peer reviewed | Contamination of land and aquatic ecosystems with heavy metals (HMs) is a global issue having the persistent potential to damage the quality of food and water. In the present study, Tagetes erecta L. plants were used to assess their potential to uptake HMs from wastewater. Plants were grown in soil for 20 days and then transplanted in hydroponic system containing Hoagland nutrient solution. After more than 15 days of growth, plants were then subjected to wastewater from tannery and surgical industries in different concentrations ranging from 25 to 100% in combination of citric acid (5 and 10 mM). After 6 weeks of treatment, plants were collected and segmented into roots, stem, and leaves for characterizing the morphological properties including plant height, roots length, fresh and dry mass of roots, stem, and leaves. For evaluation of the effect of wastewater on the plants, photosynthetic pigments; soluble proteins; reactive oxygen species (ROS); antioxidant enzymes SOD, POD, CAT, and APX; and metal accumulation were analyzed. Application of industrial wastewater revealed a significant effect on plant morphology under wastewater treatments. Overall growth and physiological attributes of plant decreased, and metal accumulation enhanced with increasing concentration of wastewater. Similarly, the production of ROS and antioxidant enzymes were also increased. Chlorophyll, protein content, and enzyme production enhanced with CA (5 and 10 mM) mediation; however, ROS production and EL were reduced. Metals analysis showed that the maximum accumulation of Pb was in roots, while Cr and Ni in the stem which further increased under CA mediation. Overall, the metal accumulation ability was in the order of Pb > Ni > Cr under CA.

Many organic materials have been used to decrease heavy-metal bioavailability in soil via in-situ remediation due to its high efficiency and easy operation; meanwhile, cheap materials have also been pursued to decrease the cost of remediation. Agricultural wastes exhibit their potential in remediation materials due to their low cost; however, raw agricultural wastes have a low ability to immobilize heavy metals in soil. Attempts have been made to modify agricultural wastes to improve the efficiency of heavy-metal passivation. In this study, novel agricultural waste-based materials, raw sugarcane bagasse (SB), citric acid modified (SSB) and citric-acid/Fe₃O₄ modified (MSB) sugarcane bagasse at 0.5% and 1% addition rates, were compared for their effectiveness in soil Cd passivation and Cd accumulations in pakchoi plants in a 30-day pot experiment. The addition of SB did not decrease soil bioavailable Cd effectively and slightly decreased Cd accumulation in plant roots and leaves. In comparison, SSB and MSB exhibited a great potential to decrease the transformation, translocation and accumulation of Cd with the decrease being greater at 1% than 0.5% rate in the soil-pakchoi system. For example, the addition of SSB and MSB at 0.5% decreased the concentration of Cd in leaves by 10%, and 16%, and at 1% decreased the concentration by 25% and 30%, respectively. High pH and abundant functional groups of three amendments played important roles in Cd immobilization. The enhanced microbial activities might also contribute to Cd passivation. However, plant growth was decreased in the amended treatments except SSB at 0.5% rate. The results suggest that citric-acid-modified sugarcane bagasse at addition rate of 0.5% has a potential to immobilize Cd in soil and decrease Cd accumulation in edible part of pakchoi effectively without decreasing vegetable growth.

Odontarrhena muralis is one of the most promissing plant species for Ni phytomining, and soil amendments can further increase its Ni phytoextraction ability. Here we investigated whether Ni phytomining/phytoremediation using this Ni hyperaccumulator can benefit from applying citric acid to a serpentine soil that is naturally enriched in Ni (>1000 mg kg⁻¹). Synchrotron micro X-ray fluorescence (μ-SXRF) was used to image Ni and other metal distributions in whole fresh leaves of O. muralis. Leaf Ni accumulation in plants grown on citric acid-amended soil increased up to 55% while Co, Cr, Fe, Mn, and Zn concentrations were 4-, 14-, 6-, 7- and 1.3-fold higher than the control treatment. O. muralis presented high bioconcentration factors (leaf to soil concentration ratio) to Ni and Zn whereas Cr was seemingly excluded from uptake. The μ-SXRF images showed a uniform distribution of Ni, preferential localization of Co in the leaf tip, and clear concentration of Mn in the base of trichomes. The citric acid treatments strongly increased the Co fluoerescence intensity in the leaf tip and altered the spatial distribution of Mn across the leaf, but there was no difference in Ni fluorescence counts between the trichome-base region and the bulk leaf. Our data from a serpentine soil suggests that citrate treatment enhances Ni uptake, but Co is excreted from leaves even in low leaf concentrations, which can make Co phytoming using O. muralis unfeasible in natural serpentine soils.

Dibenzofuran (DBF) derivatives have caused serious environmental problems, especially those produced by paper pulp bleaching and incineration processes. Prominent for its resilient mutagenicity and toxicity, DBF poses a major challenge to human health. In the present study, a new strain of Pseudomonas aeruginosa, FA-HZ1, with high DBF-degrading activity was isolated and identified. The determined optimum conditions for cell growth of strain FA-HZ1 were a temperature of 30 °C, pH 5.0, rotation rate of 200 rpm and 0.1 mM DBF as a carbon source. The biochemical and physiological features as well as usage of different carbon sources by FA-HZ1 were studied. The new strain was positive for arginine double hydrolase, gelatinase and citric acid, while it was negative for urease and lysine decarboxylase. It could utilize citric acid as its sole carbon source, but was negative for indole and H2S production. Intermediates of DBF 1,2-dihydroxy-1,2-dihydrodibenzofuran, 1,2-dihydroxydibenzofuran, 2-hydroxy-4-(3′-oxo-3′H-benzofuran-2′-yliden)but-2-enoic acid, 2,3-dihydroxybenzofuran, 2-oxo-2-(2′-hydrophenyl)lactic acid, and 2-hydroxy-2-(2′-hydroxyphenyl)acetic acid were detected and identified through liquid chromatography-mass analyses. FA-HZ1 metabolizes DBF by both the angular and lateral dioxygenation pathways. The genomic study identified 158 genes that were involved in the catabolism of aromatic compounds. To identify the key genes responsible for DBF degradation, a proteomic study was performed. A total of 1459 proteins were identified in strain FA-HZ1, of which 100 were up-regulated and 104 were down-regulated. A novel enzyme “HZ6359 dioxygenase”, was amplified and expressed in pET-28a in E. coli BL21(DE3). The recombinant plasmid was successfully constructed, and was used for further experiments to verify its function. In addition, the strain FA-HZ1 can also degrade halogenated analogues such as 2, 8-dibromo dibenzofuran and 4-(4-bromophenyl) dibenzofuran. Undoubtedly, the isolation and characterization of new strain and the designed pathways is significant, as it could lead to the development of cost-effective and alternative remediation strategies. The degradation pathway of DBF by P. aeruginosa FA-HZ1 is a promising tool of biotechnological and environmental significance.

During their lifecycle, many engineered nanoparticles (ENPs) undergo significant transformations that may modify their toxicity, behaviour, and fate in the environment. Therefore, understanding the possible environmentally relevant transformations that ENPs may undergo as a result of their surroundings is becoming increasingly important. This work considers industrially produced ceria (CeO2) and focuses on a particle library consisting of seven zirconium-doped variants (Ce1-xZrxO2) where the Zr doping range is x = 0–1. The study assesses their potential transformation in the presence of environmentally relevant concentrations of phosphate. These ENPs have an important role in the operation of automotive catalysts and therefore may end up in the environment where transformations can take place. Samples were exposed to pH adjusted (c. 5.5) solutions made up of either 1 mM or 5 mM each of KH2PO4, citric acid and ascorbic acid and the transformed particles were characterised by means of DLS – size and zeta potential, UV/VIS, TEM, FT-IR, EDX and XRD. Exposure to the phosphate solutions resulted in chemical and physical changes in all ceria-containing samples to cerium phosphate (with the monazite structure). The transformations were dependent on time, ceria concentration in the particles (Ce:Zr ratio) and phosphate to ceria ratio. The presence of Zr within the doped samples did not inhibit these transformations, yet the pure end member ZrO2 ENPs showed no conversion to phosphate. The quite dramatic changes in size, structure and composition observed raise important questions regarding the relevant form of the materials to investigate in ecotoxicity tests, and for regulations based on one or more dimensions in the nanoscale.

Aggregation, an important environmental behavior of silver nanoparticles (AgNPs) influences their bioavailability and cytotoxicity. The work studied the influence of dissolved oxygen (DO) or the redox potential on the stability of AgNPs in aqueous environments. This study employed time-resolved dynamic light scattering (TR-DLS) to investigate the aggregation kinetics of citrate-coated AgNPs. Our results demonstrated that when DO was present, the aggregation rates became much faster (e.g., 3–8 times) than those without DO. The hydrodynamic sizes of AgNPs had a linear growth within the initial 4–6 h and after the linear growth, the hydrodynamic sizes became random for AgNPs in the presence of DO, whereas in the absence of DO the hydrodynamic sizes grew smoothly and steadily. Furthermore, the effects of primary particles sizes (20, 40, and 80 nm) and initial concentrations (300 and 600 μg/L) of AgNPs on aggregation kinetics were also investigated.

Low-molecular-weight organic acids may significantly influence the mobility of metal in environment, but the kinetics are not fully understood and have not been quantified. In this study, the thermodynamic and kinetic effects of citric acid (CA) on the adsorption of Cd(II) and Ni(II) on goethite were investigated using batch-adsorption and stirred-flow experiments. A charge distribution and multisite complexation model (CD-MUSIC) and a thermodynamically based multi-rate kinetic model were employed to describe the adsorption behaviors. Two ternary surface complexes, (≡FeO)₂CitMe and (≡FeOH)₂MeCit²⁻, were involved in the adsorption. In addition, CA differed in its effects on Cd(II) and Ni(II) adsorption, enhancing Cd(II) adsorption but inhibiting Ni(II) adsorption at high levels. Kinetically, in the presence of CA, the adsorption of Cd(II) was faster than that of Ni(II). Increasing CA concentration led to faster Cd(II) adsorption, but resulted in the dissolution of the adsorbed Ni(II), possibly due to the much higher complexation constants of Ni-CA than of Cd-CA in aqueous phase. This finding implied that, in the rhizosphere, high level of CA may lead to more dissolution of Ni(II) than Cd(II); while in acidic ferrosol, CA may alleviate Cd(II) mobility and toxicity. The proposed mechanistic model sheds light on ion partition in the soil environment and may improve predictions thereof.

Heavy metal pollution in paddy fields has caused widespread concerns due to the threat to food safety. The present study used low-cost sugarcane bagasse (SB) and two sugarcane bagasse materials modified with citric-acid (SSB) and citric-acid/Fe₃O₄ (MSB) to investigate their effects on the bioavailability of Cd in soil and Cd accumulations in rice in a pot experiment. The three organic amendments significantly decreased the Cd accumulation in plants by limiting its mobilization in soil. The MSB and SSB but not SB increased the soil pH and immobilized the Cd in soil significantly during the 120-day experiment. The amendments decreased Cd bioavailability through transforming to the stable fraction throughout the whole growth stage. The functional groups in the amendments (-OH, –COOH, C–O, -COO⁻ and Fe–O) and precipitates [Cd(NO₂)₂K(NO₂)₂, Cd(OH)₂ and Cd₇₅Zn₂₅Fe₂O₄] played active roles in Cd immobilization. Moreover, the three organic materials increased the content of Fe–Mn plaque on rice roots, which prevented its transport from soil to rice roots further. We also found that Fe competed with Cd for transporters and reduced potential Cd uptake and translocation in rice tissues. The addition of MSB and SB but not SSB inhibited the rice growth compared to the unamended control, indicating the potential of SSB in situ remediation. These results provide valuable information to use organic amendments for Cd passivation in soil and food safety.

Sludge landscaping after compost stabilization is a popular recycling process; however, until trace elements (TEs) are extracted by plants and reduced to safe concentrations, they present a potential exposure risk. Three garden plants, Liriope platyphylla Wang et Tang (L. platyphylla), Iris tectorum Maxim (I. tectorum), and Photinia x fraseri Dress (P. x fraseri), were selected for field experiments, and their ability to phytoremediate TEs and the promotion effect of citric acid (CA) were studied over 3 months of observation. Among the three kinds of plants, L. platyphylla had the highest biomass per unit soil area, and the CA treatment further increased the biomass of this plant per unit soil area as well as the uptake of TEs. When treated with 3 mmol kg⁻¹ CA, L. platyphylla showed increases in the bioconcentration factors of Cu, Zn, Pb, and Cd by 24%, 63%, 27%, and 123%, respectively. Because of the large biomass and high concentrations of TEs, L. platyphylla had high phytoremediation indexes for Zn, Cu, Pb, Ni, and Cd, which reached 18.5, 3.7, 3.2, 2.2, and 0.4 mg m⁻², respectively, and were further improved by 60%–187% by the CA treatment. These advantages indicate the potential usefulness of L. platyphylla for phytoremediation. The results provide basic data and technical support for the use of sludge-based compost and phytoremediation by garden plants.

Phytoextraction using Celosia argentea Linn. can potentially decontaminate Cd-contaminated soils. However, most earlier studies have been conducted at laboratory scale and for a relatively short remediation period. To evaluate the phytoextraction efficiency of C. argentea combined with different soil amendments (ammonium chloride, Bacillus megaterium, and citric acid), an 18-month field experiment was carried out in a farmland soil contaminated with 3.68 mg kg⁻¹ Cd by mine tailings in southern China. Soil Cd concentrations were decreased by 6.34 ± 0.73% after the three harvestings (with no amendments), which was 2.27 times that of the no-planting control (p < 0.05). Application of ammonium chloride, B. megaterium, and citric acid increased the overall Cd reduction rate in soil by 40.5%, 46.1%, and 105%, respectively. The application of citric acid decreased total Cd in soil by up to 16.9% in the rhizosphere soil and 13.0% in the bulk soil. The highest annual shoot biomass yield and Cd extraction amount reached 8.79 t ha⁻¹ and 273 g ha⁻¹. Acid-soluble Cd fraction in the rhizosphere was significantly lower compared to that in the bulk soil (p < 0.05), which indicates that mobile Cd in the rhizosphere was taken up by the roots vastly. C. argentea phytoextraction also improved soil metabolic functions by increasing the activities of soil enzymes (urease, invertase, phosphatase, and catalase). These findings demonstrate that Cd phytoextraction using C. argentea with the application of soil amendments can greatly improve the quality of Cd-contaminated soils.