Toxic Potencies of Particulate Matter from Typical Industrial Plants Mediated with Acidity via Metal Dissolution.

Acidity is an important property of particulate matter (PM) in the atmosphere, but its association with PM toxicity remains unclear. Here, this study quantitively reports the effect of the acidity level on PM toxicity via pH-control experiments and cellular analysis. Oxidative stress and cytotoxicity potencies of acidified PM samples at pH of 1-2 were up to 2.8-5.2 and 2.1-13.2 times higher than those at pH of 8-11, respectively. The toxic potencies of PM samples from real-world smoke plumes at the pH of 2.3 were 9.1-18.2 times greater than those at the pH of 5.6, demonstrating a trend similar to that of acidified PM samples. Furthermore, the impact of acidity on PM toxicity was manifested by promoting metal dissolution. The dramatic increase by 2-3 orders of magnitude in water-soluble metal content dominated the variation in PM toxicity. The significant correlation between sulfate, the pH value, water-soluble Fe, IC20, and EC1.5 (p < 0.05) suggested that acidic sulfate could enhance toxic potencies by dissolving insoluble metals. The findings uncover the superficial association between sulfate and adverse health outcomes in epidemiological research and highlight the control of wet smoke plume emissions to mitigate the toxicity effects of acidity.

Distribution of acid-volatile sulfides and simultaneously extracted metals in Guanabara Bay: combination of anthropogenic, sedimentological, and geochemical processes.

Coastal sedimentary systems are affected by continental and marine metal pollutant inputs associated with different hydrodynamic characteristics and geochemical processes. These include the formation of acid-volatile sulfides (AVS) within sediments, which affects metal bioavailability and associated aquatic biota toxicity risks. Physicochemical changes in these environments in the face of extreme natural or man-made environmental influences can dramatically alter metal bioavailability and toxicity through metal binding and immobilization as insoluble sulfides. Surface sediments from Guanabara Bay, river mouths, and two mangrove areas were collected, and AVS and simultaneously extracted metals Cd, Cu, Fe, Mn, Ni, Pb, and Zn and ΣSEM were determined to assess sediment quality. A severe eutrophication history favored AVS concentrations exceeding or close to the sum-SEM concentrations, demonstrating that AVS play an important role in making trace metals unavailable for assimilation by living organisms, mitigating the risks of contamination for the local biota. This eutrophication-driven sulfide accumulation may attenuate the sediment toxicity in sites heavily polluted by metals, while some fewer eutrophic sites became more exposed to metals in excess to AVS.

Identification and quantification of trace metal(loid)s in water-extractable road dust nanoparticles using SP-ICP-MS.

Resuspension of road dust is a major source of airborne particulate matter (PM) in urban environments. Inhalation of ultrafine particles (UFP; < 0.1 µm) represents a health concern due to their ability to reach the alveoli and be translocated into the blood stream. It is therefore important to characterize chemical properties of UFPs associated with vehicle emissions. We investigated the capability of Single-Particle ICP-MS (SP-ICP-MS) to quantify key metal(loid)s in nanoparticles (NPs; < 0.1 µm) isolated from road dust collected in Toronto, Canada. Water extraction was performed to separate the <1-µm fraction from two different road dust samples (local road vs. arterial road) and a multi-element SP-ICP-MS analysis was then conducted on the samples' supernatants. Based on the particle number concentrations obtained for both supernatants, the metal(loid)-containing NPs could be grouped in the following categories: high (Cu and Zn, > 1.3 × 1011 particles/L), medium (V, Cr, Ba, Pb, Sb, Ce, La), low (As, Co, Ni, < 4.6 × 109 particles/L). The limit of detection for particle number concentration was below 5.5 × 106 particles/L for most elements, except for Cu, Co, Ni, Cr, and V (between 0.9 and 7.7 × 107 particles/L). The results demonstrate that road dust contains a wide range of readily mobilizable metal(loid)-bearing NPs and that NP numbers may vary as a function of road type. These findings have important implications for human health risk assessments in urban areas. Further research is needed, however, to comprehensively assess the NP content of road dust as influenced by various factors, including traffic volume and speed, fleet composition, and street sweeping frequency. The described method can quickly characterize multiple isotopes per sample in complex matrices, and offers the advantage of rapid sample scanning for the identification of NPs containing potentially toxic transition metal(loid)s at a low detection limit.

Oxidative stress and neurotoxicity induced by exposure to settleable atmospheric particulate matter in bullfrog tadpoles, Aquarana catesbeiana, (Shaw, 1802).

Bullfrog tadpoles, Aquarana catesbeiana, were exposed to settleable particulate matter (SePM), (1 g L-1, 96 h) and their organs were collected for analysis of metal/metalloid, oxidative stress and neurotoxicity in liver, muscle, kidney and brain. The SePM water of the exposed groups contained 18 of the 28 metals/metalloids detected in ambient particulate matter (APM). Fe56 and Al were those that presented the highest concentrations, Cr, Mn, Pb and Cu increased from 10 to 20 times and Ti, V, Sr, Rb, Cd, Sn and Ni increased from 1 to 3 times compared to the control. Bioaccumulation of metals/metalloids in the exposure water varied significantly between organs, with the muscle and liver showing the highest concentrations of metals, followed by the brain. Lipoperoxidation and malondialdehyde increased only in muscle, while carbonyl proteins increased only in the liver and brain. Regarding nitric oxide synthase, there was an increase in the liver and brain in the group exposed to SePM. Catalase activity decreased in the liver and muscle, while the activity of glutathione peroxidase, increased in the liver and kidney and decreased in muscle. Glutathione S-transferase, which is mainly responsible for detoxification, increased in the liver and decreased in muscle and the kidney. Cholinesterase activity increased only in the muscle. The results indicate oxidative stress, due to oxidation catalyzed by metals, components of SePM. Thus, the results contribute to the understanding that SePM has a deleterious effect on the aquatic environment, negatively affecting bullfrog tadpoles, in different ways and levels in relation to the analyzed organs.

Snow Contamination by Metals and Metalloids in a Polar Town: A Case Study of Nadym, Russia.

Snow composition depends on the long-range transport of pollutants. This article examines aspects of snow composition in the town of Nadym in Western Siberia. During fieldwork conducted in 2021 and 2022, we determined dust load, concentrations and ratio of dissolved and suspended forms of metals and metalloids (MMs). Moreover, we analyzed air mass trajectories using the HYSPLIT model, and the results showed that industrial regions of the southern Urals, southeastern Siberia, and Kazakhstan were the sources of MMs. Content of the insoluble fraction was increased by 23-fold in Nadym. The dust load in Nadym was higher than that in urban communities situated in the temperate zone, even though this town is relatively small in population and has little industrial infrastructure. This significant increase in dust load led to a ten- to 100-fold increase in the content MMs. Local soils (Fe, Al), vehicles (W), building dust (Mg, Ca), and anti-icing agents (Na) were found to be the sources of pollution. We found that the high dust load is caused by meteorological factors, such as temperature inversion and a large number of calm days, which reduce the dispersion of pollution. This case study demonstrates that winter air quality in polar settlements can be worse than that in urban areas in the temperate zone, even with few local sources of pollution. Furthermore, the trend toward an increase in the number of windless days, such as observed in Siberia as a result of global climate change, increases the risk of anthropogenic pollution of the atmosphere of polar cities.

What do we know about dermal bioaccessibility of metals coated on antibacterial films?

Antibacterial films have gained attention since the outbreak of the COVID-19 pandemic; however, the impact of metals contained in antibacterial films on human safety have not been sufficiently investigated. This study reports on the important features that must be considered when assessing the bioaccessibility of Ag, Cu, and Zn in antibacterial films. Specifically, the effects of the artificial sweat component (i.e., amino acid and pH), surface weathering of antibacterial films, wipe sampling, and sebum were carefully examined. Our findings suggest that amino acids greatly affect bioaccessibility as amino acids act as ligands to facilitate metal ion leaching. In addition, constant exposure to ultraviolet C causes the film surface to oxidize, which significantly increases metal bioaccessibility due to the electrostatic repulsion between metal oxides and organic substrates. The presence of sebum in artificial sweat and physical damage to the film surface had no significant effects. Furthermore, the wipe sampling used to mimic the realistic dermal contact suggests the feasibility of applying this method for the assessment of bioaccessibility of metals in antibacterial films. The method offers significant advantages for evaluating the human safety aspects of skin contact with consumer products in future research.

Ascertaining sensitive exposure biomarkers of various metal(loid)s to embryo implantation.

Close relationships exist between metal(loid)s exposure and embryo implantation failure (EIF) from animal and epidemiological studies. However, there are still inconsistent results and lacking of sensitive metal(loid) exposure biomarkers associated with EIF risk. We aimed to ascertain sensitive metal(loid) biomarkers to EIF and provide potential biological explanations. Candidate metal(loid) biomarkers were measured in the female hair (FH), female serum (FS), and follicular fluid (FF) with various exposure time periods. An analytical framework was established by integrating epidemiological association results, comprehensive literature searching, and knowledge-based adverse outcome pathway (AOP) networks. The sensitive biomarkers of metal(loid)s along with potential biological pathways to EIF were identified in this framework. Among the concerned 272 candidates, 45 metal(loid)s biomarkers across six time periods and three biomatrix were initially identified by single-metal(loid) analyses. Two biomarkers with counterfactual results according to literature summary results were excluded, and a total of five biomarkers were further determined from 43 remained candidates in mixture models. Finally, four sensitive metal(loid) biomarkers were eventually assessed by overlapping AOP networks information, including Se and Co in FH, and Fe and Zn in FS. AOP networks also identified key GO pathways and proteins involved in regulation of oxygen species biosynthetic, cell proliferation, and inflammatory response. Partial dependence results revealed Fe in FS and Co in FH at their low levels might be potential sensitive exposure levels for EIF. Our study provided a typical framework to screen the crucial metal(loid) biomarkers and ascertain that Se and Co in FH, and Fe and Zn in FS played an important role in embryo implantation.

The composition and differences of antimony isotopic in sediments affected by the world's largest antimony deposit zone.

Antimony (Sb) isotopic fingerprinting is a novel technique for stable metal isotope analysis, but the use of this technique is still limited, especially in sediments. In this study, the world's most important Sb mineralization belt (the Xikuangshan mineralization belt) was taken as the research object and the Sb isotopic composition and Sb enrichment characteristics in the sediments of water systems from different Sb mining areas located in the Zijiang River (ZR) Basin were systematically studied. The results showed that the ε123Sb values in the sediments of the ZR and its tributaries, such as those near the Longshan Sb-Au mine, the Xikuangshan Sb mine, and the Zhazixi Sb mine, were 0.50‒3.13 ε, 2.31‒3.99 ε, 3.12‒5.63 ε and 1.14‒2.91 ε, respectively, and there were obvious changes in Sb isotopic composition. Antimony was mainly enriched in the sediments due to anthropogenic sources. Dilution of Sb along the river and adsorption of Sb to Al-Fe oxides in the sediment did not lead to obvious Sb isotopic fractionation in the sediment, indicating that the Sb isotopic signature was conserved during transport along the river. The Sb isotopic signatures measured in mine-affected streams may have differed from those in the original Sb ore, and further investigation of Sb isotopic fingerprints from other possible sources and unknown geochemical processes is needed. This study reveals that the apparent differences in ε123Sb values across regions make Sb isotopic analysis a potentially suitable tool for tracing Sb sources and biogeochemical processes in the environment.

Controlling effects of terrestrial organic matter on metal contamination and toxicity risks in port sediments.

The contents of metals, total carbon, total nitrogen (TN), total organic carbon (TOC), and stable isotope composition (δ13Corg and δ15N) of sediment organic matter (SOM) were investigated to explore the sources and spatial distribution of metals and SOM in the surface sediments (Kaohsiung Port, Taiwan). Results showed that TOC and metals in estuarine sediments are high, gradually decreasing toward the port entrances. The δ13Corg, δ15N, and TOC/TN ratios indicate that SOM comes mainly from terrestrial sources. This study proposes a befitting model between metal pollution and toxicity risk index and SOM sources in port sediments by combining stable isotope composition, correlation matrix, and multiple linear regression analysis. The model indicates that the degree of metal pollution and toxicity risk in sediments are mainly affected by TOCterr content and SOM source. The results help to understand the influence of organic matter sources in port sediments on metal concentration distribution.

Growing coastal tourism: Can biomonitoring provide insights into the health of coastal ecosystems?

Coastal tourism's surge raises concerns for Morocco's Agadir marine environment, notably with Taghazout Bay's impact. Our study assesses Taghazout's health, employing a comprehensive approach. Our study evaluates Taghazout's health, adopting a comprehensive approach covering physicochemical, microbiological aspects, macrobenthic fauna, metal pollution, and biomarkers in D. trunculus mollusks. Seawater quality aligns with Moroccan standards, indicating good bathing water. The intertidal zone hosts ten species, dominated by D. trunculus. Biomarker responses in D. trunculus suggest chemical stress. Land-use maps expose significant changes driven by the Taghazout Bay project, impacting approximately 37.99 % of the landscape. Construction activities notably encroached upon the Arganeraie and the coastal zone, creating a stark contrast from 2003. These findings form a crucial database for future studies, contributing significantly to environmental management and sustainable development, aiding informed decision-making and effective coastal ecosystem preservation strategies.

Lichen biomonitoring to assess spatial variability, potential sources and human health risks of polycyclic aromatic hydrocarbons (PAHs) and airborne metal concentrations in Manchester (UK).

Airborne metals and organic pollutants are linked to severe human health impacts, i.e. affecting the nervous system and being associated with cancer. Airborne metals and polycyclic aromatic hydrocarbons (PAHs) in urban environments are derived from diverse sources, including combustion and industrial and vehicular emissions, posing a threat to air quality and subsequently human health. A lichen biomonitoring approach was used to assess spatial variability of airborne metals and PAHs, identify potential pollution sources and assess human health risks across the City of Manchester (UK). Metal concentrations recorded in lichen samples were highest within the city centre area and along the major road network, and lichen PAH profiles were dominated by 4-ring PAHs (189.82 ng g-1 in Xanthoria parietina), with 5- and 6-ring PAHs also contributing to the overall PAH profile. Cluster analysis and pollution index factor (PIF) calculations for lichen-derived metal concentrations suggested deteriorated air quality being primarily linked to vehicular emissions. Comparably, PAH diagnostic ratios identified vehicular sources as a primary cause of PAH pollution across Manchester. However, local more complex sources (e.g. industrial emissions) were further identified. Human health risk assessment found a "moderate" risk for adults and children by airborne potential harmful element (PHEs) concentrations, whereas PAH exposure in Manchester is potentially linked to 1455 (ILCR = 1.45 × 10-3) cancer cases (in 1,000,000). Findings of this study indicate that an easy-to-use lichen biomonitoring approach can aid to identify hotspots of impaired air quality and potential human health impacts by airborne metals and PAHs across an urban environment, particularly at locations that are not continuously covered by (non-)automated air quality measurement programmes.

Insights into metal tolerance and resistance mechanisms in Trichoderma asperellum unveiled by de novo transcriptome analysis during bioleaching.

This study investigates the genetic responses of the fungus Trichoderma asperellum (T. asperellum) during bioleaching of ore and tailing samples, comparing one-step, two-step, and spent media bioleaching processes. HPLC analysis quantified oxalic acid, citric acid, and propionic acids, with oxalic acid identified as the primary organic acid involved in metal bioleaching. Metal analysis revealed differences in recovery between ore and tailing samples and among bioleaching processes. The two-step bioleaching process yielded the highest zinc (>54%) and nickel (>60%) recovery in tailings and ore, respectively. Nickel's efficient recovery in ore bioleaching was attributed to the presence of manganese, while its precipitation as nickel oxalate in tailings hindered recovery. Additional metals such as Co, Mn, Mg, Cu, and As were also successfully recovered. Transcriptomic analyses showed significant upregulation of genes associated with biological processes and cellular components, particularly those related to cell membrane structure and function, indicating T. asperellum's adaptation to environmental stresses during metal bioleaching. These findings enhance our understanding of the diverse mechanisms influencing metal recovery rates in bioleaching processes.

Bacterial community in the metal(loid)-contaminated marine vertical sediments of Jinzhou Bay: Impacts and adaptations.

Metal(loid) discharge has led to severe coastal contamination; however, there remains a significant knowledge gap regarding its impact on sediment profiles and depth-resolved bacterial communities. In this study, geochemical measurements (pH, nutrient elements, total and bioavailable metal(loid) content) consistently revealed decreasing nitrogen, phosphorus, and metal(loid) levels with sediment depth, accompanied by reduced alpha diversity. Principal coordinate analysis indicated distinct community compositions with varying sediment depths, suggesting a geochemical influence on diversity. Ecological niche width expanded with depth, favoring specialists over generalists, but both groups decreased in abundance. Taxonomic shifts emerged, particularly in phyla and families, correlated with sediment depth. Microbe-microbe interactions displayed intricate dynamics, with keystone taxa varying by sediment layer. Zinc and arsenic emerged as key factors impacting community diversity and composition using random forest, network analysis, and Mantel tests. Functional predictions revealed shifts in potential phenotypes related to mobile elements, biofilm formation, pathogenicity, N/P/S cycles, and metal(loid) resistance along sediment profiles. Neutral and null models demonstrated a transition from deterministic to stochastic processes with sediment layers. This study provides insights into the interplay between sediment geochemistry and bacterial communities across sediment depths, illuminating the factors shaping these ecosystems.

Human health and environmental risk assessment of metals in community gardens of Winnipeg, Manitoba, Canada.

Fresh produce is an important component of maintaining cognitive and physical health, particularly for children. A mechanism to increase access to fresh produce is the construction of community gardens in urban centres. While reducing barriers to nutritious food, the soil of the community garden can contain contaminants (e.g. metals) depending on the location and how the garden was constructed. This study quantified, for the first time, seven metals (As, Cd, Cr, Cu, Pb, Mn, and Ni) in soil from 83 community gardens across the City of Winnipeg in Manitoba, Canada. Concentrations of metals in soil were used to create distributions for environmental exposure and estimated daily intake, which were then used to determine exceedances of soil quality guidelines and acceptable daily intakes, respectively. Raised garden beds and gardens further from roads had typically lower concentrations of metals in surface gardens and those nearer to roads. While some concentrations of metals exceeded CCME guidelines levels for the protection of environmental health, the vast majority represent a low risk. For human health, only As posed a quantifiable risk of exceeding the USEPA acceptable daily intake via the consumption of produce from gardens, though this was < 1.2% for the whole population and < 10.2% for children aged 1 to 2 years. Overall, this study is the first to show that the concentration of the metals in soil from gardens typically poses a low risk to environmental and human health. We recommend the use of raised gardens to further mitigate risk.

Seasonal impact of acid mine drainage on water quality and potential ecological risk in an old sulfide exploitation.

Sulfides are usually associated with deposits of metals and coal. The reactive wastes from their exploitation, typically stored in piles and tailings dams, are often the mining sector's primary source of environmental problems. The surrounding river waters can present signs of acid mine drainage, responsible for aquatic ecosystem degradation. So, the main target of the present study is to investigate the impact of this process on the water's environmental quality and potential ecological risk. The study area is located at the Iberian Pyrite Belt, in an old sulfide exploitation, closed without environmental rehabilitation measures. The results exhibit high sulfate concentrations (410,601 mg/L) and potentially toxic elements, with prominence of Fe (134,000 mg/L), overcoming many other extreme cases of AMD pollution. The Ficklin diagram exposes that most samples are classified as "high-acid, high-metal." Two of them have extreme classifications (high-acid, extreme-metal). The pH value is well below the acceptable range for the environmental quality of superficial waters (5-7), measuring at a minimum of 0.84. Regarding seasonal variability, the study showed a higher degree of contamination in dry conditions (e.g., 4,420 mg/L of Cu), while the rainy month had lower concentrations of PTE (186.8 mg/L of Cu for the same sampling point). In addition, the water does not accomplish the environmental objectives established by the EU Water Framework Directive. According to the new approach developed based on a scale adjustment, the potential ecological risk index studied indicates that most sampled sites present strong, very strong, and even extremely potential ecological risk. With a typical Mediterranean climate, the region suffers from water scarcity, predicting increasingly in the future more degrading scenarios for water environmental quality. Consequently, urgent mitigation and remediation measures are necessary to improve and preserve water quality and fulfill the objectives of the United Nations Sustainability Development Goals.

Understanding the variable metal concentrations in estuarine oysters Crassostrea hongkongensis: A biokinetic analysis.

Understanding the metal concentrations in oysters is important because of its relevance to human health and biomonitoring. However, metal concentrations in oysters are highly variable in nature and not well explained by metal exposure. This study examined the metal contamination in farm oysters Crassostrea hongkongensis grown in Qinzhou Bay, south China. Cadmium (Cd), zinc (Zn), nickel (Ni), and copper (Cu) concentrations in the oysters varied between 7.9 and 72.2, 282-17003, 0.37-47.7 and 37-4012 µg g-1, respectively, showing large metal variability among different individuals. Oyster metal concentrations decreased with increasing body size and significantly higher levels were observed in wet season. Low salinity and slower oyster growth due to inferior growth conditions could be responsible for the elevated metal concentrations in the wet season. Biokinetic modeling showed that the coupling of ingestion rate and growth can cause 2.8-4.2 folds differences in the oyster Cd and Zn concentrations, respectively, suggesting the significant role of oyster bioenergetics in contributing to the metal variability. Modeling data revealed that Cd and Zn concentrations in oyster tissues reach maximum levels when oysters have their lowest growth efficiency. This suggests that any factors influencing the energy budget in oysters could simultaneously alter their metal concentrations, which might be the reason why oyster metal concentrations are so variable in the natural environment.

Benchtop x-ray fluorescence to quantify elemental content in nails non-destructively.

Metals continue to impose health issues among world populations. A non-invasive alternative biomarker for assessment of metals and other elements has been explored in other studies using toenail samples. Some benefits of using toenails as biomarkers over blood samples include cost efficiency, ease of collection, and a longer biological half-life within samples. The objective of this study was to employ desktop XRF for the purpose of measuring metal concentrations in human nail samples, thus conducting a non-destructive assessment. These benefits paired with comparable accuracy in exposure detection could prove toenail samples to be a preferred biomarker for many studies. Current elemental quantification techniques in toenail samples could be improved. The standard practice for measuring metal exposure in toenails, inductively coupled plasma mass spectrometry (ICP-MS), has a counterpart in x-ray fluorescence. While maintaining similar quantification capabilities, x-ray fluorescence could provide decreased cost, preservation of samples, and ease of operation. Portable XRF machines have been tested for measuring toenail samples, but they have drastically increased detection limits in comparison to ICP-MS. New benchtop XRF systems should give comparable detection limits to ICP-MS. This study compares the benchtop XRF measurements of lead (Pb), copper (Cu), iron (Fe), and Selenium (Se) levels to that of ICP-MS measurements of toenail samples and calculates estimated detection limits for 23 other elements. We found strong correlations for the toenail lead (R2 = 0.92), copper (R2 = 0.95), selenium (R2 = 0.60), and iron (R2 = 0.77) comparison between desktop XRF and ICP-MS measurements. Median minimum detection limits over the 23 elements were found to be 0.2 µg/g using a 7.5-min measurement. Benchtop XRF provides a lower detection limit than previously studied portable XRF machines, which gives it the capability of accurately detecting almost any desired element in nail samples. Benchtop XRF provides a non-destructive alternative to ICP-MS in surveillance of nail samples.

Five years after the collapse of the Fundão Dam: lessons from temporal monitoring of chemistry and acute toxicity.

In November 2015, the Fundão Dam break released millions of tons of metal-rich tailings into the Doce River Basin (DRB), causing catastrophic damage and potential ecological effects that reached the Atlantic Ocean. This study aimed to evaluate the geochemistry and toxicity of water and sediments collected in the DRB from 2015 to 2019 and to determine the spatial and temporal trends. Water and sediment samples were analyzed for metals and As by inductively coupled plasma optical emission spectrometry (ICP-OES), and acute toxicity for Daphnia similis or D. magna. Results were explored using geochemical indices and correlation analyzes. Overall, higher concentrations of metals and As in water and sediments were observed immediately after dam breakage, but the levels exhibited a decreasing trend over time, although the levels of some elements such as As and Mn remained high in the upper DRB. The geochemical indices indicated mostly low to moderate contamination, and the enrichment factor (EF) demonstrated a higher enrichment of Mn in the upper DRB. Acute toxicity to water fleas (D. similis and D. magna) was occasionally observed in waters and sediments, but the reference samples were toxic, and the short-term effects were not correlated with metals and As. Overall, the results showed limited bioavailability of metals and As and a decreasing trend in their concentrations, indicating an ongoing recovery process in DRB. These results are important to decision-making regarding the disaster and actions for environmental restoration.

Using Bayesian and weighted regression to evaluate the association of idiopathic oligoastenoteratozoospermia with seminal plasma metal mixtures.

Idiopathic oligoastenoteratozoospermia (iOAT) affects 30% of infertile men of reproductive age. However, the associations between Cr, Fe, Cu, Se or Co levels and iOAT risk have not been determined. This research aimed to assess the associations between Cr, Fe, Cu, Se and Co levels as well as their mixtures in seminal plasma and the risk of iOAT and severe iOAT. Therefore, a case‒control study including 823 participants (416 iOAT patients and 407 controls) recruited from October 2021 to August 2022 at the reproductive medicine center of the First Affiliated Hospital of Anhui Medical University was conducted in Anhui, China. The concentrations of Cr, Fe, Cu, Se and Co in seminal plasma were detected via inductively coupled plasma‒mass spectrometry. Binary logistic regression models were used to assess the associations between the levels of Cr, Fe, Cu, Se and Co and the risk of iOAT and severe iOAT; additionally, Bayesian kernel machine regression (BKMR) and weighted quantile sum (WQS) regressions were performed to evaluate the joint effect of seminal plasma levels of Cr, Fe, Cu, Se and Co on the risk of iOAT and explore which elements contributed most to the relationship. We found significant associations between the concentrations of Fe, Cu and Se in seminal plasma and iOAT risk after adjusting for covariates (Fe, lowest tertile vs. second tertile: aOR = 1.86, 95% CI = 1.31, 2.64; Cu, lowest tertile vs. second tertile: aOR = 1.95, 95% CI = 1.37, 2.76; Se, lowest tertile vs. second tertile: aOR = 1.65, 95% CI = 1.17, 2.35). A lower Se concentration in seminal plasma (lowest tertile vs. second tertile: aOR = 1.84, 95% CI = 1.10, 3.10) was positively associated with the risk of severe iOAT. Additionally, we also observed an association between the concentration of Cr in seminal plasma and the risk of iOAT before adjusting for covariates (Cr, third tertile vs. lowest tertile: OR=1.44, 95% CI: 1.03, 2.02). According to the BKMR analyses, the risk of iOAT increased when the overall concentrations were less than the 25th percentile. The results from the WQS regression indicated that a negative WQS index was significantly associated with the iOAT risk, while a positive WQS index was not. Se and Fe had significant weights in the negative direction. In conclusion, lower Cu, Fe and Se levels in seminal plasma were positively associated with iOAT risk, while higher Cr levels in seminal plasma were positively associated with iOAT risk according to the single element model, and lower levels of Se were related to a greater risk of severe iOAT; when comprehensively considering all the results from BKMR and WQS regression, Fe, Se and Cr levels contributed most to this relationship.

Baseline metal and metalloid contamination in two marine sponge species, Hymeniacidon heliophila and Desmapsamma anchorata, from southeastern Brazil.

Sponges are not routinely employed as metal bioindicators in Brazil. In this sense, this study reports baseline metal and metalloid concentrations, determined by inductively coupled plasma mass spectrometry, for two Demospongiae sponge species, Hymeniacidon heliophila and Desmapsamma anchorata, sampled from two Southeastern Brazil areas. Sponges from Ilha Grande Bay, an Environmental Protection Area, exhibited higher Al, As, Cd, Co, Cr, Fe, and Ni levels compared to Vermelha Beach, a metropolitan area in the Rio de Janeiro city. Several strong correlations were noted between elemental pairs, indicating common contamination sources and/or similar metabolic detoxification routes. Comparisons of the means determined herein for each study site to other reports indicate mostly lower Ag, As, Co, Cd, and Cu levels, while Al levels were higher than other studies, and Cr, Ni, and Fe were within reported ranges. These baseline data further knowledge on metal pollution in Desmspongiae members, which are still limited.