Origin and Spatial Distribution of Cadmio in Farms Cacaoteras in the Province of Manabí, Ecuador
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Annals of R.S.C.B., ISSN:1583-6258, Vol. 25, Issue 6, 2021, Pages. 15142 - 15151 Received 25 April 2021; Accepted 08 May 2021. Origin and Spatial Distribution of Cadmio in Farms Cacaoteras in the Province of Manabí, Ecuador Frank Guillermo Intriago-Flor. Universidad Técnica de Manabí. Facultad de Ciencias Zootécnicas. Km 2 ½ vía Boyacá-Chone. Manabí, Ecuador, e-mail: frank.intriago@utm.edu.ec; orcid: https://orcid.org/0000-0002-0377-1930 Maritza Viviana Talledo-Solórzano. Universidad Técnica de Manabí. Facultad de Ciencias Zootécnicas. Km 2 ½ vía Boyacá-Chone. Manabí, Ecuador, e-mail: mtalledo4282@utm.edu.ec; orcid: https://orcid.org/0000-0002-5735-9490 José Ricardo Macías-Barberán. Universidad Técnica de Manabí. Facultad de Ciencias Zootécnicas. Km 2 ½ vía Boyacá-Chone. Manabí, Ecuador, e-mail: ricardo.macias@utm.edu.ec; orcid: https://orcid.org/0000-0002-7900-2222 Gerardo José Cuenca-Nevárez. Universidad Técnica de Manabí. Facultad de Ciencias Zootécnicas. Km 2 ½ vía Boyacá-Chone. Manabí, Ecuador, e-mail: gerardo.cuenca@utm.edu.ec; orcid: https://orcid.org/0000-0002-1128-3013 Juan Carlos Menjivar-Flores. Universidad Nacional de Colombia. Facultad de Ciencias Agrarias, Carrera. 32 #12. Valle del Cauca, Colombia, e-mail: jcmenjivarf@unal.edu.co; orcid: https://orcid.org/0000-0002-0985-7778 Abstract Thecultivation of cocoa is of great economic importance to many producing countries Chocolates and other by-products are made from cocoa beans, but their marketing is threatened by the presence of heavy metals. In the present study, the cadmium (Cd) content of soils and its presence in cocoa beans in the province of Manabí in Ecuador were evaluated. A total of 181 cocoa farms were selected soil samples, irrigation water, organic fertilizer, leaves and almonds were analyzed to determine the origin, content and spatial distribution of Cd. For the extraction and determination of the Cd, the standards 3050B USEPA and 6010C were used by means of spectrometry by ICP-OES ICAP respectively. The data were analyzed by descriptive statistics and Pearson correlation using SAS/STAT version 9.4.The results showthe presence of Cd in analyzed parts presenting the following order: Leaf Cd > Almond Cd > Cd soil. Cd content presented positive correlation for organic matter, N, P, K, Mn, Zn; leaf and almond Cd content presented positive correlation for bulk density, clay, field capacity, permanent wilt point, Mg, CIC and Ca respectively. Keys words: Organic farming, contaminant, heavy metal, Theobroma cacao Introduction Soil degradation is related to the excessive use of fertilizers, pesticides, burning of harvest residues and the use of heavy machinery (Santana et al., 2015), on the other hand, it is necessary to highlight a special type of degradation which is produced by the presence of harmful chemical substances, which can accumulate in the soil causing its contamination, such is the case of Cadmium (Cd) (Pereira et al., 2017). The origin of Cd in agricultural soils occurs in two ways, anthropogenic and geogenic, both can contaminate soils through different processes (Tran & Popova, 2013), in that order of ideas, at the level of Latin America agricultural soils present different Cd levels, in Peru and Venezuela in soils cultivated with cocoa and at a depth of 5-20 cm, levels of 0.79 ppm were found (Arévaloet al., 2016), and 1.71 ppm of Cd (Pedraza&Huauya , 2017), respectively, on the other hand, in soils of the Santander Colombia area, levels 2.76 ppm are reported 15142 http://annalsofrscb.ro
Annals of R.S.C.B., ISSN:1583-6258, Vol. 25, Issue 6, 2021, Pages. 15142 - 15151 Received 25 April 2021; Accepted 08 May 2021. (Bravo& Benavides, 2020), in southern Ecuador studies carried out by Chávez et al,. (2015), where the concentration of Cd in 19 farms was monitored, it was found that in the 12 farms at depths of 0-15 cm they presented accumulation of Cd due to various anthropogenic activities. The interest in studying Cd in soils cultivated with cocoa arises from the fact that in 2012, the European Food Safety Authority (EFSA) issued an alert where it is recommended that chocolate with an amount greater than or equal to 50% solids of cocoa should contain a maximum of 0.3 ppm of Cd (Zug et al.,2019), the amendment to European regulation No. 1881/2006, which establishes the maximum levels of Cd for chocolate and cocoa-derived products considering as ranges from 0.10 to 0.80 ppm (Meter et al., 2019). Cocoa producing countries are concerned about the presence of this element in cultivated almonds (Durango et al., 2019) in the African continent specifically in Ghana, 0.32 mg.kg-1 has been reported in almonds (FAO, 2018), and 0.09 mg.kg-1 (Bertoldi et al., 2016). In the same sense, Ecuador, as a producer of fine flavor and aroma cocoa, is also on alert, the presence of this element at high levels would affect exports to the international market, possibly reducing revenues by 180 million dollars, which it would affect 51 thousand farmers (Veco-Andino, 2015). In that order of ideas and given the historical importance of cocoa cultivation in Ecuador, the need arises to determine the origins, content and spatial distribution of the Cd present in the soils, in the irrigation water, fertilizers, in the foliar and almond partcocoa. Materials and methods The research was carried out in the north central zone of the province of Manabí 0º 49 ”23” South Latitude, 80º 11 ”01” West Longitude, at an altitude of 20 m.a.s.l., 181 cocoa- producing farms were selected for them, these are located on soils developed from different geologies (Aguirre, 2005). The soils were classified as Udic, HapludoitFluventic which are deep soils of variable texture (dominant loam) and Ustic, UstropeptVetic (Reyna et al., 2018). To determine the origin of the Cd, samples of soils, fertilizers, waters, leaves and cocoa beans were taken as follows: Soil sampling was carried out at a depth of 20 cm, following the INIAP methodology, (2016). The irrigation water sample was collected at the water entry points to the farm using clean and sterile 200 ml plastic containers, in order to preserve the sample, it was acidified between pH 1 to 2 with nitric acid, (NTE INEN 2169, 2013). From the organic fertilizer, random composite samples of 1 kg of each fertilizer were taken (AgroCalidad, 2015), it was placed in a previously identified ziploc-type sleeve and taken to the laboratory for the determination of total Cd+2. The foliar sampling was carried out according to the proposal of Puenteset al., (2014). The almond samples of the National-type Creole cocoa varieties (90%) and 10% of the EET-type clones, were taken according to the methodology of Rivera (2013), for this, 20 mature pods were harvested. To determine the total Cd in soil, irrigation water, fertilizer, foliar and almond, an acid digestion with HNO3 + HCl was performed and it was quantified by ICP ICAP 7200 spectrometry under the EPA 6010C Standard. The texture was determined by the Robinson pipet method (USDA, 2002), the pH and electrical conductivity (conductivity meter) were measured in deionized water (soil/water ratio 1:2) using a multiparametric (HANNA HI9829) (Chávez et al., 2015). For the determination of organic matter, the oxidation method with potassium dichromate (K2Cr2O7) by Walkey Black (1947), modified by Embrapa (2009), 15143 http://annalsofrscb.ro
Annals of R.S.C.B., ISSN:1583-6258, Vol. 25, Issue 6, 2021, Pages. 15142 - 15151 Received 25 April 2021; Accepted 08 May 2021. (Rojas et al., 2018) was used. The cation exchange capacity was determined with 1N ammonium acetate at pH 7. For the determination of Zn and Mn, the digestion method with 6M nitric perchloric HCl was used and the determination by the atomic absorption spectrophotometry method (Rodríguez & Rodríguez, 2011). The elaboration of the map of the spatial distribution of Cd in soils, leaves and almonds was carried out with ArcMap 10.4.1. The semivariograms, were adjusted using the exponential model proceeding to carry out the interpolation using a normal Kringing log (Argüelloet al., 2019). The results were subjected to a descriptive statistical analysis (mean, mode, variance, standard deviation and coefficient of variation), a Pearson correlation analysis and multiple regression between the Cd contents in soils, foliar and almonds and the physical-chemical properties of the soil. Results and Discussion Characterization of the study area The sizes of the sampled farms range from 0.25 to 10.00 hectares, of these 60% are in the Bolívar canton where Tertiary-age rocks predominate and to a lesser extent quaternary deposits, the remaining 40% are established in the cantons Chone, Portoviejo and Tosagua where quaternary geological formations predominate (IEE, 2013). The average annual temperature for the last five years is 26 ºC, with an evapotranspiration of 1256 mm and precipitation of 762 mm. Analysis of soil properties The low variation of the apparent density (13.35) is very similar to those found by Peña et al., (2009), cited by Rodríguez (2015) in Inceptisols de Colombia, similar conditions present the percentage of porosity (6.015), Not so for the humidity, clay and the capacity of water stored by the soil that present a high variation, these tendencies show an excellent porous space, low infiltration speed and increase in the capacity of retention of humidity in the soil (Delgadillo&Pérez, 2016). Table 1.Descriptive analysis of the physical properties of the soil in the study area. Standard Variationcoefficient Variable Mean (%) deviation ApparentDensity 1.38 0.184 13.350 PorosityPercentage 46.17 2.777 6.015 Field Capacity 25.27 6.468 25.591 Permanentwiltingpoint 12.55 4.945 39.378 Storablewatersheet 88.74 22.539 25.398 Nine textural classes were found where the most dominant is loam with 37%, second with clay loam (22%), silty loam (12%), silty clay loam (10%), sandy loam (9%), clay (6%), silty clay (4%), sandy (1%), the distribution of the particles presented loamy soils, with good porous space and do not present degradation by compaction, in addition they maintain an optimal water storage sheet for soils with cocoa crops. 15144 http://annalsofrscb.ro
Annals of R.S.C.B., ISSN:1583-6258, Vol. 25, Issue 6, 2021, Pages. 15142 - 15151 Received 25 April 2021; Accepted 08 May 2021. On the other hand, it is highlighted that 88.39% of the farms studied the soil pH was neutral, 10% presented slight alkalinity. In 22% of the farms the organic matter values were higher than 3%, 40% have values between 2-3% and 38% below 2%. According to Puenteset al., (2014) an optimal cation exchange capacity for cocoa is 19.40 cmol.kg-1, in this order of ideas 73% of the farms have higher values and 27% of the farms have values lower than those reported. Cadmium content in soil, leaves, almonds, irrigation water and organic fertilizer The accumulation of Cd in the soils showed mean values of 0.628 mg.kg-1 lower than the critical level established by the soils of the Junta de Andalucía where the permissible concentrations are 2 mg.kg-1 (Galánet al., 1999), meanwhile this value is considered higher than the critical level established by USEPA, (2002) for agricultural soils in the United States (0.43 mg kg-1). In figure 1, the spatial distribution of the Cd content is presented, it is observed that the higher concentrations of 0.825 to 1.97 mg.kg-1 are found in the north center of the study area. Figure 1.Spatial distribution of the Cd content in soils. In Figure 2, the trend of the mean Cd content in the soils, leaves and almonds is observed, when dividing the study area into four sectors. The average Cd content in cocoa leaves was 1.25 mg.kg-1, being higher than the values of Cd in grain and Cd in soil, this trend was also observed in studies carried out by Gramlichet al., (2017) for two varieties and four cocoa production systems in Bolivia. It is necessary to emphasize that in the study carried out the Cd values in the Nacional variety in leaf are lower than those reported by Barrazaet al., (2017) in the EET 116 clone in the Portoviejo area. 15145 http://annalsofrscb.ro
Annals of R.S.C.B., ISSN:1583-6258, Vol. 25, Issue 6, 2021, Pages. 15142 - 15151 Received 25 April 2021; Accepted 08 May 2021. 4 3.5 0.61 3 Cd (mg.kg-1) 2.5 0.69 0.58 0.68 2 1.75 1.5 1.18 1.14 1.03 1 0.5 1.18 0.87 0.93 1.05 0 North South East West Sites Cd grain Cd leaf Cd soil Figure 2.Distribution of the content of Cd+2 in the study area. For the European Food Safety Authority (EFSA), the permissible limits of Cd are 0.1 to 0.80 mg.kg-1 for different types and proportions of cocoa in chocolate production (Engbersenet al., 2019). In 60% of the farms studied, the Cd content was found in a range of 0.8 to 2.74 mg.kg- 1 , these concentrations are higher than the permissible levels, with an average of 0.99 mg.kg-1 of Cd in the cocoa bean, are distributed in the central zone and with 2% of the farms with minimum values towards the south eastern zone of the study area as shown in Figure 3. The Cd contents in the different parts analyzed present the following order: Cd leaf> Cd grain> Cd in soils, the same behavior pattern was found in other studies on Cd in cocoa (Gramlichet al., 2017; Llatanceet al., 2018;Ramtahlet al., 2016; Rodríguez et al., 2019; Romero-Estévez, 2019). Figure 3.Spatial distribution of the Cd+2 content in cocoa beans. The farms under study use compost-type fertilizers that are made with raw materials from the area and that are applied at a ratio of 3.2 t ha-1, this presented an average Cd concentration of 0.277 mg kg-1, they are considered low levels due to the criterion of European regulations through Regulation (EC) No. 1069/2009 that the concentration limits for Cd in compost should not be greater than 0.7 mg kg-1 of Cd, Fernández (2018), but are permissible between a range of 0.01 to 1.00 mg kg-1, Salmanzadehet al., (2016), establish that the continuous 15146 http://annalsofrscb.ro
Annals of R.S.C.B., ISSN:1583-6258, Vol. 25, Issue 6, 2021, Pages. 15142 - 15151 Received 25 April 2021; Accepted 08 May 2021. application of organic fertilizers in the long term will result in the accumulation of Cd in the soils, this aspect must be monitored in the study area. Irrigation water presented average Cd contents of 0.333 g L-1 considered high because they exceed the permissible limits of 0.05 g L-1 (Pozo, 2017), according to Mancillaet al., (2012), the presence of heavy metals in irrigation water represents a problem for agriculture due to the accumulation in agricultural soils, in that order of ideas in the study area, the use of water for irrigation and the application of fertilizer organic compost-type accounts for 10% and 8% respectively, which can be long-term sources of availability and accumulation of Cd in the soil and therefore its presence in leaves and cocoa beans. Argüelloet al., (2019), express that the concentration of total soil Cd has a positive relationship with the use of irrigation, pesticides, organic agriculture and forestry, the application of compost and pruning did not significantly affect the soil Cd, in the same vein, Carrillo (2016), expresses that chicken manure, fermented organic fertilizers known as bokashi and in compost the Cd content remain below 2.5 mg kg-1Nziguheba and Smoders (2008). In figure 4 the average behavior of the Cd content for soil, foliar (leaves), almond, irrigation water and fertilizer can be observed. 2.5
Annals of R.S.C.B., ISSN:1583-6258, Vol. 25, Issue 6, 2021, Pages. 15142 - 15151 Received 25 April 2021; Accepted 08 May 2021. however, considering that 67% of cocoa farms have low Zn levels, it is possible, according to Alloway (2013), that Zn deficiency in the soil stimulates Cd uptake by plants. The Cd content in the leaf has a positive correlation with the CEC, and this with the clays, similar results reported by Gramlichet al., (2018), when finding a positive relationship between the Cd of the leaf and the clays in soils with a clay texture in organic agroforestry production systems, in that order of ideas, the content of Cd in the leaf shows a correlation with Ca and Mg in soils, at the increasing these in the exchange sites, increases their concentration in the soil and the Cd content in the leaves and in the cocoa beans Huang et al., (2017), and Österas and Greger (2006). The Cd contents in the bean showed a positive correlation (0.578) with the Cd content in the leaf, as the accumulation of Cd in the leaf increases, the translocation of Cd to the cocoa kernel increases, these results coincide with studies carried out in Trinidad and Tobago and Colombia where very close correlations were found between the Cd content of the leaf and the cocoa grain (Ramtahalet al., 2016, Rodríguez et al., 2019), this in contrast to Chávez et al., (2015), found that exceeding 1 mg kg-1 of Cd in the cocoa grain had a high correlation with the cocoa pod. Conclusions The values found in soil, leaves and almonds do not exceed the reference values for Cd, however, it is advisable to continue monitoring its presence in soil, especially in farms in the south of the study area. The physical and chemical conditions of the soils are adequate for the cultivation of cocoa, and it is determined that the presence of Cd in soils and its translocation to leaves, almonds come from anthropogenic sources, that is, from the use of water for irrigation and fertilizers in different application rates. References 1. Agencia Ecuatoriana de Aseguramiento de la Calidad del Agro (AGROCALIDAD). (2015). Laboratorio de suelos, foliares y aguas: Instructivo para toma de muestras de foliares. Quito, Ecuador. 9 p. 2. Aguirre, M. (2005). Susceptibilidad al deslizamiento de los suelos y rocas de la provincia de Manabí. Tesis de Licenciatura. Guayaquil. Espol. 3. Arévalo-Gardini, E., Obando-Cerpa, M. E., Zuñiga-Cernades, L. B., Arévalo Hernández, C. O., Baligar, V., y He, Z. (2016). Metales pesados en suelos de plantaciones de cacao (Theobroma cacao L.) en tres regiones del Perú. Ecología aplicada, 15 (2), 81-89. http://dx.doi.org/10.21704/rea.v15i2.747 4. Argüello, D., Chavez, E., Lauryssen, F., Vanderschueren, R., Smolders, E., Montalvo, D. (2019). Soil properties and agronomic factors affecting cadmium concentrations in cacao beans: A nation wide survey in Ecuador. Science of the total Environment. 649: 120-127.http://dx.doi.org/10.1016/j.scitotenv.2018.08.292 5. Alloway B. J. (2013). Heavy metals in soils: Trace metals and metalloids in soils and their Bioavailability, 3 ed. Springer Science & Business Media. 6. Barraza, F., Schreck, T., Leveque, G., López, F., Prunier, J., Marquet, A., Maurice, L. (2017). Cadmium bioaccumulation and gastric bioaccesibility in cacao: A field study in areas impacted by oil activities in Ecuador. Environmental Pollution. 229: 950- 963.http://dx.doi.org/10.1016/j.envpol.2017.07.080 7. Bertoldi, D., Barbero, A., Camin, F., Caligiani, A., y Larcher, R. (2016).Multielemental fingerprinting and geographic traceability of Theobroma cacao 15148 http://annalsofrscb.ro
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