Pollution level and ecological risk assessment of triazine herbicides in Laizhou Bay and derivation of seawater quality criteria.

Triazine herbicides are widely used in agriculture and have become common pollutants in marine environments. However, the spatiotemporal distribution characteristics and water quality criteria (WQC) of triazine herbicides are still unclear. This study found that triazine herbicides had a high detection rate of 100 % in surface seawater of Laizhou Bay, China, with average concentrations of 217.61, 225.13, 21.97, and 1296.72 ng/L in March, May, August, and October, respectively. Moreover, estuaries were important sources, and especially the Yellow River estuary exhibited the highest concentrations of 16,115.86 ng/L in October. The 10 triazine herbicides were detected in the sediments of Laizhou Bay, with a concentration ranging from 0.14-1.68 µg/kg. Atrazine and prometryn accounted for 33.41 %-59.10 % and 28.93 %-50.06 % of the total triazine herbicides in the seawater, and prometryn had the highest proportion (63.50 %) in the sediments. Correlation analysis revealed that triazine herbicides led to the loss of plankton biodiversity, which further decreased the dissolved oxygen. In addition, this study collected 45 acute toxicity data and 22 chronic toxicity data of atrazine, 16 acute toxicity data of prometryn, and supplemented with toxicity experiments of prometryn on marine organisms. Based on the toxicity database, the WQCs of atrazine and prometryn were derived using species sensitivity distribution. The overall risk probability of atrazine and prometryn were both less than 1.75 % in the Laizhou Bay, indicating an acceptable risk. This study not only clarified the pollution status and ecological risk of triazine herbicides, but also provided scientific basis for their environmental management standards.

The wavelength dependence of oxygen-evolving complex inactivation in Zosteramarina.

Zostera marina, a critical keystone marine angiosperm species in coastal seagrass meadows, possesses a photosensitive oxygen evolving complex (OEC). In harsh environments, the photoinactivation of the Z. marina OEC may lead to population declines. However, the factors underlying this photosensitivity remain unclear. Therefore, this study was undertaken to elucidate the elements contributing to Z. marina OEC photosensitivity. Our results demonstrated a gradual decrease in photosystem II performance towards shorter wavelengths, especially blue light and ultraviolet radiation. This phenomenon was characterized by a reduction in Fv/Fm and the rate of O2 evolution, as well as increased fluorescence at 0.3 ms on the OJIP curve. Furthermore, exposure to shorter light wavelengths and longer exposure durations significantly reduced the relative abundance of the OEC peripheral proteins, indicating OEC inactivation. Analyses of light-screening substances revealed that carotenoids, which increased most notably under 420 nm light, might primarily serve as thermal dissipators instead of efficient light filters. In contrast, anthocyanins reacted least to short-wavelength light, in terms of changes to both their content and the expression of genes related to their biosynthesis. Additionally, the levels of aromatically acylated anthocyanins remained consistent across blue-, white-, and red-light treatments. These findings suggest that OEC photoinactivation in Z. marina may be linked to inadequate protection against short-wavelength light, a consequence of insufficient synthesis and aromatic acylation modification of anthocyanins.

Nanoplastics increase the adverse impacts of lead on the growth, morphological structure and photosynthesis of marine microalga Platymonashelgolandica.

Nanoplastics and heavy metals are common pollutants in coastal environments with high concerns, but their joint ecological risk to marine primary productivity remains unclear. In this study, the effects of 7, 70, 700 µg/L lead (Pb) single exposure and in combination with 200 µg/L polystyrene nanoplastics (NPs, 70 nm) on marine microalga Platymonas helgolandica were investigated. Pb single exposure induced a dose-dependent inhibition on the growth of P. helgolandica, which was associated with the reduced photosynthetic efficiency and nutrient accumulation. Compared to Pb single exposure, the addition of NPs significantly reduced the photosynthetic efficiency and aggravated the damage to cell structure. Reduced esterase activity and increased membrane permeability also indicated that NPs exacerbated the adverse effects of Pb on P. helgolandica. Thus, co-exposure to NPs and Pb induced more severe impacts on marine microalgae, suggesting that the joint ecological risk of NPs and heavy metals to marine primary productivity merits more attention.

Efficiency and ecological safety of herbicide haloxyfop-R-methyl on removal of coastal invasive plant Spartina alterniflora.

Spartina alterniflora is a global invasive plant and has caused considerable damage to coastal wetland ecosystem. This study evaluated the efficiency and ecological safety of herbicide haloxyfop-R-methyl (HPME) in removing S alterniflora in Laizhou Bay. The results showed that the density of regenerated S. alterniflora after 10 months of application of 0.01, 0.02 and 0.03 g/m2 HPME decreased by 86.67 %, 99.16 % and 99.31 %, respectively. Moreover, seed abortion rates were 62.25 %, 92.24 % and 94.82 %, and weight of roots in HPME groups were 56.63 %, 59.99 %, and 40.10 % of those in the control group. After 4 days of application, HPME could not be detected in S. alterniflora and sediments. In addition, HPME did not change sediment physicochemical properties, macrozoobenthos community and microbial community structure during 16 days, but increased the density of native macrozoobenthos after 1 year. Therefore, HPME might be an effective and ecologically safe chemical for the eradication of S. alterniflora.

Eelgrass (Zostera marina) and its epiphytic bacteria facilitate the sinking of microplastics in the seawater.

Marine microplastics have received considerable attention as a global environmental issue. However, despite the constant accumulation of microplastics in the ocean, their transport processes and mechanisms remain poorly understood. This study investigated microplastics in the sediments of seagrass meadows and nearby regions without seagrass along the Shandong coast and found that the sediment in the seagrass meadows was a sink for microplastics. Subsequently, we evaluated the influence of eelgrass (Zostera marina), a common coastal seagrass, on the sedimentation of suspended polystyrene microplastics. The results showed that 0.5, 1.0, and 2.0 g/L eelgrass leaves decreased the abundance of microplastics in seawater in a dose-dependent manner over a period of 3-48 h under shaking conditions at 120 rpm at 22 °C. After 48 h of shaking, microplastic abundances in the 0.5, 1.0, and 2.0 g/L eelgrass groups significantly decreased by 46.9%, 53.1%, and 88.4%, respectively. Microplastics can adhere to eelgrass leaves and form biofilms, which promoted the formation of white floc that traps the suspended microplastics, causing them to sink. Furthermore, two epiphytic bacteria (Vibrio and Exiguobacterium) isolated from the eelgrass leaves decreased the abundances of suspended microplastics by 95.7% and 94.5%, respectively, in 48 h by accelerating the formation of biofilms on the microplastics. Therefore, eelgrass and its epiphytic bacteria facilitated the sinking of microplastics and increased the accumulation of microplastics in the sediments of seagrass meadows in coastal regions.

Response of phytoplankton assemblages to nitrogen reduction in the Laizhou Bay, China.

The response of phytoplankton assemblages to decreases in nitrogen loading is an essential index to assess the recovery of aquatic ecosystems from eutrophic status. However, a positive signal is hard to observe from short-term operations considering ecosystem complexity. Here, we used decadal data from the Laizhou Bay, China to track the seasonal and annual variations in phytoplankton assemblages after ammonia reduction in the Xiaoqing and Yellow Rivers. Annual trends show reduced phytoplankton abundance and a decline in harmful algal blooms, indicating the positive recovery of phytoplankton assemblages. Phytoplankton assemblage in the sea region adjacent to the Xiaoqing River shows a lower H' index, higher cell abundance, and higher seasonal variability than the sea region neighbouring the Yellow River. The spatial variability might result from the differences of nitrogen species, runoff and sediment contents between the two rivers; this finding indicates a demand for more aggressive decreases in nitrogen loads.

An effervescence-assisted switchable fatty acid-based microextraction with solidification of floating organic droplet for determination of fluoroquinolones and tetracyclines in seawater, sediment, and seafood.

This study developed a new effervescence-assisted switchable fatty acid-based microextraction combined with solidification of a floating organic-droplet (EA-SFAM-SFO) for simple and rapid determination of fluoroquinolones and tetracyclines in seawater, sediment, and seafood. Five medium-chain fatty acids (pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, and nonanoic acid) were tested as an extraction solvent, given their ability to change between hydrophobic and hydrophilic forms by pH adjustment. As nonanoic acid had the highest extraction recovery (>92%) for the six antibiotics and the ability to transform from liquid to a solidified floating state at low temperature, it was selected as the optimum extraction solvent. The prominent advantages of the newly developed method are: (1) reaction between the procedures salt and fatty acid changed extraction solvent from the hydrophobic to hydrophilic state; (2) bubbling with CO2 greatly increased the contact area between fatty acid and analytes resulting in improved extraction recovery; and (3) solidification of the fatty acid at a low temperature provided good separation and avoided the use of specialized equipment. Single-factor screening and optimization of the main factors were conducted using Plackett-Burman design and central composite design, respectively. The main parameters were optimized as follows: 258 µL fatty acid, 406 µL H2SO4 (98%), 3.9 min vortex time, and 354 µL Na2CO3 (2 mol L-1). Under optimized conditions, limits of detection were 0.007-0.113 µg L-1 or µg kg-1 and extraction recoveries were 82.2%-116.7% for six fluoroquinolone and tetracycline antibiotics in seawater, sediments, and seafood. The newly developed method combines the advantages of effervescence-assisted dispersion, hydrophobic/hydrophilic switchable solvent, and liquid/solid transition induced by low temperature. Overall, the new method is simple, quick, and environment-friendly with low detection limits and high recoveries. Thus, the newly developed method has excellent prospects for sample pretreatment and analysis of antibiotics in marine environmental and food samples. Graphical Abstract ᅟ.

Temporal and spatial distribution of semicarbazide in western Laizhou Bay.

Semicarbazide (SEM), an industrial raw material and the marker residue of nitrofurazone as a veterinary drug, has become a new type of marine pollutant. A standard method (ultra-performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS) was used to analyze SEM in seawater, sediment, and shellfish. A series of sections and stations were set up in radical distribution in western Laizhou Bay, with six voyages and 150 monitoring samples. The concentrations of SEM in seawater and shellfish were 10-11 and 10-10kg/L, respectively, and no SEM was detected in the sediment. Distribution characteristics at each state, temporal and spatial trends, multivariate analyses, and the causes were analyzed to assess the pollution level, which aimed to offer a database for drafting the national baseline values of SEM in seawater and sediment in future. The data obtained could be used for integrated watershed management of marine environment and economic activities for constructing a blue economic zone of Shandong Peninsula in China.

Risk assessment of butyltins based on a fugacity-based food web bioaccumulation model in the Jincheng Bay mariculture area: I. Model development.

A fugacity-based model was developed to simulate the bioaccumulation of butyltins in the food web of the Jincheng Bay mariculture area. The predicted biological tissue residues of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) were 0.04-17.09, 0.14-53.54, and 0.27-108.77 ng-Sn g(-1), respectively, and the predicted values in six mollusca agreed well with the measured ones. The lipid-normalized concentrations did not significantly increase across trophic levels, indicating no biomagnification across aquatic food webs. These results were highly consistent with those observed both in the laboratory and field, which had been reported in numerous references. The explanation, from calculating their flux equilibrium in the food web, was that butyltins were primarily taken in via respiration from the water column by marine organisms. The sensitivities of the model parameters were analyzed, revealing that the hydrophobicity of butyltins played the dominant role in their bioaccumulation phenomena. The verified model predictions of the biotic tissue concentrations of the butyltins could be readily applied to perform internal ecological risk and human health risk assessments in this area.

Risk assessment of butyltins based on a fugacity-based food web bioaccumulation model in the Jincheng Bay mariculture area: II. Risk assessment.

A fugacity-based food web bioaccumulation model was constructed, and the biotic concentrations of butyltins in the food web of the Jincheng Bay mariculture area were estimated accordingly, using the water and sediment concentrations described in the accompanying paper (Part I). This paper presents an ecological risk assessment (ERA) and a human health risk assessment (HHRA) of the butyltins, based on the estimated tissue residues in the marine life in this area. The results showed that the ecological risk probability was greater than 0.05. At this level, management control is critical since sensitive marine species would be profoundly endangered by butyltin contamination. Few if any detrimental effects, however, would be generated for humans from exposure to butyltins through seafood consumption. The fugacity-based model can refine the ERA and HHRA of pollutants in marine areas, provide a basis for protecting marine ecology and the security of fishery products, and thus help determine the feasibility of a proposed aquaculture project.