Occurrence,Fate And Adsorption Of Psychiatric Pharmaceuticals In Various Typical Environmental Media Of Shanghai

Pharmaceuticals and personal care products(PPCPs)have gained growing attention since these compounds have been found to negatively affect ecosystems and environment.Psychiatric compounds as the most widely used drugs in the world have drawn great attention.These compounds have been detected in waste water,surface water,groundwater,drinking water,soil,and even animal and plant tissues.Clarifying the occurrence,fate,environmental risk and main pollution sources of psychiatric pharmaceuticals in the environment and studying the treatment of pollutants are crucial to control the pollution of psychiatric pharmaceuticals and reduce the damage to ecological environment and human health.This work studied the occurrence and fate of typical psychiatric drugs in the urban water system and psychiatric hospital by analyzing these compounds in Shanghai urban water system(waster water treatment plants,Huangpu River surface water and the residents’ drinking water)and environment medium(hospital effluent,surface water,groundwater,soil,and plant tissues)around psychiatric hospitals.In addition,adsorption removal and adsorption mechanism of psychiatric drugs on the different carbon materials was also studied.The research contents are as follows:I Establishment of trace analytical method for psychotropic drugs in the environment We established a trace analytical method for 15 psychotropic drugs in the environment by optimizing chromatographic conditions and mass spectrometric parameters based on the versatility,specificity,and selectivity recently of LC-MS/MS.We also optimized the sampling preparation technique(SPE for water sample and ultrasonic extraction + SPE for solid sample).The recovery,linearity,precision,matrix effects and sensitivity of analytical method could meet the requirements of actual research.Ⅱ The occurrence and fate of psychiatric pharmaceuticals in the typical urban water systemThe occurrence and fate of 15 selected psychiatric pharmaceuticals,including eight benzodiazepines,four antidepressants,one antiepileptic and two metabolites of benzodiazepines were investigated in wastewater treatment plant(WWTP)influents and effluents,surface water,and final drinking water in Shanghai.Psychiatric pharmaceuticals were in WWTPs influents ranging from low ng L-1 to 68.2 ng L-1,dominated by carbamazepine,doxepin,diazepam and lorazepam.Target analytes were still detected in effluents from low ng L-1 range to 47.3 ng L-1,with carbamazepine,diazepam,and oxazepam as most prevalent.WWTPs were low effective(<50%)in removing most of them,excluding amitriptyline(mean 60%),doxepin(mean 70%),temazepam(mean 78%)and lorazepam(mean 93%).In addition,carbamazepine,diazepam,oxazepam and lorazepam were detected in low ng L-1 to 75.5 ng L-1 in the surface water of Huang Pu Rive.The pattern of contaminants in surface water is similar to the effluent wastewater,which suggested the main source of organic trace pollutants might be WWTPs.Furthermore,carbamazepine(0.8-2.5 ng L-1),diazepam(0.5-3.2 ng L-1)and alprazolam(2.3 ng L-1)were also detected in drinking water and the concentrations were below the health based precautionary value.The investigation was within the range of those results reported in other countries.Our results indicate ubiquity of the investigated compounds in the aquatic system.As a consequence,these pollutants may potentially reach drinking water resources via WWTP effluents and/or surface waters and require constant attention.Ⅲ The fate and risk assessment of psychiatric pharmaceuticals from psychiatric hospital effluentThis work analyzed the occurrence and fate of 15 selected psychiatric pharmaceuticals in wastewater from 3 psychiatric hospitals in Shanghai,investigated the impact of wastewater on surface water and groundwater around hospital and researched the enrichment of these substances in soil and plant irrigated by receiving water.Finally,a screening level risk assessment was also presented.The target pharmaceuticals amitriptyline(83.57 ng L-1)and lorazepam(22.26 ng L-1)showed the highest concentration and were frequently detected in hospital effluent.Ten of fifteen analyzed compounds were detected in all 12 surface water samples.Lorazepam,carbamazepine and diazepam showed higher values.Five of fifteen analyzed compounds were detected in all 3 groundwater samples.The highest concentration for lorazepam reached up to 46.83 ng L-1 and our investigation was higher than those results reported in some countries.Only six target compounds were detected in all three soil sampling points with very low concentration(mean value<LOQ).Alkaline pharmaceuticals were more easily adsorbed by soil.Carbamazepine(1.29ng g-1),oxazepam(1.22ng g-1)and lorazepam(2.95ng g-1)showed the highest concentration and were frequently detected in plant tissues.The correlation analyses performed between hospital effluent and surface water,surface water and groundwater showed that the main source of psychiatric pharmaceuticals pollutants might be hospital effluents(from effluent to surface water;from surface water to ground water).Weak correlations between polluted surface water and soil suggested that psychiatric pharmaceuticals might be easier to degrade or transform in soil.A significant correlation between soil and plant indicated the target compounds in plant tissues were originated from soil pollution.Although the risk assessment indicated that no adverse effect was expected,the continued emissions might cause potential impact on ecosystems.Ⅳ Study on adsorption and removal of typical psychiatric pharmaceuticalsThe interaction between psychiatric pharmaceuticals and two carbon based materials(graphene oxide and biochar)were studied by experiment and density functional theory calculating.The interaction between graphene oxide and psychiatric pharmaceuticals was very strong.The adsorption mechanism of psychiatric pharmaceuticals adsorbed on graphene oxide is heavily dependent on π-π and-F/-Cl-π interaction.In addition,biochar has strong adsorption efficiency on psychiatric pharmaceuticals.The adsorption of psychiatric pharmaceuticals on biochar was mainly dependent on π-π interaction.The porous structure and the interaction between functional groups(-OH,-COOH)on graphene oxide and biochar might make contributions to adsorption.The adsorption energy by density functional theory calculating is consistent with the experimental results.In brief graphene oxide and biochar both have strong adsorption efficiency on psychiatric pharmaceuticals.However graphene oxide has faster adsorption rate due to it’s water solubility and biochar has greater adsorption quantity due to it’s porous structure.