Qian Sun

Seasonal variation in the occurrence and removal of pharmaceuticals and personal care products in a wastewater treatment plant in Xiamen, China

The occurrence and seasonal variation of 50 pharmaceuticals and personal care products (PPCPs) in a wastewater treatment plant (WWTP) in Xiamen, China was investigated over a period of one year. Among the targets, 39 PPCPs were detected in the influent. The highest concentration was observed for acetaminophen, with the average concentration in the influent of 2963.5ng/L. The seasonal variation of PPCPs in the influent was observed. For most pharmaceuticals, highest concentrations were in March 2013, followed by December 2012, while the concentrations were lower in August 2012 and May 2013. Among the detected PPCPs, 14 targets could be removed more than 50% in the WWTP. The activated sludge treatment process contributed to most of PPCP removal, while the adsorption to the particles in the primary treatment and the transformation under UV radiation in the disinfection treatment also contributed to the PPCP removal. Among the detected PPCPs in the influent, 36 PPCPs could be detected in the final effluent of the WWTP. Significantly higher concentrations of PPCPs were observed in effluent samples collected in March 2013 compared to other seasons, suggesting higher concentrations of PPCPs could be discharged into the surrounding seawater during this period.

Seasonal and spatial variations of PPCP occurrence, removal and mass loading in three wastewater treatment plants located in different urbanization areas in Xiamen, China

The occurrence and fate of 48 pharmaceuticals and personal care products (PPCPs) in three wastewater treatment plants (WWTPs) located in different urbanization areas in Xiamen, China was investigated over one year. Results showed that PPCPs were widely detected, but the major PPCPs in the influent, effluent, and sludge were different. Spatial and seasonal variations of PPCP levels in the influent and sludge were observed. The removal efficiencies for most PPCPs were similar among the three WWTPs, although they employed different biological treatment processes. Furthermore, the mass loadings per inhabitant of most pharmaceuticals had a positive correlation with the urbanization levels, indicating that most pharmaceutical usage was higher in the urban core compared to the suburban zones. The total mass loadings of all the 48 PPCPs in the effluent and waste sludge showed close proportions, which suggested the importance of proper waste sludge disposal to prevent a large quantity of PPCPs from entering the environment.

Pharmaceuticals and personal care products in a mesoscale subtropical watershed and their application as sewage markers

This study comprehensively analyzed 23 classes of 51 pharmaceuticals and personal care products (PPCPs) in the two major prongs of Jiulong River and its estuary in southeast China, where the levels of the targeted PPCPs were mostly unknown. For both Jiulong River and its estuary, nine PPCPs were detected with 100% detection frequencies including two anti-inflammatory and analgesic drugs (ketoprofen and diclofenac acid), a stimulant (caffeine), a plasticizer (bisphenol A), two preservatives (methyl paraben and propyl paraben), two antimicrobials (triclosan and triclocarban) and a β-blocks (metoprolol), among which bisphenol A and caffeine accounted for more than 60% in concentrations. PPCPs generally had higher concentrations in dry season than normal season and wet season, while certain PPCPs, such as UV filters, showed higher concentrations in wet season, which were presumed to be related to their usage patterns. The concentrations of PPCPs were significantly correlated to several quality parameters of the surface water. The selected sewage markers were also used to track sewage in the studied river and the ratios of easily removed markers and conservative markers were used to identify the contribution of raw or treated sewage input. From our result, Jiulong River and its estuary were likely polluted by potential discharge of raw sewage.

Removal of silver nanoparticles by coagulation processes

Commercial use of silver nanoparticles (AgNPs) will lead to a potential route for human exposure via potable water. Coagulation followed by sedimentation, as a conventional technique in the drinking water treatment facilities, may become an important barrier to prevent human from AgNP exposures. This study investigated the removal of AgNP suspensions by four regular coagulants. In the aluminum sulfate and ferric chloride coagulation systems, the water parameters slightly affected the AgNP removal. However, in the poly aluminum chloride and polyferric sulfate coagulation systems, the optimal removal efficiencies were achieved at pH 7.5, while higher or lower of pH could reduce the AgNP removal. Besides, the increasing natural organic matter (NOM) would reduce the AgNP removal, while Ca(2+) and suspended solids concentrations would also affect the AgNP removal. In addition, results from the transmission electron microscopy and X-ray diffraction showed AgNPs or silver-containing nanoparticles were adsorbed onto the flocs. Finally, natural water samples were used to validate AgNP removal by coagulation. This study suggests that in the case of release of AgNPs into the source water, the traditional water treatment process, coagulation/sedimentation, can remove AgNPs and minimize the silver ion concentration under the well-optimized conditions.

Enhancement of catalytic degradation of amoxicillin in aqueous solution using clay supported bimetallic Fe/Ni nanoparticles.

Despite bimetallic Fe/Ni nanoparticles have been extensively used to remediate groundwater, they have not been used for the catalytic degradation of amoxicillin (AMX). In this study, bentonite-supported bimetallic Fe/Ni (B-Fe/Ni) nanoparticles were used to degrade AMX in aqueous solution. More than 94% of AMX was removed using B-Fe/Ni, while only 84% was removed by Fe/Ni at an initial concentration of 60 mg L(-1) within 60 min due to bentonite serving as the support mechanism, leading to a decrease in aggregation of Fe/Ni nanoparticles, which was confirmed by scanning electron microscopy (SEM). The formation of iron oxides in the B-Fe/Ni after reaction with AMX was confirmed by X-ray diffraction (XRD). The main factors controlling the degradation of AMX such as the initial pH of the solution, dosage of B-Fe/Ni, initial AMX concentration, and the reaction temperature were discussed. The possible degradation mechanism was proposed, which was based on the analysis of degraded products by liquid chromatography-mass spectrometry (LC-MS).

Transformation of Bisphenol A and Alkylphenols by Ammonia-Oxidizing Bacteria through Nitration

Transformation of bisphenol A (BPA) by ammonia-oxidizing bacteria (AOB) Nitrosomonas europaea ATCC 19718 was investigated. On the basis of the ultraperformance liquid chromatography (UPLC) coupled to quadrupole time-of-flight mass spectrometry (Q-TOF MS) and nuclear magnetic resonance analysis, we found N. europaea could transform BPA into nitro- and dinitro-BPA, suggesting that abiotic nitration between the biogenic nitrite and BPA played a major role in the transformation of BPA in the batch AOB system. Nitrite concentrations, temperature, and pH values were the major factors to influence the reaction rate. Furthermore, the yeast estrogenic screening assay showed that the formed nitro- and dinitro-BPA had much less estrogenic activity as compared with its parent compound BPA. Similar reactions of abiotic nitration were considered for 4-n-nonylphenol (nNP) and 4-n-octylphenol (nOP) since nitro-nNP and nitro-nOP were detected by UPLC-Q-TOF MS. In addition, results from the local wastewater treatment plant (WWTP) showed the occurrence of nitro-BPA and dinitro-BPA during the biological treatment process and in the effluent, indicating that nitration of BPA is also a pathway for removal of BPA. Results of this study provided implication that AOB in the WWTPs might contribute to removal of selected endocrine-disrupting compounds (EDCs) through abiotic nitritation.

PPCPs in Jiulong River estuary (China): Spatiotemporal distributions, fate, and their use as chemical markers of wastewater.

The occurrence and fate of 50 pharmaceuticals and personal care products (PPCPs) were investigated in the surface water of Jiulong River estuary in the southeast of China in spring, wet season, summer, autumn and winter. Results demonstrated a wide distribution of PPCPs in Jiulong River estuary, where 34 PPCPs were detected at least once and 5 PPCPs were detected in all the samples, including caffeine, diclofenac, metoprolol, methyl paraben, and propyl paraben. Spatial and seasonal variations were observed. Special emphasis was placed on the PPCP fate in the estuary. Most PPCPs showed a non-conservative behavior in the estuary, while the non-steroidal anti-inflammatory drugs and bisphenol A showed a pseudo-conservative behavior. The non-conservative and pseudo-conservative behavior was attributed to the combination of the seawater dilution, the introduction of PPCPs via the sewage water, and the physical, chemical, or biological removal processes. Furthermore, PPCP concentrations showed drastic variations in the turbidity maximum zones. To our best knowledge, this is the first work to indicate the pseudo-conservative behavior of PPCPs in the estuary, and to show the drastic variations of PPCPs in the turbidity maximum zone. In addition, the ratio of labile to conservative PPCPs was calculated to track the source of untreated sewage contamination. Results showed a significantly higher ratio compared to the average value in WWTP effluents, indicating the ubiquitous discharge of untreated domestic wastewater in Jiulong River estuary. In addition, the high ratio of bisphenol A to conservative PPCPs implied the potential input of untreated industrial wastewater in Jiulong River estuary.

Heavy metal removal from sludge with organic chelators: Comparative study of N, N-bis(carboxymethyl) glutamic acid and citric acid.

The applicability and performance of a new generation of biodegradable chelator, N, N-Bis(carboxymethyl) glutamic acid (GLDA), for extracting heavy metals from sewage sludge was carried out and compared with citric acid (CA). Targeted metals included Cd, Co, Cu, Zn, Ni and Cr, and their contents in the raw sludge were 63.1, 73.4, 1103.2, 2060.3, 483.9 and 604.1xa0mgxa0kg(-1) (dry sludge basis), respectively. Metals were divided into six fractions including water soluble, exchangeable, carbonates bound, Fe-Mn bound, organic matters bound and residual fraction via chemical fractionation. Washing results showed that in general GLDA exhibited better performance compared with CA, with removal efficiency of 83.9, 87.3, 81.2, 85.6, 89.3 and 90.2% for Cd, Co, Cu, Zn, Ni and Cr, respectively at equilibrium pHxa0=xa03.3. Residual metals were better stabilized in the GLAD-washed sludge than in the CA-washed sludge, and were mostly tightly bonded to the residual fraction. Furthermore, CA promoted phosphorus (P) release while GLDA had an opposite effect and tended to retain P within sludge, which could be beneficial for further application in agricultural use. Findings from this study suggested that GLDA could be a potential replacement for refractory and less environmentally-friendly chelators in the extraction of metals from sludge.

Speciation of metal-EDTA complexes by flow injection analysis with electrospray ionization mass spectrometry and ion chromatography with inductively coupled plasma mass spectrometry.

Flow injection analysis (FIA) with ESI-MS and ion chromatography (IC) with inductively coupled plasma-MS (ICP-MS) as the complementary technique have been explored for the determination of metal ions as their metal-EDTA complexes. ESI-MS enabled the identification of metal-EDTA complexes such as [Mn(EDTA)](2-), [Co(EDTA)](2-), [Ni(EDTA)](2-), [Cu(EDTA)](2-), [Zn(EDTA)](2-), [Pb(EDTA)](2-), and [Fe(EDTA)](1-) and their MS spectral showed that these metal-EDTA complexes were present in solution. Based on the ESI-MS, ion chromatographic separation and ICP-MS detection of these complexes are possible because IC-ICP-MS requires stable metal-EDTA complex during the chromatographic separation. The separation of these metal-EDTA complexes was achieved on an anion-exchange column with a mobile phase containing 30 mM NH(4)(HPO(4))(2) at pH 7.5 within 7 min with ICP-MS providing element specific detection. The ICP-MS LODs for the metal-EDTA were in the range of 0.1-0.5 microg/L with the exception of Fe (15 microg/L). The proposed method was a simple procedure for sample processing, using direct injection of sample without removal of sample matrix and was successfully applied to the determination of metal-EDTA complexes in real samples.

Effect of nanoscale zero-valent iron and magnetite (Fe3O4) on the fate of metals during anaerobic digestion of sludge

Anaerobic digestion (AD) is one of the most widely used processes to stabilize waste sewage sludge and produce biogas renewable energy. In this study, two different iron nanoparticles [nanoscale zero-valent iron (nZVI) and magnetite (Fe3O4)] were used in the mesophilic AD processes (37xa0±xa01xa0°C) to improve biogas production. In addition, changes of heavy metal (Cd, Co, Cu, Zn, Ni and Cr) speciation during AD of sludge with and without iron nanoparticles have been investigated. Concentrations of metals in the initial sludge were as follows: 63.1, 73.4, 1102.2, 2060.3, 483.9 and 604.1xa0mgxa0kg(-1) (dry sludge basis) for Cd, Co, Cu, Zn, Ni and Cr, respectively. Sequential fractionation showed that metals were predominantly bonded to organic matter and carbonates in the initial sludge. Compared with AD without iron nanoparticles, the application of iron nanoparticles (at dose of 0.5% in this study) showed positive impact not only on biogas production, but also on improvement of metals stabilization in the digestate. Metals were found concentrated in Fe-Mn bound and residual fractions and little was accumulated in the liquid digestate and most mobile fractions of solid digestate (water soluble, exchangeable and carbonates bound). Therefore, iron nanoparticles when properly used, could improve not only biogas yield, but also regulate and control the mobilization of metals during AD process. However, our study also observed that iron nanoparticles could promote the immobilization of phosphorus within the sludge during AD, and more research is needed to fully address the mechanism behind this phenomenon and the impact on future phosphorus reuse.