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Composted municipal waste effects on chemical properties of a Brazilian soil
Bioresource Technology 98 (2007) 525–533
Composted municipal waste eVects on chemical properties of a Brazilian soil D.V. Pérez a,¤, S. Alcantara b, C.C. Ribeiro b, R.E. Pereira b, G.C. Fontes b, M.A. Wasserman c, T.C. Venezuela d, N.A. Meneguelli a, J.R. de Macedo a, C.A.A. Barradas e a Embrapa-Solos, R. Jardim Botânico, 1024, Rio de Janeiro (RJ), Brazil Instituto de Química, UFRJ, Av. Brig. Trompovsky, s/no, Cidade Universitária, Rio de Janeiro (RJ), Brazil c Instituto de Radioproteção e Dosimetria/CNEN. Av. Salvador Allende s/no, Recreio, Rio de Janeiro (RJ), Brazil d Fiocruz/ENSP, R. Leopoldo Bulhões, 1480, Rio de Janeiro (RJ), 21041-210, Brazil e PESAGRO-RIO, R. Euclydes Solon Pontes no 30, Nova Friburgo (RJ), 28.625-020, Brazil b
Received 4 January 2004; received in revised form 12 January 2006; accepted 7 February 2006 Available online 31 March 2006
Abstract The spread of composted municipal waste (CMW) on land can be used for sustainable crop production. Nevertheless, heavy metals availability may be a problem. Therefore, the main objective of this study was to assess the impact of CMW disposal on heavy metal accumulation in soil and plants. The treatments consisted of an untreated plot (control) and four rates of CMW application. All plots were cultivated in succession of carrot, cauliXower, sweet corn, and radish. Cu and Pb signiWcantly accumulated in the topsoil (0–5 cm) with a similar pattern in the depths of 5–10 cm and 10–20 cm. CauliXower, for Fe and Cu, and radish, for Pb and Cu, had their tissue analysis signiWcantly aVected due to the increasing rates of application of CMW. Nevertheless, the levels of accumulation in both, soil and plant, are within permissible limits. The evidences provided by this experiment indicated that heavy metals are less likely to cause problems for the estimation of CMW loadings to Brazilian agricultural land. © 2006 Elsevier Ltd. All rights reserved. Keywords: Municipal waste; Biosolid; Heavy metals; Soil properties
1. Introduction Municipal solid waste has been a serious environmental problem for many cities in developing countries (AbdelSabour and Abo El-Seoud, 1996; Soumaré et al., 2003). For instance, Rio de Janeiro, the second largest city in Brazil, has shown over the last years a signiWcant increase of solid waste handling. From 1995 to 2002, the total waste collected and the average waste collected per day increased from 2.6 to 3.6 million tons and 7.0 to 9.9 thousand tons, respectively.
*
Corresponding author. E-mail address: [email protected] (D.V. Pérez).
0960-8524/$ - see front matter © 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2006.02.025
In spite of the fact that there are many kinds of Wnal disposal available, the agricultural practice of amending soils with composted municipal waste (CMW) has received worldwide attention. This compost is rich in organic matter and its use may improve soil fertility and physical properties (He et al., 1992; Oshins, 1995; Anikwe and Nwobodo, 2002). However, repeated compost application can lead to accumulation of trace metals in soils that could eventually contaminate human and other animal food chains (Garcia et al., 1992; Pinamonti et al., 1997; National Research Council, 2003). There are currently no standards to evaluate compost quality in Brazil. Only Paraná and São Paulo states have set up guidelines based on the criteria for sludge (Sanepar, 1997; CETESB, 2001). Hence, there is a need to develop
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general standards for land application of urban waste. Our objectives were to determine: (i) the eVect of CMW application on the heavy metal composition of four vegetable crops and (ii) the residual eVects of this soil amendment on chemical properties of a Brazilian soil. 2. Methods All the composted municipal waste used during this study was taken from the largest treatment plant (Caju) of Rio de Janeiro State, and it was applied from 1995 to 1997 to a soil (Dystrochrept) located in Nova Friburgo County (22°15⬘S and 42°45⬘W), a representative mountain area of intensive vegetable production. The Köppen climate classiWcation is Cwb with mean annual temperature of 18 °C and mean annual precipitation of 1431 mm. In Caju plant, recyclable materials such as paper, glass and aluminum cans are manually removed early in the composting process. The remaining material is ground and the ferrous materials are separated using an electromagnet. The remaining organic waste is sieved and arranged into rows of long piles, and aerated by turning the pile periodically with mechanical means. Generally, 77–90 days are necessary to complete the composting. Some characteristics of the soil used in this study are presented in Table 1. The experimental Weld design was a randomized complete block, consisting of an untreated plot (control) and four rates of CMW surface application (12.5, 25, 50, 100 t ha¡1, wet basis) and four blocks. No inorganic fertilizer was applied. Irrigation was also applied so as to keep soil moisture in the range of Weld capacity. Each plot had a total area of 4.0 £ 2.4 m2 separated in all directions by a border of 1 m. All plots were cultivated with the following crop succession: carrot, planted on November 22nd 1995 and harvested on April 2nd 1996; cauliXower, planted on May 23rd 1996 and harvested on September 5th 1996; sweet corn, planted on December 10th 1996 and harvested on April 10th 1997; and radish, planted on August 20th 1997 and harvested on October 21st 1997. These species were selected due to the fact that they present diVerent edible plant parts (root, Xower, seed) and, consequently, diVerent nutrient uptake paths (Farago, 1994). They are also sensitive crops for diVerent metal toxicities (Alloway, 1990; Fergusson, 1990; Kabata-Pendias and Pendias, 1992). Rotary tilling was used in order to prepare the soil since it mixes the upper layers of soil rather than completely turning the soil over. In the present study, tillage went to the Wrst 15 cm of the soil. Moreover, the direction of the rotary tilling was inverted after each cultivation so as to avoid
Table 2 Procedure of the sequential extraction scheme used to fractionate heavy metals in soil samples Fraction
Sequence of extraction
(F1) Exchangeable + carbonate bound
HAc (2 M) + NaAc (2 M) 1:1; pH 4.7 Room temperature/16 h
(F2) Fe & Mn oxide bound
NH2OH · HCl (0,1 M); pH 2 (HNO3) Room temperature/16 h
(F3) Organically bound
H2O2 (30%) + HNO3 (0.02 M) + NH4Ac (1 M) Room temperature/16 h
(F4) Al oxide + strong Fe & Mn oxide bound
NaOH (0.1 M); pH 12 Room temperature/16 h
(F5) Residual
Aqua regia (HNO3/HCl; 1:3) 50 °C/30 min
plot-to-plot contamination. The compost treatments were superWcially applied in the same day of planting. Hence, a total amount of 50, 100, 200, and 400 t ha¡1 CMW was applied during the experiment. After the Wrst year of the last CMW spread (1998), soil samples were collected from four depths (0–5, 5–10, 10–20, 20–40 cm). The samples were dried in a forced air oven at 40 °C, passed thorough a 2-mm sieve and stored in a polyethylene bag. Vegetable edible parts were rinsed with distilled water, after that they were dried at 70 °C and ground in a stainless steel Wiley mill in order to pass a 1 mm sieve. Ground samples were stored at room temperature in acid-washed polyethylene containers. Aqua regia (HCl/HNO3, 3:1) extraction is used in order to evaluate anthropogenic inputs of heavy metals and it is rather eYcient (Hani, 1996; Walter and Cuevas, 1999; Scancar et al., 2000). Hence, this method was applied for soil and compost evaluation of Fe, Mn, Zn, Cu, Cd, Cr, Pb, and Ni. Therefore, considering the accumulation of some metals observed in the 0–5 cm, a sequential extraction method (Wasserman et al., 2005; Table 2) was used in order to specify the types of metal associations in soil. Dried plant samples were digested with a nitric/perchloric acid mixture. The content of the selected metals was analyzed by ICP-OES (Perkin–Elmer OPTIMA 3000, Norwalk, CT, USA). Duplicate analyses of each soil and plant extractions were performed throughout the work as well. The humic fractions of the soil were sequentially extracted according to Kononova and Bel’Chikova (Sastriques, 1982). In short, the free fulvic acids (not bound) were obtained by shaking 20–40 g of soil (air dried, 2 mm-sieved)
Table 1 Some physical and chemical characteristicsa of the soil used in the experiment Horizon Depth (cm) Clay (g/kg) pH (H2O) Ca2+ + Mg2+ (cmolc/kg) K+ (cmolc/kg) Al3+ (cmolc/kg) CEC (cmolc/kg) P (mg kg¡1) C (g/kg) N (g/kg) Ap Bi1 Bi2 a
0–20 20–45 45–70
330 390 380
6.0 5.2 5.1
3.6
1.1 0.8 0.7
Determined according to the procedures of EMBRAPA (1997).
0.84 0.12 0.07
0.0 0.6 0.6
11.1 12.0 9.0
251 34 34
14.8 18.0 18.4
0.22 0.25 0.25
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with 200 mL H3PO4 2 M for 30 min. After that, the sample was centrifuged at 1000 rpm for 30 min and it was also Wltered. This procedure was repeated 3 times. The residual soil was washed 3 times with demineralized water and it was shaken with 200 mL Na4P2O7 0.1 M + NaOH 0.1 M for 4 hours. Following centrifugation (3000 rpm/30 min) the supernatant solution (humic + fulvic acids) was separated. This procedure was repeated 3 times as well. The residual soil was used so as to determine the C content of the humin fraction. An aliquot of the supernatant was acidiWed with H2SO4 to pH 1.0 and, then, centrifuged (1500 rpm/5 min) in order to separate the precipitated humic acid from the supernatant fulvic acid. The carbon content of each fraction was determined by dichromate oxidation. Suprapur acids (Merck, Darmstadt, Germany) and ultrapure water (Barnstead Ultrapure Water System, Dubuque, IA, USA) were used in all laboratory procedures. All containers were soaked in 10% HNO3 and thoroughly rinsed in demineralized water before being used. An analysis of variance was used in order to test signiWcance (P < 0.05) of treatment eVects and Tukey’s test (P < 0.05) was used so as to compare the means. All statistical analyses were performed using Statistical Analysis System (SAS, 1999).
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3. Results and discussion 3.1. Chemical composition of the CMW In spite of the fact that there are currently no Brazilian standards in order to evaluate compost quality, the results (Table 3) agree well with the scarce data of chemical analysis of Brazilian CMW. Grossi (1993), during 1990 and 1991, analyzed 61 samples of CMW from 16 Brazilian cities. She found a large range of heavy metal concentrations varying with the maturity degree of the compost (Table 4). Based on it, our results match most of the ranges in heavy metals which were related to the mature compost that we used (Tables 3 and 4). Our results also match the ranges of heavy metals found by Cravo et al. (1998) during their study of the compost produced by six Brazilian waste plant treatments (Tables 3 and 4). Considering the main international legislation on the disposal of biosolids in agriculture (USEPA 40 CFR Part 503 and Council Directive 86/278/ EEC), we realized that, all the metal contents determined in the present study were under the regulation limits (Tables 3 and 4). Notwithstanding, some countries in Europe have more restricted laws (Table 4). In that case, the CMW employed in the present work failed to match the limit
Table 3 Some chemical analyses of the CMW used as amendment for the cultivation of the four vegetables in Brazil N C:N Fe (£103) Mn Cu Cd Co Cr Ni Pb Vegetable crop pH Moisture C (mg kg¡1) (mg kg¡1) (mg kg¡1) (mg kg¡1) (mg kg¡1) (mg kg¡1) (mg kg¡1) (mg kg¡1) (g kg¡1)a (g kg¡1) (g kg¡1) Carrot CauliXower Sweet corn Radish a
7.7 7.7 7.8 7.7
407.2 484.6 440.8 173.8
158.7 162.0 130.9 154.7
15.2 15.4 16.2 17.8
10 11 8 9
12.6 9.3 9.6 21.6
240.2 198.2 203.0 336.2
384.4 170.5 248.0 119.8
2.0 1.4 1.5 1.7
2.0 1.6 1.8 2.5
64.1 56.2 54.0 41.0
28.8 17.1 29.1 20.3
189.0 151.0 153.0 84.0
Wet basis. Relative standard deviation lower than 10% for all analyses.
Table 4 Some chemical analyses of the CMW produced in Brazilian cities compared with various international regulation limits for biosolids disposal in agriculture Source
Fe (£103) (mg kg¡1 dry-matter)
Mn (mg kg¡1 dry-matter)
Cu (mg kg¡1 dry-matter)
Cd (mg kg¡1 dry-matter)
Co (mg kg¡1 dry-matter)
Cr (mg kg¡1 dry-matter)
Ni (mg kg¡1 dry-matter)
Pb (mg kg¡1 dry-matter)
Brazila
23.3 (13.7) 11–23 103–572 88–252 – – –
304 (132) – – – – – –
229 (266) 61–233 72–2991 64–1970 1500 2500 1000–1750
2.8 (1.7) 0.1–0.5 0.3–12.8 0.7–4.5 39 20 20–40
10.8 (4.9)
89.8 (45.1) 76–104 60–278 33–133 1200 500–3000 –
32 (27) 20–31 19–78 17–38 420 270 300–400
238.9 (166.4) 44–342 57–1272 44–274 300 420 750–1200
– – –
– – –
1000 800 75 600
15 10 1.25 2
1000 900 75 100
200 200 30 50
800 900 100 100
Brazilb Brazilc Brazild USAe Australiaf European Communityg Franceg Germanyg Netherlandsg Swedeng a b c d e f g
Cravo et al. (1998), mean and standard deviation, in parenthesis. Grossi (1993) for mature compost. Grossi (1993) for semi-mature compost. Grossi (1993) for raw compost. USEPA (1994) for Exceptional Quality biosolid. Long (2001) for grade B biosolid. Europa (2005).
– –
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Table 5 Metal concentrations of the soil at the experimental site in Nova Friburgo county (Brazil) before the application of compost waste treatments Depth (cm)
Mn (mg kg¡1 dry-matter)
Fe (£103) (mg kg¡1 dry-matter)
Cd (mg kg¡1 dry-matter)
Co (mg kg¡1 dry-matter)
Cr (mg kg¡1 dry-matter)
Cu (mg kg¡1 dry-matter)
Ni (mg kg¡1 dry-matter)
Pb (mg kg¡1 dry-matter)
0–5 5–10 10–20 20–40
401.0 388.6 396.6 388.5
40.7 39.7 41.1 30.8
2.4 2.3 2.1 2.5
18.3 19.0 21.1 22.1
23.5 22.0 22.9 22.8
17.8 17.7 17.2 14.1
20.3 21.7 21.9 20.3
23.9 22.7 23.5 14.7
Relative standard deviation lower than 10% for all analysis.
Yield (t/ha)
20 15 10 5 0 0
25
50
75
100
Composted Municipal Waste Treatments (t/ha)
Fig. 1. Yield (fresh weight) of successively grown carrot (root 䉫), cauliXower (Xower 䊐), sweet corn (seed 䉭) and radish (root £) in nonamended and composted municipal waste (CMW) amended soil.
concentrations of Cu, Cd and Pb related to The Netherlands and Pb to Sweden laws. Concerning only the four applications of the CMW used in the experiment, we have observed that there were some variations of trace metals content (Table 3). However, they were probably related to seasonal variations in raw input of the collected municipal waste. The contents of trace metals found in the compost were much higher than in the agricultural soil used (Table 5) for Cu, Cr, and Pb. However, the concentrations of Fe, Mn, Cd, and Co were higher in the soil and the results for Ni varied. The outcomes concerning heavy metal accumulation in soil will be discussed in a coming section. No negative eVect was observed due to the increasing application of compost rates in the yield of the four cultivated vegetables (Fig. 1). Hence, the CMW used seemed to have no phytotoxicity eVect. 3.2. Plant analysis No Cd was detected in the analyzed tissues (Table 6). Depending upon the tissue, there were some other elements, among those determined, which were below limit detection. In that case, they were not shown (Table 6). The eVect of the compost on the uptake of trace metals analyzed is apparently insigniWcant for carrot and sweet corn. For cauliXower, Fe and Cu uptakes decreased after the application of higher rates of CMW. However, Cu and Pb uptakes for radish have increased, although, in the case of Cu, it occurred only with the highest amount of compost application (Table 6). When compared to other studies dealing with metal absorption from crops amended with CMW, our results
show a diVerent trend. Fritz and Venter (1988) studied, in a greenhouse experiment, the heavy metal uptake behavior of lettuce, spinach, carrot, radish, bush bean, and tomato, all of them were grown successively. Their results of leaf analysis, averaged over all species, indicated that Zn, Cu, and Pb increased signiWcantly due to the higher compost rates used. Cd, Cr, and Ni did not show any signiWcant variation. Root crops had shown a signiWcant increase of Zn. However, only carrot roots exhibited a considerable increase of Pb and Cr contents. Fruit crops have shown signiWcant diVerences for Zn, Ni, Cd, and Cr, but only for the intermediate CMW doses. Costa et al. (1994) observed, in a greenhouse experiment with lettuce, increased Zn, Cu, Cd, and Pb leaf contents with increasing compost rates. Abdel-Sabour and Abo El-Seoud (1996) observed, in sesame seeds, an increase of Pb and Cd concentrations with CMW treatments in relation to the control. Pinamonti et al. (1997) found a signiWcant increase in Ni and Cr in the leaves and fruits of an apple orchard, but only for the highest doses of CMW. Costa et al. (1997) observed in a greenhouse experiment that compost application had enhanced Zn, Cu, and Cd accumulation on dry-matter of carrot leaves and roots. The marked heterogeneity among the studies cited above and also to those found in the present work is probably related to the fact that they were dealing with diVerent plant species under diVerent and speciWc soil conditions (Fritz and Venter, 1988; Kabata-Pendias and Pendias, 1992; Pais and Jones, 1997). Based on data given in Table 6 and according to Kabata-Pendias and Pendias (1992), it is possible to aYrm that there was no metal concentration above the level considered critical for plant tissues in general. However, our results must be viewed cautiously. The experiment with composted waste endured two years only, and in some treatments a very high rate of CMW (400 t ha¡1) was employed. Consequently, we are not able to state whether any drawback would come out if CMW was used for more than two years, especially when it comes to such high rates of CMW. 3.3. Soil analysis 3.3.1. “Total” metal concentration Soil contents and variabilities (Table 7) were within the range considered normal in soils (Kabata-Pendias and Pendias, 1992; Pais and Jones, 1997), corroborating the fact that no phytotoxicity eVect was found by the application of
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Table 6 Concentration of trace metals in the tissue of four vegetables grown at diVerent rates of composted municipal waste (CMW) application mg/kg¡1a
CVb (%)
CMW rate (t ha¡1) 0.0
12.5
25.0
50.0
100.0
Carrot (root) Fe Mn Cu Cr
269.05a 14.13a 7.50a 0.37a
CauliXower (Xower) Fe Mn Cu Co
101.80a 14.23a 2.77a 0.63a
81.20ab 14.50a 2.25b 0.63a
58.55bc 12.50a 2.02b 0.62a
47.40c 12.22a 2.08b 0.68a
53.23bc 11.52a 2.08b 0.64a
26 11 10 17
30.12a 7.38a 1.75a 0.12a 0.59a 0.37a
26.34a 8.96a 1.93a 0.14a 0.37a 0.92a
29.78a 6.62a 1.60a 0.12a 0.52a 0.50a
29.32a 6.36a 1.78a 0.14a 0.57a 0.55a
28.72a 8.70a 1.45a 0.15a 0.49a 0.81a
31 22 14 26 75 70
2334.96a 28.94a 5.20b 2.11a 1.65a 1.65ab
3070.42a 38.04a 6.68b 2.41a 2.41a 3.39ab
2105.42a 24.72a 5.53b 2.25a 2.14a 2.48ab
3583.75a 42.91a 14.58a 4.33a 2.84a 7.24a
47 39 50 57 51 79
Sweet corn (seed) Fe Mn Cu Cr Ni Pb Radish (root) Fe Mn Cu Ni Co Pb
2776.25a 30.06a 3.14b 3.55a 3.40a 1.14b
219.38a 16.01a 6.96a 0.31a
257.35a 14.01a 8.21a 0.38a
259.95a 11.67a 7.42a 0.38a
251.65a 14.08a 8.81a 0.39a
32 36 19 20
Values in the same line for the same sample followed by the same letter are not signiWcantly diVerent as determined by Tukey’s test (P < 0.05). a Dry matter basis. b CoeYcient of variation from the analysis of variance.
CMW (Fig. 1). The eVect obtained with the studied treatments on the aqua regia (“Total”) heavy metal content, concerning the soil upper layer (0–5 cm) can be related to the amounts of each element introduced by the CMW. Hence, the applied composts have led to a great input of Cu, Cr, and Pb in the original soil (Tables 4 and 5), which caused an important increase in the “Total” concentration of these elements in the soil (Table 7). The “Total” Co content has consistently decreased in virtue of an increase in the amount of CMW (Table 7), due to the fact that the Co content of CMW was lower than the soil Co concentration (Tables 4 and 5). In the case of Fe and Mn, although the same pattern of diVerence between soil and CMW concentrations occurred, similar to the Co, the soil content is in an order of magnitude higher where the dilution by the CMW application is insigniWcant. The concentration of Ni in both the soil and in the CMW did not diVer signiWcantly. As a consequence, there was no signiWcant variation due to CMW application. Cabrera et al. (1989) and Pinamonti et al. (1997) observed that relationship between the soil and CMW heavy metal concentration so as to predict the soil accumulation of these elements. Data for “Total” contents of all studied metals with depth were similar to the corresponding 0–5 cm layer, with the exception of the layer below 20 cm. That is, Pb and Cu concentrations have increased signiWcantly after CMW application and the levels of the other metals have shown
no signiWcant variation. The exception was Cr, since there was no signiWcant diVerence of its content between the 5–10 and the 10–20 cm layers. However, it is possible to say that numerically, the Cr content increased when higher levels of CMW were applied. Hence, the increase of Pb and Cu concentrations, associated with the higher rates of CMW application, in the layers 0–5 cm, 5–10 cm and 10–20 cm probably resulted from the eVect of mixing caused by rototilling the soil to a depth of 15 cm. Data from Co seems to corroborate this. The dilution observed in the 0–5 cm depth, caused by the lower concentration of Co present in CMW than in the soil, occurred also in the 5–10 cm depth. At the depth of 20–40 cm, except for Cr and Ni, most of the metal contents were unaVected by the treatments. The signiWcant diVerence found for Cr at the depth of 20–40 cm was consistent with the trend observed for 5–10, and 10–20 cm layers, although, in that case, it was not statistically signiWcant. The results for Ni showed a slightly low value for the 50 t ha¡1 CMW application, which aVected the statistical mean test. 3.3.2. Sequential extraction Besides soil-to-plant transfer of heavy metals, direct ingestion of soil by humans and animals are important pollutant transport pathways to be considered for land application of biosolids (Ryan and Chaney, 1994; Iskandar and Kirkham, 2001; National Research Council, 2003). Since
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Table 7 Trace metal concentration of the soil one year after the growth of the four vegetables amended with composted municipal waste (CMW) CMW rate (t ha¡1) Fe (£103) (mg kg¡1)
Mn (mg kg¡1) Cu (mg kg¡1)
Cd (mg kg¡1)
Co (mg kg¡1)
Cr (mg kg¡1) Ni (mg kg¡1) Pb (mg kg¡1)
0–5 cm 0.0 12.5 25.0 50.0 100.0 CV (%)a
32.6 36.9 32.7 35.6 33.9 12
290.7 314.2 299.7 343.9 298.8 9
11.4d 20.7c 24.6c 42.1b 60.9a 18
1.9 2.4 1.9 2.4 2.5 2
17.2ab 18.5a 16.2ab 16.5ab 12.5b 13
15.7b 21.6ab 20.9ab 27.1a 29.1a 16
17.5 21.2 18.6 22.1 21.2 14
19.2c 26.9c 28.5c 46.7b 60.2a 14
5–10 cm 0.0 12.5 25.0 50.0 100.0 CV (%)
35.2 36.2 33.1 36.4 33.1 10
297.2 300.0 317.4 328.5 290.5 11
15.7c 17.6bc 16.0c 33.2ab 46.4a 28
1.8 2.4 1.8 2.4 2.2 23
16.5ab 16.8ab 17.2a 16.5ab 13.1b 11
17.7 19.4 18.3 29.5 26.0 23
17.4 19.9 18.0 21.4 18.1 23
23.0b 24.9b 29.8ab 37.8ab 47.4a 25
10–20 cm 0.0 12.5 25.0 50.0 100.0 CV (%)
34.5 37.8 28.6 36.0 32.9 14
313.2 304.1 278.5 326.0 292.2 16
16.0b 16.7b 13.1b 27.5ab 35.0a 30
1.8 2.5 2.4 2.2 2.1 20
17.1 17.0 15.8 18.3 16.1 17
19.4 19.2 16.0 22.6 21.9 20
19.4 18.6 18.1 19.5 18.1 20
25.6ab 22.7b 18.9b 33.5ab 37.6a 24
20–40 cm 0.0 12.5 25.0 50.0 100.0 CV (%)
30.4 33.1 32.2 30.4 31.4 14
308.2 277 318.1 273.0 278.9 8
10.6 12.1 11.0 9.9 14.8 27
1.6 2.4 1.8 1.8 1.8 22
17.4 16.0 17.2 16.6 16.8 8
15.3ab 15.8ab 15.7ab 13.3b 19.1a 14
18.2a 15.4ab 15.9ab 12.0b 15.1b 11
14.9 15.9 20.0 15.5 20.2 32
Values in the same line for the same sample followed by the same letter are not signiWcantly diVerent as determined by Tukey’s test (P < 0.05). a CoeYcient of variation from the analysis of variance.
most of the above processes occur in the upper layer of soil, only the results for the 0–5 cm layer will be discussed here. It has been shown that contrary to the determination of the total content of any heavy metal in soil, chemical fractionation may provide more useful information concerning the mobility and bioavailability of heavy metals in soil (Tack and Verloo, 1995; Quevauviller, 1998). Sequential extraction procedures allow this fractionation by assuming that diVerent extracting solutions, applied in a speciWc sequence, will act on diVerent species or binding forms in the soil (Verloo and Eeckhout, 1990; López-Sánchez et al., 2002). The binding form in the solid phase of the soil is related to the intensity of metal release to the liquid phase and hence likelihood of mobilization and bioavailability (Tack and Verloo, 1995). In the fractionation scheme used in this work (Table 2), fractions 1–3 are more likely to represent the equilibrium between the liquid and solid phases than fractions 4 and 5 which are presumed to be the more structurally bound elements occluded in Fe and Mn oxides, strongly adsorbed to Al oxides or residual forms of silicates. The concentrations of Fe, Mn, Cu, Cd, Ni, and Pb in the Wve fractions resultant from all treatments are presented in Fig. 2. Except for Cu, most of the extracted metals were associated with the residual fraction (F5). The distribution of Cu was diVerent from that of other heavy metals. The organically bound fraction (F3) concentrated most of the
Cu analyzed in all treatments and the amount of Cu in F3 has increased signiWcantly with increasing rates of CMW application. Although the other fractions were extracted in lower proportions, a signiWcant increase in the carbonate/ exchangeable and the Al oxide + strong Fe/Mn oxidebound fractions (F1 and F4, respectively) was observed towards the higher CMW applications. As it can be seen in Fig. 2, despite the large amount of the residual fraction, Mn, Pb, and Cd also showed a signiWcant increase in the carbonate/exchangeable fraction (F1) with increasing CMW rates. The organically bound fraction (F3) has signiWcantly increased for Pb and Cd as well. 3.3.3. Humic fractions Rototilling the soil with no amendment application (0 t ha¡1) changed the humus composition signiWcantly compared to the soil before the experiment started (Table 8). The non-humic fraction (NHC) decreased, because the mineralization of the organic matter increased. The lowering of the total organic carbon (TOC) content corroborates this observation (Table 8). The concentration of fulvic acids (FA) slightly increased as a consequence of this process of mineralization. With the application of higher rates of CMW, the NHC content decreased, and, in the case of the 50 t ha¡1 application, it was almost not detected. These results corroborate the Wndings of Kononova (1984) that soil cultivation
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Fig. 2. Concentrations of Mn, Fe, Cu, Pb, Cd, Ni in solid phase components of non-amended and composted municipal waste (CMW) amended soil. Fractions 1–5 represent exchangeable/carbonate, Fe/Mn oxide bound, organically bound, Al oxide plus strong Fe/Mn oxide bound, and residual fractions, respectively. Table 8 Humic fractions extracted from the soil one year after the growth of the four vegetables amended with composted municipal waste (CMW) CMW (t ha¡1) Organic C in the humic fractions
0.0 12.5 25.0 50.0 100.0 Controla
TOC (g kg¡1) FA free (g kg¡1) FA bound (g kg¡1) FA total (g kg¡1) HA (g kg¡1)
Humin (g kg¡1)
FA + HA + humin (g kg¡1)
25.0 29.5 26.4 32.1 36.7 35.2
1.78 (71.2) 2.12 (71.9) 1.93 (73.1) 2.63 (81.9) 2.92 (79.6) 1.80 (51.1)
2.29 (91.6) 2.68 (90.8) 2.41 (91.3) 3.20 (99.7) 3.53 (96.2) 2.46 (69.9)
0.20 (8.0) 0.21 (7.1) 0.22 (8.3) 0.21 (6.5) 0.22 (6.0) 0.28 (8.0)
0.19 (7.6) 0.20 (6.8) 0.10 (3.8) 0.15 (4.7) 0.16 (4.4) 0.15 (4.3)
0.39 (15.6) 0.41 (13.9) 0.32 (12.1) 0.36 (11.2) 0.38 (10.4) 0.43 (12.2)
0.12 (4.8) 0.15 (5.1) 0.16 (6.1) 0.21 (6.5) 0.23 (6.3) 0.23 (6.5)
In parenthesis, results in percentage of the total organic carbon (TOC). a Before cultivation, at the start of the experiment.
decreased the non-humic content of soil organic matter. In that case a slight increase of the humic acid fraction (HA) occurred, and, as a consequence, the fulvic acid content
diminished. However, the most important eVect observed was the increase of the humin fraction over the sum of the humic and fulvic acid fractions. This pattern was reported
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by some researchers in cultivated soils of the former Soviet Union (Shevtsova, 1972; Kononova, 1984). In Brazil, Canellas et al. (2001) also observed increased humic substances (humin + FA + HA) by the application of 80 t ha¡1 of CMW to a Brazilian Oxisol. Most of this increase was associated with the increase of the humin fraction. However, they did not observe a signiWcant increase of the HA fraction, but they did observe an increase of the FA fraction. 4. Conclusion Our data indicated that: (a) the availability of Fe, Mn, Cu, Cd, Co, Cr, Pb, and Ni for carrot and sweet corn was not aVected by increasing rates of application of CMW. In the case of cauliXower, only Fe and Cu uptakes were signiWcantly but negatively inXuenced. The only case of signiWcant and positive accumulation occurred for Pb and Cu in radish. (b) the application of CMW has changed the humic fraction distribution of the soil organic matter, mainly by increasing the humin and less so the humic acid concentration. (c) Cu and Pb have signiWcantly accumulated in 0–5 cm layer of the soil with a similar pattern in the depths of 5–10 cm and 10–20 cm. These were mainly attributed to the mixing of soil during tillage. (d) most of the Fe, Mn, Cd, Ni, and Pb were associated with the residual phase (F5) mainly related to the crystal structure of silicate minerals. However, some metals showed increased values of the carbonate/ exchangeable fractions (Pb, Cd, Mn) and of the organically bound fractions (Pb and Cd). Our results suggest that the heavy metal concentrations observed are not likely to cause problems for the estimation of CMW loadings to Brazilian agricultural land. In that case, the use of potentially mineralizable N and P should be considered a more prudent guideline for public policy to restrict the use of CMW in Brazilian soils since they could pose a potential hazard to surface waters. However, considering the short-term nature of this work, further studies will be necessary to conWrm this assumption. Acknowledgements The authors wish to express their gratitude to CNPq and FAPERJ for the scholarship granted, to FAPERJ, FUSB and Embrapa for the Wnancial support, and to the reviewers for the great improvements on our text. References Abdel-Sabour, M.F., Abo El-Seoud, M.A., 1996. EVects of organic-waste compost addition on sesame growth, yield and chemical composition. Agriculture, Ecosystems and Environment 60, 157–164.
Alloway, B.J., 1990. Soil processes and the behaviour of metals. In: Alloway, B.J. (Ed.), Heavy Metals in Soils. Blackie, London, pp. 7–28. Anikwe, M.A.N., Nwobodo, K.C.A., 2002. Long term eVect of municipal waste disposal on soil properties and productivity of site used for urban agriculture in Abakaliki, Nigeria. Bioresource Technology 83, 241–250. Cabrera, F., Diaz, E., Madrid, L., 1989. EVect of using urban compost as manure on soil contents of some nutrients and heavy metals. Journal of Science of Food and Agriculture 47, 159–169. Canellas, L.P., Santos, G. de A., Rumjanek, U.M., Moraes, A.A., Gurid, F., 2001. Distribution of the organic matter and humic acid characteristics in soils with addition of residues of urban origin. Pesquisa Agropecuaria Brasileira 36 (12), 1529–1538. CETESB, 2001. Relatório de estabelecimento de valores orientadores para solos e águas subterrâneas no estado de São Paulo. Companhia de Tecnologia de Saneamento Ambiental, São Paulo (Brazil). URL: http:// www.cetesb.sp.gov.br/Solo/relatorios/aguas_Wnal.zip. de Costa, C.A., Casali, V.W.D., Loures, E.G., Cecon, P.R., Jordão, C.P., 1994. Content level of heavy metals in lettuce (Lactuca sativa L.) fertilized with organic compost from urban waste. Revista Ceres 238, 629–640. de Costa, C.A., Casali, V.W.D., Loures, E.G., Cecon, P.R., Jordão, C.P., 1997. Content of zinc, copper, and cadmium in carrot as aVected by the use on increasing rates of organic compost from urban wastes. Horticultura Brasileira 15, 10–14. Cravo, M.S., Muraoka, T., Giné, M.F., 1998. Chemical characterization of urban waste composts from some Brazilian plants. Brazilian Journal of Soil Science 22, 547–553. EMBRAPA, 1997. Manual de métodos de análise de solo, second ed., Empresa Brasileira de Pesquisa Agropecuária, Rio de Janeiro, Brazil. Europa, 2005. Regulatory report. URL: http://europa.eu.int/comm/environment/waste/sludge/sludge_disposal2a.pdf. Farago, M.E., 1994. Plants and the Chemical Elements. VCH Publishers, New York, NY. Fergusson, J.E., 1990. The Heavy Elements: Chemistry, Environmental Impact and Health EVects. Pergamon Press, Oxford (UK). pp. 377–405. Fritz, D., Venter, F., 1988. Heavy metals in some vegetables crops as inXuenced by municipal waste composts. Acta Horticulturae 222, 51–62. Garcia, C., Hernández, T., Costa, F., Pascual, J.A., 1992. Phytotoxicity due to the agricultural use of urban wastes. Germination Experiments. Journal of the Science of Food and Agriculture 59, 313–319. Grossi, M.G. de L., 1993. Avaliação da qualidade dos produtos obtidos de usinas de compostagem brasileiras de lixo doméstico através de determinação de metais pesados e substâncias orgânicas tóxicas. Universidade de São Paulo, São Paulo (Brazil). Ph.D. Thesis. Hani, H., 1996. Soil Analysis as a tool to predict eVects on the environment. Communications in Soil Science and Plant Analysis 27 (3/4), 289–306. He, X.-T., Traina, S.J., Logan, T.J., 1992. Chemical properties of municipal solid waste composts. Journal of Environmental Quality 21, 318–329. Iskandar, I.K., Kirkham, M.B., 2001. Trace Elements in Soil: Bioavailability, Flux and Transfer. Lewis Publisher, Boca Raton, FL. Kabata-Pendias, A., Pendias, H., 1992. Trace Elements in Soils and Plants. CRC Press, Boca Raton, FL. pp. 67–87. Kononova, M.M., 1984. Organic matter and soil fertility. Soviet Soil Science 16 (4), 71–86. Long, K., 2001. The Use of Biosolids (Sewage Sludge) as a Fertilizer/Soil Conditioner on Dairy Pastures. Dairy Food Safety Victoria, Victoria (Australia). López-Sánchez, J.F., Sahuquillo, A., Rauret, G., Lachica, M., Barahona, E., Gomez, A., Ure, A.M., Muntau, H., Quevauviller, PH., 2002. Extraction procedures for soil analysis. In: Quevauviller, P.H. (Ed.), Methodologies for Soil and Sediment Fractionation Studies. Royal Society of Chemistry, Cambridge (UK), pp. 28–65. National Research Council, 2003. Bioavailability of Contaminants in Soils and Sediments: Processes, Tools and Applications. The National Academies Press, Washington, DC. pp. 52–118. Oshins, C., 1995. Strategies for encouraging the use of organic wastes in agriculture. In: Karlen, D.L., Wright, R.J., Kemper, W.O. (Eds.), Agriculture Utilization of Urban and Industrial By-Products. ASA/CSSSA/ SSSA, Madison, WI, pp. 73–86.
D.V. Pérez et al. / Bioresource Technology 98 (2007) 525–533 Pais, I., Jones Jr. J.B., 1997. The Handbook of Trace Elements. CRC Press, Boca Raton, FL. Pinamonti, F., Stringari, G., Gasperi, F., Zorzi, G., 1997. The use of compost: its eVects on heavy metal levels in soil and plants. Resources, Conservation, and Recycling 21, 129–143. Quevauviller, Ph., 1998. Operationally deWned extraction procedures for soil and sediment analysis. I. Standardization. Trends in Analytical Chemistry 17 (5), 289–298. Ryan, J.A., Chaney, R.L., 1994. Development of limits for land application of municipal sewage sludge: risk assessment. In: 5th World Congress of Soil Science. In: Transactions, vol. 3a. The International Society of Soil Science/Mexican Society of Soil Science, Acapulco (Mexico), pp. 534–553. SANEPAR, 1997. Manual técnico para utilização agrícola do lodo de esgoto no Paraná. Companhia de Saneamento do Paraná, Curitiba, Brazil. SAS, 1999. SAS System for Windows (vol. 8). SAS Institute Inc., Cary, NC. CD-ROM. Sastriques, F.O., 1982. La materia organica de los suelos y el humus de los suelos de Cuba. Editora de la Academia de Ciencia de Cuba, La Habana, Cuba. Scancar, J., Milacic, R., Strazar, M., Burica, O., 2000. Total metal concentrations and partioning of Cd, Cr, Cu, Fe, Ni and Zn in sewage sludge. The Science of the Total Environment 250, 9–19.
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Shevtsova, L.K., 1972. Methods of studying organic matter in continuously fertilized soils. Soviet Soil Science 4 (1), 479–490. Soumaré, M., Tack, F.M.G., Verloo, M.G., 2003. EVects of a municipal solid waste compost and mineral fertilization on plant growth in two tropical agricultural soils of Mali. Bioresource Technology 86, 15–20. Tack, F.M.G., Verloo, M.G., 1995. Chemical speciation and fractionation in soil and sediment heavy metal analysis: a review. International Journal of Environmental Analytical Chemistry 59, 225–238. USEPA, 1994. Land application of sewage sludge: a guide for land appliers on the requirements of the federal standards for the use or disposal of sewage sludge, 40 CFR Part 503. Environmental Protection Agency OYce of Wastewater Management. Washington, DC. URL: http:// www.epa.gov/owm/mtb/biosolids/sludge.pdf. Verloo, M., Eeckhout, M., 1990. Metal species transformation in soils: an analytical approach. International Journal of Environmental Analytical Chemistry 39, 179–186. Walter, I., Cuevas, G., 1999. Chemical fractionation of heavy metals in a soil amended with repeated sewage sludge application. The Science of the Total Environment 226, 113–119. Wasserman, M.A., Viana, A.G., Bartoly, F., Perez, D.V., Ruas Rochedo, E., Wasserman, J.C., de Conti, C.C., Vivone, R.J., 2005. Bio-geochemical behavior of 90Sr and 137Cs in tropical soil. Radioprotection 40, S135–S142.
Composted municipal waste eVects on chemical properties of a Brazilian soil D.V. Pérez a,¤, S. Alcantara b, C.C. Ribeiro b, R.E. Pereira b, G.C. Fontes b, M.A. Wasserman c, T.C. Venezuela d, N.A. Meneguelli a, J.R. de Macedo a, C.A.A. Barradas e a Embrapa-Solos, R. Jardim Botânico, 1024, Rio de Janeiro (RJ), Brazil Instituto de Química, UFRJ, Av. Brig. Trompovsky, s/no, Cidade Universitária, Rio de Janeiro (RJ), Brazil c Instituto de Radioproteção e Dosimetria/CNEN. Av. Salvador Allende s/no, Recreio, Rio de Janeiro (RJ), Brazil d Fiocruz/ENSP, R. Leopoldo Bulhões, 1480, Rio de Janeiro (RJ), 21041-210, Brazil e PESAGRO-RIO, R. Euclydes Solon Pontes no 30, Nova Friburgo (RJ), 28.625-020, Brazil b
Received 4 January 2004; received in revised form 12 January 2006; accepted 7 February 2006 Available online 31 March 2006
Abstract The spread of composted municipal waste (CMW) on land can be used for sustainable crop production. Nevertheless, heavy metals availability may be a problem. Therefore, the main objective of this study was to assess the impact of CMW disposal on heavy metal accumulation in soil and plants. The treatments consisted of an untreated plot (control) and four rates of CMW application. All plots were cultivated in succession of carrot, cauliXower, sweet corn, and radish. Cu and Pb signiWcantly accumulated in the topsoil (0–5 cm) with a similar pattern in the depths of 5–10 cm and 10–20 cm. CauliXower, for Fe and Cu, and radish, for Pb and Cu, had their tissue analysis signiWcantly aVected due to the increasing rates of application of CMW. Nevertheless, the levels of accumulation in both, soil and plant, are within permissible limits. The evidences provided by this experiment indicated that heavy metals are less likely to cause problems for the estimation of CMW loadings to Brazilian agricultural land. © 2006 Elsevier Ltd. All rights reserved. Keywords: Municipal waste; Biosolid; Heavy metals; Soil properties
1. Introduction Municipal solid waste has been a serious environmental problem for many cities in developing countries (AbdelSabour and Abo El-Seoud, 1996; Soumaré et al., 2003). For instance, Rio de Janeiro, the second largest city in Brazil, has shown over the last years a signiWcant increase of solid waste handling. From 1995 to 2002, the total waste collected and the average waste collected per day increased from 2.6 to 3.6 million tons and 7.0 to 9.9 thousand tons, respectively.
*
Corresponding author. E-mail address: [email protected] (D.V. Pérez).
0960-8524/$ - see front matter © 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2006.02.025
In spite of the fact that there are many kinds of Wnal disposal available, the agricultural practice of amending soils with composted municipal waste (CMW) has received worldwide attention. This compost is rich in organic matter and its use may improve soil fertility and physical properties (He et al., 1992; Oshins, 1995; Anikwe and Nwobodo, 2002). However, repeated compost application can lead to accumulation of trace metals in soils that could eventually contaminate human and other animal food chains (Garcia et al., 1992; Pinamonti et al., 1997; National Research Council, 2003). There are currently no standards to evaluate compost quality in Brazil. Only Paraná and São Paulo states have set up guidelines based on the criteria for sludge (Sanepar, 1997; CETESB, 2001). Hence, there is a need to develop
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general standards for land application of urban waste. Our objectives were to determine: (i) the eVect of CMW application on the heavy metal composition of four vegetable crops and (ii) the residual eVects of this soil amendment on chemical properties of a Brazilian soil. 2. Methods All the composted municipal waste used during this study was taken from the largest treatment plant (Caju) of Rio de Janeiro State, and it was applied from 1995 to 1997 to a soil (Dystrochrept) located in Nova Friburgo County (22°15⬘S and 42°45⬘W), a representative mountain area of intensive vegetable production. The Köppen climate classiWcation is Cwb with mean annual temperature of 18 °C and mean annual precipitation of 1431 mm. In Caju plant, recyclable materials such as paper, glass and aluminum cans are manually removed early in the composting process. The remaining material is ground and the ferrous materials are separated using an electromagnet. The remaining organic waste is sieved and arranged into rows of long piles, and aerated by turning the pile periodically with mechanical means. Generally, 77–90 days are necessary to complete the composting. Some characteristics of the soil used in this study are presented in Table 1. The experimental Weld design was a randomized complete block, consisting of an untreated plot (control) and four rates of CMW surface application (12.5, 25, 50, 100 t ha¡1, wet basis) and four blocks. No inorganic fertilizer was applied. Irrigation was also applied so as to keep soil moisture in the range of Weld capacity. Each plot had a total area of 4.0 £ 2.4 m2 separated in all directions by a border of 1 m. All plots were cultivated with the following crop succession: carrot, planted on November 22nd 1995 and harvested on April 2nd 1996; cauliXower, planted on May 23rd 1996 and harvested on September 5th 1996; sweet corn, planted on December 10th 1996 and harvested on April 10th 1997; and radish, planted on August 20th 1997 and harvested on October 21st 1997. These species were selected due to the fact that they present diVerent edible plant parts (root, Xower, seed) and, consequently, diVerent nutrient uptake paths (Farago, 1994). They are also sensitive crops for diVerent metal toxicities (Alloway, 1990; Fergusson, 1990; Kabata-Pendias and Pendias, 1992). Rotary tilling was used in order to prepare the soil since it mixes the upper layers of soil rather than completely turning the soil over. In the present study, tillage went to the Wrst 15 cm of the soil. Moreover, the direction of the rotary tilling was inverted after each cultivation so as to avoid
Table 2 Procedure of the sequential extraction scheme used to fractionate heavy metals in soil samples Fraction
Sequence of extraction
(F1) Exchangeable + carbonate bound
HAc (2 M) + NaAc (2 M) 1:1; pH 4.7 Room temperature/16 h
(F2) Fe & Mn oxide bound
NH2OH · HCl (0,1 M); pH 2 (HNO3) Room temperature/16 h
(F3) Organically bound
H2O2 (30%) + HNO3 (0.02 M) + NH4Ac (1 M) Room temperature/16 h
(F4) Al oxide + strong Fe & Mn oxide bound
NaOH (0.1 M); pH 12 Room temperature/16 h
(F5) Residual
Aqua regia (HNO3/HCl; 1:3) 50 °C/30 min
plot-to-plot contamination. The compost treatments were superWcially applied in the same day of planting. Hence, a total amount of 50, 100, 200, and 400 t ha¡1 CMW was applied during the experiment. After the Wrst year of the last CMW spread (1998), soil samples were collected from four depths (0–5, 5–10, 10–20, 20–40 cm). The samples were dried in a forced air oven at 40 °C, passed thorough a 2-mm sieve and stored in a polyethylene bag. Vegetable edible parts were rinsed with distilled water, after that they were dried at 70 °C and ground in a stainless steel Wiley mill in order to pass a 1 mm sieve. Ground samples were stored at room temperature in acid-washed polyethylene containers. Aqua regia (HCl/HNO3, 3:1) extraction is used in order to evaluate anthropogenic inputs of heavy metals and it is rather eYcient (Hani, 1996; Walter and Cuevas, 1999; Scancar et al., 2000). Hence, this method was applied for soil and compost evaluation of Fe, Mn, Zn, Cu, Cd, Cr, Pb, and Ni. Therefore, considering the accumulation of some metals observed in the 0–5 cm, a sequential extraction method (Wasserman et al., 2005; Table 2) was used in order to specify the types of metal associations in soil. Dried plant samples were digested with a nitric/perchloric acid mixture. The content of the selected metals was analyzed by ICP-OES (Perkin–Elmer OPTIMA 3000, Norwalk, CT, USA). Duplicate analyses of each soil and plant extractions were performed throughout the work as well. The humic fractions of the soil were sequentially extracted according to Kononova and Bel’Chikova (Sastriques, 1982). In short, the free fulvic acids (not bound) were obtained by shaking 20–40 g of soil (air dried, 2 mm-sieved)
Table 1 Some physical and chemical characteristicsa of the soil used in the experiment Horizon Depth (cm) Clay (g/kg) pH (H2O) Ca2+ + Mg2+ (cmolc/kg) K+ (cmolc/kg) Al3+ (cmolc/kg) CEC (cmolc/kg) P (mg kg¡1) C (g/kg) N (g/kg) Ap Bi1 Bi2 a
0–20 20–45 45–70
330 390 380
6.0 5.2 5.1
3.6
1.1 0.8 0.7
Determined according to the procedures of EMBRAPA (1997).
0.84 0.12 0.07
0.0 0.6 0.6
11.1 12.0 9.0
251 34 34
14.8 18.0 18.4
0.22 0.25 0.25
D.V. Pérez et al. / Bioresource Technology 98 (2007) 525–533
with 200 mL H3PO4 2 M for 30 min. After that, the sample was centrifuged at 1000 rpm for 30 min and it was also Wltered. This procedure was repeated 3 times. The residual soil was washed 3 times with demineralized water and it was shaken with 200 mL Na4P2O7 0.1 M + NaOH 0.1 M for 4 hours. Following centrifugation (3000 rpm/30 min) the supernatant solution (humic + fulvic acids) was separated. This procedure was repeated 3 times as well. The residual soil was used so as to determine the C content of the humin fraction. An aliquot of the supernatant was acidiWed with H2SO4 to pH 1.0 and, then, centrifuged (1500 rpm/5 min) in order to separate the precipitated humic acid from the supernatant fulvic acid. The carbon content of each fraction was determined by dichromate oxidation. Suprapur acids (Merck, Darmstadt, Germany) and ultrapure water (Barnstead Ultrapure Water System, Dubuque, IA, USA) were used in all laboratory procedures. All containers were soaked in 10% HNO3 and thoroughly rinsed in demineralized water before being used. An analysis of variance was used in order to test signiWcance (P < 0.05) of treatment eVects and Tukey’s test (P < 0.05) was used so as to compare the means. All statistical analyses were performed using Statistical Analysis System (SAS, 1999).
527
3. Results and discussion 3.1. Chemical composition of the CMW In spite of the fact that there are currently no Brazilian standards in order to evaluate compost quality, the results (Table 3) agree well with the scarce data of chemical analysis of Brazilian CMW. Grossi (1993), during 1990 and 1991, analyzed 61 samples of CMW from 16 Brazilian cities. She found a large range of heavy metal concentrations varying with the maturity degree of the compost (Table 4). Based on it, our results match most of the ranges in heavy metals which were related to the mature compost that we used (Tables 3 and 4). Our results also match the ranges of heavy metals found by Cravo et al. (1998) during their study of the compost produced by six Brazilian waste plant treatments (Tables 3 and 4). Considering the main international legislation on the disposal of biosolids in agriculture (USEPA 40 CFR Part 503 and Council Directive 86/278/ EEC), we realized that, all the metal contents determined in the present study were under the regulation limits (Tables 3 and 4). Notwithstanding, some countries in Europe have more restricted laws (Table 4). In that case, the CMW employed in the present work failed to match the limit
Table 3 Some chemical analyses of the CMW used as amendment for the cultivation of the four vegetables in Brazil N C:N Fe (£103) Mn Cu Cd Co Cr Ni Pb Vegetable crop pH Moisture C (mg kg¡1) (mg kg¡1) (mg kg¡1) (mg kg¡1) (mg kg¡1) (mg kg¡1) (mg kg¡1) (mg kg¡1) (g kg¡1)a (g kg¡1) (g kg¡1) Carrot CauliXower Sweet corn Radish a
7.7 7.7 7.8 7.7
407.2 484.6 440.8 173.8
158.7 162.0 130.9 154.7
15.2 15.4 16.2 17.8
10 11 8 9
12.6 9.3 9.6 21.6
240.2 198.2 203.0 336.2
384.4 170.5 248.0 119.8
2.0 1.4 1.5 1.7
2.0 1.6 1.8 2.5
64.1 56.2 54.0 41.0
28.8 17.1 29.1 20.3
189.0 151.0 153.0 84.0
Wet basis. Relative standard deviation lower than 10% for all analyses.
Table 4 Some chemical analyses of the CMW produced in Brazilian cities compared with various international regulation limits for biosolids disposal in agriculture Source
Fe (£103) (mg kg¡1 dry-matter)
Mn (mg kg¡1 dry-matter)
Cu (mg kg¡1 dry-matter)
Cd (mg kg¡1 dry-matter)
Co (mg kg¡1 dry-matter)
Cr (mg kg¡1 dry-matter)
Ni (mg kg¡1 dry-matter)
Pb (mg kg¡1 dry-matter)
Brazila
23.3 (13.7) 11–23 103–572 88–252 – – –
304 (132) – – – – – –
229 (266) 61–233 72–2991 64–1970 1500 2500 1000–1750
2.8 (1.7) 0.1–0.5 0.3–12.8 0.7–4.5 39 20 20–40
10.8 (4.9)
89.8 (45.1) 76–104 60–278 33–133 1200 500–3000 –
32 (27) 20–31 19–78 17–38 420 270 300–400
238.9 (166.4) 44–342 57–1272 44–274 300 420 750–1200
– – –
– – –
1000 800 75 600
15 10 1.25 2
1000 900 75 100
200 200 30 50
800 900 100 100
Brazilb Brazilc Brazild USAe Australiaf European Communityg Franceg Germanyg Netherlandsg Swedeng a b c d e f g
Cravo et al. (1998), mean and standard deviation, in parenthesis. Grossi (1993) for mature compost. Grossi (1993) for semi-mature compost. Grossi (1993) for raw compost. USEPA (1994) for Exceptional Quality biosolid. Long (2001) for grade B biosolid. Europa (2005).
– –
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Table 5 Metal concentrations of the soil at the experimental site in Nova Friburgo county (Brazil) before the application of compost waste treatments Depth (cm)
Mn (mg kg¡1 dry-matter)
Fe (£103) (mg kg¡1 dry-matter)
Cd (mg kg¡1 dry-matter)
Co (mg kg¡1 dry-matter)
Cr (mg kg¡1 dry-matter)
Cu (mg kg¡1 dry-matter)
Ni (mg kg¡1 dry-matter)
Pb (mg kg¡1 dry-matter)
0–5 5–10 10–20 20–40
401.0 388.6 396.6 388.5
40.7 39.7 41.1 30.8
2.4 2.3 2.1 2.5
18.3 19.0 21.1 22.1
23.5 22.0 22.9 22.8
17.8 17.7 17.2 14.1
20.3 21.7 21.9 20.3
23.9 22.7 23.5 14.7
Relative standard deviation lower than 10% for all analysis.
Yield (t/ha)
20 15 10 5 0 0
25
50
75
100
Composted Municipal Waste Treatments (t/ha)
Fig. 1. Yield (fresh weight) of successively grown carrot (root 䉫), cauliXower (Xower 䊐), sweet corn (seed 䉭) and radish (root £) in nonamended and composted municipal waste (CMW) amended soil.
concentrations of Cu, Cd and Pb related to The Netherlands and Pb to Sweden laws. Concerning only the four applications of the CMW used in the experiment, we have observed that there were some variations of trace metals content (Table 3). However, they were probably related to seasonal variations in raw input of the collected municipal waste. The contents of trace metals found in the compost were much higher than in the agricultural soil used (Table 5) for Cu, Cr, and Pb. However, the concentrations of Fe, Mn, Cd, and Co were higher in the soil and the results for Ni varied. The outcomes concerning heavy metal accumulation in soil will be discussed in a coming section. No negative eVect was observed due to the increasing application of compost rates in the yield of the four cultivated vegetables (Fig. 1). Hence, the CMW used seemed to have no phytotoxicity eVect. 3.2. Plant analysis No Cd was detected in the analyzed tissues (Table 6). Depending upon the tissue, there were some other elements, among those determined, which were below limit detection. In that case, they were not shown (Table 6). The eVect of the compost on the uptake of trace metals analyzed is apparently insigniWcant for carrot and sweet corn. For cauliXower, Fe and Cu uptakes decreased after the application of higher rates of CMW. However, Cu and Pb uptakes for radish have increased, although, in the case of Cu, it occurred only with the highest amount of compost application (Table 6). When compared to other studies dealing with metal absorption from crops amended with CMW, our results
show a diVerent trend. Fritz and Venter (1988) studied, in a greenhouse experiment, the heavy metal uptake behavior of lettuce, spinach, carrot, radish, bush bean, and tomato, all of them were grown successively. Their results of leaf analysis, averaged over all species, indicated that Zn, Cu, and Pb increased signiWcantly due to the higher compost rates used. Cd, Cr, and Ni did not show any signiWcant variation. Root crops had shown a signiWcant increase of Zn. However, only carrot roots exhibited a considerable increase of Pb and Cr contents. Fruit crops have shown signiWcant diVerences for Zn, Ni, Cd, and Cr, but only for the intermediate CMW doses. Costa et al. (1994) observed, in a greenhouse experiment with lettuce, increased Zn, Cu, Cd, and Pb leaf contents with increasing compost rates. Abdel-Sabour and Abo El-Seoud (1996) observed, in sesame seeds, an increase of Pb and Cd concentrations with CMW treatments in relation to the control. Pinamonti et al. (1997) found a signiWcant increase in Ni and Cr in the leaves and fruits of an apple orchard, but only for the highest doses of CMW. Costa et al. (1997) observed in a greenhouse experiment that compost application had enhanced Zn, Cu, and Cd accumulation on dry-matter of carrot leaves and roots. The marked heterogeneity among the studies cited above and also to those found in the present work is probably related to the fact that they were dealing with diVerent plant species under diVerent and speciWc soil conditions (Fritz and Venter, 1988; Kabata-Pendias and Pendias, 1992; Pais and Jones, 1997). Based on data given in Table 6 and according to Kabata-Pendias and Pendias (1992), it is possible to aYrm that there was no metal concentration above the level considered critical for plant tissues in general. However, our results must be viewed cautiously. The experiment with composted waste endured two years only, and in some treatments a very high rate of CMW (400 t ha¡1) was employed. Consequently, we are not able to state whether any drawback would come out if CMW was used for more than two years, especially when it comes to such high rates of CMW. 3.3. Soil analysis 3.3.1. “Total” metal concentration Soil contents and variabilities (Table 7) were within the range considered normal in soils (Kabata-Pendias and Pendias, 1992; Pais and Jones, 1997), corroborating the fact that no phytotoxicity eVect was found by the application of
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Table 6 Concentration of trace metals in the tissue of four vegetables grown at diVerent rates of composted municipal waste (CMW) application mg/kg¡1a
CVb (%)
CMW rate (t ha¡1) 0.0
12.5
25.0
50.0
100.0
Carrot (root) Fe Mn Cu Cr
269.05a 14.13a 7.50a 0.37a
CauliXower (Xower) Fe Mn Cu Co
101.80a 14.23a 2.77a 0.63a
81.20ab 14.50a 2.25b 0.63a
58.55bc 12.50a 2.02b 0.62a
47.40c 12.22a 2.08b 0.68a
53.23bc 11.52a 2.08b 0.64a
26 11 10 17
30.12a 7.38a 1.75a 0.12a 0.59a 0.37a
26.34a 8.96a 1.93a 0.14a 0.37a 0.92a
29.78a 6.62a 1.60a 0.12a 0.52a 0.50a
29.32a 6.36a 1.78a 0.14a 0.57a 0.55a
28.72a 8.70a 1.45a 0.15a 0.49a 0.81a
31 22 14 26 75 70
2334.96a 28.94a 5.20b 2.11a 1.65a 1.65ab
3070.42a 38.04a 6.68b 2.41a 2.41a 3.39ab
2105.42a 24.72a 5.53b 2.25a 2.14a 2.48ab
3583.75a 42.91a 14.58a 4.33a 2.84a 7.24a
47 39 50 57 51 79
Sweet corn (seed) Fe Mn Cu Cr Ni Pb Radish (root) Fe Mn Cu Ni Co Pb
2776.25a 30.06a 3.14b 3.55a 3.40a 1.14b
219.38a 16.01a 6.96a 0.31a
257.35a 14.01a 8.21a 0.38a
259.95a 11.67a 7.42a 0.38a
251.65a 14.08a 8.81a 0.39a
32 36 19 20
Values in the same line for the same sample followed by the same letter are not signiWcantly diVerent as determined by Tukey’s test (P < 0.05). a Dry matter basis. b CoeYcient of variation from the analysis of variance.
CMW (Fig. 1). The eVect obtained with the studied treatments on the aqua regia (“Total”) heavy metal content, concerning the soil upper layer (0–5 cm) can be related to the amounts of each element introduced by the CMW. Hence, the applied composts have led to a great input of Cu, Cr, and Pb in the original soil (Tables 4 and 5), which caused an important increase in the “Total” concentration of these elements in the soil (Table 7). The “Total” Co content has consistently decreased in virtue of an increase in the amount of CMW (Table 7), due to the fact that the Co content of CMW was lower than the soil Co concentration (Tables 4 and 5). In the case of Fe and Mn, although the same pattern of diVerence between soil and CMW concentrations occurred, similar to the Co, the soil content is in an order of magnitude higher where the dilution by the CMW application is insigniWcant. The concentration of Ni in both the soil and in the CMW did not diVer signiWcantly. As a consequence, there was no signiWcant variation due to CMW application. Cabrera et al. (1989) and Pinamonti et al. (1997) observed that relationship between the soil and CMW heavy metal concentration so as to predict the soil accumulation of these elements. Data for “Total” contents of all studied metals with depth were similar to the corresponding 0–5 cm layer, with the exception of the layer below 20 cm. That is, Pb and Cu concentrations have increased signiWcantly after CMW application and the levels of the other metals have shown
no signiWcant variation. The exception was Cr, since there was no signiWcant diVerence of its content between the 5–10 and the 10–20 cm layers. However, it is possible to say that numerically, the Cr content increased when higher levels of CMW were applied. Hence, the increase of Pb and Cu concentrations, associated with the higher rates of CMW application, in the layers 0–5 cm, 5–10 cm and 10–20 cm probably resulted from the eVect of mixing caused by rototilling the soil to a depth of 15 cm. Data from Co seems to corroborate this. The dilution observed in the 0–5 cm depth, caused by the lower concentration of Co present in CMW than in the soil, occurred also in the 5–10 cm depth. At the depth of 20–40 cm, except for Cr and Ni, most of the metal contents were unaVected by the treatments. The signiWcant diVerence found for Cr at the depth of 20–40 cm was consistent with the trend observed for 5–10, and 10–20 cm layers, although, in that case, it was not statistically signiWcant. The results for Ni showed a slightly low value for the 50 t ha¡1 CMW application, which aVected the statistical mean test. 3.3.2. Sequential extraction Besides soil-to-plant transfer of heavy metals, direct ingestion of soil by humans and animals are important pollutant transport pathways to be considered for land application of biosolids (Ryan and Chaney, 1994; Iskandar and Kirkham, 2001; National Research Council, 2003). Since
530
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Table 7 Trace metal concentration of the soil one year after the growth of the four vegetables amended with composted municipal waste (CMW) CMW rate (t ha¡1) Fe (£103) (mg kg¡1)
Mn (mg kg¡1) Cu (mg kg¡1)
Cd (mg kg¡1)
Co (mg kg¡1)
Cr (mg kg¡1) Ni (mg kg¡1) Pb (mg kg¡1)
0–5 cm 0.0 12.5 25.0 50.0 100.0 CV (%)a
32.6 36.9 32.7 35.6 33.9 12
290.7 314.2 299.7 343.9 298.8 9
11.4d 20.7c 24.6c 42.1b 60.9a 18
1.9 2.4 1.9 2.4 2.5 2
17.2ab 18.5a 16.2ab 16.5ab 12.5b 13
15.7b 21.6ab 20.9ab 27.1a 29.1a 16
17.5 21.2 18.6 22.1 21.2 14
19.2c 26.9c 28.5c 46.7b 60.2a 14
5–10 cm 0.0 12.5 25.0 50.0 100.0 CV (%)
35.2 36.2 33.1 36.4 33.1 10
297.2 300.0 317.4 328.5 290.5 11
15.7c 17.6bc 16.0c 33.2ab 46.4a 28
1.8 2.4 1.8 2.4 2.2 23
16.5ab 16.8ab 17.2a 16.5ab 13.1b 11
17.7 19.4 18.3 29.5 26.0 23
17.4 19.9 18.0 21.4 18.1 23
23.0b 24.9b 29.8ab 37.8ab 47.4a 25
10–20 cm 0.0 12.5 25.0 50.0 100.0 CV (%)
34.5 37.8 28.6 36.0 32.9 14
313.2 304.1 278.5 326.0 292.2 16
16.0b 16.7b 13.1b 27.5ab 35.0a 30
1.8 2.5 2.4 2.2 2.1 20
17.1 17.0 15.8 18.3 16.1 17
19.4 19.2 16.0 22.6 21.9 20
19.4 18.6 18.1 19.5 18.1 20
25.6ab 22.7b 18.9b 33.5ab 37.6a 24
20–40 cm 0.0 12.5 25.0 50.0 100.0 CV (%)
30.4 33.1 32.2 30.4 31.4 14
308.2 277 318.1 273.0 278.9 8
10.6 12.1 11.0 9.9 14.8 27
1.6 2.4 1.8 1.8 1.8 22
17.4 16.0 17.2 16.6 16.8 8
15.3ab 15.8ab 15.7ab 13.3b 19.1a 14
18.2a 15.4ab 15.9ab 12.0b 15.1b 11
14.9 15.9 20.0 15.5 20.2 32
Values in the same line for the same sample followed by the same letter are not signiWcantly diVerent as determined by Tukey’s test (P < 0.05). a CoeYcient of variation from the analysis of variance.
most of the above processes occur in the upper layer of soil, only the results for the 0–5 cm layer will be discussed here. It has been shown that contrary to the determination of the total content of any heavy metal in soil, chemical fractionation may provide more useful information concerning the mobility and bioavailability of heavy metals in soil (Tack and Verloo, 1995; Quevauviller, 1998). Sequential extraction procedures allow this fractionation by assuming that diVerent extracting solutions, applied in a speciWc sequence, will act on diVerent species or binding forms in the soil (Verloo and Eeckhout, 1990; López-Sánchez et al., 2002). The binding form in the solid phase of the soil is related to the intensity of metal release to the liquid phase and hence likelihood of mobilization and bioavailability (Tack and Verloo, 1995). In the fractionation scheme used in this work (Table 2), fractions 1–3 are more likely to represent the equilibrium between the liquid and solid phases than fractions 4 and 5 which are presumed to be the more structurally bound elements occluded in Fe and Mn oxides, strongly adsorbed to Al oxides or residual forms of silicates. The concentrations of Fe, Mn, Cu, Cd, Ni, and Pb in the Wve fractions resultant from all treatments are presented in Fig. 2. Except for Cu, most of the extracted metals were associated with the residual fraction (F5). The distribution of Cu was diVerent from that of other heavy metals. The organically bound fraction (F3) concentrated most of the
Cu analyzed in all treatments and the amount of Cu in F3 has increased signiWcantly with increasing rates of CMW application. Although the other fractions were extracted in lower proportions, a signiWcant increase in the carbonate/ exchangeable and the Al oxide + strong Fe/Mn oxidebound fractions (F1 and F4, respectively) was observed towards the higher CMW applications. As it can be seen in Fig. 2, despite the large amount of the residual fraction, Mn, Pb, and Cd also showed a signiWcant increase in the carbonate/exchangeable fraction (F1) with increasing CMW rates. The organically bound fraction (F3) has signiWcantly increased for Pb and Cd as well. 3.3.3. Humic fractions Rototilling the soil with no amendment application (0 t ha¡1) changed the humus composition signiWcantly compared to the soil before the experiment started (Table 8). The non-humic fraction (NHC) decreased, because the mineralization of the organic matter increased. The lowering of the total organic carbon (TOC) content corroborates this observation (Table 8). The concentration of fulvic acids (FA) slightly increased as a consequence of this process of mineralization. With the application of higher rates of CMW, the NHC content decreased, and, in the case of the 50 t ha¡1 application, it was almost not detected. These results corroborate the Wndings of Kononova (1984) that soil cultivation
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531
Fig. 2. Concentrations of Mn, Fe, Cu, Pb, Cd, Ni in solid phase components of non-amended and composted municipal waste (CMW) amended soil. Fractions 1–5 represent exchangeable/carbonate, Fe/Mn oxide bound, organically bound, Al oxide plus strong Fe/Mn oxide bound, and residual fractions, respectively. Table 8 Humic fractions extracted from the soil one year after the growth of the four vegetables amended with composted municipal waste (CMW) CMW (t ha¡1) Organic C in the humic fractions
0.0 12.5 25.0 50.0 100.0 Controla
TOC (g kg¡1) FA free (g kg¡1) FA bound (g kg¡1) FA total (g kg¡1) HA (g kg¡1)
Humin (g kg¡1)
FA + HA + humin (g kg¡1)
25.0 29.5 26.4 32.1 36.7 35.2
1.78 (71.2) 2.12 (71.9) 1.93 (73.1) 2.63 (81.9) 2.92 (79.6) 1.80 (51.1)
2.29 (91.6) 2.68 (90.8) 2.41 (91.3) 3.20 (99.7) 3.53 (96.2) 2.46 (69.9)
0.20 (8.0) 0.21 (7.1) 0.22 (8.3) 0.21 (6.5) 0.22 (6.0) 0.28 (8.0)
0.19 (7.6) 0.20 (6.8) 0.10 (3.8) 0.15 (4.7) 0.16 (4.4) 0.15 (4.3)
0.39 (15.6) 0.41 (13.9) 0.32 (12.1) 0.36 (11.2) 0.38 (10.4) 0.43 (12.2)
0.12 (4.8) 0.15 (5.1) 0.16 (6.1) 0.21 (6.5) 0.23 (6.3) 0.23 (6.5)
In parenthesis, results in percentage of the total organic carbon (TOC). a Before cultivation, at the start of the experiment.
decreased the non-humic content of soil organic matter. In that case a slight increase of the humic acid fraction (HA) occurred, and, as a consequence, the fulvic acid content
diminished. However, the most important eVect observed was the increase of the humin fraction over the sum of the humic and fulvic acid fractions. This pattern was reported
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by some researchers in cultivated soils of the former Soviet Union (Shevtsova, 1972; Kononova, 1984). In Brazil, Canellas et al. (2001) also observed increased humic substances (humin + FA + HA) by the application of 80 t ha¡1 of CMW to a Brazilian Oxisol. Most of this increase was associated with the increase of the humin fraction. However, they did not observe a signiWcant increase of the HA fraction, but they did observe an increase of the FA fraction. 4. Conclusion Our data indicated that: (a) the availability of Fe, Mn, Cu, Cd, Co, Cr, Pb, and Ni for carrot and sweet corn was not aVected by increasing rates of application of CMW. In the case of cauliXower, only Fe and Cu uptakes were signiWcantly but negatively inXuenced. The only case of signiWcant and positive accumulation occurred for Pb and Cu in radish. (b) the application of CMW has changed the humic fraction distribution of the soil organic matter, mainly by increasing the humin and less so the humic acid concentration. (c) Cu and Pb have signiWcantly accumulated in 0–5 cm layer of the soil with a similar pattern in the depths of 5–10 cm and 10–20 cm. These were mainly attributed to the mixing of soil during tillage. (d) most of the Fe, Mn, Cd, Ni, and Pb were associated with the residual phase (F5) mainly related to the crystal structure of silicate minerals. However, some metals showed increased values of the carbonate/ exchangeable fractions (Pb, Cd, Mn) and of the organically bound fractions (Pb and Cd). Our results suggest that the heavy metal concentrations observed are not likely to cause problems for the estimation of CMW loadings to Brazilian agricultural land. In that case, the use of potentially mineralizable N and P should be considered a more prudent guideline for public policy to restrict the use of CMW in Brazilian soils since they could pose a potential hazard to surface waters. However, considering the short-term nature of this work, further studies will be necessary to conWrm this assumption. Acknowledgements The authors wish to express their gratitude to CNPq and FAPERJ for the scholarship granted, to FAPERJ, FUSB and Embrapa for the Wnancial support, and to the reviewers for the great improvements on our text. References Abdel-Sabour, M.F., Abo El-Seoud, M.A., 1996. EVects of organic-waste compost addition on sesame growth, yield and chemical composition. Agriculture, Ecosystems and Environment 60, 157–164.
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