Characteristics of heavy metal accumulation and risk assessment in understory Panax notoginseng planting system.

Yunnan Province is the main planting area of the precious Chinese herbal medicines (CHM) Panax notoginseng; however, it locates the geological area with high soil heavy metals in China. The frequent land replacement due to continuous cropping obstacles and excessive application of chemicals makes P. notoginseng prone to be contaminated by heavy metals under the farmland P. notoginseng (FPn) planting. To overcome farmland shortage, understory P. notoginseng (UPn) was developed as a new ecological planting model featured by no chemicals input. However, this newly developed planting system requires urgently the soil-plant heavy metal characteristics and risk assessment. This study aimed to evaluate the pollution status of eight heavy metals in the tillage layer (0-20 cm), subsoil layer (20-40 cm) and the plants of UPn in Lancang County, Yunnan Province. Pollution index (Pi) showed that the contamination degree of heavy metals in the tillage layer and subsoil layer was Cd > Pb > Ni > Cu > Zn > Cr > Hg > As and Pb > Cd > Cu > Ni > Cr > Hg > Zn > As, respectively. Potential ecological risk index (PERI) for the tillage layer and subsoil layer was slight and middle, respectively. The exceeding standard rate of Cd, As, Pb, Hg, Cu in the UPn roots was 5.33%, 5.33%, 13.33%, 26.67% and 1.33%, respectively, while only Cd and Hg in the UPn leaves exceeded the standard 10% and 14%, respectively. The enrichment abilities of Cd and Hg in the roots and leaves of UPn were the strongest, while that of Pb was the weakest. The Hazard index (HI) and target hazard quotient (THQ) of eight heavy metals in the roots and leaves of UPn were less than 1.Therefore, our results prove that Upn has no human health risk and provide a scientific basis for the safety evaluation and extension of UPn.

Flash Fabrication of Orally Targeted Nanocomplexes for Improved Transport of Salmon Calcitonin across the Intestine.

Salmon calcitonin (sCT) is a potent calcium-regulating peptide hormone and widely applied for the treatment of some bone diseases clinically. However, the therapeutic usefulness of sCT is hindered by the frequent injection required, owing to its short plasma half-life and therapeutic need for a high dose. Oral delivery is a popular modality of administration for patients because of its convenience to self-administration and high patient compliance, while orally administered sCT remains a great challenge currently due to the existence of multiple barriers in the gastrointestinal (GI) tract. Here, we introduced an orally targeted delivery system to increase the transport of sCT across the intestine through both the paracellular permeation route and the bile acid pathway. In this system, sCT-based glycol chitosan-taurocholic acid conjugate (GC-T)/dextran sulfate (DS) ternary nanocomplexes (NC-T) were produced by a flash nanocomplexation (FNC) process in a kinetically controlled mode. The optimized NC-T exhibited well-controlled properties with a uniform and sub-60 nm hydrodynamic diameter, high batch-to-batch reproducibility, good physical or chemical stability, as well as sustained drug release behaviors. The studies revealed that NC-T could effectively improve the intestinal uptake and permeability, owing to its surface functionalization with the taurocholic acid ligand. In the rat model, orally administered NC-T showed an obvious hypocalcemia effect and a relative oral bioavailability of 10.9%. An in vivo assay also demonstrated that NC-T induced no observable side effect after long-term oral administration. As a result, the orally targeted nanocomplex might be a promising candidate for improving the oral transport of therapeutic peptides.

Resourcization of Argillaceous Limestone with Mn3O4 Modification for Efficient Adsorption of Lead, Copper, and Nickel.

Argillaceous limestone (AL) is comprised of carbonate minerals and clay minerals and is widely distributed throughout the Earth's crust. However, owing to its low surface area and poorly active sites, AL has been largely neglected. Herein, manganic manganous oxide (Mn3O4) was used to modify AL by an in-situ deposition strategy through manganese chloride and alkali stepwise treatment to improve the surface area of AL and enable its utilization as an efficient adsorbent for heavy metals removal. The surface area and cation exchange capacity (CEC) were enhanced from 3.49 to 24.5 m2/g and 5.87 to 31.5 cmoL(+)/kg with modification, respectively. The maximum adsorption capacities of lead (Pb2+), copper (Cu2+), and nickel (Ni2+) ions on Mn3O4-modified argillaceous limestone (Mn3O4-AL) in mono-metal systems were 148.73, 41.30, and 60.87 mg/g, respectively. In addition, the adsorption selectivity in multi-metal systems was Pb2+ > Cu2+ > Ni2+ in order. The adsorption process conforms to the pseudo-second-order model. In the multi-metal system, the adsorption reaches equilibrium at about 360 min. The adsorption mechanisms may involve ion exchange, precipitation, electrostatic interaction, and complexation by hydroxyl groups. These results demonstrate that Mn3O4 modification realized argillaceous limestone resourcization as an ideal adsorbent. Mn3O4-modified argillaceous limestone was promising for heavy metal-polluted water and soil treatment.

Factors controlling the heavy metal ion activity in soil contaminated by microplastics with different mulch durations: Partial least squares path model.

Film covers have been widely applied worldwide. However, the effects of long-term plastic film mulching use on heavy metal (HM) activity in soil remain unclear. This study focused on farmland in the upstream part of the Pearl River in China and collected 103 soil samples after 2, 5, and 15 years of plastic film mulching. The main environmental factors controlling microplastics (MPs), plasticizer phthalic acid esters (PAEs), HM pollution characteristics, and HM activity were analyzed. The results showed that Polyethylene (PE) and di(2-ethylhexyl) dicyclohexyl phthalate (DCHP) were the main MPs and PAEs, respectively. The abundance of MPs and the concentrations of free HM ions (Cd, Cu, and Ni) in the soil solution increased with increasing plastic film mulching duration. The Partial Least Squares Path Model (PLS-PM) indicated that after plastic film mulching, soil chemical properties (pH/amorphous Fe) and biological properties (Dissolved organic carbon/ Easily oxidizable carbon/Microbial biomass carbon) were the main controlling factors for free and complexed HM ions (Cd, Pb, Cu, and Ni). These results suggest that, after plastic film mulching, MPs indirectly regulate HM activity by altering soil properties. This study provides a new perspective for the management of MPs and HM activities in agricultural ecosystems.

Shallow wet irrigation reduces nitrogen leaching loss rate in paddy fields by microbial regulation and lowers rate of downward migration of leaching water: a 15N-tracer study.

China consumes 35% of the world's fertilizer every year; however, most of the nitrogen fertilizers, which are essential for rice cultivation, are not used effectively. In this study, factors affecting the nitrogen leaching loss rate were studied in typical soil and rice varieties in South China. The effects of various irrigation measures on rice growth and nitrogen leaching loss were investigated by conducting experiments with eight groups. These groups included traditional irrigation (TI) and shallow wet irrigation (SWI). The TI is a common irrigation method for farmers in South China, maintaining a water layer of 5-8 cm depth. For SWI, after establishing a shallow water layer usually maintaining at 1-2 cm, paddy is irrigated when the field water level falls to a certain depth, then this process is then repeat as necessary. The nitrogen distribution characteristics were determined using 15N isotope tracing. In addition, the effects of nitrification, denitrification, and microbial composition on soil nitrogen transformation at different depths were studied by microbial functional gene quantification and high-throughput sequencing. The results revealed that in the SWI groups, the total nitrogen leaching loss rate reduced by 0.3-0.8% and the nitrogen use efficiency (NUE) increased by 2.18-4.43% compared with those in the TI groups. After the 15N-labeled nitrogen fertilizer was applied, the main pathways of nitrogen were found to be related to plant absorption and nitrogen residues. Furthermore, paddy soil ammonia-oxidizing archaea were more effective than ammonia-oxidizing bacteria for soil ammonia oxidation by SWI groups. The SWI measures increased the relative abundance of Firmicutes in paddy soil, enhancing the ability of rice to fix nitrogen to produce ammonium nitrogen, thus reducing the dependence of rice on chemical fertilizers. Moreover, SWI enhanced the relative abundance of nirS and nosZ genes within surface soil bacteria, thereby promoting denitrification in the surface soil of paddy fields. SWI also promoted ammonia oxidation and denitrification by increasing the abundance and activity of Proteobacteria, Nitrospirae, and Bacteroidetes. Collectively, SWI effectively reduced the nitrogen leaching loss rate and increase NUE.

Effects of polyethylene and biodegradable microplastics on photosynthesis, antioxidant defense systems, and arsenic accumulation in maize (Zea mays L.) seedlings grown in arsenic-contaminated soils.

Arsenic (As) and microplastic (MP) co-exposure is a major environmental problem in terrestrial ecosystems. Polyethylene and biodegradable plastics decompose into MP particles under microbial-mediated and weathering conditions. However, the effects of MP particles on physiological responses and As accumulation in maize have not been thoroughly explored. In this study, the effects of polyethylene microplastic particles (PEMPs) and biodegradable microplastic particles (BPMPs) on As accumulation, growth and physio-biochemical performance of maize seedlings (Zea mays L.) in As-contaminated soil were investigated. Our study showed that 10 % PE reduced As content in maize seedlings leaves (roots) by 41.19(34.53) µg kg-1, compared to the control. The 10 % BP reduced As content in maize seedlings leaves (roots) by 64.24 (57.27) µg kg-1. 10 % PE (10 % BP) reduced maize seedlings leaf area, total chlorophyll content and photosynthetic rate by 5.05 % (21.68 %), 44.98 % (57.12 %) and 65.29 % (77.89 %) and increased H2O2 content by 38.04 % (179.6 %), respectively. The antioxidant defense system of maize seedlings leaves was damaged by PEMPs and As co-exposure. Maize seedlings has adapted to stress by regulating antioxidant enzyme activity and the AsA-GSH cycle under BPMPs and As co-exposure. This study provides new insights into the effects of PEMPs and BPMPs on phytotoxicity and As accumulation in As-contaminated soils. Preliminarily data suggests that BPMPs may exhibit greater toxic effects on maize seedlings than PEMPs, which warrants further exploration.

Polyethylene and poly (butyleneadipate-co-terephthalate)-based biodegradable microplastics modulate the bioavailability and speciation of Cd and As in soil: Insights into transformation mechanisms.

Microplastics (MPs) that enter the soil can alter the physicochemical and biochemical properties of soil and affect speciation of heavy metals (HMs), thereby perturbing the bioavailability of HMs. However, the mechanisms underlying these effects are not understood. Therefore, we investigated the effects of MPs from poly (butyleneadipate-co-terephthalate)-based biodegradable mulch (BM) and polyethylene mulch (PM) in Cd- or As-contaminated soil on soil properties and speciation of HMs. MPs were characterised using Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The addition of MPs reduced the bioavailability of HMs in soil and promoted the transformation of HMs into inert fractions. The mechanisms underlying the reduction of the bioavailability of HMs in soils could be as follows: (1) the entry of MPs into the soil changed its properties, which reduced the bioavailability of HMs; (2) FTIR and XPS analyses revealed that the hydroxyl and carboxyl groups and benzene ring present on the surface of aged MPs stabilized complexes (As(V)-O) with As(V) may have directly reduced the bioavailability of As(V) in soil; (3) aged BM exposed more amounts and types of reactive functional groups and was more effective in stabilising soil HMs than PM. Overall, this study provides new insights regarding the complexation mechanisms of soil HMs by MPs from different plastic mulch sources.

Sulfur fertiliser enhancement of Erigeron breviscapus (Asteraceae) quality by improving plant physiological responses and reducing soil cadmium bioavailability.

Erigeron breviscapus (Vant.) Hand.-Mazz. is an important medicinal plant; however, its quality is severely diminished by cadmium (Cd) pollution. Sulfur fertilisation can improve the production and application of E. breviscapus. This study examined Cd stress alleviation in the soil-plant system and determined the plant growth response after the application of sulfur fertiliser. The soil Cd concentration used in the treatments was 100 g·kg-1, and the sulfur fertiliser application rates were 0.1, 0.2, and 0.3 g·kg-1. Using pot experiments, we explored the impacts of high, medium, and low amounts of sulfur fertiliser on Cd accumulation and the quality and activity of E. breviscapus. The results showed that the application of sulfur fertiliser promoted Cd transformation to residual Cd under oxidation conditions, reducing Cd accumulation in E. breviscapus. Throughout the growth period, the application of sulfur fertiliser increased the soluble protein content and antioxidant enzyme activity, which alleviated Cd toxicity. The net photosynthetic rate, transpiration rate, intercellular CO2 concentration, chlorophyll level, and leaf width increased significantly. The biomass content of E. breviscapus also increased. Sulfur fertiliser improves the quality of herbaceous medicinal plants by reducing Cd accumulation and increasing scutellarin, chlorogenic, isochlorogenic acid B, and isochlorogenic acid C contents. A reasonable application of sulfur fertiliser is essential for improving E. breviscapus quality. This study provides a new method to reduce the ecological risk of planting herbaceous medicinal plants in Cd-contaminated soil.

Spectroscopic investigation of Cu2+, Pb2+ and Cd2+ adsorption behaviors by chitosan-coated argillaceous limestone: Competition and mechanisms.

In the present study, the competitive adsorption of Cu2+, Pb2+, and Cd2+ by a novel natural adsorbent (i.e., argillaceous limestone) modified with chitosan (C-AL) was investigated. The results demonstrated that both intraparticle diffusion and chemisorption marked significant contributions to the Cu2+ adsorption process by both raw argillaceous limestone (R-AL) and C-AL in mono-metal adsorption systems. Antagonism was found to be the predominant competitive effect for Cu2+, Pb2+ and Cd2+ adsorptions by C-AL in the multi-metal adsorption system. The three-dimensional simulation and FTIR analysis revealed that the presence of Cu2+ suppressed Pb2+ and Cd2+ adsorptions, while the effect of Cd2+ on Cu2+ and Pb2+ adsorptions was insignificant. The spectroscopic analyses evidenced that amide groups in C-AL played a crucial role in metal adsorption. The preferential adsorptions of Pb2+ > Cu2+ > Cd2+ were likely due to the different affinities of the metals to the lone pair of electrons on the N atom from the amide groups and/or the O atoms from the -OH and -COO- groups on C-AL. The interactions between C-AL and metal ions and between various metal species influenced their competitive adsorption behaviors. C-AL exhibited a superior metal adsorption capacity in comparison with that the capacities of other natural adsorbents reported during the last decade, suggesting its potential practical applications.

Glycine transformation induces repartition of cadmium and lead in soil constituents.

Heavy metal stress in soil accelerates the plant root exudation of organic ligands. The degradation of exudate ligands can be fundamental to controlling the complexation of heavy metals. However, this process remains poorly understood. Here, we investigated the relationship between the transformation of glycine, a representative amino acid exudate, and cadmium/lead mobility in soils. Two 48-h incubation experiments were conducted after glycine addition to the soils. Parameters related to glycine distribution and degradation, Cd/Pb mobility, and the formation of glycine-Cd complex were analyzed. Glycine addition gradually decreased the Cd and Pb mobility throughout the 48-h incubation. By the end of the experiment, the CaCl2-extracted Cd and Pb concentrations decreased by 63.5% and 43.6%, respectively. The glycine mineralization was strong in the first 6 h, as indicated by a sharp decrease in CO2 efflux rates from 10.04 ±â€¯0.62 to 3.51 ±â€¯0.07 mg C-CO2 kg-1 soil h-1. The mineralization rates notably decreased after 6 h. The comparisons of dissolved organic carbon and hydrolyzable amino acid contents indicated that glycine mineralization in solution (95.6%) was much stronger than that in soil solids (49.3%). At the end of incubation, 0.22 mmol kg-1 glycine remained in soil solids. The remaining glycine provided sufficient sorption sites for Cd2+ and Pb2+, resulting in enhanced metal fixation via complexation. Comparisons of zeta potentials supported the formation of the glycine-Cd complex. The Cd and Pb immobilization processes could be attributed to metal-glycine complex formation, sorption re-equilibrium, and glycine degradation. These findings emphasize that the biogeochemical processes of glycine, derived from root exudates or protein degradation products, increased the sorption of heavy metals to soils and thus reduced their toxicity to plants.

Competitive adsorption of Cd2+, Pb2+ and Ni2+ onto Fe3+-modified argillaceous limestone: Influence of pH, ionic strength and natural organic matters.

In present study, the feasibility of applying a natural adsorbent with Fe3+ modification (Fe3+-modified argillaceous limestone, FAL) on the competitive adsorption of heavy metals (i.e., Cd2+, Pb2+ and Ni2+) was evaluated. The current results revealed an efficient adsorption on Cd2+, Pb2+ and Ni2+ in mono-metal system. Further experiments demonstrated a high selectivity of Pb2+ during the competitive adsorption of Cd2+, Pb2+ and Ni2+. The adsorption selectivity of the metal ions followed the order of Pb ≫ Cd > Ni. In addition, both pH and ionic strength are important factors affecting the metal adsorptions. It is interestingly that various NOMs (i.e., humic acid (HA) and glycine (Gly)) exerted different effects on the adsorption behaviors, probably due to the different affinities for Pb2+, Cd2+ and Ni2+ and the redistribution of newly-formed metal-DOM complexes. X-ray photoelectron spectroscopy (XPS) analysis together with X-ray diffraction (XRD) and energy dispersive spectrometer (EDS) analysis revealed that the metal adsorptions were mainly regulated via the synergistic mechanisms of ion exchange by Na+, Ca2+, and Al3+, precipitation to form CdCO3 and Pb2(OH)2(CO3)2, as well as complexes of FAL-OPb and FAL-ONi by hydroxyl groups on the surface of FAL. The application of FAL would be a promising option in leading to an efficient heavy metal removal.

Factors controlling cadmium and lead activities in different parent material-derived soils from the Pearl River Basin.

Labile metals in agricultural soils are available to crops and thus pose a great health risk for human beings. Therefore, factors influencing heavy metal activity are of interest to researchers. In this study, a total of 142 soil samples representing 5 typical parent materials in the Pearl River Basin (PRB), China were collected to investigate factors impacting the distribution of labile Cd and Pb in the soils. The results showed that the labile fractions accounted for 0.03%-14.7% for Cd and 0.01%-0.39% for Pb of the total metals, and the labile fractions were linearly correlated to their corresponding total contents. The step regression analyses suggested that the key factors impacting labile Cd and Pb varied in different parent material soils. Pb activity was highly sensitive to pH in alkaline limestone soils. The quartz sand remained in granite-produced soils enhanced Cd activity. And dissolved organic matter (DOM) compositions considerably influenced Cd and Pb activities in sand shale, diluvium, and alluvium soils. Land use impacts heavy metal activities. The labile Cd and Pb in paddy soils were higher than those in non-paddy soils, although total metals in the soils were comparable. It could be ascribed to the long-term equilibrium of metals between the solution and solid phases of the paddy soils. The results provide a theoretical basis for preliminary prediction of heavy metal activity and provide a technical support for heavy metal activity management and pollution control based on soil parent materials.