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.

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.

Is entheses ultrasound reliable? A reading Latin American exercise.

The objective of this study is to evaluate inter-reader entheses ultrasound (US) reliability and the influence of the type of image or degree of sonographer experience on US reliability in patients with spondyloarthritis (SpA). Eighteen Latin American ultrasonographers with different experience took part in an US reading exercise evaluating 60 entheseal images (50 % static images and 50 % videos) from healthy controls and SpA patients. The following sonographic lesions were assessed: structure, thickness, bone proliferation/tendon calcification, erosions, bursitis, and Doppler signal. Another group of three experts with significant experience in entheses US read all images too. Inter-reader reliability among participants and experts was calculated by the Cohen's kappa coefficient. Thresholds for kappa values were <0.2 poor, 0.21-0.4 fair, 0.41-0.6 moderate, 0.61-0.8 good, and 0.81-1 excellent. Furthermore, the results for the expert group were stratified based on the type of image. Kappa correlation coefficients among participants, showed variability depending on the type of lesion, being fair for structure and thickness, moderate for calcifications, erosions, and bursitis, and excellent for Doppler signal. Inter-reader reliability among experts was higher, being moderate for structure and thickness, good for calcifications and bursitis, and excellent for erosions and Doppler. Inter-reader reliability for assessing calcification and structure using static images was significantly higher than for videos. Overall inter-reader reliability for assessing entheses by US in SpA is moderate to excellent for most of the lesions. However, special training seems fundamental to achieve better inter-reader reliability. Moreover, the type of image influenced these results, where evaluation of entheses by videos was more difficult than by static images.

Headspace sorptive extraction for the detection of combustion accelerants in fire debris.

A novel method for separation and identification of ignitable liquid residues in fire debris by gas chromatography and mass spectrometry is presented. Preconcentration of the analytes was carried out using the simple headspace sorptive extraction (HSSE) technique. Polydimethylsiloxane stir bars were used as the enrichment phase, and parameters affecting both the adsorption and desorption stages were carefully optimized. Extraction was carried out at 50°C for 1h. Stir bars were desorbed thermally in the GC injection port, thus avoiding the use of organic solvents. The results for five ignitable liquids, including gasoline and diesel fuel, using HSSE were compared with those obtained with a solid-phase microextraction method, with HSSE appearing as a more sensitive alternative.

Tumour necrosis factor-alpha (TNF-alpha) levels and influence of -308 TNF-alpha promoter polymorphism on the responsiveness to infliximab in patients with rheumatoid arthritis.

OBJECTIVE: To investigate the influence of -308 tumour necrosis factor-alpha (TNF-alpha) promoter polymorphism and circulating TNF-alpha levels in the clinical response to the infliximab treatment in patients with rheumatoid arthritis (RA). METHODS: One hundred and thirty-two RA patients were genotyped for TNF-alpha promoter by polymerase-chain reaction restriction fragment-length polymorphism (PCR-RFLP) analysis. Ten patients with the -308 TNF-alpha gene promoter genotype G/A, and 10 with the G/G genotype were selected and received 3 mg/kg of infliximab at Weeks 0, 2, 6, and 14. RESULTS: Both groups showed a significant improvement with treatment in all variables studied. Total mean TNF-alpha levels increased significantly with respect to basal levels in most of patients after treatment [probability (p)=0.04]. Only patients from G/A showed a statistically significant correlation between ACR 50 and the increase of TNF-alpha levels (p<0.03). CONCLUSION: A relationship was detected between ACR criteria of improvement and increased circulating TNF-alpha levels in RA patients subjected to anti-TNF-alpha therapy.

Structure and aggregation number of a lyotropic liquid crystal: a fluorescence quenching and molecular dynamics study.

The structure and aggregation number of a discotic lyotropic liquid crystal, prepared from tetradecyltrimethylammonium chloride (TDTMACl)/decanol (DeOH)/NaCl/H2O, have been examined using fluorescence quenching of pyrene by hexadecylpyridinium chloride and molecular dynamics (MD). The fluorescence method gives an aggregation number of 258 +/- 25 units (DeOH + TDTMACl). From the MD simulation, a lower limit for the aggregate dimension of 130 units of DeOH + TDTMACl is predicted. A stable oblate aggregate of 240 units was studied in detail. A strong polarization between the ammonium headgroups and chloride ions is observed from the calculated trajectory. DeOH headgroups are located, on average, 0.3 nm more to the interior of the aggregate than the TDTMACl headgroup and contribute to widening the interface by forming H-bonds with water. The radial distribution function of the ammonium headgroup shows that there are 16 water molecules in the first solvation sphere. The diagonal elements of the order parameter tensor of the tail atoms of both surfactants indicate that the interior of the micelle preserves about the same degree of order as at the interface, up to the last three atoms of the aliphatic chain, where the order starts to decrease.