Occurrence profiling, risk assessment, and correlations of antimicrobials in surface water and groundwater systems in Southwest Nigeria.

The presence of antimicrobials in water has grown into a major global health concern. This study thus focused on the presence, ecological implications, and potential health risks associated with nine antimicrobials: five antibiotics (ampicillin, chloramphenicol, ciprofloxacin, metronidazole, and tetracycline) and four parabens (methylparaben, ethylparaben, propylparaben, and butylparaben) in surface water and groundwater samples collected from three Southwestern States in Nigeria (Osun, Oyo, and Lagos States). These antimicrobials were widely detected across the three States with ciprofloxacin being the most dominant having maximum average concentrations of 189 µg L-1 and 319 µg L-1 in surface water and groundwater respectively. The range of average concentrations of antibiotics in surface water are 47.3-235 µg L-1 (Osun), 27.9-166 µg L-1 (Oyo) and 52.1-159 µg L-1 (Lagos). For groundwater, it is 35.3-180 µg L-1 (Osun), 26.5-181 µg L-1 (Oyo) and 32.3-319 µg L-1 (Lagos). The average concentrations of all parabens were 32.4-153 µg L-1, 53.4-80.1 µg L-1, and 83.2-132 µg L-1 for surface water and 46.7-55.7 µg L-1, 53-117 µg L-1, and 62.4-118 µg L-1 for groundwater in Osun, Oyo, and Lagos States respectively. Methylparaben was most frequently detected paraben with average concentrations of 153 µg L-1 and 117 µg L-1 in surface water and groundwater respectively. The measured environmental concentrations of these antimicrobials pose a significant ecological risk while those of ciprofloxacin and ampicillin pose a high health risk to all population groups studied. The average concentrations of antibiotics investigated in this study exceeded their threshold values for Predicted No-Effect Concentrations (PNEC) associated with resistance selection, except for tetracycline.

Distribution and toxicity of dihydroxybenzenes in drinking water sources in Nigeria.

This study provides, for the first time, data on the distribution and toxicity of catechol (CAT) and hydroquinone (HQ) in drinking water sources from Africa. Groundwater (boreholes and hand-dug wells) and surface water in three Southwestern States in Nigeria served as sampling sites. The concentrations of CAT and HQ in groundwater and surface water were determined throughout a period of 12 months, evaluating the effects of seasonal variation (rainy and dry seasons). Mean concentrations of CAT in water samples were higher than those of HQ. In this study, CAT was more frequently detected, with its mean concentration in groundwater samples higher in the rainy season (430 µg L-1) than in the dry season (175 µg L-1). Multivariate analysis using the Principal Component Analysis Software suggests that in most sample sites, CAT and HQ in water samples were from entirely different anthropogenic sources. The most impacted population groups were the toddlers and infants. Similarly, maximum and median concentrations of CAT in water samples pose serious risks to Daphnia at both acute and chronic levels. The results from this study suggest the need for further control of these dihydroxybenzenes through regular monitoring and removal from drinking water during treatment.

Cellulose-based adsorbents for solid phase extraction and recovery of pharmaceutical residues from water.

Cellulose has attracted interest from researchers both in academic and industrial sectors due to its unique structural and physicochemical properties. The ease of surface modification of cellulose by the integration of nanomaterials, magnetic components, metal organic frameworks and polymers has made them a promising adsorbent for solid phase extraction of emerging contaminants, including pharmaceutical residues. This review summarizes, compares, and contrasts different types of cellulose-based adsorbents along with their applications in adsorption, extraction and pre-concentration of pharmaceutical residues in water for subsequent analysis. In addition, a comparison in efficiency of cellulose-based adsorbents and other types of adsorbents that have been used for the extraction of pharmaceuticals in water is presented. From our observation, cellulose-based materials have principally been investigated for the adsorption of pharmaceuticals in water. However, this review aims to shift the focus of researchers to the application of these adsorbents in the effective pre-concentration of pharmaceutical pollutants from water at trace concentrations, for quantification. At the end of the review, the challenges and future perspectives regarding cellulose-based adsorbents are discussed, thus providing an in-depth overview of the current state of the art in cellulose hybrid adsorbents for extraction of pharmaceuticals from water. This is expected to inspire the development of solid phase exraction materials that are efficient, relatively cheap, and prepared in a sustainable way.

Efficient Removal of Tetracycline and Bisphenol A from Water with a New Hybrid Clay/TiO2 Composite.

New TiO2 hybrid composites were prepared from kaolin clay, predried and carbonized biomass, and titanium tetraisopropoxide and explored for tetracycline (TET) and bisphenol A (BPA) removal from water. Overall, the removal rate is 84% for TET and 51% for BPA. The maximum adsorption capacities (qm) are 30 and 23 mg/g for TET and BPA, respectively. These capacities are far greater than those obtained for unmodified TiO2. Increasing the ionic strength of the solution does not change the adsorption capacity of the adsorbent. pH changes only slightly change BPA adsorption, while a pH > 7 significantly reduces the adsorption of TET on the material. The Brouers-Sotolongo fractal model best describes the kinetic data for both TET and BPA adsorption, predicting that the adsorption process occurs via a complex mechanism involving various forces of attraction. Temkin and Freundlich isotherms, which best fit the equilibrium adsorption data for TET and BPA, respectively, suggest that adsorption sites are heterogeneous in nature. Overall, the composite materials are much more effective for TET removal from aqueous solution than for BPA. This phenomenon is assigned to a difference in the TET/adsorbent interactions vs the BPA/adsorbent interactions: the decisive factor appears to be favorable electrostatic interactions for TET yielding a more effective TET removal.

Pollution and risk assessment of phenolic compounds in drinking water sources from South-Western Nigeria.

This study reports the occurrence and risk assessment of 2,4-dinitrophenol (2,4-DNP), phenol (PHE), and 2,4,6-trichlorophenol (2,4,6-TCP) in drinking water sources in three south-western States in Nigeria (Osun, Oyo, and Lagos). Groundwater (GW) and surface water (SW) were collected during dry and rainy seasons of a year. The detection frequency of the phenolic compounds followed the trend Phenol > 2,4-DNP > 2,4,6-TCP. The mean concentrations of 2,4-DNP, Phenol, and 2,4,6-TCP in GW/SW samples from Osun State were 639/553 µg L-1, 261/262 µg L-1, and 169/131 µg L-1 during the rainy season and 154/7 µg L-1, 78/37 µg L-1, and 123/15 µg L-1 during the dry season, respectively. In Oyo State, the mean concentrations were 165/391 µg L-1 for 2,4-DNP and 71/231 µg L-1 for Phenol in GW/SW samples, respectively, during the rainy season. Generally, in the dry season, these values decreased. In any case, these concentrations are higher than those previously reported in water from other countries. The concentration of 2,4-DNP in water posed serious ecological risks to Daphnia on the acute scale while it was algae on the chronic scale. Estimated daily intake and hazard quotient calculations suggest that 2,4-DNP and 2,4,6-TCP in water pose serious toxicity concerns to humans. Additionally, the concentration of 2,4,6-TCP in water from Osun State in both seasons of the year and in both groundwater and surface water poses significant carcinogenic risks to persons ingesting water from these sources in the State. Every exposure group studied were at risk from ingesting these phenolic compounds in water. However, this risk decreased with increasing age of the exposure group. Results from the principal component analysis indicate that 2,4-DNP in water samples is from an anthropogenic source different from that for Phenol and 2,4,6-TCP. There is a strong need to treat water from GW and SW systems in these States before ingesting while assessing their quality regularly.

Antibiotic resistomes and their chemical residues in aquatic environments in Africa.

The aquatic environment is a hotspot for the transfer of antibiotic resistance to humans and animals. Several reviews have put together research efforts on the presence and distribution of antibiotic resistant bacteria (ARB), antibiotic resistance genes (ARGs), and antibiotic chemical residue (ACRs) in food, hospital wastewater, and even in other aquatic environments. However, these reports are largely focused on data from developed countries, while data from developing countries and especially those in Africa, are only marginally discussed. This review is the first effort that distills information on the presence and distribution of ARGs and ACRs in the African aquatic environments (2012-2021). This review provides critical information on efforts put into the study of ARB, ARGs, and ACRs in aquatic environments in Africa through the lens of the different sub-regions in the continent. The picture provided is compared with those from some other continents in the world. It turns out that the large economies in Africa (South Africa, Nigeria, Tunisia, Kenya) all have a few reports of ARB and ARGs in their aquatic environment while smaller economies in the continent could barely provide reports of these in their aquatic environment (in most cases no report was found) even though they have some reports on resistomes from clinical studies. Interestingly, the frequency of these reports of ARB and ARGs in aquatic environments in Africa suggests that the continent is ahead of the South American continent but behind Europe and Asia in relation to providing information on these contaminants. Common ARGs found in African aquatic environment encode resistance to sulfonamide, tetracycline, ß-lactam, and macrolide classes of antibiotics. The efforts and studies from African scientists in eliminating ARB and ARGs from the aquatic environment in Africa are also highlighted. Overall, this document is a ready source of credible information for scientists, policy makers, governments, and regional bodies on ARB, ARGs, and ACRs in aquatic environments in Africa. Hopefully, the information provided in this review will inspire some necessary responses from all stakeholders in the water quality sector in Africa to put in more effort into providing more scientific evidence of the presence of ARB, ARGs, and ACRs in their aquatic environment and seek more efficient ways to handle them to curtail the spread of antibiotic resistance among the population in the continent. This will in turn, put the continent on the right path to meeting the United Nations Sustainable Development Goals #3 and #6, which at the moment, appears to be largely missed by most countries in the continent.

Occurrence and human exposure assessment of parabens in water sources in Osun State, Nigeria.

Parabens are chemicals extensively used in pharmaceuticals, cosmetics, personal hygiene and food products as preservatives. They are classified as emerging contaminants with endocrine-disrupting capability. In this study, the concentrations of Methylparaben (MeP), Ethylparaben (EtP), Propylparaben (PrP) and Butylparaben (BuP) were obtained from groundwater, surface-water and packaged water samples collected from urban and rural areas of Osun State, Nigeria using HPLC-UV equipment. Data obtained were subjected to descriptive (Mean ± SD), inferential (Kruskal-Wallis test) and multivariate analyses. MeP had the highest average concentration of 163 and 68 µg L-1 in surface water and groundwater respectively while concentrations of MeP, EtP, PrP and BuP were higher than previously reported in other countries. Methylparaben had the highest detection frequencies (88.0 and 50.0%) followed by BuP (69.0 and 50.0%) in surface water and groundwater respectively. No significant difference was observed for concentrations of parabens in groundwater samples in urban and rural sampling sites, suggesting that people living around these sites are equally exposed to any health implications from the use of paraben-polluted potable water. Principal Component Analysis (PCA) data suggest that the pairs MeP & EtP, PrP & BuP (in surface water samples) and MeP, EtP, & PrP (in groundwater samples) are from similar pollution sources. Ecological risk assessment using Algae, Fish, and Daphnia suggests Daphnia as the most sensitive organism while BuP and PrP show the highest health risk. Human exposure assessment showed that higher overall median estimated daily intake (EDI) values for groundwater were observed in infants (1.71 µg kg-1 bw day-1, ∑PBs) compared to toddlers (1.03 µg kg-1 bw day-1, ∑PBs), children (0.64 µg kg-1 bw day-1, ∑PBs), teenagers (0.51 µg kg-1 bw day-1, ∑PBs) and adults (0.62 µg kg-1 bw day-1, ∑PBs). Although these values are below limits set in a few countries, potential bioaccumulation could lead to severe health consequences.

Toxicity and removal of parabens from water: A critical review.

Parabens are biocides used as preservatives in food, cosmetics and pharmaceuticals. They possess antibacterial and antifungal activity due to their ability to disrupt cell membrane and intracellular proteins, and cause changes in enzymatic activity of microbial cells. Water, one of our most valuable natural resource, has become a huge reservoir for parabens. Halogenated parabens from chlorination/ozonation of water contaminated with parabens have shown to be even more persistent in water than other types of parabens. Unfortunately, there is dearth of data on their (halogenated parabens) presence and fate in groundwater which serves as a major source of drinking water for a huge population in developing countries. An attempt to neglect the presence of parabens in water will expose man to it through ingestion of contaminated food and water. Although there are reviews on the occurrence, fate and behaviour of parabens in the environment, they largely omit toxicity and removal aspects. This review therefore, presents recent reports on the acute and chronic toxicity of parabens, their estrogenic agonistic and antagonistic activity and also their relationship with antimicrobial resistance. This article further X-rays several techniques that have been employed for the removal of parabens in water and their drawbacks including adsorption, biodegradation, membrane technology and advanced oxidation processes (AOPs). The heterogeneous photocatalytic process (one of the AOPs) appears to be more favoured for removal of parabens due to its ability to mineralize parabens in water. However, more work is needed to improve this ability of heterogeneous photocatalysts. Perspectives that will be relevant for future scientific studies and which will drive policy shift towards the presence of parabens in our drinking waters are also offered. It is hoped that this review will elicit some spontaneous actions from water professionals, scientists and policy makers alike that will provide more data, effective technologies, and adaptive policies that will address the growing threat of the presence of parabens in our environment with respect to human health.

Green synthesis of ZnO coated hybrid biochar for the synchronous removal of ciprofloxacin and tetracycline in wastewater.

Preparation of biochar from kaolinite and coconut husk (KCB) and further activated with HCl (KCB-A) and KOH (KCB-B) via a microwave technique for the remediation of ciprofloxacin (CIP) and tetracycline (TET) from water was carried out. Characterization using scanning electron microscopy, energy dispersive X-ray, Fourier transform infrared spectroscopy and X-ray diffraction showed the successful synthesis of functionalized biochars. Batch adsorption experiments demonstrated the potential of the adsorbents for fast and efficient removal of CIP and TET from solution. The adsorption capacities were found to be 71, 140 and 229 mg g-1 for CIP and 118, 117 and 232 mg g-1 for TET removal on KCB, KCB-A and KCB-B, respectively. For KCB, KCB-B and KCB-B, CIP adsorption best followed the pseudo second order kinetic model (PSOM), pseudo first order kinetic model (PFOM) and intraparticle diffusion (IDP) respectively. TET adsorption followed PSOM for KCB, IPD for KCB-B and PFOM for KCB-A. CIP adsorption on KCB, KCB-A and KCB-B best fit the Temkin, Langmuir and Brouers-Sotolongo isotherms, respectively, and TET adsorption on KCB best fit Brouers-Sotolongo while KCB-A and KCB-B best fit Langmuir-Freundlich. Adsorption of both contaminants was thermodynamically feasible showing that these materials are excellent adsorbents for the treatment of pharmaceuticals in water.

Clean technology for synchronous sequestration of charged organic micro-pollutant onto microwave-assisted hybrid clay materials.

The Sustainable Development Goal 6 (SDG #6) of the United Nations (UN) is hinged on the provision, availability, and sustainability of water for the global populace by 2030. In a bid to achieve this goal, the quest to seek for ubiquitous and low-cost adsorbents to treat effluents laden with industrial dyes, such as methylene blue (MB), is on the increase in recent years. Acute exposure of humans to (MB) dye causes cyanosis, necrosis, and jaundice and even leads to death. In this research, zinc-modified hybrid clay composite adsorbent (materials from kaolinite and biomass (crushed Carica papaya seeds and/or plantain peel)) was developed via microwave route. This adsorbent was characterized using field emission scanning electron microscopy (FE-SEM), Fourier transform infrared (FTIR) spectroscopy, energy-dispersive X-ray (EDX), and high-resolution transmission electron microscopy (HR-TEM). These characterization techniques confirmed the success achieved in doping hybrid clay with Zn. These adsorbents were used to sequester cationic dye (MB) from aqueous solutions and textile effluent under various experimental conditions. The adsorption and desorption data obtained were analyzed using various kinetic models, which are two-step kinetics, pseudo-first order, pseudo-second order, fractal kinetics, first-order desorption, second-order desorption, and modified statistical rate theory (MSRT) desorption models. Results showed that the adsorption of the dye occurred via several chemical interactions, while the latter models (for desorption) indicated that desorption occurred in two different desorption sites on the adsorbent surfaces, which showed that the adsorption of MB dye onto the adsorbents was stable without the emergence of any secondary pollution. Adsorption of MB was achieved within 15 min for aqueous solutions and 900 min for textile effluent, which is an improvement on previous results from other studies. The three adsorption-desorption cycles for MB uptake by the adsorbents showed that it is pragmatically applicable to treat textile effluents. Hence, low-cost composite adsorbents have a potential for the effective remediation of MB dye from textile effluents as this study confirmed.

Visible-Light-Mediated Photodynamic Water Disinfection @ Bimetallic-Doped Hybrid Clay Nanocomposites.

This study reports a new class of photocatalytic hybrid clay nanocomposites prepared from low-cost sources (kaolinite clay and Carica papaya seeds) doped with Zn and Cu salts via a solvothermal process. X-ray diffraction analysis suggests that Cu-doping and Cu/Zn-doping introduce new phases into the crystalline structure of Kaolinite clay, which is linked to the reduced band gap of kaolinite from typically between 4.9 and 8.2 eV to 2.69 eV for Cu-doped and 1.5 eV for Cu/Zn hybrid clay nanocomposites (Nisar, J.; Århammar, C.; Jämstorp, E.; Ahuja, R. Phys. Rev. B 2011, 84, 075120). In the presence of solar light irradiation, Cu- and Cu/Zn-doped nanocomposites facilitate the electron-hole pair separation. This promotes the generation of singlet oxygen which in turn improves the water disinfection efficiencies of these novel nanocomposite materials. The nanocomposite materials were further characterized using high-resolution scanning electron microscopy, fluorimetry, thermogravimetric analysis, and Raman spectroscopy. The breakthrough times of the nanocomposites for a fixed bed mode of disinfection of water contaminated with 2.32 × 107 cfu/mL E. coli ATCC 25922 under solar light irradiation are 25 h for Zn-doped, 30 h for Cu-doped, and 35 h for Cu/Zn-doped nanocomposites. In the presence of multidrug and multimetal resistant strains of E. coli, the breakthrough time decreases significantly. Zn-only doped nanocomposites are not photocatalytically active. In the absence of light, the nanocomposites are still effective in decontaminating water, although less efficient than under solar light irradiation. Electrostatic interaction, metal toxicity, and release of singlet oxygen (only in the Cu-doped and Cu/Zn-doped nanocomposites) are the three disinfection mechanisms by which these nanocomposites disinfect water. A regrowth study indicates the absence of any living E. coli cells in treated water even after 4 days. These data and the long hydraulic times (under gravity) exhibited by these nanocomposites during photodisinfection of water indicate an unusually high potential of these nanocomposites as efficient, affordable, and sustainable point-of-use systems for the disinfection of water in developing countries.

A novel route for preparation of chemically activated carbon from pistachio wood for highly efficient Pb(II) sorption.

Pistachio wood-derived activated carbon prepared by a two-stage process (PWAC-2), conducting two consecutive chemical activation processes with NH4NO3 and NaOH, respectively. The results showed that explosive characteristic of NH4NO3 can primarily be employed to produce a char, with a large surface area and a highly-ordered pore structure, which can be subjected to a second activation process with NaOH to prepare a more suitable activated carbon, with a highly porous structure and useful functional groups, for removal of lead ions from aqueous media. An L25 Taguchi experimental design was used by varying impregnation ratio, activation time and temperature in both pre- and post-activation stages, and the results showed that, in both stages, a small activating agent/precursor and a proportional low activation time suffice for preparation of an advantageous activated carbon for Pb(II) adsorption. A comprehensive study was performed on the equilibrium, kinetic and thermodynamic aspects of Pb(II) adsorption by the new activated carbon. The results exhibited that, having had a high lead adsorption capacity (190.2 mg g-1), a high adsorption rapidness, and thermodynamic favorability, PWAC-2 is a beneficial alternative for utilization in full-scale plants of lead removal from waters and wastewaters.

New micro/mesoporous nanocomposite material from low-cost sources for the efficient removal of aromatic and pathogenic pollutants from water.

A new micro/mesoporous hybrid clay nanocomposite prepared from kaolinite clay, Carica papaya seeds, and ZnCl2 via calcination in an inert atmosphere is presented. Regardless of the synthesis temperature, the specific surface area of the nanocomposite material is between ≈150 and 300 m2/g. The material contains both micro- and mesopores in roughly equal amounts. X-ray diffraction, infrared spectroscopy, and solid-state nuclear magnetic resonance spectroscopy suggest the formation of several new bonds in the materials upon reaction of the precursors, thus confirming the formation of a new hybrid material. Thermogravimetric analysis/differential thermal analysis and elemental analysis confirm the presence of carbonaceous matter. The new composite is stable up to 900 °C and is an efficient adsorbent for the removal of a water micropollutant, 4-nitrophenol, and a pathogen, E. coli, from an aqueous medium, suggesting applications in water remediation are feasible.

Adsorptive removal of 2,4,6-trichlorophenol in aqueous solution using calcined kaolinite-biomass composites.

Synergistically combined low-cost composites may be effective for the potential treatment of effluents containing organic pollutants. Hence, preparation of Carica-papaya-modified-kaolinite (CPK) and pine-cone-modified-kaolinite (PCK) composites via calcination of pure kaolinite (KAC), Carica-papaya and pine-cone seeds is demonstrated. The composites' specific surface areas were reduced by more than 57% but no structural modification in KAC lattice d-spacing, indicating impregnation of calcined biomass on clay surfaces and pores. However, composites' cation exchange capacities were enhanced over 4-fold, indicating higher potential for adsorption. Adsorption of 2,4,6-trichlorophenol on composites and KAC showed that CPK and PCK attained equilibrium relatively faster (30 min) compared to KAC (60 min). Modeling studies showed that 2,4,6-trichlorophenol removal mechanisms involved electrostatic interactions on sites of similar energy. Modification enhanced adsorption by 52 and 250% in PCK and CPK, respectively, and adsorption increased with temperature.

Disinfection of water with new chitosan-modified hybrid clay composite adsorbent.

Hybrid clay composites were prepared from Kaolinite clay and Carica papaya seeds via modification with chitosan, Alum, NaOH, and ZnCl2 in different ratios, using solvothermal and surface modification techniques. Several composite adsorbents were prepared, and the most efficient of them for the removal of gram negative enteric bacteria was the hybrid clay composite that was surface-modified with chitosan, Ch-nHYCA 1:5 (Chitosan: nHYCA = 1:5). This composite adsorbent had a maximum adsorption removal value of 4.07 × 106 cfu/mL for V. cholerae after 120 min, 1.95 × 106 cfu/mL for E. coli after ∼180 min and 3.25 × 106 cfu/mL for S. typhi after 270 min. The Brouers-Sotolongo model was found to better predict the maximum adsorption capacity (qmax ) of Ch-nHYCA1:5 composite adsorbent for the removal of E. coli with a qmax of 103.07 mg/g (7.93 × 107 cfu/mL) and V. cholerae with a qmax of 154.18 mg/g (1.19 × 108 cfu/mL) while the Sips model best described S. typhi adsorption by Ch-nHYCA 1:5 composite with an estimated qmax of 83.65 mg/g (6.43 × 107 cfu/mL). These efficiencies do far exceed the alert/action levels of ca. 500 cfu/mL in drinking water for these bacteria. The simplicity of the composite preparation process and the availability of raw materials used for its preparation underscore the potential of this low-cost chitosan-modified composite adsorbent (Ch-nHYCA 1:5 ) for water treatment.

Hybrid materials from agro-waste and nanoparticles: implications on the kinetics of the adsorption of inorganic pollutants.

This study is a first-hand report of the immobilization of Nauclea diderrichii seed waste biomass (ND) (an agro-waste) with eco-friendly mesoporous silica (MS) and graphene oxide-MS (GO + MS) nanoparticles, producing two new hybrid materials namely: MND adsorbent for agro-waste modified with MS and GND adsorbent for agro-waste modified with GO + MS nanoparticles showed improved surface area, pore size and pore volume over those of the agro-waste. The abstractive potential of the new hybrid materials was explored for uptake of Cr(III) and Pb(II) ions. Analysis of experimental data from these new hybrid materials showed increased initial sorption rate of Cr(III) and Pb(II) ions uptake. The amounts of Cr(III) and Pb(II) ions adsorbed by MND and GND adsorbents were greater than those of ND. Modification of N. diderrichii seed waste significantly improved its rate of adsorption and diffusion coefficient for Cr(III) and Pb(II) more than its adsorption capacity. The rate of adsorption of the heavy metal ions was higher with GO + MS nanoparticles than for other adsorbents. Kinetic data were found to fit well the pseudo-second-order and the diffusion-chemisorption kinetic models suggesting that the adsorption of Cr(III) and Pb(II) onto these adsorbents is mainly through chemisorption mechanism. Analysis of kinetic data with the homogeneous particle diffusion kinetic model suggests that particle diffusion (diffusion of ions through the adsorbent) is the rate-limiting step for the adsorption process.

Kinetics and thermodynamics of heavy metal ions sequestration onto novel Nauclea diderrichii seed biomass.

This study reports the sequestration of Cd(II) and Hg(II) using a new biosorbent, Nauclea diderrichii seed biomass. Experimental data obtained were fitted into kinetic and thermodynamic models. Experimental data fitted best into pseudo-second order kinetic model among others. Results obtained kinetically revealed that the biosorption of Cd(II) and Hg(II) using N. diderrichii seed biosorbent increased with increase in temperature. At the highest temperature, which was 333 K, the highest amount of metal biosorbed, q(e), for Cd(II) and Hg(II) obtained were 6.30 and 6.15 mg/g respectively. The biosorption of Cd(II) was kinetically faster than that of Hg(II), the highest initial biosorption rates for Cd(II) and Hg(II) were 56.19 and 4.39 mg/g min respectively. Thermodynamic parameters obtained by Erying equation from this study revealed that the biosorption process was spontaneous, feasible, endothermic with a decrease in the degree of chaos in the biosorption system.

Kinetic and thermodynamics of the removal of Zn2+ and Cu2+ from aqueous solution by sulphate and phosphate-modified Bentonite clay.

The modification of pristine Bentonite clay with sulphate and phosphate anions was found to increase its cation-exchange capacity (CEC), adsorption capacity and overall pseudo-second order kinetic rate constant for the adsorption of Cu(2+) and Zn(2+). Modification with sulphate and phosphate anion decreased the specific surface area of pristine Bentonite clay. Phosphate-modified Bentonite clay was found to give the highest adsorption capacity for both metal ions. The adsorption process was observed to be endothermic and spontaneous in nature for both metal ions with Zn(2+) being more adsorbed. Modification with phosphate anion increased the spontaneity of the adsorption process. The effective modification of pristine Bentonite clay with sulphate anion was confirmed from hypochromic shifts in the range of 13-18 cm(-1) which is typical of physisorption while modification with phosphate anion was confirmed by its hyperchromic shifts typical of chemisorption in the infrared red region using Fourier transformed infrared spectroscopy (FTIR). Using the model efficiency indicator, kinetic data were found to show very strong fit to the pseudo-second order kinetic model implying that the adsorption of Cu(2+) and Zn(2+) were basically by chemisorption.

Modeling of fixed-bed column studies for the adsorption of cadmium onto novel polymer-clay composite adsorbent.

Kaolinite clay was treated with polyvinyl alcohol to produce a novel water-stable composite called polymer-clay composite adsorbent. The modified adsorbent was found to have a maximum adsorption capacity of 20,400+/-13 mg/L (1236 mg/g) and a maximum adsorption rate constant of approximately = 7.45x10(-3)+/-0.0002 L/(min mg) at 50% breakthrough. Increase in bed height increased both the breakpoint and exhaustion point of the polymer-clay composite adsorbent. The time for the movement of the Mass Transfer Zone (delta) down the column was found to increase with increasing bed height. The presence of preadsorbed electrolyte and regeneration were found to reduce this time. Increased initial Cd(2+) concentration, presence of preadsorbed electrolyte, and regeneration of polymer-clay composite adsorbent reduced the volume of effluent treated. Premodification of polymer-clay composite adsorbent with Ca- and Na-electrolytes reduced the rate of adsorption of Cd(2+) onto polymer-clay composite and lowered the breakthrough time of the adsorbent. Regeneration and re-adsorption studies on the polymer-clay composite adsorbent presented a decrease in the bed volume treated at both the breakpoint and exhaustion points of the regenerated bed. Experimental data were observed to show stronger fits to the Bed Depth Service Time (BDST) model than the Thomas model.

Equilibrium, kinetic and sorber design studies on the adsorption of Aniline blue dye by sodium tetraborate-modified Kaolinite clay adsorbent.

Raw Kaolinite clay obtained Ubulu-Ukwu, Delta State of Nigeria and its sodium tetraborate (NTB)-modified analogue was used to adsorb Aniline blue dye. Fourier transformed infrared spectra of NTB-modified Kaolinite suggests that modification was effective on the surface of the Kaolinite clay with the strong presence of inner -OH functional group. The modification of Kaolinite clay raised its adsorption capacity from 1666 to 2000 mg/kg. Modeling adsorption data obtained from both unmodified and NTB-modified Kaolinite clay reveals that the adsorption of Aniline blue dye on unmodified Kaolinite clay is on heterogeneous adsorption sites because it followed strongly the Freundlich isotherm equation model while adsorption data from NTB-modified Kaolinite clay followed strongly the Langmuir isotherm equation model which suggest that Aniline blue dye was adsorb homogeneous adsorption sites on the NTB-modified adsorbent surface. There was an observed increase in the amount of Aniline blue adsorbed as initial dye concentration was increased from 10 to 30 mg/L. It was observed that kinetic data obtained generally gave better robust fit to the second-order kinetic model (SOM). The initial sorption rate was found to increased with increasing initial dye concentration (from 10 to 20 mg/L) for data obtained from 909 to 1111 mg kg(-1)min(-1) for unmodified and 3325-5000 mg kg(-1) min(-1) for NTB-modified adsorbents. Thereafter there was a decrease in initial sorption rate with further increase in dye concentration. The linearity of the plots of the pseudo-second-order model with very high-correlation coefficients indicates that chemisorption is involved in the adsorption process. From the design of a single-batch adsorber it is predicted that the NTB-modified Kaolinite clay adsorbent will require 50% less of the adsorbent to treat certain volumes of wastewater containing 30 mg/L of Aniline blue dye when it is compared with the unmodified adsorbent. This will be cost effective in the use of NTB-modified adsorbent for the adsorption of Aniline blue dye from water and wastewater.