Removal of petroleum hydrocarbon (PHC) contamination that is hazardous and often prevalent in soils would benefit from a rapid detection technique. Visible and near-infrared spectroscopy (VIS-NIRS) has a large potential as a rapid detection technique for PHC in soils. Nevertheless, the combined influence of oil concentration, moisture content and clay content on soil reflectance spectra and the accuracy of the technique have yet received little attention. The objective of this study was to investigate the combined influence of oil concentration and moisture and clay contents on the spectral characteristics of diesel-contaminated soils and the quality of calibration models developed for polycyclic aromatic hydrocarbons (PAH) in soils using VIS-NIRS. With partial least-squares regression data from a systematic experimental design using 150 artificially contaminated soil samples, results showed that soil diffuse reflectance decreased with increasing oil concentration, clay and moisture contents. The trend was less defined in relation to moisture and clay due mainly to the interaction effects of the soil matrices as mediated by the oil. The PAH partial least squares cross-validation showed best performance with the lowest oil concentration and clay content at 20 % moisture with r ² of 0.89, root mean square error of prediction of 0.201 mg/kg and ratio of the standard error of prediction to the standard deviation of the reference data in the validation set of 2.75. Analysis of variance showed that the interaction effects of oil concentration, moisture and/or clay content significantly (p < 0.05) affected the quality of the PAH models.

Buenos Aires Province (República Argentina) has undergone, in the last years, a great increase in agricultural activities based on the incorporation of new technologies and reduction of diversity to meet the increasing food demand. The increase of intensive agricultural systems in Argentina involves the use of fertilizers and pesticides such as herbicides, insecticides, and fungicides. Chlorpyrifos is one of the insecticides most widely used in these crops and constitutes a risk for human health, birds, and aquatic biota such as macroinvertebrates and fishes. In order to assess the possible contamination that the use of this product may represent for the environment, it is necessary to study its interaction with the different types of soils because fate and transport of environmental pollutants may be influenced by their interactions with soil particles. The behavior of chlorpyrifos was analyzed through the study of the recoveries from spiked solid environmental matrices. A strong dependence with organic matter content was observed along with an important dependence with the initial concentrations employed. Here, we show that chlorpyrifos behavior on solid matrices not only depends on soil chemical composition. A significant dependence of recovery percentages with initial concentrations of the pesticide was evident in all cases. Recovery percentages decreased with an increase of the initial concentration employed, no matter the variations in matrices of chemical compositions.

In this work, a coal combustion ash (CCA) has been tested as an alternative low-cost sorbent to commercial activated carbons (GAC) for cadmium and zinc removal from polluted water. To this aim, the effect of pH and metal concentration on CCA adsorption capacity has been investigated, and a comparative analysis with GAC has been carried out in the same experimental conditions. Furthermore, in order to improve CCA adsorption capacity, two different activation treatments of raw CCA have been tested. In particular, the CCA was subjected to a gasification process conducted with steam and to different acidic treatments, conducted either with hydrochloric acid or nitric acid at different acid concentrations. Experimental results showed that all the acid treatments determined a substantial reduction of both cadmium and zinc adsorption capacity. Differently, the steam gasification determined a substantial increase in adsorption capacity with respect to raw CCA, in particular for zinc as its adsorption capacity resulted even higher than the correspondent of GAC. Finally, a thorough analysis of sorbent physical and chemical properties and of adsorption data allowed the individuation of the main cadmium/zinc adsorption mechanism both on CCA and activated carbon, adequately described by the Freundlich model.

N-Nitrosodimethylamine (NDMA) is recently defined as one of nitrogenous disinfection by-products with high carcinogenicity and can be frequently detected in finished water. The decomposition of NDMA in water using nanoscale zero-valent iron (NZVI) in the presence of aluminum and iron salts was investigated in this paper. The results showed that some salts can enhance the removal of NDMA by commercial NZVI in the order of Al(SO) >> AlCl > FeSO > NaSO ≈ NZVI alone, and the highest NDMA removal was 87.3 % in the presence of Al(SO). NDMA removal varied with the addition of Al(SO), NZVI dosage, initial NDMA concentration, solution pH, and temperature. The reduction of NDMA increased with the dosage of Al(SO) and NZVI, which follows a pseudo-first-order kinetics model. The removal of NDMA by NZVI was higher in acidic pHs than in alkaline ones, and the highest removal was found at pH 5. Higher reaction temperature can improve the removal of NDMA and reduce the reaction time. Based on the total nitrogen balance, most nitrogen of NDMA was converted to ammonium and dimethylamine.

In this study, chemical oxidation was applied to treat three contaminated sediments. All the sediments were contaminated with mineral oil, polycyclic aromatic hydrocarbons and heavy metals and had an organic matter content ranging from 2.4 to 7.6 %. The natural oxidant demand of the sediments was determined during treatment with two different types of oxidants (potassium permanganate and sodium persulfate), and the effect of these oxidants on the heavy metal release and on the microbial community was investigated. The natural oxidant demands of the sediments under persulfate treatment were lower (30–100 g kg⁻¹) than the ones treated with permanganate (50–450 g kg⁻¹). Cr was released during the application of permanganate whereas Zn and Pb were released under persulfate treatment. qPCR results showed that permanganate and persulfate, both at a concentration of 150 g kg⁻¹, caused a decrease (2 log units) in the number of 16S rRNA gene of total bacteria in the sediment having the lowest organic matter content. However, the total ATP, considered as a biomarker for microbial activity, was below detection limit in all sediments in the presence of at least 150 g kg⁻¹ oxidant. Only permanganate induced a shift in the structure of the microbial community.

Four species of trees were selected to evaluate the tolerance to heavy crude oil contamination by means of a tolerance index integrating germination, height, biomass and survival as variables. Fresh seeds to Cedrela odorata (tropical cedar), Haematoxylum campechianum (tinto bush), Swietenia macrophylla (mahogany) and Tabebuia rosea (macuilis) were planted in a Vertisol to which heavy crude petroleum was added at four different treatments (C0, 0; C1, 18,940; C2, 44,000; and C3, 57,000 mg kg⁻¹), with the control being uncontaminated soil. The experiment was carried out in a greenhouse during 203 days with a completely random design. The presence of petroleum in soil stimulated and increased germination of S. macrophylla and C. odorata, accelerated the germination of T. rosea and did not affect the germination of H. campechianum. The height and biomass of all species was reduced in the presence of petroleum in the soil. The survival of S. macrophylla and H. campechianum was not affected by petroleum at any concentration studied. On the other hand, C. odorata and T. rosea showed high mortality at all concentrations. The tolerance index showed that S. macrophylla was best at tolerating petroleum in soil and could be employed as a productive alternative for the advantageous use of contaminated sites. The use of tree species could be important because of the great potential of trees for phytoremediation due to their long life, biomass and deep roots that can penetrate and remediate deeper soil layers.

Petroleum hydrocarbon contamination of soil is an emerging environmental threat on the Earth due to possible toxic impact on different ecological receptors. The present study was mainly carried out to evaluate the phytotoxicity of long-term total petroleum hydrocarbon-contaminated soils by the toxicity end points obtained from three plant species Zea mays, Lactuca sativa L., and Cucumis sativus. The tested soil exerted phytotoxicity for all the evaluated end points of plants with dose-dependent relationship. The determined IC₅₀ indicates inhibition in root elongation as the most sensitive toxicity end point for L. sativa L., while inhibition in cross-section area of meristematic zone as the most susceptible and inhibition in seed germination as the least susceptible end points for both Z. mays and C. sativus. The tested root morphometric parameters confirm their applicability as novel toxicity end points. In addition, microcalorimetric analysis confirmed the applicability of inhibition in metabolic heat emission rate as a toxicity end point. Microcalorimetry can be applied to determine the exerted phytotoxic effect on seedlings. The present combined approach concludes that the phytotoxicity of the tested soil is species-specific and varies as follows: Z. mays < C. sativus < L. sativa L. The findings of this study may have implications in planning comprehensive phytotoxicity assessment for hydrocarbon-contaminated soils or screening plant species for phytoremediation program.

A novel immobilized visible light-active photocatalyst (TiO₂/polyvinyl alcohol after thermal treatment (T-PVA)/cordierite honeycomb (CHC)) was successfully prepared by a simple and convenient method combining sol–gel and thermal treatment using tetrabutyl titanate (TBOT) as the titanium source, polyvinyl alcohol (PVA) as the precursor of conjugated polymer, and CHC as the support. The synthesized photocatalyst was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ultraviolet–visible diffuse reflectance spectroscopy, and field emission scanning electron microscopy. The results showed that PVA was dehydrated to produce conjugated unsaturated T-PVA. The T-PVA not only extended the response spectrum of TiO₂ to visible light region, but also strengthened the adhesion of TiO₂ to CHC. The TiO₂/T-PVA/CHC showed both outstanding adsorption properties and excellent photocatalytic performance under visible light on the decolorization of Rhodamine B. Over eight cycles, the photocatalyst continued to maintain perfect photocatalytic activity, showing good stability.

The fate and transport of emerging contaminants have been major concerns for ecoenvironment and human health. This study presents the adsorption behavior of an endocrine disrupting chemical estrone (E1) and its sulfate conjugate estrone-3-sulfate (E1-3S) that are released to the environment via animal waste in significant amounts and direct exposures in grazed pasture systems. Both compounds have been shown to potentially contribute to endocrine disruption in wildlife, and knowledge about the adsorption behavior of these compounds is necessary for a sound environmental risk assessment. For labile compounds such as E1 and E1-3S, however, the standard protocols might overestimate adsorption by not considering metabolite formation or allowing for equilibration that exceeds the commonly reported half-lives of these compounds. Modified batch adsorption experiments with mediator solution of 0.005 M calcium chloride (CaCl₂) and artificial urine (AU) solution were, therefore, conducted to determine the influence of these mediator solutions on the adsorption of E1 and E1-3S in three agricultural soils from Nasarawa State of Nigeria. Adsorption isotherms of both compounds were nonlinear, and the Freundlich equation was found adequate to describe the isotherms. The calculation of concentration-dependent effective distribution coefficients (K d ᵉᶠᶠ) revealed that for a range of realistic exposure concentrations in a grazed farming system, the common approach of using CaCl₂ would deliver incorrect information for a sound risk assessment.

The single-well push–pull test (SWPPT) was adapted to quantify in situ aerobic respiration and denitrification rates and to assess microbial population dynamics in a petroleum-contaminated fractured bedrock aquifer. Among three test wells, significant dissolved oxygen (DO) consumption was observed only in one well, with average zero- and first-order rate coefficients of 0.32 ± 0.63 and 7.07 ± 13.85 mmol L⁻¹ day⁻¹, respectively. Of the four test wells, significant NO₃ ⁻ consumption was noted in three wells. The average zero- and first-order rate coefficients were 2.87 ± 2.21 and 11.83 ± 7.99 mmol L⁻¹ day⁻¹, respectively. These results indicate that NO₃ ⁻ was more effectively consumed within this fractured bedrock aquifer. Significant DO or NO₃ ⁻ (electron acceptors (EAs)) consumption, the limited contribution of Fe(II) to overall EAs consumption, the production of dissolved CO₂ during aerobic respiration and denitrification tests, and N₂O production strongly suggest that the EAs consumption was largely due to microbial activity. Detection of Variovorax paradox, benzene-degrading culture, and 28 novel microbial species after the addition of O₂ or NO₃ ⁻ suggests that EA injection into a fractured rock aquifer may stimulate aerobic or denitrifying petroleum-degrading microbes. Therefore, SWPPT may be useful for quantifying in situ aerobic respiration and denitrification rates and for assessing microbial population dynamics in petroleum-contaminated fractured bedrock aquifers.