•Pollution of coastal areas with neonicotinoids and fipronil originate from riverine inputs.•Acetamiprid and thiacloprid were abundant in seawater, indicating their persistence in surface ...waters.•Photodegradation products of fipronil and imidacloprid were highly abundant in seawater.•Fipronil and its TPs represent a potential high risk to freshwater and marine species.•This study is the first to assess an ecological risk of the investigated insecticides in marine ecosystems.
Systemic insecticides like neonicotinoids and the phenylpyrazole insecticide fipronil are the most widely applied insecticides around the world. Multiple studies analyzed insecticide residues in freshwater systems, but data on seawater contamination levels are scarce. This study investigates the spatiotemporal distribution and ecological risk assessment of fipronil, neonicotinoids, sulfoxaflor and selected transformation products (TPs) in the Chinese Bohai Sea and its surrounding rivers. Well-established neonicotinoids (acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam) and TPs of fipronil and imidacloprid were frequently detected (detection frequency (DF): 42-100%) in freshwater. The median total insecticide concentration in freshwater was significantly higher in summer (72.4 ng•L-1) than in fall (23.4 ng•L-1), with major contributions from neonicotinoids, suggesting that pollution originates mostly from diffuse sources. In 2018, acetamiprid, desnitro-imidacloprid, fipronil-desulfinyl and thiacloprid were abundant in seawater (DF: 47–100%), indicating a high stability of acetamiprid and thiacloprid and a rapid photodegradation of fipronil and imidacloprid in surface waters. These results indicate that the continued use of these parent compounds may lead to their accumulation and/or of their TPs in shallow coastal seas. Consequently, this may lead to their transport to open seas, increasing their potential risk to marine organisms. Similarities between contaminant fingerprints in freshwater and seawater strongly suggest riverine discharges as main pollution source of adjacent coastal areas. This is the first study to perform an ecological risk assessment of fipronil, neonicotinoids, sulfoxaflor and selected TPs on marine ecosystems. Fipronil and its TPs demonstrated to be environmentally relevant with potential high risks for aquatic species. Our study provides novel insights into the fate and ecological risk of fipronil, neonicotinoids, sulfoxaflor and their TPs to marine species in shallow coastal seas.
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Current farm systems rely on the use of Plant Protection Products (PPP) to secure high productivity and control threats to the quality of the crops. However, PPP use may have considerable impacts on ...human health and the environment. A study protocol is presented aiming to determine the occurrence and levels of PPP residues in plants (crops), animals (livestock), humans and other non-target species (ecosystem representatives) for exposure modelling and impact assessment. To achieve this, we designed a cross-sectional study to compare conventional and organic farm systems across Europe. Environmental and biological samples were/are being/will be collected during the 2021 growing season, at 10 case study sites in Europe covering a range of climate zones and crops. An additional study site in Argentina will inform the impact of PPP use on growing soybean which is an important European protein-source in animal feed. We will study the impact of PPP mixtures using an integrated risk assessment methodology. The fate of PPP in environmental media (soil, water and air) and in the homes of farmers will be monitored. This will be complemented by biomonitoring to estimate PPP uptake by humans and farm animals (cow, goat, sheep and chicken), and by collection of samples from non-target species (earthworms, fish, aquatic and terrestrial macroinvertebrates, bats, and farm cats). We will use data on PPP residues in environmental and biological matrices to estimate exposures by modelling. These exposure estimates together with health and toxicity data will be used to predict the impact of PPP use on environment, plant, animal and human health. The outcome of this study will then be integrated with socio-economic information leading to an overall assessment used to identify transition pathways towards more sustainable plant protection and inform decision makers, practitioners and other stakeholders regarding farming practices and land use policy.
Pesticides can enter the atmosphere during spraying or after application, resulting in environmental or human exposure. The study describes the optimisation and validation of analytical methods for ...the determination of more than 300 pesticides in the particulate and gaseous phases of the air. Pesticides were sampled with high-volume air samplers on glass-fibre filters (GFFs) and glass columns filled with polyurethane foam (PUF) and XAD-2 resin. Comparing different extraction methods, a QuEChERS extraction with acetonitrile was selected for the GFFs. For the PUF/XAD-2 columns, a cold-column extraction with dichloromethane was used. Instrumental determination was performed using liquid chromatography/electrospray ionisation-time-of-flight mass spectrometry (LC/ESI-QTOF) and gas chromatography/electron impact ionisation-tandem mass spectrometry (GC/EI-MS/MS). Recovery experiments showed recovery rates between 70 and 120% for 263 compounds on the GFFs and 75 compounds on the PUF/XAD-2 columns. Semi-quantitative determination was performed for 39 compounds on the GFFs and 110 compounds on the PUF/XAD-2 columns. Finally, 27 compounds on the GFFs and 138 compounds on the PUF/XAD-2 columns could be determined only qualitatively. For the determination of the PUF/XAD-2 samples, signal suppression (LC) or signal enhancement (GC) due to matrix effects were determined. Method quantification limits of the optimised methods ranged from 30 to 240 pg/m
3
for the target compounds on the GFFs, and from 8 to 60 pg/m
3
on the PUF/XAD-2 columns. The applicability of the method was demonstrated by means of environmental air samples from an agricultural area in the Netherlands.
An analytical method has been developed for the determination of five naturally occurring estrogens (estradiol, estriol, estrone, genistein, daidzein), one synthetic hormone (ethynylestradiol) and ...three xenoestrogens (4-nonylphenol (NP), 4-
tert-octylphenol (4-
tert-OP), bisphenol A (BPA)) in coastal marine waters. The procedure includes a solid-phase extraction of approx. fifty litres of water samples on the solid-phase copolymer Oasis HLB followed by a clean-up on silica. Twenty-five percent aliquots were used for the analytical determination of the analytes using high performance liquid chromatography coupled with electrospray-ionisation tandem mass spectrometry (HPLC–ESI-MS/MS). Calculated extraction recoveries between 52 (4-
tert-octylphenol) and 91% (nonylphenol) were obtained for the method developed. Matrix interferences occurring during electrospray ionisation were quantified by spiking the extracts prior to the measurements. Method detection limits ranged from 0.02 (estrone) to 1
ng
L
−1 (estriol). The method was applied to determine environmental estrogens in coastal waters of the Baltic Sea. The analyses showed the presence of five compounds at levels between 0.10 (estrone) and 17
ng
L
−1 (ethynylestradiol).
In this case study pharmaceuticals were analysed in the Mondego river (Portugal) and their environmental risk assessed by means of risk quotients based on an extensive retrieval of ecotoxicological ...data for freshwater and saltwater species. The Mondego river crosses Coimbra, the most populated city in the Portuguese Centro Region hosting a complex of regional hospitals. Environmentally relevant and prioritised pharmaceuticals were investigated in this study and their potential hazards were evaluated by conducting a separate risk assessment for the freshwater and estuary parts of the examined river section.
A target analysis approach with method detection limits down to 0.01 ng L−1 was used to determine pharmaceuticals. Twenty-one prioritised target analytes out of seven therapeutical classes (antibiotics, iodinated X-ray contrast media (ICM), analgesics, lipid reducers, antiepileptics, anticonvulsants, beta-blockers) were investigated by applying ultra-high pressure liquid chromatography coupled to a triple quadrupole mass spectrometer equipped with an electrospray ionisation source.
The relative pattern of pharmaceuticals along the middle to the lower Mondego showed a quite uniform picture while an approximately 40fold increase of absolute concentrations was observed downstream of the wastewater treatment plant (WWTP) discharge of Coimbra. The most frequently measured substance groups were the ICM, represented by the non-ionic ICM iopromide (βmin: 3.03 ng L−1 - βmax: 2,810 ng L−1). Environmentally more critical substances such as carbamazepine, diclofenac, and bezafibrate, with concentrations up to and 52.6 ng L−1, 59.8 ng L−1, and 10.2 ng L−1 respectively, may potentially affect aquatic wildlife. Carbamazepine revealed elevated risk quotients (RQs >1) along the middle and lower Mondego with a maximum RQ of 53 downstream of Coimbra. Especially for saltwater species, carbamazepine and clarithromycin pose high potential risks.
Especially in periods of low water discharge of the Mondego river, other pharmaceuticals as diclofenac and bezafibrate may pose additional risks downstream of the WWTP.
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•WWTP of Coimbra is a major source of pharmaceuticals in the Mondego river.•Up to 40-fold increase of X-ray contrast media concentrations downstream of WWTP.•Elevated risk potentials for carbamazepine, bezafibrate, diclofenac, erythromycin.•Carbamazepine and clarithromycin pose potential adverse effects in the estuary.
In this study a target analysis approach with method detection limits down to 0.01 ng L−1 was developed in order to determine ultra-trace pharmaceuticals in seawater of the German coast and their ...estuaries. The selection of target analytes based on a prioritisation commissioned by the German Environmental Agency considering occurrence in German surface waters, production volumes and ecotoxicological data. Using ultra-high pressure liquid chromatography coupled to a triple quadrupole mass spectrometer equipped with an electrospray ionisation source 21 prioritised pharmaceuticals out of seven therapeutical classes (antibiotics, iodinated X-ray contrast media (ICM), analgesics, lipid reducers, antiepileptics, anticonvulsants, beta-blockers) have been detected in the low to medium ng L−1-range. The most frequently measured substance groups in the German Baltic Sea and German Bight are the ICM, represented by the non-ionic ICM iomeprol (German Bightmax: 207 ng L−1; Baltic Seamax: 34.5 ng L−1) and the ionic ICM amidotrizoic acid (German Bight: 86.9 ng L−1), respectively. The same pattern of substance distribution could be detected in the German Bight, the German Baltic Sea and their inflows with lower concentrations in the offshore region that are partly a result of dilution with marine water. Pharmaceuticals entering the estuaries and coastal regions are an environmental issue since data on the ecotoxicological effects on aquatic marine organisms is limited. Especially the antibiotics clarithromycin and sulfamethoxazole could be ecotoxicologically/environmentally critical.
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•A sensitive UHPLC-MS/MS method was developed to determine pharmaceuticals in the ng L−1 and sub-ng L−1-range.•19 prioritised pharmaceuticals were frequently detected in German coastal regions and their estuaries.•Riverine inputs of pharmaceuticals, largely reached coastal waters underlining their persistence in brackish and seawaters.•Clarithromycin and sulfamethoxazole are suspected of posing an ecotoxicological risk in marine and brackish water.
Pesticides present a significant risk for both humans and the environment. However, quantitative data for a broad range of airborne pesticides in agricultural areas are missing. During or after the ...application, pesticides can reach the atmosphere and partition between the particulate and gaseous phase. As part of the EU project SPRINT, weekly ambient air samples were collected from two agricultural areas in Portugal (vineyard) and the Netherlands (potatoes, onions, and sugarbeet) between April 2021 and June 2022 using high-volume air samplers. The samples were analysed for 329 pesticides, of which 99 were detected. The most frequently detected compounds included the fungicides folpet, fenpropidin and mandipropamid, the insecticide chlorpyrifos-methyl, the herbicide terbuthylazine, and the metabolite prothioconazole-desthio, which were found with detection frequencies between 40 and 57 %. Pesticide concentrations ranged between 0.003 ng/m3 and 10 ng/m3. Remarkably, 97 % of the samples contained at least one pesticide and in 95 % of the samples, pesticide mixtures were present. The calculated particle phase fractions correlated with the octanol-air partitioning coefficient for most of the investigated compounds. Furthermore, calculated daily inhalation rates for individual pesticides and pesticide mixtures were far below the Acceptable Daily Intake (ADI) with a margin of exposure (MOE) of >1000 for the highest calculated daily inhalation rate for a child. However, as this value only includes pesticide intake from food and drinking water and considering that 91 % of the detected pesticides are associated with potential adverse human health effects. These findings highlight the broad range of airborne pesticides in agricultural areas and the need for quantitative data to include the intake of mixtures of highly hazardous pesticides by inhalation in human risk assessment.
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•99 pesticides and metabolites detected (3 to 10,000 pg/m3) in ambient air.•Gas-/particle-bound fractions of frequently detected pesticides.•Multiple pesticides in most air samples.•11 pesticides reported for the first time in ambient air.•Intake by inhalation relevant for human health risk assessment.
The Elbe is one of the major rivers releasing pollutants into the coastal areas of the German North Sea. Its estuary represents the habitat of a small population of harbor seals (Phoca vitulina). ...Only little is known about the health status and contamination levels of these seals. Therefore, a first-ever seal catch was organized next to the islands of Neuwerk and Scharhörn in the region of the Hamburg Wadden Sea National Park. The investigations included a broad set of health parameters and the analysis of metals and organic pollutants in blood samples. Compared to animals of other Wadden Sea areas, the seals showed higher γ-globulin levels, suggesting higher concentrations of pathogens in this near-urban area, elevated concentrations for several metals in particular for V, Sn, Pb, and Sr, and comparable ranges for chlorinated organic contaminants, except for elevated levels of hexachlorobenzene, which indicates characteristic inputs from the Elbe.
The presence of numerous emerging organic contaminants (EOCs) and remobilization of legacy persistent organic pollutants (POPs) in polar regions have become significant concerns of the scientific ...communities, public groups and stakeholders. This work reviews the occurrences of EOCs and POPs and their long-range environmental transport (LRET) processes via atmosphere and ocean currents from continental sources to polar regions. Concentrations of classic POPs have been systematically monitored in air at several Arctic stations and showed seasonal variations and declining trends. These chemicals were also the major POPs reported in the Antarctica, while their concentrations were lower than those in the Arctic, illustrating the combination of remoteness and lack of potential local sources for the Antarctica. EOCs were investigated in air, water, snow, ice and organisms in the Arctic. Data in the Antarctica are rare. Reemission of legacy POPs and EOCs accumulated in glaciers, sea ice and snow may alter the concentrations and amplify their effects in polar regions. Thus, future research will need to understand the various biogeochemical and geophysical processes under climate change and anthropogenic pressures.
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•Legacy POPs have shown declining temporal trends in the Arctic and the Antarctica.•EOCs are widely present in various environmental matrices in polar regions.•Increasing human activities in polar regions caused the local discharge of EOCs.•Climate change induces remobilization of POPs and EOCs in polar regions.•Many EOCs have become of an emerging concern for the polar ecosystems.
Carbazole and some of its derivatives may possess dioxin-like toxicity and could be persistent in the environment, but information on their distribution and environmental fate is limited. This study ...developed and validated an ultra-trace targeted-analysis method for the determination of carbazole, 1,2-benzocarbazole, and 13 halogenated carbazoles in sediments from the river, coast, and North Sea. An 8-g sediment sample was extracted using accelerated solvent extraction combined with in-cell cleanup and analyzed using gas chromatography-tandem mass spectrometry. The method was sensitive and reliable with method detection limits ranging from 4.54 to 52.9 pg/g, and most of the quantification biases and relative standard deviations were <20 and <15%, respectively. Carbazole and 1,2-benzocarbazole were the predominant substances in the sediments (median 565 and 369 pg/g, respectively) followed by 3,6-dichlorocarbazole (median 196 pg/g). The detection frequencies of carbazole, benzo-, 3-chloro-, and 3,6-dichlorocarbazole were >75%, while those of 3,6-dibromo-, 1-bromo-3,6-dichloro-, and 1,8-dibromo-3,6-dichlorocarbazole were approximately 50%. Brominated carbazoles occurred more frequently in marine than river-influenced sediments, which could indicate halogenation after discharge into the river. This is the first study regarding these substances in coastal environments without apparent contamination history. The ubiquity and bioaccumulative potential of these substances needs to be considered.
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•Carbazole and its derivatives were analyzed using an ultra-trace targeted method.•ASE with in-cell cleanup and GC–MS/MS provided sensitive quantification.•Carbazoles are ubiquitous in coastal environment without contamination history.•Brominated carbazoles are more abundant in marine than riverine sediment.•Transformation into persistent carbazoles is likely to occur.
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