Comparison of three digestion methods for microplastic extraction from aquaculture feeds.

Microplastics (MPs) are ubiquitous pollutants found in aquaculture animals that may threaten human health through the food chain. However, there is a lack of effective methods for extracting MPs from aquaculture feeds containing complex components such as organic matter and fish bones. Therefore, in the present study, the extraction efficiency of three digestion methods using 30 % H2O2, Fenton reagent, and 30 % H2O2 + HNO3 for different particle sizes and types of MPs in aquaculture feeds was investigated and compared. The total digestion efficiency of the aquaculture feeds by 30 % H2O2 was 97.3 ± 0.1 %, while the recovery efficiency of MPs was 91.3 ± 1.1 % -103.1 ± 0.9 %. However, there was a large deviation in the extraction efficiency of MPs from aquaculture feeds by the Fenton reagent and 30 % H2O2 + HNO3. Notably, the surface morphology, particle size distribution, and oxidation degree of MPs hardly changed after 30 % H2O2 digestion. More importantly, the changes in the spectral features and carbonyl index of MPs after 30 % H2O2 digestion were smaller than those of the Fenton reagent and 30 % H2O2 + HNO3, which did not affect the identification of MPs. Overall, 30 % H2O2 was more efficient in extracting MPs from aquaculture feeds, and no significant effect on the characteristics of MPs was observed. This work provides novel insights into the effect of chemical pretreatment on the extraction of MPs in aquaculture feeds and provides an optimal protocol for the detection of MPs in aquaculture feeds.

Fabrication and optimization of paper chips from calcinated Fe-MOFs for rapid and in situ visual detection of tetracyclines in water environments.

Antibiotics such as tetracyclines (TCs) have become a major threat to ecosystem safety and human health, as their abuse has caused the occurrence and proliferation of antibiotic-resistant bacteria and genes. Currently, there is still a lack of convenient in situ methods for the detection and monitoring of TC pollution in actual water systems. This research reports a paper chip based on the complexation of iron-based metal organic frameworks (Fe-MOFs) and TCs for rapid and in situ visual detection of representative oxytetracycline (OTC) pollution in water environments. The optimized complexation sample NH2-MIL-101(Fe)- 350 obtained by calcination at 350 °C exhibited the highest catalytic activity and was then used for paper chip fabrication by printing and surface modification. Notably, the paper chip demonstrated a detection limit as low as 17.11 nmol L-1 and good practicability in reclaimed water, aquaculture wastewater, and surface water systems, with OTC recovery rates of 90.6-111.4%. More importantly, the presence of dissolved oxygen (9.13-12.7 mg L-1), chemical oxygen demand (0.52-12.1 mg L-1), humic acid (< 10 mg L-1), Ca2+, Cl-, and HPO42- (< 0.5 mol L-1) had negligible interference on the detection of TCs by the paper chip. Therefore, this work has developed a promising method for rapid and in situ visual monitoring of TC pollution in actual water environments.

Hormetic Effect of Pyroligneous Acids on Conjugative Transfer of Plasmid-mediated Multi-antibiotic Resistance Genes within Bacterial Genus.

Spread of antibiotic resistance genes (ARGs) by conjugation poses great challenges to public health. Application of pyroligneous acids (PA) as soil amendments has been evidenced as a practical strategy to remediate pollution of ARGs in soils. However, little is known about PA effects on horizontal gene transfer (HGT) of ARGs by conjugation. This study investigated the effects of a woody waste-derived PA prepared at 450°C and its three distillation components (F1, F2, and F3) at different temperatures (98, 130, and 220°C) on conjugative transfer of plasmid RP4 within Escherichia coli. PA at relatively high amount (40-100 µL) in a 30-mL mating system inhibited conjugation by 74-85%, following an order of PA > F3 ≈ F2 ≈ F1, proving the hypothesis that PA amendments may mitigate soil ARG pollution by inhibiting HGT. The bacteriostasis caused by antibacterial components of PA, including acids, phenols, and alcohols, as well as its acidity (pH 2.81) contributed to the inhibited conjugation. However, a relatively low amount (10-20 µL) of PA in the same mating system enhanced ARG transfer by 26-47%, following an order of PA > F3 ≈ F2 > F1. The opposite effect at low amount is mainly attributed to the increased intracellular reactive oxygen species production, enhanced cell membrane permeability, increased extracellular polymeric substance contents, and reduced cell surface charge. Our findings highlight the hormesis (low-amount promotion and high-amount inhibition) of PA amendments on ARG conjugation and provide evidence for selecting an appropriate amount of PA amendment to control the dissemination of soil ARGs. Moreover, the promoted conjugation also triggers questions regarding the potential risks of soil amendments (e.g., PA) in the spread of ARGs via HGT.

Potential risk of microplastics in processed foods: Preliminary risk assessment concerning polymer types, abundance, and human exposure of microplastics.

The occurrence of microplastics (MPs) has been widely reported in human foodstuffs, and their potential negative effects on human health have been brought into focus. Processed foods are more susceptible to MPs as contamination can be introduced during processing and packaging. However, the risk posed by MPs in processed foods remained unclear. This work aims to critically review the available data for MPs in 11 types of possessed foods and to conduct a preliminary risk assessment of MPs in processed foods. For a comprehensive evaluation, three indicators were selected and determined, namely chemical risk, pollution load, and estimated daily intake (EDI). Our results suggest that nori has the highest chemical risk, followed by canned fish, beverages, table salt, and other food items. In the case of pollution load, nori and milk fall into the risk category of Ⅳ and Ⅲ respectively. Table salts, bottled water, and sugar exhibited lower MPs pollution load (risk category of Ⅱ), whereas the pollution loads of other foods were calculated to be category Ⅰ. Moreover, a correlation between the pollution load of sea salts and MPs pollution level in ambient seawater was found. Regarding EDI of MPs from different processed foods, MPs intakes through bottled water (14.3 ± 3.4 n kg-1 d-1) and milk (6.6 ± 2.4 n kg-1 d-1) are significantly higher than that of the other foods (< 1 n kg-1 d-1). The probabilistic estimation of MPs daily intake indicated that children (19.7 n kg-1 d-1) are at a higher health risk than adults (female: 17.6 n kg-1 d-1, male: 12.6 n kg-1 d-1). Nevertheless, the exposure dose used in toxicological studies was about 10 times higher than the MPs intake via processed foods. Therefore, we argued that MPs in processed foods only carry limited risk. Overall, this study would provide the basis for risk management of MPs in processed food products.

Biodegradable and re-usable sponge materials made from chitin for efficient removal of microplastics.

Microplastics have attracted widespread attention due to their detrimental effects on organisms, and their efficient removal poses great challenges, especially those smaller than 3 µm that are more harmful for aquatic biota. Herein, the chitin based sponges with interconnected pores, excellent elasticity and mechanical durability were fabricated and composed with graphene oxide (GO) and oxygen-doped carbon nitride (O-C3N4). The chitin based sponges could effectively remove different functionalized microplastics (~1 µm) at pH 6-8, including carboxylate-modified polystyrene (PS-COOH), amine-modified polystyrene (PS-NH2), and polystyrene (PS). Notably, the removal efficiency of three microplastics by the chitin based sponges reached up to 71.6-92.1% at an environmentally relevant concentration of 1 mg L-1 in water system. The potential driving forces of the adsorption were electrostatic interactions, hydrogen bond interactions, and π-π interactions. In addition, the chitin based sponges are reusable and after re-used for 3 cycles due to their excellent compressibility. The algae toxicity test demonstrated good biocompatibility of the chitin based sponges and they are also biodegradable in a natural soil. This study provides a green and promising method for fabricating environmentally friendly adsorbents for small-size microplastics removal, and expands the insights into the mechanisms of microplastic adsorption onto the sponge materials.

Seasonal distribution and ecological risk of phthalate esters in surface water and marine organisms of the Bohai Sea.

The spatiotemporal variability and ecological risks related to 16 phthalate esters (PAEs) were investigated in surface water and marine organisms of the Bohai Sea. The average PAE concentrations in the surface water were 8.02, 4.53, and 3.16 µg L-1 in spring, summer, and winter, respectively. Additionally, suspended particle matter was positive related to PAE content in seawater in spring and winter. The predominant PAEs in both water and biota were dimethyl phthalate (DMP), di-butyl phthalate (DBP), di-isobutyl phthalate (DIBP), and diethylhexyl-phthalate (DEHP). Because they do not exhibit long-distance migratory behavior, Chaeturichthys hexanema, Cynoglossus lighti, and Loligo japonica were good candidate indicator organisms for PAE pollution in Bohai Sea. The risk quotient method revealed that DIBP, DBP, and DEHP posed relatively greater risks to the aquatic system. This research establishes baseline data from which future management strategies to control PAEs in the Bohai Sea can be developed.

[Pollution Characteristics and Ecological Risk Assessment of Phthalate Esters (PAEs) in the Surface Water of Jiaozhou Bay].

In order to better understand phthalate esters (PAEs) pollution in Jiaozhou Bay, surface water samples were collected for content analysis in August and November 2015 and January 2016. Fifteen kinds of PAEs were detected by stir bar sorptive extraction and gas chromatography-mass spectrometry. The content, composition, spatial distribution, seasonal variation, and ecological risk assessment of the PAEs in the surface waters were examined and analyzed. The results showed that:① The total concentrations of PAEs in the surface seawater in August and November 2015 and January 2016 were 3.63-21.20 µg·L-1, 2.24-12.60 µg·L-1, and 0.01-4.15 µg·L-1, respectively, and the average concentrations were 11.10 µg·L-1, 5.26 µg·L-1, and 0.80 µg·L-1, respectively. ② Influenced by runoff and ocean currents, the concentration of PAEs in the surface water of Jiaozhou Bay is higher near the shore and lower in the middle, and the total concentration of the east coast is higher than that of the west coast. Compared with surveys of other rivers and oceans, the PAEs content in the surface water of Jiaozhou Bay is moderate, but it is heavily polluted compared with other oceans. ③ Considering the rainfall and other factors, the distribution of PAEs in the three seasons followed the order summer > autumn > winter. The main PAEs detected were DBP, BBP, and DEHP. ④ The results of the ecological risk assessment showed that the risk quotient (RQ) of DBP at each station in Jiaozhou Bay was greater than 1; that is, the ecological risk was relatively large, while the risk of the other PAEs (RQ<1) was small. PAEs have become a potentially threatening organic pollutant in Jiaozhou Bay. Their behavior and the ecological hazards that they present to the environment still require further study.

Fate of four phthalate esters with presence of Karenia brevis: Uptake and biodegradation.

Phthalate esters (PAEs), one class of the most frequently detected endocrine-disrupting chemicals (EDCs) in marine environment, have aroused wide public concerns because of their carcinogenicity, teratogenicity, and mutagenicity. However, the environmental fate of PAEs in the occurrence of harmful algal blooms remains unclear. In this research, four PAEs with different alkyl chains, i.e., dimethyl phthalate (DMP), diethyl phthalate (DEP), diallyl phthalate (DAP), and dipropyl phtalate (DPrP) were selected as models to investigate toxicity, uptake, and degradation of PAEs in seawater grown with K. brevis, one of the common harmful red tide species. The 96-h median effective concentration (96h-EC50) values followed the order of DMP (over 0.257 mmol L-1) > DEP (0.178 mmol L-1) > DAP (0.136 mmol L-1) > DPrP (0.095 mmol L-1), and the bio-concentration factors (BCFs) were positively correlated to the alkyl chain length. These results indicate that the toxicity of PAEs and their accumulation in K. brevis increased with increasing alkyl chains, due to the higher lipophicity of the longer chain PAEs. With growth of K. brevis for 96 h, the content of DMP, DEP, DAP, and DPrP decreased by 93.3%, 68.2%, 57.4% and 46.7%, respectively, mainly attributed to their biodegradation by K. brevis, accounting for 87.1%, 61%, 46%, 40% of their initial contents, respectively. It was noticed that abiotic degradation had little contribution to the total reduction of PAEs in the algal cultivation systems. Moreover, five metabolites were detected in the K. brevis when exposed to DEP including dimethyl phthalate (DMP), monoethyl phthalate (MEP), mono-methyl phthalate (MMP), phthalic acid (PA), and protocatechuic acid (PrA). While when exposed with to DPrP, one additional intermediate compound diethyl phthalate (DEP) was detected in the cells of K. brevis in addition to the five metabolites mentioned above. These results confirm that the main biodegradation pathways of DEP and DPrP by K. brevis included de-esterification, demethylation or transesterification. These findings will provide valuable evidences for predicting the environmental fate and assessing potential risk of PAEs in the occurrence of harmful algal blooms in marine environment.

Comparison of six digestion methods on fluorescent intensity and morphology of the fluorescent polystyrene beads.

Effect of digestion methods on fluorescence intensity of fluorescent polystyrene (PS) beads was poorly understood, which may affect the accuracy of toxicity test of the fluorescent PS beads exposed to marine organisms. Therefore, six digestion approaches were compared on fluorescence intensities and properties of three commercial fluorescent PS beads. Among all the protocols, the digestion using KOH (10% w/v, 60 °C) (KOH-digestion) had no effect on the fluorescence intensity, morphology and composition of the three fluorescent PS beads. Moreover, the extraction efficiency ≥ 95.3 ±â€¯0.2% of fluorescent PS beads in Daphnia magna and zebrafish, confirming its feasibility in fluorescent PS beads quantitative analysis. However, the fluorescence intensities of fluorescent PS beads digested by other five protocols were significantly decreased, as well as the change of morphology and composition on fluorescent PS beads. Overall, the KOH-digestion is an optimal protocol for extracting fluorescent PS beads in biological samples.

Pyrolysis of Arundo donax L. to produce pyrolytic vinegar and its effect on the growth of dinoflagellate Karenia brevis.

Harmful algal blooms (HABs) have become global environmental issues, and the demand for alternative algaecides is urgent. Pyrolytic vinegars (PVs) were pyrolyzed from giant reed at 300-600°C to investigate the underlying mechanisms of their inhibitory effect on the red tide dinoflagellate Karenia brevis by sub-chronic toxicity experiments. The major components of PVs were acetic acid, phenols, aldehyde, ketone, and esters. The 96h median effective concentration (96h-EC50) values of PVs were 0.65-1.08mLL-1, and PV300 showed the strongest inhibitory effect. The increased contents of reactive oxygen species (ROS) and malondialdehyde, antioxidant enzymes activities indicated that K. brevis cells were suffering from oxidative stress, leading to lipid oxidation and cell structure damage. The sites of ROS accumulation in the treated cells were chloroplasts and mitochondria. These results suggest the suitability of PVs as potential algaecides for HAB control, and also provide a new direction for biomass valorization.

Comparative toxicity of the plasticizer dibutyl phthalate to two freshwater algae.

Phthalate esters (PAEs), a family of emerging environmental contaminants, have been frequently detected in soils and water. However, intensive studies on the toxicity of PAEs have focused on growth response of terrestrial and aquatic animals, while only limited attention has been paid to aquatic plants, especially phytoplankton, the primary producer in aquatic ecosystems. Therefore, the acute toxic effects and underlying mechanisms of dibutyl phthalate (DBP) at different concentrations (0-20mgL-1) on two typical freshwater algae (Scenedesmus obliquus and Chlorella pyrenoidosa) were investigated. The growth of S. obliquus and C. pyrenoidosa was conspicuously inhibited by DBP exposure at 2-20mgL-1. The 96-h median effective concentration values (96h-EC50) were 15.3mgL-1 and 3.14mgL-1 for S. obliquus and C. pyrenoidosa, respectively, implying that the spherical C. pyrenoidosa is more sensitive to DBP than the spindle-shaped S. obliquus. As expected from the damage done to cell organelles (i.e. cell membranes, chloroplasts, and protein rings), cell densities and chlorophyll content conspicuously decreased under DBP treatments. Moreover, the algal growth inhibition was closely linked to the increased production of intracellular reactive oxygen species and malondialdehyde content, indicating oxidative stress and lipid peroxidation in both algae. This was proved by the increased activity of antioxidant enzymes such as superoxide dismutase and catalase. Our findings will contribute to the understanding of toxic mechanisms in PAEs and the evaluation of environmental risks for primary producers in aquatic ecosystems.