Development of methods based on low-temperature partitioning (LTP) for monitoring cresols and chlorophenols in sewage sludge, soil, and water in column leaching.

Cresols and chlorophenols are chemical contaminants that are potentially toxic to humans and can be found in sewage sludge. These chemical contaminants can migrate into the sludge-soil-water system when sludge is used as a conditioner for agricultural soils. Thus, the objective of this study was to develop methodologies based on extraction with low-temperature partitioning (LTP) to determine cresols and chlorophenols in sewage sludge, soil, and water. The analysis was performed by gas chromatography coupled with mass spectrometry (GC-MS). The validated methods were applied to monitor cresols and chlorophenols in a column-leaching study of a sludge-soil-water system. Satisfactory results were achieved for selectivity, limit of quantification (LOQ), linearity, accuracy, and precision. In the column leaching study, only 2,4,6-trichlorophenol was quantified in sludge samples after 20 days of the experiment. None of the studied compounds were quantified in soil and leached water samples, due to the degradation promoted by the microorganisms present in the sewage sludge. Finally, validated methods were suitable for monitoring cresols and chlorophenols in the sludge-soil-water system.

Extraction method for determining dinotefuran insecticide in water samples.

Dinotefuran is a compound belonging to the third generation of nicotinoid insecticides, and has been effective in combating pests that are resistant to conventional insecticides, such as organophosphates, carbamates, and pyrethroids. This molecule presents high-water solubility (39,830 mg L-1 at 25 °C) compared to other pesticides, which facilitates its drag and leaching to lower soil layers. Therefore, the present study aimed to optimize and validate liquid-liquid extraction with low temperature purification (LLE-LTP) to determine dinotefuran residues in water by high performance liquid chromatography with diode array detection (HPLC-DAD). The results revealed that the analyte recovery ranged from 85.44 to 89.72% with a relative standard deviation <5.8. LLE-LTP was selective, precise, accurate, and linear in the range from 10.0 to 210 µg L-1, and presented limits of detection and quantification of 5.00 and 10.00 µg L-1, respectively. The matrix effect was <14%. The stability study of dinotefuran in water revealed significant stability of this molecule in water in the absence of light (>130 days), and a half-life of 7 days in water with sunlight. LLE-LTP coupled to HPLC-DAD was a simple, easy, and efficient method for extracting and analyzing dinotefuran in water samples.

Simultaneous and direct determination of glyphosate and AMPA in water samples from the hydroponic cultivation of eucalyptus seedlings using HPLC-ICP-MS/MS.

Glyphosate is the main herbicide currently used in the world due to wide applicability and efficiency in controlling weeds in many crops. However, its overuse may lead to undesirable impacts on the environment and to human health in the long run. This present study aimed to optimize and validate solid phase extraction (SPE) using an anionic resin for the simultaneous and direct determination of glyphosate and aminomethylphosphonic acid (AMPA) in water samples using high-performance liquid chromatography combined with inductively coupled plasma with triple quadrupole mass spectrometer (HPLC-ICP-MS/MS). The results showed that recovery percentage and relative standard deviation were 103.9 ± 7.9 and 99.40 ± 9.9% for glyphosate and AMPA, respectively. The validation certified that the method was precise, accurate, linear, and selective, with a limit of quantification of 1.09 and 0.29 µg L-1 for glyphosate and AMPA, respectively. The optimized methodology reached the concentration factor of 250 times and was successfully applied to analyze water samples from hydroponic cultivation of the eucalyptus seedlings. The results showed that the exudation process occurs at glyphosate doses starting from 2 L ha-1.

Catharanthus roseus potential for phyto-stabilizing metals in sewage sludge.

This work evaluated the potential of Catharanthus roseus in phytoremediation of As, Ba, Cd, Cu, Cr, Ni, Pb, Se and Zn in sewage sludge-based substrates. C. roseus was cultivated for 108 days in a treatment containing sewage sludge:vermiculite (70:30%) and in the control with 100% commercial substrate. The plants cultivated in sludge showed approximately four times greater height, number of leaves and stem diameter, as well as 89% higher fresh mass than those of the control. The highest concentrations of the metals were obtained in the roots of plants grown in the sludge, and ranged from 2.04 (Cd) to 1121 mg kg-1 (Zn). Cu, Cd and Zn had a higher bioconcentration factor than 1 in both treatments. On the other hand, the translocation factor value in the control was greater than 1 for Ba, Cd, Cu, Ni, Se and Zn. The results showed that C. roseus was efficient in the phytoremediation of the evaluated metals, in which the translocation process was progressive in the treatment that presented higher metal content.

Determination of three cresol isomers in sewage sludge by solid-liquid extraction with low temperature purification and gas chromatography-mass spectrometry.

Cresols are chemical contaminants derivative from phenol which can be found in sewage sludge. However, little attention has been given to monitoring these compounds in environmental matrices in the literature. Thus, the objective of this study was to develop a simple method based on solid-liquid extraction with low temperature purification for determining three cresol isomers in sludge. The quantification of these compounds was performed by gas chromatography coupled to mass spectrometry with a previous derivatization step. After a detailed study, the cresol recovery was higher than 91%, with relative standard deviation lower than 12% and a limit of quantification of 20 µg kg-1. Linearity was achieved between 10 and 90 µg L-1 (R2 > 0.98) with the standard solutions prepared in matrix extracts due to the trouble caused by the matrix effect. The proposed method was applied with success for monitoring cresols in sewage sludge samples coming from six different wastewater treatment plants. All samples showed contamination by cresols, mainly p-cresol with values between 32.3 and 516.9 µg kg-1. The majority of the analyzed samples showed a total sum of the isomers higher than the maximum residue limit established by Brazilian legislation (160 µg kg-1).

Easy and fast extraction methods to determine organochlorine pesticides in sewage sludge, soil, and water samples based at low temperature.

Organochlorine pesticides present in sewage sludge can contaminate soil and water when they are used as either fertilizer or agricultural soil conditioner. In this study, the technique solid-liquid extraction with low temperature purification was optimized and validated for determination of ten organochlorine pesticides in sewage sludge and soil samples. Liquid-liquid extraction with low temperature purification was also validated for the same compounds in water. Analyses were performed by gas chromatography-mass spectrometry operating in the selective ion monitoring mode. After optimization, the methods showed recoveries between 70% and 115% with relative standard deviation lower than 13% for all target analytes in the three matrices. The linearity was demonstrated in the range of 20 to 70 µg L-1, 0.5 to 60 µg L-1, and 3 to 13 µg L-1, for sludge, soil, and acetonitrile, respectively. The limit of quantification ranged between 2 and 40 µg kg-1, 1 and 6 µg kg-1, and 0.5 µg L-1 for sludge, soil, and water, respectively. The methods were used in the study of pesticide lixiviation carried out in a poly vinyl chlorine column filled with soil, which had its surface layer mixed with sludge. The results showed that pesticides are not leached into soil, part of them is adsorbed by the sewage sludge (4-40%), and most pesticides are lost by volatilization.

Fast extraction of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran in sewage sludge and soil samples.

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid-liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25-25 µg L-1 of 1.25-20 µg L-1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg-1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg-1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.