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.

Utilizing eco-friendly kaolinite-biochar composite adsorbent for removal of ivermectin in aqueous media.

Several emerging contaminants are currently used in an unregulated manner worldwide, resulting in their increasing stringent limits in water by regulatory bodies. Thus, more viable and cheap treatment technologies are required. Recently, synergistic combinations of low-cost adsorbents have shown huge potential for aqueous toxic metals adsorption in water treatment processes. However, there is dearth of data on their potential for emerging contaminant removal. Here, low-cost kaolinite (KAC) clay was synergistically combined with blended Carica papaya or pine cone seeds, and calcined to obtain composites of KAC-Carica papaya seeds (KPA) and KAC-pine cone seeds (KPC). These adsorbents were characterized and evaluated for ivermectin adsorption at varying operating times (15-1440 min), pH (3-11), concentration (100-600 µg/L), and temperature (19.5-39.5 °C), as well as testing adsorbents' reusability. The composites exhibited marked property differences including over 250% cation exchange capacity increases and ≥50% surface area decreases, but unchanged KAC clay primary lattice structure. Ivermectin adsorption data were explained using kinetics and adsorption isotherm models. The rate of adsorption on KAC decreased over time, while rates for KPA and KPC increased until equilibrium at 180 min; the presence of biomaterials in the composites conferred better ivermectin adsorption and retention under continuous agitation. The adsorbents exhibited dual adsorption peaks one each at the acidic and alkaline pH regions as solution pH changed from 3 to 11. The rate data fitted (≥0.9232) the homogeneous fractal Pseudo-Second Order (FPSO) better than any other kinetics model, as well as the Freundlich adsorption isotherm model (≥0.9887); these indicate complex interactions between ivermectin and the adsorption sites of both composites. Ambient temperature increase up to ≈30 °C caused higher ivermectin adsorption but beyond this temperature there was drastic drop in adsorption. The KPA and KPC adsorption capacities are 105.3 and 115.8 µg/g, respectively. The KPC was better at reducing ivermecitn in low-concentration solution (≈75 µg/L) to less than 5.0 µg/L compared with KPA with ≈20.0 µg/L. Though KPC showed better efficiency in adsorption capacity and lowering concentration in low-concentration solutions, KPA exhibited better reusability with 83.5 and 67.5% initial adsorption strengths remaining in the second and third adsorption cycles, respectively, compared to the 73.8 and 58.8% for the KPC. These results indicate that KPA and KPC composites have the economic potential for application in water treatment processes.

Comparative study of the photocatalytic degradation of 2-chlorophenol under UV irradiation using pristine and Ag-doped species of TiO2, ZnO and ZnS photocatalysts.

A comparative photocatalytic degradation of 2-chlorophenol (2CP) in aqueous solution was investigated using pristine and Ag-doped semiconductor photocatalysts obtained from TiO2, ZnO and ZnS. Varying percentages (1, 3 and 5%) of Ag nanoparticles were doped on the semiconductor photocatalysts via the sol-gel method. The pristine and Ag-doped photocatalysts were characterized using UV-Vis diffuse reflectance spectroscopy, photo-luminescence spectroscopy, X-Ray diffractometry, Fourier transform infrared spectroscopy and transmission electron microscopy; and these techniques confirmed the successful syntheses of the pristine and Ag-doped species. The photocatalytic activities of all species for the degradation of 2CP were carried in photo-reactor using UV irradiation intensity of 1.4 mW/cm2 for 150 min; and the effects of various operating parameters (such as catalyst loading, pH and 2CP initial concentrations) were studied. The results showed enhanced 2CP degradation in the Ag-doped species in comparison to the pristine species while alkaline pH region was most suitable for 2CP degradation especially at low concentration. Lower loadings of the photocatalysts were usually more effective for the 2CP degradation and the degradation trend in the TiO2 and ZnS species was 5% Ag-doped >3% Ag-doped >1% Ag-doped > Pristine, while it was 1% Ag-doped >3% Ag-doped >5% Ag-doped > Pristine in the ZnO. Thus, although the Ag doping enhanced 2CP by all semiconductor photocatalysts, the Ag-doped TiO2 was more effective than the ZnO and ZnS species.

Kinetic field dissipation and fate of endosulfan after application on Theobroma cacao farm in tropical Southwestern Nigeria.

Endosulfan, 6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano,2,4,3-benzodioxathiepin-3-oxide, is still a pesticide of choice for most cocoa farmers in Southwestern Nigeria, in spite of its persistence, bioaccumulative, toxicological properties, and restriction. A single treatment of 1.4 kg ai/ha (0.5% ai) of technical grade endosulfan (Thiodan, 35EC) was applied to 0.0227 ha of cultivated Theobroma cacao L. (Cocoa) farm at the Cocoa Research Institute of Nigeria (CRIN). Levels of parent endosulfan (α-, ß-endosulfan) and major metabolite (endosulfan sulfate) were determined in vegetation and surrounding matrices at days 0, 7, 14, 21, 28, 42, and 60 using GC-MS. Their kinetic variables were determined. Order of ∑endosulfan distribution at day 0 was dry foliage > fresh foliage > bark > pods > soil (0-15 cm). No residual endosulfan was found in cocoa seeds and subsurface soil (15-30 cm). Low residual levels in pods on day 0 may be due to endogenous enzymatic breakdown, with α-isomer more susceptible and α/ß-endosulfan ratio being 0.90. Fell dry foliage as mulch was predominantly the receiving matrix for non-target endosulfan sprayed. Volatilization was key in endosulfan dissipation between days 0 and 7 from foliage surfaces (> 60% loss), while dissipation trend was bi-phasic and tri-phasic for vegetation and soil, respectively. ∑endosulfan loss at terminal day ranged between 40.60% (topsoil) and 99.47% (fresh foliage). Iteratively computed half-lives (DT'50) ranged from 6.48 to 30.13 days for ∑endosulfan in vegetation. Endosulfan was moderately persistent in pods-a potential source for cross contamination of seeds during harvest. Iteratively determined DT'50 and initial-final day DT50 are highly correlated (R = 0.9525; n = 28) and no significant difference (P = 0.05) for both methods.

GC-MS fragmentation patterns of sprayed endosulfan and its sulphate metabolite in samples of Theobroma cacao L from a field kinetic study.

Most environmental analytical methods for the determination of organochlorine pesticides (OCPs) are multi-residual with other organic compounds co-extracted and co-eluted. This has been observed in GC spectra using classical detectors like electron-capture detector (ECD) even after appropriate clean-up. This limitation could be resolved by using GC-MS methods which are more specific and selective. Thus, a commercial-grade endosulfan treated Theobroma cacao plantation was sampled. Representative samples comprising leaves, stem bark and pulp were obtained between 0.5 h and 60 days after treatment. Samples were analyzed for residual parent endosulfan (α- and ß-isomers) as well as the metabolite endosulfan sulphate using an ion trap GC-MS. The retention times and chromatogram peaks obtained for various endosulfan were identified and compared with reference standards, and confirmed with National Institute of Standards and Technology library. Results showed that the molecular ion at m/z 407 was exhibited by α- and ß-endosulfan, representing the parent molecular ion M+• ([C9H6Cl6SO3]+•). The α-isomer was more thermally stable, hence exhibited more relative abundance. Other predominant peaks were 339, 307, 277, 265, 243, 241, 207, 195, 160, 159, 99 and 75 m/z. The peak at m/z 159 was the base molecular ion. For endosulfan sulphate, the peak at m/z 422 corresponded to parent molecular ion (M+•), while m/z 424 was due to isotopic pattern characteristic of the chlorine atom. The peaks at 387, 357, 289, 272, 229, 206, 170, and 120 m/z were characteristic for the sulphate metabolite. The m/z peak at 272 was the base molecular ion, while m/z 143 may be due to metabolite diol and lactone. These results showed that the various endosulfan species can be identified and confirmed simultaneously using a GC-MS.

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.

Distribution and interactions of pentachlorophenol in soils: The roles of soil iron oxides and organic matter.

Soil iron oxides (IOs) and organic matter (OM) play varying roles in pentachlorophenol (PCP) retention and mobility, but the extent and mechanism are still unknown. Therefore, in order to have a better understanding of the adsorption of PCP on soils, batch sorption studies were carried out on whole soils and soils selectively treated to remove IOs (IOR) and OM (OMR). The effects of pH, time, and temperature were investigated. Results showed that PCP sorption was temperature and pH dependent; sorption decreased as both temperature and pH increased. Sorption was partly surface adsorption and partly partitioning within voids of IOs components as revealed by the kinetics models. The surface adsorption was multi-layer in nature. Equilibria were faster in the IOR soils than the untreated and OMR soils. IOs played greater roles in PCP sorption than OM. Removal of soil components, especially the IOs, as experienced in soils plagued by soil erosion, may lead to increased risks of PCP pollution of environmental media especially the aquifer.

Effects of time, soil organic matter, and iron oxides on the relative retention and redistribution of lead, cadmium, and copper on soils.

In order to predict the bioavailability of toxic metals in soils undergoing degradation of organic matter (OM) and iron oxides (IOs), it is vital to understand the roles of these soil components in relation to metal retention and redistribution with time. In this present work, batch competitive sorptions of Pb(II), Cu(II), and Cd(II) were investigated between 1 and 90 days. Results showed that competition affected Cd(II) sorption more than Cu(II) and Pb(II). The sorption followed the trend Pb(II) > > Cu(II) > Cd(II), irrespective of aging, and this high preference for Pb(II) ions in soils reduced with time. Removal of OM led to reduction in distribution coefficient (K d) values of ≈33% for all cations within the first day. However, K d increased nearly 100% after 7 days and over 1000% after 90-day period. The enhanced K d values indicated that sorptions occurred on the long run on surfaces which were masked by OM. Removal of IO caused selective increases in the K d values, but this was dependent on the dominant soil constituent(s) in the absence of IO. The K d values of the IO-degraded samples nearly remained constant irrespective of aging indicating that sorptions on soil components other than the IO are nearly instantaneous while iron oxides played greater role than other constituents with time. Hence, in the soils studied, organic matter content determines the immediate relative metal retention while iron oxides determine the redistribution of metals with time.

Microscale scavenging of pentachlorophenol in water using amine and tripolyphosphate-grafted SBA-15 silica: batch and modeling studies.

Mesoporous silica SBA-15 meets most criteria for selection of water treatment adsorbents such as high specific surface area, large pore-size, chemical inertness, repertory of surface functional groups, good thermal stability, selectivity, regenerability, and low cost of manufacture. However, its use for water treatment is still largely unexplored. SBA-15 and its functionalized derivatives of aminopropyltriethoxysilane (SA) and tripolyphosphate (ST) were synthesized, characterized, and used to investigate pentachlorophenol (PCP) removal from aqueous solutions. Functionalization improved SBA-15 capacity for PCP removal from solution in accordance with the trend SBA-15 < ST < SA. Sorption rate experiments data fit the Lagergren pseudo-second order kinetics model. Intra-particle diffusion indicated that the sorption is controlled by two mechanisms: intra-particle and equilibrium diffusion. Adsorptive pore-filling and electrostatic interactions were implicated in the removal of PCP from solution. Electrostatic interaction led to ≥75% increase in sorption upon functionalization. The equilibrium sorption data of the PCP on these mesoporous materials fits the Freundlich isotherm. Desorption hysteresis was low for the pristine SBA-15, but the functionalized SBA-15 materials showed higher hysteresis. The results imply that functionalized SBA-15 sorbents are promising materials for microscale scavenging of PCP in solution.

Evaluation of pyrene sorption-desorption on tropical soils.

Sorption-desorption processes control soil-pollutant interactions. These processes determine the extent of pyrene transport in soils. Understanding sorption characteristics of pyrene is necessary in ascertaining its fate in soil. Laboratory batch experiments were conducted to study the sorptions-desorption of pyrene on eight soils from varying tropical agro-ecological zones (AEZs). The results showed that pyrene sorptions equilibria were attained within 720 min. Solution pH had a reciprocal effect on pyrene sorptions. Sorption was exothermic and increased with pyrene concentration in solution. The quantities of pyrene sorbed by each soil as well as the hysteresis were proportional to the percentage organic matter, and to some degree, the clay mineralogy. Sorption isotherms showed distributed reactivity involving several linear and non-linear isotherms. The present investigation showed that pyrene is likely to be more available to biota and reach the aquifer faster in low organic matter soils than those with relatively higher organic matter and more so in warmer climes.

Fuzzy logic modeling of bioaccumulation pattern of metals in coastal biota of Ondo State, Nigeria.

The accumulation patterns of ten metals in tissues of plant, Eichornia crassipes, and fishes, Hydrocynus forskahlii and Oreochromis mossambicus, were modeled with simple fuzzy classification (SFC) to assess toxic effects of anthropogenic activities on the coastal biota. The plant sample was separated into root, stem, and leaves and the fishes into bones, internal tissues, and muscles. They were analyzed for As, Cd, Cr, Cu, Ni, Pb, V, Fe, Mn, and Zn after wet oxidation of their dried samples. The results were converted into membership functions of five accumulation classes and aggregated with SFC. The classification results showed that there was no metal accumulation in the plant parts while the fishes were classified into low accumulation category. The internal tissues of the fishes had higher metal accumulation than the other parts. Generally, Fe and Mn had highest concentrations in the biota but are natural to the area and may not constitute significant risk. Cr had the highest transfer and accumulation from the coastal water into the aquatic lives and may be indicative of risk prone system being a toxic metal. Metal contaminations in the zone had not significantly accumulated in the biota making them less prone to risk associated with metal accumulation.

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.

Phytoremediation potential of Eichornia crassipes in metal-contaminated coastal water.

The potential of Eichornia crassipes to serve as a phytoremediation plant in the cleaning up of metals from contaminated coastal areas was evaluated in this study. Ten metals, As, Cd, Cu, Cr, Fe, Mn, Ni, Pb, V and Zn were assessed in water and the plant roots and shoots from the coastal area of Ondo State, Nigeria and the values were used to evaluate the enrichment factor (EF) and translocation factor (TF) in the plant. The critical concentrations of the metals were lower than those specified for hyperaccumulators thus classifying the plant as an accumulator but the EF and TF revealed that the plant accumulated toxic metals such as Cr, Cd, Pb and As both at the root and at the shoot in high degree, which indicates that the plant that forms a large biomass on the water surface and is not fed upon by animals can serve as a plant for both phytoextraction and rhizofiltration in phytoremediation technology.

The effect of some operating variables on the adsorption of lead and cadmium ions on kaolinite clay.

Modification of kaolinite clay mineral with orthophosphate (p-modified sample) enhanced adsorption of Pb and Cd ions from aqueous solutions of the metal ions. Increasing pH of solutions of metal ions, increasing adsorbent dose and increasing concentration of metal ion, increased the adsorption of metal ions. Adsorption of both metal ions simultaneously on both unmodified and p-modified samples indicates that adsorption of one metal ion is suppressed to some degree by the other. The presence of electrolyte and their increasing concentration reduced the adsorption capacities of both unmodified and p-modified samples for the metal ions. Ca-electrolytes had more negative effect on the adsorption capacities of the adsorbents than Na-electrolytes. Ca-electrolytes reduced adsorption capacities of the adsorbents for Pb and Cd ions. From Langmuir plots it was observed that these electrolytes increased the binding energy constant of the metal ions unto the adsorbents especially on the p-modified samples. The rate of adsorption of Pb and Cd ions on p-modified adsorbent were increased and equilibrium of metal ion solution were more quickly reached (8min for Pb ions and 12min for Cd ions) with p-modified adsorbent as against 20min for adsorption of both metal ions on unmodified adsorbent when 200mg/L of metal ion solutions were used during the kinetic studies. When adsorption data were fitted against Langmuir, Freundlich, Toth and Langmuir-Freundlich isotherms, satisfactory fits were found with the Freundlich isotherm. However, at low concentration of metal ions, data also showed satisfactory fits to Langmuir isotherm.