Sorption mechanisms of cephapirin, a veterinary antibiotic, onto quartz and feldspar minerals as detected by Raman spectroscopy

Raman spectroscopy was used to investigate sorption mechanisms of cephapirin (CHP), a veterinary antibiotic, onto quartz (SiO₂) and feldspar (KAlSi₃O₈) at different pH. Sorption occurs by electrostatic attraction, monodentate and bidentate complexation. The zwitterion (CHP^o) adsorbs to a quartz⁽⁺⁾ surface by electrostatic attraction of the carboxylate anion group (-COO⁻) at low pH, but adsorbs to a quartz⁽⁻⁾ surface through electrostatic attraction of the pyridinium cation, and possibly COO⁻ bridge complexes, at higher pH. CHP⁻ bonds to quartz⁽⁻⁾ surfaces by bidentate complexation between one oxygen of -COO⁻ and oxygen from carbonyl of an acetoxymethyl group. On a feldspar^(+/−) surface, CHP^o forms monodentate complexes between CO, and possible -COO⁻ bridges and/or electrostatic attachments to localized edge (hydr)oxy-Al surfaces. CHP⁻ adsorbs to feldspar⁽⁻⁾ through monodentate CO complexation. Similar mechanisms may operate for other cephalosporins. Results demonstrate, for the first time, that Raman techniques can be effective for evaluating sorption mechanisms of antibiotics.     

Occurrence of pharmaceuticals in a municipal wastewater treatment plant: mass balance and removal processes

Occurrence and removal efficiencies of fifteen pharmaceuticals were investigated in a conventional municipal wastewater treatment plant in Michigan. Concentrations of these pharmaceuticals were determined in both wastewater and sludge phases by a high-performance liquid chromatograph coupled to a tandem mass spectrometer. Detailed mass balance analysis was conducted during the whole treatment process to evaluate the contributing processes for pharmaceutical removal. Among the pharmaceuticals studied, demeclocycline, sulfamerazine, erythromycin and tylosin were not detected in the wastewater treatment plant influent. Other target pharmaceuticals detected in wastewater were also found in the corresponding sludge phase. The removal efficiencies of chlortetracycline, tetracycline, sulfamerazine, acetaminophen and caffeine were >99%, while doxycycline, oxytetracycline, sulfadiazine and lincomycin exhibited relatively lower removal efficiencies (e.g., <50%). For sulfamethoxazole, the removal efficiency was approximately 90%. Carbamazepine manifested a net increase of mass, i.e. 41% more than the input from the influent. Based on the mass balance analysis, biotransformation is believed to be the predominant process responsible for the removal of pharmaceuticals (22% to 99%), whereas contribution of sorption to sludge was relatively insignificant (7%) for the investigated pharmaceuticals.     

Enhancement of phosphorus sorption onto light expanded clay aggregates by means of aluminum and iron oxide coatings

Phosphorus (P) loading from non-point or point sources increases the eutrophication risk of natural waters. The functioning of constructed wetlands (CWs) used as natural water treatment systems can be improved by means of additional materials adsorbing soluble P. In this study, light expanded clay aggregates (LECA) and LECA coated with aluminum (Al) oxide (Al-LECA) or iron (Fe) oxide (Fe-LECA) were tested for their efficiency as P sorbents in the pH range 3–8. The oxide coatings duplicated the actual sorption capacity calculated from the sorption isotherms at the P concentration in the equilibrium solution of 20 μg L⁻¹, assumed to be the allowable P level in purified water. In the oxide-coated LECAs the sorption was fast and followed both the first- and second-order Lagergren kinetic models, suggesting that the formation of a binuclear surface complex was feasible. In LECA, sorption was markedly slower and followed the first-order kinetic model, indicating that retention occurred through a monodentate attachment. These findings were in harmony with the degree of P saturation (DPS) of the sorbent surfaces at the highest P addition level (200 μg L⁻¹), DPS being decisively higher for LECA than for the oxide-coated sorbents. Accordingly, at higher pH values the competition by hydroxyl ions diminished the sorption in LECA relatively more than that in the coated sorbents. In agreement with the acidity of Al³⁺ being 100 times lower than that of Fe³⁺, at elevated pH the sorption by Al-LECA proved to be less reversible than that by Fe-LECA. The results provide evidence that in CWs Al-coated sorbents are superior to Fe-coated ones that are also redox-sensitive and may lose their sorption properties in anoxic conditions.     

Sorption behavior of bensulfuron-methyl on andisols and ultisols volcanic ash-derived soils: Contribution of humic fractions and mineral-organic complexes

Bensulfuron-methyl sorption was studied in Andisol and Ultisol soils in view of their characteristic physical and chemical properties, presenting acidic pH and variable charge. Humic and fulvic acids (HA and FA) and humin (HUM) contributions were established. Sorption was studied by using two synthetic sorbents, an aluminum-silicate with iron oxide coverage and the same sorbent coated with humic acid. Freundlich model described Bensulfuron-methyl behavior in all sorbents (R² 0.969-0.998). K_f for soils (8.3-20.7 μg^1−1/n mL^1/n g⁻¹) were higher than those reported in the literature. Organic matter, halloysite or kaolinite, and specific surface area contributed to the global process. The highest K_f for HA, FA and HUM were 539.5, 82.9, and 98.7 μg^1−1/n mL^1/n g⁻¹. Model sorbents described the participation of variable charge materials with high adsorption capacity. The constant capacitance model was used to assess effects of Bensulfuron-methyl adsorption on the distribution of SOH, SOH₂⁺ and SO⁻ sites of sorbents.     

Comparison of competitive and synergetic adsorption of three phenolic compounds on river sediment

Knowledge of toxic chemical sorption by soil/sediment is critical for environmental risk assessment of toxic chemicals, especially for the multi-sorbate system in river ecosystem. Sorption characteristics of 2, 4-Dichlorophenol, 2, 4-Dinitrophenol and 2, 4-Dimethyphenol on sediment were investigated. Adsorption isotherms in single- and multi-sorbate systems fitted well the Freundlich model. The adsorption effects were different among three selected phenolic compounds in single- and multi-sorbate systems. The synergetic affect that 2, 4-Dinitrophenol and 2, 4-Dimethyphenol bring to 2, 4-Dichlorophenol can be explained by the compression of double electronic layer and the charge neutrality. Adsorption kinetic results showed that pseudo-second-order model can be used to describe the experimental data and the adsorption affinity of phenolic compounds influenced greatly by the adsorption velocity. The present study suggests that the fate and transport of emerging pollutants such as phenolic compounds could be affected in the presence of different hydrophobic pollutants in aquatic systems.     

Microbial degradation of pharmaceuticals in estuarine and coastal seawater

Microbial degradation rates were measured for 19 pharmaceuticals in estuarine and coastal surface water samples. Antipyrine, carbamazepine, cotinine, sulfamethoxazole, and trimethoprim were the most refractory (half-lives, t_1/2 = 35 to >100 days), making them excellent candidates for wastewater tracers. Nicotine, acetaminophen, and fluoxetine were labile across all treatments (t_1/2 = 0.68-11 days). Caffeine, diltiazem, and nifedipine were also and relatively labile in all but one of the treatments (t_1/2 = 3.5-13 days). Microbial degradation of caffeine was further confirmed by production ¹⁴CO₂. The fastest decay of non-refractory compounds was always observed in more sewage-affected Jamaica Bay waters. Degradation rates for the majority of these pharmaceuticals are much slower than reported rates for small biomolecules, such as glucose and amino acids. Batch sorption experiments indicate that removal of these soluble pharmaceuticals from the water column to sediments is a relatively insignificant removal process in these receiving waters.     

Enhancement effect of water associated with natural organic matter (NOM) on organic compound-NOM interactions: a case study with carbamazepine

Natural organic matter (NOM) in soils and sediments is recognized to strongly affect environmental distributions of organic compounds. Water associated with NOM may have a significant impact on NOM-organic compound interactions. The objectives of this research were (1) to determine the effect of hydration of a model NOM sorbent on interactions with a probe organic compound, carbamazepine (CBZ), and (2) based on the comparison with the literature data, to evaluate the effect of organic compound structure on the cooperative participation of water molecules in organic sorbate-NOM interactions. CBZ is one of the most widely reported water pollutants from the pharmaceutical and personal care products family. Therefore, CBZ sorption on Pahokee peat was compared from water and from n-hexadecane, using solubility-normalized solute concentrations. CBZ-NOM interactions were enhanced by one to two orders of magnitudes when NOM became fully hydrated. This enhancement is associated with the distinct ability of CBZ to undergo strong, specific interactions with NOM which was revealed by comparing the transfer of CBZ and another model sorbate, phenanthrene, from solution in n-hexadecane to the hydrated NOM sorbent. The enhancing effect of NOM hydration on CBZ-NOM interactions was also observed when CBZ sorption was examined on partially hydrated NOM. In comparison with a smaller-size organic sorbate such as phenol, CBZ needs more NOM-associated water in order to demonstrate the strengthening of interactions with NOM. Therefore, for penetration of the larger sorbate molecules into the NOM interior, a greater number of water molecules are needed to compensate for the local NOM disintegration thus suggesting the greater extent of the cooperativity in an involvement of water molecules in the CBZ-NOM interactions.     

Sorption and Desorption of Three Endocrine Disrupters in Soils

Sorption of the estrogens estrone (E1), 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) on four soils was examined using batch equilibrium experiments with initial estrogen concentrations ranging from 10 to 1000 ng mL^?1. At all concentrations, >85% of the three estrogens sorbed rapidly to a sandy soil. E1 sorbed more strongly to soil than E2 or EE2. Partial oxidation of E2 to E1 was observed in the presence of soils. Autoclaving was more effective at reducing this conversion than inhibition with sodium azide or mercuric chloride, and had little effect on sorption, relative to the chemical microbial inhibitors. Sorption of EE2 was greater for fine-textured than coarse-textured soils, but greater than 90% of EE2 sorbed onto all four soils. The greatest degree of desorption of estrogens from the sandy soil occurred with the lowest initial concentration of 10 ng mL^?1 and reached levels ≥80% for E1 and E2. Desorption of EE2 was greater in coarser textured soils than finer-textured soils. Again, relative desorption from all soils was greatest with low initial concentrations. Therefore, at environmentally relevant concentrations, estrogens quickly sorb to soils, and soils have a large capacity to bind estrogens, but these endocrine-disrupting compounds can become easily desorbed and released into the aqueous phase.     

Dissolution and sorption of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues from detonated mineral surfaces

Composition B (Comp B) is a commonly used military formulation composed of the toxic explosive compounds 2,4,6-trinitrotoluene (TNT), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Numerous studies of the temporal fate of explosive compounds in soils, surface water and laboratory batch reactors have been conducted. However, most of these investigations relied on the application of explosive compounds to the media via aqueous addition and thus these studies do not provide information on the real world loading of explosive residues during detonation events. To address this we investigated the dissolution and sorption of TNT and RDX from Comp B residues loaded to pure mineral phases through controlled detonation. Mineral phases included nontronite, vermiculite, biotite and Ottawa sand (quartz with minor calcite). High Performance Liquid Chromatography and Attenuated Total Reflectance Fourier Transform Infrared spectroscopy were used to investigate the dissolution and sorption of TNT and RDX residues loaded onto the mineral surfaces. Detonation resulted in heterogeneous loading of TNT and RDX onto the mineral surfaces. Explosive compound residues dissolved rapidly (within 9 h) in all samples but maximum concentrations for TNT and RDX were not consistent over time due to precipitation from solution, sorption onto mineral surfaces, and/or chemical reactions between explosive compounds and mineral surfaces. We provide a conceptual model of the physical and chemical processes governing the fate of explosive compound residues in soil minerals controlled by sorption-desorption processes.     

Microbial degradation of dissolved organic matter (DOM) and its influence on phenanthrene-DOM interactions

Microbial degradation-induced changes in the characteristics of dissolved organic matter (DOM), and the subsequent effects on phenanthrene-DOM interactions were investigated based on the microbial incubation of DOM collected from four different sources for 28 d. Partially biodegraded DOM presented higher specific UV absorbance (SUVA), lower protein-like fluorescence, higher humic-like fluorescence, lower aliphatic carbon fraction, and higher hydrophobic neutral fractions compared to the original DOM. Microbial changes in DOM led to an increase in the isotherm nonlinearity as well as the extent of phenanthrene binding. A negative relationship between SUVA and the Freundlich n values was established for the original and the biodegraded DOM, suggesting that aromatic condensed structures may play important roles in providing nonlinear strong binding sites irrespective of microbial degradation. In contrast, there were two separate slopes of the correlations between the percentage of hydrophobic acid (HoA) fraction and the n values for the original and the biodegraded DOM with a higher slope exhibited for the latter, implying that the microbial utilization of oxygen-containing structures in the HoA fractions may contribute to enhancing the associated isotherm nonlinearity.