Large quantities of lead/zinc (Pb/Zn) mine tailings were deposited at tailings impoundments without proper management, which have posed considerable risks to the local ecosystem and residents in mining areas worldwide. Therefore, the geochemical behaviors of potentially toxic elements (PTEs) in tailings were in–depth investigated in this study by a coupled use of batch kinetic tests, statistical analysis and mineralogical characterization. The results indicated that among these studied PTEs, Cd concentration fluctuated within a wide range of 0.83–6.91 mg/kg, and showed the highest spatial heterogeneity. The mean Cd concentrations generally increased with depth. Cd were mainly partitioned in the exchangeable and carbonate fractions. The release potential of PTEs from tailings was ranged as: Cd > Mn > Zn > Pb > As, Cd > Pb > Zn > Mn > As and Cd > Pb > Mn > Zn > As, respectively, under the assumed environmental scenarios, i.e. acid rain, vegetation restoration, human gastrointestinal digestion. The results from mineralogical characterization indicated that quartz, sericite, calcite and pyrite were typical minerals, cumulatively accounting for over 80% of the tailings. Sulfides (arsenopyrite, galena, and sphalerite), carbonates (calcite, dolomite, cerussite and kutnahorite), oxides (limonite) were identified as the most relevant PTEs–bearing phases, which significantly contributed to PTEs release from tailings. A combined result of statistical, geochemical and mineralogical approaches would be provided valuable information for the alteration characteristics and contaminant release of Pb/Zn mine tailings.

Heavy metal or metalloid contamination is a common problem in soils of urban environments. Their introduction can be due to unpremeditated anthropogenic activities like atmospheric deposition produced by diffuse sources, construction activities and landscape maintenance. Phytoremediation is a rapidly evolving, sustainable approach to remediate the contaminated lands where metals and metalloids are highly persistent in the environment. The present work sets out to determine the level of 12 heavy metals and metalloids (As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb and Zn) in soil and their accumulation by plant foliage found in nature parks and industrial sites in Singapore. The latter also involve the investigation of the remediation capacity of selected tropical plant species found at the sampling sites. The study is done using digestion and inductively coupled plasma-optical emission spectrometry. Eleven soil sampling sites across Singapore with 300 sampling points were selected, where soil (0–10 cm) and plant foliage samples were collected. Bioconcentration factors were determined to assess the phytoremediation potential of the collected plant species. Toxicity risk of heavy metals were assessed by comparing the target and intervention values from the soil quality guidelines by the Dutch Standard. Results of the study revealed there were regions where levels of heavy metals and metalloids were relatively high and could affect the environment and the health of flora and fauna in Singapore. Our study discovered that there were available tropical plant species (e.g., wildflowers, ferns and shrubs) which could potentially play a significant role in the remediation of contaminated lands that could open up a huge possibility of developing a sustainable and environmentally-friendly way of managing this emerging urban problem. Results showed that 12 plant species, including hyperaccumulator like Pteris vittata, Centella asiatica, were effective for the accumulation of heavy metals and metalloids.

In recent years, pollution of antibiotics and heavy metal has often been reported in organic wastes. Saprophytic insects have been recorded as biological control agents in organic waste management. During organic waste conversion, the intestinal bacteria of the saprophytic insects play an important role in digestion, physiology, immunity and prevention of pathogen colonization. Black soldier fly (BSF) Hermetia illucens has been widely used as saprophytic insects and showed tolerance to sulfonamides (SAs) and cadmium (Cd). Diversity and changes in gut microbiota of black soldier fly larvae (BSFL) were evaluated through 16S rRNA high-throughput sequencing, and a decrease in diversity of gut microbiota along with an increase in SAs stress was recorded. Major members identified were Actinomycetaceae, Enterobacteriaceae, and Enterococcaceae. And fourteen multi-resistance Klebsiella pneumoniae strains were isolated. Two strains BSFL7-B-5 (from middle midgut of 7-day BSFL) and BSFL11-C-1 (from posterior midgut of 11-day BSFL) were found to be low-toxic and multi-resistance. The adsorption rate of SAs in 5 mg/kg solutions by these two strains reached 65.2% and 61.6%, respectively. Adsorption rate of Cd in 20 mg/L solutions was 77.2% for BSFL7-B-5. The strain BSFL11-C-1 showed higher than 70% adsorption rates of Cd in 20, 30 and 40 mg/L solutions. This study revealed that the presence of multi-resistance bacterial strains in the gut of BSFL helped the larvae against SAs or Cd stress. After determining how and where they are used, selected BSFL gut bacterial strains might be utilized in managing SAs or Cd contamination at suitable concentrations in the future.

The unified bioaccessibility method (UBM) was harnessed to assess in vitro oral bioaccessibility pools of dialkyl phthalate congeners (with methyl, –ethyl, –butylbenzyl, –n-butyl, –2-ethylhexyl, and –n-octyl moieties) and bisphenol A at the 17 μg g⁻¹ level in beach sand contaminated with polyethylene microplastics. A variety of sample preparation approaches prior to the analysis of the UBM gastrointestinal extracts, including traditional methods (protein precipitation, liquid-liquid extraction, and solid-phase extraction) and dispersive liquid-liquid microextraction (DLLME) were comprehensively evaluated for clean-up and analyte enrichment. DLLME was chosen among all tested approaches on account of the high extraction efficiency (73–95%, excluding bis(2-ethylhexyl)phthalate and di-n-octyl phthalate), high sample throughput (∼7 min per set of samples), and environmental friendliness as demonstrated by the analytical eco-scale score of 83, and the green analytical procedure index pictogram with green/yellow labeling. The release of the less hydrophobic plastic-laden compounds (dimethyl phthalate, diethyl phthalate and bisphenol A) from the contaminated sample into the body fluids was significant, with bioaccessibility values ranging from 30 to 70%, and from 43 to 74% in gastric and gastrointestinal fluids, respectively, and with relative standard deviation < 17% in all cases. The majority of the compounds were leached during gastric digestion, likely as the combined action of the low pH and the gastric enzymes. The risk exposure analysis revealed that accumulation/concentration in the body fluids is potentially relevant for dimethyl phthalate, diethyl phthalate and bisphenol A, with relative accumulation ratios ranging from 1.1 ± 0.1 to 2.6 ± 0.4. The average daily intake values for the suite of compounds, corrected with the bioaccessibility fraction, ranged from 60 to 430 ng kg of body weight⁻¹·day⁻¹, in all cases, far below the tolerable daily intakes, thus indicating the lack of children health risk by ingestion of microplastic-laden sand with elevated concentrations of plasticizers.

Microplastic (MP) contamination is present in the entire marine environment from the sediment to the water surface and down to the deep sea. This ubiquitous presence of MP particles opens the possibility for their ingestion by nearly all species in the marine ecosystem. Reports have shown that MP particles are present in local commercial seafood species leading to the possible human ingestion of these particles. However, due to a lack of harmonized methods to identify microplastics (MPs), results from different studies and locations can hardly be compared. Hence, this study was aimed to detect, quantify, and estimate MP contamination in commercially important mussels originating from 12 different countries distributed worldwide. All mussels were obtained from supermarkets and were intended for human consumption. Using a combinatorial approach of focal plane array (FPA)-based micro- Fourier-transform infrared (FTIR) spectroscopy and micro-Raman spectroscopy allowed the detection and characterization of MP down to a size of 3 μm in the investigated mussels. Further, a gentle sample purification method based on enzymes has been modified in order to optimize the digestion of organic material in mussels. A random forest classification (RFC) approach, which allows a rapid discrimination between different polymer types and thus fast generation of data on MP abundance and size distributions with high accuracy, was implemented in the analytical pipeline for IR spectra. Additionally, for the first time we also applied a RFC approach for the automated characterization of Raman spectra of MPs.

Microplastics represent an emerging environmental issue and have been found almost everywhere including seafood, raising a great concern about the ecological and human health risks they pose. This study addressed the common technical challenges in the assessment of microplastics in seafood by developing an improved protocol based on Raman spectroscopy and using the green-lipped mussel Perna viridis and the Japanese jack mackerel Trachurus japonicus as the test models. Our findings identified a type of stainless-steel filter membranes with minimal Raman interference, and a combination of chemicals that achieved 99–100% digestion efficiency for both organic and inorganic biomass. This combined chemical treatment reached 90–100% recovery rates for seven types of microplastics, on which the surface modification was considered negligible and did not affect the accuracy of polymer identification based on Raman spectra, which showed 94–99% similarity to corresponding untreated microplastics. The developed extraction method for microplastics was further combined with an automated Raman mapping approach, from which our results confirmed the presence of microplastics in P. viridis and T. japonicus collected from Hong Kong waters. Identified microplastics included polypropylene, polyethylene, polystyrene and poly(ethylene terephthalate), mainly in the form of fragments and fibres. Our protocol is applicable to other biological samples, and provides an improved alternative to streamline the workflow of microplastic analysis for routine monitoring purposes.

The industrial production of insects for waste management or as a protein source is becoming vital to our society. Large volumes of manure are produced by concentrated animal facilities around the globe that must be managed, utilized, and disposed of properly. Flies offer a partial solution with their abilities to reduce these wastes and heavy metal pollutants. Meat and crop proteins are being supplemented by insect proteins for many feeds across the globe, yet science-based studies behind the mass-rearing of insects are still in their infancy. In the current study, the percent change in the composition of nutrients, heavy metals, and fiber, in dairy, poultry, and swine manure degraded by either black soldier fly (BSF) or house fly (HF) larvae was explored. Pre-digested and post-digested manure samples were collected from four independent studies that differed in production scale (number of larvae and feeding regimen): 1) BSF small-scale (100 larvae fed incrementally), 2) HF small-scale (100 larvae fed incrementally), 3) BSF large-scale (10,000 larvae fed a single time), and 4) HF large-scale (4,000 larvae fed a single time). Results indicate that nitrogen is a key nutrient impacted by larval digestion of manure by both species, regardless of scale. However, scale significantly impacted reductions of other nutrients, as did the type of manure in which the insects were reared. Ultimately, this study demonstrated that manure type and rearing scale impact the ability of BSF and HF larvae to reduce nutrients and heavy metals in manure, and thus insect management procedures need to be congruent with production emphases of the insects for waste management or protein products. Failure to take scale into consideration could lead to inaccurate assumptions related to industrialized efforts on this topic.

Mercury (Hg) is commonly extracted from solid phase samples using aqua regia for total Hg (tHg) analysis. However, uncertainties exist regarding the complete extraction of Hg by aqua regia, especially from carbonaceous materials. To investigate whether aqua regia can completely extract Hg from biochars, batch-style experiments were carried out to evaluate extraction efficiency of aqua regia with respect to Hg-loaded biochar and to characterize the residual Hg speciation and spatial distribution. Different types of biochars (raw, FeCl₃-modified, and FeSO₄-modified, prepared at different temperatures) were reacted with Hg-spiked solution before the digestion experiments. Adsorption analyses indicate the biochars were successfully loaded with Hg and that the Hg content was higher in biochars pyrolyzed at higher temperature (900 versus 300 or 600 °C). The results of digestion experiments indicate Hg could not be completely extracted from the biochars tested, with a greater percentage of residual Hg in biochars pyrolyzed at 600 (60 ± 15%) and 900 (75 ± 22%) than 300 °C (7 ± 2%). Furthermore, the fraction of residual Hg in FeSO₄-modified biochars after aqua regia digestion was significantly lower than in FeCl₃-modified and unmodified biochars. Confocal micro-X-ray fluorescence imaging (CMXRFI) showed residual Hg in biochars is concentrated on surfaces prior to digestion, but more homogeneously distributed after digestion, which indicates Hg on biochar surface is more easily digested. Hg extended X-ray absorption fine structure (EXAFS) spectra modelling showed residual Hg in biochars mainly exists as Hg(II)–Cl. These results indicate extra caution should be paid for tHg determinations using aqua regia digestion method in soil (especially in forest), sediment, and peat samples containing black carbon, activated carbon, or biochar.

Antimony (Sb) widely occurs in plastics as a pigment and reaction residue and through the use and recycling of electronic material enriched in Sb as a flame retardant synergist. In this study, clean estuarine sediment has been contaminated by different microplastics prepared from pre-characterised samples of different types of plastic (including a rubber) containing a range of Sb concentrations (256–47,600 μg g⁻¹). Sediment-plastic mixtures in a mass ratio of 100:1 were subject to 6-h extractions in seawater and in seawater solutions of a protein (bovine serum albumin; BSA) and a surfactant (taurocholic acid; TA) that mimic the digestive conditions of coastal deposit-feeding invertebrates. Most time-courses for Sb mobilisation could be defined by a second-order diffusion equation, with rate constants ranging from 44.6 to 0.0216 (μg g⁻¹)⁻¹ min⁻¹. Bioaccessibilities, defined as maximum extractable concentrations throughout each time course relative to total Sb content, ranged from <0.01% for a polycarbonate impregnated with Sb as a synergist exposed to all solutions, to >1% for acrylonitrile butadiene styrene containing a Sb-based colour pigment exposed to solutions of BSA and TA and recycled industrial polyethylene exposed to BSA solution. The potential for Sb to bioaccumulate or elicit a toxic effect is unknown but it is predicted that communities of deposit-feeders could mobilise significant quantities of Sb in sediment contaminated by microplastics through bioturbation and digestion.

Soil and sludge are important pools for microplastics (MPs), however standard separation methods for MPs from these pools are still missing. We tested the widely used methods for MPs extraction from water and sediment to six agriculture surface soils and three sewage sludges from municipal wastewater treatment plants and included an additional pre-digestion procedure with 30% H₂O₂ before floatation to remove soil or sludge organic matter (OM). Extraction efficiency of MPs were evaluated under different separation conditions, including floatation solution (NaCl, ZnCl₂, and NaI), filtration membrane, and oxidation solution. Results showed that H₂O₂ pre-digestion significantly increased MPs extraction in soil and sludge, especially the samples with high OM contents, particularly sludge. Floatation solution with higher densities recovered more MPs. The extra released MPs were mainly small fibrous MPs, probably because they are easily retained by aggregates. Our results provide an feasible separation method for MPs in soil and sludge, i.e., pre-digestion with 30% H₂O₂ at 70 °C, floatation with NaI solution, filtration through nylon membrane, and further oxidation with 30% H₂O₂ + H₂SO₄ or 30% H₂O₂ at 70 °C. About 420–1290 MP items/kg soil were detected in soil samples, while much higher numbers (5553–13460 MP items/kg) were found in sludge samples. The dominate morphology of MPs was white fiber with a size of 0.02–0.25 mm, while the main types of MPs, identified by a micro-Fourier transformed infrared spectroscopy (μ-FTIR), were polyethylene and polypropylene in soil samples and polyethylene, polyethylene terephthalate, and polyacrylonitrile in sludge samples.