Long-Term Polyethylene (Bio)Degradation in Landfill: Environmental and Human Health Implications from Comprehensive Analysis.

This study investigates the process of long-term (bio)degradation of polyethylene (PE) in an old municipal waste landfill (MWL) and its implications for environmental and human health. Advanced techniques, such as ICP-ES/MS and IC-LC, were used to analyze heavy metals and anions/cations, demonstrating significant concentration deviations from control samples. The soil's chemical composition revealed numerous hazardous organic compounds, further indicating the migration of additives from PE to the soil. Toxicological assessments, including Phytotoxkit FTM, Microtox® bioassay, and Ostracodtoxkit®, demonstrated phytotoxicity, acute toxicity, and high mortality in living organisms (over 85% for Heterocypris Incongruens). An unusual concentration of contaminants in the MWL's middle layers, linked to Poland's economic changes during the 1980s and 1990s, suggests increased risks of pollutant migration, posing additional environmental and health threats. Moreover, the infiltration capability of microorganisms, including pathogens, into PE structures raises concerns about potential groundwater contamination through the landfill bottom. This research underscores the need for vigilant management and updated strategies to protect the environment and public health, particularly in older landfill sites.

Assessment of Apple Peel Barrier Effect to Pesticide Permeation Using Franz Diffusion Cell and QuEChERS Method Coupled with GC-MS/MS.

In this study, a new approach to pesticide permeation through the apple peel into the pulp is discussed. The tested compounds can be classified, based on mode of action, as systemic (boscalid, cyprodinil, pirimicarb, propiconazole and tebuconazole) or contact (captan, cypermethrin and fludioxonil) pesticides. The barrier effect was assessed using a Franz flow-type vertical diffusion cell system. A residue analysis was performed using a modified quick, easy, cheap, efficient, rugged and safe (QuEChERS) extraction method coupled to gas chromatography with tandem mass spectrometry (GC-MS/MS). The limits of detection (LODs) ranged between 2.6 µg kg-1 (pirimicarb) and 17 µg kg-1 (captan), with the coefficient of variability (CV) lower than 6%, while recoveries ranged from 85% (boscalid) to 112% (captan) at 0.1 and 1 mg kg-1 spiked levels. The highest peel penetration was observed for pirimicarb, captan and cyprodinil, with cumulative permeations of 90, 19 and 17 µg cm-2, respectively. The total absorption was in the range from 0.32% (tebuconazole) to 32% (pirimicarb). Only cypermethrin was not quantitatively detected in the pulp, and its use can be recommended in crop protection techniques. The obtained results indicate that molecular weight, octanol-water partition coefficient and water solubility are important parameters determining the process of pesticide absorption.

Intensive poultry farming: A review of the impact on the environment and human health.

Poultry farming is one of the most efficient animal husbandry methods and it provides nutritional security to a significant number of the world population. Using modern intensive farming techniques, global production has reached 133.4 mil. t in 2020, with a steady growth each year. Such intensive growth methods however lead to a significant environmental footprint. Waste materials such as poultry litter and manure can pose a serious threat to environmental and human health, and need to be managed properly. Poultry production and waste by-products are linked to NH3, N2O and CH4 emissions, and have an impact on global greenhouse gas emissions, as well as animal and human health. Litter and manure can contain pesticide residues, microorganisms, pathogens, pharmaceuticals (antibiotics), hormones, metals, macronutrients (at improper ratios) and other pollutants which can lead to air, soil and water contamination as well as formation of antimicrobial/multidrug resistant strains of pathogens. Dust emitted from intensive poultry production operations contains feather and skin fragments, faeces, feed particles, microorganisms and other pollutants, which can adversely impact poultry health as well as the health of farm workers and nearby inhabitants. Fastidious odours are another problem that can have an adverse impact on health and quality of life of workers and surrounding population. This study discusses the current knowledge on the impact of intensive poultry farming on environmental and human health, as well as taking a look at solutions for a sustainable future.

The stimulating role of syringic acid, a plant secondary metabolite, in the microbial degradation of structurally-related herbicide, MCPA.

The ability of microorganisms to degrade xenobiotics can be exploited to develop cost-effective and eco-friendly bioremediation technologies. Microorganisms can degrade almost all organic pollutants, but this process might be very slow in some cases. A promising way to enhance removal of recalcitrant xenobiotics from the environment lies in the interactions between plant exudates such as plant secondary metabolites (PSMs) and microorganisms. Although there is a considerable body of evidence that PSMs can alter the microbial community composition and stimulate the microbial degradation of xenobiotics, their mechanisms of action remain poorly understood. With this in mind, our aim was to demonstrate that similarity between the chemical structures of PSMs and xenobiotics results in higher micropollutant degradation rates, and the occurrence of corresponding bacterial degradative genes. To verify this, the present study analyses the influence of syringic acid, a plant secondary metabolite, on the bacterial degradation of an herbicide, 4-chloro-2-methylphenoxyacetic acid (MCPA). In particular, the presence of appropriate MCPA degradative genes, MCPA removal efficiency and changes in samples phytotoxicity have been analyzed. Significant MCPA depletion was achieved in samples enriched with syringic acid. The results confirmed not only greater MCPA removal from the samples upon spiking with syringic acid, and thus decreased phytotoxicity, but also the presence of a greater number of genes responsible for MCPA biodegradation. 16S rRNA gene sequence analysis revealed ubiquitous enrichment of the ß-proteobacteria Rhodoferax, Achromobacter, Burkholderia and Cupriavidus. The obtained results provide further confirmation that plant metabolites released into the rhizosphere can stimulate biodegradation of xenobiotics, including MCPA.

Determination of Selected Priority Pesticides in High Water Fruits and Vegetables by Modified QuEChERS and GC-ECD with GC-MS/MS Confirmation.

A modified quick, easy, cheap, efficient, rugged and safe (QuEChERS) method coupled to gas chromatography with electron capture detector (GC-ECD) was developed for simultaneous determination of selected electronegative pesticides in fruits and vegetables with high water content. The chosen compounds are commonly detected in fruit and vegetable crops, and some of their metabolites have even been found in human urine. In addition, some of them are known or suspected carcinogens according to the International Agency for Research of Cancer. Extraction and clean up parameters were optimized, thus the original QuEChERS method was modified to decrease solvent usage, in accordance with 'green chemistry' principles. The proposed methodology was validated in terms of selectivity, specificity, linearity, precision and accuracy. The obtained limits of detection (LODs) for all investigated pesticides ranged from 5.6 µg·kg-1 to 15 µg·kg-1 and limits of quantification (LOQs) from 17 µg·kg-1 to 45 µg·kg-1. The obtained data demonstrated the good reproducibility and stability of the procedure in the tested concentration range up to 10 mg·kg-1, with relative standard deviations (RSDs) lower than 10%. Recoveries for spiked pear samples at LOQ level for each pesticide were from 90% to 107% with RSDs lower than 9.6%. The suitability of the developed procedure was tested on various fruit and vegetable samples available on the market at different seasons. The proposed methodology is applicable for detection and monitoring of selected pesticides not only in fruits and vegetables with high water content, but also in samples containing large amounts of pigments and dyes.

Advancement in Determination of Phthalate Metabolites by Gas Chromatography Eliminating Derivatization Step.

A gas chromatography-mass spectrometry (GC-MS) method to determine polar and thermally unstable phthalate metabolites [monomethyl phthalate-MMP, monoethyl phthalate-MEP, mono-n-butyl phthalate-MnBP, mono-(2-ethylhexyl) phthalate-MEHP] has been developed. This is the first report presenting the separation of monophthalates without derivatization step and any additional equipment or special injection port. Injection parameters (temperature, pressure, time, and volume of injection), chromatographic separation (retention gap, temperature program), and MS detection/identification (working parameters, ion selection) were investigated. Mechanisms and phenomena occurring under different conditions in the GC injector were evaluated and discussed. The limits of detection (LODs) of MMP, MEP, MnBP, MEHP in the protocol were 0.049, 0.036, 0.038, and 0.029 ng (per 2 µL of injection), respectively. The response of the monophthalates was found to be linear in the tested concentration range (for MMP: 0.15-100 ng, MEP and MnBP: 0.11-100 ng, MEHP: 0.087-100 ng per 2 µL) with the coefficient of determination higher than 0.9817 and inter-day precision in the range of 1.4-5.4%. The developed method is fast, easy and repeatable. Moreover, it allows for the elimination of derivatization agents, reduction of toxic waste production and simplification of analytical procedure.

Fast, sensitive and reliable multi-residue method for routine determination of 34 pesticides from various chemical groups in water samples by using dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry.

A simple and efficient dispersive liquid-liquid microextraction technique (DLLME) was developed by using a mixture of two solvents: 40 µL of tetrachlorethylene (extraction solvent) and 1.0 mL of methanol (disperser solvent), which was rapidly injected with a syringe into 10 mL of water sample. Some important parameters affecting the extraction efficiency, such as type and volume of solvents, water sample volume, extraction time, temperature, pH adjustment and salt addition effect were investigated. Simultaneous determination of 34 commonly used pesticides was performed by using gas chromatography coupled with mass spectrometry (GC-MS). The procedure has been validated in order to obtain the highest efficiency at the lowest concentration levels of analytes to fulfill the requirements of regulations on maximum residue limits. Under the optimum conditions, the linearity range was within 0.0096-100 µg L-1. The limits of detection (LODs) of the developed DLLME-GC-MS methodology for all investigated pesticides were in the range of 0.0032 (endrin)-0.0174 (diazinon) µg L-1 and limits of quantification (LOQs) from 0.0096 to 0.052 µg L-1. At lower concentration of 1 µg L-1 for each pesticide, recoveries ranged between 84% (tebufenpyrad) and 108% (deltamethrin) with relative standard deviations (RSDs) (n = 7) from 1.1% (metconazole) to 11% (parathion-mehtyl). This methodology was successfully applied to check contamination of environmental samples. The procedure has proved to be selective, sensitive and precise for the simultaneous determination of various pesticides. The optimized analytical method is very simple and rapid (less than 5 min). Graphical abstract Analytical procedure for testing water samples consists of dispersive liquid-liquid microextraction (DLLME) and gas chromatography coupled with mass spectrometry (GC-MS).

Multi-residue method for the determination of 16 recently used pesticides from various chemical groups in aqueous samples by using DI-SPME coupled with GC-MS.

A simple and solvent-free multi-residue method has been optimized to determine 16 currently used pesticides from different chemical groups in aqueous samples. The extraction of analytes was carried out with direct immersion solid-phase microextraction (DI-SPME) and for the identification and quantitative determination gas chromatography coupled with mass spectrometry (GC-MS) was applied. Two commonly used adsorbent coatings have been applied and compared: 100 µm of polydimethylsiloxane (PDMS) and 85 µm of polyacrylate (PA). The method development parameters of DI-SPME, analyte desorption and GC-MS analysis have been outlined along with the final experimental conditions. When the optimum extraction conditions were applied (extraction time 60 min, 10% (w/v) NaCl solution, 45°C) the limits of detection (LODs) were in the range of 0.015-0.13 µgL(-1) and the relative standard deviations (RSDs) were between 1.9 and 9.6%. The developed analytical method was successfully applied to the analysis of natural water samples from the following sources: river, sea, canal and rain.

Green aspects of techniques for the determination of currently used pesticides in environmental samples.

Pesticides are among the most dangerous environmental pollutants because of their stability, mobility and long-term effects on living organisms. Their presence in the environment is a particular danger. It is therefore crucial to monitor pesticide residues using all available analytical methods. The analysis of environmental samples for the presence of pesticides is very difficult: the processes involved in sample preparation are labor-intensive and time-consuming. To date, it has been standard practice to use large quantities of organic solvents in the sample preparation process; but as these solvents are themselves hazardous, solvent-less and solvent-minimized techniques are becoming popular. The application of Green Chemistry principles to sample preparation is primarily leading to the miniaturization of procedures and the use of solvent-less techniques, and these are discussed in the paper.

Solventless and solvent-minimized sample preparation techniques for determining currently used pesticides in water samples: a review.

The intensification of agriculture means that increasing amounts of toxic organic and inorganic compounds are entering the environment. The pesticides generally applied nowadays are regarded as some of the most dangerous contaminants of the environment. Their presence in the environment, especially in water, is hazardous because they cause human beings to become more susceptible to disease. For these reasons, it is essential to monitor pesticide residues in the environment with the aid of all accessible analytical methods. The analysis of samples for the presence of pesticides is problematic, because of the laborious and time-consuming operations involved in preparing samples for analysis, which themselves may be a source of additional contaminations and errors. To date, it has been standard practice to use large quantities of organic solvents in the sample preparation process; but as these solvents are themselves hazardous, solventless and solvent-minimized techniques are coming into use. This paper discusses the most commonly used over the last 15 years sample preparation techniques for monitoring organophosphorus and organonitrogen pesticides residue in water samples. Furthermore, a significant trend in sample preparation, in accordance with the principles of 'Green Chemistry' is the simplification, miniaturization and automation of analytical techniques. In view of this aspect, several novel techniques are being developed in order to reduce the analysis step, increase the sample throughput and to improve the quality and the sensitivity of analytical methods. The paper describes extraction techniques requiring the use of solvents - liquid-liquid extraction (LLE) and its modifications, membrane extraction techniques, hollow fibre-protected two-phase solvent microextraction, liquid phase microextraction based on the solidification of a floating organic drop (LPME-SFO), solid-phase extraction (SPE) and single-drop microextraction (SDME) - as well as solvent-free techniques - solid phase microextraction (SPME) and stir bar sorptive extraction (SBSE). The advantages and drawbacks of these techniques are also discussed, and some solutions to their limitations are proposed.