Spatial distribution, geochemical processes of high-content fluoride and nitrate groundwater, and an associated probabilistic human health risk appraisal in the Republic of Djibouti.

In the northern East African Rift System, the Republic of Djibouti relies exclusively on groundwater, with levels of fluoride (up to 14 mg/L) and nitrate (up to 256 mg/L) posing potential health risks. To address this, 362 samples were considered, including 133 shallow groundwater samples, along with new and previously published data dating back to 2012 on deep (88) and thermal (141) groundwater samples. To understand the enrichment mechanisms, dissolved anion and cation constituents, geochemical and thermodynamic tools, and stable isotope ratios, such as δ2H(H2O), δ18O(H2O), δ15N(NO3-), and δ18O(NO3-), were used. In particular, two activity diagrams (Mg2+ vs. Ca2+ and Na+ vs. Ca2+), focused on aqueous and solid fluoride species in an updated thermodynamic dataset of 15 fluoride-bearing minerals, are shown for the first time. The dataset offers new and valuable insights into fluoride geochemistry (classic thermodynamic datasets combined with geochemical codes rely solely on fluorapatite and fluorite F-bearing minerals). Activity diagrams and geochemical modeling indicate that mineral dissolution primarily drives groundwater fluoride enrichment in all water types, whereas the elevated nitrate levels may stem from organic fertilizers like animal manure, as indicated by nitrate isotopes and NO3-/Cl- vs Cl- diagrams. Despite the arid climate and 2H18O enrichment in shallow waters, evaporation seems to play a minor role. Monte Carlo simulations and sensitivity analysis were used to assess the health risks associated with elevated F- and NO3- concentrations. Mapping-related spatial distribution analysis identified regional contamination hotspots using a global Moran's I and GIS tools. One fluoride and three nitrate contamination hotspots were identified at a p-value of 0.05. Groundwater chemistry revealed that 88 % of groundwater being consumed exceeded the permissible levels for fluoride and nitrate, posing potential health risks, particularly for teenagers and children. This study pinpoints specific areas with excessive nitrate and fluoride contamination, highlighting a high non-carcinogenic risk.

Valorization of saffron (Crocus sativus L.) stigma as a potential natural antioxidant for soybean (Glycine max L.) oil stabilization.

Synthetic antioxidants are known for their efficiency to improve vegetable oil oxidative stability. But owing to their harmful effects on human health, edible oil industry is seeking for safe and healthy natural antioxidants. The present work was setup with the aim of improving soybean oil (SO) oxidative stability by using saffron (Crocus sativus L.) stigmas collected in Morocco. Saffron stigmas were used as a natural antioxidant at various concentrations (0.2, 0.3, and 0.6%) in soybean oil compared to tocobiol (0.3%) as a synthetic antioxidant (the positive control). Performances of such natural and synthetic antioxidants were evaluated by measuring oil basic quality indices under accelerated storage at 60 °C for 12 weeks. Such indices consisted of free fatty acids (FFA), peroxide value (PV), anisidine value (p-AV), total oxidation value (TOTOX), UV extinction coefficients (K232 and K270), fatty acids composition (FA), and iodine value (IV). The obtained data show that there were significant (p < 0.05) increases in FFA, PV, p-AV, K232, K270, and TOTOX but no much variations were observed for FA and IV especially in saffron stigmas fortified oils across storage times. However, in the case of oils fortified with saffron stigmas at different doses, such an increase was of a lesser magnitude (for FFA, PV, p-AV, K270, and TOTOX) as compared to tocobiol. These outcomes were confirmed by principal component analysis with strong positive correlations (p < 0.001) among FFA, PV, p-AV, K232, K270, and TOTOX. The most important, for which determination coefficient R2 > 0.9, were modeled through simple regressions. In conclusion, saffron stigmas with the different doses performed better than the positive control (tocobiol) regardless of the storage time. It could be concluded that saffron stigmas are a promising natural antioxidant, alternative to synthetic antioxidants, to enhance the oxidative stability of edible oils.

FTIR, 1H, and 13C NMR Characterization and Antibacterial Activity of the Combination of Euphorbia Honey and Potato Starch.

AIM AND OBJECTIVE: In recent years, natural biopolymer (potato starch) hydrogels have been widely used in the field of wound dressing material. This study aimed to develop and characterize a novel antibacterial hydrogel made from potato starch and natural honey. METHODS: The structure of the composite films was evaluated by Fourier transform infrared (FTIR) and 1H,13C nuclear magnetic resonance (NMR) spectroscopy, and the antibacterial activities were tested by agar diffusion method. FTIR analysis showed chemical interaction between the components of Euphorbia honey (EH) and potato starch hydrogel (PSH). RESULTS: The 1H-13C NMR and FTIR analyses of EH/PSH confirmed their structure and showed the presence of glucose and hydrocarbon derivatives. After 24 h of incubation, the EH/PSH hydrogel showed good antibacterial activity against three bacterial strains (K.pneumonia, P.mirabilis, and P. aeruginosa) by producing clear inhibition zones of 12.33±1.88 mm, 15.33±0.94, and 10±0 mm, respectively. In addition, K. pneumonia, P. mirabilis, and P. aeruginosa were sensitive to the EH/SPH with a minimum inhibitory concentration (MIC) of 1 %. CONCLUSION: These results suggest that EH-PS has potential as an alternative candidate to conventional antibiotics.

Proximate Composition, Physicochemical, and Lipids Profiling and Elemental Profiling of Rapeseed (Brassica napus L.) and Sunflower (Helianthus annuus L.) Grown in Morocco.

We investigate and compare the nutritional and physicochemical properties of rapeseed and sunflower grown in Morocco. In order to examine a complete physicochemical characterization, various parameters such as mineral profile, fatty acid composition, sterols contents, total flavonoids content (TFC), total polyphenols content (TPC), and quality oil parameters were evaluated. The results showed a relatively small difference in the physicochemical composition of the seeds, as sunflower seeds recorded higher amounts of protein and oil content (22.98 ± 0.01 g/100 g and 41.30 ± 0.50 g/100 g) than rapeseed (22.98 ± 0.01 and 38.80 ± 0.50), while mineral elements profile was observed to be statistically different. Nevertheless, both seeds were rich in K, Ca, P, Mg, and Na and they were relatively poor in Na, Fe, Mn, Cu, and Zn. The most represented macroelement was K with the amount of 7936.53 ± 63.87 mg/Kg in rapeseed and 7739.22 ± 59.50 mg/Kg in sunflower. On the other hand, Cu was present in the analyzed samples the least, mostly below 20 mg/kg. For TPC and TFC, the sunflower recorded higher values (49.73 ± 0.50 and 25.37 ± 0.39 mg GAE/g) than rapeseed (38.49 ± 0.24 and 22.55 ± 1.76 mg QE/g). The fatty acid composition showed that both extracted oils have beneficial proprieties, as they are rich in unsaturated fatty acids; namely, rapeseed oil contains a high level of oleic acid (C18 : 1) (62.19%), while sunflower oil was richer in linoleic acid (C18 : 2) (55.7%). As a result, we conclude that the studied varieties have major importance in terms of both nutritional and seed improvement potentials.

Origin of nitrate and sulfate sources in volcano-sedimentary aquifers of the East Africa Rift System: An example of the Ali-Sabieh groundwater (Republic of Djibouti).

Within the East African Rift System (EARS), the complex Ali-Sabieh aquifers system, located in the south of the Republic of Djibouti, was overexploited and subjected to anthropogenic and/or geogenic pollution with high concentrations of dissolved nitrate (up to 181 mg/l) and sulfates (up to 1540 mg/l). This study is the first undertaken on the hydrochemistry of this aquifer system, combining geochemical tools and multi-isotope - δ2H(H2O), δ18O(H2O), δ18O(SO4), δ34S(SO4), δ15N(NO3), δ18O(NO3), δ13C(DIC), and 14C- was used to decipher the origin and fate of different nitrate and sulfate sources to groundwater. The groundwater samples of the region show a chemical evolution from fresh Ca(Na)-bicarbonate to brackish Na-Cl , mainly due to water-rock interaction. The combined chloride and water isotope data show that evaporation and transpiration are present, with the latter occurring primarily in the shallow alluvial aquifer waters. Inspection of δ15N(NO3) vs. δ18O(NO3) and NO3/Cl vs. Cl diagrams show that dissolved nitrates are primarily of anthropogenic origin. In particular, higher nitrate concentrations may be related to animal manure used as organic fertilizers during agricultural activities. Sulfates are from a natural origin related to the interaction of water with gypsum of hydrothermal or sedimentary origin. SO4/Cl ratio and isotopic composition show that dissolved sulfates in saline and ancient groundwater of the Cretaceous sandstone aquifer (between 7.4 ± 2.2 and 5.8 ± 1.4 k-years before the present) are generated by interaction with gypsum from oxidation of pre-existing (Jurassic?) sulfides. This work highlight that isotopic ratios of the two molecules -δ18O(SO4), δ34S(SO4), δ15N(NO3), δ18O(NO3)- are not sufficient for tracing the origin of nitrate and sulfates in groundwater, but that a complete hydrogeochemical study is needed. In the absence of this, the relatively high concentration of chloride and sulfates could be wrongly linked to the anthropogenic source of nitrate (manure or sewage).

Hg and 210Po in consumed fish of the Tadjoura Gulf (Djibouti): Levels and human health risk assessment.

Hg and 210Po were measured in the muscle tissue of commercially important fish species collected in the main coastal cities of the Djiboutian coast (Tadjoura Gulf) to evaluate the potential risk associated with their consumption. The levels of Hg among the different species ranged from 0.02 to 1.69 mg/kg w.w and exceeded tolerable limits as reported by the national regulation (2000-0727/PR/MAEM) and the Codex Alimentarius. The probabilistic distributions of health hazard were evaluated through Monte-Carlo simulation, which confirmed the carcinogenic risk from Hg. The levels of 210Po ranged from 4.1 to 134.5 Bq/kg w.w among muscle tissues of the eight commercially important species. The carcinogenic risk was in an unacceptable range and simulation revealed that children were the most vulnerable population. The results obtained confirms that the health impact is reduced when consuming two servings per week.

Beyond a Seat at the Table: The Added Value of Family Stakeholders to Improve Care, Research, and Education in Neonatology.

OBJECTIVES: To analyze activities involving veteran resource parents and patients in a family partnership program; their perspectives were also explored. STUDY DESIGN: The multiple roles assumed by family stakeholders in neonatal initiatives were reviewed. Quality control questionnaires were distributed to resource parents and patients and providers who worked with them. Mixed methods were used to analyze results. RESULTS: Thirty resource parents and patients were involved in a total of 653 activities related to clinical care (n = 413), teaching (n = 31), and research (n = 209); 7 initiatives were described to illustrate the positive impact of family stakeholders on clinical care, teaching, and/or research. Resource parents and patients had different degrees and intensity of involvement: all were involved in low-risk initiatives and 9 in more complex activities. In the questionnaire, family stakeholders all described positive impacts associated with their participation and benefits to themselves, such as meaning making. Three resource parents reported traumatic memories that occurred during medical simulations. The majority of providers report that resource parents and patients improved their projects, but some also report this new collaboration is complex. CONCLUSIONS: Although stakeholder participation increasingly is recommended, practical knowledge and the impact of their participation is scarce. Having several resource parents and patients bring their contributions may be more valuable than a few "expert stakeholders." Recruiting and orienting resource parents and patients toward different types of activities should take into account the complexity and risks of the tasks. Family stakeholders are appreciated and have a positive impact on projects in which they are involved.

Levels and sources of heavy metals and PAHs in sediment of Djibouti-city (Republic of Djibouti).

Selected heavy metals and polycyclic aromatic hydrocarbons (PAHs) were determined in marine sediment from 28 sites Djibouti city. The concentrations of trace elements varied from 0 to 288.1mg/kg with relative abundance of trace metals in sediments was in the order of Zn>Cu>Ni>Cr>Co>Pb>Cd. Zn, Cu and Ni exceeded consensus based sediment quality guideline values 7, 14, 15 sites respectively. Enrichment factor and pollution load index showed relatively low to moderate contamination. The concentrations of total 16 PAHs varied widely depending on the sample location and ranged from 2.65 to 3760.11ng·g-1, with the mean concentration value of 387.87ng·g-1. Compositions and relative abundance of individual PAH using molecular diagnostic ratio using congener's m/z 178 and 202 indicated pyrolytic origin and reflecting a petroleum combustion, grass/wood and coal combustion and a petrogenic source. This study represents the first pollution baseline and a reference for future studies in Djibouti.

Solar photo-Fenton using peroxymonosulfate for organic micropollutants removal from domestic wastewater: comparison with heterogeneous TiO2 photocatalysis.

This work aims at decontaminating biologically treated domestic wastewater effluents from organic micropollutants by sulfate radical based (SO4(-)) homogeneous photo-Fenton involving peroxymonosulfate as an oxidant, ferrous iron (Fe(II)) as a catalyst and simulated solar irradiation as a light source. This oxidative system was evaluated by using several probe compounds belonging to pesticides (bifenthrin, mesotrione and clothianidin) and pharmaceuticals (diclofenac, sulfamethoxazole and carbamazepine) classes and its kinetic efficiency was compared to that to the well known UV-Vis/TiO2 heterogeneous photocatalysis. Except for carbamazepine, apparent kinetic rate constants were always 10 times higher in PMS/Fe(II)/UV-Vis than in TiO2/UV-Vis system and more than 70% of total organic carbon abatement was reached in less than one hour treatment. Hydroxyl radical (OH) and SO4(-) reactivity was investigated using mesotrione as a probe compound through by-products identification by liquid chromatography-high resolution-mass spectrometry and transformation pathways elucidation. In addition to two OH based transformation pathways, a specific SO4(-) transformation pathway which first involved degradation through one electron transfer oxidation processes followed by decarboxylation were probably responsible for mesotrione degradation kinetic improvement upon UV-Vis/PMS/Fe(II) system in comparison to UVVis/TiO2 system.

Solar photo-Fenton like using persulphate for carbamazepine removal from domestic wastewater.

This work aimed at decontaminating biologically treated domestic wastewater effluent from pharmaceutical residues by using sulphate radical based homogeneous photo-Fenton involving persulphate (PS) as an oxidant, ferrous iron (Fe(II)) as a catalyst and simulated solar irradiation as a light source. This is the first time that the beneficiary use of solar energy in PS/Fe(II)/UV-Vis system was evaluated by using carbamazepine (CBZ) as a probe compound. In wastewater, CBZ was fully degraded in 30 min for an initial CBZ concentration of 50 µM and an optimal PS:Fe(II) molar ratio of 2:1 thanks to the high selectivity in reactivity of the sulphate radical limiting scavenging effects of organic matter and inorganic ions. Seventeen by-products were identified using liquid chromatography-high resolution-mass spectrometry allowing for the establishment of degradation pathways. CBZ first underwent degradation through one electron transfer oxidation processes due to sulphate radical reactivity followed by hydroxylation processes through hydroxyl radical formed by Fe(III) photoreduction. The sequential generation of sulphate radical and hydroxyl radical has made PS/Fe(II)/UV-Vis a kinetically effective process in removing CBZ from wastewater without the accumulation of toxic intermediates and opens new remediation strategies for tertiary treatment in domestic wastewater treatment plants.

Ciprofloxacin oxidation by UV-C activated peroxymonosulfate in wastewater.

This work aimed at demonstrating the advantages to use sulfate radical anion for eliminating ciprofloxacin residues from treated domestic wastewater by comparing three UV-254nm based advanced oxidation processes: UV/persulfate (PDS), UV/peroxymonosulfate (PMS) and UV/H2O2. In distilled water, the order of efficiency was UV/PDS>UV/PMS>UV/H2O2 while in wastewater, the most efficient process was UV/PMS followed by UV/PDS and UV/H2O2 mainly because PMS decomposition into sulfate radical anion was activated by bicarbonate ions. CIP was fully degraded in wastewater at pH 7 in 60min for a [PMS]/[CIP] molar ratio of 20. Nine transformation products were identified by liquid chromatography-high resolution-mass spectrometry allowing for the establishment of degradation pathways in the UV/PMS system. Sulfate radical anion attacks prompted transformations at the piperazinyl ring through a one electron oxidation mechanism as a major pathway while hydroxyl radical attacks were mainly responsible for quinolone moiety transformations as a minor pathway. Sulfate radical anion generation has made UV/PMS a kinetically effective process in removing ciprofloxacin from wastewater with the elimination of ciprofloxacin antibacterial activity.

In vitro activity of natural honey alone and in combination with curcuma starch against Rhodotorula mucilaginosa in correlation with bioactive compounds and diastase activity.

OBJECTIVE: To evaluate the in vitro activity and synergism of the combinations of natural honey and curcuma starch against Rhodotorula mucilaginosa in correlation with total phenolic, flavonoid contents, and diastase activity. METHODS: The Folin-Ciocalteu test was used to determine the total polyphenols content and the flavonoid content was analyzed using by the aluminum chloride method. The antifungal activity of the natural honey, determined by an agar well diffusion assay and agar incorporation method. RESULTS: Total phenolic content varied from (63.930.11) to (95.366.08) mg GAE/100 g honey as gallic acid equivalent. Total flavonoids content varied from (5.41±0.04) to (9.94±0.54) mg CE/100 g. Diastase activity values were between (7.3±2.8) and (26±2.8). The zone inhibition diameter for the six honey samples without starch ranged between 6 and 20 mm. When starch was mixed with honey and then added to well, a zone inhibition increase diameter 7 and 21 mm. The percentage increase was noticed with each variety and it ranged between 5% and 62.5%. The minimal inhibitory concentrations for the six varieties of honey without starch against Rhodotorula mucilaginosa ranged between 28% and 36% (v/v). When starch was incubated with honey and then added to media, a minimal inhibitory concentration drop has been noticed with each variety. It ranged between 6.66 % and 20% (w/v). No significant correlation was established between diastase activity and bioactive compounds. CONCLUSIONS: The mixture of curcuma starch and honey could lead to the development of new combination antibiotics against Rhodotorula infections.

Wastewater reclamation using discarded reverse osmosis membranes for reuse in irrigation in Djibouti, an arid country.

The purpose of this paper is to establish the feasibility of recovering discarded reverse osmosis (RO) membranes in order to reduce the salinity of domestic treated wastewater. This study shows that the reuse of RO membranes is of particular interest for arid countries having naturally high mineralized water such as Djibouti. The pilot desalination unit reduces the electrical conductivity, the turbidity and the total dissolved salt respectively at 75-85, 96.7 and 95.4%. The water produced with this desalination unit contains an average of 254 cfu/100 mL total coliforms and 87 cfu/100 mL fecal coliforms. This effluent meets the World Health Organization standards for treated wastewater reuse for agricultural purposes. The annual cost of the desalination unit was evaluated as US $/m(3) 0.82, indicating the relatively high cost of this process. Nevertheless, such processes are required to produce an effluent, with a high reuse potential.

Antibacterial activity of various honey types of Algeria against Staphylococcus aureus and Streptococcus pyogenes

OBJECTIVE@#To assess the in vitro antibacterial activity of honey from different geographical location on Gram negative organisms.@*METHODS@#Different concentrations (Undiluted honey, 10 %, 30%, 50% and 70% wt/vol) of honey were studied in vitro using Staphylococcus aureus (S. aureus) and Streptococcus pyogenes (S. pyogenes), briefly, two-fold dilutions of honey solutions were tested to determine the minimum inhibitory concentration (MIC) against each type of microorganism, followed by more assays within a narrower dilution range to obtain more precise MIC values. MICs were determined by both visual inspection and spectrophotometric assay at 620 nm. These honey samples were compared with standard antibiotics like ampicillin, penicillin G, amoxicillin, gentamycin, tobramycin, erythromycin and chloramphenicol was determined by the disc diffusion method.@*RESULTS@#The diameter of zone of the inhibition (ZDI) of honey has various concentrations tested for the isolates ranged 0-46 mm for S. aureus, 0-44 mm for S. pyogenes. While the MIC (%) ranged 12%-95%, 25%-73% respectively.@*CONCLUSIONS@#Algeria honey, in-vitro, possess antibacterial activity.

Antifungal activity of four honeys of different types from Algeria against pathogenic yeast:Candida albicans and Rhodotorula sp

Objective: To evaluate the antifungal activity of four honeys of different types from Algeria against pathogenic yeast i.e. Candida albicans (C. albicans) and Rhodotorula sp. Methods:Four Algeria honeys of different botanical origin were analyzed to test antifungal effect against C. albicans, and Rhodotorula sp. Different concentrations (undiluted, 10%, 30%, 50%and 70%w/v) of honey were studied in vitro for their antifugal activity using C. albicans and Rhodotorula sp. as fungal strains. Results:The range of the diameter of zone of inhibition of various concentrations of tested honeys was (7-23 mm) for Rhodotorula sp., while C. albicans showed clearly resistance towards all concentrations used. The MICs of tested honey concentrations against C. albicans and Rhodotorula sp. were (70.09-93.48)%and (4.90-99.70)%v/v, respectively. Conclusions:This study demonstrates that, in vitro, these natural products have clearly an antifungal activity against Rhodotorula sp. and C. albicans.

Additive potential of ginger starch on antifungal potency of honey against Candida albicans

Objective: To evaluate the additive action of ginger starch on the antifungal activity of honey against Candida albicans (C. albicans). Methods: C. albicans was used to determine the minimum inhibitory concentration (MIC) of four varieties of Algerian honey. Lower concentrations of honey than the MIC were incubated with a set of concentrations of starch and then added to media to determine the minimum additive inhibitory concentration (MAIC). Results: The MIC for the four varieties of honey without starch against C. albicans ranged between 38% and 42% (v/v). When starch was incubated with honey and then added to media, a MIC drop was noticed with each variety. MAIC of the four varieties ranged between 32% honey (v/v) with 4% starch and 36% honey (v/v) with 2% starch. Conclusions: The use of ginger starch allows honey benefit and will constitute an alternative way against the resistance to antifungal agents.

Synergistic action of starch and honey against Aspergillus niger in correlation with Diastase Number.

To evaluate the synergistic action of starch on the antifungal activity of honey, a comparative method of adding honey with and without starch to culture media was used. Aspergillus niger was used to determine the minimum inhibitory concentration (MIC) of five varieties of honey. In the second step, lower concentrations of honey than the MIC were incubated with a set of concentrations of starch and then added to media to determine the minimum synergistic inhibitory concentration (MSIC). The MIC for the five varieties of honey without starch against A. niger ranged between 46% and 50% (v/v). When starch was incubated with honey and then added to media, an MIC drop was noticed with each variety and it ranged between 6% and 19.5%. Negative correlation has been established between the MIC drop and the Diastase Number.