Investigating the impact of microplastics on triphenyl phosphate adsorption in soil: Insights into environmental factors and soil properties.

Microplastics (MPs) pose significant environmental pollution problems owing to their diverse properties such as various shapes, sizes, compositions, surface features, and levels of degradation. Moreover, their interactions with toxic chemicals and aging processes add complexity to environmental research. This study investigated the adsorption of triphenyl phosphate (TPhP) in soil-only, MP-only, and soil-MP simulated environments under different conditions. The experiment involved three phases: initial exposure to a pH of 5.5 under fluorescent light, subsequent introduction of ultraviolet (UV) radiation, and pH adjustment to 4.0 and 7.0, while maintaining UV exposure, each lasting 7 days. The study found that environmental factors affected TPhP sorption capacity, with higher adsorption observed under UV radiation and acidic conditions. In contrast, the MP-only systems showed no clear trend for TPhP adsorption, suggesting kinetic limitations. When MPs were added to the soil, the adsorption dynamics were altered, with varying adsorption capacities observed for different MP polymers under different aging conditions. ATR-FTIR spectroscopy, micro-Raman spectroscopy, and water contact angle measurements suggested potential photooxidation processes and changes in the surface hydrophobicity of the MPs subjected to simulated environmental conditions. This study provides valuable insights into the interplay between soil properties, MP characteristics, and environmental factors in determining TPhP sorption dynamics in soil-MP environments.

Assessing emerging and priority micropollutants in sewage sludge: environmental insights and analytical approaches.

The application of sewage sludge (SS) in agriculture, as an alternative to manufactured fertilizers, is current practice worldwide. However, as wastewater is collected from households, industries, and hospitals, the resulting sludge could contaminate land with creeping levels of pharmaceuticals, pesticides, heavy metals, polycyclic aromatic hydrocarbons, and microplastics, among others. Thus, the sustainable management of SS requires the development of selective methods for the identification and quantification of pollutants, preventing ecological and/or health risks. This study presents a thorough evaluation of emerging and priority micropollutants in SS, through the lens of environmental insights, by developing and implementing an integrated analytical approach. A quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction method, coupled with gas chromatography and liquid chromatography, was optimized for the determination of 42 organic compounds. These include organophosphorus pesticides, organochlorine pesticides, pyrethroid pesticides, organophosphate ester flame retardants, polybrominated diphenyl ethers, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons. The optimization of the dispersive-solid phase for clean-up, combined with the optimization of chromatographic parameters, ensured improved sensitivity. Method validation included assessments for recovery, reproducibility, limit of detection (LOD), and limit of quantification (LOQ). Recoveries ranged from 59.5 to 117%, while LODs ranged from 0.00700 to 0.271 µg g-1. Application of the method to seven SS samples from Portuguese wastewater treatment plants revealed the presence of sixteen compounds, including persistent organic pollutants. The quantification of α-endosulfan, an organochlorine pesticide, was consistently observed in all samples, with concentrations ranging from 0.110 to 0.571 µg g-1. Furthermore, the study encompasses the analysis of agronomic parameters, as well as the mineral and metal content in SS samples. The study demonstrates that the levels of heavy metals comply with legal limits. By conducting a comprehensive investigation into the presence of micropollutants in SS, this study contributes to a deeper understanding of the environmental and sustainable implications associated with SS management.

Accumulation of organophosphorus pollutants in adipose tissue of obese women - metabolic alterations.

Organophosphorus pesticides (OPPs) and organophosphate esters (OPEs) are organophosphorus compounds created as substitutes for persistent environmental pollutants, namely organochlorines pesticides and brominated flame retardants, respectively. However, there is evidence that organophosphorus compounds are also widespread across the environment and have adverse effects on biota. In humans, OPPs and OPEs were reported to be carcinogenic, neurotoxic, hepatotoxic, nephrotoxic, amongst others. As lipophilic compounds, these accumulate in fat tissues as adipose tissue. Yet biomonitoring studies and analytical methodologies to assess these compounds in the human body are scarce, particularly in adipose tissue. In this study, the presence of six OPPs and seven OPEs was determined in samples of subcutaneous adipose tissue (scAT) and visceral adipose tissue (vAT) from 188 adult obese women. OPPs and OPEs were quantified by gas chromatography (GC) flame photometric detection and confirmed in GC tandem mass spectrometry. The detection frequencies ranged between 0.5-1.6% and 48-53%, respectively for OPPs and OPEs. Organophosphorus pollutants were present in both adipose tissues and median concentrations were 0.008 ± 0.020 µg/g scAT and 0.009 ± 0.020 µg/g vAT. A total of 32 Spearman's correlations were found between organophosphorus pollutants concentrations in adipose tissue and several biochemical parameters (18 positive and 14 negative). Our results show that anthropometric and hormonal parameters, cholesterol, glycaemia, macrominerals, urea and sedimentation velocity might be influenced by the presence of these compounds. The presence of organophosphorus pollutants in the environmental and their possible effect on female metabolic processes is concerning. Particularly because presently OPEs usage is not controlled or limited by any regulation. More studies are needed to fully understand these pollutants behaviour and hazard effects on human health, biota, and the environment so control regulations can be drawn to prevent and lessen their effects.

Assessment of the Antioxidant Capacity of Commercial Coffee Using Conventional Optical and Chromatographic Methods and an Innovative Electrochemical DNA-Based Biosensor.

As one of the most popular beverages in the world, coffee is a rich source of non-enzymatic bioactive compounds with antioxidant capacity. In this study, twelve commercial coffee beverages found in local Portuguese markets were assessed to determine their total phenolic and flavonoid contents, as well as their antioxidant capacity, by conventional optical procedures, namely, ferric reducing antioxidant power and DPPH-radical scavenging assay, and non-conventional procedures such as a homemade DNA-based biosensor against two reactive radicals: HO• and H2O2. The innovative DNA-based biosensor comprised an adenine-rich oligonucleotide adsorbed onto a carbon paste electrode. This method detects the different peak intensities generated by square-wave voltammetry based on the partial damage to the adenine layer adsorbed on the electrode surface by the free radicals in the presence/absence of antioxidants. The DNA-based biosensor against H2O2 presented a higher DNA layer protection compared with HO• in the presence of the reference gallic acid. Additionally, the phenolic profiles of the twelve coffee samples were assessed by HPLC-DAD, and the main contributors to the exhibited antioxidant capacity properties were caffeine, and chlorogenic, protocatechuic, neochlorogenic and gallic acids. The DNA-based sensor used provides reliable and fast measurements of antioxidant capacity, and is also cheap and easy to construct.

The Microplastics Iceberg: Filling Gaps in Our Understanding.

Plastic is an indispensable material in modern society; however, high production rates combined with inadequate waste management and disposal have resulted in enormous stress on ecosystems. In addition, plastics can become smaller particles known as microplastics (MPs) due to physical, chemical, and biological drivers. MP pollution has become a significant environmental problem affecting terrestrial and aquatic ecosystems worldwide. Although the topic is not entirely new, it is of great importance to the field of polymers, drawing attention to specific gaps in the existing literature, identifying future areas of research, and improving the understanding of MP pollution and its environmental impacts. Despite progress in this field, problems remain. The lack of standardized methods for MP sampling, separation, extraction, and detection makes it difficult to collect information and establish links between studies. In addition, the distribution and pathways of MPs in ecosystems remain unknown because of their heterogeneous nature and the complex matrices in which they occur. Second, toxicological tests showed that MPs can be ingested by a wide range of organisms, such as Danio rerio and Eisenia fetida, resulting in gut obstruction, physical damage, histological changes, and oxidative stress. The uptake of MP and their toxicological effects depend on their shape, size, concentration, and polymer composition. Furthermore, MPs can enter the food chain, raising concerns regarding potential contaminations for human and environmental health. This review paper sheds light on the pressing issue of MP pollution and highlights the need for interdisciplinary collaboration between scientists, policymakers, and industry leaders.

Exploring the impacts of microplastics and associated chemicals in the terrestrial environment - Exposure of soil invertebrates to tire particles.

Abrasion of tire wear is one of the largest sources of microplastics to the environment. Although most tire particles settle into soils, studies on their ecotoxicological impacts on the terrestrial environment are scarce. Here, the effects of tire particles (<180 µm) on three ecologically relevant soil invertebrate species, the enchytraeid worm Enchytraeus crypticus, the springtail Folsomia candida and the woodlouse Porcellio scaber, were studied. These species were exposed to tire particles spiked in soil or in food at concentrations of 0.02%, 0.06%, 0.17%, 0.5% and 1.5% (w/w). Tire particles contained a variety of potentially harmful substances. Zinc (21 900 mg kg-1) was the dominant trace element, whilst the highest concentrations of the measured organic compounds were detected for benzothiazole (89.2 mg kg-1), pyrene (4.85 mg kg-1), chlorpyrifos (0.351 mg kg-1), HCB (0.134 mg kg-1), methoxychlor (0.116 mg kg-1) and BDE 28 (0.100 mg kg-1). At the highest test concentration in soil (1.5%), the tire particles decreased F. candida reproduction by 38% and survival by 24%, and acetylcholinesterase (AChE) activity of P. scaber by 65%, whilst the slight decrease in the reproduction of E. crypticus was not dose-dependent. In food, the highest test concentration of tire particles reduced F. candida survival by 38%. These results suggest that micro-sized tire particles can affect soil invertebrates at concentrations found at roadsides, whilst short-term impacts at concentrations found further from the roadsides are unlikely.

Individual and mixture toxicity evaluation of three pharmaceuticals to the germination and growth of Lactuca sativa seeds.

This work aims to assess, individually and in mixtures, possible phytotoxic effects of three pharmaceuticals (paracetamol, ibuprofen and amoxicillin) on germination and early growth of Lactuca sativa seeds. Pharmaceuticals are an important group of emerging contaminants, whose presence has been described in several environmental compartments, including soils. However, knowledge on their possible impact in terrestrial organisms is still sparse and even more when mixtures are considered. Germination tests are important to evaluate the quality of soil and the toxic effects that contaminants can pose to plants. The acute effects of individual pharmaceuticals as well as binary and ternary mixtures were assessed using different endpoints, namely: percentage of seed germination, root elongation, shoot and leaf length, after an exposure time of five days. Overall, in the exposure of L. sativa seeds to individual pharmaceuticals there are indications of acute toxicity in the early plant growth. However, this inhibitory effect tends to be cancelled in the acute exposure to mixtures. This study shows the importance of evaluating the toxicity of mixtures of pharmaceuticals, since they might have distinct toxic effects when compared to the single compounds, and also because, probably, it is the closest scenario to the reality that can be found in the environment.

Ecotoxicological impact of two soil remediation treatments in Lactuca sativa seeds.

Pharmaceuticals have been identified as environmental emerging pollutants and are present in different compartments, including soils. Chemical remediation showed to be a good and suitable approach for soil remediation, though the knowledge in their impact for terrestrial organisms is still limited. Therefore, in this work, two different chemical remediation treatments (Fenton oxidation and nanoremediation) were applied to a soil contaminated with an environmental representative concentration of ibuprofen (3 ng g(-1)). The phytotoxic impact of a traditional soil remediation treatment (Fenton oxidation) and of a new and more sustainable approach for soil remediation (nanoremediation using green nano-scale zero-valent iron nanoparticles (nZVIs)) was evaluated in Lactuca sativa seeds. Percentage of seed germination, root elongation, shoot length and leaf length were considered as endpoints to assess the possible acute phytotoxicity of the soil remediation treatments as well as of the ibuprofen contaminated soil. Both chemical remediation treatments showed to have a negative impact in the germination and development of lettuce seeds, exhibiting a reduction up to 45% in the percentage of seed germination and a decrease around 80% in root elongation comparatively to the contaminated soil. These results indicate that chemical soil remediation treatments could be more prejudicial for terrestrial organisms than contaminated soils.