Plastic compounds and liver diseases: Whether bisphenol A is the only culprit.

Plastics, while providing modern conveniences, have become an inescapable source of global concern due to their role in environmental pollution. Particularly, the focus on bisphenol A (BPA) reveals its biohazardous nature and association with liver issues, specifically steatosis. However, research indicates that BPA is just one facet of the problem, as other bisphenol analogues, microplastics, nanoplastics and additional plastic derivatives also pose potential risks. Notably, BPA is implicated in every stage of non-alcoholic fatty liver disease (NAFLD) onset and progression, surpassing hepatitis B virus as a primary cause of chronic liver disease worldwide. As plastic contamination tops the environmental contaminants list, urgent action is needed to assess causative factors and mitigate their impact. This review delves into the molecular disruptions linking plastic pollutant exposure to liver diseases, emphasizing the broader connection between plastics and the rising prevalence of NAFLD.

Non-targeted analysis based on quantitative prediction and toxicity assessment for emerging contaminants in tire particle leachates.

Non-targeted analysis (NTA) has great potential to screen emerging contaminants in the environment, and some studies have conducted in-depth investigation on environmental samples. Here, we used a NTA workflow to identify emerging contaminants in used tire particle (TP) leachates, followed by quantitative prediction and toxicity assessment based on hazard scores. Tire particles were obtained from four different types of automobiles, representing the most common tires during daily transportation. With the instrumental analysis of TP leachates, a total of 244 positive and 104 negative molecular features were extracted from the mass data. After filtering by a specialized emerging contaminants list and matching by spectral databases, a total of 51 molecular features were tentatively identified as contaminants, including benzothiazole, hexaethylene glycol, 2-hydroxybenzaldehyde, etc. Given that these contaminants have different mass spectral responses in the mass spectrometry, models for predicting the response of contaminants were constructed based on machine learning algorithms, in this case random forest and artificial neural networks. After five-fold cross-validation, the random forest algorithm model had better prediction performance (MAECV = 0.12, Q2 = 0.90), and thus it was chosen to predict the contaminant concentrations. The prediction results showed that the contaminant at the highest concentration was benzothiazole, with 4,875 µg/L in the winter tire sample. In addition, the joint toxicity assessment of four types of tires was conducted in this study. According to different hazard levels, hazard scores increasing by a factor 10 were developed, and hazard scores of all the contaminants identified in each TP leachate were summed to obtain the total hazard score. All four tires were calculated to have relatively high risks, with winter tires having the highest total hazard score of 40,751. This study extended the application of NTA research and led to the direction of subsequent targeting studies on highly concentrated and toxic contaminants.

Leaching and cytotoxicity of bismuth oxide in ProRoot MTA - A laboratory investigation.

AIM: The present study examined the leaching and cytotoxicity of bismuth from ProRoot MTA and aimed to identify whether bismuth leaching was affected by the cement base and the immersion regime used. METHODOLOGY: The leaching profile of bismuth was examined from ProRoot MTA and compared with hydroxyapatite containing 20% bismuth oxide as well as hydroxyapatite and tricalcium silicate to investigate whether bismuth release changed depending on the cement base. Bismuth leaching was determined after 30 and 180 days of ageing immersed in Dulbecco's modified Eagle's medium (DMEM) using mass spectroscopy (ICP-MS). The media were either unchanged or regularly replenished. The pH, surface microstructure and phase changes of aged materials were assessed. Wistar rat femoral bone marrow stromal cells (BMSCs) and cutaneous fibroblasts were isolated, cultured and seeded for cell counting (trypan blue live/dead) after exposure to non-aged, 30- and 180-days-aged samples in regularly replenished DMEM. Aged DMEM in contact with materials was also used to culture BMSCs to investigate the effect of material leachates on the cells. Gene expression analysis was also carried out after direct exposure of cells to non-aged materials. Differences between groups were statistically tested at a significance level of 5%. RESULTS: All materials exhibited alterations after immersion in DMEM and this increased with longer exposure times. The bismuth leached from ProRoot MTA as detected by ICP-MS. Aged ProRoot MTA samples exhibited a black discolouration and surface calcium carbonate deposition. ProRoot MTA influenced cell counts after direct exposure and its 180-days leachates reduced BMSC viability. After direct BMSC contact with non-aged ProRoot MTA an upregulation of metallothionein (MT1 and MT2A) expression and down-regulation of collagen-1a (Col-1a) and bone sialoprotein (BSP) expression was identified. CONCLUSIONS: Bismuth leaching was observed throughout 180-days observation period from all materials containing bismuth oxide. This negatively influenced cell viability and gene expression associated with bismuth exposure. This is the first study to report that metallothionein gene expression was influenced by exposure to ProRoot MTA.

Strontium leaching from municipal waste subjected to incineration.

The aim of the study was to determine the content and leachability of Sr in ashes obtained through combusting municipal waste in household furnaces. The waste had been collected as a mixed stream and as separate fractions (i.e. furniture, sponges, waste paper, PCV packaging, plastic-coated paper cartons, imitation leather, rubber, textiles and polystyrene). Using single-step chemical extractions, (HCl + HNO3, H2O, 0.01 M CaCl2, 0.1 M CH3COOH), we determined the total content of Sr (TC) and proportions of the following fractions: water-leachable, phytoavailable and easily soluble and bound to carbonates. We also analyzed the effect of reducing pH in the extraction solutions on St leachability from the study material. The study showed that Sr concentration in ash generated from the combustion of conventional fuels, alternative fuels and municipal waste ranged from 114 to 1006 mg/kg. The largest amounts of Sr were found in ash generated from the combustion of alternative fuels (coal pellets 488-1006 mg/kg), conventional fuels (hard coal 430-670 mg/kg) and mixed waste (237-825 mg/kg). The most mobile fraction of Sr (water-leachable) comprised from 1.3% to nearly 91% TC; the phytoavailable fraction and the ion-exchange and carbonate-bound fraction comprised 3-92% TC and 9-72% TC, respectively. We also found that the greatest pH reductions do not always entail the greatest amounts of extracted Sr. A much more significant factor in this respect is the mineral and chemical composition of primary materials, which can buffer changes in pH. The Risk Assessment Code (RAC) values pointed to a varied environmental risk and the highest RAC values (> 70) were found for coal pellets, wood pellets, straw, rubber and plastic containers for mixed oils.

Examination of the environmental behavior of phosphogypsum with the application of lab-scale experiment.

Phosphogypsum (PG) is a reject of the phosphoric acid production process in phosphate fertilizer industries. The process results in the production of relatively large quantities of PG that it might cause serious environmental and human health concerns. The data of a laboratory investigation of PG are presented here. Lab-scale experiments with lysimeters were conducted in order to simulate and examine the environmental characteristics and the temporal behavior of PG leachates in terms of physicochemical characteristics and chemical composition. Based on the results, leachates from already deposited for many years PG or its mixture with marble powder, seemed to have better pH and conductivity values and lower elemental concentrations compared to leachates from freshly disposed PG. However, the leachates characteristics improve and stabilize in both cases after four days of irrigation or of 1080-1240 mm of rain. Most major elements were found to have minimal leachability, and the material satisfied the environmental limits for its disposal at landfills for inert and non-hazardous wastes.

Human health risks of metal contamination in Shallow Wells around waste dumpsites in Abeokuta Metropolis, Southwestern, Nigeria.

Metal contamination in shallow wells through solid waste leaching is a serious environmental problem with contribution to global cancer cases. This paper evaluated the health risks of metals in shallow wells around dumpsites in the Abeokuta metropolis, Nigeria. Five dumpsites were purposively selected to sample twenty-five shallow wells. In situ and laboratory analyses for physico-chemical parameters, copper, lead, cadmium, iron, and chromium were conducted following the APHA standard procedure. Carcinogenic and non-carcinogenic risks for oral and dermal routes were evaluated for adult males and females, children, and infants. Findings revealed that all wells were acidic (pH = 5.82-6.48), with Fe and Cd concentrations above the established limits. The wells around Obada, Obantoko, and Saje dumpsites had high EC (up to 1200 µS/cm), Cu, and Pb concentrations above the permissible limits. Non-carcinogenic risks for oral ingestion were significant for all age groups (hazard index: HI > 1), and the significance level across dumping areas increased in the order: Saje > Obantoko > Obada > Idi-aba > Lafenwa. All wells assessed in Saje and Obantoko recorded significant HI of dermal exposure for children and infants. Cancer risks were significant for all age groups (CR > 1.0E - 04), and metal contributions followed: Cd > Cr > Pb. The overall trend of significant risks for non-carcinogenic and carcinogenic via oral and dermal routes is in the order of infant > children > adult female > adult male. This suggests that groundwater users within the studied areas may experience diverse illnesses or cancer in their lifetime, particularly children and infants.

Effects of leachates from UV-weathered microplastic on the microalgae Scenedesmus vacuolatus.

Plastics undergo successive fragmentation and chemical leaching steps in the environment due to weathering processes such as photo-oxidation. Here, we report the effects of leachates from UV-irradiated microplastics towards the chlorophyte Scenedesmus vacuolatus. The microplastics tested were derived from an additive-containing electronic waste (EW) and a computer keyboard (KB) as well as commercial virgin polymers with low additive content, including polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), and polystyrene (PS). Whereas leachates from additive-containing EW and KB induced severe effects, the leachates from virgin PET, PP, and PS did not show substantial adverse effects in our autotrophic test system. Leachates from PE reduced algae biomass, cell growth, and photosynthetic activity. Experimental data were consistent with predicted effect concentrations based on the ionization-corrected liposome/water distribution ratios (Dlip/w) of polymer degradation products of PE (mono- and dicarboxylic acids), indicating that leachates from weathering PE were mainly baseline toxic. This study provides insight into algae toxicity elicited by leachates from UV-weathered microplastics of different origin, complementing the current particle- vs. chemical-focused research towards the toxicity of plastics and their leachates.

Hydraulic performance, consolidation characteristics and shear strength analysis of bentonites in the presence of fly-ash, sewage sludge and paper-mill leachates for landfill application.

A rapid upsurge in urban and industrial developments leads to increased generations of solid wastes. The most accepted technique of waste discarding around the world is landfilling. Leaching chemicals from municipal dumping grounds can pollute the groundwater source and the surrounding environment without appropriate precautionary measures. Bentonite is a low-cost constituent used as a liner material in landfills due to its low permeability, high sealing ability, high specific surface area, and the ability to hold up the impurity migration through adsorption. However, leachate interaction with bentonite may alter its properties and reduce its usefulness as a barrier material in the long term. Also, bentonite having different chemical and mineralogical compositions will behave differently due to the leachate interaction. Therefore, it is necessary to compare the performance of various bentonites in the presence of leachates. In the present investigation, two Indian bentonites of different mineralogical compositions were studied for their change in the index properties, swelling, swelling potential, swelling pressure, hydraulic conductivity, consolidation parameters and shear strength properties in the presence of fly ash, sewage sludge and paper mill leachates. The outcomes showed that in the presence of all the leachates, liquid limit, free swell, compression index, swelling potential, swelling pressure, time to complete 90% of consolidation and shear strength dropped; whereas, hydraulic conductivity and coefficient of consolidation increased. Besides, the quality of bentonite prominently influenced the hydraulic, strength and swelling behaviour. The bentonite having a higher cation exchange capacity, liquid limit, specific surface area, and swelling capability undergoes a higher variability in the free swell (80.0, 73.8 and 76.9% decline), liquid limit (73.5, 61.7 and 69.2% decline), swelling potential (61.3, 55.7 and 51.0% decline), swelling pressure (53.3 and 56.4% decrease), and hydraulic conductivity (57.5, 8.6 and 41.1 times increase at a void ratio of 1.2) values when infused with fly ash, sewage sludge and paper mill leachates, respectively. The study also showed that the fly ash leachate interaction causes a higher variation in bentonite behaviour than sewage sludge and paper mill leachates. The study's findings would prove beneficial to design engineers for selecting bentonite types for landfill liners.

Concentration profiles of per- and polyfluoroalkyl substances in major sources to the environment.

A review of published literature was conducted to present the concentrations and composition profiles of per- and polyfluoroalkyl substances (PFAS) from significant sources to the environment. The major sources of PFAS to the environment are categorized under direct and indirect sources. The characteristic compounds and concentrations are summarized as found from direct sources such as manufacturing facilities, aqueous film-forming foam (AFFF) applications, metal coating operations, and textile and paper coating operations; and from indirect sources such as landfills and wastewater treatment plants (WWTPs). The major findings are: 1) among the aqueous matrices for which data were reviewed, groundwater impacted by AFFF contamination showed the highest median concentrations for both perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), while the second-highest median concentrations were associated with landfill leachates for PFOA and metal-plating sources for PFOS; 2) many of the unknown polyfluorinated precursors present in AFFF-impacted sites could potentially convert to persistent PFAS by abiotic or biotic transformation, and therefore could act as the long-term source of contamination to the environment; 3) part per billion (ppb) concentrations of PFAS were detected in water bodies surrounding fluorochemical manufacturing plants; 4) in consumer products such as textile, paper, and personal care products, PFOA concentrations were an order of magnitude higher compared to other PFAS; 5) biotransformation products such as fluorotelomer carboxylic acids (FTCAs) and perfluoroalkyl acids (PFAAs) are detected in landfill leachates and WWTP effluents; and 6) many studies have shown increased PFAA concentrations in WWTP effluents compared to influents. This work provides a comprehensive review of the literature on the PFAS concentration and composition trends of select non-polymeric PFAS in different sources.

Bioavailability, mobility and leaching of phosphorus in a Mediterranean agricultural soil (ne Spain) amended with different doses of biosolids.

The precipitation of sparingly soluble calcium phosphate in calcareous soils decreases the bioavailability of macronutrients, which makes their addition by way of fertilisers necessary. Sludge resulting from treating urban wastewater does not only provide significant amounts of phosphorus, but also helps lower the pH, thus increasing its bioavailability. The loss of part of soil nutrients due to irrigation or rain can contaminate groundwater. In order to assess the movement of phosphorus, a experiment was conducted on percolation columns, to which different doses of wastes were applied. The pH decreased by as much as 0.89 units, as well as the assimilable and soluble P, in intervals of 20 cm of depth, obtaining maximum values of 254 mg P kg-1 and 1455 µg P kg-1 respectively, and the P present in the leached water collected, which did not surpass 95 µg PL-1. The intent was to learn which was the majoritarian inorganic formed crystalline phase that immobilised the movement of phosphorus through the percolation column. The results obtained by the diffraction of X-rays are not conclusive, although they point to the formation of octacalcium phosphate. The diffractograms of the studied samples have similar diffraction lines to those of apatites.

QuEChERS-based analysis and ecotoxicological risk of select antibiotics in dumpsite leachates, hospital wastewater and effluent receiving water in Ibadan, Nigeria.

There is currently a dearth of information on the determination, occurrence and ecotoxicological risk of antibiotics in dumpsite leachates and hospital wastewater in Africa. A quick, easy, cheap, effective, rugged and safe (QuEChERS) protocol which combines extraction and clean-up in one step was optimized for the determination of antibiotics sulfadoxine, sulfamethazine and trimethoprim in dumpsite leachates and hospital wastewater. The occurrence and ecotoxicological risk of target antibiotics were investigated in wastewater from two hospitals, effluent receiving water and leachates from three dumpsites in Ibadan, Nigeria. Recoveries in hospital wastewater ranged from 53 to 116% while recoveries ranged from 50 to 89% in leachates. Method limits of quantification ranged from 0.7 to 12.1 µg L-1 in hospital wastewater and from 6.2 to 38.8 µg L-1 in leachates. Intra-day precisions (% RSD) were ≤ 21%. High concentrations of target antibiotics were measured: up to 475 µg L-1 for sulfamethazine in leachates, 118 µg L-1 for trimethoprim in hospital wastewater and 117 µg L-1 for sulfadoxine in effluent receiving water. Sulfadoxine presented high risk to algae, daphnid and fish in hospital wastewater, effluent receiving water and leachates. This work highlights the need for adequate and sound management of wastes containing pharmaceuticals in Nigeria.

Microplastic leachates induce species-specific trait strengthening in intertidal mussels.

Plastic pollution is ubiquitous with increasing recognition of its direct effects on species' fitness. Little is known, however, about its more subtle effects, including the influence of plastic pollution on the morphological, functional and behavioral traits of organisms that are central to their ability to withstand disturbances. Among the least obvious but most pernicious forms of plastic-associated pollution are the chemicals that leach from microplastics. Here, we investigate how such leachates influence species' traits by assessing functional trait compensation across four species of intertidal mussels, through investigations of byssal thread production, movement and aggregation behavior for mussels held in natural seawater or seawater contaminated by microplastic leachates. We found no evidence for compensation of functional traits, but for each species, microplastic leachates reinforced one trait while others remained unaffected. Two species (Perna perna and Mytilus galloprovincialis), were characterized by a resistance strategy to disturbance; they produced more byssal threads in microplastic leachate seawater than in control seawater, while motility and aggregation remained essentially unaffected. In contrast, the other two species (M. edulis and Choromytilus meridionalis), showed a resilience strategy to disturbance through increased motility and aggregation in leachate seawater, while byssal thread production remained unaffected. These results suggest that the competitive abilities of intertidal mussels may be related to their sensitivity to microplastic leachates or other chemical disturbance. Importantly, the trait strengthening observed will affect the ability of these mussels to form spatially patterned beds, with implications for their quality as autogenic ecological engineers or foundation species. Thus, our findings have implications for the ability of mussel beds to tolerate disturbance, and hence for central ecosystem services, such as their ability to support biodiversity and enhance secondary and tertiary production. The results suggest that an inconspicuous aspect of plastic pollution has the potential to influence other communities and ecosystems in powerful ways.

UV-254 degradation of nicotine in natural waters and leachates produced from cigarette butts and heat-not-burn tobacco products.

Nicotine is an important emerging contaminant widely detected in water resources. The main nicotine sources are human excretions from users and leaching from discarded tobacco product waste, which represents the most commonly littered item in urban areas and coasts. In this study, the UV254 photolytical fate of nicotine in natural water and leachates produced from conventional cigarettes (CCs) and the new generation heat-not-burn (HnBs) tobacco products is examined for the first time. The effect of UV254 irradiation on nicotine depletion in ultrapure water was initially studied. The reaction was pseudo first-order with respect to nicotine concentration at low concentrations and shifted to lower order at higher concentrations, an effect associated to absorption saturation. Although nicotine removal was fast, only 9.5% of the total organic carbon was removed after irradiation due to the formation of by-products. The chemical structures of six photo-products were derived by means of liquid and gas chromatography coupled to mass spectrometry. The photodegradation kinetics was found to depend on pH and faster kinetics were recorded when the monoprotonated form of nicotine was dominant (pH = 5-8). The presence of humic acids was found to slightly delay kinetics as they competed with nicotine for lamp irradiance, whereas the presence of salt had no effect on the direct photolysis of nicotine. Direct photolysis studies were also performed using natural waters. Compared to ultra-pure water, photodegradation was found to proceed slightly slower in river water, in similar kinetics in seawater, and relatively faster in rain water. The later was assumed to be due to the lower pH compared to the rest of the natural water tested. Leachates from used HnBs and smoked CCs were also submitted to UV254 irradiation and direct photolysis was found to proceed fast despite the high complexity of these matrices. Nonetheless, the total organic carbon in the system remained the same after irradiation due to the abundance of organics and photo-products formed. We take advantage of the present investigations and report the leaching behavior of nicotine from HnBs and CCs. Among others, we found that in HnBs ~70% of the total and bioavailable nicotine content remains in the tobacco sticks after operation and this percentage drops to 15% in CCs due to the reduction in mass after smoking. This finding demonstrated the importance of properly disposing tobacco product waste to prevent nicotine leaching in water bodies.

Assessing the effects of textile leachates in fish using multiple testing methods: From gene expression to behavior.

The textile industry, while of major importance in the world economy, is a toxic industry utilizing and emitting thousands of chemical substances into the aquatic environment. The aim of this project was to study the potentially harmful effects associated with the leaching of chemical residues from three different types of textiles: sportswear, children's bath towels, and denim using different fish models (cell lines, fish larvae and juvenile fish). A combination of in vitro and in vivo test systems was used. Numerous biomarkers, ranging from gene expression, cytotoxicity and biochemical analysis to behavior, were measured to detect effects of leached chemicals. Principle findings indicate that leachates from all three types of textiles induced cytotoxicity on fish cell lines (RTgill-W1). Leachates from sportswear and towels induced mortality in zebrafish embryos, and chemical residues from sportswear reduced locomotion responses in developing larval fish. Sportswear leachate increased Cyp1a mRNA expression and EROD activity in liver of exposed brown trout. Leachates from towels induced EROD activity and VTG in rainbow trout, and these effects were mitigated by the temperature of the extraction process. All indicators of toxicity tested showed that exposure to textile leachate can cause adverse reactions in fish. These findings suggested that chemical leaching from textiles from domestic households could pose an ecotoxicological threat to the health of the aquatic environment.

Chemicals sorbed to environmental microplastics are toxic to early life stages of aquatic organisms.

Microplastics are ubiquitous in aquatic ecosystems, but little information is currently available on the dangers and risks to living organisms. In order to assess the ecotoxicity of environmental microplastics (MPs), samples were collected from the beaches of two islands in the Guadeloupe archipelago, Petit-Bourg (PB) located on the main island of Guadeloupe and Marie-Galante (MG) on the second island of the archipelago. These samples have a similar polymer composition with mainly polyethylene (PE) and polypropylene (PP). However, these two samples are very dissimilar with regard to their contamination profile and their toxicity. MPs from MG contain more lead, cadmium and organochlorine compounds while those from PB have higher levels of copper, zinc and hydrocarbons. The leachates of these two samples of MPs induced sublethal effects on the growth of sea urchins and on the pulsation frequency of jellyfish ephyrae but not on the development of zebrafish embryos. The toxic effects are much more marked for samples from the PB site than those from the MG site. This work demonstrates that MPs can contain high levels of potentially bioavailable toxic substances that may represent a significant ecotoxicological risk, particularly for the early life stages of aquatic animals.

Antibacterial Activity of Clay Soils against Food-Borne Salmonella typhimurium and Staphylococcus aureus.

Natural clays have recently been proven to possess antibacterial properties. Effective natural antimicrobial agents are needed to combat bacterial contamination on food contact surfaces, which are increasingly more prevalent in the food chain. This study sought to determine the antibacterial activity of clays against the food-borne pathogens Salmonella typhimurium ATCC 14028 and Staphylococcus aureus ATCC 13565. Soils were processed to yield leachates and suspensions from untreated and treated clays. Soil particle size, pH, cation-exchange capacity, metal composition and mineralogy were characterized. Antibacterial screening was performed on six Malaysian soils via the disc diffusion method. In addition, a time-kill assay was conducted on selected antibacterial clays after 6 h of exposure. The screening revealed that Munchong and Carey clays significantly inhibit Salmonella typhimurium (11.00 ± 0.71 mm) and S. aureus (7.63 ± 0.48 mm), respectively. Treated Carey clay leachate and suspension completely kill Salmonella typhimurium, while S. aureus viability is reduced (2 to 3 log10). The untreated Carey and all Munchong clays proved ineffective as antibacterials. XRD analysis confirmed the presence of pyrite and magnetite. Treated Carey clays had a higher soluble metal content compared to Munchong; namely Al (92.63 ± 2.18 mg/L), Fe (65.69 ± 3.09 mg/L) and Mg (88.48 ± 2.29 mg/L). Our results suggest that metal ion toxicity is responsible for the antibacterial activity of these clays.

Differentiating the Effects of Oxidative Stress Tests on Biopharmaceuticals.

PURPOSE: A rapid and broadly applicable method to assess relevant oxidative damage in biopharmaceuticals is important for lifecycle management of product quality. Multiple methods are currently employed as stress tests to induce oxidative damage for assessment of stability, safety, and efficacy. We compared two common methods for inducing oxidative damage to assess differences in impact on bioactivity and structure of the biopharmaceuticals. METHODS: Biopharmaceuticals were treated with either metal-catalyzed oxidation (MCO) conditions or the reactive-oxygen species (ROS) inducer 2,2'-Azobis(2-amidinopropane) dihydrochloride (AAPH), then analyzed for changes in structure and bioactivity. RESULTS: We demonstrate that commonly used chemical methods for assessing oxidation yield distinct oxidation profiles for each of the biotechnology products analyzed, including monoclonal antibodies. We further report oxidant- and product-specific changes in bioactivity under oxidizing conditions, along with differential oxidation on the molecular subunits of monoclonal antibodies. CONCLUSION: Our results highlight the need for product-specific optimization and selection of orthogonal, relevant oxidizers when characterizing stress responses in biopharmaceuticals.

Combination of cloud point extraction with single particle inductively coupled plasma mass spectrometry to characterize silver nanoparticles in soil leachates.

The expansion of silver nanoparticle (AgNP) applications in industry as antibacterial agents has generated an increment of their presence in the environment. Once there, their behavior is not clear because they can undergo different transformation processes that affect their transport, mobility, bioavailability, and toxicity. Therefore, the characterization and quantification of these emerging contaminants are important to understand their behavior and the toxicity effects that can be exerted on living beings. Single particle inductively coupled plasma mass spectrometry (SP-ICPMS) has demonstrated its ability to characterize and give quantitative information on AgNPs in aqueous samples. However, sometimes, the discrimination of the signal corresponding to AgNPs from the signal of dissolved species (Ag(I)) is a challenge. In the present contribution, it is shown that the presence of high amounts of Ag(I) hamper silver nanoparticle size and nanoparticle concentration determination in aqueous samples by SP-ICPMS. To facilitate signal discrimination of both chemical forms, the combination of cloud point extraction (CPE) with SP-ICPMS was studied. CPE experimental conditions to separate AgNPs from Ag(I) were assessed and adapted taking into account the characteristics of the SP-ICPMS technique. CPE and soil matrix effects on particle size were evaluated, showing that particle size was not modified after being in contact with soil matrix and after being separated by CPE. Additionally, frequently used calculation methods for SP-ICPMS data treatment were assessed. Finally, the potential of the developed methodology CPE-SP-ICPMS was evaluated in aqueous soil leachates contaminated with mixtures of AgNPs/Ag(I).

Influence of biochar particle size on biota responses.

Despite the increasing interest for biochar as a soil amendment, a knowledge gap remains on its impacts on non-target soil and aquatic species. We hypothesised that biochar particle size and application rate can play a role in the toxicity to biota. Pine woodchip biochar was incorporated in a clean soil at three particle size classes: small (<0.5 mm), medium (1-2 mm), and large (<4 mm), and at two concentrations: 1% and 6% w/w. A laboratory screening with earthworm Eisenia andrei avoidance behaviour bioassay was carried out to test the most adequate application rates, particle sizes and soil-biochar pre-incubation period. Thereafter, a 28-day greenhouse microcosm experiment was conducted as an ecologically more representative approach. Survival, vertical distribution and weight changes of E. andrei, and bait-lamina consumption were recorded. Soil leachates from the microcosms were collected to evaluate their impact on Daphnia magna immobilisation and Vibrio fischeri (Microtox®) bioluminescence. A feeding experiment with E. andrei was also performed to address earthworm weight changes and to conduct a screening of PAH-type metabolites in their tissue. The 6% <0.5 mm treatment pre-incubated for 96 h induced significant avoidance of the earthworms. Significantly lower bait-lamina consumption was observed in microcosms for the 6% <0.5 mm treatment. Moreover, particle size was a statistically significant factor regarding the loss of weight in the feeding experiment and higher concentration of naphthalene-type metabolites detected in E. andrei tissue, when exposed to <0.5 mm biochar particles. The leachates had no adverse effects on the aquatic species. The results suggest that particles <0.5 mm of pine woodchip biochar can pose sub-lethal effects on soil biota.

Impact of organic contaminants from dumpsite leachates on natural water sources in the Enugu Metropolis, southeastern Nigeria.

This study evaluates the impact of leachates from a municipal dumpsite on the quality of domestic water sources in the area for potable use. Concentrations of leachate-associated organic contaminants (such as diethyl-phthalate, total organic halogen (TOH); 2,4-dichlorophenol; nonylphenol-ethoxylate; methyl-ethyl-phthalate; borneol; total organic carbon (TOC); total Kjeldahl-nitrogen (TKN); ammonium-nitrogen (NH3-N); nitrate (NO3); nitrate-nitrogen (NO3-N); and total phosphorus (TP)) in rivers and groundwater in the Enugu Metropolis in southeastern Nigeria were assessed in this study. Results of laboratory analyses indicate that the average values of diethyl-phthalate, borneol, TOH, nonylphenol-ethoxylate and TOC are 0.08 mg/l, 0.04 mg/l, 1.05 mg/l, 0.2 mg/l and 1.64 mg/l, respectively for groundwater and 0.1 mg/l, 0.03 mg/l, 0.74 mg/l, 0.19 mg/l and 1.74 mg/l, respectively, for rivers. Three (diethyl-phthalate, borneol and TOH) out of these major five contaminants, in both rivers and groundwater, exceeded the maximum permissible limits, suggesting that the domestic water sources are marginally contaminated by the leachates. ANOVA test result suggests that the data sources were significantly variable, while principal component and correlation analyses identified TOH, 2,4-dichlorophenol, TKN, NO3, NO3-N, TP and borneol, which originated most probably from degradation of plastic materials and organic wastes in the dumpsite, as the priority contaminants. Consumption of domestic water sources within the dumpsite area, in untreated state, could lead to health risks as these priority organic contaminants are mostly carcinogenic, toxic and injurious to human systems.