Impact of olive mill wastewater (OMW) on the soil hydraulic and solute transport properties

The Mediterranean area concentrates the world’s largest production area of olive oil. The olive oil industry represents, in this basin, one of the leading sectors of the agri-food economy. Olive mill water (OMW) is the principal waste effluent produced by the olive oil industry. Due to its high pollution load, this aqueous by-product cannot be directly disposed of in domestic wastewater treatment plants (especially those with a biological treatment unit). Untreated OMW is currently used for agronomic purposes in several countries, mainly because it is rich in valuable plant nutrients. However, OMW is characterized by toxic phenols, high organic matter, high salinity, suspended solids and several other components that may have possible negative effects on chemical and physical soil properties, as well as soil biological activities. In the present research, we focused on the effects of OMW application on transport and hydraulic soil properties. Three distinct soils from a pedological point of view were selected and a series of laboratory steady-state miscible flow tests were conducted under saturated conditions, on both OMW-treated and -untreated soil columns. Tests were conducted on disturbed and undisturbed soil columns. The approach proposed by Kachanoski, based on soil impedance (Z) measurements via the time domain reflectometry (TDR) technique, was used to monitor the leaching experiments. The breakthrough curves (BTCs) exhibited different shapes that allowed the repercussions of OMW applications on soil transport behaviour to be distinguished. Several additional tests conducted on OMW-treated and -untreated soil cores to determine water retention curves (SWRCs) and saturated hydraulic conductivity Ks allowed us to infer the probable mechanisms involved in soil hydrological behaviour changes under OMW treatments. The results show that when OMW leaches into the soil immediately after its disposal there is little effect on the evaluated hydraulic and hydrodispersive properties. By contrast, we demonstrated that a short incubation period (i.e. a short contact time between OMW and soil) of 10 days is enough to exert a great influence on all the values determined (e.g. soil pore velocity v and Ks reduced by up to one order of magnitude). These effects were especially evident in undisturbed soil samples. Graphic Abstract: [Figure not available: see fulltext.

In situ estimation of soil hydraulic and hydrodispersive properties by inversion of electromagnetic induction measurements and soil hydrological modeling

Soil hydraulic and hydrodispersive properties are necessary for modeling water and solute fluxes in agricultural and environmental systems. Despite the major efforts in developing methods (e.g., laboratory-based, pedotransfer functions), their characterization at applicative scales remains an imperative requirement. Accordingly, this paper proposes a noninvasive in situ method integrating electromagnetic induction (EMI) and hydrological modeling to estimate soil hydraulic and transport properties at the plot scale. To this end, we carried out two sequential water infiltration and solute transport experiments and conducted time-lapse EMI surveys using a CMD Mini-Explorer to examine how well this methodology can be used to (i) monitor water content dynamic after irrigation and to estimate the soil hydraulic van Genuchten-Mualem parameters from the water infiltration experiment as well as (ii) to monitor solute concentration and to estimate solute dispersivity from the solute transport experiment. We then compared the results with those estimated by direct time domain reflectometry (TDR) and tensiometer probe measurements. The EMI significantly underestimated the water content distribution observed by TDR, but the water content evolved similarly over time. This introduced two main effects on soil hydraulic properties obtained by the two methods: (i) similar water retention curve shapes, but underestimated saturated water content from the EMI method, resulting in a scaled water retention curve when compared with the TDR method; the EMI-based water retention curve can be scaled by measuring the actual saturated water content at the end of the experiment with TDR probes or by weighing soil samples; (ii) almost overlapping hydraulic conductivity curves, as expected when considering that the shape of the hydraulic conductivity curve primarily reflects changes in water content over time. Nevertheless, EMI-based estimations of soil hydraulic properties and transport properties were found to be fairly accurate in comparison with those obtained from direct TDR measurements and tensiometer probe measurements

A soil non-aqueous phase liquid (NAPL) flushing laboratory experiment based on measuring the dielectric properties of soil-organic mixtures via time domain reflectometry (TDR)

The term non-aqueous phase liquid (NAPL) refers to a group of organic compounds with scarce solubility in water. They are the products of various human activities and may be accidentally introduced into the soil system. Given their toxicity level and high mobility, NAPLs constitute a serious geo-environmental problem. Contaminant distribution in the soil and groundwater contains fundamental information for the remediation of polluted soil sites. The present research explored the possible employment of time domain reflectometry (TDR) to estimate pollutant removal in a silt-loam soil that was primarily contaminated with a corn oil as a light NAPL and then flushed with different washing solutions. Known mixtures of soil and NAPL were prepared in the laboratory to achieve soil specimens with varying pollution levels. The prepared soil samples were repacked into plastic cylinders and then placed in testing cells. Washing solutions were then injected upward into the contaminated sample, and both the quantity of remediated NAPL and the bulk dielectric permittivity of the soil sample were determined. The above data were also used to calibrate and validate a dielectric model (the α mixing model) which permits the volumetric NAPL content (θNAPL m3 m-3) within the contaminated sample to be determined and quantified during the different decontamination stages. Our results demonstrate that during a decontamination process, the TDR device is NAPL-sensitive: the dielectric permittivity of the medium increases as the NAPL volume decreases. Moreover, decontamination progression can be monitored using a simple (one-parameter) mixing model

A Stochastic Texture-based Approach for Evaluating Solute Travel Times to Groundwater at Regional Scale by Coupling GIS and Transfer Function

AbstractInterpreting and predicting the evolution of non-point source (NPS) pollution of soil and surface and subsurface water from agricultural chemicals and pathogens, as well as overexploitation of groundwater resources at regional scale are continuing challenges for natural scientists. The presence and build up of NPS pollutants may be harmful for both soil and groundwater resources. Accordingly, this study mainly aims to developing a regional-scale simulation methodology for groundwater vulnerability that use real soil profiles data. A stochastic approach will be applied to account for the effect of vertical heterogeneity on variability of solute transport in the vadose zone. The approach relies on available datasets and offers quantitative answers to soil and groundwater vulnerability to non-point source of chemicals at regional scale within a defined confidence interval. The study area is located in the Metaponto agricultural site, Basilicata Region-South Italy, covering approximately 12000 hectares. Chloride will be considered as a generic pollutant for simulation purposes. The methodology is based on three sequential steps: 1) designing and building of a spatial database containing environmental and physical information regarding the study area, 2) developing travel time distributions for specific textural sequences in the soil profile, coming from texture-based transfer functions, 3) final representation of results through digital mapping. Distributed output of soil pollutant leaching behavior, with corresponding statistical uncertainties, will be visualized in GIS maps. Of course, this regional-scale methodology may be extended to any specific pollutants for any soil, climatic and land use conditions

Impact of zeolite from coal fly ash on soil hydrophysical properties and plant growth

Zeolites can be extensively employed in agricultural activities because they improve soil properties such as infiltration rates, saturated hydraulic conductivity, water holding capacity, and cation exchange capacity. Natural and synthetic zeolites can efficiently hold water. Zeolites are also believed to have the ability to lose and gain water reversibly, without changing their crystal structure. In the present study, several laboratory tests were carried out using: (i) zeolite synthesized from coal fly ash (a waste product from burning coal in thermoelectric power plants), (ii) a silty loam soil, typically found in Southern Italy, and (iii) sunflower as a reference plant. The selected soil was amended with different percentages of zeolite (1, 2, 5, and 10%) and the effects of the synthetic mineral addition on the hydrophysical properties of the soil and plant growth were evaluated. The results indicated that soil–zeolite mixtures retained water more efficiently by pore radius modification. However, this causes a variation in the range of plant-available water towards higher soil humidity values, as the amount of added zeolite increases. These data confirm that zeolite addition modifies the selected hydrophysical properties of the soil with the effect of decreasing the soil drainage capacity, making the soil less habitable for plant growt

Perylenetetracarboxy-3,4:9,10-diimide derivatives with large two-photon absorption activity

Three new perylenetetracarboxy-3,4:9,10-diimides, bearing 2,6-diisopropylphenyl groups at the imide positions and 4-(R-ethynyl)phenoxy moieties (R = 4,7-di(2-thienyl)benzo[c][1,2,5]thiadiazole (P2), pyrene (P3) or pyrene-CH2OCH2 (P4)) at the four bay positions, were prepared, along with the known related derivative (R = phenyl (P1)), and well characterized. They have large two-photon absorption (TPA) cross-sections (sigma(2)), as determined by the Z-scan technique, the highest values being reached with P2 which bears a planar -delocalized donor moiety. P3 is characterized by higher sigma(2) values than both P1, as expected for the higher -conjugation of the donor pyrene moiety with respect to phenyl, and P4, due to the presence of the flexible and non-conjugated CH2OCH2 bridge between the pyrene and the ethynyl fragment in the latter compound. The molecular geometry of P1-P4 has been optimized by DFT modeling, showing that in P2 and P3 the bay substituents are stacked due to the - interactions of both pyrene and thiophene groups. The LUMO of P1-P4 lies at the same energy and is essentially delocalized on the perylene core whereas the HOMO and HOMO-1 of both P2 and P3 are degenerate and do not show contribution from the perylene core contrarily to that of P1 and P4. The HOMO-LUMO gap is therefore essentially influenced by the HOMO which reflects the electronic charge delocalization on the bay substituents, the lower gaps being observed for P2 and P3, which are characterized by the best TPA properties

Assessing the dynamics of soil salinity with time-lapse inversion of electromagnetic data guided by hydrological modelling

Irrigated agriculture is threatened by soil salinity in numerous arid and semi-Arid areas of the world, chiefly caused by the use of highly salinity irrigation water, compounded by excessive evapotranspiration. Given this threat, efficient field assessment methods are needed to monitor the dynamics of soil salinity in salt-Affected irrigated lands and evaluate the performance of management strategies. In this study, we report on the results of an irrigation experiment with the main objective of evaluating time-lapse inversion of electromagnetic induction (EMI) data and hydrological modelling in field assessment of soil salinity dynamics. Four experimental plots were established and irrigated 12 times during a 2-month period, with water at four different salinity levels (1, 4, 8 and 12 dS m-1) using a drip irrigation system. Time-lapse apparent electrical conductivity (σa) data were collected four times during the experiment period using the CMD Mini-Explorer. Prior to inversion of time-lapse σa data, a numerical experiment was performed by 2D simulations of the water and solute infiltration and redistribution process in synthetic transects, generated by using the statistical distribution of the hydraulic properties in the study area. These simulations gave known spatio-Temporal distribution of water contents and solute concentrations and thus of bulk electrical conductivity (σb), which in turn were used to obtain known structures of apparent electrical conductivity, σa. These synthetic distributions were used for a preliminary understanding of how the physical context may influence the EMI-based σa readings carried out in the monitored transects as well as being used to optimize the smoothing parameter to be used in the inversion of σa readings. With this prior information at hand, we inverted the time-lapse field σa data and interpreted the results in terms of concentration distributions over time. The proposed approach, using preliminary hydrological simulations to understand the potential role of the variability of the physical system to be monitored by EMI, may actually allow for a better choice of the inversion parameters and interpretation of EMI readings, thus increasing the potentiality of using the electromagnetic induction technique for rapid and non-invasive investigation of spatio-Temporal variability in soil salinity over large areas.

evaluating the role of soil variability on potential groundwater pollution and recharge in a mediterranean agricultural watershed

Regional-scale studies on groundwater vulnerability assessment of non-point source agrochemical contamination suffer either from no evaluation of uncertainty in data output, in that of qualitative modelling, or from prohibitively costly computational efforts, in that of deterministic modelling. By contrast, a methodology is presented here which integrates a solute transport model based on transfer function (TF) and a geographic information system (GIS). The methodology (1) is capable of solute concentration estimation at a depth of interest within a known error confidence class, (2) uses available soil survey and climatic and irrigation information and requires minimal computational cost for application and (3) can dynamically support decision-making through thematic mapping. Raw data (coming from different sources) include: i) water table depth, ii) soil texture properties, iii) land use, and iv) climatic information with reference to a study area located in southern Italy. Such information has been then manipulated in order to generate data required for the subsequent hydrological modelling. Simulated breakthrough curves were generated for each soil textural class. They are texture-based travel time probability density functions (TFtb), describing the leaching behaviour of soil profiles with similar soil hydrological properties. The latter, in turn, were estimated by indirect estimation techniques such as pedotransfer functions (PTFs) to overcome the trouble of intensive in situ and/or laboratory determinations of soil hydraulic and hydrodispersive properties, which are generally lacking for regional-scale studies. Results showed large differences in the magnitude of the different travel times and related uncertainties among different profiles. The lower or higher vulnerability was found to be mainly related to the average silt content of the soil profiles

Fluorescent probes based on chemically-stable core/shell microcapsules for visual microcrack detection

Core/shell microcapsule-based fluorescent probes are presented in this work for potential use as early visual detection tool of microcracks in structural materials. A new microcapsule-based system is developed consisting of a UV-screening polyurea shell containing a fluorescent liquid core. The UV-screening functionality allows to prevent unwanted fluorescence emission from intact microcapsules upon UV-light exposure and yields excellent visibility contrast of the locally damaged region where fluorescent liquid core released from ruptured microcapsules is present. In addition, by carefully tuning the chemical composition of the shell material, microcapsules with enhanced chemical stability can be formed, as demonstrated by their superior solvent resistance over dwell time originating from the highly crosslinked shell structure that prevents core extraction from the microcapsules. A thorough chemical, thermal, morphological and optical characterization combined with a functional demonstration of the damage visualization capabilities of this new microcapsule-based system highlights its potential as a highly chemically-stable damage sensor for microcrack detection in structural materials