This review identifies understudied areas of emerging contaminant (EC) research in wastewaters and the environment, and recommends direction for future monitoring. Non-regulated trace organic ECs including pharmaceuticals, illicit drugs and personal care products are focused on due to ongoing policy initiatives and the expectant broadening of environmental legislation. These ECs are ubiquitous in the aquatic environment, mainly derived from the discharge of municipal wastewater effluents. Their presence is of concern due to the possible ecological impact (e.g., endocrine disruption) to biota within the environment. To better understand their fate in wastewaters and in the environment, a standardised approach to sampling is needed. This ensures representative data is attained and facilitates a better understanding of spatial and temporal trends of EC occurrence. During wastewater treatment, there is a lack of suspended particulate matter analysis due to further preparation requirements and a lack of good analytical approaches. This results in the under-reporting of several ECs entering wastewater treatment works (WwTWs) and the aquatic environment. Also, sludge can act as a concentrating medium for some chemicals during wastewater treatment. The majority of treated sludge is applied directly to agricultural land without analysis for ECs. As a result there is a paucity of information on the fate of ECs in soils and consequently, there has been no driver to investigate the toxicity to exposed terrestrial organisms. Therefore a more holistic approach to environmental monitoring is required, such that the fate and impact of ECs in all exposed environmental compartments are studied. The traditional analytical approach of applying targeted screening with low resolution mass spectrometry (e.g., triple quadrupoles) results in numerous chemicals such as transformation products going undetected. These can exhibit similar toxicity to the parent EC, demonstrating the necessity of using an integrated analytical approach which compliments targeted and non-targeted screening with biological assays to measure ecological impact. With respect to current toxicity testing protocols, failure to consider the enantiomeric distribution of chiral compounds found in the environment, and the possible toxicological differences between enantiomers is concerning. Such information is essential for the development of more accurate environmental risk assessment.
A large number of emerging contaminants (ECs) are known to persist in surface waters, and create pressure on wastewater treatment works (WWTW) for their effective removal. Although a large database for the levels of these pollutants in water systems exist globally, there is still a lack in the correlation of the levels of these pollutants with possible long-term adverse health effects in wildlife and humans, such as endocrine disruption. The current study detected a total of 55 ECs in WWTW influent surface water, 41 ECs in effluent, and 40 ECs in environmental waters located upstream and downstream of the plant. A list of ECs persisted through the WWTW process, with 28% of all detected ECs removed by less than 50%, and 18% of all ECs were removed by less than 25%. Negative mass balances of some pharmaceuticals and metabolites were observed within the WWTW, suggesting possible back-transformation of ECs during wastewater treatment. Three parental illicit drug compounds were detected within the influent of the WWTW, with concentrations ranging between 27.6 and 147.0 ng L for cocaine, 35.6-120.6 ng L for mephedrone, and 270.9-450.2 ng L for methamphetamine. The related environmental risks are also discussed for some ECs, with particular reference to their ability to disrupt endocrine systems. The current study propose the potential of the pharmaceuticals carbamazepine, naproxen, diclofenac and ibuprofen to be regarded as priority ECs for environmental monitoring due to their regular detection and persistence in environmental waters and their possible contribution towards adverse health effects in humans and wildlife.
Reported herein is new analytical methodology for the determination of 90 emerging contaminants (ECs) in liquid environmental matrices (crude wastewater, final effluent and river water). The application of a novel buffer, ammonium fluoride improved signal response for several ECs determined in negative ionisation mode. Most notably the sensitivity of steroid estrogens was improved by 4-5 times in environmental extracts. Method recoveries ranged from 40 to 152% in all matrices and method quantitation limits (MQLs) achieved were <1ngL(-1) for numerous ECs. Development of a microwave assisted extraction (MAE) protocol as an additional sample extraction step for solid matrices enabled 63 ECs to be simultaneously analysed in digested sludge. To the authors knowledge this is considerably more than any previously reported MAE method. Here, MQLs ranged from 0.1-24.1ngg(-1) dry weight. The application of MAE offers several advantages over pressurized liquid extraction including faster sample preparation, lower solvent requirements, and the ability to perform several extractions simultaneously as well as lower purchasing and running costs. To demonstrate the method's sensitivity, application to environmental samples revealed 68 and 40 ECs to be above their respective MQL in liquid environmental samples and digested sludge, respectively. To date, this is the most comprehensive multi-residue analytical method reported in the literature for the determination of ECs in both liquid and solid environmental matrices.
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