Spectrophotometric and adsorptive stripping square wave voltammetric determination of iron in olive oils,as complex with 5,5-dimethylcyclohexane-1,2,3-trione 1,2-dioxime 3-thiosemicarbazone (DCDT)

Two methods for the determination of iron in olive oil by spectrophotometry and by adsorptive stripping square wave voltammetry (Ad-SSWV) have been developed. These two methods are based on the formation of a 5,5-dimethylcyclohexane-1,2,3-trione 1,2-dioxime 3-thiosemicarbazone (DCDT)-iron(II) complex in strongly acid media. In both, iron is extracted from the olive oil by using HCl. Spectrophotometric determination of iron with DCDT is based on the feature that the DCDT-Fe complex shows an absorbance maximum at 550 nm. A calibration graph has been constructed from 0 to 4000 ng mL(-)(1), and the detection limit was 115 ng mL(-)(1) (57 ng g(-)(1) in olive oil). On the other hand, the voltammetric determination of the metal is based on the appearance of a peak due to an adsorptive reductive process of the complex that it is observed when the Ad-SSWV technique is used. A calibration graph has been constructed from 0 to 30 ng mL(-)(1), and the detection limit was 0.55 ng mL(-)(1) (13.75 ng g(-)(1) in olive oil according to the proposed procedure).     

Spectrophotometric determination of ferbam [iron(III) dimethyl dithiocarbamate] in commercial sample and wheat grains after extraction of its bathophenanthroline tetraphenylborate complex into molten naphthalene

A procedure has been developed for the determination of iron(III) dimethyldithiocarbamate by converting it into a iron(III)-bathophenanthroline-tetraphenylborate complex, which was then extracted into molten naphthalene, and the absorbance was measured at 534 nm against a reagent blank. Beer's law is obeyed over the concentration range 0.4-20 microg mL(-)(1) in final solution. The method is sensitive and highly selective and is applied for the determination of ferbam in a commercial sample, in mixtures with various dithiocarbamates (ziram, zineb, maneb, etc.), and from wheat grains.     

Sorption and degradation of azimsulfuron on iron(III)-rich soil colloids

The sorption of N-[[(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-1-methyl-4-(2-methyl-2H-tetrazole-5-yl)1H-pyrazole-5-sulfonamide (AZS) on an iron oxide, iron(III)-humate, and an Fe3+-saturated clay was studied using a batch equilibrium method. Generally, 20 mg of each colloid was equilibrated with 20 mL of AZS solution (1.5-12.7 microM). The sorption on iron-montmorillonite and iron oxide was rapid, and the equilibrium was attained within 1.5 and 5 h, respectively. In the case of Fe-saturated humic acid the equilibrium time was 20 h. After equilibration, the phases were centrifuged (19000g, 15 min) and the supernatant was sampled and analyzed by HPLC. The values of Freundlich constants indicate that iron oxide (Kads = 199.5) shows the highest sorptive capacity toward AZS, followed by iron(III)-clay (Kads = 146.6) and iron(III)-humate (Kads = 108.2). With elapsing time, AZS degradation was observed in all colloidal suspensions. Iron-humate (t(1/2) = 136 h) is most effective in promoting AZS degradation, followed by iron oxide (t(1/2) = 204 h) and iron-clay (t(1/2) = 385 h). The metabolites 2-amino-4,6-dimethoxypyrimidine and 1-methyl-4-(2-methyl-2H-tetrazole-5-yl)-1H-pyrazole-5-sulfonamide, arising from a hydrolytic cleavage of the sulfonylurea bridge, were the only byproducts observed. A Fourier transform infrared study suggests that the sorption of AZS on iron-clay involves the protonation of one of the two basic pyrimidine nitrogens induced by the acidic water surrounding the saturating Fe3+ ions. Instead, the formation of a six-membered chelated complex favors the sorption of AZS on iron oxide.     

Iron and sulfate reduction in the sediments of acidic mine lake 116 (Brandenburg,Germany): Rates and geochemical evaluation

A combination of rate measurements of iron(III)oxide and sulfate reduction, thermodynamic data, and pore-water and solid phase analyses was used to evaluate the relative significance of iron and sulfate reduction in the sediments of an acidic strip mining lake (Lake 116, Brandenburg, Germany). The rate of sulfate reduction was determined using a 35S-radiotracer method. Rates of iron turnover were quantified by mass balances based on pore-water concentration profiles. The differences in Gibbs free energy yield from reduction of iron and sulfate and from methanogenesis were calculated from individual redox couples and concentrations of reactants to account for the influence of high Fe2+ concentrations and differing mineral phases. Integrated (O-20 cm) mean rates of sulfate reduction were 1.2 (pelagial), respectively 5.2 (littoral) mmol (m2d)-1. Based on electron equivalents, the estimated iron reduction rates reached between about 50 % (pelagial) and 75 % (littoral) of the sulfate reduction rates. Compared to conditions usually assumed in the literature, in the sediments Gibbs free energy advantage of iron reduction over sulfate reduction was reduced frmm +11 KJeq-1 to a range of about +7 KJeq-1 (ferrihydrite, "reactive iron") to -6 KJeq-1 (goethite). This indicates that iron reduction was thermodynamically favored to sulfate reduction only if amorphous iron(III)oxides were available and is in accordance to the high competitiveness of sulfate reducers in the sediment. While total iron concentration in the sediments was high (up to 80% of the dryweight), reactive iron only accounted for 11-38% and was absolutely and relatively diminished in the zone of iron reduction. Pore-water concentration gradients and 137CS profiles indicated that little or no bioturbation occurred in the sediments, probably inhibiting the renewal of reactive iron. We further hypothesize that the reactivity of the iron oxide surfaces was reduced due to adsorption of DOM, suggested by IR spectra of the DOM and by a surface coverage estimate using literature data. Pelagial and littoral sediments displayed different dynamics. At the littoral relative iron reduction rate estimates were higher, iron sulfides were not accumulated and residence times of iron oxides were short compared to the pelagial. At the littoral site reoxidation of iron sulfides probably resulted in the renewal of reactive iron(III)oxides, possibly allowing for higher relative rates of iron reduction.     

Theoretical speciation of ethylenediamine-N-(o-hydroxyphenylacetic)-N'-(p-hydroxyphenylacetic) acid (o,p-EDDHA) in agronomic conditions

The presence of ethylenediamine-N-(o-hydroxyphenylacetic)-N'-(p-hydroxyphenylacetic) acid (o,p-EDDHA) as the second largest component in commercial EDDHA iron chelates has recently been demonstrated. Here is reported the speciation of o,p-EDDHA by the application of a novel methodology through the determination of the complexing capacity, protonation, and Ca(2+), Mg(2+), Cu(2+), and Fe(3+) stability constants. The pM values and species distribution in solution, hydroponic, and soil conditions were obtained. Due to the para position of one phenol group in o,p-EDDHA, the protonation constants and Ca and Mg stability constants have different values from those of o,o-EDDHA and p,p-EDDHA regioisomers. o,p-EDDHA/Fe(3+) stability constants are higher than those of EDTA/Fe(3+) but lower than those of o,o-EDDHA/Fe(3+). The sequence obtained for pFe is o,o-EDDHA/Fe(3+) >/= o,p-EDDHA/Fe(3+) > EDTA/Fe(3+). o,p-EDDHA/Fe(3+) can be used as an iron chelate in hydroponic conditions. Also, it can be used in soils with limited Cu availability.     

Lactic acid decreases Fe(II) and Fe(III) retention but increases Fe(III) transepithelial transfer by Caco-2 cells

Lactic acid (LA) has been proposed to be an enhancer for dietary iron absorption, but contradictory results have also been reported. In the present study, fully differentiated Caco-2 cell monolayers were used to evaluate the effects of LA (1-50 mmol/L) on the cellular retention and transepithelial transport of soluble non-heme iron (as ferric nitrilotriacetate). Our data revealed a linear decline in Fe(III) retention with respect to the concentration of LA added. In the presence of 50 mmol/L LA, retention of Fe(III) and Fe(II) decreased 57% and 58%, respectively. In contrast, transfer of Fe(III) across the cell monolayer was doubled, while Fe(II) transfer across the cell monolayer decreased 35%. We conclude that LA reduces cellular retention and transepithelial transport of Fe(II) by Caco-2 cells in a dose-dependent manner. However, while LA also reduces retention of Fe(III) by Caco-2 cells, the transfer of Fe(III) across cell monolayers is enhanced, possibly due to effects on paracellular transport.     

Iron uptake by Caco-2 cells from NaFeEDTA and FeSO4: Effects of ascorbic acid, pH, and a Fe(II) chelating agent

Sodium iron(III) ethylenediaminetetraacetate (NaFeEDTA) has considerable promise as an iron fortificant because of its high bioavailability in foods containing iron absorption inhibitors. In this study, uptakes of iron from NaFeEDTA, FeSO4, and FeCl3 by Caco-2 cells were compared in the absence or presence of ascorbic acid (AA), an iron absorption enhancer; at selected pH levels; and in the absence or presence of an iron absorption inhibitor, bathophenanthroline disulfonic acid (BPDS). Ferritin formation in the cells was used as the indicator of iron uptake. Uptake from all three Fe sources was similar in the absence of AA. Adding AA at a 5:1 molar excess as compared to Fe increased uptake by 5.4-, 5.1-, and 2.8-fold for FeSO4, FeCl3, and NaFeEDTA, respectively. The smaller effect of AA on uptake from NaFeEDTA may be related to the higher solubility of NaFeEDTA and/or the strong binding affinity of EDTA for Fe3+, which may prevent AA and duodenal cytochrome b from effectively reducing EDTA-bound Fe. Uptake was inversely related to the pH of the media over a range of 5.8-7.2. Because uptake by DMT-1 is proton-coupled, the inverse relationship between pH and Fe uptake in all three iron sources suggests that they all follow the DMT-1 pathway into the cell. Adding BPDS to the media inhibited uptake from all three iron compounds equally. Because BPDS binds Fe2+ but not Fe3+ and because only Fe2+ is transported by DMT-1, the finding that BPDS inhibited uptake from NaFeEDTA suggests that at least some iron dissociates from EDTA and is reduced just as simple inorganic iron at the brush border membrane of the enterocyte. Taken together, these results suggest that uptake of iron from NaFeEDTA by intestinal enterocytes is regulated similarly to uptake from iron salts.     

Development of an extractive spectrophotometric method for the determination of copper(II) in leafy vegetable and pharmaceutical samples using pyridoxal-4-phenyl-3-thiosemicarbazone (PPT)

A highly sensitive extractive spectrophotometric method has been developed for the determination of copper(II) using pyridoxal-4-phenyl-3-thiosemicarbazone(PPT) as an analytical reagent. The PPT forms reddish brown species of copper(II) at a pH range of 3.0-5.5, and the complex was extracted into n-butanol. The Cu(II)-PPT complex shows maximum absorbance at 440 nm, with molar absorptivity and Sandell's sensitivity being 2.16 x 10(4) L mol(-1) cm(-1) and 2.94 x 10(-3) microg cm(-2), respectively. The system obeys Beer's law in the range of 0.2-5.0 mg/L. The regression coefficient of the Beer's law straight line is 0.338, and the correlation coefficient is 0.96. The detection limit of the method is 0.0065 microg mL(-1). Most of the common metal ions generally found associated with copper do not interfere. The repeatability of the method was checked by finding the relative standard deviation. The developed method has been successfully employed for the determination of copper(II) in leafy vegetable and pharmaceutical samples. The method is evaluated by analyzing samples from the Bureau of Analyzed Samples (BCS 233, 266, 216/1, 207, and 179) and by intercomparison of experimental values using AAS.     

Integrated Flow-based System Displaying an In-line Mini Soil Column to Monitor Iron Species in Soils Leachates

ABSTRACT

Contamination of ground water as a consequence of soil leaching processes is an issue of major concern. In this context, a simulation of the soil leaching process was designed. A sequential injection (SI) method to monitor the soil leaching of iron complexes with in-line rain simulation for leachate production is described. The developed methodology comprises the SI determination of both iron(III) and 3-hydroxy-4-pyridinones iron(III) complexes, coupled to a mini soil column (mSC) for displaying in-line rain simulations. The described SI method enabled iron(III) determination within the range 2.0–35 µmol L^?1, with a detection limit of 0.42 µmol L^?1, and determination of iron(III) complexes in the range 1.0–45 µmol L^?1. It was successfully applied to leachates from laboratory scale soil columns (LSSC), with good precision for both iron(III) and iron complexes determinations: calculated relative standard deviation (RSD) of 5% and 6%, respectively. A step further in automation and miniaturization was attained with the incorporation of a mini soil column for the in-line leachate production. The system enabled the soil leachate production and assessment in less than 5 min, including determinations in triplicate.     

Single-drop and nanogram level determination of sulfite (SO3(2-)) in alcoholic and nonalcoholic beverage samples based on diffuse reflectance fourier transform infrared spectroscopic (DRS-FTIR) analysis on KBr matrix

The diffuse reflectance Fourier transform spectroscopic (DRS-FTIR) method, using potassium bromide matrix, has been developed for the one-drop microdetermination of sulfite in beverage samples. The present method is very simple, rapid, and precise for the determination of sulfite. The nanogram level of sulfite determination is based on the selection of a quantitative analytical peak at 495 cm (-1) among the three observed vibrational peaks obtained by diffuse reflectance Fourier transform infrared spectroscopy (DRS-FTIR). As little as a single drop of sample is sufficient for quantitative analysis of sulfite. The limit of detection (LOD) and the limit of quantification (LOQ) of the method are found to be 8 and 40 ng of SO 3 (2-) 0.1 g (-1) of KBr matrix, respectively. The linear range of the method (LR) as well as the LOD based on the concentration of sulfite in the solution are 5-500 and 0.8 microg/mL, respectively. The precision in terms of standard deviation and relative standard deviation value at a level of 100 ng of SO 3 (2-) 0.1 g (-1) of KBr for n = 10 are found to be 2 ng of SO 3 (2-) and 2.3%, respectively. The relative standard deviation ( n = 10) for the determination of sulfite in beverage samples available in the local market was observed to be in the range of 2.4-7.8%. The method is free from interionic effects of foreign species. No sample pretreatment is required in this method. The proposed method avoids the requirement of large numbers and bulk amounts of reagents. The method is well-suited to the need of green chemistry.     

Determination of Ni (II) in beverages without any sample pretreatment by adsorptive stripping chronopotentiometry (AdSCP)

The purpose of this paper was to use adsorptive stripping chronopotentiometry for the determination of Ni (II) in worldwide consumed beverages without any sample pretreatment, using dimethilglyoxime (DMG) as complexing agent and a glassy carbon mercury film electrode as the working electrode. Ni (DMG)2 complex is adsorbed onto the mercury film at an electrolysis potential of -500 mV for 60 s and then reduced by a -5 microA constant cathodic current. The sensitivity of the method was studied for certified reference water and black tea in the pH range 6.5-11. At pH 9.5 in ammonia buffer, a detection limit of 0.2 microg L(-1) was achieved; the instrumental precision (expressed as rsd %) was 1.5%, and the accuracy, expressed as obtained recoveries both from certified and not certified matrixes, ranged from 93.0 to 95.5 %. The chronopotentiometric analysis executed on commercial beverages provided evidence that black tea samples were the richest source of Ni (II) (1500-3700 microg L(-1)), followed by coffee (100.0-300.5 microg L(-1)); bottled mineral water showed a Ni (II) concentration lower than 4.6 microg L(-1). Among alcoholic beverages, red wines presented the highest content of Ni (II) (55.5-105.0 microg L(-1)). Significant differences were noticed between Ni (II) levels of fermented and distillated alcoholic beverages; moreover, canned cola and beer did not show higher Ni (II) levels with respect to the glass-bottled products.     

Spectrophotometric determination of ascorbic acid in canned fruit juices, cordials, and soft drinks with iron(III) and 1,10-phenanthroline as reagents

A simple and accurate spectrophotometric method has been developed for the determination of ascorbic acid in canned fruit juices, cordials, and soft drinks, based on the reduction of iron(III) by ascorbic acid to iron(II), which is then complexed with 1,10-phenanthroline. Background correction is necessary for most samples and can be achieved by copper(II)-catalyzed oxidation of the acid. The calibration graph was linear from 0 to 8 micrograms/mL of ascorbic acid with a slope of 0.12/ppm. The precision for the determination of ascorbic acid in a lemon drink containing 210 micrograms/mL of the acid was 0.9%. Many ingredients commonly found in fruit juices, cordials, and soft drinks do not interfere; however, tannic acid, pyrogallol, and sulfite interfere with the method. A wide range of samples was analyzed for ascorbic acid content by the proposed method. The samples included mango and lemon tea drinks and also grapefruit juices, for which no background correction is needed.     

Functional analysis of transgenic rice (Oryza sativa L.) transformed with an Arabidopsis thaliana ferric reductase (AtFR02)

Iron deficient soils limit crop production on 25-30% of the world's arable land. Both grasses (Strategy 11) and dicotyledonous crops (Strategy 1) are susceptible to iron deficiency, but each respond to iron stress by different mechanisms. In order to acquire iron from the soil, Strategy I plants utilize an iron reduction and Fe²⁺ transporter system at the root level, whereas Strategy 11 plants use a phytosiderophore-based system. Unfortunately, in some grasses such as rice, the production of phytosiderophores is low, and thus their ability to survive in iron-deficient conditions is limited. To determine whether a Strategy I root reductase can function in a Strategy 11 plant, and enhance its iron acquisition, we inserted the FRO2 gene from Arabidopsis thaliena (AtFR02) into rice (Oryza sativa). Root reductase activity was determined and was found to be low in both transgenic and control plants grown at different iron concentrations. The low activity levels were attributed to the release of soluble reductants in the assay and not to membrane-localized root reductase activity. RT-PCR analysis of rice roots and shoots of plants grown hydroponically at different iron concentrations revealed no expression of the transgene. In this paper, we discuss the lack of functionality of the AtFRO2 gene in rice, and we perform a comparative study of the 0.6 kb promoter region by PlantCARE and PLACE analysis.     

Column preconcentration and spectrophotometric determination of ziram and zineb in commercial samples and foodstuffs using (1,2'-pyridylazo)-2-naphthol (PAN)-naphthalene as adsorbate

A procedure has been developed for the determination of zinc(II) bis(dimethyldithiocarbamate) (ziram) and zinc(II) ethylenebis(dithiocarbamate) (zineb) after preconcentration on a column using naphthalene-(1,2'-pyridylazo)-2-naphthol (PAN) as adsorbent. Ziram and zineb are quantitatively retained on the column in the pH range of 9.0-12.5 and at a flow rate of 1-2 mL/min. The solid mass consisting of the Zn-PAN complex along with naphthalene is dissolved from the column with 5 mL of dimethylformamide (DMF). Absorbance of the complex was measured at 550 nm; Beer's law is obeyed over the concentration ranges of 2.0-22.0 microg of ziram and 5.0-19.8 microg of zineb in 10 mL of the final DMF solution. Ten replicate determinations on a sample solution containing 20 microg of ziram and 18 microg of zineb gave a mean absorbance of 0.33 with relative standard deviations of 0.80 and 0.70%, respectively. The interference of various ions has been studied. The method has been employed for the determination of ziram and zineb in commercial samples and in various foodstuffs, and the results were compared with the earlier reported methods.     

Development of a simple method for the determination of genistein, daidzein, biochanin A, and formononetin (biochanin B) in human urine.

A simple method was developed for the determination of free and/or total isoflavones daidzein, genistein, and their respective 4'-methoxy derivatives biochanin A and formononetin (biochanin B) at low levels in human urine. A solid-phase extraction on octadecyl silica (C(18)) columns was used for the isolation of the phytoestrogens from the matrix. An extraction on a ChemElut 1010 column connected on-line to a Florisil cartridge by a Teflon stopcock was used for effective eluate purification. A mixture of dichloromethane and ethyl acetate was used for elution of the isoflavones from the columns in tandem. The isoflavones were determined as trimethylsilyl (TMS) ethers using GC/MS-SIM after separation on an HP-5MS fused silica column. TMS ethers were obtained by using BSTFA containing 1% of TMCS. For the determination of free isoflavones 6-hydroxyflavone was used as internal standard, whereas robigenin was used in the case of total isoflavone determination. Recoveries for free isoflavones under study varied from 63.5 to 89.6% at the 25 ng mL(-)(1) level and from 63.5 to 89. 2% at the 5 ng mL(-)(1) level in urine. Analytical curves were linear between 5 and 25 ng mL(-)(1). Detection limits varied from 1 ng mL(-)(1) for formononetin to 2.3 ng mL(-)(1) for daidzein. Recoveries for total isoflavone determination after enzymatic hydrolysis with glucuronidase from Helix pomatia ranged from 56.5 to 77.1% at the 25 ng mL(-1) level.     

Stability constants of Mn(II)-complexes in soils as determined by a voltammetric method

A voltammetric method was used for the determination of stability constants (log K) of Mn(II)-complexes in soils. Log K values were of the order of 2–5, being largest at the stage of intensive decomposition of organic matter. The complexing agents were primarily negative in electric charge, and could be retained by soils containing free iron oxides.     

The relative efficiency of ionic iron(III) and iron(II) utilization by the rice plant

Uptake of iron by rice plants was equally rapid when supplied as ionic iron(II) or iron(III) at pH 3 and 4. Iron(III) uptake was reduced at pH 5 and uptake of iron when supplied as FeEDTA was relatively low at all three pH levels.

At pH 4 in the presence of plant roots, reduction of iron(III) to iron(II) occurred as indicated by Fe²⁺ BPDS formation. BPDS in a 3:1 ratio to iron(III) suppressed iron uptake by about 70%. The reduction was observed to be located in the endodermis of young roots and exodermis of older roots.

A capacity to oxidize iron(II) at the root surface was also observed under local anaerobic and relatively high pH conditions.

The significance of these two counteracting processes in affecting the oxidation state of iron at the root surface is discussed.     

Seasonal Variations of Sulphate Reduction Rates, Sulphur Pools and Iron Availability in the Sediment of a Dystrophic Lagoon (Sacca di Goro, Italy)

The aim of this work was to analyse factors which regulate sulphide mobility in the sediments of a dystrophic lagoon (Sacca di Goro, the southern lagoon of the Po river delta, Italy). In 1995-96, sediment oxygen demand and variations in organic matter content, redox potential, iron availability, inorganic sulphur concentrations and sulphate reduction rates were measured in sediment profiles at three stations (G, 4 and 17) representative of the main areas of the lagoon. Stations differed mainly in their salinity range and primary producer communities. High concentrations of reactive iron (110-275 µmol ml-1) and low sulphate reduction rates (0.8-16.1 mmol m-2 d-1) were measured in the sediment. Moreover, high concentrations of reactive ferric iron were detected in winter and spring at the stations closest to the freshwater inputs. Nevertheless, in summer, high concentrations of free sulphides were detected in the porewater, although most of the reactive ferrous iron was not sulphide-bound, indicating that not all of the reactive iron pool was available to buffer against sulphide release and thus measures of reactive iron pools may not be a good measure of the true buffering capacity of the sediment. Furthermore, a considerable production of sulphide may occur in the decaying Ulva biomass in the water column, where its concentration will be independent of the potential buffering capacity of iron in the sediment. Therefore when assessing the vulnerability of coastal lagoons to dystrophic events, both the size and availability of the reactive iron pool as well as the site of sulphide production must be taken into consideration.     

Separation and preconcentration of Cd(II), Cu(II), Ni(II), and Pb(II) in water and food samples using Amberlite XAD-2 functionalized with 3-(2-nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione and determination by inductively coupled plasma-atomic emission spectrometry

A separation and preconcentration procedure was developed for the determination of trace amounts of Cd(II), Cu(II), Ni(II), and Pb(II) in water and food samples using Amberlite XAD-2 fuctionalized with a new chelating ligand, 3-(2-nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione (Amberlite XAD-2-NPTT). The chelating resin was characterized by Fourier transform infrared spectroscopy (FT-IR) and used as a solid sorbent for enrichment of analytes from samples. The sorbed elements were subsequently eluted with 10 mL of 1.0 M HNO(3), and the eluates were analyzed by inductively coupled plasma-atomic emission spectrometry. The influences of the analytical parameters including pH, amount of adsorbent, eluent type and volume, flow rate of the sample solution, volume of the sample solution, and effect of matrix on the preconcentration of metal ions have been studied. The optimum pH for the sorption of four metal ions was about 6.0. The limits of detection were found to be 0.22, 0.18, 0.20, and 0.16 μg L(-1) for Cd(II), Cu(II), Ni(II), and Pb(II), respectively, with a preconcentration factor 60. The proposed method was applied successfully for the determination of metal ions in water and food samples.     

Interactions Between Benthic Phosphorus Release and Sulfur Cycling in Lake Scharmützelsee (Germany)

Sulfur (S) conversions were determined during summer stratification in 1995/96 to assess the extent to which benthic release of phosphorus (P) is influenced by the S cycling in eutrophic, dimictic, sulfate-rich (61.33 ± 10.41 mg SO42- l-1) freshwater Lake Schamützelsee. Hypolimnetic SO42- reduction (4.56 ± 0.73 g (S) m-2 d-1) forming ΣH2S (44.71 ± 17.57 mg ΣH2S m-2 d-1), leading to iron sulfide precipitation (5.62 ± 1.72 mg FeS m-2 d-1) and dissolved iron depletion in the hypolimnion has a major influence on benthic P mobilization and release. The most important inorganic S pool is the CRS (FeS2 + S° + H2S; 15.1 % total S), being 1.3 to 6.6 times higher than the AVS (FeS + H2S) in the uppermost 0 - 8 cm sediment. This diminishes the ability of the sediment to bind P (indicated by 14.6 % loosely bound P (NH4Cl-P) and an exhaustion of the redox-sensitive P (BD-P)), leading to interstitial water P concentrations up to 10.8 mg l-1 and P release rates of 2.64 ± 0.56 mg P m-2 d-1. As a consequence the P content of the lake increased fourfold within 58 days.