Pollution of the oceans by microplastics (<5 mm) represents a major environmental problem. To date, a limited number of studies have investigated the level of contamination of marine organisms collected in situ. For extraction and characterization of microplastics in biological samples, the crucial step is the identification of solvent(s) or chemical(s) that efficiently dissolve organic matter without degrading plastic polymers for their identification in a time and cost effective way. Most published papers, as well as OSPAR recommendations for the development of a common monitoring protocol for plastic particles in fish and shellfish at the European level, use protocols containing nitric acid to digest the biological tissues, despite reports of polyamide degradation with this chemical. In the present study, six existing approaches were tested and their effects were compared on up to 15 different plastic polymers, as well as their efficiency in digesting biological matrices. Plastic integrity was evaluated through microscopic inspection, weighing, pyrolysis coupled with gas chromatography and mass spectrometry, and Raman spectrometry before and after digestion. Tissues from mussels, crabs and fish were digested before being filtered on glass fibre filters. Digestion efficiency was evaluated through microscopical inspection of the filters and determination of the relative removal of organic matter content after digestion. Five out of the six tested protocols led to significant degradation of plastic particles and/or insufficient tissue digestion. The protocol using a KOH 10% solution and incubation at 60 °C during a 24 h period led to an efficient digestion of biological tissues with no significant degradation on all tested polymers, except for cellulose acetate. This protocol appeared to be the best compromise for extraction and later identification of microplastics in biological samples and should be implemented in further monitoring studies to ensure relevance and comparison of environmental and seafood product quality studies.

The distribution of polycyclic aromatic hydrocarbons (PAHs) in the micro-zones of mangrove sediment is a predominant factors determining PAH bioavailability. In this study, a novel method for the in situ visualization (via microscope) and quantitative investigation of the PAH distribution in the micro-zones of mangrove sediment was established using microscopic fluorescence spectral analysis combined with derivative synchronous fluorescence spectroscopy (MFSA-DSFS). The MFSA-DSFS method significantly suppressed the background fluorescence signal of the sediment (the S/N values increased by over two orders of magnitude). The proportion of the nonpolar organic carbon content in the particulate organic matter (POM) rather than its content in the total organic matter (TOM) showed a significantly positive correlation with the uneven PAH distribution (Relative DC-M values) evaluated using the established method (p < 0.05). The extent of the uneven PAH distribution in the micro-zones of aged sediment was higher than that in the spiked sediment. Moreover, the distribution pattern of the PAHs within the mangrove sediment changed to become more homogeneous in the presence of low-molecular-weight organic acids (LMWOAs), which primarily contribute to increasing the POM content.

With the development and application of graphene oxides (GO), the potential toxicity and environmental behavior of GO has become one of the most forefront environmental problems. Herein, a novel nanoscale layered double hydroxides (glycerinum-modified nanocrystallined Mg/Al layered double hydroxides, LDH-Gl), layered double oxides (calcined LDH-Gl, LDO-Gl) and metallic oxide (TiO2) were synthesized and applied as superior coagulants for the efficient removal of GO from aqueous solutions. Coagulation of GO as a function of coagulant contents, pH, ionic strength, GO contents, temperature and co-existing ions were studied and compared, and the results showed that the maximum coagulation capacities of GO were LDO-Gl (448.3 mg g−1) > TiO2 (365.7 mg g−1) > LDH-Gl (339.1 mg g−1) at pH 5.5, which were significantly higher than those of bentonite, Al2O3, CaCl2 or other natural materials due to their stronger reaction active and interfacial effect. The presence of SO32− and HCO3− inhibited the coagulation of GO on LDH-Gl and LDO-Gl significantly, while other cations (K+, Mg2+, Ca2+, Ni2+, Al3+) or anion (Cl−) had slightly effect on GO coagulation. The interaction mechanism of GO coagulation on LDO-Gl and TiO2 might due to the electrostatic interactions and strong surface complexation, while the main driving force of GO coagulation on LDH-Gl might be attributed to electrostatic interaction and hydrogen bond, which were further evidenced by TEM, SEM, FT-IR and XRD analysis. The results of natural environmental simulation showed that LDO-Gl, TiO2 or other kinds of natural metallic oxides could be superior coagulants for the efficient elimination of GO or other toxic nanomaterials from aqueous solutions in real environmental pollution cleanup.

In-situ characterization and assessment of arsenic (As) mobility in sediments was scarce. In this study, the distributions of labile As at a vertical resolution of 2 mm were obtained in the sediments of a large Lake Taihu through in-situ measurements using a Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) technique. The DGT-labile As, interpreted as DGT flux (FDGT), exhibited three different patterns in the lake, with all the patterns generally showing an increasing mobility followed by a decreasing mobility with sediment depth. The mobility of As could be characterized by the average FDGT (0.06–1.27 pg cm−2 s−1) in the top 10 mm surface sediments, the maximal FDGT (FDGT-M, 0.14–2.44 pg cm−2 s−1) in the end of the initial increasing phase of FDGT, and the diffusion length (ΔL, 28–66 mm) from the depth showing the FDGT-M to the sediment-water interface. The upward mobilization of labile As from the deep sediments to the surface sediments and overlying water became evident when FDGT-M > 1.7 pg cm−2 s−1 or ΔL < 41 mm. The results, for the first time, showed a prospect in in-situ risk assessment of the pollution of sediment As. It was suggested that the increasing mobility of As in the upper sediments was controlled by the reduction of As(V) and the reductive dissolution of Fe(III) (hydr)oxides, while the decreasing mobility in the deep sediments was attributed to immobilization of As(III) by secondary Fe(II)-bearing minerals.

Material flow analysis (MFA) is a useful tool to predict the flows of engineered nanomaterials (ENM) to the environment. The quantification of release factors is a crucial part of MFA modeling. In the last years an increasing amount of literature on release of ENM from materials and products has been published. The purpose of this review is to analyze the strategies implemented by MFA models to include these release data, in particular to derive transfer coefficients (TC). Our scope was focused on those articles that analyzed the release from applications readily available in the market in settings that resemble average use conditions. Current MFA studies rely to a large extent on extrapolations, authors’ assumptions, expert opinions and other informal sources of data to parameterize the models. We were able to qualitatively assess the following aspects of the release literature: (i) the initial characterization of ENM provided, (ii) quantitative information on the mass of ENM released and its characterization, (iii) description of transformation reactions and (iv) assessment of the factors determining release. Although the literature on ENM release is growing, coverage of exposure scenarios is still limited; only 20% of the ENMs used industrially and 36% of the product categories involved have been investigated in release studies and only few relevant release scenarios have been described. Furthermore, the information provided is rather incomplete concerning descriptions and characterizations of ENMs and the released materials. Our results show that both the development of methods to define the TCs and of protocols to enhance assessment of ENM release from nano-applications will contribute to increase the exploitability of the data provided for MFA models. The suggestions we provide in this article will likely contribute to an improved exposure modeling by providing ENM release estimates closer to reality.

Bacterial degradation of crude oil in response to nutrient treatments has been vastly studied. But there is a paucity of information on kinetic parameters of crude oil degradation. Here we report the nutrient stimulated kinetic parameters of crude oil degradation assessed in terms of CO2 production and oil removal by Pseudomonas aeruginosa AKS1 and Bacillus sp. AKS2. The hydrocarbon degradation rate of P. aeruginosa AKS1 in oil only amended sediment was 10.75 ± 0.65 μg CO2-C g−1 sediment day−1 which was similar to degradation rate in sediments with no oil. In presence of both inorganic N & P, the degradation rate increased to 47.22 ± 1.32 μg CO2-C g−1 sediment day−1. The half-saturation constant (Ks) and maximum degradation rate (Vmax) for P. aeruginosa AKS1 under increasing N and saturating P concentration were 13.57 ± 0.53 μg N g−1 sediment and 39.36 ± 1.42 μg CO2-C g−1 sediment day−1 respectively. The corresponding values at increasing P and a constant N concentration were 1.60 ± 0.13 μg P g−1 sediment and 43.90 ± 1.03 μg CO2-C g−1 sediment day−1 respectively. Similarly the degradation rate of Bacillus sp. AKS2 in sediments amended with both inorganic nutrients N & P was seven fold higher than the rates in oil only or nutrient only treated sediments. The Ks and Vmax estimates of Bacillus sp. AKS2 under increasing N and saturating P concentration were 9.96 ± 1.25 μg N g−1 sediment and 59.96 ± 7.56 μg CO2-C g−1 sediment day−1 respectively. The corresponding values for P at saturating N concentration were 0.46 ± 0.24 μg P g−1 sediment and 63.63 ± 3.54 μg CO2-C g−1 sediment day−1 respectively. The rates of CO2 production by both isolates were further stimulated when oil concentration was increased above 12.5 mg g−1 sediment. However, oil degradation activity declined at oil concentration above 40 mg g−1 sediment when treated with constant nutrient: oil ratio. Both isolates exhibited alkane hydroxylase activity but aromatic degrading catechol 1, 2-dioxygenase and catechol 2, 3-dioxygenase activities were shown by P. aeruginosa AKS1 only.

We examined the bioaccumulation of three microcystin (MC) congeners (MC-LR, MC-RR and MC-YR) in the oligochaete Limnodrilus hoffmeisteri from July 2013 through June 2014 in Lake Taihu, China. Environmental parameters and MCs in sediment, phytoplankton and water column also were examined. L. hoffmeisteri accumulated extremely high MC concentrations during the warmest months, with a maximum value of 11.99 μg/g (MC-LR: 1.76 μg/g, MC-RR: 2.51 μg/g, and MC-YR: 7.73 μg/g). Total MC concentrations in L. hoffmeisteri declined after October (2013) and began to increase in May (2014). Between July and October, MC-YR concentration was higher than MC-LR and MC-RR. MC concentrations in L. hoffmeisteri were positively correlated with pH, water temperature, conductivity, chlorophyll a, nitrite and the biomass of Microcystis, and negatively correlated with dissolved oxygen (DO), nitrate, total nitrogen (TN), dissolved total inorganic carbon and the biomass of Bacillariophyta. In addition, MCs in phytoplankton were more strongly correlated with MCs in L. hoffmeisteri than in the water column or sediment. Our results demonstrated that L. hoffmeisteri could accumulate high MC concentrations in the bloom season, which might transfer to the edible zoobenthos and fish through trophic transfer, thereby posing a significant health threat to humans.

Much research has considered the influence of biochars on the availability and phytoaccumulation of potentially toxic elements (PTEs) from soil. However, the vast majority of these studies use, what are arguably, unrealistic and unpractical amounts of biochar (10, 50 and even up to 100 t/ha). To offer a more realistic insight into the influence of biochar on PTE partitioning and phytoaccumulation, a field study, using modest rates of biochar application (1.5, 3.0 t/ha), was undertaken. Specifically, the research investigated the influence of sewage sludge biochar (SSBC) on the accumulation of Cd into rice (Oryza sativa L.) grown in Cd contaminated (0.82 ± 0.07 mg/kg) paddy soil. Results indicated, Cd concentrations in rice grains to significantly (p < 0.05) decrease from 1.35 ± 0.09 mg/kg in the control to 0.82 ± 0.07 mg/kg and 0.80 ± 0.21 mg/kg in the 1.5 t/ha and 3.0 t/ha treatments, respectively. Accordingly, the hazardous quotient (HQ) indices for Cd, associated with rice grain consumption, were also reduced by ∼40%. SSBC amendment significantly (p < 0.05) increased grain yields from 1.90 ± 0.08 g/plant in the control to 2.17 ± 0.30 g/plant and 3.40 ± 0.27 g/plant in the 1.5 t/ha and 3.0 t/ha treatments, respectively. Thus, the amendment of SSBC to contaminated paddy soils, even at low application rates, could be an effective approach to mitigate Cd accumulation into rice plants, to improve rice grain yields, and to thereby improve food security and protect public health.

Long-lived, upper trophic level marine mammals are vulnerable to bioaccumulation of persistent organic pollutants (POPs). Internal tissues may accumulate and mobilize POP compounds at different rates related to the body condition of the animal and the chemical characteristics of individual POP compounds; however, collection of samples from multiple tissues is a major challenge to ecotoxicology studies of free-ranging marine mammals and the ability to predict POP concentrations in one tissue from another tissue remains rare. Northern elephant seals (Mirounga angustirostris) forage on mesopelagic fish and squid for months at a time in the northeastern Pacific Ocean, interspersed with two periods of fasting on land, which results in dramatic seasonal fluctuations in body condition. Using northern elephant seals, we examined commonly studied tissues in mammalian toxicology to describe relationships and determine predictive equations among tissues for a suite of POP compounds, including ΣDDTs, ΣPCBs, Σchlordanes, and ΣPBDEs. We collected paired blubber (inner and outer) and blood serum samples from adult female and male seals in 2012 and 2013 at Año Nuevo State Reserve (California, USA). For females (N = 24), we sampled the same seals before (late in molting fast) and after (early in breeding fast) their approximately seven month foraging trip. For males, we sampled different seals before (N = 14) and after (N = 15) their approximately four month foraging trip. We observed strong relationships among tissues for many, but not all compounds. Serum POP concentrations were strong predictors of inner blubber POP concentrations for both females and males, while serum was a more consistent predictor of outer blubber for males than females. The ability to estimate POP blubber concentrations from serum, or vice versa, has the potential to enhance toxicological assessment and physiological modeling. Furthermore, predictive equations may illuminate commonalities or distinctions in bioaccumulation across marine mammal species.

The aim of this study was to assess the impact of treated wastewaters on native wild Prussian carp inhabiting effluent-receiving waters (ERC) receiving municipal and sugar plant treated wastewaters, further downstream waters (DW), and a detached canal unaffected by the WWTP activities. To that end, general fish health status was determined, including plasma biochemical, haematological, oxidative stress and tissue histopathological indices, over three seasons. The greatest tissue alterations were in fall in ERC during sugar beet processing, as hypertrophy of gill epithelial and interlamellar cells, necrosis and lymphocytic infiltration, hyperplasia and hypertrophy of renal tubules, distention of hepatic sinusoids. In fall the lowest leukocytes, lymphocytes and granulocytes (2467 ± 565, 1333 ± 264, 1133 ± 488 cells/μL respectively), as well as highest plasma ALP (52.7 ± 19.39 U/L) were measured. ERC in fall had the highest ammonium (20 mg/L), nitrite (1.48 mg/L), nitrate (13.4 mg/L), and lowest dissolved O2 (1.23 mg/L). Gill, kidney and liver alterations, and the highest plasma cholesterol (9.1 ± 1.98 mmol/L) were noted in DW fish in fall. Tissue morphology during sugar cane processing seems a consequence of cellular and structural tissue integrity loss. Structural heterogeneity of gills and spleen was enhanced with increasing concentrations of heavy metals and correlated with oxidative stress (SOD 392.5 ± 77.28 U/L). Monogenean infestation was moderate in ERC fish in all seasons compared with DW fish. Prussian carp biological responses to multiple stressors, measured by the effects of WWTP on blood and tissue parameters, reached far downstream and were not of localized nature. This study demonstrated that in aquatic environments impacted with complex contaminants acting synergistically, causal relationships between biological responses and environmental stressors should be interpreted. Integrated histopathological, haematological and biochemical findings are valuable biomarkers for native fish adaptive patterns and monitoring of water quality/pollution of freshwater ecosystems.