Degradation of four pesticides in five urban landscape soils: human and environmental health risk assessment.

Pesticides are the most cost-effective means of pest control; however, the serious concern is about the non-target effects due to their extensive and intensive use in both agricultural and non-agricultural settings. The degradation rate constant (k) and half-life (DT50) of four commonly used pesticides, glyphosate, 2,4-D, chlorothalonil and dimethoate were determined in five Australian urban landscape soils, with varying physicochemical characteristics, to assess their environmental and human health risks. The k values (day-1) for the selected pesticides were inversely proportional to those of organic carbon (OC), silt, clay and Fe and Al oxides, and directly proportional to pH and sand content in soils. In contrast, the calculated values of DT50 (days) of all the four pesticides in five soils positively correlated with OC, clay, silt and oxides of Fe and Al, whereas soil pH and sand content exhibited a negative correlation. The calculated values of environmental indices, GUS and LIX, for the selected pesticides indicate their potential portability into water bodies, affecting non-target organisms as well as food safety. The evaluation for human non-cancer risk of these pesticides, based on the calculated values of hazard quotient (HQ) and hazard index (HI), suggested that exposure of adults and children to soils, contaminated with 50% of initially applied concentrations, through ingestion, dermal and inhalation pathways might cause negligible to zero non-carcinogenic risks. The present data might help the stakeholders in applying recommended doses of pesticides in urban landscapes and regulatory bodies concerned in monitoring the overall environmental quality and implementing safeguard policies. Our study also clearly demonstrates the need for developing improved formulations and spraying technologies for pesticides to minimize human and environmental health risks.

Toxicity assessment of historical aqueous film-forming foams (AFFFs) using cell-based assays.

Aqueous film-forming foam (AFFF) has historically contained high concentrations of long-chain per-and polyfluoroalkyl substances (PFAS), which have been linked with adverse health outcomes. However, the toxicity of historical AFFFs remains largely unknown, presenting uncertainties in their risk assessment. This study assessed the toxicity of historical AFFFs by exposing human liver cells (HepG2) to various dilutions of 3M Light Water AFFF or Ansulite AFFF (0.001%, 0.002%, 0.005%, 0.009%, 0.019%, 0.038%, 0.075%, 0.15%, and 0.3%) for 24 h. The effects of the two AFFF formulations on the cell viability, intracellular reactive oxygen species (ROS) production, Nrf2-ARE activity, and DNA damage were assessed by CellTiter 96® Aqueous One Solution Cell Proliferation Assay (MTS kit), dichlorofluorescein diacetate assay, luciferase assay, and alkaline Comet assay, respectively. The results revealed that the two brands of AFFFs tested were toxic to HepG2 cells at dilutions lower than the recommended 3% application formulation. Specifically, exposure to 3M Light Water AFFF or Ansulite AFFF induced a dilution-dependent decrease in cell viability, increased intracellular ROS production, and increased Nrf2-ARE activity. However, except for the highest concentration (lowest dilution) of 3M Light Water AFFF tested (0.038%.), both 3M Light Water AFFF and Ansulite AFFF did not significantly induce cellular DNA damage. Overall, 3M Light Water AFFF was more toxic than Ansulite AFFF. The findings from this study provided valuable in vitro toxicity data that may better inform the health risk assessment of these historical AFFFs.

Cocoa-laden cadmium threatens human health and cacao economy: A critical view.

In the recent decades, Cd burden in cocoa-based products threatened global food safety, human health and the future of chocolateries. Increased Cd bioavailability is an acute problem in cacao-based horticulture. Poverty, poor maintenance, unjustified traditional farming, and paucity of knowledge on Cd-binding propensity in cacao discourage the application of risk-mitigation measures. Progressive accumulation of Cd, with a half-life of 10-30 years, in the human body even at ultra-trace levels may lead to serious health complications. If Cd accumulates in the food chain through cocoa products, consequences in children, who are the primary consumers of chocolates, include morbidity and mortality that may result in a significant demographic transition by the year 2050. Developing cacao clones with an innate capability of taking up low Cd levels from soils, and site-specific Cd-cacao research might contribute to limiting the trophic transfer of Cd. This review highlights the possible routes for Cd uptake in cacao plants and discusses the measures to rescue the chocolateries from Cd pollution to promote "healthy" cacao farming. The potential human health risks of chocolate-laden Cd and mitigation strategies to minimize Cd burden in the human body are also presented. The challenges and prospects in Cd-cacao research are discussed as well.

Phytoremediation efficacy assessment of polycyclic aromatic hydrocarbons contaminated soils using garden pea (Pisum sativum) and earthworms (Eisenia fetida).

Endpoint assessment using biological systems in combination with the chemical analysis is important for evaluating the residual effect of contaminants following remediation. In this study, the level of residual toxicity of polycyclic aromatic hydrocarbons (PAHs) after 120 days of phytoremediation with five different plant species:- maize (Zea mays), Sudan grass (Sorghum sudanense), vetiver (Vetiveria zizanioides), sunflower (Helianthus annuus) and wallaby grass (Austrodanthonia sp.) has been evaluated by ecotoxicological tests such as root nodulation and leghaemoglobin assay using garden pea (Pisum sativum) and acute, chronic and genotoxicity assays using earthworm (Eisenia fetida). The phytoremediated soil exhibited lesser toxicity supporting improved root nodulation and leghaemoglobin content in P. sativum and reducing DNA damage in E. fetida when compared to contaminated soil before remediation. Also, the results of the ecotoxicological assays with the legume and earthworm performed in this study complemented the results obtained by the chemical analysis of PAHs in phytoremediated soil. Therefore, these findings provide a basis for a framework in which remediation efficacy of PAHs-contaminated sites can be evaluated effectively with simple ecotoxicological bioassays using legumes and earthworms.

Toxicity assessment of fresh and weathered petroleum hydrocarbons in contaminated soil- a review.

Soil contamination with total petroleum hydrocarbons (TPH) is widespread throughout the globe due to the massive production of TPH anthropogenically and its occurrence in the soil. TPH is toxic to beneficial soil organisms and humans and thus has become a serious concern among the public. Traditionally TPH toxicity in the soil is estimated based on chemical fractions and a range of bioassays including plants, invertebrates and microorganisms. There is a large inconsistency among ecotoxicology data using these assays due to the nature of TPH and their weathering. Therefore, in this article, we critically reviewed the weathered conditions of TPH, the potential fate in soil and the bioindicators for the assessment of the ecotoxicity. Based on the current research and the state-of-the-art problem, we also highlighted key recommendations for future research scope for the real-world solution of the ecotoxicological studies of hydrocarbons.

Assessment of chromium hyper-accumulative behaviour using biochemical analytical techniques of greenhouse cultivated Sonchus asper on tannery waste dump site soils.

Keeping the sources of pollution such as chromium (Cr) under a safe limit is a daunting challenge due to the negative impact of heavy metal bioaccumulation in vegetation and the concomitant human health exposure. We took a closer look at Sonchus asper by cultivating in the green house. It resulted in 80% germination when cultivated over nine different soils collected from the tannery dump site. The biochemical analytical techniques such as mass spectrometry indicated significant bioaccumulation of Cr in the plant tissue. As per the ICP-MS analysis, this annual herb resulted in the accumulation of 601 mg kg-1 of total Cr with 212 mg kg-1 in its shoot from soil samples containing up to 41 mg kg-1 of hexavalent Cr. The energy dispersive X-ray (EDX) spectroscopy of S. asper revealed a higher level of S element indicating a sulfate-Cr binding relation. Elevated content of Cr in soil (73,721 ± 65 mg kg-1) caused biochemical changes in the shoot of S. asper as indicated by the disappearance of Fourier transform infrared spectroscopy (FTIR) bands at 935 and 872 cm-1 and further revealing aliphatic -CH2 appearing as anti-symmetry νa(CH2) and symmetric vibration νs(CH2) at the band of 2920 and 2850 cm-1, respectively.

Risk-based remediation of polluted sites: A critical perspective.

Sites contaminated with chemical pollutants represent a growing challenge, and remediation of such lands is of international concern. Risk-based land management (RBLM) is an emerging approach that integrates risk assessment practices with more traditional site-specific investigations and remediation activities. Developing countries are yet to adopt RBLM strategies for remediation. RBLM is considered to be practical, scientifically defensible and cost-efficient. However, it is inherently limited by: firstly, the accuracy of risk assessment models used; secondly, ramifications of the fact that they are more likely to leave contamination in place; and thirdly, uncertainties involved and having to consider the total concentrations of all contaminants in soils that overestimate the potential risks from exposure to the contaminants. Consideration of contaminant bioavailability as the underlying basis for risk assessment and setting remediation goals of those contaminated lands that pose a risk to environmental and human health may lead to the development of a more sophisticated risk-based approach. However, employing the bioavailability concept in RBLM has not been extensively studied and/or legalized. This review highlights the extent of global land contamination, and the concept of risk-based assessment and management of contaminated sites including its advantages and disadvantages. Furthermore, the concept of bioavailability-based RBLM strategy has been proposed, and the challenges of RBLM and the priority areas for future research are summarized. Thus, the present review may help achieve a better understanding and successful implementation of a sustainable bioavailability-based RBLM strategy.

Remediation approaches for polycyclic aromatic hydrocarbons (PAHs) contaminated soils: Technological constraints, emerging trends and future directions.

For more than a decade, the primary focus of environmental experts has been to adopt risk-based management approaches to cleanup PAH polluted sites that pose potentially destructive ecological consequences. This focus had led to the development of several physical, chemical, thermal and biological technologies that are widely implementable. Established remedial options available for treating PAH contaminated soils are incineration, thermal conduction, solvent extraction/soil washing, chemical oxidation, bioaugmentation, biostimulation, phytoremediation, composting/biopiles and bioreactors. Integrating physico-chemical and biological technologies is also widely practiced for better cleanup of PAH contaminated soils. Electrokinetic remediation, vermiremediation and biocatalyst assisted remediation are still at the development stage. Though several treatment methods to remediate PAH polluted soils currently exist, a comprehensive overview of all the available remediation technologies to date is necessary so that the right technology for field-level success is chosen. The objective of this review is to provide a critical overview in this respect, focusing only on the treatment options available for field soils and ignoring the spiked ones. The authors also propose the development of novel multifunctional green and sustainable systems like mixed cell culture system, biosurfactant flushing, transgenic approaches and nanoremediation in order to overcome the existing soil- contaminant- and microbial-associated technological limitations in tackling high molecular weight PAHs. The ultimate objective is to ensure the successful remediation of long-term PAH contaminated soils.

Genotoxicity assessment of acute exposure of 2, 4-dinitroanisole, its metabolites and 2, 4, 6-trinitrotoluene to Daphnia carinata.

The insensitive munition ingredient, 2, 4-dinitroanisole has emerged as an alternative ingredient to 2, 4, 6-trinitro toluene in melt pourable high explosive formulations mainly due to its improved insensitiveness properties. As a result, production of 2, 4-dinitroanisole has increased and as a consequence 2, 4-dinitroanisole has emerged as a potential ingredient to enter the environment and possibly persist in water and soil ecosystems. The present study showed that 2, 4-dinitroanisole, its metabolites (2-amino 4-nitroanisole and 2,4-dinitroanisole) and 2, 4, 6-trinitro toluene were found to induce DNA damages in a freshwater crustacean Daphnia carinata exposed for 48 h and which was investigated by the alkaline single-cell gel electrophoresis (comet assay) method. The value of LC50-48 h of 2, 4-dinitroanisole was determined as 14.87 ± 1.70 (mg L-1) and its metabolites exhibited the similar toxic range although the toxicity of 2, 4, 6-trinitro toluene was seven-fold more toxic (2.32 ± 0.29 mg L-1) than 2, 4-dinitroanisole and its metabolites. Exposure to sub-acute toxicity concentration ranges of 2, 4-dinitroanisole and its metabolites and 2, 4, 6-trinitro toluene showed significant (P < 0.01) DNA damage. The higher concentration of each test chemical exhibited higher tail DNA per cent and increased olive tail moment. The results from this study can be used to identify genotoxic biomarkers for the risk assessment of insensitive munitions exposure in aquatic invertebrates.

Assessment of metal toxicity and bioavailability in metallophyte leaf litters and metalliferous soils using Eisenia fetida in a microcosm study.

The leaf litters of tree species, Acacia pycnantha (Ap) and Eucalyptus camaldulensis (Ec), predominantly growing at an abandoned copper (Cu) mine and mine soils including controls, were assessed for determining the metal toxicity and bioavailability using earthworm species Eisenia fetida, in a microcosm. Significant reduction in body weight as well as mortality were observed when the worms were introduced into mine soil or its combination with mine Ap litter. Virtually, there were no juveniles when the worms were fed on substratum that contained mine soil or mine leaf litter. The extent of bioaccumulation was dependent on water-soluble fraction of a metal in soil. The accumulation of cadmium, lead and copper in worm tissue was significantly more in treatments that received mine soil with or without mine leaf litter. However, the tissue concentration of zinc did not differ much in earthworms irrespective of its exposure to control or contaminated samples. Mine leaf litter from Ec, a known Cu hyperaccumulator, was more hospitable to earthworm survival and juvenile than that of Ap litter. Validation of the data on bioaccumulation of metals indicated that the mine leaf litter significantly contributed to metal bioavailability. However, it was primarily the metal concentration in mine soil that was responsible for earthworm toxicity and bioavailability. Our data also indicate that detrivores like earthworm is greatly responsible for heavy metal transfer from mines into the ecosystem.

Managing long-term polycyclic aromatic hydrocarbon contaminated soils: a risk-based approach.

Polycyclic aromatic hydrocarbons (PAHs) are a family of contaminants that consist of two or more aromatic rings fused together. Soils contaminated with PAHs pose significant risk to human and ecological health. Over the last 50 years, significant research has been directed towards the cleanup of PAH-contaminated soils to background level. However, this achieved only limited success especially with high molecular weight compounds. Notably, during the last 5-10 years, the approach to remediate PAH-contaminated soils has changed considerably. A risk-based prioritization of remediation interventions has become a valuable step in the management of contaminated sites. The hydrophobicity of PAHs underlines that their phase distribution in soil is strongly influenced by factors such as soil properties and ageing of PAHs within the soil. A risk-based approach recognizes that exposure and environmental effects of PAHs are not directly related to the commonly measured total chemical concentration. Thus, a bioavailability-based assessment using a combination of chemical analysis with toxicological assays and nonexhaustive extraction technique would serve as a valuable tool in risk-based approach for remediation of PAH-contaminated soils. In this paper, the fate and availability of PAHs in contaminated soils and their relevance to risk-based management of long-term contaminated soils are reviewed. This review may serve as guidance for the use of site-specific risk-based management methods.

Assessment of bioavailability of heavy metal pollutants using soil isolates of Chlorella sp.

Biotests conducted with plants are presently used to estimate metal bioavailability in contaminated soils. But when plants are grown in soils, especially the plants with fine roots, root collection is easily biased and tedious. Indeed, at harvest, small amounts of soil can adhere to roots, resulting in overestimation of root metal content, and the finest roots are often discarded from the analysis because of their difficult and almost impossible recovery. This report presents a novel method for assessing the bioavailability of heavy metals in soils using microalgae. Two species of green unicellular microalgae were isolated from two highly contaminated soils and identified by phylogenetic and molecular evolutionary analyses as Chlorella sp. RBM and Chlorella sp. RHM. These two cultures were used to determine the metal uptake from metal-contaminated soils of South Australia as a novel, cost-effective, simple and rapid method for assessing the bioavailability of heavy metals in soils. The suggested method is an attempt to achieve a realistic estimate of bioavailability which overcomes the inherent drawback of root metal contamination in the bioavailability indices so far reported.

Assessment of biological and biochemical indicators in soil under transgenic Bt and non-Bt cotton crop in a sub-tropical environment.

There is concern that transgenic Bt-crops carry genes that could have undesirable effects on natural and agro-ecosystem functions. We investigated the effect of Bt-cotton (expressing the Cry 1Ac protein) on several microbial and biochemical indicators in a sandy loam soil. Bt-cotton (MRC-6301Bt) and its non-transgenic near-isoline (MRC-6301) were grown in a net-house on a sandy clay loam soil. Soil and root samples were collected 60, 90, and 120 days after sowing. Soil from a control (no-crop) treatment was also included. Samples were analysed for microbial biomass C, N and P (MBC, MBN, MBP), total organic carbon (TOC), and several soil enzyme activities. The microbial quotient (MQ) was calculated as the ratio of MBC-to-TOC. The average of the three sampling events revealed a significant increase in MBC, MBN, MBP and MQ in the soil under Bt-cotton over the non-Bt isoline. The TOC was similar in Bt and non-Bt systems. Potential N mineralization, nitrification, nitrate reductase, and acid and alkaline phosphatase activities were all higher in the soil under Bt-cotton. Root dry weights were not different (P > 0.05), but root volume of Bt-cotton was higher on 90 and 120 days than that of non-Bt cotton. The time of sampling strongly affected the above parameters, with most being highest on 90 days after sowing. We concluded from the data that there were some positive or no negative effects of Bt-cotton on the studied indicators, and therefore cultivation of Bt-cotton appears to be no risk to soil ecosystem functions.