Differences in the sorption kinetics of various non-ionisable pesticides in a limited number of agricultural soils from the Mediterranean basin.

Adsorption in soil of organic contaminants, such as pesticides, is a time-dependent process, which can be relevant for understanding and predicting the potential pollution risk of different water sources. The adsorption behavior of six different pesticides with a wide range of physicochemical properties (log KOW 1.26-5.8) was evaluated in up to three different soils with low organic carbon (OC) content (≤1.2%). Pesticide sorbed amounts were fitted to several mathematical models to unravel the mechanisms involved in the adsorption process. The linear distribution constants revealed that pendimethalin and the pyrethroid insecticides were strongly retained in soil, whereas the other three compounds were moderately or weakly adsorbed. In the three soils, the pseudo second order model described more accurately the sorption kinetics of all the contaminants. The more hydrophobic pesticides (log KOW ≥ 4.6) presented lower kinetic rates as compared with the other compounds under study. Both Elovich and intraparticle diffusion models reflected a strong contribution of a rapid initial adsorption on soil surface for thiacloprid, dimethenamid and fenarimol. For the hydrophobic pesticides this contribution was moderate according to the intraparticle diffusion model. Therefore, slower diffusion into the soil micropores was more relevant for the more hydrophobic compounds and for the bigger molecules, and less significant for the more polar pesticides because almost 90% of the total amount adsorbed was achieved in the rapid initial stage.

Adsorption-desorption of dimethenamid and fenarimol onto three agricultural soils as affected by treated wastewater and fresh sewage sludge-derived dissolved organic carbon.

The use of treated wastewaters (TWW) in agriculture is widening in areas suffering drought, such as southern Europe, to preserve freshwater supply for human consumption. The composition of TWW, especially concerning their organic carbon (OC) content, has been demonstrated to influence the processes governing the behavior of non-ionic pesticides in soils. Three OC-poor agricultural soils (SV, RM1 and RM3) from the province of Granada (Spain) were chosen for the assessment of the adsorption and desorption of the herbicide dimethenamid (DIM) and the fungicide fenarimol (FEN). TWW and sewage sludge extracts at different dissolved OC (DOC) concentrations (30, 90 and 300 mg L-1) were considered to evaluate their effect on pesticide adsorption-desorption. As expected by their properties, DIM and FEN were weakly and moderately adsorbed to the soils, respectively. Soil OC seemed to be the major factor controlling FEN adsorption, whereas the mineral fraction played a key role in DIM adsorption, especially in RM1 with high clay:OC ratio. Although TWW did not significantly modify the adsorption of pesticides, it enhanced DIM desorption from the three soils. Adsorption of FEN to SV and RM3 was directly related to the concentration of DOC, possibly due to co-sorption phenomena. Hysteretic desorption was found in all cases, indicating partially reversible adsorption. While FEN desorption was not altered by the solutions, the use of sludge extracts at the highest DOC concentration (300 mg L-1) enhanced DIM desorption as occurred with TWW. Interactions with DOC in solution seemed to predominate for this less hydrophobic compound, thus increasing the risk of natural waters contamination if TWW will be used.

Development of PLA-Waste Paper Biocomposites with High Cellulose Content.

In this study, the integration of paper industry waste with high cellulose content into biocomposites of polylactic acid (PLA), a widely used biobased polymer material, was investigated. The PLA/waste biocomposite samples (0-25 wt.%) were manufactured using the extrusion and injection moulding techniques. The mechanical test results showed improvements in terms of tensile properties and a decrease in impact strength as the percentage of residue increased. The melting temperature decreased, and the crystallinity increased in all biocomposites according to the Differential Scanning Calorimetry (DSC) analysis. Water absorption increased proportionally with the percentage of residue, attributed to the higher cellulose content in the biocomposites, determined by Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) techniques. The scanning electron microscopy (SEM) fracture analysis demonstrated effective reinforcement-matrix cohesion, supporting the previously observed behaviour of the analysed materials. This work highlights the potential of using waste from the paper industry as reinforcement in PLA matrices, opening new perspectives for sustainable applications in the framework of the manufacture of composite materials.

Characterization of Cellulosic Pulps Isolated from Two Widespread Agricultural Wastes: Cotton and Sunflower Stalks.

Globally, huge amounts of cotton and sunflower stalks are generated annually. These wastes are being underutilized since they are mostly burned in the fields. So, in this work, we proposed a three-step method consisting of acid pre-treatment, alkaline hydrolysis, and bleaching for the extraction of cellulose pulps. These pulps were characterized to assess their morpho-structural and thermal properties. The design of experiments and response surface methodology were used for the optimization of the acid pre-treatment in order to achieve maximum removal of non-cellulosic compounds and obtain pulps enriched in cellulose. For cotton stalks, optimal conditions were identified as a reaction time of 190 min, a reaction temperature of 96.2 °C, and an acid (nitric acid) concentration of 6.3%. For sunflower stalks, the optimized time, temperature, and acid concentration were 130 min, 73.8 °C, and 8.7%, respectively. The pulps obtained after bleaching contained more than 90% cellulose. However, special care must be taken during the process, especially in the acid pre-treatment, as it causes the solubilization of a great amount of material. The characterization revealed that the extraction process led to cellulose pulps with around 69-70% crystallinity and thermal stability in the range of 340-350 °C, ready to be used for their conversion into derivatives for industrial applications.

Effect of Olive Pit Reinforcement in Polylactic Acid Biocomposites on Environmental Degradation.

Polylactic acid (PLA) is a biomaterial widely used as an alternative to petroleum-based polymeric matrices in plastic components. PLA-based biocomposites reinforced with lignocellulosic waste are currently receiving special attention owing to their mechanical properties, low toxicity, recyclability, and biodegradability. The influence of the percentage of waste on their properties and resistance to degradation are some of the points of great relevance. Therefore, a series of PLA-based biocomposites containing different percentages of olive pits (5, 15, 25 and 40% wt.) were manufactured and characterized both (a) immediately after manufacture and (b) after one year of storage under environmental conditions. The results obtained were analyzed to evaluate the influence of the incorporation of olive pits on the resistance to degradation (measured through Carbonyl Indices, CI), mechanical properties (tensile, flexural and impact strength), structure (Fourier Transform Infrared Spectroscopy, FT-IR; and, X-ray Diffraction, XRD), morphology (Scanning Electron Microscopy, SEM) and water absorption capacity of the manufactured materials. PLA degradation, corroborated by Differential Scanning Calorimetry (DSC), FT-IR, and XRD, resulted in a decrease in tensile and flexural strengths and an increase in the tensile and flexural moduli. This trend was maintained for the biocomposites, confirming that reinforcement promoted the PLA degradation.

Obtaining Cellulose Nanocrystals from Olive Tree Pruning Waste and Evaluation of Their Influence as a Reinforcement on Biocomposites.

The objective of this work is to improve the mechanical properties of polylactic acid (PLA) by incorporating cellulose nanocrystals (CNC) previously obtained from a cellulose pulp extracted from olive tree pruning (OTP) waste. Composites were manufactured by melt processing and injection moulding to evaluate the effect of the introduction of CNC with conventional manufacturing methods. This OTP-cellulose pulp was subjected to a further purification process by bleaching, thus bringing the cellulose content up to 86.1%wt. This highly purified cellulose was hydrolysed with sulfuric acid to obtain CNCs with an average length of 267 nm and a degradation temperature of 300 °C. The CNCs obtained were used in different percentages (1, 3, and 5%wt.) as reinforcement in the manufacture of PLA-based composites. The effect of incorporating CNC into PLA matrix on the mechanical, water absorption, thermal, structural, and morphological properties was studied. Maximum tensile stress and Young's modulus improved by 87 and 58%, respectively, by incorporating 3 and 5%wt. CNC. Charpy impact strength increased by 21% with 3%wt. These results were attributed to the good dispersion of CNCs in the matrix, which was corroborated by SEM images. Crystallinity index, glass transition, and melting temperatures were maintained.

Horizontal transmission of Streptococcus mutans in schoolchildren.

OBJECTIVE: The aim of this study was to analyze possible horizontal transmission patterns of S. mutans among 6-7-yr-old schoolchildren from the same class, identifying genotypes and their diversity and relationship with caries disease status. STUDY DESIGN: Caries indexes and saliva mutans streptococci and lactobacilli counts were recorded in 42 schoolchildren. Mutans streptococci colonies were identified by means of biochemical tests and all S. mutans strains were genotyped by arbitrarily primed polymerase chain reaction. A child was considered free of S. mutans when it could not be isolated in 3 samples at 1-week intervals. RESULTS: S. mutans was isolated in 30 schoolchildren: 20 having one genotype and 10 two genotypes. Higher mutans streptococci and caries index values were found in those with two genotypes. Five genotypes were isolated in more than 1 schoolchild and one of these was isolated in 3 schoolchildren. Our results suggest that horizontal transmission may take place. CONCLUSION: Schoolchildren aged 6-7 yrs may be the source of mutual transmission of S. mutans.

Manufacture and Characterization of Recycled Polypropylene and Olive Pits Biocomposites.

The present work studies the use of olive pit (OP) as a reinforcement in the manufacture of composites based on a post-consumer recycled polypropylene (rPP). In this way, it is feasible to provide added value from olive pits, a by-product resulting from the olive industry operations, while promoting the circular economy and reducing the use of fossil-based polymers. For this purpose, suitable samples were manufactured using 25 wt% and 40 wt% of OP. Additionally, the effect of incorporating additives was studied: (a) a process control additive (PA), and (b) a coupling agent of maleic anhydride grafted polypropylene (MAPP). The results showed an improvement in Young's and flexural modulus with the OP addition. The incorporation of PA did not present any significant improvement in the properties of the materials, nevertheless it facilitated the biocomposite manufacturing process. As for the coupling agent, it significantly improved the mechanical properties, achieving the best results with the addition of the two types of additives and 40 wt% of OP. Moreover, the thermal properties were maintained, and there was an increase in crystallinity in all composites compared to rPP. According to the results of the fracture surface analysis, the coupling agent improves reinforcement-polymer matrix cohesion.

Sorption of hydrophobic pesticides on a Mediterranean soil affected by wastewater, dissolved organic matter and salts.

Irrigation with treated wastewaters as an alternative in countries with severe water shortage may influence the sorption of pesticides and their environmental effects, as wastewater contains higher concentrations of suspended and dissolved organic matter and inorganic compounds than freshwater. We have examined the sorption behaviour of three highly hydrophobic pesticides (the herbicide pendimethalin and the insecticides α-cypermethrin and deltamethrin) on a Mediterranean agricultural soil using the batch equilibration method. We considered wastewater, extracts from urban sewage sludge with different dissolved organic carbon contents, and inorganic salt solutions, using Milli Q water as a control. All pesticides were strongly retained by soil although some sorption occurred on the walls of the laboratory containers, especially when wastewater and inorganic salt solutions were used. The calculation of distribution constants by measuring pesticide concentrations in soil and solution indicated that pendimethalin sorption was not affected whereas α-cypermethrin and deltamethrin retention were significantly enhanced (ca. 5 and 2 times, respectively) when wastewater or salt solutions were employed. We therefore conclude that the increased sorption of the two pesticides caused by wastewater cannot be only the result of its dissolved organic carbon content, but also of the simultaneous presence of inorganic salts in the solution.

A review of the impact of wastewater on the fate of pesticides in soils: Effect of some soil and solution properties.

Reuse of wastewater (WW) as an agricultural irrigation source is being considered with increasing interest, mainly in arid and semiarid zones. However, due to the complex nature of WW its reuse can have an impact on the fate of the pesticides added to the soils and crops for pest control. This review provides a detailed insight about the main processes involved in pesticide-soil-WW interactions (adsorption/desorption, degradation, transport, plant uptake and field assays) focusing on the role of dissolved organic matter and salt content in the mentioned processes. The influence of pesticide and soil properties in these processes is also discussed. The review explores current research gaps in the pesticide-soil-WW interactions and identifies areas that merit further research, providing a perspective for further scientific exploration.

Thiacloprid adsorption and leaching in soil: Effect of the composition of irrigation solutions.

Pressure on groundwater resources has increased during the last decades due to the growing demand, especially in arid and semiarid regions, such as the Mediterranean basin, with frequent drought periods. In order to partially remediate this environmental problem of world concern, irrigation of agricultural lands with adequately treated wastewaters (TWW) is becoming a common management practice. The complex composition of these low-quality waters may influence the behavior of organic contaminants in soils. A calcareous soil with low organic carbon content was selected for the assessment of the adsorption and leaching of the neonicotinoid insecticide thiacloprid (THC). Different solutions were evaluated: TWW after a secondary treatment, a saline solution and solutions with a range of dissolved organic carbon concentration (DOC, 3-300mgL-1). The addition of an organic fertilizer (fertiormont) to the soil was also assessed, in an attempt to reduce THC mobility. Sorption of thiacloprid, a relatively polar pesticide, was similar under all the conditions considered, though an adsorption decrease was observed when DOC concentration increased. The transport of THC through soil columns was retarded with all the treatments, with the lower effects corresponding to TWW and the saline solution. Addition of fertiormont and irrigation with DOC at 3mgL-1 resulted in a reduction of pesticide leached (34% and 38%, respectively) in comparison with the control (66%), but surprisingly not for DOC at high concentration (55%), possibly due to co-elution of the pesticide with DOC. Therefore the transport of polar compounds, like THC, could be affected by the composition of the irrigation solutions, altering their impact to environmental water resources.

A comparison of the activity of tigecycline against multiresistant clinical isolates of Staphylococcus aureus and Streptococcus agalactiae.

We evaluated the activity of several antibiotics against 225 clinical isolates of Staphylococcus aureus and 252 isolates of Streptococcus agalactiae. Only tigecycline, glycopeptides, and linezolid were active against all the isolates of S. aureus, whereas the beta-lactams were also active against S. agalactiae. Tigecycline could be a good alternative to ampicillin in the treatment of group B Streptococcus infections in patients allergic to beta-lactam.

High presence of extended-spectrum beta-lactamases and resistance to quinolones in clinical isolates of Escherichia coli.

A study was conducted to detect the presence of extended-spectrum beta-lactamases (ESBLs) in 706 isolates of Escherichia coli, largely from outpatients (75.2%). The Clinical and Laboratory Standards Institute (formerly NCCLS)-recommended disk diffusion procedure was used to detect ESBL presence; the VITEK 2 system (bioMérieux, Marcy L'Etoile, France) was used to determine the susceptibility to antibiotics of clinical interest, and the ESBLs were characterized by biochemical study, determining the isoelectric point, and by molecular study with PCR. Clonal distribution was studied in eight hospital isolates. There were 115 ESBL-producing isolates (16.3%), with a predominance of CTX-M9 type (58.3%). We draw attention to the high resistance to quinolones (>70%) in CTX-M9 and SHV enzyme producing isolates and the lower aminoglycoside activity in the latter.

Laboratory persistence in soil of thiacloprid, pendimethalin and fenarimol incubated with treated wastewater and dissolved organic matter solutions. Contribution of soil biota.

Reutilization of treated wastewater (TWW) in agriculture has continued to grow, especially in areas prone to frequent drought periods. One of the major aspects derived from this practice is the addition of important amounts of organic carbon (OC) that could interfere with the fate of organic contaminants in soils. This study has evaluated the impact of irrigation with a secondary TWW and dissolved OC (DOC) solutions from sewage sludge in the dissipation of thiacloprid (THC), pendimethalin (PDM) and fenarimol (FEN) in an OC-poor agricultural soil under laboratory conditions. The effect on soil microbial activity was also assessed through the measurement of dehydrogenase activity. Biotic processes were the main responsible for the degradation of the three compounds. Results showed that while THC was rapidly degraded (DT50 ≤ 5.5 d), PDM and FEN were moderately persistent in soil (DT50 ≥ 93 d). Incubation with TWW did not modify the decay rate of the three pesticides, but initially inhibited soil biota. Solutions of DOC did not alter the dissipation of FEN, but contrasting effects were observed for THC and PDM. Low DOC concentrations (30 mg L-1) accelerated THC disappearance, a fact explained by stimulation of endogenous biota rather than by the presence of exogenous microorganisms from the solution. On the other hand, high DOC concentrations (300 mg L-1) had more influence on the activity of microorganisms at longer times, and showed a trend to enhance the disappearance of the moderately persistent PDM.

Interference of antibiotics in the growth curves of oral streptococci.

The growth curve interference (GCI) induced by different antibiotics was studied using reference strains of oral streptococci. This parameter may prove to be useful in preventing subacute endocarditis of odontological origin in high-risk patients. The growth curves using different concentrations of antibiotics and with an initial optical density (OD) of 0.05 +/- 0.01 were observed until an OD of 0.9-1.0 was reached. The GCI was defined as the lowest concentration of antibiotic that modified the growth curve with respect to a control without antibiotic. The GCI values were then compared with the minimum inhibitory concentration (MIC) values. In all cases, interference in the growth curves was at least one concentration lower than the MIC in a time ranging from 4-6 h.

Two cases of an atypical presentation of necrotizing stomatitis.

PURPOSE: The purpose of this report was to describe the clinical and microbiological characteristics of two rare cases of necrotizing stomatitis, and the outcomes of a non-invasive treatment protocol applied in both cases. METHODS: We report two cases of necrotizing stomatitis in a rare location in the hard palate of a 40-year-old woman and a 28-year-old man. Neither had a relevant medical history and both presented with highly painful ulceration in the palate and gingival margin that was accompanied by suppuration and necrosis. 3% hydrogen peroxide was applied to the lesions using sterile swabs, and antibiotic and anti-inflammatory treatment was prescribed to both patients in addition to two daily oral rinses of 0.2% chlorhexidine. RESULTS: In both cases, radiological examination ruled out bone involvement, and exfoliative cytology revealed a large inflammatory component and the presence of forms compatible with fusobacteria and spirochetes. There was a rapid response to treatment and a major improvement was observed after 48 hours, with almost complete resolution of the ulcerated lesions and detachment of necrotic areas with partial decapitation of gingival papillae. CONCLUSIONS: Necrotizing periodontal lesions can hinder periodontal probing and the mechanical removal of plaque in some cases due to the extreme pain suffered by the patients. We present a non-invasive treatment approach that can manage these situations effectively.

Pesticide mobility and leachate toxicity in two abandoned mine soils. Effect of organic amendments.

Abandoned mine areas, used in the past for the extraction of minerals, constitute a degraded landscape which needs to be reintegrated to productive or leisure activities. However these soils, mainly composed by silt or sand and with low organic matter content, are vulnerable to organic and inorganic pollutants posing a risk to the surrounding ecosystems and groundwater. Soils from two mining areas from Andalusia were evaluated: one from Nerva (NCL) in the Iberian Pyrite Belt (SW Andalusia) and another one from the iron Alquife mine (ALQ) (SE Andalusia). To improve soil properties and fertility two amendments, stabilised sewage sludge (SSL) and composted sewage sludge (CSL), were selected. The effect of amendment addition on the mobility of two model pesticides, thiacloprid and fenarimol, was assessed using soil columns under non-equilibrium conditions. Fenarimol, more hydrophobic than thiacloprid, only leached from native ALQ, a soil with lower organic carbon (OC) content than NCL (0.21 and 1.4%, respectively). Addition of amendments affected differently pesticide mobility: thiacloprid in the leachates was reduced by 14% in NCL-SSL and by 4% in ALQ-CSL. Soil OC and dissolved OC were the parameters which explained pesticide residues in soil. Chemical analysis revealed that leachates from the different soil columns did not contain toxic element levels, except As in NCL soil. Finally ecotoxicological data showed moderate toxicity in the initial leachates, with an increase coinciding with pesticide maximum concentration. The addition of SSL slightly reduced the toxicity towards Vibrio fischeri, likely due to enhanced retention of pesticides by amended soils.

Activity of daptomycin against multiresistant clinical isolates of Staphylococcus aureus and Streptococcus agalactiae.

The activity of daptomycin against 141 Staphylococcus aureus and 63 Streptococcus agalactiae isolates was assessed. The isolates were previously characterized and showed resistance to the antibiotics normally used against gram-positive cocci. Daptomycin was active against 100% of the isolates (minimum inhibitory concentration [MIC(90)] = 0.5 microg/ml, for both species). This antibiotic shows good in vitro activity; therefore, it is an excellent therapeutic alternative against these isolates.

In vitro reduction of mutans streptococci by means of ozone gas application.

OBJECTIVE: To evaluate, in vitro, the antimicrobial effect of ozone gas on strains of reference mutans streptococci and strains isolated from children at a high risk of developing caries. METHOD AND MATERIALS: A series of dilutions was obtained from a total of 41 strains, and the effect of ozone was determined for applications of 10, 20, and 40 seconds, as well as a control, in terms of the reduction of viable bacteria. RESULTS: Ozone application for 10 and 20 seconds produced a significant reduction in the number of bacteria, inversely proportional to the bacterial concentration. When exposure lasted 40 seconds, no viable bacteria were obtained. CONCLUSIONS: Both time of application and initial bacterial concentration bear an influence on the antimicrobial effect of ozone on mutans streptococci.