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1.
Sci Total Environ ; : 174800, 2024 Jul 13.
Article in English | MEDLINE | ID: mdl-39009155

ABSTRACT

The occurrence of 58 pharmaceutically active compounds (PhACs) in surface water at 28 coastal and five river sites, and in two stormwater flows in Cape Town, South Africa, was investigated in winter and summer. After accounting for quality assurance and control data, 33 PhACs were considered in detail. In winter, 25 PhACs were found at one or more sites and 27 in summer. Salicylic acid was the most widespread PhAC in each season. At least one PhAC was found at each site in each survey. The largest number found at a site was 22 at Lifebox23 Beach in winter and 23 at Macassar Beach and in the Black and Diep Rivers in summer. These sites are strongly directly or indirectly affected by wastewater treatment plant discharges. The range in ΣPhAC concentrations was 41 ng L-1 to 9.3 µg L-1 in winter and 109 ng L-1 to 18.9 µg L-1 in summer. The hazard posed by PhACs was estimated using Predicted No Effect Concentrations (PNEC) from several sources. Hazard Quotients (HQs) for numerous PhACs were >1, and for several even >10, including azithromycin, cimetidine, clarithromycin, erythromycin, and ibuprofen. The highest hazards were at coastal sites strongly indirectly affected by wastewater treatment plant discharges. Azithromycin, trimethoprim, and sulfamethoxazole at some sites may have promoted antibiotic resistance in bacteria, while irbesartan at some sites might have posed a hazard to fish according to the fish plasma model. The concentrations of several PhACs at some coastal sites are higher than concentrations reported in estuarine, coastal, and marine waters in other parts of the world.

2.
Heliyon ; 9(3): e14253, 2023 Mar.
Article in English | MEDLINE | ID: mdl-36938411

ABSTRACT

Although we have extensive datasets on the location and typology of industries, we do not know much on their generated and discharged wastewater. This lack of information compromises the achievement of the sustainable development goals focused on water (Sustainable Development Goal 6) in Europe and globally. Thus, our goal was to assess to which degree the chemical composition of industrial wastewater could be estimated based on the industry's typology according to its International Standard Industrial Classification of All Economic Activities (ISIC) class. We collected wastewater effluent water samples from 60 industrial wastewater effluents (before any wastewater treatment process), accounting for 5 samples each of 12 ISIC classes, analyzed the composition of key contaminants (i.e. European Commission rated priority compounds and watchlist), and statistically assessed the similarities and differences amongst ISIC classes using ordination and random forest analyses. The results showed statistically significant linkages between most ISIC classes and the composition of produced wastewater. Among the analytical parameters measured, the random forest methodology allowed identifying a sub-set particularly relevant for classification or eventual contamination prediction based on ISIC class. This is an important applied research topic with strong management implications to (i) determine pollution emission caps for each individual ISIC class, (ii) define monitoring schemes to sample and analyze industrial wastewater, and (iii) enable predicting pollutant loads discharged in river basins with scarce information. These encouraging results urge us to expand our work into other ISIC classes and water quality parameters to draw a full picture of the relationship between ISIC classes and produced wastewater.

3.
J Hazard Mater ; 451: 131159, 2023 Jun 05.
Article in English | MEDLINE | ID: mdl-36905908

ABSTRACT

N-nitrosamines (NAs), and N-nitrosodimethylamine (NDMA) in particular, are hazardous disinfection byproducts (DBPs) relevant when wastewater impacts drinking water sources and, in water reuse practices. Our study investigates the concentrations of NDMA and five additional NAs and their precursors in industrial wastewater effluents. Aiming to identify potential differences between industrial typologies, wastewaters from 38 industries belonging to 11 types of the UN International Standard Industrial Classification of All Economic Activities system (ISIC) were analysed. Results show that the presence of most NAs and their precursors cannot be linked to a specific industry type as these were in general very different within the classes. Nevertheless, N-nitrosomethylethylamine (NMEA) and N-nitrosopiperidine (NPIP) as well as precursors for N-nitrosodiethylamine (NDEA), NPIP and N-nitrosodibuthylamine (NDBA) could be rank with different concentrations between ISIC classes (p-value < 0.05). Specific industrial wastewater with notable high concentrations of NAs and their precursors were identified too. The effluents with the highest concentration of NDMA belong to the ISIC C2011 class (Manufacture of basic chemical), while the effluents with the highest concentration of NDMA precursors were from the ISIC C1511 class (Tanning and dressing of leather; dressing and dyeing of fur). Other relevant NAs found were NDEA in ISIC class B0810 (Quarrying of stone, sand, and clay) and ISIC class C2029 (Manufacture of other chemical products).

4.
Sci Total Environ ; 857(Pt 1): 159202, 2023 Jan 20.
Article in English | MEDLINE | ID: mdl-36208750

ABSTRACT

This study investigates the occurrence, transport, and risks associated to antibiotic residues, antibiotic resistance genes (ARGs) and antibiotic resistant Escherichia coli (AR-E. coli) in eleven natural springs in an agroecosystem environment with intense livestock production, where groundwater nitrate concentration usually sets above 50 mg L-1. Out of 23 multiple-class antibiotics monitored, tetracycline and sulfonamide residues were the most ubiquitous, and they were detected at concentrations ranging from ng L-1 to µg L-1. Five ARGs were monitored, conferring resistance to the antibiotic classes of major use in livestock production. Thus, genes conferring resistance to sulfonamides (sul1 and sul2) and tetracyclines (tetW) as well as a gene proxy for anthropogenic pollution (intI1) were present in most springs. sul1 was the most abundant, with absolute concentrations ranging from 4 × 102 to 5.6 × 106 gene copies L-1 water. AR-E. coli showing resistance to sulfonamides and tetracyclines was also detected, with a prevalence up to approximately 40 % in some sites but with poor correlations with the concentration of antibiotic residues and ARGs. The occurrence of antibiotics, ARGs and AR-E. coli was characterized by large seasonal variations which were mostly associated to both hydrological factors and reactive transport processes. Finally, a risk assessment approach pointed out towards low risk for both the groundwater environment and human health, when spring water is used for direct human consumption, associated with the occurrence of antibiotics, ARGs and AR-E. coli. However, long-term effects cannot be neglected, and proper actions must be taken to preserve groundwater quality.


Subject(s)
Anti-Bacterial Agents , Natural Springs , Humans , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/analysis , Escherichia coli/genetics , Genes, Bacterial , Drug Resistance, Microbial/genetics , Tetracyclines/analysis , Sulfonamides , Water , China
5.
Environ Pollut ; 289: 117927, 2021 Nov 15.
Article in English | MEDLINE | ID: mdl-34426209

ABSTRACT

The occurrence of veterinary antibiotics and hydro-chemical parameters in eleven natural springs in a livestock production area is evaluated, jointly with the characterization of their DOM fingerprint by Orbitrap HRMS. Tetracycline and sulfonamide antibiotics were ubiquitous in all sites, and they were detected at low ng L-1 concentrations, except for doxycycline, that was present at µg L-1 in one location. DOM analysis revealed that most molecular formulas were CHO compounds (49 %-68 %), with a remarkable percentage containing nitrogen and sulphur (16 %-23 % and 11 %-24 %, respectively). Major DOM components were phenolic and highly unsaturated compounds (~90 %), typical for soil-derived organic matter, while approximately 11 % were unsaturated aliphatic, suggesting that springs may be susceptible to anthropogenic contamination sources. Comparing the DOM fingerprint among sites, the spring showing the most different profile was the one with surface water interaction and characterized by having lower CHO and higher CHOS formulas and aliphatic compounds. Correlations between antibiotics and DOM showed that tetracyclines positively correlate with unsaturated oxygen-rich substances, while sulfonamides relate with aliphatic and unsaturated oxygen-poor compounds. This indicates that the fate of different antibiotics will be controlled by the type of DOM present in groundwater.


Subject(s)
Groundwater , Water Pollutants, Chemical , Anti-Bacterial Agents , Environmental Monitoring , Soil , Water Pollutants, Chemical/analysis
6.
J Hazard Mater ; 404(Pt A): 124102, 2021 02 15.
Article in English | MEDLINE | ID: mdl-33049635

ABSTRACT

A suspect screening methodology was developed for the fast and reliable identification of 360 contaminants of emerging concern (CECs) of anthropogenic origin in the vulnerable area of the Ebro Delta (Catalonia, Spain) and to track for potential contamination sources. The suspect screening methodology was combined with a risk assessment approach to prioritize the most ecologically relevant CECs. Out of the 360 suspects, 37 compounds were tentatively identified, 22 of which were fully confirmed using isotopically labelled standards. The detected suspect compounds included pesticides, pharmaceuticals, personal care products, stimulants and their metabolites. Pesticides were more ubiquitous in irrigation and drainage channels, while pharmaceuticals, stimulants, and personal care products were the most common in effluent wastewaters, in the receiving freshwater systems as well as in the marine environment. Ten compounds were found to be of high ecological concern, including the pharmaceuticals telmisartan, venlafaxine, and carbamazepine, the herbicides terbuthylazine, desethylterbuthylazine, and terbutryn, the fungicides azoxystrobin, tebuconazole and prochloraz and the insecticide tebufenozide. These compounds could be used as markers of anthropogenic contamination in riverine and coastal ecosystems.

7.
Environ Pollut ; 262: 114344, 2020 Jul.
Article in English | MEDLINE | ID: mdl-32443213

ABSTRACT

The present study is the first comprehensive monitoring of 13 selected endocrine disrupting compounds (EDCs) in untreated urban and industrial wastewater in Serbia to assess their impact on the Danube River basin and associated freshwaters used as sources for drinking water production in the area. Results showed that natural and synthetic estrogens were present in surface and wastewater at concentrations ranging from 0.1 to 64.8 ng L-1. Nevertheless, they were not detected in drinking water. For alkylphenols concentrations ranged from 1.1 to 78.3 ng L-1 in wastewater and from 0.1 to 37.2 ng L-1 in surface water, while in drinking water concentrations varied from 0.4 to 7.9 ng L-1. Bisphenol A (BPA) was the most abundant compound in all water types, with frequencies of detection ranging from 57% in drinking water, to 70% in surface and 84% in wastewater. Potential environmental risks were characterized by calculating the risk quotients (RQs) and the estrogenic activity of EDCs in waste, surface and drinking water samples, as an indicator of their potential detrimental effects. RQ values of estrone (E1) and estradiol (E2) were the highest, exceeding the threshold value of 1 in 60% of wastewater samples, while in surface water E1 displayed potential risks in only two samples. Total estrogenic activity (EEQt) surpassed the threshold of 1 ng E2 L-1 in about 67% of wastewater samples, and in 3 surface water samples. In drinking water, EEQt was below 1 ng L-1 in all samples.


Subject(s)
Endocrine Disruptors/analysis , Water Pollutants, Chemical/analysis , Environmental Monitoring , Estrogens/analysis , Rivers , Serbia , Wastewater
8.
Sci Total Environ ; 652: 952-963, 2019 Feb 20.
Article in English | MEDLINE | ID: mdl-30380500

ABSTRACT

This study evaluated the occurrence and distribution of 81 pharmaceutically active compounds (PhACs) in the vulnerable area of the Ebro Delta region (Catalonia, Spain), to assess the environmental impact of wastewater treatment plants discharge to coastal environments. The occurrence of PhACs was followed along the wastewater-recipient water-sediment chain until they reach estuaries and the Mediterranean Sea. Water and sediment samples were collected in an integrated way at different sampling points covering three different seasons in reaches of the Ebro River located upstream and downstream from wastewater treatment plants (WWTPs), surrounding channels, estuaries, and the associated receiving seawater. 28 out of the 57 compounds detected in effluent wastewater were positively identified in estuary and seawaters, revealing that WWTP discharges are an important source of contamination in coastal environments and that PhACs are suitable markers of urban contamination in these areas. The substances with the highest frequency of detection belonged to the groups of analgesics/anti-inflammatories (acetaminophen, salicylic acid), antihypertensives (valsartan), psychiatric drugs (carbamazepine), and antibiotics (clarithromycin, trimethoprim). In general, a decrease in concentration was observed from inland sampling points towards the Mediterranean Sea, resulting from a dilution in the recipient marine water bodies. A reduced number of PhACs, at concentrations ranging from 0.1 to 12.5 ng g-1 dry weight (d.w.) was detected in sediment samples, indicating that sorption is a minor natural attenuation pathway for these compounds. Finally, a prioritization strategy, based on the compounds concentration and frequency of detection in seawater, removal efficiency in WWTP, bioaccumulation potential, toxicity to marine organisms and persistency, was used to highlight the PhACs of major ecological concern and that could be used as relevant indicators of wastewater contamination in coastal environments.


Subject(s)
Environmental Monitoring/methods , Pharmaceutical Preparations/analysis , Water Pollutants, Chemical/analysis , Carbamazepine , Estuaries , Rivers/chemistry , Seawater/chemistry , Sewage/chemistry , Spain , Waste Disposal, Fluid , Wastewater/chemistry
9.
Anal Bioanal Chem ; 409(23): 5427-5440, 2017 Sep.
Article in English | MEDLINE | ID: mdl-28573324

ABSTRACT

An online ultra-high-performance-liquid chromatography-triple quadrupole tandem mass spectrometry (UHPLC-MS/MS) method for detection and quantification of natural and synthetic estrogens and their conjugates in aqueous matrices was developed. Target compounds include the natural estrogen estradiol (E2) and its main metabolites estrone (E1) and estriol (E3), the synthetic estrogens ethinylestradiol (EE2) and diethylstilbestrol (DES) and their conjugates estrone 3-sulfate (E1-3S), estriol 3-sulfate (E3-3S), estradiol 17-glucuronide (E2-17G), estrone 3-glucuronide (E1-3G), and estriol 16-glucuronide (E3-16G). After pH adjustment, sample filtration and addition of internal standards (IS), water samples (5 mL) were preconcentrated on a Hypersil GOLD aQ column after which chromatographic separation was achieved on a Kinetex C18 column using methanol and water as a mobile phase. The experimental parameters, such as sample loading flow rate, elution time, the percentage of organic solvent in the aqueous-organic eluent mixture, pH, and volume of analyzed samples, were optimized in detail. The benefits of the method compared to previously published methods include minimum sample manipulation, lower detection limits, reduced total analysis time, and overall increased method accuracy and precision. Method detection limits (MDLs) are in subnanogram per liter, complying with the requirements of the EC Decision 2015/495 (Watch list) for hormones listed therein. Applicability of the developed method was confirmed by analysis of river and raw wastewater samples taken directly from urban sewerage systems before being discharged into the river. Graphical abstract Sheme of online SPE-UHPLC-MS/MS system.


Subject(s)
Chromatography, Liquid/methods , Estrogens/analysis , Rivers , Tandem Mass Spectrometry/methods , Wastewater/chemistry , Estrogens/chemistry , Limit of Detection
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