Determination of anti-cancer drug emodin using a silica-gel-modified carbon paste electrode

In this paper, a silica-gel-modified carbon paste electrode (Si-gel/CPE) was used to determine the anti-cancer drug emodin by anodic stripping differential pulse voltammetry (ASDPV). The effects of the silica-gel content, the pH of the supporting electrolyte, and the scan rate on the oxidation current of emodin were investigated. The oxidation currents of emodin obtained from ASDPV measurements were linearly correlated with the concentration in the range of 5.0 × 10-9 to 300.0 × 10-9 mol L-1. The limit of detection was determined to be 1.5 × 10-9 mol L-1. The current method was successfully applied to determine emodin in a knotweed root sample, with recovery rate of 92.5% to 98.3%.

Determination of herbicides residues in soil by small scale extraction

Herbicides such as trifluralin, simazine, atrazine, metribuzin and metolachlor are used in Brazilian agriculture. The efficiency of a small scale method for determination of these herbicides and two degradation products (deisopropylatrazine and deethylatrazine) in soil samples was evaluated. The compounds were extracted from soil samples (5 g) with 20 ml of ethyl acetate in a mechanical shaker for 50 min. Following the extraction, the supernatant was dried through anhydrous sodium sulphate, concentrated and analysed by high resolution gas chromatography (HRGC) with thermionic specific detection (TSD). Mean recoveries obtained from soil samples fortified at three different levels ranged from 81 to 115% with relative standard deviation (RSD) values varying from 1.2 to 12.7%. The method detection limits ranged from 0.01 to 0.06 mg kg-1. The methodology was applied using soil samples from farms located near the town of Araraquara, in the State of São Paulo, Brazil.

Determination of carbon monoxide using a coated quartz crystal sensor

Carbon monoxide was detected and determined by a piezoelectric quartz crystal sensor coated with nickel(II)-phthalocyanine 50 % (v/v) solution in glycerine. Studies on the effect of temperature, flow rate, and some possible interferents were carried out. Calibration curves, sensor stability (lifetime) and the precision of measurements were also verified. The resulting selectivity is probably due to the coordinative binding between the electronically unsatured metal complexes and the analyte. The analytical curve is linear in the concentration range 0.10 to 1.0 % (v/v).

Ascorbic acid determination using a carbon paste electrode modified with iron(III) ions adsorbed on humic acid

An amperometric sensor was constructed, by using humic acids to immobilize Fe3+ ions on a carbon paste electrode (CPE-HA-Fe), and used for ascorbic acid (H2A) determination. The cyclic voltammogram of the electrode showed electrochemical response due to the Fe3+/Fe2+ couple at E1/2=+0.78 V vs SCE, using 0.5 mol L-1 KCl and 0.2 mol L-1 acetate/0.020 mol L-1 phosphate buffer, at pH = 5.4, as supporting electrolyte. When H2A is added to the electrolyte solution it is observed an oxidation process. The oxidation current, obtained by chronoamperommetry at +0.87 V vs SCE, is proportional to the concentration, represented by the equation I(µA) = 7.6286 [H2A] (mmol L-1) + 1.9583, r = 0.9996, for concentrations between 0.0 and 1.4 mmol L-1. The electrode showed high stability and was used for H2A determination in a natural orange juice.

Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 silica in the determination of copper

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol for determination of Cu(II) ions in sugar cane spirit (cachaça) is described, based on differential pulse anodic stripping voltammetry (DPASV) procedure. The Cu(II) oxidation peak was observed at 0.03 V (vs. SCE) in phosphate solution (pH 3.0). The results were obtained using optimised conditions such as 100 mV pulse amplitude, 3 min accumulation time, 25 mV s-1 scan rate in phosphate solution pH 3.0, resulting in a linear dynamic range from 8.0 x 10-7 to 1.0 x 10-5 mol L-1 Cu(II) and a limit of detection 2.0 x10-7 mol L-1. Cu(II) spiked in a cachaça sample was determined with 102.5 % mean recovery at mmol L-1 level. Interference from other metallic cations present in the sample was avoided by the standard addition procedure.

Mycorrhizal Association and Microbial Activity of Soil Cultivated with Cassava After Application of Mesotrione and Fluazifop-p-Butyl

Soil is a very heterogeneous environment that allows the establishment of wide range of microorganisms populations, whose balance is affected by biotic and abiotic factors. This study has aimed to assess the effect of doses of mesotrione and fluazifop-p-butyl herbicides and two assessment periods on microbial activity and biomass of soil cultivated with cassava Cacau-UFV cultivar, besides the root colonization by arbuscular mycorrhizal fungi. Two trials were conducted in a protected environment where was realized post-emergence application of mesotrione in the doses of 72, 108, 144 and 216 g ha-1 and fluazifop-p-butyl in the doses of 100, 150, 200 and 300 g ha-1, besides a control without application. Soil samples were collected for determination of soil respiratory rate (RR), microbial biomass carbon (MBC), metabolic quotient (qCO2), and colonization of roots by arbuscular mycorrhizal fungi at the 30 and 60 days after applications (DAA) of the herbicides. Fluazifop-p-butyl increased the RR, MBC and the percentage of cassava roots colonized by mycorrhizal fungi in the assessment performed at 60 DAA. The larger effects of mesotrione on soil microbial indicators were up to 30 DAA, being the changes minimized at 60 DAA. It is concluded that the herbicides alter the soil microbial indicators, with effects dependent of the product, of dose applied and also of the period of assessment.

PVC Supported Liquid Membrane and Carbon Paste Potentiometric Sensors Incorporating a Mn(III)-Porphyrin for the Direct Determination of Undissociated Paracetamol

PVC supported liquid membrane and carbon paste potentiometric sensors incorporating an Mn(III)-porphyrin complex as a neutral host molecule were developed for the determination of paracetamol. The measurements were carried out in solution at pH 5.5. Under such conditions paracetamol exists as a neutral molecule. The mechanism of molecular recognition between the Mn(III)-porphyrin and paracetamol, leading to potentiometric signal generation, is discussed.The sensitivity and selectivity toward paracetamol of carbon paste and polymeric liquid membrane electrodes incorporating an Mn(III)-porphyrin host were compared. The applicability of these sensors to the direct determination of paracetamol was checked by performing a recovery test in human plasma.

Electrochemical Reduction and Voltammetric Determination of Metronidazole Benzoate at Modified Carbon Paste Electrode

A metalloporphyrin incorporated carbon paste sensor has been developed for the determination of metronidazole benzoate (MTZB). Zn(II) complex of 5,10,15,20-tetrakis (3-methoxy-4-hydroxy phenyl) porphyrin (TMHPP) was used as the active material. The MTZB gave a well-defined reduction peak at - 0.713V in 0.1 mol l -1 phosphate buffer solution of pH around 7. Compared with bare carbon paste electrode (CPE), the TMHPP Zn(II) modified electrode significantly enhanced the reduction peak current of MTZB as well as lowered its reduction potential. Under optimum conditions the reduction peak current was proportional to MTZB concentration over the range 1×10-3 mol1-1 to 1×10-5mol1-1. The detection limit was found to be 4.36×10-6mol1-1 . This sensor has been successfully applied for the determination of MTZB in pharmaceutical formulations and urine samples.

Soil organic carbon management for sustainable land use in Sudano-Sahelian West Africa

Judged by their negative nutrient balances, low soil cover and low productivity, the predominant agro-pastoral farming systems in the Sudano-Sahelian zone of West Africa are highly unsustainable for crop production intensification. With kaolinite as the main clay type, the cation exchange capacity of the soils in this region, often less than 1 cmol_c kg^-1 soil, depends heavily on the organic carbon (Corg) content. However, due to low carbon sequestration and to the microbe, termite and temperature-induced rapid turnover rates of organic material in the present land-use systems, Corg contents of the topsoil are very low, ranging between 1 and 8 g kg^-1 in most soils. For sustainable food production, the availability of phosphorus (P) and nitrogen (N) has to be increased considerably in combination with an improvement in soil physical properties. Therefore, the adoption of innovative management options that help to stop or even reverse the decline in Corg typically observed after cultivating bush or rangeland is of utmost importance. To maintain food production for a rapidly growing population, targeted applications of mineral fertilisers and the effective recycling of organic amendments as crop residues and manure are essential. Any increase in soil cover has large effects in reducing topsoil erosion by wind and water and favours the accumulation of wind-blown dust high in bases which in turn improves P availability. In the future decision support systems, based on GIS, modelling and simulation should be used to combine (i) available fertiliser response data from on-station and on-farm research, (ii) results on soil productivity restoration with the application of mineral and organic amendments and (iii) our present understanding of the cause-effect relationships governing the prevailing soil degradation processes. This will help to predict the effectiveness of regionally differentiated soil fertility management approaches to maintain or even increase soil Corg levels.

Application of biogas slurries from energy crops to arable soils and their impact on carbon and nitrogen dynamics

The use of renewable primary products as co-substrate or single substrate for biogas production has increased consistently over the last few years. Maize silage is the preferential energy crop used for fermentation due to its high methane (CH4) yield per hectare. Equally, the by-product, namely biogas slurry (BS), is used with increasing frequency as organic fertilizer to return nutrients to the soil and to maintain or increase the organic matter stocks and soil fertility. Studies concerning the application of energy crop-derived BS on the carbon (C) and nitrogen (N) mineralization dynamics are scarce. Thus, this thesis focused on the following objectives: I) The determination of the effects caused by rainfall patterns on the C and N dynamics from two contrasting organic fertilizers, namely BS from maize silage and composted cattle manure (CM), by monitoring emissions of nitrous oxide (N2O), carbon dioxide (CO2) and CH4 as well as leaching losses of C and N. II) The investigation of the impact of differences in soil moisture content after the application of BS and temperature on gaseous emissions (CO2, N2O and CH4) and leaching of C and N compounds. III) A comparison of BS properties obtained from biogas plants with different substrate inputs and operating parameters and their effect on C and N dynamics after application to differently textured soils with varying application rates and water contents. For the objectives I) and II) two experiments (experiment I and II) using undisturbed soil cores of a Haplic Luvisol were carried out. Objective III) was studied on a third experiment (experiment III) with disturbed soil samples. During experiment I three rainfall patterns were implemented including constant irrigation, continuous irrigation with periodic heavy rainfall events, and partial drying with rewetting periods. Biogas slurry and CM were applied at a rate of 100 kg N ha-1. During experiment II constant irrigation and an irrigation pattern with partial drying with rewetting periods were carried out at 13.5°C and 23.5°C. The application of BS took place either directly before a rewetting period or one week after the rewetting period stopped. Experiment III included two soils of different texture which were mixed with ten BS’s originating from ten different biogas plants. Treatments included low, medium and high BS-N application rates and water contents ranging from 50% to 100% of water holding capacity (WHC). Experiment I and II showed that after the application of BS cumulative N2O emissions were 4 times (162 mg N2O-N m-2) higher compared to the application of CM caused by a higher content of mineral N (Nmin) in the form of ammonium (NH4+) in the BS. The cumulative emissions of CO2, however, were on the same level for both fertilizers indicating similar amounts of readily available C after composting and fermentation of organic material. Leaching losses occurred predominantly in the mineral form of nitrate (NO3-) and were higher in BS amended soils (9 mg NO3--N m-2) compared to CM amended soils (5 mg NO3--N m-2). The rainfall pattern in experiment I and II merely affected the temporal production of C and N emissions resulting in reduced CO2 and enhanced N2O emissions during stronger irrigation events, but showed no effect on the cumulative emissions. Overall, a significant increase of CH4 consumption under inconstant irrigation was found. The time of fertilization had no effect on the overall C and N dynamics. Increasing temperature from 13.5°C to 23.5°C enhanced the CO2 and N2O emissions by a factor of 1.7 and 3.7, respectively. Due to the increased microbial activity with increasing temperature soil respiration was enhanced. This led to decreasing oxygen (O2) contents which in turn promoted denitrification in soil due to the extension of anaerobic microsites. Leaching losses of NO3- were also significantly affected by increasing temperature whereas the consumption of CH4 was not affected. The third experiment showed that the input materials of biogas plants affected the properties of the resulting BS. In particular the contents of DM and NH4+ were determined by the amount of added plant biomass and excrement-based biomass, respectively. Correlations between BS properties and CO2 or N2O emissions were not detected. Solely the ammonia (NH3) emissions showed a positive correlation with NH4+ content in BS as well as a negative correlation with the total C (Ct) content. The BS-N application rates affected the relative CO2 emissions (% of C supplied with BS) when applied to silty soil as well as the relative N2O emissions (% of N supplied with BS) when applied to sandy soil. The impacts on the C and N dynamics induced by BS application were exceeded by the differences induced by soil texture. Presumably, due to the higher clay content in silty soils, organic matter was stabilized by organo-mineral interactions and NH4+ was adsorbed at the cation exchange sites. Different water contents induced highest CO2 emissions and therefore optimal conditions for microbial activity at 75% of WHC in both soils. Cumulative nitrification was also highest at 75% and 50% of WHC whereas the relative N2O emissions increased with water content and showed higher N2O losses in sandy soils. In summary it can be stated that the findings of the present thesis confirmed the high fertilizer value of BS’s, caused by high concentrations of NH4+ and labile organic compounds such as readily available carbon. These attributes of BS’s are to a great extent independent of the input materials of biogas plants. However, considerably gaseous and leaching losses of N may occur especially at high moisture contents. The emissions of N2O after field application corresponded with those of animal slurries.

Predicted soil organic carbon stocks and changes in Jordan between 2000 and 2030 made using the GEFSOC modelling system

Estimates of soil organic carbon (SOC) stocks and changes under different land use systems can help determine vulnerability to land degradation. Such information is important for countries in and areas with high susceptibility to desertification. SOC stocks, and predicted changes between 2000 and 2030, were determined at the national scale for Jordan using The Global Environment Facility Soil Organic Carbon (GEFSOC) Modelling System. For the purpose of this study, Jordan was divided into three natural regions (The Jordan Valley, the Uplands and the Badia) and three developmental regions (North, Middle and South). Based on this division, Jordan was divided into five zones (based on the dominant land use): the Jordan Valley, the North Uplands, the Middle Uplands, the South Uplands and the Badia. This information was merged using GIS, along with a map of rainfall isohyets, to produce a map with 498 polygons. Each of these was given a unique ID, a land management unit identifier and was characterized in terms of its dominant soil type. Historical land use data, current land use and future land use change scenarios were also assembled, forming major inputs of the modelling system. The GEFSOC Modelling System was then run to produce C stocks in Jordan for the years 1990, 2000 and 2030. The results were compared with conventional methods of estimating carbon stocks, such as the mapping based SOTER method. The results of these comparisons showed that the model runs are acceptable, taking into consideration the limited availability of long-term experimental soil data that can be used to validate them. The main findings of this research show that between 2000 and 2030, SOC may increase in heavily used areas under irrigation and will likely decrease in grazed rangelands that cover most of Jordan giving an overall decrease in total SOC over time if the land is indeed used under the estimated forms of land use. (C) 2007 Elsevier B.V. All rights reserved.

Modelled soil organic carbon stocks and changes in the Indo-Gangetic Plains, India from 1980 to 2030

The Global Environment Facility co-financed Soil Organic Carbon (GEFSOC) Project developed a comprehensive modelling system for predicting soil organic carbon (SOC) stocks and changes over time. This research is an effort to predict SOC stocks and changes for the Indian, Indo-Gangetic Plains (IGP), an area with a predominantly rice (Oryza sativa) - wheat (Triticum aestivum) cropping system, using the GEFSOC Modelling System and to compare output with stocks generated using mapping approaches based on soil survey data. The GEFSOC Modelling System predicts an estimated SOC stock for the IGP, India of 1.27, 1.32 and 1.27 Pg for 1990, 2000 and 2030, respectively, in the top 20 cm of soil. The SOC stock using a mapping approach based on soil survey data was 0.66 and 0.88 Pg for 1980 and 2000, respectively. The SOC stock estimated using the GEFSOC Modelling System is higher than the stock estimated using the mapping approach. This is due to the fact that while the GEFSOC System accounts for variation in crop input data (crop management), the soil mapping approach only considers regional variation in soil texture and wetness. The trend of overall change in the modelled SOC stock estimates shows that the IGP, India may have reached an equilibrium following 30-40 years of the Green Revolution. This can be seen in the SOC stock change rates. Various different estimation methods show SOC stocks of 0.57-1.44 Pg C for the study area. The trend of overall change in C stock assessed from the soil survey data indicates that the soils of the IGP, India may store a projected 1.1 Pg of C in 2030. (C) 2007 Elsevier B.V. All rights reserved.

Determination of the impact of continuous defoliation of Lolium perenne and Trifolium repens on bacterial and fungal community structure in rhizosphere soil

To determine the effects of defoliation on microbial community structure, rhizosphere soil samples were taken pre-, and post-defoliation from the root tip and mature root regions of Trifolium repens L. and Lolium perenne L. Microbial DNA isolated from samples was used to generate polymerase chain reaction-denaturing gradient gel electrophoresis molecular profiles of bacterial and fungal communities. Bacterial plate counts were also obtained. Neither plant species nor defoliation affected the bacterial and fungal community structures in both the root tip and mature root regions, but there were significant differences in the bacterial and fungal community profiles between the two root regions for each plant. Prior to defoliation, there was no difference between plants for bacterial plate counts of soils from the root tip regions; however, counts were greater in the mature root region of L. perenne than T. repens. Bacterial plate counts for T. repens were higher in the root tip than the mature root region. After defoliation, there was no effect of plant type, position along the root or defoliation status on bacterial plate counts, although there were significant increases in bacterial plate counts with time. The results indicate that a general effect existed during maturation in the root regions of each plant, which had a greater impact on microbial community structure than either plant type or the effect of defoliation. In addition there were no generic consequences with regard to microbial populations in the rhizosphere as a response to plant defoliation.