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.

In the current investigation, we presented the success of the modified hydrothermal method for synthesizing the iron-oxide nanoparticles (Fe₂O₃-NPs) efficiently. These NPs were further characterized by using different techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM) micrographs, energy-dispersive X-ray spectroscopy (EDAX)/Mapping pattern, Raman Spectroscopy Pattern, ultra violet (UV) and Photoluminescence (PL). All these analyses revealed highly pure nature of Fe₂O₃-NPs with no internal defects, and suggested its application for plant growth improvement. Therefore, we further investigated the separate as well as combined effects of the Fe₂O₃-NPs and citric acid (CA) in the alleviation of arsenic (As) toxicity in the soybean (Glycine max L.), by evaluating the different plant growth and metabolic attributes. Results of our study revealed that As-induced growth inhibition, reduction of photosynthesis, water use efficiency (WUE), and reactive oxygen species (ROS) accumulation whereas application of the Fe₂O₃-NPs and CA significantly reversed all these adverse effects in soybean plants. Moreover, the As-stress induced malondialdehyde (MDA) and hydrogen peroxide (H₂O₂) production were partially reversed by the Fe₂O₃-NPs and CA in the As-stressed plants by 16% and 10% (MDA) and 29% and 12% (H₂O₂). This might have resulted due to the Fe₂O₃-NPs and CA induced activities of the antioxidant defense in plants. Overall, the Fe₂O₃-NPs and CA supplementation separately and in combination positively regulated the As tolerance in soybean; however, the effect of the combined application on the As tolerance was more profound relative to the individual application. These results suggested the synergetic effect of the Fe₂O₃-NPs and CA on the As-tolerance in soybean. However, in-depth mechanism underlying the defense crosstalk between the Fe₂O₃-NPs and CA needs to be further explored.

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.

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.

Raw biochar with high pH possibly stimulated ammonia (NH₃) volatilization in the agricultural soil. We hypothesized that the modified biochar (MBC) with low pH can synchronically decrease the NH₃ and nitrous oxide (N₂O) losses. We performed a two-year experiment to clarify how citric acid MBC influence the NH₃ volatilization and N₂O emission as well as the underlying mechanisms. Two typical paddy soils, i.e., Hydragric Anthrosol and Haplic Acrisol, receiving equal urea N with 240 kg ha⁻¹ but varied rates of MBC with 0, 5, 10, and 20 t ha⁻¹ (named Urea, Urea + MBC5, Urea + MBC10, and Urea + MBC20, respectively) were studied. The results showed that MBC-amended treatments effectively mitigated the NH₃ volatilization from Hydragric Anthrosol and Haplic Acrisol by 29.6%–57.9% and 30.5%–62.4% in 2017, and by 16.5%–21.0% and 24.5%–35.0% in 2018, respectively, compared to Urea treatment. In addition, significantly lower N₂O emissions with averaged 38.3% and 43.1% in 2017, and 51.7% and 26.7% were recorded under Hydragric Anthrosol and Haplic Acrisol, respectively, following the MBC application (P < 0.05). Increased MBC addition performed higher efficacy on mitigating NH₃ volatilization, particularly in the first rice season, while this “dosage effect” was not found for N₂O reduction. Lowered pH in overlying water, enhanced adsorption of NH₄⁺-N and its nitrification rate likely contributed to the lower NH₃ volatilization as result of MBC addition. The nirS and nosZ gene copies were not changed by MBC, while the nirK gene copies were decreased as result of MBC amendment by 8.3%–25.2% under Hydragric Anthrosol and by 21.8%–24.9% under Haplic Acrisol. Consequent lower ratio of nirK/(nirS + nosZ) explained the mitigation effect of MBC on N₂O emission. In conclusion, the present two-year study recommends that MBC applied at a low dosage can perform positive effect on controlling the nitrogenous gas pollutants from paddy soil.

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.

Struvite recovered from swine wastewater can be used as a good slow release fertilizer. Nevertheless, the presence of heavy metals would be easily precipitated with struvite and increase the ecological risk for its agricultural use. This paper investigated the possibility of using process variables for heavy metal (Cu2+, Zn2+ and Cr3+) minimization during struvite crystallization in swine wastewater. The heavy metal content, effect ratios (ER) of the citric acid concentration under varying conditions were tested and their SEM, EDS and XRD patterns were compared for morphology analysis. The results show that an increase in pH decreased the content of Cu, Zn and Cr in recovered precipitates. Heavy metal content in the precipitates increased markedly with their initial concentrations in the solution. The effect ratio calculation indicates that Cr has the strongest co-precipitation potential, followed by Zn and Cu. An increase in citric acid concentration reduced the heavy metal removal efficiency (14.3, 27.7 and 28.1% for Cu, Zn and Cr, respectively) but did not decrease their content in struvite precipitates. What is more, increase of total ammonia nitrogen (TAN) to soluble phosphate molar ratio significantly decreased Cu, Zn removal efficiency (52.2 and 50% respectively), while Mg:PO4P molar ratio had much less effect.

This study aims to assess the role of Fe plaque in metal uptake and translocation by different wetland plants and examine the effects of organic acids on metal detoxification in wetland plants. It was found that although exposed to a similar level of metals in rhizosphere soil solution, metal uptake by shoots of Cypercus flabelliformis and Panicum paludosum was greatly reduced, consequently leading to a better growth under flooded than under drained conditions. This may be related to the enhanced Fe plaque in the former, but due to the decreased root permeability in the latter under anoxic conditions. The Fe plaque on root surface has potential to sequester metals and then reduce metal concentrations and translocation in shoot tissues. However, whether the Fe plaque acts as a barrier to metal uptake and translocation may also be dependent on the root anatomy. Although metal tolerance in wetland plants mainly depends upon their metal exclusion ability, the higher-than-toxic-level of metal concentrations in some species indicates that internal metal detoxification might also exist. It was suggested that malic or citric acid in shoots of P. paludosum and C. flabelliformis may account for their internal detoxification for Zn.