Atrazine adsorption and desorption on functionalized montmorillonite: aluminum-pillared and lithium saturated.

Atrazine is an herbicide used worldwide, and it is considered a severe environmental contaminant. The present study aims to evaluate the atrazine adsorption in aqueous media in montmorillonite samples which were either in natural state or functionalized through saturation with lithium and pillarization with aluminum by different methods. Montmorillonite saturated with lithium adsorbed significantly more atrazine than the natural montmorillonite sample. Among the samples obtained through the three aluminum-pillarization methods, the mass percentage of adsorbed atrazine was very similar. However, the best combination was the aluminum-pillarization (due to the maintenance of the open interlayer region) and saturation with lithium (due to the significant reduction of the cation exchange capacity of the mineral), because both processes facilitate the interaction of atrazine with the montmorillonite. Another advantage was that the adsorption of atrazine in the pillared and lithium saturated samples had small desorption, which is desirable in the environmental perspective. It is recommended to build filters with aluminum-hydroxy pillared, lithium saturated montmorillonite as an alternative method to rapidly remove atrazine from aqueous media. In addition to the shorter production time, this process resulted in montmorillonite with high occupancy rate and stability of the aluminum-hydroxy pillars.

Conjunctive use of synchrotron X-ray diffraction and Rietveld refinement in Fe-oxide clays for forensic applications.

Soils have distinctive chemical, physical, mineralogical and biological properties, which make it possible to differentiate them in different environments and also to test for an association of a particular questioned item with a crime scene. Mineral compositions and structures in the soil clay fraction can reflect a distinct characteristic when analyzed by powerful techniques. In this way, the aim of this study was to compare the discriminative power of Fe-oxides concentrated clay samples from the same soil class with and without differences in parent material when analyzed using the Rietveld method and two sources of X-ray diffraction: conventional and high-resolution synchrotron radiations. Clay samples were Fe concentrated (kaolinite and gibbsite removal) to clarify mineralogical composition of 12 samples from three simulated crime scenes, developed under claystone and granite. By Rietveld refinement, detailed crystallographic data were obtained to discriminate samples according their provenance. By synchrotron radiation, mineral data demonstrated the power of quantitative (crystallite size and minerals contents) and qualitative (identification of majoritarian and accessory minerals) analysis by Rietveld refinement, which provides well-resolved data able to discriminate samples from different and same geology. The techniques can be applied in other criminal investigations given their potential of discrimination.

Organic matter quality by pyrolysis-gas chromatography/mass spectrometry and lead and arsenic adsorption.

The organic soils (Histosols) are important as filters for organic and inorganic pollutants, mainly because they are usually located on the banks of rivers and lakes. The aim of this study was to evaluate which functional groups of soil organic matter (SOM) most contribute for the Pb2+ and H2AsO4- adsorption in Histosols. This study used 20 samples (160 ~ 290 g kg-1 of organic carbon (OC) collected at 0-5 cm in five areas of Histosols from Curitiba, Southern of Brazil. Hydrofluoric acid (10%) was used to solubilize minerals to concentrate organic matter (391 to 510 g kg-1 of OC) in the samples. Samples having been submitted to pyrolysis in combination with gas chromatography (Py-GC/MS) that identified 186 organic compounds grouped based on their chemical similarity. The samples were saturated separately with Pb2+ and H2AsO4- under acid conditions (pH 4.0). The exchangeable (electrostatic interactions with SOM charges) and nonexchangeable (complexed to SOM) Pb2+ and H2AsO4- were determined for sequential methods (Ca(NO3)2 and EPA 3051A, respectively. Positive correlations occurred between exchangeable Pb2+ and phenolic compounds (r = 0.6, p < 0.05), lignin phenols (r = 0.5, p < 0.05), and sterols (r = 0.6, p < 0.05). For nonexchangeable Pb2+, there was a significant correlation with alkenes (r = 0.8, p < 0.01), alkanes (r = 0.8, p < 0.01), and methyl ketones (r = 0.7 p < 0.01). The exchangeable H2AsO4- is related to alkanes, alkenes, and methyl ketones. Therefore, in acid Histosols constituted of aliphatic organic matter tend to have less environmental fragility, due to the lesser transportation of these contaminants to other compartments like surface and subsurface waters.

Hybrid technologies for remediation of highly Pb contaminated soil: sewage sludge application and phytoremediation.

Phytoremediation techniques and stabilization of heavy metals with municipal sewage sludge (SW) in soils are usually studied separately. We aimed to verify the potential of the combined use of phytoextraction method and metal stabilization with SW in the recovery of soil with high Pb content (total = 28,650 mg kg-1 and exchangeable = 1,120 mg kg-1) and to verify the effect of the association of these two techniques on the Pb fractions in the soil (stabilization). We have tested five doses of SW (0; 13.4; 26.7; 53.4; 106.8 Mg ha-1) and three cultivation conditions (uncultivated, black oats and forage turnip). The SW application in soil with a high Pb content favored the nutrition and growth of the plants (shoots and roots) and promoted an increase in the Pb absorption, a desirable combination in phytoextraction. The SW application and the cultivation of plants had a positive effect on the stabilization of Pb in the soil. It was verified decrease of the exchangeable fraction and increase precipitated and adsorbed by inner-sphere at the edges of the kaolinite and gibbsite. The combined use of SW and phytoremediation is very promising and should be tested on soils with moderate levels of heavy metals. Novelty statement: We believe that the study presents a more comprehensive methodology to assess and to recover soils highly contaminated with heavy metals. Conditions of the high toxicity of heavy metals in the soil compromise the growth of plants and limit the effectiveness of phytoremediation. We aimed to verify the potential of the combined use of phytoextraction and stabilization with sewage sludge in the recovery of soil with a high Pb content and to verify the effect of the association of these two techniques on the Pb fractions in the soil (stabilization). Often, the simple evaluation of the reduction in total Pb contents with phytoremediation is not sufficient to describe the magnitude of soil decontamination. The ideal is also to determine the different forms of Pb (such as: soluble; exchangeable; precipitate; complexed in organic matter; inner-sphere adsorption in Fe and Mn oxides; inner-sphere adsorption in gibbsite and kaolinite; residue) in soil before and after the recovery techniques to access the possible migration to more stable environmental Pb fractions.

The Use of a Sequential Extraction Technique to Characterize Soil Trace Evidence Recovered from a Spade in a Murder Case in Brazil.

Soil trace evidence can be useful in criminal investigations. A homicide which had occurred in South Brazil been concluded through the courts with a guilty conviction. A spade with soil traces adhering to it was seized from the confessed killer's house, it having been established that it had been used to bury parts of the victim's body. In the context of this confession, it provided an opportunity to test a protocol of analysis and verify the potential of discriminate soil sample analysis in such case works. This allowed us to test the practice of sequential analysis which had been developed for forensic case works in Brazil, with three sequential extractions: (i) 0.2 mol/L pH 3.0 ammonium oxalate; (ii) dithionite-citrate-bicarbonate; and (iii) 0.5 mol/L NaOH. It was possible to predict the sequence of events related to the homicide by using the sequential extraction technique and to conclude that: (i) the A horizon soil from the burial location of the torso was found to be very similar to the soil samples which had been recovered from the spade, which was able to be established despite there only being a small amount of soil adhering to the spade; (ii) the location where the legs were buried contributed a low amount of soil adhering to the spade. Therefore, it is suggested that, where possible, sequential extractions should be prioritized from a questioned sample to best provide information about the likely sequence of contact places and this test likely scenarios and criminal events.

Lead-contaminated soils with contrasting texture remediated with phosphate: chemical fractionation and chloropyromorphite stability.

Pb can be stabilized in soil as Pb-P mineral. The aims of this study were to access the distribution of Pb in organic and mineral fractions of contrasting texture of soil Pb-contaminated and remediated with P and Cl and to evaluate the stability of chloropyromorphite in these soils. A clay loam Oxisol (sandstone) and a clayey Ultisol (basalt) were used in a factorial experiment, with three replications: two soils, two Pb contamination levels, two soil pH values, and four P doses. The Pb concentrations were determined in seven soil phases. Release kinetics of Pb were performed with 0.1 mol L-1 pH 2.5 citric acid. The transfer of soil Pb to chloropyromorphite was dependent on the level of contamination in the clay loam Oxisol. In the lowest P dose (molar ratios P:Pb 3:5), the main source was the Pb complexed in the organic matter and in the highest P dose (molar ratios P:Pb 12:5) was the Pb adsorbed by inner sphere in gibbsite and kaolinite. The release of Pb in the citric acid was dependent on the texture and mineralogy of the soils. Pb recovery applied to the clay loam Oxisol was around 100% (biphasic kinetic), while for the clayey Ultisol, the recovery ranged from 43 to 52% (single-phase kinetic). Remediation of Pb-contaminated soils with P and Cl is more efficient in clayey and oxidic soils since chloropyromorphite formation is faster and its solubilization is slower, an important combination in environmental terms.

The classic aqua regia and EPA 3051A methods can mislead environmental assessments and certifications: Potentially harmful elements resorption in short-range order materials.

EPA 3051A and Aqua Regia (AR) are widely adopted by global environmental agencies to assess soil quality in relation to potentially harmful elements (PHE). However, previous study has shown the formation of large amounts of short-range order materials (SRO) in the residues of these extractions. Residues obtained from the 3051A and AR were recovered from filter papers. To characterize the SRO in these residues, sequential extractions were performed with 0.2 mol L-1 ammonium oxalate (AO) and 0.5 mol L-1 NaOH. On average (n = 15), the 3051A and AR residues contained 37% and 60% of SRO, respectively. The largest amounts of SRO formed in the AR residue was in sample 5 (99% of SRO). The main component of the SRO was Al2O3-AO, Fe2O3-AO and SiO2-NaOH. The formation of SRO and PHE resorption levels were random and highly dependent on the mineralogy of the soil clay fraction. Soils rich in smectites, which are more common in temperate regions, formed larger amounts of SRO. The association of Pb with the SRO was more pronounced in the 3051A residue than in the AR residue. If SRO was not extracted after 3051A, in sample 7, for example, 595 mg kg-1 of Pb (10.2%) would have not been accounted. The maximum PHE resorptions in SRO were (%): Pb - 10; Cu - 470; Ba - 280; As - 21. The underestimation of PHE contents due to resorption mechanisms may lead an environmental agency to certify the use of an area contaminated with PHE.

Potential of soil organic matter molecular chemistry determined by pyrolysis-gas chromatography/mass spectrometry for forensic investigations.

Wetlands near urban centers may be more isolated areas and can be chosen for the disposal of bodies or used as a crime scene. The predominant soils in these areas usually have a high content of organic matter (OM), classified as Histosols. Soil organic matter (SOM) is composed of many different compounds that can be identified by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The study aimed to use Py-GC/MS to classify small amounts of organic soil in a forensic context. We sampled Histosols from five representative sites of Curitiba, Brazil. The molecular composition of the samples was determined by byPy-GC/MS. The factor analysis was carried out, and the factor scores showed a clear differentiation between the sites. Compounds indicative of relatively fresh plant material was separated from more recalcitrant and charred material. Py-GC/MS has the potential to be a useful tool to study the composition of SOM in Histosols to track the trace sample collected from a crime suspect.

Can analysis of a small clod of soil help to solve a murder case?

Soil forensics utilizes extensive soil information to answer legal questions and test hypotheses. The main difficulty often is the determination of different variables from a small amount of soil sample collected on the suspect. We developed a sequential mineralogical and chemical analyses to assess a limited quantity of soil vestiges (0.5 g) from a suspect's vehicle (adhered to the outside rear-view mirror and to the left front fender) involved in a murder case and compared them with the surface samples found at the victim's body disposal site at the Graciosa Road, Paraná State, Brazil. All results affirm that the suspect's vehicle could have been in contact with the edge of the Graciosa Road, approximately the place where the victim's body was located. As a result of the soil analysis and comparison, the results support the likely contact of the suspect's vehicle with the crime scene.

Adsorption of glyphosate on Brazilian subtropical soils rich in iron and aluminum oxides.

We investigated the adsorption of glyphosate onto five subtropical soils of Paraná and São Paulo states, Brazil, a region of intense agricultural activities, aiming at the determination of kinetic and isotherm adsorption parameters which enable the evaluation of the potential leaching of the herbicide. The adsorption was fast, being described by the pseudo-second order and intraparticle diffusion models, thus suggesting that mixed mechanisms are involved. The Oxisol containing the highest concentrations of metal oxides (209.5 g kg-1 Fe2O3 and 160.2 g kg-1 Al2O3) was the sample with the highest rate constant, indicating the adsorption sites are readily available. All the soils are rich in aluminum and iron oxides, explaining the Freundlich coefficients (KF) between 642 and 1360 mg1-1/n kg-1 L1/n, which are higher than most of the coefficients described for other soils around the world. The maximum desorption (15% of the adsorbed amount) was observed for the Oxisol. For the other soils, desorption ranged from 2 to 7%. These results suggest that the leaching of free glyphosate to nearby surface and groundwaters is unlikely unless excessive doses are used. The adsorption parameters are useful for managing the right doses applied to the crops, thus avoiding contamination of adjacent areas.

Clay mineralogy affects the efficiency of sewage sludge in reducing lead retention of soils.

Recent studies have shown the feasibility of using of sewage sludge for the remediation of heavy metal-contaminated soils. However, there are no researches to check the influence of clay mineralogy on the efficiency of the sewage sludge to remediation of contaminated soils with heavy metals. For this purpose, we use two contrasting soils: Oxisol rich in hematite and gibbsite and Inceptisol rich in kaolinite. Thermal-treated sludge was applied to Pb-contaminated soil samples and incubated for 40 days. The soil samples were submitted to seven sequential extractions: soluble-Pb, exchangeable-Pb, precipitated-Pb, organic matter-Pb, Fe and Mn oxide-Pb, gibbsite and kaolinite-Pb, and residual-Pb. The reduction of soluble Pb forms by thermal sludge application was more pronounced in the Oxisol than in the Inceptisol because of the conversion of soluble-Pb into more stable forms, such as precipitated-Pb and oxides-Pb. For Inceptisol was necessary to apply high rates of thermal sludge to reach a significant reduction in soluble-Pb contents. The addition of humic fractions in the form of thermal sludge increased the concentration of organic matter-Pb. In confined area, the use of sewage sludge to reduce the heavy metals levels in soils must be better considered, mainly in more weathered soils.

Factor analysis of organic soils for site discrimination in a forensic setting.

Organic soils are generally located in fluvial settings such as river floodplains that are commonly used for the disposal of bodies. Therefore, the aim of this study was to provide a protocol for the analysis of small amounts of organic soils for forensic purposes. The protocol was applied in five representative sites within the Curitiba metropolitan region (Brazil), with each site supplying four composite samples separated from one another by 3m. The soil samples were collected at a depth of 0 to 5cm. One gram of soil sample was used to determine the total elemental content and perform physical fractionation of the soil (>53µm and <53µm). For both soil size fractions, total C and N contents were determined, and the elements adsorbed to organic matter was determined only for the <53µm size fraction (Na-pyrophosphate extraction). Chemometric multivariate analyses were conducted for the total data set, where more than 77% of the variation was explained by the first three factors. It was determined that Ca, Ba, and Mg adsorbed to organic matter, and total Ba, Ca, K, Mg, Mo, and C contents were most important in sample groupings. As expected in forensic science, the five sites were efficiently distinguishable from each other and the four replicates collected at the same individual site were clearly grouped. This protocol for sampling, chemical analysis, and data treatment of organic soils can be used in real crime situations.

Study of different environmental matrices to access the extension of metal contamination along highways.

Metals are indicators of contamination by anthropic activities, such as road traffic. To assess the extent of the metal contamination, more comprehensive studies analyzing different environmental matrices, such as soils, dust, and plants, collected in different sites that are potential sources of these pollutants along the highways, must be prioritized. Samples of soils, dust, and plants were collected alongside the highways of Brazil at 20 sites selected in strategic locations of metal accumulation (Cr, Pb, Zn, As, and Sb) or different situations of the high ways during two rain conditions (wet and dry weeks of sampling): nearby gutters and water supplies, tolls, petrol stations, a federal road police station, and areas associated with agriculture (yearly culture planting upstream of the highway). The geoaccumulation index (metal concentration in the sample of interest/background) varied from 0 to 6, and the decreasing order of contamination by metals during the wet and dry periods were, respectively: Zn > As > Pb = Sb > Cr and Zn > As > Pb > Cr > Sb. In the soils near the highways, the highest concentrations of metals were as follows (mg kg-1): As = 15.6, Cr = 81.9, Pb = 39.7, Sb = 5.0, and Zn = 379.3. The highest amounts of these elements in the most superficial layer in soils indicated their addition through atmospheric emissions. The most prominent metal was Sb, whose concentration was greater than the quality limits for soils. The concentration of Sb in soils was higher in the wet week than in the dry week. The emissions from road traffic promoted the increase in metals in the dust on the track, especially Zn and Pb. The highest metal concentrations in grasses (Brachiaria) were found in the roots, except for Sb and Zn, which suggests leaf absorption of atmospheric deposition. Metal contamination was widespread in all studied matrices along the highways.

Relationship between heavy metals and minerals extracted from soil clay by standard and novel acid extraction procedures.

Strong acid digestions are commonly used to determine heavy metal (HM) contents in soils. In order to understand more fully the acid digestion processes, a logical step is to determine the extent of dissolution of mineral phases. The aims of this study were to compare the efficiency of extraction of HM by different acid digestions and to monitor the associated dissolution of the clay fraction. The context of the study was to develop a milder chemical extraction method (microwave-assisted 1 mol L-1 HNO3 closed system (NACS)), which recovers more reactive HM and with little dissolution of minerals. The different acid digestion methods dissolved different amounts of minerals from the clay fraction. Both aqua regia (AR) and EPA 3051 dissolved all of the Fe and Al oxides, and the dissolution of kaolin was limited to thinner particles (c dimension), smaller particles in a and b dimensions and grains with lower crystallinity. The lower recovery of HM for AR compared with EPA 3051 was related to the large amount of short-range order phases formed during the AR extraction as these phases have the capacity to re-adsorb HM. The new method (NACS) has the potential to replace other methods of determining bioavailable forms of HM, such as AR and EPA 3051. The contents of Pb, As, Co, Zn, and Cu determined by EPA 3051 and EPA 3052 were quite close.

Three-dimensional data interpolation for environmental purpose: lead in contaminated soils in southern Brazil.

Monitoring of heavy metal contamination plume in soils can be helpful in establishing strategies to minimize its hazardous impacts to the environment. The objective of this study was to apply a new approach of visualization, based on tridimensional (3D) images, of pseudo-total (extracted with concentrated acids) and exchangeable (extracted with 0.5 mol L(-1) Ca(NO3)2) lead (Pb) concentrations in soils of a mining and metallurgy area to determine the spatial distribution of this pollutant and to estimate the most contaminated soil volumes. Tridimensional images were obtained after interpolation of Pb concentrations of 171 soil samples (57 points × 3 depths) with regularized spline with tension in a 3D function version. The tridimensional visualization showed great potential of use in environmental studies and allowed to determine the spatial 3D distribution of Pb contamination plume in the area and to establish relationships with soil characteristics, landscape, and pollution sources. The most contaminated soil volumes (10,001 to 52,000 mg Pb kg(-1)) occurred near the metallurgy factory. The main contamination sources were attributed to atmospheric emissions of particulate Pb through chimneys. The large soil volume estimated to be removed to industrial landfills or co-processing evidenced the difficulties related to this practice as a remediation strategy.