Rapid detection of multiple class pharmaceuticals in both municipal wastewater and sludge with ultra high performance liquid chromatography tandem mass spectrometry

This work described the development, optimization and validation of an analytical method for rapid detection of multiple-class pharmaceuticals in both municipal wastewater and sludge samples based on ultrasonic solvent extraction, solid-phase extraction, and ultra high performance liquid chromatography-tandem mass spectrometry quantification. The results indicated that the developed method could effectively extract all the target pharmaceuticals （25） in a single process and analyze them within 24 min. The recoveries of the target pharmaceuticals were in the range of 69%-131% for wastewater and 54%-130% for sludge at different spiked concentration levels. The method quantification limits in wastewater and sludge ranged from 0.02 to 0.73 ng/L and from 0.02 to 1.00μg/kg, respectively. Subsequently, this method was validated and applied for residual pharma- ceutical analysis in a wastewater treatment plant located in Beijing, China. All the target pharmaceuticals were detected in the influent samples with concentrations varying from 0.09 ng/L （tiamulin） to 15.24 μg/L （caffeine）; meanwhile, up to 23 pharmaceuticals were detected in sludge samples with concentrations varying from 60 ng/kg （sulfamethizole） to 8.55 mg/kg （ofloxacin）. The developed method demonstrated its selectivity, sensitivity, and reliability for detecting multiple-class pharmaceuticals in complex matrices such as municipal wastewater and sludge.  

Effect of artificial aeration on the performance of vertical-flow constructed wetland treating heavily polluted river water

Three lab-scale vertical-flow constructed wetlands (VFCWs), including the non-aerated (NA), intermittently aerated (IA) and continuously aerated (CA) ones, were operated at different hydraulic loading rates (HLRs) to evaluate the effect of artificial aeration on the treatment efficiency of heavily polluted river water. Results indicated that artificial aeration increased the dissolved oxygen (DO) concentrations in IA and CA, which significantly favored the removal of organic matter and NH₄⁺-N. The DO grads caused by intermittent aeration formed aerobic and anoxic regions in IA and thus promoted the removal of total nitrogen (TN). Although the removal efficiencies of COD_Cr, NH₄⁺-N and TN in the three VFCWs all decreased with an increase in HLR, artificial aeration enhanced the reactor resistance to the fluctuation of pollutant loadings. The maximal removal efficiencies of COD_Cr, NH₄⁺-N and total phosphorus (TP) (i.e., 81%, 87% and 37%, respectively) were observed in CA at 19 cm/day HLR, while the maximal TN removal (i.e., 57%) was achieved in IA. Although the improvement of artificial aeration on TP removal was limited, this study has demonstrated the feasibility of applying artificial aeration to VFCWs treating polluted river water, particularly at a high HLR.  

Adsorption behavior of sulfamethazine in an activated sludge process treating swine wastewater

Swine wastewater is an important pollution source of antibiotics entering the aquatic environment. In this work,the adsorption behavior of sulfamethazine(SMN),a commonlyused sulfonamide antibiotic,on activated sludge from a sequencing batch reactor treating swine wastewater was investigated. The results show that the adsorption of SMN on activated sludge was an initially rapid process and reached equilibrium after 6 hr. The removal efficiency of SMN from the water phase increased with an increasing concentration of mixed liquor suspended solids,while the adsorbed concentration of SMN decreased. Solution pH influenced both the speciation of SMN and the surface properties of activated sludge,thus significantly impacting the adsorption process. A linear partition model could give a good fit for the equilibrium concentrations of SMN at the test temperatures(i.e.,10,20 and 30°C). The partition coefficient(Kd) was determined to be 100.5 L/kg at 20°C,indicating a quite high adsorption capacity for SMN. Thermodynamic analysis revealed that SMN adsorption on activated sludge was an exothermic process. This study could help to clarify the fate and behavior of sulfonamide antibiotics in the activated sludge process and assess consequent environmental risks arising from sludge disposal as well.  

Simultaneous determination of three classes of antibiotics in the suspended solids of swine wastewater by ultrasonic extraction, solid-phase extraction and liquid chromatography-mass spectrometry

This work describes a systematic approach to the development of a method for simultaneous determination of three classes of veterinary antibiotics in the suspended solids (SS) of swine wastewater, including five sulfonamides, three tetracyclines and one macrolide (tiamulin). The entire procedures for sample pretreatment, ultrasonic extraction (USE), solid-phase extraction (SPE), and liquid chromatography-mass spectrometry (LC-MS) quantification were examined and optimized. The recovery efficiencies were found to be 76%-104% for sulfonamides, 81%-112% for tetracyclines, and 51%-64% for tiamulin at three spiking levels. The intra-day and inter-day precisions, as expressed by the relative standard deviation (RSD), were below 17%. The method detection limits (MDLs) were between 0.14 and 7.14 μg/kg, depending on a specific antibiotic studied. The developed method was applied to field samples collected from three concentrated swine feeding plants located in Beijing, Shanghai and Shandong province of China. All the investigated antibiotics were detected in both SS and liquid phase of swine wastewater, with partition coefficients (logK_d) ranging from 0.49 to 2.30. This study demonstrates that the SS can not be ignored when determining the concentrations of antibiotics in swine wastewater.  

Development of systems for detection, early warning, and control of pipeline leakage in drinking water distribution: A case study

The integrated system for the detection, early warning, and control of pipeline leakage has been successfully developed to manage the pipeline networks of Beijing.  

Adsorptive removal of antibiotics from water using magnetic ion exchange resin

The occurrence of antibiotics in the environment has recently raised serious concern regarding their potential threat to aquatic ecosystem and human health. In this study, the magnetic ion exchange(MIEX) resin was applied for removing three commonly-used antibiotics, sulfamethoxazole(SMX), tetracycline(TCN) and amoxicillin(AMX) from water.The results of batch experiments show that the maximum adsorption capacities on the MIEX resin for SMX, TCN and AMX were 789.32, 443.18 and 155.15 μg/m L at 25°C,respectively, which were 2–7 times that for the powdered activated carbon. The adsorption kinetics of antibiotics on the MIEX resin could be simulated by the pseudo-second-order model(R~2= 0.99), and the adsorption isotherm data were well described by the Langmuir model(R~2= 0.97). Solution p H exhibited a remarkable impact on the adsorption process and the absorbed concentrations of the tested antibiotics were obtained around the neutral p H.The MIEX resin could be easily regenerated by 2 mol/L Na Cl solution and maintained high adsorption removal for the tested antibiotics after regeneration. Anion exchange mechanism mainly controlled the adsorption of antibiotic and the formation of hydrogen binding between the antibiotic and resin can also result in the increase of adsorption capacity. The high adsorption capacity, fast adsorption rate and prominent reusability make the MIEX resin a potential adsorbent in the application for removing antibiotics from water.  

Fenton process for degradation of selected chlorinated aliphatic hydrocarbons exemplified by trichloroethylene, 1,1-dichloroethylene and chloroform

The degradation of selected chlorinated aliphatic hydrocarbons (CAHs) exemplified by trichloroethylene (TCE), 1,1-dichloroethylene (DCE), and chloroform (CF) was investigated with Fenton oxidation process. The results indicate that the degradation rate was primarily affected by the chemical structures of organic contaminants. Hydroxyl radicals (·OH) preferred to attack the organic contaminants with an electron-rich structure such as chlorinated alkenes (i.e., TCE and DCE). The dosing mode of Fenton’s reagent, particularly of Fe²⁺, significantly affected the degradation efficiency of studied organic compound. A new “time-squared” kinetic model, C = C _o exp(−k _obs t ²), was developed to express the degradation kinetics of selected CAHs. This model was applicable to TCE and DCE, but inapplicable to CF due to their varied reaction rate constants towards ?OH. Chloride release was monitored to examine the degree of dechlorination during the oxidation of selected CAHs. TCE was more easily dechlorinated thanDCE and CF.Dichloroacetic acid (DCAA) was identified as the major reaction intermediate in the oxidation of TCE, which could be completely removed as the reaction proceeded. No reaction intermediates or byproducts were identified in the oxidation of DCE and CF. Based on the identified intermediate, the reaction mechanism of TCE with Fenton’s reagent was proposed.  

Formation and speciation of disinfection byproducts during chlor(am)ination of aquarium seawater

The chemistry associated with the disinfection of aquarium seawater is more complicated than that of freshwater, therefore limited information is available on the formation and speciation of disinfection byproducts (DBPs) in marine aquaria. In this study, the effects of organic precursors, bromide (Br⁻) and pre-ozonation on the formation and speciation of several typical classes of DBPs, including trihalomethanes (THM4), haloacetic acids (HAAs), iodinated trihalomethanes (I-THMs), and haloacetamides (HAcAms), were investigated during the chlorination/chloramination of aquarium seawater. Results indicate that with an increase in dissolved organic carbon concentration from 4.5 to 9.4 mg/L, the concentrations of THM4 and HAAs increased by 3.2–7.8 times under chlorination and by 1.1–2.3 times under chloramination. An increase in Br⁻ concentration from 3 to 68 mg/L generally enhanced the formation of THM4, I-THMs and HAcAms and increased the bromine substitution factors of all studied DBPs as well, whereas it impacted insignificantly on the yield of HAAs. Pre-ozonation with 1 mg/L O₃ dose substantially reduced the formation of all studied DBPs in the subsequent chlorination and I-THMs in the subsequent chloramination. Because chloramination produces much lower amounts of DBPs than chlorination, it tends to be more suitable for disinfection of aquarium seawater.  

Synthesis of carbon-coated magnetic nanocomposite (Fe3O4@C) and its application for sulfonamide antibiotics removal from water

The occurrence of antibiotics in the environment has recently raised serious concerns regarding their potential threat to human health and aquatic ecosystem. A new magnetic nanocomposite, Fe304@C （Fe304 coated with carbon）, was synthesized, characterized, and then applied to remove five commonly-used sulfonamides （SAs） from water. Due to its combinational merits of the outer functionalized carbon shell and the inner magnetite core, Fe3O4@C exhibited a high adsorption affinity for selected SAs and a fast magnetic separability. The adsorption kinetics of SAs on Fe304 @ C could be expressed by the pseudo second-order model. The adsorption isotherms were fitted well with the Dual-mode model, revealing that the adsorption process consisted of an initial partitioning stage and a subsequent hole-filling stage. Solution pH exerted a strong impact on the adsorption process with the maximum removal efficiencies （74% to 96%） obtained at pH 4.8 for all selected SAs. Electrostatic force and hydrogen bonding were two major driving forces for adsorption, and electron-donor-acceptor interactions may also make a certain contribution. Because the synthesized Fe304@C showed comprehensive advantages of high adsorptivity, fast magnetic separability, and prominent reusability, it has potential applications in water treatment.  

Regioselective oxidation of tetracycline by permanganate through alternating susceptible moiety and increasing electron donating ability

Permanganate has attracted much attention in wide range of chemistry and particularly in degradation of environmental pollutants. However, few studies have discussed the feature of regioselective reactivity of permanganate with specific moiety of the target compound. Herein, we studied the reaction between permanganate and tetracycline that is an emerging micropollutant with different species containing several electron-rich groups. The second-order rate constants increased from 6.0 to 9.0 and could be quantitatively modeled by considering the speciation of both reactants, yielding k_TC⁰?=?11.7 (mol/L)^?1?sec^?1, k_TC^??=?35.7 (mol/L)^?1?sec^?1, k_TC^2??=?43.1 (mol/L)^?1?sec^?1 for individual reaction channels. Degradation products were then identified as the hydroxylated and demethylated compounds. The result suggested a rate-limiting step of simple hydroxylation at the phenolic and/or alkene moieties, while the demethylation should be caused by the unavoidably formed manganese oxide via single electron oxidation. This is supported by the DFT calculation, indicating the primary oxidation of phenolic group of TC⁰ with activation barrier of 44.5?kcal/mol and of alkene group of TC^? and TC^2? with activation barriers of 44.0 and 43.4?kcal/mol, respectively. This is in agreement with the experimental results, implying the alternation of regioselectivity associated with the deprotonation process. The result was further supported by performing the Fukui function and electrostatic potential analysis, reflecting the more probable site and better electron donating tendency beneficial to the permanganate oxidation.