Geogenic Distribution of Arsenic (As) and Antimony (Sb) in Soils of the Murcia Region in Spain

The objective of this study was to determine the As and Sb contents in soils from the Murcia Region of Spain and the possible relationship between the mineralogical composition, soil properties, and As and Sb concentrations. In this study, 490 samples were selected from areas with different characteristics in order to study As and Sb variability. Results show that As and Sb concentrations are positively correlated with the phyllosilicate and quartz content but negatively correlated with the calcite content. The generic reference level (GRL) for these elements was determined according to the Spanish legislation. Established GRL values vary according to the established mineralogical groups, suggesting that GRL has to be determined considering the lithological characteristics of the study area.     

Use of hairy roots extracts for 2,4-DCP removal and toxicity evaluation by Lactuca sativa test

2,4-Dichlorophenol (2,4-DCP) is widely distributed in wastewaters discharged from several industries, and it is considered as a priority pollutant due to its high toxicity. In this study, the use of different peroxidase extracts for 2,4-DCP removal from aqueous solutions was investigated. Tobacco hairy roots (HRs), wild-type (WT), and double-transgenic (DT) for tomato basic peroxidases (TPX1 and TPX2) were used to obtain different peroxidase extracts: total peroxidases (TPx), soluble peroxidases (SPx), and peroxidases ionically bound to the cell wall (IBPx). All extracts derived from DT HRs exhibited higher peroxidase activity than those obtained from WT HRs. TPx and IBPx DT extracts showed the highest catalytic efficiency values. The optimal conditions for 2,4-DCP oxidation were pH 6.5, H₂O₂ 0.5 mM, and 200 U mL^?1 of enzyme, for all extracts analyzed. Although both TPx extracts were able to oxidize different 2,4-DCP concentrations, the removal efficiency was higher for TPx DT. Polyethylene glycol addition slightly improved 2,4-DCP removal efficiency, and it showed some protective effect on TPx WT after 2,4-DCP oxidation. In addition, using Lactuca sativa test, a reduction of the toxicity of post removal solutions was observed, for both TPx extracts. The results demonstrate that TPx extracts from both tobacco HRs appear to be promising candidate for future applications in removing 2,4-DCP from wastewaters. This is particularly true considering that these peroxidase sources are associated with low costs and are readily available. However, TPx DT has increased peroxidase activity, catalytic efficiency, and higher removal efficiency than TPx WT, probably due to the expression of TPX1 and TPX2 isoenzymes.     

Effect of ibuprofen exposure on blood,gill, liver,and brain on common carp (Cyprinus carpio) using oxidative stress biomarkers

Although trace concentrations of ibuprofen (IBP) have been detected in diverse water bodies, there is currently insufficient information on the potentially deleterious effects of this xenobiotic. The present study aimed to determine whether IBP induces oxidative stress in brain, liver, gill, and blood of the common carp Cyprinus carpio. To this end, the median lethal concentration at 96 h (96-h LC₅₀) was determined and the lowest observed adverse effect level was established. Carp were exposed to the latter concentration (17.6 mg L^?1) for 12, 24, 48, 72, and 96 h, and the following biomarkers were evaluated: lipid peroxidation (LPX) and activity of the antioxidant enzymes superoxide dismutase, catalase, and glutathione peroxidase. Results indicated that LPX and antioxidant enzymes’ activity increased significantly (p?<?0.05) with respect to the control group in liver, gill, and blood, while no significant differences occurred in brain. In conclusion, IBP induced oxidative stress on C. carpio, the liver being the organ most affected by this damage.     

Investigation of pharmaceutical metabolites in environmental waters by LC-MS/MS

Pharmaceuticals, once ingested, are commonly metabolized in the body into more polar and soluble forms. These compounds might not be completely removed in the wastewater treatment plants and consequently being discharged into the aquatic ecosystem. In this work, a multi-class sensitive method for the analysis of 21 compounds, including 7 widely consumed pharmaceuticals and 14 relevant metabolites, has been developed based on the use of UHPLC-MS/MS in selected reaction monitoring (SRM) mode. The method was validated in six surface waters (SW) and six effluent wastewaters (EWW) at realistic concentration levels that can be found in waters. The optimized method was applied to the analysis of different types of water samples (rivers, lakes and effluent wastewater), detecting nearly all the parent compounds and metabolites investigated in this work. This fact illustrates that not only pharmaceuticals but also their metabolites are commonly present in these types of waters. Analytical research and monitoring programs should be directed not only towards parent pharmaceuticals but also towards relevant metabolites to have a realistic overview of the impact of pharmaceuticals in the aquatic environment.     

A new bioseed for determination of wastewater biodegradability: analysis of the experimental procedure

A new bioassay proposed in the patent P201300029 was applied to a pre-treated wastewater containing a mixture of commercial pesticides to simulate a recalcitrant industrial wastewater in order to determine its biodegradability. The test uses a mixture of standardized inoculum of the lyophilized bacteria Pseudomonas putida with the proper proportion of salts and minerals. The results highlight that biodegradation efficiency can be calculated using a gross parameter (chemical oxygen demand (COD)) which facilitates the biodegradability determination for routine water biodegradability analysis. The same trend was observed throughout the assay with the dehydrated and fresh inoculums, and only a difference of 5 % in biodegradation efficiency (E _f) was observed. The obtained results showed that the P. putida biodegradability assay can be used as a commercial test with a lyophilized inoculum in order to monitor the ready biodegradability of an organic pollutant or a WWTP influent. Moreover, a combination of the BOD₅/COD ratio and the P. putida biodegradability test is an attractive alternative in order to evaluate the biodegradability enhancement in water pre-treated with advanced oxidation processes (AOPs).     

Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N ², N ⁴-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.     

Bacterial diversity in paclobutrazol applied agricultural soils

The aim of this study was to investigate the bacterial communities on paclobutrazol [(2RS, 3RS)-1-(4-Chlorophenyl)-4, 4-dimethyl-2-(1H-1,2,4-triazol-1-yl) pentan-3-ol]–applied agricultural soils by denaturing gradient gel electrophoresis (DGGE) of polymerase chain reaction (PCR) amplified 16S rDNA gene fragments. Three different agricultural soil samples were collected from paclobutrazol applied mango and waxapple orchards, peanut fields and untreated rice fields as a control for DGGE analysis. The DGGE pattern of PCR- generated 16S rDNA gene fragments indicated that the bacterial populations from four paclobutrazol–applied soils of peanut fields were closely related to each other and two paclobutrazol–applied soils of mango and waxapple orchards harbored closely related bacterial communities. But, paclobutrazol–free agricultural soils comprised relatively a different bacterial group. However, the bacterial populations of mango and waxapple orchard are completely different from the bacterial communities of peanut field. Further purification and sequence analysis of 40 DGGE bands followed by phylogenetic tree assay showed similar results that soil bacteria from paclobutrazol applied mango and waxapple orchard are phylogenetically related. Based on the phylogenetic analysis, the clone M-4 was clad 100 % (bootstrap value) with Mycobacterium sp. The Mycobacterium sp. has been proved to degrade the phenolic compounds such as phenol, 4-chlorphenol, 2,4-dichlorophenol and paclobutrazol molecule containing chlorobenzene ring.     

Evaluation and validation of two different chromatographic methods (HPLC and LC-MS/MS) for the determination and confirmation of ochratoxin A in pig tissues

This study was undertaken to compare two different analytical methods for the determination and confirmation of ochratoxin A (OTA) in blood serum, kidney and liver of pigs. Sample clean-up was based on liquid-liquid phase extraction. The detection of OTA was accomplished with high-performance liquid chromatography (HPLC) combined either with fluorescence detection (FL) or electro spray ionization (ESI+) tandem mass spectrometry (MS–MS). Comparative method evaluation was based on the investigation of 90 samples of blood serum, kidney and liver per animal originating from different regions of Serbia. The analytical results are discussed in view of the respective method validation data and the corresponding experimental protocols. In general, analytical data obtained with (LC–MS–MS) liquid chromatography electro spray tandem mass spectro metry detection offered comparable good results at the sub-ppb concentration level. The results indicate that the liquid chromatography electro spray tandem mass spectrometric (LC-MS/MS) method was more specific and sensitive for the analysis and confirmation of ochratoxin A in pig tissues then high pressure liquid chromatography (HPLC) method after methylation of OTA.     

Pesticide dissipation curves in peach,pear and tomato crops in Uruguay*

Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel®. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r²=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r²=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.     

Acute toxicity and ecotoxicological risk assessment of rice pesticides to Lithobates catesbeianus tadpoles

The objective of this study was to determine the acute toxicity of some pesticides used in irrigated rice farming to Lithobates catesbeianus tadpoles. The LC_50-96h for commercial formulations containing bentazon, penoxsulam, vegetable oil, permethrin and carbofuran, separately and their mixtures, were determined at the proportions commonly used in the field. The limits of risk concentrations of these products for the studied species were also established. The LC_50-96h for tadpoles was 4,530 mg L^?1 for bentazon; 7.52 mg L^?1 for penoxsulam + 145.66 mg L^?1 of vegetable oil; 81.57 mg L^?1 for vegetable oil; 0.10 mg L^?1 for permethrin; 29.90 mg L^?1 for carbofuran (active ingredients), and 38.79 times the dose used in the field for the mixture of these products. The environmental risk was determined only for permethrin, and care should be taken when using the vegetable oil.