Ozonation, photocatalysis and photocatalytic ozonation of diuron. Intermediates identification

Authors thank economic support received from Gobierno de Extremadura and CICYT of Spain through Projects GRU10012 and CTQ2012-35789-C02-01, respectively. Mr. Rafael Rodríguez Solís also thanks Gobierno de Extremadura, Consejería de Empleo, Empresa e Innovación, and FSE Funds for his Ph.D. grant (PD12058).Aqueous 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron) has been oxidized by ozonation, photocatalysis and photocatalytic ozonation. Diuron degradation takes place via radical pathway through hydroxyl radicals in those systems involving ozone. Diuron elimination in photocatalytic ozonation is not enhanced if compared to single ozonation; however, TOC removal was significantly improved. Specifically, 80% TOC removal in 2 h was reached in photocatalytic ozonation while single ozonation just led to 25% TOC reduction. Photocatalysis required 9 h to reach 25% TOC reduction. Ten transformation by-products generated during the application of the three technologies were tentatively identified by liquid chromatography–quadrupole time-of-flight mass spectrometry (LC–QTOF–MS/MS). Single ozonation and photocatalytic ozonation led to the formation and complete elimination of all by-products. Low weight carboxylic acids evolution suggests that high TOC removal in photocatalytic ozonation is linked to its capacity to oxidize small oxygenated compounds and release of inorganic chloride and nitrate. Toxicity evolution to Vibrio fischeri in photocatalytic ozonation displayed an increase in inhibition at the initial stages (>90% of inhibition), followed by a decrease of this parameter as the reaction progressed. The final treated sample shows a lower toxicity than the initial one (55% vs 20%).Gobierno de Extremadura GRU10012CICYT of Spain CTQ2012-35789-C02-01Gobierno de Extremadura, Consejería de Empleo, Empresa e InnovaciónFSE Funds PD1205

Salt weathering impact on Nero/Ramses II Temple at El-Ashmonein archaeological site (Hermopolis Magna), Egypt

Nero’s Temple at El-Ashmonein archaeological site, in Minia (middle of Egypt), is considered one of the most important of all temples of Nero. This temple dates back to 1520 BC–1075 BC in the New Kingdom and was reused in the era of Nero (the Fifth Emperor of Rome). The temple construction materials are severely decayed from surrounding environmental impacts, especially contaminated water sources. The main objective of this paper is to identify the construction materials of Nero’s Temple and their decay by-products. To achieve them, X-ray diffraction, micro X-ray fluorescence spectrometry, and portable Raman spectroscopy were utilized to identify the compositions and alteration by-products/degradation compounds (mainly saline efflorescence and crusts) from the construction materials, such as limestone walls, and structural mortars of the temple. In addition, a polarizing microscope was used to identify the minerals inside the construction materials and reveal the alteration of the minerals because of decay. Digital microscopy and scanning electron microscopy with EDS were used to detect decayed materials’ morphological features. Finally, results showed that the main decay factor is salt attack (chlorides, sulfates, phosphates, nitrates, carbonates, and bicarbonates) for all architectural and structural elements of the temple, which have been carried to the construction materials from various sources of contaminated water (canal, sewage, and agricultural water)

Sand dune movement and flooding risk analysis for the pyramids of Meroe, Al Bagrawiya archaeological site, Sudan

The pyramids of Meroe are a signifcant archaeological place at the Al Bagrawiya archaeological site (Sudan) with hundreds of pyramids dating back to the kingdom of Kush (1070 BC–550 AD). In this area, winds, heavy rains, and fooding events are the main geohazards that need assessments and solutions because pyramids are subjected to an accumulation of sand dunes around them and the risk of fooding, afecting their durability. This research aims to assess the impacts of sand dunes on the stability of pyramid structures in addition to assessing the risk of fooding using satellite image observations, and damage and decay assessments of pyramid building materials were carried out through digital mapping. The results from satellite image analysis and monitoring showed that sand dunes along with heavy rains and fooding are the main decay factors, causing the collapse, disintegration, crumbling, alveolariza‑ tion, loss of materials, and cracking of the sandstone ashlars, detecting an increase in deterioration, even considering only the last three decades

Coastal Environment Impact on the Construction Materials of Anfushi's Necropolis (Pharos's Island) in Alexandria, Egypt

The only example and reference of Ptolemaic Alexandrian tombs, with clear integrations of Egyptian-style scenes and decorations, is considered an endangered archaeological site due to different coastal environmental risks in Alexandria and the absence of maintenance. Anfushi's Necropolis is located near the western harbour (Island of Pharos) and dates back to the 2nd century BC. Sea level rises, earthquakes, flooding, storminess, variations in temperature, rainfall, and wind are the factors that have the largest effect on the destruction and decay of Anfushi's Necropolis building materials. This paper's main objectives were to characterize this necropolis's building materials and assess its durability problems and risks regarding the coastal environment. Additionally, the vector mapping of its architectural and structural elements was applied for documentation and recording purposes for the necropolis. To achieve these aims, field (recording and photographs), desk (engineering drawing and mapping), and laboratory works (X-ray diffraction, X-ray fluorescence, binocular microscopy, polarizing microscopy, and scanning electron microscopy) were carried out. The results confirmed the probabilistic risk of sea level rises and its impact on the submergence of Anfushi's Necropolis. The structural deficiencies of the tombs were caused by the effect of earthquake tremors along with anthropogenic factors. In addition, chemical and microscopic investigations showed that salt weathering (halite and gypsum) induced the decay of the building materials

Geoenvironmental investigation of Sahure's pyramid, Abusir archeological site, Giza, Egypt

Abusir is the name of an elaborate burial area in Egypt, dotted with 19 pyramids and other temples, stretching on the western side of the Nile from the south of the Giza Plateau to the northern rim of Saqqara. It seems to have been created as the resting site for the Pharaohs dated from 2494 to 2345 BC. The name Abusir, originally spoken as Busiri, means "Temple of Osiris". Over time, the name has become so popular because more than 60 villages now carry this name, but only one is the archaeological site. This paper focused on one of its most important pyramids from the Abusir archaeological area, Sahure's pyramid, since it is one of Egypt's little-known but heavily damaged treasures. Field and laboratory studies have been carried out to investigate and understand the durability problems and construction materials of this pyramid, leading to results that confirmed the impact of the geoenvironmental conditions on the pyramid's architectural, structural, and engineering stability. Moreover, the results showed that mineralogical content in the construction materials was an intrinsic problem due to the presence of swellable (expansive) clays, which are considered responsible for pyramid decay and damage. In addition to external factors such as the effect of temperature variations, rain, pollutants, wind, and earthquakes and their interactions with intrinsic building material defects. Finally, this paper revealed a new discovery for basaltic mortar as the first trial for green concrete manufacturing in the Egyptian Old Kingdom, Fifth Dynasty

Comprehensive and heart-cutting multidimensional liquid chromatography–mass spectrometry and its applications in food analysis

In food analysis, conventional one‐dimensional liquid chromatography methods sometimes lack sufficient separation power due to the complexity and heterogeneity of the analyzed matrices. Therefore, the use of two‐dimensional liquid chromatography (2D‐LC) turns out to be a powerful tool to consider, especially when coupled to mass spectrometry (MS). This review presents the most remarkable 2D‐LC–MS food applications reported in the last 10 years, including a critical discussion of the multiple approaches, modulation strategies as well as the importance of the optimization of the different analytical aspects that will condition the 2D‐LC–MS performance. The presence of contaminants in food (food safety), the food quality, and authenticity or the relationship between the beneficial effects of food and human health are some of the fields in which most of the 2D‐LC–MS applications are mainly focused. Both heart‐cutting and comprehensive applications are described and discussed in this review, highlighting the potential of 2D‐LC–MS for the analysis of such complex samples.Consejería de Economía, Conocimiento, Empresas y Universidad, Junta de Andalucía (Project Ref. PY2018‐1211, partially supported by EU FEDER funds; postdoctoral research fellowship ref. DOC_01319). Agencia Estatal de Investigación (AEI) y Ministerio de Ciencia MCIN/AEI/10.13039/501100011033 (MACFRAUD project ref. PID2021‐123307OB‐I00; FPU20/02933; Ramón y Cajal RYC2019‐026581‐I y RYC2021‐033148‐I)

Assessment of the presence of transformation products of pharmaceuticals in agricultural environments irrigated with reclaimed water by wide-scope LC-QTOF-MS suspect screening

The transformation that pharmaceuticals can undergo during the water reclamation cycle, or by biotic/abiotic reactions when reclaimed water (RW) is used for irrigation, can lead to the presence of transformation products (TPs) in agricultural environments. However, data on TPs in real crops are scarce. Herein, a suspect screening approach was applied for the comprehensive investigation of 262 potential TPs, associated with 20 prioritised pharmaceuticals found in real tomato crops exposed to long-term RW irrigation. The occurrence and fate of the TPs was evaluated by the retrospective analysis of RW, soil, leave and tomato samples from 4 intensive production greenhouses. Sample analysis was accomplished by liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (LC-QTOF-MS). Up to 18 TPs were tentatively identified, of which 2 were not previously reported. 7 TPs were finally confirmed with analytical standards. 5 TPs were determined in RW, 15 TPs in soil and 2 TPs in leaves. Remarkably, the investigated TPs were not found in tomato fruits. These results shed light on the variety of TPs that can be found in the water reuse cycle and contribute to the assessment of the global risks of wastewater reuse and the safety of the vegetable and fruit production system