In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces. © 2005 Elsevier Ltd. All rights reserved.

We aimed to explore the effects of mixtures of lead and various metals on blood pressure (BP) and the odds of pre-hypertension (systolic blood pressure (SBP) 120–139 mmHg, and/or diastolic blood pressure (DBP) 80–89 mmHg) and hypertension (SBP/DBP ≥140/90 mmHg) among Chinese adults in a cross-sectional study. This study included 11,037 adults aged 18 years or older from the 2017–2018 China National Human Biomonitoring. Average BP and 13 metals (lead, antimony, arsenic, cadmium, mercury, thallium, chromium, cobalt, molybdenum, manganese, nickel, selenium, and tin) in blood and urine were measured and lifestyle and demographic data were collected. Weighted multiple linear regressions were used to estimate associations of metals with BP in both single and multiple metal models. Weighted quantile sum (WQS) regression was performed to assess the relationship between metal mixture levels and BP. In the single metal model, after adjusting for potential confounding factors, the blood lead levels in the highest quartile were associated with the greater odds of both pre-hypertension (odds ratio (OR): 1.56, 95% CI: 1.22–1.99) and hypertension (OR:1.75, 95% CI: 1.28–2.40) when compared with the lowest quartile. We also found that blood arsenic levels were associated with increased odds of pre-hypertension (OR:1.31, 95% CI:1.00–1.74), while urinary molybdenum levels were associated with lower odds of hypertension (OR:0.68, 95% CI:0.50–0.93). No significant associations were found for the other 10 metals. WQS regression analysis showed that metal mixture levels in blood were significantly associated with higher SBP (β = 1.56, P < 0.05) and DBP (β = 1.56, P < 0.05), with the largest contributor being lead (49.9% and 66.8%, respectively). The finding suggests that exposure to mixtures of metals as measured in blood were positively associated with BP, and that lead exposure may play a critical role in hypertension development.

Aging is a leading cause of mortality for the elderly and DNA methylation age is reported to be predictive of biological aging. However, few studies have investigated the associations between multiple metals exposure and accelerated aging in the elderly. We performed a pilot study of 288 elderly participants aged 50–115 years and measured genome-wide DNA methylation and 22 blood metals concentrations. Measures of DNA methylation age were estimated using CpGs from Illumina HumanMethylation EPIC BeadChip. Linear mixed regression and Bayesian kernel machine regression (BKMR) models were used to estimate the individual and overall associations between multiple metals and accelerated methylation aging. Single metal models revealed that each 1-standard deviance (SD) increase in log-transformed vanadium, cobalt, nickel, zinc, arsenic, and barium was associated with a −2.256, −1.318, 1.004, −1.926, 1.910 and −1.356 changes in ΔAge, respectively; meanwhile, for aging rate, the change was −0.019, −0.013, 0.010, −0.018, 0.023, and −0.012, respectively (all P < 0.05). The BKMR models showed reverse U-shaped associations of the overall metals mixture with ΔAge and aging rate. Downward trends of ΔAge and aging rate were observed for increasing quantiles of essential metals mixture, but upward trends were observed for non-essential metals mixture. Further individual analysis of the BKMR revealed that the 95% confidence interval of ΔAge and aging rate associated with vanadium, zinc, and arsenic did not cross 0, when other metals concentrations set at 25th, 50th, and 75th percentile. Our findings suggest reverse U-shaped associations of the overall metals mixture with accelerated methylation aging for the first time, and vanadium, zinc, and arsenic may be major contributors driving the associations.

Discarded micro/nano-plastic inputs into the environment are emerging global concerns. Yet the quantification of micro/nanoplastics in complex environmental matrices is still a major challenge, notably for soluble ones. We herein develop in-laboratory built nanostructures (zinc oxide, titanium oxide and cobalt) coupled to mass spectrometry techniques, for picogram quantification of micro/nanoplastics in water and snow matrices, without sample pre-treatment. In parallel, an ultra-trace quantification method for micro/nanoplastics based on nanostructured laser desorption/ionization time-of-flight mass spectrometry (NALDI-TOF-MS) is developed. The detection limit is ∼5 pg for ambient snow. Soluble polyethylene glycol and insoluble polyethylene fragments were observed and quantified in fresh falling snow in Montreal, Canada. Complementary physicochemical studies of the snow matrices and reference plastics using laser-based particle sizers, inductively coupled plasma tandem mass spectrometry, and high-resolution scanning/transmission electron microscopy, produced consistent results with NALDI, and further provided information on morphology and composition of the micro/nano-plastic particles. This work is promising as it demonstrates that a wide range of recyclable nanostructures, in-laboratory built or commercial, can provide ultra-trace capability for quantification for both soluble polymers and insoluble plastics in air, water and soil. It may thereby produce key missing information to determine the fate of micro/nanoplastics in the environment, and their impacts on human health.

Advanced oxidation processes (AOPs) based on peroxymonosulfate (PMS) activation have attracted increasing attention in recent years for organic pollutants removal. Herein, we put forward a facile method to form cobalt phosphide/carbon composite for PMS activation. Combining impregnation approach with pyrolysis treatment enabled the formation of Co₂P/biochar composites using baker’s yeast and Co²⁺ as precursors. The as-synthesized products exhibited excellent catalytic activity for sulfamethoxazole (SMX) degradation over the pH range 3.0–9.0 b y activating PMS. For example, 100% of SMX (20 mg L⁻¹) removal was achieved in 20 min with catalyst dosage of 0.4 g L⁻¹ and PMS loading of 0.4 g L⁻¹. Near zero Co²⁺ leaching was observed during catalytic reaction, which remarkably lowered the toxic risk of transition metal ion in water. Meanwhile, the reusability of catalyst could be attained by thermal treatment. SMX degradation intermediates were identified by liquid chromatography-mass spectrometry (LC-MS), which facilitated the proposal of possible SMX degradation pathways. Ecological Structure Activity Relationships (ECOSAR) analysis indicated that SMX degradation intermediates may not pose ecological toxicity to the environment. Further investigation verified that Co₂P/biochar composites could set off PMS activation not only for the degradation of SMX but also for other sulfonamides. In this study, we not only developed a facile method of utilizing environmental-benign biomass for transition metal phosphide/carbon composite formation, but also achieved highly efficient antibiotic elimination by PMS-based AOP.

Over three different seasons, seawater, porewater and sediment samples were collected from Jinzhou Bay, a previously heavily contaminated bay, to quantitatively assess the benthic flux of trace metals after a reduction in fluvial/sewage discharge for almost three decades. The spatial distribution patterns of trace metals in seawater, surface sediment, as well as the vertical distribution patterns of metals in porewater and solid phases in short sediment cores were reported. Metal concentrations in seawater and sediment all showed much higher Cd and Zn concentrations inside the Jinzhou Bay compared to the rest of Bohai Sea area. Zn, Ni, Pb and Co all had average benthic fluxes coming out of the sediments to the water column, contributing about 0.5%, 0.3%, 1.4% and 14% to their current standing stock in Jinzhou Bay. Seasonal difference was also identified in seawater and porewater, as well as in the benthic fluxes. In general, benthic fluxes and porewater concentrations all tended to be higher in summer, implying a close relationship between benthic flux and the temperature-dependent organic matter degradation process at the sediment-water interface.Currently, there are clearly still other sources, possibly fluvial/sewage discharge, as the main source of trace metals in Jinzhou Bay waters. For Cd and Cu, concentrations in the water column remain high on an annual basis indicating that sediment still acts as a sink. Conversely, for Pb, Zn, Co, and Ni, the sediment is beginning to act as a source to the water column. Although this may not yet be significant, it will become more and more important with time, and can last for hundreds to thousands of years.

Potential toxic metal(loid)s (PTMs) in road dust are a major concern in relation to urban environmental quality. Identifying pollution hotspots and sources of PTMs is an essential prerequisite for pollution control and management. Herein, the concentrations, pollution and potential health risks of 8 PTMs (As, Cd, Co, Cu, Hg, Mo, Pb and Zn) in road dust from the highly urbanized areas of Nanjing were studied. Spatial occurrences and sources of PTMs were explored using geostatistics, principal component analysis (PCA) and local Moran’s index. The contamination factor (CF) results showed that Co was mainly natural in origin, while the other PTMs were polluted, with average CFs ranging from 1.4 to 11.0 as follows: Hg > Mo > Cd > Cu > Pb > Zn > As, indicating moderate to very high contamination. Except for Co and Hg, the other PTMs were heavily loaded on PC1, which explained 44.72% of the total variance. Combining the statistical results and distributions of potential sources, we deduced that industrial emissions dominated the spatial patterns of all polluted PTMs in road dust, which showed high levels in the northern parts of the study region and generally decreasing levels southwards. Moreover, Pb and Zn in the south-central area and Cd in the north-central area displayed hotspots, with maximum CFs of 5.5 (Pb), 4.2 (Zn) and 16.2 (Cd), which were related to additional automotive and railway braking emissions, respectively. The resuspension of legacy pesticides in soil is likely responsible for the As pollution hotspot in the southwestern part. Despite the high anthropogenic contributions (27% for As and 68–88% for the other metals) to the PTMs in road dust, their noncarcinogenic and carcinogenic health risks were rarely found for children and adults based on the values of the hazard index and carcinogenic risk index. However, attention still should be paid to the pollution hotspots in the northern region.

Excessive exposure to cobalt (Co) is known to make adverse impact on the nervous system, but its detailed mechanisms of neurotoxicity have yet to be determined. In this study, C57BL/6 mice (0, 4, 8, 16 mg/kg CoCl₂, 30 days) and human neuroblastoma H4 cells (0, 100, 400, 600 μM CoCl₂) were used as in vivo and in vitro models. Our results revealed that CoCl₂ intraperitoneal injection caused significant impairments in learning and memory, as well as pathological damage in the nervous system. We further certificated the alteration of m⁶A methylation induced by CoCl₂ exposure. Our findings demonstrate for the first time, significant differences in the degree of m⁶A modification, the biological function of m⁶A-modified transcripts between cortex and H4 cell samples. Specifically, MeRIP-seq and RNA-seq elucidate that CoCl₂ exposure results in differentially m⁶A-modified and expressed genes, which were enriched in pathways involving synaptic transmission, and central nervous system (CNS) development. Mechanistic analyses revealed that CoCl₂ remarkably changed m⁶A modification level by affecting the expression of m⁶A methyltransferase and demethylase, and decreasing the activity of demethylase. We observed variation of m⁶A modification in neurodegenerative disease-associated genes upon CoCl₂ exposure and identified regulatory strategy between m⁶A and potential targets mRNA. Our novel findings provide novel insight into the functional roles of m⁶A modification in neurodegenerative damage caused by environmental neurotoxicants and identify Co-mediated specific RNA regulatory strategy for broadening the epigenetic regulatory mechanism of RNA induced by heavy metals.

Microplastics are known to be associated with co-contaminants, but little is understood about the mechanisms by which these chemicals are transferred from ingested plastic to organisms. This study simulates marine avian gastric conditions in vitro to examine the bioaccessibility of authigenic metals (Fe, Mn) and trace metals (Co, Pb) that have been acquired by polyethylene microplastic pellets from their environment. Specifically, different categories of pellet were collected from beaches in Cornwall, southwest England, and exposed to an acidified saline solution of pepsin (pH ∼ 2.5) at 40 °C over a period of 168 h with extracted metal and residual metal (available to dilute aqua regia) analysed by ICP-MS. For Fe, Mn and Co, kinetic profiles consisted of a relatively rapid initial period of mobilisation followed by a more gradual approach to quasi-equilibrium, with data defined by a diffusion model and median rate constants ranging from about 0.0002 (μg L⁻¹)⁻¹ h⁻¹ for Fe to about 7 (μg L⁻¹)⁻¹ h⁻¹ for Co. Mobilisation of Pb was more complex, with evidence of secondary maxima and re-adsorption of the metal to the progressively modified pellet surface. At the end of the time-courses, maximum total concentrations were 38.9, 0.81, 0.014 and 0.10 μg g⁻¹ for Fe, Mn, Co and Pb, respectively, with maximum respective percentage bioaccessibilities of around 60, 80, 50 and 80. When compared with toxicity reference values for seabirds, the significance of metals acquired by microplastics from the environment and exposed to avian digestive conditions is deemed to be low, but studies of a wider range of plastics and metal associations (e.g. as additives) are required for a more comprehensive risk assessment.

Herein, a new peroxymonosulfate (PMS) activation system was established using a biochar (BC)-supported Co₃O₄ composite (Co₃O₄-BC) as a catalyst to enhance chloramphenicols degradation. The effects of the amount of Co₃O₄ load on the BC, Co₃O₄-BC amount, PMS dose and solution pH on the degradation of chloramphenicol (CAP) were investigated. The results showed that the BC support could well disperse Co₃O₄ particles. The degradation of CAP (30 mg/L) was enhanced in the Co₃O₄-BC/PMS system with the apparent degradation rate constant increased to 5.1, 19.4 and 7.2 times of that in the Co₃O₄/PMS, BC/PMS and PMS-alone control systems, respectively. Nearly complete removal of CAP was achieved in the Co₃O₄-BC/PMS system under the optimum conditions of 10 wt% Co₃O₄ loading on BC, 0.2 g/L Co₃O₄-BC, 10 mM PMS and pH 7 within 10 min. The Co₃O₄/BC composites had a synergistic effect on the catalytic activity possibly because the conducting BC promoted electron transfer between the Co species and HSO₅⁻ and thus accelerated the Co³⁺/Co²⁺redox cycle. Additionally, over 85.0 ± 1.5% of CAP was still removed in the 10th run. Although both SO₄⁻ and OH were identified as the main active species, SO₄⁻ played a dominant role in CAP degradation. In addition, two other chloramphenicols, i.e., florfenicol (FF) and thiamphenicol (TAP), were also effectively degraded with percentages of 86.4 ± 1.3% and 71.8 ± 1.0%, respectively. This study provides a promising catalyst Co₃O₄-BC to activate PMS for efficient and persistent antibiotics degradation.