The Pearl River Estuary (PRE), the largest estuary in Southern China, historically has suffered from metal contamination as a result of inputs from different riverine discharges. Determining the sources of metals accumulation in local aquatic flora and fauna remains a great challenge for this estuarine system with complex water circulation. In this study, Zn isotope ratios were measured in local oysters (Crassostrea hongkongensis) collected at 8 locations in the estuary on four occasions from 2014 to 2018, to better understand and assess the contamination sources. The results showed no significant differences (p < 0.05) in δ⁶⁶Zn values in oysters among the four sampling dates within individual sites. However, approximately a 0.67‰ (range from -0.66‰ to 0.01‰) difference in average δ⁶⁶Zn values was consistently found in oysters collected from the east side of the estuary compared to the west side, despite their comparable Zn concentrations. A mixing model was subsequently used to estimate the relative contributions from various sources to the δ⁶⁶Zn values in these oysters. The mixing model predicts that zinc derived from the dissolved fraction (approximately 80 %) was the dominant uptake pathway for oysters collected at the east shore whereas approximately 50 % of the Zn in oysters collected at the west shore was derived from the particulate fraction. The mixing model also was used to estimate the relative impacts of fresh versus saline water on the measured δ⁶⁶Zn values. Contributions from these two sources also varied between the east and west shores. This study presents the first data for Zn isotope ratios in oysters from the PRE, providing new insight for using Zn isotope ratios in oysters as a powerful tracer of sources in a complex estuarine system.

Nitrogen (N) pollution and the resulting eutrophication can have deleterious consequences on estuaries, such as hypoxia, fish kills, and loss of biotic diversity. An understanding of N sources and cycling in estuaries is fundamental to determining how to effectively manage these ecologically and commercially important areas. We applied a multiple-isotopic approach to examine the transformations and sources of the N pools in the Pearl River Estuary (PRE) during winter. The surface water in the West PRE was characterized by low salinity and high NO₃⁻, while that in the east had high salinity and low NO₃⁻. The NO₃⁻ in the West PRE was largely regulated by a conservative mixing process. In contrast, assimilation and nitrification dominated in the East PRE, which was attributed to the long water-residence time. For the first time, the source contributions of NO₃⁻ and NH₄⁺ were estimated by isotope mixing models. Our results suggest that river discharge and nitrification contributed 81% and 12% to the NO₃⁻ pool, respectively. A major portion (68%) of the NH₄⁺ was from river discharge, with the remainder likely from sewage and the aquitard-aquifer system. Our study demonstrates that internal nitrification can potentially be of pivotal importance in determining the NO₃⁻ level in an estuary and its export to coastal waters.

Declining emissions of persistent organic pollutants (POPs), subject to international control under the Stockholm convention, are not consistently reflected in biotic samples. To assess spatial and temporal variation in organochlorine pesticides and PCBs in UK freshwaters, we analysed tissues of a sentinel predator, the Eurasian otter, Lutra lutra between 1992 and 2009. Past declines in otter populations have been linked to POPs and it is unclear whether otter recovery is hampered in any areas by their persistence. PCBs, DDT (and derivatives), dieldrin and HCB were detected in over 80% of 755 otter livers sampled. Concentrations of ∑PCB, ∑DDT and dieldrin in otter livers declined across the UK, but there was no significant time trend for ∑PCB-TEQ (WHO toxic equivalency, Van den Berg et al., 2006) or HCB. In general, higher concentrations were found in the midlands and eastern regions, and lowest concentrations in western regions. Concentrations of PCBs and HCB in otters increased near the coast, potentially reflecting higher pollutant levels in estuarine systems. Decades after legislative controls, concentrations of these legacy pollutants still pose a risk to otters and other freshwater predators, with spatially widespread exceedance of thresholds above which reproduction or survival has been reduced in related species.

The Pearl River Estuary (PRE) is the largest estuary in southern China and under high metal stress. In the present study, we employed an integrated method of transcriptomics and proteomics to investigate the ecotoxicological effects of trace metals on the Hong Kong oyster Crassostrea hongkongensis. Three oyster populations with distinct spatial distributions of metals were sampled, including the Control (Station QA, the lowest metal levels), the High Cd (Station JZ, the highest Cd), and the High Zn–Cu–Cr–Ni (Station LFS, with the highest levels of zinc, copper, chromium, and nickel). Dominant metals in oysters were differentiated by principal component analysis (PCA), and theirgene and protein profiles were studied using RNA-seq and iTRAQ techniques. Of the 2250 proteins identified at both protein and RNA levels, 70 proteins exhibited differential expressions in response to metal stress in oysters from the two contaminated stations. There were 8 proteins altered at both stations, with the potential effects on mitochondria and endoplasmic reticulum by Ag. The genotoxicity, including impaired DNA replication and transcription, was specifically observed in the High Cd oysters with the dominating influence of Cd. The structural components (cytoskeleton and chromosome-associated proteins) were impaired by the over-accumulated Cu, Zn, Cr, and Ni at Station LFS. However, enhanced tRNA biogenesis and exosome activity might help the oysters to alleviate the toxicities resulting from their exposure to these metals. Our study provided comprehensive information on the molecular changes in oysters at both protein and RNA levels in responding to multi-levels of trace metal stress.

The Amazon coastal zone has become contaminated with organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs). However, information about their distribution and sources in this area is scarce, despite increasing deforestation and oil exploitation. Therefore, individual PAHs were analysed in the sediments of the Oyapock estuary, which is located in the Amazon coastal zone. This study provides information about the spatial and short-term temporal distributions of PAHs and discusses the major sources of PAHs to better understand the anthropogenic processes occurring in adjacent areas. The concentrations of all sixteen priority PAHs defined by the US EPA (United States Environmental Protection Agency, ∑₁₆PAHs) ranged from 10.9 to 138.8 ng g⁻¹ with a mean and standard deviation = 37.9 ± 20.5 and indicated that this estuary is not contaminated, while the mean levels were similar to those found in other Amazon regions and pristine areas along the coast of Brazil. No significant differences were found in the sedimentary PAHs levels between the wet and dry sampling campaigns, despite the different climatic conditions. Diagnostic ratios, positive matrix factorization (PMF) and cluster analysis have shown that the majority of the investigated PAHs were derived from combustion processes (at least 55.1%, as estimated by the PMF model). Localized source inputs from oil and its by-products concomitantly with natural/biogenic sources appear to be secondary sources. The PAH contribution from biomass and wood combustion was approximately 13.6% and was relatively lower than other regions of the Amazon that are undergoing massive biomass burning. As the first study of PAHs in this region, this study provides vital information on the healthy state of the estuary and can serve as a baseline for assessing the impacts of acute oil disasters or the chronic input of PAHs as a result of human settlements.

Microplastics (MP) are defined as synthetic organic pollutants sized <5 mm and have been recorded in various environments worldwide. Due to their small size, they pose a potential risk for many organisms throughout the food web. However, little is known about MP distribution patterns and associated transport mechanisms. Rivers may act as pathways for MP into marine environments. In this study, we investigate the occurrence of MP in the estuary and lower stretch of the second-largest German River, the Weser, representative of a significant interface between fresh water and marine environments. The aim of the study was to enhance the general understanding by providing novel, comprehensive data and suggestions for future studies on estuarine systems. Surface water samples of two different size classes were collected by ship using an on-board filtration system (11–500 μm fraction) and net sampling (500–5000 μm fraction). After a thorough sample preparation, all samples were analysed with Focal Plane Array (FPA) Fourier Transform Infrared (FTIR) spectroscopy and Attenuated Total Reflection (ATR) FTIR spectroscopy in order to obtain information on MP concentrations, polymer composition and size distribution. Our findings show highest concentrations in the 11–500 μm fraction (2.3 × 10¹ − 9.7 × 10³ MP m⁻³), with the polymer cluster acrylates/polyurethanes(PUR)/varnish being dominant. The >500 μm fraction was dominated by polyethylene. Estimated MP concentrations generally increased in the Turbidity Maximum Zone (TMZ) and decreased towards the open sea. This study contributes to the current research by providing novel insights into the MP pollution of the estuary and lower stretch of an important European river and provides implications for future MP monitoring measures.

Pesticides are widely used to alleviate pest pressure in agricultural systems, and atrazine is a typical diffuse pollutant and serves a sensitivity index for environmental characteristics. Based on the physicochemical properties of parent substances, degradation products of pesticides may pose a greater threat to aquatic ecosystems than pesticides. Atrazine and three primary degradation products (deethylatrazine (DEA), deisopropylatrazine (DIA) and didealkylatrazine (DDA)) were investigated in a semienclosed bay of the western Pacific Ocean. Seasonal surface water and suspended particulate sediment (SPS) samples were collected from the estuary and bay in January, April, and August 2019. The level of pesticide contamination was lower in the bay than in the estuary, and the pesticide concentration in the dissolved phase was higher than that in the adsorbed phase. The average concentrations of atrazine and the three degradation products in the three seasons ranged from 2.42 to 328.46 ng/L in water and from 0.07 to 12.75 ng/L in SPS. The proportion of atrazine among the four detected pollutants decreased from 0.7 to 0.1 in surface water and from 0.3 to 0.1 in SPS over the seasons. As the main degradation products, the concentration proportions of DDA and DEA reached as high as 0.6 in August. The ratio of DEA to atrazine (DEA/ATR) increased from January to August, which indicated the progressive degradation process in the bay. Single-factor analysis of variance and principal component analysis indicated that atrazine degradation was sensitive to temperature, dissolved oxygen, and salinity. These three factors accounted for almost 70% of the seasonal variance in atrazine without a quantification assessment of photolysis or bacteria. The spatial distributions of DEA in the three seasons demonstrated that wind and currents also played important roles in pollutant redistribution. The seasonal temporal and spatial correlations between water and SPS demonstrated the degradation patterns of atrazine in marine conditions, supporting the need for future detailed toxicity studies.

Coastal sediments, where microplastics (MPs) accumulate, support benthic microalgae (BMA) that contribute to ecosystem functions such as primary production, nutrient recycling and sediment biostabilization. The potential interactions between MPs, BMA and associated properties and functions remain poorly understood. To examine these interactions, a survey of 22 intertidal sites was conducted. MP abundance, size and a suite of MP diversity indices (based on color and shape) were determined from surface sediments alongside biochemical and physical properties. MPs were detected at all sites and dominated by polypropylene (34%), polyester (18%) and polyethylene (11%). Fragment and fiber dominance (16–92% and 6–81% respectively) and color-shape category diversity varied significantly by site. Distance-based linear models demonstrated that estuary-wide, mean grain size and mud were the best predictors of MP abundance-diversity matrices, but variance explained was low (9%). Relationships were improved when the data was split into sandy and muddy habitats. In sandy habitats (<8% mud), physical properties of the bed (mean grain size, mud content and distance from the estuary mouth) were still selected as predictors of MP abundance-diversity (14% variance explained); but a number of bivariate relationships were detected with biochemical properties such as BMA associated pigments and organic matter. In muddy habitats (>8% mud), porewater ammonium was lower when fiber abundance and overall MP diversity were higher. The inclusion of porewater ammonium, organic matter content and pheophytins alongside physical properties explained a greater percentage of the variance in MP abundance-diversity for muddy habitats (21%). The results highlight the importance of examining plastic shapes and MP categories in addition to abundance and emphasize that functionally different habitats should be examined separately to increase our understanding of MP-biota-function relationships.

The present study aimed to assess the toxicity of seven UV-filters: zinc oxide nanoparticles (nZnO, particle size <100 nm), titanium dioxide nanoparticles (nTiO₂, primary particle size 21 nm), 2-ethylhexyl-4-methoxycinnamate (EHMC), 4-methylbenzylidene camphor (4-MBC), avobenzone (AVO), octocrylene (OCTO) and benzophenone-3 (BP-3) on three species: Aliivibrio fischeri (inhibition of bioluminescence), Phaeodactylum tricornutum (growth inhibition) and Ficopomatus enigmaticus (larval development success). Results showed nTiO₂ to be the most toxic for P. tricornutum (EC₅₀ 0.043 mg L⁻¹), while no effect was observed in A. fischeri and F. enigmaticus. EHMC was the most toxic to A. fischeri (EC₅₀ 0.868 mg L⁻¹ (15 min) and 1.06 mg L⁻¹ (30 min)) and the second most toxic to P. tricornutum. For F. enigmaticus, the lowest percentages of correct development resulted from 4-MBC exposure, with EC₅₀ of 0.836 mg L⁻¹. Overall, AVO induced low toxicity to every assessed species and OCTO was the least toxic for F. enigmaticus larvae. Considering the results obtained for F. enigmaticus, further larval development assays were performed with nZnO and EHMC under different light (light vs darkness) and temperature (20 and 25 °C) conditions, showing higher percentages of correct development at 25 °C, independently on light/darkness conditions. Under different temperature and photoperiod conditions, nZnO was more toxic than EHMC. Overall, nZnO and EHMC were among the most toxic UV filters tested and, when testing the effects of these UV-filters with temperature the results highlight that the impacts are liable to be lessened at higher temperatures (25 °C compared with 20 °C), in the case of this estuarine polychaete species. Nevertheless, further experiments are necessary to describe the effects of these two UV-filters at different organization levels, to study the toxicity of eventual degradation by-products and to provide more information on the combination of different stressors.

Chromophoric dissolved organic matter (CDOM) in rivers is mainly affected by natural conditions and human activities and can reflect the watershed pollution status to a certain extent. The Yellow River is one of the largest contributors to the global riverine sediment flux from the land to ocean, and there is a paucity of information on how the optical properties of CDOM have the potential to serve as an indicator of water quality for the sediment-laden Yellow River. In this study, a three-dimensional fluorescence parallel factor (PARAFAC) analysis method was applied to investigate the seasonal and spatial variations in CDOM fluorescence components and spectral characteristics from the source region to the estuary in the mainstream of Yellow River. The relationships of CDOM with water quality indicators and trophic state were also analyzed. Six PARAFAC components (C1–C6) were identified and grouped into two categories: humic-like components (C1–C4), which accounted for 85.8 %, and protein-like components (C5 and C6), which accounted for only 14.2 %. The CDOM components, spectral parameters, and their clear correlations with the main ions (Na⁺ and Cl⁻) all indicated that the humic-like components may be primarily derived from nonpoint source erosion, and the protein-like components were mainly derived from point source discharges in the watershed. The combination of the CDOM absorption coefficient at 254 nm (a(254)), spectral slope ratio (SR), specific UV absorbance SUVA₂₅₄, and fluorescence index (FI) had a good predictive ability for the key water quality indicators (total nitrogen (TN), dissolved total nitrogen (DTN), total phosphorus (TP), dissolved total phosphorus (DTP), and chlorophyll a (Chl a)) and trophic state index (TSI). Therefore, some fluorophores and UV spectral parameters of CDOM in the Yellow River can be used for rapid water quality monitoring and pollution source indication, especially pollutants related to nitrogen and phosphorus nutrients in the basin.