Evaluating the Effectiveness of Nanotechnology in Environmental Remediation of a Highly Metal-Contaminated Area—Minas Gerais, Brazil
Abstract
:1. Introduction
2. Geographical and Geological Characterization
3. Materials and Methods
3.1. Samples Selected for This Study
3.2. Solution of Zero-Valent Iron Nanoparticles (nZVI)
3.3. Procedure and Implementation of the Column Laboratory Test
- Blank—Deionized water
- Nanoparticles with 1 g/L concentration
- Nanoparticles with 3 g/L concentration
- Nanoparticles with 7 g/L concentration
- 1st—Before the injection of the solution of nZVI;
- 2nd—After 24 h;
- 3rd—After 48 h;
- 4th—After 72 h;
- 5th—After 1 week;
- 6th—After 2 weeks;
- 7th—After 1 month;
- 8th—After 2 months;
- 9th—After 4 months.
4. Results
4.1. Geochemical Characterization of the Samples Used for Testing nZVI at a Laboratory Scale, and Evaluation of the Contamination Degree of the Industrial Area
4.2. Data Obtained in the Laboratory-Scale Test of Injection of Nanoparticles of Zero-Valent Iron (nZVI)
4.2.1. General Remarks
4.2.2. Variation of the Physic-Chemical Parameters (pH, Redox Potential, Conductivity)
- pH:
- Redox Potential:
- Conductivity
4.2.3. Variation of the Immobilization Rate of the Target Contaminants
- pH Effect
- Effect of Suspension Concentration and Injection Time of nZVI
- (1)
- Regarding the reaction with nZVI, there is high similarity between zinc and cadmium (Figure 6); however, after 60 days, the average removal of Zn was higher than for Cd. The removal of both elements in the interstitial water of the samples over the 120 days of testing can be summarized as follows:
- (i)
- After 60 days, the removal rate of Zn varied between 80% and 100%, and for Cd between 50% and 80%, with the last element corresponding to levels ranging from 0.6 mg/L to 3 mg/L. For Zn, for the higher nZVI concentrations, the average removal was approximately 99% (7 g/L) and 95% (3 g/L), with the corresponding concentrations ranging from 0.5 and 2.0 mg/L. Although with a significant reduction in relation to the initial contents, the highest removal rates of both elements from the soluble phase of the samples were not enough to keep their concentrations below the values tabulated for groundwater by the Legislation for the State of Minas Gerais, which is 1.05 mg/L for Zn and 0.005 mg/L for Cd [53].
- (ii)
- After 120 days, an increase of the levels of these two elements in the interstitial water of the samples was observed, particularly significant in CA2-10 for Zn (removal rates between 2% and 48%), which is the sample with the highest contamination index regarding these elements, the highest sulphate content, and the lowest permeability. However, when comparing the initial values before the injection of nZVI with the final values obtained in a composite sample, a marked decrease in both elements is perceptible in all the samples (Table 4).
- (2)
- For lead, the retention rate was directly proportional to the concentration of nZVI suspensions, and the suspensions with higher concentrations proved to be very efficient in its removal, in some samples, even after 120 days (Figure 7). This is the case of soil CA1-33, which, at the end of the test, showed a removal rate of 80–85%, corresponding to a concentration of 0.05–0.07 mg/L of Pb, albeit still higher than the regulated value of 0.01 mg/L [39]. Although with a maximum immobilization of 90% in the alluvium sample CA2-10, Pb decreased to about 0.08 mg/L. Only in sample CA3-18, values below the regulated value were reached, given the removal of almost 100% after 60 days, corresponding to a concentration of 0.001 mg/L of Pb. After this period, there was, however, a slight increase.
- (3)
- Copper is the element with the most distinct behavior regarding its retention by nZVI (Figure 7): (1) all the tests showed effective removal; and (2) contrary to the other elements, there is no proportionality between the retention rate and the suspensions concentration. In all the samples and for all the nZVI concentrations, the retention rate was always high, and the temporal evolution and behavior of Cu were very similar. After 60 days of the injection and at the final stage of the test (120 days), Cu concentrations in the interstitial solution were always lower than the regulated value of 2.00 mg/L [53]. The retention rates were very similar in the soil CA1-33 (70–95%) and in the alluvium CA2-10 (80–90%), reaching 99% in CA3-18. The minimum concentrations attained after 60 days corresponded to 0.02 and 0.04 mg/L, 0.1 and 0.3 mg/L, and 0.001 mg/L, respectively. In the case of CA3-18, given the high efficiency of the Cu removal by applying nZVI, the final values were very similar for any concentration of the suspension injected.
- (4)
- Although with critical values in the sedimentary materials and soil arsenic contents in the aqueous phase were very low, some of them slightly higher than the limits proposed by Brazilian legislation for groundwater [53].
4.3. Test Data Evaluation—Risk Spatial Projection
5. Discussion
5.1. Effect of a Laboratory-Scale Injection of nZVI Solutions into Heavily Metal-Contaminated Materials from a Tropical Climate
- (1)
- In this experiment a drought situation was simulated, since the system was closed, and the extracted water was not replaced. The interstitial water became more concentrated over time and the material was always moist; however, there was no simulation of water loss by infiltration and water replacement by the rain effect. The most extreme situation of a closed system was recreated, and thus, the concentrations of metals in soluble phase reached the highest values. If there is a marked decrease of the metal concentrations over time after nanoparticles application, this decrease should have greater expression at a real scale. Since not all the conditions of a real situation could be reproduced, the achieved data cannot be considered as absolute.
- (2)
- The extractions of the interstitial water were always conducted in the same points of the sedimentary columns, in an upper and lower position; thus, the values obtained for the different metals do not reflect the whole column and they have to be considered as point sample values; this consideration results from the fact that aggregation and nanoparticles nuclei was verified in several areas of the columns and the diffusion of the particles through the soil and alluvial sediments was not uniform, due, mainly, to their low permeability. Models of aggregation of small particles have been published in many works and in most of them it is mentioned that a surface charge established on the surface of particles causes repulsive electrostatic forces between them. However, the iron particles corrode in the water, and this process can produce changes on the surface charge and on the aggregation rate [62]. Because particles are made from iron, they also have magnetic properties, which significantly affects the aggregation rate [28,63,64]. As a result of aggregate formation, the specific surface area will also decrease, resulting in a reactivity decrease [65].
- (3)
- These two factors led to the development of distinct chemical environments in the same sample, which certainly conditioned different retention reactions and rates of the various metals. Thus, the irregularities verified for pH, redox, and element concentrations in the upper and lower layers of the columns corroborate the occurrence of different removal and solubilization reactions with distinct behaviors and intensities throughout the sample. The poor diffusion of the suspension may have been due, apart from the low permeability of the material, to the injection speed, which was possibly too high. However, since the injection was made in an upward direction, a lower speed could cause sedimentation of the particles in the peristaltic pump tubes.
- (4)
- The data that will best reflect the real situation of metals immobilization correspond to the analysis of the composite porewater (Table 4) and levels of the target metals analyzed in digested samples, resulting from the homogenization of all the material in each column. However, these could only be carried out before the injection (t = 0) and in the final phase of the test (t = 120), when the soil and alluvium were removed from the columns after 4 months of the nanoparticles’ injection.
5.2. Factors Affecting the Variation of Physic-Chemical Parameters over the Batch Column Experiment
- (1)
- Chemical composition characterized by high levels of iron oxides (Fe2O3: 16–52%);
- (2)
- (3)
- Excess of metals in solution in a confined environment, where no infiltration, diffusion, and leaching of soluble ions could occur, and where permanent water saturation might decrease oxidation conditions at an early stage. After 3 days, the ZVI might have reacted directly with the metallic elements in solution in cationic form, leading to H+ release, with subsequent pH decrease and dissolution of some iron oxides, with high contents in these materials. This may also justify the increase of oxidation conditions, as can be demonstrated by Equation (2):
- (4)
- In the presence of some metals, such as Pb, with high contents in these sedimentary materials, the reduction-oxidation reaction with the nZVI particles can lead to the formation of H+, which may lower the pH (Equation (3)):
5.3. Removal Mechanisms of Contaminants by nZVI
- Metals that have an E0 that is more negative than, or similar to, that of Fe0 (e.g., Cd and Zn) are removed from solution by adsorption onto the iron oxide (hydroxide) layer surrounding the zero-valence iron (Fe0) core. Upon binding to the FeOOH layer, these metals bond through electrostatic interactions without undergoing changes in their valence state. To a lesser extent, complexation at the surface of the nanoparticles and co-precipitation may also occur.
- Metals with an E0 much more positive than Fe0 (e.g., As and Cu) are preferentially removed by precipitation and layer-mediated reduction (reductive precipitation) on the surface of nZVI [45].
- Metals with E0 slightly more positive than Fe0 (e.g., Pb) can be removed by both adsorption and partial chemical reduction.
- Reduction—As, Cu, and Pb.
- Adsorption—As, Pb, Cd, and Zn.
- Oxidation/reoxidation—As and Pb.
- Co-precipitation—As.
- Precipitation—Cu, Pb, Cd, and Zn.
- Immobilization of zinc and cadmium
- (1)
- Extremely high contents, much higher than the toxicity limits.
- (2)
- The high levels of these two elements in soluble forms may influence the retention capacity of nZVI, through competition between the two cations for chemo-adsorption sites in the (oxy)iron hydroxide layer formed on the nanoparticles surface. It has been observed by several authors [17] that, in the presence of these two cations and in view of the competitiveness between both, there is a more efficient removal and selectivity of nZVI particles for Zn2+ than for Cd2+.
- (3)
- Low pH values that decreased after the first day of the test and remained low until about 60 days after injection. Low pH accelerates the corrosion and the dissolution of the oxide layer of the nZVI, increasing the reaction rates due to greater availability of electrons from the Fe0 core [56]. Therefore, the general decrease of pH after 2 days of injection may have contributed to intense reactions that may have rapidly immobilized metallic cations by adsorption onto the iron oxide (hydroxide) layer surrounding the zero-valence iron (Fe0) core. However, the impact of pH on metal removal by nZVI depends on the oxidation state of the metal and the removal mechanism [56]. For Zn and Cd, besides the very high values in solution, both cations are easily mobilized at pH < 5.5 [70]. Thus, although a very significant immobilization of most metals was observed, the concentrations of Zn and Cd, with retention rates ranging from 80–100% for Zn and 50–80% for Cd, were not able to reach the legislated values. The high reaction rates due to the low pH values are likely to have been one of the factors responsible for the decreased reactivity of nZVI after 2 months.
- (4)
- Presence of high levels of sulphates, which is also an inhibiting factor for Zn and Cd retention, since it is a competitive anion for receiving electrons transferred by the nZVI [56]. Sulphates, in contact with nZVI, may be reduced to sulphides, which precipitate with metal cations on the surface of nanoparticles, reducing their adsorption capacity.
- Immobilization of Lead
- Immobilization of Copper
- Immobilization of Arsenic
5.4. Aging Time of nZVI
5.5. Reduction of the Risk Level of Sediments and Soils after nZVI Injection
6. Conclusions
- This was a laboratory batch study where it was not possible to simulate the drainage, diffusion, and precipitation conditions that naturally occur. This corresponded to a very complex and closed system, tested under extreme conditions, simulating a prolonged period of drought, in which there was no replacement of water during the entire test; thus, the interstitial water of the materials became progressively more concentrated.
- This experiment reflected the real situation of the surrounding area of a metallurgical plant, where most of the soils, alluvium, and river sediments showed very high concentrations of heavy metals and sulphates of anthropic origin, including high levels of lithogenic iron and manganese. The contaminant metals include elements with different standard redox potentials (E0) relative to that of Fe0, which led to multiple retention mechanisms, namely, adsorption, desorption, reduction, oxidation, complexation, and co-precipitation. This high diversity under soluble phase decreased the reactivity of the nZVI particles, probably by competition among the various cations for the exchange sites or, in the case of anionic complexes such as sulphates, by reduction and transformation into sulphides that may be precipitated together with metallic cations on the surface of the nanoparticles.
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Chemical Composition of Fe0 Nanoparticles | Fe (Core), FeO (Capsule) |
---|---|
Mass percentage of the solution | 20% |
Fe0 mass in solid fraction | 80% |
Other substances of the solid fraction | Fe3O4, FeO, C |
Other substances in the liquid fraction | Organic Stabilizer |
Particle shape | Spherical |
Fe0 particle size | D50 nm < 50 |
Specific surface | >25 m2/g |
Color | Black |
Solution density | 1210 kg/m3 |
Fe0 Density | 7870 kg/m3 |
Fe3O4 Density | 5700 kg/m3 |
Sediments and Alluvium (CONAMA, 2012) | As (mg kg−1) | Cd (mg kg−1) | Cr (mg kg−1) | Cu (mg kg−1) | Ni (mg kg−1) | Pb (mg kg−1) | Zn (mg kg−1) |
---|---|---|---|---|---|---|---|
Normal | <5.9 | <0.6 | <33.0 | <17.0 | <14.0 | <8.4 | <58.0 |
Intermediate | 33.0–37.3 | 17.0–35.7 | 14.0–18.0 | 8.4–35.0 | 58.0–123.0 | ||
Caution | 5.9–17.0 | 0.6–3.5 | 37.3–90.0 | 35.7–197.0 | 18.0–35.9 | 35.0–91.3 | 123.0–315.0 |
Critical | >17.0 | >3.5 | >90.0 | >197.0 | >35.9 | >91.3 | >315.0 |
ZVI | Layers | pH | Eh (mV) | ||||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
t0 | t24H | t48H | t72H | t7d | t14d | t30d | t60d | t120d | t0 | t24H | t48H | t72H | t7d | t14d | t30d | t60d | t120d | ||
CA1-33 | |||||||||||||||||||
1 g/L | Upper | 4.44 | 6.61 | 6.90 | 6.53 | 2.70 | 6.22 | 3.20 | 3.91 | 5.87 | 554.0 | 476.6 | 276.2 | 287.9 | 464.4 | 253.3 | 384.3 | 685.4 | 305.4 |
Lower | 4.07 | 6.76 | 6.32 | 6.26 | 6.09 | 5.62 | 4.76 | 3.27 | 5.65 | 431.2 | 424.9 | 272.8 | 466.0 | 296.4 | 233.8 | 375.4 | 639.7 | 321.6 | |
3 g/L | Upper | 3.50 | 6.88 | 7.10 | 6.72 | 4.11 | 3.00 | 3.33 | 3.23 | 4.77 | 417.4 | 169.4 | 187.8 | 184.6 | 346.3 | 444.7 | 398.7 | 449.1 | 264.8 |
Lower | 6.52 | 6.97 | 7.04 | 6.57 | 3.64 | 3.37 | 3.22 | 6.38 | 6.39 | 354.4 | 163.2 | 193.3 | 160.5 | 383.5 | 411.0 | 412.3 | 131.1 | 161.6 | |
7 g/L | Upper | 5.79 | 6.89 | 6.79 | 2.54 | 2.56 | 3.06 | 5.79 | 6.34 | 6.78 | 235.4 | 141.4 | 160.9 | 486.6 | 458.8 | 422.6 | 223.6 | 124.4 | 317.7 |
Lower | 6.71 | 6.17 | 7.05 | 2.13 | 2.07 | 3.25 | 4.43 | 6.42 | 6.60 | 233.9 | 102.5 | 160.0 | 506.0 | 444.6 | 462.8 | 288.4 | 121.1 | 305.2 | |
0 g/L | Upper | 6.70 | 6.48 | 2.94 | 3.05 | 2.50 | 3.41 | 2.85 | 3.61 | 4.61 | 245.7 | 204.8 | 277.7 | 496.7 | 683.2 | 485.5 | 567.8 | 157.6 | 301.5 |
Lower | 6.65 | 6.73 | 3.01 | 4.72 | 5.96 | 4.18 | 3.51 | 3.19 | 4.56 | 231.5 | 207.8 | 290.5 | 449.4 | 610.6 | 477.0 | 539.4 | 166.3 | 301.5 | |
CA2-10 | |||||||||||||||||||
1 g/L | Upper | 5.21 | 5.84 | 5.07 | 2.76 | 3.91 | 3.00 | 2.95 | 3.35 | 3.58 | 284.7 | 99.7 | 206.7 | 382.9 | 322.3 | 369.2 | 402.2 | 359.3 | 189.0 |
Lower | 5.16 | 5.64 | 4.61 | 2.60 | 3.90 | 3.25 | 3.99 | 3.44 | 3.71 | 310.6 | 201.9 | 216.6 | 410.8 | 357.9 | 409.8 | 418.7 | 450.8 | 234.8 | |
3 g/L | Upper | 5.51 | 6.28 | 6.13 | 2.57 | 4.19 | 4.08 | 3.26 | 4.04 | 4.87 | 245.8 | 51.3 | 129.7 | 384.6 | 290.4 | 407.4 | 430.4 | 152.3 | 275.4 |
Lower | 5.23 | 5.93 | 4.91 | 2.45 | 1.84 | 3.98 | 3.42 | 2.95 | 4.07 | 234.8 | 76.4 | 173.8 | 390.1 | 439.7 | 436.0 | 458.2 | 286.0 | 380.2 | |
7 g/L | Upper | 5.94 | 6.10 | 6.23 | 2.63 | 3.08 | 3.02 | 2.98 | 3.21 | 4.76 | 261.6 | 129.3 | 133.7 | 395.3 | 314.2 | 383.4 | 471.7 | 281.5 | 397.3 |
Lower | 5.91 | 5.79 | 6.23 | 2.25 | 2.53 | 3.77 | 3.25 | 4.38 | 5.10 | 229.7 | 147.0 | 167.2 | 457.4 | 399.1 | 417.4 | 489.2 | 128.1 | 321.5 | |
0 g/L | Upper | 2.57 | 2.93 | 2.72 | 2.77 | 2.72 | 3.20 | 3.05 | 3.63 | 3.54 | 226.2 | 551.8 | 545.3 | 643.1 | 627.0 | 593.9 | 181.6 | 569.1 | 320.7 |
Lower | 2.57 | 3.64 | 4.78 | 3.45 | 3.06 | 3.07 | 3.70 | 3.60 | 3.26 | 331.0 | 486.5 | 503.4 | 579.6 | 584.1 | 524.0 | 202.0 | 574.1 | 336.5 | |
CA3-18 | |||||||||||||||||||
1 g/L | Upper | 4.31 | 6.56 | 6.78 | 2.55 | 4.54 | 2.74 | 3.73 | 6.29 | 5.21 | 360.4 | 170.7 | 206.0 | 423.7 | 296.3 | 392.9 | 418.9 | 306.0 | 388.8 |
Lower | 5.79 | 6.73 | 6.87 | 2.87 | 5.51 | 3.19 | 3.08 | 3.61 | 6.65 | 338.8 | 179.4 | 213.2 | 475.2 | 281.6 | 478.5 | 488.9 | 442.4 | 374.1 | |
3 g/L | Upper | 5.81 | 6.65 | 6.91 | 2.19 | 4.33 | 4.30 | 2.93 | 6.38 | 5.92 | 348.3 | 133.2 | 159.1 | 486.9 | 387.3 | 336.0 | 417.3 | 121.0 | 305.3 |
Lower | 6.71 | 6.86 | 7.07 | 2.40 | 3.37 | 3.74 | 3.71 | 6.55 | 6.69 | 331.3 | 138.1 | 159.5 | 489.6 | 455.0 | 419.6 | 400.8 | 125.9 | 322.8 | |
7 g/L | Upper | 5.27 | 6.65 | 6.97 | 2.24 | 2.47 | 3.08 | 3.79 | 5.19 | 6.90 | 272.6 | 63.9 | 146.7 | 453.8 | 445.1 | 380.9 | 395.8 | 130.5 | 271.4 |
Lower | 6.04 | 6.79 | 6.95 | 2.28 | 2.68 | 3.52 | 3.13 | 6.37 | 6.98 | 255.4 | 95.1 | 148.6 | 456.7 | 458.9 | 429.7 | 502.2 | 127.4 | 262.3 | |
0 g/L | Upper | 4.65 | 6.69 | 5.22 | 2.36 | 3.75 | 3.48 | 3.41 | 3.90 | 3.87 | 343.0 | 212.6 | 258.3 | 527.0 | 537.8 | 521.7 | 528.4 | 574.9 | 543.7 |
Lower | 6.43 | 6.70 | 2.32 | 2.69 | 4.19 | 3.15 | 3.31 | 3.77 | 3.52 | 298.0 | 196.3 | 448.6 | 521.6 | 459.9 | 540.6 | 531.0 | 579.6 | 568.2 |
ZVI | As (mg/L) | As (%) | Cd (mg/L) | Cd (%) | Cu (mg/L) | Cu (%) | Pb (mg/L) | Pb (%) | Zn (mg/L) | Zn (%) | |||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
t = 0 | t = 120 | t = 120 | t = 0 | t = 120 | t = 120 | t = 0 | t = 120 | t = 120 | t = 0 | t = 120 | t = 120 | t = 0 | t = 120 | t = 120 | |
CA1-33 | |||||||||||||||
1 g/L | 0.005 | 0.001 | 20 | 0.137 | 0.081 | 59 | 0.375 | 0.044 | 12 | 0.271 | 0.111 | 41 | 29.300 | 31.957 | 109 |
3 g/L | 0.055 | 0.001 | 2 | 0.110 | 0.041 | 38 | 0.102 | 0.028 | 27 | 0.304 | 0.031 | 10 | 24.001 | 8.852 | 37 |
7 g/L | 0.023 | 0.001 | 4 | 0.093 | 0.041 | 44 | 0.061 | 0.023 | 38 | 0.290 | 0.020 | 7 | 27.596 | 9.205 | 33 |
0 g/L | 0.061 | 0.001 | 2 | 0.115 | 0.040 | 35 | 0.064 | 0.019 | 29 | 0.235 | 0.041 | 18 | 22.023 | 17.001 | 77 |
CA2-10 | |||||||||||||||
1 g/L | 0.057 | 0.003 | 5 | 4.568 | 0.813 | 18 | 0.420 | 0.123 | 29 | 1.388 | 0.750 | 54 | 950.101 | 309.307 | 33 |
3 g/L | 0.057 | 0.001 | 2 | 3.622 | 2.699 | 75 | 0.373 | 0.474 | 127 | 1.908 | 1.267 | 66 | 774.770 | 610.141 | 79 |
7 g/L | 0.062 | 0.001 | 2 | 3.808 | 2.134 | 56 | 0.185 | 0.190 | 103 | 1.125 | 0.648 | 58 | 829.836 | 546.192 | 66 |
0 g/L | 0.052 | 0.001 | 2 | 1.748 | 1.359 | 78 | 0.500 | 0.214 | 43 | 2.033 | 0.892 | 44 | 489.003 | 444.873 | 91 |
CA3-18 | |||||||||||||||
1 g/L | 0.004 | 0.001 | 23 | 2.340 | 1.382 | 59 | 0.059 | 0.068 | 116 | 0.709 | 0.060 | 8 | 49.718 | 35.870 | 72 |
3 g/L | 0.093 | 0.001 | 1 | 2.315 | 1.184 | 51 | 0.081 | 0.050 | 62 | 0.549 | 0.036 | 7 | 47.229 | 24.658 | 52 |
7 g/L | 0.003 | 0.001 | 40 | 2.560 | 1.868 | 73 | 0.061 | 0.142 | 233 | 0.414 | 0.094 | 23 | 38.016 | 48.646 | 128 |
0 g/L | 0.003 | 0.001 | 33 | 2.724 | 1.438 | 53 | 0.077 | 0.098 | 127 | 0.484 | 0.055 | 11 | 46.985 | 39.998 | 85 |
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Fonseca, R.; Araújo, J.; Pinho, C.; Albuquerque, T. Evaluating the Effectiveness of Nanotechnology in Environmental Remediation of a Highly Metal-Contaminated Area—Minas Gerais, Brazil. Geosciences 2022, 12, 287. https://doi.org/10.3390/geosciences12080287
Fonseca R, Araújo J, Pinho C, Albuquerque T. Evaluating the Effectiveness of Nanotechnology in Environmental Remediation of a Highly Metal-Contaminated Area—Minas Gerais, Brazil. Geosciences. 2022; 12(8):287. https://doi.org/10.3390/geosciences12080287
Chicago/Turabian StyleFonseca, Rita, Joana Araújo, Catarina Pinho, and Teresa Albuquerque. 2022. "Evaluating the Effectiveness of Nanotechnology in Environmental Remediation of a Highly Metal-Contaminated Area—Minas Gerais, Brazil" Geosciences 12, no. 8: 287. https://doi.org/10.3390/geosciences12080287
APA StyleFonseca, R., Araújo, J., Pinho, C., & Albuquerque, T. (2022). Evaluating the Effectiveness of Nanotechnology in Environmental Remediation of a Highly Metal-Contaminated Area—Minas Gerais, Brazil. Geosciences, 12(8), 287. https://doi.org/10.3390/geosciences12080287