine its combination with carbon monoxide, with which, like hemoglobin, it yields a true equilibrium. In all known hemoglobins the form of the equilibrium function and the vigor of the Bohr effect are similar with carbon monoxide and with oxygen, so that observations involving the former gas are relevant to the relations of the latter. The equilibrium function of cytochrome oxidase with carbon monoxide—percentage saturation vs. partial pressure of CO—is slightly inflected (in the Hill equation n = 1.26; for a hyperbola, n = 1). No Bohr effect is present in the range of pH 7–8. The pressure of carbon monoxide at which half-saturation occurs (p₅₀) is about 0.17 mm. at 10–13°C. The affinity for carbon monoxide is therefore higher than commonly supposed. These properties are consistent with the evolution argument. They are important also for the physiological functioning of cytochrome oxidase, the nearly hyperbolic equilibrium function facilitating a high degree of saturation, and the lack of Bohr effect making this enzyme impervious to hyperacidity. The slight inflection of the equilibrium function shows that the Fe-porphyrin units of cytochrome oxidase interact to a degree, hence that the enzyme must contain more than one such unit per molecule. It is suggested that in cytochrome oxidase two Fe-porphyrin groups may unite with one oxygen in the manner Fe⁺⁺-O₂-Fe⁺⁺; and that the evolution of hemoglobins proceeded over a first stage in which the hemes were separated so that each combines with only one molecule of oxygen, so tending to remain reduced; to a further stage in which the separated hemes interact through the protein to facilitate one another in combining with oxygen.     

火干扰与生态系统的碳循环

火干扰是陆地生态系统碳循环的重要影响因子。它改变着整个系统的碳循环过程与碳分布格局。正确评估火干扰在碳循环过程中的作用,对推进全球碳循环研究有着重要的意义。从4个方面系统的回顾了火干扰对碳循环的影响过程及其研究方法:(1)火烧过程中含碳痕量气体排放的估算;(2)火烧迹地恢复过程中净第一性生产力(NPP)与土壤呼吸的变化;(3)火干扰对生态系统碳源/汇的影响;(4)模型方法在火干扰与生态系统碳循环研究中的应用。目前火灾碳排量的估算方法业已成熟,但进行更精确的估算必须基于对受干扰生态系统的性质以及火势的时空变异性质的准确理解;相比之下,对于间接的、更为重要的影响,即对火烧迹地恢复过程中碳循环变化的研究则显不足。由于数据缺乏,现有研究大多限于对碳循环某一方面的观测与定量描述,缺乏全面的机理性分析。对此,实地观测、模型模拟与遥感观测的跨尺度集成将成为未来火干扰研究的一个主要方向。