Microplastics from face mask impairs sperm motility.

The COVID-19 pandemic has resulted in unprecedented plastic pollution from single-used personal protective equipment (PPE), especially face masks, in coastal and marine environments. The secondary pollutants, microplastics from face masks (mask MP), rise concern about their detrimental effects on marine organisms, terrestrial organisms and even human. Using a mouse model, oral exposure to mask MP at two doses, 0.1 and 1 mg MP/day for 21 days, caused no change in animal locomotion, total weight, or sperm counts, but caused damage to sperm motility with increased curvilinear velocity (VCL). The high-dose mask MP exposure caused a significant decrease in linearity (LIN) of sperm motility. Further testicular transcriptomic analysis revealed perturbed pathways related to spermatogenesis, oxidative stress, inflammation, metabolism and energy production. Collectively, our findings substantiate that microplastics from face masks yield adverse effects on mammalian reproductive capacity, highlighting the need for improved plastic waste management and development of environmentally friendly materials.

Size-dependent deleterious effects of nano- and microplastics on sperm motility.

INTRODUCTION: Growing concerns regarding the reproductive toxicity associated with daily life exposure to micro-/nano-plastics (abbreviated as MNPs) have become increasingly prevalent. In reality, MNPs exposure involves a heterogeneous mixture of MNPs of different sizes rather than a single size. METHODS: In this study, an oral exposure mouse model was used to evaluate the effects of MNPs of four size ranges: 25-30 nm, 1-5 µm, 20-27 µm, and 125-150 µm. Adult male C57BL/6 J mice were administered environmentally relevant concentrations of 0.1 mg MNPs/day for 21 days. After that, open field test and computer assisted sperm assessment (CASA) were conducted. Immunohistochemical analyses of organ and cell type localization of MNPs were evaluated. Testicular transcriptome analysis was carried out to understand the molecular mechanisms. RESULTS: Our result showed that MNPs of different size ranges all impaired sperm motility, with a decrease in progressive sperm motility, linearity and straight-line velocity of sperm movement. Alterations did not manifest in animal locomotion, body weight, or sperm count. Noteworthy effects were most pronounced in the smaller MNPs size ranges (25-30 nm and 1-5 µm). Linear regression analysis substantiated a negative correlation between the size of MNPs and sperm curvilinear activity. Immunohistochemical analysis unveiled the intrusions of 1-5 µm MNPs, but not 20-27 µm and 125-150 µm MNPs, into Leydig cells and testicular macrophages. Further testicular transcriptomic analysis revealed perturbations in pathways related to spermatogenesis, oxidative stress, and inflammation. Particularly within the 1-5 µm MNPs group, a heightened perturbation in pathways linked to spermatogenesis and oxidative stress was observed. CONCLUSIONS: Our data support the size-dependent impairment of MNPs on sperm functionality, underscoring the pressing need for apprehensions about and interventions against the escalation of environmental micro-/nano-plastics contamination. This urgency is especially pertinent to small-sized MNPs.

The influences of spatial-temporal variability and ecological drivers on microplastic in marine fish in Hong Kong.

This study examined microplastic (MP) occurrence and abundance in marine fish collected from the western and eastern waters of Hong Kong during the wet and dry seasons. Over half (57.1%) of the fish had MP in their gastrointestinal (GI) tracts, with overall MP abundance ranging from not detected to 44.0 items per individual. Statistical analysis revealed significant spatial and temporal differences in MP occurrence, with fish from more polluted areas having a higher likelihood of MP ingestion. Additionally, fish collected in the west during the wet season had significantly higher MP abundance, likely due to influence from the Pearl River Estuary. Omnivorous fish had significantly higher MP counts than carnivorous fish, regardless of collection location or time. Body length and weight were not significant predictors of MP occurrence or abundance. Our study identified several ecological drivers that affect MP ingestion by fish, including spatial-temporal variation, feeding mode, and feeding range. These findings provide a foundation for future research to investigate the relative importance of these factors in governing MP ingestion by fish in different ecosystems and species.

Quantitative analysis and risk assessment to full-size microplastics pollution in the coastal marine waters of Hong Kong.

Given the potential risk to the ecosystem, attention has increased in recent decades to the contamination of the aquatic environment by microplastics (MPs). Due to the limitations of conventional analysis methods of MPs, little is known about the size distribution and abundance of a full-size MPs from 1 µm to 5 mm. The present study quantified MPs with size ranges of 50 µm - 5 mm and 1-50 µm in the coastal marine waters from twelve locations in Hong Kong using fluorescence microscopy and flow cytometry respectively, during the end of wet (September 2021) and dry (March 2022) seasons. The average abundance of MPs with size ranges of 50 µm - 5 mm and 1-50 µm from twelve sampling locations marine surface waters were found ranging from 27 to 104 particles L-1 and 43,675-387,901 particles L-1 in the wet season respectively, and 13-36 particles L-1 and 23,178-338,604 particles L-1 in the dry season respectively. Significant temporal and spatial variations of small MPs abundance might be observed at the sampling locations, which were contributed by the influences of the estuary of Pearl River, sewage discharge points, land structure, and other anthropogenic activities. Based on the MPs abundance information, ecological risk assessment was conducted and revealed that the small MPs (< 10 µm) in coastal marine surface waters may pose potential health risks to aquatic organisms. Additional risk assessments are needed in order to determine whether or not the MPs exposure would cause health risks to the public.

A short review on the recent method development for extraction and identification of microplastics in mussels and fish, two major groups of seafood.

The prevalence of microplastics in the marine environment poses potential health risks to humans through seafood consumption. Relevant data are available but the diverse analytical approaches adopted to characterise microplastics have hampered data comparison among studies. Here, the techniques for extraction and identification of microplastics are summarised among studies of marine mussels and fish, two major groups of seafood. Among the reviewed papers published in 2018-2021, the most common practice to extract microplastics was through tissue digestion in alkaline chemicals (46 % for mussels, 56 % for fish) and oxidative chemicals (28 % for mussels, 12 % for fish). High-density solutions such as sodium chloride could be used to isolate microplastics from other undigested residues by flotation. Polymer analysis of microplastics was mainly carried out with Fourier-transform infrared (FTIR) spectroscopy (58 % for both mussels and fish) and Raman spectroscopy (14 % for mussels, 8 % for fish). Among these methods, we recommend alkaline digestion for microplastic extraction, and the automated mapping approach of FTIR or Raman spectroscopy for microplastic identification. Overall, this study highlights the need for a standard protocol for characterising microplastics in seafood samples.

Macroalgal morphology mediates microplastic accumulation on thallus and in sediments.

The accumulation process of microplastics (MPs) is a key to understanding their fate in the environment. However, there is limited information about the short-term accumulation of MPs on macrophytes. The ability of macrophyte to attenuate wave and reduce current velocity is potentially facilitating MPs deposition. We hypothesize that the macroalgae retain MPs with their morphologies (filamentous and non-filamentous) being one of the factors to govern retention. Our hypothesis was tested by field observation during the dry season in Hong Kong when the macroalgae communities were the most diverse. MPs per biomass, surface area, or interstitial volume were used to represent the abundances on macroalgae. We found that filamentous algae retained a 2.35 times higher number of MPs when compared with non-filamentous algae if unit per biomass was considered. Other units, however, showed insignificant differences in MPs abundances between algal morphologies. Fibre was the most dominant shape of MPs with no significant difference in their abundances between filamentous and non-filamentous algae, suggesting fibres were retained regardless of the algal morphologies. To further evaluate the potential accumulation in the environment, sediment samples were also collected under the algal mat and immediate vicinity (~50 cm) of the algal mat. We found that sediment collected under the vegetated area contained significantly higher MPs. This was 3.39 times higher than the unvegetated area. Sediment collected under/near filamentous algae retained much higher abundances of MPs than those of non-filamentous algae. Provided that the observed retention of MPs on macroalgae, we speculate macrophyte system is one of the short-term MPs accumulation hotspots where the temporal increase of MPs depends on the seasonality of macrophyte in a given region.

Fate and Effects of Macro- and Microplastics in Coastal Wetlands.

Coastal wetlands trap plastics from terrestrial and marine sources, but the stocks of plastics and their impacts on coastal wetlands are poorly known. We evaluated the stocks, fate, and biological and biogeochemical effects of plastics in coastal wetlands with plastic abundance data from 112 studies. The representative abundance of plastics that occurs in coastal wetland sediments and is ingested by marine animals reaches 156.7 and 98.3 items kg-1, respectively, 200 times higher than that (0.43 items kg-1) in the water column. Plastics are more abundant in mangrove forests and tidal marshes than in tidal flats and seagrass meadows. The variation in plastic abundance is related to climatic and geographic zones, seasons, and population density or plastic waste management. The abundance of plastics ingested by pelagic and demersal fish increases with fish length and dry weight. The dominant characteristics of plastics ingested by marine animals are correlated with those found in coastal wetland sediments. Microplastics exert negative effects on biota abundance and mangrove survival but positive effects on sediment nutrients, leaf drop, and carbon emission. We highlight that plastic pollution is widespread in coastal wetlands and actions are urged to include microplastics in ecosystem health and degradation assessment.

Bisphenol A and its analogues in sedimentary microplastics of Hong Kong.

The occurrence and spatial distribution of bisphenol A (BPA) and analogues bisphenol B (BPB), bisphenol F (BPF) and bisphenol S (BPS) were investigated in microplastic on 11 beaches in Hong Kong. At 10 sites, BPA was the only detected chemical with concentrations ranged from 82.4-989 ng g-1 microplastic. BPA, BPB and BPS co-occurred at only one site, where it is located close proximity to the outfall of a sewage treatment plant. There was no significant spatial difference of BPA concentrations in microplastic when all the sites were considered, indicating that some remote and presumably cleaner beaches have been contaminated. PE, PP and PS (represented >90% of total polymers) were the most dominated polymers, but there was no correlation between polymer types and BPA concentrations. No evidence was found that the BPA and its analogues accumulate on microplastic since the concentrations were comparable to those found in the sediment.

Effects of rubble zones from oyster cultivation on habitat utilization and foraging behaviour of the endangered tri-spine horseshoe crab: An implication for intertidal oyster cultivation practices.

Estuarine structured habitats, including benthic cultivation structure, are widely cited as substantial nursery and feeding grounds for fish and macroinvertebrates. Activities such as locomotion and foraging behaviour of sediment-dwelling species, however, may be hindered in the presence of the obstacles. In this study, collected field evidence demonstrated that habitat utilization of the juvenile tri-spine horseshoe crab Tachypleus tridentatus, an iconic and endangered macroinvertebrate, was adversely affected by high-density intertidal oyster rubble zones. Despite the fact that the utilization area of individual juvenile horseshoe crabs was independent of the presence of these obstacles, the abundance and number of positional fixes of tagged juveniles in these areas were lower. The effects of these obstacles and their associated topographic changes on the movement of the juvenile horseshoe crabs was investigated in a simulated laboratory experiment. Both the simulated oyster cultches and hummocks formed between the cultches reduced the total distance and displacement of the feeding trail, and less juveniles preferred to forage on elevated, dry hummocks (dry at low tide) formed between the cultches. Our findings suggested that oyster cultches and rubbles reduced the habitat quality for juvenile horseshoe crabs. On-bottom oyster cultivation activities seeking to conserve horseshoe cabs by avoiding nursery habitats should instead consider off-bottom or offshore cultivation methods.

Characterisation of an unexplored group of microplastics from the South China Sea: Can they be caused by macrofaunal fragmentation?

Research on plastics fragmentation is important for the estimation of amount of microplastics but the biological causes for fragmentation have not been acknowledged. From microplastics collected in the beaches of Hong Kong, we revealed an abnormal type of fragment which has not been reported before. These fragments, composing about 6% of the microplastics (pellet, foam, bead, fragment) collected, were interestingly triangular in shape with at least two of the three sides being characteristically straight and resembling a cut made by compression. Objective observations have distinguished these "trimmed triangular fragments" to those triangular fragments that were fractured randomly. By comparing with additional evidence, we proposed that these trimmed fragments were the daughter pieces of macrofaunal biting. If this was so, there would be wide implications on fragmentation modeling studies for microplastics since active biting of large plastic debris has generally not been considered as a factor of plastics fragmentation.

Heavy metals contamination of sedimentary microplastics in Hong Kong.

This is the first study of heavy metals (As, Zn, Cd, Ni, Fe, Mn, Cu) contamination of microplastics on sandy beaches in Hong Kong. Three study sites are located in the eastern waters (Pak Lap Wan, Stanley Bay, Tung Lung Chau) and the other three in the western waters (Tai Pai Tsui, Ha Pak Nai, Shui Hau Wan). The three most abundant types of microplastics were polyethylene (42.2%), polypropylene (23.3%) and polystyrene (19.5%). The median concentration of Fe (302 mg kg-1) was the highest and followed by Zn (19.6 mg kg-1) and Mn (18.6 mg kg-1). Very low concentrations of Cu (0.89 mg kg-1), Ni (0.15 mg kg-1), As (

Impacts of Typhoon Mangkhut in 2018 on the deposition of marine debris and microplastics on beaches in Hong Kong.

Storm surge and waves associated with tropical cyclones carry significant amounts of pollutants into the marine environment. This study evaluated the effects of Typhoon Mangkhut (7-18 September 2018) on marine debris pollution including macro-debris (>2.5 cm) and microplastics (5 µm-5 mm) in Hong Kong. Sampling was repeated on four beaches, two each from protected and exposed coastal areas, spanning from the eastern to western waters before and after the cyclone. For macro-debris, an average density of 0.047 items m-2 and 0.54 items m-2 was obtained before and after the cyclone, respectively or an 11.4-fold increase, with plastic being the most dominant type (61.9-93.3% and 80.7-92.4% before and after the cyclone, respectively) among total beached debris in all four beaches. Likewise, higher mean microplastic abundances were found in the post-cyclone period (335 items kg-1 sediment) when compared with the pre-cyclone period (188 items kg-1 sediment). The depositional dynamics for both macro-debris and microplastic were site-specific due to factors such as wind direction and the associated storm surge, topography and orientation of the site, and proximity to urban areas. This study has demonstrated the role cyclone induced overwash plays on introducing plastic pollution to beach environments. Considering an increase in both the intensity and frequency of cyclone in the future due to global warming, and a tremendous increase in marine plastic debris, more research effort should be spent on this understudied problem.

Microplastics in invertebrates on soft shores in Hong Kong: Influence of habitat, taxa and feeding mode.

Microplastic (MP) pollution in the marine environment has gained much concern in recent years. This study investigated the occurrence of MPs in invertebrates collected on 18 mudflats and sandy beaches in Hong Kong and its relationships to biological taxon, feeding mode and habitat. In total 38 species of gastropods, bivalves and crabs were collected and the mean number of suspected microplastics ranged from 0 to 9.68 particles g-1 wet weight or 0 to 18.4 particles individual-1. Around 26% of the suspected microplastics were confirmed to be synthetic polymers, including CP (cellophane), PET (polyethylene terephthalate), and PA (polyamide). Microplastic fibres were the most abundant type of MPs, followed by pellets. Significantly higher abundance of suspected microplastics was found in gastropods. Since MP abundance might vary with taxon, it is recommended to include different taxonomic groups in any ecological assessment of the impact of MPs.

Field test of beach litter assessment by commercial aerial drone.

The visual survey is the most common method to quantify and characterize beach litter. However, it is very labor intensive and difficult to carry out on beaches which are remote or difficult to access. We suggest an alternative approach for assessing beach litter using an unmanned aerial vehicle (UAV), or aerial drone, with automated image requisition and processing. Litter of different sizes, colours, and materials were placed randomly on two beaches. Images of beaches with different substrates were obtained by the drone at different operating heights and light conditions and litter on the beaches was identified from the photos by untrained personnel. The quantification of beach litter using the drone was three times faster than that by visual census. This study has demonstrated the potential of using the drone as a cost-effective and an efficient sampling method in routine beach litter monitoring programs.

Spatial distribution and source identification of hydrophobic organic compounds (HOCs) on sedimentary microplastic in Hong Kong.

The spatial distribution, composition and source of hydrophobic organic compounds (HOCs) including polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs) of the sedimentary microplastics (0.25-5 mm) in Hong Kong were investigated. The concentration of ΣPAHs ranged between 70.8 and 1509 ng g-1 with inter-site differences although the regional difference was insignificant, indicating localised pyrolytic and petrogenic input of PAHs. The concentration of ΣPCBs (13-1083 ng g-1) varied with both study sites and regions with higher concentrations obtained in the western waters, possibly due to the input from Pearl River. Significantly higher concentrations of OCPs on eastern shores highlighted fishing and aquaculture activities in South China Sea a potential major source of OCPs. DDT and its metabolites (DDX, ranged from 1.96 to 626 ng g-1) were the dominant forms of OCPs (45%-80%). Since most of the DDX existed as DDT, this suggested that there was a fresh input of DDT into the microplastics. As microplastics and HOCs cannot be removed effectively from the environment, reduction of potential ecotoxicological risks should rely on minimizing the use of plastics and HOCs.

Ruthenium-indolizinone complexes as a new class of metalated heterocyclic compounds: insight into unconventional alkyne activation pathways, revelation of unexpected electronic properties and exploration of medicinal application.

The two series of ruthenium-indolizinone complexes prepared by Ru-mediated cyclization of pyridine-tethered alkynes represent the first examples of metalated indolizinone complexes. Joint experimental-theoretical investigation suggests an unconventional 5-endo-dig cyclization pathway as their formation mechanism. They also exhibit moderate cytotoxicity against several human cancer cell lines.

Comparisons of microplastic pollution between mudflats and sandy beaches in Hong Kong.

Most of the previous studies of microplastic pollution on coastal habitats focused on high energy beaches although low energy areas such as mudflats are supposed to retain more microplastics, not to mention that mudflats are biologically more diverse. We quantified and characterized microplastics from 10 mudflats and 10 sandy beaches in Hong Kong spanning from the eastern to western waters. Sediment samples were collected at 1.0 m and 1.5 m above chart datum (CD) and at the strandline. Abundance of microplastics ranged between 0.58 and 2116 items kg-1 sediment with that on mudflats being ten times more than on beaches. Polyethylene (46.9%) was the most abundant and followed by polypropylene (13.8%) and polyethylene terephthalate (13.5%). Expanded polystyrene was the most abundant in the strandline samples but not at 1.0 m and 1.5 m above CD. Although previous studies have concluded that the input from Pearl River is a major source of microplastics on Hong Kong shores, this study has demonstrated that the contribution of local pollution sources such as discharge from sewage treatment plants to microplastic pollution should not be neglected.

Metalated Chromene and Chromone Complexes: pH Switchable Metal-Carbon Bonding Interaction, Photo-triggerable Chromone Delivery Application, and Antioxidative Activity.

The two families of RuII -chromene and -chromone complexes isolated in this work represent the first examples of metalated chromene and chromone complexes synthesized through transition-metal-mediated cyclization of phenol-tethered ynone. These unprecedented metalated heterocyclic compounds exhibit remarkable features, such as pH-switchable metal-carbon bonding interactions, photo-triggerable release of organic chromone upon visible-light irradiation, and superior antioxidative property to their organic analogue (1,4-benzopyrone). These findings not only offer mechanistic insights into metal-induced activation of functionalized alkynes, but also add a new dimension to rational design of antioxidants and photo-responsive drug delivery systems.

Rapid visual and spectrophotometric nitrite detection by cyclometalated ruthenium complex.

Quantitative determination of nitrite ion (NO2-) is of great importance in environmental and clinical investigations. A rapid visual and spectrophotometric assay for NO2- detection was developed based on a newly designed ruthenium complex, [Ru(npy)([9]aneS3)(CO)](ClO4) (denoted as RuNPY; npy = 2-(1-naphthyl)pyridine, [9]aneS3 = 1,4,7-trithiacyclononane). This complex traps NO+ produced in acidified NO2- solution, and yields observable color change within 1 min at room temperature. The assay features excellent dynamic range (1-840 µmol L-1) and high selectivity, and its limit of detection (0.39 µmol L-1) is also well below the guideline values for drinking water recommended by WHO and U.S. EPA. Practical use of this assay in tap water and human urine was successfully demonstrated. Overall, the rapidity and selectivity of this assay overcome the problems suffered by the commonly used modified Griess assays for nitrite determination.

Luminescent Iridium(III) Complexes Supported by N-Heterocyclic Carbene-based C

Iridium(III) hydrido complexes containing N-heterocyclic carbene (NHC)-based pincer ligand 1,3-bis(1-butylimidazolin-2-ylidene)phenyl anion (C(1)^C^C(1)) or 1,3-bis(3-butylbenzimidazolin-2-ylidene)phenyl anion (C(2)^C^C(2)) and aromatic diimine (2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 4,4'-dimethyl-2,2'-bipyridine (Me2bpy), or dipyrido-[3,2-f:2',3'-h]-quinoxaline (dpq)) in the form of [Ir(C^C^C)(N^N)(H)](+) have been prepared. Crystal structures for these complexes show that the Ir-CNHC distances are 2.043(5)-2.056(5) Å. The hydride chemical shifts for complexes bearing C(1)^C^C(1) (-20.6 to -20.3 ppm) are more upfield than those with C(2)^C^C(2) (-19.5 and -19.2 ppm), revealing that C(1)^C^C(1) is a better electron donor than C(2)^C^C(2). Spectroscopic comparisons and time-dependent density functional theory (TD-DFT) calculations suggest that the lowest-energy electronic transition associated with these complexes (λ = 340-530 nm (ε ≤ 10(3) dm(3) mol(-1) cm(-1))) originate from a dπ(Ir(III)) → π*(N^N) metal-to-ligand charge transfer transition, where the dπ(Ir(III)) level contain significant contribution from the C^C^C ligands. All these complexes are emissive in the yellow-spectral region (553-604 nm in CH3CN and CH2Cl2) upon photo-excitation with quantum yields of 10(-3)-10(-1).