Multivariate effect of inorganic wastewater matrix on the removal of pesticides by solar photo-Fenton.

An amount of works has reported the effect of wastewater matrix composition on pollutants removal by different AOPs. The biggest challenge is that each wastewater source has a challenging composition (organic and inorganic compounds, pollutants, etc.) and not only the concentration of all these species but also the interaction between them may affect the effectiveness of the studied process. This work has been carried out to evaluate the photo-degradation kinetics of six different pesticides (flutriafol, imidacloprid, myclobutanil, pirimicarb, thiamethoxam and triadimenol) by solar photo-Fenton (SPF) process at acidic pH. First, oxidant concentration (H2O2) was optimized with an actual WWTP effluent. Then, the process was validated with two different secondary and tertiary WWTP effluents, in which main intermediate transformation by-products were identified. Finally, the effect of the inorganic water matrix components (bicarbonate, chloride, sulphate, nitrate and phosphate) was evaluated by a multivariate analysis. Once H2O2 has been optimized at 30 mg L-1, the photo-degradation efficiency of pesticides in real wastewater samples was compared. DOC content of both secondary and tertiary WWTP effluents was dropped by 67%. The identification of the main intermediate transformation by-products (such as 1H-1,2,4-triazole, desmethyl-formamido pirimicarb, thiamethoxam urea, chloronicotinic acid and imidacloprid urea) was reviewed. Following, the multivariate analysis on pesticides photo-degradation, generally, predicted four significant effects in common for the studied pesticides: a positive effect (interaction bicarbonate/nitrate) and three negative ones (chloride, phosphate and the interaction chloride/sulphate); among others. In addition, optimum values of inorganic ion concentrations, to obtain an optimum desirability on studied pesticides removal by SPF at acidic pH, were also evaluated.

Remediation of pesticides in commercial farm soils by solarization and ozonation techniques.

Soil contamination by pesticides is a growing environmental problem. Even though nowadays numerous soil remediation technologies are available, most of them have not been tested at field scale. This study attempts to demonstrate the efficiency of solarization-ozonation techniques for the removal of twelve pesticides at full scale. Initial solarization and ozonation trials were conducted in plots located in a greenhouse using freshly and aged contaminated soils under controlled pilot conditions. The combination of solarization and ozonation treatment was efficient for all the studied pesticides both in freshly and in aged contaminated soils, being the lower degradation values found for the second type. This low removal suggests that the increase of pesticides' adsorption on soil resulting from ageing decreases their availability. Once the essays were carried out at pilot scale, the solarization-ozonation applicability was evaluated in a commercial farm soil. This trial was carried out in a greenhouse whose soil had previously been contaminated with some of the pesticides studied. A significant degradation (53.8%) was observed after 40 days of treatment. Pesticides' main metabolites were identified during the different remediation experiments. In addition, the cost of the combined solarization and ozonation technology was evaluated. Finally, our results suggest that this combination of techniques could be considered a promising technology to degrade pesticides in soil.

Remediation of triazole, anilinopyrimidine, strobilurin and neonicotinoid pesticides in polluted soil using ozonation and solarization.

This study aimed to investigate the effectiveness of ozonation and solarization techniques for the removal of different types of pesticides from soil during the summer season. The effect of two experimental parameters (temperature and ozone application mode) on the pesticide degradation was evaluated. The results showed that solarization (S), solarization with surface ozonation (SOS), and solarization with deep ozonation (SOD) enhanced pesticide degradation rates in comparison with the control (untreated soil, C). The triazole, anilinopyrimidine, strobilurin and neonicotinoid pesticides showed similar behaviour under S and SOS conditions. The highest decrease was found in SOD, indicating the significant effect of temperature and ozone application mode on the efficiency of the ozonation treatment. Thus, a higher soil temperature and a longer accumulated time at high temperature in treatments S, SOS and SOD were observed due to solarization process. In addition, the removal efficiency was enhanced with exposure time. Finally, the main 15 transformation products were identified during SOD treatment. The results suggest that solarization combined with ozonation techniques allows decontamination of soil containing pesticide residues.

Assessment of reclaimed agro-wastewater polluted with insecticide residues for irrigation of growing lettuce (Lactuca sativa L) using solar photocatalytic technology.

Scientific literature is full of works studying the removal of different pollutants from water through different Advanced Oxidation Processes (AOPs). Many of them only suggest it is reused for agricultural purposes or for small crops in pots. This study is based on the reuse of reclaimed agricultural wastewater contaminated with four insecticides (chlorantraniliprole, imidacloprid, pirimicarb and thiamethoxam) for growing lettuce in field conditions. First, solar photocatalysis with TiO2/Na2S2O8 was used on a pilot plant in a sunny area (Murcia, SE of Spain) as an environmentally friendly technology to remove insecticide residues and their main reaction intermediates from contaminated water. The necessary fluence (H, kJ m-2) to accomplish 90% removal (H90) ranged from 0.12 to 1212 kJ m-2 for pirimicarb and chlorantraniliprole, respectively. Only six (derived from imidacloprid, pirimicarb and thiametoxam) of 18 transformation intermediate products studied were detected in reclaimed water during the photoperiod (2000 kJ m-2 of accumulated UVA radiation) although all of them were totally photodegraded after a fluence of 1250 kJ m-2. Secondly, reclaimed agro-wastewater was used to irrigate two lettuce crops grown under greenhouse conditions and under agricultural field conditions. In no cases, insecticide residues nor their TIPs were noticed above their respective LOQs (limits of quantification) in soil and lettuce samples (between 0.03 and 0.04 µg kg-1 for pirimicarb and 2.49 and 2.23 µg kg-1 for thiamethoxam, respectively) when they were irrigated with reclaimed water, while residues of the four insecticides and some of their intermediates were found in soil and lettuce by the end of cultivation when they were irrigated with non-reclaimed contaminated water. According to the results, this technology can be applied in a sustainable way, mainly in areas with water scarcity and high solar radiation, contributing to water utilisation in drought areas and the use of renewable energy.

Reclamation of agro-wastewater polluted with thirteen pesticides by solar photocatalysis to reuse in irrigation of greenhouse lettuce grown.

In Mediterranean countries, reuse of reclaimed water is essential for crop irrigation. The occurrence of pesticides in agro-wastewater may represent a risk for human health and environment owing to their release in soil and translocation to plants. The novelty of this work relies on the reuse of reclaimed agro-wastewater polluted with thirteen pesticides for lettuce irrigation. Removing of pesticide residues in agro-wastewater was carried out using natural sunlight and TiO2/Na2S2O8 in a pilot facility located in Murcia (SE of Spain). The studied pesticides were azoxystrobin, boscalid, chlorpropham, flutolanil, flutriafol, isoxaben, methoxyfenozide, myclobutanil, napropamide, prochloraz, propamocarb, propyzamide and triadimenol, which are commonly used in southeast Spain to treat lettuces grown. Different heterogeneous and homogeneous processes were studied and compared. Previously, the optimization of the process for the selection of the best catalytic system was performed at lab-scale. TiO2+ S2O82- was selected due to the greater effectiveness, achieving almost complete disappearance after about 400 kJ m-2 of cumulative UVA exposure. No significant differences were observed in quality parameters of lettuce grown using treated and non-treated agro-wastewater.

Solar reclamation of agro-wastewater polluted with eight pesticides by heterogeneous photocatalysis using a modular facility. A case study.

In this work, we have studied the removal of eight pesticides, commonly used in fruit crops, in agro-wastewater generated in commercial farms by the cleaning of trace of phytosanitary products in containers and tanks from treatment equipment. The studied pesticides were acetamiprid, cyproconazole, cyprodinil, difenoconazole, fenhexamid, hexythiazox, myclobutanil and thiamethoxam. The trials were performed in a pilot facility located in Murcia (SE of Spain), using natural sunlight and titanium dioxide (TiO2) in tandem with Na2S2O8. Five photocatalytic treatments were carried out during autumn 2017. Results show that the mean (n = 5) final amount was about 13% of the initial pesticide mass present in agro-wastewater. Therefore, we have proved that this technology could be used for tackling the elimination of pesticide residues in agro-wastewater and has favourable prospects of being applied in the water treatment sector.

Abatement of spinosad and indoxacarb residues in pure water by photocatalytic treatment using binary and ternary oxides of Zn and Ti.

The photodegradation of indoxacarb, a broad spectrum foliar insecticide and spinosad, a natural insecticide containing two active ingredients, spinosyn A (major component) and spinosyn D (minor component), was studied in aqueous suspensions of binary (ZnO and TiO2) and ternary (Zn2TiO4 and ZnTiO3) oxides under artificial light (300-460 nm) irradiation. As expected, the influence of the semiconductor materials on the degradation of both was very significant in all cases. Photocatalytic experiments showed that the addition of semiconductors in tandem with Na2S2O8 as electron acceptor strongly improved the removal of indoxacarb and spinosad in water compared with the photolytic tests. The reaction rates significantly increased, especially for the ZnO/Na2S2O8 and TiO2/Na2S2O8 systems. The first-order equation (monophasic model) satisfactorily explained the disappearance process, although it offered no explanation for the small concentrations remaining in the process.

Comparative inhibitory activity of the stilbenes resveratrol and oxyresveratrol on African swine fever virus replication.

Stilbenols are polyphenolic phytoalexins produced by plants in response to biotic or abiotic stress. These compounds have received much attention because of their significant biological effects. One of these is their antiviral action, which has previously been documented for two members of this class, namely resveratrol and oxyresveratrol. Here we tested the antiviral effect of these two compounds on African swine fever virus, the only member of the newly created family Asfarviridae and a serious limitation to porcine production worldwide. Our results show a potent, dose-dependent antiviral effect of resveratrol and oxyresveratrol in vitro. Interestingly, this antiviral activity was found for these synthetic compounds and also for oxyresveratrol extracted from new natural sources (mulberry twigs). The antiviral effect of these two drugs was demonstrated at concentrations that do not induce cytotoxicity in cultured cells. Moreover, these antivirals achieved a 98-100% reduction in viral titers. Both compounds allowed early protein synthesis but inhibited viral DNA replication, late viral protein synthesis and viral factory formation.

Use of farming and agro-industrial wastes as versatile barriers in reducing pesticide leaching through soil columns.

Increased interest has been recently focused on assessing the influence of the addition of organic wastes related to movement of pesticides in soils of low organic matter (OM) content. This study reports the effect of two different amendments, animal manure (composted sheep manure) and agro-industrial waste (spent coffee grounds) on the mobility of 10 pesticides commonly used for pepper protection on a clay-loam soil (OM = 0.22%). The tested compounds were azoxystrobin, cyprodinil, fludioxonil, hexaconazole, kresoxim-methyl, pyrimethanil, tebuconazole, and triadimenol (fungicides), pirimicarb (insecticide), and propyzamide (herbicide). Breakthrough curves were obtained from disturbed soil columns. Cumulative curves obtained from unamended soil show a leaching of all pesticides although in different proportions (12-65% of the total mass of compound applied), showing triadimenol and pirimicarb the higher leachability. Significant correlation (r = 0.93, p<0.01) was found between the observed and bibliographical values of GUS index. The addition of the amendments used drastically reduced the movement of the studied pesticides. Only two pesticides were found in leachates from amended soils, pyrimethanil (<1%) for both, and pirimicarb (44%) in the soil amended with spent coffee grounds. A decrease in pesticide leaching was observed with the increase in dissolved organic matter (DOM) of leachates. The results obtained point to the interest in the use of organic wastes in reducing the pollution of groundwater by pesticide drainage.

Effect of ripening on protein content and enzymatic activity of Crimson Seedless table grape.

The evolution of °Brix, protein content, polyphenoloxidase activity and peroxidase activity during the ripening of Crimson Seedless table grape was studied in three consecutive years (2006, 2007 and 2008). The total protein content was determined according to Bradford's dye binding method, and polyphenoloxidase (PPO) and peroxidase (POD) were extracted using Triton X-114 and characterised using spectrophotometric methods. The year had a statistically significant effect on all the studied parameters and there was an interannual correlation in the evolution of protein, PPO, POD and °Brix. All the studied parameters were statistically correlated, except POD activity with protein content. Weather conditions during the ripening period had a greater effect on protein content than PPO and POD activity.

Photocatalytic degradation of eight pesticides in leaching water by use of ZnO under natural sunlight.

Photodegradation of eight pesticides in leaching water at pilot plant scale using the tandem ZnO/Na(2)S(2)O(8) as photosensitizer/oxidant and compound parabolic collectors under natural sunlight is reported. The pesticides, habitually used on pepper culture and belonging to different chemical groups were azoxyxtrobin, kresoxim-methyl, hexaconazole, tebuconazole, triadimenol, and pyrimethanil (fungicides), primicarb (insecticide), and propyzamide (herbicide). As expected, the influence of the semiconductor used at 150 mg L(-1) on the degradation of pesticides was very significant in all cases. Photocatalytic experiments show that the addition of photosensitizer strongly improves the elimination of pesticides in comparison with photolytic tests; significantly increasing the reaction rates. The use of Na(2)S(2)O(8) implies a significant reduction in treatment time showing a quicker reaction time than ZnO alone. On the contrary, the addition of H(2)O(2) into illuminated ZnO suspensions does not improve the rate of photooxidation. The disappearance of the pesticides followed first-order kinetics according to Langmuir-Hinshelwood model and complete degradation occurs from 60 to 120 min. The disappearance time (DT(75)), referred to the normalized illumination time (t(30 W)) was lower than 3 min in all cases.

[Facial mutilant basosquamous carcinoma]. / Carcinoma basoescamoso mutilante en región facial.

Basosquamous carcinoma is a rare epithelial malignant neoplasm with clinical and biological features of both basal and squamous cell carcinoma. This neoplasm has been characterized for years as a variant of basal cell carcinoma, although now it is widely accepted as a clinical entity. We report a 59-year-old male patient, homeless, who presented an ulcerated tumoral lesion from four years ago, located in left malar region, orbit and nasal pyramid. It caused an important destruction of these anatomic structures and spred out the skull base through optic nerve. The most important features of basosquamous carcinoma are its great local aggressiveness, high frequency of recurrences and its metastatic potential. Because of that, the most effective therapeutic measure is the early detection and complete removement of these tumours; although, as the case we report, it is not always possible.

[TVA and TOA. New adjustable mesh for the treatment of female stress incontinence. Preliminaries results]. / TVA y TOA. Nuevas mallas ajustables de tensión en el tratamiento de la incontinencia urinaria de esfuerzo. Resultados preliminares.

OBJECTIVES: Evaluation of a new mesh for incontinence (TVA/TOA) which enables the degree of tension applied during surgery to be readjusted at the post-operative stage. PATIENTS AND METHOD: 62 patients treated with the TVA mesh and monitored over a 14-month period (SD 7.8, range 6-38). In 33 patients (53%) some other pelvic prolapse was corrected. Evaluation was carried out by clinical report, examination of bladder full of 250 saline solution, flowmetry and urinary residue. 40 patients filled in 4 quality of life questionnaires (QoL; ICIQ-SF; PGI-S; PGI-I). RESULTS: 42 patients were found to be objectively continent in the post-operative evaluation. Of these, it was necessary to reduce tension in 7 cases (11%) due to urinary obstruction (flow < 10 ml/sec and/or residue). The tension of the mesh was tightened in 20 patients (32%) due to continue with a certain degree of incontinence. All patients were discharged as continent and with no residue. In the last revision, 58 patients (93%) proved to be objectively continent and 4 (6.5%) showed a notable improvement in their incontinence. The Q(MAX) is 19.8 ml/sec (SD 9.8). The mictional urgency had disappeared or improved in 32 of the patients who had this prior to operation (76%) and had appeared in 3 of the patients who didn't (15%). The clinical report showed a high level of consensus with the ICIQ-SF survey (Kappa = 0.89) regarding stress incontinence, diminishing clearly (Kappa= 0.13) when urge incontinence was taken into account. 34 (85%) patients scored over 95 out of 110 in the QoL. 30 (75%) scored less than 6 in ICIQ-SF. 32 (80%) showed a perception of normality and 4 (10%) slight illness in the PGI-S. In the PGI-I 29 (72.5%) were much better and 11 (27.5%) quite a lot better. A relation exists between urgency and dismissed quality of life. CONCLUSION: With the TVA (trans-vaginal adjustable) mesh it is possible to adjust the tension originally applied during surgery at the post-operative stage, so that any defects or excesses can be corrected.

Spectrofluorimetric determination of formaldehyde by a flow-injection method based on its catalytic effect on the acridine yellow-bromate reaction.

A flow-injection configuration for the determination of formaldehyde is proposed. The method is based on the enhancing effect of formaldehyde on the oxidation of acridine yellow by bromate in acidic medium. The proposed procedure is simple, inexpensive, sensitive and suitable for concentrations of formaldehyde between 1 and 56 microg mL(-1). A sampling-rate of 60 samples h(-1) was achieved. The effect of several organic and inorganic species was studied. The method was applied to the determination of formaldehyde in pharmaceuticals, milk and air in work environments. The accuracy of the method was confirmed by comparing the results with those obtained using the standard acetylacetone method.

Fluorimetric determination of total ascorbic acid by a stopped-flow mixing technique.

A simple, rapid and automatic fluorimetric method for the determination of total ascorbic acid is described. The method makes use of the stopped-flow mixing technique in order to achieve the rapid oxidation of ascorbic acid by dissolved oxygen to dehydroascorbic acid, which then reacts with o-phenylenediamine to form a fluorescent quinoxaline. The initial rate and fluorescence signal of this system are directly proportional to the ascorbic acid concentration. The calibration graph was linear over the range 0.1-30 microg ml(-1) (kinetic method) and 0.25-34 microg ml(-1) (equilibrium method). The precision (% RSD) was close to 0.5%. The method has been used for the determination of ascorbic acid in pharmaceutical formulations, fruit juices, soft drinks and blood serum.

Determination of proteins in serum by fluorescence quenching of rose bengal using the stopped-flow mixing technique.

The stopped-flow mixing technique was used to develop a very fast, sensitive and accurate method for determining total proteins. The method is based on the lower fluorescence of Rose Bengal caused by binding of the dye to the proteins. The decrease in the fluorescence intensity, measured at 572 nm with excitation 555 nm, was linearly related to protein concentration from 1.3 to 24.5 micrograms ml-1. The detection limit was 0.3 microgram ml-1. The method was satisfactorily applied to the determination of total proteins in different serum samples.

Sensitive determination of diquat by a kinetic method using the stopped-flow mixing technique.

A simple, sensitive, selective, fast and inexpensive assay for the determination of diquat is proposed. The method is based on the reduction of the herbicide to a strongly fluorescent monocation radical with sodium dithionite. The initial rate of this reaction is directly proportional to the diquat concentration. The stopped-flow mixing technique was used because the kinetic data can be obtained in only 7 s, meaning that the method can be automated. The calibration graph is linear over the range 5-500 ng ml-1 and the precision (RSD) is close to 1.2%. The applicability of the method was demonstrated by determining the herbicide in different kinds of samples.

Spectrofluorimetric determination of paraquat by manual and flow injection methods.

The reaction involving the formation of a fluorescent charge-transfer complex between paraquat and benzaldehyde was studied in ethanol-water medium. In the presence of a large excess of benzaldehyde, the fluorescence intensity is linearly related to paraquat concentration from 0.13 to 7.4 micrograms ml-1. The method can be easily adapted to a flow system using a two-channel manifold, the peak height being proportional to the paraquat concentration over the range 1.6-22.3 micrograms ml-1. Manual and flow-injection procedures were satisfactorily applied to the determination of paraquat in commercial herbicides, waters, soils and potatoes.

[Urodynamics of enterocystoplasty and continent diversions]. / Urodinámica de la enterocistoplastia y derivaciones continentes.

OBJECTIVE: To describe the filling and voiding urinary dynamics of enterocystoplasty and continent urinary diversion. METHODS: The different behaviour of the tubularized and detubularized intestinal segments and the different sphincteric lesions related with various surgical techniques are described. The possible causes of incontinence are discussed and the literature briefly reviewed. RESULTS/CONCLUSIONS: We underscore the importance of detubularizing the intestinal segment and preserving the sphincteric system as far as possible. Furthermore, voiding using abdominal pressure may cause post void residual urine, dilatation of the neobladder and renal changes. If warranted, self-catheterization should be performed.