Response surface methodology directed modeling of the biosorption of progesterone onto acid activated Moringa oleifera seed biomass: Parameters and mechanisms.

In this study, chemically activated fat-free powdered Moringa oleifera seed biomass (MOSB) was synthesized, characterized, and utilized as a cost-effective biosorbent for the abstraction of progesterone (PGT) hormone from synthetic wastewater. Natural PGT is a human steroid hormone from the progestogen family. Synthetic PGT is approved for the regulation of the menstrual cycle, aiding contraception, and is administered as a hormone replacement therapy in menopausal and post-menopausal women. PGT is an endocrine disrupting chemical (EDC) with negative health impacts on biota. The X-ray diffractogram (XRD), Scanning electron microscopy-Energy-dispersive X-ray spectroscopy (SEM-EDS), and Brunauer-Emmet-Teller (BET) analyses displayed a porous, amorphous biosorbent with an elemental composition of 72.5% carbon and 22.5% oxygen and a specific surface area of 210.0 m2 g-1. The process variables including temperature (298-338 K), pH (2-10), contact time (10-180 min), adsorbate concentration (20-500 µg L-1), and adsorbent dosage (0.1-2.0 g) were optimized using response surface methodology (RSM) to obtain the greatest efficacy of MOSB during biosorption of PGT. The optimum parameters for PGT biosorption onto MOSB were: 86.8 min, 500 µg L-1 adsorbate concentration, 298 K, and 0.1 g adsorbent dosage. PGT removal from aqueous solutions was pH-independent. The Langmuir isotherm best fitted the equilibrium data with maximal monolayer biosorption capacity of 135.8 µg g-1. The biosorption rate followed the pseudo-first-order (PFO) kinetic law. The thermodynamic functions (ΔG < 0, ΔH = -9.258 kJ mol-1 and ΔS = +44.16 J mol-1) confirmed that the biosorption of PGT onto MOSB is a spontaneous and exothermic process with increased randomness at the adsorbent surface. The biosorption mechanism was physisorption and was devoid of electrostatic interactions. The findings from this study indicate that MOSB is an inexpensive, low-carbon, and environmentally friendly biosorbent that can effectively scavenge PGT from aqueous solutions.

Endocrine disrupting chemicals in wastewater treatment plants in Kenya, East Africa: Concentrations, removal efficiency, mass loading rates and ecological impacts.

This study investigated the levels, mass loadings, removal efficiency, and associated ecotoxicological risks of selected endocrine disrupting chemicals (EDCs), namely, dibutylphthalate (DBP), diethylhexylphthalate (DEHP), dimethylphthalate (DMP), linuron (LNR) and progesterone (PGT) in wastewater, sludge, and untreated dry biosolid (UDBS) samples from twelve wastewater treatment plants (WWTPs) in nine major towns in Kenya. Analysis was done using high-performance liquid chromatography coupled with triple quadrupole mass spectrometry (LC-MS/MS). All the wastewater influents had quantifiable levels of EDCs with DBP being the most abundant (37.49%) with a range of 4.33 ± 0.63 to 19.68 ± 1.24 µg L-1. DEHP was the most abundant in sludge and accounted for 48.2% ranging between 278.67 and 9243.49 ng g-1 dry weight (dw). In the UDBS samples, DEHP was also the most abundant (40%) of the total EDCs detected with levels ranging from 78.77 to 3938.54 ng g-1 dw. The average removal efficiency per pollutant was as follows: DMP (98.7%) > DEHP (91.7%) > PGT (83.4%) > DBP (77.9%) > LNR (72.2%) which can be attributed to sorption onto the biosolid, biological degradation, photolysis, and phytoremediation. The pH was negatively correlated to the EDC concentrations while total dissolved solids (TDS), chemical oxygen demand (COD), biochemical oxygen demand (BOD5), and electrical conductivity (EC) were positively correlated. The mass loadings were as high as 373.33 g day-1 of DBP in the treatment plants located in densely populated cities. DEHP and PGT had their Risk Quotients (RQs) > 1, posing a high risk to biota. DMP, DBP, and LNR posed medium risks as their RQ values were between 0.1 and 1. EDCs are therefore loaded to environmental compartments through either the effluent that loads these pollutants into the receiving aquatic ecosystem or through the UDBS, which are used as fertilizers in agricultural farmlands causing potential toxicological risks to aquatic and terrestrial life.

Efficient sequestration of malachite green in aqueous solution by laterite-rice husk ash-based alkali-activated materials: parameters and mechanism.

In this work, laterite (LA) and rice husk ash (RHA)-based alkali-activated materials (AAMs) with varying %RHA contents (0, 5, 10, 15, and 20%) were prepared for the removal of malachite green (MG) dye from water. The precursors and AAMs were characterized by standard methods (XRF, XRD, TG/DTA SEM, and FTIR). The SEM micrographs and iodine index values showed that the incorporation of RHA improves the microporosity of laterite-based geopolymers. The incorporation of RHA did not result in any new mineral phases after alkalinization. Geopolymerization increased both the adsorption rate and capacity of the geopolymers relative to LA by approximately 5 times. The maximum adsorption capacity was 112.7 mg/g, corresponding to the GP95-5 (5% RHA) geopolymer. The adsorption capacity was therefore not solely controlled by the RHA fraction. The adsorption kinetics data was best predicted by the pseudo-second-order (PSO) model. The adsorption mechanism entails electrostatic interactions and ion exchange. These results show the suitability of laterite-rice husk ash (LA-RHA)-based alkali-activated materials as adsorbents for the efficient sequestration of malachite green in aqueous solution.

Synthesis of pozzolan and sugarcane bagasse derived geopolymer-biochar composites for methylene blue sequestration from aqueous medium.

In this study, four pozzolan-based geopolymers GP0, GP5, GP10, and GP20 were synthesized by alkaline activation and by substituting 0, 5, 10, and 20% of the precursor with sugarcane bagasse-derived biochar, respectively. The composites were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM/EDX), and Brunauer-Emmett-Teller (BET) surface area analyses, and applied to sequester methylene blue (MB) dye in an aqueous medium in batch mode. The alkaline activation of pozzolan-biochar blends resulted in the formation of poly (Ferro-sialate-siloxo)-biochar chains. The adsorption capacity increased with an increase in biochar content from 24.44 to 455.46 mg/g (18-fold) for GP0 and GP10, respectively. The sorption kinetics of MB onto the composites followed pseudo-second-order kinetics while the equilibrium data were best described by the Sips isotherm model. The adsorption process was thermodynamically spontaneous, endothermic (ΔH = 14.32-32.20 kJ/mol), and physical. The amount of adsorbent required for the removal of 99% of a fixed amount of MB in different volumes of effluent was predicted. Cost-analysis indicates that the composites are efficient and cheaper eco-adsorbents than commercial activated carbon and are suitable alternative candidates for the removal of dyes from water.

Polycyclic aromatic hydrocarbons in breast milk of nursing mothers: Correlates with household fuel and cooking methods used in Uganda, East Africa.

Maternal breast milk, which is a complete food for the infant's growth, development, and health, contains fats and lipids making it susceptible to accumulation of lipophilic compounds like polycyclic aromatic hydrocarbons (PAHs). This study aimed at analyzing correlates of measured levels of PAHs in breast milk of nursing mothers to frequently used household fuels and cooking methods in Uganda, and estimate the potential health risks of PAHs to infants through breastfeeding. Sixty breast milk samples were collected from healthy and non-smoking mothers who had lived in Kampala capital city (urban area) and Nakaseke district (rural area) for at least five years. Sample extracts were analyzed for PAHs using a gas chromatograph coupled with a triple quadrupole mass spectrometer. ∑13PAHs in samples from Kampala ranged from 3.44 to 696 ng/g lw while those from Nakaseke ranged from 0.84 to 87.9 ng/g lw. PAHs with 2-3 rings were more abundant in the samples than PAHs with 4-6 rings. At least 33 % of the variance in the levels of ∑13PAHs in the breast milk samples was attributable to the fuel type and cooking methods used. Nursing mothers who used charcoal for cooking accumulated higher levels of ∑13PAHs in their breast milk samples compared to those who used firewood. Levels of ∑13PAHs in breast milk of mothers increased depending on the cooking methods used in the order; boiling< grilling< deep-frying. In all samples, hazard quotients for PAHs were <1 and estimated incremental cancer risks were all between 10-6 and 10-4, indicating that the health risks to infants due to the ingestion of PAHs in breast milk was tolerable. Further studies with large datasets on PAHs and their derivatives and, larger samples sizes are needed to confirm these findings.

Adsorption-desorption and leaching behavior of diuron on selected Kenyan agricultural soils.

In this work, the adsorption-desorption dynamics of diuron in three typical Kenyan agricultural soils, Nzoia (NZ), Thika (TH) and Machakos (MK) was investigated. The equilibrium adsorption data, tested against three classical nonlinear adsorption isotherms, was best described by the Freundlich model. The Freundlich adsorption constant, (KF), increased in the order MK > TH > NZ soil. Additionally, the negative Gibb's free energy values indicate the adsorption processes were thermodynamically spontaneous and physical. Multiple linear regression analysis indicated that the adsorption-desorption behavior was controlled by the clay and phosphorus contents of the soil. Phosphorus negatively affected the adsorption of diuron and promoted desorption. The groundwater ubiquity score (GUS) indicated that diuron movement rating in MK soil was 'moderate' while the movement in TH and NZ soils was 'high'.

Occurrence of pesticides residues in French beans, tomatoes, and kale in Kenya, and their human health risk indicators.

Residue levels of seven commonly used pesticides were determined in random samples of tomatoes, French beans, and kale collected from horticultural farms in Buuri, Imenti North, and Imenti South sub-counties in Meru, Kenya, just before delivery to the consumers. QuEChERS method for extraction followed by LC-MS/MS was used to determine the concentrations. The concentrations (µg kg-1 wet weight) in French beans, kale, and tomatoes ranged from below detection limit (BDL): BDL-48.65 (carbendazim), BDL-290.76 (imidacloprid), BDL-2.81 (acetamiprid), BDL-25.76 (azoxystrobin), BDL-105.18 (metalaxyl), BDL-0.15 (diazinon), and BDL-0.17(chlorpyrifos). The maximum residue levels determined in the horticultural produce from the three regions were 290 µg kg-1 for imidacloprid in tomatoes from Buuri and 25.76 µg kg-1for azoxystrobin in French beans from Imenti South. The pesticide residue levels generally were extremely low and met the MRLs set by EU and other countries, except for carbendazim and metalaxyl in French beans, and posed no concern to human health. The estimated daily intakes (EDI) (mg kg-1 BW/day) for the population of Meru County were very low ranging from 1.685 × 10-8 (acetamiprid) to 2.381 × 10-5 (imidacloprid) in tomatoes, 2.849 × 10-9 (metalaxyl) to 3.633 × 10-7 (azoxystrobin) in French beans, and 1.392 × 10-8 (diazinon) in kale, respectively. The health risk indices were subsequently extremely low for the detectable pesticide residues, ranging from 6.74 × 10-7 (acetamiprid) to 3.97 × 10-4 (imidacloprid) in tomatoes, 3.56 × 10-8 (metalaxyl) to 5.52 × 10-5 (chlorpyrifos) in French beans, and 6.96 × 10-5 (diazinon) in kale, respectively, indicating no health risk in the population, but their presence in these vegetables cannot be ignored as long-term exposure can still cause health risks.

Insights on adsorption of carbamazepine onto iron oxide modified diatomaceous earth: Kinetics, isotherms, thermodynamics, and mechanisms.

To ameliorate adsorbent recovery by an external magnetic field, naturally occurring diatomaceous earth (DE) was modified with iron-oxide, characterized and applied for adsorption of carbamazepine (CBZ) from synthetic wastewater using batch equilibration method. The fabricated adsorbent was characterized using XRF, XRD, SEM-EDX, FT-IR, BET surface area analysis, VSM and pH of point of zero charge (pHpzc) determination. The adsorption rate was described by the pseudo-first-order (PFO) model suggesting a physisorption controlled rate-determining step. Equilibrium adsorption data were fitted to linear and nonlinear isotherm models, viz Langmuir and Freundlich models, and were best described by Freundlich nonlinear equations implying heterogeneous multilayer adsorption. The best-fitting kinetic and isotherm model was determined using four mathematical error functions. The thermodynamic parameters, namely enthalpy (ΔH = -26.4 kJ mol-1), Gibbs free energy (ΔG = -2.22 kJ mol-1 at 298 K), entropy (ΔS = -34.0 kJ mol-1), indicated that the adsorption was a spontaneous, exothermic, and physical process. The adsorption mechanism is postulated to involve cation-π interactions. Modified diatomaceous earth is a potentially excellent, low-cost, and novel sorbent for CBZ adsorption with 88% removal in 180 min and provides a possible alternative adsorbent for wastewater treatment.