Does reactive surface area depend on grain size? Results from pH 3, 25 circle C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 mu m were dissolved in pH 3, HCl at 25 degrees C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 X 10(-10) mol(feldspar) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 X 10(-10) mol(feldspar) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol(feldspar) g(-1) s(-1). For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 X 10(-12) mol(biotite) m(-2) s(-1), rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 x 10(-12) mol(biotite) m(-2) s(-1) and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 X 10(-12) mol(biotite) g(-1) s(-1). For all normalising terms rates varied significantly (p <= 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over wich they would change significantly. (c) 2006 Elsevier Inc. All rights reserved.

Effects of manure and fertilizer on grain yield, soil carbon and phosphorus in a 13-year field trial in semi-arid Kenya

Long-term indicators of soil fertility were assessed by measuring grain yield, soil organic carbon (SOC) and soil Olsen phosphorous for a P-deficient soil. In one set of treatments, goat manure was applied annually for 13 years at 0, 5 and 10 t ha(-1), and intercrops of sorghum/cowpea, millet/green gram and maize/pigeonpea were grown. Yield depended on rainfall and trends with time were not identifiable. Manure caused an upward trend in SOC, but 10 t ha(-1) manure did not give significantly more SOC than 5 t ha(-1). Only 10 t ha(-1) manure increased Olsen P. Measurements of both SOC and Olsen P are recommended. In another set of treatments, manure was applied for four years; the residual effect lasted another seven to eight years when assessed by yield, SOC and Olsen P Treatment with mineral fertilizers provided the same rates of N and P as 5 t hat manure and yields from manure and fertilizer were similar. Fertilizer increased Olsen P but not SOC. Management systems with occasional manure application and intermediate fertilizer applications should be assessed. Inputs and offtakes of C, N and P were measured for three years. Approximately 16, 25 and 11% of C, N and P respectively were stabilized into soil organic matter from 5 t ha(-1) a(-1) manure. The majority of organic P was fixed as soil inorganic P.

Tracer correlations in the northern high latitude lowermost stratosphere: Influence of cross‐tropopause mass exchange

We present an analysis of trace gas correlations in the lowermost stratosphere. In‐situ aircraft measurements of CO, N2O, NOy and O3, obtained during the STREAM 1997 winter campaign, have been used to investigate the role of cross‐tropopause mass exchange on tracer‐tracer relations. At altitudes several kilometers above the local tropopause, undisturbed stratospheric air was found with NOy/NOy * ratios close to unity, NOy/O3 about 0.003–0.006 and CO mixing ratios as low as 20 ppbv (NOy * is a proxy for total reactive nitrogen derived from NOy–N2O relations measured in the stratosphere). Mixing of tropospheric air into the lowermost stratosphere has been identified by enhanced ratios of NOy/NOy * and NOy/O3, and from scatter plots of CO versus O3. The enhanced NOy/O3 ratio in the lowermost stratospheric mixing zone points to a reduced efficiency of O3 formation from aircraft NOx emissions.

The influence of hilly terrain on canopy-atmosphere carbon dioxide exchange

Topography influences many aspects of forest-atmosphere carbon exchange; yet only a small number of studies have considered the role of topography on the structure of turbulence within and above vegetation and its effect on canopy photosynthesis and the measurement of net ecosystem exchange of CO2 (N-ee) using flux towers. Here, we focus on the interplay between radiative transfer, flow dynamics for neutral stratification, and ecophysiological controls on CO2 sources and sinks within a canopy on a gentle cosine hill. We examine how topography alters the forest-atmosphere CO2 exchange rate when compared to uniform flat terrain using a newly developed first-order closure model that explicitly accounts for the flow dynamics, radiative transfer, and nonlinear eco physiological processes within a plant canopy. We show that variation in radiation and airflow due to topography causes only a minor departure in horizontally averaged and vertically integrated photosynthesis from their flat terrain values. However, topography perturbs the airflow and concentration fields in and above plant canopies, leading to significant horizontal and vertical advection of CO2. Advection terms in the conservation equation may be neglected in flow over homogeneous, flat terrain, and then N-ee = F-c, the vertical turbulent flux of CO2. Model results suggest that vertical and horizontal advection terms are generally of opposite sign and of the same order as the biological sources and sinks. We show that, close to the hilltop, F-c departs by a factor of three compared to its flat terrain counterpart and that the horizontally averaged F-c-at canopy top differs by more than 20% compared to the flat-terrain case.

Observations of the inter-ocean exchange around South Africa

There is growing evidence that the interocean exchange south of Africa is an important link in the global overturning circulation of the ocean, the so‐called ocean conveyer belt. At this location, warm and salty Indian Ocean waters enter the South Atlantic and are pulled by currents that eventually reach the North Atlantic, where water cools and sinks. A major contributor to the exchange is the frequent shedding of ring eddies from the termination of the Agulhas Current south of the tip of Africa. This shedding is controlled by developments far upstream in the Indian Ocean, and variations in this ‘Agulhas Leakage’ can lead to changes in the rate and stability of the Atlantic overturning, with possible associated global climate variations [Weijer et al., 1999]. Regional climate variations in the tropical and subtropical Indian Ocean are known to affect the whole system of the Agulhas Current, including the interocean exchanges. This article reports on some of the seminal results of ongoing multinational, multidisciplinary projects that explore these issues.

Isolation of lactoperoxidase using different cation exchange resins by batch and column procedures

Lactoperoxidase (LP) was isolated from whey protein by cation-exchange using Carboxymethyl resin (CM-25C) and Sulphopropyl Toyopearl resin (SP-650C). Both batch and column procedures were employed and the adsorption capacities and extraction efficiencies were compared. The resin bed volume to whey volume ratios were 0.96:1.0 for CM-25C and ≤ 0.64:1.0 for SP-650 indicating higher adsorption capacity of SP-650 compared to CM-25C. The effluent LP activity depended on both the enzyme activity in the whey and the amount of whey loaded on the column within the saturation limits of the resin. The percentage recovery was high below the saturation point and fell off rapidly with over-saturation. While effective recovery was achieved with column extraction procedures, the recovery was poor in batch procedures. The whey-resin contact time had little impact on the enzyme adsorption. SDS PAGE and HPLC analyses were also carried out, the purity was examined and the proteins characterised in terms of molecular weights. Reversed phase HPLC provided clear distinction of the LP and lactoferrin (LF) peaks. The enzyme purity was higher in column effluents compared to batch effluents, judged on the basis of the clarity of the gel bands and the resolved peaks in HPLC chromatograms.

Down-regulation of the CSLF6 gene results in decreased (1,3;1,4)-beta-D-glucan in endosperm of wheat

(1,3;1,4)-beta-d-Glucan (beta-glucan) accounts for 20% of the total cell walls in the starchy endosperm of wheat (Triticum aestivum) and is an important source of dietary fiber for human nutrition with potential health benefits. Bioinformatic and array analyses of gene expression profiles in developing caryopses identified the CELLULOSE SYNTHASE-LIKE F6 (CSLF6) gene as encoding a putative beta-glucan synthase. RNA interference constructs were therefore designed to down-regulate CSLF6 gene expression and expressed in transgenic wheat under the control of a starchy endosperm-specific HMW subunit gene promoter. Analysis of wholemeal flours using an enzyme-based kit and by high-performance anion-exchange chromatography after digestion with lichenase showed decreases in total beta-glucan of between 30% and 52% and between 36% and 53%, respectively, in five transgenic lines compared to three control lines. The content of water-extractable beta-glucan was also reduced by about 50% in the transgenic lines, and the M(r) distribution of the fraction was decreased from an average of 79 to 85 x 10(4) g/mol in the controls and 36 to 57 x 10(4) g/mol in the transgenics. Immunolocalization of beta-glucan in semithin sections of mature and developing grains confirmed that the impact of the transgene was confined to the starchy endosperm with little or no effect on the aleurone or outer layers of the grain. The results confirm that the CSLF6 gene of wheat encodes a beta-glucan synthase and indicate that transgenic manipulation can be used to enhance the health benefits of wheat products.

The effects of irrigation, nitrogen fertilizer and grain size on Hagberg falling number, specific weight and blackpoint of winter wheat

The effects of irrigation and nitrogen (N) fertilizer on Hagberg falling number (HFN), specific weight (SW) and blackpoint (BP) of winter wheat (Triticum aestivum L) were investigated. Mains water (+50 and +100 mm month(-1), containing 44 mg NO3- litre(-1) and 28 mg SO42- litre(-1)) was applied with trickle irrigation during winter (17 January-17 March), spring (21 March-20 May) or summer (24 May-23 July). In 1999/2000 these treatments were factorially combined with three N levels (0, 200, 400 kg N ha(-1)), applied to cv Hereward. In 2000/01 the 400 kg N ha(-1) treatment was replaced with cv Malacca given 200 kg N ha(-1). Irrigation increased grain yield, mostly by increasing grain numbers when applied in winter and spring, and by increasing mean grain weight when applied in summer. Nitrogen increased grain numbers and SW, and reduced BP in both years. Nitrogen increased HFN in 1999/2000 and reduced HFN in 2000/01. Effects of irrigation on HFN, SW and BP were smaller and inconsistent over year and nitrogen level. Irrigation interacted with N on mean grain weight: negatively for winter and spring irrigation, and positively for summer irrigation. Ten variables derived from digital image analysis of harvested grain were included with mean grain weight in a principal components analysis. The first principal component ('size') was negatively related to HFN (in two years) and BP (one year), and positively related to SW (two years). Treatment effects on dimensions of harvested grain could not explain all of the effects on HFN, BP and SW but the results were consistent with the hypothesis that water and nutrient availability, even when they were affected early in the season, could influence final grain quality if they influenced grain numbers and size. (C) 2004 Society of Chemical Industry