The role of soil microbes in the global carbon cycle: tracking the below-ground microbial processing of plant-derived carbon for manipulating carbon dynamics in agricultural systems.

It is well known that atmospheric concentrations of carbon dioxide (CO2) (and other greenhouse gases) have increased markedly as a result of human activity since the industrial revolution. It is perhaps less appreciated that natural and managed soils are an important source and sink for atmospheric CO2 and that, primarily as a result of the activities of soil microorganisms, there is a soil-derived respiratory flux of CO2 to the atmosphere that overshadows by tenfold the annual CO2 flux from fossil fuel emissions. Therefore small changes in the soil carbon cycle could have large impacts on atmospheric CO2 concentrations. Here we discuss the role of soil microbes in the global carbon cycle and review the main methods that have been used to identify the microorganisms responsible for the processing of plant photosynthetic carbon inputs to soil. We discuss whether application of these techniques can provide the information required to underpin the management of agro-ecosystems for carbon sequestration and increased agricultural sustainability. We conclude that, although crucial in enabling the identification of plant-derived carbon-utilising microbes, current technologies lack the high-throughput ability to quantitatively apportion carbon use by phylogentic groups and its use efficiency and destination within the microbial metabolome. It is this information that is required to inform rational manipulation of the plant–soil system to favour organisms or physiologies most important for promoting soil carbon storage in agricultural soil.

Mathematical solutions for electricity networks in a low carbon future

Smart meters are becoming more ubiquitous as governments aim to reduce the risks to the energy supply as the world moves toward a low carbon economy. The data they provide could create a wealth of information to better understand customer behaviour. However at the household, and even the low voltage (LV) substation level, energy demand is extremely volatile, irregular and noisy compared to the demand at the high voltage (HV) substation level. Novel analytical methods will be required in order to optimise the use of household level data. In this paper we briefly outline some mathematical techniques which will play a key role in better understanding the customer's behaviour and create solutions for supporting the network at the LV substation level.

Land use and climate change impacts on soil organic carbon stocks in semi-arid Spain

Purpose The sensitivity of soil organic carbon to global change drivers, according to the depth profile, is receiving increasing attention because of its importance in the global carbon cycle and its potential feedback to climate change. A better knowledge of the vertical distribution of SOC and its controlling factors—the aim of this study—will help scientists predict the consequences of global change. Materials and methods The study area was the Murcia Province (S.E. Spain) under semiarid Mediterranean conditions. The database used consists of 312 soil profiles collected in a systematic grid, each 12 km2 covering a total area of 11,004 km2. Statistical analysis to study the relationships between SOC concentration and control factors in different soil use scenarios was conducted at fixed depths of 0–20, 20–40, 40–60, and 60–100 cm. Results and discussion SOC concentration in the top 40 cm ranged between 6.1 and 31.5 g kg−1, with significant differences according to land use, soil type and lithology, while below this depth, no differences were observed (SOC concentration 2.1–6.8 g kg−1). The ANOVA showed that land use was the most important factor controlling SOC concentration in the 0–40 cm depth. Significant differences were found in the relative importance of environmental and textural factors according to land use and soil depth. In forestland, mean annual precipitation and texture were the main predictors of SOC, while in cropland and shrubland, the main predictors were mean annual temperature and lithology. Total SOC stored in the top 1 m in the region was about 79 Tg with a low mean density of 7.18 kg Cm−3. The vertical distribution of SOC was shallower in forestland and deeper in cropland. A reduction in rainfall would lead to SOC decrease in forestland and shrubland, and an increase of mean annual temperature would adversely affect SOC in croplands and shrubland. With increasing depth, the relative importance of climatic factors decreases and texture becomes more important in controlling SOC in all land uses. Conclusions Due to climate change, impacts will be much greater in surface SOC, the strategies for C sequestration should be focused on subsoil sequestration, which was hindered in forestland due to bedrock limitations to soil depth. In these conditions, sequestration in cropland through appropriate management practices is recommended.

Identification and quantification of glucosinolate and flavonol compounds in rocket salad (Eruca sativa, Eruca vesicaria and Diplotaxis tenuifolia) by LC–MS: Highlighting the potential for improving nutritional value of rocket crops

Liquid Chromatography Mass Spectrometry (LC-MS) was used to obtain glucosinolate and flavonol content for 35 rocket accessions and commercial varieties. 13 glucosinolates and 11 flavonol compounds were identified. Semi-quantitative methods were used to estimate concentrations of both groups of compounds. Minor glucosinolate composition was found to be different between accessions; concentrations varied significantly. Flavonols showed differentiation between genera, with Diplotaxis accumulating quercetin glucosides and Eruca accumulating kaempferol glucosides. Several compounds were detected in each genus that have only previously been reported in the other. We highlight how knowledge of phytochemical content and concentration can be used to breed new, nutritionally superior varieties. We also demonstrate the effects of controlled environment conditions on the accumulations of glucosinolates and flavonols and explore the reasons for differences with previous studies. We stress the importance of consistent experimental design between research groups to effectively compare and contrast results.

The carbon dioxide production rate assumption biases gastric emptying parameters in healthy adults

RATIONALE: An altered gastric emptying (GE) rate has been implicated in the aetiology of obesity. The (13)C-octanoic acid breath test (OBT) is frequently used to measure GE, and the cumulative percentage of (13)C recovered (cPDR) is a common outcome measure. However, true cPDR in breath is dependent on accurate measurement of carbon dioxide production rate (VCO(2)). The current study aimed to quantify differences in the (13)C OBT results obtained using directly measured VCO(2) (VCO(2DM)) compared with (i) predicted from resting VCO(2) (VCO(2PR)) and (ii) predicted from body surface area VCO(2) (VCO(2BSA)). METHODS: The GE rate of a high-fat test meal was assessed in 27 lean subjects using the OBT. Breath samples were gathered during the fasted state and at regular intervals throughout the 6-h postprandial period for determination of (13)C-isotopic enrichment by continuous-flow isotope-ratio mass spectrometry. The VCO(2) was measured directly from exhaled air samples and the PDR calculated by three methods. The bias and the limits of agreement were calculated using Bland-Altman plots. RESULTS: Compared with the VCO(2DM), the cPDR was underestimated by VCO(2PR) (4.8%; p = 0.0001) and VCO(2BSA) (2.7%; p = 0.02). The GE T(half) was underestimated by VCO(2PR) (13 min; p = 0.0001) and VCO(2BSA) (10 min; p = 0.01), compared with VCO(2DM). CONCLUSIONS: The findings highlight the importance of directly measuring VCO(2)production rates throughout the (13)C OBT and could partly explain the conflicting evidence regarding the effect of obesity on GE rates.

The hidden organic carbon in deep mineral soils

Aims Current estimates of soil organic carbon (SOC) are based largely on surficial measurements to depths of 0.3 to 1 m. Many of the world’s soils greatly exceed 1 m depth and there are numerous reports of biological activity to depths of many metres. Although SOC storage to depths of up to 8 m has been previously reported, the extent to which SOC is stored at deeper depths in soil profiles is currently unknown. This paper aims to provide the first detailed analysis of these previously unreported stores of SOC. Methods Soils from five sites in the deeply weathered regolith in the Yilgarn Craton of south-western Australia were sampled and analysed for total organic carbon by combustion chromatography. These soils ranged between 5 and 38 m (mean 21 m) depth to bedrock and had been either recently reforested with Pinus pinaster or were under agriculture. Sites had a mean annual rainfall of between 399 and 583 mm yr−1. Results The mean SOC concentration across all sites was 2.30 ± 0.26 % (s.e.), 0.41 ± 0.05 % and 0.23 ± 0.04 % in the surface 0.1, 0.1–0.5 and 0.5 to 1.0 m increments, respectively. The mean value between 1 and 5 m was 0.12 ± 0.01 %, whereas between 5 and 35 m the values decreased from 0.04 ± 0.002 % to 0.03 ± 0.003 %. Mean SOC mass densities for each of the five locations varied from 21.8–37.5 kg C m−2, and were in toto two to five times greater than would be reported with sampling to a depth of 0.5 m. Conclusions This finding may have major implications for estimates of global carbon storage and modelling of the potential global impacts of climate change and land-use change on carbon cycles. The paper demonstrates the need for a reassessment of the current arbitrary shallow soil sampling depths for assessing carbon stocks, a revision of global SOC estimates and elucidation of the composition and fate of deep carbon in response to land use and climate change

Gross direct and embodied carbon sinks for urban inventories

Cities and urban regions are undertaking efforts to quantify greenhouse (GHG) emissions from their jurisdictional boundaries. Although inventorying methodologies are beginning to standardize for GHG sources, carbon sequestration is generally not quantified. This article describes the methodology and quantification of gross urban carbon sinks. Sinks are categorized into direct and embodied sinks. Direct sinks generally incorporate natural process, such as humification in soils and photosynthetic biomass growth (in urban trees, perennial crops, and regional forests). Embodied sinks include activities associated with consumptive behavior that result in the import and/or storage of carbon, such as landfilling of waste, concrete construction, and utilization of durable wood products. Using methodologies based on the Intergovernmental Panel on Climate Change 2006 guidelines (for direct sinks) and peer-reviewed literature (for embodied sinks), carbon sequestration for 2005 is calculated for the Greater Toronto Area. Direct sinks are found to be 317 kilotons of carbon (kt C), and are dominated by regional forest biomass. Embodied sinks are calculated to be 234 kt C based on one year's consumption, though a complete life cycle accounting of emissions would likely transform this sum from a carbon sink to a source. There is considerable uncertainty associated with the methodologies used, which could be addressed with city-specific stock-change measurements. Further options for enhancing carbon sink capacity within urban environments are explored, such as urban biomass growth and carbon capture and storage.

Quantification of chlordesmethyldiazepam by liquid chromatography-tandem mass spectrometry: application to a cloxazolam bioequivalence study

A rapid, sensitive and specific LC-MS/MS method was developed and validated for quantifying chlordesmethyldiazepam (CDDZ or delorazepam), the active metabolite of cloxazolam, in human plasma. In the analytical assay, bromazepam (internal standard) and CDDZ were extracted using a liquid-liquid extraction (diethyl-ether/hexane, 80/20, v/v) procedure. The LC-MS/MS method on a RP-C18 column had an overall run time of 5.0 min and was linear (1/x weighted) over the range 0.5-50 ng/mL (R > 0.999). The between-run precision was 8.0% (1.5 ng/mL), 7.6% (9 ng/mL), 7.4% (40 ng/mL), and 10.9% at the low limit of quantification-LLOQ (0.500 ng/mL). The between-run accuracies were 0.1, -1.5, -2.7 and 8.7% for the above mentioned concentrations, respectively. All current bioanalytical method validation requirements (FDA and ANVISA) were achieved and it was applied to the bioequivalence study (Cloxazolam-test, Eurofarma Lab. Ltda and Olcadil (R)-reference, Novartis Biociencias S/A). The relative bioavailability between both formulations was assessed by calculating individual test/reference ratios for Cmax, AUClast and AUCO-inf. The pharmacokinetic profiles indicated bioequivalence since all ratios were as proposed by FDA and ANVISA. Copyright (C) 2009 John Wiley & Sons, Ltd.

Ciprofibrate quantification in human plasma by high-performance liquid chromatography coupled with electrospray tandem mass spectrometry for pharmacokinetic studies

A rapid, sensitive and specific method for quantifying ciprofibrate in human plasma using bezafibrate as the internal standard (IS) is described. The sample was acidified prior extraction with formic acid (88%). The analyte and the IS were extracted from plasma by liquid-liquid extraction using an organic solvent (diethyl ether/dichloromethane 70/30 (v/v)). The extracts were analyzed by high performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC-MS/MS). Chromatography was performed using Genesis C18 4 mu m analytical column (4.6 x 150 mm i.d.) and a mobile phase consisting of acetonitrile/water (70/30, v/v) and 1 mM acetic acid. The method had a chromatographic run time of 3.4 min and a linear calibration curve over the range 0.1-60 mu g/mL (r > 0.99). The limit of quantification was 0.1 mu g/mL. The intra- and interday accuracy and precision values of the assay were less than 13.5%. The stability tests indicated no significant degradation. The recovery of ciprofibrate was 81.2%, 73.3% and 76.2% for the 0.3, 5.0 and 48.0 ng/mL standard concentrations, respectively. For ciprofibrate, the optimized parameters of the declustering potential, collision energy and collision exit potential were -51 V, -16 eV and -5 V, respectively. The method was also validated without the use of the internal standard. This HPLC-MS/MS procedure was used to assess the bioequivalence of two ciprofibrate 100 mg tablet formulations in healthy volunteers of both sexes. The following pharmacokinetic parameters were obtained from the ciprofibrate plasma concentration vs. time curves: AUC(last), AUC(0-168 h), C(max) and T(max). The geometric mean with corresponding 90% confidence interval (CI) for test/reference percent ratios were 93.80% (90% CI = 88.16-99.79%) for C(max), 98.31% (90% CI = 94.91-101.83%) for AUC(last) and 97.67% (90% CI = 94.45-101.01%) for AUC(0-168 h). Since the 90% Cl for AUC(last), AUC(0-168 h) and C(max) ratios were within the 80-125% interval proposed by the US FDA, it was concluded that ciprofibrate (Lipless (R) 100 mg tablet) formulation manufactured by Biolab Sanus Farmaceutica Ltda. is bioequivalent to the Oroxadin (R) (100 mg tablet) formulation for both the rate and the extent of absorption. (C) 2011 Published by Elsevier B.V.

Use of Information Visualization Methods Eliminating Cross Talk in Multiple Sensing Units Investigated for a Light-Addressable Potentiometric Sensor

The integration of nanostructured films containing biomolecules and silicon-based technologies is a promising direction for reaching miniaturized biosensors that exhibit high sensitivity and selectivity. A challenge, however, is to avoid cross talk among sensing units in an array with multiple sensors located on a small area. In this letter, we describe an array of 16 sensing units, of a light-addressable potentiometric sensor (LAPS), which was made with layer-by-Layer (LbL) films of a poly(amidomine) dendrimer (PAMAM) and single-walled carbon nanotubes (SWNTs), coated with a layer of the enzyme penicillinase. A visual inspection of the data from constant-current measurements with liquid samples containing distinct concentrations of penicillin, glucose, or a buffer indicated a possible cross talk between units that contained penicillinase and those that did not. With the use of multidimensional data projection techniques, normally employed in information Visualization methods, we managed to distinguish the results from the modified LAPS, even in cases where the units were adjacent to each other. Furthermore, the plots generated with the interactive document map (IDMAP) projection technique enabled the distinction of the different concentrations of penicillin, from 5 mmol L(-1) down to 0.5 mmol L(-1). Data visualization also confirmed the enhanced performance of the sensing units containing carbon nanotubes, consistent with the analysis of results for LAPS sensors. The use of visual analytics, as with projection methods, may be essential to handle a large amount of data generated in multiple sensor arrays to achieve high performance in miniaturized systems.

Electronic transport properties of ascorbic acid and nicotinamide adsorbed on single-walled carbon nanotubes

Ab initio simulations of carbon nanotubes interacting with ascorbic acid and nicotinamide are reported. The electronic transport properties of these systems are studied using a combination of density functional theory and non-equilibrium Green`s functions methods. The adsorptions of both molecules are observed to depend strongly on their functionalization. The interaction through the appropriate functionalized species modifies the structural and electronic properties of the original system, resulting in a chemisorption regime. Changes in the electronic transport properties are also observed, with reductions on the total electronic transmission probabilities. Nevertheless, when the molecules interact through the pristine form, a physisorption interaction is observed with insignificant structural and electronic transport changes. (c) 2011 Elsevier B.V. All rights reserved.

Carbon nanotubes in nanostructured films: Potential application as amperometric and potentiometric field-effect (bio-)chemical sensors

The assembly of carbon nanotubes (CNTs) into nanostructured films is attractive for producing functionalized hybrid materials and (bio-)chemical sensors, but this requires experimental methods that allow for control of molecular architecturcs. In this study, we exploit the layer-by-layer (LbL) technique to obtain two types of sensors incorporating CNTs. In the first, LbL films of alternating layers of multi-walled carbon nanotubes (MWNTs) dispersed in polyarninoamide (PAMAM) dendrimers and nickel phthalocyanine (NiTsPc) were used in amperometric detection of the neurotransmitter dopamine (DA). The electrochemical properties evaluated with cyclic voltammetry indicated that the incorporation of MWNTs in the PAMAM-NT/NiTsPc LbL films led to a 3-fold increase in the peak current, in addition to a decrease of 50 mV in the oxidation potential of DA. The latter allowed detection of DA even in the presence of ascorbic acid (AA), a typical interferent for DA. Another LbL film was obtained with layers of PAMAM and single-walled carbon nanotubes (SWNTs) employed in field-effect-devices using a capacitive electrolyte-insulator-semiconductor structure (EIS). The adsorption of the film components was monitored by measuring the flat-band voltage shift in capacitance-voltage (C-P) curves, caused by the charges from the components. Constant capacitance (ConCap) measurements showed that the EISPAMAM/SWNT film displayed a high pH sensitivity (ca. 54.5 mV/pH), being capable of detecting penicillin G between 10(-4) mol L(-1) and 10(-2) mol L-1, when a layer of penicillinase was adsorbed atop the PAMAM/SWNT film. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Processing of electroactive nanostructured films incorporating carbon nanotubes and phthalocyanines for sensing

The use of carbon nanotubes (CNTs) combined with other materials in nanostructured films has demonstrated their versatility in tailoring specific properties. In this study, we produced layer-by-layer (LbL) films of polyamidoamine-PAMAM-incorporating multiwalled carbon nanotubes (PAMAM-NT) alternated with nickel tetrasulfonated metallophthalocyanine (NiTsPc), in which the incorporation of CNTs enhanced the NiTsPc redox process and its electrocatalytic properties for detecting dopamine. Film growth was monitored by UV-vis spectroscopy, which pointed to an exponential growth of the multilayers, whose roughness increased with the number of bilayers according to atomic force microscopy (AFM) analysis. Strong interactions between -NH3+ terminal groups from PAMAM and -SO3- from NiTsPc were observed via infrared spectroscopy, while the micro-Raman spectra confirmed the adsorption of carbon nanotubes (CNTs) onto the LbL film containing NiTsPc. Cyclic voltammograms presented well-defined electroactivity with a redox pair at 0.86 and 0.87 V, reversibility, a charge-transfer controlled process, and high stability up to 100 cycles. The films were employed successfully in dopamine (DA) detection, with limits of detection and quantification of 10(-7) and 10(-6) mol L-1, respectively. Furthermore, films containing immobilized CNTs could distinguish between DA and its natural interferent, ascorbic acid (AA).

Study of the carbon dioxide chemical fixation-activation by guanidines

Fixation of CO(2) is one of the most important priorities of the scientific community dedicated to reduce global warming. In this work, we propose new methods for the fixation of CO2 using the guanidine bases tetramethylguanidine (TMG) and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]-pyrimidine (TBD). In order to understand the reactions occurring during the CO(2) fixation and release processes, we employed several experimental methods, including solution and solid-state NMR, FTIR, and coupled TGA-FTIR. Quantum mechanical NMR calculations were also carried out. Based on the results obtained, we concluded that CO(2) fixation with both TMG and TBD guanidines is a kinetically reversible process, and the corresponding fixation products have proved to be useful as transcarboxylating compounds. Afterward, CO(2) thermal releasing from this fixation product with TBD was found to be an interesting process for CO(2) capture and isolation purposes. (C) 2008 Elsevier Ltd. All rights reserved.

Amperometric detection of benzoyl peroxide in pharmaceutical preparations using carbon paste electrodes with peroxidases naturally immobilized on coconut fibers

This paper describes the applications of anew carbon paste electrode containing fibers of coconut (Cocus nucifera L) fruit, which are very rich in peroxidase enzymes naturally immobilized on its structure. The new sensor was applied for the amperometric quantification of benzoyl peroxide in facial creams and dermatological shampoos. The amperometric measurements were performed in 0.1 mol L(-1) phosphate buffer (pH 5.2), at 0.0 V (versus Ag/AgCl). On these conditions, benzoyl peroxide was rapidly determined in the 5.0-55 mu mol L(-1), with a detection limit of 2.5 mu mol L(-1) (s/n = 3), response time of 4.1 s (90% of the steady state) and sensitivity limit of 0.33 A mol L(-1) cm(-2). The amperometric results are in good agreement with those obtained by spectrophotometric technique, used as a standard method. (C) 2009 Elsevier B.V. All rights reserved.