An updated status of currently used pesticides in India: Human dietary exposure from an Indian food basket.

Currently used pesticides (CUPs) were introduced to have lower persistence and bioaccumulation, and lesser bioavailability towards non-target species. Nevertheless, CUPs still represent a concern for both human health and the environment. India is an important agricultural country experiencing a conversion from the use of obsolete organochlorine pesticides to a newer generation of phytosanitary products. As for other developing countries, very little is known about the transfer of CUPs to the human diet in India, where systematic monitoring is not in place. In this study, we analyzed ninety four CUPs and detected thirty CUPs in several food products belonging to five types: cereals and pulses, vegetables, fruits, animal-based foods, and water. Samples were taken from markets in Delhi (aggregating food produced all over India) and in the periurban area of Dehradun (northern India) (representing food produced locally and through more traditional practices). Overall, chlorpyrifos and chlorpropham were the most detected CUPs with a detection frequency of 33% and 25%, respectively. Except for vegetables and fruits, the levels of CUPs in all other food types were significantly higher in samples from Delhi (p < 0.05). Exposure dosage of CUPs through different food matrices was calculated, and chlorpropham detected in potatoes had the maximum exposure dosage to humans (2.46 × 10-6 mg/kg/day). Risk analysis based on the hazard quotient technique indicated that chlorpyrifos in rice (2.76 × 10-2) can be a concern.

Innovative reference materials for method validation in microplastic analysis including interlaboratory comparison exercises.

Reference materials (RMs) are vital tools in the validation of methods used to detect environmental pollutants. Microplastics, a relatively new environmental pollutant, require a variety of complex approaches to address their presence in environmental samples. Both interlaboratory comparison (ILC) studies and RMs are essential to support the validation of methods used in microplastic analysis. Presented here are results of quality assurance and quality control (QA/QC) performed on two types of candidate microplastic RMs: dissolvable gelatin capsules and soda tablets. These RMs have been used to support numerous international ILC studies in recent years (2019-2022). Dissolvable capsules containing polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene (PE), and polystyrene (PS), in different size fractions from 50 to 1000 µm, were produced for one ILC study, obtaining relative standard deviation (RSD) from 0 to 24%. The larger size fraction allowed for manual addition of particles to the capsules, yielding 0% error and 100% recovery during QA/QC. Dissolvable capsules were replaced by soda tablets in subsequent ILC studies and recovery test exercises because they were found to be a more reliable carrier for microplastic RMs. Batches of soda tablets were produced containing different single and multiple polymer mixtures, i.e., PE, PET, PS, PVC, polypropylene (PP), and polycarbonate (PC), with RSD ranging from 8 to 21%. Lastly, soda tablets consisting of a mixture of PE, PVC, and PS (125-355 µm) were produced and used for recovery testing during pretreatment of environmental samples. These had an RSD of 9%. Results showed that soda tablets and capsules containing microplastics >50 µm could be produced with sufficient precision for internal recovery tests and external ILC studies. Further work is required to optimize this method for smaller microplastics (< 50 µm) because variation was found to be too large during QA/QC. Nevertheless, this approach represents a valuable solution addressing many of the challenges associated with validating microplastic analytical methods.

Occurrence, Source and Dietary Exposure of Toxic and Essential Elements in the Indian Food Basket.

In this study, representative urban and peri-urban Indian food baskets have been studied for the presence of toxic and essential elements. The concentration of target toxic and essential elements was used to estimate dietary intakes (EDIs) and health risks. Across all food matrices, toxic elements like Cd and Pb were dominant. The highest concentrations of the target elements were found in vegetables, with Cd, Pb, and Ni being beyond permissible limits of the Food and Agriculture Organization of the United Nations and the World Health organization (0.05 mg/kg, 0.1 mg/kg, and 1.5 mg/kg, respectively) in okra, spinach, and cauliflower. The sum of concentrations of the toxic elements (As, Ni, Hg, Cr, Cd, Pb) in vegetables had a range of 0.54-12.08 mg/kg, the highest sum was found in spinach (median 12.08 mg/kg), followed by okra (median 1.68 mg/kg). The EDI was observed for vegetables with a contribution as high as 92% for Cd. Dairy products were found with the highest loading for Ni with a dietary intake of 3.1 mg/kg/day for adults and twice as much for children. Carcinogenic risk for Ni was the highest and found above the threshold for all food categories, as was the case with As. Cumulative carcinogenic and non-carcinogenic risks were mostly contributed by milk and vegetables, in particular, spinach.

Migration of Plasticizers from Polyethylene Terephthalate and Low-Density Polyethylene Casing into Bottled Water: A Case Study From India.

Mineral bottled water packed in three polymers viz., virgin polyethylene terephthalate (PET), recycled PET, and low-density polyethylene (LDPE) were investigated for the occurrence, migration, and health risk of phthalic acid esters (PAEs) at 25 °C, 35 °C, and 45 °C. The average concentration of six USEPA priority PAEs in refrigerated water samples was highest in recycled PET> LDPE > virgin PET. The highest leaching was seen at 45 °C after 2 days for LDPE water packets with ∑6PAEs amounting to 64,300 ng/L. Similarly, for recycled PET, the highest migration was seen at 45 °C after seven days (3,800 µg/L). Bis 2-ethyl hexyl phthalate (DEHP) and di-n-butyl phthalate (DnBP) were the predominant plasticizers from PET bottles and LDPE water packets, respectively. Predicted concentration after three weeks based on best fit obtained through the polynomial model for PET bottles was seen higher than the recommended limit suggested by USEPA (6 µg/L) and WHO (8 µg/L).

Interlinkage Between Persistent Organic Pollutants and Plastic in the Waste Management System of India: An Overview.

Improper handling of plastic waste and related chemical pollution has garnered much attention in recent years owing to the associated detrimental impacts on human health and the environment. This article reports an overview of the main interlinkages between persistent organic pollutants (POPs) and plastic in the waste management system of India. Both plastics and POPs share certain common traits such as persistence, resistance to biological degradation, and the ability to get transported over long distances. Throughout the processes of production, consumption, and disposal, plastics interact with and accumulate POPs through several mechanisms and end up co-existing in the environment. Plastic waste can undergo long-range transport through rivers and the oceans, break down into microplastics and get transported through the air, or remain locked in waste dump yards and landfills. Over time, environmental processes lead to the leaching and release of accumulated POPs from these plastic wastes. Plastic recycling in the Indian informal sector including smelting, scrubbing, and shredding of plastic waste, is also a potential major POPs source that demands further investigation. The presence of POPs in plastic waste and their fate in the plastic recycling process have not yet been elucidated. By enhancing our understanding of these processes, this paper may aid policy decisions to combat the release of POPs from different waste types and processes in India.

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.

Water Browning Controls Adaptation and Associated Trade-Offs in Phytoplankton Stressed by Chemical Pollution.

The acquisition of tolerance to an environmental stressor can result in organisms displaying slower growth after stress release. While well-grounded in the theory, empirical evidence of the trade-off between stress tolerance and organism fitness is scarce and blurred by the interaction with different environmental factors. Here, we report the effects of water browning on the responses, tolerance acquisition, and associated trade-offs in a population of microalgae exposed to sublethal concentrations of organic micropollutants over multiple generations. Our results show that dissolved organic matter (DOM) reduces toxic responses and modulates tolerance acquisition by the algae, possibly by complexing micropollutants. Microalgae that acquire tolerance allocate resources to fitness at the cost of reduced cell size. They yield higher productivity than nonadapted ones when grown in the presence of micropollutants but lower in their absence. The net trade-off was positive, indicating that adaptation can result in a higher productivity and fitness in tolerant species in recurrently stressed environments.

Assessing Air-Surface Exchange and Fate of Mercury in a Subtropical Forest Using a Novel Passive Exchange-Meter Device.

A novel passive exchange meter (EM) device was developed to assess air-surface exchange and leaching of Hg in a forest floor. Flux measurements were carried out in a subtropical forest ecosystem during a full year. Over 40% of the Hg fixed in fresh forest litter was remobilized in less than 60 days in warm and humid conditions as a response to rapid turnover of labile organic matter (OM). A two-block experiment including understory and clearing showed that losses of Hg covaried with seasonal conditions and was significantly affected by forest coverage. The process controlling the bulk loss of total Hg from the litter was volatilization, which typically represented 76-96% of the loss processes (Floss). The Floss ranges were 520-1370 and 165-942 ng m-2 d-1 in the understory and clearing, respectively. On a yearly basis, deposition of airborne Hg exceeded total losses by a factor of 2.5 in the clearing and 1.5 in the understory. The vegetation litter in this subtropical forest therefore represented a net sink of atmospheric Hg. This study provided a novel approach to Hg air-soil exchange measurements and further insights on the link between Hg remobilization and OM turnover along with its environmental drivers.

Modelling Environmental Impacts of Cesium-137 Under a Hypothetical Release of Radioactive Waste.

Waste tanks at the nuclear facility located at Sellafield, UK, represent a nuclear source which could release radionuclides to the atmosphere. A model chain which combines atmospheric transport, deposition as well as riverine transport to sea has been developed to predict the riverine activity concentrations of 137Cs. The source term was estimated to be 9 × 104 TBq of 137Cs, or 1% of the assumed total 137Cs inventory of the HAL (Highly Active Liquid) storage tanks. Air dispersion modelling predicted 137Cs deposition reaching 127 kBq m-2 at the Vikedal catchment in Western Norway. Thus, the riverine transport model predicted that the activity concentration of 137Cs in water at the river outlet could reach 9000 Bq m-3 in the aqueous phase and 1000 Bq kg-1 in solid phase at peak level. The lake and river reaches showed different transport patterns due to the buffering effects caused by dilution and slowing down of water velocity.

Validation of a Method for Extracting Microplastics from Complex, Organic-Rich, Environmental Matrices.

Complex and organic-rich solid substrates such as sludge and soil have been shown to be contaminated by microplastics; however, methods for extracting plastic particles have not yet been systemically tested or standardized. This study investigated four main protocols for the removal of organic material during analysis of microplastics from complex solid matrices: oxidation using H2O2, Fenton's reagent, and alkaline digestion with NaOH and KOH. Eight common polymer types were used to assess the influence of reagent exposure on particle integrity. Organic matter removal efficiencies were established for test sludge and soil samples. Fenton's reagent was identified as the optimum protocol. All other methods showed signs of particle degradation or resulted in an insufficient reduction in organic matter content. A further validation procedure revealed high microplastic extraction efficiencies for particles with different morphologies. This confirmed the suitability of Fenton's reagent for use in conjunction with density separation for extracting microplastics. This approach affords greater comparability with existing studies that utilize a density-based technique. Recommendations for further method optimization were also identified to improve the recovery of microplastic from complex, organic-rich environmental samples.

Air-Seawater Exchange of Organochlorine Pesticides along the Sediment Plume of a Large Contaminated River.

Gaseous exchange fluxes of organochlorine pesticides (OCPs) across the air-water interface of the coastal East China Sea were determined in order to assess whether the contaminated plume of the Yangtze River could be an important regional source of OCPs to the atmosphere. Hexachlorocyclohexanes (HCHs), chlordane compounds (CHLs), and dichlorodiphenyltrichloroethanes (DDTs) were the most frequently detected OCPs in air and water. Air-water exchange was mainly characterized by net volatilization for all measured OCPs. The net gaseous exchange flux ranged 10-240 ng/(m2·day) for γ-HCH, 60-370 ng/(m2·day) for trans-CHL, 97-410 ng/(m2·day) for cis-CHL, and ∼0 (e.g., equilibrium) to 490 ng/(m2·day) for p,p'-DDE. We found that the plume of the large contaminated river can serve as a significant regional secondary atmospheric source of legacy contaminants released in the catchment. In particular, the sediment plume represented the relevant source of DDT compounds (especially p,p'-DDE) sustaining net degassing when clean air masses from the open ocean reached the plume area. In contrast, a mass balance showed that, for HCHs, contaminated river discharge (water and sediment) plumes were capable of sustaining volatilization throughout the year. These results demonstrate the inconsistencies in the fate of HCHs and DDTs in this large estuarine system with declining primary sources.

Spatial distribution of old and emerging flame retardants in Chinese forest soils: sources, trends and processes.

The levels and distribution of polybrominated diphenylethers (PBDEs), novel brominated flame retardants (NBFRs) and Dechlorane Plus (DP) in soils and their dependence on environmental and anthropological factors were investigated in 159 soil samples from 30 background forested mountain sites across China. Decabromodiphenylethane (DBDPE) was the most abundant flame retardant (25-18,000 pg g(-1) and 5-13,000 pg g(-1) in O-horizon and A-horizon, respectively), followed by BDE 209 (nd-5900 pg g(-1) and nd-2400 pg g(-1) in O-horizon and A-horizon, respectively). FRs distributions were primarily controlled by source distribution. The distributions of most phasing-out PBDEs, DP isomers and TBPH were in fact correlated to a population density-based index used as proxy of areas with elevated usage and waste of FR containing products. High concentrations of some NBFRs were however observed in industrialized regions and FR manufacturing plants. Strongly positive correlations were observed between PBDEs and their replacement products suggesting similar emission pattern and environmental behavior. Exposure of mineral subsoils depended on precipitations driving leaching of FRs into the soil core. This was especially evident for some emerging BFRs (TBE, TBPH, and TBB etc.) possibly indicating potential for diffuse groundwater contamination.

Elevated mobility of persistent organic pollutants in the soil of a tropical rainforest.

Semivolatile persistent organic pollutants (POP) are bioaccumulative and toxic contaminants. Their global distribution depends on source distribution, atmospheric transport, degradation, and the exchange with ocean and land surfaces. Forests are crucial terrestrial reservoirs due to the commonly envisaged high capacity of their surface soils to store and immobilize airborne contaminants bound to soil organic matter. Our results show that POPs can be unexpectedly mobile in the soil of a tropical rainforest due to fast litter turnover (leading to rapid POP transfer to the subsoil) and leaching rates exceeding degradation rates especially for more hydrophobic congeners. Co-transport in association with leaching fine particulate and dissolved organic matter appears as a relevant driver of this PCB export. A markedly different distribution pattern is displayed in this soil in comparison to soils of colder environments with lower overall storage capacity. These findings show that biogeochemistry of organic matter degradation and weathering can influence POP soil fate. Because tropical forests represent 60% of the global terrestrial productivity, the highlighted dynamics might have an implication for the general distribution of these contaminants.

Accumulation kinetics and equilibrium partitioning coefficients for semivolatile organic pollutants in forest litter.

Soils are important stores of environmentally cycling semivolatile organic contaminants (SVOCs) and represent relevant atmospheric secondary sources whenever environmental conditions favor re-emission. The exchange between air and soil is controlled by resistances posed by interfacial matrices such as the ubiquitously distributed vegetation litter. For the first time, this study focused on the experimental characterization of accumulation parameters for SVOCs in litter under real field conditions. The logarithm of the litter-air equilibrium partitioning coefficient ranged 6.8-8.9 and had a similar dependence on logKOA as that of plant foliage and soil data. Uptake and release rates were also KOA dependent with values (relevant for real environmental conditions) ranging 30,000-150,000 d(-1) and 0.0004-0.0134 d(-1), respectively. The overall mass transfer coefficient v controlling litter-air exchange (0.03-1.4 cm s(-1)) was consistent with previously reported data of v for foliage in forest canopies after normalization on leaf area index. Obtained data suggest that litter holds the potential for influencing atmospheric fugacity in proximity to soil, likely affecting overall exchange of SVOCs between the soil reservoir and the atmosphere.

Are eco-friendly "green" tires also chemically green? Comparing metals, rubbers and selected organic compounds in green and conventional tires.

Tires are a major source of synthetic and natural rubber particles, metals and organic compounds, in which several compounds are linked to negative environmental impact. Recent advances in material technology, coupled with focus on sustainability, have introduced a new range of tires, sold as "green, sustainable, and eco-friendly". Although these "green" tires may have lower impact on the environment on a global scale, there is no current knowledge about the chemical composition of "green" tires, and whether they are more eco-friendly when considering the release of tire wear particles or tire-associated chemicals. Here we have investigated the chemical composition of nine "green" vehicle tires, one "green" bike tire and seven "conventional" vehicle tires. No significant difference was found between "green" and "conventional" tires tested in this study. For N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), the average concentration in "green" tires were higher (16 ± 7.8 µg/mg) compared to "conventional" tires (8.7 ± 4.5 µg/mg). The relationship between metals, selected organic compounds and rubbers demonstrated large variation across brands, and lower variability between tires grouped according to their seasonal use. This study indicates that more work is needed to understand how the shift towards sustainable tires might change the chemical composition of tires.

Comments to "Degli-Innocenti, F. The pathology of hype, hyperbole and publication bias is creating an unwarranted concern towards biodegradable mulch films" [J. Hazard. Mater. 463 (2024) 132923].

Some narratives present biodegradable plastic use for soil mulching practices in agriculture as "environmentally friendly" and "sustainable" alternatives to conventional plastics. To verify these narratives, environmental research recently started focusing on their potential impact on soil health, highlighting some concerns. The paper by Degli-Innocenti criticizes this unfolding knowledge arguing that it is affected by communication hypes, alarmistic writing and a focus on exposure scenarios purposedly crafted to yield negative effects. The quest of scientists for increased impact - the paper concludes - is the driver of such behavior. As scholars devoted to the safeguarding of scientific integrity, we set to verify whether this serious claim is grounded in evidence. Through a bibliometric analysis (using number of paper reads, citations and mentions on social media to measure the impact of publications) we found that: i) the papers pointed out by Degli-Innocenti as examples of biased works do not score higher than the median of similar publications; ii) the methodology used to support the conclusion is non-scientific; and iii) the paper does not fulfil the requirements concerning disclosure of conflicts of interests. We conclude that this paper represents a non-scientific opinion, potentially biased by a conflict of interest. We ask the paper to be clearly tagged as such, after the necessary corrections on the ethic section have been made. That being said, the paper does offer some useful insights for the definition of exposure scenarios in risk assessment. We comment and elaborate on these proposed models, hoping that this can help to advance the field.

Production and characterisation of environmentally relevant microplastic test materials derived from agricultural plastics.

Soil environments across the globe, particularly in agricultural settings, have now been shown to be contaminated with microplastics. Agricultural plastics - such as mulching films - are used in close or direct contact with soils and there is growing evidence demonstrating that they represent a potential source of microplastics. There is a demand to undertake fate and effects studies to understand the behaviour and potential long-term ecological risks of this contamination. Yet, there is a lack of test materials available for this purpose. This study describes the manufacture and characterisation of five large (1-40 kg) batches of microplastic test materials derived from agricultural mulching films. Batches were produced from either polyethylene-based conventional mulching films or starch-polybutadiene adipate terephthalate blend mulching films that are certified biodegradable in soil. Challenges encountered and overcome during the micronisation process provide valuable insights into the future of microplastic test material generation from these material types. This includes difficulties in micronising virgin polyethylene film materials. All five batches were subjected to a thorough physical and chemical characterisation - both of the original virgin films and the subsequent microplastic particles generated - including a screening for the presence of chemical additives. This is a critical step to provide essential information for interpreting particle fate or effects in scientific testing. Trade-offs between obtaining preferred particle typologies and time and cost constraints are elucidated. Several recommendations emerging from the experiences gained in this study are put forward to advance the research field towards greater harmonisation and utilisation of environmentally relevant test materials.

GIS mapping of agricultural plastic waste in southern Europe.

The escalating use of plastics in agriculture, driven by global population growth and increasing food demand, has concurrently led to a rise in Agricultural Plastic Waste (APW) production. Effective waste management is imperative, prompting this study to address the initial step of management, that is the quantification and localization of waste generated from different production systems in diverse regions. Focused on four Southern European countries (Italy, Spain, Greece, and Portugal) at the regional level, the study uses Geographic Information System (GIS), land use maps, indices tailored to each specific agricultural application and each crop type for plastic waste mapping. Furthermore, after the data was employed, it was validated by relevant stakeholders of the mentioned countries. The study revealed Spain, particularly the Andalusia region, as the highest contributor to APW equal to 324,000 tons per year, while Portugal's Azores region had the lowest estimate equal to 428 tons per year. Significantly, this research stands out as one of the first to comprehensively consider various plastic applications and detailed crop cultivations within the production systems, representing a pioneering effort in addressing plastic waste management in Southern Europe. This can lead further on to the management of waste in this area and the transfer of the scientific proposition to other countries.

Influence of climate and land use change on spatially resolved volatilization of persistent organic pollutants (POPs) from background soils.

The subject of this study is the assessment of the influence of climate and land use change on the potential re-emission of organochlorine pesticides (OCPs) from background and agricultural soils. A deterministic spatially and temporally explicit model of the air-surface exchange was created, fed with distributed data of soil and atmospheric concentrations from real measurements, and run under various scenarios of temperature and land use change for a case study area representative of central European conditions. To describe land use influence, some important features were implemented including effect of plowing, influence of land cover, temperature of soil, and seasonal changes of air layer stability. Results show that volatilization of pesticides from soil largely exceeded dry gas deposition in most of the area. Agricultural soils accounted for more than 90% of the total re-emissions both because of the generally higher soil fugacities (higher loads of chemicals and relatively low organic carbon content), but also due to physical characteristics and land management practices enhancing the dynamics of the exchange. An increase of 1 °C in air temperature produced an increase of 8% in the averaged total volatilization flux, however this effect can be neutralized by a change of land use of 10% of the arable lands to grassland or forest, which is consistent with projected land use change in Europe. This suggests that future assessment of climate impact on POP fate and distribution should take into consideration land use aspects.