Simultaneous Analysis including Non-Targeted Approaches for Bioactive Chemicals in Wastewater from the United Kingdom using Liquid Chromatography Tandem Mass Spectrometry
Shri Parthasarathy a, Cath Ortori b, Dave A. Barrett b, Rachel L Gomes a,*
a Bioprocess, Environmental and Chemical Technologies Research Group, Faculty of Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom.
b Centre for Analytical Bioscience, School of Pharmacy, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom.
*Corresponding author. E-mail address: firstname.lastname@example.org
The presence of bioactive chemicals (BACs) such as pharmaceuticals and steroids in wastewater and the aquatic environment is of universal concern due to observations of adverse effects in aquatic organisms. Wastewater treatment process (WWTP) effluent is the major route for BACs entering the water environment, demonstrating the vital role of WWTPs in ensuring water quality and reuse. There are growing drivers such as the Water Framework Directive WatchList and the UK Water Industry Research £140M Chemical Investigation Programme seeking to evaluate WWTP performance for removing BACs. Hence determining the BAC occurrence within the WWTP is vital and for this purpose an analytical method with high sensitivity and selectivity is essential.
A multi-class method for the simultaneous quantification of 36 BACs in UK wastewater was developed and included acidic and basic BACs belonging to different therapeutic classes, giving realistic information of the most widely used BACs in the UK. The proposed method included solid phase extraction followed by liquid chromatography and triple quadrupole mass analyser, with a chromatographic run time of 15 min. The method was validated in effluent wastewater at three different concentrations (50, 200, 750 ng/L.). The method was shown to be linear in a wide concentration range, with correlation coefficients >0.99 for all BACs. The main advantages of the developed method, besides high sensitivity (limits of detection ranging from 0.03 - 3.52 ng/L), selectivity, and reliability of results, are that all BACs were extracted in a single step, speeding up considerably sample preparation.
The applicability of the developed method was evaluated by analysing wastewater effluents in the UK. The results showed that a number of the studied BACs pose moderate to high persistency in wastewater effluents. In total, 29 out of 36 BACs were regularly detected of which several were at levels above those identified in the current literature. Higher levels in wastewater effluents were found for tramadol. Trimethoprim, carbamazepine, sulphapyridine, atenolol, erythromycin, codeine and diclofenac were found in the samples at concentrations higher than 1000 ng/L. Gemfibrozil, estriol, ethinylestradiol and clofibric acid were the compounds present in the samples at lower concentrations, from 1.36 to 3.40 ng/L. The remaining BACs were detected at concentrations between 12 and 654 ng/L.
Linear trap quadrupole velos ion trap MS for screening BACs in the influent and effluent wastewater samples was also utilised going beyond target analysis to enable better understanding of BAC biotranformations and products that ultimately inform on the WWTP efficiency. Two different workflows were developed and compared based on the two different types of acquisition modes (targeted and neutral loss) to identify the most complete and reliable manner of data collection. These workflows uniquely enable the opportunity to consider the ‘whole’ BAC (parent, metabolite and conjugate) and identified BAC metabolic contaminants of emerging concern in both influent and effluent wastewater matrices. The metabolites, 3-hydroxycarbamzapine, 10, 11-dihydro-10-hydroxycarbamazepine and O-desmethyltramadol were identified successfully in the influent and effluent wastewater by means of the methodology employed, and a metabolism pathway was proposed. Comparatively the metabolite 17β-estradiol-3-sulphate was identified in influent.
The results of chemical and isotopic analyses of waters of the Transboundary Zeravshan River, the Vakhsh River and its tributaries are presented. As an impact indicator of the mining enterprise wasterwater in the basin of the Zeravshan River on the quality of water a differential method of changing of the chemical composition of water before and after the tailing dams wasterwater is applied. The change of isotopic composition of the Zeravshan River and its tributaries from upstream to downstream is detected. The exchange of groundwater and surface waters in Muksu River Basin by isotopic methods is observed
Protection of water resources is one of today’s most significant environmental challenges. One key component in effectively implementing pollution abatement is the identification and assessment of pollution sources. Proper source evaluation is needed to target best management practices, develop watershed restoration plans, and assess human health risk.
The majority of US waterbodies do not meet water quality standards. Pathogens are the leading cause of water quality impairment in US rivers and streams, impairing 16% of river/stream miles. When a waterbody is classified as impaired, watershed restoration plans must be developed and implemented.
Computer models have historically been used to assess bacteria sources and loads in impaired watersheds. However, prior data deficiencies caused wildlife contributions to be underrepresented and other non-point sources (i.e. livestock) to be over-allocated in watershed planning efforts.
To provide better data on the predominant sources of bacteria impacting recreation, Texas initiated a bacterial source tracking (BST) program in 2003. BST is a valuable tool for identifying human and animal sources of fecal pollution. BST provides watershed planners bacteria source data not previously available. DNA fingerprinting methods selected for use were enterobacterial repetitive intergenic consensus sequence-polymerase chain reaction (ERIC-PCR) and riboPrinting® (RP). These methods required development of a BST Library. Since 2003, the library has been populated with almost 1,800 E. coli isolates collected from over 1,500 different samples and representing in excess of 50 animal classes.
Using the statewide BST library, comprehensive BST has been completed to identify the source of bacterial impairments in over 15 Texas watersheds. The BST Library has performed well, particularly for identifying broad source categories. A 100% rate of correct classification has been achieved when identifying relative contributions of human, domestic animals, and wildlife. For most studies, the majority of tested isolates were source-delineated with only a small proportion of isolates (~12%) unidentifiable.
Throughout these studies, wildlife contributions have been found to be the predominant source of bacteria, contributing 23-65% of the isolates identified, with non-avian wildlife being a primary contributor. Similarly, recent evaluations of small watershed and edge-of-field runoff from grazed and ungrazed pastures have found median background concentrations ranged from 3,500 to 5,500 cfu/100 mL. When compared to the concentration allowable (126 cfu/100 mL), these background concentrations are significant.
Background loading is not currently adequately addressed in most water quality models, watershed restoration strategies, or other water quality management efforts. This causes serious implications to application of water quality standards, particularly when applied to storm events where background runoff naturally exceeds water quality standards, as well as to watershed restoration plans where ignoring background concentrations may lead to inaccurate load allocations and reductions as well as incongruence of modeling and BST results.
This presentation will summarize the findings from watershed scale BST and small watershed runoff studies completed to date and discuss the implications of these findings on regulatory and non-regulatory water quality programs.
"OPTIMIZATION OF ACTIVATED SLUDGE PROCESS THROUGH ENERGY SAVING"
c) Study or work (“Project)
We cannot deny that the inefficient use of the water on the planet, is an old and actual problem, this is why water management has become a strategic topic worldwide, as the demand for this vital liquid grows day by day and almost twice as fast as the grow rate of global population, increasing the need to create better systems of use, care and treatment of water.
Therefore, it is a required task from governments, institutions and general population, finding viable solutions to the problems of not only the supply and quality of water, but also with energy conservation and environmental protection.
One of the wastewater treatment process that achieves a high percentage removal and results in treated water of excellent quality, is "activated sludge" in its various forms, however, the biggest drawback to using this system is the high cost associated with the consumption of energy used to meet the demand of oxygen required in this type of process to achieve oxidation of organic matter, it generally represents about 50% of total energy consumption of a plant.
This situation makes the aeration system and its control and operation a key energy saving element, so, in this study the optimization of the "activated sludge" process is analyzed but not only in the energy aspect but from a more integral perspective, performing a series of measurements and data analysis to determine all the factors that influence the process in order to optimize energy consumption and under the premise that the demand for oxygen needed to oxidize organic matter, changes throughout the day depending on the water flow and arrival concentration among other factors that have been underestimated like the process efficiency depending on weather.
The presented work gather the practical experiences gained during the operation and maintenance of several wastewater treatment plants located in Mexico, in which it has been experimented and systematically analyzed the adjustment of parameters of the process controlling air flow and aeration times, which is reflected in the optimization of energy consumption, reducing operating costs by up to 20 -30% without lowering the efficiency of removal and obtaining a high quality of treated water.
This development in the routine measurements among other experiences on operational control, enable the gathering of valuable information that we can use to achieve energy optimization and reduction in operational costs.