Cacao (Theobroma cacao) serves as the foundational raw material for all chocolate production. The burgeoning scientific interest in chocolate is driven not only by its substantial economic value but also by its complex nutritional profile and the potential benefits associated with its high cacao content. However, the co-occurrence of beneficial bioactive compounds with potentially toxic elements is a food safety concern. Consequently, this study was designed to quantify the concentrations of trace elements across a broad spectrum of commercially available chocolates (ranging from ≤40% to 92% cacao content) procured from Brazilian markets, and to rigorously assess the associated human health risk using the estimated daily intake (EDI) and the target hazard quotient (THQ). A total of thirty-two samples were analysed for Al, Mn, Fe, Zn, Se, As, Cd, Pb and Hg, and rare earth elements (REEs) using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The maximum measured concentrations were observed for Fe (438.23 mg kg⁻¹), Cd (672.69 μg kg⁻¹) and Ce (114.76 μg kg⁻¹) in chocolates with 80–82% cacao content. The maximum EDI values for the essential and non-essential elements Mn, Fe, Zn, and Se were calculated as 0.02, 0.78, 0.15 and 0.03 mg kg⁻¹ body weight day⁻¹, respectively, while Al reached 0.04 mg kg⁻¹ body weight day⁻¹. For the toxic elements As, Cd, Hg, and Pb, the maximum EDI values were 0.02, 0.27, 0.01 and 0.03 μg kg⁻¹ body weight day⁻¹, respectively. These elevated levels, particularly high in 70% and 82% cacao samples, suggest potential health risks. Despite these findings, the calculated THQ values for Al, As, Cd, Hg, and Pb remained below the threshold of 1. Principal component analysis (PCA) revealed a clear and significant relationship between cacao content, element levels, and the geographical origin of the samples. These results unequivocally underscore the critical need for simultaneous monitoring of both elemental composition and cacao percentage to effectively mitigate consumer exposure to toxic contaminants and ensure food safety standards.

Introduction

Bentazone (BTZ) is an herbicide used in rice paddies. BTZ has been detected in the Albufera Natural Park (Spain), recognized as a "Wetland of International Importance". The Albufera lake waters contain variable concentrations of sulfates and chlorides over time. This study aimed to analyze the impact that these two compounds may have on the BTZ ecotoxicity.

Methods

Ecotoxicity was determined using Lactuca sativa seeds according to US EPA OPPTS 850.4200 standard.

First, the individual ecotoxicity of BTZ was determined. Later, 64 samples were prepared using all possible combinations of 0, 300, 600, and 900 mg L⁻¹ of BTZ; 0, 0.8, 1.6, and 2.4 g L⁻¹ of NaCl; and 0, 1.4, 2.8, and 4.2 g L⁻¹ of Na₂SO₄. The maximum concentration for each compound was approximately equal to its individual ecotoxicity threshold.

Results

BTZ exhibits an EC₅₀(5 days) towards Lactuca sativa of 900 mg L^-1, showing a hormetic effect. The toxic effects of a BTZ, NaCl and Na₂SO₄ mixture are generally lower than the individual toxic effects considered additively. A statistical model was obtained to predict the ecotoxicity thresholds for combinations of the three compounds. In general, when the concentration of one compound increases, a lower concentration of the others is necessary for the mixture to be toxic. However, in the presence of NaCl, below 382 mg L^-1 of BTZ, the concentrations of both compounds need to be increased. This is attributable to the hormetic behavior of BTZ. This BTZ concentration decreases as the Na₂SO₄ concentration increases.

Conclusions

EC₅₀(5 days) for BTZ towards Lactuca sativa is 900 mg L^-1. This value decreases when concentrations of Na₂SO₄ and NaCl increase. However, below 382 mg L^-1 of BTZ (a value that is lower as the concentration of Na₂SO₄ increases), the concentration of NaCl must also be decreased.

Plastic pollution represents a major environmental issue due to its persistence and interaction with chemical contaminants in aquatic ecosystems. Once released into the environment, plastics undergo biological and chemical transformations that influence their transport and fate. The fragmentation of larger plastic items results in microplastics (MPs), defined as particles ranging from 1 µm to 5 mm, which may be ingested by organisms and act as vectors for contaminants, including potentially toxic elements (PTEs). Elevated concentrations of these elements pose significant ecological and human health concerns. This study aimed to quantify the concentrations of As, Cd, Cu, Hg, Pb, and Zn, as well as to identify and quantify plastic and microplastic particles in rivers located in the ABC Paulista region (Brazil). The relationship between water quality parameters and contaminant occurrence was also investigated. Eight sampling sites were selected along downstream sections of the Tamanduateí River, covering areas influenced by residential, industrial, and tourist activities. Chemical element concentrations were determined using inductively coupled plasma mass spectrometry. Plastic and microplastic particles were identified and quantified following standardized National Oceanic and Atmospheric Administration (NOAA) protocols, using Raman and FT-IR spectroscopy. Sediment samples contained between 2 and 1,000 plastic particles per kilogram, predominantly composed of polyethylene, polypropylene, and fibers. In the water column, an average concentration of approximately 350 microplastic particles per cubic meter was observed. Analyses of leaves, water, and sediments revealed elevated concentrations of PTEs, with Pb identified as the dominant contaminant. Maximum Pb concentrations reached 7 ppb in water, 4000 ppb in leaves, and up to 25000 ppb in sediments. Cadmium and As were detected as secondary contaminants, with concentrations reaching up to 5000 ppb..Overall, the results demonstrate the widespread occurrence of microplastics and potentially toxic elements across multiple environmental matrices, highlighting potential risks to aquatic ecosystems and human health in urban-industrial river systems.

The expansion of intensive agricultural systems leads to increasing degradation of natural habitats, caused, among other factors, by the widespread use of herbicides such as glyphosate (Gly), whichis widely used despite growing evidence of its potential adverse effects. Among the vertebrates most exposed to ecotoxicological risk are reptiles, whose populations are particularly sensitive to habitat loss and endocrine disruption. In this context, this study combines in vivo and in vitro approaches to assess the impact of glyphosate on the male reproductive system.

In the in vivo model, adult males of Podarcis siculus lizards were exposed orally, every other day for three weeks, to two concentrations of Gly (0.05 and 0.5 μg/kg bw). The analyses conducted revealed marked alterations in testicular morphology, a reduction in spermatogenesis and changes in the cell junctions. In addition, the expression and localisation of oestrogen receptors (ERα and ERβ) in germ cells were significantly altered, with a dose-dependent increase in expression. Gly, at the concentrations tested, did not cause appreciable changes in steroidogenesis parameters. Overall, these results indicate that the herbicide can compromise the reproductive morphophysiology of male lizards, potentially reducing their reproductive fitness.

At the same time, in the in vitro model based on human prostate epithelial cells PNT1A, Gly induced cytotoxicity and rapid activation of oestrogen receptors via nuclear translocation. Functional analyses of mitochondrial metabolism showed reduced ATP production, respiratory reserve capacity and proton leak, suggesting the onset of mitochondrial dysfunction. Furthermore, the data suggest the activation of apoptotic pathways in response to treatment.

Overall, the evidence gathered confirms Gly as a potential endocrine disruptor, capable of altering reproductive function in both animal models and human cells, highlighting the urgent need for more controlled use of the herbicide.

Air pollution is a major environmental health hazard. The WHO estimates that air pollution contributes more than 7 million premature deaths globally on an annual basis. This estimate is not uniformly distributed: more than two third deaths occur in developing countries of South Asia. This study evaluates the health risks of air pollution exposure in a megacity Karachi, Pakistan, using the cigarette-equivalent technique. Sampling of fine particulate matter (PM_2.5), nitrogen dioxide (NO₂), and black carbon (BC) was performed at various fixed locations throughout the four seasons of the year. We evaluated the health risks of pollutants exposure using four different health endpoints including low birth weight (<2500 g at term after 37 weeks of gestation), decreased lung function (Forced Expiratory Volume in 1 second), cardiovascular mortality, and lung cancer in residents of Karachi. The average risks of low birth weight from PM_2.5, NO₂, and BC were 37.2, 14.8, and 1.01, respectively, while the average risks of decreased lung function were 93.9, 38.8, and 2.87. Risks of cardiovascular mortality were 51.9, 14.3, and 2.79, and those of lung cancer were 31.3, 6.47, and 1.32, respectively. The remarkably high risks are attributed to high concentrations of air pollutants. These results suggests that residents of Karachi may experience other adverse health effects beyond those typically usually attributed to air pollution.

The European Green Deal (EGD) defines an ambitious pathway for the achievement of climate neutrality, pollution reduction and ecosystem restoration by 2050, with high-level goals, representing a clear challenge for effective local action. This study assesses how cities can implement EGD initiatives by integrating high-resolution environmental monitoring systems with community-driven policy mechanisms. Three European cities from different contexts (rural, coastal and urban) were chosen for a comparative evaluation: Lisbon, Aveiro and Évora.

The methods utilized were as follows: a multi-criteria evaluation framework aligned with EGD’s goals, inspired by the European Innovation Scoreboard; engagement through digital platforms, interviews with specialist-technicians, local non-governmental organizations and the local population; and the placement and incorporation of air and water quality sensors and biodiversity and energy usage monitoring systems. Data collected identified gaps, relations between environmental and policy interventions, and local priorities. The timeframe (2019-2024) aligned with the launch of the European Green Deal, allowing an assessment of recent developments and initial effects on local implementation.

Results indicate that cities with integrated environmental monitoring systems and participatory mechanisms showed alignment with the goals and targets of the European Green Deal, especially in air quality (a reduction in air pollution), urban green planning, improving biodiversity and sustainable mobility policies. Community participation contributed to acceptance and effectiveness of environmental policies, reducing local conflicts and supporting evidence-based decisions. The study formed a Local EGD Readiness Index, capable of assisting cities in assessing their annual progress and comparing data and performance across different regions.

Findings suggest that the local implementation of the EGD depends on the combination of environmental data and modern governance models. This approach allows more transparency and is able to connect the European Union’s ambitions to regional priorities in adaptive policymaking. The framework offers a scalable model for cities seeking to advance their climate neutrality and their environmental resilience.

Introduction

Directive (EU) 2024/3019 on the treatment of urban wastewater mandates using quaternary treatments for reducing both the concentration and toxicity of micropollutants. In this work the effectiveness of electrooxidation and photoelectrooxidation processes to eliminate bentazone (BTZ) was studied. BTZ is a micropollutant detected in the Albufera lake (Spain).

Methods

A new ceramic anode made of Sb-SnO₂ and coated with a Bi₂WO₆ photocatalyst was used. Three supporting electrolytes were tested: 1.65 g L^-1 of NaCl; 2 g L^-1 of Na₂SO₄; and a mixture of 0.46 g L^-1 of NaCl and 1.3 g L^-1 of Na₂SO₄ (this last being similar to Albufera lake conditions). The initial concentration of BTZ was 100 mg L^-1. Two current intensities (0.2 and 0.6 A) were applied, both in the absence and presence of light provided by a xenon lamp. After 4 h, the degradation and mineralization percentages were determined. Ecotoxicity was determined using Lactuca sativa seeds according to US EPA OPPTS 850.4200 standard, after adjusting the pH between 5.5-8, if necessary.

Results

The degradation and mineralization degrees achieved using the mixed electrolyte show intermediate values between those achieved with pure electrolytes. Applying 0.6 A, they are very close to the maximum values achieved with pure NaCl. Moreover, the final effluents toxicity is significantly lower, especially when light is applied. Therefore, the photoelectrooxidation process applying 0.6 A with the mixed electrolyte is the most effective technique from the combined point of view of final degradation (90.9%), mineralization (62.4%) and toxicity (elongation of 47.4% compared to control, p-value < 0.05). Furthermore, the degradation achieved is greater than 80%, minimum value required by Directive (EU) 2024/3019 (Table 3, Annex I) to reduce the micropollutants concentration.

Conclusions

Photoelectrooxidation is a good option as quaternary treatment in wastewater treatment plants with the following additional advantages. It does not need the addition of chemicals, and energy consumption could be supplied by alternative sources, especially in small communities.

Global climate change poses a significant threat to vulnerable island ecosystems, jeopardizing biodiversity and habitats, and potentially leading to species extinction. The paleoenvironmental history of St. Paul Island (Bering Sea), the last refuge for woolly mammoths (Mammuthus primigenius), exemplifies this threat during the 6–4 kyr BP interval. Existing research posits that, unlike mainland extinction attributed to hunting, St. Paul mammoths likely perished during the mid-Holocene due to climate-driven habitat loss, resulting in food scarcity and critical freshwater depletion. This crucial qualitative inference demands robust, direct quantitative evidence from paleoclimatic proxies. To address this need, we compiled and analyzed palynological records from over 20 sediment cores collected from St. Paul Island and the adjacent Bering Sea coastal mainland. Utilizing the Modern Analogue Technique (MAT), we reconstructed the island's biome evolution and quantitatively derived monthly (January and July) and annual precipitation throughout the Holocene. Focusing on 6–4 kyr BP, we performed a quantitative reconstruction of spatiotemporal precipitation patterns across the Bering Sea region, mapping annual precipitation isolines for five key time slices: 6, 5.5, 5, 4.5, and 4 kyr BP. Results show that before 6.6 kyr BP, the island had high annual precipitation (~600 mm/yr) and a biome oscillating between shrub tundra and cold coniferous forest, sustaining a stable relict mammoth population. However, between 6.6 and 4.1 kyr BP, precipitation consistently declined to 400~450 mm/yr, forcing the biome to transition into an arid, desert-like type. This desiccation directly induced critical food and freshwater stress that led to the extinction of the mammoths. Furthermore, annual precipitation along the western Bering Sea coastal regions plummeted to ~240 mm by 4 kyr BP. This quantitative reconstruction provides more direct paleoclimatic evidence (precipitation decline) that supports the freshwater depletion hypothesis, offering a climatic mechanism to supplement the sea-level rise driver.

The growing need for sustainable and affordable technologies for wastewater treatment has driven the development of biosorbents derived from agricultural residues. This work investigates the optimization of alkaline chemical activation applied to two widespread biomasses—spent coffee grounds (SCG) and date pits (DP)—to enhance their capacity to remove methylene blue (MB) from aqueous solutions. Using a two-level full factorial design, the impact of NaOH concentration, activation time, and activation temperature on sorbent performance was assessed.

Among the tested materials, SCG demonstrated a strong response to chemical activation, whereas DP presented limited improvement. The optimal operating conditions for SCG (0.2 M NaOH, 5.5 h activation, and 22 °C) yielded the highest adsorption capacity (140.23 mg g⁻¹), confirming the key role of activation time and temperature in shaping surface reactivity. Textural and spectroscopic analyses (BET, SEM, and FTIR) revealed a mesoporous structure (37.44 m² g⁻¹; pore diameter 4.39 nm) and the presence of functional groups (O–H, C=O, and C–O) actively involved in dye uptake. The point of zero charge (pHpzc_\text{pzc}pzc​ = 5.42) indicated enhanced surface acidity following NaOH treatment.

Adsorption performance was strongly influenced by pH, dosage, and temperature, with higher pH and moderate dosages favoring MB removal. Kinetic modeling identified the pseudo-second-order model as the most suitable (R² = 0.96), supported by intraparticle diffusion analysis indicating multi-step mass transfer. Equilibrium data were best represented by the Sips isotherm (R² = 0.99), predicting a maximum capacity of 145.59 mg g⁻¹. Thermodynamic parameters revealed a spontaneous, exothermic, and entropy-driven process.

Overall, this study demonstrates that statistically optimized alkaline activation significantly enhances the adsorption performance of SCG, validating its potential as an efficient, low-cost biosorbent for treating dye-polluted wastewater, while contributing to the valorization of agro-industrial residues within circular economy frameworks.

It is well established in the literature that green systems can reduce pollutants from urban runoff. However, they may have a negative impact on wastewater quality due to chemical leaching of nutrients from the substrate, with nitrogen and phosphorous being the key elements of concern. The process governing the release or retention of nutrients in porous media is adsorption. It is a surface phenomenon driven by molecular attraction occurring when a solid phase (the adsorbent) comes into contact with a liquid or gaseous phase (the adsorbate). This mechanism is typically investigated through batch experiments. Nevertheless, before conducting batch tests, we performed an aqueous extraction to quantify the amount of nitrogen and phosphorus already present in a green-system substrate.

The experiment was carried out by mixing distilled water and soil at well-defined ratios using a magnetic stirrer, with the mixture sealed in a beaker. An S/L (Solid/Liquid) ratio of 1:10 and a stirring time of 24 h were considered to ensure proper dilution of the medium. The sample was then centrifuged for 15 minutes at 4500 rpm to ensure proper separation of the solid and liquid phases. Afterwards, the supernatant was filtered (90 μm) under vacuum, and the extracted liquid phase was analyzed for reactive phosphorus, nitrate nitrogen, and ammonium nitrogen using a UV-VIS spectrophotometer. Results from the aqueous extract showed very low concentrations of reactive phosphorus, nitric nitrogen, and ammonium nitrogen with values of 1,24 mg L^-1, 2,83 mg L^-1, and 0,084 mg L^-1, respectively. These findings indicate that the substrate does not contribute significantly to nutrient loads through initial leaching. In addition, the results provide an essential reference point for the design and interpretation of subsequent adsorption batch experiments, and they indicate that the substrate has a negligible initial nutrient release.