Determination of total petroleum hydrocarbons in soil from different locations using infrared spectrophotometry and gas chromatography

Total petroleum hydrocarbons (TPH) are important environmental contaminants which are toxic to human and environmental receptors. Several analytical methods have been used to quantify TPH levels in contaminated soils, specifically through infrared spectrometry (IR) and gas chromatography (GC). Despite being two of the most used techniques, some issues remain that have been inadequately studied: a) applicability of both techniques to soils contaminated with two distinct types of fuel (petrol and diesel), b) influence of the soil natural organic matter content on the results achieved by various analytical methods, and c) evaluation of the performance of both techniques in analyses of soils with different levels of contamination (presumably non-contaminated and potentially contaminated). The main objectives of this work were to answer these questions and to provide more complete information about the potentials and limitations of GC and IR techniques. The results led us to the following conclusions: a) IR analysis of soils contaminated with petrol is not suitable due to volatilisation losses, b) there is a significant influence of organic matter in IR analysis, and c) both techniques demonstrated the capacity to accurately quantify TPH in soils, irrespective of their contamination levels.

An improved method for measuring soil microbial activity by gas phase flow injection analysis

The rate of carbon dioxide production is commonly used as a measure of microbial activity in the soil. The traditional method of CO2 determination involves trapping CO2 in an alkali solution and then determining CO2 concentration indirectly by titration of the remaining alkali in the solution. This method is still commonly employed in laboratories throughout the world due to its relative simplicity and the fact that it does not require expensive, specific equipment. However, there are several drawbacks: the method is time-consuming, requires large amounts of chemicals and the consistency of results depends on the operator's skills. With this in mind, an improved method was developed to analyze CO2 captured in alkali traps, which is cheap and relatively simple, with a substantially shorter sample handling time and reproducibility equivalent to the traditional titration method. A comparison of the concentration values determined by gas phase flow injection analysis (GPFIA) and titration showed no significant difference (p > 0.05), but GPFIA has the advantage that only a tenth of the sample volume of the titration method is required. The GPFIA system does not require the purchase of new, costly equipment but the device was constructed from items commonly found in laboratories, with suggestions for alternative configurations for other detection units. Furthermore, GPFIA for CO2 analysis can be equally applied to samples obtained from either the headspace of microcosms or from a sampling chamber that allows CO2 to be released from alkali trapping solutions. The optimised GPFIA method was applied to analyse CO2 released from degrading hydrocarbons from a site contaminated by diesel spillage.

Methane fluxes from waterlogged and drained Histosols of highland areas

Soil can be either source or sink of methane (CH4), depending on the balance between methanogenesis and methanotrophy, which are determined by pedological, climatic and management factors. The objective of this study was to assess the impact of drainage of a highland Haplic Histosol on CH4 fluxes. Field research was carried out in Ponta Grossa (Paraná, Brazil) based on the measurement of CH4 fluxes by the static chamber method in natural and drained Histosol, over one year (17 sampling events). The natural Histosol showed net CH4 eflux, with rates varying from 238 µg m-2 h-1 CH4, in cool/cold periods, to 2,850 µg m-2 h-1 CH4, in warm/hot periods, resulting a cumulative emission of 116 kg ha-1 yr-1 CH4. In the opposite, the drained Histosol showed net influx of CH4 (-39 to -146 µg m-2 h-1), which resulted in a net consumption of 9 kg ha-1 yr-1 CH4. The main driving factors of CH4 consumption in the drained soil were the lowering of the water-table (on average -57 cm, vs -7 cm in natural soil) and the lower water content in the 0-10 cm layer (average of 5.5 kg kg-1, vs 9.9 kg kg-1 in natural soil). Although waterlogged Histosols of highland areas are regarded as CH4 sources, they fulfill fundamental functions in the ecosystem, such as the accumulation of organic carbon (581 Mg ha-1 C to a depth of 1 m) and water (8.6 million L ha-1 = 860 mm to a depth of 1 m). For this reason, these soils must not be drained as an alternative to mitigate CH4 emission, but effectively preserved.

Soil diffuse degassing and thermal energy fluxes from the southern Lakki plain, Nisyros (Greece)

Two diffuse soil CO2 flux surveys from the southern Lakki plain show that CO2 is mainly released from the hydrothermal explosion craters. The correspondence between high CO2 fluxes and elevated soil temperatures suggests that a flux of hot hydrothermal fluids ascends towards the surface. Steam mostly condenses near the surface and the heat given off is conductively transferred to the atmosphere through the soil, accompanied by a large CO2 flux. Tt was calculated, that 68 t d(-1) of hydrothermal CO2 are released through the total surveyed area of similar to1.3 km(2) Admitting that a steam flux of 2200 t d(-1) accompanies this CO2 flux, the thermal energy released through steam condensation amounts to 58 MW.

Nitrogen fluxes from irrigated common‑bean as affected by mulching and mineral fertilization

The objective of this work was to measure the fluxes of N2O‑N and NH3‑N throughout the growing season of irrigated common‑bean (Phaseolus vulgaris), as affected by mulching and mineral fertilization. Fluxes of N2O‑N and NH3‑N were evaluated in areas with or without Congo signal grass mulching (Urochloa ruziziensis) or mineral fertilization. Fluxes of N were also measured in a native Cerrado area, which served as reference. Total N2O‑N and NH3‑N emissions were positively related to the increasing concentrations of moisture, ammonium, and nitrate in the crop system, within 0.5 m soil depth. Carbon content in the substrate and microbial biomass within 0.1 m soil depth were favoured by Congo signal grass and related to higher emissions of N2O‑N, regardless of N fertilization. Emission factors (N losses from the applied mineral nitrogen) for N2O‑N (0.01-0.02%) and NH3‑N (0.3-0.6%) were lower than the default value recognized by the Intergovernmental Panel on Climate Change. Mulch of Congo signal grass benefits N2O‑N emission regardless of N fertilization.

Incorporation of water vapour transfer in the JULES Land Surface Model: implications for key soil variables and land surface fluxes

This study focuses on the mechanisms underlying water and heat transfer in upper soil layers, and their effects on soil physical prognostic variables and the individual components of the energy balance. The skill of the JULES (Joint UK Land Environment Simulator) land surface model (LSM) to simulate key soil variables, such as soil moisture content and surface temperature, and fluxes such as evaporation, is investigated. The Richards equation for soil water transfer, as used in most LSMs, was updated by incorporating isothermal and thermal water vapour transfer. The model was tested for three sites representative of semi-arid and temperate arid climates: the Jornada site (New Mexico, USA), Griffith site (Australia) and Audubon site (Arizona, USA). Water vapour flux was found to contribute significantly to the water and heat transfer in the upper soil layers. This was mainly due to isothermal vapour diffusion; thermal vapour flux also played a role at the Jornada site just after rainfall events. Inclusion of water vapour flux had an effect on the diurnal evolution of evaporation, soil moisture content and surface temperature. The incorporation of additional processes, such as water vapour flux among others, into LSMs may improve the coupling between the upper soil layers and the atmosphere, which in turn could increase the reliability of weather and climate predictions.

The simulation of the opposing fluxes of latent heat and CO2 over various land-use types: coupling a gas exchange model to a mesoscale atmospheric model

A mesoscale meteorological model (FOOT3DK) is coupled with a gas exchange model to simulate surface fluxes of CO2 and H2O under field conditions. The gas exchange model consists of a C3 single leaf photosynthesis sub-model and an extended big leaf (sun/shade) sub-model that divides the canopy into sunlit and shaded fractions. Simulated CO2 fluxes of the stand-alone version of the gas exchange model correspond well to eddy-covariance measurements at a test site in a rural area in the west of Germany. The coupled FOOT3DK/gas exchange model is validated for the diurnal cycle at singular grid points, and delivers realistic fluxes with respect to their order of magnitude and to the general daily course. Compared to the Jarvis-based big leaf scheme, simulations of latent heat fluxes with a photosynthesis-based scheme for stomatal conductance are more realistic. As expected, flux averages are strongly influenced by the underlying land cover. While the simulated net ecosystem exchange is highly correlated with leaf area index, this correlation is much weaker for the latent heat flux. Photosynthetic CO2 uptake is associated with transpirational water loss via the stomata, and the resulting opposing surface fluxes of CO2 and H2O are reproduced with the model approach. Over vegetated surfaces it is shown that the coupling of a photosynthesis-based gas exchange model with the land-surface scheme of a mesoscale model results in more realistic simulated latent heat fluxes.

Determination of the gas diffusion coefficient of a peat grassland soil

Peatland habitats are important carbon stocks that also have the potential to be significant sources of greenhouse gases, particularly when subject to changes such as artificial drainage and application of fertilizer. Models aiming to estimate greenhouse gas release from peatlands require an accurate estimate of the diffusion coefficient of gas transport through soil (Ds). The availability of specific measurements for peatland soils is currently limited. This study measured Ds for a peat soil with an overlying clay horizon and compared values with those from widely available models. The Ds value of a sandy loam reference soil was measured for comparison. Using the Currie (1960) method, Ds was measured between an air-filled porosity (ϵ) range of 0 and 0.5 cm3 cm−3. Values of Ds for the peat cores ranged between 3.2 × 10−4 and 4.4 × 10−3 m2 hour−1, for loamy clay cores between 0 and 4.7 × 10−3 m2 hour−1 and for the sandy reference soil they were between 5.4 × 10−4 and 3.4 × 10−3 m2 hour−1. The agreement of measured and modelled values of relative diffusivity (Ds/D0, with D0 the diffusion coefficient through free air) varied with soil type; however, the Campbell (1985) model provided the best replication of measured values for all soils. This research therefore suggests that the use of the Campbell model in the absence of accurately measured Ds and porosity values for a study soil would be appropriate. Future research into methods to reduce shrinkage of peat during measurement and therefore allow measurement of Ds for a greater range of ϵ would be beneficial.

Multiresidue analysis of pesticides in soil by supercritical fluid extraction/gas chromatography with electron-capture detection and confirmation by gas chromatography-mass spectrometry

The applicability of supercritical fluid extraction (SFE) in pesticide multiresidue analysis (organohalogen, organonitrogen, organophosphorus, and pyrethroid) in soil samples was investigated. Fortification experiments were conducted to test the conventional extraction (solid-liquid) and to optimize the extraction procedure in SFE by varying the CO2 Modifier, temperature, extraction time, and pressure. The best efficiency was achieved at 400 bar using methanol as modifier at 60 degreesC. For the SFE method, C-18 cartridges were used for the cleanup. The analytical screening was performed by gas chromatography equipped with electron-capture detection (ECD). Recoveries for the majority of pesticides from spiked samples of soil at different residence times were 1, 20, and 40 days at the fortification level of 0.04-0.10 mg/kg ranging from 70 to 97% for both methods. The detection limits found were <0.01 mg/kg for ECD, and the confirmation of pesticide identity was performed by gas chromatography-mass spectrometry in a selected-ion monitoring mode. Multiresidue methods were applied in real soil samples, and the results of the methods developed were compared.

Comparative gas exchange performance during the wet season of three Brazilian Styrax species under habitat conditions of cerrado vegetation types differing in soil water availability and crown density

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A review on soil carbon accumulation due to the management change of major Brazilian agricultural activities

Áreas agrícolas trocam enormes fluxos de CO2, oferecendo uma oportunidade para mitigar o efeito estufa. Neste trabalho, estudou-se o potencial de sequestro de carbono em razão da conversão no manejo das principais atividades agrícolas do Brasil. Dados de vários estudos têm indicado que no sistema soja/milho e nas respectivas rotações, ocorre um sequestro de carbono no solo significativo ao longo dos anos de conversão do plantio convencional para o plantio direto, com uma média de 0,41 Mg C ha-1 ano-1. O mesmo efeito tem sido observado nos canaviais, porém há maiores acúmulos de carbono no solo quando as áreas de cana-de-açúcar são convertidas da colheita baseada na queima para a mecanizada, em que grandes quantidades de palha são deixadas na superfície do solo (1,8 Mg C ha-1 ano-1). Esse maior potencial de acúmulo de carbono no solo nos canaviais, comparado com outras culturas, está diretamente relacionado com a maior produção primária dessa cultura. Apesar disso, muito desse potencial de sequestro é perdido, uma vez que os canaviais são reformados, sob preparo intensivo do solo. As áreas de pasto mostram uma depleção nos estoques de carbono, quando convertidas de áreas naturais; porém, a integração dessas áreas com agricultura pode promover o aumento nos estoques de carbono do solo. Os trabalhos têm mostrado que as principais atividades agrícolas do Brasil possuem um grande potencial de mitigação, especialmente na forma de acúmulo de carbono no solo, sendo uma oportunidade para estratégias futuras.

Effects of soil and foliar application of soluble silicon on mineral nutrition, gas exchange, and growth of potato plants

Silicon can alleviate biotic and abiotic stresses in several crops, and it has beneficial effects on plants under nonstressed conditions. However, there is still doubt about foliar-applied Si efficiency and Si effects on mineral nutrition, physiological processes, and growth of potato (Solanum tuberosum L.) plants under wellwatered conditions. The objective of this study was to evaluate the effect of soil and foliar application of soluble Si on Si accumulation, nutrients, and pigments concentration as well as gas exchange and growth of potato plants. The experiment was conducted under greenhouse conditions in pots containing 35 dm3 of a Typic Acrortox soil. The treatments consisted of a control (no Si application), soil application of soluble Si (50 mg dm-3 Si), and foliar application of soluble Si (three sprays of 1.425 mM Si water solution, prepared with a soluble concentrate stabilized silicic acid), with eight replications. Both soil and foliar application of Si resulted in higher Si accumulation in the whole plant. Foliar application of Si resulted in the greatest Si concentration in leaves, and soil application increased Si concentration in leaves, stems, and roots. Silicon application, regardless of the application method, increased leaf area, specific leaf area, and pigment concentration (chlorophyll a and carotenoids) as well as photosynthesis and transpiration rates of wellwatered potato plants. However, only soil application increased P concentration in leaves and dry weight of leaves and stems. © Crop Science Society of America.

Short-term CO2-C emissions from soil prior to sugarcane (Saccharum spp.) replanting in southern Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Soil greenhouse gas emissions and their relations to soil attributes in a sugarcane area

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)