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.

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.

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.

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.

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.

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.

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.

Adequate silicon (Si) can greatly boost rice yield and improve grain quality through alleviating stresses associated with heavy metals and metalloids such as arsenic (As) and cadmium (Cd). The soil plant-available Si is relatively low in South China due to severe desilicification and allitization of the soils in this region. Conversely, pollution of heavy metals and metalloids in the soils of this region occurs widely, especially As and Cd pollution in paddy soil. Therefore, evaluating the plant availability of Si in paddy soil of South China and examining its correlation with the availability of heavy metals and metalloids are of great significance. Accordingly, in our study, 107 pairs of soil and rice plant samples were collected from paddy fields contaminated by As and Cd in South China. Significantly positive correlations between Si in rice plants and Si fractions in soils extracted with citric acid, NaOAc-HOAc buffer, and oxalate-ammonium oxalate buffer suggest that these extractants are more suitable for use in extracting plant-available Si in the soils of our present study. Significantly negative correlations between different Si fractions and As or Cd in rice plant tissues and negative exponential correlations between the molar ratios of Si to As/Cd in rice roots, straws, husks or grains and As/Cd in rice grains indicate that Si can significantly alleviate the accumulation of As/Cd from soils to the rice plants. Finally, a contribution assessment of soil properties to As/Cd accumulation in rice grains based on random forest showed that in addition to Si concentrations in soil or rice plants, other factors such as Fe fractions and total phosphorus also contributed largely to As/Cd accumulation in rice grains. Overall, Si exhibited its unique role in mitigating As or Cd stress in rice, and our study results provide strong field evidence for this role.

The degree of aggregation and/or coalescence of Au-citrate nanoparticles (AuNPs, mean size 21.5 ± 2.9 nm), after delivery in simulated seawater, are shown to be concentration-dependent. At low concentrations no coalescence and only limited aggregation of primary particles were found. Experiments were performed in which the marine bivalve (Ruditapes philippinarum) was exposed to AuNPs or dissolved Au and subsequently, bivalve tissues were studied by Scanning and Transmission Electron Microscopy and chemical analyses. We show that the bivalve accumulates gold in both cases within either the digestive gland or gill tissues, in different concentrations (including values of predicted environmental relevance). After 28 days of exposure, electron-dense deposits (corresponding to AuNPs, as proven by X-ray microanalysis) were observed in the heterolysosomes of the digestive gland cells. Although non-measurable solubility of AuNPs in seawater was found, evidence is presented of the toxicity produced by Au3+ dissolved species (chloroauric acid solutions) and its relevance is discussed.

This study investigates the column leaching of a soil contaminated mainly with Cr and Ni by using two chelants: citric acid (biodegradable) and EDTA (non-biodegradable) followed with water rinse. The chelants lead to Cr and Ni leaching, in addition to major elements (Ca, Fe, Mg, Al, Mn and Zn) showing the dissolution of soil mineral constituents. EDTA leaches more major elements and Ni than citric acid related to the respective stability of metal–chelant complexes; citric acid leaches more Cr than EDTA, certainly because of a substitution reaction with Cr(VI). In the case of alternating chelant/water applications, leaching occurs during the chelant applications, but also during water applications. In the case of chelant/water applications followed by continuous water application, both Cr and Ni leach over time. This increased mobility could be due to the residual chelant present in soil as well as to the dissolution/mobilization of mineral or organic soil fractions.