Formation of blue-green color by different chromium (VI) concentrations to 28°C and 60°C, in the presence of Litchi shell. pH 1.0. 1 g biomass.
Chromium (Cr) toxicity is one of the major causes of environmental pollution emanating from tannery effluents. This metal is used in the tanning of hides and leather, the manufacture of stainless steel, electroplating, textile dyeing and as a biocide in the cooling waters of nuclear power plants. Consequently, these industries discharged chromium (VI) bearing effluents which are of significant environmental concerns . Cr exists in nine valence states ranging from -2 to +6. From these, only the hexavalent [Cr (VI)] and trivalent chromium [Cr (III)] have primary environmental significance since they are the most stable oxidized forms in the environment.
Both are found in various bodies of water and wastewaters . Cr (VI) typically exists in one of these two forms: chromate (CrO4-2) or dichromate (Cr2O7-2), depending on the pH of the solution .These two divalent oxyanions are very water soluble and poorly adsorbed by soil and organic matter, making them mobile in groundwater. Both chromate anions represent acute and chronic risks to animals and human health, since they are extremely toxic, mutagenic, carcinogenic and teratogenic . In contrast to Cr (VI) forms, the Cr (III) species are predominantly hydroxides, oxides and sulphates, less water soluble, less mobile, 100 times less toxic  and 1,000 times less mutagenic . The principal techniques for recovering or removing Cr (VI), from wastewater are: chemical reduction and precipitation, adsorption on activated carbon, ion exchange and reverse osmosis . However, these methods have certain drawbacks, namely high cost, low efficiency, generation of toxic sludge or other wastes that require disposal and imply operational complexity . In this context, considerable attention has been focused in recent years upon the field of biosorption for the removal of heavy metal ions from aqueous effluents .
The process of heavy metal removal by biological materials is known as biosorption. Biomass viability does not affect the metal uptake. Therefore any active metabolic uptake process is currently considered to be a negligible part of biosorption. Various biosorbents have been tried, which include seaweeds, molds, yeast, bacteria, crab shells, agricultural products such modified corn stalks, , hazelnut shell , orange waste  and tamarind peel . It has also been reported that some of these biomass can reduce chromium (VI) to chromium (III), like
2. Material and methods
2.1. Biosorbents used
2.2. Preparation of stock solution
An aqueous stock solution (1000 mg/L) of Cr (VI) ions was prepared using K2Cr2O7 salt. pH of the solution was adjusted using 0.1 N HCl or NaOH. Fresh dilutions were used for each study.
2.3. Biosorption studies
The biosorption capacity of shells biomasses was determined by contacting 100 mL of solution containing different concentration of Cr (VI) (100-1000 mg/L) in 250 mL Erlenmeyer glass flasks, with 1 g of biomass. The mixture was shaken in a rotary shaker at 120 rpm followed by filtration at different times (covering minutes, days and weeks). The filtrate containing the residual concentration of Cr (VI) was determined spectrophotometrically at 540 nm after complexation with 1, 5 Diphenylcarbazide, these method have a detection limit between 0.02-0.5 mg/L of Cr (VI) , Cr (III) with Chromazurol S , and Cr total by Electrothermal Atomic Absorption Spectroscopy . For the determination of rate of metal biosorption by biomasses from 100 mL (at 100, 200, 300, 400, 500, and 1000 mg/L), the supernatant was analyzed for residual Cr (VI) after the contact period of 1-12 hours. The effect of pH and temperature on Cr (VI) sorption by natural biomass, was determined at pH values of 1, 2, 3, and 4, 28°C, 40°C, and 50°C, respectively. The effect of different doses of biomass ranging from 1 to 5 g/L, with 100 mg/L of Cr (VI) concentrations was determined. The values shown in the results section are the mean from three experiments carried out by triplicate.
2.4. Bioremediation assay
Four 250 mL Erlenmeyer glass flasks, with 5 g of shell biomass, were added with 20 g of contaminated earth and water with 297 mg Cr (VI)/g earth or 373 mg Cr(VI)/L water, of tannery (Celaya, Guanajuato, México), and the volume was complete to 100 mL with trideionized water. The mixture was shaken in a rotary shaker at 120 rpm followed by filtration using Whatman filter paper No. 1. The filtrate containing the residual concentration of Cr (VI) was determined with 1, 5 diphenylcarbazide .
3. Results and discussion
3.1. Effect of incubation time and pH
Figure 1 shows the effect of the incubation time and pH on Cr (VI) removal by
3.2. Effect of temperature on Cr (VI) removal by
L. chinensis Sonn shell
Temperature is found to be a critical parameter in the bioadsorption of Cr (VI) by
3.3. Effect of initial metal concentration
On the other hand, at low metal concentrations (100 and 200 mg/L), biomass studied, shows the best results for removal, adsorbing 100% at 10 and 20 min. respectively, while 1000 mg/L of metal is removed 100% up to 195 min of incubation at 28°C (Figure 3). Also, we observed the development of a blue-green and a white precipitate (Cr (OH)3), which changes more rapidly at higher temperatures (Figure 4). The results are coincident for tamarind peel and seeds, and
4. Time course of Cr (VI) decrease and Cr (III) production
The ability of the
Thus, after 1 h of incubation, the shell biomass caused a drop in Cr (VI) from its initial concentration of 1.0 g/L to almost undetectable levels and the decrease level occurred with no significant change in total Cr content. As expected, total Cr concentration remained constant over time, in solution control. These observations indicate that Litchi shell is able to reduce Cr (VI) to Cr (III) in solution. Furthermore, as the
|Vitamin C||N.D. **||5|
4.1. Effect of biosorbent dose
The influence of biomass on the removal capacity of Cr (VI) was depicted in Figure 7. If the researchers increase the amount of biomass also increases the removal of Cr (VI) in solution (100% of removal, with 5 g of biomass, 20 minutes), with more biosorption sites of the same, because the amount of added biosorbent determines the number of binding sites available for metal biosorption . Similar results have been reported for modified corn stalks , tamarind shell , and
4.2. Cr (VI) Removal in the presence of different heavy metals
The researchers analyzed whether the presence of different metals interfere with the Cr (VI) removal (500 mg/L) at a pH of 1.0, with 1 g of Litchi shell, finding that none of the added metals (salts of cadmium, copper, zinc and mercury) interferes with the Cr (VI) removal, but in the presence of zinc and mercury takes 10-20 min longer to remove 100% of the metal (Figure 8). This is consistent with many reports in the literature [1, 12, 13, 16, 31, 32, and 33].
4.3. Cr (VI) Removal by different biomasses
The researchers studied the Cr (VI) (100 mg/L) removal, with 1 g of different biomass. Litchi shell was the most efficient, because in 10 min at 28°C remove 100% of the metal, followed by xylan and polygalacturonic acid (150 and 300 min at 60 °C, respectively) and starch and cellulose were less efficient (43.6% at 28°C and 300 min of incubation and 21.83% at 60°C, at the same time of incubation, respectively) (Figure 9). With respect to other biomasses used, most authors report lower removal efficiencies of metal, for example: 45 mg/L for eucalyptus bark , 13.4 and 17.2 mg/L for bagasse and sugar cane pulp, 29 mg/L coconut fibers, 8.66 mg/L for wool , 25 and 250 mg/L of chitin and chitosan  and 1 mg/L for cellulose acetate .
4.4. Removal of Cr (VI) in industrial wastes with
Litchi chinensis Sonn shell
The researchers adapted a water-phase bioremediation assay to explore possible usefulness of
The chromium removal abilities of
4.5. Biorremediation assay
100 kg of contaminated soil (345 mg Cr(VI)/ g soil), with 20 g of natural biomass of
4.6. Desorption of Cr (VI) by different solutions
Furthermore, the researchers examined the ability of different solutions to desorb the metal bioadsorbed (250 mg/L) for the Litchi biomass, obtaining high efficiency with 0.1 N NaOH and 0.5 N (80 and 61% respectively (Figure 13), which are less those reported for desorption of Chromium (VI) with alkaline solutions (100%, pH 9.5), 1.0 N NaOH (95%) and a hot solution of NaOH/Na2CO3 (90%), respectively, [21, 51], and are higher than that reported (14.2%) using 0.2 M NaOH . This indicates that binding of metal to biomass is not as strong and that it can be used up to 6 desorption cycles of removal, which further lowers the metal removal process of niches contaminated with it.
4.7. Biosorption of Chromium (VI) in solution by different natural biomasses
In Table 2, the researchers show the biosorption of Chromium (VI)
|Incubation time (100 mg/L,28°C)||10 min||40 min||50 min||120 min||80 min||60 min||60 min||230 min|
|Temperature (50oC, 1.0 g/L)||35 min||90 min||110 min||120 min||200 min||140 min||80 min||105 min|
(5 g. 1.0 g/L)
|20 min||60 min||50 min||75 min||85 min||40 min||25 min||600 min|
|Presence of different heavy metals (500 mg/L)||Not Interfere||Not Interfere||Not Interfere||Not Interfere||Not Interfere||Not Interfere||Not Interfere||Not Interfere|
|Reduction of Cr VI to Cr III||Yes||Yes||Yes||Yes||Yes||Yes||Yes||Yes|
|Biorremediation of contaminated sites (100%)||Soil: 5 days
Water: 6 days
|Soil: 5 days
Water: 6 days
|Soil: 5 days
Water: 6 days
|Soil: 5 days
Water: 6 days
|Soil: 5 days
Water: 6 days
|Soil: 5 days
Water: 6 days
|Soil: 5 days
Water: 6 days
|Soil: 5 days
Water: 6 days
|Desorption (7 days)||81.2%||80.1%||78.3%||83%||79.3%||80%||78%||78%|
The use of biomaterials like natural biomasses has demonstrated to be a promising alternative for removal of Chromium hexavalent from aqueous solution. The screening and selection of the most effective biomaterial (biomasses) with sufficiently high metal binding capacity and selectivity for heavy metal ions, in this case, Chromium (VI), are prerequisite for a full process.
The natural biomasses showed complete capacity of biosorption and reduction concentrations of 1.0 g/L Cr (VI) in solution after different incubation times, and
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