Sequential fractionation of sediment phosphate

By means of sequential extractions with Ca-NTA and EDTA, a separation was performed between Fe(OOH) P and CaC0₃P in a few sediments; the remaining fraction, considered to be organic phosphate, was quantified as well. We found that with the commonly used method of extraction with NaOH and H₂S0₄, less Fe(OOH) P and much more CaC0₃ P was found than with the chelating extractants. The organic phosphate pool in live and dead algal material and in some mud samples was partly hydrolysed and therefore recovered as inorganic phosphates with classical extractions. The difference between chelating extractants and the classical ones is discussed.Abbreviations o-P: ortho phosphate (or its concentration) - org-P: organic phosphate - extr-P: extractable sediment bound phosphate - extr-Fe: extractable sediment bound iron - Fe(OOH) P: iron bound, sediment phosphate - CaCO₃ P: calcium bound, sediment phosphate - org-C: organic sediment bound carbon     

Inorganic Carbon of Sediments in the Yangtze River Estuary and Jiaozhou Bay

JGOFS results showed that the ocean is a major sink for the increasing atmospheric carbon dioxide resulting from human activity. However, the role of the coastal seas in the global carbon cycling is poorly understood. In the present work, the inorganic carbon (IC) in the Yangtze River Estuary and Jiaozhou Bay are studied as examples of offshore sediments. Sequential extraction was used to divide inorganic carbon in the sediments into five forms, NaCl form, NH₃ H₂O form, NaOH form, NH₂OH HCl form and HCl form. Studied of their content and influencing factors were also showed that NaCl form < NH₃ H₂O form<NaOH form < NH₂OH HCl form<HCl form, and that their influencing factors of pH, Eh, Es, water content, organic carbon, organic nitrogen, inorganic nitrogen, organic phosphorus and inorganic phosphorus on inorganic carbon can be divided into two groups, and that every factor has different influence on different form or on the same form in different environment. Different IC form may transform into each other in the early diagenetic process of sediment, but NaCl form, NH₃ H₂O form, NaOH form and NH₂OH HCl form may convert to HCl form ultimately. So every IC form has different contribution to carbon cycling. This study showed that the contribution of various form of IC to the carbon cycle is in the order of NaOH form>NH₂OH HCl form>NH₃ H₂O form>NaCl form>HCl form, and that the contribution of HCl form contributes little to carbon cycling, HCl form may be one of end-result of atmospheric CO₂. So Yangtze River estuary sediment may absorb at least about 40.96×10¹¹ g atmospheric CO₂ every year, which indicated that offshore sediment play an important role in absorbing atmospheric CO₂.     

Phosphorus fluctuation in water and deposition into sediment within an emergent macrophyte stand

Seasonal fluctuation of phosphorus in water, and total phosphorus and different inorganic P fractions (extracted by NH₄Cl, NH₄F, NaOH and H₂SO₄) and organic P fraction (residual P) in surface sediment, were measured in the littoral of oligotrophic Lake Pääjärvi (southern Finland). After the emergence of Equisetum fluviatile L. shoots in mid June, water exchange between the littoral and pelagial area diminished and phosphorus concentrations in water and in surface sediment increased in the inner and mid littoral zones. Phosphorus pool in flocculent, easily resuspensible sediment composed on average 62% of inorganic phosphorus and 38% of organic phosphorus. 63% of the inorganic phosphorus, on the average, was extracted from apatite-P fraction 29% from iron-P fraction 7% from aluminum-P fraction and less than 1% from loosely-bound P fraction. During the growing season, net accumulation of sediment and phosphorus was measured only in the inner littoral zone whereas the outer littoral zones acted rather as a source of phosphorus for the pelagic area. The results of this study indicated that nutrient dynamics in littoral environment was through changes in flow environment greatly governed by the macrophytes.     

Influence of the pH and redox potential on phosphate activity in the Parana Medio system

The effect of redox potential and pH on the phosphate mobility in two sediments were investigated using both consolidated and suspended sediments from the area where the Parana Medio long reservoir (Atgentina) is to be built (Smirnov, 1984). In addition to direct chemical sediment analysis, extraction techniques were carried out with a stepwise NH₄Cl-NaOH-HCl shaking method, the latter supposedly separating the weakly bound, the Fe- and Al- bound and the Ca- bound phosphates in the sediments.Phosphate released into water depends upon redox potential and pH, which both were modified in an experimental setup. The source of the phosphate was the fraction of Fe and/or Al bound phosphate present both in the sediment and in the suspended solids.Abbreviations cm centimeter - km kilometer - gg gram - l liter - ¬m micrometer - °C grade centigrades - km² square kilometer - m.s^–1 meter per second - m³.s^–1 cubic meter per second - mg.1¹ miligram per liter     

Differential extraction of sediment phosphates with NTA solutions

An extraction technique is described for the separation of iron- and calcium-bound phosphate. The iron-bound phosphate is extracted with a 0.05 M solution of Ca-NTA under reducing conditions. Iron, also, is brought into solution, which is an advantage over the NaOH extraction. The calcium-bound phosphate is extracted with a 0.05 M solution of Na-NTA. The NTA also extracts humic compounds. Organic phosphate compounds can be measured in the NTA extracts, unlike the NaOH or H₂SO₄ extracts such as are used in the (modified) Jackson procedure.Examples of some test compound extractions and of a calcareous sediment are given.     

Inorganic phosphate in exposed sediments of the River Garonne

Fractionation of inorganic phosphates in sediments of the River Garonne was carried out during a period of low water discharge. Sediments were collected under 5 cm of water (LS), in the dried river bank (MS) and in the riparian forest (RS). Sediments were sampled at two dates, during a period in which the water level fell gradually, causing sediment LS to be air exposed.Sediments were analysed for total phosphate, iron bound phosphate (Fe(OOH)P) using Ca-NTA and Ca bound phosphate (CaCO₃P) using Na-EDTA.Total-P varies from 552 (RS at date 1) to 2072 µg g^–1 (LS at date 2). There are significant differences between sediments and a significant increase from date 1 to date 2 in sediment LS only (1825 to 2072 µg g^–1). Fe(OOH)P varies from 186 (RS at date 1) to 874 µg g^–1 (LS at date 2). The highest values correspond to sediment LS. Moreover, Fe(OOH)P increased significantly between date 1 and 2 in LS (560 to 874 µg g^–1) as well as in sediment MS (248 to 432 µg g^–1). Ca bound P concentrations differed significantly between sediments (75, 112, 235 µg g^–1 for sediments RS, MS and LS respectively) but not between sampling dates.These differences are attributed to the conditions of deposition of the sediments (such as morphology and hydrology of the river) and to the changes in chemical composition during the drying out of the sediments.     

Root mucilage enhances aluminum accumulation in Melastoma malabathricum,an aluminum accumulator

Root mucilage is gelatinous polysaccharide-containing material exuded from the outer layers of the root cap. Although mucilage has been suggested to play several roles in plant growth, its role in mineral uptake has not been well understood. Melastoma malabathricum L. is an aluminum (Al) accumulator growing in tropical acid soils. This species accumulates more than 10 mg Al g⁻¹ DW in leaves and roots. Root mucilage is generally known to immobilize metal cations such as Al in the rhizosphere. However, we found that roots of M. malabathricum exuded large amounts of mucilage. Using the Zea mays L. mucilage as a control, we have recently shown that mucilage of M. malabathricum has unique physical and chemical characteristics, and facilitates Al uptake in this species. Since M. malabathricum cannot grow well in Al-deficient soil (nonacid soils), this species might have developed a mechanism for Al acquisition. We have also discussed the reason for this species'' requirement of Al, a nonessential element.Key words: aluminum accumulator, cation adsorption, Melastoma malabathricum L., polysaccharide, root mucilage, uronic acidPlant roots exude various chemical compounds. Root mucilage is a gelatinous high molecular weight compound, consisting mainly of polysaccharides, and is exuded from the outer layers of the root cap. One of the suggested roles of mucilage in plant growth is detoxification (fixation) of toxic metal cations, including Al in acidic soils.¹ Polysaccharides in mucilage contain uronic acids,² the carboxyl groups of which might adsorb and inactivate Al in the rhizosphere.³ However, Li et al.,⁴ suggested that the contribution of mucilage to Al inactivation in the rhizosphere of Zea mays L. is almost negligible owing to its small amount.Melastoma malabathricum L. is an Al accumulator growing in tropical acidic soils and is one of the dominant woody species growing in acid sulfate soils in tropical Asia, Australia and Polynesia. This species accumulates more than 10 mg Al g⁻¹ DW in leaves and roots.⁵ It is known that the growth of non-essential element-accumulating plants is often enhanced by the application of the accumulated element (e.g., Na in a Na accumulator plant). The growth of M. malabathricum is enhanced by Al application under hydroponic conditions.⁶ It has been predicted that this growth enhancement is due to alleviation of iron toxicity⁷ or a disorder of organic acid metabolism in the absence of Al.⁸ Recently, we observed that the roots of M. malabathricum exuded large amounts of mucilage under “Al deficient” conditions, raising a question about the role of mucilage in this species.Our recent study indicated that M. malabathricum mucilage facilitates Al uptake in this species.⁹ Contrastingly, uptake of other cations such as K, Ca and Mg were not affected. To the best of our knowledge, this is the first study to demonstrate that mucilage selectively enhances mineral uptake in plant. To elucidate the factors that were responsible for these characteristics of M. malabathricum mucilage, we compared the physical and chemical properties of M. malabathricum mucilage with that of Z. mays mucilage, which is known to strongly bind to Al.⁴ The results are summarized in Figure 1A. Critical differences in the physical properties that can affect Al uptake of roots were evaluated. M. malabathricum mucilage has higher adsorption affinities for trivalent cations, whereas Z. mays mucilage has a higher affinity for divalent cations. Moreover, ²⁷Al NMR analysis and bioassay indicated that the binding strength between mucilage and Al was very weak in M. malabathricum mucilage and its ionic activity was nearly equal to inorganic monomeric Al ions.Open in a separate windowFigure 1Characterization of root mucilage in Melastoma malabathricum. (A) Differences in physical and chemical properties of mucilage between M. malabathricum and Zea mays. (B) Hypothetical model of selective adsorption of cation in M. malabathricum and Z. mays. Mucilage of M. malabathricum has high affinity for trivalent cations because of its higher charge density. (C) Hypothetical scheme of Al acquisition in M. malabathricum.What is the primary factor behind such special characteristics of Al adsorption in the M. malabathricum mucilage? In general, a cation exchanger with a high charge density exhibits preferences for trivalent cations.¹⁰ The cation exchange capacity per unit volume in the M. malabathricum mucilage is nearly twice as high as that in Z. mays mucilage because of its higher proportion of uronic acid (glucuronic acid) (Fig. 1B). This high charge density is considered to be the primary reason for higher affinity of the trivalent cation in M. malabathricum mucilage. Conversely, the weak binding strength between mucilage and Al is possibly due to the higher degree of methylation in M. malabathricum mucilage. It has been suggested that like unmethylated polyuronic acid, partly methylated polyuronic acid can form “egg box” junctions;¹¹ however, the binding strength is weak.¹² In addition, the lower pH of M. malabathricum mucilage is also responsible for the weak binding strength.M. malabathricum has evolved in extremely acidic soils. This medium, with a certain level of Al ion, might be suitable for the growth of this species, as opposed to Al-free medium. Recently, we found that water-soluble Ca, Mg and oxalate concentrations in both shoots and roots of M. malabathricum grown hydroponically in the absence of Al were significantly lower than that in the presence of Al (Fig. 2). Irrespective of Al concentration in the medium, M. malabathricum synthesizes a high concentration of oxalate, which is a ligand for Al detoxification in plant tissue.⁸ The high concentration of oxalate would make insoluble precipitates with Ca and Mg when grown in the absence of Al, inducing severe deficiency of these elements in M. malabathricum. Therefore, mechanisms of Al acquisition are essential for M. malabathricum when growing in Al deficient soils (Fig. 1C).Open in a separate windowFigure 2Ratio of water-soluble K, Ca, Mg and oxalate to total concentration in Melastoma malabathricum grown in a nutrient solution with or without 0.5 mM AlCl₃ for 30 days. Water soluble K, Ca, Mg and oxalate concentrations were determined by ICP-OES or capillary electrophoresis after extracting with deionized water (lyophilized sample:water = 1:10). Total K, Ca and Mg concentrations were determined by ICP-OES after wet-digestion. Total oxalate concentrations were determined by capillary electrophoresis after extracting with 0.2 M HCl. The standard nutrient solution contained 0.54 mM N (NH₄NO₃), 32 µM P (NaH₂PO₄·2H₂O), 0.15 mM K (K₂SO₄:KCl = 1:1), 0.25 mM Ca (CaCl₂·2H₂O), 0.16 mM Mg (MgSO₄·7H₂O), 35.8 µM Fe (FeSO₄·7H₂O), 1.8 µM Mn (MnSO₄·4H₂O), 9.26 µM B (H₃BO₃), 0.62 µM Zn (ZnSO₄·7H₂O), 0.036 µM Cu (CuSO₄·5H₂O) and 0.01 µM Mo ((NH₄)₆Mo₇O₂₄·4H₂O); total SO₄ = 0.21 mM. There was no significant difference in total concentrations between the treatments.     

Some remarks on the presence of organic phosphates in sediments

This article describes a new method developed to assess the size and nature of the organic phosphate pool. Using sediment suspensions from the Rhone, Garonne and Po rivers, inorganic P compounds, Fe(OOH) and CaCO₃ were removed using mild extractants at sediment pH. The residual phosphate was then fractionated into an acid soluble organic phosphate pool and a residual organic phosphate pool by acid hydrolysis (0.5 M H⁺). Both pools were quantitatively important, accounting for between 16 and 54% and 16 and 51% of total phosphate respectively. Acid hydrolysis was chosen since it yielded a distinct plateau, with high reproducibility, within 30 minutes.This fractionation permits a further study of dynamics and bioavailability of sediment org-P, without interference of Fe(OOH) and CaCO₃.In many studies in which changes in the organic pool were examined after extraction of inorganic phosphate, 0.5 M HCl was used to extract apatite bound phosphate. The results presented here show that this is likely to result in a considerable underestimation of the organic phosphate pool.     

Phosphorus foraging root development of Brassica rapa nothovar. grown in a phosphorus-deficient nonallophanic Andisol

Lateral root of Brassica crops firmly aggregated around Ca-alginate gel beads containing dicalcium phosphate dihydrate and -cyclodextrin (DCPD gel bead) in a phosphate (P)-deficient soil (Nanzyo et al., 2002, Soil Sci. Plant Nutr. 48, 847–853). The first aim of the present study was to identify the component in the DCPD gel beads that accounts for the special root proliferation. This P-foraging root growth was observed in plots applied with either polyolefin-coated NH₄H₂PO₄ (POC-MAP) or DCPD powder instead of the DCPD gel beads. The POC-MAP neither contains Ca, alginate nor -cyclodextrin. The DCPD powder was applied in a similar number of spots with the number of DCPD gel beads. Thus, the essential component in the DCPD gel beads for the P-foraging root growth around them was P. The second aim was to examine the effect of various inorganic P sources on the P uptake of B. rapa nothovar. While significant P uptake was obtained in the plot applied with apatite from Florida, USA, sediment origin (F-Ap), almost no P uptake was obtained in that with apatite from Quebec, Canada, igneous origin in the P-deficient nonallophanic Andisol. Hence, a P-release level from F-Ap was near the lower limit for the P uptake by the B. rapa nothovar. under the present experimental conditions. These results indicate the P foraging characteristics of the Brassica roots contribute to improve the P recovery rate in the agricultural fields with localized application of moderately-soluble P fertilizers.     

Iron-bound phosphorus in marine sediments as measured by bicarbonate-dithionite extraction

A sequential five-step extraction scheme for phosphorus pools in freshwater sediment was modified for use in marine sediments. In the second step phosphate bound to reducible forms of iron and manganese (iron-bound P) is extracted by a bicarbonate buffered dithionite solution (BD-reagent). The extraction scheme was tested on sediment from 16 m water depth in Aarhus Bay, DK and used in two other marine sediments: Kattegat at 56 m and Skagerrak at 695 m depth. By comparing the BD-extractable P-pool with both the pool of iron in the BD-fraction and the pool of oxidized, amorphous or poorly crystalline iron (am.FeOOH), highly significant correlations (p < 0.001) were observed in all three sediments. Thus, we conclude that the BD-reagent was very specific for iron-bound P. Further evidence for this came from two experiments: 1) Enhanced BD treatment did not result in additional phosphate extraction and 2) by sequential extraction of phosphorus pools in pure cultures of diatoms and cyanobacteria no phosphate was recovered in the BD-fraction. The pool of am.FeOOH was very important for controlling porewater phosphate concentration which was inferred from the significant inverse relationships between the two parameters (p < 0.001) in all sediments studied. Further, an isotopic exchange experiment with ³²PO_f4/^p3– revealed that BD-extractable P was by far the most exchangeable P-pool even deep in the sediment where the pool size was small. Iron-bound P made up 33–45% of total P in the surface sediments. The ratio between iron-bound phosphate and am.FeOOH was 8–11 in Aarhus Bay and Kattegat. In Skagerrak the ratio was 17, which may indicate that the iron mineral extracted from this sediment is less capable of adsorbing phosphate or less saturated with phosphate.     

The occurrence and behaviour of phosphate fractions in Izmir Bay, Aegean Sea

The area around Izmir Bay (Turkey) is heavily urbanized and receives, therefore, high concentrations of phosphate originating from industrial and municipal inputs. During the surveys between April 1993 and July 1994, the total phosphate concentrations were highest in the Inner Bay (6.45 M and 5.59 M in the surface and bottom water, respectively) where very dense anthropogenic pollution occurs. The total phosphate value gradually decreased towards the Outer Bay where 0.70 M and 1.18 M were found in the surface and bottom water, respectively. The distribution of dissolved inorganic, dissolved organic and particulate phosphate along the bay reflected some peculiar spatial and temporal patterns. A high percentage of dissolved organic phosphate was observed in the Outer Bay while the particulate phosphate peaked in the Middle Bay where an upwelling mechanism was observed. In the bay, the biological production was strongly correlated with the variations in the dissolved inorganic, organic and particulate phosphate. The high phosphate concentration in particles caused the particulate phosphate formed in the Inner Bay to be transported to the outer parts of the bay because of the short water residence time. On the other hand, Principal Component Analysis showed that about 35% of the variation in all variables measured were related to the total phosphate, total dissolved phosphate, dissolved inorganic phosphate and particulate phosphate together with ammonium and reactive-Fe while about 14% of the variation was related to the dissolved organic phosphate and the number of phytoplankton cells, chl-a, pH and O₂.     

Hydrothermal synthesis and characterization of a novel 3D open framework structure of mixed valence ethylenediamine-vanadium phosphate: [C2H10N2][(HVO3)(HVO2) (PO4)]

A new three-dimensional open framework structure of mixed valence ethylenediamine-vanadium phosphate [C₂H₁₀N₂][(HV^IVO₃)(HV^VO₂)(PO₄)] (1), has been synthesized under mild hydrothermal conditions and characterized by elemental analyses, IR, fluorescent spectrum, TG-DTA and single crystal X-ray diffraction. Compound 1 exhibits a novel three-dimensional (3D) vanadium phosphate anion framework composed of vanadium, phosphate, and oxygen atoms through covalent bonds, with the diprotonated ethylenediamine [NH₃CH₂CH₂NH₃]²⁺ cations residing in the channels along c-axis. The organic diprotonated ethylenediamine cations interact with the O atoms in the inorganic network through hydrogen bonds. The electrochemical behavior of 1 has also been studied in detail by cyclic voltammograms, which is very important for practical applications in electrode modification. Furthermore, the strong photoluminescence property of compound 1 is also measured at room temperature.     

Seasonal changes in sediment phosphorus forms in relation to sedimentation and benthic bacterial biomass in Lake Erken

Surficial sediment and sedimenting material were sampled during spring and summer 1991 in Lake Erken. Sediment was analyzed for redox potential, P concentrations and bacterial biomass. Sedimentation and chlorophyll a concentrations of sedimenting matter were determined. Additionally, different phosphorus forms in surficial sediment were quantified using sequential fractionation. The resulting dataset was used to study the effects of sedimentation events following phytoplankton blooms and benthic bacterial biomass on the size of the various phosphorus pools in the sediment.Sedimentation of spring diatoms caused a rapid increase in the NH₄Cl- and NaOH-extractable P (NH₄Cl–P and NaOH–rP) in the sediment. During sedimentation, NaOH–rP and NH₄Cl–P increased within 3 days from 422 ± 17 g g^–1 DW to 537 ± 8.0 g g^–1 DW and from 113 ± 13 g g^–1 DW to 186 ± 26 g g^–1 DW, respectively. The NaOH–nrP (non-reactive P) fraction made up about 17% of Tot-P in sediment samples, whereas NaOH–rP and HCl–P made up 25% each. All P forms showed considerable seasonal variation. Significant relationships were found between bacterial biomass and the NaOH–nrP and NH₄Cl–P fractions in the sediment, respectively. Also regressions of NaOH–nrP and NH₄Cl–P versus the chlorophyll a concentration of sedimenting matter were highly significant. These regressions lend support to the conjecture that NaOH–nrP is a conservative measure of bacterial poly-P.     

Underestimated effects of sediments on enhanced startup performance of biofilm systems for polluted source water pretreatment

In order to evaluate the enhancement mechanisms of enhanced startup performance in biofilm systems for polluted source water pretreatment, three lab-scale reactors with elastic stereo media (ESM) were operated under different enhanced sediment and hydraulic agitation conditions. It is interesting to found the previously underestimated or overlooked effects of sediment on the enhancement of pollutants removal performance and enrichment of functional bacteria in biofilm systems. The maximum NH₄ ⁺–N removal rate of 0.35 mg L^?1 h^?1 in sediment enhanced condition was 2.19 times of that in control reactor. Sediment contributed to 42.0–56.5% of NH₄ ⁺–N removal and 15.4–41.2% of total nitrogen removal in different reactors under different operation conditions. The enhanced hydraulic agitation with sediment further improved the operation performance and accumulation of functional bacteria. Generally, Proteobacteria (48.9–52.1%), Bacteroidetes (18.9–20.8%) and Actinobacteria (15.7–18.5%) were dominant in both sediment and ESM bioiflm at  phylum level. The potentially functional bacteria found in sediment and ESM biofilm samples with some functional bacteria mainly presented in sediment samples only (e.g., Genera Bacillus and Lactococcus of Firmicutes phylum) may commonly contribute to the removal of nitrogen and organics.     

Immunological Studies on Antisera of Mice Immunized with Dried or DEPC-treated Ehrlich Ascites Tumor Cells

Intracellular arylsulfatases from Klebsiella aerogenes W70 cells grown in methionine medium (M enzyme) and inorganic sulfate medium containing tyramine (T enzyme) were purified respectively by fractionation with (NH₄)₂SO₄, followed by successive chromatographies on DEAE cellulose, hydroxylapatite, Sephadex G-100 and DEAE Sephadex A-25. On polyacrylamide gel electrophoresis, the two enzymes gave single bands with the same mobilities. Molecular weights of both, determined by SDS gel electrophoresis and by Sephadex G-100 chromatography, were 47,000 and 45,000, respectively. Their activities were maximal at pH 7.5. The affinities of the enzymes (M and T enzymes) for their substrate (Km) and the maximum velocity of hydrolysis (V_max) were enhanced by addition of electron withdrawing substituents. The enzymes were inhibited by inorganic phosphate, cyanide, hydroxylamine and tyramine. The inhibition by tyramine was competitive (Ki = 1.0 × 10^?4 m). These results show that the two enzymes were identical. This was confirmed by the fact that mutant strains, which were unable to synthesize arylsulfatase when grown with methionine, could also not synthesize the enzyme when grown with tyramine.     

Particle size-related phosphate binding and P-release at the sediment–water interface in a shallow German lake

Phosphate binding and P-release in the sediment of the eutrophic shallow Lake Bützow are described based on sediment profiles, particle size fractions and incubation experiments. Total phosphorus was about 15% higher in the upper 0.5 cm layer than in the 0.5–1 cm layer. Phosphorus binding varied with sediment depth. Hot P_NaOH and P_HCl were the dominant fractions in all sediment horizons down to 10 cm depth, with values ranging from 20 to 30%. The P_H2O, P_BD, o-P_NaOH and nr-P_NaOH decreased with depth. The P_BD contributed 21% to Tot-P in the horizon 0–0.5 cm and decreased by half in 1–2 cm. The greatest proportion of particles (35%) was found in the 100–200 m fraction. This size fraction also accumulated most of the phosphate. Moreover, P-forms were differently distributed in the various particle sizes of the sediment. Sediment particles <40 m can be resuspended by a wind velocity of 2 m s^–1, whereby 17% of the Tot-P from the topmost sediment were transported into the water column. The proportions of released labile phosphate, organic phosphate and hydrolysable phosphate were higher, with values of 24, 33 and 26%, respectively. Dissolved P was released under oxic and anoxic incubation, but anoxic release was higher. Comparison of the results shows that the P-release under anoxic conditions was equal to the P-release by resuspension, but under anoxic conditions the release of bioavailable P was higher.     

The effects of root surface charge and nitrogen forms on the adsorption of aluminum ions by the roots of rice with different aluminum tolerances

Aim

Our objectives were to compare effects of root charge properties on Al adsorption by the roots of rice that differed in Al-tolerance, and to examine effects of different nitrogen forms on charge properties of rice roots and Al adsorption.

Methods

Streaming potential and chemical methods were used to measure root zeta potential and investigate Al chemical forms adsorbed on the roots of rice obtained from solution culture experiments.

Results

Rice roots of the Al-sensitive variety Yangdao-6 carried greater negative charge than the Al-tolerant variety Wuyunjing-7, which meant the roots of Yangdao-6 adsorbed more exchangeable and complexed Al. When both rice varieties were grown in NH₄ ⁺-containing nutrient solutions, there were less functional groups and lower negative surface charge on their roots, which reduced Al adsorption compared to the rice grown in NO₃ ^? containing nutrient solutions. The decline in nutrient solution pH due to NH₄ ⁺ uptake by rice roots was responsible for the reduced numbers of functional groups and the lower negative surface charge on the roots compared to the rice grown in NO₃ ^? containing solutions.

Conclusions

Integrated root surface charge, as expressed by zeta potential, played an important role in Al adsorption by the roots of rice with different Al-tolerance.

     

Microbial activities in the burrow environment of the potamal mayfly Ephoron virgo

1. The impact of burrowing larvae of Ephoron virgo (Ephemeroptera, Polymitarcidae) on sediment microbiology has not been previously investigated because of difficulties in sampling the sediment of large rivers under in situ conditions. Therefore, we conducted experiments in the on‐ship Ecological Rhine Station of the University of Cologne (Germany), in which ambient conditions of the River Rhine can be closely mimicked. 2. In two consecutive seasons, experimental flow channels were stocked with Ephoron larvae and continuously supplied with water taken directly from the River Rhine. Sediment from the immediate vicinity of Ephoron burrows (i.e. U‐shaped cavities reaching 10–80 mm deep into the sediment) and bulk sediment samples were analysed for (i) particulate organic matter content, (ii) microscale in situ distribution of O₂, NO, and NH, and (iii) potential activities of exoenzymes. 3. Sediment surrounding the Ephoron burrows had markedly higher organic matter contents and exoenzyme activities compared with the bulk sediment. Microsensor measurements demonstrated that local O₂ and NO penetration into the sediment were greatly enhanced by larval ventilation behaviour. Volumetric O₂ and NO turnover rates that were calculated from steady state concentration profiles measured directly in the burrow lining were considerably higher than at the sediment surface. 4. In the sediment of the fast flowing River Rhine Ephoron burrows are preferential sites of organic matter accumulation and dissolved oxidant penetration. Our data suggest that the burrows are surrounded by a highly active microbial community that responds to the inputs from the water column with elevated O₂ and NO turnover, and release of exoenzymes into the sediment pore water. Especially during periods of mass occurrence, the larvae of E. virgo may thus significantly contribute (i) to the ecological connection between the water column and the sediment and (ii) to biogeochemical processing of organic matter in the riverbed.     

Use of chemical ionization for GC–MS metabolite profiling

Metabolite profiling is commonly performed by GC–MS of methoximated trimethylsilyl derivatives. The popularity of this technique owes much to the robust, library searchable spectra produced by electron ionization (EI). However, due to extensive fragmentation, EI spectra of trimethylsilyl derivatives are commonly dominated by trimethylsilyl fragments (e.g. m/z 73 and 147) and higher m/z fragment ions with structural information are at low abundance. Consequently different metabolites can have similar EI spectra, and this presents problems for identification of “unknowns” and the detection and deconvolution of overlapping peaks. The aim of this work is to explore use of positive chemical ionization (CI) as an adjunct to EI for GC–MS metabolite profiling. Two reagent gases differing in proton affinity (CH₄ and NH₃) were used to analyse 111 metabolite standards and extracts from plant samples. NH₃-CI mass spectra were simple and generally dominated by [MH]⁺ and/or the adduct [M+NH₄]⁺. For the 111 metabolite standards, m/z 73 and 147 were less than 3% of basepeak in NH₃-CI and less than 30% of basepeak in CH₄-CI. With CH₄-CI, [MH]⁺ was generally present but at lower relative abundance than for NH₃-CI. CH₄-CI spectra were commonly dominated by losses of CH₄ [M+1-16]⁺, 1–3 TMSOH [M+1-nx90]⁺, and combinations of CH₄ and TMSOH losses [M+1-nx90-16]⁺. CH₄-CI and NH₃-CI mass spectra are presented for 111 common metabolites, and CI is used with real samples to help identify overlapping peaks and aid identification via determination of the pseudomolecular ion with NH₃-CI and structural information with CH₄-CI.