Biomagnification of persistent organic pollutants (POPs) in detritivorous, phytophagous, and predatory invertebrates: How POPs enter terrestrial food web?

Invertebrates are primary contributors to fluxes of nutrients, energy, and contaminants in terrestrial food webs, but the trophodynamic of contaminants in invertebrate food chains is not fully understood. In this study, occurrence and biomagnification of persistent organic pollutants (POPs) were assessed in detritivorous, phytophagous, and predatory invertebrate food chains. Detritivorous species (earthworm and dung beetle) have higher concentrations of POPs than other species. Different composition patterns and biomagnification factors (BMFs) of POPs were observed for invertebrate species. Negative correlations were found between BMFs and log KOW of POPs for detritivorous and most phytophagous species. In contrast, parabolic relationships between BMFs and log KOW were observed in snails and predatory species, possibly attributed to the efficient digestion and absorption of diet and POPs for them. Bioenergetic characteristics are indicative of the biomagnification potential of POPs in terrestrial wildlife, as suggested by the significant and positive correlation between basal metabolic rates (BMRs) and BMFs of BDE 153 for invertebrates, amphibians, reptiles, birds, and mammals. The estimations of dietary exposure suggest that the terrestrial predators, especially feeding on the underground invertebrates, could be exposed to high level POPs from invertebrates.

Redox control of chromium in the red soils from China evidenced by Cr stable isotopes.

With chromium isotopes, we study the intricate dynamics of adsorption and redox processes in soil ecosystems, focusing on chromium's behaviour, in red soil profiles enriched with iron-manganese nodules (FMNs) in South China. Key findings reveal that the primary geological source of chromium in the red soil profiles is the weathering of colluvium parent minerals. FMNs have higher chromium concentrations (325-1451 µg/g) compared to surrounding soils (95-247 µg/g) and display stable δ53Cr values (0.78 ± 0.17‰), indicating their role as stable chromium repositories, reflecting historical processes. Furthermore, by isolating chromium associated with iron oxides (FeO) and silicate minerals (ReS) within FMNs and surrounding soils using CBD extractions, we show that FeO predominantly carry chromium, particularly in FMNs. The δ53Cr values of FeO fractions consistently exhibit heavier signatures than ReS fractions, suggesting the sequestration of isotopically heavy chromium (VI) during Fe oxide precipitation. Fluctuations in soil's redox, rather than land use, play a pivotal role in controlling the precipitation of Fe oxides in surrounding soils and the formation of FMNs, thus influencing chromium mobility. This highlights the significance of these factors when utilizing chromium isotopic techniques for source tracking in soil systems, contributing to our understanding of chromium's behaviour in soil environments.

Trophic transfer of heavy metals in a wetland food web from an abandoned e-waste recycling site in South China.

In order to understand the pollution status and trophic transfer of heavy metals across wetland food web organisms, four invertebrate species, six fish species, one snake species, and one bird species were collected from an abandoned e-waste site in South China for analysis of toxic elements (Ni, Zn, Cu, Cr, Cd, and Pb). The concentrations of Ni, Zn, Cu, Cr, Cd, and Pb were 0.16-15.6, 24.9-850, 1.49-645, 0.11-64.6, 0.01-4.53 and 0.41-40.4 mg/kg dry weight, respectively. The results demonstrated that the concentrations of six studied heavy metals decreased throughout the whole food web, but Cu and Zn concentrations increased along the bird and reptile food chains, respectively. The trophic transfer of metals for the key species should be of special attention, as the trophic biomagnification factor (TMF) in a food web may overlook the ecological risks of metals for certain species, especially those at high trophic levels. The estimated daily intake (EDI) and the target hazard quotient (THQ) results showed that Cu, Cd, and Pb posed the main risks on human health, especially through the consumption of snail and crab species.

Transcriptome profiling of genes regulated by phosphate-solubilizing bacteria Bacillus megaterium P68 in potato (Solanum tuberosum L.).

The insoluble phosphorus in the soil is extremely difficult to be absorbed and used directly through the potato root system. Although many studies have reported that phosphorus-solubilizing bacteria (PSB) can promote plant growth and uptake of phosphorus, the molecular mechanism of phosphorus uptake and growth by PSB has not been investigated yet. In the present study, PSB were isolated from rhizosphere soil in soybean. The data of potato yield and quality revealed that the strain P68 was the most effective In the present study, PSB identification, potato field experiment, pot experiment and transcriptome profiling to explored the role of PSB on potato growth and related molecular mechanisms. The results showed that the P68 strain (P68) was identified as Bacillus megaterium by sequencing, with a P-solubilizing ability of 461.86 mg·L-1 after 7-day incubation in National Botanical Research Institute's Phosphate (NBRIP) medium. Compared with the control group (CK), P68 significantly increased the yield of potato commercial tubers by 17.02% and P accumulation by 27.31% in the field. Similarly, pot trials showed that the application of P68 significantly increased the biomass, total phosphorus content of the potato plants, and available phosphorus of the soil up by 32.33, 37.50, and 29.15%, respectively. Furthermore, the transcriptome profiling results of the pot potato roots revealed that the total number of bases was about 6G, and Q30 (%) was 92.35-94.8%. Compared with the CK, there were a total of 784 differential genes (DEGs) regulated when treated with P68, which 439 genes were upregulated and 345 genes were downregulated. Interestingly, most of the DEGs were mainly related to cellular carbohydrate metabolic process, photosynthesis, and cellular carbohydrate biosynthesis process. According to the KEGG pathway analysis, a total of 46 categorical metabolic pathways in the Kyoto Encyclopedia of Genes and Genomes (KEGG) database were annotated to 101 DEGs found in potato roots. Compared with the CK, most of the DEGs were mainly enriched in glyoxylate and dicarboxylate metabolism (sot00630), nitrogen metabolism (sot00910), tryptophan metabolism (sot00380), and plant hormone signal transduction (sot04075), and these DEGs might be involved in the interactions between Bacillus megaterium P68 and potato growth. The qRT-PCR analysis of differentially expressed genes showed that inoculated treatments P68 significantly upregulated expression of the phosphate transport, nitrate transport, glutamine synthesis, and abscisic acid regulatory pathways, respectively, and the data from qRT-PCR were consistent with that obtained from RNA-seq. In summary, PSB may be involved in the regulation of nitrogen and phosphorus nutrition, glutaminase synthesis, and abscisic acid-related metabolic pathways. This research would provide a new perspective for studying the molecular mechanism of potato growth promotion by PSB in the level of gene expression and related metabolic pathways in potato roots under the application of Bacillus megaterium P68.

Immobilization and release risk of arsenic associated with partitioning and reactivity of iron oxide minerals in paddy soils.

The consumption of agricultural products grown on paddy soils contaminated with toxic element has a detrimental effect on human health. However, the processes and mechanisms of iron (Fe) mineral-associated arsenic (As) availability and As reactivity in different paddy soil profiles are not well understood. In this study, the fractions, immobilization, and release risk of As in eleven soil profiles from the Changzhutan urban agglomeration in China were investigated; these studied soils were markedly contaminated with As. Sequential extraction experiments were used to analyze fractions of As and Fe oxide minerals, and kinetic experiments were used to characterize the reactivity of Fe oxide minerals. The results showed that concentrations of total As and As fractions had a downward trend with depth, but the average proportions of As fractions only showed relatively small changes, which implied that the decrease in the total As concentrations influenced the changes in fraction concentrations along the sampling depth. Moreover, we found that easily reducible Fe (Feox1) mainly controlled the reductive dissolution of the Fe oxides, which suggest that the reductive dissolution process could potentially release As during the flooded period of rice production. In addition, a high proportion of As was specifically absorbed As (As-F2) (average 20.4%) in paddy soils, higher than that in other soils. The total organic carbon (TOC) content had a positive correlation with the amount of non-specifically bound As (As-F1) (R = 0.56), which means that TOC was one factor that affected the As extractability in the As-F1. Consequently, high inputs of organic fertilizers may elevate the release of As and accelerate the diffusion of As. Graphical abstract.

Influence of agricultural organic inputs and their aging on the transport of ferrihydrite nanoparticles: From enhancement to inhibition.

Organic matter effectively regulates nanoparticles transport. However, little is known about the effect of agricultural organic inputs on the transport of ferrihydrite nanoparticles (FHNPs) during aging. In this study, columns were filled with sand mixed with varying proportions of pristine, water-processing, or alkali-processing biochar or swine manure and used to simulate the release of organic matter and changes in surface roughness of sand grains during field aging. The influence of these factors on FHNPs transport was investigated using column experiments. The dissolved organic matter (DOM) (0.008-24.8 mg L-1) released from agricultural organic inputs decreased the zeta potential of the FHNPs from 30.8 mV to 14.6--48.9 mV and further caused electrostatic repulsion, osmotic repulsion, and elastic-steric repulsion between FHNPs and mixed sand, thus enhancing FHNPs transport. Ferrihydrite nanoparticles transport increased with increasing content of biochar and swine manure due to the increased amount of DOM. However, with the presence of organic inputs, surface roughness up to a certain degree (the increase in specific surface area up to 4.6 m2) became the dominant inhibition factor affecting FHNPs transport. After DOM release, agricultural organic inputs decreased the enhancement of FHNPs transport; with the increase input, their rougher surface gradually increased inhibition of FHNPs transport. The strongest FHNPs retention in the alkali-processing biochar (0.2-10%) or swine manure (1-2%) mixed sand columns indicated that fully aged agricultural organic inputs strongly inhibited FHNPs transport. Our findings provided novel insights into the critical influence of agricultural organic inputs and their aging on FHNPs transport, which changed gradually from enhancement to inhibition gradually.

Effects of soil acid stress on the survival, growth, reproduction, antioxidant enzyme activities, and protein contents in earthworm (Eisenia fetida).

This study focused on the study of earthworm survival, growth, reproduction, enzyme activities, and protein contents to evaluate and predict the effects of different soil pH levels and determine the optimal risk assessment indicators for the effects. Survival rate, growth rate, and cocoon number as well as four enzyme (glutathione peroxidase (GSH-PX), superoxide dismutase (SOD), peroxidase (POD), and catalase (CAT)) activities and two proteins (total protein (TP) and metallothionein (MT)) contents in earthworms were determined to characterize the responses of earthworm activity to five soil pH levels. These biological datasets (survival, growth, and reproduction) were compared with biochemical indexes (GSH-PX, SOD, POD, CAT, TP, and MT), mainly using biphasic dose-response models. The results indicated that the soil pH value had significant inhibitory effects on the survival, growth, and reproduction of earthworms beginning with 3.0, 4.0, and 5.2, respectively. The dose-response models (J-shaped and inverted U-shaped curves) statistics indicated that the critical values (ECZEP) of the GSH-PX, SOD, POD, CAT, TP, and MT inhibited by soil acid stress were 3.46, 3.76, 3.35, 3.54, 3.50, and 3.96 (average 3.60), respectively. In the present study, the fitting curve analysis showed that the responses of the CAT activities and TP and MT contents in earthworm in response to soil pH have the behavior of hormesis.

Impacts of earthworm species on soil acidification, Al fractions, and base cation release in a subtropical soil from China.

Soil-exchangeable aluminum (Al) has toxic effects on living organisms in acidic soils. Earthworm presence and activity can alter soil pH, which has a significant influence on Al toxicity. However, the effects of earthworms on soil Al toxicity and fractions are still largely unknown. This laboratory study focused on the effects of three earthworm species (endogeics Pontoscolex corethrurus and Amynthas robustus, anecis Amynthas aspergillum) on soil acidification, Al fraction distribution, and base cation release. Three native earthworm species and a soil (latosolic red soil) collected from a botanical garden in South China were incubated under laboratory conditions. After 40 days of incubation, six Al fractions in soil, namely exchangeable (AlEx), weakly organically bound (AlOrw), organically bound (AlOr), amorphous (AlAmo), Al occluded in crystalline iron oxides (AlOxi), and amorphous aluminosilicate and gibbsite (AlAag) fractions, were extracted using a sequential procedure. Soil pH; organic carbon; total nitrogen; total Al (AlTotal); exchangeable K, Na, Ca, Mg contents; and CEC were determined as well. Compared to control soil, pH values increased by 0.79, 0.41, and 0.57 units in casts in the presence of P. corethrurus, A. robustus, and A. aspergillum, and 0.70, 0.32, and 0.50 units in non-ingested soil, respectively. Compared to control soil, the 61.7%, 30.7%, and 36.1% of AlEx contents in casts and 68.5%, 25.9%, and 39.0% of AlEx in non-ingested soil significantly decreased with the addition of P. corethrurus, A. robustus, and A. aspergillum, respectively. Moreover, compared to control soil, the 78.7%, 37.7%, and 40.1% of exchangeable Ca2+ and 12.3%, 24.7%, and 26.8% of exchangeable Mg2+ contents in casts significantly increased with the presence of P. corethrurus, A. robustus, and A. aspergillum, respectively. Soil treated with P. corethrurus had higher soil pH values, exchangeable Ca2+ contents, and lower AlEx than those with A. robustus and A. aspergillum. Results of principal component analyses showed that P. corethrurus, A. robustus, and A. aspergillum casts and non-ingested soil differ for soil pH, Al fractions, and exchangeable base cations release. These results indicate that earthworms, especially P. corethrurus, can reduce soil Al toxicity, increase soil pH, and affect the release of exchangeable base cations.

Highly Compressible and Sensitive Pressure Sensor under Large Strain Based on 3D Porous Reduced Graphene Oxide Fiber Fabrics in Wide Compression Strains.

The development of highly sensitive wearable and foldable pressure sensors is one of the central topics in artificial intelligence, human motion monitoring, and health care monitors. However, current pressure sensors with high sensitivity and good durability in low, medium, and high applied strains are rather limited. Herein, a flexible pressure sensor based on hierarchical three-dimensional and porous reduced graphene oxide (rGO) fiber fabrics as the key sensing element is presented. The internal conductive structural network is formed by the rGO fibers which are mutually contacted by interfused or noninterfused fiber-to-fiber interfaces. Thanks to the unique structures, the sensor can show an excellent sensitivity from low to high applied strains (0.24-70.0%), a high gauge factor (1668.48) at an applied compression of 66.0%, a good durability in a wide range of frequencies, a low detection limit (1.17 Pa), and anultrafast response time (30 ms). The dominated mechanism is that under compression, the slide of the graphene fibers through the polydimethylsiloxane matrix reduces the connection points between the fibers, causing a surge in electrical resistance. In addition, because graphene fibers are porous and defective, the change in geometry of the fibers also causes a change in the electrical resistance of the composite under compression. Furthermore, the interfused fiber-to-fiber interfaces can strengthen the mechanical stability under 0.01-1.0 Hz loadings and high applied strains, and the wrinkles on the surface of the rGO fibers increased the sensitivity under tiny loadings. In addition, the noninterfused fiber-to-fiber interfaces can produce a highly sensitive contact resistance, leading to a higher sensitivity at low applied strains.

Tuning the Bifunctional Oxygen Electrocatalytic Properties of Core-Shell Co3O4@NiFe LDH Catalysts for Zn-Air Batteries: Effects of Interfacial Cation Valences.

The rational design of excellent electrocatalysts is significant for triggering the slow kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable metal-air batteries. Hereby, we report a bifunctional catalytic material with core-shell structure constructed by Co3O4 nanowire arrays as cores and ultrathin NiFe-layered double hydroxides (NiFe LDHs) as shells (Co3O4@NiFe LDHs). The introduction of Co3O4 nanowires could provide abundant active sites for NiFe LDH nanosheets. Most importantly, the deposition of NiFe LDHs on the surface of Co3O4 can modulate the surface chemical valences of Co, Ni, and Fe species via changing the electron donor and/or electron absorption effects, finally achieving the balance and optimization of ORR and OER properties. By this core-shell design, the maximum ORR current densities of Co3O4@NiFe LDHs increase to 3-7 mA cm-2, almost an order of magnitude increases compared to pure NiFe LDH (0.45 mA cm-2). Significantly, an OER overpotential as low as 226 mV (35 mA cm-2) is achieved in the designed core-shell catalyst, which is comparable to and/or even better than those of commercial Ir/C. Hence, the primary zinc-air battery employing Co3O4@NiFe LDH as an air electrode achieves a high specific capacity (667.5 mA h g-1) and first-class energy density (797.6 W h kg-1); the rechargeable battery can show superior reversibility, excellent stability, and voltage gaps of ∼0.8 V (∼60% of round-trip efficiency) in >1200 continuous cycles. Furthermore, the flexible quasi-solid-state zinc-air battery with bendable ability holds practical potential in portable and wearable electronic devices.

Rational Design of Layered SnS2 on Ultralight Graphene Fiber Fabrics as Binder-Free Anodes for Enhanced Practical Capacity of Sodium-Ion Batteries.

Generally, the practical capacity of an electrode should include the weight of non-active components such as current collector, polymer binder, and conductive additives, which were as high as 70 wt% in current reported works, seriously limiting the practical capacity. This work pioneered the usage of ultralight reduced graphene fiber (rGF) fabrics as conductive scaffolds, aiming to reduce the weight of non-active components and enhance the practical capacity. Ultrathin SnS2 nanosheets/rGF hybrids were prepared and used as binder-free electrodes of sodium-ion batteries (SIBs). The interfused graphene fibers endow the electrode a porous, continuous, and conductive network. The in situ phase transformation from SnO2 to SnS2 could preserve the strong interfacial interactions between SnS2 and graphene. Benefitting from these, the designed binder-free electrode delivers a high specific capacity of 500 mAh g-1 after 500 cycles at a current rate of 0.5 A g-1 with almost 100% Coulombic efficiency. Furthermore, the weight percentage of SnS2 in the whole electrode could reach up to 67.2 wt%, much higher than that of common electrode configurations using Cu foil, Al foil, or carbon cloth, significantly highlighting the ultralight characters and advantages of the rGF fabrics for using as binder-free electrodes of SIBs.

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.

Speciation and reactivity of lead and zinc in heavily and poorly contaminated soils: Stable isotope dilution, chemical extraction and model views.

Correct characterization of metal speciation and reactivity is a prerequisite for the risk assessment and remedial activity management of contaminated soil. To better understand the intrinsic reactivity of Pb and Zn, nine heavily and poorly contaminated soils were investigated using the combined approaches of chemical extractions, multi-element stable isotopic dilution (ID) method, and multi-surface modelling. The ID results show that 0.1-38% of total Pb and 3-45% of total Zn in the studied soils are isotopically exchangeable after a 3-day equilibration. The intercomparison between experimental and modelling results evidences that single extraction with 0.43 M HNO3 solubilizes part of non-isotopically exchangeable fraction of Pb and Zn in the studied soils, and cannot be used as a surrogate for ID to assess labile Pb and Zn pools in soil. Both selective sequential extraction (SSE) and modelling reveal that Mn oxides are the predominant sorption surface for Pb in the studied soils; while Zn is predicted to be mainly associated with soil organic matter in the soil with low pH and Fe/Mn oxides in the soils with high pH. Multi-surface modelling can provide a reasonable prediction of Pb and Zn adsorption onto different soil constituents for the most of the studied soils. The modelling could be a promising tool to decipher the underlying mechanism that controls metal reactivity in soil, but the submodel for Mn oxides should be incorporated and the model parameters, especially for the 2-pK diffuse layer model for Mn oxides, should be updated in the further studies.

[Effects of composting with earthworm on the chemical and biological properties of agricultural organic wastes: a principal component analysis].

Taking mixed agricultural organic wastes cattle manure and rice straw (C:N = 28.7:1) as the substrate of earthworm Eisenia foetida, an experiment was conducted to study the effects of earthworm on the changes of the chemical and biological properties of wastes during vermi-composting. After 30 days of vermi-composting, the substrate' s pH and C/N decreased while the total P content increased significantly, and the total N, available N, dissolved organic carbon, available P content, microbial biomass-C, respiration rate, and microbial quotient increased by 8.5% , 2.6%, 1.8%, 6.3%, 21.2%, 4.4%, and 30.0% whereas the organic matter content and metabolic quotient decreased by 5.0% and 21.9%, respectively, as compared with natural composting. Vermi-composting made the substrate have higher invertase, acid phosphatase, and alkaline phosphatase activities but lower catalase and urease activities. Principal component analysis and discriminant analysis confirmed the significant differences in the substrate' s chemical and biological properties between vermi-composting and natural composting. This study indicated that vermi-composting was superior to natural composting, which could obviously improve the chemical and biological properties of composted organic materials, being a high efficient technology for the management of agricultural organic wastes.