Glyphosate in the environment: interactions and fate in complex soil and water settings, and (phyto) remediation strategies.

Glyphosate (Gly) and its formulations are broad-spectrum herbicides globally used for pre- and post-emergent weed control. Glyphosate has been applied to terrestrial and aquatic ecosystems. Critics have claimed that Gly-treated plants have altered mineral nutrition and increased susceptibility to plant pathogens because of Gly ability to chelate divalent metal cations. Still, the complete resistance of Gly indicates that chelation of metal cations does not play a role in herbicidal efficacy or have a substantial impact on mineral nutrition. Due to its extensive and inadequate use, this herbicide has been frequently detected in soil (2 mg kg-1, European Union) and in stream water (328 µg L-1, USA), mostly in surface (7.6 µg L-1, USA) and groundwater (2.5 µg L-1, Denmark). International Agency for Research on Cancer (IARC) already classified Gly as a category 2 A carcinogen in 2016. Therefore, it is necessary to find the best degradation techniques to remediate soil and aquatic environments polluted with Gly. This review elucidates the effects of Gly on humans, soil microbiota, plants, algae, and water. This review develops deeper insight toward the advances in Gly biodegradation using microbial communities. This review provides a thorough understanding of Gly interaction with mineral elements and its limitations by interfering with the plants biochemical and morphological attributes.

Glyphosate (Gly) contamination in water, soil, and crops is an eminent threat globally. Various advanced and integrated approaches have been reported to remediate Gly contamination from the water-soil-crop system. This review elucidates the effects of Gly on human health, soil microbial communities, plants, algae, and water. This review develops deeper insight into the advances in Gly biodegradation using microbial communities, particularly soil microbiota. This review provides a brief understanding of Gly interaction with mineral elements and its limitations in interfering with the plants biochemical and morphological attributes.

Unveiling the significance of foliar-applied silicon, selenium and phosphorus for the management and remediation of arsenic in two different rice genotypes.

Under paddy soil conditions, rice plants are vulnerable to arsenic (As) accumulation, thus causing potential threat to human health. Here we investigated the influence of foliar-applied phosphorus (P: 10 and 20 mg L-1), silicon (Si: 0.6 and 1.5 g L-1) and selenium (Se: 5 and 10 mg L-1) on As accumulation, morphological and physiological attributes of two contrasting rice genotypes (KSK-133 and Super Basmati) under As stress (25 mg kg-1 as arsenate). Silicon foliar dressing significantly (p < 0.05) reduced grain As uptake (up to 67%) and improved rice growth and chlorophyll content (28-66%) in both rice genotypes over their controls. Phosphorus foliar application resulted in a notable decrease (17%) in grain As uptake of coarse rice genotype (KSK-133), while it slightly increased grain As uptake in the fine one (Super Basmati; 6%) compared to controls. However, foliar-applied Se did not show significant effects on rice plants growth attributes and As uptake in both genotypes. Similarly, biochemical and enzymatic attributes (i.e., lipid peroxidation, electrolyte leakage, peroxidase and catalase) were improved with Si application in rice plants, except for P treatment that was only effective for coarse one. Foliar-applied Si also resulted in reduced cancer risk and hazard quotient (< 0.10) for both rice genotypes. This study advances our understanding on critical role of different foliar-applied nutrients and rice genotypes, which is imperative to develop effective As remediation and management strategies in coarse and fine rice genotypes and protect human health.

This study provided new insights on the significance of foliar-applied phosphorus, silicon and selenium for the management and remediation of arsenic in fine (Super Basmati) and coarse (KSK-133) rice genotypes. Foliar-applied silicon was the most promising strategy to mitigate arsenic uptake and minimizing health risk in rice grain of both genotypes, while phosphorus was effective only for coarse one, thus showing a genotype dependent response. Interestingly, selenium foliar application had no significant effect on arsenic accumulation in both rice genotypes.

A critical review on the separation of heavy metal(loid)s from the contaminated water using various agricultural wastes.

Wastewater contamination with heavy metal(loids)s has become a worldwide environmental and public health problem due to their toxic and non-degradable nature. Different methods and technologies have been applied for water/wastewater treatment to mitigate heavy metal(loid)-induced toxicity threat to humans. Among various treatment methods, adsorption is considered the most attractive method because of its high ability and efficiency to remove contaminants from wastewater. Agricultural waste-based adsorbents have gained great attention because of high efficiency to heavy metal(loids)s removal from contaminated water. Chemically modified biosorbents can significantly enhance the stability and adsorption ability of the sorbents. The two mathematical models of sorption, Freundlich and Langmuir isotherm models, have mostly been studied. In kinetic modeling, pseudo-second-order model proved better in most of the studies compared to pseudo-first-order model. The ion exchange and electrostatic attraction are the main mechanisms for adsorption of heavy metal(loid)s on biosorbents. The regeneration has allowed various biosorbents to be recycled and reused up to 4-5 time. Most effective eluents used for regeneration are dilute acids. For practical perspective, biosorbent removal efficiency has been elucidated using various types of wastewater and economic analysis studies. Economic analysis of adsorption process using agricultural waste-based biosorbents proved this approach cheaper compared to traditional commercial adsorbents, such as chemically activated carbon. The review also highlights key research gaps to advance the scope and application of waste peels for the remediation of heavy metal(loid)s-contaminated wastewater.

This review provides new information and insights on the potential utilization of agriculture-based biosorbents for the removal of contaminants, especially heavy metal(loid)s from toxic water/wastewater, as well as their mechanisms, adsorption efficiency, and regeneration ability. For practical perspective, biosorbent adsorption efficiency was elucidated by using various types of wastewater and economic analysis studies.

Glucose input profit soil organic carbon mineralization and nitrogen dynamics in relation to nitrogen amended soils.

Exogenous carbon (C) inputs stimulate soil organic carbon (SOC) decomposition, strongly influencing atmospheric concentrations and climate dynamics. The direction and magnitude of C decomposition depend on the C and nitrogen (N) addition, types and pattern. Despite the importance of decomposition, it remains unclear whether organic C input affects the SOC decomposition under different N-types (Ammonium Nitrate; AN, Urea; U and Ammonium Sulfate; AS). Therefore, we conducted an incubation experiment to assess glucose impact on N-treated soils at various levels (High N; HN: 50 mg/m2, Low N; LN: 05 mg/m2). The glucose input increased SOC mineralization by 38% and 35% under HN and LN, respectively. Moreover, it suppressed the concentration of NO3--N by 35% and NH4+-N by 15% in response to HN and LN soils, respectively. Results indicated higher respiration in Urea-treated soils and elevated net total nitrogen content (TN) in AS-treated soils. AN-amended soil exhibited no notable rise in C mineralization and TN content compared to other N-type soils. Microbial biomass carbon (MBC) was higher in glucose treated soils under LN conditions than control. This could result that high N suppressed microbial N mining and enhancing SOM stability by directing microbes towards accessible C sources. Our results suggest that glucose accelerated SOC mineralization in urea-added soils and TN contents in AS-amended soils, while HN levels suppressed C release and increased TN contents in all soil types except glucose-treated soils. Thus, different N-types and levels play a key role in modulating the stability of SOC over C input.

Biochar/nano-zerovalent zinc-based materials for arsenic removal from contaminated water.

In this study, we explored the potential of a newly prepared nano-zero valent zinc (nZVZn), biochar (BC)/nZVZn and BC/hydroxyapatite-alginate (BC/HA-alginate) composites for the removal of inorganic As species from water. Relatively, higher percentage removal of As(III) and As(V) was obtained by nZVZn at pH 3.4 (96% and 94%, respectively) compared to BC/nZVZn (90% and 88%) and BC/HA-alginate (88% and 80%) at pH 7.2. Freundlich model provided the best fit (R2 = up to 0.98) for As(III) and As(V) sorption data of all the sorbents, notably for nZVZn. The pseudo-second order model well-described kinetics of As(III) and As(V) (R2 = 0.99) sorption on all the sorbents. The desorption experiments demonstrated that the As removal efficiency, up to the third sorption/desorption cycle, was in the order of nZVZn ∼ BC/HA-alginate (88%) > BC/nZVZn (84%). The Fourier transform infrared spectroscopy depicted that the -OH, -COOH, Zn-O and Zn-OH surface functional groups were responsible for the sorption of As(III) or As(V) on the sorbents investigated here. This study highlights that removal of As species from water by BC/nZVZn composite can be compared with nZVZn, suggesting that integrating BC with nZVZn could efficiently remove As from As-contaminated drinking water.

This is the first study to explore the potential of a newly prepared sugarcane bagasse biochar/nano-zerovalent zinc (BC/nZVZn) based composite for the removal of inorganic arsenic (As) species from water. The results indicated high percentage removal of As(III) and As(V) from water by BC/nZVZn that were comparable to nZVZn alone.

The role of various ameliorants on geochemical arsenic distribution and CO2-carbon efflux under paddy soil conditions.

Climate change is a global challenge that is accelerated by contamination with hazardous substances like arsenic (As), posing threat to the agriculture, ecosystem and human health. Here, we explored the impact of various ameliorants on geochemical distribution of As in two soils with contrasting textures (sandy clay loam (Khudpur Village) and clay loam (Mattital Village)) under paddy soil conditions and their influence on the CO2-carbon efflux. The exchangeable As pool in clay loam soil increased as: lignite (0.4%) < biogas slurry (6%) < cow dung (9%), and < biochar (20%). However, in the sandy clay loam soil exchangeable soil As pool was found to be maximum with farmyard manure followed by biogas slurry, biochar and cow dung (17%, 14%, 13% and 7%, respectively). Interestingly, in the sandy clay loam soil the percentage As distribution in organic fraction was: biochar (38%) > cow dung (33%) > biogas slurry (23%) > sugarcane bagasse (22%) > farmyard manure (21%) that was higher compared to the clay loam soil (< 6% for all the amendments). In addition to the highest As immobilization by biochar in sandy clay loam soil, it also led to the lowest CO2-carbon efflux (1470 CO2-C mg kg-1) among all the organic/inorganic amendments. Overall, the current study advances our understanding on the pivotal role of organic amendments, notably biochar, in immobilizing As under paddy soil conditions with low (CO2) carbon loss, albeit it is dependent on soil and ameliorant types.

The potential of microbes and sulfate in reducing arsenic phytoaccumulation by maize (Zea mays L.) plants.

Arsenic (As) contamination in soil-plant system is an important environmental, agricultural and health issue globally. The microbe- and sulfate-mediated As cycling in soil-plant system may depend on soil sulfate levels, and it can be used as a potential strategy to reduce plant As uptake and improve plant growth. Here, we investigated the role of soil microbes (SMs) to examine As phytoaccumulation using maize as a test plant, under varying sulfate levels (S-0, S-5, S-25 mmol kg-1) and As stress. The addition of sulfate and SMs promoted maize plant growth and reduced As concentration in shoots compared to sulfate-treated plants without SMs. Results revealed that the SMs-S-5 treatment proved to be the most promising in reducing As uptake by 27% and 48% in root and shoot of the maize plants, respectively. The SMs-S treatments, primarily with S-5, enhanced plant growth, shoot dry biomass, Chl a, b and total Chl (a + b) contents, and gas exchange attributes of maize plants. Similarly, the antioxidant defense in maize plants was increased significantly in SMs-S-treated plants, notably with SMs-S-5 treatment. Overall, the SMs-S-5-treated plants possessed improved plant growth, dry biomass, physiology and antioxidant defense system and decrease in plant shoot As concentration. The outcomes of this study suggest that sulfate supplementation in soil along with SMs could assist in reducing As accumulation by maize plants, thus providing a sustainable and eco-friendly bioremediation strategy in limiting As exposure.

Reforestation of Cunninghamia lanceolata changes the relative abundances of important prokaryotic families in soil.

Over the past decades, many forests have been converted to monoculture plantations, which might affect the soil microbial communities that are responsible for governing the soil biogeochemical processes. Understanding how reforestation efforts alter soil prokaryotic microbial communities will therefore inform forest management. In this study, the prokaryotic communities were comparatively investigated in a secondary Chinese fir forest (original) and a reforested Chinese fir plantation (reforested from a secondary Chinese fir forest) in Southern China. The results showed that reforestation changed the structure of the prokaryotic community: the relative abundances of important prokaryotic families in soil. This might be caused by the altered soil pH and organic matter content after reforestation. Soil profile layer depth was an important factor as the upper layers had a higher diversity of prokaryotes than the lower ones (p < 0.05). The composition of the prokaryotic community presented a seasonality characteristic. In addition, the results showed that the dominant phylum was Acidobacteria (58.86%) with Koribacteraceae (15.38%) as the dominant family in the secondary Chinese fir forest and the reforested plantation. Furthermore, soil organic matter, total N, hydrolyzable N, and NH4+-N were positively correlated with prokaryotic diversity (p < 0.05). Also, organic matter and NO3--N were positively correlated to prokaryotic abundance (p < 0.05). This study demonstrated that re-forest transformation altered soil properties, which lead to the changes in microbial composition. The changes in microbial community might in turn influence biogeochemical processes and the environmental variables. The study could contribute to forest management and policy-making.

Enhanced capacity of thiol-functionalized sugarcane bagasse and rice husk biochars for arsenite sorption in aqueous solutions.

The utilization of biowastes for producing biochar to remove potentially toxic elements from water represents an important pathway for aquatic ecosystem decontamination. Here we explored the significance of thiol-functionalization on sugarcane bagasse biochar (Th/SCB-BC) and rice husk biochar (Th/RH-BC) to enhance arsenite (As(III)) removal capacity from water and compared their efficiency with both pristine biochars (SCB-BC and RH-BC). The maximum As(III) sorption was found on Th/SCB-BC and Th/RH-BC (2.88 and 2.51 mg g-1, respectively) compared to the SCB-BC and RH-BC (1.51 and 1.40 mg g-1). Relatively, a greater percentage of As(III) removal was obtained with Th/SCB-BC and Th/RH-BC (92% and 83%, respectively) at a pH 7 compared to pristine SCB-BC and RH-BC (65% and 55%) at 6 mg L-1 initial As(III) concentration, 2 h contact time and 1 g L-1 sorbent dose. Langmuir (R2 = 0.99) isotherm and pseudo-second-order kinetic (R2 = 0.99) models provided the best fits to As(III) sorption data. Desorption experiments indicated that the regeneration ability of biochars decreased and it was in the order of Th/SCB-BC (88%) > Th/RH-BC (82%) > SCB-BC (77%) > RH-BC (69%) up to three sorption-desorption cycles. Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy results demonstrated that the thiol (-S-H) functional groups were successfully grafted on the surface of two biochars and as such contributed to enhance As(III) removal from water. Spectroscopic data indicated that the surface functional moieties, such as -S-H, - OH, - COOH, and C = O were involved to increase As(III) sorption on thiol-functionalized biochars. This study highlights that thiol-grafting on both biochars, notably on SCB-BC, enhanced their ability to remove As(III) from water, which can be used as an effective technique for the treatment of As from drinking water.

Constructed wetlands as a sustainable technology for wastewater treatment with emphasis on chromium-rich tannery wastewater.

Water scarcity is a major threat to agriculture and humans due to over abstraction of groundwater, rapid urbanization and improper use in industrial processes. Industrial consumption of water is lower than the abstraction rate, which ultimately produces large amounts of wastewater such as from tannery industry containing high concentration of chromium (Cr). Chromium-contaminated tannery industry wastewater is used for irrigation of food crops, resulting in food safety and public health issues globally. In contrast to conventional treatment technologies, constructed wetlands (CWs) are considered as an eco-friendly technique to treat various types of wastewaters, although their application and potential have not been discussed and elaborated for Cr treatment of tannery wastewater. This review briefly describes Cr occurrence, distribution and speciation in aquatic ecosystems. The significance of wetland plant species, microorganisms, various bedding media and adsorbents have been discussed with a particular emphasis on the removal and detoxification of Cr in CWs. Also, the efficiency of various types of CWs is elaborated for advancing our understanding on Cr removal efficiency and Cr partitioning in various compartments of the CWs. The review covers important aspects to use CWs for treatment of Cr-rich tannery wastewater that are key to meet UN's Sustainable Development Goals.

The significance of eighteen rice genotypes on arsenic accumulation, physiological response and potential health risk.

Rice is an important food crop that is susceptible to arsenic (As) contamination under paddy soil conditions depending on As uptake characteristics of the rice genotypes. Here we unveiled the significance of eighteen (fine and coarse) rice genotypes against As accumulation/tolerance, morphological and physiological response, and antioxidant enzymes-enabled defense pathways. Arsenic significantly affected rice plant morphological and physiological attributes, with relatively more impacts on fine compared to coarse genotypes. Grain, shoot, and root As uptake were lower in fine genotypes (0.002, 0.020, and 0.032 mg pot-1 DW, respectively) than that of coarse (0.031, 0.60, and 1.2 mg pot-1 DW, respectively). Various biochemical (pigment contents, hydrogen peroxide, lipid peroxidation) and defense (antioxidant enzymes) plant parameters indicated that the fine genotypes, notably Kainat and Basmati-385, possessed the highest As tolerance. Arsenic-induced risk indices exhibited greater hazard quotient (up to 1.47) and carcinogenic risk (up to 0.0066) for coarse genotypes compared to the fine ones, with the greatest risk for KSK-282. This study elaborates the pivotal role of genotypic variation among rice plants in As accumulation, which is crucial for mitigating the associated human health risk. Further research is required on molecular aspects, e.g., genetic sequencing, to examine rice genotypes variation in defense mechanisms to As contamination.

Distribution and ecological risk assessment of trace elements in the paddy soil-rice ecosystem of Punjab, Pakistan.

Trace elements (TEs) contamination of agricultural soils requires suitable criteria for regulating their toxicity limits in soil and food crops, which depends on their potential ecological risk spanning regional to global scales. However, no comprehensive study is available that links TE concentrations in paddy soil with ecological and human health risks in less developed regions like Pakistan. Here we evaluated the data set to establish standard guidelines for defining the hazard levels of various potentially toxic TEs (such as As, Cd, Co, Cu, Cr, Fe, Mn, Ni, Pb, Se, Zn) in agricultural paddy soils of Punjab, Pakistan. In total, 100 topsoils (at 0-15 cm depth) and 204 rice plant (shoot and grain) samples were collected from five ecological zones of Punjab (Gujranwala, Hafizabad, Vehari, Mailsi, and Burewala), representing the major rice growing regions in Pakistan. The degree of contamination (Cd) and potential ecological risk index (PERI) established from ecological risk models were substantially higher in 100% and 97% of samples, respectively. The positive matrix factorization (PMF) model revealed that the elevated TEs concentration, notably Cd, As, Cr, Ni, and Pb, in the agricultural paddy soil was attributed to the anthropogenic activities and groundwater irrigation. Moreover, the concentration of these TEs in rice grains was higher than the FAO/WHO's safe limits. This study provided a baseline, albeit critical knowledge, on the impact of TE-allied ecological and human health risks in the paddy soil-rice system in Pakistan; and it opens new avenues for setting TEs guidelines in agro-ecological zones globally, especially in underdeveloped regions.

Impact of organic and inorganic amendments on arsenic accumulation by rice genotypes under paddy soil conditions: A pilot-scale investigation to assess health risk.

In this study, we investigated the distinct effects of organic (farmyard manure (FYM), cow dung (CD), biogas slurry (BGS), sugarcane bagasse (SCB)) and inorganic (gypsum and lignite) amendments on arsenic (As) accumulation by two rice genotypes, Kainat (fine) and Basmati-385 (coarse), under As stress. Results showed that shoot As concentration was ~2-time greater in Kainat compared to Basmati-385 (3.1-28 vs. 1.7-16 mg kg-1 DW, respectively), with the minimum shoot As content observed with CD and SCB. In contrast to gypsum and lignite, grain As concentration was significantly reduced with CD and SCB for Kainat (0.29 and 0.24 mg kg-1 DW) and Basmati-385 (0.04 and 0.09 mg kg-1 DW). Data indicated that the CD and SCB also improved chlorophyll a and b contents, reduced lipid peroxidation and hydrogen peroxide production in both rice genotypes. Significantly, the CD and SCB decreased grain As concentration below the FAO safe As limit in rice grain (0.2 mg kg-1 DW), especially in coarse rice genotype (Basmati-385), resulting in negligible As-induced human health risk. This study highlights the significance of amendments and rice genotypes controlling As accumulation in rice grain, which should be considered prior to As remediation program of paddy soils for limiting exposure of humans to As via rice grain.

Arsenic biogeochemical cycling in paddy soil-rice system: Interaction with various factors, amendments and mineral nutrients.

Arsenic (As) contamination is a well-recognized environmental and health issue, threatening over 200 million people worldwide with the prime cases in South and Southeast Asian and Latin American countries. Rice is mostly cultivated under flooded paddy soil conditions, where As speciation and accumulation by rice plants is controlled by various geo-environmental (biotic and abiotic) factors. In contrast to other food crops, As uptake in rice has been found to be substantially higher due to the prevalence of highly mobile and toxic As species, arsenite (As(III)), under paddy soil conditions. In this review, we discussed the biogeochemical cycling of As in paddy soil-rice system, described the influence of critical factors such as pH, iron oxides, organic matter, microbial species, and pathways affecting As transformation and accumulation by rice. Moreover, we elucidated As interaction with organic and inorganic amendments and mineral nutrients. The review also elaborates on As (im)mobilization processes and As uptake by rice under the influence of different mineral nutrients and amendments in paddy soil conditions, as well as their role in mitigating As transfer to rice grain. This review article provides critical information on As contamination in paddy soil-rice system, which is important to develop suitable strategies and mitigation programs for limiting As exposure via rice crop, and meet the UN's key Sustainable Development Goals (SDGs: 2 (zero hunger), 3 (good health and well-being), 12 (responsible consumption and production), and 13 (climate action)).

Arsenic speciation and biotransformation pathways in the aquatic ecosystem: The significance of algae.

The contamination of aquatic systems with arsenic (As) is considered to be an internationally-important health and environmental issue, affecting over 115 countries globally. Arsenic contamination of aquatic ecosystems is a global threat as it can enter the food chain from As-rich water and cause harmful impacts on the humans and other living organisms. Although different factors (e.g., pH, redox potential, iron/manganese oxides, and microbes) control As biogeochemical cycling and speciation in water systems, the significance of algal species in biotransformation of As is poorly understood. The overarching attribute of this review is to briefly elaborate various As sources and its distribution in water bodies and factors affecting As biogeochemical behavior in aqueous ecosystems. This review elucidates the intriguing role of algae in biotransformation/volatilization of As in water bodies under environmentally-relevant conditions. Also, we critically delineate As sorption, uptake, oxidation and reduction pathways of As by algae and their possible role in bioremediation of As-contaminated water (e.g., drinking water, wastewater). The current review provides the updated and useful framework for government and water treatment agencies to implement algae in As remediation programs globally.