The study addresses the topic of suitable matrices for chemical analysis in fish monitoring and discusses the effects of data normalization in the context of the European Water Framework Directive (WFD). Differences between species are considered by comparing three frequently monitored species of different trophic levels, i.e., chub (Squalius cephalus, n = 28), (bream, Abramis brama, n = 11), and perch (Perca fluviatilis, n = 19) sampled in the German Danube. The WFD priority substances dioxins, furans and dioxin-like polychlorinated biphenyls (PCDD/F + dl-PCB), polybrominated diphenyl ethers (PBDE), α-hexabromocyclododecane (α-HBCDD), hexachlorobenzene (HCB), mercury (Hg), and perfluorooctane sulfonic acid (PFOS) as well as non-dioxin-like (ndl)-PCB were analyzed separately in fillet and carcass and whole body concentrations were calculated. Hg was analyzed in individual fish fillets and carcasses, all other substances were determined in pool samples, which were compiled on the basis of fish size (3 chub pools, 1 bream pool, 2 perch pools). The data were normalized to 5% lipid weight (or 26% dry mass in the case of Hg and PFOS) for comparison between matrices and species.Hg concentrations were generally higher in fillet than in whole fish (mean whole fish-to-fillet ratio: 0.7) whereas all other substances were mostly higher in whole fish. In the case of lipophilic substances these differences leveled after lipid normalization.Significant correlations (p ≤ .05) were detected between Hg and fish weight and age. Hg concentrations varied least among younger fish. PCDD/F, dl-PCB, ndl-PCB, PBDE, α-HBCDD and HCB correlated significantly (p ≤ .05) with lipid concentrations. Fillet-to-whole fish conversion equations and/or conversion factors were derived for all substances except α-HCBDD. Although more data also for individual fish would be desirable the results are nevertheless a step on the way to translate fillet concentrations of priority substances to whole fish concentrations.

Microplastics may lose buoyancy and occur in deeper waters and ultimately sink to the sediment and this may threaten plankton inhabiting in various water layers and benthic organisms. Here, we conduct the first survey on microplastics in the water column and corresponding sediment in addition to the surface water in the Bohai Sea. A total of 20 stations covering whole Bohai Sea were selected, which included 6 stations specified for water column studying. Seawater was sampled every 5 m, with maximal depth of 30 m in the water column using Niskin bottles coupled with a ship-based conductivity, temperature and depth sensor (CTD) system and surface sediment samples were collected using box corer. The results indicated that higher microplastic levels accumulated at a depth range of 5–15 m in the water column in some stations, suggesting the surface water survey was not sufficient to reflect microplastics loading in a water body. Fibers predominated microplastic types in both seawater and sediment of the Bohai Sea, which accounted for 75%–96.4% of the total microplastics. However the relatively proportion of the fibers in the deeper water layers and sediment was lower than that in the surface water. Microplastic shapes are more diverse in the sediment than in the seawater in general. The microplastic sizes changed with depth in the water column and the proportion of the size-fraction < 300 μm increased with depth, probably as a result of rapid biofouling on the small microplastics due to their higher specific surface area. Such depth distribution also implied that sampling with manta net (>330 μm) that commonly used in the oceanographic survey might underestimate microplastics abundance in the water column. Further studies are recommended to focus on the sinking behavior of microplastics and their effects on marine organisms.

Accurate measuring n-octanol/water partition coefficients (log Kₒw) of perfluoroalkyl carboxylic acids (PFCAs) using experimental approach has been proven to be very difficult due to their special properties. The ionizable carboxyl groups in PFCAs make their log Kₒw dependent on pH. In this study, the log Kₒw values of neutral species of PFCAs (C₄≤ₙ≤₁₄) were measured based on reversed-phase high-performance liquid chromatography (RP-HPLC) with the mobile phase pH varying in the range of 1.09–5.00. The relationship between log Kₒw and retention times was established using some reference compounds (including agrochemicals, polycyclic aromatic hydrocarbons) with known log Kₒw values, and then validated with alkyl fatty acids, which have similar chemical structures as PFCAs. The apparent log Kₒw (i.e., log Dₒw) of the C₄–₁₄ PFCAs were calculated based on their retention times using the established model, and they displayed a negative linear relationship with the mobile phase pH in the range of 1.09–4.00. Consequently, the log Dₒw values were converted to the corresponding log Kₒw values (1.05–7.19) based on the relationship of log Dₒw = log Kₒw + pKₐ – pH. The log Kₒw increased with perfluorinated carbon chain length with a greater rate for C₄ to C₅ PFCAs than for C₅–₁₄ PFCAs.

In Mediterranean areas, dry deposition is a major component of the total atmospheric N input to natural habitats, particularly to forest ecosystems. An innovative approach, combining the empirical inferential method (EIM) for surface deposition of NO₃⁻ and NH₄⁺ with stomatal uptake of NH₃, HNO₃ and NO₂ derived from the DO₃SE (Deposition of Ozone and Stomatal Exchange) model, was used to estimate total dry deposition of inorganic N air pollutants in four holm oak forests under Mediterranean conditions in Spain. The estimated total deposition varied among the sites and matched the geographical patterns previously found in model estimates: higher deposition was determined at the northern site (28.9 kg N ha⁻¹ year⁻¹) and at the northeastern sites (17.8 and 12.5 kg N ha⁻¹ year⁻¹) than at the central-Spain site (9.4 kg N ha⁻¹ year⁻¹). On average, the estimated dry deposition of atmospheric N represented 77% ± 2% of the total deposition of N, of which surface deposition of gaseous and particulate atmospheric N averaged 10.0 ± 2.9 kg N ha⁻¹ year⁻¹ for the four sites (58% of the total deposition), and stomatal deposition of N gases averaged 3.3 ± 0.8 kg N ha⁻¹ year⁻¹ (19% of the total deposition). Deposition of atmospheric inorganic N was dominated by the surface deposition of oxidized N in all the forests (means of 54% and 42% of the dry and total deposition, respectively). The relative contribution of NO₂ to dry deposition averaged from 19% in the peri-urban forests to 11% in the most natural site. During the monitoring period, the empirical critical loads provisionally proposed for ecosystem protection (10–20 kg N ha⁻¹ year⁻¹) was exceeded in three of the four studied forests.

Sediment samples from three coastal sites - two beach resorts (Beach 1 and Beach 2 sites) and an area lying between an oil refinery and a river estuary (Estuarine site) - were analyzed for antibiotic- and heavy metal (HM)-resistant enterococci.A total of 123 enterococci, 36 E. faecium, 34 E. casseliflavus, 33 E. hirae, 5 E. faecalis, 3 E. durans, 3 E. gallinarum, and 9 Enterococcus spp, were recovered. Strains resistant to erythromycin, tetracycline and quinupristin/dalfopristin (Q/D) were recovered from all sites, whereas multidrug-resistant isolates were recovered only from “Beach 2” (14%) and “Estuarine” (3.7%). As regards HM resistance, the strains showed a high frequency (68%) of cadmium and/or copper resistance and uniform susceptibility to mercury. The prevalence of cadmium-resistant strains was significantly higher among erythromycin-resistant than among erythromycin-susceptible strains. A significant association between cadmium or copper resistance and Q/D resistance was also observed at “Estuarine” site. The levels of the two HMs in sediment from all sites were fairly low, ranging from 0.070 to 0.126 μg/g, for cadmium and from 1.00 to 7.64 μg/g for copper. Mercury was always undetectable. These findings are consistent with reports that low HM concentrations may contribute to co-selection of antibiotic-resistant bacterial strains, including enterococci.

To investigate the chronic toxicity of graphene oxide (GO) and its functionalized products (GO-carboxyl, GO-imidazole and GO-polyethylene glycol), a two-generation study was conducted using the aquatic model species Daphnia magna. Each generation of daphnids were exposed for 21 days to 1.0 mg L−1 graphene material, with body length, neonate number, time of first brood and the intrinsic rate of natural increase (r) assessed as endpoints. Chronic exposure to GO, GO-carboxyl, and GO-imidazole had no adverse effect on body length or offspring number in the daphnid F0 generation, however, this exposure paradigm led to significant growth or reproduction inhibition in the following generation. Meanwhile, GO was found to show the strongest inhibitory effect, sequentially followed by GO-carboxyl and GO-imidazole. With exposure to GO-polyethylene glycol, no significant effects on growth or reproduction were observed for both F0 and F1 generation daphnids. These results reveal that carboxyl, imidazole and polyethylene glycol functional attachments alleviate the bio-toxicity of GO, especially polyethylene glycol. The increased C/O atomic ratio present in GO-carboxyl, GO-imidazole and GO-polyethylene glycol due to functionalization may mainly explain the reduced toxicity.

Microplastics are an emerging contaminants of concern in aquatic environments. The aggregation behaviors of microplastics governing their fate and ecological risks in aquatic environments is in need of evaluation. In this study, the aggregation behavior of polystyrene microspheres (micro-PS) in aquatic environments was systematically investigated over a range of monovalent and divalent electrolytes with and without natural organic matter (i.e., Suwannee River humic acid (HA)), at pH 6.0, respectively. The zeta potentials and hydrodynamic diameters of micro-PS were measured and the subsequent aggregation kinetics and attachment efficiencies (α) were calculated. The aggregation kinetics of micro-PS exhibited reaction- and diffusion-limited regimes in the presence of monovalent or divalent electrolytes with distinct critical coagulation concentration (CCC) values, followed the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The CCC values of micro-PS were14.9, 13.7, 14.8, 2.95 and 3.20 mM for NaCl, NaNO3, KNO3, CaCl2 and BaCl2, respectively. As expected, divalent electrolytes (i.e., CaCl2 and BaCl2) had stronger influence on the aggregation behaviors of micro-PS as compared to monovalent electrolytes (i.e., NaCl, NaNO3 and KNO3). HA enhanced micro-PS stability and shifted the CCC values to higher electrolyte concentrations for all types of electrolytes. The CCC values of micro-PS were lower than reported carbonaceous nanoparticles CCC values. The CCC[Ca2+]/CCC [Na+] ratios in the absence and presence of HA at pH 6.0 were proportional to Z−2.34 and Z−2.30, respectively. These ratios were in accordance with the theoretical Schulze–Hardy rule, which considers that the CCC is proportional to z−6–z−2. These results indicate that the stability of micro-PS in the natural aquatic environment and the possibility of significant aqueous transport of micro-PS.

The lotic habitats affected by trout farm waste are colonized with a particular invertebrate community of which chironomids are the most abundant group. However, there is little information available regarding how chironomid community structures respond to this type of pollution at the highest taxonomic resolution. Eight fish farms, together with their lotic systems as recipients, were used to test the variability of the chironomid community and its surrogates (taxonomic and functional metrics) across spatially arranged sampling sites to form a gradual decrease in the trout farm influence. The self organizing map (SOM) classified six different types of chironomid communities which were characteristic for both the control and affected habitats. The species indicator analyses listed 32 taxa as positive indicators of water pollution. The SOM and Kruskal-Wallis test revealed that the pattern of chironomid community structure obtained was mainly driven by six environmental parameters (Altitude, conductivity, distance from the outlet, hardness, HN₄-N, NO₃-N). Categorical principal components analysis (CATPCA) derived three models for each type of biotic metric, in which for diversity-, taxonomy- and functional feeding group-based metrics, the first two dimensions explained 55.2%, 58.3% and 55.4%, of the total variance respectively for 315 sampling sites. According to this analysis, the total number of taxa (S), abundance and the Shannon-Wiener index (H′) (as a diversity metric), as well as the proportion of Tanypodinae (as taxonomic group) and grazers/scraper (GRA) and gatherer collector (GAT)(as FFG metrics), were related to the outlet distance gradient, thus showing great potential to be used in the multimetric approach in bioassessment.

With the ever-increasing amounts of oil sands process-affected water (OSPW) accumulating from Canada's oil sands operations, its eventual release must be considered. As OSPW has been found to be both acutely and chronically toxic to aquatic organisms, remediation processes must be developed to lower its toxicity. Ozone treatment is currently being studied as a tool to facilitate the removal of organic constituents associated with toxicity. Biomarkers (e.g. gene expression) are commonly used when studying the effects of environmental contaminants, however, they are not always indicative of adverse effects at the whole organism level. In this study, we assessed the effects of OSPW exposure on developing zebrafish by linking gene expression to relevant cellular and whole organism level endpoints. We also investigated whether or not ozone treatment decreased biomarkers and any associated toxicity observed from OSPW exposure. The concentrations of classical naphthenic acids in the raw and ozonated OSPW used in this study were 16.9 mg/L and 0.6 mg/L, respectively. Ozone treatment reduced the total amount of naphthenic acids (NAs) in the OSPW sample by 92%. We found that exposure to both raw and ozonated OSPW had no effect on the survival of zebrafish embryos. The expression levels of biotransformation genes CYP1A and CYP1B were induced by raw OSPW exposure, with CYP1B being more highly expressed than CYP1A. In contrast, ozonated OSPW exposure did not increase the expression of CYP1A and only slightly induced CYP1B. A decrease in cardiac development and function genes (NKX2.5 and APT2a2a) was not associates with large changes in heart rate, arrhythmia or heart size. We did not find any indications of craniofacial abnormalities or of increased occurrence of apoptotic cells. Overall, our study found that OSPW was not overtly toxic to zebrafish embryos.

We examine the spatio-temporal trends of mercury, a well-known global legacy contaminant, in eleven fish species across all of the Canadian Great Lakes. These particular fish species are selected based on their ecological, commercial, and recreational importance to the biodiversity and fishing industry of the Great Lakes. We present a two-pronged Bayesian methodological framework to rigorously assess mercury temporal trends across multiple fish species and locations. In the first part of our analysis, we develop dynamic linear models to delineate the total mercury levels and rates of change, while explicitly accounting for the covariance between fish length and mercury levels in fish tissues. We then use hierarchical modelling to evaluate the spatial variability of mercury contamination between nearshore and offshore locations, as well as to examine the hypothesis that invasive species have induced distinct shifts on fish mercury contamination trends. Our analysis suggests that the general pattern across the Great Lakes was that the elevated mercury concentrations during the 1970s had been subjected to a declining trend throughout the late 1980s/early 1990s, followed by a gradual stabilization after the late 1990s/early 2000s. The declining trend was more pronounced with top fish predators, whereas benthivorous fish species mainly underwent wax-and-wane cycles with a weaker evidence of a long-term declining trend. Historically contaminated regions, designated as Areas of Concern, and bays receiving riverine inputs are still characterized by mercury concentrations that can lead to consumption restrictions. Lake Erie displayed the lowest mercury levels across all the fish species examined. However, several species of commercial importance showed a reversing (increasing) trend in the 2000s, although their current levels do not pose any major concerns for consumption advisories. These recent trend reversals can be linked with systematic shifts in energy trophodynamics along with the food web alterations induced from the introduction of non-native species, and the potentially significant fluxes from the atmosphere.